Conformational preferences of α,α-trehalose in gas phase and aqueous solution

This work presents an investigation on the conformational preferences of α,α-trehalose in gas phase and aqueous solution. Eighty-one systematically selected structures were studied at the B3LYP/6-311++G(d,p)//B3LYP/6-31G(d) level, giving rise to 40 unique conformers. The 19 lower energy structures and some selected other were further re-optimized at the B3LYP/6-311++G(d,p) level. The main factors accounting for the conformer’s stability were pointed out and discussed. NBO and QTAIM analyses were performed in some selected conformers in order to address the anomeric and exo-anomeric effects as well as intramolecular hydrogen bonding. The effect of solvent water on the relative stability of the conformers was accounted for by applying the conductor-like polarizable continuum model, CPCM.     

Crystallization of metastable beta glycine from gas phase via the sublimation of alpha or gamma form in vacuum

It is found that beta glycine, the metastable polymorph of glycine, can be rapidly formed from gas phase via the sublimation of its stable alpha or gamma form in vacuum. The transformation process was monitored by infrared spectroscopy and the crystal structure of the sublimate was identified by X-ray diffraction techniques. It is the first report about the transformation of stable alpha or gamma glycine into metastable beta form in "one-step" (heating then cool down spontaneously). Crystallization of beta glycine from gas phase is very different from other methods that require additives in solution. The hydrogen-bonding interaction and self-assembling of amino acid were discussed based on the observations.     

Homoleptic copper(II) and copper(I) complexes of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline. Six-coordinate copper(I) in solution

Reaction of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline (L) with Cu(ClO₄)₂·6H₂O in methanol in 3:1 M ratio at room temperature yields light green [CuL₃](ClO₄)₂·H₂O (1). The X-ray crystal structure of the hemi acetonitrile solvate [CuL₃](ClO₄)₂·0.5CH₃CN has been determined which shows Jahn-Teller distortion in the CuN₆ core present in the cation [CuL₃]²⁺. Complex 1 gives an axial EPR spectrum in acetonitrile-toluene glass with g_|| = 2.262 (A_|| = 169 × 10⁻⁴ cm⁻¹) and g_⊥ = 2.069. The Cu(II/I) potential in 1 in CH₂Cl₂ at a glassy carbon electrode is 0.32 V versus NHE. This potential does not change with the addition of extra L in the medium implicating generation of a six-coordinate copper(I) species [CuL₃]⁺ in solution. B3LYP/LanL2DZ calculations show that the six Cu-N bond distances in [CuL₃]⁺ are 2.33, 2.25, 2.32, 2.25, 2.28 and 2.25 Å while the ideal Cu(I)-N bond length in a symmetric Cu(I)N₆ moiety is estimated as 2.25 Å. Reaction of L with Cu(CH₃CN)₄ClO₄ in dehydrated methanol at room temperature even in 4:1 M proportion yields [CuL₂]ClO₄ (2). Its ¹H NMR spectrum indicates that the metal in [CuL₂]⁺ is tetrahedral. The Cu(II/I) potential in 2 is found to be 0.68 V versus NHE in CH₂Cl₂ at a glassy carbon electrode. In presence of excess L, 2 yields the cyclic voltammogram of 1. From ¹H NMR titration, the free energy of binding of L to [CuL₂]⁺ to produce [CuL₃]⁺ in CD₂Cl₂ at 298 K is estimated as −11.7 (±0.2) kJ mol⁻¹.     

