Exploration, synthesis and studies of gel forming simple sugar-chalcone derivatives

Article abstract of DOI:10.1039/c4ra06544a

Simple sugar chalcone derivatives have been obtained by the aldol condensation of various β-C-glycosidic ketones with aromatic aldehydes under the basic condition. Aglycon dimer chalcone, an unexpected cleavage product of sugar chalcone, was obtained under the same condition as a by-product. The Zn-mediated reduction of sugar-chalcone resulted in the formation of the corresponding reduced product. The products were characterized using NMR (¹H, ¹³C), mass spectroscopy and elemental analysis. Few of the sugar-chalcone derivatives exhibited the gelation property, and their morphology was studied using FESEM and HRTEM.

Full text of DOI:10.1039/c4ra06544a

View Article Online
View Journal
RSC Advances
This article can be cited before page numbers have been issued, to do this please use: A. Hemamalini
and T. Mohan das, RSC Adv., 2014, DOI: 10.1039/C4RA06544A.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. This Accepted Manuscript will be replaced by the edited,
formatted and paginated article as soon as this is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/advances

RSC Advances
Page 1 of 7Journal Name
Dynamic Article Links ►
View Article Online
DOI: 10.1039/C4RA06544A
Cite this: DOI: 10.1039/c0xx00000x
www.rsc.org/xxxxxx
ARTICLE TYPE
Exploration, synthesis and studies of gel forming simple sugar-chalcone
derivatives
Arasappan Hemamalinia and Thangamuthu Mohan Dasa,b*
aDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai – 600 025, INDIA.
bDepartment of Chemistry, School of Basic and Applied Sciences, Central University of Tamil Nadu, Thiruvarur ꢀ610 004; Ph. No. +919489054264; Fax
04366 – 225312; Eꢀmail: tmohandas@cutn.ac.in
5
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
continuation of our onꢀgoing research in the area of
saccharide and gelation chemistry,10 we have reported simple
sugarꢀchalcone derivatives, which prone to form gel with
50 different solvents and also about the dimer which has been
formed from the cleavage of the sugar chalcone derivatives.
Simple sugar chalcone derivatives have been obtained by the
10 aldol condensation of various β-C-glycosidic ketones with
aromatic aldehydes under basic condition. Aglycon dimer
chalcone, an unexpected cleavage product of sugar chalcone
was obtained under the same condition as a by-product. Zn-
mediated reduction of sugar-chalcone resulted in the
15 formation of the corresponding reduced product. Products
were characterized using NMR (1H, 13C), mass spectroscopy
and elemental analysis. Few of the sugar-chalcone derivatives
exhibited the gelation property and their morphology was
studied using FESEM and HRTEM.
Results and discussion
Synthesis and characterization of sugar chalcone derivatives
4,6ꢀOꢀbutylideneꢀ
55 by adopting the literature procedure.11 (4,6ꢀOꢀButylideneꢀβꢀ
glucopyranosyl) propanꢀ2ꢀone (2), 2,3,4,6 tetraꢀOꢀ acetylatedꢀ
βꢀ ꢀglucopyranosylꢀpropanꢀ2ꢀone (3), 2,3,4ꢀxylose tetraꢀOꢀ
acetylatedꢀβꢀ ꢀpyranosylꢀpropanꢀ2ꢀone (4) were synthesized
D
ꢀglucopyranose was synthesized
D
ꢀ
D
20 Introduction
D
following the literature procedure.12 The reaction of various
60 sugar protected propaneꢀ2ꢀone, 2-4 with aromatic aldehydes
using pyrrolidine as catalyst resulted in 80ꢀ90% of the
corresponding α,βꢀunsaturated compounds, 5-22 and 1-8 in
ESI which upon reduction13 using Zn/NH4Cl in EtOH/H2O
gave the corresponding reduced chalcone derivatives, 23-29 in
65 59ꢀ84% yield (Scheme 1, Also see ESI). Reduction was
carried out under neutral condition. Since most of the
chalcone derivatives were partially soluble in ethanol, the
reaction temperature was maintained from 40ꢀ50 oC.
