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Newsletter of North East India Research Forum

N. E. Quest; Volume 1, Issue 4, January 2008, 1


Newsletter of North East India Research Forum

Newsletter
of
NORTH EAST INDIA RESEARCH FORUM

http://tech.groups.yahoo.com/group/northeast_india_research/
www.neindiaresearch.org

N. E. Quest; Volume 1, Issue 4, January 2008, 2


Newsletter of North East India Research Forum

EDITORIAL from a complete environmental catastrophe. It


is noteworthy that the climate change will
It is my proud privilege to be the editor for affect the world’s poor most, particularly from
the fourth issue of NE Quest. I am really Africa, Asia and South America. At the recent
honored and at the outset, I could not but UN conference on climate change in Bali,
extend my heartfelt gratitude to all the global warming was the main issue. Lots of
respected and beloved members of the decisions have been taken and we have to look
beautiful forum, NE India Research Forum for forward for their implementation. Being
giving me this opportunity. Interestingly, most among the top carbon emitters, India’s stand in
of the members of the forum have never met this context has to be scrutinized in coming
and will probably never meet. Still the bond days. Here we need a change in our attitude
among us is a reason to smile and it is and have to think more globally. We should be
becoming stronger and stronger day by day. inspired by Al Gore and Rajendra Pachouri,
The increase in the number of forum members Nobel Peace Prize winners for 2007. Let’s
is very encouraging. I believe, our forum will make one resolution in this New Year to save
become one of the focus platforms to cover up our mother earth from global warming.
entire researchers of NE region. Faculty crisis in Indian academic
We heralded in the New Year feeling all institutions has been a long term problem. The
ecstatic and as the revelry over we are all back scenario in the colleges of Assam is even more
on our feet, surely on a fresh and a positive painful and the situation in other NE states is
note. From the experiences and happenings of not an exception. It is not only confined to the
the past, many thoughts have been knocking in quantity but also to the quality. Considering
the mind. Among those, in this editorial, I the Government’s stand, it seems, the situation
would like to shade light only on two points: will become more dangerous on quality
one is ‘global warming’ and the other is ‘the perspective in coming days. The future of the
faculty crisis in our colleges’. educational standard depends on the budding
In many forms, the 19th century concepts students and to produce good students we need
have become obsolete with changes in good teachers. Now the question is, who will
perception and attitude towards various issues join in a college? The answer is ‘no one’ if any
ranging from business to entertainment. other option prevails. The reason? Obviously,
Surprisingly, the environment exists as an the payment scheme. One has to work for two
antithesis of its own nature. Though we think years for a fixed payment that is one third of
ourselves as a part of globalization, in many the fellowship of a research scholar! Isn’t it a
senses, we are not globalized at all. Now, strange? We must confess that after a certain
global warming is emerging as the most severe age, we have to take some extra
warning for the mankind. We have to keep responsibilities and for that we need a good
aside the geographical barriers to fight against earning. To be honest, with knowledge, money
it. We must keep in mind that there is no is the prime necessity for living. Government
distinction like Indian carbon or American has to eye on it for betterment of our future
carbon. Recently, UN report says that there is generation. Otherwise, it is difficult to attract
a small window of opportunity in this century the creamy layer students for those jobs. The
for limiting the global temperature increase to posts can be fulfilled anyway, as there is no
2 °C. If it is not done, humanity will face a scarcity of pass out students. Still the question
series of climate changes that will wreak of quality remains unanswered. It is for sure,
havoc on the planet including flooding of we are going to be the victim and MNCs are
coastal areas, crop failures, epidermis, water ready to take that creamy layer with handful
scarcity, increased natural disaster and many packages.
more. Unfortunately, to handle the problem, At last but not the least, I
the gap between scientific evidences and wish all the members a very
political response remain still large. happy and prosperous New
Developed countries should cut their carbon Year and a fruitful ‘Bhogali
emissions at least by 80% by the year 2050 Bihu’.
with 20-30% cut by 2030 to save the earth
Pranjal Saikia

N. E. Quest; Volume 1, Issue 4, January 2008, 3


Newsletter of North East India Research Forum

CONTENTS
1. THE FORUM 05

2. NORTH EAST INDIANS MADE US PROUD 06

3. NEWS
a. Research and Developments 07
b. Forum Members in News (awards, fellowships, visit etc) 10

4. INSTRUMENT OF THE ISSUE


Single Crystal X-Ray Diffractometer
Mr. Bipul Sarma [ sarmabipul@yahoo.com ] 11

5. ARTICLES:
a. Nanomedicine: Nanoparticles in Drug Delivery
Dr. Jadab Sharma [ jadab.s@gmail.com ] 14

b. Disposable Plastics
Mr. Binoy Kumar Saikia [ binoyrrl@yahoo.com ] 17

c. Biosensor and its Applications


Mr. Manashjit Gogoi [ manash_96@rediffmail.com ] 19

d. Mushroom Poisoning-The Fact


Mr. Mahananda Chutia [ mahanaba@yahoo.co.uk ] 20

e. Nanocomposites and Their Applications


Dr. Sasanka Deka [ deka3sasanka@yahoo.co.in ] 23

f. Polyurethane Chemistry: Fundamentals and Applications


Dr. Smriti Rekha Deka [ srbaruah3003@yahoo.co.in ] 25

6. Ph.D. THESIS ABSTRACT


a. Newer Catalytic Methodologies for C-N, C-S Bonds Formation and
Oxidation of Sulfides, Bromide and Alcohols with H2O2
Dr. Sahid Hussain [ hussains@iitg.ernet.in ] 27

b. Effect of Solvent Media in Altering the Rates of Diels-Alder Reactions


and Other C-C Bond Forming Reactions
Dr. Diganta Sarma [ dsarma22@yahoo.co.in ] 34

7. FIRST FIVE IN CHEMISTRY 38

8. INTRODUCTION OF FORUM MEMBERS 39

9. THROUGH THE LENSES OF FORUM MEMBERS, MESSAGE 40

10. HIGHER STUDY ABROAD 42

N. E. Quest; Volume 1, Issue 4, January 2008, 4


Newsletter of North East India Research Forum

The Forum Choudhury, N. E. QUEST received


the maximum number of votes and
North East India Research Forum was hence it is accepted as the name of the
created on 13th November 2004. Newsletter.
How often should we publish our
1. How we are growing. newsletter '' N. E. Quest'' ?
At the beginning, it was a march 1. Every 3 months = 61%
hardly with few members and today 2. Every 6 months = 38%
the forum comprised of a force of 3. Once a year = 0%
more than 175 researchers.
4. NE-Quest Issues
2. Discussions held in the forum 1. Vol 1 Iss 1 April, 2007
• Necessity of directory of all the Editor: Dr. Arindam Adhikari
members of the forum. 2. Vol 1 Iss 2 July 2007
• Possibility of organising conference in Editor: Dr. Tankeswar Nath
the N E India. 3. Vol 1 Iss 3 Nov 2007
• Taking initiation on setting up of Editor: Dr. Ashim Jyoti Thakur
South East Asian Scientific Institute. 4. Current Issue
• On selection of Best paper award. Editor: Mr. Pranjal Saikia

3. Poll conducted and results 5. Future activities


North East India is lacking behind the rest Proper planning and consequent
of the country due to- implementation always play an
1. Geographical constrain =0% important role in every aspect. Some
2. Bad leadership = 40% of the topics/activities/suggestions
3. Lack of work culture = 36% which were being discussed, time to
4. Corruption = 18% time in the forum will get top
5. Apathy from Central Govt. = 4% priorities in our future activities.
Which area of science is going to Those are mentioned here,
dominate by creating a great impact on • Preparing complete online database of
society in next decade? N.E. researchers with details.
1. Nanoscience & nanotechnology • Organising conference in the N.E.
= 22% region-proposed by Dr. Utpal Bora.
2. Biotechnology = 11% • Research collaboration among forum
3. Nanobiotechnology = 38% members.
4. Chemical Engineering = 0% • Motivate student to opt for science
5. Medicine = 11% education.
6. Others = 16% • Help master’s students in doing
7. None = 0% projects in different organisation-
Kindly let us know your view regarding proposed by Mr. Khirud Gogoi.
the following topic. What activities of this • Supporting schools in rural areas by
group you like most ? different ways.
1. Research articles= 33% • Best paper awards.
2. Information about
vacancy/positions available=10% To run the forum smoothly, to make it
3. Way to have a contact with all more organised and to speed up activities,
members =29% formation of a committee/team is
4. Scientific discussions = 14% essential. The combined discussion of the
5. Others = 2% moderators and senior members make the
Selection of name for Newsletter forum feel the importance of Advisors, co-
There were total 36 proposals ordinator, volunteer, webmasters etc. Of
submitted by members of the forum course it needs more discussion and will
for the Newsletter. The name be approved by poll.
proposed by Mr. Abhishek

N. E. Quest; Volume 1, Issue 4, January 2008, 5


Newsletter of North East India Research Forum

NE Indians Made Us Proud prestigious Cincinnati Children's Hospital


Medical Centre. He did his B.Sc. (1989)
and M.Sc.(1992) from Manipur
University, India. Then he did his Ph.D.
Dr. Pabitra Datta from Indian Institute of Science,
Bangalore, India, in the year 2000. He
received several awards which includes,
Appreciation Award at the 2003 FARF
Scientific Symposium for the discovery of
Dr. Pabitra Datta was born in Jorhat, the FANCL gene (2003); Discovery
Assam. He received a B.S. degree in Award at the 2005 FARF Scientific
Physics and Chemistry from Gauhati Symposium for the cloning of the FANCB
University, Assam, India in June 1960; a and FANCM genes (2005); American
M.S. degree in Physical Chemistry from Society of Hematology Junior Faculty
Drexel University, Philadelphia, PA in Scholar Award (2006-08).
1962, and a Ph.D. degree in Physical
Chemistry from Case-Western Reserve His research focuses on functional
University in 1965. He spent two years of analysis of Fanconi anemia gene
post doctoral work at New York State products. The major research focus
University at Stony Brook, NY. He joined includes identification of new FA genes
Addressograph Multigraph Corporation as and signal transduction pathways that
senior chemist and was promoted to staff regulate DNA damage induced activation
scientist within two years. He joined RCA of the FA-core complex. Important
Laboratories as a Member of the Technical technologies include biochemical
Staff in 1974. purification of multiprotein complexes
from human cell extracts,
His research interests were surface immunoprecipitation, RNAi, and
chemistry, photochemistry, plasma biochemical assays. His long-term
deposition, and physical properties of research goal is to use Fanconi anemia as a
plastics. He received three RCA model system to study some of the
Laboratories' Outstanding Achievement important fundamental questions of cancer
Awards and an RCA Corporation David biology in general.
Sarnoff Award for Outstanding Technical
Achievement. His discovery of the
efficacy of a special carbon as a
conductive filler led to a practical Dr. Khwairakpam
demonstration of the viability of the Gajananda
conductive disc concept. This
breakthrough provided the direction for
developing a manufacturable disc
technology which is employed in the
present product. Dr. Pabitra Datta, at the In yet another pride for the people of
age of 55 passed away on December 13, Manipur, one young scientist from
1997 in New Jersey, USA. Manipur has participated in the 26th
Indian Scientific Expedition to Antarctica
to explore one of the east Antarctic coastal
areas known as Larsemann Hills.
Dr. Ruhikanta A.
Meetei Dr. Khwarirakpam Gajananda who
is presently a Scientist (Environment) at
the prestigious Shriram Institute for
Industrial Research, Delhi University,
Delhi was among the 34 members from
Dr. Ruhikanta A. Meetei, at present different Organisations and Universities in
is working as Assistant Professor at the India for the expedition to the harshest

N. E. Quest; Volume 1, Issue 4, January 2008, 6


Newsletter of North East India Research Forum

continent of the world, Antartica. He was NEWS:


also member of the 18th Indian Scientific Research and Developments
Expedition to Antarctica, 16th Winter
Over Team (WOT), December 1998 to ■ University of Minnesota Center for
March 2000. Drug Design and Minneapolis VA
Medical Center researchers have
He did his B.Sc.(1994) in Botany from discovered a new fast-acting antidote to
Manipur University; M.Sc. (1996) in cyanide poisoning. The antidote has
Environmental Sciences, M-Tech (1998) potential to save lives of those who are
Environmental Science and Engineering, exposed to the chemical – namely
from GJU, Hisar, India. He did his Ph.D in firefighters, industrial workers, and
2003, thesis entitled ‘Study of atmospheric victims of terrorist attacks.Current cyanide
parameters in relation to Antarctic antidotes work slowly and are ineffective
ecosystem over the Schirmacher region of when administered after a certain point,
east Antarctica’. In recognition of his said Steven Patterson, Ph.D., principal
achievement in the field of science and investigator and associate director of the
technology, he was recognized by the University of the Minnesota Center for
Marquis Who’s Who 2007 in the field of Drug Design. “It’s much, much faster
Engineering and Science and Who’s Who than current antidotes,” Patterson said.
in Asia. He was nominated from the “The antidote is also effective over a
Shriram Institute for Industrial Research, wider time window. Giving emergency
Delhi and sponsored by the (NCAOR), responders more time is important because
Vasco-da-Gama, Goa. it’s not likely that someone will be
exposed to cyanide near a paramedic.”
Special Introduction The antidote was tested on animals and
has been exceptionally effective.
Researchers hope to begin human clinical
trials during the next three years. The
antidote is also unique because it can be
taken orally (current antidotes must be
given intravenously) and may be
administered up to an hour prior to
cyanide exposure.

