A Green and Sustainable Route to Carbohydrate Vinyl Ethers for Accessing Bioinspired Materials with a Unique Microspherical Morphology

Article abstract of DOI:10.1002/cssc.201701489

Synthesizing chemicals and materials from renewable sources is one of the main aims of modern science. Carbohydrates represent excellent renewable natural raw materials that are ecofriendly, inexpensive, and biologically compatible. A green procedure has been developed for the vinylation of carbohydrates by using readily available calcium carbide. Various carbohydrates were utilized as starting materials, resulting in mono-, di-, and tetravinyl ethers in high to excellent yields (81–92 %). The synthesized biobased vinyl ethers were utilized as monomers in free radical and cationic polymerizations. A unique combination of a smooth surface and intrinsic microcompartments was achieved in the synthesized materials. Two types of biobased materials were prepared involving microspheres and intrinsic hollow compartments in polymers. Scanning electron microscopy with built-in ion beam cutting was applied to reveal the spatial hierarchical structures in 3D space.

Full text of DOI:10.1002/cssc.201701489

Accepted Article
Title: Green and sustainable route to carbohydrate vinyl ethers for
accessing bio-inspired materials with a unique microspherical
morphology
Authors: Konstantin Rodygin, Irina Werner, and Valentine P. Ananikov
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To be cited as: ChemSusChem 10.1002/cssc.201701489
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ChemSusChem
10.1002/cssc.201701489
Green and sustainable route to carbohydrate vinyl ethers for
accessing bio-inspired materials with a unique microspherical
morphology
a
a
a,b ,
Konstantin S. Rodygin, Irina Werner, Valentine P. Ananikov
*
a
Saint Petersburg State University, Universitetskii prospect, 26, Petergof, Russia.
b
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect, 47,
Moscow, Russia; e-mail: val@ioc.ac.ru
Abstract
Synthesizing chemicals and materials based on renewable sources is one of the main tasks of modern
science. Carbohydrates represent excellent renewable natural raw materials, that are eco-friendly,
inexpensive and biologically compatible. Herein, we developed a green vinylation procedure for
carbohydrates using readily available calcium carbide. Various carbohydrates were utilized as starting
materials resulting in mono-, di- and tetra-vinyl ethers in high to excellent yields (81-92 %). The
synthesized bio-based vinyl ethers were utilized as monomers in free radical and cationic
polymerizations. A unique combination of smooth surface and intrinsic microcompartments was achieved
in the synthesized materials. Two types of bio-based materials were prepared involving microspheres and
“
Swiss cheese” polymers. Scanning electron microscopy with built-in ion beam cutting was applied to
reveal the spatial hierarchical structures in three-dimensional space.
Keywords: biomass; carbohydrates; calcium carbide; vinylation; bio-based materials.
1
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ChemSusChem
10.1002/cssc.201701489
Introduction
Bio-inspired materials have found numerous applications in regenerative medicine, biochemistry,
1,2,3,4,5,6,7
organic framework preparation, soft robotics, and nano and polymer science.
developing with several breakthrough opportunities in modern science and technology.
This field is rapidly
Natural carbohydrates represent an excellent class of compounds for the development of
8
bioinspired materials. The tunable nature of carbohydrates makes it possible to protect their hydroxyl
groups to facilitate hydrophobic properties. The ability to control the hydrophobic properties is important
9
for numerous practical applications and for increasing the stability of carbohydrates against degradation.
For accessing sustainable products, it is important to develop synthetic routes based on starting
materials from renewable sources. Moreover, it is important to maintain green chemistry procedures,
which avoid toxic chemicals and minimize the amount of organic waste when processing biomass-derived
raw materials. Challenged with these requirements, in the present study, we have developed bio-inspired
materials based on sustainable biomass (Scheme 1). The carbohydrates from biomass can be easily
protected to obtain the required number of hydroxyl-groups (Scheme 1, route a). Sustainable vinylation
was carried out using calcium carbide (Scheme 1, route b), which reacts in situ with protected
carbohydrates and produces vinyl monomers (Scheme 1, route c). Vinyl monomers can be efficiently
converted to polymeric materials (Scheme 1, route d).
It is important to mention that virtually all kinds of carbon can be used to prepare calcium
10
carbide. Renewable sources of carbon, carbon obtained from waste processing, carbon-containing
10
feedstocks and natural carbon can be transformed into calcium carbide with very good efficiency.
