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Abstract: Licorice, the roots of Glycyrrhizia uralensis Fisch, is used as a medicinal herb and food additive in China. At present, the quality grading and authentication of licorice products is generally done by visual inspection, which is subjective and often biased. In this study, a rapid and nondestructive method for the classification of licorice samples according to their growing conditions, geographic areas and plant parts was developed using fiber optic diffuse reflectance near-infrared spectroscopy (FODR-NIR). With the use of multiplicative signal correlation (MSC) and Norris derivative filter, the differences of the NIR spectra among different licorice samples were enhanced even though the raw spectra were very similar. The results showed that the NIR spectra of the samples were moderately clustered in the principle component spaces, and pattern recognition technique of soft independent modeling of class analogy (SIMCA) provided satisfactory classification results. Additionally, a partial least square (PLS) method using HPLC data set as reference was constructed to predict the value of glycyrrhizic acid (GA) in licorice. The results showed that PLS models with both data normalization (DN) coupled with first derivative pretreatments, and MSC coupled with first derivative pretreatments provided acceptable results. [Copyright &y& Elsevier]

Abstract: Camellia oil is often the target for adulteration or mislabeling in China because of it is a high priced product with high nutritional and medical values. In this study, the use of attenuated total reflectance infrared spectroscopy (MIR-ATR) and fiber optic diffuse reflectance near infrared spectroscopy (FODR-NIR) as rapid and cost-efficient classification and quantification techniques for the authentication of camellia oils have been preliminarily investigated. MIR spectra in the range of 4000–650cm−1 and NIR spectra in the range of 10,000–4000cm−1 were recorded for pure camellia oils and camellia oil samples adulterated with varying concentrations of soybean oil (5–25% adulterations in the weight of camellia oil). Identifications is successfully made base on the slightly difference in raw spectra in the MIR ranges of 1132–885cm−1 and NIR ranges of 6200–5400cm−1 between the pure camellia oil and those adulterated with soybean oil with soft independent modeling of class analogy (SIMCA) pattern recognition technique. Such differences reflect the compositional difference between the two oils with oleic acid being the main ingredient in camellia oil and linoleic acid in the soybean oil. Furthermore, a partial least squares (PLS) model was established to predict the concentration of the adulterant. Models constructed using first derivative by combination of standard normal variate (SNV), variance scaling (VS), mean centering (MC) and Norris derivative (ND) smoothing pretreatments yielded the best prediction results With MIR techniques. The R value for PLS model is 0.994.The root mean standard error of the calibration set (RMSEC) is 0.645, the root mean standard error of prediction set (RMSEP) and the root mean standard error of cross validation (RMSECV) are 0.667 and 0.85, respectively. While with NIR techniques, NIR data without derivative gave the best quantification results. The R value for NIR PLS model is 0.992. The RMSEC, RMSEP and RMSECV are 0.70, 1.78 and 1.79, respectively. Overall, either of the spectral method is easy to perform and expedient, avoiding problems associated with sample handling and pretreatment than the conventional technique. [Copyright &y& Elsevier]

PM 2.5 samples were collected at six indoor public places that contained dedicated smoking lounges. Samples were taken in the smoking lounges, at two indoor locations outside of the lounges, and in outdoor air near the venues. Organic carbon (OC), elemental carbon (EC), and non-polar organic compounds including polycyclic aromatic hydrocarbons (PAHs), n -alkanes ( n -C 16 to n -C 40 ), iso/anteiso-alkanes (C 29 to C 33 ), hopanes and phthalate esters (PAEs) were quantified. Average PM 2.5 levels of 170.2 ± 85.9 μg/m 3 in the lounges exceeded limits of 25 μg/m 3 set by World Health Organization (WHO); these levels were 5.4 and 3.9 times higher than those indoors and outdoors, respectively. High ratios of OC to PM 2.5 , OC to EC, and PAHs diagnostic ratios in the lounges indicated contributions from environmental tobacco smoke (ETS). The maximum carbon number (C max ) and carbon preference indices (CPI) for n -alkanes showed ETS transport from the enclosed lounges to nearby indoor non-smoking areas. Iso/anteiso-alkanes in the lounges were 876.5 ng/m 3 , ∼80 times higher than outdoor levels. 17α(H)-21β(H),30-norhopane and 17α(H)-21β(H),(22R)-homohopane were much higher in the lounges than outdoor air, but they cannot be directly attributed to ETS. Estimated carcinogenic risks of PAHs in the lounges exceeded the acceptable level of 10 − 6 . [ABSTRACT FROM AUTHOR]

