Highly Stable Solid Contact Calcium Ion-Selective Electrodes: Rapid Ion-Electron Transduction Triggered by Lipophilic Anions Participating in Redox Reactions of CunS Nanoflowers.

Solid contact (SC) calcium ion-selective electrodes (Ca2+-ISEs) have been widely applied in the analysis of water quality and body fluids by virtue of the unique advantages of easy operation and rapid response. However, the potential drift during the long-term stability test hinders their further practical applications. Designing novel redox SC layers with large capacitance and high hydrophobicity is a promising approach to stabilize the potential stability, meanwhile, exploring the transduction mechanism is also of great guiding significance for the precise design of SC layer materials. Herein, flower-like copper sulfide (CunS-50) composed of nanosheets is meticulously designed as the redox SC layer by modification with the surfactant (CTAB). The CunS-50-based Ca2+-ISE (CunS-50/Ca2+-ISE) demonstrates a near-Nernstian slope of 28.23 mV/dec for Ca2+ in a wide activity linear range of 10-7 to 10-1 M, with a low detection limit of 3.16 × 10-8 M. CunS-50/Ca2+-ISE possesses an extremely low potential drift of only 1.23 ± 0.13 µV/h in the long-term potential stability test. Notably, X-ray absorption fine-structure (XAFS) spectra and electrochemical experiments are adopted to elucidate the transduction mechanism that the lipophilic anion (TFPB-) participates in the redox reaction of CunS-50 at the solid-solid interface of ion-selective membrane (ISM) and redox inorganic SC layer (CunS-50), thereby promoting the generation of free electrons to accelerate ion-electron transduction. This work provides an in-depth comprehension of the transduction mechanism of the potentiometric response and an effective strategy for designing redox materials of ion-electron transduction triggered by lipophilic anions.

Ultrathin Tungsten Oxide Nanowires/Reduced Graphene Oxide Composites for Toluene Sensing.

Graphene-based composites have gained great attention in the field of gas sensor fabrication due to their higher surface area with additional functional groups. Decorating one-dimensional (1D) semiconductor nanomaterials on graphene also show potential benefits in gas sensing applications. Here we demonstrate the one-pot and low cost synthesis of W18O49 NWs/rGO composites with different amount of reduced graphene oxide (rGO) which show excellent gas-sensing properties towards toluene and strong dependence on their chemical composition. As compared to pure W18O49 NWs, an improved gas sensing response (2.8 times higher) was achieved in case of W18O49 NWs composite with 0.5 wt. % rGO. Promisingly, this strategy can be extended to prepare other nanowire based composites with excellent gas-sensing performance.

Hierarchical Morphology-Dependent Gas-Sensing Performances of Three-Dimensional SnO2 Nanostructures.

Hierarchical morphology-dependent gas-sensing performances have been demonstrated for three-dimensional SnO2 nanostructures. First, hierarchical SnO2 nanostructures assembled with ultrathin shuttle-shaped nanosheets have been synthesized via a facile and one-step hydrothermal approach. Due to thermal instability of hierarchical nanosheets, they are gradually shrunk into cone-shaped nanostructures and finally deduced into rod-shaped ones under a thermal treatment. Given the intrinsic advantages of three-dimensional hierarchical nanostructures, their gas-sensing properties have been further explored. The results indicate that their sensing behaviors are greatly related with their hierarchical morphologies. Among the achieved hierarchical morphologies, three-dimensional cone-shaped hierarchical SnO2 nanostructures display the highest relative response up to about 175 toward 100 ppm of acetone as an example. Furthermore, they also exhibit good sensing responses toward other typical volatile organic compounds (VOCs). Microstructured analyses suggest that these results are mainly ascribed to the formation of more active surface defects and mismatches for the cone-shaped hierarchical nanostructures during the process of thermal recrystallization. Promisingly, this surface-engineering strategy can be extended to prepare other three-dimensional metal oxide hierarchical nanostructures with good gas-sensing performances.

Trimethylamine Sensors Based on Au-Modified Hierarchical Porous Single-Crystalline ZnO Nanosheets.

