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Sample records for nonpolar solvents including

  1. Methods for recovering a solvent from a fluid volume and methods of removing at least one compound from a nonpolar solvent

    Energy Technology Data Exchange (ETDEWEB)

    Ginosar, Daniel M.; Wendt, Daniel S.; Petkovic, Lucia M.

    2014-06-10

    A method of removing a nonpolar solvent from a fluid volume that includes at least one nonpolar compound, such as a fat, an oil or a triglyceride, is provided. The method comprises contacting a fluid volume with an expanding gas to expand the nonpolar solvent and form a gas-expanded solvent. The gas-expanded solvent may have a substantially reduced density in comparison to the at least one nonpolar compound and/or a substantially reduced capacity to solubilize the nonpolar compound, causing the nonpolar compounds to separate from the gas-expanded nonpolar solvent into a separate liquid phase. The liquid phase including the at least one nonpolar compound may be separated from the gas-expanded solvent using conventional techniques. After separation of the liquid phase, at least one of the temperature and pressure may be reduced to separate the nonpolar solvent from the expanding gas such that the nonpolar solvent may be recovered and reused.

  2. Solvent density mode instability in non-polar solutions

    Indian Academy of Sciences (India)

    Susmita Kar; Ranjit Biswas; J Chakrabarti

    2008-08-01

    We analyse the origin of the multiple long time scales associated with the long time decay observed in non-polar solvation dynamics by linear stability analysis of solvent density modes where the effects of compressibility and solvent structure are systematically incorporated. The coupling of the solute–solvent interactions at both ground and excited states of the solute with the compressibility and solvent structure is found to have important effects on the time scales. The present theory suggests that the relatively longer time constant is controlled by the solvent compressibility, while the solvent structure at the nearest-neighbour length scale dominates the shorter time constant.

  3. Measurement and Modeling of Carbon Dioxide Solubility in Polar and Nonpolar Solvent

    Directory of Open Access Journals (Sweden)

    Hojatollah Ahmadi

    2012-08-01

    Full Text Available The solubility of gases is an important issue in the industries. Carbon Dioxide Through gas transmission line exists as sour gas therefore it is eliminated by solvent in industry. Carbone Dioxide is nonpolar molecule that has lower solubility in liquid solvent. In this study the solubility of carbon dioxide in some polar and nonpolar solvents (include Acetone, Acetic Acid, Benzene, Carbon Tetra Chloride, Chlorobenzene, Chloroform, Cyclo-hexane, Di-Methyl Formamid, Ethanol, Ethyl acetate, Methanol, NButanol, N-Heptane, N-Hexane at atmospheric pressure and temperatures range from 5-35ºC was determined. A laboratory unit was made for this experience and the solubility of CO2 was reported. The solubility of carbon dioxide in these solvent was low due to unreactivity and nonpolarity nature of these material. The solubility of CO2 in Ethyl Acetate and Methanol was highest and lowest respectively. This investigation showed that the solvent with carbonyl group have higher activity than other.

  4. The role of solvent cohesion in nonpolar solvation

    NARCIS (Netherlands)

    Otto, Sijbren

    2013-01-01

    Understanding hydrophobic interactions requires a molecular-level picture of how water molecules adjust to the introduction of a nonpolar solute. New insights into the latter process are derived from the observation that the Gibbs energies of solvation of the noble gases and linear alkanes by a wide

  5. Non-polar Solvent Microwave-Assisted Extraction of Volatile Constituents from Dried Zingiber Officinale Rosc.

    Institute of Scientific and Technical Information of China (English)

    YU Yong; WANG Zi-Ming; WANG Yu-Tang; LI Tie-Chun; CHENG Jian-Hua; LIU Zhong-Ying; ZHANG Han-Qi

    2007-01-01

    A new method, non-polar solvent microwave-assisted extraction (NPSMAE), was applied to the extraction of essential oil from Zingiber officinale Rosc. in closed-vessel system. By adding microwave absorption mediumcarbonyl iron powders (CIP) into extraction system, the essential oil was extracted by the non-polar solvent (ether)which can be heated by CIP. The constituents of essential oil obtained by NPSMAE were comparable with those obtained by hydrodistillation (HD) by GC-MS analysis, which indicates that NPSMAE is a feasible way to extract essential oil from dried plant materials. The NPSMAE took much less extraction time (5 min) than HD (180 min),and its extraction efficiency was much higher than that of conventional polar solvent microwave-assisted extraction (PSMAE) and mixed solvent microwave-assisted extraction (MSMAE). It can be a good alternative for the extraction of volatile constituents from dried plant samples.

  6. Determinatin of the Dipole Moment of Polar Compounds in Nonpolar Solvents.

    Science.gov (United States)

    Janini, George M.; Katrib, Ali H.

    1983-01-01

    Proposes a simple experiment based on the procedure of Guggenheim and Smith for the determinatin of the dipole moments of two isomeric compounds in nonpolar solvents. Provides background information, laboratory procedures, sample data, results of least squares analysis and discussion of results. (JM)

  7. Modeling the structure and absorption spectra of stilbazolium merocyanine in polar and nonpolar solvents using hybrid QM/MM techniques.

    Science.gov (United States)

    Murugan, N Arul; Kongsted, Jacob; Rinkevicius, Zilvinas; Aidas, Kestutis; Ågren, Hans

    2010-10-28

    We have performed Car-Parrinello mixed quantum mechanics/molecular mechanics (CP-QM/MM) calculations for stilbazolium merocyanine (SM) in polar and nonpolar solvents in order to explore the role of solute molecular geometry, solvation shell structure, and different interaction mechanisms on the absorption spectra and its dependence on solvent polarity. On the basis of the average bond length values and group charge distributions, we find that the SM molecule remains in a neutral quinonoid form in chloroform (a nonpolar solvent) while it transforms to a charge-separated benzenoid form in water (a polar solvent). Based on a quantum mechanical/molecular mechanical response technique, with different MM descriptions for the water environment, absorption spectra were obtained as averages over configurations derived from the CP-QM/MM simulations. We show that for SM in water the solute polarization plays a major role in predictions of the λ(max) and solvatochromic shift and that once this effect is included the contributions from solvent polarization and intermolecular charge transfer become less important. For SM in chloroform and water solvents, we have also performed absorption spectra calculations using a polarizable continuum model in order to address its relative performance compared to the QM/MM response technique. In the case of SM in water, our study supports the notion that, in order to predict accurate absorption spectra and solvatochromic shifts, it is important to use a discrete description of the solvent when it, as in water, is involved in site-specific interaction with the solute molecule. The technique is thus shown to outperform the more conventional polarizable continuum model in predicting the solvatochromic shift.

  8. Lipophilic polyelectrolyte gels as super-absorbent polymers for nonpolar organic solvents.

    Science.gov (United States)

    Ono, Toshikazu; Sugimoto, Takahiro; Shinkai, Seiji; Sada, Kazuki

    2007-06-01

    Polyelectrolyte gels that are known as super-absorbent polymers swell and absorb water up to several hundred times their dried weights and have become ubiquitous and indispensable materials in many applications. Their superior swelling abilities originate from the electrostatic repulsion between the charges on the polymer chains and the osmotic imbalance between the interior and exterior of the gels. However, no super-absorbent polymers for volatile organic compounds (VOCs), and especially for nonpolar organic solvents (epsilonpolymer networks. This expands the potential of polyelectrolytes that have been used only in aqueous solutions or highly polar solvents, and provides soft materials that swell in a variety of media. These materials could find applications as protective barriers for VOCs spilled in the environment and as absorbents for waste oil.

  9. Empirical valence bond model of an SN2 reaction in polar and nonpolar solvents

    Science.gov (United States)

    Benjamin, Ilan

    2008-08-01

    A new model for the substitution nucleophilic reaction (SN2) in solution is described using the empirical valence bond (EVB) method. The model includes a generalization to three dimensions of a collinear gas phase EVB model developed by Mathis et al. [J. Mol. Liq. 61, 81 (1994)] and a parametrization of solute-solvent interactions of four different solvents (water, ethanol, chloroform, and carbon tetrachloride). The model is used to compute (in these four solvents) reaction free energy profiles, reaction and solvent dynamics, a two-dimensional reaction/solvent free energy map, as well as a number of other properties that in the past have mostly been estimated.

  10. Nitrobenzene anti-parallel dimer formation in non-polar solvents

    Directory of Open Access Journals (Sweden)

    Toshiyuki Shikata

    2014-06-01

    Full Text Available We investigated the dielectric and depolarized Rayleigh scattering behaviors of nitrobenzene (NO2-Bz, which is a benzene mono-substituted with a planar molecular frame bearing the large electric dipole moment 4.0 D, in non-polar solvents solutions, such as tetrachloromethane and benzene, at up to 3 THz for the dielectric measurements and 8 THz for the scattering experiments at 20 °C. The dielectric relaxation strength of the system was substantially smaller than the proportionality to the concentration in a concentrated regime and showed a Kirkwood correlation factor markedly lower than unity; gK ∼ 0.65. This observation revealed that NO2-Bz has a tendency to form dimers, (NO2-Bz2, in anti-parallel configurations for the dipole moment with increasing concentration of the two solvents. Both the dielectric and scattering data exhibited fast and slow Debye-type relaxation modes with the characteristic time constants ∼7 and ∼50 ps in a concentrated regime (∼15 and ∼30 ps in a dilute regime, respectively. The fast mode was simply attributed to the rotational motion of the (monomeric NO2-Bz. However, the magnitude of the slow mode was proportional to the square of the concentration in the dilute regime; thus, the mode was assigned to the anti-parallel dimer, (NO2-Bz2, dissociation process, and the slow relaxation time was attributed to the anti-parallel dimer lifetime. The concentration dependencies of both the dielectric and scattering data show that the NO2-Bz molecular processes are controlled through a chemical equilibrium between monomers and anti-parallel dimers, 2NO2-Bz ↔ (NO2-Bz2, due to a strong dipole-dipole interaction between nitro groups.

  11. Efficient Extraction of Astaxanthin from Phaffia rhodozyma with Polar and Non-polar Solvents after Acid Washing

    Institute of Scientific and Technical Information of China (English)

    YIN Chunhua; YANG Shuzhen; LIU Xiaolu; YAN Hai

    2013-01-01

    method of extracting astaxanthin from Phaffia rhodozyma with various solvents after acid washing was investigated.The extraction efficiency was distinctly increased after acid washing of P.rhodozyma cells.When the concentration of HCl was 0.4 mol·L-,the highest extraction efficiency of astaxanthin was achieved which was about three times higher than the control.Acetone or benzene as single polar or non-polar solvent was the most effective solvent in our research.With a combination of isopropanol and n-hexane (volume ratio of 2 ∶ 1),the maximal extraction efficiency was achieved,approximately 60% higher than that obtained with a single solvent.The liquid-solid ratio and the extracting time were also optimized.Under the optimum extraction conditions,the extraction yield of astaxanthin exceeded 98%.

  12. Automatic parametrization of non-polar implicit solvent models for the blind prediction of solvation free energies

    Science.gov (United States)

    Wang, Bao; Zhao, Zhixiong; Wei, Guo-Wei

    2016-09-01

    In this work, a systematic protocol is proposed to automatically parametrize the non-polar part of implicit solvent models with polar and non-polar components. The proposed protocol utilizes either the classical Poisson model or the Kohn-Sham density functional theory based polarizable Poisson model for modeling polar solvation free energies. Four sets of radius parameters are combined with four sets of charge force fields to arrive at a total of 16 different parametrizations for the polar component. For the non-polar component, either the standard model of surface area, molecular volume, and van der Waals interactions or a model with atomic surface areas and molecular volume is employed. To automatically parametrize a non-polar model, we develop scoring and ranking algorithms to classify solute molecules. The their non-polar parametrization is obtained based on the assumption that similar molecules have similar parametrizations. A large database with 668 experimental data is collected and employed to validate the proposed protocol. The lowest leave-one-out root mean square (RMS) error for the database is 1.33 kcal/mol. Additionally, five subsets of the database, i.e., SAMPL0-SAMPL4, are employed to further demonstrate that the proposed protocol. The optimal RMS errors are 0.93, 2.82, 1.90, 0.78, and 1.03 kcal/mol, respectively, for SAMPL0, SAMPL1, SAMPL2, SAMPL3, and SAMPL4 test sets. The corresponding RMS errors for the polarizable Poisson model with the Amber Bondi radii are 0.93, 2.89, 1.90, 1.16, and 1.07 kcal/mol, respectively.

  13. Stable nonpolar solvent droplet generation using a poly(dimethylsiloxane) microfluidic channel coated with poly-p-xylylene for a nanoparticle growth.

    Science.gov (United States)

    Lim, Heejin; Moon, SangJun

    2015-08-01

    Applications of microfluidic devices fabricated in poly(dimethylsiloxane) (PDMS) have been limited to water-based analysis rather than nonpolar solvent based chemistry due to a PDMS swelling problem that occurs by the absorption of the solvents. The absorption and swelling causes PDMS channel deformation in shape, and changes the cross sectional area making it difficult to control the flow rate and concentrations of solution in PDMS microfluidic channels. We propose that poly-p-xylylene polymers (parylenes) are chemical vapors deposited on the surfaces of PDMS channels that alleviate the effect of solvents on the absorption and swelling. The parylene coated surface sustains 3 h with a small volumetric change (less than 22 % of PDMS swelling ratio). By generating an air-nonpolar solvent interface based on droplets in PDMS channel, we confirmed poly-p-xylylene coated PDMS microfluidic channels have the potential to be applicable to nanocrystal growth using nonpolar solvents.

  14. The solution properties of mefenamic acid and a closely related analogue are indistinguishable in polar solvents but significantly different in nonpolar environments.

    Science.gov (United States)

    Lee, Eun Hee; Byrn, Stephen R; Pinal, Rodolfo

    2012-12-01

    This study investigates the cosolute effects of mefenamic acid (XA) and flufenamic acid (FA). These compounds serve as model of a drug discovery lead compound and a structural analogue. The activity coefficients of XA and FA in different solvents were obtained from solubility measurements at 25°C. The effect of varying concentrations of FA on the solubility of XA in four different solvents, including toluene, cyclohexane, ethanol, and an ethanol-water mixture (80:20, v/v), was investigated. The magnitude of change in the activity coefficient of XA in the presence of FA in different solvents was used to elucidate the thermodynamic effect of FA on the solubility of XA. Nuclear magnetic resonance and Fourier-transform infrared spectroscopy were used to obtain molecular level information about the interactions of the compounds in solution. The presence of FA increases XA solubility in toluene and in cyclohexane as much as seven-fold. Conversely, in ethanol and the ethanol-water mixture, similar levels of FA have essentially no effect on the solubility of XA. The solution properties investigated show that despite the close structural similarity between XA and FA, the two compounds are strongly distinguishable in nonpolar solvents. Conversely, the solution properties of the same two solutes are indistinguishable in polar solvents. A solubilization model based on solute-cosolute interactions is presented.

  15. An absorbing microwave micro-solid-phase extraction device used in non-polar solvent microwave-assisted extraction for the determination of organophosphorus pesticides

    Energy Technology Data Exchange (ETDEWEB)

    Wang Ziming, E-mail: wangziming@jlu.edu.cn [College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); College of Environment and Resources, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Zhao Xin; Xu Xu; Wu Lijie; Su Rui; Zhao Yajing; Jiang Chengfei; Zhang Hanqi [College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Ma Qiang [Chinese Academy of Inspection and Quarantine, Beijing 100123 (China); Lu Chunmei [College of Technology Center, Jilin Entry-Exit Inspection and Quarantine Bureau, Changchun 130062 (China); Dong Deming [College of Environment and Resources, Jilin University, 2699 Qianjin Street, Changchun 130012 (China)

    2013-01-14

    Highlights: Black-Right-Pointing-Pointer An absorbing microwave {mu}-SPE device packed with activated carbon was used. Black-Right-Pointing-Pointer Absorbing microwave {mu}-SPE device was made and used to enrich the analytes. Black-Right-Pointing-Pointer Absorbing microwave {mu}-SPE device was made and used to heat samples directly. Black-Right-Pointing-Pointer MAE-{mu}-SPE was applied to the extraction of OPPs with non-polar solvent only. - Abstract: A single-step extraction-cleanup method, including microwave-assisted extraction (MAE) and micro-solid-phase extraction ({mu}-SPE), was developed for the extraction of ten organophosphorus pesticides in vegetable and fruit samples. Without adding any polar solvent, only one kind of non-polar solvent (hexane) was used as extraction solvent in the whole extraction step. Absorbing microwave {mu}-SPE device, was prepared by packing activated carbon with microporous polypropylene membrane envelope, and used as not only the sorbent in {mu}-SPE, but also the microwave absorption medium. Some experimental parameters effecting on extraction efficiency was investigated and optimized. 1.0 g of sample, 8 mL of hexane and three absorbing microwave {mu}-SPE devices were added in the microwave extraction vessel, the extraction was carried out under 400 W irradiation power at 60 Degree-Sign C for 10 min. The extracts obtained by MAE-{mu}-SPE were directly analyzed by GC-MS without any clean-up process. The recoveries were in the range of 93.5-104.6%, and the relative standard deviations were lower than 8.7%.

  16. Microhydration effects on a model SN2 reaction in a nonpolar solvent

    Science.gov (United States)

    Nelson, Katherine V.; Benjamin, Ilan

    2009-05-01

    Using a recently developed empirical valence bond model for the nucleophilic substitution reaction (SN2) in solution, we examine microhydration effects on the benchmark Cl-+CH3Cl reaction in liquid chloroform. Specifically, the effect of the hydration of the reactive system by one to five water molecules on the reaction-free energy profile and the rate constant is examined. We find that the activation-free energy is highly sensitive to the number of water molecules hydrating the nucleophile, increasing the barrier by about 4 kcal/mol by the first water molecule. With five water molecules, the barrier height is 10 kcal/mol larger than the barrier in bulk chloroform and only 3 kcal/mol below the barrier in bulk water. A number of properties vary monotonically with the number of water molecules, including the rate of change in the system's electronic structure and the solvent stabilization of the transition state. These and other properties are a rapidly varying function of the reaction coordinate. Deviation from transition state theory due to barrier recrossing is not large and falls between the behavior in bulk water and bulk chloroform.

  17. Dielectric behaviour of some amides and formamides dissolved in nonpolar solvents under static electric field

    Indian Academy of Sciences (India)

    S Sahoo; S K Sit

    2011-08-01

    Structural and associational aspects of polar amides () like formamide, acetamide, Nmethyl acetamide (NMA), N,N-dimethyl formamide (DMF), N,N-dimethyl acetamide (DMA) and acetanilide dissolved in the nonpolar solvent () benzene or 1,4-dioxan have been estimated from the measured static relative permittivity 0 and high-frequency permittivity ∞ at different weight fractions s of polar solute at 35°C under static electric field using Debye model of polar liquid molecule. The static dipole moments s are compared with s reported from conductivity method and theoretical theos to get exact cal $\\cdot$ theos of the molecules are predicted from the available bond angles and bond moments where difference in electron affinity exists between two adjacent atoms of a polar group due to inductive, mesomeric and electromeric effects in them. Solute–solute molecular association for NMA in benzene and solute–solvent association for other amides are ascertained to arrive at their conformational structures.

  18. Electrolytes including fluorinated solvents for use in electrochemical cells

    Science.gov (United States)

    Tikhonov, Konstantin; Yip, Ka Ki; Lin, Tzu-Yuan

    2015-07-07

    Provided are electrochemical cells and electrolytes used to build such cells. The electrolytes include ion-supplying salts and fluorinated solvents capable of maintaining single phase solutions with the salts at between about -30.degree. C. to about 80.degree. C. The fluorinated solvents, such as fluorinated carbonates, fluorinated esters, and fluorinated esters, are less flammable than their non-fluorinated counterparts and increase safety characteristics of cells containing these solvents. The amount of fluorinated solvents in electrolytes may be between about 30% and 80% by weight not accounting weight of the salts. Fluorinated salts, such as fluoroalkyl-substituted LiPF.sub.6, fluoroalkyl-substituted LiBF.sub.4 salts, linear and cyclic imide salts as well as methide salts including fluorinated alkyl groups, may be used due to their solubility in the fluorinated solvents. In some embodiments, the electrolyte may also include a flame retardant, such as a phosphazene or, more specifically, a cyclic phosphazene and/or one or more ionic liquids.

  19. Double relaxation phenomena of associated binary polar liquid mixture in non-polar solvent under high frequency electric field

    Energy Technology Data Exchange (ETDEWEB)

    Sahoo, S. [Department of Electronics and Instrumentation Engg (India)], E-mail: swapansit@yahoo.co.in; Sit, S.K. [Department of Physics, Dr. Meghnad Saha Institute of Technology, Debhog, Haldia, Purba Medinipore, West Bengal 721657 (India)

    2009-06-25

    Double relaxation times {tau}{sub 2} and {tau}{sub 1} due to whole molecular rotation and the flexible parts of the binary polar liquid mixture (jk) 3-bromoaniline and 1-propanol dissolved in non-polar solvent (i) benzene were estimated in terms of measured real {chi}{sup '}{sub ijk}, imaginary {chi}{sup ''}{sub ijk} parts of complex high frequency orientational susceptibility {chi}{sub ijk}{sup *} and {chi}{sub 0ijk} which is real at 20, 30, 40 and 47 deg. C experimental temperatures for 0.0, 0.25, 0.50,0.75 and 1.00 mole fractions x{sub j}'s of 1-propanol under 9.1 GHz electric field. The slopes {omega}({tau}{sub 2} + {tau}{sub 1}) and intercepts {omega}{sup 2}{tau}{sub 2}{tau}{sub 1} of the analytical straight line equations used to estimate {tau}{sub 2} and {tau}{sub 1} were derived from Bergmann's equation [U. Saha, S.K. Sit, R.C. Basak, S. Acharyya, J. Phys. D: Appl. Phys. 27 (1994) 596] based on two Debye type dispersion model of binary polar mixture. The systems 3-bromoaniline in C{sub 6}H{sub 6} and 1-propanol in C{sub 6}H{sub 6} show {tau}{sub 2} and {tau}{sub 1} only at 47 deg. C temperature like 3-bromoaniline + 1-propanol in C{sub 6}H{sub 6} at 20 and 47 deg. C temperatures for 0.25 and 0.50 mole fractions x{sub j}'s of 1-propanol. The binary polar mixture for x{sub j} = 0.75 of 1-propanol is an exception exhibiting double relaxation times at all the experimental temperatures. The relative contributions c{sub 1} and c{sub 2} due to {tau}{sub 1} and {tau}{sub 2} for eight non-rigid systems were calculated from Froehlich's equation as well as graphical plots of {chi}{sup '}{sub ijk}/{chi}{sub 0ijk}-w{sub jk} and {chi}{sup ''}{sub ijk}/{chi}{sub 0ijk}-w{sub jk} curve at w{sub jk}{yields}0. c{sub 1} and c{sub 2} are positive for Froehlich's method whereas most of the c{sub 2}'s are negative for graphical method. The dipole moments {mu}{sub 2} and {mu}{sub 1} for all the systems are calculated from

  20. A combined interfacial and in-situ polymerization strategy to construct well-defined core-shell epoxy-containing SiO2-based microcapsules with high encapsulation loading, super thermal stability and nonpolar solvent tolerance

    Directory of Open Access Journals (Sweden)

    Yin Jia

    2016-10-01

    Full Text Available SiO2-based microcapsules containing hydrophobic molecules exhibited potential applications such as extrinsic self-healing, drug delivery, due to outstanding thermal and chemical stability of SiO2. However, to construct SiO2-based microcapsules with both high encapsulation loading and long-term structural stability is still a troublesome issue, limiting their further utilization. We herein design a single-batch route, a combined interfacial and in-situ polymerization strategy, to fabricate epoxy-containing SiO2-based microcapsules with both high encapsulation loading and long-term structural stability. The final SiO2-based microcapsules preserve high encapsulation loading of 85.7 wt% by controlling exclusively hydrolysis and condensed polymerization at oil/water interface in the initial interfacial polymerization step. In the subsequent in-situ polymerization step, the initial SiO2-based microcapsules as seeds could efficiently harvest SiO2 precursors and primary SiO2 particles to finely tune the SiO2 wall thickness, thereby enhancing long-term structural stability of the final SiO2-based microcapsules including high thermal stability with almost no any weight loss until 250°C, and strong tolerance against nonpolar solvents such as CCl4 with almost unchanged core-shell structure and unchanged core weight after immersing into strong solvents for up to 5 days. These SiO2-based microcapsules are extremely suited for processing them into anticorrosive coating in the presence of nonpolar solvents for self-healing application.

  1. In silico study of amphiphilic nanotubes based on cyclic peptides in polar and non-polar solvent

    DEFF Research Database (Denmark)

    Vijayakumar, Vinodhkumar; Vijayaraj, Ramadoss; Peters, Günther H.J.

    2016-01-01

    The stability of cyclic peptide assemblies (CPs) forming a macromolecular nanotube structure was investigated in solvents of different polarity using computational methods. The stability and structure of the complexes were studied using traditional molecular dynamics (MD). Energy of dissociation...... was estimated from steered MD in combination with umbrella sampling simulations. A cyclic peptide nanotube (CPNT) was constructed by stacking of eight cyclo[(d-Trp-l-Gln-d-Trp-l-Glu)2], and hereafter is referred to as (WQWE)8. Its dissociation was studied by pulling 1, 2, or 3 subunits from the nanotube....... The crucial point in the dissociation event of the CP subunit(s) is the breaking of backbone–backbone hydrogen bonds and consecutive annihilation of side chain interactions. Gibbs free energy calculations to estimate the binding affinity of CP subunit(s) reveal that the (WQWE)8 nanotube is significantly more...

  2. Colloidosomes formed by nonpolar/polar/nonpolar nanoball amphiphiles

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Hung-Yu; Sheng, Yu-Jane, E-mail: yjsheng@ntu.edu.tw, E-mail: hktsao@cc.ncu.edu.tw [Department of Chemical Engineering, National Taiwan University, Taipei 106, Taiwan (China); Tu, Sheng-Hung [Department of Chemical and Materials Engineering, National Central University, Jhongli 320, Taiwan (China); Tsao, Heng-Kwong, E-mail: yjsheng@ntu.edu.tw, E-mail: hktsao@cc.ncu.edu.tw [Department of Chemical and Materials Engineering and Department of Physics, National Central University, Jhongli 320, Taiwan (China)

    2014-08-07

    Fullerene-based amphiphiles are able to form bilayer vesicles in aqueous solution. In this study, the self-assembly behavior of polymer-tethered nanoballs (NBs) with nonpolar/polar/nonpolar (n-p-n{sup ′}) motif in a selective solvent is investigated by dissipative particle dynamics. A model NB bears two hydrophobic polymeric arms (n{sup ′}-part) tethered on an extremely hydrophobic NB (n-part) with hydrophilic patch (p-part) patterned on its surface. Dependent on the hydrophobicity and length of tethered arms, three types of aggregates are exhibited, including NB vesicle, core-shell micelle, and segmented-worm. NB vesicles are developed for a wide range of hydrophobic arm lengths. The presence of tethered arms perturbs the bilayer structure formed by NBs. The structural properties including the order parameter, membrane thickness, and area density of the inner leaflet decrease with increasing the arm length. These results indicate that for NBs with longer arms, the extent of interdigitation in the membrane rises so that the overcrowded arms in the inner corona are relaxed. The transport and mechanical properties are evaluated as well. As the arm length grows, the permeability increases significantly because the steric bulk of tethered arms loosens the packing of NBs. By contrast, the membrane tension decreases owing to the reduction of NB/solvent contacts by the polymer corona. Although fusion can reduce membrane tension, NB vesicles show strong resistance to fusion. Moreover, the size-dependent behavior observed in small liposomes is not significant for NB vesicles due to isotropic geometry of NB. Our simulation results are consistent with the experimental findings.

  3. Colloidosomes formed by nonpolar/polar/nonpolar nanoball amphiphiles.

    Science.gov (United States)

    Chang, Hung-Yu; Tu, Sheng-Hung; Sheng, Yu-Jane; Tsao, Heng-Kwong

    2014-08-01

    Fullerene-based amphiphiles are able to form bilayer vesicles in aqueous solution. In this study, the self-assembly behavior of polymer-tethered nanoballs (NBs) with nonpolar/polar/nonpolar (n-p-n') motif in a selective solvent is investigated by dissipative particle dynamics. A model NB bears two hydrophobic polymeric arms (n'-part) tethered on an extremely hydrophobic NB (n-part) with hydrophilic patch (p-part) patterned on its surface. Dependent on the hydrophobicity and length of tethered arms, three types of aggregates are exhibited, including NB vesicle, core-shell micelle, and segmented-worm. NB vesicles are developed for a wide range of hydrophobic arm lengths. The presence of tethered arms perturbs the bilayer structure formed by NBs. The structural properties including the order parameter, membrane thickness, and area density of the inner leaflet decrease with increasing the arm length. These results indicate that for NBs with longer arms, the extent of interdigitation in the membrane rises so that the overcrowded arms in the inner corona are relaxed. The transport and mechanical properties are evaluated as well. As the arm length grows, the permeability increases significantly because the steric bulk of tethered arms loosens the packing of NBs. By contrast, the membrane tension decreases owing to the reduction of NB/solvent contacts by the polymer corona. Although fusion can reduce membrane tension, NB vesicles show strong resistance to fusion. Moreover, the size-dependent behavior observed in small liposomes is not significant for NB vesicles due to isotropic geometry of NB. Our simulation results are consistent with the experimental findings.

  4. Behavior of anionic molybdenum(IV, VI) and tungsten(IV, VI) complexes containing bulky hydrophobic dithiolate ligands and intramolecular NH···S hydrogen bonds in nonpolar solvents.

    Science.gov (United States)

    Hasenaka, Yuki; Okamura, Taka-aki; Tatsumi, Miki; Inazumi, Naoya; Onitsuka, Kiyotaka

    2014-11-07

    Molybdenum(IV, VI) and tungsten(IV, VI) complexes, (Et4N)2[M(IV)O{1,2-S2-3,6-(RCONH)2C6H2}2] and (Et4N)2[M(VI)O2{1,2-S2-3,6-(RCONH)2C6H2}2] (M = Mo, W; R = (4-(t)BuC6H4)3C), with bulky hydrophobic dithiolate ligands containing NH···S hydrogen bonds were synthesized. These complexes are soluble in nonpolar solvents like toluene, which allows the detection of unsymmetrical coordination structures and elusive intermolecular interactions in solution. The (1)H NMR spectra of the complexes in toluene-d8 revealed an unsymmetrical coordination structure, and proximity of the counterions to the anion moiety was suggested at low temperatures. The oxygen-atom-transfer reaction between the molybdenum(IV) complex and Me3NO in toluene was considerably accelerated in nonpolar solvents, and this increase was attributed to the favorable access of the substrate to the active center in the hydrophobic environment.

  5. Solvent

    OpenAIRE

    Hamida Y. Mostafa; Ebaa A. El-Shamy; Amal S. Farag; Nadia G. Kandile

    2013-01-01

    Neat ethylacetoacetate (EAA) and its mixtures with a co-solvent and an anti-solvent have been studied for refining of heavy wax distillate fraction to produce substantially non-carcinogenic base oil. The co-solvent and anti-solvent used are dipropylene glycol (DPG) and ethylene glycol (EG) respectively. The solubility characteristics of the main solvent and its mixed solvent systems were studied. Selection of the optimum solvent mixture and extraction variables has been studied. The effect of...

  6. Water based on a molecular model behaves like a hard-sphere solvent for a nonpolar solute when the reference interaction site model and related theories are employed

    Science.gov (United States)

    Hayashi, Tomohiko; Oshima, Hiraku; Harano, Yuichi; Kinoshita, Masahiro

    2016-09-01

    For neutral hard-sphere solutes, we compare the reduced density profile of water around a solute g(r), solvation free energy μ, energy U, and entropy S under the isochoric condition predicted by the two theories: dielectrically consistent reference interaction site model (DRISM) and angle-dependent integral equation (ADIE) theories. A molecular model for water pertinent to each theory is adopted. The hypernetted-chain (HNC) closure is employed in the ADIE theory, and the HNC and Kovalenko-Hirata (K-H) closures are tested in the DRISM theory. We also calculate g(r), U, S, and μ of the same solute in a hard-sphere solvent whose molecular diameter and number density are set at those of water, in which case the radial-symmetric integral equation (RSIE) theory is employed. The dependences of μ, U, and S on the excluded volume and solvent-accessible surface area are analyzed using the morphometric approach (MA). The results from the ADIE theory are in by far better agreement with those from computer simulations available for g(r), U, and μ. For the DRISM theory, g(r) in the vicinity of the solute is quite high and becomes progressively higher as the solute diameter d U increases. By contrast, for the ADIE theory, it is much lower and becomes further lower as d U increases. Due to unphysically positive U and significantly larger |S|, μ from the DRISM theory becomes too high. It is interesting that μ, U, and S from the K-H closure are worse than those from the HNC closure. Overall, the results from the DRISM theory with a molecular model for water are quite similar to those from the RSIE theory with the hard-sphere solvent. Based on the results of the MA analysis, we comparatively discuss the different theoretical methods for cases where they are applied to studies on the solvation of a protein.

  7. Aggregation behavior of amphiphilic cyclodextrins in a nonpolar solvent: evidence of large-scale structures by atomistic molecular dynamics simulations and solution studies

    Directory of Open Access Journals (Sweden)

    Giuseppina Raffaini

    2016-01-01

    Full Text Available Chemically modified cyclodextrins carrying both hydrophobic and hydrophilic substituents may form supramolecular aggregates or nanostructures of great interest. These systems have been usually investigated and characterized in water for their potential use as nanocarriers for drug delivery, but they can also aggregate in apolar solvents, as shown in the present paper through atomistic molecular dynamics simulations and dynamic light scattering measurements. The simulations, carried out with a large number of molecules in vacuo adopting an unbiased bottom-up approach, suggest the formation of bidimensional structures with characteristic length scales of the order of 10 nm, although some of these sizes are possibly affected by the assumed periodicity of the simulation cell, in particular at longer lengths. In any case, these nanostructures are stable at least from the kinetic viewpoint for relatively long times thanks to the large number of intermolecular interactions of dipolar and dispersive nature. The dynamic light scattering experiments indicate the presence of aggregates with a hydrodynamic radius of the order of 80 nm and a relatively modest polydispersity, even though smaller nanometer-sized aggregates cannot be fully ruled out. Taken together, these simulation and experimental results indicate that amphiphilically modified cyclodextrins do also form large-scale nanoaggregates even in apolar solvents.

  8. Experimental study and thermodynamic modeling for determining the effect of non-polar solvent (hexane)/polar solvent (methanol) ratio and moisture content on the lipid extraction efficiency from Chlorella vulgaris.

    Science.gov (United States)

    Malekzadeh, Mohammad; Abedini Najafabadi, Hamed; Hakim, Maziar; Feilizadeh, Mehrzad; Vossoughi, Manouchehr; Rashtchian, Davood

    2016-02-01

    In this research, organic solvent composed of hexane and methanol was used for lipid extraction from dry and wet biomass of Chlorella vulgaris. The results indicated that lipid and fatty acid extraction yield was decreased by increasing the moisture content of biomass. However, the maximum extraction efficiency was attained by applying equivolume mixture of hexane and methanol for both dry and wet biomass. Thermodynamic modeling was employed to estimate the effect of hexane/methanol ratio and moisture content on fatty acid extraction yield. Hansen solubility parameter was used in adjusting the interaction parameters of the model, which led to decrease the number of tuning parameters from 6 to 2. The results indicated that the model can accurately estimate the fatty acid recovery with average absolute deviation percentage (AAD%) of 13.90% and 15.00% for the two cases of using 6 and 2 adjustable parameters, respectively.

  9. Theoretical study of electronic absorptions in aminopyridines - TCNE CT complexes by quantum chemical methods, including solvent.

    Science.gov (United States)

    Mach, Pavel; Juhász, György; Kyseľ, Ondrej

    2013-11-01

    The geometric and electronic structure of donor-acceptor complexes of TCNE with aniline, o-, m- and p- aminopyridines and pyridine has been studied in gas phase and in solution using CC2, TDDFT and CIS methods. Concerning interaction energy between particular donor and TCNE acceptor it is fairly described by both CC2 (MP2) and DFT-D approaches. Transition energies in gas phase calculated by CC2 approach are in good agreement with available experimental data for aniline. TDDFT calculations with LC-BLYP functional (with standard value of range separation factor μ = 0.47) gives transition energies too high although not as high as CIS. The red solvent shifts, calculated by PCM model with CIS method are qualitative correct, but error in the range of 0.1-0.2 eV should be expected.

  10. A molecular dynamics study of intramolecular proton transfer reaction of malonaldehyde in solution based upon a mixed quantum–classical approximation. II. Proton transfer reaction in non-polar solvent

    Energy Technology Data Exchange (ETDEWEB)

    Kojima, H.; Yamada, A.; Okazaki, S., E-mail: okazaki@apchem.nagoya-u.ac.jp [Department of Applied Chemistry, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan)

    2015-05-07

    The intramolecular proton transfer reaction of malonaldehyde in neon solvent has been investigated by mixed quantum–classical molecular dynamics (QCMD) calculations and fully classical molecular dynamics (FCMD) calculations. Comparing these calculated results with those for malonaldehyde in water reported in Part I [A. Yamada, H. Kojima, and S. Okazaki, J. Chem. Phys. 141, 084509 (2014)], the solvent dependence of the reaction rate, the reaction mechanism involved, and the quantum effect therein have been investigated. With FCMD, the reaction rate in weakly interacting neon is lower than that in strongly interacting water. However, with QCMD, the order of the reaction rates is reversed. To investigate the mechanisms in detail, the reactions were categorized into three mechanisms: tunneling, thermal activation, and barrier vanishing. Then, the quantum and solvent effects were analyzed from the viewpoint of the reaction mechanism focusing on the shape of potential energy curve and its fluctuations. The higher reaction rate that was found for neon in QCMD compared with that found for water solvent arises from the tunneling reactions because of the nearly symmetric double-well shape of the potential curve in neon. The thermal activation and barrier vanishing reactions were also accelerated by the zero-point energy. The number of reactions based on these two mechanisms in water was greater than that in neon in both QCMD and FCMD because these reactions are dominated by the strength of solute–solvent interactions.

  11. Thermomolecular Orientation of Nonpolar Fluids

    NARCIS (Netherlands)

    Römer, F.; Bresme, F.; Muscatello, J.; Bedeaux, D.; Rubi, J.M.

    2012-01-01

    We investigate the response of molecular fluids to temperature gradients. Using nonequilibrium molecular dynamics computer simulations we show that nonpolar diatomic fluids adopt a preferred orientation as a response to a temperature gradient. We find that the magnitude of this thermomolecular orien

  12. Molecular Dynamics Simulations on Parallel Computers: a Study of Polar Versus Nonpolar Media Effects in Small Molecule Solvation.

    Science.gov (United States)

    Debolt, Stephen Edward

    Solvent effects were studied and described via molecular dynamics (MD) and free energy perturbation (FEP) simulations using the molecular mechanics program AMBER. The following specific topics were explored:. Polar solvents cause a blue shift of the rm nto pi^* transition band of simple alkyl carbonyl compounds. The ground- versus excited-state solvation effects responsible for the observed solvatochromism are described in terms of the molecular level details of solute-solvent interactions in several modeled solvents spanning the range from polar to nonpolar, including water, methanol, and carbon tetrachloride. The structure and dynamics of octanol media were studied to explore the question: "why is octanol/water media such a good biophase analog?". The formation of linear and cyclic polymers of hydrogen-bonded solvent molecules, micelle-like clusters, and the effects of saturating waters are described. Two small drug-sized molecules, benzene and phenol, were solvated in water-saturated octanol. The solute-solvent structure and dynamics were analysed. The difference in their partitioning free energies was calculated. MD and FEP calculations were adapted for parallel computation, increasing their "speed" or the time span accessible by a simulation. The non-cyclic polyether ionophore salinomycin was studied in methanol solvent via parallel FEP. The path of binding and release for a potassium ion was investigated by calculating the potential of mean force along the "exit vector".

  13. Molecular dynamics study on the solvent dependent heme cooling following ligand photolysis in carbonmonoxy myoglobin.

    Science.gov (United States)

    Zhang, Yong; Fujisaki, Hiroshi; Straub, John E

    2007-03-29

    The time scale and mechanism of vibrational energy relaxation of the heme moiety in myoglobin was studied using molecular dynamics simulation. Five different solvent models, including normal water, heavy water, normal glycerol, deuterated glycerol and a nonpolar solvent, and two forms of the heme, one native and one lacking acidic side chains, were studied. Structural alteration of the protein was observed in native myoglobin glycerol solution and native myoglobin water solution. The single-exponential decay of the excess kinetic energy of the heme following ligand photolysis was observed in all systems studied. The relaxation rate depends on the solvent used. However, this dependence cannot be explained using bulk transport properties of the solvent including macroscopic thermal diffusion. The rate and mechanism of heme cooling depends upon the detailed microscopic interaction between the heme and solvent. Three intermolecular energy transfer mechanisms were considered: (i) energy transfer mediated by hydrogen bonds, (ii) direct vibration-vibration energy transfer via resonant interaction, and (iii) energy transfer via vibration-translation or vibration-rotation interaction, or in other words, thermal collision. The hydrogen bond interaction and vibration-vibration interaction between the heme and solvent molecules dominates the energy transfer in native myoglobin aqueous solution and native myoglobin glycerol solutions. For modified myoglobin, the vibration-vibration interaction is also effective in glycerol solution, different from aqueous solution. Thermal collisions form the dominant energy transfer pathway for modified myoglobin in water solution, and for both native myoglobin and modified myoglobin in a nonpolar environment. For native myoglobin in a nonpolar solvent solution, hydrogen bonds between heme isopropionate side chains and nearby protein residues, absent in the modified myoglobin nonpolar solvent solution, are key interactions influencing the

  14. Thermomolecular orientation of nonpolar fluids.

    Science.gov (United States)

    Römer, Frank; Bresme, Fernando; Muscatello, Jordan; Bedeaux, Dick; Rubí, J Miguel

    2012-03-09

    We investigate the response of molecular fluids to temperature gradients. Using nonequilibrium molecular dynamics computer simulations we show that nonpolar diatomic fluids adopt a preferred orientation as a response to a temperature gradient. We find that the magnitude of this thermomolecular orientation effect is proportional to the strength of the temperature gradient and the degree of molecular anisotropy, as defined by the different size or mass of the molecular atomic sites. We show that the preferred orientation of the molecules follows the same trends observed in the Soret effect of binary mixtures. We argue this is a general effect that should be observed in a wide range of length scales.

  15. EDITORIAL: Non-polar and semipolar nitride semiconductors Non-polar and semipolar nitride semiconductors

    Science.gov (United States)

    Han, Jung; Kneissl, Michael

    2012-02-01

    topics including growth and heteroepitaxy, bulk GaN substrates, theory and modelling, optical properties, laser diodes and LEDs as well as transport properties and electronics. Farrell et al review materials and growth issues for high-performance non- and semipolar light-emitting devices, and Scholz provides an overview of heteroepitaxial growth of semipolar GaN. Okada et al review growth mechanisms of non- and semipolar GaN layers on patterned sapphire substrates, and Vennéguès discusses defect reduction methods for heteroepitaxially grown non- and semipolar III-nitride films. Leung et al explain how kinetic Wulff plots can be used to design and control non-polar and semipolar GaN heteroepitaxy, and a contribution by Sawaki et al explores the impurity incorporation in (1-101) GaN grown on Si substrates. In the area of bulk crystal growth Kucharski et al review non- and semipolar GaN substrates by ammonothermal growth, and Chichibu et al discuss the challenges for epitaxial growth of InGaN on free-standing m-plane GaN substrates. Calculation of semipolar orientations for wurtzitic semiconductor heterostructures and their application to nitrides and oxides are reviewed by Bigenwald et al, and Ito et al present an ab initio approach to reconstruction, adsorption, and incorporation on GaN surfaces. Finally, the theoretical description of non-polar and semipolar nitride semiconductor quantum-well structures is presented by Ahn et al. In a discussion of the optical properties, Kisin et al discuss the effect of the quantum well population on the optical characteristics of polar, semipolar and non-polar III-nitride light emitters, and Jönen et al investigate the indium incorporation and optical properties of non- and semipolar GaInN QW structures. Wernicke et al explore the emission wavelength of polar, non-polar, and semipolar InGaN quantum wells and the incorporation of indium. In a contribution by Melo et al, the gain in polar and non-polar/semipolar gallium

  16. The Case for Tetrahedral Oxy-subhydride (TOSH Structures in the Exclusion Zones of Anchored Polar Solvents Including Water

    Directory of Open Access Journals (Sweden)

    Klaus Oehr

    2014-11-01

    Full Text Available We hypothesize a mechanistic model of how negatively-charged exclusion zones (EZs are created. While the growth of EZs is known to be associated with the absorption of ambient photonic energy, the molecular dynamics giving rise to this process need greater elucidation. We believe they arise due to the formation of oxy-subhydride structures (OH−(H2O4 with a tetrahedral (sp3 (OH−(H2O3 core. Five experimental data sets derived by previous researchers were assessed in this regard: (1 water-derived EZ light absorbance at specific infrared wavelengths, (2 EZ negative potential in water and ethanol, (3 maximum EZ light absorbance at 270 nm ultraviolet wavelength, (4 ability of dimethyl sulphoxide but not ether to form an EZ, and (5 transitory nature of melting ice derived EZs. The proposed tetrahedral oxy-subhydride structures (TOSH appear to adequately account for all of the experimental evidence derived from water or other polar solvents.

  17. Covalent and non-covalent functionalization and solubilization of double-walled carbon nanotubes in nonpolar and aqueous media

    Indian Academy of Sciences (India)

    L S Panchakarla; A Govindaraj

    2008-11-01

    Double-walled carbon nanotubes (DWNTs) have been functionalized by both covalent and non-covalent means. Covalent functionalization has been carried out by attaching an aliphatic amide function to DWNTs which enable solubilization in non-polar solvents. Solubilization in non-polar solvents has also been accomplished by non-covalent functionalization by using 1-pyrenebutanoicacid succinimidyl ester (PYBS). Non-covalent functionalization of DWNTs has been carried out by using polyethylene glycol (PEG) and polyoxyethylene(40)nonylphenyl ether (IGPAL), both of which enable solubilization in aqueous media. These functionalized DWNTs have been characterized by transmission electron microscopy, IR and Raman spectroscopy.

  18. Adsorption of polar, nonpolar, and substituted aromatics to colloidal graphene oxide nanoparticles

    NARCIS (Netherlands)

    Wang, Fang; Haftka, Joris J H; Sinnige, Theo L.; Hermens, Joop L M; Chen, Wei

    2014-01-01

    We conducted batch adsorption experiments to understand the adsorptive properties of colloidal graphene oxide nanoparticles (GONPs) for a range of environmentally relevant aromatics and substituted aromatics, including model nonpolar compounds (pyrene, phenanthrene, naphthalene, and 1,3-dichlorobenz

  19. Solvent substitution

    Energy Technology Data Exchange (ETDEWEB)

    1990-01-01

    The DOE Environmental Restoration and Waste Management Office of Technology Development and the Air Force Engineering and Services Center convened the First Annual International Workshop on Solvent Substitution on December 4--7, 1990. The primary objectives of this joint effort were to share information and ideas among attendees in order to enhance the development and implementation of required new technologies for the elimination of pollutants associated with industrial use of hazardous and toxic solvents; and to aid in accelerating collaborative efforts and technology transfer between government and industry for solvent substitution. There were workshop sessions focusing on Alternative Technologies, Alternative Solvents, Recovery/Recycling, Low VOC Materials and Treatment for Environmentally Safe Disposal. The 35 invited papers presented covered a wide range of solvent substitution activities including: hardware and weapons production and maintenance, paint stripping, coating applications, printed circuit boards, metal cleaning, metal finishing, manufacturing, compliance monitoring and process control monitoring. This publication includes the majority of these presentations. In addition, in order to further facilitate information exchange and technology transfer, the US Air Force and DOE solicited additional papers under a general Call for Papers.'' These papers, which underwent review and final selection by a peer review committee, are also included in this combined Proceedings/Compendium. For those involved in handling, using or managing hazardous and toxic solvents, this document should prove to be a valuable resource, providing the most up-to-date information on current technologies and practices in solvent substitution. Individual papers are abstracted separated.

  20. Birefringent non-polarizing thin film design

    Institute of Scientific and Technical Information of China (English)

    QI Hongji; HONG Ruijin; HE Hongbo; SHAO Jianda; FAN Zhengxiu

    2005-01-01

    In this paper, 2×2 characteristic matrices of uniaxially anisotropic thin film for extraordinary and ordinary wave are deduced at oblique incidence. Furthermore, the reflectance and transmittance of thin films are calculated separately for two polarizations, which provide a new concept for designing non-polarizing thin films at oblique incidence. Besides, using the multilayer birefringent thin films, non-polarizing designs, such as beam splitter thin film at single wavelength, edge filter and antireflection thin film over visible spectral region are obtained at oblique incidence.

  1. Silylation of montmorillonite surfaces: dependence on solvent nature.

    Science.gov (United States)

    Su, Linna; Tao, Qi; He, Hongping; Zhu, Jianxi; Yuan, Peng; Zhu, Runliang

    2013-02-01

    Silylation of clay mineral surfaces has attracted much attention due to their extensive applications in materials science and environmental engineering. Silylation of montmorillonite surfaces with 3-aminopropyltriethoxysilane was carried out in polar-protic and nonpolar solvents. The swelling property of the silylated montmorillonites was investigated by intercalating with cetyltrimethylammonium bromide. Silylated montmorillonites prepared in nonpolar solvents showed a larger amount of loaded silane and a higher extent of condensation among different silane molecules, comparing with those prepared in polar-protic solvents with high dielectric constant. Meanwhile, the silylated montmorillonites prepared in nonpolar solvents displayed poor swelling property due to the linkage between silane oligomers and clay layers, that is, the neighboring clay layers were locked by the silane oligomers. The present study demonstrated that the polarity of the solvents used had an important influence on the extent of grafting, interlayer structure, and swelling property of the silylated products. This is of high importance for synthesis and application of silylated clay minerals.

  2. Extended Hansen solubility approach: naphthalene in individual solvents.

    Science.gov (United States)

    Martin, A; Wu, P L; Adjei, A; Beerbower, A; Prausnitz, J M

    1981-11-01

    A multiple regression method using Hansen partial solubility parameters, delta D, delta p, and delta H, was used to reproduce the solubilities of naphthalene in pure polar and nonpolar solvents and to predict its solubility in untested solvents. The method, called the extended Hansen approach, was compared with the extended Hildebrand solubility approach and the universal-functional-group-activity-coefficient (UNIFAC) method. The Hildebrand regular solution theory was also used to calculate naphthalene solubility. Naphthalene, an aromatic molecule having no side chains or functional groups, is "well-behaved', i.e., its solubility in active solvents known to interact with drug molecules is fairly regular. Because of its simplicity, naphthalene is a suitable solute with which to initiate the difficult study of solubility phenomena. The three methods tested (Hildebrand regular solution theory was introduced only for comparison of solubilities in regular solution) yielded similar results, reproducing naphthalene solubilities within approximately 30% of literature values. In some cases, however, the error was considerably greater. The UNIFAC calculation is superior in that it requires only the solute's heat of fusion, the melting point, and a knowledge of chemical structures of solute and solvent. The extended Hansen and extended Hildebrand methods need experimental solubility data on which to carry out regression analysis. The extended Hansen approach was the method of second choice because of its adaptability to solutes and solvents from various classes. Sample calculations are included to illustrate methods of predicting solubilities in untested solvents at various temperatures. The UNIFAC method was successful in this regard.

  3. Description of excited states in [Re(Imidazole)(CO)3 (Phen)](+) including solvent and spin-orbit coupling effects: Density functional theory versus multiconfigurational wavefunction approach.

    Science.gov (United States)

    Fumanal, Maria; Daniel, Chantal

    2016-10-15

    The low-lying electronic excited states of [Re(imidazole)(CO)3 (phen)](+) (phen = 1,10-phenanthroline) ranging between 420 nm and 330 nm have been calculated by means of relativistic spin-orbit time-dependent density functional theory (TD-DFT) and wavefunction approaches (state-average-CASSCF/CASPT2). A direct comparison between the theoretical absorption spectra obtained with different methods including SOC and solvent corrections for water points to the difficulties at describing on the same footing the bands generated by metal-to-ligand charge transfer (MLCT), intraligand (IL) transition, and ligand-to-Ligand- charge transfer (LLCT). While TD-DFT and three-roots-state-average CASSCF (10,10) reproduce rather well the lowest broad MLCT band observed in the experimental spectrum between 420 nm and 330 nm, more flexible wavefunctions enlarged either by the number of roots or by the number of active orbitals and electrons destabilize the MLCT states by introducing IL and LLCT character in the lowest part of the absorption spectrum. © 2016 Wiley Periodicals, Inc.

  4. Measurement and prediction of aromatic solute distribution coefficients for aqueous-organic solvent systems. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Campbell, J.R.; Luthy, R.G.

    1984-06-01

    Experimental and modeling activities were performed to assess techniques for measurement and prediction of distribution coefficients for aromatic solutes between water and immiscible organic solvents. Experiments were performed to measure distribution coefficients in both clean water and wastewater systems, and to assess treatment of a wastewater by solvent extraction. The theoretical portions of this investigation were directed towards development of techniques for prediction of solute-solvent/water distribution coefficients. Experiments were performed to assess treatment of a phenolic-laden coal conversion wastewater by solvent extraction. The results showed that solvent extraction for recovery of phenolic material offered several wastewater processing advantages. Distribution coefficients were measured in clean water and wastewater systems for aromatic solutes of varying functionality with different solvent types. It was found that distribution coefficients for these compounds in clean water systems were not statistically different from distribution coefficients determined in a complex coal conversion process wastewater. These and other aromatic solute distribution coefficient data were employed for evaluation of modeling techniques for prediction of solute-solvent/water distribution coefficients. Eight solvents were selected in order to represent various chemical classes: toluene and benzene (aromatics), hexane and heptane (alkanes), n-octanol (alcohols), n-butyl acetate (esters), diisopropyl ether (ethers), and methylisobutyl ketone (ketones). The aromatic solutes included: nonpolar compounds such as benzene, toluene and naphthalene, phenolic compounds such as phenol, cresol and catechol, nitrogenous aromatics such as aniline, pyridine and aminonaphthalene, and other aromatic solutes such as naphthol, quinolinol and halogenated compounds. 100 references, 20 figures, 34 tables.

  5. Combined QM/MM Molecular Dynamics Study on a Condensed-Phase SN2 Reaction at Nitrogen:  The Effect of Explicitly Including Solvent Polarization.

    Science.gov (United States)

    Geerke, Daan P; Thiel, Stephan; Thiel, Walter; van Gunsteren, Wilfred F

    2007-07-01

    In a previous combined QM/MM molecular dynamics (MD) study from our laboratory on the identity SN2 reaction between a chloride anion and an amino chloride in liquid dimethyl ether (DME), an increase in the free energy activation barrier was observed in the condensed phase when compared to the gas-phase activation energy. Here we reproduce these findings, but when comparing the condensed-phase potential of mean force (PMF) with the free energy profile in the gas phase (obtained from Monte Carlo simulations), we observe a smaller solvent effect on the activation barrier of the reaction. In a next step, we introduce an explicit description of electronic polarization in the MM (solvent) part of the system. A polarizable force field for liquid DME was developed based on the charge-on-spring (COS) model, which was calibrated to reproduce thermodynamic properties of the nonpolarizable model in classical MD simulations. The COS model was implemented into the MNDO/GROMOS interface in a special version of the QM/MM software ChemShell, which was used to investigate the effect of solvent polarization on the free energy profile of the reaction under study. A higher activation barrier was obtained using the polarizable solvent model than with the nonpolarizable force field, due to a better solvation of and a stronger polarization of solvent molecules around the separate reactants. The obtained PMFs were subjected to an energy-entropy decomposition of the relative solvation free energies of the reactant complex along the reaction coordinate, to investigate in a quantitative manner whether the solvent (polarization) effects are mainly due to favorable QM-MM (energetic) interactions.

  6. Predicting the Solution Morphology of a Sulfonated Pentablock Copolymer in an Arbitrary Solvent Mixture

    Science.gov (United States)

    Ford, Jamie; Kyei-Manu, William; Winey, Karen

    2013-03-01

    Block copolymers self assemble into a wide array of morphologies in solvents. To predict the solution morphology of the polymer, we assess the interactions between the individual blocks and the solvent or solvents. Here, we use the Hansen solubility parameters to calculate the interactions between a library of solvents and an ABCBA pentablock copolymer with non-polar A and B blocks and a polar, sulfonated C block to predict the expected morphology for a given solvent and compare it to our small-angle X-ray scattering data. In non-polar solvents, we observe micelles with a C core and an A-B corona. We observe inverted micelles in polar solvents - an A-B core with a C corona. We extended our methodology to mixed polar/non-polar solvent systems to predict the solvent ratios corresponding to the transition from micelles to inverted micelles.

  7. Isolating the non-polar contributions to the intermolecular potential for water-alkane interactions.

    Science.gov (United States)

    Ballal, Deepti; Venkataraman, Pradeep; Fouad, Wael A; Cox, Kenneth R; Chapman, Walter G

    2014-08-14

    Intermolecular potential models for water and alkanes describe pure component properties fairly well, but fail to reproduce properties of water-alkane mixtures. Understanding interactions between water and non-polar molecules like alkanes is important not only for the hydrocarbon industry but has implications to biological processes as well. Although non-polar solutes in water have been widely studied, much less work has focused on water in non-polar solvents. In this study we calculate the solubility of water in different alkanes (methane to dodecane) at ambient conditions where the water content in alkanes is very low so that the non-polar water-alkane interactions determine solubility. Only the alkane-rich phase is simulated since the fugacity of water in the water rich phase is calculated from an accurate equation of state. Using the SPC/E model for water and TraPPE model for alkanes along with Lorentz-Berthelot mixing rules for the cross parameters produces a water solubility that is an order of magnitude lower than the experimental value. It is found that an effective water Lennard-Jones energy ε(W)/k = 220 K is required to match the experimental water solubility in TraPPE alkanes. This number is much higher than used in most simulation water models (SPC/E-ε(W)/k = 78.2 K). It is surprising that the interaction energy obtained here is also higher than the water-alkane interaction energy predicted by studies on solubility of alkanes in water. The reason for this high water-alkane interaction energy is not completely understood. Some factors that might contribute to the large interaction energy, such as polarizability of alkanes, octupole moment of methane, and clustering of water at low concentrations in alkanes, are examined. It is found that, though important, these factors do not completely explain the anomalously strong attraction between alkanes and water observed experimentally.

  8. Contact angles and wettability of ionic liquids on polar and non-polar surfaces.

    Science.gov (United States)

    Pereira, Matheus M; Kurnia, Kiki A; Sousa, Filipa L; Silva, Nuno J O; Lopes-da-Silva, José A; Coutinho, João A P; Freire, Mara G

    2015-12-21

    Many applications involving ionic liquids (ILs) require the knowledge of their interfacial behaviour, such as wettability and adhesion. In this context, herein, two approaches were combined aiming at understanding the impact of the IL chemical structures on their wettability on both polar and non-polar surfaces, namely: (i) the experimental determination of the contact angles of a broad range of ILs (covering a wide number of anions of variable polarity, cations, and cation alkyl side chain lengths) on polar and non-polar solid substrates (glass, Al-plate, and poly-(tetrafluoroethylene) (PTFE)); and (ii) the correlation of the experimental contact angles with the cation-anion pair interaction energies generated by the Conductor-like Screening Model for Real Solvents (COSMO-RS). The combined results reveal that the hydrogen-bond basicity of ILs, and thus the IL anion, plays a major role through their wettability on both polar and non-polar surfaces. The increase of the IL hydrogen-bond accepting ability leads to an improved wettability of more polar surfaces (lower contact angles) while the opposite trend is observed on non-polar surfaces. The cation nature and alkyl side chain lengths have however a smaller impact on the wetting ability of ILs. Linear correlations were found between the experimental contact angles and the cation-anion hydrogen-bonding and cation ring energies, estimated using COSMO-RS, suggesting that these features primarily control the wetting ability of ILs. Furthermore, two-descriptor correlations are proposed here to predict the contact angles of a wide variety of ILs on glass, Al-plate, and PTFE surfaces. A new extended list is provided for the contact angles of ILs on three surfaces, which can be used as a priori information to choose appropriate ILs before a given application.

  9. Contact angles and wettability of ionic liquids on polar and non-polar surfaces†

    Science.gov (United States)

    Sousa, Filipa L.; Silva, Nuno J. O.; Lopes-da-Silva, José A.; Coutinho, João A. P.; Freire, Mara G.

    2016-01-01

    Many applications involving ionic liquids (ILs) require the knowledge of their interfacial behaviour, such as wettability and adhesion. In this context, herein, two approaches were combined aiming at understanding the impact of the IL chemical structures on their wettability on both polar and non-polar surfaces, namely: (i) the experimental determination of the contact angles of a broad range of ILs (covering a wide number of anions of variable polarity, cations, and cation alkyl side chain lengths) on polar and non-polar solid substrates (glass, Al-plate, and poly-(tetrafluoroethylene) (PTFE)); and (ii) the correlation of the experimental contact angles with the cation–anion pair interaction energies generated by the Conductor-like Screening Model for Real Solvents (COSMO-RS). The combined results reveal that the hydrogen-bond basicity of ILs, and thus the IL anion, plays a major role through their wettability on both polar and non-polar surfaces. The increase of the IL hydrogen-bond accepting ability leads to an improved wettability of more polar surfaces (lower contact angles) while the opposite trend is observed on non-polar surfaces. The cation nature and alkyl side chain lengths have however a smaller impact on the wetting ability of ILs. Linear correlations were found between the experimental contact angles and the cation–anion hydrogen-bonding and cation ring energies, estimated using COSMO-RS, suggesting that these features primarily control the wetting ability of ILs. Furthermore, two-descriptor correlations are proposed here to predict the contact angles of a wide variety of ILs on glass, Al-plate, and PTFE surfaces. A new extended list is provided for the contact angles of ILs on three surfaces, which can be used as a priori information to choose appropriate ILs before a given application. PMID:26554705

  10. Bis{μ-cis-1,3-bis[(di-tert-butylphosphanyloxy]cyclohexane-κ2P:P′}bis[carbonylnickel(0] including an unknown solvent molecule

    Directory of Open Access Journals (Sweden)

    Klara J. Jonasson

    2014-05-01

    Full Text Available The title compound, [Ni2(C22H46P2O22(CO2], is located about a centre of inversion with the Ni0 atom within a distorted trigonal–planar geometry. The cyclohexyl rings are in the usual chair conformation with the 1,3-cis substituents equatorially oriented. No specific intermolecular interactions are noted in the crystal packing. A region of disordered electron density, most probably a disordered deuterobenzene solvent molecule, was treated using the SQUEEZE routine in PLATON [Spek (2009. Acta Cryst. D65, 148–155]. Its formula mass and unit-cell characteristics were not taken into account during refinement.

  11. Novel solvent systems for in situ extraterrestrial sample analysis

    OpenAIRE

    2010-01-01

    The life marker chip (LMC) is being designed to test for the chemical signature of life in the soil and rocks of Mars. It will use an antibody array as part of its detection and characterisation system and aims to detect both polar and non-polar molecules at the sub-ppm to tens of ppb level. It is necessary to use a solvent to transfer organic compounds from the Martian samples to the LMC itself, but organic solvents such as dichloromethane or hexane, commonly used to dissolve non-polar molec...

  12. 应用石墨为微波吸收介质非极性溶剂微波提取孜然挥发油成分%Application of graphite Powder for Non-polar Solvent Microwave Extraction of Essential Oils Cumimm Cyminum L.

    Institute of Scientific and Technical Information of China (English)

    于永; 王玉堂; 汪子明; 李铁纯; 张寒琦

    2008-01-01

    1引言微波加热效率高低主要取决于体系中物质吸收微波的能力大小,由于非极性溶剂不吸收微波因而通常不能单独作为微波辅助提取的提取溶剂。乙醚是一种常用的非极性溶剂,在蒸馏-提取法(simultaneous distillation and solvent extraction,SDE)中被用作提取溶剂,石墨是一种良好的微波吸收介质,本实验通过在乙醚中加入石墨建立了孜然中挥发油组分的非极性溶剂微波提取法(non-polar solvent microwave extraction,NPSME),

  13. Polar Solvents Trigger Formation of Reverse Micelles.

    Science.gov (United States)

    Khoshnood, Atefeh; Firoozabadi, Abbas

    2015-06-09

    We use molecular dynamics simulations and molecular thermodynamics to investigate the formation of reverse micelles in a system of surfactants and nonpolar solvents. Since the early observation of reverse micelles, the question has been whether the existence of polar solvent molecules such as water is the driving force for the formation of reverse micelles in nonpolar solvents. In this work, we use a simple coarse-grained model of surfactants and solvents to show that a small number of polar solvent molecules triggers the formation of large permanent aggregates. In the absence of polar molecules, both the thermodynamic model and molecular simulations show that small aggregates are more populated in the solution and larger ones are less frequent as the system evolves over time. The size and shape of reverse micelles depend on the size of the polar core: the shape is spherical for a large core and ellipsoidal for a smaller one. Using the coarse-grained model, we also investigate the effect of temperature and surfactant tail length. Our results reveal that the number of surfactant molecules in the micelle decreases as the temperature increases, but the average diameter does not change because the size of the polar core remains invariant. A reverse micelle with small polar core attracts fewer surfactants when the tail is long. The uptake of solvent particles by a micelle of longer surfactant tail is less than shorter ones when the polar solvent particles are initially distributed randomly.

  14. Solvent abuse: a review.

    Science.gov (United States)

    Barnes, G E

    1979-01-01

    The literature on solvent abuse is reviewed. Methods of use, symptoms of use, and effects of long-term solvent abuse are discussed. Several surveys on solvent use are summarized. The highest prevalence of solvent abuse seems to occur in native peoples undergoing periods of cultural change. Environmental conditions which are postulated as leading to psychological vulnerability and solvent abuse include: low social assets, parental drug use, peer and sibling influence, and acculturative stress. Solvent abuse seems to provide a pharmacological way out of a stressful environment for people who feel helpless to improve their situation in other ways. Methods of intervention that have been proposed for dealing with solvent abuse are discussed. Methods of intervention thus far employed generally have not been evaluated in any systematic fashion. Suggestions for future research are provided.

  15. Can Nonpolar Polyisobutylenes be Measured by Electrospray Ionization Mass Spectrometry? Anion-Attachment Proved to be an Appropriate Method

    Science.gov (United States)

    Nagy, Lajos; Nagy, Tibor; Deák, György; Kuki, Ákos; Purgel, Mihály; Narmandakh, Mijid; Iván, Béla; Zsuga, Miklós; Kéki, Sándor

    2016-03-01

    Polyisobutylenes (PIBs) with different end-groups including chlorine, exo-olefin, hydroxyl, and methyl prepared from aliphatic and aromatic initiators were studied by electrospray ionization mass spectrometry (ESI-MS). Independently of the end-groups, presence or absence of aromatic initiator moiety, these PIB derivatives were capable of forming adduct ions with NO3 - and Cl- ions, thus allowing the direct characterization of these compounds in the negative ion mode of ESI-MS. To obtain [PIB + NO3]- and [PIB + Cl]- adduct ions with appreciable intensities, addition of polar solvents such as acetone, 2-propanol, or ethanol to the dichloromethane solution of PIBs was necessary. Furthermore, increasing both the polarity (by increasing the acetone content) and the ion-source temperature give rise to enhanced intensities for both [PIB + NO3]- and [PIB + Cl]- ions. Energy-dependent collision induced dissociation studies (CID) revealed that increasing the collision voltages resulted in the shift of the apparent molecular masses to higher ones. CID studies also showed that dissociation of the [PIB + Cl]- ions requires higher collision energy than that of [PIB + NO3]-. In addition, Density Functional Theory calculations were performed to gain insights into the nature of the interactions between the highly non-polar PIB chains and anions NO3 - and Cl- as well as to determine the zero-point corrected electronic energies for the formation of [PIB + NO3]- and [PIB + Cl]- adduct ions.

  16. Solvent-dependent excited-state hydrogen transfer and intersystem crossing in 2-(2′-hydroxyphenyl)-benzothiazole

    KAUST Repository

    Aly, Shawkat Mohammede

    2015-02-12

    The excited-state intramolecular hydrogen transfer (ESIHT) of 2-(2′-hydroxyphenyl) benzothiazole (HBT) has been investigated in a series of nonpolar, polar aprotic, and polar protic solvents. A variety of state-of-the-art experimental methods were employed, including femto- and nanosecond transient absorption and fluorescence upconversion spectroscopy with broadband capabilities. We show that the dynamics and mechanism of ESIHT of the singlet excited HBT are strongly solvent-dependent. In nonpolar solvents, the data demonstrate that HBT molecules adopt a closed form stabilized by O-H⋯N chelated hydrogen bonds with no twisting angle, and the photoinduced H transfer occurs within 120 fs, leading to the formation of a keto tautomer. In polar solvents, owing to dipole-dipole cross talk and hydrogen bonding interactions, the H transfer process is followed by ultrafast nonradiative deactivation channels, including ultrafast internal conversion (IC) and intersystem crossing (ISC). This is likely to be driven by the twisting motion around the C-C bond between the hydroxyphenyl and thiazole moieties, facilitating the IC back to the enol ground state or to the keto triplet state. In addition, our femtosecond time-resolved fluorescence experiments indicate, for the first time, that the lifetime of the enol form in ACN is approximately 280 fs. This observation indicates that the solvent plays a crucial role in breaking the H bond and deactivating the excited state of the HBT. Interestingly, the broadband transient absorption and fluorescence up-conversion data clearly demonstrate that the intermolecular proton transfer from the excited HBT to the DMSO solvent is about 190 fs, forming the HBT anion excited state.

  17. Partial solubility parameters and solvatochromic parameters for predicting the solubility of single and multiple drugs in individual solvents.

    Science.gov (United States)

    Bustamante, P; Martin, A; Gonzalez-Guisandez, M A

    1993-06-01

    A modification of the extended Hansen method is used for estimating the solubility of sulfadiazine and other organic drug molecules in a number of individual solvents ranging from nonpolar to highly polar. The equations obtained for each drug involve the partial solubility parameters of the solvents and allow the prediction of solubility of these drugs in a new solvent. Furthermore, a number of drugs (e.g., sulfadiazine, sulfamethoxypyridazine, naphthalene, and some benzoic acid derivatives) are combined in a single expression including the ideal solubility of the drugs and the partial solubility parameters of the solvents. The equation fits the solubilities of these drugs in a wide variety of solvents and may be used to predict the solubility of other sulfonamides and benzoic acid derivatives in semipolar and highly polar solvents. The solvatochromic parameter approach is also used in models for predicting the solubility of single drugs in individual solvents. It was tested with multiple solutes as was the partial solubility parameter approach. However, the latter approach is superior; the parameters of the solubility parameter method are all statistically significant for drugs tested individually or together in a single equation, a condition that is not obtained with the solvatochromic model.

  18. Juniperus extraction: a comparison of species and solvents

    Science.gov (United States)

    The effectiveness of the three solvents, hexane, methanol and ethanol were compared for their ability to extract non-polar and polar materials from sawdust from three species of Juniperus (i.e., J. virginianna, J. occidentalis and J. ashei). These species studied represent the junipers with the grea...

  19. Selective nonspecific solvation under dielectric saturation and fluorescence spectra of dye solutions in binary solvents.

    Science.gov (United States)

    Bakhshiev, N G; Kiselev, M B

    1991-09-01

    The influence of selective nonspecific solvation on the fluorescence spectra of three substitutedN-methylphthalimides in a binary solvent system consisting of a nonpolar (n-heptane) and a polar (pyridine) component has been studied under conditions close to dielectric saturation. The substantially nonlinearity of the effect is confirmation that the spectral shifts of fluorescence bands depend on the number of polar solvent molecules involved in solvating the dye molecule. The measured fluorescence spectral shifts determined by substituting one nonpolar solvent molecula with a polar one in the proximity of the dye molecule agree quantitatively with the forecasts of the previously proposed semiempirical theory which describes this nonlinear solvation phenomenon.