DFT study of the gas phase proton transfer in guanine assisted by water, methanol, and hydrogen peroxide

A computational study of hydrogen-bonded complexes between the oxo-/hydroxo-amino N7/9H tautomers of guanine and water, methanol, and hydrogen peroxide has been performed at the B3LYP/6-31+G(d) level of theory. The mechanisms of the water-, methanol-, and hydrogen peroxide-assisted proton transfers in guanine were studied and compared with the intramolecular proton transfer in guanine in the gas phase. It was found that the assisted proton transfers pass through about three times lower energy barriers than those found for isolated guanine tautomers. Figure DFT study of the gas phase proton transfer in guanine assisted by water, methanol and hydrogen peroxide     

Determination of dichloromethane, trichloroethylene and perchloroethylene in urine samples by headspace solid phase microextraction gas chromatography-mass spectrometry

A method for the determination of volatile chlorinated hydrocarbons, namely dichloromethane (DCM), trichloroethylene (TCE), and perchloroethylene (PCE), in urine samples was developed using headspace solid phase microextraction (HS-SPME) gas chromatography-mass spectrometry (GC-MS). HS-SPME was performed using a 75 microm Carboxen-polydimethylsiloxane fiber. Factors, which affect the HS-SPME process, such as adsorption and desorption times, stirring, salting-out effect, and temperature of sampling have been evaluated and optimized. The highest extraction efficiency was obtained when sampling was performed at room temperature (22 degrees C), from samples saturated with salt and under agitation. Linearity of the HS-SPME-GC-MS method was established over four orders of magnitude and the limit of detection was 0.005 microg/l for all the compounds. Precision, calculated as %R.S.D. at three different concentration levels, was within 1-8% for all intra- and inter-day determinations. The method was applied to the quantitative determination of TCE and PCE in human urine samples from exposed (TCE, n=5; median, 9.32 microg/l and PCE, n=39; median, 0.58 microg/l) and non-exposed individuals (n=120; median concentrations, 0.64, 0.22 and 0.11 microg/l for DCM, TCE and PCE, respectively. In addition, two cases of acute accidental exposure to DCM are reported, and the elimination kinetics in blood and urine was followed up. The calculated half-lives of urinary and blood DCM were, respectively, 7.5 and 8.1 h for one subject and 3.8 and 4.3 h for the other.     

Examining the impact of steric and electronic variation in N2S scorpionate ligands on the properties of zinc(II) and cadmium(II) complexes

A series of LZn(II)Br (1-4) and LCd(II)Cl complexes (9-11) has been prepared by the reaction of metal halide precursors with the lithium salts of the N₂S⁻ ligands bis(3,5-diisopropylpyrazol-1-yl)dithioacetate (L¹), bis(3,5-di-tert-butylpyrazol-1-yl)dithioacetate (L²), N-phenyl-2,2-bis(3,5-diisopropylpyrazol-1-yl)thioacetamide (L³) and N-phenyl-2,2-bis(3,5-di-tert-butylpyrazol-1-yl)thioacetamide (L⁴). Characterization by X-ray crystallography and DOSY NMR studies indicate that LZnBr complexes 1-4 are mononuclear both in the solid state and in solution. Steric differences between ligands L¹-L⁴ result in distortion from an ideal tetrahedral geometry for each complex, with the degree of distortion depending on the bulk of the ligand substituents. In contrast, the related complex L³CdCl was shown by X-ray crystallography to dimerize in the solid state to form the chloride-bridged five-coordinate complex [L³CdCl]₂ (10). Despite 10 having a dinuclear structure in the solid state, DOSY NMR studies indicate 9-11 exist as mononuclear LCdCl species in solution. In addition, Zn(II) cyanide complexes of the form LZnCN [L = L¹ (5), L³ (7), L⁴ (8)] have been characterized and the X-ray structure of 8 determined. Moreover, density functional theory calculations have been conducted which yield important insight into the bonding in 1-4 and 5-8 and the electronic impact of ligands L¹-L⁴ on the zinc(II) ion and its ability to function as a Lewis acid catalyst.     

