Slater orbital molecular integrals with numerical fourier transform methods. I. (coplanar) multicenter exchange integrals over 1s orbitals

Slater orbital r₁₂^?1 integrals are calculated with a numerical Fourier-transform method based on a formulation first given by Bonham, Peacher and Cox. Spherical wave expansions are introduced that decouple the Feynman integrations for the charge distribution Fourier transforms. The Feynman integrals are evaluated semianalytically, and their properties are analyzed in detail. The final computational step involves a numerical integration over charge distribution quantities. Results for (coplanar) multicenter exchange integrals over 1s orbitals are given. As long as the charge distributions are overlapping considerably, the method gives good results, even when these distributions are highly asymmetric. The method as presently implemented fails when highly disconnected charge distributions are involved.     

Power algebras and generalized quotient algebras

The notion of a good quotient relation has been introduced as an attempt to generalize the notion of a quotient algebra to relations on an algebra which are not necessarily congruences. In order to make it possible to prove generalized versions of 'power isomorphism theorems', the more restrictive notions of very good, Hoare good and Smyth good relation have been introduced. In this paper we describe the relationships between Hoare good, Smyth good and very good relations. As a consequence, we prove that every structure preserving relation on an algebra is very good. Received September 25, 1998; accepted in final form January 14, 1999.     

Numerical calculation and experimental measurement of temperatures and welding residual stresses in a thick-walled T-joint structure

Journal of Thermal Analysis and Calorimetry - In this investigation, a T-joint numerical welding simulation of thick steel plates is performed to estimate transient temperature distributions,...     

Extraction of multiple pure component H and C NMR spectra from two mixtures: Novel solution obtained by sparse component analysis-based blind decomposition

Sparse component analysis (SCA) is demonstrated for blind extraction of three pure component spectra from only two measured mixed spectra in ¹³C and ¹H nuclear magnetic resonance (NMR) spectroscopy. This appears to be the first time to report such results and that is the first novelty of the paper. Presented concept is general and directly applicable to experimental scenarios that possibly would require use of more than two mixtures. However, it is important to emphasize that number of required mixtures is always less than number of components present in these mixtures. The second novelty is formulation of blind NMR spectra decomposition exploiting sparseness of the pure components in the wavelet basis defined by either Morlet or Mexican hat wavelet. This enabled accurate estimation of the concentration matrix and number of pure components by means of data clustering algorithm and pure components spectra by means of linear programming with constraints from both ¹H and ¹³C NMR experimental data. The third novelty is capability of proposed method to estimate number of pure components in demanding underdetermined blind source separation (uBSS) scenario. This is in contrast to majority of the BSS algorithms that assume this information to be known in advance. Presented results are important for the NMR spectroscopy-associated data analysis in pharmaceutical industry, medicine diagnostics and natural products research.     

Lah numbers and Lindström's lemma

We provide a combinatorial interpretation of Lah numbers by means of planar networks. Henceforth, as a consequence of Lindström's lemma, we conclude that the related Lah matrix possesses a remarkable property of total non-negativity.     

Temperature effect on optical properties of the cuticle of Lucilia sericata

Optical properties of the spinal cuticle taken from the species of Lucilia sericata are studied by the reflectance measurements and their structural properties by scanning electron microscopy. The multilayer structure of the cuticle has been confirmed from the scanning electron micrographs. The temperature sensitivity of the multilayer structure is documented by the modification of optical properties in a heating process. The heating process and the local heating using the focused laser beam causes the local changes of the optical properties what is finally demonstrated by the structural color shift of the reflected spectra.     

Characterization and Transport Properties of Surfactant-Templated Silica Layers for Membrane Applications

An intermediate surfactant-templated silica (STS) layer is applied between the supporting mesoporous γ-Al₂O₃ and the amorphous microporous silica overlayer resulting in dual-layered microporous silica membranes for gas separation applications that show improved values for both hydrogen flux and selectivity. Determination of thickness and porosity of as-deposited membrane layers by spectroscopic ellipsometry reveals that the STS layer is present as a distinctive layer of ～20 nm thickness, with penetration up to a depth of ～70 nm into the underlying γ-Al₂O₃support layer, whose thickness and porosity are determined to be 1.3 μm and 50%, respectively.     

