Functional polymer

  • 文章类型: Journal Article
    牙周炎是成人牙齿缺失的主要原因。组织中的细菌生物膜和高活性氧(ROS)水平是牙周炎过程的关键要素。开发具有顺序抗菌/抗氧化能力的先进治疗系统以满足牙周炎治疗的总体目标具有重要意义。在这里,具有生物膜渗透的双聚合物官能化黑色素-AgNPs(P/D-MNP-Ag),羟基磷灰石结合,和顺序处理能力制造。富含甲基丙烯酸2-(二甲基氨基)乙酯(D)的聚合物,可以在酸性环境中质子化,正电荷增强,促进生物膜中的渗透。另一种聚合物富含磷酸基(P),能螯合Ca2+,促进聚合物粘附到羟基磷灰石表面。黑色素具有良好的ROS清除和光热能力,原位还原Ag后,由于热和酸加速了Ag的释放,黑色素-AgNPs复合材料在抗菌和抗氧化能力之间依次过渡。释放的Ag+和热对细菌杀灭具有协同抗菌作用。随着Ag+的消耗,MNP的抗氧化能力恢复到清除炎症区域的ROS。当应用于牙周炎模型时,P/D-MNP-Ag对消融生物膜具有良好的治疗作用,缓解炎症状态,减少牙槽骨丢失。具有序贯治疗能力的P/D-MNP-Ag为开发先进的口腔生物膜根除系统提供了参考。
    Periodontitis is the leading cause of adult tooth missing. Thorny bacterial biofilm and high reactive oxygen species (ROS) levels in tissue are key elements for the periodontitis process. It is meaningful to develop an advanced therapeutic system with sequential antibacterial/ antioxidant ability to meet the overall goals of periodontitis therapy. Herein, a dual-polymer functionalized melanin-AgNPs (P/D-MNP-Ag) with biofilm penetration, hydroxyapatite binding, and sequentially treatment ability are fabricated. Polymer enriched with 2-(Dimethylamino)ethyl methacrylate (D), can be protonated in an acid environment with enhanced positive charge, promoting penetration in biofilm. The other polymer is rich in phosphate group (P) and can chelate Ca2+, promoting the polymer to adhere to the hydroxyapatite surface. Melanin has good ROS scavenging and photothermal abilities, after in situ reduction Ag, melanin-AgNPs composite has sequentially transitioned between antibacterial and antioxidative ability due to heat and acid accelerated Ag+ release. The released Ag+ and heat have synergistic antibacterial effects for bacterial killing. With Ag+ consumption, the antioxidant ability of MNP recovers to scavenge ROS in the inflammatory area. When applied in the periodontitis model, P/D-MNP-Ag has good therapeutical effects to ablate biofilm, relieve inflammation state, and reduce alveolar bone loss. P/D-MNP-Ag with sequential treatment ability provides a reference for developing advanced oral biofilm eradication systems.
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  • 文章类型: Journal Article
    分子相互作用对于稳定无定形固体分散体(ASD)中的无定形药物至关重要。大多数聚合物,然而,与药物形成强分子相互作用的能力有限。为适应要掺入的药物分子的物理化学性质而定制的聚合物,例如,通过允许结合特定的官能团,在这方面将是非常需要的。为此,新型烯丙基封端的聚合物甲氧基(聚乙二醇)-嵌段-聚(茉莉内酯)(mPEG-b-PJL)已被合成并官能化以潜在地增强特定的药物-聚合物相互作用。本研究调查了mPEG-b-PJL在ASD中的使用,使用卡维地洛(CAR),一种弱基础的模型药物。发现揭示了聚合物的酸性官能化形式(mPEG-b-PJL-COOH)与其非官能化对应物mPEG-b-PJL相比确实建立了与CAR的更强的分子相互作用。对形成ASD的聚合物有效性的评估表明,mPEG-b-PJL-COOH在混溶性方面优于其非官能化对应物,载药能力,和稳定性,从降低的分子迁移率推断。然而,溶出测试表明,与单独使用无定形CAR相比,使用mPEG-b-PJL-COOH的ASD并未显着改善溶出行为。尽管通过胶束形成潜在的溶解度增强。总的来说,这项研究证实了官能化聚合物在ASD配方中的潜力,而改善这些ASD的溶解性能的挑战仍然是进一步发展的领域。
    Molecular interactions are crucial to stabilize amorphous drugs in amorphous solid dispersions (ASDs). Most polymers, however, have only a limited ability to form strong molecular interactions with drugs. Polymers tailored to fit the physicochemical properties of the drug molecule to be incorporated, for instance by allowing the incorporation of specific functional groups, would be highly sought-for in this regard. For this purpose, the novel allyl-terminated polymer methoxy(polyethylene glycol)-block-poly(jasmine lactone) (mPEG-b-PJL) has been synthesized and functionalized to potentially enhance specific drug-polymer interactions. This study investigated the use of mPEG-b-PJL