Study of the structure, energetics, and vibrational properties of small ammonia clusters (NH3)n (n = 2-5) using correlated ab initio methods

Equilibrium geometries, interaction energies, and harmonic frequencies of (NH3)n isomers (n = 2-5) have been computed using correlated calculations (MP2) in conjunction with Dunning's aug-cc-pVXZ (X = D, T, Q) basis sets and the Counterpoise procedure. Whenever available, literature values for the binding energy and geometry of dimers and trimers agree well with our data. Low lying isomers for (NH3)4 and (NH3)5 have been found to have similar binding energies (roughly 16 and 20 kcal/mol for the tetramer and pentamer, respectively), perhaps suggesting the presence of a very smooth energy landscape. Using BSSE corrected forces or freezing the monomer structure to its gas phase geometry have been found to have only a weak impact on the energetic and structural properties of the clusters. The effect of zero-point energy (ZPE) on the relative stability of the clusters has been estimated using harmonic frequencies. The latter also highlighted the presence of vibrational fingerprints for the presence of double acceptor ammonia molecules. Many-body effects for (NH3)n isomers (n = 2-4) have been investigated to explore the possibility of building a pairwise interaction model for ammonia. In the frame of the work presented, we have found the 3-body effect to account for 10-15% of the total interaction energy, whereas the 4-body effects may be neglected as first approximation.     

Internal correction of hafnium oxide spectral interferences and mass bias in the determination of platinum in environmental samples using isotope dilution analysis

A method has been developed for the accurate determination of platinum by isotope dilution analysis, using enriched ¹⁹⁴Pt, in environmental samples containing comparatively high levels of hafnium without any chemical separation. The method is based on the computation of the contribution of hafnium oxide as an independent factor in the observed isotope pattern of platinum in the spiked sample. Under these conditions, the ratio of molar fractions between natural abundance and isotopically enriched platinum was independent of the amount of hafnium present in the sample. Additionally, mass bias was corrected by an internal procedure in which the regression variance was minimised. This was possible as the mass bias factor for hafnium oxide was very close to that of platinum. The final procedure required the measurement of three platinum isotope ratios (192/194, 195/194 and 196/194) to calculate the concentration of platinum in the sample. The methodology has been validated using the reference material “BCR-723 road dust” and has been applied to different environmental matrices (road dust, air particles, bulk wet deposition and epiphytic lichens) collected in the Aspe Valley (Pyrenees Mountains). A full uncertainty budget, using Kragten’s spreadsheet method, showed that the total uncertainty was limited only by the uncertainty in the measured isotope ratios and not by the uncertainties of the isotopic composition of platinum and hafnium. Figure Simultaneous correction of hafnium oxide spectral interferences and mass bias in the determination of platinum in environmental samples using isotope dilution analysis Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

Singularities of linear systems and the Waring problem

The Waring problem for homogeneous forms asks for additive decomposition of a form into powers of linear forms. A classical problem is to determine when such a decomposition is unique. In this paper we answer this question when the degree of is greater than the number of variables. To do this we translate the algebraic statement into a geometric one concerning the singularities of linear systems of with assigned singularities.

     

Association of the T allele of an intronic single nucleotide polymorphism in the colony stimulating factor 1 receptor with Crohn's disease: a case-control study

BACKGROUND: Polymorphisms in several genes (NOD2, MDR1, SLC22A4) have been associated with susceptibility to Crohn's disease. Identification of the remaining Crohn's susceptibility genes is essential for the development of disease-specific targets for immunotherapy. Using gene expression analysis, we identified a differentially expressed gene on 5q33, the colony stimulating factor 1 receptor (CSF1R) gene, and hypothesized that it is a Crohn's susceptibility gene. The CSF1R gene is involved in monocyte to macrophage differentiation and in innate immunity. METHODS: Patients provided informed consent prior to entry into the study as approved by the Institutional Review Board at LSU Health Sciences Center. We performed forward and reverse sequencing of genomic DNA from 111 unrelated patients with Crohn's disease and 108 controls. We also stained paraffin-embedded, ileal and colonic tissue sections from patients with Crohn's disease and controls with a polyclonal antibody raised against the human CSF1R protein. RESULTS: A single nucleotide polymorphism (A2033T) near a Runx1 binding site in the eleventh intron of the colony stimulating factor 1 receptor was identified. The T allele of this single nucleotide polymorphism occurred in 27% of patients with Crohn's disease but in only 13% of controls (X2 = 6.74, p < 0.01, odds ratio (O.R.) = 2.49, 1.23 < O.R. < 5.01). Using immunohistochemistry, positive staining with a polyclonal antibody to CSF1R was observed in the superficial epithelium of ileal and colonic tissue sections. CONCLUSIONS: We conclude that the colony stimulating factor receptor 1 gene may be a susceptibility gene for Crohn's disease.     

