WorldWideScience

Sample records for catalysts molecular design

  1. Molecular catalysts structure and functional design

    CERN Document Server

    Gade, Lutz H

    2014-01-01

    Highlighting the key aspects and latest advances in the rapidly developing field of molecular catalysis, this book covers new strategies to investigate reaction mechanisms, the enhancement of the catalysts' selectivity and efficiency, as well as the rational design of well-defined molecular catalysts. The interdisciplinary author team with an excellent reputation within the community discusses experimental and theoretical studies, along with examples of improved catalysts, and their application in organic synthesis, biocatalysis, and supported organometallic catalysis. As a result, readers wil

  2. POROUS ALUMINOPHOSPHATES :From Molecular Sieves to Designed Acid Catalysts

    Science.gov (United States)

    Pastore, H. O.; Coluccia, S.; Marchese, L.

    2005-08-01

    This review covers the synthesis, characterization, and physico-chemical properties of microporous and mesoporous aluminophosphates and silicoaluminophosphates molecular sieves. Particular emphasis is given to the materials that have found applications as acid catalysts. We consider the evolution of the synthesis procedures from the first discoveries to the current methodologies and give perspectives for new possible synthesis strategies. Emphasis is given to the use of specially prepared precursors/reactants designed for the use as molecular sieves. Experimental (especially MAS-NMR and FTIR spectroscopy) and theoretical approaches to the description of the Si insertion into the ALPO framework and to the acidic properties of SAPOs and MeAPSOs materials are discussed.

  3. Molecular-level Design of Heterogeneous Chiral Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Gellman, Andrew John [Carnegie Mellon University; Sholl, David S. [Georgia Institute of Technology; Tysoe, Wilfred T. [University of Wisconsin - Milwaukee; Zaera, Francisco [University of California at Riverside

    2013-04-28

    Understanding and controlling selectivity is one of the key challenges in heterogeneous catalysis. Among problems in catalytic selectivity enantioselectivity is perhaps the most the most challenging. The primary goal of the project on “Molecular-level Design of Heterogeneous Chiral Catalysts” is to understand the origins of enantioselectivity on chiral heterogeneous surfaces and catalysts. The efforts of the project team include preparation of chiral surfaces, characterization of chiral surfaces, experimental detection of enantioselectivity on such surfaces and computational modeling of the interactions of chiral probe molecules with chiral surfaces. Over the course of the project period the team of PI’s has made some of the most detailed and insightful studies of enantioselective chemistry on chiral surfaces. This includes the measurement of fundamental interactions and reaction mechanisms of chiral molecules on chiral surfaces and leads all the way to rationale design and synthesis of chiral surfaces and materials for enantioselective surface chemistry. The PI’s have designed and prepared new materials for enantioselective adsorption and catalysis. Naturally Chiral Surfaces • Completion of a systematic study of the enantiospecific desorption kinetics of R-3-methylcyclohexanone (R-3-MCHO) on 9 achiral and 7 enantiomeric pairs of chiral Cu surfaces with orientations that span the stereographic triangle. • Discovery of super-enantioselective tartaric acid (TA) and aspartic acid (Asp) decomposition as a result of a surface explosion mechanism on Cu(643)R&S. Systematic study of super-enantiospecific TA and Asp decomposition on five enantiomeric pairs of chiral Cu surfaces. • Initial observation of the enantiospecific desorption of R- and S-propylene oxide (PO) from Cu(100) imprinted with {3,1,17} facets by L-lysine adsorption. Templated Chiral Surfaces • Initial observation of the enantiospecific desorption of R- and S-PO from Pt(111) and Pd(111

  4. Metalloporphyrin catalysts for oxygen reduction developed using computer-aided molecular design

    Energy Technology Data Exchange (ETDEWEB)

    Ryba, G.N.; Hobbs, J.D.; Shelnutt, J.A. [and others

    1996-04-01

    The objective of this project is the development of a new class of metalloporphyrin materials used as catalsyts for use in fuel cell applications. The metalloporphyrins are excellent candidates for use as catalysts at both the anode and cathode. The catalysts reduce oxygen in 1 M potassium hydroxide, as well as in 2 M sulfuric acid. Covalent attachment to carbon supports is being investigated. The computer-aided molecular design is an iterative process, in which experimental results feed back into the design of future catalysts.

  5. Design of heterogeneous catalysts

    DEFF Research Database (Denmark)

    Frey, Anne Mette

    was inspired by a computational screening, suggesting that alloys such as Ni-Fe, Co-Ni, and Co-Fe should show superior activity to the industrially used nickel catalyst. Especially the Ni-Fe system was considered to be interesting, since such alloy catalysts should be both more active and cheaper than the Ni...... catalyst. The results from the screening were experimentally verified for CO hydrogenation, CO2 hydrogenation, and simultaneous CO and CO2 hydrogenation by bimetallic Ni-Fe catalysts. These catalysts were found to be highly active and selective. The Co-Ni and Co-Fe systems were investigated for CO...... well, and the best catalyst prepared had a C5+ yield almost a factor of two higher than a standard air calcined Co catalyst. In the NH3-SCR reaction it is desirable to develop an active and stable catalyst for NOx removal in automotive applications, since the traditionally used vanadium-based catalyst...

  6. Synthesis and characterization of alumina-supported vanadium oxide catalysts prepared by the molecular designed dispersion of VO(acac)2 complexes

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Baltes, M.; Voort, P. van der; Ramachandra Rao, R.; Catana, Gabriela; Schoonheydt, R.A.; Vansant, E.F.

    2000-01-01

    Alumina-supported vanadium oxide catalysts have been prepared by the molecular designed dispersion method, using the vanadyl acetylacetonate complex (VO(acac)2). The complex has been adsorbed on the support from solution, followed by thermal conversion into the corresponding supported vanadium oxide

  7. Efficient epoxidation of propene using molecular catalysts

    DEFF Research Database (Denmark)

    Markovits, Iulius I. E.; Anthofer, Michael H.; Kolding, Helene

    2014-01-01

    The epoxidation of propene is performed in homogeneous phase using various molecular catalysts and H2O2 or tert-butyl hydroperoxide as oxidants. A comparison between some molybdenum catalysts and methyltrioxorhenium (MTO) shows that the well known Re catalyst is the best among the examined...

  8. Combinatorial computational chemistry approach of tight-binding quantum chemical molecular dynamics method to the design of the automotive catalysts

    International Nuclear Information System (INIS)

    Ito, Yuki; Jung, Changho; Luo, Yi; Koyama, Michihisa; Endou, Akira; Kubo, Momoji; Imamura, Akira; Miyamoto, Akira

    2006-01-01

    Recently, we have developed a new tight-binding quantum chemical molecular dynamics program 'Colors' for combinatorial computational chemistry approach. This methodology is based on our original tight-binding approximation and realized over 5000 times acceleration compared to the conventional first-principles molecular dynamics method. In the present study, we applied our new program to the simulations on various realistic large-scale models of the automotive three-way catalysts, ultrafine Pt particle/CeO 2 (111) support. Significant electron transfer from the Pt particle to the CeO 2 (111) surface was observed and it was found to strongly depend on the size of the Pt particle. Furthermore, our simulation results suggest that the reduction of the Ce atom due to the electron transfer from the Pt particle to the CeO 2 surface is a main reason for the strong interaction of the Pt particle and CeO 2 (111) support

  9. Molecular metal catalysts on supports: organometallic chemistry meets surface science.

    Science.gov (United States)

    Serna, Pedro; Gates, Bruce C

    2014-08-19

    Recent advances in the synthesis and characterization of small, essentially molecular metal complexes and metal clusters on support surfaces have brought new insights to catalysis and point the way to systematic catalyst design. We summarize recent work unraveling effects of key design variables of site-isolated catalysts: the metal, metal nuclearity, support, and other ligands on the metals, also considering catalysts with separate, complementary functions on supports. The catalysts were synthesized with the goal of structural simplicity and uniformity to facilitate incisive characterization. Thus, they are essentially molecular species bonded to porous supports chosen for their high degree of uniformity; the supports are crystalline aluminosilicates (zeolites) and MgO. The catalytic species are synthesized in reactions of organometallic precursors with the support surfaces; the precursors include M(L)2(acetylacetonate)1-2, with M = Ru, Rh, Ir, or Au and the ligands L = C2H4, CO, or CH3. Os3(CO)12 and Ir4(CO)12 are used as precursors of supported metal clusters, and some such catalysts are made by ship-in-a-bottle syntheses to trap the clusters in zeolite cages. The simplicity and uniformity of the supported catalysts facilitate precise structure determinations, even in reactive atmospheres and during catalysis. The methods of characterizing catalysts in reactive atmospheres include infrared (IR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), and nuclear magnetic resonance (NMR) spectroscopies, and complementary methods include density functional theory and atomic-resolution aberration-corrected scanning transmission electron microscopy for imaging of individual metal atoms. IR, NMR, XANES, and microscopy data demonstrate the high degrees of uniformity of well-prepared supported species. The characterizations determine the compositions of surface metal complexes and clusters, including the ligands and the metal

  10. Nanoparticle-Supported Molecular Polymerization Catalysts

    OpenAIRE

    Amgoune, Abderramane; Krumova, Marina; Mecking, Stefan

    2008-01-01

    Homogeneous molecular catalysts are immobilzed in a well-defined fashion on individual silica nanoparticles with a narrow particle size distribution by covalent attachment. This synthetic methodology is demonstrated with modified salicylaldiminato-substituted titanium(IV) complexes incorporating a trimethoxysilane-terminated linker: dichloro-bis[κ2-N,O-6-(3-(trimethoxysilyl)propoxyphenylimino)-2-tert-butyl-phenolato]titanium(IV) (3) and dichlorobis[κ2-N,O-6-(4-(trimethoxysilyl)propoxy-2,3,5,6...

  11. Activation of molecular catalysts using semiconductor quantum dots

    Science.gov (United States)

    Meyer, Thomas J [Chapel Hill, NC; Sykora, Milan [Los Alamos, NM; Klimov, Victor I [Los Alamos, NM

    2011-10-04

    Photocatalytic materials based on coupling of semiconductor nanocrystalline quantum dots (NQD) and molecular catalysts. These materials have capability to drive or catalyze non-spontaneous chemical reactions in the presence of visible radiation, ultraviolet radiation, or both. The NQD functions in these materials as a light absorber and charge generator. Following light absorption, the NQD activates a molecular catalyst adsorbed on the surface of the NQD via transfer of one or more charges (either electrons or electron-holes) from the NQD to the molecular catalyst. The activated molecular catalyst can then drive a chemical reaction. A photoelectrolytic device that includes such photocatalytic materials is also described.

  12. Chemical engineering design of CO oxidation catalysts

    Science.gov (United States)

    Herz, Richard K.

    1987-01-01

    How a chemical reaction engineer would approach the challenge of designing a CO oxidation catalyst for pulsed CO2 lasers is described. CO oxidation catalysts have a long history of application, of course, so it is instructive to first consider the special requirements of the laser application and then to compare them to the characteristics of existing processes which utilize CO oxidation catalysts. All CO2 laser applications require a CO oxidation catalyst with the following characteristics: (1) active at stoichiometric ratios of O2 and CO, (2) no inhibition by CO2 or other components of the laser environment, (3) releases no particulates during vibration or thermal cycling, and (4) long lifetime with a stable activity. In all applications, low consumption of power is desirable, a characteristic especially critical in aerospace applications and, thus, catalyst activity at low temperatures is highly desirable. High power lasers with high pulse repetition rates inherently require circulation of the gas mixture and this forced circulation is available for moving gas past the catalyst. Low repetition rate lasers, however, do not inherently require gas circulation, so a catalyst that did not require such circulation would be favorable from the standpoint of minimum power consumption. Lasers designed for atmospheric penetration of their infrared radiation utilize CO2 formed from rare isotopes of oxygen and this application has the additional constraint that normal abundance oxygen isotopes in the catalyst must not exchange with rare isotopes in the gas mixture.

  13. Towards the computational design of solid catalysts

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Bligaard, Thomas; Rossmeisl, Jan

    2009-01-01

    Over the past decade the theoretical description of surface reactions has undergone a radical development. Advances in density functional theory mean it is now possible to describe catalytic reactions at surfaces with the detail and accuracy required for computational results to compare favourably...... with experiments. Theoretical methods can be used to describe surface chemical reactions in detail and to understand variations in catalytic activity from one catalyst to another. Here, we review the first steps towards using computational methods to design new catalysts. Examples include screening for catalysts...

  14. Immobilization of molecular catalysts in supported ionic liquid phases.

    Science.gov (United States)

    Van Doorslaer, Charlie; Wahlen, Joos; Mertens, Pascal; Binnemans, Koen; De Vos, Dirk

    2010-09-28

    In a supported ionic liquid phase (SILP) catalyst system, an ionic liquid (IL) film is immobilized on a high-surface area porous solid and a homogeneous catalyst is dissolved in this supported IL layer, thereby combining the attractive features of homogeneous catalysts with the benefits of heterogeneous catalysts. In this review reliable strategies for the immobilization of molecular catalysts in SILPs are surveyed. In the first part, general aspects concerning the application of SILP catalysts are presented, focusing on the type of catalyst, support, ionic liquid and reaction conditions. Secondly, organic reactions in which SILP technology is applied to improve the performance of homogeneous transition-metal catalysts are presented: hydroformylation, metathesis reactions, carbonylation, hydrogenation, hydroamination, coupling reactions and asymmetric reactions.

  15. Octahedral molecular sieve sorbents and catalysts

    Science.gov (United States)

    Li, Liyu [Richland, WA; King, David L [Richland, WA

    2010-04-20

    Octahedral molecular sieve sorbents and catalysts are disclosed, including silver hollandite and cryptomelane. These materials can be used, for example, to catalyze the oxidation of CO.sub.x (e.g., CO), NO.sub.x (e.g., NO), hydrocarbons (e.g., C.sub.3H.sub.6) and/or sulfur-containing compounds. The disclosed materials also may be used to catalyze other reactions, such as the reduction of NO.sub.2. In some cases, the disclosed materials are capable of sorbing certain products from the reactions they catalyze. Silver hollandite, in particular, can be used to remove a substantial portion of certain sulfur-containing compounds from a gas or liquid by catalysis and/or sorption. The gas or liquid can be, for example, natural gas or a liquid hydrocarbon.

  16. Single Turnover at Molecular Polymerization Catalysts Reveals Spatiotemporally Resolved Reactions.

    Science.gov (United States)

    Easter, Quinn T; Blum, Suzanne A

    2017-10-23

    Multiple active individual molecular ruthenium catalysts have been pinpointed within growing polynorbornene, thereby revealing information on the reaction dynamics and location that is unavailable through traditional ensemble experiments. This is the first single-turnover imaging of a molecular catalyst by fluorescence microscopy and allows detection of individual monomer reactions at an industrially important molecular ruthenium ring-opening metathesis polymerization (ROMP) catalyst under synthetically relevant conditions (e.g. unmodified industrial catalyst, ambient pressure, condensed phase, ca. 0.03 m monomer). These results further establish the key fundamentals of this imaging technique for characterizing the reactivity and location of active molecular catalysts even when they are the minor components. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Backbone Diversity Analysis in Catalyst Design

    NARCIS (Netherlands)

    Maldonado, A.G.; Hageman, J.A.; Mastroianni, S.; Rothenberg, G.

    2009-01-01

    We present a computer-based heuristic framework for designing libraries of homogeneous catalysts. In this approach, a set of given bidentate ligand-metal complexes is disassembled into key substructures (building blocks). These include metal atoms, ligating groups, backbone groups, and residue

  18. Electron beam irradiation effect on nanostructured molecular sieve catalysts

    International Nuclear Information System (INIS)

    Yuan Zhongyong; Zhou Wuzong; Parvulescu, Viorica; Su Baolian

    2003-01-01

    Electron impact can induce chemical changes on particle surfaces of zeolites and molecular sieve catalysts. Some experimental observations of electron irradiation effect on molecular sieve catalysts are presented, e.g., electron-beam-induced growth of bare silver nanowires from zeolite crystallites, formation of vesicles in calcium phosphate, migration of microdomains in iron-oxide doped mesoporous silicas, structural transformation from mesostructured MCM-41 to microporous ZSM-5, etc. The formation mechanisms of the surface structures are discussed

  19. 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

  20. Mesoporous molecular sieves as advanced supports for olefin metathesis catalysts

    Czech Academy of Sciences Publication Activity Database

    Balcar, Hynek; Čejka, Jiří

    2013-01-01

    Roč. 257, 21-22 (2013), s. 3107-3124 ISSN 0010-8545 R&D Projects: GA AV ČR IAA400400805; GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : Olefin metathesis * mesoporous molecular sieves * Heterogeneous catalysts Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 12.098, year: 2013

  1. Catalyst design for carbon nanotube growth using atomistic modeling

    International Nuclear Information System (INIS)

    Pint, Cary L; Bozzolo, Guillermo; Hauge, Robert

    2008-01-01

    The formation and stability of bimetallic catalyst particles, in the framework of carbon nanotube growth, is studied using the Bozzolo-Ferrante-Smith (BFS) method for alloys. Monte Carlo-Metropolis simulations with the BFS method are utilized in order to predict and study equilibrium configurations for nanoscale catalyst particles which are directly relevant to the catalyst state prior to growth of carbon nanotubes. At the forefront of possible catalyst combinations is the popular Fe-Mo bimetallic catalyst, which we have recently studied experimentally. We explain our experimental results, which indicate that the growth observed is dependent on the order of co-catalyst deposition, in the straightforward interpretation of BFS strain and chemical energy contributions toward the formation of Fe-Mo catalyst prior to growth. We find that the competition between the formation of metastable inner Mo cores and clusters of surface-segregated Mo atoms in Fe-Mo catalyst particles influences catalyst formation, and we investigate the role of Mo concentration and catalyst particle size in this process. Finally, we apply the same modeling approach to other prominent bimetallic catalysts and suggest that this technique can be a powerful tool to understand and manipulate catalyst design for highly efficient carbon nanotube growth

  2. Development of Molecular Catalysts to Bridge the Gap between Heterogeneous and Homogeneous Catalysts

    Science.gov (United States)

    Ye, Rong

    Catalysts, heterogeneous, homogeneous, and enzymatic, are comprised of nanometer-sized inorganic and/or organic components. They share molecular factors including charge, coordination, interatomic distance, bonding, and orientation of catalytically active atoms. By controlling the governing catalytic components and molecular factors, catalytic processes of a multichannel and multiproduct nature could be run in all three catalytic platforms to create unique end-products. Unifying the fields of catalysis is the key to achieving the goal of 100% selectivity in catalysis. Recyclable catalysts, especially those that display selective reactivity, are vital for the development of sustainable chemical processes. Among available catalyst platforms, heterogeneous catalysts are particularly well-disposed toward separation from the reaction mixture via filtration methods, which renders them readily recyclable. Furthermore, heterogeneous catalysts offer numerous handles - some without homogeneous analogues - for performance and selectivity optimization. These handles include nanoparticle size, pore profile of porous supports, surface ligands and interface with oxide supports, and flow rate through a solid catalyst bed. Despite these available handles, however, conventional heterogeneous catalysts are themselves often structurally heterogeneous compared to homogeneous catalysts, which complicates efforts to optimize and expand the scope of their reactivity and selectivity. Ongoing efforts are aimed to address the above challenge by heterogenizing homogeneous catalysts, which can be defined as the modification of homogeneous catalysts to render them in a separable (solid) phase from the starting materials and products. Specifically, we grow the small nanoclusters in dendrimers, a class of uniform polymers with the connectivity of fractal trees and generally radial symmetry. Thanks to their dense multivalency, shape persistence and structural uniformity, dendrimers have proven to

  3. Synthesis of a molecularly defined single-active site heterogeneous catalyst for selective oxidation of N-heterocycles.

    Science.gov (United States)

    Zhang, Yujing; Pang, Shaofeng; Wei, Zhihong; Jiao, Haijun; Dai, Xingchao; Wang, Hongli; Shi, Feng

    2018-04-13

    Generally, a homogeneous catalyst exhibits good activity and defined active sites but it is difficult to recycle. Meanwhile, a heterogeneous catalyst can easily be reused but its active site is difficult to reveal. It is interesting to bridge the gap between homogeneous and heterogeneous catalysis via controllable construction of a heterogeneous catalyst containing defined active sites. Here, we report that a molecularly defined, single-active site heterogeneous catalyst has been designed and prepared via the oxidative polymerization of maleimide derivatives. These polymaleimide derivatives can be active catalysts for the selective oxidation of heterocyclic compounds to quinoline and indole via the recycling of -C=O and -C-OH groups, which was confirmed by tracing the reaction with GC-MS using maleimide as the catalyst and by FT-IR analysis with polymaleimide as the catalyst. These results might promote the development of heterogeneous catalysts with molecularly defined single active sites exhibiting a comparable activity to homogeneous catalysts.

  4. Designing the molecular future

    OpenAIRE

    Schneider Gisbert

    2011-01-01

    Approximately 25 years ago the first computer applications were conceived for the purpose of automated 'de novo' drug design prominent pioneering tools being ALADDIN CAVEAT GENOA and DYLOMMS. Many of these early concepts were enabled by innovative techniques for ligand receptor interaction modeling like GRID MCSS DOCK and CoMFA which still provide the theoretical framework for several more recently developed molecular design algorithms. After a first wave of software tools and groundbreaking ...

  5. Design of sintering-stable heterogeneous catalysts

    DEFF Research Database (Denmark)

    Gallas-Hulin, Agata

    One of the major issues in the use of metal nanoparticles in heterogeneous catalysis is sintering. Sintering occurs at elevated temperatures because of increased mobility of nanoparticles, leading to their agglomeration and, as a consequence, to the deactivation of the catalyst. It is an emerging...... problem especially for the noble metals-based catalysis. These metals being expensive and scarce, it is worth developing catalyst systems which preserve their activity over time. Encapsulation of nanoparticles inside zeolites is one of the ways to prevent sintering. Entrapment of nanoparticles inside...

  6. Design criteria for stable Pt/C fuel cell catalysts

    Directory of Open Access Journals (Sweden)

    Josef C. Meier

    2014-01-01

    Full Text Available Platinum and Pt alloy nanoparticles supported on carbon are the state of the art electrocatalysts in proton exchange membrane fuel cells. To develop a better understanding on how material design can influence the degradation processes on the nanoscale, three specific Pt/C catalysts with different structural characteristics were investigated in depth: a conventional Pt/Vulcan catalyst with a particle size of 3–4 nm and two Pt@HGS catalysts with different particle size, 1–2 nm and 3–4 nm. Specifically, Pt@HGS corresponds to platinum nanoparticles incorporated and confined within the pore structure of the nanostructured carbon support, i.e., hollow graphitic spheres (HGS. All three materials are characterized by the same platinum loading, so that the differences in their performance can be correlated to the structural characteristics of each material. The comparison of the activity and stability behavior of the three catalysts, as obtained from thin film rotating disk electrode measurements and identical location electron microscopy, is also extended to commercial materials and used as a basis for a discussion of general fuel cell catalyst design principles. Namely, the effects of particle size, inter-particle distance, certain support characteristics and thermal treatment on the catalyst performance and in particular the catalyst stability are evaluated. Based on our results, a set of design criteria for more stable and active Pt/C and Pt-alloy/C materials is suggested.

  7. Molecular heterogeneous catalysts derived from bipyridine-based organosilica nanotubes for C-H bond activation.

    Science.gov (United States)

    Zhang, Shengbo; Wang, Hua; Li, Mei; Han, Jinyu; Liu, Xiao; Gong, Jinlong

    2017-06-01

    Heterogeneous metal complex catalysts for direct C-H activation with high activity and durability have always been desired for transforming raw materials into feedstock chemicals. This study described the design and synthesis of one-dimensional organosilica nanotubes containing 2,2'-bipyridine (bpy) ligands in the framework (BPy-NT) and their post-synthetic metalation to provide highly active and robust molecular heterogeneous catalysts. By adjusting the ratios of organosilane precursors, very short BPy-NT with ∼50 nm length could be controllably obtained. The post-synthetic metalation of bipyridine-functionalized nanotubes with [IrCp*Cl(μ-Cl)] 2 (Cp* = η 5 -pentamethylcyclopentadienyl) and [Ir(cod)(OMe)] 2 (cod = 1,5-cyclooctadiene) afforded solid catalysts, IrCp*-BPy-NT and Ir(cod)-BPy-NT, which were utilized for C-H oxidation of heterocycles and cycloalkanes as well as C-H borylation of arenes. The cut-short nanotube catalysts displayed enhanced activities and durability as compared to the analogous homogeneous catalysts and other conventional heterogeneous catalysts, benefiting from the isolated active sites as well as the fast transport of substrates and products. After the reactions, a detailed characterization of Ir-immobilized BPy-NT via TEM, SEM, nitrogen adsorption, UV/vis, XPS, and 13 C CP MAS NMR indicated the molecular nature of the active species as well as stable structures of nanotube scaffolds. This study demonstrates the potential of BPy-NT with a short length as an integration platform for the construction of efficient heterogeneous catalytic systems for organic transformations.

  8. Catalyst design for clean and efficient fuels

    DEFF Research Database (Denmark)

    Šaric, Manuel

    cobalt promoted MoS2 catalyst. Reactivity of a series of model molecules, found in oil prior to desulfurization, is studied on cobalt promoted MoS2. Such an approach has the potential to explain the underlying processes involved in the removal of sulfur at each specific site of the catalyst. The goal...... is to identify which sites are active towards specific molecules and in getting insight to what the ideal catalyst should look like in terms of morphology. Dimethyl carbonate is an environmentally benign compound that can be used as a solvent and precursor in chemical synthesis or as a fuel and fuel additive...... processes currently used. It is found that noble metals can be used as electrocatalysts for the synthesis of dimethyl carbonate, significantly lowering the potential when using copper instead of gold. Besides being active, copper was found to be selective towards dimethyl carbonate. A non-selective catalyst...

  9. Design of porous nanostructured solid catalysts

    DEFF Research Database (Denmark)

    Abildstrøm, Jacob Oskar

    cells, as a mean to transform chemical as the main technique explained. The chapter will also cover degradation mechanisms of the catalyst employed in PEMFC, such as carbon corrosion and particle agglomeration. Strategies on how to increase resistance towards these degradation mechanisms...

