Enantioselective solvent-free Robinson annulation reactions

Indian Academy of Sciences (India)

Unknown

solvents to effect an asymmetric synthesis is an important step forward towards ... In continuation of our preliminary communication 2, we wish to ..... formation of chiral enamine 74 from the reaction of S-proline with pro-R carbonyl group.

Asymmetric Catalysis with Organic Azides and Diazo Compounds Initiated by Photoinduced Electron Transfer.

Science.gov (United States)

Huang, Xiaoqiang; Webster, Richard D; Harms, Klaus; Meggers, Eric

2016-09-28

Electron-acceptor-substituted aryl azides and α-diazo carboxylic esters are used as substrates for visible-light-activated asymmetric α-amination and α-alkylation, respectively, of 2-acyl imidazoles catalyzed by a chiral-at-metal rhodium-based Lewis acid in combination with a photoredox sensitizer. This novel proton- and redox-neutral method provides yields of up to 99% and excellent enantioselectivities of up to >99% ee with broad functional group compatibility. Mechanistic investigations suggest that an intermediate rhodium enolate complex acts as a reductive quencher to initiate a radical process with the aryl azides and α-diazo carboxylic esters serving as precursors for nitrogen and carbon-centered radicals, respectively. This is the first report on using aryl azides and α-diazo carboxylic esters as substrates for asymmetric catalysis under photoredox conditions. These reagents have the advantage that molecular nitrogen is the leaving group and sole byproduct in this reaction.

Asymmetric Radical Cyclopropanation of Alkenes with In Situ-Generated Donor-Substituted Diazo Reagents via Co(II)-Based Metalloradical Catalysis.

Science.gov (United States)

Wang, Yong; Wen, Xin; Cui, Xin; Wojtas, Lukasz; Zhang, X Peter

2017-01-25

Donor-substituted diazo reagents, generated in situ from sulfonyl hydrazones in the presence of base, can serve as suitable radical precursors for Co(II)-based metalloradical catalysis (MRC). The cobalt(II) complex of D 2 -symmetric chiral porphyrin [Co(3,5-Di t Bu-Xu(2'-Naph)Phyrin)] is an efficient metalloradical catalyst that is capable of activating different N-arylsulfonyl hydrazones for asymmetric radical cyclopropanation of a broad range of alkenes, affording the corresponding cyclopropanes in high yields with effective control of both diastereo- and enantioselectivity. This Co(II)-based metalloradical system represents the first catalytic protocol that can effectively utilize donor-type diazo reagents for asymmetric olefin cyclopropanation.

The Development of Multidimensional Analysis Tools for Asymmetric Catalysis and Beyond.

Science.gov (United States)

Sigman, Matthew S; Harper, Kaid C; Bess, Elizabeth N; Milo, Anat

2016-06-21

In most modern organic chemistry reports, including many of ours, reaction optimization schemes are typically presented to showcase how reaction conditions have been tailored to augment the reaction's yield and selectivity. In asymmetric catalysis, this often involves evaluation of catalyst, solvent, reagent, and, sometimes, substrate features. Such an article will then detail the process's scope, which mainly focuses on its successes and briefly outlines the "limitations". These limitations or poorer-performing substrates are occasionally the result of obvious, significant changes to structure (e.g., a Lewis basic group binds to a catalyst), but frequently, a satisfying explanation for inferior performance is not clear. This is one of several reasons such results are not often reported. These apparent outliers are also commonplace in the evaluation of catalyst structure, although most of this information is placed in the Supporting Information. These practices are unfortunate because results that appear at first glance to be peculiar or poor are considerably more interesting than ones that follow obvious or intuitive trends. In other words, all of the data from an optimization campaign contain relevant information about the reaction under study, and the "outliers" may be the most revealing. Realizing the power of outliers as an entry point to entirely new reaction development is not unusual. Nevertheless, the concept that no data should be wasted when considering the underlying phenomena controlling the observations of a given reaction is at the heart of the strategy we describe in this Account. The idea that one can concurrently optimize a reaction to expose the structural features that control its outcomes would represent a transformative addition to the arsenal of catalyst development and, ultimately, de novo design. Herein we outline the development of a recently initiated program in our lab that unites optimization with mechanistic interrogation by

Cooperative catalysis designing efficient catalysts for synthesis

CERN Document Server

Peters, René

2015-01-01

Written by experts in the field, this is a much-needed overview of the rapidly emerging field of cooperative catalysis. The authors focus on the design and development of novel high-performance catalysts for applications in organic synthesis (particularly asymmetric synthesis), covering a broad range of topics, from the latest progress in Lewis acid / Br?nsted base catalysis to e.g. metal-assisted organocatalysis, cooperative metal/enzyme catalysis, and cooperative catalysis in polymerization reactions and on solid surfaces. The chapters are classified according to the type of cooperating acti

Room Temperature Reactivity Of Silicon Nanocrystals With Solvents: The Case Of Ketone And Hydrogen Production From Secondary Alcohols: Catalysis?

KAUST Repository

El Demellawi, Jehad K.; Holt, Christopher; Abou-Hamad, Edy; Al-Talla, Zeyad; Saih, Youssef; Chaieb, Saharoui

2015-01-01

Although silicon nanoparticles dispersed in liquids are used in various applications ranging from bio-labeling to hydrogen production, their reactivities with their solvents and their catalytic properties re-main still unexplored. Here, we discovered that, because of their surface structures and mechanical strain, silicon nanoparticles react strongly with their solvents and may act as catalysts for the dehydrogenation, at room temperature, of secondary alcohols (e.g. isopropanol) to ketones and hydrogen. This catalytic reaction was followed by gas chromatography, pH measurements, mass spectroscopy and solidstate NMR. This discovery provides new understanding of the role played by silicon nanoparticles, and nanosilicon in general, in their stability in solvents in general as well as being candidates in catalysis.

Room Temperature Reactivity Of Silicon Nanocrystals With Solvents: The Case Of Ketone And Hydrogen Production From Secondary Alcohols: Catalysis?

KAUST Repository

El Demellawi, Jehad K.

2015-05-29

Although silicon nanoparticles dispersed in liquids are used in various applications ranging from bio-labeling to hydrogen production, their reactivities with their solvents and their catalytic properties re-main still unexplored. Here, we discovered that, because of their surface structures and mechanical strain, silicon nanoparticles react strongly with their solvents and may act as catalysts for the dehydrogenation, at room temperature, of secondary alcohols (e.g. isopropanol) to ketones and hydrogen. This catalytic reaction was followed by gas chromatography, pH measurements, mass spectroscopy and solidstate NMR. This discovery provides new understanding of the role played by silicon nanoparticles, and nanosilicon in general, in their stability in solvents in general as well as being candidates in catalysis.

Dynamics of solvent-free grafted nanoparticles

KAUST Repository

Chremos, Alexandros

2012-01-01

The diffusivity and structural relaxation characteristics of oligomer-grafted nanoparticles have been investigated with simulations of a previously proposed coarse-grained model at atmospheric pressure. Solvent-free, polymer-grafted nanoparticles as well as grafted nanoparticles in a melt were compared to a reference system of bare (ungrafted) particles in a melt. Whereas longer chains lead to a larger hydrodynamic radius and lower relative diffusivity for grafted particles in a melt, bulk solvent-free nanoparticles with longer chains have higher relative diffusivities than their short chain counterparts. Solvent-free nanoparticles with short chains undergo a glass transition as indicated by a vanishing diffusivity, diverging structural relaxation time and the formation of body-centered-cubic-like order. Nanoparticles with longer chains exhibit a more gradual increase in the structural relaxation time with decreasing temperature and concomitantly increasing particle volume fraction. The diffusivity of the long chain nanoparticles exhibits a minimum at an intermediate temperature and volume fraction where the polymer brushes of neighboring particles overlap, but must stretch to fill the interparticle space. © 2012 American Institute of Physics.

An efficient solvent-free synthesis of meso-substituted dipyrromethanes using SnCl2•2H2O catalysis

Directory of Open Access Journals (Sweden)

Kabeer Ahmed Shaikh

2012-07-01

Full Text Available Highly rapid and simple methodology has been developed for the quantitative synthesis of meso-substituted dipyrromethanes from lowest pyrrole/aldehyde ratio. The method was carried out by using SnCl2•2H2O as a catalyst under solvent free condition. The method is environmentally friendly, easy to workup, and gives excellent yield of the products.

ODC-Free Solvent Implementation Issues for Vulcanized Rubber and Bond Systems

Science.gov (United States)

Hodgson, James R.; McCool, Alex (Technical Monitor)

2001-01-01

Thiokol Propulsion has worked extensively to replace 1,1,1-trichloroethane (TCA) with ozone depleting chemicals (ODC)-free solvents for use in the manufacture of the Reusable Solid Rocket Motor (RSRM) for the Space Shuttle Program. As Thiokol has transitioned from sub-scale to full-scale testing and implementation of these new solvents, issues have been discovered which have required special attention. The original intent of Thiokol's solvent replacement strategy was to replace TCA with a single drop-in solvent for all equivalent applications. We have learned that a single candidate does not exist for replacing TCA. Solvent incompatibility with process materials has caused us to seek for niche solvents and/or processing changes that provide an ODC-free solution for special applications. This paper addresses some of the solvent incompatibilities, which have lead to processes changes and possible niche solvent usage. These incompatibilities were discovered during full-scale testing of ODC-free solvents and relate to vulcanized rubber and bond systems in the RSRM. Specifically, the following items are presented: (1) Cure effects of d-limonene based solvents on Silica Filled Ethylene Propylene Diene Monomer (SF-EPDM) rubber. During full-scale test operations, Thiokol discovered that d-limonene (terpene) based solvents inhibit the cure of EPDM rubber. Subsequent testing showed the same issue with Nitrile Butadiene Rubber (NBR). Also discussed are efforts to minimize uncured rubber exposure to solvents; and (2) Cured bond system sensitivity to ODC-free solvents. During full scale testing it was discovered that a natural rubber to steel vulcanized bond could degrade after prolonged exposure to ODC-free solvents. Follow on testing showed that low vapor pressure and residence time seemed to be most likely cause for failure.

Supported Ionic Liquid Phase (SILP) catalysis

DEFF Research Database (Denmark)

Riisager, Anders; Fehrmann, Rasmus; Haumann, Marco

2006-01-01

Applications of ionic liquids to replace conventional solvents in homogeneous transition-metal catalysis have increased significantly during the last decade. Biphasic ionic liquid/organic liquid systems offer advantages with regard to product separation, catalyst stability, and recycling...... but utilise in the case of fast chemical reactions only a small amount of expensive ionic liquid and catalyst. The novel Supported Ionic Liquid Phase (SILP) catalysis concept overcomes these drawbacks and allows the use of fixed-bed reactors for continuous reactions. In this Microreview the SILP catalysis...

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.

The ultrasound-assisted oxidative scission of monoenic fatty acids by ruthenium tetroxide catalysis: influence of the mixture of solvents.

Science.gov (United States)

Rup, Sandrine; Zimmermann, François; Meux, Eric; Schneider, Michel; Sindt, Michele; Oget, Nicolas

2009-02-01

Carboxylic acids and diacids were synthesized from monoenic fatty acids by using RuO4 catalysis, under ultrasonic irradiation, in various mixtures of solvents. Ultrasound associated with Aliquat 336 have promoted in water, the quantitative oxidative cleavage of the CH=CH bond of oleic acid. A design of experiment (DOE) shows that the optimal mixture of solvents (H2O/MeCN, ratio 1/1, 2.2% RuCl3/4.1 eq. NaIO4) gives 81% azelaic acid and 97% pelargonic acid. With the binary heterogeneous mixture H2O/AcOEt, the oxidation of the oleic acid leads to a third product, the alpha-dione 9,10-dioxostearic acid.

Solid Base Catalysis

CERN Document Server

Ono, Yoshio

2011-01-01

The importance of solid base catalysts has come to be recognized for their environmentally benign qualities, and much significant progress has been made over the past two decades in catalytic materials and solid base-catalyzed reactions. The book is focused on the solid base. Because of the advantages over liquid bases, the use of solid base catalysts in organic synthesis is expanding. Solid bases are easier to dispose than liquid bases, separation and recovery of products, catalysts and solvents are less difficult, and they are non-corrosive. Furthermore, base-catalyzed reactions can be performed without using solvents and even in the gas phase, opening up more possibilities for discovering novel reaction systems. Using numerous examples, the present volume describes the remarkable role solid base catalysis can play, given the ever increasing worldwide importance of "green" chemistry. The reader will obtain an overall view of solid base catalysis and gain insight into the versatility of the reactions to whic...

Asymmetric synthesis with microbes; Biseibutsu wo katsuyoshita kogaku kassei kagobutsu no koritsutekina gosei

Energy Technology Data Exchange (ETDEWEB)

Kondo, S. [Ritsumeikan Univ., Tokyo (Japan). Faculty of Science and Engineering

1996-02-01

Use of microbial enzymes have been widely extended as an effective means for asymmetric synthesis. However, the asymmetric selectivity often decreases due to competitive catalysis among plural enzymes in a microbe. The author has been studied development of methods for control of the stereo-selectivity using subtle difference of enzyme characteristics. When Michaelis constant (Km) differs between two enzymes, one enzyme of lower Km becomes active with decrease in concentration of substrate, expressing its stereo-selectivity. Reduction of {alpha}-ketoesters in water by bread yeast (Saccharomyces cerevisiae) yields products of S-configuration, whereas those of R-configuration are obtained in an organic solvent in the presence of small amount of water. This is because reaction field of the yeast is in water and because R-configuration enzyme of lower Km works for substrate whose concentration in water has decreased due to two phase partition of organic solvent and water system. Further, use of difference of decrease in enzyme activity by inhibitors in stereo-selective synthesis of {alpha}-hydroxyketones (I) from {alpha}-diketone and use of difference of thermal endurance in improvement of formation ratio among I, are also introduced. 6 refs., 3 figs., 2 tabs.

Solvent-free enzymatic synthesis of feruloylated structured lipids by the transesterification of ethyl ferulate with castor oil.

Science.gov (United States)

Sun, Shangde; Zhu, Sha; Bi, Yanlan

2014-09-01

A novel enzymatic route of feruloylated structured lipids synthesis by the transesterification of ethyl ferulate (EF) with castor oil, in solvent-free system, was investigated. The transesterification reactions were catalysed by Novozym 435, Lipozyme RMIM, and Lipozyme TLIM, among which Novozym 435 showed the best catalysis performance. Effects of feruloyl donors, reaction variables, and ethanol removal on the transesterification were also studied. High EF conversion (∼100%) was obtained under the following conditions: enzyme load 20% (w/w, relative to the weight of substrates), reaction temperature 90 °C, substrate molar ratio 1:1 (EF/castor oil), 72 h, vacuum pressure 10 mmHg, and 200 rpm. Under these conditions, the transesterification product consisted of 62.6% lipophilic feruloylated structured lipids and 37.3% hydrophilic feruloylated lipids. Copyright © 2014 Elsevier Ltd. All rights reserved.

Asymmetric catalysis in Brazil: development and potential for advancement of Brazilian chemical industry; Catalise assimetrica no Brasil: desenvolvimento e potencialidades para o avanco da industria quimica brasileira

Energy Technology Data Exchange (ETDEWEB)

Braga, Antonio Luiz, E-mail: braga.antonio@ufsc.br [Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil). Departamento de Quimica; Luedtke, Diogo Seibert; Schneider, Paulo Henrique [Universidade Federal do Rio Grande do Sul (UFRS), Porto Alegre, RS (Brazil). Instituto de Quimica; Andrade, Leandro Helgueira [Universidade de Sao Paulo (USP), SP (Brazil). Instituto de Quimica; Paixao, Marcio Weber [Universidade Federal de Sao Carlos (UFSCar), SP (Brazil). Departamento de Quimica

2013-07-01

The preparation of enantiomerically pure or enriched substances is of fundamental importance to pharmaceutical, food, agrochemical, and cosmetics industries and involves a growing market of hundreds of billions of dollars. However, most chemical processes used for their production are not environmentally friendly because in most cases, stoichiometric amounts of chiral inductors are used and substantial waste is produced. In this context, asymmetric catalysis has emerged as an efficient tool for the synthesis of enantiomerically enriched compounds using chiral catalysts. More specifically, considering the current scenario in the Brazilian chemical industry, especially that of pharmaceuticals, the immediate prospect for the use of synthetic routes developed in Brazil in an enantioselective fashion or even the discovery of new drugs is practically null. Currently, the industrial production of drugs in Brazil is primarily focused on the production of generic drugs and is basically supported by imports of intermediates from China and India. In order to change this panorama and move forward toward the gradual incorporation of genuinely Brazilian synthetic routes, strong incentive policies, especially those related to continuous funding, will be needed. These incentives could be a breakthrough once we establish several research groups working in the area of organic synthesis and on the development and application of chiral organocatalysts and ligands in asymmetric catalysis, thus contributing to boost the development of the Brazilian chemical industry. Considering these circumstances, Brazil can benefit from this opportunity because we have a wide biodiversity and a large pool of natural resources that can be used as starting materials for the production of new chiral catalysts and are creating competence in asymmetric catalysis and related areas. This may decisively contribute to the growth of chemistry in our country. (author)

Acid, silver, and solvent-free gold-catalyzed hydrophenoxylation of internal alkynes

Directory of Open Access Journals (Sweden)

Marcia E. Richard

2013-10-01

Full Text Available A range of arylgold compounds have been synthesized and investigated as single-component catalysts for the hydrophenoxylation of unactivated internal alkynes. Both carbene and phosphine-ligated compounds were screened as part of this work, and the most efficient catalysts contained either JohnPhos or IPr/SIPr. Phenols bearing either electron-withdrawing or electron-donating groups were efficiently added using these catalysts. No silver salts, acids, or solvents were needed for the catalysis, and either microwave or conventional heating afforded moderate to excellent yields of the vinyl ethers.

Numerical simulation of catalysis combustion inside micro free-piston engine

International Nuclear Information System (INIS)

Wang, Qian; Zhang, Di; Bai, Jin; He, Zhixia

2016-01-01

Highlights: • A modeling study is applied on methane HCCI process of micro power device. • Mathematical formulas are established to predict the combustion characteristics. • Impacts of catalysis on the combustion characteristics are analyzed respectively. • The catalyst can improve the work steadily and reliability of micro power device. - Abstract: In order to investigate the catalytic combustion characteristics concerning homogeneous charge compression ignition (HCCI) in micro power device, numerical simulations with a 3D computation model that coupled motion of free piston and fluid dynamics of methane–air mixture flow were carried out and detailed gas-phase and surface catalytic reaction mechanisms of methane–air mixture were applied to the catalytic reactions model, a series of mathematical formula are established to predict the characteristics of compression ignition condition, impacts of catalysis on temperature, pressure, work capacity and other factors were analyzed respectively. Simulation results reveal that catalytic combustion facilitates the improvement of energy conversion efficiency and extends the ignition limit of methane–air mixture obviously, the ignition timing is brought forward as well, while compression ratio decreases and ignition delay period shrinks significantly. Numerical results demonstrate that the existence of catalytic wall helped to restrain the peak combustion pressure and maximum rate of pressure rise contributing to the steadily and reliability of operation inside micro free-piston power device.

Free Energy, Enthalpy and Entropy from Implicit Solvent End-Point Simulations.

Science.gov (United States)

Fogolari, Federico; Corazza, Alessandra; Esposito, Gennaro

2018-01-01

Free energy is the key quantity to describe the thermodynamics of biological systems. In this perspective we consider the calculation of free energy, enthalpy and entropy from end-point molecular dynamics simulations. Since the enthalpy may be calculated as the ensemble average over equilibrated simulation snapshots the difficulties related to free energy calculation are ultimately related to the calculation of the entropy of the system and in particular of the solvent entropy. In the last two decades implicit solvent models have been used to circumvent the problem and to take into account solvent entropy implicitly in the solvation terms. More recently outstanding advancement in both implicit solvent models and in entropy calculations are making the goal of free energy estimation from end-point simulations more feasible than ever before. We review briefly the basic theory and discuss the advancements in light of practical applications.

Free Energy, Enthalpy and Entropy from Implicit Solvent End-Point Simulations

Directory of Open Access Journals (Sweden)

Federico Fogolari

2018-02-01

Full Text Available Free energy is the key quantity to describe the thermodynamics of biological systems. In this perspective we consider the calculation of free energy, enthalpy and entropy from end-point molecular dynamics simulations. Since the enthalpy may be calculated as the ensemble average over equilibrated simulation snapshots the difficulties related to free energy calculation are ultimately related to the calculation of the entropy of the system and in particular of the solvent entropy. In the last two decades implicit solvent models have been used to circumvent the problem and to take into account solvent entropy implicitly in the solvation terms. More recently outstanding advancement in both implicit solvent models and in entropy calculations are making the goal of free energy estimation from end-point simulations more feasible than ever before. We review briefly the basic theory and discuss the advancements in light of practical applications.

Structural Transitions of Solvent-Free Oligomer-Grafted Nanoparticles

KAUST Repository

Chremos, Alexandros

2011-09-01

Novel structural transitions of solvent-free oligomer-grafted nanoparticles are investigated by using molecular dynamics simulations of a coarse-grained bead-spring model. Variations in core size and grafting density lead to self-assembly of the nanoparticles into a variety of distinct structures. At the boundaries between different structures, the nanoparticle systems undergo thermoreversible transitions. This structural behavior, which has not been previously reported, deviates significantly from that of simple liquids. The reversible nature of these transitions in solvent-free conditions offers new ways to control self-assembly of nanoparticles at experimentally accessible conditions. © 2011 American Physical Society.

Catalysis in the Service of Green Chemistry: Nobel Prize-Winning Palladium-Catalysed Cross-Couplings, Run in Water at Room Temperature: Heck, Suzuki-Miyaura and Negishi reactions carried out in the absence of organic solvents, enabled by micellar catalysis.

Science.gov (United States)

Lipshutz, Bruce H; Taft, Benjamin R; Abela, Alexander R; Ghorai, Subir; Krasovskiy, Arkady; Duplais, Christophe

2012-04-01

Palladium-catalysed cross-couplings, in particular Heck, Suzuki-Miyaura and Negishi reactions developed over three decades ago, are routinely carried out in organic solvents. However, alternative media are currently of considerable interest given an increasing emphasis on making organic processes 'greener'; for example, by minimising organic waste in the form of organic solvents. Water is the obvious leading candidate in this regard. Hence, this review focuses on the application of micellar catalysis, in which a 'designer' surfactant enables these award-winning coupling reactions to be run in water at room temperature.

Green Michael addition of thiols to electron deficient alkenes using KF/alumina and recyclable solvent or solvent-free conditions

Energy Technology Data Exchange (ETDEWEB)

Lenardao, Eder J.; Trecha, Danusia O.; Ferreira, Patricia da C.; Jacob, Raquel G.; Perin, Gelson [Universidade Federal de Pelotas (UFPEL), Pelotas, RS (Brazil). Inst. de Quimica e Geociencias. Lab. de Sintese Organica Limpa (LASOL)]. E-mail: lenardao@ufpel.edu.br

2009-07-01

A general, clean and easy method for the conjugated addition of thiols to citral promoted by KF/Al{sub 2}O{sub 3} under solvent-free or using glycerin as recyclable solvent at room temperature is described. It was found that the solvent-free protocol is applicable to the direct reaction of thiophenol with the essential oil of lemon grass (Cymbopogon citratus) to afford directly 3,7-dimethyl-3-(phenylthio)oct-6-enal, a potential bactericide agent. The method was extended to other electron-poor alkenes with excellent results. For the solvent-free protocol, the use of microwave irradiation facilitated the procedure and accelerates the reaction. The catalytic system and glycerin can be reused up to three times without previous treatment with comparable activity. (author)

Cyclodextrins in Asymmetric and Stereospecific Synthesis

Directory of Open Access Journals (Sweden)

Fliur Macaev

2015-09-01

Full Text Available Since their discovery, cyclodextrins have widely been used as green and easily available alternatives to promoters or catalysts of different chemical reactions in water. This review covers the research and application of cyclodextrins and their derivatives in asymmetric and stereospecific syntheses, with their division into three main groups: (1 cyclodextrins promoting asymmetric and stereospecific catalysis in water; (2 cyclodextrins’ complexes with transition metals as asymmetric and stereospecific catalysts; and (3 cyclodextrins’ non-metallic derivatives as asymmetric and stereospecific catalysts. The scope of this review is to systematize existing information on the contribution of cyclodextrins to asymmetric and stereospecific synthesis and, thus, to facilitate further development in this direction.

Heterobimetallic transition metal/rare earth metal bifunctional catalysis: a Cu/Sm/Schiff base complex for syn-selective catalytic asymmetric nitro-Mannich reaction.

Science.gov (United States)

Handa, Shinya; Gnanadesikan, Vijay; Matsunaga, Shigeki; Shibasaki, Masakatsu

2010-04-07

The full details of a catalytic asymmetric syn-selective nitro-Mannich reaction promoted by heterobimetallic Cu/Sm/dinucleating Schiff base complexes are described, demonstrating the effectiveness of the heterobimetallic transition metal/rare earth metal bifunctional catalysis. The first-generation system prepared from Cu(OAc)(2)/Sm(O-iPr)(3)/Schiff base 1a = 1:1:1 with an achiral phenol additive was partially successful for achieving the syn-selective catalytic asymmetric nitro-Mannich reaction. The substrate scope and limitations of the first-generation system remained problematic. After mechanistic studies on the catalyst prepared from Sm(O-iPr)(3), we reoptimized the catalyst preparation method, and a catalyst derived from Sm(5)O(O-iPr)(13) showed broader substrate generality as well as higher reactivity and stereoselectivity compared to Sm(O-iPr)(3). The optimal system with Sm(5)O(O-iPr)(13) was applicable to various aromatic, heteroaromatic, and isomerizable aliphatic N-Boc imines, giving products in 66-99% ee and syn/anti = >20:1-13:1. Catalytic asymmetric synthesis of nemonapride is also demonstrated using the catalyst derived from Sm(5)O(O-iPr)(13).

GRINDING SOLVENT-FREE PAAL-KNORR PYRROLE SYNTHESIS ...

African Journals Online (AJOL)

Paal-Knorr pyrrole synthesis on smectites as recyclable and green catalysts. Bull. Chem. Soc. .... 1-Propyl-2,5-dimethyl-1H-pyrrole (8a). Oil (reported as oil .... of pyrroles catalyzed by zirconium chloride under solvent-free conditions . Ultrason.

SHORT COMMUNICATION SOLVENT FREE PREPARATION OF N ...

African Journals Online (AJOL)

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KEYWORDS: Solvent free, Maleanilic acids, Maleic anhydride, Aniline derivatives ... associated with the carboxylic group between 3275-2877 cm-1, the weak –NH .... Chemical shifts (σ/ppm) relative to TMS*. O-H N-H Ha. Hb. Hc. Hd. He. Hf.

Free-standing graphene/vanadium oxide composite as binder-free electrode for asymmetrical supercapacitor.

Science.gov (United States)

Deng, Lingjuan; Gao, Yihong; Ma, Zhanying; Fan, Guang

2017-11-01

Preparation of free-standing electrode materials with three-dimensional network architecture has emerged as an effective strategy for acquiring advanced portable and wearable power sources. Herein, graphene/vanadium oxide (GR/V 2 O 5 ) free-standing monolith composite has been prepared via a simple hydrothermal process. Flexible GR sheets acted as binder to connect the belt-like V 2 O 5 for assembling three-dimensional network architecture. The obtained GR/V 2 O 5 composite can be reshaped into GR/V 2 O 5 flexible film which exhibits more compact structure by ultrasonication and vacuum filtration. A high specific capacitance of 358Fg -1 for GR/V 2 O 5 monolith compared with that of GR/V 2 O 5 flexible film (272Fg -1 ) has been achieved in 0.5molL -1 K 2 SO 4 solution when used as binder free electrodes in three-electrode system. An asymmetrical supercapacitor has been assembled using GR/V 2 O 5 monolith as positive electrode and GR monolith as negative electrode, and it can be reversibly charged-discharged at a cell voltage of 1.7V in 0.5molL -1 K 2 SO 4 electrolyte. The asymmetrical capacitor can deliver an energy density of 26.22Whkg -1 at a power density of 425Wkg -1 , much higher than that of the symmetrical supercapacitor based on GR/V 2 O 5 monolith electrode. Moreover, the asymmetrical supercapacitor preserves 90% of its initial capacitance over 1000 cycles at a current density of 5Ag -1 . Copyright © 2017 Elsevier Inc. All rights reserved.

Solvent Free Preparation of p-Cymene from Limonene Using Vietnamese Montmorillonite

DEFF Research Database (Denmark)

Nguyen, Thao-Tran Thi; Duus, Fritz; Le, Thach Ngoc

2013-01-01

p-Cymene, an important intermediate in industrial chemistry, has been prepared in good yields by thermally induced dehydrogenation of limonene under solvent-free reaction conditions using Vietnamese montmorillonite as an efficient green catalyst.......p-Cymene, an important intermediate in industrial chemistry, has been prepared in good yields by thermally induced dehydrogenation of limonene under solvent-free reaction conditions using Vietnamese montmorillonite as an efficient green catalyst....

Structural Transitions of Solvent-Free Oligomer-Grafted Nanoparticles

KAUST Repository

Chremos, Alexandros; Panagiotopoulos, Athanassios Z.

2011-01-01

that of simple liquids. The reversible nature of these transitions in solvent-free conditions offers new ways to control self-assembly of nanoparticles at experimentally accessible conditions. © 2011 American Physical Society.

Microwave-assisted silica-promoted solvent-free synthesis of ...

Indian Academy of Sciences (India)

method using microwave irradiation with an excellent yield. The newly ... Table 1. Silica promoted microwave-assisted solvent-free synthesis of quinazolinone ... Time (min). Yield (%)a ..... thanks SC/ST cell of Bangalore University for research.

Solvent-free microwave extraction of essential oil from Melaleuca leucadendra L.

Directory of Open Access Journals (Sweden)

Widya Ismanto Aviarina

2018-01-01

Full Text Available Cajuput (Melaleuca leucadendra L. oil is one of potential commodity that provides an important role for the country’s foreign exchange but the extraction of these essential oil is still using conventional method such as hydrodistillation which takes a long time to produce essential oil with good quality. Therefore it is necessary to optimize the extraction process using a more effective and efficient method. So in this study the extraction is done using solvent-free microwave extraction method that are considered more effective and efficient than conventional methods. The optimum yield in the extraction of cajuput oil using solvent-free microwave extraction method is 1.0674%. The optimum yield is obtained on the feed to distiller (F/D ratio of 0.12 g/mL with microwave power of 400 W. In the extraction of cajuput oil using solvent-free microwave extraction method is performed first-order and second-order kinetics modelling. Based on kinetics modelling that has been done, it can be said that the second-order kinetic model (R2 = 0.9901 can be better represent experimental results of extraction of cajuput oil that using solvent-free microwave extraction method when compared with the first-order kinetic model (R2 = 0.9854.

Chiral ferrocenes in asymmetric catalysis: synthesis and applications

National Research Council Canada - National Science Library

Dai, Li-Xin; Hou, Xue-Long

2010-01-01

.... It provides a thorough overview of the synthesis and characterization of different types of chiral ferrocene ligands, their application to various catalytic asymmetric reactions, and versatile chiral...

Transition-Metal-Free Biomolecule-Based Flexible Asymmetric Supercapacitors.

Science.gov (United States)

Yang, Yun; Wang, Hua; Hao, Rui; Guo, Lin

2016-09-01

A transition-metal-free asymmetric supercapacitor (ASC) is successfully fabricated based on an earth-abundant biomass derived redox-active biomolecule, named lawsone. Such an ASC exhibits comparable or even higher energy densities than most of the recently reported transition-metal-based ASCs, and this green ASC generation from renewable resources is promising for addressing current issues of electronic hazard processing, high cost, and unsustainability. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Homogeneous Catalysis with Metal Complexes Fundamentals and Applications

CERN Document Server

Duca, Gheorghe

2012-01-01

The book about homogeneous catalysis with metal complexes deals with the description of the reductive-oxidative, metal complexes  in a liquid phase (in polar solvents, mainly in water, and less in nonpolar solvents). The exceptional importance of the redox processes in chemical systems, in the reactions occuring in living organisms, the environmental processes, atmosphere, water, soil, and in industrial technologies (especially in food-processing industries) is discussed. The detailed practical aspects of the established regularities are explained for solving the specific practical tasks in various fields of industrial chemistry, biochemistry, medicine, analytical chemistry and ecological chemistry. The main scope of the book is the survey and systematization of the latest advances in homogeneous catalysis with metal complexes. It gives an overview of the research results and practical experience accumulated by the author during the last decade.

Cosmic strings and baryon decay catalysis

Energy Technology Data Exchange (ETDEWEB)

Gregory, R.; Perkins, W.B.; Davis, A.C.; Brandenberger, R.H. (Fermi National Accelerator Lab., Batavia, IL (USA); Cambridge Univ. (UK); Brown Univ., Providence, RI (USA). Dept. of Physics)

1989-09-01

Cosmic strings, like monopoles, can catalyze proton decay. For integer charged fermions, the cross section for catalysis is not amplified, unlike in the case of monopoles. We review the catalysis processes both in the free quark and skyrmion pictures and discuss the implications for baryogenesis. We present a computation of the cross section for monopole catalyzed skyrmion decay using classical physics. We also discuss some effects which can screen catalysis processes. 32 refs., 1 fig.

Cosmic strings and baryon decay catalysis

International Nuclear Information System (INIS)

Gregory, R.; Perkins, W.B.; Davis, A.C.; Brandenberger, R.H.; Cambridge Univ.; Brown Univ., Providence, RI

1989-09-01

Cosmic strings, like monopoles, can catalyze proton decay. For integer charged fermions, the cross section for catalysis is not amplified, unlike in the case of monopoles. We review the catalysis processes both in the free quark and skyrmion pictures and discuss the implications for baryogenesis. We present a computation of the cross section for monopole catalyzed skyrmion decay using classical physics. We also discuss some effects which can screen catalysis processes. 32 refs., 1 fig

Surface functionalization of SBA-15 by the solvent-free method

International Nuclear Information System (INIS)

Wang Yimeng; Zheng Yingwu; Zhu Jianhua

2004-01-01

A solvent-free technique was employed for fast modification of mesoporous materials. Copper, chromium and iron oxide species could be highly dispersed in SBA-15 by manually grinding the corresponding precursor salts and the host, followed by calcinations for the first time. This method is more effective to spontaneously disperse oxide species onto SBA-15 than impregnation, probably forming monolayer or submonolayer dispersion of salts or oxides. Besides, Cr(VI) species dominate in the mixing sample while Cr(III) species dominate in the impregnation one. In the temperature programmed surface reaction of nitrosamines, the sample prepared by solvent-free method showed a higher catalytic activity than the impregnation one

Competing role of catalysis-coagulation and catalysis-fragmentation in kinetic aggregation behaviours

International Nuclear Information System (INIS)

Li Xiao-Dong; Lin Zhen-Quan; Song Mei-Xia; Ke Jian-Hong

2010-01-01

We propose a kinetic aggregation model where species A aggregates evolve by the catalysis-coagulation and the catalysis-fragmentation, while the catalyst aggregates of the same species B or C perform self-coagulation processes. By means of the generalized Smoluchowski rate equation based on the mean-field assumption, we study the kinetic behaviours of the system with the catalysis-coagulation rate kernel K(i,j;l) ∝ l ν and the catalysis-fragmentation rate kernel F(i,j;l) ∝ l μ , where l is the size of the catalyst aggregate, and ν and μ are two parameters reflecting the dependence of the catalysis reaction on the size of the catalyst aggregate. The relation between the values of parameters ν and μ reflects the competing roles between the two catalysis processes in the kinetic evolution of species A. It is found that the competing roles of the catalysis-coagulation and catalysis-fragmentation in the kinetic aggregation behaviours are not determined simply by the relation between the two parameters ν and μ, but also depend on the values of these two parameters. When ν > μ and ν ≥ 0, the kinetic evolution of species A is dominated by the catalysis-coagulation and its aggregate size distribution a k (t) obeys the conventional or generalized scaling law; when ν k (t) approaches the scale-free form; and in other cases, a balance is established between the two competing processes at large times and a k (t) obeys a modified scaling law. (cross-disciplinary physics and related areas of science and technology)

Liquid Quinones for Solvent-Free Redox Flow Batteries.

Science.gov (United States)

Shimizu, Akihiro; Takenaka, Keisuke; Handa, Naoyuki; Nokami, Toshiki; Itoh, Toshiyuki; Yoshida, Jun-Ichi

2017-11-01

Liquid benzoquinone and naphthoquinone having diethylene glycol monomethyl ether groups are designed and synthesized as redox active materials that dissolve supporting electrolytes. The Li-ion batteries based on the liquid quinones using LiBF 4 /PC show good performance in terms of voltage, capacity, energy efficiency, and cyclability in both static and flow modes. A battery is constructed without using intentionally added organic solvent, and its high energy density (264 W h L -1 ) demonstrates the potential of solvent-free organic redox flow batteries using liquid active materials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of solvent-free ambient mass spectrometry for green chemistry applications.

Science.gov (United States)

Liu, Pengyuan; Forni, Amanda; Chen, Hao

2014-04-15

Green chemistry minimizes chemical process hazards in many ways, including eliminating traditional solvents or using alternative recyclable solvents such as ionic liquids. This concept is now adopted in this study for monitoring solvent-free reactions and analysis of ionic liquids, solids, and catalysts by mass spectrometry (MS), without using any solvent. In our approach, probe electrospray ionization (PESI), an ambient ionization method, was employed for this purpose. Neat viscous room-temperature ionic liquids (RTILs) in trace amounts (e.g., 25 nL) could be directly analyzed without sample carryover effect, thereby enabling high-throughput analysis. With the probe being heated, it can also ionize ionic solid compounds such as organometallic complexes as well as a variety of neat neutral solid chemicals (e.g., amines). More importantly, moisture-sensitive samples (e.g., [bmim][AlCl4]) can be successfully ionized. Furthermore, detection of organometallic catalysts (including air-sensitive [Rh-MeDuPHOS][OTf]) in ionic liquids, a traditionally challenging task due to strong ion suppression effect from ionic liquids, can be enabled using PESI. In addition, PESI can be an ideal approach for monitoring solvent-free reactions. Using PESI-MS, we successfully examined the alkylation of amines by alcohols, the conversion of pyrylium into pyridinium, and the condensation of aldehydes with indoles as well as air- and moisture-sensitive reactions such as the oxidation of ferrocene and the condensation of pyrazoles with borohydride. Interestingly, besides the expected reaction products, the reaction intermediates such as the monopyrazolylborate ion were also observed, providing insightful information for reaction mechanisms. We believe that the presented solvent-free PESI-MS method would impact the green chemistry field.

Solvent-free, catalyst-free aza-Michael addition of cyclohexylamine to diethyl maleate: reaction mechanism and kinetics

Czech Academy of Sciences Publication Activity Database

Bláha, Michal; Trhlíková, Olga; Podešva, Jiří; Abbrent, Sabina; Steinhart, Miloš; Dybal, Jiří; Dušková-Smrčková, Miroslava

2018-01-01

Roč. 74, č. 1 (2018), s. 58-67 ISSN 0040-4020 Institutional support: RVO:61389013 Keywords : Aza-Michael addition * solvent-free * catalyst-free Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 2.651, year: 2016

A short model excitation of an asymmetric force free superconducting transmission line magnet

Energy Technology Data Exchange (ETDEWEB)

Wake, M.; Sato, H.; /KEK, Tsukuba; Carcagno, R.; Foster, W.; Hays, S.; Kashikhin, V.; Oleck, A.; Piekarz, H.; Rabehl, R,; /Fermilab

2005-09-01

A short model of asymmetric force free magnet with single beam aperture was tested at Fermilab together with the excitation test of VLHC transmission line magnet. The design concept of asymmetric force free superconducting magnet was verified by the test. The testing reached up to 104 kA current and no indication of force imbalance was observed. Since the model magnet length was only 10cm, A 0.75m model was constructed and tested at KEK with low current to ensure the validity of the design. The cool down and the excitation at KEK were also successful finding very small thermal contraction of the conductor and reasonable field homogeneity.

Predicting the activity coefficients of free-solvent for concentrated globular protein solutions using independently determined physical parameters.

Directory of Open Access Journals (Sweden)

Devin W McBride

Full Text Available The activity coefficient is largely considered an empirical parameter that was traditionally introduced to correct the non-ideality observed in thermodynamic systems such as osmotic pressure. Here, the activity coefficient of free-solvent is related to physically realistic parameters and a mathematical expression is developed to directly predict the activity coefficients of free-solvent, for aqueous protein solutions up to near-saturation concentrations. The model is based on the free-solvent model, which has previously been shown to provide excellent prediction of the osmotic pressure of concentrated and crowded globular proteins in aqueous solutions up to near-saturation concentrations. Thus, this model uses only the independently determined, physically realizable quantities: mole fraction, solvent accessible surface area, and ion binding, in its prediction. Predictions are presented for the activity coefficients of free-solvent for near-saturated protein solutions containing either bovine serum albumin or hemoglobin. As a verification step, the predictability of the model for the activity coefficient of sucrose solutions was evaluated. The predicted activity coefficients of free-solvent are compared to the calculated activity coefficients of free-solvent based on osmotic pressure data. It is observed that the predicted activity coefficients are increasingly dependent on the solute-solvent parameters as the protein concentration increases to near-saturation concentrations.

Asymmetric Baylis-Hillman Reaction between Chiral Activated Alkenes and Aromatic Aldehydes in Me3N/H2O/Solvent Medium

Institute of Scientific and Technical Information of China (English)

Ke HE; Zheng Hong ZHOU; Hong Ying TANG; Guo Feng ZHAO; Chu Chi TANG

2005-01-01

Chiral activated alkene, L-menthyl acrylate and (+)-N-α-phenylethyl acrylamide,induced asymmetric Baylis-Hillman reaction of aromatic aldehydes was realized at 25℃ for 7 days in Me3N/H2O/solvent homogeneous medium. The corresponding Baylis-Hillman adducts were obtained in good chemical yield with moderate to excellent diastereoselectivity (up to 99% de).

Ultrathin-skinned asymmetric membranes by immiscible solvents treatment

Science.gov (United States)

Friesen, Dwayne T.; Babcock, Walter C.

1989-01-01

Improved semipermeable asymmetric fluid separation membranes useful in gas, vapor and liquid separations are disclosed. The membranes are prepared by substantially filling the pores of asymmetric cellulosic semipermeable membranes having a finely porous layer on one side thereof with a water immiscible organic liquid, followed by contacting the finely porous layer with water.

Evaluation of commercial and sulfated ZrO_2 aiming application catalysis

International Nuclear Information System (INIS)

Silva, F.N.; Dantas, J.; Costa, A.C.F.M.; Pallone, E.M.J.A.; Dutra, R.C.L.

2014-01-01

This study evaluates the performance of commercial and sulfated ZrO_2 for future application in catalysis. Commercial ZrO_2 was provided by the company Saint-Gobain Zirpro. The sulfation occurred with SO_4"-"2 ion content of 30% compared to the mass of ZrO_2. The samples were characterized by XRD, FTIR, EDX and GD. The results revealed the formation of a monoclinic phase for the commercial sample, and a monoclinic major phase with tetragonal traces for the sulfated sample. The commercial ZrO_2 showed a narrow, bimodal and asymmetric agglomerates distribution, while the sulfated sample showed a narrow, tetramodal and asymmetric agglomerates distribution. The presence of traces of the tetragonal phase in the SO_4"-"2/ZrO_2 XRD, and the presence of SO_3 in the EDX were good indicators for future use in catalysis to provide ester. (author)

Solvent density inhomogeneities and solvation free energies in supercritical diatomic fluids: a density functional approach.

Science.gov (United States)

Husowitz, B; Talanquer, V

2007-02-07

Density functional theory is used to explore the solvation properties of a spherical solute immersed in a supercritical diatomic fluid. The solute is modeled as a hard core Yukawa particle surrounded by a diatomic Lennard-Jones fluid represented by two fused tangent spheres using an interaction site approximation. The authors' approach is particularly suitable for thoroughly exploring the effect of different interaction parameters, such as solute-solvent interaction strength and range, solvent-solvent long-range interactions, and particle size, on the local solvent structure and the solvation free energy under supercritical conditions. Their results indicate that the behavior of the local coordination number in homonuclear diatomic fluids follows trends similar to those reported in previous studies for monatomic fluids. The local density augmentation is particularly sensitive to changes in solute size and is affected to a lesser degree by variations in the solute-solvent interaction strength and range. The associated solvation free energies exhibit a nonmonotonous behavior as a function of density for systems with weak solute-solvent interactions. The authors' results suggest that solute-solvent interaction anisotropies have a major influence on the nature and extent of local solvent density inhomogeneities and on the value of the solvation free energies in supercritical solutions of heteronuclear molecules.

Biomass catalysis and solvents; Biomasse catalyse et solvants

Energy Technology Data Exchange (ETDEWEB)

Pioch, D [CIRAD-AMIS, programme Agro-Alimentaire, 34 - Montpellier (France); Pouilloux, Y; Barrault, J [Centre National de la Recherche Scientifique (CNRS UMR 6503), ESIP, Lab. de Catalyse en Chimie Organique, 86 - Poitiers (France); and others

2000-07-01

How to develop new technics and products and at the same time to respect the environment? The biomass seems to be an interesting domain in this framework and this document allows the selection of performing products obtain by biomass. Among these products the solvents economic and environmental advantages or consequences are discussed. A great part is also devoted to the voc emissions, bound to the solvents.

CO- and HCl-free synthesis of acid chlorides from unsaturated hydrocarbons via shuttle catalysis

Science.gov (United States)

Fang, Xianjie; Cacherat, Bastien; Morandi, Bill

2017-11-01

The synthesis of carboxylic acid derivatives from unsaturated hydrocarbons is an important process for the preparation of polymers, pharmaceuticals, cosmetics and agrochemicals. Despite its industrial relevance, the traditional Reppe-type carbonylation reaction using pressurized CO is of limited applicability to laboratory-scale synthesis because of: (1) the safety hazards associated with the use of CO, (2) the need for special equipment to handle pressurized gas, (3) the low reactivity of several relevant nucleophiles and (4) the necessity to employ different, often tailor-made, catalytic systems for each nucleophile. Herein we demonstrate that a shuttle-catalysis approach enables a CO- and HCl-free transfer process between an inexpensive reagent, butyryl chloride, and a wide range of unsaturated substrates to access the corresponding acid chlorides in good yields. This new transformation provides access to a broad range of carbonyl-containing products through the in situ transformation of the reactive acid chloride intermediate. In a broader context, this work demonstrates that isodesmic shuttle-catalysis reactions can unlock elusive catalytic reactions.

Solvent-free Oxidation of Alcohols and Mild Catalytic Deprotection of ...

African Journals Online (AJOL)

tetrabromobenzene- 1,3-disulphonamide (TBBDA) can be used for solvent-free oxidation of primary and secondary alcohols to the corresponding carbonyl compounds without over-oxidation, and efficient catalytic deprotection of various silyl ...

Grinding solvent-free Paal-Knorr pyrrole synthesis on smectites as ...

African Journals Online (AJOL)

Journal Home > Vol 32, No 1 (2018) > ... An environmentally benign method for the synthesis of N-substituted pyrroles from one-pot solvent-free ... conditions make this protocol practical, environmentally friendly and economically attractive.

Innovative polymeric system (IPS) for solvent-free lipophilic drug transdermal delivery via dissolving microneedles.

Science.gov (United States)

Dangol, Manita; Yang, Huisuk; Li, Cheng Guo; Lahiji, Shayan Fakhraei; Kim, Suyong; Ma, Yonghao; Jung, Hyungil

2016-02-10

Lipophilic drugs are potential drug candidates during drug development. However, due to the need for hazardous organic solvents for their solubilization, these drugs often fail to reach the pharmaceutical market, and in doing so highlight the importance of solvent free systems. Although transdermal drug delivery systems (TDDSs) are considered prospective safe drug delivery routes, a system involving lipophilic drugs in solvent free or powder form has not yet been described. Here, we report, for the first time, a novel approach for the delivery of every kind of lipophilic drug in powder form based on an innovative polymeric system (IPS). The phase transition of powder form of lipophilic drugs due to interior chemical bonds between drugs and biodegradable polymers and formation of nano-sized colloidal structures allowed the fabrication of dissolving microneedles (DMNs) to generate a powerful TDDS. We showed that IPS based DMN with powder capsaicin enhances the therapeutic effect for treatment of the rheumatic arthritis in a DBA/1 mouse model compared to a solvent-based system, indicating the promising potential of this new solvent-free platform for lipophilic drug delivery. Copyright © 2016 Elsevier B.V. All rights reserved.

Porous asymmetric SiO2-g-PMMA nanoparticles produced by phase inversion

KAUST Repository

Munirasu, Selvaraj

2014-07-22

A new kind of asymmetric organic-inorganic porous structure has been proposed. Asymmetric lattices of polymer grafted silica nanoparticles were manufactured by casting and phase inversion in water. Silica nanoparticles were first functionalized with 3-(dimethylethoxysilyl)propyl-2-bromoisobutyrate, followed by grafting of poly(methylmethacrylate) (PMMA) segments, performed by atom-transfer radical polymerization. Mechanically stable self-standing films were prepared by casting a dispersion of functionalized nanoparticles in different solvents and immersion in water. The resulting asymmetrically porous morphology and nanoparticle assembly was characterized by scanning electron and atomic force microscopy. The PMMA functionalized SiO2 hybrid material in acetone or acetone/dioxane led to the best-assembled structures. Porous asymmetric membranes were prepared by adding free PMMA and PMMA terminated with hydrophilic hydroxyl group. Nitrogen flow of 2800 L m-2 h -1 was measured at 1.3 bar demonstrating the porosity and potential application for membrane technology. © 2014 Springer Science+Business Media New York.

Heterogeneous Catalysis of Polyoxometalate Based Organic–Inorganic Hybrids

Directory of Open Access Journals (Sweden)

Yuanhang Ren

2015-03-01

Full Text Available Organic–inorganic hybrid polyoxometalate (POM compounds are a subset of materials with unique structures and physical/chemical properties. The combination of metal-organic coordination complexes with classical POMs not only provides a powerful way to gain multifarious new compounds but also affords a new method to modify and functionalize POMs. In parallel with the many reports on the synthesis and structure of new hybrid POM compounds, the application of these compounds for heterogeneous catalysis has also attracted considerable attention. The hybrid POM compounds show noteworthy catalytic performance in acid, oxidation, and even in asymmetric catalytic reactions. This review summarizes the design and synthesis of organic–inorganic hybrid POM compounds and particularly highlights their recent progress in heterogeneous catalysis.

Recyclable enantioselective catalysts based on copper(II) complexes of 2-(pyridine-2-yl)imidazolidine-4-thione: their application in asymmetric Henry reactions

Czech Academy of Sciences Publication Activity Database

Nováková, G.; Drabina, P.; Frumarová, Božena; Sedlák, M.

2016-01-01

Roč. 358, č. 15 (2016), s. 2541-2552 ISSN 1615-4150 Institutional support: RVO:61389013 Keywords : asymmetric catalysis * enantioselectivity * heterogeneous catalysis Subject RIV: CC - Organic Chemistry Impact factor: 5.646, year: 2016

Microwave-Assisted Solvent-Free Synthesis of Zeolitic Imidazolate Framework-67

Directory of Open Access Journals (Sweden)

Heng Zhang

2016-01-01

Full Text Available A microporous metal-organic framework (MOF, cobalt-based zeolitic imidazolate framework-67 (ZIF-67, was synthesized by the combination of solvent-free hand-mill and microwave irradiation, without any organic solvent and within 30 minutes. The hand-milling process can mix the reactants well by the virtue of high moisture/water absorption capacity of reactants. In addition, the outstanding electromagnetic wave absorption capability of cobalt leads to efficient conversion to MOF structures before carbonization. The obtained ZIF-67 possesses high surface area and micropore volume.

Build/Couple/Pair and Multifunctional Catalysis Strategies for the Synthesis of Heterocycles from Simple Starting Materials

DEFF Research Database (Denmark)

Ascic, Erhad

. Multifunctional Catalysis: Synthesis of Heterocycles from Simple Starting Materials A multifunctional catalysis approach, involving a ruthenium-catalyzed tandem ringclosing metathesis/isomerization/N-acyliminium cyclization sequence, is described. Double bonds created during ring-closing metathesis isomerize......, a series of interesting indolizidinones are formed in good yields with excellent diastereoselectivities, including a formal total synthesis of the antiparasitic natural product harmicine and the first total synthesis of mescalotam. Furthermore, preliminary asymmetric variants of the tandem process have...

An efficient synthesis of quinolines under solvent-free conditions

Indian Academy of Sciences (India)

Unknown

An efficient synthesis of quinolines under solvent-free conditions. 201 was then irradiated with microwaves in a microwave oven (Samsung model# CE118KF) at 1050W (70% of total power) for 5 minutes (3 + 2 with an inter- mission of 5 minutes). The reaction mixture was cooled at room temperature and rendered basic (pH.

Photo-triggered solvent-free metamorphosis of polymeric materials.

Science.gov (United States)

Honda, Satoshi; Toyota, Taro

2017-09-11

Liquefaction and solidification of materials are the most fundamental changes observed during thermal phase transitions, yet the design of organic and polymeric soft materials showing isothermal reversible liquid-nonliquid conversion remains challenging. Here, we demonstrate that solvent-free repeatable molecular architectural transformation between liquid-star and nonliquid-network polymers that relies on cleavage and reformation of a covalent bond in hexaarylbiimidazole. Liquid four-armed star-shaped poly(n-butyl acrylate) and poly(dimethyl siloxane) with 2,4,5-triphenylimidazole end groups were first synthesized. Subsequent oxidation of the 2,4,5-triphenylimidazoles into 2,4,5-triphenylimidazoryl radicals and their coupling with these liquid star polymers to form hexaarylbiimidazoles afforded the corresponding nonliquid network polymers. The resulting nonliquid network polymers liquefied upon UV irradiation and produced liquid star-shaped polymers with 2,4,5-triphenylimidazoryl radical end groups that reverted to nonliquid network polymers again by recoupling of the generated 2,4,5-triphenylimidazoryl radicals immediately after terminating UV irradiation.The design of organic and polymeric soft materials showing isothermal reversible liquid-nonliquid conversion is challenging. Here, the authors show solvent-free repeatable molecular architectural transformation between liquid-star and non-liquid-network polymers by the cleavage and reformation of covalent bonds in the polymer chain.

Pickering interfacial catalysis for biphasic systems: from emulsion design to green reactions.

Science.gov (United States)

Pera-Titus, Marc; Leclercq, Loïc; Clacens, Jean-Marc; De Campo, Floryan; Nardello-Rataj, Véronique

2015-02-09

Pickering emulsions are surfactant-free dispersions of two immiscible fluids that are kinetically stabilized by colloidal particles. For ecological reasons, these systems have undergone a resurgence of interest to mitigate the use of synthetic surfactants and solvents. Moreover, the use of colloidal particles as stabilizers provides emulsions with original properties compared to surfactant-stabilized emulsions, microemulsions, and micellar systems. Despite these specific advantages, the application of Pickering emulsions to catalysis has been rarely explored. This Minireview describes very recent examples of hybrid and composite amphiphilic materials for the design of interfacial catalysts in Pickering emulsions with special emphasis on their assets and challenges for industrially relevant biphasic reactions in fine chemistry, biofuel upgrading, and depollution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel Cinchona derived organocatalysts: new asymmetric transformations and catalysis

NARCIS (Netherlands)

Breman, A.C.

2014-01-01

Cinchona alkaloids have a long history as being a powerful medicine against malaria. Since a relative short period (about 50 years) chemist have also used these alkaloids as chiral catalyst for a wide variety of asymmetric transformations. Especially since the beginning of this century, when strong

Oligoquinolines under Solvent-free Microwave Irradiation

Energy Technology Data Exchange (ETDEWEB)

Park, Kwi-Jeon; Kwon, Tae-Woo [Kyungsung University, Busan (Korea, Republic of)

2015-01-15

Quinolines are thermally stable and can be used as an excellent n-type semiconducting materials. Since quinolines are also known to be electron acceptor molecules, combination of various electron donor building blocks can be utilized in photonic and electronic organic light-emitting diode (OLED) applications. For example, donor.acceptor systems with phenothiazine (or carbazole) molecules as electron donors and the phenylquinoline group as an electron acceptor provide an efficient approach for the design of new materials exhibiting highly efficient charge-transfer photophysics and electroluminescence in OLEDs. We have described the Friedlander quinoline synthesis between aminobenzophenones and symmetrical diacetyl compounds having phenothiazine, carbazole, biphenyl, and phenyl moieties under solvent-free microwave irradiation in 12.98% isolated yields.

Solvent-Free Wittig Reaction: A Green Organic Chemistry Laboratory Experiment

Science.gov (United States)

Leung, Sam H.; Angel, Stephen A.

