Molecular beam measurements and Monte Carlo simulations of the kinetics of N2O decomposition on Rh(111) single-crystal surfaces

The kinetics of N2O decomposition on Rh(111) single-crystal surfaces were investigated both experimentally by isothermal molecular beam measurements and theoretically using a Monte Carlo algorithm. The present work was directed to the understanding of two unusual observations derived from our previous work on this system, namely, (1) the lower rates for N2O decomposition seen at higher reaction temperatures, and (2) the lower total nitrogen yields and final oxygen surface coverages that accompany that behavior. Experimentally, it was determined here that after the rhodium surface is rendered inactive by N2O decomposition at high (520 K) temperatures, significant activity is still possible at lower (350 K) temperatures. The Monte Carlo simulations explain these observations by assuming that the surface sites required for the activation of adsorbed N2O increase in size with increasing reaction temperature.     

Investigation of intramolecular proton migration in a series of model, metal-cationized tripeptides using in situ generation of an isotope label

In this study we used an isotope label, generated in situ, to investigate intramolecular proton migration or scrambling during formation of [b(2)+17+Li](+) products by collision-induced dissociation (CID) of Li(+)-cationized tripeptides. To generate the isotope label, we used a McLafferty-type rearrangement of N-terminally acetylated, C-terminal peptide tert-butyl esters in which all amide positions were exchanged with deuterium. Using a set of small, model peptides, we show that intramolecular proton scrambling occurs during CID, particularly amongst adjacent sites along a peptide backbone, on the time scales employed for low-energy collisional activation in an ion-trap mass spectrometer.     

Comparison of various detection limit estimates for volatile sulphur compounds by gas chromatography with pulsed flame photometric detection

This paper addresses the variations that presently exist regarding the definition, determination, and reporting of detection limits for volatile sulphur compounds by gas chromatography with pulsed flame photometric detection (GC-PFPD). Gas standards containing hydrogen sulphide (H(2)S), carbonyl sulphide (COS), sulphur dioxide (SO(2)), methyl mercaptan (CH(3)SH), dimethyl sulphide (DMS), carbon disulphide (CS(2)), and dimethyl disulphide (DMDS) in concentrations varying from 0.36ppb (v/v) up to 1.5ppm (v/v) in nitrogen were prepared with permeation tubes and introduced in the gas chromatograph using a 0.25-ml gas sampling loop. After measuring the PFPD response versus concentration, the method detection limit (MDL), the Hubaux-Vos detection limit (x(D)), the absolute instrument sensitivity (AIS), and the sulphur detectivity (D(s)) were determined for each sulphur compound. The results show that the MDL determined by the US Environmental Protection Agency procedure consistently underestimates the minimum concentrations of volatile sulphur compounds that can be practically distinguished from the background noise with the PFPD. The Hubaux-Vos detection limits and the AIS values are several times higher than the MDL, and provide more conservative estimates of the lowest concentrations that can be reliably detected. Sulphur detectivities are well correlated with AIS values but only poorly correlated with MDL values. The AIS is recommended as a reliable and cost-effective measure of detection limit for volatile sulphur compounds by GC-PFPD, since the AIS is easier and faster to determine than the MDL and the Hubaux-Vos detection limit. In addition, this study confirmed that the PFPD response is nearly quadratic with respect to concentration for all volatile sulphur compounds.     

Modeling of ligation-induced helix/loop displacements in myoglobin: toward an understanding of hemoglobin allostery

Combining quantum and molecular mechanics (QM/MM) methods and protein structure prediction algorithms, helix and loop movements are computed along the pathway of CO dissociation from myoglobin (Mb). The results are compared with high-resolution crystallographic data using sequence-displacement graphs. These graphs provide an unbiased method for evaluating main-chain segmental motions; they resolve an apparent disagreement between two sets of high-resolution crystal structures for MbCO and deoxyMb. The QM/MM modeling of the CO deligation reproduces the experimentally observed spin states and photodissociated crystal structure. The principal effect of CO dissociation is shown to be a concerted rotation of the E and F helices, which hold the heme like a clamshell. The rotation is a response to deligation forces, which impel the F helix away from the heme because of the Fe spin conversion, and which allow the E helix to collapse toward the heme as nonbonded contacts on the distal side are relieved. Additional helix and loop displacements stem from these primary events. In particular, the CD loop is found to be repositioned as a result of steric interactions with the water molecule that becomes H-bonded to the distal histidine in deoxyMb. A similar EF rotation and CD loop displacement are proposed to be the first steps along the allosteric pathway from the R to the T state in hemoglobin.     