However, the compound, 29 was obtained in good yield by the
70 reduction of its precursor13 using Ethanol:DMSO solvent
mixture in the ratio 9:1. But, the reduction of partially
protected sugarꢀbased ferrocenylꢀchalcone14 did not give any
expected product under the given condition. Remarkable
chemoselective carbonꢀcarbon double bond reductions were
75 observed in all the cases and the labile functionality like
ketone was unaffected under these conditions. Structure of the
synthesized sugar chalcone derivatives, 5-22 and 1-8 in ESI
were determined by (1H, 13C) NMR spectroscopy, mass
spectroscopy and elemental analysis. The appearance of two
Lowꢀmolecularꢀweight organogelator (LMOG) is an
important class of soft matters which has received an
increasing attention in recent years due to their easy
fabrication into soft materials. It also has a wide applications
25 in the field of sensing, catalysis, oil recovery, template
synthesis of nanoporous materials etc.1 It is very important to
design suitable gelator molecules involving Hꢀbond forming
site and π−π stacking unit including van der Waals forces,
electrostatic attraction and hydrophobic interaction which are
30 necessary for the gelation.2
Chalcone and their derivatives are found to be wellꢀknown
intermediates for the synthesis of various heterocyclic
compounds. They exhibit a broad spectrum of biological
activities3 such as antiinflammatory, antituberculosis,
35 antifungal, antimalarial, antileishꢀmanicidal, anticancer etc..
The simple unsubstituted chalcone itself shown to inhibit the
proliferation of human breast cancer cells.4 In addition,
hydroxy chalcones are also reported to induce apoptosis in
melanoma cells.5 Few of the chalcones are under investigation
40 for antiblood platelet coagulation and antihaemostasis.6
Isoliquiritigenin, a liquorice chalcone has been used as a
phosphodiesterase III inhibitor for the treatment of
cardiovascular diseases.7 Moreover, there are only few reports
on the organogelator based simple chalcone derivatives.
45 However, chalcones with nitro group8 and polycatenar type
derivatives9 have shown to exhibit gelation property. In
80 doublets at
δ 7.89 and δ 6.94 with J value of 16.5 Hz each,
corresponds to the transꢀalkene protons whereas the two
aromatic protons appeared as two singlets and the unreacted
aldehyde proton appeared as a singlet at
δ
9.95 in 1H NMR
spectrum for the compound, 15. It also notably exhibited a
This journal is © The Royal Society of Chemistry [year]
[journal], [year], [vol], 00–00 | 1

RSC Advances
Page 2 of 7
View Article Online
DOI: 10.1039/C4RA06544A
large coupling constant for the Hꢀ1 signal (3JH1,H2 ~ 9.5 Hz), 30 benzaldehyde respectively [Scheme 2]. Reaction condition
indicating a transꢀdiaxial orientation of Hꢀ1 and Hꢀ2 as
expected for a βꢀ
ꢀconfigured glucopyranose moiety.13 The
aldehyde carbon appeared at 198 ppm whereas the ꢀ,
unsaturated carbonyl carbon resonated at 195 ppm in 13C
was optimized to increase the yield of the dimer. However, Oꢀ
alkylation was carried out as first step followed by aldol
condensation to reduce the polarity of the dimer which inturn
reduces the resolution factor (Rf) of the product thus
D
α
βꢀ
5
NMR, gave further confirmation for the formation of sugarꢀ 35 minimizes the difficulty in isolation of the product using
chalcone product, 15. The pyrene based sugarꢀchalcone
derivative,15 was synthesized and reduced using Zn to furnish
the pyrene based sugar ketone derivative, 29. In 1H NMR
column chromatography. The yield of the dimer was obtained
in the range of 5ꢀ20%.
10 spectrum of compound, 29 the characteristic methylene peaks
were appeared as two multiplets in the region 3.1ꢀ3.0 and 2.8ꢀ
2.6 ppm whereas two peaks at 45 ppm and 27 ppm
corresponds to the methylene carbons in 13C NMR confirmed
the formation of the reduced product. From the DEPTꢀ135
15 experiment (See ESI) the appearance of six peaks on one side
of the base line corresponds to the six methylene carbons
further confirmed the formation of the sugar ketone
derivative, 29.
