Macromolecular Chemistry and Physics最新文献_第3页

Enantioselective Induction of Helical Chirality in Coil-Structured Amino Acid-Based Polymers by Conjugated Molecules 共轭分子对螺旋手性的对映选择性诱导

IF 2.5 4区化学

Macromolecular Chemistry and Physics Pub Date : 2025-03-29 DOI: 10.1002/macp.202500007

Guoqiang Ji, Huimin Duan, Xinlei Wu, Chengshuo Shen

{"title":"Enantioselective Induction of Helical Chirality in Coil-Structured Amino Acid-Based Polymers by Conjugated Molecules","authors":"Guoqiang Ji, Huimin Duan, Xinlei Wu, Chengshuo Shen","doi":"10.1002/macp.202500007","DOIUrl":"https://doi.org/10.1002/macp.202500007","url":null,"abstract":"Chirality induction in aprotic polar solvents is challenging due to disrupted intermolecular interactions and the high conformational flexibility of random-coil polymers. Herein, a scalable strategy using chiral BINOL as the sole chiral source to induce helical chirality in random-coil polymers is presented. Circular dichroism (CD), ultraviolet-visible (UV– vis), and resonance Raman spectroscopy confirm that chiral BINOL effectively induces cis-transoidal helical conformations through hydrogen bonding and π–π stacking interactions. CD and circularly polarized luminescence (CPL) measurements reveal efficient chirality transfer and amplification, with mirror-image CPL signals observed at 390 nm. Resonance Raman spectra demonstrate enhanced structural order and reduced irregularities, evidenced by a blue shift and narrowed C═C Raman peak, while achiral BINOL exhibits minimal induction ability. This study highlights the mechanisms of chirality induction and CPL excitation in random-coil polymers in aprotic polar solvents, providing a versatile pathway for designing advanced materials with exceptional chiral optical and fluorescence properties.","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 11","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144220377","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Glucan Phosphorylase-Catalyzed Enzymatic Synthesis of a New Unnatural Heteroaminopolysaccharide, Glucosamino-2-deoxyglucan, and Its N-Benzylation for pH Responsive Property 葡聚糖磷酸化酶催化合成一种新的非天然异氨基多糖葡氨基-2-脱氧葡聚糖及其n -苄基化对pH响应特性的影响

IF 2.5 4区化学

Macromolecular Chemistry and Physics Pub Date : 2025-03-29 DOI: 10.1002/macp.202500052

Yuta Miyahara, Tao Takagagki, Masayasu Totani, Jun-ichi Kadokawa

{"title":"Glucan Phosphorylase-Catalyzed Enzymatic Synthesis of a New Unnatural Heteroaminopolysaccharide, Glucosamino-2-deoxyglucan, and Its N-Benzylation for pH Responsive Property","authors":"Yuta Miyahara, Tao Takagagki, Masayasu Totani, Jun-ichi Kadokawa","doi":"10.1002/macp.202500052","DOIUrl":"https://doi.org/10.1002/macp.202500052","url":null,"abstract":"Based on the fact that the enzymatic approach has been identified as a powerful tool to prepare polysaccharides with well-defined structure, this study investigates the enzymatic synthesis of a new unnatural heteroaminopolysaccharide, that is, α(<math>\u0000 <semantics>\u0000 <mrow>\u0000 <mn>1</mn>\u0000 <mo>→</mo>\u0000 </mrow>\u0000 <annotation>$1{to} $4</annotation>\u0000 </semantics></math>)-linked glucosamino-2-deoxyglucan. The desired heteroaminopolysaccharide is obtained by thermostable glucan phosphorylase (from Aquifex aeolicus VF5)-catalyzed enzymatic copolymerization of α-d-glucosamine 1-phosphate/d-glucal as comonomers from maltotriose as a primer in 0.10 m ammonia buffer containing MgCl2 at 40 °C. The MALDI-TOF MS and 1H NMR spectrum of the isolated product fully supported the heteroaminopolysaccharide structure. The effects of comonomer feed ratios and reaction times on unit ratios and degrees of polymerization (molecular weights), respectively, are precisely investigated. As a representative derivatization using reactive amino groups in the produced heteroaminopolysaccharide, its N-benzylation is attempted using benzyl bromide in DMSO. The N-benzylated derivative exhibited pH responsive property, where the polymeric molecules assembled by hydrophobic interaction among benzyl groups under the neutral aqueous condition, whereas the assemblies are dissociated by electrostatic repulsion via protonation on nitrogen atoms under the acidic condition. The result indicates the potential of the present heteroaminopolysaccharide as biomedical materials in the practical application field.","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 11","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/macp.202500052","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144220375","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Artificial Metal-Ion Doped Spider Silk Fibers with Excellent Mechanical Property and Humidity-Driven Actuator Property 具有优异机械性能和湿度驱动致动性能的人造金属离子掺杂蜘蛛丝纤维

