Time-resolved gas-phase kinetic, quantum chemical, and RRKM studies of reactions of silylene with alcohols

Time-resolved kinetic studies of silylene, SiH2, generated by laser flash photolysis of 1-silacyclopent-3-ene and phenylsilane, have been carried out to obtain rate constants for its bimolecular reactions with methanol, ethanol, 1-propanol, 1-butanol and 2-methyl-1-butanol. The reactions were studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas, at room temperature. In the study with methanol several buffer gases were used. All five reactions showed pressure dependences characteristic of third body assisted association reactions. The rate constant pressure dependences were modelled using RRKM theory, based on Eo values of the association complexes obtained by ab initio calculation (G3 level). Transition state models were adjusted to fit experimental fall-off curves and extrapolated to obtain k∞ values in the range 1.9 to 4.5 × 10-10 cm3 molecule-1 s-1. These numbers, corresponding to the true bimolecular rate constants, indicate efficiencies of between 16 and 67% of the collision rates for these reactions. In the reaction of SiH2 + MeOH there is a small kinetic component to the rate which is second order in MeOH (at low total pressures). This suggests an additional catalysed reaction pathway, which is supported by the ab initio calculations. These calculations have been used to define specific MeOH-for-H2O substitution effects on this catalytic pathway. Where possible our experimental and theoretical results are compared with those of previous studies.

The reaction between silylene and ammonia: some gas-phase kinetic and quantum chemical studies

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by 193 nm laser flash photolysis of silacyclopent-3-ene, have been carried out in the presence of ammonia, NH3. Second order kinetics were observed. The reaction was studied in the gas phase at 10 Torr total pressure in SF6 bath gas at each of the three temperatures, 299, 340 and 400 K. The second order rate constants (laser pulse energy of 60 mJ/pulse) fitted the Arrhenius equation: log(k/cm3 molecule-1 s-1) = (-10.37 ± 0.17) + (0.36 ± 1.12 kJ mol-1)/RTln10 Experiments at other pressures showed that these rate constants were unaffected by pressure in the range 10-100 Torr, but showed small decreases in value at 3 and 1 Torr. There was also a weak intensity dependence, with rate constants decreasing at laser pulse energies of 30 mJ/pulse. Ab initio calculations at the G3 level of theory, show that SiH2 + NH3 should form an initial adduct (donor-acceptor complex), but that energy barriers are too great for further reaction of the adduct. This implies that SiH2 + NH3 should be a pressure dependent association reaction. The experimental data are inconsistent with this and we conclude that SiH2 decays are better explained by reaction of SiH2 with the amino radical, NH2, formed by photodissociation of NH3 at 193 nm. The mechanism of this previously unstudied reaction is discussed.

A review of studies performed to assess metal uptake by earthworms

Earthworms perform a number of essential functions in soil; the impacts of metals on earthworms are often investigated. In this review we consider the range of earthworm species, types of soil and forms of metal for which metal uptake and accumulation have been studied, the design of these experiments and the quantitative relationships that have been derived to predict earthworm metal body burden. We conclude that there is a need for more studies on earthworm species other than Eisenia fetida in order to apply the large existing database on this earthworm to other, soil dwelling species. To aid comparisons between studies agreement is needed on standard protocols that define exposure and deputation periods and the parameters, such as soil solution composition, soil chemical and physical properties to be measured. It is recommended that more field or terrestrial model ecosystem studies using real contaminated soil rather than metal-amended artificial soils are performed. (c) 2006 Elsevier Ltd. All rights reserved.