CH3
O
CH3
O
Scheme 2 Synthesis of chalcone-dimer, 37-41.
O
O
O
H3C
CH3
O
O
40 The structure of the synthesized dimers are shown in Figure
1. The formation of the dimer was confirmed from [1H, 13C]
NMR and also from DEPTꢀ135 experiments [See ESI for
O
CH3
OH
HO
HO
NaHCO3, THF-
H2O, 9:1, reflux,
36 h, 85%
OH
OH
O
1
2
Pyrrolidine (30% mol)
R-CHO
DCM, rt
1
45-93%
more details]. It is very clear from the H NMR spectrum of
CH3
CH3
O
compound 38, that the dimer would have been formed only
45 from the aldol condensed product because of the retainity of
the transꢀalkene double bonds which has a J value of 16.2 Hz.
The dimer formation is also confirmed from 13C NMR where
the alkene carbons were observed at 136 ppm and 114 ppm. In
addition, the characteristic carbonyl carbon was observed at
50 191 ppm. The cleavage of the sugar part was further
confirmed from DEPTꢀ135 experiment where one single peak
for ꢀOCH2 group only was observed. The formation of the
dimer product is also characterized from 2D experiments [See
ESI for more details].
O
NaOAc, Ac2O
80-90 o
O
C
O
O
R
O
R
AcO
80-85%
HO
OAc
OH
5-18
O
O
19-22
Zn, NH4Cl
EtOH/H2O
(5:1)
40-50 o
59-84%
CH3
O
C
O
O
R
HO
OH
O
23-29
OH
55 Mechanism for the formation of dimer product may be
through the imine formation of the sugarꢀchalcone with the
base (pyrrolidine) and the mechanistic pathway is not so clear.
Pyrrolidine is a weak base and it could not produce the
intermediate (enolate). Thus, the addition of pyrrolidine to the
60 sugarꢀchalcone is expected to undergo enamine reaction
followed by sugar cleavage which may result in the formation
of the dimer. However, the exact mechanism is still
ambiguous.
R =
O
Br
F
OH
OH
9
Cl
10,26
5,19,23
6,20,24
7,21,25
8
OH
CHO
N
H
HO
COOH
CHO
CN
Br
11
Br
15
13
12
14
16
N
O
O
N
H
HO
17
18,28
22
27
29
20 Scheme 1 Synthesis of sugar-chalcones, 5-22 and its reduced derivatives,
23-29.
Dimer formation
The unexpected allyl and propargyl dimers, 37-41 was
obtained as a byꢀproduct in the aldol condensation between
25 2,3,4ꢀtriꢀOꢀacetylꢀ
allyloxybenzaldehyde and also from the aldol condensation of
4,6ꢀOꢀbutylidene ꢀglucopyranosylꢀpropaneꢀ2ꢀone with
βꢀDꢀxylopyranosylpropaneꢀ2ꢀone with 4ꢀ
β
ꢀD
propargyloxyꢀnapthaldehyde/oꢀpropargyloxybenzaldehyde/mꢀ
chloropropargyloxybenzaldehyde/pꢀpropargyloxyꢀ
2
|
Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 3 of 7
RSC Advances
View Article Online
DOI: 10.1039/C4RA06544A
Figure 2 Representation of the formation of gel, 9 in CHCl3, (a), after
heating; (b), on cooling and (c), gel in inverted position.
35 Morphological studies
Morphology of the compounds that form gel were studied
using FESEM and HRTEM analysis. SEM images of the
compounds 7-9, 21, 3 (see ESI), 30, 32 & 35 were obtained
and its representative images are shown in Figure 3.