On the relative stabilities of the alkali cations 222 cryptates in the gas phase and in water-methanol solution

The relative stabilities of the alkali [M ⊂ 222]⁺ cryptates (M = Na, K, Rb and Cs) in the gas phase and in solution (80:20 v/v methanol:water mixture) at 298 K, are computed using a combination of ab initio quantum-chemical calculations (HF/6-31G and MP2/6-31+G*//HF/6-31+G*) and explicit-solvent Monte Carlo free-energy simulations. The results suggest that the relative stabilities of the cryptates in solution are due to a combination of steric effects (compression of large ions within the cryptand cavity), electronic effects (delocalization of the ionic charge onto the cryptand atoms) and solvent effects (dominantly the ionic dessolvation penalty). Thus, the relative stabilities in solution cannot be rationalized solely on the basis of a simple match or mismatch between the ionic radius and the cryptand cavity size as has been suggested previously. For example, although the [K ⊂ 222]⁺ cryptate is found to be the most stable in solution, in agreement with experimental data, it is the [Na ⊂ 222]⁺ cryptate that is the most stable in the gas phase. The present results provide further support to the notion that the solvent in which supramolecules are dissolved plays a key role in modulating molecular recognition processes. Figure Alkali cryptates [M ⊂ 222]+ (M = Na, K, Rb and Cs) relative stabilities in gas and methanol:water solution: solvent effects and molecular recognition

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Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

The effect of industrial pollution on copper,lead, zinc and cadmium concentration in xylem rings of resistant (Populus marilandica) and sensitive (P. balsamifera) species of poplar

Summary The patterns of radial distribution of copper, lead, zinc and cadmium in two species of poplar, growing under polluted conditions near a copper smelter, were investigated. Populus marilandica is very resistant to such pollution, but P. balsamifera is sensitive. Soils were examined for concentrations of these metals, and only a surface layer of soil was polluted with copper and lead. P. balsamifera absorbed much more cadmium than P. marilandica under the same conditions. P. marilandica shows a pattern of copper radial distribution with significantly increased concentration of the meral in the layers in the middle of the trunk compared to P. balsamifera. Zinc and cadmium have a pattern with increased metal concentration from the bark towards the pith of the tree. In the case of copper and lead the pattern indicates increased concentrations of these metals in the rings adjacent to the pith while the pattern in other parts of the tree remains unconfirmed due to poor precision. Poplar xylem seems to accumulate zinc and cadmium while the content of lead in xylem is much lower than in the adjacent soil.This paper is dedicated to the memory of Professor Stefan Bialobok, Institute of Dendrology, Polish Academy of Sciences in Kornik     

Comparative gas exchange performance during the wet season of three Brazilian Styrax species under habitat conditions of cerrado vegetation types differing in soil water availability and crown density

We studied the influence of environmental conditions in different vegetation types of the Brazilian savanna (cerrado s.l.) on CO₂ assimilation and water use efficiency of Styrax ferrugineus, S. camporum and S. pohlii, which are morphologically similar but have distinct distribution patterns. We measured leaf gas exchange and water relations in adult and young plants. Adult plants of S. ferrugineus were measured in the cerrado s. str.; plants of S. camporum at the edge of cerradão, a woodland vegetation; and in a riparian forest those of S. pohlii. Eight-month-old young plants were planted in the cerrado s. str., at the edge and in the understory of the cerradão, and in the understory of the riparian forest. For young plants, the high light availability in the cerrado s. str. resulted in a threefold greater CO₂ assimilation rate (A) compared to the other sites. A of adult plants under full irradiation (1800 μmol photons m⁻² s⁻¹) was significantly lower in S. pohlii compared to S. ferrugineus and S. camporum. Although sufficient soil water was available at every site at the end of the wet season, the extreme high water content in the riparian forest soil led to increased stomatal conductance (gs) and transpiration rate (E) for young plants of S. camporum and S. pohlii, but not of S. ferrugineus. However, the large gs in S. pohlii and S. camporum young plants did not result in higher A rates. The differences may indicate some specialization of S. ferrugineus to best growth in open savanna and of S. pohlii in riparian forest habitats. The high water use efficiency of S. camporum young plants in the understory of cerradão seems not yet sufficient to emphasize that this species benefits from this particular habitat. Because, while water supply during the wet season is quite sufficient, soil water deficits and frequent fires can occur during the dry season and might modify strongly the habitat conditions for the three Styrax species.     

