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Heterogeneous Systems (heterogeneous + system)
Terms modified by Heterogeneous Systems Selected Abstracts1,3-Dihalo-5,5-dimethylhydantoin or Citric Acid/NaNO2 as a Heterogeneous System for the Selective Mononitration of Phenols under Mild Conditions.CHEMINFORM, Issue 28 2006Mohammad A. Zolfigol Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] SiBr4/Wet Silica Gel as an Efficient Heterogeneous System for Cleavage of C=N.CHEMINFORM, Issue 12 2004Surya Kanta De Abstract For Abstract see ChemInform Abstract in Full Text. [source] Aromatic Hydrocarbon-Catalyzed Direct Reaction of Sulfur and Sodium in a Heterogeneous System: Selective and Facile Synthesis of Sodium Monosulfide and Disulfide.CHEMINFORM, Issue 37 2003Toshikazu Takata Abstract For Abstract see ChemInform Abstract in Full Text. [source] Reactions of Silica Chloride (SiO2Cl)/DMSO, a Heterogeneous System for the Facile Regeneration of Carbonyl Compounds from Thioacetals and Ring-Expansion Anellation of Cyclic Thioacetals.CHEMINFORM, Issue 38 2002Habib Firouzabadi Abstract For Abstract see ChemInform Abstract in Full Text. [source] Investigation of electrical conduction mechanism in double-layered polymeric systemJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2009Prashant Shukla Abstract The electrical conduction in solution-grown polymethylmethacrylate (PMMA), polyvinylidenefluoride (PVDF) and PMMA-PVDF double-layered samples in the sandwich configuration (metal-polymer-metal) was investigated at different fields in the range 100,120 kV/cm as a function of temperature in the range 293,423 K for samples of constant thickness of about 50 ,m. Certain effects which lead to a large burst of current immediately after the application of field were observed in double-layered samples. An attempt was made to identify the nature of the current by comparing the observed dependence on electric field, electrode material and temperature with the respective characteristic features of the existing theories on electrical conduction. The observed linear I-V characteristics show that the electrical conduction follows Pool-Frenkel mechanism in PMMA and PVDF samples. Whereas, the non-linear behavior of current-voltage measurements in PMMA-PVDF double-layered samples have been interpreted on the basis of space charge limited conduction (SCLC) mechanism. The conductivity of the polymer films increased on formation of their double-layer laminates. The polymer-polymer interface act as charge carrier trapping centres and provides links between the polymer molecules in the amorphous region. The interfacial phenomenon in polymer-polymer heterogeneous system has been interpreted in terms of Maxwell-Wagner model. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] The role of a novel p -phenylen-bis-maleamic acid grafted atactic polypropylene interfacial modifier in polypropylene/mica composites as evidenced by tensile propertiesJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2009J. M. García-Martínez Abstract Present work is devoted to the study of the tensile behavior of polypropylene (PP)/mica composites with improved interfacial interactions from the matrix side caused by the presence of a p -phenylen-bis-maleamic acid grafted atactic polypropylene (aPP- pPBM) as an interfacial agent. Hence, aPP- pPBM was previously obtained, in our laboratories, by reactive processing in the melt of a by-product (atactic PP) from industrial polymerization reactors. Present article is two-fold, on one hand it has been planned to evidence the so called interfacial effects caused by this novel interfacial agent (aPP- pPBM) yielding better final properties of the heterogeneous system as a whole as revealed by tensile mechanical properties, and on the other to obtain models to forecast the overall behavior of the system. For such purpose, a Box-Wilson experimental design considering the amount of mica particles and of interfacial agent as independent variables was used to obtain polynomials to forecast the behavior of the PP/Mica system in the experimental space scanned. The existence of a critical amount of aPP- pPBM to optimize mechanical properties appears to emerge. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Synthesis of 1H -quinazoline-2,4-diones from 2-aminobenzonitriles by fixation of carbon dioxide with amidine moiety supported polymer at atmospheric pressureJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 3 2009Daisuke Nagai Abstract 1H -Quinazoline-2,4-diones, which are key intermediates in the synthesis of medicines, were successfully synthesized from 2-aminobenzonitriles by the fixation of CO2 in the presence of a polystyrene derivative bearing amidine moiety [poly(amidine)]. A model reaction, that is, the reaction of 2-aminobenzonitrile (1a) with CO2 in the presence of N -methyltetrahydropyrimidine (MTHP) revealed that a catalytic amount of MTHP afforded 1H -quinazoline-2,4-dione (2a) quantitatively at atmospheric pressure. Several 1H -quinazoline-2,4-diones (2a - 2c) were successfully synthesized from the corresponding 2-aminobenzonitriles (1a - 1c) in the presence of poly(amidine). The poly(amidine) could easily be separated from the reaction mixture by filtration and reused in subsequent reactions owing to the heterogeneous system. These demonstrated that poly(amidine) is a useful heterogeneous polymer-supported reagent for the synthesis of 1H -quinazoline-2,4-diones from CO2. