			Home About us Contact

E Values (e + value)

Distribution by Scientific Domains

Chemistry	38%
Polymers and Materials Science	19%
Medical Sciences	7%
Life Sciences	7%

Selected Abstracts

Soil solution concentration of Cd and Zn canbe predicted with a CaCl2 soil extract

EUROPEAN JOURNAL OF SOIL SCIENCE, Issue 1 2003
F. Degryse
Summary Risk assessment of heavy metals in soil requires an estimate of the concentrations in the soil solution. In spite of the numerous studies on the distribution of Cd and Zn in soil, few measurements of the distribution coefficient in situ, Kd, have been reported. We determined the Kd of soils contaminated with Cd and Zn by measuring metal concentrations in the soil and in the soil solution and attempted to predict them from other soil variables by regression. Soil pH explained most of the variation in logKd (R2 = 0.55 for Cd and 0.70 for Zn). Introducing organic carbon content or cation exchange capacity (CEC) as second explanatory variable improved the prediction (R2 = 0.67 for Cd and 0.72 for Zn), but these regression models, however, left more than a factor of 10 of uncertainty in the predicted Kd. This large degree of uncertainty may partly be due to the variable degree of metal fixation in contaminated soils. The labile metal content was measured by isotopic dilution (E value). The E value ranged from 18 to 92% of the total metal content for Cd and from 5 to 68% for Zn. The prediction of Kd improved when metals in solution were assumed to be in equilibrium with the labile metal pool instead of the total metal pool. It seems necessary therefore to discriminate between ,labile' and ,fixed' pools to predict Kd for Cd and Zn in field contaminated soils accurately. Dilute salt extracts (e.g. 0.01 m CaCl2) can mimic soil solution and are unlikely to extract metals from the fixed pool. Concentrations of Cd and Zn in the soil solution were predicted from the concentrations of Cd and Zn in a 0.01 m CaCl2 extract. These predictions were better correlated with the observations for field contaminated soils than the predictions based on the regression equations relating logKd to soil properties (pH, CEC and organic C). [source]

Methods for determining labile cadmium and zinc in soil

EUROPEAN JOURNAL OF SOIL SCIENCE, Issue 1 2000
S. D. Young
Summary Isotopically exchangeable cadmium and zinc (,E values') were measured on soils historically contaminated by sewage sludge and ones on zinc-rich mine spoil. The E -value assay involves determining the distribution of an added metal isotope, e.g. 109Cd, between the solid and solution phases of a soil suspension. The E values for both metals were found to be robust to changes in the position of the metal solid,solution equilibrium, even though the concentration of dissolved metal varied substantially with electrolyte composition and soil:solution ratio. Concentration of labile metal was also invariant over isotope equilibration times of 2,6 days. The use of a submicron filtration procedure, in addition to centrifuging at 2200 g, proved unnecessary if 0.1 m Ca electrolyte was used to suspend the soils. The proportion of ,fixed' metal, in non-labile forms, apparently increased with increasing pH, although there was considerable variation in both sets of contaminated soil. Zinc and cadmium in the sludged soils were similarly labile. Several possible methods for the measurement of chemically reactive metal were explored for comparison with E values, including single extraction with 1 m CaCl2 and a ,pool depletion' (PD) method. The latter involves comparing solid,solution metal equilibria in two electrolytes with differing degrees of (solution) complex formation, 0.1 m Ca(NO3)2 and CaCl2. Both the single extraction and the PD method gave good estimates of E value for Cd, although the single extraction was more consistent. Neither technique was a useful substitute for determining labile Zn, because of weak chloro-complexation of Zn2+. We therefore suggest that 1 m CaCl2 extraction of Cd alone be used as an alternative to E values to avoid the inconvenience of isotopic dilution procedures. [source]

Ab initio QM/MM study of excited state electron transfer between pyrene and 4,4,-bis(dimethylamino)-diphenylmethane with different solvent systems: Role of hydrogen bonding within solvent molecules

