新型分子印迹荧光传感器的构建与应用

分子印迹聚合物因具有构效预定性、特异识别性和广泛实用性,将其作为传感器识别单元的研究已成为当前的研究热点.分子印迹荧光传感器结合了分子印迹的高选择性与荧光检测的高灵敏度,非常适合复杂样品中痕量目标物的分析测定,在分离检测等领域备受关注.根据荧光材料的不同,本文详细介绍了以量子点、有机荧光染料、化学发光反应物质以及其他材料为荧光信号单元的新型分子印迹荧光传感器的构建与应用,总结了不同荧光传感器的构建方法、检测机理,探讨了基于比率型荧光的分子印迹传感器的制备与发展,并对分子印迹荧光传感器的发展前景进行了展望.     

反应型汞离子光化学传感器*

化学传感器提供了方便、快捷、廉价的分析检测有毒重金属离子的方法,具有很高的灵敏度和选择性。检测对象专一的反应型光化学传感器受到越来越多的关注。本文综述了识别Hg²⁺的反应型光化学传感器的最新研究进展。按照化学反应类型来分类,包括汞促进脱硫和脱硫醇反应、汞促进硫脲衍生物脱硫化氢分子内成环反应、羟汞化及加汞化反应等。     

L-半胱氨酸可视化传感器/体系的研究进展

由于L-半胱氨酸(Cysteine,Cys)在病理生理学以及临床医学等学科领域的重要性,Cys的高选择性检测长期以来受到高度关注.重点综述2010年至今可视化检测Cys的传感器/体系,并根据传感机制的不同分为反应型单分子传感器以及基于金属配合物和纳米材料的传感体系.还简单展望了Cys传感器/体系的发展趋势.     

反应型化学传感器在阴离子检测中的应用

阴离子在生物、化学化工及环境领域扮演着极其重要的角色,对阴离子的高灵敏度、高选择性识别与传感已成为研究的热点.其中,反应型化学传感器是基于传感器与客体分子之间的特殊化学反应而实现的,通过巧妙地设计分子结构,将反应活性基团与荧光团或发色团结合起来,利用反应前后化合物光物理性质的不同,可以实现对被分析物的检测.这种不可逆体系充分利用了化学反应的专一性,因此通常具有较好的选择性.自1992年被首次报道以来,反应型化学传感器的应用越来越广泛,并表现出优秀的传感性能.综述了基于化学反应的荧光和比色阴离子传感器的研究进展,包括氰离子、氟离子、亚硫酸氢根、硫氢根离子、次氯酸及次氯酸根、次溴酸及次溴酸根、过氧亚硝酸根传感器的研究进展,并展望了该领域的发展趋势.     

中科院首次发展高选择性检测GSH荧光传感器

不久前,中科院理化技术研究所超分子光化学研究组首次发展了一类在活体细胞中选择性检测谷胱甘肽(GSH)的反应型荧光传感器。相关研究结果日前发表于《美国化学会志》。自由基损伤是组织损伤的重要分子机制之一,许多疾病,如心脏病、阿尔茨海默氏症、帕金森氏症和肿瘤等的损伤     

基于蛋白A定向固定的Love波免疫传感技术研究

报道了一种基于蛋白A固定技术的新型Love波免疫传感器,可用于检测B型葡萄球菌肠毒素(SEB).本传感器由压电石英基片、叉指换能器和SiO2声波导层构成.为提高传感器对SEB分子的响应能力和检测灵敏度,设计了抗体分子的蛋白A定向固定路线,通过APTES和戊二醛层交联蛋白A,随即用100mmol/LNaBH4还原蛋白A与戊二醛层之间形成的Schiff's base结构,实现抗体分子在Love波器件表面高效率的定向固定.该固定化方案使传感器的再生能力和检测灵敏度都得到显著提高,对10 mg/L SEB进行连续5次检测后,其响应能力没有明显下降;而对SEB的浓度检出限度达到了10μg/L.原子力显微镜对传感器表面形态的成像结果表明,与戊二醛共价交联法相比,蛋白A结合法使抗体分子探针在传感器表面拥有更高的覆盖度和活性,对SEB具有更强的结合能力.     

