基于多肽识别的电化学生物传感技术

多肽具有分子量小、易于合成、生物兼容性好、稳定性高及序列灵活多样等优点。因此,多肽作为新型生物识别元件,已被广泛应用于生物传感器的构建。电化学分析灵敏度高、准确度好、设备简单、检测范围广且易于操作。本文介绍了基于多肽识别的电化学生物传感器技术,包括多肽的修饰与固定化、多肽与待测物的识别及检测原理;综述了近五年多肽电化学生物传感器对重金属离子、小分子、蛋白质、细菌和病毒的检测;展望了肽基电化学生物传感器的发展趋势。     

基于纳米材料自组装的传感器在生化分析中的应用研究进展

纳米材料可以通过自组装技术可控地形成具有不同空间结构的材料,该技术使其及其自组装体在多种生化物质（如蛋白质、多肽、DNA等）和金属离子的超灵敏检测中具有重要应用。本文对基于半导体量子点、贵金属纳米材料和碳基纳米材料自组装体系的传感器在生化分析中的应用进行了总结。     

功能核酸生物传感器检测金属离子的研究进展

功能核酸是具有特定结构和功能的天然或人工核酸序列。一些金属离子是人体必需的微量元素,但过量的金属离子会对人体健康带来危害。功能核酸具有易于修饰、价格低廉、稳定性高、特异性强等优点,被广泛应用于金属离子的检测。本文详细介绍了功能核酸与金属之间的相互作用,主要包括DNA/RNA切割型、连接型、错配型、点击化学型、构象改变型以及其它类型;以及功能核酸与不同信号输出方式相结合的生物传感器。最后讨论了功能核酸在金属离子检测过程中的优势以及现存的问题,对功能核酸生物传感器未来的发展方向以及应用前景进行了展望。     

生物纳米孔道技术在非基因测序方面的研究与应用

纳米孔道分析技术是一种低成本、快速、无需标记的单分子检测技术,仅有20多年的发展历史,在DNA单分子测序领域展示出较好的应用前景,现已有商业化的产品面世且趋于成熟.越来越多的研究表明,纳米孔可作为一个通用的单分子传感器.本文综述了生物纳米孔道分析技术对蛋白质、多肽和核酸等单个分子与孔道间相互作用、动力学和热力学过程的实时监测以及多种生物大分子和金属离子的定量检测等方面的研究进展.在纳米孔技术中,电化学检测系统也十分重要,本文还特别介绍了高带宽及超低电流分辨仪器和相关软件的相关进展.     

肽适体修饰纳米孔道对L-精氨酸的灵敏检测

氨基酸是生命之源,其中L-精氨酸(L-Arg)是生物体进行新陈代谢的一种重要氨基酸,同时也是重要的肿瘤标志物之一.因此，开发高选择性的L-Arg检测方法在生物分析领域十分重要.本文在Uniprot数据库29185个蛋白质序列中筛选出特异性结合L-Arg的多肽序列(序列为CFGHIHEGY),经ITC验证后,将其作为识别元件固定在子弹形纳米孔道尖端表面.在纳米空间限域效应下,利用多肽与L-Arg特异性结合前后构象由伸展状态向蜷缩状态的变化,调控纳米孔道离子输运特性变化,从而实现对L-Arg的选择性检测.实验结果表明,多肽修饰纳米孔道对L-Arg具有高灵敏度和高选择性,线性范围为1～100 nmol/L,检出限低至1 nmol/L.该研究为氨基酸高选择性、高灵敏检测提供了新方法,同时也为多肽修饰仿生离子通道的构建提供了新思路.     

基于热电材料的新型传感器研究进展

传感器作为现代智能工业的核心部件之一,凭借其优良的性能,越来越受到关注.本文总结了热电材料在传感器应用方面的研究成果,特别是硅基、碳基、铅基、碲基、贵金属类、有机类以及催化类的热电材料对传感器高灵敏度、高响应值、高稳定性等方面的影响.已有研究表明,通过在微米纳米尺度合成及加工所形成的低维微纳结构的热电材料,能够获得高ZT值和更高的热电性能.这一特性与传感器微型化方向发展一致.低维微纳结构的热电材料未来必将能够拓展传感器的特性和适用领域,促进传感器朝着高精尖模式的发展.     