Mr. Anirban Adhikari ■ A study which has found an answer to


one of the most intractable squabbles in
The cover pages of the N. E. Quest
family life -- argumentative and disruptive
have been designed by Mr Anirban
children are born, not made.
Adhikari. Basically from Tinsukia, Assam,
A team of international researchers has
he did his graduation from Fergusson
carried out a study and found a strong
College, Pune in Geology. Then he did his
genetic influence on whether a child
masters in Mass Communication. At
becomes a bully or a victim of bullying,
present, he is working as a Sr. multimedia
The Guardian reported. In fact, according
Developer in a company based in Pune.
to the researchers, genetic influences
explain 73 per cent of kids' risk of being a
[The entire members of the forum take the
victim and 61 per cent of their chance of
opportunity to acknowledge Mr. Adhikari
being a bully. "It's in line with a large
for his constant support and co-operation.]
body of research which shows that
……….Editor psychological traits have quite a high
---------------------0---------------------- degree of genetic influence," lead
researcher Harriet Ball said.
“We are what we repeatedly do.” According to Ball of the Institute of
Aristotle Psychiatry at King's College in London,
---------------------0---------------------- the findings do not imply that genetics

N. E. Quest; Volume 1, Issue 4, January 2008, 7


Newsletter of North East India Research Forum

should be used to blame a child for being scientists have found that a protein called
involved in bullying. "The information Ecadherin is essential to keeping cells
should help schools and parents find new stuck together and when its levels fall,
ways to deal with bullying." (Courtesy: other proteins move to the surface of the
Times of India) cells and they manage to break away and
spread, the Daily Mail reported on
■ South Korean scientists have cloned Thursday. "Understanding how cancer
cats that glow red under ultraviolet light, cells spread is tremendously important for
as part of research aimed at developing cancer research. It is the ability of tumours
treatments for human genetic diseases, say to invade other tissues and spread around
officials. the body that makes them so dangerous.
The cancer just overwhelms the body,"
lead researcher Chris Ward was quoted as
saying. "Potentially, our findings can be
applied to the most common form of
cancer, carcinoma, found in the breast,
lung and gut for example, which makes up
80 to 90 per cent of all cancers," Ward
added. The researchers, who used
embryonic stem cells to unlock the secret
A team of scientists led by Professor Kong behind how cancer spreads around the
Il-keun, a cloning expert at Gyeongsang body, now plan to create drugs that
National University in Jinju, produced interfere with this process. "These findings
three glowing Turkish Angoras cats, say may enhance our ability to come up with
the country's Ministry of Science and more effective drugs". Norman Barrett of
Technology. According to the Korea the Association for International Cancer
Times, the scientists added red Research, which funded the study, said,
fluorescence protein (RFP) genes to the "Dr Ward and his team are pursuing
skin cells of the mother cat. They then research which could change the lives of
inserted the skin cells into ova to produce tens of thousands of people in the United
cloned cats genetically modified to contain Kingdom and many more across the
the RFP gene. "It marked the first time in world". (Courtesy: Nature)
the world that cats with RFP genes have
been cloned," says the ministry of science
■ The Department of Science and
and technology. "The ability to produce
Technology (DST) is looking at ensuring
cloned cats with the manipulated genes is
enrolment of at least 250 PhD students in
significant as it could be used for
nanosciences over the next five years.
developing treatments for genetic diseases
They will be registered in leading central
and for reproducing model [cloned]
and state universities and specialized
animals suffering from the same diseases
research institutes. While it is not clear
as humans." The technology will also help
how many will graduate in a year, 50 pass-
to develop stem cell treatments - noting
outs a year are needed to ensure India has
that cats have some 250 kinds of genetic
at least 250 nano scholars by 2012.
diseases that also affect humans. The
However, fresh scholars cannot register as
technology will also help clone
it would take them a minimum of three
endangered animals like tigers, leopards
years, if not four, to complete their PhD.
and wildcats, Kong says. (Courtesy: The
But as nanoscience is an inter-disciplinary
Ministry of Science and Technology/AFP)
subject, students already enrolled in
courses relating to or contributing to
■ British scientists claim to have nanosciences could be considered nano
discovered the mechanism cancer cells use research scholars. What exactly the
to spread around the body - a research will focus on will have to be
breakthrough which could stop the disease decided by the institution concerned after
right in its tracks. In their research, the consulting senior academics and policy-

N. E. Quest; Volume 1, Issue 4, January 2008, 8


Newsletter of North East India Research Forum

makers in DST. While this move may Two Poems


ensure that India has a fair number of Dr. Tankeswar Nath
nano-scholars in five years, scientists are,
in fact, looking at a much higher number -
500. The fear is that India will fall (1)
desperately short of nano-scholars in five Happy New Year'2008
years, by which time the US, Japan and
China would have a high number of
New year'2008 is in your door step
scholars as well as nano-products. The
Following your remarkable foot-step
doubling would mean 100 PhDs per year
With a bagful magic sticks
and this requires a high rate of enrolment.
The question is whether this will happen at To apply all the latest techniques
a time when there is a declining interest in To bring you a bright change
science in general. There’s hope because In all audible, visible and assessable range
DST has planned 14 nano-centres in the You would be the leader of the leaders
country, some of which will be labs, and To help ride poorest of the poor,
other institutes. If prospects of Weakest of the weak
employment after graduation are good, To the top of the ladder
enrolment is expected to go up rapidly. To unfold the flag of peace and prosperity
The allotment of Rs 1,000 crore for Heralding the world Happy New Year.
nanosciences made by the ministry of
science and technology includes a high (2)
number of scholarships for students as New Yew Wish’ 2006
well as for the new labs and centres.
(Courtesy:Times of India) May you have this NEW YEAR, 2006
As an ocean of inspiration, fresh spirit,
confidence and resolve,
■ A 20-year-old boy of Golaghat, Arnab To drive yourselves and to helps others to
Kakati, has been selected by the National do so
Aeronautics and Space Administration Keeping all the problems in the
(NASA) as its Junior Scientist. Arnab, the perspective,
only son of Manik Kakati, a junior Aligning all the goals with the God's good-
engineer of ASEB and Sikha Kakati of
will
Old Amolapatty, Golaghat, is studying
Moving all the loving ways in millions of
Engineering at Gandhi Institute of
relationship,
Engineering and Technology of Orissa.
Accepting everything you have as the gift
Arnab was interested in space science
since Class VIII and sent his research of God
paper on Big Bang theory to the World That might be come wrapped in the foil of
Junior NASA Competition and was later hardship,
selected as a Junior Scientist of the space As you know better that, even God in His
agency, which invited Arnab to join and human form
study at NASA. It is pertinent to mention Couldn't escape the sufferings of body
here that no person has ever joined NASA and mind
before 32 years of age. So Arnab being On the eventual journey, that is
just 20 years old, is all set to create a preordained and predestined.
world record. Initially, Arnab’s parents
were not interested in sending Arnab to (Dr. Tankeswar Nath is an active member of the
the US but Dr Kalam insisted that he must forum and presently working as a Scientist at
go there. The Junior Scientist will leave Jubilant Organosys, Noida, India.)
for Delhi on January 15 after signing some
documents at Raj Bhavan. He will fly to ---------------------0----------------------
New York on January 20. (Courtesy:
Assam Tribune)

N. E. Quest; Volume 1, Issue 4, January 2008, 9


Newsletter of North East India Research Forum

Forum Members in News of Medicine, Department of Cellular


and Molecular Medicine, University
™ Dr. Pranjal Gogoi has of California, San Diego, La Jolla,
joined the group of United States. He has recently
Prof. Antonio Mourino, completed his Ph.D. work under the
Department of Organic guidance of Dr. A. Vayjanyanti
Chemistry, University Kumar, NCL, Pune.
of Santiago de Compostela, Spain as a
post doctoral fellow from 15th
September 2007. He completed his ™ Mr. Lakshindra Chetia
Ph.D. under the guidance of Dr. Dilip will be joining the
Konwar, Senior Scientist, NEIST, group of Prof. Prabhat
Jorhat in the year 2007. Arya of Ontario
Institute for Cancer
™ Dr. Pranjal Baruah has Research, Canada as a post doctoral
joined as a post doctoral fellow from the month of Feb. 2008.
associate at Department He has recently completed his Ph.D.
of Chemistry, North under the guidance of Dr. J. S. Yadav,
Carolina State Director, IICT, Hyderabad.
University with Prof. Daniel L.
Comins. He completed his Ph.D. from ™ Mr. Saitanya Kumar
National Chemical Laboratory (NCL), Bharadwaj visited
Pune. California to present
his research paper on
™ Dr. Smriti Rekha Deka “Oxidative Extraction
joined National of Bromide from Seawater” in the
Nanotechnology “PAN IIT Global Conference 2007”
Laboratory of CNR- held at Santa Clara (Silicon Valley),
INFM-ISUFI, California, USA from 6-8 July 2007.
University of Lecce , Italy for her post He is currently doing his doctoral
doctoral research in the month of research at Indian Institute of
January, 2008. Currently she is Technology, Guwahati under Prof.
working on functionalization of Mihir Kanti Chaudhuri, Vice
nanoparticles with polymers. Chancellor, Tezpur University.

™ Dr. Mukut Gohain ™ Mr. Pankaj Bharali


will be joining shortly visited Ruhr University
the group of Prof. of Bochum (RUB),
Roberto Sanz of Germany under a
University of Burgos, bilateral collaborative
Spain as a post doctoral fellow. He did project funded jointly by DST, India
his Ph.D. under the guidance of Dr. and DAAD, Germany during October
J.S. Sandhu, former Director of to December 2007. He is currently
NEIST (RRL), Jorhat in the year pursuing his doctoral research at
2005. He is presently working as a Indian Institute of Chemical
research scientist in Orchid Chemical Technology (IICT), Hyderabad under
and Pharmaceutical Ltd., Chennai. Dr. B. M. Reddy.
---------------------0----------------------
™ Mr. Khirud Gogoi is
going to join as a
Research Specialist at “Honest differences are often a
the Howard Houghes healthy sign of progress.”
Medical Institute, Prof. Mahatma Gandhi
Steven F. Dowdy Laboratory School ---------------------0----------------------

N. E. Quest; Volume 1, Issue 4, January 2008, 10


Newsletter of North East India Research Forum

Instrument of the Issue: Based upon the lattice constants and


Single Crystal X-ray Diffractometer symmetry the system may be classified as
triclinic, monoclinic, orthorhombic,
tetragonal, cubic, trigonal or hexagonal.
Finally, each substance may be further
classified as belonging to one of 230 three
dimensional space groups.
When a beam of parallel
Mr. Bipul Sarma monochromatic x-rays strikes a single
crystal, the crystal acts as a three-
Fundamentals: dimensional diffraction grating and
produces an x-ray diffraction pattern
It is known to all that in 1895, (Figure 2). This diffraction consists of a
Wilhelm Roentgen, Professor of Physics three dimensional array of reflections that
from Worzburg, Bavaria who discover the satisfy the conditions of Bragg’s law.
possibility of using electromagnetic Bragg’s law:
radiation what we now know as the X-ray. n λ= 2d sin θ
Single-crystal X-ray diffraction or X-ray
crystallography is an analytical technique where n is a small integer giving the order
in which X-ray methods are employed to of diffraction, λ is the wavelength of the
determine the complete three dimensional incident x-rays, d is the distance between a
molecular structures including the absolute set of parallel lattice planes, and θ is the
stereochemistry of chemical substances. angle between the incident x-ray beam and
Max von Laue, in 1912, discovered that the atomic lattice plane in the crystal
crystalline substances act as three-
dimensional diffraction gratings for X-ray
wavelengths similar to the spacing of
planes in a crystal lattice. The precise
knowledge of the molecular geometry is
becoming increasingly important in nearly
all fields of chemical and biological
research.
The basic building block in a crystal
(arrangement of molecules in a precisely
regular way repeated in all directions) is Fig. 2
the unit cell. A crystal is made up of
millions of identical unit cells arranged in The spatial arrangement of the
a three-dimensional crystal lattice. Each reflections in an x-ray diffraction pattern
crystalline substance has a unique set of bears a reciprocal relationship to the
lattice constants (a, b, c, α, β, γ) which dimensions of the unit cell in the crystal.
define the size and shape of the unit cell Each reflection may be assigned a set of
(Figure 1). indices (hkl) which indicate its location in
the diffraction pattern or reciprocal space.
The diffraction pattern in reciprocal space
has a Fourier transform relationship to the
electron density in the unit cell in real
space. Experimentally, the unit-cell
parameters for a crystalline specimen may
be determined from an analysis of the
spatial arrangement of the reflections in its
x-ray diffraction pattern. The X-ray
diffraction pattern consists of the
Fig. 1 superposition of scattered waves of
varying amplitude and phase. Each

N. E. Quest; Volume 1, Issue 4, January 2008, 11


Newsletter of North East India Research Forum

diffraction maximum or reflection has be 0.1 mm to 0.5 mm, not cracked and not
associated with it a structure factor F(hkl) twinned.
measured relative to the scattering by a 2. Stable crystals of typical organic,
single electron. The structure factor may organometallic or coordination complexes
be represented as a complex vector: F(hkl) can usually be grown by slow
= A(hkl) + iB(hkl) where A(hkl) and recrystallization from common solvents.
B(hkl) are the real and imaginary Other types of compounds may require the
components of F(hkl). use of sublimation, zone refinement,
solvent diffusion, low temperature and
Instrumentation: inert-atmosphere techniques.

The basic components of typical


single-crystal X-ray diffractometer
include:
1. An X-ray source consisting of a high
voltage X-ray generator.
2. Copper or Molybdenum target X-ray
tube.
3. Associated shutter shield tube.
4. Attenuators and safety interlocks.
5. Monochromator or X-ray mirror Goniometer Head
system.
6. An incident-beam collimator.
7. Three or four circle goniometer system
that allows the specimen to be precisely
oriented in any position while remaining
in the X-ray beam.
8. Video camera or microscope for
aligning the specimen and indexing crystal
faces.
9. CCD (Charge-Coupled Device)-based
two-dimensional X-ray detector system. 3 Cycle goniometer
10. Low-temperature attachment for
cooling the specimen during data
collection.
11. Microprocessor-based interface
module that receives commands from a
host computer and carries out all real-time
instrument control functions to drive
goniometer motors, monitor the detector
system, open and close the shutter and
monitor collision sensors and safety
interlocks. Charge Coupled Device (CCD)
12. Host computer with a large hard disk
mass storage device.
13. Video monitor and keyboard, and
diffractometer control programs to control
the data collection strategy and to send
commands to the microprocessor.

Steps taken in the experiments:

1. Selection and mounting of a suitable


crystal. Ideal size of a single crystal must Bruker-AXS CCD diffractometer

N. E. Quest; Volume 1, Issue 4, January 2008, 12


Newsletter of North East India Research Forum

Suitable single crystal is glued or securely Reference:


attached to a goniometer head (sample
holder) in an arbitrary orientation. The 1. Clegg, W. 1998, Crystal Structure
goniometer head is then placed on the base Determination, Oxford University
of the goniometer and the crystal is Press, Oxford
optically aligned in the center of the 2. Glusker, J. P., Trueblood, K. N. 1985,
incident X-ray beam using a video camera Crystal Structure Analysis, A Primer;
or microscope. The orthogonal X, Y, and Oxford University Press, New York.
Z translations on the goniometer head are 3. BRUKER AXS INC. 5465 East Cheryl
adjusted until the crystal is centered. A Parkway Madison, WI 53711-5373,
preliminary rotational image is then USA; BRUKER AXS GmbH, D-
collected for one minute with the CCD 76181 Karlshuhe, Germany.
detector to screen the crystal (also known 4. Stout G. H., Jensen, L. H. 1989, X-Ray
as rotaframe) for analysis and to select Structure Determination; A Practical
suitable parameter values for subsequent Guide; John Wiley & Sons, New
steps. In order to determine the unit cell, a York.
preliminary set of frames is measured. For
example, three sets of frames are collected ---------------------0----------------------
in different parts of reciprocal space.
These frames are then processed to locate
spots on individual frames and to then ”An investment in knowledge
determine the centers of reflections. An always pays the best interest”
auto-indexing routine selects the
appropriate reduced primitive unit cell and
Benjamin Franklin
calculates the corresponding orientation
matrix and lattice constants. This
preliminary unit cell is then refined using
a non-linear least-squares algorithm and ---------------------0----------------------
converted automatically to the appropriate
crystal system and Bravais lattice. This
new cell is refined by the non-linear least- “The important thing is not
squares algorithm to yield an accurate to stop questioning.
orientation matrix which may be used to Curiosity has its own
index crystal faces and to carry out reason for existing. One
integration calculations after intensity data cannot help but be in awe when he
collection. When electrons have sufficient contemplates the mysteries of eternity, of
energy to dislodge inner shell electrons of life, of the marvelous structure of reality. It
the target material, characteristic X-ray is enough if one tries merely to comprehend a
spectra are produced. Molybdenum is the little of this mystery every day. Never lose a
most common target material for single- holy curiosity.”
crystal diffraction, with MoKα radiation =
0.7107Å. These X-rays are collimated and
Albert Einstein
directed onto the sample. When the
geometry of the incident X-rays impinging ---------------------0----------------------
the sample satisfies the Bragg Equation,
constructive interference occurs. A
detector records and processes this X-ray
signal and converts the signal to a count “Education: that which
rate which is then output to a device such reveals to the wise, and
as a printer or computer monitor. In final conceals from the stupid,
stage, data reduction and refinement using the vast limits of their
specific software (SAINT, SHELXTL etc) knowledge.”
we can visualize the molecule in 3D.
Mark Twain

N. E. Quest; Volume 1, Issue 4, January 2008, 13


Newsletter of North East India Research Forum

Articles: used clinically and in research protocols.


