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181.
Kimmo Smolander Risto J?rnstr?m Annika Sajalinna 《Fresenius' Journal of Analytical Chemistry》1989,335(4):392-394
Summary The matric effect of boric acid was investigated in the determination of iron in the primary circuit coolant water of nuclear power plants by furnace atomic absorption spectrometry. The effect of boric acid was of particular interest. The method was applied during refuelling and maintenance periods and the results were used to interpret the chemical changes in the water.
Einfluß von Borsäure auf die Bestimmung von Eisen in Reaktorkühlwasser durch GF-AAS相似文献
182.
The title compound, (isopropylxanthato)(phenyl)mercury(I), was synthesized and characterized by elemental analysis, IR and thermogravimetric analysis. Density functional theory (DFT) method calculations were performed at B3LYP/CEP-121G and B3LYP/CEP-31G levels of theory, respectively. Vibrational frequencies were predicted, assigned, compared with the experimental values, and they are supported each other. The calculated results show that the strength of bond Hg—C is stronger than that of Hg—S, which is good agreement with the experimental data. The calculations of the second order optical nonlinearity and electronic absorption spectra are also performed. 相似文献
183.
Host-guest complexes of cucubit[8]uril with phenanthrolines and some methyl derivatives 总被引:1,自引:0,他引:1
DAY Anthony I 《中国科学B辑(英文版)》2005,48(4):305-314
Cucurbituril a molecular container (or host) has a rigid hollow interior cavity which is large enough to accommodate, one or more, smaller molecules (or guests). The cavity is accessible through two carbonyl portal openings. Molecules or guests enter the … 相似文献
184.
185.
This paper reports the results of a variety of experiments carried out for understanding the solvation behavior of potassium thiocyanate in methanol–water mixtures. Electrical conductivity, speed of sound, viscosity, and FT-Raman spectra of potassium thiocyanate solutions in 5 and 10% methanol–water (w/w) mixtures were measured as functions of concentration and temperature. The conductivity and structural relaxation time suggest the ion–solvent and solvent-separated ion–ion associations increase as the salt concentration increases in the mixtures. The Raman band shifts due to the C–O stretching mode of methanol for the solvent mixtures reveal the formation of methanol–water complexes. The significant changes in the Raman bands for the C–N, C–S and O–H stretching modes indicate the presence of SCN−−solvent interactions through the N-end, “free” SCN− and the solvent-shared ion pairs as potassium thiocyanate is added to the methanol–water mixtures. The relative changes corresponding to H–O–H bending and C–O stretching frequencies indicate that K+ is preferentially solvated by water in these solvent mixtures. The appearance and increase of the intensity of a broad band at ≈940 cm−1 upon salt addition was attributed to the SCN−–H2O–K+ solvent-shared ion pairs. No Raman spectral evidence for K+(H2O)n species was observed. The preferential solvation of K+ and SCN− in the methanol−water mixtures was verified by the application of the Kirkwood−Buff theory of solutions. This theory confirms that K+ is strongly preferentially solvated by water, whereas SCN− is preferentially solvated by the methanol component. 相似文献
186.
Mohamed M.?KhalilEmail author Mohamed?Taha 《Monatshefte für Chemie / Chemical Monthly》2004,135(4):385-395
Summary. The formation equilibria for the binary complexes of CoII, NiII, CuII, ZnII, CdII, MnII, PbII, ThIV, UO2II, and CeIII with tricine and for the ternary complexes involving some -amino acids (glycine, -alanine, proline, serine, asparagine, and aspartic acid) were investigated using pH-metric technique. The formation of binary and ternary complexes was inferred from the pH-metric titration curves. It was deduced that tricine acts as a primary ligand in the ternary complexes involving the monocarboxylic amino acids (glycine, -alanine, proline, serine, and asparagine), whereas it behaves as a secondary ligand in the ternary systems containing the dicarboxylic aspartic acid. The ternary complex formation was found to take place in a stepwise manner. The stability constants of the complexes formed in aqueous solutions were determined potentiometrically under the experimental conditions (t=25°C, I=0.1moldm–3 NaNO3). The order of stability of the ternary complexes in terms of the nature of the amino acids is investigated and discussed. The values of log K for the ternary complexes have been evaluated and discussed. Evaluation of the effects of ionic strength and temperature of the medium on the stability of the ternary system MII-tricine--alanine (MII=CoII, NiII, and CuII) has been studied. The thermodynamic parameters were calculated and discussed. 相似文献
187.
