表面增强拉曼光谱法快速检测纺织品中的偶氮染料

建立纺织品中偶氮染料的表面增强拉曼光谱快速筛查方法。以24种芳香胺为研究对象,利用表面增强拉曼光谱技术,结合使用金纳米粒子增强剂,对纺织品中的偶氮染料进行检测。通过对样品纳米金溶胶的用量、缓冲溶液种类和pH值的优化,确定了最佳优化条件:纳米金溶胶的用量为50μL,缓冲溶液为柠檬酸溶液,pH值为6.0。同时对24种芳香胺的特征峰进行采集、分析和分类,确定分为以下几类:苯胺类、联苯类、含硝基类、萘类。该方法操作简单,易于掌握,可以快速筛选出纺织品中的偶氮染料。     

聚亚甲基蓝和纳米金修饰玻碳电极的葡萄糖生物传感器

用循环伏安法在玻碳电极上电聚合一层稳定的亚甲蓝聚合物膜,研究了这层膜在0.1mol/L磷酸缓冲溶液(pH7.0)中的电化学性质。用纳米金溶胶与聚乙烯醇缩丁醛(PVB)构成复合固酶基质,采用溶胶-凝胶法固定葡萄糖氧化酶(GOD)于亚甲蓝修饰的玻碳电极表面,制成了新型葡萄糖生物传感器。实验发现,加入纳米金后提高了酶电极对葡萄糖的电流响应,所制备的传感器具有响应快、灵敏度高、稳定性好,对葡萄糖的线性响应范围为1×10-6~3×10-3mol/L,检出限为5×10-7mol/L。并具有抗尿酸、抗坏血酸干扰的特点。     

天青Ⅰ为电子媒介体金纳米颗粒修饰葡萄糖生物传感器

用纳米金溶胶与聚乙烯醇缩丁醛(PVB)构成复合固酶基质,采用溶胶凝胶法固定葡萄糖氧化酶(GOx)于铂金电极表面,并在葡萄糖溶液中加入天青Ⅰ作为电子媒介体,制成了新型葡萄糖生物传感器。实验证明,葡萄糖氧化酶吸附在纳米金颗粒表面上稳定且保持其生物活性;而电子媒介体的存在,显著提高了传感器的响应灵敏度。该传感器对葡萄糖响应的线性范围为2.5×10-5～7.5×10-3mol/L;检出限为8.5×10-6mol/L(S/N=3)。该生物传感器用于人体血清中的葡萄糖测定,结果令人满意。     

PVP 稳定的纳米 Au 溶胶对葡萄糖液相选择氧化的催化性能

 采用化学还原法制备了聚乙烯吡咯烷酮 (PVP) 稳定的纳米 Au 溶胶, 这种 Au 溶胶在葡萄糖空气氧化制葡萄糖酸反应中具有良好的催化性能. 考察了 PVP 加入量和氯金酸前驱液的浓度对反应活性的影响. 紫外-可见吸收光谱和透射电镜分析结果表明, 含有较小 Au 粒子的 Au 溶胶体系具有较高的催化活性. 当 PVP/Au 质量比为 40, 氯金酸浓度为100 μg/ml 时, 得到稳定的 Au 溶胶体系具有金粒子尺寸小、分布均匀的特点, 对葡萄糖氧化反应活性高, 葡萄糖的转化率达到 54.4%.     

pH值对硫醇修饰的金纳米粒子聚集态的影响

制备了3 巯基丙酸修饰的金纳米颗粒,溶胶的pH值变化导致颗粒表面的电荷发生变化.随着pH值的降低,颗粒的聚集体增大,在pH值小于4时颗粒下沉.加碱增大溶胶的pH值,聚集的颗粒会重新分散.     

