NMR analysis of Nile Blue (C I Basic Blue 12) and Thionine (C I 52000) in solution

The dyes Nile Blue (C I Basic Blue 12) and Thionine (C I 52000) were examined in both ionic and neutral forms in different solvents using NMR and UV-visible spectroscopy to firmly establish the structures of the molecules and to assess the nature and extent of their aggregation H-1 and C-13 NMR assignments and chemical shift data were used together with nuclear Overhauser effect information to propose a self-assembly structure These data were supplemented with variable temperature dilution and diffusion-based experimental results using H-1 NMR spectroscopy thereby enabling extended aggregate structures to be assessed in terms of the relative strength of self-association and the extent to which extended aggregates could form (C) 2010 Elsevier Ltd All rights reserved

Low energy C-13(+) and C-13(2+) ion irradiation of water ice

In this paper we report the results of the first experimental study of the irradiation of low temperature water ice (30 and 90 k) using low energy (4keV) C-13(+) and C-(2+) ions. (CO2)-C-13 and H2o2 were readily formed within the H2O ice with the product ion yield and grwoth rate observed to be highly dependent on both the sample temperature and the ion charge state.

delta C-13 and delta N-15 reveal significant differences in the coastal foodwebs of the seas surrounding Trinidad and Tobago

This study assessed nearshore, marine ecosystem function around Trinidad and Tobago (TT). The coastline of TT is highly complex, bordered by the Atlantic Ocean, the Caribbean Sea, the Gulf of Paria and the Columbus Channel, and subject to local terrestrial runoff and regional riverine inputs (e.g. the Orinoco and Amazon rivers). Coastal organisms can assimilate energy from allochthonous and autochthonous Sources, We assessed whether stable isotopes delta C-13 and delta N-15 Could be used to provide a rapid assessment of trophic interactions in primary consumers around the islands. Filter-feeding (bivalves and barnacles) and grazing organisms (gastropods and chitons) were collected from 40 marine sites during the wet season. The flesh of organisms was analysed for delta C-13 and delta N-15. Results indicate significant variation in primary consumers (by feeding guild and sampling zone). This variation was linked to different energy Sources being assimilated by consumers. Results suggest that offshore production is fuelling intertidal foodwebs; for example, a depleted delta C-13 signature in grazers from the Gulf of Paria, Columbus Channel and the Caribbean and Atlantic coastline of 9 Tobago indicates that carbon with an offshore origin (e.g. phytoplankton and dissolved organic matter) is more important than benthic or littoral algae (luring the wet season. Results also confirm findings from other studies indicating that much of the coastline is subject to Cultural eutrophication. This Study revealed that ecosystem function is spatially variable around the coastline of TT, This has clear implications for marine resource management, as a single management approach is unlikely to be successful at a national level.

DENSE GAS IN NEARBY GALAXIES .6. A LARGE C-12/C-13 RATIO IN A NUCLEAR STARBURST ENVIRONMENT

Toward the starburst nucleus of NGC 253, C-12/C-13 line intensity ratios from six carbon bearing molecules (CO, CN, CS, HCN, HCO+, and HNC) are used to confine the possible range of carbon and oxygen isotope ratios. A detailed analysis yields C-12/C-13 approximately 40 and O-16/O-18 approximately 200. Also reported are first detections of (CS)-C-13 and of the 0(0) - 1(-1) E line of methanol (CH3OH) in an extragalactic source.

1-Alkyl-3-methylimidazolium alkanesulfonate ionic liquids, [C(n)H(2n+1)mim][CkH2k+1SO3]: synthesis and physicochemical properties

A set of 1-alkyl-3-methylimidazolium alkanesulfonate ionic liquids, [C(n)mim][CkSO3], formed by the variation of the alkyl chain lengths both in the cation and the anion (n = 1-6, 8, or 10; k = 1-4, or 6), was synthesised, with sixteen of them being novel. The ionic liquids were characterised by H-1 and C-13 NMR spectroscopy, and mass spectrometry. Their viscosities and densities as a function of temperature, as well as melting points and decomposition temperatures, were determined. The molecular volumes, both experimental and calculated, were found to depend linearly on the sum (n + k).

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).