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4 2005
Kakali Sen
Abstract The exciplex is a charge transfer species formed in the process of electron transfer between an electron donor and an electron acceptor and hence is very sensitive to solvent polarity. In order to understand the role of solvent in exciplex formation between pyrene (PY) and 4,4,-bis(dimethylamino)diphenylmethane (DMDPM), we used two types of solvent approximations: an implicit solvent model and an explicit solvent model. The difference in energies between the excited and the meta-stable Frank,Condon state (,E) of the structures were assumed to correspond to the emission maximum of the exciplex in different solvents. The ,E values show the trend of stabilization of the exciplex with an increase in solvent polarity. This trend in stabilization is substantially more prominent in the explicit solvent model than that with the implicit solvent model. The ,E value obtained in methanol reflects equal stabilization compared to that in a more polar solvent, N,N-dimethylformamide. This extra stabilization of the exciplex may be explained on the basis of the H-bonding capability of the protic solvent, methanol. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 [source]

On the Resolution of Chiral Substrates by a retro- Claisenase Enzyme: Biotransformations of Heteroannular Bicyclic ,-Diketones by 6-Oxocamphor Hydrolase

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 8-9 2007
Cheryl
Abstract The enzyme 6-oxocamphor hydrolase (OCH) from Rhodococcus sp. NCIMB 9784 catalyses the cleavage of a carbon-carbon bond between two carbonyl groups in both mono- and bicyclic non-enolisable ,-diketone substrates. In this mode OCH has been shown to effect the desymmetrisation of both bridged symmetrical bicyclic [2.2.1] and [2.2.2] systems and a series of 1-alkylbicyclo[3.3.0]octane-2,8-diones, yielding chiral substituted cyclopentanone and cyclohexanone products in high optical purity. In the present study, OCH has been challenged with a series of heteroannular substrates including 1-methylbicyclo[4.3.0]nonane-2,9-dione (7a-methylhexahydroindene-1,7-dione) in an effort to assess the competence of the enzyme for kinetic resolutions of asymmetric, racemic substrates. OCH was shown to catalyse the resolution of 1-methylbicyclo[4.3.0]nonane-2,9-dione with an E value of 2.9. The effect of increasing the length of the alkyl chain in the 1-position, or enlarging one of the rings, was to increase the enantioselectivity of the enzyme to 5.7 and 3.1 for the substrates 1-allylbicyclo[4.3.0]nonane-2,9-dione (7a-allylhexahydroindene-1,7-dione) and 1-methylbicyclo[5.3.0]decane-2,10-dione (8a-methyloctahydroazulene-1,8-dione), respectively. 1-Methylbicyclo[5.4.0]undecane-2,10-dione (9a-methyloctahydrobenzocycloheptene-1,9-dione) was not a substrate for OCH. These experiments constitute the first description of the resolution behaviour of such a retro -Claisenase enzyme, and suggest a maximum steric limit for substrate recognition by OCH. [source]

The statistics of the highest E value

ACTA CRYSTALLOGRAPHICA SECTION A, Issue 4 2007
Grzegorz Chojnowski
In a previous publication, the Gumbel,Fisher,Tippett (GFT) extreme-value analysis has been applied to investigate the statistics of the intensity of the strongest reflection in a thin resolution shell. Here, a similar approach is applied to study the distribution, expectation value and standard deviation of the highest normalized structure-factor amplitude (E value). As before, acentric and centric reflections are treated separately, a random arrangement of scattering atoms is assumed, and E -value correlations are neglected. Under these assumptions, it is deduced that the highest E value is GFT distributed to a good approximation. Moreover, it is shown that the root of the expectation value of the highest `normalized' intensity is not only an upper limit for the expectation value of the highest E value but also a very good estimate. Qualitatively, this can be attributed to the sharpness of the distribution of the highest E value. Although the formulas were derived with various simplifying assumptions and approximations, they turn out to be useful also for real small-molecule and protein crystal structures, for both thin and thick resolution shells. The only limitation is that low-resolution data (below 2.5,Å) have to be excluded from the analysis. These results have implications for the identification of outliers in experimental diffraction data. [source]

Investigating pH and Cu (II) effects on lipase activity and enantioselectivity via kinetic and spectroscopic methods

