Maximum radius of convergence perturbation theory: test calculations on Be,Ne, H<Subscript>2</Subscript> and HF

Maximum radius of convergence (MAXR _c) perturbation theory [(2000) Journal of Chemical Physics 112:6997] is tested on the beryllium and neon atoms using calculations that are truncated in high orders. Calculations are also performed on the ground-state potential-energy curves of H₂ and HF. The neon atom calculations use the 3-21G basis set with added diffuse s and p functions. All other calculations use the STO-3G minimum basis set. MAXR _c perturbation theory consistently performs well. The Epstein–Nesbet and Møller–Plesset perturbative expansions frequently diverge or exhibit slow convergence compared to the expansions obtained from MAXR _c. AcknowledgementsJ.P. Fi. acknowledges support for a grant from the Japanese Society for the Promotion of Science.Contribution to the Björn Roos Honorary Issue     

Identification of Photooxidation Sites in Bovine α-Crystallin

Abstract— Because UV irradiation of proteins can produce reactive oxygen species and exposure to UV light has been implicated in cataractogenesis, the sites of photooxidation of bovine α-crystallin, a major lens protein with molecular chaperone activity, were identified using tandem mass spectrometry (MS/MS). Bovine α-crystallin was irradiated with UV light (293 nm) for 1, 4 and 8 h, digested with trypsin and analyzed by matrix-assisted laser de-sorption ionization, time-of-flight mass spectrometry (MALDI) to identify the oxidized sequences. Tryptic peptides were purified by reverse-phase HPLC and oxidized peptides were sequenced by MS/MS to determine the sites of oxidation. Tryptophan fluorescence decreased exponentially with increasing time of UV exposure and peptides containing residues 1-11 of α-crystallin and 1-11, 12-22 and 57-69 of α-crystallin were determined to be oxidized by shifts of 16 D or multiples of 16 Da above the mass of the unmodified peptide. The MALDI analysis revealed single oxidation of all four sequences, which increased with increasing time of UV exposure and possible double oxidation of α 12-22. The specific sites of photooxidation indicate that the N-terminal regions of α-and β-crystallin are exposed to an aqueous environment and are in the vicinity of tryptophan residues from neighboring subunits.     

PHOTOCHEMICAL SENSITIZATION BY AZATHIOPRINE AND ITS METABOLITES—II. AZATHIOPRINE AND NITROIMIDAZOLE METABOLITES

Abstract— The photochemical reactivity of the immunosuppressant drug, azathioprine (AZT) and two representative metabolites of the nitroimidazole moiety, 1-methyl-4-nitroimidazole (MNI) and lmethyl-4-nitro-5-thioimidazole (MNTI) has been examined. No transient species of AZT were observed by laser flash photolysis, inferring a low triplet yield or its rapid deactivation. Consequently AZT, MNI and MNTI displayed little or no photodynamic sensitization via photooxidation reactions. However, AZT and MNI are highly reactive radical scavengers when photoexcited, as determined by reaction with polyacrylamide radicals. The photoreactivity of the metabolites of AZT is greater than that of the parent drug. an observation which may be relevant to the photocarcinogenicity of AZT.     

Direct observation of controlled coupling in an individual quantum dot molecule

We report the direct observation of quantum coupling in individual quantum dot molecules and its manipulation using static electric fields. A pronounced anticrossing of different excitonic transitions is observed as the electric field is tuned. A comparison of our experimental results with theory shows that the observed anticrossing occurs between excitons with predominant spatially direct and indirect character and reveals a field driven transition of the nature of the molecular ground state exciton wave function. Finally, the interdot quantum coupling strength is deduced optically and its dependence on the interdot separation is calculated.     

Multiple focal nodular hyperplasia syndrome: diagnosis with dynamic, gadolinium-enhanced MRI

We present a rare case of multiple focal nodular hyperplasia (FNH) with greater than 20 FNH lesions and coexistent liver hemangiomata. Particular attention is paid to the MRI characteristics of this disease process and the features of "multiple FNH syndrome" are discussed.     

Prolongations to higher jets of Estabrook-Wahlquist coverings for PDE's

Using a definition of the (infinite-dimensional) Lie algebras introduced by Estabrook and Wahlquist (EW) that lives directly on the jet bundle, we establish explicit methods to determine prolongations of these algebras to higher jet spaces, and calculate these prolongations for Burgers' equation and the KdV equation, to arbitrary level on the infinite jet bundle. Each level of prolongation introduces additional generator(s) of the algebra. For Burgers' equation, we first find the Kac-Moody algebra that is the (universal) completion of that algebra on the lowest-order jet space. We then show how each new generator creates a free flow of the lower-order algebra over the jet bundle, without requiring any new commutation relations. For the KdV equation, one new generator creates a flow, but the other introduces into the structure of the prolonged total derivative operators the characteristics for the hierarchy of conserved quantities of the PDE, thereby mixing together these nonlocal symmetries with the local ones in a way that may be valuable. In the limit to the infinite jet bundle, we acquire the EW algebra for the entire KdV hierarchy of PDE's, moving toward a comparison of this approach with the work of the Japanese school.     

Using the local density approximation and the LYP,BLYP and B3LYP functionals within reference-state one-particle density-matrix theory

For closed-shell systems, the local density approximation (LDA) and the LYP, BLYP and B3LYP functionals are shown to be compatible with reference-state one-particle density-matrix theory, where this recently introduced formalism is based on Brueckner-orbital theory and an energy functional that includes exact exchange and a non-universal correlation-energy functional. The method is demonstrated to reduce to a density functional theory when the exchange-correlation energy-functional has a simplified form, i.e. its integrand contains only the coordinates of two electrons, say r ₁ and r ₂, and it has a Dirac delta function δ(r ₁ - r ₂ as a factor. Since Brueckner and Hartree–Fock orbitals are often very similar, any local exchange functional that works well with Hartree–Fock theory is a reasonable approximation with reference-state one-particle density-matrix theory. The LDA approximation is also a reasonable approximation. However, the Colle–Salvetti correlation-energy functional and the LYP variant are not ideal for the method, since these are universal functionals. Nevertheless, they appear to provide reasonable approximations. The B3LYP functional is derived using a linear combination of two functionals: one is the BLYP functional; the other uses exact exchange and a correlation-energy functional from the LDA.