Abstract  We studied the relationships between environmental variables and the physiology of two (semi-)aquatic mosses (Bryum pseudotriquetrum and Fontinalis antipyretica) in an unforested headwater stream over a three year period. Neither environmental or physiological variables showed significant interannual variations. Most environmental variables (water temperature, stratospheric ozone, and photosynthetic, UV-A and UV-B radiation) showed distinct seasonal variations, but only a few physiological ones did. In both species, photoprotection variables (the activity of the xanthophyll cycle and the bulk UV absorbance of the methanol-extractable UV-absorbing compounds, MEUVAC) varied more seasonally than variables related to physiological activity, such as the sclerophylly index and chlorophyll fluorescence parameters (F-v/F-m and Phi(PSII)). Changes in physiological activity would be attenuated by the buffering capacity of water with respect to the influence of environmental factors, and dynamic variables like F-v/F-m and Phi(PSII) would be little determined by cyclic environmental factors. In B. pseudotriquetrum, both MEUVAC and kaempferol 3,7-O-diglycoside (a potentially UV-protective flavonoid) were positively associated with radiation levels, whereas in F. antipyretica photoprotection mechanisms were not correlated with any environmental variable. In addition, MEUVAC was 3-4 fold higher in B. pseudotriquetrum than in F. antipyretica. Thus, different photoprotection mechanisms, with a different environmental regulation, can be suggested for these two species. DNA damage was not found in any sample, probably because both species displayed efficient DNA repair mechanisms.

Abstract  A new HILIC method has been developed for the simultaneous determination of pseudoephedrine hydrochloride (PSH), diphenhydramine hydrochloride (DPH) and dextromethorphan hydrobromide (DXH) in cough-cold syrup. Mobile phase consists of methanol:water (containing 6.0 g of ammonium acetate and 10 mL of triethylamine per liter, pH adjusted to 5.2 with orthophosphoric acid), 95:5 (v/v). Column containing porous silica particles (Supelcosil LC-Si, 25 cm x 4.6 mm, 5 microm) is used as stationary phase. Detection is carried out using a variable wavelength UV-vis detector at 254 nm for PSH and DPH, and at 280 nm for DXH. Solutions are injected into the chromatograph under isocratic condition at constant flow rate of 1.2 mL/min. Linearity range and percent recoveries for PSH, DPH and DXH were 150-600, 62.5-250, 75-300 microg/mL and 100.7%, 100.1% and 100.8%, respectively. Method is stability indicating and excipients like saccharin sodium, sodium citrate, flavour and sodium benzoate did not interfere in the analysis. Compounds elute in order of increasing ionization degree caused by cation-exchange mechanism in a run time of less than 15 min. Mobile phase pH is manipulated to regulate ionization and ion-exchange interaction and thereby retention of compounds.

Abstract  Chromatographic effects of dedicated stationary and mobile phase variations in hydrophilic interaction chromatography (HILIC) were investigated using a set of nucleobases, nucleosides and deoxynucleosides as polar test solutes. Retention and selectivity profiles were comparatively mapped on four in-house developed silica materials modified with short alkyl chains (C4, C5) which carry hydroxyl functionalities (including diol motifs) as well as embedded sulphide or sulphoxide groups. These data were complemented by results obtained with two commercially available diol-type phases and a bare silica column. Besides elucidation of packing-related aspects this work concentrated specifically on extending aqueous HILIC (AQ-HILIC) to nonaqueous polar-organic elution conditions herein termed NA-HILIC. The exchange of the polar modifier water by various alcohols in ACN-rich mobile phases containing 5 mM ammonium acetate decreased the eluotropic strength of the resulting eluents. The gain in retention largely followed the order ethanol (EtOH)>methanol (MeOH)>1,2-ethanediol (Et(OH)2) and was accompanied by distinct effects on chromatographic selectivity. For example, on the most polar home-made packing the purine nucleoside selectivity guanosine/adenosine increased from 2.25 in the AQ-HILIC (kguanosine=8.3) to 7.33 (kguanosine=59) in the NA-HILIC mode when EtOH was employed as NA modifier while this value was 5.84 and 2.93 with MeOH and Et(OH)2, respectively (eluent: 5 mM ammonium acetate in ACN/modifier 90:10 v/v). Besides the type of protic modifier its percentage as well the retention and selectivity effects upon varying the ammonium acetate concentration and column temperature, respectively, were also investigated. Notable inter-column differences were found for all of these elution parameters. A mixed-mode retention model composed of partitioning and adsorption is proposed for both AQ- and NA-HILIC retention processes. The potential of (i) the implementation of novel polar bondings (such as ones containing sulphoxide functionalities) and (ii) the comprehensive exploitation of elution variables (type of protic modifiers, salt, etc.) for providing new selectivity increments to the separation of polar analytes in HILIC is emphasised.

