介孔金属氧化物/复合物的合成方法

介孔金属氧化物及其复合物由于其特有的组成与结构, 在催化、传感、光、电、磁等领域有着广泛的应用, 是近年来国内外跨学科领域研究的热点。本文对近几年来介孔金属氧化物及其复合物的合成方法进行了归纳总结, 其合成途径大致可以分为软模板法、硬模板法及纳米晶粒组装法。     

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。     

非酶葡萄糖传感器电极材料构建策略

电化学传感器因具有灵敏度高、检测限低等优点而得到广泛应用,将非酶电化学传感器应用于葡萄糖浓度的检测具备重要的研究价值。以金属有机骨架、碳材料和导电聚合物为基底与金属及其衍生物复合,构建的纳米复合材料修饰电极对于葡萄糖的检测具有极高的灵敏度、较低的检测限和快速响应的能力,可应用于实际样品的检测。本文综述了近年来非酶葡萄糖电化学传感器的研究进展,通过对纳米复合材料的性能比较,为非酶葡萄糖传感器的构建提供思路。     

Differentiating between fluorescence-quenching metal ions with polyfluorophore sensors built on a DNA backbone

A common problem in detecting metal ions with fluorescentchemosensors is the emission-suppressing effects of fluorescence-quenching metal ions. This quenching tendency makes it difficult to design sensors with turn-on signal, and differentiate between several metal ions that may yield a strong quenching response. To address these challenges, we investigate a new sensor design strategy, incorporating fluorophores and metal ligands as DNA base replacements in DNA-like oligomers, for generating a broader range of responses for quenching metal ions. The modular molecular design enabled rapid synthesis and discovery of sensors from libraries on PEG-polystyrene beads. Using this approach, water-soluble sensors 1-5 were identified as strong responders to a set of eight typically quenching metal ions (Co(2+), Ni(2+), Cu(2+), Hg(2+), Pb(2+), Ag(+), Cr(3+), and Fe(3+)). They were synthesized and characterized for sensing responses in solution. Cross-screening with the full set of metal ions showed that they have a wide variety of responses, including emission enhancements and red- and blue-shifts. The diversity of sensor responses allows as few as two sensors (1 and 2) to be used together to successfully differentiate these eight metals. As a test, a set of unknown metal ion solutions in blind studies were also successfully identified based on the response pattern of the sensors. The modular nature of the sensor design strategy suggests a broadly applicable approach to finding sensors for differentiating many different cations by pattern-based recognition, simply by varying the sequence and composition of ligands and fluorophores on a DNA synthesizer.     

Progress in developing polymerized crystalline colloidal array sensors for point-of-care detection of myocardial ischemia

The difficulty of rapid, definitive diagnosis of myocardial ischemia leads to unnecessary hospital admissions and treatment delays. Previously, decreased metal binding affinity in human serum was investigated as a marker for myocardial ischemia. Polymerized Crystalline Colloidal Array (PCCA) sensors for Ni2+ may be useful in developing a point-of-care test to determine metal binding affinity in plasma and to help rule out myocardial ischemia. PCCA sensors for Ni2+, with 5-amino-8-hydroxyquinoline as a chelating agent, were tested in aqueous solutions and diluted human plasma. The peak wavelength diffracted by the sensors was monitored by reflectance spectrometry and correlated with Ni2+ concentration. The PCCA sensors show a linear response to aqueous Ni2+ concentrations between 0.2 and 1.0 mmol L(-1), and can detect changes in free Ni2+ concentration of <60 micromol L(-1). The sensors respond at physiologic pH and can be reversibly dehydrated. The PCCA sensors developed here can report on free Ni2+ concentration in the presence of human plasma. These sensors can be used to detect a decrease in the Ni2+ affinity of plasma proteins, which may indicate recent myocardial ischemia. PCCA sensors offer a practical approach to rapid, point-of-care detection of a proposed biochemical signature of myocardial ischemia.     

Development of Optical Sensors Based on Luminescent Transition-Metal Complexes

Luminescence-based optical sensors are becoming increasingly important particularly in the area of fibber optic sensors. Most luminescence sensors detect analyses based on the change in luminescent intensity or excited-state lifetime of the sensing material as a function of analyst concentration. Luminescent materials with long excited-state lifetime are essential for the development of inexpensive sensors because it is much simpler and less expensive to measure lifetime in microseconds than in nanoseconds. Luminescent dyes with absorption in the visible region would allow the use of inexpensive light sources such as light emitting diodes (LEDs). Recent studies indicate that luminescent transition metal complexes, especially those with platinum group metals, have desirable spectral characteristics and features including long excited state lifetimes, high luminescence quantum yields and intense visible absorptions. They also tend to be thermally, chemically and photochemically robust. We have been investigating new luminescent sensor materials with the aims to understand the behaviour of luminescent materials in polymer and gel support and to develop new sensor materials with desirable properties.     