It is of great significance for dynamic monitoring of foods in storage or during the transportation process through on-line detecting trimethylamine (TMA). Here, TMA were sensitively detected by Au-modified hierarchical porous single-crystalline ZnO nanosheets (HPSCZNs)-based sensors. The HPSCZNs were synthesized through a one-pot wet-chemical method followed by an annealing treatment. Polyethyleneimine (PEI) was used to modify the surface of the HPSCZNs, and then the PEI-modified samples were mixed with Au nanoparticles (NPs) sol solution. Electrostatic interactions drive Au nanoparticles loading onto the surface of the HPSCZNs. The Au-modified HPSCZNs were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive spectrum (EDS), respectively. The results show that Au-modified HPSCZNs-based sensors exhibit a high response to TMA. The linear range is from 10 to 300 ppb; while the detection limit is 10 ppb, which is the lowest value to our knowledge.

Porous and single-crystalline ZnO nanobelts: fabrication with annealing precursor nanobelts, and gas-sensing and optoelectronic performance.

Porous and single-crystalline ZnO nanobelts have been prepared through annealing precursors of ZnSe · 0.5N2H4 well-defined and smooth nanobelts, which have been synthesized via a simple hydrothermal method. The composition and morphology evolutions with the calcination temperatures have been investigated in detail for as-prepared precursor nanobelts, suggesting that they can be easily transformed into ZnO nanobelts by preserving their initial morphology via calcination in air. In contrast, the obtained ZnO nanobelts are densely porous, owing to the thermal decomposition and oxidization of the precursor nanobelts. More importantly, the achieved porous ZnO nanobelts are single-crystalline, different from previously reported ones. Motivated by the intrinsic properties of the porous structure and good electronic transporting ability of single crystals, their gas-sensing performance has been further explored. It is demonstrated that porous ZnO single-crystalline nanobelts exhibit high response and repeatability toward volatile organic compounds, such as ethanol and acetone, with a short response/recovery time. Furthermore, their optoelectronic behaviors indicate that they can be promisingly employed to fabricate photoelectrochemical sensors.

Learning Subspace-Based RBFNN Using Coevolutionary Algorithm for Complex Classification Tasks.

Many real-world classification problems are characterized by samples of a complex distribution in the input space. The classification accuracy is determined by intrinsic properties of all samples in subspaces of features. This paper proposes a novel algorithm for the construction of radial basis function neural network (RBFNN) classifier based on subspace learning. In this paper, feature subspaces are obtained for every hidden node of the RBFNN during the learning process. The connection weights between the input layer and the hidden layer are adjusted to produce various subspaces with dominative features for different hidden nodes. The network structure and dominative features are encoded in two subpopulations that are cooperatively coevolved using the coevolutionary algorithm to achieve a better global optimality for the estimated RBFNN. Experimental results illustrate that the proposed algorithm is able to obtain RBFNN models with both better classification accuracy and simpler network structure when compared with other learning algorithms. Thus, the proposed model provides a more flexible and efficient approach to complex classification tasks by employing the local characteristics of samples in subspaces.

Two bisthienylethene-Ir(III) complexes showing acid/base-induced structural transformation and on-off luminescence switching in solution.

Complexes [Ir(dfppy)2(pbdtiH)](PF6)·2CHCl3 (1-H) and [Ir(dfppy)2(pbdti)] (1) were synthesized by the reaction of bisthienylethene pbdtiH and an [Ir(dfppy)2Cl]2 dimer under neutral and basic conditions, respectively. Thus, the {Ir(dfppy)2}(+) unit is coordinated by pbdtiH in 1-H, and by pbdti(-) in 1, which are confirmed by their crystal structures. The structures of 1-H and 1 could be interconverted in solution, upon alternately adding NEt3 and TFA, thus resulting in reversible luminescence switching between the on-state of 1-H and the off-state of 1 at room temperature. In addition, both 1-H and 1 show solid-state luminescence, with a broad emission at 534 nm and 525 nm, respectively. The free pbdtiH ligand shows photochromic behavior in CH2Cl2 solution. However, no photochromism has been observed in 1-H and 1, indicating that the coordination of the pbdtiH/pbdti(-) ligand to the {Ir(dfppy)2}(+) unit could suppress their photochromic behaviors.

