电化学DNA生物传感器研究的应用进展*

电化学DNA生物传感器因快速、灵敏、低耗和易于操作等优点在基因序列测定中受到了广泛的关注,已逐渐成为分子生物学和生物技术研究的重要领域。具有电活性的小分子和纳米材料因它们独特的性质,已被应用到电化学DNA生物传感器中。本文介绍了电化学DNA生物传感器的基本概念和分类,综述了近年来电活性小分子和纳米材料在电化学DNA生物传感器中的应用进展,并对此领域的未来发展做了展望。     

基于功能纳米材料的灵敏生物传感策略

21世纪的第一个十年被称为＂传感的十载＂.功能纳米材料为灵敏的生物传感器件（包括光学和电生物传感）的制备提供了优秀的平台.这方面的大多数工作主要聚焦于不同纳米材料的生物功能化,例如金属纳米粒子、半导体纳米粒子和碳纳米粒子,功能化方式包括物理吸附、静电结合、特异性识别或共价键合.这些生物功能化纳米材料可以用作催化剂、电导体、光发射剂、载体或示踪剂,以获取被放大的检测信号、稳定的识别探针或生物传感界面.设计的信号放大策略已经极大地促进了不同领域中稳定、特异、具有选择性和灵敏的生物传感器的发展.本文介绍了基于功能纳米材料的一些生物传感新原理和检测新策略,也讨论了纳米材料的生物功能化方法和生物传感在蛋白质的免疫分析、DNA检测、糖分析和细胞传感中的应用.     

纳米材料在电化学生物传感器及生物电分析领域中的应用

纳米尺度上的生物分析化学是当今国际生物分析领域研究的前沿和热点.该文阐述了纳米粒子在电化学免疫传感器及电化学DNA传感器领域的应用,着重介绍了以纳米材料为载体设计新型的具有生物分子识别和电信号增强作用的纳米标记粒子在构建高灵敏电化学生物传感器以及多组分同时检测中的应用.     

荧光纳米材料在病原微生物检测中的应用

病原菌污染给人类的健康带来极大的安全隐患,对病原菌快速、准确和灵敏的检测是减少污染的重要手段。传统检测病原菌的方法存在耗时长和操作繁琐等缺点。荧光纳米材料具有荧光强度高、稳定性好以及良好的生物相容性等优势,为应用其构造传感器用于病原菌检测提供了新的研究途径。本文对近年来常见荧光纳米材料,包括半导体量子点、金属纳米簇、碳纳米材料、上转换纳米粒子和荧光硅纳米颗粒,在病原菌检测方面的应用进行了概述,着重将不同类别荧光纳米材料的光学性质和检测机理进行了分析和比较。纳米材料的生物修饰是实现病原菌特异性识别的重要环节,本文对抗体、适配体、噬菌体和抗生素等病原菌识别方式的特点及其与纳米材料的连接方式进行了介绍。最后对不同荧光纳米材料在检测病原菌中具有的优势和局限性进行了总结,并对其在未来的应用与研究重点进行了展望。     

新型碳纳米材料——石墨烯及其衍生物在生物传感器中的应用

纳米生物检测是目前纳米科学、生物化学及诊断技术相结合的新的重要研究方向。石墨烯由于具有优良的电子、光学、热学、化学和机械性质,使其具有构筑探针分子和信号传递并放大的三重作用,成为应用于超灵敏生物传感器的理想材料。快速的电子传递和可多重修饰的化学性质使其能够实现准确而高选择性的生物分子检测。石墨烯及其复合材料越来越多地被应用到生物传感器的制备中。本文综述了近几年石墨烯及其衍生物在生物传感器研究中的进展,包括修饰石墨烯的各种材料、多种生物活性物质在石墨烯表面的直接电子转移和石墨烯在酶传感器、免疫传感器、基因传感器以及一些生物小分子的检测等方面的研究。     

生物传感器在POCT中的应用研究

即时检测（POCT）是在病人旁边或现场进行的检测,因其简单、快速、便携且不受场所限制已成为目前体外分子诊断技术发展的一支风向标。而生物传感器以其快速、灵敏、高效、便携及易于自动化、微型化等优点在发展现场即时检测技术中具有非常大的潜力。近年来,随着生物传感技术、互联网技术的发展及各种新技术、新方法的兴起和融合,POCT技术和方法得到了实质性发展。本文简要介绍了生物传感器的分类和生物传感器在POCT中的应用现状,综述了近年来各类生物传感器在面向POCT检测应用的研究进展。生物传感器根据类型主要分为基于微流控芯片的生物传感器、基于纸的生物传感器、基于纳米材料的生物传感器、基于手机检测平台的生物传感器及集成的生物传感器等,并对这些传感器平台在POCT检测方面的应用做了阐述,最后对生物传感器在POCT应用中存在的问题进行了讨论,并对其发展趋势及前景做了展望。     

基于新型纳米传感材料的DNA生物传感器的应用

DNA是构建纳米技术和生物传感技术新设备的良好构建体。DNA生物传感器由于具有灵敏度高、选择性好等特点,近年来获得了飞速发展。研究发现,金属纳米粒子(MNPs)、碳基纳米材料等一系列纳米材料在传感器设计中提高了电化学DNA传感器的传感性能。本文侧重介绍了场效应晶体管、石墨烯、碳纳米管等新型纳米传感材料,以及基于这些材料的DNA生物传感器的最新进展,最后展望了DNA生物传感器的应用前景。     

基于纳米材料的电化学免疫传感器在传染性病原体POCT中的应用

传染性病原体POCT对于及时有效控制传染病尤为关键。相比于传统检测方法,基于电化学免疫传感器的传染性病原体检测具有快速、灵敏、准确、易于小型化和集成化等优势,尤其适用于传染病POCT。新兴的纳米材料因其独特的理化性质可用于修饰传感器界面或作为生物分子的固载基质以及信号标记物等,有助于构建出高选择性和高灵敏度的电化学免疫传感器。在本文中,我们着重阐述了不同结构的纳米材料修饰的电化学免疫传感器在传染性病原体POCT检测中的应用,进一步介绍了基于纳米材料的电化学免疫传感器与不同检测技术联用在传染性病原体POCT中的应用,并对其发展前景做出了展望。     

酶标记的电化学DNA传感器

对特异DNA序列的检测,在基因相关疾病的诊断、军事反恐和环境监测等方面均具有非常重要的意义.DNA传感器的研究就是为了满足对特异DNA序列的快速、便捷、高灵敏度和高选择性检测的需要.近年来涌现出多种传感策略,根据其检测方法大致可以分为光学传感器、电化学传感器和声学传感器等.由于电化学检测方法本身所具有的灵敏、快速、低成本和低能耗等特点,电化学DNA传感器已成为一个非常活跃的研究领域并得到了快速发展.     

纳米电化学生物传感器

纳米电化学生物传感器是将纳米材料作为一种新型的生物传感介质,与特异性分子识别物质如酶、抗原/抗体、DNA等相结合,并以电化学信号为检测信号的分析器件。本文简要介绍了生物传感器的分类和纳米材料在电化学生物传感器中的应用及其优势,综述了近年来各类纳米电化学生物传感器在生物检测方面的研究进展,包括纳米颗粒生物传感器,纳米管、纳米棒、纳米纤维与纳米线生物传感器,以及纳米片与纳米阵列生物传感器等。     

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.     

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.     

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.     

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%).