Science and Engineering Research Council

On the basis of a new first-principles, electronic model for the forces driving clustering and short-range order in metallic alloys, it is argued that observed concentration-dependent peaks in the x-ray and electron diffuse scattering intensities are due to parallel sheets of flat Fermi surface. The positions of the peaks are directly related to the spanning vector ${\stackrel{\ensuremath{\rightarrow}}{\mathrm{k}}}_{0}$.

We present a new approach to photofragmentation which through its explicit time dependence avoids the difficulties normally associated with calculation of Franck–Condon processes. No scattering eigenfunctions or Franck–Condon overlaps are required, yet the formulae are exact within the same assumptions as the usual time independent theory. Semiclassical implementation of the method is described in connection with a successful application to H+3, which involves, in our model, a multiple continuum breakup final state on one of two excited state surfaces treated. Full arrangement and energy partitioning information are given on both surfaces in a calculation whose main numerical effort involves running five classical trajectories.

We report a synthetic material, [Co2(bipy)3(SO4)2(H2O)2](bipy) (CH3OH), (1, where bipy = 4,4'-bipyridyl) that contains discrete reactive and inert structural motifs that undergo a reversible substitution reaction involving the concerted and spatially controlled introduction of bipyridine and methanol molecules at the reactive sites. This reaction defines the pore geometry of the resulting open-framework structure and controls the manner in which this structure sorbs small molecules. The molecules involved in the reaction are positioned by an array of well-defined interactions during their path to binding to the metal centers.

Two hydrogen ordered phases of ice were prepared by cooling the hydrogen disordered ices V and XII under pressure. Previous attempts to unlock the geometrical frustration in hydrogen-bonded structures have focused on doping with potassium hydroxide and have had success in partially increasing the hydrogen ordering in hexagonal ice I (ice Ih). By doping ices V and XII with hydrochloric acid, we have prepared ice XIII and ice XIV, and we analyzed their structures by powder neutron diffraction. The use of hydrogen chloride to release geometrical frustration opens up the possibility of completing the phase diagram of ice.

New Pb isotopic data are presented for 10 young Mesozoic to their variation in age can provide valuable insights into Cenozoic (0-116 Ma) carbonatites from a 1400 km long segment the nature of the sub-continental mantle over a period of the East African Rift. Patterns observed in Pb vs Pb, Sr vs Pb of >27 by. On the basis of stable isotope data (Deines, and Nd vs Pb isotope diagrams define unusual, nearly linear, trends 1989; Keller & Hoefs, 1995), Pb, Sr and Nd isotope that are interpreted as mixing between two components that are compositions (Bell et al., 1982; data From these data, generated within the mantle. One of the most intriguing EM1 and HIMU are now known to occur in both continental features to emerge from the studies of young carbonatites and oceanic settings that are associated with plumes or rifts. is that they share isotope similarities with many oceanic Moreover, these isotopic signatures tend to occur in regions where island lavas For these reasons, we favour a model for the origin Kwon et al., 1989), thus raising the question as to whether of the East African Rift carbonatites that involves melting and parts of the sub-continental mantle and the sub-oceanic mixing of HIMU and EM1 components contained within an mantle are essentially the same in terms of their isotopic isotopically heterogeneous mantle plume. We consider the HIMU signatures. and EM1 sources to be stored within the deep (lower 1000 km)