40 Sugar chalcone derivatives, 7, 21 & 3 (see ESI) which
possessed allyloxy as side chain showed fibrous network,
smooth nonꢀfibrous surface and also embedded flakeꢀlike
morphology respectively. The difference in the morphology is
due to the difference in the protecting group present in the
45 saccharide moieties. Thus, it is obvious from the results that
nature of the protecting group in the saccharide also affects
the morphology of the gel. Compound, 9 which has the
hydroxy group in the meta position self assembles to form
globules which was linked to each other through thin
50 nanometer sized tapeꢀlike structure. Compound, 8 showed
nonꢀfibrous clusterꢀlike morphology. Similar morphology has
been observed with propargylated sugarꢀchalcone derivative,
35. Compound, 30 did not form gel and the morphology was
observed as particleꢀlike structure. SEM image of the
55 compound 32, showed baggasseꢀlike morphology, which on
magnification was observed as a lamellar structure. Moreover,
compounds which possess the fibrous network could trap
more solvent compared to that of the lamellar structure has
been well documented from FESEM analysis. Thus, the
60 compound 32, could not trap the solvent much as in the case
of compound, 7 because of its lamellar morphology.
Figure 1 Proposed structure of the unexpected dimers, 37-41.
Gelation experiment
Gels which are viscoꢀelastic material was obtained by
inversion tube method where the compound was reluctant to
flow after heating followed by cooling [Figure 2]. Critical
gelation concentration (CGC) means the minimum amount of
compound which is trapped by the solvent. It actually judges
the quality of the gel. In general, low CGC refers to a good
5
10 gelator.
Forty six different sugar derivatives such as sugarꢀchalcone
derivatives, sugar ketones, aldol product and the dimer were
synthesized and tested for gelation in both solvents as well as
solvent mixtures [See ESI for more details]. An appropriate
15 amount of gelator was weighed and dissolved in a suitable
solvent. It is then heated until dissolution or boiling point of
the solvent and the homogeneous solution is allowed to cool
at room temperature to obtain the gel. The sugarꢀchalcone
derivatives, 8, 9, 21, 33 & 35 formed gel in different solvent
20 at low CGC of 1.5, 1.5, 1.9, 1.6 and 1.8 wt/v% respectively.
However, compounds 7 & 32 (CGC: 1.0 & 1.2%) form gel at
The internal morphology of the compound, 7 before and after
gelation was studied using HRTEM analysis. The compound,
a
relatively lower concentration compared to the other
7
before gelation had rod like morphology whereas
derivatives. This may presumably be due to the high degree of
hydrogen bonding and also because of the molecular
25 architecture core and surface moiety. From the gelation
studies, it is found that the sugar ketones, aldol product and
the dimers did not form gel. It may be due to the absence of
conjugation in the case of sugar ketone and aldol product and
absence of the hexose sugar in the case of dimers. This further
30 confirmed the necessity of the presence of hexose sugar and
conjugation for gelation.
65 interestingly the same compound after gelation showed
intertwined fibrousꢀlike morphological structure. Moreover
the gelator compound, 7 has a fibrillar network where the
fibres which are in the nanometer scale join together to form a
ropeꢀlike morphology. Also the joined fibres found to be
70 intertwined in the rightꢀhand side fashion. Hence, the
appearance of intertwined structure clearly confirms the self
assembly of the molecule. The HRTEM image of the
compound, 7 before and after gelation is shown in Figure 4.
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 3

RSC Advances
Page 4 of 7
View Article Online
DOI: 10.1039/C4RA06544A
Figure 4 HRTEM image fo compound, 7 (200 nm): (a) solid and (b) gel in
DMSO;H2O mixture (10;1)
10 Correlation of present and previously reported results:
Gel formation was not observed for the compound, 31 which
has the pentose sugar, allyloxy functionality and also α,βꢀ
unsaturated group. This clearly picturises that only the
presence of π−π interaction is not sufficient for gel formation.
15 However, the formation of gel is also favoured by the
presence of hexose sugar moiety. The previous work
reported16 in our laboratory which was related to the
transformation of chalcone into various heterocyclic
derivatives like pyrazole, spirooxindolopyrrolidines and
20 pyrrolizidines failed to form gel. Recently, it was reported17
that the sugar chalcone containing the halogen group
crystallized but does not favour the gel formation and the
crystallization is due to the presence of hydrogen bonding
whereas similar derivative containing the hydroxy or allyl
25 group substituent does not form crystal but rather formed gel.
