Flow systems exploiting in-line prior assays

An expert sequential injection system involving a prior assay is proposed for spectrophotometric determination of phosphate and eventually zinc in soil extracts. The result of phosphate determination is the basis for a concentration-oriented decision regarding to the need or not for zinc determination. Zinc was only determined if a threshold value (peak height corresponding to 5.0 mg l⁻¹ P) was surpassed. The methods involved formation of molybdenum blue and the Rhodamine 6G/ammonium thiocyanate/Zn²⁺ ternary complex. Variations in the threshold value were < 2% during 4 h operating periods, false responses were not verified, and the analytical time was reduced in about 30%. Precise results (R.S.D. <3% P and < 1% Zn) in agreement with spectrophotometry and flame atomic absorption spectrometry were obtained. The innovation permits faster information processing, as well as a reduction in the number of measurements, number of analytical steps, laboratorial time, and consumption of sample and reagents, thus waste generation.     

Detection of processed genetically modified food using CIM monolithic columns for DNA isolation

The availability of sufficient quantities of DNA of adequate quality is crucial in polymerase chain reaction (PCR)-based methods for genetically modified food detection. In this work, the suitability of anion-exchange CIM (Convective Interaction Media; BIA Separations, Ljubljana, Slovenia) monolithic columns for isolation of DNA from food was studied. Maize and its derivates corn meal and thermally pretreated corn meal were chosen as model food. Two commercially available CIM disk columns were tested: DEAE (diethylaminoethyl) and QA (quaternary amine). Preliminary separations were performed with standard solution of salmon DNA at different pH values and different NaCl concentrations in mobile phase. DEAE groups and pH 8 were chosen for further isolations of DNA from a complex matrix-food extract. The quality and quantity of isolated DNA were tested on agarose gel electrophoresis, with UV-scanning spectrophotometry, and by amplification with real-time PCR. DNA isolated in this way was of suitable quality for further PCR analyses. The described method is also applicable for DNA isolation from processed foods with decreased DNA content. Furthermore, it is more effective and less time-consuming in comparison with the existing proposed methods for isolation of DNA from plant-derived foods.     

Lifetime prediction of ABS polymers based on thermoanalytical data

The service life of ABS polymer, stabilized by 2-(3,5-di-tert-butyl-4-hydroxyanilino)-4,6-bis(octylthio)-1,3,5-triazine and containing 50% of a modifying rubber component, was estimated from oxidative induction times measured by DSC in isothermal mode in the temperature interval 140–170°C. The lifetime of ABS powder at the actual temperature of drying was predicted by linear extrapolation according to Arrhenius. However, the extrapolated value was much longer than the real lifetime determined from the long-term oven aging tests at 70 and 90°C, simulating the industrial drying process. The effect of changes in the apparent activation energy of oxidation due to antioxidant consumption during polymer aging is discussed.     

Bioelectronics and biometallocatalysis for production of fuels and chemicals by photosynthetic water splitting

Applied Biochemistry and Biotechnology - By inserting metallocatalysts (such as platinum, osmium, or ruthenium) at the reducing site of photosystem I (PSI), electrons that emerge from PSI can be...     

Efficiency of decomposition procedures for the determination of some elements in soils by atomic spectroscopic methods

Nine decomposition procedures for soil samples, such as via acid mixtures and fusion in open systems and microwave and autoclave dissolution (in closed systems under elevated temperature and pressure) were assessed using certified soil reference materials. The determination of various elements in solutions was performed by FAAS and ICP-OES and the results were compared with certified values and with direct current arc OES analysis. Received: 3 March 1997 / Revised: 30 May 1997 / Accepted: 3 June 1997     

Titanocene(III) mediated radical cyclization of α-bromo carbonyl compounds: synthesis of tri-substituted tetrahydrofurans

A novel and efficient methodology has been developed for the construction of synthetically important tri-substituted tetrahydrofuran derivatives from bromo-alkenes and bromo-alkynes by radical cyclization reactions using the radical initiator Cp₂TiCl, generated in situ from commercially available titanocene dichloride and Zn dust in tetrahydrofuran under argon.     

On the origin of optical activity in tris-diamine complexes of Co(III) and Rh(III): a simple model based on time-dependent density function theory

Time-dependent density functional theory (TD-DFT) is applied to the CD spectra of Lambda(deltadeltadelta)-(+)-[Co(S-pn)n(en)(3-n)]3+ (n = 1, 2, 3) and Lambda(deltadeltadelta)-(+)-[Co(en)3]3+ as well as the stereoisomers Delta-((delta)n(lambda)(3-n))-(-)-[Co(S-pn)n(en)(3-n)]3+ (n = 1, 2, 3) and Delta(deltadeltadelta)-(-)-[Co(en)3]3+. Theory is able to reproduce the major differences in the CD spectra of the species with a Lambda-configuration and their isomers with a Delta-configuration in both the d-d and ligand-to-metal CT region. It is further possible to rationalize the trend in terms of a larger azimuthal distortion away from the octahedral geometry in the Lambda-conformation compared to the Delta-configuration. Considerations were also given to the CD spectra of the lel3-isomer, Delta(lambdalambdalambda)-(-)-[Rh(R-pn)3]3+ and the ob-isomer, Lambda(lambdalambdalambda)-(+)-[Rh(S-pn)3]3+.     

Copper corrosion in buffered and non-buffered synthetic seawater: a comparative study

The electrochemical behaviour of copper in neutral buffered and non-buffered synthetic seawater and in pure chloride solutions has been studied by cyclic voltammetry, weight loss measurements, open circuit potential and scanning electron microscopy (SEM). Values of the repassivation potentials of Cu in non-buffered and buffered synthetic seawater, at 50 mV s^–1, were 0.12 and 0.46 V vs. SCE, respectively. The sharpness, heights and location of the different peaks as well as their charges were shown to be influenced by the composition of the solution, buffering conditions, deoxygenation, polarization potential and time. High chloride concentrations lead to higher oxidation charges. The anodic and the cathodic charges were shown to increase as the chloride concentration increases. The open circuit potential transients of copper in non-deoxygenated, non-buffered synthetic seawater indicate pitting from the beginning of the exposure, while in buffered solutions the pitting appeared only after a quite long exposure period, i.e. after 40 days. Corrosion rates of Cu samples after 3 months of immersion were higher in solutions of pure chloride (0.5 M) than in synthetic seawater. After six months the differences were even more noticeable. SEM images have showed a somewhat higher density of pits on copper samples immersed in the chloride solution (0.5 M), in comparison with those in synthetic seawater.     

An experimental and theoretical study of the Cp2VO2CO: use of 13CO3(2-) for structure investigation of d1-metallocene complexes

EPR study has shown that the anticancer agent vanadocene dichloride (Cp2VCl2) interacts with carbonate contained in physiological solutions. Chelate complex Cp2VO2CO (|A(iso)(51V)| = 175.1 MHz, g(iso) = 1.9861) is the only paramagnetic species formed in the range about the physiological pH (5.5-11.0). The super-hyperfine coupling (|a(iso)(13C)| = 24.1 MHz) was evidenced at measurements using 13C labelled carbonate. The structure of carbonate complex was validated by comparison of observed and theoretical calculated HFC tensors (at the density functional level of theory).