Supramolecular gels derived from nucleoside based bolaamphiphiles as a light-sensitive soft material

Article abstract of DOI:10.1039/d0cc00336k

Light-sensitive Low Molecular Weight Gelators (LMWGs) derived from glyconucleoside bolaamphiphiles containing a stilbene unit displayed gelation abilities in hydroalcoholic mixtures. These materials showed a gel-sol transition under UV irradiation thanks to E-Z isomerization of stilbene and could find potential applications as drug delivery systems.

Full text of DOI:10.1039/d0cc00336k

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Supramolecular gels derived from nucleoside based
bolaamphiphiles as a light-sensitive soft material
Julie Baillet,a Alexandra Gaubert,a Dario M. Bassani,b Julien Verget,a Laurent Latxague*a and
Received 00th January 20xx,
Accepted 00th January 20xx
Philippe Barthélémy*a
DOI: 10.1039/x0xx00000x
control and has successfully been applied in nanotechnology or
biomedicine.23–25 Light-responsive gels generally rely on the
presence of photochromic moieties that undergo ring-opening / -
closing reactions (spiropyrans, diarylethenes) or E / Z isomerization
(azobenzene, stilbene and derivatives).26–34 Stilbene has been
particularly studied thanks to its well-known photoswitching
behavior35 to give light-sensitive gels based on cholesterol,36 oxalyl
amide,37,38 N,N’-dimethyldodecylamine39 or amino acid40 derivatives
displaying gel-sol or sol-gel transitions under irradiation. To the best
of our knowledge, hydroalcoholic supramolecular gels sensitive to an
external stimulus such as light have not been reported so far. These
materials could be used as models for drug delivery in the case of
external use for example. However, the design of such stimuli-
sensitive gels can profoundly impact the likelihood of successful gel
responsiveness for a given application. The introduction of large
hydrophobic photochromic units in a LMWG framework may disturb
the self-assembly process and imped effective photoisomerization in
gel state due to steric hindrance. This behavior might be accentuated
when photosensitive moieties are simultaneously tightly packed and
strongly involved in the supramolecular assembly.41,42
Bio-inspired amphiphilic substrates combining carbohydrate,
nucleoside and lipid units have shown promising applications as
LMWGs.43–46 Among them, bolaamphiphiles derivatives in which two
glyconucleoside headgroups are linked covalently by a hydrophobic
spacer have emerged as attractive scaffolds for biomedical
applications.47–49 In this work, we present a series of light-sensitive
supramolecular gels based on glyco-nucleoside-bolaamphiphile
derivatives (GNBAs) featuring a thymidine, a glucose or a lactose and
a stilbene, as photochromic moiety, within the hydrophobic part. The
resulting responsive GNBAs led to the formation of thixotropic gels
in hydroalcoholic solvents and a photoinduced gel-sol transition
upon irradiation due to the stilbene photoisomerization.
Light-sensitive Low Molecular Weight Gelators (LMWGs) derived
from glyconucleoside bolaamphiphiles containing a stilbene unit
displayed gelation abilities in hydroalcoholic mixtures. These
materials showed a gel-sol transition under UV irradiation thanks
to E - Z isomerization of stilbene and could find potential
applications as drug delivery systems.
