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Varying the Core Topology in All-Glycidol Hyperbranched Polyglycerols: Synthesis and Physical Characterization. 改变全缩水甘油超支化甘油的核心拓扑结构:合成与物理特性。
IF 4.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-11-05 DOI: 10.1002/marc.202400791
Carlo Andrea Pagnacco, Alberto Alvarez-Fernandez, Armando Maestro, Estíbaliz González de San Román, Reidar Lund, Fabienne Barroso-Bujans

In the present study, low molecular weight cyclic polyglycidol is used as a macroinitiator for hypergrafting glycidol and producing cyclic graft hyperbranched polyglycerol (cPG-g-hbPG) in the molecular weight range of 103-106 g mol-1. Linear graft hyperbranched polyglycerol (linPG-g-hbPG) and hyperbranched polyglycerol (hbPG) are prepared as reference samples. This creates a family of hbPG structures with cyclic, linear, and star cores, allowing to evaluate their properties in solution and in bulk. The morphology study of the high molecular weight structures using atomic force microscopy revealed a spherical shape for cPG-g-hbPG and hbPG, and a cylindrical shape for linPG-g-hbPG in the nanometric range. Small angle X-ray scattering confirmed the compact particle-like structure of this family of hbPG architectures. Interestingly, the glass transition temperature showed a structure dependence, with cPG-g-hbPG having the highest values and hbPG having the lowest values for the same molecular weight. This study is a step forward in the generation of water-soluble polymers with tailored structure and functionality for advanced applications.

在本研究中,低分子量环状聚缩水甘油被用作超接枝缩水甘油的大引发剂,并生成分子量范围为 103-106 g mol-1 的环状接枝超支化聚甘油(cPG-g-hbPG)。线性接枝超支化聚甘油(linPG-g-hbPG)和超支化聚甘油(hbPG)被制备为参考样品。这样就形成了具有环状、线性和星形核心的 hbPG 结构系列,从而可以评估它们在溶液和块体中的特性。使用原子力显微镜对高分子量结构进行的形态学研究表明,cPG-g-hbPG 和 hbPG 呈球形,而 linPG-g-hbPG 则呈纳米级的圆柱形。小角 X 射线散射证实了这一系列 hbPG 结构的紧凑颗粒状结构。有趣的是,玻璃化转变温度与结构有关,在相同分子量下,cPG-g-hbPG 的玻璃化转变温度最高,而 hbPG 的玻璃化转变温度最低。这项研究在为先进应用生成具有定制结构和功能的水溶性聚合物方面向前迈进了一步。
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引用次数: 0
α-Trifluoromethylated Quinolines as Safe and Storable PET-Donor for Radical Polymerizations. α-三氟甲基化喹啉作为用于自由基聚合的安全稳定的 PET 给体。
IF 4.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-11-05 DOI: 10.1002/marc.202400710
Arona Fall, Guillaume Tintori, Marion Rollet, Yuxi Zhao, Amandine Avenel, Laurence Charles, David Bergé-Lefranc, Jean Louis Clément, Sébastien Redon, Didier Gigmes, Miquel Huix-Rotllant, Patrice Vanelle, Julie Broggi

In the quest for powerful, safe, and storable photoinduced-electron transfer (PET) donors, the attention is turned to the α-trihalomethylated amine moiety that is not studied in the context of PET-reductants. The thermal and photophysical properties of α-trifluoromethylated quinolines are thus studied and their reducing abilities evaluated as initiators of polymerization reactions. Polymers of high molecular weights are obtained through a radical polymerization process and the PET-donor can be stored within the monomer for several months without losing its efficiency. Mechanistic investigations, combining spectroscopic analysis and theoretical calculations, confirm the mode of activation of these electron donors and the generation of radical intermediates through single electron transfer.

