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PubMed1975

Effect of salts and polyamines on T4 polynucleotide kinase.

The activity of T4 polynucleotide kinase (EC 2.7.1.78) was found to be greatly stimulated by salts, such as NaCl and KCl, and polyamines such as spermine and spermidine. Up to a sixfold increase in initial rates was observed with a variety of different single-stranded DNAs and mono- and oligonucleotides. The optimal concentrations of salts were 0.125 M, corresponding to a total ionic strength of mu equals 0.19. For polyamines the optimal concentrations were found to be at approximately 2 mM. With low enzyme concentration and in the absence of activators complete phosphorylation was not achieved for a number of substrates. In the presence of salts or polyamines or high concentration of enzyme the phosphorylation proceeded to completion. Addition of salt led to an increase in both the apparent V-max and the Michaelis constant for the DNA substrate whereas the Michaelis constant of ATP remained unchanged. Polyamines had a similar influence on the kinetic constants for the DNA substrate whereas a decrease was found for the apparent Michaelis constant for ATP. The overall mechanism in the presence of activators was found to be sequential but probably of a rapid equilibrium random type. Of the inorganic anions tested both P-i and PP-i inhibited the enzyme in a competitive manner with both substrates.

Coliphages↗
PubMed2003

Epimer interconversion, isomerization, and hydrolysis of tetrahydrouridine: implications for cytidine deaminase inhibition.

Tetrahydrouridine (THU) is an inhibitor of cytidine deaminase (CDA), the enzyme responsible for the deactivation of ara-C and other cytidine analogues in vivo, and therefore is capable of improving the therapeutic efficacy of these antitumor agents. In aqueous solution formulations, THU exists as a mixture of epimers differing in stereochemistry of the 4-OH substituent. The aims of this study were to investigate the interconversion kinetics of the epimers of THU, the CDA inhibitory effects of these epimers, and the stability and degradation mechanisms of THU epimer mixtures in aqueous solution with the ultimate goal of developing optimal conditions for a parenteral formulation of THU. A stability indicating HPLC assay utilizing a derivatized beta-cyclodextrin column was developed to separate the two epimers of THU and to monitor their reversible isomerization to their beta-ribopyranosyl counterparts and their hydrolysis to form N-glycosidic bond cleavage products. MS and one- and two-dimensional (1)H- and (13)C-NMR measurements were conducted to identify THU epimers and degradation products and to quantitatively model the degradation kinetics. The interconversion reaction between the two THU epimers is acid catalyzed with a first-order rate constant for conversion of epimer 1(1) to epimer 1(2) of (7.4 +/- 0.3) x 10(-3) h(-1) and an equilibrium constant ([1(2)]/[1(1)] of 1.7 +/- 0.1 at pH 7.4 and 25 degrees C. Epimer interconversion was therefore sufficiently slow at pH 7.4 to allow the isolation of each and evaluation of their CDA inhibitory activities utilizing 1% (w/v) mouse kidney homogenates as a source for cytidine deaminase and cytidine as a substrate. Inhibition constants for the two THU epimers (1(1) and 1(2)) were determined to be 8 +/- 1 x 10(-7) M and 6.2 +/- 0.2 x 10(-8) M, respectively. Studies at elevated temperature suggested that THU degradation from epimer mixtures is biphasic with the initial rate of disappearance being acid catalyzed and first order in initial THU concentration, thus ruling out dimerization as a potential reaction mechanism. NMR/MS analyses revealed that the major degradation products included the beta-ribopyranosyl THU isomers (two epimers), the reduced pyrimidinone base (tetrahydrouracil), and various anomers of D-ribose formed through N-glycosidic bond cleavage, and the products of subsequent reactions of the base. Kinetic modeling of the data obtained from both HPLC and NMR measurements indicated that in an acidic solution THU beta-ribofuranosyl --> beta-ribopyranosyl isomerization is a rapid equilibrium reaction, which proceeds through an intermediate observable in 1H-NMR, and is followed by slower N-glycosidic bond hydrolysis. All the reactions between THU, its ribopyranosyl isomers, the intermediate, and the base are acid catalyzed and appear to proceed through the same sugar ring-opened intermediate (carbinolamine), consistent with previous literature.

