Electronic structure of 4H-pyrido[1,2-a]pyrimidin-4-ones

The characteristic features of ir and uv spectra of 43 4H-pyrido[1,2-a]pyrimidin-4-one derivatives with electron donor or acceptor groups in position 3, and positions 6, 7, 8, or 9, respectively, have been systematically studied. On the basis of the spectra some conclusions have been drawn for the molecular structure. The negative solvent effect of the lowest-energy π → π* transition is investigated by the PPP method.     

Generalized stability of the Cauchy and the Jensen functional equations on spheres

We study a generalized stability problem for Cauchy and Jensen functional equations satisfied for all pairs of vectors x,y from a linear space such that γ(x)=γ(y) or γ(x+y)=γ(x−y) with a given function γ.     

Basis property of eigenfunctions of nonselfadjoint operator pencils generated by the equation of nonhomogeneous damped string

We consider a class of nonselfadjoint quadratic operator pencils generated by the equation, which governs the vibrations of a string with nonconstant bounded density subject to viscous damping with a nonconstant damping coefficient. These pencils depend on a complex parameterh, which enters the boundary conditions. Depending on the values ofh, the eigenvalues of the above pencils may describe the resonances in the scattering of elastic waves on an infinite string or the eingenmodes of a finite string. We obtain the 7asymptotic representations for these eigenvalues. Assuming that the proper multiplicity of each eigenvalue is equal to one, we prove that the eigenfunctions of these pencils form Riesz bases in the weightedL ²-space, whose weight function is exactly the density of the string. The general case of multiple eigenvalues will be treated in another paper, based on the results of the present work.     

Asymptotic analysis of nonselfadjoint operators generated by coupled Euler‐Bernoulli and Timoshenko beam model

In the current paper, we present a series of results on the asymptotic and spectral analysis of coupled Euler‐Bernoulli and Timoshenko beam model. The model is well‐known in the different branches of the engineering sciences, such as in mechanical and civil engineering (in modelling of responses of the suspended bridges to a strong wind), in aeronautical engineering (in predicting and suppressing flutter in aircraft wings, tails, and control surfaces), in engineering and practical aspects of the computer science (in suppressing bending‐torsional flutter of a new generation of hard disk drives, which is expected to pack high track densities (20,000+TPI) and rotate at very high speeds (25,000+RPM)), in medical science (in bio mechanical modelling of bloodcarrying vessels in the body, which are elastic and collapsible). The aforementioned mathematical model is governed by a system of two coupled differential equations and a two parameter family of boundary conditions representing the action of the self‐straining actuators. This linear hyperbolic system is equivalent to a single operator evolution equation in the energy space. That equation defines a semigroup of bounded operators and a dynamics generator of the semigroup is our main object of interest. We formulate and proof the following results: (a) the dynamics generator is a nonselfadjoint operator with compact resolvent from the class ??p with p > 1; (b) precise spectral asymptotics for the two‐branch discrete spectrum; (c) a nonselfadjoint operator, which is the inverse of the dynamics generator, is a finite‐rank perturbation of a selfadjoint operator. The latter fact is crucial for the proof that the root vectors of the dynamics generator form a complete and minimal set. In our forthcoming paper, we will use the spectral results to prove that the dynamics generator is Riesz spectral, which will allow us to solve several boundary and distributed controllability problems via the spectral decomposition method. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Asymmetric [3+2] Photocycloadditions of Cyclopropanes with Alkenes or Alkynes through Visible‐Light Excitation of Catalyst‐Bound Substrates

The herein reported visible‐light‐activated catalytic asymmetric [3+2] photocycloadditions between cyclopropanes and alkenes or alkynes provide access to chiral cyclopentanes and cyclopentenes, respectively, in 63–99 % yields and with excellent enantioselectivities of up to >99 % ee. The reactions are catalyzed by a single bis‐cyclometalated chiral‐at‐metal rhodium complex (2–8 mol %) which after coordination to the cyclopropane generates the visible‐light‐absorbing complex, lowers the reduction potential of the cyclopropane, and provides the asymmetric induction and overall stereocontrol. Enabled by a mild single‐electron‐transfer reduction of directly photoexcited catalyst/substrate complexes, the presented transformations expand the scope of catalytic asymmetric photocycloadditions to simple mono‐acceptor‐substituted cyclopropanes affording previously inaccessible chiral cyclopentane and cyclopentene derivatives.     

