Jiping Chen

Porous nanosheet-based ZnO microspheres for the construction of direct electrochemical biosensors.

Nanosheet-based ZnO microsphere with porous nanostructures was synthesized by a facile chemical bath deposition method followed by thermal treatment, which was explored for the construction of electrochemical biosensors. Spectroscopic and electrochemical researches revealed the ZnO-based composite was a biocompatible immobilization matrix for enzymes with good enzymatic stability and bioactivity. With advantages of nanostructured inorganic-organic hybrid materials, a pair of stable and well-defined quasi-reversible redox peaks of hemoglobin was obtained with a formal potential of -0.345 V (vs. Ag/AgCl) in pH 7.0 buffer. Facilitated direct electron transfer of the metalloenzymes with an apparent heterogeneous electron transfer rate constant (k(s)) of 3.2s(-1) was achieved on the ZnO-based enzyme electrode. Comparative studies demonstrated the nanosheet-based ZnO microspheres were more effective in facilitating the electron transfer of immobilized enzyme than solid ZnO microspheres, which may result from the unique nanostructures and larger surface area of the porous ZnO. The prepared biosensor displayed good performance for the detection of H(2)O(2) and NaNO(2) with a wide linear range of 1-410 and 10-2700 microM, respectively. The entrapped hemoglobin exhibits high peroxidase-like activity for the catalytic reduction of H(2)O(2) with an apparent Michaelis-Menten constant (K(M)(app)) of 143 microM. The nanosheet-based ZnO could be a promising matrix for the fabrication of direct electrochemical biosensors, and may find wide potential applications in biomedical detection and environmental analysis.

Palladium-catalyzed cross-coupling of internal alkenes with terminal alkenes to functionalized 1,3-butadienes using C-H bond activation: efficient synthesis of bicyclic pyridones.

Transition-metal-catalyzed cross-coupling through C H bond activation is emerging as one of the most important tools for carbon–carbon bond formation. In general, vinylogous compounds can be synthesized by Wittig, Heck, and Suzuki reactions, from the condensation of carbonyl compounds, C H addition to alkynes, or by means of organometallic alkenyl compounds, but direct alkenylation using C H bond activation remains particularly attractive for constructing carbon–carbon double bonds owing to their synthetic simplicity and use of readily available reagents. Vinylborates, vinyl halides, alkenyl acetates, and cyclic 1,3-dicarbonyls have been known for the direct alkenylation of arene and (hetero)arene C H bonds. In a more simple and synthetically useful alkenylation, terminal alkenes have been applied as the coupling partners. However, little attention has been paid to the direct alkenylation of alkenyl C H bonds with an alkene as the coupling partner using C H bond activation. 1,3-Butadienes, as a class of versatile organic synthetic reagents, have usually been prepared by indirect methods. To date, only two reports have been documented for their direct synthesis, involving coupling two simple terminal alkenes, owing to the difficulty in activating two alkene substrates at the same time (Scheme 1). Although two examples involving the reaction of 3-methyl-1H-indenes with tert-butyl acrylate were also reported, no work has been directed to the direct alkenylation of open-chain internal alkenes with another alkene as the coupling partner. In order to realize the direct cross-coupling of an internal alkene with a terminal alkene, the low reactivity of an internal alkenyl C H bond should be overcome. We envisioned the introduction of a structural element that could increase the reactivity of an internal alkenyl C H bond. Thus, we hypothesized that a 1,2-dithiane group at the terminal position of an alkene should satisfy the requirement on activating an internal alkenyl C H bond, and a-oxoketene dithioacetals were chosen as the internal alkenes. Herein, we report the palladium(II)-catalyzed direct cross-coupling of a-oxoketene dithioacetals with terminal alkenes as well as the synthesis of bicyclic pyridones [Eq. (1)].

Pt-Sn/γ-Al2O3-catalyzed highly efficient direct synthesis of secondary and tertiary amines and imines.

