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CHINESE JOURNAL OF POLYMER SCIENCE · 2021 ·Vol. 39 ·期 9 ·1161-1168 · IF 3.603

Reversible Chain Transfer Catalyzed Polymerization with Alkyl Iodides Generated from Alkyl Bromides by in Situ Halogen Exchange

Gao Dan-Ni,Zhao Yu-Lai,Cai Jing-Yu,Hou Lin-Xi,Xiao Long-Qiang

Reversible chain transfer catalyzed polymerization (RTCP) is a practical and efficient process for the precise synthesis of polymers with special architecture by using simple phenols (2,4,6-trimethylphenol, TMP) or hydrocarbons (xanthene, XT) as efficient organocatalysts. Herein, alkyl iodide (R-I), which was generated from in situ bromine-iodine transformation of alkyl bromide (R-Br) with sodium iodide (NaI), was served as initiator to mediate RTCP with TMP or XT. MMA and other functional methacrylates, including GMA, DEAM, DMAEMA and BzMA, were successfully initiated by combining organocatalysts and azo initiators to yield polymers with low-polydispersity ( M w / M n =1.1–1.5) and ideal monomer conversions (50%–90%) at moderate temperature. Moreover, 3-armstar polymers were also obtained by this method. The high chain-end fidelity of the obtained poly(methyl methacrylate) with iodine as chain-end group (PMMA-I) was confirmed by chain-extension reaction. The environmentally friendly initiators and organocatalysts exhibit powerful polymerization properties toward RTCP, providing a significant method to synthesize functional polymers.

研究领域: 高分子化学 · 材料科学 · 有机化学
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Polymer Chemistry · 2021 ·Vol. 12 ·期 40 ·5803-5814 · IF 5.582

A highly hydrophilic cation exchange nonwoven with a further modifiable epoxy group prepared by radiation-induced graft polymerization

Xiao-han Pan,Jian-hua Zu

Novel cation exchange nonwoven PP-g-SSS/GMA containing epoxy and sulfonic groups was successfully prepared via radiation-induced simultaneous grafting polymerization by attaching glycidyl methacrylate (GMA) and styrene sulfonic sodium (SSS) monomers onto nonwoven polypropylene (PP). The ion exchange capacity of the obtained PP-g-SSS/GMA reached more than 1.5 mmol g−1 and the content of the epoxy groups with potential modifiable properties was above 3 mmol g−1. The relative content of the two functional groups could be adjusted via changing the initial monomer concentration ratio. Scanning electron microscope (SEM) images showed that the polymer surface was fully covered with grafts after modification and those amorphous grafts diluted the crystallinity of the matrix, as revealed via differential scanning calorimetry (DSC). Attenuated total reflection spectroscopy (ATR) confirmed the successful grafting of GMA and SSS onto PP nonwovens. Water contact angle measurements showed that the contact angle decreased from 100.94° for the PP matrix to 0° for PP-g-SSS/GMA with a 56% degree of grafting, indicating the outstanding hydrophilicity of PP-g-SSS/GMA upon the introduction of SSS. Besides this, the epoxy groups on PP-g-SSS/GMA could be further modified via reacting them with chemical compounds with selective adsorption groups. Ag(I) adsorption tests proved that PP-g-SSS/GMA@EDA obtained via the ethanediamine (EDA) modification of epoxy groups on PP-g-SSS/GMA shows excellent selectivity towards Ag(I), and the hydrophilicity brought about by sulfonic groups also ensured a fast adsorption rate. The novel cation exchange nonwoven PP-g-SSS/GMA fabric has potential applications in water treatment, as its strong hydrophilicity could speed up the diffusion rates of adsorbed ions, and further functionalization of the epoxy groups could enable it to selectively adsorb ions in aqueous solutions.

研究领域: 材料科学 · 环境工程 · 高分子化学
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CARBOHYDRATE POLYMERS · 2022 · IF 10.723

A chitosan derivative-crosslinked hydrogel with controllable release of polydeoxyribonucleotides for wound treatment

