Chiral thiouronium salts: synthesis, characterisation and application in NMR enantio-discrimination of chiral oxoanions

Chiral thioureas and functionalised chiral thiouronium salts were synthesised starting from the relatively cheap and easily available chiral amines: (S)-methylbenzylamine and rosin-derived (+)-dehydroabietylamine. The introduction of a delocalised positive charge to the thiourea functionality, by an alkylation reaction at the sulfur atom, enables dynamic rotameric processes: hindered rotations about the delocalised CN and CS bonds. Hence, four different rotamers/isomers may be recognised: syn-syn, syn-anti, anti-syn and anti-anti. Extensive H-1 and C-13 NMR studies have shown that in hydrogen-bond acceptor solvents, such as perdeuteriated dimethyl sulfoxide, the syn-syn conformation is preferable. On the other hand, when using non-polar solvents, such as CDCl3, the mixture of syn-syn and syn-anti isomers is detectable, with an excess of the latter. Apart from this, in the case of S-butyl-N,N'-bis(dehydroabietyl)thiouronium ethanoate in CDCl3, the H-1 NMR spectrum revealed that strong bifurcated hydrogen bonding between the anion and the cation causes global rigidity without signs of hindered rotamerism observable on the NMR time scale. This suggested that these new salts might be used as NMR discriminating agents for chiral oxoanions, and are indeed more effective than their archetypal guanidinium analogues or the neutral thioureas. The best results in recognition of a model substrate, mandelate, were obtained with S-butyl-N,N'-bis(dehydroabietyl) thiouronium bistriflamide. It was confirmed that the chiral recognition occurred not only for carboxylates but also for sulfonates and phosphonates. Further H-1 NMR studies confirmed a 1 : 1 recognition mode between the chiral agent (host) and the substrate (guest); binding constants were determined by H-1 NMR titrations in solutions of DMSO-d(6) in CDCl3. It was also found that the anion of the thiouronium salt had a significant influence on the recognition process: anions with poor hydrogen-bond acceptor abilities led to the best discrimination. The presence of host-guest hydrogen bonding was confirmed in the X-ray crystal structure of S-butyl-N,N'-bis(dehydroabietyl)thiouronium bromide and by computational studies (density functional theory).

Palladium-catalyzed liquid-phase hydrogenation/hydrogenolysis of disulfides

For the first time, the hydrogenation/hydrogenolysis of a range of disulfides has been achieved over a supported palladium catalyst using hydrogen under relatively benign conditions. These unexpected results demonstrate that it is possible to avoid the poisoning of the catalyst by either the nitrogen-containing groups or the sulfur species, allowing both efficient reaction and recycling of the catalyst under the proper conditions (e.g., at low temperatures). A slight loss in activity was found on recycling; however, the catalyst activity can be recovered using hydrogen pretreatment. The reaction mechanism for the hydrogenolysis and hydrogenation of ortho-, meta-, and para-dinitrodiphenyldisulfide to the corresponding aminothiophenol has been elucidated. Density functional theory calculations were used to investigate the adsorption mode of the dinitrodiphenyldisulfides; a clear dependence on adsorption geometry was found regarding whether the molecule is cleaved at the S-S bond before the reduction of the nitro group or vice versa. This study demonstrates the versatility of these catalysts for the hydrogenation/hydrogenolysis of sulfur-containing molecules, which normally are considered poisons, and will extend their use to a new family of substrates. (C) 2007 Elsevier Inc. All rights reserved.

The synthesis and chemistry of formylphosphonate

New methods of synthesis and reactions of formylphosphonate have been investigated. Attempts to deprotect the corresponding diethyl acetal with Ti-IV halides led instead to the formation of halo(ethoxy)methylphosphonates which undergo substitution reactions with a wide range of nucleophiles. The products of reactions of formylphosphonate with bifunctional nucleophiles are determined in most cases by Baldwin's Roles, while the imines derived from formylphosphonate undergo Diels-Alder reactions only in those cases which carry a strongly electron-withdrawing N-substituent.

A spectroscopic study of the chemistry and reactivity of SO2 on Pt{111}: Reactions with O-2, CO and C3H6

The chemisorption and reactivity of SO2 on Pt{111} have been studied by HREELS, XPS, NEXAFS and temperature-programmed desorption. At 160 K SO2 adsorbs intact at high coverages, with eta(2) S-O coordination to the surface. On annealing to 270 K, NEXAFS indicates the SO2 molecular plane essentially perpendicular to the surface. Preadsorbed O-a reacts with SO2 to yield adsorbed SO4, identified as the key surface species responsible for SO2-promoted catalytic alkane oxidation. Coadsorbed CO or propene efficiently reduce SO2 overlayers to deposit S-a, and the implications of this for catalytic systems are discussed.

