Geometry optimization using symmetry coordinates

The use of symmetry coordinates (SC ) in geometry optimization is discussed. A computer program incorporating the use of sc, together with analytical calculation of the gradient and quadratic acceleration, is described. Also reported are careful test results on a series of small molecules and typical results with a long series of molecules up to quite large size (40–60 atoms).     

Anomalous Tc-behavior of LaSn3 under pressure

The superconducting transition temperature T_c of LaSn₃ has been measured up to ～ 22 kbar and was observed to increase through a maximum under hydrostatic compression. The anomalous T_c-behavior is attributed to a pressure induced Fermi surface topology change.     

High dimensional model representation constructed by support vector regression. I. Independent variables with known probability distributions

High dimensional model representation (HDMR) is a general set of quantitative model assessment and analysis tools for capturing high dimensional input-output system behavior. In practice, the HDMR component functions are each approximated by an appropriate basis function expansion. This procedure often requires many input-output samples which can restrict the treatment of high dimensional systems. In order to address this problem we introduce svr-based HDMR to efficiently and effectively construct the HDMR expansion by support vector regression (SVR) for a function \(f(\mathbf{x})\). In this paper the results for independent variables sampled over known probability distributions are reported. The theoretical foundation of the new approach relies on the kernel used in SVR itself being an HDMR expansion (referred to as the HDMR kernel ), i.e., an ANOVA kernel whose component kernels are mutually orthogonal and all non-constant component kernels have zero expectation. Several HDMR kernels are constructed as illustrations. While preserving the characteristic properties of HDMR, the svr-based HDMR method enables efficient construction of high dimensional models with satisfactory prediction accuracy from a modest number of samples, which also permits accurate computation of the sensitivity indices. A genetic algorithm is employed to optimally determine all the parameters of the component HDMR kernels and in SVR. The svr-based HDMR introduces a new route to advance HDMR algorithms. Two examples are used to illustrate the capability of the method.     

Starch biosynthesis and modification of starch structure in transgenic plants

Starch is synthesised through the ADP-glucose pathway, involving the three enzymes ADP-glucose pyrophosphorylase, starch synthase and starch branching enzyme. ADP-glucose pyrophosphorylase is the key enzyme of the pathway, determining the flux of carbon into starch. It generates ADP-glucose, which is the substrate for the starch synthases, from glucose-1-phosphate and ATP releasing pyrophosphate. The enzyme is stimulated by 3-phosphoglycerate and inhibited through inorganic phosphate. The starch synthases, which catalyse the transfer of glucose from ADP-glucose to the nonreducing end of a growing α-1,4-glucan, are divided into two classes, the granule-bound starch synthases (GBSS) and the soluble starch synthases (SS). In both classes several isoforms have been described from many different plant species. The branching enzyme, which introduces branchpoints into the amylopectin, can also occur in different isoforms. Other enzymes present in plants, which also act on α-1,4-glucans, such as the starch phosphorylases, disproportionating enzyme and different starch hydrolases, might also be important for dertermining the starch structure and, therefore, its processibility. Many aspects of starch synthesis are not fully understood to date. Starch metabolism can be manipulated through genetic engineering, either by the ectopic expression of different heterologous genes, or through the repression of the expression of endogenous genes using antisense RNA technology. This not only allows the functional analysis of starch biosynthetic proteins, but also the manipulation of starch structure in order to widen its industrial applications. In this way many different potato lines have been generated, containing either different amounts of starch, or which synthesize a structurally modified starch. These structural changes relate to the amylose content, the phosphate content, or the gelatinisation and gelation characteristics of the starch.     

Logical Analysis of Data in Structure‐Activity Investigation of Polymeric Gene Delivery

To date semi‐empirical or surrogate modeling has demonstrated great success in the prediction of the biologically relevant properties of polymeric materials. For the first time, a correlation between the chemical structures of poly(β‐amino esters) and their efficiency in transfecting DNA was established using the novel technique of logical analysis of data (LAD). Linear combination and explicit representation models were introduced and compared in the framework of the present study. The most successful regression model yielded satisfactory agreement between the predicted and experimentally measured values of transfection efficiency (Pearson correlation coefficient, 0.77; mean absolute error, 3.83). It was shown that detailed analysis of the rules provided by the LAD algorithm offered practical utility to a polymer chemist in the design of new biomaterials.

     

Anionic N-heterocyclic carbenes with N,N'-bis(fluoroaryl) and N,N'-bis(perfluoroaryl) substituents

A series of rhodium complexes, [Rh(cod)(NHC-F(x))(OH(2))] (cod = 1,5-cyclooctadiene; NHC = N-heterocyclic carbene), incorporating anionic N-heterocyclic carbenes with 2-tert-butylmalonyl backbones and 2,6-dimethylphenyl (x = 0), 2,6-difluorophenyl (x = 4), 2,4,6-trifluorophenyl (x = 6), and pentafluorophenyl (x = 10) N,N'-substituents, respectively, has been prepared by deprotonation of the corresponding zwitterionic precursors with potassium hexamethyldisilazide, followed by immediate reaction of the resulting potassium salts with [{RhCl(cod)}(2)]. These complexes could be converted to the related carbonyl derivatives [Rh(CO)(2)(NHC-F(x))(OH(2))] by displacement of the COD ligand with CO. IR and NMR spectroscopy demonstrated that the degree of fluorination of the N-aryl substituents has a considerable influence on the σ-donating and π-accepting properties of the carbene ligands and could be effectively used to tune the electronic properties of the metal center. The carbonyl groups on the carbene ligand backbone provided a particularly sensitive probe for the assessment of the metal-to-ligand π donation. The ortho-fluorine substituents on the N-aryl groups in the carbene ligands interacted with the other ligands on rhodium, determining the conformation of the complexes and creating a pocket suitable for the coordination of water to the metal center. Computational studies were used to explain the influence of the fluorinated N-substituents on the electronic properties of the ligand and evaluate the relative contribution of the σ- and π-interactions to the ligand-metal interaction.     

Diagnosing unknown aberrations in an adaptive optics system by use of phase diversity

We outline a novel method for estimating a fixed aberration that is in the image path but not in the wave-front-sensor (WFS) path of an adaptive optics (AO) imaging system. We accomplish this through a nontraditional application of the Gonsalves [Proc. SPIE 207, 32 (1997)] least-squares phase-diversity technique, using an ensemble of images and WFS data. The diversity phases required for this technique are provided by the temporal differences in WFS residual phase measurements for different members of the ensemble. We demonstrate the technique by using actual observations from an operational AO system exhibiting such an aberration. An estimate of this aberration was obtained by the proposed algorithm that agrees reasonably well with the observed point-spread function.     

Crispin St J. A. Nash-Williams (1932-2001)

Crispin St John Alvah Nash-Williams was born in Cardiff on 19December 1932. His father was Keeper of Archaeology at the NationalMuseum of Wales and also Senior Lecturer in Archaeology at UniversityCollege, Cardiff. War broke out when Crispin was six; his fatherjoined the army and his consequent absence changed the family'slife.