Abstract  An integrated method of liquid chromatography-heated electrospray ionization/tandem mass spectrometry was evaluated for high throughput screening of various abused drugs in urine. Chromatographic analysis was performed on a C18 reverse phase column using a linear gradient of 10mM ammonium acetate containing 0.1% formic acid-methanol as mobile phase and the total separation time was 7 min. A simple and rapid sample preparation method used was by passing urine samples through a 0.22 microm PVDF syringe filter. The detection limits of the studied abused drugs in urine were from 0.6 ng mL(-1) (ketamine) to 9.0 ng mL(-1) (norcodeine). According to the results, the linear range was from 1 to 1200 ng mL(-1) with relative standard deviation (R.S.D.s) value below 14.8% (intra-day) and 24.6% (inter-day). The feasibility of applying the proposed method to determine various abused drugs in real samples was examined by analyzing urine samples from drug-abused suspects. The abused drugs including ketamines and amphetamines were detected in suspected urine samples. The results demonstrate the suitability of LC-HESI-MS/MS for high throughput screening of the various abused drugs in urine.

Abstract  A rapid and sensitive method is described for the determination of scopolamine and its metabolites in rat urine by combining liquid chromatography and tandem mass spectrometry (LC-MS/MS). Various extraction techniques (free fraction, acid hydrolyses and enzyme hydrolyses) and their comparison were carried out for investigation of the metabolism of scopolamine. After extraction procedure, the pretreated samples were injected into a reversed-phase C18 column with mobile phase of methanol/ ammonium acetate (2mM, adjusted to pH 3.5 with formic acid) (70:30, v/v) and detected by an on-line MS/MS system. Identification and structural elucidation of the metabolites were performed by comparing their changes in molecular masses (DeltaM), retention-times and full scan MS(n) spectra with those of the parent drug. The results revealed that at least 18 metabolites (norscopine, scopine, tropic acid, aponorscopolamine, aposcopolamine, norscopolamine, hydroxyscopolamine, hydroxyscopolamine N-oxide, p-hydroxy-m-methoxyscopolamine, trihydroxyscopolamine, dihydroxy-methoxyscopolamine, hydroxyl-dimethoxyscopolamine, glucuronide conjugates and sulfate conjugates of norscopolamine, hydroxyscopolamine and the parent drug) and the parent drug existed in urine after ingesting 55mg/kg scopolamine to healthy rats. Hydroxyscopolamine, p-hydroxy-m-methoxyscopolamine and the parent drug were detected in rat urine for up 106h after ingestion of scopolamine.

Abstract  A pilot study has been carried out to define typical characteristics of the trace gas compounds in exhaled breath of non-smokers and smokers to assist interpretation of breath analysis data from patients who smoke with respiratory diseases and lung cancer. Exhaled breath was analyzed using proton transfer reaction-mass spectrometry (PTR-MS) for 370 volunteers (81 smokers, 210 non-smokers, 79 ex-smokers). Volatile organic compounds corresponding to product ions at seven mass-to-charge ratios (m/z 28, 42, 69, 79, 93, 97, 123) in the PTR-MS spectra differentiated between smokers and non-smokers. The Youden index (= maximum of sensitivity + specificity - 1, YI) as a measure for differentiation between smokers and non-smokers was YI = 0.43 for ions at the m/z values 28 (tentatively identified as HCN), YI = 0.75 for m/z = 42 (tentatively identified as acetonitrile) and YI = 0.53 for m/z = 79 (tentatively identified as benzene). No statistically significant difference between smokers and non-smokers was observed for the product ions at m/z = 31 and 33 (compounds tentatively identified as formaldehyde and methanol). When interpreting the exhaled breath of lung cancer or COPD patients, who often smoke, compounds appearing at the above-mentioned seven mass-to-charge ratios should be considered with appropriate care to avoid misdiagnosis. Validation studies in larger numbers of patients with more precise delineation of their smoking behavior and using additional analytical techniques such as GC/MS and SIFT-MS should be carried out.

