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Recent advances in chemoenzymatic synthesis of oligosaccharides and polysaccharides 化学酶法合成低聚糖和多糖的研究进展
IF 3.9 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2025-11-14 DOI: 10.1039/D5PY00938C
Tomonari Tanaka

Chemoenzymatic methods are essential tools for synthesising a wide range of saccharides and their derivatives, including oligosaccharides, polysaccharides, and glycoconjugates, in the fields of glycotechnology and polymer chemistry. This review summarises recent progress and provides an overview of research on chemoenzymatic synthesis of oligosaccharides and polysaccharides through the combined use of chemical and enzymatic reactions. The methodologies are discussed separately for each class of enzyme: glycosyltransferases, glycan phosphorylases, and glycosyl hydrolases.

在糖技术和聚合物化学领域,化学酶方法是合成各种糖及其衍生物的基本工具,包括低聚糖、多糖和糖缀合物。本文综述了近年来化学酶法合成低聚糖和多糖的研究进展,并对化学酶法合成低聚糖和多糖的研究进展进行了综述。方法分别讨论了每一类酶:糖基转移酶,聚糖磷酸化酶和糖基水解酶。
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引用次数: 0
Unravelling the mechanisms of nanomedicines: analytical tools to characterise the interaction between synthetic macromolecules and lipid membranes 揭示纳米药物的机制:表征合成大分子和脂质膜之间相互作用的分析工具
IF 3.9 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2025-11-13 DOI: 10.1039/D5PY00850F
Ayomi Vidana Pathiranage, Mark-Jefferson Buer Boyetey, Oluwatoosin B. A. Agbaje and Nathan R. B. Boase

Polymer nanomedicines are a transformative class of therapeutics, offering tunable architectures for targeted delivery, controlled release, and improved pharmacokinetics. However, limited understanding of how these systems interact with cellular membranes, undergo internalization, and release their cargo continues to hinder their clinical translation. Membrane interactions are a key determinant of these processes yet remain underexplored in nanomedicine research. This review provides an overview of analytical techniques used to study the interaction of polymers with lipid membranes, drawing on methods from biophysics, physical chemistry, and colloid science. We introduce common model membrane systems and explain how they can complement in vitro studies. A wide range of characterization approaches are discussed, from microscopy and spectroscopy to more advanced scattering and nanomechanical techniques. By illustrating how these methods can be integrated to build a complete mechanistic understanding of dynamic interfacial behaviour, this review aims to bridge disciplinary gaps and support the development of more effective nanomedicines.

聚合物纳米药物是一种变革性的治疗药物,为靶向递送、控制释放和改善药代动力学提供了可调的结构。然而,对这些系统如何与细胞膜相互作用、经历内化和释放其货物的了解有限,继续阻碍了它们的临床转化。膜相互作用是这些过程的关键决定因素,但在纳米医学研究中仍未得到充分探索。这篇综述提供了用于研究聚合物与脂质膜相互作用的分析技术的概述,从生物物理学、物理化学和胶体科学中汲取方法。我们介绍了常见的模型膜系统,并解释了它们如何补充体外研究。广泛的表征方法进行了讨论,从显微镜和光谱学更先进的散射和纳米机械技术。通过说明如何整合这些方法来建立对动态界面行为的完整机制理解,本综述旨在弥合学科差距并支持更有效的纳米药物的开发。
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引用次数: 0
Structural dependence of the solution behavior of HPMA-based polymers hpma基聚合物溶液行为的结构依赖性
IF 3.9 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2025-11-10 DOI: 10.1039/d5py01007a
Lenka Kotrchová , Martina Nevoralová , Michaela Hrochová , Zdeněk Starý , Tomáš Etrych , Libor Kostka
Water-soluble polymers are extensively studied materials in the field of biomedical chemistry research. This study investigates the behavior of methacrylamide-based homopolymers and copolymers with linear, two-arm, and star-like structures in aqueous solutions. The research focuses on how the polymer structure affects its solution behavior. The study uses intrinsic and shear viscosity measurements to examine the influence of these structures on solution behavior at both molecular and macroscopic levels.
