汞离子荧光、比色传感器

基于主客体识别的汞离子比色、荧光传感器由于使用方法简单、灵敏度高、不需要昂贵仪器等优势,受到了越来越多的关注。本文综述了近年来汞离子比色和荧光传感器的研究进展。本文根据作用机理将汞离子比色、荧光传感器分成三类,即通过特殊反应识别汞离子的传感器,通过配位作用识别汞离子的传感器以及基于纳米材料的汞离子传感器。其中通过特殊反应识别的传感器根据具体反应类型又可分成汞离子诱导的罗丹明上的内酰胺环开环型、汞离子与含硫(硒)的受体发生脱硫(硒)反应使受体氧化或关环型、汞离子与受体发生加汞化反应型和汞离子使受体发生汞离子催化的化学反应型这四类。本文对这些类型的汞离子传感器从设计原理、识别性能和机理等方面进行了介绍,并展望了该领域的研究方向。     

铁基纳米材料功能化及对水中汞离子的去除

在水体重金属污染中,汞污染问题日益严峻,已成为全球性环境问题之一。近年来,纳米FeS_x、Fe₃O₄、Fe等铁基材料凭借优越的吸附性能以及比表面积优势,受到研究者的广泛关注。对铁基纳米材料进行稳定化、官能团改性之后可以增强纳米粒子的分散度,为汞离子提供更多的吸附点位,进一步加强对水中汞离子的去除效果。本文重点阐述了纳米FeS_x的稳定化、Fe₃O₄等铁基材料的巯基化（-SH）、氨基化（-NH₂）等功能化改性方法及对Hg的去除;总结了功能化铁基纳米材料对水中Hg的去除效果和影响因素;探究了功能化铁基纳米材料去除水中汞的机理;最后展望了铁基功能化纳米材料处理水体汞离子的发展方向。     

核酸功能化稀土基纳米材料在生物检测中的应用

体内一些生物分子和离子的水平通常与细胞、组织、器官等结构和功能的变化相关,从而直接影响到疾病的预防、诊断和治疗,因此对体内这些物质的生物检测在医疗和健康领域具有重要的意义.基于稀土基纳米材料构建的纳米荧光探针具有灵敏度高、简单高效、抗干扰能力强等优点,在生物检测方面具有巨大的潜力.对稀土基纳米材料的核酸功能化能够进一步为纳米荧光探针提供更好的特异性识别能力和生物相容性,从而增强其在复杂样品中的生物检测能力.本综述总结了核酸功能化的稀土基纳米材料作为纳米荧光探针在生物检测领域的研究进展,简要介绍了其主要种类和性能、检测机理及检测物质,最后对该领域面临的挑战及未来的发展方向进行了展望.     

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。     

纳米比色化学传感器的设计及其在生物分子检测中的应用

<正>近年来,人们一直致力于制作能够在复杂实际样品中高灵敏度和选择性地检测被测物种的比色型光化学传感器.具备高选择性和灵敏度的比色型传感器的研究已经成为目前传感器领域的研究热点.纳米科技爆炸式的发展为优化比色型化学传感器的性能提供了可能.本论文基于对比色型光化学传感器的充分认识,和对纳米材料在构建比色型传感器     

LDHs薄膜基纳米荧光传感器的制备及其研究进展

层状复合氢氧化物(LDHs)是一种层板金属元素和层间离子可调的无机层状材料,利用其独特的插层组装特性,基于静电、氢键、范德华力等相互作用力,功能性荧光客体分子可与LDHs纳米片复合构筑多功能荧光薄膜材料.LDHs薄膜基荧光材料用于荧光传感器,在有机挥发性气体(VOCs)、温度、压力、重要生物分子等的检测中显示了良好性能.本文总结了LDHs复合薄膜的制备方法以及近年来其在纳米荧光传感领域的进展,并对其未来发展做出了展望.     

