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Inhibition of α-Synuclein Misfolding into β-Sheet Domains on Medium-Sized Gold Nanoclusters: Evidence from Enhanced Sampling MD Simulations
IF 5.8 Q1 POLYMER SCIENCE Pub Date : 2024-10-22 DOI: 10.1021/acsmacrolett.4c00533
Shuai Gong, Guanbin Gao, Taolei Sun, Lei Shen
Targeting Parkinson’s disease (PD) related protein, α-synuclein (αS), via gold nanoclusters (AuNCs) has received considerable attention in PD treatments, but its molecular basis on the initial interactions between αS and AuNCs remains elusive due to the absence of a unique secondary structure of αS chains. Here, at the single-cluster level, we incorporate well-tempered metadynamics simulations to explore the structural and thermodynamic characteristics of the full length αS adsorbed on different-sized AuNCs (Aun, n = 25, 36, 44, 68, 102) with modeled thiolated ligands (Aun@Lig). The conformational landscapes of αS indicate that uncharged Aun@SCH2OH chaperones the native intrinsically disordered conformations of αS, while negatively and positively charged AuNCs greatly increase the likelihood of forming intramolecular β-sheet domains, which are necessary for αS fibrillation and are a hallmark of PD. The binding details further demonstrate the significant inhibitory effect of the medium-sized Au36@SCH2OH on αS misfolding into β-sheet domains. This provides a valuable guideline for customizing AuNCs to precisely manipulate protein folding and misfolding behaviors, with potential implications for disease treatments.
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引用次数: 0
Room-Temperature Synthesis of a Fluorine-Functionalized Nanoporous Organic Polymer for Highly Efficient SF6 Adsorption and Separation 用于高效吸附和分离 SF6 的氟官能化纳米多孔有机聚合物的室温合成
IF 5.8 Q1 POLYMER SCIENCE Pub Date : 2024-10-21 DOI: 10.1021/acsmacrolett.4c00559
Sihan Tong, Lu Yao, Qilin Wang, Jiangli Zhu, Zefeng Wang, Jun Yan
Sulfur hexafluoride (SF6) is widely used in the power industry and significantly contributes to the greenhouse effect, necessitating the development of efficient materials for SF6 capture, particularly fluorine-containing materials. However, existing fluorine-containing materials often require complex monomers and high synthesis temperatures. Herein, we report the synthesis of a fluorine-functionalized carbazole-based nanoporous organic polymer (CNOP-7) at room temperature, using commercially available 4,4′-bis(9H-carbazole-9-yl)-1,1′-biphenyl and 1,1,1-trifluoroacetone. CNOP-7 contains 14.7% fluorine atoms and exhibits a high specific surface area of 1270 m2·g–1, demonstrating excellent SF6 adsorption and separation performance. The SF6/N2 selectivity of CNOP-7 reaches 107 at 273 K and 73 at 298 K. Furthermore, dynamic breakthrough experiments confirm that CNOP-7 can efficiently and repeatedly separate SF6 from SF6/N2 mixtures. Molecular simulations reveal the mechanism behind its efficient separation. This work offers fresh perspectives on the development and fabrication of adsorbents for efficient SF6 sequestration.