2004-01-01

Some Wittig reactions can be carried out by grinding the reactants in a mortar with a pestle for about 20 minutes, as per investigation. A laboratory experiment involving a solvent-free Wittig reaction that can be completed in a three-hour sophomore organic chemistry laboratory class period, are developed.

Origin of Stereodivergence in Cooperative Asymmetric Catalysis with Simultaneous Involvement of Two Chiral Catalysts.

Science.gov (United States)

Bhaskararao, Bangaru; Sunoj, Raghavan B

2015-12-23

Accomplishing high diastereo- and enantioselectivities simultaneously is a persistent challenge in asymmetric catalysis. The use of two chiral catalysts in one-pot conditions might offer new avenues to this end. Chirality transfer from a catalyst to product gets increasingly complex due to potential chiral match-mismatch issues. The origin of high enantio- and diastereoselectivities in the reaction between a racemic aldehyde and an allyl alcohol, catalyzed by using axially chiral iridium phosphoramidites PR/S-Ir and cinchona amine is established through transition-state modeling. The multipoint contact analysis of the stereocontrolling transition state revealed how the stereodivergence could be achieved by inverting the configuration of the chiral catalysts that are involved in the activation of the reacting partners. While the enantiocontrol is identified as being decided in the generation of PR/S-Ir-π-allyl intermediate from the allyl alcohol, the diastereocontrol arises due to the differential stabilizations in the C-C bond formation transition states. The analysis of the weak interactions in the transition states responsible for chiral induction revealed that the geometric disposition of the quinoline ring at the C8 chiral carbon of cinchona-enamine plays an anchoring role. The quinolone ring is noted as participating in a π-stacking interaction with the phenyl ring of the Ir-π-allyl moiety in the case of PR with the (8R,9R)-cinchona catalyst combination, whereas a series of C-H···π interactions is identified as vital to the relative stabilization of the stereocontrolling transition states when PR is used with (8S,9S)-cinchona.

Preparation of Ultra-fine Calcium Carbonate by a Solvent-free ...

African Journals Online (AJOL)

The treatment of calcium chloride with sodium carbonate under solvent-free conditions with a supersonic airflow and at a low heating temperature leads to the synthesis of ultra-fine calcium carbonate. The reaction not only involves mild conditions, a simple operation, and high yields but also gives a high conversion rate.

Formation of defect-free 6FDA-DAM asymmetric hollow fiber membranes for gas separations

KAUST Repository

Xu, Liren; Zhang, Chen; Rungta, Meha; Qiu, Wulin; Liu, Junqiang; Koros, William J.

2014-01-01

This paper reports the formation of defect-free 6FDA-DAM asymmetric hollow fiber membranes. 6FDA-polyimides are of great interest for advanced gas separation membranes, and 6FDA-DAM polyimide is a representative polymer in this family

Synthesis and characterization of solvent-free ionic molybdenum disulphide (MoS2) nanofluids

International Nuclear Information System (INIS)

Gu, Shu-Ying; Gao, Xie-Feng; Zhang, Yi-Han

2015-01-01

A development of the novel and stable solvent-free ionic MoS 2 nanofluids by a facile and scalable hydrothermal method is presented. The nanofluids were synthesized by surface functionalizing nanoscale MoS 2 from hydrothermal synthesis with a charged corona, and ionically tethering with oligomeric chains as a canopy. The structures and properties of the nanofluids were characterized by Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR, 1 H), differential scanning calorimeter (DSC), thermogravimetric analysis (TGA) and ARES rheometer. The obtained solvent-free nanofluids are homogeneous, stable amber-like fluids with no evidence of phase separation. The nanofluids could be easily dispersed in both aqueous and organic solvents to form transparent and stable liquids due to the ionic nature and the presence of oligomeric polymer chains. It was found that the solvent-free nanofluids with up to 32 wt% inorganic content show Newtonian rheological behaviors due to the high graft density and uniform dispersion of inorganic cores, indicating that the nanofluids would have a stable lubricating performance. As reported in our previous communication, the nanofluids showing lower, more stable friction coefficients of less than 0.1 with self-healing lubricating behaviors. For deeper understanding of the nanofluids, the details of synthesis, chemical structures, rheological behaviors and molecular dynamics of the nanofluids were investigated in details. The rheological behaviors can be tailored by varying the grafting density of the canopy. Dynamic results of the canopy of the MoS 2 nanofluids show that inorganic MoS 2 cores have hindrance effect on the canopy segmental motions above 253 K due to their effect to the mobility of anions and the departing-recombining motions between the paired cations and anions. - Highlights: • A development of the novel synthesis of solvent-free MoS 2 nanofluids is presented. • The rheological behaviors can be tailored by

Solvent-free porous framework resulted from 3D entanglement of 1D zigzag coordination polymer

KAUST Repository

Kole, Goutam Kumar Umar; Cairns, Amy J.; Eddaoudi, Mohamed; Vittal, Jagadese J.

2010-01-01

A solvent-free porous metal organic framework is constructed by the 3D entanglement of 1D zigzag coordination polymeric chains. The role of solvents and the effect of reaction conditions on such unique entanglement are addressed. © 2010 The Royal

Molecular accessibility in solvent swelled coals. Final report

Energy Technology Data Exchange (ETDEWEB)

Kispert, L.D.

1994-04-01

The conversion of coal by an economically feasible catalytic method requires the catalyst to diffuse into the coal sample so that hydrogenation catalysis can occur from within as well as the normal surface catalysis. Thus an estimate of the size, shape, and reactivity, of the pores in the coal before and after the swelling with different solvents is needed so that an optimum sized catalyst will be used. This study characterizes the accessible area found in Argonne Premium Coal Samples (APCS) using a EPR spin probe technique. The properties deduced in this manner correlate well with the findings deduced from SANS, NMR, SEM, SAXS and light scattering measurements. The use of nitroxide spin probes with swelling solvents is a simple way in which to gain an understanding of the pore structure of coals, how it changes in the presence of swelling solvents and the chemistry that occurs at the pore wall. Hydrogen bonding sites occur primarily in low-rank coals and vary in reactive strength as rank is varied. Unswelled coals contain small, spherical pores which disappear when coal is swelled in the presence of polar solvents. Swelling studies of polystyrene-divinyl benzene copolymers implied that coal is polymeric, contains significant quantities of covalent cross-links and the covalent cross-link density increases with rank.

New chiral ligands in asymmetric catalysis. Application in stabilization of metal nanoparticles

OpenAIRE

Axet Martí, M. Rosa

2006-01-01

Thesis M. Rosa AxetThis thesis deals with the development and application of diphosphite ligands derived from carbohydrates to rhodium-catalysed asymmetric hydroformylation and hydrogenation reactions. The use of various carbohydrate derivative ligands as stabilisers of metal nanoparticles is also studied. The synthesis and the characterisation of the series of diphosphite ligands are described in Chapter 2. The results of the asymmetric hydroformylation of styrene and related vinyl arenes ar...

Microwave-assisted clean synthesis of amides via aza-wittig reaction under solvent-free condition

Energy Technology Data Exchange (ETDEWEB)

Sathishkumar, Murugan; Nagarajan, Sangaraiah; Velan, Poovan Shanmuga; Dinesh, Murugan; Ponnuswamy, Alagusundaram [Department of Organic Chemistry, School of Chemistry, Madurai Kamaraj University, Tamilnadu (India)

2011-09-15

A solvent-free microwave-assisted coupling of phosphazenes with acyl chlorides or carboxylic anhydrides in presence of triethylphosphite has been accomplished resulting in a clean synthesis of amides in good yields. Unlike the prevailing time-consuming solution phase methodologies employing chlorinated solvents, benzene (carcinogenic), etc, the present protocol is an eco friendly, rapid and simple approach. (author)

Multicomponent One-Pot Synthesis of Substituted Hantzsch Thiazole Derivatives Under Solvent Free Conditions

Directory of Open Access Journals (Sweden)

Bhaskar S. Dawane

2009-01-01

Full Text Available Thiazole derivatives were prepared by one-pot procedure by the reaction of α-haloketones, thiourea and substituted o-hydroxybenzaldehyde under environmentally solvent free conditions.

studies on solvent extraction of free hydrogen cyanide from river water

African Journals Online (AJOL)

A method for free and strongly complexed cyanide measurement in river water was developed. Recovery tests from solution with and without river water, using various solvent combinations and background control were investigated to obtain an accurate and precise extraction method for the measurement of hydrogen ...

Ester-free Thiol-X Resins: New Materials with Enhanced Mechanical Behavior and Solvent Resistance.

Science.gov (United States)

Podgórski, Maciej; Becka, Eftalda; Chatani, Shunsuke; Claudino, Mauro; Bowman, Christopher N

A series of thiol-Michael and radical thiol-ene network polymers were successfully prepared from ester-free as well as ester-containing monomer formulations. Polymerization reaction rates, dynamic mechanical analysis, and solvent resistance experiments were performed and compared between compositions with varied ester loading. The incorporation of ester-free alkyl thiol, vinyl sulfone and allylic monomers significantly improved the mechanical properties when compared with commercial, mercaptopropionate-based thiol-ene or thiol-Michael networks. For polymers with no hydrolytically degradable esters, glass transition temperatures (T g 's) as high as 100 °C were achieved. Importantly, solvent resistance tests demonstrated enhanced stability of ester-free formulations over PETMP-based polymers, especially in concentrated basic solutions. Kinetic analysis showed that glassy step-growth polymers are readily formed at ambient conditions with conversions reaching 80% and higher.

Predicting the Disorder–Order Transition of Solvent-Free Nanoparticle–Organic Hybrid Materials

KAUST Repository

Yu, Hsiu-Yu

2013-07-02

The transition from a disordered to a face-centered-cubic phase in solvent-free oligomer-tethered nanoparticles is predicted using a density-functional theory for model hard spheres with tethered bead-spring oligomers. The transition occurs without a difference of volume fraction for the two phases, and the phase boundary is influenced by the loss of oligomer configurational entropy relative to an ideal random system in one phase compared with the other. When the particles are localized in the ordered phase, the cooperation of the oligomers in filling the space is hindered. Therefore, shorter oligomers feel a stronger entropic penalty in the ordered solid and favor the disordered phase. Strikingly, we found that the solvent-free system has a later transition than hard spheres for all investigated ratios of oligomer radius of gyration to particle radius. © 2013 American Chemical Society.

An Expedient Method for the Synthesis of Thiosemicarbazones under Microwave Irradiation in Solvent-free Medium

Institute of Scientific and Technical Information of China (English)

LI, Jian-Ping; ZHENG, Peng-Zhi; ZHU, Jun-Ge; LIU, Rui-Jie; QU, Gui-Rong

2006-01-01

A simple, efficient and eco-friendly method for the synthesis of thiosemicarbazones from thiosemicarbazides and aldehyde under microwave irradiation has been reported, and no solvent and catalyst were used. And the technique of microwave irradiation coupled with solvent-free condition proved to be a quite valuable method in the organic synthesis.

Solvent-free porous framework resulted from 3D entanglement of 1D zigzag coordination polymer

KAUST Repository

Kole, Goutam Kumar Umar

2010-01-01

A solvent-free porous metal organic framework is constructed by the 3D entanglement of 1D zigzag coordination polymeric chains. The role of solvents and the effect of reaction conditions on such unique entanglement are addressed. © 2010 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

Catalyst-free and solvent-free Michael addition of 1,3-dicarbonyl compounds to nitroalkenes by a grinding method

Science.gov (United States)

Xie, Zong-Bo; Wu, Ming-Yu; He, Ting; Le, Zhang-Gao

2012-01-01

Summary An environmentally benign, fast and convenient protocol has been developed for the Michael addition of 1,3-dicarbonyl compounds to β-nitroalkenes in good to excellent yields by a grinding method under catalyst- and solvent-free conditions. PMID:22563352

Deuterium labelling of tryptamine, serotonin and their N-methylated metabolites using solvent exchange reactions

Energy Technology Data Exchange (ETDEWEB)

Raeisaenen, M; Kaerkkaeinen, J [Helsinki Univ. (Finland). Dept. of Medical Chemistry

1979-01-01

Technically uncomplicated methods based on catalytic isotope exchange in deuterated solvents are described for the deuteration of tryptamine, serotonin and their N-methylated metabolites. Heterogeneous platinum catalysis, homogeneous acid catalysis and their combination have been employed. The properties of the labelled derivatives prepared with each technique as well as their use in mass spectrometric work are discussed.

Deuterium labelling of tryptamine, serotonin and their N-methylated metabolites using solvent exchange reactions

International Nuclear Information System (INIS)

Raeisaenen, M.; Kaerkkaeinen, J.

1979-01-01

Technically uncomplicated methods based on catalytic isotope exchange in deuterated solvents are described for the deuteration of tryptamine, serotonin and their N-methylated metabolites. Heterogeneous platinum catalysis, homogeneous acid catalysis and their combination have been employed. The properties of the labelled derivatives prepared with each technique as well as their use in mass spectrometric work are discussed. (author)

Asymmetric synthesis II more methods and applications

CERN Document Server

Christmann, Mathias

2012-01-01

After the overwhelming success of 'Asymmetric Synthesis - The Essentials', narrating the colorful history of asymmetric synthesis, this is the second edition with latest subjects and authors. While the aim of the first edition was mainly to honor the achievements of the pioneers in asymmetric syntheses, the aim of this new edition was bringing the current developments, especially from younger colleagues, to the attention of students. The format of the book remained unchanged, i.e. short conceptual overviews by young leaders in their field including a short biography of the authors. The growing multidisciplinary research within chemistry is reflected in the selection of topics including metal catalysis, organocatalysis, physical organic chemistry, analytical chemistry, and its applications in total synthesis. The prospective reader of this book is a graduate or undergraduate student of advanced organic chemistry as well as the industrial chemist who wants to get a brief update on the current developments in th...

Predicting the Disorder–Order Transition of Solvent-Free Nanoparticle–Organic Hybrid Materials

KAUST Repository

Yu, Hsiu-Yu; Koch, Donald L.

2013-01-01

in the ordered phase, the cooperation of the oligomers in filling the space is hindered. Therefore, shorter oligomers feel a stronger entropic penalty in the ordered solid and favor the disordered phase. Strikingly, we found that the solvent-free system has a

The extraction of essential oil from patchouli leaves (Pogostemon cablin Benth) using microwave hydrodistillation and solvent-free microwave extraction methods

Science.gov (United States)

Putri, D. K. Y.; Kusuma, H. S.; Syahputra, M. E.; Parasandi, D.; Mahfud, M.

2017-12-01

Patchouli plant (Pogostemon cablin Benth) is one of the important essential oil-producing plant, contributes more than 50% of total exports of Indonesia’s essential oil. However, the extraction of patchouli oil that has been done in Indonesia is generally still used conventional methods that require enormous amount of energy, high solvent usage, and long time of extraction. Therefore, in this study, patchouli oil extraction was carried out by using microwave hydrodistillation and solvent-free microwave extraction methods. Based on this research, it is known that the extraction of patchouli oil using microwave hydrodistillation method with longer extraction time (240 min) only produced patchouli oil’s yield 1.2 times greater than solvent-free microwave extraction method which require faster extraction time (120 min). Otherwise the analysis of electric consumption and the environmental impact, the solvent-free microwave extraction method showed a smaller amount when compared with microwave hydrodistillation method. It is conclude that the use of solvent-free microwave extraction method for patchouli oil extraction is suitably method as a new green technique.

Development of Ar-BINMOL-Derived Atropisomeric Ligands with Matched Axial and sp(3) Central Chirality for Catalytic Asymmetric Transformations.

Science.gov (United States)

Xu, Zheng; Xu, Li-Wen

2015-10-01

Recently, academic chemists have renewed their interest in the development of 1,1'-binaphthalene-2,2'-diol (BINOL)-derived chiral ligands. Six years ago, a working hypothesis, that the chirality matching of hybrid chirality on a ligand could probably lead to high levels of stereoselective induction, prompted us to use the axial chirality of BINOL derivatives to generate new stereogenic centers within the same molecule with high stereoselectivity, obtaining as a result sterically favorable ligands for applications in asymmetric catalysis. This Personal Account describes our laboratory's efforts toward the development of a novel class of BINOL-derived atropisomers bearing both axial and sp(3) central chirality, the so-called Ar-BINMOLs, for asymmetric synthesis. Furthermore, on the basis of the successful application of Ar-BINMOLs and their derivatives in asymmetric catalysis, the search for highly efficient and enantioselective processes also compelled us to give special attention to the BINOL-derived multifunctional ligands with multiple stereogenic centers for use in catalytic asymmetric reactions. Copyright © 2015 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of a new solvent-free flow efficiency coating for natural gas pipelines

Energy Technology Data Exchange (ETDEWEB)

Fogg, Graham A.; Morse, Jennifer [Bredero Shaw, Houston, TX (United States)

2005-07-01

Pipeline design engineers have traditionally considered external anti-corrosion coatings for the protection of gas transmission pipelines, with less consideration given to the benefits of internal flow efficiency coatings. This paper reviews the benefits of using a traditional solvent-based flow efficiency coating, and the relationship between the internal surface roughness of a pipe, the pressure drop across the pipeline, and the maximum flow rate of gas through the pipeline. To improve upon existing solvent-based flow efficiency coatings, a research program was undertaken to develop a solvent-free coating. The stages in the development of this coating are discussed, resulting in the plant application of the coating and final qualification to API RP 5L2. (author)

Synthesis of halide- and solvent free metal borohydrides

DEFF Research Database (Denmark)

Grinderslev, Jakob; Møller, Kasper Trans; Richter, Bo

have challenges due to their high desorption kinetics and limited reversibility at moderate conditions.[2],[3],[4] In this work, we present a new approach to synthesize halide- and solvent free metal borohydrides starting from the respective metal hydride. The synthetic strategy ensures that no metal...... to the metal. Hence, the powdered M(BH4)3∙DMS is heated to 140 °C for 4 hours to obtain pure M(BH4)3. The rare-earth metal borohydrides have been investigated by infrared spectroscopy and thermal analysis (TGA-DSC-MS). Furthermore, the structural trends are investigated by synchrotron radiation powder X...

A Highly Efficient Solvent-Free Acetalization of Aldehydes to 1,1 ...

African Journals Online (AJOL)

1,1-Diacetates are prepared in excellent yields from aldehydes and acetic anhydride under solvent-free conditions at room temperature in short reaction times using catalytic amount of sulfonic acid functionalized silica (SiO2-Pr-SO3H) which could be easily handled and removed from the mixture of reaction. Keywords: 1 ...

A combined continuous microflow photochemistry and asymmetric organocatalysis approach for the enantioselective synthesis of tetrahydroquinolines

Directory of Open Access Journals (Sweden)

Erli Sugiono

2013-11-01

Full Text Available A continuous-flow asymmetric organocatalytic photocyclization–transfer hydrogenation cascade reaction has been developed. The new protocol allows the synthesis of tetrahydroquinolines from readily available 2-aminochalcones using a combination of photochemistry and asymmetric Brønsted acid catalysis. The photocylization and subsequent reduction was performed with catalytic amount of chiral BINOL derived phosphoric acid diester and Hantzsch dihydropyridine as hydrogen source providing the desired products in good yields and with excellent enantioselectivities.

Fe–Al/clay as an efficient heterogeneous catalyst for solvent-free ...

Indian Academy of Sciences (India)

SiO2,27 amberlyst-15,28 etc. ... tometer, using Ni-filtered Cu Ka (0.15418 nm) radia- ... The spectral data of some ... C).29 1H NMR ... 3.99(q, j = 7.1 Hz, 2H), 5.12 (s,1H), 7.23 (d, j = 8.35 .... Recyclability was studied in both solvent-free and.

Green catalysis by nanoparticulate catalysts developed for flow processing? case study of glucose hydrogenation

NARCIS (Netherlands)

Gericke, D.; Ott-Reinhardt, D.; Matveeva, V.; Sulman, E.M.; Aho, A.; Murzin, D.Y.; Roggan, S.; Danilova, L.; Hessel, V.; Löb, P.; Kralisch, D.

2015-01-01

Heterogeneous catalysis, flow chemistry, continuous processing, green solvents, catalyst immobilization and recycling are some of the most relevant, emerging key technologies to achieve green synthesis. However, a quantification of potential effects on a case to case level is required to provide a

Comparison of microwave hydrodistillation and solvent-free microwave extraction of essential oil from Melaleuca leucadendra Linn

Science.gov (United States)

Ismanto, A. W.; Kusuma, H. S.; Mahfud, M.

2017-12-01

The comparison of solvent-free microwave extraction (SFME) and microwave hydrodistillation (MHD) in the extraction of essential oil from Melaleuca leucadendra Linn. was examined. Dry cajuput leaves were used in this study. The purpose of this study is also to determine optimal condition (microwave power). The relative electric consumption of SFME and MHD methods are both showing 0,1627 kWh/g and 0,3279 kWh/g. The results showed that solvent-free microwave extraction methods able to reduce energy consumption and can be regarded as a green technique for extraction of cajuput oil.

Changing the Mechanism for CO ₂ Hydrogenation Using Solvent-Dependent Thermodynamics

Energy Technology Data Exchange (ETDEWEB)

Burgess, Samantha A. [Catalysis Science Group, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Appel, Aaron M. [Catalysis Science Group, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Linehan, John C. [Catalysis Science Group, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Wiedner, Eric S. [Catalysis Science Group, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA

2017-10-23

A critical scientific challenge for utilization of CO2 is the development of catalyst systems that do not depend upon expensive or environmentally unfriendly reagents, such as precious metals, strong organic bases, and organic solvents. We have used thermodynamic insights to predict and demonstrate that the HCoI(dmpe)2 catalyst system, previously described for use in organic solvents, can hydrogenate CO2 to formate in water with bicarbonate as the only added reagent. Replacing tetrahydrofuran as the solvent with water changes the mechanism for catalysis by altering the thermodynamics for hydride transfer to CO2 from a key dihydride intermediate. The need for a strong organic base was eliminated by performing catalysis in water due to the change in mechanism. These studies demonstrate that the solvent plays a pivotal role in determining the reaction thermodynamics and thereby catalytic mechanism and activity. The research was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

Synthesis and characterization of solvent-free ionic molybdenum disulphide (MoS{sub 2}) nanofluids

Energy Technology Data Exchange (ETDEWEB)

Gu, Shu-Ying, E-mail: gushuying@tongji.edu.cn [School of Materials Science and Engineering, Tongji University, Shanghai 201804 (China); Key Laboratory of Advanced Civil Engineering Materials, Ministry of Education, School of Materials Science and Engineering, Tongji University, Shanghai 201804 (China); Gao, Xie-Feng; Zhang, Yi-Han [School of Materials Science and Engineering, Tongji University, Shanghai 201804 (China)

2015-01-15

A development of the novel and stable solvent-free ionic MoS{sub 2} nanofluids by a facile and scalable hydrothermal method is presented. The nanofluids were synthesized by surface functionalizing nanoscale MoS{sub 2} from hydrothermal synthesis with a charged corona, and ionically tethering with oligomeric chains as a canopy. The structures and properties of the nanofluids were characterized by Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR, {sup 1}H), differential scanning calorimeter (DSC), thermogravimetric analysis (TGA) and ARES rheometer. The obtained solvent-free nanofluids are homogeneous, stable amber-like fluids with no evidence of phase separation. The nanofluids could be easily dispersed in both aqueous and organic solvents to form transparent and stable liquids due to the ionic nature and the presence of oligomeric polymer chains. It was found that the solvent-free nanofluids with up to 32 wt% inorganic content show Newtonian rheological behaviors due to the high graft density and uniform dispersion of inorganic cores, indicating that the nanofluids would have a stable lubricating performance. As reported in our previous communication, the nanofluids showing lower, more stable friction coefficients of less than 0.1 with self-healing lubricating behaviors. For deeper understanding of the nanofluids, the details of synthesis, chemical structures, rheological behaviors and molecular dynamics of the nanofluids were investigated in details. The rheological behaviors can be tailored by varying the grafting density of the canopy. Dynamic results of the canopy of the MoS{sub 2} nanofluids show that inorganic MoS{sub 2} cores have hindrance effect on the canopy segmental motions above 253 K due to their effect to the mobility of anions and the departing-recombining motions between the paired cations and anions. - Highlights: • A development of the novel synthesis of solvent-free MoS{sub 2} nanofluids is presented. • The rheological

Metal nanoparticles in liquid phase catalysis; from recent advances to future goals.

Science.gov (United States)

Zahmakıran, Mehmet; Ozkar, Saim

2011-09-01

Metal nanoparticles have attracted much attention over the last decade owing to their unique properties, different to their bulk counterparts, which pave the way for their application in different fields from materials science and engineering to biomedical applications. Of particular interest, the use of metal nanoparticles in catalysis has brought superior efficiency in terms of activity, selectivity and lifetime to heterogeneous catalysis. This article reviews the recent developments in the synthesis routes and the catalytic performance of metal nanoparticles depending on the solvent used for various organic and inorganic transformations. Additionally, we also discuss the prevalent complications and their possible solutions plus future prospects in the field of nanocatalysis.

Effects of Extraction Solvents on the Quantification of Free Amino Acids in Lyophilised Brewer’s Yeast

Directory of Open Access Journals (Sweden)

Andreea STĂNILĂ

2018-05-01

Full Text Available The aim of this work was to test some solvents in order to improve the free amino acids extraction from lyophilised brewer’s yeast. The brewer’ yeast was treated with four types of extraction solvents: Solvent I – acetonitrile 25%/HCl 0.01M (ACN; Solvent II – ethanol 80%; solvent III – HCl 0.05M/deionized water (1/1 volume; Solvent IV – HCl 0.05M/ethanol 80% (1/1 volume. The supernatants were analysed by HPLC-DAD-ESI-MS method. Acetonitrile provided the less quantities and number of amino acids extracted due to its weaker polarity. Solvent II and IV (ethanol, respectively acidified ethanol, which have an increased polarity, extracted 15 amino acids due to the addition of HCl in solvent IV. Solvent III (acidified water proved to be the best extraction solvent for the amino acids from brewer’s yeast providing the separation of 17 compounds: GLN, ASN, SER, GLY, ALA, ORN, PRO, HIS, LYS, GLU, TRP, LEU, PHE, ILE, AAA, HPHE, TYR.

Asymmetric split-ring resonator-based biosensor for detection of label-free stress biomarkers

Science.gov (United States)

Lee, Hee-Jo; Lee, Jung-Hyun; Choi, Suji; Jang, Ik-Soon; Choi, Jong-Soon; Jung, Hyo-Il

2013-07-01

In this paper, an asymmetric split-ring resonator, metamaterial element, is presented as a biosensing transducer for detection of highly sensitive and label-free stress biomarkers. In particular, the two biomarkers, cortisol and α-amylase, are used for evaluating the sensitivity of the proposed biosensor. In case of cortisol detection, the competitive reaction between cortisol-bovine serum albumin and free cortisol is employed, while alpha-amylase is directly detected by its antigen-antibody reaction. From the experimental results, we find that the limit of detection and sensitivity of the proposed sensing device are about 1 ng/ml and 1.155 MHz/ng ml-1, respectively.

Solvent-free synthesis of nanosized hierarchical sodalite zeolite with a multi-hollow polycrystalline structure

KAUST Repository

Zeng, Shangjing; Wang, Runwei; Li, Ang; Huang, Weiwei; Zhang, Zongtao; Qiu, Shilun

2016-01-01

A solvent-free route is developed for preparing nanoscale sodalite zeolite with a multi-hollow structure. Furthermore, the synthesis of nanosized hollow sodalite polycrystalline aggregates with a mesoporous structure and high crystallinity

Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling in a Green Alcohol Solvent for an Undergraduate Organic Chemistry Laboratory

Science.gov (United States)

Hie, Liana; Chang, Jonah J.; Garg, Neil K.

2015-01-01

A modern undergraduate organic chemistry laboratory experiment involving the Suzuki-Miyaura coupling is reported. Although Suzuki-Miyaura couplings typically employ palladium catalysts in environmentally harmful solvents, this experiment features the use of inexpensive nickel catalysis, in addition to a "green" alcohol solvent. The…

Efficient synthesis of sulfonamide derivatives on solid supports catalyzed using solvent-free and microwave-assisted methods

Energy Technology Data Exchange (ETDEWEB)

Camargo-Ordonez, Argelia; Moreno-Reyes, Christian; Olazaran-Santibanez, Fabian; Martinez-Hernandez, Sheila; Bocanegra-Garcia, Virgilio; Rivera, Gildardo [Universidad Autonoma de Tamaulipas, Reynosa (Mexico). Dep. de Farmacia y Quimica Medicinal

2011-07-01

In this work we report the synthesis of sulfonamide derivatives using a conventional procedure and with solid supports, such as silica gel, florisil, alumina, 4A molecular sieves, montmorillonite KSF, and montmorillonite K10 using solvent-free and microwave-assisted methods. Our results show that solid supports have a catalytic activity in the formation of sulfonamide derivatives. We found that florisil, montmorillonite KSF, and K10 could be used as inexpensive alternative catalysts that are easily separated from the reaction media. Additionally, solvent-free and microwave-assisted methods were more efficient in reducing reaction time and in increasing yield. (author)

Efficient synthesis of sulfonamide derivatives on solid supports catalyzed using solvent-free and microwave-assisted methods

International Nuclear Information System (INIS)

Camargo-Ordonez, Argelia; Moreno-Reyes, Christian; Olazaran-Santibanez, Fabian; Martinez-Hernandez, Sheila; Bocanegra-Garcia, Virgilio; Rivera, Gildardo

2011-01-01

In this work we report the synthesis of sulfonamide derivatives using a conventional procedure and with solid supports, such as silica gel, florisil, alumina, 4A molecular sieves, montmorillonite KSF, and montmorillonite K10 using solvent-free and microwave-assisted methods. Our results show that solid supports have a catalytic activity in the formation of sulfonamide derivatives. We found that florisil, montmorillonite KSF, and K10 could be used as inexpensive alternative catalysts that are easily separated from the reaction media. Additionally, solvent-free and microwave-assisted methods were more efficient in reducing reaction time and in increasing yield. (author)

Antimicrobial nanocapsules: from new solvent-free process to in vitro efficiency

Directory of Open Access Journals (Sweden)

Steelandt J

2014-09-01

Full Text Available Julie Steelandt,1 Damien Salmon,1,2 Elodie Gilbert,1 Eyad Almouazen,3 François NR Renaud,4 Laurène Roussel,1 Marek Haftek,5 Fabrice Pirot1,2 1University Claude Bernard Lyon 1, Faculty of Pharmacy, Fundamental, Clinical and Therapeutic Aspects of Skin Barrier Function, FRIPharm, Laboratoire de Pharmacie Galénique Industrielle, 2Hospital Pharmacy, FRIPharm, Hospital Edouard Herriot, Hospices Civils de Lyon, 3Laboratoire d’Automatique et de Génie des Procédés, University Claude Bernard Lyon 1, 4University Claude Bernard Lyon 1, UMR CNRS 5510/MATEIS, 5University Claude Bernard Lyon 1, Faculty of Pharmacy, Fundamental, Clinical and Therapeutic Aspects of Skin Barrier Function, FRIPharm, Laboratoire de Dermatologie, Lyon, France Abstract: Skin and mucosal infections constitute recurrent pathologies resulting from either inappropriate antiseptic procedures or a lack of efficacy of antimicrobial products. In this field, nanomaterials offer interesting antimicrobial properties (eg, long-lasting activity; intracellular and tissular penetration as compared to conventional products. The aim of this work was to produce, by a new solvent-free process, a stable and easily freeze-dryable chlorhexidine-loaded polymeric nanocapsule (CHX-NC suspension, and then to assess the antimicrobial properties of nanomaterials. The relevance of the process and the physicochemical properties of the CHX-NCs were examined by the assessment of encapsulation efficiency, stability of the nanomaterial suspension after 1 month of storage, and by analysis of granulometry and surface electric charge of nanocapsules. In vitro antimicrobial activities of the CHX-NCs and chlorhexidine digluconate solution were compared by measuring the inhibition diameters of two bacterial strains (Escherichia coli and Staphylococcus aureus and one fungal strain (Candida albicans cultured onto appropriate media. Based on the findings of this study, we report a new solvent-free process for the

Modeling Loop Reorganization Free Energies of Acetylcholinesterase: A Comparison of Explicit and Implicit Solvent Models

National Research Council Canada - National Science Library

Olson, Mark

2004-01-01

... screening of charge-charge interactions. This paper compares different solvent models applied to the problem of estimating the free-energy difference between two loop conformations in acetylcholinesterase...

Tuning of Activated Carbon for Solvent-Free Oxidation of Cyclohexane

Directory of Open Access Journals (Sweden)

Mohammad Sadiq

2017-01-01

Full Text Available Activated carbon (AC was prepared from carbonization of phosphoric acid soaked peanut shell at 380°C under inert atmosphere followed by activation with hydrogen peroxide. The AC was characterized by SEM, EDX, FTIR, TGA, and BET surface area and pore size analyzer. The potential of AC as a catalyst for solvent-free oxidation of cyclohexane to cyclohexanol and cyclohexanone (the mixture is known as KA oil in the presence of molecular oxygen at moderate temperature was investigated in a self-designed double-walled three-necked batch reactor. The effect of different reaction parameters/additive was optimized. The maximum productivity value (2.14 mmolg−1 h−1, without base, and 4.85 mmolg−1 h−1, with 0.2 mmol NaOH of the desired product was achieved under optimal reaction parameters: vol 12.5 mL, cat 0.4 g, time 14 h, oxygen flow 40 mL/min (pO2 760 Torr, stirring 1100 rpm, and temp 75°C. The AC shows recyclability for multiple runs without any significant loss in activity. Thus, the AC can be an efficient catalyst, due to low cost, ease of synthesis, easy recovery, nonleaching, and recyclability for multiple uses for the solvent-free oxidation of cyclohexane.

Ester-free Thiol-X Resins: New Materials with Enhanced Mechanical Behavior and Solvent Resistance

OpenAIRE

Podgórski, Maciej; Becka, Eftalda; Chatani, Shunsuke; Claudino, Mauro; Bowman, Christopher N.

2015-01-01

A series of thiol-Michael and radical thiol-ene network polymers were successfully prepared from ester-free as well as ester-containing monomer formulations. Polymerization reaction rates, dynamic mechanical analysis, and solvent resistance experiments were performed and compared between compositions with varied ester loading. The incorporation of ester-free alkyl thiol, vinyl sulfone and allylic monomers significantly improved the mechanical properties when compared with commercial, mercapto...

Ultrasound-assisted phase-transfer catalysis method in an aqueous medium to promote the Knoevenagel reaction: advantages over the conventional and microwave-assisted solvent-free/catalyst-free method.

Science.gov (United States)

De-la-Torre, Pedro; Osorio, Edison; Alzate-Morales, Jans H; Caballero, Julio; Trilleras, Jorge; Astudillo-Saavedra, Luis; Brito, Iván; Cárdenas, Alejandro; Quiroga, Jairo; Gutiérrez, Margarita

2014-09-01

Given the broad spectrum of uses of acrylonitrile derivatives as fluorescent probes, AChE inhibitors, and others, it is necessary to find easy, efficient and simple methods to synthesize and diversify these compounds. We report the results of a comparative study of the effects of three techniques on the reactions between heterocyclic aldehydes and 2-(benzo[d]thiazol-2-yl)acetonitrile: stirring; ultrasound coupled to PTC conditions (US-PTC); and MW irradiation (MWI) under solvent and catalyst-free conditions. The effects of conditions on reaction parameters were evaluated and compared in terms of reaction time, yield, purity and outcomes. The US-PTC method is more efficient than the MWI and conventional methods. The reaction times were considerably shorter, with high yields (>90%) and good levels of purity. In addition, X-ray diffraction analysis and quantum mechanical calculations, at the level of density functional theory (DFT), ratify obtaining acrylonitrile isomers with E configurations. The crystal structure of 3c is stabilized by weak C-Ho⋯N intermolecular interactions (Ho⋯NC=2.45 Å, Co⋯NC=3.348(3) Å, Ho⋯NC=162°), forming centrosymmetric ring R2(2) (20) along the crystallographic a axis. Copyright © 2014 Elsevier B.V. All rights reserved.

Effects of Solvent and Temperature on Free Radical Formation in Electronic Cigarette Aerosols.

Science.gov (United States)

Bitzer, Zachary T; Goel, Reema; Reilly, Samantha M; Foulds, Jonathan; Muscat, Joshua; Elias, Ryan J; Richie, John P

2018-01-16

The ever-evolving market of electronic cigarettes (e-cigarettes) presents a challenge for analyzing and characterizing the harmful products they can produce. Earlier we reported that e-cigarette aerosols can deliver high levels of reactive free radicals; however, there are few data characterizing the production of these potentially harmful oxidants. Thus, we have performed a detailed analysis of the different parameters affecting the production of free radical by e-cigarettes. Using a temperature-controlled e-cigarette device and a novel mechanism for reliably simulating e-cigarette usage conditions, including coil activation and puff flow, we analyzed the effects of temperature, wattage, and e-liquid solvent composition of propylene glycol (PG) and glycerol (GLY) on radical production. Free radicals in e-cigarette aerosols were spin-trapped and analyzed using electron paramagnetic resonance. Free radical production increased in a temperature-dependent manner, showing a nearly 2-fold increase between 100 and 300 °C under constant-temperature conditions. Free radical production under constant wattage showed an even greater increase when going from 10 to 50 W due, in part, to higher coil temperatures compared to constant-temperature conditions. The e-liquid PG content also heavily influenced free radical production, showing a nearly 3-fold increase upon comparison of ratios of 0:100 (PG:GLY) and 100:0 (PG:GLY). Increases in PG content were also associated with increases in aerosol-induced oxidation of biologically relevant lipids. These results demonstrate that the production of reactive free radicals in e-cigarette aerosols is highly solvent dependent and increases with an increase in temperature. Radical production was somewhat dependent on aerosol production at higher temperatures; however, disproportionately high levels of free radicals were observed at ≥100 °C despite limited aerosol production. Overall, these findings suggest that e-cigarettes can be

Advances in catalysis

CERN Document Server

Gates, Bruce C

2012-01-01

Advances in Catalysis fills the gap between the journal papers and the textbooks across the diverse areas of catalysis research. For more than 60 years Advances in Catalysis has been dedicated to recording progress in the field of catalysis and providing the scientific community with comprehensive and authoritative reviews. This series in invaluable to chemical engineers, physical chemists, biochemists, researchers and industrial chemists working in the fields of catalysis and materials chemistry. * In-depth, critical, state-of-the-art reviews * Comprehensive, covers of all as

Catalysis as a foundational pillar of green chemistry

Energy Technology Data Exchange (ETDEWEB)

Anastas, Paul T. [White House Office of Science and Technology Policy, Department of Chemistry, University of Nottingham Nottingham, (United Kingdom); Kirchhoff, Mary M. [U.S. Environmental Protection Agency and Trinity College, Washington, DC (United States); Williamson, Tracy C. [U.S. Environmental Protection Agency, Washington, DC (United States)

2001-11-30

Catalysis is one of the fundamental pillars of green chemistry, the design of chemical products and processes that reduce or eliminate the use and generation of hazardous substances. The design and application of new catalysts and catalytic systems are simultaneously achieving the dual goals of environmental protection and economic benefit. Green chemistry, the design of chemical products and processes that reduce or eliminate the use and generation of hazardous substances, is an overarching approach that is applicable to all aspects of chemistry. From feedstocks to solvents, to synthesis and processing, green chemistry actively seeks ways to produce materials in a way that is more benign to human health and the environment. The current emphasis on green chemistry reflects a shift away from the historic 'command-and-control' approach to environmental problems that mandated waste treatment and control and clean up through regulation, and toward preventing pollution at its source. Rather than accepting waste generation and disposal as unavoidable, green chemistry seeks new technologies that are cleaner and economically competitive. Utilizing green chemistry for pollution prevention demonstrates the power and beauty of chemistry: through careful design, society can enjoy the products on which we depend while benefiting the environment. The economic benefits of green chemistry are central drivers in its advancement. Industry is adopting green chemistry methodologies because they improve the corporate bottom line. A wide array of operating costs are decreased through the use of green chemistry. When less waste is generated, environmental compliance costs go down. Treatment and disposal become unnecessary when waste is eliminated. Decreased solvent usage and fewer processing steps lessen the material and energy costs of manufacturing and increase material efficiency. The environmental, human health, and the economic advantages realized through green chemistry

Asymmetric Organocatalysis and Photoredox Catalysis for the α-Functionalization of Tetrahydroisoquinolines

KAUST Repository

Hou, Hong

2018-03-14

The asymmetric α‐alkylation of tetrahydroisoquinolines with cyclic ketones has been accomplished in the presence of a combined catalytic system consisting of a visible‐light photoredox catalyst and a chiral primary amine organocatalyst. The desired products were obtained in good yields, high enantioselectivity, and good to excellent diastereoselectivity. (PC: photoredox cycle, EN: enamine cycle).

Asymmetric Organocatalysis and Photoredox Catalysis for the α-Functionalization of Tetrahydroisoquinolines

KAUST Repository

Hou, Hong; Zhu, Shaoqun; Atodiresei, Iuliana; Rueping, Magnus

2018-01-01

The asymmetric α‐alkylation of tetrahydroisoquinolines with cyclic ketones has been accomplished in the presence of a combined catalytic system consisting of a visible‐light photoredox catalyst and a chiral primary amine organocatalyst. The desired products were obtained in good yields, high enantioselectivity, and good to excellent diastereoselectivity. (PC: photoredox cycle, EN: enamine cycle).

Solvent-free preparation of co-crystals of phenazine and acridine with vanillin

Energy Technology Data Exchange (ETDEWEB)

Braga, Dario, E-mail: dario.braga@unibo.it [Dipartimento di Chimica ' G.Ciamician' , Universita degli studi di Bologna, Via Selmi 2, 40126 Bologna (Italy); Grepioni, Fabrizia; Maini, Lucia; Mazzeo, Paolo P.; Rubini, Katia [Dipartimento di Chimica ' G.Ciamician' , Universita degli studi di Bologna, Via Selmi 2, 40126 Bologna (Italy)

2010-08-10

Co-crystals of phenazine and acridine with vanillin have been obtained by solvent-free reaction or thermal treatment of the solid reactants: their structures, thermal behaviour and eutectic formation have been investigated via single crystal X-ray diffraction, differential scanning calorimetry (DSC), variable temperature X-ray powder diffraction and hot-stage microscopy (HSM). Polymorph screening of the reagents has also been carried out.

Solvent-free preparation of co-crystals of phenazine and acridine with vanillin

International Nuclear Information System (INIS)

Braga, Dario; Grepioni, Fabrizia; Maini, Lucia; Mazzeo, Paolo P.; Rubini, Katia

2010-01-01

Co-crystals of phenazine and acridine with vanillin have been obtained by solvent-free reaction or thermal treatment of the solid reactants: their structures, thermal behaviour and eutectic formation have been investigated via single crystal X-ray diffraction, differential scanning calorimetry (DSC), variable temperature X-ray powder diffraction and hot-stage microscopy (HSM). Polymorph screening of the reagents has also been carried out.

Solvent-free ZnO dye-sensitised solar cells

Energy Technology Data Exchange (ETDEWEB)

Guillen, E.; Anta, J.A. [Departamento de Sistemas Fisicos, Quimicos y Naturales, Universidad Pablo de Olavide, 41013 Sevilla (Spain); Fernandez-Lorenzo, C.; Alcantara, R.; Martin-Calleja, J. [Departamento de Quimica Fisica, Universidad de Cadiz, Cadiz (Spain)

2009-10-15

Dye-sensitised solar cells (DSSC) based on commercial nanostructured zinc oxide combined with imidazolium-based room temperature ionic-liquid electrolytes are characterized. The electrolytes are based on a binary mixture of two ionic liquids, one of them used as source of iodide ions. The composition of this solvent-free electrolyte is optimized with respect to the concentration of iodine and iodide and the effect of additives such as lithium and tert-butylpyridine (TBP) on the photovoltaic performance and the recombination rate is analyzed and discussed. A maximum photoconversion efficiency of 3.4% at 1 sun illumination has been obtained for cells of 0.64 cm{sup 2} active area with the best performing compositions. Diffusion limitations due to slow transport processes are analyzed and discussed. (author)

Minimum detection efficiencies for a loophole-free observable-asymmetric Bell-type test

International Nuclear Information System (INIS)

Garbarino, G.

2010-01-01

We discuss the problem of finding the most favorable conditions for closing the detection loophole in a test of local realism with a Bell inequality. For a generic nonmaximally entangled two-qubit state and two incompatible bases to be adopted for alternative measurements of two observables a and b on each party, we apply Hardy's proof of nonlocality without inequality and derive an Eberhard-like inequality. For an infinity of nonmaximally entangled states we find that it is possible to refute local realism by requiring perfect detection efficiency for only one of the two observables, say b, to be measured on each party: The test is free from the detection loophole for any value of the detection efficiency corresponding to the other observable a. The maximum tolerable noise in such a loophole-free observable-asymmetric test is also evaluated.

Solvent-Free Synthesis of Aryl Iodide Using Nano SiO2/HIO4 as a Reusable Acid Catalyst

Directory of Open Access Journals (Sweden)

A. Bamoniri

2014-07-01

Full Text Available An efficient and environmentally benign   method for the synthesis of aryl iodides have been developed by diazotization of aromatic amines with NaNO2 and nanosilica periodic acid (nano-SPIA as a green catalyst via grinding followed by a sandmeyer iodination by KI under solvent-free conditions at room temperature. The ensuing aryl diazonium salts supported on nano-SPIA were sufficiently stable to be kept at room temperature in the dry state. This method is a novel, efficient, eco-friendly route for solvent-free synthesis of aryl iodides.

Theory of solvent effects on the hyperfine splitting constants in ESR spectra of free radicals

International Nuclear Information System (INIS)

Abe, T.; Tero-Kubota, S.; Ikegami, Y.

1982-01-01

An expression for the effects of solvation and hydrogen bonding on the hyperfine splitting constants of a free radical has been derived by obtaining π-electron spin densities of the radical in solution by perturbation theory. When no hydrogen bonding occurs between the radical and a solvent molecule, the splitting constant is approximately proportional to the Block and Walker parameter of theta(epsilon/sub r/) identical with 3 epsilon/sub r/ (ln epsilon/sub r/)/(epsilon/sub r/ ln epsilon/sub r/ - epsilon/sub r/ + 1) - 6/(ln epsilon/sub r/) - 2, where epsilon/sub r/ is the relative permittivity of the solvent. The expression is successfully applied to the di-tert-butyl nitroxide radical, the 1-methyl-4-(methoxycarbonyl)pyridinyl radical, and other free radicals. The effects of hydrogen bonding are discussed

Extremely efficient catalysis of carbon-carbon bond formation using "click" dendrimer-stabilized palladium nanoparticles.

Science.gov (United States)

Astruc, Didier; Ornelas, Cátia; Diallo, Abdou K; Ruiz, Jaime

2010-07-20

This article is an account of the work carried out in the authors' laboratory illustrating the usefulness of dendrimer design for nanoparticle palladium catalysis. The "click" synthesis of dendrimers constructed generation by generation by 1-->3 C connectivity, introduces 1,2,3-triazolyl ligands insides the dendrimers at each generation. Complexation of the ligands by Pd(II) followed by reduction to Pd(0) forms dendrimer-stabilized Pd nanoparticles (PdNPs) that are extremely reactive in the catalysis of olefin hydrogenation and C-C bond coupling reactions. The stabilization can be outer-dendritic for the small zeroth-generation dendrimer or intra-dendritic for the larger first- and second-generation dendrimers. The example of the Miyaura-Suzuki reaction that can be catalyzed by down to 1 ppm of PdNPs with a "homeopathic" mechanism (the less, the better) is illustrated here, including catalysis in aqueous solvents.

A Diazonium Salt-Based Ionic Liquid for Solvent-FreeModification of Carbon.

Energy Technology Data Exchange (ETDEWEB)

Liang, Chengdu [ORNL; Huang, Jing-Fang [ORNL; Li, Zuojiang [ORNL; Luo, Huimin [ORNL; Dai, Sheng [ORNL

2006-01-01

A novel ionic liquid that consists of p-butylbenzenediazonium ions and bis(trifluoromethanesulfonyl)amidates (Tf{sub 2}N{sup -}) has been synthesized as a task-specific ionic liquid for the solvent-free modification of carbon materials. The use of anions Tf{sub 2}N{sup =} is the key to rendering the hydrophobicity, low liquidus temperature, and ionicity to this novel molten salt. This diazonium salt has a melting point of 7.2 C and a moderate electric conductivity of 527 {micro} s/cm at 25 C. The thermal stability of this diazonium ionic liquid has been investigated by high-resolution thermogravimetric analysis (HRTGA). The compound is stable up to about 90 C in nitrogen, which is only 10 C less than its solid tetrafluoroborate counterpart. The modification of carbon materials has been carried out through both thermal and electrochemical activations of diazonium ions to generate free radical intermediates without the use of any solvent. The surface-coverage loadings of 3.38 {micro} mol/m{sup 2} and 6.07 {micro} mol/m{sup 2} for covalently attached organic functionalities have been achieved by the thermally induced functionalization and electrochemically assisted reaction, respectively.

Silica Gel-Mediated Organic Reactions under Organic Solvent-Free Conditions

Directory of Open Access Journals (Sweden)

Satoaki Onitsuka

2012-09-01

Full Text Available Silica gel was found to be an excellent medium for some useful organic transformations under organic solvent-free conditions, such as (1 the Friedel-Crafts-type nitration of arenes using commercial aqueous 69% nitric acid alone at room temperature, (2 one-pot Wittig-type olefination of aldehydes with activated organic halides in the presence of tributyl- or triphenylphosphine and Hunig’s base, and (3 the Morita-Baylis-Hillman reaction of aldehydes with methyl acrylate. After the reactions, the desired products were easily obtained in good to excellent yields through simple manipulation.

Solvent free low-melt viscosity imide oligomers and thermosetting polymide composites

Science.gov (United States)

Chuang, Chun-Hua (Inventor)

2012-01-01

.[.This invention relates to the composition and a solvent-free process for preparing novel imide oligomers and polymers specifically formulated with effective amounts of a dianhydride such as 2,3,3',4-biphenyltetra carboxylic dianydride (a-BPDA), at least one aromatic diamine and an endcapped of 4-phenylethynylphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260-280.degree. C. When the imide oligomer melt is cured at about 371.degree. C. in a press or autoclave under 100-500 psi, the melt resulted in a thermoset polyimide having a glass transition temperature (T.sub.g) equal to and above 310.degree. C. A novel feature of this process is that the monomers; namely the dianhydrides, diamines and the endcaps, are melt processable to form imide oligomers at temperatures ranging between 232-280.degree. C. (450-535.degree. F.) without any solvent. These low-melt imide oligomers can be easily processed by resin transfer molding (RTM), vacuum-assisted resin transfer molding (VARTM) or the resin infusion process with fiber preforms e.g. carbon, glass or quartz preforms to produce polyimide matrix composites with 288-343.degree. C. (550-650.degree. F.) high temperature performance capability..]. .Iadd.This invention relates to compositions and a solvent-free reaction process for preparing imide oligomers and polymers specifically derived from effective amounts of dianhydrides such as 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), at least one aromatic polyamine and an end-cap such as 4-phenylethynyphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260.degree. C.-280.degree. C..Iaddend.

Magnetic catalysis and inverse magnetic catalysis in QCD

International Nuclear Information System (INIS)

Mueller, N.

2015-01-01

We investigate the effects of strong magnetic fields on the QCD phase structure at vanishing density by solving the gluon and quark gap equations. The chiral crossover temperature as well as the chiral condensate is computed. For asymptotically large magnetic fields we find magnetic catalysis, while we find inverse magnetic catalysis for intermediate magnetic fields. Moreover, for large magnetic fields the chiral phase transition for massless quarks turns into a crossover. The underlying mechanisms are then investigated analytically within a few simplifications of the full numerical analysis. We find that a combination of gluon screening effects and the weakening of the strong coupling is responsible for the phenomenon of inverse catalysis seen in lattice studies. In turn, the magnetic catalysis at large magnetic field is already indicated by simple arguments based on dimensionality. (author)

Small-Molecule Organic Photovoltaic Modules Fabricated via Halogen-Free Solvent System with Roll-to-Roll Compatible Scalable Printing Method.

Science.gov (United States)

Heo, Youn-Jung; Jung, Yen-Sook; Hwang, Kyeongil; Kim, Jueng-Eun; Yeo, Jun-Seok; Lee, Sehyun; Jeon, Ye-Jin; Lee, Donmin; Kim, Dong-Yu

2017-11-15

For the first time, the photovoltaic modules composed of small molecule were successfully fabricated by using roll-to-roll compatible printing techniques. In this study, blend films of small molecules, BTR and PC 71 BM were slot-die coated using a halogen-free solvent system. As a result, high efficiencies of 7.46% and 6.56% were achieved from time-consuming solvent vapor annealing (SVA) treatment and roll-to-roll compatible solvent additive approaches, respectively. After successful verification of our roll-to-roll compatible method on small-area devices, we further fabricated large-area photovoltaic modules with a total active area of 10 cm 2 , achieving a power conversion efficiency (PCE) of 4.83%. This demonstration of large-area photovoltaic modules through roll-to-roll compatible printing methods, even based on a halogen-free solvent, suggests the great potential for the industrial-scale production of organic solar cells (OSCs).

Solvent-free synthesis of nanosized hierarchical sodalite zeolite with a multi-hollow polycrystalline structure

KAUST Repository

Zeng, Shangjing

2016-08-03

A solvent-free route is developed for preparing nanoscale sodalite zeolite with a multi-hollow structure. Furthermore, the synthesis of nanosized hollow sodalite polycrystalline aggregates with a mesoporous structure and high crystallinity is investigated by adding an organosilane surfactant as a mesopore-generating agent.

An Efficient, Mild and Solvent-Free Synthesis of Benzene Ring Acylated Harmalines

Directory of Open Access Journals (Sweden)

Sabira Begum

2009-12-01

Full Text Available A facile synthesis of a series of benzene ring acylated analogues of harmaline has been achieved by Friedel-Crafts acylation under solvent-free conditions at room temperature using acyl halides/acid anhydrides and AlCl3. The reaction afforded 10- and 12-acyl analogues of harmaline in good yield, along with minor quantities of N-acyl-tryptamines and 8-acyl analogues of N-acyltryptamines.

Solvent-Free Synthesis of Silver-Nanoparticles and their Use as Additive in Poly (Dicyclopentadiene)

International Nuclear Information System (INIS)

Abbas, M.; Kienberger, J.

2013-01-01

A solvent-free environmentally benign synthesis of oleylamine capped silver nanoparticles is presented. Upon heating 10 equivalents of oleylamine and silver nitrate at 165 degree C for 30 min followed by a precipitation step using ethanol as the precipitant particles characterized by an Z-average diameter of 63 nm were obtained. Dried particles can be easily redispersed in unpolar solvents or monomers, which pave the way for using them as an antimicrobial additive in polymeric materials. In particular, newly prepared Ag-particles were dispersed in dicyclopentadiene and the mixture was cured using ring opening metathesis polymerization yielding an antimicrobially equipped duroplastic material. (author)

Communication: modeling charge-sign asymmetric solvation free energies with nonlinear boundary conditions.

Science.gov (United States)

Bardhan, Jaydeep P; Knepley, Matthew G

2014-10-07

We show that charge-sign-dependent asymmetric hydration can be modeled accurately using linear Poisson theory after replacing the standard electric-displacement boundary condition with a simple nonlinear boundary condition. Using a single multiplicative scaling factor to determine atomic radii from molecular dynamics Lennard-Jones parameters, the new model accurately reproduces MD free-energy calculations of hydration asymmetries for: (i) monatomic ions, (ii) titratable amino acids in both their protonated and unprotonated states, and (iii) the Mobley "bracelet" and "rod" test problems [D. L. Mobley, A. E. Barber II, C. J. Fennell, and K. A. Dill, "Charge asymmetries in hydration of polar solutes," J. Phys. Chem. B 112, 2405-2414 (2008)]. Remarkably, the model also justifies the use of linear response expressions for charging free energies. Our boundary-element method implementation demonstrates the ease with which other continuum-electrostatic solvers can be extended to include asymmetry.

Communication: Modeling charge-sign asymmetric solvation free energies with nonlinear boundary conditions

International Nuclear Information System (INIS)

Bardhan, Jaydeep P.; Knepley, Matthew G.

