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The Valence-Dependent Activity of Colloidal Molecules as Ice Recrystallization Inhibitors. 作为冰再结晶抑制剂的胶体分子的价态依赖性活性
IF 5.1 Q1 POLYMER SCIENCE Pub Date : 2024-07-15 DOI: 10.1021/acsmacrolett.4c00331
Xiaoqian Tian, Huangbing Xu, Teng Qiu, Fengjiao Wu, Xiaoyu Li, Longhai Guo

Inspired by advances in cryopreservation techniques, which are essential for modern biomedical applications, there is a special interest in the ice recrystallization inhibition (IRI) of the antifreeze protein (AFPs) mimics. There are in-depth studies on synthetic materials mimicking AFPs, from simple molecular structure levels to complex self-assemblies. Herein, we report the valence-dependent IRI activity of colloidal organic molecules (CMs). The CMs were prepared through polymerization-induced particle-assembly (PIPA) of the ABC-type triblock terpolymer of poly(acryloxyethyl trimethylammonium chloride)-b-poly(benzyl acrylate)-b-poly(diacetone acrylamide) (PATAC-b-PBzA-b-PDAAM) at high monomer conversions. Stabilized by the cationic block of PATAC, the strong intermolecular H-bonding and incompatibility of the PDAAM block with PBzA contributed to the in situ formation of Janus particles (AX1) beyond the initial spherical seed particles (AX0), as well as the high valency clusters of linear AX2 and trigonal AX3. Their distribution was controlled mainly by the polymerization degrees (DPs) of PATAC and PDAAM blocks. IRI activity results of the CMs suggest that the higher fraction of AX1 results in the better IRI activity. Increasing the fraction of AX1 from 27% to 65% led to a decrease of the mean grain size from 39.8% to 10.9% and a depressed growth rate of ice crystals by 58%. Moreover, by replacing the PDAAM block with the temperature-responsive one of poly(N-isopropylacrylamide) (PNIPAM), temperature-adjustable IRI activity was observed, which is well related to the reversible transition of AX0 to AX1, providing a new idea for the molecular design of amphiphilic polymer nanoparticle-based IRI activity materials.

