Transferable atom equivalent multicentered multipole expansion method

The transferability of atomic and functional group properties is an implicit concept in chemistry. The work presented here describes the use of Transferable Atom Equivalents (TAE) to represent molecular electrostatic potential fields through the use of integrated atomic multipole moments that are associated with each TAE atom type used in the reconstruction. TAE molecular surface distributions of electrostatic potentials are compared with analytical ab initio and empirical (Gasteiger) partial charge reference models for several conformations of test peptides. Surface electrostatic potential distributions computed using TAE multipole representations were found to converge at the octopole level, with incremental improvement observed when hexadecapoles were included. Molecular electrostatic potential fields that were produced using the TAE method were observed to be responsive to conformational changes and to compare well with ab initio reference distributions. Generation of TAE atom types and their associated multipoles does not involve fitting to sample electrostatic potential fields, but rather utilizes integrated AIM atomic electron density distributions within representative chemical environments. The RECON program was used for TAE reconstruction. RECON is capable of processing 5,000 drug-sized molecules or 25 proteins per minute per 1.7 GHz P4 Linux processor.     

Extended Koopmans' theorem ionization potentials for beryllium atom shake-up transitions

The ionization potentials were calculated for Be using the extended Koopmans' theorem (EKT ) using several full configuration interaction (CI ) and multiconfigurational-self-consistent-field (MCSCF ) wave functions as reference wave functions. The wave functions used account for 89.7–96.7% of the correlation energy. Comparisons are made with experimental values and with δCI values calculated as the difference in energy obtained from CI wave functions for Be and Be⁺. The best EKT IP differed from the δCI value by 0.0003 eV for the lowest IP and by 0.0006 eV for ionization into the lowest ²P state of Be⁺. A calculation of ionization into the second ²P state of Be⁺ requires diffuse orbitals that are unimportant in the wave function for the ground state of Be. This results in small natural orbital occupation numbers for natural orbitals needed in the EKT calculation. © 1994 John Wiley & Sons, Inc.     

A study of nuclear prenylation of 2,4-dihydroxy phenyl benzyl ketone: Syntheses of linear and angular 6″,6″-dimethyl pyrano-isoflavones,and their 2-methyl and 2-phenyl analogues

2,4-Dihydroxyphenyl benzyl ketone (I) condenses with 2-methyl but-3-en-2-ol in the presence of boron trifluoride etherate to afford a mixture of 3-C-, 5-C- and 3,5-di C C-prenyl derivatives separable by chromatography. The above mixture without the 5-C-prenyl but with the 4-O-prenyl derivative results when ketone I is treated with prenyl bromide in the presence of methanolic potash. 3-C-(III a) and 5-C-(IV) prenyl derivatives undergo ready oxidative cyclization with DDQ to yield the corresponding pyrano derivatives VIII and XII respectively which form good starting materials for various isoflavone condensations. Thus both linear and angular 6″,6″-dimethyl pyrano-isoflavones and their 2-methyl and 2-phenyl analogues have been synthesized.     

Über die gemeinsame Umsetzung von α-Mercaptoketonen mit Oxoverbindungen und α-Aminocarbonsäureestern

Zusammenfassung Bei der Umsetzung von -Mercaptoketonen mitSchiffschen Basen aus Glykokolläthylester und Oxoverbindungen (Aldehyden, Cyclohexanon) bzw. bei der gemeinsamen Einwirkung derSchiffschen Base-Komponenten Glykokolläthylester und Oxoverbindungen auf -Mercaptoketone entstehen in glatter Reaktion ⁴-Thiazolin-3-yl-essigsäureäthylester.Als cyclische Enamine lassen sich diese ⁴-Thiazoline mit Ameisensäure zu den entsprechenden beständigen Thiazolidinyl-3-essigsäureäthylestern hydrieren.Die ⁴-Thiazolin-3-yl-essigsäureäthylester, die in 2-Stellung monosubstituiert sind, erleiden beim Erhitzen auf etwa 150° Thermolyse, wobei es unter Abspaltung von Essigsäureäthylester zur Bildung von Thiazolen kommt.