Airborne measurements of the spatial distribution of aerosol chemical composition across Europe and evolution of the organic fraction

The spatial distribution of aerosol chemical composition and the evolution of the Organic Aerosol (OA) fraction is investigated based upon airborne measurements of aerosol chemical composition in the planetary boundary layer across Europe. Sub-micron aerosol chemical composition was measured using a compact Time-of-Flight Aerosol Mass Spectrometer (cToF-AMS). A range of sampling conditions were evaluated, including relatively clean background conditions, polluted conditions in North-Western Europe and the near-field to far-field outflow from such conditions. Ammonium nitrate and OA were found to be the dominant chemical components of the sub-micron aerosol burden, with mass fractions ranging from 20--50% each. Ammonium nitrate was found to dominate in North-Western Europe during episodes of high pollution, reflecting the enhanced NO_x and ammonia sources in this region. OA was ubiquitous across Europe and concentrations generally exceeded sulphate by 30--160%. A factor analysis of the OA burden was performed in order to probe the evolution across this large range of spatial and temporal scales. Two separate Oxygenated Organic Aerosol (OOA) components were identified; one representing an aged-OOA, termed Low Volatility-OOA and another representing fresher-OOA, termed Semi Volatile-OOA on the basis of their mass spectral similarity to previous studies. The factors derived from different flights were not chemically the same but rather reflect the range of OA composition sampled during a particular flight. Significant chemical processing of the OA was observed downwind of major sources in North-Western Europe, with the LV-OOA component becoming increasingly dominant as the distance from source and photochemical processing increased. The measurements suggest that the aging of OA can be viewed as a continuum, with a progression from a less oxidised, semi-volatile component to a highly oxidised, less-volatile component. Substantial amounts of pollution were observed far downwind of continental Europe, with OA and ammonium nitrate being the major constituents of the sub-micron aerosol burden. Such anthropogenically perturbed air masses can significantly perturb regional climate far downwind of major source regions.

Preparation and properties of gallaborane, GaBH6: structure of the gaseous molecule H2Ga(μ-H)2BH2 as determined by vibrational, electron diffraction, and ab initio studies, and structure of the crystalline solid at 110 K as determined by x-ray diffraction``

Gallaborane (GaBH6, 1), synthesized by the metathesis of LiBH4 with [H2GaCl]n at ca. 250 K, has been characterized by chemical analysis and by its IR and 1H and 11B NMR spectra. The IR spectrum of the vapor at low pressure implies the presence of only one species, viz. H2Ga(μ-H)2BH2, with a diborane-like structure conforming to C2v symmetry. The structure of this molecule has been determined by gas-phase electron diffraction (GED) measurements afforced by the results of ab initio molecular orbital calculations. Hence the principal distances (rα in Å) and angles ( α in deg) are as follows: r(Ga•••B), 2.197(3); r(Ga−Ht), 1.555(6); r(Ga−Hb), 1.800(6); r(B−Ht), 1.189(7); r(B−Hb), 1.286(7); Hb−Ga−Hb, 71.6(4); and Hb−B−Hb, 110.0(5) (t = terminal, b = bridging). Aggregation of the molecules occurs in the condensed phases. X-ray crystallographic studies of a single crystal at 110 K reveal a polymeric network with helical chains made up of alternating pseudotetrahedral GaH4 and BH4 units linked through single hydrogen bridges; the average Ga•••B distance is now 2.473(7) Å. The compound decomposes in the condensed phases at temperatures exceeding ca. 240 K with the formation of elemental Ga and H2 and B2H6. The reactions with NH3, Me3N, and Me3P are also described.

C–H local modes in cyclobutene. II. Laser photoacoustic studies 10 000–17 000 cm−1. Vibrational structure and C–H local mode dynamics

In part I of this study [Baggott, Clase, and Mills, Spectrochim. Acta Part A 42, 319 (1986)] we presented FTIR spectra of gas phase cyclobutene and modeled the v=1–3 stretching states of both olefinic and methylenic C–H bonds in terms of a local mode model. In this paper we present some improvements to our original model and make use of recently derived ‘‘x,K relations’’ to find the equivalent normal mode descriptions. The use of both the local mode and normal mode approaches to modeling the vibrational structure is described in some detail. We present evidence for Fermi resonance interactions between the methylenic C–H stretch overtones and ring C–C stretch vibrations, revealed in laser photoacoustic spectra in the v=4–6 region. An approximate model vibrational Hamiltonian is proposed to explain the observed structure and is used to calculate the dynamics of the C–H stretch local mode decay resulting from interaction with lower frequency ring modes. The implications of our experimental and theoretical studies for mode‐selective photochemistry are discussed briefly.