在寻找功能强大、安全和可储存的光诱导电子转移(PET)供体的过程中,人们将注意力转向了 α-三氟甲基化胺分子,而这种分子在 PET 还原剂方面尚未得到研究。因此,我们研究了 α-三氟甲基化喹啉的热和光物理特性,并评估了它们作为聚合反应引发剂的还原能力。通过自由基聚合过程可以获得高分子量的聚合物,PET 供体可以在单体中保存几个月而不会失去其功效。结合光谱分析和理论计算进行的机理研究证实了这些电子供体的活化模式以及通过单电子转移生成自由基中间体的过程。
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引用次数: 0
Surface Engineering of Polymeric Colloidal Crystals by Temperature - Pressure Annealing. 通过温度-压力退火实现聚合物胶体晶体的表面工程。
IF 4.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-11-05 DOI: 10.1002/marc.202400668
Jeena Varghese, Visnja Babacic, Mikolaj Pochylski, Jacek Gapinski, Hans-Juergen Butt, George Fytas, Bartlomiej Graczykowski

Polymer colloidal crystals (PCCs) have been widely explored as acoustic and optical metamaterials and as templates for nanolithography. However, fabrication impurities and fragility of the self-assembled structures are critical bottlenecks for the device's efficiency and applications. We have demonstrated that temperature-assisted pressure [ T , p ] $T,p]$ annealing results in the mechanical strengthening of PCCs, which improves with the annealing temperature. Here, the enhancement of elastic properties and morphological features of self-assembled PCC's is evaluated using Brillouin light scattering and scanning electron microscopy. The pressure-induced effects on the vibrational modes of PCCs are also illustrated at temperatures well below the polymer glass transition. While the PCCs colloid constituents display reversibility, the PCC material is strongly irreversible in the performed thermodynamic cycle. The effective elastic modulus enhances from 0.7 GPa for the pristine sample to 0.8 GPa, solely by pressure annealing at room temperature. [ T , p ] $T,p]$ annealing at higher temperatures leads to a maximum effective elastic modulus of 1.7 GPa, more than twice the value in the pristine sample. Above a cross-over pressure, p c ( ${{p}_{c }}( approx $ 725 bar at 348 K), the PCCs respond elastically and, hence, reversibly to pressure changes.

聚合物胶体晶体(PCCs)作为声学和光学超材料以及纳米光刻的模板已被广泛探索。然而,制造过程中的杂质和自组装结构的脆弱性是影响设备效率和应用的关键瓶颈。我们已经证明,温度辅助压力[ T , p ] $T,p]$退火会导致 PCC 的机械强化,并随着退火温度的升高而改善。在此,我们使用布里渊光散射和扫描电子显微镜评估了自组装 PCC 的弹性特性和形态特征的增强。此外,还说明了在远低于聚合物玻璃化转变温度时压力对 PCC 振动模式的影响。虽然 PCCs 胶体成分显示出可逆性,但在所执行的热力学循环中,PCC 材料具有很强的不可逆性。仅通过室温下的压力退火,有效弹性模量就从原始样品的 0.7 GPa 提高到了 0.8 GPa。[ T , p ] $T,p]$退火温度越高,有效弹性模量最大可达 1.7 GPa,是原始样品的两倍多。在交叉压力 p c ( ≈ ${{p}_{c }}( (大约 725 巴,348 K 时)以上,PCC 会对压力变化做出弹性响应,因此是可逆的。
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引用次数: 0
Uniform Polymer Microspheres by Photoinduced Metal-Free Atom Transfer Radical Precipitation Polymerization. 通过光诱导无金属原子转移自由基沉淀聚合技术制备均匀聚合物微球。
IF 4.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-11-05 DOI: 10.1002/marc.202400502
Tugrul Cem Bicak, Huiyin Liu, Karsten Haupt, Carlo Gonzato, Jérôme Fresnais, Christine Ménager, Louis Fensterbank, Cyril Ollivier, Nébéwia Griffete

Herein, a photoinduced method is introduced for the synthesis of highly cross-linked and uniform polymer microspheres by atom transfer radical polymerization (ATRP) at room temperature and in the absence of stabilizers or surfactants. Uniform particles are obtained at monomer concentrations as high as 10% (by volume), with polymers being exempt from contamination by residual transition metal catalysts, thereby overcoming the two major longstanding problems associated with thermally initiated ATRP-mediated precipitation polymerization. Moreover, the obtained particles have also immobilized ATRP initiators on their surface, which directly enables the controlled growth of densely grafted polymer layers with adjustable thickness and a well-defined chemical composition. The method is then employed successfully for the synthesis of molecularly imprinted polymer microspheres.

