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Carbidopa and ZnCarbidopa Induce Reductive Stress in MDA-MB-231 Cells. 卡比多巴和锌卡比多巴诱导MDA-MB-231细胞的还原应激。
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-12-23 DOI: 10.1002/cplu.202400596
Agustin B Actis Dato, Luciana G Naso, Valeria R Martínez, Evelina G Ferrer, Patricia A M Williams

The redox imbalance, caused by depletion or generation of reactive oxygen species (ROS), is a key mechanism by which metal complexes exert anticancer effects. Carbidopa has shown the ability to inhibit the MDA-MB-231 cell line, a highly aggressive triple-negative human breast adenocarcinoma, by inducing reductive stress. The metal complex of carbidopa with zinc (ZnCarbi) was designed to modify carbidopa's structure and exhibited increased cytotoxicity against MDA-MB-231 cells. Interestingly, ZnCarbi selectively targets certain cancer cells, showing no impact on the viability of normal HEK293 (human embryonic kidney) cells or other cancer cell lines like A549 (human lung adenocarcinoma), LM3 (murine breast adenocarcinoma), or HCT116 (human colon cancer). Treatment with carbidopa and ZnCarbi induces reductive stress, decreases ROS levels, increases the GSH/GSSG ratio, and protects cells from H2O2-induced death. Both compounds also cause mitochondrial damage, leading to cell death, and exhibit antimetastatic effects by inhibiting cell migration and invasion of MDA-MB-231 cells. Interaction studies with bovine serum albumin showed moderate binding through hydrophobic association. Overall, ZnCarbi demonstrates enhanced anticancer properties compared to carbidopa alone, highlighting its potential as an anticancer and antimetastatic compound.

氧化还原失衡是金属配合物发挥抗癌作用的关键机制,是由活性氧(ROS)的消耗或产生引起的。Carbidopa已经显示出通过诱导还原应激来抑制MDA-MB-231细胞系(一种高度侵袭性的三阴性人乳腺腺癌)的能力。卡比多巴与锌的金属配合物(ZnCarbi)被设计用于修饰卡比多巴的结构,并显示出对MDA-MB-231细胞增强的细胞毒性。有趣的是,ZnCarbi选择性靶向某些癌细胞,对正常HEK293(人胚胎肾)细胞或其他癌细胞系如A549(人肺腺癌)、LM3(小鼠乳腺腺癌)或HCT116(人结肠癌)的活力没有影响。卡比多巴和ZnCarbi处理诱导还原应激,降低ROS水平,增加GSH/GSSG比值,并保护细胞免受h2o2诱导的死亡。这两种化合物也会引起线粒体损伤,导致细胞死亡,并通过抑制细胞迁移和MDA-MB-231细胞的侵袭表现出抗转移作用。与牛血清白蛋白的相互作用研究表明,通过疏水结合适度结合。总的来说,与单独的卡比多巴相比,ZnCarbi显示出增强的抗癌特性,突出了其作为抗癌和抗转移化合物的潜力。
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引用次数: 0
Alkyl 4-Alkoxyvalerates: Characterization and Application in Pd-Catalyzed Aminocarbonylation of Iodo(hetero)arene Compounds. 4-烷氧戊酸烷基酯:表征及其在pd催化碘(杂)芳烃化合物氨基羰基化中的应用。
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-12-23 DOI: 10.1002/cplu.202400713
Nuray Uzunlu Ince, Péter Pongrácz, László Kollár, András Szilágyi, Attila Takács, László T Mika

