Third-order RKR procedure

Potential energy curves for the X¹Σ⁺state of ⁶LiH, ⁷LiH and ⁶LiD, ⁷LiD molecules have been calculated by the third-order RKR inversion procedure by including the Kaise correction. The results are in agreement with previously obtained curves by other authors using differents methods. As a check, the exact vibrational eigenfunctions, appropriate to these potentials, are obtained by direct numerical solutions of the radical Schrödinger equation.     

A six-dimensional quadrature procedure

An account is given of the use of Gaussian quadrature product formulae in the evaluation of certain six-dimensional, two-centre integrals involving one-electron Green's functions. These integrals occur in a new molecular variational principle recently proposed by Hall, Hyslop and Rees [1] from which an approximate energy may be derived which can be shown to be at least as good as that obtained from the Rayleigh-Ritz principle. Reductions in computing time are realized by removing certain singularities using a subtraction technique and also by using an empirically determined Richardson-type extrapolation formula.This paper was presented during the session on numerical integration methods for molecules of the 1970 Quantum Theory Conference in Nottingham. It has been revised in the light of the interesting discussion which followed.     

Investigation of a hybrid TCSCF-DFT procedure

In this work a family of hybrid TCSCF-DFT procedures for treating inherently two-configurational species is introduced and applied to the low-lying singlet and triplet states of B₂ and C₂H₄. The hybrid procedures permit self-consistent determination of the orbitals in both the TCSCF and Kohn-Sham subspaces. Received: 15 October 1997 / Accepted: 13 January 1998     

A new procedure for dethioacetalization

A simple procedure has been developed for the conversion ofthioacetals to the corresponding carbonyl compounds using the combination of phenyl dichlorophosphate, dimethylformamide and sodium iodide.     

A rapid iodine radiochemical procedure

A radiochemical procedure was developed to determine fission yields and radiation characteristics of short-lived iodine fission products.Iodine was separated from other fission products of uranium in less than 10 sec after completion of irradiation. High decontamination factors of iodine from Sn, Sb, Te, Xe, Cs and Ba, and high chemical yields were obtained. The sample was prepared by dissolving uranium peroxide in molten periodic acid; the melt was cooled, ground and mixed with activated carbon. After irradiation, the periodic acid was decomposed by heat and the gaseous iodine formed was collected in carbon tetrachloride or in a cooled counting chamber. Higher temperatures could be used than in conventional aqueous systems, thus enhancing the exchange of carrier and fission product iodine.     

A practical procedure of propargylation of aldehydes

An operationally simple procedure of propargylation of aldehydes in moist solvent (distilled THF) has been developed through direct addition of propargyl bromide to aldehyde substrates mediated with low valent iron or tin. The metals were spontaneously prepared in situ employing bimetal redox strategy. Using different aldehydes as substrates (3a-k) both these metal mediated reactions took place producing homopropargyl alcohols (4a-k) in good yields in all cases and with high chemoselectivity in most of the cases (Table 1). Due to its efficacy, operational simplicity, performance in moist solvent, and being comprised of the use of inexpensive metal/metal salts, the procedure is practically viable and potentially scalable.     