Applying CaC is one of the best approaches for the incorporation of vinyl functional groups into organic
2
11
compounds. From an environmental viewpoint, it is a clean process since calcium salts can be
regenerated and reused (Scheme 1, route e). Overall, the polymeric materials developed here are
accessible only when using renewable natural resources (carbohydrates and carbon) as raw starting
materials.
Scheme 1. Sustainable route to the bioinspired carbohydrate polymers proposed in the present study.
The key step is to develop a rapid and green methodology for the one-pot reaction of CaC with
2
carbohydrates (Scheme 1, route c). It is important to carry out the reaction in a one-pot manner instead of
12,13
using dangerous and highly flammable acetylene gas.
In the present work, we report a green route for
2
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ChemSusChem
10.1002/cssc.201701489
the vinylation of carbohydrates with calcium carbide, synthesis of vinyl ethers of natural carbohydrates
and preparation of the corresponding polymeric material (Scheme 1).
Results and discussion
Carbohydrates contain several OH groups; however, only certain OH groups should be vinylated,
while the other OH groups should be protected to maintain the hydrophobic properties. We protected four
OH groups with isopropylidene protecting groups to obtain a pure monovinylated product while avoiding a
mixture of vinyl ethers. To demonstrate the applicability of the method, we have also vinylated two and
four OH groups (divinyl and tetravinyl products were isolated in their pure form).
The protection of D-(-)-fructose (1a) and synthesis of 2a was carried out using an acetone/H SO
2
4
14
system according to the standard procedure (see the experimental part). To study the vinylation
process, we used a model reaction of protected D-(-)-fructose with calcium carbide under basic conditions
(
Scheme 2). Acetylene was generated in situ upon the reaction of CaC with water. The base was
2
required to facilitate nucleophilic addition of the hydroxyl group to the triple bond of acetylene. The
optimization of the reaction conditions for the vinylation of the protected D-(-)-fructose with CaC is
2
summarized in Table 1.
Scheme 2. Synthesis of the vinyl ethers of carbohydrates using calcium carbide.
Table 1. Optimization of the reaction conditions for the vinylation of the protected D-(-)-fructose (see
a
Scheme 2 for the reaction).
b
Entry Solvent
System
CaC : H O ratio
Yield , (%)
2
2
1
2
3
4
5
6
7
DMF
KOH/KF
1 : 4
1 : 4
1 : 4
1 : 4
1 : 4
1 : 2
1 : 0
NR
NR
NR
NR
92
Dioxane KOH/KF
Toluene KOH/KF
THF
KOH/KF
KOH/KF
KOH/KF
KOH/KF
DMSO
DMSO
63
c
DMSO
NR
3
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ChemSusChem
10.1002/cssc.201701489
8
9
DMSO
DMSO
DMSO
-
1 : 4
1 : 4
1 : 4
Traces
Traces
NR
K CO
2
3
10
Et N
3
a
Reaction conditions for the vinylation: substrate (1 mmol), CaC (6 mmol), base (1.1 mmol), solvent (5
2
b
c
mL), and additive (4 mmol). Isolated yield. Anhydrous DMSO.
The experiments in different solvents showed that DMSO is the solvent of choice for carrying out
vinylation with calcium carbide (entries 1-5; Table 1). An optimal CaC : H O ratio of 1 : 4 was utilized;
2
2
decreasing the amount of water lowered the yield, and without added water, the reaction did not proceed
entries 5-7; Table 1). Using a base was important for promoting the reaction (entries 5, 8), and a
(
combination of KOH and KF improved the performance (entries 5, 9, 10; Table 1). Thus, a one-pot
procedure was developed to perform vinylation under simple conditions in excellent yield (92 %). The
vinylation reaction was carried using only simple inorganic compounds (CaC , KOH and KF), which
2
readily simplified the isolation and purification of the synthesized organic product 3a. The isopropylidene
protecting group was stable under the studied experimental conditions. It should be emphasized that
granulated calcium carbide from commercial sources may release varying amounts of acetylene (i.e.
15
typically around 75%). The exact amount of acetylene may be measured by volumetric analysis in each
particular batch, however a more flexible solution is to apply an excess of CaC . This will also account for
2
plausible traces of water, which may be available in the system.
