Reactive & Functional Polymers 52 (2002) 163188

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Polyphenolic compounds: an overview

J.G. Handique, J.B. Baruah*
Department of Chemistry, Indian Institute of Technology, Guwahati, North-Guwahati 781 039, India

Received 12 January 2002; received in revised form 4 May 2002; accepted 20 May 2002

Abstract

A comprehensive review on the polyphenolic compounds is presented. The emphasis is placed on the structural and
functional implications on the regiochemistry as well as on the stereochemistry of oligomeric polyphenols. A correlation
between the natural polyphenolic compounds and the synthetic ones is highlighted by making a general classification of
polyphenolic compounds. The uses and applications of polyphenolic compounds are discussed in detail.
2002 Elsevier Science B.V. All rights reserved.

Keywords: Polyphenols; Calixarenes; Classification; Conformations; Supramolecular chemistry

1. Introduction supramolecular interaction. Stacking of aromatic

Polyphenolic compounds are usually referred
to as a diverse group of naturally occurring
compounds containing multiple phenolic func-
tionalities [1]. These compounds are commonly
found in higher plants. They have synthetic,
medicinal and industrial value. Naturally occur-
ring polyphenols are known to have numerous
biological activities. They are found to be
potential candidates for use as drugs, for exam-
ple [1], in diseases like AIDS, heart ailments,
ulcer formation, bacterial infection, mutagenesis
and neural disorders. Plant polyphenols are also
responsible for flower colouration [25]. The
prime factor for the colouration of flowers is
*Corresponding author.
E-mail address: juba@iitg.ernet.in (J.B. Baruah).
nuclei, keto-enol tautomerism and pH also
effect the change of colour in polyphenols.
From a chemical point of view, polyphenols
can react with one-electron oxidants, which
prevents free radical formation in biological
systems. Such single electron oxidation pro-
cesses are considered to be the key steps of
polyphenols while acting as drugs [6]. The
ability of these compounds to interact with
metal ions such as Fe 21 , which is capable of
generating free radicals, has significance in their
bioactivity. However, some polyphenols under
special circumstances may behave as pro-oxid-
ants [1]. The other important aspects of these
polyphenols are the interactions of available
multiple polar functional groups for selective
and unselective binding with biologically im-
portant molecules such as proteins. Because of
the presence of multiple phenol functionalities,
they interact with proteins so strongly, that

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164 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188

precipitation of proteinpolyphenol complexes chanically stronger than other organic polymeric

occurs frequently, which is the basis of their use supports like polystyrene [15].
in the tanning process of leather [7]. The classification of natural polyphenols is
The foregoing discussion gives us a descrip- mainly based on the types of building blocks
tion of polyphenolic compounds referring to a that appear as repeated units. The prominent
few naturally occurring systems, as classified by textbooks and synthetic chemists have classified
phytochemists. While making a general classifi- the different naturally occurring polyphenols on
cation of polyphenolic compounds it would be the basis of the three repeated building blocks
inappropriate if we do not account for the [16] namely (i) leucoanthocyanidins [I] (ii)
synthetic compounds possessing multiple units flavone glycosides [II] and (iii) esters and
of phenolic groups. For this purpose, the sim- amides of hydroxycinnamic acids [III].
plest building blocks of polyphenols and their
possible arrangements which construct them in
a repeated manner is important. Again, those
polymers indirectly derived from phenols, but
having functionalised phenolic units also need
to be taken into account in such a classification.
The tailor-made polyphenolic compounds hav-
ing a multiple number of phenolic units have
their own importance. Novolacs and resols are
well known industrial polymers because of their
excellent toughness and temperature-resistance.
Nowadays, phenolic resins have numerous ap-
plications in modern technological fields, such
as in synthetic fibres, computer technology
(photoresists, microchips) and aerospace tech-
nology [8]. About 68% of worldwide pro-
duction of phenolic resins, mainly resols, A general classification of polyphenol would
novolacs, alkylphenol resins and esterified res- not be complete if simple systems (Scheme 1)
ins are used as coating and printing inks. Some irrespective of cyclic and open nature are not
calixarene analogues, having a bowl shape and included.
with long flexible alkyl substituents have been Compounds having repeated phenolic build-
found to show mesogenic properties [9]. Chro- ing blocks with direct CC bonds or with some
matographic separation materials also have been intervening atoms, represented by [IV] are also
designed from polyphenolic compounds. Some
calixarenes have been used as a gas chromatog-
raphy stationary phase [1012]. Recently, two
resorcarene derivatives have been used for
separation of substituted benzenes [13]. Poly-
(phenylene oxide) polymers have been used to
support metal complex catalysts. Functionalised
poly(2,6-dimethylphenylene oxide) and
poly(2,6-diphenylphenylene oxide) have been
used to support titanium hydrogenation and
rhodium hydroformylation catalysts [14]. These
polymers are also thermally stable and me- Scheme 1.
 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188 165

referred to as polyphenols. The building blocks
in such systems may generally be comprised of
two repeated entities, one is the phenolic aro-
matic part and other is the linker. Schematically
one can represent such system with Scheme 1.
Besides the polyphenolic compounds that are
included in the above classifications, phenolic
compounds arranged in organised arrays in
space through weak interactions with or without
intervening molecules also needs attention. Such
systems can have replication of reactivity of
aggregated multiple phenolic groups in an orga-
nised manner. In addition to these, more com-
plicated systems may also be created by star or
dendrimeric types of polyphenolic compounds,
which are compiled as a miscellaneous category
and discussed separately.
2. Classification of polyphenolic compounds
A general classification of polyphenols is
represented in Scheme 2.
In the following subsections, the descriptions
of polyphenols and their synthetic and structural
aspects are presented.

