Home About us Contact
|
Home About us Contact | ||
|
|
||
Mole Fraction (mole + fraction)
Selected AbstractsEffect of Cellulase Mole Fraction and Cellulose Recalcitrance on Synergism in Cellulose Hydrolysis and BindingBIOTECHNOLOGY PROGRESS, Issue 1 2006Tina Jeoh Elucidating the molecular mechanisms that govern synergism is important for the rational engineering of cellulase mixtures. Our goal was to observe how varying the loading molar ratio of cellulases in a binary mixture and the recalcitrance of the cellulose to enzymatic degradation influenced the degree of synergistic effect (DSE) and degree of synergistic binding (DSB). The effect of cellulose recalcitrance was studied using a bacterial microcrystalline cellulose (BMCC), which was exhaustively hydrolyzed by a catalytic domain of Cel5A, an endocellulase. The remaining prehydrolyzed BMCC (PHBMCC) was used to represent a recalcitrant form of cellulose. DSE was observed to be sensitive to loading molar ratio. However, on the more recalcitrant cellulose, synergism decreased. Furthermore, the results from this study reveal that when an exocellulase (Cel6B) is mixed with either an endocellulase (Cel5A) or a processive endocellulase (Cel9A) and reacted with BMCC, synergism is observed in both hydrolysis and binding. This study also revealed that when a "classical" endocellulase (Cel5A) and a processive endocellulase (Cel9A) are mixed and reacted with BMCC, only limited synergism is observed in reducing sugar production; however, binding is clearly increased by the presence of the Cel5A. [source] Unconventional Spin Crossover in Dinuclear and Trinuclear Iron(III) Complexes with Cyanido and Metallacyanido BridgesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 21 2009alitro Abstract A nonsymmetrical triamine, 1,6-diamino-4-azahexane, was Schiff-condensed with (X-substituted) o -salicylaldehyde to yield pentadentate ligands X-L5: salpet and MeBu-salpet. These ligands form mononuclear, dinuclear, and trinuclear FeIII complexes, whose structures were determined by single-crystal X-ray analysis. Of the mononuclear complexes, [FeIII(salpet)Cl] and [FeIII(MeBu-salpet)Cl] are high spin (S = 5/2), whereas [FeIII(salpet)CN]·MeOH is low spin (S = 1/2). The dinuclear and trinuclear complexes show a kind ofthermally induced spin crossover. The dinuclear complex [L5FeIII(CN)FeIIIL5](ClO4)·2H2O (L5 = salpet) is a mixed-spin assembly: the C -coordinated FeIII center is low spin (L) and the N -coordinated FeIII center is high spin (H) at low temperature; an antiferromagnetic interaction occurs between them. This LH reference state is mixed with the LL one. Upon heating, the system shows an increasing content of the HH state. Also, the dinuclear complex [L5FeIII(CN)FeIIIL5](BPh4)·2MeCN (L5 = MeBu-salpet) exhibits a spin transition between LH and HH spin pairs. The mixed-valence trinuclear complex [L5FeIII{FeII(CN)5(NO)}FeIIIL5]·0.5MeOH·3.75H2O (L5 = salpet) shows spin crossover with a residual high-spin fraction at liquid He temperature owing to the LL + LH ground state. The metallacyanido-bridged complex [L5FeIII{Ni(CN)4}FeIIIL5]·2MeOH (L5 = MeBu-salpet) contains a high-spin pair, HH, over the whole temperature interval with a ferromagnetic exchange interaction. A theoretical model was outlined that allows simultaneous fitting of all available experimental data (magnetic susceptibility, magnetization, high-spin mole fraction obtained from the Mössbauer spectra) on a common set of parameters. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Chemical effects of CO2 addition to oxidizer and fuel streams on flame structure in H2,O2 counterflow diffusion flamesINTERNATIONAL JOURNAL OF ENERGY RESEARCH, Issue 13 2003Jeong Park Abstract Numerical simulation of CO2 addition effects to fuel and oxidizer streams on flame structure has been conducted with detailed chemistry in H2,O2 diffusion flames of a counterflow configuration. An artificial species, which displaces added CO2 in the fuel- and oxidizer-sides and has the same thermochemical, transport, and radiation properties to that of added CO2, is introduced to extract pure chemical effects in flame structure. Chemical effects due to thermal dissociation of added CO2 causes the reduction flame temperature in addition to some thermal effects. The reason why flame temperature due to chemical effects is larger in cases of CO2 addition to oxidizer stream is well explained though a defined characteristic strain rate. The produced CO is responsible for the reaction, CO2+H=CO+OH and takes its origin from chemical effects due to thermal dissociation. It is also found that the behavior of produced CO mole fraction is closely related to added CO2 mole fraction, maximum H mole fraction and its position, and maximum flame temperature and its position. Copyright © 2003 John Wiley & Sons, Ltd. [source] Analysis of supersaturation and nucleation in a moving solution droplet with flowing supercritical carbon dioxideJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 4 2005Mamata Mukhopadhyay Abstract A supercritical antisolvent (SAS) process is employed for production of solid nanoparticles from atomized droplets of dilute solution in a flowing supercritical carbon