Using the optimized conditions, we synthesized a series of vinylated carbohydrates (Table 2).
Different procedures were utilized for the vinylation of carbohydrates bearing both even and odd numbers
of hydroxyl groups. Carbohydrates with an odd number of hydroxyl groups (fructose, galactose, glucose,
and sorbose) were protected using isopropylidene protecting groups, leaving one –OH group for the
reaction with acetylene (entries 1-5; Table 2). Carbohydrates with an even number of hydroxyl groups
(
arabinose, lyxose, and ribose) were protected using isopropylidene and a methyl protecting group in
order to leave a single –OH group for the reaction with acetylene (entries 6-8; Table 2). At the end of the
reaction, the final products (2a – 2h) were isolated after extraction with hexane. Products 2a – 2h were
synthesized in excellent yields of 81 – 92 %.
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ChemSusChem
10.1002/cssc.201701489
a
Table 2. Vinylation of different carbohydrates using the developed procedure with CaC2.
Protected
Vinylated product
and isolated yield
Entry
Starting material
carbohydrate
1
1a
D-(-)-Fructose
2a
3a, 92%
2
1a
D-(-)-Fructose
2b
3b, 81%
3
4
5
1
c
D-(+)-Galactose
2c
3c, 91%
1d
2d
D-(+)-Glucose
3d, 83%
1e
L-(-)-Sorbose
2e
3e, 85%
6
7
1
f
L-(+)-Arabinose
2f
3f, 86%
1g
D-(-)-Lyxose
2g
3g, 82%
5
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10.1002/cssc.201701489
8
1h
D-(-)-Ribose
2h
3h, 92%
a
Reaction conditions: protected carbohydrate (1 mmol), CaC (6 mmol), H O (24 mmol), DMSO (5 mL),
2
2
KOH (1.1 mmol), KF (4 mmol), 130 °C, and 3 h.
To assess the possibility of double vinylation, the developed procedure was applied to 1,2-
isopropylidene-α-L-xylofuranose (2i). In this carbohydrate, two hydroxyl groups were protected in the form
of monoacetonide, and two hydroxyl groups were available for the reaction (Scheme 3). The one-pot
transformation with calcium carbide in the presence of KF/KOH led to double vinylation with an excellent
isolated yield of 75 % divinyl ether 3i.
Scheme 3. Double vinylation of protected xylose using calcium carbide.
The developed vinylation reaction involving calcium carbide proceeded efficiently for the studied
substrates. In all the studied cases, isopropylidene protective groups were found to be completely stable
(
130 °C, 3 h). Important for practical applications, we also monitored the stability of the benzylidene
protecting groups under these reaction conditions. The reliable performance of the protective groups was
16
completely consistent with previous investigations. Methyl 4,6-O-benzylidene-α-D-glucopyranoside (2j)
was obtained from methyl-α-D-glucopyranoside (1j) and was utilized as a starting material (Scheme 4).
Double vinylation was successfully carried out in the developed system, and product 3j was isolated in
74 % yield. After extraction with hexane, only the completely vinylated product was soluble in the organic
phase. The presence of a single –OH group caused the sugars to remain in the DMSO/KOH phase. This
is a crucial advantage of this synthetic procedure; independent of the number of hydroxyl groups
presented in the starting sugar, only the final vinylated products are isolated. The vinylated products
extracted with hexane were usually of sufficient purity, but when required, further purification was carried
out using distillation under vacuum.
6
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10.1002/cssc.201701489
Scheme 4. Double vinylation of methyl-4,6-O-benzylidene-α-D-glucopyranoside (2j) using
calcium carbide.
The possibility of multiple vinylations was an interesting option to explore. Using methyl α-D-
glucopyranoside (1k), one-pot tetravinylation was carried out in the presence of KF (Scheme 3). Minor
amounts of incompletely vinylated sugars were also present in the reaction mixture at the end of the
reaction (i.e., mono-, bis- and tris-vinylated compounds). Nevertheless, pure product 3k was isolated in
75 % yield using the same simple separation procedure. The yield of the product was significantly lower
in the presence of KOH due to side-reactions causing product degradation. The yield was improved by
using a larger excess of KF in the absence of KOH. Most likely, on one hand the bases facilitate the
addition reaction and improve the product yield. On the other hand, the base additives may initiate
polymerization of the product (which represents a vinyl monomer) through a base-promoted
polymerization. Therefore, the optimal amounts of KOH and KF should be determined for a particular
carbohydrate substrate.