现代生物医学应用离不开低温保存技术的发展,受此启发,人们对抗冻蛋白(AFPs)模拟物的冰再结晶抑制(IRI)产生了特别的兴趣。从简单的分子结构到复杂的自组装,人们对模仿 AFPs 的合成材料进行了深入研究。在此,我们报告了胶体有机分子(CMs)的价依赖性 IRI 活性。CMs是通过高单体转化率下聚(丙烯酰氧乙基三甲基氯化铵)-b-聚(丙烯酸苄酯)-b-聚(双丙酮丙烯酰胺)ABC型三嵌段三元共聚物的聚合诱导粒子组装(PIPA)制备的。在 PATAC 阳离子嵌段的稳定作用下,PDAAM 嵌段与 PBzA 之间的强分子间 H 键和不相容性有助于在初始球形种子粒子(AX0)之外原位形成 Janus 粒子(AX1),以及线性 AX2 和三棱 AX3 的高价团。它们的分布主要受 PATAC 和 PDAAM 嵌段聚合度 (DP) 的控制。CM 的 IRI 活性结果表明,AX1 的比例越高,IRI 活性越好。将 AX1 的比例从 27% 提高到 65%,可使平均晶粒尺寸从 39.8% 减小到 10.9%,冰晶的生长率降低了 58%。此外,用具有温度响应性的聚(N-异丙基丙烯酰胺)(PNIPAM)取代 PDAAM 嵌段,观察到了温度可调的 IRI 活性,这与 AX0 向 AX1 的可逆转变密切相关,为基于两亲性聚合物纳米粒子的 IRI 活性材料的分子设计提供了新思路。
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引用次数: 0
Salt-Screened Transition toward Bulk-Like Water Dynamics near Polymeric Zwitterions 盐筛向聚合物齐聚物附近大块水动力学的转变
IF 5.8 Q1 POLYMER SCIENCE Pub Date : 2024-07-12 DOI: 10.1021/acsmacrolett.4c00347
Shawn D. Mengel, Audra J. DeStefano, Thomas Webber, Anton Semerdjiev, Songi Han, Rachel A. Segalman
The superior antifouling performance of zwitterionic materials is commonly linked to their hydration structure, in which tight surface binding of water molecules inhibits solute adsorption. However, there is comparatively little direct experimental data on the hydration water structure and dynamics around zwitterionic moieties, including the longer-range behavior of the hydration shell that modulates the approach of solutes to the polymer surface. This work experimentally probes the dynamics of the diffusing hydration water molecules around a series of zwitterion chemistries using Overhauser dynamic nuclear polarization relaxometry. Surprisingly, water dynamics measured within ∼1 nm of the zwitterions were minimally inhibited compared to those near uncharged hydrophilic or cationic side chains. Specific dissolved ions further enhance the water diffusivity near the zwitterions, rendering the hydration shell bulk water-like. These results that the hydration of a zwitterion surface is nearly indistinguishable from bulk water suggest that these surfaces are “invisible” to biological constituents in a manner tunable by the ionic environment and the chemical design of the zwitterionic surface.
通常,人们将具有优异防污性能的齐聚物材料与其水合结构联系起来,在这种结构中,水分子的紧密表面结合抑制了溶质的吸附。然而,有关聚合物表面水合水结构和动态的直接实验数据却相对较少,其中包括水合壳的长程行为,这种行为可调节溶质对聚合物表面的接近。这项研究利用奥弗豪斯动态核极化弛豫测量法,通过实验探测了一系列齐聚物化学结构周围扩散的水合水分子的动态。令人惊讶的是,与不带电的亲水或阳离子侧链附近的水分子相比,在齐聚物附近 1 nm 范围内测得的水动力学抑制很小。特定的溶解离子进一步提高了水在齐聚物附近的扩散性,使水合壳呈现出类似于散装水的状态。齐聚物表面的水合作用与散装水几乎没有区别,这一结果表明,这些表面对生物成分来说是 "隐形 "的,其方式可通过离子环境和齐聚物表面的化学设计进行调整。
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引用次数: 0
Norbornene Dicarboximide: A Green Alternative for Thiol-Norbornene Photopolymers. 降冰片烯二甲酰亚胺:硫醇-降冰片烯光聚合物的绿色替代品。
IF 5.1 Q1 POLYMER SCIENCE Pub Date : 2024-07-11 DOI: 10.1021/acsmacrolett.4c00334
Warrick Ma, Nathaniel Wright, Yadong Wang

Carbic anhydride is an underappreciated starting material for 3D-printable, non-hydrogel photopolymers. Compared with other norbornene precursors, carbic anhydride is cheaper and reactive via aminolysis. As a result, the generalized and efficient functionalization with carbic anhydride can increase the utilization of thiol-norbornene photopolymers. Here, we report carbic anhydride's catalyst-free condensation with two commodity polymers: amine-functionalized polypropylene glycol and polydimethylsiloxane. The reaction completes in 1 h, produces water as the only byproduct, and does not require purification. It is therefore affordable, facile, and green. Mixing the product with thiol cross-linkers and the appropriate photoadditives produces photopolymers that are printable via Digital Light Processing. The photopolymers exhibit tunable tensile properties and a functional surface by varying the polymer backbone and thiol stoichiometry. Moreover, the photopolymers are 3D-printed into true-to-scale human aorta models and porous scaffolds with high resolution. The simple yet versatile platform will benefit additive manufacturing of soft materials and beyond.

碳酐是一种未得到充分重视的起始材料,可用于制造可三维打印的非水凝胶光聚合物。与其他降冰片烯前体相比,碳酸酐更便宜,而且通过氨基溶解可产生反应。因此,用碳酸酐进行通用、高效的官能化可以提高硫醇降冰片烯光聚合物的利用率。在此,我们报告了碳酸酐与两种商品聚合物(胺功能化聚丙二醇和聚二甲基硅氧烷)的无催化剂缩合反应。反应在 1 小时内完成,唯一的副产品是水,且无需净化。因此,该方法经济、简便、绿色。将该产品与硫醇交联剂和适当的光添加剂混合,可制成通过数字光处理技术打印的光聚合物。通过改变聚合物骨架和硫醇的化学计量,光聚合物可表现出可调的拉伸性能和功能性表面。此外,光聚合物还能以高分辨率三维打印成真实比例的人体主动脉模型和多孔支架。这种简单而多用途的平台将有利于软材料及其他材料的增材制造。
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引用次数: 0
Mechanism of Interconnected Pore Formation in High Internal Phase Emulsion-Templated Polymer. 高内相乳液模板聚合物中相互连接的孔隙形成机理。
IF 5.1 Q1 POLYMER SCIENCE Pub Date : 2024-07-11 DOI: 10.1021/acsmacrolett.4c00207
Shengmiao Zhang, Mingjun Chen, Yijing You, Yiling Wang, Yun Zhu