六氟化硫(SF6)被广泛应用于电力行业,严重加剧了温室效应,因此有必要开发用于捕获 SF6 的高效材料,尤其是含氟材料。然而,现有的含氟材料通常需要复杂的单体和较高的合成温度。在此,我们报告了利用市售的 4,4′-双(9H-咔唑-9-基)-1,1′-联苯和 1,1,1-三氟丙酮在室温下合成氟功能化咔唑基纳米多孔有机聚合物(CNOP-7)的情况。CNOP-7 含有 14.7% 的氟原子,比表面积高达 1270 m2-g-1,具有出色的 SF6 吸附和分离性能。CNOP-7 的 SF6/N2 选择性在 273 K 时达到 107,在 298 K 时达到 73。此外,动态突破实验证实,CNOP-7 可从 SF6/N2 混合物中高效、反复地分离 SF6。分子模拟揭示了其高效分离背后的机理。这项研究为开发和制造高效封存 SF6 的吸附剂提供了新的视角。
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引用次数: 0
Effects of a Mechanically Interlocked Structure on Ionic Conductivity in Polyrotaxane-Based Polymer Electrolytes 机械互锁结构对聚罗双环烷基聚合物电解质离子电导率的影响
IF 5.8 Q1 POLYMER SCIENCE Pub Date : 2024-10-16 DOI: 10.1021/acsmacrolett.4c00480
Bitgaram Kim, Eunji Lee, Ji-Hun Seo
Polyrotaxane (PR) is a mechanically interlocked polymer (MIP) utilized as an electrolyte because of its distinctive property of dynamic molecular mobility. While numerous studies have concentrated on modifying external properties to decrease high crystallinity, few have explored the control of intrinsic properties. This study examines the crystalline properties and molecular mobility of PR-based electrolytes, along with their effects on ionic conductivity, by manipulating intrinsic properties. By systematically varying the inclusion ratio, we demonstrate that lower inclusion ratios lead to reduced crystallinity, enhancing molecular mobility. Consequently, 100PRE exhibits decreased crystallinity due to lower aggregation probabilities of α-cyclodextrins (α-CDs), longer T2 relaxation times (0.215 s), and higher ionic conductivity (3.4 × 10–3 S cm–1 at 25 °C).
聚对二甲苯(PR)是一种机械互锁聚合物(MIP),因其独特的动态分子流动性而被用作电解质。虽然许多研究都集中于改变外在特性以降低高结晶度,但很少有研究探讨如何控制内在特性。本研究探讨了基于 PR 的电解质的结晶特性和分子流动性,以及它们对离子电导率的影响。通过系统地改变包合比,我们证明较低的包合比会降低结晶度,从而提高分子流动性。因此,由于α-环糊精(α-CD)的聚集概率降低、T2弛豫时间延长(0.215 s)和离子电导率提高(25 °C时为3.4 × 10-3 S cm-1),100PRE的结晶度也随之降低。
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引用次数: 0
Crafting Nanostructured Hybrid Block Copolymer-Gold Nanoparticles by Confined Self-Assembly in Evaporative Droplets. 通过蒸发液滴中的受限自组装,制作纳米结构的嵌段共聚物-金纳米颗粒。
IF 5.1 Q1 POLYMER SCIENCE Pub Date : 2024-10-15 Epub Date: 2024-09-23 DOI: 10.1021/acsmacrolett.4c00519
Andrea Escher, Gianluca Bravetti, Simone Bertucci, Davide Comoretto, Christoph Weder, Ullrich Steiner, Paola Lova, Andrea Dodero

Hybrid organic-inorganic nanostructures offer significant potential for developing advanced functional materials with numerous technological applications. However, the fabrication process is often tedious and time-consuming. This study presents a facile method for fabricating block copolymer-based photonic microspheres incorporating plasmonic gold nanoparticles. Specifically, the confined self-assembly of poly(styrene)-b-poly(2-vinylpyridine) in emulsion droplets allows the formation of spherical, noniridescent, concentric lamellar structures, i.e., onion-like particles that are subsequently infiltrated with gold salt. Using ethanol as a preferential solvent allows the loading of metal ions exclusively into the poly(2-vinylpyridine) domains, which are subsequently reduced, leading to the in situ, spatially controlled formation of gold nanoparticles. The hybrid structures exhibit a well-defined photonic bandgap and plasmonic resonance at low gold concentrations. These results demonstrate the feasibility of fabricating optically active photonic structures comprising metal nanoparticles in a block copolymer array via a simple two-step fabrication process.