液晶型化学传感器检测甲基膦酸二甲酯的研究

液晶型化学传感器是利用传感器检测目标化合物前后,液晶分子在敏感膜表面的取向发生变化,改变液晶折射光线的能力,导致传感器的颜色和光亮度发生变化,实现对生物分子、有害化学物质的检测。本实验报道了一种以μm级沟槽状金膜为基底的液晶型化学传感器,通过在具有μm级沟槽(一个沟槽周期5μm)的玻璃基底上进行平面镀金,制备了具有相同沟槽周期的金膜,并在金膜上制备Cu2 修饰的巯基十一酸自组装敏感膜。通过检测甲基膦酸二甲酯时液晶织构的变化,阐明了液晶型化学传感器的作用机理,并证实微米级沟槽状金膜为基底制作的液晶型化学传感器可以用于检测目标化合物。传感器对甲基膦酸二甲酯检测的线性范围0.03~1.00g/m3;线性方程Y=0.14X 0.0035,相关系数r=0.9957。     

阴离子荧光化学传感器新进展

本文主要介绍自2004年以来阴离子荧光化学传感器的最新进展.按照受体分子和阴离子的作用类型来分类,包括以氢键或静电作用键合阴离子的受体（胺和酰胺类、脲和硫脲类、五元杂环类和其他类型）、路易斯酸和含金属的荧光受体以及反应型化学传感器.     

多壁碳纳米管和分子印迹膜修饰电极检测猪尿液中莱克多巴胺

采用原位热聚合技术,分别以多壁碳纳米管(MWCNs)和分子印迹膜(MIM)修饰丝网印刷电极(SPE),与多壁碳纳米管和非分子印迹膜(NIM)修饰的丝网印刷电极组合在一起,并将其组合的丝网印刷电极通过电极插口与便携式电导仪相连接,组装成检测莱克多巴胺残留的电导型传感器,优化检测条件,并建立了检测莱克多巴胺的标准曲线,测试了实际猪尿样中莱克多巴胺的含量.通过扫描电镜分析了该分子印迹膜的表征结构.结果表明,在莱克多巴胺分子印迹膜表面形成了大量印迹微孔.本传感器装置检测莱克多巴胺具有很高的灵敏度和特异性,检出限为0.033 mg/L,线性范围为0.33～8.0 mg/L,基于猪尿样的检测回收率达到91％～98％,可实现现场快速检测.     

基于电化学双共价键法构建可再生高灵敏的电化学发光适体传感器检测可卡因

基于点击化学和重氮盐法的双共价键固定化方法,制备了一种高灵敏、可重复使用的电化学发光(ECL)适体传感器. 该方法以可卡因为分析物,以可卡因适体为分子识别物质,以钌联吡啶衍生物为ECL信号物质. 采用电化学方法在玻碳电极表面重氮化叠氮苯胺,通过点击反应连接炔基功能化的钌联吡啶衍生物标记可卡因适体,获得适体传感器. 该传感器在共反应剂存在下,产生弱的电化学发光信号,可卡因存在下,电化学发光信号增加. 基于此,建立了“信号增强”型检测可卡因的电化学发光分析新方法. 电化学发光信号与可卡因浓度在0.1 nmol·L^-1 ~ 100 nmol·L^-1范围内呈良好的线性关系,检出限为60 pmol·L^-1. 该传感器具有良好的稳定性,可重复多次使用. 该双共价键法在构建ECL传感器方面具有很好的应用前景.     

