Multicommutation as an environmentally friendly analytical tool in the hydride generation atomic fluorescence determination of tellurium in milk

The aim of this study is to show the advantages of the emerging multicommutation methodology based on the use of solenoid valves for Te determination in milk by hydride generation atomic fluorescence spectrometry (HG-AFS). The delivery of a series of alternating sequential insertions of small volumes of samples and reagents gives rise to new hydrodynamic processes and exciting analytical potentials by controlling the time of flow through the on/off-switched solenoid valves. This drastically reduces the reagent consumption by a factor of 4 and the generation of effluents (590 mL h^–1 instead of 750 mL h^–1 generated by the continuous-mode measurement) and also provides an improvement in the laboratory productivity by an increase of the sample throughput (85 h^–1 compared to 20 h^–1 found in the continuous mode). So, multicommutation is an environmentally and economically sustainable alternative to the methodology based on continuous measurements. The multicommutation-based method developed was applied to tellurium determination in commercially available milk samples; a calibration range of 0.0–0.5 ng mL^–1 and a detection limit of 0.20 ng L^–1 with average relative standard deviation of 2.1% were found. Comparable results were obtained for a series of samples using both continuous and multicommutation HG-AFS modes.     

Gas Chromatographic Method for Routine Determination of Oleanolic and Ursolic Acids in Medicinal Plants

Summary A rapid and simple gas chromatographic method has been established for routine analysis of free oleanolic and ursolic acids in dried samples of medicinal herbs. Soxhlet extraction of triterpenes was followed by solid-phase extraction (SPE). Amounts of the compounds were measured by gas chromatography after silylation of the purified samples. Experiments were performed to establish the optimum conditions (e.g. solvent, and mode and duration of extraction) for calibration curve linearity, sensitivity, reproducibility, and recovery. The conditions used for derivatization and gas chromatographic analysis resulted in an improvement on literature data. The method devised enables accurate routine measurement of many samples in quite a short time (e.g. for chemotaxonomical screening, or quality control of herbal drugs). The practical application of the method was illustrated on five Lamiaceae species.     

Transfection mediated by gemini surfactants: engineered escape from the endosomal compartment

The structure of the lipoplex formed from DNA and the sugar-based cationic gemini surfactant 1, which exhibits excellent transfection efficiency, has been investigated in the pH range 8.8-3.0 utilizing small-angle X-ray scattering (SAXS) and cryo-electron microscopy (cryo-TEM). Uniquely, three well-defined morphologies of the lipoplex were observed upon gradual acidification: a lamellar phase, a condensed lamellar phase, and an inverted hexagonal (H(II)) columnar phase. Using molecular modeling, we link the observed lipoplex morphologies and physical behavior to specific structural features in the individual surfactant, illuminating key factors in future surfactant design, viz., a spacer of six methylene groups, the presence of two nitrogens that can be protonated in the physiological pH range, two unsaturated alkyl tails, and hydrophilic sugar headgroups. Assuming that the mechanism of transfection by synthetic cationic surfactants involves endocytosis, we contend that the efficacy of gemini surfactant 1 as a gene delivery vehicle can be explained by the unprecedented observation of a pH-induced formation of the inverted hexagonal phase of the lipoplex in the endosomal pH range. This change in morphology leads to destabilization of the endosome through fusion of the lipoplex with the endosomal wall, resulting in release of DNA into the cytoplasm.     

Towards a better understanding of the cisplatin mode of action

We have studied how platinum(II) complexes [Pt(dien)Cl]Cl, [Pt(en)Cl2] and cisplatin react with hybrid molecules that contain sulfur and nitrogen ligands, in particular Phac-Met-linker-p5'dG (Phac = phenylacetyl), Phac-His-linker-p5'dG, Phac-His-Met-linker-p5'dG and Phac-His-Gly-Met-linker-p5'dCATGGCT. The progress of the reactions was monitored by HPLC, and by [1H,15N]-HSQC NMR when 15N-cisplatin was used. The products were isolated and characterised by using enzymatic and chemical reactions and spectroscopic techniques (UV and/or NMR spectroscopy, electrospray or MALDI-TOF mass spectrometry). The combined use of digestion with proteases and reaction with hydrogen peroxide followed by mass spectrometric analysis indicated the platinum coordination positions on the peptide moiety of the largest hybrid. Monofunctional Pt-S adducts were transformed into Pt-N complexes in which Pt-N7 bonds were formed preferentially. Most of the chelates isolated had Pt-S bonds, and, in the case of cisplatin complexes, loss of the ammine trans to sulfur gave rise to the formation of tricoordinate species with platinum-mediated peptide-nucleotide cross-links. 1,2-Intrachain platinum GpG adducts were only obtained in very small amounts (1-4%).     