dioxide (SC CO2) stream by attaining extremely high, very rapid, and uniform supersaturation. This is facilitated by a two-way mass transfer of CO2 and solvent, to and from the droplet respectively, rendering rapid reduction in equilibrium solubility of the solid solute in the ternary solution. The present work analyses the degree of supersaturation and nucleation kinetics in a single droplet of cholesterol solution in acetone during its flight in a flowing SC CO2 stream. Both temperature and composition are assumed to be uniform within the droplet, and their variations with time are calculated by balancing the heat and mass transfer fluxes to and from the droplet. The equilibrium solubility of cholesterol with CO2 dissolution has been predicted as being directly proportional to the Partial Molar Volume Fraction (PMVF) of acetone in the binary (CO2,acetone) system. The degree of supersaturation has been simulated up to the time required to attain almost zero cholesterol solubility in the droplet for evaluating the rate of nucleation and the size of the stable critical nuclei formed. The effects of process parameters have been analysed in the pressure range of 7.1,35.0 MPa, temperature range of 313,333 K, SC CO2 flow rate of 0.1136,1.136 mol s,1, the ratio of the volumetric flow rates of CO2 -to-solution in the range of 100,1000, and the initial mole fraction of cholesterol in acetone solution in the range of 0.0025,0.010. The results confirm an extremely high and rapid increase in degree of supersaturation, very high nucleation rates and stable critical nucleus diameter of the order of a nanometre. Copyright © 2005 Society of Chemical Industry [source] Active Packaging of Fresh Chicken Breast, with Allyl Isothiocyanate (AITC) in Combination with Modified Atmosphere Packaging (MAP) to Control the Growth of PathogensJOURNAL OF FOOD SCIENCE, Issue 2 2010Joongmin Shin ABSTRACT:,Listeria monocytogenes,and,Salmonella typhimurium,are major bacterial pathogens associated with poultry products. Ally isothiocyanate (AITC), a natural antimicrobial compound, is reportedly effective against these pathogenic organisms. A device was designed for the controlled release of AITC with modified atmosphere packaging (MAP), and then evaluated for its ability to control the growth of,L. monocytogenes,and,S. typhimurium,on raw chicken breast during refrigerated storage. In order to obtain controlled release during the test period, a glass vial was filled with AITC and triglyceride. It was then sealed using high-density polyethylene film. The release of AITC was controlled by the concentration (mole fraction) of AITC in the triglyceride and by the AITC vapor permeability through the film. The fresh chicken samples were inoculated with one or the other of the pathogens at 104 CFU/g, and the packages (with and without AITC-controlled release device) were flushed with ambient air or 30% CO2/70% N2 before sealing, and then stored at 4 °C for up to 21 d. The maximum reduction in MAP plus AITC (compared to MAP alone) was 0.77 log CFU/g for,L.,monocytogenes,and 1.3 log CFU/g for,S.,typhimurium. The color of the chicken breast meat was affected by the concentration of AITC. Overall, a release rate of 0.6 ,g/h of AITC was found to not affect the color, whereas at 1.2 ,g/h of AITC the surface of the chicken was discolored. [source] The structural organization in aqueous solutions of ionic liquidsAICHE JOURNAL, Issue 1 2009Xiao Zhu Abstract The 1H NMR combined with the local composition (LC) model has been employed to investigate the structural organization of two aqueous solutions of ionic liquids (ILs), namely 1-ethyl-3-methylimidazolium tetrafluoroborate (EmimBF4) and n-butylammonium nitrate (N4NO3). The correlation of chemical shifts using the LC model shows that the self-association of IL plays the leading role, and water prefers to interact with IL rather than self-association in IL-rich region. Instead the network of water molecules is established in water-rich region, because the self-association of water predominates. Furthermore, the difference between the local and the bulk composition presents the turnover at x(IL) (mole fraction of IL) close to 0.6 for EmimBF4/water, which is in accordance with the change of excess function. Accordingly, it could be presumed that the excess properties for N4NO3/water system should behave turnover at x(IL) , 0.55 since the local and the bulk exhibit maximal difference at this composition. © 2008 American Institute of Chemical Engineers AIChE J, 2009 [source] Simulation of binary mixture adsorption of methane and CO2 at supercritical conditions in carbonsAICHE JOURNAL, Issue 3 2006Yohanes Kurniawan Abstract Knowledge of the adsorption behavior of coal-bed gases, mainly under supercritical high-pressure conditions, is important for optimum design of production processes to recover coal-bed methane and to sequester CO2 in coal-beds. Here, we compare the two most rigorous adsorption methods based on the statistical mechanics approach, which are Density Functional Theory (DFT) and Grand Canonical Monte Carlo (GCMC) simulation, for single and binary mixtures of methane and carbon dioxide in slit-shaped pores ranging from around 0.75 to 