An environmental friendly method for the automatic determination of hypochlorite in commercial products using multisyringe flow injection analysis

A multisyringe flow injection analysis system was used for the determination of hypochlorite in cleaning agents, by measurement of the native absorbance of hypochlorite at 292 nm. The methodology was based on the selective decomposition of hypochlorite by a cobalt oxide catalyst giving chloride and oxygen. The difference of the absorbance of the sample before and after its pass through a cobalt oxide column was selected as analytical signal. As no further reagent was required this work can be considered as a contribution to environmental friendly analytical chemistry. The entire analytical procedure, including in-line sample dilution in three steps was automated by first, dilution in a stirred miniature vessel, second by dispersion and third by in-line addition of water using multisyringe flow injection technique. The dynamic concentration range was 0.04-0.78 g L⁻¹ (relative standard deviation lower than 3%), where the extension of the hypochlorite decomposition was of 90 ± 4%. The proposed method was successfully applied to the analysis of commercial cleaning products. The accuracy of the method was established by iodometric titration.     

Capillary electrophoresis-based methods for the determination of lipids--a review

Capillary electrophoresis (CE) is a high-resolution technique for the separation of complex biological and chemical mixtures. CE continues to emerge as a powerful tool in the determination of lipids. Here we review the analytical potential of CE for the determination of a wide range of lipids. The different classes of lipids are introduced, and the different modes of CE and optimization methods for the separation of lipids are described. The advantages and disadvantages of the different modes of CE compared to traditional methods like gas chromatography (GC) and liquid chromatography (LC) in the determination of lipids are discussed. Finally, the potential of CE in the determination of lipids in the future is illustrated.     

Nested Arg-specific bifunctional crosslinkers for MS-based structural analysis of proteins and protein assemblies

The combination of chemical probing and high-resolution mass spectrometry constitutes a powerful alternative for the structural elucidation of biomolecules possessing unfavorable size, solubility, and flexibility. We have developed nested Arg-specific bifunctional crosslinkers to obtain complementary information to typical Cys- and Lys-specific reagents available on the market. The structures of 1,4-phenyl-diglyoxal (PDG) and 4,4′-biphenyl-diglyoxal (BDG) include two identical 1,2-dicarbonyl functions capable of reacting with the guanido group of Arg residues in proteins, as well as the base-pairing face of guanine in nucleic acids. The reactive functions are separated by modular spacers consisting of one or two benzene rings, which confer greater rigidity to the crosslinker structure than it is afforded by typical aliphatic spacers. Analysis by electrospray ionization (ESI) Fourier transform ion cyclotron resonance (FTICR) mass spectrometry has shown that the probes provide both mono- and bifunctional products with model protein substrates, which are stabilized by the formation of diester derivatives in the presence of borate buffer. The identification of crosslinked sites was accomplished by employing complementary proteolytic procedures and peptide mapping by ESI-FTICR. The results showed excellent correlation with the solvent accessibility and structural context of susceptible residues, and highlighted the significance of possible dynamic effects in determining the outcome of crosslinking reactions. The application of nested reagents with different spacing has provided a new tool for experimentally recognizing flexible regions that may be involved in prominent dynamics in solution. The development of new bifunctional crosslinkers with diverse target specificity and different bridging spans is expected to facilitate the structure elucidation of progressively larger biomolecular assemblies by increasing the number and diversity of spatial constraints available for triangulating the position of crosslinked structures in the three dimensions.     

A caffeine-sensitive membrane electrode: previous misleading report and present approach

Although a previous study [S.S.M. Hassan, M.A. Ahmed, M.M. Saoudi, Anal. Chem. 57 (1985) 1126] had shown that a caffeine-sensitive electrode made with picrylsulfonate and 1-octanol as a cation-exchanger and a solvent mediator, respectively, had a wide working pH range (5.5–9.5) and exhibited a Nernstian response, we could not find such response in this electrode. The present result was reasonable, because the pK_a value of caffeinium ion was reported to be around 0.7 and the neutral form of caffeine was predominant in the pH range examined. Thus, we reinvestigated the response characteristics of a caffeine electrode, taking into consideration the pK_a value, and constructed a new electrode with a combination of the lipophilic cation-exchanger, tetrakis[3,5-bis(2-methoxyhexafluoro-2-propyl)phenyl]borate (HFPB), and the solvent mediator with high degree of dielectric constant, 2-fluoro-2′-nitrodiphenyl ether (FNDPE). This electrode showed a pH-dependent response to caffeinium ion and gave a detection limit of 50 μM with a slope of 55 mV per concentration decade at pH 2. The use of other solvent mediators was less effective than that of FNDPE. The electrode was applied for the determination of caffeine in some central stimulants.     

Simultaneous Determination of Atenolol,Rosuvastatin, Spironolactone,Glibenclamide and Naproxen Sodium in Pharmaceutical Formulations and Human Plasma by RP‐HPLC

A rapid and sensitive high‐performance liquid chromatographic method was developed and validated for the simultaneous determination and quantification of atenolol, rosuvastatin, spirnolactone, glibenclamide and naproxen sodium in bulk drugs, pharmaceutical formulations and in human plasma in the presence of internal standard (flurbiprofen). Chromatograms were developed with methanol and water (80:20, v/v) solvent system on a Purospher start, C₁₈ (5 μm, 250 × 4.6 mm) column and pH was adjusted to 3.40 with ortho‐phosphoric acid. Mobile phase was pumped with a flow rate of 0.90 mL/minute with 235 nm UV detection. Standard curves were linear over the concentration range 0.25‐30 μg/mL^?1. The coefficients of variation (C.V.%), were < 3% and LOD and LOQ were <0.0154 & 0.06 for inter‐ and intra‐day, respectively. The method was applied to drug interaction studies of atenolol with rosuvastatin, spironolactone, glibenclamide and naproxen to illustrate the scope and application of the methods to manage four different therapeutic classes of drugs, as they are co‐administered.     