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-Mercapto ketones react with aldehydes (or cyclohexanone) and esters of -amino acids (or their hydrochlorides) or with theSchiff bases formed by these compounds to form esters of ⁴-thiazolin-3-ylacetic acids. These esters can be hydrogenated with formic acid to the corresponding thiazolidines.Esters of ⁴-thiazolinylacetic acids which have a H atom in position 2, can be pyrolysed by heating at about 150° to form the corresponding thiazoles and alkyl acetate. These reactions are illustrated for the case of 2-mercaptopentan-3-on as -mercapto ketone, glycinethylester as amine component and various aldehydes or cyclohexanone as oxo compound.

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60. Mitt.:F. Asinger, W. Schäfer, H. Kersten undA. Saus, Mh. Chem.98, 1841 (1967).

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Teil der DiplomarbeitC. Dudeck, Techn. Hochschule Aachen, 1967.     

PHOTOREACTION OF BENZ(A)PYRENE IN SOLUTIONS CONTAINING POLYMER

Abstract— An unusual photo-reaction of benz(a)pyrene has been investigated by measuring prompt and delayed fluorescence spectra. The proposed mechanism involves adsorption of triplet benz(a)pyrene by the polymer and its reaction to give substitution products. Further work is in progress with pyrene, which also undergoes photo-reaction in the presence of polymer.     

Synthesis of substituted carbazoles by a vinylic to aryl palladium migration involving domino C-H activation processes

Substituted carbazoles are readily prepared in good yields by the palladium-catalyzed cross-coupling of alkynes and N-(3-iodophenyl)anilines. This process proceeds by carbopalladation of the alkyne, heteroatom-directed vinylic to aryl palladium migration, and ring closure involving two consecutive C-H activation processes. The process has also been expanded to the synthesis of an indole. [Structure: see text]     

Ab initio stochastic optimization of conformational and many-body degrees of freedom

Moderate to large size molecules in solution have complex energy surfaces due to intramolecular (conformational) and intermolecular (many-body) interactions. The first principles Monte Carlo (FPMC) method, previously shown to effectively locate minimum-energy structures for systems with only many-body complexity, has been extended to address conformational flexibility by adding three new Monte Carlo move types. The primary advantage of the FPMC method is the ability to efficiently locate minimum energy structures of molecules with conformational flexibility in the presence of explicit solvent molecules using highly accurate quantum chemical calculations. The additions to FPMC were validated by studying conformers of glycerol, glyceraldehyde, and a large humic acid monomer unit. The structure of glyceraldehyde in the presence of one and two water molecules was also explored to demonstrate the power of FPMC to study systems with both conformational and many-body degrees of freedom.     

Chemical synthesis of lymphotactin: a glycosylated chemokine with a C-terminal mucin-like domain

The synthesis of a 93-residue chemokine, lymphotactin, containing eight sites of O-linked glycosylation, was achieved using the technique of native chemical ligation. A single GalNAc residue was incorporated at each glycosylation site using standard Fmoc-chemistry to achieve the first total synthesis of a mucin-type glycoprotein. Using this approach quantities of homogeneous material were obtained for structural and functional analysis.     

Simultaneous determination of metal ion concentrations in binary mixtures with a multi-LED photometer

 A compact photometer is based on up to seven different light-emitting diodes whose light is guided into a photometric cell by means of a fibre-optic coupler. The wavelength is selected by switching on the appropriate light source. The application of this multi-wavelength photometer to the determination of binary metal ion samples is demonstrated using model mixtures. Solutions of Fe, Co, Cu, Ni, Cr and Mn were used in combination with several photometric reagents. It was found that the instrument yielded concentration measurements which were usually within a few percent of the correct concentration. These results are comparable to reported data obtained with conventional instruments for similar measurements. The application of the instrument for simultaneous determination in flow-injection analysis employing rapid computer controlled switching of the light-emitting diodes is also demonstrated. A limitation in the use of light-emitting diodes for the simultaneous determination was found to arise from the fact that in some instances non-linear calibration curves are obtained when employing light-emitting diodes as light sources. This occurs when the absorptivity of the measured compound changes over the emission band of the diodes. Multiple regression analysis is then not easily possible. Received: 16 September 1996/Revised: 14 October 1996/Accepted: 16 October 1996