Whole crop cereals 1. Effect of method of harvest and preservation on chemical composition, apparent digestibility and energy value

A total of 133 samples (53 fermented unprocessed, 19 fermented processed. 62 urea-treated processed) of whole crop wheat (WCW) and 16 samples (five fermented unprocessed, six fermented processed, five urea-treated processed) of whole crop barley (WCB) were collected from commercial farms over two consecutive years (2003/2004 and 2004/2005). Disruption of the maize grains to increase starch availability was achieved at the point of harvest by processors fitted to the forage harvesters. All samples were subjected to laboratory analysis whilst 50 of the samples (24 front Year 1, 26 front Year 2 all WCW except four WCB in Year 2) were subjected to in vivo digestibility and energy value measurements using mature wether sheep. Urea-treated WCW had higher (P<0.05) pH, and dry matter (DM) and crude protein contents and lower concentrations of fermentation products than fermented WCW. Starch was generally lower in fermented, unprocessed WCW and no effect of crop maturity at harvest (as indicated by DM content) on starch concentrations was seen. Urea-treated WCW had higher (P<0.05) in vivo digestible organic matter contents in the DM (DOMD) in Year 1 although this was not recorded in Year 2. There was a close relationship between the digestibility values of organic matter and gross energy thus aiding the use of DOMD to predict metabolisable energy (ME) content. A wide range of ME values was observed (WCW. 8.7-11.8 MJ/kg DM; WCB 7.9-11.2 MJ/kg DM) with the overall ME/DOMD ratio (ME = 0.0156 DOMD) in line With Studies in other forages. There was no evidence that a separate ME/DOMD relationship was needed for WCB which is helpful for practical application. This ratio and other parameters were affected by year of harvest (P<0.05) highlighting the influence of environmental and Other undefined factors. The variability in the composition and nutritive value of WCW and WCB highlights the need for reliable and accurate evaluation methods to be available to assess the Value of these forages before they are included in diets for dairy cows. (C) 2008 Elsevier B.V. All rights reserved.

Chemical characterisation of wild populations of Thymus from different climatic regions in southeast Spain

Thymus is taxonomically a very complex genus with a high frequency of hybridisation and introgression among sympatric species. The variation in accumulation of leaf-surface flavonoids was investigated in 71 wild populations of Thymus front different putative hybrid swarm areas in Andalucia, Spain. Twenty-two flavones, five flavanones, two dihydroflavonols, a flavonol and two unknowns were detected by HPLC-DAD combined with LC-APCI-MS analysis. The majority of compounds were flavones with a lutelin-type substitution of the B-ring, in contrast to previous reports on Macedonian taxa, which predominantly accumulate flavones with apigenin-type substitution of the B-ring. Anatomical and morphometric studies, supported by cluster analysis, identified pure Thymus hyemalis and Thymus baeticus populations, and a large number of putative hybrids. Flavonoid variation was closely related to morphological variation in all populations and is suspected to be a result of genetic polymorphism. Principal component analysis identified the presence of species-specific and geographically linked chemotypes and putative hybrids with mixed morphological and chemical characteristics. Qualitative and quantitative flavonoid accumulation appears to be genetically regulated, while external factors play a secondary role. Flavonoid profiles can thus provide diagnostic markers for the taxonomy of Thymus and are also useful in detecting hybridising taxa. (C) 2007 Elsevier Ltd. All rights reserved.