金＠壳聚糖复合材料的合成、表征及其葡萄糖选择氧化性能

采用硼氢化钠化学还原氯金酸的碱性溶液制备了纳米金溶胶, 利用紫外-可见吸收光谱研究了金与壳聚糖的相互作用. 结果表明, 壳聚糖能够捕获金纳米粒子并易于形成金@壳聚糖复合材料. 利用X-光粉末衍射(XRD)、紫外-可见漫反射光谱(UV-vis DRS)、透射电镜(TEM)、红外光谱(IR)、微分热重及差热分析(DTG-DTA)等对这种复合材料进行了表征, 发现该材料具有较小的金纳米粒子, 壳聚糖的存在改变了金纳米粒子的等离子共振吸收, 二者之间存在一定的键合作用. 以分子氧为氧化剂, 在温和条件下, 该材料对葡萄糖选择氧化制葡萄糖酸反应具有良好的催化性能.     

纳米金的绿色合成与CTAB对金纳米聚集体的解聚集作用

室温下利用鞣酸(TA)既作还原剂又作保护剂,通过绿色还原方法制备了鞣酸包裹的金纳米粒子,并通过紫外可见光谱(UV-Vis)、透射电镜(TEM)、X射线衍射(XRD)、红外光谱(FTIR)等分别进行了表征和分析。结果表明,随着nTA/nHAuCl4比率的增加,紫外可见光谱显示鞣酸稳定的金溶胶最大吸收波长明显增大且吸收带变宽,而最大吸光率逐渐减小。TEM观察证实增加鞣酸用量会导致溶胶体系中花状金纳米聚集体的形成。实验发现,阳离子型表面活性剂十六烷基三甲基溴化铵(CTAB)对鞣酸保护的金纳米聚集体具有强烈的解聚集作用,在剧烈搅拌的条件下CTAB能使金纳米聚集体成功解聚为单分散状态的金纳米粒子,提高体系温度可明显促进CTAB对金纳米聚集体的解聚集作用。     

pH敏感的金纳米颗粒的制备及表征

利用立方硅氧烷(odaaps)作为保护剂合成了金纳米颗粒,利用紫外-可见(UV-vis)吸收光谱、透射电镜(TEM)对纳米颗粒进行了表征。通过改变纳米溶胶的pH值,从而改变立方硅氧烷上羧基的存在形式,控制纳米颗粒表面的电荷,实现金纳米颗粒的可逆聚集与分散;当将其pH值降低至2.5时,颗粒能够完全沉淀,加碱调节其pH与原始值(pH=9)一致时,聚集的颗粒会自动重新分散形成溶胶,其具有与起始一致的高分散性。     

藤茶干粉提取液还原制备金纳米粒子

用藤茶干粉提取液生物还原氯金酸溶液实现了金纳米粒子绿色制备,通过紫外-可见分光光度计、透射电子显微镜和粒度分布等技术手段对金纳米粒子形态等物性进行了表征,运用控制变量法探究了金纳米粒子生物合成的规律。研究发现,金纳米粒子的粒径、粒径分布、形状和稳定性受反应体系pH值、温度以及氯金酸的用量影响。pH6.47或藤茶干粉提取液过量时会引起纳米金的团聚;温度升高,金纳米粒子平均粒径会减小。通过变量控制,可以实现金纳米粒子绿色合成的有效控制。     

丝素蛋白质原位还原制备纳米贵金属胶体及表征

室温下, 不加任何还原剂, 丝素蛋白质溶液可以原位还原贵金属前驱体制备纳米贵金属胶体, 用光谱法研究了还原反应机理以及pH和反应物摩尔比对反应的影响, 用FT-IR, TEM, AFM对所得溶胶结构作了表征. TEM照片显示丝素-金溶胶为新颖核-壳纳米结构的生物缀合物(bioconjugate), 丝素-银溶胶为十几个核-壳型结构的丝素-银纳米颗粒聚集成的簇状物. 金溶胶具有高度的分散性和稳定性, 而银溶胶相对而言较差.     

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.     

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.     

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.     

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.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.