  20. Effect of Solvent Dielectric Constant and Acidity on the OH Vibration Frequency in Hydrogen-Bonded Complexes of Fluorinated Ethanols.

    Science.gov (United States)

    Pines, Dina; Keinan, Sharon; Kiefer, Philip M; Hynes, James T; Pines, Ehud

    2015-07-23

    Infrared spectroscopy measurements were used to characterize the OH stretching vibrations in a series of similarly structured fluoroethanols, RCH2OH (R = CH3, CH2F, CHF2, CF3), a series which exhibits a systematic increase in the molecule acidity with increasing number of F atoms. This study, which expands our earlier efforts, was carried out in non-hydrogen-bonding solvents comprising molecules with and without a permanent dipole moment, with the former solvents being classified as polar solvents and the latter designated as nonpolar. The hydrogen bond interaction in donor-acceptor complexes formed in solution between the fluorinated ethanol H-donors and the H-acceptor base DMSO was investigated in relation to the solvent dielectric and to the differences ΔPA of the gas phase proton affinities (PAs) of the conjugate base of the fluorinated alcohols and DMSO. We have observed that νOH decreases as the acidity of the alcohol increases (ΔPA decreases) and that νOH varies inversely with ε, exhibiting different slopes for nonpolar and polar solvents. These 1/ε slopes tend to vary linearly with ΔPA, increasing with increasing acidity. These experimental findings, including the ΔPA trends, are described with our recently published two-state Valence Bond-based theory for acid-base H-bonded complexes. Lastly, the correlation of the alcohol's conjugate base PAs with Taft σ* values of the fluorinated ethyl groups CH(n)F(3-n)CH2- provides a connection of the inductive effects for these groups with the acidity parameter ΔPA associated with the H-bonded complexes.

  1. Long-Wavelength Phonon Scattering in Nonpolar Semiconductors

    DEFF Research Database (Denmark)

    Lawætz, Peter

    1969-01-01

    The long-wavelength acoustic- and optical-phonon scattering of carriers in nonpolar semiconductors is considered from a general point of view. The deformation-potential approximation is defined and it is shown that long-range electrostatic forces give a nontrivial correction to the scattering. Fo...

  2. Solvent effects on hydrogen bonding between primary alcohols and esters

    Institute of Scientific and Technical Information of China (English)

    DHARMALINGAM K.; RAMACHANDRAN K.; SIVAGURUNATHAN P.

    2006-01-01

    The interaction by hydrogen bond formation of some primary alcohols (1-heptanol, 1-octanol and 1-decanol) with esters (methyl methacrylate, ethyl methacrylate and butyl methacrylate) was investigated in non-polar solvents viz., n-heptane,CCh and benzene by means of FTIR spectroscopy. Formation constants and free energy changes of complex formation were determined. The dependence of the equilibrium constants and free energy changes of complex formation on the alkyl chain length of both the alcohols and esters are discussed. The solvent effect on the hydrogen bond formation is discussed in terms of specific interaction between the solute and solvent.

  3. Alternative solvents for improving the greenness of normal phase liquid chromatography of lipid classes.

    Science.gov (United States)

    Prache, Nolwenn; Abreu, Sonia; Sassiat, Patrick; Thiébaut, Didier; Chaminade, Pierre

    2016-09-16

    An evaluation of solvents alternative to n-heptane (d-limonene and hexamethyldisiloxane) and chloroform (cyclopentyl methyl ether, 2-methyltetrahydrofuran and isopentyl acetate) was developed for lipid classes separation of non-polar cholesteryl ester to highly polar phospholipids by high-performance liquid chromatography on bare silica stationary phase and evaporative light-scattering detection. Screening of alternative solvents was used to estimate their compatibility with liquid chromatography and evaporative light-scattering detection and to evaluate their chromatographic selectivity. This work shows that n-heptane can be advantageously replaced by hexamethyldisiloxane. An increase of non-polar lipids retention is observed with hexamethyldisiloxane as weak solvent. Chloroform, which is largely used for lipid analysis, might be replaced efficaciously by cyclopentyl methyl ether, 2-methyltetrahydrofuran or isopentyl acetate. Aside from offering a different selectivity, the gradients composed by one or both alternative solvents gave efficient and comparable or even better separations than those obtained with conventional solvents.

  4. Strong guest binding by cyclodextrin hosts in competing nonpolar solvents and the unique crystalline structure.

    Science.gov (United States)

    Kida, Toshiyuki; Iwamoto, Takuya; Fujino, Yoshinori; Tohnai, Norimitsu; Miyata, Mikiji; Akashi, Mitsuru

    2011-09-02

    6-O-Modified β-cyclodextrins, such as heptakis(6-O-triisopropylsilyl)-β-cyclodextrin (TIPS-β-CD) and heptakis(6-O-tert-butyldimethylsilyl)-β-cyclodextrin (TBDMS-β-CD), formed 2:1 inclusion complexes with pyrene in benzene and cyclohexane with high association constants. The X-ray crystalline structure of the TIPS-β-CD-pyrene complex obtained from the benzene solution showed that one pyrene molecule was incorporated in the form of a sandwich-type complex with two benzene molecules within the cavity of the dimer formed by two TIPS-β-CD molecules.

  5. Liquid crystalline phases in suspensions of pigments in non-polar solvents

    Science.gov (United States)

    Klein, Susanne; Richardson, Robert M.; Eremin, Alexey

    We will discuss colloid suspensions of pigments and compare their electro-optic properties with those of traditional dyed low molecular weight liquid crystal systems. There are several potential advantages of colloidal suspensions over low molecular weight liquid crystal systems: a very high contrast because of the high orientational order parameter of suspensions of rod shaped nano-particles, the excellent light fastness of pigments as compared to dyes and high colour saturations resulting from the high loading of the colour stuff. Although a weak `single-particle' electro-optic response can be observed in dilute suspensions, the response is very much enhanced when the concentration of the particles is sufficient to lead to a nematic phase. Excellent stability of suspensions is beneficial for experimental observation and reproducibility, but it is a fundamental necessity for display applications. We therefore discuss a method to achieve long term stability of dispersed pigments and the reasons for its success. Small angle X-ray scattering was used to determine the orientational order parameter of the suspensions as a function of concentration and the dynamic response to an applied electric field. Optical properties were investigated for a wide range of pigment concentrations. Electro-optical phenomena, such as field-induced birefringence and switching, were characterised. In addition, mixtures of pigment suspensions with small amounts of ferrofluids show promise as future magneto-optical materials.

  6. Green solvents and technologies for oil extraction from oilseeds.

    Science.gov (United States)

    Kumar, S P Jeevan; Prasad, S Rajendra; Banerjee, Rintu; Agarwal, Dinesh K; Kulkarni, Kalyani S; Ramesh, K V

    2017-01-01

    Oilseeds are crucial for the nutritional security of the global population. The conventional technology used for oil extraction from oilseeds is by solvent extraction. In solvent extraction, n-hexane is used as a solvent for its attributes such as simple recovery, non-polar nature, low latent heat of vaporization (330 kJ/kg) and high selectivity to solvents. However, usage of hexane as a solvent has lead to several repercussions such as air pollution, toxicity and harmfulness that prompted to look for alternative options. To circumvent the problem, green solvents could be a promising approach to replace solvent extraction. In this review, green solvents and technology like aqueous assisted enzyme extraction are better solution for oil extraction from oilseeds. Enzyme mediated extraction is eco-friendly, can obtain higher yields, cost-effective and aids in obtaining co-products without any damage. Enzyme technology has great potential for oil extraction in oilseed industry. Similarly, green solvents such as terpenes and ionic liquids have tremendous solvent properties that enable to extract the oil in eco-friendly manner. These green solvents and technologies are considered green owing to the attributes of energy reduction, eco-friendliness, non-toxicity and non-harmfulness. Hence, the review is mainly focussed on the prospects and challenges of green solvents and technology as the best option to replace the conventional methods without compromising the quality of the extracted products.

  7. Determining the orientation of protegrin-1 in DLPC bilayers using an implicit solvent-membrane model.

    Directory of Open Access Journals (Sweden)

    Abdallah Sayyed-Ahmad

    Full Text Available Continuum models that describe the effects of solvent and biological membrane molecules on the structure and behavior of antimicrobial peptides, holds a promise to improve our understanding of the mechanisms of antimicrobial action of these peptides. In such methods, a lipid bilayer model membrane is implicitly represented by multiple layers of relatively low dielectric constant embedded in a high dielectric aqueous solvent, while an antimicrobial peptide is accounted for by a dielectric cavity with fixed partial charge at the center of each one of its atoms. In the present work, we investigate the ability of continuum approaches to predict the most probable orientation of the beta-hairpin antimicrobial peptide Protegrin-1 (PG-1 in DLPC lipid bilayers by calculating the difference in the transfer free energy from an aqueous environment to a membrane-water environment for multiple orientations. The transfer free energy is computed as a sum of two terms; polar/electrostatic and non-polar. They both include energetic and entropic contributions to the free energy. We numerically solve the Poisson-Boltzmann equation to calculate the electrostatic contribution to the transfer free energy, while the non-polar contribution to the free energy is approximated using a linear solvent accessible surface area relationships. The most probable orientation of PG-1 is that with the lowest relative transfer free energy. Our simulation results indicate that PG-1 assumes an oblique orientation in DLPC lipid bilayers. The predicted most favorable orientation was with a tilt angle of 19 degrees, which is in qualitative agreement with the experimentally observed orientations derived from solid-state NMR data.

  8. Wetting films of polar and nonpolar liquids.

    Science.gov (United States)

    Vazquez, Rosa; Nogueira, Rui; Busquets, Sandra; Mata, José Luís; Saramago, Benilde

    2005-04-15

    Disjoining pressure isotherms for water and n-octane films on glass obtained using a recently developed apparatus, based on the interferometric technique, are compared with other values reported in the literature. Our method, including a simple cleaning procedure, yields experimental results in excellent agreement both with other experimental results and with theoretical predictions. An error analysis was made which quantifies the uncertainty of our results and simultaneously allows the minimization of the errors.

  9. Fluctuation capture in non-polar gases and liquids

    CERN Document Server

    Cocks, D G

    2016-01-01

    We present a new model to identify natural fluctuations in fluids, allowing us to describe localization phenomena in the transport of electrons, positrons and positronium through non-polar fluids. The theory contains no free parameters and allows for the calculation of capture cross sections $\\sigma_{cap}(\\epsilon)$ of light-particles in any non-polar fluid, required for non-equilibrium transport simulations. We postulate that localization occurs through large shallow traps before stable bound states are formed. Our results allow us to explain most of the experimental observations of changes in mobility and annihilation rates in the noble gases and liquids as well as make predictions for future experiments. Quantities which are currently inaccessible to experiment, such as positron mobilities, can be obtained from our theory. Unlike other theoretical approaches to localization, the outputs of our theory can be applied in non-equilibrium transport simulations and an extension to the determination of waiting ti...

  10. Nanoencapsulation of Fullerenes in Organic Structures with Nonpolar Cavities

    Science.gov (United States)

    Murthy, C. N.

    2005-01-01

    The formation of supramolecular structures, assemblies, and arrays held together by weak intermolecular interactions and non-covalent binding mimicking natural processes has been used in applications being anticipated in nanotechnology, biotechnology and the emerging field of nanomedicine. Encapsulation of C60 fullerene by cyclic molecules like cyclodextrins and calixarenes has potential for a number of applications. Similarly, biomolecules like lysozyme also have been shown to encapsulate C60 fullerene. This poster article reports the recent trends and the results obtained in the nanoencapsulation of fullerenes by biomolecules containing nonpolar cavities. Lysozyme was chosen as the model biomolecule and it was observed that there is no covalent bond formed between the bimolecule and the C60 fullerene. This was confirmed from fluorescence energy transfer studies. UV Vis studies further supported this observation that it is possible to selectively remove the C60 fullerene from the nonpolar cavity. This behavior has potential in biomedical applications

  11. Nanoencapsulation of Fullerenes in Organic Structures with Nonpolar Cavities

    Energy Technology Data Exchange (ETDEWEB)

    Murthy, C. N. [M.S. University of Baroda, Applied Chemistry Department, Faculty of Technology and Engineering (India)

    2005-01-15

    The formation of supramolecular structures, assemblies, and arrays held together by weak intermolecular interactions and non-covalent binding mimicking natural processes has been used in applications being anticipated in nanotechnology, biotechnology and the emerging field of nanomedicine. Encapsulation of C{sub 60} fullerene by cyclic molecules like cyclodextrins and calixarenes has potential for a number of applications. Similarly, biomolecules like lysozyme also have been shown to encapsulate C{sub 60} fullerene. This poster article reports the recent trends and the results obtained in the nanoencapsulation of fullerenes by biomolecules containing nonpolar cavities. Lysozyme was chosen as the model biomolecule and it was observed that there is no covalent bond formed between the bimolecule and the C{sub 60} fullerene. This was confirmed from fluorescence energy transfer studies. UV-Vis studies further supported this observation that it is possible to selectively remove the C{sub 60} fullerene from the nonpolar cavity. This behavior has potential in biomedical applications

  12. Study on Surface Properties for Non-polar Fluids with Density Functional Theory

    Institute of Scientific and Technical Information of China (English)

    吴畏; 陆九芳; 付东; 刘金晨; 李以圭

    2004-01-01

    The density functional theory, simplified by the local density approximation and mean-field approximation, is applied to study the surface properties of pure non-polar fluids. A reasonable long rang correction is adopted to avoid the truncation of the potential. The perturbation theory is applied to establish the equation for the phase equilibrium, in which the hard-core chain fluid is as the reference fluid and the Yukawa potential is used as the perturbation term. Three parameters, elk, d and ms, are regressed from the vapor-liquid equilibria, and the surface properties, including density profile, surface tension and local surface tension profile are predicted with these parameters.

  13. Thermodiffusion in binary and ternary nonpolar hydrocarbon + alcohol mixtures

    Science.gov (United States)

    Eslamian, Morteza; Saghir, M. Ziad

    2012-12-01

    Thermodiffusion in complex mixtures, such as associating, molten metal, and polymer mixtures is difficult to model usually owing to the occurrence of a sign change in the thermodiffusion coefficient when the mixture concentration and temperature change. A mixture comprised of a nonpolar hydrocarbon and an alcohol is a complex and highly non-ideal mixture. In this paper an existing binary non-equilibrium thermodynamics model (Eslamian and Saghir, Physical Review E 80, 061201, 2009) developed for aqueous mixtures of alcohols is examined against the experimental data of binary nonpolar hydrocarbon and alcohol mixtures. For ternary mixtures, non-equilibrium thermodynamic expressions developed by the authors for aqueous mixtures of alcohols (Eslamian and Saghir, Canadian Journal of Chemical Engineering, DOI 10.1002/cjce.20581) is used to predict thermodiffusion coefficients of ternary nonpolar hydrocarbon and alcohol mixtures. The rationale behind the sign change is elucidated and attributed to an anomalous change in the molecular structure and therefore viscosity of such mixtures. Model predictions of thermodiffusion coefficients of binary mixtures predict a sign change consistent with the experimental data although the model is still too primitive to capture all structural complexities. For instance, in the methanol-benzene mixture where the model predictions are poorest, the viscosity data show that when concentration varies, the mixture's molecular structure experiences a severe change twice, the first major change leading to a maximum in the thermodiffusion coefficient, whereas the second change causes a sign change.

  14. In Vitro Anticancer Activity of a Nonpolar Fraction from Gynostemma pentaphyllum (Thunb.) Makino

    Science.gov (United States)

    Li, Yantao; Huang, Jiajun; Lin, Wanjun; Yuan, Zhongwen; Feng, Senling; Xie, Ying; Ma, Wenzhe

    2016-01-01

    Gynostemma pentaphyllum (Thunb.) Makino (GpM) has been widely used in traditional Chinese medicine (TCM) for the treatment of various diseases including cancer. Most previous studies have focused primarily on polar fractions of GpM for anticancer activities. In this study, a nonpolar fraction EA1.3A from GpM showed potent growth inhibitory activities against four cancer cell lines with IC50 ranging from 31.62 μg/mL to 38.02 μg/mL. Furthermore, EA1.3A also inhibited the growth of breast cancer cell MDA-MB-453 time-dependently, as well as its colony formation ability. EA1.3A induced apoptosis on MDA-MB-453 cells both dose-dependently and time-dependently as analyzed by flow cytometry and verified by western blotting analysis of apoptosis marker cleaved nuclear poly(ADP-ribose) polymerase (cPARP). Additionally, EA1.3A induced cell cycle arrest in G0/G1 phase. Chemical components analysis of EA1.3A by GC-MS revealed that this nonpolar fraction from GpM contains 10 compounds including four alkaloids, three organic esters, two terpenes, and one catechol substance, and all these compounds have not been reported in GpM. In summary, the nonpolar fraction EA1.3A from GpM inhibited cancer cell growth through induction of apoptosis and regulation of cell cycle progression. Our study shed light on new chemical bases for the anticancer activities of GpM and feasibilities to develop new anticancer agents from this widely used medicinal plant. PMID:27034692

  15. In Vitro Anticancer Activity of a Nonpolar Fraction from Gynostemma pentaphyllum (Thunb. Makino

    Directory of Open Access Journals (Sweden)

    Yantao Li

    2016-01-01

    Full Text Available Gynostemma pentaphyllum (Thunb. Makino (GpM has been widely used in traditional Chinese medicine (TCM for the treatment of various diseases including cancer. Most previous studies have focused primarily on polar fractions of GpM for anticancer activities. In this study, a nonpolar fraction EA1.3A from GpM showed potent growth inhibitory activities against four cancer cell lines with IC50 ranging from 31.62 μg/mL to 38.02 μg/mL. Furthermore, EA1.3A also inhibited the growth of breast cancer cell MDA-MB-453 time-dependently, as well as its colony formation ability. EA1.3A induced apoptosis on MDA-MB-453 cells both dose-dependently and time-dependently as analyzed by flow cytometry and verified by western blotting analysis of apoptosis marker cleaved nuclear poly(ADP-ribose polymerase (cPARP. Additionally, EA1.3A induced cell cycle arrest in G0/G1 phase. Chemical components analysis of EA1.3A by GC-MS revealed that this nonpolar fraction from GpM contains 10 compounds including four alkaloids, three organic esters, two terpenes, and one catechol substance, and all these compounds have not been reported in GpM. In summary, the nonpolar fraction EA1.3A from GpM inhibited cancer cell growth through induction of apoptosis and regulation of cell cycle progression. Our study shed light on new chemical bases for the anticancer activities of GpM and feasibilities to develop new anticancer agents from this widely used medicinal plant.

  16. Dermoscopic features of basal cell carcinomas: differences in appearance under non-polarized and polarized light.

    Science.gov (United States)

    Liebman, Tracey N; Jaimes-Lopez, Natalia; Balagula, Yevgeniy; Rabinovitz, Harold S; Wang, Steven Q; Dusza, Stephen W; Marghoob, Ashfaq A

    2012-03-01

    Basal cell carcinomas (BCCs) can be diagnosed using different dermoscopic modalities. To evaluate dermoscopic features of BCCs using nonpolarized and polarized dermoscopy to highlight similarities and differences between dermoscopic modalities. Retrospective study of 149 BCCs under nonpolarized dermoscopy (NPD), polarized contact dermoscopy (PCD), and polarized noncontact dermoscopy (PNCD). Images were evaluated for a range of dermoscopic colors, structures, and vessels. Features were compared according to histopathologic subtype. The most common dermoscopic structures in BCCs across all modalities included globules (50.3-51.0%), dots (49.7-50.3%), white structureless areas (63.1-74.5%), structureless gray-brown areas (24.2-24.8%), and ulcerations (28.2%). The most frequently observed vasculature included arborizing vessels (18.8-38.3%), short fine telangiectasias (SFTs) (73.8-82.6%), and vascular blush (41.6-83.2%). Structures with higher levels of agreement across modalities included pigmented structures and ulcerations. Lower levels of agreement existed between contact and noncontact modalities for certain vascular features. White shiny structures, which include shiny white lines (chrysalis and crystalline structures) (0-69.1%), shiny white areas (0-25.5%), and rosettes (0-11.4%), exhibited no agreement between NPD and polarized modalities. This study highlights differences in dermoscopic features of BCCs under three dermoscopic modalities. Shiny white lines (chrysalis and crystalline structures) and shiny white areas may be used as additional criteria to diagnose BCCs. © 2011 by the American Society for Dermatologic Surgery, Inc. Published by Wiley Periodicals, Inc.

  17. Solvent effects on some new meso-aryl substituted octabromoporphyrins

    Indian Academy of Sciences (India)

    Regimol G George; M Padmanabhan

    2003-08-01

    A series of porphyrins with tolyl and naphthyl substituents at the meso positions, their octabromoderivatives (OBP) with Br substituents at -pyrrole positions are synthesised and characterised by chemical analysis, 1H NMR and electronic spectral studies. It is seen that all the OBPs exhibit pronounced red shifts in both the Soret and bands of their electronic spectra compared to their nonbrominated form in various polar and nonpolar solvents, the energy difference $\\bar{v}$ being in the range 2300-2700 cm-1. The high energy band of naphthyl porphyrins (both brominated and nonbrominated) are found to be more red-shifted than that of tolyl porphyrins, owing to the noticeable mesomeric effect of the naphthyl groups. Detailed spectral studies reveal that while none of the nonbrominated porphyrin show solvent-dependent change in their and bands, all the OBPs manifest significant shifts depending on the nature of solvents. Solvent-solute interaction can be considered to be of strong dipole-dipole nature for OBPs with polar solvents and of - type with aromatic non-polar solvents. In the brominated form we find two categories of porphyrins exhibiting distinctly different absorption phenomena in aromatic solvents. The OBPs having meso-groups not shielding the porphyrin -framework exhibit additional absorption peaks (split Soret peaks and broadened Q bands) in some aromatic solvents. This could be explained in terms of - type donor-acceptor (DA) complex formation between such bromoporphyrins (acceptor) and the aromatic solvent molecules (donor) that is not possible for OBPs that have bulky meso groups that block the approach of aromatic solvent molecules close to the porphyrin framework.

  18. Halogenated solvent remediation

    Science.gov (United States)

    Sorenson, Kent S.

    2004-08-31

    Methods for enhancing bioremediation of ground water contaminated with nonaqueous halogenated solvents are disclosed. A preferred method includes adding a composition to the ground water wherein the composition is an electron donor for microbe-mediated reductive dehalogenation of the halogenated solvents and enhances mass transfer of the halogenated solvents from residual source areas into the aqueous phase of the ground water. Illustrative compositions effective in these methods include surfactants such as C.sub.2 -C.sub.4 carboxylic acids and hydroxy acids, salts thereof, esters of C.sub.2 -C.sub.4 carboxylic acids and hydroxy acids, and mixtures thereof. Especially preferred compositions for use in these methods include lactic acid, salts of lactic acid, such as sodium lactate, lactate esters, and mixtures thereof. The microbes are either indigenous to the ground water, or such microbes can be added to the ground water in addition to the composition.

  19. Understanding surface interactions in aqueous miscible organic solvent treated layered double hydroxides.

    OpenAIRE

    Erastova, Valentina; Degiacomi, Matteo T.; O'Hare, Dermot; Greenwell, H. Chris

    2016-01-01

    Layered materials are of interest for use in a wealth of technological applications, many of which require a high surface area for optimal properties and performance. Recently, an industrially scalable method to create high surface area layered double hydroxide (LDH) materials, which may be readily dispersed in non-polar solvents, has been developed. This method involves treatment of LDHs with aqueous miscible organic (AMO) solvents. Here, molecular modeling is exploited to elucidate the AMO ...

  20. Photonic Crystal Polarizing and Non-Polarizing Beam Splitters

    Institute of Scientific and Technical Information of China (English)

    GUAN Chun-Ying; SHI Jin-Hui; YUAN Li-Bo

    2008-01-01

    A polarizing beam splitter(PBS)and a non-polarizing beam splitter(NPBS)based on a photonic crystal(PC)directional coupler are demonstrated.The photonic crystal directional coupler consists of a hexagonal lattice of dielectric pillars in air and has a complete photonic band gap.The photonic band structure and the band gap map are calculated using the plane wave expansion(PWE)method.The splitting properties of the splitter are investigated numerically using the finite difference time domain(FDTD)method.

  1. Computer Aided Solvent Selection and Design Framework

    DEFF Research Database (Denmark)

    Mitrofanov, Igor; Conte, Elisa; Abildskov, Jens

    , millions of tons solvents have to be wasted every year [2]. Therefore, it becomes important to minimize and optimize the use of organic solvents as much as possible, to satisfy the “Green Chemistry Principles” [3]. Another challenge is that currently solvent selection relies very much on previous...... is to develop a systematic framework and implement it as software for selection and design of solvents for many applications including organic synthesis, complex reaction systems and solvent-based separations. The solvent selection framework is based on a combination of knowledge from industrial practice...... identification of solvent candidates using special software ProCAMD and ProPred, which are the implementations of computer-aided molecular techniques. The second consists of assigning the RS-indices following the reaction–solvent and then consulting the known solvent database and identifying the set of solvents...

  2. Organic solvent topical report

    Energy Technology Data Exchange (ETDEWEB)

    Cowley, W.L.

    1998-04-30

    This report is the technical basis for the accident and consequence analyses used in the Hanford Tank Farms Basis for Interim Operation. The report also contains the scientific and engineering information and reference material needed to understand the organic solvent safety issue. This report includes comments received from the Chemical Reactions Subcommittee of the Tank Advisory Panel.

  3. Roles of urea and TMAO on the interaction between extended non-polar peptides

    Science.gov (United States)

    Su, Zhaoqian; Dias, Cristiano

    Urea and trimethylamine n-oxide (TMAO) are small molecules known to destabilize and stabilize, respectively, the structure of proteins when added to aqueous solution. To unravel the molecular mechanisms of these cosolvents on protein structure we perform explicit all-atom molecular dynamics simulations of extended poly-alanine and polyleucine dimers. We use an umbrella sampling protocol to compute the potential of mean force (PMF) of dimers at different concentrations of urea and TMAO. We find that the large non-polar side chain of leucine is affected by urea whereas backbone atoms and alanine's side chain are not. Urea is found to occupy positions between leucine's side chains that are not accessible to water. This accounts for extra Lennard-Jones bonds between urea and side chains that favors the unfolded state. These bonds compete with urea-solvent interactions that favor the folded state. The sum of these two energetic terms provide the enthalpic driving force for unfolding. We show here that this enthalpy correlate with the potential of mean force of poly-leucine dimers. Moreover, the framework developed here is general and may be used to provide insights into effects of other small molecules on protein interactions. The effect of the TMAO will be in the presentation. Department of Physics, University Heights, Newark, New Jersey, 07102-1982.

  4. Electrophoretic Retardation of Colloidal Particles in Nonpolar Liquids

    Directory of Open Access Journals (Sweden)

    Filip Strubbe

    2013-04-01

    Full Text Available We have measured the electrophoretic mobility of single, optically trapped colloidal particles, while gradually depleting the co-ions and counterions in the liquid around the particle by applying a dc voltage. This is achieved in a nonpolar liquid, where charged reverse micelles act as co-ions and counterions. By increasing the dc voltage, the mobility first increases when the concentrations of co-ions and counterions near the particle start to decrease. At sufficiently high dc voltage (around 2 V, the mobility reaches a saturation value when the co-ions and counterions are fully separated. The increase in mobility is larger when the equilibrium ionic strength is higher. The dependence of the experimental data on the equilibrium ionic strength and on the applied voltage is in good agreement with the standard theory of electrophoretic retardation, assuming that the bare particle charge remains constant. This method is useful for studying the electrophoretic retardation effect and charging mechanisms for nonpolar colloids, and it sheds light on previously unexplained particle acceleration in electronic ink devices.

  5. Observation of water dangling OH bonds around dissolved nonpolar groups.

    Science.gov (United States)

    Perera, P N; Fega, K R; Lawrence, C; Sundstrom, E J; Tomlinson-Phillips, J; Ben-Amotz, Dor

    2009-07-28

    We report the experimental observation of water dangling OH bonds in the hydration shells around dissolved nonpolar (hydrocarbon) groups. The results are obtained by combining vibrational (Raman) spectroscopy and multivariate curve resolution (MCR), to reveal a high-frequency OH stretch peak arising from the hydration shell around nonpolar (hydrocarbon) solute groups. The frequency and width of the observed peak is similar to that of dangling OH bonds previously detected at macroscopic air-water and oil-water interfaces. The area of the observed peak is used to quantify the number of water dangling bonds around hydrocarbon chains of different length. Molecular dynamics simulation of the vibrational spectra of water molecules in the hydration shell around neopentane and benzene reveals high-frequency OH features that closely resemble the experimentally observed dangling OH vibrational bands around neopentyl alcohol and benzyl alcohol. The red-shift of approximately 50 cm(-1) induced by aromatic solutes is similar to that previously observed upon formation of a pi-H bond (in low-temperature benzene-water clusters).

  6. Solvent cleaning system and method for removing contaminants from solvent used in resin recycling

    Science.gov (United States)

    Bohnert, George W.; Hand, Thomas E.; DeLaurentiis, Gary M.

    2009-01-06

    A two step solvent and carbon dioxide based system that produces essentially contaminant-free synthetic resin material and which further includes a solvent cleaning system for periodically removing the contaminants from the solvent so that the solvent can be reused and the contaminants can be collected and safely discarded in an environmentally safe manner.

  7. Large organized surface domains self-assembled from nonpolar amphiphiles.

    Science.gov (United States)

    Krafft, Marie Pierre

    2012-04-17

    unambiguously demonstrated the presence of surface micelles in monolayers of diblocks prior to LB transfer for atomic force microscopy imaging. We characterized an almost perfect two-dimensional crystal, with 12 assignable diffraction peaks, which established that self-assembly and regular nanopatterning were not caused by transfer or induced by the solid support. These experiments also provide the first direct identification of surface micelles on water, and the first identification of such large-size domains using GISAXS. Revisiting Langmuir film compression behavior after we realized that it actually was a compression of nanometric objects led to further unanticipated observations. These films could be compressed far beyond the documented film "collapse", eventually leading to the buildup of two superimposed, less-organized bilayers of diblocks on top of the initially formed monolayer of hemimicelles. Remarkably, the latter withstood the final, irreversible collapse of the composite films. "Gemini" tetrablocks, di(FnHm), with two Fn-chains and two Hm-chains, provided two superposed layers of discrete micelles, apparently the first example of thin films made of stacked discrete self-assembled nanoobjects. Decoration of solid surfaces with domains of predetermined size of these small "nonpolar" molecules is straightforward. Initial examples of applications include deposition of metal dots and catalytic oxidation of CO, and nanopatterning of SiO(2) films.

  8. Reactivity trends of hydroxide ion attack on high spin Fe(II complexes including bromosalicylidene amino acid ligands in some mixed aqueous solvents: Gibb’s Free Energy of Transfer and initial-transition state analysis

    Directory of Open Access Journals (Sweden)

    Laila H. Abdel-Rahman

    2017-05-01

    Full Text Available The kinetics of hydroxide ion attack on bis(bromosalicylidene alanateiron (II (bsali, bis(bromosalicylidene phenylalanateiron(II (bsphali, bis(bromosalicylidene aspartateiron(II (bsasi, (bromosalicylidene histidinateiron(II (bshi, bis(bromosalicylidene arginateiron(II (bsari have been reported in different binary aqueous solvent mixtures at 298 K. The observed reactivity trends are discussed in terms of the hydrophilic and hydrophobic forms of the complexes investigated, as well as the transfer chemical potentials of hydroxide ion and the complex. Both the solvent–solute and solvent–solvent interactions have been considered. The hydrophobic character of the complexes studied was manifested by decreasing in reactivity. Solvent effect on reactivity trends of the investigated complexes has been analyzed into initial and transition state components by using the transfer chemical potentials of the reactants and the kinetic data of the studied compounds. The decrease in the observed rate constant values (kobs of the base hydrolysis of the investigated complexes with increasing of solvent % is dominated by the initial state (IS.

  9. Solvent effects on microstructures and properties of three-dimensional hierarchical TiO2 microsphere structures synthesized via solvothermal approach

    Science.gov (United States)

    Xu, Shiping; Sun, Xiang; Gao, Yuan; Yue, Min; Yue, Qinyan; Gao, Baoyu

    2017-09-01

    One-step solvothermal method has been proved to be a simple and efficient route to synthesize three-dimensional (3D) hierarchical TiO2 microsphere structures, but discrepant properties of the solvent media had been claimed as the major factors determining microstructures and properties of the final products. In this study, several typical solvents, including alkane, aromatic hydrocarbons, halohydrocarbon, ketone, organic acid, mono- and dihydric alcohols, were selected to comprehensively investigate the effect of solvents on the morphology, crystal structure, specific surface area, porous property and light harvesting capability of the final products. According to the experimental results, a good interface separating titanium precursor with aqueous phase in the reaction solution, created by non-polar solvents, or polar solvents which are immiscible with titanium precursor, was the decisive factor for the formation of quasi-3D urchin-like TiO2 microspheres self-assembled from one-dimensional (1D) nanostructures, and concentrated H+ induced by organic acid medium was also helpful. Meanwhile, without the liquid-liquid interface or extremely low solution pH, anatase TiO2 sphere structures with big specific surface area comprising of nanoparticles or nanosheets would be formed, and performed well in photodegradation of pollutants in water.

  10. Temperature dependence of the positronium yields in polar and nonpolar pure liquids; an experimental test of a phenomenological model

    Energy Technology Data Exchange (ETDEWEB)

    Levay, B

    2004-08-02

    A phenomenological model describing the temperature dependence of the positronium yields (I{sub Ps}, %) was tested in pure liquids of different polarity. The investigated solvents were: m-xylene (m-Xy) and iso-octane (i-C8) as aromatic and aliphatic nonpolar hydrocarbons, methanol (MeOH), water and dimethyl formamide as polar solvents with and without OH group. Arrhenius type linear relationship predicted by the model for the lnQ vs 1/T function, where Q=(100/I{sub Ps}-1), was found to be valid in all cases. The slopes of the lines correspond to the activation energy differences ({delta}E{sup *}=E{sub rec}-E{sub Ps}) between the two main competing reaction pathways in the positron spur, i.e., solvent recombination (e{sup -} + M{sup +}) and positronium formation (e{sup -} + e{sup +}). The slopes were positive, i.e., {delta}E{sup *}<0 and E{sub rec}

  11. Predicting Partitioning and Diffusion Properties of Nonpolar Chemicals in Biotic Media and Passive Sampler Phases by GC × GC.

    Science.gov (United States)

    Nabi, Deedar; Arey, J Samuel

    2017-02-14

    The chemical parameters needed to explain and predict bioavailability, biodynamics, and baseline toxicity are not readily available for most nonpolar chemicals detected in the environment. Here, we demonstrate that comprehensive two-dimensional gas chromatography (GC × GC) retention times can be used to predict 26 relevant properties for nonpolar chemicals, specifically: partition coefficients for diverse biotic media and passive sampler phases; aquatic baseline toxicity; and relevant diffusion coefficients. The considered biotic and passive sampler phases include membrane and storage lipids, serum and muscle proteins, carbohydrates, algae, mussels, polydimethylsiloxane, polyethylene, polyoxymethylene, polyacrylate, polyurethane, and semipermeable membrane devices. GC × GC-based chemical property predictions are validated with a compilation of 1038 experimental property data collected from the literature. As an example application, we overlay a map of baseline toxicity to fathead minnows onto the separated analyte signal of a polychlorinated alkanes (chlorinated paraffins) technical mixture that contains 7820 congeners. In a second application, GC × GC-estimated properties are used to parametrize multiphase partitioning models for mammalian tissues and organs. In a third example, we estimate chemical depuration kinetics for mussels. Finally, we illustrate an approach to screen the GC × GC chromatogram for nonpolar chemicals of potentially high concern, defined based on their GC × GC-estimated biopartitioning properties, diffusion properties, and baseline toxicity.

  12. Coherent Control of Vibrational State Population in a Nonpolar Molecule

    CERN Document Server

    Picón, A; Jaron-Becker, A; Becker, A; 10.1103/PhysRevA.83.023412

    2011-01-01

    A coherent control scheme for the population distribution in the vibrational states of nonpolar molecules is proposed. Our theoretical analysis and results of numerical simulations for the interaction of the hydrogen molecular ion in its electronic ground state with an infrared laser pulse reveal a selective two-photon transition between the vibrational states via a coupling with the first excited dissociative state. We demonstrate that for a given temporal intensity profile the population transfer between vibrational states, or a superposition of vibrational states, can be made complete for a single chirped pulse or a train of chirped pulses, which accounts for the accumulated phase difference due to the AC Stark effect. Effects of a spatial intensity (or, focal) averaging are discussed.

  13. Polarity inversion in polar-nonpolar-polar heterostructures.

    Science.gov (United States)

    Cho, S; Youn, S J; Kim, Y; DiVenere, A; Wong, G K; Freeman, A J; Ketterson, J B

    2001-09-17

    We have observed an epilayer-thickness-dependent polarity inversion for the growth of CdTe on Sb(Bi)/CdTe(111)B. For films with Sb(Bi) thicknesses of less than 40 A (15 A), the CdTe layer shows a B (Te-terminated) face, but it switches to an A (Cd-terminated) face for thicker layers. On the other hand, a CdTe layer grown on Bi(Sb)/CdTe(111)A always shows the A face regardless of Sb or Bi layer thicknesses. In order to address the observations we have performed ab initio calculations, which suggest that the polarity of a polar material on a nonpolar one results from the binding energy difference between the two possible surface configurations.

  14. Solvent Extraction and Characterization of Neutral Lipids in Oocystis sp.

    Directory of Open Access Journals (Sweden)

    Renil eAnthony

    2015-01-01

    Full Text Available Microalgae are a favorable feedstock for bioproducts and biofuels due to their high oil content, fast growth rates and low resource demands. Solvent lipid extraction efficiency from microalgae is dependent on algal strain and the extraction solvent. Four non-polar extraction solvents were evaluated for the recovery of neutral cellular lipids from microalgae Oocystis sp. (UTEX LB2396. Methylene chloride, hexane, diethyl ether, and cyclohexane were selected as the extraction solvents. All solvent extracts contained hexadecanoic acid, linoleic acid and linolenic acid; accounting for 70% of total lipid content with a proportional wt% composition of the three fatty acids, except for the hexane extracts that showed only hexadecanoic acid and linoleic acid. While not statistically differentiated, methylene chloride proved to be the most effective solvent for Oocystis sp. among the four solvents tested with a total average neutral lipid recovery of 0.25% of dry weight followed by diethyl ether (0.18%, cyclohexane (0.14% and hexane (0.11%. This research presents a simple methodology to optimize the selection of lipid specific extraction solvents for the microalgal strain selected.

  15. Variability of non-polar secondary metabolites in the red alga Portieria.

    Science.gov (United States)

    Payo, Dioli Ann; Colo, Joannamel; Calumpong, Hilconida; de Clerck, Olivier

    2011-01-01

    Possible sources of variation in non-polar secondary metabolites of Portieria hornemannii, sampled from two distinct regions in the Philippines (Batanes and Visayas), resulting from different life-history stages, presence of cryptic species, and/or spatiotemporal factors, were investigated. PCA analyses demonstrated secondary metabolite variation between, as well as within, five cryptic Batanes species. Intraspecific variation was even more pronounced in the three cryptic Visayas species, which included samples from six sites. Neither species groupings, nor spatial or temporal based patterns, were observed in the PCA analysis, however, intraspecific variation in secondary metabolites was detected between life-history stages. Male gametophytes (102 metabolites detected) were strongly discriminated from the two other stages, whilst female gametophyte (202 metabolites detected) and tetrasporophyte (106 metabolites detected) samples were partially discriminated. These results suggest that life-history driven variations, and possibly other microscale factors, may influence the variation within Portieria species.

  16. Variability of Non-Polar Secondary Metabolites in the Red Alga Portieria

    Directory of Open Access Journals (Sweden)

    Olivier de Clerck

    2011-11-01

    Full Text Available Possible sources of variation in non-polar secondary metabolites of Portieria hornemannii, sampled from two distinct regions in the Philippines (Batanes and Visayas, resulting from different life-history stages, presence of cryptic species, and/or spatiotemporal factors, were investigated. PCA analyses demonstrated secondary metabolite variation between, as well as within, five cryptic Batanes species. Intraspecific variation was even more pronounced in the three cryptic Visayas species, which included samples from six sites. Neither species groupings, nor spatial or temporal based patterns, were observed in the PCA analysis, however, intraspecific variation in secondary metabolites was detected between life-history stages. Male gametophytes (102 metabolites detected were strongly discriminated from the two other stages, whilst female gametophyte (202 metabolites detected and tetrasporophyte (106 metabolites detected samples were partially discriminated. These results suggest that life-history driven variations, and possibly other microscale factors, may influence the variation within Portieria species.

  17. ASSOCIATION OF ETHYLENE VINYL ACETATE COPOLYMER IN DILUTE SOLUTIONS Ⅳ.SOLVENT MIXTURE AND ADDITIVE EFFECT ON CA

    Institute of Scientific and Technical Information of China (English)

    Jin-wen Qian; Jing Li; Guo-rong Qi; Lin-xian Feng

    1999-01-01

    Critical association concentration (CA) of ethylene-vinyl acetate copolymer (EVA) in selective solvent mixtures of 1,2-dichloroethane (DCE) (polar solvent) and cyclohexane (CYH) (non-polar solvent)was investigated. DCE is a good solvent for polyvinyl acetate (PVAc) and a poor solvent for paraffin,whereas CYH is a good solvent for the paraffin and a precipitant for PVAc. Viscosities of EVA in different compositions of the solvent mixture with and without additives were measured. Viscosity results were used to determine the CA value of the systems. It is shown that CA was markedly dependent on the composition of the solvent mixture and concentration and structure of the additive. Solvation and competition between hydrogen bonding and micellisation were suggested for qualitative description of the changing of CA value observed.

  18. ON THE APPROXIMATION OF SOLVENT EFFECTS ON THE CONFORMATION AND DYNAMICS OF CYCLOSPORIN A BY STOCHASTIC DYNAMICS SIMULATION TECHNIQUES

    NARCIS (Netherlands)

    Shi Yun-yu, [No Value; Wang Lu, [No Value; Van Gunsteren, W. F.

    1988-01-01

    The molecular simulation technique of stochastic dynamics (SD) is tested by application to the immunosuppressive drug cyclosporin A (CPA). Two stochastic dynamics simulations are performed, one (SDCCl4) with atomic friction coefficients proportional to the viscosity of the nonpolar solvent CCl4, and

  19. Effect of Solvents on the Product Distribution and Reaction Rate of a Buchwald-Hartwig Amination Reaction

    DEFF Research Database (Denmark)

    Christensen, H.; Kiil, Søren; Dam-Johansen, Kim;

    2006-01-01

    The Buchwald-Hartwig amination reaction between p-bromotoluene and piperazine in the presence of the homogeneous catalytic system Pd(dba)(2)/(+/-)-BINAP and the base NaO-t-Bu was investigated in two different classes of solvents: aprotic, nonpolar and aprotic, polar. The reaction was carried out...... solvent for the Buchwald-Hartwig amination reaction under the conditions applied was m-xylene....

  20. Defensive Armor of Potato Tubers: Nonpolar Metabolite Profiling, Antioxidant Assessment, and Solid-State NMR Compositional Analysis of Suberin-Enriched Wound-Healing Tissues.

    Science.gov (United States)

    Dastmalchi, Keyvan; Kallash, Linda; Wang, Isabel; Phan, Van C; Huang, Wenlin; Serra, Olga; Stark, Ruth E

    2015-08-05

    The cultivation, storage, and distribution of potato tubers are compromised by mechanical damage and suboptimal healing. To investigate wound-healing progress in cultivars with contrasting russeting patterns, metabolite profiles reported previously for polar tissue extracts were complemented by GC/MS measurements for nonpolar extracts and quantitative (13)C NMR of interfacial solid suspensions. Potential marker compounds that distinguish cultivar type and wound-healing time point included fatty acids, fatty alcohols, alkanes, glyceryl esters, α,ω-fatty diacids, and hydroxyfatty acids. The abundant long-chain fatty acids in nonpolar extracts and solids from the smooth-skinned Yukon Gold cultivar suggested extensive suberin biopolymer formation; this hypothesis was supported by high proportions of arenes, alkenes, and carbonyl groups in the solid and among the polar markers. The absence of many potential marker classes in nonpolar Atlantic extracts and interfacial solids suggested a limited extent of suberization. Modest scavenging activities of all nonpolar extracts indicate that the majority of antioxidants produced in response to wounding are polar.

  1. Non-polar Extraction Effect Analysis of Mimusops elengi (L. bark to Larvae of Aedes aegypti (L.

    Directory of Open Access Journals (Sweden)

    Mutiara Widawati

    2012-11-01

    Full Text Available Tanjung or Mimusops elengi is one of a tree that has many therapeutic effects and has been widely studied as an alternative drug like anti-inflammatory agent, diarrhea, and asthma. This study tested the larvicidal ability of Tanjung bark extract for larvae of Aedes aegypti. The solvent that will be used for Mimusops elengi stem extraction in this research is semi-polar and non-polar solvent, which is ethyl acetate and hexane. The method used in this research was reflux extraction and proceed further with fractionation that has been analyzed by thin layer chromatography. The larvicidal activity of Mimusops elengi extract was tested using a bioassay method that has been established by WHO to determine LC50 and LC9O which can be processed further in order to compare the ejjicacy ofsolvent used. The LC50 value of the extract 1,2 and 3, were each 59.36 ppm, 82.53 ppm, and 110.42 ppm. The experimental results showed that hexane has the most powerful larvicidal ability compared to other extracts.

  2. The solvent component of macromolecular crystals

    Energy Technology Data Exchange (ETDEWEB)

    Weichenberger, Christian X. [European Academy of Bozen/Bolzano (EURAC), Viale Druso 1, Bozen/Bolzano, I-39100 Südtirol/Alto Adige (Italy); Afonine, Pavel V. [Lawrence Berkeley National Laboratory (LBNL), 1 Cyclotron Road, Mail Stop 64R0121, Berkeley, CA 94720 (United States); Kantardjieff, Katherine [California State University, San Marcos, CA 92078 (United States); Rupp, Bernhard, E-mail: br@hofkristallamt.org [k.-k. Hofkristallamt, 991 Audrey Place, Vista, CA 92084 (United States); Medical University of Innsbruck, Schöpfstrasse 41, A-6020 Innsbruck (Austria)

    2015-04-30

    On average, the mother liquor or solvent and its constituents occupy about 50% of a macromolecular crystal. Ordered as well as disordered solvent components need to be accurately accounted for in modelling and refinement, often with considerable complexity. The mother liquor from which a biomolecular crystal is grown will contain water, buffer molecules, native ligands and cofactors, crystallization precipitants and additives, various metal ions, and often small-molecule ligands or inhibitors. On average, about half the volume of a biomolecular crystal consists of this mother liquor, whose components form the disordered bulk solvent. Its scattering contributions can be exploited in initial phasing and must be included in crystal structure refinement as a bulk-solvent model. Concomitantly, distinct electron density originating from ordered solvent components must be correctly identified and represented as part of the atomic crystal structure model. Herein, are reviewed (i) probabilistic bulk-solvent content estimates, (ii) the use of bulk-solvent density modification in phase improvement, (iii) bulk-solvent models and refinement of bulk-solvent contributions and (iv) modelling and validation of ordered solvent constituents. A brief summary is provided of current tools for bulk-solvent analysis and refinement, as well as of modelling, refinement and analysis of ordered solvent components, including small-molecule ligands.

  3. Diamex solvent regeneration studies

    Energy Technology Data Exchange (ETDEWEB)

    Nicol, C.; Cames, B.; Margot, L.; Ramain, L. [CEA/VALRHO - site de Marcoule, Dept. de Recherche en Retraitement et en Vitrification, DRRV, 30 - Marcoule (France)

    2000-07-01

    The CEA has undertaken the development of the DIAMEX process as the first step in the strategy aiming at recovering minor actinides which could then be transmuted or separately conditioned. The scientific feasibility of this process was demonstrated during counter current hot tests operated in 1993. Then experimental works were conducted, on one hand to optimise the extractant formula, on the other hand to improve the flowsheet. Reference extractant and flowsheet were then chosen, respectively in 1995 and 1996. The next step, still in progress, is the demonstration of the DIAMEX technical feasibility (in 2002); this means that the flowsheet should include solvent regeneration treatments. In this aim, degradation studies were performed to quantify main degradation products, and identify those which could be disturbing in the process. This paper deals with experimental studies performed with intend to propose a regeneration treatment, included in the flowsheet, so that the solvent could be recycled. It comprises: - Quantification of the main degradation products issued from radiolysis or hydrolysis, which are methyl octyl amine (MOA) and carboxylic acids; - Effects of these products on extracting and hydrodynamics performances of the process; - Study of methods able to remove mainly disturbing degradation products. Acidic scrubbing, which are performed in the scrubbing and stripping sections of the DIAMEX process, should allow the quantitative removal of methyl octyl amine. Then basic scrubbings, which were more especially studied, should eliminate at least 80% of carboxylic acids, and part of the cations remaining in the solvent. (authors)

  4. Solvent Immersion Imprint Lithography

    Energy Technology Data Exchange (ETDEWEB)

    Vasdekis, Andreas E.; Wilkins, Michael J.; Grate, Jay W.; Kelly, Ryan T.; Konopka, Allan; Xantheas, Sotiris S.; Chang, M. T.

    2014-06-21

    The mechanism of polymer disolution was explored for polymer microsystem prototyping, including microfluidics and optofluidics. Polymer films are immersed in a solvent, imprinted and finally brought into contact with a non-modified surface to permanently bond. The underlying polymer-solvent interactions were experimentally and theoretically investigated, and enabled rapid polymer microsystem prototyping. During imprinting, small molecule integration in the molded surfaces was feasible, a principle applied to oxygen sensing. Polystyrene (PS) was employed for microbiological studies at extreme environmental conditions. The thermophile anaerobe Clostridium Thermocellum was grown in PS pore-scale micromodels, revealing a double mean generation lifetime than under ideal culture conditions. Microsystem prototyping through directed polymer dissolution is simple and accessible, while simultaneous patterning, bonding, and surface/volume functionalization are possible in less than one minute.

  5. Influence of Nonpolar Substances on the Extraction Efficiency of Six Alkaloids in Zoagumhwan Investigated by Ultra Performance Liquid Chromatography and Photodiode Array Detection

    Directory of Open Access Journals (Sweden)

    Shijing Liu

    2012-11-01

    Full Text Available A reverse phase ultra performance liquid chromatography and photodiode array (UPLC-PDA detection method was established for the determination of six alkaloids in Zoagumhwan (ZGW, and further for investigating the influence of nonpolar substances on the extraction efficiency of these alkaloids. The method was based on a BEH C18 (50 mm × 2.1 mm, 1.7 μm column and mobile phase of aqueous phosphoric acid and acetonitrile including 0.05% buffer solution under gradient elution. ZGW samples of ZGW I, II, III and IV were obtained and prepared by pre-processing the crude materials of Coptidis rhizoma and Evodiae fructus using four technologies, namely direct water decoction, removal of nonpolar substances in Evodiae fructus by supercritical fluid extraction (SFE, removal of nonpolar substances in ZGW by SFE and removal of nonpolar substances in ZGW by steam distillation. The developed and validated UPLC-PDA method was precise, accurate and sensitive enough based on the facts that the six alkaloids showed good regression (r > 0.9998, the limit of detections and quantifications for six alkaloids were less than 28.8 and 94.5 ng/mL, respectively, and the recovery was in the range of 98.56%–103.24%. The sequence of the total contents of six alkaloids in these samples was ZGW II > ZGW IV > ZGW III > ZGW I. ZGW II, in which nonpolar substances, including essential oils, were firstly removed from Evodiae fructus by SFE, had the highest content of the total alkaloids, indicating that extraction efficiency of the total alkaloids could be remarkably increased after Evodiae fructus being extracted by SFE.

  6. Density and Phase State of a Confined Nonpolar Fluid

    Science.gov (United States)

    Kienle, Daniel F.; Kuhl, Tonya L.

    2016-07-01

    Measurements of the mean refractive index of a spherelike nonpolar fluid, octamethytetracylclosiloxane (OMCTS), confined between mica sheets, demonstrate direct and conclusive experimental evidence of the absence of a first-order liquid-to-solid phase transition in the fluid when confined, which has been suggested to occur from previous experimental and simulation results. The results also show that the density remains constant throughout confinement, and that the fluid is incompressible. This, along with the observation of very large increases (many orders of magnitude) in viscosity during confinement from the literature, demonstrate that the molecular motion is limited by the confining wall and not the molecular packing. In addition, the recently developed refractive index profile correction method, which enables the structural perturbation inherent at a solid-liquid interface and that of a liquid in confinement to be determined independently, was used to show that there was no measurable excess or depleted mass of OMCTS near the mica surface in bulk films or confined films of only two molecular layers.

  7. Design of non-polarizing thin film edge filters

    Institute of Scientific and Technical Information of China (English)

    GU Pei-fu; ZHENG Zhen-rong

    2006-01-01

    The separation between s- and p-polarization components invariably affects thin film edge filters used for tilted incidence and is a difficult problem for many applications, especially for optical communication. This paper presents a novel design method to obtain edge filters with non-polarization at incidence angle of 45°. The polarization separation at 50% transmittance for a long-wave-pass filter and a short-wave-pass filter is 0.3 nm and 0.1 nm respectively. The design method is based on a broadband Fabry-Perot thin-film interference filter in which the higher or lower interference band at both sides of the main transmittance peak can be used for initial design of long-wave-pass filter or short-wave-pass filter and then can be refined to reduce the transmittance ripples. The spacer 2H2L2H or 2L2H2L of the filter is usually taken. Moreover, the method for expanding the bandwidth of rejection and transmission is explained. The bandwidth of 200 nm for both rejection region and transmission band is obtained at wavelength 1550 nm. In this way, the long-wave-pass and short-wave-pass edge filters with zero separation between two polarization components can easily be fabricated.

  8. Dramatic effects of halogen substitution and solvent on the rates and mechanisms of nucleophilic substitution reactions of aziridines.

    Science.gov (United States)

    Banks, Harold D

    2008-04-04

    In a previous study we reported that fluorine substitution at the carbon positions of aziridine results in profound enhancements of the rate of reaction with ammonia, a typical nucleophile, in the gas phase. In this study the investigation is extended to include chloro- and bromoaziridines. Because syntheses are largely performed in the condensed phase, the present computational investigation [(MP2(Full)/6-311++G(d,p)//MP2(Full)/6-31+G(d) level] was conducted with three typical solvents that cover a wide range of polarity: THF, CH3CN, and H2O. Nucleophiles can react with haloaziridines 1 by displacing a substituted amide ion by means of an SN2 mechanism (pathway a), producing 1,2-diaminohaloethanes (from the initially formed dipolar species 2). Alternatively, a rearrangement mechanism involving rate-determining departure of a halide ion (pathway b) to form an imidoyl halide, 3, is possible. Transition-state theory was used to compute relative reaction rates of these mechanistic possibilities and to assess the role of the halogen substituents and the reaction solvent. Gas-phase results provided the basis of mechanistic insights that were more apparent in the absence of intermolecular interactions. Fluoroaziridines were found to react at accelerated rates relative to aziridine exclusively by means of the a Menshutkin-type mechanism (SN2) in each solvent tested, while the reactions of the chloro- and bromoaziridines could be directed toward 2 in the highly nonpolar solvent, cyclohexane, or toward 3 in the more polar solvents. An assessment is made of the feasibility of using this chemistry of the haloazirdines in the synthetic laboratory.

  9. Waste reduction using carbon dioxide: A solvent substitute for precision cleaning applications

    Energy Technology Data Exchange (ETDEWEB)

    Phelphs, M.R.; Hogan, M.O.; Snowden-Swan, L.J. [and others

    1995-05-01

    The U.S. Department of Energy`s (DOE) Industrial Waste Program (IWP) has been sponsoring the research, development, and commercialization of supercritical fluid cleaning technology for replacement of traditional solvent cleaning processes. Los Alamos National Laboratory and Pacific Northwest Laboratory have been working through this collaborative effort to test the efficacy of carbon dioxide (CO{sub 2}) cleaning. Tests were performed on a variety of substrates at various solvent conditions for a large number of common contaminants to characterize cleaning performance. Cleaning efficiencies with respect to system dynamics were also studied. Results of these tests show that supercritical and near-critical carbon dioxide is not only an effective solvent for precision cleaning applications of parts such as gyroscopes, bearing assemblies, and machine tools but is also feasible for bulk cleaning operations for a variety of industrial needs. It has been tested and shown to be effective for a range of substrates including laser optics components, computer disk drives, and cloth rags. Metals, including stainless steel, beryllium, gold, silver, copper and others; ceramics; and elastomeric seals such as Teflon, silicone, and epoxy potting compounds are highly compatible with SuperCritical CO{sub 2} (SCCO{sub 2}). Many contaminants, including silicones, Krytox, hydrocarbons, esters, fluorocarbons, gyroscope damping and fill fluids, and machining oils and lubricating oils, will dissolve in SCCO{sub 2}. In general, nonpolar, hydrophobic contaminants such as oils dissolve well, while hydrophilic contaminants such as inorganic salts do not. The parts and contaminants mentioned here are not the only applications for SCCO, cleaning, as the full range of possibilities is still being defined by developers and users of the technology. The many advantages of SCCO{sub 2} indicate that it is a technology that should carry industrial cleaning operations into the future.

  10. Metabolic Activation of Nonpolar Sediment Extracts Results in enhanced Thyroid Hormone Disrupting Potency

    NARCIS (Netherlands)

    Montano, M.; Weiss, J.; Hoffmann, L.; Gutleb, A.C.; Murk, A.J.

    2013-01-01

    Traditional sediment risk assessment predominantly considers the hazard derived from legacy contaminants that are present in nonpolar sediment extracts, such as polychlorinated biphenyls (PCBs), dioxins, furans (PCDD/Fs), and polyaromatic hydrocarbons (PAHs). Although in vivo experiments with these

  11. Acousto-optic modulation and deflection of terahertz electromagnetic radiation in nonpolar liquids

    Science.gov (United States)

    Nikitin, P. A.; Voloshinov, V. B.; Gerasimov, V. V.; Knyazev, B. A.

    2017-07-01

    The results of a series of experiments on controlled deflection of electromagnetic radiation of a free-electron laser upon diffraction by an acoustic wave in nonpolar liquids are presented. Acoustic and optical properties of liquids that are transparent in the terahertz range are discussed. It is demonstrated that nonpolar liquids may turn out to be a more efficient acousto-optic interaction medium than dielectric crystals or semiconductors.

  12. Polar-Nonpolar Radical Copolymerization under Li+ Catalysis

    Science.gov (United States)

    2008-09-21

    description of our copolymerization results. The polyisobutylene (b- PIB ) that is produced by homopolymerization of IB in an inert solvent such as 1,2...the linear polyisobutylene (l- PIB ) produced under the usual cationic initiation. The difference is clear in spectral (NMR) and physical (DSC, TGA...HPLC) properties. A detailed 2D-NMR examination of b- PIB obtained from ordinary IB and several isotopically labeled versions of IB revealed that its

  13. Critical concentration of ion-pairs formation in nonpolar media.

    Science.gov (United States)

    Dukhin, Andrei

    2014-07-01

    It is known that nonpolar liquids can be ionized by adding surfactants, either ionic or nonionic. Surfactant molecules serve as solvating agents, building inverse micelles around ions, and preventing their association back into neutral molecules. According to the Bjerrum-Onsager-Fuoss theory, these inverse micelle ions should form "ion pairs." This, in turn, leads to nonlinear dependence of the conductivity on the concentration. Surprisingly, ionic surfactants exhibit linear conductivity dependence, which implies that these inverse micelle ions do not form ion pairs. Theory predicts the existence of two ionic strength ranges, which are separated by a certain critical ion concentration. Ionic strength above the critical one is proportional to the square root of the ion concentration, whereas it becomes linear below the critical concentration. Critical ion concentration lies within the range of 10(-11) -10(-7) mol/L when ion size ranges from 1 to 3 nm. Critical ion concentration is related, but not equal, to a certain surfactant concentration (critical concentration of ion-pairs formation (CIPC)) because only a fraction of the surfactant molecules is incorporated into the micelles ions. The linear conductivity dependence for ionic surfactants indicates that the corresponding CIPC is above the range of studied concentrations, perhaps, due to rather large ion size. The same linearity is a sign that charged inverse micelles structure and fraction are concentration independent due to strong charge-dipole interaction in the charge micelle core. This also proves that CIPC is independent of critical concentration of micelle formation. Nonionic surfactants, on the other hand, exhibit nonlinear conductivity dependence apparently due to smaller ion sizes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. The influence of non-polar lipids on tear film dynamics

    KAUST Repository

    Bruna, M.

    2014-04-04

    © 2014 Cambridge University Press. In this paper we examine the effect that physiological non-polar lipids, residing on the surface of an aqueous tear film, have on the film evolution. In our model we track the evolution of the thickness of the non-polar lipid layer, the thickness of the aqueous layer and the concentration of polar lipids which reside at the interface between the two. We also utilise a force balance in the non-polar lipid layer in order to determine its velocity. We show how to obtain previous models in the literature from our model by making particular choices of the parameters. We see the formation of boundary layers in some of these submodels, across which the concentration of polar lipid and the non-polar lipid velocity and film thickness vary. We solve our model numerically for physically realistic parameter values, and we find that the evolution of the aqueous layer and the polar lipid layer are similar to that described by previous authors. However, there are interesting dynamics for the non-polar lipid layer. The effects of altering the key parameters are highlighted and discussed. In particular, we see that the Marangoni number plays a key role in determining how far over the eye the non-polar lipid spreads.

  15. Mechanism of Nonpolar Model Substances to Inhibit Primary Gushing Induced by Hydrophobin HFBI.

    Science.gov (United States)

    Shokribousjein, Zahra; Riveros Galan, David; Losada-Pérez, Patricia; Wagner, Patrick; Lammertyn, Jeroen; Arghir, Iulia; Golreihan, Asefeh; Verachtert, Hubert; Aydın, Ahmet Alper; De Maeyer, Marc; Titze, Jean; Ilberg, Vladimír; Derdelinckx, Guy

    2015-05-13

    In this work, the interactions of a well-studied hydrophobin with different types of nonpolar model substances and their impact on primary gushing is evaluated. The nature, length, and degree of saturation of nonpolar molecules are key parameters defining the gushing ability or inhibition. When mixed with hydrophobins, the nonpolar molecule-hydrophobin assembly acts as a less gushing or no gushing system. This effect can be explained in the framework of a competition effect between non-polar systems and CO2 to interact with the hydrophobic patch of the hydrophobin. Interactions of these molecules with hydrophobins are promoted as a result of the similar size of the nonpolar molecules with the hydrophobic patch of the protein, at the expense of the formation of nanobubbles with CO2. In order to prove the presence of interactions and to unravel the mechanisms behind them, a complete set of experimental techniques was used. Surface sensitive techniques clearly show the presence of the interactions, whose nature is not covalent nor hydrogen bonding according to infrared spectroscopy results. Interactions were also reflected by particle size analysis in which mixtures of particles displayed larger size than their pure component counterparts. Upon mixing with nonpolar molecules, the gushing ability of the protein is significantly disrupted.

  16. Miscellaneous hydrocarbon solvents.

    Science.gov (United States)

    Bebarta, Vikhyat; DeWitt, Christopher

    2004-08-01

    The solvents discussed in this article are common solvents not categorized as halogenated, aromatic, or botanical. The solvents discussed are categorized into two groups: hydrocarbon mixtures and single agents. The hydrocarbon mixtures discussed are Stoddard solvent, naphtha, and kerosene. The remaining solvents described are n-hexane, methyl n-butyl ketone, dimethylformamide, dimethyl sulfoxide, and butyl mercaptans. Effects common to this group of agents and their unique effects are characterized. Treatment of exposures and toxic effects of these solvents is described, and physiochemical properties and occupational exposure levels are listed.

  17. Deviations from sorption linearity on soils of polar and nonpolar organic compounds at low relative concentrations

    Science.gov (United States)

    Chiou, C.T.; Kile, D.E.

    1998-01-01

    A series of single-solute and binary-solute sorption data have been obtained on representative samples of polar compounds (substituted ureas and phenolic compounds) and of nonpolar compounds (e.g., EDB and TCE) on a peat soil and a mineral (Woodburn) soil; the data extend to low relative solute concentrations (C(e)/S(w)). At relatively low C(e)/S(w), both the nonpolar and the polar solutes exhibit nonlinear sorption. The sorption nonlinearity approaches apparent saturation at about C(e)/S(w) = 0.010-0.015 for the nonpolar solutes and at about C(e)/S(w) = 0.10-0.13 for the polar solutes; above these C(e)/S(w) regions, the isotherms are practically linear. The nonlinear sorption capacities are greater for polar solutes than for nonpolar solutes and the peat soil shows a greater effect than the Woodburn soil. The small nonlinear sorption capacity for a nonpolar solute is suppressed indiscriminately by either a nonpolar or a polar cosolute at relatively low C(e)/S(w) of the cosolute. By contrast, the abilities of different cosolutes to suppress the nonlinear capacity of a nominal polar solute differ drastically. For polar solutes, a nonpolar cosolute exhibits a limited suppression even at high cosolute C(e)/S(w); effective suppression occurs when the cosolute is relatively polar and at various C(e)/S(w). These differences suggest that more than a single mechanism is required to account for the nonlinear sorption of both nonpolar and polar compounds at low C(e)/S(w). Mechanistic processes consistent with these observations and with soil surface areas are discussed along with other suggested models. Some important consequences of the nonlinear competitive sorption to the behavior of contaminants in natural systems are discussed.A number of conceptual models was postulated to account for the nonlinear solute sorption on soils of significant soil organic matter. A series of single-solute and binary-route sorption data was obtained representing samples of polar compounds of

  18. Solvent-induced red-shifts for the proton stretch vibrational frequency in a hydrogen-bonded complex. 1. A valence bond-based theoretical approach.

    Science.gov (United States)

    Kiefer, Philip M; Pines, Ehud; Pines, Dina; Hynes, James T

    2014-07-17

    A theory is presented for the proton stretch vibrational frequency νAH for hydrogen (H-) bonded complexes of the acid dissociation type, that is, AH···B ⇔ A(-)···HB(+)(but without complete proton transfer), in both polar and nonpolar solvents, with special attention given to the variation of νAH with the solvent's dielectric constant ε. The theory involves a valence bond (VB) model for the complex's electronic structure, quantization of the complex's proton and H-bond motions, and a solvent coordinate accounting for nonequilibrium solvation. A general prediction is that νAH decreases with increasing ε largely due to increased solvent stabilization of the ionic VB structure A(-)···HB(+) relative to the neutral VB structure AH···B. Theoretical νAH versus 1/ε slope expressions are derived; these differ for polar and nonpolar solvents and allow analysis of the solvent dependence of νAH. The theory predicts that both polar and nonpolar slopes are determined by (i) a structure factor reflecting the complex's size/geometry, (ii) the complex's dipole moment in the ground vibrational state, and (iii) the dipole moment change in the transition, which especially reflects charge transfer and the solution phase proton potential shapes. The experimental proton frequency solvent dependence for several OH···O H-bonded complexes is successfully accounted for and analyzed with the theory.

  19. Solvent resistant nanofiltration membranes

    OpenAIRE

    Dutczak, S.M.

    2011-01-01

    This thesis describes preparation and characterization of membranes for organic solvent filtration (OSF). The main aim was developing membranes for solvent resistant nanofiltration (SRNF) with molecular weight cut-off below 500 g mol-1.

  20. Solvents in novolak synthesis

    Science.gov (United States)

    Sobodacha, Chet J.; Lynch, Thomas J.; Durham, Dana L.; Paradis, Valerie R.

    1993-09-01

    Novolac resins may be prepared with or without a solvent present. We have found that solvent power greatly affects the properties of the finished resin and thus gives the resist chemist another variable with which to `fine-tune' resist properties. Using designed experiments, we investigated the effect of solvent power, as measured by Hansen's Solubility Parameters, of a number of solvents and solvent mixtures on the final properties of the novolac resin. We found that the relative molecular weight (RMW) and dissolution rate of a novolac resin can be varied by selection of a solvent or solvent mixture with the appropriate polarity and hydrogen- bonding characteristics. The solvent polarity and hydrogen-bonding characteristics may affect the stability of the cresol/formaldehyde transition state, thus causing the observed changes in RMW and dissolution rate.

  1. Solvent-polarity-tuned morphology and inversion of supramolecular chirality in a self-assembled pyridylpyrazole-linked glutamide derivative: nanofibers, nanotwists, nanotubes, and microtubes.

    Science.gov (United States)

    Jin, Qingxian; Zhang, Li; Liu, Minghua

    2013-07-01

    The self-assembly of a low-molecular-weight organogelator into various hierarchical structures has been achieved for a pyridylpyrazole linked L-glutamide amphiphile in different solvents. Upon gel formation, supramolecular chirality was observed, which exhibited an obvious dependence on the polarity of the solvent. Positive supramolecular chirality was obtained in nonpolar solvents, whereas it was inverted into negative supramolecular chirality in polar solvents. Moreover, the gelator molecules self-assembled into a diverse array of nanostructures over a wide scale range, from nanofibers to nanotubes and microtubes, depending on the solvent polarity. Such morphological changes could even occur for the xerogels in the solvent vapors. We found that the interactions between the pyridylpyrazole headgroups and the solvents could subtly change the stacking of the molecules and, hence, their self-assembled nanostructures. This work exemplifies that organic solvents can significantly involve the gelation, as well as tune the structure and properties, of a gel.

  2. The effect of solvent-conditioning on soil organic matter sorption affinity for diuron and phenanthrene.

    Science.gov (United States)

    Ahangar, Ahmad Gholamalizadeh; Smernik, Ronald J; Kookana, Rai S; Chittleborough, David J

    2009-08-01

    The effect of solvent-conditioning on the sorption of diuron and phenanthrene was investigated. The organic carbon-normalized sorption coefficients (K(OC)) for diuron and phenanthrene (determined from single initial concentrations of 0.8mgL(-1) and 1.5mgL(-1), respectively) were consistently higher following solvent-conditioning of a whole soil with five organic solvents (acetonitrile, acetone, methanol, chloroform and dichloromethane). The relative increase in K(OC) was inversely related to the polarity of the conditioning solvent (i.e. greater increases in K(OC) were observed for the least polar solvents: chloroform and dichloromethane). The effect of solvent-conditioning on the sorption properties of the same soil that had been lipid-extracted using accelerated solvent extraction (ASE) was also investigated. Since lipid extraction involves treatment with a non-polar solvent (95:5 dichloromethane:methanol) one may have expected no further increase in K(OC) on solvent-conditioning. On the contrary, the lipid-extracted soil exhibited very similar increases in K(OC) as the whole soil. This demonstrated that lipid removal and solvent-conditioning, which both increased K(OC) for this soil, are quite separate phenomena.

  3. Modeling structure and flexibility of Candida antarctica lipase B in organic solvents

    Directory of Open Access Journals (Sweden)

    Pleiss Jürgen

    2008-02-01

    Full Text Available Abstract Background The structure and flexibility of Candida antarctica lipase B in water and five different organic solvent models was investigated using multiple molecular dynamics simulations to describe the effect of solvents on structure and dynamics. Interactions of the solvents with the protein and the distribution of water molecules at the protein surface were examined. Results The simulated structure was independent of the solvent, and had a low deviation from the crystal structure. However, the hydrophilic surface of CALB in non-polar solvents decreased by 10% in comparison to water, while the hydrophobic surface is slightly increased by 1%. There is a large influence on the flexibility depending on the dielectric constant of the solvent, with a high flexibility in water and a low flexibility in organic solvents. With decreasing dielectric constant, the number of surface bound water molecules significantly increased and a spanning water network with an increasing size was formed. Conclusion The reduced flexibility of Candida antarctica lipase B in organic solvents is caused by a spanning water network resulting from less mobile and slowly exchanging water molecules at the protein-surface. The reduced flexibility of Candida antarctica lipase B in organic solvent is not only caused by the interactions between solvent-protein, but mainly by the formation of a spanning water network.

