Kailai Xu

Oxidation of Ethyl Ether on Borate Glass: Chemiluminescence, Mechanism, and Development of a Sensitive Gas Sensor

A gas sensor was developed by using the chemiluminescence (CL) emission from the oxidation of ethyl ether by oxygen in the air on the surface of borate glass. Theoretical calculation, together with experimental investigation, revealed the main CL reactions: ethyl ether is first oxidized to acetaldehyde and then to acetic acid, during which main luminous intermediates such as CH 3CO (*) are generated and emit light with a peak at 493 nm. At a reaction temperature of 245 degrees C, the overall maximal emission was found at around 460 nm, and the linear range of the CL intensity versus the concentration of ethyl ether was 0.12-51.7 microg mL (-1) ( R = 0.999, n = 7) with a limit of detection (3sigma) of 0.04 microg mL (-1). Interference from foreign substances including alcohol (methanol, ethanol and isopropanol), acetone, ethyl acetate, n-hexane, cyclohexane, dichloromethane, or ether ( n-butyl ether, tetrahydrofuran, propylene oxide, isopropyl ether and methyl tert-butyl ether) was not significant except a minimal signal from n-butyl ether (<2%). It is a simple, sensitive and selective gas sensor for the determination of trace ethyl ether.

Dielectric barrier discharge molecular emission spectrometer as multichannel GC detector for halohydrocarbons.

A novel microplasma molecular emission spectrometer based on an atmospheric pressure dielectric barrier discharge (DBD) is described and further used as a promising multichannel GC detector for halohydrocarbons. The plasma is generated in a DBD device consisting of an outer electrode (1.2 mm in diameter) and an inner electrode (1.7 mm in diameter) within a small quartz tube (3.0 mm i.d. × 5.0 mm o.d. × 50 mm), wherein analyte molecules are excited by the microplasma to generate molecular emission. Therefore, the analytes are selectively and simultaneously detected with a portable charge-coupled device (CCD) via multichannel detection of their specific emission lines. The performance of this method was evaluated by separation and detection of a model mixture of chlorinated hydrocarbons (CHCl(3) and CCl(4)), brominated hydrocarbons (CH(2)Br(2) and CH(2)BrCH(2)Br), and iodinated hydrocarbons (CH(3)I and (CH(3))(2)CHI) undergoing GC with the new detector. The completely resolved identification of the tested compounds was achieved by taking advantages of both chromatographic and spectral resolution. Under the optimized conditions with the CCD spectrometer set at 258, 292, and 342 nm channels for determination of chlorinated hydrocarbons, brominated hydrocarbons, and iodinated hydrocarbons, respectively, this detector with direct injection provided detection limits of 0.07, 0.06, 0.3, 0.04, 0.05, and 0.02 μg mL(-1) for CCl(4), CHCl(3), CH(2)Cl(2), CH(3)I, CH(3)CH(2)I, and (CH(3))(2)CHI, respectively.

A cataluminescence gas sensor for carbon tetrachloride based on nanosized ZnS

A novel and sensitive gas sensor was proposed for the determination of carbon tetrachloride based on its cataluminescence (CTL) by oxidation in the air on the surface of nanosized ZnS. The luminescence characteristics and the optimal conditions were investigated in detail. Under the optimized conditions, the linear range of the CTL intensity versus the concentration of carbon tetrachloride was 0.4-114microg mL(-1), with a correlation coefficient (R) of 0.9986 and a limit of detection (S/N=3) of 0.2microg mL(-1). The relative standard deviation (R.S.D.) for 5.9microg mL(-1) carbon tetrachloride was 2.9% (n=5). There was no or weak response to common foreign substances including methanol, ethanol, benzene, acetone, formaldehyde, acetaldehyde, dichloromethane, xylene, ammonia and trichloromethane. There was no significant change of the catalytic activity of the sensor for 40h over 4 days, with a R.S.D. of less than 5% by collecting the CTL intensity once an hour. The proposed method was simple and sensitive, with a potential of detecting carbon tetrachloride in environment and industry grounds. The possible mechanism was also discussed briefly.

Inorganic arsenic speciation analysis of water samples by trapping arsine on tungsten coil for atomic fluorescence spectrometric determination.