Animals↗
PubMed2005

High precision measurements of 17O/16O and 18O/16O ratios in H2O.

We have optimized the method of water fluorination using the solid reagent CoF3 to produce O2. This allows isotope ratio measurements by dual-inlet mass spectrometry with very high precision of 0.01 to 0.03/1000 for both delta17O and delta18O. Using this method, delta17O and delta18O of atmospheric O2 were determined as 12.08 and 23.88/1000 vs. VSMOW, respectively. Likewise, delta17O and delta18O of GISP were -13.12 and -24.73/1000, and for SLAP they were -29.48 and -55.11/1000 vs. VSMOW, respectively. Analysis of these data in a ln(delta17O + 1) vs. ln(delta18O + 1) plot yields a line with a regression coefficient (lambda) of 0.5279 +/- 0.0001 (R2 = 0.999999). We also determined the fractionation factors 17alpha and 18alpha in liquid-vapor equilibrium, and found that the ratio ln 17alpha/ln 18alpha is constant (0.529 +/- 0.001) over the temperature range 11.4 to 41.5 degrees C.

Journal Article↗
PubMed2001

Electronic spectral studies of molybdenyl complexes. 2. MCD spectroscopy of [MoOS4]- centers.

Magnetic circular dichroism (MCD) and absorption spectroscopies have been used to probe the electronic structure of [PPh4][MoO(p-SC6H4X)4] (X = H, Cl, OMe) and [PPh4][MoO(edt)2] complexes (edt = ethane-1,2-dithiolate). The results of density functional calculations (DFT) on [MoO(SMe)4]- and [MoO(edt)2]- model complexes were used to provide a framework for the interpretation of the spectra. Our analysis shows that the lowest energy transitions in [MoVOS4] chromophores (S4 = sulfur donor ligand) result from S-->Mo charge transfer transitions from S valence orbitals that lie close to the ligand field manifold. The energies of these transitions are strongly dependent on the orientation of the S lone-pair orbitals with respect to the Mo atom that is determined by the geometry of the ligand backbone. Thus, the lowest energy transition in the MCD spectrum of [PPh4][MoO(p-SC6H4X)4] (X = H) occurs at 14,800 cm-1, while that in [PPh4][MoO(edt)2] occurs at 11,900 cm-1. The identification of three bands in the absorption spectrum of [PPh4][MoO(edt)2] arising from LMCT from S pseudo-sigma combinations to the singly occupied Mo 4d orbital in the xy plane suggests that there is considerable covalency in the ground-state electronic structures of [MoOS4] complexes. DFT calculations on [MoO(SMe)4]- reveal that the singly occupied HOMO is 53% Mo 4dxy and 35% S p for the equilibrium C4 geometry. For [MoO(edt)2]- the steric constraints imposed by the edt ligands result in the S pi orbitals being of similar energy to the Mo 4d manifold. Significant S pseudo-sigma and pi donation may also weaken the Mo identical to O bond in [MoOS4] centers, a requirement for facile active site regeneration in the catalytic cycle of the DMSO reductases. The strong dependence of the energies of the bands in the absorption and MCD spectra of [PPh4][MoO(p-SC6H4X)4] (X = H, Cl, OMe) and [PPh4][MoO(edt)2] on the ligand geometry suggests that the structural features of the active sites of the DMSO reductases may result in an electronic structure that is optimized for facile oxygen atom transfer.

Circular Dichroism↗
PubMed2002

The stability curve of bovine adenosine deaminase is bimodal.