  4. Vacuum-UV spectroscopy of interstellar ice analogs. II. Absorption cross-sections of nonpolar ice molecules

    CERN Document Server

    Cruz-Diaz, G A; Chen, Y -J; Yih, T -S

    2014-01-01

    Dust grains in cold circumstellar regions and dark-cloud interiors at 10-20 K are covered by ice mantles. A nonthermal desorption mechanism is invoked to explain the presence of gas-phase molecules in these environments, such as the photodesorption induced by irradiation of ice due to secondary ultraviolet photons. To quantify the effects of ice photoprocessing, an estimate of the photon absorption in ice mantles is required. In a recent work, we reported the vacuum-ultraviolet (VUV) absorption cross sections of nonpolar molecules in the solid phase. The aim was to estimate the VUV-absorption cross sections of nonpolar molecular ice components, including CH4, CO2, N2, and O2. The column densities of the ice samples deposited at 8 K were measured in situ by infrared spectroscopy in transmittance. VUV spectra of the ice samples were collected in the 120-160 nm (10.33-7.74 eV) range using a commercial microwave-discharged hydrogen flow lamp. We found that, as expected, solid N2 has the lowest VUV-absorption cros...

  5. Chemically assisted ion beam etching of laser diode facets on nonpolar and semipolar orientations of GaN

    Science.gov (United States)

    Kuritzky, L. Y.; Becerra, D. L.; Saud Abbas, A.; Nedy, J.; Nakamura, S.; DenBaars, S. P.; Cohen, D. A.

    2016-07-01

    We demonstrate a vertical (beam etching (CAIBE) in Cl2 chemistry that is suitable for forming laser diode (LD) facets on nonpolar and semipolar oriented III-nitride devices. The etch profiles were achieved with photoresist masks and optimized CAIBE chamber conditions including the platen tilt angle and Cl2 flow rate. Co-loaded studies showed similar etch rates of ˜60 nm min-1 for (20\\bar{2}\\bar{1}),(20\\bar{2}1), and m-plane orientations. The etched surfaces of LD facets on these orientations are chemically dissimilar (Ga-rich versus N-rich), but were visually indistinguishable, thus confirming the negligible orientation dependence of the etch. Continuous-wave blue LDs were fabricated on the semipolar (20\\bar{2}\\bar{1}) plane to compare CAIBE and reactive ion etch (RIE) facet processes. The CAIBE process resulted in LDs with lower threshold current densities due to reduced parasitic mirror loss compared with the RIE process. The LER, degree of verticality, and model of the 1D vertical laser mode were used to calculate a maximum uncoated facet reflection of 17% (94% of the nominal) for the CAIBE facet. The results demonstrate the suitability of CAIBE for forming high quality facets for high performance nonpolar and semipolar III-N LDs.

  6. Mechanism and energetics of O and O2 adsorption on polar and non-polar ZnO surfaces

    Science.gov (United States)

    Gorai, Prashun; Seebauer, Edmund G.; Ertekin, Elif

    2016-05-01

    Polar surfaces of semiconducting metal oxides can exhibit structures and chemical reactivities that are distinct from their non-polar surfaces. Using first-principles calculations, we examine O adatom and O2 molecule adsorption on 8 different known ZnO reconstructions including Zn-terminated (Zn-ZnO) and O-terminated (O-ZnO) polar surfaces, and non-polar surfaces. We find that adsorption tendencies are largely governed by the thermodynamic environment, but exhibit variations due to the different surface chemistries of various reconstructions. The Zn-ZnO surface reconstructions which appear under O-rich and H-poor environments are found to be most amenable to O and O2 adsorption. We attribute this to the fact that on Zn-ZnO, the O-rich environments that promote O adsorption also simultaneously favor reconstructions that involve adsorbed O species. On these Zn-ZnO surfaces, O2 dissociatively adsorbs to form O adatoms. By contrast, on O-ZnO surfaces, the O-rich conditions required for O or O2 adsorption tend to promote reconstructions involving adsorbed H species, making further O species adsorption more difficult. These insights about O2 adsorption on ZnO surfaces suggest possible design rules to understand the adsorption properties of semiconductor polar surfaces.

  7. Solvent-dependent enthalpic versus entropic anion binding by biaryl substituted quinoline based anion receptors.

    Science.gov (United States)

    Sun, Zhan-Hu; Albrecht, Markus; Raabe, Gerhard; Pan, Fang-Fang; Räuber, Christoph

    2015-01-08

    Anion receptors based on an 8-thiourea substituted quinoline with pentafluorinated (1a) or nonfluorinated (1b) biarylamide groups in the 2-position show similar binding of halide anions with somewhat higher association constants for the more acidic fluorinated derivative. Surprisingly, binding affinities for the halides in the case of the nonfluorinated 1b are similar in nonpolar chloroform or polar DMSO as solvent. Thorough thermodynamic investigations based on NMR van't Hoff analysis show that anion binding in chloroform is mainly enthalpically driven. In DMSO, entropy is the driving force for the binding of the ions with replacement of attached solvent.

  8. Simulation of Nonpolar p-GaN/i-N/n-GaN Solar Cells

    Directory of Open Access Journals (Sweden)

    Ming-Jer Jeng

    2012-01-01

    Full Text Available It is well known that nitride-based devices suffer the polarization effects. A promising way to overcome the polarization effects is growth in a direction perpendicular to the c-axis (nonpolar direction. Nonpolar devices do not suffer polarization charge, and then they have a chance to achieve the high solar efficiency. The understanding of the solar performance of non-polar InGaN-based solar cells will be interesting. For a pin non-polar solar cell with GaN p- and n-cladding layers, the conduction band offset (or barrier height, between an intrinsic layer and n-GaN layer is an important issue correlating to the efficiency and fill factor. The efficiency and fill factor will be seriously degraded due to sufficiently high barrier height. To reduce a high barrier height, some graded layers with an energy bandgap between the energy bandgap of n-GaN and InxGa1−xN intrinsic layer can be inserted to the interface of n-GaN and InxGa1-xN layers. From simulation, it indicates that the insertion of graded layer is an effective method to lower energy barrier when there exists a high energy band offset in non-polar nitride devices.

  9. Adsorption of polar, nonpolar, and substituted aromatics to colloidal graphene oxide nanoparticles.

    Science.gov (United States)

    Wang, Fang; Haftka, Joris J-H; Sinnige, Theo L; Hermens, Joop L M; Chen, Wei

    2014-03-01

    We conducted batch adsorption experiments to understand the adsorptive properties of colloidal graphene oxide nanoparticles (GONPs) for a range of environmentally relevant aromatics and substituted aromatics, including model nonpolar compounds (pyrene, phenanthrene, naphthalene, and 1,3-dichlorobenzene) and model polar compounds (1-naphthol, 1-naphthylamine, 2,4-dichlorophenol, and 2,4-dinitrotoluene). GONPs exhibited strong adsorption affinities for all the test compounds, with distribution coefficients on the order of 10(3)-10(6) L/kg. Adsorption to GONPs is much more linear than to carbon nanotubes (CNTs) and C60, likely because GO nanoflakes are essentially individually dispersed (rendering adsorption sites of similar adsorption energy) whereas CNT/C60 are prone to bundling/aggregation. For a given compound GONPs and CNTs often exhibit different adsorption affinities, which is attributable to the differences in both the morphology and surface chemistry between the two nanomaterials. Particularly, the high surface O-content of GONPs enables strong H-bonding and Lewis acid-base interactions with hydroxyl- and amino-substituted aromatics.

  10. Piezoelectricity and rotostriction through polar and non-polar coupled instabilities in bismuth-based piezoceramics

    Science.gov (United States)

    Acosta, Matias; Schmitt, Ljubomira A.; Cazorla, Claudio; Studer, Andrew; Zintler, Alexander; Glaum, Julia; Kleebe, Hans-Joachim; Donner, Wolfgang; Hoffman, Mark; Rödel, Jürgen; Hinterstein, Manuel

    2016-07-01

    Coupling of order parameters provides a means to tune functionality in advanced materials including multiferroics, superconductors, and ionic conductors. We demonstrate that the response of a frustrated ferroelectric state leads to coupling between order parameters under electric field depending on grain orientation. The strain of grains oriented along a specific crystallographic direction, , is caused by converse piezoelectricity originating from a ferrodistortive tetragonal phase. For hhh> oriented grains, the strain results from converse piezoelectricity and rotostriction, as indicated by an antiferrodistortive instability that promotes octahedral tilting in a rhombohedral phase. Both strain mechanisms combined lead to a colossal local strain of (2.4 ± 0.1) % and indicate coupling between oxygen octahedral tilting and polarization, here termed “rotopolarization”. These findings were confirmed with electromechanical experiments, in situ neutron diffraction, and in situ transmission electron microscopy in 0.75Bi1/2Na1/2TiO3-0.25SrTiO3. This work demonstrates that polar and non-polar instabilities can cooperate to provide colossal functional responses.

  11. New Vistas on the Anionic Polymerization of Styrene in Non-Polar Solvents by Means of Density Functional Theory

    Directory of Open Access Journals (Sweden)

    Hideo Morita

    2016-10-01

    Full Text Available The elementary processes of anionic styrene polymerization in the gas phase and in cyclohexane were studied using M062X (a recently developed density functional theory (DFT method combined with the 6-31+G(d basis sets, in order to clarify the complicated phenomena caused by the association of the active chain-ends and elucidate the details of the polymerization mechanism. Three types of HSt2Li (a model structure of polystyryllithium chain-ends were obtained; the well-known first structure in which Li is coordinated to the side chain, the second structure in which Li is coordinated to the phenyl ring, (both without the penultimate unit coordination, and the third structure in which Li is coordinated to both the chain-end unit and the penultimate styrene unit. Although the third HSt2Li is the most stable as expected, the free energy for the transition state of its reaction with styrene is higher than those for the other two transition states due to its steric hindrance. The free energy for the transition state of the reaction of the second HSt2Li with styrene is the lowest, suggesting that the route through it is the predominant reaction path. The penultimate unit effect, slower addition of styrene to HSt2Li than to HStLi, is attributed to coordination of the penultimate styrene units of the polystyryllithium dimer (one of the starting materials to its Li atoms. The calculated enthalpy for the reaction barrier of the second HSt2Li with styrene in cyclohexane was found to agree with the observed apparent activation energy in benzene.

  12. Handbook of green chemistry, green solvents, supercritical solvents

    CERN Document Server

    Anastas, Paul T; Jessop, Philip G

    2014-01-01

    Green Chemistry is a vitally important subject area in a world where being as green and environmentally sound as possible is no longer a luxury but a necessity. Its applications include the design of chemical products and processes that help to reduce or eliminate the use and generation of hazardous substances. The Handbook of Green Chemistry comprises 12 volumes, split into subject-specific sets as follows: Set I: Green Catalysis Set II: Green Solvents Volume 4: Supercritical Solvents Volume 5: Reactions in Water Volume 6: Ionic Liquids

  13. Molecular dynamics study of self-agglomeration of charged fullerenes in solvents.

    Science.gov (United States)

    Banerjee, Soumik

    2013-01-28

    The agglomeration of fullerenes in solvents is an important phenomenon that is relevant to controlled synthesis of fullerene-based nanowires as well as fullerene-based composites. The molecular aggregation in solvents depends on the atomistic interactions of fullerene with the solvent and is made complicated by the fact that fullerenes accrue negative surface charges when present in solvents such as water. In the present work, we simulated fullerenes of varying size and shape (C60, C180, C240, and C540) with and without surface charges in polar protic (water), polar aprotic (acetone), and nonpolar (toluene) solvents using molecular dynamics method. Our results demonstrate that uncharged fullerenes form agglomerates in polar solvents such as water and acetone and remain relatively dispersed in nonpolar toluene. The presence of surface charge significantly reduces agglomerate size in water and acetone. Additionally, the relative influence of surface charge on fullerene agglomeration depends on the size and geometry of the fullerene with larger fullerenes forming relatively smaller agglomerates. We evaluated the diffusion coefficients of solvent molecules within the solvation shell of fullerenes and observed that they are much lower than the bulk solvent and are strongly associated with the fullerenes as seen in the corresponding radial distribution functions. To correlate agglomerate size with the binding energy between fullerenes, we evaluated the potential of mean force between fullerenes in each solvent. Consistent with the solubility of fullerenes, binding energy between fullerenes is the greatest in water followed by acetone and toluene. The presence of charge decreases the binding energy of fullerenes in water and thus results in dispersed fullerenes.

  14. Development of deep eutectic solvents applied in extraction and separation.

    Science.gov (United States)

    Li, Xiaoxia; Row, Kyung Ho

    2016-09-01

    Deep eutectic solvents, as an alternative to ionic liquids, have greener credentials than ionic liquids, and have attracted considerable attention in related chemical research. Deep eutectic solvents have attracted increasing attention in chemistry for the extraction and separation of various target compounds from natural products. This review highlights the preparation of deep eutectic solvents, unique properties of deep eutectic solvents, and synthesis of deep-eutectic-solvent-based materials. On the other hand, application in the extraction and separation of deep eutectic solvents is also included in this report. In this paper, the available data and references in this field are reviewed to summarize the applications and developments of deep eutectic solvents. Based on the development of deep eutectic solvents, an exploitation of new deep eutectic solvents and deep eutectic solvents-based materials is expected to diversify into extraction and separation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Relaxation phenomena of polar non-polar liquid mixtures under low and high frequency electric field

    Indian Academy of Sciences (India)

    K Dutta; S K Sit; S Acharyya

    2003-10-01

    Simultaneous calculation of the dipole moment and the relaxation time of a certain number of non-spherical rigid aliphatic polar liquid molecules () in non-polar solvents () under 9.8 GHz electric field is possible from real $'$ and imaginary $''$ parts of the complex relative permittivity $^{*}_{}$. The low frequency and infinite frequency permittivities 0 and ∞ measured by Purohit et al [1,2] and Srivastava and Srivastava [3] at 25, 35 and 30°C respectively are used to obtain static . The ratio of the individual slopes of imaginary and real $'$ parts of high frequency (hf) complex conductivity $^{*}_{}$ with weight fractions at → 0 and the slopes of $''_{}-'_{}$ curves for different s [4] are employed to obtain s. The former method is better in comparison to the existing one as it eliminates polar–polar interaction. The hf s in Coulomb metre (C m) when compared with static and reported s indicate that ss favour the monomer formations which combine to form dimers in the hf electric field. The comparison among s shows that a part of the molecule is rotating under X-band electric field [5]. The theoretical theos from available bond angles and bond moments of the substituent polar groups attached to the parent molecules differ from the measured s and s to establish the possible existence of mesomeric, inductive and electromeric effects in polar liquid molecules.

  16. Passive Sampling in Regulatory Chemical Monitoring of Nonpolar Organic Compounds in the Aquatic Environment

    DEFF Research Database (Denmark)

    Booij, Kees; Robinson, Craig D; Burgess, Robert M;

    2016-01-01

    We reviewed compliance monitoring requirements in the European Union, the United States, and the Oslo-Paris Convention for the protection of the marine environment of the North-East Atlantic, and evaluated if these are met by passive sampling methods for nonpolar compounds. The strengths and shor...... is the best available technology for chemical monitoring of nonpolar organic compounds. Key issues to be addressed by scientists and environmental managers are outlined.......We reviewed compliance monitoring requirements in the European Union, the United States, and the Oslo-Paris Convention for the protection of the marine environment of the North-East Atlantic, and evaluated if these are met by passive sampling methods for nonpolar compounds. The strengths...... and shortcomings of passive sampling are assessed for water, sediments, and biota. Passive water sampling is a suitable technique for measuring concentrations of freely dissolved compounds. This method yields results that are incompatible with the EU's quality standard definition in terms of total concentrations...

  17. Bitumen recovery from oil sands using deep eutectic solvent and its aqueous solutions

    Science.gov (United States)

    Pulati, Nuerxida

    Oil sands compose a significant proportion of the world's known oil reserves. Oil sands are also known as tar sands and bituminous sands, are complex mixtures of sand, clays, water and bitumen, which is "heavy" and highly viscous oil. The extraction and separation of bitumen from oil sands requires significant amount of energy and large quantities of water and poses several environmental challenges. Bitumen can be successfully separated from oil sands using imidazolium based ionic liquids and nonpolar solvents, however, ionic liquids are expensive and toxic. In this thesis, the ionic liquid alternatives- deep eutectic solvent, were investigated. Oil sands separation can be successfully achieved by using deep eutectic solvents DES (choline chloride and urea) and nonpolar solvent naphtha in different types of oil sands, including Canadian ("water-wet"), Utah ("oil-wet") and low grade Kentucky oil sands. The separation quality depends on oil sands type, including bitumen and fine content, and separation condition, such as solvent ratio, temperature, mixing time and mechanical centrifuge. This separation claims to the DES ability to form ion /charge layering on mineral surface, which results in reduction of adhesion forces between bitumen and minerals and promote their separation. Addition of water to DES can reduce DES viscosity. DES water mixture as a media, oil sands separation can be achieved. However, concentration at about 50 % or higher might be required to obtain a clear separation. And the separation efficiency is oil sands sample dependent. The highest bitumen extraction yield happened at 75% DES-water solution for Utah oil sands samples, and at 50 60% DES-water solutions for Alberta oil sands samples. Force curves were measured using Atomic Force Microscopy new technique, PeakForce Tapping Quantitative Nanomechanical Mapping (PFTQNM). The results demonstrate that, by adding DES, the adhesion force between bitumen and silica and dissipation energy will

  18. Vegetable Oils as Alternative Solvents for Green Oleo-Extraction, Purification and Formulation of Food and Natural Products.

    Science.gov (United States)

    Yara-Varón, Edinson; Li, Ying; Balcells, Mercè; Canela-Garayoa, Ramon; Fabiano-Tixier, Anne-Sylvie; Chemat, Farid

    2017-09-05

    Since solvents of petroleum origin are now strictly regulated worldwide, there is a growing demand for using greener, bio-based and renewable solvents for extraction, purification and formulation of natural and food products. The ideal alternative solvents are non-volatile organic compounds (VOCs) that have high dissolving power and flash point, together with low toxicity and less environmental impact. They should be obtained from renewable resources at a reasonable price and be easy to recycle. Based on the principles of Green Chemistry and Green Engineering, vegetable oils could become an ideal alternative solvent to extract compounds for purification, enrichment, or even pollution remediation. This review presents an overview of vegetable oils as solvents enriched with various bioactive compounds from natural resources, as well as the relationship between dissolving power of non-polar and polar bioactive components with the function of fatty acids and/or lipid classes in vegetable oils, and other minor components. A focus on simulation of solvent-solute interactions and a discussion of polar paradox theory propose a mechanism explaining the phenomena of dissolving polar and non-polar bioactive components in vegetable oils as green solvents with variable polarity.

  19. DOE solvent handbook information sheet

    Energy Technology Data Exchange (ETDEWEB)

    Chavez, A.A.

    1992-01-01

    Solvents and cleaners are used in the Department of Defense (DOD) and the Department of Energy-Defense Program (DOE-DP) maintenance facilities for removing wax, grease, oil, carbon, machining fluids, solder fluxes, mold releases, and other contaminants before repairing or electroplating parts. Private industry also uses cleaners and degreasers for surface preparation of various metals. Growing environmental and worker safety concerns have brought attention to these solvents and cleaners, most of which are classified as toxic. Tightening government regulations have already excluded the use of some chemicals, and restrict the use of various halogenated hydrocarbons because of their atmospheric-ozone depleting effects, as well as their cancer-related risks. As a result, a program was established to develop an efficient, easily accessible, electronic solvent utilization handbook. This is being accomplished by: (1) identifying solvents (alternatives) that are not currently restricted by government regulations for use DOE-DP facilities, and private industry, (2) evaluating their cleaning performance, (3) evaluating their corrosivity, (4) evaluating their air emissions, (5) evaluating the possibility of recycling or recovering all or portions of the alternative degreasers, (6) testing substitute solvents compatibility with non-metallic materials, (7) inputting all of the data gathered (including previous biodegradability information) into a database, and (8) developing a methodology for efficient, widespread access to the data base information system.

  20. DOE solvent handbook information sheet

    Energy Technology Data Exchange (ETDEWEB)

    Chavez, A.A.

    1992-05-01

    Solvents and cleaners are used in the Department of Defense (DOD) and the Department of Energy-Defense Program (DOE-DP) maintenance facilities for removing wax, grease, oil, carbon, machining fluids, solder fluxes, mold releases, and other contaminants before repairing or electroplating parts. Private industry also uses cleaners and degreasers for surface preparation of various metals. Growing environmental and worker safety concerns have brought attention to these solvents and cleaners, most of which are classified as toxic. Tightening government regulations have already excluded the use of some chemicals, and restrict the use of various halogenated hydrocarbons because of their atmospheric-ozone depleting effects, as well as their cancer-related risks. As a result, a program was established to develop an efficient, easily accessible, electronic solvent utilization handbook. This is being accomplished by: (1) identifying solvents (alternatives) that are not currently restricted by government regulations for use DOE-DP facilities, and private industry, (2) evaluating their cleaning performance, (3) evaluating their corrosivity, (4) evaluating their air emissions, (5) evaluating the possibility of recycling or recovering all or portions of the alternative degreasers, (6) testing substitute solvents compatibility with non-metallic materials, (7) inputting all of the data gathered (including previous biodegradability information) into a database, and (8) developing a methodology for efficient, widespread access to the data base information system.

  1. Multiple sclerosis and organic solvents

    DEFF Research Database (Denmark)

    Mortensen, J T; Brønnum-Hansen, Henrik; Rasmussen, K

    1998-01-01

    We investigated a possible causal relation between exposure to organic solvents in Danish workers (housepainters, typographers/printers, carpenters/cabinetmakers) and onset of multiple sclerosis. Data on men included in the Danish Multiple Sclerosis Register (3,241 men) were linked with data from......, and butchers. Over a follow-up period of 20 years, we observed no increase in the incidence of multiple sclerosis among men presumed to be exposed to organic solvents. It was not possible to obtain data on potential confounders, and the study design has some potential for selection bias. Nevertheless......, the study does not support existing hypotheses regarding an association between occupational exposure to organic solvents and multiple sclerosis....

  2. Investigation of the Phase Equilibria and Interfacial Properties for Non-polar Fluids

    Institute of Scientific and Technical Information of China (English)

    付东; 赵毅

    2005-01-01

    A self-consistent density-functional theory (DFT) was applied to investigate the phase behavior and interfacial properties of non-polar fluids. For the bulk phases, the theory was reduced to the statistical associating fluid theory(SAFF) that provides accurate descriptions of vapor-liquid phase diagrams below the critical region. The phase diagrams in the critical region were corrected by the renormalization group theory (RGT). The density profile in the surface was obtained by minimizing the grand potential. With the same set of molecular parameters, both the phase equilibria and the interfacial properties of non-polar fluids were investigated satisfactorily.

  3. The Ideal Solvent for Paper Chromatography of Food Dyes.

    Science.gov (United States)

    Markow, Peter G.

    1988-01-01

    Uses paper chromatography with food dyes to provide a simple and inexpensive basis for teaching chromatography. Provides experimental methodology and tabled results. Includes a solvent system comparison (Rf) for seven dyes and twenty-two solvents. (MVL)

  4. Free-Energy Barriers and Reaction Mechanisms for the Electrochemical Reduction of CO on the Cu(100) Surface, Including Multiple Layers of Explicit Solvent at pH 0.

    Science.gov (United States)

    Cheng, Tao; Xiao, Hai; Goddard, William A

    2015-12-03

    The great interest in the photochemical reduction from CO2 to fuels and chemicals has focused attention on Cu because of its unique ability to catalyze formation of carbon-containing fuels and chemicals. A particular goal is to learn how to modify the Cu catalysts to enhance the production selectivity while reducing the energy requirements (overpotential). To enable such developments, we report here the free-energy reaction barriers and mechanistic pathways on the Cu(100) surface, which produces only CH4 (not C2H4 or CH3OH) in acid (pH 0). We predict a threshold potential for CH4 formation of -0.52 V, which compares well to experiments at low pH, -0.45 to -0.50 V. These quantum molecular dynamics simulations included ∼5 layers of explicit water at the water/electrode interface using enhanced sampling methodology to obtain the free energies. We find that that chemisorbed hydroxyl-methylene (CH-OH) is the key intermediate determining the selectivity for methane over methanol.

  5. Influence of Solvent-Solvent and Solute-Solvent Interaction Properties on Solvent-Mediated Potential

    Institute of Scientific and Technical Information of China (English)

    ZHOU Shi-Qi

    2005-01-01

    A recently proposed universal calculational recipe for solvent-mediated potential is applied to calculate excess potential of mean force between two large Lennard-Jones (LJ) or hard core attractive Yukawa particles immersed in small LJ solvent bath at supercritical state. Comparison between the present prediction with a hypernetted chain approximation adopted for solute-solute correlation at infinitely dilute limit and existing simulation data shows high accuracy for the region with large separation, and qualitative reliability for the solute particle contact region. The calculational simplicity of the present recipe allows for a detailed investigation on the effect of the solute-solvent and solvent-solvent interaction details on the excess potential of mean force. The resultant conclusion is that gathering of solvent particles near a solute particle leads to repulsive excess PMF, while depletion of solvent particles away from the solute particle leads to attractive excess PMF, and minor change of the solvent-solvent interaction range has large influence on the excess PMF.

  6. Molecular and ionic hydrogen bond formation in fluorous solvents.

    Science.gov (United States)

    O'Neal, Kristi L; Weber, Stephen G

    2009-01-08

    There are only a few studies of noncovalent association in fluorous solvents and even fewer that are quantitative. A full understanding, particularly of stoichiometry and binding strength of noncovalent interactions in fluorous solvents could be very useful in improved molecular-receptor-based extractions, advancements in sensor technologies, crystal engineering, and supramolecular chemistry. This work investigates hydrogen bonding between heterocyclic bases and a perfluoropolyether with a terminal carboxylic acid group (Krytox 157FSH (1)), chiefly in FC-72 (a mixture of perfluorohexanes). In particular, we were interested in whether or not proton transfer occurs, and if so, under what conditions in H-bonded complexes. Continuous variations experiments show that in FC-72 weaker bases (pyrazine, pyrimidine, and quinazoline) form 1:1 complexes with 1, whereas stronger bases (quinoline, pyridine, and isoquinoline) form 1:3 complexes. Ultraviolet and infrared spectral signatures reveal that the 1:1 complexes are molecular (B.HA) whereas the 1:3 complexes are ionic (BH+.A-HAHA). Infrared spectra of 1:3 ionic complexes are discussed in detail. Literature and experimental data on complexes between N-heterocyclic bases and carboxylic acids in a range of solvents are compiled to compare solvent effects on proton transfer. Polar solvents support ionic hydrogen bonds at a 1:1 mol ratio. In nonpolar organic solvents, ionic hydrogen bonds are only observed in complexes with 1:2 (base/acid) stoichiometries. In fluorous solvents, a larger excess of acid, 1:3, is necessary to facilitate proton transfer in hydrogen bonds between carboxylic acids and the bases studied.

  7. Separation of the Mixed Solvent Including Methanol,Acetone and Ethyl acetate in Cefotaxime sodium Production%头孢噻肟钠生产中甲醇、丙酮与乙酸乙酯混合溶媒的分离

    Institute of Scientific and Technical Information of China (English)

    王亚其; 李科

    2012-01-01

    通过萃取精馏、精馏对甲醇、丙酮与乙酸乙酯的混合溶媒加以分离,通过对生产数据的调整,确定了萃取精馏过程中混合溶媒与萃取水加入比例为1∶1,此条件下,萃取效果最好。萃取塔顶可以得到丙酮与乙酸乙酯和水的共沸物,塔底可以得到纯度为99.5%的甲醇。%To separate the mixture solvent including methanol,acetone and ethyl acetate by extractive distillation and distillation.Through adjusting production data,to determine the ratio of the mixture solvent to water was 1∶1 in the the extractive distillation process,and under the conditions,the extraction results were the best.To obtain the azeotrope including acetone ethyl acetate and water in the top of the tower,99.5% methanol in the bottom.

  8. Passive sampling in regulatory chemical monitoring of nonpolar organic compounds in the aquatic environment

    NARCIS (Netherlands)

    Booij, K.; Robinson, C.D.; Burgess, R.M.; Mayer, P.; Roberts, C.A.; Ahrens, L.; Allan, I.J.; Brant, J.; Jones, L.; Kraus, U.R.; Larsen, M.M.; Lepom, P.; Petersen, J.; Pröfrock, D.; Roose, P.; Schäfer, S.; Smedes, F.; Tixier, C.; Vorkamp, K.; Whitehouse, P.

    2016-01-01

    We reviewed compliance monitoring requirements in the EuropeanUnion, the United States, and the Oslo-Paris Convention for the protection of themarine environment of the North-East Atlantic, and evaluated if these are met bypassive sampling methods for nonpolar compounds. The strengths andshortcoming

  9. Interaction of Polar and Nonpolar Organic Pollutants with Soil Organic Matter: Sorption Experiments and Molecular Dynamics Simulation

    CERN Document Server

    Ahmed, Ashour A; Aziz, Saadullah G; Hilal, Rifaat H; Elroby, Shaaban A; Al-Youbi, Abdulrahman O; Leinweber, Peter; Kühn, Oliver

    2014-01-01

    The fate of organic pollutants in the environment is influenced by several factors including the type and strength of their interactions with soil components especially SOM. However, a molecular level answer to the question How organic pollutants interact with SOM? is lacking. In order to explore mechanisms of this interaction, we have developed a new SOM model followed by carrying out molecular dynamics (MD) simulations in parallel with sorption experiments. The new SOM model comprises free SOM functional groups (carboxylic acid and naphthalene) as well as SOM cavities (with two different sizes), representing the soil voids, containing the same SOM functional groups. To examine the effect of the hydrophobicity on the interaction, the organic pollutants hexachlorobenzene (HCB, non-polar) and sulfanilamide (SAA, polar) were considered. The experimental and the theoretical outcomes explored four major points regarding sorption of SAA and HCB on soil. 1. The interaction depends on the SOM chemical composition mo...

  10. Surface chemistry and electronic structure of nonpolar and polar GaN films

    Energy Technology Data Exchange (ETDEWEB)

    Mishra, Monu; Krishna, T.C. Shibin; Aggarwal, Neha; Gupta, Govind, E-mail: govind@nplindia.org

    2015-08-01

    Highlights: • Surface chemistry and electronic structure of polar and nonpolar GaN is reported. • Influence of polarization on electron affinity of p & np GaN films is investigated. • Correlation between surface morphology and polarity has been deduced. - Abstract: Photoemission and microscopic analysis of nonpolar (a-GaN/r-Sapphire) and polar (c-GaN/c-Sapphire) epitaxial gallium nitride (GaN) films grown via RF-Molecular Beam Epitaxy is reported. The effect of polarization on surface properties like surface states, electronic structure, chemical bonding and morphology has been investigated and correlated. It was observed that polarization lead to shifts in core level (CL) as well as valence band (VB) spectra. Angle dependent X-ray Photoelectron Spectroscopic analysis revealed higher surface oxide in polar GaN film compared to nonpolar GaN film. On varying the take off angle (TOA) from 0° to 60°, the Ga−O/Ga−N ratio varied from 0.11–0.23 for nonpolar and 0.17–0.36 for polar GaN film. The nonpolar film exhibited N-face polarity while Ga-face polarity was perceived in polar GaN film due to the inherent polarization effect. Polarization charge compensated surface states were observed on the polar GaN film and resulted in downward band bending. Ultraviolet photoelectron spectroscopic measurements revealed electron affinity and ionization energy of 3.4 ± 0.1 eV and 6.8 ± 0.1 eV for nonpolar GaN film and 3.8 ± 0.1 eV and 7.2 ± 0.1 eV for polar GaN film respectively. Field Emission Scanning Electron Microscopy measurements divulged smooth morphology with pits on polar GaN film. The nonpolar film on the other hand showed pyramidal structures having facets all over the surface.

  11. Solvent effects on photophysical properties of copper and zinc porphyrins

    Institute of Scientific and Technical Information of China (English)

    LI Ye

    2008-01-01

    The photophysics of Zn(tetraphenylporphyrin,TPP), Zn(tetra-2,4,6-trimethylphenyl porphyrin, TMP), Zn (tetra-(o-dichlorophenyl) porphyrin, TPPCI8), Cu(tetraphenylporphyrin,TPP), Cu(tetra-2,4,6-trimethyl-phenyl porphyrin,TMP), and Cu(tetra-(o-dichlorophenyl) porphyrin, TPPCI8,TPPCI8) in several solvents have been investigated on steady state and time-resolved spectroscopy. The Cu(TPPCI8) is normal and shows no evidence of CT transition in the visible or near UV regions in nonpolar solvent. However,Cu(TPPCI8)shows a blue shift in the absorption spectrum and intramolecular CT bands at absorption spectra in polar solvent, which shows a fluorescence maximum emission at 650 nm and 8.4 ns lifetime.The reason can be attributed to two points. Firstly, the increase of solvent polarity can enlarge outer reorganisational energy, which is favorable to reduce the activation free energy of charger-transfer transition based on Marcus theory of electron transfer. Moreover, the internal heavy-atom effect on Cu(TPPCI8) is encouraging to stabilize the 2T1 state also, which increases the possibility of population to CT band from 2T1 state. This result is in accord with an earlier estimate of a 10 ns lifetime and CT absorption at 640 nm bands for the CT state of Cu (Ⅱ) octethylporphyrins. Other possible reasons arousing unusual fluorescence like H-bonding, axial ligands, molecular aggregation are excluded.

  12. Alternative Green Solvents Project

    Science.gov (United States)

    Maloney, Phillip R.

    2012-01-01

    Necessary for safe and proper functioning of equipment. Mainly halogenated solvents. Tetrachloride, Trichloroethylene (TCE), CFC-113. No longer used due to regulatory/safety concerns. Precision Cleaning at KSC: Small % of total parts. Used for liquid oxygen (LOX) systems. Dual solvent process. Vertrel MCA (decafluoropentane (DFP) and trons-dichloroethylene) HFE-7100. DFP has long term environmental concerns. Project Goals: a) Identify potential replacements. b) 22 wet chemical processes. c) 3 alternative processes. d) Develop test procedures. e) Contamination and cleaning. f) Analysis. g) Use results to recommend alternative processes. Conclusions: a) No alternative matched Vertrel in this study. b) No clear second place solvent. c) Hydrocarbons- easy; Fluorinated greases- difficult. d) Fluorinated component may be needed in replacement solvent. e) Process may need to make up for shortcoming of the solvent. f) Plasma and SCC02 warrant further testing.

  13. Photonic Crystal Based Sensor for Organic Solvents and for Solvent-Water Mixtures

    Directory of Open Access Journals (Sweden)

    Otto S. Wolfbeis

    2012-12-01

    Full Text Available Monodisperse polystyrene nanoparticles with a diameter of 173 nm were incorporated into a polydimethylsiloxane matrix where they display an iridescent color that can be attributed to the photonic crystal effect. The film is of violet color if placed in plain water, but turns to red in the presence of the non-polar solvent n-hexane. Several solvents were studied in some detail. We show that such films are capable of monitoring the water content of ethanol/water mixtures, where only 1% (v/v of water leads to a shift of the peak wavelength of reflected light by 5 nm. The method also can be applied to determine, both visually and instrumentally, the fraction of methanol in ethanol/methanol mixtures. Here, a fraction of 1% of methanol (v/v results in a wavelength shift of 2 nm. The reflected wavelength is not influenced by temperature changes nor impeded by photobleaching. The signal changes are fully reversible and response times are <1 s.

  14. Schottky contact formation on polar and non-polar AlN

    Energy Technology Data Exchange (ETDEWEB)

    Reddy, Pramod; Bryan, Isaac; Bryan, Zachary; Tweedie, James; Kirste, Ronny; Collazo, Ramon; Sitar, Zlatko [Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695-7919 (United States)

    2014-11-21

    The interfaces of m- and c-plane AlN with metals of different work functions and electro-negativities were characterized and the Schottky barrier heights were measured. The Schottky barrier height was determined by measuring the valence band maximum (VBM) with respect to the Fermi level at the surface (interface) before (after) metallization. VBM determination included accurate modeling and curve fitting of density of states at the valence band edge with the XPS data. The experimental behavior of the barrier heights could not be explained by the Schottky-Mott model and was modeled using InterFace-Induced Gap States (IFIGS). A slope parameter (S{sub X}) was used to incorporate the density of surface states and is a measure of Fermi level pinning. The experimental barriers followed theoretical predictions with a barrier height at the surface Fermi level (Charge neutrality level (CNL)) of ∼2.1 eV (∼2.7 eV) on m-plane (c-plane) and S{sub X} ∼ 0.36 eV/Miedema unit. Slope parameter much lower than 0.86 implied a surface/interface states dominated behavior with significant Fermi level pinning and the measured barrier heights were close to the CNL. Titanium and zirconium provided the lowest barriers (1.6 eV) with gold providing the highest (2.3 eV) among the metals analyzed on m-plane. It was consistently found that barrier heights decreased from metal polar to non-polar surfaces, in general, due to an increasing CNL. The data indicated that charged IFIGS compensate spontaneous polarization charge. These barrier height and slope parameter measurements provided essential information for designing Schottky diodes and other contact-based devices on AlN.

  15. Efficient cellulose solvent: quaternary ammonium chlorides.

    Science.gov (United States)

    Kostag, Marc; Liebert, Tim; El Seoud, Omar A; Heinze, Thomas

    2013-10-01

    Pure quaternary tetraalkylammonium chlorides with one long alkyl chain dissolved in various organic solvents constitute a new class of cellulose solvents. The electrolytes are prepared in high yields and purity by Menshutkin quaternization, an inexpensive and easy synthesis route. The pure molten tetraalkylammonium chlorides dissolve up to 15 wt% of cellulose. Cosolvents, including N,N-dimethylacetamide (DMA), may be added in large excess, leading to a system of decreased viscosity. Contrary to the well-established solvent DMA/LiCl, cellulose dissolves in DMA/quaternary ammonium chlorides without any pretreatment. Thus, the use of the new solvent avoids some disadvantages of DMA/LiCl and ionic liquids, the most extensively employed solvents for homogeneous cellulose chemistry.

  16. Green-solvent-processable organic solar cells

    Directory of Open Access Journals (Sweden)

    Shaoqing Zhang

    2016-11-01

    Full Text Available Solution-processable organic photovoltaics (OPV has emerged as a promising clean energy-generating technology due to its potential for low-cost manufacturing with a high power/weight ratio. The state-of-the-art OPV devices are processed by hazardous halogenated solvents. Fabricating high-efficiency OPV devices using greener solvents is a necessary step toward their eventual commercialization. In this review, recent research efforts and advances in green-solvent-processable OPVs are summarized, and two basic strategies including material design and solvent selection of light-harvesting layers are discussed. In particular, the most recent green-solvent-processable OPVs with high efficiencies in excess of 9% are highlighted.

  17. Automatic parametrization of implicit solvent models for the blind prediction of solvation free energies

    CERN Document Server

    Wang, Bao; Wei, Guowei

    2016-01-01

    In this work, a systematic protocol is proposed to automatically parametrize implicit solvent models with polar and nonpolar components. The proposed protocol utilizes the classical Poisson model or the Kohn-Sham density functional theory (KSDFT) based polarizable Poisson model for modeling polar solvation free energies. For the nonpolar component, either the standard model of surface area, molecular volume, and van der Waals interactions, or a model with atomic surface areas and molecular volume is employed. Based on the assumption that similar molecules have similar parametrizations, we develop scoring and ranking algorithms to classify solute molecules. Four sets of radius parameters are combined with four sets of charge force fields to arrive at a total of 16 different parametrizations for the Poisson model. A large database with 668 experimental data is utilized to validate the proposed protocol. The lowest leave-one-out root mean square (RMS) error for the database is 1.33k cal/mol. Additionally, five s...

  18. Vacuum-UV spectroscopy of interstellar ice analogs. II. Absorption cross-sections of nonpolar ice molecules

    Science.gov (United States)

    Cruz-Diaz, G. A.; Muñoz Caro, G. M.; Chen, Y.-J.; Yih, T.-S.

    2014-02-01

    Context. Dust grains in cold circumstellar regions and dark-cloud interiors at 10-20 K are covered by ice mantles. A nonthermal desorption mechanism is invoked to explain the presence of gas-phase molecules in these environments, such as the photodesorption induced by irradiation of ice due to secondary ultraviolet photons. To quantify the effects of ice photoprocessing, an estimate of the photon absorption in ice mantles is required. In a recent work, we reported the vacuum-ultraviolet (VUV) absorption cross sections of nonpolar molecules in the solid phase. Aims: The aim was to estimate the VUV-absorption cross sections of nonpolar molecular ice components, including CH4, CO2, N2, and O2. Methods: The column densities of the ice samples deposited at 8 K were measured in situ by infrared spectroscopy in transmittance. VUV spectra of the ice samples were collected in the 120-160 nm (10.33-7.74 eV) range using a commercial microwave-discharged hydrogen flow lamp. Results: We found that, as expected, solid N2 has the lowest VUV-absorption cross section, which about three orders of magnitude lower than that of other species such as O2, which is also homonuclear. Methane (CH4) ice presents a high absorption near Ly-α (121.6 nm) and does not absorb below 148 nm. Estimating the ice absorption cross sections is essential for models of ice photoprocessing and allows estimating the ice photodesorption rates as the number of photodesorbed molecules per absorbed photon in the ice. Data can be found at http://ghosst.osug.fr/

  19. Chemical profiling of Curcuma aeruginosa Roxb. rhizome using different techniques of solvent extraction

    Institute of Scientific and Technical Information of China (English)

    Sanimah; Simoh; Alizah; Zainal

    2015-01-01

    Objective:To investigate the possible phytochemical constituents of Curcuma aeruginosa Roxb.(C. aeruginosa) rhizome using two different techniques of direct solvent extraction. Methods: Two different techniques of direct solvent extractions, i.e. methyl tert-butyl ether(MTBE) extraction and two-phase methanol/chloroform(M/C) system, were used in this study. The analysis of the phytochemical constituents in MTBE and M/C extracts was performed using gas chromatography-mass spectrometry/mass spectrometry. The mass spectra of the compounds was matched with the NIST 08 mass spectral library. Results: The present study revealed that the extraction using two-phase M/C have resulted in higher metabolite coverage compared to the extraction with MTBE. Direct solvent extraction using MTBE revealed the presence of 27 compounds; whereas, M/C allowed the extraction of 18 and 36 compounds in polar(methanol) and nonpolar(chloroform) fractions respectively. The major compounds detected in the MTBE extract that based on the peak area percentage were methenolone(16.64%), cycloisolongifolene, 8,9-dehydro-9-formyl-(15.93%), labd-13-en-15-oic acid,8,12-epoxy-12-hydroxy-γ-lactone(10.77%), propiolic acid, 3-(1-hydroxy)-2 isopropyl-1,5-methylcyclohexyl)(7.84%), 4-oxo-β-isodamascol(5.17%), velleral(3.11%) and Z-α-farnesene(2.00%). The most prevailing major compounds identified in the polar fraction of the M/C extraction were α-D glucopyranoside, 1,3,4,6 tetrakis-O-(TMS)(trimethylsilyl)-β-D-fructofuranosyl 2,3,4,6-tetrakis-O-(TMS)-(38.08%), d-glucose, 2,3,4,5,6-pentakis-O-(TMS)-, O-methyloxime(14.61%), D-fructose, 1,3,4,5,6-pentakis-O-(TMS)-, O-methyloxime(5.28%), isocitric acid(TMS)(3.06%), oxalic acid, bis(TMS) ester(2.96%), hexadecanoic acid, TMS ester(2.16%), citric acid, ethyl ester, tri-TMS(1.91%) and butanedioic acid, [(TMS) oxy]-, bis(TMS) ester(1.14%); whereas in the nonpolar extract, among the major compounds detected were cycloisolongifolene, 8, 9-dehydro-9-formyl(15

  20. Insulin adsorption on crystalline SiO2: Comparison between polar and nonpolar surfaces using accelerated molecular-dynamics simulations

    Science.gov (United States)

    Nejad, Marjan A.; Mücksch, Christian; Urbassek, Herbert M.

    2017-02-01

    Adsorption of insulin on polar and nonpolar surfaces of crystalline SiO2 (cristobalite and α -quartz) is studied using molecular dynamics simulation. Acceleration techniques are used in order to sample adsorption phase space efficiently and to identify realistic adsorption conformations. We find major differences between the polar and nonpolar surfaces. Electrostatic interactions govern the adsorption on polar surfaces and can be described by the alignment of the protein dipole with the surface dipole; hence spreading of the protein on the surface is irrelevant. On nonpolar surfaces, on the other hand, van-der-Waals interaction dominates, inducing surface spreading of the protein.

  1. Supercritical solvent coal extraction

    Science.gov (United States)

    Compton, L. E. (Inventor)

    1984-01-01

    Yields of soluble organic extract are increased up to about 50% by the supercritical extraction of particulate coal at a temperature below the polymerization temperature for coal extract fragments (450 C.) and a pressure from 500 psig to 5,000 psig by the conjoint use of a solvent mixture containing a low volatility, high critical temperature coal dissolution catalyst such as phenanthrene and a high volatility, low critical temperature solvent such as toluene.

  2. Effect of solvents on propylene epoxidation over TS-1 catalyst

    Institute of Scientific and Technical Information of China (English)

    Yulong WU; Qingshan LIU; Xueli SU; Zhentao MI

    2008-01-01

    Solvents have an important effect on the epoxidation of propylene catalyzed by TS-1. The experimental results show that, in different solvents, the catalytic activity of epoxidation is in the following order: methanol > 2-propanol > 2-butanol > acetoni-trile > acetone > tetrahydrofuran. Based on the reaction mechanism, the effects of solvents on the epoxidation were studied from eight aspects, which included the electronic effect, the steric effect, the polarity of solvent, the effect of solvent on sorption and diffusion of reactant, the oxidation of alcohol, the etherification of PO, the deactivation of TS-1 and the solubility of propylene in the solvents. The electronic effect, steric effect and the polarity of solvent were considered to be the main aspects. This work may provide theoretical guidance for choosing solvents for these kinds of reactions and also may serve as basis for further industrialization.

  3. Cleaning without chlorinated solvents

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, L.M.; Simandl, R.F.

    1994-12-31

    Because of health and environmental concerns, many regulations have been passed in recent years regarding the use of chlorinated solvents. The Oak Ridge Y-12 Plant has had an active program to find alternatives for these solvents used in cleaning applications for the past 7 years. During this time frame, the quantity of solvents purchased has been reduced by 92%. The program has been a twofold effort. Vapor degreasers used in batch cleaning-operations have been replaced by ultrasonic cleaning with aqueous detergent, and other organic solvents have been identified for use in hand-wiping or specialty operations. In order to qualify these alternatives for use, experimentation was conducted on cleaning ability as well as effects on subsequent operations such as welding, painting and bonding. Cleaning ability was determined using techniques such as X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared Spectroscopy (FTIR) which are capable of examining monolayer levels of contamination on a surface. Solvents have been identified for removal of rust preventative oils, lapping oils, machining coolants, lubricants, greases, and mold releases. Solvents have also been evaluated for cleaning urethane foam spray guns, swelling of urethanes and swelling of epoxies.

  4. Light- and Solvent-Controlled Self-Assembly Behavior of Spiropyran-Polyoxometalate-Alkyl Hybrid Molecules.

    Science.gov (United States)

    Chu, Yang; Saad, Ali; Yin, Panchao; Wu, Jiayingzi; Oms, Olivier; Dolbecq, Anne; Mialane, Pierre; Liu, Tianbo

    2016-08-08

    A molecular photochromic spiropyran-polyoxometalate-alkyl organic-inorganic hybrid has been synthesized and fully characterized. The reversible switching of the hydrophobic spiropyran fragment to the hydrophilic merocyanine one can be easily achieved under light irradiation at different wavelengths. This switch changes the amphiphilic feature of the hybrid, leading to a light-controlled self-assembly behavior in solution. It has been shown that the hybrid can reversibly self-assemble into vesicles in polar solvents and irreversibly into reverse vesicles in non-polar solvents. The sizes of the vesicles and the reverse vesicles are both tunable by the polarity of the solvent, with the hydrophobic interactions being the main driving force.

  5. Chemical reactions in solvents and melts

    CERN Document Server

    Charlot, G

    1969-01-01

    Chemical Reactions in Solvents and Melts discusses the use of organic and inorganic compounds as well as of melts as solvents. This book examines the applications in organic and inorganic chemistry as well as in electrochemistry. Organized into two parts encompassing 15 chapters, this book begins with an overview of the general properties and the different types of reactions, including acid-base reactions, complex formation reactions, and oxidation-reduction reactions. This text then describes the properties of inert and active solvents. Other chapters consider the proton transfer reactions in

  6. Caustic-Side Solvent Extraction: Chemical and Physical Properties of the Optimized Solvent

    Energy Technology Data Exchange (ETDEWEB)

    Delmau, L.H.

    2002-10-08

    This work was undertaken to optimize the solvent used in the Caustic Side Solvent Extraction (CSSX) process and to measure key chemical and physical properties related to its performance in the removal of cesium from the alkaline high-level salt waste stored in tanks at the Savannah River Site. The need to adjust the solvent composition arose from the prior discovery that the previous baseline solvent was supersaturated with respect to the calixarene extractant. The following solvent-component concentrations in Isopar{reg_sign} L diluent are recommended: 0.007 M calix[4]arene-bis(tert-octylbenzo-crown-6) (BOBCalixC6) extractant, 0.75 M 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol (Cs-7SB) phase modifier, and 0.003 M tri-n-octylamine (TOA) stripping aid. Criteria for this selection included BOBCalixC6 solubility, batch cesium distribution ratios (D{sub Cs}), calculated flowsheet robustness, third-phase formation, coalescence rate (dispersion numbers), and solvent density. Although minor compromises within acceptable limits were made in flowsheet robustness and solvent density, significant benefits were gained in lower risk of third-phase formation and lower solvent cost. Data are also reported for the optimized solvent regarding the temperature dependence of D{sub Cs} in extraction, scrubbing, and stripping (ESS); ESS performance on recycle; partitioning of BOBCalixC6, Cs-7SB, and TOA to aqueous process solutions; partitioning of organic anions; distribution of metals; solvent phase separation at low temperatures; solvent stability to elevated temperatures; and solvent density and viscosity. Overall, the technical risk of the CSSX process has been reduced by resolving previously identified issues and raising no new issues.

  7. Quantum theory of interfacial tension quantitatively predicts spontaneous charging of nonpolar aqueous interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Fernández, Ariel, E-mail: ariel@afinnovation.com [Argentine Institute of Mathematics (I. A. M.), National Research Council (CONICET), Buenos Aires 1083 (Argentina); Collegium Basilea – Institute for Advanced Study, Basel CH4053 (Switzerland)

    2015-10-16

    The spontaneous negative charging of aqueous nonpolar interfaces has eluded quantitative first-principle prediction, possibly because it steadfastly challenges the classical Debye dielectric picture. In this work we show that quantitative prediction requires a substantive revision of Debye's linear dielectric ansatz to incorporate an anomalous polarization component yielding electrostatic energy stored as interfacial tension and detailed enough to account for the differences in electronic structure between water and its ionized states. The minimization of this interfacial tension is due to a quantum effect resulting in the reduction in hydrogen-bond frustration that takes place upon hydroxide ion adsorption. The quantitative predictions are validated vis-à-vis measurements of the free energy change associated with hydroxide adsorption obtained using sum-frequency vibrational spectroscopy. - Highlights: • Spontaneous charging of aqueous nonpolar interfaces challenges Debye dielectrics. • A quantum non-Debye theory of interfacial tension is developed. • The minimization of the interfacial tension promotes hydroxide ion adsorption.

  8. A Simple Method for Estimation of Dielectric Constants and Polarizabilities of Nonpolar and Slightly Polar Hydrocarbons

    Science.gov (United States)

    Panuganti, Sai R.; Wang, Fei; Chapman, Walter G.; Vargas, Francisco M.

    2016-07-01

    Many of the liquids that are used as electrical insulators are nonpolar or slightly polar petroleum-derived hydrocarbons, such as the ones used for cable and/or transformer oils. In this work, semi-empirical expressions with no adjustable parameters for the dielectric constant and the polarizability of nonpolar and slightly polar hydrocarbons and their mixtures are proposed and validated. The expressions that were derived using the Vargas-Chapman One-Third rule require the mass density and the molecular weight of the substance of interest. The equations were successfully tested for various hydrocarbons and polymers with dipole moments eliminate the need of extensive experimental data and require less input parameters compared to existing correlations.

  9. Influence of oxygen in architecting large scale nonpolar GaN nanowires

    CERN Document Server

    Patsha, Avinash; Pandian, Ramanathaswamy; Dhara, S

    2015-01-01

    Manipulation of surface architecture of semiconducting nanowires with a control in surface polarity is one of the important objectives for nanowire based electronic and optoelectronic devices for commercialization. We report the growth of exceptionally high structural and optical quality nonpolar GaN nanowires with controlled and uniform surface morphology and size distribution, for large scale production. The role of O contamination (~1-10^5 ppm) in the surface architecture of these nanowires is investigated with the possible mechanism involved. Nonpolar GaN nanowires grown in O rich condition show the inhomogeneous surface morphologies and sizes (50 - 150 nm) while nanowires are having precise sizes of 40(5) nm and uniform surface morphology, for the samples grown in O reduced condition. Relative O contents are estimated using electron energy loss spectroscopy studies. Size-selective growth of uniform nanowires is also demonstrated, in the O reduced condition, using different catalyst sizes. Photoluminescen...

  10. Vertical nonpolar growth templates for light emitting diodes formed with GaN nanosheets

    Science.gov (United States)

    Yeh, Ting-Wei; Lin, Yen-Ting; Ahn, Byungmin; Stewart, Lawrence S.; Daniel Dapkus, P.; Nutt, Steven R.

    2012-01-01

    We demonstrate that nonpolar m-plane surfaces can be generated on uniform GaN nanosheet arrays grown vertically from the (0001)-GaN bulk material. InGaN/GaN multiple quantum wells (MQWs) grown on the facets of these nanosheets are demonstrated by cross-sectional transmission electron microscopy. Owing to the high aspect ratio of the GaN nanosheet structure, the MQWs predominantly grow on nonpolar GaN planes. The results suggest that GaN nanosheets provide a conduction path for device fabrication and also a growth template to reduce the piezoelectric field inside the active region of InGaN-based light emitting diodes.

  11. Electrokinetics of Polar Liquids in Contact with Non-Polar Surfaces

    CERN Document Server

    Lin, Chih-Hsiu; Chaudhury, Manoj K

    2014-01-01

    Zeta potentials of several polar protic (water, ethylene glycol, formamide) as well as polar aprotic (dimethyl sulfoxide) liquids were measured in contact with three non-polar surfaces using closed-cell electro-osmosis. The test surfaces were chemisorbed monolayers of alkyl siloxanes, fluoroalkyl siloxanes and polydimethylsiloxanes (PDMS) grafted on glass slides. All these liquids exhibited substantial electrokinetics in contact with the non-polar surfaces with these observations: the electrokinetic effect on the fluorocarbon-coated surface is the strongest; and on a PDMS grafted surface, the effect is the weakest. Even though these hygroscopic liquids contain small amounts of water, the current models of charging based on the adsorption of hydroxide ions at the interface or the dissociation of preexisting functionalities (e.g., silanol groups) appear to be insufficient to account for the various facets of the experimental observations. The results illustrate how ubiquitous the phenomenon of electro-kinetics ...

  12. Stable and efficient colour enrichment powders of nonpolar nanocrystals in LiCl

    Science.gov (United States)

    Erdem, Talha; Soran-Erdem, Zeliha; Sharma, Vijay Kumar; Kelestemur, Yusuf; Adam, Marcus; Gaponik, Nikolai; Demir, Hilmi Volkan

    2015-10-01

    In this work, we propose and develop the inorganic salt encapsulation of semiconductor nanocrystal (NC) dispersion in a nonpolar phase to make a highly stable and highly efficient colour converting powder for colour enrichment in light-emitting diode backlighting. Here the wrapping of the as-synthesized green-emitting CdSe/CdZnSeS/ZnS nanocrystals into a salt matrix without ligand exchange is uniquely enabled by using a LiCl ionic host dissolved in tetrahydrofuran (THF), which simultaneously disperses these nonpolar nanocrystals. We studied the emission stability of the solid films prepared using NCs with and without LiCl encapsulation on blue LEDs driven at high current levels. The encapsulated NC powder in epoxy preserved 95.5% of the initial emission intensity and stabilized at this level while the emission intensity of NCs without salt encapsulation continuously decreased to 34.7% of its initial value after 96 h of operation. In addition, we investigated the effect of ionic salt encapsulation on the quantum efficiency of nonpolar NCs and found the quantum efficiency of the NCs-in-LiCl to be 75.1% while that of the NCs in dispersion was 73.0% and that in a film without LiCl encapsulation was 67.9%. We believe that such ionic salt encapsulated powders of nonpolar NCs presented here will find ubiquitous use for colour enrichment in display backlighting.In this work, we propose and develop the inorganic salt encapsulation of semiconductor nanocrystal (NC) dispersion in a nonpolar phase to make a highly stable and highly efficient colour converting powder for colour enrichment in light-emitting diode backlighting. Here the wrapping of the as-synthesized green-emitting CdSe/CdZnSeS/ZnS nanocrystals into a salt matrix without ligand exchange is uniquely enabled by using a LiCl ionic host dissolved in tetrahydrofuran (THF), which simultaneously disperses these nonpolar nanocrystals. We studied the emission stability of the solid films prepared using NCs with and

  13. Broadband non-polarizing terahertz beam splitters with variable split ratio

    KAUST Repository

    Wei, Minggui

    2017-08-15

    Seeking effective terahertz functional devices has always aroused extensive attention. Of particular interest is the terahertz beam splitter. Here, we have proposed, designed, manufactured, and tested a broadband non-polarizing terahertz beam splitter with a variable split ratio based on an all-dielectric metasurface. The metasurface was created by patterning a dielectric surface of the N-step phase gradient and etching to a few hundred micrometers. The conversion efficiency as high as 81% under the normal incidence at 0.7 THz was achieved. Meanwhile, such a splitter works well over a broad frequency range. The split ratio of the proposed design can be continuously tuned by simply shifting the metasurface, and the angle of emergences can also be easily adjusted by choosing the step of phase gradients. The proposed design is non-polarizing, and its performance is kept under different polarizations.

  14. Solvent- and guest-responsive supramolecular self-assembly of 1,3,5-tris(10-carboxydecyloxy) benzene by scanning tunneling microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Cui, Lihua; Miao, Xinrui, E-mail: msxrmiao@scut.edu.cn; Xu, Li; Deng, Wenli, E-mail: wldeng@scut.edu.cn

    2014-09-15

    Graphical abstract: - Highlights: • TCDB can entrap solvent molecules or π-electron-conjugated guest molecules. • We calculate hydrogen bonding which is crucial to stabilize the assembly networks. • Structural properties rely on the solvent- and guest-responsive assembly. • Kinetics and thermodynamics explain the morphology character of polarity. - Abstract: Two-dimensional hydrogen-bonded networks formed in the self-assembly of 1,3,5-tris(10-carboxydecyloxy) benzene (TCDB) show regular solvent- and guest-induced supramolecular structural properties, which have been presented by scanning tunneling microscopy at the liquid–solid interface at ambient conditions. TCDB acting as a host template can entrap solvent molecules or π-electron-conjugated guest molecules to fabricate the flexible co-adsorption architectures, which are subject to the balance between the hydrogen bonding of the host lattice and the van der Waals forces between the host and the guest molecules. Hydrogen bonding among TCDB molecules is crucial to stabilize the host networks to settle the system into a global minimum of Gibbs free energy. We also find a strong correlation between the structural parameters and the physical properties of the solvent. Statistical analysis shows that the unit cell volume of TCDB dissolved in nonpolar 1-phenylotane and n-tetradecane shrank significantly compared with that of host–guest system, which fully reflects the coadsorption effect of nonpolar solvent molecules. Our results identify that the kinetic effect of adsorption/desorption as well as the solvent viscosity comes into play in tuning the two-dimensional self-assembled structures. Furthermore, mechanical calculations demonstrate that TCDB incline to adsorb with a larger dipole configuration in nonpolar solvents due to its dissolvability. It is believed that the results are of significance to supramolecular host–guest chemistry and surface science.

  15. Solvent selection methodology for pharmaceutical processes: Solvent swap

    DEFF Research Database (Denmark)

    Papadakis, Emmanouil; Kumar Tula, Anjan; Gani, Rafiqul

    2016-01-01

    A method for the selection of appropriate solvents for the solvent swap task in pharmaceutical processes has been developed. This solvent swap method is based on the solvent selection method of Gani et al. (2006) and considers additional selection criteria such as boiling point difference, volati...

  16. A comparative DFT study of the structural and electronic properties of nonpolar GaN surfaces

    Energy Technology Data Exchange (ETDEWEB)

    González-Hernández, Rafael, E-mail: rhernandezj@uninorte.edu.co [Grupo de Investigación en Física Aplicada, Departamento de Física, Universidad del Norte, Barranquilla (Colombia); González-García, Alvaro [Grupo de Investigación en Física Aplicada, Departamento de Física, Universidad del Norte, Barranquilla (Colombia); Barragán-Yani, Daniel [Fachgebiet Material modellierung, Institut für Materialwissenschaft, Technische Universität Darmstadt, Jovanka-Bontschits-Straße 2, 64287 Darmstadt (Germany); López-Pérez, William [Grupo de Investigación en Física Aplicada, Departamento de Física, Universidad del Norte, Barranquilla (Colombia)

    2014-09-30

    Highlights: • A comparative analysis of the geometry and the electronic characteristics of nonpolar GaN surfaces was carried out. • Surface energies are too low for LDA, but lower still for GGA and MGGA functionals, except for PBEsol. • PBEsol exhibits good lattice parameters and surface energies. • Surface intra-gap states reduce the band gap of the nonpolar GaN surfaces. • Slight changes in the dispersion of surface states were observed for the LDA, GGA, and MGGA functionals. - Abstract: A comparative analysis of the geometry and the electronic characteristics of nonpolar GaN surfaces was carried out using density-functional theory (DFT) with different approximations for the exchange-correlation energy (LDA, PBE, PBEsol, RPBE, TPSS, revTPSS, and HSE). The obtained data show that the GaN(101{sup ¯}0) (m-plane) is more energetically stable than the GaN(112{sup ¯}0) (a-plane) surface. However, these surfaces have similar surface relaxation geometry, with a Ga-N surface bond-length contraction of around 6–7% and a Ga-N surface rotational angle in the range of 6–9°. Our results show that the use of different exchange-correlation functionals does not significantly change the surface energy and surface geometry. In addition, we found the presence of surface intra-gap states that reduce the band gap of the nonpolar GaN surface with respect to the bulk value, in agreement with recent photoelectron and surface optical spectroscopy experiments.

  17. Modeling diffusion coefficients in binary mixtures of polar and non-polar compounds

    DEFF Research Database (Denmark)

    Medvedev, Oleg; Shapiro, Alexander

    2005-01-01

    The theory of transport coefficients in liquids, developed previously, is tested on a description of the diffusion coefficients in binary polar/non-polar mixtures, by applying advanced thermodynamic models. Comparison to a large set of experimental data shows good performance of the model. Only...... components and to only one parameter for mixtures consisting of non-polar components. A possibility of complete prediction of the parameters is discussed....

  18. Hydrophobic monolayered nanoflakes of tungsten oxide: coupled exfoliation and fracture in a nonpolar organic medium.

    Science.gov (United States)

    Honda, Masashi; Oaki, Yuya; Imai, Hiroaki

    2015-06-21

    Coupled exfoliation and fracture induced formation of hydrophobic monolayered nanoflakes in a nonpolar organic medium. The hydrophobic monolayered nanoflakes 5-20 nm in lateral size consisted of a tungstate layer with surface modification by stearylammonium ions (C18H37NH3)0.397 H0.603Cs3W11O35·xH2O (x < 0.625).

  19. Solvent Extraction Developments in Southern Africa

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The largest solvent-extraction plant in the world at the time, the Nchanga Copper Operation, was in Zambia. The first commercial process using solvent extraction for the refining of the platinum-group metals was in South Africa. More recently, the Southern African region has seen the implementation of solvent extraction for other base metals, precious metals, and specialty metals. These include the world firsts of primary production of zinc at Skorpion Zinc in Namibia and the large-scale refining of gold by Harmony Gold in South Africa. Several other flowsheets that use solvent-extraction technology are currently under commissioning, development, or feasibility study for implementation in this part of the world, including those for the recovery of copper, cobalt, nickel, tantalum, and niobium.

  20. Effects of organic solvents and substrate binding on trypsin in acetonitrile and hexane media.

    Science.gov (United States)

    Meng, Yanyan; Yuan, Yuan; Zhu, Yanyan; Guo, Yanzhi; Li, Menglong; Wang, Zhimeng; Pu, Xuemei; Jiang, Lin

    2013-09-01

    In this work, we used molecular dynamic (MD) simulation to study trypsin with and without a six-amino-acid peptide bound in three different solvents (water, acetonitrile and hexane) in order to provide molecular information for well understanding the structure and function of enzymes in non-aqueous media. The results show that the enzyme is more compact and less native-like in hexane than in the other two polar solvents. The substrate could stabilize the native protein structure in the two polar media, but not in the non-polar hexane. There are no significant differences in the conformation of the S1 pocket upon the substrate binding in water and acetonitrile media while a reverse behavior is observed in hexane media, implying a possible induced fit binding mechanism in the non-polar media. The substrate binding enhances the stability of catalytic H-bond network since it could expel the solvent molecules from the active site. The enzyme and the substrate appear to be more appropriate to the reactive conformation in the organic solvents compared with aqueous solution. There is much greater substrate binding strength in hexane media than the water and acetonitrile ones since the polar solvent significantly weakens electrostatic interactions, which are observed to be the main driving force to the binding. In addition, some residues of the S1 pocket could remain favorable contribution to the binding despite the solvent change, but with differences in the contribution extent, the number and the type of residues between the three media.

  1. Electric Charge Accumulation in Polar and Non-Polar Polymers under Electron Beam Irradiation

    Science.gov (United States)

    Nagasawa, Kenichiro; Honjoh, Masato; Takada, Tatsuo; Miyake, Hiroaki; Tanaka, Yasuhiro

    The electric charge accumulation under an electron beam irradiation (40 keV and 60 keV) was measured by using the pressure wave propagation (PWP) method in the dielectric insulation materials, such as polar polymeric films (polycarbonate (PC), polyethylene-naphthalate (PEN), polyimide (PI), and polyethylene-terephthalate (PET)) and non-polar polymeric films (polystyrene (PS), polypropylene (PP), polyethylene (PE) and polytetrafluoroethylene (PTFE)). The PE and PTFE (non-polar polymers) showed the properties of large amount of electric charge accumulation over 50 C/m3 and long saturation time over 80 minutes. The PP and PS (non-polar polymer) showed the properties of middle amount of charge accumulation about 20 C/m3 and middle saturation time about 1 to 20 minutes. The PC, PEN, PI and PET (polar polymers) showed the properties of small amount of charge accumulation about 5 to 20 C/m3 and within short saturation time about 1.0 minutes. This paper summarizes the relationship between the properties of charge accumulation and chemical structural formula, and compares between the electro static potential distribution with negative charged polymer and its chemical structural formula.

  2. Enhanced UV detection by non-polar epitaxial GaN films

    Energy Technology Data Exchange (ETDEWEB)

    Mukundan, Shruti; Chandan, Greeshma; Mohan, Lokesh; Krupanidhi, S. B., E-mail: sbk@mrc.iisc.ernet.in [Materials Research Centre, Indian Institute of Science, Bangalore (India); Roul, Basanta [Materials Research Centre, Indian Institute of Science, Bangalore (India); Central Research Laboratory, Bharat Electronics, Bangalore (India); Shetty, Arjun [Department of Electrical Communication Engineering, Indian Institute of Science, Bangalore (India)

    2015-12-15

    Nonpolar a-GaN (11-20) epilayers were grown on r-plane (1-102) sapphire substrates using plasma assisted molecular beam epitaxy. High resolution x-ray diffractometer confirmed the orientation of the grown film. Effect of the Ga/N ratio on the morphology and strain of a-GaN epilayers was compared and the best condition was obtained for the nitrogen flow of 1 sccm. Atomic force microscopy was used to analyze the surface morphology while the strain in the film was quantitatively measured using Raman spectroscopy and qualitatively analyzed by reciprocal space mapping technique. UV photo response of a-GaN film was measured after fabricating a metal-semiconductor-metal structure over the film with gold metal. The external quantum efficiency of the photodetectors fabricated in the (0002) polar and (11-20) nonpolar growth directions were compared in terms of responsivity and nonpolar GaN showed the best sensitivity at the cost of comparatively slow response time.

  3. Chemical etching behaviors of semipolar (11̄22) and nonpolar (11̄20) gallium nitride films.

    Science.gov (United States)

    Jung, Younghun; Baik, Kwang Hyeon; Mastro, Michael A; Hite, Jennifer K; Eddy, Charles R; Kim, Jihyun

    2014-08-14

    Wet chemical etching using hot KOH and H3PO4 solutions was performed on semipolar (11̄22) and nonpolar (11̄20) GaN films grown on sapphire substrates. An alternating KOH/H3PO4/KOH etch process was developed to control the orientation of the facets on the thin-film surface. The initial etch step in KOH produced c- and m-plane facets on the surface of both semipolar (11̄22) and nonpolar (11̄20) GaN thin-films. A second etch step in H3PO4 solution additionally exposed a (̄1̄12̄2) plane, which is chemically stable in H3PO4 solution. By repeating the chemical etch with KOH solution, the m-plane facets as seen in the original KOH etch step were recovered. The etching methods developed in our work can be used to control the surface morphologies of nonpolar and semipolar GaN-based optoelectronic devices such as light-emitting diodes and solar cells.

  4. Enhanced sensing of nonpolar volatile organic compounds by silicon nanowire field effect transistors.

    Science.gov (United States)

    Paska, Yair; Stelzner, Thomas; Christiansen, Silke; Haick, Hossam

    2011-07-26

    Silicon nanowire field effect transistors (Si NW FETs) are emerging as powerful sensors for direct detection of biological and chemical species. However, the low sensitivity of the Si NW FET sensors toward nonpolar volatile organic compounds (VOCs) is problematic for many applications. In this study, we show that modifying Si NW FETs with a silane monolayer having a low fraction of Si-O-Si bonds between the adjacent molecules greatly enhances the sensitivity toward nonpolar VOCs. This can be explained in terms of an indirect sensor-VOC interaction, whereby the nonpolar VOC molecules induce conformational changes in the organic monolayer, affecting (i) the dielectric constant and/or effective dipole moment of the organic monolayer and/or (ii) the density of charged surface states at the SiO(2)/monolayer interface. In contrast, polar VOCs are sensed directly via VOC-induced changes in the Si NW charge carriers, most probably due to electrostatic interaction between the Si NW and polar VOCs. A semiempirical model for the VOC-induced conductivity changes in the Si NW FETs is presented and discussed.

  5. Solvent-induced O-H vibration red-shifts of oxygen-acids in hydrogen-bonded O-H···base complexes.

    Science.gov (United States)

    Keinan, Sharon; Pines, Dina; Kiefer, Philip M; Hynes, James T; Pines, Ehud

    2015-01-22

    Infrared spectroscopy has been used to characterize the solvent effect on the OH stretching vibrations νOH of phenol, 1-naphthol, 2-naphthol, 1-hydroxypyrene, and ethanol. We distinguish the dielectric (nonspecific) effect of the solvent on ΔνOH, the observed red-shifts in νOH, from the much larger red-shift caused by direct hydrogen (H)-bonding interactions with the solvents. To isolate the solvent dielectric constant ε effect on νOH, the OH oscillator was also studied when it is already H-bonded with an invariant oxygen base, dimethyl sulfoxide. We find that ΔνOH depends importantly on ΔPA, the difference between the proton affinities of the conjugate base of the proton donor and the proton acceptor. For a given H-bonded complex, νOH tends to vary inversely with ε, exhibiting different slopes for polar and nonpolar solvents, i.e., solvents comprising molecules with and without a permanent dipole moment, respectively. We use a two-state valence-bond-based theory to analyze our experimental data. This demonstrates that the OH oscillator acquires a more ionic-like character in the vibrational excited state, i.e., charge transfer; this results in a stronger H-bond in a more anharmonic potential for the OH vibration. The theory distinguishes between nonpolar and polar solvents and successfully accounts for the observed 1/ε and ΔPA variations.

