高灵敏共轭聚合物化学传感器

金属离子和化学小分子的检测在人类健康、环境污染以及食品安全等领域具有重要意义,科学工作者们已经在设计、发展高灵敏化学传感器方面进行了大量研究。在过去的几十年里,共轭聚合物由于其卓越的光电性质,引起了人们极大的关注,并取得了众多革命性科技进展。最近,利用共轭聚合物的荧光信号放大机制,人们设计、发展了一系列新型的化学和生物传感体系。共轭聚合物的信号传感机制包括电子转移,荧光共振能量转移以及共轭聚合物聚集或构象改变。本文主要介绍我们实验室在利用共轭聚合物实现金属离子和化学小分子荧光检测方面取得的进展,并对未来发展方向与面临的挑战进行了讨论。     

水溶性聚芴衍生物的合成、性质与生物检测应用

共轭聚合物具有强的光捕获能力,可用来放大荧光传感信号,大大提高检测的灵敏度.基于共轭聚合物的新型生物传感体系对于阐明生物体系中的信息传递,特别是对疾病的早期诊断方面具有重要的应用前景.水溶性聚芴衍生物由于具有很好的化学和热稳定性、高的荧光量子产率以及C9位易于修饰等特性,近年来在生物传感领域得到了广泛应用.本文简要介绍...     

荧光共轭聚合物在生物大分子检测中的应用*

共轭聚合物因其具有π-电子体系及共轭离域结构,一般都具有优异的发光性能,其发光强度和发射波长会随被检测化合物结构的不同而发生特异性响应,特别是在与被检测物相互作用过程中所产生电荷和能量能够沿共轭分子链进行有效传递,成倍放大这种作用,从而有效提高了检测灵敏度,这比相应的小分子化合物更具有优越性。目前共轭聚合物已被用于开发新型化学、生物传感器,尤其是在生物分子检测方面的应用得到迅速的发展。本文总结了近年来荧光共轭聚合物在生物传感方面的研究进展,主要讨论共轭聚合物在蛋白质、核酸及毒素检测中的应用。     

共轭聚合物荧光传感器的研究进展

共轭聚合物具有共轭分子导线结构,局部微扰在整个聚合物分子链甚至整个聚合物体系内即能得到放大利用,这一性质决定了其具有检测超低含量待测物的能力,且表现出强于小分子荧光传感器的灵敏度.本文概述了荧光共轭聚合物的传感机理,并举例介绍了近年报道的以共轭聚合物为基础的荧光传感器在检测离子及有机小分子方面的应用.     

共轭聚合物为基础的荧光传感器

近年来,借助共轭聚合物的荧光发射与淬灭过程开发化学与生物传感技术成为倍受关注并获得迅速发展的研究领域。由于共轭聚合物能够沿分子链进行能量和电荷传导,从而产生信号放大现象,这类传感器通常都具有较高的灵敏度。本文主要通过对几种具有代表性的此类化学/生物传感器的举例说明,概述荧光共轭聚合物的传感机理,并简要介绍这一领域的发展状况。     

基于共轭聚合物的核酸生物传感器的应用

共轭聚合物的π电子体系及共轭离域结构,使其具有良好的发光性能。聚合物链可充当“分子导线”,能够成倍放大光学信号,从而有效提高检测灵敏度。而核酸适体(aptamer)在特异性、与靶物质亲合力、信号传导方面比其他识别元件具有更大的优势,因此共轭聚合物的核酸生物传感器在生物检测方面得到了迅速发展。本文主要总结了近年来共轭聚合物的核酸生物传感器在生物检测方面的应用,并进一步对该类型传感器的发展趋势作出了展望。     

基于共轭聚合物的传感器荧光发射红移的策略:pH响应和酶活性检测中的应用

近年来,共轭聚合物(CPs)由于具有独特的光电特性而备受关注。CPs由大量重复的共轭单元组成,相对于小分子,它具有长程π电子共轭、强吸光能力、能带可调以及结构修饰多样性等特点。共轭聚合物受激发后,其能量可沿着分子主链快速迁移到一个受体分子,使受体分子的荧光信号成倍的增加,从而可以提高检测的灵敏度。国内外多个研究组利用CPs的传感信号放大效应设计了一系列高选择性和高灵敏性的生物传感器和化学传感器,用来检测DNA,RNA,     

水溶性聚噻吩的合成与可视化生物检测

共轭聚合物具有强的光捕获能力,可放大荧光传感信号,提高生物检测的灵敏度。基于共轭聚合物的新型生物传感体系对获取生命过程中的化学与生物信息、阐明生物体系中的信息传递、特别是对疾病的诊断与治疗都具有重要的意义。水溶性聚噻吩衍生物在外界环境影响下主链结构易发生变化,从而引起紫外吸收光谱与溶液颜色的变化,近年来在可视化生物检测...     

NEWS

近年来,水溶性共轭聚合物(WSCPs)以其独特的光电性质,在核酸、蛋白质和离子检测方面的研究备受关注。相对于单个小分子而言,共轭聚合物具有多个吸收单元,因此具有很强的吸光能力,在参与能量转移的过程中,可大幅放大响应信号,提高检测灵敏度。荧光共振能量转移(FRET)作为常用的技术手段,在生物大分子相互作用分析、细胞生理     

基于水溶性共轭聚合物及FRET检测腺苷脱氨酶

近年来,水溶性共轭聚合物( WSCPs)以其独特的光电性质,在核酸、蛋白质和离子检测方面的研究备受关注。相对于单个小分子而言,共轭聚合物具有多个吸收单元,因此具有很强的吸光能力,在参与能量转移的过程中,可大幅放大响应信号,提高检测灵敏度。荧光共振能量转移( FRET)作为常用的技术手段,在生物大分子相互作用分析、细胞生理研究、免疫分析等方面有着广泛应用。     

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.     

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.     

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.     

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.     

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.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.