Abstract  Collection of exhaled breath condensate (EBC) is a relatively simple noninvasive method of breath analysis; however, no data have been reported that would relate concentration of volatile compounds in EBC to their gaseous concentrations in exhaled air. The aim of the study was to investigate which volatile compounds are present in EBC and how their concentrations relate to results of direct breath analysis. Thus, samples of EBC were collected in a standard way from several subjects and absolute levels of several common volatile breath metabolites (ammonia, acetone, ethanol, methanol, propanol, isoprene, hydrogen cyanide, formaldehyde and acetaldehyde) were then determined in their headspace using selected ion flow tube mass spectrometry (SIFT-MS). Results are compared with those from on-line breath analyses carried out immediately before collecting the EBC samples. It has been demonstrated that SIFT-MS can be used to quantify the concentrations of volatiles in EBC samples and that, for methanol, ammonia, ethanol and acetone, the EBC concentrations correlate with the direct breath levels. However, the EBC concentrations of isoprene, formaldehyde, acetaldehyde, hydrogen cyanide and propanol do not correlate with direct breath measurements.

Abstract  The developmental toxicity of the alternative motor vehicle fuel methanol was assessed in mice by the inhalation route. Pregnant CD-1 mice were exposed to 1,000, 2,000, 5,000, 7,500, 10,000 or 15,000 ppm methanol for 7 hr/day on days 6-15 of gestation. Mice were provided with water but not food during the exposure period. Sham-exposed controls were exposed to filtered air under conditions similar to those of methanol exposure. Additional control groups were left in their home cages either unhandled or food-deprived for seven hr/day to match the food deprivation experienced by the exposed mice. Maternal weight gain was monitored throughout the exposure period. Some exposed mice were killed for determination of blood methanol concentrations on gestation days 6, 10 and 15. On day 17 of gestation, remaining mice were weighed, killed and the gravid uterus was removed. Numbers of implantation sites, live and dead fetuses and resorptions were counted, and fetuses were examined externally and weighed as a litter. Half of each litter was examined for skeletal morphology and the other half of each litter was examined for internal soft tissue anomalies using a freehand scalpel dissection. One dam died in each of the 2,000, 7,500, 10,000 and 15,000 ppm methanol exposure groups. The sham-exposed and food-deprived control as well as all methanol exposed dams gained less weight than did unexposed dams fed ad libitum, but methanol did not exacerbate this effect, as all exposure groups showed similar weight gain. Significant increases in the incidence of exencephaly and cleft palate were observed at 5,000 ppm and above, increased postimplantation mortality at 7,500 ppm and above (including an increasing incidence of full-litter resorption), and reduced fetal weight at 10,000 ppm and above. A dose-related increase in cervical ribs or ossification sites lateral to the seventh cervical vertebra was significant at 2,000 ppm and above. Thus, the NOAEL for the developmental toxicity in this study is 1,000 ppm. A logistic dose response model was applied to the incidence data for exencephaly, cleft palate, resorption and cervical rib, and maximum likelihood estimates (MLEs) and benchmark dosages (BDs, the lower 95% confidence interval of the MLEs) corresponding to 1% and 5% added risk were calculated. The MLE for 5% added risk of exencephaly, cleft palate or resorption was 3,667 ppm, and the corresponding BD was 3,078 ppm. For cervical rib, the 5% added risk values for the MLE and BD were 824 and 305 ppm, respectively. The BDs for 1% added risk were 1,915 ppm for exencephaly, cleft palate or resorption, and 58 ppm for cervical rib. Quantitative modeling of these dose-response data for estimates of added risk offers more complete use of the data and less subjectivity than determining a NOAEL, and the lowest MLE for 5% added risk of developmental toxicity was in the dose range of the NOAEL. The results of this study indicate that inhaled methanol is developmentally toxic in the mouse at exposure levels which were not maternally toxic. Litters of pregnant mice gavaged orally with 4 g methanol/kg displayed developmental toxic effects very similar to those seen in the 10,000 ppm methanol exposure group.