  6. Theoretical study of chlorophyll a hydrates formation in aqueous organic solvents.

    Science.gov (United States)

    Ben Fredj, Arij; Ruiz-López, Manuel F

    2010-01-14

    A theoretical analysis of chlorophyll a (Chla) hydration processes in aqueous organic solvents has been carried out by means of quantum chemistry calculations. A detailed knowledge of the thermodynamics of these processes is fundamental in order to better understand the organization of chlorophyll molecules in vivo, specifically the structure of chlorophyll pairs in photosystems I and II. In the present work, we assumed a Chla model in which the phytyl chain is replaced by a methyl group. Calculations were performed at the B3LYP/6-31G(d) level corrected for basis set superposition errors and dispersion interaction energy. This computational scheme was previously shown to provide data close to MP2/6-311++(2d,2p) results. Solvents effects were taken into account using either continuum (for nonpolar solvents) or discrete-continuum (for polar coordinating solvents) methods. In the latter case, we first examined the structure of Chla in rigorously dry solutions. Two types of solvents were characterized according to Mg-atom coordination: In type I solvents (acetone, acetonitrile, DMSO), Mg exhibits five-coordination, whereas in type II solvents (THF, pyridine), Mg exhibits six-coordination. Hydration processes are quite dependent on solvent nature. In nonpolar or low-polarity solvents such as cyclohexane or chloroform, hydration is always exothermic and exergonic, despite a large entropy term that strongly opposes hydration. In polar solvents of type II, hydration is quite unfavorable, and essentially no hydrates are expected in these media, except perhaps at very large water concentrations (although, in such a case, the medium cannot be simply described as an organic solvent). In polar solvents of type I, the situation is intermediate, and dihydration is favorable in some cases (acetone, acetonitrile) and unfavorable in others (DMSO). It is interesting to note that first hydration processes in coordinating solvents (of either type I or type II), where a water molecule

  7. Purex process solvent: literature review

    Energy Technology Data Exchange (ETDEWEB)

    Geier, R.G.

    1979-10-01

    This document summarizes the data on Purex process solvent presently published in a variety of sources. Extracts from these various sources are presented herein and contain the work done, the salient results obtained, and the original, unaltered conclusions of the author of each paper. Three major areas are addressed: solvent stability, solvent quality testing, and solvent treatment processes. 34 references, 44 tables.

  8. Chemical Potential of the Solvent: a Crucial Player for Rationalizing Host-Guest Affinities.

    Science.gov (United States)

    Piguet, Claude; Baudet, Karine; Guerra, Sebastiano

    2017-08-08

    An access to reliable values of the thermodynamic constants which controls simple host-guest association, is crucial in medicine, biology, pharmacy and chemistry since the optimum concentration of an effector (i.e. a drug) acting on a receptor is set to the inverse of these constants. Intermolecular association between charged species in polar solvents largely obeys this principle. Any deviation from ideality is mastered by the Debye-Hückel theory of ionic atmosphere. Much less is known for related association reactions involving neutral species in non-polar (lipophilic) media such as membranes, bilayers or organic polymers. Taking the intermolecular association between [La(hfa)3dig] guest and tridentate polyaromatic host receptors L1-L3 in dichloromethane as a proof-of-concept, we show that the progress of the association reactions disrupt the chemical potential of the solvent to such an extent that may seemingly be shifted by two orders of magnitude, thus leading to erroneous dose-response prescriptions. A simple chemical model, which considers a subset of solvent molecules in surface contact with the partners of the association reaction, restores a reliable access to true and interpretable thermodynamic constants. This 'complement' to the law of mass action offers a simple method for safely taking care of the non-predictable variations of the activity coefficients of the various partners when host-guest reactions are conducted in non-polar media. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Method for Predicting Solubilities of Solids in Mixed Solvents

    DEFF Research Database (Denmark)

    Ellegaard, Martin Dela; Abildskov, Jens; O'Connell, J. P.

    2009-01-01

    A method is presented for predicting solubilities of solid solutes in mixed solvents, based on excess Henry's law constants. The basis is statistical mechanical fluctuation solution theory for composition derivatives of solute/solvent infinite dilution activity coefficients. Suitable approximations...... are made for a single parameter characterizing solute/solvent interactions. Comparisons with available data show that the method is successful in describing a variety of observed mixed solvent solubility behavior, including nearly ideal systems with small excess solubilities, systems with solute......-independent excess solubilities, and systems deviating from these simple rules. Successful predictions for new solvent mixtures cat? be made using limited data from other mixtures....

  10. Apparatus and method for removing solvent from carbon dioxide in resin recycling system

    Science.gov (United States)

    Bohnert, George W.; Hand, Thomas E.; DeLaurentiis, Gary M.

    2009-01-06

    A two-step resin recycling system and method solvent that produces essentially contaminant-free synthetic resin material. The system and method includes one or more solvent wash vessels to expose resin particles to a solvent, the solvent contacting the resin particles in the one or more solvent wash vessels to substantially remove contaminants on the resin particles. A separator is provided to separate the solvent from the resin particles after removal from the one or more solvent wash vessels. The resin particles are next exposed to carbon dioxide in a closed loop carbon dioxide system. The closed loop system includes a carbon dioxide vessel where the carbon dioxide is exposed to the resin, substantially removing any residual solvent remaining on the resin particles after separation. A separation vessel is also provided to separate the solvent from the solvent laden carbon dioxide. Both the carbon dioxide and the solvent are reused after separation in the separation vessel.

  11. Evaluation of various techniques for separation of non-polar modifier concentrates from petroleum waxy by-products

    Directory of Open Access Journals (Sweden)

    Fathi S. Soliman

    2014-09-01

    Full Text Available Two petroleum waxy by-products (light and middle slack wax crudes were evaluated for separation of non-polar modifiers by using different techniques. The results showed that, the light slack wax is selected as a suitable wax for separation of n-alkanes with even number of carbon atoms ranging from C20 to C26 for their high n-paraffin contents and can be used as non-polar structural modifiers. Different separation techniques; multistage fractional crystallization and liquid–solid chromatography; followed by the urea adduction technique have been used to separate non-polar modifier concentrates from the light slack wax crude. The light slack wax, its saturate components, the hard wax fractions isolated from light slack wax by the multistage fractional crystallization technique and their adducts were analyzed by GC to characterize and compare the produced components. The resulting data reveal that, the adducts of light slack wax and its saturate components; can be used as non-polar modifier concentrates of low carbon atoms (C20 + C22. From an economic point of view, the light slack wax adduct is selected as a non-polar modifier concentrate whereas, the separation step can be neglected to save energy. Meanwhile, the adduct of the hard wax isolated at 30 °C can be used as the preferable non-polar modifier concentrate of the high carbon number atoms (C24 + C26.

  12. Safe battery solvents

    Science.gov (United States)

    Harrup, Mason K.; Delmastro, Joseph R.; Stewart, Frederick F.; Luther, Thomas A.

    2007-10-23

    An ion transporting solvent maintains very low vapor pressure, contains flame retarding elements, and is nontoxic. The solvent in combination with common battery electrolyte salts can be used to replace the current carbonate electrolyte solution, creating a safer battery. It can also be used in combination with polymer gels or solid polymer electrolytes to produce polymer batteries with enhanced conductivity characteristics. The solvents may comprise a class of cyclic and acyclic low molecular weight phosphazenes compounds, comprising repeating phosphorus and nitrogen units forming a core backbone and ion-carrying pendent groups bound to the phosphorus. In preferred embodiments, the cyclic phosphazene comprises at least 3 phosphorus and nitrogen units, and the pendent groups are polyethers, polythioethers, polyether/polythioethers or any combination thereof, and/or other groups preferably comprising other atoms from Group 6B of the periodic table of elements.

  13. Cyclodextrin Films with Fast Solvent Transport and Shape-Selective Permeability.

    Science.gov (United States)

    Villalobos, Luis Francisco; Huang, Tiefan; Peinemann, Klaus-Viktor

    2017-07-01

    This study describes the molecular-level design of a new type of filtration membrane made of crosslinked cyclodextrins-inexpensive macrocycles of glucose, shaped like hollow truncated cones. The channel-like cavities of cyclodextrins spawn numerous paths of defined aperture in the separation layer that can effectively discriminate between molecules. The transport of molecules through these membranes is highly shape-sensitive. In addition, the presence of hydrophobic (cavity) and hydrophilic (ester-crosslinked outer part) domains in these films results in high permeances for both polar and nonpolar solvents. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Cyclodextrin Films with Fast Solvent Transport and Shape-Selective Permeability

    KAUST Repository

    Villalobos, Luis Francisco

    2017-04-24

    This study describes the molecular-level design of a new type of filtration membrane made of crosslinked cyclodextrins-inexpensive macrocycles of glucose, shaped like hollow truncated cones. The channel-like cavities of cyclodextrins spawn numerous paths of defined aperture in the separation layer that can effectively discriminate between molecules. The transport of molecules through these membranes is highly shape-sensitive. In addition, the presence of hydrophobic (cavity) and hydrophilic (ester-crosslinked outer part) domains in these films results in high permeances for both polar and nonpolar solvents.

  15. Energy requirements for wet solvent extraction of lipids from microalgal biomass.

    Science.gov (United States)

    Martin, Gregory J O

    2016-04-01

    Biofuel production from microalgae requires energy efficient processes for extracting and converting triacylglyceride lipids to fuel, compatible with coproduction of protein feeds and nutraceuticals. Wet solvent extraction involves mechanical cell rupture, lipid extraction via solvent contacting, physical phase separation, thermal solvent recovery, and transesterification. A detailed analysis of the effect of key process parameters on the parasitic energy demand of this process was performed. On a well-to-pump basis, between 16% and 320% of the resultant biodiesel energy was consumed depending solely on the process parameters. Highly positive energy balances can be achieved, but only if a correctly designed process is used. This requires processing concentrated biomass (ca 25%w/w) with a high triacylglyceride content (ca 30%w/w), and an efficient extraction process employing a non-polar solvent, low solvent-to-paste ratio, and efficient energy recovery. These requirements preclude many laboratory scale processes and polar co-solvents as viable options for large-scale biofuel production. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Organic solvent topical report

    Energy Technology Data Exchange (ETDEWEB)

    COWLEY, W.L.

    1999-05-13

    This report provides the basis for closing the organic solvent safety issue. Sufficient information is presented to conclude that risk posed by an organic solvent fire is within risk evaluation guidelines. This report updates information contained in Analysis of Consequences of Postulated Solvent Fires in Hanford Site Waste Tanks. WHC-SD-WM-CN-032. Rev. 0A (Cowley et al. 1996). However, this document will not replace Cowley et al (1996) as the primary reference for the Basis for Interim Operation (BIO) until the recently submitted BIO amendment (Hanson 1999) is approved by the US Department of Energy. This conclusion depends on the use of controls for preventing vehicle fuel fires and for limiting the use of flame cutting in areas where hot metal can fall on the waste surface.The required controls are given in the Tank Waste Remediation System Technical Safety Requirements (Noorani 1997b). This is a significant change from the conclusions presented in Revision 0 of this report. Revision 0 of this calcnote concluded that some organic solvent fire scenarios exceeded risk evaluation guidelines, even with controls imposed.

  17. Uniform Treatment of Solute-Solvent Dispersion in the Ground and Excited Electronic States of the Solute Based on a Solvation Model with State-Specific Polarizability.

    Science.gov (United States)

    Marenich, Aleksandr V; Cramer, Christopher J; Truhlar, Donald G

    2013-08-13

    We present a new kind of treatment of the solute-solvent dispersion contribution to the free energy of solvation using a solvation model with state-specific polarizability (SMSSP). To evaluate the solute-solvent dispersion contribution, the SMSSP model utilizes only two descriptors, namely, the spherically averaged dipole polarizability of the solute molecule (either in its ground or excited electronic state) and the refractive index of the solvent. The model was parametrized over 643 ground-state solvation free energy data for 231 solutes in 14 nonpolar, non-hydrogen-bonding solvents. We show that the SMSSP model is applicable to solutes in both the ground and the excited electronic state. For example, in comparison to available experimental data, the model yields qualitatively accurate predictions of the solvatochromic shifts for a number of systems where solute-solvent dispersion is the dominant contributor to the shift.

  18. Permeability of starch gel matrices and select films to solvent vapors.

    Science.gov (United States)

    Glenn, Gregory M; Klamczynski, Artur P; Ludvik, Charles; Shey, Justin; Imam, Syed H; Chiou, Bor-Sen; McHugh, Tara; DeGrandi-Hoffman, Gloria; Orts, William; Wood, Delilah; Offeman, Rick

    2006-05-03

    Volatile agrochemicals such as 2-heptanone have potential in safely and effectively controlling important agricultural pests provided that they are properly delivered. The present study reports the permeability of starch gel matrices and various coatings, some of which are agricultural-based, that could be used in controlled release devices. Low-density, microcellular starch foam was made from wheat, Dent corn, and high amylose corn starches. The foam density ranged from 0.14 to 0.34 g/cm3, the pore volume ranged from 74 to 89%, and the loading capacity ranged from 2.3 to 7.2 times the foam weight. The compressive properties of the foam were not markedly affected by saturating the pore volume with silicone oil. The vapor transmission rate (VTR) and vapor permeability (VP) were measured in dry, porous starch foam and silicone-saturated starch gels. VTR values were highest in foam samples containing solvents with high vapor pressures. Silicone oil-saturated gels had lower VTR and VP values as compared to the dry foam. However, the silicone oil gel did not markedly reduce the VP for 2-heptanone and an additional vapor barrier or coating was needed to adequately reduce the evaporation rate. The VP of films of beeswax, paraffin, ethylene vinyl alcohol, a fruit film, and a laminate comprised of beeswax and fruit film was measured. The fruit film had a relatively high VP for polar solvents and a very low VP for nonpolar solvents. The laminate film provided a low VP for polar and nonpolar solvents. Perforating the fruit film portion of the laminate provided a method of attaining the target flux rate of 2-heptanone. The results demonstrate that the vapor flux rate of biologically active solvents can be controlled using agricultural materials.

  19. Nonpolar and semipolar InGaN/GaN multiple-quantum-well solar cells with improved carrier collection efficiency

    Science.gov (United States)

    Huang, Xuanqi; Fu, Houqiang; Chen, Hong; Zhang, Xiaodong; Lu, Zhijian; Montes, Jossue; Iza, Michael; DenBaars, Steven P.; Nakamura, Shuji; Zhao, Yuji

    2017-04-01

    We demonstrate the nonpolar and semipolar InGaN/GaN multiple-quantum-well (MQW) solar cells grown on the nonpolar m-plane and semipolar ( 20 2 ¯ 1 ) plane bulk GaN substrates. The optical properties and photovoltaic performance of the nonpolar and semipolar InGaN solar cells were systematically studied, and the results were compared to the conventional polar c-plane devices. The absorption spectra, current density-voltage (J-V) characteristics, external quantum efficiency (EQE), and internal quantum efficiency (IQE) were measured for nonpolar m-plane, semipolar ( 20 2 ¯ 1 ) plane, and polar c-plane InGaN/GaN MQW solar cells. Nonpolar m-plane InGaN/GaN MQW solar cells showed the best performance across all devices, with a high open-circuit voltage of 2.32 V, a low bandgap-voltage offset of 0.59 V, and the highest EQE and IQE. In contrast, the polar c-plane device showed the lowest EQE despite the highest absorption spectra. This huge difference is attributed to the better carrier transport and collection on nonpolar m-plane devices due to the reduced polarization effects, which were further confirmed by bias-dependent EQE measurements and energy band diagram simulations. This study demonstrates the high potential of nonpolar and semipolar InGaN solar cells and can serve as guidance for the future design and fabrication of high efficiency III-nitride solar cells.

  20. Solvent Vapour Detection with Cholesteric Liquid Crystals—Optical and Mass-Sensitive Evaluation of the Sensor Mechanism

    Directory of Open Access Journals (Sweden)

    Adnan Mujahid

    2010-05-01

    Full Text Available Cholesteric liquid crystals (CLCs are used as sensitive coatings for the detection of organic solvent vapours for both polar and non-polar substances. The incorporation of different analyte vapours in the CLC layers disturbs the pitch length which changes the optical properties, i.e., shifting the absorption band. The engulfing of CLCs around non-polar solvent vapours such as tetrahedrofuran (THF, chloroform and tetrachloroethylene is favoured in comparison to polar ones, i.e., methanol and ethanol. Increasing solvent vapour concentrations shift the absorbance maximumto smaller wavelengths, e.g., as observed for THF. Additionally, CLCs have been coated on acoustic devices such as the quartz crystal microbalance (QCM to measure the frequency shift of analyte samples at similar concentration levels. The mass effect for tetrachloroethylene was about six times higher than chloroform. Thus, optical response can be correlated with intercalation in accordance to mass detection. The mechanical stability was gained by combining CLCs with imprinted polymers. Therefore, pre-concentration of solvent vapours was performed leading to an additional selectivity.

  1. A semiempirical model for estimating the hydration free energy of neutral nonpolar compounds

    Science.gov (United States)

    Ratkova, E. L.

    2012-10-01

    An improved semiempirical model for determining the hydration free energy of neutral nonpolar compounds is presented. The model is based on a combination of the RISM approach of the integral equation theory and empirical correlations. It is demonstrated that the developed model has high predictive ability for alkanes, alkenes, and dienes (present only in the test set of compounds). It is concluded that this semiempirical model can be applied in estimating the hydration free energy of more complicated structures based on saturated and nonsaturated aliphatic hydrocarbons.

  2. Dynamic solvation shell and solubility of C60 in organic solvents.

    Science.gov (United States)

    Wang, Chun I; Hua, Chi C; Chen, Show A

    2014-08-21

    The notion of (static) solvation shells has recently proved fruitful in revealing key molecular factors that dictate the solubility and aggregation properties of fullerene species in polar or ionic solvent media. Using molecular dynamics schemes with carefully evaluated force fields, we have scrutinized both the static and the dynamic features of the solvation shells of single C60 particle for three nonpolar organic solvents (i.e., chloroform, toluene, and chlorobenzene) and a range of system temperatures (i.e., T = 250-330 K). The central findings have been that, while the static structures of the solvation shell remain, in general, insensitive to the effects of changing solvent type or system temperature, the dynamic behavior of solvent molecules within the shell exhibits prominent dependence on both factors. Detailed analyses led us to propose the notion of dynamically stable solvation shell, effectiveness of which can be characterized by a new physical parameter defined as the ratio of two fundamental time constants representing, respectively, the solvent relaxation (or residence) time within the first solvation shell and the characteristic time required for the fullerene particle to diffuse a distance comparable to the shell thickness. We show that, for the five (two from the literature) different solvent media and the range of system temperatures examined herein, this parameter bears a value around unity and, in particular, correlates intimately with known trends of solubility for C60 solutions. We also provide evidence revealing that, in addition to fullerene-solvent interactions, solvent-solvent interactions play an important role, too, in shaping the dynamic solvation shell, as implied by recent experimental trends.

  3. Solvent tuned single molecule dual emission in protic solvents: effect of polarity and H-bonding.

    Science.gov (United States)

    Chevreux, S; Allain, C; Wilbraham, L; Nakatani, K; Jacques, P; Ciofini, I; Lemercier, G

    2015-01-01

    Phen-PENMe2 has recently been proposed as a promising new molecule displaying solvent-tuned dual emission, highlighting an original and newly-described charge transfer model. The study of the photophysical behaviour of this molecule was extended to include protic solvents. The effects of polarity and hydrogen bonding lead to an even more evident dual emission associated with a large multi-emission band in some solvents like methanol, highlighting Phen-PENMe2 as a promising candidate for white light emission.

  4. Fatty acid profiles of polar and non-polar lipids of Pleurotus ostreatus and P. cornucopiae var. 'citrino-pileatus' grown at different temperatures.

    Science.gov (United States)

    Pedneault, Karine; Angers, Paul; Avis, Tyler J; Gosselin, André; Tweddell, Russell J

    2007-10-01

    The application of fatty acid (FA) composition data has now extended to studies of physiology, chemotaxonomy, and intrageneric differentiation, as well as to studies of human nutrition. Environmental factors such as nutritional components, oxygen, and temperature are known to affect lipid content and composition in living organisms, including fungi. In the present study, the polar and non-polar lipid content of Pleurotus ostreatus and P. cornucopiae var. citrino-pileatus fruiting bodies produced at temperatures ranging from 12-27 degrees C and from 17-27 degrees C, respectively, were analysed to evaluate the effect of temperature on lipid composition in these mushrooms. Results showed that lowering the growth temperature below 17 degrees C generally provided an expected increase in FA unsaturation in polar and non-polar lipids of P. ostreatus. Although raising the temperature above 17 degrees C did not show any clear-cut tendency in FA unsaturation, it did reveal that growth temperature had a differential effect on the FA profiles in fruiting bodies of P. ostreatus and P. cornucopiae. This study suggests that care should be taken when using FA content and unsaturation data for physiological, chemotaxonomic, and intrageneric differentiation studies, and that it may be possible to manipulate lipid unsaturation in Pleurotus spp. through modified growth temperatures.

  5. Fluorescent derivatization combined with aqueous solvent-based dispersive liquid-liquid microextraction for determination of butyrobetaine, l-carnitine and acetyl-l-carnitine in human plasma.

    Science.gov (United States)

    Chen, Yi-Ching; Tsai, Chia-Ju; Feng, Chia-Hsien

    2016-09-16

    A novel aqueous solvent-based dispersive liquid-liquid microextraction (AS-DLLME) method was combined with narrow-bore liquid chromatography and fluorescence detection for the determination of hydrophilic compounds. A remover (non-polar solvent) and extractant (aqueous solution) were introduced into the derivatization system (acetonitrile) to obtain a water-in-oil emulsion state that increased the mass transfer of analytes. As a proof of concept, three quaternary ammonium substances, including butyrobetaine, l-carnitine and acetyl-l-carnitine, were also used as analytes and determined in pharmaceuticals, personal care products, food and human plasma. The analytes were derivatized with 4-bromomethylbiphenyl for fluorescence detection and improved retention in the column. The linear response was 10-2000nM for l-carnitine and acetyl-l-carnitine with a good determination coefficient (r(2)>0.998) in the standard solution. The detection limit for l-carnitine and acetyl-l-carnitine was 4.5 fmol. The method was also successfully applied to a 1μL sample of human plasma. In the linearity calculations for determining butyrobetaine, l-carnitine and acetyl-l-carnitine in human plasma, the determination coefficients ranged from 0.996 to 0.999. Linear regression exhibited good reproducibility and a relative standard deviation better than 7.50% for the slope and 9.06% for the intercept. To characterize highly hydrophilic compounds in various samples, the proposed method provides good sensitivity for a small sample volume with a low consumption of toxic solvents.

  6. Storage lipids of yeasts: a survey of nonpolar lipid metabolism in Saccharomyces cerevisiae, Pichia pastoris, and Yarrowia lipolytica.

    Science.gov (United States)

    Koch, Barbara; Schmidt, Claudia; Daum, Günther

    2014-09-01

    Biosynthesis and storage of nonpolar lipids, such as triacylglycerols (TG) and steryl esters (SE), have gained much interest during the last decades because defects in these processes are related to severe human diseases. The baker's yeast Saccharomyces cerevisiae has become a valuable tool to study eukaryotic lipid metabolism because this single-cell microorganism harbors many enzymes and pathways with counterparts in mammalian cells. In this article, we will review aspects of TG and SE metabolism and turnover in the yeast that have been known for a long time and combine them with new perceptions of nonpolar lipid research. We will provide a detailed insight into the mechanisms of nonpolar lipid synthesis, storage, mobilization, and degradation in the yeast S. cerevisiae. The central role of lipid droplets (LD) in these processes will be addressed with emphasis on the prevailing view that this compartment is more than only a depot for TG and SE. Dynamic and interactive aspects of LD with other organelles will be discussed. Results obtained with S. cerevisiae will be complemented by recent investigations of nonpolar lipid research with Yarrowia lipolytica and Pichia pastoris. Altogether, this review article provides a comprehensive view of nonpolar lipid research in yeast.

  7. Role of solvent/non-solvent ratio on microsphere formation using the solvent removal method.

    Science.gov (United States)

    Godbee, J; Scott, E; Pattamunuch, P; Chen, S; Mathiowitz, E

    2004-03-01

    The importance of good solvent concentration in the non-solvent mixture and the non-solvent viscosity on the ability to form microspheres using solvent removal process was investigated. The higher the viscosity of the polymer solutions, the higher the concentration of good solvent needed in the nonsolvent mixture to produce microspheres. This finding was due to faster precipitation of the polymer phase. Also, the addition of a model drug, fluorescein isothiocyanate conjugated-labelled bovine serum albumin, to the polymer solution (10% poly-L-lactic acid:poly(fumaric-co-sebacic) anhydride in methylene chloride) resulted in an overall lower polymer solution viscosity (15.5 cP with fluorescein isothiocyanate conjugated-labelled bovine serum albumin as compared with 18.25 cP for blank polymer at 25 degrees C). Additionally, the effect of good solvent concentration on non-solvent viscosity was evaluated, and the viscosity decreased as the concentration of good solvent increased. The effect of good solvent concentration on the non-solvent mixture on sphere formation was of great importance. Microspheres would not form when the good polymer solvent (methylene chloride) in the non-solvent phase was too low (below 175 ml for poly-L-lactic acid or 150 ml for poly(D,L-lactidco-glycolid)) or was replaced by another good solvent such as ethyl acetate, even though the same viscosity was achieved. It was shown that the concentration of the good solvent in the non-solvent mixture was more of a controlling factor than the viscosity of the non-solvent mixture in microsphere formation and the findings support the conclusion that diffusion is the main controlling parameter in solvent removal.

  8. Iridium(I) complexes with anionic N-heterocyclic carbene ligands as catalysts for the hydrogenation of alkenes in nonpolar media.

    Science.gov (United States)

    Kolychev, Eugene L; Kronig, Sabrina; Brandhorst, Kai; Freytag, Matthias; Jones, Peter G; Tamm, Matthias

    2013-08-21

    A series of lithium complexes of anionic N-heterocyclic carbenes that contain a weakly coordinating borate moiety (WCA-NHC) was prepared in one step from free N-heterocyclic carbenes by deprotonation with n-butyl lithium followed by borane addition. The reaction of the resulting lithium-carbene adducts with [M(COD)Cl]2 (M = Rh, Ir; COD = 1,5-cyclooctadiene) afforded zwitterionic rhodium(I) and iridium(I) complexes of the type [(WCA-NHC)M(COD)], in which the metal atoms exhibit an intramolecular interaction with the N-aryl groups of the carbene ligands. For M = Rh, the neutral complex [(WCA-NHC)Rh(CO)2] and the ate complex (NEt4)[(WCA-NHC)Rh(CO)2Cl] were prepared, with the latter allowing an assessment of the donor ability of the ligand by IR spectroscopy. The zwitterionic iridium-COD complexes were tested as catalysts for the homogeneous hydrogenation of alkenes, which can be performed in the presence of nonpolar solvents or in the neat alkene substrate. Thereby, the most active complex showed excellent stability and activity in hydrogenation of alkenes at low catalyst loadings (down to 10 ppm).

  9. Determination of vapor pressures for nonpolar and semipolar organic compounds from gas chromatographic retention data

    Science.gov (United States)

    Hinckley, D.A.; Bidleman, T.F.; Foreman, W.T.; Tuschall, J.R.

    1990-01-01

    Vapor pressures for nonpolar and moderately polar organochlorine, pyrethroid, and organophosphate insecticides, phthalate esters, and organophosphate flame retardants were determined by capillary gas chromatography (GC). Organochlorines and polycyclic aromatic hydrocarbons with known liquid-phase vapor pressures (P??L) (standard compounds) were chromatographed along with two reference compounds n-C20 (elcosane) and p,p???-DDT on a 1.0-m-long poly(dimethylsiloxane) bonded-phase (BP-1) column to determine their vapor pressures by GC (P??GC). A plot of log P??L vs log P??GC for standard compounds was made to establish a correlation between measured and literature values, and this correlation was then used to compute P??L of test compounds from their measured P??GC. P??L of seven major components of technical chlordane, endosulfan and its metabolites, ??-hexachlorocyclohexane, mirex, and two components of technical toxaphene were determined by GC. This method provides vapor pressures within a factor of 2 of average literature values for nonpolar compounds, similar to reported interlaboratory precisions of vapor pressure determinations. GC tends to overestimate vapor pressures of moderately polar compounds. ?? 1990 American Chemical Society.

  10. A polarity-induced defect mechanism for conductivity and magnetism at polar-nonpolar oxide interfaces.

    Science.gov (United States)

    Yu, Liping; Zunger, Alex

    2014-10-13

    The discovery of conductivity and magnetism at the polar-nonpolar interfaces of insulating nonmagnetic oxides such as LaAlO3 and SrTiO3 has raised prospects for attaining interfacial functionalities absent in the component materials. Yet, the microscopic origin of such emergent phenomena remains unclear, posing obstacles to design of improved functionalities. Here we present first principles calculations of electronic and defect properties of LaAlO3/SrTiO3 interfaces and reveal a unifying mechanism for the origins of both conductivity and magnetism. We demonstrate that the polar discontinuity across the interface triggers thermodynamically the spontaneous formation of certain defects that in turn cancel the polar field induced by the polar discontinuity. The ionization of the spontaneously formed surface oxygen vacancy defects leads to interface conductivity, whereas the unionized Ti-on-Al antisite defects lead to interface magnetism. The proposed mechanism suggests practical design principles for inducing and controlling both conductivity and magnetism at general polar-nonpolar interfaces.

  11. Nonpolar III-nitride vertical-cavity surface-emitting lasers incorporating an ion implanted aperture

    KAUST Repository

    Leonard, J. T.

    2015-07-06

    © 2015 AIP Publishing LLC. We report on our recent progress in improving the performance of nonpolar III-nitride vertical-cavity surface-emitting lasers (VCSELs) by using an Al ion implanted aperture and employing a multi-layer electron-beam evaporated ITO intracavity contact. The use of an ion implanted aperture improves the lateral confinement over SiNx apertures by enabling a planar ITO design, while the multi-layer ITO contact minimizes scattering losses due to its epitaxially smooth morphology. The reported VCSEL has 10 QWs, with a 3nm quantum well width, 1nm barriers, a 5nm electron-blocking layer, and a 6.95- λ total cavity thickness. These advances yield a single longitudinal mode 406nm nonpolar VCSEL with a low threshold current density (∼16kA/cm2), a peak output power of ∼12μW, and a 100% polarization ratio. The lasing in the current aperture is observed to be spatially non-uniform, which is likely a result of filamentation caused by non-uniform current spreading, lateral optical confinement, contact resistance, and absorption loss.

  12. Nonpolar III-nitride vertical-cavity surface-emitting lasers incorporating an ion implanted aperture

    Science.gov (United States)

    Leonard, J. T.; Cohen, D. A.; Yonkee, B. P.; Farrell, R. M.; Margalith, T.; Lee, S.; DenBaars, S. P.; Speck, J. S.; Nakamura, S.

    2015-07-01

    We report on our recent progress in improving the performance of nonpolar III-nitride vertical-cavity surface-emitting lasers (VCSELs) by using an Al ion implanted aperture and employing a multi-layer electron-beam evaporated ITO intracavity contact. The use of an ion implanted aperture improves the lateral confinement over SiNx apertures by enabling a planar ITO design, while the multi-layer ITO contact minimizes scattering losses due to its epitaxially smooth morphology. The reported VCSEL has 10 QWs, with a 3 nm quantum well width, 1 nm barriers, a 5 nm electron-blocking layer, and a 6.95- λ total cavity thickness. These advances yield a single longitudinal mode 406 nm nonpolar VCSEL with a low threshold current density (˜16 kA/cm2), a peak output power of ˜12 μW, and a 100% polarization ratio. The lasing in the current aperture is observed to be spatially non-uniform, which is likely a result of filamentation caused by non-uniform current spreading, lateral optical confinement, contact resistance, and absorption loss.

  13. Characterizations of nonlinear optical properties on GaN crystals in polar, nonpolar, and semipolar orientations

    Science.gov (United States)

    Chen, Hong; Huang, Xuanqi; Fu, Houqiang; Lu, Zhijian; Zhang, Xiaodong; Montes, Jossue A.; Zhao, Yuji

    2017-05-01

    We report the basic nonlinear optical properties, namely, two-photon absorption coefficient ( β ), three-photon absorption coefficient ( γ ), and Kerr nonlinear refractive index ( n kerr), of GaN crystals in polar c-plane, nonpolar m-plane, and semipolar ( 20 21 ¯ ) plane orientations. A typical Z-scan technique was used for the measurement with a femtosecond Ti:S laser from wavelengths of 724 nm to 840 nm. For the two-photon absorption coefficient ( β ), similar values were obtained for polar, nonpolar, and semipolar samples, which are characterized to be ˜0.90 cm/GW at 724 nm and ˜0.65 cm/GW at 730 nm for all the three samples. For the Kerr nonlinear refractive index ( n kerr), self-focusing features were observed in this work, which is different from previous reports where self-defocusing features were observed on GaN in the visible and near-UV spectral regions. At 724 nm, n kerr was measured to be ˜2.5 0 × 10 - 14 cm 2 / W for all three samples. Three-photon absorption coefficients ( γ ) were also determined, which were found to be consistent with previous reports. This study provides valuable information on the basic nonlinear optical properties of III-nitride semiconductors, which are vital for a wide range of applications such as integrated photonics and quantum photonics.

  14. Non-Polar Natural Products from Bromelia laciniosa, Neoglaziovia variegata and Encholirium spectabile (Bromeliaceae

    Directory of Open Access Journals (Sweden)

    Ole Johan Juvik

    2017-09-01

    Full Text Available Extensive regional droughts are already a major problem on all inhabited continents and severe regional droughts are expected to become an increasing and extended problem in the future. Consequently, extended use of available drought resistant food plants should be encouraged. Bromelia laciniosa, Neoglaziovia variegata and Encholirium spectabile are excellent candidates in that respect because they are established drought resistant edible plants from the semi-arid Caatinga region. From a food safety perspective, increased utilization of these plants would necessitate detailed knowledge about their chemical constituents. However, their chemical compositions have previously not been determined. For the first time, the non-polar constituents of B. laciniosa, N. variegata and E. spectabile have been identified. This is the first thorough report on natural products from N. variegata, E. spectabile, and B. laciniosa. Altogether, 20 non-polar natural products were characterized. The identifications were based on hyphenated gas chromatography-high resolution mass spectrometry (GC-HRMS and supported by 1D and 2D Nuclear Magnetic Resonance (NMR plant metabolomics.

  15. Relative effectiveness of pretreatments on performance of Rhizomucor miehei lipase in nonpolar reaction media.

    Science.gov (United States)

    Garcia, Rafael A; Riley, Mark R

    2005-02-01

    Enzymes can be used in nonpolar reaction media to modify water-insoluble substrates. A variety of pretreatments, applied to the enzyme prior to introduction to the nonpolar media, can improve enzyme activity. However, the various pretreatments have not been studied using directly comparable conditions, nor have they been applied simultaneously to test for interactive effects. This work evaluates pretreatment of lipase with various classes of additives. The pretreated lipase is used to catalyze esterification between citronellol and acetic acid in a medium of n-hexane. The effectiveness of a particular pretreatment is presented in terms of relative performance (RP), which is equal to the number of times faster the pretreated lipase catalyzes the reaction relative to untreated lipase. The individual and interactive effects of the pretreatment factors were studied and compared. Buffer salts had a much stronger performance-enhancing effect than nonbuffer salts; pretreatment with 90% (w/w) sodium phosphate yielded lipase with an RP of approx 64. A strong interaction was found between the treatments with sodium phosphate and pH adjustment. These treatments may mitigate the inhibitory effect of acetic acid. Activating effects of phase interfaces and active-site protectants are shown to be complementary to other treatments, demonstrating that they likely act by distinct mechanisms.

  16. High indium non-polar InGaN clusters with infrared sensitivity grown by PAMBE

    Directory of Open Access Journals (Sweden)

    Shruti Mukundan

    2015-03-01

    Full Text Available Studies on the optical properties of InGaN alloy of relatively higher indium content are of potential interest to understand the effect of indium content on the optical band gap of epitaxial InGaN. We report the growth of self assembled non-polar high indium clusters of In0.55Ga0.45N over non-polar (11-20 a-plane In0.17Ga0.83N epilayer grown on a-plane (11-20GaN/(1-102 r-plane sapphire substrate using plasma assisted molecular beam epitaxy (PAMBE. Such structures are potential candidates for high brightness LEDs emitting in longer wavelengths. The high resolution X-ray diffraction studies revealed the formation of two distinct compositions of InxGa1−xN alloys, which were further confirmed by photoluminescence studies. A possible mechanism for the formation of such structure was postulated which was supported with the results obtained by energy dispersive X-ray analysis. The structure hence grown when investigated for photo-detecting properties, showed sensitivity to both infrared and ultraviolet radiations due to the different composition of InGaN region.

  17. Morphological, structural and electrical investigations on non-polar a-plane ZnO epilayers

    Science.gov (United States)

    Lautenschlaeger, Stefan; Eisermann, Sebastian; Hofmann, Michael N.; Roemer, Udo; Pinnisch, Melanie; Laufer, Andreas; Meyer, Bruno K.; von Wenckstern, Holger; Lajn, Alexander; Schmidt, Florian; Grundmann, Marius; Blaesing, Juergen; Krost, Alois

    2010-07-01

    We report on the growth of non-polar a-plane ZnO by CVD on r-plane-sapphire-wafers, a-plane GaN-templates and a-plane ZnO single-crystal substrates. Only the homoepitaxial growth approach leads to a Frank-van-der-Merwe growth mode, as shown by atomic force microscopy. The X-ray-diffraction spectra of the homoepitaxial thin films mirror the excellent crystalline quality of the ZnO substrate. The morphological and the structural quality of the homoepitaxial films is comparable to the best results for the growth on c-plane ZnO-substrates. The impurity incorporation, especially of group III elements, seems to be reduced when growing on the non-polar a-plane surface compared to the c-plane films as demonstrated by secondary ion mass spectrometry (SIMS). Optical properties have been investigated using low temperature photoluminescence measurements. We employed capacitance-voltage measurements ( C- V) to measure the background carrier density and its profile from substrate/film interface throughout the film to the surface. In thermal admittance spectroscopy (TAS) specific traps could be distinguished, and their thermal activation energies and capture cross sections could be determined.

  18. High indium non-polar InGaN clusters with infrared sensitivity grown by PAMBE

    Energy Technology Data Exchange (ETDEWEB)

    Mukundan, Shruti; Mohan, Lokesh; Chandan, Greeshma; Krupanidhi, S. B., E-mail: sbk@mrc.iisc.ernet.in; Shinde, Satish; Nanda, K. K. [Materials Research Centre, Indian Institute of Science, Bangalore 560012 (India); Roul, Basanta [Materials Research Centre, Indian Institute of Science, Bangalore 560012 (India); Central Research Laboratory, Bharat Electronics, Bangalore 560013 (India); Maiti, R.; Ray, S. K. [Department of Physics, Indian Institute of Technology, Kharagpur (India)

    2015-03-15

    Studies on the optical properties of InGaN alloy of relatively higher indium content are of potential interest to understand the effect of indium content on the optical band gap of epitaxial InGaN. We report the growth of self assembled non-polar high indium clusters of In{sub 0.55}Ga{sub 0.45}N over non-polar (11-20) a-plane In{sub 0.17}Ga{sub 0.83}N epilayer grown on a-plane (11-20)GaN/(1-102) r-plane sapphire substrate using plasma assisted molecular beam epitaxy (PAMBE). Such structures are potential candidates for high brightness LEDs emitting in longer wavelengths. The high resolution X-ray diffraction studies revealed the formation of two distinct compositions of In{sub x}Ga{sub 1−x}N alloys, which were further confirmed by photoluminescence studies. A possible mechanism for the formation of such structure was postulated which was supported with the results obtained by energy dispersive X-ray analysis. The structure hence grown when investigated for photo-detecting properties, showed sensitivity to both infrared and ultraviolet radiations due to the different composition of InGaN region.

  19. Barrierity of hydrogenated butadiene-acrylonitrile rubber and butyl rubber after exposure to organic solvents.

    Science.gov (United States)

    Krzemińska, Sylwia; Rzymski, Władysław M

    2011-01-01

    Resistance of antichemical clothing primarily depends on the type of material it is made from, in particular on the type of polymer used for coating the fabric carrier. This paper reports on systematic investigations on the influence of the cross-linking density of an elastomer and the composition of a cross-linked elastomer on its resistance to permeation of selected organic solvents. Tests of barrier material samples made from nonpolar butyl rubber (IIR) and polar hydrogenated butadiene-acrylonitrile rubber (HNBR) showed that (a) in rubber-solvent systems with medium thermodynamic affinity, cross-linking density influenced resistance to permeation and (b) the polarity of the system had a significant influence on barrierity.

  20. Variation in Scent Compounds of Oil-Bearing Rose (Rosa damascena Mill.) Produced by Headspace Solid Phase Microextraction, Hydrodistillation and Solvent Extraction

    OpenAIRE

    Sabri Erbaş; Hasan Baydar

    2016-01-01

    In this research, rose oil and rose water were hydro-distilled from the fresh oil-bearing rose flowers (Rosa damascena Mill.) using Clevenger-type apparatus. Rose concretes were extracted from the fresh rose flowers by using non-polar solvents, e.g. diethyl ether, petroleum ether, cyclo-hexane, chloroform and n-hexane, and subsequently by evaporation of the solvents under vacuum. Absolutes were produced from the concretes with ethyl alcohol extraction at -20°C, leaving behind the wax and othe...

  1. Next Generation Solvent Performance in the Modular Caustic Side Solvent Extraction Process - 15495

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Tara E. [Savannah River Remediation, LLC., Aiken, SC (United States); Scherman, Carl [Savannah River Remediation, LLC., Aiken, SC (United States); Martin, David [Savannah River Remediation, LLC., Aiken, SC (United States); Suggs, Patricia [Savannah River Site (SRS), Aiken, SC (United States)

    2015-01-14

    Changes to the Modular Caustic Side Solvent Extraction Unit (MCU) flow-sheet were implemented in the facility. Implementation included changing the scrub and strip chemicals and concentrations, modifying the O/A ratios for the strip, scrub, and extraction contactor banks, and blending the current BoBCalixC6 extractant-based solvent in MCU with clean MaxCalix extractant-based solvent. During the successful demonstration period, the MCU process was subject to rigorous oversight to ensure hydraulic stability and chemical/radionuclide analysis of the key process tanks (caustic wash tank, solvent hold tank, strip effluent hold tank, and decontaminated salt solution hold tank) to evaluate solvent carryover to downstream facilities and the effectiveness of cesium removal from the liquid salt waste. Results indicated the extraction of cesium was significantly more effective with an average Decontamination Factor (DF) of 1,129 (range was 107 to 1,824) and that stripping was effective. The contactor hydraulic performance was stable and satisfactory, as indicated by contactor vibration, contactor rotational speed, and flow stability; all of which remained at or near target values. Furthermore, the Solvent Hold Tank (SHT) level and specific gravity was as expected, indicating that solvent integrity and organic hydraulic stability were maintained. The coalescer performances were in the range of processing results under the BOBCalixC6 flow sheet, indicating negligible adverse impact of NGS deployment. After the Demonstration period, MCU began processing via routine operations. Results to date reiterate the enhanced cesium extraction and stripping capability of the Next Generation Solvent (NGS) flow sheet. This paper presents process performance results of the NGS Demonstration and continued operations of MCU utilizing the blended BobCalixC6-MaxCalix solvent under the NGS flowsheet.

  2. A study of the solvent effect on the morphology of RDX crystal by molecular modeling method.

    Science.gov (United States)

    Chen, Gang; Xia, Mingzhu; Lei, Wu; Wang, Fengyun; Gong, Xuedong

    2013-12-01

    Molecular dynamics simulations have been performed to investigate the effect of acetone solvent on the crystal morphology of RDX. The results show that the growth morphology of RDX crystal in vacuum is dominated by the (111), (020), (200), (002), and (210) faces using the BFDH laws, and (111) face is morphologically the most important. The analysis of surface structures of RDX crystal indicates that (020) face is non-polar, while (210), (111), (002), and (200) faces are polar among which (210) face has the strongest polarity. The interaction between acetone solvent and each RDX crystal face is different, and the order of binding energy on these surfaces is (210) > (111) > (002) > (200) > (020). The analysis of interactions among RDX and acetone molecules reveal that the system nonbond interactions are primary strong van der Waals and electrostatic interactions containing π-hole interactions, the weak hydrogen bond interactions are also existent. The effect of acetone on the growth of RDX crystal can be evaluated by comparing the binding energies of RDX crystalline faces. It can be predicted that compared to that in vacuum, in the process of RDX crystallization from acetone, the morphological importance of (210) face is increased more and (111) face is not the most important among RDX polar surfaces, while the non-polar (020) face probably disappears. The experimentally obtained RDX morphology grown from acetone is in agreement with the theoretical prediction.

  3. Conformation stability, halogen and solvent effects on CO stretching of 4-chloro-3-halogenobenzaldehydes.

    Science.gov (United States)

    Tursun, Mahir; Parlak, Cemal

    2015-04-15

    The effects of halogen and solvent on the conformation and carbonyl stretching of 4-chloro-3-halogenobenzaldehydes [C7H4ClXO; X=F (CFB), Cl (CCB) or Br (CBB)] were investigated using the density functional theory (DFT) method. The B3LYP functional was used by the 6-311+G(3df,p) basis set in combination with the polarizable continuum model (PCM). Computations were focused on the cis and trans isomers of the compounds in 18 different polar or non-polar organic solvents. The theoretical frequencies of the solvent-induced CO stretching vibrations were correlated with the empirical solvent parameters such as the Kirkwood-Bauer-Magat (KBM) equation, the solvent acceptor number (AN), Swain parameters and the linear solvation energy relationships (LSER). The present work explores the effect of both the halogen and medium on the conformational preference and CO vibrational frequency. The findings of this work can be useful to those systems involving changes in the conformations analogous to the compounds studied.

  4. Spectroscopic, solvent influence and thermal studies of ternary copper(II) complexes of diester and dinitrogen base ligands.

    Science.gov (United States)

    Emara, Adel A A; Abu-Hussein, Azza A A; Taha, Ahmed A; Mahmoud, Nelly H

    2010-10-15

    New mixed-ligand copper(II) complexes containing the bidentate dinitrogen ligands [N,N,N',N'-tetramethylethylenediamine (tmen), 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen)] and the bidentate dioxygen ligands [diethylmalonate (DEM), ethylacetoacetate (EAA) and ethylbenzoylacetate (EBA)] were prepared. The complexes were characterized by elemental analysis, infrared, mass and ESR spectral data, magnetic and molar conductance measurements and thermal gravimetric analysis. From the investigation, the geometries of the complexes are square planar for perchlorate complexes and a square pyramid or octahedral for the nitrate complexes. Solvatochromic behavior of the Cu(II) complexes indicates strong solvatochromism of their solutions in polar and non-polar solvents. The observed solvatochromism is due to the solute-solvent interaction between the chelate cation and the solvent molecules.

  5. Chiroptical Properties and the Racemization of Pyrene and Tetrathiafulvalene-Substituted Allene: Substitution and Solvent Effects on Racemization in Tetrathiafulvalenylallene

    Directory of Open Access Journals (Sweden)

    Masashi Hasegawa

    2014-03-01

    Full Text Available Dissymmetric 1,3-diphenylallene derivative 3 connected with 4,5-bis(methyl-thiotetrathiafulvalenyl and 1-pyrenyl substituents was prepared and characterized. The molecular structure was determined by X-ray crystallographic analysis. Optical resolution was accomplished using a recycling chiral HPLC, and its chiroptical properties were examined with optical rotation and electronic circular dichroism (ECD spectra. The title compound underwent photoracemization under daylight. This behavior was investigated in various solvents and compared with that of 1,3-bis(tetrathiafulvalenylallene (bis-TTF-allene derivative 2. The first-order rate plot of the intensity of the ECD spectra at a given time interval gave the rate of racemization. Mild racemization was observed in polar solvents, whereas a relatively fast rate was obtained in less polar solvents. In addition, the TTF groups of the allene also accelerate the racemization rate. These results suggest that the racemization mechanism occurs via a non-polar diradical structure.

  6. Polar-solvent-free colloidal synthesis of highly luminescent alkylammonium lead halide perovskite nanocrystals

    Science.gov (United States)

    Vybornyi, Oleh; Yakunin, Sergii; Kovalenko, Maksym V.

    2016-03-01

    A novel synthesis of hybrid organic-inorganic lead halide perovskite nanocrystals (CH3NH3PbX3, X = Br or I) that does not involve the use of dimethylformamide or other polar solvents is presented. The reaction between methylamine and PbX2 salts is conducted in a high-boiling nonpolar solvent (1-octadecene) in the presence of oleylamine and oleic acid as coordinating ligands. The resulting nanocrystals are characterized by high photoluminescence quantum efficiencies of 15-50%, outstanding phase purity and tunable shapes (nanocubes, nanowires, and nanoplatelets). Nanoplatelets spontaneously assemble into micrometer-length wires by face-to-face stacking. In addition, we demonstrate amplified spontaneous emission from thin films of green-emitting CH3NH3PbBr3 nanowires with low pumping thresholds of 3 μJ cm-2.A novel synthesis of hybrid organic-inorganic lead halide perovskite nanocrystals (CH3NH3PbX3, X = Br or I) that does not involve the use of dimethylformamide or other polar solvents is presented. The reaction between methylamine and PbX2 salts is conducted in a high-boiling nonpolar solvent (1-octadecene) in the presence of oleylamine and oleic acid as coordinating ligands. The resulting nanocrystals are characterized by high photoluminescence quantum efficiencies of 15-50%, outstanding phase purity and tunable shapes (nanocubes, nanowires, and nanoplatelets). Nanoplatelets spontaneously assemble into micrometer-length wires by face-to-face stacking. In addition, we demonstrate amplified spontaneous emission from thin films of green-emitting CH3NH3PbBr3 nanowires with low pumping thresholds of 3 μJ cm-2. Electronic supplementary information (ESI) available: Materials and methods, additional figures. See DOI: 10.1039/c5nr06890h

  7. Is Water a Universal Solvent for Life?

    Science.gov (United States)

    Pohorill, Andrew

    2012-01-01

    There are strong reasons to believe that the laws, principles and constraints of physics and chemistry are universal. It is much less clear how this universality translates into our understanding of the origins of life. Conventionally, discussions of this topic focus on chemistry that must be sufficiently rich to seed life. Although this is clearly a prerequisite for the emergence of living systems, I propose to focus instead on self-organization of matter into functional structures capable of reproduction, evolution and responding to environmental changes. In biology, most essential functions are largely mediated by noncovalent interactions (interactions that do not involve making or breaking chemical bonds). Forming chemical bonds is only a small part of what living systems do. There are specific implications of this point of view for universality. I will concentrate on one of these implications. Strength of non-covalent interactions must be properly tuned. If they were too weak, the system would exhibit undesired, uncontrolled response to natural fluctuations of physical and chemical parameters. If they were too strong kinetics of biological processes would be slow and energetics costly. This balance, however, is not a natural property of complex chemical systems. Instead, it has to be achieved with the aid of an appropriate solvent for life. In particular, potential solvents for life must be characterized by a high dielectric constant to ensure solubility of polar species and sufficient flexibility of biological structures stabilized by electrostatic interactions. Among these solvents, water exhibits a remarkable trait that it also promotes solvophobic (hydrophobic) interactions between non-polar species, typically manifested by a tendency of these species to aggregate and minimize their contacts with the aqueous solvent. Hydrophobic interactions are responsible, at least in part, for many self-organization phenomena in biological systems, such as the formation

  8. Occupational solvent exposure and cognition

    Science.gov (United States)

    Sabbath, E.L.; Glymour, M.M.; Berr, C.; Singh-Manoux, A.; Zins, M.; Goldberg, M.

    2012-01-01

    Objective: Chronic occupational solvent exposure is associated with long-term cognitive deficits. Cognitive reserve may protect solvent-exposed workers from cognitive impairment. We tested whether the association between chronic solvent exposure and cognition varied by educational attainment, a proxy for cognitive reserve. Methods: Data were drawn from a prospective cohort of French national gas and electricity (GAZEL) employees (n = 4,134). Lifetime exposure to 4 solvent types (chlorinated solvents, petroleum solvents, benzene, and nonbenzene aromatic solvents) was assessed using a validated job-exposure matrix. Education was dichotomized at less than secondary school or below. Cognitive impairment was defined as scoring below the 25th percentile on the Digit Symbol Substitution Test at mean age 59 (SD 2.8; 88% of participants were retired at testing). Log-binomial regression was used to model risk ratios (RRs) for poor cognition as predicted by solvent exposure, stratified by education and adjusted for sociodemographic and behavioral factors. Results: Solvent exposure rates were higher among less-educated patients. Within this group, there was a dose-response relationship between lifetime exposure to each solvent type and RR for poor cognition (e.g., for high exposure to benzene, RR = 1.24, 95% confidence interval 1.09–1.41), with significant linear trends (p < 0.05) in 3 out of 4 solvent types. Recency of solvent exposure also predicted worse cognition among less-educated patients. Among those with secondary education or higher, there was no significant or near-significant relationship between any quantification of solvent exposure and cognition. Conclusions: Solvent exposure is associated with poor cognition only among less-educated individuals. Higher cognitive reserve in the more-educated group may explain this finding. PMID:22641403

  9. Effect of Solvents on Microalbuminuria Among Automobile Painters

    Directory of Open Access Journals (Sweden)

    T Shushtarizadeh

    2008-06-01

    Full Text Available Background: The health risk associated with chronic exposure to organic solvents investigated in several epidemiologic studies indicates a significant relationship between solvent exposure and glomerulonephritis. Solvents are the most commonly used chemicals in industry. According to European statistics 43% of all solvent consumption takes place in the painting industry, 10% in metal cleansing, 6.7% in adhesives and 3.9 percent in the laundry (dry cleaning industries. Although BUN and creatinine indicate massive loss of glomerular function, microalbumin is a sensitive urinary marker for nephrotoxins in the early detection of solvent-induced effects on the glomerulus. The purpose of our study was to use microalbumin, serum BUN and serum creatinine levels to identify occupational solvent-induced effects on the glomerulus.Methods: Renal dysfunction was monitored by microalbumin, BUN and creatinine serum levels in a cohort study of 92 workers currently exposed to solvents (solvent group. A control group of 92 individuals were selected from parts of the same factory not exposed to solvents. All individuals in the study were men, without diabetes or hypertension. The percentage of smokers was equal between the two groups. The solvent group was selected using environmental monitoring of organic solvents in different parts of the painting room. The individuals were chosen by simple random selection. Exclusion factors included less than one year of work in the painting room, use analgesic or aminoglycoside one month before the study and medically diagnosed renal disease, such as glomerulonephritis or renal failure. Data was gathered using a questionnaire requesting demographic information, history of present and past diseases, present and past occupational history, drug history, history of illness in their colleagues and safety conditions at work (use of safety gloves, masks, clothing, goggles and general and local ventilation. The results analyzed with

  10. Ionic liquids and deep eutectic solvents in natural products research: mixtures of solids as extraction solvents.

    Science.gov (United States)

    Dai, Yuntao; van Spronsen, Jaap; Witkamp, Geert-Jan; Verpoorte, Robert; Choi, Young Hae

    2013-11-22

    Mixtures of solid chemicals may become liquid under certain conditions. These liquids are characterized by the formation of strong ionic (ionic liquids) or hydrogen bonds (deep eutectic solvents). Due to their extremely low vapor pressure, they are now widely used in polymer chemistry and synthetic organic chemistry, yet little attention has been paid to their use as extraction solvents of natural products. This review summarizes the preparation of ionic liquids and deep eutectic solvents with natural product components and recent progress in their applications to the extraction and analysis of natural products as well as the recovery of extracted compounds from their extracts. Additionally, various factors affecting extraction features of ionic liquids and deep eutectic solvents, as well as potential useful technologies including microwave and ultrasound to increase the extraction efficiency, are discussed.

  11. Solvent effects in chemistry

    CERN Document Server

    Buncel, Erwin

    2015-01-01

    This book introduces the concepts, theory and experimental knowledge concerning solvent effects on the rate and equilibrium of chemical reactions of all kinds.  It begins with basic thermodynamics and kinetics, building on this foundation to demonstrate how a more detailed understanding of these effects may be used to aid in determination of reaction mechanisms, and to aid in planning syntheses. Consideration is given to theoretical calculations (quantum chemistry, molecular dynamics, etc.), to statistical methods (chemometrics), and to modern day concerns such as ""green"" chemistry, where ut

  12. Alternative Solvents through Green Chemistry Project

    Science.gov (United States)

    Hintze, Paul E.; Quinn, Jacqueline

    2014-01-01

    Components in the aerospace industry must perform with accuracy and precision under extreme conditions, and surface contamination can be detrimental to the desired performance, especially in cases when the components come into contact with strong oxidizers such as liquid oxygen. Therefore, precision cleaning is an important part of a components preparation prior to utilization in aerospace applications. Current cleaning technologies employ a variety of cleaning agents, many of which are halogenated solvents that are either toxic or cause environmental damage. Thus, this project seeks to identify alternative precision cleaning solvents and technologies, including use of less harmful cleaning solvents, ultrasonic and megasonic agitation, low-pressure plasma cleaning techniques, and supercritical carbon dioxide extraction. Please review all data content found in the Public Data tab located at: https:techport.nasa.govview11697public

  13. Demonstration of Solvent Differences by Visible Polymer Swelling.

    Science.gov (United States)

    Ross, Joseph H.

    1983-01-01

    Effect of the "polarity" of low-polarity solvents on the amount of swelling produced in a solid polymer (demonstrated in an organic chemistry lecture) is also suitable as a laboratory experiment. Students can be assigned to a small group of solvents from the list provided. Procedures and materials needed are included. (Author/JN)

  14. Role of the electronegativity for the interface properties of non-polar heterostructures

    KAUST Repository

    Nazir, Safdar

    2012-04-01

    Density functional theory is used to investigate the interfaces in the non-polar ATiO 3/SrTiO 3 (A=Pb, Ca, Ba) heterostructures. All TiO 2-terminated interfaces show an insulating behavior. By reduction of the O content in the AO, SrO, and TiO 2 layers, metallic interface states develop, due to the occupation of the Ti 3d orbitals. For PbTiO 3/SrTiO 3, the Pb 6p states cross the Fermi energy. O vacancy formation energies depend strictly on the electronegativity and the effective volume of the A ion, while the main characteristics of the interface electronic states are maintained. © Europhysics Letters Association, 2012.

  15. Homoepitaxial HVPE-GaN growth on non-polar and semi-polar seeds

    Science.gov (United States)

    Amilusik, M.; Sochacki, T.; Lucznik, B.; Fijalkowski, M.; Smalc-Koziorowska, J.; Weyher, J. L.; Teisseyre, H.; Sadovyi, B.; Bockowski, M.; Grzegory, I.

    2014-10-01

    In this work homoepitaxial HVPE-GaN growth on non-polar and semi-polar GaN seeds was described. Two crystallization processes, in the same experimental conditions but using different carrier gases: N2 and H2, were performed. An influence of growth directions and growth conditions on the growth rate and properties (morphology, structural quality and oxygen and silicon contaminations) of obtained crystals were investigated and discussed. It was shown that the growth rate strongly depends on the growth direction and the carrier gas. It was demonstrated that for the semi-polar [20-21] direction it was possible to obtain high quality and highly conductive (without intentional doping) gallium nitride layers.

  16. ADSORPTION OF LATERALLY INTERACTING 1-NAPHTHOL/1-NAPHTHYL AMINE MIXTURES ON NONPOLAR SURFACES FROM AQUEOUS SOLUTIONS

    Institute of Scientific and Technical Information of China (English)

    Wei-ming Zhang; Jin-long Chen; Qun Chen; Ming-yang He; Bing-cai Pan; Quan-xing Zhang

    2006-01-01

    The binary adsorption behavior of 1-naphthol/1-naphthylamine mixtures in water on nonpolar adsorbent Amberlite XAD4 was investigated at 293 K, 303 K and 313 K, respectively. The experimental uptakes of 1-naphthol and 1-naphthylamine in all binary-component systems of different molar ratios were obviously higher than the corresponding uptakes predicted by the extended Langmuir model, assuming no interaction between the adsorbed molecules of the two components. This phenomenon was attributed to the cooperative adsorption effect arising from the hydrogen bonding interaction between 1-naphthol and 1-naphthylamine molecules. A modified extended Langmuir model was proposed to describe the binary adsorption behavior by means of introducing a fitting parameter related with the cooperative adsorption effect of the adsorbates.

  17. On the rotational energy distributions of reactive, non-polar species in the interstellar medium

    CERN Document Server

    Glinski, Robert J; Downum, Clark R

    2013-01-01

    A basic model for the formation of non-equilibrium rotational energy distributions is described for reactive, homo-polar diatomic molecules and ions in the interstellar medium. Kinetic models were constructed to calculate the rotational populations of C2+ under the conditions it would experience in the diffuse interstellar medium. As the non-polar ion reacts with molecular hydrogen, but not atomic hydrogen, the thermalization of a hot nascent rotational population will be arrested by chemical reaction when the H2 density begins to be significant. Populations that deviate strongly from the local thermodynamic equilibrium are predicted for C2+ in environments where it may be detectable. Consequences of this are discussed and a new optical spectrum is calculated.

  18. Dynamics of electric field induced particle alignment in nonpolar polymer matrix

    Science.gov (United States)

    Tai, Xiangyang; Wu, Guozhang; Yui, Hiroshi; Asai, Shigeo; Sumita, Masao

    2003-11-01

    The dynamics of electric field induced particle alignment in nonpolar polymer matrix to build one-dimensional conductive materials was investigated. The influence of electric field on particle alignment was real-time traced by dynamic percolation measurement using carbon black (CB) filled polyethylene as a model system. The activation energy of the continuous CB path formation was calculated and found to be unchanged with CB alignment. The critical percolation concentration at thermodynamic equilibrium state φc* was deduced to characterize the anisotropism of network structure, by which the thermodynamic prerequisite electric field E* for the transition from three-dimensional isotropic network to one-dimensional chain could be easily found out.

  19. Application of classical thermodynamics to the conductivity in non-polar media

    Science.gov (United States)

    Gourdin-Bertin, S.; Chassagne, C.

    2016-06-01

    Electrical conductivity in non-polar media is a subject which recently regained interest. If most of experiments and theoretical developments were done more than 50 years ago, new experiments and theories have been recently published. As the electrical conductivity describes, at low field, the equilibrium state of a system, it is natural to apply theories based on equilibrium thermodynamics. In this article, well-established classical thermodynamics and solvations models are applied to recently published data. This enables to get a new insight in intriguing phenomena, such as the linear dependence of the conductivity on the concentration of ionic surfactant and the evaluation of conductivity for the mixture of two miscible fluids, such as alcohol and alcane, which have very different conductivities.

  20. Comparison of solvent mixtures for pressurized solvent extraction of soil fatty acid biomarkers.

    Science.gov (United States)

    Jeannotte, Richard; Hamel, Chantal; Jabaji, Suha; Whalen, Joann K

    2008-10-19

    The extraction and transesterification of soil lipids into fatty acid methyl esters (FAMEs) is a useful technique for studying soil microbial communities. The objective of this study was to find the best solvent mixture to extract soil lipids with a pressurized solvent extractor system. Four solvent mixtures were selected for testing: chloroform:methanol:phosphate buffer (1:2:0.8, v/v/v), chloroform:methanol (1:2, v/v), hexane:2-propanol (3:2, v/v) and acetone. Soils were from agricultural fields and had a wide range of clay, organic matter and microbial biomass contents. Total lipid fatty acid methyl esters (TL-FAMEs) were the extractable soil lipids identified and quantified with gas chromatography and flame ionization detection. Concentrations of TL-FAMEs ranged from 57.3 to 542.2 nmole g(-1) soil (dry weight basis). The highest concentrations of TL-FAMEs were extracted with chloroform:methanol:buffer or chloroform:methanol mixtures than with the hexane:2-propanol or acetone solvents. The concentrations of TL-FAMEs in chemical groups, including saturated, branched, mono- and poly-unsaturated and hydroxy fatty acids were assessed, and biological groups (soil bacteria, mycorrhizal fungi, saprophytic fungi and higher plants) was distinguished. The extraction efficiency for the chemical and biological groups followed the general trend of: chloroform:methanol:buffer> or =chloroform:methanol>hexane:2-propanol=acetone. Discriminant analysis revealed differences in TL-FAME profiles based on the solvent mixture and the soil type. Although solvent mixtures containing chloroform and methanol were the most efficient for extracting lipids from the agricultural soils in this study, soil properties and the lipid groups to be studied should be considered when selecting a solvent mixture. According to our knowledge, this is the first report of soil lipid extraction with hexane:2-propanol or acetone in a pressurized solvent extraction system.

  1. Important factors influencing molecular weight cut-off determination of membranes in organic solvents

    NARCIS (Netherlands)

    Zwijnenberg, Harmen Jan; Dutczak, S.M.; Boerrigter, M.E.; Hempenius, Mark A.; Luiten-Olieman, Maria W.J.; Benes, Nieck Edwin; Wessling, Matthias; Stamatialis, Dimitrios

    2012-01-01

    In solvent resistant nanofiltration (SRNF), sensible selection of a membrane for a particular solvent/solute system is recognized as challenging. Prospective methods for suitability analysis of membranes include molecular weight cut off (MWCO) characterization. However, insufficient understanding of

  2. 78 FR 46447 - Conditional Exclusions From Solid Waste and Hazardous Waste for Solvent-Contaminated Wipes

    Science.gov (United States)

    2013-07-31

    ..., Chlorobenzene, Cresols, Cyclohexanone, Ethyl acetate, Ethyl benzene, Ethyl ether, Isobutanol, Methanol, Methyl..., Ethyl ether, Nitrobenzene, 2-Nirtopropane, and Pyridine. For a detailed discussion on these solvents... solvents include 2-Nitropropane, Nitrobenzene, Methyl ethyl ketone, Methylene chloride, Pyridine,...

  3. Chronic toxicity and body residues of the nonpolar narcotic 1,2,3,4-tetrachrlorobenzene in Chironomus riparius

    NARCIS (Netherlands)

    Leslie, H.A.; Kraak, M.H.S.; Hermens, J.L.

    2004-01-01

    The use of internal concentrations as a dose parameter for baseline toxicity requires an understanding of the relationship between accumulation level and toxic effects, not only for acute but also for chronic exposure. In this study of chronic toxicity of the nonpolar narcotic 1,2,3,4-tetrachloroben

  4. Chronic toxicity and body residues of the nonpolar narcotic 1,2,3,4-tetrachrlorobenzene in Chironomus riparius

    NARCIS (Netherlands)

    Leslie, H.A.; Kraak, M.H.S.; Hermens, J.L.

    2004-01-01

    The use of internal concentrations as a dose parameter for baseline toxicity requires an understanding of the relationship between accumulation level and toxic effects, not only for acute but also for chronic exposure. In this study of chronic toxicity of the nonpolar narcotic

  5. Evaluation of Extraction Protocols for Simultaneous Polar and Non-Polar Yeast Metabolite Analysis Using Multivariate Projection Methods

    Directory of Open Access Journals (Sweden)

    Nicolas P. Tambellini

    2013-07-01

    Full Text Available Metabolomic and lipidomic approaches aim to measure metabolites or lipids in the cell. Metabolite extraction is a key step in obtaining useful and reliable data for successful metabolite studies. Significant efforts have been made to identify the optimal extraction protocol for various platforms and biological systems, for both polar and non-polar metabolites. Here we report an approach utilizing chemoinformatics for systematic comparison of protocols to extract both from a single sample of the model yeast organism Saccharomyces cerevisiae. Three chloroform/methanol/water partitioning based extraction protocols found in literature were evaluated for their effectiveness at reproducibly extracting both polar and non-polar metabolites. Fatty acid methyl esters and methoxyamine/trimethylsilyl derivatized aqueous compounds were analyzed by gas chromatography mass spectrometry to evaluate non-polar or polar metabolite analysis. The comparative breadth and amount of recovered metabolites was evaluated using multivariate projection methods. This approach identified an optimal protocol consisting of 64 identified polar metabolites from 105 ion hits and 12 fatty acids recovered, and will potentially attenuate the error and variation associated with combining metabolite profiles from different samples for untargeted analysis with both polar and non-polar analytes. It also confirmed the value of using multivariate projection methods to compare established extraction protocols.

  6. Non-polar lipids accumulate during storage of transfusion products and do not contribute to the onset of transfusion-related acute lung injury.

    Science.gov (United States)

    Peters, A L; Vervaart, M A T; van Bruggen, R; de Korte, D; Nieuwland, R; Kulik, W; Vlaar, A P J

    2017-01-01

    The accumulation of non-polar lipids arachidonic acid, 5-hydroxyeicosatetraenoic acid (HETE), 12-HETE and 15-HETE during storage of transfusion products may play a role in the onset of transfusion-related acute lung injury (TRALI), a syndrome of respiratory distress after transfusion. We investigated non-polar lipid accumulation in red blood cells (RBCs) stored for 42 days, plasma stored for 7 days at either 4 or 20°C and platelet (PLT) transfusion products stored for 7 days. Furthermore, we investigated whether transfusion of RBCs with increased levels of non-polar lipids induces TRALI in a 'two-hit' human volunteer model. All products were produced following Dutch Blood Bank protocols and are according to European standards. Non-polar lipids were measured with high-performance liquid chromotography followed by mass spectrometry. All non-polar lipids increased in RBCs after 21 days of storage compared to baseline. The non-polar lipid concentration in plasma increased significantly, and the increase was even more pronounced in products stored at 20°C. In platelets, baseline levels of 5-HETE and 15-HETE were higher than in RBCs or plasma. However, the non-polar lipids did not change significantly during storage of PLT products. Infusion of RBCs with increased levels of non-polar lipids did not induce TRALI in LPS-primed human volunteers. We conclude that non-polar lipids accumulate in RBC and plasma transfusion products and that accumulation is temperature dependent. Accumulation of non-polar lipids does not appear to explain the onset of TRALI (Dutch Trial Register - NTR4455). © 2016 International Society of Blood Transfusion.

  7. Green Solvents for Precision Cleaning

    Science.gov (United States)

    Grandelli, Heather; Maloney, Phillip; DeVor, Robert; Surma, Jan; Hintze, Paul

    2013-01-01

    Aerospace machinery used in liquid oxygen (LOX) fuel systems must be precision cleaned to achieve a very low level of non-volatile residue (< 1 mg0.1 m2), especially flammable residue. Traditionally chlorofluorocarbons (CFCs) have been used in the precision cleaning of LOX systems, specifically CFC 113 (C2Cl3F3). CFCs have been known to cause the depletion of ozone and in 1987, were banned by the Montreal Protocol due to health, safety and environmental concerns. This has now led to the development of new processes in the precision cleaning of aerospace components. An ideal solvent-replacement is non-flammable, environmentally benign, non-corrosive, inexpensive, effective and evaporates completely, leaving no residue. Highlighted is a green precision cleaning process, which is contaminant removal using supercritical carbon dioxide as the environmentally benign solvent. In this process, the contaminant is dissolved in carbon dioxide, and the parts are recovered at the end of the cleaning process completely dry and ready for use. Typical contaminants of aerospace components include hydrocarbon greases, hydraulic fluids, silicone fluids and greases, fluorocarbon fluids and greases and fingerprint oil. Metallic aerospace components range from small nuts and bolts to much larger parts, such as butterfly valves 18 in diameter. A fluorinated grease, Krytox, is investigated as a model contaminant in these preliminary studies, and aluminum coupons are employed as a model aerospace component. Preliminary studies are presented in which the experimental parameters are optimized for removal of Krytox from aluminum coupons in a stirred-batch process. The experimental conditions investigated are temperature, pressure, exposure time and impeller speed. Temperatures of 308 - 423 K, pressures in the range of 8.3 - 41.4 MPa, exposure times between 5 - 60 min and impeller speeds of 0 - 1000 rpm were investigated. Preliminary results showed up to 86 cleaning efficiency with the

  8. A high-performance theory for thermodynamic study of solvation in mixed solvents

    Energy Technology Data Exchange (ETDEWEB)

    Rezaei Behbehani, G. [Department of Chemistry, Imam Khomeini International University Qazvin Iran, Imam Khomeini Street, Qazvin (Iran, Islamic Republic of)], E-mail: grb402003@yahoo.com; Waghorne, W.E. [School of Chemistry and Chemical Biology, UCD, Dublin 4 (Ireland)

    2008-11-20

    The enthalpies of transfer, {delta}H{sub t}{sup {theta}}, of the solutes from pure solvent A to mixtures of A and a second solvent B were studied by isothermal titration calorimetry and analysed in terms of the new extended solvation theory. These data are considered in terms of the new developed solvation theory including variable ({alpha}n + {beta}N), the net effect of the solute on the solvent-solvent bonding and is positive if there is a net breaking or weakening of solvent-solvent bonds.