Yanzhen Sun,Xiaodong Jing,Yang Liu,Bing Yu,Hao Hu,Hailin Cong,Youqing Shen

Nucleic acid-based agents have advantages in therapeutic efficacy and biological safety. However, due to its facile degradability, it lacks an effective route of administration in wound treatment. Designing smart hydrogels for the spatiotemporally controllable delivery of nucleic acids is of great significance for clinical applications. Here, a near-infrared (NIR)-responsive nanocomposite hydrogel was prepared using methyl methacrylate (GMA)-modified chitosan as the macromolecular cross-linker, N-isopropylacrylamide (NIPAAm) as the backbone, and molybdenum disulfide nanosheets (MoS 2 NSs) as the nanocomponents. The polydeoxyribonucleotide (PDRN), a nucleic acid-based agent that promotes tissue regeneration , was loaded and delivered. The photothermal conversion capability of MoS 2 NSs enables customized care of PDRNs and antibacterial enhancement. In a full-thickness skin defect model, high-quality wound healing effects were demonstrated under the action of nanocomposite hydrogels. The proposed nanocomposite hydrogel provides a new reference for local delivery of nucleic acid-based agents.

研究领域: 材料科学 · 生物医学工程 · 药剂学
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JOURNAL OF POLYMER RESEARCH · 2025 ·Vol. 32 ·期 9 ·1-17 · IF 2.8

Fully biodegradable poly (lactic acid)/poly (butylene adipate-co-terephthalate) blends with highly toughness based on in situ interfacial compatibilization by functional Epoxy compound

Shen Yunda,Jin Bingrui,Ren Liang,Gan Hongnian,Li Jiankun,Zhao Dan,Shen Huizhong,Zhang Mingyao

Synergistically integrating poly(butylene adipate-co-terephthalate) (PBAT) with polylactic acid (PLA) presents an economical strategy to develop biodegradable materials by leveraging their complementary characteristics. However, the inherent phase incompatibility between PBAT and induces severe interfacial defects, fundamentally limiting the development of high-strength biodegradable composites. In this study, glycidyl methacrylate (GMA) is grafted onto PBAT through reactive blending during the melting process, whereupon PLA/PBAT-g-GMA blends are prepared by means of an in-situ compatibilization approach, in an attempt to achieve PLA/PBAT blends with satisfactory comprehensive properties. The effects of PBAT content and GMA grafting rate on the interfacial compatibility, microstructure, mechanical properties, thermal performance, crystalline behavior and rheological processability of PLA/PBAT blends are investigated in detail. Systematic research has shown that the compatibility of PLA/PBAT blends has been significantly improved by implementing reactive compatibilization methods, and when the PBAT-g-GMA (2.84, the number refers to the grafting rate of GMA) content is 40%, the impact strength of the blend can reach 961 J/m without affecting rigidity, which indicates that our work proposes an effective approach to fabricate high-toughness PLA/PBAT blends through simple, environmentally friendly, and low-cost processing methods. Furthermore, the PLA/PBAT blends exhibit enhanced crystallization behavior while showing a slight decrease in thermal performance. The rheological analysis shows that the storage modulus, loss modulus, and complex viscosity significantly increase with the increase of PBAT content and GMA grafting rate, which improves processing performance of blends. SEM shows that as the grafting rate of GMA increases, the particle size distribution of PBAT becomes smaller and more uniform.

CAS / MDL: 106-91-2
研究领域: 材料科学 · 高分子科学与工程 · 生物可降解高分子 · 复合材料
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JOURNAL OF MOLECULAR LIQUIDS · 2024 · IF 5.3

De novo synthesis of α-Alk-β-CD: An organic–inorganic hybrid chiral stationary phase for enhanced enantioseparation efficiency and its recognition mechanism research

Jianbin Zhang,Qiufang Bai,Mei Han,Xizhe Sun,Feixue Zhou,Xin Fang,Yuran Shi,Hongna Wang,Yaowen Zhang,Linwei Li,Linlin Fang

Herein, two highly stable β -CD and α-Alkenyl- β -CD ( α -Alk- β -CD) monolithic columns were fabricated by copolymerizing β -CD and α -Alk- β -CD with GMA onto the pretreated capillary by a simple one-pot strategy. 1 H NMR, SEM, FT-IR, TGA and BET surface area analyses were applied to characterize the prepared monolithic columns. The monoliths were evaluated on the enantioseparations of antibiotic drugs, antihistamine drugs, anticholinergic agents, antifungal drugs and pesticides. In contrast to the native β -CD monolith, the derived α -Alk- β -CD reveals significantly improved enantiodiscrimination performance for the analytes especially for pesticides. Through run-to-run (n = 6), day-to-day (n = 9), and column-to-column (n = 9) investigations, the RSDs values were all lower than 3.72 %. Molecular simulation reveled that the chiral recognition between α -Alk- β -CD and chiral drugs was an exothermic process mainly governed by interaction hydrogen bindings, resulting in different binding strength between a pair of isomers compounds and α -Alkenyl- β -CD, and then leading to different migration and finally achieving effective chiral separation.

