Crystallization of Arthrobacter sp. strain 1C N-(1-D-carboxyethyl)-L-norvaline dehydrogenase and its complex with NAD+

The novel NAD+-linked opine dehydrogenase from a soil isolate Arthrobacter sp. strain 1C belongs to an enzyme superfamily whose members exhibit quite diverse substrate specificites. Crystals of this opine dehydrogenase, obtained in the presence or absence of co-factor and substrates, have been shown to diffract to beyond 1.8 ? resolution. X-ray precession photographs have established that the crystals belong to space group P21212, with cell parameters a = 104.9, b = 80.0, c = 45.5 ? and a single subunit in the asymmetric unit. The elucidation of the three-dimensional structure of this enzyme will provide a structural framework for this novel class of dehydrogenases to enable a comparison to be made with other enzyme families and also as the basis for mutagenesis experiments directed towards the production of natural and synthetic opine-type compounds containing two chiral centres.     

Isolation and Crystallographic Characterization of Two,Nonisolated Pentagon Endohedral Fullerenes: Ho3N@C2(22010)-C78 and Tb3N@C2(22010)-C78

Purified samples of Ho₃N@C₂(22010)-C₇₈ and Tb₃N@C₂(22010)-C₇₈ have been isolated by two distinct processes from the rich array of fullerenes and endohedral fullerenes present in carbon soot from graphite rods doped with Ho₂O₃ or Tb₄O₇. Crystallographic analysis of the endohedral fullerenes as cocrystals with Ni(OEP) (in which OEP is the dianion of octaethylporphyrin) shows that both molecules contain the chiral C₂(22010)-C₇₈ cage. This cage does not obey the isolated pentagon rule (IPR) but has two sites where two pentagons share a common C−C bond. These pentalene units bind two of the metal ions, whereas the third metal resides near a hexagon of the cage. Inside the cages, the Ho₃N or Tb₃N unit is planar. Ho₃N@C₂(22010)-C₇₈ and Tb₃N@C₂(22010)-C₇₈ use the same cage previously found for Gd₃N@C₂(22010)-C₇₈ rather than the IPR-obeying cage found in Sc₃N@D_3h-C₇₈.     

Study of Nb2O(y) (y = 2-5) anion and neutral clusters using anion photoelectron spectroscopy and density functional theory calculations

A study combining anion photoelectron spectroscopy and density functional theory calculations on the transition metal suboxide series, Nb(2)O(y)(-) (y = 2-5), is described. Photoelectron spectra of the clusters are obtained, and Franck-Condon simulations using calculated anion and neutral structures and frequencies are used to evaluate the calculations and assign transitions observed in the spectra. The spectra, several of which exhibit partially resolved vibrational structure, show an increase in electron affinity with increasing cluster oxidation state. Hole-burning experiments suggest that the photoelectron spectra of both Nb(2)O(2)(-) and Nb(2)O(3)(-) have contributions from more than one structural isomer. Reasonable agreement between experiment and computational results is found among all oxides.     

Computable error bounds for pointwise derivatives of a Neumann problem

In this paper we discuss the recovery of derivatives and thecomputation of rigorous and useful upper bounds for the pointwiseerror in the recovered derivatives, for finite element approximationsof the Laplace equation with Neumann boundary conditions, especiallyat points close to or on a smooth, curved boundary. We analyzethe dipole image technique for the case of curved boundaries,and show how to compute reliable recovered derivatives and errorbounds even in the limiting case of points lying on the curvedboundary. Numerical experiments show reasonably tight errorbounds for points both close to and away from a curved boundary.     