  10. Chemical Posttranslational Modification with Designed Rhodium(II) Catalysts.

    Science.gov (United States)

    Martin, S C; Minus, M B; Ball, Z T

    2016-01-01

    Natural enzymes use molecular recognition to perform exquisitely selective transformations on nucleic acids, proteins, and natural products. Rhodium(II) catalysts mimic this selectivity, using molecular recognition to allow selective modification of proteins with a variety of functionalized diazo reagents. The rhodium catalysts and the diazo reactivity have been successfully applied to a variety of protein folds, the chemistry succeeds in complex environments such as cell lysate, and a simple protein blot method accurately assesses modification efficiency. The studies with rhodium catalysts provide a new tool to study and probe protein-binding events, as well as a new synthetic approach to protein conjugates for medical, biochemical, or materials applications. © 2016 Elsevier Inc. All rights reserved.

  11. Design of a surface alloy catalyst for steam reforming

    DEFF Research Database (Denmark)

    Besenbacher, F.; Chorkendorff, Ib; Clausen, B.S.

    1998-01-01

    Detailed studies of elementary chemical processes on well-characterized single crystal surfaces have contributed substantially to the understanding of heterogeneous catalysis. insight into the structure of surface alloys combined with an understanding of the relation between the surface compositi...... and reactivity is shown to lead directly to new ideas for catalyst design, The feasibility of such an approach is illustrated by the synthesis, characterization, and tests of a high-surface area gold-nickel catalyst for steam reforming....

  12. An artificial molecular machine that builds an asymmetric catalyst

    Science.gov (United States)

    De Bo, Guillaume; Gall, Malcolm A. Y.; Kuschel, Sonja; De Winter, Julien; Gerbaux, Pascal; Leigh, David A.

    2018-05-01

    Biomolecular machines perform types of complex molecular-level tasks that artificial molecular machines can aspire to. The ribosome, for example, translates information from the polymer track it traverses (messenger RNA) to the new polymer it constructs (a polypeptide)1. The sequence and number of codons read determines the sequence and number of building blocks incorporated into the biomachine-synthesized polymer. However, neither control of sequence2,3 nor the transfer of length information from one polymer to another (which to date has only been accomplished in man-made systems through template synthesis)4 is easily achieved in the synthesis of artificial macromolecules. Rotaxane-based molecular machines5-7 have been developed that successively add amino acids8-10 (including β-amino acids10) to a growing peptide chain by the action of a macrocycle moving along a mono-dispersed oligomeric track derivatized with amino-acid phenol esters. The threaded macrocycle picks up groups that block its path and links them through successive native chemical ligation reactions11 to form a peptide sequence corresponding to the order of the building blocks on the track. Here, we show that as an alternative to translating sequence information, a rotaxane molecular machine can transfer the narrow polydispersity of a leucine-ester-derivatized polystyrene chain synthesized by atom transfer radical polymerization12 to a molecular-machine-made homo-leucine oligomer. The resulting narrow-molecular-weight oligomer folds to an α-helical secondary structure13 that acts as an asymmetric catalyst for the Juliá-Colonna epoxidation14,15 of chalcones.

  13. Templating Routes to Supported Oxide Catalysts by Design

    Energy Technology Data Exchange (ETDEWEB)

    Notestein, Justin M. [Northwestern Univ., Evanston, IL (United States)

    2016-09-08

    The rational design and understanding of supported oxide catalysts requires at least three advancements, in order of increasing complexity: the ability to quantify the number and nature of active sites in a catalytic material, the ability to place external controls on the number and structure of these active sites, and the ability to assemble these active sites so as to carry out more complex functions in tandem. As part of an individual investigator research program that is integrated with the Northwestern University Institute for Catalysis in Energy Processes (ICEP) as of 2015, significant advances were achieved in these three areas. First, phosphonic acids were utilized in the quantitative assessment of the number of active and geometrically-available sites in MOx-SiO2 catalysts, including nanocrystalline composites, co-condensed materials, and grafted structures, for M=Ti, Zr, Hf, Nb, and Ta. That work built off progress in understanding supported Fe, Cu, and Co oxide catalysts from chelating and/or multinuclear precursors to maximize surface reactivity. Secondly, significant progress was made in the new area of using thin oxide overcoats containing ‘nanocavities’ from organic templates as a method to control the dispersion and thermal stability of subsequently deposited metal nanoparticles or other catalytic domains. Similar methods were used to control surface reactivity in SiO2-Al2O3 acid catalysts and to control reactant selectivity in Al2O3-TiO2 photocatalysts. Finally, knowledge gained from the first two areas has been combined to synthesize a tandem catalyst for hydrotreating reactions and an orthogonal tandem catalyst system where two subsequent reactions in a reaction network are independently controlled by light and heat. Overall, work carried out under this project significantly advanced the knowledge of synthesis-structure-function relationships in supported

  14. Design Innovation Catalysts: Education and Impact

    Directory of Open Access Journals (Sweden)

    Cara Wrigley

    Full Text Available Organizations globally look to design to help them innovate, differentiate, and compete in a changing economic climate. Consequently, design is increasingly being regarded as a dynamic and central tactical business resource. Considering this, the question is raised: how can the specific knowledge and skills of designers be better articulated, understood, implemented, and valued as core components of strategic innovation in businesses? In seeking to answer this question, this paper proposes a new frontier for the design profession, coined the “Design Innovation Catalyst” (DIC. This paper reflects on both extant literature and the teaching of seven DICs embedded in industry, conducting innovation projects run over a twelve to twenty-four month period. This paper reports on a unique set of six capabilities analyzed as being not only essential for the implementation of design-led innovation, but of great assistance in overcoming its associated challenges. This paper outlines the role of these new design professionals, and discusses the value these novel capabilities provide organizations through employing DICs. Furthermore, questions surrounding how designers will develop these new capabilities, and how the design-led innovation framework in application can contribute to the future of design will also be presented.

  15. Catalyst design for enhanced sustainability through fundamental surface chemistry.

    Science.gov (United States)

    Personick, Michelle L; Montemore, Matthew M; Kaxiras, Efthimios; Madix, Robert J; Biener, Juergen; Friend, Cynthia M

    2016-02-28

    Decreasing energy consumption in the production of platform chemicals is necessary to improve the sustainability of the chemical industry, which is the largest consumer of delivered energy. The majority of industrial chemical transformations rely on catalysts, and therefore designing new materials that catalyse the production of important chemicals via more selective and energy-efficient processes is a promising pathway to reducing energy use by the chemical industry. Efficiently designing new catalysts benefits from an integrated approach involving fundamental experimental studies and theoretical modelling in addition to evaluation of materials under working catalytic conditions. In this review, we outline this approach in the context of a particular catalyst-nanoporous gold (npAu)-which is an unsupported, dilute AgAu alloy catalyst that is highly active for the selective oxidative transformation of alcohols. Fundamental surface science studies on Au single crystals and AgAu thin-film alloys in combination with theoretical modelling were used to identify the principles which define the reactivity of npAu and subsequently enabled prediction of new reactive pathways on this material. Specifically, weak van der Waals interactions are key to the selectivity of Au materials, including npAu. We also briefly describe other systems in which this integrated approach was applied. © 2016 The Author(s).

  16. Coupling molecular catalysts with nanostructured surfaces for efficient solar fuel production

    Science.gov (United States)

    Jin, Tong

    Solar fuel generation via carbon dioxide (CO2) reduction is a promising approach to meet the increasing global demand for energy and to minimize the impact of energy consumption on climate change. However, CO2 is thermodynamically stable; its activation often requires the use of appropriate catalysts. In particular, molecular catalysts with well-defined structures and tunability have shown excellent activity in photochemical CO2 reduction. These homogenous catalysts, however, suffer from poor stability under photochemical conditions and difficulty in recycling from the reaction media. Heterogenized molecular catalysts, particularly those prepared by coupling molecular catalysts with solid-state surfaces, have attracted more attention in recent years as potential solutions to address the issues associated with molecular catalysts. In this work, solar CO2 reduction is investigated using systems coupling molecular catalysts with robust nanostructured surfaces. In Chapter 2, heterogenization of macrocyclic cobalt(III) and nickel (II) complexes on mesoporous silica surface was achieved by different methods. Direct ligand derivatization significantly lowered the catalytic activity of Co(III) complex, while grafting the Co(III) complex onto silica surface through Si-O-Co linkage resulted in hybrid catalysts with excellent activity in CO2 reduction in the presence of p-terphenyl as a molecular photosensitizer. An interesting loading effect was observed, in which the optimal activity was achieved at a medium Co(III) surface density. Heterogenization of the Ni(II) complex on silica surface has also been implemented, the poor photocatalytic activity of the hybrid catalyst can be attributed to the intrinsic nature of the homogeneous analogue. This study highlighted the importance of appropriate linking strategies in preparing functional heterogenized molecular catalysts. Coupling molecular complexes with light-harvesting surfaces could avoid the use of expensive molecular

  17. Oxidations of amines with molecular oxygen using bifunctional gold–titania catalysts

    DEFF Research Database (Denmark)

    Klitgaard, Søren Kegnæs; Egeblad, Kresten; Mentzel, Uffe Vie

    2008-01-01

    –titania catalysts can be employed to facilitate the oxidation of amines into amides with high selectivity. Furthermore, we report that pure titania is in fact itself a catalyst for the oxidation of amines with molecular oxygen under very mild conditions. We demonstrate that these new methodologies open up for two......Over the past decades it has become clear that supported gold nanoparticles are surprisingly active and selective catalysts for several green oxidation reactions of oxygen-containing hydrocarbons using molecular oxygen as the stoichiometric oxidant. We here report that bifunctional gold...

  18. Catalysis Science Initiative: Catalyst Design by Discovery Informatics

    Energy Technology Data Exchange (ETDEWEB)

    Delgass, William Nicholas [Purdue Univ., West Lafayette, IN (United States). Chemical Engineering; Abu-Omar, Mahdi [Purdue Univ., West Lafayette, IN (United States) Department of Chemistry; Caruthers, James [Purdue Univ., West Lafayette, IN (United States). Chemical Engineering; Ribeiro, Fabio [Purdue Univ., West Lafayette, IN (United States). Chemical Engineering; Thomson, Kendall [Purdue Univ., West Lafayette, IN (United States). Chemical Engineering; Schneider, William [Univ. of Notre Dame, IN (United States)

    2016-07-08

    Catalysts selectively enhance the rates of chemical reactions toward desired products. Such reactions provide great benefit to society in major commercial sectors such as energy production, protecting the environment, and polymer products and thereby contribute heavily to the country’s gross national product. Our premise is that the level of fundamental understanding of catalytic events at the atomic and molecular scale has reached the point that more predictive methods can be developed to shorten the cycle time to new processes. The field of catalysis can be divided into two regimes: heterogeneous and homogeneous. For the heterogeneous catalysis regime, we have used the water-gas shift (WGS) reaction (CO + H2O + CO2 + H2O) over supported metals as a test bed. Detailed analysis and strong coupling of theory with experiment have led to the following conclusions: • The sequence of elementary steps goes through a COOH intermediate • The CO binding energy is a strong function of coverage of CO adsorbed on the surface in many systems • In the case of Au catalysts, the CO adsorption is generally too weak on surface with close atomic packing, but the enhanced binding at corner atoms (which are missing bonding partners) of cubo-octahedral nanoparticles increases the energy to a near optimal value and produces very active catalysts. • Reaction on the metal alone cannot account for the experimental results. The reaction is dual functional with water activation occurring at the metal-support interface. It is clear from our work that the theory component is essential, not only for prediction of new systems, but also for reconciling data and testing hypotheses regarding potential descriptors. Particularly important is the finding that the interface between nano-sized metal particles and the oxides that are used to support them represent a new state of matter in the sense that the interfacial bonding perturbs the chemical state of both metals atoms and the support

  19. Synthesis of cerium oxide catalysts supported on MCM-41 molecular sieve

    International Nuclear Information System (INIS)

    Souza, E.L.S.; Barros, T.R.B.; Sousa, B.V. de

    2016-01-01

    Porous materials have been widely studied as catalysts and catalyst support. The MCM-41 structure is the one that has been most studied because of its application possibilities in chemical processes. This work aimed to obtain and characterize cerium oxide catalysts supported on MCM-41 molecular sieve. The molecular sieve was synthesized by the conventional method with the following molar composition: 1 SiO2: 0.30 CTABr: NH3 11: 144 H2O. Then, 25% w/w cerium was incorporated into the MCM-41 using the wet impregnation process and the material obtained was activated by calcination. From the XRD patterns was confirmed the structure of the molecular sieve, and were identified the cerium oxide phases in its structure. The textural catalysts characteristics were investigated by isotherms of N2 adsorption/desorption (BET method). (author)

  20. The role of reticular chemistry in the design of CO2 reduction catalysts

    Science.gov (United States)

    Diercks, Christian S.; Liu, Yuzhong; Cordova, Kyle E.; Yaghi, Omar M.

    2018-02-01

    The problem with current state-of-the-art catalysts for CO2 photo- or electroreduction is rooted in the notion that no single system can independently control, and thus optimize, the interplay between activity, selectivity and efficiency. At its core, reticular chemistry is recognized for its ability to control, with atomic precision, the chemical and structural features (activity and selectivity) as well as the output optoelectronic properties (efficiency) of porous, crystalline materials. The molecular building blocks that are in a reticular chemist's toolbox are chosen in such a way that the structures are rationally designed, framework chemistry is performed to integrate catalytically active components, and the manner in which these building blocks are connected endows the material with the desired optoelectronic properties. The fact that these aspects can be fine-tuned independently lends credence to the prospect of reticular chemistry contributing to the design of next-generation CO2 reduction catalysts.

  1. Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts.

    Science.gov (United States)

    Easter, Quinn T; Blum, Suzanne A

    2018-02-05

    Catalytic cycles are typically depicted as possessing time-invariant steps with fixed rates. Yet the true behavior of individual catalysts with respect to time is unknown, hidden by the ensemble averaging inherent to bulk measurements. Evidence is presented for variable chemical kinetics at individual catalysts, with a focus on ring-opening metathesis polymerization catalyzed by the second-generation Grubbs' ruthenium catalyst. Fluorescence microscopy is used to probe the chemical kinetics of the reaction because the technique possesses sufficient sensitivity for the detection of single chemical reactions. Insertion reactions in submicron regions likely occur at groups of many (not single) catalysts, yet not so many that their unique kinetic behavior is ensemble averaged. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. De novo molecular design

    CERN Document Server

    Schneider, Gisbert

    2013-01-01

    Systematically examining current methods and strategies, this ready reference covers a wide range of molecular structures, from organic-chemical drugs to peptides, Proteins and nucleic acids, in line with emerging new drug classes derived from biomacromolecules. A leader in the field and one of the pioneers of this young discipline has assembled here the most prominent experts from across the world to provide first-hand knowledge. While most of their methods and examples come from the area of pharmaceutical discovery and development, the approaches are equally applicable for chemical probes an

  3. Highly efficient bioinspired molecular Ru water oxidation catalysts with negatively charged backbone ligands.

    Science.gov (United States)

    Duan, Lele; Wang, Lei; Li, Fusheng; Li, Fei; Sun, Licheng

    2015-07-21

    The oxygen evolving complex (OEC) of the natural photosynthesis system II (PSII) oxidizes water to produce oxygen and reducing equivalents (protons and electrons). The oxygen released from PSII provides the oxygen source of our atmosphere; the reducing equivalents are used to reduce carbon dioxide to organic products, which support almost all organisms on the Earth planet. The first photosynthetic organisms able to split water were proposed to be cyanobacteria-like ones appearing ca. 2.5 billion years ago. Since then, nature has chosen a sustainable way by using solar energy to develop itself. Inspired by nature, human beings started to mimic the functions of the natural photosynthesis system and proposed the concept of artificial photosynthesis (AP) with the view to creating energy-sustainable societies and reducing the impact on the Earth environments. Water oxidation is a highly energy demanding reaction and essential to produce reducing equivalents for fuel production, and thereby effective water oxidation catalysts (WOCs) are required to catalyze water oxidation and reduce the energy loss. X-ray crystallographic studies on PSII have revealed that the OEC consists of a Mn4CaO5 cluster surrounded by oxygen rich ligands, such as oxyl, oxo, and carboxylate ligands. These negatively charged, oxygen rich ligands strongly stabilize the high valent states of the Mn cluster and play vital roles in effective water oxidation catalysis with low overpotential. This Account describes our endeavors to design effective Ru WOCs with low overpotential, large turnover number, and high turnover frequency by introducing negatively charged ligands, such as carboxylate. Negatively charged ligands stabilized the high valent states of Ru catalysts, as evidenced by the low oxidation potentials. Meanwhile, the oxygen production rates of our Ru catalysts were improved dramatically as well. Thanks to the strong electron donation ability of carboxylate containing ligands, a seven

  4. Modeling of molecular weight and molecular weight distribution in slurry polymerization of propylene by Ziegler-Natta catalysts

    International Nuclear Information System (INIS)

    Khorasani, R.; Pourmahdian, S.

    2007-01-01

    The Precise prediction of polypropylene synthesized by heterogeneous Ziegler-Natta catalysts needs good knowledge of parameters affecting on polymerization. molecular weight and molecular weight distribution are among important characteristics of a polymer determining physical-mechanical properties. broadening of molecular weight distribution is an important and well known characteristic of polypropylene synthesized by heterogeneous Ziegler-Natta catalysts, So it is important to understand the origin of broad molecular weight. Two main factors in broadening molecular weight, namely mass transfer resistances and multiplicity of active sites, are discussed in this paper and a model including these factors is presented. Then we calculate molecular weight and molecular weight distribution by the model and compare our results with

  5. From fundamental studies of reactivity on single crystals to the design of catalysts

    Science.gov (United States)

    H. Larsen, Jane; Chorkendorff, Ib

    One of the prominent arguments for performing surface science studies have for many years been to improve and design new and better catalysts. Although surface science has provided the fundamental framework and tools for understanding heterogeneous catalysis until now there have been extremely few examples of actually designing new catalysts based solely on surface science studies. In this review, we shall demonstrate how a close collaboration between different fundamental disciplines like structural-, theoretical-and reactivity-studies of surfaces as well as a strong interaction with industry can have strong synergetic effects and how this was used to develop a new catalyst. As so often before the studies reviewed here were not initiated with the objective to solve a specific problem, but realizing that a new class of very stable two-dimensional alloys could be synthesized from otherwise immiscible metals made it possible to present a new solution to a specific problem in the industrial catalysis relating to methane activation in the steam reforming process. Methane is the main constituent of natural gas and it is an extremely important raw material for many large scale chemical processes such as production of hydrogen, ammonia, and methanol. In the steam reforming process methane and water are converted into a mixture of mainly hydrogen and carbon monoxide, the so-called synthesis gas. Industrially the steam reforming process usually takes place over a catalyst containing small nickel crystallites highly dispersed on a porous support material like aluminum/magnesium oxides in order to achieve a high active metal area. There is a general consensus that the rate limiting step of this process is the dissociative sticking of methane on the nickel surface. Driven by the desire to understand this step and hopefully be able to manipulate the reactivity, a large number of investigations of the methane/nickel interaction have been performed using nickel single crystals as

  6. Designing Pd-based supported bimetallic catalysts for environmental applications

    OpenAIRE

    Nowicka, Ewa; Meenakshisundaram, Sankar

    2018-01-01

    Supported bimetallic nanoparticulate catalysts are an important class of heterogeneous catalysts for many reactions including selective oxidation, hydrogenation/hydrogenolysis, reforming, biomass conversion reactions, and many more. The activity, selectivity, and stability of these catalysts depend on their structural features including particle size, composition, and morphology. In this review, we present important structural features relevant to supported bimetallic catalysts focusing on Pd...

  7. Design, synthesis, and characterization of novel fine-particle, unsupported catalysts for coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Klein, M.T.

    1991-12-30

    The purpose of this work is to investigate the kinetics-assisted design, synthesis and characterization of fme-pardcle, unsupported catalysts for coal liquefaction. The goal is to develop a fundamental understanding of coal catalysis and catalysts that will, in turn, allow for the specification of a novel optimal catalyst for coal liquefaction.

  8. Pharmaceutical structure montages as catalysts for design and discovery.

    Science.gov (United States)

    Njarðarson, Jon T

    2012-05-01

    Majority of pharmaceuticals are small molecule organic compounds. Their structures are most effectively described and communicated using the graphical language of organic chemistry. A few years ago we decided to harness this powerful language to create new educational tools that could serve well for data mining and as catalysts for discovery. The results were the Top 200 drug posters, which we have posted online for everyone to enjoy and update yearly. This article details the origin and motivation for our design and highlights the value of this graphical format by presenting and analyzing a new pharmaceutical structure montage (poster) focused on US FDA approved drugs in 2011.

  9. Silica-supported, single-site titanium catalysts for olefin epoxidation. A molecular precursor strategy for control of catalyst structure.

    Science.gov (United States)

    Jarupatrakorn, Jonggol; Don Tilley, T

    2002-07-17

    A molecular precursor approach involving simple grafting procedures was used to produce site-isolated titanium-supported epoxidation catalysts of high activity and selectivity. The tris(tert-butoxy)siloxy titanium complexes Ti[OSi(O(t)Bu)(3)](4) (TiSi4), ((i)PrO)Ti[OSi(O(t)Bu)(3)](3) (TiSi3), and ((t)BuO)(3)TiOSi(O(t)Bu)(3) (TiSi) react with the hydroxyl groups of amorphous Aerosil, mesoporous MCM-41, and SBA-15 via loss of HO(t)Bu and/or HOSi(O(t)Bu)(3) and introduction of titanium species onto the silica surface. Powder X-ray diffraction, nitrogen adsorption/desorption, infrared, and diffuse reflectance ultraviolet spectroscopies were used to investigate the structures and chemical natures of the surface-bound titanium species. The titanium species exist mainly in isolated, tetrahedral coordination environments. Increasing the number of siloxide ligands in the molecular precursor decreases the amount of titanium that can be introduced this way, but also enhances the catalytic activity and selectivity for the epoxidation of cyclohexene with cumene hydroperoxide as oxidant. In addition, the high surface area mesoporous silicas (MCM-41 and SBA-15) are more effective than amorphous silica as supports for these catalysts. Supporting TiSi3 on the SBA-15 affords highly active cyclohexene epoxidation catalysts (0.25-1.77 wt % Ti loading) that provide turnover frequencies (TOFs) of 500-1500 h(-1) after 1 h (TOFs are reduced by about half after calcination). These results demonstrate that oxygen-rich siloxide complexes of titanium are useful as precursors to supported epoxidation catalysts.

  10. Intracellular Chemistry: Integrating Molecular Inorganic Catalysts with Living Systems.

    Science.gov (United States)

    Ngo, Anh H; Bose, Sohini; Do, Loi H

    2018-03-23

    This concept article focuses on the rapid growth of intracellular chemistry dedicated to the integration of small-molecule metal catalysts with living cells and organisms. Although biological systems contain a plethora of biomolecules that can deactivate inorganic species, researchers have shown that small-molecule metal catalysts could be engineered to operate in heterogeneous aqueous environments. Synthetic intracellular reactions have recently been reported for olefin hydrogenation, hydrolysis/oxidative cleavage, azide-alkyne cycloaddition, allylcarbamate cleavage, C-C bond cross coupling, and transfer hydrogenation. Other promising targets for new biocompatible reaction discovery will also be discussed, with a special emphasis on how such innovations could lead to the development of novel technologies and chemical tools. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Optimal catalyst curves: Connecting density functional theory calculations with industrial reactor design and catalyst selection

    DEFF Research Database (Denmark)

    Jacobsen, C.J.H.; Dahl, Søren; Boisen, A.

    2002-01-01

    For ammonia synthesis catalysts a volcano-type relationship has been found experimentally. We demonstrate that by combining density functional theory calculations with a microkinetic model the position of the maximum of the volcano curve is sensitive to the reaction conditions. The catalytic...... ammonia synthesis activity, to a first approximation, is a function only of the binding energy of nitrogen to the catalyst. Therefore, it is possible to evaluate which nitrogen binding energy is optimal under given reaction conditions. This leads to the concept of optimal catalyst curves, which illustrate...... the nitrogen binding energies of the optimal catalysts at different temperatures, pressures, and synthesis gas compositions. Using this concept together with the ability to prepare catalysts with desired binding energies it is possible to optimize the ammonia process. In this way a link between first...

  12. Hoveyda–Grubbs first generation type catalyst immobilized on mesoporous molecular sieves

    Czech Academy of Sciences Publication Activity Database

    Pastva, Jakub; Čejka, Jiří; Žilková, Naděžda; Mestek, O.; Rangus, M.; Balcar, Hynek

    2013-01-01

    Roč. 378, NOV 2013 (2013), s. 184-192 ISSN 1381-1169 R&D Projects: GA AV ČR IAA400400805 Institutional support: RVO:61388955 Keywords : Hoveyda–Grubbs type catalysts * Olefin metathesis * Mesoporous molecular sieves Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.679, year: 2013

  13. 08-ERD-071 Final Report: New Molecular Probes and Catalysts for Bioenergy Research

    Energy Technology Data Exchange (ETDEWEB)

    Thelen, M P; Rowe, A A; Siebers, A K; Jiao, Y

    2011-03-07

    A major thrust in bioenergy research is to develop innovative methods for deconstructing plant cell wall polymers, such as cellulose and lignin, into simple monomers that can be biologically converted to ethanol and other fuels. Current techniques for monitoring a broad array of cell wall materials and specific degradation products are expensive and time consuming. To monitor various polymers and assay their breakdown products, molecular probes for detecting specific carbohydrates and lignins are urgently needed. These new probes would extend the limited biochemical techniques available, and enable realtime imaging of ultrastructural changes in plant cells. Furthermore, degradation of plant biomass could be greatly accelerated by the development of catalysts that can hydrolyze key cell wall polysaccharides and lignin. The objective of this project was to develop cheap and efficient DNA reagents (aptamers) used to detect and quantify polysaccharides, lignin, and relevant products of their breakdown. A practical goal of the research was to develop electrochemical aptamer biosensors, which could be integrated into microfluidic devices and used for high-throughput screening of enzymes or biological systems that degrade biomass. Several important model plant cell wall polymers and compounds were targeted for specific binding and purification of aptamers, which were then tested by microscopic imaging, circular dichroism, surface plasmon resonance, fluorescence anisotropy, and electrochemical biosensors. Using this approach, it was anticiated that we could provide a basis for more efficient and economically viable biofuels, and the technologies established could be used to design molecular tools that recognize targets sought in medicine or chemical and biological defense projects.

