Functionalized gold nanoparticle supported sensory mechanisms applied in detection of chemical and biological threat agents: A review

There is a great necessity for development of novel sensory concepts supportive of smart sensing capabilities in defense and homeland security applications for detection of chemical and biological threat agents. A smart sensor is a detection device that can exhibit important features such as speed, sensitivity, selectivity, portability, and more importantly, simplicity in identifying a target analyte. Emerging nanomaterial based sensors, particularly those developed by utilizing functionalized gold nanoparticles (GNPs) as a sensing component potentially offer many desirable features needed for threat agent detection. The sensitiveness of physical properties expressed by GNPs, e.g. color, surface plasmon resonance, electrical conductivity and binding affinity are significantly enhanced when they are subjected to functionalization with an appropriate metal, organic or biomolecular functional groups. This sensitive nature of functionalized GNPs can be potentially exploited in the design of threat agent detection devices with smart sensing capabilities. In the presence of a target analyte (i.e., a chemical or biological threat agent) a change proportional to concentration of the analyte is observed, which can be measured either by colorimetric, fluorimetric, electrochemical or spectroscopic means. This article provides a review of how functionally modified gold colloids are applied in the detection of a broad range of threat agents, including radioactive substances, explosive compounds, chemical warfare agents, biotoxins, and biothreat pathogens through any of the four sensory means mentioned previously.     

Optochemical sensing by immobilizing fluorophore-encapsulating liposomes in sol–gel thin films

The chemical stability of optochemical sensors depends largely on the physiochemical properties of the supportive matrix of the sensor and on the method used to immobilize sensing reagents to the supportive matrix of the sensor. Leaking of physically immobilized sensing reagents from the matrix support decreases the stability of the sensor and its overall usefulness. Covalent immobilization eliminates leakage of the sensing reagent from the support but may lead to alteration of spectral properties and loss of analyte response. This paper presents a new method for physical immobilization of polar fluorescence dyes in a sensing support. The method is based on the immobilization of fluorescent dye encapsulating liposomes in a sol–gel film of micrometer thickness. The encapsulation of the dye molecules in the liposomes effectively increases the molecular dimensions of the sensing reagent, thus preventing its leakage from the matrix support. This paper describes the analytical properties of a pH sensor fabricated by immobilizing carboxyfluorescein-encapsulating liposomes in a sol–gel thin film. The sensor shows excellent stability with respect to dye leaking which in turn leads to high reproducibility and sensitivity of about 0.01 pH units. The linear dynamic range of the sensor is between pH 6 and 7.5 and its response time is at the sub-seconds time scale.     

The pillar[5]arene-based spun thin films: preparation,characterization, development of optical and mass sensitive sensors for swelling dynamics and gas sensing abilities

Pillar[5]arene (P5)-based materials can be preferable one of the most sensing elements in chemical sensor applications due to their high cavity and their special chiral structure. While the P5-based macrocycle molecules have been utilized as thin-film materials, the reports of chemical sensor application by performing P5 as sensor molecules have been very limited in the available literature. In this report, quinoline P5 (P5-Q) molecules were used to produce thin films via spin coating technique. P5-Q spun films were characterized with Atomic Force Microscopy (AFM) and Ultraviolet–Visible (UV–Vis) spectrophotometer. The gas sensing abilities of these P5-Q spun films were investigated by Quartz Crystal Microbalance (QCM) and Surface Plasmon Resonance (SPR) techniques. In order to illuminate the gas sensing properties of P5-Q spun films, they were prepared as mass-sensitive and optical sensors. These sensors were utilized for its sensing abilities against organic vapours (acetone, methyl alcohol, and ethyl alcohol) by the mechanism of host–guest interaction. The current study also describes the diffusion coefficients of these organic vapors to illuminate the swelling dynamics of P5-Q spun films by performing Fick’s diffusion equation. The responses of P5-based optical (SPR) or mass sensitive (QCM) sensor in terms of the change in reflective intensity or the change in frequency and the values of diffusion coefficients showed that P5-Q molecules can be developed as potential chemical sensor element for acetone vapor compared to alcohol vapors.