We have determined the stability curve of bovine adenosine deaminase via titrations with guanidine hydrochloride at pH = 6.3 from 5 to 65 degrees C. The data indicate that the enzyme undergoes an abrupt conformational transition at approximate, equals 29 degrees C, a finding supported by a temperature scan of the intrinsic enzyme fluorescence emission. Analysis of the data above and below this temperature with the modified Gibbs-Helmholtz equation allows for complete description of the equilibrium unfolding thermodynamics for either enzyme conformation. The high-temperature form of the enzyme is described by DeltaH degrees = 648 +/- 37 kJ/mole, DeltaC(P) = 23.2 +/- 2.5 kJ/mole-K, and a heat denaturational temperature T(h)(dn) = 72.5 +/- 0.9 degrees C. The low-temperature form is described by DeltaH degrees = 1284 +/- 47 kJ/mole, DeltaCP = 73.2 +/- 4.9 kJ/mole-K, and T(h)(dn) = 32.6 +/- 0.6 degrees C. Further thermodynamic analysis of the conformations that predominate at 38.3 degrees C, the bovine normal body temperature, and at 4 degrees C, where the crystals for x-ray structural analyses were formed, suggest that the stability of either form is due to favorable amino acid side chain nonpolar interactions with these interactions being much more optimized in the low-temperature conformation. We therefore conclude that the structure as determined by x-ray crystallographic methods cannot be the physiological structure. The data also suggest that the general calculation of enzyme stability curves from the extrapolation of heat denaturation data may inaccurately represent the enzyme stability as a low-temperature, nondenaturational transition is assumed not to exist. Further consequences in terms of general enzyme catalysis are also discussed.

Adenosine Deaminase↗
PubMed2006

T2 measurement and quantification of glutamate in human brain in vivo.

The proton NMR transverse relaxation time T(2) of glutamate (Glu) in human brain was measured by means of spectrally selective refocusing at 3.0 T in vivo. An 81.4-ms-long dual-band Gaussian 180 degrees RF pulse, designed for refocusing at 2.35 and 3.03 ppm, was employed within point-resolved spectroscopy (PRESS) to generate the Glu C4-proton target multiplet and the total creatine (tCr) singlet. Six optimal echo times (TEs) between 128 and 380 ms were selected from numerical analysis of the filtering performance for effective detection of the Glu signal with minimal contamination from glutamine (Gln), N-acetylaspartate (NAA), and glutathione (GSH). The magnetization of Glu and tCr was extracted from spectral fitting of experimental and calculated spectra. Apparent T(2) values of Glu and tCr were estimated as 201 +/- 18 and 164 +/- 12 ms for the medial prefrontal (PF) cortex, and 198 +/- 22 and 169 +/- 15 ms (mean +/- SD, N = 5) for the left frontal (LF) cortex, respectively. With water segmentation data, the magnetization values of Glu and tCr of the two adjacent voxels, calculated from the T(2) values and spectra following the thermal equilibrium magnetization, were combined to give the Glu and tCr concentrations as 10.37 +/- 1.06 and 8.87 +/- 0.56 mM for gray matter (GM), and 5.06 +/- 0.57 and 5.16 +/- 0.45 mM (mean +/- SD, N = 5) for white matter (WM), respectively.

Adult↗
PubMed2005

Electron-conformational model of ryanodine receptor lattice dynamics.

We propose a simple, physically reasonable electron-conformational model for the ryanodine receptor (RyR) and, on that basis, present a theory to describe RyR lattice responses to L-type channel triggering as an induced non-equilibrium phase transition. Each RyR is modelled with a single open and a single closed (electronic) state only, described utilizing a s=12 pseudospin approach. In addition to the fast electronic degree of freedom, the RyR channel is characterized by a slow classical conformational coordinate, Q, which specifies the RyR channel calcium conductance and provides a multimodal continuum of possible RyR states. The cooperativity in the RyR lattice is assumed to be determined by inter-channel conformational coupling. Given a threshold sarcoplasmic reticulum (SR) calcium load, the RyR lattice fires due to a nucleation process with a step-by-step domino-like opening of a fraction of lattice channels, providing for a sufficient release to generate calcium sparks. The optimal mode of RyR lattice functioning during calcium-induced calcium release implies a fractional release with a robust termination due to a decrease in SR calcium load, accompanied by a respective change in effective conformational strain of the lattice. SR calcium overload is shown to result in excitation of RyR lattice auto-oscillations with spontaneous RyR channel opening and closure.

Animals↗
PubMed2001

Synthesis and characterisation of inulin-azo hydrogels designed for colon targeting.