  14. Visible-light-driven methane formation from CO2 with a molecular iron catalyst

    Science.gov (United States)

    Rao, Heng; Schmidt, Luciana C.; Bonin, Julien; Robert, Marc

    2017-08-01

    Converting CO2 into fuel or chemical feedstock compounds could in principle reduce fossil fuel consumption and climate-changing CO2 emissions. One strategy aims for electrochemical conversions powered by electricity from renewable sources, but photochemical approaches driven by sunlight are also conceivable. A considerable challenge in both approaches is the development of efficient and selective catalysts, ideally based on cheap and Earth-abundant elements rather than expensive precious metals. Of the molecular photo- and electrocatalysts reported, only a few catalysts are stable and selective for CO2 reduction; moreover, these catalysts produce primarily CO or HCOOH, and catalysts capable of generating even low to moderate yields of highly reduced hydrocarbons remain rare. Here we show that an iron tetraphenylporphyrin complex functionalized with trimethylammonio groups, which is the most efficient and selective molecular electro- catalyst for converting CO2 to CO known, can also catalyse the eight-electron reduction of CO2 to methane upon visible light irradiation at ambient temperature and pressure. We find that the catalytic system, operated in an acetonitrile solution containing a photosensitizer and sacrificial electron donor, operates stably over several days. CO is the main product of the direct CO2 photoreduction reaction, but a two-pot procedure that first reduces CO2 and then reduces CO generates methane with a selectivity of up to 82 per cent and a quantum yield (light-to-product efficiency) of 0.18 per cent. However, we anticipate that the operating principles of our system may aid the development of other molecular catalysts for the production of solar fuels from CO2 under mild conditions.

  15. Toward Catalyst Design from Theoretical Calculations (464th Brookhaven Lecture)

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Ping (BNL Chemistry Dept)

    2010-12-15

    Catalysts have been used to speed up chemical reactions as long as yeast has been used to make bread rise. Today, catalysts are used everywhere from home kitchens to industrial chemical factories. In the near future, new catalysts being developed at Brookhaven Lab may be used to speed us along our roads and highways as they play a major role in solving the world’s energy challenges. During the lecture, Liu will discuss how theorists and experimentalists at BNL are working together to formulate and test new catalysts that could be used in real-life applications, such as hydrogen-fuel cells that may one day power our cars and trucks.

  16. [Synergetic effects of silicon carbide and molecular sieve loaded catalyst on microwave assisted catalytic oxidation of toluene].

    Science.gov (United States)

    Wang, Xiao-Hui; Bo, Long-Li; Liu, Hai-Nan; Zhang, Hao; Sun, Jian-Yu; Yang, Li; Cai, Li-Dong

    2013-06-01

    Molecular sieve loaded catalyst was prepared by impregnation method, microwave-absorbing material silicon carbide and the catalyst were investigated for catalytic oxidation of toluene by microwave irradiation. Research work examined effects of silicon carbide and molecular sieve loading Cu-V catalyst's mixture ratio as well as mixed approach changes on degradation of toluene, and characteristics of catalyst were measured through scanning electron microscope, specific surface area test and X-ray diffraction analysis. The result showed that the fixed bed reactor had advantages of both thermal storage property and low-temperature catalytic oxidation when 20% silicon carbide was filled at the bottom of the reactor, and this could effectively improve the utilization of microwave energy as well as catalytic oxidation efficiency of toluene. Under microwave power of 75 W and 47 W, complete-combustion temperatures of molecular sieve loaded Cu-V catalyst and Cu-V-Ce catalyst to toluene were 325 degrees C and 160 degrees C, respectively. Characteristics of the catalysts showed that mixture of rare-earth element Ce increased the dispersion of active components in the surface of catalyst, micropore structure of catalyst effectively guaranteed high adsorption capacity for toluene, while amorphous phase of Cu and V oxides increased the activity of catalyst greatly.

  17. Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts

    KAUST Repository

    Pelletier, Jeremie

    2016-03-09

    ConspectusHeterogeneous catalysis, a field important industrially and scientifically, is increasingly seeking and refining strategies to render itself more predictable. The main issue is due to the nature and the population of catalytically active sites. Their number is generally low to very low, their "acid strengths" or " redox properties" are not homogeneous, and the material may display related yet inactive sites on the same material. In many heterogeneous catalysts, the discovery of a structure-activity reationship is at best challenging. One possible solution is to generate single-site catalysts in which most, if not all, of the sites are structurally identical. Within this context and using the right tools, the catalyst structure can be designed and well-defined, to reach a molecular understanding. It is then feasible to understand the structure-activity relationship and to develop predictable heterogeneous catalysis. Single-site well-defined heterogeneous catalysts can be prepared using concepts and tools of surface organometallic chemistry (SOMC). This approach operates by reacting organometallic compounds with surfaces of highly divided oxides (or of metal nanoparticles). This strategy has a solid track record to reveal structure-activity relationship to the extent that it is becoming now quite predictable. Almost all elements of the periodical table have been grafted on surfaces of oxides (from simple oxides such as silica or alumina to more sophisticated materials regarding composition or porosity).Considering catalytic hydrocarbon transformations, heterogeneous catalysis outcome may now be predicted based on existing mechanistic proposals and the rules of molecular chemistry (organometallic, organic) associated with some concepts of surface sciences. A thorough characterization of the grafted metal centers must be carried out using tools spanning from molecular organometallic or surface chemistry. By selection of the metal, its ligand set, and the

  18. Mechanism-Based Design of Green Oxidation Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Rybak-Akimova, Elena [Tufts Univ., Medford, MA (United States)

    2015-03-16

    In modern era of scarce resources, developing chemical processes that can eventually generate useful materials and fuels from readily available, simple, cheap, renewable starting materials is of paramount importance. Small molecules, such as dioxygen, dinitrogen, water, or carbon dioxide, can be viewed as ideal sources of oxygen, nitrogen, or carbon atoms in synthetic applications. Living organisms perfected the art of utilizing small molecules in biosynthesis and in generating energy; photosynthesis, which couples carbohydrate synthesis from carbon dioxide with photocatalytic water splitting, is but one impressive example of possible catalytic processes. Small molecule activation in synthetic systems remains challenging, and current efforts are focused on developing catalytic reactions that can convert small molecules into useful building blocks for generating more complicated organic molecules, including fuels. Modeling nature is attractive in many respects, including the possibility to use non-toxic, earth-abundant metals in catalysis. Specific systems investigated in our work include biomimetic catalytic oxidations with dioxygen, hydrogen peroxide, and related oxygen atom donors. More recently, a new direction was been also pursued in the group, fixation of carbon dioxide with transition metal complexes. Mechanistic understanding of biomimetic metal-catalyzed oxidations is critical for the design of functional models of metalloenzymes, and ultimately for the rational synthesis of useful, selective and efficient oxidation catalysts utilizing dioxygen and hydrogen peroxide as terminal oxidants. All iron oxidases and oxygenases (both mononuclear and dinuclear) utilize metal-centered intermediates as reactive species in selective substrate oxidation. In contrast, free radical pathways (Fenton chemistry) are common for traditional inorganic iron compounds, producing hydroxyl radicals as very active, non-selective oxidants. Recent developments, however, changed this

  19. Molecular metal-Oxo catalysts for generating hydrogen from water

    Science.gov (United States)

    Long, Jeffrey R; Chang, Christopher J; Karunadasa, Hemamala I

    2015-02-24

    A composition of matter suitable for the generation of hydrogen from water is described, the positively charged cation of the composition having the general formula [(PY5W.sub.2)MO].sup.2+, wherein PY5W.sub.2 is (NC.sub.5XYZ)(NC.sub.5H.sub.4).sub.4C.sub.2W.sub.2, M is a transition metal, and W, X, Y, and Z can be H, R, a halide, CF.sub.3, or SiR.sub.3, where R can be an alkyl or aryl group. The two accompanying counter anions, in one embodiment, can be selected from the following Cl.sup.-, I.sup.-, PF.sub.6.sup.-, and CF.sub.3SO.sub.3.sup.-. In embodiments of the invention, water, such as tap water containing electrolyte or straight sea water can be subject to an electric potential of between 1.0 V and 1.4 V relative to the standard hydrogen electrode, which at pH 7 corresponds to an overpotential of 0.6 to 1.0 V, with the result being, among other things, the generation of hydrogen with an optimal turnover frequency of ca. 1.5 million mol H.sub.2/mol catalyst per h.

  20. Molecular modelling and radiopharmaceutical design

    International Nuclear Information System (INIS)

    Neves, M.; Gano, L.; Costa, M.C.; Raminhos, H.; Rosado, M.; Fausto, R.

    2002-01-01

    Aim: Among several headings for radiopharmaceuticals (RPs) design, molecular modelling (MM) could be used for the prediction of ligands and metal-complexes structures. Using MM it is also possible to simulate molecular interactions between predicted structures and specific biomolecules. Bisphosphonates (BPs) are ligands that are able to coordinate radioactive metals, such as 153 Sm, 166 Ho, 186 Re, etc., but they are all polymeric complexes difficult to characterize. It is reported that the bone uptake does not depend on the nature of metal center, but is primarily driven by the nature of the ligand, as in the case of HEDP-M (M= 99m Tc, 186 Re, 113 Sn). So, it would be interesting to estimate the relevant molecular properties of BPs by MM, simulate their interaction with hydroxyapatite (HAP) the main bone component, and then correlate the predicted molecular parameters with experimental data obtained from HAP binding and biodistribution studies of BPs carrying radioactive metals. Materials and Methods: The molecular structures and preferred conformations of BPs differing in the length of the aliphatic chain attached to their substituted amine groups (pami-dronate, olpadronate and ibandronate) were obtained using the second-generation CVFF 950 (version 1.01) force field of Hwang et al. Simulation of the interactions between the studied BPs and HAP were performed using a Cerius-2 system of programs running on a Silicon Graphics O2 workstation. BPs- 153 Sm complexes were synthesized and characterized by ITLC. Their binding to HAP and in vivo biodistribution studies were carried out as usual described in literature. Results: A direct correlation could be established between in vitro BPs affinity towards HAP and their corresponding energies from the Coulomb interactions involving the N and P atoms of the studied BPs bound to the HAP (0,0,1) surface and the nearest Ca atoms of HAP. The BPs- 153 Sm showing the highest binding to HAP and skeletal uptake are those which

  1. Kinetics assisted design of catalysts for coal liquefaction. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Klein, M.T.; Foley, H.C.; Calkins, W.H.; Scouten, C.

    1998-02-01

    The thermal and catalytic reactions of 4-(1-naphthylmethyl)bibenzyl (NBBM), a resid and coal model compound, were examined. Catalytic reaction of NBBM was carried out at 400 C under hydrogen with a series of transition metal-based catalytic materials including Fe(CO){sub 4}PPh{sub 3}, Fe(CO){sub 3}(PPh{sub 3}){sub 2}, Fe(CO){sub 2}(PPh{sub 3}){sub 2}CS{sub 2}, Fe(CO){sub 5}, Mo(CO){sub 6}, Mn{sub 2}(CO){sub 10}, Fe{sub 2}O{sub 3} and MoS{sub 2}. Experimental findings and derived mechanistic insights were organized into molecular-level reaction models for NBBM pyrolysis and catalysis. Hydropyrolysis and catalysis reaction families occurring during NBBM hydropyrolysis at 420 C were summarized in the form of reaction matrices which, upon exhaustive application to the components of the reacting system, yielded the mechanistic reaction model. Each reaction family also had an associated linear free energy relationship (LFER) which provided an estimate of the rate constant k{sub i} given a structural property of species i or its reaction. Including the catalytic reaction matrices with those for the pyrolysis model provided a comprehensive NBBM catalytic reaction model and allowed regression of fundamental LFER parameters for the catalytic reaction families. The model also allowed specification of the property of an optimal catalyst. Iron, molybdenum and palladium were predicted to be most effective for model compound consumption. Due to the low costs associated with iron and its disposal, it is a good choice for coal liquefaction catalysis and the challenge remains to synthesize small particles able to access the full surface area of the coal macromolecule.

  2. Grubbs Catalysts Immobilized on Mesoporous Molecular Sieves via Phosphine and Pyridine Linkers

    Czech Academy of Sciences Publication Activity Database

    Bek, David; Balcar, Hynek; Žilková, Naděžda; Zukal, Arnošt; Horáček, Michal; Čejka, Jiří

    2011-01-01

    Roč. 1, č. 7 (2011), s. 709-718 ISSN 2155-5435 R&D Projects: GA AV ČR IAA400400805; GA AV ČR KAN100400701; GA ČR GD203/08/H032 Institutional research plan: CEZ:AV0Z40400503 Keywords : Grubbs catalyst * mesoporous molecular sieves * olefin metathesis Subject RIV: CF - Physical ; Theoretical Chemistry

  3. Advanced technologies in biodiesel new advances in designed and optimized catalysts

    CERN Document Server

    Islam, Aminul

    2015-01-01

    The inadequacy of fossil fuel is the main driving force of the future sustainable energy around the world. Since heterogeneous catalysis is used in chemical industry for biodiesel production, achieving optimal catalytic performance is a significant issue for chemical engineers and chemists. Enormous attention has been placed in recent years on the selection of heterogeneous catalyst in biodiesel industry, where the catalyst could be facilitated highly selective toward desired products, easily handled, separated from the reaction medium, and subsequently reused. This book stresses an overview on the contributions of tailored solid acid and base catalysts to catalytic biodiesel synthesis, and the in uences of heterogeneous catalyst properties on biodiesel yield in order to develop a better understanding of catalyst design for the green production process as well as practical applications in the biodiesel industry.

  4. Hydrocarbon reforming catalysts and new reactor designs for compact hydrogen generators

    Energy Technology Data Exchange (ETDEWEB)

    Schaefer, A.; Schwab, E.; Urtel, H. [BASF SE, Ludwigshafen (Germany); Farrauto, R. [BASF Catalysts LLC, Iselin, NJ (United States)

    2010-12-30

    A hydrogen based future energy scenario will use fuel cells for the conversion of chemically stored energy into electricity. Depending upon the type of fuel cell, different specifications will apply for the feedstock which is converted in the cell, ranging from very clean hydrogen for PEM-FC's to desulfurized methane for SOFC and MCFC technology. For the foreseeable future, hydrogen will be supplied by conventional reforming, however operated in compact and dynamic reformer designs. This requires that known catalyst formulations are offered in specific geometries, giving flexibility for novel reactor design options. These specific geometries can be special tablet shapes as well as monolith structures. Finally, also nonhydrocarbon feedstock might be used in special applications, e.g. bio-based methanol and ethanol. BASF offers catalysts for the full process chain starting from feedstock desulfurization via reforming, high temperature shift, low temperature shift to CO fine polishing either via selective oxidation or selective methanation. Depending upon the customer's design, most stages can be served either with precious metal based monolith solutions or base metal tablet solutions. For the former, we have taken the automobile catalyst monolith support and extended its application to the fuel cell hydrogen generation. Washcoats of precious metal supported catalysts can for example be deposited on ceramic monoliths and/or metal heat exchangers for efficient generation of hydrogen. Major advantages are high through puts due to more efficient heat transfer for catalysts on metal heat exchangers, lower pressure drop with greater catalyst mechanical and thermal stability compared to particulate catalysts. Base metal tablet catalysts on the other hand can have intrinsic cost advantages, larger fractions of the reactor can be filled with active mass, and if produced in unconventional shape, again novel reactor designs are made possible. Finally, if it comes to

  5. Designing bifunctional alkene isomerization catalysts using predictive modelling

    NARCIS (Netherlands)

    Landman, I.R.; Paulson, E.R.; Rheingold, A.L.; Grotjahn, D.B.; Rothenberg, G.

    2017-01-01

    Controlling the isomerization of alkenes is important for the manufacturing of fuel additives, fine-chemicals and pharmaceuticals. But even if isomerization seems to be a simple unimolecular process, the factors that govern catalyst performance are far from clear. Here we present a set of models

  6. Macromolecular Architectures Designed by Living Radical Polymerization with Organic Catalysts

    Directory of Open Access Journals (Sweden)

    Miho Tanishima

    2014-01-01

    Full Text Available Well-defined diblock and triblock copolymers, star polymers, and concentrated polymer brushes on solid surfaces were prepared using living radical polymerization with organic catalysts. Polymerizations of methyl methacrylate, butyl acrylate, and selected functional methacrylates were performed with a monofunctional initiator, a difunctional initiator, a trifunctional initiator, and a surface-immobilized initiator.

  7. Preparation and application of zirconium sulfate supported on SAPO-34 molecular sieve as solid acid catalyst for esterification

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Dongyan, E-mail: xdy0156@sina.com; Ma, Hong; Cheng, Fei

    2014-05-01

    Graphical abstract: - Highlights: • SAPO-34 supported zirconium sulfate solid acid catalyst was prepared. • Esterification of acetic acid with ethanol can be catalyzed by ZS/SAPO-34. • The hydration of ZS is vital to the acidic property and catalytic performance. • The ZS/SAPO-34 catalyst treated at 200 °C shows good reusability. - Abstract: Zirconium sulfate (ZS) was supported on SAPO-34 molecular sieve by using an incipient wetness impregnation method with zirconium sulfate as the precursor. The as-prepared catalysts were used as solid acid catalyst for esterification reaction of acetic acid with ethanol. The influence of calcination temperature on the acidic property, catalytic activity, and reusability of ZS/SAPO-34 catalysts were mainly investigated. FT-IR, SEM, EDS and TG analysis have been carried out to demonstrate the characteristics of ZS/SAPO-34 catalysts. It was found that the 30 wt%ZS/SAPO-34 catalysts display the property of superacid irrespective of calcination temperature. The ZS/SAPO-34 catalyst treated at 200 °C can enhance the interaction between the supported ZS and SAPO-34 and keep the catalyst remaining substantially active after several reaction cycles. However, further increasing calcination temperature will cause the transfer of ZS from hydrate to anhydrous phase, and thus the decrease of activity.

  8. Preparation and application of zirconium sulfate supported on SAPO-34 molecular sieve as solid acid catalyst for esterification

    International Nuclear Information System (INIS)

    Xu, Dongyan; Ma, Hong; Cheng, Fei

    2014-01-01

    Graphical abstract: - Highlights: • SAPO-34 supported zirconium sulfate solid acid catalyst was prepared. • Esterification of acetic acid with ethanol can be catalyzed by ZS/SAPO-34. • The hydration of ZS is vital to the acidic property and catalytic performance. • The ZS/SAPO-34 catalyst treated at 200 °C shows good reusability. - Abstract: Zirconium sulfate (ZS) was supported on SAPO-34 molecular sieve by using an incipient wetness impregnation method with zirconium sulfate as the precursor. The as-prepared catalysts were used as solid acid catalyst for esterification reaction of acetic acid with ethanol. The influence of calcination temperature on the acidic property, catalytic activity, and reusability of ZS/SAPO-34 catalysts were mainly investigated. FT-IR, SEM, EDS and TG analysis have been carried out to demonstrate the characteristics of ZS/SAPO-34 catalysts. It was found that the 30 wt%ZS/SAPO-34 catalysts display the property of superacid irrespective of calcination temperature. The ZS/SAPO-34 catalyst treated at 200 °C can enhance the interaction between the supported ZS and SAPO-34 and keep the catalyst remaining substantially active after several reaction cycles. However, further increasing calcination temperature will cause the transfer of ZS from hydrate to anhydrous phase, and thus the decrease of activity

  9. Synthesis of cerium oxide catalysts supported on MCM-41 molecular sieve; Sintese de catalisadores de oxido de cerio suportados na peneira molecular MCM-41

    Energy Technology Data Exchange (ETDEWEB)

    Souza, E.L.S.; Barros, T.R.B.; Sousa, B.V. de, E-mail: emylle.souza@gmail.com [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Unidade Academica de Engenharia Quimica

    2016-07-01

    Porous materials have been widely studied as catalysts and catalyst support. The MCM-41 structure is the one that has been most studied because of its application possibilities in chemical processes. This work aimed to obtain and characterize cerium oxide catalysts supported on MCM-41 molecular sieve. The molecular sieve was synthesized by the conventional method with the following molar composition: 1 SiO2: 0.30 CTABr: NH3 11: 144 H2O. Then, 25% w/w cerium was incorporated into the MCM-41 using the wet impregnation process and the material obtained was activated by calcination. From the XRD patterns was confirmed the structure of the molecular sieve, and were identified the cerium oxide phases in its structure. The textural catalysts characteristics were investigated by isotherms of N2 adsorption/desorption (BET method). (author)

  10. MOLECULAR SIEVES AS CATALYSTS FOR METHANOL DEHYDRATION IN THE LPDMEtm PROCESS; TOPICAL

    International Nuclear Information System (INIS)

    Andrew W. Wang

    2002-01-01

    Several classes of molecular sieves were investigated as methanol dehydration catalysts for the LPDME(trademark) (liquid-phase dimethyl ether) process. Molecular sieves offer a number of attractive features as potential catalysts for the conversion of methanol to DME. These include (1) a wide range of acid strengths, (2) diverse architectures and channel connectivities that provide latitude for steric control, (3) high active site density, (4) well-investigated syntheses and characterization, and (5) commercial availability in some cases. We directed our work in two areas: (1) a general exploration of the catalytic behavior of various classes of molecular sieves in the LPDME(trademark) system and (2) a focused effort to prepare and test zeolites with predominantly Lewis acidity. In our general exploration, we looked at such diverse materials as chabazites, mordenites, pentasils, SAPOs, and ALPOs. Our work with Lewis acidity sought to exploit the structural advantages of zeolites without the interfering effects of deleterious Broensted sites. We used zeolite Ultrastable Y (USY) as our base material because it possesses a high proportion of Lewis acid sites. This work was extended by modifying the USY through ion exchange to try to neutralize residual Broensted acidity

  11. Photocatalytic oxidation of organic compounds in a hybrid system composed of a molecular catalyst and visible light-absorbing semiconductor.

    Science.gov (United States)

    Zhou, Xu; Li, Fei; Li, Xiaona; Li, Hua; Wang, Yong; Sun, Licheng

    2015-01-14

    Photocatalytic oxidation of organic compounds proceeded efficiently in a hybrid system with ruthenium aqua complexes as catalysts, BiVO4 as a light absorber, [Co(NH3)5Cl](2+) as a sacrificial electron acceptor and water as an oxygen source. The photogenerated holes in the semiconductor are used to oxidize molecular catalysts into the high-valent Ru(IV)=O intermediates for 2e(-) oxidation.

  12. Computational Design of Molecularly Imprinted Polymers

    Science.gov (United States)

    Subrahmanyam, Sreenath; Piletsky, Sergey A.

    Artificial receptors have been in use for several decades as sensor elements, in affinity separation, and as models for investigation of molecular recognition. Although there have been numerous publications on the use of molecular modeling in characterization of their affinity and selectivity, very few attempts have been made on the application of molecular modeling in computational design of synthetic receptors. This chapter discusses recent successes in the use of computational design for the development of one particular branch of synthetic receptors - molecularly imprinted polymers.

  13. Molecular Weight and Structural Properties of Biodegradable PLA Synthesized with Different Catalysts by Direct Melt Polycondensation

    Directory of Open Access Journals (Sweden)

    Hyung Woo Lee

    2015-09-01

    Full Text Available Production of biodegradable polylactic acid (PLA from biomassbased lactic acid is widely studied for substituting petro-based plastics or polymers. This study investigated PLA production from commercial lactic acid in a batch reactor by applying a direct melt polycondensation method with two kinds of catalyst, γ-aluminium(III oxide (γ-Al2O3 or zinc oxide (ZnO, in reduced pressure. The molecular weight of the synthesized PLA was determined by capillary viscometry and its structural properties were analyzed by functional group analysis using FT-IR. The yields of polymer production with respect to the theoretical conversion were 47% for γ-Al2O3 and 35% for ZnO. However, the PLA from ZnO had a higher molecular weight (150,600 g/mol than that from γ-Al2O3 (81,400 g/mol. The IR spectra of the synthesized PLA from both catalysts using polycondensation show the same behavior of absorption peaks at wave numbers from 4,500 cm-1 to 500 cm-1, whereas the PLA produced by two other polymerization methods – polycondensation and ring opening polymerization –showed a significant difference in % transmittance intensity pattern as well as peak area absorption at a wave number of 3,500 cm-1 as –OH vibration peak and at 1,750 cm-1 as –C=O carbonyl vibrational peak.