  9. Methods of producing adsorption media including a metal oxide

    Science.gov (United States)

    Mann, Nicholas R; Tranter, Troy J

    2014-03-04

    Methods of producing a metal oxide are disclosed. The method comprises dissolving a metal salt in a reaction solvent to form a metal salt/reaction solvent solution. The metal salt is converted to a metal oxide and a caustic solution is added to the metal oxide/reaction solvent solution to adjust the pH of the metal oxide/reaction solvent solution to less than approximately 7.0. The metal oxide is precipitated and recovered. A method of producing adsorption media including the metal oxide is also disclosed, as is a precursor of an active component including particles of a metal oxide.

  10. Molecular, vibrational and electronic structure of 4-bromo-2-halogenobenzaldehydes: Halogen and solvent effects

    Science.gov (United States)

    Fernández, David; Parlak, Cemal; Bilge, Metin; Kaya, Mehmet Fatih; Tursun, Mahir; Keşan, Gürkan; Rhyman, Lydia; Ramasami, Ponnadurai; Şenyel, Mustafa

    2017-09-01

    The halogen and solvent effects on the structure of 4-bromo-2-halogenobenzaldehydes [C7H4BrXO; X = F (BFB), Cl (BCB) or Br (BBB)] were investigated by the density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. The B3LYP functional and HF and MP2 levels of theory were used with the 6-311+G(3df,p) or aug-cc-pVDZ basis sets. Computations were focused on the cis and trans conformers of the investigated compounds in the gas phase and solutions of 18 different polar or non-polar organic solvents. The computed frequencies of the C=O stretching vibration of the compounds were correlated with some empirical solvent parameters such as the Kirkwood-Bauer-Magat (KBM) equation, solvent acceptor number (AN), Swain parameters and linear solvation energy relationships (LSERs). The electronic properties of the compounds were also examined. The present work explores the effects of the medium and halogen on the conformation, geometrical parameters, dipole moment, ν(C=O) vibration, UV data, frontier orbitals and density-of-states diagram of the compounds. The findings of this research can be useful for studies on benzaldehydes.

  11. SOLVENT EXTRACTION OF URANIUM VALUES

    Science.gov (United States)

    Feder, H.M.; Ader, M.; Ross, L.E.

    1959-02-01

    A process is presented for extracting uranium salt from aqueous acidic solutions by organic solvent extraction. It consists in contacting the uranium bearing solution with a water immiscible dialkylacetamide having at least 8 carbon atoms in the molecule. Mentioned as a preferred extractant is dibutylacetamide. The organic solvent is usually used with a diluent such as kerosene or CCl/sub 4/.

  12. Supercritical multicomponent solvent coal extraction

    Science.gov (United States)

    Corcoran, W. H.; Fong, W. S.; Pichaichanarong, P.; Chan, P. C. F.; Lawson, D. D. (Inventor)

    1983-01-01

    The yield of organic extract from the supercritical extraction of coal with larger diameter organic solvents such as toluene is increased by use of a minor amount of from 0.1 to 10% by weight of a second solvent such as methanol having a molecular diameter significantly smaller than the average pore diameter of the coal.

  13. Selection and design of solvents

    DEFF Research Database (Denmark)

    Gani, Rafiqul

    . With increasing interest on issues such as waste, sustainability, environmental impact and green chemistry, the selection and design of solvents have become important problems that need to be addressed during chemical product-process design and development. Systematic methods and tools suitable for selection......Solvents are liquid solutions consisting of one or more chemicals. They have a very wide use and their use is not necessarily restricted to the process industries. This lecture will discuss the different roles and uses of solvents in chemical products and processes that manufacture them...... and design of solvents will be presented together with application examples. The selection problem is defined as finding known chemicals that match the desired functions of a solvent for a specified set of applications. The design problem is defined as finding the molecular structure (or mixture of molecules...

  14. Solvent degradation products in nuclear fuel processing solvents

    Energy Technology Data Exchange (ETDEWEB)

    Shook, H.E. Jr.

    1988-06-01

    The Savannah River Plant uses a modified Purex process to recover enriched uranium and separate fission products. This process uses 7.5% tri-n-butyl phosphate (TBP) dissolved in normal paraffin hydrocarbons for the solvent extraction of a nitric acid solution containing the materials to be separated. Periodic problems in product decontamination result from solvent degradation. A study to improve process efficiency has identified certain solvent degradation products and suggested mitigation measures. Undecanoic acid, lauric acid, and tridecanoic acid were tentatively identified as diluent degradation products in recycle solvent. These long-chain organic acids affect phase separation and lead to low decontamination factors. Solid phase extraction (SPE) was used to concentrate the organic acids in solvent prior to analysis by high performance liquid chromatography (HPLC). SPE and HPLC methods were optimized in this work for analysis of decanoic acid, undecanoic acid, and lauric acid in solvent. Accelerated solvent degradation studies with 7.5% TBP in normal paraffin hydrocarbons showed that long-chain organic acids and long-chain alkyl butyl phosphoric acids are formed by reactions with nitric acid. Degradation of both tributyl phosphate and hydrocarbon can be minimized with purified normal paraffin replacing the standard grade presently used. 12 refs., 1 fig., 3 tabs.

  15. Switchable Polarity Solvents: Are They Green?

    Science.gov (United States)

    Plaumann, Heinz

    2017-03-01

    Solvents play an incredibly important role in large scale chemical reactions. Switchable polarity solvents may prove to be a class of solvent that offers energy and material efficiencies greater than existing solvents. This paper examines such solvents and their potential in a variety of chemical reactions.

  16. Expanding solvent SAGD in heavy oil reservoirs

    Energy Technology Data Exchange (ETDEWEB)

    Govind, P.A. [Society of Petroleum Engineers, Canadian Section, Calgary, AB (Canada)]|[ConocoPhillips Canada Resources Corp., Calgary, AB (Canada); Das, S.; Wheeler, T.J. [Society of Petroleum Engineers, Richardson, TX (United States)]|[ConocoPhillips Co., Houston, TX (United States); Srinivasan, S. [Society of Petroleum Engineers, Richardson, TX (United States)]|[Texas Univ., Austin, TX (United States)

    2008-10-15

    Steam assisted gravity drainage (SAGD) projects have proven effective for the recovery of oil and bitumen. Expanding solvent (ES) SAGD pilot projects have also demonstrated positive results of improved performance. This paper presented the results of a simulation study that investigated several important factors of the ES-SAGD process, including solvent types; concentration; operating pressure; and injection strategy. The objectives of the study were to examine the effectiveness of the ES-SAGD process in terms of production acceleration and energy requirements; to optimize solvent selection; to understand the effect of dilation in unconsolidated oil sands and the directional impact on reservoir parameters and oil production rate in ES-SAGD; and to understand the impact of operating conditions such as pressure, solvent concentration, circulation preheating period and the role of conduction heating and grid size in this process. The advantages of ES-SAGD over SAGD were also outlined. The paper presented results of sensitivity studies that were conducted on these four factors. Conclusions and recommendations for operating strategy were also offered. It was concluded that dilation is an important factor for SAGD performance at high operating pressure. 8 refs., 15 figs.

  17. Heme and non-heme iron transporters in non-polarized and polarized cells

    Directory of Open Access Journals (Sweden)

    Yasui Yumiko

    2010-06-01

    Full Text Available Abstract Background Heme and non-heme iron from diet, and recycled iron from hemoglobin are important products of the synthesis of iron-containing molecules. In excess, iron is potentially toxic because it can produce reactive oxygen species through the Fenton reaction. Humans can absorb, transport, store, and recycle iron without an excretory system to remove excess iron. Two candidate heme transporters and two iron transporters have been reported thus far. Heme incorporated into cells is degraded by heme oxygenases (HOs, and the iron product is reutilized by the body. To specify the processes of heme uptake and degradation, and the reutilization of iron, we determined the subcellular localizations of these transporters and HOs. Results In this study, we analyzed the subcellular localizations of 2 isoenzymes of HOs, 4 isoforms of divalent metal transporter 1 (DMT1, and 2 candidate heme transporters--heme carrier protein 1 (HCP1 and heme responsive gene-1 (HRG-1--in non-polarized and polarized cells. In non-polarized cells, HCP1, HRG-1, and DMT1A-I are located in the plasma membrane. In polarized cells, they show distinct localizations: HCP1 and DMT1A-I are located in the apical membrane, whereas HRG-1 is located in the basolateral membrane and lysosome. 16Leu at DMT1A-I N-terminal cytosolic domain was found to be crucial for plasma membrane localization. HOs are located in smooth endoplasmic reticulum and colocalize with NADPH-cytochrome P450 reductase. Conclusions HCP1 and DMT1A-I are localized to the apical membrane, and HRG-1 to the basolateral membrane and lysosome. These findings suggest that HCP1 and DMT1A-I have functions in the uptake of dietary heme and non-heme iron. HRG-1 can transport endocytosed heme from the lysosome into the cytosol. These localization studies support a model in which cytosolic heme can be degraded by HOs, and the resulting iron is exported into tissue fluids via the iron transporter ferroportin 1, which is

  18. Membrane augmented distillation to separate solvents from water

    Science.gov (United States)

    Huang, Yu; Baker, Richard W.; Daniels, Rami; Aldajani, Tiem; Ly, Jennifer H.; Alvarez, Franklin R.; Vane, Leland M.

    2012-09-11

    Processes for removing water from organic solvents, such as ethanol. The processes include distillation to form a rectified overhead vapor, compression of the rectified vapor, and treatment of the compressed vapor by two sequential membrane separation steps.

  19. Solvent effects and driving forces in pillararene inclusion complexes.

    Science.gov (United States)

    Schönbeck, Christian; Li, Hui; Han, Bao-Hang; Laursen, Bo W

    2015-06-04

    Pillararenes, a recently discovered class of aromatic macrocycles, form inclusion complexes with a large number of guest molecules, but not much is known about the driving forces of complexation, including the role of the solvent. We have measured the binding thermodynamics for a small number of model complexes in several solvents and used computational chemistry to rationalize the obtained results and identify the driving forces of complexation. Favorable electrostatic interactions between the host and guest are obtained when the charge distribution in the guest matches the negative electrostatic potential in the cavity of the pillararene. Polar guests, however, also interact strongly with polar solvents, thereby shifting the complexation equilibrium away from the complex. The shape of the solvent molecules is another important factor as some solvents are sterically hindered from entering the pillararene cavity. By changing solvent from acetonitrile to o-xylene the binding constant in one case increased more than 4 orders of magnitude. Even electrostatically similar solvents such as o-xylene and p-xylene have very different impacts on the binding constants due to their different abilities to fit into the cavity. The study illustrates the importance of taking into account the interactions between the solvent and the complexing species in the investigation and design of molecular host:guest systems.

  20. Remarks on energetic conditions for positronium formation in non-polar solids. Coupled Dipole Method application

    CERN Document Server

    Pietrow, Marek

    2015-01-01

    A numerical program calculating an energy of a positron or (and) an electron near the free volume in solid n-alkanes has been build. The theory of interaction of e+ or (and) e- with this non-polar media based on polarizability has been introduced. The energy of the e+ -- e- pair in the bulk was compared to that calculated when the pair forms a positronium (Ps) inside the free volume. The calculations are based on the Coupled Dipole Method and the dipole-dipole interaction energy for induced dipoles is taken into account. Furthermore, a correction of a local permittivity for the e+ -- e- interaction is calculated taking into account the non-isotropic medium between them. The method is a step toward more accurate calculations of energetic conditions during the Ps formation in matter. The possibility of emission of the excess energy of the Ps formation as electromagnetic radiation is discussed. It is argued that if this radiation is observed, it can be used as a new spectroscopic tool providing information about...

  1. Nonpolarized signaling reveals two distinct modes of 3D cell migration.

    Science.gov (United States)

    Petrie, Ryan J; Gavara, Núria; Chadwick, Richard S; Yamada, Kenneth M

    2012-04-30

    We search in this paper for context-specific modes of three-dimensional (3D) cell migration using imaging for phosphatidylinositol (3,4,5)-trisphosphate (PIP3) and active Rac1 and Cdc42 in primary fibroblasts migrating within different 3D environments. In 3D collagen, PIP3 and active Rac1 and Cdc42 were targeted to the leading edge, consistent with lamellipodia-based migration. In contrast, elongated cells migrating inside dermal explants and the cell-derived matrix (CDM) formed blunt, cylindrical protrusions, termed lobopodia, and Rac1, Cdc42, and PIP3 signaling was nonpolarized. Reducing RhoA, Rho-associated protein kinase (ROCK), or myosin II activity switched the cells to lamellipodia-based 3D migration. These modes of 3D migration were regulated by matrix physical properties. Specifically, experimentally modifying the elasticity of the CDM or collagen gels established that nonlinear elasticity supported lamellipodia-based migration, whereas linear elasticity switched cells to lobopodia-based migration. Thus, the relative polarization of intracellular signaling identifies two distinct modes of 3D cell migration governed intrinsically by RhoA, ROCK, and myosin II and extrinsically by the elastic behavior of the 3D extracellular matrix.

  2. Optical Kerr Effect Spectroscopy of a Nonpolar Solute in Dicationic versus Monocationic Ionic Liquids

    Science.gov (United States)

    Gurung, Eshan; Xue, Lianjie; Tamas, George; Quitevis, Edward

    2014-03-01

    A comparison of the intermolecular dynamics of small nonpolar solute molecules in monocationic and dicationic ionic liquids (ILs) was performed using optical heterodyne-detected Raman-induced Kerr effect spectroscopy (OHD-RIKES). The optical Kerr effect (OKE) spectrum of CS2 in 1-methyl-3-propylimidazolium bis(trifluoromethane-sulfonyl)amide [C3mim][NTf2] and 1,6-bis(3-methylimidazolium-1-yl) hexane bis(trifluoromethane-sulfonyl)amide [C6(mim)2][NTf2]2 was investigated as a function of concentration at 295 K. An additivity model with components from the subpicosecond dynamics of IL and CS2 was used to interpret the OKE spectra of the mixtures. The spectrum of CS2 in the two ILs is lower in frequency and narrower than that of neat CS2. The spectrum of CS2 in the dicationic IL is higher in frequency than in the monocationic IL. This result shows that CS2 molecule experiences a stiffer potential in dicationic ILs as compared to monocationic ILs. Higher stiffness in C6(mim)2][NTf2]2 might be due to a more ordered arrangement and lower mobility of the alkyl chains linking the imidazolium rings. This work was supported by NSF Grant CHE-1153077.

  3. Effects of polar and nonpolar groups on the solubility of organic compounds in soil organic matter

    Science.gov (United States)

    Chiou, C.T.; Kile, D.E.

    1994-01-01

    Vapor sorption capacities on a high-organic-content peat, a model for soil organic matter (SOM), were determined at room temperature for the following liquids: n-hexane, 1,4-dioxane, nitroethane, acetone, acetonitrile, 1-propanol, ethanol, and methanol. The linear organic vapor sorption is in keeping with the dominance of vapor partition in peat SOM. These data and similar results of carbon tetrachloride (CT), trichloroethylene (TCE), benzene, ethylene glycol monoethyl ether (EGME), and water on the same peat from earlier studies are used to evaluate the effect of polarity on the vapor partition in SOM. The extrapolated liquid solubility from the vapor isotherm increases sharply from 3-6 wt % for low-polarity liquids (hexane, CT, and benzene) to 62 wt % for polar methanol and correlates positively with the liquid's component solubility parameters for polar interaction (??P) and hydrogen bonding (??h). The same polarity effect may be expected to influence the relative solubilities of a variety of contaminants in SOM and, therefore, the relative deviations between the SOM-water partition coefficients (Kom) and corresponding octanol-water partition coefficients (Kow) for different classes of compounds. The large solubility disparity in SOM between polar and nonpolar solutes suggests that the accurate prediction of Kom from Kow or Sw (solute water solubility) would be limited to compounds of similar polarity.

  4. Improving oil recovery in the CO2 flooding process by utilizing nonpolar chemical modifiers☆

    Institute of Scientific and Technical Information of China (English)

    Yong Yang; Xiangliang Li; Ping Guo; Yayun Zhuo; Yong Sha

    2016-01-01

    By means of experiments of CO2 miscibility with crude oil, four nonpolar chemicals were evaluated in order to enhance the miscibility of CO2 with crude oil. Through pre-slug injection and joint injection of toluene in CO2, crude oil displacement experiments in the slim-tube were conducted to investigate effects of the toluene-enhanced CO2 flooding under simulated subterranean reservoir conditions. Experimental results showed that toluene can enhance extraction of oil into CO2 and dissolution of CO2 into oil with the increment of 251%and 64%respectively. Addition of toluene can obviously improve the oil recovery in either pre-slug injection or joint injection, and the crude oil recovery increased with the increase of the toluene concentration. The oil recov-ery can increase by 22.5%in pre-slug injection with the high toluene concentration. Pre-slug injection was recom-mended because it can consume less toluene than joint injection. This work could be useful to development and application of the CO2 flooding in the oil recovery as wel as CO2 emission reduction.

  5. Competitive and cooperative adsorption behaviors of phenol and aniline onto nonpolar macroreticular adsorbents

    Institute of Scientific and Technical Information of China (English)

    ZHANG Wei-ming; CHEN Jin-long; PAN Bing-cai; ZHANG Quan-xing

    2005-01-01

    The adsorption behaviors of phenol and aniline on nonpolar macroreticular adsorbents( NDA100 and Amberlite XAD4) were investigated in single or binary batch system at 293K and 313K respectively in this study. The results indicated that the adsorption isotherms of phenol and aniline on both adsorbents in both systems fitted well Langmuir equation, which indicated a favourable and exothermic process. At the lower equilibrium concentrations, the individual amount adsorbed of phenol or aniline or macroreticular adsorbents in single-component systems was higher than those in binary-component systems because of the competition between phenol and aniline towards the adsorption sites. It is noteworthy, on the contrast, that at higher concentrations, the total uptake amounts of phenol and aniline in binary-component systems were obviously larger than that in single-component systems, and a large excess was noted on the adsorbent surface at saturation, which is presumably due to the cooperative effect primarily arisen from the hydrogen bonding or weak acidbase interaction between phenol and aniline.

  6. A silicone column for GC analysis of polar and nonpolar chemicals

    Science.gov (United States)

    Shen, T. C.

    1991-10-01

    The investigation of the Saturnian System is being proposed jointly by NASA and the European Space Agency (ESA). The mission is scheduled for a launch in 1996. The mission provides an opportunity for close observation and exploration of Saturn's atmosphere, the complex Saturnian System of satellites and rings, Titan (Saturn's planet-sized moon), and Saturn's magnetosphere. The mission gives special attention to Titan which is blanketed by a thick, opaque atmosphere. An atmospheric probe will be deposited into the Titan Atmosphere for in situ measurement during a slow, three hour descent to the surface. The results from this analysis may provide the information which is important to the research of chemical evolution, and the origin of life. An analytical system was developed as a part of the Titan Aerosol Gas Experiment (TAGEX), a proposed experiment for the Cassini Mission. This system will use two highly sensitive detectors, the Metastable Ionization Detector (MID) and the Ion Mobility Spectrometer (IMS). Unfortunately, when commercial columns are utilized with these highly sensitive detectors, volatile components continuously bleed from the column and interfere with the detector. In addition, light columns must be able to separate polar and nonpolar organic chemicals within 10-15 minutes under isothermal conditions for the Titan Mission. Therefore, a highly crosslinked silicone polymeric packed column was developed which is able to efficiently separate amines, alcohols, and hydrocarbons with retention times less that 15 minutes at 100 C isothermal condition.

  7. Self-consistent theory of nanodomain formation on nonpolar surfaces of ferroelectrics

    Science.gov (United States)

    Morozovska, Anna N.; Ievlev, Anton V.; Obukhovskii, Vyacheslav V.; Fomichov, Yevhen; Varenyk, Oleksandr V.; Shur, Vladimir Ya.; Kalinin, Sergei V.; Eliseev, Eugene A.

    2016-04-01

    We propose a self-consistent theoretical approach capable of describing the features of the anisotropic nanodomain formation induced by a strongly inhomogeneous electric field of a charged scanning probe microscopy tip on nonpolar cuts of ferroelectrics. We obtained that a threshold field, previously regarded as an isotropic parameter, is an anisotropic function that is specified from the polar properties and lattice pinning anisotropy of a given ferroelectric in a self-consistent way. The proposed method for the calculation of the anisotropic threshold field is not material specific, thus the field should be anisotropic in all ferroelectrics with the spontaneous polarization anisotropy along the main crystallographic directions. The most evident examples are uniaxial ferroelectrics, layered ferroelectric perovskites, and low-symmetry incommensurate ferroelectrics. Obtained results quantitatively describe the differences at several times in the nanodomain length experimentally observed on X and Y cuts of LiNb O3 and can give insight into the anisotropic dynamics of nanoscale polarization reversal in strongly inhomogeneous electric fields.

  8. Molecular Dynamics Simulation of Behaviours of Non-Polar Droplets Merging and Interactions with Hydrophobic Surfaces

    Institute of Scientific and Technical Information of China (English)

    Y.Y.Yan; C.Y.Ji

    2008-01-01

    This paper presents a molecular dynamics simulation of the behaviours of non-polar droplets merging and also the fluid molecules interacting with a hydrophobic surface. Such behaviours and transport phenomena are popular in general micro-channel flow boiling and two-phase flow. The droplets are assumed to be composed of Lennards-Jones type molecules. Periodic boundary conditions are applied in three coordinate directions ofa 3-D system, where there exist two liquid droplets and their vapour. The two droplets merge when they come within the prescribed small distance. The merging of two droplets apart from each other at different initial distances is tested and the possible larger (or critical) non-dimensional distance, in which droplets merging can occur, is discussed. The evolution of the merging process is simulated numerically by employing the Molecular Dynamics (MD) method. For interactions with hydrophobic solid wail, a system with fluid confined between two walls is used to study the wetting phenomena of fluid and solid wail. The results are compared with those of hydrophilic wall to show the unique characteristics of hydrophobic interactions by microscopic methods.

  9. Composition of the non-polar extracts and antimicrobial activity of Chorisia insignis HBK. leaves

    Directory of Open Access Journals (Sweden)

    Salma Ahmed Mahmoud El Sawi

    2014-12-01

    Full Text Available Objective: To investigate the chemical constituents of the petroleum ether extract and the ether fraction of the 70% ethanol extract of Chorisia insignis HBK. leaves, as well as screen its antimicrobial activity. Methods: Different chromatographic methods were applied to investigate the non-polar extracts and the diffusion assay method was applied to study the antimicrobial activity. Results: A total of 50 compounds from the unsaponifiable matter and 20 fatty acid methyl esters were identified from the petroleum ether extract by GC/MS analysis. n-Hentriacontane, n-tritriacontane, stigmastanol, 3-methoxy-5, 6-dihydrostigmasterol, 7,8-dihydroergosterol, 4-methylcholesterol, cholestanol, multiflorenol, cholest-5-en-3-one, cholest-6-one, 5,6- dihydroergosterol, stigmasterol, dihydroalbigenin and 11-methyl-Δ5,7,9,15,17,23-triacont-hex-ene were isolated from the petroleum ether extract. Methyl heptacosanoate and quinic acid ester of rhamnose were isolated from the ether fraction of the 70% ethanol extract. Antimicrobial activity of the total alcohol extract and the successive fractions showed that the ether and the ethyl acetate fractions have potent antibacterial activity against Bacillus subtilis and Bacillus cereus. Conclusions: The ether and the ethyl acetate fractions could be used in pharmaceutical formulations as antibacterial agents against Bacillus subtilis and Bacillus cereus, and further clinical trials should be performed in order to support the above investigations.

  10. Analysis of current transport properties in nonpolar a-plane ZnO-based Schottky diodes

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hogyoung [Seoul National University of Science and Technology, Seoul (Korea, Republic of); Kim, Haeri; Kim, Dongwook [Ewha Womans University, Seoul (Korea, Republic of)

    2014-09-15

    Using current-voltage (I - V) measurements, we investigated the temperature-dependent transport properties in Ag/nonpolar a-plane ZnO Schottky diodes. The bias-dependent ideality factors were altered by the different temperatures and showed a hump at lower temperatures. The series resistance of the diode depended on the temperatures, which was related to the number of free carriers contributing to the series resistance. For high forward bias, the slope m obtained from the lnI - lnV curves decreased with increasing temperature, assuring the space-charge-limited-current (SCLC) model controlled by an exponential distribution of traps. The reverse-biased current transport was associated with the Schottky effect, with a thermally-assisted tunneling for lower voltages and the Poole-Frenkel effect for higher voltages. The density of localized states (N{sub t}) was obtained by applying the theory of SCLC transport, which yielded a N{sub t} value of 8.32 x 10{sup 11} eV{sup -1}cm{sup -3}.

  11. Handbook of organic solvent properties

    CERN Document Server

    Smallwood, Ian

    2012-01-01

    The properties of 72 of the most commonly used solvents are given, tabulated in the most convenient way, making this book a joy for industrial chemists to use as a desk reference. The properties covered are those which answer the basic questions of: Will it do the job? Will it harm the user? Will it pollute the air? Is it easy to handle? Will it pollute the water? Can it be recovered or incinerated? These are all factors that need to be considered at the early stages of choosing a solvent for a new product or process.A collection of the physical properties of most commonly used solvents, their

  12. The Solvent Selection framework: solvents for organic synthesis, separation processes and ionic-organic synthesis

    DEFF Research Database (Denmark)

    Mitrofanov, Igor; Sansonetti, Sascha; Abildskov, Jens

    2012-01-01

    problems are presented: 1) solvent selection and design for organic synthesis, 2) solvent screening and design of solvent mixtures for pharmaceutical applications and 3) ionic liquids selection and design as solvents. The application of the framework is highlighted successfully through case studies...... focusing on solvent replacement problem in organic synthesis and solvent mixture design for ibuprofen respectively....

  13. Electroluminescence from nonpolar n-ZnO/p-AlGaN heterojunction light-emitting diode on r-sapphire

    Science.gov (United States)

    Chen, Jingwen; Zhang, Jun; Dai, Jiangnan; Wu, Feng; Wang, Shuai; Chen, Cheng; Long, Hanling; Liang, Renli; Zhao, Chong; Chen, Changqing; Tang, Zhiwu; Cheng, Hailing; He, Yunbin; Li, Mingkai

    2017-03-01

    Nonpolar a-plane n-ZnO/p-AlGaN heterojunction light-emitting diodes (LEDs) have been prepared on r-sapphire substrate using metal organic chemical vapor deposition and a pulsed laser deposition method. The dominant electroluminescence emission at 390 nm from the interband transition in n-ZnO layer under a forward bias was observed. Interestingly, electroluminescence with emission at 385 nm based on an avalanche mechanism was also achieved under reverse bias. The mechanisms of both the electroluminescence and I–V characteristics are discussed in detail by considering the avalanche effect. It is demonstrated that the crystalline quality of n-ZnO, not the p-AlGaN, is what affects the performance of the nonpolar ZnO based avalanche LED.

  14. Homoepitaxial nonpolar (10-10) ZnO/ZnMgO monolithic microcavities: Towards reduced photonic disorder

    Energy Technology Data Exchange (ETDEWEB)

    Zuniga-Perez, J., E-mail: jzp@crhea.cnrs.fr; Kappei, L.; Deparis, C.; Chenot, S.; Leroux, M. [CRHEA-CNRS, Rue Bernard Gregory, 06560 Valbonne (France); Reveret, F.; Jamadi, O.; Leymarie, J. [Clermont Université, Institut Pascal (IP), BP 10448, F-63000 Clermont-Ferrand (France); CNRS, UMR 6602, IP, F-63171 Aubière (France); Grundmann, M. [CRHEA-CNRS, Rue Bernard Gregory, 06560 Valbonne (France); Institut für Experimentelle Physik II, Fakultät für Physik und Geowissenschaften, Universität Leipzig, Linnestr. 5, 04103 Leipzig (Germany); Prado, E. de [CRHEA-CNRS, Rue Bernard Gregory, 06560 Valbonne (France); Departamento de Física Aplicada y Electromagnetismo, Universitat de Valencia, c/Dr Moliner 50, Burjassot, Valencia 46100 (Spain)

    2016-06-20

    Nonpolar ZnO/ZnMgO-based optical microcavities have been grown on (10-10) m-plane ZnO substrates by plasma-assisted molecular beam epitaxy. Reflectivity measurements indicate an exponential increase of the cavity quality factor with the number of layers in the distributed Bragg reflectors. Most importantly, microreflectivity spectra recorded with a spot size in the order of 2 μm show a negligible photonic disorder (well below 1 meV), leading to local quality factors equivalent to those obtained by macroreflectivity. The anisotropic character of the nonpolar heterostructures manifests itself both in the surface features, elongated parallel to the in-plane c direction, and in the optical spectra, with two cavity modes being observed at different energies for orthogonal polarizations.

  15. An analytical method of predicting Lee-Kesler-Ploecker binary interaction coefficients: Part 1, For non-polar hydrocarbon mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Sand, J.R.

    1994-12-31

    An analytical method is proposed for finding numerical values of binary interaction coefficients for non-polar hydrocarbon mixtures when the Lee-Kesler (LK) equation of state is applied. The method is based on solving simultaneous equations, which are Ploecker`s mixing rules for pseudocritical parameters of a mixture, and the Lee-Kesler equation for the saturation line. For a hydrocarbon mixture, the method allows prediction of {kappa}{sub ij} interaction coefficients (ICs) which are close to values obtained by processing experimental p-v-t data on the saturation line and subsequent averaging. For mixtures of hydrocarbon molecules containing from 2 to 9 carbon atoms, the divergence between calculated and experimentally based ICs is no more than {plus_minus}0.4%. The possibility of extending application of this method to other non-polar substances is discussed.

  16. Extraction of hydrocarbons from microalga Botryococcus braunii with switchable solvents.

    Science.gov (United States)

    Samorì, Chiara; Torri, Cristian; Samorì, Giulia; Fabbri, Daniele; Galletti, Paola; Guerrini, Franca; Pistocchi, Rossella; Tagliavini, Emilio

    2010-05-01

    Lipid extraction is a critical step in the development of biofuels from microalgae. Here a new procedure was proposed to extract hydrocarbons from dried and water-suspended samples of the microalga Botryococcus braunii by using switchable-polarity solvents (SPS) based on 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and an alcohol. The high affinity of the non-ionic form of DBU/alcohol SPS towards non-polar compounds was exploited to extract hydrocarbons from algae, while the ionic character of the DBU-alkyl carbonate form, obtained by the addition of CO(2), was used to recover hydrocarbons from the SPS. DBU/octanol and DBU/ethanol SPS were tested for the extraction efficiency of lipids from freeze-dried B. braunii samples and compared with n-hexane and chloroform/methanol. The DBU/octanol system was further evaluated for the extraction of hydrocarbons directly from algal culture samples. DBU/octanol exhibited the highest yields of extracted hydrocarbons from both freeze-dried and liquid algal samples (16% and 8.2% respectively against 7.8% and 5.6% with n-hexane).

  17. Study on Surface Properties for Non-polar Fluids with Density Functional Theory%密度泛函理论在非极性纯流体表面性质研究中的应用

    Institute of Scientific and Technical Information of China (English)

    吴畏; 陆九芳; 付东; 刘金晨; 李以圭

    2004-01-01

    The density functional theory, simplified by the local density approximation and mean-field approximation, is applied to study the surface properties of pure non-polar fluids. A reasonable long rang correction is adopted to avoid the truncation of the potential. The perturbation theory is applied to establish the equation for the phase equilibrium, in which the hard-core chain fluid is as the reference fluid and the Yukawa potential is used as the perturbation term. Three parameters, ε/k, d and ms, are regressed from the vapor-liquid equilibria, and the surface properties, including density profile, surface tension and local surface tension profile are predicted with these parameters.

  18. The atomic structure of polar and non-polar InGaN quantum wells and the green gap problem.

    Science.gov (United States)

    Humphreys, C J; Griffiths, J T; Tang, F; Oehler, F; Findlay, S D; Zheng, C; Etheridge, J; Martin, T L; Bagot, P A J; Moody, M P; Sutherland, D; Dawson, P; Schulz, S; Zhang, S; Fu, W Y; Zhu, T; Kappers, M J; Oliver, R A

    2017-02-03

    We have used high resolution transmission electron microscopy (HRTEM), aberration-corrected quantitative scanning transmission electron microscopy (Q-STEM), atom probe tomography (APT) and X-ray diffraction (XRD) to study the atomic structure of (0001) polar and (11-20) non-polar InGaN quantum wells (QWs). This paper provides an overview of the results. Polar (0001) InGaN in QWs is a random alloy, with In replacing Ga randomly. The InGaN QWs have atomic height interface steps, resulting in QW width fluctuations. The electrons are localised at the top QW interface by the built-in electric field and the well-width fluctuations, with a localisation energy of typically 20meV. The holes are localised near the bottom QW interface, by indium fluctuations in the random alloy, with a localisation energy of typically 60meV. On the other hand, the non-polar (11-20) InGaN QWs contain nanometre-scale indium-rich clusters which we suggest localise the carriers and produce longer wavelength (lower energy) emission than from random alloy non-polar InGaN QWs of the same average composition. The reason for the indium-rich clusters in non-polar (11-20) InGaN QWs is not yet clear, but may be connected to the lower QW growth temperature for the (11-20) InGaN QWs compared to the (0001) polar InGaN QWs.

  19. Practical Approaches to Green Solvents

    National Research Council Canada - National Science Library

    Joseph M. DeSimone

    2002-01-01

    Solvents are widely used in commercial manufacturing and service industries. Despite abundant precaution, they inevitably contaminate our air, land, and water because they are difficult to contain and recycle...

  20. Hansen Cleaning Solvent Research Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Environmental regulation will force current baseline  precision cleaning solvent (AK-225) to be phased out starting 2015. We plan to develop  a new...

  1. Tailoring of polar and nonpolar ZnO planes on MgO (001) substrates through molecular beam epitaxy.

    Science.gov (United States)

    Zhou, Hua; Wang, Hui-Qiong; Liao, Xia-Xia; Zhang, Yufeng; Zheng, Jin-Cheng; Wang, Jia-Ou; Muhemmed, Emin; Qian, Hai-Jie; Ibrahim, Kurash; Chen, Xiaohang; Zhan, Huahan; Kang, Junyong

    2012-03-09

    Polar and nonpolar ZnO thin films were deposited on MgO (001) substrates under different deposition parameters using oxygen plasma-assisted molecular beam epitaxy (MBE). The orientations of ZnO thin films were investigated by in situ reflection high-energy electron diffraction and ex situ X-ray diffraction (XRD). The film roughness measured by atomic force microscopy evolved as a function of substrate temperature and was correlated with the grain sizes determined by XRD. Synchrotron-based X-ray absorption spectroscopy (XAS) was performed to study the conduction band structures of the ZnO films. The fine structures of the XAS spectra, which were consistent with the results of density functional theory calculation, indicated that the polar and nonpolar ZnO films had different electronic structures. Our work suggests that it is possible to vary ZnO film structures from polar to nonpolar using the MBE growth technique and hence tailoring the electronic structures of the ZnO films.PACS: 81; 81.05.Dz; 81.15.Hi.

  2. The nature of carrier localisation in polar and nonpolar InGaN/GaN quantum wells

    Science.gov (United States)

    Dawson, P.; Schulz, S.; Oliver, R. A.; Kappers, M. J.; Humphreys, C. J.

    2016-05-01

    In this paper, we compare and contrast the experimental data and the theoretical predictions of the low temperature optical properties of polar and nonpolar InGaN/GaN quantum well structures. In both types of structure, the optical properties at low temperatures are governed by the effects of carrier localisation. In polar structures, the effect of the in-built electric field leads to electrons being mainly localised at well width fluctuations, whereas holes are localised at regions within the quantum wells, where the random In distribution leads to local minima in potential energy. This leads to a system of independently localised electrons and holes. In nonpolar quantum wells, the nature of the hole localisation is essentially the same as the polar case but the electrons are now coulombically bound to the holes forming localised excitons. These localisation mechanisms are compatible with the large photoluminescence linewidths of the polar and nonpolar quantum wells as well as the different time scales and form of the radiative recombination decay curves.

  3. Interactions of methanol, ethanol, and 1-propanol with polar and nonpolar species in water at cryogenic temperatures.

    Science.gov (United States)

    Souda, Ryutaro

    2017-01-18

    Methanol is known as a strong inhibitor of hydrate formation, but clathrate hydrates of ethanol and 1-propanol can be formed in the presence of help gases. To elucidate the hydrophilic and hydrophobic effects of alcohols, their interactions with simple solute species are investigated in glassy, liquid, and crystalline water using temperature-programmed desorption and time-of-flight secondary ion mass spectrometry. Nonpolar solute species embedded underneath amorphous solid water films are released during crystallization, but they tend to withstand water crystallization under the coexistence of methanol additives. The CO2 additives are released after crystallization along with methanol desorption. These results suggest strongly that nonpolar species that are hydrated (i.e., caged) associatively with methanol can withstand water crystallization. In contrast, ethanol and 1-propanol additives weakly affect the dehydration of nonpolar species during water crystallization, suggesting that the former tend to be caged separately from the latter. The hydrophilic vs. hydrophobic behavior of alcohols, which differs according to the aliphatic group length, also manifests itself in the different abilities of surface segregation of alcohols and their effects on the water crystallization kinetics.

  4. Applied biotransformations in green solvents.

    Science.gov (United States)

    Hernáiz, María J; Alcántara, Andrés R; García, José I; Sinisterra, José V

    2010-08-16

    The definite interest in implementing sustainable industrial technologies has impelled the use of biocatalysts (enzymes or cells), leading to high chemo-, regio- and stereoselectivities under mild conditions. As usual substrates are not soluble in water, the employ of organic solvents is mandatory. We will focus on different attempts to combine the valuable properties of green solvents with the advantages of using biocatalysts for developing cleaner synthetic processes.

  5. The fluorescence of 5-cyano-2-(1-pyrrolyl)-pyridine (CPP) in different solvents and in solid argon: An experimental and theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Abramov, S.; Schweke, D.; Zilberg, S. [Department of Physical Chemistry and the Farkas Center for Light Induced Processes, Hebrew University of Jerusalem, Jerusalem (Israel); Haas, Y. [Department of Physical Chemistry and the Farkas Center for Light Induced Processes, Hebrew University of Jerusalem, Jerusalem (Israel)], E-mail: yehuda@chem.ch.huji.ac.il

    2007-05-21

    The fluorescence spectrum of 5-cyano-2-(1-pyrrolyl)-pyridine (CPP) was measured in several solvents as well as in an argon matrix. Based on comparison with other compounds and on ab initio calculations it is proposed that the fluorescence in the argon matrix and in non-polar solvents is due to two electronic excited states: one is of locally excited nature, the other a charge transfer (CT) state. In polar solvents the spectrum is dominated by the CT emission. The photo-physical behavior of CPP is discussed by comparison with that of other molecules exhibiting dual fluorescence and in view of a recent model developed for the benzene analog.

  6. Spectrophotometric and spectroscopic studies of charge transfer complexes of p-toluidine as an electron donor with picric acid as an electron acceptor in different solvents.

    Science.gov (United States)

    Singh, Neeti; Khan, Ishaat M; Ahmad, Afaq

    2010-04-01

    The charge transfer complexes of the donor p-toluidine with pi-acceptor picric acid have been studied spectrophotometrically in various solvents such as carbon tetrachloride, chloroform, dichloromethane acetone, ethanol, and methanol at room temperature using absorption spectrophotometer. The results indicate that formation of CTC in non-polar solvent is high. The stoichiometry of the complex was found to be 1:1 ratio by straight-line method between donor and acceptor with maximum absorption bands. The data are discussed in terms of formation constant (K(CT)), molar extinction coefficient (epsilon(CT)), standard free energy (DeltaG(o)), oscillator strength (f), transition dipole moment (mu(EN)), resonance energy (R(N)) and ionization potential (I(D)). The results indicate that the formation constant (K(CT)) for the complex was shown to be dependent upon the nature of electron acceptor, donor and polarity of solvents that were used.

  7. Spectrophotometric studies on the charge-transfer interaction between p-nitroaniline with chloranilic acid as π-acceptor in different polar solvents

    Science.gov (United States)

    Singh, Neeti; Ahmad, Afaq

    2017-01-01

    The charge transfer interaction between the donor p-nitroaniline with the acceptor chloranilic acid has been studied spectrophotometrically in various solvents such as chloroform, ethanol, and methanol at room temperature. The results indicate that formation of CTC in non-polar solvent is high. The stoichiometry of the complex was found to be 1:1 ratio by straight-line method between donor and acceptor with maximum absorption bands. The data are discussed in terms of formation constant (KCT), molar extinction coefficient (εCT), standard free energy (ΔG), oscillator strength (f), transition dipole moment (μN), resonance energy (RN) and ionization potential (ID). The results indicate that the formation constant (KCT) for the complex was shown to be dependent upon the nature of electron acceptor, donor and polarity of solvents that were used. The formation of the complex has been confirmed by UV-visible, FT-IR, and 1H NMR techniques.

  8. Recent Advances in Anhydrous Solvents for CO2 Capture: Ionic Liquids, Switchable Solvents, and Nanoparticle Organic Hybrid Materials

    Directory of Open Access Journals (Sweden)

    YOUNGJUNE ePARK

    2015-10-01

    Full Text Available CO2 capture by amine scrubbing, which has a high CO2 capture capacity and a rapid reaction rate, is the most employed and investigated approach to date. There are a number of recent large-scale demonstrations including the Boundary Dam Carbon Capture Project by SaskPower in Canada that have reported successful implementations of aqueous amine solvent in CO2 capture from flue gases. The findings from these demonstrations will significantly advance the field of CO2 capture in the coming years. While the latest efforts in aqueous amine solvents are exciting and promising, there are still several drawbacks to amine-based CO2 capture solvents including high volatility and corrosiveness of the amine solutions, as well as the high parasitic energy penalty during the solvent regeneration step. Thus, in a parallel effort, alternative CO2 capture solvents, which are often anhydrous, have been developed as the third-generation CO2 capture solvents. These novel classes of liquid materials include: Ionic Liquids (ILs, CO2-triggered switchable solvents (i.e., CO2 Binding Organic Liquids (CO2BOLs, Reversible Ionic Liquids (RevILs, and Nanoparticle Organic Hybrid Materials (NOHMs. This paper provides a review of these various anhydrous solvents and their potential for CO2 capture. Particular attention is given to the mechanisms of CO2 absorption in these solvents, their regeneration and their processability – especially taking into account their viscosity. While not intended to provide a complete coverage of the existing literature, this review aims at pointing the major findings reported for these new classes of CO2 capture media.

  9. Comparative Study of the Characteristics of the Basal Plane Stacking Faults of Nonpolar a-Plane and Semipolar (11(2)2) GaN

    Institute of Scientific and Technical Information of China (English)

    XU Sheng-Rui; HAO Yue; LIN Zhi-Yu; XUE Xiao-Yong; LIU Zi-Yang; MA Jun-Cai; JIANG Teng; MAO Wei; WANG Dang-Hui; ZHANG Jin-Cheng

    2012-01-01

    Nonpolar (11-20) and semipolar (11222) GaN are grown on r-plane and m-plane sapphire by MOCVD to investigate the characteristics of basal plane stacking faults (BSFs). Transmission electron microscopy reveals that the density of BSFs for the semipolar (11-22) and nonpolar a-plane GaN template is 3×105cm-1 and 8×10 cm'1, respectively. The semipolar (11-22) GaN shows an arrowhead-like structure, and the nonpolar a-plane GaN has a much smoother morphology with a streak along the c-axis. Both nonpolar (11-20) and semipolar (11-22) GaN have very strong BSF luminescence due to the optically active character of the BSFs.%Nonpolar (11(2)0) and semipolar (11(2)2) GaN are grown on r-plane and m-plane sapphire by MOCVD to investigate the characteristics of basal plane stacking faults (BSFs).Transmission electron microscopy reveals that the density of BSFs for the semipolar (11(2)2) and nonpolar a-plane GaN template is 3x105 cm-1 and 8×105 cm-1,respectively.The semipolar (11(2)2) GaN shows an arrowhead-like structure,and the nonpolar a-plane GaN has a much smoother morphology with a streak along the c-axis.Both nonpolar (11(2)0) and semipolar (11(2)2) GaN have very strong BSF luminescence due to the optically active character of the BSFs.

  10. Solvent/Non-Solvent Sintering To Make Microsphere Scaffolds

    Science.gov (United States)

    Laurencin, Cato T.; Brown, Justin L.; Nair, Lakshmi

    2011-01-01

    A solvent/non-solvent sintering technique has been devised for joining polymeric microspheres to make porous matrices for use as drug-delivery devices or scaffolds that could be seeded with cells for growing tissues. Unlike traditional sintering at elevated temperature and pressure, this technique is practiced at room temperature and pressure and, therefore, does not cause thermal degradation of any drug, protein, or other biochemical with which the microspheres might be loaded to impart properties desired in a specific application. Also, properties of scaffolds made by this technique are more reproducible than are properties of comparable scaffolds made by traditional sintering. The technique involves the use of two miscible organic liquids: one that is and one that is not a solvent for the affected polymer. The polymeric microspheres are placed in a mold having the size and shape of the desired scaffold, then the solvent/non-solvent mixture is poured into the mold to fill the void volume between the microspheres, then the liquid mixture is allowed to evaporate. Some of the properties of the resulting scaffold can be tailored through choice of the proportions of the liquids and the diameter of the microspheres.

  11. Recent Advances in Nonpolar and Semipolar InGaN Light-Emitting Diodes (LEDs).

    Science.gov (United States)

    Jang, Jongjin; Woo, Seohwi; Min, Daehong; Nam, Okhyun

    2015-03-01

    The III-nitrides have attracted much attention because of their applicability in optoelectronic devices, whose emission wavelengths range from green to ultraviolet light due to their wide band gap. However, conventional c-plane GaN-based devices are influenced significantly by spontaneous and piezoelectric polarization effects, which could pose a limitation for increased luminous efficiency as a result of the quantum confined stark effect. Since the early 2000s, many groups have tried to solve these problems by examining the growth of GaN on non- or semipolar surface planes. High power non- and semipolar LEDs can be realized by the growth of a thick active layer. In addition, it is expected that it is possible to grow nonpolar InGaN LEDs with high quality p-GaN layers due to lower hole activation energy, and also long-wavelength semipolar InGaN LEDs because of the capacity for high indium incorporation in the quantum wells (QWs). However, non- and semipolar structures grown on sapphire substrate usually contain a high density of basal stacking faults and threading dislocations. For this reason, the growth of non- and semipolar GaN-based LEDs on a sapphire substrate has been attempted through the introduction of defect reduction techniques such as epitaxial lateral overgrowth, patterned sapphire substrate and re-growth techniques on a porous GaN layer, etc. Also, some researchers have grown high quality non- and semipolar GaN-based LEDs using non- and semipolar freestanding GaN substrates. In this review paper, we introduce and discuss recent progress in the development of non- and semipolar GaN-based LEDs and freestanding GaN substrates.

  12. Foaming properties of monoglycerol fatty acid esters in nonpolar oil systems.

    Science.gov (United States)

    Shrestha, Lok Kumar; Aramaki, Kenji; Kato, Hiroyuki; Takase, Yoshihiko; Kunieda, Hironobu

    2006-09-26

    Foaming properties of monoglycerol fatty acid esters that have different alkyl chain lengths were studied in different nonpolar oils, namely liquid paraffin (LP 70), squalane, and squalene. The effect of the hydrocarbon chain length of the surfactant, the concentration, the nature of the oil, and the temperature on the nonaqueous foam stability was mainly studied. Five weight percent of glycerol alpha-monododecanoate (monolaurin) formed highly stable foams in squalane at 25 degrees C, and the foams were stable for more than 14 h. Foam stability of the monolaurin/LP 70 and the monolaurin/squalene systems are almost similar, and the foams were stable for more than 12 h. Foam stability was decreased as the hydrocarbon chain length of the monoglyceride decreased. In the glycerol alpha-monodecanoate (monocaprin)-oil systems, the foams were stable only for 3-4 h, depending on the nature of the oil. However, the foams formed in the glycerol alpha-monooctanoate (monocaprylin)-oil systems coarsened very quickly, leading to the progressive destruction of foam films, and all of the foams collapsed within a few minutes. Foam stability decreased when the oil was changed from squalane to squalene, in both monocaprin and monolaurin systems. It was observed that, in the dilute regions, these monoglycerides form fine solid dispersions in the aforementioned oils at 25 degrees C. At higher temperatures, the solid melts to isotropic single-liquid or two-liquid phases and the foams formed collapsed within 5 min. Judging from the wide-angle X-ray scattering (WAXS) and the foaming test, it is concluded that the stable foams are mainly caused by the dispersion of the surfactant solids (beta-crystal) and foam stability is largely influenced by the shape and size of the dispersed solid particles.

  13. Exploring assembly energetics of the 30S ribosomal subunit using an implicit solvent approach.

    Science.gov (United States)

    Trylska, Joanna; McCammon, J Andrew; Brooks Iii, Charles L

    2005-08-10

    To explore the relationship between the assembly of the 30S ribosomal subunit and interactions among the constituent components, 16S RNA and proteins, relative binding free energies of the T. thermophilus 30S proteins to the 16S RNA were studied based on an implicit solvent model of electrostatic, nonpolar, and entropic contributions. The late binding proteins in our assembly map were found not to bind to the naked 16S RNA. The 5' domain early kinetic class proteins, on average, carry the highest positive charge, get buried the most upon binding to 16S RNA, and show the most favorable binding. Some proteins (S10/S14, S6/S18, S13/S19) have more stabilizing interactions while binding as dimers. Our computed assembly map resembles that of E. coli; however, the central domain path is more similar to that of A. aeolicus, a hyperthermophilic bacteria.

  14. Psychomotor Effects of Mixed Organic Solvents on Rubber Workers

    Directory of Open Access Journals (Sweden)

    O Aminian

    2014-04-01

    Full Text Available Background: Exposure to organic solvents is common among workers.Objective: To assess neurobehavioral effects of long-term exposure to organic solvents among rubber workers in Tehran, Iran.Methods: Across-sectional study was conducted on 223 employees of a rubber industry. The participants completed a data collection sheet on their occupational and medical history, and demographic characteristics including age, work experience, education level; they performed 6 psychiatric tests on the neurobehavioral core test battery (NCTB that measure simple reaction time, short-term memory (digit span, Benton, eye-hand coordination (Purdue pegboard, pursuit aiming, and perceptual speed (digit symbol.Results: Workers exposed and not exposed to organic solvents had similar age and education distribution. The mean work experience of the exposed and non-exposed workers was 5.9 and 4.4 years, respectively. The exposed workers had a lower performance compared to non-exposed workers in all psychomotor tests. After controlling for the confounders by logistic regression analysis, it was found that exposure to organic solvents had a significant effect on the results of digit symbols, digit span, Benton, aiming, and simple reaction time tests. No significant effect was observed in pegboard test.Conclusion: Occupational exposure to organic solvent can induce subtle neurobehavioral changes among workers exposed to organic solvents; therefore, periodical evaluation of the central nervous system by objective psychomotor tests is recommended among those who are chronically exposed to organic solvents.

  15. Solvents and supporting electrolytes for vanadium acetylacetonate flow batteries

    Science.gov (United States)

    Shinkle, Aaron A.; Pomaville, Timothy J.; Sleightholme, Alice E. S.; Thompson, Levi T.; Monroe, Charles W.

    2014-02-01

    Properties of supporting electrolytes and solvents were examined for use with vanadium acetylacetonate - a member of the class of metal(β-diketonate) active species - in non-aqueous redox flow batteries. Twenty supporting-electrolyte/solvent combinations were screened for ionic conductivity and supporting-electrolyte solubility. Hexane, tetrahydrofuran, and dimethylcarbonate solvents did not meet minimal conductivity and solubility criteria for any of the electrolytes used, which included tetraethylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, and (1-butyl, 3-methyl)imidazolium bis(trifluoromethanesulfonyl)imide. Ionic conductivities and solubilities for solutions of these electrolytes passed screening criteria in acetonitrile and dimethylformamide solvents, in which maximum supporting-electrolyte and active-species solubilities were determined. Active-species electrochemistry was found to be reversible in several solvent/support systems; for some systems the voltammetric signatures of unwanted side reactions were suppressed. Correlations between supporting-solution properties and performance metrics suggest that an optimal solvent for a vanadium acetylacetonate RFB should have a low solvent molar volume for active-species solubility, and a high Hansen polarity for conductivity.

  16. Alternative Solvents and Technologies for Precision Cleaning of Aerospace Components

    Science.gov (United States)

    Grandelli, Heather; Maloney, Phillip; DeVor, Robert; Hintze, Paul

    2014-01-01

    Precision cleaning solvents for aerospace components and oxygen fuel systems, including currently used Vertrel-MCA, have a negative environmental legacy, high global warming potential, and have polluted cleaning sites. Thus, alternative solvents and technologies are being investigated with the aim of achieving precision contamination levels of less than 1 mg/sq ft. The technologies being evaluated are ultrasonic bath cleaning, plasma cleaning and supercritical carbon dioxide cleaning.

  17. Green solvent-based approaches for synthesis of nanomaterials

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The use of green solvents (including supercritical fluids and ionic liquids) in the synthesis of nanomaterials is highlighted. The methods described can not only reduce or eliminate the use or generation of substances hazardous to health and the environment, but can also be used to efficiently prepare nanomaterials with high performances. The unique characteristics of green solvents are responsible for the green features and unusual advantages of these approaches.

  18. Phase Behavior of Mixtures of Ionic Liquids and Organic Solvents

    DEFF Research Database (Denmark)

    Abildskov, Jens; Ellegaard, Martin Dela; O’Connell, J.P.

    2010-01-01

    A corresponding-states form of the generalized van der Waals equation, previously developed for mixtures of an ionic liquid and a supercritical solute, is here extended to mixtures including an ionic liquid and a solvent (water or organic). Group contributions to characteristic parameters...... solvents. Here we show results for heavier and more-than-sparingly solutes such as carbon dioxide and propane in ionic liquids....

  19. Use of solvent mixtures for total lipid extraction of Chlorella vulgaris and gas chromatography FAME analysis.

    Science.gov (United States)

    Moradi-Kheibari, Narges; Ahmadzadeh, Hossein; Hosseini, Majid

    2017-06-07

    Lipid extraction is the bottleneck step for algae-based biodiesel production. Herein, 12 solvent mixture systems (mixtures of three non-polar and two polar organic solvents) were examined to evaluate their effects on the total lipid yield from Chlorella vulgaris (C. vulgaris). Moreover, the extraction yields of three solvent systems with maximum extraction efficiency of esterifiable lipids were determined by acidic transesterification and GC-FID analysis. Three solvent systems, which resulted in a higher extraction yield, were further subjected to fatty acid methyl ester (FAME) analysis. The total lipid extraction yields (based on dry biomass) were (38.57 ± 1.51), (25.33 ± 0.58), and (25.17 ± 1.14) %, for chloroform-methanol (1:2) (C1M2), hexane-methanol (1:2) (H1M2), and chloroform-methanol (2:1) (C2M1), respectively. The extraction efficiency of C1M2 was approximately 1.5 times higher than H1M2 and C2M1, whereas the FAME profile of extracted lipids by H1M2 and C1M2 were almost identical. Moreover, the esterifiable lipid extraction yields of (18.14 ± 2.60), (16.66 ± 0.35), and (13.22 ± 0.31) % (based on dry biomass) were obtained for C1M2, H1M2, and C2M1 solvent mixture systems, respectively. The biodiesel fuel properties produced from C. vulgaris were empirically predicted and compared to that of the EN 14214 and ASTM 6751 standard specifications.

  20. Pretreatment of Lignocellulosic Biomass with Ionic Liquids and Ionic Liquid-Based Solvent Systems.

    Science.gov (United States)

    Hou, Qidong; Ju, Meiting; Li, Weizun; Liu, Le; Chen, Yu; Yang, Qian

    2017-03-20

    Pretreatment is very important for the efficient production of value-added products from lignocellulosic biomass. However, traditional pretreatment methods have several disadvantages, including low efficiency and high pollution. This article gives an overview on the applications of ionic liquids (ILs) and IL-based solvent systems in the pretreatment of lignocellulosic biomass. It is divided into three parts: the first deals with the dissolution of biomass in ILs and IL-based solvent systems; the second focuses on the fractionation of biomass using ILs and IL-based solvent systems as solvents; the third emphasizes the enzymatic saccharification of biomass after pretreatment with ILs and IL-based solvent systems.

  1. THE EFFECTS OF SOLVENTS ON SUB-BITUMINOUS COAL BELOW ITS PYROLYSIS TEMPERATURE

    Energy Technology Data Exchange (ETDEWEB)

    Grens III., Edward A.; Dorighi, Gary P.; Lindsey, David

    1979-12-01

    The action of organic solvents on a sub-bituminous coal has been examined over the temperature range of 150-350°C. The solvents studied included benzene, tetralin, pyridine, quinoline, piperidine, and ethylenediamine. The yield of extracted material varied widely with solvent and temperature, exceeding 60% (daf) for ethylenediamine at 250°C. The extracts were anlayzed for molecular weight, elemental composition and proton aromaticity. When mixtures of strong amine-type solvents with toluene were used, the yield of extract was linearly related mol fraction of strong solvent in the mixture.

  2. Producing highly charged ions without solvent using laserspray ionization: a total solvent-free analysis approach at atmospheric pressure.

    Science.gov (United States)

    Wang, Beixi; Lietz, Christopher B; Inutan, Ellen D; Leach, Samantha M; Trimpin, Sarah

    2011-06-01

    First examples of highly charged ions in mass spectrometry (MS) produced from the solid state without using solvent during either sample preparation or mass measurement are reported. Matrix material, matrix/analyte homogenization time and frequency, atmospheric pressure (AP) to vacuum inlet temperature, and mass analyzer ion trap conditions are factors that influence the abundance of the highly charged ions created by laserspray ionization (LSI). LSI, like matrix-assisted laser desorption/ionization (MALDI), uses laser ablation of a matrix/analyte mixture from a surface to produce ions. Preparing the matrix/analyte sample without the use of solvent provides the ability to perform total solvent-free analysis (TSA) consisting of solvent-free ionization and solvent-free gas-phase separation using ion mobility spectrometry (IMS) MS. Peptides and small proteins such as non-β-amyloid components of Alzheimer's disease and bovine insulin are examples in which LSI and TSA were combined to produce multiply charged ions, similar to electrospray ionization, but without the use of solvent. Advantages using solvent-free LSI and IMS-MS include simplicity, rapid data acquisition, reduction of sample complexity, and the potential for an enhanced effective dynamic range. This is achieved by more inclusive ionization and improved separation of mixture components as a result of multiple charging.

  3. Crystal structure of 5-amino-5'-chloro-6-(4-chloro-benzo-yl)-8-nitro-2,3-di-hydro-1H-spiro-[imidazo[1,2-a]pyridine-7,3'-indolin]-2'-one including an unknown solvent mol-ecule.

    Science.gov (United States)

    Nagalakshmi, R A; Suresh, J; Sivakumar, S; Kumar, R Ranjith; Lakshman, P L Nilantha

    2014-09-01

    The asymmetric unit of the title compound, C21H15Cl2N5O4, contains two independent mol-ecules (A and B) having similar conformations. The amine (NH2) group forms an intra-molecular hydrogen bond with the benzoyl group, giving an S(6) ring motif in both mol-ecules. The central six-membered rings adopt sofa conformations and the imidazole rings are planar (r.m.s deviations = 0.0150 and 0.0166 Å). The pyridine and imidazole rings are inclined to one another by 3.54 (1) and 3.03 (1)° in mol-ecules A and B, respectively. In the crystal, mol-ecules are linked by N-H⋯O hydrogen bonds, forming chains along the a axis which enclose R 2 (2)(16) ring motifs. The rings are linked by weak N-H⋯O and C-H⋯O hydrogen bonds and C-H⋯π inter-actions forming sheets lying parallel to (001). A region of disordered electron density, most probably disordered solvent mol-ecules, occupying voids of ca 753 Å(3) for an electron count of 260, was treated using the SQUEEZE routine in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148-155]. Their formula mass and unit-cell characteristics were not taken into account during refinement.

  4. Glycerol based solvents: synthesis, properties and applications

    OpenAIRE

    García, José I.; García-Marín, Héctor; Pires, Elísabet

    2014-01-01

    The most recent advances in the use of glycerol and glycerol derivatives as solvents are reviewed. There are an increasing number of examples of the use of glycerol itself as a reaction medium, solvent-reagent or a dispersive medium for a large variety of applications. In the case of glycerol derivatives, new synthetic methods, physico-chemical properties and application examples as solvents are revised. Recent studies in the field of solvent classification, as well as solvent substitution is...

  5. Solubility of C60 in solvent mixtures.

    Science.gov (United States)

    Kulkarni, Pradnya P; Jafvert, Chad T

    2008-02-01

    The potential large-scale production of fullerene C60 and its widespread use in consumer products may translate into occupational and public exposure and in long-term environmental exposure. To assess the risk and fate of C60 in the environment, it is important to understand its solvate formation in common industrial solvents as the solvates may affect various properties of C60 including reactivity and toxicity, particularly when solvates occur in C60 clusters. In this study, the solubility measurements in mixed solvent system can provide useful information about solvate formation. The solubility of C60 was measured in pure toluene, tetrahydrofuran, ethanol, and acetonitrile to be 3000, 11, 1.4, and 0.04 mg/L, respectively. Additionally, the solubility of C60 was measured in mixtures of toluene-acetonitrile, toluene-ethanol, toluene-tetrahydrofuran, and acetonitrile-tetrahydrofuran. The solubility data were modeled with some accuracy using Wohl's equation. The estimated crystal energy term for C60 in tetrahydrofuran was different than that in the other solvents, indicating that the C60 solid phase in equilibrium with tetrahydrofuran solution may be a solvated crystal.

  6. Solvent for urethane adhesives and coatings and method of use

    Science.gov (United States)

    Simandl, Ronald F.; Brown, John D.; Holt, Jerrid S.

    2010-08-03

    A solvent for urethane adhesives and coatings, the solvent having a carbaldehyde and a cyclic amide as constituents. In some embodiments the solvent consists only of miscible constituents. In some embodiments the carbaldehyde is benzaldehyde and in some embodiments the cyclic amide is N-methylpyrrolidone (M-pyrole). An extender may be added to the solvent. In some embodiments the extender is miscible with the other ingredients, and in some embodiments the extender is non-aqueous. For example, the extender may include isopropanol, ethanol, tetrahydro furfuryl alcohol, benzyl alcohol, Gamma-butyrolactone or a caprolactone. In some embodiments a carbaldehyde and a cyclic amide are heated and used to separate a urethane bonded to a component.

  7. Kinetic and fluid descriptions of charged particle swarms in gases and nonpolar fluids: Theory and applications

    Science.gov (United States)

    Dujko, Sasa

    2016-09-01

    In this work we review the progress achieved over the last few decades in the fundamental kinetic theory of charged particle swarms with the focus on numerical techniques for the solution of Boltzmann's equation for electrons, as well as on the development of fluid models. We present a time-dependent multi term solution of Boltzmann's equation valid for electrons and positrons in varying configurations of electric and magnetic fields. The capacity of a theory and associated computer code will be illustrated by considering the heating mechanisms for electrons in radio-frequency electric and magnetic fields in a collision-dominated regime under conditions when electron transport is greatly affected by non-conservative collisions. The kinetic theory for solving the Boltzmann equation will be followed by a fluid equation description of charged particle swarms in both the hydrodynamic and non-hydrodynamic regimes, highlighting (i) the utility of momentum transfer theory for evaluating collisional terms in the balance equations and (ii) closure assumptions and approximations. The applications of this theory are split into three sections. First, we will present our 1.5D model of Resistive Plate Chambers (RPCs) which are used for timing and triggering purposes in many high energy physics experiments. The model is employed to study the avalanche to streamer transition in RPCs under the influence of space charge effects and photoionization. Second, we will discuss our high-order fluid model for streamer discharges. Particular emphases will be placed on the correct implementation of transport data in streamer models as well as on the evaluation of the mean-energy-dependent collision rates for electrons required as an input in the high-order fluid model. In the last segment of this work, we will present our model to study the avalanche to streamer transition in non-polar fluids. Using a Monte Carlo simulation technique we have calculated transport coefficients for electrons in

  8. White light-emitting diodes based on nonpolar and semipolar gallium nitride orientations

    Science.gov (United States)

    Demille, Natalie Fellows

    Gallium nitride has become one of the key components when fabricating white light-emitting diodes. Its use as the blue source in conjunction with a wavelength converter such as the yellow emitting phosphor YAG:Ce 3+ is a technology that is commercially available and usable for solid state lighting applications. Currently available white phosphor-based LEDs (pcLEDs) use the basal plane of wurtzite GaN as their source. Although research over the past couple decades has developed this technology into devices with good photometric performance and high reliability, the introduction of nonbasal plane wurtzite GaN orientations have benefits over basal plane GaN that can be incorporated into the white LED. The focus of this research deals with exploring white illumination on nonpolar and semipolar planes of GaN. Light extraction techniques will be described that allowed for high output powers and efficiencies on the c-plane as well as the (1100), (10 11), and (1122) planes of GaN. With higher performing devices, white pcLEDs were fabricated on c-plane, m-plane, and the (1011) semipolar plane. The novelty in the present research is producing white LEDs with nonbasal plane diodes which exhibit optical polarization anisotropy. This feature, absent on the basal plane, allows for tuning photometric quantities both electrically and optically. This is demonstrated on pcLEDs as well as dichromatic LEDs comprised solely of InGaN diodes. As a consequence of these measurements, an apparent optical polarization was seen to be occurring in the luminescence of the YAG:Ce3+ when the system absorbed linearly polarized light. Polarized emission in YAG:Ce3+ was explored by obtaining single crystals of YAG:Ce3+ with different planar orientations. The experiments led to the conclusion that crystal orientation plays no part in the optical polarization. It is suggested that the cause is a result of electric dipole transitions given by various selection rules between the Ce 3+ ion's 4f and 5d

  9. Ionic liquids as green solvents and electrolytes for robust chemical sensor development.

    Science.gov (United States)

    Rehman, Abdul; Zeng, Xiangqun

    2012-10-16

    Ionic liquids (ILs) exhibit complex behavior. Their simultaneous dual nature as solvents and electrolytes supports the existence of structurally tunable cations and anions, which could provide the basis of a novel sensing technology. However, the elucidation of the physiochemical properties of ILs and their connections with the interaction and redox mechanisms of the target analytes requires concerted data acquired from techniques including spectroscopic investigations, thermodynamic and solvation models, and molecular simulations. Our laboratory is using these techniques for the rational design and selection of ILs and their composites that could serve as the recognition elements in various sensing platforms. ILs show equal utility in both piezoelectric and electrochemical formats through functionalized ionics that provide orthogonal chemo- and regioselectivity. In this Account, we summarize recent developments in and applications of task-specific ILs and their surface immobilization on solid supports. Such materials can serve as a replacement for conventional recognition elements and electrolytic media in piezoelectric and electrochemical sensing approaches, and we place a special focus on our contributions to these fields. ILs take advantage of both the physical and chemical forces of interaction and can incorporate various gas analytes. Exploiting these features, we have designed piezoelectric sensors and sensor arrays for high-temperature applications. Vibrational spectroscopy of these ILs reveals that hydrogen bonding and dipole-dipole interactions are typically responsible for the observed sensing profiles, but the polarization and cavity formation effect as an analyte approaches the recognition matrix can also cause selective discrimination. IL piezoelectric sensors can have low sensitivity and reproducibility. To address these issues, we designed IL/conducting polymer host systems that tune existing molecular templates with highly selective structure

  10. Methods for recovering a polar solvent from a fluid stream contaminated with at least one polar impurity

    Science.gov (United States)

    Ginosar, Daniel M.; Wendt, Daniel S.

    2012-11-13

    A method of removing a polar solvent from a fluid volume contaminated with at least one polar impurity, such as a free fatty acid, is provided. The method comprises providing a fluid volume that includes at least one polar impurity dissolved in at least one solvent. The fluid volume is contacted with an expanding gas to remove the at least one solvent. The expanding gas may be dissolved into the at least one solvent in the fluid volume to form a gas-expanded solvent. The immiscibility of the polar impurities in the gas-expanded solvent enables separation of the polar impurities from the gas-expanded solvent. After separation of the polar impurities, at least one of the temperature and pressure may be reduced to separate the solvent from the expanding gas such that the clean solvent may be reused.

  11. The flotation of Roşia Poieni copper ore in column machine, with non-polar oils addition

    Directory of Open Access Journals (Sweden)

    Ciocani V.

    2005-11-01

    Full Text Available The most important natural resource of copper in Romania is the ore deposit of Roşia Poieni. At present, the utilization of Roşia Poieni poorphyry copper ore is possible by extraction in quarry of the mass ore and mineral processing into a technological flux with modest results for the value of metal recovery in concentrate 70-72 % and an average contents of 16,5 % Cu. Our researches were directed to studies regarding test and utilisation of special procedure of flotation – addition of the non-polar oil – applied to advanced grinding ore with column type machines.

  12. Free ion yields for nonpolar liquids exposed to 1.6-3.5 keV X-rays

    CERN Document Server

    Holroyd, R A

    1998-01-01

    The yields of free ions formed following absorption of 1.6-3.5 keV X-rays were determined for several nonpolar liquids using a conductivity technique. The yields are much less for X-rays than for gamma rays; this effect is largest for branched hydrocarbons. A minimum in yield is observed around 2 keV. The dependence of G sub f sub i sup o on X-ray energy is in good agreement with computer simulations. For tetramethylsilane a sharp dip in ion yield is observed at the Si ls -> sigma sup * resonance, indicating that the free electron yield is even less at this energy.

  13. Solvent effects on the photophysical properties of poly[1,4-dihydroxyanthraquinoneimine-1,3-bis(phenylene-ester-methylene)tetramethyldisiloxane].

    Science.gov (United States)

    Dorneanu, Petronela Pascariu; Homocianu, Mihaela; Tigoianu, Ionut Radu; Airinei, Anton; Zaltariov, Mirela; Cazacu, Maria

    2015-01-05

    Absorption and fluorescence spectra of a polyquinoneimine, PQI, built on 1,4-dihydroxyanthraquinone and a siloxane diamine, 1,3-bis(amino-phenylene-ester-methylene)tetramethyldisiloxane, have been investigated in solvents of different polarities. The effect of solvents on the spectral properties was investigated using Lippert-Mataga and Bakhshiev polarity functions and Catalán's multiple linear regression approach. Absorption and fluorescence spectra in studied solvents exhibit hypsochromic and bathochromic shifts, respectively. The polarity of the solvent was the main parameter which changes the spectral properties of PQI. Also, the binary mixtures of chloroform with methanol and dimethyl sulfoxide were used to analyze the intermolecular interactions and preferential solvation. The preferential solvation parameters (local mole fraction (X₂(L)), excess function (δs₂) and preferential solvation constant (KPS)) were calculated from spectral data and discussed as a function of cosolvent content. The values of quantum yield, decreased linearly with increasing solvent polarity (for non-polar and polar solvents).