Scheme 2.
166 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188

2.1. Naturally occurring polyphenolic
compounds
2.1.1. Proanthocyanidin derivatives
These are oligomers containing two to six
units of flavan-3-ol or high molecular weight
polymer of flavan-3-ol [16]. The flavan-3-ol
units are joined to each other at 4- to 8-positions
and in some cases at 4- to 6-positions by direct
CC bonds, as shown in Scheme 3. The syn-
thesis of oligomer of proanthocyanidin starts
from the phenolic flavan-3-ols which undergoes
stereospecific nucleophilic condensation with a
quinone methide unit. This dimer further con-
denses with a quinone methide and the process
proceeds to form oligomers and polymers with
C-4 to C-8 and to a lesser extent with C-4 to
C-6 interflavan bonds.
2.1.2. Galloyl and hexahydroxydiphenyl ester
derivatives
In this class, different gallic and hexahydro-
diphenic acid derivatives are present as esters of
a polyol (usually D-glucose) at the core of the
polyphenolic ester [16]. The pentagalloyl-D-glu-
cose [V] is the principal precursor, from which
some other member of this class have been
chemically synthesised [17].

Scheme 3.
 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188 167

from these lactones. There are different struc-

Higher oligomers and polymers of this type
of ester comprise two very well known subclas-
ses of polyphenols, namely, gallotannins and
ellagitannins. It is assumed that the hexahydrox-
ydiphenoyl esters and their derivatives are
formed by oxidative coupling reactions of adja-
cent galloyl ester groups (Scheme 4).
Lactonisation of hexahydroxydiphenic ester
by acid yields ellagic acid (bis-lactone of hexa-
hydroxydiphenic acid); ellagitannins are derived
tures of ellagitannins which mainly originate
from (a) the different extent of galloylation, (b)
the intramolecular oxidative CC coupling of
galloyl groups, (c) the dehydrogenative and
hydrolytic cleavage of galloyl group / s of aro-
matic rings and (d) oligmerisation via oxidative
CO coupling reaction [18].
Alternatively, intramolecular CC coupling
of galloyl ester groups results in the formation
of hexahydroxydiphenoyl esters with decreased
conformational flexibility (Scheme 5).
2.1.3. Hydroxy cinnamic acid derivatives
These are the condensation oligomers of
mono lignols, namely, p-coumaryl alcohol,

Scheme 4.

Scheme 5.
168 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188

coniferyl alcohol and sinapyl alcohol [1,19,20].

Lignin is one such example formed from the
oxidative polymerization of coniferyl alcohol.
Lignin is a reticulated polyphenol, having three
main functions in plants. They provide me-
chanical support, play role in conduction of
water and also provide protection against
biodegradation in plants. The formation of
lignin involves various radicals of coniferyl
alcohol as shown in Scheme 6.
2.2. Synthetic polyphenolic compounds
2.1.4. Phloroglucinol derivatives
These oligomers are derived from phlorog- In the case of a naturally occurring poly-
lucinol subunits. They are formed by oxidative phenolic compound one has to make a retros-
CC and CO coupling reactions of phlorog- pection of the natural product to get the mono-
lucinol. One example [16] of this class is meric building blocks. This may and may not
furofureckol [VI]. It has four units of phlorog- lead to identifying a less complicated phenolic
lucinol that are condensed by both CC and counterpart. This happens primarily due to the
CO coupling. They are found in marine brown fact that biological processes are complicated
algae. and original simple phenolic components may