     

Metal Ion‐Assisted Infrared Optical Sensor for Selective Determination of Tryptophan in Urine Samples

In this study, a simple infrared chemical sensor was developed for the selective detection of tryptophan in biological fluids. This sensor was capable of trapping tryptophan molecules through the formation of relatively stable metal ion complexes on the surface of the sensing element. A proline‐modified sensing phase was immobilized on the surface of the internal reflection element. With the assistance of appropriate metal ions, tryptophan molecules were selectively attracted nearby the evanescent field such that analytical signals were generated. Factors that affected the chemical equilibria in this detection system were examined including the species and concentration of metal ion, the pH of the sample solution, and the concentration of the chelating agent. Among the examined metal ions, nickel provided the best selectivity toward the detection of tryptophan as a result of its extremely high formation constant with tryptophan. Under the optimal conditions, the detected signals were related linearly (R² > 0.99) to concentrations of tryptophan up to 600 μM. Based on three times the baseline variation of blank samples, the detection limit was ca. 5 μM. From a study of possible interfering agents—metal ions and organic species—in the sample solution, the recoveries of tryptophan were greater than 95%.     

Nanostructured Substrates for Optical Sensing

Sensors that change color have the advantages of versatility, ease of use, high sensitivity, and low cost. The recent development of optically based chemical sensing platforms has increasingly employed substrates manufactured with advanced processing or fabrication techniques to provide precise control over shape and morphology of the sensor micro- and nano-structure. New sensors have resulted with improved capabilities for a number of sensing applications, including the detection of biomolecules and environmental monitoring. This perspective focuses on recent optical sensor devices that utilize nanostructured substrates.     

现场侦检装备在应对化学威胁中的应用与发展

近年来,国内外不断发生的化学恐怖袭击和化学事故仍然是当今人类生存、国家安全所面临的重大威胁。化学侦检是防化应急处置与救援的眼睛,熟练掌握和正确使用侦检装备是应对化学威胁、降低损失和伤亡的关键因素。基于化学传感等技术的侦检装备具有响应快速、智能便携的特点,并且在远程监测和实时值守等方面具有优势。该文针对涵盖电化学传感器、质量敏感型传感器、红外传感器、拉曼传感器、离子迁移谱仪、火焰光度检测器、光致电离检测器、远程遥测传感装备等在内的现场侦检装备,从原理、性能、优势和不足等方面进行了概述,重点阐述了侦检装备在应对化学威胁方面的最新进展,并对其发展趋势、应用前景进行了展望,以期为化学侦检装备在应对化学威胁中的深入研究与应用提供参考。     

Evaluation of the performance of sensors based on optical imaging of a chemically sensitive layer

Interest in the use of the optical properties of chemical indicators is growing steadily. Among the optical methods that can be used to capture changes in sensing layers, those producing images of large-area devices are particularly interesting for chemical sensor array development. Until now, few studies addressed the characterization of image sensors from the point of view of their chemical sensor application. In this paper, a method to evaluate such performance is proposed. It is based on the simultaneous measurement of absorption events in a metalloporphyrin layer with an image sensor and a quartz microbalance (QMB). Exploiting the well-known behaviour of QMB, comparison of signals enables estimation of the minimum amount of absorbed molecules that the image sensor can detect. Results indicate that at the single pixel level a standard image sensor (for example a webcam) can easily detect femtomoles of absorbed molecules. It should therefore be possible to design sensor arrays in which the pixels of images of large-area sensing layers are regarded as individual chemical sensors providing a ready and simple method for large sensor array development.     

正丁胺等离子体膜TSM声波传感器的性能研究

等离子体聚合物在结构上与普通的聚合物显著不同,它能形成含有活性基团的高度交联的网络结构,从而具有良好的均匀性及对基质的附着性^[1,2].有关采用等离子体聚合膜的TSM传感器的报道不多^[3,4].     

Applications of microfabrication techniques in electrochemical sensor development

Electrochemical sensors have been used either as a whole or as an integral part of a chemical and biological sensing device. Microfabrication technology has been used in the development of electrochemical sensors. The recent advancement of micromachining techniques adds new impetus to electrochemical sensor development. Most noticable is the application of anisotropic chemical etching, plasma etching, sacrificial layer methods, and high aspect ratio X-ray lithography to enhance the opportunity to produce scientifically and commercially viable electrochemical sensors. Examples will be used to illustrate the potential of microfabrication and micromachining techniques in electrochemical sensor development.     