Exotic and indigenous freshwater gammarid species: physiological tolerance to water temperature in relation to ionic content of the water

Bioinvasions by closely related species often lead to niche competition between exotic and indigenous species. The outcome of this competition is partly determined by differences in physiological tolerance of the competing species to the environmental conditions of the colonised habitat. Physiological tolerance of the invading gammarid species Gammarus tigrinus, Echinogammarus ischnus and Dikerogammarus villosus and the indigenous gammarid species Gammarus pulex, Gammarus roeseli and Gammarus fossarum from Dutch waters was studied in the laboratory by comparing their pleopod beats at rest at different water temperatures, which reflect the gammarid's oxygen consumption. Pleopod beat frequencies increased from a minimum ventilatory activity of 0 beats per minute at 1 °C to maximum activity of up to 300 beats per minute at temperatures between 25 °C and 35 °C. At the state of maximum activity, a further increase in temperature was followed by a strong decrease in pleopod beat frequency, indicating acute stress, and subsequently mortality. Frequency response patterns of invading and indigenous gammarids were found to be highly similar, indicating a wide tolerance to temperature for all species. The tolerance of D. villosus, however, was reduced in brook water, indicating a lower competitive ability in relatively ion-poor water. G. tigrinus survived at higher temperatures in the more ion-rich, polluted waters than the indigenous gammarids, indicating a wider physiological tolerance and thus a higher competitive ability in these waters.     

Physiological effects of the presence and absence of gas vacuoles in the blue-green alga,Microcystis aeruginosa Kuetz. emend. Elenkin

Physiological evidence was obtained for a light shielding role for gas vacuoles inMicrocystis aeruginosa Kuetz. emend. Elenkin, by comparing photosynthetic oxygen evolution, growth behaviour and pigment composition of cells with intact or collapsed gas vacuoles. The oxygen evolution rates were strongly dependent on cell concentration, a maximum rate for cells with intact gas vacuoles occurring at about 1.4×10⁹ cells/ml and for cells with collapsed gas vacuoles at about 2.5×10⁹ cells/ml. By using light saturation curves for oxygen evolution, it was estimated that at low light intensities up to 30% of the photosynthetically useable light was shielded at a cell concentration of 6×10⁸ cells/ml. Collapsing the gas vacuoles twice daily did not alter the initial growth rate of the cultures, but enabled them to reach a higher final cell density. Collapsing of gas vacuoles during growth for about four generations resulted in a lower level of all acetone soluble pigments with a greater relative reduction in carotenoids than in chlorophyll a. Collapse of the gas vacuoles does not alter the cell volume. Various optical interactions which could account for light shielding are discussed.     

The contributions of apoplastic,symplastic and gas phase pathways for water transport outside the bundle sheath in leaves

Water movement from the xylem to stomata is poorly understood. There is still no consensus about whether apoplastic or symplastic pathways are more important, and recent work suggests vapour diffusion may also play a role. The objective of this study was to estimate the proportions of hydraulic conductance outside the bundle sheath contributed by apoplastic, symplastic and gas phase pathways, using a novel analytical framework based on measurable anatomical and biophysical parameters. The calculations presented here suggest that apoplastic pathways provide the majority of conductance outside the bundle sheath under most conditions, whereas symplastic pathways contribute only a small proportion. The contributions of apoplastic and gas phase pathways vary depending on several critical but poorly known or highly variable parameters namely, the effective Poiseuille radius for apoplastic bulk flow, the thickness of cell walls and vertical temperature gradients within the leaf. The gas phase conductance should increase strongly as the leaf centre becomes warmer than the epidermis – providing up to 44% of vertical water transport for a temperature gradient of 0.2 K. These results may help to explain how leaf water transport is influenced by light absorption, temperature and differences in leaf anatomy among species.     

The role of the gas phase in the greening and growth of illuminated cell suspension cultures of spinach (Spinacia oleracea,L.)

Summary The gas phase developed above spinach suspension cultures critically affected their growth and greening. Ethylene accumulation inhibited greening; this effect of ethylene was antagonised when the culture gas phase was enriched with carbon dioxide. Greening was enhanced by reducing the partial pressure of oxygen below the air level; this effect was observed when oxygen supply did not restrict growth. One of the authors (C.C.D.) was supported by an S.R.C. studentship grant during this work.     