BIOTECHNOLOGY JOURNAL, Issue 11 2006
Tian-Wen Xu
Abstract For Candida rugosa lipase (CRL) catalyzed hydrolysis of racemic 1-phenethyl acetate, both the weakly acidic pH (pH 6.0) and the addition of 1 mM copper (II) ion enhanced the enzyme activity and enantioselectivity (E value) about twofold, as compared with that under neutral pH and noadditive conditions. The decrease of activation free energy (,G) and increase of kcat(R)/kcat(S) at weakly acidic pH and/or in the presence of copper (II) characterized the kinetic behavior of CRL. On the other hand, for providing reasonable insights into the catalytic mechanism and the structural basis for enantioselectivity alteration, spectroscopic techniques were employed to probe conformational changes of the enzyme in each medium assayed. The fluorescence emission spectra revealed that pH and copper (II) might exert different effects on the microenvironment of Trp residue and thereby on the protein conformation, which could be further verified by UV-visible and Raman spectra. The conformational modulation of CRL associated with either pH or copper (II) concentration in the reaction medium could be attributed to the flexible and sensitive conformation of the enzyme, which is responsible for the significant variation of apparent activity and enantioselectivity with the tuning of biocatalyst microenvironment. [source]

The effect of aging biosolids on the availability of cadmium and zinc in soil

EUROPEAN JOURNAL OF SOIL SCIENCE, Issue 2 2001
S. Stacey
Summary A major concern with the safe re-use of biosolids on land is the potential for release of metals from organic matter in the biosolids, due to decomposition proceeding as biosolids age. To quantify the effects of biosolid aging on Cd and Zn bioavailability, two sewage sludges (Lagoon sludge and Filtered sludge) and a garden compost were incubated at 25°C and 35°C for 100 days. Changes in availability of Cd and Zn were determined using isotope dilution principles, with the materials being labelled with carrier-free 109Cd and 65Zn. We determined isotopically exchangeable metal pools (E values) and plant available metal pools (L values) by measuring specific activities of Cd and Zn in soil extracts and in wheat plants, respectively. Changes in carbon content over time were determined using 13C-NMR spectroscopy and chemical extraction methods, and related to changes in availability of metal pools as determined by isotopic procedures. Hot-water-extractable carbon content, assumed to represent easily decomposable organic matter, decreased during the 100 days by 80,190 mg kg,1. The Compost and Lagoon sludge showed no change in L values for Cd or Zn with time, but in the Filtered sludge the L values for Cd and Zn increased significantly, by 43% and 56%, respectively. The isotopically exchangeable pools of Cd and Zn did not change with incubation treatment of the biosolids. These data indicate that the potential for metal release from biosolids as organic matter decomposes depends to a large extent on the biosolid composition. [source]

Relationship between the isotopically exchangeable and resin-extractable phosphate of deficient to heavily fertilized soil

EUROPEAN JOURNAL OF SOIL SCIENCE, Issue 4 2000
A. Schneider
Summary The rate and extent of soil,solution transfer of orthophosphate ions (Pi) depend both on soil solution Pi concentration and on time. This is so both in experiments on sorption,desorption and in those on isotopic exchange. Because the two methods are based on different principles, it is questionable whether they give a similar quantification of Pi transfer. The amount of isotopically exchangeable Pi, E, was determined over periods of 100 minutes and described as a function of both time and Pi concentration in solution for three soil samples taken from field plots having different P fertilizer histories over 26 years of annual application. In separate experiments, amounts of Pi, Qd, were extracted from soil suspensions using three levels of anion exchange resin strips for periods ranging from 10 minutes to 7 days. Both initial and final solution Pi concentrations were measured. These concentrations and periods of resin-contact were used to predict the difference in E, ,E, between the initial and final states of the suspension,resin system using extrapolations of the equations fitted to the exchange data. Under conditions in which the solution concentration of Pi decreased during extraction the ,E values and the resin-extracted Pi values, Qd, were equal. It is thus possible, using the description of E, to predict the amount of Pi released from soil suspension knowing the initial and final solution Pi concentrations and the time it took for the system to pass from the initial to the final state. For the soil studied, identical amounts of mobile Pi, i.e. the Pi which participates in the soil,solution dynamics, may therefore be assessed by either isotopic exchange or desorption. [source]