Interestingly, combining the surface
Nanomedicine: Nanoparticles in Drug chemistry and self-assembly processes
Delivery leads to the development of gold
Dr. Jadab Sharma nanoparticles based nanovectors, which
offers several advantages in respect to its
The field ‘Nanomedicine’ is emerging multiple application possibilities. In
as a major area of research recently, the essence, the requirements/strategies for
process of diagnosing, treating, and polymer based drug delivery systems are
preventing disease and traumatic injury, essentially the same with nanoparticles
relieving pain, and preserving and based delivery systems, while both the
improving human health, using molecular systems have several advantages and
tools and molecular knowledge of the disadvantages one over another. However,
human body. Traditional treatment lacks the most significant aspect of drug
precision, i.e., inadequacies in the ability delivery systems is to combine vast
to administer therapeutic moieties so that knowledge of nanomaterials,
they will selectively reach the desired biochemistry, supramolecular chemistry,
targets with marginal or no collateral polymer chemistry, and the appropriate
damage has largely accounted for the development of superior mathematical
discrepancy. models. The scheme 1 shows the major
requirements and strategy adopted for
The major component for the developing nanomaterials based controlled
controlled drug delivery is ‘Nanovector’- drug delivery systems.
for the administration of targeted NANOPARTICLES
therapeutic and imaging moieties, for (SYNTHESIS)

which the precise patterning of surfaces of


FUNCTIONALIZATION
nanoparticles is the most essential part.
These nanovectors are mainly developed LOADING MAKE THEM TARGET
SPECIFIC

for the use in cancer treatment and are IMAGING BIO COMPATIBILITY
(FLOURESCEIN PROBE)
intravascularly injectable. Their
CELL PERMEABILITY
envisioned use is for the in vivo, non- DRUG MOLECULES

invasive visualization of molecular


markers of early stages of disease; the NANOVECTOR

argeted delivery of therapeutic agents,


with a concurrent, substantial reduction of INTRODUCTION INTO THE BODY FLUID

deleterious side effects; and by a DETECTION CONTROLLED RELEASE TRACING THE


OF TARGET OF DRUGS TRAJECTORY & IMAGING
combination of first two- the interception OF TARGET

and containment of lesions before they Scheme 1.


reach the lethal or even the malignant
phenotype, with minimal or no concurrent
loss of quality of life. There are two ways We wish to employ our knowledge on
to achieve this goal: polymer therapeutics nanomaterials advantageously to develop
and nanoparticles based therapeutics or a different nanovectors by a combination of
combination of both. Polymer supramolecular techniques, nanomaterial
therapeutics includes rationally designed science, bio-chemistry, polymer science,
macromolecular drugs, polymer-drug, and and self-assembly methods. Accordingly,
polymer-protein conjugates, polymer following two major areas will be
micelles. Similarly, several types of discussed briefly:
nanoparticles for the controlled drug 1. Nanomaterials: Nanovectors in general
delivery have been attempted, for have at least a tripartite constitution: (a) a
example, gadolinium-based, iron oxide core constituent material, (b) a therapeutic
based nanoparticles and multiple-mode and/or imaging payload, (c) biological
imaging contrast nano-agents that combine surface modifiers, which enhance the bio-
magnetic resonance with biological distribution and tumor targeting of the
targeting and optical detection have been nanoparticles dispersion.

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Newsletter of North East India Research Forum

and needs active and innovative research


efforts. Another class of targeting methods
uses external energy as a trigger for the
localized activation of cytotoxic action
and has been demonstrated in animal
models. Examples are the use of focused
ultrasound to burst lipid encapsulated
microbubles, photodynamic therapy on
silica based carriers, and the localized
thermal ablation of cancer lesions using
Drug A PEG gold nanoplates and nanocages by optical
Drug B
Contrast enhancer Targeting moieties activation in the near-infrared region.
Permeation enhancer Another emerging class of nanovectors is
made of silicon and silica nanoparticles.
Therefore, a comprehensive Porosified silicon is biodegradable, with
investigation should be carried out kinetics that is much more rapid than those
focusing three main areas: (a) finding of biodegradable polymers, and therefore,
appropriate nanoparticles as core, (b) releases drugs with previously
suitable therapeutic materials for curing unattainable time profile.
and early diagnostic, and (c)
biocompatible surface layers or coating Currently, there are limited methods
materials. Several types of nanoparticles available for longitudinal and non-invasive
have been developed and many more are in vivo assessment of the transport kinetics
still to come. A judicious choice of of carrier-based therapeutics, such as those
synthesis protocol will help to find relying on liposomes. Increased interest in
suitable nanomaterials as core, for nanocrystal quantum dot (QD) technology
example spherical gold nanoparticles of as fluorescent probes possessing
various sizes, gold nanoplates, gold unprecedented brightness, photostability,
nanocages, alloy nanoparticles, and core and multi-color capability has made
shell nanoparticles. Nanoparticles have the apparent their promising potential for live
advantage of stability and tenability over tracking of single cell and in vivo
conventional staining methods. Attaching processes. Presently, QD biorecognition is
gold nanoparticles to specific largely achieved through attachment of
oligonucleotides that, when added to a antibodies to the QD surface, resulting in a
sample of DNA, would bind to bio–inorganic complex combining
complementary gene sequences. The gold biomolecular-specificity with
nanoparticles can also be attached to fluorescence. A less explored approach is
proteins, opening up the possibility of to use small ligands or synthetic analogs
controlling more complex biological that when conjugated to the QD, would
processes such as protein folding and bind not only to receptor proteins, but also
enzymatic activity. Magnetic nanoparticles serve to activate signaling cascades that
have been used as MRI contrast enhancer, regulate cellular phenotype and behavior.
e.g. gadolinium-based nanoparticles, iron- Surface modification and composition of
oxide-based nanoparticles, and many other complexed QD nanostructures have been
magnetic nanoparticles. Interestingly, confirmed and bioactivity of ligands and
Dextran-coated, ultra small paramagnetic ligand-QD complexes have also been
iron-oxide nanoparticles were shown to tested using functional imaging based
outperform conventional gadolinium MRI assays. Development of this QD-based
contrast in terms of intra-operative capability bears significance for
permanence of imaging enhancement, development of tools for studying inter-
inflammatory targeting, and detectability molecular interactions, assessing
at low magnet strength in the surgical effectiveness of drug compounds, and
treatment of brain tumors. In essence, this visualization of cellular function for a
area of research is comparatively difficult variety of biological studies.
in terms of functionalization of surfaces

N. E. Quest; Volume 1, Issue 4, January 2008, 15


Newsletter of North East India Research Forum

2. Therapeutic (imaging) payload and The gel particles have to be designed to


biological surface modifiers: Drug eluting exhibit behaviors responsive to
stents, cage-like metal devices coated with temperature and pH in solutions,
a drug/polymer mixture, significantly consequently protecting the incorporated
advance the treatment of cardiovascular peptide drug under harsh acidic conditions
disease. The molecular targeting of in the stomach, adhere and penetrate to the
nanovectors containing active agents mucin layer in the small intestine, and
might be attained by the conjugation of thereafter release the drugs.
active recognition moieties to the surface Photodynamic therapy (PDT) is a
of a nanovector. Specificity is then novel photochemical process for
increased at the expense of added producing localized tissue necrosis, which
complexity in the nanoparticles involves the activation of a
preparation. The use of molecularly photosensitizing drug in the target tissue
targeted nanovectors has several potential with light of a specific wavelength
advantages over conventional antibody- matched to an absorption peak of the
guided therapy: the delivery of much photosensitizer in the presence of
greater therapeutic payloads per target molecular oxygen. However, the
recognition event; the ability to carry photosensitivity is still a major side effect
multiple, potentially different targeting of PDT in clinical treatment. Micelles as
agents, providing selectivity enhancement; photosensitizer carriers are able to provide
the ability to integrate means to bypass many advantages, including improvement
biological barriers; and co-localized of drug solubility, reduction in
delivery of multiple agents, resulting in photosensitivity, long circulation time and
targeted combination therapy. The metal tumor targeting. An investigation towards
cage keeps weakened blood vessel walls new class of carriers will be helpful to
open and the polymer coating elutes a solve this problem (e.g. shell cross-linked
drug which prevents scar tissue formation, (SCK) nanoparticle based on poly(ε-
which can re-block the vessel. caprolactone)-poly(ethylene glycol)-
Formulation of drug eluting coatings aldehyde have been demonstrated to
remains a challenge since the coating must successful delivery of protoporphyrin IX).
be thin and conformal, the polymer matrix A viable strategy to non-invasively track
must be tailored to incorporate high the carrier in vivo is to employ the same
concentrations of drug and to control the carrier loaded with contrast-enhancing
elution of the drug, and the coating must agents such as iodine and gadolinium. If
withstand the severe deformations of the these agents are retained within the carrier,
metal cage upon insertion into the vessel. they may act as surrogates for therapeutic
Polymer blend coatings often offer molecules and allow for non-invasive
advantages not found in single polymer tracking of the carrier in vivo using
coatings: ability to tune drug elution rates computed tomography (CT) and magnetic
and mechanical properties by varying the resonance (MR) imaging devices.
ratio of the two polymers.
Cationic nanoparticles have been
The characterization of structural formulated from a polycationic
properties of novel dicationic (gemini) Polyhydroxylamine (PT) with low pKa
surfactant-based DNA complexes as and polyanionic PolyAcrylic Acid (PA)
micro/nano-scale self-assembling delivery that form binary polyelectrolyte
systems for cutaneous gene therapy has complexes (PECs). It has been observed
been described and discussed as related to
(L1)
measured transfection efficiencies. In O H O
order to characterize and control the HS N
N
N
O

adhesive behaviors of nanometer scaled H O H O

stimuli-responsible gel particles designed


for oral peptide delivery, their interaction Peptide with permanent dipole moment
(Variable chain length and charge)
with artificial mucin layer in the small
intestinal solutions has to be determined.

N. E. Quest; Volume 1, Issue 4, January 2008, 16


Newsletter of North East India Research Forum

that particles spontaneously form on in Chemistry, under the supervision of


component mixing with sizes between 80- Prof. K. Vijayamohanan, at the National
700nm and particle charge 3-30mV. Chemical Laboratory, Pune, India. After a
Plasmid containing GFP (Green short Postdoctoral Fellowship at the
fluorescing protein, pGFP) can be University of Padova under Prof. Flavio
incorporated (by pre-binding pGFP to PT) Maran, he has joined the reaseach group
and assessed. Nanoparticle polymer of Prof. T. Imae, Keio University, Japan
systems below 1 micron in size have and is continuing his research at National
potential roles as carrier systems. An Taiwan University of Science and
advantage of using polyhydroxlamine Technology, Taiwan under her
based PECs is that they should allow supervision. His areas of research interest
release of bound DNA as a polyanion are electrochemistry, functionalized
from a PEC at relatively mild pH nanomaterials, organic synthesis (small
conditions, due to the low pKa (below 9) ligands for nanoparticles, such as
of the polycationic Polyhydroxylamine. peptides), and solar cell.

HO O OH (L2) Disposable Plastics

HN CH2 CH2 SH
14
O

Mr. Binoy Kumar Saikia


Ligand with fluorescein properties
The use of certain chemicals such as
plasticizers and chlorofluorocarbons in the
manufacture of plastics produces
Such nanoparticles have potential use as ecological and environmental problems.
cationic transfection agents that can The tremendous amount of plastic items
release under benign physiological used today creates waste disposal
conditions compared to similar particles problems. Plastic waste in the sea poses
formulated with ‘hard’ polyamines with direct danger to fishes. Small fishes have
higher pKa (>pH9). Simple addition of been found dead with their digestive tracts
polyhydroxylamine and poly-acrylic acid clogged by fragments of plastic foam they
(w/w), under mildly acidic conditions, had ingested. Plastic bags have suffocated
causes spontaneous formation of cationic sea animals to death. The disposal of
nanoparticulate PEC dispersions with a plastic waste by landfilling and
range of size and charge. Several other incineration has both caused certain
examples include nanoconjugates of β- problems. As plastics are chemically
poly(L-malic acid) (PMLA), Lysolipid tailored for long life, they do not generally
temperature sensitive liposomes (LTSLs) undergo decomposition in the landfill site.
etc. We had synthesized ligand and Thus the plastic waste can last for a long
fluorescein probe for their application as period in the environment. Incineration of
imaging material and surface modifier plastic waste produces air pollutants such
(shown above as L1 and L2). as hydrogen chloride from polyvinyl
chloride and other chlorine containing
About the author:
polymers. The hydrogen chloride
Jadab Sharma was born in India in 1974. produced can cause acid rain, which
He obtained the B.S. (1997), the Master damages the environment.
(2000), and then the Ph.D. (2006) degrees

N. E. Quest; Volume 1, Issue 4, January 2008, 17


Newsletter of North East India Research Forum

Development of degradable plastics reserve, disposal of plastics by way of land


and recycling of plastics as possible filling or incineration is a waste of useful
solutions to pollution problems as the use resources. Such wastage may be reduced
of plastics can hardly be divorced from by recycling, in one form or another, as
modern living, the associated pollution outlined below:
problems have to be solved. To tackle the
problem of waste disposal, degradable
plastics are being developed and processes
for recycling of plastic waste are now
underway.

Degradable plastics:

Plastics normally undergo extremely


slow degradation because the enzymes in
microorganisms tend to attack only at the
ends of the polymer chains. Attempts have
been made to develop plastics, which are
more degradable. There are several types
of degradable plastics:

(1) Biopolymers – polymers made by


living organisms. Poly (hydroxybutyrate),
PHB, is natural polyester made by certain
bacteria. Microorganisms found in soil and
natural water sources are able to break
down the polymer. The degradation of this
polymer in the environment is usually
completed within 9 months. However, (1) Direct recycling – this applies only to
PHB is 15 times more expensive than poly thermoplastics. The plastics in the waste
(ethene). are separated, cleaned, pulverized, and
(2) Photodegradable plastics – light- remoulded into plastic items. The success
sensitive functional groups such as of this method depends on the collection
carbonyl group (C=O) can be incorporated of clean and uncontaminated plastic waste,
into the polymer chains. The long polymer which is the most difficult step. In 1988,
chains will be broken down under the the Society of the Plastics Industry (SPI)
action of sunlight into shorter fragments, developed a uniform coding system that
which can then be biodegraded. makes it possible to sort waste plastics.
(3) Synthetic biodegradable plastics– The SPI (Society of the Plastic Industry)
made by incorporating starch or cellulose coding symbols are shown next. Code
into the polymer during production. As numbers 1 to 6 refer to specific polymers,
microorganisms digest the starch or while 7 number refers to all other types.
cellulose, the plastic is broken down into Once the waste plastics are separated, they
tiny pieces. The very small pieces left over can be reprocessed into new plastic items.
have a large surface area, which greatly The regenerated plastics usually have
speeds up their biodegradation. deteriorated properties due to repeated
thermal and mechanical processing, and
Degradable plastics have been used can only be used for articles, which are not
for making six-pack beverage rings, trash subject to high stress. Recent development
bags and disposable diapers. on recycled plastics focuses on converting
the plastic products with short service
Recycling of plastics: lives, such as foam, wrap and containers,
to products with longer service lives, such
Since plastics are essentially derived as construction materials and plastic pipes.
from petroleum, which has limited

