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21.
Analytical properties of hydrogen-like atomic orbitals (HAO ) that are used in the MOLCAO approach to the quantum theory of molecules have been studied. Addition and expansion theorems for HAO have been proved, both in coordinate and momentum representations. A close relation has been established between HAO and the reduced Bessel functions of half-integer indices. New methods are suggested to calculate integrals for atomic and molecular form factors, and multicenter integrals, for the HAO basis in the MO LCAO theory. 相似文献
22.
A simple and sensitive field detection and spectrophotometric method for determination of copper described herewith is based on the formation of a red coloured species of copper(II) with 1-[pyridyl-(2)-azo]-naphthol-(2) (PAN), TX-100 and N,N'-diphenylbenzamidine (DPBA) at pH range 7.8-9.4. The red coloured Cu(II)-PAN-(TX-100)-DPBA complex in chloroform shows maximum absorbance at 520 nm with molar absorptivity value of 1.14x10(5) l mol(-1) cm(-1). The detection limit of the method is 2 ng ml(-1) organic phase. The system obeys Beer's law up to 0.6 mug Cu(II) ml(-1) in organic solution. Most of the common metal ions generally found associated with copper do not interfere. The repeatability of the method was checked by finding relative standard deviation (RSD) (n=10) value for solutions each containing 0.2 mug ml(-1) of Cu(II) and the RSD value of the method was found to be 1.5%. The validity of the method has been satisfactorily examined for the determination of copper in soil and airborne dust particulate samples. 相似文献
23.
Novel anionic dinuclear mixed-ligand peroxo complexes of the type [(UO2)2(O2)3L(H2O)2]3− (L = Histidinate, aspartate, salicylate, Imidazolate and glutamate) have been synthesized from the interaction of uranyl ion (UO22+) with peroxide (O22−) in the presence of the respective coligand (L) at pH 9–10. The sparingly soluble complexes were characterized by elemental analyses, FT-IR, laser Raman (LR) and UV-vis spectroscopy and solution electrical conductance measurements. Based on these studies, a double bridged dinuclear structure involving one peroxo and the mixed ligand L (via-COO−) has been tentatively proposed. Infra-red coupled with LR spectra evidenced structurally different metal bound peroxides (ν2 and σ:σ). An aqueous solution of the salicylate and aspartate complexes have been shown to convert triphenylphosphine (PPh3), cyclohexene, styrene and SO2 to the corresponding OPPh3, 1,2 cyclohexanediol, phenylethyleneglycol and SO42−, respectively. 相似文献
24.
Caignan GA Deshmukh R Wilks A Zeng Y Huang HW Moënne-Loccoz P Bunce RA Eastman MA Rivera M 《Journal of the American Chemical Society》2002,124(50):14879-14892
The origin of the unusual regioselectivity of heme oxygenation, i.e. the oxidation of heme to delta-biliverdin (70%) and beta-biliverdin (30%), that is exhibited by heme oxygenase from Pseudomonas aeruginosa (pa-HO) has been studied by (1)H NMR, (13)C NMR, and resonance Raman spectroscopies. Whereas resonance Raman indicates that the heme-iron ligation in pa-HO is homologous to that observed in previously studied alpha-hydroxylating heme oxygenases, the NMR spectroscopic studies suggest that the heme in this enzyme is seated in a manner that is distinct from that observed for all other alpha-hydroxylating heme oxygenase enzymes for which a structure is known. In pa-HO, the heme is rotated in-plane approximately 110 degrees, so the delta-meso-carbon of the major orientational isomer is located within the HO-fold in the place where the alpha-hydroxylating enzymes typically place the alpha-meso-carbon. The unusual heme seating displayed by pa-HO places the heme propionates so that these groups point in the direction of the solvent-exposed heme edge and appears to originate in large part from the absence of stabilizing interactions between the polypeptide and the heme propionates, which are typically found in alpha-hydroxylating heme oxygenase enzymes. These interactions typically involve Lys-16 and Tyr-112, in Neisseriae meningitidis HO, and Lys-16 and Tyr-134, in human and rat HO-1. The corresponding residues in pa-HO are Asn-19 and Phe-117, respectively. In agreement with this hypothesis, we found that the Asn-19 Lys/Phe-117 Tyr double mutant of pa-HO exists as a mixture of molecules exhibiting two distinct heme seatings; one seating is identical to that exhibited by wild-type pa-HO, whereas the alternative seating is very similar to that typical of alpha-hydroxylating heme oxygenase enzymes and is related to the wild-type seating by approximately 110 degrees in-plane rotation of the heme. Furthermore, each of these heme seatings in the pa-HO double mutant gives rise to a subset of two heme isomeric orientations that are related to each other by 180 degrees rotation about the alpha-gamma-meso-axis. The coexistence of these molecules in solution, in the proportions suggested by the corresponding area under the peaks in the (1)H NMR spectrum, explains the unusual regioselectivity of heme oxygenation observed with the double mutant, which we found produces alpha- (55%), delta- (35%), and beta-biliverdin (10%). Alpha-biliverdin is obtained by oxidation of the heme seated similar to that of alpha-hydroxylating enzymes, whereas beta- and delta-biliverdin are formed from the oxidation of heme seated as in wild-type pa-HO. 相似文献
25.