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 653,657, 2009 [source] Efficient oxidative coupling polymerization for synthesis of thermosetting poly(phenylene ether) copolymer with a low dielectric lossJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2008Jun Nunoshige A novel oxidative coupling polymerization using a water/toluene heterogeneous system for the synthesis of thermosetting Poly(phenylene ether) copolymer (Allyl-PPE) was developed. Allyl-PPE with a narrow molecular weight distribution and a low copper content was obtained in the presence of a Cu/TMEDA catalyst dissolved in water droplets. This method solved the problems during the synthesis of the Allyl-PPE with conventional Cu/pyridine catalysts. The resulting Allyl-PPE exhibited excellent dielectric properties (,, = 2.4, tan , = 0.002 at 10 GHz), and it will be useful for applications to high-speed and high-frequency printed circuit boards. [source] Stress-Driven Morphological Instabilities in Rocks, Glass, and CeramicsJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 3 2007M. A. Grinfeld The purpose of this study is to further investigate the classical Gibbs analysis of the heterogeneous system "stressed crystal,melt." It is demonstrated that each equilibrium configuration is stable with respect to a special class of variations introduced by Gibbs. This basic result is compared with the opposite result on the universal morphological instability of phase interface separating a stressed crystal with its melt. Some plausible manifestations of the instabilities implied by the Gibbs model are qualitatively discussed. [source] Simulation of dc conductance of two-dimensional heterogeneous system: application to carbon wires made by ion irradiation on polycrystalline diamondPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 6 2006N. A. Poklonski Abstract A percolation model of two-dimensional heterogeneous system composed of two conductive phases and a method for calculating the macroscopic electric conductance of such a system in direct current regime is proposed. The parameters of the model are its geometrical dimensions, the conductance of the two phases and the relative fractions of the phases in the system. The model satisfactorily describes the non-linear dependence on width of conductance of the carbon nano- and microwires made on polycrystalline diamond surface by focused ion beam irradiation. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Reactive blending of functionalized acrylic rubbers and epoxy resinsPOLYMER ENGINEERING & SCIENCE, Issue 9 2001C. Dispenza A high molecular weight acrylonitrile/butadiene/methacrylic acid (Nipol 1472) rubber is chosen to control processability and mechanical properties of a TGDDM (tetra glycidyl diphenyl methane) based epoxy resin formulation for aerospace composite applications. The physical blend of rubber and epoxy resin, achieved by dissolution of all the components in a common solvent, forms a heterogeneous system after solvent removal and presents coarse phase separation during cure that impairs any practical relevance of this material. A marked improvement of rubberepoxy miscibility is achieved by reactive blending (,pre-reaction') the epoxy oligomer with the functional groups present in the rubber. The epoxy-rubber ,adduct' so obtained appears as a homogeneous system at room temperature and also after compounding with the curing agent. Depending on the nature and extent of interactions developed between the rubber and the epoxy resin during ,pre-reaction,' materials with different resin flow characteristics, distinctive morphologies and mechanical properties after curing were obtained. The effect of ,pre-reaction' on the resin cure reaction kinetics has been also investigated. [source] Structural information from quadrupolar nuclei in solid state NMRCONCEPTS IN MAGNETIC RESONANCE, Issue 3 2006Sharon E. Ashbrook Abstract Solid-state NMR has become the method of choice for determining details of molecular-level structure in heterogeneous systems. Though spin-1/2 nuclei still form the core of most such studies, quadrupolar nuclei are increasingly being used. This review assesses what is currently possible, from achieving high-resolution spectra for quadrupolar nuclei (a prerequisite for most structure determination work), to forming correlation spectra which give qualitative details of spatial proximity of nuclei and the determination of internuclear distances, between quadrupolar spins and quadrupolar and spin-1/2 nuclei. Examples are given of each method discussed, and the advantages and disadvantages of the various experiments for different possible applications are assessed. © 2006 Wiley Periodicals, Inc. Concepts Magn Reson Part A 28A: 183,248, 2006. [source] On the inversion of multicomponent NMR relaxation and diffusion decays in heterogeneous systemsCONCEPTS IN MAGNETIC RESONANCE, Issue 2 2005Raffaele Lamanna Abstract The analysis