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91.
We have computed vibrational high-frequency overtone spectra of the water-ammonia complex, H(2)O-NH(3), and its isotopomers. The complex has been modeled as two independently vibrating monomer units. The internal coordinate Hamiltonians for each monomer unit have been constructed using exact gas phase kinetic energy operators. The potential energy and dipole moment surfaces have been calculated with the explicitly correlated coupled cluster method CCSD(T)-F12A and the valence triple-ζ VTZ-F12 basis around the equilibrium geometry of the complex. The vibrational eigenvalues have been calculated variationally and the eigenfunctions obtained have been used to compute the intensities of the absorption transitions. In H(2)O-NH(3), the water molecule acts as the proton donor and its symmetry is broken. The hydrogen-bonded OH bond oscillator undergoes a large redshift and intensity enhancement compared to the free hydrogen bond. Broken degeneracy of the asymmetric vibrations, quenched inversion splittings, and blueshift of the symmetric bending mode are the most visible changes in the ammonia unit. 相似文献
92.
Elina Manova Daniela Paneva Nikolay Velinov Krassimir Tenchev 《Journal of solid state chemistry》2011,184(5):1153-1158
Nanodimensional powders of cubic copper ferrite are synthesized by two-steps procedure of co-precipitation of copper and iron hydroxide carbonates, followed by mechanochemical treatment. X-ray powder diffraction, Mössbauer spectroscopy and temperature-programmed reduction are used for the characterization of the obtained materials. Their catalytic behavior is tested in methanol decomposition to hydrogen and CO and total oxidation of toluene. Formation of nanosized ferrite material is registered even after one hour of milling time. It is established that the prolonging of treatment procedure decreases the dispersion of the obtained product with the appearance of Fe2O3. It is demonstrated that the catalytic behavior of the samples depends not only on their initial phase composition, but on the concomitant ferrite phase transformations by the influence of the reaction medium. 相似文献
93.
Abstract: Steroids are an important class of organic compounds containing a vast array of biologically and physiologically essential molecules. Due to their availability, relatively straightforward derivatizability, and endogeneity, they are widely used in pharmacological applications. The investigation of molecular and physicochemical properties of active pharmaceutical ingredients (APIs) in the solid state is important, because these properties are directly related to their pharmacological activity. Several methods are available for this purpose. Solid-state NMR spectroscopy offers a nondestructive and flexible technique, providing both structural and dynamic information. It can be applied to every solid physical state (both crystalline and amorphous) as well as to materials with different compositions. The current article aims at gathering together some of the recent and most important studies in the area of high-resolution solid-state NMR spectroscopy of steroids and their derivatives completed with related theoretical reports not forgetting to outline the future remarks. 相似文献
94.
Antti J. Koivisto Maija M?kinen Elina M. Rossi Hanna K. Lindberg Mirella Miettinen Ghita C.- M. Falck Hannu Norppa Harri Alenius Anne Korpi Joakim Riikonen Esa Vanhala Minnamari Vippola Pertti Pasanen Vesa-Pekka Lehto Kai Savolainen Jorma Jokiniemi Kaarle H?meri 《Journal of nanoparticle research》2011,13(7):2949-2961
This study presents a novel exposure protocol for synthesized nanoparticles (NPs). NPs were synthesized in gas phase by thermal decomposition of metal alkoxide vapors in a laminar flow reactor. The exposure protocol was used to estimate the deposition fraction of titanium dioxide (TiO2) NPs to mice lung. The experiments were conducted at aerosol mass concentrations of 0.8, 7.2, 10.0, and 28.5 mg m?3. The means of aerosol geometric mobility diameter and aerodynamic diameter were 80 and 124 nm, and the geometric standard deviations were 1.8 and 1.7, respectively. The effective density of the particles was approximately from 1.5 to 1.7 g cm?3. Particle concentration varied from 4 × 105 cm?3 at mass concentrations of 0.8 mg m?3 to 12 × 106 cm?3 at 28.5 mg m?3. Particle phase structures were 74% of anatase and 26% of brookite with respective crystallite sized of 41 and 6 nm. The brookite crystallites were approximately 100 times the size of the anatase crystallites. The TiO2 particles were porous and highly agglomerated, with a mean primary particle size of 21 nm. The specific surface area of TiO2 powder was 61 m2 g?1. We defined mice respiratory minute volume (RMV) value during exposure to TiO2 aerosol. Both TiO2 particulate matter and gaseous by-products affected respiratory parameters. The RMV values were used to quantify the deposition fraction of TiO2 matter by using two different methods. According to individual samples, the deposition fraction was 8% on an average, and when defined from aerosol mass concentration series, it was 7%. These results show that the exposure protocol can be used to study toxicological effects of synthesized NPs. 相似文献
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98.