7.5 nm in width, for pressure up to 300 bar, and temperature range of 308-348 K, as a preliminary study for the CO2 sequestration problem. For single component adsorption, the isotherms generated by DFT, especially for CO2, do not match well with GCMC calculation, and simulation is subsequently pursued here to investigate the binary mixture adsorption. For binary adsorption, upon increase of pressure, the selectivity of carbon dioxide relative to methane in a binary mixture initially increases to a maximum value, and subsequently drops before attaining a constant value at pressures higher than 300 bar. While the selectivity increases with temperature in the initial pressure-sensitive region, the constant high-pressure value is also temperature independent. Optimum selectivity at any temperature is attained at a pressure of 90-100 bar at low bulk mole fraction of CO2, decreasing to approximately 35 bar at high bulk mole fractions. © 2005 American Institute of Chemical Engineers AIChE J, 2006 [source] Analysis of multicomponent adsorption kinetics on activated carbonAICHE JOURNAL, Issue 4 2003L. P. Ding An integrated mathematical model for the kinetics of multicomponent adsorption on microporous carbon was developed. Transport in this bidisperse solid is represented by balance equations in the macropore and micropore phases, in which gas-phase diffusion dominates the mass transfer in the macropores, with the phenomenological diffusivities represented by the generalized Maxwell,Stefan (GMS) formulation. Viscous flow also contributes to the macropore fluxes and is included in the MS expressions. Diffusion of the adsorbed phase controls the mass transfer in the micropore phase, which is also described in a similar way by the MS method. The adsorption isotherms are represented by a new heterogeneous modified vacancy solution theory formulation of adsorption, which has proved to be a robust method for adsorption on activated carbons. The model is applied to the coadsorption and codesorption of C2H6 and C3H8 on Ajax and Norit carbon, as well as the displacement on Ajax carbon. The effect of the viscous flow in the macropore phase is not significant for the cases studied. The model accurately predicts the overshoot behavior and rollup of C2H6 during coadsorption. The prediction for the heavier compound C3H8 is always satisfactory, though at higher C3H8 mole fraction, the overshoot extent of C2H6 is overpredicted, possibly due to neglect of heat effects. [source] Liquid,liquid miscibility gaps and hydrate formation in drug,water binary systems: Pressure,temperature phase diagram of lidocaine and pressure,temperature,composition phase diagram of the lidocaine,water systemJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 6 2010René Ceolin Abstract The pressure,temperature (P,T) melting curve of lidocaine was determined (dP/dT,=,3.56,MPa,K,1), and the lidocaine,water system was investigated as a function of temperature and pressure. The lidocaine,water system exhibits a monotectic equilibrium at 321,K (ordinary pressure) whose temperature increases as the pressure increases until the two liquids become miscible. A hydrate, unstable at ordinary pressure, was shown to form, on increasing the pressure, from about 70,MPa at low temperatures (200,300,K). The thermodynamic conditions of its stability were inferred from the location of the three-phase equilibria involving the hydrate in the lidocaine,water pressure,temperature,mole fraction (P,T,x) diagram. © 2009 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 99: 2756,2765, 2010 [source] Aromatic nitro substitution reaction between 4-nitro- N - n -butyl-1,8-naphthalimide and n -heptanethiol in water,methanol binary mixturesJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 7 2009Eduardo Rezende Triboni Abstract The second-order rate constants of thiolysis by n -heptanethiol on 4-nitro- N - n -butyl-1,8-naphthalimide (4NBN) are strongly affected by the water,methanol binary mixture composition reaching its maximum at around 50% mole fraction. In parallel solvent effects on 4NBN absorption molar extinction coefficient also shows a maximum at this composition region. From the spectroscopic study of reactant and product and the known H-bond capacity of the mixture a rationalization that involves specific solvent H-donor interaction with the nitro group is proposed to explain the kinetic data. Present findings also show a convenient methodology to obtain strongly fluorescent imides, valuable for peptide and analogs labeling as well as for thio-naphthalimide derivatives preparations. Copyright © 2008 John Wiley & Sons, Ltd. [source] Hydrolysis of 2-(p -nitrophenoxy)tetrahydropyran: solvent and ,-deuterium secondary kinetic isotope effects and relationships with the solvolysis of simple secondary alkyl arenesulfonates and the enzyme-catalyzed hydrolysis of glycosides,JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 6-7 2004Imran A. Ahmad Abstract The effect of solvent composition in aqueous ethanol, trifluoroethanol and hexafluoropropan-2-ol on the rate constant and activation parameters for the uncatalysed hydrolysis of 2-(p -nitrophenoxy)tetrahydropyran (1) was investigated, and the m(YOTs) value