Experimental and theoretical evidence for homogeneous catalysis in the gas-phase reaction of SiH2 with H2O (and D2O): a combined kinetic and quantum chemical study

Time-resolved kinetic studies of the reaction of silylene, SiH2, with H2O and with D2O have been carried out in the gas phase at 297 K and at 345 K, using laser flash photolysis to generate and monitor SiH2. The reaction was studied independently as a function of H2O (or D2O) and SF6 (bath gas) pressures. At a fixed pressure of SF6 (5 Torr), [SiH2] decay constants, k(obs), showed a quadratic dependence on [H2O] or [D2O]. At a fixed pressure of H2O or D2O, k(obs) Values were strongly dependent on [SF6]. The combined rate expression is consistent with a mechanism involving the reversible formation of a vibrationally excited zwitterionic donor-acceptor complex, H2Si...OH2 (or H2Si...OD2). This complex can then either be stabilized by SF6 or it reacts with a further molecule of H2O (or D2O) in the rate-determining step. Isotope effects are in the range 1.0-1.5 and are broadly consistent with this mechanism. The mechanism is further supported by RRKM theory, which shows the association reaction to be close to its third-order region of pressure (SF6) dependence. Ab initio quantum calculations, carried out at the G3 level, support the existence of a hydrated zwitterion H2Si...(OH2)(2), which can rearrange to hydrated silanol, with an energy barrier below the reaction energy threshold. This is the first example of a gas-phase-catalyzed silylene reaction.

What have we learnt about heavy carbenes through laser flash photolysis studies?

Time resolved gas-phase kinetic studies have contributed a great deal of fundamental information about the reactions and reactivity of heavy carbenes (silylenes, germylenes and stannylenes) during the past two decades. In this article we trace the development of our understanding through the mechanistic themes of intermediate complexes, third body assisted associations, catalysed reactions, non-observed reactions and substituent effects. Ab initio (quantum chemical) calculations have substantially assisted mechanistic interpretation and are discussed where appropriate. Trends in reactivity are identified and some signposts to future studies are indicated. This review, although detailed, is not comprehensive.

Gas-phase kinetic and theoretical studies of reactions of germylenes and dimethylstannylene

The results of time-resolved gas phase studies of labile germylenes (GeH2 and GeMe2) and dimethylstannylene (SnMe2) reactions reported to date are considered together with data of quantum-chemical investigations of the potential energy surfaces of these systems. Reaction mechanisms are discussed. A comparison of reactivity in the series of carbene analogs, ER2 (E = Si, Ge, Sn, R = H, Me), is made.

13C-2H correlation NMR spectroscopy studies of the in vivo transformations of natural products from Artemisia annua

13C-2H correlation NMR spectroscopy (13C-2H COSY) permits the identification of 13C and 2H nuclei which are connected to one another by a single chemical bond via the sizeable 1JCD coupling constant. The practical development of this technique is described using a 13C-2H COSY pulse sequence which is derived from the classical 13C-1H correlation experiment. An example is given of the application of 13C-2H COSY to the study of the biogenesis of natural products from the anti-malarial plant Artemisia annua, using a doubly-labelled precursor molecule. Although the biogenesis of artemisinin, the anti-malarial principle from this species, has been extensively studied over the past twenty years there is still no consensus as to the true biosynthetic route to this important natural product – indeed, some published experimental results are directly contradictory. One possible reason for this confusion may be the ease with which some of the metabolites from A. annua undergo spontaneous autoxidation, as exemplified by our recent in vitro studies of the spontaneous autoxidation of dihydroartemisinic acid, and the application of 13C-2H COSY to this biosynthetic problem has been important in helping to mitigate against such processes. In this in vivo application of 13C-2H COSY, [15-13C2H3]-dihydroartemisinic acid (the doubly-labelled analogue of the natural product from this species which was obtained through synthesis) was fed to A. annua plants and was shown to be converted into several natural products which have been described previously, including artemisinin. It is proposed that all of these transformations occurred via a tertiary hydroperoxide intermediate, which is derived from dihyroartemisinic acid. This intermediate was observed directly in this feeding experiment by the 13C-2H COSY technique; its observation by more traditional procedures (e.g., chromatographic separation, followed by spectroscopic analysis of the purified product) would have been difficult owing to the instability of the hydroperoxide group (as had been established previously by our in vitro studies of the spontaneous autoxidation of dihydroartemisinic acid). This same hydroperoxide has been reported as the initial product of the spontaneous autoxidation of dihydroartemisinic acid in our previous in vitro studies. Its observation in this feeding experiment by the 13C-2H COSY technique, a procedure which requires the minimum of sample manipulation in order to achieve a reliable identification of metabolites (based on both 13C and 2H chemical shifts at the 15-position), provides the best possible evidence for its status as a genuine biosynthetic intermediate, rather than merely as an artifact of the experimental procedure.

