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Phase diagram for the gelation of temperature-responsive and biocompatible poly(oligo ethylene glycol methyl ether methacrylate) polymers in aqueous free-radical polymerization reactions 水基自由基聚合反应中温度响应型生物兼容聚(低聚乙二醇甲醚甲基丙烯酸酯)聚合物凝胶化的相图
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2024-06-18 DOI: 10.1038/s41428-024-00929-2
Takuma Kureha, Takuto Hirayama, Taichi Nishi

In this study, gel-phase diagrams of temperature-responsive and biocompatible polymers were obtained, and the characteristic gelation behaviors of the polymers were examined. The polymers are based on three oligoethylene glycol methyl ether methacrylate (OEGMA) monomers with different numbers of ethylene oxide (EO) units, i.e., with side chains that differ in length. The gelation thresholds depend on the OEGMA and crosslinker concentrations as well as the side chain length. Long EO side chains fill the polymerization system and reduce the concentration of polymer overlap, resulting in a high ability to occupy the system. Furthermore, the EO side chains may engage in self-crosslinking, i.e., polymers can branch and grow from the side chains depending on their length, resulting in a high bond probability. Based on these unique behavior patterns, gelation occurs more readily as the length of the side chains increases. We also synthesized ultralow crosslinked pOEGMA gels by tuning the gelation conditions; these gels exhibited improved swelling capacity and temperature responsiveness. These results should facilitate the development of a synthesis strategy to control the physical properties and structures of these materials for advanced applications, such as biofilms, actuators, and carriers.

本研究获得了具有温度响应性和生物相容性的聚合物的凝胶相图,并研究了这些聚合物的凝胶化特性。这些聚合物基于三种具有不同环氧乙烷(EO)单元数(即侧链长度不同)的低聚乙二醇甲醚甲基丙烯酸酯(OEGMA)单体。凝胶化阈值取决于 OEGMA 和交联剂的浓度以及侧链的长度。长的 EO 侧链可填充聚合体系,降低聚合物重叠的浓度,从而提高占据体系的能力。此外,环氧乙烷侧链可能会发生自交联,即聚合物会根据侧链的长度发生分支和生长,从而产生较高的键合概率。基于这些独特的行为模式,随着侧链长度的增加,凝胶化更容易发生。我们还通过调整凝胶化条件合成了超低交联 pOEGMA 凝胶;这些凝胶显示出更强的溶胀能力和温度响应性。这些结果将有助于开发一种合成策略,以控制这些材料的物理性质和结构,从而应用于生物膜、致动器和载体等先进领域。
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引用次数: 0
Carbon nanotubes functionalized with α-aminoisobutyric acid-containing peptide increase gene delivery efficiency in plant mitochondria 含有α-氨基异丁酸肽的功能化碳纳米管提高了植物线粒体中的基因传递效率
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2024-06-14 DOI: 10.1038/s41428-024-00927-4
Simon Sau Yin Law, Mako Kuzumoto, Seiya Fujita, T. Fujigaya, Keiji Numata
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引用次数: 0
Optimizing crystal transitions in low-temperature, low-concentration NaOH solutions to prepare cellulose I and II composite materials 优化低温、低浓度 NaOH 溶液中的晶体转变,制备纤维素 I 和 II 复合材料
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2024-06-12 DOI: 10.1038/s41428-024-00928-3
Yukio Kugo, Takuya Isono, Masashi Fujiwara, Toshifumi Sato, Hirofumi Tani, T. Erata, K. Tajima
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引用次数: 0
Supramolecular methodologies for the assembly of optical microresonators from functional organic materials 用功能有机材料组装光学微谐振器的超分子方法学
IF 2.8 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2024-06-12 DOI: 10.1038/s41428-024-00925-6
Hiroshi Yamagishi
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引用次数: 0
Development of Pd-immobilized porous polymer catalysts via Bayesian optimization 通过贝叶斯优化技术开发钯固定多孔聚合物催化剂
IF 2.3 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2024-06-06 DOI: 10.1038/s41428-024-00923-8
Xincheng Zhou, Hikaru Matsumoto, Masanori Nagao, Shuji Hironaka, Yoshiko Miura
In this study, a Pd-polymeric porous immobilized catalyst is prepared for the Suzuki–Miyaura coupling reactions by employing a Bayesian optimization method to optimize the catalyst. This research represents the first endeavor to utilize machine learning for the optimization of polymer-immobilized catalysts and provides a novel perspective on utilizing machine learning for the optimization of complex materials. This study presented the workflow of machine learning-guided optimization of Pd-immobilized porous polymer catalysts. Two independent variables (DVB and 1-decanol content) were involved in polymerization to maximize TOF as target variable in Suzuki–Miyaura coupling reaction. Bayesian optimization was applied for predictive modeling, and the optimized conditions were experimentally validated in subsequent iterations. By applying this workflow, the catalytic activity of immobilized polymer porous catalysts was successfully optimized using machine learning.
