功能化聚丙烯腈纤维促进有机反应的研究进展

聚丙烯腈纤维(PANF)具有出色的机械强度、耐化学性和良好的热稳定性,而且易于进行改性.在聚丙烯腈纺丝原液中加入添加剂或功能单体,或对PANF进行热处理等方法可以实现物理改性.而PANF的化学表面改性包括胺化、酰胺化、氧化、还原、交联、水解、酸处理和化学枝接等方法,表面改性给PANF带来许多特殊官能团,使其可以进一步被用作有机物、有机配体、酶以及过渡金属的载体.通过负载催化活性位点从而得到具有催化活性的功能化PANF.近年功能化PANF作为非均相催化剂被广泛应用于有机合成领域,综述了功能化PANF催化剂在有机反应中的研究成果与进展,包括缩合反应、偶联反应、加成反应、氧化还原反应及多组分一锅法反应等.介绍了纤维催化剂的合成及结构,讨论了催化性能,分析了可能的催化机理,为开发更优的功能化PANF做铺垫.     

聚乳酸在生物医药领域的改性研究进展

聚乳酸类材料是一种用途广泛的生物降解高分子材料,已经成为生物医用材料中最受重视的材料之一。但由于聚乳酸本身的缺陷,限制了其在生物医学工程中的应用。对聚乳酸的改性工作就一直备受关注。本文综述了近几年聚乳酸生物降解材料的物理改性和化学改性研究进展,经改性后聚乳酸的力学性能、降解性能、亲水性能和生物活性得到有效改善,从而更好地满足了生物医用需要。     

羧甲基香菇多糖表面修饰的聚乳酸材料的表面性能研究

制备了香菇多糖羧甲基衍生物,再通过化学接枝方法利用共价键将羧甲基香菇多糖固定在氨基化聚乳酸基材表面,得到羧甲基香菇多糖化学接枝修饰的聚乳酸材料.此外,通过在氨基化聚乳酸基材表面进行羧甲基香菇多糖与壳聚糖的层层自组装,得到生物多糖层层自组装修饰的聚乳酸材料.采用扫描电子显微镜、水接触角测量仪、抗菌活性测试、溶血试验和血栓试验等方法对被修饰聚乳酸材料的表面性能和生物性能进行了分析和比较.结果表明采用2种表面修饰方法得到的羧甲基香菇多糖修饰的聚乳酸材料的亲水性、血液相容性以及对大肠杆菌抗菌活性得到改善.与化学接枝方法相比,经过羧甲基香菇多糖与壳聚糖层层自组装修饰的聚乳酸材料具有更好的亲水性、血液相容性和抗菌活性.     

苯乙烯马来酸酐共聚物化学改性研究进展

苯乙烯-马来酸酐共聚物具有优异的乳化、成膜、增稠等特性,是一种重要的功能化聚合物.从酯化、胺化、苯环接枝、带上电荷、引入功能性基团和引入第三单体等方面对于苯乙烯-马来酸酐共聚物化学改性进行了全面的总结,简评了各种化学改性的方法及改性共聚物的优点,报道了化学改性方法近年来出现的新进展.     

聚合物晶胶的制备、性能及生物医学应用

利用低温凝胶化技术制备的聚合物晶胶,具有贯通多孔结构,因其化学/机械稳定性,可用于生物微粒（质粒、病毒、细胞器）和细胞的分离、生物分子和细胞的固定化载体以及组织工程三维支架等领域。本文详细介绍了聚合物晶胶的制备条件（如单体浓度、冷冻过程、引发剂浓度、溶剂等）与其结构、性能的关系;同时,对聚合物晶胶功能化改性及其在生物物质的色谱分离和生物医学领域的应用进行了总结与展望。     