有机-无机杂化纳米结构为开发具有多种技术应用的先进功能材料提供了巨大潜力。然而,其制造过程往往繁琐耗时。本研究提出了一种结合了等离子体金纳米粒子的嵌段共聚物基光子微球的简便制备方法。具体来说,聚(苯乙烯)-b-聚(2-乙烯基吡啶)在乳液液滴中的密闭自组装可形成球形、无彩虹色、同心层状结构,即洋葱状颗粒,随后再将金盐渗入其中。使用乙醇作为优先溶剂,可以将金属离子完全装入聚(2-乙烯基吡啶)结构域,然后将其还原,从而在原位形成空间可控的金纳米粒子。这种混合结构具有明确的光子带隙,并能在低金浓度下产生等离子共振。这些结果表明,通过简单的两步制造工艺,在嵌段共聚物阵列中制造包含金属纳米粒子的光学活性光子结构是可行的。
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引用次数: 0
A Total Internal Reflection Microscopy (TIRM)-Based Approach for Direct Characterization of Polymer Brush Conformational Change in Aqueous Solution. 基于全内反射显微镜 (TIRM) 的直接表征水溶液中聚合物刷构象变化的方法。
IF 5.1 Q1 POLYMER SCIENCE Pub Date : 2024-10-15 Epub Date: 2024-10-04 DOI: 10.1021/acsmacrolett.4c00476
Jiahao Wu, Feng Cao, Pui Wo Felix Yeung, Manjia Li, Kohji Ohno, To Ngai

This study presents a novel approach utilizing total internal reflection microscopy (TIRM) to effectively characterize the swelling and collapse of polymer brushes in aqueous solutions. Zwitterionic poly(carboxybetaine methacrylate) (PCBMA) and nonionic poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA) brushes are chosen as model systems. By investigation of an intriguing theory-experiment discrepancy observed during the measurement of near-wall hindered diffusion, valuable insights into the compressibility of polymer brushes are obtained, revealing their conformational information in aqueous solution. The results demonstrate that zwitterionic PCBMA brushes exhibit minimal antipolyelectrolyte effects in 0.1-10 mM NaCl solution but undergo significant swelling with increasing pH. On the other hand, nonionic POEGMA brushes exhibit similar responses to ionic strength as weak polyelectrolyte brushes. These unexpected findings enhance our understanding of polymer brushes beyond classical theories. The TIRM-based approach proves to be effective for characterizing polymer brushes and other soft nanomaterials.

本研究提出了一种利用全内反射显微镜(TIRM)有效描述聚合物刷在水溶液中溶胀和塌陷特性的新方法。研究选择了聚羧基甜菜碱甲基丙烯酸酯(PCBMA)和非离子聚[寡(乙二醇)甲基醚甲基丙烯酸酯](POEGMA)刷作为模型系统。通过研究在测量近壁受阻扩散过程中观察到的一个有趣的理论-实验差异,获得了关于聚合物刷的可压缩性的宝贵见解,揭示了它们在水溶液中的构象信息。结果表明,在 0.1-10 mM NaCl 溶液中,齐聚物 PCBMA 刷的抗聚电解质效应极小,但随着 pH 值的升高,会出现明显的膨胀。另一方面,非离子 POEGMA 电刷对离子强度的反应与弱聚电解质电刷相似。这些意想不到的发现增强了我们对聚合物刷的理解,超越了经典理论。事实证明,基于 TIRM 的方法可有效表征聚合物刷和其他软纳米材料。
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引用次数: 0
Alkyl-Substituted Polycaprolactone Poly(urethane-urea)s as Mechanically Competitive and Chemically Recyclable Materials 作为具有机械竞争力和化学可回收材料的烷基取代聚己内酯聚脲
IF 5.8 Q1 POLYMER SCIENCE Pub Date : 2024-10-15 DOI: 10.1021/acsmacrolett.4c00474
Derek C. Batiste, Michaela R. Pfau-Cloud, Hee Joong Kim, Christopher J. Ellison, Marc A. Hillmyer
We report the mechanical performance and chemical recycling advantages of implementing alkyl-substituted poly(ε-caprolactones) (PCLs) as soft segments in thermoplastic poly(urethane-urea) (TPUU) materials. Poly(4-methylcaprolactone) (P4MCL) and poly(4-propylcaprolactone) (P4PrCL) were prepared, reacted with isophorone diisocyanate, and chain-extended with water to form TPUUs. The resulting materials’ tensile properties were similar or superior to a commercially available polyester thermoplastic poly(urethane) and had superior elastic recovery properties compared to a PCL analogue due to the noncrystalline nature of P4MCL and P4PrCL. Additionally, monomers were recovered from the TPUU materials in high yields via ring-closing depolymerization using a reactive distillation approach at an elevated temperature and a reduced pressure (240–260 °C, 25–140 mTorr) with zinc chloride (ZnCl2) as the catalyst. The thermodynamics of polymerization were estimated using Van’t Hoff analyses for 4MCL and 4PrCL; these results indicated that the propyl group in 4PrCL results in a lower practical ceiling temperature (Tc) for P4PrCL.