2014-01-01

We show that charge-sign-dependent asymmetric hydration can be modeled accurately using linear Poisson theory after replacing the standard electric-displacement boundary condition with a simple nonlinear boundary condition. Using a single multiplicative scaling factor to determine atomic radii from molecular dynamics Lennard-Jones parameters, the new model accurately reproduces MD free-energy calculations of hydration asymmetries for: (i) monatomic ions, (ii) titratable amino acids in both their protonated and unprotonated states, and (iii) the Mobley “bracelet” and “rod” test problems [D. L. Mobley, A. E. Barber II, C. J. Fennell, and K. A. Dill, “Charge asymmetries in hydration of polar solutes,” J. Phys. Chem. B 112, 2405–2414 (2008)]. Remarkably, the model also justifies the use of linear response expressions for charging free energies. Our boundary-element method implementation demonstrates the ease with which other continuum-electrostatic solvers can be extended to include asymmetry

Communication: Modeling charge-sign asymmetric solvation free energies with nonlinear boundary conditions

Energy Technology Data Exchange (ETDEWEB)

Bardhan, Jaydeep P. [Department of Mechanical and Industrial Engineering, Northeastern University, Boston, Massachusetts 02115 (United States); Knepley, Matthew G. [Computation Institute, The University of Chicago, Chicago, Illinois 60637 (United States)

2014-10-07

We show that charge-sign-dependent asymmetric hydration can be modeled accurately using linear Poisson theory after replacing the standard electric-displacement boundary condition with a simple nonlinear boundary condition. Using a single multiplicative scaling factor to determine atomic radii from molecular dynamics Lennard-Jones parameters, the new model accurately reproduces MD free-energy calculations of hydration asymmetries for: (i) monatomic ions, (ii) titratable amino acids in both their protonated and unprotonated states, and (iii) the Mobley “bracelet” and “rod” test problems [D. L. Mobley, A. E. Barber II, C. J. Fennell, and K. A. Dill, “Charge asymmetries in hydration of polar solutes,” J. Phys. Chem. B 112, 2405–2414 (2008)]. Remarkably, the model also justifies the use of linear response expressions for charging free energies. Our boundary-element method implementation demonstrates the ease with which other continuum-electrostatic solvers can be extended to include asymmetry.

Solvent-free, visible-light photocatalytic alcohol oxidations applying an organic photocatalyst

Directory of Open Access Journals (Sweden)

Martin Obst

2016-11-01

Full Text Available A method for the solvent-free photocatalytic conversion of solid and liquid substrates was developed, using a novel rod mill apparatus. In this setup, thin liquid films are realized which is crucial for an effective photocatalytic conversion due to the low penetration depth of light in heterogeneous systems. Several benzylic alcohols were oxidized with riboflavin tetraacetate as photocatalyst under blue light irradiation of the reaction mixture. The corresponding carbonyl compounds were obtained in moderate to good yields.

Effect of solvent evaporation and coagulation on morphology development of asymmetric membranes

Science.gov (United States)

Chandrasekaran, Neelakandan; Kyu, Thein

2008-03-01

Miscibility behavior of blends of amorphous polyamide (PA) and polyvinylpyrrolidone (PVP) was studied in relation to membrane formation. Dimethylsulfoxide (DMSO) and water were used as solvent and non-solvent, respectively. Differential scanning calorimetry and cloud point measurements revealed that the binary PA/PVP blends as well as the ternary PA/PVP/DMSO system were completely miscible at all compositions. However, the addition of non-solvent (water) to this ternary system has led to phase separation. Visual turbidity study was used to establish a ternary liquid-liquid phase diagram of the PA-PVP/DMSO/water system. Scanning Electron Microscopy (SEM) showed the development of finger-like and sponge-like cross sectional morphologies during coagulation. Effects of polymer concentration, PA/PVP blend ratio, solvent/non-solvent quality, and evaporation time on the resulting membrane morphology will be discussed.

Estimate of electrostatic solvation free energy of electron in various polar solvents by using modified born equation

International Nuclear Information System (INIS)

Yamashita, Kazuo; Kitamura, Mitsutaka; Imai, Hideo

1976-01-01

The modified Born equation was tentatively applied to estimate the electrostatic free energies of solvation of the electron in various polar solvents. The related data of halide ions and a datum of the hydration free energy of the electron obtained by radiation chemical studies were used for the numerical calculations. (auth.)

Modification of cellulose with succinic anhydride in TBAA/DMSO mixed solvent under catalyst-free conditions

Science.gov (United States)

Homogeneous modification of cellulose with succinic anhydride was performed in tetrabutylammonium acetate (TBAA)/dimethyl sulfoxide (DMSO) mixed solvent. The molar ratio of succinic anhydride (SA) to free hydroxyl groups in the anhydroglucose units (AGU) and TBAA dosage were investigated as paramete...

Nafion®-catalyzed microwave-assisted Ritter reaction: An atom-economic solvent-free synthesis of amides

Science.gov (United States)

An atom-economic solvent-free synthesis of amides by the Ritter reaction of alcohols and nitriles under microwave irradiation is reported. This green protocol is catalyzed by solid supported Nafion®NR50 with improved efficiency and reduced waste production.

A Selenium-Based Ionic Liquid as a Recyclable Solvent for the Catalyst-Free Synthesis of 3-Selenylindoles

Directory of Open Access Journals (Sweden)

Eder J. Lenardão

2013-04-01

Full Text Available The ionic liquid 1-butyl-3-methylimidazolium methylselenite, [bmim][SeO2(OCH3], was successfully used as solvent in the catalyst-free preparation of 3-arylselenylindoles by the reaction of indole with ArSeCl at room temperature. The products were obtained selectively in good yields without the need of any additive and the solvent was easily reused for several cycles with good results.

New Tools for CO2 Fixation by Homogeneous Catalysis - Final Technical Report

Energy Technology Data Exchange (ETDEWEB)

Jessop, Phillip G.

2006-01-20

The overall goal is the development of new or more efficient methods for the conversion of CO{sub 2} into useful organic products, via the design or discovery of new catalysts, ligands, solvents, and methods. Specific objectives for this funded period: (1) To develop a high-throughput screening technique and use it to develop an efficient catalyst/reagent/solvent system for the synthesis of ureas or carboxylic acids. (2) To use in-situ spectroscopic and kinetic methods to study the mechanism of the synthesis of ureas or carboxylic acids. (3) To develop bifunctional ligands capable of secondary interactions with CO{sub 2}, to detect the interactions, and to demonstrate applications to catalysis.

A Solvent-Free Base Liberation of a Tertiary Aminoalkyl Halide by Flow Chemistry

DEFF Research Database (Denmark)

Pedersen, Michael Jønch; Skovby, Tommy; Mealy, Michael J.

2016-01-01

A flow setup for base liberation of 3-(N,N-dimethylamino)propyl chloride hydrochloride and solvent-free separation of the resulting free base has been developed. Production in flow profits from an on-demand approach, useful for labile aminoalkyl halides. The requirement for obtaining a dry product...... has been fulfilled by the simple use of a saturated NaOH solution, followed by isolation of the liquid phases by gravimetric separation. The flow setup has an E factor reduction of nearly 50%, and a distillation step has been avoided. The method exemplifies how flow chemistry can be exploited...

Dark catalysis

Energy Technology Data Exchange (ETDEWEB)

Agrawal, Prateek; Cyr-Racine, Francis-Yan; Randall, Lisa; Scholtz, Jakub, E-mail: prateekagrawal@fas.harvard.edu, E-mail: fcyrraci@physics.harvard.edu, E-mail: randall@physics.harvard.edu, E-mail: jscholtz@physics.harvard.edu [Department of Physics, Harvard University, 17 Oxford St., Cambridge, MA 02138 (United States)

2017-08-01

Recently it was shown that dark matter with mass of order the weak scale can be charged under a new long-range force, decoupled from the Standard Model, with only weak constraints from early Universe cosmology. Here we consider the implications of an additional charged particle C that is light enough to lead to significant dissipative dynamics on galactic times scales. We highlight several novel features of this model, which can be relevant even when the C particle constitutes only a small fraction of the number density (and energy density). We assume a small asymmetric abundance of the C particle whose charge is compensated by a heavy X particle so that the relic abundance of dark matter consists mostly of symmetric X and X-bar , with a small asymmetric component made up of X and C . As the universe cools, it undergoes asymmetric recombination binding the free C s into ( XC ) dark atoms efficiently. Even with a tiny asymmetric component, the presence of C particles catalyzes tight coupling between the heavy dark matter X and the dark photon plasma that can lead to a significant suppression of the matter power spectrum on small scales and lead to some of the strongest bounds on such dark matter theories. We find a viable parameter space where structure formation constraints are satisfied and significant dissipative dynamics can occur in galactic haloes but show a large region is excluded. Our model shows that subdominant components in the dark sector can dramatically affect structure formation.

Adiabatic Field-Free Alignment of Asymmetric Top Molecules with an Optical Centrifuge.

Science.gov (United States)

Korobenko, A; Milner, V

2016-05-06

We use an optical centrifuge to align asymmetric top SO_{2} molecules by adiabatically spinning their most polarizable O-O axis. The effective centrifugal potential in the rotating frame confines the sulfur atoms to the plane of the laser-induced rotation, leading to the planar molecular alignment that persists after the molecules are released from the centrifuge. The periodic appearance of the full three-dimensional alignment, typically observed only with linear and symmetric top molecules, is also detected. Together with strong in-plane centrifugal forces, which bend the molecules by up to 10 deg, permanent field-free alignment offers new ways of controlling molecules with laser light.

At the frontier between heterogeneous and homogeneous catalysis : hydrogenation of olefins and alkynes with soluble iron nanoparticles

NARCIS (Netherlands)

Rangheard, Claudine; Julián Fernández, César de; Phua, Pim-Huat; Hoorn, Johan; Lefort, Laurent; Vries, Johannes G. de

2010-01-01

The use of non-supported Fe nanoparticles in the hydrogenation of unsaturated C–C bonds is a green catalytic concept at the frontier between homogeneous and heterogeneous catalysis. Iron nanoparticles can be obtained by reducing Fe salts with strong reductants in various solvents. FeCl3 reduced by 3

Communication: Modeling charge-sign asymmetric solvation free energies with nonlinear boundary conditions

Science.gov (United States)

Bardhan, Jaydeep P.; Knepley, Matthew G.

2014-01-01

We show that charge-sign-dependent asymmetric hydration can be modeled accurately using linear Poisson theory after replacing the standard electric-displacement boundary condition with a simple nonlinear boundary condition. Using a single multiplicative scaling factor to determine atomic radii from molecular dynamics Lennard-Jones parameters, the new model accurately reproduces MD free-energy calculations of hydration asymmetries for: (i) monatomic ions, (ii) titratable amino acids in both their protonated and unprotonated states, and (iii) the Mobley “bracelet” and “rod” test problems [D. L. Mobley, A. E. Barber II, C. J. Fennell, and K. A. Dill, “Charge asymmetries in hydration of polar solutes,” J. Phys. Chem. B 112, 2405–2414 (2008)]. Remarkably, the model also justifies the use of linear response expressions for charging free energies. Our boundary-element method implementation demonstrates the ease with which other continuum-electrostatic solvers can be extended to include asymmetry. PMID:25296776

Three Component Synthesis of Substituted 4H-[1,3]Dioxin Derivatives Under Solvent-Free Conditions

Directory of Open Access Journals (Sweden)

Mohammad Reza Hosseini-Tabatabaei

2012-01-01

Full Text Available Reaction between aryl aldehydes, acetylacetone and alkyl isocyanides in solvent-free conditions provided a simple and efficient one-pot route for the synthesis of 1-(2-alkylamino-6-methyl-4-aryl-4H-[1,3]dioxin-5-ylethanone derivatives in excellent yields.

Solvent Effects in Asymmetric Hetero Diels-Alder and Ene Reactions

DEFF Research Database (Denmark)

Johannsen, Mogens; Jørgensen, Karl Anker

1996-01-01

The use of polar solvents such as nitromethane or 2-nitropropane leads to a significant improvement of the catalytic properties of a cationic copper-Lewis acid in the hetero Diels-Alder reaction of alkyl glyoxylates with dienes; The scope of a newly developed copper(II)-bisoxazoline catalyst...... for the hetero Diels-Alder reaction is demonstrated by the reaction of different dienes with alkyl glyoxylates in nitroalkane solvents with the formation of the hetero Diels-Alder adduct in high enantiomeric excess as the major product. The synthetic application of the reaction is exemplified by an improved...

SOLVENT-FREE TETRAHYDROPYRANYLATION (THP) OF ALCOHOLS AND PHENOLS AND THEIR REGENERATION BY CATALYTIC ALUMINUM CHLORIDE HEXAHYDRATE

Science.gov (United States)

Catalytic amount of aluminum chloride hexahydrate enables solvent-free tetrahydropyranylation (THP) of alcohols and phenols at moderate temperatures. A simple addition of methanol helps to regenerate the corresponding alcohols and phenols thus rendering these protection and depro...

Direct Detection of the Ion Pair to Free Ions Transformation upon Complexation with an Ion Receptor in Non‐Polar Solvents by using Conductometry

Science.gov (United States)

Iseda, Kazuya

2018-01-01

Abstract In this study, we performed conductometry in various organic solvents to directly detect the transformation from tetrabutylammonium chloride (TBACl) ion‐pair salt to the free ions through complexation with meso‐octamethylcalix[4]pyrrole (CP), which is a well‐known receptor for chloride anions. In the presence of CP, the conductivity of TBACl increases in various non‐polar solvents, indicating that complexation with CP enhances the ionic dissociation of TBACl in such non‐polar solvents. In other words, CP recognizes chloride as an ion‐paired salt as well as a free anion in non‐polar solvents. Additionally, the TBA(CP–Cl) complex exhibited a considerably lower ion‐pairing constant (K ip) than TBACl in non‐polar solvents, resulting in enhanced conductivity. Based on these findings, we can conclude that complexation of an anion with a hydrophobic anion receptor will be useful for creating functional and stimuli‐responsive soft materials in organic solvents using coulombic forces. PMID:29610717

Direct Detection of the Ion Pair to Free Ions Transformation upon Complexation with an Ion Receptor in Non-Polar Solvents by using Conductometry.

Science.gov (United States)

Iseda, Kazuya; Kokado, Kenta; Sada, Kazuki

2018-03-01

In this study, we performed conductometry in various organic solvents to directly detect the transformation from tetrabutylammonium chloride ( TBACl ) ion-pair salt to the free ions through complexation with meso -octamethylcalix[4]pyrrole ( CP ), which is a well-known receptor for chloride anions. In the presence of CP , the conductivity of TBACl increases in various non-polar solvents, indicating that complexation with CP enhances the ionic dissociation of TBACl in such non-polar solvents. In other words, CP recognizes chloride as an ion-paired salt as well as a free anion in non-polar solvents. Additionally, the TBA(CP - Cl ) complex exhibited a considerably lower ion-pairing constant ( K ip ) than TBACl in non-polar solvents, resulting in enhanced conductivity. Based on these findings, we can conclude that complexation of an anion with a hydrophobic anion receptor will be useful for creating functional and stimuli-responsive soft materials in organic solvents using coulombic forces.

A Correlation between the Activity of Candida antarctica Lipase B and Differences in Binding Free Energies of Organic Solvent and Substrate

DEFF Research Database (Denmark)

Banik, Sindrila Dutta; Nordblad, Mathias; Woodley, John

2016-01-01

in an inhibitory effect which is also confirmed by the binding free energies for the solvent and substrate molecules estimated from the simulations. Consequently, the catalytic activity of CALB decreases in polar solvents. This effect is significant, and CALB is over 10 orders of magnitude more active in nonpolar...... of the enzyme may be ascribed to binding of solvent molecules to the enzyme active site region and the solvation energy of substrate molecules in the different solvents. Polar solvent molecules interact strongly with CALB and compete with the substrate to bind to the active site region, resulting...

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

Science.gov (United States)

Bohnert, George W [Harrisonville, MO; Hand, Thomas E [Lee's Summit, MO; DeLaurentiis, Gary M [Jamestown, CA

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.

Modification of cellulose with succinic anhydride in TBAA/DMSO mixed solvent under catalyst-free conditions

Science.gov (United States)

Ping-Ping Xin; Yao-Bing Huang; Chung-Yun Hse; Huai N. Cheng; Chaobo Huang; Hui. Pan

2017-01-01

Homogeneous modification of cellulose with succinic anhydride was performed using tetrabutylammonium acetate (TBAA)/dimethyl sulfoxide (DMSO) mixed solvent. The molar ratio of succinic anhydride (SA) to free hydroxyl groups in the anhydroglucose units (AGU), TBAA dosage, reaction temperature, and reaction time were investigated. The highest degree of substitution (DS)...

Chiral phosphites as ligands in asymmetric metal complex catalysis and synthesis of coordination compounds

International Nuclear Information System (INIS)

Gavrilov, Konstantin N; Bondarev, Oleg G; Polosukhin, Aleksei I

2004-01-01

The data published during the last five years on the application of chiral derivatives of phosphorous acid in coordination chemistry and enantioselective catalysis are summarised and discussed. The effect of the nature of these ligands on the structure of metal complexes and on the efficiency of catalytic organic syntheses is shown. Hydroformylation, hydrogenation, allylic substitution and conjugate addition catalysed by transition metal complexes with optically active phosphites and hydrophosphoranes are considered. The prospects for the development of this field of research are demonstrated.

Controlled trifluoromethylation reactions of alkynes through visible-light photoredox catalysis.

Science.gov (United States)

Iqbal, Naeem; Jung, Jaehun; Park, Sehyun; Cho, Eun Jin

2014-01-07

The control of a reaction that can form multiple products is a highly attractive and challenging concept in synthetic chemistry. A set of valuable CF3 -containing molecules, namely trifluoromethylated alkenyl iodides, alkenes, and alkynes, were selectively generated from alkynes and CF3 I by environmentally benign and efficient visible-light photoredox catalysis. Subtle differences in the combination of catalyst, base, and solvent enabled the control of reactivity and selectivity for the reaction between an alkyne and CF3 I. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solvent free oxidation of primary alcohols and diols using thymine iron(III) catalyst.

Science.gov (United States)

Al-Hunaiti, Afnan; Niemi, Teemu; Sibaouih, Ahlam; Pihko, Petri; Leskelä, Markku; Repo, Timo

2010-12-28

In this study, we developed an efficient and selective iron-based catalyst system for the synthesis of ketones from secondary alcohols and carboxylic acids from primary alcohol. In situ generated iron catalyst of thymine-1-acetate (THA) and FeCl(3) under solvent-free condition exhibits high activity. As an example, 1-octanol and 2-octanol were oxidized to 1-octanoic acid and 2-octanone with 89% and 98% yields respectively.

FATTY ACID ETHYL ESTERS FROM MICROALGAE OF Scenedesmus ecornis BY ENZYMATIC AND ACID CATALYSIS

Directory of Open Access Journals (Sweden)

Gabryelle F. de Almeida

Full Text Available Microalgae are an indispensable food source for the various growth stages of mollusks, crustaceans, and several fish species. Using a microalgae biomass present in the Amazonian ecosystem (Macapá-AP, we study extraction methods for fatty acid such as solvent extraction (magnetic stirring and/or Soxhlet and/or hydrolysis (acid and/or enzymatic catalysis followed by esterification and/or direct transesterification. Extraction of crude triacylglycerides by mechanical stirring at room temperature was more efficient than continuous reflux (Soxhlet. Subsequently, the lipid extract was subject to transesterification with ethanol and CAL-B as a biocatalyst, leading to production of fatty acid ethyl esters (FAEE. Additionally, FAEEs were prepared by hydrolysis of crude triacylglycerides followed by acid-mediated esterification or enzymatic catalysis (lipase. In this case, the type of catalyst did not significantly influence FAEE yields. In the lipid extract, we identified palmitic, linoleic, oleic, and stearic acids with palmitic acid being the most abundant. Our results suggest that enzymatic catalysis is a viable method for the extraction of lipids in the microalga, Scenedesmus ecornis.

Towards room temperature, direct, solvent free synthesis of tetraborohydrides

International Nuclear Information System (INIS)

Remhof, A; Yan, Y; Friedrichs, O; Kim, J W; Mauron, Ph; Borgschulte, A; Züttel, A; Wallacher, D; Buchsteiner, A; Hoser, A; Oh, K H; Cho, Y W

2012-01-01

Due to their high hydrogen content, tetraborohydrides are discussed as potential synthetic energy carriers. On the example of lithium borohydride LiBH 4 , we discuss current approaches of direct, solvent free synthesis based on gas solid reactions of the elements or binary hydrides and/or borides with gaseous H 2 or B 2 H 6 . The direct synthesis from the elements requires high temperature and high pressure (700°C, 150bar D 2 ). Using LiB or AlB 2 as boron source reduces the required temperature by more than 300 K. Reactive milling of LiD with B 2 H 6 leads to the formation of LiBD 4 already at room temperature. The reactive milling technique can also be applied to synthesize other borohydrides from their respective metal hydrides.

Hot Melt Extrusion as Solvent-Free Technique for a Continuous Manufacturing of Drug-Loaded Mesoporous Silica

DEFF Research Database (Denmark)

Genina, Natalja; Hadi, Batol; Löbmann, Korbinian

2018-01-01

The aim of this study is to explore hot melt extrusion (HME) as a solvent-free drug loading technique for preparation of stable amorphous solid dispersions using mesoporous silica (PSi). Ibuprofen and carvedilol were used as poorly soluble active pharmaceutical ingredients (APIs). Due to the high...... friction of an API:PSi mixture below the loading limit of the API, it was necessary to add the polymer Soluplus(®) (SOL) in order to enable the extrusion process. As a result, the APIs were distributed between the PSi and SOL phase after HME. Due to its higher affinity to PSi, ibuprofen was mainly adsorbed...... into the PSi, whereas carvedilol was mainly found in the SOL phase. Intrinsic dissolution rate was highest for HME formulations, containing PSi, compared to pure crystalline (amorphous) APIs and HME formulations without PSi. HME is a feasible solvent-free drug loading technique for preparation of PSi...

Solvent free one pot synthesis of amidoalkyl naphthols over phosphotungstic acid

Directory of Open Access Journals (Sweden)

Divya P. Narayanan

2017-07-01

Full Text Available Montmorillonite KSF clay was effectively modified by the encapsulation of phosphotungstic acid into the clay layers via sonication followed by incipient wet impregnation method. The prepared catalysts were characterized by X-ray diffraction (XRD, Fourier-transform infrared spectroscopy (FTIR and scanning electron microscopy (SEM techniques. The catalytic activities of the prepared systems were investigated in the solvent free synthesis of amidoalkyl naphthols by the multicomponent one-pot condensation of an aldehyde, β-naphthol and an amide or urea. Excellent yield, shorter reaction time, easy work-up, and reusability of the catalyst are the main attractions of this green procedure.

Recent efforts directed to the development of more sustainable asymmetric organocatalysis.

Science.gov (United States)

Hernández, José G; Juaristi, Eusebio

2012-06-04

In line with the principles of "green" chemistry, organocatalysis seeks to reduce energy consumption and to optimize the use of the available resources, aiming to become a sustainable strategy in chemical transformations. Nevertheless, during the last decade diverse experimental protocols have made organocatalysis an even "greener" alternative by the use of friendlier reaction conditions, or via the application of solvent-free methodologies, or through the design and synthesis of more selective catalysts, or via the development of multicomponent one-pot organocatalytic reactions, or by the recycling and reuse of organocatalysts, or by means of the application of more energy-efficient activation techniques, among other approaches. In this feature article we review some of the remarkable advancements that have made it possible to develop even more sustainable asymmetric organocatalyzed methodologies.

21 CFR 182.40 - Natural extractives (solvent-free) used in conjunction with spices, seasonings, and flavorings.

Science.gov (United States)

2010-04-01

... conjunction with spices, seasonings, and flavorings. 182.40 Section 182.40 Food and Drugs FOOD AND DRUG... in conjunction with spices, seasonings, and flavorings. Natural extractives (solvent-free) used in conjunction with spices, seasonings, and flavorings that are generally recognized as safe for their intended...

21 CFR 582.40 - Natural extractives (solvent-free) used in conjunction with spices, seasonings, and flavorings.

Science.gov (United States)

2010-04-01

... conjunction with spices, seasonings, and flavorings. 582.40 Section 582.40 Food and Drugs FOOD AND DRUG... in conjunction with spices, seasonings, and flavorings. Natural extractives (solvent-free) used in conjunction with spices, seasonings, and flavorings that are generally recognized as safe for their intended...

Evaluation of commercial and sulfated ZrO{sub 2} aiming application catalysis; Avaliacao de ZrO{sub 2} comercial e sulfatada visando aplicacao em catalise

Energy Technology Data Exchange (ETDEWEB)

Silva, F.N.; Dantas, J.; Costa, A.C.F.M., E-mail: nilson.s@hotmail.com [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Pos-Graduacao em Engenharia de Materiais; Pallone, E.M.J.A. [Universidade de Sao Paulo (USP), Pirassununga, SP (Brazil). Departamento de Ciencias Basicas; Dutra, R.C.L. [Instituto de Aeronautica e Espaco (AQI/IAE), Sao Jose dos Campos, SP (Brazil). Divisao de Quimica

2014-07-01

This study evaluates the performance of commercial and sulfated ZrO{sub 2} for future application in catalysis. Commercial ZrO{sub 2} was provided by the company Saint-Gobain Zirpro. The sulfation occurred with SO{sub 4}{sup -2} ion content of 30% compared to the mass of ZrO{sub 2}. The samples were characterized by XRD, FTIR, EDX and GD. The results revealed the formation of a monoclinic phase for the commercial sample, and a monoclinic major phase with tetragonal traces for the sulfated sample. The commercial ZrO{sub 2} showed a narrow, bimodal and asymmetric agglomerates distribution, while the sulfated sample showed a narrow, tetramodal and asymmetric agglomerates distribution. The presence of traces of the tetragonal phase in the SO{sub 4}{sup -2}/ZrO{sub 2} XRD, and the presence of SO{sub 3} in the EDX were good indicators for future use in catalysis to provide ester. (author)

The Effects of Introducing Advertising in Pay TV: A Model of Asymmetric Competition between Pay TV and Free TV

OpenAIRE

Helmut Dietl; Markus Lang; Panlang Lin

2012-01-01

This paper develops a theoretical model of asymmetric competition between a pay TV and a free TV broadcaster. Our model shows that the pay TV broadcaster has incentives to place advertising on its channel if the marginal return on advertising exceeds the viewers' disutility from advertising. In this case, however, the pay TV advertising level is always below the corresponding level on free TV. The pay TV advertising level can increase with a higher viewer disutility from advertising but the p...

New pathway to C2-symmetric atropoisomeric bipyridine N,N’-dioxides and solvent effect in enantioselective allylation of aldehydes

Czech Academy of Sciences Publication Activity Database

Hrdina, R.; Dračínský, Martin; Valterová, Irena; Hodačová, Jana; Císařová, I.; Kotora, Martin

2008-01-01

Roč. 350, č. 10 (2008), s. 1449-1456 ISSN 1615-4150 Grant - others:GA MŠk(CZ) LC06070 Program:LC Institutional research plan: CEZ:AV0Z40550506 Keywords : asymmetric catalysis * cobalt * cyclotrimerization Subject RIV: CC - Organic Chemistry Impact factor: 5.619, year: 2008

Immobilization of Acetobacter sp. CCTCC M209061 for efficient asymmetric reduction of ketones and biocatalyst recycling.

Science.gov (United States)

Chen, Xiao-Hong; Wang, Xiao-Ting; Lou, Wen-Yong; Li, Ying; Wu, Hong; Zong, Min-Hua; Smith, Thomas J; Chen, Xin-De

2012-09-04

The bacterium Acetobacter sp. CCTCC M209061 is a promising whole-cell biocatalyst with exclusive anti-Prelog stereoselectivity for the reduction of prochiral ketones that can be used to make valuable chiral alcohols such as (R)-4-(trimethylsilyl)-3-butyn-2-ol. Although it has promising catalytic properties, its stability and reusability are relatively poor compared to other biocatalysts. Hence, we explored various materials for immobilizing the active cells, in order to improve the operational stability of biocatalyst. It was found that Ca-alginate give the best immobilized biocatalyst, which was then coated with chitosan to further improve its mechanical strength and swelling-resistance properties. Conditions were optimized for formation of reusable immobilized beads which can be used for repeated batch asymmetric reduction of 4'-chloroacetophenone. The optimized immobilized biocatalyst was very promising, with a specific activity of 85% that of the free-cell biocatalyst (34.66 μmol/min/g dw of cells for immobilized catalyst vs 40.54 μmol/min/g for free cells in the asymmetric reduction of 4'-chloroacetophenone). The immobilized cells showed better thermal stability, pH stability, solvent tolerance and storability compared with free cells. After 25 cycles reaction, the immobilized beads still retained >50% catalytic activity, which was 3.5 times higher than degree of retention of activity by free cells reused in a similar way. The cells could be recultured in the beads to regain full activity and perform a further 25 cycles of the reduction reaction. The external mass transfer resistances were negligible as deduced from Damkohler modulus Da internal mass transfer restriction affected the reduction action but was not the principal rate-controlling step according to effectiveness factors η < 1 and Thiele modulus 0.3<∅ <1. Ca-alginate coated with chitosan is a highly effective material for immobilization of Acetobacter sp. CCTCC M209061 cells for repeated use in

Immobilization of Acetobacter sp. CCTCC M209061 for efficient asymmetric reduction of ketones and biocatalyst recycling

Directory of Open Access Journals (Sweden)

Chen Xiao-Hong

2012-09-01

Full Text Available Abstract Background The bacterium Acetobacter sp. CCTCC M209061 is a promising whole-cell biocatalyst with exclusive anti-Prelog stereoselectivity for the reduction of prochiral ketones that can be used to make valuable chiral alcohols such as (R-4-(trimethylsilyl-3-butyn-2-ol. Although it has promising catalytic properties, its stability and reusability are relatively poor compared to other biocatalysts. Hence, we explored various materials for immobilizing the active cells, in order to improve the operational stability of biocatalyst. Results It was found that Ca-alginate give the best immobilized biocatalyst, which was then coated with chitosan to further improve its mechanical strength and swelling-resistance properties. Conditions were optimized for formation of reusable immobilized beads which can be used for repeated batch asymmetric reduction of 4′-chloroacetophenone. The optimized immobilized biocatalyst was very promising, with a specific activity of 85% that of the free-cell biocatalyst (34.66 μmol/min/g dw of cells for immobilized catalyst vs 40.54 μmol/min/g for free cells in the asymmetric reduction of 4′-chloroacetophenone. The immobilized cells showed better thermal stability, pH stability, solvent tolerance and storability compared with free cells. After 25 cycles reaction, the immobilized beads still retained >50% catalytic activity, which was 3.5 times higher than degree of retention of activity by free cells reused in a similar way. The cells could be recultured in the beads to regain full activity and perform a further 25 cycles of the reduction reaction. The external mass transfer resistances were negligible as deduced from Damkohler modulus Da η ∅ Conclusions Ca-alginate coated with chitosan is a highly effective material for immobilization of Acetobacter sp. CCTCC M209061 cells for repeated use in the asymmetric reduction of ketones. Only a small cost in terms of the slightly lower catalytic activity compared to

Development of solvent-free offset ink using vegetable oil esters and high molecular-weight resin.

Science.gov (United States)

Park, Jung Min; Kim, Young Han; Kim, Sung Bin

2013-01-01

In the development of solvent-free offset ink, the roles of resin molecular weight and used solvent on the ink performance were evaluated by examining the relationship between the various properties of resin and solvent and print quality. To find the best performing resin, the soy-oil fatty acid methyl ester (FAME) was applied to the five modified-phenolic resins having different molecular weights. It is found from the experimental results that the ink made of higher molecular weight and better solubility resin gives better printability and print quality. It is because larger molecular weight resin with better solubility gives higher rate of ink transfer. From the ink application of different esters to high molecular weight resin, the best printing performance was yielded from the soy-oil fatty acid butyl ester (FABE). It is due to its high kinematic viscosity resulting in the smallest change of ink transfer weight upon multiple number of printing, which improves the stability of ink quality.

Horizons in catalysis

Energy Technology Data Exchange (ETDEWEB)

Idol, J D

1979-04-21

A discussion covers a brief historical review of industrial catalysis; a survey of major present-day catalytic processes in the petroleum and petrochemical industries; the outlook for the industrial catalyst applications in coal liquefaction, conversion of coal liquids, shale oil, and other synthetic crude sources for transportation fuels, and synthesis gas-based processes; some important directions for future developments, including phase transfer catalysis, photocatalysis, and advanced techniques for catalyst studies; and the need for closer industry-university and industry-government cooperation in the field of catalysis.

Constructing Asymmetric Polyion Complex Vesicles via Template Assembling Strategy: Formulation Control and Tunable Permeability

Directory of Open Access Journals (Sweden)

Junbo Li

2017-11-01

Full Text Available A strategy for constructing polyion complex vesicles (PICsomes with asymmetric structure is described. Poly(methylacrylic acid-block-poly(N-isopropylacrylamide modified gold nanoparticles (PMAA-b-PNIPAm-@-Au NPs were prepared and then assembled with poly(ethylene glycol-block-poly[1-methyl-3-(2-methacryloyloxy propylimidazolium bromine] (PEG-b-PMMPImB via polyion complex of PMMA and PMMPImB. After removing the Au NPs template, asymmetric PICsomes composed of a PNIPAm inner-shell, PIC wall, and PEG outer-corona were obtained. These PICsomes have low protein absorption and thermally tunable permeability, provided by the PEG outer-corona and the PNIPAm inner-shell, respectively. Moreover, PICsome size can be tailored by using templates of predetermined sizes. This novel strategy for constructing asymmetric PICsomes with well-defined properties and controllable size is valuable for applications such as drug delivery, catalysis and monitoring of chemical reactions, and biomimetics.

The effect of solvent relaxation time constants on free energy gap law for ultrafast charge recombination following photoinduced charge separation.

Science.gov (United States)

Mikhailova, Valentina A; Malykhin, Roman E; Ivanov, Anatoly I

2018-05-16

To elucidate the regularities inherent in the kinetics of ultrafast charge recombination following photoinduced charge separation in donor-acceptor dyads in solutions, the simulations of the kinetics have been performed within the stochastic multichannel point-transition model. Increasing the solvent relaxation time scales has been shown to strongly vary the dependence of the charge recombination rate constant on the free energy gap. In slow relaxing solvents the non-equilibrium charge recombination occurring in parallel with solvent relaxation is very effective so that the charge recombination terminates at the non-equilibrium stage. This results in a crucial difference between the free energy gap laws for the ultrafast charge recombination and the thermal charge transfer. For the thermal reactions the well-known Marcus bell-shaped dependence of the rate constant on the free energy gap is realized while for the ultrafast charge recombination only a descending branch is predicted in the whole area of the free energy gap exceeding 0.2 eV. From the available experimental data on the population kinetics of the second and first excited states for a series of Zn-porphyrin-imide dyads in toluene and tetrahydrofuran solutions, an effective rate constant of the charge recombination into the first excited state has been calculated. The obtained rate constant being very high is nearly invariable in the area of the charge recombination free energy gap from 0.2 to 0.6 eV that supports the theoretical prediction.

Acid catalyzed solvent free synthesis of new 1-acyl-4-benzhydryl substituted pyrazoles

International Nuclear Information System (INIS)

Sher, M.; Kausar, T.; Riaz, N.; Sharif, A.

2016-01-01

A convenient, cost effective and environmentally benign methodology has been developed, which delivered fourteen new 1-acyl-4-benzhyrdyl substituted pyrazole derivatives under solvent free conditions. Target compounds were synthesized in good to excellent yields simply by grinding reactants in a pestle and mortar with catalytic amount of conc. H/sub 2/SO/sub 4/. All the newly formed compounds were fully characterized with the help of detailed spectroscopic techniques including FTIR, NMR and GC-MS. (author)

Synthesis of β-phenylchalcogeno-α, β-unsaturated esters, ketones and nitriles using microwave and solvent-free conditions

International Nuclear Information System (INIS)

Lenardao, Eder J.; Silva, Marcio S.; Mendes, Samuel R.; Azambuja, Francisco de; Jacob, Raquel G.; Perin, Gelson; Santos, Paulo Cesar Silva dos

2007-01-01

A simple, clean and efficient solvent-free protocol was developed for hydrochalcogenation of alkynes containing a Michael acceptor (ester, ketone and nitrile) with phenylchalcogenolate anions generated in situ from the respective diphenyl dichalcogenide (Se, Te, S), using alumina supported sodium borohydride. This efficient and improved method is general and furnishes the respective (Z)-β-phenylchalcogeno-α,β-unsaturated esters, ketones and nitriles, in good yield and higher selectivity, compared with those that use organic solvent and inert atmosphere. The use of microwave (MW) irradiation facilitates the procedure and accelerates the reaction. (author)

Porous fiber formation in polymer-solvent system undergoing solvent evaporation

Science.gov (United States)

Dayal, Pratyush; Kyu, Thein

2006-08-01

Temporal evolution of the fiber morphology during dry spinning has been investigated in the framework of Cahn-Hilliard equation [J. Chem. Phys. 28, 258 (1958)] pertaining to the concentration order parameter or volume fraction given by the Flory-Huggins free energy of mixing [P. J. Flory, Principles of Polymer Chemistry (Cornell University Press, Ithaca, NY, 1953), p. 672] in conjunction with the solvent evaporation rate. To guide the solvent evaporation induced phase separation, equilibrium phase diagram of the starting polymer solution was established on the basis of the Flory-Huggins free energy of mixing. The quasi-steady-state approximation has been adopted to account for the nonconserved nature of the concentration field caused by the solvent loss. The process of solvent evaporation across the fiber skin-air interface was treated in accordance with the classical Fick's law [R. B. Bird et al., Transport Phenomena (J. Wiley, New York, 1960), p. 780]. The simulated morphologies include gradient type, hollow fiber type, bicontinuous type, and host-guest type. The development of these diverse fiber morphologies is explicable in terms of the phase diagram of the polymer solution in a manner dependent on the competition between the phase separation dynamics and rate of solvent evaporation.

Comparison of the free and bound phenolic profiles and cellular antioxidant activities of litchi pulp extracts from different solvents

Science.gov (United States)

2014-01-01

Background The phenolic contents and antioxidant activities of fruits could be underestimated if the bound phenolic compounds are not considered. In the present study, the extraction efficiencies of various solvents were investigated in terms of the total content of the free and bound phenolic compounds, as well as the phenolic profiles and antioxidant activities of the extracts. Methods Five different solvent mixtures were used to extract the free phenolic compounds from litchi pulp. Alkaline and acidic hydrolysis methods were compared for the hydrolysis of bound phenolic compounds from litchi pulp residue. The phenolic compositions of the free and bound fractions from the litchi pulp were identified using HPLC-DAD. The antioxidant activities of the litchi pulp extracts were determined by oxygen radical absorbance capacity (ORAC) and cellular antioxidant activity (CAA) assays. Results Of the solvents tested, aqueous acetone extracted the largest amount of total free phenolic compounds (210.7 mg GAE/100 g FW) from litchi pulp, followed sequentially by aqueous mixtures of methanol, ethanol and ethyl acetate, and water itself. The acid hydrolysis method released twice as many bound phenolic compounds as the alkaline hydrolysis method. Nine phenolic compounds were detected in the aqueous acetone extract. In contrast, not all of these compounds were found in the other four extracts. The classification and content of the bound phenolic compounds released by the acid hydrolysis method were higher than those achieved by the alkaline hydrolysis. The aqueous acetone extract showing the highest ORAC value (3406.9 μmol TE/100 g FW) for the free phenolic extracts. For the CAA method, however, the aqueous acetone and methanol extracts (56.7 and 55.1 μmol QE/100 g FW) showed the highest levels of activity of the five extracts tested. The ORAC and CAA values of the bound phenolic compounds obtained by acid hydrolysis were 2.6- and 1.9-fold higher than those obtained using the

Asymmetric Michael Addition Mediated by Chiral Ionic Liquids.

Science.gov (United States)

Suzuki, Yumiko

2018-06-01

Chiral ionic liquids with a focus on their applications in asymmetric Michael additions and related reactions were reviewed. The examples were classified on the basis of the mode of asymmetric induction (e.g., external induction/non-covalent interaction or internal induction/covalent bond formation), the roles in reactions (as a solvent or catalyst), and their structural features (e.g., imidazolium-based chiral cations, other chiral oniums; proline derivatives). Most of the reactions with high chiral induction are Michael addition of ketones or aldehydes to chalcones or nitrostyrenes where proline-derived chiral ionic liquids catalyze the reaction through enamine/ iminium formation. Many reports demonstrate the recyclability of ionic liquid-tagged pyrrolidines.

Porous asymmetric SiO2-g-PMMA nanoparticles produced by phase inversion

KAUST Repository

Munirasu, Selvaraj; Nunes, Suzana Pereira

2014-01-01

of functionalized nanoparticles in different solvents and immersion in water. The resulting asymmetrically porous morphology and nanoparticle assembly was characterized by scanning electron and atomic force microscopy. The PMMA functionalized SiO2 hybrid material

Using solvent-free sample preparation to promote protonation of poly(ethylene oxide)s with labile end-groups in matrix-assisted laser desorption/ionisation.

Science.gov (United States)

Mazarin, Michael; Phan, Trang N T; Charles, Laurence

2008-12-01

Protonation is usually required to observe intact ions during matrix-assisted laser desorption/ionization (MALDI) of polymers containing fragile end-groups while cation adduction induces chain-end degradation. These polymers, generally obtained via living free radical polymerization techniques, are terminated with a functionality in which a bond is prone to homolytic cleavage, as required by the polymerization process. A solvent-free sample preparation method was used here to avoid salt contaminant from the solvent traditionally used in the dried-droplet MALDI procedure. Solvent-based and solvent-free sample preparations were compared for a series of three poly(ethylene oxide) polymers functionalized with a labile end-group in a nitroxide-mediated polymerization reaction, using 2,4,6-trihydroxyacetophenone (THAP) as the matrix without any added salt. Intact oligomer ions could only be produced as protonated molecules in solvent-free MALDI while sodium adducts of degraded polymers were formed from the dried-droplet samples. Although MALDI analysis was performed at the laser threshold, fragmentation of protonated macromolecules was still observed to occur. However, in contrast to sodiated molecules, dissociation of protonated oligomers does not involve the labile C--ON bond of the end-group. As the macromolecule size increased, protonation appeared to be less efficient and sodium adduction became the dominant ionization process, although no sodium salt was added in the preparation. Formation of sodiated degraded macromolecules would be dictated by increasing cation affinity as the size of the oligomers increases and would reveal the presence of salts at trace levels in the MALDI samples.

NeoPHOX – a structurally tunable ligand system for asymmetric catalysis

Directory of Open Access Journals (Sweden)

Jaroslav Padevět

2016-06-01

Full Text Available A synthesis of new NeoPHOX ligands derived from serine or threonine has been developed. The central intermediate is a NeoPHOX derivative bearing a methoxycarbonyl group at the stereogenic center next to the oxazoline N atom. The addition of methylmagnesium chloride leads to a tertiary alcohol, which can be acylated or silylated to produce NeoPHOX ligands with different sterical demand. The new NeoPHOX ligands were tested in the iridium-catalyzed asymmetric hydrogenation and palladium-catalyzed allylic substitution. In both reactions high enantioselectivities were achieved, that were comparable to the enantioselectivities obtained with the up to now best NeoPHOX ligand derived from expensive tert-leucine.

Synthesis of quinoxaline 1,4-di-n-oxide derivatives on solid support using room temperature and microwave-assisted solvent-free procedures

International Nuclear Information System (INIS)

Gomez-Caro, Lilia C.; Sanchez-Sanchez, Mario; Bocanegra-Garcia, Virgilio; Rivera, Gildardo; Monge, Antonio

2011-01-01

We describe the synthesis of 12 new ethyl and methyl quinoxaline-7-carboxylate 1,4-di-N-oxide derivatives on solid supports with room temperature and microwave-assisted solvent-free procedures. Results show that solid supports have good catalytic activity in the formation of quinoxaline 1,4-di-N-oxide derivatives. We found that florisil and montmorillonite KSF and K10 could be used as new, easily available, inexpensive alternatives of catalysts. Additionally, room temperature and microwave-irradiation solvent-free synthesis was more efficient than a conventional procedure (Beirut reaction), reducing reaction time and increasing yield. (author)

Synthesis of quinoxaline 1,4-di-n-oxide derivatives on solid support using room temperature and microwave-assisted solvent-free procedures

Energy Technology Data Exchange (ETDEWEB)

Gomez-Caro, Lilia C.; Sanchez-Sanchez, Mario; Bocanegra-Garcia, Virgilio; Rivera, Gildardo [Universidad Autonoma de Tamaulipas, Reynosa (Mexico). Dept. de Farmacia y Quimica Medicinal; Monge, Antonio [Universidad de Navarra, Pamplona (Spain). Centro de Investigacion en Farmacobiologia Aplicada. Unidad de Investigacion y Desarrollo de Medicamentos

2011-07-01

We describe the synthesis of 12 new ethyl and methyl quinoxaline-7-carboxylate 1,4-di-N-oxide derivatives on solid supports with room temperature and microwave-assisted solvent-free procedures. Results show that solid supports have good catalytic activity in the formation of quinoxaline 1,4-di-N-oxide derivatives. We found that florisil and montmorillonite KSF and K10 could be used as new, easily available, inexpensive alternatives of catalysts. Additionally, room temperature and microwave-irradiation solvent-free synthesis was more efficient than a conventional procedure (Beirut reaction), reducing reaction time and increasing yield. (author)

A three-dimensional graphene aerogel containing solvent-free polyaniline fluid for high performance supercapacitors.

Science.gov (United States)

Gao, Zhaodongfang; Yang, Junwei; Huang, Jing; Xiong, Chuanxi; Yang, Quanling

2017-11-23

Conducting polymer based supercapacitors usually suffer from the difficulty of achieving high specific capacitance and good long-term stability simultaneously. In this communication, a long-chain protonic acid doped solvent-free self-suspended polyaniline (S-PANI) fluid and reduced graphene oxide (RGO) were used to fabricate a three-dimensional RGO/S-PANI aerogel via a simple self-assembled hydrothermal method, which was then applied as a supercapacitor electrode. This 3D RGO/S-PANI composite exhibited a high specific capacitance of up to 480 F g -1 at a current density of 1 A g -1 and 334 F g -1 even at a high discharge rate of 40 A g -1 . An outstanding cycling performance, with 96.14% of the initial capacitance remaining after 10 000 charging/discharging cycles at a rate of 10 A g -1 , was also achieved. Compared with the conventional conducting polymer materials, the 3D RGO/S-PANI composite presented more reliable rate capability and cycling stability. Moreover, S-PANI possesses excellent processability, thereby revealing its enormous potential in large scale production. We anticipate that the solvent-free fluid technique is also applicable to the preparation of other 3D graphene/polymer materials for energy storage.

Enzymes from solvent-tolerant microbes: useful biocatalysts for non-aqueous enzymology.

Science.gov (United States)

Gupta, Anshu; Khare, S K

2009-01-01

Solvent-tolerant microbes are a newly emerging class that possesses the unique ability to thrive in the presence of organic solvents. Their enzymes adapted to mediate cellular and metabolic processes in a solvent-rich environment and are logically stable in the presence of organic solvents. Enzyme catalysis in non-aqueous/low-water media is finding increasing applications for the synthesis of industrially important products, namely peptides, esters, and other trans-esterification products. Solvent stability, however, remains a prerequisite for employing enzymes in non-aqueous systems. Enzymes, in general, get inactivated or give very low rates of reaction in non-aqueous media. Thus, early efforts, and even some recent ones, have aimed at stabilization of enzymes in organic media by immobilization, surface modifications, mutagenesis, and protein engineering. Enzymes from solvent-tolerant microbes appear to be the choicest source for studying solvent-stable enzymes because of their unique ability to survive in the presence of a range of organic solvents. These bacteria circumvent the solvent's toxic effects by virtue of various adaptations, e.g. at the level of the cytoplasmic membrane, by degradation and transformation of solvents, and by active excretion of solvents. The recent screening of these exotic microbes has generated some naturally solvent-stable proteases, lipases, cholesterol oxidase, cholesterol esterase, cyclodextrin glucanotransferase, and other important enzymes. The unique properties of these novel biocatalysts have great potential for applications in non-aqueous enzymology for a range of industrial processes.

Molybdenum carbide nanoparticles as catalysts for oil sands upgrading: Dynamics and free-energy profiles

International Nuclear Information System (INIS)

Liu, Xingchen; Salahub, Dennis R.

2015-01-01

There is no doubt that a huge gap exists in understanding heterogeneous catalysis between a cluster model of a few atoms and a bulk model of periodic slabs. Nanoparticles, which are crucial in heterogeneous catalysis in industry, lie in the middle of the gap. We present here our work on the computational modelling of molybdenum carbide nanoparticles (MCNPs) as the catalysts for the upgrading of oil sands in the in-situ environment, using benzene hydrogenation as a model reaction. With a cluster model, efforts were first made to understand the mechanism of the reaction with a density functional theory (DFT) study on the adsorption of benzene and its hydrogenation product – cyclohexane, as well as the cyclic hydrogenation reaction intermediates on the Mo 2 C(0001) surface. From the thermodynamic data, along with literature information, it was found that the benzene hydrogenation reaction on molybdenum carbide happens most likely through a Langmuir-Hinshelwood mechanism with the gradual lifting up of the benzene molecule. The electron localization function (ELF) was then used to help understand the nature of the interactions between the MCNPs, identifying strong multi-center interactions between the adsorbates and the MCNPs. To enable the treatment of larger nanoparticles, a fast semi-empirical density functional tight-binding (DFTB) method was parameterized. With this method, the potential energy profiles of benzene hydrogenation reactions on different sizes of MCNPs are calculated. The study was then extended to consider a MCNP embedded in solvent (benzene), using a quantum mechanical (DFTB) / molecular mechanical approach. Calculations on the free energies profiles with the umbrella sampling method show that the entropy of the MCNPs and the solvent are essential in understanding the catalytic activity of the transition metal related nanoparticles for solid/liquid heterogeneous catalysis

Molybdenum carbide nanoparticles as catalysts for oil sands upgrading: Dynamics and free-energy profiles

Energy Technology Data Exchange (ETDEWEB)

Liu, Xingchen; Salahub, Dennis R. [Department of Chemistry, Institute for Quantum Science and Technology, and Centre for Molecular Simulation, University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4 (Canada)

2015-12-31

There is no doubt that a huge gap exists in understanding heterogeneous catalysis between a cluster model of a few atoms and a bulk model of periodic slabs. Nanoparticles, which are crucial in heterogeneous catalysis in industry, lie in the middle of the gap. We present here our work on the computational modelling of molybdenum carbide nanoparticles (MCNPs) as the catalysts for the upgrading of oil sands in the in-situ environment, using benzene hydrogenation as a model reaction. With a cluster model, efforts were first made to understand the mechanism of the reaction with a density functional theory (DFT) study on the adsorption of benzene and its hydrogenation product – cyclohexane, as well as the cyclic hydrogenation reaction intermediates on the Mo{sub 2}C(0001) surface. From the thermodynamic data, along with literature information, it was found that the benzene hydrogenation reaction on molybdenum carbide happens most likely through a Langmuir-Hinshelwood mechanism with the gradual lifting up of the benzene molecule. The electron localization function (ELF) was then used to help understand the nature of the interactions between the MCNPs, identifying strong multi-center interactions between the adsorbates and the MCNPs. To enable the treatment of larger nanoparticles, a fast semi-empirical density functional tight-binding (DFTB) method was parameterized. With this method, the potential energy profiles of benzene hydrogenation reactions on different sizes of MCNPs are calculated. The study was then extended to consider a MCNP embedded in solvent (benzene), using a quantum mechanical (DFTB) / molecular mechanical approach. Calculations on the free energies profiles with the umbrella sampling method show that the entropy of the MCNPs and the solvent are essential in understanding the catalytic activity of the transition metal related nanoparticles for solid/liquid heterogeneous catalysis.

Mechanochemical Solvent-Free and Catalyst-Free One-Pot Synthesis of Pyrano[2,3-d]Pyrimidine-2,4(1H,3H-Diones with Quantitative Yields

Directory of Open Access Journals (Sweden)

M. Reza Naimi-Jamal

2009-01-01

Full Text Available Solvent-free synthesis of pyrano[2,3-d]pyrimidine-2,4(1H,3H-diones by ball-milling and without any catalyst is described. This method provides several advantages such as being environmentally friendly, using a simple workup procedure, and affording high yields.

Enantioselective syntheses of aeruginosin 298-A and its analogues using a catalytic asymmetric phase-transfer reaction and epoxidation.

Science.gov (United States)

Ohshima, Takashi; Gnanadesikan, Vijay; Shibuguchi, Tomoyuki; Fukuta, Yuhei; Nemoto, Tetsuhiro; Shibasaki, Masakatsu

2003-09-17

We developed a versatile synthetic process for aeruginosin 298-A as well as several attractive analogues, in which all stereocenters were controlled by a catalytic asymmetric phase-transfer reaction and epoxidation. Furthermore, drastic counteranion effects in phase-transfer catalysis were observed for the first time, making it possible to three-dimensionally fine-tune the catalyst (ketal part, aromatic part, and counteranion).

A modified free-volume-based model for predicting vapor-liquid and solid-liquid equilibria for size asymmetric systems

DEFF Research Database (Denmark)

Radfarnia, H.R.; Ghotbi, C.; Taghikhani, V.

2005-01-01

The main purpose of this work is to present a free-volume combinatorial term in predicting vapor-liquid equilibrium (VLE) and solid-liquid equilibrium (SLE) of polymer/solvent and light and heavy hydrocarbon/hydrocarbon mixtures. The proposed term is based on a modification of the original Freed ...

Solvent Free Low-Melt Viscosity Imide Oligomers And Thermosetting Polyimide Composites

Science.gov (United States)

Chuang, CHun-Hua (Inventor)

2006-01-01

This invention relates to the composition and a solvent-free process for preparing novel imide oligomers and polymers specifically formulated with effective amounts of a dianhydride such as 2,3,3',4-biphenyltetra carboxylic dianydride (a-BPDA), at least one aromatic diamine' and an endcapped of 4-phenylethynylphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260-280" C. When the imide oligomer melt is cured at about 371 C. in a press or autoclave under 100-500 psi, the melt resulted in a thermoset polyimide having a glass transition temperature (T(sub g)) equal to and above 310 C. A novel feature of this process is that the monomers; namely the dianhydrides, diamines and the endcaps, are melt processable to form imide oligomers at temperatures ranging between 232-280 C. (450-535 F) without any solvent. These low-melt imide oligomers can be easily processed by resin transfer molding (RTM), vacuum-assisted resin transfer molding (VARTM) or the resin infusion process with fiber preforms e.g. carbon, glass or quartz preforms to produce polyimide matrix composites with 288-343C (550-650 F) high temperature performance capability.

An Efficient, Solvent-Free Process for Synthesizing Anhydrous MgCl₂

Energy Technology Data Exchange (ETDEWEB)

Motkuri, Radha K.; Vemuri, Venkata Rama S.; Barpaga, Dushyant; Schaef, Herbert T.; Loring, John S.; Martin, Paul F.; Lao, David; Nune, Satish K.; McGrail, Bernard P.

2018-01-02

A new efficient and solvent-free method for the synthesis of anhydrous MgCl2 from its hexahydrate is proposed. Fluidized dehydration of MgCl₂·6H₂O feedstock at 200 °C in a porous bed reactor yields MgCl2·nH2O (0 < n < 1), which has a similar diffraction pattern as activated MgCl2. The MgCl₂·nH₂O is then ammoniated directly using liquefied NH₃ in the absence of solvent to form MgCl₂·6NH₃. Calcination of the hexammoniate complex at 300 °C then yields anhydrous MgCl₂. Both dehydration and deammoniation were thoroughly studied using in situ as well as ex situ characterization techniques. Specifically, a detailed understanding of the dehydration process was monitored by in situ PXRD and in situ FTIR techniques where formation of salt with nH₂O (n = 4, 2, 1, <1) was characterized. Given the reduction in thermal energy required to produce dehydrated feedstock with this method compared with current strategies, significant cost benefits are expected. Overall, the combined effect of activation, macroporosity, and coordinated water depletion allows the formation of hexammoniate without using solvent, thus minimizing waste formation.

Asymmetric Michael Addition Mediated by Chiral Ionic Liquids

Science.gov (United States)

Suzuki, Yumiko

2018-01-01

Chiral ionic liquids with a focus on their applications in asymmetric Michael additions and related reactions were reviewed. The examples were classified on the basis of the mode of asymmetric induction (e.g., external induction/non-covalent interaction or internal induction/covalent bond formation), the roles in reactions (as a solvent or catalyst), and their structural features (e.g., imidazolium-based chiral cations, other chiral oniums; proline derivatives). Most of the reactions with high chiral induction are Michael addition of ketones or aldehydes to chalcones or nitrostyrenes where proline-derived chiral ionic liquids catalyze the reaction through enamine/ iminium formation. Many reports demonstrate the recyclability of ionic liquid-tagged pyrrolidines. PMID:29861702

Solvent extraction

Energy Technology Data Exchange (ETDEWEB)

Coombs, D.M.; Latimer, E.G.