Abstract  Sputter deposition was investigated as a tool for manufacturing proton-exchange membrane fuel cell (PEMFC) electrodes with improved performance and better catalyst utilization vs. commercial electrode. Nanosized (diameter 2-5 nm) platinum...

Abstract  To characterize the pharmacokinetics of cefuroxime in rat blood and brain, microdialysis probes were inserted into the jugular vein and brain striatum, respectively. Cefuroxime (20 mg/kg, i.v.) was administered via the femoral vein. Blood microdialysates were automatic injected onto microbore liquid chromatography via an on-line injectors. The mobile phase consisted of methanol-100 mM monosodium phosphoric acid (25:75, v/v, pH 5.0) with a flow-rate of 0.05 ml/min. Ultraviolet detector was set at a wavelength of 280 nm for cefuroxime. The present assay enhanced the detection sensitivity and enabled the determination of cefuroxime down to 5 ng/ml. The pharmacokinetic data demonstrated that the area under the concentration curve (AUC) ratio of unbound cefuroxime in rat brain and blood was about 4.2% after cefuroxime (20 mg/kg, i.v.) administration. These results provided further evidence that cefuroxime could penetrate the blood-brain barrier.

Abstract  Large-scale aerobic windrow composting has been used to bioremediate washout lagoon soils contaminated with the explosives TNT (2,4,6-trinitrotoluene) and RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) at several sites within the United States. We previously used 15N NMR to investigate the reduction and binding of T15NT in aerobic bench-scale reactors simulating the conditions of windrow composting. These studies have been extended to 2,4-dinitrotoluene (2,4DNT) and 2,6-dinitrotoluene (2,6DNT), which, as impurities in TNT, are usually presentwherever soils have been contaminated with TNT. Liquid-state 15N NMR analyses of laboratory reactions between 4-methyl-3-nitroaniline-15N, the major monoamine reduction product of 2,4DNT, and the Elliot soil humic acid, both in the presence and absence of horseradish peroxidase, indicated that the amine underwent covalent binding with quinone and other carbonyl groups in the soil humic acid to form both heterocyclic and non-heterocyclic condensation products. Liquid-state 15N NMR analyses of the methanol extracts of 20 day aerobic bench-scale composts of 2,4-di-15N-nitrotoluene and 2,6-di-15N-nitrotoluene revealed the presence of nitrite and monoamine, but not diamine, reduction products, indicating the occurrence of both dioxygenase enzyme and reductive degradation pathways. Solid-state CP/MAS 15N NMR analyses of the whole composts, however, suggested that reduction to monoamines followed by covalent binding of the amines to organic matter was the predominant pathway.

Abstract  The grain boundary formation in PtRu/C catalyst obtained in a polyol process with post-treatment was investigated by scanning transmission electron microscopy, transmission electron microscopy (TEM) and High resolution TEM. The crystalline structure and surface composition of the PtRu/C catalysts were characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The electrochemical activities were evaluated by CO stripping voltammetry and linear sweep voltammetry measurements in combination with in situ IR reflection-absorption spectroscopy. As-prepared isolated spherical nanoparticles on the carbon support started to interconnect after washing procedure, and the interconnection between the particles was greatly promoted by reduction post-treatment at 80 degrees C; grain boundary formation occurred in the interconnected particles with increasing reduction temperature to 200 degrees C, and the particles reconstructed severely with further increasing reduction temperature to 400 degrees C. The defects at the grain boundary served as active sites for methanol electro-oxidation by weakening COads adsorption on Pt sites and facilitating OHads formation, and the PtRu/C catalyst treated in 5% H-2/Ar at 200 degrees C for 10 h had the greatest catalytic activity for methanol electro-oxidation among the PtRu/C catalysts treated under various atmospheres and temperatures. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Abstract  Carbon supported Pt-Ru catalysts were prepared by multiple cycles of potentiostatic pulses from aqueous diluted chloroplatinic acid and ruthenium chloride solutions in the presence of ethanol or ethylene glycol at pH 2 and 5. SEM images showed that the metallic deposit prepared at pH 2 consisted of large irregular agglomerates, whereas smaller globular particles were obtained at pH 5. In addition, the average particle size was considerably decreased in the presence of the stabilizers. The supported Pt-Ru alloys were tested as catalysts for methanol electro-oxidation in acid media. Electrocatalytic activity measurements indicated that the most active electrode was obtained with ethylene glycol as additive at pH 5. (C) 2011 Elsevier B.V. All rights reserved.