A new dayside source of O + ions for the polar magnetosphere is described, and a statistical survey presented of upward flows of O + ions using 2 years of data from the retarding ion mass spectrometer (RIMS) experiment on board DE 1, at geocentric distances below 3 R E and invariant latitudes above 40°. The flows are classified according to their spin angle distributions. It is believed that the spacecraft potential near perigee is generally less than +2 V, in which case the entire O + population at energies below about 60 eV is sampled. Examples are given of field‐aligned flow and of transversely accelerated “core” O + ions; in the latter events a large fraction of the total O + ion population has been transversely accelerated, and in some extreme cases all the observed ions (of all ion species) have been accelerated, and no residual cold population is observed (“toroidal” distributions). However, by far the most common type of O + upflow seen by DE RIMS lies near the dayside polar cap boundary (particularly in the prenoon sector) and displays an asymmetric spin angle distribution. In such events the ions carry an upward heat flux, and strong upflow of all species is present (H + , He + , O + , O ++ , and N + have all been observed with energies up to about 30 eV, but with the majority of ions below about 2 eV); hence, these have been termed upwelling ion events. The upwelling ions are embedded in larger regions of classical light ion polar wind and are persistently found under the following conditions: at geocentric distances greater than 1.4 R E ; at all Kp in summer, but only at high Kp in winter. Low‐energy conical ions (<30 eV) are only found near the equatorial edge of the events, the latitude of which moves equatorward with increasing Kp and is highly correlated with the location of field‐aligned currents. The RIMS data are fully consistent with a “mass spectrometer effect,” whereby light ions and the more energetic O + ions flow into the lobes and mantle and hence the far‐tail plasma sheet, but lower‐energy O + is swept across the polar cap by the convection electric field, potentially acting as a source for the nightside auroral acceleration regions. The occurrence probability of upwelling ion events, as compared to those of low‐altitude transversely accelerated core ions and of field‐aligned flow, suggests this could be the dominant mechanism for supplying the nightside auroral acceleration region, and subsequently the ring current and near‐earth plasma sheet, with ionospheric O + ions. It is shown that the total rate of O + outflow in upwelling ion events (greater than 10 25 s −1 ) is sufficient for the region near the dayside polar cap boundary to be an important ionospheric heavy ion source.

The nm23 gene, a putative metastasis suppressor gene, was originally identified by its reduced expression in highly metastatic K-1735 murine melanoma cell lines, as compared to related, low metastatic melanoma cell lines. Transfection of nm23 cDNA has been reported to suppress malignant progression in Drosophila and mammalian cells. Highly conserved homologues of nm23 have been found in organisms ranging from the prokaryote Myxococcus xanthus to Drosophila, where the gene is involved in normal development and differentiation. The product of the nm23 gene exhibits a nucleoside diphosphate kinase activity, yet the nucleoside diphosphate kinase activity of Nm23 does not correlate with its apparent biological functions. We review recent cellular, genetic, biochemical and X-ray crystallographic data to formulate and evaluate hypotheses concerning the molecular mechanism of nm23 action.

The binding of the carotenoid astaxanthin (AXT) in the protein multimacromolecular complex crustacyanin (CR) is responsible for the blue coloration of lobster shell. The structural basis of the bathochromic shift mechanism has long been elusive. A change in color occurs from the orange red of the unbound dilute AXT (lambda(max) 472 nm in hexane), the well-known color of cooked lobster, to slate blue in the protein-bound live lobster state (lambda(max) 632 nm in CR). Intriguingly, extracted CR becomes red on dehydration and on rehydration goes back to blue. Recently, the innovative use of softer x-rays and xenon derivatization yielded the three-dimensional structure of the A(1) apoprotein subunit of CR, confirming it as a member of the lipocalin superfamily. That work provided the molecular replacement search model for a crystal form of the beta-CR holo complex, that is an A(1) with A(3) subunit assembly including two bound AXT molecules. We have thereby determined the structure of the A(3) molecule de novo. Lobster has clearly evolved an intricate structural mechanism for the coloration of its shell using AXT and a bathochromic shift. Blue/purple AXT proteins are ubiquitous among invertebrate marine animals, particularly the Crustacea. The three-dimensional structure of beta-CR has identified the protein contacts and structural alterations needed for the AXT color regulation mechanism.

Epidermal growth factor receptor (EGFR) signalling is activated by ligand-induced receptor dimerization. Notably, ligand binding also induces EGFR oligomerization, but the structures and functions of the oligomers are poorly understood. Here, we use fluorophore localization imaging with photobleaching to probe the structure of EGFR oligomers. We find that at physiological epidermal growth factor (EGF) concentrations, EGFR assembles into oligomers, as indicated by pairwise distances of receptor-bound fluorophore-conjugated EGF ligands. The pairwise ligand distances correspond well with the predictions of our structural model of the oligomers constructed from molecular dynamics simulations. The model suggests that oligomerization is mediated extracellularly by unoccupied ligand-binding sites and that oligomerization organizes kinase-active dimers in ways optimal for auto-phosphorylation in trans between neighbouring dimers. We argue that ligand-induced oligomerization is essential to the regulation of EGFR signalling.