水溶性高分子是生物医学化学研究领域中被广泛研究的材料。本研究探讨了甲基丙烯酰胺基均聚物和具有线性、双臂和星形结构的共聚物在水溶液中的行为。研究的重点是聚合物结构如何影响其溶液行为。该研究使用固有粘度和剪切粘度测量来检查这些结构在分子和宏观水平上对溶液行为的影响。
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引用次数: 0
Expanding the polymerization potential of itaconic acid through methacrylate functionalization 通过甲基丙烯酸酯功能化扩大衣康酸的聚合潜力
IF 3.9 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2025-11-10 DOI: 10.1039/d5py00911a
Mary Hnatyshyn , Matthew Halloran , Maxwell Laykish , Jim A. Nicell , Richard L. Leask , Milan Maric
Itaconic acid (IA) is a bio-renewable molecule with increasing industrial availability. However, IA-based polymers have been limited by low molecular weights and conversions. In this work, we report the synthesis of two novel methacrylate-functionalized IA monomers. Using various reversible-deactivation radical polymerization methods, we achieved well-defined polymers with high conversions (≥98%) and moderate reaction times (e.g., 70 minutes by atom transfer radical polymerization at 80 °C). Homopolymers of these two monomers exhibited a range of properties, with glass transition temperatures (Tg) ranging from −40 °C for heptyl-functionalized moieties to 14 °C for benzyl-functionalized moieties. Controllable reaction kinetics enabled the synthesis of pre-designed AB-type diblock copolymers, demonstrating the potential of the heptyl-functionalized moiety as a soft block in phase-separated materials. The favorable reaction kinetics of these methacrylate-functionalized IA monomers make this approach one of the most promising pathways for incorporating renewably sourced IA into polymeric materials.
衣康酸(Itaconic acid, IA)是一种生物可再生分子,工业利用率越来越高。然而,基于ia的聚合物受到低分子量和转化率的限制。在这项工作中,我们报道了两种新型甲基丙烯酸酯功能化IA单体的合成。使用各种可逆失活自由基聚合方法,我们获得了具有高转化率(≥98%)和中等反应时间(例如,在80°C下原子转移自由基聚合70分钟)的定义良好的聚合物。这两种单体的均聚物表现出一系列的性质,庚基功能化部分的玻璃化转变温度(Tg)从-40°C到苯功能化部分的14°C不等。可控的反应动力学使得预先设计的ab型二嵌段共聚物得以合成,证明了庚基功能化部分在相分离材料中作为软嵌段的潜力。这些甲基丙烯酸酯功能化的IA单体的良好反应动力学使这种方法成为将可再生IA纳入聚合物材料的最有前途的途径之一。
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引用次数: 0
Correlating chlorinated polyethylene molecular structure to compatibilization efficiency for mixed polymer waste 氯化聚乙烯分子结构与混合聚合物废物增容效率的关系
IF 3.9 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2025-11-10 DOI: 10.1039/d5py00719d
Christine W. Barker , Bailey Eberle , Mark D. Dadmun , Brian K. Long
There is growing interest in the management of end-of-life plastic waste due to the lack of recycling of these materials into valuable products. This is due, in part, to the challenge of waste plastics collection, sorting, and limitations arising from the immiscibility of reprocessed plastic blends. Mixtures of these immiscible polymer components have poor properties due to weak interfaces, driven by phase separation. To address this, compatibilizers are often used to strengthen the interface between phases and stabilize the blend morphology. Previous research by our group has examined the ability of chlorinated polyethylene (c-PE) to compatibilize polyvinyl chloride (PVC) and polyolefin elastomers (POE). However, the specific molecular level processes that improve the interface of these amorphous–semicrystalline materials are not fully understood. To address this knowledge gap, a series of gradient c-PE copolymers were synthesized via ring-opening metathesis polymerization (ROMP) with varying ratios of dichlorinated cyclooctene and cyclooctene monomers. The ability of these polymers, with molar masses ranging from ∼25–150 kg mol−1, to strengthen the PVC/POE interface were compared to that of commercial blocky c-PEs. The results of this study elucidate the role of crystallinity and molecular sequence distribution of the compatibilizer on its efficacy as a compatibilizer. Herein, we show that the blockiest and most crystalline commercial samples exhibit the greatest improvement in interfacial adhesion whereas the synthesized gradient copolymer compatibilizers increase interfacial adhesion as a function of increasing PE-like segment block length. This indicates that while co-crystallization between semicrystalline components is important in compatibilization, entanglement between polymer phases is also necessary and may be notably impacted by the comonomer sequence distribution along the compatibilizer backbone. These studies provide insight into the molecular design and crucial molecular-level processes that drive the development of morphology and properties of compatibilized phase-separated amorphous–semicrystalline polymer blends, including those that are most relevant for mixed waste streams in polymer recycling.