in ASDs, using carvedilol (CAR), a weakly basic model drug. The findings revealed that the acidic functionalized form of the polymer (mPEG-b-PJL-COOH) indeed established stronger molecular interactions with CAR compared to its non-functionalized counterpart mPEG-b-PJL. Evaluations on polymer effectiveness in forming ASDs demonstrated that mPEG-b-PJL-COOH outperformed its non-functionalized counterpart in miscibility, drug loading ability, and stability, inferred from reduced molecular mobility. However, dissolution tests indicated that ASDs with mPEG-b-PJL-COOH did not significantly improve the dissolution behaviour compared to amorphous CAR alone, despite potential solubility enhancement through micelle formation. Overall, this study confirms the potential of functionalized polymers in ASD formulations, while the challenge of improving dissolution performance in these ASDs remains an area of further development.
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  • 文章类型: Journal Article
    最近,多组分反应(MCRs)在聚合物合成中备受关注。作为最著名的MCR之一,Kabachnik-Fields(KF)反应已广泛用于开发新型功能聚合物。KF反应可以有效地将官能团引入到聚合物结构中;因此,通过KF反应制备的聚合物具有独特的α-氨基膦酸酯,并显示出重要的生物活性,金属螯合能力,和阻燃性能。在这个小型审查中,主要总结了KF反应合成功能聚合物制备重金属吸附剂的最新进展,多功能水凝胶,阻燃剂,和生物成像探针。我们还讨论了通过KF反应制备的功能聚合物的一些新兴应用。最后,对高分子化学中KF反应的进一步发展提出了自己的观点。
    Recently, multicomponent reactions (MCRs) have attracted much attention in polymer synthesis. As one of the most well-known MCRs, the Kabachnik-Fields (KF) reaction has been widely used in the development of new functional polymers. The KF reaction can efficiently introduce functional groups into polymer structures; thus, polymers prepared via the KF reaction have unique α-aminophosphonates and show important bioactivity, metal chelating abilities, and flame-retardant properties. In this mini-review, we mainly summarize the latest advances in the KF reaction to synthesize functional polymers for the preparation of heavy metal adsorbents, multifunctional hydrogels, flame retardants, and bioimaging probes. We also discuss some emerging applications of functional polymers prepared by means of the KF reaction. Finally, we put forward our perspectives on the further development of the KF reaction in polymer chemistry.
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  • 文章类型: Journal Article
    聚(N-乙烯基咪唑)的催化活性,生物相容性和生物可降解的合成功能聚合物,作为一种有效的肟合成方法,无卤素,和可重复使用的多相催化剂。使用行星式球磨机技术在室温和短时间内以高至优异的产率提供相应的肟。一些优点,如反应时间短,活性差的羰基化合物收率好,避免有毒,贵,含金属催化剂,危险和易燃溶剂,可以提到目前的肟的催化合成。此外,非均相有机催化剂在反应后容易分离,再生后的催化剂多次重复使用,催化活性没有明显损失。
    The catalytic activity of poly(N-vinylimidazole), a biocompatible and biodegradable synthetic functional polymer, was investigated for the synthesis of oximes as an efficient, halogen-free, and reusable heterogeneous catalyst. The corresponding oximes were afforded in high to excellent yields at room temperature and in short times using the planetary ball mill technique. Some merits, such as the short reaction times and good yields for poorly active carbonyl compounds, and avoiding toxic, expensive, metal-containing catalysts, and hazardous and flammable solvents, can be mentioned for the current catalytic synthesis of the oximes. Furthermore, the heterogeneous organocatalyst could be easily separated after the reaction, and the regenerated catalyst was reused several times with no significant loss of its catalytic activity.
