Direct time-resolved study of the kinetics of the reaction of silylene with phenylsilane in the gas phase. Does SiH2 react with the aromatic ring?

Laser flash photolysis studies of silylene, SiH2, generated by the 193 nm laser flash photolysis phenylsilane, PhSiH3, have been carried out to obtain rate constants for its bimolecular reaction with PhSiH3 itself, in the gas phase. The reaction was studied in SF6 (mostly at 10 Torr total pressure) over the temperature range 298-595 K. The rate constants (also found to be pressure independent) gave the following Arrhenius equation: log(k/cm(3) molecule(-1) s(-1)) = (-9.92 +/- 0.04) + (3.31 +/- 0.27) kJ mol(-1)/RT ln 10 Similar investigations of the reaction of silylene with benzene, C6H6, (295-410 K) gave data suggestive of the fact that SiH2 might be reacting with photochemical products of C6H6 as well as with C6H6 itself. However, in the latter system, apparent rate constants were sufficiently low to indicate that in the reaction of SiH2 with PhSiH3 addition to the aromatic ring was unlikely to be in excess of 3% of the total. Quantum chemical calculations of the energy surface for SiH2 + C6H6 indicate that 7-silanorcaradiene and 7-silacycloheptatriene are possible products but that PhSiH3 formation is unlikely. RRKM calculations suggest that 7-silanorcaradiene should be the initial product but that it cannot be collisionally stabilized under experimental conditions

Rational modification of the hierarchy of intermolecular interactions in molecular crystal structures by using tunable halogen bonds

A family of 16 isomolecular salts (3-XpyH)(2)[MX'(4)] (3-XpyH=3-halopyridinium; M=Co, Zn; X=(F), Cl, Br, (I); X'=Cl, Br, I) each containing rigid organic cations and tetrahedral halometallate anions has been prepared and characterized by X-ray single crystal and/or powder diffraction. Their crystal structures reflect the competition and cooperation between non-covalent interactions: N-H center dot center dot center dot X'-M hydrogen bonds, C-X center dot center dot center dot X'-M halogen bonds and pi-pi stacking. The latter are essentially unchanged in strength across the series, but both halogen bonds and hydrogen bonds are modified in strength upon changing the halogens involved. Changing the organic halogen (X) from F to I strengthens the C-X center dot center dot center dot X'-M halogen bonds, whereas an analogous change of the inorganic halogen (X') weakens both halogen bonds and N-H center dot center dot center dot X'-M hydrogen bonds. By so tuning the strength of the putative halogen bonds from repulsive to weak to moderately strong attractive interactions, the hierarchy of the interactions has been modified rationally leading to systematic changes in crystal packing. Three classes of crystal structure are obtained. In type A (C-F center dot center dot center dot X'-M) halogen bonds are absent. The structure is directed by N-H center dot center dot center dot X'-M hydrogen bonds and pi-stacking interactions. In type B structures, involving small organic halogens (X) and large inorganic halogens (X'), long (weak) C-X center dot center dot center dot X'-M interactions are observed with type I halogen-halogen interaction geometries (C-X center dot center dot center dot X' approximate to X center dot center dot center dot X'-M approximate to 155 degrees), but hydrogen bonds still dominate. Thus, minor but quite significant perturbations from the type A structure arise. In type C, involving larger organic halogens (X) and smaller inorganic halogens (X'), stronger halogen bonds are formed with a type II halogen-halogen interaction geometry (C-X center dot center dot center dot X' approximate to 180 degrees; X center dot center dot center dot X'-M approximate to 110 degrees) that is electrostatically attractive. The halogen bonds play a major role alongside hydrogen bonds in directing the type C structures, which as a result are quite different from type A and B.