1988-01-05

It is an object of this invention to provide for the demetallization and general upgrading of heavy oil via a solvent extracton process, and to improve the efficiency of solvent extraction operations. The yield and demetallization of product oil form heavy high-metal content oil is maximized by solvent extractions which employ either or all of the following techniques: premixing of a minor amount of the solvent with feed and using countercurrent flow for the remaining solvent; use of certain solvent/free ratios; use of segmental baffle tray extraction column internals and the proper extraction column residence time. The solvent premix/countercurrent flow feature of the invention substantially improves extractions where temperatures and pressures above the critical point of the solvent are used. By using this technique, a greater yield of extract oil can be obtained at the same metals content or a lower metals-containing extract oil product can be obtained at the same yield. Furthermore, the premixing of part of the solvent with the feed before countercurrent extraction gives high extract oil yields and high quality demetallization. The solvent/feed ratio features of the invention substanially lower the captial and operating costs for such processes while not suffering a loss in selectivity for metals rejection. The column internals and rsidence time features of the invention further improve the extractor metals rejection at a constant yield or allow for an increase in extract oil yield at a constant extract oil metals content. 13 figs., 3 tabs.

Dynamics of solvent-free grafted nanoparticles

KAUST Repository

Chremos, Alexandros; Panagiotopoulos, Athanassios Z.; Koch, Donald L.

2012-01-01

as well as grafted nanoparticles in a melt were compared to a reference system of bare (ungrafted) particles in a melt. Whereas longer chains lead to a larger hydrodynamic radius and lower relative diffusivity for grafted particles in a melt, bulk solvent

Environmental catalysis

International Nuclear Information System (INIS)

Montes Consuelo; Villa, Aida Luz

1996-01-01

The term environmental catalysis has been used lately to refer to a variety of applications of the catalysis, those which, they have grouped in the following categories: a) Control of emissions (chimney Gases and gases of the vehicles, Compound Organic Volatile (VOC), Scents, Chlorofluorocarbons) b) Conversion of having undone solids or liquids. C) Selective obtaining of alternating products that replace polluting compounds. d)replacement of catalysis environmentally dangerous And e)Development of catalysts for the obtaining of valuable chemical products without the formation of polluting by-products. In the group of Environmental Catalysis comes working in the first category, Particularly, in the exploration of active catalysts in the decrease of the emissions coming from combustion systems, carbon monoxide, hydrocarbons, nitrogen oxides (NOx), N20 and sulfur (SOx). Our fundamental premise is that the molecular meshes are catalytic potential for the development of a technology environmentally clean. These materials understand a class of inorganic compound with unique properties and intimately related with the structure. The net of the molecular meshes consists on tetrahedral configuration atoms (Al,Si, P, etc.) united to each other by oxygen atoms. As a result they are not formed three-dimensional structures alone with channels and cavities but also, with openings bounded by rings that consist of a certain number of tetrahedral atoms

Physicochemical and catalytic properties of Au nanorods micro-assembled in solvents of varying dipole moment and refractive index

Energy Technology Data Exchange (ETDEWEB)

Kaur, Rupinder; Pal, Bonamali, E-mail: bpal@thapar.edu

2015-02-15

Highlights: • Physicochemical activities of Au nanorods in water largely differ from organic solvents. • Au nanorods agglomeration increased with dipole moments of different polar solvents. • Refractive indexes of Au nanorods dispersion in various polar solvents are enhanced. • Electrokinetics significantly altered depending on agglomerated size of Au nanorods. • Catalysis or co-catalysis activity is varied as per the extent of Au nanorods coagulation. - Abstract: This paper deals with the impact of dipole moment (1.66–3.96 D) and refractive index (1.333–1.422) of the dispersion solvent on the plasmon absorption, surface charge, zeta potential, and adsorption properties of Au nanorods (AuNRs). AuNRs (length ≈ 53 nm and width ≈ 20 nm) undergo agglomeration (size 50–180 nm) with increase in the dipole moment of solvent (iPrOH < MeOH < DMF < DMSO). Whereas, no such coagulation occurs in H{sub 2}O and CCl{sub 4} suspension as confirmed by DLS and TEM size distribution. The electrostatic interaction of AuNRs with its surface adsorbed solvent dipoles leads to alteration of the their ionic state, absolute electronic charge and zeta potential (+49.79 mV in H{sub 2}O, +8.99 mV in DMF and −4.65 mV in MeOH dispersion) to a greater extent. This interaction distinctly modifies the adsorption behavior of polar molecules like p-nitrophenol and salicylic acid on AuNRs surface, as evidenced by the measured changes in their electro-kinetic parameters. As a result, we observe a substantial difference in catalytic and co-catalytic activities of AuNRs dispersed in various solvents as mentioned above because the catalytic properties of AuNRs are strongly dependent on the type of solvent in which they are dispersed.

Gaussian-Based Smooth Dielectric Function: A Surface-Free Approach for Modeling Macromolecular Binding in Solvents

Directory of Open Access Journals (Sweden)

Arghya Chakravorty

2018-03-01

Full Text Available Conventional modeling techniques to model macromolecular solvation and its effect on binding in the framework of Poisson-Boltzmann based implicit solvent models make use of a geometrically defined surface to depict the separation of macromolecular interior (low dielectric constant from the solvent phase (high dielectric constant. Though this simplification saves time and computational resources without significantly compromising the accuracy of free energy calculations, it bypasses some of the key physio-chemical properties of the solute-solvent interface, e.g., the altered flexibility of water molecules and that of side chains at the interface, which results in dielectric properties different from both bulk water and macromolecular interior, respectively. Here we present a Gaussian-based smooth dielectric model, an inhomogeneous dielectric distribution model that mimics the effect of macromolecular flexibility and captures the altered properties of surface bound water molecules. Thus, the model delivers a smooth transition of dielectric properties from the macromolecular interior to the solvent phase, eliminating any unphysical surface separating the two phases. Using various examples of macromolecular binding, we demonstrate its utility and illustrate the comparison with the conventional 2-dielectric model. We also showcase some additional abilities of this model, viz. to account for the effect of electrolytes in the solution and to render the distribution profile of water across a lipid membrane.

Solvent-free functionalization of fullerene C{sub 60} and pristine multi-walled carbon nanotubes with aromatic amines

Energy Technology Data Exchange (ETDEWEB)

Ramírez-Calera, Itzel J. [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510, México, D.F. (Mexico); Meza-Laguna, Victor [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510 México, D.F. (Mexico); Gromovoy, Taras Yu. [O.O. Chuiko Institute of Surface Chemistry, National Academy of Sciences of the Ukraine, Gen. Naumova 17, 03164 Kiev (Ukraine); Chávez-Uribe, Ma. Isabel [Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510 México, D.F. (Mexico); Basiuk, Vladimir A., E-mail: basiuk@nucleares.unam.mx [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510 México, D.F. (Mexico); Basiuk, Elena V., E-mail: elbg1111@gmail.com [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510, México, D.F. (Mexico)

2015-02-15

Highlights: • Pristine multi-walled carbon nanotubes were functionalized with aromatic amines. • The amines add onto nanotube defects, likewise they add onto fullerene C{sub 60}. • The addition takes place at elevated temperature and without organic solvents. • Functionalized nanotubes were characterized by a number of instrumental techniques. - Abstract: We employed a direct one-step solvent-free covalent functionalization of solid fullerene C{sub 60} and pristine multi-walled carbon nanotubes (MWCNTs) with aromatic amines 1-aminopyrene (AP), 2-aminofluorene (AF) and 1,5-diaminonaphthalene (DAN). The reactions were carried out under moderate vacuum, in a wide temperature range of 180–250 °C, during relatively short time of about 2 h. To confirm successful amine attachment, a large number of analytical techniques were used (depending on the nanomaterial functionalized) such as Fourier transform infrared, Raman, X-ray photoelectron, {sup 13}C cross-polarization magic angle spinning NMR spectroscopy, thermogravimetric analysis, laser-desorption ionization time-of-flight mass spectrometry, temperature-programmed desorption with mass spectrometric detection, as well as scanning and transmission electron microscopy. The nucleophilic addition of the aromatic amines to C{sub 60} molecule was studied theoretically by using density functional theory (PBE GGA functional with Grimme dispersion correction in conjunction with the DNP basis set). In the case of crystalline C{sub 60}, the solvent-free technique has a limited applicability due to poor diffusion of vaporous aromatic amines into the bulk. Nevertheless, the approach proposed allows for a facile preparation of aromatic amine-functionalized pristine MWCNTs without contamination with other chemical reagents, detergents and solvents, which is especially important for a vast variety of nanotube applications spanning from nanoelectronics to nanomedicine.

Ball Milling Assisted Solvent and Catalyst Free Synthesis of Benzimidazoles and Their Derivatives.

Science.gov (United States)

El-Sayed, Taghreed H; Aboelnaga, Asmaa; Hagar, Mohamed

2016-08-24

Benzoic acid and o-phenylenediamine efficiently reacted under the green solvent-free Ball Milling method. Several reaction parameters were investigated such as rotation frequency; milling balls weight and milling time. The optimum reaction condition was milling with 56.6 g weight of balls at 20 Hz frequency for one hour milling time. The study was extended for synthesis of a series of benzimidazol-2-one or benzimidazol-2-thione using different aldehydes; carboxylic acids; urea; thiourea or ammonium thiocyanate with o-phenylenediamine. Moreover; the alkylation of benzimidazolone or benzimidazolthione using ethyl chloroacetate was also studied.

A template-free solvent-mediated synthesis of high surface area boron nitride nanosheets for aerobic oxidative desulfurization.

Science.gov (United States)

Wu, Peiwen; Zhu, Wenshuai; Chao, Yanhong; Zhang, Jinshui; Zhang, Pengfei; Zhu, Huiyuan; Li, Changfeng; Chen, Zhigang; Li, Huaming; Dai, Sheng

2016-01-04

Hexagonal boron nitride nanosheets (h-BNNs) with rather high specific surface area (SSA) are important two-dimensional layer-structured materials. Here, a solvent-mediated synthesis of h-BNNs revealed a template-free lattice plane control strategy that induced high SSA nanoporous structured h-BNNs with outstanding aerobic oxidative desulfurization performance.

Preparation of ultra-fine calcium carbonate by a solvent-free reaction using supersonic airflow and low temperatures

OpenAIRE

Cai, Yan-Hua; Ma, Dong-Mei; Peng, Ru-Fang; Chu, Shi-Jin

2008-01-01

The treatment of calcium chloride with sodium carbonate under solvent-free conditions with a supersonic airflow and at a low heating temperature leads to the synthesis of ultra-fine calcium carbonate. The reaction not only involves mild conditions, a simple operation, and high yields but also gives a high conversion rate.

Stereodirection of an α-ketoester at sub-molecular sites on chirally modified Pt(111): Heterogeneous asymmetric catalysis

DEFF Research Database (Denmark)

Demers-Carpentier, V.; Rasmussen, A.M.H.; Goubert, G.

2013-01-01

Chirally modified Pt catalysts are used in the heterogeneous asymmetric hydrogenation of α-ketoesters. Stereoinduction is believed to occur through the formation of chemisorbed modifier–substrate complexes. In this study, the formation of diastereomeric complexes by coadsorbed methyl 3,3,3-triflu......Chirally modified Pt catalysts are used in the heterogeneous asymmetric hydrogenation of α-ketoesters. Stereoinduction is believed to occur through the formation of chemisorbed modifier–substrate complexes. In this study, the formation of diastereomeric complexes by coadsorbed methyl 3...

A Combined Synthetic and DFT Study on the Catalyst-Free and Solvent-Assisted Synthesis of 1,3,4-Oxadiazole-2-thiol Derivatives

Directory of Open Access Journals (Sweden)

Mohammad Soleiman-Beigi

2013-01-01

Full Text Available A novel practical and efficient catalyst-free method for the synthesis of 5-substituted 1,3,4-oxadiazole-2-thiols has been developed, which is assisted by reaction solvent (DMF. The solvent effects on product selectivity were studied based on Onsager’s reaction field theory of electrostatic solvation. The ab initio theoretical studies on the effect of solvents on the process also supported the suitability of DMF as the reaction medium for the preparation of 1,3,4-oxadiazole-2-thiol derivatives.

Surface and nanomolecular catalysis

CERN Document Server

Richards, Ryan

2006-01-01

Using new instrumentation and experimental techniques that allow scientists to observe chemical reactions and molecular properties at the nanoscale, the authors of Surface and Nanomolecular Catalysis reveal new insights into the surface chemistry of catalysts and the reaction mechanisms that actually occur at a molecular level during catalysis. While each chapter contains the necessary background and explanations to stand alone, the diverse collection of chapters shows how developments from various fields each contributed to our current understanding of nanomolecular catalysis as a whole. The

Free-Standing Bilayered Nanoparticle Superlattice Nanosheets with Asymmetric Ionic Transport Behaviors.

Science.gov (United States)

Rao, Siyuan; Si, Kae Jye; Yap, Lim Wei; Xiang, Yan; Cheng, Wenlong

2015-11-24

Natural cell membranes can directionally and selectively regulate the ion transport, which is critical for the functioning of living cells. Here, we report on the fabrication of an artificial membrane based on an asymmetric nanoparticle superlattice bilayered nanosheet, which exhibits similar ion transport characteristics. The superlattice nanosheets were fabricated via a drying-mediated self-assembly of polystyrene-capped gold nanoparticles at the liquid-air interface. By adopting a layer-by-layer assembly process, an asymmetric nanomembrane could be obtained consisting of two nanosheets with different nanoparticle size. The resulting nanomembranes exhibit an asymmetric ion transport behavior, and diode-like current-voltage curves were observed. The asymmetric ion transport is attributed to the cone-like nanochannels formed within the membranes, upon which a simulation map was established to illustrate the relationship between the channel structure and the ionic selectivity, in consistency with our experimental results. Our superlattice nanosheet-based design presents a promising strategy for the fabrication of next-generation smart nanomembranes for rationally and selectively regulating the ion transport even at a large ion flux, with potential applications in a wide range of fields, including biosensor devices, energy conversion, biophotonics, and bioelectronics.

FreeSASA: An open source C library for solvent accessible surface area calculations.

Science.gov (United States)

Mitternacht, Simon

2016-01-01

Calculating solvent accessible surface areas (SASA) is a run-of-the-mill calculation in structural biology. Although there are many programs available for this calculation, there are no free-standing, open-source tools designed for easy tool-chain integration. FreeSASA is an open source C library for SASA calculations that provides both command-line and Python interfaces in addition to its C API. The library implements both Lee and Richards' and Shrake and Rupley's approximations, and is highly configurable to allow the user to control molecular parameters, accuracy and output granularity. It only depends on standard C libraries and should therefore be easy to compile and install on any platform. The library is well-documented, stable and efficient. The command-line interface can easily replace closed source legacy programs, with comparable or better accuracy and speed, and with some added functionality.

An Organocatalyzed and Ultrasound Accelerated Expeditious Synthetic Route to 1,5-Benzodiazepines under Solvent-Free Conditions

Energy Technology Data Exchange (ETDEWEB)

Shinde, Pravin V.; Shingate, Bapurao B.; Shingare, Murlidhar S. [Babasaheb Ambedkar Marathwada University, Aurngabad (India)

2011-04-15

In the present work, successful implementation of ultrasound irradiations for the rapid synthesis of 1,5- benzodiazepine derivatives under solvent-free conditions is demonstrated. Use of a novel catalyst i.e. camphor sulphonic acid in combination with ultrasound technique is reported for the first time. Comparative study for the synthesis of 1,5-benzodiazepines using conventional as well as ultrasonication method is discussed.

Aminomethylation of enals through carbene and acid cooperative catalysis: concise access to β(2)-amino acids.

Science.gov (United States)

Xu, Jianfeng; Chen, Xingkuan; Wang, Ming; Zheng, Pengcheng; Song, Bao-An; Chi, Yonggui Robin

2015-04-20

A convergent, organocatalytic asymmetric aminomethylation of α,β-unsaturated aldehydes by N-heterocyclic carbene (NHC) and (in situ generated) Brønsted acid cooperative catalysis is disclosed. The catalytically generated conjugated acid from the base plays dual roles in promoting the formation of azolium enolate intermediate, formaldehyde-derived iminium ion (as an electrophilic reactant), and methanol (as a nucleophilic reactant). This redox-neutral strategy is suitable for the scalable synthesis of enantiomerically enriched β(2) -amino acids bearing various substituents. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular water oxidation catalysis

CERN Document Server

Llobet, Antoni

2014-01-01

Photocatalytic water splitting is a promising strategy for capturing energy from the sun by coupling light harvesting and the oxidation of water, in order to create clean hydrogen fuel. Thus a deep knowledge of the water oxidation catalysis field is essential to be able to come up with useful energy conversion devices based on sunlight and water splitting. Molecular Water Oxidation Catalysis: A Key Topic for New Sustainable Energy Conversion Schemes presents a comprehensive and state-of-the-art overview of water oxidation catalysis in homogeneous phase, describing in detail the most importan

Traceable atomic force microscopy of high-quality solvent-free crystals of [6,6]-phenyl-C61-butyric acid methyl ester

OpenAIRE

Lazzerini, GM; Paterno, GM; Tregnago, G; Treat, N; Stingelin, N; Yacoot, A; Cacialli, F

2016-01-01

We report high-resolution, traceable atomic force microscopymeasurements of high-quality, solvent-free single crystals of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). These were grown by drop-casting PCBM solutions onto the spectrosil substrates and by removing the residual solvent in a vacuum. A home-built atomic force microscope featuring a plane mirror differential optical interferometer, fiber-fed from a frequency-stabilized laser (emitting at 632.8???nm), was used to measure the cr...

Traceable atomic force microscopy of high-quality solvent-free crystals of [6,6]-phenyl-C-61-butyric acid methyl ester

OpenAIRE

Lazzerini, G. M.; Paterno, G. M.; Tregnago, G.; Treat, N.; Stingelin, N.; Yacoot, A.; Cacialli, F.

2016-01-01

We report high-resolution, traceable atomic force microscopymeasurements of high-quality, solvent-free single crystals of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). These were grown by drop-casting PCBM solutions onto the spectrosil substrates and by removing the residual solvent in a vacuum. A home-built atomic force microscope featuring a plane mirror differential optical interferometer, fiber-fed from a frequency-stabilized laser (emitting at 632.8 nm), was used to measure the crys...

Silica sulfuric acid: a reusable solid catalyst for one pot synthesis of densely substituted pyrrole-fused isocoumarins under solvent-free conditions

Directory of Open Access Journals (Sweden)

Sudipta Pathak

2013-11-01

Full Text Available A convenient and efficient methodology for the synthesis of densely substituted pyrrole-fused isocoumarins, which employs solid-supported silica sulfuric acid (SSA as catalyst, has been developed. When the mixture of ninhydrin adducts of acetylacetone/ethyl acetoacetate and primary amines was heated on the solid surface of SSA under solvent-free conditions, the pyrrole-fused isocoumarins were formed in good yields. This synthetic method has several advantages such as the employment of solvent-free reaction conditions without the use of any toxic reagents and metal catalysts, the ease of product isolation, the use of a recyclable catalyst, the low cost, the easy availability of the starting materials, and the excellent yields of products.

Concepts in catalysis

International Nuclear Information System (INIS)

Boudart, M.

1992-01-01

This paper reports on concept in catalysis which are very important in heterogeneous catalysis, even today, when in spite of surface science, the complexity of events at a real catalytic surface is still evading the understanding necessary for design. In this paper the authors will attempt to give an update on evolving concepts in heterogeneous catalysis. The topics include: counting active centers on metal surfaces; the notion of turnover frequency for a catalytic cycle; the concept of structure (in) sensitive reactions; the ensemble (geometric) vs. The ligand (electronic) effect following Sachtler's school; the idea of a rate determining step and of a most abundant reactive intermediate; the effect of surface non-uniformity on catalytic kinetics; what makes catalytic cycles turnover

Practical Engineering Aspects of Catalysis in Microreactors

Czech Academy of Sciences Publication Activity Database

Křišťál, Jiří; Stavárek, Petr; Vajglová, Zuzana; Vondráčková, Magdalena; Pavlorková, Jana; Jiřičný, Vladimír

2015-01-01

Roč. 41, č. 12 (2015), s. 9357-9371 ISSN 0922-6168. [Pannonian Symposium on Catalysis /12./. Castle Trest, 16.09.2014-20.09.2014] Institutional support: RVO:67985858 Keywords : heterogeneous catalysis * homogeneous catalysis * photo catalysis Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.833, year: 2015

Application of 2k Full Factorial Design in Optimization of Solvent-Free Microwave Extraction of Ginger Essential Oil

Directory of Open Access Journals (Sweden)

Mumtaj Shah

2014-01-01

Full Text Available The solvent-free microwave extraction of essential oil from ginger was optimized using a 23 full factorial design in terms of oil yield to determine the optimum extraction conditions. Sixteen experiments were carried out with three varying parameters, extraction time, microwave power, and type of sample for two levels of each. A first order regression equation best fits the experimental data. The predicted values calculated by the regression model were in good agreement with the experimental values. The results showed that the extraction time is the most prominent factor followed by microwave power level and sample type for extraction process. An average of 0.25% of ginger oil can be extracted using current setup. The optimum conditions for the ginger oil extraction using SFME were the extraction time 30 minutes, microwave power level 640 watts, and sample type, crushed sample. Solvent-free microwave extraction proves a green and promising technique for essential oil extraction.

Catalysis seen in action

NARCIS (Netherlands)

Tromp, M.

2015-01-01

Synchrotron radiation techniques are widely applied in materials research and heterogeneous catalysis. In homogeneous catalysis, its use so far is rather limited despite its high potential. Here, insights in the strengths and limitations of X-ray spectroscopy technique in the field of homogeneous

Flexible Fe2O3 and V2O5 nanofibers as binder-free electrodes for high-performance all-solid-state asymmetric supercapacitors.

Science.gov (United States)

Jiang, He; Niu, Hao; Yang, Xue; Sun, Zhiqin; Li, Fuzhi; Wang, Qian; Qu, Fengyu

2018-04-16

Flexible highly porous Fe2O3 and V2O5 nanofibers are synthesized by a facile electrospinning method followed by calcination treatment and directly used as binder-free electrodes for high-performance supercapacitors. These Fe2O3 and V2O5 nanofibers interconnect with each other and construct three-dimensional hierarchical porous films with high specific surface area. Benefiting from the unique structural features, the intriguing binder-free Fe2O3 and V2O5 porous nanofiber electrodes possess high specific capacitance of 255 F g-1 and 256 F g-1 at 2 mV s-1 in 1 M Na2SO4 electrolyte, respectively. An all-solid-state asymmetric supercapacitor is fabricated using Fe2O3 and V2O5 nanofibers as negative and positive electrodes, respectively, and the all-solid-state asymmetric supercapacitor can be operated up to 1.8 V attributed to the wide and opposite potential window of both electrodes. The assembled all-solid-state asymmetric supercapacitor achieves a high energy density up to 32.2 Wh kg-1 at an average power density of 128.7 W kg-1 as well as excellent cycling stability and power capability. The effective and facile synthesis method and superior electrochemical performance provided in this work make electrospun Fe2O3 and V2O5 nanofibers promising electrode materials for high performance asymmetric supercapacitors. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Palladium catalysed asymmetric alkylation of benzophenone Schiff ...

Indian Academy of Sciences (India)

some time in the application of phase transfer catalysis to the preparation of ... to free them from moisture contamination. Ionic liq- ... mined by chiral HPLC analysis (chiracel OD, hexane: 2-propanol ... chromatography on alumina 90 active basic (0.063–. 0.200 mm) ..... ing solubility of ionic liquids in water at 20. ◦. C, for the.

Nanocrystalline copper(II oxide-catalyzed one-pot four- component synthesis of polyhydroquinoline derivativesunder solvent-free conditions

Directory of Open Access Journals (Sweden)

J. Safaei-Ghomi

2011-07-01

Full Text Available The efficient and environmentally friendly method for the one-pot synthesis of polyhydroquinolines has been developed in the presence of CuO nanoparticles. The multi-component reactions of aldehydes, dimedone, ethyl acetoacetate andammonium acetate were carried out under solvent-free conditions to afford some polyhydroquinoline derivatives. This method provides several advantages including high yields, low reaction times and little catalyst loading.

Natrolite zeolite: A natural and reusable catalyst for one-pot synthesis of α-aminophosphonates under solvent-free conditions

Directory of Open Access Journals (Sweden)

Siavash Bahari

2017-02-01

Full Text Available α-Aminophosphonates are synthesized efficiently by one-pot reaction of aldehydes or ketones, amines, trialkyl phosphites in the presence of Natrolite zeolite as a natural catalyst under solvent-free conditions. Furthermore, the catalyst can be reused several times without any significant loss of catalytic activity.

Synthesis of Main-Chain Chiral Quaternary Ammonium Polymers for Asymmetric Catalysis Using Quaternization Polymerization

Directory of Open Access Journals (Sweden)

Md. Masud Parvez

2012-06-01

Full Text Available Main-chain chiral quaternary ammonium polymers were successfully synthesized by the quaternization polymerization of cinchonidine dimer with dihalides. The polymerization occurred smoothly under optimized conditions to give novel type of main-chain chiral quaternary ammonium polymers. The catalytic activity of the polymeric chiral organocatalysts was investigated on the asymmetric benzylation of N-(diphenylmethylideneglycine tert-butyl ester.

Preferential solvation and solvation shell composition of free base and protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin in aqueous organic mixed solvents

Science.gov (United States)

Farajtabar, Ali; Jaberi, Fatemeh; Gharib, Farrokh

2011-12-01

The solvatochromic properties of the free base and the protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) were studied in pure water, methanol, ethanol (protic solvents), dimethylsulfoxide, DMSO, (non-protic solvent), and their corresponding aqueous-organic binary mixed solvents. The correlation of the empirical solvent polarity scale ( ET) values of TPPS with composition of the solvents was analyzed by the solvent exchange model of Bosch and Roses to clarify the preferential solvation of the probe dyes in the binary mixed solvents. The solvation shell composition and the synergistic effects in preferential solvation of the solute dyes were investigated in terms of both solvent-solvent and solute-solvent interactions and also, the local mole fraction of each solvent composition was calculated in cybotactic region of the probe. The effective mole fraction variation may provide significant physico-chemical insights in the microscopic and molecular level of interactions between TPPS species and the solvent components and therefore, can be used to interpret the solvent effect on kinetics and thermodynamics of TPPS. The obtained results from the preferential solvation and solvent-solvent interactions have been successfully applied to explain the variation of equilibrium behavior of protonation of TPPS occurring in aqueous organic mixed solvents of methanol, ethanol and DMSO.

Molecular ingredients of heterogeneous catalysis

International Nuclear Information System (INIS)

Somorjai, G.A.

1982-06-01

The purpose of this paper is to present a review and status report to those in theoretical chemistry of the rapidly developing surface science of heterogeneous catalysis. The art of catalysis is developing into science. This profound change provides one with opportunities not only to understand the molecular ingredients of important catalytic systems but also to develop new and improved catalyst. The participation of theorists to find answers to important questions is sorely needed for the sound development of the field. It is the authors hope that some of the outstanding problems of heterogeneous catalysis that are identified in this paper will be investigated. For this purpose the paper is divided into several sections. The brief Introduction to the methodology and recent results of the surface science of heterogeneous catalysis is followed by a review of the concepts of heterogeneous catalysis. Then, the experimental results that identified the three molecular ingredients of catalysis, structure, carbonaceous deposit and the oxidation state of surface atoms are described. Each section is closed with a summary and a list of problems that require theoretical and experimental scrutiny. Finally attempts to build new catalyst systems and the theoretical and experimental problems that appeared in the course of this research are described

Molecular ingredients of heterogeneous catalysis

Energy Technology Data Exchange (ETDEWEB)

Somorjai, G.A.

1982-06-01

The purpose of this paper is to present a review and status report to those in theoretical chemistry of the rapidly developing surface science of heterogeneous catalysis. The art of catalysis is developing into science. This profound change provides one with opportunities not only to understand the molecular ingredients of important catalytic systems but also to develop new and improved catalyst. The participation of theorists to find answers to important questions is sorely needed for the sound development of the field. It is the authors hope that some of the outstanding problems of heterogeneous catalysis that are identified in this paper will be investigated. For this purpose the paper is divided into several sections. The brief Introduction to the methodology and recent results of the surface science of heterogeneous catalysis is followed by a review of the concepts of heterogeneous catalysis. Then, the experimental results that identified the three molecular ingredients of catalysis, structure, carbonaceous deposit and the oxidation state of surface atoms are described. Each section is closed with a summary and a list of problems that require theoretical and experimental scrutiny. Finally attempts to build new catalyst systems and the theoretical and experimental problems that appeared in the course of this research are described.

Bringing Catalysis with Gold Nanoparticles in Green Solvents to Graduate Level Students

Science.gov (United States)

Raghuwanshi, Vikram Singh; Wendt, Robert; O'Neill, Maeve; Ochmann, Miguel; Som, Tirtha; Fenger, Robert; Mohrmann, Marie; Hoell, Armin; Rademann, Klaus

2017-01-01

We demonstrate here a novel laboratory experiment for the synthesis of gold nanoparticles (AuNPs) by using a low energy gold-sputtering method together with a modern, green, and biofriendly deep eutectic solvent (DES). The strategy is straightforward, economical, ecofriendly, rapid, and clean. It yields uniform AuNPs of 5 nm in diameter with high…

Monopole catalysis: an overview

International Nuclear Information System (INIS)

Dawson, S.

1983-11-01

A summary of the talks presented in the topological workshop on monopole catalysis at this conference is given. We place special emphasis on the conservation laws which determine the allowed monopole-fermion interactions and on catalysis as a probe of the structure of a grand unified theory. 11 references

Synthesis of asymmetric polyetherimide membrane for CO2/N2 separation

Science.gov (United States)

Ahmad, A. L.; Salaudeen, Y. O.; Jawad, Z. A.

2017-06-01

Large emission of carbon dioxide (CO2) to the environment requires mitigation to avoid unbearable consequences on global climate change. The CO2 emissions generated by fossil fuel combustion within the power and industrial sectors need to be quickly curbed. The gas emission can be abated using membrane technology; this is one of the most promising approaches for selective separation of CO2/N2. The purpose of the study is to synthesis an asymmetric polyetherimide (PEI) membrane and to establish its morphological characteristics for CO2/N2 separation. The PEI flat-sheet asymmetric membrane was fabricated using phase inversion with N-methyl-2-pyrrolidone (NMP) as solvent and water-isopropanol as a coagulant. Particularly, polymer concentration of 20, 25, and 30 wt. % were studied. In addition, the structure and morphology of the produced membrane were observed using scanning electron microscopy (SEM). Importantly, results showed that the membrane with high PEI concentration of 30 wt. % yield an optimal selectivity of 10.7 for CO2/Nitrogen (N2) separation at 1 bar and 25 ºC for pure gas, aided by the membrane surface morphology. The dense skin present was as a result of non-solvent (water) while isopropanol generates a porous sponge structure. This appreciable separation performance makes the PEI asymmetric membrane an attractive alternative for CO2/N2 separation.

In-Vitro Characterization and Oral Bioavailability of Organic Solvent-free Solid Dispersions Containing Telmisartan

DEFF Research Database (Denmark)

Cao, Yue; Shi, Li-Li; Cao, Qing-Ri

2016-01-01

Poorly water-soluble drugs often suffer from limited or irreproducible clinical response due to their low solubility and dissolution rate. In this study, organic solvent-free solid dispersions (OSF-SDs) containing telmisartan (TEL) were prepared using polyvinylpyrrolidone K30 (PVP K30....... The results from DSC, XRD showed that TEL was molecularly dispersed in the OSF-SDs as an amorphous form. The FT-IR results suggested that intermolecular hydrogen bonding had formed between TEL and its carriers. The OSF-SDs exhibited significantly higher AUC0-24 h and Cmax, but similar Tmax as compared...

NaHSO4-SiO2-Promoted Solvent-Free Synthesis of Benzoxazoles, Benzimidazoles, and Benzothiazole Derivatives

Directory of Open Access Journals (Sweden)

K. Ravi Kumar

2013-01-01

Full Text Available An efficient protocol has been developed for the preparation of a library of benzoxazole, benzimidazole, and benzothiazole derivatives from reactions of acyl chlorides with o-substituted aminoaromatics in the presence of catalytic amount of silica-supported sodium hydrogen sulphate under solvent-free conditions. Simple workup procedure, high yield, easy availability, reusability, and use of ecofriendly catalyst are some of the striking features of the present protocol.

Solvent-free covalent functionalization of nanodiamond with amines

Energy Technology Data Exchange (ETDEWEB)

Basiuk, Elena V., E-mail: elenagd@unam.mx [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México D.F. (Mexico); Santamaría-Bonfil, Adriana; Meza-Laguna, Victor [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México D.F. (Mexico); Gromovoy, Taras Yu. [Institute of Surface Chemistry, National Academy of Sciences of the Ukraine, Gen. Naumova 17, 03164 Kiev (Ukraine); Alvares-Zauco, Edgar [Facultad de Ciencias, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México D.F. (Mexico); Contreras-Torres, Flavio F.; Rizo, Juan [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México D.F. (Mexico); Zavala, Guadalupe [Instituto de Biotecnología, Universidad Nacional Autónoma de México, Av. Universidad 2001, Col. Chamilpa, 62210, Cuernavaca, Morelos (Mexico); Basiuk, Vladimir A. [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México, D.F. (Mexico)

2013-06-15

Covalent functionalization of pristine nanodiamond (ND) with 1,12-diaminododecane (DAD), 1,5-diaminonaphthalene (DAN), poly(ethylene glycol) diamine (PEGDA), and polyethylenimine (PEI) was carried out by employing solvent-free methodology, which is based on thermal instead of chemical activation of carboxylic groups at ND surface. A simple solubility/dispersibility test in water and isopropanol showed an increased lipophilicity of the functionalized samples. The conversion of intrinsic carboxylic groups into the corresponding amide derivatives was characterized by means of Fourier-transform infrared spectroscopy. Thermogravimetric analysis found the highest organic content of about 18% for ND-PEI, followed by ND-DAD, for which the contribution of covalently bonded diamine was estimated to be of ca. 10%. In temperature programmed desorption measurements with mass spectrometric detection, the presence of organic functionalizing groups changed both mass spectra and thermodesorption curves of ND. The changes in morphology of primary and secondary ND aggregates were characterized by scanning and transmission electron microscopy, as well as by atomic force microscopy. The current–voltage measurements under atmospheric pressure found an increased conductivity for ND-DAN, as compared to that of pristine ND, whereas for ND-DAD, ND-PEGDA and ND-PEI a dramatic decrease in conductivity due to functionalization was observed.

Solvent-free covalent functionalization of nanodiamond with amines

International Nuclear Information System (INIS)

Basiuk, Elena V.; Santamaría-Bonfil, Adriana; Meza-Laguna, Victor; Gromovoy, Taras Yu.; Alvares-Zauco, Edgar; Contreras-Torres, Flavio F.; Rizo, Juan; Zavala, Guadalupe; Basiuk, Vladimir A.

2013-01-01

Covalent functionalization of pristine nanodiamond (ND) with 1,12-diaminododecane (DAD), 1,5-diaminonaphthalene (DAN), poly(ethylene glycol) diamine (PEGDA), and polyethylenimine (PEI) was carried out by employing solvent-free methodology, which is based on thermal instead of chemical activation of carboxylic groups at ND surface. A simple solubility/dispersibility test in water and isopropanol showed an increased lipophilicity of the functionalized samples. The conversion of intrinsic carboxylic groups into the corresponding amide derivatives was characterized by means of Fourier-transform infrared spectroscopy. Thermogravimetric analysis found the highest organic content of about 18% for ND-PEI, followed by ND-DAD, for which the contribution of covalently bonded diamine was estimated to be of ca. 10%. In temperature programmed desorption measurements with mass spectrometric detection, the presence of organic functionalizing groups changed both mass spectra and thermodesorption curves of ND. The changes in morphology of primary and secondary ND aggregates were characterized by scanning and transmission electron microscopy, as well as by atomic force microscopy. The current–voltage measurements under atmospheric pressure found an increased conductivity for ND-DAN, as compared to that of pristine ND, whereas for ND-DAD, ND-PEGDA and ND-PEI a dramatic decrease in conductivity due to functionalization was observed.

One-pot solvent-free rapid and green synthesis of 3,4-dihydropyrano[c]chromenes using grindstone chemistry

Directory of Open Access Journals (Sweden)

Devji S. Patel

2016-09-01

Full Text Available An easy solvent-free method is described for the synthesis of 3,4-dihydropyrano[c]chromenes by a one pot three component coupling reaction of aromatic aldehydes, malononitrile, and 4-hydroxycoumarin using basic ionic liquid as the catalyst by grindstone chemistry. The salient features of this one pot protocol are short reaction times, cleaner reaction profiles and simple workup.

STUDIES ON SOLVENT EXTRACTION OF FREE HYDROGEN ...

African Journals Online (AJOL)

synthesized through glucose degradation (glycolysis) to lactic acid. ... g sample into a well stoppered plastic bottle and mixed with 20 mL of distilled .... Recovery of used solvent is necessary because methylchloroform is toxic to the bacteria.

Catalysis of Supramolecular Hydrogelation

NARCIS (Netherlands)

Trausel, F.; Versluis, F.; Maity, C.; Poolman, J.M.; Lovrak, M.; van Esch, J.H.; Eelkema, R.

2016-01-01

ConspectusOne often thinks of catalysts as chemical tools to accelerate a reaction or to have a reaction run under more benign conditions. As such, catalysis has a role to play in the chemical industry and in lab scale synthesis that is not to be underestimated. Still, the role of catalysis in

Tipping Point for Expansion of Layered Aluminosilicates in Weakly Polar Solvents: Supercritical CO ₂

Energy Technology Data Exchange (ETDEWEB)

Schaef, Herbert T.; Loganathan, Narasimhan; Bowers, Geoffrey M.; Kirkpatrick, Robert J.; Yazaydin, A. O.; Burton, Sarah D.; Hoyt, David W.; Thanthiriwatte, Sahan; Dixon, David A.; McGrail, Bernard P.; Rosso, Kevin M.; Ilton, Eugene S.; Loring, John S.

2017-10-11

Layered aluminosilicates play a dominant role in the mechanical and gas storage properties of the subsurface, are used in diverse industrial applications, and serve as model materials for understanding solvent-ion-support systems. Although expansion in the presence of H2O is well known to be systematically correlated with the hydration free energy of the interlayer cation, in environments dominated by non-polar solvents (i.e. CO2), uptake into the interlayer is not well-understood. Using novel high pressure capabilities, we investigated the interaction of super-critical CO2 with Na+-, NH4+-, and Cs+-saturated montmorillonite, comparing results with predictions from molecular dynamics simulations. Despite the known trend in H2O, and that cation solvation energies in CO2 suggest a stronger interaction with Na+, both the NH4+- and Cs+-clays readily absorbed CO2 and expanded while the Na+-clay did not. The apparent inertness of the Na+-clay was not due to kinetics, as experiments seeking a stable expanded state showed that none exists. Molecular dynamics simulations revealed a large endothermicity to CO2 intercalation in the Na+-clay, but little or no energy barrier for the NH4+- and Cs+-clays. Consequently, we have shown for the first time that in the presence of a low dielectric constant gas swelling depends more on the strength of the interaction between interlayer cation and aluminosilicate sheets and less on that with solvent. The finding suggests a distinct regime in layered aluminosilicates swelling behavior triggered by low solvent polarizability, with important implications in geomechanics, storage and retention of volatile gases, and across industrial uses in gelling, decoloring, heterogeneous catalysis, and semi-permeable reactive barriers.

Solvent effect on Rb+ to K+ ion mutation: Monte Carlo simulation study

International Nuclear Information System (INIS)

Kim, Hag Sung

2000-01-01

The solvent effects on the relative free energies of solvation and the difference in partition coefficients (log P) for Rb + to K + mutation in several solvents have been investigated using Monte Carlo simulation (MCS) of statistical perturbation theory (SPT). In comparing the relative free energies for interconversion of one ion pair, Rb + to K + , in H 2 O (TIP4P) in this study with the relative free energies of the computer simulations and the experimental, we found that the figure in this study is -5.00 ± 0.11 kcal/mol. There is good agreement among various studies, taking into account both methods used to obtain the hydration free energies and standard deviations. There is also good agreement between the calculated structural properties of this study and the simulations, ab initio and the experimental results. We have explained the deviation of the relationship between the free energy difference and the Onsager dielectric function of solvents by the electron pair donor properties of the solvents. For the Rb + and K + ion pair, the Onsager dielectric function of solvents (or solvent permittivity), donor number of solvent and the differences in solvation dominate the differences in the relative free energies of solvation and partition coefficients

Solvent-free and catalyst-free chemistry: A benign pathway to sustainability

Science.gov (United States)

In the past decade, alternative benign organic methodologies have become an imperative part of organic syntheses and novel chemical reactions. The various new and innovative sustainable organic reactions and methodologies using no solvents or catalysts and employing alternative ...

Chemoselective Synthesis of Dithioacetals from Bio-aldehydes with Zeolites under Ambient and Solvent-free Conditions

DEFF Research Database (Denmark)

Li, Hu; Yang, Tingting; Riisager, Anders

2017-01-01

of commercial and modified zeolites are excellent catalysts for thioacetalization of different thiols with carbonyl compounds, including biomass-derived aldehydes, at room temperature under solvent-free conditions. A near quantitative yield of dithioacetal was obtained over H-beta(19) at room temperature......Dithioacetals are an important class of versatile compounds extensively applied in pharmaceuticals, separations, electrochemistry, and organic synthesis, but few heterogeneous catalytic systems are reported to be generally applicable for their synthesis from a wide range of substrates. A series...

Solvent-Free Lipase-Catalyzed Synthesis of Technical-Grade Sugar Esters and Evaluation of Their Physicochemical and Bioactive Properties

Directory of Open Access Journals (Sweden)

Ran Ye

2016-05-01

Full Text Available Technical-grade oleic acid esters of sucrose and fructose were prepared using solvent-free biocatalysis at 65 °C, without any downstream purification applied, and their physicochemical and bioactivity-related properties were evaluated and compared to a commercially available sucrose laurate emulsifier. To increase the conversion of sucrose and fructose oleate, prepared previously using solvent-free lipase-catalyzed esterification catalyzed by Rhizomucor miehei lipase (81% and 83% ester, respectively, the enzymatic reaction conditions was continued using CaSO4 to control the reactor’s air headspace and a lipase (from Candida antarctica B with a hydrophobic immobilization matrix to provide an ultralow water activity, and high-pressure homogenation, to form metastable suspensions of 2.0–3.3 micron sized saccharide particles in liquid-phase reaction media. These measures led to increased ester content of 89% and 96% for reactions involving sucrose and fructose, respectively. The monoester content among the esters decreased from 90% to <70% due to differences in regioselectivity between the lipases. The resultant technical-grade sucrose and fructose lowered the surface tension to <30 mN/m, and possessed excellent emulsification capability and stability over 36 h using hexadecane and dodecane as oils, comparable to that of sucrose laurate and Tween® 80. The technical-grade sugar esters, particularly fructose oleate, more effectively inhibited gram-positive foodborne pathogens (Lactobacillus plantarum, Pediococcus pentosaceus and Bacillus subtilis. Furthermore, all three sugar esters displayed antitumor activity, particularly the two sucrose esters. This study demonstrates the importance of controlling the biocatalysts’ water activity to achieve high conversion, the impact of a lipase’s regioselectivity in dictating product distribution, and the use of solvent-free biocatalysis to important biobased surfactants useful in foods, cosmetics

Catalysis for alternative energy generation

CERN Document Server

2012-01-01

Summarizes recent problems in using catalysts in alternative energy generation and proposes novel solutions  Reconsiders the role of catalysis in alternative energy generation  Contributors include catalysis and alternative energy experts from across the globe

Green chemistry by nano-catalysis

KAUST Repository

Polshettiwar, Vivek; Varma, Rajender S.

2010-01-01

the homogeneous catalysts. This review focuses on the use of nano-catalysis for green chemistry development including the strategy of using microwave heating with nano-catalysis in benign aqueous reaction media which offers an extraordinary synergistic effect

Editorial: Nanoscience makes catalysis greener

KAUST Repository

Polshettiwar, Vivek; Basset, Jean-Marie; Astruc, Didier

2012-01-01

Green chemistry by nanocatalysis: Catalysis is a strategic field of science because it involves new ways of meeting energy and sustainability challenges. The concept of green chemistry, which makes the science of catalysis even more creative, has

Fabrication of oxide-free graphene suspension and transparent thin films using amide solvent and thermal treatment

International Nuclear Information System (INIS)

Oh, Se Young; Kim, Sung Hwan; Chi, Yong Seung; Kang, Tae Jin

2012-01-01

Graphical abstract: New methodology for suspended graphene sheets of high-quality (oxide-free), high-yield (high concentration) using amide solvent exfoliation and thermal treatment at 800 °C. We confirmed that the van der Waals force between the graphene layers decreases as increasing thermal treatment temperatures as shown XRD data (b). Highlights: ► Propose of new methodology to prepare oxide-free graphene sheets suspension. ► The graphene suspension concentration is enhanced by thermal treatment. ► Decrease of van der Waals force between the graphene layers by high temperature and pressure. ► This method has the potential as technology for mass production. ► It could be applied in transparent and flexible electronic devices. - Abstract: High quality graphene sheets were produced from graphite by liquid phase exfoliation using N-methyl-2-pyrrolidone (NMP) and a subsequent thermal treatment to enhance the exfoliation. The exfoliation was enhanced by treatment with organic solvent and high thermal expansion producing high yields of the high-quality and defect-free graphene sheets. The graphene was successfully deposited on a flexible and transparent polymer film using the vacuum filtration method. SEM images of thin films of graphene treated at 800 °C showed uniform structure with no defects commonly found in films made of graphene produced by other techniques. Thin films of graphene prepared at higher temperatures showed superior transmittance and conductivity. The sheet-resistance of the graphene film treated at 800 °C was 2.8 × 10 3 kΩ/□ with 80% transmittance.

Solid acid catalysis from fundamentals to applications

CERN Document Server

Hattori, Hideshi

2014-01-01

IntroductionTypes of solid acid catalystsAdvantages of solid acid catalysts Historical overviews of solid acid catalystsFuture outlookSolid Acids CatalysisDefinition of acid and base -Brnsted acid and Lewis acid-Acid sites on surfacesAcid strengthRole of acid sites in catalysisBifunctional catalysisPore size effect on catalysis -shape selectivity-Characterization of Solid Acid Catalysts Indicator methodTemperature programmed desorption (TPD) of ammoniaCalorimetry of adsorption of basic moleculesInfrare

Neutrons for Catalysis: A Workshop on Neutron Scattering Techniques for Studies in Catalysis

International Nuclear Information System (INIS)

Overbury, Steven H.; Coates, Leighton; Herwig, Kenneth W.; Kidder, Michelle

2011-01-01

This report summarizes the Workshop on Neutron Scattering Techniques for Studies in Catalysis, held at the Spallation Neutron Source (SNS) at Oak Ridge National Laboratory (ORNL) on September 16 and 17, 2010. The goal of the Workshop was to bring experts in heterogeneous catalysis and biocatalysis together with neutron scattering experimenters to identify ways to attack new problems, especially Grand Challenge problems in catalysis, using neutron scattering. The Workshop locale was motivated by the neutron capabilities at ORNL, including the High Flux Isotope Reactor (HFIR) and the new and developing instrumentation at the SNS. Approximately 90 researchers met for 1 1/2 days with oral presentations and breakout sessions. Oral presentations were divided into five topical sessions aimed at a discussion of Grand Challenge problems in catalysis, dynamics studies, structure characterization, biocatalysis, and computational methods. Eleven internationally known invited experts spoke in these sessions. The Workshop was intended both to educate catalyst experts about the methods and possibilities of neutron methods and to educate the neutron community about the methods and scientific challenges in catalysis. Above all, it was intended to inspire new research ideas among the attendees. All attendees were asked to participate in one or more of three breakout sessions to share ideas and propose new experiments that could be performed using the ORNL neutron facilities. The Workshop was expected to lead to proposals for beam time at either the HFIR or the SNS; therefore, it was expected that each breakout session would identify a few experiments or proof-of-principle experiments and a leader who would pursue a proposal after the Workshop. Also, a refereed review article will be submitted to a prominent journal to present research and ideas illustrating the benefits and possibilities of neutron methods for catalysis research.

Neutrons for Catalysis: A Workshop on Neutron Scattering Techniques for Studies in Catalysis

Energy Technology Data Exchange (ETDEWEB)

Overbury, Steven {Steve} H [ORNL; Coates, Leighton [ORNL; Herwig, Kenneth W [ORNL; Kidder, Michelle [ORNL

2011-10-01

This report summarizes the Workshop on Neutron Scattering Techniques for Studies in Catalysis, held at the Spallation Neutron Source (SNS) at Oak Ridge National Laboratory (ORNL) on September 16 and 17, 2010. The goal of the Workshop was to bring experts in heterogeneous catalysis and biocatalysis together with neutron scattering experimenters to identify ways to attack new problems, especially Grand Challenge problems in catalysis, using neutron scattering. The Workshop locale was motivated by the neutron capabilities at ORNL, including the High Flux Isotope Reactor (HFIR) and the new and developing instrumentation at the SNS. Approximately 90 researchers met for 1 1/2 days with oral presentations and breakout sessions. Oral presentations were divided into five topical sessions aimed at a discussion of Grand Challenge problems in catalysis, dynamics studies, structure characterization, biocatalysis, and computational methods. Eleven internationally known invited experts spoke in these sessions. The Workshop was intended both to educate catalyst experts about the methods and possibilities of neutron methods and to educate the neutron community about the methods and scientific challenges in catalysis. Above all, it was intended to inspire new research ideas among the attendees. All attendees were asked to participate in one or more of three breakout sessions to share ideas and propose new experiments that could be performed using the ORNL neutron facilities. The Workshop was expected to lead to proposals for beam time at either the HFIR or the SNS; therefore, it was expected that each breakout session would identify a few experiments or proof-of-principle experiments and a leader who would pursue a proposal after the Workshop. Also, a refereed review article will be submitted to a prominent journal to present research and ideas illustrating the benefits and possibilities of neutron methods for catalysis research.

Thin-film composite crosslinked polythiosemicarbazide membranes for organic solvent nanofiltration (OSN)

KAUST Repository

Aburabie, Jamaliah

2015-01-01

In this work we report a new class of solvent stable thin-film composite (TFC) membrane fabricated on crosslinked polythiosemicarbazide (PTSC) as substrate that exhibits superior stability compared with other solvent stable polymeric membranes reported up to now. Integrally skinned asymmetric PTSC membranes were prepared by the phase inversion process and crosslinked with an aromatic bifunctional crosslinker to improve the solvent stability. TFC membranes were obtained via interfacial polymerization using trimesoyl chloride (TMC) and diaminopiperazine (DAP) monomers. The membranes were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and contact angle measurement.The membranes exhibited high fluxes toward solvents like tetrahydrofuran (THF), dimethylformamide (DMF) and dimethylsulfoxide (DMSO) ranging around 20L/m2 h at 5bar with a molecular weight cut off (MWCO) of around 1000g/mol. The PTSC-based thin-film composite membranes are very stable toward polar aprotic solvents and they have potential applications in the petrochemical and pharmaceutical industry.

Next-Generation Catalysis for Renewables: Combining Enzymatic with Inorganic Heterogeneous Catalysis for Bulk Chemical Production

DEFF Research Database (Denmark)

Vennestrøm, Peter Nicolai Ravnborg; Christensen, C.H.; Pedersen, S.

2010-01-01

chemical platform under different conditions than those conventionally employed. Indeed, new process and catalyst concepts need to be established. Both enzymatic catalysis (biocatalysis) and heterogeneous inorganic catalysis are likely to play a major role and, potentially, be combined. One type...... of combination involves one-pot cascade catalysis with active sites from bio- and inorganic catalysts. In this article the emphasis is placed specifically on oxidase systems involving the coproduction of hydrogen peroxide, which can be used to create new in situ collaborative oxidation reactions for bulk...

Solvent-free synthesis of C10 and C11 branched alkanes from furfural and methyl isobutyl ketone.

Science.gov (United States)

Yang, Jinfan; Li, Ning; Li, Guangyi; Wang, Wentao; Wang, Aiqin; Wang, Xiaodong; Cong, Yu; Zhang, Tao

2013-07-01

Our best results jet: C10 and C11 branched alkanes, with low freezing points, are synthesized through the aldol condensation of furfural and methyl isobutyl ketone from lignocellulose, which is then followed by hydrodeoxygenation. These jet-fuel-range alkanes are obtained in high overall yields (≈90%) under solvent-free conditions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Computational Design of Clusters for Catalysis

Science.gov (United States)

Jimenez-Izal, Elisa; Alexandrova, Anastassia N.

2018-04-01

When small clusters are studied in chemical physics or physical chemistry, one perhaps thinks of the fundamental aspects of cluster electronic structure, or precision spectroscopy in ultracold molecular beams. However, small clusters are also of interest in catalysis, where the cold ground state or an isolated cluster may not even be the right starting point. Instead, the big question is: What happens to cluster-based catalysts under real conditions of catalysis, such as high temperature and coverage with reagents? Myriads of metastable cluster states become accessible, the entire system is dynamic, and catalysis may be driven by rare sites present only under those conditions. Activity, selectivity, and stability are highly dependent on size, composition, shape, support, and environment. To probe and master cluster catalysis, sophisticated tools are being developed for precision synthesis, operando measurements, and multiscale modeling. This review intends to tell the messy story of clusters in catalysis.

Computational scheme for pH-dependent binding free energy calculation with explicit solvent.

Science.gov (United States)

Lee, Juyong; Miller, Benjamin T; Brooks, Bernard R

2016-01-01

We present a computational scheme to compute the pH-dependence of binding free energy with explicit solvent. Despite the importance of pH, the effect of pH has been generally neglected in binding free energy calculations because of a lack of accurate methods to model it. To address this limitation, we use a constant-pH methodology to obtain a true ensemble of multiple protonation states of a titratable system at a given pH and analyze the ensemble using the Bennett acceptance ratio (BAR) method. The constant pH method is based on the combination of enveloping distribution sampling (EDS) with the Hamiltonian replica exchange method (HREM), which yields an accurate semi-grand canonical ensemble of a titratable system. By considering the free energy change of constraining multiple protonation states to a single state or releasing a single protonation state to multiple states, the pH dependent binding free energy profile can be obtained. We perform benchmark simulations of a host-guest system: cucurbit[7]uril (CB[7]) and benzimidazole (BZ). BZ experiences a large pKa shift upon complex formation. The pH-dependent binding free energy profiles of the benchmark system are obtained with three different long-range interaction calculation schemes: a cutoff, the particle mesh Ewald (PME), and the isotropic periodic sum (IPS) method. Our scheme captures the pH-dependent behavior of binding free energy successfully. Absolute binding free energy values obtained with the PME and IPS methods are consistent, while cutoff method results are off by 2 kcal mol(-1) . We also discuss the characteristics of three long-range interaction calculation methods for constant-pH simulations. © 2015 The Protein Society.

2010 CATALYSIS GORDON RESEARCH CONFERENCE, JUNE 27 - JULY 2, 2010, NEW LONDON, NEW HAMPSHIRE

Energy Technology Data Exchange (ETDEWEB)

Abhaya Datye

2010-07-02

Catalysis is a key technology for improving the quality of life while simultaneously reducing the adverse impact of human activities on the environment. The discovery of new catalytic processes and the improvement of existing ones are also critically important for securing the nation's energy supply. The GRC on Catalysis is considered one the most prestigious conference for catalysis research, bringing together leading researchers from both academia, industry and national labs to discuss the latest, most exciting research in catalysis and the future directions for the field. The 2010 GRC on Catalysis will follow time-honored traditions and feature invited talks from the world's leading experts in the fundamentals and applications of catalytic science and technology. We plan to have increased participation from industry. The extended discussions in the company of outstanding thinkers will stimulate and foster new science. The conference will include talks in the following areas: Alternative feedstocks for chemicals and fuels, Imaging and spectroscopy, Design of novel catalysts, Catalyst preparation fundamentals, Molecular insights through theory, Surface Science, Catalyst stability and dynamics. In 2010, the Catalysis conference will move to a larger conference room with a new poster session area that will allow 40 posters per session. The dorm rooms provide single and double accommodations, free WiFi and the registration fee includes all meals and the famous lobster dinner on Thursday night. Afternoons are open to enjoy the New England ambiance with opportunities for hiking, sailing, golf and tennis to create an outstanding conference that will help you network with colleagues, and make long lasting connections.

Catalysis seen in action.

Science.gov (United States)

Tromp, Moniek

2015-03-06

Synchrotron radiation techniques are widely applied in materials research and heterogeneous catalysis. In homogeneous catalysis, its use so far is rather limited despite its high potential. Here, insights in the strengths and limitations of X-ray spectroscopy technique in the field of homogeneous catalysis are given, including new technique developments. A relevant homogeneous catalyst, used in the industrially important selective oligomerization of ethene, is taken as a worked-out example. Emphasis is placed on time-resolved operando X-ray absorption spectroscopy with outlooks to novel high energy resolution and emission techniques. All experiments described have been or can be done at the Diamond Light Source Ltd (Didcot, UK). © 2015 The Author(s) Published by the Royal Society. All rights reserved.

