The effects of media properties on the horseradish peroxidase-catalyzed fluorogenic reaction

The effects of media properties including buffers, acidity, solvents and surfactant on horseradish peroxidase-catalyzed fluorogenic reaction were investigated. The results showed that the so-called non-fluorescent hydrogen donors were in fact fluorescent. There existed an acid—base equilibrium in the fluorescent dimer product. For p -hydroxyphenylpropionic acid, a pK_a value of 8.0 for the product was obtained from its titration curve. The product fluorescence increased with higher pH, however, a longer time was needed to reach the reaction equilibrium due to the pH mismatch problem. Cationic micelles cetyltrimethylammonium bromide and cetyltrimethylammonium chloride could reduce the pH mismatch and offered a way to further increase the determination sensitivity. Finally, a micelle-enhanced flow-injection analysis of horseradish peroxidase is suggested.     

NLS-tupe equations in 2+1 dimensions: New type of solutions and non-isospectral problems

Integrable systems of NLS type in 2+1 dimensions are studied in three ways: their special solutions by Lie point symmetries, breaking-solutions by the ISM, as well as the non-isospectral problems.Department of Mathematics, Statistics and Computing Science, University of New England, Armidale N.S.W. 2351, Australia. E-mail: zhuhan@neumann.une.edu.au, xhe@metz.une.edu.au Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 99, No. 3, pp. 382–389, June, 1994.     

Separation of polycyclic aromatic hydrocarbons by micellar electrokinetic chromatography with aqueous short-chain alcohol solvent

Micellar electrokinetic capillary chromatography (MEKC) with aqueous organic solvent has been developed to separate polycyclic aromatic hydrocarbons (PAHs). Methanol, ethanol or propanol as an organic modifier was added to sodium dodecyl sulfate (SDS) micellar solution in order to increase the solubility of very hydrophobic solutes in mobile phase. Both methanol and ethanol can be used as co-solvents for the separation of PAHs. Use of ethanol resulted in a shorter analysis time than use of methanol. The separations of some PAHs were unsatisfactory using propanol although the analysis time was much shorter than with ethanol. The influence of ethanol content, SDS concentration and temperature on the separations was studied. Benzene and nine polycyclic aromatic hydrocarbons were successfully separated using 50 mM SDS-20 mM phosphate-5 mM borate, containing 40% (v/v) ethanol at 35 degrees C. The relative standard deviation (R.S.D.) of t(R) ranged from 0.5 to 1.5% for six repeat injections.     

TheΛ b →Λ c decay form factors

The recently measured cross-sections for diffractive dissociation of nuclei in high-energy proton nucleus (pA) collisions show a strikingA ^1/3 dependence on the target massA. Such a dependence emerges from an optical model which incorporates a simple mechanism to produce the absorption fluctuations required for inelastic diffraction. The observed momentum transfer (t) dependence of the differential cross-section, dσ/dt∝ exp(?B|t|), is described in terms of a correlation length \(R_F = \sqrt {2B} \) of the absorption fluctuations which turns out to be of the size of a nucleon. The excitation massM dependence, dσ/dM ²∝M ^?2, is explained by a bremsstrahlung mechanism.     

Study of occupational health impact of atmospheric pollution on exposed workers at an iron and steel complex by using neutron activation analysis of scalp hair

The occupational health impact of atmospheric pollution on exposed workers at one iron and steel complex was studied by instrumental neutron activation analysis of workers' hair samples and medical examination. The experimental results indicate that there is a positive correlation between the high inhalation amounts of iron and other trace elements by the exposed workers and the symptom of their high blood pressure and hypoglycemia, which implies that the atmospheric environment polluted by iron and steel industry has an adverse health impact on the exposed workers. The measures to relieve and abate the occupational diseases caused by air-borne particulate matter should be taken     

NMR determination of absolute site-specific natural isotope ratios of hydrogen in organic molecules. Analytical and mechanistic applications