Gas-solid reactions of single crystals: a study of the reaction of bromine with single crystals of trans-cinnamic acid and a range of its derivatives by infrared and Raman microspectroscopy

Single crystals of trans-cinnamic acid and of a range of derivatives of this compound containing halogen substituents on the aromatic ring have been reacted with 165 Torr pressure of bromine vapour in a sealed desiccator at 20 degrees C for 1 week. Infrared and Raman microspectroscopic examination of the crystals shows that bromination of the aliphatic double bond, but not of the aromatic ring, has occurred. It is demonstrated also that the reaction is truly gas-solid in nature. A time-dependent study of these reactions shows that they do not follow a smooth diffusion-controlled pathway. Rather the reactions appear to be inhomogeneous and to occur at defects within the crystal. The reaction products are seen to flake from the surface of the crystal. It is shown, therefore, that these are not single crystal to single crystal transitions, as have been observed previously for the photodimerisation of trans-cinnamic acid and several of its derivatives. It is shown that there are no by-products of the reaction and that finely ground samples react to form the same products as single crystals.

Sea-breeze modification of the growth of a marine internal boundary layer

A numerical mesoscale model is used to make a high-resolution simulation of the marine boundary layer in the Persian Gulf, during conditions of offshore flow from Saudi Arabia. A marine internal boundary layer (MIBL) and a sea-breeze circulation (SBC) are found to co-exist. The sea breeze develops in the mid-afternoon, at which time its front is displaced several tens of kilometres offshore. Between the coast and the sea-breeze system, the MIBL that occurs is consistent with a picture described in the existing literature. However, the MIBL is perturbed by the SBC, the boundary layer deepening significantly seaward of the sea-breeze front. Our analysis suggests that this strong, localized deepening is not a direct consequence of frontal uplift, but rather that the immediate cause is the retardation of the prevailing, low-level offshore wind by the SBC. The simulated boundary-layer development can be accounted for by using a simple 1D Lagrangian model of growth driven by the surface heat flux. This model is obtained as a straightforward modification of an established MIBL analytic growth model.

NMR studies of the conformational effect of single and double 3'-S-phosphorothiolate substitutions within deoxythymidine trinucleotides

NMR spectroscopy has been used to investigate the conformational effects of single and two consecutive 3′-S-phosphorothiolate modifications within a deoxythymidine trinucleotide. The presence of a single 3′-phosphorothioate modification shifts the conformation of the sugar ring it is attached to, from a mainly south to north pucker; this effect is also transmitted to the 3′-neighbour deoxyribose. This transmission is thought to be caused by favourable stacking of the heterocyclic bases. Similar observations have been made previously by this group. When two adjacent modifications are present, the conformations of the attached deoxyribose rings are again shifted almost completely to the north, however, there is no transmission to the 3′ deoxyribose ring. Base proton chemical shift analysis and molecular modelling have been used to aid elucidation of the origin of this feature. The observation for the dimodified sequence is consistent with our previously reported results for a related system in which spaced modifications are more thermodynamically stable than consecutive ones.

The interplay of secondary Hg⋯S, Hg⋯N and Hg⋯π bonding interactions in supramolecular structures of phenylmercury(ii) dithiocarbamates

Three new phenylmercury(II) and one mercury(II) dithiocarbamate complexes viz. PhHg S2CN(PyCH2) Bz (1), PhHg S2CN(PyCH2)CH3 (2), PhHg S2CN(Bz)CH3 (3), and [Hg (NCS2(PyCH2)Bz)(2)] (4) (Py = pyridine; Bz = benzyl) have been synthesized and characterized by elemental analyses, IR, electronic absorption, H-1 and C-13 NMR spectroscopy. The crystal structures of 1, 2 and 3 showed a linear S-Hg-C core at the centre of the molecule, in which the metal atom is bound to the sulfur atom of the dithiocarbamate ligand and a carbon atom of the aromatic ring. In contrast the crystal structure of 4 showed a linear S-Hg-S core at the Hg(II) centre of the molecule. Weak intermolecular Hg center dot center dot center dot N (Py) interactions link molecules into a linear chain in the case of 1, whereas chains of dimers are formed in 2 through intermolecular Hg center dot center dot center dot N (Py) and Hg center dot center dot center dot S interactions. 3 forms a conventional face-to-edge dimeric structure through intermolecular Hg center dot center dot center dot S secondary bonding and 4 forms a linear chain of dimers through face-to-face Hg center dot center dot center dot S secondary bonding. In order to elucidate the nature of these secondary bonding interactions and the electronic absorption spectra of the complexes, ab initio quantum chemical calculations at the MP2 level and density functional theory calculations were carried out for 1-3. Complexes 1 and 2 exhibited photoluminescent properties in the solid state as well as in the solution phase. Studies indicate that Hg center dot center dot center dot S interactions decrease and Hg center dot center dot center dot N interactions increase the chances of photoluminescence in the solid phase