Nonselfadjoint operators generated by the equation of a nonhomogeneous damped string

We consider a one-dimensional wave equation, which governs the vibrations of a damped string with spatially nonhomogeneous density and damping coefficients. We introduce a family of boundary conditions depending on a complex parameter . Corresponding to different values of , the problem describes either vibrations of a finite string or propagation of elastic waves on an infinite string. Our main object of interest is the family of non-selfadjoint operators in the energy space of two-component initial data. These operators are the generators of the dynamical semigroups corresponding to the above boundary-value problems. We show that the operators are dissipative, simple, maximal operators, which differ from each other by rank-one perturbations. We also prove that the operator coincides with the generator of the Lax-Phillips semigroup, which plays an important role in the aforementioned scattering problem. The results of this work are applied in our two forthcoming papers both to the proof of the Riesz basis property of the eigenvectors and associated vectors of the operators and to establishing the exact and approximate controllability of the system governed by the damped wave equation.

     

Amperometric Glucose Determination by Means of Glucose Oxidase Immobilized on a Cellulose Acetate Film: Dependence on the Immobilization Procedures

Glucose microelectrodes were prepared by immobilizing glucose oxidase onto a cellulose acetate film coating a platinum wire. Hexamethylenediamine (HMDA) and Glutaraldehyde (GA) were employed as spacer and coupling agent, respectively. Sensitivities and linear response ranges were studied as a function of the relative amounts of HMDA and GA. The best sensitivity was found when HMDA and GA were 5% and 2.5% in aqueous solutions, respectively. Taking as a reference the functioning of this biosensor, the roles of HMDA and GA percentages appear to be opposed when the extension of the linear response range is considered. Indeed, an increase of one unit in HMDA percentage (from 5 to 6 %) induces an increase in the extension of the linear response range equal to that obtained with a decrease of one unit of GA percentage (from 2.5 to 1.5%).     

Intraresidue distribution of energy in proteins

Boltzmann-like distributions appear in many properties and energy-related quantities of proteins. A few examples are hydrophobicity, various types of side-chain/side-chain interactions, proline isomerization, hydrogen bonds, internal cavities, interactions at the level of specific atom types, and the propensity of the phi/'phi' ratio. Here, we conjecture that the Boltzmann hypothesis also holds for the intra-residue energy distribution. We confirm the conjecture by calculating the energies of 41,672 residues of the structures of highly resolved proteins, where at least 12 out of 20 naturally occurring amino acids follow Boltzmann's law. We further examine the entire set of all residue energies and find that the convolution of the individual distributions gives a Poisson function, which is followed by approximately 50% of individual proteins' structures.     

Determination of the enantiomeric composition of phenylalanine samples by chemometric analysis of the fluorescence spectra of cyclodextrin guest-host complexes

A novel strategy for determining the enantiomeric composition of phenylalanine samples that combines ordinary fluorescence spectroscopy, guest-host cyclodextrin chemistry, and multivariate regression modeling is investigated. Partial-least-squares regression (PLS-1) models were developed from fluorescence spectral data obtained with a series of samples containing cyclodextrin guest-host complexes of phenylalanine with different known enantiomeric compositions. The regression models were subsequently validated by determining the enantiomeric composition of a set of independently prepared phenylalanine samples. The ability of the models to correctly predict the enantiomeric compositions of future samples was evaluated in terms of the root-mean-square percent relative error (RMS%RE). The RMS%RE in the mol fraction of D-phenylalanine ranged from 1.3% to 3.0% when beta-cyclodextrin was used as the host molecule for different guest-host concentrations. The RMS%RE in the mol fraction of D-phenylalanine obtained in a similar validation study conducted with gamma-cyclodextrin ranged between 1.8% and 4.0% for different guest-host concentrations. Compared with previous studies done in absorption, fluorescence data were found to be more sensitive and the spectral differences observed as a function of enantiomeric composition were more uniformly spaced, making regression modeling more reliable. As a result, good regression models could be made at lower concentrations than were possible previously when absorption measurements were used.