Synthesis of silica-gold nanocomposites and their porous nanoparticles by an in-situ approach

We demonstrate the one-step synthesis of a silica-gold nanocomposite by simultaneous hydrolysis and reduction of gold chloride. The aminophenyl group was used as a reducing agent, and the trimethoxy silane group acts a precursor for the formation of silica. The porous gold nanoparticles were formed by etching out the silica-gold nanocomposite by hydrofluoric acid. The electron diffraction of porous gold nanoparticles showed that the particle are polycrystalline with FCC structure. The silica-gold nanocomposite exhibited nonlinear current-voltage behavior, and the porous gold nanoparticles displayed linear current-voltage behavior.     

Surface properties of inclusion complexes between alpha-cyclodextrin and poly(ethylene oxide)

The surface properties of the supramolecular inclusion complex (IC) obtained from the threading of alpha-cyclodextrin (alpha-CD) onto poly(ethylene oxide) (PEO) free in solution are studied. The complexes were characterized by IR, (1)H NMR spectroscopy, and thermal analysis. The variation of the interfacial tension, gamma(int), with inclusion complex (IC) concentration and temperature were determined. The results were compared with those found for PEO under the same conditions. alpha-CD does not present surface activity. To quantify the adsorption process of IC and PEO in aqueous medium, the Gibbs equation was used. The driving force for adsorption of IC at the air/aqueous interface seems to arise from an enthalpic contribution. The wettability of the alpha-CD, PEO, and IC films with two liquids was determined by static contact angle measurements. The hydrophobicity degree was estimated. IC is more hydrophobic than PEO and alpha-CD.     

Synthesis, characterization, and solution properties of a novel cross-bridged cyclam manganese(IV) complex having two terminal hydroxo ligands

A novel monomeric tetravalent manganese complex with the cross-bridged cyclam ligand 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (Me2EBC), [Mn(IV)(Me2EBC)(OH)2](PF6)2, was synthesized by oxidation of Mn(II)(Me2EBC)Cl2 with H2O2 in the presence of NH4PF6)in aqueous solution. The X-ray crystal structure determination of this manganese(IV) compound revealed that it contains two rare terminal hydroxo ligands. EPR studies in dry acetonitrile at 77 K show two broad resonances at g = 1.96 and 3.41, indicating that the manganese(IV) exists as a high-spin d3 species. Resonance Raman (rR) spectra of this manganese(IV) species reveal that the dihydroxy moiety, Mn(IV)(OH)2, is also the dominant species in aqueous solution (pH < 7). pH titration provides two pK(a) values, 6.86(4) and 10.0(1), associated with stepwise removal of the last two oxygen-bound protons from [Mn(IV)(Me2EBC)(OH)2](2+). The cyclic voltammetry of this manganese(IV) complex in dry acetonitrile at 298 K demonstrates two reversible redox processes at +0.756 and -0.696 V (versus SHE) for the Mn4+/Mn3+ and Mn3+/Mn2+ couples, respectively. This manganese(IV) complex is relatively stable in weak acidic aqueous solution but easily degrades in basic solution to manganese(III) derivatives with an 88 +/- 1% yield.     

The origin of chemo- and enantioselectivity in the hydrogenation of diketones on platinum

In the Pt-catalyzed hydrogenation of 1,1,1-trifluoro-2,4-diketones, addition of trace amounts of cinchonidine, O-methyl-cinchonidine, or (R,R)-pantoyl-naphthylethylamine induces up to 93% ee and enhances the chemoselectivity up to 100% in the hydrogenation of the activated carbonyl group to an OH function. A combined catalytic, NMR and FTIR spectroscopic, and theoretical study revealed that the two phenomena are coupled, offering the unique possibility for understanding the substrate-modifier-metal interactions. The high chemo- and enantioselectivities are attributed to the formation of an ion pair involving the protonated amine function of the chiral modifier and the enolate form of the substrate. DFT calculations including the simulation of the interaction of a protonated amine with the enolate adsorbed on a Pt 31 cluster revealed that only the C-O bond next to the CF3 group of the substrate is in direct contact with Pt and can be hydrogenated. The present study illustrates the fundamental role played by the metal surface and indicates that also the enol form can be the reactive species in the hydrogenation of the activated ketone on chirally modified Pt.     