Baseline nitrate concentration in groundwater of the Chalk in south Dorset, UK

Determining the degree of nitrate pollution in Chalk groundwater is difficult without a clear understanding of concentrations naturally present. In the UK, a general shortage of long-term records of nitrate concentrations in Chalk groundwater prevents a full quantification of baseline concentrations. This paper presents late nineteenth and early twentieth century data on nitrate concentrations in Chalk groundwater in south Dorset, UK and compares them with corresponding data for the last 25 years. The nitrate record is instructive in (1) providing an insight into the baseline nitrate concentration of groundwater; (2) defining the level of nitrate pollution in potable supplies from the Chalk aquifer; and (3) identifying the long-term variations in local nitrate concentrations. Over a period exceeding 100 years mean nitrate concentrations increased from 1.04 mg NO3-N l(-1) to 6.37 mg NO3-N l(-1). Anthropogenic modification of the local groundwater composition is not evident in the early nitrate record. Nitrate data throughout this early period reflect natural background concentrations of approximately I mg NO3-N l(-1) Intensified fertilser use and increased livestock numbers are suggested as the fundamental cause of the rise in nitrate concentrations. The implications of the nitrate record for regional hydrogeological processes are discussed. (C) 2003 Elsevier Science B.V. All rights reserved.

Evaluation of the cumulative evidence for freedom from BSE in birth cohorts

Substantial resources are used for surveillance of bovine spongiform encephalopathy (BSE) despite an extremely low detection rate, especially in healthy slaughtered cattle. We have developed a method based on the geometric waiting time distribution to establish and update the statistical evidence for BSE-freedom for defined birth cohorts using continued surveillance data. The results suggest that currently (data included till September 2004) a birth cohort of Danish cattle born after March 1999 is free from BSE with probability (power) of 0.8746 or 0.8509, depending on the choice of a model for the diagnostic sensitivity. These results apply to an assumed design prevalence of 1 in 10,000 and account for prevalence heterogeneity. The age-dependent, diagnostic sensitivity for the detection of BSE has been identified as major determinant of the power. The incorporation of heterogeneity was deemed adequate on scientific grounds and led to improved power values. We propose our model as a decision tool for possible future modification of the BSE surveillance and discuss public health and international trade implications.

Anion-pi, Lone-Pair-pi, pi-pi and Hydrogen-Bonding Interactions in a Cu-II Complex of 2-Picolinate and Protonated 4,4 '-Bipyridine: Crystal Structure and Theoretical Studies

A Cu-II complex of protonated 4,4'-bipyridine (Hbyp) and 2-picolinate (pic), [Cu-2(pic)(3)(Hbyp)(H2O)(ClO4)(2)], has been synthesised and characterised by single-crystal X-ray analysis. The structure consists of two copper atoms that have different environments, bridged by a carboxylate group. The equatorial plane is formed by the two bidentate picolinate groups in one Cu-II, and one picolinate, one monodentate 4,4'-bipyridyl ligand and a water molecule in the other. Each copper atom is also weakly bonded to a perchlorate anion in an axial position. One of the coordinated perchlorate groups displays anion-pi interaction with the coordinated pyridine ring. The noncoordinated carboxylate oxygen is involved in lone-pair (l.p.)-pi interaction with the protonated pyridine ring. In addition there are pi-pi and H-bonding interactions in the structure. Bader's theory of "atoms in molecules" (AIM) is used to characterise the anion-pi and l.p.-pi interactions observed in the solid state. A high-level ab initio study (RI-MP2/aug-cc-pVTZ level of theory) has been performed to analyse the anion-pi binding affinity of the pyridine ring when it is coordinated to a transition metal and also when the other pyridine ring of the 4,4'-bipyridine moiety is protonated. Theoretical investigations support the experimental findings of an intricate network of intermolecular interactions, which is characterised in the studied complex, and also indicate that protonation as well as coordination to the transition metal have important roles in influencing the pi-binding properties of the aromatic ring. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Canonical description of the perspective projections