本研究采用贝叶斯优化方法制备了一种钯聚合物多孔固定化催化剂,用于Suzuki-Miyaura偶联反应。该研究首次尝试利用机器学习优化聚合物固定化催化剂,为利用机器学习优化复杂材料提供了新的视角。本研究介绍了机器学习指导下的多孔聚合物钯固定化催化剂优化工作流程。聚合反应涉及两个自变量(DVB 和 1-癸醇含量),以最大化 TOF 作为铃木-宫浦偶联反应的目标变量。贝叶斯优化法用于预测建模,优化条件在随后的迭代中得到了实验验证。通过应用这一工作流程,利用机器学习成功优化了固定化聚合物多孔催化剂的催化活性。
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引用次数: 0
Polymer replica of microcrystalline surface with dual wettability, mimicking a termite wing 具有双重润湿性的微晶表面聚合物复制品,模仿白蚁翅膀
IF 2.3 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2024-06-06 DOI: 10.1038/s41428-024-00926-5
Yuki Hashimoto, Amane Hase, Ayumu Tani, Ryo Nishimura, Yohei Hattori, Hiroyuki Mayama, Satoshi Yokojima, Shinichiro Nakamura, Kingo Uchida
Termite wings are covered with hair shafts and micrasters, which provide it with dual wettability. Although the surface is superhydrophobic for bulk water and large droplets, it is adhesive for microdroplets of water. We mimicked this rough surface by applying a photoinduced crystal growth phenomenon on a photoreactive crystalline surface consisting of two photochromic diarylethene derivatives. This crystalline surface showed dual wettability, but the photoreactive crystalline system was not applicable under daylight. This lack of applicability was apparent because the rough crystalline structures on the surface melted under visible light irradiation. We used soft lithography and transcribed the rough structure of the crystalline film to a stable polycycloolefin polymer (ZEONEX 480) surface. In this case, ultrasonic treatment was indispensable for molding complex structured surfaces. The transcribed surface showed the same characteristics of dual wettability as the crystalline surface. The crystalline surface using two photochromic diarylethenes was prepared to mimic a termite wing showing dual wettability. The surface is useful to correct small water droplets in the air. However, the crystalline system was not applicable for the use because crystalline structures on the surface melt under daylight. We copied the rough structure of crystalline film to a stable polycycloolefin polymer (Zeonex 480) surface. The copied surface showed the dual wettability as same as that of the crystalline surface.