Specific acid catalysis and Lewis acid catalysis of Diels–Alder reactions in aqueous media

NARCIS (Netherlands)

Mubofu, Egid B.; Engberts, Jan B.F.N.

2004-01-01

A comparative study of specific acid catalysis and Lewis acid catalysis of Diels–Alder reactions between dienophiles (1, 4 and 6) and cyclopentadiene (2) in water and mixed aqueous media is reported. The reactions were performed in water with copper(II) nitrate as the Lewis acid catalyst whereas

Specific acid catalysis and Lewis acid catalysis of Diels-Alder reactions in aqueous media

NARCIS (Netherlands)

Mubofu, E.B.; Engberts, J.B.F.N.

A comparative study of specific acid catalysis and Lewis acid catalysis of Diells-Alder reactions between dienophiles (1, 4 and 6) and cyclopentadiene (2) in water and mixed aqueous media is reported. The reactions were performed in water with copper(II) nitrate as the Lewis acid catalyst whereas

Orthogonal protection of saccharide polyols through solvent-free one-pot sequences based on regioselective silylations

Directory of Open Access Journals (Sweden)

Serena Traboni

2016-12-01

Full Text Available tert-Butyldimethylsilyl (TBDMS and tert-butyldiphenylsilyl (TBDPS are alcohol protecting groups widely employed in organic synthesis in view of their compatibility with a wide range of conditions. Their regioselective installation on polyols generally requires lengthy reactions and the use of high boiling solvents. In the first part of this paper we demonstrate that regioselective silylation of sugar polyols can be conducted in short times with the requisite silyl chloride and a very limited excess of pyridine (2–3 equivalents. Under these conditions, that can be regarded as solvent-free conditions in view of the insolubility of the polyol substrates, the reactions are faster than in most examples reported in the literature, and can even be further accelerated with a catalytic amount of tetrabutylammonium bromide (TBAB. The strategy proved also useful for either the selective TBDMS protection of secondary alcohols or the fast per-O-trimethylsilylation of saccharide polyols. In the second part of the paper the scope of the silylation approach was significantly extended with the development of unprecedented “one-pot” and “solvent-free” sequences allowing the regioselective silylation/alkylation (or the reverse sequence of saccharide polyols in short times. The developed methodologies represent a very useful and experimentally simple tool for the straightforward access to saccharide building-blocks useful in organic synthesis.

Chemical catalysis in biodiesel production (I): enzymatic catalysis processes

International Nuclear Information System (INIS)

Jachmarian, I.; Dobroyan, M.; Veira, J.; Vieitez, I.; Mottini, M.; Segura, N.; Grompone, M.

2009-01-01

There are some well known advantages related with the substitution of chemical catalysis by enzymatic catalysis processes.Some commercial immobilized lipases are useful for the catalysis of bio diesel reaction, which permits the achievement of high conversions and the recovery of high purity products, like a high quality glycerine. The main disadvantage of this alternative method is related with the last inactivation of the enzyme (by both the effect of the alcohol and the absorption of glycerol on catalyst surface), which added to the high cost of the catalyst, produces an unfavourable economical balance of the entire process. In the work the efficiency of two commercial immobilized lipases (Lipozyme TL IM y Novozyme 435 NNovozymes-Dinamarca) in the catalysis of the continuous transesterification of sunflower oil with different alcohols was studied. The intersolubility of the different mixturesinvolving reactans (S oil/alkyl esters/alcohol) and products (P mixtures with a higher content of 1% of glycerol,while for ethanol homogeneous mixtures were obtained at 12% of glycerol (44.44 12).Using and ethanolic substrate at the proportion S=19:75:6 and Lipozyme TL IM, it was possible to achieve a 98% of convertion to the corresponding biodiesel.When Novozymes 435 catalyzed the process it was possible to increase the oil concentration in the substrateaccording to proportion S=35:30:35, and a 78% conversion was obtained. The productivity shown by the firt enzyme was 70mg biodiesel g enzime-1, hora-1 while with the second one the productivity increased to 230. Results suggested that the convenient adjustement of substrate composition with the addition of biodiesel to reactants offers an efficient method for maximizing the enzyme productivity, hence improving the profitability of the enzymatic catalyzed process. (author)

Stochastic level-set variational implicit-solvent approach to solute-solvent interfacial fluctuations

Energy Technology Data Exchange (ETDEWEB)

Zhou, Shenggao, E-mail: sgzhou@suda.edu.cn, E-mail: bli@math.ucsd.edu [Department of Mathematics and Mathematical Center for Interdiscipline Research, Soochow University, 1 Shizi Street, Jiangsu, Suzhou 215006 (China); Sun, Hui; Cheng, Li-Tien [Department of Mathematics, University of California, San Diego, La Jolla, California 92093-0112 (United States); Dzubiella, Joachim [Soft Matter and Functional Materials, Helmholtz-Zentrum Berlin, 14109 Berlin, Germany and Institut für Physik, Humboldt-Universität zu Berlin, 12489 Berlin (Germany); Li, Bo, E-mail: sgzhou@suda.edu.cn, E-mail: bli@math.ucsd.edu [Department of Mathematics and Quantitative Biology Graduate Program, University of California, San Diego, La Jolla, California 92093-0112 (United States); McCammon, J. Andrew [Department of Chemistry and Biochemistry, Department of Pharmacology, Howard Hughes Medical Institute, University of California, San Diego, La Jolla, California 92093-0365 (United States)

2016-08-07

Recent years have seen the initial success of a variational implicit-solvent model (VISM), implemented with a robust level-set method, in capturing efficiently different hydration states and providing quantitatively good estimation of solvation free energies of biomolecules. The level-set minimization of the VISM solvation free-energy functional of all possible solute-solvent interfaces or dielectric boundaries predicts an equilibrium biomolecular conformation that is often close to an initial guess. In this work, we develop a theory in the form of Langevin geometrical flow to incorporate solute-solvent interfacial fluctuations into the VISM. Such fluctuations are crucial to biomolecular conformational changes and binding process. We also develop a stochastic level-set method to numerically implement such a theory. We describe the interfacial fluctuation through the “normal velocity” that is the solute-solvent interfacial force, derive the corresponding stochastic level-set equation in the sense of Stratonovich so that the surface representation is independent of the choice of implicit function, and develop numerical techniques for solving such an equation and processing the numerical data. We apply our computational method to study the dewetting transition in the system of two hydrophobic plates and a hydrophobic cavity of a synthetic host molecule cucurbit[7]uril. Numerical simulations demonstrate that our approach can describe an underlying system jumping out of a local minimum of the free-energy functional and can capture dewetting transitions of hydrophobic systems. In the case of two hydrophobic plates, we find that the wavelength of interfacial fluctuations has a strong influence to the dewetting transition. In addition, we find that the estimated energy barrier of the dewetting transition scales quadratically with the inter-plate distance, agreeing well with existing studies of molecular dynamics simulations. Our work is a first step toward the

Solvent-free functionalization of silicone rubber and efficacy of PAAm brushes grafted from an amino-PPX layer against bacterial adhesion

NARCIS (Netherlands)

Fundeanu, Irina; Klee, Doris; Schouten, Arend J.; Busscher, Henk J.; van der Mei, Henny C.

Silicone rubber is a frequently employed biomaterial that is prone to bacterial adhesion and biofilm formation. In this study, the surface of silicone rubber was solvent-free functionalized by chemical vapor deposition (CVD) of poly(o-amino-p-xylylene-co-p-xylylene (amino-PPX). Subsequently, the

Solvent-Free Patterning of Colloidal Quantum Dot Films Utilizing Shape Memory Polymers

Directory of Open Access Journals (Sweden)

Hohyun Keum

2017-01-01

Full Text Available Colloidal quantum dots (QDs with properties that can be tuned by size, shape, and composition are promising for the next generation of photonic and electronic devices. However, utilization of these materials in such devices is hindered by the limited compatibility of established semiconductor processing techniques. In this context, patterning of QD films formed from colloidal solutions is a critical challenge and alternative methods are currently being developed for the broader adoption of colloidal QDs in functional devices. Here, we present a solvent-free approach to patterning QD films by utilizing a shape memory polymer (SMP. The high pull-off force of the SMP below glass transition temperature (Tg in conjunction with the conformal contact at elevated temperatures (above Tg enables large-area, rate-independent, fine patterning while preserving desired properties of QDs.

CATALYSIS OF CHEMICAL PROCESSES: PARTICULAR ...

African Journals Online (AJOL)

IICBA01

secondary/high schools and universities, the inhibition of the chemical reactions is frequently ... As a result, the lesson catalysis is frequently included in chemistry education curricula at ... Misinterpretations in teaching and perception of catalysis ... profile is shown as a dependence of energy on reaction progress, without ...

Spectroscopy in catalysis : an introduction

NARCIS (Netherlands)

Niemantsverdriet, J.W.

2007-01-01

Spectroscopy in Catalysis is an introduction to the most important analytical techniques that are nowadays used in catalysis and in catalytic surface chemistry. The aim of the book is to give the reader a feeling for the type of information that characterization techniques provide about questions

Nickel-catalyzed direct synthesis of dialkoxymethane ethers

Indian Academy of Sciences (India)

MURUGAN SUBARAMANIAN

Nickel catalysis; alcohol; paraformaldehyde; ether; solvent-free condition. 1. Introduction ..... oxidation and Dopamine Release with Protective Effects. Against Central ... P, Ghosh A, Saha R and Saha B 2016 A Review on the. Advancement of ...

Asymmetric Shaped-Pattern Synthesis for Planar Antenna Arrays

Directory of Open Access Journals (Sweden)

T. M. Bruintjes

2016-01-01

Full Text Available A procedure to synthesize asymmetrically shaped beam patterns is developed for planar antenna arrays. As it is based on the quasi-analytical method of collapsed distributions, the main advantage of this procedure is the ability to realize a shaped (null-free region with very low ripple. Smooth and asymmetrically shaped regions can be used for Direction-of-Arrival estimation and subsequently for efficient tracking with a single output (fully analog beamformer.

Diffusivities, viscosities, and conductivities of solvent-free ionically grafted nanoparticles

KAUST Repository

Hong, Bingbing; Panagiotopoulos, Athanassios Z.

2013-01-01

A new class of conductive composite materials, solvent-free ionically grafted nanoparticles, were modeled by coarse-grained molecular dynamics methods. The grafted oligomeric counterions were observed to migrate between different cores, contributing to the unique properties of the materials. We investigated the dynamics by analyzing the dependence on temperature and structural parameters of the transport properties (self-diffusion coefficients, viscosities and conductivities) and counterion migration kinetics. Temperature dependence of all properties follows the Arrhenius equation, but chain length and grafting density have distinct effects on different properties. In particular, structural effects on the diffusion coefficients are described by the Rouse model and the theory of nanoparticles diffusing in polymer solutions, viscosities are strongly influenced by clustering of cores, and conductivities are dominated by the motions of oligomeric counterions. We analyzed the migration kinetics of oligomeric counterions in a manner analogous to unimer exchange between micellar aggregates. The counterion migrations follow the "double-core" mechanism and are kinetically controlled by neighboring-core collisions. © 2013 The Royal Society of Chemistry.

Analysis of solvent extracts from coal liquefaction in a flowing solvent reactor

Energy Technology Data Exchange (ETDEWEB)

Li, Wen-Ying; Feng, Jie; Xie, Ke-Chang [Key Laboratory of Coal Science and Technology, Taiyuan University of Technology, Ministry of Education and Shanxi Province, No. 79 Yingze West Street, Taiyuan 030024 (China); Kandiyoti, R. [Department of Chemical Engineering and Chemical Technology, Imperial College, University of London, London SW7 2BY (United Kingdom)

2004-10-15

Point of Ayr coal has been extracted using three solvents, tetralin, quinoline and 1-methyl-2-pyrrolidinone (NMP) at two temperatures 350 and 450 C, corresponding approximately to before and after the onset of massive covalent bond scission by pyrolysis. The three solvents differ in solvent power and the ability to donate hydrogen atoms to stabilise free radicals produced by pyrolysis of the coal. The extracts were prepared in a flowing solvent reactor to minimise secondary thermal degradation of the primary extracts. Analysis of the pentane-insoluble fractions of the extracts was achieved by size exclusion chromatography, UV-fluorescence spectroscopy in NMP solvent and probe mass. With increasing extraction temperature, the ratio of the amount having big molecular weight to that having small molecular weight in tetralin extracts was increased; the tetralin extract yield increased from 12.8% to 75.9%; in quinoline, increasing extraction temperature did not have an effect on the molecular weight of products but there was a big increase in extract yield. The extracts in NMP showed the enhanced solvent extraction power at both temperatures, with a shift in the ratio of larger molecules to smaller molecules with increasing extraction temperature and with the highest conversion of Point of Ayr coal among these three solvents at both temperatures. Solvent adducts were detected in the tetralin and quinoline extracts by probe mass spectrometry; solvent products were formed from NMP at both temperatures.

Solvent-free microwave-mediated Michael addition reactions

Indian Academy of Sciences (India)

Unknown

obviously difficult to scale up. In this context ... eco-friendly features such as, (i) no solvent is required to conduct the ... water soluble, addition of reaction mixture after com- ..... Yield: 855 mg (89%; viscous liquid). 3.4 Ethyl .... Jung M E 1993 Comprehensive organic synthesis ... Leshcheva I F and Bundel Y G 1997 Mendeleev.

Effect of non-solvents used in the coagulation bath on morphology of PVDF membranes

Directory of Open Access Journals (Sweden)

Mônica Beatriz Thürmer

2012-12-01

Full Text Available The aim of this paper was to prepare a poly (vinylidene fluoride (PVDF membrane using different non-solvents in the coagulation bath for the phase inversion method. In order to increase the mechanical strength of membranes, facing the pressure of work, was used a macro-porous polyester support. The morphology and structure of the resulting membranes were evaluated by scanning electron microscopy, porosity measurements, water and 1-octanol uptake, contact angle, pure water flux, hydraulic permeability and hydraulic resistance. The morphology and pure water flux changed significantly using ethanol (symmetric membrane and/or water (asymmetric membrane as the non-solvent. The symmetric membrane presented a high hydrophobic surface (water contact angle ~136º and a higher pure water flux and porosity than the asymmetric membrane, which presented a lower hydrophobicity surface (water contact angle ~90º. The morphologies obtained suggest different applications.

Magnetic monopole catalysis of proton decay

International Nuclear Information System (INIS)

Marciano, W.J.; Salvino, D.

1986-09-01

Catalysis of proton decay by GUT magnetic monopoles (the Rubakov-Callan effect) is discussed. Combining a short-distance cross section calculation by Bernreuther and Craigie with the long-distance velocity dependent distortion factors of Arafune and Fukugita, catalysis rate predictions which can be compared with experiment are obtained. At present, hydrogen rich detectors such as water (H 2 O) and methane (CH 4 ) appear to be particularly well suited for observing catalysis by very slow monopoles. 17 refs., 1 fig

Influences of surface and solvent on retention of HEMA/mixture components after evaporation.

Science.gov (United States)

Garcia, Fernanda C P; Wang, Linda; Pereira, Lúcia C G; de Andrade e Silva, Safira M; Júnior, Luiz M; Carrilho, Marcela Rocha de Oliveira

2010-01-01

This study examined the retention of solvents within experimental HEMA/solvent primers after two conditions for solvent evaporation: from a free surface or from dentine surface. Experimental primers were prepared by mixing 35% HEMA with 65% water, methanol, ethanol or acetone (v/v). Aliquots of each primer (50 microl) were placed on glass wells or they were applied to the surface of acid-etched dentine cubes (2mm x 2mm x 2mm) (n=5). For both conditions (i.e. from free surface or dentine cubes), change in primers mass due to solvent evaporation was gravimetrically measured for 10min at 51% RH and 21 degrees C. The rate of solvent evaporation was calculated as a function of loss of primers mass (%) over time. Data were analysed by two-way ANOVA and Student-Newman-Keuls (pevaporation rate (%/min) depending on the solvent present in the primer and the condition for evaporation (from free surface or dentine cubes) (pevaporation for HEMA/acetone primer was almost 2- to 10-times higher than for HEMA/water primer depending whether evaporation occurred, respectively, from a free surface or dentine cubes. The rate of solvent evaporation varied with time, being in general highest at the earliest periods. The rate of solvent evaporation and its retention into HEMA/solvent primers was influenced by the type of the solvent and condition allowed for their evaporation.

Hydrogen Production by Homogeneous Catalysis: Alcohol Acceptorless Dehydrogenation

DEFF Research Database (Denmark)

Nielsen, Martin

2015-01-01

in hydrogen production from biomass using homogeneous catalysis. Homogeneous catalysis has the advance of generally performing transformations at much milder conditions than traditional heterogeneous catalysis, and hence it constitutes a promising tool for future applications for a sustainable energy sector...

Solvent-Free Manufacturing of Electrodes for Lithium-ion Batteries

Science.gov (United States)

Ludwig, Brandon; Zheng, Zhangfeng; Shou, Wan; Wang, Yan; Pan, Heng

2016-03-01

Lithium ion battery electrodes were manufactured using a new, completely dry powder painting process. The solvents used for conventional slurry-cast electrodes have been completely removed. Thermal activation time has been greatly reduced due to the time and resource demanding solvent evaporation process needed with slurry-cast electrode manufacturing being replaced by a hot rolling process. It has been found that thermal activation time to induce mechanical bonding of the thermoplastic polymer to the remaining active electrode particles is only a few seconds. Removing the solvent and drying process allows large-scale Li-ion battery production to be more economically viable in markets such as automotive energy storage systems. By understanding the surface energies of various powders which govern the powder mixing and binder distribution, bonding tests of the dry-deposited particles onto the current collector show that the bonding strength is greater than slurry-cast electrodes, 148.8 kPa as compared to 84.3 kPa. Electrochemical tests show that the new electrodes outperform conventional slurry processed electrodes, which is due to different binder distribution.

Solvent-free functionalization of carbon nanotube buckypaper with amines

International Nuclear Information System (INIS)

Basiuk, Elena V.; Ramírez-Calera, Itzel J.; Meza-Laguna, Victor; Abarca-Morales, Edgar; Pérez-Rey, Luis A.; Re, Marilena; Prete, Paola; Lovergine, Nico

2015-01-01

Graphical abstract: - Abstract: We demonstrate the possibility of fast and efficient solvent-free functionalization of buckypaper (BP) mats prefabricated from oxidized multiwalled carbon nanotubes (MWCNTs-ox), by using three representative amines of different structure: one monofunctional aliphatic amine, octadecylamine (ODA), one monofunctional aromatic amine, 1-aminopyrene (AP), and one aromatic diamine, 1,5-diaminonaphthalene (DAN). The functionalization procedure, which relies on the formation of amide bonds with carboxylic groups of MWCNTs-ox, is performed at 150–180 °C under reduced pressure and takes about 4 h including auxiliary degassing. The amine-treated BP samples (BP-ODA, BP-AP and BP-DAN, respectively) were characterized by means of a variety of analytical techniques such as Fourier-transform infrared and Raman spectroscopy, thermogravimetric and differential thermal analysis, scanning and transmission electron microscopy, scanning helium ion microscopy, and atomic force microscopy. The highest amine content was found for BP-ODA, and the lowest one was observed for BP-DAN, with a possible contribution of non-covalently bonded amine molecules in all three cases. Despite of some differences in spectral and morphological characteristics for amine-functionalized BP samples, they have in common a dramatically increased stability in water as compared to pristine BP and, on the other hand, a relatively invariable electrical conductivity.

Tuning of Preparational Factors Affecting the Morphological Structure and Gas Separation Property of Asymmetric Polysulfone Membranes

Science.gov (United States)

Yuenyao, C.; Ruangdit, S.; Chittrakarn, T.

2017-09-01

The aim of this work was to study the effect of preparational factors such as solvent type, evaporation time (ET) and non-solvent additive, on the morphological structure, physical and gas separation properties of the prepared membrane samples by tuning of these parameters. Flat sheet asymmetric polysulfone (PSF) membranes were prepared by the dry/wet phase inversion process combined with the double coagulation bath method. The alteration of the prepared membranes were analyzed through scientific techniques such as Scanning Electron Microscope (SEM) and Dynamic Mechanical Thermal Analysis (DMTA). Furthermore, gas separation performance of membrane samples was measured in term of gas permeation and ideal selectivity of CO2/CH4. Experimental results showed that the change of preparational factors affected to the gas permeation of asymmetric PSF membranes. For example, the selective layer thickness increased with increasing of ET. This lead to increase significantly of ideal selectivity of CO2/CH4. The CO2/CH4 ideal selectivity was also increased with increase of ethanol (non-solvent additive) concentration in casting solution. In summary, the tuning of preparational factors affected to morphological structure, physical and gas separation properties of PSF membranes.

Molecular complexity from polyunsaturated substrates: the gold catalysis approach.

Science.gov (United States)

Fensterbank, Louis; Malacria, Max

2014-03-18

Over the last two decades, electrophilic catalysis relying on platinum(II), gold(I), and gold(III) salts has emerged as a remarkable synthetic methodology. Chemists have discovered a large variety of organic transformations that convert a great assortment of highly functionalized precursors into valuable final products. In many cases, these methodologies offer unique features, allowing access to unprecedented molecular architectures. Due to the mild reaction conditions and high function compatibility, scientists have successfully developed applications in total synthesis of natural products, as well as in asymmetric catalysis. In addition, all these developments have been accompanied by the invention of well-tailored catalysts, so that a palette of different electrophilic agents is now commercially available or readily synthesized at the bench. In some respects, researchers' interests in developing homogeneous gold catalysis can be compared with the Californian gold rush of the 19th century. It has attracted into its fervor thousands of scientists, providing a huge number of versatile and important reports. More notably, it is clear that the contribution to the art of organic synthesis is very valuable, though the quest is not over yet. Because they rely on the intervention of previously unknown types of intermediates, new retrosynthetic disconnections are now possible. In this Account, we discuss our efforts on the use of readily available polyunsaturated precursors, such as enynes, dienynes, allenynes, and allenenes to give access to highly original polycyclic structures in a single operation. These transformations transit via previously undescribed intermediates A, B, D, F, and H that will be encountered later on. All these intermediates have been determined by both ourselves and others by DFT calculations and in some cases have been confirmed on the basis of experimental data. In addition, dual gold activation can be at work in some of these transformations

Outage Analysis of Asymmetric RF-FSO Systems

KAUST Repository

Ansari, Imran Shafique; Abdallah, Mohamed M.; Alouini, Mohamed-Slim; Qaraqe, Khalid A.

2017-01-01

In this work, the outage performance analysis of a dual-hop transmission system composed of asymmetric radio frequency (RF) channels cascaded with free-space optical (FSO) links is presented. The RF links are modeled by the Rayleigh fading

CATALYST-FREE REACTIONS UNDER SOLVENT-FEE CONDITIONS: MICROWAVE-ASSISTED SYNTHESIS OF HETEROCYCLIC HYDRAZONES BELOW THE MELTING POINT OF NEAT REACTANTS: JOURNAL ARTICLE

Science.gov (United States)

NRMRL-CIN-1437 Jeselnik, M., Varma*, R.S., Polanc, S., and Kocevar, M. Catalyst-free Reactions under Solvent-fee Conditions: Microwave-assisted Synthesis of Heterocyclic Hydrazones below the Melting Point of Neat Reactants. Published in: Chemical Communications 18:1716-1717 (200...

Glutathione reductase: solvent equilibrium and kinetic isotope effects

International Nuclear Information System (INIS)

Wong, K.K.; Vanoni, M.A.; Blanchard, J.S.

1988-01-01

Glutathione reductase catalyzes the NADPH-dependent reduction of oxidized glutathione (GSSG). The kinetic mechanism is ping-pong, and we have investigated the rate-limiting nature of proton-transfer steps in the reactions catalyzed by the spinach, yeast, and human erythrocyte glutathione reductases using a combination of alternate substrate and solvent kinetic isotope effects. With NADPH or GSSG as the variable substrate, at a fixed, saturating concentration of the other substrate, solvent kinetic isotope effects were observed on V but not V/K. Plots of Vm vs mole fraction of D 2 O (proton inventories) were linear in both cases for the yeast, spinach, and human erythrocyte enzymes. When solvent kinetic isotope effect studies were performed with DTNB instead of GSSG as an alternate substrate, a solvent kinetic isotope effect of 1.0 was observed. Solvent kinetic isotope effect measurements were also performed on the asymmetric disulfides GSSNB and GSSNP by using human erythrocyte glutathione reductase. The Km values for GSSNB and GSSNP were 70 microM and 13 microM, respectively, and V values were 62 and 57% of the one calculated for GSSG, respectively. Both of these substrates yield solvent kinetic isotope effects greater than 1.0 on both V and V/K and linear proton inventories, indicating that a single proton-transfer step is still rate limiting. These data are discussed in relationship to the chemical mechanism of GSSG reduction and the identity of the proton-transfer step whose rate is sensitive to solvent isotopic composition. Finally, the solvent equilibrium isotope effect measured with yeast glutathione reductase is 4.98, which allows us to calculate a fractionation factor for the thiol moiety of GSH of 0.456

Theory of competitive solvation of polymers by two solvents and entropy-enthalpy compensation in the solvation free energy upon dilution with the second solvent.

Science.gov (United States)

Dudowicz, Jacek; Freed, Karl F; Douglas, Jack F

2015-06-07

We develop a statistical mechanical lattice theory for polymer solvation by a pair of relatively low molar mass solvents that compete for binding to the polymer backbone. A theory for the equilibrium mixture of solvated polymer clusters {AiBCj} and free unassociated molecules A, B, and C is formulated in the spirit of Flory-Huggins mean-field approximation. This theoretical framework enables us to derive expressions for the boundaries for phase stability (spinodals) and other basic properties of these polymer solutions: the internal energy U, entropy S, specific heat CV, extent of solvation Φsolv, average degree of solvation 〈Nsolv〉, and second osmotic virial coefficient B2 as functions of temperature and the composition of the mixture. Our theory predicts many new phenomena, but the current paper applies the theory to describe the entropy-enthalpy compensation in the free energy of polymer solvation, a phenomenon observed for many years without theoretical explanation and with significant relevance to liquid chromatography and other polymer separation methods.

High-sensitivity green resist material with organic solvent-free spin-coating and tetramethylammonium hydroxide-free water-developable processes for EB and EUV lithography

Science.gov (United States)

Takei, Satoshi; Hanabata, Makoto; Oshima, Akihiro; Kashiwakura, Miki; Kozawa, Takahiro; Tagawa, Seiichi

2015-03-01

We investigated the eco-friendly electron beam (EB) and extreme-ultraviolet (EUV) lithography using a high-sensitive negative type of green resist material derived from biomass to take advantage of organic solvent-free water spin-coating and tetramethylammonium hydroxide(TMAH)-free water-developable techniques. A water developable, non-chemically amplified, high sensitive, and negative tone resist material in EB lithography was developed for environmental affair, safety, easiness of handling, and health of the working people, instead of the common developable process of TMAH. The material design concept to use the water-soluble resist material with acceptable properties such as pillar patterns with less than 100 nm in high EB sensitivity of 10 μC/cm2 and etch selectivity with a silicon-based middle layer in CF4 plasma treatment was demonstrated for EB and EUV lithography.

Asymmetric ZnO panel-like hierarchical architectures with highly interconnected pathways for free-electron transport and photovoltaic improvements.

Science.gov (United States)

Shi, Yantao; Zhu, Chao; Wang, Lin; Li, Wei; Fung, Kwok Kwong; Wang, Ning

2013-01-02

Through a rapid and template-free precipitation approach, we synthesized an asymmetric panel-like ZnO hierarchical architecture (PHA) for photoanodes of dye-sensitized solar cells (DSCs). The two sides of the PHA are constructed differently using densely interconnected, mono-crystalline and ultrathin ZnO nanosheets. By mixing these PHAs with ZnO nanoparticles (NPs), we developed an effective and feasible strategy to improve the electrical transport and photovoltaic performance of the composite photoanodes of DSCs. The highly crystallized and interconnected ZnO nanosheets largely minimized the total grain boundaries within the composite photoanodes and thus served as direct pathways for the transport and effective collection of free electrons. Through low-temperature (200 °C) annealing, these novel composite photoanodes achieved high conversion efficiencies of up to 5.59% for ZnO-based quasi-solid DSCs. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalysis studies

International Nuclear Information System (INIS)

Taylor, T.N.; Ellis, W.P.

1977-11-01

The New Research Initiatives Program (NRIP) project on catalysis in Los Alamos Scientific Laboratory (LASL) Group CMB-8 has made significant progress towards performing the first basic in situ experimental studies of heterogeneous catalysis on solid compound surfaces in a LEED-Auger system. To further understand the surface crystallography of a possible catalyst compound, LEED-Auger measurements were made on UO 2 (approximately 100) vicinal surfaces. These (approximately 100) vicinal surfaces were shown to decompose irreversibly into lower index facets, including prominent (100) facets, at temperatures below those needed for creation of lowest index faceting on (approximately 111) vicinal surfaces. LEED examination of fully faceted surfaces from both types of UO 2 vicinal cuts did not show evidence of cyclopropane or propene chemisorption. The existing LEED-Auger system was modified to allow catalytic reactions at approximately less than 10 -3 torr. A sample holder, specifically designed for catalysis measurements in the modified system, was tested while examining single crystals of CoO and Cr 2 O 3 . Extensive LEED-Auger measurements were made on CoO in vacuo and in the presence of light hydrocarbons and alcohols plus H 2 O, NO, and NH 3 . No chemisorptive behavior was observed except with H 2 O in the presence of the electron beam. Although only examined briefly, the Cr 2 O 3 was remarkable for the sharp LEED features obtained prior to any surface treatment in the vacuum system

Flexible all-solid-state asymmetric supercapacitors based on free-standing carbon nanotube/graphene and Mn3O4 nanoparticle/graphene paper electrodes.

Science.gov (United States)

Gao, Hongcai; Xiao, Fei; Ching, Chi Bun; Duan, Hongwei

2012-12-01

We report the design of all-solid-state asymmetric supercapacitors based on free-standing carbon nanotube/graphene (CNTG) and Mn(3)O(4) nanoparticles/graphene (MG) paper electrodes with a polymer gel electrolyte of potassium polyacrylate/KCl. The composite paper electrodes with carbon nanotubes or Mn(3)O(4) nanoparticles uniformly intercalated between the graphene nanosheets exhibited excellent mechanical stability, greatly improved active surface areas, and enhanced ion transportation, in comparison with the pristine graphene paper. The combination of the two paper electrodes with the polymer gel electrolyte endowed our asymmetric supercapacitor of CNTG//MG an increased cell voltage of 1.8 V, a stable cycling performance (capacitance retention of 86.0% after 10,000 continuous charge/discharge cycles), more than 2-fold increase of energy density (32.7 Wh/kg) compared with the symmetric supercapacitors, and importantly a distinguished mechanical flexibility.

Faraday Discussions meeting Catalysis for Fuels.

Science.gov (United States)

Fischer, Nico; Kondrat, Simon A; Shozi, Mzamo

2017-05-02

Welcome to Africa was the motto when after more than 100 years the flag ship conference series of the Royal Society of Chemistry, the Faraday Discussions was hosted for the first time on the African Continent. Under the fitting topic 'Catalysis for Fuels' over 120 delegates followed the invitation by the conference chair Prof. Graham Hutchings FRS (Cardiff Catalysis Institute), his organizing committee and the co-organizing DST-NRF Centre of Excellence in Catalysis c*change (). In the presentations of 21 invited speakers and 59 posters, cutting edge research in the field of catalysis for fuels, designing new catalysts for synthetic fuels, hydrocarbon conversion in the production of synthetic fuels and novel photocatalysis was presented over the two-day meeting. The scene was set by the opening lecture of Prof. Enrique Iglesias (UC Berkeley) and wrapped-up with the concluding remarks by Philip Gibson (SASOL).

Catalysis induced by radiations

International Nuclear Information System (INIS)

Jimenez B, J.; Gonzalez J, J. C.

2010-01-01

In Mexico is generated a great quantity of residuals considered as dangerous, for its capacity of corrosion, reactivity, toxicity to the environment, inflammability and biological-infectious potential. It is important to mention that the toxic compounds cannot be discharged to the sewerage systems and much less to the receiving bodies of water. The usual treatment that receives the dangerous residuals is the incineration and the bordering. The incineration is an efficient form of treating the residuals, but it can be dioxins source and benzofurans, being the phenol and chloro phenol the precursors of these compounds. At the present time the radiolytic degradation of organic compounds has been broadly studied, especially the 4-chloro phenol and of same form the photo catalysis of organic compounds. However the combination of both processes, called radio catalysis is barely reported. In this work the results of the experiments realized for to degrade the 4-chloro phenol by means of radio catalysis are reported. (Author)

Driving Forces Controlling Host-Guest Recognition in Supercritical Carbon Dioxide Solvent.

Science.gov (United States)

Ingrosso, Francesca; Altarsha, Muhannad; Dumarçay, Florence; Kevern, Gwendal; Barth, Danielle; Marsura, Alain; Ruiz-López, Manuel F

2016-02-24

The formation of supramolecular host-guest complexes is a very useful and widely employed tool in chemistry. However, supramolecular chemistry in non-conventional solvents such as supercritical carbon dioxide (scCO2 ), one of the most promising sustainable solvents, is still in its infancy. In this work, we explored a successful route to the development of green processes in supercritical CO2 by combining a theoretical approach with experiments. We were able to synthesize and characterize an inclusion complex between a polar aromatic molecule (benzoic acid) and peracetylated-β-cyclodextrin, which is soluble in the supercritical medium. This finding opens the way to wide, environmental friendly, applications of scCO2 in many areas of chemistry, including supramolecular synthesis, reactivity and catalysis, micro and nano-particle formation, molecular recognition, as well as enhanced extraction processes with increased selectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new magnetically recoverable catalyst promoting the synthesis of 1,4-dihydropyridine and polyhydroquinoline derivatives via the Hantzsch condensation under solvent-free conditions

Energy Technology Data Exchange (ETDEWEB)

Taheri, Narges; Heidarizadeh, Fariba; Kiasat, Alireza

2017-04-15

In the current study, 1,4-dihydropyridine and polyhydroquinoline derivatives were efficiently synthesized under solvent-less conditions with a magnetic catalyst containing novel acidic ionic liquid functionalized silica modified Fe{sub 3}O{sub 4} nanoparticles through a four component combination of β-ketoester, aldehydes and ammonium acetate (1, 2, 2). Several approaches have been reported for synthesizing these derivatives, while each of these approaches have some weaknesses including long time of reaction, excess of volatile organic solvent, low efficiency, costly reagents, complex operation, high temperatures, production of a number of side products, and difficult catalyst recovery. The simple operation, short time of reaction (5–30 min) and the high efficiency (80–94%) are the special advantages of this technique. The immobilized catalyst exhibited an appropriate thermal stability and excellent recyclability. Different methods such as FT-IR, SEM, EDX, TGA-DTA, and VSM were used to confirm and characterize the catalyst. - Highlights: • A new acidic ionic liquid were first synthesized and applied in both symmetric and asymmetric hantzsch reactions for preparing 1, 4-dihydropyridine and polyhydroquinoline derivatives with high efficiencies under solvent-less conditions. • The immobilized catalyst exhibited an appropriate thermal stability and excellent recyclability. • The nanomagnetic catalyst could be recovered from solution with an external magnet at once, allowing undemanding recovery and reuse. • The catalyst was reused for five times with no considerable decrease in catalytic activity.

Structure of solvent-free grafted nanoparticles: Molecular dynamics and density-functional theory

KAUST Repository

Chremos, Alexandros

2011-01-01

The structure of solvent-free oligomer-grafted nanoparticles has been investigated using molecular dynamics simulations and density-functional theory. At low temperatures and moderate to high oligomer lengths, the qualitative features of the core particle pair probability, structure factor, and the oligomer brush configuration obtained from the simulations can be explained by a density-functional theory that incorporates the configurational entropy of the space-filling oligomers. In particular, the structure factor at small wave numbers attains a value much smaller than the corresponding hard-sphere suspension, the first peak of the pair distribution function is enhanced due to entropic attractions among the particles, and the oligomer brush expands with decreasing particle volume fraction to fill the interstitial space. At higher temperatures, the simulations reveal effects that differ from the theory and are likely caused by steric repulsions of the expanded corona chains. © 2011 American Institute of Physics.

Asymmetric dominance and asymmetric mate choice oppose premating isolation after allopatric divergence.

Science.gov (United States)

Sefc, Kristina M; Hermann, Caroline M; Steinwender, Bernd; Brindl, Hanna; Zimmermann, Holger; Mattersdorfer, Karin; Postl, Lisbeth; Makasa, Lawrence; Sturmbauer, Christian; Koblmüller, Stephan

2015-04-01

Assortative mating promotes reproductive isolation and allows allopatric speciation processes to continue in secondary contact. As mating patterns are determined by mate preferences and intrasexual competition, we investigated male-male competition and behavioral isolation in simulated secondary contact among allopatric populations. Three allopatric color morphs of the cichlid fish Tropheus were tested against each other. Dyadic male-male contests revealed dominance of red males over bluish and yellow-blotch males. Reproductive isolation in the presence of male-male competition was assessed from genetic parentage in experimental ponds and was highly asymmetric among pairs of color morphs. Red females mated only with red males, whereas the other females performed variable degrees of heteromorphic mating. Discrepancies between mating patterns in ponds and female preferences in a competition-free, two-way choice paradigm suggested that the dominance of red males interfered with positive assortative mating of females of the subordinate morphs and provoked asymmetric hybridization. Between the nonred morphs, a significant excess of negative assortative mating by yellow-blotch females with bluish males did not coincide with asymmetric dominance among males. Hence, both negative assortative mating preferences and interference of male-male competition with positive assortative preferences forestall premating isolation, the latter especially in environments unsupportive of competition-driven spatial segregation.

Organic solvents, electrolytes, and lithium ion cells with good low temperature performance

Science.gov (United States)

Smart, Marshall C. (Inventor); Bugga, Ratnakumar V. (Inventor); Surampudi, Subbarao (Inventor); Huang, Chen-Kuo (Inventor)

2002-01-01

Multi-component organic solvent systems, electrolytes and electrochemical cells characterized by good low temperature performance are provided. In one embodiment, an improved organic solvent system contains a ternary mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate. In other embodiments, quaternary systems include a fourth component, i.e, an aliphatic ester, an asymmetric alkyl carbonate or a compound of the formula LiOX, where X is R, COOR, or COR, where R is alkyl or fluoroalkyl. Electrolytes based on such organic solvent systems are also provided and contain therein a lithium salt of high ionic mobility, such as LiPF.sub.6. Reversible electrochemical cells, particularly lithium ion cells, are constructed with the improved electrolytes, and preferably include a carbonaceous anode, an insertion type cathode, and an electrolyte interspersed therebetween.

Probing short-range correlations in asymmetric nuclei with quasi-free pair knockout reactions

Science.gov (United States)

Stevens, Sam; Ryckebusch, Jan; Cosyn, Wim; Waets, Andreas

2018-02-01

Short-range correlations (SRC) in asymmetric nuclei with an unusual neutron-to-proton ratio can be studied with quasi-free two-nucleon knockout processes following the collision between accelerated ions and a proton target. We derive an approximate factorized cross section for those SRC-driven p (A ,p‧N1N2) reactions. Our reaction model hinges on the factorization properties of SRC-driven A (e ,e‧N1N2) reactions for which strong indications are found in theory-experiment comparisons. In order to put our model to the test we compare its predictions with results of 12C (p ,p‧ pn) measurements conducted at Brookhaven National Laboratory (BNL) and find a fair agreement. The model can also reproduce characteristic features of SRC-driven two-nucleon knockout reactions, like back-to-back emission of the correlated nucleons. We study the asymmetry dependence of nuclear SRC by providing predictions for the ratio of proton-proton to proton-neutron knockout cross sections for the carbon isotopes 9-15C thereby covering neutron excess values (N - Z) / Z between -0.5 and +0.5.

Efficient and Highly Selective Solvent-Free Oxidation of Primary Alcohols to Aldehydes Using Bucky Nanodiamond.

Science.gov (United States)

Lin, Yangming; Wu, Kuang-Hsu Tim; Yu, Linhui; Heumann, Saskia; Su, Dang Sheng

2017-09-11

Selective oxidation of alcohols to aldehydes is widely applicable to the synthesis of various green chemicals. The poor chemoselectivity for complicated primary aldehydes over state-of-the-art metal-free or metal-based catalysts represents a major obstacle for industrial application. Bucky nanodiamond is a potential green catalyst that exhibits excellent chemoselectivity and cycling stability for the selective oxidation of primary alcohols in diverse structures (22 examples, including aromatic, substituted aromatic, unsaturated, heterocyclic, and linear chain alcohols) to their corresponding aldehydes. The results are comparable to reported transition-metal catalysts including conventional Pt/C and Ru/C catalysts for certain substrates under solvent-free conditions. The possible activation process of the oxidant and substrates by the surface oxygen groups and defect species are revealed with model catalysts, ex situ electrochemical measurements, and ex situ attenuated total reflectance. The zigzag edges of sp 2 carbon planes are shown to play a key role in these reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improving Pullulanase Catalysis via Reversible Immobilization on Modified Fe3O4@Polydopamine Nanoparticles.

Science.gov (United States)

Wang, Jianfeng; Liu, Zhongmei; Zhou, Zhemin

2017-08-01

To improve the catalysis of pullulanase from Anoxybacillus sp.WB42, Fe 3 O 4 @polydopamine nanoparticles (Fe 3 O 4 @PDA) were prepared and modified with functional groups for immobilization of pullulanases via covalent binding or ionic adsorption. Immobilized pullulanases had lower thermal stability than that of free pullulanase, whereas their catalysis depended on the surface characteristics of nanoparticles. As for covalent immobilization of pullulanases onto Fe 3 O 4 @PDA derivatives, the spacer grafted onto Fe 3 O 4 @PDA made the catalytic efficiency of pullulanase increase up to the equivalence of free enzyme but dramatically reduced the pullulanase thermostability. In contrast, pullulanases bounded ionically to Fe 3 O 4 @PDA derivatives had higher activity recovery and catalytic efficiency, and their catalytic behaviors varied with the modifier grafted onto Fe 3 O 4 @PDA. Among these immobilized pullulanases, ionic adsorption of pullulanase on Fe 3 O 4 @PDA-polyethyleneimine-glycidyltrimethylammonium gave a high-performance and durable catalyst, which displayed not only 1.5-fold increase in catalytic efficiency compared to free enzyme but also a significant improvement in operation stability with a half of initial activity after 27 consecutive cycles with a total reaction time of 13.5 h, and was reversible, making this nanoparticle reusable for immobilization.

Porous polymeric membranes with thermal and solvent resistance

KAUST Repository

Pulido, Bruno

2017-05-30

Polymeric membranes are highly advantageous over their ceramic counterparts in terms of the simplicity of the manufacturing process, cost and scalability. Their main disadvantages are low stability at temperatures above 200 °C, and in organic solvents. We report for the first time porous polymeric membranes manufactured from poly(oxindolebiphenylylene) (POXI), a polymer with thermal stability as high as 500 °C in oxidative conditions. The membranes were prepared by solution casting and phase inversion by immersion in water. The asymmetric porous morphology was characterized by scanning electronic microscopy. The pristine membranes are stable in alcohols, acetone, acetonitrile and hexane, as well as in aqueous solutions with pH between 0 and 14. The membrane stability was extended for application in other organic solvents by crosslinking, using various dibromides, and the efficiency of the different crosslinkers was evaluated by thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). POXI crosslinked membranes are stable up to 329 °C in oxidative conditions and showed organic solvent resistance in polar aprotic solvents with 99% rejection of Red Direct 80 in DMF at 70 °C. With this development, the application of polymeric membranes could be extended to high temperature and harsh environments, fields currently dominated by ceramic membranes.

EMSL and Institute for Integrated Catalysis (IIC) Catalysis Workshop

Energy Technology Data Exchange (ETDEWEB)

Campbell, Charles T.; Datye, Abhaya K.; Henkelman, Graeme A.; Lobo, Raul F.; Schneider, William F.; Spicer, Leonard D.; Tysoe, Wilfred T.; Vohs, John M.; Baer, Donald R.; Hoyt, David W.; Thevuthasan, Suntharampillai; Mueller, Karl T.; Wang, Chong M.; Washton, Nancy M.; Lyubinetsky, Igor; Teller, Raymond G.; Andersen, Amity; Govind, Niranjan; Kowalski, Karol; Kabius, Bernd C.; Wang, Hongfei; Campbell, Allison A.; Shelton, William A.; Bylaska, Eric J.; Peden, Charles HF; Wang, Yong; King, David L.; Henderson, Michael A.; Rousseau, Roger J.; Szanyi, Janos; Dohnalek, Zdenek; Mei, Donghai; Garrett, Bruce C.; Ray, Douglas; Futrell, Jean H.; Laskin, Julia; DuBois, Daniel L.; Kuprat, Laura R.; Plata, Charity

2011-05-24

Within the context of significantly accelerating scientific progress in research areas that address important societal problems, a workshop was held in November 2010 at EMSL to identify specific and topically important areas of research and capability needs in catalysis-related science.

Isotopes in heterogeneous catalysis

CERN Document Server

Hargreaves, Justin SJ

2006-01-01

The purpose of this book is to review the current, state-of-the-art application of isotopic methods to the field of heterogeneous catalysis. Isotopic studies are arguably the ultimate technique in in situ methods for heterogeneous catalysis. In this review volume, chapters have been contributed by experts in the field and the coverage includes both the application of specific isotopes - Deuterium, Tritium, Carbon-14, Sulfur-35 and Oxygen-18 - as well as isotopic techniques - determination of surface mobility, steady state transient isotope kinetic analysis, and positron emission profiling.

Recovery of hafnium values from loaded extraction solvent

International Nuclear Information System (INIS)

Abodishish, H.A.

1989-01-01

This patent describes an improvement in a process for recovering high purity hafnium hydroxide from a methyl isobutyl ketone organic solvent that is substantially free of sulfate ions and contains hafnium thiocyanate and thiocyanic acid. The improvement comprising reacting the organic solvent with ammonia to produce a reaction product in the form of a methyl isobutyl ketone organic solvent that is substantially free of sulfate ions and contains ammonium thiocyanite solution and hafnium hydroxide; separating the constituents of the reaction product in accordance with their respective specific gravities to produce a hafnium hydroxide sludge as one of the separation products; and removing the liquid component of the sludge to yield a high purity hafnium hydroxide ready for calcination to hafnium oxide

Solvent-free directed patterning of a highly ordered liquid crystalline organic semiconductor via template-assisted self-assembly for organic transistors.

Science.gov (United States)

Kim, Aryeon; Jang, Kwang-Suk; Kim, Jinsoo; Won, Jong Chan; Yi, Mi Hye; Kim, Hanim; Yoon, Dong Ki; Shin, Tae Joo; Lee, Myong-Hoon; Ka, Jae-Won; Kim, Yun Ho

2013-11-20

Highly ordered organic semiconductor micropatterns of the liquid-crystalline small molecule 2,7-didecylbenzothienobenzothiophene (C10 -BTBT) are fabricated using a simple method based on template-assisted self-assembly (TASA). The liquid crystallinity of C10 -BTBT allows solvent-free fabrication of high-performance printed organic field-effect transistors (OFETs). © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemoselective Preparation of 1,1-Diacetates from Aldehydes, Mediated by a Keggin Heteropolyacid Under Solvent Free Conditions at Room Temperature

Directory of Open Access Journals (Sweden)

G. Romanelli

2007-01-01

Full Text Available A simple, general and efficient method has been developed for the conversion of aldehydes to 1,1-diacetates using acetic anhydride, a catalytic amount of non commercial Keggin heteropolyacid (H6 PalMo11O40 (1% mol in solvent free conditions at room temperature. Aromatic and aliphatic, simple and conjugated aldehydes were protected with excellent yields.

Elucidation of the conformational free energy landscape in H.pylori LuxS and its implications to catalysis

Directory of Open Access Journals (Sweden)

Bhattacharyya Moitrayee

2010-08-01

Full Text Available Abstract Background One of the major challenges in understanding enzyme catalysis is to identify the different conformations and their populations at detailed molecular level in response to ligand binding/environment. A detail description of the ligand induced conformational changes provides meaningful insights into the mechanism of action of enzymes and thus its function. Results In this study, we have explored the ligand induced conformational changes in H.pylori LuxS and the associated mechanistic features. LuxS, a dimeric protein, produces the precursor (4,5-dihydroxy-2,3-pentanedione for autoinducer-2 production which is a signalling molecule for bacterial quorum sensing. We have performed molecular dynamics simulations on H.pylori LuxS in its various ligand bound forms and analyzed the simulation trajectories using various techniques including the structure network analysis, free energy evaluation and water dynamics at the active site. The results bring out the mechanistic details such as co-operativity and asymmetry between the two subunits, subtle changes in the conformation as a response to the binding of active and inactive forms of ligands and the population distribution of different conformations in equilibrium. These investigations have enabled us to probe the free energy landscape and identify the corresponding conformations in terms of network parameters. In addition, we have also elucidated the variations in the dynamics of water co-ordination to the Zn2+ ion in LuxS and its relation to the rigidity at the active sites. Conclusions In this article, we provide details of a novel method for the identification of conformational changes in the different ligand bound states of the protein, evaluation of ligand-induced free energy changes and the biological relevance of our results in the context of LuxS structure-function. The methodology outlined here is highly generalized to illuminate the linkage between structure and function in

Physico-chemical properties of Pd nanoparticles produced by Pulsed Laser Ablation in different organic solvents

International Nuclear Information System (INIS)

Cristoforetti, Gabriele; Pitzalis, Emanuela; Spiniello, Roberto; Ishak, Randa; Giammanco, Francesco; Muniz-Miranda, Maurizio; Caporali, Stefano

2012-01-01

Palladium nanoparticles are arousing an increasing interest because of their strong activity in heterogeneous catalysis in a wide range of reactions. Driven by the interest of producing Pd nanoparticles to be deposited for catalysis over hydrophobic supports, we investigated their synthesis via Pulsed Laser Ablation in Liquid in several organic solvents, as acetone, ethanol, 2-propanol, toluene, n-hexane. The colloids were produced by using a Nd:YAG ns laser and without the addition of surfactant agents. The morphology, composition, stability and oxidation state of the obtained nanoparticles were investigated by TEM-EDS analysis, UV-vis spectroscopy, X-ray Photoelectron Spectroscopy and micro-Raman spectroscopy. The results evidence that the nature of the solvent influences both the yield and the physico-chemical properties of the produced nanoparticles. While in acetone and alcohols spheroidal, non aggregated and stable particles are obtained, in case of toluene and n-hexane few unstable particles surrounded by a gel-like material are produced. Raman/XPS measurements suggest the presence of amorphous or graphitic carbon onto crystalline Pd nanoparticles, which could have hindered their growth and determined the observed smaller sizes if compared to nanoparticles produced in water. The stability of Pd colloids obtained in acetone and alcohols was attributed to adsorbed anions like enolates or alcoholates; non polar solvents like toluene and n-hexane, unable to give rise to adsorbed anionic species, cannot provide any stabilization to the palladium nanoparticles. XPS analyses also evidenced a partial oxidation of particles surface, with a ratio Pd 2+ :Pd 0 of 1:2.5 and 1:4 in acetone and ethanol, respectively.

Analysis of recovered solvents from coal liquefaction in a flowing-solvent reactor by SEC and UV-fluorescence

Energy Technology Data Exchange (ETDEWEB)

Li, W.Y.; Feng, J.; Xie, K.C.; Kandiyoti, R. [Taiyuan University of Technology, Taiyuan (China)

2005-08-01

Point of Ayr coal has been extracted using three solvents: tetralin, quinoline and 1-methyl-2-pyrrolidinone (NMP); at two temperatures: 350 {sup o}C and 450{sup o}C, corresponding approximately to before and after the onset of massive covalent bond scission by pyrolysis. These solvents differ in solvent power and the ability to donate hydrogen atoms to stabilize free radicals produced by pyrolysis of the coal. Analysis of the fresh solvents and recovered solvents from coal liquefaction was achieved by size exclusion chromatography and UV-fluorescence spectroscopy. In the blank run, it was testified that the filling material sand and the steel powder did not react with solvent with increasing reaction temperature. The role of hydrogen donation in the tetralin extracts was to increase the proportion of large molecules with increasing extraction temperature. Quinoline and NMP both have the powerful extracting capability to get more materials out of coal with increasing extraction temperature.

Analysis of recovered solvents from coal liquefaction in a flowing-solvent reactor by SEC and UV-fluorescence

Energy Technology Data Exchange (ETDEWEB)

Wen-Ying Li; Jie Feng; Ke-Chang Xie; R. Kandiyoti [Taiyuan University of Technology, Taiyuan (China). Key Laboratory of Coal Science and Technology for Ministry of Education and Shanxi Province

2005-08-01

Point of Ayr coal has been extracted using three solvents: tetralin, quinoline and 1-methyl-2-pyrrolidinone (NMP); at two temperatures: 350{sup o}C and 450{sup o}C, corresponding approximately to before and after the onset of massive covalent bond scission by pyrolysis. These solvents differ in solvent power and the ability to donate hydrogen atoms to stabilize free radicals produced by pyrolysis of the coal. Analysis of the fresh solvents and recovered solvents from coal liquefaction was achieved by size exclusion chromatography and UV-fluorescence spectroscopy. In the blank run, it was testified that the filling material sand and the steel powder did not react with solvent with increasing reaction temperature. The role of hydrogen donation in the tetralin extracts was to increase the proportion of large molecules with increasing extraction temperature. Quinoline and NMP both have the powerful extracting capability to get more materials out of coal with increasing extraction temperature.

An Efficient Solvent-Free Protocol for the Synthesis of 1-Amidoalkyl-2-naphthols using Silica-Supported Molybdatophosphoric Acid

Directory of Open Access Journals (Sweden)

Abdolkarim Zare

2010-01-01

Full Text Available A highly efficient, green and simple solvent-free method for the synthesis of 1-amidoalkyl-2-naphthols via one-pot multi-components condensation of 2-naphthol, aromatic aldehydes and amides in the presence of catalytic amount of silica-supported molybdatophosphoric acid (H3PMo12O40.xH2O/SiO2, 3.17 mol% is described. The reactions proceed rapidly and the title compounds are produced in high to excellent yields.

Solvent-free Hydrodeoxygenation of Bio-oil Model Compounds Cyclopentanone and Acetophenone over Flame-made Bimetallic Pt-Pd/ZrO2 Catalysts

Science.gov (United States)

Jiang, Yijiao; Büchel, Robert; Huang, Jun; Krumeich, Frank; Pratsinis, Sotiris E.; Baiker, Alfons

2013-01-01

Bimetallic Pt-Pd/ZrO2 catalysts with different Pt/Pd atomic ratio and homogeneous dispersion of the metal nanoparticles were prepared in a single step by flame-spray pyrolysis. The catalysts show high activity and tuneable product selectivity for the solvent-free hydrodeoxygenation of the bio-oil model compounds cyclopentanone and acetophenone. PMID:22674738

Green chemistry by nano-catalysis

KAUST Repository

Polshettiwar, Vivek

2010-01-01

Nano-materials are important in many diverse areas, from basic research to various applications in electronics, biochemical sensors, catalysis and energy. They have emerged as sustainable alternatives to conventional materials, as robust high surface area heterogeneous catalysts and catalyst supports. The nano-sized particles increase the exposed surface area of the active component of the catalyst, thereby enhancing the contact between reactants and catalyst dramatically and mimicking the homogeneous catalysts. This review focuses on the use of nano-catalysis for green chemistry development including the strategy of using microwave heating with nano-catalysis in benign aqueous reaction media which offers an extraordinary synergistic effect with greater potential than these three components in isolation. To illustrate the proof-of-concept of this "green and sustainable" approach, representative examples are discussed in this article. © 2010 The Royal Society of Chemistry.

On the Collisionless Asymmetric Magnetic Reconnection Rate

Science.gov (United States)

Liu, Yi-Hsin; Hesse, M.; Cassak, P. A.; Shay, M. A.; Wang, S.; Chen, L.-J.

2018-04-01

A prediction of the steady state reconnection electric field in asymmetric reconnection is obtained by maximizing the reconnection rate as a function of the opening angle made by the upstream magnetic field on the weak magnetic field (magnetosheath) side. The prediction is within a factor of 2 of the widely examined asymmetric reconnection model (Cassak & Shay, 2007, https://doi.org/10.1063/1.2795630) in the collisionless limit, and they scale the same over a wide parameter regime. The previous model had the effective aspect ratio of the diffusion region as a free parameter, which simulations and observations suggest is on the order of 0.1, but the present model has no free parameters. In conjunction with the symmetric case (Liu et al., 2017, https://doi.org/10.1103/PhysRevLett.118.085101), this work further suggests that this nearly universal number 0.1, essentially the normalized fast-reconnection rate, is a geometrical factor arising from maximizing the reconnection rate within magnetohydrodynamic-scale constraints.