High internal phase emulsion-templated polymer, named polyHIPE, has received widespread attention due to its great potential applications in many fields, such as separation, adsorption, heterogeneous catalysis, and sound absorption. The broad applicability is largely dependent on its adjustable opening structure. However, the question of why polyHIPE has an interconnected pore network structure is still to be discussed. Herein, different types (w/o, o/w, and o/o) of HIPEs are prepared and subsequently detected with laser scanning confocal microscopy (LSCM), and the polyHIPEs obtained by curing the HIPEs are characterized by SEM. The observations suggest that the interconnected pore formation is primarily due to the presence of the surfactant-rich phase in the film between the neighboring droplets in HIPE. The interconnected pores are generated by removal of the surfactant-rich domains in the postcuring procedure, and their sizes would be enlarged if the solubility of the surfactant in the continuous phase decreases in the curing stage.

被命名为 polyHIPE 的高内相乳液模板聚合物因其在分离、吸附、异相催化和吸音等多个领域的巨大应用潜力而受到广泛关注。其广泛的应用性在很大程度上取决于其可调节的开口结构。然而,polyHIPE 为何具有相互连接的孔网络结构这一问题仍有待探讨。本文制备了不同类型(w/o、o/w 和 o/o)的 HIPE,随后用激光扫描共聚焦显微镜(LSCM)对其进行了检测,并用扫描电镜对固化 HIPE 后得到的聚 HIPE 进行了表征。观察结果表明,互连孔隙的形成主要是由于 HIPE 中相邻液滴之间的薄膜中存在富含表面活性剂的相。相互连接的孔隙是在后固化过程中去除富含表面活性剂的畴而产生的,如果在固化阶段表面活性剂在连续相中的溶解度降低,这些孔隙的尺寸就会增大。
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引用次数: 0
Dynamic Ion Gels from the Complex Coacervation of Oppositely Charged Poly(ionic liquid)s. 带相反电荷的聚(离子液体)的复合凝聚产生的动态离子凝胶。
IF 5.1 Q1 POLYMER SCIENCE Pub Date : 2024-07-11 DOI: 10.1021/acsmacrolett.4c00253
Malak Alaa Eddine, Daniil R Nosov, Luiz Fernando Lepre, Anatoli Serghei, Daniel F Schmidt, Damien Montarnal, Alexander S Shaplov, Eric Drockenmuller

A cationic poly(ionic liquid) (PIL) with pendent butyl imidazolium cations and free bis(trifluoromethylsulfonyl)imide (TFSI) anions and an anionic PIL with pendent TFSI anions and free 1-butyl-3-methylimidazolium cations are synthesized by postpolymerization chemical modification and reversible addition-fragmentation chain-transfer radical copolymerization, respectively. Upon mixing solutions of these two PILs in acetone with stoichiometric amounts of ion pairs, ionic exchanges induce coacervation and, after solvent evaporation, lead to the formation of a dynamic ion gel (DIG) and the concomitant release of free [1-methyl-3-butyl imidazolium]TFSI ionic liquid (IL). A comparison of thermal (Tg), ion conducting (σDC), and viscoelastic (elastic moduli (G')) properties for DIGs and their parent polyelectrolytes, as well as extracted and IL-doped DIGs, demonstrates the formation of ionic cross-links and the ability to easily produce polymer electrolytes with enhanced ionic conductivity (σDC up to 4.5 × 10-5 S cm-1 at 30 °C) and higher elastic moduli (G' up to 4 kPa at 25 °C and 1 rad s-1), making them highly desirable in many electrochemical applications, including supercapacitors, soft robotics, electrochromic devices, sensors, and solar cells.