Scheme 5. Quadruple vinylation of methyl α-D-glucopyranoside with calcium carbide.
To demonstrate synthetic utility of the reaction we have carried out the vinylation on a large scale
and isolated 3.5 g of 3a in 88 % yield under the same optimized conditions (Table 1, entry 5). The
reaction may be performed in a suitable sealed flask or small autoclave. Acetylene has a good solubility
in DMSO and it was readily consumed during the reaction.
Vinyl ethers are well known as excellent monomer that easily undergo polymerization using ionic
1
7,18
or free radical initiators.
fructopyranose (3a) as a monomer using both free radical and cationic polymerization mechanisms
Scheme 6). The free radical polymerization of 3a in the presence of AIBN (2 mol%) and DMF yielded a
To address this possibility, we used 2,3:4,5-di-O-isopropylidene-β-D-
(
well-defined oligomer (4a) as a gum (Scheme 5). Cationic polymerization with boron trifluoride etherate
under an inert atmosphere yielded crystalline solid 5a (Scheme 6). Reprecipitation from a
methanol/hexane mixture resulted in pure polymeric materials, which were characterized by NMR
spectroscopy and size exclusion chromatography (SEC). The values of Mn,SEC = 3500 and 8500 [g/mol]
were obtained for 4a and 5a, respectively (Scheme 6).
Achieving higher molecular weights and accessing large polymers is a well-developed area for
19
vinyl ethers. This topic was not addressed in the present study since we were interested in tuning the
morphology of soft and soluble polymeric materials using dissolution/precipitation procedures. Polymers
with high molecular weights typically possess poor solubility and are not suitable for the liquid-phase-
7
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10.1002/cssc.201701489
controlled design of flexible morphologies. In the present case, polymers with medium molecular weights
were synthesized and exhibited controlled solubility in commonly used solvents (toluene and methanol).
Scheme 6. Free-radical (left) and cationic (right) polymerization of 2,3:4,5-di-O-isopropylidene-β-D-
fructopyranose (3a).
a
b
d
c
8
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e
f
Figure 1. Electron microscopy images of the polymeric materials with a microspherical morphology (a, b)
and fused hierarchical morphology (c, d) and the intrinsic structure found in the cut of the fused
hierarchical material. Scale bars: 10 µm (a, c), 1 µm (b, d, e), and 200 nm (f).
As determined experimentally, the synthesized polymers with medium molecular weights enabled
the possibility of designing unique morphologies upon precipitation from solution and the controlled
removal of the solvent. The morphology of the isolated polymeric materials was characterized using
scanning electron microscopy (SEM). A simple procedure involving the dissolution of the polymer in
toluene, followed by reprecipitation with hexane and drying under vacuum generated a microspherical
morphology (Figure 1a and 1b). Excellent shape uniformity and a relatively narrow size distribution (1 - 5
µm) were revealed in the SEM study. By changing the reprecipitation and drying conditions, it was
possible to induce fusion of the microspheres into hierarchical 3D structures with smooth outer surfaces
(
Figure 1c and 1d). Mechanical cutting of the hierarchical material revealed a number of cavities inside
the polymer (Figure 1e and 1f). The cavities possessed spherical shapes with diameters of 0.2 – 2 µm
Figure 1e and 1f).
(
To examine the intrinsic organization of the cavities, spatially controlled cutting with a focused ion
beam was carried out inside the electron microscope (Figure 2). The focused ion beam removes thin
layers slice-by-slice from the selected area of the material. Indeed, the intrinsic organization of the studied
material showed the presence of boundaries between the cavities and the absence of networking
connections between them (Figure 2; see also the video in the Supporting Information).
9
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ChemSusChem
10.1002/cssc.201701489
Figure 2. SEM images of polymer 5a after cutting with a focused ion beam. In the first and last images,
the purple rectangles show the examined area. The yellow and red arrows show changes in the surface
after each cutting; the green arrows indicate the existing boundaries of the cavities.
Thus, the arrangement of the microspherical outer morphologies (Figure 1a and 1b) of the
individual particles and the incorporation of spherical cavities inside the hierarchical fused material
(
Figure 1c – 1f) were observed. The prepared morphologies are applied for encapsulation and controlled-
release applications. Typically, rather complicated experimental protocols are utilized to prepare such
materials. In contrast, in the present study a straightforward and simple procedure was developed using
biobased monomeric building blocks. Innovative materials containing natural carbohydrate units have
been successfully utilized in a number of important applications including access to glycoconjugates, drug
20
delivery, and biocompatible materials, among many others.
