IR spectra simulation as auxiliary tool for gas chromatography/Fourier transform IR spectroscopy/mass spectrometry identification of unknown compounds. 2. PM3, AM1, MNDO and MINDO3 simulations for simple nitriles

A set of the semi-empirical methods (PM3, AM1, MNDO and MINDO3) supplied by the HyperChem™ package has been tested to find the best auxiliary tool for the gas chromatography/Fourier transform IR spectroscopy/mass spectrometry identification of nitriles, taking 23 relatively simple nitriles as test compounds. Of the four methods, MNDO can be considered as the most advantageous since: (1) for 17 compounds of 23 tested, the IR spectra simulated by this method best match the experimental spectra (and in additional 3 cases, the results are as good as those obtained by AM1 method); (2) within the range of experimental wavenumbers of 900–3100 cm⁻¹, MNDO provides the best linearity between the calculated and experimental values (with a correlation coefficient of 0.989). A scaling factor of 0.85 can be used to afford better correspondence between the calculated and experimental wavenumbers. A disadvantage of the MINDO simulations is underestimation of ν_CN (and sometimes ν_CH) band intensities.     

Michael additions to trifluoromethylvinyl sulfone

Michael addition reactions of trifluoromethyl vinyl sulfone with organic compounds with labile hydrogen atoms are studied. Such additions can be successfully accomplished using potassium fluoride and 18-crown-6-ether or benzyltrimethylammonium hydroxide (Triton B) as catalysts.     

Medium-size polarized basis sets for high-level-correlated calculations of molecular electric properties

Summary The first-order polarized basis sets for the use in high-level-correlated investigations of molecular electric properties have been generated for Pb, Bi, Po, and At. The performance of the standard [10.17.14.5/13.11.8.2] and extended [20.17.14.9/13.11.8.4] basis sets has been examined in nonrelativistic and quasirelativistic calculations for atoms and simple closed-shell hydrides. The relativistic contributions to electric dipole properties of those systems have been evaluated by using the recently developed quasirelativistic scheme. The predicted dipole polarizability of At is in good agreement with the results of other relativistic calculations. The calculated quasirelativistic dipole moments of BiH₃ (–0.499 a.u.), PoH₂ (–0.207 a.u.), and AtH (+0.036 a.u.) involve a significant relativistic contribution which amounts to —0.230 a.u., –0.177 a.u., and –0.097 a.u., respectively. The basis set details append this paper. They are also available as a part of the basis set library of the MOLCAS system.     

Artificial neural network modification of simulation-based fitting: application to a protein-lipid system

Simulation-based fitting has been applied to data analysis and parameter determination of complex experimental systems in many areas of chemistry and biophysics. However, this method is limited because of the time costs of the calculations. In this paper it is proposed to approximate and substitute a simulation model by an artificial neural network during the fitting procedure. Such a substitution significantly speeds up the parameter determination. This approach is tested on a model of fluorescence resonance energy transfer (FRET) within a system of site-directed fluorescence labeled M13 major coat protein mutants incorporated into a lipid bilayer. It is demonstrated that in our case the application of a trained artificial neural network for the substitution of the simulation model results in a significant gain in computing time by a factor of 5 x 10(4). Moreover, an artificial neural network produces a smooth approximation of the noisy results of a stochastic simulation.     

Solubility Behavior in Ternary Water-Salt Systems under Sub- and Supercritical Conditions

Summary.  Two main types of binary systems with distinctive solubility behavior under sub- and supercritical conditions were used to subdivide ternary water-salt systems into three classes. Characteristic features of solubility behavior and phase equilibria in ternary water-salt systems of each class at temperatures above 200°C are discussed on the basis of available experimental data and some conclusions obtained as a result of theoretical derivation of fluid and complete phase diagrams. Corresponding author. E-mail: Valyashko@IGIC.RAS.RU Received September 25, 2002; accepted (revised) November 28, 2002 Published online April 24, 2003 RID="a" ID="a" Dedicated to Prof. Dr. H. Gamsjaeger on the occasion of his 70^th birthday anniversary     