本文介绍了一种光诱导方法,用于在室温、无稳定剂或表面活性剂的条件下,通过原子转移自由基聚合(ATRP)合成高度交联和均匀的聚合物微球。在单体浓度高达 10%(体积比)的情况下就能获得均匀的颗粒,聚合物不会受到残留过渡金属催化剂的污染,从而克服了与热引发 ATRP 介导的沉淀聚合相关的两大长期存在的问题。此外,所获得的颗粒表面还固定了 ATRP 起始剂,这就直接实现了厚度可调、化学成分明确的高密度接枝聚合物层的可控生长。该方法随后被成功用于合成分子印迹聚合物微球。
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引用次数: 0
Design of Functional Gyroid Minimal Surfaces Transporting Proton Based Solely on Surface Hopping Conduction Mechanism. 完全基于表面跳频传导机制设计输送质子的功能性陀螺仪最小表面
IF 4.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-11-03 DOI: 10.1002/marc.202400619
Nanami Aoki, Yumin Tang, Xiangbing Zeng, Takahiro Ichikawa

Surface proton hopping conduction (SPHC) mechanisms is an important proton conduction mechanism in conventional polymer electrolytes, along with the Grotthuss and vehicle mechanisms. Due to the small diffusion coefficient of protons in the SPHC mechanism, few studies have focused on the SPHC mechanism. Recently, it has been found that a dense alignment of SO3 - groups significantly lowers the activation energy in the SPHC mechanism, enabling fast proton conduction. In this study, a series of polymerizable amphiphilic-zwitterions is prepared, forming bicontinuous cubic liquid-crystalline assemblies with gyroid symmetry in the presence of suitable amounts of bis(trifluoromethanesulfonyl) imide (HTf2N) and water. In situ polymerization of these compounds yields gyroid-nanostructured polymer films, as confirmed by synchrotron small-angle X-ray scattering experiments. The high proton conductivity of the films on the order of 10-2 S cm-1 at 40 °C and relative humidity of 90% is based solely on the SPHC mechanism.

表面质子跳跃传导(SPHC)机制是传统聚合物电解质中一种重要的质子传导机制,与格罗图斯机制和载流子机制并列。由于 SPHC 机制中质子的扩散系数较小,很少有研究关注 SPHC 机制。最近的研究发现,SO3-基团的密集排列大大降低了 SPHC 机制中的活化能,从而实现了质子的快速传导。在本研究中,制备了一系列可聚合的两亲齐聚物,在适量双(三氟甲烷磺酰)亚胺(HTf2N)和水的存在下,形成了具有陀螺对称性的双连续立方液晶组装体。同步加速器小角 X 射线散射实验证实,这些化合物的原位聚合可产生陀螺状纳米结构聚合物薄膜。在 40 °C 和相对湿度为 90% 的条件下,薄膜具有 10-2 S cm-1 数量级的高质子传导性,这完全是基于 SPHC 机制。
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引用次数: 0
Synthesis and Binding Properties of High-Affinity Histidine-Bearing Polymers for Wood Lignin. 木质素高亲和性组氨酸载体聚合物的合成与结合特性。
IF 4.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-11-03 DOI: 10.1002/marc.202400487
Rika Hinohara, Yuji Aso, Naoko Kobayashi, Kaori Saito, Takashi Watanabe, Tomonari Tanaka

