Increase in rice grain arsenic for regions of Bangladesh irrigating paddies with elevated arsenic in groundwaters.

Concern has been raised by Bangladeshi and international scientists about elevated levels of arsenic in Bengali food, particularly in rice grain. This is the first inclusive food market-basket survey from Bangladesh, which addresses the speciation and concentration of arsenic in rice, vegetables, pulses, and spices. Three hundred thirty aman and boro rice, 94 vegetables, and 50 pulse and spice samples were analyzed for total arsenic, using inductivity coupled plasma mass spectrometry (ICP-MS). The districts with the highest mean arsenic rice grain levels were all from southwestern Bangladesh:? Faridpur (boro) 0.51 > Satkhira (boro) 0.38 > Satkhira (aman) 0.36 > Chuadanga (boro) 0.32 > Meherpur (boro) 0.29 µg As g-1. The vast majority of food ingested arsenic in Bangladesh diets was found to be inorganic; with the predominant species detected in Bangladesh rice being arsenite (AsIII) or arsenate (AsV) with dimethyl arsinic acid (DMAV) being a minor component. Vegetables, pulses, and spices are less important to total arsenic intake than water and rice. Predicted inorganic arsenic intake from rice is modeled with the equivalent intake from drinking water for a typical Bangladesh diet. Daily consumption of rice with a total arsenic level of 0.08 µg As g-1 would be equivalent to a drinking water arsenic level of 10 µg L-1. Concern has been raised by Bangladeshi and international scientists about elevated levels of arsenic in Bengali food, particularly in rice grain. This is the first inclusive food market-basket survey from Bangladesh, which addresses the speciation and concentration of arsenic in rice, vegetables, pulses, and spices. Three hundred thirty aman and boro rice, 94 vegetables, and 50 pulse and spice samples were analyzed for total arsenic, using inductivity coupled plasma mass spectrometry (ICP-MS). The districts with the highest mean arsenic rice grain levels were all from southwestern Bangladesh:? Faridpur (boro) 0.51 > Satkhira (boro) 0.38 > Satkhira (aman) 0.36 > Chuadanga (boro) 0.32 > Meherpur (boro) 0.29 µg As g-1. The vast majority of food ingested arsenic in Bangladesh diets was found to be inorganic; with the predominant species detected in Bangladesh rice being arsenite (AsIII) or arsenate (AsV) with dimethyl arsinic acid (DMAV) being a minor component. Vegetables, pulses, and spices are less important to total arsenic intake than water and rice. Predicted inorganic arsenic intake from rice is modeled with the equivalent intake from drinking water for a typical Bangladesh diet. Daily consumption of rice with a total arsenic level of 0.08 µg As g-1 would be equivalent to a drinking water arsenic level of 10 µg L-1.

Hierarchical zeolites prepared by organosilane templating: A study of the synthesis mechanism and catalytic activity

The crystallization of hierarchical ZSM-5 in the presence of the organosilane octadecyl-dimethyl-(3-trimethoxysilyl-propyl)-ammonium chloride as the mesoporogen was investigated as a function of time and temperature. The synthesis by this method proceeds in two steps. The rapid formation of a predominantly amorphous disordered mesoporous aluminosilicate precursor phase is followed by the formation of globular highly mesoporous zeolite particles involving dissolution of the precursor phase. It is difficult to completely convert the initial phase into the final hierarchical zeolite. This limits the amount of aluminium built into the MFI network and the resulting Bronsted acidity. In the presence of iron, more crystalline hierarchical zeolite is obtained. These Fe-containing zeolites are excellent catalysts for the selective oxidation of benzene to phenol. Their hierarchical pore structure leads to higher reaction rates due to increased mass transfer and increased catalyst longevity despite more substantial coke formation. (C) 2011 Elsevier B.V. All rights reserved.