Assessment of the solubility and bioaccessibility of arsenic in realgar wine using a simulated gastrointestinal system

Consumption of arsenic (As) wine is a traditional activity during the classic Chinese festival of Duanwu, colloquially known worldwide as the Dragon Boat Day. Arsenic wine is drunk on the morning of the fifth day of the fifth lunar calendar month to commemorate the death of Qu Yuan, a famed Chinese poet who drowned himself in protest of a corrupt government, and to protect against ill fortune. Although realgar minerals are characteristically composed of sparingly soluble tetra-arsenic tetra-sulfides (As(4)S(4)), purity does vary with up to 10% of As being present as non-sulfur bound species, such as arsenate (As(v)) and arsenite (As(III)). Despite, the renewed interest in As speciation and the bioaccessibility of the active As components in realgar based Chinese medicines, little is known about the safety surrounding the cultural practice of drinking As wine. In a series of experiments the speciation and solubility of As in a range of wines were investigated. Furthermore, a simulated gastrointestinal system was employed to predict the impact of digestive processes on As bioavailability. The predominant soluble As species found in all the wines were As(III) and As(v). Based on typical As wine recipes employing 0.1 g realgar mL(-1) wine, the concentration of dissolved As ranged from ca. 100 to 400 mg L(-1) depending on the ethanol content of the preparation: with the As solubility found to be higher in wines with a lower proportion of ethanol. Based on a common 100 mL measure of wine with a concentration of 400 mg As L(-1), the amount of soluble As would equate to around half of the acute minimal lethal dose for adults. This is likely an underestimate of the bioaccessible concentration, as a three-fold increase in bioaccessibility could be observed in the intestinal phase based on the results from the stimulated gastrointestinal system. (C) 2011 Elsevier B.V. All rights reserved.

Tracking the Fate of Microbially Sequestered Carbon Dioxide in Soil Organic Matter

The microbial contribution to soil organic matter (SOM) has recently been shown to be much larger than previously thought and thus its role in carbon sequestration may also be underestimated. In this study we employ C-13 ((CO2)-C-13) to assess the potential CO2 sequestration capacity of soil chemoautotrophic bacteria and combine nuclear magnetic resonance (NMR) with stable isotope probing (SIP), techniques that independently make use of the isotopic enrichment of soil microbial biomass. In this way molecular information generated from NMR is linked with identification of microbes responsible for carbon capture. A mathematical model is developed to determine real-time CO2 flux so that net sequestration can be calculated. Twenty-eight groups of bacteria showing close homologies with existing species were identified. Surprisingly, Ralstonia eutropha was the dominant group. Through NMR we observed the formation of lipids, carbohydrates, and proteins produced directly from CO2 utilized by microbial biomass. The component of SOM directly associated with CO2 capture was calculated at 2.86 mg C (89.21 mg kg(-1)) after 48 h. This approach can,differentiate between SOM derived through microbial uptake of CO2 and other SOM constituents and represents a first step in tracking the fate and dynamics of microbial biomass in soil.

Determination of geographical origin of distillers dried grains and solubles using isotope ratio mass spectrometry

In recent years distillers dried grains and solubles (DDGS), co-products of the bio-ethanol and beverages industries, have become globally traded commodity for the animal feed sector. As such it is becoming increasingly important to be able to trace the geographical origin of commodities in case of a contamination incident or authenticity issue arise. In this study, 137 DDGS samples from a range of different geographical origins (China, USA, Canada and European Union) were collected and analyzed. Isotope ratio mass spectrometry (IRMS) was used to analyze the DDGS for ²H/¹H, ¹³C/¹²C, ¹⁵N/¹⁴N, ¹⁸O/¹⁶O and ³⁴S/³²S isotope ratios which can vary depending on geographical origin and processing. Univariate and multivariate statistical techniques were employed to investigate the feasibility of using the IRMS data to determine botanical and geographical origin of the DDGS. The results indicated that this commodity could be differentiated according to their place of origin by the analysis of stable isotopes of hydrogen, carbon, nitrogen and oxygen but not with sulfur. By adding data to the models produced in this study, potentially an isotope databank could be set up for traceability procedures for DDGS, similar to the one established already for wine which will help in feed and food security issues arising worldwide.

