柔性抗结冰表面的制备及其性能

冰的附着和累积是常见自然现象,但给人类社会带来诸多不便甚至发生重大事故。抗结冰表面是当前研究的热点课题之一,其表面特性是影响结冰最为关键的因素。但是结冰条件的复杂性及结冰类型的多样性致使抗结冰材料的研究面临很大挑战,存在的稳定性差、应用条件局限性等诸多问题尚未解决,不能满足实际应用的需求。本文根据表面分子的柔性或滑移性对抗结冰性能的影响,提出了柔性抗结冰表面的概念,总结了柔性抗结冰表面的种类(本征柔性表面、缓释柔性表面、润滑柔性表面)及其抗结冰机理和近年来取得的一些重要研究成果,并对柔性抗结冰表面存在的问题进行了分析,以期为抗结冰材料的研究提供新的研究思路和方法。     

超疏水涂层表面粗糙结构对防覆冰性能的影响

结冰给交通、电力输送和航空等领域带来极大的安全隐患,研究防覆冰技术具有重要的应用价值。目前最具前景的防冰方法是涂层防冰,本文介绍了疏水涂层的构建方法,阐述了涂层疏水性和疏冰性之间的关系;重点论证了涂层表面粗糙结构对其防覆冰性能的影响,指出防覆冰涂层研发中存在的问题,并对该领域的发展趋势进行了分析和展望。     

表面抗菌功能涂层的构建及在生物医用材料中的应用研究

近年来,生物医用材料在使用过程中产生的医源性感染问题层出不穷,对人们健康和生命造成严重威胁.表面抗菌涂层构建是解决该类医源性感染问题最有效的策略之一.目前,按照作用机制和功能不同将表面抗菌涂层分为接触式抗菌涂层、抗黏附抑菌涂层、抗黏附杀菌涂层以及智能抗菌涂层.表面抗菌涂层的构建不仅赋予了生物医用材料抗菌性能,有效解决了上述医源性感染问题,还可以提高材料的生物相容性,赋予其抗黏附、抗氧化、生物识别、传感等功能.本文旨在对目前表面抗菌涂层的种类、构建方法以及其在生物医用材料领域中的应用做一全面论述,为进一步开发高性能表面抗菌涂层并扩展其应用提供新思路.     

化学气相反应法制备不同碳基体表面SiC涂层组织结构分析

采用化学气相反应法, 以同种工艺分别在石墨和C/C复合材料表面制备了SiC涂层, 借助X射线衍射仪(XRD)、扫描电镜(SEM)及能谱分析等手段分析了涂层的微观结构, 研究了不同碳基体对SiC涂层结构和表面形貌的影响, 并初步对比考察了涂层的高温抗氧化性能. 结果表明: 制备的SiC涂层整体致密, 与基体结合良好, 但存在明显的结构差异. 石墨表面制得的SiC涂层呈梯度分布, 涂层主要由致密外层及过渡内层组成, 而C/C复合材料表面制得的SiC涂层仅由致密外层组成; 在1823 K的空气氧化氛围中, 与C/C复合材料SiC涂层试样相比, 石墨SiC涂层试样表现出更好的高温抗氧化性能, 经30 h氧化及7次循环热震实验后, 涂层试样的氧化失重率仅为0.182%.     

抗失水抗结冰水凝胶的研究进展

水凝胶在柔性可穿戴式器件、电子皮肤和软体机器人等领域具有巨大的应用潜力.然而,大部分水凝胶材料仍然面临容易失水变干,在严寒气候下容易冻结失效等挑战,严重限制了水凝胶材料的应用范围和发展前景.近年来,为了解决水凝胶在干旱地域和严寒气候的失效问题,研究人员设计和制备了一系列抗失水抗结冰的水凝胶材料.在本综述里,我们主要从制备策略和应用这两方面归纳并总结了抗失水和抗结冰水凝胶在近些年来的发展情况,着重讨论了表面修饰弹性体的水凝胶、盐凝胶、有机-水双溶剂凝胶以及纳米限域水凝胶各类水凝胶材料的制备原理和研究进展.这些策略极大地改善了水凝胶材料的抗失水性和抗结冰性.基于这些制备方法,介绍了抗失水抗结冰水凝胶在储能器件、柔性可穿戴设备、传感器和集水等领域的应用.最后,我们对这个领域的发展现状进行总结,指出当前所面临的挑战,并讨论了未来可能的发展方向.     