From micelle supramolecular assemblies in selective solvents to isoporous membranes

KAUST Repository

Nunes, Suzana Pereira; Karunakaran, Madhavan; Neelakanda, Pradeep; Behzad, Ali Reza; Hooghan, Bobby; Sougrat, Rachid; He, Haoze; Peinemann, Klaus-Viktor

2011-01-01

The supramolecular assembly of PS-b-P4VP copolymer micelles induced by selective solvent mixtures was used to manufacture isoporous membranes. Micelle order in solution was confirmed by cryo-scanning electron microscopy in casting solutions, leading to ordered pore morphology. When dioxane, a solvent that interacts poorly with the micelle corona, was added to the solution, polymer-polymer segment contact was preferential, increasing the intermicelle contact. Immersion in water gave rise to asymmetric porous membranes with exceptional pore uniformity and high porosity. The introduction of a small number of carbon nanotubes to the casting solution improved the membrane stability and the reversibility of the gate response in the presence of different pH values. © 2011 American Chemical Society.

From micelle supramolecular assemblies in selective solvents to isoporous membranes

KAUST Repository

Nunes, Suzana Pereira

2011-08-16

The supramolecular assembly of PS-b-P4VP copolymer micelles induced by selective solvent mixtures was used to manufacture isoporous membranes. Micelle order in solution was confirmed by cryo-scanning electron microscopy in casting solutions, leading to ordered pore morphology. When dioxane, a solvent that interacts poorly with the micelle corona, was added to the solution, polymer-polymer segment contact was preferential, increasing the intermicelle contact. Immersion in water gave rise to asymmetric porous membranes with exceptional pore uniformity and high porosity. The introduction of a small number of carbon nanotubes to the casting solution improved the membrane stability and the reversibility of the gate response in the presence of different pH values. © 2011 American Chemical Society.

Multi-catalysis cascade reactions based on the methoxycarbonylketene platform: diversity-oriented synthesis of functionalized non-symmetrical malonates for agrochemicals and pharmaceuticals.

Science.gov (United States)

Ramachary, Dhevalapally B; Venkaiah, Chintalapudi; Reddy, Y Vijayendar; Kishor, Mamillapalli

2009-05-21

In this paper we describe new multi-catalysis cascade (MCC) reactions for the one-pot synthesis of highly functionalized non-symmetrical malonates. These metal-free reactions are either five-step (olefination/hydrogenation/alkylation/ketenization/esterification) or six-step (olefination/hydrogenation/alkylation/ketenization/esterification/alkylation), and employ aldehydes/ketones, Meldrum's acid, 1,4-dihydropyridine/o-phenylenediamine, diazomethane, alcohols and active ethylene/acetylenes, and involve iminium-, self-, self-, self- and base-catalysis, respectively. Many of the products have direct application in agricultural and pharmaceutical chemistry.

Asymmetric Catalytic Aza-Diels-Alder/Ring-Closing Cascade Reaction Forming Bicyclic Azaheterocycles by Trienamine Catalysis.

Science.gov (United States)

Li, Yang; Barløse, Casper; Jørgensen, Julie; Carlsen, Bjørn Dreiø; Jørgensen, Karl Anker

2017-01-01

An asymmetric catalytic aza-Diels-Alder/ring-closing cascade reaction between acylhydrazones and in situ formed trienamines is presented. The reaction proceeds through a formal aza-Diels-Alder cycloaddition, followed by a ring-closing reaction forming the hemiaminal ring leading to chiral bicyclic azaheterocycles in moderate to good yield (up to 71 %), good enantio- (up to 92 % ee) and diastereoselectivity (up to >20:1 d.r.). Furthermore, transformations are presented to show the potential application of the formed product. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Laboratory Catalysis Research Symposium - Abstracts

Energy Technology Data Exchange (ETDEWEB)

Dunham, T.

1999-02-01

The conference consisted of two sessions with the following subtopics: (1) Heterogeneous Session: Novel Catalytic Materials; Photocatalysis; Novel Processing Conditions; Metals and Sulfides; Nuclear Magnetic Resonance; Metal Oxides and Partial Oxidation; Electrocatalysis; and Automotive Catalysis. (2) Homogeneous Catalysis: H-Transfer and Alkane Functionalization; Biocatalysis; Oxidation and Photocatalysis; and Novel Medical, Methods, and Catalyzed Reactions.

Nitropyrroles, Diels-Alder reactions assisted by microwave irradiation and solvent effect. An experimental and theoretical study

Science.gov (United States)

Mancini, Pedro M. E.; Kneeteman, María N.; Cainelli, Mauro; Ormachea, Carla M.; Domingo, Luis R.

2017-11-01

The behaviors of N-tosylnitropyrroles acting as electrophilic dienophiles in polar Diels-Alder reactions joint to different dienes of increeased nucleophilicity are analyzed. The reactions were developed under microwave irradiation using toluene or protic ionic liquids (PILs) as solvents and in free solvent conditions. In all the cases explored we observed good yields in short reaction times. For these reactions, the free solvent condition and the use of protic ionic liquids as solvents offer similar results. However, the free solvent conditions favor environmental sustainability. The role of PILs in these polar Diels-Alder reactions has been theoretically studied within the Molecular Electron Density Theory.

Metal-Free Approaches to Sterically-Hindered Bonds

Science.gov (United States)

Dunham, Veronica Vin-yi

Developing methods to perform cross coupling reactions by means of catalysis is highly desirable in chemistry. Many industries in today's society, such as the petroleum, agriculture, pharmaceutical, electronics, and polymer industry, use catalysis to some extent whether it is to make molecules that offer crop protection or toward the synthesis of the active ingredient of a medication. It is noteworthy that over 90% of chemicals are made through catalytic processes and that the catalyst market reached $17 billion in 2014, which demonstrates the demand for such methods. While transition metal catalysts have advantages such as low catalyst loading, broad reactivity, and that they have been well studied, some disadvantages are that they can be relatively expensive and sometimes air sensitive which can make them challenging to use. Organocatalysis, specifically noncovalent catalysis operating through hydrogen bond donating interactions, offers an environmentally-friendly alternative to transition metal catalysis. Our lab utilizes organocatalysis as a strategy to synthesize challenging, sterically-hindered bonds. Nitrimines have been identified as powerful coupling partners for the sustainable construction of new sterically congested carbon-carbon and carbon-heteroatom bonds. Using urea catalysis, a metal-free method to synthesize previously inaccessible enamines has been developed. Conventional routes to synthesize enamines as important building blocks toward target molecules generally require Lewis/Bronsted acids or expensive transition metals; however, these methods are often unsuccessful when stericallyhindered substrates are used. To address this synthetic challenge, it was hypothesized that hydrogen bonding interactions between a urea organocatalyst and nitrimine would generate a reactive species suited for the effective carbon-nitrogen coupling with amines to give the desired enamine products. This reaction provides high yields (up to 99%) of enamines using a

New and future developments in catalysis catalysis by nanoparticles

CERN Document Server

Suib, Steven L

2013-01-01

New and Future Developments in Catalysis is a package of seven books that compile the latest ideas concerning alternate and renewable energy sources and the role that catalysis plays in converting new renewable feedstock into biofuels and biochemicals. Both homogeneous and heterogeneous catalysts and catalytic processes will be discussed in a unified and comprehensive approach. There will be extensive cross-referencing within all volumes. The use of catalysts in the nanoscale offers various advantages (increased efficiency and less byproducts), and these are discussed in this volume along with the various catalytic processes using nanoparticles. However, this is not without any risks and the safety aspects and effects on humans and the environment are still unknown. The present data as well as future needs are all part of this volume along with the economics involved. Offers in-depth coverage of all catalytic topics of current interest and outlines future challenges and research areas A clear and visual descr...

Rationalization of an unusual solvent-induced inversion of enantiomeric excess in organocatalytic selenylation of aldehydes.

Science.gov (United States)

Burés, Jordi; Dingwall, Paul; Armstrong, Alan; Blackmond, Donna G

2014-08-11

An unusual solvent-induced inversion of the sense of enantioselectivity observed in the α-selenylation of aldehydes catalyzed by a diphenylprolinol silyl ether catalyst is correlated to the presence of intermediates formed subsequent to the highly selective C-Se bond-forming step in the catalytic cycle. This work provides support for a mechanistic concept for enamine catalysis and includes a general role for "downstream intermediates" in selectivity outcomes in organocatalysis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Editorial: Nanoscience makes catalysis greener

KAUST Repository

Polshettiwar, Vivek

2012-01-09

Green chemistry by nanocatalysis: Catalysis is a strategic field of science because it involves new ways of meeting energy and sustainability challenges. The concept of green chemistry, which makes the science of catalysis even more creative, has become an integral part of sustainability. This special issue is at the interface of green chemistry and nanocatalysis, and features excellent background articles as well as the latest research results. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic Synthesis under Solvent-free Condition. An Environmentally ...

Indian Academy of Sciences (India)

Though it is a common practice to run the organic reactions in solvent media, the ... this concept is simple. That is, the ... to vigorous research activity and reinvestigation of known reac- tions to achieve ... experimental procedure, work up technique and saving in labour. These would be ... This is true not only of the crystals of ...

Asymmetric Flexible MXene-Reduced Graphene Oxide Micro-Supercapacitor

KAUST Repository

Couly, Cedric

2017-11-27

Current microfabrication of micro-supercapacitors often involves multistep processing and delicate lithography protocols. In this study, simple fabrication of an asymmetric MXene-based micro-supercapacitor that is flexible, binder-free, and current-collector-free is reported. The interdigitated device architecture is fabricated using a custom-made mask and a scalable spray coating technique onto a flexible, transparent substrate. The electrode materials are comprised of titanium carbide MXene (Ti3C2Tx) and reduced graphene oxide (rGO), which are both 2D layered materials that contribute to the fast ion diffusion in the interdigitated electrode architecture. This MXene-based asymmetric micro-supercapacitor operates at a 1 V voltage window, while retaining 97% of the initial capacitance after ten thousand cycles, and exhibits an energy density of 8.6 mW h cm−3 at a power density of 0.2 W cm−3. Further, these micro-supercapacitors show a high level of flexibility during mechanical bending. Utilizing the ability of Ti3C2Tx-MXene electrodes to operate at negative potentials in aqueous electrolytes, it is shown that using Ti3C2Tx as a negative electrode and rGO as a positive one in asymmetric architectures is a promising strategy for increasing both energy and power densities of micro-supercapacitors.

Symmetrization of the beam-beam interaction in an asymmetric collider

International Nuclear Information System (INIS)

Chin, Y.H.

1990-07-01

This paper studies the idea of symmetrizing both the lattice and the beams of an asymmetric collider, and discusses why this regime should be within the parametric reach of the design in order to credibly ensure its performance. Also examined is the effectiveness of a simple compensation method using the emittance as a free parameter and that it does not work in all cases. At present, when there are no existing asymmetric colliders, it seems prudent to design an asymmetric collider so as to be similar to a symmetric one (without relying on a particular theory of the asymmetric beam-beam interaction that has not passed tests of fidelity). Nevertheless, one must allow for the maximum possible flexibility and freedom in adjusting those parameters that affect luminosity. Such a parameter flexibility will be essential in tuning the collider to the highest luminosity

Solvent extraction of Au(III) for preparation of a carrier-free multitracer and an Au tracer from an Au target

International Nuclear Information System (INIS)

Weginwar, R.G.; Kobayashi, Y.; Ambe, S.; Liu, B.; Enomoto, S.; Ambe, F.

1996-01-01

Separation of Au(III) and various carrier-free radionuclides by solvent extraction was investigated using an Au target irradiated by an energetic heavy-ion beam. Percentage extraction of Au(III) and coextraction of the radionuclides were determined with varying parameters such as kinds of solvent, molarity of HCl or pH, and Au concentration. Under the conditions where Au(III) was effectively extracted, namely extraction with ethyl acetate or isobutyl methyl ketone from 3 mol*dm -3 HCl, carrier-free radionuclides of many elements were found to be more or less coextracted. Coextraction of radionuclides of some elements was found to increase with an increase in the concentration of Au(III). This finding is ascribed to the formation of strong association of the complex of these elements with chloroauric acid. In order to avoid serious loss of these elements by the extraction, lowering of the Au(III) concentration or the use of a masking agent such as sodium citrate is necessary. Gold(III) was shown to be effectively back extracted with a 0.1 mol*dm -3 aqueous solution of 2-amino-2-hydroxymethyl-1,3-propanediol. Thus, a radiochemical procedure has been established for preparing a carrier-free multitracer and an Au tracer with carrier form from an Au target irradiated with a heavy-ion beam. Both tracers are now used individually for chemical and biological experiments. (author). 22 refs., 3 figs., 2 tabs

New Polymeric Membranes for Organic Solvent Nanofiltration

KAUST Repository

Aburabie, Jamaliah

2017-05-01

The focus of this dissertation was the development, synthesis and modification of polymers for the preparation of membranes for organic solvent nanofiltration. High chemical stability in a wide range of solvents was a key requirement. Membranes prepared from synthesized polymers as well as from commercial polymers were designed and chemically modified to reach OSN requirements. A solvent stable thin-film composite (TFC) membrane is reported, which is fabricated on crosslinked polythiosemicarbazide (PTSC) as substrate. The membranes exhibited high fluxes towards solvents like THF, DMF and DMSO ranging around 20 L/m2 h at 5 bar with a MWCO of around 1000 g/mol. Ultrafiltration PTSC membranes were prepared by non-solvent induced phase separation and crosslinked with GPTMS. The crosslinking reaction was responsible for the formation of an inorganic-type-network that tuned the membrane pore size. The crosslinked membranes acquired high solvent stability in DMSO, DMF and THF with a MWCO above 1300 g/mol. Reaction Induced Phase Separation (RIPS) was introduced as a new method for the preparation of skinned asymmetric membranes. These membranes have two distinctive layers with different morphologies both from the same polymer. The top dense layer is composed of chemically crosslinked polymer chains while the bottom layer is a porous structure formed by non-crosslinked polymer chains. Such membranes were tested for vitamin B12 in solvents after either crosslinking the support or dissolving the support and fixing the freestanding membrane on alumina. Pebax® 1657 was utilized for the preparation of composite membranes by simple coating. Porous PAN membranes were coated with Pebax® 1657 which was then crosslinked using TDI. Crosslinked Pebax® membranes show high stability towards ethanol, propanol and acetone. The membranes were also stable in DMF once crosslinked PAN supports were used. Sodium alginate polymer was investigated for the preparation of thin film composite

The solvent effects on dimethyl phthalate investigated by FTIR characterization, solvent parameter correlation and DFT computation

Science.gov (United States)

Chen, Yi; Zhang, Hui; Zhou, Wenzhao; Deng, Chao; Liao, Jian

2018-06-01

This study set out with the aim of investigating the solvent effects on dimethyl phthalate (DMP) using FTIR characterization, solvent parameter correlation and DFT calculation. DMP exposed to 17 organic solvents manifested varying shift in the carbonyl stretching vibration frequency (νCdbnd O). Non-alkanols induced Band I and alkanols produced Band I and Band II. Through correlating the νCdbnd O with the empirical solvent scales including acceptor parameter (AN), Schleyer's linear free energy parameter (G), and linear free salvation energy relationships (LSER), Band I was mainly ascribed to non-specific effects from either non-alkanols or alkanol polymers ((alkanol)n). νCdbnd O of the latter indicated minor red shift and less variability compared to the former. An assumption was made and validated about the sequestering of hydroxyl group by the bulky hydrophobic chain in (alkanol)n, creating what we refer to as "screening effects". Ab initio calculation, on the other hand, provided insights for possible hydrogen binding between DMP and (ethanol)n or between ethanol monomers. The two components of Band I observed in inert solvents were assigned to the two Cdbnd O groups adopting differentiated conformations. This in turn prompted our consideration that hydrogen binding was highly selective in favor of lowly associated (alkanol)n and the particular Cdbnd O group having relatively less steric hindrance and stronger electron-donating capacity. Band II was therefore believed to derive from hydrogen-bond interactions mainly in manner of 1:1 and 1:2 DMP-(alkanol)n complexes.

Dipyridine cobalt chloride as an efficient and chemoselective catalyst for the synthesis of 1,1-diacetates under solvent-free conditions

Directory of Open Access Journals (Sweden)

Sobhan Rezayati

2014-02-01

Full Text Available 1,1-Diacetates(acylals were prepared by direct condensation of various aldehydes with acetic anhydride using dipyridine cobalt chloride (CoPy2Cl2 as an efficient and green catalyst under solvent-free conditions at room temperature. The important features of this catalyst method are that the catalyst is solid, stable at high temperatures, soluble in water, stable in air, immiscible in common organic solvents, and low toxic and, above all, it is reusable. CoPy2Cl2 can be recycled after a simple work-up and reused at least five runs without appreciable loss of its catalytic activity. High chemo-selectivity toward aldehyde in the presence of ketones is another advantage of the present method which provides selective protection of aldehydes in their mixtures with ketones.

A Solvent-Free Surface Suspension Melt Technique for Making Biodegradable PCL Membrane Scaffolds for Tissue Engineering Applications

Directory of Open Access Journals (Sweden)

Ratima Suntornnond

2016-03-01

Full Text Available In tissue engineering, there is limited availability of a simple, fast and solvent-free process for fabricating micro-porous thin membrane scaffolds. This paper presents the first report of a novel surface suspension melt technique to fabricate a micro-porous thin membrane scaffolds without using any organic solvent. Briefly, a layer of polycaprolactone (PCL particles is directly spread on top of water in the form of a suspension. After that, with the use of heat, the powder layer is transformed into a melted layer, and following cooling, a thin membrane is obtained. Two different sizes of PCL powder particles (100 µm and 500 µm are used. Results show that membranes made from 100 µm powders have lower thickness, smaller pore size, smoother surface, higher value of stiffness but lower ultimate tensile load compared to membranes made from 500 µm powder. C2C12 cell culture results indicate that the membrane supports cell growth and differentiation. Thus, this novel membrane generation method holds great promise for tissue engineering.

Kinetic evolutionary behavior of catalysis-select migration

International Nuclear Information System (INIS)

Wu Yuan-Gang; Lin Zhen-Quan; Ke Jian-Hong

2012-01-01

We propose a catalysis-select migration driven evolution model of two-species (A- and B-species) aggregates, where one unit of species A migrates to species B under the catalysts of species C, while under the catalysts of species D the reaction will become one unit of species B migrating to species A. Meanwhile the catalyst aggregates of species C perform self-coagulation, as do the species D aggregates. We study this catalysis-select migration driven kinetic aggregation phenomena using the generalized Smoluchowski rate equation approach with C species catalysis-select migration rate kernel K(k;i,j) = Kkij and D species catalysis-select migration rate kernel J(k;i,j)= Jkij. The kinetic evolution behaviour is found to be dominated by the competition between the catalysis-select immigration and emigration, in which the competition is between JD 0 and KC 0 (D 0 and C 0 are the initial numbers of the monomers of species D and C, respectively). When JD 0 −KC 0 > 0, the aggregate size distribution of species A satisfies the conventional scaling form and that of species B satisfies a modified scaling form. And in the case of JD 0 −KC 0 0 −KC 0 > 0 case. (interdisciplinary physics and related areas of science and technology)

Nano catalysis: Academic Discipline and Industrial Realities

International Nuclear Information System (INIS)

Olveira, S.; Forster, S.P.; Seeger, S.

2014-01-01

Nano technology plays a central role in both academic research and industrial applications. Nano enabled products are not only found in consumer markets, but also importantly in business to business markets (B2B). One of the oldest application areas of nano technology is nano catalysis—an excellent example for such a B2 B market. Several existing reviews illustrate the scientific developments in the field of nano catalysis. The goal of the present review is to provide an up-to-date picture of academic research and to extend this picture by an industrial and economic perspective. We therefore conducted an extensive search on several scientific databases and we further analyzed more than 1,500 nano catalysis-related patents and numerous market studies. We found that scientists today are able to prepare nano catalysts with superior characteristics regarding activity, selectivity, durability, and recoverability, which will contribute to solve current environmental, social, and industrial problems. In industry, the potential of nano catalysis is recognized, clearly reflected by the increasing number of nano catalysis-related patents and products on the market. The current nano catalysis research in academic and industrial laboratories will therefore enable a wealth of future applications in the industry

Reference-free unwarping of single-shot spatiotemporally encoded MRI using asymmetric self-refocused echoes acquisition

Science.gov (United States)

Chen, Ying; Chen, Song; Zhong, Jianhui; Chen, Zhong

2015-05-01

This paper presents a phase evolution rewinding algorithm for correcting the geometric and intensity distortions in single-shot spatiotemporally encoded (SPEN) MRI with acquisition of asymmetric self-refocused echo trains. Using the field map calculated from the phase distribution of the source image, the off-resonance induced phase errors are successfully rewound through deconvolution. The alias-free partial Fourier transform reconstruction helps improve the signal-to-noise ratio of the field maps and the output images. The effectiveness of the proposed algorithm was validated through 7 T MRI experiments on a lemon, a water phantom, and in vivo rat head. SPEN imaging was evaluated using rapid acquisition by sequential excitation and refocusing (RASER) which produces uniform T2 weighting. The results indicate that the new technique can more robustly deal with the cases in which the images obtained with conventional single-shot spin-echo EPI are difficult to be restored due to serious field variations.

Operando research in heterogeneous catalysis

CERN Document Server

Groot, Irene

2017-01-01

This book is devoted to the emerging field of techniques for visualizing atomic-scale properties of active catalysts under actual working conditions, i.e. high gas pressures and high temperatures. It explains how to understand these observations in terms of the surface structures and dynamics and their detailed interplay with the gas phase. This provides an important new link between fundamental surface physics and chemistry, and applied catalysis. The book explains the motivation and the necessity of operando studies, and positions these with respect to the more traditional low-pressure investigations on the one hand and the reality of industrial catalysis on the other. The last decade has witnessed a rapid development of new experimental and theoretical tools for operando studies of heterogeneous catalysis. The book has a strong emphasis on the new techniques and illustrates how the challenges introduced by the harsh, operando conditions are faced for each of these new tools. Therefore, one can also read th...

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

International Nuclear Information System (INIS)

Zhou Shiqi

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.

Combining MOSCED with molecular simulation free energy calculations or electronic structure calculations to develop an efficient tool for solvent formulation and selection

Science.gov (United States)

Cox, Courtney E.; Phifer, Jeremy R.; Ferreira da Silva, Larissa; Gonçalves Nogueira, Gabriel; Ley, Ryan T.; O'Loughlin, Elizabeth J.; Pereira Barbosa, Ana Karolyne; Rygelski, Brett T.; Paluch, Andrew S.

2017-02-01

Solubility parameter based methods have long been a valuable tool for solvent formulation and selection. Of these methods, the MOdified Separation of Cohesive Energy Density (MOSCED) has recently been shown to correlate well the equilibrium solubility of multifunctional non-electrolyte solids. However, before it can be applied to a novel solute, a limited amount of reference solubility data is required to regress the necessary MOSCED parameters. Here we demonstrate for the solutes methylparaben, ethylparaben, propylparaben, butylparaben, lidocaine and ephedrine how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here the SMD or SM8 solvation model, can instead be used to generate the necessary reference data, resulting in a predictive flavor of MOSCED. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. We find the method is able to well correlate the (mole fraction) equilibrium solubility in non-aqueous solvents over four orders of magnitude with good quantitative agreement.

An Efficient Synthesis of 3,4-Dihydropyrimidin-2(1H-Ones and Thiones Catalyzed by a Novel Brønsted Acidic Ionic Liquid under Solvent-Free Conditions

Directory of Open Access Journals (Sweden)

Yonghong Zhang

2015-02-01

Full Text Available We report here an efficient and green method for Biginelli condensation reaction of aldehydes, β-ketoesters and urea or thiourea catalyzed by Brønsted acidic ionic liquid [Btto][p-TSA] under solvent-free conditions. Compared to the classical Biginelli reaction conditions, the present method has the advantages of giving good yields, short reaction times, near room temperature conditions and the avoidance of the use of organic solvents and metal catalyst.

Advancing Sustainable Catalysis with Magnetite Surface ...

Science.gov (United States)

This article surveys the recent developments in the synthesis, surface modification, and synthetic applications of magnetitenanoparticles. The emergence of iron(II,III) oxide (triiron tetraoxide or magnetite; Fe3O4, or FeO•Fe2O3) nanoparticles as a sustainable support in heterogeneous catalysis is highlighted. Use of an oxide of earth-abundant iron for various applications in catalysis and environmental remediation.

Keynotes in energy-related catalysis

CERN Document Server

Kaliaguine, S

2011-01-01

Catalysis by solid acids, which includes (modified) zeolites, is of special relevance to energy applications. Acid catalysis is highly important in modern petroleum refining operations - large-scale processes such as fluid catalytic cracking, catalytic reforming, alkylation and olefin oligomerization rely on the transformation of hydrocarbons by acid catalysts. (Modified) zeolites are therefore essential for the improvement of existing processes and for technical innovations in the conversion of crude. There can be little doubt that zeolite-based catalysts will play a major role in the futu

An Expeditious and Greener Synthesis of 2-Aminoimidazoles in Deep Eutectic Solvents

Directory of Open Access Journals (Sweden)

Martina Capua

2016-07-01

Full Text Available A high-yield one-pot two-step synthesis of 2-aminoimidazoles (2-AI, exploiting an under-air heterocyclodehydration process between α-chloroketones and guanidine derivatives, and using deep eutectic solvents (DESs as nonconventional, “green” and “innocent” reaction media, has been accomplished successfully. The combination of either glycerol or urea with choline chloride (ChCl proved to be effective for decreasing the reaction time to about 4–6 h in contrast to the 10–12 h usually required for the same reaction run in toxic and volatile organic solvents and under an argon atmosphere. In addition, the use of the ChCl–urea as a DES also enables the direct isolation of triaryl-substituted 2-AI derivatives by means of a simple work-up procedure consisting in filtration and crystallization, and allows the recycle of the DES mixture. A plausible mechanism highlighting the potential role played by hydrogen bonding catalysis has also been illustrated.

Organic carbonates as solvents in macrocyclic Mn(III) salen catalyzed asymmetric epoxidation of non-functionalized olefins

Czech Academy of Sciences Publication Activity Database

Maity, N. Ch.; Rao, G. V. S.; Prathap, Kaniraj Jeya; Abdi, S. H. R.; Kureshy, R. I.; Khan, N. H.; Bajaj, H. C.

2013-01-01

Roč. 366, January (2013), s. 380-389 ISSN 1381-1169 Institutional support: RVO:61388963 Keywords : asymmetric epoxidation * organic carbonate * macrocyclic Mn(III) salen complex Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.679, year: 2013

Apparent Molal Volumes of Sodium Fluoride in Mixed Aqueous-Ethanol Solvents

Directory of Open Access Journals (Sweden)

E. Gomaa

2010-09-01

Full Text Available The densities of different molal concentrations of sodium fluoride at ethanol-water mixtures, as solvent, have been measured over the whole composition range at three different temperatures, 293.15, 303.15 and 313.15oK. From the measured densities, the apparent and limiting molal volumes of the electrolytes have been evaluated. The limiting molal volumes for sodium and fluoride ions were estimated by splitting the ionic contributions as an asymmetric assumption.

Catalytic asymmetric dihydroxylation of olefins using a recoverable and reusable OsO(4)2- in ionic liquid [bmim][PF6].

Science.gov (United States)

Branco, Luís C; Afonso, Carlos A M

2002-12-21

The use of the solvent systems water/ionic liquid or water/ionic liquid/tert-butanol provides a recoverable, reusable, robust and simple system for the asymmetric dihydroxylation of olefins, based on the immobilization of the osmium-ligand catalyst in the ionic liquid phase.

Asymmetric aza-Diels-Alder reaction of Danishefsky's diene with imines in a chiral reaction medium

Directory of Open Access Journals (Sweden)

Pégot Bruce

2006-09-01

Full Text Available Abstract The asymmetric aza-Diels-Alder reaction of chiral imines with Danishefsky's diene in chiral ionic liquids provides the corresponding cycloadduct with moderate to high diastereoselectivity. The reaction has proved to perform better at room temperature in ionic liquids without either Lewis acid catalyst or organic solvent. Chiral ionic liquids are recycled while their efficiency is preserved.

[Prediction of common buffer catalysis in hydrolysis of fenchlorazole-ethyl].

Science.gov (United States)

Lin, Jing; Chen, Jing-wen; Zhang, Si-yu; Cai, Xi-yun; Qiao, Xian-liang

2008-09-01

The purpose of this study was to elucidate the effects of temperatures, pH levels and buffer catalysis on the hydrolysis of FCE. The hydrolysis of FCE follows first-order kinetics at different pH levels and temperatures. FCE hydrolysis rates are greatly increased at elevated pH levels and temperatures. The maximum contribution of buffer catalysis to the hydrolysis of FCE was assessed based on application of the Bronsted equations for general acid-base catalysis. The results suggest that the buffer solutions play an obvious catalysis role in hydrolysis of FCE and the hydrolysis rates of FCE are quickened by the buffer solutions. Besides, the buffer catalysis capacity of different buffer solutions is diverse, and the buffer catalysis capacity at different pH levels with the same buffer solutions is different, too. The phosphate buffer at pH = 7 shows the maximal buffer catalysis capacity. The hydrolysis rate constants of FCE as a function of temperature and pH, which were remedied by the buffer catalysis factor, were mathematically combined to predict the hydrolytic dissipation of FCE. The equation suggests that the hydrolysis half-lives of FCE ranged from 7 d to 790 d. Hydrolysis metabolites of FCE were identified by liquid chromatography-mass spectrometry. In basic conditions (pH 8-10), fenchlorazole was formed via breakdown of the ester bond of the safener.

Tandem catalysis: a new approach to polymers.

Science.gov (United States)

Robert, Carine; Thomas, Christophe M

2013-12-21

The creation of polymers by tandem catalysis represents an exciting frontier in materials science. Tandem catalysis is one of the strategies used by Nature for building macromolecules. Living organisms generally synthesize macromolecules by in vivo enzyme-catalyzed chain growth polymerization reactions using activated monomers that have been formed within cells during complex metabolic processes. However, these biological processes rely on highly complex biocatalysts, thus limiting their industrial applications. In order to obtain polymers by tandem catalysis, homogeneous and enzyme catalysts have played a leading role in the last two decades. In the following feature article, we will describe selected published efforts to achieve these research goals.

Solution small-angle x-ray scattering as a screening and predictive tool in the fabrication of asymmetric block copolymer membranes

KAUST Repository

Dorin, Rachel Mika; Marques, Debora S.; Sai, Hiroaki; Vainio, Ulla; Phillip, William A.; Peinemann, Klaus; Nunes, Suzana Pereira; Wiesner, Ulrich B.

2012-01-01

Small-angle X-ray scattering (SAXS) analysis of the diblock copolymer poly(styrene-b-(4-vinyl)pyridine) in a ternary solvent system of 1,4-dioxane, tetrahydrofuran, and N,N-dimethylformamide, and the triblock terpolymer poly(isoprene-b-styrene-b-(4-vinyl)-pyridine) in a binary solvent system of 1,4-dioxane and tetrahydrofuran, reveals a concentration-dependent onset of ordered structure formation. Asymmetric membranes fabricated from casting solutions with polymer concentrations at or slightly below this ordering concentration possess selective layers with the desired nanostructure. In addition to rapidly screening possible polymer solution concentrations, solution SAXS analysis also predicts hexagonal and square pore lattices of the final membrane surface structure. These results suggest solution SAXS as a powerful tool for screening casting solution concentrations and predicting surface structure in the fabrication of asymmetric ultrafiltration membranes from self-assembled block copolymers. (Figure presented) © 2012 American Chemical Society.

Solution small-angle x-ray scattering as a screening and predictive tool in the fabrication of asymmetric block copolymer membranes

KAUST Repository

Dorin, Rachel Mika

2012-05-15

Small-angle X-ray scattering (SAXS) analysis of the diblock copolymer poly(styrene-b-(4-vinyl)pyridine) in a ternary solvent system of 1,4-dioxane, tetrahydrofuran, and N,N-dimethylformamide, and the triblock terpolymer poly(isoprene-b-styrene-b-(4-vinyl)-pyridine) in a binary solvent system of 1,4-dioxane and tetrahydrofuran, reveals a concentration-dependent onset of ordered structure formation. Asymmetric membranes fabricated from casting solutions with polymer concentrations at or slightly below this ordering concentration possess selective layers with the desired nanostructure. In addition to rapidly screening possible polymer solution concentrations, solution SAXS analysis also predicts hexagonal and square pore lattices of the final membrane surface structure. These results suggest solution SAXS as a powerful tool for screening casting solution concentrations and predicting surface structure in the fabrication of asymmetric ultrafiltration membranes from self-assembled block copolymers. (Figure presented) © 2012 American Chemical Society.

An efficient and high-yielding one-pot synthesis of 1H-pyrazolo[1,2-b]phthalazine-5,10-diones catalyzed by sodium hydrogen carbonate under solvent-free conditions

OpenAIRE

Asieh Vafaee; Abolghasem Davoodnia; Mehdi Pordel; Mohammad Reza Bozorgmehr

2015-01-01

Sodium hydrogen carbonate, NaHCO3, efficiently catalyzes the one-pot, three-component reaction of phthalhydrazide, an aromatic aldehyde, and malononitrile or ethyl cyanoacetate under solvent-free conditions, to afford the corresponding 1H-pyrazolo[1,2-b]phthalazine-5,10-diones in high yields. Easy work‐up, inexpensive and readily available catalyst and avoiding the use of harmful organic solvents are other advantages of this simple procedure.

Controllable Catalysis with Nanoparticles: Bimetallic Alloy Systems and Surface Adsorbates

KAUST Repository

Chen, Tianyou

2016-05-16

Transition metal nanoparticles are privileged materials in catalysis due to their high specific surface areas and abundance of active catalytic sites. While many of these catalysts are quite useful, we are only beginning to understand the underlying catalytic mechanisms. Opening the “black box” of nanoparticle catalysis is essential to achieve the ultimate goal of catalysis by design. In this Perspective we highlight recent work addressing the topic of controlled catalysis with bimetallic alloy and “designer” adsorbate-stabilized metal nanoparticles.

Controllable Catalysis with Nanoparticles: Bimetallic Alloy Systems and Surface Adsorbates

KAUST Repository

Chen, Tianyou; Rodionov, Valentin

2016-01-01

Transition metal nanoparticles are privileged materials in catalysis due to their high specific surface areas and abundance of active catalytic sites. While many of these catalysts are quite useful, we are only beginning to understand the underlying catalytic mechanisms. Opening the “black box” of nanoparticle catalysis is essential to achieve the ultimate goal of catalysis by design. In this Perspective we highlight recent work addressing the topic of controlled catalysis with bimetallic alloy and “designer” adsorbate-stabilized metal nanoparticles.

Catalysis and sustainable (green) chemistry

Energy Technology Data Exchange (ETDEWEB)

Centi, Gabriele; Perathoner, Siglinda [Dipartimento di Chimica Industriale ed Ingegneria dei Materiali, University of Messina, Salita Sperone 31, 98166 Messina (Italy)

2003-01-15

Catalysis is a key technology to achieve the objectives of sustainable (green) chemistry. After introducing the concepts of sustainable (green) chemistry and a brief assessment of new sustainable chemical technologies, the relationship between catalysis and sustainable (green) chemistry is discussed and illustrated via an analysis of some selected and relevant examples. Emphasis is also given to the concept of catalytic technologies for scaling-down chemical processes, in order to develop sustainable production processes which reduce the impact on the environment to an acceptable level that allows self-depuration processes of the living environment.

Molecular catalysis science: Perspective on unifying the fields of catalysis.

Science.gov (United States)

Ye, Rong; Hurlburt, Tyler J; Sabyrov, Kairat; Alayoglu, Selim; Somorjai, Gabor A

2016-05-10

Colloidal chemistry is used to control the size, shape, morphology, and composition of metal nanoparticles. Model catalysts as such are applied to catalytic transformations in the three types of catalysts: heterogeneous, homogeneous, and enzymatic. Real-time dynamics of oxidation state, coordination, and bonding of nanoparticle catalysts are put under the microscope using surface techniques such as sum-frequency generation vibrational spectroscopy and ambient pressure X-ray photoelectron spectroscopy under catalytically relevant conditions. It was demonstrated that catalytic behavior and trends are strongly tied to oxidation state, the coordination number and crystallographic orientation of metal sites, and bonding and orientation of surface adsorbates. It was also found that catalytic performance can be tuned by carefully designing and fabricating catalysts from the bottom up. Homogeneous and heterogeneous catalysts, and likely enzymes, behave similarly at the molecular level. Unifying the fields of catalysis is the key to achieving the goal of 100% selectivity in catalysis.

YCl3-Catalyzed Highly Selective Ring Opening of Epoxides by Amines at Room Temperature and under Solvent-Free Conditions

Directory of Open Access Journals (Sweden)

Wuttichai Natongchai

2017-11-01

Full Text Available A simple, efficient, and environmentally benign approach for the synthesis of β-amino alcohols is herein described. YCl3 efficiently carried out the ring opening of epoxides by amines to produce β-amino alcohols under solvent-free conditions at room temperature. This catalytic approach is very effective, with several aromatic and aliphatic oxiranes and amines. A mere 1 mol % concentration of YCl3 is enough to deliver β-amino alcohols in good to excellent yields with high regioselectivity.

Colloidal Magnetic Heterostructured Nanocrystals with Asymmetric Topologies: Seeded-Growth Synthetic Routes and Formation Mechanisms

Science.gov (United States)

Scarfiello, Riccardo; Nobile, Concetta; Cozzoli, P. Davide

2016-12-01

Colloidal inorganic nanocrystals, free-standing crystalline nanostructures generated and processed in solution phase, represent an important class of advanced nanoscale materials owing to the flexibility with which their physical-chemical properties can be controlled through synthetic tailoring of their compositional, structural and geometric features and the versatility with which they can be integrated in technological fields as diverse as optoelectronics, energy storage/ conversion/production, catalysis and biomedicine. In recent years, building upon mechanistic knowledge acquired on the thermodynamic and kinetic processes that underlie nanocrystal evolution in liquid media, synthetic nanochemistry research has made impressive advances, opening new possibilities for the design, creation and mastering of increasingly complex “colloidal molecules”, in which nanocrystal modules of different materials are clustered together via solid-state bonding interfaces into free-standing, easily processable multifunctional nanocomposite systems. This Review will provide a glimpse into this fast-growing research field by illustrating progress achieved in the wet-chemical development of last-generation breeds of all-inorganic heterostructured nanocrystals (HNCs) in asymmetric non-onionlike geometries, inorganic analogues of polyfunctional organic molecules, in which distinct nanoscale crystalline modules are interconnected in hetero-dimer, hetero-oligomer and anisotropic multidomain architectures via epitaxial heterointerfaces of limited extension. The focus will be on modular HNCs entailing at least one magnetic material component combined with semiconductors and/or metals, which hold potential for generating enhanced or unconventional magnetic properties, while offering diversified or even new chemical-physical properties and functional capabilities. The available toolkit of synthetic strategies, all based on the manipulation of seeded-growth techniques, will be described

Colloidal Magnetic Heterostructured Nanocrystals with Asymmetric Topologies: Seeded-Growth Synthetic Routes and Formation Mechanisms

Directory of Open Access Journals (Sweden)

Riccardo Scarfiello

2016-12-01

Full Text Available Colloidal inorganic nanocrystals, free-standing crystalline nanostructures generated and processed in solution phase, represent an important class of advanced nanoscale materials owing to the flexibility with which their physical–chemical properties can be controlled through synthetic tailoring of their compositional, structural and geometric features and the versatility with which they can be integrated in technological fields as diverse as optoelectronics, energy storage/ conversion/production, catalysis and biomedicine. In recent years, building upon mechanistic knowledge acquired on the thermodynamic and kinetic processes that underlie nanocrystal evolution in liquid media, synthetic nanochemistry research has made impressive advances, opening new possibilities for the design, creation and mastering of increasingly complex colloidal molecules, in which nanocrystal modules of different materials are clustered together via solid-state bonding interfaces into free-standing, easily processable multifunctional nanocomposite systems. This Review will provide a glimpse into this fast-growing research field by illustrating progress achieved in the wet-chemical development of last-generation breeds of all-inorganic heterostructured nanocrystals (HNCs in asymmetric non-onionlike geometries, inorganic analogues of polyfunctional organic molecules, in which distinct nanoscale crystalline modules are interconnected in hetero-dimer, hetero-oligomer and anisotropic multidomain architectures via epitaxial heterointerfaces of limited extension. The focus will be on modular HNCs entailing at least one magnetic material component combined with semiconductors and/or metals, which hold potential for generating enhanced or unconventional magnetic properties, while offering diversified or even new chemical-physical properties and functional capabilities. The available toolkit of synthetic strategies, all based on the manipulation of seeded-growth techniques

Decoding Pure Rotational Molecular Spectra for Asymmetric Molecules

Directory of Open Access Journals (Sweden)

S. A. Cooke

2013-01-01

Full Text Available Rotational spectroscopy can provide insights of unparalleled precision with respect to the wavefunctions of molecular systems that have relevance in fields as diverse as astronomy and biology. In this paper, we demonstrate how asymmetric molecular pure rotational spectra may be analyzed “pictorially” and with simple formulae. It is shown that the interpretation of such spectra relies heavily upon pattern recognition. The presentation of some common spectral line positions in near-prolate asymmetric rotational spectra provides a means by which spectral assignment, and approximate rotational constant determination, may be usefully explored. To aid in this endeavor we have created a supporting, free, web page and mobile web page.

Instantaneous sediment transport model for asymmetric oscillatory sheet flow.

Directory of Open Access Journals (Sweden)

Xin Chen

Full Text Available On the basis of advanced concentration and velocity profiles above a mobile seabed, an instantaneous analytical model is derived for sediment transport in asymmetric oscillatory flow. The applied concentration profile is obtained from the classical exponential law based on mass conservation, and asymmetric velocity profile is developed following the turbulent boundary layer theory and the asymmetric wave theory. The proposed model includes two parts: the basic part that consists of erosion depth and free stream velocity, and can be simplified to the total Shields parameter power 3/2 in accordance with the classical empirical models, and the extra vital part that consists of phase-lead, boundary layer thickness and erosion depth. The effects of suspended sediment, phase-lag and asymmetric boundary layer development are considered particularly in the model. The observed instantaneous transport rate proportional to different velocity exponents due to phase-lag is unified and summarised by the proposed model. Both instantaneous and half period empirical formulas are compared with the developed model, using extensive data on a wide range of flow and sediment conditions. The synchronous variation in instantaneous transport rate with free stream velocity and its decrement caused by increased sediment size are predicted correctly. Net transport rates, especially offshore transport rates with large phase-lag under velocity skewed flows, which existing instantaneous type formulas failed to predict, are predicted correctly in both direction and magnitude by the proposed model. Net sediment transport rates are affected not only by suspended sediment and phase-lag, but also by the boundary layer difference between onshore and offshore.

Solvent-free synthesis of azomethines, spectral correlations and antimicrobial activities of some E-benzylidene-4-chlorobenzenamines

Directory of Open Access Journals (Sweden)

R. Suresh

2015-07-01

Full Text Available Some azomethines including substituted benzylidene-4-chlorobenzenamines (E-imines have been synthesized by fly-ash: PTS catalyzed microwave assisted condensation of 4-chloroaniline and substituted benzaldehydes under solvent-free conditions. The yield of the imines has been found to be more than 85%. The purity of all imines has been checked using their physical constants and UV, IR and NMR spectral data. These spectral data have been correlated with Hammett substituent constants and F and R parameters using single and multi-linear regression analysis. From the results of statistical analysis, the effect of substituents on the above spectral data has been studied. The antimicrobial activities of all imines have been studied using standard methods.

Quantum catalysis : the modelling of catalytic transition states

NARCIS (Netherlands)

Hall, M.B.; Margl, P.; Naray-Szabo, G.; Schramm, Vern; Truhlar, D.G.; Santen, van R.A.; Warshel, A.; Whitten, J.L.; Truhlar, D.G.; Morokuma, K.

1999-01-01

A review with 101 refs.; we present an introduction to the computational modeling of transition states for catalytic reactions. We consider both homogeneous catalysis and heterogeneous catalysis, including organometallic catalysts, enzymes, zeolites and metal oxides, and metal surfaces. We summarize

Microwave-Enhanced Sulphated Zirconia and SZ/MCM-41 Catalyzed Regioselective Synthesis of β-Amino Alcohols Under Solvent-Free Conditions

Directory of Open Access Journals (Sweden)

Eduardo González-Zamora

2008-04-01

Full Text Available A solvent-free approach for the regioselective synthesis of β-amino alcohols inshorter reaction times and higher yields, compared to conventional heating is described. Itinvolves microwave (MW exposure of undiluted reactants in the presence of sulphatedzirconia (SZ or sulphated zirconia over MCM-41 (SZM as catalyst. Both acid materialscan be easily recovered and reused.

Rhodium-Catalyzed Asymmetric N-H Functionalization of Quinazolinones with Allenes and Allylic Carbonates: The First Enantioselective Formal Total Synthesis of (-)-Chaetominine.

Science.gov (United States)

Zhou, Yirong; Breit, Bernhard

2017-12-22

An unprecedented asymmetric N-H functionalization of quinazolinones with allenes and allylic carbonates was successfully achieved by rhodium catalysis with the assistance of chiral bidentate diphosphine ligands. The high efficiency and practicality of this method was demonstrated by a low catalyst loading of 1 mol % as well as excellent chemo-, regio-, and enantioselectivities with broad functional group compatibility. Furthermore, this newly developed strategy was applied as key step in the first enantioselective formal total synthesis of (-)-chaetominine. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel, Solvent-Free, Single Ion Conductive Polymer Electrolytes

Science.gov (United States)

2008-01-20

liquid oligomeric analogue PEODME (ε = 8, dioxane:CH3CN mass ratio 48:7). The choice of the solvent mixture was a compromise between the...trifluoride – a derivative of Lewis acid properties. An increase in the degree of dissociation, decrease in the share of ionic associates and increase in...diphenylphosphinate this product is a solid, and in reaction with lithium diphenylphosphate the second fraction is a viscous, light-brown liquid , and

Dendritic brushes under theta and poor solvent conditions

Science.gov (United States)

Gergidis, Leonidas N.; Kalogirou, Andreas; Charalambopoulos, Antonios; Vlahos, Costas

2013-07-01

The effects of solvent quality on the internal stratification of polymer brushes formed by dendron polymers up to third generation were studied by means of molecular dynamics simulations with Langevin thermostat. The distributions of polymer units, of the free ends, the radii of gyration, and the back folding probabilities of the dendritic spacers were studied at the macroscopic states of theta and poor solvent. For high grafting densities we observed a small decrease in the height of the brush as the solvent quality decreases. The internal stratification in theta solvent was similar to the one we found in good solvent, with two and in some cases three kinds of populations containing short dendrons with weakly extended spacers, intermediate-height dendrons, and tall dendrons with highly stretched spacers. The differences increase as the grafting density decreases and single dendron populations were evident in theta and poor solvent. In poor solvent at low grafting densities, solvent micelles, polymeric pinned lamellae, spherical and single chain collapsed micelles were observed. The scaling dependence of the height of the dendritic brush at high density brushes for both solvents was found to be in agreement with existing analytical results.

Microwave Assisted Convenient One-Pot Synthesis of Coumarin Derivatives via Pechmann Condensation Catalyzed by FeF3 under Solvent-Free Conditions and Antimicrobial Activities of the Products

Directory of Open Access Journals (Sweden)

Vahid Vahabi

2014-08-01

Full Text Available A rapid and efficient solvent-free one-pot synthesis of coumarin derivatives by Pechmann condensation reactions of phenols with ethyl acetoacetate using FeF3 as a catalyst under microwave irradiation is described. This one-pot synthesis on a solid inorganic support provides the products in good yields. The newly synthesized compounds were systematically characterized by IR, 1H-NMR, 13C-NMR, MS and elemental CHN analyses. The proposed solvent-free microwave irradiation method using the environmentally friendly catalyst FeF3 offers the unique advantages of high yields, shorter reaction times, easy and quick isolation of the products, excellent chemoselectivity, and a one-pot, green synthesis. The products were screened for antimicrobial activity, and the results showed that the compounds reacted against all the tested bacteria.

Intensification of the Use of Ionic Liquids as Efficient Reaction Co-Solvents in Asymmetric Hydrogenations

Czech Academy of Sciences Publication Activity Database

Černá, I.; Klusoň, Petr; Bendová, Magdalena; Floriš, Tomáš; Pelantová, Helena; Pekárek, T.

2011-01-01

Roč. 50, č. 3 (2011), s. 264-272 ISSN 0255-2701 R&D Projects: GA AV ČR KAN400720701; GA AV ČR IAA400720710 Institutional research plan: CEZ:AV0Z40720504; CEZ:AV0Z50200510 Keywords : Ionic liquids * asymmetric hydrogenations * BmimPF6 Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.924, year: 2011

Exploring the ab initio/classical free energy perturbation method: The hydration free energy of water

International Nuclear Information System (INIS)

Sakane, Shinichi; Yezdimer, Eric M.; Liu, Wenbin; Barriocanal, Jose A.; Doren, Douglas J.; Wood, Robert H.

2000-01-01

The ab initio/classical free energy perturbation (ABC-FEP) method proposed previously by Wood et al. [J. Chem. Phys. 110, 1329 (1999)] uses classical simulations to calculate solvation free energies within an empirical potential model, then applies free energy perturbation theory to determine the effect of changing the empirical solute-solvent interactions to corresponding interactions calculated from ab initio methods. This approach allows accurate calculation of solvation free energies using an atomistic description of the solvent and solute, with interactions calculated from first principles. Results can be obtained at a feasible computational cost without making use of approximations such as a continuum solvent or an empirical cavity formation energy. As such, the method can be used far from ambient conditions, where the empirical parameters needed for approximate theories of solvation may not be available. The sources of error in the ABC-FEP method are the approximations in the ab initio method, the finite sample of configurations, and the classical solvent model. This article explores the accuracy of various approximations used in the ABC-FEP method by comparing to the experimentally well-known free energy of hydration of water at two state points (ambient conditions, and 973.15 K and 600 kg/m3). The TIP4P-FQ model [J. Chem. Phys. 101, 6141 (1994)] is found to be a reliable solvent model for use with this method, even at supercritical conditions. Results depend strongly on the ab initio method used: a gradient-corrected density functional theory is not adequate, but a localized MP2 method yields excellent agreement with experiment. Computational costs are reduced by using a cluster approximation, in which ab initio pair interaction energies are calculated between the solute and up to 60 solvent molecules, while multi-body interactions are calculated with only a small cluster (5 to 12 solvent molecules). Sampling errors for the ab initio contribution to

A Facile Solvent Free Microwave Induced Synthesis and Antibacterial Activity of Some 3-(2’-Hydroxyphenyl-5-(Substituted Aryl-2-Pyrazoline-N1-Caboxaldehydes

Directory of Open Access Journals (Sweden)

Birbal Bajia

2007-01-01

Full Text Available A novel one pot formylation of 3-(2’-hydroxyphenyl-5-(substituted 2-pyrazolines has been carried out using microwave irradiation with formic acid. solvent free reaction afforded title compounds in 80-90% yield with high purity.synthesized compounds were tested for their antibacterial activity using standard drug.

Advances in catalysis

International Nuclear Information System (INIS)

Eley, D.D.; Pine, H.; Weisz, P.B.

1989-01-01

This book reports on the current state of knowledge concerning structure and catalysis of metals and metal oxide particles, old and new. It addresses the basic and broad problems of what the catalytically relevant surface structures of metals are, where we stand in techniques capable of attacking this problem, and what the current state of knowledge is. The focus is on long-standing, important, and central problem of general investigative methodology and strategy: the pressure gap is created by the fact that the best techniques of surface analysis require high-vacuum conditions, while useful catalysis is confined to conditions of near ambient or higher pressures. The authors review the basic question of the influence of particle size on catalytic behavior of metal particles which involves questions of the basic sciences as much as practical considerations of catalyst design and use. They discuss preparatory techniques, analytical technology, and methods of characterization of these materials

Thermodynamic constrains for life based on non-aqueous polar solvents on free-floating planets.

Science.gov (United States)

Badescu, Viorel

2011-02-01

Free-floating planets (FFPs) might originate either around a star or in solitary fashion. These bodies can retain molecular gases atmospheres which, upon cooling, have basal pressures of tens of bars or more. Pressure-induced opacity of these gases prevents such a body from eliminating its internal radioactive heat and its surface temperature can exceed for a long term the melting temperature of a life-supporting solvent. In this paper two non-aqueous but still polar solvents are considered: hydrogen sulfide and ammonia. Thermodynamic requirements to be fulfilled by a hypothetic gas constituent of a life-supporting FFP's atmosphere are studied. The three gases analyzed here (nitrogen, methane and ethane) are candidates. We show that bodies with ammonia oceans are possible in interstellar space. This may happen on FFPs of (significantly) smaller or larger mass than the Earth. Generally, in case of FFP smaller in size than the Earth, the atmosphere exhibits a convective layer near the surface and a radiative layer at higher altitudes while the atmosphere of FFPs larger in size than Earth does not exhibit a convective layer. The atmosphere mass of a life-hosting FFP of Earth size is two or three orders of magnitude larger than the mass of Earth atmosphere. For FFPs larger than the Earth and specific values of surface pressure and temperature, there are conditions for condensation (in the ethane atmosphere). Some arguments induce the conclusion than the associated surface pressures and temperatures should be treated with caution as appropriate life conditions.

Theoretical Study on the Extraction of Alkaline Earth Salts by 18-Crown-6: Roles of Counterions, Solvent Types and Extraction Temperatures

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Saprizal Hadisaputra

2014-07-01

Full Text Available The roles of counterions, solvent types and extraction temperatures on the selectivity of 18-crown-6 (L toward alkaline earth salts MX2 (M = Ca, Sr, Ba; X = Cl-, NO3- have been studied by density functional method at B3LYP level of theory in gas and solvent phase. In gas phase, the chloride anion Cl- is the preference counterion than nitrate anion NO3-. This result is confirmed by the interaction energies, the second order interaction energies, charge transfers, energy difference between HOMO-LUMO and electrostatic potential maps. The presence of solvent reversed the gas phase trend. It is found that NO3- is the preference counterion in solvent phase. The calculated free energies demonstrate that the solvent types strongly change the strength of the complex formation. The free energies are exothermic in polar solvent while for the non polar solvent the free energies are endothermic. As the temperature changes the free energies also vary where the higher the temperatures the lower the free energy values. The calculated free energies are correlated well with the experimental stability constants. This theoretical study would have a strong contribution in planning the experimental conditions in terms of the preference counterions, solvent types and optimum extraction temperatures.

Effect of the Solvent Temperatures on Dynamics of Serine Protease Proteinase K

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Peng Sang

2016-02-01

Full Text Available To obtain detailed information about the effect of the solvent temperatures on protein dynamics, multiple long molecular dynamics (MD simulations of serine protease proteinase K with the solute and solvent coupled to different temperatures (either 300 or 180 K have been performed. Comparative analyses demonstrate that the internal flexibility and mobility of proteinase K are strongly dependent on the solvent temperatures but weakly on the protein temperatures. The constructed free energy landscapes (FELs at the high solvent temperatures exhibit a more rugged surface, broader spanning range, and higher minimum free energy level than do those at the low solvent temperatures. Comparison between the dynamic hydrogen bond (HB numbers reveals that the high solvent temperatures intensify the competitive HB interactions between water molecules and protein surface atoms, and this in turn exacerbates the competitive HB interactions between protein internal atoms, thus enhancing the conformational flexibility and facilitating the collective motions of the protein. A refined FEL model was proposed to explain the role of the solvent mobility in facilitating the cascade amplification of microscopic motions of atoms and atomic groups into the global collective motions of the protein.

FreeSASA: An open source C library for solvent accessible surface area calculations [version 1; referees: 2 approved

Directory of Open Access Journals (Sweden)

Simon Mitternacht

2016-02-01

Full Text Available Calculating solvent accessible surface areas (SASA is a run-of-the-mill calculation in structural biology. Although there are many programs available for this calculation, there are no free-standing, open-source tools designed for easy tool-chain integration. FreeSASA is an open source C library for SASA calculations that provides both command-line and Python interfaces in addition to its C API. The library implements both Lee and Richards’ and Shrake and Rupley’s approximations, and is highly configurable to allow the user to control molecular parameters, accuracy and output granularity. It only depends on standard C libraries and should therefore be easy to compile and install on any platform. The library is well-documented, stable and efficient. The command-line interface can easily replace closed source legacy programs, with comparable or better accuracy and speed, and with some added functionality.

Using Pd-salen complex as an efficient catalyst for the copper- and solvent-free coupling of acyl chlorides with terminal alkynes under aerobic conditions

Institute of Scientific and Technical Information of China (English)

Mohammad

2010-01-01

The palladium-salen complex palladium(Ⅱ) N,N'-bis{[5-(triphenylphosphonium)-methyl]salicylidene}-l,2-ethanediamine chloride was found to be a highly active catalyst for the copper- and solvent-free coupling reaction of terminal alkynes with different acyl chlorides in the presence of triethylamine as base, giving excellent ynones under aerobic conditions.