Abstract: In China, fast increase in passenger cars and gasoline consumption with yet quite limited vapor recovery during gasoline distribution has procured growing concern about gasoline evaporation as an important emission source of volatile organic compounds (VOCs), particularly in megacities hard-hit by air quality problems. This study presents VOC species profiles related to major pathways of gasoline evaporative loss in China, including headspace displacement, refueling operations and spillage/leakage. Apart from liquid gasoline and headspace vapors, gasoline vapors emitted when refueling cars in service stations or tank trucks in oil marketing depots were also sampled in situ with vapor recovery units (VRUs) turning on/off. Alkanes, alkenes and aromatic hydrocarbons accounted for 55–66, 21–35 and 4–8% in refueling vapors, 59–72, 18–28 and 4–10% in headspace vapors and 33–51, 8–15 and 38–48% in liquid gasoline samples, respectively. During refueling with VRUs turning on, total VOCs in vapors were less than one fifth of that with VRUs turning off, and aromatic hydrocarbons had higher weight percentages of about 8% in contrast with that of about 4% during refueling with VRUs turning off. Refueling vapors, especially for that with VRUs turning off, showed a larger fraction of light hydrocarbons including C3–C5 light alkenes when compared to headspace vapors, probably due to splashing and disturbance during filling operation. In refueling or headspace vapors the ratios of i-pentane/benzene, i-pentane/toluene, and MTBE (methyl tert-butyl ether)/benzene ranged 8.7–57, 2.7–4.8, and 1.9–6.6, respectively; and they are distinctively much higher than those previously reported in vehicle exhausts. Calculated normalized reactivity or ozone formation potential of the gasoline vapors in China ranged 3.3–4.4 g O3 g−1 VOC, about twice that of gasoline headspace vapors reported in USA as a result of larger fractions of alkenes in China's gasoline vapors. The results suggested that reducing VOC emission from gasoline distribution sector would particularly benefit ground-level ozone control in China. [Copyright &y& Elsevier]

Enhanced anticoagulation and/or even bleeding are often observed when patients on long-term warfarin (WAR) therapy consumed Danshen, a well-known medicinal herb in traditional Chinese medicine (TCM). This study demonstrates that altered WAR metabolism, arising from its interaction with the active components in Danshen, played a significant role in this curative effect. Mass spectrometric techniques including ESI-ITMS (electrospray ionization ion-trap mass spectrometry) and ESI-TOF (time-of-flight)-MS have been developed for the study of such drug–herb interactions. The experimental approach involved a detailed analysis and comparison of WAR metabolites in vivo from blood or urine of rats that had been orally administrated with WAR, either singly or together with the representative bioactive component of Danshen–lipid soluble TIIA (Tanshinon IIA), and a study of the interaction of human serum albumin (HSA), WAR, and water-soluble sodium tanshinone IIA sulfonate (STS) in vitro. Results demonstrate that TIIA accelerates the metabolic rate of WAR, whereas STS displaces WAR from the WAR–HSA complex, resulting in an increase of free WAR concentration in blood. It is suggested that the elevated level and enhanced metabolism of WAR is responsible for the over-anticoagulation effect observed. [Copyright &y& Elsevier]