Solvolysis of 1,1-dimethyl-4-alkenyl chlorides: evidence for pi-participation

Tertiary 1,1-dimethyl-4-alkenyl chloride (1) solvolyzes with significantly reduced secondary beta-deuterium kinetic isotope effect (substrate with two trideuteromethyl groups) and has a lower entropy and enthalpy of activation than the referent saturated analogue 4 (k(H)/k(D) = 1.30 +/- 0.03 vs k(H)/k(D) = 1.79 +/- 0.01; Delta Delta H(++) = -9 kJ mol(-1), Delta Delta S(++) = -36 J mol(-1) K(-1), in 80% v/v aqueous ethanol), indicating participation of the double bond in the rate-determining step. Transition structure 1-TS computed at the MP2(fc)/6-31G(d) level of theory revealed that the reaction proceeds through a late transition state with considerably pronounced double bond participation and a substantially cleaved C-Cl bond. The doubly unsaturated compound 3 (1,1-dimethyl-4,8-alkadienyl chloride) solvolyzes with further reduction of the isotope effect, and a drastically lower entropy of activation (k(H)/k(D) = 1.14 +/- 0.01; DeltaS(++) = -152 +/- 12 J mol(-1) K(-1), in 80% v/v aqueous ethanol), suggesting that the solvolysis of 3 proceeds by way of extended pi-participation, i.e., the assistance of both double bonds in the rate-determining step.     

Microdialysate analysis of monoamine neurotransmitters—A versatile and sensitive LC–MS/MS method

We have developed and validated a sensitive method for the simultaneous determination of some monoamine neurotransmitters like dopamine (DA), norepinephrine (NE) and serotonin (5-HT) in rat brain microdialysate using high-performance liquid chromatography coupled to tandem mass spectrometry (LC/MS/MS). Sensitivity enhancement has been achieved by amine derivatization with the reagent (5-N-succinimidoxy-5-oxopentyl)triphenylphosphonium bromide (SPTPP) under mild conditions. The use of the selected reaction monitoring (SRM) mode has allowed detection of the analytes at a concentration of 30 pM (lower limit of quantification, LLOQ, signal-to-noise ratio higher than 5) with an accuracy of ≤3.80% and a precision of ±7.39 (%CV) for all neurotransmitters. Derivatization improves resolution and chromatographic retention times (3 min) by lipophilization. Linearity has been good (R > 0.99) over a large concentration range (30–50,000 pM). The intra and inter-batch accuracy and precision were not greater than 4.8% and 6.4%, respectively. Therefore, the method was successfully applied for monitoring the concentration changes of neurotransmitters in microdialysis samples deriving from striatum rat brain region after amphetamine administration (3 mg kg⁻¹, i.p.).     

HPLC Separation of Fluorescent Products of Lipid Peroxidation in Erythrocytes and Mitochondria

Polyunsaturated fatty acids found in membrane phospholipids are readily oxidized by free radicals producing highly reactive aldehydes such as malondialdehyde. These aldehydes react with biological material to form fluorescent lipid peroxidation end products known as lipofuscin-like pigments. We studied fluorescent pigments from beef heart mitochondria incubated with malondialdehyde in vitro and from erythrocytes of patients with Alzheimer’s disease to evaluate their potential as markers of oxidative stress and to develop HPLC methods for their qualitative analysis. We used tridimensional fluorescence spectral arrays and synchronous fluorescence spectra in connection with HPLC separation with fluorescence detection. Stable fluorophores were found in both models and were successfully resolved into several distinctive fractions. This creates the basis for further characterization of this relatively less studied group of products of oxidative damage.