Low pressure carbon dioxide solubility in lithium-ion batteries based electrolytes as a function of temperature. Measurement and prediction

We present in this study the effect of nature and concentration of lithium salt, such as the lithium hexafluorophosphate, LiPF6; lithium tris(pentafluoroethane)-trifluorurophosphate LiFAP; lithium bis(trifluoromethylsulfonyl)imide, LiTFSI, on the CO2 solubility in four electrolytes for lithium ion batteries based on pure solvent that include ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), as well as, in the EC:DMC, EC:EMC and EC:DEC (50:50) wt.% binary mixtures as a function of temperature from (283 to 353) K and atmospheric pressure. Based on experimental solubility values, the Henry’s law constant of the carbon dioxide in these solutions with the presence or absence of lithium salt was then deduced and compared with reported values from the literature, as well as with those predicted by using COSMO-RS methodology within COSMOThermX software. From this study, it appears that the addition of 1 mol · dm-3 LiPF6 salt in alkylcarbonate solvents decreases their CO2 capture capacity. By using the same experimental conditions, an opposite CO2 solubility trend was generally observed in the case of the addition of LiFAP or LiTFSI salts in these solutions. Additionally, in all solutions investigated during this work, the CO2 solubility is greater in electrolytes containing the LiFAP salt, followed by those based on the LiTFSI case. The precision and accuracy of the experimental data reported therein, which are close to (1 and 15)%, respectively. From the variation of the Henry’s law constant with temperature, the partial molar thermodynamic functions of dissolution such as the standard Gibbs energy, the enthalpy, and the entropy, as well as the mixing enthalpy of the solvent with CO2 in its hypothetical liquid state were calculated. Finally, a quantitative analysis of the CO2 solubility evolution was carried out in the EC:DMC (50:50) wt.% binary mixture as the function of the LiPF6 or LiTFSI concentration in solution to elucidate how ionic species modify the CO2 solubility in alkylcarbonates-based Li-ion electrolytes by investigating the salting effects at T = 298.15 K and atmospheric pressure.

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).

Changed reactivity of the 1-bromo-4-nitrobenzene radical anion in a room temperature ionic liquid

Radical anions of 1-bromo-4-nitrobenzene (p-BrC6H4NO2) are shown to be reactive in the room temperature ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, ([C(4)mPyrr][NTf2]), by means of voltammetric measurements. In particular, they are shown to react via a DISP type mechanism such that the electrolysis of p-BrC6H4NO2 occurs consuming between one and two electrons per reactant molecule, leading to the formation of the nitrobenzene radical anion and bromide ions. This behaviour is a stark contrast to that in conventional non-aqueous solvents such as acetonitrile, dimethyl sulfoxide or N,N-dimethylformamide, which suggests that the ionic solvent promotes the reactivity of the radical anion, probably via stabilisation of the charged products.

Heterogeneous oxidation of pyrimidine and alkyl thioethers in ionic liquids over mesoporous Ti or Ti/Ge catalysts

Heterogeneous catalytic oxidation of a series of thioethers (2-thiomethylpyrimidine, 2-thiomethyl-4,6-dimethyl-pyrimidine, 2-thiobenzylpyrimidine, 2-thiobenzyl-4,6-dimethylpyrimidine, thioanisole, and n-heptyl methyl sulfide) was performed in ionic liquids by using MCM-41 and UVM-type mesoporous catalysts containing Ti, or Ti and Ge. A range of triflate, tetrafluoroborate, trifluoroacetate, lactate and bis(trifluoromethanesulfonyl)imide-based ionic liquids were used. The oxidations were carried out by using anhydrous hydrogen peroxide or the urea-hydrogen peroxide adduct and showed that ionic liquids are very effective solvents, achieving greater reactivity and selectivity than reactions performed in dioxane. The effects of halide and acid impurities on the reactions were also investigated. Recycling experiments on catalysts were carried out in order to evaluate Ti leaching and its effect on activity and selectivity.

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.

Facile synthesis of thiol-functionalized amphiphilic polylactide–methacrylic diblock copolymers