Additional experiment was conducted to rule out the existence
of hydrogen bonding. In this process, compound, 8 which
possess the hydroxyl group was propargylated but it was
observed that the propargylated product, 35 did not lose its
30 gelation property. Futhermore, it was reported14 in the
literature that the sugarꢀchalcone having the hydroxy group in
the ortho position formed
a crystal whereas the same
derivative which possess the hydroxyl group in the meta or
para position forms gel. Morphology of both the compound, 8
35 & 9 were analyzed using SEM and its representative images
were shown in Figure 3.
Gel properties depend on various factors, such as time18,
temperature,19 solvent,20 composition, structure of the
gelators21 and even the use of different isomers. Solvent plays
40 a vital role in the gelation process. The polarity of the solvent
and the gelator has significant importance in the gelation.
Hence the choice of solvent should be made with utmost care.
Gelator, 7 has a good selfꢀassembled structure (Figure 3b)
with less polar solvents and it failed to gelate with more polar
45 solvent like methanol or ethanol. Moreover from the SEM
image, it is very clear that a minimal change in the structure
of the chalcone and also with the change of the solvent, there
has been a dramatic change in the morphological structure
(Figure 3). This clearly portrays the high significance on the
50 effect of solvent on gelation. When DMSO and water mixture
was used in the ratio 10:1, the compound, 7 formed a clear gel
whereas on increasing the volume of water resulted in
precipitation. Hence, it is not only the solvent but also the
solvent ratio has a severe impact on gelation. Moreover, it is
55 also reported in the literature22 that the solution or precipitate
Figure 3 FESEM images (with different magnification) of compounds, (a),
7 before gelation [50 ꢀm]; (b), 7 in DMSO+H2O, after gelation [500 nm];
(c), 3 (see ESI) in DMSO+H2O [2 ꢀm]; (d), 21 in DMSO+H2O [2 ꢀm]; (e), 8
in CHCl3+MeOH [5 ꢀm]; (f), 9 in CHCl3 [500 nm]; (g), 35 in EtOAc [5 ꢀm];
(h),30 in EtOAc [2 ꢀm]; (i), 32 in CHCl3 [30 ꢀm] and (j), 32 in CHCl3 [5 ꢀm].
5
4
|
Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 5 of 7
RSC Advances
View Article Online
DOI: 10.1039/C4RA06544A
would be formed if the gelatorꢀsolvent interaction is too
strong or too weak.
1H NMR experiment of gelator
The gel formation of compound 8 is also evident from 1H
NMR experiment which was carried out before and after
heating [Figure 5]. It was observed from the experiment that
the peaks were broad before heating. It may be because of the
self assembly of the compound whereas the same derivative
5
after heating gave
a well resolved spectra. Generally,
10 broadening of NMR signal can be infuenced by either selfꢀ
assembly or ligand exchange. In this case, the association of
molecules was obtained from the 1H NMR studies of the
compound, 8. The aggregation of molecule was observed in
CDCl3ꢀDMSO solvent mixture in the ratio 1:4 at room
15 temperature. On increasing the temperature by maintaining the
solvent mixture ratio, the disaggregation was observed as
evidenced from the splitting of broad peaks. In addition, the
broadening may be either due to the exchange of the
molecules between the solution and the gel states or limited
20 tumbling of the molecules resulting in increased anisotrophy.
Figure 6 Differential Scanning Calorimetry (DSC) of the organogelator, 7,
(a) solid and (b) gel (DMSO + H2O)
The melting peak of 7 was observed at 208 °C with ꢁH value
35 of 138.9 J/g in the solid phase whereas the same compound in
the gel state melted at 201 °C with ꢁH value of 124.1 J/g. The
o
peak observed at 140 C represents the liberation of both the
water as well as the DMSO. Generally, the ꢁH value of the
gel dependent on the nature of the solvent used for gelation
40 was well reported in literature.23 The difference between the
melting point of the solid 7 and the same compound in its gel
form gives the stability of the gel formed. In general, if the
difference is too wide it is said to be a good gelator. Here, in
this case the difference in the melting temperature (Tm)
45 between the solid and gel was found to be exactly 7 oC.