Simultaneous determination of carbaryl and azinphos-methyl in water by first-derivative synchronous spectrofluorimetry

A method is proposed for the simultaneous determination of the pesticides carbaryl (CBL) and azinphos-methyl (AZM) in water by first-derivative synchronous spectrofluorimetry. It is based on the alkaline hydrolysis of both pesticides to their metabolites 1-naphthol (from CBL) and anthranilic acid (from AZM). The constant wavelength difference chosen to optimize the determination is Δλ=λ_em?λ_ex=103 nm. CBL is measured at 302/405 nm and AZM at 333/436 nm. The calibration graphs are linear between 2.0 and 500.0 ng/ml for CBL and between 1.2 and 500.0 ng/ml for AZM with detection limits of 0.62 ng/ml and 0.35 ng/ml, respectively. The precision of the method (RSD) is 2.4% at the 80.0 ng/ml level for CBL and 2.5% at the 80.0 ng/ml level for AZM. The method is applied to the determination of both analytes in samples of natural waters.     

ICP-AES detection of silicon carbide impurities volatilized in a graphite furnace with the use of carbon tetrachloride vapour

The analytical capability of high-temperature halogenation with carbon tetrachloride vapour in a graphite furnace was investigated for silicon carbide powder with known chemical composition and particle size. Intensity vs heating time curves were determined for analytical lines of Al, B, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Ti, V and Si constituents, volatilized with and without the presence of CCl₄ vapour in the furnace atmosphere. Igniting 10 mg SiC at 2100 °C for 60 s in chlorinating atmosphere, the evaporated fraction of most of the constituents was higher than 90% (for Al about 50%). The line intensity vs sample mass (4–26 mg) relationships were linear for all impurities studied, while the intensity of silicon line showed a relatively small change with the sample mass. BEC (background equivalent concentration) values for this solid sampling technique (10 mg loaded sample) were 2–20 fold lower than those calculated for the conventional solution sample introduction method.     

Effect of the specific activity of the tracer on rat luteinizing hormone radioimmunoassay

Rat luteinizing hormone /LH/ was labelled with¹²⁵I by the Chloramine T method.¹²⁵I-LH, used as tracer in radioimmunoassay, was separated from the labelling reaction mixture by gel filtration. By using the proper protein/radioiodine ratio in the labelling reaction mixture the specific activity of¹²⁵I-LH was adjusted to 2.5–20.5 MBq g^–1. The influence of the specific activity on the assay parameters as well as on the tracer stability was investigated.     

Resolution of benzo[a]pyrene in complex mixtures of other polycyclic aromatic hydrocarbons. Comparison of two spectrofluorimetric methods applied to water samples

Two spectrofluorimetric methods, second-derivative constant-energy synchronous luminescence (SDCESL) and constant-wavelength synchronous luminescence (CWSL) in combination with multiple linear regression (MLR), for the quantification of benzo[a]pyrene (BaP) at sub-ng mL-1 levels, in the presence of benzo[b]fluoranthene (BbFt), benzo[k]fluoranthene (BkFt), benzo[ghi]perylene (BghiP) and indeno[1,2,3-cd]pyrene (IP), were developed and compared in detail. SDCESL presents lower limits of detection and quantification than CWSL/MLR and also gives more exact and precise results for levels close to the quantification limit. For BaP, SDCESL achieved quantification limits of 0.019 ng mL-1 in river waters and 0.007 ng mL-1 in drinking waters. This work offers a sensitive, precise, accurate, rapid, simple and economic methodology for monitoring BaP in waters for public consumption, meeting all the requirements of the EC Directive 98/83/CE that fixes the maximum admissible limit for this polycyclic aromatic hydrocarbon in drinking waters at of 0.010 ng mL-1.     

Rapid determination of PAHs in soil samples by HPLC with fluorimetric detection following sonication extraction

A rapid method for the determination of PAHs in soil samples based on their extraction with methylene chloride by sonication and subsequent separation by HPLC with fluorimetric detection is proposed. A Hypersil Green PAH column was used with a gradient of acetonitrile/water as the mobile phase, together with a program of nine excitation and emission wavelength pairs. Recoveries were in the range 70-98%, except for acenaphthene and naphthalene, at concentration levels 1.08-442 microg/kg with relative standard deviations in the range 2-15% (n = 4). Total PAHs found in soil samples were in the range 15-282 microg/kg. The results were compared with those obtained by applying the 3540 EPA method for two samples.     

Selectivity assessment of a sequential extraction procedure for metal mobility characterization using model phases

This study considers the selectivity of the extractants used in a sequential extraction scheme for metals mobility assessment by analyzing individual mineral phases previously coprecipitated or sorbed with trace metals. The scheme evaluated was a modification of the Tessier et al. [A. Tessier, P.G.C. Campbell, M. Bisson, Anal. Chem. 51 (1979) 844] sequential procedure proposed by the authors. The phases studied were calcite, amorphous iron oxide, hausmannite, humic acid, kaolinite and illite. Selective extractions were obtained for As, Cr, Cu, Ni, Pb and Zn in metal-coprecipitated phases whereas NH(2)OH-HCl was not selective for the extraction of Hg and Cd coprecipitated in hausmannite and amorphous iron oxide, respectively. Otherwise, Cd, Hg, Ni and Zn sorbed on the different phases were released with MgCl(2) and NaOAc/HOAc, but stronger reagents were needed to release As, Cr, Cu and Pb.