Cluster Build-up Reactions using Di-gold Cationic Fragments: Synthesis and Structural Characterization of [Os7(CO)19(Au2dppm)]

The reaction of the di-gold cation [Au₂(dppx)]²⁺ with the heptanuclear cluster dianion [Os₇(CO)₂₀]^2– affords the mixed metal cluster [Os₇(CO)₂₀{Au₂(dppx)}] (x=m (1), e (2), b (3)). On standing, in solution, this complex undergoes decarbonylation to give the cluster [Os₇(CO)₁₉{Au₂(dppx)}] (x=m (4), e (5), b (6)). The complexes have been characterised spectroscopically, and an X-ray structure determination of the dppm derivative shows that it contains a metal core based on an Os₇ edge-bridged bicapped tetrahedron with the two ₃-Au atoms capping adjacent triangular Os₃ faces of the central tetrahedron. In an analogous reaction, the carbido anion [Os₇(H)C(CO)₁₉]^– affords the neutral cluster [Os₇C(CO)₁₉{Au₂(dppm)}] (7) when treated with [Au₂(dppm)]²⁺ in the presence of base.     

Doubly-charged ethane ions: Solution to the dilemma of stability predicted by theory and instability observed in experiment

Potential energy curves have been computed for [C₂H₆]²⁺ ions and the results used to interpret the conspicuous absence of these ions in 2E mass spectra and in charge-stripping experiments. The energies and structures of geometry-optimized ground-state singlet and excited-state triplet [C₂H₆]²⁺ ions have been determined along with energies for different decomposition barriers and dissociation asymptotes. Although singlet and triplet [C₂H₆]²⁺ ions can exist as stable entities, they possess low energy barriers to decomposition. Vertical Franck-Condon transitions, involving electron impact ionization of ethane as well as charge-stripping collisions of [C₂H₆]⁺ ions, produce [C₂H₆]²⁺ ions which promptly dissociate since they are formed with energies in excess of various decomposition barriers. Appearance energies computed for doubly-charged ethane fragment ions are in accordance with experimental values.     

Radioimmunoassay of PCBs in Milk and Blood

A radioimmunoassay was developed capable of determining Aroclor 1260 in milk at levels of from 20 to 80 ppb and in blood from 2 to 16 ppb. The values obtained by radioimmunoassay correlate well with those determined by gas-liquid chromatography (r² = 0.96 for milk and 0.99 for blood) but were lower. Antiserum was produced in rabbits and was specific for 2, 2′, 4, 4′, 5, 5′-hexachlorobiphenyl. It cross-reacted with congeners and isomers in Aroclor 1254 and 1260 to the extent that a 20% decrease in binding was observed with 0.1 ng of either mixture. The method requires preliminary cleanup of the extract on alumina and utilizes 25 % dimethyl sulfoxide in the assay medium to promote solubilization of the substrates.     

Nucleation and Growth Synthesis of Siloxane Gels to Form Functional,Monodisperse, and Acoustically Programmable Particles

Nucleation and growth methods offer scalable means of synthesizing colloidal particles with precisely specified size for applications in chemical research, industry, and medicine. These methods have been used to prepare a class of silicone gel particles that display a range of programmable properties and narrow size distributions. The acoustic contrast factor of these particles in water is estimated and can be tuned such that the particles undergo acoustophoresis to either the pressure nodes or antinodes of acoustic standing waves. These particles can be synthesized to display surface functional groups that can be covalently modified for a range of bioanalytical and acoustophoretic sorting applications.     

Hydrogen Bond Cooperativity and the Three‐Dimensional Structures of Water Nonamers and Decamers

Broadband rotational spectroscopy of water clusters produced in a pulsed molecular jet expansion has been used to determine the oxygen atom geometry in three isomers of the nonamer and two isomers of the decamer. The isomers for each cluster size have the same nominal geometry but differ in the arrangement of their hydrogen bond networks. The nearest neighbor O? O distances show a characteristic pattern for each hydrogen bond network isomer that is caused by three‐body effects that produce cooperative hydrogen bonding. The observed structures are the lowest energy cluster geometries identified by quantum chemistry and the experimental and theoretical O? O distances are in good agreement. The cooperativity effects revealed by the hydrogen bond O? O distance variations are shown to be consistent with a simple model for hydrogen bonding in water that takes into account the cooperative and anticooperative bonding effects of nearby water molecules.     

Origin of the oscillator strength of the triplet state of a trion in a magnetic field

The dynamics of the spin-triplet trion state, under high magnetic field in a GaAs/AlGaAs quantum well, are studied using time resolved spectroscopy. The oscillator strength of the triplet transition is shown to rise with increasing electron density, in good agreement with a theoretical model where the trion interacts with excess electrons in the quantum well. This analysis suggests that the spin-triplet trion state, which is expected to be an optically "dark" state, is experimentally observable due to the interactions with the excess electrons, demonstrating that X- cannot be regarded as an isolated three particle complex.     

A determination of the Cabibbo-Kobayashi-Maskawa parameter |V us| using KL decays

We present a determination of the Cabibbo-Kobayashi-Maskawa parameter |V(us)| based on new measurements of the six largest K(L) branching fractions and semileptonic form factors by the KTeV (E832) experiment at Fermilab. We find |V(us)|=0.2252+/-0.0008(KTeV)+/-0.0021(ext), where the errors are from KTeV measurements and from external sources. We also use the measured branching fractions to determine the CP violation parameter |eta(+-)|=(2.228+/-0.005(KTeV)+/-0.009(ext))x10(-3).