The hemophilia A mutation database lists more than 160 missense mutations: each represents a molecular defect in the FVIII molecule, resulting in the X-linked bleeding disorder hemophilia A with a clinical presentation varying from mild to severe. Without a three-dimensional FVIII structure it is in most cases impossible to explain biological dysfunction in terms of the underlying molecular pathology. However, recently the crystal structure of the homologous human plasma copper-binding protein ceruloplasmin (hCp) has been solved, and the A domains of FVIII share approximately 34% sequence identity with hCp. This advance has enabled the building of a molecular model of the A domains of FVIII based on the sequence identity between the two proteins. The model allows exploration of predictions regarding the general features of the FVIII molecule, such as the binding-sites for factor IXa and activated protein C; it has also allowed the mapping of more than 30 selected mutations with known phenotype from the database, and the prediction of hypothetical links to dysfunction in all but a few cases. A computer-generated molecular model such as that reported here cannot substitute for a crystal structure. However, until such a structure for FVIII becomes available, the model represents a significant advance in modeling FVIII; it should prove a useful tool for exploiting the increasing amount of information in the hemophilia A mutation database, and for selecting appropriate targets for investigation of the structure-function relationships via mutagenesis and expression in vitro.

This paper reports the latest results from a near-infrared search for hidden broad-line regions (BLRs: FWHM >~ 2,000 km/s) in ultraluminous infrared galaxies (ULIGs). The new sample contains thirty-nine ULIGs from the 1-Jy sample selected for their lack of BLRs at optical wavelengths. The results from this new study are combined with those from our previous optical and near-infrared surveys to derive the fraction of all ULIGs with optical or near-infrared signs of genuine AGN activity (either a BLR or [Si VI] emission). Comparisons of the dereddened emission-line luminosities of the optical or obscured BLRs detected in the ULIGs of the 1-Jy sample with those of optical quasars indicate that the obscured AGN/quasar in ULIGs is the main source of energy in at least 15 -- 25% of all ULIGs in the 1-Jy sample. This fraction is 30 -- 50% among ULIGs with L_ir > 10^{12.3} L_sun. These results are compatible with those from recent mid-infrared spectroscopic surveys carried out with ISO. (abridged)

We survey and compare a wide variety of techniques for estimating the condition number of a triangular matrix, and make recommendations concerning the use of the estimates in applications. Each of the methods is shown to bound the condition number; the bounds can broadly be categorised as upper bounds from matrix theory and lower bounds from heuristic or probabilistic algorithms. For each bound we examine by how much, at worst, it can overestimate or underestimate the condition number. Numerical experiments are presented in order to illustrate and compare the practical performance of the condition estimators.

Silicate dust grains in the interstellar medium are known to be mostly amorphous, yet crystalline silicate grains have been observed in many long-period comets and in protoplanetary disks. Annealing of amorphous silicate grains into crystalline grains requires temperatures > 1000 K, but exposure of dust grains in comets to such high temperatures is incompatible with the generally low temperatures experienced by comets. This has led to the proposal of models in which dust grains were thermally processed near the protoSun, then underwent considerable radial transport until they reached the gas giant planet region where the long-period comets originated. We hypothesize instead that silicate dust grains were annealed in situ, by shock waves triggered by gravitational instabilities. We assume a shock speed of 5 km/s, a plausible value for shocks driven by gravitational instabilities. We calculate the peak temperatures of micron and submicron amorphous pyroxene grains of chondritic composition under conditions typical in protoplanetary disks at 5 - 10 AU. Our results also apply to chondritic amorphous olivine grains. We show that {\\it in situ} thermal annealing of submicron and micron-sized silicate dust grains can occur, obviating the need for large-scale radial transport.

