Synthesis and characterization of an air-stable gallium hydride, [t-Bu(H)Ga(mu-NEt(2))](2), and related chloride derivatives

The synthesis of [t-Bu(H)Ga(mu-NEt(2))](2) (1) was accomplished by the addition of 4 t-BuLi to [Cl(2)Ga(mu-NEt(2))](2). Evidence suggests that two tert-butyl groups are lost as isobutylene and result in Ga-H bond formation. The gallium hydride 1 is remarkably stable toward ambient air, oxygen, photolysis, and moderate heating; however, in CHCl(3) the hydride is replaced by chloride, producing [t-Bu(Cl)Ga(mu-NEt(2))](2) (2). Compound 1 may also be synthesized by sequential tert-butyl additions to [Cl(2)Ga(mu-NEt(2))](2). A singly substituted tert-butyl dimer, t-Bu(Cl)Ga(mu-NEt(2))(2)GaCl(2) (3), was also isolated, and interconversions between 1, 2, and 3 are described. Compound 1 was tested for utility in the chemical vapor deposition of GaN and produced gallium-rich films at low temperatures (<250 degrees C) with limited nitrogen incorporation due to facile Et(2)NH elimination.     

Osteoblast and Chrondrocyte Proliferation in the Presence of Alumina And Titania Nanoparticles

Proliferation of osteoblasts (bone-forming cells) and chondrocytes (cartilage-synthesizing cells) exposed to different sizes of alumina as well as titania particles at various concentrations (from 10,000 to 100g/ml of culture media) was investigated in the present in vitro study. Compared to respective conventional (i.e., micron) particle size ceramics, results provided the first evidence of increased osteoblast and chondrocyte proliferation in the presence of nanoparticles. Material characterization studies revealed that the only difference between respective ceramic particles was nano- and conventional-dimensions; specifically, phase, charge, and chemical properties were similar between different size alumina and titania particles, respectively. Thus, the present study provided the first evidence of a less detrimental effect of nano- as compared to conventional-dimension wear debris on cell function; such wear debris may result from friction between articulating components of orthopedic implants composed of novel nanophase ceramic materials. In this manner, results provided additional evidence to the literature that nanophase ceramics may become the next generation of bone prosthetic materials with improved osseointegrative (i.e., ability to bond to juxtaposed bone in situ) properties.     

Laser impulse coupling at 130 fs

We measured the momentum coupling coefficient C_m and laser-generated ion drift velocity and temperature in the femtosecond (fs) region, over a laser intensity range from ablation threshold to about one hundred times threshold. Targets were several pure metals and three organic compounds. The organic compounds were exothermic polymers specifically developed for the micro-laser plasma thruster, and two of these used “tuned absorbers” rather than carbon particles for laser absorption. The metals ranged from Li to W in atomic weight. We measured time of flight (TOF) profiles for ions. Specific impulse reached record values for this type of measurement and ablation efficiency was near 100%. These measurements extend the laser pulsewidth three orders of magnitude downward in pulsewidth relative to previous reports. Over this range, we found C_m to be essentially constant. Ion velocity ranged from 60 to 180 km/s.     

Horning-crown macrocycles: novel hybrids of calixarenes and crown ethers

[reaction: see text] Novel macrocycles possessing ether linkages and 2,6-disubstituted phenolics were produced in one step and with 100% atom economy by isoaromatization of chameleon macrocyclic precursors possessing 2,6-diarylidenecyclohexanone moieties. Intramolecular hydrogen bonding of the phenolic hydrogen atoms influenced the shape of the macrocycles and dictated host-guest behavior.     

Facile resolution of constrained geometry indenyl-phenoxide ligation

The 2-(inden-3-yl)phenoxide ligand can be resolved at both tetrahedral and octahedral Group 4 metal centers using chiral binaphthoxide ligands.     

Fingerprint IR spectroscopy to probe amino acid conformations in the gas phase

We report the infrared (IR) absorption spectra of different conformational isomers of gas phase amino acid molecules in the molecular fingerprint region of 330-1500 cm(-1). The IR absorption spectra for three conformers of the amino acid tryptophan show absorption bands that uniquely identify the conformational structure of the molecule and that are well matched by density functional theory calculations. The present observations hold great promise for future identification of conformational folding of larger molecules by means of their IR absorption characteristics.     

Superconductivity and field-induced magnetism in Pr2-xCexCuO4 single crystals

We report muon-spin rotation and relaxation (muSR) measurements on single crystals of the electron-doped high-T(c) superconductor Pr2-xCexCuO4. In a zero external magnetic field, superconductivity is found to coexist with dilute Cu spins that are static on the muSR time scale. In an applied field, we observe a mu(+)-Knight shift that is primarily due to the magnetic moment induced on the Pr ions. Below the superconducting transition temperature T(c), an additional source of local magnetic field appears throughout the volume of the sample. This finding is shown to be consistent with field-induced antiferromagnetic ordering of the Cu spins. Measurements of the temperature dependence of the in-plane magnetic penetration depth lambda(ab) in the vortex state are also presented.