白蚁翅膀上覆盖着毛轴和微嵴,这使其具有双重润湿性。虽然其表面对大量水和大水滴具有超疏水性,但对微水滴却具有粘附性。我们通过在由两种光致变色二元蒽衍生物组成的光敏晶体表面上应用光诱导晶体生长现象来模拟这种粗糙表面。这种晶体表面显示出双重润湿性,但光活性晶体系统在日光下并不适用。这种不适用性是显而易见的,因为表面粗糙的晶体结构在可见光照射下会融化。我们使用软光刻技术,将结晶膜的粗糙结构转录到稳定的聚环烯烃聚合物(ZEONEX 480)表面。在这种情况下,超声波处理对于复杂结构表面的成型是必不可少的。转录表面显示出与结晶表面相同的双重润湿特性。使用两种光致变色二元酚制备的晶体表面模仿了白蚁翅膀,显示出双重润湿性。该表面可用于校正空气中的小水滴。然而,由于表面的晶体结构在日光下会融化,因此晶体系统并不适用。我们将结晶薄膜的粗糙结构复制到稳定的聚环烯烃聚合物(Zeonex 480)表面。复制表面显示出与晶体表面相同的双重润湿性。
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引用次数: 0
PJ ZEON Award for outstanding papers in Polymer Journal 2023 2023 年《聚合物学报》杰出论文 PJ ZEON 奖
IF 2.8 4区 化学 Q2 Materials Science Pub Date : 2024-06-05 DOI: 10.1038/s41428-024-00905-w
Keiji Tanaka
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引用次数: 0
Structure and mechanical properties of biobased polyamide 11 specimens subjected to different heat treatments 经不同热处理的生物基聚酰胺 11 试样的结构和机械性能
IF 2.3 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2024-06-03 DOI: 10.1038/s41428-024-00924-7
Toyoshi Yoshida, Mei Touji, Hideaki Takagi, Nobutaka Shimizu, Noriyuki Igarashi, Shinichi Sakurai, Makoto Uchida, Yoshihisa Kaneko
The macroscopic mechanical properties of polyamides depend on their microscopic structural properties, such as the crystalline phase, lamellar thickness, and long period, which change depending on the heat treatment conditions. In this study, the relationships between the macroscopic mechanical properties and lamellar structures of polyamide 11 obtained from different heat treatments were investigated. Heat treatments include quench, isothermal, and quench–annealing conditions. Wide-angle X-ray scattering measurements indicated that different crystalline phases formed depending on the heat treatment conditions. Polarized optical microscopy and differential scanning calorimetry revealed spherulite and crystal morphologies that were not spherulite. Small-angle X-ray scattering revealed that the lamellar thickness and long period increased with the heat treatment temperature. With increasing the long period of lamellae, the number of stress transmitters, which are stress transfer factors (entanglements, loop chains, etc.) between lamellae, increases. The lamellar thickness and long period of polyamide 11 were ~1.5 times greater than that of polyamide 6 under similar heat treatment. In uniaxial tensile tests, polyamide 6 specimens heat-treated at high temperatures fractured and did not elongate. Polyamide 11 elongated without fracture. The thick lamellar and long-period structure of polyamide 11 obtained from heat treatments in this study might explain its excellent elongation until the late stage of deformation. The relationships between the macroscopic mechanical properties and lamellar structures of polyamide 11 obtained from different heat treatments were investigated. From the tensile tests, the maximum stress and strain at necking increase with the heat treatment temperature. WAXS measurements indicated that different crystalline phases formed depending on the heat treatment conditions. SAXS revealed that the lamellar thickness and long period increased with the heat treatment temperature. Based on these results, we elucidated that the macroscopic mechanical properties correlate with the lamellar thickness and long period.
聚酰胺的宏观机械特性取决于其微观结构特性,例如结晶相、薄片厚度和长周期,而这些特性会随着热处理条件的不同而发生变化。本研究探讨了不同热处理条件下聚酰胺 11 的宏观机械性能与薄片结构之间的关系。热处理包括淬火、等温和淬火-退火条件。广角 X 射线散射测量结果表明,不同的热处理条件会形成不同的结晶相。偏光光学显微镜和差示扫描量热法显示了球晶和非球晶的晶体形态。小角 X 射线散射显示,片层厚度和长周期随着热处理温度的升高而增加。随着薄片长周期的增加,薄片之间的应力传递因子(缠结、环链等)数量也随之增加。在类似的热处理条件下,聚酰胺 11 的薄片厚度和长周期是聚酰胺 6 的 1.5 倍。在单轴拉伸试验中,高温热处理的聚酰胺 6 试样会断裂,但不会拉长。聚酰胺 11 则拉长而没有断裂。本研究中通过热处理获得的聚酰胺 11 厚层和长周期结构可能是其直到变形后期都具有出色伸长率的原因。
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引用次数: 0
Supracolloidal step-growth polymerization of isotropic silica nanoparticles: a time-resolved small-angle X-ray scattering study 各向同性二氧化硅纳米颗粒的超胶体阶跃生长聚合:时间分辨小角 X 射线散射研究
IF 2.8 4区 化学 Q2 Materials Science Pub Date : 2024-06-03 DOI: 10.1038/s41428-024-00922-9
Tatsuki Oishi, Ayae Sugawara-Narutaki, Rintaro Takahashi
We have investigated the self-assembly kinetics of silica nanoparticles (SNPs) into the polymer-like structure by time-resolved small-angle X-ray scattering (SAXS). The analysis of the SAXS data with a kinetic model revealed that the SNPs undergo self-assembly in a process akin to the step-growth polymerization of bifunctional monomers. This study offers a facile strategy to construct polymer-like structures from isotropic spherical nanoparticles.