A unique parameterization of the perspective projections in all whole-numbered dimensions is reported. The algorithm for generating a perspective transformation from parameters and for recovering parameters from a transformation is a modification of the Givens orthogonalization algorithm. The algorithm for recovering a perspective transformation from a perspective projection is a modification of Roberts' classical algorithm. Both algorithms have been implemented in Pop-11 with call-out to the NAG Fortran libraries. Preliminary monte-carlo tests show that the transformation algorithm is highly accurate, but that the projection algorithm cannot recover magnitude and shear parameters accurately. However, there is reason to believe that the projection algorithm might improve significantly with the use of many corresponding points, or with multiple perspective views of an object. Previous parameterizations of the perspective transformations in the computer graphics and computer vision literature are discussed.

An assessment of the MODIS collection 5 leaf area index product for a region of mixed coniferous forest

Canopy leaf area index (LAI), defined as the single-sided leaf area per unit ground area, is a quantitative measure of canopy foliar area. LAI is a controlling biophysical property of vegetation function, and quantifying LAI is thus vital for understanding energy, carbon and water fluxes between the land surface and the atmosphere. LAI is routinely available from Earth Observation (EO) instruments such as MODIS. However EO-derived estimates of LAI require validation before they are utilised by the ecosystem modelling community. Previous validation work on the MODIS collection 4 (c4) product suggested considerable error especially in forested biomes, and as a result significant modification of the MODIS LAI algorithm has been made for the most recent collection 5 (c5). As a result of these changes the current MODIS LAI product has not been widely validated. We present a validation of the MODIS c5 LAI product over a 121 km2 area of mixed coniferous forest in Oregon, USA, based on detailed ground measurements which we have upscaled using high resolution EO data. Our analysis suggests that c5 shows a much more realistic temporal LAI dynamic over c4 values for the site we examined. We find improved spatial consistency between the MODIS c5 LAI product and upscaled in situ measurements. However results also suggest that the c5 LAI product underestimates the upper range of upscaled in situ LAI measurements.

Analyzing the persuasion context of the persuasive systems design model with the 3D-RAB model

Research into design methodology is one of the most challenging issues in the field of persuasive technology. However, the introduction of the Persuasive Systems Design model, and the consideration of the 3-Dimensional Re-lationship between Attitude and Behavior, offer to make persuasive technolo-gies more practically viable. In this paper we demonstrate how the 3-Dimensional Relationship between Attitude and Behavior guides the analysis of the persuasion context in the Persuasive System Design model. As a result, we propose a modification of the persuasion context and assert that the technology should be analyzed as part of strategy instead of event.

Bayesian estimation of the double hurdle model in the presence of fixed costs

We present a model of market participation in which the presence of non-negligible fixed costs leads to random censoring of the traditional double-hurdle model. Fixed costs arise when household resources must be devoted a priori to the decision to participate in the market. These costs, usually of time, are manifested in non-negligible minimum-efficient supplies and supply correspondence that requires modification of the traditional Tobit regression. The costs also complicate econometric estimation of household behavior. These complications are overcome by application of the Gibbs sampler. The algorithm thus derived provides robust estimates of the fixed-costs, double-hurdle model. The model and procedures are demonstrated in an application to milk market participation in the Ethiopian highlands.