NANOPARTICLES

A nanometer (nm) is one thousand millionth of a metre. A human hair is about 80,000nm across and the diameter of a human blood cell is in the region of 7,000nm. Research into nanotechnologies considers sizes of around 100nm down to the size of atoms (appro imatel! 0." nm). A nanoparticle is considered to be an! three dimensional ob#ect that falls within this scale although for simplicit! this also includes one dimensional entities (e.g $er! thin films) and two dimensional ob#ects (e.g nanowires and nanotubes).

%ar from being a recent in$ention, nanoparticles ha$e e isted since before the ascent of man and can be found in nature in the form of $olcanic ash, ocean spra!, smo&e from forest fires, cla! and clouds.

Research is so interested in de$eloping nanotechnologies for two main reasons. %irstl!, nanoparticles ha$e a much larger surface area when compared to a similar material on a larger scale and this can ma&e some materials more chemicall! reacti$e to the e tent that some materials become reacti$e at the nanoscale that would be considered inert in larger form. 'econdl!, (uantum effects can begin to dominate the beha$iour of matter at the nanoscale affecting the optical, electrical and magnetic beha$iour of materials.

What Makes Nanoparticles Different? )anoparticles are larger than indi$idual atoms and molecules but are smaller than bul& solid. *ence the! obe! neither absolute (uantum chemistr! nor laws of classical ph!sics and ha$e properties that differ mar&edl! from those e pected. +here are two ma#or phenomenons that are responsible for these differences. %irst is the high dispersit! of nanocr!stalline s!stems. As the size of a cr!stal is reduced, the number of atoms at the surface of the cr!stal compared to the number of atoms in the cr!stal itself, increases. %or e ample, a , nm diameter -d' nanoparticle has about 1.00 atoms, of which about a third are on the surface. /roperties, which are usuall! determined b! the molecular structure of the bul& lattice, now become increasingl! dominated b! the defect structure of the surface.

+he diagram abo$e shows a schematic representation of the different sizes.

+he second phenomenon occurs noticeabl! onl! in metals and semiconductors. 0t is called size (uantisation and arises because the size of a nanoparticle is comparable to the de 1roglie wa$elength of its charge carriers ( i.e. electrons and holes). 2ue to the spatial confinement of the charge carriers, the edge of the $alance and conduction bands split into discrete, (uantized, electronic le$els. +hese electronic le$els are similar to those in atoms and molecules.

0n

diagrams the conduction and $alence bands in the solid, nanoparticle and atom state of a semiconductor (left) and a metal (abo$e) are compared. 0t can be seen here again that nanoparticles represent a state of matter in the transition state between bul& solids and indi$idual atoms.

+he spacing of the electronic le$els and the bandgap increases with decreasing particle size. +his is because the electron hole pairs are now much closer together and the -oulombic interaction between them can no longer be neglected gi$ing an o$erall higher &inetic energ!. +his increase in bandgap can be obser$ed e perimentall! b! the blue3shift in the absorption spectrum or sometimes e$en $isuall! b! the colour of the samples. A larger bandgap means that more energ! is re(uired to e cite an electron from the $alance band to the conduction band and hence light of a higher fre(uenc! and lower wa$elength would be absorbed. +he increase in molar absorption coefficient shows that the oscillator strength also increases as particle size decreases. +his is due to the strong o$erlapping of the wa$e functions of confined charge carriers. 4 periments carried out in the past ha$e found the absorption spectrum to be potential dependent, with decreasing wa$elengths as applied potential decreases. +his change is full! re$ersible before the threshold potential.

NEW TECHNIQUE MAPS TWIN FACES OF SMALLEST JANUS NANOPARTICLES

-hemists ha$e de$eloped the first method that can rapidl! and accuratel! map the surfaces of 5anus nanoparticles, tin! particles that possess two chemicall! distinct faces. +he findings ha$e broad potential applications ranging from drug deli$er! to $ideo displa!s. +hese particles are named after the two3faced Roman god 5anus and their twin chemical faces allow them to form no$el structures and new materials. *owe$er, as scientists ha$e reduced the size of 5anus particles down to a few nanometers in diameter 6 about the size of indi$idual proteins, which has the greatest potential for drug therap! 6 their efforts ha$e been hampered because the! ha$en7t had a wa! to accuratel! map the surfaces of the particles that the! produce. +his uncertaint! has made it difficult to e$aluate the effecti$eness of these particles for $arious applications and to impro$e the methods researchers are using to produce them. )ow, a team of 8anderbilt chemists has o$ercome this obstacle b! de$eloping the first method that can rapidl! and accuratel! map the chemical properties of the smallest of these 5anus nanoparticles. +he results, published online this month in the 9erman chemistr! #ournal Angewandte Chemie, address a ma#or obstacle that has slowed the de$elopment and application of the smallest 5anus nanoparticles. +he fact that 5anus particles ha$e two chemicall! distinct faces ma&es them potentiall! more $aluable than chemicall! uniform particles. %or e ample, one face can hold onto drug molecules while the other is coated with lin&er molecules that bind to the target cells. +his ad$antage is greater when the different surfaces are cleanl! separated into hemispheres than when the two t!pes of surfaces are intermi ed. %or larger nanoparticles (with sizes abo$e 10 nanometers), researchers can use e isting methods, such as scanning electron microscop!, to map their surface composition. +his has helped researchers impro$e their manufacturing methods so the! can produce cleanl! segregated 5anus particles. *owe$er, con$entional methods do not wor& at sizes below 10 nanometers. +he 8anderbilt chemists 6 Associate /rofessor 2a$id -liffel, Assistant /rofessor 5ohn :c;ean, graduate student <ellen *ar&ness and ;ecturer Andrze# 1alins&i 6 too& ad$antage of the capabilities of a state3of3the3art instrument called an ion mobilit!6mass spectrometer (0:3:') that can simultaneousl! identif! thousands of indi$idual particles.

+he team coated the surfaces of gold nanoparticles ranging in size from two to four nanometers with two different chemical compounds. +hen the! bro&e the nanoparticles down into clusters of four gold atoms and ran these fragments through the 0:3:'. :olecules from the two coatings were still attached to the clusters. 'o, b! anal!zing the resulting pattern, the chemists showed that the! could distinguish between original nanoparticles where the two surface compounds were completel! separated, those where the! were randoml! mi ed and those that had an intermediate degree of separation.

5ohn :c;ean >ni$ersit!)

(5ohn

Russell

8anderbilt

?+here is no other wa! to anal!ze structure at this scale e cept @3ra! cr!stallograph!,A said -liffel, ?and @3ra! cr!stallograph! is e tremel! difficult and can ta&e months to get a single structure.A ?0:3:' isn7t (uite as precise as @3ra! cr!stallograph! but it is e tremel! practical,A added :c;ean, who has helped pioneer the new instrument7s de$elopment. ?0t can pro$ide structural information in a few seconds. +wo !ears ago a commercial $ersion became a$ailable so people who want to use it no longer ha$e to build one for themsel$es.A +he research was funded in part b! a grant from the )ational 0nstitutes of *ealth.