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  • 文章类型: Journal Article
    锂硫电池被认为具有在未来为电动汽车供电的可行性,这归因于竞争的能量密度。然而,可溶性多硫化物连续穿梭在硫电极和锂阳极之间穿过隔膜,这极大地削弱了电池的容量。在这里,聚丙烯隔膜(PP膜)的表面成功地用精心设计的阳离子选择性聚合物层改性,以抑制多硫化物的传输。原则上,由于聚合物主链上的双磺酰亚胺阴离子基团被固定,只有阳离子可以通过聚合物层。此外,聚合物中大量的乙氧基链可以促进锂离子的迁移。因此,除了通过固定阴离子的静电排斥力阻碍带负电的多硫化物的运动之外,PP薄膜上的多功能涂层也保证了锂离子的顺利传导。研究表明,具有原始PP膜的电池在2C下进行300次循环后仅提供228.5mAhg-1,具有60.9%的高容量衰减率。相比之下,在相同的测试条件下,聚合物涂层样品可释放409.4mAhg-1,容量衰减率急剧下降至43.2%,说明优越的循环性能。
    Lithium-sulfur batteries are believed to possess the feasibility to power electric vehicles in the future ascribed to the competitive energy density. However, soluble polysulfides continuously shuttle between the sulfur electrode and lithium anode across the separator, which dramatically impairs the battery\'s capacity. Herein, the surface of a polypropylene separator (PP film) is successfully modified with a delicately designed cation-selective polymer layer to suppress the transport of polysulfides. In principle, since bis-sulfonimide anions groups on the backbone of the polymer are immobilized, only cations can pass through the polymer layer. Furthermore, plenty of ethoxy chains in the polymer can facilitate lithium-ion mobility. Consequently, in addition to obstructing the movement of negatively charged polysulfides by the electrostatic repulsive force of fixed anions, the coated multi-functional layer on the PP film also guarantees the smooth conduction of lithium ions. The investigations demonstrate that the battery with the pristine PP film only delivers 228.5 mAh g-1 after 300 cycles at 2 C with a high capacity fading rate of 60.9 %. By contrast, the polymer-coated sample can release 409.4 mAh g-1 under the identical test condition and the capacity fading rate sharply declines to 43.2 %, illustrating superior cycle performance.
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  • 文章类型: Journal Article
    食物垃圾的环境和经济负担需要新的保存技术来减少腐败的降解作用,例如水分,氧气,和微生物。直接食品添加剂可以帮助保持产品质量;然而,这些添加剂的寿命有限,再加上消费者对“清洁标签”产品的渴望,促使人们研究新的食品制造技术,如可以预防和检测食品腐败的活性和智能包装。在这项工作中,姜黄素通过反应性挤出接枝到聚丙烯(PP-g-Cur),通过无溶剂生产非迁移活性和智能包装,高效,和连续方法。姜黄素的固定化通过标准迁移试验证实,其最大迁移量为0.011mg/cm2。显着低于欧盟对食品接触材料的迁移限制(0.1mg/cm2)。与天然PP薄膜相比,PP-g-Cur薄膜阻挡了93%的紫外光,同时在可见光区域保持64%的透明度,允许所需的产品可见性,同时抑制包装商品的紫外线降解。与对照PP相比,PP-g-Cur抑制大肠杆菌和单核细胞增生李斯特菌生长的能力微不足道,游离姜黄素的细菌抑制作用也很差,这表明没有亲水改性,天然姜黄素具有有限的抗菌功效。PP-g-Cur薄膜在有机(11.71±3.02TroloxEq(nmol/cm2))和水性(3.18±1.04TroloxEq(nmol/cm2))基质中均显示出显着的自由基清除作用,在亲脂性和亲水性应用中表现出抗氧化行为的潜力。最后,当PP-g-Cur薄膜暴露于氨时,微生物生长的指标,颜色在视觉上和数量上从黄色变为红色,表现出潜在的腐败迹象。这些发现证明了可扩展技术的潜力,可以生产活性和智能包装,以限制食物浪费并提高功能材料在各种应用中的能力。
    The environmental and economic burden of food waste demands new preservation technologies to reduce the degradative actions of spoilage such as moisture, oxygen, and microorganisms. Direct food additives can help maintain product quality; however, the limited life span of these additives combined with consumer desire for \"clean label\" products has motivated research into new food manufacturing technologies like active and intelligent packaging that can prevent and detect food spoilage. In this work, curcumin was grafted to polypropylene (PP-g-Cur) via reactive extrusion to produce nonmigratory active and intelligent packaging through a solvent-free, efficient, and continuous method. Immobilization of curcumin was confirmed by a standard migration assay exhibiting a maximum of 0.011 mg/cm2 migration, significantly below the EU migratory limit for food contact materials (0.1 mg/cm2). Compared to native PP films, PP-g-Cur films blocked 93% of UV light while retaining 64% transparency in the visible region, allowing