Preface: Catalysis Today

DEFF Research Database (Denmark)

Li, Yongdan

2016-01-01

This special issue of Catalysis Today with the theme “Sustain-able Energy” results from a great success of the session “Catalytic Technologies Accelerating the Establishment of Sustainable and Clean Energy”, one of the two sessions of the 1st International Symposium on Catalytic Science and Techn...

From furfural to fuel: synthesis of furoins by organocatalysis and their hydrodeoxygenation by cascade catalysis.

Science.gov (United States)

Wegenhart, Benjamin L; Yang, Linan; Kwan, Soon Cheong; Harris, Remi; Kenttämaa, Hilkka I; Abu-Omar, Mahdi M

2014-09-01

The synthesis of furoins from biomass-derived furfural and 2-methylfurfural is demonstrated in high yields in green and renewable solvents using N-heterocyclic carbene organocatalysts. The resulting furoin molecules are used as precursors for fuels using cascade catalysis, first by using Pd/C with acidic co-catalysts under very mild conditions to yield oxygenated C12 molecules. Two main products were formed, which we identified as 1,2-bis(5-methyltetrahydrofuran-2-yl)ethane and 1-(5-methyltetrahydrofuran-2-yl)heptanol. The use of a Pd/Zeolite-β catalyst under more extreme conditions resulted in the complete hydrodeoxygenation of 5,5'-dimethylfuroin to dodecanes in high yields (76%) and exceptional selectivity (94%) for n-dodecane. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Regio- and Stereoselective Diels-Alder Cycloadditions via Two-Step and Multicomponent Reactions Promoted by Infrared Irradiation under Solvent-Free Conditions

Science.gov (United States)

Flores-Conde, Maria Ines; Reyes, Leonor; Herrera, Rafael; Rios, Hulme; Vazquez, Miguel A.; Miranda, Rene; Tamariz, Joaquin; Delgado, Francisco

2012-01-01

Infrared irradiation promoted the Diels-Alder cycloadditions of exo-2-oxazolidinone dienes 1–3 with the Knoevenagel adducts 4–6, as dienophiles, leading to the synthesis of new 3,5-diphenyltetrahydrobenzo[d]oxazol-2-one derivatives (7, 9, 11 and 13–17), under solvent-free conditions. These cycloadditions were performed with good regio- and stereoselectivity, favoring the para-endo cycloadducts. We also evaluated the one-pot three-component reaction of active methylene compounds 20, benzaldehydes 21 and exo-2-oxazolidinone diene 2 under the same reaction conditions. A cascade Knoevenagel condensation/Diels-Alder cycloaddition reaction was observed, resulting in the final adducts 13–16 in similar yields. These procedures are environmentally benign, because no solvent and no catalyst were employed in these processes. The regioselectivity of these reactions was rationalized by Frontier Molecular Orbital (FMO) calculations. PMID:22489113

Highly Regio- and Stereoselective Diels-Alder Cycloadditions via Two-Step and Multicomponent Reactions Promoted by Infrared Irradiation under Solvent-Free Conditions

Directory of Open Access Journals (Sweden)

Francisco Delgado

2012-02-01

Full Text Available Infrared irradiation promoted the Diels-Alder cycloadditions of exo-2-oxazolidinone dienes 1–3 with the Knoevenagel adducts 4–6, as dienophiles, leading to the synthesis of new 3,5-diphenyltetrahydrobenzo[d]oxazol-2-one derivatives (7, 9, 11 and 13–17, under solvent-free conditions. These cycloadditions were performed with good regio- and stereoselectivity, favoring the para-endo cycloadducts. We also evaluated the one-pot three-component reaction of active methylene compounds 20, benzaldehydes 21 and exo-2-oxazolidinone diene 2 under the same reaction conditions. A cascade Knoevenagel condensation/Diels-Alder cycloaddition reaction was observed, resulting in the final adducts 13–16 in similar yields. These procedures are environmentally benign, because no solvent and no catalyst were employed in these processes. The regioselectivity of these reactions was rationalized by Frontier Molecular Orbital (FMO calculations.

Vinylimidazole-Based Asymmetric Ion Pair Comonomers: Synthesis, Polymerization Studies and Formation of Ionically Crosslinked PMMA

NARCIS (Netherlands)

Jana, S.; Vasantha, V.A.; Stubbs, L.P.; Parthiban, A.; Vancso, Gyula J.

2013-01-01

Vinylimidazole-based asymmetric ion pair comonomers (IPCs) which are free from nonpolymerizable counter ions have been synthesized, characterized and polymerized by free radical polymerization (FRP), atom transfer radical polymerization (ATRP), and reversible addition-fragmentation chain transfer

Novel asymmetrical pyrene derivatives as light emitting materials: Synthesis and photophysics

International Nuclear Information System (INIS)

Li Yang; Wang Dong; Wang Lei; Li Zhengqiang; Cui Qing; Zhang Haiquan; Yang Huai

2012-01-01

A series of novel substituted pyrene derivatives with asymmetrical groups have been successfully synthesized in excellent yield. Structures of the asymmetrical compound were fully characterized by 1 H-NMR, IR spectroscopy and mass spectrometry. By introducing ethynyl functions to pyrene, we obtained highly efficient blue and green light emitting materials. It has been demonstrated that the emission characteristics of pyrene derivatives have been bathochromatically tuned in the visible region by extending the π-conjugation. The photophysical properties of these compounds were carefully examined in different organic solvents and different concentrations. The electrochemical properties and geometrical electronic structures of the new pyrene derivatives have been investigated by cyclic voltammograms and density functional theory (DFT) calculations. - Highlights: ► It is the first research about asymmetrial pyrene derivatives as highly efficient light emitting materials. ► The solvatochromism and concentration effect of the new compounds have been discussed. ► Furthermore, the electrochemical properties and geometrical electronic structures were also investigated in this paper.

Dedicated Beamline Facilities for Catalytic Research. Synchrotron Catalysis Consortium (SCC)

Energy Technology Data Exchange (ETDEWEB)

Chen, Jingguang [Columbia Univ., New York, NY; Frenkel, Anatoly [Yeshiva Univ., New York, NY (United States); Rodriguez, Jose [Brookhaven National Lab. (BNL), Upton, NY (United States); Adzic, Radoslav [Brookhaven National Lab. (BNL), Upton, NY (United States); Bare, Simon R. [UOP LLC, Des Plaines, IL (United States); Hulbert, Steve L. [Brookhaven National Lab. (BNL), Upton, NY (United States); Karim, Ayman [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Mullins, David R. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Overbury, Steve [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2015-03-04

Synchrotron spectroscopies offer unique advantages over conventional techniques, including higher detection sensitivity and molecular specificity, faster detection rate, and more in-depth information regarding the structural, electronic and catalytic properties under in-situ reaction conditions. Despite these advantages, synchrotron techniques are often underutilized or unexplored by the catalysis community due to various perceived and real barriers, which will be addressed in the current proposal. Since its establishment in 2005, the Synchrotron Catalysis Consortium (SCC) has coordinated significant efforts to promote the utilization of cutting-edge catalytic research under in-situ conditions. The purpose of the current renewal proposal is aimed to provide assistance, and to develop new sciences/techniques, for the catalysis community through the following concerted efforts: Coordinating the implementation of a suite of beamlines for catalysis studies at the new NSLS-II synchrotron source; Providing assistance and coordination for catalysis users at an SSRL catalysis beamline during the initial period of NSLS to NSLS II transition; Designing in-situ reactors for a variety of catalytic and electrocatalytic studies; Assisting experimental set-up and data analysis by a dedicated research scientist; Offering training courses and help sessions by the PIs and co-PIs.

Positron studies in catalysis research

International Nuclear Information System (INIS)

1994-01-01

During the past eight months, the authors have made progress in several areas relevant to the eventual use of positron techniques in catalysis research. They have come closer to the completion of their positron microscope, and at the same time have performed several studies in their non-microscopic positron spectrometer which should ultimately be applicable to catalysis. The current status of the efforts in each of these areas is summarized in the following sections: Construction of the positron microscope (optical element construction, data collection software, and electronic sub-assemblies); Doppler broadening spectroscopy of metal silicide; Positron lifetime spectroscopy of glassy polymers; and Positron lifetime measurements of pore-sizes in zeolites

Facile and solvent-free routes for the synthesis of size-controllable Fe3O4 nanoparticles

International Nuclear Information System (INIS)

Ngo, Thanh Hieu; Tran, Dai Lam; Do, Hung Manh; Le, Van Hong; Nguyen, Xuan Phuc; Tran, Vinh Hoang

2010-01-01

Magnetite nanoparticles are one of the most important materials that are widely used in both medically diagnostic and therapeutic research. In this paper, we present some facile and non-toxic synthetic approaches for size-controllable preparations of magnetite nanoparticles, which are appropriate for biomedical applications, namely (i) co-precipitation; (ii) reduction–precipitation and (iii) oxidation–precipitation. Magnetic characterizations of the obtained nanoparticles have been studied and discussed. The oxidation precipitation route was chosen for investigation of the dependence of kinetic driven activation energy and that of coercive force on particle size (and temperature) during the course of the reaction. The structural–magnetic behavior was also correlated. Being solvent and surfactant-free, these methods are advantageous for synthesis and further functionalization towards biomedical applications

Sustainable green catalysis by supported metal nanoparticles.

Science.gov (United States)

Fukuoka, Atsushi; Dhepe, Paresh L

2009-01-01

The recent progress of sustainable green catalysis by supported metal nanoparticles is described. The template synthesis of metal nanoparticles in ordered porous materials is studied for the rational design of heterogeneous catalysts capable of high activity and selectivity. The application of these materials in green catalytic processes results in a unique activity and selectivity arising from the concerted effect of metal nanoparticles and supports. The high catalytic performances of Pt nanoparticles in mesoporous silica is reported. Supported metal catalysts have also been applied to biomass conversion by heterogeneous catalysis. Additionally, the degradation of cellulose by supported metal catalysts, in which bifunctional catalysis of acid and metal plays the key role for the hydrolysis and reduction of cellulose, is also reported. Copyright 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

Wet SiO2 As a Suitable Media for Fast and Efficient Reduction of Carbonyl Compounds with NaBH3CN under Solvent-Free and Acid-Free Conditions

International Nuclear Information System (INIS)

Kouhkan, Mehri; Zeynizadeh, Behzad

2010-01-01

Reduction of carbonyl compounds such as aldehydes, ketones, α,β-unsaturated enals and enones, α-diketones and acyloins was carried out readily with NaBH 3 CN in the presence of wet SiO 2 as a neutral media. The reactions were performed at solvent-free conditions in oil bath (70 - 80 .deg. C) or under microwave irradiation (240 W) to give the product alcohols in high to excellent yields. Regioselective 1,2-reduction of conjugated carbonyl compounds took place in a perfect selectivity without any side product formation

The local phase transitions of the solvent in the neighborhood of a solvophobic polymer at high pressures

Energy Technology Data Exchange (ETDEWEB)

Budkov, Yu. A., E-mail: urabudkov@rambler.ru [G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Ivanovo (Russian Federation); National Research University Higher School of Economics, Moscow (Russian Federation); Department of Chemistry, Lomonosov Moscow State University, Moscow (Russian Federation); Vyalov, I. I. [Istituto Italiano di Tecnologia, via Morego 30, Genova 16163 (Italy); Kolesnikov, A. L. [Ivanovo State University, Ivanovo (Russian Federation); Institut für Nichtklassische Chemie e.V., Universitat Leipzig, Leipzig (Germany); Georgi, N., E-mail: bancocker@mail.ru [Max Planck Institute for Mathematics in the Sciences, Leipzig (Germany); Chuev, G. N. [Max Planck Institute for the Physics of Complex Systems, Dresden (Germany); Institute of Theoretical and Experimental Biophysics, Russian Academy of Science, Pushchino, Moscow Region (Russian Federation); Kiselev, M. G. [G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Ivanovo (Russian Federation); Department of Chemistry, Lomonosov Moscow State University, Moscow (Russian Federation)

2014-11-28

We investigate local phase transitions of the solvent in the neighborhood of a solvophobic polymer chain which is induced by a change of the polymer-solvent repulsion and the solvent pressure in the bulk solution. We describe the polymer in solution by the Edwards model, where the conditional partition function of the polymer chain at a fixed radius of gyration is described by a mean-field theory. The contributions of the polymer-solvent and the solvent-solvent interactions to the total free energy are described within the mean-field approximation. We obtain the total free energy of the solution as a function of the radius of gyration and the average solvent number density within the gyration volume. The resulting system of coupled equations is solved varying the polymer-solvent repulsion strength at high solvent pressure in the bulk. We show that the coil-globule (globule-coil) transition occurs accompanied by a local solvent evaporation (condensation) within the gyration volume.

New and future developments in catalysis catalysis for remediation and environmental concerns

CERN Document Server

Suib, Steven L

2013-01-01

New and Future Developments in Catalysis is a package of seven books that compile the latest ideas concerning alternate and renewable energy sources and the role that catalysis plays in converting new renewable feedstock into biofuels and biochemicals. Both homogeneous and heterogeneous catalysts and catalytic processes will be discussed in a unified and comprehensive approach. There will be extensive cross-referencing within all volumes. The various sources of environmental pollution are the theme of this volume. The volume lists all current environmentally friendly catalytic chemical processes used for environmental remediation and critically compares their economic viability. Offers in-depth coverage of all catalytic topics of current interest and outlines future challenges and research areas A clear and visual description of all parameters and conditions, enabling the reader to draw conclusions for a particular case Outlines the catalytic processes applicable to energy generation and design of green proce...

A molecular view of heterogeneous catalysis

DEFF Research Database (Denmark)

Christensen, Claus H.; Nørskov, Jens Kehlet

2008-01-01

The establishment of a molecular view of heterogeneous catalysis has been hampered for a number of reasons. There are, however, recent developments, which show that we are now on the way towards reaching a molecular-scale picture of the way solids work as catalysts. By a combination of new...... by enabling a rational design of new catalysts. We illustrate this important development in heterogeneous catalysis by highlighting recent examples of catalyst systems for which it has been possible to achieve such a detailed understanding. In particular, we emphasize examples where this progress has made...

Density functional theory studies of transition metal nanoparticles in catalysis

DEFF Research Database (Denmark)

Greeley, Jeffrey Philip; Rankin, Rees; Zeng, Zhenhua

2013-01-01

Periodic Density Functional Theory calculations are capable of providing powerful insights into the structural, energetics, and electronic phenomena that underlie heterogeneous catalysis on transition metal nanoparticles. Such calculations are now routinely applied to single crystal metal surfaces...... and to subnanometer metal clusters. Descriptions of catalysis on truly nanosized structures, however, are generally not as well developed. In this talk, I will illustrate different approaches to analyzing nanocatalytic phenomena with DFT calculations. I will describe case studies from heterogeneous catalysis...... and electrocatalysis, in which single crystal models are combined with Wulff construction-based ideas to produce descriptions of average nanocatalyst behavior. Then, I will proceed to describe explicitly DFT-based descriptions of catalysis on truly nanosized particles (

Fast and efficient method for reduction of carbonyl compounds with NaBH4 /wet SiO2 under solvent free condition

International Nuclear Information System (INIS)

Zeynizadeh, Behzad; Bahyar, Tarifeh

2005-01-01

Reduction of structurally different carbonyl compounds such as aldehydes, ketones, α,β-unsaturated enals and enones, α-diketones and acyloins were accomplished efficiently by sodium borohydride in the presence of wet SiO 2 (30% m/m) under solvent free condition. The reactions were performed at room temperature or 75-80 deg C with high to excellent yields of the corresponding products. The chemoselective reduction of aldehydes over ketones was achieved successfully with this reducing system. (author)

ELECTROCHEMICAL BEHAVIOUR OF METHYLENE BLUE IN NON-AQUEOUS SOLVENTS

International Nuclear Information System (INIS)

Caram, J.A.; Suárez, J.F. Martínez; Gennaro, A.M.; Mirífico, M.V.

2015-01-01

Graphical abstract: Display Omitted - Highlights: • The dye is electro-reduced in two separated monoelectronic charge transfers. • Solvent/supporting electrolyte/acid/base modifies the electrochemical parameters. • A dissociation equilibrium of the dye in non-aqueous solvent is proposed. • The electro-generated and stable dye-radical is also chemically produced in EDA or KOH/DMF. • A new species is reversibly formed in KOH/EtOH or ACN. - Abstract: The electrochemical behaviour of methylene blue in solution of non-aqueous solvents with different supporting electrolytes was studied by cyclic voltammetry. Dye electro-reduction presents two well-defined processes of monoelectronic charge transfer yielding a free radical in the first process and an anion in the second electron transfer. Free radical and anion are long living species in some of the studied media. Effects of supporting electrolyte and solvent on the peak potentials, the peak current functions and the reversibility of the charge transfer processes are reported. A dissociation equilibrium of the dye in solution of non-aqueous solvents and the acid or base added determine markedly the electrochemical responses. In the particular cases of KOH/DMF or EDA basic media the chemical formation of the stable methylene blue radical was detected and it was characterized by EPR spectroscopy. A general reaction scheme is proposed

Combination of sunlight irradiated oxidative processes for landfill leachate: heterogeneous catalysis (TiO2 versus homogeneous catalysis (H2O2

Directory of Open Access Journals (Sweden)

Oswaldo Luiz Cobra Guimarães

2013-04-01

Full Text Available The objective of this work was to study the treatment of landfill leachate liquid in nature, after the use of a combination of advanced oxidation processes. More specifically, it compared heterogeneous catalysis with TiO2 to homogeneous catalysis with H2O2, both under photo-irradiated sunlight. The liquid used for the study was the leachate from the landfill of the city of Cachoeira Paulista, São Paulo State, Brazil. The experiments were conducted in a semi-batch reactor open to the absorption of solar UV radiation, with 120 min reaction time. The factors and their respective levels (-1, 0 and 1 were distributed in a experimental design 24-1 with duplicate and triplicate in the central point, resulting in an array with 19 treatment trials. The studied factors in comparing the two catalytic processes were: liquid leachate dilution, TiO2 concentration on the reactor plate, the H2O2 amount and pH level. The leachate had low photo-catalytic degradability, with NOPC reductions ranging from 1% to a maximum of 24.9%. When considering each factor alone, neither homogeneous catalysis with H2O2, nor heterogeneous catalysis with TiO2, could degrade the percolated liquid without significant reductions (5% level in total NOPC. On the other hand, the combined use of homogenous catalysis with H2O2 and heterogeneous catalysis H2O2 resulted in the greatest reductions in NOPC. The optimum condition for the NOPC reduction was obtained at pH 7, dilution of percolated:water at 1:1 (v v-1 rate; excess of 12.5% H2O2 and coating plate reactor with 0.025 g cm-2 TiO2.

SOLVENT FREE OXIDATION OF ALCOHOLS USING IRON (III) NITRATE NONAHYDRATE

Science.gov (United States)

Oxidation of alcohols have been conducted with metal nitrate reagents on various mineral supports such as clay, silica and zeolite etc. To circumvent the limitations of these supported reagents namely their preparation using solvents and short shelf-life, we explored the use of i...

Solvent refining of low-temperature tar with liquid ammonia

Energy Technology Data Exchange (ETDEWEB)

Ishida, K

1953-01-01

The middle fractions of low-temperature tar were treated with mixed solutions of H/sub 2/O and liquid NH/sub 3/ at 0/sup 0/ and 20/sup 0/, and with liquid NH/sub 3/ at -10, 0, + 10, and 20/sup 0/, and phase equilibrium between tar acids, neutral oil, and solvents were studied. The distribution ratio ranged from less than 1 to greater than 1 when the solvent contained about 20 percent (by weight) H/sub 2/O. When the solvent contained less than 85 percent (by weight) NH/sub 3/, the yield of extract was small but the purity of phenols in the extracted oil was above 90 percent. Solvent containing about 85 percent NH/sub 3/ (by weight) is considered optimum for separating tar acids from oils. A novel definition is proposed for solvent selectivity as the difference between the concentration of the solute in the extract layer, on a solvent-free basis, and the concentration in the raffinate layer.

Nonequilibrium dissipation-free transport in F₁-ATPase and the thermodynamic role of asymmetric allosterism.

Science.gov (United States)

Kawaguchi, Kyogo; Sasa, Shin-Ichi; Sagawa, Takahiro

2014-06-03

F1-ATPase (or F1), the highly efficient and reversible biochemical engine, has motivated physicists as well as biologists to imagine the design principles governing machines in the fluctuating world. Recent experiments have clarified yet another interesting property of F1; the dissipative heat inside the motor is very small, irrespective of the velocity of rotation and energy transport. Conceptual interest is devoted to the fact that the amount of internal dissipation is not simply determined by the sequence of equilibrium pictures, but also relies on the rotational-angular dependence of nucleotide affinity, which is a truly nonequilibrium aspect. We propose that the totally asymmetric allosteric model (TASAM), where adenosine triphosphate (ATP) binding to F1 is assumed to have low dependence on the angle of the rotating shaft, produces results that are most consistent with the experiments. Theoretical analysis proves the crucial role of two time scales in the model, which explains the universal mechanism to produce the internal dissipation-free feature. The model reproduces the characteristic torque dependence of the rotational velocity of F1 and predicts that the internal dissipation upon the ATP synthesis direction rotation becomes large at the low nucleotide condition. Copyright © 2014 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Disentangled solid state and metastable polymer melt; a solvent free route to high-modulus high-strength tapes and films of UHMWPE

Science.gov (United States)

Rastogi, Sanjay

2013-03-01

Ultra High Molecular Weight Polyethylene (UHMWPE) having average molar mass greater than a million g/mol is an engineering polymer. Due to its light-weight, high abrasion resistance and biocompatibility it is used for demanding applications such as body armour, prostheses etc. At present, because of its high melt viscosity to achieve the uniaxial/biaxial properties in the form of fibers/films the polymer is processed via solution route where nearly 95wt% of the solvent is used to process 5wt% of the polymer. In past several attempts have been made to process the polymer without using any solvent. However, compared to the solvent processing route the achieved mechanical properties were rather poor. Here we show that by controlled synthesis it is feasible to obtain UHMWPE that could be processed free of solvent to make uniaxial tapes and biaxial films, having unprecedented mechanical properties, exceeding that of the solution spun fibers. We address some of the fundamental aspects of chemistry, physics, rheology and processing for the development of desired morphological features to achieve the ultimate mechanical properties in tapes and films. The paper will also address the metastable melt state obtained on melting of the disentangled crystals and its implication on rheology in linear and nonlinear viscoelastic region. Solid state NMR studies will be applied to establish disentangled state in solid state to the polymerisation conditions. References: Macromolecules 2011, 44(14), 5558-5568; Nature Materials 2005, 4, 635-641; Phys Rev Lett 2006, 96(21), 218303-218205. The authors acknowledge financial support by the Dutch Polymer Institute.

Effect of Organic Solvent on the Characteristics of Free and Immobilized Inulinase from Kluyveromyces marxianus ATCC 16045

Directory of Open Access Journals (Sweden)

Fernanda V. A. Risso

2010-01-01

Full Text Available The aim of this work is to evaluate the effects of the butyl acetate concentration on the characteristics of free and immobilized inulinase from Kluyveromyces marxianus ATCC 16045. The mass fractions of organic solvent (OS in sodium acetate buffer (0.1 M were studied in the range from 25 to 70 %. The characteristics of both free and immobilized enzymes were not significantly affected by the OS mass fraction. The optimal temperature for the free enzyme was 55 °C at all OS mass fractions studied, whereas for the immobilized enzyme the optimum was 55 °C at 70 % of butyl acetate, and in the range from 50 to 60 °C at 25 and 50 % of OS. The optimum pH values, at all OS mass fractions, were 4.8 and 4.4 for the free and immobilized enzymes, respectively. The immobilized enzyme showed more stability at 50 °C and pH=4.8 for the whole range of OS mass fractions, since its stability was improved about 3 times. The kinetics parameters were calculated using Lineweaver-Burk plots. For the free enzyme, the vmax values were 12.5, 58.5 and 37.6 U/mL and the Km values 17.5, 280.7 and 210.4 mM at butyl acetate mass fractions of 25, 50 and 70 %, respectively. Similarly, for the immobilized enzyme, the vmax values were 38.9, 59.5 and 72.5 U/mL and the Km values 3.1, 5.4 and 14.0 mM at the same butyl acetate mass fractions, respectively.

Asymmetric photoelectron angular distributions from interfering photoionization processes

International Nuclear Information System (INIS)

Yin, Y.; Chen, C.; Elliott, D.S.; Smith, A.V.

1992-01-01

We have measured asymmetric photoelectron angular distributions for atomic rubidium. Ionization is induced by a one-photon interaction with 280 nm light and by a two-photon interaction with 560 nm light. Interference between the even- and odd-parity free-electron wave functions allows us to control the direction of maximum electron flux by varying the relative phase of the two laser fields

Synthesis of 1-amidoalkyl-2-naphthols based on a three-component reaction catalyzed by boric acid as a solid heterogeneous catalyst under solvent-free conditions

Directory of Open Access Journals (Sweden)

Zahed Karimi-Jaberi

2012-12-01

Full Text Available An efficient method for the preparation of 1-amidoalkyl-2-naphthols has been described using a multi-component, one-pot condensation reaction of 2-naphthol, aldehydes and amides in the presence of boric acid under solvent-free conditions.DOI: http://dx.doi.org/10.4314/bcse.v26i3.18

Seventh BES [Basic Energy Sciences] catalysis and surface chemistry research conference

International Nuclear Information System (INIS)

1990-03-01

Research programs on catalysis and surface chemistry are presented. A total of fifty-seven topics are included. Areas of research include heterogeneous catalysis; catalysis in hydrogenation, desulfurization, gasification, and redox reactions; studies of surface properties and surface active sites; catalyst supports; chemical activation, deactivation; selectivity, chemical preparation; molecular structure studies; sorption and dissociation. Individual projects are processed separately for the data bases

Seventh BES (Basic Energy Sciences) catalysis and surface chemistry research conference

Energy Technology Data Exchange (ETDEWEB)

1990-03-01

Research programs on catalysis and surface chemistry are presented. A total of fifty-seven topics are included. Areas of research include heterogeneous catalysis; catalysis in hydrogenation, desulfurization, gasification, and redox reactions; studies of surface properties and surface active sites; catalyst supports; chemical activation, deactivation; selectivity, chemical preparation; molecular structure studies; sorption and dissociation. Individual projects are processed separately for the data bases. (CBS)

Olive oil glycero lysis with the immobilized lipase Candida antarctica in a solvent free system

Energy Technology Data Exchange (ETDEWEB)

Singh, A. K.; Mukhopadhyay, M.

2012-11-01

In the present work, the solvent free lipase glycerolysis of olive oil for the production of monoglyceride (MG) and diglyceride (DG) with an immobilized Lipase B Candida antarctica was studied. The experiments were performed in batch mode by varying different process parameters. The Results showed that the MG and DG yields were dependent on operating conditions such as time, temperature, glycerol/ oil molar ratio, enzyme concentration and the water content in glycerol. The optimum operating time for maximum MG, 26 wt% and DG, 30 wt% production was 3h. The initial reaction rate was studied by varying different process parameters for 1h. The initial reaction rate increased at 30 degree centigrade temperature, 2:1 glycerol/oil molar ratio, 3.5% (w/w) water content in glycerol and 0.015g of enzyme loading. Comparative data for MG and DG yields for different oils and enzyme combinations were presented.

Asymmetric synthesis including enzymatic catalysis of 11C and 13N labelled amino acids

International Nuclear Information System (INIS)

Langstrom, B.; Antonio, G.; Bjurling, P.; Fasth, K.J.; Westerberg, G.; Watanabe, Y.

1993-01-01

Use of asymmetric synthesis in production of 11 C- and 13 N-labelled amino acids has been shown to be a useful approach in order to prepare amino acids routinely for PET-studies. Such PET-studies are focused either on problems related to amino acid transport, protein synthesis rate or the turnover of neurotransmitters from amino acids. The paper discusses matters regarding synthetic strategies and techniques involving production of precursors, labelled intermediates and main reaction sequences. In synthesis using the short-lived β + -emitters like 11 C and 13 N with T 1/2 of 20.3 and 10.0 min respectively, many special aspects have to be considered. The use of enzymes as catalysts has shown to be a useful tool in such preparations. The design of the labelled amino acids especially considering the stereochemistry, the position of the label will be addressed since these points are important both with regard to the application of the labelled amino acids as well as to the synthesis itself. In this presentation of the synthesis of labelled amino acids these various aspects are discussed

Asymmetric polivinylidenfluoride (PVDF) radiation grafted membranes: Preparation and performance in reverse osmosis application

International Nuclear Information System (INIS)

Vigo, F.; Capannelli, G.; Uliana, C.; Munari, S.

1981-01-01

A new type of reverse osmosis membrane has been synthesized. Membranes were prepared starting from asymmetric PVDF films, obtained by the casting and gelation technique and modified by radiochemical grafting and sulphonation. These membranes were tested in an RO laboratory plant and their performances were determined as a function of preparative parameters. The influences of evaporation time and temperature grafting and solvents were investigated. These membranes exhibit permeabilities as high as 2000 1/m 2 d and sodium chloride rejections up to 70%. (orig.)

Benchmarking Continuum Solvent Models for Keto-Enol Tautomerizations.

Science.gov (United States)

McCann, Billy W; McFarland, Stuart; Acevedo, Orlando

2015-08-13

Experimental free energies of tautomerization, ΔGT, were used to benchmark the gas-phase predictions of 17 different quantum mechanical methods and eight basis sets for seven keto-enol tautomer pairs dominated by their enolic form. The G4 method and M06/6-31+G(d,p) yielded the most accurate results, with mean absolute errors (MAE's) of 0.95 and 0.71 kcal/mol, respectively. Using these two theory levels, the solution-phase ΔGT values for 23 unique tautomer pairs composed of aliphatic ketones, β-dicarbonyls, and heterocycles were computed in multiple protic and aprotic solvents. The continuum solvation models, namely, polarizable continuum model (PCM), polarizable conductor calculation model (CPCM), and universal solvation model (SMD), gave relatively similar MAE's of ∼1.6-1.7 kcal/mol for G4 and ∼1.9-2.0 kcal/mol with M06/6-31+G(d,p). Partitioning the tautomer pairs into their respective molecular types, that is, aliphatic ketones, β-dicarbonyls, and heterocycles, and separating out the aqueous versus nonaqueous results finds G4/PCM utilizing the UA0 cavity to be the overall most accurate combination. Free energies of activation, ΔG(‡), for the base-catalyzed keto-enol interconversion of 2-nitrocyclohexanone were also computed using six bases and five solvents. The M06/6-31+G(d,p) reproduced the ΔG(‡) with MAE's of 1.5 and 1.8 kcal/mol using CPCM and SMD, respectively, for all combinations of base and solvent. That specific enolization was previously proposed to proceed via a concerted mechanism in less polar solvents but shift to a stepwise mechanism in more polar solvents. However, the current calculations suggest that the stepwise mechanism operates in all solvents.

Piper-betle-shaped nano-S-catalyzed synthesis of 1-amidoalkyl-2-naphthols under solvent-free reaction condition: a greener "nanoparticle-catalyzed organic synthesis enhancement" approach.

Science.gov (United States)

Das, Vijay K; Borah, Madhurjya; Thakur, Ashim J

2013-04-05

Nano-S prepared by an annealing process showed excellent catalytic activity for the synthesis of 1-amidoalkyl-2-naphthols under solvent-free reaction condition at 50 °C. The catalyst could be reused up to the fifth cycle without loss in its action. The green-ness of the present protocol was also measured using green metrics drawing its superiority.

Exploring Cooperative Effects in Oxidative NHC Catalysis: Regioselective Acylation of Carbohydrates.

Science.gov (United States)

Cramer, David L; Bera, Srikrishna; Studer, Armido

2016-05-23

The utility of oxidative NHC catalysis for both the regioselective and chemoselective functionalization of carbohydrates is explored. Chiral NHCs allow for the highly regioselective oxidative esterification of various carbohydrates using aldehydes as acylation precursors. The transformation was also shown to be amenable to both cis/trans diol isomers, free amino groups, and selective for specific sugar epimers in competition experiments. Efficiency and regioselectivity of the acylation can be improved upon using two different NHC catalysts that act cooperatively. The potential of the method is documented by the regioselective acylation of an amino-linked neodisaccharide. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new face of phenalenyl-based radicals in the transition metal-free C-H arylation of heteroarenes at room temperature: trapping the radical initiator via C-C σ-bond formation.

Science.gov (United States)

Ahmed, Jasimuddin; P, Sreejyothi; Vijaykumar, Gonela; Jose, Anex; Raj, Manthan; Mandal, Swadhin K

2017-11-01

The radical-mediated transition metal-free approach for the direct C-H bond functionalization of arenes is considered as a cost effective alternative to transition metal-based catalysis. An organic ligand-based radical plays a key role by generating an aryl radical which undergoes a subsequent functionalization process. The design principle of the present study takes advantage of a relatively stable odd alternant hydrocarbon-based phenalenyl (PLY) radical. In this study, the first transition metal-free catalyzed direct C-H arylation of a variety of heteroarenes such as azoles, furan, thiophene and pyridine at room temperature has been reported using a phenalenyl-based radical without employing any photoactivation step. This protocol has been successfully applied to the gram scale synthesis of core moieties of bioactive molecules. The phenalenyl-based radical initiator has been characterized crystallographically by trapping it via the formation of a C-C σ-bond between the phenalenyl radical and solvent-based radical species.

Exploiting nanospace for asymmetric catalysis: confinement of immobilized, single-site chiral catalysts enhances enantioselectivity.

Science.gov (United States)

Thomas, John Meurig; Raja, Robert

2008-06-01

In the mid-1990s, it became possible to prepare high-area silicas having pore diameters controllably adjustable in the range ca. 20-200 Å. Moreover, the inner walls of these nanoporous solids could be functionalized to yield single-site, chiral, catalytically active organometallic centers, the precise structures of which could be determined using in situ X-ray absorption and FTIR and multinuclear magic angle spinning (MAS) NMR spectroscopy. This approach opened up the prospect of performing heterogeneous enantioselective conversions in a novel manner, under the spatial restrictions imposed by the nanocavities within which the reactions occur. In particular, it suggested an alternative method for preparing pharmaceutically and agrochemically useful asymmetric products by capitalizing on the notion, initially tentatively perceived, that spatial confinement of prochiral reactants (and transition states formed at the chiral active center) would provide an altogether new method of boosting the enantioselectivity of the anchored chiral catalyst. Initially, we anchored chiral single-site heterogeneous catalysts to nanopores covalently via a ligand attached to Pd(II) or Rh(I) centers. Later, we employed a more convenient and cheaper electrostatic method, relying in part on strong hydrogen bonding. This Account provides many examples of these processes, encompassing hydrogenations, oxidations, and aminations. Of particular note is the facile synthesis from methyl benzoylformate of methyl mandelate, which is a precursor in the synthesis of pemoline, a stimulant of the central nervous system; our procedure offers several viable methods for reducing ketocarboxylic acids. In addition to relying on earlier (synchrotron-based) in situ techniques for characterizing catalysts, we have constructed experimental procedures involving robotically controlled catalytic reactors that allow the kinetics of conversion and enantioselectivity to be monitored continually, and we have access to

Solvent-free functionalization of silicone rubber and efficacy of PAAm brushes grafted from an amino-PPX layer against bacterial adhesion.

Science.gov (United States)

Fundeanu, Irina; Klee, Doris; Schouten, Arend J; Busscher, Henk J; van der Mei, Henny C

2010-11-01

Silicone rubber is a frequently employed biomaterial that is prone to bacterial adhesion and biofilm formation. In this study, the surface of silicone rubber was solvent-free functionalized by chemical vapor deposition (CVD) of poly(o-amino-p-xylylene-co-p-xylylene (amino-PPX). Subsequently, the amino groups of the amino-PPX layer were used to introduce the initiator from a vapor phase for atom transfer radical polymerization of acrylamide to form polyacrylamide (PAAm) brushes. The modification steps were verified by means of X-ray photoelectron spectroscopy and attenuated total reflection-Fourier transform infrared spectroscopy. Adhesion of Staphylococcus aureus ATCC 12600 and Escherichia coli 3.14 to an amino-PPX-PAAm brush coating in a parallel plate flow chamber was strongly reduced with respect to non-coated silicone rubber - by 93% and 99%, respectively. For E. coli 3.14, this reduction is larger than that obtained for solvent functionalization of γ-aminopropyltriethoxysilane-PAAm brushes due to the higher density of amino groups introduced by the CVD of amino-PPX. Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Calculation of liquid-liquid phase separation in a ternary system of a polymer in a mixture of a solvent and a nonsolvent

NARCIS (Netherlands)

Altena, Frank W.; Smolders, C.A.

1982-01-01

A numerical method for the calculation of the binodal of liquid-liquid phase separation in a ternary system is described. The Flory-Huggins theory for three-component systems is used. Binodals are calculated for polymer/solvent/nonsolvent systems which are used in the preparation of asymmetric

Effect of coagulant bath on the gas permeation properties of cellulose acetate asymmetric membrane

Science.gov (United States)

Mohamed, F.; Hasbullah, H.; Jami'an, W. N. R.; Salleh, W. N. H. W.; Ibrahim, N.; Ali, R. R.

2016-06-01

Membrane based gas separation process technology has been recognized as one of the most efficient and advanced unit operation for gas separation. One of the problems in membrane gas separation is membrane performance. This paper explores the application of cellulose acetate (CA) membrane for natural gas purification and separation by improving its permeability and selectivity. The main interest in this research is to study the effect of quench medium on the gas separation performance towards its physical characteristics and gas separation performance of CA membrane. Cellulose acetate polymer was dissolved in n- methyl-2-pyrrolidone solvent and casted onto a glass plate using a pneumatically controlled casting system with fixed shear rate and solvent evaporation times. The parameter varied was the non-solvent used as quench medium during membrane post treatment that were methanol and n-hexane. The different quench media as post treatment affected the O2 and N2 gas permeation and O2/N2 selectivity as well as the tensile strength of the flat sheet asymmetric membrane. Combination of methanol and n-hexane as quench media gave the best result than the other steps. This solvent exchange step influenced the morphology by producing thin skin layer and thus gives better gas separation performance than other steps

One Pot Synthesis of α-Aminophosphonates Containing Bromo and 3,4,5-Trimethoxybenzyl Groups under Solvent-free Conditions

Directory of Open Access Journals (Sweden)

Wei Xue

2007-02-01

Full Text Available New α-aminophosphonates were synthesized by the Kabachnik-Fields reactionof 3,4,5-trimethoxybenzaldehyde (TMB with p- or m-bromoaniline and a dialkylphosphite under solvent-free conditions. TMB was prepared from gallic acid via a fourstep synthetic sequence involving etherification, esterification, hydrazidation andpotassium ferricyanide oxidation. The structures of all synthesized compounds wereconfirmed by elemental analysis, IR, 1H-, 13C- and 31P-NMR spectral data. Compound 7gwas also characterized by X-ray crystallography. A half-leaf method was used todetermine the in vivo curative efficacy of the eight title products against tobacco mosaicvirus (TMV. It was found that compounds 7g and 7h possess good in vivo curativeeffects against TMV.

Wet SiO{sub 2} As a Suitable Media for Fast and Efficient Reduction of Carbonyl Compounds with NaBH{sub 3}CN under Solvent-Free and Acid-Free Conditions

Energy Technology Data Exchange (ETDEWEB)

Kouhkan, Mehri; Zeynizadeh, Behzad [Urmia University, Urmia (Iran, Islamic Republic of)

2010-10-15

Reduction of carbonyl compounds such as aldehydes, ketones, α,β-unsaturated enals and enones, α-diketones and acyloins was carried out readily with NaBH{sub 3}CN in the presence of wet SiO{sub 2} as a neutral media. The reactions were performed at solvent-free conditions in oil bath (70 - 80 .deg. C) or under microwave irradiation (240 W) to give the product alcohols in high to excellent yields. Regioselective 1,2-reduction of conjugated carbonyl compounds took place in a perfect selectivity without any side product formation.

Catalysis in electrochemistry: from fundamentals to strategies for fuel cell development

National Research Council Canada - National Science Library

Santos, Elizabeth; Schmickler, Wolfgang

2011-01-01

"Catalysis in Electrochemistry: From Fundamentals to Strategies for Fuel Cell Development is a modern, comprehensive reference work on catalysis in electrochemistry, including principles, methods, strategies, and applications...

Catalysis in the Primordial World

Directory of Open Access Journals (Sweden)

Nenad Raos

2017-11-01

Full Text Available Catalysis provides orderly prebiotic synthesis and eventually its evolution into autocatalytic (self-reproduction systems. Research on homogeneous catalysis is concerned mostly with random peptide synthesis and the chances to produce catalytic peptide oligomers. Synthesis of ribose via formose reaction was found to be catalysed by B(OH4−, presumably released by weathering of borate minerals. Oxide and clay mineral surfaces provide catalytic sites for the synthesis of oligopeptides and oligonucleotides. Chemoautotrophic or iron-sulphur-world theory assumes that the first (pioneer organisms developed by catalytic processes on (Fe/NiS particles formed near/close hydrothermal vents. The review provides an overlay of possible catalytic reactions in prebiotic environment, discussing their selectivity (regioselectivity, stereoselectivity as well as geological availability of catalytic minerals and geochemical conditions enabling catalytic reactions on early Earth.

Pollution Control by Catalysis

DEFF Research Database (Denmark)

Eriksen, Kim Michael; Fehrmann, Rasmus

1998-01-01

The report summarises the results of two years of collaboration supported by INTAS between Department of Chemistry,DTU,DK , IUSTI,Universite de Provence,FR, ICE/HT University 6of Patras,GR, and Boreskov Institute of Catalysis,RU.The project has been concerned with mechanistic studies of deNOx and...

Performance prediction of asymmetrical bladed H-Darrieus VAWT rotors in low wind speed condition using CFD

Science.gov (United States)

Mazarbhuiya, Hussain Mahamed Sahed Mostafa; Biswas, Agnimitra; Sharma, Kaushal Kumar

2018-04-01

Wind energy is an essential and carbon free form of renewable energy resources. Energy can be easily extracted from wind with the use of Horizontal axis and Vertical axis wind turbine(VAWT). The performance of turbine depends on airfoil shape. The present work emphasizes the aerodynamics of different asymmetrical airfoils used in VAWT rotors. This investigation is conducted for the selection of efficient asymmetrical bladed H-Darrieus VAWT rotor. Five numbers of thick and cambered asymmetrical airfoil is considered for this investigation. A free stream velocity of 6.0 m/s is considered to simulate 2D CFD analysis using k-ɛ turbulence model. The power coefficient (Cp) of all H-Darrieus VAWT rotor increase with increase in TSR value to a certain limit and after it starts decrease with further increase of TSR. In the present investigation the Cp and TSR of NACA 63415 (RT-30%) are found to be higher among all considered asymmetrical airfoils. Moreover, Ct values of NACA 63415 (RT-30%) are also high corresponding to all TSR values. This is due to the long duration of attachment of flow with blade surroundings. Hence, NACA 63415 (RT- 30%) airfoil may be considered as an efficient airfoil among S818, GOE 561, GU25-5(11)8, and KENNEDY AND MARSDEN (kenmar) asymmetrical airfoils.

The nature of the active site in heterogeneous metal catalysis

DEFF Research Database (Denmark)

Nørskov, Jens Kehlet; Bligaard, Thomas; Larsen, Britt Hvolbæk

2008-01-01

This tutorial review, of relevance for the surface science and heterogeneous catalysis communities, provides a molecular-level discussion of the nature of the active sites in metal catalysis. Fundamental concepts such as "Bronsted-Evans-Polanyi relations'' and "volcano curves'' are introduced...

Molecular-Level Design of Heterogeneous Chiral Catalysis

International Nuclear Information System (INIS)

Zaera, Francisco

2012-01-01

The following is a proposal to continue our multi-institutional research on heterogeneous chiral catalysis. Our team combines the use of surface-sensitive analytical techniques for the characterization of model systems with quantum and statistical mechanical calculations to interpret experimental data and guide the design of future research. Our investigation focuses on the interrelation among the three main mechanisms by which enantioselectivity can be bestowed to heterogeneous catalysts, namely: (1) by templating chirality via the adsorption of chiral supramolecular assemblies, (2) by using chiral modifiers capable of forming chiral complexes with the reactant and force enantioselective surface reactions, and (3) by forming naturally chiral surfaces using imprinting chiral agents. Individually, the members of our team are leaders in these various aspects of chiral catalysis, but the present program provides the vehicle to generate and exploit the synergies necessary to address the problem in a comprehensive manner. Our initial work has advanced the methodology needed for these studies, including an enantioselective titration procedure to identify surface chiral sites, infrared spectroscopy in situ at the interface between gases or liquids and solids to mimic realistic catalytic conditions, and DFT and Monte Carlo algorithms to simulate and understand chirality on surfaces. The next step, to be funded by the monies requested in this proposal, is to apply those methods to specific problems in chiral catalysis, including the identification of the requirements for the formation of supramolecular surface structures with enantioselective behavior, the search for better molecules to probe the chiral nature of the modified surfaces, the exploration of the transition from supramolecular to one-to-one chiral modification, the correlation of the adsorption characteristics of one-to-one chiral modifiers with their physical properties, in particular with their configuration

Molecular microenvironments: Solvent interactions with nucleic acid bases and ions

Science.gov (United States)

Macelroy, R. D.; Pohorille, A.

1986-01-01

The possibility of reconstructing plausible sequences of events in prebiotic molecular evolution is limited by the lack of fossil remains. However, with hindsight, one goal of molecular evolution was obvious: the development of molecular systems that became constituents of living systems. By understanding the interactions among molecules that are likely to have been present in the prebiotic environment, and that could have served as components in protobiotic molecular systems, plausible evolutionary sequences can be suggested. When stable aggregations of molecules form, a net decrease in free energy is observed in the system. Such changes occur when solvent molecules interact among themselves, as well as when they interact with organic species. A significant decrease in free energy, in systems of solvent and organic molecules, is due to entropy changes in the solvent. Entropy-driven interactioins played a major role in the organization of prebiotic systems, and understanding the energetics of them is essential to understanding molecular evolution.

Special section on Nano-Catalysis

CSIR Research Space (South Africa)

Makgwane, PR

2013-01-01

Full Text Available to achieve sustainable and green catalytic processes. The special issue contains 40 peer reviewed scientific papers that include four comprehensive review articles contributions from the invited experts in the respective catalysis fields....

Diverse modes of reproduction in the marine free-living ciliate Glauconema trihymene

Directory of Open Access Journals (Sweden)

Zufall Rebecca A

2010-04-01

Full Text Available Abstract Background Most free-living ciliates reproduce by equal fission or budding during vegetative growth. In certain ciliates, reproduction occurs inside the cyst wall, viz. reproductive cysts, but more complex reproductive strategies have generally been thought to be confined to parasitic or symbiotic species, e.g. Radiophrya spp. Results In addition to equal fission, asymmetric binary division and reproductive cysts were discovered in the free-living bacterivorous scuticociliate Glauconema trihymene Thompson, 1966. Asymmetric division is an innate physiological state that can be induced by sufficient food, and the higher the food concentration, the longer the asymmetric division persists. During asymmetric division, nuclear and somatic structures divide with transiently arrested cytokinesis and variable positioning of macronuclei. Phylogenetic analysis, based on the small subunit of ribosomal DNA (SSU rDNA sequences, showed that the G. trihymene isolate studied here nests with typical scuticociliates and is paraphyletic to both the symbiotic apostome and astome ciliates, some of which also produce progeny by asymmetric division. Conclusions The asymmetric division in G. trihymene has no precedent among undisturbed free-living ciliates. The coexistence of multiple modes of reproduction may represent a previously undescribed reproductive strategy for ciliates living on food patches in coastal waters. This may also be indicative of similar reproductive strategies among other polyphenic ciliates, which have not been intensively studied. Asymmetric division provides a special opportunity for studying ciliates' phenotypic plasticity and may also illuminate the origins of multicellularity.

Continuous Preparation of 1:1 Haloperidol-Maleic Acid Salt by a Novel Solvent-Free Method Using a Twin Screw Melt Extruder.

Science.gov (United States)

Lee, Hung Lin; Vasoya, Jaydip M; Cirqueira, Marilia de Lima; Yeh, Kuan Lin; Lee, Tu; Serajuddin, Abu T M

2017-04-03

Salts are generally prepared by acid-base reaction in relatively large volumes of organic solvents, followed by crystallization. In this study, the potential for preparing a pharmaceutical salt between haloperidol and maleic acid by a novel solvent-free method using a twin-screw melt extruder was investigated. The pH-solubility relationship between haloperidol and maleic acid in aqueous medium was first determined, which demonstrated that 1:1 salt formation between them was feasible (pH max 4.8; salt solubility 4.7 mg/mL). Extrusion of a 1:1 mixture of haloperidol and maleic acid at the extruder barrel temperature of 60 °C resulted in the formation of a highly crystalline salt. The effects of operating temperature and screw configuration on salt formation were also investigated, and those two were identified as key processing parameters. Salts were also prepared by solution crystallization from ethyl acetate, liquid-assisted grinding, and heat-assisted grinding and compared with those obtained by melt extrusion by using DSC, PXRD, TGA, and optical microscopy. While similar salts were obtained by all methods, both melt extrusion and solution crystallization yielded highly crystalline materials with identical enthalpies of melting. During the pH-solubility study, a salt hydrate form was also identified, which, upon heating, converted to anhydrate similar to that obtained by other methods. There were previous reports of the formation of cocrystals, but not salts, by melt extrusion. 1 H NMR and single-crystal X-ray diffraction confirmed that a salt was indeed formed in the present study. The haloperidol-maleic acid salt obtained was nonhygroscopic in the moisture sorption study and converted to the hydrate form only upon mixing with water. Thus, we are reporting for the first time a relatively simple and solvent-free twin-screw melt extrusion method for the preparation of a pharmaceutical salt that provides material comparable to that obtained by solution

Asymmetric block copolymer membranes with ultrahigh porosity and hierarchical pore structure by plain solvent evaporation

KAUST Repository

Yu, H.

2016-09-14

Membranes with a hierarchical porous structure could be manufactured from a block copolymer blend by pure solvent evaporation. Uniform pores in a 30 nm thin skin layer supported by a macroporous structure were formed. This new process is attractive for membrane production because of its simplicity and the lack of liquid waste.

Asymmetric block copolymer membranes with ultrahigh porosity and hierarchical pore structure by plain solvent evaporation

KAUST Repository

Yu, H.; Qiu, Xiaoyan; Behzad, Ali Reza; Musteata, Valentina-Elena; Smilgies, D.-M.; Nunes, Suzana Pereira; Peinemann, Klaus-Viktor

2016-01-01

Membranes with a hierarchical porous structure could be manufactured from a block copolymer blend by pure solvent evaporation. Uniform pores in a 30 nm thin skin layer supported by a macroporous structure were formed. This new process is attractive for membrane production because of its simplicity and the lack of liquid waste.

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

Science.gov (United States)

Bohnert, George W [Harrisonville, MO; Hand, Thomas E [Lee's Summit, MO; DeLaurentiis, Gary M [Jamestown, CA

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.

Hierarchical polypyrrole based composites for high performance asymmetric supercapacitors

Science.gov (United States)

Chen, Gao-Feng; Liu, Zhao-Qing; Lin, Jia-Ming; Li, Nan; Su, Yu-Zhi

2015-06-01

An advanced asymmetric supercapacitor with high energy density, exploiting hierarchical polypyrrole (PPy) based composites as both the anode [three dimensional (3D) chuzzle-like Ni@PPy@MnO2] and (3D cochleate-like Ni@MnO2@PPy) cathode, has been developed. The ultrathin PPy and flower-like MnO2 orderly coating on the high-conductivity 3D-Ni enhance charge storage while the unique 3D chuzzle-like and 3D cochleate-like structures provide storage chambers and fast ion transport pathways for benefiting the transport of electrolyte ions. The 3D cochleate-like Ni@MnO2@PPy possesses excellent pseudocapacitance with a relatively negative voltage window while preserved EDLC and free transmission channels conducive to hold the high power, providing an ideal cathode for the asymmetric supercapacitor. It is the first report of assembling hierarchical PPy based composites as both the anode and cathode for asymmetric supercapacitor, which exhibits wide operation voltage of 1.3-1.5 V with maximum energy and power densities of 59.8 Wh kg-1 and 7500 W kg-1.

Francois Garin: Pioneer work in catalysis through synchrotron radiation

International Nuclear Information System (INIS)

Bazin, Dominique

2014-01-01

Starting from the late seventies, the progressively increased availability of beamlines dedicated to X-ray absorption spectroscopy allowed the execution of experiments in chemistry. In this manuscript, I describe the contribution of Francois Garin at the frontier of heterogeneous catalysis and synchrotron radiation. Working at LURE as a scientific in charge of a beamline dedicated to X-ray absorption spectroscopy during almost twenty years and thus, having the opportunity to discuss with research groups working in heterogeneous catalysis in Europe as well as in the United States, it was quite easy to show that his work is clearly at the origin of current research in heterogeneous catalysis, not only in France, but in different synchrotron radiation centres. (authors)

Spectroscopy in catalysis : an introduction

NARCIS (Netherlands)

Niemantsverdriet, J.W.

2000-01-01

Spectroscopy in Catalysis describes the most important modern analytical techniques used to investigate catalytic surfaces. These include electron spectroscopy (XPS, UPS, AES, EELS), ion spectroscopy (SIMS, SNMS, RBS, LEIS), vibrational spectroscopy (infrared, Raman, EELS), temperature-programmed

Heterogeneous catalysis at nanoscale for energy applications

CERN Document Server

Tao, Franklin (Feng); Kamat, Prashant V

2015-01-01

This book presents both the fundamentals concepts and latest achievements of a field that is growing in importance since it represents a possible solution for global energy problems.  It focuses on an atomic-level understanding of heterogeneous catalysis involved in important energy conversion processes. It presents a concise picture for the entire area of heterogeneous catalysis with vision at the atomic- and nano- scales, from synthesis, ex-situ and in-situ characterization, catalytic activity and selectivity, to mechanistic understanding based on experimental exploration and theoretical si

Catalysis by nonmetals rules for catalyst selection

CERN Document Server

Krylov, Oleg V

1970-01-01

Catalysis by Non-metals: Rules of Catalyst Selection presents the development of scientific principles for the collection of catalysts. It discusses the investigation of the mechanism of chemosorption and catalysis. It addresses a series of properties of solid with catalytic activity. Some of the topics covered in the book are the properties of a solid and catalytic activity in oxidation-reduction reactions; the difference of electronegativities and the effective charges of atoms; the role of d-electrons in the catalytic properties of a solid; the color of solids; and proton-acid and proton-ba

“Flash” Solvent-free Synthesis of Triazoles Using a Supported Catalyst

Directory of Open Access Journals (Sweden)

Ibtissem Jlalia

2009-01-01

Full Text Available A solvent-free synthesis of 1,4-disubstituted-1,2,3-triazoles using neat azides and alkynes and a copper(I polymer supported catalyst (Amberlyst® A21•CuI is presented herein. As it provides the products in high yields and purities within minutes, this method thus being characterized as a "flash" synthesis, and was exemplified through the synthesis of a 24-compound library on a small scale.

Parameters affecting incorporation and by-product formation during the production of structured phospholipids by lipase-catalyzed acidolysis in solvent free system

DEFF Research Database (Denmark)

Vikbjerg, Anders Falk; Mu, Huiling; Xu, Xuebing

2005-01-01

By-product formation is a serious problem in the lipase-catalyzed acyl exchange of phospholipids (PL). By-products are formed due to parallel hydrolysis reactions and acyl migration in the reaction system. A clear elucidation of these side reactions is important for practical operation in order...... to minimize by-products during reaction. In the present study we examined the Lipozyme RM IM-catalyzed acidolysis for the production of structured phospholipids between phosphatidylcholine (PC) and caprylic acid in the solvent free system. A five-factor response surface design was used to evaluate...