The present paper describes the synthesis and characterisation of new hydrogel systems designed for colon targeting. The gels were composed of methacrylated inulin (MA-IN), copolymerized with the aromatic azo agent bis(methacryloylamino)azobenzene (BMAAB) and 2-hydroxyethyl methacrylate (HEMA) or methacrylic acid (MA). The gels were assessed by studying the influence of various parameters on the dynamic and equilibrium degree of swelling. It was shown that the uptake of water in the gels was inversely proportional to the MA-IN feed concentration, the degree of substitution of the inulin backbone, and the concentration of BMAAB. The latter can probably be explained by the hydrophobic nature and rigidity of the aromatic azo agent. Incorporation of the hydrophilic monomers HEMA or MA also reduced the equilibrium degree of swelling. An increasing network density and hydrogen bonding propensity, can suggested to be responsible for this observation. It was shown that water uptake in the hydrogels was controlled by both relaxation and diffusion mechanisms (anomalous behaviour). When the release of the model drug prednisolone was studied in phosphate buffer, it was shown that >80% of the drug was released during the first 3 h from hydrogels of MA-IN:HEMA. Although drug release decreased significantly from MA-IN:HEMA:BMAAB hydrogels, it remained too high: approximately 50% of the drug was released after 5 h. The same observation was made for hydrogels containing MA instead of HEMA. These results clearly point out the difficulty in finding the optimal balance between swelling to allow degradation in the colon (high swelling of the gels) and low premature drug release before the colonic environment is reached (low swelling properties).

Anti-Inflammatory Agents↗
PubMed2006

Contribution of cooperativity and the Bohr effect to efficient oxygen transport by hemoglobins from five mammalian species.

By using published experimental values of the standard oxygen (O2) equilibrium curve and the in vivo arterial and venous O2 pressure (PO2) of fetal and maternal blood in five mammalian species (human, cow, pig, sheep, and horse), we investigated the relationship between the efficiency of O2 delivery and the effectiveness of the Bohr shift, and discussed the significance of cooperativity for mammalian Hb. The O2 delivery of fetal blood was more efficient than that of maternal blood, and the effectiveness of the Bohr shift at both O2 loading and release sites of fetal blood was high. A linear relationship was observed between the efficiency of O2 delivery and the effectiveness of the Bohr shift at O2 loading sites of the five mammalian species. In both fetal and maternal blood, the theoretically obtained optimal P50 value for O2 delivery (optP50(OD)) was nearly equal to the optimal P50 value for the effectiveness of the Bohr shift at the O2 loading site (optP50(BS)(loading)). This phenomenon was favorable for fetal blood to uptake O2 from maternal blood with the aid of the Bohr shift and to deliver a large amount of O2 to the tissues. The optP50s for the effectiveness of the Bohr shift at given arterial PO2 (PaO2) and venous PO2 (PvO2) were derived as follows: optP50(BS)(loading) = PaO2((n+1)/(n-1))(1/n), and optP50(BS)(release) = PvO2((n+1)/(n-1))(1/n). The relationship between in vivo PO2s and n, PaO2/PvO2 = ((n+1)/(n-1))(2/n), was derived by letting optP50 for the efficiency of O2 delivery be equal to that for the effectiveness of the Bohr shift.

Animals↗
PubMed1983

Immunoquantification of total apolipoprotein B in serum by nephelometry: influence of lipase treatment and detergents.

The immunoquantification of total apolipoprotein B in human serum has been evaluated by rate and equilibrium nephelometry. The presence of triglyceride-rich lipoproteins spoiled all immunochemical assays and yielded too-high values for apolipoprotein B. The use of detergents improved the results substantially, but results were inaccurate at high triglyceride concentrations. Of many detergents investigated, only Thesit, Kryo Ebo, and Apovax were useful, decreasing the light-scatter signals almost linearly with increasing detergent concentrations. The regression lines, however, were not parallel among the different apo B-containing lipoproteins. Incubating sera or apo B-containing lipoproteins with bovine milk lipoprotein lipase or bacterial triacylglycerol lipase, at concentrations of 100 kU/L, hydrolyzed all of the triglycerides and most of the phosphatidylcholine within 18 h at 37 degrees C Lipase-pretreatment of samples gave optimal correlation between apo B values as determined by nephelometry with those obtained gravimetrically. We also assessed the influence of sample storage, freezing, and thawing on the nephelometric apo B assays.