of the decay of NMR signals in heterogeneous samples requires the solution of an ill-posed inverse problem to evaluate the distributions of relaxation and diffusion parameters. Laplace transform is the most widely accepted algorithm used to describe the NMR decay in heterogeneous systems. In this article we suggest that a superposition of Fredholm integrals, with different kernels, is a more suitable model for samples in which liquid and solid-like phases are both present. In addition, some algorithms for the inversion of Laplace and Fredholm inverse problems are illustrated. The quadrature methods and regularization function in connection with the use of nonlinear discretization grids are also discussed. The described inversion algorithms are tested on simulated and experimental data, and the role of noise is discussed. © 2005 Wiley Periodicals, Inc. Concepts Magn Reson Part A 26A: 78,90, 2005 [source] Towards workflow simulation in service-oriented architecture: an event-based approachCONCURRENCY AND COMPUTATION: PRACTICE & EXPERIENCE, Issue 4 2008Yanchong Zheng Abstract The emergence of service-oriented architecture (SOA) has brought about a loosely coupled computing environment that enables flexible integration and reuse of heterogeneous systems. On building a SOA for application systems, more and more research has been focused on service composition, in which workflow and simulation techniques have shown great potential. Simulation of services' interaction is important since the services ecosystem is dynamic and in continuous evolution. However, there is a lack in the research of services' simulation, especially models, methods and systems to support the simulation of interaction behavior of composite services. In this paper, an enhanced workflow simulation method with the support of interactive events mechanism is proposed to fulfill this requirement. At build time, we introduce an event sub-model in the workflow meta-model, and our simulation engine supports the event-based interaction pattern at run time. With an example simulated in the prototype system developed according to our method, the advantages of our method in model verification and QoS evaluation for service compositions are also highlighted. Copyright © 2007 John Wiley & Sons, Ltd. [source] Pipelines on heterogeneous systems: models and toolsCONCURRENCY AND COMPUTATION: PRACTICE & EXPERIENCE, Issue 9 2005F. Almeida Abstract We study the performance of pipeline algorithms in heterogeneous networks. The concept of heterogeneity is not only restricted to the differences in computational power of the nodes, but also refers to the network capabilities. We develop a skeleton tool that allows us an efficient block-cyclic mapping of pipelines on heterogeneous systems. The tool supports pipelines with a number of stages much larger than the number of physical processors available. We derive an analytical formula that allows us to predict the performance of pipelines in heterogeneous systems. According to the analytical complexity formula, numerical strategies to solve the optimal mapping problem are proposed. The computational results prove the accuracy of the predictions and effectiveness of the approach. Copyright © 2005 John Wiley & Sons, Ltd. [source] JOPI: a Java object-passing interfaceCONCURRENCY AND COMPUTATION: PRACTICE & EXPERIENCE, Issue 7-8 2005Jameela Al-Jaroodi Abstract Recently there has been an increasing interest in developing parallel programming capabilities in Java to harness the vast resources available in clusters, grids and heterogeneous networked systems. In this paper, we introduce a Java object-passing interface (JOPI) library. JOPI provides Java programmers with the necessary functionality to write object-passing parallel programs in distributed heterogeneous systems. JOPI provides a Message Passing Interface (MPI)-like interface that can be used to exchange objects among processes. In addition to the well-known benefits of the object-oriented development model, using objects to exchange information in JOPI is advantageous because it facilitates passing complex structures and enables the programmer to isolate the problem space from the parallelization problem. The run-time environment for JOPI is portable, efficient and provides the necessary functionality to deploy and execute parallel Java programs. Experiments were conducted on a cluster system and a collection of heterogeneous platforms to measure JOPI's performance and compare it with MPI. The results show good performance gains using JOPI. Copyright © 2005 John Wiley & Sons, Ltd. [source] Impedance Spectroscopy: A Powerful Tool for Rapid Biomolecular Screening and Cell Culture MonitoringELECTROANALYSIS, Issue 23 2005Isaac Abstract Dielectric spectroscopy or Electrochemical impedance spectroscopy (EIS) is traditionally used in corrosion monitoring, coatings evaluation, batteries, and electrodeposition and semiconductor characterization. However, in recent years, it is gaining widespread application in biotechnology, tissue engineering, and characterization of biological cells, disease diagnosis and cell culture monitoring. This article discusses the principles and implementation of