Probing shapes of bichromophoric metal-organic complexes using ion mobility mass spectrometry

Ion mobility mass spectrometry (IM-MS) was used to probe the structures of several metal complexes carrying pendant chromophores. The three complexes investigated were the copper(II) complex Cu(DAC)2+ (DAC = 1,8-bis(9-methylanthracyl)cyclam, cyclam = 1,4,8,11-tetraazacyclotetradecane), the N-nitrosylated ligand DAC-NO, and the Roussin's red salt ester (mu-S,mu-S')-protoporphyrin-IX-bis(2-thioethyl ester)tetranitrosyldiiron (PPIX-RSE). From the IM-MS data coupled with theoretical calculations, it was found that [Cu(II)(DAC - H)]+ exists as a single conformer, with one anthracenyl group above the cyclam and the other below, similar to the crystal structure of Cu(II)(DAC)2+. The metal-free N-nitrosylated ligand (DAC-NO + H)+ has two conformations: one family of structures has one anthracenyl group above the cyclam and one below, while the other has both anthracenyl groups on the same side of the cyclam. These observations are consistent with 1H NMR data for the neutral DAC-NO complex that indicate the presence of two geometric isomers in solution. The third species, PPIX-RSE, has a porphyrin chromophore covalently linked to an Fe2S2(NO)4 cluster for use as a precursor for the photochemical delivery of nitric oxide in single- and two-photon excitation processes. Ion mobility indicates the presence of two (PPIX-RSE + H)+ conformations, consistent with the previous interpretation of the bimodal fluorescence lifetime decay seen for PPIX-RSE. DFT structures, in good agreement with the IM-MS cross sections, indicate two "bent" conformations with the planes of the porphyrin and Fe2S2 rings at different angles with respect to each other.     

Determination of the indirect band edge of GaAs by quantum-well bandfilling (Lz∼100Å)

Photoexcitation-bandfilling of a quantum-well Al_xGa_1?xAs-GaAs-Al_xGa_1?xAs (x～0.6, L_z～100Å) heterostructure is used to generate visible-red recombination radiation that cuts-off at high energy (1.864 eV, 4.2°K) due to electron transfer to indirect minima. This leads to an estimate of ΔE = E_L?E_Γ～310 meV.     

The growth of Al x Ga1−x As-GaAs heterostructure lasers by metalorganic chemical vapor deposition

Al _x Ga_1–x As-GaAs double-heterostructure lasers have been grown by the metalorganic chemical vapor deposition process. Conventional DH lasers have exhibited excellent performance characteristics that are equal to or better than comparable devices grown by liquid-phase epitaxy. Other unique laser structures have been grown that demonstrate the flexibility of the metalorganic chemical vapor deposition materials technology. This paper will describe the preparation and properties of Ga_1–x Al_xAs-GaAs lasers grown by this process.The author thanks J. J. Coleman, J. E. Cooper, L. L. Gray, R. G. Imerson, R. E., Johnson, F. F. Kinoshita, N. L. Lind, D. Medellin, L. A. Moudy, C. D. Sallee, and R. D. Yingling for assistance in the work described here. Helpful discussions with H. M. Manasevit and W. I. Simpson are greatly appreciated. The Auger profilling studies performed by C. M. Garner and T. J. Raab are gratefully acknowledged. The collaboration on quantum-well lasers with the research group of Prof. N. Holonyak, Jr. (University of Illinois at Urbana-Champaign) has been extremely beneficial. Discussions with and the support of P. D. Dapkus was essential to the achievement of the results described here. In addition, the support of J. E. Mee is greatly appreciated. This work has been partially supported by the Office of Naval Research under Contract N 00014-78-C-0711.     

Alkyl ketoximes as analytical reagents. XI

Summary The 4-heptanone oxime extraction procedure may be used for the quantitative separation of trace amounts of palladium from a noble-metals-bearing sulfide concentrate. An average palladium value of 0.335 oz/ton was obtained on a standard sample compared to the recommended value of 0.37 oz/ton.

