基于荧光熄灭的二氧化硫选择性光化学敏感膜的研究

本文基于二氧硫对固定于增塑的聚氯乙烯膜上的芳香稠环化合物蒽的荧光熄灭，研制了二氧化硫选择性光化学敏感膜，经过组成优化 的敏感膜测定二氧化硫的浓度范围为6．59×10^-3-5.23×10^-1mol/L，校正曲线与理论推导的模拟曲线相吻合，且荧光信号具有较高的重现性，信号响应时间为5－30s.     

Ag@Au core/shell triangular nanoplates with dual enzyme-like properties for the colorimetric sensing of glucose

Due to the serious harm of diabetes to human health, development of sensitive assays for glucose level is of high significance for early prevention and treatment of diabetes. Currently, most conventional enzyme-based glucose sensors suffer from high cost and low stability due to the inherent defects of natural enzymes. Herein, we develop a pure nanozyme-based glucose detection method using Ag@Au core/shell triangular nanoplates (TNPs), which combines glucose oxidase (GOD)- and horseradish peroxidase (HRP)-like activities of the Au shell and inherent plasmonic properties of Ag TNPs. The sensing mechanism is based on the fact that the Au shell possessed GOD-like activity, enabling the oxidation of glucose to produce H₂O₂, which can further etch the silver core, leading to the decrease of absorbance at 800 nm and the color change from blue to colorless. Compared with the previous nanozymes-based glucose sensors, our method avoids the use of enzymes and organic chromogenic agent. Moreover, the stability of the Ag@Au core/shell TNPs is much better than that of Ag TNPs due to the protection by the coating of the Au shell. This method was successfully applied to the detection of urine samples from patients with diabetes, indicating its practical applicability for real sample analysis.     

A High Sensitivity Fluorescent Chemo-sensory System Based on β-Cyclodextrin Dimer Modified with Dansyl Moieties

-Cyclodextrin dimer linked with ethylenediamine at the upper rim of the cyclodextrin has been synthesized and then modified with two dansyl moieties inthe presence of N,N'-dicyclohexylcarbodiimide. The sensing ability and bindingproperty of the title compound were investigated for steroids and terpenoids. Thefluorescence intensity of this dimer was decreased when a host–guest complex was formed. The value I/I⁰, where I⁰ and I are fluorescence intensitiesin the absence and presence of a guest and I is I⁰- I, was used as a parameter of sensitivity. This host exhibited a much higher sensitivity and selective molecular recognition ability for bile acids such as ursodeoxycholic acid andchenodeoxycholic acid and terpenoids such as (-)-borneol than the dansyl-modifiedcyclodextrins reported previously including -cyclodextrin dimer. The behaviors of the appended moieties of the host during the formation of host–guest complexes were studied using induced circular dichroism (ICD) and fluorescence spectra. The ICD intensityof this dimer was decreased on accommodation of a guest and this spectral pattern of the title dimer was opposite to that of bis dansyl-modified -cyclodextrin monomer. Theguest-induced variations in the fluorescence and ICD intensities suggest that this dimer formed a 1 : 1 host–guest complex and the appended moieties act as a hydrophobic cap.     

Creation of highly functional thin films using electrochemical nanotechnology

This overview describes the results of our recent study of the application of electrochemical nanotechnology to the fabrication of magnetic recording materials, interconnects in ultra-large-scale integrated (ULSI) devices, energy storage materials, and on-chip biosensors. It is important to note that electrochemical processes play significant roles in developing and fabrication such sophisticated materials and devices. In the field of magnetic recording, electrodeposition methods for preparing CoNiFe and CoFe soft magnetic thin films with a high saturation magnetic flux density were newly developed, and the significant issues for obtaining those films are highlighted. In the area of ULSI interconnects, we developed a technique using a self-assembled monolayer (SAM) for direct bonding of the interconnect layer to SiO2, and proposed a novel electroless deposition method for fabricating a diffusion barrier layer. In the field of batteries, electrodeposited SnNi alloy was proposed as a future anode material for Li batteries, and electrochemical MEMS processes were shown to be useful for fabricating micro-sized direct methanol fuel cells (DMFCs) as portable batteries for electronics applications. In the area of chemical sensors, we developed a new process for fabricating field effect transistors (FETs) modified with SAMs for on-chip biosensing applications.     

Progress in the realisation of an autonomous environmental monitoring device for ammonia

Progress in the development of a micro-fluidic system for colorimetric monitoring of ammonia in drinking and wastewater is described. The ultimate goal is to have a miniaturised instrument that can produce accurate, reliable measurements, is easy to operate, has minimal power consumption, and can operate autonomously for a year. In this study, the indophenol reaction is incorporated into a simple, reliable analytical micro-fluidic system. Absorbance measurements for the blue ammonia-indophenol complex formed in the micro-fluidic system are shown. A key issue is the limiting stability of hypochlorite, a reagent used in the assay. The effects of hypochlorite concentration and impurities on the stability of hypochlorite are investigated and discussed. Decomposition is shown to be very dependent on the presence of heavy-metal impurities. With low levels of these catalytic metals and careful storage, hypochlorite has been shown to be stable for over a year.     

