An electrochemical investigation on (MoO<Subscript>3</Subscript>+PVP+PVA) nanobelts for lithium batteries

Molybdenum trioxide (MoO₃) xerogel films modified with poly(vinyl alcohol)+poly(vinyl pyrrolidone) (PVP+PVA) polyblends were obtained by ion-exchange method with sol-gel technique. Investigations were conducted using X-ray “diffractometry”, Fourier transform infrared spectroscopy, and cyclic voltammetry. The results show that the H atoms in polyblend are H-bonded with the O atoms in the Mo=O bonds of MoO₃ xerogel, which effectively shield the electrostatic interaction between MoO₃ interlayer and Li⁺ ions when MoO₃ xerogel is modified by the intercalation of (PVP+PVA). The reversibility of the insertion/extraction of Li⁺ ions is greatly improved by the modification with polyblend of MoO₃ nanocomposite films. MoO₃ and (PVP+PVA) _x MoO₃ (x = 0, 0.5) nanobelts were obtained by a simple hydrothermal process from MoO₃ sol. The electrochemical cells with configuration Li/(LiPF₆+EC+DMC)/MoO₃ modified by (PVP+PVA) were fabricated and their discharge profiles studied.     

Beyond the benzene dimer: an investigation of the additivity of pi-pi interactions

The benzene dimer is the simplest prototype of pi-pi interactions and has been used to understand the fundamental physics of these interactions as they are observed in more complex systems. In biological systems, however, aromatic rings are rarely found in isolated pairs; thus, it is important to understand whether aromatic pairs remain a good model of pi-pi interactions in clusters. In this study, ab initio methods are used to compute the binding energies of several benzene trimers and tetramers, most of them in 1D stacked configurations. The two-body terms change only slightly relative to the dimer, and except for the cyclic trimer, the three- and four-body terms are negligible. This indicates that aromatic clusters do not feature any large nonadditive effects in their binding energies, and polarization effects in benzene clusters do not greatly change the binding that would be anticipated from unperturbed benzene-benzene interactions, at least for the 1D stacked systems considered. Three-body effects are larger for the cyclic trimer, but for all systems considered, the computed binding energies are within 10% of what would be estimated from benzene dimer energies at the same geometries.     

Calculation of Franck-Condon factors including anharmonicity: simulation of the C2H4+X2B3u<--C2H4X1A(g) band in the photoelectron spectrum of ethylene

Our new simple method for calculating accurate Franck-Condon factors including nondiagonal (i.e., mode-mode) anharmonic coupling is used to simulate the C2H4+X2B3u<--C2H4X1A(g) band in the photoelectron spectrum. An improved vibrational basis set truncation algorithm, which permits very efficient computations, is employed. Because the torsional mode is highly anharmonic it is separated from the other modes and treated exactly. All other modes are treated through the second-order perturbation theory. The perturbation-theory corrections are significant and lead to a good agreement with experiment, although the separability assumption for torsion causes the C2D4 results to be not as good as those for C2H4. A variational formulation to overcome this circumstance, and deal with large anharmonicities in general, is suggested.     

Kinetic studies of some substituted hexarhodium carbonyl clusters

Reactions of the halides X- (X- = chloride, bromide or iodide) with the substituted cluster Rh6(CO)15(PPh3) in oxygen-free chloroform lead to [Rh5(CO)14(PPh3)]-, Rh(CO)2(PPh3)2X and [Rh(CO)2X2]- in the molar ratios 2:1: approximately 13. Oxidation by the solvent is assumed to lead to most of the Rh(I) product, and the stoichiometry for reactions with I- can be defined as 4Rh6(CO)15(PPh3) + 27I- + 12CHCl3 --> 2[Rh5(CO)14(PPh3)]- + Rh(CO)2(PPh3)2I + 13[Rh(CO)2I2]- + 6C2H2Cl4 + 4CO + 12Cl-. This can be rationalized quite simply with the aid of a few generally justifiable assumptions. Rate constants for reactions with bromide increase to a limiting value with increasing [Br-] in a way that shows that breaking of one Rh-Rh bond, with an unusual closo to nido structural change, is rate determining. This opening of the cluster might be spontaneous or solvent induced. To complete the reaction, the bromide has to compete with the reverse nido to closo change. The same closo to nido change is also a major rate determining step for reactions with P(OPh)3 in oxygen-free solutions, and for reactions with bromide in oxygenated solutions in the presence of trifluoroacetic and some other acids. The limiting rates increase slightly with increasing basicity of the ligands P(p-XC6H4)3 along the series X = F3C, Cl, F, H and MeO. Activation parameters for these reactions are reported.     

syn-2,3-Disubstituted-2,3-dihydro-1,4-benzoxathiin rings: preparation from quinone ketals and 2-mercaptoethanols

A general method for the preparation of syn-2,3-disubstituted-2,3-dihydro-1,4-benzoxathiin rings from 2-mercaptoethanols and quinone ketals is presented. This ring system is produced by Michael addition of a 2-mercaptoethanol to a quinone ketal, followed by cyclization of the initial Michael adduct, and subsequent aromatization to afford a syn-2,3-disubstituted-1,4-benzoxathiin in fair to good chemical yield. Several chiral syn-2,3-disubstituted-2,3-dihydro-1,4-benzoxathiin rings were prepared with this method from enantioenriched 2-mercaptoethanols. No loss of enantiopurity was observed.     