我们报告了在热塑性聚氨酯(TPUU)材料中采用烷基取代的聚(ε-己内酯)(PCL)作为软段的机械性能和化学回收优势。制备了聚(4-甲基己内酯)(P4MCL)和聚(4-丙基己内酯)(P4PrCL),与异佛尔酮二异氰酸酯反应,并用水扩链形成 TPU。由于 P4MCL 和 P4PrCL 具有非结晶性,因此与 PCL 类似物相比,所得材料的拉伸性能与市售的聚酯热塑性聚氨酯相似或更优。此外,以氯化锌(ZnCl2)为催化剂,在高温减压(240-260 °C,25-140 mTorr)条件下采用反应蒸馏法,通过闭环解聚从 TPUU 材料中高产率地回收了单体。利用 Van't Hoff 分析法估算了 4MCL 和 4PrCL 的聚合热力学;这些结果表明,4PrCL 中的丙基导致 P4PrCL 的实际上限温度 (Tc) 较低。
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引用次数: 0
Controlled Fabrication of Distinct Nanostructures from Discrete Oligourethanes via Thermal Annealing 通过热退火从离散低聚氨基甲酸酯中可控地制造出独特的纳米结构
IF 5.8 Q1 POLYMER SCIENCE Pub Date : 2024-10-15 DOI: 10.1021/acsmacrolett.4c00615
Qiangqiang Shi, Yong Yu, Lingxiao Guo, Jialin Zhang, Jiajia Tan, Jin Zhang, Jinming Hu, Shiyong Liu
The self-assembly of sequence-defined polymers (SDPs) enables the formation of a diverse array of nanostructures; however, the construction of complex hierarchical structures via thermal annealing from SDPs remains relatively unexplored. In this study, two series of oligourethanes, 2Cit-pBn-OH and 2Cit-mBn-OH, were synthesized to investigate their thermal annealing behaviors. Nanorod clusters were generated from 2Cit-pB6-OH in a mixture of 1,4-dioxane and toluene, whereas 2Cit-pB8-OH formed nanosheets after thermal annealing. Upon modifying the structure of the repeating units, 2Cit-mB6-OH self-assembled into ultrathin nanosheets, transitioning from nanospheres after thermal annealing in a mixture of isopropanol and cyclohexane, while “flower” micelles were produced from 2Cit-mB8-OH. Interestingly, when isopropanol was replaced with a mixture of isopropanol and tetrahydrofuran (THF), uniform nanotubes were generated by 2Cit-mB6-OH under the same thermal annealing conditions. Additionally, a discrete amphiphile (2Cit-mB4-(S)DPEG) was synthesized, leading to the formation of uniform nanosheets in aqueous solution after thermal annealing. This work highlights the significant effects of sequence and repeating unit structure of SDPs on their self-assembly behaviors and presents a novel strategy for the controlled fabrication of unique nanostructures from SDPs.