由于缺乏回收利用这些材料制成有价值的产品,人们对报废塑料废物的管理越来越感兴趣。这在一定程度上是由于废塑料收集、分类的挑战,以及再加工塑料混合物的不混溶性所带来的限制。这些不相混的聚合物组分的混合物由于相分离驱动的弱界面而具有较差的性能。为了解决这个问题,通常使用相容剂来加强相之间的界面并稳定共混物的形态。我们小组之前的研究已经检测了氯化聚乙烯(c-PE)与聚氯乙烯(PVC)和聚烯烃弹性体(POE)的相容能力。然而,改善这些非晶半晶材料界面的具体分子水平过程尚不完全清楚。为了解决这一知识空白,通过开环复分解聚合(ROMP),用不同比例的二氯环烯和环烯单体合成了一系列梯度c-PE共聚物。摩尔质量在~25 ~ 150 kg/mol之间的聚合物增强PVC/POE界面的能力与商用块状c-PEs进行了比较。本研究结果阐明了增容剂的结晶度和分子序列分布对增容效果的影响。在此,我们表明,最块状和最结晶的商业样品在界面附着力方面表现出最大的改善,而合成的梯度共聚物相容剂增加了界面附着力,作为增加pe类段嵌段长度的函数。这表明,虽然半晶组分之间的共结晶在增容作用中很重要,但聚合物相之间的纠缠也是必要的,并且可能受到增容剂主链上共单体序列分布的显著影响。这些研究提供了对分子设计和关键分子水平过程的见解,这些过程推动了相容相分离非晶半晶聚合物共混物的形态和性能的发展,包括那些与聚合物回收中混合废物流最相关的研究。
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引用次数: 0
Emission-tunable aggregation-induced emission thermoplastics via ketyl-mediated polymerization-induced emission 通过基基介导聚合诱导发射的可调聚集体诱导发射热塑性塑料
IF 3.9 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2025-11-10 DOI: 10.1039/d5py00814j
Xiang Wu , Xin-Hui Wang , Chen-Xi Chen , Yu-Jiao Chen , Song-Wei Yang , Hai Nan , Xiao-Li Sun , Li-Ren Xiao , Wen-Ming Wan
Thermoplastics are an important class of polymer materials and dominantly used in industries because of their versatility, remoldability, cost performance, etc.; however, they are mainly used as matrices and lack functionalities, e.g., luminescence. Herein, a ketyl-mediated polymerization-induced emission (KMPIE) strategy is demonstrated to achieve emission-tunable aggregation-induced emission (AIE) thermoplastics, including a general thermoplastic (polystyrene as an example) and a degradable thermoplastic (polycaprolactone as an example). Through KMPIE of styrene and caprolactone in the presence of different enone initiators, polystyrene and polycaprolactone with different end groups were prepared with emission-tunable AIE properties from blue to green. Investigations revealed that a single-fluorophore end group can trigger different nontraditional intrinsic luminescence (NTIL) in AIE polystyrene and polycaprolactone with quantum yields of up to >20%. Investigations into further applications in explosive detection at ppm levels in solution and ng levels on test paper and in enhancement of luminescence in films were carried out. Chemical degradation of the prepared thermoplastics was investigated as well. This work therefore expands the functionality library of general and degradable thermoplastics with AIE-type NTIL properties and may inspire developments in luminescent materials, polymer chemistry, NTIL, AIE and PIE.