防覆冰涂层构建机理及制备

航空、通信、电力和运输设备的覆冰现象给人们的生产、生活带来许多不便,甚至引起重大经济损失,防覆冰涂层主要通过材料表面特殊物理化学性能与微相形貌来实现抗冰目的,这类材料需要兼具防结冰性和疏冰性,从延长结冰时间和降低冰的附着力两方面来减轻甚至消除冰雪积聚,是目前研究的热点。本文从防覆冰机理入手,深入探讨了防结冰性和疏冰性的影响因素,阐述了防覆冰涂层材料的设计与制备方面的最新进展,并对防覆冰涂层目前存在的问题与发展方向进行了分析和展望。     

石墨烯用于金属腐蚀防护的研究

单层无缺陷石墨烯具有优异的屏蔽性能,能阻隔氧气、水分子等腐蚀因子到达金属基体表面,被认为是已知最薄的腐蚀防护涂层。基于石墨烯在金属腐蚀防护领域巨大的应用潜力,本文从石墨烯薄膜防护涂层、石墨烯/有机防护涂层以及石墨烯-导电高分子/有机防护涂层等方面进行系统总结,重点围绕石墨烯薄膜存在的问题以及石墨烯在有机涂层中均匀分散等进行详细分析和介绍,同时对石墨烯基防腐涂料的未来发展进行了展望。     

聚合物抗污涂层的研究进展

构筑聚合物抗污涂层表面是解决生物污损的有效策略. 聚合物具有耐酸碱性和易于功能化及表面修饰等优点, 聚合物抗污涂层在降低生物污损对材料的影响和减少经济损失中发挥着重要作用. 本文综合评述了聚合物抗污涂层的各种研究策略和研究进展, 介绍了相关新型聚合物抗污涂层的成果, 并展望了该领域面临的挑战.     

功能性POSS聚合物及其应用

多面体低聚倍半硅氧烷(POSS)是一类具有纳米分子尺寸和有机-无机杂化结构的化合物。这种以无机Si—O—Si键组成的框架为核,外围被有机取代基所包围的特殊结构,具有独特的物理性质和化学反应性。采用物理或共聚的方法使其与其他聚合物复合,得到具有特殊功能的有机/无机纳米复合高分子材料,可用于诸多领域,近年来备受关注。本文在介绍POSS分子结构特点的基础上,详细阐述POSS聚合物的合成方法、特点和功能性,着重讨论了POSS在超疏水表面与抗结冰涂层、两亲聚合物、形状记忆材料中的应用及研究现状,并展望了功能性POSS聚合物的发展前景。     

电化学方法在钛表面制备Co-YSZ/HAp纳米复合涂层

采用复合电沉积和电泳沉积两步法在钛基体上制备了Co-YSZ/HAp纳米复合涂层, 与只采用电泳沉积法在钛基体上制备纳米HAp单一涂层进行了比较研究.采用场发射扫描电镜、X 射线衍射和能量散射谱对复合涂层的微观形貌, 纳米HAp外层表面形貌, 晶相, 复合涂层的断面形貌及元素组成分布进行分析研究. 通过粘结-拉伸实验测定了涂层与基体的结合强度, 结果表明, Co-YSZ/HAp 纳米复合涂层与钛基体的结合强度明显高于纳米HAp 单一涂层与钛基体的结合强度, 说明复合涂层具有更好的力学性能.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.