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51.
Formation and reactivity of free radicals in 5-hydroxymethyl-2-furaldehyde--the effect on isoprenaline photostability 总被引:1,自引:0,他引:1
Brustugun J Tønnesen HH Edge R Navaratnam S 《Journal of photochemistry and photobiology. B, Biology》2005,79(2):109-119
Solutions of glucose are used as diluents for drugs in various drug infusions. When sterilized by heat small amounts of the substance 5-hydroxymethyl-2-furaldehyde (5-HMF) is produced from glucose. At a hospital ward such infusions may be exposed to irradiation; including UV-light. The photoreactivity of the furaldehyde is investigated. It is shown to photodestabilize the catecholamine isoprenaline. It is shown to be a producer, but also a consumer, of singlet oxygen. The excited triplet, cation and anion radical have been produced by pulse radiolysis and flash photolysis and their absorbance characteristics have been determined. The triplet absorption spectrum showed absorption bands at 320 and 430 nm with molar absorption coefficients of 4700 and 2600 M-1 cm-1, respectively. The anion radical showed absorption bands at 330 and 420 nm with molar absorption coefficients of 2000 and 300 M-1 cm-1, respectively. The cation radical had an absorption band at 320 nm with a molar absorption coefficient of 5000 M-1 cm-1. The quantum yield for the production of singlet oxygen, sensitized by the 5-HMF triplet, was determined to be 0.6, whilst the quantum yield for the triplet formation was 1.0. Aqueous solutions of 5-HMF were found to photoionize to yield the hydrated electron and the cation radical of 5-HMF in a biphotonic process. The influences of pH, buffer and glucose on the formation of transients were evaluated. The reactions between 5-HMF and the solvated electron, the hydroxyl radical and the superoxide were also studied. 相似文献
52.
The rate of the reaction between D2O and the calcium aluminum oxides Ca3Al2O6, Ca5Al6O14, CaAl2O4, and CaAl4O7 was investigated by on-line neutron diffraction powder methods at temperatures from room temperature to 100°C. The rate of the reaction increases with increasing calcium content of the compounds and with increasing temperature for each of the compounds. The crystallographic stable hydrate Ca3Al2(OD)12 is obtained from CaAl4O7 and CaAl2O4 at temperatures above 63°C, from Ca5Al6O14 at temperatures above 49°C, and from Ca3Al2O6 at temperatures as low as 7°C. 相似文献
53.
A practical approach to high performance capillary electrophoresis with biosynthetic human growth hormone as a model protein 总被引:1,自引:0,他引:1
Biosynthetic human Growth Hormone (B-hGH) is a protein comprising 191 amino acids. The molecular weight is 22,125 and the isoelectric point is close to pH 5. Due to the ready availability of closely related analogues B-hGH was used as a model protein thus allowing for the demonstration and evaluation of the high resolution capability of high performance capillary electrophoresis (HPCE). The same apparatus was used throughout the experiments and an optimum signal-to-noise ratio was found at 200 nm. Linearity was observed between peak area, retention time and the hGH concentration or sample introduction time. Baseline separation of hGH, desamido hGH and didesamido hGH was obtained. Examples showing analysis with 1 million theoretical plates per meter, high speed separation, simultaneous analysis of multiple samples, sample stacking, hGH tryptic digest, and hGH lysate are reported. The use of electrophoretic velocities instead of apparent velocities for peak identification is illustrated. 相似文献
54.
Mikkelsen Ø Skogvold SM Schrøder KH Gjerde MI Aarhaug TA 《Analytical and bioanalytical chemistry》2003,377(2):322-326
Evaluation of different solid electrode systems for detection of zinc, lead, cobalt, and nickel in process water from metallurgical nickel industry with use of differential pulse stripping voltammetry has been performed. Zinc was detected by differential pulse anodic stripping voltammetry (DPASV) on a dental amalgam electrode as intermetallic Ni–Zn compound after dilution in ammonium buffer solution. The intermetallic compound was observed at –375 mV, and a linear response was found in the range 0.2–1.2 mg L–1 (r2=0.98) for 60 s deposition time. Simultaneous detection of nickel and cobalt in the low g L–1 range was successfully performed by use of adsorptive cathodic stripping voltammetry (AdCSV) of dimethylglyoxime complexes on a silver–bismuth alloy electrode, and a good correlation was found with corresponding AAS results (r2=0.999 for nickel and 0.965 for cobalt). Analyses of lead in the g L–1 range in nickel-plating solution were performed with good sensitivity and stability by DPASV, using a working electrode of silver together with a glassy carbon counter electrode in samples diluted 1:3 with distilled water and acidified with H2SO4 to pH 2. A new commercial automatic at-line system was tested, and the results were found to be in agreement with an older mercury drop system. The stability of the solid electrode systems was found to be from one to several days without any maintenance needed. 相似文献
55.