多肽基金属离子传感器

多肽基金属离子传感器作为一种基于多肽序列而设计的新型传感器,越来越受到研究者的关注.多肽作为一类重要的生物小分子,具有合成方法成熟、简便、成本低,且能够以多齿配位状态与金属离子结合等优点.多肽基传感器对金属离子具有高灵敏性和高选择性,且可以通过调节多肽序列进一步优化.与其他类型传感器相比,多肽基金属离子传感器具有良好的...     

Thin‐Film Metal Hydrides

The goal of the medieval alchemist, the chemical transformation of common metals into nobel metals, will forever be a dream. However, key characteristics of metals, such as their electronic band structure and, consequently, their electric, magnetic and optical properties, can be tailored by controlled hydrogen doping. Due to their morphology and well‐defined geometry with flat, coplanar surfaces/interfaces, novel phenomena may be observed in thin films. Prominent examples are the eye‐catching hydrogen switchable mirror effect, the visualization of solid‐state diffusion and the formation of complex surface morphologies. Thin films do not suffer as much from embrittlement and/or decrepitation as bulk materials, allowing the study of cyclic absorption and desorption. Therefore, thin‐metal hydride films are used as model systems to study metal–insulator transitions, for high throughput combinatorial research or they may be used as indicator layers to study hydrogen diffusion. They can be found in technological applications as hydrogen sensors, in electrochromic and thermochromic devices. In this review, we discuss the effect of hydrogen loading of thin niobium and yttrium films as archetypical examples of a transition metal and a rare earth metal, respectively. Our focus thereby lies on the hydrogen induced changes of the electronic structure and the morphology of the thin films, their optical properties, the visualization and the control of hydrogen diffusion and on the study of surface phenomena and catalysis.     

Modulating the selectivity of near-IR fluorescent probes toward various metal ions by judicious choice of aqueous buffer solutions

The near-infrared fluorescent probes S1 and S2 based on the BODIPY skeleton were designed and synthesized. They showed different selectivity in various aqueous buffer solutions. Judicious choice of buffer solutions can modulate the selectivity of fluorescent sensors toward a specific metal ion.     

铅、汞、镉离子的荧光传感器研究进展

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,并具有很高的灵敏度和选择性.它在环境科学、分析化学以及生命科学等领域有广泛的应用前景.本文分别综述了pb²⁺、Hg²⁺、Cd²⁺几种有毒重离子化学传感器的最新研究进展,并展望了该领域的发展趋势.     

Cantilever biosensors

This review will provide a general introduction to the field of cantilever biosensors by discussing the basic principles and the basic technical background necessary to understand and evaluate this class of sensors. Microfabricated cantilever sensors respond to changes in their environment or changes on their surface with a mechanical bending in the order of nanometers which can easily be detected. They are able to detect pH and temperature changes, the formation of self-assembled monolayers, DNA hybridization, antibody-antigen interactions, or the adsorption of bacteria. The review will focus on the surface stress mode of microfabricated cantilever arrays and their application as biosensors in molecular life science. A general background on biosensors, an overview of the different modes of operation of cantilever sensors and some details on sensor functionalization will be given. Finally, key experiments and current theoretical efforts to describe the surface stress mode of cantilever sensors will be discussed.     

New Promises and Opportunities in 3D Printable Inks Based on Coordination Compounds for the Creation of Objects with Multiple Applications