Calculating the binding free energies of charged species based on explicit-solvent simulations employing lattice-sum methods: An accurate correction scheme for electrostatic finite-size effects

Energy Technology Data Exchange (ETDEWEB)

Rocklin, Gabriel J. [Department of Pharmaceutical Chemistry, University of California San Francisco, 1700 4th St., San Francisco, California 94143-2550, USA and Biophysics Graduate Program, University of California San Francisco, 1700 4th St., San Francisco, California 94143-2550 (United States); Mobley, David L. [Departments of Pharmaceutical Sciences and Chemistry, University of California Irvine, 147 Bison Modular, Building 515, Irvine, California 92697-0001, USA and Department of Chemistry, University of New Orleans, 2000 Lakeshore Drive, New Orleans, Louisiana 70148 (United States); Dill, Ken A. [Laufer Center for Physical and Quantitative Biology, 5252 Stony Brook University, Stony Brook, New York 11794-0001 (United States); Hünenberger, Philippe H., E-mail: phil@igc.phys.chem.ethz.ch [Laboratory of Physical Chemistry, Swiss Federal Institute of Technology, ETH, 8093 Zürich (Switzerland)

2013-11-14

-periodic PB calculations for a given system, its dependence on the box size being analytical. The latter scheme also provides insight into the physical origin of the finite-size effects. These two schemes also encompass a correction for discrete solvent effects that persists even in the limit of infinite box sizes. Application of either scheme essentially eliminates the size dependence of the corrected charging free energies (maximal deviation of 1.5 kJ mol{sup −1}). Because it is simple to apply, the analytical correction scheme offers a general solution to the problem of finite-size effects in free-energy calculations involving charged solutes, as encountered in calculations concerning, e.g., protein-ligand binding, biomolecular association, residue mutation, pK{sub a} and redox potential estimation, substrate transformation, solvation, and solvent-solvent partitioning.

Calculating the binding free energies of charged species based on explicit-solvent simulations employing lattice-sum methods: An accurate correction scheme for electrostatic finite-size effects

Science.gov (United States)

Rocklin, Gabriel J.; Mobley, David L.; Dill, Ken A.; Hünenberger, Philippe H.

2013-11-01

calculations for a given system, its dependence on the box size being analytical. The latter scheme also provides insight into the physical origin of the finite-size effects. These two schemes also encompass a correction for discrete solvent effects that persists even in the limit of infinite box sizes. Application of either scheme essentially eliminates the size dependence of the corrected charging free energies (maximal deviation of 1.5 kJ mol-1). Because it is simple to apply, the analytical correction scheme offers a general solution to the problem of finite-size effects in free-energy calculations involving charged solutes, as encountered in calculations concerning, e.g., protein-ligand binding, biomolecular association, residue mutation, pKa and redox potential estimation, substrate transformation, solvation, and solvent-solvent partitioning.

Calculating the binding free energies of charged species based on explicit-solvent simulations employing lattice-sum methods: an accurate correction scheme for electrostatic finite-size effects.

Science.gov (United States)

Rocklin, Gabriel J; Mobley, David L; Dill, Ken A; Hünenberger, Philippe H

2013-11-14

calculations for a given system, its dependence on the box size being analytical. The latter scheme also provides insight into the physical origin of the finite-size effects. These two schemes also encompass a correction for discrete solvent effects that persists even in the limit of infinite box sizes. Application of either scheme essentially eliminates the size dependence of the corrected charging free energies (maximal deviation of 1.5 kJ mol(-1)). Because it is simple to apply, the analytical correction scheme offers a general solution to the problem of finite-size effects in free-energy calculations involving charged solutes, as encountered in calculations concerning, e.g., protein-ligand binding, biomolecular association, residue mutation, pKa and redox potential estimation, substrate transformation, solvation, and solvent-solvent partitioning.

Cu and Cu-Based Nanoparticles: Synthesis and Applications in Catalysis.

Science.gov (United States)

Gawande, Manoj B; Goswami, Anandarup; Felpin, François-Xavier; Asefa, Tewodros; Huang, Xiaoxi; Silva, Rafael; Zou, Xiaoxin; Zboril, Radek; Varma, Rajender S

2016-03-23

The applications of copper (Cu) and Cu-based nanoparticles, which are based on the earth-abundant and inexpensive copper metal, have generated a great deal of interest in recent years, especially in the field of catalysis. The possible modification of the chemical and physical properties of these nanoparticles using different synthetic strategies and conditions and/or via postsynthetic chemical treatments has been largely responsible for the rapid growth of interest in these nanomaterials and their applications in catalysis. In addition, the design and development of novel support and/or multimetallic systems (e.g., alloys, etc.) has also made significant contributions to the field. In this comprehensive review, we report different synthetic approaches to Cu and Cu-based nanoparticles (metallic copper, copper oxides, and hybrid copper nanostructures) and copper nanoparticles immobilized into or supported on various support materials (SiO2, magnetic support materials, etc.), along with their applications in catalysis. The synthesis part discusses numerous preparative protocols for Cu and Cu-based nanoparticles, whereas the application sections describe their utility as catalysts, including electrocatalysis, photocatalysis, and gas-phase catalysis. We believe this critical appraisal will provide necessary background information to further advance the applications of Cu-based nanostructured materials in catalysis.

Approaches to single-nanoparticle catalysis.

Science.gov (United States)

Sambur, Justin B; Chen, Peng

2014-01-01

Nanoparticles are among the most important industrial catalysts, with applications ranging from chemical manufacturing to energy conversion and storage. Heterogeneity is a general feature among these nanoparticles, with their individual differences in size, shape, and surface sites leading to variable, particle-specific catalytic activity. Assessing the activity of individual nanoparticles, preferably with subparticle resolution, is thus desired and vital to the development of efficient catalysts. It is challenging to measure the activity of single-nanoparticle catalysts, however. Several experimental approaches have been developed to monitor catalysis on single nanoparticles, including electrochemical methods, single-molecule fluorescence microscopy, surface plasmon resonance spectroscopy, X-ray microscopy, and surface-enhanced Raman spectroscopy. This review focuses on these experimental approaches, the associated methods and strategies, and selected applications in studying single-nanoparticle catalysis with chemical selectivity, sensitivity, or subparticle spatial resolution.

Asymmetric diketopyrrolopyrrole conjugated polymers for field-effect transistors and polymer solar cells processed from a non-chlorinated solvent

NARCIS (Netherlands)

Ji, Y.; Xiao, C.; Wang, Q.; Zhang, J.; Li, C.; Wu, Y.; Wei, Z.; Zhan, X.; Hu, W.; Wang, Z.; Janssen, R.A.J.; Li, W.W.

2016-01-01

Newly designed asymmetric diketopyrrolopyrrole conjugated polymers with two different aromatic substituents possess a hole mobility of 12.5 cm2 V−1 s−1 in field-effect transistors and a power conversion efficiency of 6.5% in polymer solar cells, when solution processed from a nonchlorinated

Continuum model of non-equilibrium solvation and solvent effect on ultra-fast processes

International Nuclear Information System (INIS)

Li Xiangyuan; Fu Kexiang; Zhu Quan

2006-01-01

In the past 50 years, non-equilibrium solvation theory for ultra-fast processes such as electron transfer and light absorption/emission has attracted particular interest. A great deal of research efforts was made in this area and various models which give reasonable qualitative descriptions for such as solvent reorganization energy in electron transfer and spectral shift in solution, were developed within the framework of continuous medium theory. In a series of publications by the authors, we clarified that the expression of the non-equilibrium electrostatic free energy that is at the dominant position of non-equilibrium solvation and serves as the basis of various models, however, was incorrectly formulated. In this work, the authors argue that reversible charging work integration was inappropriately applied in the past to an irreversible path linking the equilibrium or the non-equilibrium state. Because the step from the equilibrium state to the nonequilibrium state is factually thermodynamically irreversible, the conventional expression for non-equilibrium free energy that was deduced in different ways is unreasonable. Here the authors derive the non-equilibrium free energy to a quite different form according to Jackson integral formula. Such a difference throws doubts to the models including the famous Marcus two-sphere model for solvent reorganization energy of electron transfer and the Lippert-Mataga equation for spectral shift. By introducing the concept of 'spring energy' arising from medium polarizations, the energy constitution of the non-equilibrium state is highlighted. For a solute-solvent system, the authors separate the total electrostatic energy into different components: the self-energies of solute charge and polarized charge, the interaction energy between them and the 'spring energy' of the solvent polarization. With detailed reasoning and derivation, our formula for non-equilibrium free energy can be reached through different ways. Based on the

Study on electrohydrodynamic jetting performance of organic solvents

Energy Technology Data Exchange (ETDEWEB)

Lee, Soo Hong; Nguyen, Xuan Hung; Gim, Yeong Hyeon; Ko, Han Seo [Sungkyunkwan University, Suwon (Korea, Republic of)

2015-11-15

The electrohydrodynamic (EHD) inkjet method is a printing technology using electricity. This technique allows for the printing of EML (Emission layer) materials, usually used for OLED devices, on a substrate. In this study, ejection experiments were performed with various solvents to verify which of them is properly ejected in the EHD method. The solvents employed were dielectric liquids with low viscosity and it was confirmed that among them two solvents, 1,2-Dichlorobenzene (DCB) and 1,2-Dichloroethane (DCE), produced the pulsating cone-Jet mode and stable cone-jet mode well. In addition, experiments were conducted to find out how the voltage and applied flux influence the ejection mode, in order to apply the result to the ejection control. It was found that the selected solvent was easily ejected and printed, due to the free surface charge and charge density determined by the dielectric constant. Finally, a patterning experiment was performed to verify proper printing.

Asymmetric supercapacitors with metal-like ternary selenides and porous graphene electrodes

KAUST Repository

Xia, Chuan

2016-04-14

Asymmetric supercapacitors provide a promising approach to fabricate capacitive energy storage devices with high energy and power densities. In this work, asymmetric supercapacitors with excellent performance have been fabricated using ternary (Ni, Co)0.85Se on carbon fabric as bind-free positive electrode and porous free-standing graphene films as negative electrode. Owing to their metal-like conductivity (~1.67×106 S m−1), significant electrochemical activity, and superhydrophilic nature, our nanostructured ternary nickel cobalt selenides result in a much higher areal capacitance (2.33 F cm−2 at 4 mA cm−2), better rate performance and cycling stability than their binary selenide equivalents, and other ternary oxides and chalcogenides. Those hybrid supercapacitors can afford impressive areal capacitance and stack capacitance of 529.3 mF cm−2 and 6330 mF cm−3 at 1 mA cm−2, respectively. More impressively, our optimized asymmetric device operating at 1.8 V delivers a very high stack energy density of 2.85 mWh cm−3 at a stack power density of 10.76 mW cm−3, as well as 85% capacitance retention after 10,000 continuous charge-discharge cycles. Even at a high stack power density of 1173 mW cm−3, this device still deliveries a stack energy density of 1.19 mWh cm−3, superior to most of the reported supercapacitors.

Cleaning of spent solvent and method of processing cleaning liquid waste

International Nuclear Information System (INIS)

Ozawa, Masaki; Kawada, Tomio; Tamura, Nobuhiko.

1993-01-01

Spent solvents discharged from a solvent extracting step mainly comprise n-dodecane and TBP and contain nuclear fission products and solvent degradation products. The spent solvents are cleaned by using a sodium chloride free detergent comprising hydrazine oxalate and hydrazine carbonate in a solvent cleaning device. Nitric acid is added to the cleaning liquid wastes containing spent detergents extracted from the solvent cleaning device, to control an acid concentration. The detergent liquid wastes of controlled acid concentration are sent to an electrolysis oxidation bath as electrolytes and electrochemically decomposed in carbonic acid gas, nitrogen gas and hydrogen gas. The decomposed gases are processed as off gases. The decomposed liquid wastes are processed as a waste nitric acid solution. This can provide more effective cleaning. In addition, the spent detergent can be easily decomposed in a room temperature region. Accordingly, the amount of wastes can be decreased. (I.N.)

Cyclopalladated complexes in enantioselective catalysis

Energy Technology Data Exchange (ETDEWEB)

Dunina, Valeria V; Gorunova, Olga N; Zykov, P A; Kochetkov, Konstantin A

2011-01-31

The results of the use of optically active palladacycles in enantioselective catalysis of [3,3]-sigmatropic rearrangements, aldol condensation, the Michael reaction and cross-coupling are analyzed. Reactions with allylic substrates or reagents and some other transformations are considered.

Fast and efficient method for reduction of carbonyl compounds with NaBH{sub 4} /wet SiO{sub 2} under solvent free condition

Energy Technology Data Exchange (ETDEWEB)

Zeynizadeh, Behzad; Bahyar, Tarifeh [Urmia University, Urmia (Iran, Islamic Republic of). Faculty of Sciences. Dept. of Chemistry]. E-mail: b.zeynizadeh@mail.urmia.ac.ir

2005-11-15

Reduction of structurally different carbonyl compounds such as aldehydes, ketones, {alpha},{beta}-unsaturated enals and enones, {alpha}-diketones and acyloins were accomplished efficiently by sodium borohydride in the presence of wet SiO{sub 2} (30% m/m) under solvent free condition. The reactions were performed at room tempere or 75-80 deg C with high to excellent yields of the corresponding products. The chemoselective reduction of aldehydes over ketones was achieved successfully with this reducing system. (author)

On the (ungreenness of Biocatalysis: Some challenging figures and some promising options

Directory of Open Access Journals (Sweden)

Pablo eDomínguez de María

2015-11-01

Full Text Available Biocatalysis is generally regarded as a ‘green’ technology. This statement is justified by the mild reaction conditions, the use of aqueous reaction media – with water as the paradigm of green solvents –, and the renewable nature of the biocatalysts. However, researchers making these statements frequently do not take into account the entire picture of their processes. Aspects like water consumption, wastewater production, titers and metrics of the (diluted? biocatalytic processes are important as well. With those figures at hand, many biocatalytic reactions do not appear so green anymore. This article critically discusses some common wrong assumptions given for biocatalytic approaches, with regard to their environmental impact and actual greenness. Some promising biocatalytic approaches, such as the use of biphasic systems involving biogenic solvents, deep-eutectic-solvents (and biogenic ionic liquids, water-free media, solvent-free processes, are briefly introduced, showing that enzyme catalysis can actually be a robust sustainable alternative for chemical processes.

Output voltage calculations in double barrier magnetic tunnel junctions with asymmetric voltage behavior

KAUST Repository

Useinov, Arthur; Mryasov, Oleg; Kosel, Jü rgen

2011-01-01

In this paper we study the asymmetric voltage behavior (AVB) of the tunnel magnetoresistance (TMR) for single and double barrier magnetic tunnel junctions (MTJs) in range of a quasi-classical free electron model. Numerical calculations of the TMR

Sequential Dy(OTf)3 -Catalyzed Solvent-Free Per-O-Acetylation and Regioselective Anomeric De-O-Acetylation of Carbohydrates.

Science.gov (United States)

Yan, Yi-Ling; Guo, Jiun-Rung; Liang, Chien-Fu

2017-09-19

Dysprosium(III) trifluoromethanesulfonate-catalyzed per-O-acetylation and regioselective anomeric de-O-acetylation of carbohydrates can be tuned by adjusting the reaction medium. In this study, the per-O-acetylation of unprotected sugars by using a near-stoichiometric amount of acetic anhydride under solvent-free conditions resulted in the exclusive formation of acetylated saccharides as anomeric mixtures, whereas anomeric de-O-acetylation in methanol resulted in a moderate-to-excellent yield. Reactions with various unprotected monosaccharides or disaccharides followed by a semi-one-pot sequential conversion into the corresponding acetylated glycosyl hemiacetal also resulted in high yields. Furthermore, the obtained hemiacetals could be successfully transformed into trichloroimidates after Dy(OTf) 3 -catalyzed glycosylation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solvent free hydroxylation of the methyl esters of Blighia unijugata seed oil in the presence of cetyltrimethylammonium permanganate

Directory of Open Access Journals (Sweden)

Adewuyi Adewale

2011-12-01

Full Text Available Abstract Extraction of oil from the seed of Blighia unijugata gave a yield of 50.82 ± 1.20% using hexane in a soxhlet extractor. The iodine and saponification values were 67.60 ± 0.80 g iodine/100 g and 239.20 ± 1.00 mg KOH/g respectively with C18:1 being the dominant fatty acid. Unsaturated methyl esters of Blighia unijugata which had been previously subjected to urea adduct complexation was used to synthesize methyl 9, 10-dihydroxyoctadecanoate via hydroxylation in the presence of cetyltrimethylammonium permanganate (CTAP. The reaction was monitored and confirmed using FTIR and GC-MS. This study has revealed that oxidation reaction of mono unsaturated bonds using CTAP could be achieved under solvent free condition.

Facile synthesis of 1-naphthol azo dyes with nano SiO2/HIO4 under solvent-free conditions

Directory of Open Access Journals (Sweden)

A.R. Pourali

2013-09-01

Full Text Available Nano-silica supported periodic acid (nano-SPIA has been utilized as a heterogeneous reagent for a highly efficient and one pot synthesis of azo dyes based on 1-naphthol under solvent-free conditions at room temperature. This method has some advantages, the reaction workup is very easy and the catalyst can be easily separated from the reaction mixture and one-pot procedure. The related products have been obtained in good to excellent yields, high purity and short reaction times. The structures of the products have been characterized by several techniques using UV-Vis, FT-IR, 1H NMR, 13C NMR and mass spectra.DOI: http://dx.doi.org/10.4314/bcse.v27i3.13

Asymmetric catalysis in organic synthesis

Energy Technology Data Exchange (ETDEWEB)

Reilly, S.D.; Click, D.R.; Grumbine, S.K.; Scott, B.L.; Watkins, J.G.

1998-11-01

This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The goal of the project was to prepare new catalyst systems, which would perform chemical reactions in an enantioselective manner so as to produce only one of the possible optical isomers of the product molecule. The authors have investigated the use of lanthanide metals bearing both diolate and Schiff-base ligands as catalysts for the enantioselective reduction of prochiral ketones to secondary alcohols. The ligands were prepared from cheap, readily available starting materials, and their synthesis was performed in a ''modular'' manner such that tailoring of specific groups within the ligand could be carried out without repeating the entire synthetic procedure. In addition, they have developed a new ligand system for Group IV and lanthanide-based olefin polymerization catalysts. The ligand system is easily prepared from readily available starting materials and offers the opportunity to rapidly prepare a wide range of closely related ligands that differ only in their substitution patterns at an aromatic ring. When attached to a metal center, the ligand system has the potential to carry out polymerization reactions in a stereocontrolled manner.

Series asymmetric supercapacitors based on free-standing inner-connection electrodes for high energy density and high output voltage

Science.gov (United States)

Tao, Jiayou; Liu, Nishuang; Rao, Jiangyu; Ding, Longwei; Al Bahrani, Majid Raissan; Li, Luying; Su, Jun; Gao, Yihua

2014-11-01

Asymmetric supercapacitors (ASCs) based on free-standing membranes with high energy density and high output voltage are reported. MnO2 nanowire/carbon nanotube (CNT) composites and MoO3 nanobelt/CNT composites are selected as the anode and the cathode materials of the devices, respectively. The ASC has a high volumetric capacitance of 50.2 F cm-3 at a scan rate of 2 mV s-1 and a high operation voltage window of 2.0 V. Especially, after a middle layer with an inner-connection structure was inserted between the anode and the cathode, the output voltage of the whole device can achieve 4.0 V. The full cell of series ASCs (SASC) with an inner-connection middle layer has a high energy density of 28.6 mW h cm-3 at a power density of 261.4 mW cm-3, and exhibits excellent cycling performance of 99.6% capacitance retention over 10 000 cycles. This strategy of designing the hybridized structure for SASCs provides a promising route for next-generation SCs with high energy density and high output voltage.Asymmetric supercapacitors (ASCs) based on free-standing membranes with high energy density and high output voltage are reported. MnO2 nanowire/carbon nanotube (CNT) composites and MoO3 nanobelt/CNT composites are selected as the anode and the cathode materials of the devices, respectively. The ASC has a high volumetric capacitance of 50.2 F cm-3 at a scan rate of 2 mV s-1 and a high operation voltage window of 2.0 V. Especially, after a middle layer with an inner-connection structure was inserted between the anode and the cathode, the output voltage of the whole device can achieve 4.0 V. The full cell of series ASCs (SASC) with an inner-connection middle layer has a high energy density of 28.6 mW h cm-3 at a power density of 261.4 mW cm-3, and exhibits excellent cycling performance of 99.6% capacitance retention over 10 000 cycles. This strategy of designing the hybridized structure for SASCs provides a promising route for next-generation SCs with high energy density and high

High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates

KAUST Repository

Stoltz, Brian

2010-06-14

The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates

KAUST Repository

Stoltz, Brian; McDougal, Nolan; Virgil, Scott

2010-01-01

The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

Amine-free reversible hydrogen storage in formate salts catalyzed by ruthenium pincer complex without pH control or solvent change.

Science.gov (United States)

Kothandaraman, Jotheeswari; Czaun, Miklos; Goeppert, Alain; Haiges, Ralf; Jones, John-Paul; May, Robert B; Prakash, G K Surya; Olah, George A

2015-04-24

Due to the intermittent nature of most renewable energy sources, such as solar and wind, energy storage is increasingly required. Since electricity is difficult to store, hydrogen obtained by electrochemical water splitting has been proposed as an energy carrier. However, the handling and transportation of hydrogen in large quantities is in itself a challenge. We therefore present here a method for hydrogen storage based on a CO2 (HCO3 (-) )/H2 and formate equilibrium. This amine-free and efficient reversible system (>90 % yield in both directions) is catalyzed by well-defined and commercially available Ru pincer complexes. The formate dehydrogenation was triggered by simple pressure swing without requiring external pH control or the change of either the solvent or the catalyst. Up to six hydrogenation-dehydrogenation cycles were performed and the catalyst performance remained steady with high selectivity (CO free H2 /CO2 mixture was produced). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Asymmetric excitation of surface plasmons by dark mode coupling

KAUST Repository

Zhang, X.

2016-02-19

Control over surface plasmons (SPs) is essential in a variety of cutting-edge applications, such as highly integrated photonic signal processing systems, deep-subwavelength lasing, high-resolution imaging, and ultrasensitive biomedical detection. Recently, asymmetric excitation of SPs has attracted enormous interest. In free space, the analog of electromagnetically induced transparency (EIT) in metamaterials has been widely investigated to uniquely manipulate the electromagnetic waves. In the near field, we show that the dark mode coupling mechanism of the classical EIT effect enables an exotic and straightforward excitation of SPs in a metasurface system. This leads to not only resonant excitation of asymmetric SPs but also controllable exotic SP focusing by the use of the Huygens-Fresnel principle. Our experimental findings manifest the potential of developing plasmonic metadevices with unique functionalities.

Asymmetric excitation of surface plasmons by dark mode coupling

KAUST Repository

Zhang, X.; Xu, Q.; Li, Q.; Xu, Y.; Gu, J.; Tian, Z.; Ouyang, C.; Liu, Y.; Zhang, S.; Zhang, Xixiang; Han, J.; Zhang, W.

2016-01-01

Control over surface plasmons (SPs) is essential in a variety of cutting-edge applications, such as highly integrated photonic signal processing systems, deep-subwavelength lasing, high-resolution imaging, and ultrasensitive biomedical detection. Recently, asymmetric excitation of SPs has attracted enormous interest. In free space, the analog of electromagnetically induced transparency (EIT) in metamaterials has been widely investigated to uniquely manipulate the electromagnetic waves. In the near field, we show that the dark mode coupling mechanism of the classical EIT effect enables an exotic and straightforward excitation of SPs in a metasurface system. This leads to not only resonant excitation of asymmetric SPs but also controllable exotic SP focusing by the use of the Huygens-Fresnel principle. Our experimental findings manifest the potential of developing plasmonic metadevices with unique functionalities.

Traceable atomic force microscopy of high-quality solvent-free crystals of [6,6]-phenyl-C61-butyric acid methyl ester

Science.gov (United States)

Lazzerini, Giovanni Mattia; Paternò, Giuseppe Maria; Tregnago, Giulia; Treat, Neil; Stingelin, Natalie; Yacoot, Andrew; Cacialli, Franco

2016-02-01

We report high-resolution, traceable atomic force microscopy measurements of high-quality, solvent-free single crystals of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). These were grown by drop-casting PCBM solutions onto the spectrosil substrates and by removing the residual solvent in a vacuum. A home-built atomic force microscope featuring a plane mirror differential optical interferometer, fiber-fed from a frequency-stabilized laser (emitting at 632.8 nm), was used to measure the crystals' height. The optical interferometer together with the stabilized laser provides traceability (via the laser wavelength) of the vertical measurements made with the atomic force microscope. We find that the crystals can conform to the surface topography, thanks to their height being significantly smaller compared to their lateral dimensions (namely, heights between about 50 nm and 140 nm, for the crystals analysed, vs. several tens of microns lateral dimensions). The vast majority of the crystals are flat, but an isolated, non-flat crystal provides insights into the growth mechanism and allows identification of "molecular terraces" whose height corresponds to one of the lattice constants of the single PCBM crystal (1.4 nm) as measured with X-ray diffraction.

A facile solvent-free Synthesis Route for the Assembly of Highly CO2 Selective and H2S tolerant NiSIFSIX Metal-Organic Framework

KAUST Repository

Eddaoudi, Mohamed; Shekhah, Osama; Belmabkhout, Youssef; Adil, Karim; Cairns, Amy J.; Bhatt, Prashant

2015-01-01

The development of materials for CO2 capture with high selectivity and high tolerance to H2S is of prime importance for various industrially relevant gas streams (e.g. natural gas and biogas upgrading as well as pre-combustion capture). Here, we report the successful fabrication of a MOF with combined exceptional CO2 capture properties and H2S tolerance, namely Ni SIFSIX based-MOF using both solvothermal and solvent-free methodologies.

A facile solvent-free Synthesis Route for the Assembly of Highly CO2 Selective and H2S tolerant NiSIFSIX Metal-Organic Framework

KAUST Repository

Eddaoudi, Mohamed

2015-07-06

The development of materials for CO2 capture with high selectivity and high tolerance to H2S is of prime importance for various industrially relevant gas streams (e.g. natural gas and biogas upgrading as well as pre-combustion capture). Here, we report the successful fabrication of a MOF with combined exceptional CO2 capture properties and H2S tolerance, namely Ni SIFSIX based-MOF using both solvothermal and solvent-free methodologies.

Eco-friendly all-carbon paper electronics fabricated by a solvent-free drawing method

International Nuclear Information System (INIS)

Kanaparthi, Srinivasulu; Badhulika, Sushmee

2016-01-01

Here we report the fabrication of high-performance all-carbon temperature and infrared (IR) sensors with a solvent-free multiwalled carbon nanotube (MWCNT) trace as the sensing element and commercial graphite pencil trace as the electrical contact on recyclable and biodegradable cellulose filter paper without using any toxic materials or complex procedures. The temperature sensor shows a large negative temperature coefficient of resistance (TCR) in the range of −3100 ppm K −1 to −4900 ppm K −1 , which is comparable to available commercial temperature sensors, and an activation energy of 34.85 meV. The IR sensor shows a high responsivity of 58.5 V W −1 , which is greater than reported IR sensors with similar dimensions. A detailed study of the conduction mechanism in MWCNTs with temperature and the photo response with IR illumination was done and it was found that the conduction is due to thermally assisted hopping in band tails and the photo response is bolometric in nature. The successful fabrication of these sensors on cellulose filter paper with a comparable performance to existing components indicates that it is possible to fabricate high-performance electronics using low-cost, eco-friendly materials without the need for expensive clean-room processing techniques or harmful chemicals. (paper)

3. International conference on catalysis in membrane reactors

Energy Technology Data Exchange (ETDEWEB)

NONE

1998-09-01

The 3. International Conference on Catalysis in Membrane Reactors, Copenhagen, Denmark, is a continuation of the previous conferences held in Villeurbanne 1994 and Moscow 1996 and will deal with the rapid developments taking place within membranes with emphasis on membrane catalysis. The approx. 80 contributions in form of plenary lectures and posters discuss hydrogen production, methane reforming into syngas, selectivity and specificity of various membranes etc. The conference is organised by the Danish Catalytic Society under the Danish Society for Chemical Engineering. (EG)

Free Energy Landscapes of Alanine Oligopeptides in Rigid-Body and Hybrid Water Models.

Science.gov (United States)

Nayar, Divya; Chakravarty, Charusita

2015-08-27

Replica exchange molecular dynamics is used to study the effect of different rigid-body (mTIP3P, TIP4P, SPC/E) and hybrid (H1.56, H3.00) water models on the conformational free energy landscape of the alanine oligopeptides (acAnme and acA5nme), in conjunction with the CHARMM22 force field. The free energy landscape is mapped out as a function of the Ramachandran angles. In addition, various secondary structure metrics, solvation shell properties, and the number of peptide-solvent hydrogen bonds are monitored. Alanine dipeptide is found to have similar free energy landscapes in different solvent models, an insensitivity which may be due to the absence of possibilities for forming i-(i + 4) or i-(i + 3) intrapeptide hydrogen bonds. The pentapeptide, acA5nme, where there are three intrapeptide backbone hydrogen bonds, shows a conformational free energy landscape with a much greater degree of sensitivity to the choice of solvent model, though the three rigid-body water models differ only quantitatively. The pentapeptide prefers nonhelical, non-native PPII and β-sheet populations as the solvent is changed from SPC/E to the less tetrahedral liquid (H1.56) to an LJ-like liquid (H3.00). The pentapeptide conformational order metrics indicate a preference for open, solvent-exposed, non-native structures in hybrid solvent models at all temperatures of study. The possible correlations between the properties of solvent models and secondary structure preferences of alanine oligopeptides are discussed, and the competition between intrapeptide, peptide-solvent, and solvent-solvent hydrogen bonding is shown to be crucial in the relative free energies of different conformers.

High temperature solvent extraction of oil shale and bituminous coal using binary solvent mixtures

Energy Technology Data Exchange (ETDEWEB)

Goetz, G.K.E. [Lehrstuhl fuer Geologie, Geochemie und Lagerstaetten des Erdoels und der Kohle, RWTH Aachen (Germany)

1997-12-31

A high volatile bituminous coal from the Saar Basin and an oil shale from the Messel deposit, both Germany, were extracted with binary solvent mixtures using the Advanced Solvent Extraction method (ASE). Extraction temperature and pressure were kept at 100 C, respectively 150 C, and 20,7 MPa. After the heating phase (5 min) static extractions were performed with mixtures (v:v, 1:3) of methanol with toluene, respectively trichloromethane, for further 5 min. Extract yields were the same or on a higher level compared to those from classical soxhlet extractions (3 days) using the same solvents at 60 C. Comparing the results from ASE with those from supercritical fluid extraction (SFE) the extract yields were similar. Increasing the temperature in ASE releases more soluble organic matter from geological samples, because compounds with higher molecular weight and especially more polar substances were solubilized. But also an enhanced extraction efficiency resulted for aliphatic and aromatic hydrocarbons which are used as biomarkers in Organic Geochemistry. Application of thermochemolysis with tetraethylammonium hydroxide (TEAH) using pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) on the extraction residues shows clearly that at higher extraction temperatures minor amounts of free fatty acids or their methyl esters (original or produced by ASE) were trapped inside the pore systems of the oil shale or the bituminous coal. ASE offers a rapid and very efficient extraction method for geological samples reducing analysis time and costs for solvents. (orig.)

Substitution of carcinogenic solvent dichloromethane for the extraction of volatile compounds in a fat-free model food system.

Science.gov (United States)

Cayot, Nathalie; Lafarge, Céline; Bou-Maroun, Elias; Cayot, Philippe

2016-07-22

Dichloromethane is known as a very efficient solvent, but, as other halogenated solvents, is recognized as a hazardous product (CMR substance). The objective of the present work is to propose substitution solvent for the extraction of volatile compounds. The most important physico-chemical parameters in the choice of an appropriate extraction solvent of volatile compounds are reviewed. Various solvents are selected on this basis and on their hazard characteristics. The selected solvents, safer than dichloromethane, are compared using the extraction efficiency of volatile compounds from a model food product able to interact with volatile compounds. Volatile compounds with different hydrophobicity are used. High extraction yields were positively correlated with high boiling points and high Log Kow values of volatile compounds. Mixtures of solvents such as azeotrope propan-2-one/cyclopentane, azeotrope ethyl acetate/ethanol, and mixture ethyl acetate/ethanol (3:1, v/v) gave higher extraction yields than those obtained with dichloromethane. Copyright © 2016 Elsevier B.V. All rights reserved.

Asymmetric free vibrations of laminated annular cross-ply circular plates including the effects of shear deformation and rotary inertia. Spline method

Energy Technology Data Exchange (ETDEWEB)

Viswanathan, K.K.; Kim, Kyung Su; Lee, Jang Hyun [Inha Univ., Incheon (Korea). Dept. of Naval Architecture and Ocean Engineering

2009-12-15

Asymmetric free vibrations of annular cross-ply circular plates are studied using spline function approximation. The governing equations are formulated including the effects of shear deformation and rotary inertia. Assumptions are made to study the cross-ply layered plates. A system of coupled differential equations are obtained in terms of displacement functions and rotational functions. These functions are approximated using Bickley- type spline functions of suitable order. Then the system is converted into the eigenvalue problem by applying the point collocation technique and suitable boundary conditions. Parametric studies have been made to investigate the effect of transverse shear deformation and rotary inertia on frequency parameter with respect to the circumferential node number, radii ratio and thickness to radius ratio for both symmetric and anti-symmetric cross-ply plates using various types of material properties. (orig.)

A smooth and differentiable bulk-solvent model for macromolecular diffraction

Energy Technology Data Exchange (ETDEWEB)

Fenn, T. D. [Department of Molecular and Cellular Physiology and Howard Hughes Medical Institute, Stanford, California (United States); Schnieders, M. J. [Department of Chemistry, Stanford, California (United States); Brunger, A. T., E-mail: brunger@stanford.edu [Department of Molecular and Cellular Physiology and Howard Hughes Medical Institute, Stanford, California (United States); Departments of Neurology and Neurological Sciences, Structural Biology and Photon Science, Stanford, California (United States)

2010-09-01

A new method for modeling the bulk solvent in macromolecular diffraction data based on Babinet’s principle is presented. The proposed models offer the advantage of differentiability with respect to atomic coordinates. Inclusion of low-resolution data in macromolecular crystallography requires a model for the bulk solvent. Previous methods have used a binary mask to accomplish this, which has proven to be very effective, but the mask is discontinuous at the solute–solvent boundary (i.e. the mask value jumps from zero to one) and is not differentiable with respect to atomic parameters. Here, two algorithms are introduced for computing bulk-solvent models using either a polynomial switch or a smoothly thresholded product of Gaussians, and both models are shown to be efficient and differentiable with respect to atomic coordinates. These alternative bulk-solvent models offer algorithmic improvements, while showing similar agreement of the model with the observed amplitudes relative to the binary model as monitored using R, R{sub free} and differences between experimental and model phases. As with the standard solvent models, the alternative models improve the agreement primarily with lower resolution (>6 Å) data versus no bulk solvent. The models are easily implemented into crystallographic software packages and can be used as a general method for bulk-solvent correction in macromolecular crystallography.

A smooth and differentiable bulk-solvent model for macromolecular diffraction

International Nuclear Information System (INIS)

Fenn, T. D.; Schnieders, M. J.; Brunger, A. T.

2010-01-01

A new method for modeling the bulk solvent in macromolecular diffraction data based on Babinet’s principle is presented. The proposed models offer the advantage of differentiability with respect to atomic coordinates. Inclusion of low-resolution data in macromolecular crystallography requires a model for the bulk solvent. Previous methods have used a binary mask to accomplish this, which has proven to be very effective, but the mask is discontinuous at the solute–solvent boundary (i.e. the mask value jumps from zero to one) and is not differentiable with respect to atomic parameters. Here, two algorithms are introduced for computing bulk-solvent models using either a polynomial switch or a smoothly thresholded product of Gaussians, and both models are shown to be efficient and differentiable with respect to atomic coordinates. These alternative bulk-solvent models offer algorithmic improvements, while showing similar agreement of the model with the observed amplitudes relative to the binary model as monitored using R, R free and differences between experimental and model phases. As with the standard solvent models, the alternative models improve the agreement primarily with lower resolution (>6 Å) data versus no bulk solvent. The models are easily implemented into crystallographic software packages and can be used as a general method for bulk-solvent correction in macromolecular crystallography

ACETANILIDA: SÍNTESE VERDE SEM SOLVENTE

Directory of Open Access Journals (Sweden)

Silvio Cunha

2015-07-01

Full Text Available We described herein a solvent-free synthesis of acetanilide developed in the context of green chemistry. The synthetic approach consisted of the reaction of aniline with acetic anhydride without additives, while using smaller amounts of reagents and water than previously described for this undergraduate experiment. The E Factor was 0.6 by experienced chemists and 0.9 by students.

Benign and efficient preparation of thioethers by solvent-free S-alkylation of thiols with alkyl halides catalyzed by potassium fluoride on alumina

DEFF Research Database (Denmark)

Nguyen, Kha Ngoc; Duus, Fritz; Luu, Thi Xuan Thi

2016-01-01

The preparation of thioethers by S-alkylation of various thiols with alkyl halides under solvent-free reaction conditions using potassium fluoride on alumina (KF/Al2O3) as a solid catalyst has been investigated in detail with respect to three different modes of reaction activation (ultrasound...... irradiation, microwave irradiation, and conventional heating) for obtaining maximum yield of the thioether. The importance of KF/Al2O3 as a particularly efficient catalyst was corroborated for all three modes of reaction activation, although the reaction time was found to be strongly dependent on the mode...

Synthesis and application of aryl-ferrocenyl(pseudo-biarylic) complexes. Part 5. Design and synthesis of a new type of ferrocene-based planar chiral DMAP analogues. A new catalyst system for asymmetric nucleophilic catalysis

DEFF Research Database (Denmark)

Seitzberg, J.G; Dissing, C; Søtofte, Inger

2005-01-01

A new first-generation catalyst system for nucleophilic catalysis has been developed. It is based on a planar chiral ferrocene skeleton with either the potent nucleophile 4-(dimethylamino)pyridine (DMAP) or the related 4-nitropyridine N-oxide attached in either the 2- or the 3-position. The synth......A new first-generation catalyst system for nucleophilic catalysis has been developed. It is based on a planar chiral ferrocene skeleton with either the potent nucleophile 4-(dimethylamino)pyridine (DMAP) or the related 4-nitropyridine N-oxide attached in either the 2- or the 3-position...

Effect of Different Solvents on the Measurement of Phenolics and the Antioxidant Activity of Mulberry (Morus atropurpurea Roxb.) with Accelerated Solvent Extraction.

Science.gov (United States)

Yang, Jiufang; Ou, XiaoQun; Zhang, Xiaoxu; Zhou, ZiYing; Ma, LiYan

2017-03-01

The effects of 9 different solvents on the measurement of the total phenolics and antioxidant activities of mulberry fruits were studied using accelerated solvent extraction (ASE). Sixteen to 22 types of phenolics (flavonols, flavan-3-ols, flavanol, hydroxycinnamic acids, hydroxybenzoic acids, and stilbenes) from different mulberry extracts were characterized and quantified using HPLC-MS/MS. The principal component analysis (PCA) was used to determine the suitable solvents to distinguish between different classes of phenolics. Additionally, the phenolic extraction abilities of ASE and ultrasound-assisted extraction (UAE) were compared. The highest extraction efficiency could be achieved by using 50% acidified methanol (50MA) as ASE solvents with 15.14 mg/gallic acid equivalents g dry weight of mulberry fruit. The PCA results revealed that the 50MA followed by 50% acidified acetone (50AA) was the most efficient solvent for the extraction of phenolics, particularly flavonols (627.12 and 510.31 μg/g dry weight, respectively), while water (W) was not beneficial to the extraction of all categories of phenolics. Besides, the results of 3 antioxidant capability assays (DPPH, ABTS free radical-scavenging assay, and ferric-reducing antioxidant power assay) showed that water-based organic solvents increased the antioxidant capabilities of the extracts compared with water or pure organic solvents. ASE was more suitable for the extraction of phenolics than UAE. © 2017 Institute of Food Technologists®.

µ-reactors for Heterogeneous Catalysis

DEFF Research Database (Denmark)

Jensen, Robert

is described in detail. Since heating and temperature measurement is an extremely important point in heterogeneous catalysis an entire chapter is dedicated to this subject. Three different types of heaters have been implemented and tested both for repeatability and homogeneity of the heating as well...

Synthesis of biodiesel from soybean oil by coupling catalysis with subcritical methanol

International Nuclear Information System (INIS)

Yin Jianzhong; Xiao Min; Wang Aiqin; Xiu Zhilong

2008-01-01

Biodiesel synthesis from soybean oil and methanol was investigated under supercritical and subcritical conditions. Under the supercritical conditions, the maximum methyl ester yield exceeded 98% when the molar ratio of methanol to oil was 42:1 and the reaction temperature ranged from 260 deg. C to 350 deg. C. In order to decrease the operational temperature and pressures and to increase the conversion efficiency of methanol, first co-solvent was added to the reaction mixture to improve the reaction process, and then a novel idea was presented in which catalysis and supercritical effect were coupled together. Thus, with 2.5 wt% hexane, temperature of 300 deg. C, methanol to oil ratio of 42, a 85.5% conversion is observed in 30 min, while a 62.2% conversion is observed without hexane in the same condition; with less carbon dioxide, temperature of 300 deg. C, methanol to oil ratio of 42, a 91.6% conversion is observed in 20 min, while a 51.4% conversion is observed without carbon dioxide in the same condition; With only a little amount of potassium hydroxide as the catalyst (KOH/oil = 0.1 wt%), a 98% yield of methyl esters was obtained in 10 min at a reaction temperature of 160 deg. C and the molar ratio (methanol/oil) of 24:1. In contrast, above 1 wt% of catalyst is required in the conventional alkali-catalyzed method; while only 6% yield of methyl ester was obtained at 260 deg. C (corresponding to subcritical conditions) without the catalyst. This result demonstrated that by coupling the catalysis and subcritical operation, the amount of catalyst could be largely reduced and the methanol utilization could be significantly enhanced. Thus, the present method offers some advantages over both the conventional alkali-catalyst method and the expensive supercritical method

Standardization of solvent extraction procedure for determination of uranium in seawater

International Nuclear Information System (INIS)

Sukanta Maity; Sahu, S.K.; Pandit, G.G.

2015-01-01

Solvent extraction procedure using ammonium pyrolidine dithiocarbamate complexing agent in methyl isobutyl ketone organic phase and acid exchange back-extraction is described for the simultaneous quantitative pre-concentration of uranium in seawater followed by its determination by differential pulse adsorptive stripping voltammetry. Solvent extraction time is optimized for extraction of uranium from seawater. Solvent extraction efficiency for uranium in seawater at different pH was carried out. The method gives a recovery of 98 ± 2 % for 400 mL sample at pH 3.0 ± 0.02, facilitating the rapid and interference free analysis of seawater samples. (author)

Experimental measurement and modelling of solubility of inosine-5′-monophosphate disodium in pure and mixed solvents

International Nuclear Information System (INIS)

Zou, Fengxia; Zhuang, Wei; Wu, Jinglan; Zhou, Jingwei; Liu, Qiyan; Chen, Yong; Xie, Jingjing; Zhu, Chenjie; Guo, Ting; Ying, Hanjie

2014-01-01

Graphical abstract: - Highlights: • Solubility of 5′-IMPNa 2 in various solvents was studied for the first time. • The solubility could be ranked as follows: water > methanol > ethanol > acetone. • Modified Apelblat equation gave the best correlating results. • Mixing Gibbs free energies, enthalpies, and entropies were predicted. • Solubility data and equations can optimise the crystallization conditions. - Abstract: The solubility of biological chemicals in solvents provide important fundamental data and is generally considered as an essential factor in the design of crystallization processes. The equilibrium solubility data of inosine-5′-monophosphate disodium (5′-IMPNa 2 ) in water, methanol, ethanol, acetone, as well as in the solvent mixtures (methanol + water, ethanol + water, acetone + water), were measured by an isothermal method at temperatures ranging from (293.15 to 313.15) K. The measured data in pure and mixed solvents were then modelled using the modified Apelblat equation, van’t Hoff equation, λh equation, ideal model and the Wilson model. The modified Apelblat equation showed the best modelling results, and it was therefore used to predict the mixing Gibbs free energies, enthalpies, and entropies of 5′-IMPNa 2 in pure and binary solvents. The positive values of the calculated partial molar Gibbs free energies indicated the variations in the solubility trends of 5′-IMPNa 2 . Water and ethanol (in the binary mixture with water) were found to be the most effective solvent and anti-solvent, respectively

Protective role of salt in catalysis and maintaining structure of halophilic proteins against denaturation

Science.gov (United States)

Sinha, Rajeshwari; Khare, Sunil K.

2014-01-01

Search for new industrial enzymes having novel properties continues to be a desirable pursuit in enzyme research. The halophilic organisms inhabiting under saline/ hypersaline conditions are considered as promising source of useful enzymes. Their enzymes are structurally adapted to perform efficient catalysis under saline environment wherein n0n-halophilic enzymes often lose their structure and activity. Haloenzymes have been documented to be polyextremophilic and withstand high temperature, pH, organic solvents, and chaotropic agents. However, this stability is modulated by salt. Although vast amount of information have been generated on salt mediated protection and structure function relationship in halophilic proteins, their clear understanding and correct perspective still remain incoherent. Furthermore, understanding their protein architecture may give better clue for engineering stable enzymes which can withstand harsh industrial conditions. The article encompasses the current level of understanding about haloadaptations and analyzes structural basis of their enzyme stability against classical denaturants. PMID:24782853

Biodiesel forming reactions using heterogeneous catalysis

Science.gov (United States)

Liu, Yijun

Biodiesel synthesis from biomass provides a means for utilizing effectively renewable resources, a way to convert waste vegetable oils and animal fats to a useful product, a way to recycle carbon dioxide for a combustion fuel, and production of a fuel that is biodegradable, non-toxic, and has a lower emission profile than petroleum-diesel. Free fatty acid (FFA) esterification and triglyceride (TG) transesterification with low molecular weight alcohols constitute the synthetic routes to prepare biodiesel from lipid feedstocks. This project was aimed at developing a better understanding of important fundamental issues involved in heterogeneous catalyzed biodiesel forming reactions using mainly model compounds, representing part of on-going efforts to build up a rational base for assay, design, and performance optimization of solid acids/bases in biodiesel synthesis. As FFA esterification proceeds, water is continuously formed as a byproduct and affects reaction rates in a negative manner. Using sulfuric acid (as a catalyst) and acetic acid (as a model compound for FFA), the impact of increasing concentrations of water on acid catalysis was investigated. The order of the water effect on reaction rate was determined to be -0.83. Sulfuric acid lost up to 90% activity as the amount of water present increased. The nature of the negative effect of water on esterification was found to go beyond the scope of reverse hydrolysis and was associated with the diminished acid strength of sulfuric acid as a result of the preferential solvation by water molecules of its catalytic protons. The results indicate that as esterification progresses and byproduct water is produced, deactivation of a Bronsted acid catalyst like H2SO4 occurs. Using a solid composite acid (SAC-13) as an example of heterogeneous catalysts and sulfuric acid as a homogeneous reference, similar reaction inhibition by water was demonstrated for homogeneous and heterogeneous catalysis. This similarity together with

Active sites engineering of metal-organic frameworks for heterogeneous catalysis

Energy Technology Data Exchange (ETDEWEB)

Li, Xinle [Iowa State Univ., Ames, IA (United States)

2016-12-17

In conclusion, we have for the first time developed a novel solid base catalyst, Ndoped MOF-253 derived porous carbons (Cz-MOF-253). Cz-MOF-253 is highly porous and exhibit high efficiency in Knoevenagel condensation reaction. Furthermore, Cz-MOF-253 is robust and can be reused up to five times. In comparison, the analogous nitrogen-free catalyst-Cz-DUT-5, and other nitrogen- MOFs derived carbon showed an inferior performance. Moreover, the high basicity and porous nature enable the design of bifunctional catalyst and facilitate tandem condensation-hydrogenation reactions. This work delineates the first attempt that demonstrates MOF-derived carbons as solid base catalyst and its potential application in tandem catalysis. Future work on exploring new catalytic reactions based on such porous Lewis basic MOF-derived carbons is currently underway.

Curvature bound from gravitational catalysis

Science.gov (United States)

Gies, Holger; Martini, Riccardo

2018-04-01

We determine bounds on the curvature of local patches of spacetime from the requirement of intact long-range chiral symmetry. The bounds arise from a scale-dependent analysis of gravitational catalysis and its influence on the effective potential for the chiral order parameter, as induced by fermionic fluctuations on a curved spacetime with local hyperbolic properties. The bound is expressed in terms of the local curvature scalar measured in units of a gauge-invariant coarse-graining scale. We argue that any effective field theory of quantum gravity obeying this curvature bound is safe from chiral symmetry breaking through gravitational catalysis and thus compatible with the simultaneous existence of chiral fermions in the low-energy spectrum. With increasing number of dimensions, the curvature bound in terms of the hyperbolic scale parameter becomes stronger. Applying the curvature bound to the asymptotic safety scenario for quantum gravity in four spacetime dimensions translates into bounds on the matter content of particle physics models.

Simulation of seismic signals from asymmetric LANL hydrodynamic calculations

International Nuclear Information System (INIS)

Stevens, J.L.; Rimer, N.; Halda, E.J.; Barker, T.G.; Davis, C.G.; Johnson, W.E.

1993-01-01

Hydrodynamic calculations of an asymmetric nuclear explosion source were propagated to teleseismic distances to investigate the effects of the asymmetric source on seismic signals. The source is an explosion in a 12 meter long canister with the device at one end of the canister and a metal plate adjacent to the explosion. This produces a strongly asymmetric two-lobed source in the hydrodynamic region. The hydrodynamic source is propagated to the far field using a three-step process. The Eulerian hydrodynamic code SOIL was used by LANL to calculate the material velocity, density, and internal energy up to a time of 8.9 milliseconds after the explosion. These quantities were then transferred to an initial grid for the Lagrangian elastic/plastic finite difference code CRAM, which was used by S-CUBED to propagate the signal through the region of nonlinear deformation into the external elastic region. The cavity size and shape at the time of the overlay were determined by searching for a rapid density change in the SOIL grid, and this interior region was then rezoned into a single zone. The CRAM calculation includes material strength and gravity, and includes the effect of the free surface above the explosion. Finally, far field body waves were calculated by integrating over a closed surface in the elastic region and using the representation theorem. A second calculation was performed using an initially spherical source for comparison with the asymmetric calculation

Cyclic Solvent Vapor Annealing for Rapid, Robust Vertical Orientation of Features in BCP Thin Films

Science.gov (United States)

Paradiso, Sean; Delaney, Kris; Fredrickson, Glenn

2015-03-01

Methods for reliably controlling block copolymer self assembly have seen much attention over the past decade as new applications for nanostructured thin films emerge in the fields of nanopatterning and lithography. While solvent assisted annealing techniques are established as flexible and simple methods for achieving long range order, solvent annealing alone exhibits a very weak thermodynamic driving force for vertically orienting domains with respect to the free surface. To address the desire for oriented features, we have investigated a cyclic solvent vapor annealing (CSVA) approach that combines the mobility benefits of solvent annealing with selective stress experienced by structures oriented parallel to the free surface as the film is repeatedly swollen with solvent and dried. Using dynamical self-consistent field theory (DSCFT) calculations, we establish the conditions under which the method significantly outperforms both static and cyclic thermal annealing and implicate the orientation selection as a consequence of the swelling/deswelling process. Our results suggest that CSVA may prove to be a potent method for the rapid formation of highly ordered, vertically oriented features in block copolymer thin films.

Tailoring the Variational Implicit Solvent Method for New Challenges: Biomolecular Recognition and Assembly

Directory of Open Access Journals (Sweden)

Clarisse Gravina Ricci

2018-02-01

Full Text Available Predicting solvation free energies and describing the complex water behavior that plays an important role in essentially all biological processes is a major challenge from the computational standpoint. While an atomistic, explicit description of the solvent can turn out to be too expensive in large biomolecular systems, most implicit solvent methods fail to capture “dewetting” effects and heterogeneous hydration by relying on a pre-established (i.e., guessed solvation interface. Here we focus on the Variational Implicit Solvent Method, an implicit solvent method that adds water “plasticity” back to the picture by formulating the solvation free energy as a functional of all possible solvation interfaces. We survey VISM's applications to the problem of molecular recognition and report some of the most recent efforts to tailor VISM for more challenging scenarios, with the ultimate goal of including thermal fluctuations into the framework. The advances reported herein pave the way to make VISM a uniquely successful approach to characterize complex solvation properties in the recognition and binding of large-scale biomolecular complexes.

Tailoring the Variational Implicit Solvent Method for New Challenges: Biomolecular Recognition and Assembly

Science.gov (United States)

Ricci, Clarisse Gravina; Li, Bo; Cheng, Li-Tien; Dzubiella, Joachim; McCammon, J. Andrew

2018-01-01

Predicting solvation free energies and describing the complex water behavior that plays an important role in essentially all biological processes is a major challenge from the computational standpoint. While an atomistic, explicit description of the solvent can turn out to be too expensive in large biomolecular systems, most implicit solvent methods fail to capture “dewetting” effects and heterogeneous hydration by relying on a pre-established (i.e., guessed) solvation interface. Here we focus on the Variational Implicit Solvent Method, an implicit solvent method that adds water “plasticity” back to the picture by formulating the solvation free energy as a functional of all possible solvation interfaces. We survey VISM's applications to the problem of molecular recognition and report some of the most recent efforts to tailor VISM for more challenging scenarios, with the ultimate goal of including thermal fluctuations into the framework. The advances reported herein pave the way to make VISM a uniquely successful approach to characterize complex solvation properties in the recognition and binding of large-scale biomolecular complexes. PMID:29484300

ELECTROCHEMICAL PROMOTED CATALYSIS: TOWARDS PRACTICAL UTILIZATION

Directory of Open Access Journals (Sweden)

DIMITRIOS TSIPLAKIDES

2008-07-01

Full Text Available Electrochemical promotion (EP of catalysis has already been recognized as “a valuable development in catalytic research” (J. Pritchard, 1990 and as “one of the most remarkable advances in electrochemistry since 1950” (J. O’M. Bockris, 1996. Laboratory studies have clearly elucidated the phenomenology of electrochemical promotion and have proven that EP is a general phenomenon at the interface of catalysis and electrochemistry. The major progress toward practical utilization of EP is surveyed in this paper. The focus is given on the electropromotion of industrial ammonia synthesis catalyst, the bipolar EP and the development of a novel monolithic electropromoted reactor (MEPR in conjunction with the electropromotion of thin sputtered metal films. Future perspectives of electrochemical promotion applications in the field of hydrogen technologies are discussed.

Solvent-free and room temperature synthesis of 3-arylquinolines from different anilines and styrene oxide in the presence of Al2O3/MeSO3H

Directory of Open Access Journals (Sweden)

Hashem Sharghi

2017-09-01

Full Text Available A highly efficient, simple and environmentally friendly synthesis of 3-arylquinolines has been developed in the presence of Al2O3/MeSO3H via one-pot reaction of anilines and styrene oxide. This methodology provides very rapid access to 3-arylquinolines in good to excellent yields under solvent-free conditions at room temperature in air.

Karakteristik Membran Asimetris Polietersufone (PES dengan Pelarut Dimetil Formamide dan N-Metil-2-Pyrolidone - (Characteristic of Poliethersulfone (PES Asymmetric Membrane with Dimethyl Formamide and N-Methyl Pyrolidone as Solvent

Directory of Open Access Journals (Sweden)

Sri Mulyati

2017-06-01

Full Text Available Membrane that is generally used for separation process could be made using phase inversion technique. This research aims to create polyethersulfone (PES asymmetric membranes via phase inversion technique using solvent and Trans Membrane Pressure (TMP as variable. SEM analysis indicated that membranes had asymmetric structure that consits of two layers which denser skin layer on the top surface and the porous support on the bottom. PES/DMF membrane showed larger pore structure than PES/NMP. The permeability coefficients of both membranes were in the ultrafiltration range. The coefficient permeability (Lp of PES/DMF membrane was 35.769 L/m2.hour, much greater compared to PES/NMP membrane which was 15.364 L/m2.hour.bar. Molecular Weight Cut-Off (MWCO of PES/DMF membrane was 177 Kda, meanwhile PES/NMP was 186 Kda. Performances of the membranes were evaluated  using dextrane as feed solution. PES/DMF membrane resulted in an higher flux and lower rejection than PES/NMP.Keywords: asymmetric membrane, membrane performance, Molecular Weight Cut-Off (MWCO, morphology, permeability ABSTRAKMembran yang umumnya digunakan untuk proses pemisahan dapat dibuat menggunakan teknik inversi fasa. Penelitian ini bertujuan untuk mengetahui karakteristik membran asimetris polietersulfone (PES yang dibuat menggunakan teknik inversi fasa dengan variabel jenis pelarut dan Trans Membrane Pressure (TMP. Hasil analisis Scanning Electron Microscopy (SEM terhadap morfologi membran membuktikan bahwa membran yang dihasilkan merupakan membran asimetris yang terdiri dari dua lapisan yaitu bagian atas merupakan lapisan tipis dan lapisan bawah adalah lapisan berpori. Membran PES/DMF memiliki struktur pori yang lebih besar dibandingkan membran PES/NMP. Koefisien permeabilitas kedua membran yang dihasilkan berada dalam jangkauan ultrafiltrasi. Koefisien permeabilitas (Lp membran PES/DMF sebesar 35,769 L/m2.jam, nilai ini jauh lebih besar dibandingkan PES/NMP yaitu 15,364 L/m2.jam