我们通过时间分辨小角 X 射线散射(SAXS)研究了二氧化硅纳米颗粒(SNPs)自组装成聚合物状结构的动力学。利用动力学模型对 SAXS 数据进行分析后发现,SNP 的自组装过程类似于双功能单体的阶跃生长聚合过程。这项研究为利用各向同性球形纳米粒子构建类聚合物结构提供了一种简便的策略。
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引用次数: 0
Optimizing a self-solidifying hydrogel as an endoscopically deliverable hydrogel coating system: a proof-of-concept study on porcine endoscopic submucosal dissection-induced ulcers 将自凝固水凝胶优化为内镜下可递送水凝胶涂层系统:对猪内镜粘膜下剥离引起的溃疡进行概念验证研究
IF 2.3 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2024-05-31 DOI: 10.1038/s41428-024-00921-w
Rina Cho, Hiroyuki Kamata, Yosuke Tsuji, Ayano Fujisawa, Yuko Miura, Shohei Ishikawa, Ren Sato, Takuya Katashima, Takamasa Sakai, Mitsuhiro Fujishiro
Endoscopic submucosal dissection (ESD) benefits patients in the early stages of cancer, but it poses various risks of complication. Strategies involving the application of clinically approved products to cover ulcers caused by ESD can reduce these complications, but the fixed nature of their properties limit the understanding of their effects on ulcer healing. This study was focused on Tetra–PEG gel, an innovative hydrogel with controllable physical properties made from a sulfhydryl–maleimide pair. The use of biocompatible polyethylene glycol (PEG) in Tetra–PEG gel may allow for its application as a biomaterial. The aims of our study were to identify the characteristics of a self-solidifying hydrogel for endoscopic application and to develop a new ulcer coating agent for post-ESD treatment. We developed a specialized double-lumen catheter and determined the optimal application conditions of the hydrogel. We examined the hydrodynamic properties of the gelling solutions and elucidated the pressure drop that occurred during device operation. Finally, by considering previous experimental results, we successfully applied the hydrogel to post-ESD ulcers in porcine stomachs. We believed that by further optimizing hydrogels with effectively controlled properties and by continuing to investigate them through animal experiments, we could expand our understanding of the relationships among material and ulcer healing properties and apply this knowledge to clinical applications. We explored the feasibility of Tetra-PEG gel, a controllable hydrogel, as a new biomaterial to develop a coating agent for post-ESD ulcers. We examined the optimal conditions for hydrogel application and developed a specialized catheter, then investigated its properties. Ultimately, we successfully used the optimized hydrogel and device to cover post-ESD ulcers in the porcine stomach. Further optimization of the hydrogel and ongoing research through animal experiments are expected to deepen our understanding of the material’s effects on ulcer healing and contribute to its clinical applications.
内镜黏膜下剥离术(ESD)可使癌症早期患者获益,但也会带来各种并发症风险。在ESD引起的溃疡上使用临床认可的产品可以减少这些并发症,但这些产品的固定特性限制了人们对其对溃疡愈合影响的了解。这项研究的重点是 Tetra-PEG 凝胶,这是一种创新的水凝胶,由一对巯基马来酰亚胺制成,具有可控的物理特性。Tetra-PEG 凝胶中使用的生物相容性聚乙二醇(PEG)可使其作为生物材料应用。我们研究的目的是确定内窥镜应用的自凝固水凝胶的特性,并开发出一种新的溃疡涂层剂,用于ESD后治疗。我们开发了一种专用的双腔导管,并确定了水凝胶的最佳应用条件。我们研究了胶凝溶液的流体力学特性,并阐明了设备运行过程中出现的压降。最后,考虑到之前的实验结果,我们成功地将水凝胶应用于猪胃ESD后溃疡。我们相信,通过进一步优化具有有效控制特性的水凝胶,并继续通过动物实验对其进行研究,可以扩大我们对材料和溃疡愈合特性之间关系的理解,并将这些知识应用到临床应用中。
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引用次数: 0
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Polymer Journal
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