Ion exchangers as catalysts. II. Catalytic decomposition of hydrogen peroxide with resin-ethylenediamine-copper(II) complex ions

Summary The slow decomposition of H₂O₂ in the presence of Dowex-50 W resin in the form of an ethylenediaminecopper(II) complex ion in water is accompanied by an induction period. The reaction is first order with respect to [H₂O₂] and the rate constant (perg of dry resin) was deduced. Autocatalytic behaviour was found for the H₂O₂ decomposition with 2% crosslinked divinylbenzene. The induction period disappeared and the reaction rate increased when the decomposition was carried out with a resin in the form of a peroxo-copper complex, which proves that the formation of an intermediate (active species) retards the reaction rate. The precursor of the active species, formed during the induction period, was not the amine-copper(II) complex ion but a product of the latter with H₂O₂. It proved impossible to carry out the decomposition in acid or buffer solutions, in which the resin is regenerated.     

The thermal dissociation of some metal cupferrate chelates

The thermal dissociation of the cupferron complexes with Cu(II), Ni, Co(II), Zn, Cd, Mn(II), Hg(II), Mg, Ca, Ba, Sr, Al, Fe(III). Ce(III), La, and Nd was studied by differential thermal analysis (DTA) and by pyrolysis into a mass spectrometer. The DTA curves consisted mainly of endothermic peaks although some contained exothermic peaks as well. The mass spectrometer showed that cupferron decomposes slightly above room temperature, giving off N₂, NO, N₂O, NH₃ and H₂O. A mechanism for the thermal dissociation of the coppcr(II) cupferrate is proposed.     

Comparison of analytical techniques to quantify malondialdehyde in milk powders

Several analytical methods were compared to quantify malondialdehyde (MDA) in milk powders. Modified thiobarbituric acid (TBA) methods, using either visible spectrophotometry (direct absorbance reading or after third derivative transformation of the spectrum) or HPLC, required derivatisation at elevated temperature, which appeared to catalyse artefactual MDA formation and thus overestimate the MDA content. In contrast to the TBA derivatisation method, the measurement of MDA as the dinitrophenylhydrazone derivative by HPLC or as the phenylhydrazone product by GC-MS with a deuterated internal standard resulted in lower estimates in the ranges of 2-17- and 3-30-fold, respectively; apparently due to the milder derivatisation conditions. The estimates of MDA determined by both HPLC-UV and GC-MS techniques result in lower values which are similar in magnitude even though the GC-MS technique is more sensitive.     

Analysis of selected pesticides and alkylphenols in human cord blood by gas chromatograph-mass spectrometer

A total of seven pesticides and eight alkylphenols were monitored using this method for the determination of their trace levels in human cord blood. The pesticides are lindane, diazinon, α-endosulfan, β-endosulfan, endosulfan sulfate, chlorpyrifos and endrin; while the alkylphenols are 4-n-butylphenol, 4-n-pentylphenol, 4-n-hexylphenol, 4-t-octylphenol, 4-n-heptylphenol, nonylphenol, 4-n-octylphenol and bisphenol A. The pesticides and alkylphenols in the cord blood samples were extracted with solid phase extraction IST C18 cartridges and analyzed by selected ion monitoring mode using quadrapole detector in Shimadzu QP-5000 gas chromatograph-mass spectrometer. Trace levels of pesticide and alkylphenols in the range of non-detectable to 15.17 ng ml⁻¹, were detected in the human cord blood samples. This technique of monitoring the levels of endocrine-disruptors in blood samples is consistent, reliable and cost effective while reducing wastage of time and solvents.     

Computer-assisted optimization of reversed-phase HPLC isocratic separation of neutral compounds

An appropriate optimization strategy should be used to find a desired resolution or selectivity with a minimum number of experiments in a limited time, which could assure the baseline separation of all target compounds. It was usually realized by means of a specialized computer program. In this paper, mapping optimization method and overlapping resolution mapping were compared for the optimization of a reversed-phase high-performance liquid chromatography (HPLC) isocratic separation of neutral compounds. The calculated resolutions and separation time of 7 to 10 experiments are fitted by different equations, which were used to build a contour plot with a minimum effective resolution and maximum retention time as a function of a mobile phase composition. The balance between resolution and analysis time could be easily realized by the overlapping of the final overlapping resolution mapping and analysis time mapping. The validity of the two methods was confirmed by some typical experiments. The models are simple, visual, and common without theoretical arithmetic.     