  14. A combined molecular dynamic and quantum mechanic study of the solvent and guest molecule effect on the stability and length of heterocyclic peptide nanotubes.

    Science.gov (United States)

    Izadyar, Mohammad; Khavani, Mohammad; Housaindokht, Mohammad Reza

    2015-05-07

    Molecular dynamic simulations were performed to investigate the stability of heterocyclic peptide nanotubes composed of 1,4-disubstituted-1,2,3-triazol ε-amino acid. 45 ns MD simulations were conducted on the cyclic peptide nanotube (CPNT) and cyclic peptide dimer in methanol, chloroform, and water and revealed that these structures are more stable in nonpolar solvents. MM-PBSA and MM-GBSA calculations were employed to analyze the solvent effect on the stability and length of the CPNT. These calculations showed that CPNT in chloroform was more stable and longer as compared to other solvents. In addition, the effect of the guest molecule (ethanol) inside the dimer and CPNT was investigated. The obtained results confirmed that guest molecule(s) stabilized the dimer and CPNT in all solvents. Quantum chemistry calculations on the cyclic peptide dimer were performed at the M06-2X/6-31G(d) level in the gas phase and three solvents. The obtained results from the quantum chemistry study were in good agreement with the MD simulation results. DFT calculations showed that the guest molecule stabilized the dimer structure and electrostatically interacted with the cyclic peptide dimer. Finally, for investigation of the solvent effects on the hydrogen bonds of the cyclic peptide dimer, NBO and AIM analysis were performed.

  15. Which solvent for olfactory testing?

    Science.gov (United States)

    Philpott, C M; Goodenough, P C; Wolstenholme, C R; Murty, G E

    2004-12-01

    The physical properties of any carrier can deteriorate over time and thus alter the results in any olfactory test. The aim of this study was to evaluate clinically potential solvents as a clean odourless carrier for olfactory testing. Sweet almond oil, pure coconut oil, pure peach kernel oil, dipropylene glycol, monopropylene glycol, mineral oil and silicone oil were studied. The experimentation was conducted in two parts. First, an olfactory device was used to conduct air through the solvents on a weekly basis using a cohort of six volunteers to assess the perceived odour of each solvent at weekly intervals. Secondly a cross-reference test was performed using small bottled solutions of phenylethyl-alcohol and 1-butanol in 10-fold dilutions to compare any perceived difference in concentrations over a period of 8 weeks. We concluded that mineral oil is the most suitable carrier for the purpose of olfactory testing, possessing many desirable characteristics of an olfactory solvent, and that silicone oil may provide a suitable alternative for odorants with which it is miscible.

  16. Effect of some organic solvents on oxidative phosphorylation in rat liver mitochondria: Choice of organic solvents.

    Science.gov (United States)

    Syed, Muzeeb; Skonberg, Christian; Hansen, Steen Honoré

    2013-12-01

    The effect of acetone, acetonitrile, dimethyl sulfoxide (DMSO), ethanol and methanol on oxidative phosphorylation (ATP synthesis) in rat liver mitochondria has been studied. All the organic solvents inhibited the oxidative phosphorylation in a concentration dependent manner, but with differences in potencies. Among the tested organic solvents, acetonitrile and acetone were more potent than ethanol, methanol, and DMSO. There was no significant difference in oxidative phosphorylation, compared to controls, when the concentrations of acetone was below 1% (v/v), of acetonitrile below 2% (v/v), of DMSO below 10% (v/v), of ethanol below 5% or of methanol below 2%, respectively. There was complete inhibition of oxidative phosphorylation at 50% (v/v) of acetone, acetonitrile and ethanol. But in the case of DMSO and methanol there were some residual activities observed at the 50% concentration level. DMSO showed least effect on oxidative phosphorylation with an IC50 value of 13.3±1.1% (v/v), followed by methanol (IC50 value 8.3±1.0), ethanol (IC50 value 4.6±1.1), acetone (IC50 value 4.3±1.0) and finally acetonitrile (IC50 value 2.1±1.0). All the organic solvents showed modulatory effects on 2,4-dinitrophenol (DNP) mediated inhibition of oxidative phosphorylation with potentiation of the action of DNP. Acetonitrile showed the highest potentiation effect followed by acetone, ethanol, methanol, and DMSO in presence of DNP. The use of organic solvents for investigation of the effects of compounds on oxidative phosphorylation in mitochondria should therefore include the use of relevant concentrations of the organic solvent in order to validate the contribution.

  17. Combining a polarizable force-field and a coarse-grained polarizable solvent model. II. Accounting for hydrophobic effects.

    Science.gov (United States)

    Masella, Michel; Borgis, Daniel; Cuniasse, Philippe

    2011-09-01

    A revised and improved version of our efficient polarizable force-field/coarse grained solvent combined approach (Masella, Borgis, and Cuniasse, J. Comput. Chem. 2008, 29, 1707) is described. The polarizable pseudo-particle solvent model represents the macroscopic solvent polarization by induced dipoles placed on mobile pseudo-particles. In this study, we propose a new formulation of the energy term handling the nonelectrostatic interactions among the pseudo-particles. This term is now able to reproduce the energetic and structural response of liquid water due to the presence of a hydrophobic spherical cavity. Accordingly, the parameters of the energy term handling the nonpolar solute/solvent interactions have been refined to reproduce the free-solvation energy of small solutes, based on a standard thermodynamic integration scheme. The reliability of this new approach has been checked for the properties of solvated methane and of the solvated methane dimer, as well as by performing 10 × 20 ns molecular dynamics (MD) trajectories for three solvated proteins. A long-time stability of the protein structures along the trajectories is observed. Moreover, our method still provides a measure of the protein solvation thermodynamic at the same accuracy as standard Poisson-Boltzman continuum methods. These results show the relevance of our approach and its applicability to massively coupled MD schemes to accurately and intensively explore solvated macromolecule potential energy surfaces.

  18. Solvent-Dependent Structure of Iridium Dihydride Complexes: Different Geometries at Low and High Dielectricity of the Medium.

    Science.gov (United States)

    Polukeev, Alexey V; Marcos, Rocío; Ahlquist, Mårten S G; Wendt, Ola F

    2016-03-14

    The hydride iridium pincer complex [(PCyP)IrH2] (PCyP=cis-1,3-bis[(di-tert-butylphosphino)methyl]cyclohexane, 1) reveals remarkably solvent-dependent hydride chemical shifts, isotope chemical shifts, JHD and T1(min), with rHH increasing upon moving to more polar medium. The only known example of such behaviour (complex [(POCOP)IrH2], POCOP=2,6-(tBu2PO)2C6H3) was explained by the coordination of a polar solvent molecule to the iridium (J. Am. Chem. Soc. 2006, 128, 17114). Based on the existence of an agostic bond between α-C-H and iridium in 1 in all solvents, we argue that the coordination of solvent can be rejected. DFT calculations revealed that the structures of 1 and [(POCOP)IrH2] depend on the dielectric permittivity of the medium and these compounds adopt trigonal-bipyramidal geometries in non-polar media and square-pyramidal geometries in polar media.

  19. Method for analyzing solvent extracted sponge core

    Energy Technology Data Exchange (ETDEWEB)

    Ellington, W.E.; Calkin, C.L.

    1988-11-22

    For use in solvent extracted sponge core measurements of the oil saturation of earth formations, a method is described for quantifying the volume of oil in the fluids resulting from such extraction. The method consists of: (a) separating the solvent/oil mixture from the water in the extracted fluids, (b) distilling at least a portion of the solvent from the solvent/oil mixture substantially without co-distillation or loss of the light hydrocarbons in the mixture, (c) determining the volume contribution of the solvent remaining in the mixture, and (d) determining the volume of oil removed from the sponge by substracting the determined remaining solvent volume.

  20. Cleaning with solvents methods and machinery

    CERN Document Server

    Durkee, John

    2014-01-01

    High-precision cleaning is required across many sectors, including aerospace, defense, medical device manufacturing, pharmaceutical processing, semiconductor/electronics, and more. In this comprehensive reference work, solvent cleaning equipment is thoroughly covered with a focus on the engineering details of its operation and selection. Key data is provided alongside practical guidance, giving scientists and engineers in multiple sectors the information they need not only to choose the correct machine in the first place, but also how to operate it effectively and efficiently. Low emission

  1. Coal extraction by aprotic dipolar solvents. Final report. [Tetramethylurea, hexa-methylphosphoramide

    Energy Technology Data Exchange (ETDEWEB)

    Sears, J T

    1985-12-01

    The overall goals of this project were to examine the rate and amount of extraction of coals at low temperature by a class of solvents with a generic structure to include tetramethylurea (TMU) and hexa-methylphosphoramide (HMPA) and to examine the nature of the extracted coal chemicals. The class of solvents with similar action, however, can be classified as aprotic, base solvents or, somewhat more broadly, specific solvents. The action of solvents by this last classification was then examined to postulate a mechanism of attack. Experimental work was conducted to explain the specific solvent attack including (1) pure solvent extraction, (2) extraction in mixtures with otherwise inert solvents and inhibitors, and (3) extraction with simultaneous catalytic enhancement attempts including water-gas shift conversion. Thus nuclear magnetic resonance (NMR) and gas-chromatograph mass spectrometer (GC-MS) analysis of extract molecules and extraction with high-pressure CO in TMU (plus 2% H2O) was performed. Effects of solvent additives such as cumene and quinone of large amounts of inert solvents such as tetralin, liminone, or carbon disulfide on extraction were also determined. Results are discussed. 82 refs., 36 figs., 37 tabs.

  2. Initiate test loop irradiations of ALSEP process solvent

    Energy Technology Data Exchange (ETDEWEB)

    Peterman, Dean R. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Olson, Lonnie G. [Idaho National Lab. (INL), Idaho Falls, ID (United States); McDowell, Rocklan G. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2014-09-01

    This report describes the initial results of the study of the impacts of gamma radiolysis upon the efficacy of the ALSEP process and is written in completion of milestone M3FT-14IN030202. Initial irradiations, up to 100 kGy absorbed dose, of the extraction section of the ALSEP process have been completed. The organic solvent used for these experiments contained 0.05 M TODGA and 0.75 M HEH[EHP] dissolved in n-dodecane. The ALSEP solvent was irradiated while in contact with 3 M nitric acid and the solutions were sparged with compressed air in order to maintain aerated conditions. The irradiated phases were used for the determination of americium and europium distribution ratios as a function of absorbed dose for the extraction and stripping conditions. Analysis of the irradiated phases in order to determine solvent composition as a function of absorbed dose is ongoing. Unfortunately, the failure of analytical equipment necessary for the analysis of the irradiated samples has made the consistent interpretation of the analytical results difficult. Continuing work will include study of the impacts of gamma radiolysis upon the extraction of actinides and lanthanides by the ALSEP solvent and the stripping of the extracted metals from the loaded solvent. The irradiated aqueous and organic phases will be analyzed in order to determine the variation in concentration of solvent components with absorbed gamma dose. Where possible, radiolysis degradation product will be identified.

  3. Radiative recombination mechanisms in polar and non-polar InGaN/GaN quantum well LED structures

    Science.gov (United States)

    Badcock, T. J.; Ali, M.; Zhu, T.; Pristovsek, M.; Oliver, R. A.; Shields, A. J.

    2016-10-01

    We study the photoluminescence internal quantum efficiency (IQE) and recombination dynamics in a pair of polar and non-polar InGaN/GaN quantum well (QW) light-emitting diode (LED) structures as a function of excess carrier density and temperature. In the polar LED at 293 K, the variation of radiative and non-radiative lifetimes is well described by a modified ABC type model which accounts for the background carrier concentration in the QWs due to unintentional doping. As the temperature is reduced, the sensitivity of the radiative lifetime to excess carrier density becomes progressively weaker. We attribute this behaviour to the reduced mobility of the localised electrons and holes at low temperatures, resulting in a more monomolecular like radiative process. Thus we propose that in polar QWs, the degree of carrier localisation determines the sensitivity of the radiative lifetime to the excess carrier density. In the non-polar LED, the radiative lifetime is independent of excitation density at room temperature, consistent with a wholly excitonic recombination mechanism. These findings have significance for the interpretation of LED efficiency data within the context of the ABC recombination model.

  4. Effects of growth temperature on nonpolar a-plane InN grown by molecular beam epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Rajpalke, Mohana K.; Bhat, Thirumaleshwara N.; Krupanidhi, S.B. [Materials Research Centre, Indian Institute of Science, Bangalore-560012 (India); Roul, Basanta [Materials Research Centre, Indian Institute of Science, Bangalore-560012 (India); Central Research Laboratory, Bharat Electronics, Bangalore-560013 (India); Kumar, Mahesh [Materials Research Centre, Indian Institute of Science, Bangalore-560012 (India); Centre of Excellence in Information and Communication Technology, Indian Institute of Technology, Jodhpur-342011 (India); Sinha, Neeraj [Office of Principal Scientific Advisor, Government of India, New Delhi 110011 (India); Department of Materials Science, Gulbarga University, Gulbarga 585 106 (India); Jali, V.M. [Department of Physics, Gulbarga University, Gulbarga 585 106 (India)

    2014-04-15

    Nonpolar a-plane InN films were grown on r-plane sapphire substrate by plasma assisted molecular beam epitaxy with GaN underlayer. Effect of growth temperature on structural, morphological, and optical properties has been studied. The growth of nonpolar a-plane (1 1 -2 0) orientation was confirmed by high resolution X-ray diffraction study. The film grown at 500 C shows better crystallinity with the rocking curve FWHM 0.67 and 0.85 along [0 0 0 1] and [1 -1 0 0] directions, respectively. Scanning electron micrograph shows formation of Indium droplets at higher growth temperature. Room tem-perature absorption spectra show growth temperature dependent band gap variation from 0.74-0.81 eV, consistent with the expected Burstein-Moss effect. The rectifying behaviour of the I-V curve indicates the existence of Schottky barrier at the InN and GaN interface. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  5. Effects of n-alkanes on compositions of cellular non-polar lipids in Aspergillus sp. isolated from soils

    Energy Technology Data Exchange (ETDEWEB)

    Miyazima, M.; Iida, M.; Iizuka, H.

    1985-01-01

    A strain of hydrocarbon-using filamentous fungi, Aspergillus sp. No. 250-2, was grown on n-alkanes (C/sub 11/ to C/sub 16/) and glucose as the sole carbon and energy sources, and the distribution of cellular non-polar lipids was determined. The non-polar lipids were examined by thin-layer chromatography; they were sterols, sterol esters, diglycerides, triglycerides, and free fatty acids, and the major lipids were free fatty acids and triglycerides on all substrates. Free fatty acids were mainly even-chain saturated acids on all substrates. When grown on n-C/sub 11/ to 15, the unsaturated fatty acids were mainly incorporated into triglyceride, but there were saturated fatty acids with n-C/sub 16/ and glucose. The proportion of C/sub 16/.0 acid was increased markedly in n-C/sub 16/-grown cells, but C18:0 acid was increased in glucose-grown cells. Compositions of odd-chain fatty acids were slightly increased in both free fatty acids and triglycerides from n-C/sub 15/-grown cells. It is suggested that n-alkanes as substrates influenced the incorporation of fatty acids into triglyceride.

  6. Solvent effect on polystyrene surface roughness on top of QCM sensor

    Science.gov (United States)

    Sakti, Setyawan P.; Rahmawati, Eka; Robiandi, Fadli

    2016-03-01

    Quartz Crystal Microbalance (QCM) has been used as a basis for many chemical sensors and biosensor. Its sensitivity to mass change which can detect a mass change on its surface down to sub ng/cm2 is one of its interesting aspects. Another interesting feature is its ability to work in liquid environment. However, there are many aspects which influence QCM sensor properties in contact with liquid. One of the aspects is surface roughness of the matrix layer where on top of it a biological sensitive layer will be immobilized. One of matrix layers in the immobilizing biological sensitive layer was polystyrene. Polystyrene was coated on the QCM sensor by using the spin coating method. During the coating process, polystyrene was solved using non-polar solvent. It is known that the physical and chemical properties of the solvent affect a transition process from soluble polymer becoming rigid polymer layer. In this work, we show that polystyrene solved in chloroform has a higher surface roughness compare to one solved in toluene, xylene, or tetrahydrofuran. Surface roughness of the polystyrene coating were measured using a non-contact profilometer. However, we also found that there is no difference on the electrical impedance of the QCM sensor coated with polystyrene resulted from differing solvent when the sensor was in contact with air and water. Thus, all of the mentioned solvent can be used to solve the polystyrene as a coating material for QCM sensor without affecting the electrical performance of the sensor, but the choice of the solution can be used as a simple method to control the difference roughness of the polystyrene coating.

  7. Conversion of polar and non-polar algae oil lipids to fatty acid methyl esters with solid acid catalysts--A model compound study.

    Science.gov (United States)

    Asikainen, Martta; Munter, Tony; Linnekoski, Juha

    2015-09-01

    Bio-based fuels are becoming more and more important due to the depleting fossil resources. The production of biodiesel from algae oil is challenging compared to terrestrial vegetable oils, as algae oil consists of polar fatty acids, such as phospholipids and glycolipids, as well as non-polar triglycerides and free fatty acids common in vegetable oils. It is shown that a single sulphonated solid acid catalyst can perform the esterification and transesterification reactions of both polar and non-polar lipids. In mild reaction conditions (60-70 °C) Nafion NR50 catalyst produces methyl palmitate (FAME) from the palmitic acid derivatives of di-, and tri-glyceride, free fatty acid, and phospholipid with over 80% yields, with the glycolipid derivative giving nearly 40% yields of FAME. These results demonstrate how the polar and non-polar lipid derivatives of algal oil can be utilised as feedstocks for biodiesel production with a single catalyst in one reaction step.

  8. Structural stability of scandium on nonpolar GaN (112{sup ¯}0) and (101{sup ¯}0) surfaces: A first-principles study

    Energy Technology Data Exchange (ETDEWEB)

    González-Hernández, Rafael, E-mail: rhernandezj@uninorte.edu.co [Grupo de Investigación en Física Aplicada, Departamento de Física, Universidad del Norte, Barranquilla (Colombia); Martínez, Gustavo; López-Perez, William [Grupo de Investigación en Física Aplicada, Departamento de Física, Universidad del Norte, Barranquilla (Colombia); Rodriguez, Jairo Arbey [Grupo de Estudio de Materiales, Departamento de Física, Universidad Nacional de Colombia, Bogotá (Colombia)

    2014-01-01

    First-principles calculations based on density-functional theory have been implemented to study the scandium (Sc) adsorption and incorporation on nonpolar GaN (112{sup ¯}0) and (101{sup ¯}0) surfaces. It is found that Sc adatom prefers to reside at bridge positions, between the hollow and top sites, on both GaN nonpolar surfaces. In addition, calculating the relative surface energy of several Sc configurations, we constructed a phase diagram showing the energetically most stable surfaces as a function of the Ga chemical potentials. Based on these results, we have found that incorporation of Sc adatoms in the Ga-substitutional site is energetically more favorable compared with the adsorption on the top layers. This effect leads to the formation of ScN interlayers on nonpolar GaN (112{sup ¯}0) and (101{sup ¯}0) surfaces, which reduces the dislocation densities between GaN and ScN.

  9. Scalable synthesis of organic-soluble carbon quantum dots: superior optical properties in solvents, solids, and LEDs.

    Science.gov (United States)

    Wu, Minghong; Zhan, Jing; Geng, Bijiang; He, Piaopiao; Wu, Kuan; Wang, Liang; Xu, Gang; Li, Zhen; Yin, Luqiao; Pan, Dengyu

    2017-09-14

    Carbon quantum dots (CQDs) have attracted much attention owing to their unique optical properties and a wide range of applications. The fabrication and control of CQDs with organic solubility and long-wavelength emission are still urgent issues to be addressed for their practical use in LEDs. Here, organic-soluble CQDs were produced at a high yield of ∼90% by a facile solvent engineering treatment of 1,3,6-trinitropyrene, which were simultaneously used as the nitrogen and carbon sources. The optical properties of the organic-soluble CQDs (o-CQDs) were investigated in nonpolar and polar solvents, films, and LED devices. The CQDs have a narrow size distribution around 2.66 nm, and can be dispersed in different organic solvents. Significantly, the as-prepared CQDs present an excitation-independent emission at 607 nm with fluorescence quantum yields (QYs) up to 65.93% in toluene solution. A pronounced solvent effect was observed and their strong absorption bands can be tuned in the whole visible region (400-750 nm) by changing the solvent. The CQDs in various solvents can emit bright, excitation-independent, long-wavelength fluorescence (orange to red). Furthermore, benefiting from the unique oil-solution properties, the as-prepared CQDs can be processed in thin film and device forms to meet the requirements of various applications, such as phosphor-based white-light LEDs. The color coordinate for these CQD modified LEDs is realized at (0.32, 0.31), which is close to pure white light (0.33, 0.33).

  10. Reactions and Separations in Green Solvents

    NARCIS (Netherlands)

    Van Spronsen, J.

    2010-01-01

    Most chemical processes involve solvents in the reaction and the separation step. These solvents give rise to a heavy environmental and economical burden. Moreover, these solvents are based on non-sustainable resources like petroleum. The aim of this thesis has been to develop a number of alternativ

  11. Reactions and Separations in Green Solvents

    NARCIS (Netherlands)

    Van Spronsen, J.

    2010-01-01

    Most chemical processes involve solvents in the reaction and the separation step. These solvents give rise to a heavy environmental and economical burden. Moreover, these solvents are based on non-sustainable resources like petroleum. The aim of this thesis has been to develop a number of

  12. The hype with ionic liquids as solvents

    Science.gov (United States)

    Kunz, Werner; Häckl, Katharina

    2016-09-01

    In this mini review, we give our personal opinion about the present state of the art concerning Ionic Liquids, proposed as alternative solvents. In particular, we consider their different drawbacks and disadvantages and discuss the critical aspects of the research of Ionic Liquids as solvents. Finally, we point out some aspects on potentially promising Ionic Liquid solvents.

  13. Effects of Si-doping on structural, electrical, and optical properties of polar and non-polar AlGaN epi-layers

    Science.gov (United States)

    Yang, Hongquan; Zhang, Xiong; Wang, Shuchang; Wang, Yi; Luan, Huakai; Dai, Qian; Wu, Zili; Zhao, Jianguo; Cui, Yiping

    2016-08-01

    The polar (0001)-oriented c-plane and non-polar (11 2 bar 0) -oriented a-plane wurtzite AlGaN epi-layers were successfully grown on polar (0001)-oriented c-plane and semi-polar (1 1 bar 02) -oriented r-plane sapphire substrates, respectively with various Si-doping levels in a low pressure metal organic chemical vapor deposition (MOCVD) system. The morphological, structural, electrical, and optical properties of the polar and non-polar AlGaN epi-layers were studied with scanning electron microscopy (SEM), X-ray diffraction (XRD), Hall effect, and Raman spectroscopy. The characterization results show that Si dopants incorporated into the polar and non-polar AlGaN films induced a relaxation of compressive residual strain and a generation of biaxial tensile strain on the surface in consequence of the dislocation climbing. In particular, it was found that the Si-induced compressive strain relaxation in the non-polar AlGaN samples can be promoted by the structural anisotropy as compared with the polar counterparts. The gradually increased relaxation of compressive residual strain in both polar and non-polar AlGaN samples with increasing Si-doping level was attributed to the Si-induced enhancement in the opportunity for the dislocations to interact and annihilate. This implies that the crystal quality for both polar and non-polar AlGaN epi-layers can be remarkably improved by Si-doping.

  14. Ion Exchange and Solvent Extraction: Supramolecular Aspects of Solvent Exchange Volume 21

    Energy Technology Data Exchange (ETDEWEB)

    Gloe, Karsten [Technischen Universität Dresden; Tasker, Peter A [ORNL; Oshima, Tatsuya [University of Miyazaki; Watarai, Hitoshi [Institute for NanoScience Design at Osaka University; Nilsson, Mikael [University of California, Irvine

    2013-01-01

    Preface The theme of supramolecular chemistry (SC), entailing the organization of multiple species through noncovalent interactions, has permeated virtually all aspects of chemical endeavor over the past several decades. Given that the observed behavior of discrete molecular species depends upon their weak interactions with one another and with matrix components, one would have to conclude that SC must indeed form part of the fabric of chemistry itself. A vast literature now serves to categorize SC phenomena within a body of consistent terminology. The word supramolecular itself appears in the titles of dozens of books, several journals, and a dedicated encyclopedia. Not surprisingly, the theme of SC also permeates the field of solvent extraction (SX), inspiring the framework for this volume of Ion Exchange and Solvent Extraction. It is attempted in the six chapters of this volume to identify both how supramolecular behavior occurs and is studied in the context of SX and how SC is influencing the current direction of SX. Researchers and practitioners have long dealt with supramolecular interactions in SX. Indeed, the use of polar extractant molecules in nonpolar media virtually assures that aggregative interactions will dominate the solution behavior of SX. Analytical chemists working in the 1930s to the 1950s with simple mono- and bidentate chelating ligands as extractants noted that extraction of metal ions obeyed complicated mass-action equilibria involving complex stoichiometries. As chemists and engineers developed processes for nuclear and hydrometallurgical applications in the 1950s and 1960s, the preference for aliphatic diluents only enhanced the complexity and supramolecular nature of extraction chemistry. Use of physical techniques such as light scattering and vapor-pressure measurements together with various spectroscopic methods revealed organic-phase aggregates from well-defined dimers to small aggregates containing a few extractant molecules to large

  15. EPR character of gadolinium complexes with noncyclic polyether Schiff bases and its solvent effects

    Institute of Scientific and Technical Information of China (English)

    姚克敏; 陈德余; 王晓南; 邓宁

    1996-01-01

    EPR characters of three new gadolinium complexes with noncydic polyether Schiff bases in powder or organic solvents, including various oxyethylene chain lengths and different substituting groups in ligands, are investigated respectively. Some regularities are summed up. The difference of EPR character in various solvents, particularly at different temperatures, has been examined. The ’single peak effect’ due to THF solvent at low temperature is observed for the first time. This phenomenon is explicated.

  16. An Analytic Equation of State Based on SAFT-CP for Binary Non-Polar Alkane Mixtures Across the Critical Point

    Institute of Scientific and Technical Information of China (English)

    周文来; 密建国; 贺刚; 于燕梅; 陈健

    2003-01-01

    The description using an analytic equation of state of thermodynamic properties near the critical points of fluids and their mixtures remains a challenging problem in the area of chemical engineering. Based on the statistical associating fluid theory across the critical point (SAFT-CP), an analytic equation of state is established in this work for non-polar mixtures. With two binary parameters, this equation of state can be used to calculate not only vapor-liquid equilibria but also critical properties of binary non-polar alkane mixtures with acceptable deviations.

  17. Analytical methods for residual solvents determination in pharmaceutical products.

    Science.gov (United States)

    Grodowska, Katarzyna; Parczewski, Andrzej

    2010-01-01

    Residual solvents (RS) are not desirable substances in the final pharmaceutical product and their acceptable limits have been published in pharmacopoeias and ICH guidelines. The intension of this paper was to review and discuss some of the current analytical procedures including gas chromatographic (GC) and other alternative techniques which are used for residual solvents determination. GC methods have been developed to monitor this kind of impurities routinely. The most popular techniques of sample introduction into the gas chromatograph include direct injection, static or dynamic headspace, solid-phase microextraction and single drop microextraction. Different separation techniques like two dimensional chromatography or multicapillary chromatography were compared with classical separation mode with use of single capillary column. Also alternative methodologies for residual solvents testing were discussed in this review. In conclusions, gas chromatography-based procedures were described as the most appropriate because of the lowest detection limits, ease of sample preparation and specificity.

  18. Solvent desorption dynamic headspace sampling of fermented dairy product volatiles.

    Science.gov (United States)

    Rankin, S A

    2001-01-01

    A method was developed based on solvent desorption dynamic headspace analysis for the identification and relative quantification of volatiles significant to the study of fermented dairy product aroma. Descriptions of applications of this method are presented including the measurement of diacetyl and acetoin in fermented milk, the evaluation of volatile-hydrocolloid interactions in dairy-based matrices, and the identification of volatiles in cheeses for canonical discriminative analysis. Advantages of this method include rapid analysis, minimal equipment investment, and the ability to analyze samples with traditional GC split/splitless inlet systems. Limitations of this method are that the sample must be in the liquid state and the inherent analytical limitation to those compounds that do not coelute with the solvent or solvent impurity peaks.

  19. Oil recovery from petroleum sludge through ultrasonic assisted solvent extraction.

    Science.gov (United States)

    Hu, Guangji; Li, Jianbing; Huang, Shuhui; Li, Yubao

    2016-09-18

    The effect of ultrasonic assisted extraction (UAE) process on oil recovery from refinery oily sludge was examined in this study. Two types of UAE treatment including UAE probe (UAEP) system and UAE bath (UAEB) system were investigated. Their oil recovery efficiencies were compared to that of mechanical shaking extraction (MSE). Three solvents including cyclohexane (CHX), ethyl acetate (EA), and methyl ethyl ketone (MEK) were examined as the extraction solvents. The influence of experimental factors on oil and solvent recovery was investigated using an orthogonal experimental design. Results indicated that solvent type, solvent-to-sludge (S/S) ratio, and treatment duration could have significant effects on oil recovery in UAE treatment. Under the optimum conditions, UAEP treatment can obtain an oil recovery of 68.8% within 20 s, which was higher than that (i.e., 62.0%) by MSE treatment after 60 min' extraction. UAEB treatment can also obtain a promising oil recovery within shorter extraction duration (i.e., 15 min) than MSE. UAE was thus illustrated as an effective and improved approach for oily sludge recycling.

  20. Effect of Concentration on Isomerization of Rhodanine Derivatives of Merocyanine Dyes in Polar Solvents

    Directory of Open Access Journals (Sweden)

    O. P. Dimitriev

    2014-01-01

    Full Text Available Rhodanine derivatives of merocyanine dyes with residues of 1,3,3-trimethyl-3H-indole and 3-ethylbenzothiazoline have been found to possess two molecular forms in diluted solutions of polar solvents such as dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidinone. The first molecular form was observed to prevail at low concentrations of the dyes, normally up to 10−5 M. The second one prevails at higher concentrations and is displayed through a new band in the electronic absorption spectrum, which is red-shifted with respect to the absorption band of the first form. No similar effect was found for these dyes by use of nonpolar solvents or upon alkyl-substitution of the molecules at nitrogen atom in the rhodanine moiety. We assign the above two forms to different molecular isomers and the analogous spectral changes were shown to take place by light or heat influence which correspond to a typical isomerization effect for the related merocyanine dyes. It is discussed that the isomer transformation is facilitated by the increased mobility of the proton bonded to the nitrogen atom of the rhodanine moiety in the polar environment and the increased amount of dye-dye collisions.

  1. Modification of glucose oxidase for the development of biocatalytic solvent inks.

    Science.gov (United States)

    Talbert, Joey N; He, Fei; Seto, Kayla; Nugen, Sam R; Goddard, Julie M

    2014-02-05

    Inkjet printing of enzymes onto hydrophobic polymeric material offers the potential for economical rapid deposition and patterning of biocatalysts for biosensor, microarray, and intelligent packaging applications. Non-polar solvent based inks provide simple vehicles for direct printing on these materials; however, enzymes are not readily soluble in such inks. Glucose oxidase (Aspergillus niger) was made soluble in toluene by hydrophobic ion pairing with didodecyldimethylammonium bromide. Following modification, single enzyme composites with a mean diameter of 12.5 nm were formed. The enzymes showed no significant change in K'(m) and a 46% decrease in k'(cat) compared to the native enzyme. Modification allowed for direct printing and patterning on PET using piezoelectric inkjet printing. Specific activity of the modified enzyme was reduced from 889 × 10³ μmol/min/g to 2×10³ μmol/min/g after printing. These results suggest that direct inkjet printing of enzymes onto hydrophobic polymers may be accomplished using enzyme modification as a means to induce solubility in solvent inks.

  2. Use of polar and nonpolar fractions as additional information sources for studying thermoxidized virgin olive oils by FTIR

    Directory of Open Access Journals (Sweden)

    Tena, N.

    2014-09-01

    Full Text Available Fourier transform infrared (FTIR spectroscopy has been proposed to study the degradation of virgin olive oils (VOO in samples undergoing thermoxidation. The polar and nonpolar fractions of oxidized oils have been analyzed by FTIR to provide further information on the minor spectral changes taking place during thermoxidation. This information assists in the interpretation of the spectra of the samples. For this purpose polar and nonpolar fractions of 47 VOO samples thermoxidized (190 °C in a fryer were analyzed by FTIR. The time-course change of the band area assigned to single cis double bonds was explained by their correlation with the decrease in oleic acid (adjusted-R2=0.93. The bands assigned to the hydroxyl groups and the first overtone of ester groups was better studied in the spectra collected for the polar and nonpolar fractions, respectively. The bands assigned to peroxide, epoxy, tertiary alcohols and fatty acids were clearly observed in the spectra of the polar fraction while they are not noticeable in the spectra of the oils.La espectroscopía de infrarrojos por transformada de Fourier (FTIR se ha propuesto para estudiar la degradación de los aceites de oliva vírgenes (AOV sujetas a termoxidación. Las fracciones polares y no polares de aceites oxidados se analizaron mediante FTIR para obtener más información sobre los cambios espectrales menores que tienen lugar durante la termoxidación. Esa información ayuda en la interpretación de los espectros de las muestras puras. Con este objetivo, fracciones polares y no polares de 47 AOV termoxidados (190 °C en una freidora se analizaron mediante FTIR. La banda asignada a dobles enlaces cis se explica por su correlación con la disminución de ácido oleico (R2-ajustado=0,93. Las bandas asignadas a los grupos hidroxilos y del primer sobretono de los grupos éster se estudió mejor en los espectros recogidos para la fracción polar y no polar, respectivamente. Grupos asignados a per

  3. Comparison of the mobilities of negative and positive ions in nonpolar solutions.

    Science.gov (United States)

    Ivanishko, Irina S; Borovkov, Vsevolod I

    2010-08-01

    The mobilities of organic radical ions of different molecular volumes have been determined in squalane and hexane solutions to study the influence of the ion charge sign on the ionic mobility in a weakly polar liquid. The relative mobility of geminate radical ions was measured using the method of time-resolved electric field effect in the recombination fluorescence. To determine the mobility of cations and anions separately, a trend in the value of the relative mobility was analyzed by varying the mobility of one of the geminate partners. The ratios between the mobilities of the anion and the cation of the same molecules were found to be about 1.1. It was shown that in liquid alkanes, the solvent electrostriction was the main factor determining a decrease in the mobility of an ion as compared to the parent neutral molecule. The strong dependence of the electrostrictive effect on the radius of the ionic solvation shell allows the observed difference between negative and positive charge carriers by a small but systematic difference in the effective radii of the ions to be explained.

  4. Effect of solvents on the characteristics of rosin walled microcapsules prepared by a solvent evaporation technique.

    Science.gov (United States)

    Sheorey, D S; Dorle, A K

    1991-01-01

    Rosin microcapsules were prepared by a solvent evaporation technique using solvents with different rates of evaporation. Sulphadiazine was used as a model drug. The microcapsules were studied for their size, drug content, wall thickness, surface characteristics and in vitro release. The mean diameter increased and the drug content decreased as the rate of evaporation of the solvent increased. Fast evaporating solvents produced thick walled microcapsules with innumerable surface pores/cracks compared with slow evaporating solvents.

  5. Mechanism of extractant loss in solvent extraction process (Ⅰ)——Transfer of saponified D2EHPA from organic phase to aqueous phase and its aggregation behaviour

    Institute of Scientific and Technical Information of China (English)

    王笃金; 吴瑾光; 李彦; 翁诗甫; 吴佩强; 徐光宪

    1995-01-01

    The phenomenon of the loss of saponified D2EHPA(di(2-ethylhexyl)phosphoric acid,HA)from organic phase to aqueous phase and its aggregation behaviour were studied with FT-IR and DLS(dynamic light scattering)techniques based on the fact that saponified extractant can form reversed micelles orw/o microemulsions in n-heptane,a non-polar diluent.The results indicate that "normal rnioelles" or o/wmicroemulsions are formed from acidic extractant and its sodium salt in aqueous phase,and the micelle ormicroemulsion drop has a non-polar core which can solubilize nheptane,so the equilibrated aqueous phasecontaining extractant is a complex fluid rather than a "real solution".Therefore,the aqueous aggregate for-mation leads to the extractant loss in solvent extraction process.Strong electrolytes can prevent or lessen theextractant loss.The results of this paper provide a theoretical possibility for solving the problem ofextractant and solvent loss in liquid-liquid extraction industry.

  6. How membrane permeation is affected by donor delivery solvent.

    Science.gov (United States)

    Binks, Bernard P; Fletcher, Paul D I; Johnson, Andrew J; Elliott, Russell P

    2012-11-28

    We investigate theoretically and experimentally how the rate and extent of membrane permeation is affected by switching the donor delivery solvent from water to squalane for different permeants and membranes. In a model based on rate-limiting membrane diffusion, we derive explicit equations showing how the permeation extent and rate depend mainly on the membrane-donor and membrane-receiver partition coefficients of the permeant. Permeation results for systems containing all combinations of hydrophilic or hydrophobic donor solvents (aqueous solution or squalane), permeants (caffeine or testosterone) and polymer membranes (cellulose or polydimethylsiloxane) have been measured using a cell with stirred donor and re-circulating receiver compartments and continuous monitoring of the permeant concentration in the receiver phase. Relevant partition coefficients are also determined. Quantitative comparison of model and experimental results for the widely-differing permeation systems successfully enables the systematic elucidation of all possible donor solvent effects in membrane permeation. For the experimental conditions used here, most of the permeation systems are in agreement with the model, demonstrating that the model assumptions are valid. In these cases, the dominant donor solvent effects arise from changes in the relative affinities of the permeant for the donor and receiver solvents and the membrane and are quantitatively predicted using the separately measured partition coefficients. We also show how additional donor solvent effects can arise when switching the donor solvent causes one or more of the model assumptions to be invalid. These effects include a change in rate-limiting step, permeant solution non-ideality and others.

  7. Solvent Extraction in Hydrometallurgy: Present and Future

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    During the past 10 years, there have been incremental advances in the application of solvent extraction to process hydrometallurgy. The most cited areas in the literature include chemistry, chemical engineering, pilot plants, and plant operation. Within these areas, there were considerable interest in synergism,diluents, degradation, contactors, surfactants, hydrometallurgical applications, environmental and secondary applications, and health and safety. The summary to the present is followed by a prediction for the future in the above areas of interest. These include the use of speciation; improved understanding of the role of surfactants on the system; optimization through modelling, pilot plants, and contactor selection; improvements in plant operation; further new applications; and plant safety. The review has indicated that considerable knowledge is now available to optimize and improve on process design and plant applications.

  8. Theoretical study of solvent effects on the ground and low-lying excited free energy surfaces of a push-pull substituted azobenzene.

    Science.gov (United States)

    Corchado, Jose C; Sánchez, M Luz; Fdez Galván, Ignacio; Martín, M Elena; Muñoz-Losa, Aurora; Barata-Morgado, Rute; Aguilar, Manuel A

    2014-10-30

    The ground and low-lying excited free energy surfaces of 4-amino-4'-cyano azobenzene, a molecule that has been proposed as building block for chiroptical switches, are studied in gas phase and a variety of solvents (benzene, chloroform, acetone, and water). Solvent effects on the absorption and emission spectra and on the cis-trans thermal and photo isomerizations are analyzed using two levels of calculation: TD-DFT and CASPT2/CASSCF. The solvent effects are introduced using a polarizable continuum model and a QM/MM method, which permits one to highlight the role played by specific interactions. We found that, in gas phase and in agreement with the results found for other azobenzenes, the thermal cis-trans isomerization follows a rotation-assisted inversion mechanism where the inversion angle must reach values close to 180° but where the rotation angle can take almost any value. On the contrary, in polar solvents the mechanism is controlled by the rotation of the CN═NC angle. The change in the mechanism is mainly related to a better solvation of the nitrogen atoms of the azo group in the rotational transition state. The photoisomerization follows a rotational pathway both in gas phase and in polar and nonpolar solvents. The solvent introduces only small modifications in the nπ* free energy surface (S1), but it has a larger effect on the ππ* surface (S2) that, in polar solvents, gets closer to S1. In fact, the S2 band of the absorption spectrum is red-shifted 0.27 eV for the trans isomer and 0.17 eV for the cis. In the emission spectrum the trend is similar: only S2 is appreciably affected by the solvent, but in this case a blue shift is found.

  9. NIST ThermoData Engine: Extension to Solvent Design and Propagation of Uncertainties for Process Simulation

    DEFF Research Database (Denmark)

    Diky, Vladimir; Chirico, Robert D.; Muzny, Chris

    property values and expert system for data analysis and generation of recommended property values at the specified conditions along with uncertainties on demand. The most recent extension of TDE covers solvent design and multi-component process stream property calculations with uncertainty analysis......ThermoData Engine (TDE, NIST Standard Reference Databases 103a and 103b) is the first product that implements the concept of Dynamic Data Evaluation in the fields of thermophysics and thermochemistry, which includes maintaining the comprehensive and up-to-date database of experimentally measured....... Solvent Design function serves three tasks: (1) selection of best solvent for a solid solute, (2) search for a selective solvent for a solid binary mixture, and (3) selection of best solvent for extraction. Solvents are selected from the list of registered compounds encountering more than 27,000 entries...

  10. Hydrogenation of Isophthalonitrile with 1-Methylimidazole as an Effective Solvent for m-Xylenediamine Production

    Energy Technology Data Exchange (ETDEWEB)

    Chae, Tae Young; Row, Sung Wook; Yoo, Kye Sang; Lee, Sang Duek [Environment and Process Technology Division, Seoul (Korea, Republic of); Lee, Do Weon [University of Seoul, Seoul (Korea, Republic of)

    2006-03-15

    1-methylimidazole was shown to outperform the other organic solvents in this reaction. Moreover, amount of ammonia with using 1-methylimidazole as a solvent was lower than other processes. Thus, 1-methylimidazole is an attractive solvent in IPN hydrogenation for the production of MXDA. The correct choice of a solvent is a critical factor to govern the catalytic activity with desirable hydrogenation. Conventionally, organic materials such as aromatic hydrocarbons, aliphatic alcohols, aliphatic hydrocarbons, dimethylformamide and dioxane were employed in this reaction. Several MXDA producing processes with the organic solvent including m-xylene, pseudocumene, mesitylene, ethylbenzene, methylpyridine, benzonitrile, m-tolunitrile, MXDA and cyanopyridine were disclosed. However, the solvents and ammonia were vaporized under the operation conditions leading to amine cleavage with the resulting formation of methylbenzyl amines or the consumption of ammonia was still significant. Recently, some researchers reported that a high yield of MXDA was achieved using isopropanol under relatively low pressure condition; however, the consumption of ammonia was very significant.

  11. Reduction of chlorinated solvents at the Y-12 Oak Ridge Plant

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, L.M.; Simandl, R.F.; Richards, H.L. [Oak Ridge Y-12 Plant, TN (United States)

    1989-11-01

    The Oak Ridge Y-12 Plant has been actively seeking replacements for chlorinated solvents for several years. The first step in the reduction program was the identification of the solvents and their usages. The four main solvents used at the plant include Freon, methyl chloroform, perchloroethylene, and methylene chloride. The main reduction has been in the use of perchloroethylene. Other significant reductions have occurred in the area of changing out vapor degreasers which utilized perchloroethylene or methyl chloroform. These degreasers were replaced with ultrasonic cleaners which utilize aqueous detergent for cleaning. Ultrasonic cleaning has many advantages, but the one disadvantage is that it requires a rinse step. Currently, the work on reduction of chlorinate solvents is focused on finding solvents which can be substituted for squirt bottle type applications. Concerns which were addressed when looking at replacement solvents were disposal, compatibility, and health effects.

  12. Reduction of chlorinated solvents at the Y-12 Oak Ridge Plant

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, L.M.; Simandl, R.F.; Richards, H.L. [Oak Ridge Y-12 Plant, TN (United States)

    1989-11-01

    The Oak Ridge Y-12 Plant has been actively seeking replacements for chlorinated solvents for several years. The first step in the reduction program was the identification of the solvents and their usages. The four main solvents used at the plant include Freon, methyl chloroform, perchloroethylene, and methylene chloride. The main reduction has been in the use of perchloroethylene. Other significant reductions have occurred in the area of changing out vapor degreasers which utilized perchloroethylene or methyl chloroform. These degreasers were replaced with ultrasonic cleaners which utilize aqueous detergent for cleaning. Ultrasonic cleaning has many advantages, but the one disadvantage is that it requires a rinse step. Currently, the work on reduction of chlorinate solvents is focused on finding solvents which can be substituted for squirt bottle type applications. Concerns which were addressed when looking at replacement solvents were disposal, compatibility, and health effects.

  13. Microstructure of non-polar GaN on LiGaO2 grown by plasma-assisted MBE.

    Science.gov (United States)

    Shih, Cheng-Hung; Huang, Teng-Hsing; Schuber, Ralf; Chen, Yen-Liang; Chang, Liuwen; Lo, Ikai; Chou, Mitch Mc; Schaadt, Daniel M

    2011-06-15

    We have investigated the structure of non-polar GaN, both on the M - and A-plane, grown on LiGaO2 by plasma-assisted molecular beam epitaxy. The epitaxial relationship and the microstructure of the GaN films are investigated by transmission electron microscopy (TEM). The already reported epi-taxial relationship and for M -plane GaN is confirmed. The main defects are threading dislocations and stacking faults in both samples. For the M -plane sample, the density of threading dislocations is around 1 × 1011 cm-2 and the stacking fault density amounts to approximately 2 × 105 cm-1. In the A-plane sample, a threading dislocation density in the same order was found, while the stacking fault density is much lower than in the M -plane sample.

  14. Critical thickness for the formation of misfit dislocations originating from prismatic slip in semipolar and nonpolar III-nitride heterostructures

    Science.gov (United States)

    Smirnov, A. M.; Young, E. C.; Bougrov, V. E.; Speck, J. S.; Romanov, A. E.

    2016-01-01

    We calculate the critical thickness for misfit dislocation (MD) formation in lattice mismatched semipolar and nonpolar III-nitride wurtzite semiconductor layers for the case of MDs originated from prismatic slip (PSMDs). It has been shown that there is a switch of stress relaxation modes from generation of basal slip originated MDs to PSMDs after the angle between c-axis in wurtzite crystal structure and the direction of semipolar growth reaches a particular value, e.g., ˜70° for Al0.13Ga0.87N/GaN ( h 0 h ¯ 1 ) semipolar heterostructures. This means that for some semipolar growth orientations of III-nitride heterostructures biaxial relaxation of misfit stress can be realized. The results of modeling are compared to experimental data on the onset of plastic relaxation in AlxGa1-xN/GaN heterostructures.

  15. Simultaneous analysis method for polar and non-polar ginsenosides in red ginseng by reversed-phase HPLC-PAD.

    Science.gov (United States)

    Lee, Sa-Im; Kwon, Ha-Jeong; Lee, Yong-Moon; Lee, Je-Hyun; Hong, Seon-Pyo

    2012-02-23

    The paper describes the development of a simultaneous determination method for polar and non-polar ginsenosides in red ginseng with a reversed-phase high-performance liquid chromatography-pulsed amperometric detection method. This method could be applied directly without any pretreatment steps and enabled the performance of highly sensitive analysis within 1h. The detection (S/N=3) and quantification (S/N=10) limits for the ginsenosides ranged 0.02-0.10 ng and 0.1-0.3 ng, respectively. The linear regression coefficients ranged 0.9975-0.9998. Intra- and inter-day precisions were <9.91%. The mean recoveries ranged 98.08-103.06%. The total amount of ginsenosides in the hairy root of red ginseng was higher than that in the main root.

  16. Critical thickness for the formation of misfit dislocations originating from prismatic slip in semipolar and nonpolar III-nitride heterostructures

    KAUST Repository

    Smirnov, A. M.

    2016-01-20

    We calculate the critical thickness for misfit dislocation (MD) formation in lattice mismatched semipolar and nonpolar III-nitride wurtzite semiconductor layers for the case of MDs originated from prismatic slip (PSMDs). It has been shown that there is a switch of stress relaxation modes from generation of basal slip originated MDs to PSMDs after the angle between c-axis in wurtzite crystal structure and the direction of semipolar growth reaches a particular value, e.g., ∼70° for Al0.13Ga0.87N/GaN (h0h̄ 1) semipolar heterostructures. This means that for some semipolar growth orientations of III-nitride heterostructures biaxial relaxation of misfit stress can be realized. The results of modeling are compared to experimental data on the onset of plastic relaxation in AlxGa1−xN/GaN heterostructures.

  17. High-resolution field desorption/ionization fourier transform ion cyclotron resonance mass analysis of nonpolar molecules.

    Science.gov (United States)

    Schaub, Tanner M; Hendrickson, Christopher L; Qian, Kuangnan; Quinn, John P; Marshall, Alan G

    2003-05-01

    We report the first field desorption ionization broadband high-resolution (m/Deltam(50%) approximately 65 000) mass spectra. We have interfaced a field ionization/field desorption source to a home-built 9.4-T FT-ICR mass spectrometer. The instrumental configuration employs convenient sample introduction (in-source liquid injection) and external ion accumulation. We demonstrate the utility of this configuration by generating high-resolution positive-ion mass spectra of C(60) and a midboiling crude oil distillate. The latter contains species not accessible by common soft-ionization methods, for example, low-voltage electron ionization, electrospray ionization, and matrix-assisted laser desorption/ionization. The present work demonstrates significant advantages of FI/FD FT-ICR MS for analysis of nonpolar molecules in complex mixtures.

  18. Critical thickness for the formation of misfit dislocations originating from prismatic slip in semipolar and nonpolar III-nitride heterostructures

    Directory of Open Access Journals (Sweden)

    A. M. Smirnov

    2016-01-01

    Full Text Available We calculate the critical thickness for misfit dislocation (MD formation in lattice mismatched semipolar and nonpolar III-nitride wurtzite semiconductor layers for the case of MDs originated from prismatic slip (PSMDs. It has been shown that there is a switch of stress relaxation modes from generation of basal slip originated MDs to PSMDs after the angle between c-axis in wurtzite crystal structure and the direction of semipolar growth reaches a particular value, e.g., ∼70° for Al0.13Ga0.87N/GaN ( h 0 h ̄ 1 semipolar heterostructures. This means that for some semipolar growth orientations of III-nitride heterostructures biaxial relaxation of misfit stress can be realized. The results of modeling are compared to experimental data on the onset of plastic relaxation in AlxGa1−xN/GaN heterostructures.

  19. Advanced integrated solvent extraction systems

    Energy Technology Data Exchange (ETDEWEB)

    Horwitz, E.P.; Dietz, M.L.; Leonard, R.A. [Argonne National Lab., IL (United States)

    1997-10-01

    Advanced integrated solvent extraction systems are a series of novel solvent extraction (SX) processes that will remove and recover all of the major radioisotopes from acidic-dissolved sludge or other acidic high-level wastes. The major focus of this effort during the last 2 years has been the development of a combined cesium-strontium extraction/recovery process, the Combined CSEX-SREX Process. The Combined CSEX-SREX Process relies on a mixture of a strontium-selective macrocyclic polyether and a novel cesium-selective extractant based on dibenzo 18-crown-6. The process offers several potential advantages over possible alternatives in a chemical processing scheme for high-level waste treatment. First, if the process is applied as the first step in chemical pretreatment, the radiation level for all subsequent processing steps (e.g., transuranic extraction/recovery, or TRUEX) will be significantly reduced. Thus, less costly shielding would be required. The second advantage of the Combined CSEX-SREX Process is that the recovered Cs-Sr fraction is non-transuranic, and therefore will decay to low-level waste after only a few hundred years. Finally, combining individual processes into a single process will reduce the amount of equipment required to pretreat the waste and therefore reduce the size and cost of the waste processing facility. In an ongoing collaboration with Lockheed Martin Idaho Technology Company (LMITCO), the authors have successfully tested various segments of the Advanced Integrated Solvent Extraction Systems. Eichrom Industries, Inc. (Darien, IL) synthesizes and markets the Sr extractant and can supply the Cs extractant on a limited basis. Plans are under way to perform a test of the Combined CSEX-SREX Process with real waste at LMITCO in the near future.

  20. Comparison and Combination of Solvent Extraction and Adsorption for Crude Glycerol Enrichment

    OpenAIRE

    Hunsom, Mali; Saila, Payia; Chaiyakam, Penpisuth; Kositnan, Winata

    2016-01-01

    A comparative study of enrichment of crude glycerol via solvent extraction and adsorption was performed at a laboratory scale at ambient temperature (30 oC). Effect of various parameters on the properties of the obtained glycerol including glycerol-, ash- and contaminant contents and color, was explored. The results showed that the enrichment of glycerol by solvent extraction was significantly affected by the solvent type and ratio of solvent to pre-treated crude glycerol. The use of n-C3H7OH...

  1. Phase-Change Aminopyridines as Carbon Dioxide Capture Solvents

    Energy Technology Data Exchange (ETDEWEB)

    Malhotra, Deepika [Energy Processes and Materials; Page, Jordan P. [Energy Processes and Materials; Bowden, Mark E. [Energy Processes and Materials; Karkamkar, Abhijeet [Energy Processes and Materials; Heldebrant, David J. [Energy Processes and Materials; Glezakou, Vassiliki-Alexandra [Energy Processes and Materials; Rousseau, Roger [Energy Processes and Materials; Koech, Phillip K. [Energy Processes and Materials

    2017-06-22

    Carbon dioxide is the main atmospheric greenhouse gas released from industrial point sources. In order to mitigate adverse environmental effects of these emissions, carbon capture, storage and utilization is required. To this end, several CO2 capture technologies are being developed for application in carbon capture, which include aqueous amines and water-lean solvents. Herein we report new aminopyridine solvents with the potential for CO2 capture from coal-fired power plants. These four solvents 2-picolylamine, 3-picolylamine, 4-picolylamine and N’-(pyridin-4-ylmethyl)ethane-1,2-diamine are liquids that rapidly bind CO2 to form crystalline solids at standard room temperature and pressure. These solvents have displayed high CO2 capture capacity (11 - 20 wt%) and can be regenerated at temperatures in the range of 120 - 150 C. The advantage of these primary aminopyridine solvents is that crystalline salt product can be separated, making it possible to regenerate only the CO2-rich solid ultimately resulting in reduced energy penalty.

  2. Difference between Chitosan Hydrogels via Alkaline and Acidic Solvent Systems

    Science.gov (United States)

    Nie, Jingyi; Wang, Zhengke; Hu, Qiaoling

    2016-10-01

    Chitosan (CS) has generated considerable interest for its desirable properties and wide applications. Hydrogel has been proven to be a major and vital form in the applications of CS materials. Among various types of CS hydrogels, physical cross-linked CS hydrogels are popular, because they avoided the potential toxicity and sacrifice of intrinsic properties caused by cross-linking or reinforcements. Alkaline solvent system and acidic solvent system are two important solvent systems for the preparation of physical cross-linked CS hydrogels, and also lay the foundations of CS hydrogel-based materials in many aspects. As members of physical cross-linked CS hydrogels, gel material via alkaline solvent system showed significant differences from that via acidic solvent system, but the reasons behind are still unexplored. In the present work, we studied the difference between CS hydrogel via alkaline system and acidic system, in terms of gelation process, hydrogel structure and mechanical property. In-situ/pseudo in-situ studies were carried out, including fluorescent imaging of gelation process, which provided dynamic visualization. Finally, the reasons behind the differences were explained, accompanied by the discussion about design strategy based on gelation behavior of the two systems.

  3. [Generic method for determination of volatile organic solvents in cosmetics].

    Science.gov (United States)

    Da, Jing; Huang, Xianglu; Wang, Gangli; Cao, Jin; Zhang, Qingsheng

    2014-11-01

    A generic screening, confirmation and determination method was established based on 36 commonly used volatile organic solvents in cosmetics by headspace gas chromatography- mass spectrometry (GC-MS). This method included a database for pilot screening and identifi- cation of those solvents and their quantitative method. Pilot screening database was composed by two sections, one was household section built by two columns with opposite polarities (col- umn VF-1301 ms and DB-5 ms) using retention index in different column systems as qualitative parameter, and the other was NIST MS search version 2.0. Meanwhile, the determination method of the 36 volatile solvents was developed with GC-MS. Cosmetic samples were dissolved in water and transferred to a headspace vial. After 30 min equilibration at 60 °C, the samples were analyzed by GC-MS equipped with a capillary chromatographic column VF-1301 ms. The external calibration was used for quantification. The limits of detection were from 0.01 to 3.3 μg/g, and the recoveries were from 60.77% to 126.6%. This study provided a generic method for pilot screening, identification, and quantitation of volatile organic solvents in cosmetics, and may solve the problem that different analytical methods need to be developed for different targeted compounds and pilot screening for potential candidate solvent residues.

  4. Behavioral evaluation of workers exposed to mixtures of organic solvents

    Energy Technology Data Exchange (ETDEWEB)

    Maizlish, N.A.; Langolf, G.D.; Whitehead, L.W.; Fine, L.J.; Albers, J.W.; Goldberg, J.; Smith, P.

    1985-09-01

    Reports from Scandinavia have suggested behavioral impairment among long term workers exposed to solvents below regulatory standards. A cross sectional study of behavioral performance was conducted among printers and spray painters exposed to mixtures of organic solvents to replicate the Scandinavian studies and to examine dose-response relationships. Eligible subjects consisted of 640 hourly workers from four midwestern United States companies. Of these, 269 responded to requests to participate and 240 were selected for study based on restrictions for age, sex, education, and other potentially confounding variables. The subjects tested had been employed on average for six years. Each subject completed an occupational history, underwent a medical examination, and completed a battery of behavioural tests. These included the Fitts law psychomotor task, the Stroop color-word test, the Sternberg short term memory scanning test, the short term memory span test, and the continuous recognition memory test. Solvent exposure for each subject was defined as an exposed or non-exposed category based on a plant industrial hygiene walk-through and the concentration of solvents based on an analysis of full shift personal air samples by gas chromatography. The first definition was used to maintain consistency with Scandinavian studies, but the second was considered to be more accurate. The average full shift solvent concentration was 302 ppm for the printing plant workers and 6-13 ppm for the workers at other plants. Isopropanol and hexane were the major components, compared with toluene in Scandinavian studies.

  5. Neurotoxicity of industrial solvents: a review of the literature

    Energy Technology Data Exchange (ETDEWEB)

    Baker, E.L. Jr.; Smith, T.J.; Landrigan, P.J.

    1985-01-01

    Organic solvents, particularly stryrene, are used widely in boatbuilding. They may be absorbed by workers either through the respiratory tract or the skin. Uptake is influenced by level and duration of exposure, work load, and specific physiochemical features of each solvent, as well as by work practices and use of protective equipment. Kinetics of metabolism and excretion kinetics are highly variable among compounds. Metabolites can be measured in blood, urine, or exhaled breath and may serve as indirect indices of absorption. Acute high-dose exposure to organic solvents can produce a transient narcotic effect on the central nervous system. This effect occurs in proportion to brain dose, which in turn is determined by intensity and duration of exposure. Additionally, chronic exposures to organic solvents have been reported to produce an increased frequency of neurologic signs and symptoms. These findings include peripheral neuropathies and toxic encephalopathies. The latter are characterized by alterations in affect, memory loss, and impaired cognition. Concern exists that prolonged excessive exposure to organic solvents may lead to premature and persistent dementia in certain workers. 65 references.

  6. Handbook of green chemistry, green solvents, ionic liquids

    CERN Document Server

    Anastas, Paul T; Stark, Annegret

    2014-01-01

    Green chemistry is a vitally important subject area in the world where being as green and environmentally sound as possible is no longer a luxury but a necessity. Its applications include the design of chemical products and processes that help to reduce or eliminate the use and generation of hazardous substances. The Handbook of Green Chemistry comprises 12 volumes, split into subject-specific sets as follow: Set I: Green Catalysis Set II: Green Solvents Volume 4: Supercritical Solvents Volume 5: Reactions in Water Volume 6: Ionic Liquids Set III: Green

  7. A new model for solvent extraction in columns

    Energy Technology Data Exchange (ETDEWEB)

    Leonard, R.A.; Regalbuto, M.C.; Chamberlain, D.B.; Vandegrift, G.F.

    1989-12-08

    A new model was developed for analyzing solvent extraction processes carried out in columns. Each column is treated as a series of well-defined equilibrium stages where the backmixing (other-phase carryover) between stages can be large. By including all mass transfer effects in the backmixing value, the same number of stages can be used for all extracted components no matter what their distribution coefficients. This greatly simplifies the calculations required when modeling multicomponent solvent extraction processes. Initial testing shows the new model to be better than either the Height of an Equivalent Theoretical Plate (HETP) or the Height of a Transfer Unit (HTU) method.

  8. Measurement of oxygen transfer from air into organic solvents

    DEFF Research Database (Denmark)

    Ramesh, Hemalata; Mayr, Torsten; Hobisch, Mathias;

    2016-01-01

    For the first time, we demonstrate on-line oxygen measurements in non-aqueous media using a novel optical sensor. The sensor was used to measure oxygen concentration in various organic solvents including toluene, THF, isooctane, DMF, heptane and hexane (which have all been shown suitable for several biological...

  9. Surface tension of a coal extract in an organic solvent; Sekitan chushutsu seibun no kaigo to hyomen choryoku

    Energy Technology Data Exchange (ETDEWEB)

    Kikuchi, T.; Hayasaka, K.; Takanohashi, T.; Iino, M. [Tohoku University, Sendai (Japan). Institute for Chemical Reaction Science

    1996-10-28

    The behavior and properties of associated bodies were studied through measurement of surface tension considering acetone-soluble fraction relatively light among various solvent extracts of coal. In experiment, the acetone-soluble fraction was extracted from the substances extracted from Upper Freeport coal as standard specimen using the mixed solvent of carbon disulfide (CS2) and N-methyl-2-pyrrolidinone (NMP), and it was dissolved into NMP after drying. Surface tension was measured by Wilhelmy method. The experimental results are as follows. Equilibrium surface tension is equal to the surface tension of pure solvent in a low concentration range of solution, and decreases with an increase in concentration approaching a fixed value at 0 in log concentration, nearly showing an S curve. Adsorption of species with non-polar aromatic ring of the acetone-soluble fraction on a solution surface probably decreases surface tension. Change with time in surface tension is observed which suggests fast initial reaction and slow subsequent reaction. 4 figs.

  10. Effect of different solvents extracts and mode of action of Loktanella spp. Gb03 on toxic dinoflagellate

    Science.gov (United States)

    Hameed, Anmar; Usup, Gires; Ahmad, Asmat

    2016-11-01

    This study was aimed to evaluate the algicidal activity of Loktanella sp. Gb-03 bacterial extracts against toxic dinoflagellate, using various polar and non-polar solvents. For this purpose, six different solvent extracts were prepared (i.e. methanol, ethyl acetate, hexane, chloroform, acetonitrile and water). Ratio of 1:100 (v:v) (extract to dinoflagellate culture) of each extract was used for preliminary algicidal activity screening against toxic dinoflagellate Coolia malaynesis. Dinoflagellate cells at the stationary phase (1.0 × 103 cells/ mL) were treated with 1% (v/v) of each extract by using 24-well microplate. The plates were then incubated for 24 hours at dinoflagellate culture condition (under a light intensity of 140 µmol m-2s-1 and 12:12 hours light:dark photoperiod). The result of algicidal activity screening showed that all 6 extracts from Loktanella sp. Gb-03 had different ranges of algicidal activity against the toxic dinoflagellates. Ethyl acetate extract showed the highest activity against C. malaynesis and also other harmful dinoflagellate (Alexandrium sp. Alexandrium leei, Alexandrium affine, Alexandrium tamiyavanichi, Alexandrium tamarense, Gambierdiscus belizeanus, and Ostreopsis). This study was the first to explore the algicidal activity of Loktanella sp. Gb-03 extracts against toxic dinoflagellate with ethyl acetate as the best solvent to extract algicidal active compounds.

  11. Indium incorporation in semipolar (20 2 ̅ 1) and nonpolar (10 1 ̅ 0) InGaN grown by plasma assisted molecular beam epitaxy

    Science.gov (United States)

    Sawicka, M.; Feduniewicz-Żmuda, A.; Kryśko, M.; Turski, H.; Muziol, G.; Siekacz, M.; Wolny, P.; Skierbiszewski, C.

    2017-02-01

    Semipolar (20 2 ̅ 1) , nonpolar m-plane (10 1 ̅ 0) and polar c-plane (0001) GaN and InGaN layers were grown by plasma-assisted molecular beam epitaxy. The surface of semipolar and nonpolar GaN grown under Ga-rich conditions is very smooth. The indium incorporation efficiency in InGaN layers grown under In-rich growth conditions is studied on three surface orientations (i) as a function of temperature from 570 to 650 °C and (ii) for varied active nitrogen flux from 0.41 to 2.03 μm/h. The In content follows the relation (10 1 ̅ 0) experiments. Indium composition in InGaN layers can be increased (i) by the decrease of the growth temperature and (ii) increase of the applied nitrogen flux for all studied surface orientations. Additionally, surface morphology of semipolar, nonpolar and c-polar InGaN layers grown at 650, 640 and 620 °C is compared. No increase in surface roughness for semipolar and nonpolar InGaN was observed in contrast to c-plane counterparts.

  12. Non-polar In x Ga1-x N/GaN quantum dots: impact of dot size and shape anisotropies on excitonic and biexcitonic properties

    Science.gov (United States)

    Kanta Patra, Saroj; Schulz, Stefan

    2017-01-01

    In this work, we present a theoretical analysis of the built-in potential, the excitonic and biexcitonic properties of non-polar InGaN/GaN quantum dots by means of self-consistent Hartree calculations using \\mathbf{k}\\centerdot \\mathbf{p} theory. Special attention is paid to the impact of dot size and shape anisotropies on the results. Our calculations reveal that even though non-polar InGaN/GaN quantum dots exhibit strongly reduced built-in fields when compared to c-plane dots, the excitonic and biexcitonic properties are significantly affected by these residual fields. Furthermore, changes in the built-in field when the geometrical dot features are modified, result in an unusual variation of the exciton binding energy. All these findings highlight that the dot geometry significantly affects electronic and optical properties of non-polar InGaN/GaN systems. This is further supported by comparing our theoretical data with experimental literature results. Here, we analyze also trends in exciton and biexciton binding energies and discuss the potential use of non-polar InGaN/GaN dots for entangled photon emission via the time reordering scheme.

  13. Dynamics around solutes and solute-solvent complexes in mixed solvents.

    Science.gov (United States)

    Kwak, Kyungwon; Park, Sungnam; Fayer, M D

    2007-09-04

    Ultrafast 2D-IR vibrational echo experiments, IR pump-probe experiments, and FT-IR spectroscopy of the hydroxyl stretch of phenol-OD in three solvents, CCl4, mesitylene (1, 3, 5 trimethylbenzene), and the mixed solvent of mesitylene and CCl4 (0.83 mole fraction CCl4), are used to study solute-solvent dynamics via observation of spectral diffusion. Phenol forms a complex with Mesitylene. In the mesitylene solution, there is only complexed phenol; in the CCl4 solution, there is only uncomplexed phenol; and in the mixed solvent, both phenol species are present. Dynamics of the free phenol in CCl4 or the mixed solvent are very similar, and dynamics of the complex in mesitylene and in the mixed solvent are very similar. However, there are differences in the slowest time scale dynamics between the pure solvents and the mixed solvents. The mixed solvent produces slower dynamics that are attributed to first solvent shell solvent composition variations. The composition variations require a longer time to randomize than is required in the pure solvents, where only density variations occur. The experimental results and recent MD simulations indicate that the solvent structure around the solute may be different from the mixed solvent's mole fraction.

  14. Solvent removal during synthetic and Nephila fiber spinning.

    Science.gov (United States)

    Kojic, Nikola; Kojic, Milos; Gudlavalleti, Sauri; McKinley, Gareth

    2004-01-01

    The process by which spiders make their mechanically superior fiber involves removal of solvent (water) from a concentrated protein solution while the solution flows through a progressively narrowing spinning canal. Our aim was to determine a possible mechanism of spider water removal by using a computational model. To develop appropriate computational techniques for modeling of solvent removal during fiber spinning, a study was first performed using a synthetic solution. In particular, the effect of solvent removal during elongational flow (also exhibited in the spinning canal of the spider) on fiber mechanical properties was examined. The study establishes a model for solvent removal during dry spinning of synthetic fibers, assuming that internal diffusion governs solvent removal and that convective resistance is small. A variable internal solvent diffusion coefficient, dependent on solvent concentration, is also taken into account in the model. An experimental setup for dry (air) spinning was used to make fibers whose diameter was on the order of those made by spiders (approximately 1 microm). Two fibers of different thickness, corresponding to different spinning conditions, were numerically modeled for solvent removal and then mechanically tested. These tests showed that the thinner fiber, which lost more solvent under elongational flow, had 5-fold better mechanical properties (elastic modulus of 100 MPa and toughness of 15 MJ/m3) than the thicker fiber. Even though the mechanical properties were far from those of dragline spider silk (modulus of 10 GPa and toughness of 150 MJ/m3), the experimental methodology and numerical principles developed for the synthetic case proved to be valuable when establishing a model for the Nephila spinning process. In this model, an assumption of rapid convective water removal at the spinning canal wall was made, with internal diffusion of water through the fiber as the governing process. Then the diffusion coefficient of water

  15. Effect of some organic solvents on oxidative phosphorylation in rat liver mitochondria

    DEFF Research Database (Denmark)

    Syed, Muzeeb; Skonberg, Christian; Hansen, Steen Honoré

    2013-01-01

    The effect of acetone, acetonitrile, dimethyl sulfoxide (DMSO), ethanol and methanol on oxidative phosphorylation (ATP synthesis) in rat liver mitochondria has been studied. All the organic solvents inhibited the oxidative phosphorylation in a concentration dependent manner, but with differences...... on oxidative phosphorylation in mitochondria should therefore include the use of relevant concentrations of the organic solvent in order to validate the contribution....

  16. Mathematical modelling of simultaneous solvent evaporation and chemical curing in thermoset coatings: A parameter study

    DEFF Research Database (Denmark)

    Kiil, Søren

    2011-01-01

    A mathematical model, describing the curing behaviour of a two-component, solvent-based, thermoset coating, is used to conduct a parameter study. The model includes curing reactions, solvent intra-film diffusion and evaporation, film gelation, vitrification, and crosslinking. A case study with a ...

  17. Influence of water content in mixed solvent on surface morphology, wettability, and photoconductivity of ZnO thin films.

    Science.gov (United States)

    Zhao, Min; Shang, Fengjiao; Lv, Jianguo; Song, Ying; Wang, Feng; Zhou, Zhitao; He, Gang; Zhang, Miao; Song, Xueping; Sun, Zhaoqi; Wei, Yiyong; Chen, Xiaoshuang

    2014-01-01

    ZnO thin films have been synthesized by means of a simple hydrothermal method with different solvents. The effect of deionized water content in the mixed solvents on the surface morphology, crystal structure, and optical property has been investigated by scanning electron microscopy, X-ray diffraction, and UV-Vis spectrophotometer. A large number of compact and well-aligned hexagonal ZnO nanorods and the maximal texture coefficient have been observed in the thin film, which is grown in the mixed solvent with x = 40%. A lot of sparse, diagonal, and pointed nanorods can be seen in the ZnO thin film, which is grown in the 40-mL DI water solution. The optical band gap decreases firstly and then increases with the increase of x. Reversible wettability of ZnO thin films were studied by home-made water contact angle apparatus. Reversible transition between hydrophobicity and hydrophilicity may be attributed to the change of surface chemical composition, surface roughness and the proportion of nonpolar planes on the surface of ZnO thin films. Photocurrent response of ZnO thin films grown at different solvents were measured in air. The response duration of the thin film, which is grown in the solvent with x = 40%, exhibits a fast growth in the beginning but cannot approach the saturate current value within 100 s. The theoretical mechanism for the slower growth or decay duration of the photocurrent has been discussed in detail.

