Computational study of the aminolysis of esters. The reaction of methylformate with ammonia

The aminolysis of esters is a basic organic reaction considered as a model for the interaction of carbonyl group with nucleophiles. In the present computational study the different possible mechanistic pathways of the reaction are reinvestigated by applying higher level electronic structure theory, examining the general base catalysis by the nucleophile, and a more comprehensive study the solvent effect. Both the ab initio QCISD/6-31(d,p) method and density functional theory at the B3LYP/6-31G(d) level were employed to calculate the reaction pathways for the simplest model aminolysis reaction between methylformate and ammonia. Solvent effects were assessed by the PCM method. The results show that in the case of noncatalyzed aminolysis the addition/elimination stepwise mechanism involving two transition states and the concerted mechanism have very similar activation energies. However, in the case of catalyzed aminolysis by a second ammonia molecule the stepwise mechanism has a distinctly lower activation energy. All transition states in the catalyzed aminolysis are 10-17 kcal/mol lower than those for the uncatalyzed process.     

Inhomogeneity in Distribution and Conformation of Bovine Serum Albumin in Sol–Gel: A Closer Look with a Near-Infrared Multispectral Imaging Technique

Concentration distributions and conformations of bovine serum albumin (BSA) entrapped in sol–gels were successfully determined for the first time by use of the recently developed NIR multispectral imaging instrument. It was found that BSA molecules were inhomogeneously distributed within the sol–gel matrix, independent of its concentration. At relatively high concentration (366 mg/mL) the encapsulation process does not seem to produce any observable changes in the conformation of BSA. However, when the concentration of BSA was decreased to 220 mg/mL, pronounced changes in the spectra of the protein were observed as a function of (sol–gel reaction) time. The observed inhomogenity might be traced to both a non-uniform concentration distribution of BSA and changes in protein native conformation resulting from interactions between the charged protein and the silicate anions. Results obtained seem to suggest that the protein molecules might adapt themselves to accommodate evolving geometry and sites of the silica network.     

Anyons and the Bose--Fermi Duality in the Finite-Temperature Thirring Model [Erratum]

Corrections to the paper published in Vol. 121, No. 1, October, 1999     

Quantum gauge fields and flat connections in 2-dimensional BF theory

The 2-dimensional BF theory is both a gauge theory and a topological Poisson σ-model corresponding to a linear Poisson bracket. In [3], Torossian discovered a connection which governs correlation functions of the BF theory with sources for the B-field. This connection is flat, and it is a close relative of the KZ connection in the WZW model. In this Letter, we show that flatness of the Torossian connection follows from (properly regularized) quantum equations of motion of the BF theory.     

Experimental and theoretical study on the absorption and fluorescence properties of substituted aryl hydrazones of 1,8-naphthalimide

Absorption and fluorescence spectra in acetonitrile for a series of substituted aryl hydrazones of N-hexyl-1,8-naphthalimide are studied with the aim of potential application of the compounds for enzyme activity localization. The influence of the substituents on the spectral characteristics has been evaluated. The absorption and fluorescence energies of substituted aryl-1,8-naphthalimide hydrazones have been calculated with the PCM TDDFT formalism. The M06 and PBE0 functionals, combined with the 6-31+G(d) atomic basis set, have been found to accurately model the excited state properties of the present set of solvated fluorophores. Absorption and fluorescence spectral characteristics have been rationalized in terms of experimental and theoretical electronic indices in order to assess their predictive abilities for application in designing analogues with good emitting properties. An excellent linear dependence is established between the experimental fluorescence and Hammett σ(p)(+) substituent constants and on the other hand σ(p)(+) constants correlate with the theoretically calculated values for the electrostatic potential at nuclei (EPN). A model for predicting the fluorescence properties of substituted hydrazones by means of EPN is drawn, including the polysubstituted derivatives, where Hammett constants are not applicable.     

Copolymerization of benzoquinone with norbornene

For the first time, the conjugated dicarbonyl compound benzoquinone has been copolymerized with the strained cyclo-olefin norbornene using catalytic amounts of the Friedel-Crafts metathesis catalytic system WOCl₄+AlCl₃. All analyses reveal that the products consist of conjugated blocks originating from benzoquinone connected with spacers originating from norbornene. The products are soluble in benzene, toluene, chlorobenzene, etc. but possess properties of the conjugated polymers. They have been synthesized via a very simple one-pot procedure.     

Correlation between IR-characteristics vibrations and solvent parameters. Koppel-Palm's multiparameter equation

Using the medium's parameters introduced by Koppel and Palm, correlation equations are derived, which describe the solvatochromic shift of the CO and NH stretching vibrations for acetophenone and pyrrole. The statistical properties of the equations are examined using data on a set of 37 solvents and it is proved that the influence of the nonspecific solvation cannot be described as a sum of the terms dependent on the medium's polarity and polarizability.