Arsenic biogeochemistry as affected by phosphorus fertilizer addition, redox potential and pH in a west Bengal (India) soil

This laboratory experiment systematically examines arsenic, iron, and phosphorus solubilities in soil suspensions as affected by addition of phosphorus fertilizer under different redox potential (Eh) and pH conditions. Under aerobic conditions, As solubility was low, however, under moderately reducing conditions (0, -150 mV), As solubility significantly increased due to dissolution of iron oxy-hydroxides. Upon reduction to -250 mV, As solubility was controlled by the formation of insoluble sulfides, and as a result soluble As contents significantly decreased. Soluble Fe concentration increased from moderate to highly anaerobic conditions; however, it decreased under aerobic conditions likely due to formation of insoluble oxy-hydroxides. A low pH, 5.5, led to increased soluble concentrations of As, Fe, and P. Finally, addition of P-fertilizers resulted in higher soluble P and As, even though the concentration of As did not increased after an addition rate of 600 mg P kg(-1) soil. (c) 2006 Elsevier B.V. All rights reserved.

Ionic liquids for efficient hydrogen sulfide and thiol scavenging

Functionalised pyridinium and ammonium ionic liquids bearing a Michael acceptor are shown to scavenge H₂S gas and various thiols, in most cases, without the aid of any added bases. Utilising the effective non-volatility of ionic liquids and ‘tagging’ malodourous substances to an ionic matrix renders them odourless.

A review of biomass co-firing in North America

Biomass fuels have long been accepted as useful renewable energy sources, especially in mitigating greenhouse gases (GHG), nitrogen oxides, and sulfur oxide emissions. Biomass fuel is carbon neutral and is usually low in both nitrogen and sulfur. For the past decade, various forms of biomass fuels have been co-combusted in existing coal-fired boilers and gas-fired power plants. Biomass is used as a supplemental fuel to substitute for up to 10% of the base fuel in most full commercial operations. There are several successful co-firing projects in many parts of the world, particularly in Europe and North America. However, despite remarkable commercial success in Europe, most of the biomass co-firing in North America is limited to demonstration levels. This review takes a detailed look at several aspects of biomass co-firing with a direct focus on North America. It also explores the benefits, such as the reduction of GHG emissions and its implications. This paper shows the results of our studies of the biomass resources available in North America that can be used in coal-fired boilers, their availability and transportation to the power plant, available co-firing levels and technologies, and various technological and environmental issues associated with biomass co-firing. Finally, the paper proffers solutions to help utility companies explore biomass co-firing as a transitional option towards a completely carbon-free power sector in North America.

Radiative charge transfer in cold and ultracold sulphur atoms colliding with protons

Radiative decay processes at cold and ultra cold temperatures for sulfur atoms colliding with protons are investigated. The MOLPRO quantum chemistry suite of codes was used to obtain accurate potential energies and transition dipole moments, as a function of internuclear distance, between low-lying states of the SH+ molecular cation. A multi-reference configuration-interaction approximation together with the Davidson correction is used to determine the potential energy curves and transition dipole moments, between the states of interest, where the molecular orbitals are obtained from state-averaged multi-configuration-self-consistent field calculations. The collision problem is solved approximately using an optical potential method to obtain radiative loss, and a fully two-channel quantum approach for radiative charge transfer. Cross sections and rate coefficients are determined for the first time for temperatures ranging from 10 μK up to 10 000 K. Results are obtained for all isotopes of sulfur, colliding with H+ and D+ ions and comparison is made to a number of other collision systems.

Hydroprocessing of waste cooking oil over a dispersed nano catalyst: Kinetics study and temperature effect

The kinetics of hydrodeoxygenation of waste cooking oil (WCO) is investigated with unsupported CoMoS catalysts. A kinetic model is established and a comprehensive analysis of each reaction pathway is carried out. The results show that hydrodecarbonylation/decarboxylation (HDC) routes are the predominant reaction pathways in the elimination of oxygen, with the rate constant three times as high as that of hydrodeoxygenation (HDO). However, the HDC activity of the CoMoS catalyst deactivates due to gradual loss of sulfur from the catalyst. HDO process is insensitive to the sulfur deficiency. The kinetic modeling shows that direct hydrodecarbonylation of fatty acids dominates the HDC routes and, in the HDO route, fatty acids are transferred to aldehydes/alcohols and then to C-18 hydrocarbons, a final product, and the reduction of acids is the rate limiting step. The HDO route via alcohols is dominant over aldehydes due to a significantly higher reaction rate constant. The difference of C-18/C-17 ratio in unsupported and supported catalysts show that a support with Lewis acid sites may play an important role in the selectivity for the hydrodeoxygenation pathways and promoting the final product quality

The Bdellovibrio bacteriovorus twin-arginine transport system has roles in predatory and prey-independent growth