  14. Design of Embedded Metal Catalysts via Reverser Micro-Emulsion System: a Way to Suppress Catalyst Deactivation by Metal Sintering

    KAUST Repository

    AlMana, Noor

    2016-06-19

    The development of highly selective and active, long-lasting, robust, low-cost and environmentally benign catalytic materials is the greatest challenge in the area of catalysis study. In this context, core-shell structures where the active sites are embedded inside the protecting shell have attracted a lot of researchers working in the field of catalysis owing to their enhanced physical and chemical properties suppress catalyst deactivation. Also, a new active site generated at the interface between the core and shell may increases the activity and efficiency of the catalyst in catalytic reactions especially for oxide shells that exhibit redox properties such as TiO2 and CeO2. Moreover, coating oxide layer over metal nanoparticles (NPs) can be designed to provide porosity (micropore/mesopore) that gives selectivity of the various reactants by the different gas diffusion rates. In this thesis, we will discuss the concept of catalyst stabilization against metal sintering by a core-shell system. In particular we will study the mechanistic of forming core-shell particles and the key parameters that can influence the properties and morphology of the Pt metal particle core and SiO2 shell (Pt@SiO2) using the reverse micro-emulsion method. The Pt@SiO2 core-shell catalysts were investigated for low-temperature CO oxidation reaction. The study was further extended to other catalytic applications by varying the composition of the core as well as the chemical nature of the shell material. The Pt NPs were embedded within another oxide matrix such as ZrO2 and TiO2 for CO oxidation reaction. These materials were studied in details to identify the factors governing the coating of the oxide around the metal NPs. Next, a more challenging system, namely, bimetallic Ni9Pt NPs embedded in TiO2 and ZrO2 matrix were investigated for dry reforming of methane reaction at high temperatures. The challenges of designing Ni9Pt@oxide core-shell structure with TiO2 and ZrO2 and their tolerance

  15. Designing Multifunctionality into Single Phase and Multiphase Metal-Oxide-Selective Propylene Ammoxidation Catalysts

    Directory of Open Access Journals (Sweden)

    James F. Brazdil

    2018-03-01

    Full Text Available Multifunctionality is the hallmark of most modern commercial heterogeneous catalyst systems in use today, including those used for the selective ammoxidation of propylene to acrylonitrile. It is the quintessential principle underlying commercial catalyst design efforts since petrochemical process development is invariably driven by the need to reduce manufacturing costs. This is in large part achieved through new and improved catalysts that increase selectivity and productivity. In addition, the future feedstocks for chemical processes will be invariably more refractory than those currently in use (e.g., replacing alkenes with alkanes or using CO2, thus requiring a disparate combination of chemical functions in order to effect multiple chemical transformations with the fewest separate process steps. This review summarizes the key chemical phenomena behind achieving the successful integration of multiple functions into a mixed-metal-oxide-selective ammoxidation catalyst. An experiential and functional catalyst design model is presented that consists of one or both of the following components: (1 a mixed-metal-oxide–solid solution where the individual metal components serve separate and necessary functions in the reaction mechanism through their atomic level interaction in the context of a single crystallographic structure; (2 the required elemental components and their catalytic function existing in separate phases, where these phases are able to interact for the purposes of electron and lattice oxygen transfer through the formation of a structurally coherent interface (i.e., epitaxy between the separate crystal structures. Examples are provided from the literature and explained in the context of this catalyst design model. The extension of the model concepts to the design of heterogeneous catalysts in general is also discussed.

  16. Electro and photo-assisted carbon dioxide reduction on molecular catalysts

    International Nuclear Information System (INIS)

    Stanbury, Matthew

    2016-01-01

    The general context of this thesis is on CO 2 valorisation, and recounts fundamental research aimed at finding new molecular catalysts in order to achieve CO 2 conversion. The results obtained provide additional knowledge in view of developing an efficient and selective catalytic CO 2 reduction process. The first chapter begins with the general picture of CO 2 utilisation and contains a bibliographical overview on the use of molecular catalysts for CO 2 photo- and electroreduction. This short review demonstrates the wide variety of transition metal complexes used as catalysts, in particularly those based on rhenium. An analysis on the current state of CO 2 reduction research using molecular catalyst complexes of the manganese carbonyl type is then reported. In Chapter II, the discussion begins with a brief overview of the research developed during this thesis relating to new complexes of the general formula: [Mn(L)(CO) 3 (X)] (X = Br, n = 0 ou CH 3 CN, n = 1; L = terpyridine derivatives). The interest in these complexes is twofold, as their physico-chemical properties give them potential catalytic CO 2 reduction applications, as well as applications in the field relating to controlled CO release molecules. Developing new complexes based on ligands derived from terpy is one of the main routes that were chosen for catalyst performance optimisation and improvement. In this context, Mn complexes were synthesised, their photo- and electrochemical properties were studied in detail, before testing their activity with respect to catalytic CO 2 reduction. The most remarkable result comes from the unique ability of these species to release one of their carbonyl ligands in a controlled fashion, which led to the discovery of novel Mn dicarbonyl complexes which are selective catalysts for CO 2 reduction, and also to new molecules which are applicable in the release of small quantities of CO for therapeutic purposes. Chapter III covers the study of the complex [Mn

  17. Cobalt-Catalyzed C(sp(2))-H Borylation: Mechanistic Insights Inspire Catalyst Design.

    Science.gov (United States)

    Obligacion, Jennifer V; Semproni, Scott P; Pappas, Iraklis; Chirik, Paul J

    2016-08-24

    A comprehensive study into the mechanism of bis(phosphino)pyridine (PNP) cobalt-catalyzed C-H borylation of 2,6-lutidine using B2Pin2 (Pin = pinacolate) has been conducted. The experimentally observed rate law, deuterium kinetic isotope effects, and identification of the catalyst resting state support turnover limiting C-H activation from a fully characterized cobalt(I) boryl intermediate. Monitoring the catalytic reaction as a function of time revealed that borylation of the 4-position of the pincer in the cobalt catalyst was faster than arene borylation. Cyclic voltammetry established the electron withdrawing influence of 4-BPin, which slows the rate of C-H oxidative addition and hence overall catalytic turnover. This mechanistic insight inspired the next generation of 4-substituted PNP cobalt catalysts with electron donating and sterically blocking methyl and pyrrolidinyl substituents that exhibited increased activity for the C-H borylation of unactivated arenes. The rationally designed catalysts promote effective turnover with stoichiometric quantities of arene substrate and B2Pin2. Kinetic studies on the improved catalyst, 4-(H)2BPin, established a change in turnover limiting step from C-H oxidative addition to C-B reductive elimination. The iridium congener of the optimized cobalt catalyst, 6-(H)2BPin, was prepared and crystallographically characterized and proved inactive for C-H borylation, a result of the high kinetic barrier for reductive elimination from octahedral Ir(III) complexes.

  18. Combinatorial computational chemistry approach to the design of metal catalysts for deNOx

    International Nuclear Information System (INIS)

    Endou, Akira; Jung, Changho; Kusagaya, Tomonori; Kubo, Momoji; Selvam, Parasuraman; Miyamoto, Akira

    2004-01-01

    Combinatorial chemistry is an efficient technique for the synthesis and screening of a large number of compounds. Recently, we introduced the combinatorial approach to computational chemistry for catalyst design and proposed a new method called ''combinatorial computational chemistry''. In the present study, we have applied this combinatorial computational chemistry approach to the design of precious metal catalysts for deNO x . As the first step of the screening of the metal catalysts, we studied Rh, Pd, Ag, Ir, Pt, and Au clusters regarding the adsorption properties towards NO molecule. It was demonstrated that the energetically most stable adsorption state of NO on Ir model cluster, which was irrespective of both the shape and number of atoms including the model clusters

  19. Surface Termination of M1 Phase and Rational Design of Propane Ammoxidation Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Guliants, Vadim [Univ. of Cincinnati, OH (United States)

    2015-02-16

    This final report describes major accomplishments in this research project which has demonstrated that the M1 phase is the only crystalline phase required for propane ammoxidation to acrylonitrile and that a surface monolayer terminating the ab planes of the M1 phase is responsible for their activity and selectivity in this reaction. Fundamental studies of the topmost surface chemistry and mechanism of propane ammoxidation over the Mo-V-(Te,Sb)-(Nb,Ta)-O M1 and M2 phases resulted in the development of quantitative understanding of the surface molecular structure – reactivity relationships for this unique catalytic system. These oxides possess unique catalytic properties among mixed metal oxides, because they selectively catalyze three alkane transformation reactions, namely propane ammoxidation to acrylonitrile, propane oxidation to acrylic acid and ethane oxidative dehydrogenation, all of considerable economic significance. Therefore, the larger goal of this research was to expand this catalysis to other alkanes of commercial interest, and more broadly, demonstrate successful approaches to rational design of improved catalysts that can be applied to other selective (amm)oxidation processes.

  20. A rational design approach to nanostructured catalysts for the oxidation of carbon monoxide

    Science.gov (United States)

    Karwacki, Christopher

    . The role of the support is to provide lattice oxygen in an activated state (O2-) for oxidation of adsorbed CO the Au NP:support interface. Furthermore, the primary interest is the energy associated Au NP in proximity to the support surface. Advancing the understanding of this region is believed to be crucial to the future design of active nanostructured materials that function under ambient conditions. The proposed model involves a structure consisting of properly sized and highly dispersed Au NP supported on a hydroxylated form of nanocrystalline zirconia. This type of zirconia is in a highly polymorphic form consisting of aggregates of small crystals less than 10 nm. The structure is highly porous, containing undercoordinated zirconium atoms, and provides an environment for rapid dissociation of molecular water. In this research and in collaboration with Mogilevsky et al., 37 I introduce a novel method for quantifying the surface concentration of two major forms of hydroxide that form on zirconia. Furthermore, in this research I show how both the porosity of the zirconia support and the size of the crystalline aggregates affect the type and surface concentration of hydroxyl groups. This relationship is thus directly related to the oxidation activity of the catalyst consisting of Au NP supported on hydroxylated ZrO 2. These phenomena are exemplified by a reduction in structural porosity and surface hydroxyl groups with increasing temperature treatments of the zirconia support. Gold NP and ZrO2 supports were extended to studies that included interactions with activated carbons. This work was done on the premise that graphitic carbons, based on their tunable porosities and surface chemistries, can enhance or stabilize the catalytic activity of neighboring Au NP. Gold dispersed on active carbon and hybrid structures consisting of Au/ZrO 2/C shows interesting properties, which lend themselves to catalytic particle stabilization and to the advancement of multifunctional

  1. Bioinspired molecular co-catalysts bonded to a silicon photocathode for solar hydrogen evolution

    DEFF Research Database (Denmark)

    Hou, Yidong; Abrams, Billie L.; Vesborg, Peter Christian Kjærgaard

    2011-01-01

    The production of fuels from sunlight represents one of the main challenges in the development of a sustainable energy system. Hydrogen is the simplest fuel to produce and although platinum and other noble metals are efficient catalysts for photoelectrochemical hydrogen evolution, earth...... that harvests red photons in the solar spectrum. The current densities at the reversible potential match the requirement of a photoelectrochemical hydrogen production system with a solar-to-hydrogen efficiency in excess of 10% (ref. 16). The experimental observations are supported by density functional theory......-abundant alternatives are needed for large-scale use. We show that bioinspired molecular clusters based on molybdenum and sulphur evolve hydrogen at rates comparable to that of platinum. The incomplete cubane-like clusters (Mo3S 4) efficiently catalyse the evolution of hydrogen when coupled to a p-type Si semiconductor...

  2. Non-sensitized selective photochemical reduction of CO2 to CO under visible light with an iron molecular catalyst.

    Science.gov (United States)

    Rao, Heng; Bonin, Julien; Robert, Marc

    2017-03-02

    A substituted tetraphenyl iron porphyrin, bearing positively charged trimethylammonio groups at the para position of each phenyl ring, demonstrates its ability as a homogeneous molecular catalyst to selectively reduce CO 2 to CO under visible light irradiation in organic media without the assistance of a sensitizer and no competitive hydrogen evolution for several days.

  3. Characterization and Design of Zeolite Catalysts Solid Acidity, Shape Selectivity and Loading Properties

    CERN Document Server

    Niwa, Miki; Okumura, Kazu

    2010-01-01

    Zeolites are microporous, aluminosilicate minerals commonly used as commercial adsorbents. Zeolite-based catalysts are used by industrial chemical companies in the interconversion of hydrocarbons and the alkylation of aromatic compounds. The current book deals with the characterization of specific properties of Zeolites and calculations for the design of catalysts. Measurements and utilization of solid acidity, shape selectivity, and loading properties, that are three prominent properties of a Zeolite catalyst, are treated in detail. These features concern chemical vapor deposition of silica, shape selectivity, loading properties, solid activity, Brønsted or Lewis character, ammonia temperature programmed desorption, control of the pore-opening size by chemical vapor deposition of silica and XAFS analysis of metals being highly dispersed inside and outside a framework.

  4. Newly designed PdRuBi/N-Graphene catalysts with synergistic effects for enhanced ethylene glycol electro-oxidation

    International Nuclear Information System (INIS)

    Li, Tengfei; Huang, Yiyin; Ding, Kui; Wu, Peng; Abbas, Syed Comail; Ghausi, Muhammad Arsalan; Zhang, Teng; Wang, Yaobing

    2016-01-01

    Graphical abstract: We rationally design and synthesize a ternary PdRuBi/NG catalyst with significantly enhanced catalytic activity with synergetic effect of Ru and Bi towards ethylene glycol electro-oxidation. - Abstract: Palladium (Pd)-based catalysts are appealing electro-catalysts for alcohol oxidation reaction in fuel cell, but still not efficient as the complicated oxidation process and sluggish kinetic. Here we rationally design and synthesize a PdRuBi/NG tri-metallic catalyst with space synergetic effect for enhanced ethylene glycol electro-oxidation, in which both Ru and Bi in the catalyst are synergistic effective in promoting catalytic activity of Pd catalytic interlayer by electronic effect and surface modification mechanism respectively. It shows 4.2 times higher peak current density towards ethylene glycol electro-oxidation than commercial Pd/C catalyst, and the catalytic durability is also greatly improved.

  5. Advancing Fenton and photo-Fenton water treatment through the catalyst design.

    Science.gov (United States)

    Vorontsov, Alexander V

    2018-04-20

    The review is devoted to modern Fenton, photo-Fenton, as well as Fenton-like and photo-Fenton-like reactions with participation of iron species in liquid phase and as heterogeneous catalysts. Mechanisms of these reactions were considered that include hydroxyl radical and oxoferryl species as the reactive intermediates. The barriers in the way of application of these reactions to wastewater treatment were discussed. The following fundamental problems need further research efforts: inclusion of more mechanism steps and quantum calculations of all rate constants lacking in the literature, checking the outer sphere electron transfer contribution, determination of the causes for the key changes in the homogeneous Fenton reaction mechanism with a change in the reagents concentration. The key advances for Fenton reactions implementation for the water treatment are related to tremendous hydrodynamical effects on the catalytic activity, design of ligands for high rate and completeness of mineralization in short time, and design of highly active heterogeneous catalysts. While both homogeneous and heterogeneous Fenton and photo-Fenton systems are open for further improvements, heterogeneous photo-Fenton systems are most promising for practical applications because of the inherent higher catalyst stability. Modern methods of quantum chemistry are expected to play a continuously increasing role in development of such catalysts. Copyright © 2018 Elsevier B.V. All rights reserved.

  6. The Manipulation of Hydrophobicity in Catalyst Design for Applications of Aerobic Alcohols Oxidation and Electrocatalytic Water Oxidation

    KAUST Repository

    Chen, Batian

    2016-05-17

    Hydrophobicity is the generalized characteristic of non-polar substances that brings about their exclusion from aqueous phases. This property, entropic in its nature, drives key self-assembly and phase separation processes in water. Protein folding, the formation of DNA double helix, the existence of lipid bilayers and the wetting properties of leaf surfaces are all due to hydrophobic interactions. Inspired by Nature, we aimed to use hydrophobicity for creating novel and improved catalytic systems. (I) A number of fluorous amphiphilic star block-copolymers containing a tris(benzyltriazolylmethyl)amine motif have been prepared. These polymers assembled into well-defined nanostructures in water, and their mode of assembly could be controlled by changing the composition of the polymer. The polymers were used for enzyme-inspired catalysis of alcohol oxidation. (II) An enzyme-inspired catalytic system based on a rationally designed multifunctional surfactant was developed. The resulting micelles feature metal-binding sites and stable free radical moieties as well as fluorous pockets that attract and preconcentrate molecular oxygen. In the presence of copper ions, the micelles effect chemoselective aerobic alcohol oxidation under ambient conditions in water, a transformation that is challenging to achieve nonenzymatically. (III) Development of a facile means of photo/electrocatalytic water splitting is one of the main barriers to establishing of a solar hydrogen economy. Of the two half-reactions involved in splitting water into O2 and H2, water oxidation presents the most challenge due to its mechanistic complexity. A practical water oxidation catalyst must be highly active, yet inexpensive and indefinitely stable under harsh oxidative conditions. Here, I shall describe the synthesis of a library of molecular water oxidation catalysts based on the Co complex of tris(2-benzimidazolylmethyl)amine, (BimH)3. A wide range of catalysts differing in their electronic properties

  7. Design of Embedded Metal Catalysts via Reverser Micro-Emulsion System: a Way to Suppress Catalyst Deactivation by Metal Sintering

    KAUST Repository

    Al Mana, Noor

    2016-01-01

    are embedded inside the protecting shell have attracted a lot of researchers working in the field of catalysis owing to their enhanced physical and chemical properties suppress catalyst deactivation. Also, a new active site generated at the interface between

  8. Highly active, recyclable catalyst for the manufacture of viscous, low molecular weight, CO–ethene–propene-based polyketone, base component for a new class of resins

    NARCIS (Netherlands)

    Broekhuis, Antonius A.; Dirkzwager, Hendrik; Mul, Wilhelmus P.; Heeres, Hero J.; Linden, Adrianus J. van der; Orpen, A. Guy

    2002-01-01

    A highly active, recyclable homogeneous palladium(II) catalyst is described for the manufacture of viscous, low molecular weight CO–ethene–propene-based polyketone (Carilite Oligomer), used for the manufacture of a new class of resins (Carilite Resins). The catalyst is composed of palladium acetate,

  9. Solid-State Polymerization of Poly(ethylene furanoate Biobased Polyester, I: Effect of Catalyst Type on Molecular Weight Increase

    Directory of Open Access Journals (Sweden)

    Nejib Kasmi

    2017-11-01

    Full Text Available In this work, we report the synthesis of poly(ethylene furanoate (PEF, catalyzed by three different catalysts, namely, titanium (IV isopropoxide (TIS, tetrabutyltitanate (TBT, and dibutyltin (IV oxide (DBTO, via the two-stage melt polycondensation method. Solid-state polymerization (SSP was conducted at different reaction times (1, 2, 3.5, and 5 h and temperatures 190, 200, and 205 °C, under vacuum. The resultant polymers were analyzed according to their intrinsic viscosity (IV, end groups (–COOH, and thermal properties, via differential scanning calorimetry. DSC results showed that the post polymerization process was favorable to enhance the melting point of the prepared PEF samples. As was expected, the intrinsic viscosity and the average molecular weight of PEF increased with the SSP time and temperature, whereas the number of carboxyl end-groups was decreased. A simple kinetic model was also developed and used to predict the time evolution of polymers IV, as well as the carboxyl and hydroxyl content of PEF during the SSP. From both the experimental measurements and the theoretical simulation results it was proved that the presence of the TIS catalyst resulted in higher transesterification kinetic rate constants and higher reaction rates. The activation energies were not much affected by the presence of different catalysts. Finally, using DBTO as a catalyst, the polyesters produced have higher crystallinity, and as a consequence, higher number of inactive carboxyl and hydroxyl groups.

  10. Design of Molecular Materials: Supramolecular Engineering

    Science.gov (United States)

    Simon, Jacques; Bassoul, Pierre

    2001-02-01

    This timely and fascinating book is destined to be recognised as THE book on supramolecular engineering protocols. It covers this sometimes difficult subject in an approachable form, gathering together information from many sources. Supramolecular chemistry, which links organic chemistry to materials science, is one of the fastest growth areas of chemistry research. This book creates a correlation between the structure of single molecules and the physical and chemical properties of the resulting materials. By making systematic changes to the component molecules, the resulting solid can be engineered for optimum performance. There is a clearly written development from synthesis of designer molecules to properties of solids and further on to devices and complex materials systems, providing guidelines for mastering the organisation of these systems. Topics covered include: Systemic chemistry Molecular assemblies Notions of symmetry Supramolecular engineering Principe de Curie Organisation in molecular media Molecular semiconductors Industrial applications of molecular materials This superb book will be invaluable to researchers in the field of supramolecular materials and also to students and teachers of the subject.

  11. Molecular Rift: Virtual Reality for Drug Designers.

    Science.gov (United States)

    Norrby, Magnus; Grebner, Christoph; Eriksson, Joakim; Boström, Jonas

    2015-11-23

    Recent advances in interaction design have created new ways to use computers. One example is the ability to create enhanced 3D environments that simulate physical presence in the real world--a virtual reality. This is relevant to drug discovery since molecular models are frequently used to obtain deeper understandings of, say, ligand-protein complexes. We have developed a tool (Molecular Rift), which creates a virtual reality environment steered with hand movements. Oculus Rift, a head-mounted display, is used to create the virtual settings. The program is controlled by gesture-recognition, using the gaming sensor MS Kinect v2, eliminating the need for standard input devices. The Open Babel toolkit was integrated to provide access to powerful cheminformatics functions. Molecular Rift was developed with a focus on usability, including iterative test-group evaluations. We conclude with reflections on virtual reality's future capabilities in chemistry and education. Molecular Rift is open source and can be downloaded from GitHub.

  12. Design of Pd-Based Bimetallic Catalysts for ORR: A DFT Calculation Study

    Directory of Open Access Journals (Sweden)

    Lihui Ou

    2015-01-01

    Full Text Available Developing Pd-lean catalysts for oxygen reduction reaction (ORR is the key for large-scale application of proton exchange membrane fuel cells (PEMFCs. In the present paper, we have proposed a multiple-descriptor strategy for designing efficient and durable ORR Pd-based alloy catalysts. We demonstrated that an ideal Pd-based bimetallic alloy catalyst for ORR should possess simultaneously negative alloy formation energy, negative surface segregation energy of Pd, and a lower oxygen binding ability than pure Pt. By performing detailed DFT calculations on the thermodynamics, surface chemistry and electronic properties of Pd-M alloys, Pd-V, Pd-Fe, Pd-Zn, Pd-Nb, and Pd-Ta, are identified theoretically to have stable Pd segregated surface and improved ORR activity. Factors affecting these properties are analyzed. The alloy formation energy of Pd with transition metals M can be mainly determined by their electron interaction. This may be the origin of the negative alloy formation energy for Pd-M alloys. The surface segregation energy of Pd is primarily determined by the surface energy and the atomic radius of M. The metals M which have smaller atomic radius and higher surface energy would tend to favor the surface segregation of Pd in corresponding Pd-M alloys.

  13. Molecular designing of nanoparticles and functional materials

    Directory of Open Access Journals (Sweden)

    Ignjatović Nenad L.

    2017-01-01

    Full Text Available The interdisciplinary research team implemented the program titled “Molecular designing of nanoparticles with controlled morphological and physicochemical characteristics and functional materials based on them” (MODENAFUNA, between 2011 and 2016, gaining new knowledge significant to the further improvement of nanomaterials and nanotechnologies. It gathered under its umbrella six main interrelated topics pertaining to the design and control of morphological and physicochemical properties of nanoparticles and functional material based on them using new methods of synthesis and processing: 1 inorganic nanoparticles, 2 cathode materials for lithium-ion batteries, 3 functional ceramics with improved electrical and optical properties, 4 full density nanostructured calcium phosphate and functionally-graded materials, 5 nano-calcium phosphate in bone tissue engineering and 6 biodegradable micro- and nano-particles for the controlled delivery of medicaments. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. III45004: Molecular designing of nanoparticles with controlled morphological and physicochemical characteristics and functional materials based on them

  14. An Efficient and Stable Hydrophobic Molecular Cobalt Catalyst for Water Electro-oxidation at Neutral pH

    KAUST Repository

    Chen, Ba-Tian

    2016-06-14

    The synthesis of a library of molecular water oxidation catalysts based on the Co complex of tris(2-benzimidazolylmethyl)amine is described. Hydrophobicity was identified as the key variable in mediating the catalytic competence of the complexes. The change in this parameter correlates with both the conformational mobility of the ligand core and the structural changes in the local solvent environment around the metal site. The optimal Co complex identified is hydrophobic, because of three semifluorinated side chains. It catalyzes water electro-oxidation efficiently at neutral pH, with an overpotential of 390 mV and a turnover frequency (TOF) of 1.83 s-1 in the absence of soluble Co salts. The catalyst can be immobilized through physisorption, and it remains stable in prolonged electrolysis experiments. © 2016 American Chemical Society.

  15. An Efficient and Stable Hydrophobic Molecular Cobalt Catalyst for Water Electro-oxidation at Neutral pH

    KAUST Repository

    Chen, Batian; Morlanes, Natalia Sanchez; Adogla, Enoch; Takanabe, Kazuhiro; Rodionov, Valentin

    2016-01-01

    The synthesis of a library of molecular water oxidation catalysts based on the Co complex of tris(2-benzimidazolylmethyl)amine is described. Hydrophobicity was identified as the key variable in mediating the catalytic competence of the complexes. The change in this parameter correlates with both the conformational mobility of the ligand core and the structural changes in the local solvent environment around the metal site. The optimal Co complex identified is hydrophobic, because of three semifluorinated side chains. It catalyzes water electro-oxidation efficiently at neutral pH, with an overpotential of 390 mV and a turnover frequency (TOF) of 1.83 s-1 in the absence of soluble Co salts. The catalyst can be immobilized through physisorption, and it remains stable in prolonged electrolysis experiments. © 2016 American Chemical Society.

  16. An introduction to catalyst

    International Nuclear Information System (INIS)

    Jeon, Hak Je

    1988-11-01

    This book explains basic conception of catalyst such as definition, velocity of chemical reaction and velocity of catalyst reaction, absorption with absorption energy and chemical absorption, pore structure with the role of pore and measurement of pore structure, catalyst activity on solid structure, electrical property on catalyst activity, choice and design of catalyst, catalytic reaction with reaction velocity and chemical equilibrium and reaction velocity model, measurement of reaction velocity and material analysis, catalyst for mixed compound, catalyst for solid acid and catalyst for supported metal.

  17. Design, synthesis, and characterization of novel fine-particle, unsupported catalysts for coal liquefaction. Technical progress report, October 25, 1990--October 24, 1991: Draft

    Energy Technology Data Exchange (ETDEWEB)

    Klein, M.T.

    1991-12-30

    The purpose of this work is to investigate the kinetics-assisted design, synthesis and characterization of fme-pardcle, unsupported catalysts for coal liquefaction. The goal is to develop a fundamental understanding of coal catalysis and catalysts that will, in turn, allow for the specification of a novel optimal catalyst for coal liquefaction.

