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71.
J. M. Hernndez Ana M. Herrera J. García‐Serrano J. F. Rivas‐Silva 《International journal of quantum chemistry》2002,88(3):342-346
Conformations of p‐methacryloylaminophenylarsonic acid (p‐MAPHA) are determined through molecular mechanics and DFT/B3LYP calculations. Solvation effects are studied within the self‐consistent isodensity continuum model (SCI‐PCM). The stationary points were found to correspond to minima as verified by the analysis of vibrational frequencies in the molecule. The molecular optical absorption was obtained by using different solvent environments. The present results are in good agreement with the available experimental data. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 相似文献
72.
Maria Fernanda Silva Estela Soledad Cerutti Luis D. Martinez 《Mikrochimica acta》2006,155(3-4):349-364
The purpose of this article is to review and evaluate cloud point extraction of metals and its coupling to different contemporary
instrumental methods of analysis. This review covers a selection of the literature published on this topic over the period
mainly between 1997 and September 2005 (consisting of 50 publications). The current state of the art for CPE concerning metals
and metal chelates is presented with special emphasis on the hyphenation of this interesting extraction/preconcentration approach
mediated by surfactants to spectrophotometry, atomic spectroscopy and separation techniques. We present contemporary CPE developments
concerning metal speciation and determination and their application to different environmental, clinical, geological and food
samples. Strategies for method development as well as future perspectives are also covered. 相似文献
73.
Pinotti Laura M. Silva Rosineide G. Giordano Roberto C. Giordano Raquel L. C. 《Applied biochemistry and biotechnology》2002,98(1-9):679-686
This article reports studies concerning the production of penicillin G acylase (PGA) by Bacillus megaterium. This enzyme has industrial use in the hydrolysis of penicillin G to obtain 6-aminopenicillanic acid, an essential intermediate
for the production of semisynthetic β-lactam antibiotics. Although most microorganisms produce the enzyme intracellularly,
B. megaterium provides extracellular PGA. The enzyme production by microorganisms involves several steps, resulting in a many operational
variables to be studied. The study of the inoculum is an important step to be accomplished, before addressing other issues
such as culture optimization and downstream processing. In this study, using a standard inoculum as reference, several runs
were performed aiming at the definition of operational conditions in the PGA production. Cell concentration and PGA activity
in the production medium were measured after 24, 48, and 72 h of the beginning of the production phase. This study encompasses
the duration of the inoculum germination phase and the concentration of cells used to startup the germination. Based on these
results, PGA productivity during the production phase was maximized. The selected values for these variables were 1.5 × 107 spores/mL of germination medium, germination during 24 h, and 72 h for the production phase. 相似文献
74.
E. A. Guimares Costa F. De Brito Mota A. Ferreira Da Silva 《International journal of quantum chemistry》1992,41(3):517-524
The density of states is calculated for a random distribution of donor-pairs of hydrogenlike impurities in three- and two-dimensional systems. Recent investigations of the hydrogen molecule in the alternant–molecular–orbital approximation are here extended. We found that the lowest excited state 1Σu (i.e., H+H?), which is optically connected to the ground state, plays a relevant role in the absorption spectra of semiconductor systems. 相似文献
75.
rico Marlon de Moraes Flores Ana Paula Fleig Saidelles Eder Lisandro de Moraes Flores Mrcia Foster Mesko Mrcio Pozzobon Pedroso Valderi Luiz Dressler Celso Figueiredo Bittencourt Adilson Ben da Costa 《Microchemical Journal》2004,77(2):113-118
An alternative device for the direct solid analysis (DSA) for copper determination by flame atomic absorption spectrometry (FAAS) is proposed. Copper was directly determined in commercial medicinal plants used as dietary supplements. The determination of copper in solid samples by DSA–FAAS was made by using a conventional air–acetylene flame. Between 0.05 and 1.5 mg of each test, sample was weighed directly into a small polyethylene vial connected to the device used for solid introduction into the flame. Test samples were introduced into the flame as a dry aerosol using a T-quartz cell set between the burner and the optical path. The T-quartz cell has a slit in the superior part by which the solid aerosol passes to the flame. A transient signal, evaluated as integrated absorbance, is produced and it is totally integrated in 2 s. Background signals always presented absorbance values less than 0.1. It was found a characteristic mass of 0.8 ng Cu and absolute limit of detection of 1.2 ng (3 s), or 1.2 μg g−1 if a sample mass of 1 mg was used. Optimized conditions for air flow rate, flame stoichiometry, and so on were established as well. No excessive grinding of the samples was needed and samples with particle of size less than 80 μm were used throughout. No statistical difference between the results from the proposed system and those obtained by sample digestion and determination by conventional FAAS was observed. With the proposed procedure, more than 50 test samples can be analyzed in 1 h and it can be easily adapted to conventional spectrometers for FAAS. 相似文献
76.
