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Cross-Linked Polymeric Gels and Nanocomposites: New Materials and Phenomena Enabling Technological Applications 交联聚合物凝胶和纳米复合材料:新材料和现象使技术应用
Pub Date : 2022-09-02 DOI: 10.3390/macromol2030028
C. Barbero, M. V. Martínez, D. Acevedo, M. Molina, C. Rivarola
Cross-linked gels are synthesized by homo- and copolymerization of functionalized acrylamides. The gels swell in aqueous solution, and some of them (e.g., poly(N-isopropylacrylamide (PNIPAM)) also in organic solvents of low polarity (e.g., dichloromethane), making the gels amphiphilic materials. Nanocomposites can be made by dispersing nanoparticles (metallic, graphene, nanotubes, and conducting polymers) inside the gels. Additionally, true semi-interpenetrated networks of polyaniline (PANI) inside PNIPAM gels can be prepared by swelling the gel in true solutions of PANI in NMP. PNIPAM-based nanocomposites show a lower critical solution temperature (LCST) transition of the gel matrix, which can be reached by thermal heating or absorption of electromagnetic radiation (light, microwaves, radiofrequency) in the conductive nanomaterials. The characteristic properties (swelling degree and rate, LCST, solute partition, mass transport, hydrophilicity, biocompatibility) can be tuned by changing the functional groups in the copolymers and/or the other components in the nanocomposite. Mass transport and mechanical properties can be adjusted by forming materials with macro- (nanoporous and macroporous), micro- (microgels, thin films, Pickering emulsions), or nano- (nanogels, stabilized nanoparticles) sized features. The material properties are used to produce technological applications: sensors, actuators, controlled release, biological cell scaffolds and surfaces, antimicrobial, carriers of bioactive substances, and matrixes to immobilize enzymes and yeast cells.
交联凝胶是由功能化丙烯酰胺的同源和共聚合成的。凝胶在水溶液中膨胀,其中一些(如聚n -异丙基丙烯酰胺(PNIPAM))也在低极性有机溶剂(如二氯甲烷)中膨胀,使凝胶成为两亲性材料。纳米复合材料可以通过在凝胶中分散纳米颗粒(金属、石墨烯、纳米管和导电聚合物)来制造。此外,通过将凝胶溶胀在NMP中真正的聚苯胺溶液中,可以在PNIPAM凝胶中制备聚苯胺(PANI)的真正半互穿网络。pnipam基纳米复合材料表现出较低的凝胶基质临界溶液温度(LCST)转变,这可以通过加热或吸收导电纳米材料中的电磁辐射(光、微波、射频)来实现。通过改变共聚物和/或纳米复合材料中其他组分的官能团,可以调节共聚物的特性(膨胀度和速率、LCST、溶质分配、质量传递、亲水性、生物相容性)。通过形成具有宏观(纳米多孔和大孔)、微观(微凝胶、薄膜、皮克林乳液)或纳米(纳米凝胶、稳定纳米颗粒)尺寸特征的材料,可以调节质量传递和机械性能。材料特性用于生产技术应用:传感器,执行器,控制释放,生物细胞支架和表面,抗菌剂,生物活性物质的载体,以及固定酶和酵母细胞的基质。
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引用次数: 6
Soft Elastomers Based on the Epoxy–Amine Chemistry and Their Use for the Design of Adsorbent Amphiphilic Magnetic Nanocomposites 基于环氧胺化学的软弹性体及其在吸附性两亲磁性纳米复合材料设计中的应用
Pub Date : 2022-09-02 DOI: 10.3390/macromol2030027
Magda Lorena Arciniegas Vaca, Jimena S. González, C. Hoppe
Poly(ethylene glycol) (PEG)-based soft elastomers, bearing tertiary amine and hydroxyl groups, were synthesized in bulk from the epoxy–amine reaction between poly(ethylene glycol) diglycidyl ether (PEGDE) and a poly(etherdiamine), Jeffamine ED600. High gel fractions (≥0.95) and low glass transition temperatures (Tg ≈ −50 °C) were attained after complete curing of the systems in bulk. The amphiphilicity of the network allowed the swelling of the materials in both aqueous solutions and a variety of organic solvents. Magnetic nanocomposites were synthesized by in situ coprecipitation of magnetic nanoparticles (MNPs) in the elastomeric matrix. The obtained materials were processed by cryogenic milling to obtain powders that were tested as potential magnetic adsorbents and that showed a fast and strong response to the action of a permanent magnet. These materials showed removal rates of at least 50% in 10 min when used in the adsorption of Cu+2 ions from an aqueous solution, making them interesting candidates for the design of magnetically separable metal ion adsorbents.
