Synthesis of polysaccharide-based block copolymers via olefin cross-metathesis

Chen, Junyi; Kamitakahara, Hiroshi; Edgar, Kevin J.

doi:10.1016/j.carbpol.2019.115530

Cited by 10 publications

(13 citation statements)

References 30 publications

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“…The longer SEC retention time of the product is consistent with the higher molecular weight expected for the Dextran-b-PEG condensation product. There is too much overlap between peaks from the starting Dex-Br and the product to be certain of the absence of Dex-Br, but its absence is indicated by 13 C NMR spectroscopy results. However, SEC confirms the absence of PEG-amine from the product (Figure S1).…”

Section: ■ Results and Discussionmentioning

confidence: 97%

Regioselective Bromination of the Dextran Nonreducing End Creates a Pathway to Dextran-Based Block Copolymers

Chen¹,

Spiering²,

Mosquera-Giraldo

et al. 2020

Biomacromolecules

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Preparation of polysaccharide-based block copolymers with linear architectures is an important goal, opening up clear application potential and requiring significant advances in polysaccharide regio-and chemoselectivity. Herein we report a simple approach to prepare dextran-based block copolymers. Reaction with N-bromosuccinimide (NBS)/triphenyl phosphine (PPh 3 ) regioselectively brominates the sole primary alcohol of linear, unbranched dextran at C-6 of the nonreducing end monosaccharide. The resulting dextran, monofunctionalized with a terminal C-6 bromide, was coupled with various amine terminated polymers to prepare block copolymers, including dextran-b-poly(ethylene glycol), dextran-b-polystyrene, and dextran-b-poly(N-isopropylacrylamide). These renewable-based block copolymers, prepared in two selective, high-yielding steps from native linear dextran, exhibit various interesting properties. Dextran-b-poly(N-isopropylacrylamide) undergoes thermally induced micellization as revealed by dynamic light scattering (DLS), forming micelles upon exceeding 33 °C. We also observed microphase separation in dextran-bpolystyrene by using small-angle X-ray scattering (SAXS). Overall, this methodology provides a new, highly chemo-and regioselective, versatile route to diverse dextran-based block copolymers with useful properties, enabling drug delivery, compatibilization, and other applications.

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Section: ■ Results and Discussionmentioning

confidence: 97%

Regioselective Bromination of the Dextran Nonreducing End Creates a Pathway to Dextran-Based Block Copolymers

Chen¹,

Spiering²,

Mosquera-Giraldo

et al. 2020

Biomacromolecules

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“…In recent decades, "click chemistry" methods have been developed that share attractive features (e.g., rapid kinetics, mild conditions, high efficiency, high yield) and some have been applied to polysaccharides [4]. Azide-alkyne Huisgen cycloaddition [5], olefin cross-metathesis [6][7][8], and the thiol-ene reaction [9,10], are among those reported to have been applied to polysaccharides [6,11,12], affording a broad range of pathways for designing bioconjugates.…”

Section: Introductionmentioning

confidence: 99%

A Versatile Method for Preparing Polysaccharide Conjugates via Thiol-Michael Addition

Chen

Edgar

2021

Polymers

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Polysaccharide conjugates are important renewable materials. If properly designed, they may for example be able to carry drugs, be proactive (e.g., with amino acid substituents) and can carry a charge. These aspects can be particularly useful for biomedical applications. Herein, we report a simple approach to preparing polysaccharide conjugates. Thiol-Michael additions can be mild, modular, and efficient, making them useful tools for post-modification and the tailoring of polysaccharide architecture. In this study, hydroxypropyl cellulose (HPC) and dextran (Dex) were modified by methacrylation. The resulting polysaccharide, bearing α,β-unsaturated esters with tunable DS (methacrylate), was reacted with various thiols, including 2-thioethylamine, cysteine, and thiol functional quaternary ammonium salt through thiol-Michael addition, affording functionalized conjugates. This click-like synthetic approach provided several advantages including a fast reaction rate, high conversion, and the use of water as a solvent. Among these polysaccharide conjugates, the ones bearing quaternary ammonium salts exhibited competitive antimicrobial performance, as supported by a minimum inhibitory concentration (MIC) study and tracked by SEM characterization. Overall, this methodology provides a versatile route to polysaccharide conjugates with diverse functionalities, enabling applications such as antimicrobial activity, gene or drug delivery, and biomimicry.