Arsine trapping on resistively heated tungsten coil was investigated and an analytical method for ultratrace arsenic determination in environmental samples was established. Several chemical modifiers, including Re, Pt, Mo, Ta and Rh, were explored as permanent chemical modifiers for tungsten coil on-line trapping and Rh gave the best performance. Arsine was on-line trapped on Rh-coated tungsten coil at 640 degrees C, then released at 1930 degrees C and subsequently delivered to an atomic fluorescence spectrometer (AFS) by a mixture of Ar and H(2) for measurement. In the medium of 2% (v/v) HCl and 3% (m/v) KBH(4), arsine can be selectively generated from As(III). Total inorganic arsenic was determined after pre-reduction of As(V) to As(III) in 0.5% (m/v) thiourea-0.5% (m/v) ascorbic acid solution. The concentration of As(V) was calculated by difference between the total inorganic arsenic and As(III), and inorganic arsenic speciation was thus achieved. With 8 min on-line trapping, the limit of detection was 10 ng L(-1) for As(III) and 9 ng L(-1) for total As; and the precision was found to be <5% R.S.D. (n=7) for 0.2 ng mL(-1) As. The proposed method was successfully applied in total arsenic determination of several standard reference materials and inorganic arsenic speciation analysis of nature water samples.

Single Drop Solution Electrode Glow Discharge for Plasma Assisted-Chemical Vapor Generation: Sensitive Detection of Zinc and Cadmium in Limited Amounts of Samples

A simple and sensitive approach is proposed and evaluated for determination of ultratrace Zn and Cd in limited amounts of samples or tens of cells based on a novel single drop (5-20 μL) solution electrode glow discharge assisted-chemical vapor generation technique. Volatile species of Zn and Cd were immediately generated and separated from the liquid phase for transporting to atomic fluorescence or atomic mass spectrometric detectors for their determination only using hydrogen when the glow discharge was ignited between the surface of a liquid drop and the tip of a tungsten electrode. Limits of detection are better than 0.01 μg L(-1) (0.2 pg) for Cd and 0.1 μg L(-1) (2 pg) for Zn, respectively, and comparable or better than the previously reported results due to only a 20 μL sampling volume required, which makes the proposed technique convenient for the determination of Zn and Cd in limited amounts of samples or even only tens of cells. The proposed method not only retains the advantages of conventional chemical vapor generation but also provides several unique advantages, including better sensitivity, lower sample and power consumption, higher chemical vapor generation efficiencies and simpler setup, as well as greener analytical chemistry. The utility of this technique was demonstrated by the determination of ultratrace Cd and Zn in several single human hair samples, Certified Reference Materials GBW07601a (human hair powder) and paramecium cells.

Hydride Generation for Headspace Solid-Phase Extraction with CdTe Quantum Dots Immobilized on Paper for Sensitive Visual Detection of Selenium

A low-cost, simple, and highly selective analytical method was developed for sensitive visual detection of selenium in human urine both outdoors and at home, by coupling hydride generation with headspace solid-phase extraction using quantum dots (QDs) immobilized on paper. The visible fluorescence from the CdTe QDs immobilized on paper was quenched by H2Se from hydride generation reaction and headspace solid-phase extraction. The potential mechanism was investigated by using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) as well as Density Functional Theory (DFT). Potential interferences from coexisting ions, particularly Ag(+), Cu(2+), and Zn(2+), were eliminated. The selectivity was significantly increased because the selenium hydride was effectively separated from sample matrices by hydride generation. Moreover, due to the high sampling efficiency of hydride generation and headspace solid phase extraction, the sensitivity and the limit of detection (LOD) were significantly improved compared to conventional methods. A LOD of 0.1 μg L(-1) and a relative standard deviation (RSD, n = 7) of 2.4% at a concentration of 20 μg L(-1) were obtained when using a commercial spectrofluorometer as the detector. Furthermore, a visual assay based on the proposed method was developed for the detection of Se, 5 μg L(-1) of selenium in urine can be discriminated from the blank solution with the naked eye. The proposed method was validated by analysis of certified reference materials and human urine samples with satisfactory results.