N. E. Quest; Volume 1, Issue 4, January 2008, 18


Newsletter of North East India Research Forum

About the author: quantitative analytical information using a


biological recognition element which is
Binoy Kumar Saikia passed M.Sc. in
connected with the transducer element
Inorganic Chemistry from Cotton College
(IUPAC, 1969). The biological
(Gauhati University) in 2000. He then
recognition element may be an enzyme,
joined in North East Institute of Sciences
antibody or a binding protein and a
& Technology, Jorhat, as a Project
transducer to convert the biochemical
Assistant and completed his research work
reactions into quantifiable electronic
on X-ray diffraction and spectroscopic
signals that can be processed, transmitted
investigation of Assam coal. Presently he
and measured. A biosensor has two
is engaged as a Technical staff in the
components i.e. a receptor and a detector.
Department of Chemical Sciences, Tezpur
The receptor is responsible for selectivity
University, Tezpur, India. His areas of
of the sensor
research interest include X-ray diffraction,
FT-IR spectroscopy, coal chemistry, acid
mine drainage, water & soil pollution. Microelectronics
Biosensor DataProcessing

-Enzymes Electrodes
Biosensor and its applications -Cells, Microorganisms
Tissues and organelles
Transistors
Thermistors
Sample Optical detectors Amplifier
-Antibodies and
Receptors Piezoelectric
Mr. Manashjit Gogoi -Nucleic Acids crystal

0.12345
Bioreceptors Physical
Introduction: Transducer

Biological systems are the most (Fig1).


efficient systems as they reached the
present state after hundreds of thousands Type of biosensors:
of years of continuous evolution. In order
to increase our efficiency, we learn from Biosensors can be classified based on
biological systems and mimic them. biological parts and the basis of their
People are trying to employ the ways, transducers.
living being exchange messages and Based on biological components:
communicate with the surrounding i.e.
how they sense signals from the a) Catalytic (Enzyme) based
surrounding and how they process the b) Tissue/cell biosensor based
signals. Biosensor is a result of
biomimicry of biological sensing system. c) Affinity biosensor based
Biosensors are analytical devices that Based on the transducers:
combine a biological recognition element
with a physical or chemical transducer to a) Eectrochemical biosensors
selectively and quantitatively detect the b) Piezoelectric crystal
presence of specific compound(s) in a
c) Optical biosensor
given environment. These biosensors are
accurate, reliable and simple to operate, d) Calorimetric
can be easily fabricated with minimal
Application of biosensors:
sample preparation. Biosensors have many
advantages such as simple, low cost Clinical: Biosensors can play a vital role
instrumentation, highly selective and fast in disease diagnosis. Implantable
response time. biosensors can provide real time
measurements in critical condition and
Biosensor: supply data of important pathological
parameters. Research is going on for the
Biosensor is defined as a self development of lab-on-chip device where
contained integrated device that is capable biosensor will provide complete data for a
of providing quantitative or semi- given analysis.

N. E. Quest; Volume 1, Issue 4, January 2008, 19


Newsletter of North East India Research Forum

Agriculture: In this field, biosensors can About the author:


be used to monitor the degree of ripening
Manashjit Gogoi hails from Jorhat,
of fruits, presence of pesticides and
Assam. He did B.E. in Chemical
herbicides in food products and sugar
Engineering from Assam Engineering
analysis from sugarcane in sugar industry
College in 2001 and completed M. Tech.
etc.
from Tezpur University in Bioelectronics
Bioprocess industry: In this area, in 2006. In between this period, he worked
biosensors can play a vital role in online in NEIST, Jorhat as a project Assistant
monitoring of substrate and product and CFTRI, Mysore as a GATE-JRF.
analysis in microbial fermentation and Presently he is in IIT, Bombay pursuing
downstream processing of biological his Ph.D. on the topic "Temperature
samples. sensitive nanostructured magnetic
Environmental: In environmental sector, materials and nanovesicles for combined
biosensors can be used for monitoring of cancer hyperthermia and drug delivery".
organophosphate pollutants, Heavy metals
and toxic radicals in the environment and
determination of Biological Oxygen Mushroom Poisoning – The Fact
Demand in industrial effluents.

Food industry: Biosensors are being used


for monitoring of sugar concentration in
soft drinks and confectionery syrups and
pulps and detection of food adulterants
and food toxins.
Defence: Biosensors can be used in
defence application to detect the presence Mr. Mahananda Chutia
of detection of explosives like RDX and
TNT and Chemical and Biological warfare
agents. Mushrooms are not a taxonomic
group. They are the macrofungus with a
Conclusion: distinctive hypogeous or epigeous fruiting
body, large enough to be seen with the
Biosensor is a multidisciplinary area; naked eye and to be picked by hand
it needs the expertise knowledge of life (Chang & Miles, 1992). The number of
sciences, chemistry, material science, mushroom species on the earth is
electronics, software, MEMS and VLSI estimated to be 140 000, suggesting that
technologies. With the progress of these only 10% are known (Lindequist et al,
areas, compact, cheap, robust, high 2005).
sensitive, accurate biosensors are hitting Assuming
the market everyday. The research and that the
development and commercial exploitation proportion of
of biosensor is not fully explored yet. useful
Presently, biosensor market is growing at mushrooms
a rate of 6.3% per annum, the market among the
volume will be $8.2 billion by 2009[1]. undiscovered
So, there is huge potential in this field to and unexamined mushrooms will be only
explore. In India, the biosensor research is 5%, which implies 7000 yet undiscovered
in infancy stage. If we do not start to species will be of possible benefit to
work on biosensor now, we will be great mankind (Hawksworth, 2001).
loser in near future in terms of jobs, Mushrooms can be used for successful
money and market. So, it is right time to bio-prospecting for the benefits of
explore the opportunities in the field of mankind as both the macro and
biosensor. macroscopic fungus have the potential for

N. E. Quest; Volume 1, Issue 4, January 2008, 20


Newsletter of North East India Research Forum

the production of commercially important is also an important feature for


bioactive secondary metabolites. Again, identification. There are no such
some of the mushrooms are deadly traditional common tests or rules that can
poisonous too. Naturally, majority of the accurately determine the safety or toxicity
wild mushrooms are known as poisonous; of a poisonous mushroom. However, there
for which many people affect on are some common guidelines to know
mushroom poisoning due to the about the poisonous group of mushroom
consumption of wild mushroom. although it is not the scientific or correct
one which could prove to be a deadly
The habit of eating wild mushrooms is mistake.
very common in India especially in the
rural areas. Many people are admitted to Anyway, a mushroom is considered
hospitals due to mushroom poisoning poisonous if:
every year and many lose their lives
because of the complications (Erguven et ƒ The mushroom stains when bruised
al, 2007). Mushroom poisoning is ƒ The mushroom turns garlic blue or
common especially among people from black when cooked together
low socioeconomic level who consume ƒ The mushroom has scales, warts or
mushroom in daily nutrition. other types of rough surfaces
ƒ The mushroom secretes a milky sap
Why some wild mushrooms are ƒ The mushroom turns a silver coin
poisonous? black when rubbed against it
ƒ The mushroom tarnishes a silver
Poisonous mushrooms contain at least spoon when cooked with it
two different types of toxins, each of
which can cause death if taken in large A mushroom is considered safe if:
enough quantities. All the mushroom
poisoning (called as mycetism) is due to • If it is cultivated
its chemical constituents in that particular • The mushroom grows on wood
species. These chemical goups are alpha- • Slugs or other insects eat the
amanitin (deadly), bolesatine (in Boletus mushroom
satanas), coprine (poisonous with • Squirrels, rabbits, or other wildlife eat
alcohol), orellanine (deadly), gyromitrin the mushroom
(deadly), muscarine (sometimes deadly), • The mushroom does not have a ring or
arabitol (cause gastrointestinal irritation). skirt on the stalk
One group of poisons, known as • The mushroom is dried, boiled, salted
amatoxins, blocks the production of DNA, or pickled in vinegar
the basis of cell reproduction. This leads to
• The mushroom is pure white in color
the death of many cells, especially in the
liver, intestines and kidney. Other
What are the symptoms of mushroom
mushroom poisons affect the proteins
poisoning?
needed for muscle contraction and
therefore reduce the ability of certain
The type of symptoms of mushroom
muscle groups to perform. The type of
poisoning is also different species to
poisoning of different group of toxins is
species due to their different groups of
also different.
toxins present (Unluoglu and Tayfur
2003). The symptoms are –
How to identify poisonous mushroom?
Toxin groups CYCLOPEPTIDES
Identifying of poisonous mushrooms
Symptoms begin with sharp
is very difficult, costly and time-
abdominal pains, violent vomiting and
consuming. Identification is done basically
persistent diarrhea. In 3-4 days, the patient
on the characteristic features of the color,
begins to worsen with symptoms of kidney
gills, spores, stalks and base portion of the
and liver failure and may die.
mushroom. The habitat of the mushroom

N. E. Quest; Volume 1, Issue 4, January 2008, 21


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Toxin groups ORELLANINE gastrointestinal tract by inducing vomiting


Symptoms are nausea, lack of or by stomach pumping.
appetite, headache, severe burning thirst Early removal of mushroom poison by
and kidney failure. way of an artificial kidney machine
(dialysis) has become part of the treatment
Toxin groups IBOTENIC ACID- program now a day. This is combined with
MUSCIMOL the correction of any imbalances of salts
Common symptoms are confusion, (electrolytes) dissolved in the blood, such
muscle spasms, delirium and continuous as sodium or potassium. An enzyme called
visual disturbances. Vomiting usually does thioctic acid and corticosteroids also
not occur. Patient can recover after appear to be beneficial, as well as high
treatment. doses of penicillin (Benjamin, 1995). In
Europe, a chemical taken from the milk
Toxin groups ONOMETHYLHYDRAZINE thistle plant, Silybum marianum, is also
The patient experiences a feeling of part of treatment. When liver failure
fullness in the stomach, vomiting and develops, liver transplantation may be the
watery diarrhea, headache, fatigue, only treatment option. The mortality rate
cramps. Pain in the liver and stomach has decreased with improved and rapid
followed by jaundice. treatment. However, according to some
medical reports death still occurs in 20-
Toxin groups MUSCARINE-HISTAMINE 30% of cases with a higher mortality rate
Symptoms are sweating, drooling, of 50% in children less than 10 years old.
diarrhea, watery eyes, blurred vision,
pinpoint pupils, decreased heart rate and Conclusion
blood pressure.
It is also important to remember that
Toxin groups COPRINE most mushroom poisons are not destroyed
Symptoms occur if taken with alcohol. or deactivated by cooking, canning,
Flushing of the face and neck, a metallic freezing, drying or other means of food
taste in the mouth and an increased heart preparation. So, the important factor to
rate. prevent mushroom poisoning is to avoid
eating wild or noncultivated mushrooms.
Toxin groups PSILOCYBIN-PSILOCYN Early diagnosis and treatment in
Symptoms are in thinking which alter mushroom poisoning can be life saving.
consciousness. Hallucinogenic begins after Alpha amanitin levels should be checked
30-60 minutes of ingestion. It may cause as soon as possible, if amanita poisoning is
anxiousness or uncontrolled laughter. suspected. If laboratory tests to detect the
toxin cannot be performed the time of
Toxin groups ARABITOL occurrence of symptoms, the features of
Sudden severe vomiting and mild to the ingested mushroom, the clinical
severe diarrhea with abdominal cramps are picture and the family anamnesis can give
the symptoms. defined important clues about the type of
intoxication (Erguven et al, 2007).
Diagnosis and treatment Moreover, providing public education on
mushroom poisoning is very much
There is no specific antidote for important in prevention of intoxication as
mushroom poisoning. However, the death well as encouraging early admission to
rate of the mushroom poisoning may be hospitals.
decreased. Early replacement of lost body
fluids has been a major factor in Reference:
improving survival rates. Therapy is aimed 1. Chang ST, Miles PG (1992)
at decreasing the amount of toxin in the Mushrooms biology—a new
body. Initially, attempts are made to discipline. Mycologist. 6: 64–65.
remove toxins from the upper

N. E. Quest; Volume 1, Issue 4, January 2008, 22


Newsletter of North East India Research Forum

2. Hawksworth DL (2001) Mushrooms: examples are; SiC in high strength ceramic


the extent of the unexplored potential. materials, ZrO2 in superplastic ceramics,
Int. J Med Mushrooms, 3:333–7. magnetic metallic phases of Fe and Co in
3. Lindequist U, Niedermeyer THJ, magnetic materials, etc. Composite
Julich WD (2005) the materials are used in large number of
Pharmacological Potential of multifunctional applications, from
Mushrooms. eCAM. 2(3):285–299 cryogenic to corrosion resistance, from
4. Benjamin DR (1995) Amatoxin biomedical to engineering, from
syndrome. In: Mushrooms: poisons automotive to thermoplastics, from high
and panaceas — a handbook for density recording to GMR, etc [1,2]. A
naturalists, mycologists and ‘nanocomposite’ is defined as a composite
physicians. New York: WH Freeman in which the distinctive component(s)
and Company. pp 198–214 is/are in the nanometer range. The
5. Erguven M, Yilmaz O, Deveci M, accepted length scale for the nanophase is
Aksu N, Dursun F, Pelit M, Cebeci N less than 100 nm in at least one dimension.
(2007) Mushroom poisoning. Indian The continuous materials can be ceramic,
J. of Pediatric, 74 (9): 847-852 metallic, organic or polymers, either in the
6. Unluoglu I, Tayfur M (2003) bulk form or as a thin film.
Mushroom poisoning: an analysis of Nanocomposites are a special class of
the data between 1996-2000. Eur J materials originating from suitable
Emeg Med, 10: 23-26. combinations of two or more nanoparticle
samples or nanosized objects in some
About the author: suitable medium, resulting in materials
having unique physical properties and
Mahananda Chutia did his M.Sc. (2003) in wide application potential in diverse areas.
Botany with specialization in Novel properties for the nanocomposites
Microbiology from Gauhati University, can be derived from the successful
Assam. After qualifying NE SLET, he combination of the characteristics of
joined as a project assistant at NEIST, parent constituents into a single material.
Jorhat, Assam in the Plant Science Moreover, these materials typically consist
Division. His research interests include of an inorganic (host) solid containing an
Microbial diversity and Molecular organic component or vice versa. Or they
Biology, Cell Biology and Immunology. can consist of two or more
inorganic/organic phases in some
combinational form with the constraint
Nanocomposites and Their Applications that at least one of the phase of various
features be in nanosize [3].

