Introduction

CHAPTER-1
INTRODUCTION
1.1 Cyclodextrins
1.1.1 History of Cyclodextrins
1.1.1.1 Discovery Period
The first paper was published in 1891 by Villiers that reported the formation of
some unidentified crystalline substance during fermentation of starch [1]. Villiers, the
French author, assumed that this substance is some kind of cellulose and named it
cellulosine. An Australian Microbiologist, Franz Schardinger about 15 years later,
whilst studying those microorganisms which play a role in the deterioration of foods,
isolated a microorganism (named Bacillus macerans) which produced reproducibly two
distinct crystalline substances when cultivated on starch medium [2]. Because most of
their properties were similar to the already known partial degradation products of starch,
he named them as -dextrin and -dextrin Freudenberg and his co-workers elucidated the
cyclic structure of these two dextrins in the mid 1930s. This period from 1891-1936 is
called the discovery stage in the history of CDs.

1.1.1.2 The exploratory period from 1936-1970

After 1930s, Freudenberg and his co-workers came to the conclusion that the
crystalline Schardinger dextrins are built from maltose units and contain only

-(1,

4) glycosidic linkages [3]. In 1950, -CD was discovered and its structure elucidated.
Freudenberg, Cramer and Plieninger were granted a patent in 1953 [4]. D. French published
the first fundamental review on cyclodextrins 1957 [5].

1.1.1.3 The utilization period: from 1970-onward

The first international symposium on CDs was organized in 1981 [6]. An international
CD symposium has been organised every 2

nd

year from 1984 onwards. By the end of

2003, the total numbers of CD related papers/publications were over 26000. P. R.

Sundrarajan and V. S. R. Rao demonstrated by conformation energy map calculations that
CDs with less than six members cannot be formed due to steric considerations [7]. F. V.
Lichtenthaler and S. Immel

Introduction
coined the term cyclodextrin as a generic nomenclature for all the Cyclooligosaccharides depending upon the numbers of glucose units present in a ring [8].
The spectacular development of CD technology relies on a series of reasons such as:
They are natural products, produced form a renewable natural material (starch)
by a
relatively simple enzymatic conversion;
They are produced in 1000 tons/yr amounts by environmental technologies;
Their initial high price have dropped to levels where they become acceptable for
most of the industrial purposes;
Through their inclusion complex forming ability, important properties of
the complexed substances can be modified significantly. This unprecedented
molecular encapsulation is utilized in many industrial products, technologies
and analytical methods;
Any of their toxic effects is of secondary character and can be eliminated by
selecting the appropriate CD type, derivative, or mode of application;
CDs can consequently be consumed by humans as ingredients of drugs, foods
and cosmetics.

1.1.2 Structural features of Cyclodextrins (CDs)

Cyclodextrins comprises a family of three well known industrially produced major,
several rare and minor cyclic oligosaccharides. The three major CDs are crystalline,
homogeneous, nonhygroscopic substances, which are torus like macro rings built up
from

gluocopyranose

units.

The

-cyclodextrin

(Schardingers

-dextrin,

cyclomaltohexose, cyclohexaglucan, cyclohexaamylose, -CD, ACD, C6A) consisting

six gluocopyranose units, -cyclodextrin (Schardingers -dextrin, cyclomaltoheptaose,
cycloheptaglucan,

cycloheptaamylose,

-CD, BCD,

C7B)

consisting

gluocopyranose units and -cyclodextrin (Schardingers -dextrin,

cyclooctaglucan,

cyclooctaamylose,

gluocopyranose units.

-CD,

GCD,

of

seven

cyclomaltooctaose,

C8A) consisting of eight

1.1.3 Shapes and size of Cyclodextrins (CDs)

Cyclodextrins (CDs) have been described as seductive molecules, appealing to
investigators both in pure research and applied technologies. Cyclodextrins have
truncated cone or bucket shaped structure (Fig. 1.1.1). CDs are water soluble, cyclic,
non-reducing oligosaccharides consisting of D-(+)-gluocopyranose units linked through
-(1, 4) glycosidic linkages. The major and most common three cyclodextrins, cyclodextrin, -cyclodextrin and -