  18. Advancements in rationally designed PGM-free fuel cell catalysts derived from metal–organic frameworks

    International Nuclear Information System (INIS)

    Barkholtz, Heather M.; Liu, Di-Jia

    2016-01-01

    Over the past several years, metal-organic framework (MOF)-derived platinum group metal free (PGM-free) electrocatalysts have gained considerable attention due to their high efficiency and low cost as potential replacement for platinum in catalyzing oxygen reduction reaction (ORR). In this review, we summarize the recent advancements in design, synthesis and characterization of MOF-derived ORR catalysts and their performances in acidic and alkaline media. As a result, we also discuss the key challenges such as durability and activity enhancement critical in moving forward this emerging electrocatalyst science.

  19. From First Principles Design to Realization of Bimetallic Catalysts for Enhanced Selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Lobo, Raul F.; Crooks, Richard M.; Mavrikakis, Manos

    2014-04-08

    “Catalysis by design” has been a dream for decades. To specify the composition and structure of matter to effect a desired catalytic transformation with desired and predicted rate and selectivity remains a monumental challenge, especially in heterogeneous catalysis. Our research thrusts have been chosen not only for their practical and scientific relevance, e.g. for more efficient and sustainable chemicals and fuels production, but also because they provide a foundation for developing and exploring broadly applicable principles and strategies for catalyst design.

  20. Three-site mechanism and molecular weight: Time dependency in liquid propylene batch polymerization using a MgCl2-supported Ziegler-Natta catalyst

    NARCIS (Netherlands)

    Shimizu, Fumihiko; Pater, J.T.M.; Weickert, G.

    2001-01-01

    This article demonstrates that the molecular weight of propylene homopolymer decreases with time, and that the molecular weight distribution (MWD) narrows when a highly active MgCl2-supported catalyst is used in a liquid pool polymerization at constant H2 concentration and temperature. To track the

  1. Design Criteria, Operating Conditions, and Nickel-Iron Hydroxide Catalyst Materials for Selective Seawater Electrolysis.

    Science.gov (United States)

    Dionigi, Fabio; Reier, Tobias; Pawolek, Zarina; Gliech, Manuel; Strasser, Peter

    2016-05-10

    Seawater is an abundant water resource on our planet and its direct electrolysis has the advantage that it would not compete with activities demanding fresh water. Oxygen selectivity is challenging when performing seawater electrolysis owing to competing chloride oxidation reactions. In this work we propose a design criterion based on thermodynamic and kinetic considerations that identifies alkaline conditions as preferable to obtain high selectivity for the oxygen evolution reaction. The criterion states that catalysts sustaining the desired operating current with an overpotential seawater-mimicking electrolyte. The catalyst was synthesized by a solvothermal method and the activity, surface redox chemistry, and stability were tested electrochemically in alkaline and near-neutral conditions (borate buffer at pH 9.2) and under both fresh seawater conditions. The Tafel slope at low current densities is not influenced by pH or presence of chloride. On the other hand, the addition of chloride ions has an influence in the temporal evolution of the nickel reduction peak and on both the activity and stability at high current densities at pH 9.2. Faradaic efficiency close to 100 % under the operating conditions predicted by our design criteria was proven using in situ electrochemical mass spectrometry. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Design of Highly Selective Platinum Nanoparticle Catalysts for the Aerobic Oxidation of KA-Oil using Continuous-Flow Chemistry.

    Science.gov (United States)

    Gill, Arran M; Hinde, Christopher S; Leary, Rowan K; Potter, Matthew E; Jouve, Andrea; Wells, Peter P; Midgley, Paul A; Thomas, John M; Raja, Robert

    2016-03-08

    Highly active and selective aerobic oxidation of KA-oil to cyclohexanone (precursor for adipic acid and ɛ-caprolactam) has been achieved in high yields using continuous-flow chemistry by utilizing uncapped noble-metal (Au, Pt & Pd) nanoparticle catalysts. These are prepared using a one-step in situ methodology, within three-dimensional porous molecular architectures, to afford robust heterogeneous catalysts. Detailed spectroscopic characterization of the nature of the active sites at the molecular level, coupled with aberration-corrected scanning transmission electron microscopy, reveals that the synthetic methodology and associated activation procedures play a vital role in regulating the morphology, shape and size of the metal nanoparticles. These active centers have a profound influence on the activation of molecular oxygen for selective catalytic oxidations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Examining Rhodium Catalyst complexes for Use with Conducting Polymers Designed for Fuel Cells in Preparing Biosensors

    Energy Technology Data Exchange (ETDEWEB)

    Carpio, M.M.; Kerr, J.B.

    2005-01-01

    Biosensing devices are important because they can detect, record, and transmit information regarding the presence of, or physiological changes in, different chemical or biological materials in the environment. The goal of this research is to prepare a biosensing device that is effective, quick, and low cost. This is done by examining which chemicals will work best when placed in a biosensor. The first study involved experimenting on a rhodium catalyst complexed with ligands such as bipyridine and imidazole. The rhodium catalyst is important because it is reduced from RhIII to RhI, forms a hydride by reaction with water and releases the hydride to react with nicotinamide adenine dinucleotide (NAD+) to selectively produce 1,4-NADH, the reduced form of NAD+. The second study looked at different types of ketones and enzymes for the enzyme-substrate reaction converting a ketone into an alcohol. Preliminary results showed that the rhodium complexed with bipyridine was able to carry out all the reactions, while the rhodium complexed with imidazole was not able to produce and release hydrides. In addition, the most effective ketone to use is benzylacetone with the enzyme alcohol dehydrogenase from baker’s yeast. Future work includes experimenting with bis-imidazole, which mimics the structure of bipyridine to see if it has the capability to reduce and if the reduction rate is comparable to the bipyridine complex. Once all testing is completed, the fastest catalysts will be combined with polymer membranes designed for fuel cells to prepare biosensing devices that can be used in a variety of applications including ones in the medical and environmental fields.

  4. Reactivation of a Palladium Catalyst during Glucose Oxidation by Molecular Oxygen

    Czech Academy of Sciences Publication Activity Database

    Gogová, Zuzana; Hanika, Jiří

    2009-01-01

    Roč. 63, č. 5 (2009), s. 520-526 ISSN 0366-6352 R&D Projects: GA ČR(CZ) GD203/08/H032 Institutional research plan: CEZ:AV0Z40720504 Keywords : glucose * palladium catalyst * deactivation Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 0.791, year: 2009

  5. Hoveyda-Grubbs type metathesis catalyst immobilized on mesoporous molecular sieves MCM-41 and SBA-15

    Czech Academy of Sciences Publication Activity Database

    Balcar, Hynek; Shinde, Tushar; Žilková, Naděžda; Bastl, Zdeněk

    2011-01-01

    Roč. 7, January (2011), s. 22-28 ISSN 1860-5397 R&D Projects: GA AV ČR IAA400400805; GA AV ČR KAN100400701 Institutional research plan: CEZ:AV0Z40400503 Keywords : alkene metathesis * catalyst immobilization * hybrid catalysis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.517, year: 2011

  6. Synthesis and application of different phthalocyanine molecular sieve catalyst for oxidative desulfurization

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Na; Li, Siwen; Wang, Jinyi; Zhang, Ronglan [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry & Material Science, Northwest University, Xi’an 710069, Shaanxi (China); Composites Research Institute, Weinan Normal University, Weinan 714000 (China); Gao, Ruimin [Research Institute of Shaanxi Yanchang Petroleum Group Corp. Ltd., Xi’an 710075 (China); Composites Research Institute, Weinan Normal University, Weinan 714000 (China); Zhao, Jianshe, E-mail: jszhao@nwu.edu.cn [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry & Material Science, Northwest University, Xi’an 710069, Shaanxi (China); Composites Research Institute, Weinan Normal University, Weinan 714000 (China); Wang, Junlong [Research Institute of Shaanxi Yanchang Petroleum Group Corp. Ltd., Xi’an 710075 (China); Composites Research Institute, Weinan Normal University, Weinan 714000 (China)

    2015-05-15

    M{sub 2}(PcAN){sub 2} (M=Fe, Co, Ni, Cu, Zn and Mn) anchored onto W-HZSM-5 (M{sub 2}(PcAN){sub 2}–W-HZSM-5) or the M{sub 2}(PcTN){sub 2} doping W-HZSM-5 (M{sub 2}(PcTN){sub 2}/W-HZSM-5) were prepared and their catalytic performances were tested for oxidative desulfurization in the presence of oxygen. Thiophene (T), benzothiophene (BT), and dibenzothiophene (DBT) were considered as sulfur compounds. Among zeolite-based catalysts, the Cu{sub 2}(PcAN){sub 2}–W-HZSM-5 and Cu{sub 2}(PcTN){sub 2}/W-HZSM-5 showed superior desulfurization performance and the activity of selectivity followed the order: T>BT>DBT. The effects of phthalocyanine concentration were studied by UV–Vis and calcination temperature was obtained by TG-DSC for Cu{sub 2}(PcTN){sub 2}/W-HZSM-5. Catalysts were characterized by EA, IR, XRD, SEM, TEM, ICP, and N{sub 2} adsorption. Reaction time, temperature and the amount of catalyst were investigated as the important parameters for optimization of the reaction. Furthermore, a possible process of oxidative desulfurization and the reaction products were proposed. - Graphical abstract: The ODS reaction schematic shows the reaction mechanism of ultra-deep desulfurization. The sulfur compounds are oxidized to their corresponding sulfoxides or sulfones through the use of oxygen and catalysts. The reaction process of ultra-deep desulfurization. - Highlights: • A kind of novel catalyst for deep desulfurization was synthesized. • Cu{sub 2}(PcAN){sub 2}–W-HZSM-5 exhibits excellent catalytic performance for desulfurization. • The reaction conditions that affect desulfurization efficiency are investigated. • The reaction process of model sulfur compounds is proposed.

  7. Synthesis and application of different phthalocyanine molecular sieve catalyst for oxidative desulfurization

    International Nuclear Information System (INIS)

    Zhao, Na; Li, Siwen; Wang, Jinyi; Zhang, Ronglan; Gao, Ruimin; Zhao, Jianshe; Wang, Junlong

    2015-01-01

    M 2 (PcAN) 2 (M=Fe, Co, Ni, Cu, Zn and Mn) anchored onto W-HZSM-5 (M 2 (PcAN) 2 –W-HZSM-5) or the M 2 (PcTN) 2 doping W-HZSM-5 (M 2 (PcTN) 2 /W-HZSM-5) were prepared and their catalytic performances were tested for oxidative desulfurization in the presence of oxygen. Thiophene (T), benzothiophene (BT), and dibenzothiophene (DBT) were considered as sulfur compounds. Among zeolite-based catalysts, the Cu 2 (PcAN) 2 –W-HZSM-5 and Cu 2 (PcTN) 2 /W-HZSM-5 showed superior desulfurization performance and the activity of selectivity followed the order: T>BT>DBT. The effects of phthalocyanine concentration were studied by UV–Vis and calcination temperature was obtained by TG-DSC for Cu 2 (PcTN) 2 /W-HZSM-5. Catalysts were characterized by EA, IR, XRD, SEM, TEM, ICP, and N 2 adsorption. Reaction time, temperature and the amount of catalyst were investigated as the important parameters for optimization of the reaction. Furthermore, a possible process of oxidative desulfurization and the reaction products were proposed. - Graphical abstract: The ODS reaction schematic shows the reaction mechanism of ultra-deep desulfurization. The sulfur compounds are oxidized to their corresponding sulfoxides or sulfones through the use of oxygen and catalysts. The reaction process of ultra-deep desulfurization. - Highlights: • A kind of novel catalyst for deep desulfurization was synthesized. • Cu 2 (PcAN) 2 –W-HZSM-5 exhibits excellent catalytic performance for desulfurization. • The reaction conditions that affect desulfurization efficiency are investigated. • The reaction process of model sulfur compounds is proposed

  8. Design of ultrathin Pt-Mo-Ni nanowire catalysts for ethanol electrooxidation.

    Science.gov (United States)

    Mao, Junjie; Chen, Wenxing; He, Dongsheng; Wan, Jiawei; Pei, Jiajing; Dong, Juncai; Wang, Yu; An, Pengfei; Jin, Zhao; Xing, Wei; Tang, Haolin; Zhuang, Zhongbin; Liang, Xin; Huang, Yu; Zhou, Gang; Wang, Leyu; Wang, Dingsheng; Li, Yadong

    2017-08-01

    Developing cost-effective, active, and durable electrocatalysts is one of the most important issues for the commercialization of fuel cells. Ultrathin Pt-Mo-Ni nanowires (NWs) with a diameter of ~2.5 nm and lengths of up to several micrometers were synthesized via a H 2 -assisted solution route (HASR). This catalyst was designed on the basis of the following three points: (i) ultrathin NWs with high numbers of surface atoms can increase the atomic efficiency of Pt and thus decrease the catalyst cost; (ii) the incorporation of Ni can isolate Pt atoms on the surface and produce surface defects, leading to high catalytic activity (the unique structure and superior activity were confirmed by spherical aberration-corrected electron microscopy measurements and ethanol oxidation tests, respectively); and (iii) the incorporation of Mo can stabilize both Ni and Pt atoms, leading to high catalytic stability, which was confirmed by experiments and density functional theory calculations. Furthermore, the developed HASR strategy can be extended to synthesize a series of Pt-Mo-M (M = Fe, Co, Mn, Ru, etc.) NWs. These multimetallic NWs would open up new opportunities for practical fuel cell applications.

  9. Towards a rational design of ruthenium CO2 hydrogenation catalysts by Ab initio metadynamics.

    Science.gov (United States)

    Urakawa, Atsushi; Iannuzzi, Marcella; Hutter, Jürg; Baiker, Alfons

    2007-01-01

    Complete reaction pathways relevant to CO2 hydrogenation by using a homogeneous ruthenium dihydride catalyst ([Ru(dmpe)2H2], dmpe=Me2PCH2CH2PMe2) have been investigated by ab initio metadynamics. This approach has allowed reaction intermediates to be identified and free-energy profiles to be calculated, which provide new insights into the experimentally observed reaction pathway. Our simulations indicate that CO2 insertion, which leads to the formation of formate complexes, proceeds by a concerted insertion mechanism. It is a rapid and direct process with a relatively low activation barrier, which is in agreement with experimental observations. Subsequent H2 insertion into the formate--Ru complex, which leads to the formation of formic acid, instead occurs via an intermediate [Ru(eta2-H2)] complex in which the molecular hydrogen coordinates to the ruthenium center and interacts weakly with the formate group. This step has been identified as the rate-limiting step. The reaction completes by hydrogen transfer from the [Ru(eta2-H2)] complex to the formate oxygen atom, which forms a dihydrogen-bonded Ru--HHO(CHO) complex. The activation energy for the H2 insertion step is lower for the trans isomer than for the cis isomer. A simple measure of the catalytic activity was proposed based on the structure of the transition state of the identified rate-limiting step. From this measure, the relationship between catalysts with different ligands and their experimental catalytic activities can be explained.

  10. Polymerization of aliphatic alkynes with heterogeneous Mo catalysts supported on mesoporous molecular sieves

    Czech Academy of Sciences Publication Activity Database

    Balcar, Hynek; Topka, Pavel; Sedláček, J.; Zedník, J.; Čejka, Jiří

    2008-01-01

    Roč. 46, č. 7 (2008), s. 2593-2599 ISSN 0887-624X R&D Projects: GA ČR GA203/05/2194; GA AV ČR IAA4040411; GA AV ČR KAN100400701 Institutional research plan: CEZ:AV0Z40400503 Keywords : alkyne polymerization * conjugated polymers * metathesis * Mo heterogeneous catalysts Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.821, year: 2008

  11. Synthesis and application of different phthalocyanine molecular sieve catalyst for oxidative desulfurization

    Science.gov (United States)

    Zhao, Na; Li, Siwen; Wang, Jinyi; Zhang, Ronglan; Gao, Ruimin; Zhao, Jianshe; Wang, Junlong

    2015-05-01

    M2(PcAN)2 (M=Fe, Co, Ni, Cu, Zn and Mn) anchored onto W-HZSM-5 (M2(PcAN)2-W-HZSM-5) or the M2(PcTN)2 doping W-HZSM-5 (M2(PcTN)2/W-HZSM-5) were prepared and their catalytic performances were tested for oxidative desulfurization in the presence of oxygen. Thiophene (T), benzothiophene (BT), and dibenzothiophene (DBT) were considered as sulfur compounds. Among zeolite-based catalysts, the Cu2(PcAN)2-W-HZSM-5 and Cu2(PcTN)2/W-HZSM-5 showed superior desulfurization performance and the activity of selectivity followed the order: T>BT>DBT. The effects of phthalocyanine concentration were studied by UV-Vis and calcination temperature was obtained by TG-DSC for Cu2(PcTN)2/W-HZSM-5. Catalysts were characterized by EA, IR, XRD, SEM, TEM, ICP, and N2 adsorption. Reaction time, temperature and the amount of catalyst were investigated as the important parameters for optimization of the reaction. Furthermore, a possible process of oxidative desulfurization and the reaction products were proposed. The reaction process of ultra-deep desulfurization.

  12. Molecular Recognition Units: Design and diagnostic applications

    International Nuclear Information System (INIS)

    Alvarez, V.L.; Radcliffe, R.D.; Coughlin, D.J.; Lopes, A.D.; Rodwell, J.D.

    1992-01-01

    Molecular Recognition Units (MRUs), small peptides derived from complementarity-determining region (CDR) of IgM antibodies, can mimic the recognition site found in the antibody. One example of an MRU fusion peptide designed to image thrombi was derived from PAC 1.1, an IgM monoclonal antibody specific for the GPIIb/IIa receptor on platelets. The peptide sequence from the third CDR of the heavy chain was engineered for optimal binding activity and synthesized with a metal-binding peptide sequence. After labeling with 99m-Tc, the peptides were injected into either animal models of experimentally induced thrombi in order to determine their effectiveness in imaging model thrombi. Data are presented which demonstrate enhanced binding with open-quotes tandem repeatsclose quotes of the MRU domain and no loss of activity after incorporation of the metal-binding domain. These studies have led to a clinical candidate consisting of 17 amino acids. Extension of this concept to other MRUs and fusion peptides is also discussed

  13. Molecular Modeling: A Powerful Tool for Drug Design and Molecular ...

    Indian Academy of Sciences (India)

    eling studies is generally a two-dimensional drawing of a re- quired molecule. ... The most active area of theoretical research using molecular orbi tal theory has been in ... minimum energy structure for example, by using conjugated gradient algorithm .... QSARwas applied to understand how the structure might be modified ...

  14. Rational Catalyst Design of Titanium-Silica Materials Aided by Site-Specific Titration Tools

    Science.gov (United States)

    Eaton, Todd Robert

    between particle and crystal size, as obtained from XRD. In the course of establishing these relationships we've gained the knowledge of how to control TiO x structure, which enables the design of new and better catalysts. Understanding the synthesis-structure-function relationships allow for the design of a tandem photo/thermocatalytic reaction system for producing and consuming H2O2. By partially overcoating a TiO 2 photocatalyst with a ˜2 nm silica layer we observe a 56-fold rate improvement compared to bare-TiO2 for H2O2 synthesis from the proton-assisted reduction of O2. Addition of metal-SiO2 thermocatalysts (metal=Ti, Nb, or Ta) with sites needed for H2O2 activation creates a tandem system wherein the H2O2 produced in situ is utilized for alkene epoxidation. Compared to a thermocatalytic-only system, the tandem system accelerates epoxidation for cis-cyclooctene(11x faster), styrene(20x) and 1-octene(30x). This approach demonstrates a means for epoxidation with O2 that avoids H2O2 purification and transport, simplifies the total process, provides new opportunities for control by independent H2O2 production and consumption in the same reactor, and enhances rates relative to thermocatalytic-only epoxidation by intimately coupling H2O2 generation and consumption. Critically, establishment of titanium-silica synthesis-structure-function relationships enables the design of new catalysts and systems that are less energy- and material-intensive, leading towards more sustainable chemistry.

  15. Benign by design: catalyst-free in-water, on-water green chemical methodologies in organic synthesis

    Science.gov (United States)

    The development of organic synthesis under sustainable conditions is a primary goal of practicing green chemists who want to prevent pollution and design safer pathways. Although, it is challenging to avoid the use of catalysts, or solvents in all the organic reactions but progre...

  16. A molecular molybdenum–schiff base electro-catalyst for generating hydrogen from acetic acid or water

    International Nuclear Information System (INIS)

    Cao, Jie-Ping; Fang, Ting; Zhou, Ling-Ling; Fu, Ling-Zhi; Zhan, Shuzhong

    2014-01-01

    Highlights: • The reaction of ligand, H 2 L and MoCl 5 gives a Mo(VI) complex [MoL(O) 2 ] 1. • Complex 1 is capable of catalyzing hydrogen evolution from acetic acid and water. • TOF reaches a maximum of 68 (DMF) and 356 (buffer, pH 6) moles/h, respectively. • Sustained proton reduction catalysis occurs over a 69 h period and no decomposition of 1. - ABSTRACT: The reaction of 2-pyridylamino-N,N-bis(2-methylene-4-ethyl-6-tert-butylphenol) (H 2 L) and MoCl 5 gives a molybdenum(VI) complex [MoL(O) 2 ] 1, a new molecular electrocatalyst, which has been determined by X-ray crystallography. Electrochemical studies show that complex 1 can catalyze hydrogen evolution from acetic acid or aqueous buffer. Turnover frequency (TOF) reaches a maximum of 68 (in N,N-Dimethylformamide (DMF)) and 356 (in buffer, pH 6.0) moles of hydrogen per mole of catalyst per hour, respectively. Sustained proton reduction catalysis occurs at glassy carbon (GC) electrode to give H 2 over a 69 h electrolysis period and no observable decomposition of the catalyst

  17. Report on DOE - industry workshop on Computer-Aided Catalyst Design (CACD)

    Energy Technology Data Exchange (ETDEWEB)

    Hay, P.J. [comp.

    1994-07-01

    Representatives from industry, national laboratories, and the DOE met to review the status of the DOE-sponsored Computer-Aided Catalyst Design (CACD) program and to assess current industrial needs in CACD. Of the 40 participants at the workshop, nearly half were from industry representing 12 companies--Arco Chemical, Amoco Chemical, Biosym, Dow, DuPont, Exxon, Ford, General Motors, Mobil, Monsanto, W.R. Grace and Union Carbide--that included nine of the largest chemical producers in the U.S. representing $61 billion in chemical sales in 1993. An overview of developments in catalyst modeling at the national laboratories was presented, and current CACD-related activities at each of the companies were described by the industrial participants. The CACD program is addressing important industry needs and is having a significant impact despite the current limited scope and budget. The industrial participants urged the program to continue to target specific areas and to encourage collaborative work among the national labs. Industrial participants expressed strong interest in increased interactions with CACD activities at the national labs, where competencies in theory, modeling, and simulation complement the traditional strengths of catalysis expertise in industry. The chemical, refining and automotive industries face continual economic and environmental pressures for now or improved catalytic processes that are more efficient and produce fewer undesirable byproducts. CACD is viewed as an effective means to enhance experimental catalysis research. The industrial participants attested to the importance of developing and applying catalysis modeling capabilities. The companies represented at the meeting had varying degrees of activity in this area, and many already had significant interactions with national labs. As potential users of this technology, they strongly endorsed the work in the CACD program in the development of modeling capabilities.

  18. Electrocatalytic oxidation of organic substrates with molecular oxygen using tetradentate ruthenium(III)-Schiff base complexes as catalysts

    International Nuclear Information System (INIS)

    Ourari, Ali; Khelafi, Mostefa; Aggoun, Djouhra; Jutand, Anny; Amatore, Christian

    2012-01-01

    Three complexes Ru(III)ClL n involving different tetradentate Schiff base ligands L n (see L 1 , L 2 and L 3 in ) were used as catalysts in the oxidation of cyclooctene and tetraline in the presence of molecular dioxygen associated with benzoic anhydride. The efficiency of this oxidation reaction was tested in the presence of two apical bases: 1- or 2-methylimidazole. All complexes exhibit a quasi-reversible redox system. The electrolysis experiments were carried out at controlled potential for each complex, using different substrates such as cyclooctene and tetraline. The oxidized products are cyclooctene oxide (turnover 6.7), a mixture of 1-tetralol and 1-tetralone (turnover 7.6) respectively.

  19. Molecular and Silica-Supported Molybdenum Alkyne Metathesis Catalysts: Influence of Electronics and Dynamics on Activity Revealed by Kinetics, Solid-State NMR, and Chemical Shift Analysis.

    Science.gov (United States)

    Estes, Deven P; Gordon, Christopher P; Fedorov, Alexey; Liao, Wei-Chih; Ehrhorn, Henrike; Bittner, Celine; Zier, Manuel Luca; Bockfeld, Dirk; Chan, Ka Wing; Eisenstein, Odile; Raynaud, Christophe; Tamm, Matthias; Copéret, Christophe

    2017-12-06

    Molybdenum-based molecular alkylidyne complexes of the type [MesC≡Mo{OC(CH 3 ) 3-x (CF 3 ) x } 3 ] (MoF 0 , x = 0; MoF 3 , x = 1; MoF 6 , x = 2; MoF 9 , x = 3; Mes = 2,4,6-trimethylphenyl) and their silica-supported analogues are prepared and characterized at the molecular level, in particular by solid-state NMR, and their alkyne metathesis catalytic activity is evaluated. The 13 C NMR chemical shift of the alkylidyne carbon increases with increasing number of fluorine atoms on the alkoxide ligands for both molecular and supported catalysts but with more shielded values for the supported complexes. The activity of these catalysts increases in the order MoF 0 molecular and supported species. Detailed solid-state NMR analysis of molecular and silica-supported metal alkylidyne catalysts coupled with DFT/ZORA calculations rationalize the NMR spectroscopic signatures and discernible activity trends at the frontier orbital level: (1) increasing the number of fluorine atoms lowers the energy of the π*(M≡C) orbital, explaining the more deshielded chemical shift values; it also leads to an increased electrophilicity and higher reactivity for catalysts up to MoF 6 , prior to a sharp decrease in reactivity for MoF 9 due to the formation of stable metallacyclobutadiene intermediates; (2) the silica-supported catalysts are less active than their molecular analogues because they are less electrophilic and dynamic, as revealed by their 13 C NMR chemical shift tensors.