以聚乙二醇二缩水甘油醚(PEGDE)和聚乙二胺(Jeffamine ED600)为原料,以环氧胺为原料,合成了含叔胺和羟基的聚乙二醇(PEG)基软弹性体。在体系整体完全固化后,获得了高凝胶分数(≥0.95)和低玻璃化转变温度(Tg≈−50℃)。网络的两亲性使得材料在水溶液和各种有机溶剂中都能膨胀。采用磁性纳米颗粒在弹性基体中原位共沉淀法合成磁性纳米复合材料。所得到的材料经过低温铣削加工得到的粉末被测试为潜在的磁性吸附剂,并且对永磁体的作用表现出快速而强烈的反应。当用于从水溶液中吸附Cu+2离子时,这些材料在10分钟内的去除率至少为50%,使其成为设计磁性可分离金属离子吸附剂的有趣候选者。
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引用次数: 2
Removal of Heavy Metal Ions from Wastewaters by Using Chitosan/Poly(Vinyl Alcohol) Adsorbents: A Review 壳聚糖/聚乙烯醇吸附剂去除废水中重金属离子的研究进展
Pub Date : 2022-08-06 DOI: 10.3390/macromol2030026
Dimitrios G. Trikkaliotis, N. Ainali, A. Tolkou, A. Mitropoulos, D. Lambropoulou, D. Bikiaris, G. Kyzas
Through epistemic efforts in water remediation, numerous sorbents have emerged as either low-cost or more expensive. This review article describes the properties, functions and modifications of cost-effective sorbents based on chitosan and poly(vinyl alcohol) blends for aqueous solutions treatment from heavy metals. Interesting synthesis routes have been reported for the production of membranes, beads, foams and mats, while the kinetic and thermodynamic studies provide spherical knowledge of the system. Tables with the adsorbent’s capacity and enthalpy change are included, while indicative images from the synthesis and characterization techniques of the adsorbents are presented.
通过在水修复方面的认知努力,许多吸附剂要么成本低,要么更昂贵。本文综述了壳聚糖与聚乙烯醇共混吸附剂的性能、功能及改性研究进展。有趣的合成路线已被报道用于生产膜,珠,泡沫和垫,而动力学和热力学研究提供了系统的球形知识。附着剂的容量和焓变表包括在内,而从吸附剂的合成和表征技术的指示性图像提出。
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引用次数: 9
The Stability Consequences Promoted by Doping Metallic Atoms on the Degradation of Poly (ε-Caprolactone) 掺杂金属原子对聚ε-己内酯降解的稳定性影响
Pub Date : 2022-08-05 DOI: 10.3390/macromol2030025
T. Zaharescu, T. Borbath, M. Mariș, I. Borbath, M. Mariș
The stability of polymer materials is essentially determined by the molecular structure and the presence of additives and impurities. When a polymer substrate is subjected to vigorous damage by an energetic treatment, the molecular scission generates fragments, which may be oxidized by the diffused oxygen. The traces of oxide catalysts that may be accidentally incorporated into the polymer materials initiate a faster oxidation that influences the material durability. This study presents the behavior of poly (ε-caprolactone) (PCL) loaded with 2 wt% PbZrO3 previously doped with foreign atoms (Cr, Nd, Mg, Mn, Ti) at the concentration of 0.1 mol%. The investigation procedure, chemiluminescence, reveals the acceleration of the degradation of PCL. The contribution of the metallic traces existing in the structure of PbTiO3 powder is characterized by the activation energies (Ea) involved in the propagation of oxidation. The free radicals are involved in a faster oxidation, when the polymer substrate is heated at superior rates. The comparison of the oxidation levels at the extended period of heating and irradiation indicates the sustained activities of metallic traces acting in oxide powder fillers, especially at temperatures exceeding 150 °C. The essential considerations on material strength against oxidation are presented.