Composites are expected to exhibit


superior properties or better performance
than their elemental or monolithic
counterpart. Most of the property changes
can be estimated by some rule of mixtures.
The simplest change of a composite
property, Pc, is monotonic increases or
Dr. Sasanka Deka decrease with the increase of volume
fraction, Vi, of the added components;
A composite is one or more distinctive which is represented by the following
components dispersed in a continuous equation
matrix creating a compositional
heterogeneity of the final solid structure.
A typical conventional composite is glass-
fibre-reinforced plastic (GFRP) that is
widely used in aircrafts, large containers
and automotive parts. Some other

N. E. Quest; Volume 1, Issue 4, January 2008, 23


Newsletter of North East India Research Forum

where Pi is the added component property morphologies and device geometries, etc
and n is an experimental parameter ( 1 ≤ [6]. Polymer based magnetic
n ≤ 1). Nanocomposites differ from their nanocomposites with high initial
bulk components in terms of the strong permeability and high dielectric constant
interactions of grains around the grain are interesting because of their flexibility,
boundaries. There are six properties of compatibility and easy fabrication nature.
interest in nanocomposites. These are: Polymer/metal/ferrite composites consist
mechanical, magnetic, electrical, optical, of a polymer, a magnetic metal and a
quantum dots and catalytic properties. ferrite material either on the coronal
Nanocomposites exhibit unique behavior surface or in the interior core of the
due to three effects (i) the smaller size polymer microdomains as filler. This is a
effect, (ii) the large grain boundary effect, totally innovative composite material,
and (iii) the quantum confinement effect. where properties of both the matrix
Moreover, they exhibit high reactiveness polymer and the nanocomposite
during synthesis and in processing components are synergized. In such
situations. Thus, these conditions leads to polymer/metal/ferrite composites, high
increase in strength and hardness of initial permeability can be obtained by
ceramic matrix nanocomposites, lowering dispersing ferrite particles with large
in melting point and increase in electrical initial permeability in the polymer matrix
resistivity of metallic matrix as filler, and in addition, dielectric
nanocomposites, increase in absorption of constant can be enhanced over their
UV wavelength in polymer matrix polymer matrix. Thus, merging these two
nanocomposites, increase in shielding the different properties in polymer based
electrostatic field for semiconducting composites, it will be easier to overcome
matrix nanocomposites, etc. the disadvantages of purely ceramic based
Nanocomposites find their applications in composites. Finally we can expect some
various areas, such as electromagnetic more enhanced applications from the
wave absorber, biocompatible magnetic nanocomposites.
nanofibre, conducting polymer
nanocomposites, cheaper optoelectronic, References:
photonic and electronic devices, integrated
circuit (IC) products, etc [4]. 1. J. B. Schutz, Cryogenics 38 (1998) 3.
2. D. Xie, I.-D. Chung, G. Wang and J.
Out of the application oriented Mays, J. Biomater. Appl. 20 (2006)
nanocomposites, magnetic 221.
nanocomposites in which magnetic species 3. P. M. Ajayan, L. S. Schadler and P. V.
are dispersed within nonmagnetic or Braun, Nanocomposite Science and
magnetic matrices are practically very Technology, (Wiley-VCH GmbH &
useful. Magnetic recording, GMR, Co. KGaA, Weinheim, 2003).
magnetic refrigeration, etc., are some 4. H.-L. Tasi, J. L. Schindler, C. R.
important areas in which magnetic Kannewurf and M. G. Kanatzidis,
nanocomposites have importance [3,5]. Chem. Mater. 9 (1997) 875.
One newly studied nanocomposite 5. H. Zeng, J. Li, J. P. Liu, Z. L. Wang
material is the polymer/metal/ferrite and S. Sun, Nature 420 (2002) 395.
composite. The importance of such a 6. D. Y. Godovsky, Adv. Poly. Sci. 153
system is that after little modification, (2000) 163.
these can be used as capacitors and
inductors. Moreover, they have advantages About the author:
over the current ferromagnetic-
ferroelectric ceramic composites in Sasanka Deka hails from Kamrup, Assam.
various terms. The main advantages of He has completed his B.Sc. degree from B.
magneto-polymer composites are the Barooah College, Guwahati in 1998 and
ability to tailor materials for special Master degree from the department of
purposes, low cost of production, Chemistry, Gauhati University in 2000.
availability to develop totally new material After clearing CSIR-UGC-NET he joined

N. E. Quest; Volume 1, Issue 4, January 2008, 24


Newsletter of North East India Research Forum

in the National Chemical Laboratory and formation are schematically drawn in


obtained Ph.D. degree in 2007. His Figure 1 and Figure 2 respectively.
primary interest of research areas are
materials science, nanomaterials, oxide Soft Segment
nanoparticles, magnetism and
semiconductor. He has 11 publications in
peer-reviewed international journals with
few more in the national journals, Hard Segment
symposia and conference proceedings.
Currently he is a postdoctoral fellow in Figure 1. The structure of a segmented
National Nanotechnology laboratory, polyurethane molecule.
Lecce, Italy. The present supervisor of his
work is Dr. Liberto Manna.
The soft segment is either polyester,
polyether or polyalkyl glycol with a
molecular weight between 600-3000. The
Polyurethane Chemistry: Fundamentals hard segment is normally an aromatic
and Applications diisocyanate that has been chain extended
with a low molecular weight diol. The
polymerization reaction is catalyzed by
tertiary amines, such as
dimethylcyclohexylamine, and
organometallic compounds, such as
dibutyltin dilaurate or bismuth octanoate.
Furthermore, catalysts can be chosen
based on whether they favor the urethane
(gel) reaction, such as 1,4-
Dr. Smriti Rekha Deka diazabicyclo[2.2.2]octane (also called
DABCO or TEDA), or the urea (blow)
Polyurethanes constitute a very reaction, such as bis-(2-
important class of industrial polymer. It is dimethylaminoethyl)ether, or specifically
available in different forms such as drive the isocyanate trimerization reaction,
elastomers, toughened polymers, blends such as potassium octoate. The most
and foams. The different classes of important and widely used synthetic route
polyurethanes are characterized by the for the preparation of polyurethane is the
presence of urethane linkage as common addition polymerization between a
feature. The initial discovery of diisocyanate and a diol. As the
polyurethane was made by Otto Bayer and polymerization proceeds through a step-
his co-workers of I.G. Farbenindustrie at wise mechanism, it is often named as step-
Leverkusen, Germany in 1937.1 growth polymerization.

Segmented polyurethanes are block


copolymers of (AB)n type consisting of
alternating rigid and flexible segments.
They exhibit properties characteristic of
cross linked elastomers over a wide
temperature range and can be processed by
techniques used for plastics and fibres.
They are a unique class of thermoplastic
material. Due to the different polarity and
chemical nature of the rigid and flexible
segments, they tend to separate into two Figure 2. The two phase structure of bulk-
phases referred to as soft and hard polymer (polyurethane)
phases. The structure of a segmented
polyurethane molecule and domain

N. E. Quest; Volume 1, Issue 4, January 2008, 25


Newsletter of North East India Research Forum

Polyurethanes with flexible polyol polymer backbone makes it a polymeric or


backbone have generally good retention of macrophotoinitiator. Irradiation of such
properties at low temperature which make macrophotoinitiator in presence of vinylic
them suitable candidates for use in monomers such as methyl methacrylate
adhesives, coatings etc. Toughened (MMA), styrene (St), acrylonitrile (AN),
polyurethanes are engineering polymers. 2-hydroxy ethyl methacrylate (HEMA)
They also have biomedical applications. result in block copolymers.
Modification of polymers to improve their
performance as well as to widen their field
Polyurethane–vinyl block copolymers
of application has been a fascinating field
are high-performance polymers which can
of research. The scope of utility of
be used as thermoplastic elastomers. Most
polyurethanes can be further widened by
applications of block copolymers are
block copolymerization with vinylic
stemming from their ability to form
monomers.
microdomains in solution and in bulk.
Current applications of block copolymers
Block copolymerization in general include thermoplastic elastomers and
could be achieved through anionic, compatibilization of polymer blends. The
cationic and radical polymerization. The potential uses of block copolymers in
synthesis of block copolymers through immerging technologies like
free-radical polymerization technique has nanotechnology, nanolithography,
always been more attractive than through photonics, and controlled drug delivery are
anionic and cationic polymerization enormous. Due to their potential
techniques. Free radical polymerization biocompatibility they are widely employed
can be initiated either by thermally or in the manufacture of biomedical devices.
photochemicaly. Compared to thermal Recent studies have also demonstrated that
initiation of free-radical polymerization, these materials can exhibit fascinating
light induced initiation has the advantage electro-responsive and optical properties.
of being applicable at room temperature. It References
also provides selective activation of 1. Hepburn. C., Polyurethanes
photolabile groups in the monomer, Elastomers, Applied Sci., London,
macromonomer etc. A polymer with 1991.
inchain or pendent photo labile groups is 2. Otsu. T., Yoshida. M., Makromol.
termed as polymeric photoinitiator or Chem. Rapid. Commun., 3, 127, 1982.
macrophotoinitiator. Polymeric initiators 3. Otsu. T., Yoshida. M., Tazaki. T.,
having photolabile groups in the main Makromol. Chem. Rapid. Commun.,
chain could be used to initiate light 3(2), 133, 1982.
induced free-radical block
copolymerization. The applicability of this About the author:
method however depends on the
availability of synthetic procedures Smriti Rekha Deka was born in Jorhat,
appropriate to incorporate photolabile Assam. She did her B.Sc. from J.B.
groups into the main chain of polymers College, Jorhat and completed her M.Sc
which can then act as photoinitiators. and Ph.D. from Gauhati University
Various organic disulphides act as (Organic Chemistry). Recently she has
photoinitiators on being irradiated in the joined National Nanotechnology
range 254 nm to 366 nm. The disulphides Laboratory of CNR-INFM-ISUFI,
are further found to act as iniferters University of Lecce , Italy for her post
(initiator, transfer agent and terminator). doctoral research. Currently she is
This concept of iniferters and the model working on functionalization of
for living radical polymerization were nanoparticles with polymers. The title of
proposed by Otsu et al.2,3 Besides her thesis is 'Synthesis of Polyurethane
disulphides, benzoin group also acts as Macrophotoinitiator and its application in
photoinitiator. Incorporation of photolabile Block Copolymerization with Vinylic
disulphide group or benzoin into a Monomers'.

N. E. Quest; Volume 1, Issue 4, January 2008, 26


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Ph.D. Thesis Abstract: transformations include aza- and thia-


Michael condensations, selective oxidation
Newer Catalytic Methodologies for C-N, C-S of organic sulfides to the corresponding
Bonds Formation and Oxidation of Sulfides, sulfoxides and the peroxo form of
Bromide and Alcohols with H2O2 vanadium bromoperoxidase cofactor
mimicking radical bromination of toluenes
and electrophillic oxidation of benzylic
alcohols to the corresponding aldehydes.
The catalysts have been drawn from
Cu(acac)2[acac = acetylacetonate, C5H7O2–
], B(OH)3, Na2B4O7.10H2O, (NH4)2HPO4
and two newly synthesized and fully
characterized compounds, [VO2F(dmpz)2]
and K[V(O2)3]. Water has been used as
solvent as far as practicable and H2O2 has
Dr. Sahid Hussain been our oxidant of choice. H2O2 is an
innocuous reagent that produces water as
Catalysis plays an important part in the only by product thereby rendering it be
rendering chemical transformations very an ecobenevolent chemical species.3 It can
effective, highly selective and be highly cost effective if used in a
environmentally safer. Catalysis is in deed controlled fashion.
not only one of the principal tenets of
‘Green Chemistry’ but also is an integral The text of the thesis has been
part of it. The timely publication of a distributedover a total of six chapters.
compendium on ‘Green Chemistry and
Catalysis’ by Sheldon1 puts this point Chapter 1: Introduction and Scope of
affirm beyond any scope of imagination. Work in the Area:
The invention of a new clean and
appropriate catalyst for a chosen This chapter presents a brief account
transformation is extremely important. of prior arts of hetero-Michael reactions
And for this, a clear understanding of the and the peroxo-based oxidation chemistry.
chemistry of a prospective catalyst or a Importance of C-N, C-S bonds formation
catalytic system and the transformation on and oxidations of sulfides, bromide and
which the catalyst is to be applied upon is alcohols with H2O2 in the field organic
an essential prerequisite. The domain of synthesis are highlighted. It also
catalysis thus expands by crossing emphasizes the need for development of
boundaries of several sub-disciplines safe and cost effective catalysts and
including bio and abio chemistry and catalytic systems for various industrially
material science, for instance. The world important reactions.
market of catalysts is ca 12 billion US
dollars, and the chemical transformations Contemporary importance of the
leading to specific products through chosen aspects of chemistry selected for
catalysis is estimated to be 1.2-6.0 trillion the present Ph. D. research provides a
US dollars.2 This in itself underscores the large scope of the work and much more
need to develop practical catalytic beyond.
processes involving homogeneous,
heterogeneous and bio-catalysts. In fact Chapter 2. Details of Materials and
catalysis in one form or the other Methods, and Equipment
dominates the contemporary chemical
literature. In consonance with the current The sources of chemicals and
trend and appreciating the need for clean solvents, methods for quantitative
chemistry practices, the present thesis has chemical estimations, determination of
been framed mainly on the development of elements and details of all the equipment
newer catalysts. The chosen organic used for physico-chemical studies are
provided in this chapter. The

N. E. Quest; Volume 1, Issue 4, January 2008, 27


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characterization was done using reactions and X-ray structure of three β-


appropriate physico-chemical techniques. sulfidocarbonyls. In order to make the
presentation expressive, Chaper 3 has been
Chapter 3. Catalytic Hetero-Michael divided into four section.
Reactions: 3.1 Cu(acac)2 Immobilized in Ionic
Liquids: A Recoverable and Reusable
The Michael reaction since its Catalytic System for Aza-Michael
discovery in 1889 has been one of the Reactions
most frequently studied reactions in
organic synthesis for C-C, C-N, C-O and Copper(II) acetylacetonate
C-S bonds formation. The conjugate immobilized in ionic liquids has been
addition of a nitrogen or sulfur nucleophile shown to efficiently catalyze the aza-
to an electron rich or electron deficient Michael reaction of amines with α,β-
electrophile, known as aza- or thia- unsaturated carbonyl compounds to
Michael reaction to form a C-N or C-S produce the corresponding β-amino
bond, respectively, constitutes a key carbonyl compounds with great alacrity in
reaction in biosynthesis as well as organic excellent yields (Scheme 3.1). The
synthesis. β-Aminocarbonyl and β- reactions are far more facile than those
thiocarbonyl compounds are the adducts reported earlier. The methodology works
of aza- and thia-Michael reactions, very well using a low catalyst loading with
respectively, usually encountered in easy catalyst and solvent recycling. This
naturally occurring biologically active method is capable of being scaled up, if
compounds such as alkaloids and desired.
polyketides and are widely used
throughout the chemical industry as a R1
R R'
Cu(acac)2, [Bmim]BF4 R1
basic intermediate to prepare NH +
X N
X
rt, 10-120 min
pharmaceutically or agrochemically useful R2
R' R2 R
chemicals. Owing to their wide ranging R= alkyl, H; R'=alkyl, aryl, H 60-98%
biological properties, they are much
R1=R2= alkyl, benzyl, aryl, H
sought after as chemotherapeutic agents
for the treatment of various diseases. They X = CO2Me, CONH2, CN, COCH3, NO2

serve as essential intermediates in the Scheme 3.1


synthesis of γ-amino alcohols, diamines,
β-amino acid derivatives, β-lactam 3.2 Boric Acid: A Novel and Safe Metal-
antibiotics, β-acylvinyl cation, Free Catalyst for Aza- and Thia-Michael
homoenolate anion equivalents, β-calcium Reactions
antagonist diltiazem and natural products.
The thia-Michael reaction also provides an Boric acid efficiently catalyzes the
elegant strategy for the chemoselective conjugate addition of amines or thiols to
protection of the olefinic double bond of α,β-unsaturated compounds to produce β-
conjugated enones due to ease of amino and thia-compounds, with great
generation of the double bond through alacrity and excellent yields, in water
removal of the sulfur moiety by copper(I) under mild conditions (Scheme 3.2).
induced oxidative elimination. Some thia- Aromatic amines do not participate
adducts of amides are known to have effectively in the reaction. The use of
topical relevance to the investigation of boric acid, being a safe chemical, as the
host-guest interactions and are also useful catalyst and water as the reaction medium
as photographic development accelerators. are important attributes in the present
Consequently, the development of newer protocol. The reaction is capable of being
and practical synthetic routes to these performed neatly in the chosen solvent at
important compounds has stimulated ambient temperature without catalyst
constant interest of many research groups poisoning. The thia-Michael reactions can
over the years. Chapter 3 reports a few be performed in ethanol or methanol, as
newer methods for aza-, thia-Michael reported in this section.

N. E. Quest; Volume 1, Issue 4, January 2008, 28


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than amines in aqueous alkaline solution.