Ruthenium (III) complexes of tetradentate NSNO pyridylthioazophenolates: Synthesis, spectral studies, crystal structure and redox properties

A family of ruthenium (III) complexes of tetradentate monobasic NSNO donor chelators (HL) have been synthesized and isolated in their pure form. On chromatographic separation, trans-dichloro and cis-dichloro ruthenium (111) complexes of pyridylthioazophenolates are eluted using 19:1 and 7:3 (v/v) DCM-MeOH mixtures, respectively. Both cis and trans isomers of the dark brown colored ruthenium (111) complexes, having the general formula of [Ru(L)Cl-2], have been characterized by elemental analyses, spectroscopic and other physico-chemical tools. The magnetic moments of both the cis- and trans-[Ru(L)Cl-2] complexes are in the range of 1.71-1.79 BM. One of the complexes, trans-[Ru(L1)Cl-2] (2a), has been subjected to single-crystal X-ray analysis which confirms that the chlorines are in mutually trans positions in the molecule. The EPR spectra of the cis-[Ru(L)Cl-2] complexes (1) in DMF are consistent with the fact that the complexes are low-spin octahedral with one unpaired electron having three different g values (g(x) not equal g(y) not equal g(z)) complexes are monomeric with an octahedral coordination sphere. The electrochemical studies of [Ru(L)Cl,] in DMF show a quasi-reversible voltammogram. The reduction potentials for the cis-isomers are comparatively lower than those of the corresponding trans isomers. On reaction with the bidentate bipyridyl ligand in the presence of AgNO3, the cis-[Ru(L)Cl-2] complexes (1) produce a series of complexes with the general formula [Ru(L)(bpy)(2)](PF6)(2) (3). which have also been characterized by elemental analyses, spectroscopic and other physico-chemical tools. (c) 2006 Elsevier Ltd. All rights reserved.

Chemical, physical and electrical properties of aged dodecylbenzene 2: thermal ageing of single isomers in air

The linear isomer of dodecylbenzene (DDB), 1-phenyldodecane, was aged at temperatures of 105 and 135 degrees C in air and the resultant products were analyzed using a range of analytical techniques. On ageing, the 1-phenyldodecane darkened, the acid number, dielectric loss and water content increased and significant oxidation peaks were detected in the infrared spectrum. When aged in the presence of copper, a characteristic peak at 680 nm was also detected by UV/visible spectroscopy but, compared with previous studies of a cable-grade DDB, the strength of this peak was much increased and no appreciable precipitate formation occurred. At the same time, very high values of dielectric loss were recorded. On ageing in the absence of copper, an unusually strong infrared carbonyl band was seen, which correlates well with the detection of dodecanophenone by gas chromatography / mass spectrometry and nuclear magnetic resonance spectroscopy. It was therefore concluded that the ageing process proceeds via the initial production of aromatic ketones, which may then be further oxidized to carboxylic acids. In the presence of copper, these oxidation products are present in lower quantities, most of these oxidation products being combined with the copper present in the oil to give copper carboxylates. The behavior is described in terms of a complex autoxidation mechanism, in which copper acts as both an oxidizing and a reducing agent, depending on its oxidation state and, in particular, promotes elimination via the oxidation of intermediate alkyl radical species to carbocations.