The pursuit of molecules capable of binding to wood lignin is pivotal for advancing lignin degradation technology, particularly when combined with lignin degradation catalysts. In this study, synthetic polymers bearing histidine moieties, demonstrating remarkable affinity for wood lignin are reported. These polymers, featuring varying degrees of histidine substitution in the form of histidine methyl esters, are synthesized through controlled radical polymerization of an activated ester-bearing monomer, employing a fluorescein-labeled chain transfer agent and subsequent postpolymerization amidation with histidine methyl ester. The binding properties of these histidine-bearing polymers with milled wood lignin under aqueous conditions are investigated. Qualitative assessment of lignin-binding capabilities involve spectroscopic analysis of changes in absorbance of visible light and fluorescence intensity. Furthermore, quantitative evaluation is conducted through surface plasmon resonance measurements to determine the binding parameters of the polymers with wood lignin. Notably, polymers with higher histidine substitution exhibit enhanced binding affinity compared to those with lower histidine substitution levels.

寻找能够与木材木质素结合的分子对于推动木质素降解技术的发展至关重要,尤其是在与木质素降解催化剂结合时。本研究报告介绍了含有组氨酸分子的合成聚合物,它们对木材木质素具有显著的亲和力。这些聚合物以组氨酸甲酯的形式存在不同程度的组氨酸取代,是通过活化的含酯单体的受控自由基聚合反应合成的,采用了荧光素标记的链转移剂,随后与组氨酸甲酯进行后聚合酰胺化。研究了这些含组氨酸聚合物在水性条件下与碾磨木质素的结合特性。木质素结合能力的定性评估包括可见光吸光度和荧光强度变化的光谱分析。此外,还通过表面等离子共振测量进行了定量评估,以确定聚合物与木质素的结合参数。值得注意的是,与组氨酸取代度较低的聚合物相比,组氨酸取代度较高的聚合物表现出更强的结合亲和力。
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引用次数: 0
A Review on Advances and Challenges in Core-Shell Scaffolds for Bone Tissue Engineering: Design, Fabrication, and Clinical Translation. 骨组织工程核壳支架的进展与挑战综述:设计、制造和临床转化。
IF 4.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-11-03 DOI: 10.1002/marc.202400620
Bee Chin Ang, Hui Yin Nam, Muhammad Faiq Abdullah, Farina Muhammad, Yen Bach Truong

This review explores core-shell scaffolds in bone tissue engineering, highlighting their osteoconductive and osteoinductive properties critical for bone growth and regeneration. Key design factors include material selection, porosity, mechanical strength, biodegradation kinetics, and bioactivity. Electrospun core-shell nanofibrous scaffolds demonstrate potential in delivering therapeutic agents and enhancing bone regeneration. Critical characterization techniques include structural, surface, chemical composition, mechanical, and degradation analyses. Scaling up production poses challenges, addressed by innovative electrospinning techniques. Future research focuses on regulatory and commercial considerations, while exploring advanced materials and fabrication methods to optimize scaffold performance for improved clinical outcomes.

这篇综述探讨了骨组织工程中的核壳支架,重点介绍了其对骨生长和再生至关重要的骨诱导和骨诱导特性。关键设计因素包括材料选择、孔隙率、机械强度、生物降解动力学和生物活性。电纺核壳纳米纤维支架在递送治疗药物和促进骨再生方面具有潜力。关键的表征技术包括结构、表面、化学成分、机械和降解分析。扩大生产规模带来了挑战,创新的电纺技术解决了这一问题。未来的研究重点是监管和商业方面的考虑,同时探索先进的材料和制造方法,以优化支架性能,改善临床效果。
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引用次数: 0
Linker Group Fluorination Boosts Photovoltaic Performance of Branch-Connected Dimerized Acceptors. 连接基团氟化可提高分支连接二聚受体的光伏性能。
IF 4.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-11-03 DOI: 10.1002/marc.202400687
Yuxin Wang, Xinyuan Jia, Kangqiao Ma, Wenkai Zhao, Huazhe Liang, Zhaoyang Yao, Guankui Long, Chenxi Li, Xiangjian Wan, Yongsheng Chen