dielectric spectroscopy in these bioanalytical applications. It provides examples of EIS as label-free, mediator-free strategies for rapid screening of biocompatible surfaces, monitoring pathogenic bacteria, as well as the analysis of heterogeneous systems, especially biological cells and tissues. Descriptions are given of the application of nanoparticles to improve the analytical sensitivities in EIS. Specific examples are given of the detection of base pair mismatches in the DNA sequence of Hepatitis B disease, TaySach's disease and Microcystis spp. Others include the EIS detection of viable pathogenic bacteria and the influence of nanomaterials in enhancing biosensor performance. Expanding applications in tissue engineering such as adsorption of proteins onto thiolated hexa(ethylene glycol)-terminated (EG6) self-assembled monolayer (SAM) are discussed. [source] Ground Water Modeling Applications Using the Analytic Element MethodGROUND WATER, Issue 1 2006Randall J. Hunt Though powerful and easy to use, applications of the analytic element method are not as widespread as finite-difference or finite-element models due in part to their relative youth. Although reviews that focus primarily on the mathematical development of the method have appeared in the literature, a systematic review of applications of the method is not available. An overview of the general types of applications of analytic elements in ground water modeling is provided in this paper. While not fully encompassing, the applications described here cover areas where the method has been historically applied (regional, two-dimensional steady-state models, analyses of ground water,surface water interaction, quick analyses and screening models, wellhead protection studies) as well as more recent applications (grid sensitivity analyses, estimating effective conductivity and dispersion in highly heterogeneous systems). The review of applications also illustrates areas where more method development is needed (three-dimensional and transient simulations). [source] Extremely High Silver Ionic Conductivity in Composites of Silver Halide (AgBr, AgI) and Mesoporous Alumina,ADVANCED FUNCTIONAL MATERIALS, Issue 4 2006H. Yamada Abstract The silver ionic conductivity in heterogeneous systems of AgBr:Al2O3 and AgI:Al2O3 is highly enhanced by utilizing mesoporous Al2O3 as the insulating phase. The highest Ag+ conductivity of 3.1,×,10,3,,,1,cm,1 (at 25,°C) has been obtained for the AgI:Al2O3 composite with an Al2O3 volume fraction of 0.3. For AgBr:Al2O3, the enhancement of the conductivity is satisfactorily explained in the framework of the ideal space-charge model, while in the case of AgI:Al2O3 stacking disorder is also considered to contribute to the ionic conductivity. [source] Thermodynamics of Nanosystems with a Special View to Charge CarriersADVANCED MATERIALS, Issue 25-26 2009Joachim Maier Abstract Basic ingredients of interfacial thermodynamics are recapitulated with a special eye on the nanometer-size regime. Questions are then briefly tackled that arise if, in heterogeneous systems, the constituent phases shrink to atomistic dimensions. Particularly helpful in this context are thermodynamic approaches, in which the introduction of interfacial tension is avoided. While the first part addresses ground structure quantities, the second part deals with questions of size and confinement effects on entropy and energy of ionic and electronic defects. These defects represent the respective excitations within this ground structure. The article emphasizes the similarities between ions and electrons manifested in the statistics rather than elaborating on the discrepancies that are primarily reflected by different densities of states and mobilities. It is, therefore, not the intention of the article to address aspects of nanoelectronics that rely on quantum transport for which many reviews are available. Nonetheless all these discussed aspects are directly relevant for both nanoionics and nanoelectronics. [source] User involvement in developing mobile and temporarily interconnected systemsINFORMATION SYSTEMS JOURNAL, Issue 2 2010Ola Henfridsson Abstract Information systems (IS) research on user involvement has primarily theorized relationships between developers, managers and users in systems development. However, so far, marginal attention has been paid to differences in user involvement practices between information systems. This paper explores user involvement in developing mobile and temporarily interconnected systems (MTIS). We refer to MTIS as heterogeneous systems that rely on network technologies for increasing the ubiquity of information services for users on the move. Such systems are becoming increasingly important in leveraging, e.g. car infotainment, supply chain management and wireless e-commerce. With particular emphasis on the nature of MTIS and its implications for user involvement, the paper analyses the systems development process of an action research project. The findings suggest that user involvement practices need to be adapted to accommodate features of this class of systems. Being an early attempt to trace the implications of technology features such as use context switches and temporary system relationships, the paper contributes to the development of an updated theory of the user role in an era of increased system complexity and stakeholder ambiguity. [source] Silica-Supported Zirconium Complexes and their Polyoligosilsesquioxane Analogues in the Transesterification of Acrylates: Part 2.ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 13 2009Activity, Recycling, Regeneration Abstract The catalytic activity of both supported and soluble molecular zirconium complexes was studied in the transesterification reaction of ethyl acrylate by butanol. Two series of catalysts were employed: three well defined silica-supported acetylacetonate and n -butoxy zirconium(IV) complexes linked to the surface by one or three siloxane bonds, (SiO)Zr(acac)3 (1) (SiO)3Zr(acac) (2) and (SiO)3Zr(O- n -Bu) (3), and their soluble polyoligosilsesquioxy analogues (c -C5H9)7Si8O12(CH3)2Zr(acac)3 (1,), (c -C5H9)7Si7O12Zr(acac) (2,), and (c -C5H9)7Si7O12Zr(O- n -Bu) (3,). The reactivity of these complexes were compared to relevant molecular catalysts [zirconium tetraacetylacetonate, Zr(acac)4 and zirconium tetra- n -butoxide, Zr(O- n- Bu)4]. Strong activity relationships between the silica-supported complexes and their polyoligosilsesquioxane analogues were established. Acetylacetonate complexes were found to be far superior to alkoxide complexes. The monopodal complexes 1 and 1, were found to be the most active in their respective series. Studies on the recycling of the heterogeneous catalysts showed significant degradation of activity for the acetylacetonate complexes (1 and 2) but not for the less active tripodal alkoxide catalyst, 3. Two factors are thought to contribute to the deactivation of catalyst: the lixivation of zirconium by cleavage of surface siloxide bonds and exchange reactions between acetylacetonate ligands and alcohols in the substrate/product solution. It was shown that the addition of acetylacetone to the low activity catalyst Zr(O- n- Bu)4 produced a system that was as active as Zr(acac)4. The applicability of ligand addition to heterogeneous systems was then studied. The addition of acetylacetone to the low activity solid catalyst 3 produced a highly active catalyst and the addition of a stoichiometric quantity of acetylacetone at each successive batch catalytic run greatly reduced catalyst deactivation for the highly active catalyst 1. [source] Efficient Heterogeneous Asymmetric Catalysis of the Mukaiyama Aldol Reaction by Silica- and Ionic Liquid-Supported Lewis Acid Copper(II) Complexes of Bis(oxazolines)ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 2 2008S. Doherty Abstract Lewis acid complexes based on copper(II) and an imidazolium-tagged bis(oxazoline) have been used to catalyse the asymmetric Mukaiyama aldol reaction between methyl pyruvate and 1-methoxy-1-trimethylsilyloxypropene under homogeneous and heterogeneous conditions. Although the ees obtained in ionic liquid were similar to those found in dichloromethane, there was a significant rate enhancement in the ionic liquid with reactions typically reaching completion within 2,min compared with only 55,% conversion after 60,min in dichloromethane. However, this rate enhancement was offset by lower chemoselectivity in ionic liquids due to the formation of 3-hydroxy-1,3-diphenylbutan-1-one as a by-product. Supporting the catalyst on silica or an imidazolium-modified silica using the ionic liquid or in an ionic liquid-diethyl ether system completely suppressed the formation of this by-product without reducing the enantioselectivity. Although the heterogeneous systems were characterised by a drop in catalytic activity the system could be recycled up to five times without any loss in conversion or ee. [source] Influence of transverse rotating magnetic field on enhancement of solid dissolution processAICHE JOURNAL, Issue 6 2010Rakoczy Abstract The main objective of this work is to study the effect of transverse rotating magnetic field (TRMF) on the enhancement of solid dissolution process in the novel type reactor (TRMFR). The application of magnetically driven fluidization (MDF with homogeneous and heterogeneous systems) on mass transfer process is presented. A study of the effect of ferromagnetic particles content on solid,liquid mass transfer has been made. The experimental investigations are provided for the explanation of the influence on the dissolution process of a solid body to surrounding its dilute solution in a novel type reactor with the ferromagnetic particles suspended. The mass transfer coefficient is calculated from a kinetic equation and correlated in the relationship including standard and magnetic dimensionless numbers. The overall enhancements due to TRMF and MDF were compared. Unique correlating relations were obtained to generalize the experimental database. © 2009 American Institute of Chemical Engineers AIChE J, 2010 [source] Does avian species richness in natural patch mosaics follow the forest fragmentation paradigm?ANIMAL CONSERVATION, Issue 1 2007D. C. Pavlacky Jr. Abstract As one approaches the north-eastern limit of pinyon (Pinus spp.) juniper (Juniperus spp.) vegetation on the Colorado Plateau, USA, woodland patches become increasingly disjunct, grading into sagebrush (Artemisia spp.)