Markedly different selectivity in the rhodium catalyzed hydroformylation of vinyl olefins containing a chiral alkoxy or alkyl group: good agreement between theory and experiment

A theoretical investigation on the regio- and stereoselective outcomes of the hydroformylation reaction with an unmodified rhodium catalyst (H-Rh(CO)₃) was carried out at the B3LYP/SBK(d) level on related chiral olefins, namely (1-vinyloxy-ethyl)-benzene (1) and (1-methyl-but-3-enyl)-benzene (2). A thorough and computationally expensive examination of the various possible H-Rh(CO)₃-olefin complex intermediates was performed, in order to determine, interpret, and eventually predict, the regio- and diastereoselectivity of the aforementioned reactions, whose products are a mixture of the linear aldehyde and of two diastereomers of the branched aldehyde. Regio- and diastereoselectivity of the reaction have been experimentally determined via hydroformylation runs at 20° and 100 °C for 1 and at 20 °C for 2. The theoretical results obtained are in good agreement with the experimental ones, which put forward a high chiral discrimination for chiral vinyl ether substrates in contrast to the lack of regio- and diastereoselectivity observed in the hydroformylation of 2. For the hydroformylation of 1, a regioselectivity ratio (B:L) of 72:28 and a diastereoselectivity ratio (b:b^′) of 97:3 have been computed which compare well to the corresponding experimental results (85:15 and 88:12). Therefore, theoretical calculations can give reliable estimates of regio- and diastereoselectivity provided a careful and accurate surface scan is performed for the alkyl-rhodium intermediates and the reaction is carried out at room temperature and, hence, in the absence of branched to linear alkyl isomerization.     

Bark stripping in cork oak (Quercus suber L.): effect of an antitranspirant application on gas exchange and water relations of the stripped surface

Quercus suber L. is the primary source of industrial cork, which can be legally collected every 9 years. The main objective of this work was to test the efficiency of an application of an antitranspirant, at three different concentrations, after the bark stripping. For this purpose, several measurements of the gas exchange, water potential, total chlorophylls and the carotenoids contents were determined in cork oak trees, at two times in a day, morning and afternoon. The antitranspirant film was applied immediately after stripping. Transpiration rate showed a significant increase in the afternoon. The parameters, water potential, photosynthetic rates, stomatal conductance and the intrinsic water use efficiency, showed a significant decrease from morning to afternoon. The difference between pigments concentration was not significant throughout the day. Water potential and transpiration rate were high in the treatments with lower antitranspirant concentration. However, the treatment with a higher paraffin concentration showed larger photosynthesis rate. This result suggests that the loss of water observed for the stripping surface can be minimized by a larger concentration of the antitranspirant.     

Phase quilibria in the system dimyristoylphosphatidyl choline/N-hexadecyl-N,N,N,-trimethylammoniumbromide/water at 30°C. Swelling behaviour of the lamellar phase with different electrolyte solutions

The phase equilibria of a swelling amphiphile, dimyristoylphosphatidylcholine (DMPC) and a cationic soap, cetyltrimethylammoniumbromide (CTAB) has been investigated in water at 30°C. The swelling of the lamellar phase of DMPC in water increases dramatically in the presènce of a few mol% of CTAB. Maximum swelling of the lamellar phase in water is obtained when the lamellar phase is in equilibrium with aqueous solution whose concentration of CTAB is less than the critical micell concentration (cmc). Vesicles are easily formed by the lamellar phase in this region. When the cme of CTAB is exceeded, DMPC is solubilized in micelles. The solubilizing capacity corresponds to about 1 mol of DMPC per 3 mol of CTAB. The phase behaviour of DMPC and CTAB in water is very similar to the corresponding equilibria for amphiphite compounds with shorter hydrocarbon chains. The swelling of DMPC and CTAB is influenced by the presence of electrolytes in the water phase. Due to electrostatic effects the swelling of the lamellar phase is lower in electrolyte solutions than in pure water.     