通过聚合后化学修饰和可逆加成-断裂链转移自由基共聚,分别合成了具有下垂丁基咪唑阳离子和游离双(三氟甲基磺酰基)亚胺(TFSI)阴离子的阳离子聚(离子液体)(PIL),以及具有下垂 TFSI 阴离子和游离 1-丁基-3-甲基咪唑阳离子的阴离子聚(离子液体)(PIL)。将这两种 PIL 溶液在丙酮中与等当量的离子对混合后,离子交换会引起共凝结,溶剂蒸发后会形成动态离子凝胶(DIG),同时释放出游离的[1-甲基-3-丁基咪唑鎓]TFSI 离子液体(IL)。通过比较 DIG 及其母体聚电解质以及提取的和掺杂 IL 的 DIG 的热(Tg)、离子传导性(σDC)和粘弹性(弹性模量(G'))特性,证明了离子交联的形成以及轻松制备具有增强离子传导性的聚合物电解质的能力(σDC 高达 4.5 × 10-5 S cm-1)和更高的弹性模量(G'在 25 °C 和 1 rad s-1 条件下高达 4 kPa),使它们在超级电容器、软机器人、电致变色装置、传感器和太阳能电池等许多电化学应用中非常理想。
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引用次数: 0
Quantifying and Modeling the Crystallinity of Polymers Confined in Nanopores. 纳米孔中封闭聚合物结晶度的量化与建模。
IF 5.1 Q1 POLYMER SCIENCE Pub Date : 2024-07-11 DOI: 10.1021/acsmacrolett.4c00287
Ming Wang, Chun Li, Simone Napolitano, Dujin Wang, Guoming Liu

We propose a methodology to characterize the crystalline content of interfacial polymer layers in systems confined at the nanoscale level in a 2D geometry. Based on the crystallinity data of a set of polymers, we introduce a simple model to describe the gradient in crystallinity introduced by confining polymer chains in nanopores. Our model underscores the pivotal role that interfaces play in crystallization and unequivocally contradicts the existence of interfacial "dead" layers where crystallization cannot take place. Further, we verified that the organization of crystals near the pore walls resembles the macromolecular architecture of adsorbed layers, hinting at a strong interplay between crystallization and adsorption.

我们提出了一种方法来表征二维几何中纳米级限制体系中界面聚合物层的结晶含量。根据一组聚合物的结晶度数据,我们引入了一个简单的模型,用于描述将聚合物链限制在纳米孔中所引入的结晶度梯度。我们的模型强调了界面在结晶过程中的关键作用,并明确否定了存在无法结晶的界面 "死 "层的说法。此外,我们还验证了孔壁附近晶体的组织结构与吸附层的大分子结构相似,这表明结晶与吸附之间存在着强烈的相互作用。
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引用次数: 0
Dynamic Implications of Noncovalent Interactions in Amphiphilic Single-Chain Polymer Nanoparticles. 两性单链聚合物纳米粒子中的非共价相互作用的动态影响
IF 5.1 Q1 POLYMER SCIENCE Pub Date : 2024-07-03 DOI: 10.1021/acsmacrolett.4c00269
Peter A Dykeman-Bermingham, Laura R Stingaciu, Changwoo Do, Abigail S Knight

Single-chain polymer nanoparticles (SCNPs) combine the chemical diversity of synthetic polymers with the intricate structure of biopolymers, generating versatile biomimetic materials. The mobility of polymer chain segments at length scales similar to secondary structural elements in proteins is critical to SCNP structure and thus function. However, the influence of noncovalent interactions used to form SCNPs (e.g., hydrogen-bonding and biomimetic secondary-like structure) on these conformational dynamics is challenging to quantitatively assess. To isolate the effects of noncovalent interactions on SCNP structure and conformational dynamics, we synthesized a series of amphiphilic copolymers containing dimethylacrylamide and monomers capable of forming these different interactions: (1) di(phenylalanine) acrylamide that forms intramolecular β-sheet-like cross-links, (2) phenylalanine acrylamide that forms hydrogen-bonds but lacks a defined local structure, and (3) benzyl acrylamide that has the lowest propensity for hydrogen-bonding. Each SCNP formed folded structures comparable to those of intrinsically disordered proteins, as observed by size exclusion chromatography and small angle neutron scattering. The dynamics of these polymers, as characterized by a combination of dynamic light scattering and neutron spin echo spectroscopy, was well described using the Zimm with internal friction (ZIF) model, highlighting the role of each noncovalent interaction to additively restrict the internal relaxations of SCNPs. These results demonstrate the utility of local scale interactions to control SCNP polymer dynamics, guiding the design of functional biomimetic materials with refined binding sites and tunable kinetics.