The extent of organochlorine pesticides (OCPs) contamination in coastal waters around LaiZhou Bay and JiaoZhou Bay in Shandong Peninsula, northern China, was investigated. The areas around the two bays are both densely populated, thrived with intensive agriculture and industrial activities. Multi-techniques including GC–MS, GC–μECD coupled with chemical peak confirmation and strict QC procedures were used for the quantitative determination of 15 OCPs including alpha, beta, gamma and delta isomers of hexachlorocyclohexane (HCH), pentachloronitrobenzene (PCNB), heptachlor, aldrin, endosulfan, p,p′-DDE, dieldrin, endrin, p,p′-DDD, o,p′-DDT, p,p′-DDT and methoxychlor. The survey results show that contaminations by OCP residues remain widespread in the areas, but the averaged concentration levels are all below the regulatory limits, e.g., CMC limits (acute criterion values) specified in US Environmental Protection Agency (USEPA) and China national standards. Average concentration of OCPs in water samples were from undetectable to 3. 8ngl−1 in LaiZhou Bay and from 0. 1 to 3. 9ngl−1 in JiaoZhou Bay, respectively. A comparison between the current and historical data shows a rapidly decreasing trend of OCPs over the past twenty years in the study areas. [Copyright &y& Elsevier]

Abstract: The biodegradation of the organophosphorus insecticide methyl parathion (MP) in aqueous environment by bacteria isolated from river sediment has been studied. Two species of bacteria which show strong MP degradation ability are identified as Shewanella and Vibrio parahaemolyticus. The biodegradation of MP proceeded rapidly with the formation of a series of intermediate products, which were analyzed using a combination of GC/MS and HPLC/ESI-TOFMS techniques. The major products tentatively identified include a series of reduced products of MP. Results demonstrate that the coupling of TOFMS to HPLC enhances further the capability of LC–MS in the identification of polar organic species in complex environmental samples. Degradation pathways leading to the formation of these products are proposed which involves first the reduction of nitro to amino group in MP, followed by combination with some intrinsic matters of bacteria. The mechanism and products from biodegradation are quite different from those of photocatalytic process for which the main intermediates included methyl paraoxon and 4-nitrophenol. [Copyright &y& Elsevier]

Abstract: Polymerization of metallothioneins (MTs) is one of the commonly encountered puzzles in researching the structure and function of metallothioneins. In this work, a method involving SEC coupled with negative ion electrospray ionization mass spectrometry (ESI-MS) detection has been developed for the study of zinc binding MTs’ polymerization in tris(hydroxymethyl)-aminomethane (TRIS) acetate buffer at physiological pH. This hyphenated technique allows separating the different polymeric states of MTs by SEC, followed by on-line identification of the individual MT subisoforms in each polymeric peak by ESI-MS detection. Purified MT subisoforms (MT-2d and MT-2a), MT-2d and MT-2a mixture and rabbit liver MT complexes were investigated in the experiments to confirm the results obtained. From the results, both oxidative polymerization and non-oxidative oligomerization were found. The cystein-dependent oxidation results in the tetrameric peak as shown in the chromatograms of oxidized MT-2d, and stable dimeric and monomeric of MT were detected in this peak by MS. For the dimeric and trimeric peaks, different MT subisoforms were detected. In the five major subisoforms detected in rabbit liver MT complexes, MT-2a and MT-2c exist primarily as trimer, while MT-2e, MT-2d and MT-1a exist mainly as dimer. Our results suggest that in the three kinds of polymers, dimer, trimer and tetramer that were found in samples, the tetramer comes from the oxidation of MT molecular; for the dimer and trimer resulting from cystein independent oligomerization, they are closely associated with the charge of subisoform. [Copyright &y& Elsevier]