Apolipoproteins↗
PubMed2000

Optimal specimen geometry in bonded-disk shrinkage-strain measurements on light-cured biomaterials.

OBJECTIVES: The aim was to determine the effect on apparent shrinkage-strain values of varying specimen aspect ratio in the bonded-disk configuration. Thereby one source of possible inter-laboratory variation might be understood and eliminated. METHODS: The bonded-disk procedure was followed and applied to three representative resin-composites. However, specimen sub-groups were examined, each of different diameters (3.5, 5.0, 7.0 and 9.0 mm), corresponding to C-factors in the range 0.45-7.0. RESULTS: For each material, no statistically significant difference was apparent between data obtained with 7 and 9 mm diameter specimens. However, statistically significant reductions (p < 0.05, Scheffé and SNK) were apparent at 5.0 and 3.5 mm diameter, in the range 14-18% of the maximum 'true' value. For each material, the diameter (d)-dependence of apparent shrinkage-strain (epsilon) was given by the curve fit expression: epsilon = A - B/d2. SIGNIFICANCE: For accurate determination of maximum final equilibrium shrinkage-strain values, a high aspect ratio (7-9:1) of the bonded-disk should be utilised. This is important for accurate comparison of data from proposed low-shrinkage amalgam-replacement materials.

Analysis of Variance↗
PubMed1992

Periosteal and endosteal control of bone remodeling under torsional loading.

The shape changes that occur in the mid-diaphysis of a long bone due to adaptive remodeling induced by increasing or decreasing the axial and/or torsional loading of the bone are investigated using a simple model. In this model the mid-diaphysis of a long bone is represented as a hollow thick-walled right-circular cylinder, and different optimal strategies for bone remodeling are considered. It is shown that if such a thick-walled right-circular cylinder capable of surface remodeling is subjected to an axial compressive load and a twisting torque, then the remodeling patterns depend on whether the periosteal surface or the endosteal surface controls the limits of the remodeling process. It is shown that the effect of increasing the torque is always opposite to the effect of increasing the compressive load. Thus, similar remodeling patterns are obtained by increasing one type of loading and decreasing the other. Aside from the restriction of idealized cylindrical geometry, the only assumptions made are that the bone tissue is linearly elastic and that there exists a finite range of remodeling equilibrium stresses. Only those loading situations which maintain the bone in remodeling equilibrium are considered in this work. It follows that the results presented are independent of the specific type of rule governing the temporal evolution of the bone shape, since any such rule applies only in situations where there is active remodeling and, hence, no remodeling equilibrium.

Biomechanical Phenomena↗
PubMed2002

Receptor modeling application framework for particle source apportionment.

Receptor models infer contributions from particulate matter (PM) source types using multivariate measurements of particle chemical and physical properties. Receptor models complement source models that estimate concentrations from emissions inventories and transport meteorology. Enrichment factor, chemical mass balance, multiple linear regression, eigenvector. edge detection, neural network, aerosol evolution, and aerosol equilibrium models have all been used to solve particulate air quality problems, and more than 500 citations of their theory and application document these uses. While elements, ions, and carbons were often used to apportion TSP, PM10, and PM2.5 among many source types, many of these components have been reduced in source emissions such that more complex measurements of carbon fractions, specific organic compounds, single particle characteristics, and isotopic abundances now need to be measured in source and receptor samples. Compliance monitoring networks are not usually designed to obtain data for the observables, locations, and time periods that allow receptor models to be applied. Measurements from existing networks can be used to form conceptual models that allow the needed monitoring network to be optimized. The framework for using receptor models to solve air quality problems consists of: (1) formulating a conceptual model; (2) identifying potential sources; (3) characterizing source emissions; (4) obtaining and analyzing ambient PM samples for major components and source markers; (5) confirming source types with multivariate receptor models; (6) quantifying source contributions with the chemical mass balance; (7) estimating profile changes and the limiting precursor gases for secondary aerosols; and (8) reconciling receptor modeling results with source models, emissions inventories, and receptor data analyses.