序列定义聚合物(SDPs)的自组装可以形成多种多样的纳米结构;然而,通过热退火从 SDPs 构建复杂的分层结构的研究相对来说仍处于空白。本研究合成了两个系列的低聚氨基甲酸酯(2Cit-pBn-OH 和 2Cit-mBn-OH),以研究它们的热退火行为。2Cit-pB6-OH在1,4-二氧六环和甲苯的混合物中生成了纳米棒簇,而2Cit-pB8-OH在热退火后形成了纳米片。改变重复单元的结构后,2Cit-mB6-OH 自组装成超薄纳米片,在异丙醇和环己烷的混合物中热退火后从纳米球过渡,而 2Cit-mB8-OH 则产生了 "花 "状胶束。有趣的是,当用异丙醇和四氢呋喃(THF)的混合物代替异丙醇时,在相同的热退火条件下,2Cit-mB6-OH 产生了均匀的纳米管。此外,还合成了一种离散的双亲化合物(2Cit-mB4-(S)DPEG),热退火后在水溶液中形成了均匀的纳米片。这项研究强调了 SDPs 的序列和重复单元结构对其自组装行为的重要影响,并提出了一种利用 SDPs 控制制造独特纳米结构的新策略。
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引用次数: 0
Nonconjugated Polyurethane Derivatives with Aggregation-Induced Luminochromism for Multicolor and White Photoluminescent Films. 用于多色和白色光致发光薄膜的具有聚合诱导发光变色作用的非共轭聚氨酯衍生物。
IF 5.1 Q1 POLYMER SCIENCE Pub Date : 2024-10-15 Epub Date: 2024-09-09 DOI: 10.1021/acsmacrolett.4c00534
Nan Jiang, Ya-Jie Meng, Chang-Yi Zhu, Ke-Xin Li, Xin Li, Yan-Hong Xu, Jia-Wei Xu, Martin R Bryce

A simple and effective strategy to obtain solid-state multicolor emitting materials is a particularly attractive topic. Nonconventional/nonconjugated polymers are receiving widespread attention because of their advantages of rich structural diversity, low cost, and good processability. However, it is difficult to control the molecular conformation or to obtain the crystal structure of amorphous molecules, which means it is a challenge to obtain nontraditional polymeric materials with multicolor emission. In this work, a polyurethane derivative (PUH) with red-shifted emission was synthesized by a simple one-pot polymerization reaction. By exploiting the aggregation-induced luminochromism of PUH, a series of plastic films with tunable emission from blue to orange, and white-light emission, was obtained by doping different amounts of PUH into poly(methyl methacrylate) (PMMA), thereby changing the aggregation degree of PUH. This work demonstrates the excellent promise of polyurethane derivatives for the simple fabrication of large-scale flexible luminescent films.

采用简单有效的策略获得固态多色发光材料是一个特别有吸引力的课题。非常规/非共轭聚合物因其结构丰富多样、成本低廉、加工性能良好等优点而受到广泛关注。然而,非晶态分子的分子构象很难控制,晶体结构也很难获得,这就意味着获得多色发光的非传统聚合物材料是一项挑战。本研究通过简单的一锅聚合反应合成了一种具有红移发射的聚氨酯衍生物(PUH)。利用聚氨酯的聚合诱导发光变色特性,通过在聚甲基丙烯酸甲酯(PMMA)中掺入不同量的聚氨酯,从而改变聚氨酯的聚合度,获得了一系列具有从蓝色到橙色以及白光发射的可调发射塑料薄膜。这项研究成果证明了聚氨酯衍生物在简单制造大规模柔性发光薄膜方面的卓越前景。
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引用次数: 0
Highly Alternating Copolymer of [1.1.1]Propellane and Perfluoro Vinyl Ether: Forming a Hydrophobic and Oleophobic Surface with <50% Fluorine Monomer Content. 1.1.1]Propellane 与全氟乙烯基醚的高度交替共聚物:形成氟单体含量小于 50% 的疏水疏油表面。
IF 5.1 Q1 POLYMER SCIENCE Pub Date : 2024-10-11 DOI: 10.1021/acsmacrolett.4c00558
Mizuki Okuda, Midori Akiyama, Kosuke Funahashi, Junki Masuda, Ai Kohata, Shintaro Nakagawa, Kimiaki Kashiwagi, Norihide Sugiyama, Takashi Okazoe, Daisuke Kawaguchi

Utilizing the unique properties of fluorine substitution is an effective strategy for constructing highly functional materials. Here, we synthesized a novel copolymer composed of [1.1.1]propellane and perfluoro(propyl vinyl ether) (PPVE), rich in alternating sequences. The spin-coated copolymer film was amorphous, and its surface exhibited an extremely low surface free energy (γ). The γ value was lower than that of polytetrafluoroethylene despite containing only 40 mol % PPVE units. This can be attributed to the cancellation of the C-F dipole moments by the entirely random orientation of the fluorine units.