The palladium-catalyzed aminocarbonylation is one of the most effective methods for the synthesis of carboxamides having great importance. Replacing fossil-based organic solvents in this routinely used catalytic protocol with biomass-derived media is crucial for developing environmentally safe alternatives and towards sustainability considerations. In this study, the open-chain derivatives of bio-originated substance γ-valerolactone i. e. alkyl 4-alkoxyvalerates (alkyl: methyl, ethyl, and propyl) were characterized and tested as potential polar aprotic alternatives of fossil-based common N,N-dimethylformamide (DMF) in aminocarbonylation protocols. First, the temperature-dependent physicochemical properties of alkyl 4-alkoxyvalerates were determined. Based on their characteristics, methyl 4-methoxyvalerate (Me-4MeOV) was selected and introduced in the Pd-catalyzed aminocarbonylation of iodobenzene and morpholine as a model reaction, and an optimization study was carried out. Using the optimized conditions, several substituted iodobenzenes, as well as heteroaryl iodides, were successfully applied resulting in the target carboxamides selectively in short reaction time. Furthermore, the aminocarbonylation of iodobenzene in the presence of various amines was also accomplished extending the scope of the carboxamides produced in this alternative medium. Considering our observations, such as high conversions (up to 95 %) in short reaction time and selective amide formation, it has been justified that Me-4MeOV could be an appropriate alternative medium in aminocarbonylation protocols.

钯催化氨基羰基化反应是合成羧酰胺最有效的方法之一,具有重要意义。在这种常规使用的催化方案中,用生物质衍生介质取代化石基有机溶剂对于开发环境安全的替代品和实现可持续性考虑至关重要。在本研究中,生物源物质g-戊内酯的开链衍生物,即烷基4-烷氧基戊酸酯(烷基:甲基、乙基和丙基)被表征并测试为氨基羰基化方案中化石基常见N,N-二甲基甲酰胺(DMF)的潜在极性非质子替代品。首先,测定了4-烷氧基戊酸烷基酯随温度变化的理化性质。基于其特点,选择4-甲氧基戊酸甲酯(Me-4MeOV)作为模型反应引入pd催化的碘苯和啉氨基羰基化反应,并进行优化研究。在优化的条件下,几种取代碘苯和杂芳基碘化物在较短的反应时间内选择性地合成了目标羧胺。此外,在各种胺的存在下,也完成了碘苯的氨基羰基化,扩大了在这种替代介质中生产的羧酰胺的范围。考虑到我们的观察结果,例如在短反应时间内的高转化率(高达95%)和选择性酰胺形成,证明Me-4MeOV可能是氨基羰基化方案中合适的替代培养基。
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引用次数: 0
Continuous Flow Synthesis and Applications of Metal-Organic Frameworks: Advances and Innovations. 金属-有机骨架的连续流合成与应用:进展与创新。
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-12-23 DOI: 10.1002/cplu.202400634
Rashed Rahman, Fazal Malik, Zaw Min Hein, Junrong Huang, Hengzhi You, Yuxiang Zhu

Metal-Organic Frameworks (MOFs) are an emerging class of solid-state materials comprising inorganic elements and organic molecules. These hybrid materials are widely recognized for their diverse properties, rendering them indispensable in the field of organic synthesis, material science and the pharmaceutical industry. Although the traditional batch methods for MOFs synthesis are well-developed, they often struggle with reproducibility, scalability and environmental issues. However, the development of continuous flow techniques has emerged as a promising alternative, offering more efficient mass and heat transfer, precise reaction control, greater potential for automation, improved safety, and reduced environmental impact. This review primarily focuses on advanced continuous flow synthesis of MOFs incorporating techniques such as air flow, spray drying, microwave, micro-droplets, supercritical carbon dioxide, and ultrasound. Additionally, the recent advancements in applying MOFs as heterogeneous catalysts for various organic transformations under continuous flow conditions are discussed, categorized by the type of bond formation, including C-H bond formation (hydrogen reduction), C-C bond formation, and C-O bond formation.

金属有机骨架(MOFs)是一类由无机元素和有机分子组成的新型固态材料。这些杂化材料因其多样的性能而得到广泛的认可,在有机合成、材料科学和制药工业等领域发挥着不可或缺的作用。尽管传统的批量合成mof的方法已经发展得很好,但它们经常受到再现性、可扩展性和环境问题的困扰。然而,连续流技术的发展已经成为一个有前途的替代方案,提供更有效的质量和热传递,精确的反应控制,更大的自动化潜力,提高安全性,减少对环境的影响。本文主要综述了采用气流、喷雾干燥、微波、微液滴、超临界二氧化碳和超声波等技术合成mof的先进连续流技术。此外,还讨论了mof在连续流动条件下作为各种有机转化的多相催化剂的最新进展,并按键形成类型进行了分类,包括C-H键形成(氢还原)、C-C键形成和C-O键形成。
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引用次数: 0
Foxing of Watercolor Paper and Environmental Control as Preventive Actions. 水彩纸的复色与环境控制作为预防措施。
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-12-23 DOI: 10.1002/cplu.202400647
Woon Lam Ng, Huanlong Hu, Zeyan Zhuang