Sevim?Hamamci Veysel?T.?YilmazEmail author William?T.?A.?Harrison 《Structural chemistry》2005,16(4):379-383
The first silver(I) complex of saccharinate (sac) with pyridine (py), [Ag(sac)(py)]n has been synthesized and characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffractometry. The complex crystallizes in chiral, trigonal space group P3121 (No. 152) with unit cell parameters of a = 11.2605(2) Å, c = 17.3300(4) Å, V = 1903.02(6) Å3 and Z = 6. [Ag(sac)(py)]n contains monomeric [Ag(sac)(py)] units linked into infinite helices by way of Ag⋅sAg interactions [d(Ag⋅sAg) = 2.909(2) and 2.985(1) Å]. The distorted square-planar environment of Ag is completed by an N-bonded sac [Ag—N = 2.084(2) Å] and a py molecule [Ag—N = 2.116(2) Å]. The Nsac—Ag—Npy angle is 173.85(10)∘. The one-dimensional chains are crosslinked by C—H⋅sO interactions involving the carbonyl and sulfonyl O atoms of sac and aromatic-ring hydrogen atoms of both sac and py. The thermal stability of the title complex was investigated using thermogravimetry and differential thermal analysis in a static atmosphere of air. The first decomposition stage between 90 and 160∘C corresponds to removal of the py molecule in a single stage, while the degradation of the sac moiety occurs at two stages in the temperature range 370–515∘C, giving an end product of metallic Ag. 相似文献
188.
An enzymatic assay for glucose based on the use of the fluorescent probe for hydrogen peroxide, europium(III) tetracycline (EuTc), is described. The weakly fluorescent EuTc and enzymatically generated H2O2 form a strongly fluorescent complex (EuTc–H2O2) whose fluorescence decay profile is significantly different. Since the decay time of EuTc–H2O2 is in the microseconds time domain, fluorescence can be detected in the time-resolved mode, thus enabling substantial reduction of background fluorescence. The scheme represents the first H2O2-based time-resolved fluorescence assay for glucose not requiring the presence of a peroxidase. The time-resolved assay (with a delay time of 60 s and using endpoint detection) enables glucose to be determined at levels as low as 2.2 mol L–1, with a dynamic range of 2.2–100 mol L–1. The method also was adapted to a kinetic assay in order to cover higher glucose levels (mmol L–1 range). The latter was validated by analyzing spiked serum samples and gave a good linear relationship for glucose levels from 2.5 to 55.5 mmol L–1. Noteworthy features of the assay include easy accessibility of the probe, large Stokes shift, a line-like fluorescence peaking at 616 nm, stability towards oxygen, a working pH of approximately 7, and its suitability for both kinetic and endpoint determination. 相似文献
189.
The apparent molar volumes, V,2, of glycine, L-alanine, DL--amino-n-butyric acid, L-valine, and L-leucine have been determined in aqueous 0.25, 0.75, 1.0, and 1.5 mol-dm–3 tetraethylammonium bromide (TEAB) solutions by density measurements at 298.15 K. These data have been used to calculate the infinite dilution apparent molar volumes, V2,m, for the amino acids in aqueous tetraethylammonium bromide and the standard partial molar volumes of transfer (tr V2,m) of the amino acids from water to the aqueous salt solutions. The linear correlation of V2,m for a homologous series of amino acids has been utilized to calculate the contribution of the charged end groups (NH3+, COO–), CH2 group, and other alkyl chains of the amino acids to V2,m. The results of the standard partial molar volumes of transfer from water to aqueous tetraethylammonium bromide have been interpreted in terms of ion–ion, ion–polar, and hydrophobic–hydrophobic group interactions. The volume of transfer data suggest that ion–ion or ion–hydrophilic interactions are predominant in the case of glycine and alanine, and hydrophobic–hydrophobic group interactions are predominant in the case of DL--amino butyric acid, L-valine, and L-leucine. 相似文献
190.
Redox-active tyrosine residues play important roles in long-distance electron reactions in enzymes, including prostaglandin H synthase, galactose oxidase, ribonucleotide reductase, and photosystem II. Magnetic resonance and vibrational spectroscopy provide methods with which to study the structures of redox-active amino acids in proteins. In this report, ultraviolet photolysis was used to generate tyrosyl radicals from polycrystalline tyrosinate or dipeptides, and the structure of the radical was investigated with EPR and reaction-induced FT-IR spectroscopy at 77 K. Photolysis at 77 K is expected to generate a neutral tyrosyl radical through oxidation of the aromatic ring. EPR and FT-IR results obtained from (13)C-labeled tyrosine were consistent with that expectation. Surprisingly, labeling of the tyrosyl amino group with (15)N also resulted in isotope-shifted bands in the photolysis spectrum. The force constant of a NH deformation mode increased when the tyrosyl radical was generated. These data suggest an interaction between the pi system of the tyrosyl radical and the amino group. In spectra acquired from the dipeptides, evidence for a sequence-dependent interaction between the tyrosyl radical and the amide bond of the dipeptide was also obtained. We postulate that perturbation of the amino or the amide/imide groups may occur through a spin polarization mechanism, which is indirectly detected as a change in NH force constant. This conclusion is supported by density functional calculations, which suggest a conformationally sensitive delocalization of spin density onto the amino and carboxylate groups of the tyrosyl radical. These experiments provide a step toward a detailed spectral interpretation for protein-based tyrosyl radicals. 相似文献