This review focuses on the usefulness of coordination bonds to create 3D printable inks and shows how the union of chemistry and 3D technology contributes to new scientific advances, by allowing amorphous or polycrystalline solids to be transformed into objects with the desired shape for successful applications. The review clearly shows how there has been considerable increase in the manufacture of objects based on the combination of organic matrices and coordination compounds. These coordination compounds are usually homogeneously dispersed within the matrix, anchored onto a proper support or coating the printed object, without destroying their unique properties. Advances are so rapid that today it is already possible to 3D print objects made exclusively from coordination compounds without additives. The new printable inks are made mainly with nanoscale nonporous coordination polymers, metal–organic gels, or metal–organic frameworks. The highly dynamic coordination bond allows the creation of objects, which respond to stimuli, that can act as sensors and be used for drug delivery. In addition, the combination of metal–organic frameworks with 3D printing allows the adsorption or selective capacity of the object to be increased, relative to that of the original compound, which is useful in energy storage, gas separation, or water pollutant elimination. Furthermore, the presence of the metal ion can give them new properties, such as luminescence, that are useful for application in sensors or anticounterfeiting. Technological advances, the combination of various printing techniques, and the properties of coordination bonds lead to the creation of surprising, new, printable inks and objects with highly complex shapes that will close the gap between academia and industry for research into coordination compounds.     

DNAzyme‐Mediated Genetically Encoded Sensors for Ratiometric Imaging of Metal Ions in Living Cells

Genetically encoded fluorescent proteins (FPs) have been used for metal ion detection. However, their applications are restricted to a limited number of metal ions owing to the lack of available metal‐binding proteins or peptides that can be fused to FPs and the difficulty in transforming the binding of metal ions into a change of fluorescent signal. We report herein the use of Mg²⁺‐specific 10–23 or Zn²⁺‐specific 8–17 RNA‐cleaving DNAzymes to regulate the expression of FPs as a new class of ratiometric fluorescent sensors for metal ions. Specifically, we demonstrate the use of DNAzymes to suppress the expression of Clover2, a variant of the green FP (GFP), by cleaving the mRNA of Clover2, while the expression of Ruby2, a mutant of the red FP (RFP), is not affected. The Mg²⁺ or Zn²⁺ in HeLa cells can be detected using both confocal imaging and flow cytometry. Since a wide variety of metal‐specific DNAzymes can be obtained, this method can likely be applied to imaging many other metal ions, expanding the range of the current genetically encoded fluorescent protein‐based sensors.     

Overview of N-Rich Antennae Investigated in Lanthanide-Based Temperature Sensing

The market share of noncontact temperature sensors is expending due to fast technological and medical evolutions. In the wide variety of noncontact sensors, lanthanide-based temperature sensors stand out. They benefit from high photostability, relatively long decay times and high quantum yields. To circumvent their low molar light absorption, the incorporation of a light-harvesting antenna is required. This Review provides an overview of the nitrogen-rich antennae in lanthanide-based temperature sensors, emitting in the visible light spectrum, and discusses their temperature sensor ability. The N-rich ligands are incorporated in many different platforms. The investigation of different antennae is required to develop temperature sensors with diverse optical properties and to create a diverse offer for the multiple application fields. Molecular probes, consisting of small molecules, are first discussed. Furthermore, the thermometer properties of ratiometric temperature sensors, based on di- and polynuclear complexes, metal–organic frameworks, periodic mesoporous organosilicas and porous organic polymers, are summarized. The antenna mainly determines the application potential of the ratiometric thermometer. It can be observed that molecular probes are operational in the broad physiological range, metal–organic frameworks are generally very useful in the cryogenic region, periodic mesoporous organosilica show temperature dependency in the physiological range, and porous organic polymers are operative in the cryogenic-to-medium temperature range.     

DNAzyme-Mediated Genetically Encoded Sensors for Ratiometric Imaging of Metal Ions in Living Cells

Genetically encoded fluorescent proteins (FPs) have been used for metal ion detection. However, their applications are restricted to a limited number of metal ions owing to the lack of available metal-binding proteins or peptides that can be fused to FPs and the difficulty in transforming the binding of metal ions into a change of fluorescent signal. We report herein the use of Mg²⁺-specific 10–23 or Zn²⁺-specific 8–17 RNA-cleaving DNAzymes to regulate the expression of FPs as a new class of ratiometric fluorescent sensors for metal ions. Specifically, we demonstrate the use of DNAzymes to suppress the expression of Clover2, a variant of the green FP (GFP), by cleaving the mRNA of Clover2, while the expression of Ruby2, a mutant of the red FP (RFP), is not affected. The Mg²⁺ or Zn²⁺ in HeLa cells can be detected using both confocal imaging and flow cytometry. Since a wide variety of metal-specific DNAzymes can be obtained, this method can likely be applied to imaging many other metal ions, expanding the range of the current genetically encoded fluorescent protein-based sensors.     