Contributions to the Chemistry of the Binary Compounds of the Transition Elements

Phase and structural relationships of the sulfur, selenium, and tellurium compounds of the 4d and 5d transition elements of groups IV to VII of the periodic system are discussed. Homologous elements behave very similarly with respect to the chalcogens, and this is particularly the case for niobium and tantalum, and for molybdenum and tungsten. However, zirconium, niobium, and molybdenum have a greater tendency towards formation of chalcogen-poor phases than their homologues hafnium, tantalum, and tungsten. Subchalcogenides are known only for zirconium and niobium. The number of phases and the tendency towards formation of solid solutions are considerably smaller among the tellurides than among the sulfides and selenides. The crystal structures of the telluride phases also differ from those of the sulfide and selenide phases of analogous composition. In addition, a review of the phase and structural relationships of the arsenic and antimony compounds of the 4d and 5d transition elements of groups V to VII is given.     

Semiconductor quantum dots and metal nanoparticles: syntheses,optical properties,and biological applications

We review the syntheses, optical properties, and biological applications of cadmium selenide (CdSe) and cadmium selenide–zinc sulfide (CdSe–ZnS) quantum dots (QDs) and gold (Au) and silver (Ag) nanoparticles (NPs). Specifically, we selected the syntheses of QDs and Au and Ag NPs in aqueous and organic phases, size- and shape-dependent photoluminescence (PL) of QDs and plasmon of metal NPs, and their bioimaging applications. The PL properties of QDs are discussed with reference to their band gap structure and various electronic transitions, relations of PL and photoactivated PL with surface defects, and blinking of single QDs. Optical properties of Ag and Au NPs are discussed with reference to their size- and shape-dependent surface plasmon bands, electron dynamics and relaxation, and surface-enhanced Raman scattering (SERS). The bioimaging applications are discussed with reference to in vitro and in vivo imaging of live cells, and in vivo imaging of cancers, tumor vasculature, and lymph nodes. Other aspects of the review are in vivo deep tissue imaging, multiphoton excitation, NIR fluorescence and SERS imaging, and toxic effects of NPs and their clearance from the body. Figure Semiconductor quantum dots and metal nanoparticles have extensive applications, e.g., in vitro and in vivo bioimaging Tamitake Itoh and Abdulaziz Anas contributed equally to this article.     

Simultaneous analysis of serotonin, melatonin, piceid and resveratrol in fruits using liquid chromatography tandem mass spectrometry

An analytical method was developed for the simultaneous quantification of serotonin, melatonin, trans- and cis-piceid, and trans- and cis-resveratrol using reversed-phase high performance liquid chromatography coupled to mass spectrometry (HPLC-MS) with electrospray ionization (ESI) in both positive and negative ionization modes. HPLC optimal analytical separation was achieved using a mixture of acetonitrile and water with 0.1% formic acid as the mobile phase in linear gradient elution. The mass spectrometry parameters were optimized for reliable quantification and the enhanced selectivity and sensitivity selected reaction monitoring mode (SRM) was applied. For extraction, the direct analysis of initial methanol extracts was compared with further ethyl acetate extraction. In order to demonstrate the applicability of this analytical method, serotonin, melatonin, trans- and cis-piceid, and trans- and cis-resveratrol from 24 kinds of commonly consumed fruits were quantified. The highest serotonin content was found in plantain, while orange bell peppers had the highest melatonin content. Grape samples possessed higher trans- and cis-piceid, and trans- and cis-resveratrol contents than the other fruits. The results indicate that the combination of HPLC-MS detection and simple sample preparation allows the rapid and accurate quantification of serotonin, melatonin, trans- and cis-piceid, and trans- and cis-resveratrol in fruits.     