UV-Induced Surface Photovoltage and Photoluminescence on n-Si/TiO2/TiO2:Eu for Dual-Channel Sensing of Volatile Organic Compounds

In this work, a novel dual-channel sensing mode, i.e., UV-induced surface photovoltage (SPV) and photoluminescence (PL) on n-type Si/TiO(2)/Eu(3+)-doped TiO(2) (n-Si/TiO(2)/TiO(2):Eu), was demonstrated for the discrimination of 20 volatile compounds. The SPV signaling in this work employed a laboratory-constructed microvoltammeter with good analytical performances. This device also features wireless communication, portability, along with low cost and power consumption. The SPV and PL pattern of each analyte was distinct, and the hierarchical clustering analysis (HCA) result showed that these 20 volatile species were distinguishable, even for structural isomers. Linear discriminant analysis (LDA) further demonstrated the robustness of this sensor: 180 unknown samples from three groups at concentrations of 15.3, 31.7, and 79.2 mg/L were classified with accuracies of 96.7%, 95.0%, and 100%, respectively. Principal component analysis (PCA) revealed that SPV and PL channels contributed equally to the good discrimination ability due to two distinct sensing mechanisms. This dual-channel sensor was also successfully applied in the discrimination of beverage samples such as liquor, wine, and vinegar.

UV-induced atomization of gaseous mercury hydrides for atomic fluorescence spectrometric detection of inorganic and organic mercury after high performance liquid chromatographic separation

A novel, simple, low power, low temperature (<45 °C) and high efficiency atomization technique using ultraviolet (UV) radiation was proposed for the atomization of gaseous mercury hydrides for their determination by atomic fluorescence spectrometry (AFS). This technique was used for the detection of inorganic mercury (Hg2+) and organic mercury (MeHg+ and EtHg+) after high performance liquid chromatographic separation. In the proposed method, with 0.5% (m/v) KBH4 used as a reductant, inorganic mercury was reduced to elemental mercury, whereas the organic mercury species formed their respective volatile organic mercury hydrides (MeHgH and EtHgH) which were flushed to the UV atomizer for atomization and AFS detection. Under the optimized experimental conditions, the limits of detection were found to be 0.38, 0.41 and 0.56 μg L−1, and the relative standard deviations (n = 3) were 1.1%, 2.6% and 1.4% for Hg2+, MeHg+ and EtHg+, respectively. The accuracy of the proposed method was validated by analyzing a certified reference sample (fish muscle tissue) with a satisfactory analytical result, and two water samples with recoveries in the range of 93.8–97.4%.

Simple and sensitive determination of arsenic by volatile arsenic trichloride generation atomic fluorescence spectrometry

A simple, sensitive and interference-free method was proposed for the determination of arsenic, based on the generation of volatile arsenic trichloride coupled with atomic fluorescence spectrometry. Thiourea, together with l-ascorbic acid, was used to reduce As(V) to As(III), and the chloride generation was based on the reaction between As(III) and hydrochloric acid. Under the optimized experimental conditions, the present procedure allows for the quantification of arsenic in the concentration range of 0.01-4.0 mg L(-1), with a limit of detection (3sigma) of 6.0 microg L(-1). The relative standard deviation (R.S.D.) is 4.0% for 0.1 mg L(-1) arsenic (n=7). Finally, the proposed method was successfully applied to the determination of arsenic in several certified reference samples (stainless steel, alloy steel, copper alloy and water sample) and real samples (brass material and spiked cobalt material), with analytical results well-agreed with those by ICP-MS.

Modulation of the Singlet Oxygen Generation from the Double Strand DNA-SYBR Green I Complex Mediated by T-Melamine-T Mismatch for Visual Detection of Melamine

Singlet oxygen (1O2), generated via photosensitization, has been proved to oxidize chromogenic substrates with neither H2O2 oxidation nor enzyme (horseradish peroxidase, HRP) catalysis. Of the various methods for modulation of the 1O2 generation, DNA-controlled photosensitization received great attention. Therefore, integration of the formation/deformation DNA structures with DNA-controlled photosensitization will be extremely appealing in visual biosensor developments. Here, the stable melamine-thymine complex was explored in combination with DNA-controlled photosensitization for visual detection of melamine. A T-rich single stand DNA was utilized as the recognition unit. Upon the formation of the T-M-T complex, double stand DNA was formed, which was ready for the binding of SYBR Green I and activated the photosensitization. Subsequent oxidation of TMB allowed visual detection of melamine in dairy products, with spike-recoveries ranging from 94% to 106%.