Scheme 6.
 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188 169

get first transformed to another one through
multiple or single step transformations and this
particular part may appear as the repeated
building block.
But for synthetic polyphenolic compounds
having relatively simple building blocks such
complications can be avoided as the synthetic
protocol for the monomeric unit is known.
While visualizing a polyphenolic compound the
representative pictures having repeated phenolic
units with the linker are illustrated in Scheme 1.
Hence, it can be stated that while in the
biological field making a correlation between a
polyphenol with its simple building blocks is
retrospective, in the synthetic field, one usually
starts with the primary units. The other im-
portant point in synthetic chemistry is to look
for a reagent that would provide a basis for a
polymerisation reaction in the desired direction.
Thus, the construction of polyphenolic com-
pounds from certain simple building blocks with
a synthetic methodology is important. These are
highlighted in the following subsections with
the possible application and their physicochemi-
cal properties.
2.3. Polyphenolics without intervening atoms
These are the simplest polyphenols that can
be formed by multiple phenolic units via direct
CC bond between aromatic parts of phenols.
They can either be open chain or cyclic.
are required which may also degrade the oligo-
mers [21].
The oxidative reactions of naphthols give C
C bonded low molecular weight compounds and
the majority of the products obtained from such
reactions are binaphthols [22]. One of the
promising reactions that provides a route for
synthesising a CC bonded polyphenolic is the
palladium catalysed coupling reaction of aro-
matic boric esters with a halobenzene (Scheme
7) [23].
In a recent report, a poly-naphthalenic com-
pound namely a methylether of 2,3-naphtha-
lenediol [24] is studied. The helical structure
and interesting optical properties are observed
in such compounds.
The enzyme catalysed reaction of phenolic
compounds also leads to CC bonded poly-
phenols. The first example of enzymatic poly-
merisation of various phenol derivatives was
done by an enzyme called horseradish peroxi-
dase (HRP) [25]. Enzymatic polymerisation of
phenols and alkyl phenols by HRP showed that

2.3.1. Open chain

It is very easy to visualise the phenolic
oligomers having direct CC bonds. But in
reality there is a limited number of such systems
due to their instability toward oxidations and
also limited chemical methodology to construct
a uniform chain. Oxidative radical coupling
reaction is used for synthesis of such oligomers.
For example, phenols with one or two of its
reactive positions blocked by alkyl groups, on
oxidation by a Cu(II) salt yield dimer or trimer
[VII,VIII]. However, drastic reaction conditions Scheme 7.
170 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188
the position and chain length of the alkyl group
highly affects the chain length of the oligomer.
The medium of polymerisation also has a role in
the molecular weight of the resultant poly-
phenol. It has been observed that polymerisation
of phenols in the reverse micellar system re-
sulted in the formation of higher molecular
weight polyphenols in comparison to those
formed in aqueous organic solvents.
2.3.2. Cyclic
Spherands are cyclic oligomers of aromatic
compounds and the first report of this type was
that of a cyclohexametaphenylene system. This
compound was synthesised [26] from p-cresol,
which was first oxidatively coupled by using
FeCl 3 to get a trimer. Bromination of the trimer,
followed by methylation and further treatment
with butyl lithium leads to the corresponding
spherand (Scheme 8).
2.4. Polyphenols with intervening carbon
atoms
2.4.1. Phenolaldehyde oligomers
The controlled condensation reaction between
Scheme 8.
phenol and an aldehyde, such as formaldehyde
[27] gives either cyclic or open chain poly-
phenolic compounds. Depending on the reaction
conditions, the condensation leads to a range of
products.
Baeyer in 1872 [27,28] first reported the
condensation reaction of phenols and aldehydes.
The reaction of aldehyde and phenol in both
basic and acidic media leads to the formation of
methylol groups (CH 2 OH) at 2 and 6 (ortho)
and / or at 4 ( para) positions with respect to the
phenolic OH. Subsequent chain growth may
result from two types of condensations: (i)
condensation between two methylol phenols
resulting in CH 2 OCH 2 bridges and / or (ii) fur-
ther condensation of the methylol group with
ortho and para position of phenols resulting in
CH 2 bridges between phenolic rings (Scheme
9).
Such oligomers can be classified into the
following groups:
2.4.2. Open chain
Novolacs are open chain condensation oligo-
mers of phenol with aldehyde. The term novolac
has come from the Latin word novo (new) and
 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188
Scheme 9.
Sanskrit lac (hundred thousand). These oligo-
mers were used as a substitute for shellac, the
purified secretions (lac) of the larvae of the
insect Kerria lacca [20]. A hundred thousand
insects are needed to produce one ounce (28.4
g) of shellac. These oligomers / polymers are
prepared by reacting phenol with formaldehyde
under acidic conditions. The molar ratio of
phenolaldehyde below 1:1 gives limited cros-
slinks, however, use of excess formaldehyde
leads to crosslinked products [IX].
171
To construct the uniform polyphenol units as
shown in [VIII] one needs to address the ortho
and para selectivity on the aromatic part during
the condensation reaction. It is generally ob-
served that at a low pH, condensation is at the
para position and at a pH of about 35,
condensation at the ortho position is favoured.
An unsubstituted phenol having o- and p-
positions free yields condensation products
without selectivity, thereby giving highly irregu-
lar crosslinked products. Hunter et al. [29]
prepared phenolaldehyde linear oligomers of
up to five phenolic rings starting with appro-
priately functionalised diphenylmethane deriva-
tives (Scheme 10).
2.4.3. Cyclic
2.4.3.1. Calixarenes
Phenols with para-substituted alkyl groups,
upon condensation with aldehydes under spe-
cific reaction conditions give cyclic oligomers,
which are called calixarenes [27,28]. The term
calixarene was introduced by Gutsche, as these
172 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188

Scheme 10.