Dramatic solvent effects on ring-opening metathesis polymerization of cycloalkenes

A series of metathesis polymers and copolymers have been formed and their structures were analysed by C-13 NMR spectroscopy. Noble metal and non-noble metal salt catalysts are distinguished by their behaviour in various solvents. Thus, in phenolic solvents, the former class produce alternating copolymers from cyclopentene and norbornene, while the latter are unaffected and produce random copolymers. In contrast, ether solvents have the effect of markedly increasing the cis content of polymers from the latter catalysts while the former are unaffected.

Characteristics of RuCl2(CHPh)(PCy3)(2) as a catalyst for ring-opening metathesis polymerization

Ring-opened metathesis polymers and copolymers have been formed from norbornene, norbornadiene, a range of their derivatives, and cyclopentene using RuCl2(CHPh)(PCy3)(2), as catalyst. C-13 NMR analysis of the polymers illustrate a rather selective propagation reaction. The catalyst is highly regioselective, and the polymers are generally high trans with a strong isotactic bias. However, polymers from diene monomers tend to be less isotactic than those from the corresponding monoenes, and in the case of 7-methylnorbornadiene the polymer has an overall syndiotactic bias. A rate enhancing effect, noted previously, due to an oxygen atom proximate to the monomer double bond, is less pronounced than with other initiators. Catalyst activity, in the case of certain diene monomers, was shown to be monomer dependent and rate enhancements were also achieved using phenol as solvent. The results are interpreted in terms of the steric and electronic properties of both the catalyst and the monomers.

Novel chiral ionic liquids:physicochemical properties and investigation of the internal rotameric behaviour in the neat system

Optically active S-alkyl-N, N'-bis((S)-1-phenylethyl) thiouronium salts, abbreviated as (S)-[Cnpetu] Y (where Y is an anion; n = 1, 2, 3, 4, 6, 8, 10, 12 or 16), have been prepared and studied by a broad spectrum of analyses. This consists of density, viscosity, and conductivity determination, followed by a discussion of relevant correlations. Unusual trends depending on the S-alkyl chain length were documented for (S)-[Cnpetu][ NTf2] series (where [NTf2] = bis{(trifluoromethyl) sulfonyl} amide), including the viscosity decreasing with increasing chain length, and the conductivity showing a maximum between the S-butyl and the S-hexyl derivative. In addition, a hindered rotamerism of the thiouronium cation in dmso-d(6) solution was recognised by H-1 and C-13 NMR techniques. Thorough analysis of NMR spectra confirmed that the main contribution comes from rotation about the partial double C-S bond. For the first time, a neat thiouronium ionic liquid system has been subjected to quantitative analysis of hindered rotamerism by dynamic NMR coalescence studies, with estimated activation energy for rotation of 63.9 +/- 0.4 kJ mol(-1). Finally, the application of (S)-[C(n)petu] Y salts as chiral discriminating agents for carboxylates by 1H NMR spectroscopy was further investigated, demonstrating the influence of the S-alkyl chain length on chiral recognition; (S)-[C(2)petu][NTf2] ionic liquid with the mandelate anion gave the best results.

CO2 Capture in Wet and Dry Superbase Ionic Liquids

The solubility of carbon dioxide in five tetraalkylphosphonium superbase ionic liquids, namely the trihexyltetradecylphoshonium phenoxide, trihexyltetradecylphoshonium benzotriazolide, trihexyltetradecylphoshonium benzimidazolide, trihexyltetradecylphoshonium 1,2,3-triazolide, and trihexyltetradecylphoshonium 1,2,4-triazolide was studied experimentally under dry and wet conditions at 22 A degrees C and at atmospheric pressure, using a gravimetric saturation technique. The effects of anion structure and of the presence or absence of water in the solution on the carbon dioxide solubility were then deduced from the data. H-1 and C-13-NMR spectroscopy and ab initio calculations were also conducted to probe the interactions in these solutions, as carbon dioxide and water can compete in the ionic liquid structure during the absorption process. Additionally, the viscosity of selected superbase ionic liquids was measured under dry and wet conditions, in the presence or absence of CO2, to evaluate their practical application in carbon dioxide capture processes. Finally, the recyclability of the trihexyltetradecylphoshonium 1,2,4-triazolide under dry and wet conditions was determined to probe the ability of selected solvents to solubilize chemically a high concentration of carbon dioxide and then release it in a low energy demand process.