Methods for determining labile cadmium and zinc in soil

Investigation of the Mekong River basin hydrology for 1980,2000 using the YHyM

HYDROLOGICAL PROCESSES, Issue 9 2008
Hapu Arachchige Prasantha Hapuarachchi
Abstract This study investigates the Mekong River basin hydrology for the 1980,2000 period using a grid-based distributed hydrological model called Yamanashi Hydrological Model (YHyM). The performance of the model is evaluated using data observed at different locations and the results justify the physical soundness of the model. The seasonal variations of climatic and hydrological characteristics of the basin such as soil moisture, ground water saturation deficit, runoff, precipitation, evapotranspiration, etc. are analysed. On the basis of the simulated results, it is noticeable that there is no significant trend in the precipitation, discharge, or soil moisture state of the basin during the simulated period, though there are some seasonal variations which seem to be natural. However the analysis on the precipitation elasticity (E) of the river flow shows that the E values for all sub-basins are greater than unity, which indicates that x% change in annual precipitation can cause > x% change in annual river flow. Further the basin hydrological responses are analysed for a long term synthetically-induced drought the results of which show the significance of the base flow of the Mekong River basin. Copyright © 2008 John Wiley & Sons, Ltd. [source]

Ab initio QM/MM study of excited state electron transfer between pyrene and 4,4,-bis(dimethylamino)-diphenylmethane with different solvent systems: Role of hydrogen bonding within solvent molecules

One-Pot, Regioselective Synthesis of Substituted Arylglycines for Kinetic Resolution by Penicillin G Acylase

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2008
Peter Grundmann
Abstract Amido-alkylation of electron-rich arenes with phenylacetamide and glyoxylic acid offers an inexpensive route to a large variety of N -phenylacetylated arylglycines that are suited for immediate enzymatic resolution by penicillin G acylase. When performed under mild conditions at 5,°C in acetic acid/HCl, this simple one-pot operation resulted in the formation of single regioisomers only (,98%). Subsequent kinetic resolution of the amino acid derivatives by penicillin G acylase at pH,8.0 occurred generally with E values>100 and thus furnished free (S)-configurated arylglycines with high enantiomeric purity. The corresponding enantiopure (R)-substrates, easily separable by a phase-selective extraction process, provided the corresponding (R)-enantiomers upon conventional hydrolysis. This one-pot, two-step procedure for arylglycine synthesis, resolution and work-up requires a minimum of equipment and grants rapid access to both enantiopure (S)- and (R)-antipodes of non-natural ,-amino acids in small- to large-scale quantities. [source]

In vivo spectroradiometric evaluation of colour matching errors among five shade guides

JOURNAL OF ORAL REHABILITATION, Issue 1 2009
Q. LI
Summary, The purpose of this study was to evaluate the colour errors of visual shade selection by five different shade guides. The maxillary left central incisors of sixty participants were visually evaluated by two groups of prosthodontists, with different clinical experience. The shade selection results were recorded and the most selected tab was determined as the resultant shade for each tooth. If totally different opinions were obtained, consensus was needed to determine the resultant shade among the observers. The colour distributions (L*, a* and b*) of each tooth and shade tab were measured using a spectroradiometer. The coverage errors (CEs) of each shade guide and colour differences (,E values) between a tooth and the selected shade tabs were calculated. Two-way anova and Tukey's post hoc analysis were used to evaluate the differences of CE and ,E values among shade guides and clinical experience (, = 0·05). Coverage errors and ,E values in all of the five shade guide systems were all beyond the clinical threshold of 3·3 units. The consensus led to a better colour matching than that of the single decision group in Vitapan 3D-Master and Shofu NCC shade guides. A significant difference (P < 0·001) was found among ,E values of the shade guide system and clinical experience. In conclusion, all five of the shade guide systems used did not achieve clinically compatible shade matching. However, the Vitapan 3D Master shade guide system resulted in the lowest CEs and ,E values. Consensus could be helpful in enhancing the aesthetic results using Vitapan 3D Master and Shofu NCC shade guides. [source]

Influences of alkyl group chain length and polar head group on chemical skin permeation enhancement