Branch-connected dimerized acceptors can take full advantages of four end units in enhancing molecular packing comparing to that of terminal-connected ones, thus potentially reaching the best balance between stability and power conversion efficiency (PCE) of organic solar cells (OSCs). Herein, two branch-connected dimerized acceptors, namely D1 and D2, are developed by employing bithiophene and difluorinated bithiophene as linker groups, respectively. Induced by the fluorine atoms on linker group, D2 affords a larger molar extinction coefficient, more importantly, the optimized nanoscale film morphology and superior charge transport behavior comparing to D1. Consequently, D2-based binary OSCs render a good PCE of 16.66%, outperforming that of 15.08% for D1-based ones. This work highlights the great significance of linker group screening in designing high-performance branch-connected dimerized acceptors.

与末端连接的受体相比,分支连接的二聚受体可以充分利用四个末端单元来增强分子填料,从而有可能在有机太阳能电池(OSC)的稳定性和功率转换效率(PCE)之间达到最佳平衡。在此,通过分别使用双噻吩和二氟化噻吩作为连接基团,开发出了两种分支连接的二聚受体,即 D1 和 D2。在连接基团上的氟原子的诱导下,D2 与 D1 相比具有更大的摩尔消光系数,更重要的是,它具有优化的纳米薄膜形态和更优越的电荷传输行为。因此,基于 D2 的二元 OSC 具有 16.66% 的良好 PCE,优于基于 D1 的 15.08%。这项工作凸显了连接基团筛选在设计高性能分支连接二聚受体中的重要意义。
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引用次数: 0
Precise Control of Molecular Weight Characteristics of Charge-Shifting Poly(2-(N,N-Dimethylamino)Ethylacrylate) Synthesized by Reversible Addition-Fragmentation Chain Transfer Polymerization. 精确控制通过可逆加成-断裂链转移聚合法合成的电荷变换聚(2-(N,N-二甲基氨基)乙基丙烯酸酯)的分子量特性。
IF 4.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-11-03 DOI: 10.1002/marc.202400640
Radoslava Sivkova, Rafal Konefal, Libor Kostka, Richard Laga, Gabriela S García-Briones, Olga Kočková, Ognen Pop-Georgievski, Dana Kubies

Poly(2-(N,N-dimethylamino)ethyl acrylate) (PDMAEA) is a promising charge-shifting polycation with the capacity to form a range of morphologically distinct polyelectrolyte assemblies. Nevertheless, the basic character of the monomer and its hydrolytic instability impedes its controlled synthesis to higher molecular weight (MW). Herein, the reversible addition-fragmentation chain transfer polymerization of DMAEA is reported using a tert-butanol/V70 initiator/trithiocarbonate-based chain transfer agent (CTA) polymerization setup. The CTA instability is demonstrated in the presence of the unprotonated tertiary amino group of the DMAEA monomer, which limits the control over the conversion and MW of the polymer. In contrast, the shielding of the amino groups by their protonation leads to polymerization with high conversions and excellent control over MWs of polymer up to 100 000 g mol-1. Hydrolytic degradation study at pH values ranging from 5 to 9 reveals that both basic and protonated PDMAEA undergo a pH-dependent hydrolysis. The proposed polymerization conditions provide a means of synthesizing PDMAEA with well-controlled characteristics, which are beneficial for controlling the complexation processes during the formation of various polyelectrolyte assemblies.