A comparison of the present results with
R3 R2 those of the corresponding boric acid
R1
NH +
10mol% Boric Acid R1
X catalyzed aza-Michael reactions suggests
N
R
X H2O, rt, 1-6 h
R
that under similar experimental conditions
70 95%
R2 R3
borax appears to be either as good as or
R = alkyl; R1=
alkyl, H ;
X = CO2Me, COMe, CN, CONH2
R2 =
= alkyl, H R3 somewhat better than boric acid in
catalyzing the chosen reactions.
R2
R3
10-20 mol% Boric Acid
3.4 X-Ray Studies on β-Sulfidocarbonyls
RSH +
X
water, rt , 2-12h
RS
X
Evidencing Intermolecular Hydrogen
R2 79 – 82% R3 Bonded Self-Assembled β-Pleated Sheet
R = alkyl, aryl; R1=
alkyl, H ; R2 = R3 = alkyl, H
Structures
X = CO2Me, COMe, CN, CONH2

Scheme 3.2

3.3 Borax as an Efficient Metal-Free


Catalyst for Hetero-Michael Reactions

Borax, a naturally occurring material, Crystal packing in adduct 1


very efficiently catalyzes the conjugate
addition of thiols, dithiols and amines to
α,β-unsaturated ketones, nitriles, amides, In the course of our research endeavor
aldehydes and esters in aqueous medium in this area, three crystalline compounds
to afford the corresponding Michael were obtained by the conjugate addition of
adducts in good yields at room cysteine, 1,2 and 1, 3 dithiols each to
temperature (Scheme 3.3). Recycling of acrylamide catalyzed by borax in water at
the catalyst and scaling up of the reactions room temperature. The compounds have
are important attributes in this catalysis. been characterized well by chemical
The reactions of thiols and dithiols were analyses, IR and NMR spectroscopic
relatively more facile than the studies. The hitherto unprecedented crystal
corresponding amines.
SR
EWG
1 Borax (10 mol%) EWG
RSH + R
R1
r.t., water
R2
5–180 min / 70–97 % R2

R Borax (10 mol %) R 3 EWG


3
NH + EWG N
r.t., water
R4 R4
1.5–8 h / 25–92 %
Crystal packing in adduct 2
R = alkyl / aryl; R 1 = alkyl / aryl / –(CH 2)–;
EWG = CO 2Me, CN,CONH2 , COMe, COPh
Scheme 3.3 structures of the chosen compounds not
only support their molecular structures but
also provide evidence for strong
intermolecular hydrogen bonding with β-
An internal comparison of the results sheet type of molecular rearrangement in
of thiol additions with those of amine addition to the occurrence of rather
additions, under similar experimental unconventional C–H---O and C–H---S
conditions, shows that the former are more type of H-bonding in the crystal lattice.
facile than the latter. Indeed, this
observation is in agreement with the result
It is expected that the chosen
of some earlier kinetic studies. Based on
compounds might serve as suitable probes
kinetic data it was predicted that –SH
to study hydrogen-bonding interactions in
groups were many times more reactive

N. E. Quest; Volume 1, Issue 4, January 2008, 29


Newsletter of North East India Research Forum

(c.f. protein structure) and obtain insights brief account of this experiment has been
into the realm of sulfidoamide chemistry. included in this chapter.

4.1 Development of a New Catalyst


[VO2F(dmpz)2] for Oxidation of Organic
Sulfides

The synthesis VO2F(dmpz)2 has been


achieved by conducting the reaction of
V2O5 with NH4HF2 and 3,5-dimethyl
Crystal packing in adduct 3 pyrazole under the specified conditions. It
has been ascertained from repeated
reactions that pH=4.2 of the reaction is
crucial for its successful synthesis. The
Chapter 4. Development of New lemon yellow compound is stable for a
Catalysts for Selective Oxidation of long period. The single crystal X-ray
Sulfides with H2O2 analysis shows that the compound is a
Apart from the transformations penta coordinated vanadium (V)
highlighted above, oxidation is a widely mononuclear species.
used multifarious chemical process having
application in almost all of the important Methanolic soln. of Dmpz

fine and specialty chemical industries V2O5 + NH4HF2


manufacturing pharmaceuticals,
agrochemicals etc. A wide variety of
reagents, catalysts and catalystic systems ORTEP view of VO2F(dmpz)2

were developed and well documented.


Endeavour has been made to overcome the Coordinative unsaturation of vanadium(V)
problems associated with oxidation such in [VO2F(dmpz)2] provides an additional
as overoxidation and less selectivity. Some site for H2O2 coordination and
success has been achieved but search is resemblance of pyrazole with imidazole
still on to get an ideal process. In the set some arguments in favor of VBrPO
current scenario, the bio-inspired, or mimic. And with the so designed mimic,
metal-free, catalysis seems to be the safest we carried out oxidation reactions of
option since the nature allows the sulfides with H2O2.
bioorganic reactions utilizing enzyme
vanadium bromoperoxidase (VBrPO) as Various aliphatic and aromatic groups
the catalyst for bromination and oxidation attached to sulfur atom and refractory
(c.f. organic sulfides) of the required sulfur (e.g. dibenzothiophene (DBT), 4-
organic molecules. The knowledge methyl-DBT and 4,6-dimethyl DBT)
obtained from our studies on peroxo compounds were subjected to oxidation
vanadium chemistry and the literature with H2O2 catalyzed by VO2F(dmpz)2. The
information on VBrPO reactivity oxidations were selective affording
encouraged us to develop new and cleaner sulfoxides. In case of allylic sulfides
protocols for oxidations. oxidation, sulfoxides were formed without
the cleavage of carbon-carbon bond.
In this chapter, we have described the
oxidation of sulfides with a newly As a sequel to our research and in
synthesized vanadium complex view of the pressing need for reducing the
[VO2F(dmpz)2], borax and phosphate as sulfur content of diesel to an ultra low
the catalyst and H2O2 as the oxidant. As a level, it was thought worthwhile to try out
logical extension, oxidative the efficacy of the newly developed
desulfurization of diesel was attempted catalyst for the purpose. Accordingly, the
with [VO2F(dmpz)2]–H2O2 and a [VO2F(dmpz)2]–H2O2 system was applied
reasonable success has been achieved. A to diesel containing >2200 ppm of sulfur.

N. E. Quest; Volume 1, Issue 4, January 2008, 30


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The fuel containing oxidized organic Chapter 5. VBrPO-Mimicking Catalysis


sulfurs was purified by passing through an in Water for Radical Bromination as
adsorption column packed with Al2O3 and well as Electrophillic Oxidation, and
activated charcoal (90:10). The output was Oxidative Extraction of Bromide from
found to contain 150-700 ppm of sulfur. Sea Water
This process has been scaled up to 2 L.
Environmentally cleaner access to
4.2 Borax and Phosphate Catalyzed benzyl bromides that serves as precursors
Selective Oxidation of Organic Sulfides of benzyl alcohols appears to be quite a
synthetic challenge, while the global
The selective oxidation of sulfides to requirement for benzaldehydes that are
sulfoxides and sulfones has been achieved obtained from the corresponding alcohols
in high yields at room temperature with is very high (> 20,000 tons per year).
borax as a recyclable catalyst and H2O2 as Benzyl halides including benzyl bromides
the terminal oxidant by varying pH of the are synthesized from the corresponding
reaction medium (Scheme 4.2). The toluenes. Benzylic bromination of toluenes
borax–H2O2 system can chemoselectively is accomplished by radical bromination.
oxidize alkyl as well as aryl sulfides in The bromination of organics with
presence of oxidation prone functional molecular bromine is fraught with the
groups such as C=C, –CN, –OH. Some problems of handling transportation and
refractory sulfides, viz, dibenzothiophene use owing to its high toxicity and
(DBT) and 4-methyl-DBT are also capable corrosive nature. To ease out the problems
of being oxidized quite effectively though several methods were developed, but the
with less selectivity. The oxidations of brominating agents used therein are not
DBTs are especially important in the ecobenevolent, not easy to handle and are
context of transportation fuel chemistry highly toxic. In the given situation, bio-
research targeting desulfurization of diesel inspired catalysis seems to be the
and gasoline, for instance. promising option since the nature allows
such reactions utilizing vanadium
O
pH 6 or 7 pH 10 or 11
O O bromoperoxidase (VBrPO) enzyme as the
S
S Borax (10 mol%) R R' Borax (10 mol%) R
S
R'
catalyst for bromination of the required
organic molecules.
R R' H2O2, CH3OH H2O2, CH3OH
45-92% 5–24h 3–24h 10-95%
Scheme 4.2

Besides the radical bromination,


Selective oxidation of organic sulfides oxidation of alcohols to aldehydes or
to the corresponding sulfoxides seems to ketones is a fundamental transformation in
be possible with (NH4)2HPO4, as well. chemical industries. However, green
Thus, (NH4)2HPO4–H2O2 oxidized a catalytic oxidation of benzyl alcohols as
variety of organic sulfides at pH 7 or 8 opposed to the spate of stoichiometric
(Scheme 4.3). The reaction worked well in oxidations is a relatively grey area that
the chemoselective oxidation of sulfides in needs attention because most of the
presence of C=C, –CN –OH groups. several green procedures have been based
Unfortunately, the catalytic system could on costly metals thereby rendering the
not bring about the oxidation of refractory process economically non viable, in many
sulfurs. A comparison of the results of instances.
borax catalyzed reaction with those of
(NH4)2HPO4, clearly suggests that the In view of this and also because of the
former is a better catalyst. availability of a highly peroxygenated
vanadium(V) species, [V(O2)3]–, at our
O
disposal, it was considered quite apt to use
(NH4)2HPO4 (10 mol%)
S this as a precatalyst for oxidative
S
R R' H2O2, H2O or CH3OH R R'
brominations, and selective oxidation of
pH 7 or 8 alcohols with H2O2. While we are engaged
2–12h 65-89%
in the triperoxovanadate(V) catalyzed
Scheme 4.3

N. E. Quest; Volume 1, Issue 4, January 2008, 31


Newsletter of North East India Research Forum

reactions, it was observed that our Br


[VO2F(dmpz)2] catalyst very efficiently CH3
K[V(O2)3].3H2O / H2O2 / H+ Br Br
catalyzed the oxidation of bromide to KBr, CTAB, water, 6h +
tribromide, Br3–, by H2O2. This X
ambient light X X
5-9%
encouraged us to try out the oxidative 72-78%
O
extraction of bromide from sea water K[V(O2)3].3H2O / H2O2 / H+
OH H
using this catalyst. CTAB, water
X X
55-85%
5.1 An Improved Synthesis of
[K(V(O2)3] and its Use as a Precatalyst for
Radical Bromination and Oxidation Scheme. 5.1

The synthesis of [K(V(O2)3] has been


achieved from the reaction of V2O5 with
H2O2 in the presence of relatively large 5.2 [VO2F(dmpz)2] Catalyzed Oxidative
concentration of alkaline medium with the Extraction of Bromide from Sea Water
molar ratio of V2O5 : H2O2 : KOH being
maintained at 1: 42 : 42.5. The complex The fact that the peroxo form of the
was obtained by the addition of ethanol, enzyme vanadium bromoperoxidase
which fascilated precipitation. The (VBrPO) catalyzes the oxidative
temperature, time and order of addition of bromination of organic molecules in the
the reagents play crucial role in the marine environment, and that VBrPO
successful synthesis of the catalyst. A mimicking catalysts catalyzes the in situ
minor change in the reaction conditions oxidation of Br – to Br3– by H2O2 in the
leads to the formation of mixed peroxo presence of catalytic amount of acid is
complexes. highly significant in the realm of
peroxovanadium(V) chemistry. By
We have investigated benzylic conjuring the bio and abiotic events, it was
bromination of toluene and selective anticipated that a suitable VBrPO
oxidation of benzyl alcohols with H2O2 as mimicking catalyst might enable extraction
the terminal oxidant and the optimal of bromide from sea water in a very soft
reaction conditions have been worked out. way. Accordingly, several catalysts have
Under the optimized reaction conditions, a been developed in our laboratories and the
wide variety of toluene and benzylic performance of [VO2F(dmpz)2] as a
alcohols were converted to their representative example has been reported in
corresponding benzyl bromide and this section (Scheme 5.2a). A slightly
benzaldehyde selectively and efficiently in concentarted pre-analysed sea water
good yields (Scheme 5.1). The catalyst can generally known as ‘bittern’ was obtained
be recycled five times without the loss of from a bromine producing industry (Tata
activity. The procedures are scaled up upto Chemicals Ltd., India). The bromide
10 g and 5 g for toluene and benzyl content of the bittern was 2 g/L.
alcohol, respectively. The
peroxovanadium complex isolated from In the present study, [VO2F(dmpz)2]
the aqueous solution at pH 4 or 5 before has been shown to efficiently and
the reactions as well as after extracting the selectively catalyze the oxidation of Br – in
oxidized product from the reaction bittern by H2O2 in the presence of a small
mixture was identified as K3[(O2)2OV-(µ- amount of acid. The oxidised bromide has
OH)-VO(O2)2].H2O. This is indeed the been isolated from the water solution using
active catalyst. Based on the present either tetrabutyl ammonium or
studies and the knowledge gathered from benzyltriethyl ammonium ion as the
the studies of peroxovanadium chemistry, corresponding tribromide. The extraction of
we proposed the reaction mechanisms. the Br– has beeen found to be nearly
The yield of the targeted product in each quantitative (85%, Scheme 5.2b).
case has been good to very good.

N. E. Quest; Volume 1, Issue 4, January 2008, 32


Newsletter of North East India Research Forum

VO2F(dmpz)2, H2O2, H+ QA
+ Traditional synthesis
– –
3Br Br3 QABr3 O
0.01 : 3.2 : 1.2 CHO CHO
Reduction
+
QA = Tetrabutylammonium or Benzyl triethyl ammonium NO2
Condensation N
NH2
Scheme 5.2a
Scheme 6.1

VO2F(dmpz)2, H2O2/ H+ In view of the above, a relatively more


Br– (Sea bittern) QABr 3
versatile yet simplified procedure was
85, 87%
QA+ perceived based on the reasoning that the
QA+= Tetrabutyl ammonium or Benzyltriethyl ammonium substrates like o-nitrobenzaldehyde and
enolizable ketones could be made to
Scheme 5.2b
interact in the presence of SnCl2 under
microwave irradiation without using any
The identity of the compound has solvent. Our arguments have been that
been ascertained from the results of IR, under microwave irradiation, the reduction
UV and X-ray crystallography. of o-nitrobenzaldehyde by SnCl2 to the
corresponding amino derivatives, in situ
enolization of the chosen ketones, and
enhanced dipole-dipole interactions
between the activated reaction
intermediates would lead to an
instantaneous condensation to afford
quinolines without the use of any solvent
or catalyst. The strategy worked well
affording the desired products in
respectable yields (Scheme 6.2).
CHO SnCl .2H O
2 2 + O

Chapter 6. Microwave Assisted NO2


MW
N
Synthesis of Quinolines Scheme 6.2

The Friedlaender synthesis of


quinolines is a classic method, that
involves two steps, wherein reduction of This protocol is applicable to a wide
o-nitro aryl aldehyde is first achieved range of enolizable ketones (cycloalkyl, n-
followed by the condensation of alkyl, alkyl aryl). It is evident from the
enolizable carbonyl compound in presence results that alkyl and cycloalkyl enolizable
of a Brønsted acid or a Lewis acid ketones readily cyclized with the in situ
catalyst. The relative instability of the generated o-amino benzaldehyde to afford
intermediate, o-amino aldehyde, with its the corresponding quinolines in good to
strong tendency to undergo self- very good yields. Chapter 6 is based on a
condensation rendered such reactions relatively small piece of work entailing
rather complicated. Subsequently, the this work.
synthesis has undergone several Conclusion
modifications over the years. Considering
the development, it was quite imperative In conclusion, we have developed
that quinolines synthesis required further some newer catalytic methodologies for
attention to obviate the need to maintain the aza- and thia-Michael reactions, and
stringent experimental conditions, use of oxidation of sulfides, bromide and
expensive catalysts, and prepare and alcohols. The catalytic protocols are very
isolate the o-amino carbonyls as synthetic
easy to operate, safe, cost-effective and
precursors.
efficient. We have also developed bio-
mimetic catalysts for radical bromination
and electrophillic oxidation of alcohols,