IL-10, an immunoregulatory cytokine produced by T cells and monocytes, inhibits the expression of inflammatory and hemopoietic cytokines as well as its own expression. To evaluate the regulation of IL-10 production by T cells and monocytes, we measured IL-10 levels by ELISA in supernatants of PHA-stimulated PBMC following depletion of either T cells or monocytes. IL-10 production was significantly down-regulated in both T cell- and monocyte-depleted PBMC compared with undepleted PBMC, and IL-10 production could be restored by the addition of monocyte-conditioned medium (supernatant of PHA-stimulated, T cell-depleted PBMC), suggesting that IL-10 production by T cells is regulated by a monokine(s) produced by activated monocytes. To further clarify the monokine(s) responsible for IL-10 induction, we stimulated monocyte-depleted PBMC, purified CD4+, and CD8+ T cells with PHA and measured IL-10 production by ELISA and semiquantitative reverse transcriptase-PCR following monokine(s) addition. Addition of IL-6 and IL-12 enhanced IL-10 production in monocyte-depleted PBMC in a dose-dependent and additive manner. Furthermore, anti-IL-6 and anti-IL-12 Abs neutralized the IL-10-inductive effect of monocyte-conditioned medium. Similarly, IL-12 and IL-6 induced IL-10 production by purified CD4+ and CD8+ T cells. With respect to regulation of IL-10 produced by monocytes, TNF-alpha was found to induce IL-10 production by resting as well as by LPS-stimulated purified monocytes/macrophages. Taken together, these findings suggest that IL-10 production by human T cells and monocytes is differentially regulated. IL-12 and/or IL-6 can induce the expression of IL-10 by PHA-stimulated T cells, whereas TNF-alpha induces IL-10 production by monocytes. Since IL-10 inhibits the production of IL-6, IL-12, and TNF-alpha, these results may indicate a potential mechanism of negative feedback regulation of the immune response.

Occupancy of only one of two hydrolytic sites on beef heart mitochondrial ATPase (F1) by the radioactive ATP analog, 2',3'-O-(2,4,6-trinitrophenyl) adenosine 5'-[gamma-32P]-triphosphate (TNP-[gamma-32P]ATP) is associated with a low rate of hydrolysis of the substrate even under conditions otherwise favoring catalysis. Addition of excess nonradioactive TNP-ATP, in concentrations sufficient to fill catalytic Site 2 on the enzyme (Grubmeyer, C., and Penefsky, H. S. (1981) J. Biol. Chem. 256, 3718-3727), accelerates the rate of hydrolysis of the radioactive substrate 15- to 20-fold. Since the excess nonradioactive substrate serves as an effective isotope trap, the involvement of medium TNP-[gamma-32P]-ATP as an intermediate is ruled out. These observations constitute direct evidence for catalytic cooperativity between active sites on F1. It is proposed that the use of high binding affinity substrates or substrate analogs, combined with the isotope trap technique, offers a new approach to the detection and study of catalytic site cooperativity in enzymes. The hydrolyzable nucleotides GTP, ITP, and ATP are excellent promoters of the hydrolysis of previously bound TNP-[gamma-32P]ATP whereas addition of nonhydrolyzable nucleotides such as TNP-ADP, ADP, and adenylyl imidodiphosphate result in a lower rate and extent of hydrolysis. AMP is without effect. Studies of the hydrolysis of [gamma-32P]ATP and TNP-[gamma-32P]ITP, under appropriate conditions, also provide evidence consistent with promoted catalysis. Based upon these findings, a model is presented for the mechanism of action of F1 in which site-site cooperativity reflects promoter-dependent hydrolysis of bound substrate.

In recent years, lattice Boltzmann methods have been increasingly used to simulate rarefied gas flows in microscale and nanoscale devices. This is partly due to the fact that the method is computationally efficient, particularly when compared to solution techniques such as the direct simulation Monte Carlo approach. However, lattice Boltzmann models developed for rarefied gas flows have difficulty in capturing the nonlinear relationship between the shear stress and strain rate within the Knudsen layer. As a consequence, these models are equivalent to slip-flow solutions of the Navier-Stokes equations. In this paper, we propose an effective mean-free path to address the Knudsen layer effect, so that the capabilities of lattice Boltzmann methods can be extended beyond the slip-flow regime. The model has been applied to rarefied shear-driven and pressure-driven flows between parallel plates at Knudsen numbers between 0.01 and 1. Our results show that the proposed approach significantly improves the near-wall accuracy of the lattice Boltzmann method and provides a computationally economic solution technique over a wide range of Knudsen numbers.