Hence, the gel formed from the compound 7 was found to be a
good gelator.
XRD studies
One of the side product which is the aldol product that
50 was obtained from the aldol condensation of 4,6ꢀOꢀbutylidineꢀ
βꢀDꢀglucopyranosylpropanꢀ2ꢀone with 2ꢀnitro benzaldehyde
crystallized in ethylacetate and its ORTEP view is shown in
the Figure 7. The crystallographic parameters of the crystal
30 are represented in Table 1.
Figure 5: 1HNMR spectra of compound 8 recorded in CDCl3 + DMSO
solvent mixture in 1:4 ratio (a) after heating, (b) before heating.
55
Thermal studies
AcO
O
AcO
25 The thermal properties of the sugarꢀchalcone was understood
from DSC studies. DSC was taken for the compound as such
in the solid state. The compound was then formed gel in
DMSOꢀH2O solvent mixture. DSC was then taken for the gel
sample prepared. The peaks observed in both the cases were
30 overlapped. The overlapped DSC graph is shown in Figure 6
AcO
OAc
O
OH NO2
30
Figure 7 ORTEP view of compound 30 (top), Structure of the compound
60 38 (below).
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 5

RSC Advances
Page 6 of 7
View Article Online
DOI: 10.1039/C4RA06544A
Table 1 Crystallographicic data for compounds, 30
30 Acknowledgement
Parameters
Formula
Formula weight
Crystal system
30
Authors acknowledge SERCꢀDST, New Delhi for financial
support. T. M. thank DST, New Delhi for use of NMR facility
underDSTꢀFIST programme to the Department of Organic
Chemistry, University of Madras, Guindy Campus, Chennai,
35 India. A. H. thank CSIR, New Delhi for SRF. We
acknowledge Centre for Nanoscience and Nanotechnology,
University of Madras, Chennai for recording FESEM and
HRTEM. Authors thank SAIF, IIT Madras for solving crystal
structure. The CCDC number obtained for compound 30 is
40 864128.
C24H29NO13
539.48
Monoclinic
P21
9.523(5)
5.419(5)
26.034(5)
90.000(5)
95.631(5)
90.000(5)
1337.0(14)
2
Space group
a (A)
b (A)
c (A)
α (deg)
β (deg)
γ (deg)
V (A3)
Z
Calculated density (mg/m3)
ꢀ (mmꢀ1)
1.340
0.110
293 (2)
4783
Notes and references
T (K)
a Department of Organic Chemistry, University of Madras, Guindy
Campus, Chennaiꢀ600 025, INDIA. Fax: (+) 91ꢀ44ꢀ22352494; Tel: +91
44 22202814; Eꢀmail: tmdas_72@yahoo.com
No. of unique reflections
No. of observed reflections
R1, Rw
4630
0.0396, 0.0963
568
45
50
†
Electronic Supplementary Information (ESI) available: [Experimental
details]. See DOI: 10.1039/b000000x/
GOF
Crystal habit
Needle, Colorless
1. (a) Terech, P., Weiss, R. G., Chem. Rev., 1997, 97, 3133ꢀ3159; (b)
Estroff, L. A., Hamilton, A. D., Chem. Rev., 2004, 104, 1201ꢀ1218;
(c) Sanchez, C., Arribart, H., Guille, M. G., Nat.Mater., 2005, 4, 277ꢀ
288; (d) Sangeetha N. M., Maitra, U., Chem.Soc. Rev., 2005, 34, 821ꢀ
836; (e) de Loos, M., Feringa, B. L., van Esch, J. H., Eur. J. Org.
Chem., 2005, 3615ꢀ3631; (f) George, M., Weiss, R.G., Acc. Chem.
Res., 2006, 39, 489ꢀ497; (g) Yang, Z., Liang, G., Xu, B., Acc. Chem.
