Zongwei Cai

Synthesis and near-infrared luminescence of 3d-4f bi-metallic Schiff base complexes

The reaction of the zinc(II) Schiff base complex ZnL [H2L=N,N′-bis(3-methoxysalicylidene)ethylene-1,2-diamine] with one equivalent of Ln(NO3)3·xH2O (Ln=Nd, Ho, Er or Yb) gives the neutral 3d-4f bi-metallic Schiff base complexes [Zn(NO3)(μ-L)Ln(NO3)2(H2O)], which in solution exhibit emission corresponding to the Ln(III) ions (Ln=Nd, Er and Yb) in the near-infrared region.

Analytical chemistry of the persistent organic pollutants identified in the Stockholm Convention: A review.

Persistent organic pollutants (POPs) are major environmental concern due to their persistence, long-range transportability, bio-accumulation and potentially adverse effects on living organisms. Analytical chemistry plays an essential role in the measurement of POPs and provides important information on their distribution and environmental transformations. Much effort has been devoted during the last two decades to the development of faster, safer, more reliable and more sensitive analytical techniques for these pollutants. Since the Stockholm Convention (SC) on POPs was adopted 12 years ago, analytical methods have been extensively developed. This review article introduces recent analytical techniques and applications for the determination of POPs in environmental and biota samples, and summarizes the extraction, separation and instrumental analyses of the halogenated POPs. Also, this review covers important aspects for the analyses of SC POPs (e.g. lipid determination and quality assurance/quality control (QA/QC)), and finally discusses future trends for improving the POPs analyses and for potential new POPs.

Matrix interference-free method for the analysis of small molecules by using negative ion laser desorption/ionization on graphene flakes.

This work presents a new approach for the analysis of small molecules with direct negative ion laser desorption/ionization (LDI) on graphene flakes. A series of matrix interference-free mass spectra were obtained for the analysis of a wide range of small molecules including peptides, amino acids, fatty acids, as well as nucleosides and nucleotides. The mixture of analytes and graphene flakes suspension were directly pipetted onto a sample plate for LDI-time-of-flight mass spectrometry (TOFMS) analysis. Deprotonated monomeric species [M-H](-) ions were homogeneously obtained on uniform graphene flakes film when negative ion mode was applied. In positive ion mode, the analytes were detected in form of multiple adduct ions such as sodium adduct [M+Na](+), potassium adduct [M+K](+), double sodium adduct [M+2Na-H](+), double potassium adduct [M+2K-H](+), as well as sodium and potassium mixed adduct [M+Na+K-H](+). Better sensitivity and reproducibility were achieved in negative ion mode compared to positive ion mode. It is believed that the new method of matrix interference-free negative ion LDI on graphene flakes may be expanded for LDI-MS analysis of various small molecules.

Proteomics analysis of differential expression of cellular proteins in response to avian H9N2 virus infection in human cells

We present the first proteomic analysis on the cellular responses to avian influenza virus (H9N2) infection in a human cell line in different time courses in order to search for target proteins for viral pathogenesis/adaptation studies. By using 2‐DE coupled with MALDI‐TOF MS and nano‐ESI‐MS/MS, we identified a set of differentially expressed cellular proteins, including cytoplasmic actin, cytokeratin, prohibitin, enoyl‐CoA hydratase, peptide‐prolyl cis–trans isomerase A (PPIase A), chloride intracellular channel protein 1, pyruvate dehydrogenase E1 component subunit beta, adenine phosphoribosyltransferase, guanine nucleotide‐binding protein subunit beta, nucleoside diphosphate kinase A, elongation factor 1‐beta and splicing factor, arginine/serine rich 1. The most significant changes in different time courses were found in cytoplasmic actin and cytokeratin, both of which constituted the major components of cytoskeleton network in the cells. The obtained data suggested a possible role of the cytoskeleton during avian influenza virus infection of mammalian cells, which might help for better understanding of the dynamics of avian influenza virus and host interaction in mammalian cell setting.

Comparison on gestation and lactation exposure of perfluorinated compounds for newborns.

Perfluorinated compounds (PFCs) are worldwide present in the environment and the general population. Animal studies have shown developmental toxicity of these compounds. To investigate the PFCs exposure of neonates from mother during gestation and lactation, we analyzed twelve PFCs in matched maternal serum, cord serum and breast milk samples collected from 50 pairs of women and their newborns between June and July 2009 in Jinhu, China. Eight PFCs were detected in serum samples, and five of them were also detectable in breast milk. A significant intercorrelation between PFCs concentrations in matched maternal serum, cord serum and breast milk was observed (p<0.01, r=0.435-0.911). The median partition ratio was from 0.39:1 (PFDA) to 1.74:1 (PFTrDA) for seven PFCs through the placenta, and was from 0.02:1 (PFOS) to 0.09:1 (PFOA) for five PFCs through the lactation. A high transport efficiency of PFOA both through placental barrier and lactation was observed. The postnatal exposure of PFCs through lactation was higher compared to prenatal exposure, especially for PFOA.

