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41.
A. Baştuğ Ö. Söğüt Y. Şahin M. Ertuğrul 《Journal of Radioanalytical and Nuclear Chemistry》2002,251(2):323-327
La and Lb X-ray fluorescence cross sections in Er, Ta, W and Au at excitation energies of 16.896, 22.581, 25.770, 32.890, 38.184, 43.949, 50.214 and 59.5 keV were investigated. Measurements were made using a low energy Si(Li) detector coupled to a model 4096 computerized multi-channel analyser. The experimental results were compared with the theoretically calculated values of L X-rays fluorescence cross sections and other experimental results. Good agreement was observed between experimental and theoretical values. 相似文献
42.
43.
4-(4′-Dioctylaminocarbonylbiphenyloxy) phthalonitrile was synthesized from 4-(4′-carboxybiphenyloxy)phthalonitrile and dioctylamine
in the presence of Et3N. Metallophthalocyanines (Zn, Co and Cu) substituted with four dioctylaminocarbonyl biphenyloxy groups on the peripheral
positions were prepared from 4-(4′-dioctylaminocarbonylbiphenyloxy)phthalonitrile and the corresponding divalent metal salts
(Zn(CH3COO)2, CoCl2 and CuCl2). The new phthalocyanines are soluble in common organic solvents. These compounds were characterised by 1H-NMR, 13C-NMR, FT-IR, UV-Vis and mass spectroscopies. 相似文献
44.
L. A. Wall S. Straus R. E. Florin 《Journal of polymer science. Part A, Polymer chemistry》1966,4(2):349-365
Quantitative comparisons were made between the rates of thermal volatilization of several fluoropolymers before and after exposure to γ-radiation. The effects of γ-irradiation on poly(vinyl fluoride) and poly(vinylidene fluoride) were also investigated by swelling and sol-gel ratios. With both polymers as well as with polytrifluoroethylene, crosslinks occur predominantly, though there is an appreciable number of scissions. The rates of volatilization and char formation were enhanced by γ-radiation, whereas the previously studied polytrifluoroethylene did not produce more char upon irradiation, although radiation did accelerate its volatilization. It is believed that in polytrifluoroethylene the enhanced rates of volatilization occur by a different mechanism than in the case of the vinyl and vinylidene fluoride polymers. 相似文献
45.
A new liquid chromatographic (LC)-chemometric approach was developed for the determination of sunset yellow (SUN) and tartrazine (TAR) in commercial preparations. This approach uses LC and chemometric calibration methods, i.e., classical least-squares (CLS), principal component regression (PCR), and partial-least squares (PLS), simultaneously. The combined LC-chemometric approaches, denoted as LC-CLS, LC-PCR, and LC-PLS, are based on photodiode array (PDA) detection at multiple wavelengths. Optimum chromatographic separation of SUN and TAR with allura red as the internal standard (IS) was obtained by using a Waters Symmetry C18 column, 5 microm, 4.6 x 250 mm, and 0.2 M acetate buffer (pH 5)-acetonitrile-methano-bidistilled water (55 + 20 + 15 + 10, v/v) as the mobile phase at a flow rate of 1.9 mL/min. The LC data sets consisting of the ratios of analyte peak areas to the IS peak area were obtained by using PDA detection at 5 wavelengths (465, 470, 475, 480, and 485 nm). LC-chemometric calibrations for SUN and TAR were separately constructed by using the relationship between the peak-area ratio and the training sets for each colorant. LC-chemometric approaches were tested for different synthetic mixtures containing SUN and TAR in the presence of the IS. These LC-chemometric calibrations were applied to a commercial preparation of the 2 colorants. The experimental results of the LC-chemometric approaches were compared with those obtained by a developed classical LC method using single-wavelength detection. 相似文献
46.
On the applicability of the HSAB principle through the use of improved computational schemes for chemical hardness evaluation 总被引:1,自引:0,他引:1
Finite difference schemes, named Compact Finite Difference Schemes with Spectral-like Resolution, have been used for a less crude approximation of the analytical hardness definition as the second-order derivative of the energy with respect to the electron number. The improved computational schemes, at different levels of theory, have been used to calculate global hardness values of some probe bases, traditionally classified as hard and soft on the basis of their chemical behavior, and to investigate the quantitative applicability of the HSAB principle. Exchange acid-base reactions have been used to test the HSAB principle assuming the reaction energies as a measure of the stabilization of product adducts. 相似文献
47.
The 1,10-phenanthroline (phen) complexes of Co(II), Ni(II), Cu(II) and
Cd(II) orotates were synthesized and characterized by elemental analysis,
magnetic susceptibility, spectral methods (UV-vis and FTIR) and thermal analysis
techniques (TG, DTG and DTA). The Co(II), Ni(II), Cu(II) and Cd(II) ions in
diaquabis(1,10-phenanthroline)metal(II) diorotate octahedral complexes [M(H2O)2(phen)2](H2Or)2·nH2O
(M=Co(II), n=2.25; Ni(II), n=3;
Cu(II) and Cd(II), n=2) are coordinated
by two aqua ligands and two moles of phen molecules as chelating ligands through
their two nitrogen atoms. The monoanionic orotate behaves as a counter ion
in the complexes. On the basis of the first DTGmax,
the thermal stability of the hydrated complexes follows the order: Cd(II),
68°C 68°C 相似文献
48.