Bdellovibrio bacteriovorus grows in one of two ways: either (i) predatorily [in a host-dependent (HD) manner], when it invades the periplasm of another Gram-negative bacterium, exporting into the prey co-ordinated waves of soluble enzymes using the prey cell contents for growth; or (ii) in a host-independent (HI) manner, when it grows (slowly) axenically in rich media. Periplasmic invasion potentially exposes B. bacteriovorus to extremes of pH and exposes the need to scavenge electron donors from prey electron transport components by synthesis of metalloenzymes. The twin-arginine transport system (Tat) in other bacteria transports folded metalloenzymes and the B. bacteriovorus genome encodes 21 potential Tat-transported substrates and Tat transporter proteins TatA1, TatA2 and TatBC. GFP tagging of the Tat signal peptide from Bd1802, a high-potential iron-sulfur protein (HiPIP), revealed it to be exported into the prey bacterium during predatory growth. Mutagenesis showed that the B. bacteriovorus tatA2 and tatC gene products are essential for both HI and HD growth, despite the fact that they partially complement (in SDS resistance assays) the corresponding mutations in Escherichia coli where neither TatA nor TatC are essential for life. The essentiality of B. bacteriovorus TatA2 was surprising given that the B. bacteriovorus genome encodes a second tatA homologue, tatA1. Transcription of tatA1 was found to be induced upon entry to the bdelloplast, and insertional inactivation of tatA1 showed that it significantly slowed the rates of both HI and HD growth. B. bacteriovorus is one of a few bacterial species that are reliant on a functional Tat system and where deletion of a single tatA1 gene causes a significant growth defect(s), despite the presence of its tatA2 homologue.

In Helicobacter pylori auto-inducer-2, but not LuxS/MccAB catalysed reverse transsulphuration, regulates motility through modulation of flagellar gene transcription

BACKGROUND: LuxS may function as a metabolic enzyme or as the synthase of a quorum sensing signalling molecule, auto-inducer-2 (AI-2); hence, the mechanism underlying phenotypic changes upon luxS inactivation is not always clear. In Helicobacter pylori, we have recently shown that, rather than functioning in recycling methionine as in most bacteria, LuxS (along with newly-characterised MccA and MccB), synthesises cysteine via reverse transsulphuration. In this study, we investigated whether and how LuxS controls motility of H. pylori, specifically if it has its effects via luxS-required cysteine metabolism or via AI-2 synthesis only.

RESULTS: We report that disruption of luxS renders H. pylori non-motile in soft agar and by microscopy, whereas disruption of mccAHp or mccBHp (other genes in the cysteine provision pathway) does not, implying that the lost phenotype is not due to disrupted cysteine provision. The motility defect of the DeltaluxSHp mutant was complemented genetically by luxSHp and also by addition of in vitro synthesised AI-2 or 4, 5-dihydroxy-2, 3-pentanedione (DPD, the precursor of AI-2). In contrast, exogenously added cysteine could not restore motility to the DeltaluxSHp mutant, confirming that AI-2 synthesis, but not the metabolic effect of LuxS was important. Microscopy showed reduced number and length of flagella in the DeltaluxSHp mutant. Immunoblotting identified decreased levels of FlaA and FlgE but not FlaB in the DeltaluxSHp mutant, and RT-PCR showed that the expression of flaA, flgE, motA, motB, flhA and fliI but not flaB was reduced. Addition of DPD but not cysteine to the DeltaluxSHp mutant restored flagellar gene transcription, and the number and length of flagella.

CONCLUSIONS: Our data show that as well as being a metabolic enzyme, H. pylori LuxS has an alternative role in regulation of motility by modulating flagellar transcripts and flagellar biosynthesis through production of the signalling molecule AI-2.

A density functional theory study on the interaction between chemisorbed CO and S on Rh(111)

Density functional theory calculations are carried out for Rh(111)-p(2 x 2)-CO, Rh(111)-p(2 x 2)-S, Rh(111)-p(2 x 2)-(S + CO), Rh(111)-p(3 x 3)-CO, Rh(111)-p(3 x 3)-S and Rh(111)-p(3 x 3)-(S + CO), aiming to shed some light on the S poisoning effect. Geometrical structures of these systems are optimized and chemisorption energies are determined. The presence of S does not significantly influence the geometrical structure and chemisorption energy of CO and vice versa, which strongly suggests that the interaction between CO and S on the Rh(111) surface is mainly short-range in nature. The long range electronic effect for the dramatic attenuation of the CO methanation activity by sulfur is likely to be incorrect. It is suggested that an ensemble effect may be dominant in the catalytic deactivation. (C) 1999 Elsevier Science B.V. All rights reserved.