Susan Kunnas‐Hiltunen Elina Laurila Matti Haukka Jouko Vepsäläinen Markku Ahlgrén 《无机化学与普通化学杂志》2010,636(5):710-720
Four new cobalt, manganese, and copper bis(phosphonates), [Co2{Cl2C(PO3)2}(H2O)7 · 4H2O] ( 1 ), [Co{Cl2C(PO2O(C(O)C6H5))2(H2O)5} · 2H2O{Cl2C(PO2O(C(O)C6H5))2}{Co(H2O)6}] ( 2 ), [Mn{[Cl2C(PO2O(C(O)C6H5))2](H2O)3}] ( 3 ), and [Cu{(CH2C5H5N)C(OH)(PO3H)2}2 · 4H2O] ( 4 ), were prepared by gel, liquid, and evaporation crystallisation methods. Compounds 1 – 4 were characterised by X‐ray single‐crystal diffraction, elemental analysis, infrared spectroscopy, and thermogravimetric analysis. The effects of metal and various substituted groups in bis(phosphonate) ligands on the structure formation of bis(phosphonates) were studied. In the structure of 1 , the clodronic acid ligand ( L1 ) is in bischelating bonding mode, and the dinuclear units of 1 are surrounded by two‐dimensional water cluster patterns. The hydrogen bond network of compound 1 is extended to a three‐dimensional framework when the phosphonate oxygen atoms serve as hydrogen‐bond acceptors. In complex 2 , the CoO6 octahedron shares a corner of one PCO3 tetrahedron of the dibenzoyl derivative of clodronic acid ligand ( L2 ), and forms a two‐dimensional hydrogen bonding network, which consists of [Co(H2O)6}]2+ cations, lattice water molecules and L2 ligand molecules. Compound 3 , in turn, consists of dimeric building blocks built up of PCO3 tetrahedra of the ligand L2 , which connect the corner‐sharing MnO6 octahedra and form an overall 2D structure through hydrogen bonds of coordinated and crystal water molecules and phosphonate oxygen atoms. Complex 4 is among the first metal complexes of risedronic acid ( L3 ). In compound 4 , two L3 ligand molecules chelate tridentately the CuII atom at the center of symmetry, and the monomeric units of 4 are connected to a 3D structure through hydrogen bonding of coordinated and lattice water molecules to both protonated and deprotonated phosphonate oxygen atoms and protonated nitrogen atoms in the pyridine ring. 相似文献
99.
Ventola E Hyyryläinen A Vainiotalo P 《Rapid communications in mass spectrometry : RCM》2006,20(8):1218-1224
Noncovalent complex formation between a tetramesityl sulfonated tetramethyl resorcarene and primary, secondary, and tertiary alkylammonium ions was investigated by electrospray ionization (ESI) Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Competition measurements, collision-induced dissociation, and gas-phase hydrogen/deuterium (H/D)-exchange reactions were employed to elucidate the interactions involved in complexation, the stability of the complexes, and the position of the guest with relation to the resorcarene. The complex formation ability of tetramesityl sulfonated resorcarene and the stability of the compexes were compared with the corresponding properties of tetratosylium tetraethyl resorcarene, which has been studied previously. Complex formation and the properties of the complexes were most strongly determined by the steric properties of the guests and their ability to form hydrogen bonds. Comparison of the two host molecules revealed the impact of steric hindrance in tetramesityl sulfonated tetramethyl resorcarene. 相似文献
100.
When di-N-oxides of -hydroxymethyl derivatives of quinoxaline are heated with dimethyl sulfoxide, the oxidation of a CH2OH group and the reduction of a neighboring NO group takes place. The N-oxides of 2,3-bis(hydroxymethyl)qninoxaline undergo similar redox processes in the presence of alkaline reagents.For part XV, see [5]. 相似文献