热塑性塑料是一类重要的高分子材料,以其通用性、可重塑性、性价比等优势在工业中占据主导地位,但主要用作基体,缺乏发光等功能。本文展示了一种由基基介导的聚合诱导发射(KMPIE)策略,以实现可调节排放的聚集诱导发射(AIE)热塑性塑料,包括一般热塑性塑料(以聚苯乙烯为例)和可降解热塑性塑料(以聚己内酯为例)。通过在不同烯酮引发剂存在下对苯乙烯和己内酯进行KMPIE反应,制备了具有不同端基的聚苯乙烯和聚己内酯,其AIE性能从蓝色到绿色可调。研究表明,单荧光团端基可以触发AIE聚苯乙烯和聚己内酯的不同的非传统本征发光(NTIL),量子产率高达20%。进一步应用于ppm级溶液和ng级试纸及增强发光膜的爆炸检测。对制备的热塑性塑料的化学降解进行了研究。因此,这项工作扩展了具有AIE型NTIL特性的通用和可降解热塑性塑料的功能库,并可能对发光材料、聚合物化学、NTIL、AIE和PIE产生启发。
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引用次数: 0
Preparation and performance evaluation of rare earth metal Eu(iii)-mediated docosahexaenoic acid-imprinted microspheres 稀土金属Eu(III)介导的二十二碳六烯酸印迹微球的制备及性能评价
IF 3.9 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2025-11-10 DOI: 10.1039/d5py00738k
Zehui Wei , Shuangxian Yan , Jilei Yin , Yu Cheng , Shuxian Ge , Yukai He , Weiling Wang , Mei Tian
Docosahexaenoic acid (DHA), widely found in marine organisms, is subject to continuously growing demand in the fields of pharmaceuticals, infant nutrition, and biomaterials. However, due to the low content of DHA in biological samples and the complexity of the matrices, a complicated extraction process is required to obtain a high-purity product. In this experiment, an imprinted polymer microsphere with specific selectivity for DHA was successfully synthesized using a rare earth metal ion-mediated strategy with europium(iii) acetate hydrate (Eu(CH3COO)3·4H2O) as the mediator, DHA as the template molecule, and methacrylic acid (MAA) as the functional monomer. The imprinted polymer microsphere was used for the enrichment and purification of DHA from Antarctic krill meal (AKM). Through systematic optimization of key synthesis parameters, including mediating ion species and concentration, functional monomer content, etc., the adsorption capacity of the developed molecular-imprinted polymers (MIPs) has been enhanced to 0.054 g g−1, with an imprinting factor reaching 4.203. Physical characterization methods, such as scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy, were used to confirm the successful preparation of the porous imprinted microspheres. The solid phase extraction of AKM under the optimal adsorption conditions yielded DHA with 62.18% purity, while the total purity of DHA + EPA could reach 95.98%, which was a 2.4-fold increase in purity, and the recoveries of MIPs ranged from 86.58% to 93.35% (RSD = 3.19%). The linear range of the method was 58.77–100 000 μg mL−1, the limit of detection was 19.40 μg mL−1, and the limit of quantification was 58.77 μg mL−1. In summary, the imprinted microspheres prepared in this experiment demonstrate the selective enrichment and purification of DHA from AKM, offering a novel extraction method for isolating DHA.
二十二碳六烯酸(二十二碳六烯酸,DHA)广泛存在于海洋生物中,在医药、婴儿营养和生物材料等领域的需求不断增长。然而,由于生物样品中DHA含量较低,且基质复杂,需要复杂的提取工艺才能获得高纯度的产品。本实验以铕(III)醋酸水合物(Eu(CH3COO)3·4H2O)为介质,DHA为模板分子,甲基丙烯酸(MAA)为功能单体,采用稀土金属离子介导策略,成功合成了对DHA具有特异性选择性的印迹聚合物微球。采用印迹聚合物微球富集纯化南极磷虾粕(AKM)中的DHA。通过对中介离子种类和浓度、功能单体含量等关键合成参数的系统优化,制备的分子印迹聚合物(MIPs)的吸附容量提高到0.054 g g−1,印迹因子达到4.203。利用扫描电镜、傅里叶变换红外光谱、x射线光电子能谱等物理表征方法证实了多孔印迹微球的成功制备。在最佳吸附条件下,AKM的固相萃取得到的DHA纯度为62.18%,DHA + EPA的总纯度可达95.98%,纯度提高了2.4倍,MIPs的回收率为86.58% ~ 93.35% (RSD = 3.19%)。方法线性范围为58.77 ~ 10万μ mL−1,检出限为19.40 μ mL−1,定量限为58.77 μ mL−1。综上所述,本实验制备的印迹微球证明了从AKM中选择性富集和纯化DHA,为分离DHA提供了一种新的提取方法。
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引用次数: 0
Sub-Tg self-healing in glassy hyperbranched polyurethanes governed by mobile peripheral sub-segment units 由移动外围子段单元控制的玻璃化超支化聚氨酯的亚tg自修复
IF 3.9 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2025-11-10 DOI: 10.1039/d5py00821b
Lang Shuai , Guangwei Xu , Jianglong Li , Jianlong Wen , Boyu Ding , Shui Yu , Yingying Xu , Yijing Nie
To address environmental challenges and advance sustainable development, it has become imperative to develop engineering glassy polymers with autonomous and room-temperature self-healing capability. Although several strategies for achieving self-healing in glassy polymers have been reported, the underlying mechanism dominating the self-healing process below glass transition temperature (Tg) remains elusive. Herein, we synthesized hyperbranched polyurethanes (HPUs) to leverage their abundant hydroxyl end groups for constructing a dense hydrogen-bonding network. The HPUs exhibit a good self-healing ability below Tg (the self-healing efficiency can reach ∼50% and ∼90% after 0.5 h and 48 h of self-healing, respectively). Both experimental and simulation results revealed that a large number of end groups and branching units in the HPUs undergo secondary relaxation and can move locally at temperatures below Tg, which is beneficial for sub-Tg self-healing. In addition, the HPUs containing lower hydrogen bond contents exhibit stronger sub-segment mobility and higher self-healing efficiency, indicating that the mobility of sub-segmental units plays a more important role in promoting the self-healing of glassy hyperbranched polymers rather than the recombination of hydrogen bond content.