molecules have cup-like coformation when the

all aryl groups orient in the same direction
(Latin: calix, [cup-like]) [28]. These cyclic
oligomers are designated as calixarenes and a
bracketed number between the prefix calix and
the suffix arene is used to show the size of the
ring. The prefix of the substituted phenol is
written ahead of these. For example, the cyclic
tetramer, obtained from p-t-butyl phenol with
formaldehyde is designated as p-t-butylcalix-
[4]arene.
The ring size also varies [28] depending upon
reaction conditions. A base catalysed condensa-
tion reaction of para alkyl-substituted phenols
with formaldehyde affords tetra-, hexa- and
octameric macrocyclic products [X,X1,XII],
whereas acid catalysed condensation of resor-
cinol with aliphatic and aromatic aldehyde give
cyclic tetrameric products [XIII] [28]. Increase
in number of hydroxy groups in the aromatic
part drastically effects the conformation and
physical as well as chemical properties of these
systems. On alkylation and silylation of the
phenolic hydroxyls [30] or on functionalisation
of the ring, the cavity size changes. For exam- Cyclic tetrameric condensation products from
ple, the resorcinol derived cyclic tetramer, 1- and 2-naphthol and formaldehyde analogous
termed as resorc[4]arene [XIII] provides deeper to calixarenes also have been prepared [3336].
cavities than a usual calix[n]arene. The cyclic These are termed as calix[n]naphthalenes. For
trimer, cycloveratrylene prepared from catechol example, reaction of 1-naphthol can occur at the
[31], after transformation into chiral derivatives, C-2 and C-4 positions which are ortho- and
was used as a preorganising matrix for the para- to the hydroxyl group and three isomeric
design of receptors for transition metals [32]. bis(1-hydroxynaphthyl)methanes can be ob-
 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188 173

tained in the first condensation step. These are
oo, pp and op products and on further
condensation should yield four isomers (Scheme
11). Three isomers, [XIV,XV,XVI], have only
been isolated. These cyclic compounds are
reported to have deeper cavities than calixarenes
for inclusion.
However, condensation of p-t-butylphenol
with formaldehyde in the basic medium leads to
a mixture of cyclic compounds containing not
only methylene, but also a dimethylene ether
bridge [27]. They are shown in Scheme 12.
Under drastic reaction conditions, cleavage of
methylene bridges and restructuring of phenolic
units were observed. This kind of rearrangement
allows the formation of calix[4]arenes from
calix[8]arenes. Calixarenes can be synthesised
either by stepwise conversion so as to prepare a
synthetic precursor ready for cyclisation (step-
wise synthesis, Scheme 11) [28] or by taking a
synthetic precursor that would combine to give
the desired cyclic calix[n]arenes (straightfor-
ward synthesis, Scheme 13).
2.4.3.2. Spherand-type calixarene
These are calixarene analogues, synthesised
by the condensation of bisphenol [XVII] with
formaldehyde in the presence of a base (Scheme
14) [37]. These can be considered as hybrids of
calixarenes and spherands and in turn, their
stereochemistry is also more complex than
calixarenes with two arrangements (R- and S-)

Scheme 11.
174 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188

Scheme 12.

Scheme 13.

Scheme 14.
 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188
being inherently present in bisphenol. Mild
oxidation of calixarenes affords spirodienone
derivatives of calixarenes (Scheme 14).
Spherand-type calixarenes [XVIII] have also
been modified to yield spirodienone derivatives
[XIX] [38].
2.5. Polyphenols with intervening heteroatoms
2.5.1. Open chain
Different types of open chain polyphenols
having intervening heteroatoms are possible.
They can be as follows:
2.5.1.1. Poly-phenylene-ether
These compounds are derived from phenolic
compounds, having intervening oxygen bridges.
One example is shown in Scheme 15 [39].
This class of oligomer has interesting optical
properties [40], and they also have applications
as engineering plastics [4143]. Oxidative cou-
pling reactions are used to prepare this kind of
oligomer [44]. Enzyme-catalysed oxidative
polymerisation reactions are also useful in syn-
thesising such polyphenols [27].
2.5.1.2. Polyphenolic compounds with interven-
ing sulphur atom /s
A series of acyclic p-methyl- and p-t-butyl
Scheme 15.
175
phenol and formaldehyde tetramers [XX], in
which some, or all, of the methylene bridge(s)
are replaced by sulphur bridge(s) have been
synthesised [45].
2.5.2. Cyclic
2.5.2.1. Calixarenes with other hetero- atoms
Oxacalixarenes and thiacalixarene are calix-
arenes in which methylene bridges are replaced
by oxygen or sulphur atoms, respectively. Each
of these classes can be divided to homobridged
and heterobridged depending on uniformity of
distribution of the heteroatoms [46].
2.5.2.2. Oxacalixarenes
These are calixarene analogues, in which,
CH 2 OCH 2 bridges replace CH 2 bridges com-
pletely (homooxacalixarenes) or partially
(heterooxacalixarenes) between the aromatic
units [47]. Gutsche and co-workers [48] re-
176 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188

Scheme 16.