单链聚合物纳米粒子(SCNPs)结合了合成聚合物的化学多样性和生物聚合物的复杂结构,可生成多功能仿生材料。聚合物链段在长度尺度上的流动性与蛋白质中的二级结构元素相似,这对 SCNP 的结构和功能至关重要。然而,用于形成 SCNP 的非共价相互作用(如氢键和仿生物二级结构)对这些构象动态的影响却很难进行定量评估。为了分离非共价相互作用对 SCNP 结构和构象动力学的影响,我们合成了一系列含有二甲基丙烯酰胺和能够形成这些不同相互作用的单体的两亲共聚物:(1) 二(苯丙氨酸)丙烯酰胺可形成分子内β片状交联;(2) 苯丙氨酸丙烯酰胺可形成氢键,但缺乏确定的局部结构;(3) 苯基丙烯酰胺的氢键倾向最低。根据尺寸排阻色谱法和小角中子散射法的观察,每种 SCNP 形成的折叠结构都与内在无序蛋白质的结构相当。通过动态光散射和中子自旋回波光谱相结合的方法,这些聚合物的动力学特征用齐姆内摩擦(ZIF)模型得到了很好的描述,凸显了每种非共价相互作用对 SCNPs 内部松弛的加成限制作用。这些结果证明了局部相互作用在控制 SCNP 聚合物动力学方面的实用性,为设计具有精细结合位点和可调动力学的功能性仿生材料提供了指导。
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引用次数: 0
Entanglement Kinetics in Polymer Melts Are Chemically Specific. 聚合物熔体中的纠缠动力学具有化学特异性
IF 5.1 Q1 POLYMER SCIENCE Pub Date : 2024-07-03 DOI: 10.1021/acsmacrolett.4c00092
Benjamin E Dolata, Marco A Galvani Cunha, Thomas O'Connor, Austin Hopkins, Peter D Olmsted

We investigate the universality of entanglement kinetics in polymer melts. We compare predictions of a recently developed constitutive equation for disentanglement to molecular dynamics simulations of both united-atom polyethylene and Kremer-Grest models for polymers in shear and extensional flow. We confirm that entanglements recover on the retraction time scale, rather than the reptation time scale. We find that the convective constraint release parameter β is independent of molecular weight, but that it increases with the ratio of Kuhn length bK to packing length p as β ∼ (bK/p)α, with an exponent α = 1.9, which may suggest that disentanglement rate correlates with an increase in the tube diameter. These results may help shed light on which polymers are more likely to undergo shear banding.

我们研究了聚合物熔体中纠缠动力学的普遍性。我们将最近开发的解缠构成方程的预测结果与联合原子聚乙烯和 Kremer-Grest 模型的分子动力学模拟结果进行了比较。我们证实,缠结是在回缩时间尺度上恢复的,而不是在回缩时间尺度上恢复的。我们发现对流约束释放参数 β 与分子量无关,但它会随着库恩长度 bK 与堆积长度 p 的比值 β ∼ (bK/p)α 而增加,指数 α = 1.9,这可能表明解缠速度与管直径的增加有关。这些结果可能有助于揭示哪些聚合物更容易发生剪切带化。
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引用次数: 0
Stably Grafting Polymer Brushes on Both Active and Inert Surfaces Using Tadpole-Like Single-Chain Particles with an Interactive "Head". 利用带有交互式 "头部 "的蝌蚪状单链粒子在活性和惰性表面上稳定接枝聚合物刷。
IF 5.1 Q1 POLYMER SCIENCE Pub Date : 2024-07-02 DOI: 10.1021/acsmacrolett.4c00341
Xiaoya Zhao, Dahua Li, Jie Zhu, Yanbin Fan, Jiayin Xu, Xiayun Huang, Zhihong Nie, Daoyong Chen