Conclusions
To summarize, we have developed a green route for the one-pot vinylation of carbohydrates
using easily available calcium carbide. The developed procedure involved only inexpensive inorganic
compounds (KF, KOH and CaC ) and did not include toxic or environmentally unfriendly components. The
2
straightforward synthetic procedure was combined with efficient separation: simple extraction with hexane
resulted in the isolation of pure vinylated products. Further purification was performed using vacuum
distillation (chromatography and the excessive use of solvents was completely avoided). This synthetic
transformation was universally applied to prepare a number of mono-vinylated carbohydrates in excellent
yields (82 - 92 %) and bis- and tetra-vinylated carbohydrates in high yields (75 %).
10
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The polymerization reactions were studied using free radical and cationic conditions using a
synthesized carbohydrate vinyl monomer. Polymers with suitable molecular weights exhibited medium-
dependent solubility and flexible access to the unique morphologies demanded by practical applications.
The synthesized materials were characterized using electron microscopy, and the intrinsic organization
was studied using a focused ion beam technique.
Using the developed methodology, the vinyl ethers of carbohydrates and their corresponding
polymeric materials were obtained from renewable resources (biomass and carbon). Sustainably sourced
starting materials were combined with atom-economic vinylation (i.e., the addition reaction of a hydroxyl
group to the triple bond of acetylene is atom-economic and does not produce waste). Overall, a cost-
efficient and environmentally friendly procedure was developed.
Experimental section
General. The chemicals were obtained from commercial sources (Acros Organics and Sigma-
15
Aldrich) and tested with NMR and GC before use. Calcium carbide was utilized in the granulated form.
AIBN was recrystallized from dry methanol twice and dried under vacuum overnight. Boron trifluoride
etherate was redistilled prior to use. Deuterated NMR solvents (CDCl and acetone) were purchased from
3
Cambridge Isotope Laboratories. In some cases, deuterated chloroform was purified from traces of acid
through aluminum oxide, molecular sieves and Ag foil, since synthesized vinyl ethers may undergo
hydrolysis in the presence of acidic impurities.
NMR spectra of the complexes were recorded using a Bruker Avance DRX 400 spectrometer at
1
13
2
98 K. The H and C NMR chemical shifts were reported in ppm vs. SiMe and were determined by
4
referencing the peaks to the residual solvent peaks. HRMS (ESI) was performed using a Bruker
microTOF. Size exclusion chromatography (SEC) was carried out using a Shimadzu LC-20AD modular
system equipped with a TSkgel G5000HHR column (7.8 mm × 300 mm) and an RID-10A differential
/ )
refractive index detector. The average molar mass ( M n SEC) and molar mass distribution ( M w M n
1
values were determined using SEC in THF at 30 °C (flow rate = 1.0 mL·min ) vs. polystyrene standards.
The unit calibration was conducted using commercially available narrow molecular-weight-distribution
polystyrene standards (0.5-1000 kDa, Polymer Laboratories). The chromatograms were processed using
Shimadzu LCsolution software. The polymer samples were initially filtered through a PTFE filter (0.45 µm,
1
1
3 mm, Macherey-Nagel) and dissolved in THF (2 mg·mL ).
The investigations of the polymer materials were carried out using low-voltage scanning electron
microscopy (LV-SEM) through a double-beam FIP-REM Zeiss Auriga station. The accelerating voltage of
the electron column was 1 kV, and the beam current was 300 pA. The pressure in the chamber was
-
6
approximately 3·10 mbar. To obtain the images, a secondary electron emission signal was recorded
using an Everhart-Torley detector. To reduce the noise of the image, row averaging was used. The
polymer particles were cut by etching with a focused beam of gallium ions using a double-beam FIP-REM
Zeiss Auriga station. The accelerating voltage of the ion column was 30 kV, and the beam current was
600 pA.
11
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10.1002/cssc.201701489
All manipulations with vinyl ethers were performed under a purified argon atmosphere using
standard Schlenk techniques. Synthetic transformations were carried out using a suitable sealed vessel
or autoclave, compatible with some internal pressure, which may develop due to reaction of calcium
carbide with water.