Abstract: The purpose of this study is to develop and apply a mercury analyzer system capable of quantitative analysis of mercury in Traditional Chinese Medicines (TCM) drugs in the concentrations range from ngg−1 to mgg−1. No sample pre-treatment was needed and this greatly simplifies the analytical procedure and minimizes potential sources of contamination. The precisions of analyzing solid mercury standard sample and real TCM materials were 2.1% and 2.5–8.2%, respectively; and the recovery based on the analysis of standard reference materials ranged from 95.2% to 105%. The performance of the method has been compared with inductively coupled plasma-mass spectrometry (ICP-MS) technique and excellent agreements were observed between the two methods. The method has been applied to the investigation of Hg content in several TCM drugs containing or not containing cinnabar. Mercury concentration in the same TCM products differs widely with different manufacturers, suggesting that external contamination and the Hg presence in raw herbal materials are the main sources of Hg. In addition, comparison of mercury thermal releasing profiles between TCM drug and cinnabar suggests that mercury conversion from cinnabar to biological matrices-bound Hg could occur because of the aid of other ingredients in the formulated drug. [Copyright &y& Elsevier]

Abstract: Glycyrrhizic acid (GA) and licorice flavonoids (LF) are the two classes of bioactive components in licorice with known pharmacological effects. But long-term excessive intake of GA may cause sodium retention and hypertension. In this study, the performance and adsorption characteristics of four widely used macroporous resins for the separation of deglycyrrhizinated, flavonoids enriched licorice has been critically evaluated. The sorption and desorption properties of LF and GA on macroporous resins including XDA-1, LSA-10, D101 and LSA-20 have been compared. The adsorption capacity was found to depend strongly on the pH of the feed solution. XDA-1 offers much higher adsorption capacity for GA and LF than other resins, and its adsorption data fit the best to the Freundlich isotherm. XDA-1 also shows much higher adsorption affinity towards LF than that of GA based on calculated results from the measured adsorption isotherms. Dynamic adsorption and desorption experiments have been carried out on a XDA-1 resin packed column to obtain optimal parameters for separating GA and LF. An enriched LF extract (about 21.9% purity) free of GA, and an enriched GA extract with 66% purity can be separated from crude licorice extract in one run. [Copyright &y& Elsevier]

Abstract: Although positive-ion (PI) electrospray ionisation mass spectrometry (ESI-MS) has been usually applied for the analysis of native metallothioneins (MT) isoforms binding with metal ions, it suffers from the lack of insensitivity under neural conditions because of the low efficiency of protonation during ESI process. In this study, multiply deprotonated metallothionein (Zn7-MT-2a), produced from tris(hydroxymethyl)aminomethane (TRIS) acetate solutions under near neutral condition, was analyzed by negative-ion (NI) ESI-MS. Compared with the ammonium acetate buffer system which has been normally used for ESI-MS experiments, the use of TRIS acetate buffer results in the formation of more abundant ions and higher charge states of MT-2a, and consequently higher intensity is attained. The sensitivity enhancement of the system could be explained by the high gas-phase proton affinity, small molecular volume of the anion (acetate), and the high hydrogen consumption by TRIS in the buffer system, which would all favor the deprotonation of the analyte during NI-ESI process. Factors that may affect the NI-ESI responses, such as acid added in buffer, pH and concentration of TRIS acetate had been evaluated, and the result showed that using acetic acid, lower pH under the pH range evaluated, higher concentration of TRIS acetate all favored the MS detection of MT-2a. Our finding sheds light on a buffer system that may offer substantial sensitivity advantages in the studying of weakly bound, non-covalent complexes such as metal binding MTs, which are usually analyzed under near neutral conditions. [Copyright &y& Elsevier]