Effect of artificial destratification on iron,manganese, and zinc in the water,sediments, and two species of benthic macroinvertebrates in an Oklahoma lake

Ham's Lake was destratified in the summers of 1977 and 1978 by pumping surface water to the bottom. However, an arm was prevented from mixing by a submerged dam of a former farm pond and remained stratified. The concentration of manganese in the water increased to over 5 000 µg 1^–1 in the hypolimnion of the anoxic arm in summer. Soluble manganese averaged 28% of total concentration. Total iron concentrations were relatively high in the water and sorbed iron values were extremely low in the sediments. Soluble iron averaged 12% of total concentration. Zinc values were low in the water and sediments. Chaoborus punctipennis and Chironomus riparius concentrated iron and zinc and discriminated against manganese. Concentration factors were unaffected by mixing.     

Effects of a genetic variant rs13266634 in the zinc transporter 8 gene (SLC30A8) on insulin and lipid levels before and after a high-fat mixed macronutrient tolerance test in U.S. adults

BackgroundThe common C-allele of rs13266634 (c.973C>T or p.Arg325Trp) in SLC30A8 (ZNT8) is associated with increased risk of type 2 diabetes. While previous studies have examined the correlation of the variant with insulin and glucose metabolism, the effects of this variant on insulin and lipid responses after a lipid challenge in humans remain elusive. The goal of this study was to determine whether the C-allele had an impact on an individual’s risk to metabolic syndromes in U.S. adults.MethodWe studied the genotypes of rs13266634 in 349 individuals aged between 18 and 65 y with BMI ranging from 18.5 to 45 kg/m². The subjects were evaluated for insulin, glucose, HbA1c, ghrelin, and lipid profiles before and after a high-fat mixed macronutrient tolerance test (MMTT).ResultsWe found that the effects of variants rs13266634 on glucose and lipid metabolism were sex-dimorphic, greater impact on males than on females. Insulin incremental area under the curve (AUC) after MMTT was significantly decreased in men with the CC genotype (p < 0.05). Men with the CC genotype also had the lowest fasting non-esterified fatty acid (NEFA) concentrations. On the other hand, the TT genotype was associated with a slower triglyceride removal from the circulation in men after MMTT. The reduced triglyceride removal was also observed in subjects with BMI ≥ 30 carrying either the heterozygous or homozygous T-allele. Nevertheless, the SNP had little effect on fasting or postprandial blood glucose and cholesterol concentrations.ConclusionWe conclude that the CC genotype negatively affects insulin response after MMTT while the T-allele may negatively influence lipolysis during fasting and postprandial blood triglyceride removal in men and obese subjects, a novel finding in this study.     

Effect of the sulphur atom on geometry and spectra of the biomolecule 2-thiouracil and in the WC base pair 2-thiouridine-adenosine. Influence of water in the first hydration shell

The effect of the sulphur atom on 2-thiouracil (2TU) and 2-thiouridine molecules, as compared with uracil and uridine molecules, respectively, was carried out in several environments. The predicted IR spectrum of 2TU in the isolated state was compared with that obtained for uracil molecule and with those reported experimentally in matrix isolation. Its crystal unit cell in the solid state was simulated through a tetramer form using DFT methods for the first time. The calculated Raman spectrum was compared to the experimental ones in the solid state. A linear scaling procedure was used for this task. The first hydration shell was simulated by explicit number of water molecules surrounding 2TU up to 30 and was compared with that obtained in uracil molecule. Water molecules ‘distributed’ around 2TU was preferred over that ‘clustering’, because it can better reproduce the hydration and their effects on different parameters of the molecular structure of 2TU and uracil. The total atomic charges and several calculated thermodynamic parameters were discussed. The effect of the sulphur atom on the Watson-Crick (WC) and reverse WC base pair uridine-adenosine was estimated, and the CP corrected interaction energies were calculated. 2-thiouridine has a weaker WC pair than that with uridine, although its slight higher dipole moment (μ) facilitates the interaction with the water molecules. Several helical parameters were determined.