JOURNAL OF PHARMACEUTICAL SCIENCES, Issue 8 2001
Kevin S. Warner
Abstract Previous investigations in our laboratory on the influence of the n -alkanols and the 1-alkyl-2-pyrrolidones as skin permeation enhancers for steroid molecules as permeants demonstrated that the enhancer potencies (based on aqueous concentration values) of these two homologous series were the same when compared at the same alkyl chain length; that is, the contribution of the hydroxyl group and that of the pyrrolidone group to enhancer potency were the same. The purpose of the present study was to further investigate what was believed to be a somewhat surprising finding, and two additional homologous series, the 1,2-alkanediols and N,N -dimethylalkanamides, were selected for study as enhancers. Corticosterone (CS) flux enhancement along the lipoidal pathway of hairless mouse skin stratum corneum was determined with 1,2-hexane-, 1,2-octane-, and 1,2-decanediol and with N,N -dimethylhexanamide, N,N - dimethylheptanamide, N,N -dimethyloctanamide, and N,N -dimethylnonanamide as enhancers. The enhancement factor (E) for the lipoidal pathway was calculated from the CS permeability coefficient and the CS solubility data over a 4 to 100 range of E values. Comparisons of the enhancer potencies of all four homologous series revealed that the enhancer potencies of all were very nearly the same when compared at equal alkyl group chain length. Moreover, the contribution of each of the polar head groups toward the enhancer potency was essentially constant, independent of the alkyl group chain length. It was reasoned that this outcome was either the result of the random selection of four polar head groups making the same contribution to enhancer potency or the result of these particular polar head groups not contributing to enhancer potency. To test the hypothesis that the former was more likely than the latter and that a suitable semipolar organic phase may mimic the microenvironment of the polar head group at the site of enhancer action, n -octanol,phosphate buffered saline (PBS) and n -hexane,PBS partition coefficients were determined for all the enhancers. The n -octanol,PBS partition coefficients for the enhancers, but not the n -hexane,PBS partition coefficients, were very nearly the same when compared at equal alkyl group chain lengths; this result supports the hypothesis that each of the four polar head groups likely contributes the same toward the enhancer potency and locates in the semipolar region of the hairless mouse skin stratum corneum lipid bilayers, which is well-approximated by water-saturated n -octanol. © 2001 Wiley-Liss, Inc. and the American Pharmaceutical Association J Pharm Sci 90:1143,1153, 2001 [source]

Evaluation of heat and oxidative damage during storage of processed tomato products.

JOURNAL OF THE SCIENCE OF FOOD AND AGRICULTURE, Issue 11 2002

Abstract The evolution of heat damage during storage of tomato pulp, puree and paste was studied by accelerated aging tests. Heat damage indices,5-hydroxymethyl-2-furfural (HMF), furosine and colour changes (,E),were evaluated for tomato products stored at 30, 40 and 50,°C for up to 90 days. Furosine and ,E values increased following pseudo-zero-order kinetics, and the higher the solid content of the products, the higher were the rate constant values. HMF formation followed pseudo-first-order kinetics in tomato pulp and pseudo-zero-order kinetics in puree and paste samples. Data show that heat damage reactions in tomato products proceed even at room temperature, and the kinetic model provided can be used to predict changes occurring during shelf-life. © 2002 Society of Chemical Industry [source]

Particle size effect on the film-forming process of PS/PBA composite latexes

POLYMER COMPOSITES, Issue 9 2010
aziye U
In this work, the effect of hard particle size and blend ratio on the film formation behavior of hard polystyrene (PS) and soft poly(n -butyl acrylate) (PBA) latex blends was studied by means of steady-state fluorescence and UV,visible techniques in conjunction with atomic force microscopy. Three different sets of latexes were synthesized: PBA latex (diameter 97 nm), pyrene (P)-labeled large PS (LgPS; diameter 900 nm), and small PS (SmPS; diameter 320 nm). Two different series of latex blends (LgPS/PBA and SmPS/PBA) were prepared with varying blend composition at room temperature separately. Films were then annealed at elevated temperatures above glass transition (Tg) temperature of PS. Fluorescence intensity (IP) from P and photon transmission intensity (Itr) were measured after each annealing step to monitor the stages of film formation. The results showed that a significant change occurred in IP and Itr at a certain critical weight fraction (Rc) of PBA. Below Rc, two distinct film formation stages, which are named as void closure and interdiffusion, were seen. However, at PBA concentrations nearer to or above Rc, no film formation can be achieved. Comparing to the LgPS/PBA, the sintering process of SmPS/PBA particles occurred at much lower temperatures. Film formation stages for R < Rc were modeled, and related activation energies were calculated. Void closure (,H) and interdiffusion (,E) activation energies for SmPS/PBA were also found smaller in comparing with LgPS/PBA series. However, ,H and ,E values were not changed much with the blend composition for both series. POLYM. COMPOS., 31:1637,1652, 2010. © 2009 Society of Plastics Engineers [source]