N. K. Tunali H. N. Erten S. Kinikoğlu Ş. Gümüş 《Journal of Radioanalytical and Nuclear Chemistry》1979,49(2):225-237
The extraction of iodine and bromine under various conditions from their saturated aqueous solutions by CCl4, C6H6 and o-xylene has been studied. The data obtained from the experiments carried out at various temperatures, for H2O(I2)−CCl4 and H2O(I2)−C6H6 systems, exhibit an Arrhenius behaviour. The overall activation energy calculated for the extraction in the H2O(I2)−CCl4 system, 650±50 cal·mol−1 is lower than that of H2O(I2)−C6H6, 3600±300 cal·mol−1. The use of the solubility parameter for the interpretation of the data in the extraction of iodine is investigated. The
data obtained in multiple extractions are treated by using the analogy between extraction and radioactive decay. The half
number of extraction for each system is determined. The complex curves obtained in the H2O(I2)−CCl4 and H2O(I2) −Br2)−CCl4 systems are resolved into two components. 相似文献
49.
A method is described to evaluate backbone interactions in proteins via computational unnatural amino acid mutagenesis. Several N-acetyl polyalanyl amides (AcA(n)NH(2)) were optimized in the representative helical (3(10)-, 4(13)-, and a "hybrid" kappa-helix, n = 7, 9, 10, 14) and hairpin (two- and three-stranded antiparallel beta-sheets with type I turns betaalphaalphaepsilon, n = 6, 9, 10) conformations, and extended conformers of N-acetyl polyalanyl methylamides (n = 2, 3) were used to derive multistranded beta-sheet fragments. Subsequently, each residue of every model structure was substituted, one at a time, with l-lactic acid. The resulting mutant structures were again optimized, and group-transfer energies DeltaE(GT) were obtained as heats of the isodesmic reactions: AcA(n)NHR + AcOMe --> AcA(x)LacA(y)NHR + AcNHMe (R = H, CH(3)). These group-transfer energies correlate with the degree of charge polarization of the substituted peptide linkages as measured by the difference Deltae in H and O Mulliken populations in HN-C=O and with the H-bond distances in the "wild-type" structures. A good correlation obtains for the HF/3-21G and B3LYP/6-31G* group-transfer energies. The destabilization effects are interpreted in terms of loss of interstrand and intrastrand H-bonds, decrease in Lewis basicity of the C=O group, and O...O repulsion. On the basis of several comparisons of Ala --> Lac DeltaE(GT)'s with heats of the NH --> CH(2) substitutions, the latter contribution is estimated (B3LYP/6-31G*) to range between 1.5 and 2.4 kcal mol(-1), a figure close to the recent experimental DeltaDeltaG(o) value of 2.6 kcal mol(-1) (McComas, C. C.; Crowley, B. M.; Boger, D. L. J. Am.Chem. Soc. 2003, 125, 9314). The partitioning yields the following maximum values of the electronic association energy of H-bonds in the examined sample of model structures (B3LYP/6-31G* estimates): 3(10)-helix D(e) = -1.7 kcal mol(-1), alpha-helix D(e) = -3.8 kcal mol(-1), beta-sheet D(e) = -6.1 kcal mol(-1). The premise of experimental evaluations of the backbone-backbone H-bonding that Ala --> Lac substitution in proteins is isosteric (e.g., Koh, J. T.; Cornish, V. W.; Schultz, P. G. Biochemistry 1997, 36, 11314) is often but not always corroborated. Examination of the integrity of H-bonding pattern and phi(i), psi(i) distribution identified several mutants with significant distortions of the "wild-type" structure resulting inter alia from the transitions between i, i + 3 and i, i + 4 H-bonding in helices, observed previously in the crystallographic studies of depsipeptides (Ohyama, T.; Oku, H.; Hiroki, A.; Maekawa, Y.; Yoshida, M.; Katakai, R. Biopolymers 2000, 54, 375; Karle, I. L.; Das, C.; Balaram, P. Biopolymers 2001, 59, 276). Thus, the isodesmic reaction approach provides a simple way to gauge how conformation of the polypeptide chain and dimensions of the H-bonding network affect the strength of backbone-backbone C=O...HN bonds. The results indicate that the stabilization provided by such interactions increases on going from 3(10)-helix to alpha-helix to beta-sheet. 相似文献
50.
Mixed gels of starch and bentonite are investigated in the interval 0.056–0.089 of total solids/water ratio and 0-100% starch in the solids. The bentonite was a sodium calcium bentonite with a Na/Ca ratio of 1.76. In water it forms gels consisting of a network of band-type structures. Starch forms gels through hydrogen bonds between granules and/or amylose and amylopectin present on the external surfaces of granules and/or in fully stretched form. Mixed gels of bentonite and starch were obtained by adding corn starch granules to the already formed bentonite gels and heating the mixture above the Kofler gelatinization temperature. Amylose and amylopectin were adsorbed on strands of band-type structures of mont-morillonite lamellae. Starch gellation, e.g. diffusion of amylose out of the granule, was facilitated in the presence of bentonite. On the other hand, the presence of starch favored delamination of the montmorillonite particle into thinner lamellae. Maximum gelatinization and polymer adsorption were observed for gels with 20% starch and 80% bentonite. Montmorillonite networks formed the continuous phase for 0-80% starch. At higher starch concentrations, montmorillonite flakes were dispersed within the polymer network. Increase in the water content of the gels caused segregation of the bentonite and starch. 相似文献