Res., 2008, 41, 315ꢀ326.
The hydrogen bonding in the compound, 30 is represented
in Figure 8. Eventhough it possessed hydroxy group it did not
favour gelation, it may be because of the presence of electron
withdrawing substituent (ꢀNO2 group attached to the phenyl
moiety). Though it does not form gel, the SEM image of the
compound 30 was obtained for comparison with the gel
forming sugarꢀchalcones. From the SEM image, the
5
55 2. Kartha, K. K., Mukhopadhyay, R. D., Ajayaghosh, A., Chimia, 2013,
67, 51ꢀ63.
10 morphology of the compound 30 was found to be particleꢀlike
structure.
3. (a) Won, S., Liu, C., Tsao, L., Weng, J., Ko, H., Wang, J., Lin, C., Eur.
J. Med. Chem., 2005, 40, 103ꢀ112; (b) Lin, Y., Zhou, Y., Flavin, M.,
Zhou, L., Niea, W., Chen, F., Bioorg. Med. Chem. Lett., 2002, 10,
60
65
70
75
80
85
90
2795ꢀ2802; (c) Lahtchev, K. L., Batovska, D. I., Parushev, P.,
Ubiyvovk, V. M., Sibirny, A. A., Eur. J. Med. Chem., 2008, 43,
2220ꢀ2228; (d) Agarwal, A., Srivastava, K., Puri, S. K., Chauhan, P.
M. S., Bioorg. Med. Chem. Lett., 2005, 15, 3133ꢀ3136; (e) Kayser,
O., Kiderlen, A. F., Phytother. Res., 2001, 15, 148ꢀ152; (f) Aponte,
J., Verastegui, M., Malaga, E., Zimic, M., Quiliano, M., Vaisberg, A.
J., Gilman, R. H., Hammond, G. B., J. Med. Chem., 2008, 51, 6230ꢀ
6234; (g) Quintin, J., Desrivot, J., Thoret, S., Menez, P., Cresteil, T.,
Lewin, G., Bioorg. Med. Chem. Lett., 2009, 19, 167ꢀ169.
4. Hsu, Y. L., Kuo, P. L., Tzeng, w. S., Lin, C. C., Food Chem. Toxicol.,
2006, 44, 704ꢀ713.
5. Navarini, A.L. F., Chiaradia, L.D., Mascarello, A., Fritzen, M., Nunes,
R. J., Yunes, R. A., CreczynskiꢀPasa, T. B., Eur. J. Med. Chem.,
2009, 44, 1630ꢀ1637.
6. He, W. Y., Li, Y., Liu, J. Q., Hu, Z, D., Chen, X. G., Biopolymers,
2005, 79, 48ꢀ57.
7. J.W. Wegener, H. Nawrath, Eur. J. Pharmacol., 1997, 326, 37ꢀ44.
8. Simon, F. –X., Nguyen, T.ꢀT.ꢀT., Schmutz, M. Decher, G., Nicoud, J.ꢀ
F., Mesini, P. J., New. J. Chem., 2009, 33, 2028ꢀ2033.
9. Lim, G. S., Jung, B. M., Lee, S. J., Song, H. H., Kim, C., Chang, J. Y.,
Chem. Mater., 2007, 19, 460ꢀ467.
10. (a) Rajaganesh, R., Gopal, A., Mohan Das, T., Ajayaghosh, A., Org.
Lett., 2012, 14, 748ꢀ751; (b) Nagarajan, S., Khumbar, A., Varghese,
B., Mohan Das, T., Carbohydr. Res., 2010, 345, 1077ꢀ1083; (c)
Hemamalini, A., Mohan Das, T., New. J. Chem., 2013, 37, 2419ꢀ
2425; (d) Hemamalini, A., Mohan Das, T., New. J. Chem., 2014, 38,
3015ꢀ3021; (e) Hemamalini, A., Mohan Das, T., RSC Adv., 2014,
doi:10.1039/c4ra04084h.