  20. Hydration effects on the molecular structure of silica-supported vanadium oxide catalysts: A combined IR, Raman, UV–vis and EXAFS study

    NARCIS (Netherlands)

    Keller, D.E.; Visser, T.; Soulimani, F.; Koningsberger, D.C.; Weckhuysen, B.M.

    2007-01-01

    The effect of hydration on the molecular structure of silica-supported vanadium oxide catalysts with loadings of 1–16 wt.% V has been systematically investigated by infrared, Raman, UV–vis and EXAFS spectroscopy. IR and Raman spectra recorded during hydration revealed the formation of V–OH groups,

  1. Pore design of pelletised VOX/ZrO2-SO4/Sepiolite composite catalysts

    DEFF Research Database (Denmark)

    Rasmussen, Søren Birk; Due-Hansen, Johannes; Yates, M.

    2010-01-01

    The NH3-SCR activities of a series of extruded and calcined VOX/ZrO2-SO4 - sepiolite catalysts were determined. The pore structures were heavily influenced by the clay content with macropore sizes ranging from 50 to >1000 nm. Mechanical strength and SCR activity measurements suggested that 25% w/....../w sepiolite is the optimal catalyst composition....

  2. Broadening of molecular weight distribution of polymers synthesized by metallocene-based dual-site catalysts; Alargamento da distribuicao de massa molar de polimeros sintetizados com catalisadores metalocenicos dual-site

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Joao H.Z. dos [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Inst. de Quimica]. E-mail: jhzds@iq.ufrgs.br; Fisch, Adriano G.; Cardozo, Nilo S.M.; Secchi, Argimiro R. [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Dept. de Engenharia Quimica

    2008-07-01

    The main topics related to the use of dual-site catalysts in the production of polymers with broad molecular weight distribution are reviewed. The polymerization using dual-site catalysts is more economical and allows to produce a higher quality product than other processes, such as polymer blend and multistage reactors. However, the formulation of these catalysts is quite complicated since the same catalyst must produce distinct polymer grades. In addition, the release of patents concerning the combination of metallocenes and new technologies for polymerization shows that polymerization processes using dual-site catalysts are of current industrial interest. (author)

  3. Rhodium(II) metallopeptide catalyst design enables fine control in selective functionalization of natural SH3 domains.

    Science.gov (United States)

    Vohidov, Farrukh; Coughlin, Jane M; Ball, Zachary T

    2015-04-07

    Chemically modified proteins are increasingly important for use in fundamental biophysical studies, chemical biology, therapeutic protein development, and biomaterials. However, chemical methods typically produce heterogeneous labeling and cannot approach the exquisite selectivity of enzymatic reactions. While bioengineered methods are sometimes an option, selective reactions of natural proteins remain an unsolved problem. Here we show that rhodium(II) metallopeptides combine molecular recognition with promiscuous catalytic activity to allow covalent decoration of natural SH3 domains, depending on choice of catalyst but independent of the specific residue present. A metallopeptide catalyst succeeds in modifying a single SH3-containing kinase at endogenous concentrations in prostate cancer (PC-3) cell lysate. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Architectonics: Design of Molecular Architecture for Functional Applications.

    Science.gov (United States)

    Avinash, M B; Govindaraju, Thimmaiah

    2018-02-20

    The term architectonics has its roots in the architectural and philosophical (as early as 1600s) literature that refers to "the theory of structure" and "the structure of theory", respectively. The concept of architectonics has been adapted to advance the field of molecular self-assembly and termed as molecular architectonics. In essence, the methodology of organizing molecular units in the required and controlled configurations to develop advanced functional systems for materials and biological applications comprises the field of molecular architectonics. This concept of designing noncovalent systems enables to focus on different functional aspects of designer molecules for biological and nonbiological applications and also strengthens our efforts toward the mastery over the art of controlled molecular self-assemblies. Programming complex molecular interactions and assemblies for specific functions has been one of the most challenging tasks in the modern era. Meticulously ordered molecular assemblies can impart remarkable developments in several areas spanning energy, health, and environment. For example, the well-defined nano-, micro-, and macroarchitectures of functional molecules with specific molecular ordering possess potential applications in flexible electronics, photovoltaics, photonic crystals, microreactors, sensors, drug delivery, biomedicine, and superhydrophobic coatings, among others. The functional molecular architectures having unparalleled properties are widely evident in various designs of Nature. By drawing inspirations from Nature, intended molecular architectures can be designed and developed to harvest various functions, as there is an inexhaustible resource and scope. In this Account, we present exquisite designer molecules developed by our group and others with an objective to master the art of molecular recognition and self-assembly for functional applications. We demonstrate the tailor-ability of molecular self-assemblies by employing

  5. Molecular design of Mycoplasma hominis Vaa adhesin

    DEFF Research Database (Denmark)

    Boesen, Thomas; Fedosova, Natalya U.; Kjeldgaard, Morten

    2001-01-01

    The variable adherence-associated (Vaa) adhesin of the opportunistic human pathogen Mycoplasma hominis is a surface-exposed, membrane-associated protein involved in the attachment of the bacterium to host cells. The molecular masses of recombinant 1 and 2 cassette forms of the protein determined...

  6. PSII as an in vivo molecular catalyst for the production of energy rich hydroquinones - A new approach in renewable energy.

    Science.gov (United States)

    Das, Sai; Maiti, Soumen K

    2018-03-01

    One of the pertinent issues in the field of energy science today is the quest for an abundant source of hydrogen or hydrogen equivalents. In this study, phenyl-p-benzoquinone (pPBQ) has been used to generate a molecular store of hydrogen equivalents (phenyl-p-hydroquinone; pPBQH 2 ) from thein vivo splitting of water by photosystem II of the marine cyanobacterium Synechococcus elongatus BDU 70542. Using this technique, 10.8 μmol of pPBQH 2 per mg chlorophyll a can be extracted per minute, an efficiency that is orders of magnitude higher when compared to the techniques present in the current literature. Moreover, the photo-reduction process was stable when tested over longer periods of time. Addition of phenyl-p-benzoquinone on an intermittent basis resulted in the precipitation of phenyl-p-hydroquinone, obviating the need for costly downstream processing units for product recovery. Phenyl-p-hydroquinone so obtained is a molecular store of free energy preserved through the light driven photolysis of water and can be used as a cheap and a renewable source of hydrogen equivalents by employing transition metal catalysts or fuel cells with the concomitant regeneration of phenyl-p-benzoquinone. The cyclic nature of this technique makes it an ideal candidate to be utilized in mankind's transition from fossil fuels to solar fuels. Copyright © 2018 Elsevier B.V. All rights reserved.

  7. Design of Pt/Carbon Xerogel Catalysts for PEM Fuel Cells

    Directory of Open Access Journals (Sweden)

    Nathalie Job

    2015-01-01

    Full Text Available The design of efficient catalytic layers of proton exchange membrane fuel cells (PEMFCs requires the preparation of highly-loaded and highly-dispersed Pt/C catalysts. During the last few years, our work focused on the preparation of Pt/carbon xerogel electrocatalysts, starting from simple impregnation techniques that were further optimized via the strong electrostatic adsorption (SEA method to reach high dispersion and a high metal weight fraction. The SEA method, which consists of the optimization of the precursor/support electrostatic impregnation through an adequate choice of the impregnation pH with regard to the support surface chemistry, leads to very well-dispersed Pt/C samples with a maximum 8 wt.% Pt after drying and reduction under H2. To increase the metal loading, the impregnation-drying-reduction cycle of the SEA method can be repeated several times, either with fresh Pt precursor solution or with the solution recycled from the previous cycle. In each case, a high dispersion (Pt particle size ~3 nm is obtained. Finally, the procedure can be simplified by combination of the SEA technique with dry impregnation, leading to no Pt loss during the procedure.

  8. 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

  9. Photo-driven electron transfer from the highly reducing excited state of naphthalene diimide radical anion to a CO 2 reduction catalyst within a molecular triad

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, Jose F. [Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center; Northwestern University; Evanston; USA; La Porte, Nathan T. [Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center; Northwestern University; Evanston; USA; Mauck, Catherine M. [Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center; Northwestern University; Evanston; USA; Wasielewski, Michael R. [Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center; Northwestern University; Evanston; USA

    2017-01-01

    The naphthalene-1,4:5,8-bis(dicarboximide) radical anion (NDI-˙), which is easily produced by mild chemical or electrochemical reduction (-0.5 Vvs.SCE), can be photoexcited at wavelengths as long as 785 nm, and has an excited state (NDI-˙*) oxidation potential of -2.1 Vvs.SCE, making it a very attractive choice for artificial photosynthetic systems that require powerful photoreductants, such as CO2 reduction catalysts. However, once an electron is transferred from NDI-˙* to an acceptor directly bound to it, a combination of strong electronic coupling and favorable free energy change frequently make the back electron transfer rapid. To mitigate this effect, we have designed a molecular triad system comprising an NDI-˙ chromophoric donor, a 9,10-diphenylanthracene (DPA) intermediate acceptor, and a Re(dmb)(CO)3carbon dioxide reduction catalyst, where dmb is 4,4'-dimethyl-2,2'-bipyridine, as the terminal acceptor. Photoexcitation of NDI-˙ to NDI-˙* is followed by ultrafast reduction of DPA to DPA-˙, which then rapidly reduces the metal complex. The overall time constant for the forward electron transfer to reduce the metal complex is τ = 20.8 ps, while the time constant for back-electron transfer is six orders of magnitude longer, τ = 43.4 μs. Achieving long-lived, highly reduced states of these metal complexes is a necessary condition for their use as catalysts. The extremely long lifetime of the reduced metal complex is attributed to careful tuning of the redox potentials of the chromophore and intermediate acceptor. The NDI-˙–DPA fragment presents many attractive features for incorporation into other photoinduced electron transfer assemblies directed at the long-lived photosensitization of difficult-to-reduce catalytic centers.

  10. Computer aided molecular design with combined molecular modeling and group contribution

    DEFF Research Database (Denmark)

    Harper, Peter Mathias; Gani, Rafiqul; Kolar, Petr

    1999-01-01

    Computer-aided molecular design (CAMD) provides a means for determining molecules or mixtures of molecules (CAMMD) having a desirable set of physicochemical properties. The application range of CAMD is restricted due to limitations on the complexity of the generated molecular structures and on th......Computer-aided molecular design (CAMD) provides a means for determining molecules or mixtures of molecules (CAMMD) having a desirable set of physicochemical properties. The application range of CAMD is restricted due to limitations on the complexity of the generated molecular structures...

  11. Toward Rational Design of Cu/SSZ-13 Selective Catalytic Reduction Catalysts: Implications from Atomic-Level Understanding of Hydrothermal Stability

    Energy Technology Data Exchange (ETDEWEB)

    Song, James [Institute; The; amp, Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, P.O. Box 646515, Pullman, Washington 99164, United States; Wang, Yilin [Institute; Walter, Eric D. [Environmental; Washton, Nancy M. [Environmental; Mei, Donghai [Institute; Kovarik, Libor [Environmental; Engelhard, Mark H. [Environmental; Prodinger, Sebastian [Institute; Wang, Yong [Institute; The; amp, Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, P.O. Box 646515, Pullman, Washington 99164, United States; Peden, Charles H. F. [Institute; Gao, Feng [Institute

    2017-11-03

    The hydrothermal stability of Cu/SSZ-13 SCR catalysts has been extensively studied, yet atomic level understanding of changes to the zeolite support and the Cu active sites during hydrothermal aging are still lacking. In this work, via the utilization of spectroscopic methods including solid-state 27Al and 29Si NMR, EPR, DRIFTS, and XPS, together with imaging and elemental mapping using STEM, detailed kinetic analyses, and theoretical calculations with DFT, various Cu species, including two types of isolated active sites and CuOx clusters, were precisely quantified for samples hydrothermally aged under varying conditions. This quantification convincingly confirms the exceptional hydrothermal stability of isolated Cu2+-2Z sites, and the gradual conversion of [Cu(OH)]+-Z to CuOx clusters with increasing aging severity. This stability difference is rationalized from the hydrolysis activation barrier difference between the two isolated sites via DFT. Discussions are provided on the nature of the CuOx clusters, and their possible detrimental roles on catalyst stability. Finally, a few rational design principles for Cu/SSZ-13 are derived rigorously from the atomic-level understanding of this catalyst obtained here. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. Computing time was granted by a user proposal at the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) and by the National Energy Research Scientific Computing Center (NERSC). The experimental studies described in this paper were performed in the EMSL, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

  12. Catalytic Hydrogenation and Hydrodeoxygenation of Furfural over Pt(111): A Model System for the Rational Design and Operation of Practical Biomass Conversion Catalysts.

    Science.gov (United States)

    Taylor, Martin J; Jiang, Li; Reichert, Joachim; Papageorgiou, Anthoula C; Beaumont, Simon K; Wilson, Karen; Lee, Adam F; Barth, Johannes V; Kyriakou, Georgios

    2017-04-20

    Furfural is a key bioderived platform chemical whose reactivity under hydrogen atmospheres affords diverse chemical intermediates. Here, temperature-programmed reaction spectrometry and complementary scanning tunneling microscopy (STM) are employed to investigate furfural adsorption and reactivity over a Pt(111) model catalyst. Furfural decarbonylation to furan is highly sensitive to reaction conditions, in particular, surface crowding and associated changes in the adsorption geometry: furfural adopts a planar geometry on clean Pt(111) at low coverage, tilting at higher coverage to form a densely packed furfural adlayer. This switch in adsorption geometry strongly influences product selectivity. STM reveals the formation of hydrogen-bonded networks for planar furfural, which favor decarbonylation on clean Pt(111) and hydrogenolysis in the presence of coadsorbed hydrogen. Preadsorbed hydrogen promotes furfural hydrogenation to furfuryl alcohol and its subsequent hydrogenolysis to methyl furan, while suppressing residual surface carbon. Furfural chemistry over Pt is markedly different from that over Pd, with weaker adsorption over the former affording a simpler product distribution than the latter; Pd catalyzes a wider range of chemistry, including ring-opening to form propene. Insight into the role of molecular orientation in controlling product selectivity will guide the design and operation of more selective and stable Pt catalysts for furfural hydrogenation.

  13. Visible-Light-Responsive Photocatalysis: Ag-Doped TiO2 Catalyst Development and Reactor Design Testing

    Science.gov (United States)

    Coutts, Janelle L.; Hintze, Paul E.; Meier, Anne; Shah, Malay G.; Devor, Robert W.; Surma, Jan M.; Maloney, Phillip R.; Bauer, Brint M.; Mazyck, David W.

    2016-01-01

    In recent years, the alteration of titanium dioxide to become visible-light-responsive (VLR) has been a major focus in the field of photocatalysis. Currently, bare titanium dioxide requires ultraviolet light for activation due to its band gap energy of 3.2 eV. Hg-vapor fluorescent light sources are used in photocatalytic oxidation (PCO) reactors to provide adequate levels of ultraviolet light for catalyst activation; these mercury-containing lamps, however, hinder the use of this PCO technology in a spaceflight environment due to concerns over crew Hg exposure. VLR-TiO2 would allow for use of ambient visible solar radiation or highly efficient visible wavelength LEDs, both of which would make PCO approaches more efficient, flexible, economical, and safe. Over the past three years, Kennedy Space Center has developed a VLR Ag-doped TiO2 catalyst with a band gap of 2.72 eV and promising photocatalytic activity. Catalyst immobilization techniques, including incorporation of the catalyst into a sorbent material, were examined. Extensive modeling of a reactor test bed mimicking air duct work with throughput similar to that seen on the International Space Station was completed to determine optimal reactor design. A bench-scale reactor with the novel catalyst and high-efficiency blue LEDs was challenged with several common volatile organic compounds (VOCs) found in ISS cabin air to evaluate the system's ability to perform high-throughput trace contaminant removal. The ultimate goal for this testing was to determine if the unit would be useful in pre-heat exchanger operations to lessen condensed VOCs in recovered water thus lowering the burden of VOC removal for water purification systems.

  14. Approach to photocatalysis at the molecular level. Design of photocatalysts, detection of intermediate species, and reaction mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Anpo, Masakazu [Department of Applied Chemistry, University of Osaka Prefecture, Gakuen-cho, Sakai, Osaka (Japan)

    1995-08-01

    The characterization of the Cu{sup +}/ZSM-5 catalysts prepared via reduction of ion-exchanged Cu{sup 2+}/ZSM-5 samples and highly dispersed Ti-oxide catalysts anchored on Vycor glass has been undertaken by in-situ photoluminescence, EPR, XAFS (XANES and FT-EXAFS), and FT-IR spectroscopy. UV-irradiation of the Cu{sup +}/ZSM-5 catalyst in the presence of NO leads to the direct photocatalytic decomposition of NO into N{sub 2} and O{sub 2} at normal temperatures. UV-irradiation of the highly dispersed anchored Ti-oxide catalyst in the presence of CO{sub 2} and H{sub 2}O also leads to the evolution of CH{sub 4}, CO, and CH{sub 3}OH at normal temperatures. The clarification of the coordination structure of the active surface sites and the direct detection of the reaction precursors and intermediate species in these photocatalytic systems contributed significantly in characterizing the molecular scale reaction mechanisms. Based on these results, the design of highly concentrated and efficient photocatalysts has successfully been achieved by application of the sol-gel method

  15. Tunable, Chemo- and Site-Selective Nitrene Transfer Reactions through the Rational Design of Silver(I) Catalysts.

    Science.gov (United States)

    Alderson, Juliet M; Corbin, Joshua R; Schomaker, Jennifer M

    2017-09-19

    Carbon-nitrogen (C-N) bonds are ubiquitous in pharmaceuticals, agrochemicals, diverse bioactive natural products, and ligands for transition metal catalysts. An effective strategy for introducing a new C-N bond into a molecule is through transition metal-catalyzed nitrene transfer chemistry. In these reactions, a metal-supported nitrene can either add across a C═C bond to form an aziridine or insert into a C-H bond to furnish the corresponding amine. Typical catalysts for nitrene transfer include Rh 2 L n and Ru 2 L n complexes supported by bridging carboxylate and related ligands, as well as complexes based on Cu, Co, Ir, Fe, and Mn supported by porphyrins and related ligands. A limitation of metal-catalyzed nitrene transfer is the ability to predictably select which specific site will undergo amination in the presence of multiple reactive groups; thus, many reactions rely primarily on substrate control. Achieving true catalyst-control over nitrene transfer would open up exciting possibilities for flexible installation of new C-N bonds into hydrocarbons, natural product-inspired scaffolds, existing pharmaceuticals or biorenewable building blocks. Silver-catalyzed nitrene transfer enables flexible control over the position at which a new C-N bond is introduced. Ag(I) supported by simple N-donor ligands accommodates a diverse range of coordination geometries, from linear to tetrahedral to seesaw, enabling the electronic and steric parameters of the catalyst to be tuned independently. In addition, the ligand, Ag salt counteranion, Ag/ligand ratio and the solvent all influence the fluxional and dynamic behavior of Ag(I) complexes in solution. Understanding the interplay of these parameters to manipulate the behavior of Ag-nitrenes in a predictable manner is a key design feature of our work. In this Account, we describe successful applications of a variety of design principles to tunable, Ag-catalyzed aminations, including (1) changing Ag/ligand ratios to influence

  16. Protein Scaffolding for Small Molecule Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Baker, David [Univ. of Washington, Seattle, WA (United States)

    2014-09-14

    We aim to design hybrid catalysts for energy production and storage that combine the high specificity, affinity, and tunability of proteins with the potent chemical reactivities of small organometallic molecules. The widely used Rosetta and RosettaDesign methodologies will be extended to model novel protein / small molecule catalysts in which one or many small molecule active centers are supported and coordinated by protein scaffolding. The promise of such hybrid molecular systems will be demonstrated with the nickel-phosphine hydrogenase of DuBois et. al.We will enhance the hydrogenase activity of the catalyst by designing protein scaffolds that incorporate proton relays and systematically modulate the local environment of the catalyticcenter. In collaboration with DuBois and Shaw, the designs will be experimentally synthesized and characterized.

  17. MOLECULAR THERMODYNAMICS IN THE DESIGN OF SUBSTITUTE SOLVENTS

    Science.gov (United States)

    The use of physical properties and fluid behavior from molecular thermodynamics can lead to better decision making in the design of substitute solvents and can greatly reduce the expense and time required to find substitutes compared to designing solvents by experiment. this pape...

  18. Reductive dehalogenation of aryl halides over palladium catalysts deposited on SBA-15 type molecular sieve modified with amine donor groups

    Czech Academy of Sciences Publication Activity Database

    Štěpnička, P.; Semler, M.; Demel, J.; Zukal, Arnošt; Čejka, Jiří

    2011-01-01

    Roč. 341, č. 1-2 (2011), s. 97-102 ISSN 1381-1169 R&D Projects: GA ČR GA104/09/0561 Institutional research plan: CEZ:AV0Z40400503 Keywords : heterogeneous catalysts * supported catalysts * palladium Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.947, year: 2011

  19. MOLECULAR DESIGN OF COLLOIDS IN SUPERCRITICAL FLUIDS

    Energy Technology Data Exchange (ETDEWEB)

    Keith P. Johnston

    2009-04-06

    The environmentally benign, non-toxic, non-flammable fluids water and carbon dioxide (CO2) are the two most abundant and inexpensive solvents on earth. Emulsions of these fluids are of interest in many industrial processes, as well as CO2 sequestration and enhanced oil recovery. Until recently, formation of these emulsions required stabilization with fluorinated surfactants, which are expensive and often not environmentally friendly. In this work we overcame this severe limitation by developing a fundamental understanding of the properties of surfactants the CO2-water interface and using this knowledge to design and characterize emulsions stabilized with either hydrocarbon-based surfactants or nanoparticle stabilizers. We also discovered a new concept of electrostatic stabilization for CO2-based emulsions and colloids. Finally, we were able to translate our earlier work on the synthesis of silicon and germanium nanocrystals and nanowires from high temperatures and pressures to lower temperatures and ambient pressure to make the chemistry much more accessible.

  20. Design strategies for organic semiconductors beyond the molecular formula.

    Science.gov (United States)

    Henson, Zachary B; Müllen, Klaus; Bazan, Guillermo C

    2012-09-01

    Organic semiconducting materials based on polymers and molecular systems containing an electronically delocalized structure are the basis of emerging optoelectronic technologies such as plastic solar cells and flexible transistors. For isolated molecules, guidelines exist that rely on the molecular formula to tailor the frontier (highest occupied or lowest unoccupied) molecular orbital energy levels and optical absorption profiles. Much less control can be achieved over relevant properties, however, as one makes the transition to the ensemble behaviour characteristic of the solid state. Polymeric materials are also challenging owing to the statistical description of the average number of repeat units. Here we draw attention to the limitations of molecular formulae as predictive tools for achieving properties relevant to device performances. Illustrative examples highlight the relevance of organization across multiple length scales, and how device performances--although relevant for practical applications--poorly reflect the success of molecular design.

  1. Oxidation catalyst

    Science.gov (United States)

    Ceyer, Sylvia T.; Lahr, David L.

    2010-11-09

    The present invention generally relates to catalyst systems and methods for oxidation of carbon monoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbon monoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

  2. Dispersed metal cluster catalysts by design. Synthesis, characterization, structure, and performance

    Energy Technology Data Exchange (ETDEWEB)

    Arslan, Ilke [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Dixon, David A. [Univ. of Alabama, Tuscaloosa, AL (United States); Gates, Bruce C. [Univ. of California, Davis, CA (United States); Katz, Alexander [Univ. of California, Berkeley, CA (United States)

    2015-09-30

    To understand the class of metal cluster catalysts better and to lay a foundation for the prediction of properties leading to improved catalysts, we have synthesized metal catalysts with well-defined structures and varied the cluster structures and compositions systematically—including the ligands bonded to the metals. These ligands include supports and bulky organics that are being tuned to control both the electron transfer to or from the metal and the accessibility of reactants to influence catalytic properties. We have developed novel syntheses to prepare these well-defined catalysts with atomic-scale control the environment by choice and placement of ligands and applied state-of-the art spectroscopic, microscopic, and computational methods to determine their structures, reactivities, and catalytic properties. The ligands range from nearly flat MgO surfaces to enveloping zeolites to bulky calixarenes to provide controlled coverages of the metal clusters, while also enforcing unprecedented degrees of coordinative unsaturation at the metal site—thereby facilitating bonding and catalysis events at exposed metal atoms. With this wide range of ligand properties and our arsenal of characterization tools, we worked to achieve a deep, fundamental understanding of how to synthesize robust supported and ligand-modified metal clusters with controlled catalytic properties, thereby bridging the gap between active site structure and function in unsupported and supported metal catalysts. We used methods of organometallic and inorganic chemistry combined with surface chemistry for the precise synthesis of metal clusters and nanoparticles, characterizing them at various stages of preparation and under various conditions (including catalytic reaction conditions) and determining their structures and reactivities and how their catalytic properties depend on their compositions and structures. Key characterization methods included IR, NMR, and EXAFS spectroscopies to identify

  3. Molecular Level Control Through Dual Site Participation Using Bimetallic Catalysts - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    d' Itri, Julie, L.; Kovalchuk, Vladimir, I.

    2010-02-08

    The overall goal of this research program was to explore the hypothesis that it is possible to design a bimetallic surface such that each metal catalyzes different elementary reaction steps in an overall reaction pathway. A corollary to this hypothesis is that the different ensemble size requirements for an elementary reaction step can be used to force an elementary reaction step to occur on only one of the metals. The research program involved a combination of materials synthesis, chemical kinetics experiments, spectroscopic studies and computational investigations. The major outcome of this research program was the development and dissemination of the Dual Site Model, for which chlorocarbon reactions in the presence of hydrogen were used as model systems.