高分子材料的稳定性本质上是由分子结构和添加剂及杂质的存在所决定的。当聚合物衬底受到高能处理的剧烈破坏时,分子断裂产生碎片,这些碎片可以被扩散的氧氧化。微量的氧化物催化剂可能意外地掺入到聚合物材料中,引发更快的氧化,从而影响材料的耐久性。本文研究了在0.1 mol%的浓度下,负载2 wt%掺有外源原子(Cr, Nd, Mg, Mn, Ti)的PbZrO3的聚ε-己内酯(PCL)的行为。化学发光的研究过程揭示了PCL的加速降解。存在于PbTiO3粉末结构中的金属痕量的贡献通过参与氧化传播的活化能(Ea)来表征。当聚合物基材以较高的加热速率加热时,自由基参与了更快的氧化。在长时间加热和辐照下氧化水平的比较表明,在氧化物粉末填料中,特别是在超过150°C的温度下,金属痕量的持续活性。提出了材料抗氧化强度的基本考虑因素。
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引用次数: 0
Magnetic Nanoparticles for Medical Applications: Updated Review 磁性纳米颗粒在医学上的应用:最新综述
Pub Date : 2022-08-02 DOI: 10.3390/macromol2030024
G. G. Flores-Rojas, F. López-Saucedo, R. Vera-Graziano, E. Mendizábal, E. Bucio
Magnetic nanoparticles (MNPs) represent an advanced tool in the medical field because they can be modified according to biomedical approaches and guided by an external magnetic field in the human body. The first objective of this review is to exemplify some promising applications in the medical field, including smart drug-delivery systems, therapies against cancer cells, radiotherapy, improvements in diagnostics using magnetic resonance imaging (MRI), and tissue engineering. Complementarily, the second objective is to illustrate the mechanisms of action and theoretical foundations related to magnetoresponsive materials.
磁性纳米颗粒(MNPs)是医学领域的一种先进工具,因为它们可以根据生物医学方法进行修饰,并在人体内的外部磁场引导下进行修饰。本综述的第一个目的是举例说明一些在医学领域有前景的应用,包括智能药物输送系统、抗癌治疗、放射治疗、磁共振成像(MRI)诊断的改进和组织工程。另外,第二个目标是说明与磁响应材料有关的作用机制和理论基础。
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引用次数: 26
Rheological and Stability Evaluation of Emulsions Containing Fenugreek Galactomannan—Xanthan Gum Mixtures: Effect of Microwave and Ultrasound Treatments 含胡芦巴半乳甘露-黄原胶混合物乳剂的流变性和稳定性评价:微波和超声处理的影响
Pub Date : 2022-08-01 DOI: 10.3390/macromol2030023
Rasoul Niknam, M. Soudi, M. Mousavi
The effects of treating two biopolymers (Trigonella foenum—graceum galactomannan and xanthan gum mixtures) with microwaves and ultrasound on the rheological aspects of O/W emulsions were investigated. The data obtained from steady shear flow were fitted with various models and the best were chosen due to the values of R2 and RMSE. The oscillatory shear rheology data demonstrated that the emulsions not treated with microwaves or ultrasound had viscous-like behavior and treated samples demonstrated weak gel behavior. The values obtained for various rheological parameters (especially apparent viscosity, storage modulus and loss modulus) indicated that fenugreek galactomannan had more impact on the rheological aspects of emulsions in comparison with xanthan gum. In addition, the synergistic interaction between two biopolymers, particularly in samples treated with ultrasound, resulted in better rheological aspects which could be affiliated with the strong bonds between the hydrocolloids. By treating the samples with microwaves and ultrasound, the emulsion stability values of the samples (especially those with a high ratio of galactomannan) significantly increased, which might be connected with various parameters, especially viscosity.
研究了微波和超声处理两种生物聚合物(三角Trigonella foenum-graceum半乳甘露聚糖和黄原胶混合物)对油水乳状液流变学的影响。对稳态剪切流得到的数据进行了各种模型的拟合,并根据R2和RMSE的值选择了最佳模型。振荡剪切流变学数据表明,未经过微波或超声处理的乳剂具有粘样行为,处理后的样品表现出弱凝胶行为。各种流变性参数(特别是表观粘度、储存模量和损失模量)的数值表明,胡芦巴半乳甘露聚糖比黄原胶对乳剂流变性的影响更大。此外,两种生物聚合物之间的协同相互作用,特别是在超声处理的样品中,导致更好的流变性方面,这可能与水胶体之间的强键有关。经微波和超声处理后,样品(尤其是半乳甘露聚糖含量高的样品)的乳状液稳定性值明显提高,这可能与各种参数,尤其是粘度有关。
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引用次数: 1
Advances in Alkylated Chitosan and Its Applications for Hemostasis 烷基化壳聚糖及其止血应用研究进展
Pub Date : 2022-07-27 DOI: 10.3390/macromol2030022
Huiyang Jin, Zhengke Wang
Chitosan, a natural polysaccharide, has been widely used as a biomaterial, especially for hemostasis. However, hemostatic materials processed from pure chitosan have limited hemostatic effect and are extremely unstable in some cases; chemical modification is therefore needed to improve the hemostatic properties of chitosan. Through chemical reactions with hydroxyl and amino groups in chitosan macromolecules, such as alkylation, carboxylation, quaternization, etc., different groups can be introduced into the repeating units. Moreover, the introduction of different substituents can endow chitosan with more functions. For example, the introduction of long alkyl chains can improve its hydrophobic property, and greatly improve its hemostatic property. However, there is still no review of alkylated chitosan for hemostasis. Therefore, we introduce in detail several methods (direct alkylation, reductive alkylation and acylation reaction) for preparing alkylated chitosan and its applications for hemostasis.
