Fully rotationally resolved ZEKE photoelectron spectroscopy of C6H6 and C6D6: photoionization dynamics and geometry of the benzene cation

A comprehensive set of spectra for the benzene cation and the perdeuterated benzene cation has been recorded with full rotational resolution using zero kinetic energy photoelectron spectroscopy (ZEKE) at high resolution (up to 0.2 cm^?1), using a slow-rising extraction pulse. With different rovibronic levels in the S₁ 6^l state as intermediate resonance, the rotational transitions to the vibronic ground state of the cation have been recorded using two-colour, two-photon resonance enhanced multiphoton ionization. A simple spectator model has been employed to simulate the intensities of the ZEKE transitions. By fitting the simulations to the recorded spectra, improved values for the rotational constants and the Coriolis coupling parameters of benzene and perdeuterated benzene have been obtained. The CC and CH bond lengths of the cation have been deduced. The spectator model is shown to be reliable despite the fact that no specific allowance is made for the effect of final state interactions on the signal intensity.     

Estimating vaccine coverage by using computer algebra

Email: altmannd{at}rki.deEmail: altmann{at}mathematik.hu-berlin.de The approach of N Gay for estimating the coverage of a multivalentvaccine from antibody prevalence data in certain age cohortsis complemented by using computer aided elimination theory ofvariables. Hereby, Gay's usage of numerical approximation canbe replaced by exact formulae which are surprisingly nice, too.     

The Numerical Solution of Constrained Linear Least-squares Problems

The paper describes a numerically stable algorithm to solveconstrained linear least-squares problems and allows rank deficientor underdetermined observation matrices. The method starts withthe calculation of the rank of the observation matrix and thetransformation into a least distance problem. The proposed techniquefor solving the least distance problem can be considered asa generalization of the projection method of Stoer (1971). Startingwith a feasible point, a sequence of iterates is calculatedby minimizing the objective function on the linear boundarymanifold determined by the active constraints. Numerical examplesshow the feasibility of the algorithm.     

AN AXIOMATIC APPROACH TO SUSTAINABILITY

ABSTRACT. In this paper a new concept for sustainable development is proposed. Unlike the usual present value maximizing approach, the discount rates are determined endoge‐nously. For a standard model of renewable natural resources it is shown that a solution can be found by solving an appropriate system of equations.     

Molecular orbital study of polarity and hydrogen bonding effects on the g and hyperfine tensors of site directed NO spin labelled bacteriorhodopsin

Semiempirical molecular orbital methods (PM3, INDO, ZINDO/S) have been used to calculate the effects of local electric fields and of hydrogen bonding on the g and hyperfine tensors of a nitroxide spin label model system. The results yield a linear correlation between the two principal tensor components g _xx and A ^N _zz at label sites of varying polarity. Hydrogen bonding with a single water molecule produces a constant shift of Δg _xx ? ?4 × 10^?4. These theoretical results are used to interpret recent high field (3.4 T, 95 GHz) electron paramagnetic resonance investigations on site-directed spin labelled bacteriorhodopsin. This protein reveals a close correlation between proticity and polarity at the various label sites. The slope of the g _xx versus A ^N _zz dependence is affected strongly by polarity induced structural strains of the spin label.     

ECONOMIC MODELING OF THE PERSISTENCE OF ANTIMICROBIAL RESISTANCE

Abstract According to the dynamic relationship between antibiotic use and the incidence of multidrug‐resistant bacteria, the effectiveness of antibiotics is characterized as a natural resource exploited by antibiotic use. A major question is whether antibiotic effectiveness should be considered a renewable or an exhaustible resource. This paper presents a model combining epidemiological aspects of the decrease of resistance over time with an economic approach, modeling antimicrobial resistance as a negative externality of antibiotic use. The article concludes that the relative fitness of resistant bacteria is one driving factor for an estimation of the externality. If we, for instance, assume a low degree of relative fitness of resistant bacteria it is shown that resistance decreases fastest directly after antibiotic treatment. Accordingly, cycling of nonidentical drugs improves antibiotic effectiveness because cycling lowers the frequency of use of the individual antibiotic. In this case, antibiotic effectiveness must be characterized as a renewable resource in much the same way as a stock of fish in a lake. In contrast, if we assume a high degree of relative fitness of resistant bacteria, antibiotic effectiveness must be treated as an exhaustible resource because it is declined by every use of antibiotics.     

Fast and Accurate Phase Retardation Measurement of 0° Twisted Nematic Liquid Crystal Panels Based on the Principle of Homodyne Receiving

We describe herein a method to measure quickly (in less than 2 min) and accurately the phase retardation between the extraordinary and ordinary axis of homogeneous or 0° twisted nematic liquid crystal panels. Owing to the homodyne detection scheme, the setup allows us to probe liquid crystal (LC) panels with an optical power down to a fraction of 1 nW and, hence makes it possible to focus the light beam to a spot of only a few wavelengths in diameter without heating or inducing observable variations in the liquid crystal. The dependence of the phase retardation on the LC driver frequency and the temperature are presented and compared with the theoretical prediction.     

PHOTOLYSIS OF CYSTINE IN THE PRESENCE OF AROMATIC AMINO ACIDS

Se dan evidencias para explicar los distintos rendimientos cuánticos de fotólisis con lux u.v. para distintos residuos de cisteina en lisozima e insulina. En sistemas modelos de mezclas de aminoácidos, el aminoácido triptofano muestra un marcado aumento en el rendimiento cuántico en la fotólisis de la cisteina. La fotosensibilidad de los residuos de cisteina en la lisozima se interpretan usando la conformación terciaria de la enzima la cual provee una relación espacial entre los residuos de triptofano y cisteina.     

Branch switching at a corank-4 bifurcation point of semi-linear elliptic problems with symmetry

Branch switching of the problem at a corank-4 bifurcation point is investigated by exploitingsymmetry and other properties of the operator. Here f :RR isa smooth odd function. The singularity of the corank-4 bifurcationpoint is decomposed into various subspaces via symmetries suchthat all solution branches can be followed by continuation methodsand their modifications. At the same time, a modified Lyapunov-Schmidtmethod is used to determine solution branches having littlesymmetry on a slightly enlarged system in appropriate subspaces.We find altogether 40 different solution branches. Among themwe have 13 solutions, such that none of these solutions canbe generated by conjugation or hidden symmetries from any othersolutions.     

Core-halogenated,helical-chiral triphenylene-based columnar liquid crystals

It is shown that chlorination and even bromination of the mesogenic hexahexyloxytriphenylene 1 can take place at the sterically congested tetracyclic core delivering the respective monohalogenated, sevenfold substituted enantiotropic mesogens 3 and 4 in 32 and 17% yields, respectively, giving mesophases over greater temperature ranges. Miscibility tests among all mesogenic compounds of this study prove formation of the columnar hexagonal type of phase. The steric and electronic effects of those substituents, different from the six equal alkoxy groups, on the mesophase are discussed in detail. In our hands and to our surprise, the sterically hindered acceptor (nitro or halogeno) substituents of 2, 3, or 4 could not be replaced by an alkylthio group in nucleophilic aromatic substitution reactions using the aprotic polar solvent DMEU. Semi-empirical calculations on numerous hexaethers with one or two substituents, e.g. halogens or others, in one of the three bay regions of the triphenylene core reveal that these molecules are helically deformed due to the crowding in the molecule. In this new case of atropisomerism, the 1,12-disubstituted derivatives should offer the possibility of resolution into enantiomers and, therefore, of studying disc-like mesomorphic compounds possessing for the first time the origin of chirality within their molecular centre.