利用氟取代的独特性质是构建高功能材料的有效策略。在这里,我们合成了一种由富含交替序列的[1.1.1]丙烷和全氟(丙基乙烯基醚)(PPVE)组成的新型共聚物。旋涂共聚物薄膜是无定形的,其表面表现出极低的表面自由能(γ)。尽管 PPVE 单元的含量仅为 40 摩尔%,但其 γ 值却低于聚四氟乙烯。这可归因于氟单元的完全随机取向抵消了 C-F 偶极矩。
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引用次数: 0
Functionalization and Repurposing of Polypropylene to a Thermoset Polyurethane 聚丙烯的功能化和热固性聚氨酯的再利用
IF 5.8 Q1 POLYMER SCIENCE Pub Date : 2024-10-10 DOI: 10.1021/acsmacrolett.4c00505
Ronard Herrera Monegro, Ramanan Krishnamoorti, Megan L. Robertson
Developing effective recycling pathways for polyolefin waste, enabling a move to a circular economy, is an imperative that must be met. Postuse modification has shown promising results in upcycling polyolefins, removing the limitation of inertness, and improving the final physical properties of the recycled material while extending its useful lifetime. Grafting of maleic anhydride groups to polypropylene is an established industrial process that enhances its reactivity and provides a convenient route to further functionalization and upcycling. In this work, maleic anhydride grafted polypropylene was hydroxylated and subsequently cured with a diisocyanate to form a thermoset polyurethane (PU). The crystal structure (unit cell and lamellar structure) of the polypropylene (PP) was preserved in the PU. At room temperature, the PU showed a high modulus due to the crystallization behavior of the PP; upon increasing the temperature above the melting temperature, the modulus decreased to a rubbery plateau, consistent with formation of a network. The resulting PU showed a higher glass transition temperature and lower degree of crystallinity than its PP predecessor due to the crosslinked nature of the polymer. The mechanical integrity of the PU was maintained through several reprocessing cycles due to the melt processability enabled by the presence of a urethane exchange catalyst. This functionalization and upcycling route thus offers a promising alternative to repurposing PP waste in which the creation of melt-processable thermoset polymers expands applications for the materials.
为聚烯烃废料开发有效的回收途径,从而实现循环经济,是当务之急。使用后改性在聚烯烃的升级再循环、消除惰性限制、改善再循环材料的最终物理性质以及延长其使用寿命方面取得了可喜的成果。将马来酸酐基团接枝到聚丙烯上是一种成熟的工业工艺,可提高聚丙烯的反应活性,并为进一步功能化和升级再循环提供便捷的途径。在这项工作中,马来酸酐接枝聚丙烯经过羟基化,随后用二异氰酸酯固化,形成热固性聚氨酯(PU)。聚氨酯中保留了聚丙烯(PP)的晶体结构(单胞和层状结构)。在室温下,由于聚丙烯的结晶行为,聚氨酯显示出较高的模量;当温度升至熔化温度以上时,模量下降至橡胶状高原,这与网络的形成一致。由于聚合物的交联特性,与聚丙烯相比,聚氨酯的玻璃化温度更高,结晶度更低。由于聚氨酯交换催化剂的存在使其具有熔融加工性,因此聚氨酯在多次再加工循环中仍能保持机械完整性。因此,这种功能化和升级再循环路线为聚丙烯废料的再利用提供了一种前景广阔的替代方案,可熔融加工的热固性聚合物的产生扩大了材料的应用范围。
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引用次数: 0
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ACS Macro Letters
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