for desirable product visibility while inhibiting UV degradation of packaged goods. While the ability of PP-g-Cur to inhibit growth of E. coli and L. monocytogenes was insignificant compared to control PP, free curcumin exhibited poor bacterial inhibition as well, suggesting that without hydrophilic modification, native curcumin has limited antimicrobial efficacy. PP-g-Cur films displayed significant radical scavenging in both organic (11.71 ± 3.02 TroloxEq (nmol/cm2)) and aqueous (3.18 ± 1.04 TroloxEq (nmol/cm2)) matrices, exhibiting potential for antioxidant behavior in both lipophilic and hydrophilic applications. Finally, when PP-g-Cur films were exposed to ammonia, an indicator of microbial growth, the color visually and quantitatively changed from yellow to red, demonstrating potential to indicate spoilage. These findings demonstrate the potential of a scalable technology to produce active and intelligent packaging to limit food waste and advance the capabilities of functional materials in a variety of applications.
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  • 文章类型: Journal Article
    最近,环状聚合物由于其独特的拓扑结构而吸引了越来越多的兴趣,属性,和与线性类似物相比的函数。这篇小型综述集中在环状聚合物的合成和应用方面的最新进展。首先,环状聚合物的主要合成方法,即环形闭合和环形膨胀方法,被介绍和讨论,然后对合成环状聚合物的性能和应用进行了综述。最后,对探索环状聚合物的有效合成和潜在应用的初步研究进行了批判性评估,将讨论该领域的剩余挑战以及解决这些挑战的想法。
    Recently, cyclic polymers have attracted increasing interest due to their unique topologies, properties, and functions compared to the linear analogues. This mini-review focuses on the recent advances in the synthesis and applications of cyclic polymers. First, the main synthetic methods for cyclic polymers, namely ring closure and ring expansion methods, are presented and discussed, followed by a review on the exploration of the properties and applications of synthetic cyclic polymers. Finally, a critical assessment of the preliminary studies exploring the efficient synthesis and potential applications of cyclic polymers are presented, and the remaining challenges in the field as well as ideas for solving these challenges will be discussed.
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  • 文章类型: Journal Article
    The article presents the results of the synthesis and characteristics of the amphiphilic block terpolymers, built of a hydrophilic polyesteramine block, and hydrophobic blocks made of lactidyl and glycolidyl units. These terpolymers were obtained during the copolymerization of L-lactide with glycolide carried out in the presence of previously produced macroinitiators with protected amine and hydroxyl groups. The terpolymers were prepared to produce a biodegradable and biocompatible material containing active hydroxyl and/or amino groups, with strong antibacterial properties and high surface wettability by water. The control of the reaction course, the process of deprotection of functional groups, and the properties of the obtained terpolymers were made based on 1H NMR, FTIR, GPC, and DSC tests. Terpolymers differed in the content of amino and hydroxyl groups. The values of average molecular mass oscillated from about 5000 g/mol to less than 15,000 g/mol. Depending on the length of the hydrophilic block and its composition, the value of the contact angle ranged from 50° to 20°. The terpolymers containing amino groups, capable of forming strong intra- and intermolecular bonds, show a high degree of crystallinity. The endotherm responsible for the melting of L-lactidyl semicrystalline regions appeared in the range from about 90 °C to close to 170 °C, with a heat of fusion from about 15 J/mol to over 60 J/mol.