基于桑蚕丝蛋白的多肽/两亲性多肽及其组装和功能化

多肽的自组装因其独特性质和作用已成为超分子化学、高分子功能材料和生物医用材料等领域的研究热点.桑蚕丝蛋白具有高度重复的多肽序列,其组装行为和相应的结构对动物丝及丝蛋白基材料的形成和特有的优异综合性能起到了至关重要的作用.通过特定的酶降解桑蚕丝蛋白能够以较为经济的方式获得多种明确序列的多肽,并可进一步方便地制备功能性的两亲性多肽.本文结合国内外多肽自组装的研究现状,对本课题组在桑蚕丝蛋白多肽/两亲性多肽的制备、组装以及功能化等方面的研究成果进行了总结,同时也展望了其在若干领域中的实际应用.     

光电化学传感器的研究进展

光电化学传感器以光作为激发源,以光电流或光电压作为检测信号,具有响应快速、灵敏度高、设备简单等特点,目前已在环境、食品、医学等多个领域的分析测试中得到广泛应用。该文阐述了光电转换材料与光电化学传感器的制备方法,介绍了光电化学传感器的原理和分类。光电化学传感器包含光寻址电位型传感器和电流型光电化学传感器,其中,电流型光电化学传感器由于优良的光电性能、检出限低、所需材料低廉且易加工等优势而被广泛应用。文中着重介绍了电流型光电化学传感器在金属离子、有机污染物、核酸、蛋白质、细胞等方面的应用,并对光电化学传感器的发展前景进行了展望。     

具有双活性序列的新型抗菌肽的设计及性质

设计合成了具有2个活性序列的线性和环状多肽及具有单个活性序列的短链多肽, 研究了它们的杀菌活性、 细胞毒性及溶血性. 结果表明, 线性肽和环状肽的杀菌活性高于短链肽. 利用计算模拟的方法计算了多肽与细菌细胞膜中一种重要的成分磷脂酰甘油(DMPG)的结合能. 结果表明, 多肽-DMPG的结合能与多肽的杀菌活性具有较高的相关性, 线性和环状多肽与DMPG的结合能大于短链肽. 线性和环状多肽均含有2个活性序列, 可提供多个荷正电氨基酸与荷负电的磷脂结合, 结合能较大, 杀菌活性较强. 采用模拟生物膜对其中几条多肽的作用机理进行了初步研究. 结果表明, 该类多肽有可能使正常哺乳动物细胞的细胞膜产生孔洞; 而对于细菌细胞膜, 多肽并未在膜上产生明显孔洞, 而是引起了细菌细胞膜的聚集.     

用于识别金属离子的超分子荧光/磷光传感器*

本文总结了近年来用于金属离子识别的超分子荧光/磷光传感器的研究工作进展,着重介绍了光诱导电子转移及单体-激基缔合物体系在金属离子识别中的应用.     

Gas phase hydrogen deuterium exchange reactions of a model peptide: FT-ICR and computational analyses of metal induced conformational mutations

We utilized gas phase hydrogen/deuterium (H/D) exchange reactions and ab initio calculations to investigate the complexation between a model peptide (Arg-Gly-AspRGD) with various alkali metal ions. The peptide conformation is drastically altered upon alkali metal ion complexation. The associated conformational changes depend on both the number and type of complexing alkali metal ions. Sodium has a smaller ionic diameter and prefers a multidentate interaction that involves all three amino acids of the peptide. Conversely, potassium and cesium form different types of complexes with the RGD. The [RGD + 2Cs − H]⁺ species exhibit the slowest H/D exchange reactivity (reaction rate constant of 6 × 10⁻¹³ cm³molecule⁻¹s⁻¹ for the fastest exchanging labile hydrogen with ND₃). The reaction rate constant of the protonated RGD is two orders of magnitude faster than that of the [RGD + 2Cs − H]⁺. Addition of the first cesium to the RGD reduces the H/D exchange reaction rate constant (i.e., D₀) by a factor of seven whereas sodium reduces this value by a factor of thirty. Conversely, addition of the second alkali metal ions has the opposite effect; the rate of D₀ disappearance for all [RGD + 2Met − H]⁺ species (MetNa, K, and Cs) decreases with the alkali metal ion size.     

Detection of metal ions using ion-channel sensor based on self-assembled monolayer of thioctic acid

Gold electrodes were chemically modified with thioctic acid monolayer designed to mimic biological ion-channel membranes. The technique was then used in the determination of alkali, alkaline earth, thallium(I), and lanthanum metal cations as analytes. Cyclic voltammograms (CV) of [Fe(CN)6]³⁻ an electroactive marker, were measured in the presence of the various types of analyte cations. In the absence of the analyte cation, electrostatic repulsion between the marker anions and the carboxylate groups of the receptor monolayer hindered the approach of the marker anion to the electrode surface and hence hindered its reduction. The modified electrodes responded well to the metal cations except the alkali metal cations. The sensors could detect the trivalent cation La³⁺ at concentrations as low as 10⁻⁸ M. The response of the sensor to the metal cations increase in the order alkali metal3+ can be discriminated in the ratio 1:100. This makes it possible to determine the trivalent ion in a sample matrix containing monovalent and divalent cations. Thallium(I) ion showed marked deviation in its response as compared to monovalent ions of the alkali metals. The ion-channel sensor based on self-assembled monolayer of thioctic acid therefore offers a potential alternative technique for the selective determination of metal ions.     