  18. Organogels thermodynamics, structure, solvent role, and properties

    CERN Document Server

    Guenet, Jean-Michel

    2016-01-01

    This book provides a physics-oriented introduction to organogels with a comparison to polymer thermoreversible gels whenever relevant. The past decade has seen the development of a wide variety of newly-synthesized molecules that can spontaneously self-assemble or crystallize from their organic or aqueous solutions to produce fibrillar networks, namely organogels, with potential applications in organic electronics, light harvesting, bio-imaging, non-linear optics, and the like. This compact volume presents a detailed outlook of these novel molecular systems with special emphasis upon their thermodynamics, morphology, molecular structure, and rheology. The definition of these complex systems is also tackled, as well as the role of the solvent. The text features numerous temperature-phase diagrams for a variety of organogels as well as illustrations of their structures at the microscopic, mesoscopic and macroscopic level. A review of some potential applications is provided including hybrid functional materials ...

  19. Simultaneous detection of polar and nonpolar compounds by ambient mass spectrometry with a dual electrospray and atmospheric pressure chemical ionization source.

    Science.gov (United States)

    Cheng, Sy-Chyi; Jhang, Siou-Sian; Huang, Min-Zong; Shiea, Jentaie

    2015-02-03

    A dual ionization source combining electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) was developed to simultaneously ionize both polar and nonpolar compounds. The source was constructed by inserting a fused silica capillary into a stainless steel column enclosed in a glass tube. A high dc voltage was applied to a methanol solution flowing in the fused silica capillary to generate an ESI plume at the capillary tip. A high ac voltage was applied to a ring electrode attached to the glass tube to generate plasma from the nitrogen gas flowing between the glass tube and the stainless steel column. The concentric arrangement of the ESI plume and the APCI plasma in the source ensured that analytes entering the ionization region interacted with both ESI and APCI primary ion species generated in the source. Because the high voltages required for ESI and APCI were independently applied and controlled, the dual ion source could be operated in ESI-only, APCI-only, or ESI+APCI modes. Analytes were introduced into the ESI and/or APCI plumes by irradiating sample surfaces with a continuous-wavelength laser or a pulsed laser beam. Analyte ions could also be produced by directing the dual ESI+APCI source toward sample surfaces for desorption and ionization. The ionization mechanisms involved in the dual ion source include Penning ionization, ion molecule reactions, and fused-droplet electrospray ionization. Standards of polycyclic aromatic hydrocarbons, angiotensin I, lidocaine, ferrocene, diesel, and rosemary oils were used for testing. Protonated analyte ions were detected in ESI-only mode, radical cations were detected in APCI-only mode, and both types of ions were detected in ESI+APCI mode.

  20. General baseline toxicity QSAR for nonpolar, polar and ionisable chemicals and their mixtures in the bioluminescence inhibition assay with Aliivibrio fischeri.

    Science.gov (United States)

    Escher, Beate I; Baumer, Andreas; Bittermann, Kai; Henneberger, Luise; König, Maria; Kühnert, Christin; Klüver, Nils

    2017-03-22

    The Microtox assay, a bioluminescence inhibition assay with the marine bacterium Aliivibrio fischeri, is one of the most popular bioassays for assessing the cytotoxicity of organic chemicals, mixtures and environmental samples. Most environmental chemicals act as baseline toxicants in this short-term screening assay, which is typically run with only 30 min of exposure duration. Numerous Quantitative Structure-Activity Relationships (QSARs) exist for the Microtox assay for nonpolar and polar narcosis. However, typical water pollutants, which have highly diverse structures covering a wide range of hydrophobicity and speciation from neutral to anionic and cationic, are often outside the applicability domain of these QSARs. To include all types of environmentally relevant organic pollutants we developed a general baseline toxicity QSAR using liposome-water distribution ratios as descriptors. Previous limitations in availability of experimental liposome-water partition constants were overcome by reliable prediction models based on polyparameter linear free energy relationships for neutral chemicals and the COSMOmic model for charged chemicals. With this QSAR and targeted mixture experiments we could demonstrate that ionisable chemicals fall in the applicability domain. Most investigated water pollutants acted as baseline toxicants in this bioassay, with the few outliers identified as uncouplers or reactive toxicants. The main limitation of the Microtox assay is that chemicals with a high melting point and/or high hydrophobicity were outside of the applicability domain because of their low water solubility. We quantitatively derived a solubility cut-off but also demonstrated with mixture experiments that chemicals inactive on their own can contribute to mixture toxicity, which is highly relevant for complex environmental mixtures, where these chemicals may be present at concentrations below the solubility cut-off.

  1. Modeling Solvent Broadening on the Vibronic Spectra of a Series of Coumarin Dyes. From Implicit to Explicit Solvent Models.

    Science.gov (United States)

    Cerezo, Javier; Avila Ferrer, Francisco J; Prampolini, Giacomo; Santoro, Fabrizio

    2015-12-08

    We present a protocol to estimate the solvent-induced broadening of electronic spectra based on a model that explicitly takes into account the environment embedding the solute. Starting from a classical approximation of the solvent contribution to the spectrum, the broadening arises from the spread of the excitation energies due to the fluctuation of the solvent coordinates, and it is represented as a Gaussian line shape that convolutes the vibronic spectrum of the solute. The latter is computed in harmonic approximation at room temperature with a time-dependent approach. The proposed protocol for the computation of spectral broadening exploits molecular dynamics (MD) simulations performed on the solute-solvent system, keeping the solute degrees of freedom frozen, followed by the computation of the excitation properties with a quantum mechanics/molecular mechanics (QM/MM) approach. The factors that might influence each step of the protocol are analyzed in detail, including the selection of the empirical force field (FF) adopted in the MD simulations and the QM/MM partition of the system to compute the excitation energies. The procedure is applied to a family of coumarin dyes, and the results are compared with experiments and with the predictions of a very recent work (Cerezo et al., Phys. Chem. Chem. Phys. 2015, 17, 11401-11411), where an implicit model was adopted for the solvent. The final spectra of the considered coumarins were obtained without including ad hoc phenomenological parameters and indicate that the broadenings computed with explicit and implicit models both follow the experimental trend, increasing as the polarity change from the initial to the final state increases. More in detail, the implicit model provides larger estimations of the broadening that are closer to the experimental evidence, while explicit models appear to better capture relative differences arising from different solvents or different solutes. Possible inaccuracies of the adopted

  2. Biological Treatment of Solvent-Based Paint

    Science.gov (United States)

    2011-01-01

    solvent. In addition, hydrocarbon mixtures, aromatic hydrocarbon, and Medium Aliphatic Solvent Naphtha are descriptors used by the manufactures to...Enamel Aromatic Hydrocarbon 14 Mineral Spirits 10 Naphtha 10 Ethyl Benzene 0.21 Xylene 1.0 Sherwin Williams Co Enamel Mineral Spirits 49...Solvent Naphtha 31.5 Non-hazardous Ingredients 68 Parker Paints Enamel Mineral Spirits 17 Naphtha 7 Aromatic Hydrocarbons 3 1,2,4

  3. Increased risk for hepatitis C associated with solvent use among Canadian Aboriginal injection drug users

    Directory of Open Access Journals (Sweden)

    Jolly Ann M

    2010-07-01

    Full Text Available Abstract Background Solvent abuse is a particularly serious issue affecting Aboriginal people. Here we examine the association between solvent use and socio-demographic variables, drug-related risk factors, and pathogen prevalence in Aboriginal injection drug users (IDU in Manitoba, Canada. Methods Data originated from a cross-sectional survey of IDU from December 2003 to September 2004. Associations between solvent use and variables of interest were assessed by multiple logistic regression. Results A total of 266 Aboriginal IDU were included in the analysis of which 44 self-reported recent solvent use. Hepatitis C infection was 81% in solvent-users, compared to 55% in those reporting no solvent use. In multivariable models, solvent-users were younger and more likely to be infected with hepatitis C (AOR: 3.5; 95%CI: 1.3,14.7, to have shared needles in the last six months (AOR: 2.6; 95%CI:1.0,6.8, and to have injected talwin & Ritalin (AOR: 10.0; 95%CI: 3.8,26.3. Interpretation High hepatitis C prevalence, even after controlling for risky injection practices, suggests that solvent users may form closed networks of higher risk even amongst an already high-risk IDU population. Understanding the social-epidemiological context of initiation and maintenance of solvent use is necessary to address the inherent inequalities encountered by this subpopulation of substance users, and may inform prevention strategies for other marginalized populations.

  4. Understanding Solvent Manipulation of Morphology in Bulk-Heterojunction Organic Solar Cells.

    Science.gov (United States)

    Chen, Yuxia; Zhan, Chuanlang; Yao, Jiannian

    2016-10-06

    Film morphology greatly influences the performance of bulk-heterojunction (BHJ)-structure-based solar cells. It is known that an interpenetrating bicontinuous network with nanoscale-separated donor and acceptor phases for charge transfer, an ordered molecular packing for exciton diffusion and charge transport, and a vertical compositionally graded structure for charge collection are prerequisites for achieving highly efficient BHJ organic solar cells (OSCs). Therefore, control of the morphology to obtain an ideal structure is a key problem. For this solution-processing BHJ system, the solvent participates fully in film processing. Its involvement is critical in modifying the nanostructure of BHJ films. In this review, we discuss the effects of solvent-related methods on the morphology of BHJ films, including selection of the casting solvent, solvent mixture, solvent vapor annealing, and solvent soaking. On the basis of a discussion on interaction strength and time between solvent and active materials, we believe that the solvent-morphology-performance relationship will be clearer and that solvent selection as a means to manipulate the morphology of BHJ films will be more rational.

  5. Molecular Thermodynamic Modeling of Mixed Solvent Solubility

    DEFF Research Database (Denmark)

    Ellegaard, Martin Dela; Abildskov, Jens; O’Connell, John P.

    2010-01-01

    A method based on statistical mechanical fluctuation solution theory for composition derivatives of activity coefficients is employed for estimating dilute solubilities of 11 solid pharmaceutical solutes in nearly 70 mixed aqueous and nonaqueous solvent systems. The solvent mixtures range from...... nearly ideal to strongly nonideal. The database covers a temperature range from 293 to 323 K. Comparisons with available data and other existing solubility methods show that the method successfully describes a variety of observed mixed solvent solubility behaviors using solute−solvent parameters from...

  6. A solvent tolerant isolate of Enterobacter aerogenes.

    Science.gov (United States)

    Gupta, Anshu; Singh, Rajni; Khare, S K; Gupta, M N

    2006-01-01

    A solvent tolerant strain of Enterobacter aerogenes was isolated from soil by cyclohexane enrichment. Presence of cyclohexane (20%) in culture media prolonged the lag phase and caused reduction in biomass. Transmission electron micrographs showed convoluted cell membrane and accumulation of solvent in case of the cells grown in cyclohexane. The Enterobacter isolate was able to grow in the range of organic solvents having log P above 3.2 and also in presence of mercury, thus showing potential for treatment of solvent rich wastes.

  7. Organic solvent use in enterprises in Japan.

    Science.gov (United States)

    Nagasawa, Yasuhiro; Ukai, Hirohiko; Okamoto, Satoru; Samoto, Hajime; Itoh, Kenji; Moriguchi, Jiro; Sakuragi, Sonoko; Ohashi, Fumiko; Takada, Shiro; Kawakami, Tetsuya; Ikeda, Masayuki

    2011-01-01

    This study was initiated to elucidate possible changes in types of organic solvents (to be called solvents in short) used in enterprises in Japan through comparison of current solvent types with historical data since 1983. To investigate current situation in solvent use in enterprises, surveys were conducted during one year of 2009 to 2010. In total, workroom air samples in 1,497 unit workplaces with solvent use were analyzed in accordance with regulatory requirements. Typical use pattern of solvents was as mixtures, accounting for >70% of cases. Adhesives spreading (followed by adhesion) was relatively common in small-scale enterprises, whereas printing and painting work was more common in middle-scale ones, and solvent use for testing and research purpose was basically in large-scaled enterprises. Through-out printing, painting, surface coating and adhesive application, toluene was most common (being detected in 49 to 82% of workplaces depending on work types), whereas isopropyl alcohol was most common (49%) in degreasing, cleaning and wiping workplaces. Other commonly used solvents were methyl alcohol, ethyl acetate and acetone (33 to 37%). Comparison with historical data in Japan and literature-retrieved data outside of Japan all agreed with the observation that toluene is the most commonly used solvent. Application of trichloroethylene and 1,1,1-trichloroethane, once common in 1980s, has ceased to exist in recent years.

  8. Extractive Distillation with Salt in Solvent

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    Extractive distillation with salt in solvent is a new process for producing anhydrous ethanol by combining the principle of "salt effect" and some traditional extractive distillation methods. Compared with the common extractive distillation the performance of solvent is improved, the recycling amount of solvent is reduced to 1/4-1/5, and the number of theoretical plates is reduced to 1/3. Energy consumption and cost of equipment are also reduced and continuous production is realized. High efficiency and low solvent wastage make this technique feasible.

  9. OCCUPATIONAL SOLVENT EXPOSURE ASSOCIATED WITH DEVELOPMENTAL TOXICITY

    Directory of Open Access Journals (Sweden)

    Alina-Costina LUCA

    2016-05-01

    Full Text Available Organic solvent is a broad term that applies to many classes of chemicals. The solvent (benzene, toluene etc. aspects of occupational exposure are reviewed via the examination of the use, occurrence, and disposition as well as population’s potential of risk. The general public can be exposed to solvent in ambient air as a result of its occurrence in paint process. Solvents are primarily irritants to the skin and mucous membranes and have narcotic properties at high concentrations. Published epidemiological data identified various types of birth defects in certain occupations.

  10. Optical modulator including grapene

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Ming; Yin, Xiaobo; Zhang, Xiang

    2016-06-07

    The present invention provides for a one or more layer graphene optical modulator. In a first exemplary embodiment the optical modulator includes an optical waveguide, a nanoscale oxide spacer adjacent to a working region of the waveguide, and a monolayer graphene sheet adjacent to the spacer. In a second exemplary embodiment, the optical modulator includes at least one pair of active media, where the pair includes an oxide spacer, a first monolayer graphene sheet adjacent to a first side of the spacer, and a second monolayer graphene sheet adjacent to a second side of the spacer, and at least one optical waveguide adjacent to the pair.

  11. Air and biological monitoring of solvent exposure during graffiti removal.

    Science.gov (United States)

    Anundi, H; Langworth, S; Johanson, G; Lind, M L; Akesson, B; Friis, L; Itkes, N; Söderman, E; Jönsson, B A; Edling, C

    2000-11-01

    The principal aim of the study was to estimate the level of exposure to organic solvents of graffiti removers, and to identify the chemicals used in different cleaning agents. A secondary objective was to inform about the toxicity of various products and to optimise working procedures. Exposure to organic solvents was determined by active air sampling and biological monitoring among 38 graffiti removers during an 8-h work shift in the Stockholm underground system. The air samples and biological samples were analysed by gas chromatography. Exposure to organic solvents was also assessed by a questionnaire and interviews. Solvents identified were N-methylpyrrolidone (NMP), dipropylene glycol monomethyl ether (DPGME), propylene glycol monomethyl ether (PGME), diethylene glycol monoethyl ether (DEGEE), toluene, xylene, pseudocumene, hemimellitine, mesitylene, ethylbenzene, limonene, nonane, decane, undecane, hexandecane and gamma-butyrolactone. The 8-h average exposures [time-weighted average (TWA)] were below 20% of the Swedish permissible exposure limit value (PEL) for all solvents identified. In poorly ventilated spaces, e.g. in elevators etc., the short-term exposures exceeded occasionally the Swedish short-term exposure limit values (STEL). The blood and urine concentrations of NMP and its metabolites were low. Glycol ethers and their metabolites (2-methoxypropionic acid (MPA), ethoxy acetic acid (EAA), butoxy acetic acid (BAA), and 2-(2-methoxyethoxy) acetic acid (MEAA)) were found in low concentrations in urine. There were significant correlation between the concentrations of NMP in air and levels of NMP and its metabolites in blood and urine. The use of personal protective equipment, i.e. gloves and respirators, was generally high. Many different cleaning agents were used. The average exposure to solvents was low, but some working tasks included relatively high short-term exposure. To prevent adverse health effects, it is important to inform workers about the

  12. Self-reported hearing performance in workers exposed to solvents

    Directory of Open Access Journals (Sweden)

    Adrian Fuente

    2013-02-01

    Full Text Available OBJECTIVE: To compare hearing performance relating to the peripheral and central auditory system between solvent-exposed and non-exposed workers. METHODS: Forty-eight workers exposed to a mixture of solvents and 48 non-exposed control subjects of matched age, gender and educational level were selected to participate in the study. The evaluation procedures included: pure-tone audiometry (500 - 8,000 Hz, to investigate the peripheral auditory system; the Random Gap Detection test, to assess the central auditory system; and the Amsterdam Inventory for Auditory Disability and Handicap, to investigate subjects' self-reported hearing performance in daily-life activities. A Student t test and analyses of covariance (ANCOVA were computed to determine possible significant differences between solvent-exposed and non-exposed subjects for the hearing level, Random Gap Detection test and Amsterdam Inventory for Auditory Disability and Handicap. Pearson correlations among the three measures were also calculated. RESULTS: Solvent-exposed subjects exhibited significantly poorer hearing thresholds for the right ear than non-exposed subjects. Also, solvent-exposed subjects exhibited poorer results for the Random Gap Detection test and self-reported poorer listening performance than non-exposed subjects. Results of the Amsterdam Inventory for Auditory Disability and Handicap were significantly correlated with the binaural average of subject pure-tone thresholds and Random Gap Detection test performance. CONCLUSIONS: Solvent exposure is associated with poorer hearing performance in daily life activities that relate to the function of the peripheral and central auditory system.

  13. Self-reported hearing performance in workers exposed to solvents

    Directory of Open Access Journals (Sweden)

    Adrian Fuente

    2013-02-01

    Full Text Available OBJECTIVE: To compare hearing performance relating to the peripheral and central auditory system between solvent-exposed and non-exposed workers. METHODS: Forty-eight workers exposed to a mixture of solvents and 48 non-exposed control subjects of matched age, gender and educational level were selected to participate in the study. The evaluation procedures included: pure-tone audiometry (500 - 8,000 Hz, to investigate the peripheral auditory system; the Random Gap Detection test, to assess the central auditory system; and the Amsterdam Inventory for Auditory Disability and Handicap, to investigate subjects' self-reported hearing performance in daily-life activities. A Student t test and analyses of covariance (ANCOVA were computed to determine possible significant differences between solvent-exposed and non-exposed subjects for the hearing level, Random Gap Detection test and Amsterdam Inventory for Auditory Disability and Handicap. Pearson correlations among the three measures were also calculated. RESULTS: Solvent-exposed subjects exhibited significantly poorer hearing thresholds for the right ear than non-exposed subjects. Also, solvent-exposed subjects exhibited poorer results for the Random Gap Detection test and self-reported poorer listening performance than non-exposed subjects. Results of the Amsterdam Inventory for Auditory Disability and Handicap were significantly correlated with the binaural average of subject pure-tone thresholds and Random Gap Detection test performance. CONCLUSIONS: Solvent exposure is associated with poorer hearing performance in daily life activities that relate to the function of the peripheral and central auditory system.

  14. Visual Impairment, Including Blindness

    Science.gov (United States)

    ... Who Knows What? Survey Item Bank Search for: Visual Impairment, Including Blindness Links updated, April 2017 En ... doesn’t wear his glasses. Back to top Visual Impairments in Children Vision is one of our ...

  15. Driven polymer translocation in good and bad solvent: effects of hydrodynamics and tension propagation

    CERN Document Server

    Moisio, Jaakko E; Linna, Riku P

    2016-01-01

    We investigate the driven polymer translocation through a nanometer-scale pore in the presence and absence of hydrodynamics both in good and bad solvent. We measure tension of the polymer segment on the {\\it cis} side of the pore in the course of translocations simulated using stochastic rotation dynamics, also called multi-particle collision dynamics. We find that in the good solvent the tension propagates similarly whether hydrodynamics is included or not. Only the tensed segment is by a constant factor shorter in the presence of hydrodynamics. The shorter tensed segment and the hydrodynamic interactions contribute to a smaller friction for the translocating polymer when hydrodynamics is included, which shows as smaller waiting times and a smaller exponent in the scaling of the translocation time with the polymer length. Hydrodynamics speeds up translocation in the good solvent, whereas it has a minimal effect on polymer translocation in the bad solvent. Under bad-solvent conditions tension does not spread ...

  16. Solvents and Parkinson disease: A systematic review of toxicological and epidemiological evidence

    Energy Technology Data Exchange (ETDEWEB)

    Lock, Edward A., E-mail: e.lock@ljmu.ac.uk [Liverpool John Moores University, School of Pharmacy and Biomolecular Sciences, Byrom Street, Liverpool (United Kingdom); Zhang, Jing [University of Washington, Department of Pathology, School of Medicine, Seattle, WA (United States); Checkoway, Harvey [University of Washington, Department of Environmental and Occupational Health Sciences, Seattle, WA (United States)

    2013-02-01

    Parkinson disease (PD) is a debilitating neurodegenerative motor disorder, with its motor symptoms largely attributable to loss of dopaminergic neurons in the substantia nigra. The causes of PD remain poorly understood, although environmental toxicants may play etiologic roles. Solvents are widespread neurotoxicants present in the workplace and ambient environment. Case reports of parkinsonism, including PD, have been associated with exposures to various solvents, most notably trichloroethylene (TCE). Animal toxicology studies have been conducted on various organic solvents, with some, including TCE, demonstrating potential for inducing nigral system damage. However, a confirmed animal model of solvent-induced PD has not been developed. Numerous epidemiologic studies have investigated potential links between solvents and PD, yielding mostly null or weak associations. An exception is a recent study of twins indicating possible etiologic relations with TCE and other chlorinated solvents, although findings were based on small numbers, and dose–response gradients were not observed. At present, there is no consistent evidence from either the toxicological or epidemiologic perspective that any specific solvent or class of solvents is a cause of PD. Future toxicological research that addresses mechanisms of nigral damage from TCE and its metabolites, with exposure routes and doses relevant to human exposures, is recommended. Improvements in epidemiologic research, especially with regard to quantitative characterization of long-term exposures to specific solvents, are needed to advance scientific knowledge on this topic. -- Highlights: ► The potential for organic solvents to cause Parkinson's disease has been reviewed. ► Twins study suggests etiologic relations with chlorinated solvents and Parkinson's. ► Animal studies with TCE showed potential to cause damage to dopaminergic neurons. ► Need to determine if effects in animals are relevant to human

  17. 21 CFR 582.20 - Essential oils, oleoresins (solvent-free), and natural extractives (including distillates).

    Science.gov (United States)

    2010-04-01

    ... Klotzsch. Basil Ocimum basilicum L. Bay leaves Laurus nobilis L. Bay (myrcia oil) Pimenta racemosa (Mill.) J. W. Moore. Bergamot (bergamot orange) Citrus aurantium L. subsp. bergamia Wright et Arn. Bitter.... Turmeric Curcuma longa L. Vanilla Vanilla planifolia Andr. or Vanilla tahitensis J. W. Moore....

  18. 21 CFR 182.20 - Essential oils, oleoresins (solvent-free), and natural extractives (including distillates).

    Science.gov (United States)

    2010-04-01

    ... Klotzsch. Basil Ocimum basilicum L. Bay leaves Laurus nobilis L. Bay (myrcia oil) Pimenta racemosa (Mill.) J. W. Moore. Bergamot (bergamot orange) Citrus aurantium L. subsp. bergamia Wright et Arn. Bitter.... Moore. Violet flowers Viola odorata L. Violet leaves Do. Violet leaves absolute Do. Wild cherry...

  19. Additive diffusion from LDPE slabs into contacting solvents as a function of solvent absorption

    NARCIS (Netherlands)

    Helmroth, I.E.; Dekker, M.; Hankemeier, Th.

    2003-01-01

    This article describes the simultaneous diffusion of a migrant and a solvent in low density polyethylene (LDPE). The migrant (Irganox 1076) moves out of the slab, while the solvent (isooctane, n-heptane or cyclohexane) moves inwards. Solvent absorption was measured separately by following the increa

  20. Additive Diffusion from LDPE Slabs into Contacting Solvents as a Function of Solvent Absorption

    NARCIS (Netherlands)

    Helmroth, I.E.; Dekker, M.; Hankemeier, T.

    2003-01-01

    This article describes the simultaneous diffusion of a migrant and a solvent in low density polyethylene (LDPE). The migrant (Irganox 1076) moves out of the slab, while the solvent (isooctane, n-heptane or cyclohexane) moves inwards. Solvent absorption was measured separately by following the increa

  1. Solvent effect in the Walden inversion reactions

    Science.gov (United States)

    Jaume, J.; Lluch, J. M.; Oliva, A.; Bertrán, J.

    1984-04-01

    The solvent effect on the fluoride exchange reaction has been studied by means of ab initio calculations using the 3-21G basis set. It is shown that the motion of the solvent molecules is an important part of the reaction coordinate.

  2. Solvation of rhodamine575 in some solvents

    Science.gov (United States)

    Sharma, Amit

    2016-05-01

    FTIR spectra of Rhodamine575 dye in powder form and in different solvents are reported. Positions of some of the observed FTIR bands show noticeable change in solvents. The bands, which shift, have contributions from the vibrational motion of nitrogen atoms of the ethylamine groups, oxygen atom of the carboxylic group attached to the phenyl ring and oxygen atom of the Xanthene ring.

  3. Composite capillary membrane for solvent resistant nanofiltration

    NARCIS (Netherlands)

    Dutczak, S.M.; Luiten-Olieman, Maria W.J.; Zwijnenberg, Harmen Jan; Bolhuis-Versteeg, Lydia A.M.; Winnubst, Aloysius J.A.; Hempenius, Mark A.; Benes, Nieck Edwin; Wessling, Matthias; Stamatialis, Dimitrios

    2011-01-01

    Solvent resistant nanofiltration (SRNF) is a membrane separation process allowing for an efficient separation of small molecules of 200–1000 g mol−1 from organic solvents. The application of SRNF in industry applications is currently hindered by a limited choice of SRNF membranes and configurations.

  4. Supercritical-Multiple-Solvent Extraction From Coal

    Science.gov (United States)

    Corcoran, W.; Fong, W.; Pichaichanarong, P.; Chan, P.; Lawson, D.

    1983-01-01

    Large and small molecules dissolve different constituents. Experimental apparatus used to test supercritical extraction of hydrogen rich compounds from coal in various organic solvents. In decreasing order of importance, relevant process parameters were found to be temperature, solvent type, pressure, and residence time.

  5. Improved Supercritical-Solvent Extraction of Coal

    Science.gov (United States)

    Compton, L.

    1982-01-01

    Raw coal upgraded by supercritical-solvent extraction system that uses two materials instead of one. System achieved extraction yields of 20 to 49 weight percent. Single-solvent yields are about 25 weight percent. Experimental results show extraction yields may be timedependent. Observed decreases in weight of coal agreed well with increases in ash content of residue.

  6. Solvent-vapor-assisted imprint lithography

    NARCIS (Netherlands)

    Voicu, Nicoleta E.; Ludwigs, Sabine; Crossland, Edward J. W.; Andrew, Piers; Steiner, Ullrich

    2007-01-01

    Sub-micrometer features are replicated into high-molecular-weight polymer resists by using solvent-assisted nanoimprint lithography (see figure). By swelling the polymer in a controlled solvent-vapor atmosphere, millibar pressures and ambient temperatures are sufficient to achieve high-fidelity

  7. Relationship between Fermi Resonance and Solvent Effects

    Institute of Scientific and Technical Information of China (English)

    JIANG Xiu-Lan; LI Dong-Fei; SUN Cheng-Lin; LI Zhan-Long; YANG Guang; ZHOU Mi; LI Zuo-Wei; GAO Shu-Qin

    2011-01-01

    We theoretically and experimentally study the relationship between Fermi resonance and solvent effects and investigate the Fermi resonance of p-benzoquinone and cyclopentanone in different solvents and the Fermi resonance of CS2 in C6H6 at different concentrations. Also, we investigate the Fermi resonance of C6H6 and CCl4 in their solution at different pressures. It is found that solvent effects can be utilized to search Fermi resonance parameters such as coupling coefficient and spectral intensity ratio, etc., on the other hand, the mechanism of solvent effects can be revealed according to Fermi resonance at high pressure.%@@ We theoretically and experimentally study the relationship between Fermi resonance and solvent effects and investigate the Fermi resonance of p-benzoquinone and cyclopentanone in different solvents and the Fermi resonance of CS2 in C6H6 at different concentrations.Also,we investigate the Fermi resonance of C6H6 and CCl4 in their solution at different pressures.It is found that solvent effects can be utilized to search Fermi resonance parameters such as coupling coefficient and spectral intensity ratio,etc.,on the other hand,the mechanism of solvent effects can be revealed according to Fermi resonance at high pressure.

  8. Toxic hepatitis in occupational exposure to solvents

    Institute of Scientific and Technical Information of China (English)

    Giulia Malaguarnera; Emanuela Cataudella; Maria Giordano; Giuseppe Nunnari; Giuseppe Chisari; Mariano Malaguarnera

    2012-01-01

    The liver is the main organ responsible for the metabolism of drugs and toxic chemicals,and so is the primary target organ for many organic solvents.Work activities with hepatotoxins exposures are numerous and,moreover,organic solvents are used in various industrial processes.Organic solvents used in different industrial processes may be associated with hepatotoxicity.Several factors contribute to liver toxicity; among these are:species differences,nutritional condition,genetic factors,interaction with medications in use,alcohol abuse and interaction,and age.This review addresses the mechanisms of hepatotoxicity.The main pathogenic mechanisms responsible for functional and organic damage caused by solvents are:inflammation,dysfunction of cytochrome P450,mitochondrial dysfunction and oxidative stress.The health impact of exposure to solvents in the workplace remains an interesting and worrying question for professional health work.

  9. Assessment of solvents for cellulose dissolution.

    Science.gov (United States)

    Ghasemi, Mohammad; Tsianou, Marina; Alexandridis, Paschalis

    2017-03-01

    A necessary step in the processing of biomass is the pretreatment and dissolution of cellulose. A good solvent for cellulose involves high diffusivity, aggressiveness in decrystallization, and capability of disassociating the cellulose chains. However, it is not clear which of these factors and under what conditions should be improved in order to obtain a more effective solvent. To this end, a newly-developed phenomenological model has been applied to assess the controlling mechanism of cellulose dissolution. Among the findings, the cellulose fibers remain crystalline almost to the end of the dissolution process for decrystallization-controlled kinetics. In such solvents, decreasing the fiber crystallinity, e.g., via pretreatment, would result in a considerable increase in the dissolution rate. Such insights improve the understanding of cellulose dissolution and facilitate the selection of more efficient solvents and processing conditions for biomass. Specific examples of solvents are provided where dissolution is limited due to decrystallization or disentanglement.

  10. Preparation of coal slurry with organic solvents.

    Science.gov (United States)

    Shin, Yu-Jen; Shen, Yun-Hwei

    2007-06-01

    In this study, various organic solvents were used to prepare coal slurries and the rheological and thermal properties of coal-organic solvent slurries were examined. Solvents with molecules containing unpaired electrons (high basicity) show high extraction power and cause swelling of coal. Therefore, coal-organic solvent slurries usually showed higher viscosities compared to coal-water slurry. In addition, coal slurries prepared by alcohols and cyclohexanone demonstrated lower settling rates but a high specific sedimentation volume presumably because these solvents swelled coal particles well and led to the formation of weak gel structures in the bulk. In addition, ethanol and cyclohexanone are capable of breaking a considerable amount of hydrogen bonds in coal and subsequently opening up the structures. Thus, more surface area is available for combustion and the combustion rate of coal slurries was increased.

  11. Analytic device including nanostructures

    KAUST Repository

    Di Fabrizio, Enzo M.

    2015-07-02

    A device for detecting an analyte in a sample comprising: an array including a plurality of pixels, each pixel including a nanochain comprising: a first nanostructure, a second nanostructure, and a third nanostructure, wherein size of the first nanostructure is larger than that of the second nanostructure, and size of the second nanostructure is larger than that of the third nanostructure, and wherein the first nanostructure, the second nanostructure, and the third nanostructure are positioned on a substrate such that when the nanochain is excited by an energy, an optical field between the second nanostructure and the third nanostructure is stronger than an optical field between the first nanostructure and the second nanostructure, wherein the array is configured to receive a sample; and a detector arranged to collect spectral data from a plurality of pixels of the array.

  12. Modular Polymer Biosensors by Solvent Immersion Imprint Lithography

    Energy Technology Data Exchange (ETDEWEB)

    Moore, Jayven S.; Xantheas, Sotiris S.; Grate, Jay W.; Wietsma, Thomas W.; Gratton, Enrico; Vasdekis, Andreas

    2016-01-01

    We recently demonstrated Solvent Immersion Imprint Lithography (SIIL), a rapid benchtop microsystem prototyping technique, including polymer functionalization, imprinting and bonding. Here, we focus on the realization of planar polymer sensors using SIIL through simple solvent immersion without imprinting. We describe SIIL’s impregnation characteristics, including an inherent mechanism that not only achieves practical doping concentrations, but their unexpected 4-fold enhancement compared to the immersion solution. Subsequently, we developed and characterized optical sensors for detecting molecular O2. To this end, a high dynamic range is reported, including its control through the immersion duration, a manifestation of SIIL’s modularity. Overall, SIIL exhibits the potential of improving the operating characteristics of polymer sensors, while significantly accelerating their prototyping, as it requires a few seconds of processing and no need for substrates or dedicated instrumentation. These are critical for O2 sensing as probed by way of example here, as well as any polymer permeable reactant.

  13. Solvent effects on the absorption and emission spectra of novel (E)-4-((4-(heptyloxy)phenyl)diazenyl)benzyl (((9H-fluoren-9-yl)methoxy)carbonyl)-D-alaninate (Fmoc-al-az): Determination of dipole moment by experimental and theoretical study

    Science.gov (United States)

    Y, Tej Varma; Agarwal, Devesh S.; Sarmah, Amrit; Joshi, Lata; Sakhuja, Rajeev; Pant, Debi D.

    2017-02-01

    Amino acid appended azobenzene hybrid has been synthesized (Fmoc-al-az) and its electronic absorbance and fluorescence spectra were recorded at room temperature in a series of polar and non-polar solvents. The ground state and excited state dipole moments were calculated using solvatochromic shift method. A DFT based study was also performed using- Gaussian09 program package. We have observed that the absorption spectra don't show sensitive behavior to the change in the polarity of the solvent, whereas a bathochromic shift was observed in the fluorescence spectra as we moved from non-polar to polar solvents indicating a π→π* transition. It was observed that the dipole moment in the excited state is much higher than the ground state, due to the amino acid containing hydrogen bond acceptor (Osbnd Cdbnd O) and hydrogen bond donor (sbnd NH) in Fmoc-al-az increasing the reorientation tendency of the solvent molecule around the dye therefore enhancing the stabilization of the excited state which is attributed to the high polarity of the excited states. DFT level electronic structure calculations are also performed for a better molecular level understanding of the experimental observations. We obtained a good correlation between the theoretical studies and experimental results.

  14. [Neurotoxicity of organic solvents--recent findings].

    Science.gov (United States)

    Matsuoka, Masato

    2007-06-01

    In this review, the recent findings of central nervous system (CNS) or peripheral nervous system (PNS) dysfunction induced by occupational exposure to organic solvents are described. While acute, high-level exposure to almost all organic solvents causes the general, nonspecific depression of CNS, it is still not clear whether chronic, low-level occupational exposure causes the chronic neurological dysfunction which has been called "organic solvent syndrome", "painters syndrome", "psycho-organic syndrome" or "chronic solvent encephalopathy". At least at lower than occupational exposure limits, chronic and low-level organic solvent exposure does not appear to cause the "sy mptomatic" neurological dysfunction. The chronic, moderate- to high-level exposure to a few organic solvents (such as carbon disulfide, n-hexane and methyl n-butyl ketone) affects CNS or PNS specifically. The substitutes for chlorofluorocarbons, 2-bromopropane and 1-bromopropane were shown to have the peripheral nerve toxicity in the experimental animals. Shortly after these observations, human cases of 1-bromopropane intoxication with the dysfunction of CNS and PNS were reported in the United States. Neurological abnormalities in workers of a 1-bromopropane factory in China were also reported. Thus, the possible neurotoxicity of newly introduced substitutes for ozone-depleting solvents into the workplace must be considered. Enough evidences indicate that some common solvents (such as toluene and styrene) induce sensorineural hearing loss and acquired color vision disturbances in workers. In some studies using magnetic resonance imaging (MRI), cerebral atrophy, patchy periventricular hyperintensities and hypointensities in the basal ganglia were found in solvent-exposed workers as have been shown in toluene abusers (toluene leukoencephalopathy). Further studies using the neurobehavioral test batteries, neurophysiological measurements and advanced neuroimaging techniques are required to detect the

  15. The chemistry of nonaqueous solvents v.4 solution phenomena and aprotic solvents

    CERN Document Server

    Lagowski, J J

    1976-01-01

    The Chemistry of Nonaqueous Solvents, Volume IV: Solution Phenomena and Aprotic Solvents focuses on the chemistry of nonaqueous solvents, with emphasis on solution phenomena and aprotic solvents such as tetramethylurea, inorganic acid chlorides, cyclic carbonates, and sulfolane. This book is organized into seven chapters and begins with an overview of the theory of electrical conductivity and elementary experimental considerations, along with some of the interesting research on nonaqueous solvents. It then turns to a discussion on hydrogen bonding phenomena in nonaqueous systems as probed

  16. PARIS II: Computer Aided Solvent Design for Pollution Prevention

    Science.gov (United States)

    This product is a summary of U.S. EPA researchers' work developing the solvent substitution software tool PARIS II (Program for Assisting the Replacement of Industrial Solvents, version 2.0). PARIS II finds less toxic solvents or solvent mixtures to replace more toxic solvents co...

  17. Atomistic simulation studies on the dynamics and thermodynamics of nonpolar molecules within the zeolite imidazolate framework-8.

    Science.gov (United States)

    Pantatosaki, Evangelia; Pazzona, Federico G; Megariotis, Gregory; Papadopoulos, George K

    2010-02-25

    Statistical-mechanics-based simulation studies at the atomistic level of argon (Ar), methane (CH(4)), and hydrogen (H(2)) sorbed in the zeolite imidazolate framework-8 (ZIF-8) are reported. ZIF-8 is a product of a special kind of chemical process, recently termed as reticular synthesis, which has generated a class of materials of critical importance as molecular binders. In this work, we explore the mechanisms that govern the sorption thermodynamics and kinetics of nonpolar sorbates possessing different sizes and strength of interactions with the metal-organic framework to understand the outstanding properties of this novel class of sorbents, as revealed by experiments published elsewhere. For this purpose, we have developed an in-house modeling procedure involving calculations of sorption isotherms, partial internal energies, various probability density functions, and molecular dynamics for the simulation of the sorbed phase over a wide range of occupancies and temperatures within a digitally reconstructed unit cell of ZIF-8. The results showed that sorbates perceive a marked energetic inhomogeneity within the atomic framework of the metal-organic material under study, resulting in free energy barriers that give rise to inflections in the sorption isotherms and guide the dynamics of guest molecules.

  18. Treatment of tunnel wash waters - experiments with organic sorbent materials. Part I: Removal of polycyclic aromatic hydrocarbons and nonpolar oil

    Institute of Scientific and Technical Information of China (English)

    PARUCH AdamM; ROSETH Roger

    2008-01-01

    Tunnel wash waters characterize all waters that run off after washing procedures of tunnels are performed. These waters represent a wide spectrum of organic and inorganic pollutants, such as polycyclic aromatic hydrocarbons (PAHs) and toxic metals. Removal of such contaminants from water runoff was investigated using laboratory tests after washing procedure was performed on two road tunnels in eastern Norway (Hanekleiv and Bragernes). Due to diverse character of both, treatment media and treated wash waters, the whole investigation was divided into two separate laboratory experiments. The treatment efficiencies were established based on the levels of concentrations and reductions of the measured contaminants in the effluents released from the tested media. In the first part of the article, the contents of nonpolar oil (NPO), 16 individual PAHs, and total PAHs (∑PAH16) are described. This part revealed that the combination of two organic sorbent materials provided the highest treatment efficiency for wash waters released from the road tunnel and from electrostatic filters. The greatest reduction levels reached 97.6% for NPO, 97.2% for benzo[a]pyrene, and 96.5% for the total PAHs. In the second part of the article, the concentrations and the removal rates of toxic metals are reported

  19. Short-wavelength, mid- and far-infrared intersubband absorption in nonpolar GaN/Al(Ga)N heterostructures

    Science.gov (United States)

    Lim, Caroline B.; Beeler, Mark; Ajay, Akhil; Lähnemann, Jonas; Bellet-Amalric, Edith; Bougerol, Catherine; Schörmann, Jörg; Eickhoff, Martin; Monroy, Eva

    2016-05-01

    This paper assesses nonpolar m-oriented GaN:Si/Al(Ga)N heterostructures grown on free-standing GaN for intersubband optoelectronics in the short-wavelength, mid- and far-infrared ranges. Characterization results are compared with reference c-plane samples and interpreted by correlation with self-consistent Schrödinger-Poisson calculations. In the near- and mid-infrared regions, we demonstrate m-GaN/Al(Ga)N multi-quantum-wells exhibiting room-temperature intersubband absorption tunable in the range of 1.5-5.8 µm (827-214 meV), the long wavelength limit being set by the second order of the Reststrahlen band in the GaN substrates. Extending the study to the far-infrared region, low-temperature intersubband transitions in the 1.5-9 THz range (6.3-37.4 meV) are observed in larger m-plane GaN/AlGaN multi-quantum-wells, covering most of the 7-10 THz band forbidden to GaAs-based technologies.

  20. Photo-Stimulated Electron Detrapping and the Two-State Model for Electron Transport in Nonpolar Liquids

    CERN Document Server

    Shkrob, I A

    2004-01-01

    In common nonpolar liquids, such as saturated hydrocarbons, a dynamic equilibrium between trapped (localized) and quasifree (extended) states has been postulated for the excess electron (the two-state model). Using time-resolved dc conductivity, the effect of 1064 nm laser photoexcitation of trapped electrons on the charge transport has been observed in liquid n-hexane and methylcyclohexane. The light promotes the electron from the trap into the conduction band of the liquid, instantaneously increasing the conductivity by orders of magnitude. From the analysis of the two-pulse, two-color photoconductivity data, the residence time of the electrons in traps has been estimated as ca. 8.4 ps for n-hexane and ca. 13 ps for methylcyclohexane (at 295 K). The rate of detrapping decreases at lower temperature with an activation energy of ca. 200 meV (280-320 K); the lifetime-mobility product for quasifree electrons scales linearly with the temperature. We suggest that the properties of trapped electrons in hydrocarbon...

  1. Antimicrobial activity of ultrasound-assisted solvent-extracted spices.

    Science.gov (United States)

    Thongson, C; Davidson, P M; Mahakarnchanakul, W; Weiss, J

    2004-01-01

    The objective of this research was to determine the antimicrobial activity of conventional and high-intensity ultrasound-assisted (HI-US) solvent-extracted Thai spices, including ginger (Zingiber officinale Rose), fingerroot (Bosenbergia pandurata Holtt) and turmeric (Curouma longa Linn). Extracts were obtained using hexane, isopropanol and a 7 : 3 isopropanol : hexane mixture as solvents with and without HI-US. The antimicrobial activity of the extracts was assayed against four strains each of Listeria monocytogenes and Salmonella Typhimurium DT 104 using an agar dilution assay. Application of HI-US did not alter antibacterial activity against S. Typhimurium, but antilisterial activity of some HI-US spice extracts decreased. Solvent type affected antimicrobial efficacy of extracts with hexane producing the least antimicrobial activity. Fingerroot extracted with isopropanol-hexane and without HI-US had the best antilisterial effect while HI-US-isopropanol fingerroot extract had the greatest antimicrobial efficacy against S. Typhimurium. Application of HI-US reduced time of extraction to 5 min, compared with the 24 h required for conventional extraction and maintained antimicrobial activity against Salmonella but slightly reduced activity against Listeria. HI-US in combination with proper solvent selection may offer a new tool to optimize extraction of spice essential oil for use as antimicrobial agents, and reduce processing time and costs.

  2. In situ aerobic cometabolism of chlorinated solvents: a review.

    Science.gov (United States)

    Frascari, Dario; Zanaroli, Giulio; Danko, Anthony S

    2015-01-01

    The possible approaches for in situ aerobic cometabolism of aquifers and vadose zones contaminated by chlorinated solvents are critically evaluated. Bioaugmentation of resting-cells previously grown in a fermenter and in-well addition of oxygen and growth substrate appear to be the most promising approaches for aquifer bioremediation. Other solutions involving the sparging of air lead to satisfactory pollutant removals, but must be integrated by the extraction and subsequent treatment of vapors to avoid the dispersion of volatile chlorinated solvents in the atmosphere. Cometabolic bioventing is the only possible approach for the aerobic cometabolic bioremediation of the vadose zone. The examined studies indicate that in situ aerobic cometabolism leads to the biodegradation of a wide range of chlorinated solvents within remediation times that vary between 1 and 17 months. Numerous studies include a simulation of the experimental field data. The modeling of the process attained a high reliability, and represents a crucial tool for the elaboration of field data obtained in pilot tests and for the design of the full-scale systems. Further research is needed to attain higher concentrations of chlorinated solvent degrading microbes and more reliable cost estimates. Lastly, a procedure for the design of full-scale in situ aerobic cometabolic bioremediation processes is proposed.

  3. Effect of solvent selection on froth treatment for mining operations

    Energy Technology Data Exchange (ETDEWEB)

    Hamza, H.A. [Natural Resources Canada, Devon, AB (Canada). CANMET Energy Technology Centre

    2003-07-01

    The heavy oil (bitumen) industry is important for the Canadian economy. The oil sands are unique to Canada and government support is crucial for continued research into the development of technologies and products which make less of an impact on the environment. This paper describes a successful collaboration between the Canada Centre for Mineral and Energy Technology (CANMET) and Shell Canada which led to the 2003 award for Advanced Separation Technologies (AST). This PowerPoint presentation reviews feeds for a naphtha solvent treatment versus a paraffinic solvent treatment. The feeds include bitumen froth, low quality bitumen emulsions, in-situ heavy oil emulsions, and bitumen. Microscope images for each of these feeds were illustrated. The typical elements of the solvent treatment process were also outlined in a flow chart. The main feature of the naphtha process is that it is well established plus it renders a product with 1.5 to 4 per cent water and 0.5 per cent solids. It needs chemical demulsifiers and no asphaltene is rejected. The main feature of the paraffinic process is that it produces a product with low water/solids content and asphaltene levels can be controlled. The process requires less solvent for pipelining because of its reduced viscosity and if offers flexibility in terms of upgrading options. The presentation listed achievements in AST by Albian Sands, TrueNorth, Canadian Natural Resources Ltd., Suncor, Syncrude, and AEC Pipelines Ltd. tabs., figs.

  4. Predicting the Solubility of Pharmaceutical Cocrystals in Solvent/Anti-Solvent Mixtures

    Directory of Open Access Journals (Sweden)

    Linda Lange

    2016-05-01

    Full Text Available In this work, the solubilities of pharmaceutical cocrystals in solvent/anti-solvent systems were predicted using PC-SAFT in order to increase the efficiency of cocrystal formation processes. Modeling results and experimental data were compared for the cocrystal system nicotinamide/succinic acid (2:1 in the solvent/anti-solvent mixtures ethanol/water, ethanol/acetonitrile and ethanol/ethyl acetate at 298.15 K and in the ethanol/ethyl acetate mixture also at 310.15 K. The solubility of the investigated cocrystal slightly increased when adding small amounts of anti-solvent to the solvent, but drastically decreased for high anti-solvent amounts. Furthermore, the solubilities of nicotinamide, succinic acid and the cocrystal in the considered solvent/anti-solvent mixtures showed strong deviations from ideal-solution behavior. However, by accounting for the thermodynamic non-ideality of the components, PC-SAFT is able to predict the solubilities in all above-mentioned solvent/anti-solvent systems in good agreement with the experimental data.

  5. Distribution of multi-component solvents in solvent vapor extraction chamber

    Energy Technology Data Exchange (ETDEWEB)

    Das, S. [Society of Petroleum Engineers, Richardson, TX (United States)]|[Marathon Oil Corp., Houston, TX (United States)

    2008-10-15

    Vapex process performance is sensitive to operating pressures, temperatures and the types of solvent used. The hydrocarbon solvents used in Vapex processes typically have between 5 and 10 per cent hydrocarbon impurities, and the accumulation of dense phases inside the vapor chamber reduces gravity drainage potential. This study investigated the partitioning of solvent compounds inside the vapor chamber during in situ Vapex processes.The aim of the study was to examine how the different components of the mixed solvent partitioned inside the extracted chamber during the oil and vapor phase. A 2-D homogenous reservoir model was used to simulate the Vapex process with a solvent mixture comprised of propane and methane at various percentages. The effect of injecting a hot solvent vapor was also investigated. The study showed that injected methane accumulated at both the top and the extraction interface. Accumulations near the top had a positive impact on solvent confinement in thin reservoirs. Diffusion of the solvent component was controlled by gas phase molecular diffusion, and was much faster than the diffusion of solvent molecules in the liquid phase. The use of hot solvent mixtures slowed the extraction process due to lower solvent solubility in the oil phase. It was concluded that the negative impact on viscosity reduction by dilution was not compensated by rises in temperature. 6 refs., 11 figs.

  6. Systematic study on the effect of solvent removal rate on the morphology of solvent vapor annealed ABA triblock copolymer thin films.

    Science.gov (United States)

    Albert, Julie N L; Young, Wen-Shiue; Lewis, Ronald L; Bogart, Timothy D; Smith, Jasmine R; Epps, Thomas H

    2012-01-24

    Nanoscale self-assembly of block copolymer thin films has garnered significant research interest for nanotemplate design and membrane applications. To fulfill these roles, control of thin film morphology and orientation is critical. Solvent vapor annealing (SVA) treatments can be used to kinetically trap morphologies in thin films not achievable by traditional thermal treatments, but many variables affect the outcome of SVA, including solvent choice, total solvent concentration/swollen film thickness, and solvent removal rate. In this work, we systematically examined the effect of solvent removal rate on the final thin film morphology of a cylinder-forming ABA triblock copolymer. By kinetically trapping the film morphologies at key points during the solvent removal process and then using successive ultraviolet ozone (UVO) etching steps followed by atomic force microscopy (AFM) imaging to examine the through-film morphologies of the films, we determined that the mechanism for cylinder reorientation from substrate-parallel to substrate-perpendicular involved the propagation of changes at the free surface through the film toward the substrate as a front. The degree of reorientation increased with successively slower solvent removal rates. Furthermore, the AFM/UVO etching scheme permitted facile real-space analysis of the thin film internal structure in comparison to cross-sectional transmission electron microscopy.

  7. Water-enhanced solubility of carboxylic acids in organic solvents and its applications to extraction processes

    Energy Technology Data Exchange (ETDEWEB)

    Starr, J.N.; King, C.J.

    1991-11-01

    The solubilities of carboxylic acids in certain organic solvents increase remarkably with an increasing amount of water in the organic phase. This phenomenon leads to a novel extract regeneration process in which the co-extracted water is selectively removed from an extract, and the carboxylic acid precipitates. This approach is potentially advantageous compared to other regeneration processes because it removes a minor component of the extract in order to achieve a large recovery of acid from the extract. Carboxylic acids of interest include adipic acid, fumaric acid, and succinic acid because of their low to moderate solubilities in organic solvents. Solvents were screened for an increase in acid solubility with increased water concentration in the organic phase. Most Lewis-base solvents were found to exhibit this increased solubility phenomena. Solvents that have a carbonyl functional group showed a very large increase in acid solubility. 71 refs., 52 figs., 38 tabs.

  8. Pretreatment of Lignocellulosic Biomass with Ionic Liquids and Ionic Liquid-Based Solvent Systems

    Directory of Open Access Journals (Sweden)

    Qidong Hou

    2017-03-01

    Full Text Available Pretreatment is very important for the efficient production of value-added products from lignocellulosic biomass. However, traditional pretreatment methods have several disadvantages, including low efficiency and high pollution. This article gives an overview on the applications of ionic liquids (ILs and IL-based solvent systems in the pretreatment of lignocellulosic biomass. It is divided into three parts: the first deals with the dissolution of biomass in ILs and IL-based solvent systems; the second focuses on the fractionation of biomass using ILs and IL-based solvent systems as solvents; the third emphasizes the enzymatic saccharification of biomass after pretreatment with ILs and IL-based solvent systems.

  9. Enzyme molecular dynamics simulations in different solvents: Fundamental effects and a new paradigm for rational design

    Energy Technology Data Exchange (ETDEWEB)

    Ornstein, R.L. [Pacific Northwest National Lab., Richland, WA (United States)

    1997-12-31

    Developing enzymes that are functional in nonaqueous solutions may prove useful in the development of new strategies for environmental remediation and monitoring, as well as in developing `green` processes. To gain a fundamental understanding of the structural and dynamic consequences to an enzyme induced by such solvents, we compared simulation results for the well characterized protease enzyme subtilisin Carlsberg in different solvents, including water, carbon tetrachloride, and dimethyl sulfoxide. Serendipitously, we observed a small number of solvent-dependent `tight-binding` site between the enzyme and each solvent. Such solvent-dependent `tight-binding` site information may offer a new simulation paradigm for protein engineering and drug design. Examples will be offered for the cases of subtilisin and a glutathione S-transferase.

  10. Substituent and Solvent Effects on the Absorption Spectra of Cation-π Complexes of Benzene and Borazine: A Theoretical Study.

    Science.gov (United States)

    Sarmah, Nabajit; Bhattacharyya, Pradip Kr; Bania, Kusum K

    2014-05-14

    Time-dependent density functional theory (TDDFT) has been used to predict the absorption spectra of cation-π complexes of benzene and borazine. Both polarized continuum model (PCM) and discrete solvation model (DSM) and a combined effect of PCM and DSM on the absorption spectra have been elucidated. With decrease in size of the cation, the π → π* transitions of benzene and borazine are found to undergo blue and red shift, respectively. A number of different substituents (both electron-withdrawing and electron-donating) and a range of solvents (nonpolar to polar) have been considered to understand the effect of substituent and solvents on the absorption spectra of the cation-π complexes of benzene and borazine. Red shift in the absorption spectra of benzene cation-π complexes are observed with both electron-donating groups (EDGs) and electron-withdrawing groups (EWGs). The same trend has not been observed in the case of substituted borazine cation-π complexes. The wavelength of the electronic transitions corresponding to cation-π complexes correlates well with the Hammet constants (σp and σm). This correlation indicates that the shifting of spectral lines of the cation-π complexes on substitution is due to both resonance and inductive effect. On incorporation of solvent phases, significant red or blue shifting in the absorption spectra of the complexes has been observed. Kamlet-Taft multiparametric equation has been used to explain the effect of solvent on the absorption spectra of complexes. Polarity and polarizability are observed to play an important role in the solvatochromism of the cation-π complexes.

  11. Observation of mid-infrared intersubband absorption in non-polar m-plane AlGaN/GaN multiple quantum wells

    Energy Technology Data Exchange (ETDEWEB)

    Kotani, Teruhisa, E-mail: kotani.teruhisa@sharp.co.jp [Institute for Nano Quantum Information Electronics, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8505 (Japan); Institute of Industrial Science, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8505 (Japan); Life and Environment Laboratories, Sharp Corporation, 2613-1 Ichinomoto-cho, Tenri, Nara 632-8567 (Japan); Arita, Munetaka [Institute for Nano Quantum Information Electronics, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8505 (Japan); Arakawa, Yasuhiko [Institute for Nano Quantum Information Electronics, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8505 (Japan); Institute of Industrial Science, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8505 (Japan)

    2014-12-29

    Mid-infrared (4.20–4.84 μm) intersubband absorption in non-polar m-plane Al{sub 0.5}Ga{sub 0.5}N/GaN multiple-quantum wells is observed at room temperature. 10 period Al{sub 0.5}Ga{sub 0.5}N/GaN multiple-quantum wells were grown on free-standing m-plane GaN substrates by metalorganic chemical vapor deposition (MOCVD), and the high-quality structural and optical properties are revealed by x-ray diffraction and photoluminescence studies. Through this we have demonstrated that MOCVD grown non-polar m-plane AlGaN/GaN quantum wells are a promising material for mid-infrared intersubband devices.

  12. Life Cycle Assessment of an Ionic LIquid versus Traditional Solvents and Their Applications

    Science.gov (United States)

    Ionic liquids (ILs) have been claimed as "greener" replacements to traditional solvents. HOwever, the environmental impacts of the life cycle phases including the making of ILs, their application, separation, etc., and comparison with alternative methods have not been studied. Su...

  13. Critical Casimir interactions and colloidal self-assembly in near-critical solvents

    Science.gov (United States)

    Tasios, Nikos; Edison, John R.; van Roij, René; Evans, Robert; Dijkstra, Marjolein

    2016-08-01

    A binary solvent mixture close to critical demixing experiences fluctuations whose correlation length, ξ, diverges as the critical point is approached. The solvent-mediated (SM) interaction that arises between a pair of colloids immersed in such a near-critical solvent can be long-ranged and this so-called critical Casimir interaction is well-studied. How a (dense) suspension of colloids will self-assemble under these conditions is poorly understood. Using a two-dimensional lattice model for the solvent and hard disks to represent the colloids, we perform extensive Monte Carlo simulations to investigate the phase behaviour of this model colloidal suspension as a function of colloid size and wettability under conditions where the solvent reservoir is supercritical. Unlike most other approaches, where the solvent is modelled as an implicit background, our model employs an explicit solvent and treats the suspension as a ternary mixture. This enables us to capture important features, including the pronounced fractionation of the solvent in the coexisting colloidal phases, of this complex system. We also present results for the partial structure factors; these shed light on the critical behaviour in the ternary mixture. The degree to which an effective two-body pair potential description can describe the phase behaviour and structure of the colloidal suspension is discussed briefly.

  14. Quantifying Volatile Organic Compound Emissions from Solvents and their Impacts on Urban Air Quality

    Science.gov (United States)

    Mcdonald, B. C.; De Gouw, J. A.; Gilman, J.; Ahmadov, R.; Cappa, C. D.; Frost, G. J.; Goldstein, A. H.; Jathar, S.; Jimenez, J. L.; Kim, S. W.; McKeen, S. A.; Roberts, J. M.; Trainer, M.

    2016-12-01

    Solvents, which consist of personal care products, paints, degreasing agents, and other chemical products, are an important anthropogenic source of volatile organic compound (VOC) emissions. Yet there are many unresolved questions related to their emission rates, chemical composition, and relative importance on urban air quality problems. Using atmospheric measurements of speciated VOCs collected at a ground site located in the Los Angeles basin during the California Nexus (CalNex) Study in 2010, and utilizing data on the composition of solvent emissions from the California Air Resources Board (CARB), we are able to reconcile solvent emissions with ambient observations. Our analysis indicates that solvent emissions are underestimated by a factor of 2-3 in the CARB inventory. We then estimate the reactivity of solvent emissions with the hydroxyl (OH) radical, and also estimate the propensity of solvent emissions to form secondary organic aerosol (SOA). Solvents contain significant fractions of oxygenated compounds, including intermediate volatility compounds, which if released to the atmosphere are potentially reactive and can lead to the formation of SOA. Overall, our results suggest that in the Los Angeles basin, solvents are now the largest anthropogenic source of VOC emissions, OH reactivity, and SOA formation, and larger than the contribution from motor vehicles. This suggests that more research is needed in better constraining this potentially important source of urban VOC emissions.

  15. Use of liquid hydrocarbon and amide transfer data to estimate contributions to thermodynamic functions of protein folding from the removal of nonpolar and polar surface from water.

    Science.gov (United States)

    Spolar, R S; Livingstone, J R; Record, M T

    1992-04-28

    This extension of the liquid hydrocarbon model seeks to quantify the thermodynamic contributions to protein stability from the removal of nonpolar and polar surface from water. Thermodynamic data for the transfer of hydrocarbons and organic amides from water to the pure liquid phase are analyzed to obtain contributions to the thermodynamics of folding from the reduction in water-accessible surface area. Although the removal of nonpolar surface makes the dominant contribution to the standard heat capacity change of folding (delta C0fold), here we show that inclusion of the contribution from removal of polar surface allows a quantitative prediction of delta C0fold within the uncertainty of the calorimetrically determined value. Moreover, analysis of the contribution of polar surface area to the enthalpy of transfer of liquid amides provides a means of estimating the contributions from changes in nonpolar and polar surface area as well as other factors to the enthalpy of folding (delta H0fold). In addition to estimates of delta H0fold, this extension of the liquid hydrocarbon model provides a thermodynamic explanation for the observation [Privalov, P. L., & Khechinashvili, N. N. (1974) J. Mol. Biol. 86, 665-684] that the specific enthalpy of folding (cal g-1) of a number of globular proteins converges to a common value at approximately 383 K. Because amounts of nonpolar and polar surface area buried by these proteins upon folding are found to be linear functions of molar mass, estimates of both delta C0fold and delta H0fold may be obtained given only the molar mass of the protein of interest.(ABSTRACT TRUNCATED AT 250 WORDS)

  16. Organic Solvent Tolerant Lipases and Applications

    Directory of Open Access Journals (Sweden)

    Shivika Sharma

    2014-01-01

    Full Text Available Lipases are a group of enzymes naturally endowed with the property of performing reactions in aqueous as well as organic solvents. The esterification reactions using lipase(s could be performed in water-restricted organic media as organic solvent(s not only improve(s the solubility of substrate and reactant in reaction mixture but also permit(s the reaction in the reverse direction, and often it is easy to recover the product in organic phase in two-phase equilibrium systems. The use of organic solvent tolerant lipase in organic media has exhibited many advantages: increased activity and stability, regiospecificity and stereoselectivity, higher solubility of substrate, ease of products recovery, and ability to shift the reaction equilibrium toward synthetic direction. Therefore the search for organic solvent tolerant enzymes has been an extensive area of research. A variety of fatty acid esters are now being produced commercially using immobilized lipase in nonaqueous solvents. This review describes the organic tolerance and industrial application of lipases. The main emphasis is to study the nature of organic solvent tolerant lipases. Also, the potential industrial applications that make lipases the biocatalysts of choice for the present and future have been presented.

  17. Auditory dysfunction associated with solvent exposure

    Directory of Open Access Journals (Sweden)

    Fuente Adrian

    2013-01-01

    Full Text Available Abstract Background A number of studies have demonstrated that solvents may induce auditory dysfunction. However, there is still little knowledge regarding the main signs and symptoms of solvent-induced hearing loss (SIHL. The aim of this research was to investigate the association between solvent exposure and adverse effects on peripheral and central auditory functioning with a comprehensive audiological test battery. Methods Seventy-two solvent-exposed workers and 72 non-exposed workers were selected to participate in the study. The test battery comprised pure-tone audiometry (PTA, transient evoked otoacoustic emissions (TEOAE, Random Gap Detection (RGD and Hearing-in-Noise test (HINT. Results Solvent-exposed subjects presented with poorer mean test results than non-exposed subjects. A bivariate and multivariate linear regression model analysis was performed. One model for each auditory outcome (PTA, TEOAE, RGD and HINT was independently constructed. For all of the models solvent exposure was significantly associated with the auditory outcome. Age also appeared significantly associated with some auditory outcomes. Conclusions This study provides further evidence of the possible adverse effect of solvents on the peripheral and central auditory functioning. A discussion of these effects and the utility of selected hearing tests to assess SIHL is addressed.

  18. Solvent Effect on the Photolysis of Riboflavin.

    Science.gov (United States)

    Ahmad, Iqbal; Anwar, Zubair; Ahmed, Sofia; Sheraz, Muhammad Ali; Bano, Raheela; Hafeez, Ambreen

    2015-10-01

    The kinetics of photolysis of riboflavin (RF) in water (pH 7.0) and in organic solvents (acetonitrile, methanol, ethanol, 1-propanol, 1-butanol, ethyl acetate) has been studied using a multicomponent spectrometric method for the assay of RF and its major photoproducts, formylmethylflavin and lumichrome. The apparent first-order rate constants (k obs) for the reaction range from 3.19 (ethyl acetate) to 4.61 × 10(-3) min(-1) (water). The values of k obs have been found to be a linear function of solvent dielectric constant implying the participation of a dipolar intermediate along the reaction pathway. The degradation of this intermediate is promoted by the polarity of the medium. This indicates a greater stabilization of the excited-triplet states of RF with an increase in solvent polarity to facilitate its reduction. The rate constants for the reaction show a linear relation with the solvent acceptor number indicating the degree of solute-solvent interaction in different solvents. It would depend on the electron-donating capacity of RF molecule in organic solvents. The values of k obs are inversely proportional to the viscosity of the medium as a result of diffusion-controlled processes.

  19. Hydrothermal liquefaction of de-oiled Jatropha curcas cake using Deep Eutectic Solvents (DESs) as catalysts and co-solvents.

    Science.gov (United States)

    Alhassan, Yahaya; Kumar, Naveen; Bugaje, Idris M

    2016-01-01

    Biomass liquefaction using ionic liquids (ILs) as catalysts has received appreciable attention, in renewable fuels and chemicals production, recently. However, issues associated with the production cost, long reaction time and use of volatile solvents are undeniably challenging. Thus, Deep Eutectic Solvents (DESs) emerged as promising and potential ILs substitutes. The hydrothermal liquefaction of de-oiled Jatropha curcas cake was catalyzed by four synthesized DESs as catalysts and co-solvents for selective extraction. Proximate and ultimate analyses including ash, moisture and carbon contents of bio-crude produced varied slightly. The higher heating values found ranges from 21.15 ± 0.82 MJ/kg to 24.30 ± 0.98 MJ/kg. The bio-crude yields obtained using ChCl-KOH DES was 43.53 wt% and ChCl-p-TsOH DES was 38.31 wt%. Bio-crude yield using ChCl-FeCl3 DES was 30.80 wt%. It is suggested that, the selectivity of bio-crude could be improved, by using DESs as catalyst and co-solvent in HTL of biomass such as de-oiled J. curcas cake.

  20. Steady state recycling chromatography with solvent removal-effect of solvent removal constraints on process operation under ideal conditions.

    Science.gov (United States)

    Siitonen, Jani; Sainio, Tuomo

    2014-05-09

    Steady state recycling chromatography (SSR) offers a means to reduce eluent consumption and increase productivity in preparative and production scale chromatographic separations. Even better performance is obtained with an integrated process by coupling solvent removal unit to the chromatographic separation unit. Here a design method for SSR with an integrated solvent removal unit (SSR-SR) is presented. The method is more practical than previous work as the effect of physical constraints, such as solubility or viscosity, imposed on the amount of solvent removed is included. The method holds under ideal conditions for binary systems with competitive Langmuir isotherm model. The design equations allow calculation of the regions of feasible operating parameters when either the maximum concentrations in the solvent removal unit or of the solution fed into the chromatographic column is restricted. The method was applied to analyze the performance of different SSR-SR configurations in two case studies: the separation of mandelic acid enantiomers and the separation of EMD 53986 enantiomers. The benefits of SSR-SR are relatively small under ideal conditions but the design method developed here can give a good starting point for designing SSR-SR processes under non-ideal conditions.

  1. Nonpolar organic compounds as PM2.5 source tracers: Investigation of their sources and degradation in the Pearl River Delta, China

    Science.gov (United States)

    Wang, Qiongqiong; Feng, Yongming; Huang, X. H. Hilda; Griffith, Stephen M.; Zhang, Ting; Zhang, Qingyan; Wu, Dui; Yu, Jian Zhen

    2016-10-01

    A group of nonpolar organic compounds (NPOCs) in five compound classes including alkanes, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, and 1,3,5-triphenylbenzene were quantified in samples of particulate matter of aerodynamic diameter less than 2.5 μm collected at four sites in the Pearl River Delta (PRD) region, China, over a 2 year period from 2011 to 2012. The four sites include industrial (Nanhai), urban (Guangzhou), urban outskirt (Dongguan), and suburban (Nansha) locations. Some NPOCs are uniquely emitted from particular combustion sources and thereby serving as markers in source apportionment. Based on this multiyear and multisite NPOC data set, spatial and seasonal variations, correlation analysis, and ratio-ratio plots were used to investigate the source information and degradation of NPOC tracers. In summer, NPOCs showed distinct local emission characteristics, with urban sites having much higher concentrations than suburban sites. In winter, regional transport was an important influence on NPOC levels, driving up concentrations at all sampling sites and diminishing an urban-suburban spatial gradient. The lighter NPOCs exhibited more prominent seasonal variations. Such spatiotemporal features suggest that their particle-phase abundance is more influenced by temperature, which is a critical factor in controlling the extent of semivolatile organics partitioned into the aerosol phase. The heavier NPOCs, especially PAHs, showed negligible correlation among the four sites, suggesting more influence from local emissions. Ratio-ratio plots indicate photodegradation and mixing of various sources for the NPOCs in the PRD. A positive matrix factorization (PMF) analysis of this large NPOC data set suggests that heavier NPOCs are more suitable source indicators than lighter NPOCs. Incorporating particle-phase light NPOC concentrations in PMF produces a separate factor, which primarily contains those light NPOCs and likely is not a source factor. Total

  2. Characterization of nonpolar lipids and steroids by using laser-induced acoustic desorption/chemical ionization, atmospheric pressure chemical ionization, and electrospray ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Z; Daiya, S; Kenttämaa, Hilkka I

    Laser-induced acoustic desorption (LIAD) combined with ClMn(H{sub 2}O){sup +} chemical ionization (CI) was tested for the analysis of nonpolar lipids and selected steroids in a Fourier-transform ion cyclotron resonance mass spectrometer (FT-ICR). The nonpolar lipids studied, cholesterol, 5α-cholestane, cholesta-3,5-diene, squalene, and β-carotene, were found to solely form the desired water replacement product (adduct-H{sub 2}O) upon reaction with the ClMn(H{sub 2}O){sup +} ions. The steroids, androsterone, dehydroepiandrosterone (DHEA), estrone, estradiol, and estriol, also form abundant adduct-H{sub 2}O ions, but less abundant adduct-2H{sub 2}O ions were also observed. Neither (+)APCI nor (+)ESI can ionize the saturated hydrocarbon lipid, cholestane. APCI successfully ionizes the unsaturated hydrocarbon lipids to form exclusively the intact protonated analytes. However, it causes extensive fragmentation for cholesterol and the steroids. The worst case is cholesterol that does not produce any stable protonated molecules. On the other hand, ESI cannot ionize any of the hydrocarbon analytes, saturated or unsaturated. However, ESI can be used to protonate the oxygen-containing analytes with substantially less fragmentation than for APCI in all cases except for cholesterol and estrone. In conclusion, LIAD/ClMn(H{sub 2}O){sup +} chemical ionization is superior over APCI and ESI for the mass spectrometric characterization of underivatized nonpolar lipids and steroids.