Versatile syntheses of secondary and tertiary amines by highly efficient direct N-alkylation of primary and secondary amines with alcohols or by deaminative self-coupling of primary amines have been successfully realized by means of a heterogeneous bimetallic Pt-Sn/γ-Al(2)O(3) catalyst (0.5 wt % Pt, Pt/Sn molar ratio=1:3) through a borrowing-hydrogen strategy. In the presence of oxygen, imines were also efficiently prepared from the tandem reactions of amines with alcohols or between two primary amines. The proposed mechanism reveals that an alcohol or amine substrate is initially dehydrogenated to an aldehyde/ketone or NH-imine with concomitant formation of a [PtSn] hydride. Condensation of the aldehyde/ketone species or deamination of the NH-imine intermediate with another molecule of amine forms an N-substituted imine which is then reduced to a new amine product by the in-situ generated [PtSn] hydride under a nitrogen atmosphere or remains unchanged as the final product under an oxygen atmosphere. The Pt-Sn/γ-Al(2)O(3) catalyst can be easily recycled without Pt metal leaching and has exhibited very high catalytic activity toward a wide range of amine and alcohol substrates, which suggests potential for application in the direct production of secondary and tertiary amines and N-substituted imines.

Thin-layer chromatography of mycotoxins and comparison with other chromatographic methods

This paper highlights the status of thin-layer chromatography (TLC) of mycotoxins in various sample matrices. The outstanding merits of TLC in the field of the qualitative and quantitative determination of mycotoxins have been briefed. A comparison between different TLC methods and TLC with HPLC, enzyme-linked immunosorbent assay and GC methods, etc. is made, in general.

Emissions of PCDD/Fs from municipal solid waste incinerators in China

Gas emission of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) from 19 commercial municipal solid waste (MSW) incinerators in China are investigated. The emission concentrations of PCDD/Fs were 0.042-2.461 ng TEQ Nm(-3) with an average value of 0.423 ng TEQ Nm(-3). The emissions of PCDD/Fs from 16 MSW incinerators were below the MEP regulation level (1.0 ng I-TEQ Nm(-3)), while only six systems have the dioxin emission levels below the limit established by the European Union Directive of 0.1 ng I-TEQ Nm(-3). The emission factors of PCDD/Fs from 19 MSW incinerators were calculated to be 0.169-10.72 microg TEQ ton(-1) MSW with an average value of 1.728 microg I-TEQ ton(-1) MSW. The total amount of PCDD/Fs emitted from MSW incinerators to the atmosphere in China was estimated to 19.64 g TEQ year(-1) in 2006.

Nanographene-based tyrosinase biosensor for rapid detection of bisphenol A.

Hydrophilic nanographene (NGP) prepared by ball milling of graphite was used as the support to construct a novel tyrosinase biosensor for determination of bisphenol A (BPA). The performances of the nanographene-based tyrosinase biosensor were systematically compared with those of multiwall carbon nanotubes (MWNTs) modified tyrosinase biosensors. The results indicated that the nanographene-based tyrosinase biosensor provided significant advantages over MWNTs-based tyrosinase biosensor in term of response, repeatability, background current and limit of detection (LOD), which could be attributed to its larger specific surface area and unique hierarchical tyrosinase-NGP nanostructures. The nanographene-based tyrosinase biosensor displayed superior analytical performance over a linear range from 100 nmol L(-1) to 2000 nmol L(-1), with LOD of 33 nmol L(-1) and sensitivity of 3108.4 mA cm(-2)M(-1). The biosensor was further used for detecting BPA (leaching from different vessels) in tap water, and the accuracy of the results was validated by high performance liquid chromatography (HPLC). The nanographene-based tyrosinase biosensor proved to be a promising and reliable tool for rapid detection of BPA leached from polycarbonate plastic products and for on-site rapid analysis of emergency pollution affairs of BPA.

Environmental Occurrence and Distribution of Short Chain Chlorinated Paraffins in Sediments and Soils from the Liaohe River Basin, P. R. China

Chlorinated paraffins (CPs) are industrially produced in large quantities in the Liaohe River Basin. Their discharge inevitably causes environmental contamination. However, very limited information is available on their environmental levels and distributions in this typical industrial region. In this study, short chain CPs (SCCPs) were analyzed in sediments, paddy soils, and upland soils from the Liaohe River Basin, with concentrations ranging from 39.8 to 480.3 ng/g dry weight. A decreasing trend in SCCP concentrations was found with increasing distance from the cities, suggesting that local industrial activity was the major source of SCCP contamination. A preliminary sediment inventory of SCCPs indicated approximately 30.82 tonnes of SCCPs residual in the sediments from the Liaohe River. The average discharge of SCCPs was estimated to be about 74.4 mg/tonne industrial wastewater. The congener group profiles showed that the relative abundances of shorter chain and lower chlorinated CP congeners (C(10)-CPs with 5 or 6 chlorine atoms) in soils in rural areas were higher than in sites near cities, which demonstrated that long-range atmospheric transportation could be the major transport pathway. Environmental degradation of SCCPs might occur, where higher chlorinated congeners could dechlorinate to form the lower chlorinated congeners.