Photo‐hardenable and patternable PDMS/SU‐8 hybrid functional material: A smart substrate for flexible systems

The fabrication of flexible electronics and systems, using rigid and brittle materials directly produced on stretchable substrate, leads to some issues and incompatibilities. These include rigidity for processing and modular flexibility for applications, macroscopic flexibility, and local rigidity to shield components from strain, compatibility with technological steps, and at the same time allowing patterning and machining. The development of smart substrate materials which meet such needs is therefore a promising route for flexible systems. Here, we demonstrate that by mixing polydimethylsiloxane (PDMS) and SU‐8 photoresist, we obtain both a photo‐hardenable and patternable stretchable hybrid material. A set of PDMS/SU‐8 and baking process combinations have been tested to determine an effective photo‐sensitive mixture. A standard photolithographic approach has been used on tensile test samples demonstrating a local hardening of millimeter‐sized ultraviolet exposed features and a local strain reduction reaching 35%. In addition, surface topography analysis and wet‐etching techniques have been used to demonstrate a light‐induced molding process and a selective etching of micrometer‐sized ultraviolet exposed patterns. The combined functional properties of the following material, its simplicity of implementation, and the well‐known assets of PDMS and SU‐8 make the PDMS/SU‐8 material very interesting and promising for various applications, especially stretchable systems. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1281–1291     

常温常压下吡咯及其衍生物的镍催化加氢反应考察

为进一步研究常温常压下吡咯及其衍生物的镍催化加氢反应,我们对试剂吡咯、吡咯烷和吡咯烷酮做了相应的催化加氢实验。并采用电镜（TEM-HREM）、X射线衍射（XRD）对Ni基催化剂的形貌、结构、加氢活性和超声波对其影响进行了检测,同时还用紫外吸收光谱、气相色谱等对加氢产物进行了分析考察。结果表明超声波能促进镍基催化剂活性,使镍微晶(111)晶面间距增大1.5%、并保持高分散态。常温常压下纳米镍基催化剂对吡咯、吡咯烷和吡咯烷酮的加氢反应显示一定的催化活性;吡咯加氢首先生成吡咯烷,进而使环打开生成低碳烃、氨等产物,总反应为零级,符合表面接触反应特征。     

Emerging Lipids from Arecaceae Palm Fruits in Brazil

Arecaceae palm tree fruits (APTFs) with pulp or kernel rich in oil are widely distributed in six Brazilian biomes. APTFs represent a great potential for the sustainable exploitation of products with high added value, but few literature studies have reported their properties and industrial applications. The lack of information leads to underutilization, low consumption, commercialization, and processing of these fruit species. This review presents and discusses the occurrence of 13 APTFs and the composition, physicochemical properties, bioactive compounds, and potential applications of their 25 oils and fats. The reported studies showed that the species present different lipid profiles. Multivariate analysis based on principal component analysis (PCA) and hierarchical cluster analysis (HCA) indicated a correlation between the composition of pulp and kernel oils. Myristic, caprylic, capric, and lauric acids are the main saturated fatty acids, while oleic acid is the main unsaturated. Carotenoids and phenolic compounds are the main bioactive compounds in APTFs, contributing to their high oxidative stability. The APTFs oils have a potential for use as foods and ingredients in the cosmetic, pharmaceutical, and biofuel industries. However, more studies are still necessary to better understand and exploit these species.     

智能响应材料在磷酸化肽和糖肽富集中的应用

蛋白质的磷酸化和糖基化作为研究最广泛的两种翻译后修饰(PTMs),在疾病的早期无创诊断、预后和治疗评估中表现出越来越大的潜力。蛋白质的异常磷酸化和糖基化经常被用于临床蛋白质组学研究和疾病相关生物标志物的发现。目前已有多种材料被开发用于磷酸化肽和糖肽的富集研究,其中,智能响应材料由于具有独特的响应特性,已被陆续报道用于磷酸化肽和糖肽的富集。智能响应材料可对外界刺激做出响应,发生结构和性质上的变化,将光、电、热、机械等信号转化为生物化学信号。响应分子是决定智能响应材料响应特性的先决条件,它们在不同刺激条件下(如温度、pH、光、机械应力、电磁场等)的可逆异构化将导致材料的宏观物理和化学性质的动态变化。与传统材料相比,智能响应材料可以可逆地“打开”和“关闭”,具有更好的可调控性。由于引起智能材料响应的刺激信号对其性能具有重要的影响,综述根据施加的刺激种类对智能响应材料进行分类,具体分为外源性响应材料和内源性响应材料,且分别总结了外源性响应材料、内源性响应材料以及内外源共同响应材料在磷酸化肽和糖肽富集方面的工作。此外,综述对智能响应材料在磷酸化肽和糖肽富集方面的发展前景进行了展望,并且提出了智能响应材料在其他蛋白质翻译后修饰方面的应用中存在的挑战。     