ported a general and direct method for prepara-

tion of oxacalixarenes by thermal dehydration
of bishydroxymethylated phenols, which is
shown in Scheme 16.
Hexahomotrioxacalix[3]arenes have been pre-
pared by stepwise synthesis based on cyclisation
of the linear trimer [XXI] (Scheme 17). But in
the process an irregular cyclic compound, that
is, heptahomotetraoxacalix[3]arene [XXII] was
also formed.
Recently, oxacalixnaphthalenes (e.g. [XX- 2.5.2.3. Thiacalixarene
III,XXIV]) also have been synthesized to com- Thiacalixarenes have S bridges instead of
bine both the features of oxacalixarene, that is CH 2 bridges in a typical calixarene. First
additional CH 2 OCH 2 groups for more binding report of this type are 2,8,14,20-
sites and of calixnaphthalenes, having deeper tetrathiacalix[4]arene [XXV] and 5,11,17,23-
cavities [49]. tetra-tert-butyl-2,8,14,20-tetrathiacalix[4]arene
 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188
Scheme 17.
[XXVI] [50]. These compounds after alkylation
have been found to possess interesting prop-
erties both in the solid state and in solution [51].
Different conformers of thiacalixarenes can
be prepared by alkylation. It has been observed
that in the case of smaller alkyl groups like
ethyl, all four conformers, namely, cone, partial
cone, 1,2-alternate, 1,3-alternate are present at
room temperature. However in the case of
177
bigger groups, like propyl, the interconversion
takes place only at high temperature [52].
These thiacalixarenes are also found to have a
larger cavity than that of analogous calixarenes
[53]. Oxidation of the sulphur bridges to sul-
phones or sulphoxide moieties can create new
ligands out of these groups with potentially
interesting complexation abilities [5456].
2.6. Miscellaneous
This category includes the polyphenols that
could not be fit into the earlier groups because
of having a diverse nature.
2.6.1. Repeated phenolic units in polymeric
chain
This class of compounds is not strictly poly-
phenol but oligomers with phenolic units in
regular intervals. Two examples of such oligo-
mers or polymers are the polystyrene containing
phenolic functionality [XXVII] and epoxy res-
178 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188

ins containing phenolic functionality [XXVIII]

[57].

Chiral binaphthyl compound [XXIX] cata-

lyses asymmetric addition of dialkyl and diaryl
zinc to aldehydes. However, the recoverability
of the catalyst could be improved when its
polymeric counterpart [XXX] [58] is used.

2.6.2. Branched chain type

This is a class of polyphenolic compound
where branches of polyphenolic units are an-
chored to a central core molecule. The first of
its kind [XXXI] was synthesised by acid cata-
lysed crosslinking of novolac by using an N-
methoxy methylated melamine cross-linker [59]
(Scheme 18).

2.6.3. Star-type polyphenol

In this type of polyphenol multiple numbers
of phenolic units are grown in a sequential
manner from a central core molecule in differ-
ent directions in an organised manner and
several repeated branchings can occur. One such ring enterobactin. This is involved in iron
type of polyphenol [60,61] is naturally occur- transport by complexation of Fe 31 . Such poly-
 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188 179

Scheme 18.

phenolic compounds serve as hexadentate che- is an amorphous 1:2 co-ordination polymer

late ligands called siderophores. [XXXIII] is the composed of tetraanionic polyphenoxide and
iron complex of a siderophore [XXXII]. For hydroxylanthanum dications with O 2-
21 2
understanding the ion transport in biological [LaOH] O bridges.
systems, this type of synthetic polyphenolic
compound can be of immense help.

2.6.4. Polyphenols held by weak forces

As already stated, polyphenolic compounds
have the provision for extensive H-bonding, in
many cases they are found to exist as H-bonded
clusters or aggregates [62]. In these aggregates
charge transfer interactions, keto-enol tautomer-
ism are factors that contribute to make the
aggregates / clusters well defined [63]. For ex-
ample, hydroquinone is the simplest example of
dihydroxyphenol, which exists in the form of an
aggregate. Depending on the arrangement of the
aggregated units it can exist in a, b or g form.
Of late, Aoyama and his co-workers have
reported some polyphenolic systems that are
held together by intervening atoms to give
interesting structures [64] as well as catalytic
activities [65]. They have developed a solid In another report, they have designed a
Bronsted base catalyst [65] for some base-pro- diamondoid organic lattice by using a tetra-
moted organic reaction by immobilising La 31 in phenol as a node and benzoquinone as a spacer
a H-bonded tetraphenol network [XXXIV]. This [64] [XXXV].
180 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188

substituent-through-the annulus rotation

[XXXVI] [66].

These are the two mechanisms of rotation by

3. Special features of polyphenolic
compounds
Assisted by both intra- and intermolecular
H-bonding, polyphenolic compounds show in-
teresting conformational, inclusion and com-
plexation behaviour.
which the calixarenes adopt cup or cone
coformation. These conformers are stabilized by
the intramolecular hydrogen-bonding interaction
between OH groups. For a typical calixarene,
there are two different zones in its cone-like
conformation. The lower zone contains the
phenolic hydroxy groups and the upper zone
contains the alkyl-substituted para-positions of
the constituent phenols, which are called the
lower rim and upper rim, respectively.