We report a "grafting to" method for stably grafting high-molecular-weight polymer brushes on both active and inert surfaces using tadpole-like single-chain particles (TSCPs) with an interactive "head" as grafting units. The TSCPs can be efficiently synthesized through intrachain cross-linking one block of a diblock copolymer; the "head" is the intrachain cross-linked single-chain particle, and the "tail" is a linear polymer chain that has a contour length up to micrometers. When grafted to a surface, the "head", integrating numerous interacting groups, can synergize multiple weak interactions with the surface, thereby enabling stable grafting of the "tail" on both active and traditionally challenging inert surfaces. Because the structural parameters and composition of the "heads" and "tails" can be separately adjusted over a wide range, the interactivity of the "heads" with the surface and properties of the brushes can be controlled orthogonally, accomplishing surface brushes that cannot be achieved by existing methods.

我们报告了一种 "接枝到 "方法,该方法使用带有交互式 "头部 "的蝌蚪状单链粒子(TSCPs)作为接枝单元,在活性和惰性表面上稳定地接枝高分子量聚合物刷。TSCPs 可以通过链内交联二嵌段共聚物的一个嵌段而高效合成;"头部 "是链内交联的单链颗粒,"尾部 "是轮廓长度可达微米的线性聚合物链。当 "头部 "接枝到表面时,整合了众多相互作用基团的 "头部 "可以协同表面的多种弱相互作用,从而使 "尾部 "能够稳定地接枝到活性表面和传统上具有挑战性的惰性表面上。由于 "头部 "和 "尾部 "的结构参数和组成可以在很大范围内分别调整,因此 "头部 "与表面的相互作用和刷子的特性可以正交控制,从而实现现有方法无法实现的表面刷。
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引用次数: 0
Glycopolymer with Sulfated Fucose and 6'-Sialyllactose as a Dual-Targeted Inhibitor on Resistant Influenza A Virus Strains. 含硫酸化岩藻糖和 6'-Sialyllactose 的聚糖作为抗性甲型流感病毒株的双靶向抑制剂。
IF 5.1 Q1 POLYMER SCIENCE Pub Date : 2024-07-01 DOI: 10.1021/acsmacrolett.4c00221
Ping Zhang, Chenning Li, Xiaoyao Ma, Jinfeng Ye, Depeng Wang, Hongzhi Cao, Guangli Yu, Wei Wang, Xun Lv, Chao Cai

The frequent mutations of influenza A virus (IAV) have led to an urgent need for the development of innovative antiviral drugs. Glycopolymers offer significant advantages in biomedical applications owing to their biocompatibility and structural diversity. However, the primary challenge lies in the design and synthesis of well-defined glycopolymers to precisely control their biological functionalities. In this study, functional glycopolymers with sulfated fucose and 6'-sialyllactose were successfully synthesized through ring-opening metathesis polymerization and a postmodification strategy. The optimized heteropolymer exhibited simultaneous targeting of hemagglutinin and neuraminidase on the surface of IAV, as evidenced by MU-NANA assay and hemagglutination inhibition data. Antiviral experiments demonstrated that the glycopolymer displayed broad and efficient inhibitory activity against wild-type and mutant strains of H1N1 and H3N2 subtypes in vitro, thereby establishing its potential as a dual-targeted inhibitor for combating IAV resistance.

甲型流感病毒(IAV)的频繁变异导致人们迫切需要开发创新型抗病毒药物。由于具有生物兼容性和结构多样性,糖聚合物在生物医学应用方面具有显著优势。然而,如何设计和合成定义明确的糖聚合物,以精确控制其生物功能,是目前面临的主要挑战。本研究通过开环元合成聚合和后修饰策略,成功合成了硫酸化岩藻糖和 6'-sialyllactose 的功能性糖聚合物。从 MU-NANA 分析和血凝抑制数据可以看出,优化后的杂多聚合物能同时靶向 IAV 表面的血凝素和神经氨酸酶。抗病毒实验表明,该聚糖在体外对 H1N1 和 H3N2 亚型的野生型和突变株具有广泛而有效的抑制活性,从而确立了其作为双靶向抑制剂对抗 IAV 抗药性的潜力。
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引用次数: 0
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ACS Macro Letters
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