Biodegradable amphiphilic diblock copolymers based on an aliphatic ester block and various hydrophilic methacrylic monomers were synthesized using a novel hydroxyl-functionalized trithiocarbonate-based chain transfer agent. One protocol involved the one-pot simultaneous ring-opening polymerization (ROP) of the biodegradable monomer (3S)-cis-3,6-dimethyl-1,4-dioxane-2,5-dione (L-lactide, LA) and reversible addition–fragmentation chain transfer (RAFT) polymerization of 2-(dimethylamino)ethyl methacrylate (DMA) or oligo(ethylene glycol) methacrylate (OEGMA) monomer, with 4-dimethylaminopyridine being used as the ROP catalyst and 2,2′-azobis(isobutyronitrile) as the initiator for the RAFT polymerization. Alternatively, a two-step protocol involving the initial polymerization of LA followed by the polymerization of DMA, glycerol monomethacrylate or 2-(methacryloyloxy)ethyl phosphorylcholine using 4,4′-azobis(4-cyanovaleric acid) as a RAFT initiator was also explored. Using a solvent switch processing step, these amphiphilic diblock copolymers self-assemble in dilute aqueous solution. Their self-assembly provides various copolymer morphologies depending on the block compositions, as judged by transmission electron microscopy and dynamic light scattering. Two novel disulfide-functionalized PLA-branched block copolymers were also synthesized using simultaneous ROP of LA and RAFT copolymerization of OEGMA or DMA with a disulfide-based dimethacrylate. The disulfide bonds were reductively cleaved using tributyl phosphine to generate reactive thiol groups. Thiol–ene chemistry was utilized for further derivatization with thiol-based biologically important molecules and heavy metals for tissue engineering or bioimaging applications, respectively.

Synthesis of the C(7)-C(22)-Sector of (+)-Acutiphycin Via O-Directed Double Free Radical Alkyne Hydrostannation with Ph3SnH/Et3B, Double I-Sn Exchange and Double Stille Coupling

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Herein a new double O-directed free radical hydrostannation reaction is reported on the structurally complex dialkyldiyne 11. Through our use of a conformation-restraining acetal to help prevent stereocenter-compromising 1,5-H-atom abstraction reactions by vinyl radical intermediates, the two vinylstannanes of 10 were concurrently constructed with high stereocontrol using Ph3SnH/Et3B/O2. Distannane 10 was thereafter elaborated into the bis-vinyl iodide 9 via O-silylation and double I–Sn exchange; double Stille coupling of 9, O-desilylation, and oxidation thereafter furnished 8.

Low pressure methane solubility in lithium-ion batteries based solvents and electrolytes as a function of temperature. Measurement and prediction

The methane solubility in five pure electrolyte solvents and one binary solvent mixture for lithium ion batteries – such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC) and the (50:50 wt%) mixture of EC:DMC was studied experimentally at pressures close to atmospheric and as a function of temperature between (280 and 343) K by using an isochoric saturation technique. The effect of the selected anions of a lithium salt LiX (X = hexafluorophosphate,

Concomitant osmotic and chaotropicity-induced stresses in Aspergillus wentii: compatible solutes determine the biotic window

Whereas osmotic stress response induced by solutes has been well-characterized in fungi, less is known about the other activities of environmentally ubiquitous substances. The latest methodologies to define, identify and quantify chaotropicity, i.e. substance-induced destabilization of macromolecular systems, now enable new insights into microbial stress biology (Cray et al. in Curr Opin Biotechnol 33:228–259, 2015a, doi:10.​1016/​j.​copbio.​2015.​02.​010; Ball and Hallsworth in Phys Chem Chem Phys 17:8297–8305, 2015, doi:10.​1039/​C4CP04564E; Cray et al. in Environ Microbiol 15:287–296, 2013a, doi:10.​1111/​1462-2920.​12018). We used Aspergillus wentii, a paradigm for extreme solute-tolerant fungal xerophiles, alongside yeast cell and enzyme models (Saccharomyces cerevisiae and glucose-6-phosphate dehydrogenase) and an agar-gelation assay, to determine growth-rate inhibition, intracellular compatible solutes, cell turgor, inhibition of enzyme activity, substrate water activity, and stressor chaotropicity for 12 chemically diverse solutes. These stressors were found to be: (i) osmotically active (and typically macromolecule-stabilizing kosmotropes), including NaCl and sorbitol; (ii) weakly to moderately chaotropic and non-osmotic, these were ethanol, urea, ethylene glycol; (iii) highly chaotropic and osmotically active, i.e. NH4NO3, MgCl2, guanidine hydrochloride, and CaCl2; or (iv) inhibitory due primarily to low water activity, i.e. glycerol. At ≤0.974 water activity, Aspergillus cultured on osmotically active stressors accumulated low-M r polyols to ≥100 mg g dry weight−1. Lower-M r polyols (i.e. glycerol, erythritol and arabitol) were shown to be more effective for osmotic adjustment; for higher-M r polyols such as mannitol, and the disaccharide trehalose, water-activity values for saturated solutions are too high to be effective; i.e. 0.978 and 0.970 (25 ºC). The highly chaotropic, osmotically active substances exhibited a stressful level of chaotropicity at physiologically relevant concentrations (20.0–85.7 kJ kg−1). We hypothesized that the kosmotropicity of compatible solutes can neutralize chaotropicity, and tested this via in-vitro agar-gelation assays for the model chaotropes urea, NH4NO3, phenol and MgCl2. Of the kosmotropic compatible solutes, the most-effective protectants were trimethylamine oxide and betaine; but proline, dimethyl sulfoxide, sorbitol, and trehalose were also effective, depending on the chaotrope. Glycerol, by contrast (a chaotropic compatible solute used as a negative control) was relatively ineffective. The kosmotropic activity of compatible solutes is discussed as one mechanism by which these substances can mitigate the activities of chaotropic stressors in vivo. Collectively, these data demonstrate that some substances concomitantly induce chaotropicity-mediated and osmotic stresses, and that compatible solutes ultimately define the biotic window for fungal growth and metabolism. The findings have implications for the validity of ecophysiological classifications such as ‘halophile’ and ‘polyextremophile’; potential contamination of life-support systems used for space exploration; and control of mycotoxigenic fungi in the food-supply chain.