  4. Surface Functionalization of g-C 3 N 4 : Molecular-Level Design of Noble-Metal-Free Hydrogen Evolution Photocatalysts

    KAUST Repository

    Chen, Yin

    2015-06-12

    A stable noble-metal-free hydrogen evolution photocatalyst based on graphite carbon nitride (g-C3N4) was developed by a molecular-level design strategy. Surface functionalization was successfully conducted to introduce a single nickel active site onto the surface of the semiconducting g-C3N4. This catalyst family (with less than 0.1 wt% of Ni) has been found to produce hydrogen with a rate near to the value obtained by using 3 wt% platinum as co-catalyst. This new catalyst also exhibits very good stability under hydrogen evolution conditions, without any evidence of deactivation after 24h. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Improvement of Electrochemical Water Oxidation by Fine-Tuning the Structure of Tetradentate N4 Ligands of Molecular Copper Catalysts.

    Science.gov (United States)

    Shen, Junyu; Wang, Mei; Gao, Jinsuo; Han, Hongxian; Liu, Hong; Sun, Licheng

    2017-11-23

    Two copper complexes, [(L1)Cu(OH 2 )](BF 4 ) 2 [1; L1=N,N'-dimethyl-N,N'-bis(pyridin-2-ylmethyl)-1,2-diaminoethane] and [(L2)Cu(OH 2 )](BF 4 ) 2 [2, L2=2,7-bis(2-pyridyl)-3,6-diaza-2,6-octadiene], were prepared as molecular water oxidation catalysts. Complex 1 displayed an overpotential (η) of 1.07 V at 1 mA cm -2 and an observed rate constant (k obs ) of 13.5 s -1 at η 1.0 V in pH 9.0 phosphate buffer solution, whereas 2 exhibited a significantly smaller η (0.70 V) to reach 1 mA cm -2 and a higher k obs (50.4 s -1 ) than 1 under identical test conditions. Additionally, 2 displayed better stability than 1 in controlled potential electrolysis experiments with a faradaic efficiency of 94 % for O 2 evolution at 1.58 V, when a casing tube was used for the Pt cathode. A possible mechanism for 1- and 2-catalyzed O 2 evolution reactions is discussed based on the experimental evidence. These comparative results indicate that fine-tuning the structures of tetradentate N 4 ligands can bring about significant change in the performance of copper complexes for electrochemical water oxidation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. A New Design Strategy for Observing Lithium Oxide Growth-Evolution Interactions Using Geometric Catalyst Positioning.

    Science.gov (United States)

    Ryu, Won-Hee; Gittleson, Forrest S; Li, Jinyang; Tong, Xiao; Taylor, André D

    2016-08-10

    Understanding the catalyzed formation and evolution of lithium-oxide products in Li-O2 batteries is central to the development of next-generation energy storage technology. Catalytic sites, while effective in lowering reaction barriers, often become deactivated when placed on the surface of an oxygen electrode due to passivation by solid products. Here we investigate a mechanism for alleviating catalyst deactivation by dispersing Pd catalytic sites away from the oxygen electrode surface in a well-structured anodic aluminum oxide (AAO) porous membrane interlayer. We observe the cross-sectional product growth and evolution in Li-O2 cells by characterizing products that grow from the electrode surface. Morphological and structural details of the products in both catalyzed and uncatalyzed cells are investigated independently from the influence of the oxygen electrode. We find that the geometric decoration of catalysts far from the conductive electrode surface significantly improves the reaction reversibility by chemically facilitating the oxidation reaction through local coordination with PdO surfaces. The influence of the catalyst position on product composition is further verified by ex situ X-ray photoelectron spectroscopy and Raman spectroscopy in addition to morphological studies.

  7. Catalysts and methods for converting carbonaceous materials to fuels

    Energy Technology Data Exchange (ETDEWEB)

    Hensley, Jesse; Ruddy, Daniel A.; Schaidle, Joshua A.; Behl, Mayank

    2017-07-25

    Catalysts and processes designed to convert DME and/or methanol and hydrogen (H.sub.2) to desirable liquid fuels are described. These catalysts produce the fuels efficiently and with a high selectivity and yield, and reduce the formation of aromatic hydrocarbons by incorporating H.sub.2 into the products. Also described are process methods to further upgrade these fuels to higher molecular weight liquid fuel mixtures, which have physical properties comparable with current commercially used liquid fuels.

  8. Catalysts and methods for converting carbonaceous materials to fuels

    Energy Technology Data Exchange (ETDEWEB)

    Hensley, Jesse; Ruddy, Daniel A.; Schaidle, Joshua A.; Behl, Mayank

    2017-10-24

    This disclosure relates to catalysts and processes designed to convert DME and/or methanol and hydrogen (H.sub.2) to desirable liquid fuels. These catalysts produce the fuels efficiently and with a high selectivity and yield, and reduce the formation of aromatic hydrocarbons by incorporating H.sub.2 into the products. This disclosure also describes process methods to further upgrade these fuels to higher molecular weight liquid fuel mixtures, which have physical properties comparable with current commercially used liquid fuels.

  9. Catalysts and methods for converting carbonaceous materials to fuels

    Energy Technology Data Exchange (ETDEWEB)

    Hensley, Jesse; Ruddy, Daniel A.; Schaidle, Joshua A.; Behl, Mayank

    2017-10-31

    Catalysts and processes designed to convert DME and/or methanol and hydrogen (H.sub.2) to desirable liquid fuels are described. These catalysts produce the fuels efficiently and with a high selectivity and yield, and reduce the formation of aromatic hydrocarbons by incorporating H.sub.2 into the products. Also described are process methods to further upgrade these fuels to higher molecular weight liquid fuel mixtures, which have physical properties comparable with current commercially used liquid fuels.

  10. Computationally Probing the Performance of Hybrid, Heterogeneous, and Homogeneous Iridium-Based Catalysts for Water Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    García-Melchor, Max [SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford CA (United States); Vilella, Laia [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST),Tarragona (Spain); Departament de Quimica, Universitat Autonoma de Barcelona, Barcelona (Spain); López, Núria [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Tarragona (Spain); Vojvodic, Aleksandra [SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park CA (United States)

    2016-04-29

    An attractive strategy to improve the performance of water oxidation catalysts would be to anchor a homogeneous molecular catalyst on a heterogeneous solid surface to create a hybrid catalyst. The idea of this combined system is to take advantage of the individual properties of each of the two catalyst components. We use Density Functional Theory to determine the stability and activity of a model hybrid water oxidation catalyst consisting of a dimeric Ir complex attached on the IrO2(110) surface through two oxygen atoms. We find that homogeneous catalysts can be bound to its matrix oxide without losing significant activity. Hence, designing hybrid systems that benefit from both the high tunability of activity of homogeneous catalysts and the stability of heterogeneous systems seems feasible.

  11. Nano-nitride cathode catalysts of Ti, Ta, and Nb for polymer electrolyte fuel cells: Temperature-programmed desorption investigation of molecularly adsorbed oxygen at low temperature

    KAUST Repository

    Ohnishi, Ryohji

    2013-01-10

    TiN, NbN, TaN, and Ta3N5 nanoparticles synthesized using mesoporous graphitic (mpg)-C3N4 templates were investigated for the oxygen reduction reaction (ORR) as cathode catalysts for polymer electrolyte fuel cells. The temperature-programmed desorption (TPD) of molecularly adsorbed O2 at 120-170 K from these nanoparticles was examined, and the resulting amount and temperature of desorption were key factors determining the ORR activity. The size-dependent TiN nanoparticles (5-8 and 100 nm) were then examined. With decreasing particle size, the density of molecularly adsorbed O2 per unit of surface area increased, indicating that a decrease in particle size increases the number of active sites. It is hard to determine the electrochemical active surface area for nonmetal electrocatalysts (such as oxides or nitrides), because of the absence of proton adsorption/desorption peaks in the voltammograms. In this study, O2-TPD for molecularly adsorbed O2 at low temperature demonstrated that the amount and strength of adsorbed O2 were key factors determining the ORR activity. The properties of molecularly adsorbed O2 on cathode catalysts are discussed against the ORR activity. © 2012 American Chemical Society.

  12. Evaluation report on the design of solid catalysts for saving energy in petrochemical industry; Sekiyu kagaku no tame no sho energy gata kotai shokubai sekkei hyoka hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2001-03-01

    The aim is to improve on hydrocarbon oxidation which is a difficult reaction (analogous to combustion and having potential for heat generation or explosion, with restrictions therefore imposed on reaction conditions) by use of a catalyst supporting porous membrane. The fiscal 1999-2000 results are stated. In this effort, the target reaction is promoted by a catalyst supported by a porous membrane while combustion is controlled by the said porous membrane that separates oxygen and hydrocarbon from each other. Such a design was not available since a catalyst supporting inorganic membrane withstanding so high a temperature was difficult to prepare. Recently, however, a porous membrane with its pores regulated to microstructural dimensions was developed. The activity of a Pd membrane catalyst is evaluated in view of the degree of oxidation of propylene, cyclohexene, and benzene. It is then found that hydrogen that has passed the Pd membrane participates in the reaction. In a propylene oxidation test using a membrane type Ag/Al{sub 2}O{sub 3} catalyst, it is found that acetone is generated and that oxygen after passing through the membrane participates in the reaction. Methods are studied for preparing a metal membrane in which the catalyst system comprises a catalyst supporting porous membrane and a Pd membrane. In the fabrication of metal membranes, a highly selective hydrogen permeable membrane is stably prepared by the thermal CVD (chemical vapor deposition) method. (NEDO)

  13. Design of optimal laser pulses to control molecular rovibrational ...

    Indian Academy of Sciences (India)

    Optimal control theory in combination with time-dependent quantum dynamics is employed to design laser ... area of quantum computing,22 use of molecular states of various systems ..... frequency) and ωv=0, j=1→v=1, j=0, along with small con- tributions from ... discussed here for three rovibrational excitation pro- cesses.

  14. Molecular Design and Functional Control of Novel Self-Oscillating Polymers

    Directory of Open Access Journals (Sweden)

    Ryo Yoshida

    2010-02-01

    Full Text Available If we could realize an autonomous polymer system driven under biological conditions by a tailor-made molecular design, human beings could create unprecedented biomimetic functions and materials such as heartbeats, autonomous peristaltic pumps, etc. In order to achieve this objective, we have investigated the molecular design of such a polymer system. As a result, we were the first to demonstrate a self-oscillating polymer system driven in a solution where only malonic acid existed, which could convert the chemical energy of the Belousov-Zhabotinsky (BZ reaction into a change in the conformation of the polymer chain. To cause the self-oscillation in solution, we have attempted to construct a built-in system where the required BZ system substrates other than the organic acid are incorporated into the polymer itself. That is, the novel polymer chain incorporated the metal catalyst of the BZ reaction, a pH-control site and an oxidant supply site at the same time. As a result of introducing the pH control and oxidant supply sites into the conventional-type self-oscillating polymer chain, the novel polymer chain caused aggregation-disaggregation self-oscillations in the solution. We clarified that the period of the self-oscillation of the novel self-oscillating polymer chain was proportional to the concentration of the malonic acid. Therefore, the concentration of the malonic acid can be determined by measuring the period of the novel self-oscillating polymer solution. In this review, we introduce the detailed molecular design of the novel self-oscillating polymer chain and its self-oscillating behavior. Moreover, we report an autonomous self-oscillating polymer gel actuator that causes a bending-stretching motion under the constant conditions.

  15. Micro-/nanostructured multicomponent molecular materials: design, assembly, and functionality.

    Science.gov (United States)

    Yan, Dongpeng

    2015-03-23

    Molecule-based micro-/nanomaterials have attracted considerable attention because their properties can vary greatly from the corresponding macro-sized bulk systems. Recently, the construction of multicomponent molecular solids based on crystal engineering principles has emerged as a promising alternative way to develop micro-/nanomaterials. Unlike single-component materials, the resulting multicomponent systems offer the advantages of tunable composition, and adjustable molecular arrangement, and intermolecular interactions within their solid states. The study of these materials also supplies insight into how the crystal structure, molecular components, and micro-/nanoscale effects can influence the performance of molecular materials. In this review, we describe recent advances and current directions in the assembly and applications of crystalline multicomponent micro-/nanostructures. Firstly, the design strategies for multicomponent systems based on molecular recognition and crystal engineering principles are introduced. Attention is then focused on the methods of fabrication of low-dimensional multicomponent micro-/nanostructures. Their new applications are also outlined. Finally, we briefly discuss perspectives for the further development of these molecular crystalline micro-/nanomaterials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Mesoporous molecular sieve catalysts

    DEFF Research Database (Denmark)

    Højholt, Karen Thrane

    of the mode of deactivation revealed that the zeolites deactivated due to coke formation and that the Ga-MFI zeotypes deactivated due to loss of the catalytically active Brønsted acid sites caused by hydrolysis of Ga-O bonds leading to formation of inactive extra-framework gallium. Zeolites can not only...

  17. Central composite design approach towards optimization of flamboyant pods derived steam activated carbon for its use as heterogeneous catalyst in transesterification of Hevea brasiliensis oil

    International Nuclear Information System (INIS)

    Dhawane, Sumit H.; Kumar, Tarkeshwar; Halder, Gopinath

    2015-01-01

    Highlights: • Activated carbon was prepared from novel precursor flamboyant pods (Delonix regia). • Activation process was optimized using central composite design approach. • Prepared activated carbon at optimized condition was used as support for KOH. • Carbon based heterogeneous catalyst was used in transesterification of HBO. • Effect of catalyst loading and alcohol ratio on biodiesel yield was studied. - Abstract: The present investigation emphasises the preparation of carbon based KOH impregnated heterogeneous catalyst from flamboyant pods (Delonix regia) for the production of biodiesel from novel feedstock Hevea brasiliensis oil (HBO). Initially, carbonized char was physically activated by superheated steam and the process was optimized to study the effects of activation time and temperature by central composite design approach (CCD) using response surface methodology (RSM). Activated carbon was impregnated with KOH at four different ratios. Biodiesel production process was carried out at constant temperature 60 °C, reaction time 1 h, and 5 g of carbon based catalyst at varying quantities of catalyst loading (0.5, 2, 3.5, 5 wt%) and methanol to oil ratio (5:1–20:1). The influence of parameters on the biodiesel yield at varied condition was studied. Maximum yield of 89.3% was obtained at methanol to oil ratio 15:1 and catalyst loading 3.5 wt% and corresponding yield at same process parameters was observed to be 88.7% implying the significant activity of catalyst in reutilization. Produced biodiesel was characterized following ASTM standards. The experimental analysis confirmed that the carbonaceous catalyst developed from flamboyant pods under optimized condition is capable of transesterifying HBO into biodiesel

  18. Design of Carborane Molecular Architectures via Electronic Structure Computations

    International Nuclear Information System (INIS)

    Oliva, J.M.; Serrano-Andres, L.; Klein, D.J.; Schleyer, P.V.R.; Mich, J.

    2009-01-01

    Quantum-mechanical electronic structure computations were employed to explore initial steps towards a comprehensive design of poly carborane architectures through assembly of molecular units. Aspects considered were (i) the striking modification of geometrical parameters through substitution, (ii) endohedral carboranes and proposed ejection mechanisms for energy/ion/atom/energy storage/transport, (iii) the excited state character in single and dimeric molecular units, and (iv) higher architectural constructs. A goal of this work is to find optimal architectures where atom/ion/energy/spin transport within carborane superclusters is feasible in order to modernize and improve future photo energy processes.

  19. Design of high-activity single-atom catalysts via n-p codoping

    Science.gov (United States)

    Wang, Xiaonan; Zhou, Haiyan; Zhang, Xiaoyang; Jia, Jianfeng; Wu, Haishun

    2018-03-01

    The large-scale synthesis of stable single-atom catalysts (SACs) in experiments remains a significant challenge due to high surface free energy of metal atom. Here, we propose a concise n-p codoping approach, and find it can not only disperse the relatively inexpensive metal, copper (Cu), onto boron (B)-doped graphene, but also result in high-activity SACs. We use CO oxidation on B/Cu codoped graphene as a prototype example, and demonstrate that: (1) a stable SAC can be formed by stronger electrostatic attraction between the metal atom (n-type Cu) and support (p-type B-doped graphene). (2) the energy barrier of the prototype CO oxidation on B/Cu codoped graphene is 0.536 eV by the Eley-Rideal mechanism. Further analysis shows that the spin selection rule can provide well theoretical insight into high activity of our suggested SAC. The concept of n-p codoping may lead to new strategy in large-scale synthesis of stable single-atom catalysts.

  20. Probing the molecular design of hyper-branched aryl polyesters towards lubricant applications.

    Science.gov (United States)

    Robinson, Joshua W; Zhou, Yan; Bhattacharya, Priyanka; Erck, Robert; Qu, Jun; Bays, J Timothy; Cosimbescu, Lelia

    2016-01-05

    We report novel polymeric materials that may be used as viscosity index improvers (VII) for lubricant applications. Our efforts included probing the comb-burst hyper-branched aryl polyester architecture for beneficial viscosity and friction behavior when utilized as an additive in a group I oil. The monomer was designed as to undergo polymerization via polycondensation within the architectural construct (AB2), typical of hyperbranched polymers. The monomer design was comprised of aliphatic arms (12 or 16 methylenes) to provide the necessary lipophilicity to achieve solubility in a non-polar medium. Once polymerized, via catalyst and heat, the surface alcohols were functionalized with fatty acids (lauric and palmitic). Controlling the aliphatic nature of the internal arms and peripheral end-groups provided four unique flexible polymer designs. Changing the reaction time and concentration provided opportunities to investigate the influence of molecular weight and branching density on oil-solubility, viscosity, and friction. Oil-solubility was found to decrease with fewer internal carbons, but the number of internal carbons appears to have little influence on the bulk solution viscosity. At concentrations of 2 wt % in a group I base oil, these polymer additives demonstrated an improved viscosity index and reduced friction coefficient, validating the basic approach.

  1. Probing the molecular design of hyper-branched aryl polyesters towards lubricant applications

    Science.gov (United States)

    Robinson, Joshua W.; Zhou, Yan; Bhattacharya, Priyanka; Erck, Robert; Qu, Jun; Bays, J. Timothy; Cosimbescu, Lelia

    2016-01-01

    We report novel polymeric materials that may be used as viscosity index improvers (VII) for lubricant applications. Our efforts included probing the comb-burst hyper-branched aryl polyester architecture for beneficial viscosity and friction behavior when utilized as an additive in a group I oil. The monomer was designed as to undergo polymerization via polycondensation within the architectural construct (AB2), typical of hyperbranched polymers. The monomer design was comprised of aliphatic arms (12 or 16 methylenes) to provide the necessary lipophilicity to achieve solubility in a non-polar medium. Once polymerized, via catalyst and heat, the surface alcohols were functionalized with fatty acids (lauric and palmitic). Controlling the aliphatic nature of the internal arms and peripheral end-groups provided four unique flexible polymer designs. Changing the reaction time and concentration provided opportunities to investigate the influence of molecular weight and branching density on oil-solubility, viscosity, and friction. Oil-solubility was found to decrease with fewer internal carbons, but the number of internal carbons appears to have little influence on the bulk solution viscosity. At concentrations of 2 wt % in a group I base oil, these polymer additives demonstrated an improved viscosity index and reduced friction coefficient, validating the basic approach.

  2. Bottom-Up Design of a Copper-Ruthenium Nanoparticulate Catalyst for Low-Temperature Ammonia Oxidation

    DEFF Research Database (Denmark)

    Chakraborty, Debasish; Damsgaard, Christian Danvad; Silva, Hugo José Lopes

    2017-01-01

    that for Ru and forty-fold higher than that for Cu. X-ray absorption spectroscopy suggests that in the most active catalyst Cu forms one or two monolayer thick patches on Ru and the catalysts are less active once 3D Cu islands form. The good performance of the tuned Cu/Ru catalyst is attributed to changes...

  3. A computer-aided molecular design framework for crystallization solvent design

    DEFF Research Database (Denmark)

    Karunanithi, Arunprakash T.; Achenie, Luke E.K.; Gani, Rafiqul

    2006-01-01

    One of the key decisions in designing solution crystallization processes is the selection of solvents. In this paper, we present a computer-aided molecular design (CAMD) framework for the design and selection of solvents and/or anti-solvents for solution crystallization. The CAMD problem is formu......One of the key decisions in designing solution crystallization processes is the selection of solvents. In this paper, we present a computer-aided molecular design (CAMD) framework for the design and selection of solvents and/or anti-solvents for solution crystallization. The CAMD problem...... solvent molecules. Solvent design and selection for two types of solution crystallization processes namely cooling crystallization and drowning out crystallization are presented. In the first case study, the design of single compound solvent for crystallization of ibuprofen, which is an important...

  4. Supported nano gold as a recyclable catalyst for green, selective and efficient oxidation of alcohol using molecular oxygen

    Directory of Open Access Journals (Sweden)

    Bashir Dar

    2011-09-01

    Full Text Available The myth that gold cannot act as a catalyst has been discarded in view of recent studies, which have demonstrated the high catalytic efficiency of pure nano-gold and supported nano-gold catalysts. In recent years, numerous papers have described the use of supported nano-gold particles for catalysis in view of their action on CO and O2 to form CO2, as well as a variety of other reactions. Special emphasis is placed on the oxidation studies undertaken on model nano-Au systems. In this work a solvent free oxidation of 1-phenyl ethanol was carried out using gold supported on ceria-silica, ceria-titania, ceria- zirconia and ceria-alumina at 160 0C. Almost 88-97% conversion was obtained with >99% selectivity. Temperature screening was done from 70 to 160 0C.Catalysts were prepared by deposition co-precipitation method and deposition was determined by EDEX analysis.

  5. Photocatalytic water splitting: Materials design and high-throughput screening of molecular compositions

    Science.gov (United States)

    Khnayzer, Rony S.

    , photons of low energy are converted into higher energy light using a process termed photon upconversion. Using this technique, low energy photons supplied by the sun can be converted into light of appropriate energy to trigger electronic transitions in high energy absorbing photoactive materials without any chemical modification of the latter. We have shown, that this technology is capable of upconverting visible sunlight to sensitize wide-bandgap semiconductors such as WO3, subsequently extending the photoaction of these materials to cover a larger portion of the solar spectrum. Besides the engineering of different compositions that serve as either sensitizers or catalysts in these solar energy conversion schemes, we have designed an apparatus for parallel high-throughput screening of these photocatalytic compositions. This combinatorial approach to solar fuels photocatalysis has already led to unprecedented fundamental understanding of the generation of hydrogen gas from pure water. The activity of a series of new Ru(II) sensitizers along with Co(II) molecular WRCs were optimized under visible light excitation utilizing different experimental conditions. The multi-step mechanism of activity of selected compositions was further elucidated by pump-probe transient absorption spectroscopy.

  6. Molecular design of flotation collectors: A recent progress.

    Science.gov (United States)

    Liu, Guangyi; Yang, Xianglin; Zhong, Hong

    2017-08-01

    The nature of froth flotation is to selectively hydrophobize valuable minerals by collector adsorption so that the hydrophobized mineral particles can attach air bubbles. In recent years, the increasing commercial production of refractory complex ores has been urgent to develop special collectors for enhancing flotation separation efficiency of valuable minerals from these ores. Molecular design methods offer an effective way for understanding the structure-property relationship of flotation collectors and developing new ones. The conditional stability constant (CSC), molecular mechanics (MM), quantitative structure-activity relationship (QSAR), and first-principle theory, especially density functional theory (DFT), have been adopted to build the criteria for designing flotation collectors. Azole-thiones, guanidines, acyl thioureas and thionocarbamates, amide-hydroxamates, and double minerophilic-group surfactants such as Gemini, dithiourea and dithionocarbamate molecules have been recently developed as high-performance collectors. To design hydrophobic groups, the hydrophilic-hydrophobic balance parameters have been extensively used as criteria. The replacement of aryl group with aliphatic group or CC single bond(s) with CC double bond(s), reduction of carbon numbers, introduction of oxygen atom(s) and addition of trisiloxane to the tail terminal have been proved to be useful approaches for adjusting the surface activity of collectors. The role of molecular design of collectors in practical flotation applications was also summarized. Based on the critical review, some comments and prospects for further research on molecular design of flotation collectors were also presented in the paper. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Development of Optimal Catalyst Designs and Operating Strategies for Lean NOx Reduction in Coupled LNT-SCR Systems

    Energy Technology Data Exchange (ETDEWEB)

    Harold, Michael [Univ. of Houston, TX (United States); Crocker, Mark [Univ. of Kentucky, Lexington, KY (United States); Balakotaiah, Vemuri [Univ. of Houston, TX (United States); Luss, Dan [Univ. of Houston, TX (United States); Choi, Jae-Soon [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Dearth, Mark [Ford Motor Company, Dearborn, MI (United States); McCabe, Bob [Ford Motor Company, Dearborn, MI (United States); Theis, Joe [Ford Motor Company, Dearborn, MI (United States)

    2013-09-30

    alternative reductants such as propylene, representing the hydrocarbon component of diesel exhaust. First-principle models of the LNT and SCR converters, which utilized the mechanistic-based kinetics and realistic treatments of the flow and transport processes, in combination with bench-scale reactor experiments helped to identify the best designs for combining the NSR and SCR catalysts over a range of operating conditions encountered in practice. This included catalysts having multiple zones and layers and additives with the focus on determining the minimal precious metal component needed to meet emission abatement targets over a wide range of operating conditions. The findings from this study provide diesel vehicle and catalyst companies valuable information to develop more cost effective diesel emissions catalysts which helps to expand the use of more fuel efficient diesel power. The fundamental modeling and experimental tools and findings from this project can be applied to catalyst technologies used in the energy and chemical industries. Finally, the project also led to training of several doctoral students who were placed in research jobs in industry and academia.

  8. Molecular heterogeneous catalysts derived from bipyridine-based organosilica nanotubes for C–H bond activation† †Electronic supplementary information (ESI) available: Experimental details, material characterization data, catalytic measurement details. See DOI: 10.1039/c7sc00713b Click here for additional data file.