Development of a capillary gas chromatographic procedure

A simple and fast capillary gas chromatographic method with flame ionisation detection (FID) has been developed for the analysis of fluoxetine, fluvoxamine, citalopram, sertraline and paroxetine in their pharmaceutical preparations, using clomipramine as internal standard in order to achieve quantification. The reported method is the first screening one that allows the determination of the five selective serotonin reuptake inhibitors by GC, permitting also to avoid prederivatization for the first time and it is even a pioneering work including an extensive analytical validation and robustness treatment on placebo pharmaceutical formulations too. Optimal conditions for the quantitative gas capillary separation were investigated: column head pressure (100 kPa), injector and detector (FID) temperatures (210 and 260 °C), time and temperature for the splitless step (0.80 min and 80 °C, respectively), volume injected (2 μL) and oven temperature program, providing analysis times shorter than 7 min. Aspects such as stability of solutions, linearity, accuracy, precision, detection and quantitation limits are examined on a selected placebo in order to validate this method. Peak purity is assessed using mass-selective detection (DMS). The robustness of this method was evaluated using the Plackett-Burman fractional factorial experimental design with a matrix of 15 experiments and the statistical treatment proposed by Youden and Steinner. The scope of the validated method is proved in the analysis of almost existing pharmaceutical preparations, with recoveries between 98.5% and 102.4% with regard to their nominal contents. Finally, the proposed method could be also a very successfully option for the analysis of these SSRIs in real urine samples introducing a previous solid phase extraction-preconcentration step.     

A procedure for analysis of densitometric spectra

Computer-aided quantitative analysis of densitometric spectra is presented. The densitometric spectra are decomposed into component bands using the Powell and Marquardt minimizers. Several different functions for the component bands are utilized. It is shown that the densitometric spectra can be decomposed into component bands with high accuracy only if the proper shapes of the bands are chosen. The method described was used for quantitative analysis of densitometric spectra of DNA cleaved by neocarzinostatin. The procedure is general and can be applied to analyses of autoradiographic films and to direct scans of electrophoretic gels. It is shown that densitometric spectra which show highly overlapped bands are well approximated by asymmetric Cauchy and Gauss functions. Well separated densitometric bands which have substantial asymmetry can be fitted to more sophisticated shapes formed by combinations of symmetric and asymmetric Cauchy and Gauss functions. High accuracy fitting to asymmetric densitometric curves may only be achieved using the cosine function introduced by Mignot and Rondot, J. Appl. Cryst. 1976, 9,460-465.     

Characteristics and design procedure of hyperbolic dies

Nozzle profiles capable of generating constant extensional strain rates are termed hyperbolic dies. When used in polymer extrusion, they exhibit greater potential in inducing and retaining polymer molecular orientation than conventional capillary dies. Most mathematical expressions found in the literature involve several processing variables in describing and designing such nozzle profiles. This report reveals that a hyperbolic die profile, although rather complicated, can be expressed with equations in terms of two ordinary geometrical parameters—the exit diameter and the hyperbolic length. This finding greatly simplifies the design procedure of hyperbolic dies. The extensional strain rate of a hyperbolic die can be related to the length-to-diameter ratio for any given exit diameter. Examples of various types of die profiles are presented and their constant extensional strain-rate characteristics are discussed.     

Improvement of the super-modified simplex optimization procedure

The performance of the super-modified simplex optimization procedure can be improved substantially. Three modifications of this procedure, involving application of Gaussian fit, weighted reflection point, and estimation of response at the reflection point, are described and tested by means of computer simulation. Combined application of the first two modifications leads to an improvement of about 30% in the number of required experiments, and of 56–73% in the variance of this number. Improvements are achieved in 98% of the cases studied.     

A procedure for “iodolactamization”

Treatment of an unsaturated amide with TMS-OTf, then iodine in THF gives the iodolactam.     

A procedure for filling calixarene nanotubes

Alkyl nitrites readily transfer nitrosonium into calixarene-based synthetic nanotubes thus offering a mild, effective and precise method to fill them.     

Improved oxidation procedure with aromatic peroxyacids

The application of the $\text{m}$-Chloroperbenzoic acid-potassium fluoride system in the Baeyer-Villiger oxidation of aromatic aldehydes and in the epoxidation of olefins has been studied.     

A rapid radiochemical procedure for indium

A rapid radiochcmical procedure was developed for the separation of indium radionuclides from a mixed fission-product solution. An alcoholic pyridine solution is added to a uranium solution containing indium and tin carriers. The resulting tin precipitate is separated from the indium-containing solution by filtering through a cellulose membrane filter. The decontamination factor for tin is 2·10³. Other fission products are only partially removed. The chemical yield of indium is about 44%, and the time required for the separation is about 10 sec. After the tin-separated indium has decayed, the tin daughters of indium are removed from all the other fission products at a specified time and measured, so that the amount of indium present at the time of the tin precipitation is determined.     