3.1. Conformational flexibility

Conformational flexibility of polyphenolic

compounds is best understood in calixarenes.
This can also be manipulated to the desired
direction by introducing appropriate functional
groups either in the upper rim or in the lower
rim or in both. In calixarenes, phenolic units are
held by methylene bridges and are flexible for
conformational changes. They show spectacular
conformational behaviour on changing solvent,
temperature and on further funtionalisation. This
flexibility is due to the possible orientation of
phenol units. Such conformational flexibility
may occur through two mechanisms: the oxy-
gen-through-the annulus rotation and the para-
 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188
In the case of O-alkylated calixarenes, the
intramolecular H-bonding is not present and the
through the annulus rotation of the aryl ring
changes from the hydroxy counterpart. Thus,
they give different type of conformations, which
is illustrated by taking the example of tetra-O-
alkylated calix[4]arene.
For higher calixarenes, the number of pos-
sible conformations are much higher than
calix[4]arene. Because of their unique molecular
structure with the possibility of shaping and
tuning, they have been widely investigated as
molecular scaffolds and as building blocks in
designing suitable molecular structures for sup-
ramolecular studies [28,66].
One very striking complexation behaviour of
resorcarene with ammonium ion is studied
[67,68] in the light of their different conforma-
tional changes (Scheme 19). As a function of
pH, the resorc[4]arene shows three different
conformations (A, B and C). Only one con-
former (B) is capable of complexing with
ammonium ion. Out of the other two confor-
mers, one can complex with ammonium ion
when it changes its conformation. In this pro-
cess it has to absorb two protons from the
solution, thus showing the behaviour of a proton
pump.
These features were discussed in the section
dealing with calixarenes and are not discussed
181
Scheme 19.
further. However, to show the utility of such
conformational outcomes, the behaviour of a
resorcarene to work as a proton pump is high-
lighted here.
3.2. Non-covalent interactions
3.2.1. H-bonding
Phenols, and in turn polyphenolic com-
pounds, show amphiphatic behaviour since the
phenolic hydroxy groups are hydrophilic while
the aromatic rings are hydrophobic. Because of
the presence of multiple hydroxyl groups, phen-
olic compounds can form extensive hydrogen
bonding. The binding with a substrate with
H-bonding becomes very strong as a result of
multiple site binding and this explains the
complexation of polyphenols with various sub-
strates capable of making H-bonds. Conforma-
tional mobility also contributes to a great extent,
which facilitates multiple site binding. As an
example, complexation of polyphenols with
proteins may be cited, where strong association
results from the conformational mobility in both
substrates. Again, the binding of polyphenols
182 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188

with a protein with a loose, random coil con-

formation results in strong binding in com-
parison to complexation of polyphenols with
globular protein [16].
In the case of natural polyphenolics, there are
numerous examples of molecular recognition.
Complexation between caffeine and poly-
phenols due to weak intermolecular forces has
long been studied. The black tea polyphenol
theoflavin [XXXVIII] has been found to com-
plex with caffeine [XXXVII] [69], which is the
cause of formation of turbidity in tea infusion at
temperature ,60 8C.