Josef Ischtwan Peter Schwerdtfeger Sigrid D. Peyerimhoff Michael A. Collins Trygve Helgaker Poul Jørgensen Hans Jørgen Aa. Jensen 《Theoretical chemistry accounts》1994,89(2-3):157-168
Summary The intrinsic reaction-path, reactants, transition state and products for the reaction of NH (3–)+H2 (1
g
+
) NH2 (2B1)+H (2S) involving the lowest triplet electronic state of NH3 were calculated using multi-configuration (MC) SCF methods. The calculated change of internal energy for the reaction of 11.0 kcal mol–1 agrees with the experimental value within 2 kcal mol–1. The barrier to reaction is 23.4 kcal mol–1 high. The harmonic MCSCF reaction-path potential was calculated and canonical variational transition state theory calculations of the rate constants performed over a temperature range from 400 to 2500 K. The computed rate constants are generally two orders of magnitude smaller than those of the comparable reaction of OH with H2, whereas those of the reverse reaction are by a factor of 20 larger than those of OH2 with H. 相似文献
56.
The International Measurement Evaluation Programme (IMEP) is an interlaboratory comparison scheme, founded, owned and coordinated by the Institute for Reference Materials and Measurements (IRMM) since 1988. IMEP-9 is the third round of trace elements in water evaluation following IMEP-3 and IMEP-6. Reference values for 15 elements stating total concentrations and combined uncertainties (according to GUM) were established. The reference values were established mainly by isotope dilution mass spectrometry (IDMS) as a primary method of measurement, and values traceable to the SI were obtained. The four elements that could not be certified by IDMS were assigned values by means of other measurement techniques. Results from 201 laboratories from 35 countries and four continents were evaluated against the reference values and the comparability between the laboratories is presented graphically. 相似文献
57.
Summary A method is described for the determination of small quantities of hydrochloric acid in two chlorinated organic solvents (CHCl3 and CCl4). An excess of gaseous ethylene oxide is added to a liquid sample; the 2-chloroethanol formed is then analyzed by gas chromatography. The procedure is simpler and more sensitive in comparison with other conventional methods. It can be modified for other organic solvents.D.G.R.C.S.T. grant. 相似文献
58.
First-order relativistic corrections to the energy of closed-shell molecular systems are calculated, using all terms in the two-component Breit-Pauli Hamiltonian. In particular, we present the first implementation of the two-electron Breit orbit-orbit integrals, thus completing the first-order relativistic corrections within the two-component Pauli approximation. Calculations of these corrections are presented for a series of small and light molecules, at the Hartree-Fock and coupled-cluster levels of theory. Comparisons with four-component Dirac-Coulomb-Breit calculations demonstrate that the full Breit-Pauli energy corrections represent an accurate approximation to a fully relativistic treatment of such systems. The Breit interaction is dominated by the spin-spin interaction, the orbit-orbit interaction contributing only about 10% to the total two-electron relativistic correction in molecules consisting of light atoms. However, the relative importance of the orbit-orbit interaction increases with increasing nuclear charge, contributing more than 20% in H(2)S. 相似文献
59.
This paper is concerned with idealizing brownian motion as a random walk, using the diffusion equation, and finding the boundary condition at an absorbing surface - all with an eye towards chemical kinetics. Three models of random walk (due to Smoluchowski, Fermi, and Lorentz) are considered, and it is concluded that the lorentzian model is the most appropriate. 相似文献
60.
Nielsen UG Topsøe NY Brorson M Skibsted J Jakobsen HJ 《Journal of the American Chemical Society》2004,126(15):4926-4933
The first observations of the complete manifold of spinning sidebands (ssbs) including both the central and satellite transitions in (51)V MAS NMR spectra of surface vanadia nanoparticles on titania in DeNO(x) catalysts are presented. (51)V quadrupole coupling and chemical shift anisotropy parameters for the dominating vanadia structure are determined from (51)V MAS NMR spectra recorded at 9.4 and 14.1 T. Based on correlations previously established between (51)V NMR parameters and crystal structure data for inorganic vanadates, the NMR data are consistent with vanadium in a distorted octahedral oxygen coordination environment for the so-called strongly bonded vanadia species on the surface. The investigation includes two vanadia-titania model catalysts and six industrial-type DeNO(x) catalysts. 相似文献