In Singapore's hot and humid climate, watercolor papers are particularly prone to a paper oxidation issue known as foxing, which refers to the discoloration forming yellowish-brown stains on paper, changing the visual outcome of the watercolor artworks. This research investigates two most popular types of watercolor paper, made from 100 % cotton and cotton-wood-pulp mixture. Foxing was generally categorized into two types: biotic and abiotic foxing caused by fungi activities and the presence of metallic contaminants catalytic fungi growth. However, recent hypotheses further relate it to heterogeneous cellulose structures. Watercolor paper is typically produced in a well-controlled environment, which should theoretically reduce the occurrence of foxing, catalyzed by metallic contaminants. The research involved a comprehensive analysis of aged samples, from old watercolors, dating back to the 1990s and fresh watercolor paper samples. focusing on understanding the origin and causes of watercolor paper foxing based on cellulose content & structures. By comparing 100 % cotton and cotton wood-pulp blended watercolor paper, the susceptivity of foxing was hinted to be related to cellulose packing density. These findings will support further research in developing strategies for the conservation and storage of watercolor artworks.

在新加坡炎热潮湿的气候下,水彩画纸特别容易出现纸张氧化问题,即“foxing”,指的是在纸上形成黄褐色污渍的变色,改变了水彩画作品的视觉效果。本研究调查了两种最流行的水彩纸,由100%棉花和棉花-木浆混合物制成。氧化氧化一般分为两种类型:由真菌活性和金属污染物的存在催化真菌生长引起的生物氧化和非生物氧化。然而,最近的假设进一步将其与异质纤维素结构联系起来。水彩纸通常是在一个控制良好的环境中生产的,理论上应该减少由金属污染物催化的foxing的发生。这项研究包括对年代久远的水彩画样本和新鲜的水彩画样本进行全面分析。重点了解基于纤维素含量和结构的水彩纸成型的起源和原因。通过对100%纯棉和纯棉木浆混纺水彩纸的对比,发现纤维素的包装密度与纸张的光敏度有关。这些发现将支持进一步研究制定保护和储存水彩艺术品的策略。
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引用次数: 0
Cover Feature: Probing Self-Assembly of Ammeline in Chloroform and Aqueous Media: Interplay Between Hydrogen Bonding Diversity and Dimerization (ChemPlusChem 12/2024) 封面专题:探究氨酰在氯仿和水介质中的自组装:氢键多样性和二聚化之间的相互作用(ChemPlusChem 12/2024)
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-12-13 DOI: 10.1002/cplu.202481202
Silvana Carina Pamies, Nélida María Peruchena, Andre Nicolai Petelski

The cover feature shows the structure of ammeline in the center, surrounded by its hydrogen bond palette, which gives rise to all the most stable possibilities of dimerization. In the background are two solvents that can affect the self-recognition of this supramolecular building block: water and chloroform. More information can be found in the Research Article by Andre Nicolai Petelski, Silvana Carina Pamies, and Nélida María Peruchena (DOI: 10.1002/cplu.202400436).