Stereoselectivity of Pseudomonas cepacia lipase toward secondary alcohols: A quantitative model

PROTEIN SCIENCE, Issue 6 2000
Tanja Schulz
Abstract The lipase from Pseudomonas cepacia represents a widely applied catalyst for highly enantioselective resolution of chiral secondary alcohols. While its stereopreference is determined predominantly by the substrate structure, stereoselectivity depends on atomic details of interactions between substrate and lipase. Thirty secondary alcohols with published E values using P. cepacia lipase in hydrolysis or esterification reactions were selected, and models of their octanoic acid esters were docked to the open conformation of P. cepacia lipase. The two enantiomers of 27 substrates bound preferentially in either of two binding modes: the fast-reacting enantiomer in a productive mode and the slow-reacting enantiomer in a nonproductive mode. Nonproductive mode of fast-reacting enantiomers was prohibited by repulsive interactions. For the slow-reacting enantiomers in the productive binding mode, the substrate pushes the active site histidine away from its proper orientation, and the distance d(HN, , Oalc) between the histidine side chain and the alcohol oxygen increases. d(HN, , Oalc) was correlated to experimentally observed enantioselectivity: in substrates for which P. cepacia lipase has high enantioselectivity (E > 100), d(HN, , Oalc) is>2.2 Å for slow-reacting enantiomers, thus preventing efficient catalysis of this enantiomer. In substrates of low enantioselectivity (E < 20), the distance d(HN, , Oalc) is less than 2.0 Å, and slow- and fast-reacting enantiomers are catalyzed at similar rates. For substrates of medium enantioselectivity (20 < E< 100), d(HN, , Oalc) is around 2.1 Å. This simple model can be applied to predict enantioselectivity of P. cepacia lipase toward a broad range of secondary alcohols. [source]

Role of foods in irregular aggravation of skin lesions in children with atopic dermatitis

THE JOURNAL OF DERMATOLOGY, Issue 7 2008
Toshiaki UENISHI
ABSTRACT Atopic dermatitis is a common inflammatory skin disease that especially affects children and adolescents. Many environmental factors have been recognized as relevant in aggravating skin lesions of the disease. However, it remains to be determined whether foods play a role in worsening of skin lesions in children with atopic dermatitis. In the present study, we investigated whether foods play a role in irregular aggravation of skin lesions in children with the disease. The study population consisted of 69 patients aged 3,15 years with atopic dermatitis. They were hospitalized and open challenge tests were performed with suspected foods. Photographs of representative skin lesion sites were taken at baseline and before and after the challenge. We determined challenge-positive foods by evaluating the comparable before/after challenge photographs. One to three (average, 1.9) challenge-positive foods were confirmed in 52 (75%) of the 69 patients examined. Predominant offending foods were chocolate, cheese and yogurt. Specific immunoglobulin E values to offending foods were mostly negative. We asked patients to exclude challenge-positive foods from their diets. They were then discharged and followed up for 3 months at our outpatient clinic. Exclusion of the offending foods for 3 months brought about a remarkable improvement in the disease. These results suggest that foods play an important role in irregular aggravation of skin lesions in children with atopic dermatitis. [source]

Strategic Selection of Hyperthermophilic Esterases for Resolution of 2-Arylpropionic Esters