-dominated landscapes. Patterns of avian species richness in naturally heterogeneous forests may or may not respond to patch discontinuity in the same manner as bird assemblages in fragmented agricultural systems. We used observational data from naturally patchy woodlands and predictions derived from studies of human-modified agricultural forests to estimate the effects of patch area, shape, isolation and distance to contiguous woodland on avian species richness. We predicted that patterns of species richness in naturally patchy juniper woodlands would differ from those observed in fragmented agricultural systems. Our objectives were to (1) estimate the effect of naturally occurring patch structure on avian species richness with respect to habitat affinity and migratory strategy and (2) assess the concordance of the effects to predictions from agricultural forest systems. We used the analogy between populations and communities to estimate species richness, where species are treated as individuals in the application of traditional capture,recapture theory. Information-theoretic model selection showed that overall species richness was explained primarily by the species area relationship. There was some support for a model with greater complexity than the equilibrium theory of island biogeography where the isolation of large patches resulted in greater species richness. Species richness of woodland-dwelling birds was best explained by the equilibrium hypothesis with partial landscape complementation by open-country species in isolated patches. Species richness within specific migratory strategies showed concomitant increases and no shifts in species composition along the patch area gradient. Our results indicate that many patterns of species richness considered to be fragmentation effects may be general consequences of patch discontinuity and are ubiquitous in naturally heterogeneous systems. There was no evidence for the effects of patch shape and distance to contiguous woodland in juniper woodland, suggesting edge effects and dependence upon regional species pools are characteristics of fragmented agricultural systems. Natural patch mosaics may provide benchmarks for evaluating fragmentation effects and managing forests by mimicking natural landscape patterns. [source] Autocatalytic Enantiomerisation at the Crystal Surface in Deracemisation of Scalemic ConglomeratesCHEMISTRY - A EUROPEAN JOURNAL, Issue 39 2009Shengwei Wei Dr. Abstract Deracemisation of racemic or scalemic conglomerates of intrinsically chiral compounds appears to be a promising method of chiral resolution. By combining the established methods of asymmetric synthesis and the physical process of crystal growth, we were able to achieve a complete deracemisation (with 100,%,ee) of an asymmetric Mannich product conglomerate,vigorously stirred in its saturated solution,from a starting enantiomeric excess value of 15.8,% in the presence of pyrrolidine (8,mol,%) as an achiral catalyst for the CC bond-forming reaction. Strong activation of this deracemisation process was observed on mild isothermal heating to only 40,°C, resulting in dramatic acceleration by a factor of about 20 with respect to the results obtained at room temperature. Despite the fact that the racemisation half-life time of the nearly enantiopure Mannich product (with 99,%,ee) in the homogenous solution at the reaction temperature is eight days, the deracemisation process took only hours in a small-scale experiment. This apparent paradox is explained by a proposed rapid enantiomerisation at the crystal/solution interface, which was corroborated by a 13C labelling experiment that confirmed the involvement of rapid enantiomerisation. Frequent monitoring of the solution-phase ee of the slowly racemising compound further revealed that the minor enantiomer dominated in solution, supporting an explanation based on a kinetic model. A generalisation of the process of "aymmetric autocatalysis" (resulting in automultiplication of chiral products in homogenous media) to encompass heterogeneous systems is also suggested. [source] Determination of linear response in the detection of mixtures of aroma compounds by atmospheric pressure ionization,mass spectrometry (API,MS)FLAVOUR AND FRAGRANCE JOURNAL, Issue 1 2008Roberto A. Buffo Abstract The linearity of atmospheric pressure ionization,mass spectrometry (API,MS) response in mixtures of aroma compounds was determined for a ,homogeneous' system (four esters) and a ,heterogeneous' system (five compounds of different chemical functionality). All combinations analysed within each system followed a saturation pattern as concentration increased. Total linear responses were determined by the linear behaviour of individual compounds. Ionization patterns within each mixture were explained by proton affinity data (i.e. the species' ability to accept protons), molecular reaction rates (defined by molecular weight), and product ion distribution (according to fragmentation of the corresponding parent ion). Copyright © 2007 John Wiley & Sons, Ltd. [source] | ||||||||||||||||||||||||||||