研究领域: 分析化学 · 色谱学 · 材料科学 · 药学
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LAB ON A CHIP · 2023 ·Vol. 23 ·期 10 ·2477-2486 · IF 6.1

Non-fouling polymer brush grafted fluorine-doped tin oxide enabled optical and chemical enhancement for sensitive label-free antibody microarrays

Xiaoyi Li,Zhihao Feng,Changxiang Fang,Yunpeng Wei,Dandan Ji,Weihua Hu

Oblique-incidence reflectivity difference (OIRD) is a compelling technique for real-time, label-free and non-destructive detection of antibody microarray chips, but its sensitivity needs essential improvement for clinical diagnosis. In this study, we report an innovative high-performance OIRD microarray by using poly[oligo(ethylene glycol) methacrylate-co-glycidyl methacrylate] (POEGMA-co-GMA) brush grafted fluorine-doped tin oxide (FTO) as the chip substrate. The polymer brush enhances the interfacial binding reaction efficiency of targets from the complicated sample matrix due to its high antibody loading and excellent anti-fouling merits; the FTO-polymer brush layered structure, on the other hand, excites the interference enhancement effect of OIRD to achieve enhanced intrinsic optical sensitivity. Synergistically, the sensitivity of this chip is significantly improved compared to rival chips, achieving a limit of detection (LOD) as low as 25 ng mL−1 for the model target C-reactive protein (CRP) in 10% human serum. This work explores the tremendous influence of the chip interfacial structure on the OIRD sensitivity and proposes a rational interfacial engineering strategy to boost the performance of the label-free OIRD based microarray and other bio-devices.

研究领域: 材料科学 · 生物医学工程 · 分析化学 · 光学
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JOURNAL OF DENTISTRY · 2024 · IF 4.8

Light-curable urushiol enhanced bisphenol A glycidyl dimethacrylate dentin bonding agent

Fei Wei,Tingting Bai,Huan Chen,Guangdi Sun,Xue Chen,Song Zhu

Objectives The low durability of composite resin restorations can be attributed to the degradation of the resin dentin bonding interface. Owing to the presence of hydrophilic components in the adhesive, the integrity of the resin dentin bonding interface is easily compromised, which, in turn, leads to a reduction in bond strength. The hydrophilic nature of the adhesive leads to water sorption, phase separation, and leaching of the resin component. Therefore, hydrophobic adhesives could effectively be used to stabilize the integrity and durability of the resin dentin bonding interface. Methods We synthesized a novel hydrophobic dentin adhesive by partially replacing bisphenol A glycidyl dimethacrylate (Bis-GMA) with a light-curable urushiol monomer. The properties of the produced adhesive, including the degree of conversion, viscosity, contact angle, water sorption/solubility, and mechanical strength, were comprehensively examined and compared to those of the commercially adhesive Adper Single Bond 2 as a positive control. The adhesive properties were determined using microtensile bond strength measurements, laser confocal microscopy, scanning electron microscopy observations, and nanoleakage tests. Finally, the novel adhesive was subjected to biocompatibility testing to determine its potential cytotoxicity. Results At a light-curable urushiol content of 20 %, the synthesized adhesive exhibited high degrees of conversion and hydrophobicity, low cytotoxicity, good mechanical properties, and outstanding adhesive strength. Conclusions The introduction of the light-curable urushiol into dentin adhesives can significantly enhance their hydrophobic, mechanical, and bonding properties, demonstrating potential to significantly improve restoration longevity. Clinical significance The integration of light-curable urushiol has endowed the experimental adhesives with several enhanced functionalities. These notable benefits underscore the suitability of this monomer for expanded applications in clinical practice.

研究领域: 牙科材料 · 粘接牙科学 · 高分子科学 · 生物相容性
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Journal of Materials Chemistry C · 2016 ·Vol. 4 ·期 29 ·7083-7092 · IF 5.066

Temperature responsive polymer brushes grafted from graphene oxide: an efficient fluorescent sensing platform for 2,4,6-trinitrophenol