De novo sequencing of two novel peptides homologous to calcitonin-like peptides, from skin secretion of the Chinese Frog, Odorrana schmackeri

An MS/MS based analytical strategy was followed to solve the complete sequence of two new peptides from frog (Odorrana schmackeri) skin secretion. This involved reduction and alkylation with two different alkylating agents followed by high resolution tandem mass spectrometry. De novo sequencing was achieved by complementary CID and ETD fragmentations of full-length peptides and of selected tryptic fragments. Heavy and light isotope dimethyl labeling assisted with annotation of sequence ion series. The identified primary structures are GCD[I/L]STCATHN[I/L]VNE[I/L]NKFDKSKPSSGGVGPESP-NH2 and SCNLSTCATHNLVNELNKFDKSKPSSGGVGPESF-NH2, i.e. two carboxyamidated 34 residue peptides with an aminoterminal intramolecular ring structure formed by a disulfide bridge between Cys2 and Cys7. Edman degradation analysis of the second peptide positively confirmed the exact sequence, resolving I/L discriminations. Both peptide sequences are novel and share homology with calcitonin, calcitonin gene related peptide (CGRP) and adrenomedullin from other vertebrates. Detailed sequence analysis as well as the 34 residue length of both O. schmackeri peptides, suggest they do not fully qualify as either calcitonins (32 residues) or CGRPs (37 amino acids) and may justify their classification in a novel peptide family within the calcitonin gene related peptide superfamily. Smooth muscle contractility assays with synthetic replicas of the S–S linked peptides on rat tail artery, uterus, bladder and ileum did not reveal myotropic activity.

Biomass-derived oxymethylene ethers as diesel additives: A techno-economic assessment

Conversion of agricultural biomass such as wood chips, wheat straw and forest residue for the production of fuels can help in reducing GHG emissions since they are considered as nearly carbon neutral. Around the world there is a significant amount of forest and agricultural-biomass available which could be used for the production of liquid fuels that can be blended with the petroleum-based diesel. Oxymethylene ethers (OMEs) can be derived from biomass via gasification, water-gas shift reaction and methanol production. The addition of OMEs to conventional diesel fuel has great potential to reduce soot formation during the combustion in diesel engines. Unlike methanol and dimethyl ether (DMM) which can also reduce soot formation, the physical properties of OMEs allow the use in modern diesel engines without significant change of the engines infrastructure. In this study, a detailed and data intensive process simulation model was developed to simulate all the unit operations involved in the production of OMEs from biomass. The unit operation considered include biomass drying, gasification, gas cleaning, water gas shift reaction, methanol production and OMEs synthesis. The simulation results were then utilized to conduct a detailed techno-economic assessment study of the whole biomass conversion chain to determine the most attractive pathways for OMEs production. Our recent study shows that the key parameters affecting the OMEs production are equivalence ratio, H2/CO ratio and optimal air flow. Overall, the cost of production ($/liter) of OMEs from different biomass feedstock in Alberta will be determined