Electrochemical detection of ultratrace nitroaromatic explosives using ordered mesoporous carbon

A sensitive electrochemical sensor has been fabricated to detect ultratrace nitroaromatic explosives using ordered mesoporus carbon (OMC). OMC was synthesized and characterized by scanning electron microscopy, transmission electron microscopy and nitrogen adsorption/desorption measurements. Glassy carbon electrodes functionalized with OMC show high sensitivity of 62.7 μA cm⁻² per ppb towards 2,4,6-trinitrotoluene (TNT). By comparison with other materials such as carbon nanotubes and ordered mesoporous silica, it is found that the high performance of OMC toward sensing TNT is attributed to its large specific surface area and fast electron transfer capability. As low as 0.2 ppb TNT, 1 ppb 2,4-dinitrotoluene and 1 ppb 1,3-dinitrobenzene can be detected on OMC based electrodes. This work renders new opportunities to detect ultratrace explosives for applications of environment protections and home securities against chemical warfare agents.     

Self-powered sensors

One of the problems associated with miniaturization and portability of sensors is the power supply. Power supplies, such as batteries, are difficult to miniaturize and require a sensor design that allows for easy replacement or recharging. This review describes the field of self-powered sensing, where the sensor itself provides the power for the sensing device. Most self-powered-sensing strategies employ either nuclear energy conversion or electrochemical energy conversion. Nuclear energy conversion is employed for radioisotope or nuclear reactor sensing. Electrochemical energy conversion is employed for chemical and biological sensing. This review details the common strategies for self-powered nuclear, chemical, and biological sensing and discusses the future of the technology.     

α-Fe2O3负载Ag复合纳米材料的制备、表征和气敏性能

采用简单的FeCl3溶液水热方法, 结合焙烧处理合成了α-Fe2O3 纳米粉体; 以所制备的α-Fe2O3为载体负载Ag纳米粒子, 得到Ag/α-Fe2O3 复合纳米材料. 使用X射线衍射、 透射电子显微镜、 氮气吸附-脱附和X射线光电子能谱等对样品进行表征, 并考察了Ag/α-Fe2O3复合材料在260℃下对甲醇、 乙醇、 乙醚、 丙酮、 正丁醇和正己醇等挥发性有机物的气敏行为. 结果表明, Ag/α-Fe2O3传感器对这几种挥发性有机物展示了较高的灵敏度和快速、 可逆的响应-恢复特性; 与纯α-Fe2O3相比, Ag/α-Fe2O3复合材料的气敏性能显著提高, 这可能与该复合材料表面独特的多孔结构和活性Ag纳米粒子对敏感反应的催化作用有关.     

Investigation of the reliability of piezoelectric chemical sensors

The aim of the research was to study the functional change of sensitivity, selectivity and overall stability of piezoelectric chemical sensors. A test device was built and experiments have been carried out to estimate the degradation of the piezoelectric sensor performance. Sensing materials were inspected by a scanning electron microscope (SEM) to investigate the surface structures. Strong correlation was found between the reliability and the quality of the sensing material surface. The surface formation depended upon the physical and chemical properties of the sensing materials. Both the electrostatic and structural features influenced the interactions between the sensor surface and the analytes. Interactions during the adsorption and desorption of volatile compounds could not only be estimated by the van der Waals interactions. The contact area of interactions, where the secondary chemical forces play a significant role, was determined by the surface structure and the molecular structure of the sensing material. Polarity and different surface formation were found to be the most important factors to improve the discrimination capability of piezoelectric chemical sensors. The same investigations were repeated after 3 months. The most remarkable comparison was the appearance of the SEM images. A relationship was also recognized between the elapsed time and the degradation of the selectivity of the detectors. The method developed can be used to estimate the applicability of a piezoelectric chemical sensor.     