Cellulolytic and Xylanolytic Enzymes from Yeasts: Properties and Industrial Applications

Lignocellulose, the main component of plant cell walls, comprises polyaromatic lignin and fermentable materials, cellulose and hemicellulose. It is a plentiful and renewable feedstock for chemicals and energy. It can serve as a raw material for the production of various value-added products, including cellulase and xylanase. Cellulase is essentially required in lignocellulose-based biorefineries and is applied in many commercial processes. Likewise, xylanases are industrially important enzymes applied in papermaking and in the manufacture of prebiotics and pharmaceuticals. Owing to the widespread application of these enzymes, many prokaryotes and eukaryotes have been exploited to produce cellulase and xylanases in good yields, yet yeasts have rarely been explored for their plant-cell-wall-degrading activities. This review is focused on summarizing reports about cellulolytic and xylanolytic yeasts, their properties, and their biotechnological applications.     

蛋白质、凝胶电泳及其分析应用

蛋白质是重要的生物高分子，具有催化、传输、运动、防御和调节等重要生理功能，其分离、纯化和表征对理解和利用它们在生命过程中的作用具有重大理论意义和实际价值。凝胶电泳是蛋白质测定中应用最广泛和最强有力的工具。本文讨论凝胶电泳方法及其在蛋白质分析方面的新进展。首先介绍蛋白质的性质和功能，然后讨论蛋白质试样制备方法，最后评述各种凝胶电泳分离技术及其在蛋白质分离、纯化和表征等方面的应用。     

SYNTHESIS, CHARACTERIZATION, THERMAL DEGRADATION AND ELECTROCHEMICAL PROPERTIES OF OLIGO-4-m-TOLYLAZOMETHINEPHENOL

The oxidative polycondensation reaction conditions of 4-m-tolylazomethinephenol （4-TAMP） in the presence of air O2 and NaOCl as oxidants were studied in an aqueous alkaline medium between 50 and 90℃. The structures of the obtained monomer and oligomer were confirmed by FT-IR, UV-Vis, ^1H- and ^13C-NMR and elemental analysis techniques. The physical characterization was made by TG-DTA, size exclusion chromatography （SEC） and solubility tests. At the optimum reaction conditions, the yield of oligo-4-m-tolylazomethinephenol （O-4-TAMP） was found to be 62.50% （for air O2 oxidant） and 90.0% （for NaOCl oxidant）, respectively. According to the SEC analysis, the number-average molecular weight （Mn）, weight-average molecular weight （Mw） and polydispersity index （PDI） values of O-4-TAMP were found to be 2310, 2610 g tool 1 and 1. 13, respectively, using air O2, and 1390, 1710 g mol^-1 and 1.23, using NaOCl, respectively. According to TG-DTA analyses, O-4-TAMP was more stable than 4-TAMP against thermal decomposition. The weight losses of 4-TAMP and O-4-TAMP were found to be 68% and 58% at 1000℃. Electrical conductivity of the O-4-TAMP was measured, showing that the polymer is a typical semiconductor. Electrochemically, the highest occupied molecular orbital （HOMO）, the lowest unoccupied molecular orbital （LUMO） and electrochemical energy gaps （E＇g） for 4-TAMP are -5.96, -3.22 and 2.74 eV, respectively. The HOMO, LUMO and （E＇g） for O-4-TAMP are -5.78, -3.44 and 2.34 eV, respectively. According to UV-Vis measurements, optical band gaps （Eg） of 4-TAMP and O-4-TAMP were found to be 3.45 and 3. 1 0 eV, respectively.