应用于基因分析的最新SERS技术*

表面增强拉曼散射（SERS）是一种基于拉曼散射原理识别生物及化学分子的分析方法。SERS具有灵敏度高、水干扰小、分辨率高、稳定性好等优点,广泛应用于生物分析和生物医学研究领域。近年来,SERS技术在基因分析领域得到迅速的发展,成为国内外研究的热点。本文对应用于基因分析的一些最新SERS技术（包括基因的免标记检测和标记检测）进行较为全面的综述,着重介绍了免标记检测中基于金属纳米粒子和针尖增强拉曼散射的SERS技术,标记检测中基于拉曼活性物、PCR技术、分子信标、基底和标记物的SERS信号放大技术,并概括了基因多组分检测技术及SERS技术的应用前景。     

SERS生物传感技术及其应用进展

表面增强拉曼散射(SERS)生物传感技术是以生物成分为敏感元件或探测对象,研究生物分子间相互作用的重要工具之一,被广泛应用于环境监测、食品安全、临床检验及疾病诊断等众多领域.本文总结了耦合增强SERS生物传感技术方面的进展及其在分析检测和癌症诊断方面的应用.主要包括基于耦合增强SERS生物传感技术方法、高灵敏度的SERS传感芯片的制备及其应用和新型SERS技术研究癌细胞及组织.     

适配体生物传感器在病原微生物检测中的应用

适配体是通过指数富集系统进化技术(SELEX)体外筛选得到的一类能够特异性地结合小分子物质、蛋白,甚至整个细胞的寡核苷酸序列.由于具有制备简便、易于修饰、稳定性好等特点,适配体已广泛应用于构建生物传感器,实现对病原微生物的识别和检测.本文在阐述适配体基本原理的基础之上,结合近年来病原微生物适配体研究领域的最新研究成果,综述以病原微生物为目标的适配体筛选技术的最新进展;列举目前已经筛选获得的病原微生物(原生生物、病毒、细菌)适配体;综述适配体生物传感器在病原微生物检测中的应用.并展望了适配体生物传感器在病原微生物检测领域的发展趋势.     

基于SERS探针技术的细胞识别、成像与诊疗

表面增强拉曼散射(surface-enhanced Raman scattering, SERS),是指吸附在粗糙的金属纳米结构表面的被分析物,在光照射下其拉曼光谱获得显著增强的异常表面光学现象。近年来,SERS技术已广泛地用于物质检测和生物传感等研究,在生物医学领域表现出巨大的应用潜力并取得了令人瞩目的研究成果。本文回顾了SERS探针技术在细胞识别、成像与诊疗等方面的应用及最新研究进展,重点介绍了SERS细胞探针的构建方法与原理,以及基于SERS探针的细胞检测应用策略,并讨论了SERS探针技术在细胞检测中仍有待解决的关键问题。     

生物大分子印迹聚合物研究进展及其应用

介绍了生物大分子印迹技术及其印迹聚合物的研究进展,其中包括对蛋白质、核酸、微生物细胞进行分子印迹所采用的印迹方法、机理以及存在的问题,最后简要探讨了生物大分子印迹聚合物在医学研究中的应用前景。     

原位冷冻电子断层扫描的发展及在生物研究方面的应用

对生物大分子复合物的研究和结构分析对于全面了解其功能和生物学意义至关重要. 冷冻电子显微镜在提供生物大分子结构及大分子分布等方面起到重要的作用. 近年来, 冷冻电子显微镜的硬件和软件的发展进一步提高了冷冻电子显微镜的有效性, 使其对各种生物结构、 蛋白质结构的解析更加准确快捷. 但是, 对于生物系统来说, 蛋白质和大分子复合物等均处于复杂的生理环境中, 因此原位检测生物分子的三维结构对于生物体系和结构生物学具有重要意义. 冷冻电子断层扫描作为一种功能强大的技术, 可以无需标记直接通过冷冻样品的固有衬度识别生物大分子的结构, 并且可在原位生理环境中对生物分子进行纳米级分辨率的三维成像. 本文综述了与冷冻电子断层扫描相关的样品制备和数据处理技术, 并总结了冷冻电子断层扫描技术在分离的大分子复合物和整个细胞或组织中的生物学应用.     

核酸适配体功能化的稀土上转换纳米材料在生物检测中的应用

稀土上转换纳米材料可以吸收近红外光并发射出可见光或紫外光,在生物传感领域得到了广泛研究。核酸适配体能高特异性和高亲和性地与靶标物结合,被广泛应用于生物传感、疾病诊断等领域。将稀土上转换纳米材料与核酸适配体结合构建的检测体系,可实现对目标物灵敏、高选择性的检测。本文介绍了近几年核酸适配体功能化的稀土上转换纳米材料在生物小分子、蛋白质、核酸、病原微生物、细胞等方面的应用,并展望了其在分析检测领域的发展前景。     

Au@4-硝基苯硫酚@Ag@牛血清白蛋白内标化表面增强拉曼散射探针的制备及其在细胞拉曼成像中的应用

制备了Au@4-硝基苯硫酚@Ag内标化表面增强拉曼散射（SERS）探针,进一步以牛血清白蛋白（BSA）置换探针表面的稳定剂十六烷基三甲基溴化铵（CTAB）,发展了Au@NT@Ag@BSA内标化SERS探针。Au@NT@Ag@BSA探针保留了原探针的单分散性和高灵敏度,同时显著提高了信号稳定性和生物相容性。进一步将Au@NT@Ag@BSA探针和SMMC7721肺癌细胞共孵育,实现了细胞的探针标记和拉曼光谱成像。Au@NT@Ag@BSA内标化SERS探针在活体生物成像等方面展示了良好的应用潜力。     

生物大分子印迹传感器研究进展

分子印迹传感器在有机小分子分析检测方面的应用已趋近成熟,在生物大分子检测方面的应用近年来也逐渐增多.本文就近年来分子印迹技术在大分子生物传感器中的构建及应用进行综述,包括光学传感器、电化学传感器、质量型传感器等,并对目前分子印迹传感器在生物大分子检测方面存在的问题进行分析,对生物大分子印迹传感器的未来发展方向提出展望.     

基于量子点标记的适配体技术在分析检测中的研究进展

由于光学性质独特,量子点成为近年来发展起来的极具应用前景的半导体纳米材料,作为荧光标记物在生物和化学领域备受关注。随着生物技术的发展,适配体以其高特异性、强亲和力等特点被用作生物探针或生物传感元件,在分析检测中得到广泛应用。将量子点与适配体结合构建的纳米生物识别体系,互补结合适配体和量子点的特殊性质,可实现对靶标物质的超灵敏、高选择性及快速检测。本文概述了量子点的合成、修饰及其与适配体的偶联,重点介绍了近几年基于量子点标记的适配体技术在生物分子、病原微生物、细胞、真菌毒素等方面的应用,并展望了该技术在分析检测领域的发展趋势。     

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.