3.4. Consequences of non-covalent interaction

and preferential structure

3.4.1. Recognition of neutral species

Resorcarene derivative [XXXIX] binds selec-
tively with cytidine [71]. It was attributed to
possible complementary hydrogen bonding. The
host resorc[4]arene has a bowl-shaped aromatic
3.3. Effect of H-bonding on acidity cavity equipped with four distinct H-bonding
sites.
Calixarenes are the best examples for demon-
strating the effect of H-bonding in their con-
formational and binding behaviour. Large num-
ber of hydroxyl groups in polyphenolic com-
pounds may undergo intramolecular H-bonding,
which can persist even in aqueous solution. This
is reflected in an anomalously low first pKa
value of the following calixarenes, in com-
parison to their respective phenols [68,70]. This
lowering of pKa is attributed to H-bond stabili-
zation of the respective phenolate anions. In
another example of resorcarene, pKa for the first
four protons is two units lower than that of
resorcinol, whereas the pKa of the remaining Recognition of amino acids by calixarenes
four protons involved in the especially strong involves simultaneous recognition of the am-
H-bonds is above even methanol. monium group, carboxylate group and side
 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188
chain. This is however, sometimes difficult,
because strong solvation shields zwitterionic
heads from attractive interactions of ionic bind-
ing sites. Again, proximity of countercharges in
an amino acid also reduces the complexing
ability. Hence the side chain should be the
decisive factor for selectivity, which is exploited
to some extent by taking the weak hydrophobic
interaction and mere repulsion of the recognis-
ing molecule.
Kobayashi et al. [72] used calixarene tetra-
sulphonate [XL] for this purpose, where the side
chain length and the size of aromatic ring in the
side chain contributed to the recognition of
different amino acids.
3.4.2. Cation recognition
Selective recognition of cations is very much
necessary in both analytical and clinical chemis-
try. For example, the selective recognition of
NH 1 4 from monovalent metal ions, particularly
K 1 , has attracted considerable interest in clini-
cal chemistry [73]. In measuring urea content in
blood after converting it into NH 14 , K
1
always
cause problems because of its similar size.
Functional calixarenes, exhibiting chemoselec-
tive properties in the recognition of these cat-
ions have been reported by Swager and co-
workers [74,75].
3.4.3. Chiral recognition
Chiral recognition has been of immense
importance in biological as well as analytical
chemistry. Polyphenolic compounds have the
183
potential for designing the molecular host for
chiral recognition. Araki et al. [76] have shown
the ability of homooxacalixarenes for chiral
recognition of a-amino acid derivatives.
The origin of many flower colours has been
attributed to anthocyanins. The pattern of as-
sembly of various components also has a major
role in the variation of colour. Precise molecular
recognition like chiral recognition also occurs in
these assemblies [77]. For the blue colour of
Salvia patens, it has been demonstrated that, the
gross structure of the pigment is the result of
chiral molecular recognition of six molecules of
anthocyanin, six molecules of a flavone and two
metal atoms, where multiple phenolic function-
alities of the anthocyanin and flavone units play
a major role [78].
3.4.4. Inclusion
Polyphenolic compounds and their parent
phenols are widely used for their ability to
include organic and inorganic compounds and
hence they modify the properties of a large
variety of guest molecules. Whether it is cyclic
or open chain compounds, they can form inclu-
sion complexes. Many of them can trap com-
mon solvent molecules such as CH 2 Cl 2 , toluene
etc. However, in the case of cyclic counterparts,
two types of inclusion complex have been
observed. In the first type one molecule of guest
is held inside the cavity of one host molecule,
whereas in the second type two molecules of
host face each other by the upper rim to
encapsulate one guest molecule. The first report
of the type having ingested molecule is a 1:1
complex between p-tert.-butyl-calix[4]arene and
toluene [79,80] and an example of the other
type is the 1:2 complex between anisole and
p-t-butyl-calix[4]arene [81].
Although calixarenes have been studied for
their inclusion of charged organic species or
a-amino acids, of late, inclusion of radicals by
calixarenes has also been reported [82]. In this
report, inclusion of benzyl tert.-butyl nitroxide
[XLI] was used to probe its inclusion in two
water-soluble calixarene viz. Pentasodium-
184 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188
25,26,27,28-tetrahydroxycalix[4]arene-
5,11,17,23-tetrasulphonate [XLII]
tetrasodium-25,26,27,28-tetrakis(carbox-
ymethoxy)-calix[4]arene [XLIII].
Homooxacalixarenes also have been tuned to
generate dimeric capsules which have served as
a versatile host for fullerene [8385]. Certain
calixarenes have shown their ability for selec-
tive inclusion [8689], p-tert.-butyl-calix-
[8]arene can be used to selectively separate
fullerene from a mixture containing C 60 and C 70
fullerenes. There is a formation of 1:1 clathrate
in which a C 60 guest molecule is bound within
the cavity of the host molecule. The inclusion
behaviour of calixnaphthalenes in different sol-
vents also has been studied with fullerene as the
guest [90]. There are also examples in which
aggregating units of calixarenes can trap an
amine [91].
3.4.5. Cation-p -interaction
Among the non-covalent interactions, cation-
p interaction [92] plays a significant role in
designing utility material as well as in molecu-
lar biology. Understanding of this interaction in
model systems provides evidence that a hydro-
phobic binding site comprised of aromatic rings
can compete with full aqueous solvation in the
and binding of highly solvated cations. Polyphenolic
compounds bind quaternary ammonium and
some iminium ions [67]. Schneider et al. [67,68]
have reported resorcarene hosts to show cation-
p interaction. However, in these cases it was
difficult to quantify the relative importance of
cation-p vs. conventional ion pair interactions,
since the anionic groups used to solubilise the
hosts also made their way in close proximity to
the cationic centres on the hosts.
3.5. Metal binding
3.5.1. Ionophoric character
The ligands, which are capable of forming
stable complexes with charged hydrophilic
species, are ionophores. The resultant complex-
es are most often lipophilic and thus they are
easily transported into lipophilic phases. Many
natural and synthetic ionophores, hence, can be
used as transmembrane carriers for ions and as
phase transfer catalysts. Ionophoric complex-
ation is fairly specific and ionophores can