Cation Exchange Synthesis and Unusual Resistive Switching Behaviors of Ag2Se Nanobelts.

Ag2Se nanobelts are prepared through employing ZnSe nanobelts as templates via a facile cation exchange approach. The templates are derived from precursor ZnSe·0.5N2 H4 nanobelts, which are synthesized by a simple hydrothermal method. As-synthesized precursor nanobelts are with 200 nm in width and several hundreds of micrometers in length. Annealed in N2 , they are transformed into ZnSe nanobelts with preserving their initial morphology. Following with a complete replacement of Zn(2+) by Ag(+), Ag2Se nanobelts with single crystalline are obtained via a cation-exchange reaction. Combined with the Langmuir-Blodgett assembly technique, regular films of ZnSe nanobelts can be achieved on transparent glass substrates and Si wafers with interdigital Au electrode arrays. Further, the optical and electrical evolutions are investigated from ZnSe nanobelts to Ag2 Se nanobelts. Finally, the resistive switching characteristic are carefully explored for Ag2Se nanobelts regularly arranged on interdigital Au microelectrodes. The results indicate that it is analogous to complementary resistive switching behaviors, which is different from that of traditional two terminal devices about previously reported Ag2Se. In order to clarify this phenomenon, a possible mechanism has been proposed and indirectly demonstrated through in situ SEM (scanning electron microscropy) observation.

A novel paper rag as 'D-SERS' substrate for detection of pesticide residues at various peels.

Many important considerations in the design of practical Surface enhanced Raman spectroscopy (SERS) substrates are necessary, such as the low cost, simple preparation, mass production and high efficiency of sample collection, which the conventional rigid substrates are lack of. In this work, practical SERS substrates based on deposition of silver nanoparticles (Ag NPs) on commercially available low-cost filter paper were prepared by simple silver mirror reaction in a large scale, and utilized for rapid, portable and accurate identification and detection of pesticide residues at various peels. Compared with conventional substrates, this novel SERS substrate dramatically enhanced the sample collection efficiency by simply swabbing paper-based device across different surfaces without destroying the sample, meanwhile avoiding the substrate signal of real-world samples. Considering their low cost, portability, simplicity and high sample collection efficiency, Ag NP-decorated filter paper, as practical SERS substrate, are used in solving critical problems for detection of pesticide residues at various peels. SERS experiments were carried out on Ag NP-decorated filter paper combined with 'dynamic SERS' (D-SERS) due to its high detection sensitivity. The excellent detection performance of the Ag NP-based filter paper was demonstrated by detection thiram and paraoxon residues at various peels. Besides, the stability and reproducibility of the practical substrates were also involved.

Sensitive and selective system of benzene detection based on a cataluminescence sensor.

Au/La2 O3 nanomaterials were prepared through calcining Au-modified La(OH)3 precursors. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffractometry (XRD) were employed to characterize the as-prepared samples. Benzene, a common volatile organic compound, was selected as a model to investigate the cataluminescence (CTL)-sensing properties of the Au/La2 O3 nanomaterials. Results indicated that the as-prepared Au/La2 O3 exhibited outstanding CTL properties such as stable intensity, high signal-to-noise values, and short response and recovery times. Under optimized conditions, the benzene assay exhibited a broad linear range of 1-4000 ppm, with a limit of detection of 0.7 ppm, which was below the standard permitted concentrations. Furthermore, the gas sensor system showed outstanding selectivity for benzene compared with seven other types of common volatile organic compounds (VOCs). The proposed gas sensor showed good characteristics with high selectivity, fast response time and long lifetime, which suggested the promising application of the Au/La2 O3 nanomaterials as a novel highly efficient CTL-sensing material.

The analysis of time-resolved optical waveguide absorption spectroscopy based on positive matrix factorization.