A rapid radioimmunoassay procedure for thyroxin

A sensitive thyroxin /T₄/ radioimmunoassay procedure with a short incubation time /10 min/ similar to a conventional stat test in clinical chemistry is described. The assay parameters such as concentration of antisera and¹²⁵I-T₄, and incubation temperature that affect the kinetics of antigen-antibody reaction have been studied. Within- and between-assay variations were less than 7% CV. Analysis of 45 serum samples by the proposed method and by a conventional assay gave similar results /Y=1.05X–0.187; r=0.990/.     

Calibration procedure for gel permeation chromatography

A novel procedure is presented for calibrating a gel permeation chromatograph by using broad polymer fractions. The limit in accuracy is set by the accuracy of number-average and weight-average molecular weight measurements and the reproducibility of the chromatograph. In the particular calibration for linear polyethylene described here, low molecular weight fractions were prepared by nitric acid oxidation of annealed single crystals. The calibration is then of particular value in morphological studies of polyethylene. The influence in the calibration of polar endgroups on the polymer, as produced in these oxidized samples is discussed.     

A sorption-catalytic procedure for determining histamine

It has been found that histamine acts as an inhibitor in the reaction of hydroquinone peroxidation catalyzed by Cu(II), when it is carried out in a solution, and as an activator, when this reaction is carried out on paper carriers. A supposition on the reasons for the inhibiting and activating effects has been made on the basis of the theory of the intermediate active complex. A procedure for the determination of (3−9) × 10⁻¹³ M histamine using copper-containing paper filters with chemically attached hexamethylenediamine groups has been developed. The strongest interference with the determination of histamine is observed for diethylamine and triethylamine. The procedure has been used for the sorption-catalytic determination of histamine in human saliva at the nM level.     

Orbital deletion procedure and its applications

The orbital deletion procedure is introduced, which is suited to quantitatively investigating the electronic delocalization effiect in earboeations and boranes. While the routine, ab initio molecular orbital methods can generate wavefunetions for real systems where all electrons are delocalized, the present orbital deletion procedure can generate wavefunctions for hypothetical reference molecules where electronic delocalization effect is deactivated. The latter wavefunetion normlly corresponds In the most stable resonance structure in terms of the resonance theory. By comparing and analyzing the delocalized and the localized wavefunetions, one can obtain a quantitative and instinct pieture to show how electronic deloealizalion inside a molecule affects the molecular structure, energy as well as other physical properties. Two examples are detailedly discussed. The first is related to the hypercoujugation of alkyl groups in carbocations and a comparison of the order of stability of carbocations is made, T     

Multicanonical procedure for continuum peptide models

The multicanonical (Muca) Monte Carlo method enables simulating a system over a wide range of temperatures and thus has become an efficient tool for studying spin glasses, first‐order phase transitions, the helix–coil transition of polypeptides, and protein folding. However, implementation of the method requires calculating the multicanonical weights by an iterative procedure that is not straightforward and is a stumbling block for newcomers. A recursive procedure that takes into account the statistical errors of all previous iterations and thus enables an automatic calculation of the weights without the need for human intervention after each iteration has been proposed. This procedure, which has already been tested successfully for lattice systems, is extended here to continuum models of peptides and proteins. The method is examined in detail and tested for models of the pentapeptide Leu‐enkephalin (Tyr‐Gly‐Gly‐Phe‐Leu) described by the potential energy function ECEPP. Because of the great interest in the structural mapping of the low‐energy region of biomolecules, the energy of structures selected from the Muca trajectory is minimized. The extent of conformational coverage provided by the method is examined and found to be very satisfactory. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 1251–1261, 2000