discriminate between metal cations of different
size and different charge.
Certain polyphenolic compounds also have
the potential of being ionophores. Particularly,
calixcrownethers have high discriminative abili-
ty for K 1 / Na 1 [93].
3.5.2. Chemical sensor
The presence of a cation guest in the cavity
of an appropriately functionalised calixarene
can be sensed by fluorescence study. The calix-
arene [XLIV], containing a fluorescent pyrene
group and a p-nitrobenzyl quencher [94] is not
fluorescent. But the presence of a cation in the
cavity makes the lower rim more open, thereby
compelling the fluorophore and the quencher
spatially apart. As a result of this new con-
formation, the complex becomes fluorescent.
These types of receptor are thus, potential
 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188
candidates for ion sensors based on fluores-
cence.
4. Biomimicing
Polyphenolic compounds can provide a wide
scope for mimicing biological systems. For
example, after proper funtionalisation, calix-
arenes provide dynamic preorganisation of mo-
lecular structures to mimic catalytic activity of
many biological enzymes. Although, the lower
rim, namely the phenolic OH groups can
easily be functionalised, it can be strongly
speculated that functionalisation at the upper
rim will provide more flexibility to the mole-
cule, thereby providing more scope for design-
ing enzyme models with different steric require-
ments [95].
Phosphodiesters are the functional groups
linking nucleosides in RNA and DNA, the
development of synthetic catalysts capable of
leaving these linkages have medical applica-
tions. Appropriately functionalised calixarenes
can act as dinuclear metallophosphodiesterase.
In the models [XLV] and [XLVI] of this kind of
bimimicing has been demonstrated [96,97].
185
Understanding and manipulating proteinpro-
tein interactions is of prime interest in medicinal
chemistry as these provide insights into many
biological processes. Enzyme active sites are
most often present in the interior of protein
structures.
In one of the examples of antibody mimicing,
calixarene skeleton has been found to bind to
basic residues on surface of a-chymotrypsin
[98].
5. Electrochemical study of polyphenolic
compounds
Polyphenolic compounds such as calixarenes
on appropriate functionalisation are expected to
pave the way for designing redox switches
having analogy to enzyme [99]. Elegant electro-
chemical study is demonstrated by Gomez-
Kaifer et al. [100] on the calixarenes having an
electroactive site in the cyclic counterpart. In
this study the redox properties of free quinines
are compared with the quinoniods present in the
calix unit. The study also has relevance to one
electron oxidising properties of biological poly-
phenols. In such studies [101] the one electron
redox processes are observed instead of conven-
tional two redox processes of free quinines.
Similar methodology also applied to hostguest
chemistry complements the results [102,103].
186 J.G. Handique, J.B. Baruah / Reactive & Functional Polymers 52 (2002) 163 188
6. Scope for further study
In the previous discussion illustrations are
made to provide a general classification of
polyphenolic compounds with a critical view to
evaluate their emerging applications. Scope for
designing different types of molecular architec-
ture from structural variations in polyphenolic
compounds has been a key factor for obtaining
insight to biologically important processes.
Polyphenols with intervening carbon as a linker
have proved to have potential in analytical,
biological and material chemistry. Cyclic coun-
terparts of this type of polyphenol such as
calixarenes, resorcarenes, cycloveratrylenes etc.
have been extensively studied for their ability to
recognise guest molecules. Open chain counter-
parts of such polyphenolic compounds are ex-
pected to provide a wider scope for conforma-
tional variation than the cyclic oligomers. But in
comparison to the cyclic oligomers, the syn-
thesis and application of linear counterparts has
not been explored with equal endeavour. The
cyclic systems have some preorganised con-
formations, but the linear polyphenolic com-
pounds ought to have flexibility that may bring
forth increased number of preferred conforma-
tions as well as complexity to the system.
Another aspect, which can be explored in the
case of linear oligomers, is the projection of the
hydroxyl groups in different dielectric media.
Variations on hydrophobic and hydrophilic units
on the chain of polyphenolic oligomers may
lead to solvent-induced or guest-induced con-
formational changes that in turn might provide
new optical or electronic properties.
The proton transfer processes are being
studied with great interest to understand the
photochemical as well as electrochemical pro-
cesses. In this regard special attention is given
to quinonoid types of compounds. In biological
systems the quinone units are in supramolecular
environment, thus, their electrochemical prop-
erties in a confined environment have great
importance. The calixarenes have provided
scope for such studies, with the quinonoid units
either being anchored to the ring or encapsu-
lated in the cavity. However, open chain poly-
phenolic compounds with folded structures
which recognise quinones are not being studied.
This leaves a wide scope for pursuing such
chemistry.
It has been mentioned earlier that the poly-
phenolic compounds are of prime concern in
supported catalysis for their close relevance to
biological transformations. For such supported
catalytic reactions the polyphenolic support can
be either in the form of an isolated polyphenolic
compound that binds to substrates or in the form
of a supported catalyst formed in situ for further
reaction. The metal catalysed oxidative as well
as reductive reactions can be the best choice for
study of such reactions.
Other aspects, such as detection of ions at
very low concentration, use of polyphenols in
liquid crystal display, use as optical and elec-
tronic materials, membrane mimics in purifica-
tion process, ion transport across membrane etc.
will no doubt continue to attract attention in
recent days to come. The natural polyphenols
will continue to have a major use as drugs and
achieving their synthesis will remain a chal-
lenge; this aspect dealt with in a recent review
[104]. The use of polyphenolic compounds to
provide nanolevel confinement [105], self as-
sembling of polyphenols in a guest-recognized
state [106], and functionalisation of poly-
phenolic compounds for sensor devices [107]
will be central points in the study of poly-
phenolics.
Acknowledgements
The authors thank the Council of Scientific
and Industrial Research (New Delhi, India) for
financial assistance [Grant No. 01(1748) / 02 /
EMR-II].
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