Time-resolved optical waveguide absorption spectroscopy (OWAS) makes use of an evanescent field to detect the polarized absorption spectra of sub-monomolecular adlayers. This technique is suitable for the investigation of kinetics at the solid/liquid interface of dyes, pigments, fluorescent molecules, quantum dots, metallic nanoparticles, and proteins with chromophores. In this work, we demonstrate the application of positive matrix factorization (PMF) to analyze time-resolved OWAS for the first time. Meanwhile, PCA is researched to compare with PMF. The absorption/desorption kinetics of Rhodamine 6G (R6G) onto a hydrophilic glass surface and the dynamic process of Meisenheimer complex between Cysteine and TNT are selected as samples to verify experimental system and analytical methods. The results are shown that time-resolved OWAS can well record the absorption/desorption of R6G onto a hydrophilic glass surface and the dynamic formation process of Meisenheimer complexes. The feature of OWAS extracted by PMF is dynamic and consistent with the results analyzed by the traditional function of time/wavelength-absorbance. Moreover, PMF prevents the negative factors from occurring, avoids contradicting physical reality, and makes factors more easily interpretable. Therefore, we believe that PMF will provide a valuable analysis route to allow processing of increasingly large and complex data sets.

Novel facile detection of persistent organic pollutants using highly sensitive gas sensor.

Persistent organic pollutants (POPs) are greatly noxious chemicals in environment, and they can cumulate in organisms and transfer between different species. Therefore, it is significant to detect POPs for both environmental evaluation and further treatment. However, developing facile approach for the detection of POPs still remains a challenge so far. In this paper, we report an innovative method for facile detection of POPs using gas sensor for the first time. Porous SnO(2) nanostructures with a special tri-walled structure prepared via hydrothermal route and annealing process, were employed as gas-sensing materials. Through gas measurements, it was revealed that the as-fabricated gas sensor exhibited highly sensitive performance towards target POPs, including methoxychlor, mirex, p,p'-DDT, and aldrin. Moreover, we found that target POPs were distinguishable by extracting characteristics in kinetic curves of gas adsorption-desorption. As the presented detecting approach is facile without the requirements of complex operations, expensive and bulky instruments, it is expected that it would be developed as a promising method for the detection of POPs, and thereby showing its significance for environmental monitoring.

A novel coral-like porous SnO2 hollow architecture: biomimetic swallowing growth mechanism and enhanced photovoltaic property for dye-sensitized solar cell application.

A unique coral-like porous SnO(2) hollow architecture with enhanced photovoltaic property for dye-sensitized solar cell application was prepared, and a biomimetic swallowing growth mechanism for the formation of the special structure was also proposed for the first time.

Novel porous single-crystalline ZnO nanosheets fabricated by annealing ZnS(en)0.5 (en = ethylenediamine) precursor. Application in a gas sensor for indoor air contaminant detection.

Novel single-crystalline ZnO nanosheets with porous structure have been fabricated by annealing ZnS(en)(0.5) (en = ethylenediamine) complex precursor. The morphology and structure observations performed by field emission scanning electronic microscopy (FESEM) and high-resolution transmission electron microscopy (HRTEM) indicate that numerous mesopores with a diameter of about 26.1 nm distribute all through each nanosheet with a high density. The transformation of structure and composition of samples obtained during thermal treatment processes were investigated by x-ray diffraction (XRD), x-ray photoelectron spectrometry (XPS), thermogravimetric analysis (TGA), and Fourier transform infrared (FTIR) absorption spectroscopy. The formation mechanism of the porous structure is proposed. For indoor air contaminant detection in which formaldehyde and ammonia are employed as target gases, the as-prepared ZnO nanosheets were applied for the fabrication of gas sensors. It was found that the as-fabricated sensors not only exhibit highly sensitive performance, e.g., high gas-sensing responses, short response and recovery time, but also possess significant long-term stability. It is indicated that these ZnO nanostructures could promisingly be applied in electronic devices for environmental evaluation.

Morphogenesis and crystallization of ZnS microspheres by a soft template-assisted hydrothermal route: synthesis, growth mechanism, and oxygen sensitivity.

Almost monodisperse ZnS microspheres have been synthesized on a large scale by a hydrothermal route, in which tungstosilicate acid (TSA) was used as a soft template. By controlling the reaction conditions, such as reaction temperature, pH value of the solutions, and the reaction medium, almost monodisperse microspheres can be synthesized. The structure of these microspheres is sensitive to the reaction conditions. The growth mechanism of these nearly monodisperse microspheres was examined. Oxygen sensing is realized from ZnS microspheres. The current through the ZnS microspheres under UV illumination increases as the oxygen concentration decreases.