IF 2.5 4区化学

Macromolecular Chemistry and Physics Pub Date : 2025-03-29 DOI: 10.1002/macp.202400502

Mengya Chang, Xiaohua Zhang, Zhaohui Yang

引用次数: 0

Influence of Dissolution Temperature and Storage Time on Hydroxyethyl Cellulose Viscosity: Insights Into Molecular Structure Evolution 溶解温度和储存时间对羟乙基纤维素粘度的影响：对分子结构演变的见解

IF 2.5 4区化学

Macromolecular Chemistry and Physics Pub Date : 2025-03-27 DOI: 10.1002/macp.202400495

Jihao Lu, Jiaying Qu, Shiying Luo, Yue Li, Yu Cao

{"title":"Influence of Dissolution Temperature and Storage Time on Hydroxyethyl Cellulose Viscosity: Insights Into Molecular Structure Evolution","authors":"Jihao Lu, Jiaying Qu, Shiying Luo, Yue Li, Yu Cao","doi":"10.1002/macp.202400495","DOIUrl":"https://doi.org/10.1002/macp.202400495","url":null,"abstract":"In this paper, the structures and molar substitutions (MS) of the two HECs are first determined by Fourier Transform Infrared Spectroscopy (FTIR), Nuclear Magnetic Resonance (NMR) dissolution, and Gel Permeation Chromatography (GPC) characterization. By analyzing two HEC variants with differing viscosities across various concentrations, temperatures, and storage durations, this study finds that viscosity is significantly affected by dissolution temperature and storage time, with these effects dependent on the MS degree of HEC. For low MS HEC, the viscosity remains stable at high dissolution temperatures (40–90 °C) in dilute solutions (0.1–1.5% w/v) but decreases in concentrated environments. In contrast, highly viscous HEC (0.1–1.0% w/v) shows minimal viscosity changes in dilute conditions, with reductions occurring in concentrated solutions. Increasing dissolution temperature causes a shift in molecular conformation from a loose random nematic structure to a more compact one, resulting in larger spacing between molecular chains, reduced interaction forces, and lower viscosity. Over time, low MS HEC transitions from a random coil to a compact structure, while high MS HEC maintains its disrupted form. This work enhances the understanding of HEC behavior under varying conditions and provides a theoretical foundation for optimizing its applications in diverse fields.","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 10","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144091870","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Chemical Structure-Dependence of the Thermal Transition in Thermoresponsive Ethylene-Glycol-Containing Polymers as Characterized by EPR Spectroscopy 热响应型含乙二醇聚合物中热转变的化学结构依赖及其EPR光谱表征

IF 2.5 4区化学

Macromolecular Chemistry and Physics Pub Date : 2025-03-27 DOI: 10.1002/macp.202500050

Haleh Hashemi Haeri, Andreas H. Kampe, Zhanna Evgrafova, Johnny A. Siegert, Wolfgang H. Binder, Dariush Hinderberger

{"title":"Chemical Structure-Dependence of the Thermal Transition in Thermoresponsive Ethylene-Glycol-Containing Polymers as Characterized by EPR Spectroscopy","authors":"Haleh Hashemi Haeri, Andreas H. Kampe, Zhanna Evgrafova, Johnny A. Siegert, Wolfgang H. Binder, Dariush Hinderberger","doi":"10.1002/macp.202500050","DOIUrl":"https://doi.org/10.1002/macp.202500050","url":null,"abstract":"Variations in main and side chain lengths, along with the use of end groups of differing natures, are often identified as key parameters influencing phase transition temperatures (cloud point temperatures) in thermoresponsive polymers. Here, the phase transition behavior of thermoresponsive poly(oligo(ethylene glycol)acrylates) is systematically examined with respect to these three factors. Spin-probing electron paramagnetic resonance (EPR) spectroscopy is employed to investigate the impact of these parameters below and at the macroscopically observable thermal transition, as well as to characterize the nanoscale inhomogeneities associated with the transition. Optical transmission measurements are conducted to provide a comprehensive understanding of both, macroscopic and nanoscopic, events. Conducting EPR enables the early detection of the onset of the transition temperature range, well before optical detection. This combined approach enables us to establish the relative significance of these factors in determining the transition temperatures and the collapse processes. With this approach, this study finds that the (de)hydration behavior of the polymer chains is mainly determined by the length of ethylene glycol side chains but the individual single polymer end groups also have remarkable influence on the collapse behavior. The main chain length is identified as, relatively viewed, having the smallest effect on the thermal collapse on the molecular level.","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 10","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/macp.202500050","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144091871","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Acceleration and Amplification of Physical Aging in Thermo-Oxidized Epoxy Networks 热氧化环氧树脂网络中物理老化的加速和放大