BIOTECHNOLOGY PROGRESS, Issue 5 2003
Amitabh C. Sehgal
Homologues to Carboxylesterase NP and Candida rugosa lipase, used for the chiral separation of racemic mixtures of 2-arylpropionic methyl esters, were identified by BLAST searches of available genome sequences for hyperthermophilic microorganisms. Two potential candidates were identified: a putative lysophospholipase from Pyrococcus furiosus (Pfu-LPL) and a carboxylesterase from Sulfolobussolfataricus P1 (Sso-EST1). Although both enzymes showed hydrolytic preference toward the (S) methyl ester, only Sso-EST1 yielded highly optically pure (S) naproxen (%eep , 90) and was thus further investigated. Changes in pH or reaction time showed little improvement in %eep or E values with Sso-EST1. However, the addition of 25% methanol resulted in a 25% increase in E. The effect of various cosolvents on the enantiomeric ratio showed no correlation with the log P or dielectric constant values of the solvent. However, an inverse relationship between E and the denaturation capacity (DC) of the water miscible cosolvents was observed. This was attributed to an increase in enzyme flexibility with increasing solvent DC values leading to a concomitant reduction in the resolving power of Sso-EST1. The results here show that although bioinformatics tools can be used to select candidate biocatalysts for chiral resolution of 2-arylpropionic esters, biochemical characterization is needed to definitively determine functional characteristics. [source]

Methods for determining labile cadmium and zinc in soil

Lower critical solution temperature determination of smart, thermosensitive N -isopropylacrylamide- alt -2-hydroxyethyl methacrylate copolymers: Kinetics and physical properties

JOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2008
Mohammad M. Fares
Abstract The lower critical solution temperatures (LCSTs) were verified and determined for different molar feed ratios of N -isopropylacrylamide (NIPAAm) and 2-hydroxyethyl methacrylate (HEMA) monomers with ultraviolet spectroscopy and differential scanning calorimetry techniques. Increases in the NIPAAm monomer content played a crucial role in the LCST, which increased up to 36.7°C at 50 mol %. However, a further increase in the NIPAAm monomer content steadily reduced the LCST, which decreased to 33°C at 100 mol % NIPAAm [i.e., pure poly(N -isopropylacrylamide)]. The rate of copolymerization, assessed by the conventional conversion (%),time method, and the apparent activation energies were determined. The reactivity ratios of the monomers, determined by the Kelen,Tudos and Fineman,Ross techniques, together with the results of an equation, showed that the copolymer which formed was an alternating copolymer. The Q,e values for the NIPAAm monomer were determined. The equation showed the linear Arrhenius behavior of ln(r1r2) versus the reciprocal of the temperature (where r1 and r2 are the reactivity ratios of NIPAAm and HEMA, respectively): the activation energy difference [i.e., (E12 + E21) , (E11 + E22), where E12, E21, E11, and E22 are various activation energies] was found to be ,109 kJ/mol. The copolymers were characterized with 1H-NMR, 13C-NMR, Fourier transform infrared, ultraviolet,visible, thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, and scanning electron microscopy techniques. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source]

Radical copolymerization of vinylidene fluoride with 1-bromo-2,2-difluoroethylene

JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 18 2010
G. K. Kostov
Abstract The radical copolymerization of vinylidene fluoride (VDF) and 1-bromo-2,2-difluoroethylene (BDFE) in 1,1,1,3,3-pentafluorobutane solution at different monomer molar ratios (ranging from 96/4 to 25/75 mol %) and initiated by tert -butylperoxypivalate (TBPPI, mainly) is presented. Poly(VDF- co -BDFE) copolymers of various aspects (from white powders to yellow viscous liquids) were produced depending on the copolymer compositions. The microstructures of the obtained copolymers were characterized by 19F and 1H NMR spectroscopy and by elementary analysis and these techniques enabled one to assess the contents of both comonomers in the produced copolymers. VDF was shown to be more incorporated in the copolymer than BDFE. From the extended Kelen and Tudos method, the kinetics of the radical copolymerization led to the determination of the reactivity ratios, ri, of both comonomers (rVDF = 1.20 ± 0.50 and rBDFE = 0.40 ± 0.15 at 75 °C) showing that VDF is more reactive than BDFE. Alfrey-Price's Q and e values of BDFE monomer were calculated to be 0.009 (from QVDF = 0.008) or 0.019 (from QVDF = 0.015) and +1.22 (vs. eVDF = 0.40) or +1.37 (vs. eVDF = 0.50), respectively, indicating that BDFE is an electron-accepting monomer. Statistic cooligomers were produced with molar masses ranging from 1,800 to 5,500 g/mol (assessed by GPC with polystyrene standards). A further evidence of the successful copolymerization was shown by the selective reduction of bromine atoms in poly(VDF- co -BDFE) cooligomers that led to analog PVDF. The thermal properties of the poly(VDF- co -BDFE) cooligomers were also determined and those containing a high VDF amount exhibited a high thermal stability. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3964,3976, 2010. [source]