Application of full factorial design for the preconcentration of chromium by solid phase extraction with Amberlyst 36 resin

The preconcentration of chromium(III) by solid phase extraction and its determination from aqueous solutions by flame atomic absorption spectrometry (FAAS) is investigated by applying an experimental design. The optimization of the preconcentration variables such as pH of the sample solution, flow rate of the sample solution and concentration of elution solution was carried out using 2³ full factorial design. The most important parameter affecting the preconcentration of chromium is the concentration of eluent. In the established experimental conditions, chromium can be determined with a relative standard deviation of 2.0% (N = 7) for a chromium concentration of 100 μg L⁻¹. The detection limit for chromium was 1 μg L⁻¹ (N = 20). The adsorption capacity of Amberlyst 36 is found to be 90.9 mg g⁻¹ for chromium. Effect of other ions on the procedure was also evaluated. The method was validated by the analysis of certified reference materials (tea leaves GBW 07605 and fish tissue IAEA-407). The method was applied to the determination of chromium in waste water, dam water, carrot, parsley and lettuce. Correspondence: Ali Rehber Türker, Department of Chemistry, Faculty of Science and Arts, Gazi University, TR-06500 Ankara, Turkey     

Design of a field flow system for the on-line spectrophotometric determination of phosphate, nitrite and nitrate in natural water and wastewater

This study describes the design and optimisation of a field flow system for the in-situ collection and on-line determination of phosphate, nitrate and nitrite by flow injection analysis-spectrophotometry. The method is based on the initial determination of phosphate as its phosphoantimonylmolybdenum blue complex which is then oxidized on-line by nitrite and the decrease in absorbance is monitored at 880 nm. Nitrate is determined as the difference between total and initial nitrite content in a separate flow after reduction to nitrite in a cadmium reductive column. The calibration curves were linear in the range 0–2.00 mg L⁻¹ P-phosphate, 0–10.00 mg L⁻¹ nitrite and 0–7.00 mg L⁻¹ nitrate with correlation coefficients of 0.9979, 0.9993 and 0.9995, respectively. The detection limits, calculated as 3S/N, were 0.15 mg L⁻¹ for P-phosphate, 0.17 mg L⁻¹ for nitrite and 0.09 mg L⁻¹ for nitrate. The reproducibility was below 3.0% (n = 7). Method validation in the analysis of natural water and wastewater samples revealed that it can efficiently be applied to the determination of the target analytes, with recoveries in the range of 92–108%. Correspondence: Athanasios G. Vlessidis, Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina, Ioannina 45110, Greece     

Boron-Catalyzed α-Functionalizations of Carboxylic Acids

Catalytic, chemoselective, and asymmetric α-functionalizations of carboxylic acids promise up-grading simple feedstock materials to value-added functional molecules, as well as late-stage structural diversifications of multifunctional molecules, such as drugs and their leads. In this personal account, we describe boron-catalyzed α-functionalizations of carboxylic acids developed in our group (five reaction types). The reversible boron carboxylate formation is key to the acidification of the α-protons and enolization using mild organic bases, allowing for chemoselective and asymmetric bond formations of carboxylic acids. The ligand effects on reactivity and stereoselectivity, substrate scopes, and mechanistic insights are summarized.     

Production of polyhydroxyalkanoate from sesame seed wastewater by sequencing batch reactor cultivation process of Haloferax mediterranei

Due to the high cost of bioplastic production, sesame wastewater, generated from the sesame seed hulling process, was investigated to be used as inexpensive and renewable carbon source for the production of biodegradable polyhydroxyalkanoate (PHA) by extreme Haloferax mediterranei. The sesame wastewater (SWW) was hydrolyzed using different concentrations of hydrochloric acid (0.4. 1.00 and 2.00 M) at different period of times (15, 60 and 90 min). The concentration of salt (NaCl) and nitrogen source (NH₄Cl and yeast) required for H. mediterranei cells growth and the accumulation of PHA biopolymer was optimized. A maximum 0.53 g/L concentration of PHA was achieved when the SWW extract media was supplemented with 100 g/L NaCl and 6.0 g/L yeast extract. The cultivation was scaled-up using sequencing batch reactor (SBR) fermentation under non-sterile conditions. The SBR results showed that SWW needs an auxiliary carbon source to obtain high PHA production. Consequently, the system fed with SWW and glucose produced higher PHA (20.9 g/L) than the system fed with SWW.     

不同预处理方法对准东高碱煤中碱金属含量测定的影响

以四种不同的准东高碱煤及气化飞灰为研究对象,对高碱煤及气化飞灰中碱金属(Na、K)的赋存形态,以及不同预处理方法(低温灰化法、直接消解法、中国国标法、萃取法及氧弹燃烧法)对准东高碱煤及气化飞灰中碱金属(Na、K)含量测定的影响进行了测试分析。结果表明,准东高碱煤中碱金属Na主要以水溶态形式存在,碱金属K主要以水不溶态形式存在;不同的预处理方法对准东高碱煤中碱金属(Na、K)含量的测定结果影响显著,对于准东高碱煤及气化飞灰中碱金属(Na、K)含量测定,建议采用氧弹燃烧法,萃取法也可以相对准确地反映煤中碱金属Na的含量。