通过“点击化学”对石墨烯和氧化石墨烯进行功能化改性

点击化学具有操作简单方便、灵活高效等特点,在石墨烯的功能化改性上具有极其重要的应用.本工作针对点击化学对石墨烯和氧化石墨烯功能化改性方面进行了综述.将石墨烯点击功能化改性方法分为两种情况:共价键结合的点击功能化改性和非共价键作用的点击功能化改性,其中共价键结合又可细分为边缘点击功能化改性和表面点击功能化改性.首先,本工作对石墨烯点击功能化改性的反应过程和反应条件及其研究方法作了详细的归类和系统的总结.一方面,在石墨烯点击功能化改性的分类上包括:氧化石墨烯边缘点击,氧化石墨烯表面点击,石墨烯表面点击,石墨烯表面经过Diels-Alder[4+2]的点击反应,以及通过非共价键作用的π-π堆积之后的点击反应;另一方面,在点击反应的合成路线上,详细列出了对石墨烯或者氧化石墨烯进行炔基化或者叠氮基化以及功能化分子进行相应地叠氮基化或者炔基化的连接方法和反应条件,通过点击反应将两部分连接起来,并指出石墨烯功能化复合物的功能特性和应用前景.对这部分工作进行列表总结,然后作图列出石墨烯和氧化石墨烯的点击功能化反应的具体分类和反应过程.另外,本工作列表总结了IR,Raman,UV,1H NMR,13C NMR,XPS,XRD,AFM,TEM,SEM,CV,TGA等对石墨烯和氧化石墨烯进行表征的常用方法,指出了常见的出峰位置以及表征结果和测试目的,并作了简要的分析和说明.最后,对点击化学在石墨烯和氧化石墨烯上的功能化应用作出了总结和展望.     

PNVA-g-PSt微球的功能化与离子吸附研究

由大分子单体法合成了表面聚N-乙烯基乙酰胺接枝聚苯乙烯(PNVA-g-PSt)微球,通过对该接枝链进行化学改性得到了新型功能化高分子微球.用透射电子显微镜、激光光散射和X射线光电子能谱对高分子微球的形态、表面组成和直径大小进行了表征,发现微球经水解后形态更加规整,在分散状态下直径有所增加且保持核-壳型结构.实验比较了几种高分子微球对Cu2 ,Pb2 离子的吸附效果.定量测定结果表明:高分子微球经功能化处理后,其吸附效果有了很大的改进,在较低浓度范围,Pb2 离子的脱除率可达100%.     

接枝改性PVDF基含氟聚合物

聚偏氟乙烯(PVDF基)含氟聚合物由于其独特的性能受到了广泛的关注。将功能化链段引入PVDF基含氟聚合物可以进一步提升其性能并拓展其应用领域。相较于物理共混法和直接共聚改性法,通过接枝改性法将功能化单体引入含氟聚合物的侧链具有更显著的优势,可便捷、高效地得到组成精确,结构可控的接枝共聚物。本文综述了通过活性自由基聚合(包括ATRP、SET-LRP、有机催化原子转移自由基聚合(O-ATRP)、光诱导Cu(Ⅱ)介导RDRP)和高能射线辐射(γ射线,紫外,电子束)等对PVDF基含氟聚合物功能化接枝改性的方法,并对其发展趋势以及改性聚合物的应用前景进行了展望。     

AB_2型β-环糊精功能单体及其水溶性超支化聚合物的合成与表征

为了得到结构确定的β-环糊精大单体并用于超支化聚合,通过对β-环糊精上6位伯羟基和2位仲羟基的多步功能化改性得到了同时含有Si—H和—CH CH2基团的AB2型β-环糊精大单体,并利用硅氢加成反应一步法合成了一种新型的水溶性超支化聚合物,其具有β-环糊精空腔和超支化空穴两种疏水单元,从而可构建出一种新颖的超分子体系.采用1H-NMR、13C-NMR、飞行时间质谱和元素分析对AB2单体及其聚合物的结构进行了表征.结果表明,单体和聚合物的结构与所设计的分子结构相符合.凝胶渗透色谱/多角度激光光散射(SEC/MALLS)联用仪测得该聚合物的数均分子量、分子量分布及特性黏数分别为36690、1.887和15.8mL/g.     

聚乳酸耐热改性的研究进展

聚乳酸(PLA)是一种兼具良好生物相容性、力学以及加工性能的生物基可降解脂肪族聚酯,因此,在医药、食品包装等领域得到广泛应用。然而,PLA结晶速率慢、所得制品结晶度低、耐热性差,严重制约了其在高温环境下的使用。本文综述了国内外聚乳酸耐热改性方面的研究进展,重点阐述通过化学共聚、交联、共混以及外场作用(热处理、拉伸)等手段提高PLA耐热性的方法,并对耐热聚乳酸材料的发展前景进行了展望。     

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.     

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.     

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.     

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.     

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.     

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.     

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.