IF 2.5 4区化学

Macromolecular Chemistry and Physics Pub Date : 2025-03-27 DOI: 10.1002/macp.202400528

Blandine Quélennec, Romain Delannoy, Nicolas Delpouve, Emmanuel Richaud, Laurent Delbreilh

{"title":"Acceleration and Amplification of Physical Aging in Thermo-Oxidized Epoxy Networks","authors":"Blandine Quélennec, Romain Delannoy, Nicolas Delpouve, Emmanuel Richaud, Laurent Delbreilh","doi":"10.1002/macp.202400528","DOIUrl":"https://doi.org/10.1002/macp.202400528","url":null,"abstract":"The durability of civil engineering constructions is enhanced by protecting the concrete structures with epoxy coatings, which sustainability for decades of service is also conditioned by their aptitude to keep their dimensional stability under physical aging. This phenomenon, involving structural relaxation in the glassy state, is generally slow far from the glass transition, but has long-term consequences that may be detrimental for the macroscopic properties. Based on the premise that the structural relaxation rate is modified by the chemical modifications affecting the molecular mobility, this study investigates the effect of thermo-oxidative degradation on the physical aging kinetics. In a first step, the degradation by chain scission is suggested by results from thermal analyses, evidencing a decrease of the glass transition, an increase of the heat capacity step, and a lower thermal stability. Then, the kinetics of physical aging are compared between neat and thermo-oxidized epoxy networks. Using fast scanning calorimetry (FSC), the structural relaxation is followed for various aging temperatures, showing that physical aging proceeds faster while its intensity is amplified. Eventually, the relaxation functions fitted according to the Tool–Narayanaswamy–Moynihan (TNM) equation reveal lower activation energy in the oxidized networks in consistence with the chain scission scenario.","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 11","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144220242","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Tailoring Piezoresistive Behavior of Compressive Strain Sensors by 3D-Printed Structure and Filler Dispersity 用3d打印结构和填料分散度裁剪压缩应变传感器的压阻性能

IF 2.5 4区化学

Macromolecular Chemistry and Physics Pub Date : 2025-03-27 DOI: 10.1002/macp.202400480

Haidong Yin, Chenyang Zhang, Yu Liu, Fengmei Yu, Ai Lu, Chengzhen Geng

{"title":"Tailoring Piezoresistive Behavior of Compressive Strain Sensors by 3D-Printed Structure and Filler Dispersity","authors":"Haidong Yin, Chenyang Zhang, Yu Liu, Fengmei Yu, Ai Lu, Chengzhen Geng","doi":"10.1002/macp.202400480","DOIUrl":"https://doi.org/10.1002/macp.202400480","url":null,"abstract":"Flexible strain sensors are in high demand for wearable devices and smart healthcare applications. However, compressive strain sensors receive less attention than stretchable counterparts due to their limited sensitivity under compression. Emerging 3D printing technology enables precise control over cellular structures, offering a promising approach to enhance their sensing performance. This study investigates the effects of carbon nanotube (CNT) content, dispersion, and printed structural parameters on 3D-printed polydimethylsiloxane (PDMS)/CNT compressive sensors. Sensors fabricated with 3 wt% CNT ink, prepared via two-roll milling, exhibit a positive resistance change rate under compression, improving sensitivity. The resistance change rate further increases as the printed line spacing decreases and the number of layers increases. Significant variations in sensing behavior, such as resistance increase or decrease under strain, are observed and explained through a unified structural change model. The cyclability of sensors exhibiting different resistance responses is compared, demonstrating the reliability of the optimized sensors for human motion monitoring and spatial force detection. This work deepens the understanding of the piezoresistive behavior of 3D-printed compressive sensors and provides valuable guidance for their design, fabrication, and application.","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 10","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144091869","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Hybrid Polymers Bearing Mono/Oligo-L-Lysine(Z)s: ADMET Polymerization and Structural Investigations in the Solid State 含单/低聚l -赖氨酸的杂化聚合物：ADMET聚合和固态结构研究