Metabonomics Study on the Effects of the Ginsenoside Rg3 in a β-Cyclodextrin-Based Formulation on Tumor-Bearing Rats by a Fully Automatic Hydrophilic Interaction/Reversed-Phase Column-Switching HPLC−ESI-MS Approach

The goal of this study was the application of a novel, fully automatic column-switching approach in a metabonomics study combining the orthogonal selectivities of hydrophilic interaction chromatography (HILIC) and reversed-phase chromatography. The temporal, pharmacodynamic effects of the ginsenoside Rg3 on the metabonome in urine of healthy and liver-tumor-bearing rats have been investigated. Within a total analysis time of 52 min we detected 5686 polar, and on the second column an additional 1808 apolar, urinary metabolite ions. The administration of a single, high dose of Rg3 in a beta-cyclodextrin-based formulation led to a considerable change of the metabolic pattern in cancer rats during 3 days studied. Seventeen biomarker candidates including three apolar metabolites, which were not retained on the HILIC column, were detected. Overall, the results suggest that the developed liquid chromatography-mass spectrometry strategy is a promising tool in metabonomics studies for global analysis of highly complex biosamples. It may not only increase the number of discovered biomarkers but consequently improve the comprehensive information on metabolic changes in a fully automatic manner.

Studies on the aconitine-type alkaloids in the roots of Aconitum Carmichaeli Debx. by HPLC/ESIMS/MSn

Studies of aconitine-type alkaloids in the Chinese herb Aconitum Carmichaeli were performed by HPLC/ESIMS/MS(n) and FTICR/ESIMS in positive ion mode. The characteristic fragmentation pathways in the MS(n) spectra were summarized based on previously published research literature and further study. According to the fragmentation pathways of mass spectrometry, results from the analysis of standard compounds and reports from literature, 111 compounds were identified or deduced in a total of 117 found compounds in A. Carmichaeli. In the 11 monoester-diterpenoid alkaloids (MDA), 10 diesterditerpenoid alkaloids (DDA) and 81 lipo-alkaloids, the novel alkaloids including 1 MDA, 2 DDA and 48 lipo-alkaloids were detected. In addition, 1 DDA, 7 lipo-alkaloids and 2 alkaloids with small molecular weights that possess C19-norditerpenoid skeleton were reported in A. Carmichaeli for the first time.

Determination of polybrominated diphenyl ethers in soil from e-waste recycling site

Soil samples collected from an electronic waste recycling site were prepared by using Soxhlet extraction and multiple-step column chromatographic clean-up. Gas chromatography/ion trap mass spectrometry method was developed to determine polybrominated diphenyl ethers (PBDEs) in the sample extracts. The method performance was evaluated by the recovery of (13)C-labeled internal standards and by analyzing quality assurance and quality control samples. Relative error and relative standard deviation obtained from the analysis of duplicated samples and spiked matrix were better than 10%. PBDEs were detected in the field soil samples collected from an e-wastes disposal site at levels from low parts-per-billions to 600 parts-per-billions.

Triclosan determination in water related to wastewater treatment.

Triclosan in the waste, river and sea water samples collected in Hong Kong was analyzed by using gas chromatography-ion trap mass spectrometry method. (13)C(12)-triclosan was used as internal standard for the quantitative analysis. Water samples were prepared and cleaned-up by using a C(18) solid-phase extraction cartridge. The recoveries of triclosan in spiked coastal water at three different concentrations ranged from 83 to 110%. The method detection limit was 0.25 ng/L for triclosan in 1-L water and the relative standard deviations and relative error were less than 11.0 and 12.3%, respectively (n=3). The method was successfully applied to analyze water samples collected from rivers, coastal water bodies and wastewater treatment plants at ng/L levels.

Degradation of diphenylamine by persulfate: Performance optimization, kinetics and mechanism

The degradation of diphenylamine (DPA) in aqueous solution by persulfate is investigated. Effects of pH, persulfate concentration, ionic strength, temperature and catalytic ions Fe(3+) and Ag(+) on the degradation efficiency of DPA by persulfate are examined in batch experiments. The degradation of DPA by persulfate is found to follow the pseudo-first-order kinetic model. Increasing the reaction temperature or persulfate concentration may significantly accelerate the DPA degradation. Fe(3+) and Ag(+) ions can enhance the degradation of DPA, and Ag(+) ion is more efficient than Fe(3+) ion. However, the increase of either the pH value or ionic strength will decrease the rate of DPA degradation. N-Phenyl-4-quinoneimine, N-carboxyl-4-quinoneimine, 4-quinoneimine and oxalic acid are identified as the major intermediates of DPA degradation, and a primary pathway for the degradation of DPA is proposed. The degradation of DPA in surface water, groundwater and seawater is also tested by persulfate, and more than 90% of DPA can be degraded at room temperature in 45min at an initial concentration of 20mgL(-1).