Umbellactal, a novel diterpenoid from the Formosan soft coral Xenia umbellata

Umbellactal, isolated from the soft coral Xenia umbellata, is an unprecedented diterpenoid. The structure of umbellactal was established by extensive analysis of spectroscopic data.     

Structures and energies of seleno derivatives of biuret.Ab Initio comparative studies of diselenobiuret, selenobiuret, and selenothiobiuret

Ab initio studies (LCAO-MO method) on conformers of three seleno derivatives of the biuret molecules diselenobiuret [I], selenobiuret [II], and selenothiobiuret [III] were carried out at the Hartree-Fock (HF) and MP2 levels. The molecular geometries of these species were fully optimized at the HF level and characterized by analysis of the harmonic vibrational frequencies using a split-valence triple-zeta basis set augmented by a set ofd polarization functions on heavy atoms andp polarization functions on hydrogen atoms [TZP(d, p)]. The total energies of the HF-optimized structures were calculated at the MP2 (frozen core) level using a larger TZP (2df, 2pd) basis set. The potential energy searches revealed a total of 11 minimum-energy conformers (assigned astrans-trans, trans-cis, cis-trans, andcis-cis) and seven transition-state species for the title molecules. The two predicted conformers for diselenobiuret (Ia=trans-trans andIc=cis-cis) are characterized byC ₂ and the third byC _s symmetry. For selenothiobiuret two forms (IIIa=trans-trans andIIId=cis-cis) possessC ₁ and two (IIIb=trans-cis andIIIc=cis-trans) possessC _s symmetries, respectively. For selenobiuret, four formsIIa=trans-trans (C₁),IIb=trans-cis (C _s),IIc=cis-trans (C ₁), andIId=cis-cis (C₁), were obtained as a result of gradient optimization. Comparison of the relative energies for the considered species indicated that thecis-trans forms are the most stable conformations for all three systems at both the HF and MP2 levels of theory.     

Transient streaming potential in a finite length microchannel

Pressure-driven flow of an electrolyte solution in a microchannel with charged solid surfaces induces a streaming potential across the microchannel. Such a flow also causes rejection of ions by the microchannel, leading to different concentrations in the feed and permeate reservoirs connecting the capillary, which forms the basis of membrane based separation of electrolytes. Modeling approaches traditionally employed to assess the streaming potential development and ion rejection by capillaries often present a confusing picture of the governing electrochemical transport processes. In this paper, a transient numerical simulation of electrochemical transport process leading to the development of a streaming potential across a finite length circular cylindrical microchannel connecting two infinite reservoirs is presented. The solution based on finite element analysis shows the transient development of ionic concentrations, electric fields, and the streaming potential over the length of the microchannel. The transient analysis presented here resolves several contradictions between the two types of modeling approaches employed in assessing streaming potential development and ion rejection. The simulation results show that the streaming potential across the channel is predominantly set up at the timescale of the developing convective transport, while the equilibrium ion concentrations are developed over a considerably longer duration.     

Chemical Sensors for Electronic Nose Systems

Chemical sensors have been widely used for the analysis of volatile organic compounds. Employing chemical sensors in an array format with pattern recognition provides a higher degree of selectivity and reversibility leading to an extensive range of applications. When such systems are used for odour analysis they are termed electronic noses. Application of electronic noses ranges from the food industry, medical industry to environmental monitoring and process control. Many types of different gas sensors have been employed in the array. These include conducting polymers, metal oxide semiconductors, piezoelectric, optical fluorescence and amperometric gas sensors The transducer principle of these sensors is varied and is discussed in detail within this review. Examples of the current trends in sensor array technology as well as the applications to which the sensor-based noses have been applied are also discussed.     

From a biogenetic scenario to a synthesis of the ABC ring of manzamine A

On the basis of a biogenetic proposal for explaining the biogenesis of manzamine A, the cycloaddition of dihydropyridinium salt 26 with diene derivative 5 leads to adducts 27. These adducts, as well as their related and previously described analogues 9, are now shown to be precursors of diene derivatives such as 10, 13, and 28. Treatment of diene 32 with sodium azide resulted in a one-step formation of the tricyclic imino derivative 34. This key intermediate was further transformed into tricyclic derivative 40, which possesses the essential features of the ABC ring of manzamine A.