在脉冲微反装置上考察了不同的预处理条件对Zn/Al-CLM催化剂的丙烷芳构化反应的影响。结果表明,丙烷在Zn/Al-CLM催化剂上具有一定的的反应活性和芳烃选择性,而且芳构化主要转化为苯;载体Al-CLM的焙烧温度、金属锌负载量、活化温度等对Zn/Al-CLM催化剂的丙烷芳构化性能具有重要影响。载体经500℃预焙烧制备的Zn/Al-CLM催化剂具有最好的柱结构保留度,从而表现出最佳的芳构化性能;随着锌含量的增加,Zn/Al-CLM催化剂的酸量增大,从而使丙烷转化率增大,而选择性则是锌含量质量分数为5.8%时具有极大值;400℃活化处理可使Zn与Al-CLM之间具有适中的相互作用,从而使得Zn/Al-CLM具有较高的芳烃收率。 相似文献
77.
Dehydroluciferyl-coenzyme A (L-CoA) was chemically synthesized and characterized by MS, UV-vis spectrometry and RP-HPLC. The identity of the chemically synthesized compound with the one that was produced by firefly luciferase was confirmed. Moreover, the reversibility of the enzymatic conversion of dehydroluciferin ? dehydroluciferyl-adenylate ? L-CoA was also confirmed. The chemical synthesis of L-CoA, described here, may help the clarification of the activator effect of CoA on luciferase bioluminescent assays, in which the enzyme catalyzed formation of L-CoA and the consequent destruction of L-AMP is one of the possible explanations for that effect. 相似文献
78.
Hiléia K. S. Souza V. R. da Silveira F. M. M. Borges Dulce M. A. Melo H. Scatena Jr. O. A. de Oliveira A. G. Souza 《Journal of Thermal Analysis and Calorimetry》2007,87(2):433-436
Thermal behavior of rare earth nitrate complexes
with 2-azacyclononanone (AZA) with Ln(NO3)3·3(AZA)
composition (where Ln=Gd, Er and Ho) was
analyzed in kinetic point of view. Kinetic parameters were calculated from
thermogravimetric data. All obtained results were similar. The first decomposition
step was representative to the loss of ligand and the residue was essentially
Ln2O3. Furthermore, a reaction
path was proposed for the thermal decomposition of the Ln(NO3)3·3(AZA). 相似文献
79.
Detailed spectral simulations based on ab initio density functional theory computations of the amide I and II infrared (IR) and vibrational circular dichroism (VCD) spectra for Ac-(Ala)(4)-NH(2), Ac-(Aib-Ala)(2)-NH(2), and Ac-(Aib)(4)-NH(2) constrained to 3(10)- and alpha-helical conformations are presented. Parameters from these ab initio calculations are transferred onto corresponding larger oligopeptides to simulate the spectra for dodecamers. The differences between conformations and for different Aib substitution patterns within a conformation are reflected in observable spectral patterns where data are available. Simulated IR spectra show small frequency shifts in the amide I maxima between 3(10)- and alpha-helices, but the same magnitude shifts occur within one conformation upon Aib substitution. Thus, from a computational basis, the frequency of the amide I maximum does not discriminate between the 3(10)- or alpha-helical conformations. Calculated VCD band shapes for 3(10)-helices showed more significant changes in amplitude, with change in the fraction of Aib, than those for alpha-helices. Generally, with increasing Aib content, the overall amide I VCD intensity becomes weaker and the amide I couplet becomes more conservative, while the amide II VCD is less affected. Although the detailed band shape is shown to be sensitive to alpha-Me substitution, the basic pattern of amide I and II relative VCD intensities still differs between alpha- and 3(10)-helices and, as a consequence, successfully discriminates between them. These predictions are all borne out in experimental spectra of Aib, mixed Aib-Ala, and Ala-based helical peptides, where available. 相似文献
80.
Study of the behaviour of amino acids in aqueous solution by time-domain NMR and high-resolution NMR
Khallouk M Rutledge DN Silva AM Delgadillo I 《Magnetic resonance in chemistry : MRC》2005,43(4):309-315
The study of protein hydration by time-domain NMR is complicated by the great number of interactions involved, resulting from the presence of several amino acids and the possible modifications produced by the various structures. Moreover, a good comprehension of the molecular interactions of the simple amino acids in solution is essential to elucidate the mechanism of the biological functions of proteins. Measurements of transverse relaxation rates of the protons of water (R(2) = 1/T(2)) in aqueous solutions of amino acids such as L-glycine, L-asparagine, L-arginine and L-tryptophan were carried out in order to study the effects of chemical exchange and molecular diffusion on the amplitude of R(2). The values of R(2) measured by the Carr-Purcell-Meiboom-Gill (CPMG) sequence were studied while varying the solution pH and the parameters of the CPMG sequence. The dependence of R(2) on pH and tau (inter-pulse delay between the first and the second pulses of the CPMG sequence) is interpreted in terms of chemical exchange between the protons of water and those of the labile amino acid groups. This interpretation was confirmed by the analysis of the proton spectra acquired using a 300 MHz NMR spectrometer. 相似文献