Air Pollutants↗
PubMed1983

Contribution to the methodology of optimization and in-process control of some physical properties of pharmaceutical bulk substances and granulates.

Many experts consider drug analysis exclusively as a chemical measuring technique. In the pharmaceutical industry, physical and physico-chemical parameters form an integrated part of the quality specification, because they play an essential role both in quality assurance and in the technical and economic aspects of production on the commercial scale. Such physical and physico-chemical properties are analysed by special, non-chemical methods. In their programme of systematic research in this field, the authors have elaborated new methods to test some essential properties of powders and granulates used in the production of compressed tablets. The following test and production methods have been developed: (i) the determination of flowing-sliding characteristics of granulates based on the measurement of the mass-flow (g s(-1)) and mass-flow density (g s(-1) cm(-2)); (ii) the determination of optimum granulometric parameters with regard to tablet diameter; (iii) the direct determination of the temperature-dependent equilibrium vapour pressure; and (iv) the compression of tablets under controlled temperature.

Journal Article↗
PubMed2006

The effect of erbium on the adsorption and photodegradation of orange I in aqueous Er3+-TiO2 suspension.

Pure TiO(2) and erbium ion-doped TiO(2) (Er(3+)-TiO(2)) catalysts prepared by the sol-gel method were characterized by means of XRD and diffusive reflectance spectra (DRS). The XRD results showed that erbium ion doping could enhance the thermal stability of TiO(2) and inhibit the increase of the crystallite size, and the DRS results showed that the optical absorption edge slightly shifted to red direction owing to erbium ion doping and the Er(3+)-TiO(2) catalysts had three typical absorption peaks located at 490, 523 and 654 nm owing to the transition of 4f electron from (4)I(15/2) to (4)F(7/2), (2)H(11/2) and (4)F(9/2). With a purpose of azo dyes degradation, orange I was used as a model chemical. And the adsorption isotherm, degradation and mineralization of orange I were investigated in aqueous suspension of pure TiO(2) or Er(3+)-TiO(2) catalysts. The results showed that Er(3+)-TiO(2) catalysts had higher adsorption equilibrium constants and better adsorption capacity than pure TiO(2). The adsorption equilibrium constants (K(a)) of Er(3+)-TiO(2) catalysts were about twice of that of pure TiO(2). The maximum adsorption capacity (Q(max)) of 2.0% Er(3+)-TiO(2) catalyst was 13.08x10(-5)mol/g, which was much higher than that of pure TiO(2) with 9.03x10(-5)mol/g. Among Er(3+)-TiO(2) catalysts, 2.0% Er(3+)-TiO(2) catalyst achieved the highest Q(max) and K(a) values. The kinetics of the orange I degradation using different Er(3+)-TiO(2) catalysts were also studied. The results demonstrated that the degradation and mineralization of orange I under both UV radiation and visible light were more efficient with Er(3+)-TiO(2) catalyst than with pure TiO(2), and an optimal dosage of erbium ion at 1.5% achieved the highest degradation rate. The higher photoactivity under visible light might be attributable to the transitions of 4f electrons of Er(3+) and red shifts of the optical absorption edge of TiO(2) by erbium ion doping.

Adsorption↗
PubMed2005

Quantum chemical studies of mononuclear zinc species of hydration and hydrolysis.