is 0.60. This appreciable but less than maximal value is in accordance with an SN1 mechanism with rate-limiting ionization. The ,-deuterium secondary kinetic isotope effect (,-kie) for the uncatalysed hydrolysis of 1 is 1.17 in water (46°C), 1.15 in aqueous trifluoroethanol (50% mole fraction, 70.6°C) and 1.13 in aqueous ethanol (50% mole fraction, 70.6°C). These values correspond to about 1.19 at 25°C, which is characteristic of rate-limiting ionization in an SN1 reaction and appreciably higher than values for enzyme-catalysed glycolysis. The ,-kie is smaller under aqueous acidic conditions (1.07, 0.1,mol,dm,3 hydrochloric acid, 20.2°C) when 1 hydrolyses with acid catalysis. The previously reported ,-kie for the hydrolysis of 1 in buffered aqueous dioxan (1.063, 25°C) is now seen to correspond to acid-catalysed hydrolysis. These new results for 1 indicate that transition structures in enzyme-catalysed glycolyses with ,-kie values of less than about 1.15 at 25°C involve a lower degree of carbenium ion character than has hitherto been assumed. Copyright © 2004 John Wiley & Sons, Ltd. [source] Intermolecular H-bond in propan-2-ol and its solutions with acetonitrileJOURNAL OF RAMAN SPECTROSCOPY, Issue 12 2007F. H. Tukhvatullin Abstract Formation of propan-2-ol,acetonitrile dimers is manifested in the Raman spectra as an appearance of a band of aggregates in the high-wavenumber side of the CN vibrational band of liquid acetonitrile (,2 cm,1). The intensity of the band of aggregates changes with a change in the concentration of the mixture (1,0.05 mole fraction). For propan-2-ol we carried out nonempirical calculations of a structure of isolated dimer aggregates. The formation of an intramolecular H-bond between the H and the O atom of the \newbox\osprulebox \newdimen\osprulewd \def\osprule#1#2{ \global\setbox\osprulebox=\hbox{#1} \osprulewd=\wd\osprulebox\advance\osprulewd by -8pt \raise0.5pc\hbox{$\matrix{\hskip-1pt\lower6.5pt\hbox{\vrule height #2pt}\lower4.5pt\hbox to \osprulewd{\hrulefill}\lower6.5pt\hbox{\vrule height #2pt}\cr \noalign{\vskip-1pt} \hbox{#1}\cr}$} } $\osprule{{\rm HCO}}{2.5} \hbox{H}$ group of length 2.045 Å is possible in the monomer molecule. The CH3 groups of alcohol are not equivalent. In the dimer formation, intramolecular H-bond in the \newbox\osprulebox \newdimen\osprulewd \def\osprule#1#2{ \global\setbox\osprulebox=\hbox{#1} \osprulewd=\wd\osprulebox\advance\osprulewd by -8pt \raise0.5pc\hbox{$\matrix{\hskip-1pt\lower6.5pt\hbox{\vrule height #2pt}\lower4.5pt\hbox to \osprulewd{\hrulefill}\lower6.5pt\hbox{\vrule height #2pt}\cr \noalign{\vskip-1pt} \hbox{#1}\cr}$} } $\osprule{{\rm HCO}}{2.5} \hbox{H}$ group is preserved. An intermolecular H-bond of length 2.045 Å and energy 15 kJ/mole is formed between the H atom of one molecule and the O atom of another molecule of the OH. The length and energy of the H-bond for the propan-2-ol,acetonitrile dimer formations calculate to 2.27 Å and 12.9 kJ/mole, respectively. The H-bond is formed by ,-electrons of nitrogen. The experimental data and the results of calculations are in good agreement. Copyright © 2007 John Wiley & Sons, Ltd. [source] Changes in spectral features with varying mole fractions of anisaldehyde in binary mixturesJOURNAL OF RAMAN SPECTROSCOPY, Issue 3 2007A. Anis Fathima Abstract Raman and IR spectra of neat anisaldehyde (4-methoxybenzaldehyde (4MeOBz)) and its binary mixtures (in polar and nonpolar solvents) with varying mole fraction of 4MeOBz were investigated. The concentration dependence of the wavenumber position and line width (full width at half maximum, FWHM) was analyzed to study the interaction of the solute vibrational modes with the microscopic solvent environment. The wavenumbers of Raman modes of 4MeOBz, namely, the carbonyl stretching, aldehydic , (CH) and ring-breathing modes, showed a linear variation in the peak position for varying concentrations of 4MeOBz in the different solvents. The dependence of Raman line width with concentration of 4MeOBz of these modes was also taken into account. The solute,solvent interaction is stronger in 2-propanol and acetonitrile because of the formation of hydrogen bonds between them, whereas in benzene the interaction is too weak to affect the Raman modes. The modes, , (CO) in 2-propanol and aldehydic , (CH) in acetonitrile, gave a Gaussian-type line width variation, which was explained by the concentration fluctuation model, and the linear variation of the line widths was also interpreted by solute,solvent interactions. IR spectra were taken for these binary mixtures, which also give further support to these data. Copyright © 2006 John Wiley & Sons, Ltd. [source] Oxygen Diffusion in Yttria-Stabilized Zirconia: A New Simulation ModelJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 10 2004R. Krishnamurthy We present a multiscale modeling approach to study oxygen diffusion in cubic yttria-stabilized zirconia. In this approach, we employ density functional theory methods to calculate activation energies for oxygen migration in different cation environments. These are used in a kinetic Monte Carlo framework to calculate long-time oxygen diffusivities. Simulation results show that the oxygen diffusivity