M. Patri Varsha R. Hande Swati Phadnis B. Somaiah Suhasini Roychoudhury P. C. Deb 《先进技术聚合物》2004,15(5):270-274
A Novel solid polymer electrolyte (SPE) membrane containing both ? COOH and ? SO3H group has been prepared by simultaneous method of radiation grafting of acrylic acid onto FEP followed by sulfonation. The presence of weakly acidic acrylic acid controls the swelling in water while ? SO3H group provides conductivity due to its strongly ionic characteristic. FEP‐g‐acrylic acid and its sulfonated derivatives were characterized by their properties. While the mechanical properties decreased, other properties such as ion exchange capacity (IEC), water uptake and ionic conductivity increased with increase in graft content. These properties further changed on sulfonation. Acrylic acid being weakly acidic in nature, conductivity values of the grafted membrane were quite low. However, introduction of strong ? SO3H group resulted in conductivity closer to Nafion 117. Few sulfonated membranes have been tested with respect to H2/O2 fuel cell performance. Short‐term fuel cell test for 100 hr gave a stable performance. These membranes are less expensive compared to Nafion. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
26.
The feasibility of DNA microarray sensor technology as a routine technique of molecular pharmacology to perform high throughput drug screening and the advantages of directly labeled RNA for a high throughput experiment are presented in this paper. A novel, single-step direct chemical labeling method for DNA microarray target samples has been developed to reduce the sample amount, cost, time and error of the experiment by eliminating the need for enzyme mediated labeling. Reproducibility of the data for high throughput drug screening is demonstrated by monitoring differential gene expression of a set of 45 gene targets involved in the genotoxic stress response pathways. 相似文献
27.
Hussain SA Deb S Biswas S Bhattacharjee D 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(11-12):2448-2454
This communication reports the surface pressure (pi) versus area per molecule (A) isotherm characteristics of the mixed films of 9-phenyl anthracene (PA) in stearic acid (SA) and polymethyl methacrylate (PMMA) matrices, at the air-water interface. The mixed Langmuir films at the air-water interface have been observed to be easily transferred onto solid substrates to form uniform Langmuir-Blodgett films. By changing various parameters, namely molefraction, surface pressure of lifting and number of layers, the mixed Langmuir-Blodgett (LB) films of various types have been fabricated successfully and their spectroscopic characteristics have been reported. From the isotherm characteristics and the area per molecule versus molefraction plot, it is evident that the PA molecules are successfully incorporated into mixed Langmuir-Blodgett films. UV-vis absorption spectroscopic study of the mixed LB films at various molefractions of PA in two different matrices reveal that formation of I-type aggregate in PMMA matrix whereas both I- and H-type aggregates are playing their dominant role in SA matrix. Moreover, fluorescence spectroscopic study reveals reabsorption effect. Molecular movement persists in the freshly prepared LB films, as is evident from the time dependent changes in both UV-vis absorption and fluorescence spectra of the mixed LB films in both matrices. From our observation it is evident that about 200 h is required to get the LB films in a stable condition. Dimers and higher order n-mers are formed at a higher surface pressure of 30 mNm(-1). 相似文献
28.
Subir Ghosh Sanpei Kageyama Rahul Mukerjee 《Annals of the Institute of Statistical Mathematics》1992,44(3):593-603
In this paper the problem of finding the design efficiency is considered when a single observation is unavailable in a connected binary block design. The explicit expression of efficiency is found for the resulting design when the original design is a balanced incomplete block design or a group divisible, singular or semiregular or regular with 1>0, design. The efficiency does not depend on the position of the unavailable observation. For a regular group divisible design with 1>0, the efficiency depends on the position of the unavailable observation. The bounds, both lower and upper, on the efficiency are given in this situation. The efficiencies of designs resulting from a balanced incomplete block design and a group divisible design are in fact high when a single observation is unavailable.The work of the first author is sponsored by the Air Force Office of Scientific Research under Grant AFOSR-90-0092.On leave from Indian Statistical Institute, Calcutta, India. The work of the third author was supported by a grant from the CMDS, Indian Institute of Management, Calcutta. 相似文献
29.
Rahul Mukerjee 《The Journal of the Operational Research Society》1982,33(10):957-959
The problem of minimising E(X) subject to the constraints X ? 0, P(X ? b) ? a(0 < a < 1) has been considered, where b is a non-negative random variable with continuous probability distribution. A necessary and sufficient condition for randomised decisions to be superior to the non-randomised one has been derived. 相似文献
30.
Thermal noise in Hg0.795Cd0.205Te detectors is estimated for large biasing fields at a lattice temperature of 77 K, by computing the correlation functions of the velocity fluctuations with the Monte Carlo technique. The noise temperature for current components transverse to the field is almost independent of the field, but that corresponding to the parallel component increases by a factor of about 1.3 at 50 V/cm and by a factor of 3.0 at 300V/cm. The thermal noise voltage for a detector of 85 resistance increases from 0.6nV/Hz1/2 at low biasing fields to about 3nV/Hz1/2 at a field of 300 V/cm. The noise power is also found to remain constant up to about 75 GHz, and it decreases thereafter by a factor of 0.25 for doubling of the frequency. 相似文献