金属氧化物异质结气体传感器气敏增强机理

金属氧化物异质结由于费米能级效应、不同组分之间的协同作用,常被用来提高电阻型金属氧化物半导体气体传感器的气敏特性。本文简述了近年来国内外金属氧化物异质结材料的类别,主要分为混合氧化物结构、层状结构、第二相粒子修饰结构、一维纳米结构和核-壳结构;重点综述了金属氧化物异质结的气敏增强机理,包括异质结效应、协同效应、催化溢流效应、响应反型、载流子分离及微结构调控六大机理;分析了当前异质结气体传感器面临的瓶颈。最后对纳米异质结气体传感器的发展进行了展望,今后金属氧化物异质结气体传感器可以从明确异质结界面机理展开,这将为自下而上地设计出符合实际需要的气体传感器提供一定参考。     

聚类卟啉金属配合物*

为模拟天然卟啉所具有的特殊生理活性,结构与性能各异的多种金属卟啉被合成并应用于许多领域。实际上,天然金属卟啉是在特定天然高分子-蛋白质营造的空穴中才能发挥其独特的性质,因此,类卟啉金属配合物的高分子化逐渐受到关注,并在载氧、催化、导电等领域取得重要成果。基于结合方式不同,高分子类卟啉金属配合物可分为高分子担载类卟啉金属配合物与聚类卟啉金属配合物。其中,后者以稳定的类卟啉环作为高分子链,不但使高分子骨架稳定,而且活性中心与类卟啉金属配合物之间有效间隔,同时活性中心相对密集,使其表现出较高的稳定性与活性。线形与平面型聚金属卟啉与金属酞菁表现出良好的导电性与催化活性;手性Salen席夫碱易于聚合得到线形或网状聚Salen希夫碱金属配合物,其表现出较强的催化活性、高ee值和可循环性。异双核聚类卟啉金属配合物也表现出较强的催化活化分子氧性能。     

金属有机框架及其衍生的金属氧化物在电阻式气体传感器中的应用

高灵敏和选择性的气体传感器对于实时监测大气中有毒有害气体和早期的疾病诊断具有重要的意义。目前,传统的气敏材料仍然存在着许多问题亟待解决,例如：选择性差、检测极限不够低、使用寿命短等。作为一种多孔的配位聚合物,金属有机框架材料(MOFs)由于其超高的比表面积和较大的孔隙率在气体传感器领域已经得到广泛的应用。利用MOFs自身或者由它们衍生的不同纳米结构的金属氧化物可以提升气体传感器的灵敏度和选择性,为制备新型高性能的气体传感器提供了新的思路和方向。本文结合金属氧化物半导体(MOS)的气敏机理,综述了不同结构的MOFs及其衍生的金属氧化物在电阻式气体传感器领域的研究进展,并对其应用前景和发展方向作出了展望。     

Fluorescent cyclodextrins bearing metal binding sites and their use for chemo- and enantioselective sensing of amino acid derivatives

Ditopic receptors based on cyclodextrins bearing a metal binding site were used as enantioselective fluorescence sensors, which were able to generate different responses in the presence of d- or l-amino acids. The performances of the selectors as a function of their structure were evaluated, and the same analysis was extended to other analytes. In this work, this approach is used for the enantiomers of a series of amino acid derivatives and in particular of 2-aminocaprolactam. The results showed that the ability of these sensors to perform enantiomeric analysis can be extended to other analytes of interest in organic synthesis such as amino acid amides and α-aminolactams.     

Silica-based optical chemosensors for detection and removal of metal ions

Because some metal ions are highly toxic even at trace level, a constant demand of developing methods for monitoring and removing these metal ions is extremely urgent. Silica-based optical chemosensors are supposed as good alternatives to classical instrumental methods for detecting and adsorbing metal ions, due to their effect and lower price. Silica nanoparticles, silica gel and mesoporous silica are used as supporting platforms to fabricate optical chemosensors. They have certain properties containing high porosity and expectant adsorption capacity. Chromogenic-type and fluorogenic-type optical probes, such as azobenzene, naphthalimide and rhodamine, are grafted to the surface of silica-based materials by sol–gel reaction, the limit of detection, response time and selective properties of optical sensors are improved sequentially. In this paper, the articles of silica-based optical chemosensors are retrospected since 2008, describing silica-based optical sensors used for sensing metal ions. The sensing mechanism, optical phenomenon, detection limit, adsorption capacity and application are also reviewed.