Mono- and oligosaccharide sensing by phenylboronic acid-appended 5,15-bis(diarylethynyl)porphyrin complexes

Porphyrin derivatives bearing a pair of boronic acid groups (1, 1·Zn, and 1·Cu) were designed and synthesized from 2 to construct a saccharide sensing system. Compounds 1, 1·Zn, and 1·Cu have a diethynyl porphyrin rotational axis, which is expected to act as a saccharide-binding modulator. Saccharide binding studies were conducted by UV-vis, fluorescence, and circular dichroism (CD) spectroscopies. In a water-methanol 1:1 (v/v) mixed solvent, we have found that 1·Zn can bind mono- and oligosaccharides including Lewis oligosaccharides to produce 1:1 host-saccharide complexes with the association constants of 10²−10³ M⁻¹ range. This paper thus demonstrates a new principle to design a boronic acid-based saccharide receptor.     

Comparison of Methionine α,γ‐Lyase and Homocysteine α,γ‐Lyase for Electrochemical Determination of Homocysteine

Recently, a novel enzymatic method was developed for determination of homocysteine. This method utilizes the electrochemical hydrogen sulfide sensor along with methionine α,γ‐lyase to accomplish the fast, accurate, sensitive and selective measurements. As a continuation of this work, another enzyme, homocysteine α,γ‐lyase, was used and the parallel experiments of using both enzymes were carried out against the effect of pH, sensitivity, linearity, and interferences, in an intended comparison between these two enzymes. The excellent linearity of amperometric currents against homocysteine concentrations, high sensitivities and low detection limits for both enzymes reconfirmed that the electrochemical method is superior over other analytical means. The high enzymatic activity of methionine α,γ‐lyase surpassing homocysteine α,γ‐lyase endowed the former higher sensitivity, lower detection limit and faster response than the latter, suggesting methionine α,γ‐lyase a better candidate for homocysteine measurement by electrochemical method. The differences between these two enzymes on the trends of response time and sensitivity at different pH environments, reactivity toward several forms of homocysteine as well as on the interference from several agents were also addressed and discussed.     

Real-time sensing and three-dimensional display of far outdoor scenes based on asymmetric integral imaging

A new asymmetric integral imaging (AII) system for real-time pickup and three-dimensional (3-D) display of far outdoor scenes based on dynamic-pixel-mapping (DPM) is proposed. DPM is a digital process to transform the elemental images captured with a lens array into the perspective-variant object images (POIs) whose structures are matched with those of display lenses, where the orders of pixels in each POI are reversely mapped, and then capture a set of virtual elemental images (EIs) at the specific depth planes from the back-propagated POIs. This DPM enables an asymmetrical use of pickup and display lens arrays, allowing the long-ranged pickup of far outdoor scenes and their resolution-enhanced 3-D reconstruction. Experiments with a pair of pickup and display lens arrays whose pitches and focal lengths are given by 7.5 mm, 30 mm and 1.2 mm, 8 mm, respectively, show that the effective pickup-range and resolution of the proposed system have been increased up to 6 m and 1600×1600 pixels, respectively, from 0.064 m and 480×480 pixels of the conventional systems employing the same pickup and display lens arrays. In addition, experiments with an implemented test bed confirms that the proposed system can provide real-time 3-D images in 25 frames per second.     

Specific ionic effect for simple and rapid colorimetric sensing assays of amino acids using gold nanoparticles modified with task-specific ionic liquid

In this study, a novel task-specific ionic liquid functionalized gold nanoparticle (TSIL-GNP) was successfully prepared and applied in the recognition of amino acids. Particularly, the surface of GNP was modified with the ionic liquid containing carbamido and ester group via thiol, which was characterized by Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). The stability of this material in aqueous solution improves apparently and can remain unchanged for more than three months. The effect of pH was also discussed in this study. Attractive ionic interaction would effectively weaken intensity of the covalent coupling between the metal ion and the functional groups of amino acids. Thus, TSIL-GNP was successfully applied to recognizing serine, aspartic acid, lysine, arginine, and histidine in the presence of Cu²⁺ through distinctive color changes. Suspension would be generated once a spot of cysteine was added into the GNPs solution. Results indicated that it had a good linear relationship between extinction coefficients and concentration of amino acids in a wide range of 10⁻³–10⁻⁶ M. Moreover, the proposed strategy was successfully used to analyze the histidine in urinary samples. In brief, TSIL-GNP is a suitable substrate for discrimination of five amino acids in a rapid and simple way without sophisticated instruments.     

Carbon dots with strong excitation-dependent fluorescence changes towards pH. Application as nanosensors for a broad range of pH

In this study, preparation of novel pH-sensitive N-doped carbon dots (NCDs) using glucose and urea is reported. The prepared NCDs present strong excitation-dependent fluorescence changes towards the pH that is a new behavior from these nanomaterials. By taking advantage of this unique behavior, two separated ratiometric pH sensors using emission spectra of the NCDs for both acidic (pH 2.0 to 8.0) and basic (pH 7.0 to 14.0) ranges of pH are constructed. Additionally, by considering the entire Excitation–Emission Matrix (EEM) of NCDs as analytical signal and using a suitable multivariate calibration method, a broad range of pH from 2.0 to 14.0 was well calibrated. The multivariate calibration method was independent from the concentration of NCDs and resulted in a very low average prediction error of 0.067 pH units. No changes in the predicted pH under UV irradiation (for 3 h) and at high ionic strength (up to 2 M NaCl) indicated the high stability of this pH nanosensor. The practicality of this pH nanosensor for pH determination in real water samples was validated with good accuracy and repeatability.