Optimal geometries, charge distributions, bond analysis, changes of Gibbs free energy, entropies and enthalpies of hydration, and hydrolysis reactions for mononuclear species of Zn(2+) including hydrated and hydrolysis complexes were investigated using quantum chemical calculations in the gas phase. Optimized geometrical structures showed that the stable hydrated and hydrolysis zinc species without outer-sphere water molecules were Zn(H(2)O)(6)(2+), Zn(OH)(H(2)O)(3)(+), Zn(OH)(2)(H(2)O)(2), Zn(OH)(3)(-), and Zn(OH)(4)(2-). Results of NPA (Natural Population Analysis) indicated that the charge on the Zn atom of the hydrated ions decreased but the charge on the zinc atom of the hydrolysis species increased with the increase of inner-sphere water molecules. NBO (Natural Bond Orbital) analyses demonstrated that hydrated and hydrolysis species of zinc were mainly electrostatic bonding compounds. Calculations of reaction energies indicated that inner-sphere water molecules became more unfavorable as the hydrolysis increased. Stepwise hydrolysis equilibrium constants decreased successively and the order remained unchanged when the inner-sphere dehydration occurred.

Hydrolysis↗
PubMed2007

Computational approach to nuclear magnetic resonance in 1-Alkyl-3-methylimidazolium ionic liquids.

A quantum-chemical computational approach to accurately predict the nuclear magnetic resonance (NMR) properties of 1-alkyl-3-methylimidazolium ionic liquids has been performed by the gauge-including atomic orbitals method at the B3LYP/6-31++G** level using different simulated ionic liquid environments. The first molecular model chosen to describe the ionic liquid system includes the gas-phase optimized structures of ion pairs and separated ions of a series of imidazolium salts containing methyl, butyl, and octyl substituents and PF6-, BF4-, and Br- anions. In addition, a continuum polarizable model of solvation has been applied to predict the effects of the medium polarity on the molecular properties of 1,3-dimethylimidazolium hexafluorophosphate (MmimPF6). Furthermore, the specific acidic and basic solute-solvent interactions have been simulated by a discrete solvation model based on molecular clusters formed by MmimPF6 species and a discrete number of water molecules. The computational prediction of the NMR spectra allows a consistent interpretation of the dispersed experimental evidence in the literature. The following are main contributions of this work: (a) Theoretical results state the presence of a chemical equilibrium between ion-pair aggregates and solvent-separated counterions of 1-alkyl-3-methylimidazolium salts which is tuned by the solvent environment; thus, strong specific (acidic and basic) and nonspecific (polarity and polarizability) solvent interactions are predicted favoring the dissociated ionic species. (b) The calculated 1H and 13C NMR properties of these ionic liquids are revealed as highly dependent on the nature of solute-solvent interactions. Thus, the chemical shift of the hydrogen atom in position two of the imidazolium ring is deviated to high values by the specific interactions with water molecules, whereas nonspecific interaction with water (as a solvent) affects, in the opposite direction, this 1H NMR parameter. (c) Last, current calculations support the presence of hydrogen bonding between counterions, suggesting the importance of this interaction in the properties of the solvent in the 1-alkyl-3-methylimidazolium ionic liquids.

Journal Article↗
PubMedDate not supplied

Phosphorus desorption dynamics in soil and the link to a dynamic concept of bioavailability.

Soils under intensive livestock farming and heavily fertilized with animal manure may have elevated soil phosphorus (P) contents. We determined P desorption kinetics in batch experiments using soils from a pot experiment where grass was cropped on a P-rich noncalcareous sandy soil without P addition, to lower the soil P content. A diffusion model was used to describe P desorption kinetics from a spherical aggregate. The model was calibrated with data from the batch experiments. Simulation results show that in the pot experiment, P desorption from the solid phase of the inner layers was initially far from equilibrium with the rest of the aggregate, but desorption came closer to equilibrium as the soil P content decreased further. A simple tool is presented, referred to as the dynamic bioavailability index (DBI), to determine whether kinetics of P desorption limits plant uptake. This tool is the dimensionless ratio of the modeled maximal diffusive flux from soil aggregates to solution and the plant uptake rate measured in the pot experiment. The DBI was initially much larger than one; the maximal possible P desorption rate exceeded the uptake rate, so uptake was not limited by desorption. The DBI stabilized at a value somewhat larger than one after a while, due to soil transport limitations. This decrease coincided with a large decrease of the P content in the grass to a value (far) below what is considered as optimal; the supply rate of P from soil to the root cannot meet the demand needed for optimal P uptake. The DBI could be seen as a promising onset to a new dynamic approach of bioavailability.

Adsorption↗