---

Zusammenfassung Für die quantitative Abtrennung von Palladiumspuren aus einem edelmetallhaltigen Sulfidkonzentrat eignet sich die Extraktion mit 4-Heptanonoxim. In einer Standardprobe, deren Palladiumgehalt mit 0,37 Unzen/Tonne angegeben war, wurden durchschnittlich 0,335 Unzen/Tonne gefunden.

     

Thermochemistry of aqueous hydroxyl radical from advances in photoacoustic calorimetry and ab initio continuum solvation theory

Photoacoustic signals from dilute ( approximately 30 mM) solutions of H2O2 were measured over the temperature range from 10 to 45 degrees C to obtain the reaction enthalpy and volume change for H2O2(aq) --> 2 OH(aq) from which we ultimately determined DeltafG degrees , DeltafH degrees and partial molal volume, v degrees , of OH (aq). We find DeltarH = 46.8 +/- 1.4 kcal/mol, which is 4 kcal/mol smaller than the gas-phase bond energy, and DeltaVr = 6.5 +/- 0.4 mL/mol. The v degrees for OH in water is 14.4 +/- 0.4 mL/ml: smaller than the v degrees of water. Using ab intio continuum theory, the hydration free energy is calculated to be -3.9 +/- 0.3 kcal/mol (for standard states in number density concentration units) by a novel approach devised to capture in the definition of the solute cavity the strength and specific interactions of the solute with a water solvent molecule. The shape of the cavity is defined by "rolling" a three-dimensional electron density isocontour of water on the ab initio water-OH minimum interaction surface. The value of the contour is selected to reproduce the volume of OH in water. We obtain for OH(aq): DeltafH degrees = -0.2 +/- 1.4 and DeltafG degrees = 5.8 +/- 0.4 kcal/mol that are in agreement with literature values. The results provide confidence in the pulsed PAC technique for measuring aqueous thermochemistry of radicals and open the way to obtaining thermochemistry for most radicals that can be formed by reaction of OH with aqueous substrates while advancing the field of continuum solvation theory toward ab initio-defined solute cavities.     

Large deviations for small noise diffusions with discontinuous statistics

This paper proves the large deviation principle for a class of non-degenerate small noise diffusions with discontinuous drift and with state-dependent diffusion matrix. The proof is based on a variational representation for functionals of strong solutions of stochastic differential equations and on weak convergence methods. Received: 26 May 1998 / Revised version: 24 February 1999     

Experimental evidence for violation of the fluctuation-dissipation theorem in a superspin glass

We present the experimental observation of the fluctuation-dissipation theorem violation in an assembly of interacting magnetic nanoparticles in the low temperature superspin-glass phase. The magnetic noise is measured with a two-dimension electron gas Hall probe and compared to the out of phase ac susceptibility of the same ferrofluid. For "intermediate" aging times of the order of 1 h, the ratio of the effective temperature T(eff) to the bath temperature T grows from 1 to 6.5 when T is lowered from T(g) to 0.3 T(g), regardless of the noise frequency. These values are comparable to those measured in an atomic spin glass as well as those calculated for a Heisenberg spin glass.     

Ionic magnetic fluid based on cobalt ferrite nanoparticles: Influence of hydrothermal treatment on the nanoparticle size

Magnetic fluid based on cobalt ferrite nanoparticles was obtained using a hydrothermal treatment added to the Massart procedure. This treatment increases the average size of the nanoparticles from 11.9 to 18.7 nm and also improves the dispersity and crystallinity of the cobalt ferrite particles. The nanoparticles obtained after the hydrothermal treatment were dispersed in aqueous solvent by the classical procedure for ionic magnetic fluids. The ferrofluid thus obtained is stable at pH 7 and may be useful for hyperthermia applications.