Bioremediation Process and Bioremoval Mechanism of Heavy Metal Ions inAcidic Mine Drainage

Acidic mine drainage(AMD) containing acidity and a broad range of heavy metal ions is classified as hazardous, and must be properly treated. The removal mechanism of heavy metal ions in acidic mine drainage contai- ning Cu²⁺, Fe²⁺, and Zn²⁺ with biological method was studied here. Using 20 mmol/L ethanol as carbon source, Desulfovibrio marrakechensis,one of sulfate reducing bacteria(SRB) species, grew best at 35 ℃ and pH=6.72 with concentrations of 10, 55 and 32 mg/L for Cu²⁺, Fe²⁺ and Zn²⁺, respectively. The removal efficiency for each ion mentioned above was 99.99%, 87.64% and 99.88%, respectively. The mineralogy and surface chemistry of precipitates were studied by means of energy dispersive spectrometer(EDS), X-ray photoelectron spectroscopy(XPS), X-ray diffraction(XRD) combined with control tests. The experimental results demonstrate that the removal mechanism of heavy metal ions by Desulfovibrio marrakechensis is comprehensive function of chemical precipitation, adsorption and bioprecipitation. The biogenic iron sulfide solid was characterized as greigite(Fe₃S₄), while the zinc sulfide solid was characterized as sphalerite(ZnS).     

基于有机物电极的电化学能量存储与转化

由于高安全的特性,水系二次电池被认为是未来大型储能的有效解决方案之一. 然而,现有水系电池主要以含金属元素的无机化合物为电极活性材料,其在大型储能中的实际应用仍受到循环寿命、环境问题、原料成本或金属元素丰度的限制. 相较于无机电极材料,部分有机电极材料具有原料丰富、结构丰富、可持续及环境友好等优点. 此外,有机物材料分子内空间大,能够存储不同价态电荷,因此近年来被广泛关注. 本文综述了课题组近期在有机物电极方面的研究进展,内容聚焦含羰基有机物通过C=O/C-O-的可逆转化存储单价金属阳离子(Li⁺, Na⁺)、双价金属阳离子(Zn²⁺)、质子(H⁺)所涉及的电化学过程,及其在水系锂、钠离子电池、水系锌离子电池、质子电池以及分步电解水中的应用.     

一种新的镧系金属有机骨架材料的合成、 结构及荧光检测性质

利用溶剂热方法合成了一种以Tb³⁺离子为中心的金属有机骨架材料［Tb₂(bpt)₂(H₂O)₂］·(DMA)_4.5, 并通过单晶X射线衍射(SXRD)、 粉末X射线衍射(PXRD)、 元素分析(EA)、 热重分析(TGA)、 傅里叶变换红外光谱 (FTIR)以及荧光光谱技术(FS)表征了该材料的结构与基本物理化学性质. 单晶衍射分析结果显示该材料具有包含一维直孔道的三维结构, 结构中孔道窗口尺寸约为1.23 nm×1.10 nm. 荧光分析测试结果表明该材料对Cr³⁺离子有荧光响应, 离子检测限低至0.22 mg/L, 同时具有良好的选择性, 在Cr³⁺离子的荧光检测领域具有重要的应用潜力.     

Synthesis and Characterization of a New Neutral Ionophore for Use in Bulk Optode

Chemical sensors based on optical signal detection are of increasing importance. Optical sensors of bulk optodes have the advantage of being robust and showing a highly reversible response explainable by means of the chemical equilibria involved. Therefore, a great number of new ion-selective bulk optodes have reported within a few years. Several sensors for detecting toxicologically revalant ions,such as Pb²⁺,Ag⁺,Hg²⁺ and UO₂²⁺ have been developed recently and exhibit the low detection limit required. Although a number of ionophores have been used in optodes and ISEs,the sensors described so far are inadequate for monitoring Ag⁺ in water, especially in drinking water because of their limited selectivity and/or insufficient sensitivity. More recently Pretsch et al designed and synthesized an improved optical sensor, methylene bis(2-thiobenzothiazole),which was Ag⁺-selective. Here we report synthesis of another ionophore,1,2-bis(2-thiobenzothiazole) ethane, and its IR, ESI-MS, ¹HNMR and UV-Vis.     