壳聚糖是一种天然多糖,已被广泛用作生物材料,特别是止血材料。然而,由纯壳聚糖加工而成的止血材料止血效果有限,在某些情况下极不稳定;因此,需要化学改性来改善壳聚糖的止血性能。通过与壳聚糖大分子中的羟基和氨基的化学反应,如烷基化、羧化、季铵化等,可以在重复单元中引入不同的基团。此外,不同取代基的引入可以赋予壳聚糖更多的功能。例如,引入长烷基链可以改善其疏水性,并大大提高其止血性能。然而,烷基化壳聚糖在止血方面的应用尚未见综述。为此,我们详细介绍了几种制备烷基化壳聚糖的方法(直接烷基化、还原烷基化和酰化反应)及其在止血方面的应用。
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引用次数: 9
Biodegradable Films from Kefiran-Based Cryogel Systems 基于kefiran的低温凝胶系统的可生物降解膜
Pub Date : 2022-07-13 DOI: 10.3390/macromol2030021
S. Exarhopoulos, A. Goulas, G. Dimitreli
Kefiran, which was isolated from kefir grains, was used for the fabrication of cryogel-films in the presence of plasticizers, such as glycerol and sorbitol. Varying concentration ratios of the exopolysaccharide/plasticizer system were employed in the process of the cryogel-film formulation and their effect on the physical (film thickness, moisture content, and solubility) and the mechanical (tensile strength and elongation at break) properties of the films was monitored. Kefiran-film vapor adsorption isotherms were calculated, and a thermal analysis of the samples was also performed. The structural characteristics of the cryogel-films were observed using confocal laser scanning microscopy. The cryo-treatment, alongside the plasticizer addition, affected the physical and mechanical properties of the kefiran films, as well as their morphology. Increasing kefiran concentration resulted in increasing the film thickness, the moisture content, and the tensile strength, while decreased their solubility and their elongation at break. Kefiran-film adsorption isotherms were affected by the cryo-treatment, the kefiran concentration, and the plasticizer use and concentration. The thermal analysis of the kefiran films showed thermal stability. The presence of the plasticizers and their increment concentration resulted in decreasing the glass transition and the melting temperatures. The cryo-treatment and the presence of plasticizers resulted in the films appearing smoother. Glycerol proved to affect more than the sorbitol–water vapor adsorption and the morphology of kefiran films.
从开非尔颗粒中分离出来的开非尔酸被用于在甘油和山梨醇等增塑剂存在的情况下制造低温薄膜。在低温薄膜的制备过程中,采用不同浓度比例的外多糖/增塑剂体系,并监测其对薄膜物理性能(薄膜厚度、含水率和溶解度)和力学性能(拉伸强度和断裂伸长率)的影响。计算了凯菲兰膜蒸汽吸附等温线,并对样品进行了热分析。用激光共聚焦扫描显微镜观察了低温膜的结构特征。低温处理和增塑剂的加入影响了kefiran薄膜的物理和机械性能以及它们的形态。随着kefiran浓度的增加,膜的厚度、含水率和抗拉强度增加,而溶解度和断裂伸长率降低。低温处理、丙酮浓度、增塑剂用量和浓度对丙酮膜吸附等温线均有影响。热分析表明,薄膜具有热稳定性。增塑剂的存在及其浓度的增加导致玻璃化转变和熔融温度的降低。冷冻处理和增塑剂的存在使薄膜看起来更光滑。结果表明,甘油对山梨醇-水蒸气吸附和凯菲兰膜形貌的影响大于山梨醇-水蒸气吸附。
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引用次数: 3
Morphological and Viscoelastic Properties of the Cicada Tymbal 蝉鼓室的形态和粘弹性
Pub Date : 2022-07-07 DOI: 10.3390/macromol2030020
Fahrunnida, P. R. Sayekti, C. Robert, B. Retnoaji, Parvez Alam
This paper focusses on the morphological and viscoelastic properties of the cicada tymbal from the species Dundubia rufivena. Morphological details were determined by scanning electron and fluorescence microscopy, while the viscoelastic properties were determined by dynamic mechanical thermal analysis, and further supported by differential scanning calorimetry. We find that water evaporation from the tymbal begins at 71.1 °C and the glass transition for the tymbal, which is a chitin–resilin composite, is on average 150 °C, though there is considerable heterogeneity in the material of the tymbal, as indicated by the half height peak width of the tymbal (35.3 °C) and the shoulder peak indicative of a second phase and hence glass transition at on average, 168 °C. This second phase is assumed to reflect the effects of large-scale molecular pinning and restructuring at resilin–chitin interfaces (possibly via specific binding domains). In addition, we elucidate that the predominantly resilin regions of the tymbal of Dundubia rufivena is reinforced by a polygonal mesh of chitin, a morphological feature that has not been described in any previous research on the cicada tymbal. We provide evidence for nonlinear elasticity in the tymbal by comparing the storage modulus of the tymbal at different frequencies and loading amplitudes.