Influence of Hartree-Fock exchange on the calculated Mössbauer isomer shifts and quadrupole splittings in ferrocene derivatives using density functional theory

Influence of molecular geometry, type of exchange-correlation functional, and contraction scheme of basis set applied at the iron nuclei have been tested in the calculation of 57Fe M?ssbauer isomer shifts and quadrupole splittings for a wide range of ligand types, as well as oxidation and spin states, in inorganic and organometallic systems. It has been found that uncontraction of the s-part of Wachter's full-electron basis set at the iron nuclei does not appreciably improve the calculated isomer shifts. The observed correlations for all tested sets of geometries are close to each other and predominantly depend on the employed exchange-correlation functional with B3LYP functional being slightly better as compared to BPW91. Both hybrid (B3LYP) and pure (BPW91) exchange-correlation functionals are suitable for the calculation of isomer shifts in organometallic compounds. Surprisingly, it has been found that the hybrid B3LYP exchange-correlation functional completely fails in accurate prediction of quadrupole splittings in ferrocenes, while performance of the pure BPW91 functional for the same systems was excellent. This observation has been explained on the basis of relationship between the amount of Hartree-Fock exchange involved in the applied exchange-correlation functional and the calculated HOMO-LUMO energy gap in ferrocenes. On the basis of this explanation, use of only pure exchange-correlation functionals has been suggested for accurate prediction of M?ssbauer spectra parameters in ferrocenes.     

Synthesis, structure, and magnetic properties of (6-9)-nuclear Ni(II) trimethylacetates and their heterospin complexes with nitroxides

New polynuclear nickel trimethylacetates [Ni6(OH)4(C5H9O2)8(C5H10O2)4] (6), [Ni7(OH)7(C5H9O2)7(C5H10O2)6(H2O)] x 0.5 C6H14 x 0.5 H2O (7), [Ni8(OH)4(H2O)2(C5H9O2)12] (8), and [Ni9(OH)6(C5H9O2)12(C5H10O2)4] x C5H10O2 x 3 H2O (9), where C5H9O2 is trimethylacetate and C5H10O2 is trimethylacetic acid, have been found. Their structures were determined by X-ray crystallography. Because of their high solubility in low-polarity organic solvents, compounds 6-9 reacted with stable organic radicals to form the first heterospin compounds based on polynuclear Ni(II) trimethylacetate and nitronyl nitroxides containing pyrazole (L(1)-L(3)), methyl (L(4)), or imidazole (L(5)) substituent groups, respectively, in side chain [Ni7(OH)5(C5H9O2)9(C5H10O2)2(L(1))2(H2O)] x 0.5 C6H14 x H2O (6+1a), [Ni7(OH)5(C5H9O2)9(C5H10O2)2(L2)2(H2O)] x H2O (6+1b), [Ni7(OH)5(C5H9O2)9(C5H10O2)2(L(3))2(H2O)] x H2O (6+1c), [Ni6(OH)3(C5H9O2)9(C5H10O2)4(L(4))] x 1.5 C6H14 (6'), and [Ni4OH)3(C5H9O2)5(C5H10O2)4(L(5))] x 1.5 C7H8 (4). Their structures were also determined by X-ray crystallography. Although Ni(II) trimethylacetates may have varying nuclearity and can change their nuclearity during recrystallization or interactions with nitroxides, this family of compounds is easy to study because of its topological relationship. For any of these complexes, the polynuclear framework may be derived from the [Ni6] polynuclear fragment {Ni6(mu4-OH)2(mu3-OH)2(mu2-C5H9O2-O,O')6(mu2-C5H9O2-O,O)(mu4-C5H9O2-O,O,O',O')(C5H10O2)4}, which is shaped like an open book. On the basis of this fragment, the structure of 7-nuclear compounds (7 and 6+1a-c) is conveniently represented as the result of symmetric addition of other mononuclear fragments to the four Ni(II) ions lying at the vertexes of the [Ni6] open book. The 9-nuclear complex is formed by the addition of trinuclear fragments to two Ni(II) ions lying on one of the lateral edges of the [Ni6] open book. This wing of the 9-nuclear complex preserves its structure in another type of 6-nuclear complex (6') with the boat configuration. If, however, two edge-sharing Ni(II) ions are removed from [Ni6] (one of these lies at a vertex of the open book and the other, on the book-cover line), we obtain a 4-nuclear fragment recorded in the molecular structure of 4. Twinning of this 4-nuclear fragment forms highly symmetric molecule 8, which is a new chemical version of cubane.