  3. Effect of solvent environment on the Photophysics of a newly synthesized bioactive 7-oxy(5-selenocyanato-pentyl)-2H-1-benzopyran-2-one

    Energy Technology Data Exchange (ETDEWEB)

    Dhar, Sayaree [Department of Chemistry, Jadavpur University, Kolkata 700032 (India); Rana, Dipak Kumar [Department of Chemistry, Saldiha College, The University of Burdwan, Bankura 722173 (India); Singha Roy, Somnath [Department of Cancer Chemoprevention, Chittaranjan National Cancer Institute, 37, S. P. Mukherjee Road, Kolkata 700026 (India); Roy, Swapnadip [Department of Chemistry, Jadavpur University, Kolkata 700032 (India); Bhattacharya, Sudin [Department of Cancer Chemoprevention, Chittaranjan National Cancer Institute, 37, S. P. Mukherjee Road, Kolkata 700026 (India); Bhattacharya, Subhash Chandra, E-mail: sbjuchem@yahoo.com [Department of Chemistry, Jadavpur University, Kolkata 700032 (India)

    2012-04-15

    The synthesis and solvatochromic behavior of the compound, 7-oxy(5-selenocyanato-pentyl)-2H-1-benzopyran-2-one (PCM), a pervasive, bioactive coumarin derivative, which is expected to possess antioxidative properties and other important therapeutic activities of significant potency with low systematic toxicity, have been reported employing steady state and time resolved fluorescence techniques. Spectroscopic studies reveal that the solvatochromic behavior of the probe depends not only on the polarity of the medium but also on the hydrogen bonding properties of the solvents. Specific hydrogen bonding interaction of PCM in polar solvents modulated the order of the two close-lying lowest singlet states. The photophysical response of PCM in different solvents has been explained considering solute-solvent interactions. To corroborate these results, we performed the ground-state geometry, lowest energy transition and the UV-vis spectrum of PCM using the density functional theory (DFT) and the time-dependent density functional theory (TD-DFT) at B3LYP/6-31G{sup Low-Asterisk} level. We found excellent correlation between the predicted and experimental spectral data, providing a useful tool in the design of new fluorogenic probes having potential therapeutic activity. - Highlights: Black-Right-Pointing-Pointer Synthesis and photophysical behavior of the bioactive PCM. Black-Right-Pointing-Pointer The order of the two close-lying lowest singlet states is modulated by H-bonding interaction in polar solvents. Black-Right-Pointing-Pointer In non-polar solvent non-radiative path favor due to mixing of n,{pi}{sup Low-Asterisk} and {pi},{pi}{sup Low-Asterisk} singlet states. Black-Right-Pointing-Pointer Quantum chemical calculation has been employed to corroborate with experimental finding.

  4. Purification and characterization of an extracellular halophilic and organic solvent-tolerant amylopullulanase from a haloarchaeon, Halorubrum sp. strain Ha25.

    Directory of Open Access Journals (Sweden)

    Mostafa Fazeli

    2013-01-01

    Full Text Available Introduction: Halophiles, especially haloarchaea are one of the most important groups of extremophiles. Halophilic hydrolases have been studied worldwide and have been considered for biotechnology and industrial technologies. This study is the first report in amylopullulanase production in halophilic microorganisms.Materials and methods: A halophilic archaeon, Halorubrum sp. strain Ha25, produced extracellular halophilic organic solvent-tolerant amylopullulanase. The enzyme was purified using ethanol precipitation and anion exchange chromatography method. Molecular mass of purified enzyme was determined by SDS–PAGE method. After purification, the enzyme was characterized. To study the effects of organic solvents in the stability of the enzyme, the enzyme solution was incubated in the presence of various organic compounds and then, residual enzyme activity was measured. Mode of action of the enzyme was determined by thin-layer chromatography.Results: Molecular weight of the purified enzyme was estimated to be 140 kDa by SDS–PAGE method. Optimum temperature for amylolitic and pullulytic activities was 50 °C. Optimum pH for amylolitic activity was 7.0 and for pullulytic activity was 7.5. This enzyme was active over a wide range of concentrations (0-4.5 M of NaCl. The effect of organic solvents on the amylolitic and pullulytic activities showed that this enzyme was more stable in the presence of non-polar organic solvents than polar solvents. The enzyme solely hydrolyzed pullulan and soluble starch to glucose.Discussion and conclusion: Halorubrum sp. strain Ha25 produces thermophilic and extremely halophilic amylopullulanase. The catalytic function under multi extreme condition of high temperature, high salinity, and low water activity might possess biotechnological and commercial values such as treatment waste solutions with starch residues, high salt content and solvents.

  5. Solvent dependence of Stokes shift for organic solute-solvent systems: A comparative study by spectroscopy and reference interaction-site model-self-consistent-field theory.

    Science.gov (United States)

    Nishiyama, Katsura; Watanabe, Yasuhiro; Yoshida, Norio; Hirata, Fumio

    2013-09-01

    The Stokes shift magnitudes for coumarin 153 (C153) in 13 organic solvents with various polarities have been determined by means of steady-state spectroscopy and reference interaction-site model-self-consistent-field (RISM-SCF) theory. RISM-SCF calculations have reproduced experimental results fairly well, including individual solvent characteristics. It is empirically known that in some solvents, larger Stokes shift magnitudes are detected than anticipated on the basis of the solvent relative permittivity, ɛr. In practice, 1,4-dioxane (ɛr = 2.21) provides almost identical Stokes shift magnitudes to that of tetrahydrofuran (THF, ɛr = 7.58), for C153 and other typical organic solutes. In this work, RISM-SCF theory has been used to estimate the energetics of C153-solvent systems involved in the absorption and fluorescence processes. The Stokes shift magnitudes estimated by RISM-SCF theory are ∼5 kJ mol(-1) (400 cm(-1)) less than those determined by spectroscopy; however, the results obtained are still adequate for dipole moment comparisons, in a qualitative sense. We have also calculated the solute-solvent site-site radial distributions by this theory. It is shown that solvation structures with respect to the C-O-C framework, which is common to dioxane and THF, in the near vicinity (∼0.4 nm) of specific solute sites can largely account for their similar Stokes shift magnitudes. In previous works, such solute-solvent short-range interactions have been explained in terms of the higher-order multipole moments of the solvents. Our present study shows that along with the short-range interactions that contribute most significantly to the energetics, long-range electrostatic interactions are also important. Such long-range interactions are effective up to 2 nm from the solute site, as in the case of a typical polar solvent, acetonitrile.

  6. Modeling of Salt Solubilities in Mixed Solvents

    DEFF Research Database (Denmark)

    Chiavone-Filho, O.; Rasmussen, Peter

    2000-01-01

    A method to correlate and predict salt solubilities in mixed solvents using a UNIQUAC+Debye-Huckel model is developed. The UNIQUAC equation is applied in a form with temperature-dependent parameters. The Debye-Huckel model is extended to mixed solvents by properly evaluating the dielectric...... constants and the liquid densities of the solvent media. To normalize the activity coefficients, the symmetric convention is adopted. Thermochemical properties of the salt are used to estimate the solubility product. It is shown that the proposed procedure can describe with good accuracy a series of salt...

  7. Modeling of Salt Solubilities in Mixed Solvents

    DEFF Research Database (Denmark)

    Chiavone-Filho, O.; Rasmussen, Peter

    2000-01-01

    A method to correlate and predict salt solubilities in mixed solvents using a UNIQUAC+Debye-Huckel model is developed. The UNIQUAC equation is applied in a form with temperature-dependent parameters. The Debye-Huckel model is extended to mixed solvents by properly evaluating the dielectric...... constants and the liquid densities of the solvent media. To normalize the activity coefficients, the symmetric convention is adopted. Thermochemical properties of the salt are used to estimate the solubility product. It is shown that the proposed procedure can describe with good accuracy a series of salt...

  8. The contributions to solvent uptake by skin and inhalation exposure

    Energy Technology Data Exchange (ETDEWEB)

    Daniell, W.; Stebbins, A.; Kalman, D.; O' Donnell, J.F.; Horstman, S.W. (Department of Environmental Health, University of Washington, Seattle (United States))

    1992-02-01

    Solvent exposures were assessed among 97 auto body repair workers in order to determine whether skin contact represented a significant route of exposure. Each subject's cumulative skin exposure was ranked categorically based on simple observation: 49 none, 33 incidental or low, and 15 moderate or high. The median time-weighted average air exposure to solvents was 8.4% of the American Conference of Governmental Industrial Hygienists (ACGIH) combined solvent threshold limit value (TLV) with a range of 0-62% TLV, including toluene (median 4 ppm) and xylenes (median 0.9 ppm). Urine methyl hippuric acids (MHAs, metabolites of xylenes) were low compared to the ACGIH biological exposure index (BEI) with a median of 2% and a range of 0-12% BEI but were strongly correlated with both the level of airborne xylenes and skin exposure when considered simultaneously by using analysis of covariance (R = 0.91, p less than 0.0001). MHA excretion attributable to skin exposure for 15 min or more generally was comparable to or greater than that from associated air exposure over the full work shift. This study had limited ability to assess quantitatively the contributions of toluene exposures, but there was evidence that skin exposures also contributed significantly to toluene absorption. Air sampling will substantially underestimate a worker's total solvent dose in the setting of moderate or high skin exposure. Simple observation was effective in identifying workers in this sample who appeared to have sufficient skin exposure to produce a measurable increase in solvent uptake.

  9. Solvent substitution: an analysis of comprehensive hazard screening indices.

    Science.gov (United States)

    Debia, M; Bégin, D; Gérin, M

    2011-06-01

    The air index (ψ(i)(air)) of the PARIS II software (Environmental Protection Agency), the Indiana Relative Chemical Hazard Score (IRCHS), and the Final Hazard Score (FHS) used in the P2OASys system (Toxics Use Reduction Institute) are comprehensive hazard screening indices that can be used in solvent substitution. The objective of this study was to evaluate these indices using a list of 67 commonly used or recommended solvents. The indices ψ(i)(air), IRCHS and FHS were calculated considering 9, 13, and 33 parameters, respectively, that summarized health and safety hazards, and environmental impacts. Correlation and sensitivity analyses were performed. The vapor hazard ratio (VHR) was used as a reference point. Two good correlations were found: (1) between VHR and ψ(i)(air) (ρ = 0.84), (2) and between IRCHS and FHS (ρ = 0.81). Values of sensitivity ratios above 0.2 were found with ψ(i)(air) (4 of 9 parameters) and IRCHS (3 of 13 parameters), but not with FHS. Overall, the three indices exhibited important differences in the way they integrate key substitution factors, such as volatility, occupational exposure limit, skin exposure, flammability, carcinogenicity, photochemical oxidation potential, atmospheric global effects, and environmental terrestrial and aquatic effects. These differences can result in different choices of alternatives between indices, including the VHR. IRCHS and FHS are the most comprehensive indices but are very tedious and complex to use and lack sensitivity to several solvent-specific parameters. The index ψ(i)(air) is simpler to calculate but does not cover some parameters important to solvents. There is presently no suitably comprehensive tool available for the substitution of solvents. A two-tier approach for the selection of solvents is recommended to avoid errors that could be made using only a global index or the consideration of the simple VHR. As a first tier, one would eliminate solvent candidates having crucial impacts. As a

  10. Apparatus To Test Solvent Stress Crazing Of Polymer Sheets

    Science.gov (United States)

    Simpson, Gareth L.; Hoult, William S.

    1996-01-01

    Apparatus simple to make, operate, and maintain used to determine abilities of transparent polymeric seal materials to resist stress crazing when exposed to various cleaning solvents. Includes pulleys, cable, and weights to apply constant tension to specimen sheet immersed in test fluid in glass vessel. Provides visual observation of specimen at any time during test and ease of removal of fluid via drain port at bottom of glass vessel.

  11. A Peptide Amphiphile Organogelator of Polar Organic Solvents

    Science.gov (United States)

    Rouse, Charlotte K.; Martin, Adam D.; Easton, Christopher J.; Thordarson, Pall

    2017-01-01

    A peptide amphiphile is reported, that gelates a range of polar organic solvents including acetonitrile/water, N,N-dimethylformamide and acetone, in a process dictated by β-sheet interactions and facilitated by the presence of an alkyl chain. Similarities with previously reported peptide amphiphile hydrogelators indicate analogous underlying mechanisms of gelation and structure-property relationships, suggesting that peptide amphiphile organogel design may be predictably based on hydrogel precedents. PMID:28255169

  12. Fatal fulminant hepatic failure in a 'solvent abuser'.

    OpenAIRE

    McIntyre, A S; Long, R G

    1992-01-01

    The case of a 17 year old abuser of butane aerosols who developed fulminant hepatic failure after taking a proprietary engine or carburetor cleaner is described. Fatalities as a result of liver failure due to volatile hydrocarbons or solvents have not previously been reported. The likely toxins included isopropyl alcohol, methyl amyl alcohol, butylated hydroxytoluene as well as petroleum products, and evidence for their toxicity is reviewed. The possibility of increased susceptibility to hepa...

  13. An electrolyte CPA equation of state for mixed solvent electrolytes

    DEFF Research Database (Denmark)

    Maribo-Mogensen, Bjørn; Thomsen, Kaj; Kontogeorgis, Georgios M.

    2015-01-01

    that the predictive capabilities could be improved through the development of an electrolyte equation of state. In this work, the Cubic Plus Association (CPA) Equation of State is extended to handle mixtures containing electrolytes by including the electrostatic contributions from the Debye-Hückel and Born terms...... depression. Finally, the model is applied to predict VLE, LLE, and SLE in aqueous salt mixtures as well as in mixed solvents....

  14. DAPI binding to the DNA minor groove: a continuum solvent analysis.

    Science.gov (United States)

    De Castro, L F Pineda; Zacharias, M

    2002-01-01

    A continuum solvent model based on the generalized Born (GB) or finite-difference Poisson-Boltzmann (FDPB) approaches has been employed to compare the binding of 4'-6-diamidine-2-phenyl indole (DAPI) to the minor groove of various DNA sequences. Qualitative agreement between the results of GB and FDPB approaches as well as between calculated and experimentally observed trends regarding the sequence specificity of DAPI binding to B-DNA was obtained. Calculated binding energies were decomposed into various contributions to solvation and DNA-ligand interaction. DNA conformational adaptation was found to make a favorable contribution to the calculated total interaction energy but did not change the DAPI binding affinity ranking of different DNA sequences. The calculations indicate that closed complex formation is mainly driven by nonpolar contributions and was found to be disfavored electrostatically due to a desolvation penalty that outbalances the attractive Coulomb interaction. The calculated penalty was larger for DAPI binding to GC-rich sequences compared with AT-rich target sequences and generally larger for the FDPB vs the GB continuum model. A radial interaction profile for DAPI at different distances from the DNA minor groove revealed an electrostatic energy minimum a few Angstroms farther away from the closed binding geometry. The calculated electrostatic interaction up to this distance is attractive and it may stabilize a nonspecific binding arrangement.

  15. Analysis of metabolic pathways by the growth of cells in the presence of organic solvents.

    Science.gov (United States)

    Spinnler, H E; Ginies, C; Khan, J A; Vulfson, E N

    1996-01-01

    A new approach to the analysis of metabolic pathways involving poorly water-soluble intermediates is proposed. It relies upon the ability of the hydrophobic intermediates formed by a sequence of intracellular reactions to cross the membrane(s) and partition between aqueous and organic phases, when cells are incubated in the presence of a nonpolar and nontoxic organic solvent. As a result of this thermodynamically driven efflux of the formed intermediates from the cell, they accumulate in the organic medium in sufficient quantities for GC-MS analysis and identification. This enables direct determination of the sequence of chemical reactions involved with no requirement for the isolation of each individual metabolite from a cell-free extract. The feasibility of the proposed methodology has been demonstrated by the elucidation of the biosynthesis of (R)-gamma-decalactone from (R)-ricinoleic acid catalyzed by the yeast Sporidiobolus ruinenii grown in the presence of decane. The corresponding 4-hydroxy-acid intermediates, formed in the course of beta-oxidation of (R)-ricinoleic acid, were simultaneously observed in a single experiment on the same chromatogram. Potential applications of this proposed methodology are briefly discussed. Images Fig. 1 PMID:11607651

  16. Supramolecular complexes of multivalent cholesterol-containing polymers to solubilize carbon nanotubes in apolar organic solvents.

    Science.gov (United States)

    Nguendia, Jules Zeuna; Zhong, Weiheng; Fleury, Alexandre; De Grandpré, Guillaume; Soldera, Armand; Sabat, Ribal Georges; Claverie, Jerome P

    2014-05-01

    Copolymers of 2-ethylhexyl acrylate (EHA) and cholesteryloxycarbonyl-2-hydroxymethacrylate (CEM) were prepared by reversible addition-fragmentation chain-transfer (RAFT) polymerization. Supramolecular complexes of these copolymers with carbon nanotubes (CNTs) were soluble in THF, toluene, and isooctane. The colloidal solutions remained stable for months without aggregation. The rationale for the choice of CEM was based on the high adsorption energy of cholesterol on the CNT surface, as computed by DFT calculations. Adsorption isotherms were experimentally measured for copolymers of various architectures (statistical, diblock, and star copolymers), thereby demonstrating that 2-5 cholesterol groups were adsorbed per polymer chain. Once the supramolecular complex had dried, the CNTs could be easily resolubilized in isooctane without the need for high-power sonication and in the absence of added polymer. Analysis by atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) indicated that the CNTs were devoid of bundles. The supramolecular complexes could also be employed in an inverse emulsion polymerization of 2-hydroxyethylmethacrylate (HEMA) in isooctane and dodecane, thereby leading to the formation of a continuous polymeric sheath around the CNTs. Thus, this technique leads to the formation of very stable dispersions in non-polar organic solvents, without altering the fundamental properties of the CNTs. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. GaN nanowire arrays with nonpolar sidewalls for vertically integrated field-effect transistors

    Science.gov (United States)

    Yu, Feng; Yao, Shengbo; Römer, Friedhard; Witzigmann, Bernd; Schimpke, Tilman; Strassburg, Martin; Bakin, Andrey; Schumacher, Hans Werner; Peiner, Erwin; Suryo Wasisto, Hutomo; Waag, Andreas

    2017-03-01

    Vertically aligned gallium nitride (GaN) nanowire (NW) arrays have attracted a lot of attention because of their potential for novel devices in the fields of optoelectronics and nanoelectronics. In this work, GaN NW arrays have been designed and fabricated by combining suitable nanomachining processes including dry and wet etching. After inductively coupled plasma dry reactive ion etching, the GaN NWs are subsequently treated in wet chemical etching using AZ400K developer (i.e., with an activation energy of 0.69 ± 0.02 eV and a Cr mask) to form hexagonal and smooth a-plane sidewalls. Etching experiments using potassium hydroxide (KOH) water solution reveal that the sidewall orientation preference depends on etchant concentration. A model concerning surface bonding configuration on crystallography facets has been proposed to understand the anisotropic wet etching mechanism. Finally, NW array-based vertical field-effect transistors with wrap-gated structure have been fabricated. A device composed of 99 NWs exhibits enhancement mode operation with a threshold voltage of 1.5 V, a superior electrostatic control, and a high current output of >10 mA, which prevail potential applications in next-generation power switches and high-temperature digital circuits.

  18. The conformation of acetylated virginiamycin M1 and virginiamycin M1 in explicit solvents.

    Science.gov (United States)

    Ng, Chai Ann; Zhao, Wen; Dang, Jason; Bergdahl, Mikael; Separovic, Frances; Brownlee, Robert T C; Metzger, Robert P

    2007-05-01

    The three-dimensional structure of acetylated virginiamycin M(1) (acetylated VM1) in chloroform and in a water/acetonitrile mixture (83:17 v/v) have been established through 2D high resolution NMR experiments and molecular dynamics modeling and the results compared with the conformation of the antibiotic VM1 in the same and other solvents. The results indicated that acetylation of the C-14 OH group of VM1 caused it to rotate about 90 degrees from the position it assumed in non-acetylated VM1. The conformation of both VM1 and acetylated VM1 appear to flatten in moving from a nonpolar to polar solvent. However, the acetylated form has a more hydrophobic nature. The acetylated VM1 in chloroform and in water/acetonitrile solution had a similar configuration to that of VM1 bound to 50S ribosomes and to the Vat(D) active sites as previously determined by X-ray crystallography. Docking studies of VM1 to the 50S ribosomal binding site and the Vat(D) gave conformations very similar to those derived from X-ray crystallographic studies. The docking studies with acetylated VM1 suggested the possibility of a hydrogen bond from the acetyl carbonyl group oxygen of acetylated VM1 to the 2' hydroxyl group of ribose of adenosine 2538 at the ribosomal VM1 binding site. No hydrogen bonds between acetylated VM1 and the Vat(D) active sites were found; the loss of this binding interaction partly accounts for the release of the product from the active site.

  19. Solvent-Free Synthesis of New Coumarins

    Directory of Open Access Journals (Sweden)

    Redah I. Al-Bayati

    2012-01-01

    Full Text Available A solvent-free synthesis of five series of coumarin derivatives using microwave assistant is presented herein. The synthesized compounds are fully characterized by UV-VIS, FT-IR, and NMR spectroscopy.

  20. "Solvent Effects" in 1H NMR Spectroscopy.

    Science.gov (United States)

    Cavaleiro, Jose A. S.

    1987-01-01

    Describes a simple undergraduate experiment in chemistry dealing with the "solvent effects" in nuclear magnetic resonance (NMR) spectroscopy. Stresses the importance of having students learn NMR spectroscopy as a tool in analytical chemistry. (TW)

  1. Energy efficiency for the removal of non-polar pollutants during ultraviolet irradiation, visible light photocatalysis and ozonation of a wastewater effluent.

    Science.gov (United States)

    Santiago-Morales, Javier; Gómez, María José; Herrera-López, Sonia; Fernández-Alba, Amadeo R; García-Calvo, Eloy; Rosal, Roberto

    2013-10-01

    This study aims to assess the removal of a set of non-polar pollutants in biologically treated wastewater using ozonation, ultraviolet (UV 254 nm low pressure mercury lamp) and visible light (Xe-arc lamp) irradiation as well as visible light photocatalysis using Ce-doped TiO2. The compounds tracked include UV filters, synthetic musks, herbicides, insecticides, antiseptics and polyaromatic hydrocarbons. Raw wastewater and treated samples were analyzed using stir-bar sorptive extraction coupled with comprehensive two-dimensional gas chromatography (SBSE-CG × GC-TOF-MS). Ozone treatment could remove most pollutants with a global efficiency of over 95% for 209 μM ozone dosage. UV irradiation reduced the total concentration of the sixteen pollutants tested by an average of 63% with high removal of the sunscreen 2-ethylhexyl trans-4-methoxycinnamate (EHMC), the synthetic musk 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene (tonalide, AHTN) and several herbicides. Visible light Ce-TiO2 photocatalysis reached ~70% overall removal with particularly high efficiency for synthetic musks. In terms of power usage efficiency expressed as nmol kJ(-1), the results showed that ozonation was by far the most efficient process, ten-fold over Xe/Ce-TiO2 visible light photocatalysis, the latter being in turn considerably more efficient than UV irradiation. In all cases the efficiency decreased along the treatments due to the lower reaction rate at lower pollutant concentration. The use of photocatalysis greatly improved the efficiency of visible light irradiation. The collector area per order decreased from 9.14 ± 5.11 m(2) m(-3) order(-1) for visible light irradiation to 0.16 ± 0.03 m(2) m(-3) order(-1) for Ce-TiO2 photocatalysis. The toxicity of treated wastewater was assessed using the green alga Pseudokirchneriella subcapitata. Ozonation reduced the toxicity of treated wastewater, while UV irradiation and visible light photocatalysis limited by 20-25% the algal growth due to

  2. Nonpolar III-nitride vertical-cavity surface-emitting laser with a photoelectrochemically etched air-gap aperture

    Energy Technology Data Exchange (ETDEWEB)

    Leonard, J. T., E-mail: jtleona01@gmail.com; Yonkee, B. P.; Cohen, D. A.; Megalini, L.; Speck, J. S. [Materials Department, University of California, Santa Barbara, California 93106 (United States); Lee, S. [Department of Electrical and Computer Engineering, University of California, Santa Barbara, California 93106 (United States); DenBaars, S. P.; Nakamura, S. [Materials Department, University of California, Santa Barbara, California 93106 (United States); Department of Electrical and Computer Engineering, University of California, Santa Barbara, California 93106 (United States)

    2016-01-18

    We demonstrate a III-nitride nonpolar vertical-cavity surface-emitting laser (VCSEL) with a photoelectrochemically (PEC) etched aperture. The PEC lateral undercut etch is used to selectively remove the multi-quantum well (MQW) region outside the aperture area, defined by an opaque metal mask. This PEC aperture (PECA) creates an air-gap in the passive area of the device, allowing one to achieve efficient electrical confinement within the aperture, while simultaneously achieving a large index contrast between core of the device (the MQW within the aperture) and the lateral cladding of the device (the air-gap formed by the PEC etch), leading to strong lateral confinement. Scanning electron microscopy and focused ion-beam analysis is used to investigate the precision of the PEC etch technique in defining the aperture. The fabricated single mode PECA VCSEL shows a threshold current density of ∼22 kA/cm{sup 2} (25 mA), with a peak output power of ∼180 μW, at an emission wavelength of 417 nm. The near-field emission profile shows a clearly defined single linearly polarized (LP) mode profile (LP{sub 12,1}), which is in contrast to the filamentary lasing that is often observed in III-nitride VCSELs. 2D mode profile simulations, carried out using COMSOL, give insight into the different mode profiles that one would expect to be displayed in such a device. The experimentally observed single mode operation is proposed to be predominantly a result of poor current spreading in the device. This non-uniform current spreading results in a higher injected current at the periphery of the aperture, which favors LP modes with high intensities near the edge of the aperture.

  3. Nonpolar III-nitride vertical-cavity surface-emitting laser with a photoelectrochemically etched air-gap aperture

    Science.gov (United States)

    Leonard, J. T.; Yonkee, B. P.; Cohen, D. A.; Megalini, L.; Lee, S.; Speck, J. S.; DenBaars, S. P.; Nakamura, S.

    2016-01-01

    We demonstrate a III-nitride nonpolar vertical-cavity surface-emitting laser (VCSEL) with a photoelectrochemically (PEC) etched aperture. The PEC lateral undercut etch is used to selectively remove the multi-quantum well (MQW) region outside the aperture area, defined by an opaque metal mask. This PEC aperture (PECA) creates an air-gap in the passive area of the device, allowing one to achieve efficient electrical confinement within the aperture, while simultaneously achieving a large index contrast between core of the device (the MQW within the aperture) and the lateral cladding of the device (the air-gap formed by the PEC etch), leading to strong lateral confinement. Scanning electron microscopy and focused ion-beam analysis is used to investigate the precision of the PEC etch technique in defining the aperture. The fabricated single mode PECA VCSEL shows a threshold current density of ˜22 kA/cm2 (25 mA), with a peak output power of ˜180 μW, at an emission wavelength of 417 nm. The near-field emission profile shows a clearly defined single linearly polarized (LP) mode profile (LP12,1), which is in contrast to the filamentary lasing that is often observed in III-nitride VCSELs. 2D mode profile simulations, carried out using COMSOL, give insight into the different mode profiles that one would expect to be displayed in such a device. The experimentally observed single mode operation is proposed to be predominantly a result of poor current spreading in the device. This non-uniform current spreading results in a higher injected current at the periphery of the aperture, which favors LP modes with high intensities near the edge of the aperture.

  4. Comparison of nonpolar III-nitride vertical-cavity surface-emitting lasers with tunnel junction and ITO intracavity contacts

    Science.gov (United States)

    Leonard, J. T.; Young, E. C.; Yonkee, B. P.; Cohen, D. A.; Shen, C.; Margalith, T.; Ng, T. K.; DenBaars, S. P.; Ooi, B. S.; Speck, J. S.; Nakamura, S.

    2016-02-01

    We report on the lasing of III-nitride nonpolar, violet, vertical-cavity surface-emitting lasers (VCSELs) with IIInitride tunnel-junction (TJ) intracavity contacts and ion implanted apertures (IIAs). The TJ VCSELs are compared to similar VCSELs with tin-doped indium oxide (ITO) intracavity contacts. Prior to analyzing device results, we consider the relative advantages of III-nitride TJs for blue and green emitting VCSELs. The TJs are shown to be most advantageous for violet and UV VCSELs, operating near or above the absorption edge for ITO, as they significantly reduce the total internal loss in the cavity. However, for longer wavelength III-nitride VCSELs, TJs primarily offer the advantage of improved cavity design flexibility, allowing one to make the p-side thicker using a thick n-type III-nitride TJ intracavity contact. This offers improved lateral current spreading and lower loss, compare to using ITO and p-GaN, respectively. These aspects are particularly important for achieving high-power CW VCSELs, making TJs the ideal intracavity contact for any III-nitride VCSEL. A brief overview of III-nitride TJ growth methods is also given, highlighting the molecular-beam epitaxy (MBE) technique used here. Following this overview, we compare 12 μm aperture diameter, violet emitting, TJ and ITO VCSEL experimental results, which demonstrate the significant improvement in differential efficiency and peak power resulting from the reduced loss in the TJ design. Specifically, the TJ VCSEL shows a peak power of ~550 μW with a threshold current density of ~3.5 kA/cm2, while the ITO VCSELs show peak powers of ~80 μW and threshold current densities of ~7 kA/cm2.

  5. Non-polar organic compounds in marine aerosols over the northern South China Sea: Influence of continental outflow.

    Science.gov (United States)

    Zhao, Yan; Zhang, Yingyi; Fu, Pingqing; Ho, Steven Sai Hang; Ho, Kin Fai; Liu, Fobang; Zou, Shichun; Wang, Shan; Lai, Senchao

    2016-06-01

    Filter samples of total suspended particle (TSP) collected during a cruise campaign over the northern South China Sea (SCS) from September to October 2013 were analyzed for non-polar organic compounds (NPOCs) as well as organic carbon (OC), elemental carbon (EC) and water-soluble ions. A total of 115 NPOCs species in groups of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), iso-/antiso-alkanes, hopanes, steranes, methylalkanes, branched alkanes, cycloalkanes, alkenes and phthalates were detected. The characteristics of NPOCs in marine TSP samples were investigated to understand the sources from the Asian continent and other regions. The concentrations of total NPOCs ranged from 19.8 to 288.2 ng/m(3) with an average of 87.9 ng/m(3), which accounted for 0.8-1.7% (average 1.0%) of organic matter (OM). n-Alkanes was the predominant group, accounting for 43.1-79.5%, followed by PAHs (5.5-44.4%) and hopanes (1.6-11.4%). We found that primary combustion (biomass burning/fossil fuel combustion) was the dominant source for the majority of NPOCs (89.1%). Biomass burning in southern/southeastern China via long-range transport was proposed to be a major contributor of NPOCs in marine aerosols over the northern SCS, suggested by the significant correlations between nss-K(+) and NPOCs groups as well as the analysis of air mass back-trajectory and fire spots. For the samples with strong continental influence, the strong enhancement in concentrations of n-alkanes, PAHs, hopanes and steranes were attributed to fossil fuel (coal/petroleum) combustion. In addition, terrestrial plants waxes were another contributor to NPOCs.

  6. Comparison of nonpolar III-nitride vertical-cavity surface-emitting lasers with tunnel junction and ITO intracavity contacts

    KAUST Repository

    Leonard, J. T.

    2016-03-01

    We report on the lasing of III-nitride nonpolar, violet, vertical-cavity surface-emitting lasers (VCSELs) with III-nitride tunnel-junction (TJ) intracavity contacts and ion implanted apertures (IIAs). The TJ VCSELs are compared to similar VCSELs with tin-doped indium oxide (ITO) intracavity contacts. Prior to analyzing device results, we consider the relative advantages of III-nitride TJs for blue and green emitting VCSELs. The TJs are shown to be most advantageous for violet and UV VCSELs, operating near or above the absorption edge for ITO, as they significantly reduce the total internal loss in the cavity. However, for longer wavelength III-nitride VCSELs, TJs primarily offer the advantage of improved cavity design flexibility, allowing one to make the p-side thicker using a thick n-type III-nitride TJ intracavity contact. This offers improved lateral current spreading and lower loss, compare to using ITO and p-GaN, respectively. These aspects are particularly important for achieving high-power CW VCSELs, making TJs the ideal intracavity contact for any III-nitride VCSEL. A brief overview of III-nitride TJ growth methods is also given, highlighting the molecular-beam epitaxy (MBE) technique used here. Following this overview, we compare 12 mu m aperture diameter, violet emitting, TJ and ITO VCSEL experimental results, which demonstrate the significant improvement in differential efficiency and peak power resulting from the reduced loss in the TJ design. Specifically, the TJ VCSEL shows a peak power of similar to 550 mu W with a threshold current density of similar to 3.5 kA/cm(2), while the ITO VCSELs show peak powers of similar to 80 mu W and threshold current densities of similar to 7 kA/cm

  7. One-pot synthesis of stable colloidal solutions of MFe{sub 2}O{sub 4} nanoparticles using oleylamine as solvent and stabilizer

    Energy Technology Data Exchange (ETDEWEB)

    Pérez-Mirabet, Leonardo [Departament de Química, Universitat Autònoma de Barcelona, Campus de la UAB, 08193 Bellaterra (Spain); Solano, Eduardo, E-mail: eduardo.solano@uab.cat [Departament de Química, Universitat Autònoma de Barcelona, Campus de la UAB, 08193 Bellaterra (Spain); Martínez-Julián, Fernando; Guzmán, Roger [Institut de Ciència de Materials de Barcelona, ICMAB-CSIC, Campus de la UAB, 08193 Bellaterra (Spain); Arbiol, Jordi [Institut de Ciència de Materials de Barcelona, ICMAB-CSIC, Campus de la UAB, 08193 Bellaterra (Spain); Institució Catalana de Recerca i Estudis Avançats (ICREA), 08019 Barcelona (Spain); Puig, Teresa; Obradors, Xavier; Pomar, Alberto [Institut de Ciència de Materials de Barcelona, ICMAB-CSIC, Campus de la UAB, 08193 Bellaterra (Spain); Yáñez, Ramón; Ros, Josep [Departament de Química, Universitat Autònoma de Barcelona, Campus de la UAB, 08193 Bellaterra (Spain); Ricart, Susagna [Institut de Ciència de Materials de Barcelona, ICMAB-CSIC, Campus de la UAB, 08193 Bellaterra (Spain)

    2013-03-15

    Highlights: ► One-pot synthesis of ferrite magnetic nanoparticles (<10 nm) in non-polar media. ► Nanoparticles present high monocrystal quality and monodispersion. ► Superparamagnetic behavior at room temperature. ► Nanoparticles transfer to polar media via ligand exchange. - Abstract: An easy, efficient, reproducible and scalable one-pot synthetic methodology to obtain magnetic spinel ferrite nanoparticles has been developed. This approach is based on one-pot thermal decomposition of Fe(acac){sub 3} and M(acac){sub 2} (M = Co, Mn, Cu and Zn) in oleylamine, which also acts as a capping ligand, by producing stable colloidal dispersions of nanoparticles in non-polar solvents. The properties of the nanoparticles have been studied via different techniques, such as transmission electron microscopy, which shows that nanoparticles are monocrystallines and a narrow dispersion in size; magnetic analyses have demonstrated that the resulting ferrite nanoparticles show high saturation values and superparamagnetic behavior at room temperature; X-ray diffraction has also been performed, and it confirms that the synthesized nanoparticles have a spinel structure. Complementarily, ligand exchange has been also carried out in order to produce dispersions of the synthesized nanoparticles in polar media.

  8. Water as a Solvent for Life

    Science.gov (United States)

    Pohorille, Andrew; Pratt, Lawrence R.

    2015-01-01

    "Follow the water" is our basic strategy in searching for life in the universe. The universality of water as the solvent for living systems is usually justified by arguing that water supports the rich organic chemistry that seeds life, but alternative chemistries are possible in other organic solvents. Here, other, essential criteria for life that have not been sufficiently considered so far, will be discussed.

  9. Biofiltration of solvent vapors from air

    Energy Technology Data Exchange (ETDEWEB)

    Oh, Young-sook.

    1993-01-01

    For various industrial solvent vapors, biofiltration promises to offer a cost-effective emission control technology. Exploiting the full potential of this technology will help attain the goals of the Clean Air Act Amendments of 1990. Concentrating on large volumes of volatile industrial solvents, stable multicomponent microbial enrichments capable of growing a mineral medium with solvent vapors as their only source of carbon and energy were obtained from soil and sewage sludge. These consortia were immobilized on an optimized porous solid support (ground peat moss and perlite). The biofilter material was packed in glass columns connected to an array of pumps and flow meters that allowed the independent variation of superficial velocity and solvent vapor concentrations. In various experiments, single solvents, such as methanol, butanol, acetonitrile, hexane and nitrobenzene, and solvent mixtures, such as benzene-toluene-xylene (BTX) and chlorobenzene-o-dichlorobenzene (CB/DCB) were biofiltered with rates ranging from 15 to334 g solvent removed per m[sup 3] filter volume /h. Pressure drops were low to moderate (0-10 mmHg/m) and with periodic replacement of moisture, the biofiltration activity could be maintained for a period of several months. The experimental data on methanol biofiltration were subjected to mathematical analysis and modeling by the group of Dr. Baltzis at NJIT for a better understanding and a possible scale up of solvent vapor biofilters. In the case of chlorobenzenes and nitrobenzene, the biofilter columns had to be operated with water recirculation in a trickling filter mode. To prevent inactivation of the trickling filter by acidity during CB/DCB removal, pH control was necessary, and the removal rate of CB/DCB was strongly influenced by the flow rate of the recyling water. Nitrobenzene removal in a trickling filter did not require pH control, since the nitro group was reduced and volatilized as ammonia.

  10. Competitive solvent-molecule interactions govern primary processes of diphenylcarbene in solvent mixtures

    Science.gov (United States)

    Knorr, Johannes; Sokkar, Pandian; Schott, Sebastian; Costa, Paolo; Thiel, Walter; Sander, Wolfram; Sanchez-Garcia, Elsa; Nuernberger, Patrick

    2016-10-01

    Photochemical reactions in solution often proceed via competing reaction pathways comprising intermediates that capture a solvent molecule. A disclosure of the underlying reaction mechanisms is challenging due to the rapid nature of these processes and the intricate identification of how many solvent molecules are involved. Here combining broadband femtosecond transient absorption and quantum mechanics/molecular mechanics simulations, we show for one of the most reactive species, diphenylcarbene, that the decision-maker is not the nearest solvent molecule but its neighbour. The hydrogen bonding dynamics determine which reaction channels are accessible in binary solvent mixtures at room temperature. In-depth analysis of the amount of nascent intermediates corroborates the importance of a hydrogen-bonded complex with a protic solvent molecule, in striking analogy to complexes found at cryogenic temperatures. Our results show that adjacent solvent molecules take the role of key abettors rather than bystanders for the fate of the reactive intermediate.

  11. Solvent dependent photophysical properties of dimethoxy curcumin

    Science.gov (United States)

    Barik, Atanu; Indira Priyadarsini, K.

    2013-03-01

    Dimethoxy curcumin (DMC) is a methylated derivative of curcumin. In order to know the effect of ring substitution on photophysical properties of curcumin, steady state absorption and fluorescence spectra of DMC were recorded in organic solvents with different polarity and compared with those of curcumin. The absorption and fluorescence spectra of DMC, like curcumin, are strongly dependent on solvent polarity and the maxima of DMC showed red shift with increase in solvent polarity function (Δf), but the above effect is prominently observed in case of fluorescence maxima. From the dependence of Stokes' shift on solvent polarity function the difference between the excited state and ground state dipole moment was estimated as 4.9 D. Fluorescence quantum yield (ϕf) and fluorescence lifetime (τf) of DMC were also measured in different solvents at room temperature. The results indicated that with increasing solvent polarity, ϕf increased linearly, which has been accounted for the decrease in non-radiative rate by intersystem crossing (ISC) processes.

  12. SCENARIOS EVALUATION TOOL FOR CHLORINATED SOLVENT MNA

    Energy Technology Data Exchange (ETDEWEB)

    Vangelas, K; Brian02 Looney, B; Michael J. Truex; Charles J. Newell

    2006-08-16

    Over the past three decades, much progress has been made in the remediation of chlorinated solvents from the subsurface. Yet these pervasive contaminants continue to present a significant challenge to the U.S. Department of Energy (DOE), other federal agencies, and other public and private organizations. The physical and chemical properties of chlorinated solvents make it difficult to rapidly reach the low concentrations typically set as regulatory limits. These technical challenges often result in high costs and long remediation time frames. In 2003, the DOE through the Office of Environmental Management funded a science-based technical project that uses the U.S. Environmental Protection Agency's technical protocol (EPA, 1998) and directives (EPA, 1999) on Monitored Natural Attenuation (MNA) as the foundation on which to introduce supporting concepts and new scientific developments that will support remediation of chlorinated solvents based on natural attenuation processes. This project supports the direction in which many site owners want to move to complete the remediation of their site(s), that being to complete the active treatment portion of the remedial effort and transition into MNA. The overarching objective of the effort was to examine environmental remedies that are based on natural processes--remedies such as Monitored Natural Attenuation (MNA) or Enhanced Attenuation (EA). The research program did identify several specific opportunities for advances based on: (1) mass balance as the central framework for attenuation based remedies, (2) scientific advancements and achievements during the past ten years, (3) regulatory and policy development and real-world experience using MNA, and (4) exploration of various ideas for integrating attenuation remedies into a systematic set of ''combined remedies'' for contaminated sites. These opportunities are summarized herein and are addressed in more detail in referenced project documents and

  13. Computer-aided tool for solvent selection in pharmaceutical processes: Solvent swap

    DEFF Research Database (Denmark)

    Papadakis, Emmanouil; K. Tula, Anjan; Gernaey, Krist V.

    In the pharmaceutical processes, solvents have a multipurpose role since different solvents can be used in different stages (such as chemical reactions, separations and purification) in the multistage active pharmaceutical ingredients (APIs) production process. The solvent swap and selection task......-aided framework with the objective to assist the pharmaceutical industry in gaining better process understanding. A software interface to improve the usability of the tool has been created also....

  14. Influence of solvent polarity on preferential solvation of molecular recognition probes in solvent mixtures.

    Science.gov (United States)

    Amenta, Valeria; Cook, Joanne L; Hunter, Christopher A; Low, Caroline M R; Vinter, Jeremy G

    2012-12-13

    The association constants for formation of 1:1 complexes between a H-bond acceptor, tri-n-butylphosphine oxide, and a H-bond donor, 4-phenylazophenol, have been measured in a range of different solvent mixtures. Binary mixtures of n-octane and a more polar solvent (ether, ester, ketone, nitrile, sulfoxide, tertiary amide, and halogenated and aromatic solvents) have been investigated. Similar behavior was observed in all cases. When the concentration of the more polar solvent is low, the association constant is identical to that observed in pure n-octane. Once a threshold concentration of the more polar solvent in reached, the logarithm of the association constant decreases in direct proportion to the logarithm of the concentration of the more polar solvent. This indicates that one of the two solutes is preferentially solvated by the more polar solvent, and it is competition with this solvation equilibrium that determines the observed association constant. The concentration of the more polar solvent at which the onset of preferential solvation takes place depends on solvent polarity: 700 mM for toluene, 60 mM for 1,1,2,2-tetrachloroethane, 20 mM for the ether, ester, ketone, and nitrile, 0.2 mM for the tertiary amide, and 0.1 mM for the sulfoxide solvents. The results can be explained by a simple model that considers only pairwise interactions between specific sites on the surfaces of the solutes and solvents, which implies that the bulk properties of the solvent have little impact on solvation thermodynamics.

  15. Microfluidic Extraction of Biomarkers using Water as Solvent

    Science.gov (United States)

    Amashukeli, Xenia; Manohara, Harish; Chattopadhyay, Goutam; Mehdi, Imran

    2009-01-01

    A proposed device, denoted a miniature microfluidic biomarker extractor (mu-EX), would extract trace amounts of chemicals of interest from samples, such as soils and rocks. Traditionally, such extractions are performed on a large scale with hazardous organic solvents; each solvent capable of dissolving only those molecules lying within narrow ranges of specific chemical and physical characteristics that notably include volatility, electric charge, and polarity. In contrast, in the mu-EX, extractions could be performed by use of small amounts (typically between 0.1 and 100 L) of water as a universal solvent. As a rule of thumb, in order to enable solvation and extraction of molecules, it is necessary to use solvents that have polarity sufficiently close to the polarity of the target molecules. The mu-EX would make selection of specific organic solvents unnecessary, because mu-EX would exploit a unique property of liquid water: the possibility of tuning its polarity to match the polarity of organic solvents appropriate for extraction of molecules of interest. The change of the permittivity of water would be achieved by exploiting interactions between the translational states of water molecules and an imposed electromagnetic field in the frequency range of 300 to 600 GHz. On a molecular level, these interactions would result in disruption of the three-dimensional hydrogen-bonding network among liquid-water molecules and subsequent solvation and hydrolysis of target molecules. The mu-EX is expected to be an efficient means of hydrolyzing chemical bonds in complex macromolecules as well and, thus, enabling analysis of the building blocks of these complex chemical systems. The mu-EX device would include a microfluidic channel, part of which would lie within a waveguide coupled to an electronically tuned source of broad-band electromagnetic radiation in the frequency range from 300 to 600 GHz (see figure). The part of the microfluidic channel lying in the waveguide would

  16. CHEMICAL STABILITY OF POLYPHENYLENE SULFIDE IN THE NEXT GENERATION SOLVENT FOR CAUSTIC-SIDE SOLVENT EXTRACTION

    Energy Technology Data Exchange (ETDEWEB)

    Fondeur, F.; Fink, S.

    2011-12-08

    The Office of Waste Processing, within the Office of Technology Innovation and Development, is funding the development of an enhanced solvent for deployment at the Savannah River Site for removal of cesium from High Level Waste. For simplicity, this solvent is referred to as the Next Generation Solvent (NGS). The technical effort is collaboration between Oak Ridge National Laboratory (ORNL), Savannah River National Laboratory (SRNL), and Argonne National Laboratory. The initial deployment target envisioned for the technology was within the Modular Caustic-Side Solvent Extraction Unit (MCU). Deployment of a new chemical within an existing facility requires verification that the chemical components are compatible with the installed equipment. In the instance of a new organic solvent, the primary focus is on compatibility of the solvent with polyphenylene sulfide (PPS), the polymer used in the coalescers within MCU. This report provides the data from exposing PPS polymer to NGS. The test was conducted over a three month period. PPS is remarkably stable in the presence of the next generation solvent. Testing showed no indication of swelling or significant leaching. Preferential sorption of the Modifier on PPS was observed but the same behavior occurs with the baseline solvent. Therefore, PPS coalescers exposed to the NGS are expected to perform comparably to those in contact with the baseline solvent.

  17. The use of environmentally sustainable bio-derived solvents in solvent extraction applications-A review

    Institute of Scientific and Technical Information of China (English)

    Zheng Li; Kathryn H. Smith; Geoffrey W. Stevens

    2016-01-01

    Replacement of volatile organic compounds (VOCs) by greener or more environmental y sustainable solvents is becoming increasingly important due to the increasing health and environmental concerns as wel as economic pressures associated with VOCs. Solvents that are derived from biomass, namely bio-derived solvents, are a type of green solvent that have attracted intensive investigations in recent years because of their advantages over con-ventional VOCs, such as low toxicity, biodegradability and renewability. This review aims to summarize the use of bio-derived solvents in solvent extraction applications, with special emphasis given to utilization of biodiesels and terpenes. Compared with the conventional VOCs, the overall performance of these bio-derived solvents is comparable in terms of extraction yields and selectivity for natural product extraction and no difference was found for metal extraction. To date most researchers have focused on laboratory scale thermodynamics studies. Future work is required to develop and test new bio-derived solvents and understand the kinetic performance as well as solvent extraction pilot plant studies.

  18. CHEMICAL STABILITY OF POLYPHENYLENE SULFIDE IN THE NEXT GENERATION SOLVENT FOR CAUSTIC-SIDE SOLVENT EXTRACTION

    Energy Technology Data Exchange (ETDEWEB)

    Fondeur, F.; Fink, S.

    2011-12-08

    The Office of Waste Processing, within the Office of Technology Innovation and Development, is funding the development of an enhanced solvent for deployment at the Savannah River Site for removal of cesium from High Level Waste. For simplicity, this solvent is referred to as the Next Generation Solvent (NGS). The technical effort is collaboration between Oak Ridge National Laboratory (ORNL), Savannah River National Laboratory (SRNL), and Argonne National Laboratory. The initial deployment target envisioned for the technology was within the Modular Caustic-Side Solvent Extraction Unit (MCU). Deployment of a new chemical within an existing facility requires verification that the chemical components are compatible with the installed equipment. In the instance of a new organic solvent, the primary focus is on compatibility of the solvent with polyphenylene sulfide (PPS), the polymer used in the coalescers within MCU. This report provides the data from exposing PPS polymer to NGS. The test was conducted over a three month period. PPS is remarkably stable in the presence of the next generation solvent. Testing showed no indication of swelling or significant leaching. Preferential sorption of the Modifier on PPS was observed but the same behavior occurs with the baseline solvent. Therefore, PPS coalescers exposed to the NGS are expected to perform comparably to those in contact with the baseline solvent.

  19. Influence of Energy on Solvent Diffusion in Polymer/Solvent Systems

    Institute of Scientific and Technical Information of China (English)

    HUHuijun; JIANGWenhua; 等

    2002-01-01

    The Vrentas-Duda free-volume theory has been extensively used to correlate or predict the solvent diffusion coefficient of a polymer/solvent system.The energy term in the free volume diffusion equation is difficult to estimate,so the energy term was usually neglected in previous predictive versions of the free volume diffusion coefficient equation.Recent studies show that the energy effect is very important even above the glass transition temperature of the system. In this paper, a new evaluation method of the energy term is proposed,that is the diffusion energy at different solvent concentrations is assumed to be a linear function of the solvent diffusion energy in pure solvents and that in polymers under the condition that the solvent in infinite dilution.By taking consideration of the influence of energy on the solvent diffustion,the prediction of solvent diffusion coefficient was preformed for three polymer/solvent systems over a wide range of concentrations and temperatures.The results show an improvement on the predictive capability of the free volume diffusion theory.

  20. Connecting free energy surfaces in implicit and explicit solvent: an efficient method to compute conformational and solvation free energies.

    Science.gov (United States)

    Deng, Nanjie; Zhang, Bin W; Levy, Ronald M

    2015-06-09

    The ability to accurately model solvent effects on free energy surfaces is important for understanding many biophysical processes including protein folding and misfolding, allosteric transitions, and protein–ligand binding. Although all-atom simulations in explicit solvent can provide an accurate model for biomolecules in solution, explicit solvent simulations are hampered by the slow equilibration on rugged landscapes containing multiple basins separated by barriers. In many cases, implicit solvent models can be used to significantly speed up the conformational sampling; however, implicit solvent simulations do not fully capture the effects of a molecular solvent, and this can lead to loss of accuracy in the estimated free energies. Here we introduce a new approach to compute free energy changes in which the molecular details of explicit solvent simulations are retained while also taking advantage of the speed of the implicit solvent simulations. In this approach, the slow equilibration in explicit solvent, due to the long waiting times before barrier crossing, is avoided by using a thermodynamic cycle which connects the free energy basins in implicit solvent and explicit solvent using a localized decoupling scheme. We test this method by computing conformational free energy differences and solvation free energies of the model system alanine dipeptide in water. The free energy changes between basins in explicit solvent calculated using fully explicit solvent paths agree with the corresponding free energy differences obtained using the implicit/explicit thermodynamic cycle to within 0.3 kcal/mol out of ∼3 kcal/mol at only ∼8% of the computational cost. We note that WHAM methods can be used to further improve the efficiency and accuracy of the implicit/explicit thermodynamic cycle.

  1. Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

    Energy Technology Data Exchange (ETDEWEB)

    Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

    2017-08-01

    The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

  2. Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

    Energy Technology Data Exchange (ETDEWEB)

    Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

    2017-01-24

    The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

  3. ThermoData Engine: Extension to Solvent Design and Multi-component Process Stream Property Calculations with Uncertainty Analysis

    DEFF Research Database (Denmark)

    Diky, Vladimir; Chirico, Robert D.; Muzny, Chris

    property values and expert system for data analysis and generation of recommended property values at the specified conditions along with uncertainties on demand. The most recent extension of TDE covers solvent design and multi-component process stream property calculations with uncertainty analysis......ThermoData Engine (TDE, NIST Standard Reference Databases 103a and 103b) is the first product that implements the concept of Dynamic Data Evaluation in the fields of thermophysics and thermochemistry, which includes maintaining the comprehensive and up-to-date database of experimentally measured....... Solvent Design function serves three tasks: (1) selection of best solvent for a solid solute, (2) search for a selective solvent for a solid binary mixture, and (3) selection of best solvent for extraction. Solvents are selected from the list of registered compounds encountering more than 27,000 entries...

  4. Fluoroalkyl containing salts combined with fluorinated solvents for electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Tikhonov, Konstantin; Yip, Ka Ki; Lin, Tzu-Yuan; Erickson, Michael Jason

    2015-04-21

    Provided are electrochemical cells and electrolytes used to build such cells. An electrolyte may include a fluoroalkyl-substituted LiPF.sub.6 salt or a fluoroalkyl-substituted LiBF.sub.4 salt. In some embodiments, at least one fluorinated alkyl of the salt has a chain length of from 1 to 8 or, more specifically, between about 2 and 8. These fluorinated alkyl groups, in particular, relatively large fluorinated alkyl groups improve solubility of these salts in fluorinated solvents that are less flammable than, for example, conventional carbonate solvents. At the same time, the size of fluoroalkyl-substituted salts should be limited to ensure adequate concentration of the salt in an electrolyte and low viscosity of the electrolyte. In some embodiments, the concentration of a fluoroalkyl-substituted salt is at least about 0.5M. Examples of fluorinated solvents include various fluorinated esters, fluorinated ethers, and fluorinated carbonates, such a 1-methoxyheptafluoropropane, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane, 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane, and 1,1,1,2,3,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)-pentane.

  5. Solvent extraction of radionuclides from aqueous tank waste

    Energy Technology Data Exchange (ETDEWEB)

    Bonnesen, P.; Sachleben, R.; Moyer, B. [Oak Ridge National Lab., TN (United States)

    1996-10-01

    The purpose of this task is to develop an efficient solvent-extraction and stripping process to remove the fission products {sup 99}Tc, {sup 90}Sr, and {sup 137}Cs from alkaline tank waste, such as those stored at Hanford and Oak Ridge. As such, this task expands on FY 1995`s successful development of a solvent-extraction and stripping process for technetium separation from alkaline tank-waste solutions. This process now includes the capability of removing both technetium and strontium simultaneously. In this form, the process has been named SRTALK and will be developed further in this program as a prelude to developing a system capable of removing technetium, strontium, and cesium.

  6. Stability and selectivity of alkaline proteases in hydrophilic solvents

    DEFF Research Database (Denmark)

    Pedersen, Lars Haastrup; Ritthitham, Sinthuwat; Pleissner, Daniel

    2008-01-01

    proteases, but at higher concentrations and particularly in anhydrous systems most enzymes including alkaline proteases will denature and consequently loose activity [1]. However, partial denaturing and increased structural flexibility due to the interaction between hydrophilic solvents and alkaline...... proteases has been agued as the primary reasons for increasing activity, influencing regio-selectivity and improving the enantio-selectivity of these enzymes [2]. Alkaline proteases have been shown to be active not only on peptides, but on a wide range of renewable resources for synthesis of biologically...... active molecules and carriers, and in synthesis of carbohydrate derivatives with designed functional properties.  When it comes to regio-selectivity of alkaline proateses on carbohydrates both the properties of the particular enzyme and the influence of the solvent is determining for the position...

  7. Bimetallic Nanoparticles in Alternative Solvents for Catalytic Purposes

    Directory of Open Access Journals (Sweden)

    Trung Dang-Bao

    2017-07-01

    Full Text Available Bimetallic nanoparticles represent attractive catalytic systems thanks to the synergy between both partners at the atomic level, mainly induced by electronic effects which in turn are associated with the corresponding structures (alloy, core-shell, hetero-dimer. This type of engineered material can trigger changes in the kinetics of catalyzed processes by variations on the electrophilicity/nucleophilicity of the metal centers involved and also promote cooperative effects to foster organic transformations, including multi-component and multi-step processes. Solvents become a crucial factor in the conception of catalytic processes, not only due to their environmental impact, but also because they can preserve the bimetallic structure during the catalytic reaction and therefore increase the catalyst life-time. In this frame, the present review focuses on the recent works described in the literature concerning the synthesis of bimetallic nanoparticles in non-conventional solvents, i.e., other than common volatile compounds, for catalytic applications.

  8. Solvent effects on zero-point vibrational corrections to optical rotations and nuclear magnetic resonance shielding constants

    Science.gov (United States)

    Kongsted, Jacob; Ruud, Kenneth

    2008-01-01

    We present a study of solvent effects on the zero-point vibrational corrections (ZPVC) to optical rotations and nuclear magnetic resonance shielding constants of solvated molecules. The model used to calculate vibrational corrections rely on an expansion of the potential and property surfaces around an effective molecular geometry and includes both harmonic and anharmonic corrections. Numerical examples are presented for ( S)-propylene oxide in various solvents as well as for acetone and the three diazene molecules. We find that solvent effects on the ZPVCs may be significant and in some cases crucial to accurately predict solvent shifts on molecular properties.

  9. Driven polymer translocation in good and bad solvent: Effects of hydrodynamics and tension propagation.

    Science.gov (United States)

    Moisio, J E; Piili, J; Linna, R P

    2016-08-01

    We investigate the driven polymer translocation through a nanometer-scale pore in the presence and absence of hydrodynamics both in good and bad solvent. We present our results on tension propagating along the polymer segment on the cis side that is measured for the first time using our method that works also in the presence of hydrodynamics. For simulations we use stochastic rotation dynamics, also called multiparticle collision dynamics. We find that in the good solvent the tension propagates very similarly whether hydrodynamics is included or not. Only the tensed segment is by a constant factor shorter in the presence of hydrodynamics. The shorter tensed segment and the hydrodynamic interactions contribute to a smaller friction for the translocating polymer when hydrodynamics is included, which shows as smaller waiting times and a smaller exponent in the scaling of the translocation time with the polymer length. In the bad solvent hydrodynamics has a minimal effect on polymer translocation, in contrast to the good solvent, where it speeds up translocation. We find that under bad-solvent conditions tension does not spread appreciably along the polymer. Consequently, translocation time does not scale with the polymer length. By measuring the effective friction in a setup where a polymer in free solvent is pulled by a constant force at the end, we find that hydrodynamics does speed up collective polymer motion in the bad solvent even more effectively than in the good solvent. However, hydrodynamics has a negligible effect on the motion of individual monomers within the highly correlated globular conformation on the cis side and hence on the entire driven translocation under bad-solvent conditions.

  10. Stability of the Caustic-Side Solvent Extraction (CSSX) Process Solvent: Effect of High Nitrite on Solvent Nitration

    Energy Technology Data Exchange (ETDEWEB)

    Bonnesen, P.V.

    2002-06-26

    The purpose of this investigation was to determine whether nitrated organic compounds could be formed during operation of the Caustic-Side Solvent Extraction (CSSX) process, and whether such compounds would present a safety concern. The CSSX process was developed to remove cesium from alkaline high-level salt waste stored at the US Department of Energy Savannah River Site (SRS). The solvent is composed of the cesium extractant calix[4]arene-bis-(4-tert-octylbenzo-crown-6) (BOBCalixC6), a fluorinated alcohol phase modifier, tri-n-octylamine (TOA), and an isoparaffinic diluent (Iospar{reg_sign}). During the CSSX process, the solvent is expected to be exposed to high concentrations of nitrate and nitrite dissolved in the alkaline waste feed. The solvent will also be exposed to dilute (50 mM) nitric acid solutions containing low concentrations of nitrite during scrubbing, followed by stripping with 1 mM nitric acid. The solvent is expected to last for one year of plant operation, and the temperatures the solvent may experience during the process could range from as low as 15 C to as high as 35 C. Excursions from standard process conditions could result in the solvent experiencing higher temperatures, as well as concentrations of nitrate, nitrite, and most importantly nitric acid, that exceed normal operating conditions. Accordingly, conditions may exist where nitration reactions involving the solvent components, possibly leading to other chemical reactions stemming from nitration reactions, could occur. To model such nitration reactions, the solvent was exposed to the types of nitrate- and nitrite-containing solutions that might be expected to be encountered during the process (even under off-normal conditions), as a function of time, temperature, and concentration of nitrate, nitrite, and nitric acid. The experiments conducted as part of this report were designed to examine the more specific effect that high nitrite concentrations could have on forming nitrated

  11. ELECTRONS IN NONPOLAR LIQUIDS.

    Energy Technology Data Exchange (ETDEWEB)

    HOLROYD,R.A.

    2002-10-22

    Excess electrons can be introduced into liquids by absorption of high energy radiation, by photoionization, or by photoinjection from metal surfaces. The electron's chemical and physical properties can then be measured, but this requires that the electrons remain free. That is, the liquid must be sufficiently free of electron attaching impurities for these studies. The drift mobility as well as other transport properties of the electron are discussed here as well as electron reactions, free-ion yields and energy levels, Ionization processes typically produce electrons with excess kinetic energy. In liquids during thermalization, where this excess energy is lost to bath molecules, the electrons travel some distance from their geminate positive ions. In general the electrons at this point are still within the coulombic field of their geminate ions and a large fraction of the electrons recombine. However, some electrons escape recombination and the yield that escapes to become free electrons and ions is termed G{sub fi}. Reported values of G{sub fi} for molecular liquids range from 0.05 to 1.1 per 100 eV of energy absorbed. The reasons for this 20-fold range of yields are discussed here.

  12. Kinetic solvent effects on hydrogen abstraction from phenol by the cumyloxyl radical. Toward an understanding of the role of protic solvents.

    Science.gov (United States)

    Bietti, Massimo; Salamone, Michela; DiLabio, Gino A; Jockusch, Steffen; Turro, Nicholas J

    2012-02-03

    A time-resolved kinetic study of the hydrogen atom abstraction reactions from phenol by the cumyloxyl radical (CumO(•)) was carried out in different solvents. The hydrogen atom abstraction rate constant (k(H)) was observed to decrease by almost 3 orders of magnitude on going from isooctane to MeOH. In TFE, MeCN/H(2)O 2:1, and MeOH, the measured k(H) values were lower than expected on the basis of the Snelgrove-Ingold (SI) equation that correlates log k(H) to the solvent hydrogen bond acceptor (HBA) ability parameter β(2)(H). As these solvents also act as hydrogen bond donors (HBDs), we explored the notion that a more thorough description of solvent effects could be provided by including a solvent HBD ability term, α(2)(H), into the SI equation via β(2)(H)(1 + α(2)(H)). The inclusion of such a term greatly improves the fitting for TFE, MeCN/H(2)O 2:1, and MeOH but at the expense of that for tertiary alkanols. This finding suggests that, for the reaction of CumO(•) with phenol, the HBA and HBD abilities of both the solvent and the substrate could be responsible for the observed KSEs. but this requires that primary and tertiary alkanols exhibit different solvation behaviors. Possible explanations for this different behavior are explored.

  13. Lipase catalyzed esterification of glycidol in nonaqueous solvents: solvent effects on enzymatic activity.

    Science.gov (United States)

    Martins, J F; de Sampaio, T C; de Carvalho, I B; Barreiros, S

    1994-06-05

    We studied the effect of organic solvents on the kinetics of porcine pancreatic lipase (pp) for the resolution of racemic glycidol through esterification with butyric acid. We quantified ppl hydration by measuring water sorption isotherms for the enzyme in the solvents/mixtures tested. The determination of initial rates as a function of enzyme hydration revealed that the enzyme exhibits maximum apparent activity in the solvents/mixtures at the same water content (9% to 11% w/w) within the associated experimental error. The maximum initial rates are different in all the media and correlate well with the logarithm of the molar solubility of water in the media, higher initial rates being observed in the solvents/mixtures with lower water solubilities. The data for the mixtures indicate that ppl apparent activity responds to bulk property of the solvent. Measurements of enzyme particle sizes in five of the solvents, as function of enzyme hydration, revealed that mean particle sizes increased with enzyme hydration in all the solvents, differences between solvents being more pronounced at enzyme hydration levels close to 10%. At this hydration level, solvents having a higher water content lead to lower reaction rates; these are the solvents where the mean enzyme particle sizes are greater. Calculation of the observable modulus indicates there are no internal diffusion limitations. The observed correlation between changes in initial rates and changes in external surface area of the enzyme particles suggests that interfacial activation of ppl is only effective at the external surface of the particles. Data obtained for the mixtures indicate that ppl enantioselectivity depends on specific solvent-enzyme interactions. We make reference to ppl hydration and activity in supercritical carbon dioxide.

  14. Solvent systems with n-hexane and/or cyclohexane in countercurrent chromatography--Physico-chemical parameters and their impact on the separation of alkyl hydroxybenzoates.

    Science.gov (United States)

    Englert, Michael; Vetter, Walter

    2014-05-16

    Countercurrent chromatography (CCC) is an efficient preparative separation technique based on the liquid-liquid distribution of compounds between two phases of a biphasic liquid system. The crucial parameter for the successful application is the selection of the solvent system. Especially for nonpolar analytes the selection options are limited. On the search for a suitable solvent system for the separation of an alkyl hydroxybenzoate homologous series, we noted that the substitution of cyclohexane with n-hexane was accompanied with unexpected differences in partitioning coefficients of the individual analytes. In this study, we investigated the influence of the subsequent substitution of n-hexane with cyclohexane in the n-hexane/cyclohexane/tert-butylmethylether/methanol/water solvent system family. Exact phase compositions and polarity, viscosity and density differences were determined to characterize the different mixtures containing n-hexane and/or cyclohexane. Findings were confirmed by performing CCC separations with different mixtures, which led to baseline resolution for positional isomers when increasing the amount of cyclohexane while the resolution between two pairs of structural isomers decreased. With the new methodology described, structurally similar compounds could be resolved by choosing a certain ratio of n-hexane to cyclohexane.

  15. Non-Hodgkin's lymphoma risk derived from exposure to organic solvents: a review of epidemiologic studies

    Directory of Open Access Journals (Sweden)

    Marco Antônio V. Rêgo

    Full Text Available The rate of non-Hodgkin's lymphomas (NHL has increased around the world during the last decades. Apart from the role of the human immunodeficiency virus (HIV infection in the development of NHL, exposure to chemical agents like phenoxyacetic pesticides, hair dyes, metal fumes and organic solvents are suspected to be involved. The present review evaluates the results of studies that directly or indirectly searched for an association between solvent exposure and NHL. The selected studies comprised those published from 1979 to 1997, designed to investigate risk factors for NHL, whether specifically looking for solvent exposure or for general risks in which solvent exposure could be included. In 25 of the 45 reviewed studies (55.5%, fifty-four statistically significant associations between NHL and solvent exposure related occupations or industries were reported. Statistical significance was more frequently shown in studies where solvent exposure was more accurately defined. In eighteen of such studies, 13 (72.2% defined or suggested organic solvents as possible risk factors for NHL.

  16. Properties of polylactide inks for solvent-cast printing of three-dimensional freeform microstructures.

    Science.gov (United States)

    Guo, Shuang-Zhuang; Heuzey, Marie-Claude; Therriault, Daniel

    2014-02-04

    Solvent-cast printing is a highly versatile microfabrication technique that can be used to construct various geometries such as filaments, towers, scaffolds, and freeform circular spirals by the robotic deposition of a polymer solution ink onto a moving stage. In this work, we have performed a comprehensive characterization of the solvent-cast printing process using polylactide (PLA) solutions by analyzing the flow behavior of the solutions, the solvent evaporation kinetics, and the effect of process-related parameters on the crystallization of the extruded filaments. Rotational rheometry at low to moderate shear rates showed a nearly Newtonian behavior of the PLA solutions, while capillary flow analysis based on process-related data indicated shear thinning at high shear rates. Solvent vaporization tests suggested that the internal diffusion of the solvent through the filaments controlled the solvent removal of the extrudates. Different kinds of three-dimensional (3D) structures including a layer-by-layer tower, nine-layer scaffold, and freeform spiral were fabricated, and a processing map was given to show the proper ranges of process-related parameters (i.e., polymer content, applied pressure, nozzle diameter, and robot velocity) for the different geometries. The results of differential scanning calorimetry revealed that slow solvent evaporation could increase the ability of PLA to complete its crystallization process during the filament drying stage. The method developed here offers a new perspective for manufacturing complex structures from polymer solutions and provides guidelines to optimize the various parameters for 3D geometry fabrication.

  17. Pretreatment of Lignocellulosic Biomass with Ionic Liquids and Ionic Liquid-Based Solvent Systems

    OpenAIRE

    Qidong Hou; Meiting Ju; Weizun Li; Le Liu; Yu Chen; Qian Yang

    2017-01-01

    Pretreatment is very important for the efficient production of value-added products from lignocellulosic biomass. However, traditional pretreatment methods have several disadvantages, including low efficiency and high pollution. This article gives an overview on the applications of ionic liquids (ILs) and IL-based solvent systems in the pretreatment of lignocellulosic biomass. It is divided into three parts: the first deals with the dissolution of biomass in ILs and IL-based solvent systems; ...

  18. Green analytical chemistry - the use of surfactants as a replacement of organic solvents in spectroscopy

    Science.gov (United States)

    Pharr, Daniel Y.

    2017-07-01

    This chapter gives an introduction to the many practical uses of surfactants in analytical chemistry in replacing organic solvents to achieve greener chemistry. Taking a holistic approach, it covers some background of surfactants as chemical solvents, their properties and as green chemicals, including their environmental effects. The achievements of green analytical chemistry with micellar systems are reviewed in all the major areas of analytical chemistry where these reagents have been found to be useful.

  19. Prediction of Corrosion of Alloys in Mixed-Solvent Environments

    Energy Technology Data Exchange (ETDEWEB)

    Anderko, Andrzej [OLI Systems Inc. Morris Plains (United States); Wang, Peiming [OLI Systems Inc. Morris Plains (United States); Young, Robert D. [OLI Systems Inc. Morris Plains (United States); Riemer, Douglas P. [OLI Systems Inc. Morris Plains (United States); McKenzie, Patrice [OLI Systems Inc. Morris Plains (United States); Lencka, Malgorzata M. [OLI Systems Inc. Morris Plains (United States); Babu, Sudarsanam Suresh [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Angelini, Peter [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2003-06-05

    Corrosion is much less predictable in organic or mixed-solvent environments than in aqueous process environments. As a result, US chemical companies face greater uncertainty when selecting process equipment materials to manufacture chemical products using organic or mixed solvents than when the process environments are only aqueous. Chemical companies handle this uncertainty by overdesigning the equipment (wasting money and energy), rather than by accepting increased risks of corrosion failure (personnel hazards and environmental releases). Therefore, it is important to develop simulation tools that would help the chemical process industries to understand and predict corrosion and to develop mitigation measures. To create such tools, we have developed models that predict (1) the chemical composition, speciation, phase equilibria, component activities and transport properties of the bulk (aqueous, nonaqueous or mixed) phase that is in contact with the metal; (2) the phase equilibria and component activities of the alloy phase(s) that may be subject to corrosion and (3) the interfacial phenomena that are responsible for corrosion at the metal/solution or passive film/solution interface. During the course of this project, we have completed the following: (1) Development of thermodynamic modules for calculating the activities of alloy components; (2) Development of software that generates stability diagrams for alloys in aqueous systems; these diagrams make it possible to predict the tendency of metals to corrode; (3) Development and extensive verification of a model for calculating speciation, phase equilibria and thermodynamic properties of mixed-solvent electrolyte systems; (4) Integration of the software for generating stability diagrams with the mixed-solvent electrolyte model, which makes it possible to generate stability diagrams for nonaqueous or mixed-solvent systems; (5) Development of a model for predicting diffusion coefficients in mixed-solvent electrolyte

  20. Cellulose solvent- and organic solvent-based lignocellulose fractionation enabled efficient sugar release from a variety of lignocellulosic feedstocks.

    Science.gov (United States)

    Sathitsuksanoh, Noppadon; Zhu, Zhiguang; Zhang, Y-H Percival

    2012-08-01

    Developing feedstock-independent biomass pretreatment would be vital to second generation biorefineries that would fully utilize diverse non-food lignocellulosic biomass resources, decrease transportation costs of low energy density feedstock, and conserve natural biodiversity. Cellulose solvent- and organic solvent-based lignocellulose fractionation (COSLIF) was applied to a variety of feedstocks, including Miscanthus, poplar, their mixture, bagasse, wheat straw, and rice straw. Although non-pretreated biomass samples exhibited a large variation in enzymatic digestibility, the COSLIF-pretreated biomass samples exhibited similar high enzymatic glucan digestibilities and fast hydrolysis rates. Glucan digestibilities of most pretreated feedstocks were ∼93% at five filter paper units per gram of glucan. The overall glucose and xylose yields for the Miscanthus:poplar mixture at a weight ratio of 1:2 were 93% and 85%, respectively. These results suggested that COSLIF could be regarded as a feedstock-independent pretreatment suitable for processing diverse feedstocks by adjusting pretreatment residence time only.