封面特征显示了中心的苯胺结构,周围环绕着它的氢键调色板,这产生了所有最稳定的二聚化可能性。背景中有两种溶剂可以影响这种超分子的自我识别:水和氯仿。更多信息可以在Andre Nicolai Petelski, Silvana Carina Pamies和n lida María Peruchena (DOI: 10.1002/cplu.202400436)的研究文章中找到。
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引用次数: 0
Front Cover: Introducing the Bis(mesitoyl)phosphide Ligand into Dinuclear Trivalent Rare Earth Metal Coordination Chemistry (ChemPlusChem 12/2024) 封面:在双核三价稀土金属配位化学中引入双(mesitoyl)磷化体(ChemPlusChem 12/2024)
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-12-13 DOI: 10.1002/cplu.202481201
Saroshan Deshapriya, Francis Delano IV, Selvan Demir

The front cover image showcases the first dinuclear trivalent lanthanide complexes with bis(mesitoyl)phosphide ligands, one of which is illuminated. The molecules are grown as yellow plate-shaped crystals, stored in a treasure chest. The rock has engraved magnetic susceptibility data featured through red and blue clams. The swimming fish are releasing bubbles that correspond to the traces of the UV-Vis spectra. The ocean scenery also shows orange spheres symbolizing the lanthanide ions. More information can be found in the Research Article by Selvan Demir, Saroshan Deshapriya, and Francis Delano IV (DOI: 10.1002/cplu.202400311).

封面图像显示了第一个双核三价镧系化合物与双(三聚咪甲酰基)磷化体配体,其中一个被照亮。这些分子生长成黄色的盘状晶体,储存在一个宝箱里。岩石上刻有红色和蓝色蛤蜊的磁化率数据。游动的鱼正在释放气泡,这些气泡对应于紫外可见光谱的痕迹。海洋风景也显示橙色球体,象征镧系离子。更多信息可以在Selvan Demir, Saroshan Deshapriya和Francis Delano IV的研究文章中找到(DOI: 10.1002/cplu.202400311)。
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引用次数: 0
Valorization of Industrial Waste Graphite Fines into Graphene Oxide-Based Nanohybrids. 工业废石墨粉制备氧化石墨烯基纳米杂化材料的研究。
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-12-13 DOI: 10.1002/cplu.202400692
Mohammed Subrati, Kyriaki-Marina Lyra, Konstantinos Spyrou, Ilektra Magdalini Toliou, George Petrou, Petros Manganiaris, Aggeliki Papavasiliou, Elias Sakellis, Chrysoula P Athanasekou, Antonella Glisenti, Zili Sideratou, Fotios Katsaros

The rapid growth of graphite market is highly coupled with the increasing demand for Li-ion grade graphite, the production of which results in significant losses of the graphitic material in the form of graphite fines. Herein, for the first time, we report an effective strategy to utilize industrial waste graphite fines through the development of graphene oxide-based nanohybrids as non-toxic and efficient antibacterial agents. To achieve this, graphene oxide (GO) was initially synthesized using industrial waste graphite fines as a graphitic precursor. Subsequently, hyperbranched polyethyleneimine (PEI), or either of its guanidinylated (GPEI) and N-sulfopropylated (SPEI) derivatives were successfully and homogenously attached onto GO, as confirmed by various characterization techniques, yielding GO-PEI, and novel GO-GPEI and GO-SPEI nanohybrids. The antibacterial activity of these nanohybrids was assessed against Gram (-) Escherichia coli and Gram (+) Staphylococcus Aureus bacteria. Both GO-GPEI and GO-SPEI were found to exhibit higher antibacterial activity, specifically against E. coli bacteria, compared to the pristine GO and GO-PEI nanohybrid, with GO-SPEI being more active than GO-GPEI. Finally, GO-GPEI and GO-SPEI were found to exhibit low cytotoxicity against mammalian cells, signifying that they can be used as potential antibacterial agents in various applications, including those in the disinfection industry.

