Measurements of L-shell X-ray emission lines of neonlike europium on an electron beam ion trap

We report a measurement of the two X-ray transitions that proceed from the and (1s²2s_1/22p⁶3p_1/2)_{J = 1} upper levels to the (1s²2s²2p⁶)_{J = 0} ground level in neonlike Eu⁵³⁺ (Z = 63), that is,  near the previously documented avoided crossing of the two upper levels at Z = 68. The measurement was carried out using the calorimeter spectrometer on the Livermore EBIT-I electron beam ion trap. It affirms the trends set by the neighboring neonlike ions both in terms of the relative intensity of the two lines and in terms of the magnitude of disagreement with theoretical energy level predictions.     

A pointwise quasi-Newton method for unconstrained optimal control problems

Summary For a class of unconstrained optimal control problems we propose a quasi-Newton method that exploits the structure of the problem. We define a new type of superlinear convergence for sequences in function spaces and prove superlinear convergence of the iterates generated by the quasi-Newton method in this sense.This author supported by NSF grants # DMS-8300841 and # DMS-8500844     

Synthesis and spectroelectrochemistry of Ir(bpy)(phen)(phi)(3+), a tris(heteroleptic) metallointercalator

A tris(heteroleptic) phenanthrenequinone diimine (phi) complex of Ir(III), Ir(bpy)(phen)(phi)(3+), was synthesized through the stepwise introduction of three different bidentate ligands, and the Lambda- and Delta-enantiomers were resolved and characterized by CD spectroscopy. Like other phi complexes, this tris(heteroleptic) iridium complex binds avidly to DNA by intercalation. Electrochemical studies show that Ir(bpy)(phen)(phi)(3+) undergoes a reversible one-electron reduction at E(0) = -0.025 V in 0.1 M TBAH/DMF (versus Ag/AgCl), and spectroelectrochemical studies indicate that this reduction is centered on the phi ligand. The EPR spectrum of electrochemically generated Ir(bpy)(phen)(phi)(2+) is consistent with a phi-based radical. The electrochemistry of Ir(bpy)(phen)(phi)(3+) was also probed at a DNA-modified electrode, where a DNA binding affinity of K = 1.1 x 10(6) M(-1) was measured. In contrast to Ir(bpy)(phen)(phi)(3+) free in solution, the complex bound to DNA undergoes a concerted two-electron reduction, to form a diradical species. On the basis of UV-visible and EPR spectroscopies, it is found that disproportionation of electrochemically generated Ir(bpy)(phen)(phi)(2+) occurs upon DNA binding. These results underscore the rich redox chemistry associated with metallointercalators bound to DNA.     

Synthesis and antimicrobial testing of 2-amino-6-hydroxymethyl-4-(3H)pyrido[3,2-d]pyrimidinone

Synthesis of 2-amino-6-hydroxymethyl-4-(3H)pyrido[3,2-d]pyrimidinone ( 5 ) from 2-amino-6-methyl-4-(3H)-pyrido[3,2-d]pyrimidinone ( 2 ) was accomplished by selenium dioxide oxidation of 2 to the aldehyde 4 followed by sodium borohydride reduction. Compound 2 was available in four steps from 5-aminouracil or in two steps from 5-nitroisocytosine ( 3a ). Catalytic reduction of 4 or 5 gave a mixture of 2-amino-6-methyl-5,6,7,8-tetrahydro-4-(3H)pyrido[3,2-d]pyrimidinone ( 6a ) and the 6-hydroxymethyl compound 6b . These compounds showed only weak inhibitory activity in the coupled reactions catalyzed by 7,8-dihydro-6-hydroxymethylpterin pyrophosphokinase and 7,8-dihydropteroate synthetase from E. Coli. No significant antibacterial activity was observed.     

The spectroscopy of InSe nanoparticles

The synthesis of several different sizes of InSe nanoparticles from organometallic precursors is reported. These particles are characterized by transmission electron microscopy, electron diffraction, and optical spectroscopy. The electron diffraction results and optical properties indicate that these particles are two-dimensional disks, consisting of single Se-In-In-Se tetralayer sheets. The absorption spectra indicate strong quantum confinement along the z axis and, for the smaller particles, in the x,y plane. The z-axis quantum confinement may be quantitatively understood in terms of the band structure of bulk InSe. The results indicate that the z-axis quantum confinement reverses the order of the direct and indirect transitions in the case of the largest particles. The smaller particles exhibit strong, polarized fluorescence, and the fluorescence polarization may also be understood in terms of the band structure of bulk InSe.