It has been shown that the “internal” isotope distribution within a given molecular species at the natural abundance level is accessible by a new method, SNIF-NMR, which is based on deuterium NMR. Relative internal factors, R_i/j,have been defined which enable the isotope content of a given site, i, to be compared to that of another molecular site, j, taken as the reference. Several referencing methods intended to provide direct access to relative $\text{externals}$, T_i , and $\text{absolute}$, (D/H)_i , site-specific parameters, are now discussed from both the theoretical and the experimental points of view. In the $\text{intramolecular referencing method}$, which involves a time-consuming chemical transformation of the sample, the risk exists of more or leas systematic errors resulting from discriminating fractionation effects. However this technique offers, conversely, an interesting way of investigating kinetic isotope effects without the need for specific labelling. In spite of its lower spectral precision the $\text{external referencing method}$ has the advantage of being fast and less sensitive to systematic errois and may be used for direct rough routine determinations of the site-specific isotope contents. More precise results can be obtained, at the price of contaminating the sample, when an $\text{intermolecular reference}$ is added and signal heights are used, remembering however that the intensity parameters then have no strict physical meaning in terms of absolute isotope contents. The site-specific parameters, T_i and (D/H)_i thus accessible, provide new information on the mechanisms of the fractionation effects occurring in natural conditions and examples are considered.     

Tandem mass spectrum of a farnesyl transferase inhibitor--gas-phase rearrangements involving imidazole

Compound 1 (1-(3-chlorophenyl)-4-[1-(4-cyanobenzyl)imidazolylmethyl]-2-piperazinone hydrochloride) is a farnesyl transferase inhibitor intended for treatment of cancer. A detailed analysis of the electrospray ionization mass spectrometry and tandem mass spectrometry data of protonated 1 shows that in the gas phase, upon collision-induced dissociation, this ion undergoes complicated rearrangement and fragmentation. These processes include a novel two-step rearrangement. The first step involves a gas-phase intramolecular S(N)2 reaction that forms an intermediate. The second step consists of three competitive rearrangement/fragmentation pathways of the intermediate, giving rise to protonated 2, protonated methylene-imidazole, and a distonic methylimidazole radical cation. Deuterated 1 was studied under the same experimental conditions, and the results strongly support the proposed two-step rearrangement process. It is noted that the unique structure of 1, especially the imidazole ring of 1, plays a critical role in the rearrangement of protonated 1.     

Heck-reaction on alpha-C-p-bromophenyl delta2-glycopyranodise: an easy access to functionalized C-aryl glycoside

Palladium-catalyzed Heck condensation of C-p-bromophenyl delta2-glycopyranoside with methyl vinyl ketone, methyl acrylate, acrylonitrile, or N-acetyldehydroalanine methyl ester occurred in quite good yields (60-82%).     

The uranium-Xylidyl Blue I complex and its application in linear sweep polarography

The linear sweep polarographic wave of the uranium-Xylidyl Blue I complex in ethylenediamine-1,10-phenanthroline-hydrochloric acid medium has been studied. The complex, corresponding to UO(2)(XBI)(2-)(2) with log beta' = 9.09 (by polarography), 8.81 (by spectrophotometry), is strongly adsorbed on the surface of the mercury electrode. The polarographic wave is attributed to the reduction of Xylidyl Blue I in the complex. The method is very sensitive with a detection limit of 3 x 10(-8)M. The wave height is proportional to the concentration of uranium over the range 8 x 10(-8)-7 x 10(-6)M. Solvent extraction is used to separate possible interferences. The recommended procedure has been applied to the determination of trace amounts of uranium in ores.     

Separation and determination of podophyllum lignans by micellar electrokinetic chromatography

A micellar electrokinetic chromatography method was established for the quantitative analysis of seven podophyllum lignans in Podophyllum emodi Wall. var. chinesis sprague. The optimum buffer system was 10 mM NaH2PO4-5 mM borate-100 mM sodium dodecylsulfate-30% isopropanol (pH 7.20). Voltage was 18 kV and detection at 214 nm. The second derivative chromatogram was used to determine a low-content component and those not fully separated from adjacent ones. The RSD values of migration times and peak areas were <2.2 and <5.5%, respectively. The effects of several CE parameters on the resolutions were studied systematically.