本文主要研究了鸣蝉(Dundubia rufivena)的蝉鼓的形态和粘弹性特性。形貌细节通过扫描电子显微镜和荧光显微镜确定,粘弹性性能通过动态机械热分析确定,并进一步通过差示扫描量热法支持。我们发现,鼓的水分蒸发开始于71.1°C,而鼓的玻璃化转变平均为150°C,这是一种甲壳素-弹性蛋白复合材料,尽管鼓的材料存在相当大的异质性,如鼓的半高峰宽(35.3°C)和表明第二阶段的肩峰,因此玻璃化转变平均为168°C。这第二阶段被认为反映了大规模分子钉钉和重组在弹性蛋白-几丁质界面的影响(可能通过特定的结合域)。此外,我们阐明了Dundubia rufivena鼓室的主要弹性区域是由几丁质多边形网格加强的,这是以往任何关于蝉鼓室的研究都没有描述过的形态学特征。我们通过比较不同频率和加载幅值下鼓的存储模量,为鼓的非线性弹性提供了证据。
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引用次数: 0
Assessment of Bio-Based Polyurethanes: Perspective on Applications and Bio-Degradation 生物基聚氨酯的评价:应用前景和生物降解
Pub Date : 2022-07-04 DOI: 10.3390/macromol2030019
R. Kaur, Pooja Singh, Surya Tanwar, Gunjan Varshney, S. Yadav
Among numerous synthetic macromolecules, polyurethane in its different forms has proven its sheer dominance and established a reputation as a reliable and trusted material due to its proficiency in terms of superior properties, which include: high mechanical strength and abrasion resistance, good durability, good adhesion, good thermal stability, excellent chemical and weathering resistance. Synthetic polyurethane materials are non-biodegradable, poisonous, and use petrochemical-based raw materials, which are now depleting, leading to a surge in polyurethane production costs. Bio-based polyurethanes (PU) have been synthesized by researchers in recent decades and have mostly overtaken petrochemical-based PU in terms of challenges such as solid pollution, economic effectiveness, and availability of raw materials. Enormous kinds of available bio-renewable sources as predecessors for the production of polyols and isocyanates have been explored for the development of “greener” PU materials; these bio-based polyurethanes have significant potential to be used as future PU products, with a partial or total replacement of petroleum-based polyurethanes, due to increasing concern about the environment, their relatively low cost and biodegradability. This critical review concentrates on the possibilities of renewable sources to be used for polyurethane production and gives a clear perspective on the journey, utilization, and recent advancements in the field of different bio-based polyurethane polymers that have arisen over the last decade.
在众多的合成大分子中,不同形式的聚氨酯已经证明了它的绝对优势,并建立了可靠和值得信赖的材料声誉,因为它具有优越的性能,包括:高机械强度和耐磨性,良好的耐久性,良好的附着力,良好的热稳定性,优异的耐化学和耐风化性。合成聚氨酯材料是不可生物降解的,有毒的,并且使用基于石化的原材料,这些原材料现在正在耗尽,导致聚氨酯生产成本激增。生物基聚氨酯(PU)是近几十年来由研究人员合成的,在固体污染、经济效益和原材料可用性等方面,生物基聚氨酯(PU)在很大程度上已经超过了石化基聚氨酯。为开发“绿色”PU材料,探索了多种可用的生物可再生资源,作为生产多元醇和异氰酸酯的前身;由于人们对环境的日益关注,这些生物基聚氨酯具有相对较低的成本和可生物降解性,因此它们在未来的PU产品中具有很大的潜力,可以部分或完全取代石油基聚氨酯。这篇重要的综述集中在可再生资源用于聚氨酯生产的可能性上,并对过去十年中出现的不同生物基聚氨酯聚合物领域的历程、利用和最新进展给出了清晰的观点。
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引用次数: 31
期刊
Macromol
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