Towards mechanically-linked polymers

This short review describes the progress which is being made towards the self-assembly of mechanically-linked polymers. A new concept in polymer synthesis - self-assembly - is demonstrated to have the potential to create novel high molecular weight polymers which possess repeat units that do not just consist of a main chain backbone built up of entirely covalent bonds, but are constructed of mechanical linkages comprised of catenane and rotaxane motifs.     

Infrared spectroscopy studies of cation effects on lipopolysaccharides in aqueous solution

The conformation of amphiphilic lipopolysaccharides (LPS) influences the behavior of free and cell-bound LPS in aqueous environments, including their adhesion to surfaces. Conformational changes in Pseudomonas aeruginosa serotype 10 LPS aggregates resulting from changes in solution pH (3, 6, and 9), ionic strength [I] 1, 10, and 100 mmol L⁻¹, and electrolyte composition (NaCl and CaCl₂) were investigated via attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy. ATR-FTIR data indicate that LPS forms more stable aggregates in NaCl relative to CaCl₂ solutions. Time- and cation-dependent changes in ATR-FTIR data suggest that LPS aggregates are perturbed by Ca²⁺ complexation at lipid A phosphoryl groups, which leads to reorientation of the lipid A at the surface of a ZnSe ATR internal reflection element (IRE). Polarized ATR-FTIR investigations reveal orientation of LPS dipoles approximately perpendicular to the IRE plane for both Na- and Ca-LPS. The results indicate that changes in solution chemistry strongly impact the conformation, intermolecular and interfacial behavior of LPS in aqueous systems.     

QUADRATURE METHODS FOR HIGHLY OSCILLATORY SINGULAR INTEGRALS

We address the evaluation of highly oscillatory integrals,with power-law and logarithmic singularities.Such problems arise in numerical methods in engineering.Notably,the evaluation of oscillatory integrals dominates the run-time for wave-enriched boundary integral formulations for wave scattering,and many of these exhibit singularities.We show that the asymptotic behaviour of the integral depends on the integrand and its derivatives at the singular point of the integrand,the stationary points and the endpoints of the integral.A truncated asymptotic expansion achieves an error that decays faster for increasing frequency.Based on the asymptotic analysis,a Filon-type method is constructed to approximate the integral.Unlike an asymptotic expansion,the Filon method achieves high accuracy for both small and large frequency.Complex-valued quadrature involves interpolation at the zeros of polynomials orthogonal to a complex weight function.Numerical results indicate that the complex-valued Gaussian quadrature achieves the highest accuracy when the three methods are compared.However,while it achieves higher accuracy for the same number of function evaluations,it requires signi cant additional cost of computation of orthogonal polynomials and their zeros.     

Reconstructing Binary Signals from Local Histograms

In this paper, we considered the representation power of local overlapping histograms for discrete binary signals. We give an algorithm that is linear in signal size and factorial in window size for producing the set of signals, which share a sequence of densely overlapping histograms, and we state the values for the sizes of the number of unique signals for a given set of histograms, as well as give bounds on the number of metameric classes, where a metameric class is a set of signals larger than one, which has the same set of densely overlapping histograms.     

Improvement of modified analytic embedded atom method potentials for noble metals and Cu

The modified analytic embedded atom model (EAM) potentials considering farther neighbor atoms are improved for the noble metals (Ag, Au, Pt, Pd, Rh) and Cu. We not only adopt an end processing function and an enhanced smooth continuous condition for the pair potential, but also adjust the model parameters of multi-body potential by fitting a cohesive energy, a mono-vacancy formation energy, the Rose equation curve for the cohesive energy as a function of lattice parameter, a structure energy difference, elastic parameters and an equilibrium condition of crystal. The calculation results of structure energy differences misfit the experiment data for the noble metals and Cu in the unimproved EAM, because anyone of these differences have not been considered in the calculation of its model parameters. After the modification, the model showed better simulation results for the noble metals and Cu.     

TEM characterization of chemically synthesized copper–gold nanoparticles

Dodecanethiol-capped Cu–Au nanoparticles, synthesized via a successive two-phase (water/toluene) and galvanic-exchange procedure, were characterized using transmission electron microscopy (TEM). The size range of the particles is around 1–7 nm. Electron-induced morphological evolution was observed under high resolution (HR) TEM. Cuboctahedral morphology was found to be thermodynamically stable. Electron-induced aggregation of two particles was also observed. Chemical ordering of cuboctahedral particles was studied by atomic-resolution high angle annular dark field (HAADF) imaging in scanning TEM (STEM) mode and energy dispersive X-ray (EDX) element mapping using a silicon drift detector (SDD). The particles were found to be Cu–Au mixed, and to be stable in air. Surface plasmon resonance (SPR), which is dependent on local structure and morphology, was investigated by electron energy loss spectroscopy (EELS).     

Torsional Splittings in Small-Amplitude Vibrational Fundamental States of Methanol-Type Molecules

Group-theoretical methods are used to show that inverted torsional splittings in fundamental levels of small-amplitude vibrations of methanol-like molecules can be parameterized and understood in terms of the energy level patterns induced when a pair of high-barrier torsionally split components of given v(t) and (t)A+(t)E symmetry species in the molecular symmetry group G(6) is allowed to interact with small-amplitude vibrational modes of symmetry (v)E. Such doubly degenerate (v)E vibrational modes arise rather naturally in G(6) (isomorphic with the point-group C(3v)) for those methyl-group vibrations in point-group-C(s) asymmetric tops such as CH(3)-CHO that are analogs of the degenerate methyl-group stretch, bend, and rocking vibrations in point-group-C(3v) symmetric tops such as CH(3)-C identical withC-H. The present group-theoretical treatment is somewhat different from, but (as a comparison of model parameters shows) still fundamentally similar to, the recent local mode explanation of inverted torsional splittings in the C-H stretching fundamental region in methanol. Copyright 2001 Academic Press.     

Evaluating environmental quality management programmes in which dischargers are grouped

A method is presented for evaluating management programmes in which the dischargers are divided into groups. Analogous non-linear mathematical formulations are presented for direct regulation and effluent charge programmes, and a non-linear branch-and-bound solution procedure is described. A detailed algorithm is described for the effluent charge case; it is shown to be very practical in an application to data for the Delaware estuary.     

Conformational Dynamics Underlies Different Functions of Human KDM7 Histone Demethylases

The human KDM7 subfamily histone H3 Nϵ-methyl lysine demethylases PHF8 (KDM7B) and KIAA1718 (KDM7A) have different substrate selectivities and are linked to genetic diseases and cancer. We describe experimentally based computational studies revealing that flexibility of the region linking the PHD finger and JmjC domains in PHF8 and KIAA1718 regulates interdomain interactions, the nature of correlated motions, and ultimately H3 binding and demethylation site selectivity. F279S an X-linked mental retardation mutation in PHF8 is involved in correlated motions with the iron ligands and second sphere residues. The calculations reveal key roles of a flexible protein environment in productive formation of enzyme-substrate complexes and suggest targeting the flexible KDM7 linker region is of interest from a medicinal chemistry perspective.