Structural analysis of phosphatidylcholines by post-source decay matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

The utility of post-source decay (PSD) matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) was investigated for the structural analysis of phosphatidylcholine (PC). PC did not produce detectable negative molecular ion from MALDI, but positive ions were observed as both [PC+H](+) and [PC+Na](+). The PSD spectra of the protonated PC species contained only one fragment corresponding to the head group (m/z 184), while the sodiated precursors produced many fragment ions, including those derived from the loss of fatty acids. The loss of fatty acid from the C-1 position (sn-1) of the glycerol backbone was favored over the loss of fatty acid from the C-2 position (sn-2). Ions emanating from the fragmentation of the head group (phosphocholine) included [PC+Na-59](+), [PC+Na-183](+) and [PC+Na-205](+), which corresponded to the loss of trimethylamine (TMA), non-sodiated choline phosphate and sodiated choline phosphate, respectively. Other fragments reflecting the structure of the head group were observed at m/z 183, 146 and 86. The difference in the fragmentation patterns for the PSD of [PC+Na](+) compared to [PC+H](+) is attributed to difference in the binding of Na(+) and H(+). While the proton binds to a negatively charged oxygen of the phosphate group, the sodium ion can be associated with several regions of the PC molecule. Hence, in the sodiated PC, intermolecular interaction of the negatively charged oxygen of the phosphate group, along with sodium association at multiple sites, can lead to a complex and characteristic ion fragmentation pattern. The preferential loss of sn-1 fatty acid group could be explained by the formation of an energetically favorable six-member ring intermediate, as apposed to the five-member ring intermediate formed prior to the loss of sn-2 fatty acid group.     

Direct decompositions of Artinian modules over hypercyclic groups

Let G be a hypercyclic group and A be an Artianian G-module. A class of simple G-modules is defined and it is proved that there exists a direct decomposition A=C B, where C is a G-submodule, each G-composition factor of which belongs to the class , and B is a G-submodule that does not have G-composition factors belonging to .Deceased.Translated from Ukrainskii Matematicheskii Zhurnal, Vol. 43, Nos. 7 and 8, pp. 930–934, July–August, 1991.     

Principal part of resolvent and factorization of an increasing nonanalytic operator-function

Let a selfadjoint operator-valued functionL() be given on the interval [a,b] such thatL(a)0,L(b)0,L()0 (ab), andL() has a certain smoothness (for instance, it satisfies Hölder's condition). It turns out that the spectral theory of the operator-valued functionL() can be reduced to the spectral theory of one operatorZ, the spectrum of which lies on (a, b) and which is similar to a selfadjoint operator. In particular, the factorization takes place:L()=M()(I–Z), where the operator-valued functionM() is invertible on [a, b]. Earlier similar results were known only for analytic operator-valued functions. The authors had to use new methods for the proof of the described theorem. The key moment is the decomposition ofL ^–1() into the sume of its principal and regular parts.     

Photon-deuteron diffractive scattering

One expects a similarity of the energy dependence of the difference _tot(*p)– _tot(*n) for virtual (deep inelastic scatteringQ ²m ²) and real (Q ²=0) photons. Previous analysis of D structure functions with allowence for nuclear shadowing (NS) in the deuteron has led to conclusion that _tot(*p)– _tot(*n)<0>x<0.015. the=" early=" evidence=" from=" the=" real=" photoproduction=" data="> _tot(p)– _tot(n)<0. we=" critically=" reexamine=" determinations=" of=" the="> _tot(p)– _tot(n), using more accurate calculations of NS correction to _tot(D), and discuss a possibility of _tot(n) _tot(p) at moderately high energies.     

Observation of the decaya 2 − (1320)→π − η′

The reaction ^– C ^– C has been studied at 36 GeV/c. A clear signal for the decaya ₂ ^– (1320) ^– · is observed in the ^– mass spectrum. The measured ratio of branchings is BR (a ₂ ^{– –} )/BR(a ₂ ^{– –} );(3.4±0.8±0.5)·10^–2.