attains a maximum value at around 0.1 mole fraction yttria. This variation in the oxygen diffusivity with yttria mole fraction and the calculated values for the diffusivity agree well with experiment. The competing effects of increased oxygen vacancy concentration and increasing activation energy and correlation effects for oxygen diffusion with increasing yttria mole fraction are responsible for the observed dopant content dependence of the oxygen diffusivity. We provide a detailed analysis of cation-dopant-induced correlation effects in support of the above explanation. [source] Density, Surface Tension, and Viscosity of PbO-B2O3 -SiO2 Glass MeltsJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 1 2004Shigeru Fujino The density, surface tension, and viscosity of the melts from the PbO-B2O3 -SiO2 system have been measured at temperatures in the range 1073,1473 K. The effect of composition on these properties was also investigated. The density of the melt was found to increase linearly with increasing PbO content. Molar volume was derived from the density data, and its deviation from the additivity of partial molar volumes was calculated. These deviations in molar volume from those obtained from additivity rules have been used along with the ratio of various coordination numbers of boron (as reported by Bray) to discuss the structure of the melts. The surface tension was found to decrease with decreasing SiO2/B2O3 ratio, and to increase in the range of the PbO content between 30 and 60 mol%, showing a maximum at ,60 mol% PbO, and then decreased with further additions. This result suggested that the surface tension would be affected primarily by the B2O3 content in the range of the PbO content between 30,60 mol%, and mainly by the PbO content in the range of the PbO content >60 mol%, respectively. The viscosity of the melt was found to decrease linearly with increasing PbO content. The results obtained indicate that the increase in viscosity with B2O3 was half that of SiO2 (on a molar basis), and an empirical equation has been proposed for the viscosity as a function of mole fraction. [source] Tandem Action of TpMsNiCl and Supported Cp2ZrCl2 Catalysts for the Production of Linear Low-Density PolyethyleneMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 9 2006Maria Cristina A. Kuhn Abstract Summary: Linear low-density polyethylene (LLDPE) samples with different properties were prepared from ethylene, without the addition of an , -olefin co-monomer, using a combination of the catalyst precursors TpMsNiCl (TpMs,=,hydridotris(3-mesitylpyrazol-1-yl) and Cp2ZrCl2/SMAO-4, by varying the nickel loading mole fraction (xNi). Upon activation with methylaluminoxane (MAO), this binary catalytic system showed activities varying from 12.3 to 309.1 kg of PE,·,(mol[M],·,atm,·,h),1. The properties of the polymeric materials are influenced by xNi as well as by the temperature of polymerization, affording the copolymers with a melting point (Tm) between 118 and 135,°C. The GPC results show that the molecular weight () of the polymers is sensitive to the xNi. In all of the cases studied, the GPC curves displayed monomodal molecular weight distributions (MWDs) with the average molecular weight varying from 30,000 to 507,000 g,·,mol,1. Studies using dynamic mechanical thermal analysis (DMTA) show that the formation of different polymeric materials is associated with the branching content, with the stiffness varying according to the xNi and the temperature used in the polymerization reaction. Overview of the copolymerization process, from ethylene in the presence of MAO, mediated by catalysts 1 and 2/SMAO. [source] New Poly(sodium carboxylate)s Based on Saccharides, 1.MACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 18 2002Characterization of Ionic Allyl Glycoside Polymers, Synthesis Abstract New poly(sodium carboxylate)s, containing monosaccharide side groups with ether linkages to the main chain, are presented as substitutes for water-soluble homo- and copolymers of acrylic acid. Neutral and ionic allyl glycoside monomers, namely allyl- , - D -galactopyranoside and allyl- , - D -glucofuranosidurono-6,3-lactone, were synthesized by Fischer glycosidation. These monomers were copolymerized with maleic anhydride and itaconic acid in aqueous and nonaqueous solution. The corresponding copolymers with different structures, degrees of functionalization, and charge densities were characterized by 13C NMR spectroscopy, molecular-weight measurements, and intrinsic viscosity [,] determination. From these, the monomer reactivity ratios and Mark,Houwink relations were established (see Figure). Copolymerization curves of maleic acid copolymers 6 and 10. M1: mole fraction of allyl monomer 2, and 5, in the feed; m1: mole fraction of allyl monomer in the copolymer. The dashed line shows the course of an ideal alternating copolymerization (excepted: M1,=,0 mol-%, M1,=,100 mol-%). [source] Multi-Component Kinetic Modeling for Controlling Local Compositions in Thermosensitive PolymersMACROMOLECULAR THEORY AND SIMULATIONS, Issue 8 2006Todd Hoare Abstract Summary: An explicit terminal copolymerization kinetic model accounting for the copolymerization of up to four