微孔尼龙-6膜的催化水解改性和DNA芯片的原位合成

基因芯片常用的载体有玻璃片、硅片、聚丙烯膜、硝酸纤维膜和尼龙膜等[1～ 4 ] .其中有机高分子膜载体由于自身荧光背景较强 ,寡核苷酸探针或 c DNA片段通常用点样法固定 ,并以同位素标记的靶基因与其杂交 ,用放射显影进行检测 ,探针密度不高且损害人体健康 .生物分子纳米标记和时间分辨荧光等检测技术可以非常有效地克服载体荧光背景[5,6 ] .因此 ,若将高分子材料进行改性 ,使其表面带有羟基、氨基和巯基等活性基团并应用于 DNA的原位合成 ,再结合新开发的生物分子标记和检测方法 ,将拓展生物芯片基材选择范围 ,并开发出新的生物芯片制…     

PDMS微芯片吸附牛血清白蛋白的研究

材料表面的物理和化学性质对蛋白质的吸附具有很大的影响[1].对蛋白质吸附的研究是研制生物传感器、生物芯片和生物材料的基础.     

一维生物芯片蛋白质检测技术平台

本文提出和构建了一种新型的生物芯片平台技术,这种芯片平台技术将微流控芯片[1～3]与基于高通量并行分析方法的生物芯片[4]原理相结合,发展成基于微流控串行分析技术的一维生物芯片.这种芯片设计的优势在于不仅试样用量极微,自动化程度高,不易污染,而且有望在"芯片实验室"上实现将单细胞水平上的基因、蛋白表达谱分析.     

5,7,9-桃柘三烯类化合物的合成研究

生物标志物[1] 最初来自于生物体 ,是由碳、氢和其他元素组成的复杂有机化合物。它们存在于页岩、沉积物和原油中 ,与生物体的母体有机分子结构差别很小或基本没有差别。由于其复杂的结构能提供许多成因和地质历史的有用信息。Ｇａｌｌｅｇｏｓ[2 ] 研究格林河页岩时 ,提取许多单芳三环二萜类化合物 ,认为这类化合物是由三环和五环萜类或甾类经过断裂及芳构化作用而形成的。这类化合物的结构在地质样品中经ＧＣ ＭＳ和计算机检索而推测出来。本文合成的标准样品与其地质样品的质谱图基本吻合[3 ] ,同时为进一步研究页岩地质环境、成因和历史…     

提高MALDI-MS测量溶菌酶分子量灵敏度的研究

近 1 0年来 ,基质辅助激光解吸质谱 (MALDI- MS)作为一种新兴的“软电离”质谱技术 [1,2 ] ,已很快地应用于生物大分子特别是蛋白质研究领域 [3 ] .MALDI- MS可在 1 0 - 12 mol甚至 1 0 - 15mol的水平上 ,准确地测定分子量高达几万到几十万的生物大分子 ;还可通过改变基质、溶液条件和样品的制备方法等实现大分子蛋白质非共价复合物的质谱检测 [4 ] .MALDI- MS能够得到如此广泛的应用 ,在很大程度上要归功于基质的辅助效应 .基质的作用主要可以概括如下 [5～ 7] :(1 )削弱样品分子间的相互作用 ;(2 )与样品分子结合并使之快速结晶 …     

利用DPN技术直接构建磁性纳米图形

在纳米尺度下构建有序的磁性模板和图形是当前的研究热点之一 [1,2 ] .这种模板在生物样品的分离[1] 、磁电子学研究和信息存储 [2 ] 等领域具有重要意义 .目前 ,光刻 [3] 、微触点印刷 [4 ] 和自组装 [5] 等多项技术已被用来构建各种纳米模板 .1 999年 ,美国西北大学 Mirkin小组 [6 ]发明的 Dip- pen纳米刻蚀技术 (简称 DPN技术 )更在可控组装方面显示出巨大优越性 .这项技术是在一定驱动力作用下 ,使吸附在原子力显微镜 ( AFM)针尖上的分子“墨水”逐渐转移到基底表面上 ,实现纳米模板的可控构建 .与传统技术相比 ,DPN技术可在纳米尺…     

基于微流控芯片电泳的生物分子间相互作用研究*

用合适的手段表征生物分子的相互作用对于深刻理解生命过程的本质以及进行医药开发都具有重要意义。将微流控芯片和毛细管电泳相结合的微流控芯片电泳技术具有快速、高效、高通量、样品用量少和易于整合等诸多优势。本文对近年来进行生物分子间相互作用结合常数测定以及结合动力学研究的微流控芯片电泳分离模式、分析方法和芯片检测方法分别做了介绍;简单对比了微流控芯片技术和微阵列生物芯片生物分子间相互作用研究技术;最后分析了微流控芯片技术目前的不足,并对其未来的发展进行了展望。     

Dip-pen刻蚀技术直接制造蛋白质纳米阵列

美国西北大学 Mirkin等 [1～ 3] 发明的 Dip- pen( DPN,译为蘸水笔技术 )纳米刻蚀技术是以 SPM的针尖为笔 ,通过超分子相互作用使被书写的分子或纳米材料粘在针尖上 ,以某种材料为基底 ,通过合理的超分子相互作用的设计将针尖上的分子或纳米材料书写到基底上 ,从而实现纳米刻蚀和纳米制造的目的 .很显然 ,这种技术对纳米器件、纳米传感器、高密度存储以及生物芯片的制造具有重要意义[4～ 7] .近年来 ,Mirkin研究组和其他几个研究集体利用这种技术成功地制造了有机分子纳米图形与阵列 [8] ;无机氧化物 [9]、金属纳米粒子 [10 ,11]、高分…     

镍邻菲绕啉对DNA固定作用的原子力显微镜表征

原子力显微镜 ( AFM)自 1 986年发明以来得到了广泛的应用和发展 [1,2 ] ,成为众多研究领域中的强有力工具 ,并为其它的研究技术提供了良好的互补手段 .DNA是 AFM首次研究的生物样品之一 ,它使人类首次观察到 DNA分子的原始形貌 ,并实现了接近生理条件下的操作 ,使得随时监测生物大分子的生化反应过程成为现实 [3,4 ] .在 DNA的 AFM研究中 ,样品的制备是其关键 .以阳离子 (如 Mg2 + ,Ba2 + ,Mn2 +和 Ca2 +等 [5] )固定法较为常见 ,其操作简单 ,固定效果好 ,基底效应小 ,但也有一定的局限性 ,如存在限制性内切酶时 ,这些简单离子会…     

XRD物相定量分析外标法标准曲线库的建立

X射线衍射(XRD)物相定量分析已被广泛应用于材料科学与工程的研究中。XRD物相定量分析方法有内标法[1-2]、外标法[3]、绝热法[4]、增量法[5]、无标样法[6]、基体冲洗法[7]和全谱拟合法[8]等。内标法、绝热法和增量法等都需要在待测样品中加入参考标相并绘制工作曲线,如果样品含     

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.     

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.     

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.     

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.     

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.