Atomistic simulations of matter, especially those that leverage first-principles (ab initio) electronic structure theory, provide a microscopic view of the world, underpinning much of our understanding of chemistry and materials science. Over the last decade or so, machine-learned force fields have transformed atomistic modeling by enabling simulations of ab initio quality over unprecedented time and length scales. However, early machine-learning (ML) force fields have largely been limited by (i) the substantial computational and human effort required to develop and validate potentials for each particular system of interest and (ii) a general lack of transferability from one chemical system to the next. Here, we show that it is possible to create a general-purpose atomistic ML model, trained on a public dataset of moderate size, that is capable of running stable molecular dynamics for a wide range of molecules and materials. We demonstrate the power of the MACE-MP-0 model-and its qualitative and at times quantitative accuracy-on a diverse set of problems in the physical sciences, including properties of solids, liquids, gases, chemical reactions, interfaces, and even the dynamics of a small protein. The model can be applied out of the box as a starting or "foundation" model for any atomistic system of interest and, when desired, can be fine-tuned on just a handful of application-specific data points to reach ab initio accuracy. Establishing that a stable force-field model can cover almost all materials changes atomistic modeling in a fundamental way: experienced users obtain reliable results much faster, and beginners face a lower barrier to entry. Foundation models thus represent a step toward democratizing the revolution in atomic-scale modeling that has been brought about by ML force fields.

The relationships between the environments of cations in alkali silicates measured by X-ray absorption fine structure (XAFS) and magic angle spinning nuclear magnetic resonance (MASNMR) are considered. Both are consistent with the modified random network for glass structure in which modifiers form channels percolating through the network. It is proposed that the mechanisms determining the distribution of bridging and non-bridging oxygen atoms at the glass transition are the same as those that promote ionic transport at lower temperatures in the glass. In particular the results of XAFS and MASNMR can be used to predict the activation energy for ionic transport and the magnitude of the electrical conductivity. Values of these parameters for alkali disilicates are in good agreement with those measured directly from transport properties.

Abstract An experiment has been set up at the Daresbury Synchrotron Radiation Facility to make absolute absorption cross section measurements over a wide range of photon energies. New data are reported for helium, neon, argon and krypton over the range 340-40 Å which are believed to be reliable to ± 5%. A critical evaluation of published cross section data has been carried out to produce best value data from the ionization thresholds throughout the vacuum ultraviolet and X-ray region. Agreement with theoretical calculations on helium is demonstrated to be within ± 2-3% from threshold down to the double ionization threshold at 79 eV. Comparison with recent calculations of photoionization cross sections has shown that the effect of electron correlations is significant for the heavier inert gases. Contrary to previous claims, the position of the M shell maximum in krypton is located at 184 + 10 eV in good agreement with r. p. a. e. calculations. Oscillator strength sum rules have been examined and their moments calculated. Discrepancies developing towards the heavier inert gases suggests a decrease in polarizabilities and other atomic factors from those predicted by Hartree-Fock calculations.

A computational scheme for the treatment of Coulomb sums in the Hartree-Fock approach to periodic systems in one, two, and three dimensions is presented. The philosophy is as follows: (a) The interaction of two charge distributions contributing to the total charge in cells $\stackrel{\ensuremath{\rightarrow}}{0}$ and $\stackrel{\ensuremath{\rightarrow}}{\mathrm{m}}$ is treated exactly at short range; (b) when the reciprocal penetration of the distributions is sufficiently small, the charge distribution at $\stackrel{\ensuremath{\rightarrow}}{\mathrm{m}}$ is partitioned into "shell-charge distributions" which are then expanded in a multipole series; (c) for $|\stackrel{\ensuremath{\rightarrow}}{\mathrm{m}}|$ larger than a given threshold, a Madelung sum of atomic charges is performed. Results are reported for the $\mathrm{S}{\mathrm{N}}_{x}$ polymer, the graphite, boron nitride, and beryllium monolayers, for the beryllium monolayer with hydrogen chemisorbed thereon, and for three-dimensional silicon, with a view to compare two charge-partitioning schemes, and the convergence of the results with respect to the order of the multipole expansions. It is shown that the inclusion of all terms to hexadecapole confines the error in the Coulomb contribution to the total energy for all the systems considered to within 0.001 a.u./atom, with the exactly treated zone reduced to a few neighbors, and that at this level the results are essentially independent of the particular charge-partitioning scheme adopted.