different comonomers is developed and applied to model the conversion profiles and local compositional gradients in functionalized PNIPAM-based polymer and hydrogel systems. The kinetics of the functional comonomer(s) have a large influence on both the mole fraction and chain distribution of functional groups in polymers. Strategies are developed to synthesize polymers with uniform compositions by applying semi-batch techniques or via copolymerization of multiple monomers with the same target functionality but with divergent reactivities relative to NIPAM. Synthetic protocols are also designed to maximize the compositional uniformity and randomness of ampholytic polymers. Instantaneous mole fractions of monomers in polymers as a function of the overall monomer conversion for the copolymerizations of NIPAM, MBA, and two functional monomers: MMA and acrylamide. [source] Ordering in Stretched Bernoullian CopolymersMACROMOLECULAR THEORY AND SIMULATIONS, Issue 1 2003Arkady D. Litmanovich Abstract A new approach is suggested to estimate the theoretical maximum capability to order for stretched Bernoullian copolymers AB, provided interchain AB contacts are unfavorable. A simple Monte Carlo procedure simulating the ordering of such copolymers via rotation of ring-shaped chains reveals the capability to order even for quite long copolymer chains. The analytical probabilistic consideration is elaborated, which enables one to interpret the ordering via rotation in terms of a sliding of periodic Bernoullian chains. Using both the probabilistic analysis and Monte Carlo simulations it is shown that estimations of a capability to order given by the rotation procedure are also good for a sliding of true Bernoullian copolymers. Therefore, the simple Monte Carlo procedure seems suitable for estimating ordering in other classes of copolymers for which an analytical approach is more complicated. Such estimations might be useful for a consideration of various properties of irregular copolymers connected with their tendency to order. Ordering by rotation of rings. As an example, an ordering for M,=,10,000 chains of length N,=,20 and composition p,=,0.50 (p is the mole fraction of A units) is shown. See text. [source] Pulsed field gradient NMR investigation of solubilization equilibria in amino acid and dipeptide terminated micellar and polymeric surfactant solutionsMAGNETIC RESONANCE IN CHEMISTRY, Issue 12 2002Robin S. Hickok Abstract Pulsed field gradient NMR spectroscopy was used to investigate the association of toluene, chlorobenzene and benzyl alcohol with amino acid and dipeptide terminated polymerized surfactants (PS). The diffusion coefficient for each probe was measured in the presence and absence of the polymers and the mole fraction of bound probe molecules, fb, was calculated. For all solutions investigated, the probes associated more strongly with unpolymerized surfactant micelles than with corresponding PS. For example, the toluene fb values for association with sodium undecanoyl valinate micelles and the PS poly(sodium undecanoyl valinate) were 0.88 and 0.15, respectively. The relatively weak probe,polymer association was attributed to the polarity and fluidity of the polymers' hydrocarbon cores and to the fact that these PS have smaller aggregation numbers than the corresponding unpolymerized surfactant micelles. Copyright © 2002 John Wiley & Sons, Ltd. [source] Characterization of Mixtures Part 1: Prediction of Infinite-Dilution Activity Coefficients Using Neural Network-Based QSPR ModelsMOLECULAR INFORMATICS, Issue 11-12 2008Subhash Ajmani Abstract The major problem in building QSAR/QSPR models for mixtures lies in their characterization. It has been shown that it is possible to construct QSPR models for the density of binary liquid mixtures using simple mole fraction weighted physicochemical descriptors. Such parameters are unsatisfactory; however, from the point of view of interpretation of the resultant models. In this paper, an alternative mechanism-based approach to the characterization of mixtures has been investigated. It has been shown that while it is not possible to build significant linear models using these descriptors, it has been possible to construct satisfactory artificial neural network models. The performance of these models and the importance of the individual descriptors are discussed. [source] Prediction of the Solubility, Activity Coefficient and Liquid/Liquid Partition Coefficient of Organic CompoundsMOLECULAR INFORMATICS, Issue 9 2004H. Hilal Abstract Solvation models, based on fundamental chemical structure theory, were developed in the SPARC mechanistic tool box to predict a large array of physical properties of organic compounds in water and in non-aqueous solvents strictly from molecular structure. The SPARC self-interaction solvation models that describe the intermolecular interaction between like molecules (solute-solute or solvent-solvent) were extended to quantify solute-solvent interaction energy in order to estimate the activity coefficient in almost any solvent. Solvation models that include dispersion, induction, dipole-dipole and hydrogen bonding interactions are used to describe the intermolecular