聚(2-(N,N-二甲基氨基)乙基丙烯酸酯)(PDMAEA)是一种前景广阔的电荷转移多阳离子,能够形成一系列形态各异的聚电解质组合体。然而,该单体的基本特性及其水解不稳定性阻碍了其可控合成至更高分子量(MW)。本文报告了使用叔丁醇/V70引发剂/三硫代碳酸酯为基础的链转移剂(CTA)聚合装置对 DMAEA 进行可逆加成-断裂链转移聚合的情况。CTA 在 DMAEA 单体的未质子化叔氨基存在时表现出不稳定性,这限制了对聚合物转化率和分子量的控制。与此相反,通过质子化屏蔽氨基,聚合反应的转化率很高,对聚合物分子量的控制也很出色,最高可达 100 000 g mol-1。在 pH 值为 5 到 9 的条件下进行的水解降解研究表明,碱性和质子化的 PDMAEA 都会发生随 pH 值变化的水解。所提出的聚合条件为合成具有良好控制特性的 PDMAEA 提供了一种方法,有利于控制各种聚电解质组合物形成过程中的复合过程。
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引用次数: 0
Chemical Vapor Deposition Toward Efficient Bimetallic Atomically Dispersed Oxygen Reduction Catalysts. 化学气相沉积实现高效双金属原子分散氧还原催化剂
IF 4.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-11-01 Epub Date: 2024-08-06 DOI: 10.1002/marc.202400442
Xudong Jia, Bolong Yang, Qian Cheng, Xueli Li, Zhonghua Xiang

Non-precious metal-based nitrogen-doped carbon (M-Nx/C) shows great potential as a substitute for precious metal Pt-based catalysts. However, the conventional pyrolytic methods for forming M-Nx/C active sites are prone to issues such as the lack of synergistic interactions among bimetallic atoms and the potential encasement of active sites, leading to compromised catalytic efficiency and hindered mass transfer. In this work, a highly active FeCo-N-C@U-AC electrocatalyst is developed with a high density of active sites, adequate exposure of catalytic sites, and robust mass transfer capability using the chemical vapor-phase deposition (CVD) technique. The resulting catalyst demonstrates impressive oxygen reduction reaction (ORR) catalytic performance and stability, with half-wave potentials of 0.820 V (0.1 M HClO4) and 0.911 V (0.1 M KOH), respectively. It also exhibits significantly enhanced stability, retaining 93.25% and 98.38% of current after continuous 50 000 s of durability testing, surpassing the retention rates of Pt/C (80.31% in HClO4 and 84.96% in KOH electrolytes). Notably, when employed as a cathode catalyst in proton exchange membrane fuel cells (PEMFCs) and zinc-air flow batteries (ZAFBs), the FeCo-N-C@U-AC catalyst delivers peak power densities of 859 and 162 mW·cm-2, respectively, showcasing competitive performance comparable to benchmark Pt/C.

非贵金属掺氮碳(M-Nx/C)作为贵金属铂催化剂的替代品具有巨大潜力。然而,传统的热解方法在形成 M-Nx/C 活性位点时容易出现一些问题,如双金属原子之间缺乏协同作用以及活性位点可能被包裹,从而导致催化效率降低和传质受阻。在这项研究中,利用化学气相沉积(CVD)技术开发了一种高活性的 FeCo-N-C@U-AC电催化剂,它具有高密度的活性位点、充分的催化位点暴露和强大的传质能力。催化剂的半波电位分别为 0.820 V(0.1 M HClO4)和 0.911 V(0.1 M KOH),氧还原反应(ORR)催化性能和稳定性令人印象深刻。它的稳定性也明显增强,在连续 50 000 秒的耐久性测试后,电流保持率分别为 93.25% 和 98.38%,超过了 Pt/C 的保持率(在 HClO4 电解质中为 80.31%,在 KOH 电解质中为 84.96%)。值得注意的是,在质子交换膜燃料电池(PEMFC)和锌-空气流动电池(ZAFB)中用作阴极催化剂时,FeCo-N-C@U-AC 催化剂的峰值功率密度分别为 859 mW-cm-2 和 162 mW-cm-2,显示出与基准 Pt/C 相媲美的竞争性能。
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引用次数: 0
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Macromolecular Rapid Communications
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