近红外荧光探针检测金属离子、小分子和生物大分子

荧光探针技术是近年来发展迅速的一种荧光分析方法,具有灵敏度高、选择性好、操作简便和响应迅速等特点,受到环境及生命科学领域的青睐.随着荧光探针技术的发展,近红外一区荧光探针由于具有发射波长长(600～ 900 nm)、对细胞损伤小、组织穿透性强和自发荧光背景低等优点,被广泛应用于细胞、组织等复杂生物体系中生物分子的检测、...     

EFFECT OF METAL IONS ON THE LUMINESCENCE OF ACRIDINE DYES BOUND TO DNA

Abstract— The luminescence of acridine dyes intercalated in DNA was studied as a function of the concurrent binding of metal ions to DNA, in an effort to deduce specific site interactions of the dyes. Two dyes, proflavine (PF) and acridine orange (AO), and two metal ions, silver and mercuric, were used. Both ions quench the fluorescence of the dyes in aqueous solution at room temperature. The metal ions have a different effect on the fluorescence of these dyes when they are intercalated between the base pairs of DNA. The fluorescence of AO is decreased when silver is bound, while the fluorescence of PF is enhanced. Since Ag⁺ initially binds to GC sites in DNA, which quench the PF fluorescence, it ostensibly 'turns off' the quenching by DNA at these sites, and this effect is greater than the quenching effect of the silver ion itself. Hg²⁺ ion initially binds to AT sites in DNA. Since both dyes fluoresce from AT sites, Hg²⁺ is expected to quench their fluorescence. This behavior is observed at low r (metal ion/base). At higher r values, however, where Hg²⁺ is expected to begin binding to GC sites, the fluorescence of PF is enhanced. These quenching turn-off effects are tentatively interpreted in terms of a change in the structure of the dye/DNA complex which occurs when a metal ion binds at the intercalation site. At 77 K. no fluorescence enhancement is observed when metal ions bind; Ag⁺ quenches the fluorescence and enhances the phosphorescence of both dyes. Qualitatively similar results are obtained with Hg²⁺.     

Quadruple-stranded Eu-helicate Assembled from Bis-β-diketonate: Its Stability Towards Metal Ions

Herein, we reported the synthesis and investigation of highly luminescent quadruple-stranded helicate (C₆H₁₆N)₄[Eu₂(MBDA)₄]₂^.3C₄H₁₀O·4C₂H₃N(1-Eu)[H₂MBDA=N-methyl-4,4'-bis(4,4,4-trifluoro-1,3-dioxobutyl)di- phenylamine] for its stability toward metal ions in the solution. The material was characterized via X-ray crystallographic technique, Fourier transform infrared(FTIR) spectroscopy and electrospray ionization quadrupole time-of- flight(ESI-TOF) mass spectrometry. The results on the luminescence quantum yields clearly demonstrate that the ligand can effectively sensitize the luminescence of the Eu³⁺ ions(Φ_overall=15%). Upon the addition of different metal ions(i. e., Ag⁺, Cd²⁺, Zn²⁺, Fe³⁺, Al³⁺ and Ni²⁺) to the CH₃CN solution of compound 1-Eu, the emission intensities of Eu³⁺ ions at 612 nm were affected to some extent, which could be attributed to the presence of ion exchanges between Eu³⁺ ions and the metals ions, and the result was confirmed by ESI-TOF mass spectrometry.     

荧光素衍生物水杨醛荧光素腙的合成及对铜(Ⅱ)离子的检测

以荧光素酰肼与5-溴水杨醛反应合成了一种新型荧光素衍生物5-溴水杨醛荧光素腙(BSFH),采用红外、核磁、质谱、元素分析等技术手段对其进行了表征。 通过吸收光谱考察了在水溶液中BSFH对常见金属离子的选择性响应,发现BSFH在可见光区几乎无吸收,当加入常见金属离子时,吸收光谱上除了Cu²⁺之外的其它金属离子在496 nm处出现非常弱的吸收,而当Cu²⁺存在时,可以裸眼看到溶液颜色迅速从无色变为黄色,吸收光谱上在496 nm处出现了相对很强的吸收峰,并且随着Cu²⁺浓度的增加溶液的吸收强度不断增强,说明在水溶液中BSFH对Cu²⁺有很好的选择性。 实验结果表明,该化合物与Cu²⁺的化学计量比为1:1,Cu²⁺浓度线性范围为0.30~10 μmol/L,许多常见的金属离子不干扰Cu²⁺的测定,检测限为0.30 μmol/L,说明在水溶液中BSFH对铜离子具有很高的灵敏度。 据此,BSFH可以简单、快速、灵敏地在水溶液中识别和检测低浓度的铜离子。