Aza-annulation of enaminones with itaconic anhydride:kinetic preference for exocyclic enamide products

Enaminones react with itaconic anhydride in methylene chloride at room temperature to give exocyclic enamides sis the major products. These can be readily equilibrated to the thermodynamically more stable endocyclic enamides. In substrates where the exocyclic isomer could not be formed only intractable materials were produced from this reaction. An intermediate in this two step process was detected and identified by proton and C-13 NMR spectroscopy. In two cases chiral enaminones were employed and the relative stereochemistry at the new chiral centre in the product was established by a crystal structure of compound 27.

Speciation of Rare-Earth Metal Complexes in Ionic Liquids: A Multiple-Technique Approach

The dissolution process of metal complexes in ionic liquids was investigated by a multiple-technique approach to reveal the solvate species of the metal in solution. The task-specific ionic liquid betainium bis(trifluoromethylsulfonyl)imide ([Hbet][Tf2N]) is able to dissolve stoichiometric amounts of the oxides of the rare-earth elements. The crystal structures of the compounds [Eu-2(bet)(8)(H2O)(4)][Tf2N](6), [Eu-2(bet)(8)(H2O)(2)][Tf2N](6)center dot 2H(2)O, and [Y-2(bet)(6)(H2O)(4)][Tf2N](6) were found to consist of dimers. These rare-earth complexes are well soluble in the ionic liquids [Hbet][Tf2N] and [C(4)mim]- [Tf2N] (C(4)mim = 1-butyl-3-methylimidazolium). The speciation of the metal complexes after dissolution in these ionic liquids was investigated by luminescence spectroscopy, H-1, C-13, and Y-89 NMR spectroscopy, and by the synchrotron techniques EXAFS (extended X-ray absorption fine structure) and HEXS (high-energy X-ray scattering). The combination of these complementary analytical techniques reveals that the cationic dimers decompose into monomers after dissolution of the complexes in the ionic liquids. Deeper insight into the solution processes of metal compounds is desirable for applications of ionic liquids in the field of electrochemistry, catalysis, and materials chemistry.

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.

Photocatalytic organic synthesis in an NMR tube:CC coupling of phenoxyacetic acid and acrylamide

NMR was used to study the semiconductor photocatalytic (SPC) CC coupling of phenoxyacetic acid (PAA) with acrylamide (ACM) in an NMR tube photoreactor. Using an NMR tube with a sol-gel titania inner coating as a photoreactor, this reaction is relatively clean, forming only 1 product, 4-phenoxybutanamide (4-PB), in yields up to 78%. This SPC reaction is used to assess the activity of the sol-gel titania coating as a function of their annealing temperature, which alters the surface area and phase of the titania, and the general reusability of the TiO coated NMR tubes. The optimum temperature range for annealing the sol-gel titania films is between 450 °C and 800 °C, with the maximum yield and rate attained at 450 °C. Despite a decrease in the initial rates of formation of 4-PB above an annealing temperature of 450 °C, the final product yields remained similar, giving maximum yields within 60 min of irradiation. The reusability study reveals that the activity of the sol-gel titania can quickly deteriorate with repeated use due to the adsorption of yellow/brown coloured, insoluble, most likely organic polymeric, material and its screening effect on the underlying photocatalyst. The titania can, however, be restored to its original activity by a simple heat treatment at 450 °C for 30 min.

Lipid extraction has little effect on the delta N-15 of aquatic consumers

Proper application of stable isotopes (e. g., delta N-15 and delta C-13) to food web analysis requires an understanding of all nondietary factors that contribute to isotopic variability. Lipid extraction is often used during stable isotope analysis (SIA), because synthesized lipids have a low delta C-13 and can mask the delta C-13 of a consumer's diet. Recent studies indicate that lipid extraction intended to adjust delta C-13 may also cause shifts in delta N-15, but the magnitude of and reasons for the shift are highly uncertain. We examined a large data set (n = 854) for effects of lipid extraction (using Bligh and dyer's [ 1959] chloroform-methanol solvent mixtures) on the delta N-15 of aquatic consumers. We found no effect of chemically extracting lipids on the delta N-15 of whole zooplankton, unionid mussels, and fish liver samples, and found a small increase in fish muscle delta N-15 of similar to 0.4%. We also detected a negative relationship between the shift in delta N-15 following extraction and the C:N ratio in muscle tissue, suggesting that effects of extraction were greater for tissue with lower lipid content. As long as appropriate techniques such as those from Bligh and dyer (1959) are used, effects of lipid extraction on delta N-15 of aquatic consumers need not be a major consideration in the SIA of food webs.