Multi-stage countercurrent extraction (MCE) technique has been developed for the extraction of glycyrrhizic acid (GA) from Glycyrrhiza uralensis Fisch, a particular plant species of licorice. The effects of extraction stage numbers, temperature, extraction time and solvent to licorice ratio on the extraction yield of GA were investigated in detail. The process conditions of MCE were optimized using orthogonal array experimental design (OAD) technique. Under optimum process conditions (five stages, 60 min extracting time for every stage, 60 °C temperature and 6 ml/g solvent to licorice ratio), the extraction efficiency of MCE has been compared with those of conventional techniques including batch single pot extraction (SPE), microwave-assisted extraction (MAE), ultrasonic extraction (USE), Soxhlet extraction (SHE) and room temperature extraction (RTE). Results show that the MCE process offers the highest GA extraction yield and considerable savings in time, energy and solvent consumption. [Copyright &y& Elsevier]

The determination of trace lead in a CaCO3 matrix by isotope dilution coupled anion-exchange and quadrupole-based inductively coupled plasma-mass spectrometry was established. The matrix of CaCO3 seriously affected the determination by clogging the cones of the instrument was removed by the anion-exchange resin column. Effects such as dead time, mass bias, dwell time and the amount of isotopic agent spiked were discussed and corrected. The detection limit estimated by 3× standard deviation of the procedure blank was 2.94 ng g−1. The results indicated that the lead concentration in all samples tested was far less than 3%, the legislated limit. The recovery mostly ranged from 90 to 110%. The relative standard deviation was found to be <1%. [Copyright &y& Elsevier]

Isotope dilution analysis method coupled with flow injection and inductively coupled plasma mass spectrometry (ID-FI-ICP-MS), enabled trace lead concentration in seawater to be determined and the high salt concentration in the matrix, such as Na+, Ca2+ and Mg2+, to be removed on-line. The operational parameters of the FI system including pH for the chelating reaction, concentration of 8-hydroxyquinoline-5-sulfonic acid (8-HQS), sample loading time and injection speed, washing time and speed, eluting acid concentration and eluting speed, and instrumental parameters for ICP-MS were optimized and selected. Accurate results could be achieved because the isotope ratios required can be precisely measured in the range of the eluting peak by means of ID-FI-ICP-MS. The 3σ detection limit was 0.204 ng ml−1. The trace lead concentration of seawater in south Xiamen, China was 0.988 ± 0.039 ng ml−1. The recoveries of spiked Pb standard in seawater and standard reference water (GBW 08607) were 97.9 and 101.0%, respectively, with a relative standard deviation of 0.98%. This method can be used to determine trace lead concentration in high salt matrix samples, and is especially useful when the eluting peaks do not have a Gaussian-distribution. [Copyright &y& Elsevier]

The purpose of this study is to investigate the amounts and characteristics of heavy metals (As, Hg) leachable from several Chinese medicinal materials (CMM) under conditions simulating stomach and intestine digestion and absorption. Analysis by inductively coupled plasma mass spectrometry (ICP-MS) was compared with that by hydride generation atomic fluorescence spectrometry (HG-AFS). Focused microwave assisted extraction (MAE) and Soxhlet extraction were carried out to compare with the conventional sequential extraction method. The CMM studied included two mineral drugs: realgar and cinnabar, and two formulated drugs containing the two minerals. The leachable amounts of the target elements into artificial stomach fluid, artificial intestinal fluid, and artificial intestinal fluid in 0.5% trypsin were compared. The last solvent gave the greatest amounts of leachable As (0.41%) from realgar and Hg (1×10−4%) from cinnabar, but otherwise no significant effect on the leachable amounts was observed upon changing the following parameters: temperature (37–60 °C), HCl concentration (0.5–6 M), and CMM sample particle size (74 and 250 μm). The low leaching efficiencies observed confirmed the presence of As and Hg as insoluble species (sulfides)in these mineral drugs. Sequential extraction schemes were used to determine the species of mercury and arsenic in formulated drugs containing the minerals. Trace amounts of organic forms of arsenic (0.43%) and mercury (2.9×10−4%) were observed which could be the transformation products derived from the original cinnabar or realgar minerals in drug formulation. [Copyright &y& Elsevier]