Sandia National Laboratories

About: Sandia National Laboratories is a facility organization based out in Livermore, California, United States. It is known for research contribution in the topics: Laser & Combustion. The organization has 21501 authors who have published 46724 publications receiving 1484388 citations. The organization is also known as: SNL & Sandia National Labs.

Ruffling in a Series of Nickel(II) meso-Tetrasubstituted Porphyrins as a Model for the Conserved Ruffling of the Heme of Cytochromes c.

Abstract: Metalloporphyrins undergo remarkable nonplanar distortions of the macrocycle that perturb the chemical and photochemical properties of these important protein cofactors. Further, the tertiary structure of the surrounding protein can manipulate these distortions as a means of regulating biological function. For cytochromes c, for example, an energetically unfavorable, conserved nonplanar distortion of the heme exists and likely plays a role in its electron- transfer function. The heme distortion is primarily of the ruffling (ruf, type (corresponding to the lowest frequency BI,-symmetry normal mode) in which the pyrroles are twisted about the metal-Npyrrole bond. This BI.-symmetry nonplanar distortion is commonly observed in metalloporphyrin crystal structures, as are the saddling (sad) B2,- symmetry distortion, waving (wau) E,-symmetry distortions, and doming (dom) Az,-symmetry distortion. Each of these nonplanar distortions is expected to result in unique alterations of the chemical and physical properties of the nominally planar porphyrin macrocycle. Symmetrical porphyrin substitution with tetrahedrally bonded atoms at the four meso bridging carbons generally results in the BI, ruffling distortion; therefore, we investigated a series of meso-tetrasubstituted porphyrins for which the substituents vary in size (methyl, ethyl, propyl, pentyl, isopropyl, cyclopropyl derivative lla, cyclohexyl, apopinenyl (lo), tert-butyl, adamantyl), increasing the steric crowding at the periphery. Molecular mechanics calculations show increasing degree of ruffling (CaNNCa angle for opposite pyrroles varies from 0 to 57") for this series of porphyrins, generally agreeing with the X-ray structures that are available. In addition, the frequencies of the structure-sensitive Raman lines decrease nonlinearly with increasing ruffling angle. The localization of the Bl, nonplanar distortion in only the C,-C, bond torsion (not the case for the B2" sad distortion) suggests a means by which the B1, distortion might be distinguished from other types of nonplanar distortion by using resonance Raman spectroscopy. Also, the size of the red shifts in the n - n* absorption bands depends on Ca-Cm torsion angle in a nonlinear fashion and the shift is accurately predicted by INDO/s molecular orbital calculations when the nonplanar structures obtained from molecular mechanics are used.

Heat transfer and fluid flow during laser spot welding of 304 stainless steel

Abstract: The evolution of temperature and velocity fields during laser spot welding of 304 stainless steel was studied using a transient, heat transfer and fluid flow model based on the solution of the equations of conservation of mass, momentum and energy in the weld pool. The weld pool geometry, weld thermal cycles and various solidification parameters were calculated. The fusion zone geometry, calculated from the transient heat transfer and fluid flow model, was in good agreement with the corresponding experimentally measured values for various welding conditions. Dimensional analysis was used to understand the importance of heat transfer by conduction and convection and the roles of various driving forces for convection in the weld pool. During solidification, the mushy zone grew at a rapid rate and the maximum size of the mushy zone was reached when the pure liquid region vanished. The solidification rate of the mushy zone/liquid interface was shown to increase while the temperature gradient in the liquid zone at this interface decreased as solidification of the weld pool progressed. The heating and cooling rates, temperature gradient and the solidification rate at the mushy zone/liquid interface for laser spot welding were much higher than those for the moving and spot gas tungsten arc welding.

Computational protein design enables a novel one-carbon assimilation pathway

Abstract: We describe a computationally designed enzyme, formolase (FLS), which catalyzes the carboligation of three one-carbon formaldehyde molecules into one three-carbon dihydroxyacetone molecule. The existence of FLS enables the design of a new carbon fixation pathway, the formolase pathway, consisting of a small number of thermodynamically favorable chemical transformations that convert formate into a three-carbon sugar in central metabolism. The formolase pathway is predicted to use carbon more efficiently and with less backward flux than any naturally occurring one-carbon assimilation pathway. When supplemented with enzymes carrying out the other steps in the pathway, FLS converts formate into dihydroxyacetone phosphate and other central metabolites in vitro. These results demonstrate how modern protein engineering and design tools can facilitate the construction of a completely new biosynthetic pathway.

Factors influencing graphene growth on metal surfaces

Abstract: Graphene forms from a relatively dense, tightly bound C-adatom gas when elemental C is deposited on or segregates to the Ru(0001) surface. Nonlinearity of the graphene growth rate with C-adatom density suggests that growth proceeds by addition of C atom clusters to the graphene edge. The generality of this picture has now been studied by use of low-energy electron microscopy (LEEM) to observe graphene formation when Ru(0001) and Ir(111) surfaces are exposed to ethylene. The finding that graphene growth velocities and nucleation rates on Ru have precisely the same dependence on adatom concentration as for elemental C deposition implies that hydrocarbon decomposition only affects graphene growth through the rate of adatom formation. For ethylene, that rate decreases with increasing adatom concentration and graphene coverage. Initially, graphene growth on Ir(111) is like that on Ru: the growth velocity is the same nonlinear function of adatom concentration (albeit with much smaller equilibrium adatom concentrations, as we explain with DFT calculations of adatom formation energies). In the later stages of growth, graphene crystals that are rotated relative to the initial nuclei nucleate and grow. The rotated nuclei grow much faster. This difference suggests firstly, that the edge-orientation of the graphene sheets relative to the substrate plays an important role in the growth mechanism, and secondly, that attachment of the clusters to the graphene is the slowest step in cluster addition, rather than formation of clusters on the terraces.

On the classification of ideal secret sharing schemes

Abstract: In a secret sharing scheme a dealer has a secret key. There is a finite set P of participants and a set ? of subsets of P. A secret sharing scheme with ? as the access structure is a method which the dealer can use to distribute shares to each participant so that a subset of participants can determine the key if and only if that subset is in ?. The share of a participant is the information sent by the dealer in private to the participant. A secret sharing scheme is ideal if any subset of participants who can use their shares to determine any information about the key can in fact actually determine the key, and if the set of possible shares is the same as the set of possible keys. In this paper we show a relationship between ideal secret sharing schemes and matroids.