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  • 文章类型: Journal Article
    将可生物降解的聚酯聚丁二酸丁二醇酯(PBS)和聚己二酸丁二醇酯-共对苯二甲酸酯(PBAT)与没食子酸(GA)通过流延挤出法共混,以生产除氧聚合物。研究了聚酯和GA含量(5至15%)对聚合物/包装性能的影响。由于不混溶性,增加GA形成了不均匀的微观结构和表面粗糙度。与PBS相比,GA与PBAT具有良好的相互作用,赋予更均匀的微观结构,降低机械松弛温度,以及改进的PBAT聚合物的X射线衍射和结晶形态。GA的非均匀分散降低了机械性能,并使水蒸气和氧气的渗透性增加了2倍和7倍,分别。增加量的GA和更高的湿度增强氧吸收能力,这也取决于GA在基质中的分散特性。由于更好的分散和更高的反应表面积,PBAT给出比PBS更高的氧吸收。与PBAT和PBS混合的GA使用功能性可生物降解聚合物作为可持续的活性食品包装增加了氧清除活性。
    Biodegradable polyesters polybutylene succinate (PBS) and polybutylene adipate-co-terephthalate (PBAT) were blended with gallic acid (GA) via cast extrusion to produce oxygen scavenging polymers. The effects of polyesters and GA contents (5 to 15%) on polymer/package properties were investigated. Increasing GA formed non-homogeneous microstructures and surface roughness due to immiscibility. GA had favorable interaction with PBAT than PBS, giving more homogeneous microstructures, reduced mechanical relaxation temperature, and modified X-ray diffraction and crystalline morphology of PBAT polymers. Non-homogenous dispersion of GA reduced mechanical properties and increased water vapor and oxygen permeability by two and seven folds, respectively. Increasing amounts of GA and higher humidity enhanced oxygen absorption capacity, which also depended on the dispersion characteristics of GA in the matrices. PBAT gave higher oxygen absorption than PBS due to better dispersion and higher reactive surface area. GA blended with PBAT and PBS increased oxygen scavenging activity as sustainable active food packaging using functional biodegradable polymers.
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  • 文章类型: Journal Article
    多组分反应(MCR)已用于制备具有吸引人的功能的聚合物。Biginelli的反应,最古老最著名的MCR之一,自2013年以来引发了聚合物化学的新科学发现。近年来,Biginelli反应已从简单的耦合工具进一步发展;例如,Biginelli产物3,4-二氢嘧啶-2(1H)-(thi)酮(DHPM(T))的功能已逐渐被开发出新的功能聚合物。在这个小型审查中,我们主要总结了使用Biginelli反应鉴定用于生物医学应用的聚合物的最新进展。这些聚合物已被记录为抗氧化剂,抗癌剂,和生物成像探针。此外,我们还简要介绍了Biginelli反应在材料和聚合物科学中的一些新兴应用。最后,我们对聚合物化学中Biginelli反应的进一步发展提出了看法。
    Multicomponent reactions (MCRs) have been used to prepare polymers with appealing functions. The Biginelli reaction, one of the oldest and most famous MCRs, has sparked new scientific discoveries in polymer chemistry since 2013. Recent years have seen the Biginelli reaction stepping further from simple coupling tools; for example, the functions of the Biginelli product 3,4-dihydropyrimidin-2(1H)-(thi)ones (DHPM(T)) have been gradually exploited to develop new functional polymers. In this mini-review, we mainly summarize the recent progress of using the Biginelli reaction to identify polymers for biomedical applications. These polymers have been documented as antioxidants, anticancer agents, and bio-imaging probes. Moreover, we also provide a brief introduction to some emerging applications of the Biginelli reaction in materials and polymer science. Finally, we present our perspectives for the further development of the Biginelli reaction in polymer chemistry.
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