Sucrose Methacrylate-Based Amphiphilic Block Copolymers

J of Chemical Tech & Biotech

2018

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BACKGROUND Carbohydrates are important renewable raw materials and their modification by enzymatic reactions with polymerizable groups is of great importance due the possibility of production of polymers with properties for biomedical applications. In this study, D‐fructose‐ and D‐glucose‐based monomers were prepared by enzymatic reactions and structurally characterized. Moreover, hydrogels based on poly(methacryloyl‐D‐fructose) were also prepared and characterized. RESULTS The conversions of 99% and 34% for D‐fructose and D‐glucose, respectively, were achieved using 2,2,2‐trifluoroethyl methacrylate as the methacrylic donor and commercial lipase Novozyme® 435 (EC 3.1.1.3) as enzymatic catalyst in t‐butanol. The molar ratios of D‐fructose and D‐glucose mono‐ and dimethacrylate were 57/43 and 87/13, respectively. These monomers are an isomeric mixture related to the tautomeric equilibrium of the carbohydrates in solution. Methacryloyl‐D‐fructose was polymerized in the presence of a controlled amount of ethyleneglycol dimethacrylate as crosslinker achieving hydrogels with different crosslinking densities which are mechanically stable when subject to compression–decompression cycles and have a high water swelling capability. CONCLUSION The combination of 2,2,2‐trifluoroethylmethacrylate and Novozym® 435 in a heterogeneous media lead to the continuous carbohydrate solubilization and reaction with the formation of carbohydrates‐based monomers. The control of the monomer functionality enables the synthesis of hydrogels with different crosslinking densities that tune their properties. © 2017 Society of Chemical Industry

Section: Introductionmentioning

confidence: 99%

Enzymatic synthesis and structural characterization of methacryloyl‐D‐fructose‐ and methacryloyl‐D‐glucose‐based monomers and poly(methacryloyl‐D‐fructose)‐based hydrogels

Perin

J of Chemical Tech & Biotech

2018

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“…These copolymers show LCST behavior in aqueous solution, whose critical temperature is influenced by composition. In another study, poly(alkyl methacrylate‐ b ‐SMA) was synthesized by atom radical transfer polymerization . The introduction of a few SMA units in the poly(alkyl methacrylate) chains affects their solubility, swelling capability, thermal stability, glass transition temperature, and morphology.…”

Section: Introductionmentioning

confidence: 99%

Thermoresponsive hydrogels based on sucrose 1‐O′‐methacrylate and N‐isopropylacrylamide: Synthesis, properties, and applications

Menezes

Camilo

J of Applied Polymer Sci

2017

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Chemically crosslinked hydrogels composed of carbohydrate‐based and thermoresponsive monomers, sucrose 1‐O′‐methacrylate (SMA), sucrose dimethacrylate, and N‐isopropylacrylamide, respectively, were synthesized by free radical polymerization. These materials were characterized with respect to their composition, thermoresponsiveness, porosity, degradability, and as drug and protein delivery systems. Swelling studies, thermomechanical analysis, and differential scanning calorimetry showed that the lower critical solution temperature behavior of the hydrogels can be controlled by the SMA amount in the copolymers. On the other hand, thermoporometry showed that the pore size is somewhat dependent on the composition, which is confirmed by scanning electron microscopy. Hydrolytic degradation studies indicated that SMA side chains, as well as the crosslinker (sucrose dimethacrylate), are hydrolysable at corporeal temperature and pH 10, and the water swelling capability of the resulting materials increases as the hydrolysis degree increases. Finally, protein delivery studies revealed that the kinetics of release can be tailored by the copolymer composition. The results of this study suggest the potential application of these hydrogels in drug delivery systems and tissue engineering. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45495.

“…In the last decade, our group has reported the synthesis of carbohydrate‐based monomers, [ 14,15 ] and their homo and copolymers via conventional [ 14–16 ] and controlled radical polymerization. [ 17,18 ] Amphiphilic diblock copolymers based on sucrose methacrylate (SMA) and alkyl methacrylates [ 18 ] synthesized by atom transfer radical polymerization (ATRP) presented the capability of self‐assembly in solution and in solid‐state‐forming lamellar structures. Moreover, they acted as emulsifier for water/oil emulsion.…”

Section: Introductionmentioning

confidence: 99%

Triblock Copolymers Based on Sucrose Methacrylate and Methyl Methacrylate: RAFT Polymerization and Self‐Assembly

Marcilli

Petzhold

Macro Chemistry & Physics

2020

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delivering systems, [2] nanoelectronics and nano-optics, energy-efficient bottom-up structuring of bulk materials, [3] and so on. One of the most notable features of amphiphilic block copolymers is the capability to self-assemble in solid state and in solution. This behavior results from the different chemical characteristics and solubility of the blocks, which are typically immiscible and soluble in different solvents. [4] The morphology of structures built from copolymer self-assembly is directly correlated with the copolymer structure, composition, and molar mass and demands synthetic strategies that provide accurate control over the polymerization. [4] In this context, controlled radical polymerization (CRP) [5][6][7] or reversible-deactivation radical polymerization (RDRP), [8] a more accurate denomination for specific cases such as for the reversible additionfragmentation chain transfer (RAFT) poly merization, plays an important role. RAFT has attracted a lot of interest from researchers in the last twenty years due to its versatility to synthesize copolymers with controlled molar mass, architecture, and narrow molar mass dispersity (Đ M ). [9] (Co)polymerization in sequential steps by RAFT is an efficient strategy to synthesize amphiphilic block copolymers, as reported elsewhere. [9][10][11][12] Sequential multistep polymerization allows designing the architecture of multiblock copolymers with different properties depending on the mono mer characteristics and the addition sequence. Another important issue with RAFT polymerization is the chain transfer agent (CTA), which determines polymerization control and, mainly, the architecture of copolymer (star-like copolymers, symmetric and nonsymmetric polymeric chains, and so on). Keddie et al. [6] and Moad et al. [9] published a very broad and in-depth discussion about RAFT polymerization of different monomers and CTA and their special features and applications. The information in these works facilitates the rational choice of CTA for certain monomers and desired polymer architectures.ABA and BAB triblock amphiphilic copolymers based on sucrose methacrylate and methyl methacrylate are synthesized by sequential reversible additionfragmentation chain transfer polymerization using S,S′-bis(R,R′-dimethyl-R′′-acetic acid)-trithiocarbonate as a chain transfer agent. The copolymers present narrow molar mass dispersity, controlled molar mass and architecture as determined by gel permeation chromatography and 1 H and 13 C nuclear magnetic resonance. The copolymers with molar and mass fractions of poly(sucrose methacrylate) block ranging from 1 to 22 mol% and 3 to 52 wt%, respectively, and different molar masses present characteristics of a surfactant such as self-assembly. The self-assembly of the triblock copolymers in water, N,N-dimethylformamide (DMF), dichloromethane, tetrahydrofuran, or benzene results mostly in vesicles as confirmed by scanning electron microscopy images and small-angle X-ray of the dispersions. Moreover, the copolymers present the capability to st...