IF 2.5 4区化学

Macromolecular Chemistry and Physics Pub Date : 2025-03-27 DOI: 10.1002/macp.202400510

Merve Basak Canalp, Wolfgang H. Binder

{"title":"Hybrid Polymers Bearing Mono/Oligo-L-Lysine(Z)s: ADMET Polymerization and Structural Investigations in the Solid State","authors":"Merve Basak Canalp, Wolfgang H. Binder","doi":"10.1002/macp.202400510","DOIUrl":"https://doi.org/10.1002/macp.202400510","url":null,"abstract":"Advancing novel polymers for biomedical applications requires in-depth knowledge between their chemical structure and physical properties under conditions such as assembly or folding. The secondary structure of hybrid-polymers containing lysine-residues (Lys) inside their main chain, separated by a stretch of n-alkyl-chains is here investigated. The polymer (A-[Lysn = 1]m = 18) is prepared by ADMET polymerization of the bis-ω-ene-functional mono-L-lysine(Z)s (Lysn = 1) optimizing conditions for ADMET polymerization of Lysn = 1 monomers in bulk. The hybrid-polymers, A-[Lysn = 1]m = 3, 7, 9, 18, 44 with molecular weights ranging from 1.3 to 17.6 kDa, display polydispersity (Đ) values in the range of 1.3–2.6. Comparison between these polymers and previously reported hybrid ADMET polymer, oligo-L-lysine(carboxybenzyl(Z)), (A-[Lysn]m) (i.e., n = 4, m = 24), containing longer stretches of the embedded lysine-unit was accomplished. Solid-state investigations (FT-IR and DSC) of the hybrid-polymers, A-[Lysn = 1]m = 18, A-[Lysn = 12]m = 8, and A-[Lysn = 24]m = 4, and the pre-polymers, Lysn = 12 and Lysn = 24 proved the presence of α-helices and β-folds at elevated temperatures in the range of 20 to 200 °C, further gaining understanding of the influence of the chain length of polymers on the formation of secondary structures.","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 11","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/macp.202400510","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144220243","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Thermo-Mechanical Processing of Chitosan Using Cyclic Carbonates as Green Plasticizers 环状碳酸盐绿色增塑剂在壳聚糖热机械加工中的应用

IF 2.5 4区化学

Macromolecular Chemistry and Physics Pub Date : 2025-03-26 DOI: 10.1002/macp.202500072

Sukanya Satapathy, Aruna Palanisamy, Kavya Lekha Sunkara, Sunil Misra, Ramanuj Narayan

引用次数: 0

Designing Nanofibrillar Macroporous Hydrogels via Aqueous Foam Templating 用泡沫水模板法设计纳米纤维大孔水凝胶

IF 2.5 4区化学

Macromolecular Chemistry and Physics Pub Date : 2025-03-26 DOI: 10.1002/macp.202400492

Shunpu Yang, Wenzhi Bi, Huan Yu, Huaiming Wang, Ketong Wu, Yunhua Chen

{"title":"Designing Nanofibrillar Macroporous Hydrogels via Aqueous Foam Templating","authors":"Shunpu Yang, Wenzhi Bi, Huan Yu, Huaiming Wang, Ketong Wu, Yunhua Chen","doi":"10.1002/macp.202400492","DOIUrl":"https://doi.org/10.1002/macp.202400492","url":null,"abstract":"The emulsion templating method is a versatile approach for fabricating macroporous hydrogels, appreciated for its simplicity, high porosity, and the formation of interconnected pores. However, traditional templates using liquid phases as the dispersed medium often suffer from challenges like organic solvent residues, limiting their applicability in biomaterials. To address these limitations, air-in-water foams have emerged as a promising alternative but are constrained by the high surface tension of prepolymer solutions, which hampers the formation of stable templates. In this study, tannic acid (TA)-modified lysozyme amyloid nanofibrils (TA@AF) were integrated with gelatin methacrylate (GelMA) and methacryloylethylsulfobetaine (SBMA) monomers to stabilize air-in-water foams and fabricate nanofibrillar macroporous hydrogels (NMH) via free radical polymerization. The TA@AF nanofibrils played a dual role in controlling air bubbles and pore sizes and reinforcing the mechanical properties of the hydrogels. The resulting NMH hydrogels demonstrated excellent antioxidant and hemostatic capabilities while preventing protein adhesion. These attributes highlight the potential of air-in-water foam-templated nanofibrillar macroporous hydrogels as innovative materials for biomedical applications.","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 10","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144091663","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0