Supramolecular gels resulting from the self-assembly of functional
low molecular weight gelators (LMWGs) have gained an increasing
interest in many fields ranging from tissue engineering to electronic
devices.1–6 The dynamic nature of non-covalent interactions
represents a powerful tool to modulate the physical behavior of
LMWGs. Many changes or modifications, occurring at the molecular
level (supramolecular structure, geometry) and
/ or at the
macroscopic scale (gel - sol states, physico-chemical properties) have
been reported.7,8 According to their hydrophilic to hydrophobic
balance among other parameters, LMWGs can provide hydro-,
organo- or oleogels. Falling between hydro- and organogels,
hydroalcoholic gels are of particular interest for the formulation of
various active pharmaceutical ingredients (APIs) as anti-
inflammatory (including non-steroid molecules),9,10 anti-epileptic11
or antifungal12 drugs. However, these gels are mainly composed of
mixtures of synthetic or natural polymers and penetration
enhancers. In the last decade, responsive supramolecular gels
sensitive to enzymes,13–16 magnetic/electric fields,17,18 or pH19,20
among other triggers have been extensively designed for diverse
applications ranging from controlling cell behavior21 to drug
release.22 Recently, light stimulation has attracted much attention as
a minimally invasive stimulus allowing precise spatiotemporal
a. J. Baillet, Dr. A. Gaubert, J. Verget, Dr. L. Latxague, Prof. P. Barthélémy
University of Bordeaux, INSERM U1212, UMR CNRS 5320, F-33076 Bordeaux
(France)
A synthetic route was developed in 6 steps based on CuAAC
chemistry
/ metathesis reactions, starting from commercial
E-mail: philippe.barthelemy@inserm.fr; laurent.latxague@u-bordeaux.fr
thymidine (Scheme 1A). The introduction of a propargyl unit at the
N3 position under microwave conditions allowed the formation of
N3-propargylthymidine 1. The latter was then submitted to a CuAAC
reaction with the desired peracetylated azidosugar to form the
b. Dr. D. M. Bassani
University of Bordeaux, CNRS, Bordeaux INP, ISM, UMR 5255, F-33400 Talence
(France)
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
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corresponding 1,2,3-triazole derivative, followed by the 5’ position homometathesis reaction using the Hoveyda-Grubbs II catalyst.
functionalization with an azide group. Intermediates 3 and 3’ were Deprotection of the acetyl sugar groups DuOnId: e10r.1b0a3V9sii/ecDw0cACortCinc0lde0iOt3ino3l6innKes
then involved in a second CuAAC reaction with the desired allowed to reach the final general structure 9. Using this strategy,
propargylic carbon chain 6a or 6b gathering a styrene ending group three GNBAs 9a, 9’a, 9’b, displaying different hydrophobic chain
to form the corresponding glyconucleolipids. E-bolaamphiphile lengths and sugar moieties, were synthetized (Scheme 1B).
structures were then obtained via the stereoselective
O
N
O
N
O
N
9a
H
O
Sug(OAc)n
N
N
A
O
B
a
b, c
d, e
N
N
N
X
N
N3
OH
HO
HO
HO
O
OH
O
O
O
O
HO
O
N
O
O
O
O
+
HO
O
OH
N
N
N
1
3
Lac(OAc)7
6
a
b
X = -(CH2)6-O-CH2-
X = -CH2-
OH
OH
OH
OH
N
O
N
N
O
3’ Glu(OAc)4
O
N
O
f
OH
2
O
O
N
Sug(OAc)n
9’a
N
N
N
X
O
N
N
N
O
O
11
N
OH
O
O
OH
OH
HO
N
O
7a 7’a 7’b
O
OH
N
N
N
O
O
O
N
N
O
N
O
N
O
OH
O
g, h
12
OH
2
O
N
N
N
O
N
O
O
N
N
O
X
N
N
9’b
Sug(OH)n
n(HO)Sug
N
N
N
X
N
N
N
O
OH
N
O
N
O
O
OH
OH
HO
N
N
O
9
N
OH
N
N
N
O
N
O
N
O
OH
2
Scheme 1. Synthetic route leading to light-sensitive bolaamphiphiles (A) and chemical structures of GNBAs 9a, 9’a and 9’b (B)
Reagents and conditions: a - NaH (60 % dispersion in oil, 1.15 equiv), propargylbromide (80 % wt. in toluene, 1.2 equiv), anhydrous DMF, 45 min, microwaves (40 °C, 200 W), 84 %;
b - Peracetylated azidosugar (1 equiv), CuSO4, 5H2O (0.1 equiv), sodium ascorbate (0.2 equiv), tBuOH/H2O (1:1), 15 h, 65 °C, 64-71 %; c - PPh3 (1.2 equiv), NaN3 (5 equiv), CBr4 (1.2
equiv), anhydrous DMF, 24 h, RT, 61-71 %; d - KOH aqueous solution (1.5 M, 2.5 equiv), 4 h, 0 °C; e - Alkyl bromide (1.2 equiv), K2CO3 (1.2 equiv), anhydrous DMF, 48 h, RT; f - CuSO4,
5H2O (0.1 equiv), sodium ascorbate (0.2 equiv), tBuOH/H2O (1:1), 15 h, 65 °C, 83-90 %; g - Hoveyda Grubbs II catalyst (0.05 equiv), anhydrous DCM, 16 h, 40 °C, 27-47 %; h - Sodium
methoxide solution (1M in anhydrous MeOH), anhydrous DCM/MeOH, 1-2 h, RT, 51-70 %.