Reactions of Molecules with Two Equivalent Functional Groups. 5. Anomalous Reactivity of 1,10-Cyclooctadecanedione. Crystal and Molecular Structures of cis,cis-1,10-Diphenyl-1,10-cyclooctadiene and the Stereoisomers of 1,10-Diphenyl-1,10-cyclooctadecanediol(1)

The reaction of the title diketone (3) with phenyl Grignard produces (with rate constant k(1)) the conjugate base (6-M) of 10-hydroxy-10-phenylcyclooctadecanone (6), which is subsequently converted (with rate constant k(2)) to the conjugate base of the title diol, as a mixture of the cis (7, 55%) and trans (8, 45%) isomers. The ratio k(2)/k(1), 2.2 +/- 0.4, indicates that the carbonyl group in 6-M is 4.4 times as reactive as each carbonyl in 3. Competition experiments further demonstrate that the relative rates (per carbonyl) for addition of phenylmagnesium bromide to 3, 10-methylenecyclooctadecanone (11), and cyclopentadecanone (12) are 1.0:0.60:1.92. Possible reasons for this order of reactivity are discussed. Diols 7 and 8 undergo facile double dehydration to form the title diene 13, which is predicted by molecular mechanics calculations to be the most stable of the four possible symmetrical diene isomers. The structures of 7, 8, and 13 were secured by single-crystal X-ray studies.     

Potentiometric measurements of the first hydrolysis quotient of magnesium(II) to 250°C and 5 molal ionic strength (NaCl)

The first molal hydrolysis quotient, Q_1.1, of Mg²⁺ was measured potentiometrically from 1 to 250°C at ionic strengths of 0.11, 0.31, 1.01, and 5.0 mol-kg^-1 in an aqueous NaCl medium using a hydrogen-electrode, concentration cell. Only hydrolysis of the first four percent of the magnesium in solution could be followed before precipitation of brucite, Mg(OH)₂(cr), occurred. The log Q_1.1 values were fitted as a function of temperature and ionic strength using four adjustable parameters. The resulting constants are compared with the limited existing low temperature data. At infinite dilution and 25°C the following quantities are reported: logK _1.1 = -11.68±0.05, †H_so = 70.1±1.2 kJ-mol^-1, †S^o = 11±4 J-K^-1-mol^-1, and †C _p ^o = 0 J-K^-1-mor^-1. At each ionic strength, including the values extrapolated to infinite dilution, the heat capacity change for the hydrolysis reaction was zero,i.e., logQ _1.1 was found to be a linear function of the reciprocal temperature in Kelvin, at least over the measured range of l-250°C. The hydrolysis constants at infinite dilution were modeled to 550°C and two kbar pressure with a function incorporating solvent density using published results obtained at these extreme conditions.     

A new method for the direct calculation of resonance parameters with application to the quasibound states of the H2X1Σ g + system

A new method for the direct calculation of resonance parameters is presented. It is based upon searching for poles of the scattering matrix at complex energies. This search is expedited by the use of analytic derivatives of the scattering matrix with respect to the total energy. This procedure is applied initially to a single channel problem, but is generalizable to more complicated systems. Using the most accurate available potential energy data, we calculate resonance parameters for all of the physically important quasibound states of the ground electronic state of the hydrogen molecule. Corrections to the Born-Oppenheimer potential are included and assessed. The new method has no difficulty locating resonances with widths greater than about 1×10^–7 cm^–1. It is easier to find narrow resonances by monitoring the dependence of the imaginary part of the reactance matrix on the real part of a complex energy than to monitor the dependence of the eigenphase sum on energy at real energies.     

Synthesis of pyridone and pyridine rings by [4+2] hetero-cyclocondensation

Substituted pyridones and pyridines have been synthesised efficiently by employing iminium salt as a key precursor. These compounds were prepared using tandem [4+2] cycloaddition/deamination between azabutadiene and dienophiles.     

Rapid biomass analysis

New, rapid, and inexpensive methods that monitor the chemical composition of corn stover and corn stover-derived samples are a key element to enabling the commercialization of processes that convert stover to fuels and chemicals. These new techniques combine near infrared (NIR) spectroscopy and projection to latent structures (PLS) multivariate analysis to allow the compositional analysis of hundreds of samples in 1 d at a cost of about $10 each. The new NIR/PLS rapid analysis methods can also be used to support a variety of research projects that would have been too costly to pursue by traditional methods.