基于纳米石墨和单链脱氧核糖核酸混合物的荧光传感器对溶液中汞离子的检测

利用纳米石墨、单链脱氧核糖核酸开发了一个新型的荧光生物传感器并使用脱氧核糖核酸酶作为信号放大器对溶液中的汞离子进行检测。在最佳实验条件下,这种新型荧光生物传感器对汞离子的检出限达到0.5 nmol/L,比传统未经信号放大的传感器低20倍。得益于汞离子(Hg~(2+))可以结合两个胸腺嘧啶碱基(T)形成强力且稳定的T-Hg~(2+)-T复合结构(T-Hg~(2+)-T)的作用,该传感器对汞离子有着出色的选择性。此新型荧光生物传感器有望成为未来检测其他金属离子和生物分子的新工具。     

基于金属纳米簇的荧光传感平台的最新研究进展

荧光纳米生物传感平台由于具有灵敏度高、选择性好、操作简单、成本低、实时监测等特点,吸引了广泛的关注。近年来,随着纳米技术的飞速发展,具有纳米结构的材料(纳米材料)在生物传感领域显示出独特的优势。与传统材料相比,纳米材料显示出独特的物化性质,如光学、电学、机械、催化和磁性等。金属(如Au、Ag、Cu及其合金)纳米簇(MNCs)是纳米科学和纳米技术领域中一种新颖的多功能纳米材料,其通常由几个到几十个金属原子组成,其核的尺寸通常小于2 nm。由于其发光能力强、易于合成和进行表面功能化、生物相容性好、尺寸超小、毒性低等优点,金属纳米簇在能源催化、医学诊断、电子器件、生物传感等领域得到了广泛的应用。此外,金属纳米簇的荧光性能极佳(如大的斯托克斯位移、可调节的荧光、高的光学稳定性和荧光量子产率等),因此被作为荧光纳米探针广泛应用于生物传感领域。该综述介绍了近年来基于不同构建机制的金属纳米簇基的传感平台的研究进展,及其在检测离子、生物分子、pH和温度传感等方面的应用。相信该综述能为从不同传感机理构建更具前景的生物传感器提供一些新见解和理论指导。     

基于T-T碱基错配的荧光传感器特异性检测汞离子

在本文中,我们研制了一种基于T-T碱基错配特异性键合汞离子的荧光传感器用于汞离子的检测。该传感器由两条分别标记了荧光基团（F）和淬灭基团（Q）的DNA探针组成,并且含有两对用于结合汞离子的T-T错配碱基。当汞离子存在时,两条探针之间形成T-Hg2+-T结构,作用力增强,从而拉近了荧光基团与淬灭基团之间的距离,发生能量转移,使荧光信号在一定程度上被淬灭。在优化的条件下,我们使用该传感器对汞离子进行检测,动力学响应范围为50nM到1000nM,线性相关方程为y= 5281.13 - 1650.56 lg[Hg2+] ( R2 = 0.985),检测下限为79nM。此外,我们还考察了该传感器的选择性,当用其它干扰离子（浓度都为1.0µM）代替待测离子进行实验时,没有发生明显的荧光淬灭,说明该传感器具有较高的选择性。该传感器的构建为汞离子的检测提供了一条快速、简便的新途径。     

基于纸基的荧光碳量子点传感器的可视化检测研究进展

碳量子点作为一种新型的纳米材料,其独特的荧光性能使其在物质检测领域得到了越来越多的关注。利用碳量子点与物质反应导致荧光强度发生变化的特性,可将其应用于可视化检测,检测方法分为荧光猝灭型和荧光恢复型。基于纸基的荧光传感器与基于液相反应的荧光检测相比,其快速、现场和可视化的特点更加突出,因此有着更为广泛的应用。本文针对碳量子点的荧光特性、可视化荧光检测、纸基传感器的研究现状,并结合本课题组相关研究进展进行论述,以期为今后纸基碳量子点荧光传感器的研究和应用提供参考。     

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.     

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.     

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.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.