interaction upon placing an organic solute molecule in any single or mixed solvent system. In addition to estimation of the activity coefficient for 2674 organic compounds, these solvation models were validated on solubility and liquid/liquid distribution coefficient in more than 163 solvents including water. The RMS deviations of the calculated versus observed activity coefficients, solubilities and liquid/liquid distribution coefficients were 0.272,log mole fraction, 0.487,log mole fraction and 0.44,log units, respectively. [source] Spectroscopic ellipsometry studies of Mg-doped ZnO thin films prepared by the sol,gel methodPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 7 2009Shenghong Yang Abstract Zn1,xMgx O (ZMO) thin films with x = 0, 0.1, 0.2, and 0.3 were prepared on Si(100) substrates by the sol,gel method. The influence of Mg content on the structural and the optical properties was studied by X-ray diffraction and spectroscopic ellipsometry (SE) in the UV,visible region. The measured SE spectra were analyzed with an appropriate procedure to accurately determine the thickness and the optical constants of the thin films. It was found that the optical constants of the ZMO films are functions of the film composition. The refractive indices of the ZMO films decrease with increasing Mg content, and the optical bandgap energy exhibits nonlinear behavior or a bowing effect with the change of Mg mole fraction. A maximum band gap of ,3.91 eV was achieved at x = 0.3. (© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Hg(1-x)CdxTe from short to long wave infrared on Si substrates grown by MBEPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 10 2010M. F. Vilela Abstract In this paper, we show the power of using molecular beam epitaxy (MBE) for the growth of the mercury cadmium telluride (HgCdTe) system. Abrupt composition profiles, changes in doping levels, or switching doping types are easily performed. It is shown that high quality material is achieved with Hg(1- x)CdxTe grown by MBE from a cadmium mole fraction of x =0.15 to x =0.72. Doping elements incorporation as low as 1015 cm -3 for both n-type and p-type material as well as high incorporation levels >1018cm -3 for both carrier types were achieved. Secondary ion mass spectrometry (SIMS) data, x-ray data, Hall data, the influence of doping incorporation with cadmium content and growth rate, etch pit density (EPD), composition uniformity determined from Fourier transform infrared (FTIR) transmission spectroscopy, and surface defect maps from low to high x values are presented to illustrate the versatility and quality of HgCdTe material grown by MBE. (© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Growth and characterization of ZnMgTe/ZnTe layered structures grown by molecular beam epitaxyPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 6 2010S. Imada Abstract ZnMgTe/ZnTe layered structures were grown on ZnTe substrates by molecular beam epitaxy, and the crystal structures were characterized using X-ray diffraction methods. This structure would be the waveguide for various optoelectronic devices. Therefore, the crystal quality of this layered structure would be very crucial for the realization of high performance devices. ZnMgTe is lattice mismatched to ZnTe, and the increase of the ZnMgTe layer thickness or Mg mole fraction ratio would result in the crystal quality deterioration of the layered structure. The critical layer thickness (CLT) was theoretically derived, and various structures with various ZnMgTe layer thickness and Mg mole fraction were grown. The lattice mismatch strain relief and crystal quality of those samples were investigated by means of X-ray reciprocal space mapping (RSM) and cross sectional transmission electron microscopy (TEM). The dislocation formation and the lattice mismatch relaxation were confirmed for various samples and it was revealed that the calculated CLT values could be used as an appropriate guideline to design the dislocation free and high performance device structures (© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Electron microscopy of InGaN nanopillars spontaneously grown on Si(111) substratesPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 5 2010Th. Kehagias Abstract The mopholological, structural and chemical properties of InxGa1,xN nanopillars directly grown on Si (111) substrates, by molecular beam epitaxy, were investigated employing transmission electron microscopy related techniques. Single crystalline, single phase nanopillars were observed exhibiting a low density of crystal defects, which contribute to good crystal quality. Initial nanostructures merge through subgrain boundaries to form final nanopillars. Energy dispersive X-ray analysis revealed a very low InN mole fraction near the interface with the substrate, owing to high desorption rates from the elevated growth temperature, and gradually higher In incorporation rates near the tips of the nanopillars. This compositional fluctuation is maintained due to poor segregation of indium adatoms along the c-axis of the nanopillars towards the Si interface. A second species of long and narrow nanopillars was found In-free. (© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Luminescence of anthracene molecules in single crystal matricesPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 10 2006T. Aoki-Matsumoto Abstract Optical properties of single fluorene/phenanthrene crystals doped with various mole fraction of anthracene, 10,5 to a few %, were investigated at 10 K. In low concentration samples, sharp structures attributed to isolated anthracene molecules were observed. Inhomogeneous width in their 0-0 energy were found to be ,20 cm,1. When concentration is higher, spectral species, which are distinctly different from the isolated molecule spectrum, were observed and their origins are discussed. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] AlGaN/GaN high electron mobility transistor structures for pressure and pH sensingPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 7 2005B. S. Kang Abstract Nitride High Electron Mobility Transistor(HEMT) structures are excellent candidates for polar liquid detectors, pressure sensors and piezoelectric-related applications. The changes in conductance of the channel of AlGaN/GaN high electron mobility transistor structures during application of both tensile and compressive strain are reported. For fixed Al mole fraction, the changes in conductance were roughly linear over the range up to 2.7 × 108 N.cm,2 , with coefficients for planar devices of ,6.0 +/,2.5 × 10,10 S.N,1 m,2 for tensile strain and +9.5+/,3.5 × 10,10 S.N,1m,2 for compressive strain . The large changes in conductance demonstrate that simple AlGaN/GaN heterostructures are promising for pressure and strain sensor applications. A gateless HEMT structure was also used for sensing different liquids present in the gate region. The forward current showed significant decreases upon exposure of the gate area to solvents (water, acetone) or acids (HCl). Milli ampere changes in the source-drain current are observed relative to the value measured in air ambient . The pH sensitivity is due to changes in net surface charge that affects the relative depletion in the channel of the transistor. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Preparation, characterization, and thermal properties of hydrophilic copolymers: p -chlorophenylmaleimides with hydroxylethyl methacrylate and ,-methyl itaconatePOLYMER INTERNATIONAL, Issue 9 2007Guadalupe del C Pizarro Abstract This work describes the synthesis, characterization, and thermal behavior of copolymers of p -chlorophenylmaleimide (Cl-PhMI) with ,-methyl itaconate (,-MHI) and 2-hydroxyethyl methacrylate (HEMA). Copolymerization was carried out with a radical initiator by varying the feed mole fraction of Cl-PhMI from 0.25 to 0.75. The copolymer composition was determined from the N/C ratio based on elemental analysis data and with 1H NMR spectroscopy for poly(Cl-PhMI- co -HEMA) using a proton signal attributed to the CH3 of HEMA (, = 0.7,1.4 ppm) and the area of aromatic ring protons (, = 7.2,7.8 ppm), where the proton/area relationship confirmed the copolymer compositions calculated by elemental analysis. The monomer reactivity ratios r1 and r2 were determined using the Kelen,Tüdös method. These values demonstrated that copolymerization produced random copolymers with an alternation tendency. The molecular weight and polydispersity were also determined. The thermal behavior can be correlated with the copolymer composition. An increase of the thermal decomposition temperature occurred when the content of Cl-PhMI increased. The glass transition temperature and thermal stability of poly(,-MHI) or poly(HEMA) increased with an increasing amount of Cl-PhMI in the polymer backbone. Copyright © 2007 Society of Chemical Industry [source] Blood cell separation using crosslinkable copolymers containing N,N -dimethylacrylamidePOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 4 2007Shizue Hayashi Natori Abstract Amphiphilic copolymers using hydrophilic N,N -dimethylacrylamide (DMA), hydrophobic methyl methacrylate (MMA) and a crosslinkable monomer, 3-methacryloyloxypropyl trimethoxysilane (MTSi), were synthesized and evaluated as coating materials for leukocyte removal filters for whole blood. When filters composed of non-woven fabrics were coated with crosslinked synthesized copolymers, the elution ratios of the copolymers to water were adequately low because of the crosslinking with trimethoxysilane groups of MTSi units in the copolymers. Filters coated with crosslinked poly(DMA- co -MTSi) having a 0.96 mole fraction of DMA units showed a 0.35,±,0.44% platelet permeation ratio and a logarithmic reduction of 4.0,±,0.68 for leukocytes. On the other hand, an increase in the content of MMA units in the DMA-containing copolymers improved the permeation ratio of the platelets dramatically. Filters coated with crosslinked poly(DMA- co -MMA- co -MTSi) containing a 0.39 mole fraction of MMA units and a 0.58 mole fraction of DMA units showed an 86,±,3.0% platelet permeation ratio and a logarithmic reduction of 2.1,±,1.2 for leukocytes. This indicates that an adequate content of hydrophobic monomer units, such as MMA units, is necessary for effective platelet permeation. Copyright © 2007 John Wiley & Sons, Ltd. [source] | ||||||||||||||||||||||