Reactions of d0 group 4 amides with dioxygen. Preparation of unusual oxo aminoxy complexes and theoretical studies of their formation

Reactions of d0 amides M(NMe2)4 (M = Zr, 1; Hf, 2) with O2 have been found to yield unusual trinuclear oxo aminoxide complexes M3(NMe2)6(mu-NMe2)3(mu3-O)(mu3-ONMe2) (M = Zr, 3; Hf, 4) in high yields. Tetramethylhydrazine Me2N-NMe2 was also observed in the reaction mixtures. Crystal structures of 3 and 4 have been determined. Density functional theory calculations have been performed to explore the mechanistic pathways in the reactions of model complexes Zr(NR2)4 (R = H, 5; Me, 1) and [Zr(NR2)4]2 (R = H, 5a; Me, 1a) with triplet O2. Monomeric and dimeric reaction pathways in the formation of the Zr complex 3 are proposed.     

183-W, M(2) = 2.4 Yb:YAG Q-switched laser

We have fabricated a diode-array end-pumped Yb:YAG rod laser with output powers greater than 200 W cw and 195 W Q -switched at 5 kHz. At an output power of 183 W and a repetition rate of 5 kHz, the beam quality was measured to be M(2)=2.4 . The laser design incorporates a hollow lens duct to concentrate the diode pump light for delivery to the end of the laser rod while maintaining access to the laser beam. This configuration provides increased flexibility for the resonator design and permits the use of birefringence compensation in the cavity to yield polarized output with increased efficiency. Using the recently described birefringence compensation method of Clarkson et al. [in Conference on Lasers and Electro-Optics (Optical Society of America, Washington, D.C., 1998), paper CTuI3], we obtained 112 W of cw power with a polarized beam of M(2)=3.2.     

Current-induced domain wall motion

The present understanding of domain wall motion induced by spin-polarized electric current is assessed by considering a subset of experiments, analytical models, and numerical simulations based on an important model system: soft magnetic nanowires. Examination of this work demonstrates notable progress in characterizing the experimental manifestations of the “spin-torque” interaction, and in describing that interaction at a phenomenological level. At the same time, an experimentally verified microscopic understanding of the basic mechanisms will require substantial future efforts, both experimental and theoretical.     

Carbon nanotube salts. Arylation of single-wall carbon nanotubes

[reaction: see text] Carbon nanotube salts prepared by treating single-wall carbon nanotubes (SWNTs) with lithium in liquid ammonia react readily with aryl iodides to give SWNTs functionalized by aryl groups.     

High-average-power diode-pumped femtosecond Cr:LiSAF lasers

Received: 27 February 1997/Revised version: 14 April 1997     

Tautomerization in gas-phase ion chemistry of isomeric C-8 deoxyguanosine adducts from phenol-induced DNA damage

Collision-induced dissociation (CID) of 8-(4'-hydroxyphenyl)-2'-deoxyguanosine and 8-(2'-hydroxyphenyl)-2'-deoxyguanosine was investigated using sequential tandem mass spectrometry. These adducts represent biomarkers of DNA damage linked to phenolic radicals and were investigated to gain insight into the effects of chemical structure of a C-8 modification on fragmentation pathways of modified 2'-deoxyguanosine (dG). CID in MS(2) of the deprotonated molecules of both the isomers generated the same product ion having the same m/z values. CID in MS(3) of the product ion at m/z 242 and CID in MS(4) experiments carried out on the selected product ions at m/z 225 and m/z 218 afford distinct fragmentation patterns. The conformational properties of isomeric product ions from CID showed that the ortho-isomers possess the unique ability to tautomerize through an intramolecular proton transfer between the phenolic OH group and the imine nitrogen (N7). Tautomerization of ortho-isomers to their keto-tautomers led to differences in their system of conjugated double bonds compared with either their enol-tautomer or the para-isomer. The charge redistribution through the N-7 site on the imidazole ring is a critical step in guanosine adduct fragmentation which is disrupted by the formation of the keto-tautomer. For this reason, different reaction pathways are observed for 8-(4'-hydroxyphenyl)-2'-deoxyguanosine and 8-(2'-hydroxyphenyl)-2'-deoxyguanosine. We present herein the dissociation and the gas-phase ion-molecule reactions for highly conjugated ions involved in the CID ion chemistry of the investigated adducts. These will be useful for those using tandem mass spectrometry for structural elucidation of C-8 modified dG adducts. This study demonstrates that the modification at the C-8 site of dG has the potential to significantly alter the reactivity of adducts. We also show the ability of tandem mass spectrometry to completely differentiate between the isomeric dG adducts investigated.