Abstract  Herein we report the covalent functionalization of multiwall carbon nanotubes by grafting sulfanilic acid and their dispersion into sulfonated poly(ether ether ketone). The nanocomposites were explored as an option for tuning the proton and electron conductivity, swelling, water and alcohol permeability aiming at nanostructured membranes and electrodes for application in alcohol or hydrogen fuel cells and other electrochemical devices. The nanocomposites were extensively characterized, by studying their physicochemical and electrochemical properties. They were processed as self-supporting films with high mechanical stability, proton conductivity of 4.47 x 10 super(-2) S cm super(-1) at 30 C and 16.8 x 10 super(-2) S cm super(-1) at 80 C and 100% humidity level, electron conductivity much higher than for the plain polymer. The methanol permeability could be reduced to 1/20, keeping water permeability at reasonable values. The ratio of bound water also increases with increasing content of sulfonated filler, helping in keeping water in the polymer in conditions of low external humidity level.

Abstract  The electrochemical behaviour of fuel cell catalysts (mesoporous Pt (MPPt), MPPtRu, MPPt modified by adsorbed Ru (MPPt/Ru) and carbon supported PtRu alloy) was studied using the thin layer flow cell differential electrochemical mass spectrometry (TLFC-DEMS) technique. The catalysts present high catalytic activity towards the methanol oxidation reaction (MOR), being the PtRu/C electrode the least active for MOR, while MPPt/Ru presents higher current densities for this reaction than MPPtRu. The results suggest that the diffusion properties obtained in the porous structure of the MP electrodes and the surface atomic arrangement in the electrode are the main reasons for the higher catalytic activity achieved. Finally, TLFC-DEMS was proved to be a powerful technique which evaluates and correlates the CO sub(2) efficiency with the catalytic activity and the porous structure of the catalysts.

Abstract  Nanodimensional powders of cubic copper ferrite are synthesized by two-steps procedure of co-precipitation of copper and iron hydroxide carbonates, followed by mechanochemical treatment. X-ray powder diffraction, Mossbauer spectroscopy and temperature-programmed reduction are used for the characterization of the obtained materials. Their catalytic behavior is tested in methanol decomposition to hydrogen and CO and total oxidation of toluene. Formation of nanosized ferrite material is registered even after one hour of milling time. It is established that the prolonging of treatment procedure decreases the dispersion of the obtained product with the appearance of Fe(2)O(3). It is demonstrated that the catalytic behavior of the samples depends not only on their initial phase composition, but on the concomitant ferrite phase transformations by the influence of the reaction medium. (C) 2011 Elsevier Inc. All rights reserved.

Abstract  Manganese and cerium composite oxide (MnOx-CeO2) hollow nanospheres were successfully prepared by precipitating manganese acetylacetonate and cerium acetylacetonate from their mixed methanol solution using supercritical carbon dioxide as an anti-solvent. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) were employed to characterize the precursor and as-prepared MnOx-CeO2. XRD analysis reveals the cubic fluorite structure of the MnOx-CeO2. HRTEM results indicate that the MnOx-CeO2 hollow spheres have an average diameter of about 50 nm, and a wall thickness of 10-20 nm. A new formation mechanism of these nano-sized hollow spheres has also been proposed based on the experimental results. (C) 2011 Elsevier B.V. All rights reserved.