Agile Detection of Chemical Warfare Agents by Machine Vision: a Supramolecular Approach

The supramolecular detection by image analysis of a simulant chemical warfare agent on a solid device containing a selective molecular sensor based on a BODIPY scaffold is reported. The recognition properties were investigated in solution, demonstrating high affinity (log K 6.60) and sensitivity (LOD 10 ppt). A test strip also confirmed the sensing properties in gas phase. Image analysis of the solid device allows quantitative information about the simulant to be obtained, recovering the sensor almost 5 times and thus confirming the goal of the supramolecular approach.     

基于荧光内滤效应的荧光增强型钠离子光纤传感器

在吸收型钠离子光化学传感器的敏感膜中加入合适的荧光试剂,应用荧光内滤效应研制成的荧光增强型光纤传感器,在测量灵敏度和抗背景干扰能力方面均有较大的改善,对血清和矿泉水样品中的钠离子含量进行了分析,获得了满意的结果。     

Acoustic Wave Mass Sensors

The application of acoustic wave microsensors for mass sensing will be reviewed with focus on the quartz crystal microbalance (QCM) and surface acoustic wave (SAW) devices. The use of QCM and SAW devices in chemical sensing as well as in the determination of solid and liquid properties will be described. In chemical sensing, it is unlikely that a single sensor with a single coating will display a selective and reversible response to a given analyte in a mixture. Alternative strategies such as the use of sensor arrays and the use of sampling devices can be used to improve performance. QCM sensors (QCMs) will oscillate under liquids; their use in under-liquid sensing will be discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Survey on mass determination with oscillating systems: Part III. Acoustic wave mass sensors for chemical and biological sensing

We will review the application of acoustic wave mass sensors in chemical and biological sensing with focus on quartz crystal microbalance and surface acoustic wave devices. In chemical sensing, it is unlikely that a single sensor will display a selective and reversible response to a given analyte in a mixture. Alternative strategies such as use of sensor arrays and sampling devices will be discussed to improve performance. We will also discuss applications of quartz crystal microbalance as biosensor in the liquid phase.This revised version was published online in November 2005 with corrections to the Cover Date.     

纤维素接枝改性芴-苯和咔唑-苯共聚物及其对硝基芳烃的检测

采用Suzuki偶联反应将合成的芴-苯和咔唑-苯共聚物接枝到经化学改性的纸纤维素上,制备了可用于硝基芳烃检测的传感纸纤维素.荧光猝灭研究显示,由于两种传感纸纤维素具有的大比表面积和孔道结构有利于2,4-二硝基甲苯(DNT)蒸气分子的快速扩散,因此二者比薄膜态具有更高的荧光猝灭效率.荧光猝灭的可逆性研究显示,两种传感纤维素经过四次猝灭-恢复循环后,对DNT气态分子依然具有较高的猝灭效率,表明制备的纸纤维素具有良好的荧光猝灭可逆性和稳定性.     

Transistor-Based Work-Function Measurement of Metal–Organic Frameworks for Ultra-Low-Power,Rationally Designed Chemical Sensors

A classic challenge in chemical sensing is selectivity. Metal–organic frameworks (MOFs) are an exciting class of materials because they can be tuned for selective chemical adsorption. Adsorption events trigger work-function shifts, which can be detected with a chemical-sensitive field-effect transistor (power ≈microwatts). In this work, several case studies were used towards generalizing the sensing mechanism, ultimately towards our metal-centric hypothesis. HKUST-1 was used as a proof-of-principle humidity sensor. The response is thickness independent, meaning the response is surface localized. ZIF-8 is demonstrated to be an NO₂-sensing material, and the response is dominated by adsorption at metal sites. Finally, MFM-300(In) shows how standard hard–soft acid–base theory can be used to qualitatively predict sensor responses. This paper sets the groundwork for using the tunability of metal–organic frameworks for chemical sensing with distributed, scalable devices.     

Amphiphilic block copolymers directed synthesis of mesoporous nickel-based oxides with bimodal mesopores and nanocrystal-assembled walls

Ordered mesoporous Fe-doped NiO with dual mesopores, high surface area and well-interconnected crystalline porous frameworks have been synthesized via solvent evaporation-induced co-assembly (EICA) method, by using PS-b-P4VP as structure-directing agent, Ni(acac)₂ and Fe (acac)₃ as binary inorganic precursor, and showed superior ethanol sensing performances with good sensitivity, high selectivity and fast response-recovery dynamics.