Experimental procedure for the monovinylation of the protected carbohydrates.
First, 1.0 mmol of a carbohydrate, 1.1 mmol of KOH, 4.0 mmol of KF and 6.0 mmol of powdered
calcium carbide were added to an 18 mL glass tube followed by the addition of 5 mL of DMSO. After
adding water (24.0 mmol), the tube was sealed, and the mixture was stirred at 130 °C for 3 hours. After
completion, the reaction mixture was extracted with hexane (6 x 5 mL), and the collected hexane
solutions were passed through a 2 cm thick celite pad. After solvent removal under a reduced pressure,
further purification was not required in most cases, and the desired products were obtained with sufficient
purity.
Experimental procedure for the divinylation of the protected carbohydrates.
First, 1.0 mmol of a carbohydrate, 2.2 mmol of KOH, 6.0 mmol of KF and 8.0 mmol of powdered
calcium carbide were added to an 18 mL glass tube, followed by the addition of 5 mL of DMSO. After
adding water (32.0 mmol), the tube was sealed, and the mixture was stirred at 130 °C for 3 hours. After
completion, the reaction mixture was extracted with hexane (6 x 5 mL), and the collected hexane
solutions were passed through a 2 cm thick celite pad. After solvent removal under a reduced pressure,
further purification was not required in most cases, and the desired products were obtained with sufficient
purity.
Experimental procedure for the tetravinylation of the methyl α-D-glucopyranoside.
First, 1.0 mmol of a carbohydrate, 17.0 mmol of KF and 8.0 mmol of powdered calcium carbide
were added to a 25 mL glass tube, followed by the addition of 10 mL of DMSO. After adding water (32.0
mmol), the tube was sealed, and the mixture was stirred at 130 °C for 3 hours. After completion, the
reaction mixture was extracted with diethyl ether (3 x 10 mL). After solvent removal under a reduced
pressure, the crude product was dissolved in hexane (20 mL) and passed through a 3 cm thick aluminum
oxide pad. After solvent removal under a reduced pressure, the residue was recrystallized from hexane at
–18 °C to obtain colorless crystals.
Purification of the vinyl ethers.
The vinyl ethers can be further purified using distillation under vacuum over calcium hydride.
Experimental procedure for the radical polymerization of 2,3:4,5-di-O-isopropylidene-1-O-
vinyl-β-D-fructopyranose (3a).
First, 400 mg (1.4 mmol) of 3a and 5 mg (0.03 mmol) of AIBN were added to an 8 mL glass tube
containing 22 mg of dry and degassed DMF. The tube was sealed, and the reaction was performed with
stirring under an inert atmosphere at 70 °C for 48 hours. Then, the reaction mixture was precipitated in
methanol (3 mL), and the residue was washed with hexane (3 x 3 mL). The crude product was dissolved
in DMF (3 mL) and again precipitated in methanol (5 mL). After the residue was washed with hexane (3 x
12
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ChemSusChem
10.1002/cssc.201701489
3
mL), the work up procedure was repeated twice. The residue was dried under a reduced pressure for
two days at 40 °C to obtain a colorless gum (200 mg, 0.7 mmol, 50% yield, Mn,SEC = 3500 [g/mol], Đ =
.73).
1
Experimental procedure for the cationic polymerization of 2,3:4,5-di-O-isopropylidene-1-O-
vinyl-β-D-fructopyranose (3a).
First, 400 mg (1.4 mmol) of 3a was placed into a Schlenk tube under an inert atmosphere at 0 °C.
Then, 1 mL of degassed dry toluene was injected into the tube. After three degassing cycles, a toluene
solution of boron trifluoride diethyl etherate (2 mol %) was injected into the tube under stirring. After 12
hours, the toluene solution was poured into methanol. The white solid was collected through a filter,
washed with hexane, dissolved in chloroform and precipitated in methanol again. The powder was dried
under a reduced pressure for two days at 40 °C (160 mg, 40% yield, Mn,SEC = 8500 [g/mol], Đ = 1.84).
Acknowledgements
This work was supported by a grant of the Russian Science Foundation (RSF grant 16-13-10301). The
authors also express their gratitude to the Centers of Saint Petersburg State University: Magnetic
Resonance; Chemical Analysis and Materials Research; Nanotechnology.
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