Polybrominated diphenyl ethers in sediments of the Daliao River Estuary, China: levels, distribution and their influencing factors.

The concentrations, compositional profiles, possible sources of polybrominated diphenyl ethers (PBDEs) in sediments of the Daliao River Estuary as well as the factors influencing the distribution of PBDEs were investigated. The total concentrations of PBDEs ranged from 0.13 to 1.98 ng g(-1)d.w. BDE209 was the dominating congener in all sediment samples, indicating the pollution of PBDEs in the Daliao River Estuary mainly came from the use of deca-BDE commercial mixtures. The intrusion of sea waters promoted the deposition of the colloid-associated PBDEs in the estuary. There were significantly negative correlations between PBDE concentration in sediment with pH value and salinity in the bottom water. The higher river flow in the flood season (summer) obviously accelerated the transport of PBDEs, and thereby increased the risk of PBDE contamination to the deep ocean. Moreover, a positive correlation between TOC and PBDE distributions was observed, suggesting that TOC regulated the distributions of PBDEs in sediments of Daliao River Estuary.

Molecularly imprinted polymer microspheres prepared by Pickering emulsion polymerization for selective solid-phase extraction of eight bisphenols from human urine samples.

The bisphenol A (BPA) imprinted polymer microspheres were prepared by simple Pickering emulsion polymerization. Compared to traditional bulk polymerization, both high yields of polymer and good control of particle sizes were achieved. The characterization results of scanning electron microscopy and nitrogen adsorption-desorption measurements showed that the obtained molecularly imprinted polymer microsphere (MIPMS) particles possessed regular spherical shape, narrow diameter distribution (30-60 μm), a specific surface area (S(BET)) of 281.26 m(2) g(-1) and a total pore volume (V(t)) of 0.459 cm(3) g(-1). Good specific adsorption capacity for BPA was obtained in the sorption experiment and good class selectivity for BPA and its seven structural analogs (bisphenol F, bisphenol B, bisphenol E, bisphenol AF, bisphenol S, bisphenol AP and bisphenol Z) was demonstrated by the chromatographic evaluation experiment. The MIPMS as solid-phase extraction (SPE) packing material was then evaluated for extraction and clean-up of these bisphenols (BPs) from human urine samples. An accurate and sensitive analytical method based on the MIPMS-SPE coupled with HPLC-DAD has been successfully established for simultaneous determination of eight BPs from human urine samples with detection limits of 1.2-2.2 ng mL(-1). The recoveries of BPs for urine samples at two spiking levels (100 and 500 ng mL(-1) for each BP) were in the range of 81.3-106.7% with RSD values below 8.3%.

3D metal-organic framework as highly efficient biosensing platform for ultrasensitive and rapid detection of bisphenol A

As is well known, bisphenol A (BPA), usually exists in daily plastic products, is one of the most important endocrine disrupting chemicals. In this work, copper-centered metal-organic framework (Cu-MOF) was synthesized, which was characterized by SEM, TEM, XRD, FTIR and electrochemical method. The resultant Cu-MOF was explored as a robust electrochemical biosensing platform by choosing tyrosinase (Tyr) as a model enzyme for ultrasensitive and rapid detection of BPA. The Cu-MOF provided a 3D structure with a large specific surface area, which was beneficial for enzyme and BPA absorption, and thus improved the sensitivity of the biosensor. Furthermore, Cu-MOF as a novel sorbent could increase the available BPA concentration to react with tyrosinase through π-π stacking interactions between BPA and Cu-MOF. The Tyr biosensor exhibited a high sensitivity of 0.2242A M(-1) for BPA, a wide linear range from 5.0×10(-8) to 3.0×10-6moll(-1), and a low detection limit of 13nmoll(-1). The response time for detection of BPA is less than 11s. The proposed method was successfully applied to rapid and selective detection of BPA in plastic products with satisfactory results. The recoveries are in the range of 94.0-101.6% for practical applications. With those remarkable advantages, MOFs-based 3D structures show great prospect as robust biosensing platform for ultrasensitive and rapid detection of BPA.