Yajiao Song,Jianhua Lü,Bingxin Liu,Changli Lü

Thermo-responsive block copolymer brushes of PNIPAM-b-P(MQ-co-GMA) were successfully grafted from graphene oxide (GO) by consecutive reversible addition–fragmentation chain transfer (RAFT) polymerization based on the monomers of N-isopropylacrylamide (NIPAM), 5-(2-methacryloyl-ethyloxymethyl)-8-quinolinol (MQ) and glycidyl methacrylate (GMA). The 8-hydroxyquinoline units in the polymer brushes could coordinate with Al3+ to form green luminescent copolymer brushes containing tris(8-hydroxyquinoline)aluminum (Alq3) on the GO surface. The resulting fluorescent hybrid could be used as a nano-platform for the sensitive and robust detection of 2,4,6-trinitrophenol (TNP). The green fluorescence of the polymer brush modified GO hybrid in aqueous solution could be quenched by TNP via charge transfer and the observed linear fluorescence intensity change allowed the quantitative detection of TNP with a detection limit down to 2.38 × 10−9 M. The fluorescent nanohybrids exhibited a robust temperature-responsive behavior as a result of the conformation change in PNIPAM chains of polymer brushes.

研究领域: 材料科学 · 高分子化学 · 纳米技术 · 分析化学 · 环境科学
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Polymers · 2024 ·Vol. 16 ·期 10 ·1365 · IF 4.7

Preparation and Adsorption Performance of Boron Adsorbents Derived from Modified Waste Feathers

Dongxing Li,Hui Jiang,Zhengwei Luo,Wenhua Geng,Jianliang Zhu

This research focuses on modifying discarded feathers by grafting glycidyl methacrylate (GMA) onto their surface through thiolation, followed by an epoxy ring-opening reaction with N-methyl-D-glucamine (NMDG) to synthesize feather-based boron adsorbents. Optimization of the adsorbent preparation conditions was achieved through single-factor experiments, varying temperature, time, GMA concentration, and initiator dosage. The synthesized adsorbent (F-g-GMA-NMDG) underwent characterization using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and X-ray diffraction (XRD). The adsorption behavior of the adsorbent was studied, and its boron adsorption capacity at different temperatures was determined through static adsorption kinetic curves. Analysis of adsorption isotherms, kinetics, and thermodynamics was conducted. Results indicate that the boron adsorption process by F-g-GMA-NMDG follows a pseudo-second-order model. The adsorption process is endothermic, with higher temperatures promoting adsorption efficiency. Gibbs free energy (ΔG) confirms the spontaneity of the adsorption process. Enhanced adsorption efficacy was observed under neutral and acidic pH conditions. After four cycles, the adsorbent maintained its adsorption efficiency, demonstrating its stability and potential for reuse. This study provides novel insights into both the treatment of discarded feathers and the development of boron adsorbents.

研究领域: 环境科学 · 材料科学 · 化学工程 · 废物管理
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PROGRESS IN ORGANIC COATINGS · 2024 · IF 6.5

Photopolymerization initiated by p-diethylene glycol monomethyl ether cinnamyl formamide-based disulfide under 455 nm LED with minimized volume shrinkage

Yuhan Zhang,Nan Xiao,Yanjing Gao,Fang Sun

This study introduces a novel p -diethylene glycol monomethyl ether cinnamyl formamide-based disulfide monomer , N,N′ -(disulfanediylbis(2,1-phenylene)) bis(4-(4-(2-(2-methoxyethoxy)ethoxy) phenyl)-2-oxobut-3-enamide) (Mp-BSCF), designed to reduce the volume shrinkage of photosensitive resins and initiate monomer polymerization under 455 nm LED light irradiation. The photochemical properties and photoinitiation efficiency of Mp-BSCF are systematically investigated using UV–vis absorption spectroscopy , electron paramagnetic resonance (EPR) and real-time infrared spectroscopy . Although its weak absorption around 455 nm, Mp-BSCF can generate arylthiyl radicals under 455 nm LED irradiation, and then effectively initiate the polymerization of triethylene glycol dimethacrylate (TEGDMA)/A glycerolate dimethacrylate (Bis-GMA) system. Increasing Mp-BSCF addition enhances the final double bond conversion and maximum polymerization rate of the TEGDMA/Bis-GMA system, reaching up to 82.0 % and 2.02 % s −1 , respectively. Notably, Mp-BSCF significantly reduces the volume shrinkage of the photopolymerization system, with the addition of 10 % Mp-BSCF resulting in a 50 % reduction compared to the control system. This reduction is attributed to the dynamic reversible nature of the S S bond “breaking-recovery” and the intermolecular hydrogen bond interaction. Additionally, Mp-BSCF improves the thermal stability, friction resistance, and hardness of the TEGDMA/Bis-GMA photopolymerization system.

研究领域: 材料科学 · 高分子化学 · 光化学
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