Improved importance sampling distribution for rate constant calculation

An efficient method to compute the thermal rate constant for rare events within the correlation function C(t) approach is presented. This method, which is based on a modification of the sampling function used to evaluate the dynamical correlation function C(t), can be applied to high-dimensional systems having a rough energy landscape without previous knowledge on the transition states location. In this work, the sampling of a Boltzmann-like distribution for the linear momenta with a lower inverse temperature (beta(*)=1/kT(*)) than the correct one (beta=1/kT) is proposed as a way to increase the number of reactive trajectories. The mismatch between the beta(*) and beta distributions is then corrected by a reweighting procedure which allows one to obtain the exact correlation function C(t). The efficiency of this scheme in computing the rate of a particle jumping across the barrier of a simple 2D double well potential is improved by a factor 4-25 depending on the relative value of the original beta and modified beta(*) temperatures. When merged with the "puddle potential" method [S. A. Corcelli, J. A. Rohman, and J. C. Tully, J. Chem. Phys., 118, 1085 (2003)], the new importance sampling function improves the efficiency of the correlation function approach by a factor 16-800 with respect to the unbiased sampling. To test the method in a more challenging case, the previous model system was extended by adding six harmonically restrained particles, each one interacting with the diffusing particle. This model introduces both the possibility of energy exchange and a rougher energy landscape. The new sampling function alone is found to produce an improvement in efficiency of, at least, an order of magnitude when compared with the unbiased case; when merged with the puddle potential method, a 400-fold saving in computer time is found.     

Photochemical alkylation of ketene dithioacetal S,S-dioxides. An example of captodative olefin functionalization

Radical alkylation of some ketene dithioacetal S,S-dioxides failed through the tin hydride promoted chain process but was successfully performed through stoichiometric photochemical initiation, either by electron transfer or hydrogen abstraction. In the first case, alkyl radicals were produced from tetralkylstannanes (t-Bu-, i-Pr-, n-Bu-SnR(3)) via radical cation fragmentation, while in the second case these were produced from alkanes (cyclohexane, adamantane) by benzophenone triplet. When bulky radicals (t-Bu, adamantyl) were involved, the addition occurred with complete diastereoselectivity.     

Predicting atomic dopant solvation in helium clusters: the MgHe(n) case

We present a quantum Monte Carlo study of the solvation and spectroscopic properties of the Mg-doped helium clusters MgHe(n) with n=2-50. Three high-level [MP4, CCSD(T), and CCSDT] MgHe interaction potentials have been used to study the sensitivity of the dopant location on the shape of the pair interaction. Despite the similar MgHe well depth, the pair distribution functions obtained in the diffusion Monte Carlo simulations markedly differ for the three pair potentials, therefore indicating different solubility properties for Mg in He(n). Moreover, we found interesting size effects for the behavior of the Mg impurity. As a sensitive probe of the solvation properties, the Mg excitation spectra have been simulated for various cluster sizes and compared with the available experimental results. The interaction between the excited 1P Mg atom and the He moiety has been approximated using the diatomics-in-molecules method and the two excited 1pi and 1sigma MgHe potentials. The shape of the simulated MgHe50 spectra shows a substantial dependency on the location of the Mg impurity, and hence on the MgHe pair interaction employed. To unravel the dependency of the solvation behavior on the shape of the computed potentials, exact density-functional theory has been adapted to the case of doped He(n) and various energy distributions have been computed. The results indicate the shape of the repulsive part of the MgHe potential as an important cause of the different behaviors.     

Optimisation of the formulation of a bubble bath by a chemometric approach market segmentation and optimisation

The optimisation of the formulation of a commercial bubble bath was performed by chemometric analysis of Panel Tests results. A first Panel Test was performed to choose the best essence, among four proposed to the consumers; the best essence chosen was used in the revised commercial bubble bath. Afterwards, the effect of changing the amount of four components (the amount of primary surfactant, the essence, the hydratant and the colouring agent) of the bubble bath was studied by a fractional factorial design. The segmentation of the bubble bath market was performed by a second Panel Test, in which the consumers were requested to evaluate the samples coming from the experimental design. The results were then treated by Principal Component Analysis. The market had two segments: people preferring a product with a rich formulation and people preferring a poor product. The final target, i.e. the optimisation of the formulation for each segment, was obtained by the calculation of regression models relating the subjective evaluations given by the Panel and the compositions of the samples. The regression models allowed to identify the best formulations for the two segments ofthe market.