石墨市场的快速增长与锂离子级石墨需求的不断增长密切相关,锂离子级石墨的生产导致石墨材料以石墨粉的形式大量损失。在此,我们首次报道了一种有效的策略,通过开发基于氧化石墨烯的纳米杂化物作为无毒高效的抗菌剂来利用工业废弃石墨粉。为了实现这一目标,氧化石墨烯(GO)最初是用工业废石墨粉作为石墨前驱体合成的。随后,超支化聚乙烯亚胺(PEI)或其胍基化(GPEI)和n -磺丙基化(SPEI)衍生物被成功地均匀地附着在氧化石墨烯上,通过各种表征技术证实,得到了GO-PEI,以及新型的GO-GPEI和GO-SPEI纳米杂化物。研究了这些纳米杂交种对革兰氏(-)大肠杆菌和革兰氏(+)金黄色葡萄球菌的抑菌活性。与原始氧化石墨烯和氧化石墨烯- pei纳米杂种相比,GO- gpei和GO- spei都表现出更高的抗菌活性,特别是对大肠杆菌,其中GO- spei比GO- gpei更有活性。最后,GO-GPEI和GO-SPEI被发现对哺乳动物细胞具有低细胞毒性,这表明它们可以作为潜在的抗菌剂用于各种应用,包括消毒行业。
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引用次数: 0
Covalent Functionalisation of rGO and Nanodiamonds: Complementary Versatility and Applicability of Azomethine Ylide, Nitrile Oxide and Nitrone. 还原氧化石墨烯和纳米金刚石的共价功能化:亚甲酰亚胺、氧化腈和硝酮的互补多功能性和适用性。
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-12-12 DOI: 10.1002/cplu.202400510
Katia Martina, Silvia Tagliapietra, Federica Calsolaro, Andrei Paraschiv, Mirko Sacco, Federico Picollo, Sofia Sturari, Pietro Arpà, Lorenzo Mino, Alessandro Barge, Giancarlo Cravotto

The existing synthetic protocols for the direct functionalization of carbon-based nanomaterials often entail limitations due to their harsh reaction conditions, which require the use of high temperatures for extended periods. This study aims to overcome these limitations by developing mild and efficient synthetic protocols around 1,3-dipolar cycloaddition. Beginning with the well-established azomethine ylide derivatization, we progress to the utilization of nitrile oxide, and of nitrone derivatives for the functionalization of reduced graphene oxide (rGO) as well as of nanodiamonds (NDs). This comparative work employs both classical heating and microwave activation with the aim of reducing reaction times and enhancing efficacy. Results demonstrate that nitrone can react at 60 °C and that the reaction temperature may be decreased to 30 °C with nitrile oxide. Excellent progress was made in reducing the large excess of dipoles typically required for derivatization. Nitrile oxide was proved to be the most efficient in terms of derivatization degree, while nitrone was the most versatile reagent, facilitating the decoration of the carbon nanolayer with disubstituted dihydroisoxazole. To accurately assess the degree of functionalization, the reaction products underwent characterization using various spectroscopic and analytical techniques. Additionally, an indirect evaluation of the reaction outcome was conducted through Fmoc deprotection and quantification.

现有的碳基纳米材料直接功能化的合成方案由于其苛刻的反应条件而受到限制,这需要长时间使用高温。本研究旨在通过开发温和高效的1,3偶极环加成合成方案来克服这些局限性。从建立良好的亚甲基酰化开始,我们进展到利用氧化腈和硝基衍生物来官能化还原氧化石墨烯(rGO)和纳米金刚石(NDs)。这项比较工作采用经典加热和微波活化,目的是减少反应时间和提高疗效。结果表明,硝基酮在60℃下可与氧化腈反应,反应温度可降至30℃。在减少衍生化通常需要的大量过量偶极子方面取得了重大进展。在衍生化程度上,氧化腈是最有效的,而硝基酮是最通用的试剂,有利于用二取代的二氢异恶唑修饰碳纳米层。为了准确地评估功能化程度,使用各种光谱和分析技术对反应产物进行了表征。此外,通过Fmoc脱保护和定量对反应结果进行了间接评价。
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引用次数: 0
Diffusion Coefficient Analysis by Dynamic Light Scattering Enables Determination of Critical Micelle Concentration. 动态光散射扩散系数分析可以确定临界胶束浓度。
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-12-11 DOI: 10.1002/cplu.202400645
Lena Nielinger, Katharina Alker, Wolf Hiller, Leonhard H Urner

The critical micelle concentration is an important property of supramolecular detergents. Two dynamic light scattering approaches have been developed for critical micelle concentration analysis, i. e., concentration-dependent light scattering intensity analysis and diffusion coefficient analysis. Their utility as complementary tools for a reproducible determination of critical micelle concentration remains to be clarified. Herein, we address the question which of the two approaches is more suitable for obtaining reproducible critical micelle concentration values. We systematically compare both approaches in context with common detergent classes and benchmark utility by means of literature values. Our results show that the diffusion coefficient analysis delivers reproducible critical micelle concentration values in aqueous solutions. Our findings outline a roadmap to guide the critical micelle concentration analysis of detergents by dynamic light scattering in the future.