N. E. Quest; Volume 1, Issue 4, January 2008, 33


Newsletter of North East India Research Forum

bromide and sulfides using H2O2 as the (2008) degrees in Chemistry, under the
oxidant. The use of cost-effective, supervision of Prof. M. K. Chaudhury,
innocuous, recyclable catalysts and from the Indian Institute of Technology,
environmentally benign oxidant and eco- Guwahati, India. Presently, he is working
friendly solvents are some of the important as a post doctoral fellow in Nanophotonics
and Nanomedical Research Group,
attributes in the protocols. The work
Pohang University of Science and
embodied in the thesis satisfies the tenets
Technology, Pohang, Republic of Korea.
of “Green Chemistry” and it is anticipated
that the results reported herein will
provide scope for further studies. Effect of Solvent Media in Altering The
Rates of Diel-Alder Reactions an Other C-C
Reference Bond Forming Reactions:
1. A. Sheldon, I. Arends and U.
Hanefeld, Green Chemistry and
Catalysis Wiley-VCH, Weinheim, 1st
Ed., 2007.
2. R. Noyori, Proceedings of Indian
National Science Academy 2006, 72,
267.
3. R. Noyori, M. Aoki and K. Sato,
Chem. Commun. 2003, 1977. Dr. Diganta Sarma
4. M. L. Kantam, V. Neeraja, B. Kavita,
B. Neelima, M. K. Chaudhuri and S. Conventionally most of the organic
Hussain, Adv. Synth. Catal. 2005, 347, reactions are carried out in solution phase.
763. The solution phase, that contains pure or
5. (a) M. K. Chaudhuri, S. Hussain, M. mixed solvents, plays a pivotal role in
L. Kantam and B. Neelima, determining the course of reactions and
Tetrahedron Lett. 2005, 46, 8329; (b) the amount of product formed. There are
M. K. Chaudhuri and S. Hussain, J. other parameters like temperature,
Mol.Catal. A: Chemical 2007, 269, pressure, concentration of reactants and
214. stability of product that are also essential
6. S. Hussain, S. K. Bharadwaj, M. K. in governing the course of reactions.
Chaudhuri and H. Kalita, Eur. J. Org.
Chem. 2007 361.
7. S. Hussain, G. Das and Mihir K.
Chaudhuri, J. Mol. Structure 2007,
837, 190-196
8. M. K. Chaudhuri, S. K. Dehury, S.
Hussain, A. Duarah, N. Gogoi and M.
L. Kantam, Adv. Synth. Catal. 2005,
347, 1349. Scheme I
9. M. K. Chaudhuri, S. K. Dehury, Sahid
Hussain, A. Duarah and N. Gogoi,
Org. Prep. Proc. Int. 2006, 38, 331. However, the change of a solvent in
10. M. K. Chaudhuri and S. Hussain, J. an organic reaction can bring about great
Chem Sci. 2006, 118, 199. changes in its kinetic profiles. There are
several interesting properties of solvents,
About the author: which may be considered significant in
altering the reaction kinetics of organic
Sahid Hussain obtained his B.S. (1999) reactions. The solvent media may promote
from Science College, Jorhat; the Master the reaction rates by stabilizing the
(2001) from Cotton College, Gauhati transition state. The polarity, dielectric
University, Assam. He qualified CSIR-JRF constant, ionizing power, surface tension,
examination and then completed his Ph.D.

N. E. Quest; Volume 1, Issue 4, January 2008, 34


Newsletter of North East India Research Forum

viscosity, etc. of solvents can play crucial environmental pollution caused by the use
role in directing the kinetics of organic of these volatile organic solvents, there is
reactions in a specific manner. a greater need to replace them by
environmentally benign solvents. In this
The Diels-Alder reaction is one of the regard ionic liquids have emerged as
most important C-C bond forming important substitutes for several organic
reactions in organic chemistry to form solvents. Many ionic liquids have been
cyclic structures. It is a class of developed for specific synthetic problems.
cycloaddition reaction between a For this reason, ionic liquids have been
conjugated diene and an alkene, termed “designer solvent”. Ionic liquids
commonly termed the dienophile, to form are considered green solvents in
a cyclohexene system. The remarkable substituting many volatile organic solvents
importance of Diels-Alder reaction lies in as they possess some special properties
the synthesis of natural products and like: (1) They are nonvolatile, (2) They are
physiologically active molecules. For a nonflammable, (3) They have
long time solvent polarity was believed to physicochemical properties that can be
have no effect on the course of a Diels- altered / controlled by judicious selection
Alder reaction due to involvement of of the cation and/or anion and (4) Most
isopolar activated complex. Berson, importantly they can be recycled for a
however, showed a clear relationship number of times without loss of activity.
between the endo/exo product ratio and
solvent polarity in the Diels-Alder reaction Several parameters have been
of cyclopentadiene and acrylates. Diels- discussed to explain dramatic variation in
Alder reactions in aqueous media were reaction rates as well as stereoselectivities
first carried out back in the 1930s, but no in the above mentioned solvent media.
particular attention was paid to this fact The possible origin of forces includes
until 1980, when Breslow and coworkers hydrophobic packing, solvent pressure,
made the startling observation that the hydrogen bonding, hydrophobic hydration,
reaction of cyclopentadiene with butenone and salting-out (S-O) and salting-in (S-I)
in water was more than 700 times faster effects, etc. However, no single parameter
than the same reaction in 2,2,6- can explain the rate profiles of all
trimethylpentane; whereas the reaction reactions studied.
rate in methanol is comparable to that in a
hydrocarbon solvent. Such an unusual The present thesis deals with
acceleration of the Diels-Alder reaction by delineation and understanding of origins
water was attributed to the “hydrophobic of possible forces responsible for rate
effect”, in which the hydrophobic acceleration and stereoselectivities in
interactions brought together the two water, aqueous salt solutions and ionic
nonpolar groups in the transition state. liquids. These have been discussed in
detail in seven separate chapters:
Another important C-C bond
formation reaction is Michael addition. Chapter I describes a critical literature
The reaction is the addition of an enolate survey of the physical organic, green
of a ketone or aldehyde (Michael donors) chemistry and asymmetric aspects of
to an α,β-unsaturated carbonyl compound carbon-carbon bond forming reactions, in
(Michael acceptors) at the β-carbon and particular Diels-Alder and Michael
involves conjugate addition. The reaction reactions. The frontier orbital description
donors are active methylenes such as of cycloaddition as well as mechanistic
malonates and nitroalkanes, and the aspects of Diels-Alder reaction has been
acceptors are activated olefins such as α,β- discussed. The role of secondary orbital
unsaturated carbonyl compounds. interaction in understanding the
stereochemistry of Diels-Alder reactions
The conventional organic solvents has been introduced. Efforts have been
used in organic reactions are known to be made to explain the special role of water
environment pollutants. In view of the highlighting the possible factors like

N. E. Quest; Volume 1, Issue 4, January 2008, 35


Newsletter of North East India Research Forum

hydrophobic effect, hydrogen bonding, The role of cosolvents on the


polarity, Lewis acid catalysis etc. for rate stereoslectivity of Diels-Alder reaction
variation. Ionic liquids are emerging as between cyclopentadiene and methyl trans
potential green solvents over volatile crotonate has also been examined.
organic solvents. Various Diels-Alder Chapter IV discusses the Diels-Alder
reactions carried out in ionic liquids have reactions of different dienes and
been emphasized. Asymmetric aspects of dienophiles (Scheme II) in room
Diels-Alder and Michael reactions are also temperature ionic liquids (Figure I).
reported.

Chapter II deals with the objectives of O

O
the investigations carried out based on the +
literature survey. It also describes the O O
organization of the thesis.
O O
Chapter III is concerned with the
competing role of secondary orbital +
interaction and hydrophobic effect in O O

determining the stereoselectivity of Diels-


Alder reactions.
O O O O
R

In general, Diels-Alder reactions in + R N O O + R


N O

water offer higher endo/exo ratios as O N O

compared to those in conventional organic R = H, CH3, Ph

solvents, but this is not the case for the


reaction of cyclopentadiene with methyl
trans crotonate (Scheme I). Secondary Scheme II
orbital interactions favor Diels-Alder
reactions to be endo selective. But in this
case hydrophobic effect of the methyl The reactions have also been carried
group influences the stabilization of the out in the presence of rare earth metal
geometry of the transition states. triflates to reveal increase in yields and
endo/exo products. It suggests
The effects of aqueous salt solutions enhancement in the catalytic power of the
on the reaction of cyclopentadiene and triflates in room temperature ionic liquids.
methyl trans crotonate have been It is possible to recover and reuse the ionic
investigated. The increase in endo/exo liquid phase with triflates to give
ratios with salting-in agents like GnCl, comparative yields and stereoselectivities
LiClO4, urea etc and the decrease in even after six cycles.
endo/exo ratios with salting-out agents like
LiCl, NaCl, NaBr, KCl, MgCl2, CaCl2 et.
have been discussed in terms of
N
H R
O R

hydrophobic effect. .
N
MeO O
O O H
N OMe

R = H, CH3
(CH2)n N
N N X
+ 1. Hydrolysis
2. Methanolysis

n=1 [EMIM]=1-ethyl-3-methylimidazolium X=BF4, PF6, Lactate, R


+ COOMe
n=3 [BMIM]=1-butyl-3-methylimidazolium TFA, NTf2 R
COOMe
n=7 [OMIM]=1-octyl-3-methylimidazolium

Scheme III
Figure I. Ionic liquids studied

N. E. Quest; Volume 1, Issue 4, January 2008, 36


Newsletter of North East India Research Forum

Chapter V emphasizes the role of solvents About the author:


in asymmetric Diels-Alder and Michael
Diganta Sarma was born in Golaghat
reactions. Methodology is based on the
District, Assam. After completing his
use of quinine as a chiral auxiliary.
M.Sc. degree (2000) from the Department
Quinine derived dienophiles are used to
of Chemistry, Gauhati University, he went
carry out asymmetric Diels-Alder
to Tezpur University to work in a MNES
reactions. After the reaction the chiral
sponsored project. Then he moved to
auxiliary is removed by hydrolysis
NEIST, Jorhat to work in the Natural
(Scheme III).
Product Chemistry Division. He then
joined National Chemical Laboratory,
Quinine derived α,β-unsaturated
Pune to pursue his Ph.D. degree. After
compounds are used to carry out
submitting his Ph.D. thesis in February,
asymmetric Michael reactions (Scheme
2007, he immediately joined the research
IV).
group of Prof. Yoshiaki Kiso, in the
Department of Medicinal Chemistry,
H
O
N
CH3 O
Kyoto PharmaceuticalUniversity, Kyoto,
MeO O
O
H
O
N
N O Japan. Currently, he is working on
NaH, THF
N
+ HN O
MeO O “Synthesis and structure activity
N
relationship study of peptidomimetic
1. Hydrolysis coronavirus protease inhibitors.”
2. Methanolysis

MeO N O

O
---------------------0----------------------
Scheme IV.

Chapter VI reveals the conclusions of the “True knowledge exists in


research work and future prospects of the knowing that you know
studies. nothing. And in knowing
that you know nothing,
Chapter VII is a detailed description of that makes you the
the experimental procedures to carry out smartest of all.”
Diels-Alder reactions in water, salt
solutions and ionic liquids. Stereochemical Socrates
assignments and solubility measurements
are discussed in detail. Synthesis of ---------------------0----------------------
different ionic liquids, dienophiles and
compounds for asymmetric reactions are
reported. NMR spectra for product
confirmation and gas chromatographs for
quantitative determination of the endo/exo
ratios as well as enantiomeric excess are “Wise men talk because
presented.
they have something to
Thus the present work focuses on the
say; fools, because they
possible origin of forces responsible for have to say
the rate enhancement in Diels-Alder something.”
reactions in water, aqueous salt solutions
and ionic liquids. The effect of solvents on Plato
asymmetric Diels-Alder and Michael ---------------------0----------------------
reactions are quantified through various
solvent parameters.

N. E. Quest; Volume 1, Issue 4, January 2008, 37


Newsletter of North East India Research Forum

Five Firsts in Chemistry: 3. Advances in environmental


contamination:
American Chemical Society has
compiled a Top 5 from its own The research appeared in the August
publications. "Five Firsts of 2007" issue of Environmental Science &
introduces, Technology. According to Neil Bruce and
colleagues at the University of York, toxic
1. Advances in personal security: TNT contamination is a major
environmental problem at many World
The first molecular keypad lock appeared War II sites, military training areas, and
in January in the Journal of the American explosive manufacturing sites. The
Chemical Society, promising defense and researchers inserted a gene for a TNT-
intelligence agencies a way to safeguard transforming bacterial enzyme into a
top-secret data using a device the size of a tobacco plant and found that the novel
single molecule. Abraham Shanzer and bacteria could metabolize the compound
colleagues at the Weizmann Institute of into a non-toxic, non-explosive form.
Science in Rehovot, Israel, based their "This is the first report to demonstrate that
molecular keypad lock on molecules that transgenic plants engineered for the
fluoresce only in response to the correct phytoremediation of organic pollutants can
sequences of three input signals. "By increase the functional and genetic
harnessing the principles of molecular diversity of the bacterial community in
Boolean logic, they have designed a acutely polluted soil compared to wild
molecular device that mimics the type plants.
operation of an electronic keypad, a
common security circuit used for 4. Advances in renewable energy:
numerous applications in which access to
an object or data is to be restricted to a This advances allowed
limited number of persons. nanotechnologists to "wire up" enzymes
for producing hydrogen in fuel cells.
2. Advances in cardiovascular disease: Writing in Nano Letters, Michael Heben,
Paul King, and colleagues at the National
The first study appeared in the Journal Renewable Energy Laboratory, in Golden,
of Proteome Research in July aimed at Colorado, have combined hydrogenases
finding more effective treatments for with electrically conducting carbon
patients for whom aspirin simply doesn't nanotubes to make "biohybrid" conjugate
work. Blood proteins are involved in materials as components of a future
aspirin resistance, a condition that hydrogen fuel cell technology.
prevents thousands of patients from
reaping aspirin's beneficial effects in 5. Advances in genetic disease:
protecting against cardiovascular disease.
Antonio Lopez-Farre, Carlos Macaya, and Scientists in California this year
their colleagues at the Hospital Clinico reported an advance toward rapid
San Carlos in Madrid, used the novel antenatal testing of Down syndrome and
technique of two-dimensional other chromosomal abnormalities. In an
electrophoresis to study changes in October issue of Analytical Chemistry,
different proteins present in two groups of Stephen Quake and Christina Fan of
patients (e.g: aspirin-sensitive and aspirin Stanford University point out that most
resistance) with coronary artery disease, existing pre-natal test depend on the time-
the underlying cause of most heart attacks. consuming method of karyotyping. The
They found increased levels of three new test is based on the polymerase chain
proteins involved in the binding of vitamin reaction (PCR) and allows DNA to be
D in patients with aspirin resistance. These tested without the two-week cell culture
results may aid future development of step traditionally needed for karyotyping.
more effective therapies for aspirin-
resistant patients. (Compiled by Mr. Bipul Sarma)

N. E. Quest; Volume 1, Issue 4, January 2008, 38


Newsletter of North East India Research Forum

Introduction of Forum Members:

Miss Babita Baruwati (12th September, Mr. Bolin Chetia from Sivasagar, Assam,
1980) is originally from Jamugurihat, received Bachelor degree in Chemistry
Sonitpur, Asom. She did her B Sc in from Govt. Science College, Jorhat
Physics from Cotton College, Guwahati (Dibrugarh University) in 1999. After
(Gauhati University) securing first class receiving Master degree in Chemistry
10th position with distinction in the year (First class first position, in 2002) from
2000. She finished her M Sc Physics Dibrugarh University, Assam (Organic
(High Energy, Nuclear Physics) in the Chemistry specialization), he joined as a
year 2002 from Gauhati University Lecturer in the department of Chemistry,
securing first class 7th position. She Dibrugarh University in January 2003 and
cleared her CSIR-JRF exam in June 2002 serve there till April 2004. Then he moved
and joined the Nanomaterials Group, to Regional Research Laboratory (RRL),
Indian Institute of Chemical Technology, Jorhat, as a research fellow where he
Hyderabad for her PhD under Dr. S. V. worked for almost four months. He
Manorama in March 2003. Her PhD thesis qualified CSIR-UGC JRF and GATE held
entitles “Studies on the Synthesis, in 2003. Currently he is doing his doctoral
Characterization, Surface Modification research in Indian Institute of Technology
and Application of Nanocrystalline Guwahati, since December 2004. His area
Nickel Ferrite”. She has published her of research is to develop better techniques
works in eight international journals for getting nanomaterials, synthesize new
including Applied Physics Letters and hybrid materials with tunable properties
Organic Letters. She has attended many and testing their catalytic, electronic
national and international symposia held at properties as well as look for newer
several places. She will be joining Dr. R. applications for chemical & biological
S. Varma at National Risk Management sensors, light emitting devices,
Laboratory, Cinncinati, Ohio, USA as a solar/photovoltaic cells (PVC) etc. During
postdoctoral fellow in February, 2008. this period, he visited Kyushu Institute of
Technology, Kitakyushu, Japan from 28th
---------------------0---------------------- Aug. to 10th Sept. 2005 to deliver an
invited talk entitled “Energy efficient
organic-inorganic hybrid materials”.