Structures of trimetallic molybdenum and tungsten suboxide cluster anions

Anion photoelectron spectra of Mo(3)O(y)(-) and W(3)O(y)(-) (y = 3-6) are reported and analyzed using density functional theory results in an attempt to determine whether electronic and structural trends in the less oxidized clusters (y = 3, 4) could elucidate the disparate chemical properties of the M(3)O(y)(-) (M = Mo, W, y = 5, 6) species. In general, cyclic structures are calculated to be more stable by at least 1 eV than extended structures, and the lowest energy structures calculated for the most reduced species favor M = O terminal bonds. While the numerous low-energy structures found for Mo(3)O(y)(-)/Mo(3)O(y) and W(3)O(y)(-)/W(3)O(y) were, in general, similar, various structures of W(3)O(y)(-)/W(3)O(y) were found to be energetically closer lying than analogous structures of Mo(3)O(y)(-)/Mo(3)O(y). Additionally, the Mo-O-Mo bridge bond was found to be a more stabilizing structural motif than the W-O-W bridge bond, with the oxygen center in the former having the highest negative charge. Based on this, the observation of trapped intermediates in reactions between Mo(3)O(y)(-) and water or CO(2) that are not observed in analogous W(3)O(y)(-) reactivity studies may be partially attributed to the role of bridge bond fluxionality.     

An instrumented fastener for shear force measurements in joints

A preliminary investigation has been conducted on instrumented fasteners for use as sensors to measure the shear loads transmitted by individual fasteners installed in double-splice joints. Calibration and load verification tests were conducted for instrumented fasteners installed at three fastener torque levels. Results from calibration tests show that the shear strains obtained from the instrumented fasteners vary linearly with the applied load and that the instrumented fasteners can be effectively used to measure shear loads transmitted by individual fasteners installed in double-splice joints. Tests were also conducted with three instrumented fasteners installed in a typical double-splice joint. The test results showed that the load distribution between individual fasteners is dependent on the location of the fastener in the joint and the fastener torque level. The fastener located near the end of the joint with the single plate carried more load than the fasteners located near the end of the joint with the two plates. Installing the fasteners with a torque greater than finger tight results in a significant amount of the load being carried by friction between the faying surfaces of the plates even if the faying surfaces are polished and lubricated. Increasing the fastener torque increases the load being carried by friction between the faying surfaces of the joint. Increasing friction between the faying surfaces of the joint. Increasing the fastener torque also results in a more uniform distribution of the loads between the individual fasteners for joints in aluminum plates with two fasteners, but does not have a significant effect for joints in steel plates with three fasteners. Paper was presented at the 1992 SEM Spring Conference on Experimental Mechanics held in Las Vegas, NV on June 8–11.     

Solvation of O(2)(-) and O(4)(-) by p-difluorobenzene and p-xylene studied by photoelectron spectroscopy

Anion photoelectron spectra of the O(2)(-) . arene and O(4)(-) . arene complexes with p-xylene and p-difluorobenzene are presented and analyzed with the aid of calculations on the anions and corresponding neutrals. Relative to the adiabatic electron affinity of O(2), the O(2)(-) . arene spectra are blueshifted by 0.75-1 eV. Solvation energy alone does not account for this shift, and it is proposed that a repulsive portion of the neutral potential energy surface is accessed in the detachment, resulting in dissociative photodetachment. O(2)(-) is found to interact more strongly with the p-difluorobenzene than the p-xylene. The binding motif involves the O(2)(-) in plane with the arene, interacting via electron donation along nearby C-H bonds. A peak found at 4.36(2) eV in the photoelectron spectrum of O(2)(-) . p-difluorobenzene (p-DFB) is tentatively attributed to the charge transfer state, O(2)(-) . p-DFB(+). Spectra of O(4)(-) . arene complexes show less blueshift in electron binding energy relative to the spectrum of bare O(4)(-), which itself undergoes dissociative photodetachment. The striking similarity between the profiles of the O(4)(-) . arene complexes with the O(4)(-) spectrum suggests that the O(4)(-) molecule remains intact upon complex formation, and delocalization of the charge across the O(4)(-) molecule results in similar structures for the anion and neutral complexes.