The E-configuration of the stilbene chromophore was assessed from experiments on the intermediate 12. Characteristic bands of E-
1H NMR of the model structure (11). Chemical shifts associated to configuration at 965.2 cm-1 and 940.1 cm-1 (C-H bending vibration)
aromatic (δ = 6.85-6.91 and 7.38-7.45 ppm) and ethylenic protons (δ decreased in intensity after irradiation combined with the
= 6.92 ppm) are in agreement with the sole formation of the E-isomer appearance of a new band at 879.4 cm-1 (C-H bending vibration),
as reported in the literature.50 Thus, no signal corresponding to the corroborating the E - Z transition (Figure SI16).
Z-stilbene configuration was detected (Figure SI7). The
photoresponse of 11 in MeOH and DMSO solutions was investigated
using monochromatic UV irradiation at 336 nm (Figures 2 and SI10).
The spectral changes were monitored by UV-Vis and NMR
spectroscopies to determine the temporal evolution of the
absorbance and composition of the samples. During irradiation, the
absorbance at long wavelength was found to decrease in agreement
with photoinduced E - Z isomerization.
In the case of 11, the composition of the photostationary state (PSS)
was determined by 1H NMR to be 0.15 and 0.28 (E : Z) in MeOH and
DMSO respectively (Figure SI14, Table SI15). The greater proportion
of E-isomer in DMSO reflects a greater efficiency for the Z→E process
Figure 2. Spectral changes in the electronic absorption spectrum of 11 (88.0 µM in
DMSO) upon irradiation at 336 nm and the variation of the composition of the solution
versus irradiation time.
in this solvent and some solvatochromism of the Z-isomer. However,
the isomerization E - Z was moderately sensitive to solvent effects
(E→Z = 0.37 in MeOH and 0.39 in DMSO). Calculated quantum yields

E→Z of bolaamphiphiles 9a, 9’a, 9’b were found to be 0.31, 0.30 and
The gelation abilities of bolaamphiphiles 9a, 9’a and 9’b were
evaluated in organic and aqueous solvents. All molecules were
insoluble in the majority of solvents but different behaviors were
noticed in solvent mixtures (Table SI17). While 9’b remained
insoluble, 9a and 9’a in water / ethanol mixtures led to gels of
0.36 respectively. These values are similar to E→Z of 11 in DMSO,
indicating a limited impact of the two glyconucleoside heads on the
photoisomerization process (Table SI15, Figures SI11-SI13). The
photoisomerization was also qualitatively observed in FT-IR
2 | J. Name., 2012, 00, 1-3
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qualitatively different stabilities based on the inversion test tube stilbene. However, the rigidity conferred by the interpenetrating
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DOI: 10.1039/D0CC00336K
method. The viscoelastic moduli G' and G" of 9a and 9’a based-gels network led to a slow process (5 to 6 hours). Irradiation with a more
at 2.4 % (w/v) and 2 % (w/v) respectively in H2O/EtOH (1:1) were powerful lamp at 312 nm allowed to reduce the time of exposure to
measured by oscillatory rheology (molar concentration of 13.25 2 hours even if the proportion of Z-isomer in the PSS was lower at
mM). Over the entire frequency range, G' exceeded more than five this wavelength (PSS = 0.54 for 11 in solution in DMSO). Liquid states
times G" and values displayed a weak dependence, indicating a solid- highlighted a network of smaller nanofibers in transmission electron
like behavior (G' = 30.0 ± 2.6 kPa for 9a and 8.0 ± 0.9 kPa for 9’a at 1 microscopy, responsible thereby for the absence of gelation (Figures
Hz; Figures 3 and SI18). Interestingly, 9a based-gel displayed higher 4 and SI24). Interestingly, the destruction of a stiffer material (9a
G’ values than 9’a indicating a stiffer material probably due to an based-gel at 5 % (w/v), G’ = 64.4 ± 5.7 kPa) did not require an increase
increase of hydrogen bonding capabilities provided by the lactose of the irradiation time (Figures SI21 and SI23).