11. (a) Mellis, R. L., Mehltretter, C. L., Rist, C. E., J. Am. Chem. Soc.,
1951, 73, 294ꢀ296; (b) Bonner, T. G., Bourne, E. J., Lewis, D., J.
Chem. Soc., 1965, 7453ꢀ7458.
Figure 8 Hydrogen bonding interaction of compound, 38
Conclusion
15 Thus, we have designed and synthesized several sugarꢀ
chalcone derivatives, which prone to form organogel. From
the gelation studies it was obvious that even the position of
hydrogen bonding substituent affect the gelation. Thus, it is
concluded that for gelation of the propargylated or allylic
20 sugarꢀbased compound, π−π stacking of the double or triple
bond plays a vital role. In addition, the self assembly of the
sugarꢀchalcone compounds also depends on the position of the
hydrogen bonding substituent. Moreover, it was found that the
compounds which have electron donating groups formed gel
25 whereas the compounds which possess the electron
withdrawing group did not favour gelation. It was summarised
that the compound for gel formation in sugar chalcone system
should possess a hexose sugar, chalcone system, hydrogen
bond forming site and also the π−π stacking.
12. (a) Bragnier, N., Scherrmann, M. C., Synthesis, 2005, 5, 814ꢀ818; (b)
Rodrigues, F., Canac, Y., Lubineau, A., Chem. Commun.
(Cambridge), 2000, 2049ꢀ2059; (c) Riemann, I., Papadopoulos, M.
A., Knorst, M., Fessner, W. D., Aust. J. Chem., 2002, 55, 147ꢀ154.
6
|
Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 7 of 7
RSC Advances
View Article Online
DOI: 10.1039/C4RA06544A
13. Li, J.–P., Zhang, Y.ꢀX., Ji, Y., J. Chin. Chem. Soc., 2008, 55, 390ꢀ
393.
14. Nagarajan, S., Mohan Das, T., Arjun, P., Raaman, N., J. Mater.
Chem., 2009, 19, 4587ꢀ4596.
5
10
15
15. Nagarajan, S., Mohan Das, T., New J. Chem., 2009, 33, 2391ꢀ2396.
16. (a) Hemamalini, A., Nagarajan, S., Mohan Das, T., Carbohydr. Res.,
2011, 346, 1814ꢀ1819; (b) Hemamalini, A., Nagarajan, S., Mohan
Das, T., Carbohydr.Res.,2012, 352, 12ꢀ17.
17. Hemamalini, A., Nagarajan, S., Ravinder, P., Subramanian, V.,
Mohan Das, T., Synthesis, 2011, 15, 2495ꢀ2504.
18. Smith, M. M., Smith, D. K., Soft Matter, 2011, 7, 4856ꢀ4860.
19. Roy, B., Saha, A, Esterrani, A., Nandi, A. K., Soft Matter, 2010, 6,
3337ꢀ3345.
20. (a) Dasgupta, D., srinivasan, S., Rochas, C., Ajayaghosh, A., Guenet,
J. M., Soft Matter, 2011, 7, 9311ꢀ9315, (b) Velazquez, D. G., Luque,
R., Chem. –Eur. J., 2011, 17, 3847ꢀ3849, (c) Zhu, P. L., Yan, X. H.,
Su, Y., Yang, Y., Li, J. B., Chem. –Eur. J., 2010, 16, 3176ꢀ3183, (d)
Bielejewski, M., Laoinski, A., Luboradzki, R., TrittꢀGoc, J.,
Tetrahedron, 2011, 67, 7222ꢀ7230.
20 21. (a) Suzuki, M., Saito, H., Shirai, H., Hanabusa, K. New. J. Chem.,
2007, 31, 1654ꢀ1660, (b) Wang, T. Y., Li, Y. G., Liu, M. H., Soft
Matter, 2009, 5, 1066ꢀ1073.
22. Niu, L., Song, J., Li, J., Tao, N., Lu, M., Fan, K., Soft Matter, 2013, 9,
7780ꢀ7786.
25 23. Park, S. M., Lee, Y. S., Kim, B. H., Chem. Commun., 2003, 2912ꢀ
2913.
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 7