为了应对环境挑战,促进可持续发展,开发具有自主和室温自愈能力的工程玻璃聚合物已成为当务之急。虽然已经报道了几种在玻璃化聚合物中实现自愈的策略,但在玻璃化转变温度(Tg)下主导自愈过程的潜在机制仍然难以捉摸。在此,我们合成了超支化聚氨酯(hpu),利用其丰富的羟基端基来构建致密的氢键网络。hpu在Tg以下表现出良好的自愈能力(自愈0.5 h和48 h后的自愈率分别可达50%和90%)。实验和模拟结果表明,hpu中大量的端基和分支单元发生二次弛豫,并在低于Tg的温度下局部移动,这有利于亚Tg的自修复。此外,氢键含量较低的hpu表现出更强的亚段迁移率和更高的自愈效率,表明亚段迁移率对玻璃化超支化聚合物的自愈起着更重要的作用,而不是氢键含量的重组。
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引用次数: 0
Synthesis of sterically unhindered Lewis acidic boron-doped π-conjugated polymers 无位阻路易斯酸性硼掺杂π共轭聚合物的合成
IF 3.9 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2025-11-06 DOI: 10.1039/d5py00783f
Naoki Takahashi , Yuta Nishina
We report the synthesis of sterically unhindered boron-doped π-conjugated polymers via polymerization of organo-dilithium reagents with boron trichloride. The resulting polymer exhibits Lewis acidity and catalyzes the transesterification of methyl benzoate. This performance is attributed to the electron-accepting ability, and thermally labile Lewis acid–base interactions, facilitating catalytic turnover.
本文报道了有机二锂试剂与三氯化硼聚合合成无位阻掺杂硼π共轭聚合物。所得聚合物表现出路易斯酸并催化酯交换反应。密度泛函理论计算表明,该聚合物采用平面构象,允许适度的刘易斯酸碱相互作用,并促进热处理下吡啶的释放。
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引用次数: 0
Ureate anion-catalyzed ring-opening polymerization (ROP) of CO2-derived lactones: rapid catalysis through pKa matching 尿素阴离子催化CO2衍生内酯开环聚合(ROP):通过pK a匹配的快速催化
IF 3.9 2区 化学 Q2 POLYMER SCIENCE Pub Date : 2025-11-06 DOI: 10.1039/d5py00950b
Madhur M. Bhatt , Arron C. Deacy , Ian A. Tonks
The kinetics of ureate anion-catalyzed ring-opening polymerization (ROP) of 3,6-diethyltetrahydro-2H-pyran-2-one () and 3-ethyl-6-vinyltetrahydro-2H-pyran-2-one (), CO2-derived lactones, is reported. Polymerization rates were significantly enhanced by matching the pKa of a particular urea and the pKa-H of the base, with stronger bases and more weakly acidic ureas leading to universally fast catalysis—reducing reaction times from earlier-reported days to minutes/seconds. In parallel, 2-ethylheptanoic acid (), a byproduct from monomer synthesis, was discovered to completely suppress polymerization, even in trace amounts. This highlights the need for rigorous purification protocols to ensure high monomer purity. These results demonstrate the dual importance of chemical purity and rational catalyst design for achieving rapid ROP of CO2-derived and offer a framework for advancing sustainable polymer synthesis.
报道了脲酸盐阴离子催化3,6-二乙基四氢- 2h -吡喃-2-酮(DEtP)和3-乙基-6-乙烯基四氢- 2h -吡喃-2-酮(EtVP)的开环聚合动力学。通过匹配特定尿素的pK - h和碱的pKa-H,聚合速度显著提高,碱性强,酸性弱的尿素导致普遍最快的催化还原反应时间从先前报道的几天缩短到几分钟/秒。与此同时,DEtP单体合成的副产物2-乙基庚酸(EHA)被发现可以完全抑制聚合,即使是微量的。这突出了需要严格的纯化方案,以确保高单体纯度。这些结果表明,化学纯度和合理的催化剂设计对于实现二氧化碳衍生DEtP的快速ROP具有双重重要性,并为推进可持续聚合物合成提供了框架。
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引用次数: 0
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Polymer Chemistry
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