“Animals have these ---------------------0----------------------


advantages over man:
they never hear the clock
strike, they die without
any idea of death, they have no theologians
to instruct them, their last moments are not I am not one who was born
disturbed by unwelcome and unpleasant in the possession of
ceremonies, their funerals cost them nothing, knowledge; I am one who is fond of
and no one starts lawsuits over their wills.” antiquity, and earnest in seeking it there.
Confucius
Voltaire ---------------------0----------------------
---------------------0----------------------

N. E. Quest; Volume 1, Issue 4, January 2008, 39


Newsletter of North East India Research Forum

Through The Lenses of Forum Members:

Drops of love Free will

I am the queen
Twilight at Bharalu

First light

Looking ahead

[From: Mr. Mohen Konwar and


Togetherness
Mr. Bipul Sarma]

N. E. Quest; Volume 1, Issue 4, January 2008, 40


Newsletter of North East India Research Forum

Message:

“Helping Hands Are Better Than Praying Lips”

Think and look at this………….


When you complain about your food and the food we wasted daily

Hope this picture will always serve as a reminder to us that how fortunate we are
and that we must never ever take things for granted.

---------------------0----------------------

Have a merry- X-mas day.

Jesus is reborn inside you like the earlier years


As you asking your every prayer
Because He knows,
You are the right person to be His place for reincarnation
Just you need to search out Him and give Him the place inside you
Before His return for wrong reason to heaven
I know, you could handle His tenderness and delicacy
Against all hardship to win peace and prosperity
Only for thousands lives
Who thrives to achieve
A smile with eternal beauty
Lasting ever and forever
To make this wonderful Universe always mesmerizing
And marry making just like today
A very very happy merry X-mas day.

(by: Dr. Tankeswar Nath)

---------------------0----------------------

N. E. Quest; Volume 1, Issue 4, January 2008, 41


Newsletter of North East India Research Forum

Higher Study Abroad

Postdoctoral Positions:

(1) Brookhaven National Laboratory


Department: Biology
Location: Upton, NY, U.S.A.
Start Date: 1st quater 2008
Duration: Two years

Description: This new project is under the direction of A. M. Orville, and is also
associated with the PXRR group (www.px.nsls.bnl.gov) at Brookhaven National
Laboratory (BNL). The PXRR group conducts research, technology development,
operations, and training at six beamlines (X8, X12b, X12c, X25, X26c, X29) at the
National Synchrotron Light Source (NSLS). A long-term goal for the PXRR group
is to create a resource for macromolecular crystallography at NSLS-II, the new
synchrotron light source that is being created at BNL during the next five to
seven years. Microcrystals only a few microns along an edge are often easy to
obtain; but, are typically of no use for traditional diffraction studies. In contrast,
the brightness and focused beam anticipated at NSLS-II provides an ideal
opportunity to use microcrystals for diffraction studies. A major barrier that
remains to be overcome is how to manipulate microcrystals for structure
determination. Part of the research strategy will be to use a large number of
randomly oriented microcrystals, from each of which only a small fraction of the
whole dataset is collected, in order to build-up the complete dataset. Full
expression of these methods may approach the physical limits of crystal
diffraction and will clearly help motivate the optimum performance of NSLS-II.
Consequently, we will develop novel microcrystallography methods at the NSLS
and look forward to utilizing the outstanding characteristics of NSLS-II facility.
The position requires a Ph.D. in biochemistry, structural biology, chemistry, or
physics. Experience in macromolecular crystallography and/or synchrotron x-ray
sources is desired. The prospective candidate must be able to interact with a
diverse group of scientists and engineers, as well as work independently. Send
CV and contact information for four mentors or referees to felicia@bnl.gov
referring to Position No. FH4835.

Other details: referring to Position No. FH4835


Please submit: CV and contact info to request 4 letters of reference
Person to contact: Felicia Hartsough, FH4835
Surface mail address: Human Resources and Occupational Medicine Division,
Brookhaven Nationial Lab, Upton, NY 11973
Email address: felicia@bnl.gov
Phone number: 631-344-2213
Fax number: 631-344-7170
Job Posted: 01/10/08
Job ID Number: 1199972727

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(2) University of Dublin, Trinity College


School of Pharmacy and Pharmaceutical Sciences
Status: 1-2 Year Post
Closing Date: Until position is filled
Salary: Approximately €36,000 per annum depending on experience and
qualifications

A Postdoctoral position is available in the School of Pharmacy and


Pharmaceutical Sciences.The interdisciplinary project is funded by Enterprise
Ireland under the Commercialization Phase; Technology Development. It
involves the preclinical development of novel prodrugs capable of delivering
aspirin and nitric oxide. The project is being conducted in collaboration with Prof
Marek Radomski also of the School of Pharmacy. The candidate must have a PhD
in Pharmaceutical or Medicinal Chemistry. He/she is expected to be highly
motivated, independent and have a strong background in organic synthesis but
with significant analytical experience for example in HPLC or CE.
To apply, please send your CV, application letter and the name of three referees
to:
Dr. John F Gilmer, Pharmacy and Pharmaceutical Sciences, Trinity College
Dublin,
College Green, Dublin 2, Ireland , E-mail: gilmerjf@tcd.ie
We welcome applications by e-mail. Please note there is no application form to be
completed.

(3) In Functional Organic Materials


Company/Institution: ENS Cachan
Location: Cachan, France
Date Posted: 7 January 2008

The Photophysics and Photochemistry of Supra- and Macromolecules laboratory


(PPSM) at Ecole Normale Superieure de Cachan (ENS Cachan), located in the
Paris area, is offering a one-year postdoctoral position to work on a new concept
combining the photo structuration of functionalized organic or silica
nanoparticles and non-destructive nonlinear read-out for 3D-optical data storage.
The studies will focus on the elaboration and optical studies of novel hybrid
materials in tight collaborations with physics laboratories at ENS Cachan and
CEA Saclay. The PPSM lab is provided with numerous facilities for organic
synthesis, material elaboration, characterizations (spin-coating, evaporation,
metal sputtering, profilometer, AFM, MEB), spectroscopic equipments (steady-
state UV-Vis, IR and time-resolved nano- and pico-second studies), as well as
optical studies (holography, second-order NLO setups, confocal microscopes).
Candidates must possess a PhD in chemistry and a solid background in organic
synthesis as well as in spectroscopy or in material sciences. They must supply a
covering letter describing their expertise and interest for the position, a detailed
curriculum vitae and recommendation letters or list of references to the address
mentioned
Contract: 1-year contract with ~2200 euros gross income per month
Email: ishow@ppsm.ens-cachan.fr
Web: http://www.ppsm.ens-cachan.fr and http://www.ida.ens-cachan.fr

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(4) Harvard Medical School


Department: BCMP in collaboration with Children's Hospital; Center for
Molecular and Cellular Dynamics
Location: The Hub (a.k.a. Boston, USA)
URL: www.employment.harvard.edu
Start Date: immediately

Description: A postdoctoral position is available for a highly motivated


individual to study proteins from the microRNA processing pathway. Preference
will be given to candidates who have a strong background in molecular biology as
well as in protein and RNA biochemistry. Experience with crystallography will be
advantageous and although it is not required you must be willing to learn. Please
submit application materials electronically in the pdf format.

Please submit: CV, 3 references, date of availability


Person to contact: Piotr Sliz, Assistant Professor of Pediatrics
Surface mail address: 250 Longwood Ave, Rm SGM-130
Email address: sliz@crystal.harvard.edu
Phone number: 617-432-5608, ext 70
Fax number: 617-432-5600
Job Posted: 01/07/08
Job ID Number: 1199768331

(5) In Nanomagnetism
Universität Konstanz
Fachbereich Physik
Dr. Mathias Kläui
E-mail: M.Klaeui@uni-konstanz.de

In the Department of Physics, University of Konstanz, PhD and Postdoc positions


are immediately available in the field of magnetism on the nanoscale within the
Junior Research Group “Nanomagnetism” funded by the European Research
Council. Magnetization switching by spin-polarized current injection, rather than
by using external magnetic fields has recently stirred much attention [1-3], since
this novel effect has the potential for fast, reliable and simple switching, which is
of great interest for applications in sensors, storage, logic [1-2] and microwave
devices [3]. The underlying fundamental physical principles governing the
electron-magnetization interaction are presently not well understood and in a
combined experimental and theoretical study this effect will be investigated
using a range of experimental techniques and numerical simulations. Low
temperature magneto-transport measurements (300mK to room temperatures
with fields up to 14T) will be carried out and the magnetoresistance effects will
be correlated with the spin structure, which is imaged using high resolution
photoemission electron microscopy, electron holography and other techniques.
Using nanosecond current pulses and microwave excitations, domain walls can
be displaced and the dynamics of the domain wall propagation can be measured
using time-resolved magnetotransport and magnetooptical techniques. It is
intended that part of the PhD/Postdoc stay can be carried out abroad at the
partner institutions, such as the University of Cambridge, the École
Polytechnique in Paris and others from the SpinSwitch Network
(www.spinswitch.de).

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Newsletter of North East India Research Forum

Requirements: Diplom (Master or equivalent) in physics, electrical engineering,


materials sciences, etc.) for a PhD position / PhD for a postdoctoral position.
Knowledge in condensed matter, in particular magnetism would be
advantageous.
The University of Konstanz has recently been designated as one of the 9 German
Elite Research Universities and the Physics department at the University of
Konstanz has been consistently ranked as one of the leading departments in
Germany. It is particularly strong in the area of condensed matter physics and it
houses the national German Collaborative Research Centre on “Controlled
Nanosystems” (SFB 767).
The salary scale is TVL13 (3/4) (PhD) and TVL13 (Postdoc); in exceptional
circumstances other arrangements might be possible. For enquiries and
applications including a full CV contact Dr. M. Kläui (Email:
nanomagnetism_applications@uni-konstanz.de,Tel.+49-7531-883786,Fax.883789

(6) Purdue University


Department: Department of Biological Sciences
Location: West Lafayette, Inadiana
URL: www.biology.purdue.edu/people/faculty/index.php?refID=188
Start Date: ASAP

Description: A Postdoctoral position is available in the area of membrane protein


structural biology at the Markey Center for Structural Biology, Department of
Biological Sciences, Purdue University. We are actively pursuing structures and
mechanistic studies of transporters, ion channels and receptors of biomedical
importance. Preference will be given to candidates who have a strong background
in X-ray crystallography and/or biophysics. Experience in protein purification
and crystallization and/or membrane protein biochemistry are desirable but not
necessary. The Markey Center for Structural Biology provides state of the art
facilities for research and a highly interactive environment with multiple
laboratories working in the area of membrane protein structural biology. Please
submit via email: curriculum vita, brief summary of previous work, and the
names and contact information of three references
Please submit: CV, brief summary of previous work, and contact information of
three references
Person to contact: Dinesh Yernool
Surface mail address: 915 W State St., B220, Lilly Hall, West Lafayette, IN
47907
Email address: dyernool@purdue.edu
Phone number: 765-494-1960
Fax number: 765- 496-1189
Job Posted: 12/30/07
Job ID Number: 1199059394

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Newsletter of North East India Research Forum

Details about the Northeast India Research Forum

Date of creation of the forum: 13th November 2004


Area: Science and Technology
Total number of members till date: 175
Cover page designed by: Mr. Anirban Adhikari
Logo designed by: Dr. Manab Sharma

Moderators:

1. Arindam Adhikari, Ph.D. 2. Jadab Sharma, Ph.D.


Institute of Surface Chemistry, Royal Email: js_in1@yahoo.co.in
Institute of Technology, Stockholm, Sweden
Email: arindam_tsk@yahoo.com

3. Utpal Borah, Ph.D. 4. Ashim J. Thakur, Ph.D.


Gifu Pharmaceutical University, Japan Chemical Science Dept, Tezpur University,
Email: utbora@yahoo.co.in Tezpur, Assam
Email: ajtthax@yahoo.com

Editorial Team of NE Quest

1. Dhanapati Deka, Ph.D. 2. Tankeswar Nath, Ph.D.


Reader, School of Energy, Environment and Scientist, R&D, Biotechnology,
natural reseources, Tezpur University, Jubilant Organosys Ltd. Gajraula, UP, India
Assam Email: tankeswar_nath@jubl.com
Email: dhanapati@tezu.ernet.in

3. Manab Sharma, Ph.D. 4. Rashmi Rekha Devi, Ph.D


Dept of Chemistry, Technion-Israel Institute Scientist, Defence Material & Stores
of Technology, Israel. Research & Dev. Establishment, DRDO,
Email: mansharma123@yahoo.com Kanpur.
Email: devi_rashmi@yahoo.com

5. Joshodeep Boruwa, Ph.D. 6. Pankaj Bharali,


Fachbereich Chemie, L-940 Indian Institute of Chemical Technology,
Universitat Konstanz Hyderabad, India.
D-78457, Konstanz, Germany Email: pankaj_rrlj@yahoo.co.in
Email: jboruwa@googlemail.com

7. Pranjal Saikia 8. Ashim Thakur, Ph.D.


I&PC Division
IICT, Hyderabad, India 9. Utpal Borah, Ph.D.
Email: psjorhat@yahoo.co.uk
(Volunteer editor of this Issue )
10. Arindam Adhikari, Ph.D.
http://tech.groups.yahoo.com/group/northeast_india_research/

www.neindiaresearch.org

N. E. Quest; Volume 1, Issue 4, January 2008, 46


Newsletter of North East India Research Forum

N. E. Quest; Volume 1, Issue 4, January 2008, 47

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