阻燃抗菌羊毛织物的制备及其性能

利用分子间氢键和电荷相互作用力,通过层层喷涂组装技术,将带负电的氧化石墨烯(GO)与带正电的支化聚乙烯亚胺(bPEI)交替沉积到羊毛织物表面,制备(GO/bPEI)_n涂层,再喷涂上一层聚磷酸铵(APP),获得(GO/bPEI)_n-APP修饰的阻燃抗菌羊毛织物。通过阻燃性能测试、热失重分析、导热性能测试和抗菌性能分析证明:相比于纯羊毛织物,通过层层喷涂组装技术获得的(GO/bPEI)_n-APP修饰的羊毛织物的阻燃和抗菌性能显著提高。(GO/bPEI)₇-APP修饰的羊毛织物的极限氧指数为30%,对金黄色葡萄糖球菌的抗菌率47%。实验进一步证实,将氧化石墨烯还原成还原氧化石墨烯(rGO)后,(rGO/bPEI)₇-APP修饰的羊毛织物由于表面吸附更多的APP,所以其极限氧指数高达35%,对金黄色葡萄糖球菌的抗菌率也得到提升(64%)。     

聚乳酸的层层自组装修饰及其内皮细胞相容性研究

通过胺解反应在生物降解聚(L-乳酸)表面引入带有正电荷的自由氨基,并通过静电吸引层层(Layer-by-layer,LBL)自组装技术将具有良好生物相容性的硫酸软骨素(CS)和细胞外基质成分型胶原组装到该PLLA材料表面.通过反应性荧光探针标记、紫外-可见吸收光谱以及荧光能量转移等测试技术跟踪并表征了自组装过程的进行.组装层的厚度开始随组装层数的增加而线性增加,而后增加变缓.内皮细胞的体外培养证明,表面组装CS和胶原(以胶原为最外层)以后,细胞的增殖率和细胞活性显著提高,材料的细胞相容性得到明显改善.细胞体现了充分铺展的多角形内皮细胞形貌,而且局部已融合形成了一单层内皮细胞层.     

层层自组装聚烯丙胺盐酸盐/Pd纳米复合薄膜的制备及其电催化特性

利用层层静电自组装技术将聚烯丙胺盐酸盐(PAH)和四氯合钯酸根离子( )交替沉积在基底上, 然后用硼氢化钠还原, 构筑了含钯纳米粒子的PAH/Pd纳米复合薄膜. 通过紫外-可见吸收光谱(UV-Vis)、扫描电子显微镜(FESEM), X射线光电子能谱(XPS)和循环伏安(CV)等手段对复合膜的组装、成分、微结构、表面形貌和光学性能进行了测试分析. FESEM图形显示膜表面有一定的粗糙度, 膜上生成了粒径在50～100 nm 范围的钯纳米粒子; UV-Vis结果显示多层膜在特征吸收峰处的吸光度数值随膜双层数增加逐渐增大, 呈良好的线性关系, 表明多层膜是均匀组装的; XPS结果证实了复合膜上有Pd生成, CV结果说明复合薄膜对尿酸的氧化具有较好的电催化活性, 有望用于电化学传感器.     

静电层层组装的微量热研究

利用静电层层组装技术,在CaCO3微球表面交替沉积带相反电荷的聚电解质制备多层膜。在静电层层组装过程中伴随热效应出现,借助微量热仪对该热效应进行精确测定,从而为层层组装过程提供一种新的表征手段。     

银/聚电解质复合纳滤膜的制备及表征

利用层层自组装技术(LbL),采用原位还原方法在聚醚砜(PES)基膜上制备了银/聚电解质复合纳滤膜.SEM分析表明:膜表面结构致密,Ag粒子在复合膜中分布均匀,粒径100～200 nm,UV-vis图谱证明膜中粒子为Ag粒子,所得银/聚电解质纳滤膜呈现出优异的抗菌性能.[PSS/PDADMAC]3[PAS/PAH-Ag]3PSS膜对负二价离子显示出较高的截留性能,达到93%.     

一种噻吩基双偶极半菁与普鲁士蓝的静电自组装薄膜

通过交替沉积普鲁士蓝和一种含噻吩的半菁, 制备了一种新的无机-有机杂化静电自组装膜. 用紫外-可见吸收光谱、循环伏安技术和光电化学实验对薄膜进行了表征或光电性质研究. 376和698 nm处薄膜的吸光度随薄膜层数增加线性增加, 表明薄膜的沉积是均匀和可重复的. 薄膜中的普鲁士蓝具有良好的表面控制而非扩散控制的电化学活性, 膜的层数从1增加至5时, 阳极峰电流随膜层数增加而线性增加. 100 mW·cm^-2的白光照射下, 薄膜产生稳定的阴极光电流, 随层数增加线性增长, 层数增加到4层时, 光电流达到最大值. 饱和甘汞电极为参比电极, -0.4 V 偏压下, 4层薄膜产生的光电流密度高达0.28 μA·cm^-2.     

光交联交替层状自组装(LBL)抗菌膜的制备及其性能研究

针对静电超分子作用的交替层状自组装(LBL)膜稳定性差、易分解和难以实现应用的问题,设计合成了一种光交联型抗菌LBL多层膜.该LBL多层膜由修饰有光敏邻硝基苄醇分子的透明质酸(HANB)与季铵化的壳聚糖(ACS)通过静电作用在基片上交替沉积而成.光照后,HANB上的邻硝基苄醇分子产生活性醛基,与邻近壳聚糖上的氨基发生亚...     

塑料表面载银微凝胶层层组装膜的制备及抗菌活性

以载银聚烯丙基胺盐酸盐-葡聚糖微凝胶与聚苯乙烯磺酸钠为构筑基元,利用层层组装技术制备了一种可直接沉积在疏水的塑料基底表面的载银抗菌微凝胶膜. 研究结果表明,该载银抗菌微凝胶膜具有很好的抗菌能力,并且其抗菌活性可以通过控制载银微凝胶膜的组装层数方便地进行调控. 这种制备在塑料表面的载银抗菌微凝胶膜具有良好的稳定性和基底粘附力,能够保障其长效抗菌的实现.     

三聚氰胺甲醛微球的制备及模板法构建聚谷氨酸基微胶囊

以分散聚合法制备低交联度三聚氰胺甲醛(MF)微球, 研究了pH和反应时间等对MF微球粒径、表面电位和溶解性的影响. 以MF微球为模板, 采用层层自组装法交替吸附聚谷氨酸(PGA)和壳聚糖(CS), 构建中空的PGA/CS微胶囊. 采用偏光显微镜、纳米粒度及电位分析仪、红外和透射电镜等进行表征. 结果表明, MF粒径及表面电位随pH值降低而减小, 在盐酸中的溶解性随反应时间延长而变差. 在自组装过程中, 微球表面电位呈正负交替变化, 表明以静电力为主要驱动力制得的空心微胶囊粒径均匀, 分散良好, 模型药物罗丹明可成功载入其中, 有望成为优良的水溶性药物载体.     

含金属纳米粒子的层层自组装及单壁碳纳米管的催化生长

利用层间的静电吸附作用，重氮树脂和不同种类的含金属纳米粒子被依次吸附到硅片表面形成层层自组装膜。通过改变自组装膜的层数可以控制纳米粒子在表面吸附的量，同时利用重氮树脂的光敏特性可以实现纳米粒子在表面的图案化排布。以这些纳米粒子为催化剂，研究了单壁碳纳米管在硅片表面的化学气相沉积生长。     

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%.     

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.     

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.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

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.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.