Nanomaterial-assisted signal enhancement of hybridization for DNA biosensors: a review.

Detection of DNA sequences has received broad attention due to its potential applications in a variety of fields. As sensitivity of DNA biosensors is determined by signal variation of hybridization events, the signal enhancement is of great significance for improving the sensitivity in DNA detection, which still remains a great challenge. Nanomaterials, which possess some unique chemical and physical properties caused by nanoscale effects, provide a new opportunity for developing novel nanomaterial-based signal-enhancers for DNA biosensors. In this review, recent progress concerning this field, including some newly-developed signal enhancement approaches using quantum-dots, carbon nanotubes and their composites reported by our group and other researchers are comprehensively summarized. Reports on signal enhancement of DNA biosensors by non-nanomaterials, such as enzymes and polymer reagents, are also reviewed for comparison. Furthermore, the prospects for developing DNA biosensors using nanomaterials as signal-enhancers in future are also indicated.

Template synthesis, organic gas-sensing and optical properties of hollow and porous In(2)O(3) nanospheres.

Hollow and porous In(2)O(3) nanospheres have been prepared by the hydrolysis of InCl(3) using carbonaceous spheres as templates in combination with calcination. Based on the observation of scanning electronic microscopy (SEM) and transmission electron microscopy (TEM), it has been revealed that the as-prepared In(2)O(3) nanospheres have a uniform diameter of around 200 nm and hollow structures with thin shells of about 30 nm consisting of numerous nanocrystals and nanopores. Owing to the hollow and porous structures, In(2)O(3) nanospheres possessing more active surface area exhibit a good response and reversibility to some organic gases such as methanol, alcohol, acetone and ethyl ether. In addition, the response mechanism of hollow and porous In(2)O(3) nanospheres to organic gases has been proposed. Furthermore, these prepared In(2)O(3) spheres showed a UV-visible absorption peak centered at around 309 nm, and their photoluminescence spectra have also been investigated.

Highly porous CdO nanowires: preparation based on hydroxy- and carbonate-containing cadmium compound precursor nanowires, gas sensing and optical properties.

Highly porous cadmium oxide (CdO) nanowires have been prepared by calcining the hydroxy- and carbonate-containing cadmium compound precursor nanowires. The large-scale precursor nanowires were synthesized through a hydrothermal method. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to characterize and analyze the as-synthesized precursor nanowires as well as the calcined products. It was revealed that the wire-like morphology of the precursor was fundamentally retained during the process of calcination and the CdO nanowires obtained were polycrystalline with highly porous structures. In order to illustrate the formation mechanism of the porous structures, the morphology and composition evolutions of the precursor nanowires under different stages of the calcining process were further investigated via SEM, x-ray diffraction (XRD) and infrared (IR) absorbance spectroscopy. Gas sensing has been explored for the sensor device fabricated with highly porous CdO nanowires, which demonstrates that it has good response owing to its special structures and great selectivity to NO(x). Furthermore, the UV-visible and photoluminescence spectra of highly porous CdO nanowires have also been investigated.

A novel microcomputer temperature-compensating method for an overtone crystal oscillator.

In this paper, a novel microcomputer temperature-compensating method for an overtone crystal oscillator (MCOXO) is presented. In this method, a ceramic oscillator is chosen, and its output frequency is mixed with the output frequency of an overtone crystal oscillator. A crystal filter is used to suppress the spurious mixing products. A microcomputer is used to control the switch capacitance array that is connected to the ceramic oscillator circuit. The frequency deviation of the crystal oscillator is directly compensated by the output frequency of the ceramic oscillator. As a result, the method is able to overcome the disadvantages of frequency stability degradation and phase noise deterioration that are provoked by adding inductance or frequency multiplication in traditional compensating approaches. At the same time, this method is able to compensate a quite wide frequency range and many types of oscillators, not just crystal oscillators. The experimental compensating results show that, using this method, the frequency-temperature stability of a 100 MHz 5th overtone temperature-compensated crystal oscillator can achieve < or = +/-2 x 10(-6) for 0-70 degrees C.