Synthesis and polymerization of fluorinated monomers bearing a reactive lateral group.

JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 19 2003

Abstract The radical copolymerization in solution of vinylidene fluoride (VDF; or 1,1-difluoroethylene) with methyl 1,1-dihydro-4,7-dioxaperfluoro-5,8-dimethyl non-1-enoate (MDP) initiated by di- tert -butyl peroxide is presented. Six copolymerization reactions were investigated with initial [VDF]0/[MDP]0 molar ratios of 35/65 to 80/20. Both of these comonomers copolymerized in this range of copolymerization. Moreover, these comonomers homopolymerized separately under these conditions. The copolymer compositions of these random copolymers were calculated by means of 19F NMR spectroscopy, which allowed the quantification of the respective amounts of each monomeric unit in the copolymers. The Tidwell,Mortimer method was used for the assessment of the reactivity ratios (ri) of both comonomers, which showed a higher incorporation of MDP in the copolymers (rMDP = 2.41 ± 2.28 and rVDF = 0.38 ± 0.21 at 120 °C). The Alfrey,Price Q and e values of the trifluoroallyl monomer MDP were calculated to be 0.024 (from QVDF = 0.008) or 0.046 (from QVDF = 0.015) and 0.70 (vs eVDF = 0.40) or 0.80 (vs eVDF = 0.50), respectively, indicating that MDP was an electron-accepting monomer. The thermal properties of these fluorinated copolymers were also determined. Except for those containing a high amount of VDF, the copolymers were amorphous. Each showed one glass-transition temperature (Tg) only, and with known laws of Tg's, Tg of the MDP homopolymer was assessed. It was compared to that obtained from the direct radical homopolymerization of MDP and discussed. Indeed, these two values were close (Tg = ,3 °C). Thermogravimetric analyses were performed, and they showed that the copolymers were rather thermostable because the thermal degradation occurred at 280 °C. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3109,3121, 2003 [source]

Termination in Dilute-Solution Free-Radical Polymerization: A Composite Model

MACROMOLECULAR THEORY AND SIMULATIONS, Issue 5 2003
Gregory B. Smith
Abstract Literature data are summarized for the chain-length-dependence of the termination rate coefficient in dilute solution free-radical polymerizations. In essence such experiments have yielded two parameter values: the rate coefficient for termination between monomeric free radicals, k, and a power-law exponent e quantifying how kt values decrease with increasing chain length. All indications are that the value e,,,0.16 in good solvent is accurate, however the values of k which have been deduced are considerably lower than well-established values for small molecule radicals. This seeming impasse is resolved by putting forward a ,composite' model of termination: it is proposed that the value e,,,0.16 holds only for long chains, with e being higher for small chains , the value 0.5 is used in this paper, although it is not held to dogmatically. It is then investigated whether this model is consistent with experimental data. This is a non-trivial task, because although the experiments themselves and the ways in which they are analyzed are elegant and not too complicated, the underlying theory is sophisticated, as is outlined. Simulations of steady-state polymerization experiments are first of all carried out, and it is shown that the composite model of termination both recovers the e values which have been found and beautifully explains why these experiments considerably underestimate the true value of k. Simulations of pulsed-laser polymerizations find the same, although not quite so strikingly. It is therefore concluded that our new termination model, which retains the virtue of simplicity and in which all parameter values are physically reasonable, is consistent with experimental data. Taking a wider view, it seems likely that the situation of the exponent e varying with chain length will not just be the case in dilute solution, but will be the norm for all conditions, which would give our model and our work a general relevance. Normalized chain length distributions from PLP simulations. [source]