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“…Recently, the groups of Matson, Edgar, and Kamitakahara reported BCPs containing cellulose derivatives such as cellulose acetate-b-polybutadieneb-cellulose acetate, 37 cellulose acetate-b-oligoamide, 38 and trimethyl cellulose-b-poly(ethylene glycol). 39 However, the microphase-separation behavior and mechanical properties of these BCPs have not been investigated. Furthermore, the advantages of using cellulose derivatives over other carbohydrates remain unclear.…”

Section: ■ Introductionmentioning

confidence: 99%

“…In addition, cellulose acetate has recently gained considerable attention because of its potential biodegradability. , Therefore, carbohydrate-based BCPs containing cellulose acetate segments are of significant interest in terms of their synthesis, self-assembly, and physical properties. Recently, the groups of Matson, Edgar, and Kamitakahara reported BCPs containing cellulose derivatives such as cellulose acetate- b -polybutadiene- b -cellulose acetate, cellulose acetate- b -oligoamide, and trimethyl cellulose- b -poly(ethylene glycol) . However, the microphase-separation behavior and mechanical properties of these BCPs have not been investigated.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Self-Assembly and Mechanical Properties of Cellulose-Based Triblock Copolymers: Comparisons with Amylose-Based Triblock Copolymers

Katsuhara

Takagi

Sunagawa

et al. 2021

ACS Sustainable Chem. Eng.

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Herein, we compared the microphase-separation behavior and mechanical properties of cellulose- and amylose-based block copolymers (BCPs). Various cellooligosaccharide triacetate-b-poly(δ-decanolactone)-b-cellooligosaccharide triacetates (AcCel n -b-PDL-b-AcCel n s), which are cellulose-based ABA-type BCPs, with PDL molecular weights of approximately 5, 10, and 20 kg mol–1 and PDL volume fractions of 0.65, 0.77, and 0.87, were synthesized from α,ω-diazido-end-functionalized PDLs and propargyl-end-functionalized cellooligosaccharide triacetates via click chemistry. We adopted the cellodextrin-phosphorylase-mediated oligomerization of α-d-glucose-1-phosphase in the presence of a propargyl-end-functionalized cellobiose primer to synthesize the functional cellooligosaccharide segment. The maltooligosaccharide triacetate-b-poly(δ-decanolactone)-b-maltooligosaccharide triacetate (AcMal n -b-PDL-b-AcMal n s) amylose counterparts were also synthesized in a similar manner. Small-angle X-ray scattering experiments and atomic force microscopy revealed that AcCel n -b-PDL-b-AcCel n s are more likely to microphase-separate into ordered nanostructures compared to AcMal n -b-PDL-b-AcMal n s, despite their comparable chemical compositions and molecular weights. Furthermore, AcCel n -b-PDL-b-AcCel n s exhibited significantly superior mechanical performance compared to their amylose counterparts under tensile testing, with Young’s modulus and stress at break of AcCel n -b-PDL10k-b-AcCel n being 2.3 and 1.8 times higher, respectively, than those of AcMal n -b-PDL10k-b-AcMal n . The enhanced microphase-separation and mechanical properties of AcCel n -b-PDL-b-AcCel n s were found to be attributable to the stiffness and crystalline nature of the AcCel n segments. These results demonstrate the advantages of using cellulose derivatives to synthesize novel biofunctional materials.

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Synthesis of polysaccharide-based block copolymers via olefin cross-metathesis

Cited by 10 publications

References 30 publications

Regioselective Bromination of the Dextran Nonreducing End Creates a Pathway to Dextran-Based Block Copolymers

Regioselective Bromination of the Dextran Nonreducing End Creates a Pathway to Dextran-Based Block Copolymers

A Versatile Method for Preparing Polysaccharide Conjugates via Thiol-Michael Addition

Enhanced Self-Assembly and Mechanical Properties of Cellulose-Based Triblock Copolymers: Comparisons with Amylose-Based Triblock Copolymers

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