临界胶束浓度是超分子洗涤剂的一个重要性质。针对临界胶束浓度分析,提出了两种动态光散射方法,即浓度相关光散射强度分析和扩散系数分析。它们作为可重复测定临界胶束浓度的补充工具的效用仍有待澄清。在这里,我们解决了这两种方法中哪一种更适合获得可重复的临界胶束浓度值的问题。我们通过文献价值系统地比较了两种方法在普通洗涤剂类别和基准效用的背景下。我们的研究结果表明,扩散系数分析提供了可重复的水溶液临界胶束浓度值。我们的发现概述了一个路线图,以指导未来的动态光散射洗涤剂的临界胶束浓度分析。
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引用次数: 0
Chemically Crosslinked Alginate Hydrogel with Polyaziridine: Effects on Physicochemical Properties and Promising Applications. 聚氮吡啶交联藻酸盐水凝胶:对其理化性质的影响及其应用前景。
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-12-10 DOI: 10.1002/cplu.202400649
Chaehoon Lee, Giacomo Fiocco, Barbara Vigani, Teresa Recca, Chiara Milanese, Chiara Delledonne, Maurizio Licchelli, Silvia Rossi, Yongjae Chung, Francesca Volpi, Maduka L Weththimuni, Marco Malagodi

Alginate biopolymer is widely employed in many industrial fields thanks to its pleasing features of biodegradability, biocompatibility, low toxicity, and relatively low cost. The gelling process of alginate with divalent cations is fairly simple and thus it is used as a versatile biomaterial to tailor the desired mechanical and moisture properties. This study focused on developing new gel formulations to enhance the properties of calcium-alginate hydrogel (CA). The newly synthesized hydrogels, referred to as CA-CHEM gels, were chemically cross-linked with different ratios of pentaerythritol tris[3-(1-aziridinyl)propionate] (PTAP) through the reaction between the carboxylic groups of alginate and aziridines of PTAP. The reaction was successfully monitored by NMR. The new CA-CHEM gels were chemically characterized using FTIR-ATR, while SEM analysis confirmed the changes in the porosity and homogeneity of the network. Additionally, thermogravimetric analyses and mechanical properties showed improvement in degradation stability and in structural strength, compared to plain CA, with an increasing PTAP content up to 1 % w/w. Finally, the new CA-CHEM gels effectively controlled water absorption and release. In particular, CA-CHEM-1 performed as the most controlled system, making it promising for delivering aqueous cleaning solutions on water-sensitive surfaces such as a wooden historical musical instrument.

藻酸盐生物聚合物以其可生物降解、生物相容性好、低毒、成本低等特点,广泛应用于许多工业领域。海藻酸盐与二价阳离子的胶凝过程相当简单,因此它被用作一种通用的生物材料,以定制所需的机械和水分性能。本研究的重点是开发新的凝胶配方来提高海藻酸钙水凝胶(CA)的性能。新合成的水凝胶称为CA-CHEM凝胶,通过海藻酸盐的羧基与PTAP的aziridines之间的反应,与不同比例的季戊四醇三[3-(1-aziridinyl)丙酸酯](PTAP)进行化学交联。通过核磁共振成功地监测了该反应。利用FTIR-ATR对新型CA-CHEM凝胶进行了化学表征,SEM分析证实了网络孔隙度和均匀性的变化。此外,热重分析和力学性能表明,与普通CA相比,PTAP含量增加了1% w/w,降解稳定性和结构强度得到了改善。最后,新型CA-CHEM凝胶有效地控制了水分的吸收和释放。特别是,CA-CHEM-1作为最受控制的系统,使其有望在水敏感表面(如木制历史乐器)上提供水清洁溶液。
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引用次数: 0
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