moieties. Besides, both gels showed thixotropic properties. This
behavior was first estimated using rheology by applying successive
A
B
low (inside the LVR region) / high strain values (above the flow point,
50 %) to disrupt the 3D network until the flow and test its recovery
ability when the high strain is stopped. A high strain led to an
immediate collapse of gels as G" became superior to G' but
instantaneously after its removal, G' recovered nearly 70 % of its
initial value and reached 100 % in 50 minutes (Figure 3). This
behavior was then evaluated by gel extrusion through a syringe and
the gel state was confirmed by a G' value superior to G" (SI video,
Figure SI20). Finally, high transition temperatures from gel to sol
were measured at 54 °C (9a) and 60 °C (9’a) (Figure SI18).
1 µm
1 µm
UV light
  312 nm
Transmission electron microscopy performed on bolaamphiphiles 9a
and 9’a based-gels at 2.4 % (w/v) and 2 % (w/v) respectively exhibited
similar entangled network composed of helicoidal nanofibers of
around 20 nm in diameter and 140 nm in pitch (Figures 4 and SI22).
100,000
10,000
1 µm
1 µm
Figure 4. Optical and transmission electron microscopy images of A - 9a based-gel at 2.4
% (w/v) and B - 9’a based-gel at 2 % (w/v) before and after UV irradiation at 312 nm.
Scale bars: 1 µm.
1,000
9a
9’a
100
As a gel-sol transition was observed in response to light-stimuli, we
would expect the E - Z transition and a majority of Z-isomer in
solution states. UV spectra of irradiated 9a and 9’a gels at 312 nm
exhibited a Z-isomer pattern due to the * electronic transitions,
indicating therefore the proper photoisomerization (Figure SI25).
Besides, the absorbance measured at the maximum of absorption of
the E-isomer (332 nm) allowed to estimate the proportion of E- and
Z-isomers after irradiation. A high proportion of Z-isomer, estimated
at 75 %, was highlighted in both cases. This result suggested that the
complete destruction of the supramolecular architecture into sol
states required a similar proportion of Z-isomer calculated in the PSS
in solution.
0.1
1.0
10.0
Frequency (Hz)
100,000
10,000
1,000
100
60
50
40
30
20
10
0
10
1
0
1000
2000
3000
Time (sec)
Figure 3. Frequency sweep experiments on 9a and 9’a based-gels at 2.4 % (w/v) and 2 %
(w/v) respectively (constant strain: 0.05 % for 9a and 0.02 % for 9’a) and step-strain assay
on 9’a based-gel at 2 % (w/v) (constant frequency: 1 Hz, successive cycles: 1/ strain of
0.02 % for 5 minutes, 2/ strain of 50 % for 2 minutes, 3/ identical to 1/ for 60 minutes).
In this study, we have synthesized GNBAs featuring a photo
switchable stilbene moiety as light-sensitive LMWGs. The self-
assembly of 9a and 9’a in water / ethanol mixture at low
concentrations revealed the formation of fibrillar networks. Besides,
these physical gels featured high elastic moduli, thixotropic
properties and gel-sol transitions compatible with biomedical
applications. By using photosensitive GNBAs, in which the stilbene
To investigate the potential of these systems as light-sensitive
materials, gels were submitted to UV light. Irradiation at 336 nm
allowed the destruction of supramolecular architectures to form
liquid solutions caused by the expected photoisomerization of E- moiety changed its configuration from E to Z under irradiation, the
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2436.
self-assembly could be controlled by UV light leading to macroscopic
changes i.e. gel-sol transition. These new supramolecular responsive
hydroalcoholic materials could be an alternative to the existing
polymer based-drug delivery systems for external use as the UV light
stimulation may provide a faster drug release when needed.
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