    Science.gov (United States)

    Zhang, Shengbo; Wang, Hua; Li, Mei; Han, Jinyu

    2017-01-01

    Heterogeneous metal complex catalysts for direct C–H activation with high activity and durability have always been desired for transforming raw materials into feedstock chemicals. This study described the design and synthesis of one-dimensional organosilica nanotubes containing 2,2′-bipyridine (bpy) ligands in the framework (BPy-NT) and their post-synthetic metalation to provide highly active and robust molecular heterogeneous catalysts. By adjusting the ratios of organosilane precursors, very short BPy-NT with ∼50 nm length could be controllably obtained. The post-synthetic metalation of bipyridine-functionalized nanotubes with [IrCp*Cl(μ-Cl)]2 (Cp* = η5-pentamethylcyclopentadienyl) and [Ir(cod)(OMe)]2 (cod = 1,5-cyclooctadiene) afforded solid catalysts, IrCp*-BPy-NT and Ir(cod)-BPy-NT, which were utilized for C–H oxidation of heterocycles and cycloalkanes as well as C–H borylation of arenes. The cut-short nanotube catalysts displayed enhanced activities and durability as compared to the analogous homogeneous catalysts and other conventional heterogeneous catalysts, benefiting from the isolated active sites as well as the fast transport of substrates and products. After the reactions, a detailed characterization of Ir-immobilized BPy-NT via TEM, SEM, nitrogen adsorption, UV/vis, XPS, and 13C CP MAS NMR indicated the molecular nature of the active species as well as stable structures of nanotube scaffolds. This study demonstrates the potential of BPy-NT with a short length as an integration platform for the construction of efficient heterogeneous catalytic systems for organic transformations. PMID:28970878

  9. Design of Polymer-Coated Multi-Walled Carbon Nanotube/Carbon Black-based Fuel Cell Catalysts with High Durability and Performance Under Non-humidified Condition

    International Nuclear Information System (INIS)

    Yang, Zehui; Berber, Mohamed R.; Nakashima, Naotoshi

    2015-01-01

    To realize a high catalyst utilization, better fuel cell performance and durability as well as low production cost, an efficient design strategy of the catalyst layer that can improve both the oxygen accessibility and structure stability is highly required. Here, we describe the preparation of fuel cell electrocatalysts with an efficient fuel cell performance and better stability based on hybrids of multi-walled carbon nanotubes (MWNTs) and carbon black (CB) which were wrapped by a proton conducting polymer, poly[2,2′-(2,6-pyridine)-5,5′-bibenzimidazole], before deposition of the platinum (Pt) metal catalyst. The catalyst mass activity after feeding only 10%-MWNTs to CB increased by 1.5 and 2 times than those of the MWNTs-based- and CB-based catalysts, respectively. The results also demonstrated that 90 wt% of the MWNTs in the catalyst layer allows it to be replaced by CB without any significant change in its durability and performance under 120 °C and non-humidified condition

  10. Developing Selective Oxidation Catalysts of Light Alkanes:. from Fundamental Understanding to Rational Design

    Science.gov (United States)

    Fu, Gang; Yi, Xiaodong; Huang, Chuanjing; Xu, Xin; Weng, Weizheng; Xia, Wensheng; Wan, Hui-Lin

    Selective oxidation of light alkanes remains to be a great challenge for the wider use of alkanes as feedstocks. To achieve high activity and at the same time high selectivity, some key issues have to be addressed: (1) the stability of the desired products with respect to the reactants; (2) the roles of the active components in the catalysts, the structure and the functionality of the active centers; (3) the reducibility of the metal cations, the Lewis acid sites and their synergic effects with the basic sites of the lattice oxygen anions; (4) spatial isolation of the active centers; and (5) the mechanisms for the formation and transformation of the intermediates and their kinetic controls. In this contribution, we took selective oxidation of propane to acrolein as our target reaction, and reviewed mainly our own work, trying to provide some thinking and answers to these five questions.

  11. Nanostructured platinum-free electrocatalysts in alkaline direct alcohol fuel cells: catalyst design, principles and applications

    CSIR Research Space (South Africa)

    Ozoemena, Kenneth I

    2016-01-01

    Full Text Available in nanoparticles and semi-innite surfaces. Table 1Table 1 Typical calculated segregation energies (eV) for binary alloy nanoparticles Core Shell Ag Pd Ni Ir Co Fe Ag 0 �0.82 �2.29 �3.54 �2.15 �5.20 Pd 0.70 0 �1.09 �1.71 �1.29 �3.26 Ni 0.67 0.46 0 �0.67 �0.20 �2... compares the Wigner–Seitz radii and electron densities of somemetallic elements that are useful for making alloy catalysts for AFC systems. Table 2 clearly indicates that Pd, for example, has a stronger tendency to surface-segregate in Ni, Fe, or Fe...

  12. Predictive Modelling of Phase-Transfer Catalyst Systems for Improved and Innovative Design

    DEFF Research Database (Denmark)

    Anantpinijwatna, Amata; Hyung Kim, Sun; Sales-Cruz, Mauricio

    2016-01-01

    Phase-transfer catalyst (PTC) systems contain two immiscible liquid phases with a heterogeneous PTC transferring active ion from one phase to the other for converting the reactant to the desired product, and in the process generating the inactive ion. This type of reacting systems is receiving...... increasing attention as a novel organic synthesis option due to its flexible and easier operation, higher production yield, and ability to eliminate expensive solvents, although, not eliminating the use of solvents. New mathematical models of the PTC system, which includes physical and chemical equilibrium......, reaction mechanism and unit operation has been developed. In the developed model, the PTC system is divided into four sub-systems of aqueous-organic solvent partition, inorganic salt in aqueous phase, PTC in aqueous phase, and PTC in aqueous phase. Each subsystem requires an appropriate thermodynamic model...

  13. Influence of Multi-Valency, Electrostatics and Molecular Recognition on the Adsorption of Transition Metal Complexes on Metal Oxides: A Molecular Approach to Catalyst Synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Rioux, Robert M. [Pennsylvania State Univ., University Park, PA (United States)

    2017-03-31

    In this work, we have primarily utilized isothermal titration calorimetry (ITC) and complimentary catalyst characterization techniques to study and assess the impact of solution conditions (i.e., solid-liquid) interface on the synthesis of heterogeneous and electro-catalysts. Isothermal titration calorimetry is well-known technique from biochemistry/physics, but has been applied to a far lesser extent to characterize buried solid-liquid interfaces in materials science. We demonstrate the utility and unique information provided by ITC for two distinct catalytic systems. We explored the thermodynamics associated catalyst synthesis for two systems: (i) ion-exchange or strong electrostatic adsorption for Pt and Pd salts on silica and alumina materials (ii) adsorption to provide covalent attachment of metal and metal-oxo clusters to Dion-Jacobsen perovskite materials.

  14. Nanosized ruthenium particles decorated carbon nanofibers as active catalysts for the oxidation of p-cymene by molecular oxygen

    CSIR Research Space (South Africa)

    Makgwane, PR

    2013-07-01

    Full Text Available demonstrated that the direct participation of the catalyst in p-cymene C-H bond activation occurred via catalytic decomposition of tertiary-butyl hydroperoxide (TBHP), which was added as an initiator, into a free-radical chain initiator rather than the direct H...

  15. Synthesis and catalytic evaluation in the Heck reaction of deposited palladium catalysts immobilized via amide linkers and their molecular analogues

    Czech Academy of Sciences Publication Activity Database

    Semler, M.; Čejka, Jiří; Štěpnička, P.

    2014-01-01

    Roč. 227, MAY 2014 (2014), s. 207-214 ISSN 0920-5861 R&D Projects: GA ČR GA104/09/0561; GA ČR(CZ) GA13-08944S Institutional support: RVO:61388955 Keywords : deposited catalysts * palladium * amide linkers Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.893, year: 2014

  16. Transformation of levoglucosan over H-MCM-22 zeolite and H-MCM-41 mesoporous molecular sieve catalysts

    International Nuclear Information System (INIS)

    Kaeldstroem, M.; Kumar, N.; Heikkilae, T.; Tiitta, M.; Salmi, T.; Murzin, D. Yu.

    2011-01-01

    Catalytic transformation of levoglucosan (1-6-anhdyro-β-D-glucopyranose) was carried out in a fixed bed reactor at 573 K over zeolite and mesoporous material catalysts. Proton forms of MCM-22-30 and MCM-41-20 catalysts were tested in the conversion, changing also the residence time. The yield of the transformation product phases was substantially influenced by the structures, at the same time the formation of the different compounds were dependent on the structures of the acidic zeolite catalysts. Oxygenated species were the main liquid product, consisting mainly of aldehydes and furfurals (glycolaldehyde, formaldehyde, acetaldehyde, furfural, 5-methylfurfural, acetic acid). The formation of the liquid products was higher over MCM-41-20 than over MCM-22-30 for all the oxygenated species except acetic acid, indicating larger formation of non-condensable products over the microporous material. By increasing the residence time the formation of acetic acid increased in transformations over MCM-22, however, such increase also led to generation of more gases with both catalysts. The deactivation due to coking was more severe over the zeolite compared to the mesoporous material. It was, however, possible to successfully regenerate the spent zeolites without changing the structure. -- Highlights: → Transformation of levoglucosan (1-6-anhdyro-β-D-glucopyranose) was done at 573 K. → MCM-22-30 and MCM-41-20 catalysts were tested. → Oxygenated species (glycolaldehyde, formaldehyde, acetaldehyde, furfural, 5-methylfurfural, acetic acid) were the main liquid products. → Acidity had an influence on product distribution and deactivation.

  17. Gold-catalyzed aerobic epoxidation of trans-stilbene in methylcyclohexane. Part I: Design of a reference catalyst

    KAUST Repository

    Guillois, Kevin

    2012-02-01

    The kinetics of the heterogeneous gold-catalyzed aerobic epoxidation of stilbene in the liquid phase has been shown to be hindered by diffusion limitations, due to the use of supports which are unsuitable to apolar reaction media. The choice of these supports is generally dictated by the ability of standard methods of preparation to stabilize highly dispersed gold nanoparticles on them. Hence, new methods need to be designed in order to produce catalytically active gold nanoparticles on hydrophobic supports in general and on passivated silicas in particular. By investigating Tsukuda\\'s method to produce colloidal solutions of gold nanoparticles upon reduction of the triphenylphosphine gold chloride complex in solution, we found that direct reduction of AuPPh3Cl in the presence of a commercially available silica support functionalized with dimethylsiloxane, Aerosil R972, leads, in a highly reproducible and potentially scalable way, to the best catalyst ever reported for this reaction. (C) 2011 Elsevier BM. All rights reserved.

  18. Gold-catalyzed aerobic epoxidation of trans-stilbene in methylcyclohexane. Part I: Design of a reference catalyst

    KAUST Repository

    Guillois, Kevin; Burel, Laurence; Tuel, Alain; Caps, Valerie

    2012-01-01

    The kinetics of the heterogeneous gold-catalyzed aerobic epoxidation of stilbene in the liquid phase has been shown to be hindered by diffusion limitations, due to the use of supports which are unsuitable to apolar reaction media. The choice of these supports is generally dictated by the ability of standard methods of preparation to stabilize highly dispersed gold nanoparticles on them. Hence, new methods need to be designed in order to produce catalytically active gold nanoparticles on hydrophobic supports in general and on passivated silicas in particular. By investigating Tsukuda's method to produce colloidal solutions of gold nanoparticles upon reduction of the triphenylphosphine gold chloride complex in solution, we found that direct reduction of AuPPh3Cl in the presence of a commercially available silica support functionalized with dimethylsiloxane, Aerosil R972, leads, in a highly reproducible and potentially scalable way, to the best catalyst ever reported for this reaction. (C) 2011 Elsevier BM. All rights reserved.

  19. Biomimetic molecular design tools that learn, evolve, and adapt

    Directory of Open Access Journals (Sweden)

    David A Winkler

    2017-06-01

    Full Text Available A dominant hallmark of living systems is their ability to adapt to changes in the environment by learning and evolving. Nature does this so superbly that intensive research efforts are now attempting to mimic biological processes. Initially this biomimicry involved developing synthetic methods to generate complex bioactive natural products. Recent work is attempting to understand how molecular machines operate so their principles can be copied, and learning how to employ biomimetic evolution and learning methods to solve complex problems in science, medicine and engineering. Automation, robotics, artificial intelligence, and evolutionary algorithms are now converging to generate what might broadly be called in silico-based adaptive evolution of materials. These methods are being applied to organic chemistry to systematize reactions, create synthesis robots to carry out unit operations, and to devise closed loop flow self-optimizing chemical synthesis systems. Most scientific innovations and technologies pass through the well-known “S curve”, with slow beginning, an almost exponential growth in capability, and a stable applications period. Adaptive, evolving, machine learning-based molecular design and optimization methods are approaching the period of very rapid growth and their impact is already being described as potentially disruptive. This paper describes new developments in biomimetic adaptive, evolving, learning computational molecular design methods and their potential impacts in chemistry, engineering, and medicine.

  20. Biomimetic molecular design tools that learn, evolve, and adapt

    Science.gov (United States)

    2017-01-01

    A dominant hallmark of living systems is their ability to adapt to changes in the environment by learning and evolving. Nature does this so superbly that intensive research efforts are now attempting to mimic biological processes. Initially this biomimicry involved developing synthetic methods to generate complex bioactive natural products. Recent work is attempting to understand how molecular machines operate so their principles can be copied, and learning how to employ biomimetic evolution and learning methods to solve complex problems in science, medicine and engineering. Automation, robotics, artificial intelligence, and evolutionary algorithms are now converging to generate what might broadly be called in silico-based adaptive evolution of materials. These methods are being applied to organic chemistry to systematize reactions, create synthesis robots to carry out unit operations, and to devise closed loop flow self-optimizing chemical synthesis systems. Most scientific innovations and technologies pass through the well-known “S curve”, with slow beginning, an almost exponential growth in capability, and a stable applications period. Adaptive, evolving, machine learning-based molecular design and optimization methods are approaching the period of very rapid growth and their impact is already being described as potentially disruptive. This paper describes new developments in biomimetic adaptive, evolving, learning computational molecular design methods and their potential impacts in chemistry, engineering, and medicine. PMID:28694872

  1. Theoretical Studies in Heterogenous Catalysis: Towards a Rational Design of Novel Catalysts for Hydrodesulfurization and Hydrogen Production

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez,J.A.; Liu, P.

    2008-10-01

    potential to become the next generation of industrial HDS catalysts. Then, systematic studies concerned with the hydrogen-evolution reaction (HER) on extended surfaces, organometallic complexes and enzymes are presented. Finally, the reasons for the high catalytic activity of Au-CeO{sub 2} and Cu-CeO{sub 2} in the production of hydrogen through the water-gas shift reaction (CO + H{sub 2}O {yields} H{sub 2} + CO{sub 2}) are analyzed. It is shown that theoretical methods are very valuable tools for helping in the rational design of heterogeneous catalysts.

  2. Application of Generative Autoencoder in De Novo Molecular Design.

    Science.gov (United States)

    Blaschke, Thomas; Olivecrona, Marcus; Engkvist, Ola; Bajorath, Jürgen; Chen, Hongming

    2018-01-01

    A major challenge in computational chemistry is the generation of novel molecular structures with desirable pharmacological and physiochemical properties. In this work, we investigate the potential use of autoencoder, a deep learning methodology, for de novo molecular design. Various generative autoencoders were used to map molecule structures into a continuous latent space and vice versa and their performance as structure generator was assessed. Our results show that the latent space preserves chemical similarity principle and thus can be used for the generation of analogue structures. Furthermore, the latent space created by autoencoders were searched systematically to generate novel compounds with predicted activity against dopamine receptor type 2 and compounds similar to known active compounds not included in the trainings set were identified. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  3. Fundamental Studies of Butane Oxidation over Model-Supported Vanadium Oxide Catalysts: Molecular Structure-Reactivity Relationships

    NARCIS (Netherlands)

    Wachs, I.E.; Jehng, J.M.; Deo, G.; Weckhuysen, B.M.; Guliants, V.V.; Benziger, J.B.; Sundaresan, S.

    1997-01-01

    The oxidation of n-butane to maleic anhydride was investigated over a series of model-supported vanadia catalysts where the vanadia phase was present as a two-dimensional metal oxide overlayer on the different oxide supports (TiO2, ZrO2, CeO2, Nb2O5, Al2O3, and SiO2). No correlation was found

  4. Homogeneous activation of molecular hydrogen: on the development of effective catalysts for isotopic exchange in protolytic media

    International Nuclear Information System (INIS)

    Sakharovskij, Yu.A.

    1987-01-01

    Comparison of different catalytic systems for hydrogen isotopic exchange with protolytic solvent based on activation enthalpy and entropy values is carried out. Particular attention is paid to the effect of ligand environment of complex forming metallic central ion and solvent composition on free activation energy and stability of catalytic system. A conclusion is drawn on impossibility of absolutely stable and high-temperature catalyst in an isolated system

  5. Oxidation of primary amines to oximes with molecular oxygen using 1,1-diphenyl-2-picrylhydrazyl and WO3/Al2O3 as catalysts.

    Science.gov (United States)

    Suzuki, Ken; Watanabe, Tomonari; Murahashi, Shun-Ichi

    2013-03-15

    The oxidative transformation of primary amines to their corresponding oximes proceeds with high efficiency under molecular oxygen diluted with molecular nitrogen (O2/N2 = 7/93 v/v, 5 MPa) in the presence of the catalysts 1,1-diphenyl-2-picrylhydrazyl (DPPH) and tungusten oxide/alumina (WO3/Al2O3). The method is environmentally benign, because the reaction requires only molecular oxygen as the terminal oxidant and gives water as a side product. Various alicyclic amines and aliphatic amines can be converted to their corresponding oximes in excellent yields. It is noteworthy that the oxidative transformation of primary amines proceeds chemoselectively in the presence of other functional groups. The key step of the present oxidation is a fast electron transfer from the primary amine to DPPH followed by proton transfer to give the α-aminoalkyl radical intermediate, which undergoes reaction with molecular oxygen and hydrogen abstraction to give α-aminoalkyl hydroperoxide. Subsequent reaction of the peroxide with WO3/Al2O3 gives oximes. The aerobic oxidation of secondary amines gives the corresponding nitrones. Aerobic oxidative transformation of cyclohexylamines to cyclohexanone oximes is important as a method for industrial production of ε-caprolactam, a raw material for Nylon 6.

  6. "Intelligent" design of molecular materials: Understanding the concepts of design in supramolecular synthesis of network solids

    Science.gov (United States)

    Moulton, Brian D.

    This work endeavors to delineate modern paradigms for crystal engineering, i.e. the design and supramolecular synthesis of functional molecular materials. Paradigms predicated on an understanding of the geometry of polygons and polyhedra are developed. The primary focus is on structural determination by single crystal X-ray crystallography, structural interpretation using a suite of graphical visualization and molecular modeling software, and on the importance of proper graphical representation in the presentation and explanation of crystal structures. A detailed analysis of a selected series of crystal structures is presented. The reduction of these molecular networks to schematic representations that illustrate their fundamental connectivity facilitates the understanding of otherwise complex supramolecular solids. Circuit symbols and Schlafli notation are used to describe the network topologies, which enables networks of different composition and metrics to be easily compared. This reveals that molecular orientations in the crystals and networks are commensurate with networks that can be derived from spherical close packed lattices. The development of a logical design strategy for a new class of materials based on our understanding of the chemical composition and topology of these networks is described. The synthesis and crystal structure of a series of new materials generated by exploitation of this design strategy is presented, in addition to a detailed analysis of the topology of these materials and their relationship to a 'parent' structure. In summary, this dissertation demonstrates that molecular polygons can self-assemble at their vertexes to produce molecular architectures and crystal structures that are consistent with long established geometric dogma. The design strategy represents a potentially broad ranging approach to the design of nanoporous structures from a wide range of chemical components that are based on molecular shape rather than chemical

  7. EDITORIAL: Design and function of molecular and bioelectronics devices

    Science.gov (United States)

    Krstic, Predrag; Forzani, Erica; Tao, Nongjian; Korkin, Anatoli

    2007-10-01

    Further rapid progress of electronics, in particular the increase of computer power and breakthroughs in sensor technology for industrial, medical diagnostics and environmental applications, strongly depends on the scaling of electronic devices, ultimately to the size of molecules. Design of controllable molecular-scale devices may resolve the problem of energy dissipation at the nanoscale and take advantage of molecular self-assembly in the so-called bottom-up approach. This special issue of Nanotechnology is devoted to a better understanding of the function and design of molecular-scale devices that are relevant to future electronics and sensor technology. Papers contained in this special issue are selected from the symposium Nano and Giga Challenges in Electronics and Photonics: From Atoms to Materials to Devices to System Architecture (12-16 March, 2007, Phoenix, Arizona, USA), as well as from original and novel scientific contributions of invited world-renown researchers. It addresses both theoretical and experimental achievements in the fields of molecular and bioelectronics, chemical and biosensors at the molecular level, including carbon nanotubes, novel nanostructures, as well as related research areas and industrial applications. The conference series Nano and Giga Challenges in Electronics and Photonics was launched as a truly interdisciplinary forum to bridge scientists and engineers to work across boundaries in the design of future information technologies, from atoms to materials to devices to system architecture. Following the first two successful meetings in Moscow, Russia (NGCM2002) and Krakow, Poland (NGCM2004), the third Nano and Giga Forum (NGC2007) was held in 2007 hosted by Arizona State University. Besides this special issue of Nanotechnology, two other collections (in the journal Solid State Electronics and the tutorial book in the series Nanostructure Science and Technology Springer) have published additional selected and invited papers

  8. Molecular Design of Branched and Binary Molecules at Ordered Interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Genson, Kirsten Larson [Iowa State Univ., Ames, IA (United States)

    2005-01-01

    This study examined five different branched molecular architectures to discern the effect of design on the ability of molecules to form ordered structures at interfaces. Photochromic monodendrons formed kinked packing structures at the air-water interface due to the cross-sectional area mismatch created by varying number of alkyl tails and the hydrophilic polar head group. The lower generations formed orthorhombic unit cell with long range ordering despite the alkyl tails tilted to a large degree. Favorable interactions between liquid crystalline terminal groups and the underlying substrate were observed to compel a flexible carbosilane dendrimer core to form a compressed elliptical conformation which packed stagger within lamellae domains with limited short range ordering. A twelve arm binary star polymer was observed to form two dimensional micelles at the air-water interface attributed to the higher polystyrene block composition. Linear rod-coil molecules formed a multitude of packing structures at the air-water interface due to the varying composition. Tree-like rod-coil molecules demonstrated the ability to form one-dimensional structures at the air-water interface and at the air-solvent interface caused by the preferential ordering of the rigid rod cores. The role of molecular architecture and composition was examined and the influence chemically competing fragments was shown to exert on the packing structure. The amphiphilic balance of the different molecular series exhibited control on the ordering behavior at the air-water interface and within bulk structures. The shell nature and tail type was determined to dictate the preferential ordering structure and molecular reorganization at interfaces with the core nature effect secondary.

  9. Design of slurry bubble column reactors: novel technique for optimum catalyst size selection contractual origin of the invention

    Science.gov (United States)

    Gamwo, Isaac K [Murrysville, PA; Gidaspow, Dimitri [Northbrook, IL; Jung, Jonghwun [Naperville, IL

    2009-11-17

    A method for determining optimum catalyst particle size for a gas-solid, liquid-solid, or gas-liquid-solid fluidized bed reactor such as a slurry bubble column reactor (SBCR) for converting synthesis gas into liquid fuels considers the complete granular temperature balance based on the kinetic theory of granular flow, the effect of a volumetric mass transfer coefficient between the liquid and the gas, and the water gas shift reaction. The granular temperature of the catalyst particles representing the kinetic energy of the catalyst particles is measured and the volumetric mass transfer coefficient between the gas and liquid phases is calculated using the granular temperature. Catalyst particle size is varied from 20 .mu.m to 120 .mu.m and a maximum mass transfer coefficient corresponding to optimum liquid hydrocarbon fuel production is determined. Optimum catalyst particle size for maximum methanol production in a SBCR was determined to be in the range of 60-70 .mu.m.

  10. Ceria-Based Mixed Oxide Supported Nano-Gold as an Efficient and Durable Heterogeneous Catalyst for Oxidative Dehydrogenation of Amines to Imines Using Molecular Oxygen

    Directory of Open Access Journals (Sweden)

    Bashir Ahmad Dar

    2012-06-01

    Full Text Available The present work is intended to determine the catalytic activity of Mixed Oxide supported gold for aerobic oxidative dehydrogenation of amines to imines using Ceria as a main constituent of the each support. The model catalysts Au/CeO2:TiO2 Au/CeO2:SiO2, Au/CeO2:ZrO2 and Au/CeO2:Al2Os were prepared by deposition co-precipitation method and deposition of gold was determined by EDEX analysis. The supported nano-gold catalyzes the dehydrogenation of secondary amines to imines without loss of activity. On recycling good amount of product yield is obtained. Oxidation of secondary amines to imines is carried at 100˚C and almost 90 % conversion was obtained with >99% selectivity. © 2012 BCREC UNDIP. All rights reservedReceived: 26th December 2011; Revised: 7th June 2012; Accepted: 13rd June 2012[How to Cite: B.A. Dar, M. Sharma, B. Singh. (2012. Ceria-Based Mixed Oxide Supported Nano-Gold as an Efficient and Durable Heterogeneous Catalyst for Oxidative Dehydrogenation of Amines to Imines Using Molecular Oxygen. Bulletin of Chemical Reaction Engineering & Catalysis, 7(1: 79-84.  doi:10.9767/bcrec.7.1.1257.79-84][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.1.1257.79-84 ] | View in 

  11. From molecular design and materials construction to organic nanophotonic devices.

    Science.gov (United States)

    Zhang, Chuang; Yan, Yongli; Zhao, Yong Sheng; Yao, Jiannian

    2014-12-16

    CONSPECTUS: Nanophotonics has recently received broad research interest, since it may provide an alternative opportunity to overcome the fundamental limitations in electronic circuits. Diverse optical materials down to the wavelength scale are required to develop nanophotonic devices, including functional components for light emission, transmission, and detection. During the past decade, the chemists have made their own contributions to this interdisciplinary field, especially from the controlled fabrication of nanophotonic molecules and materials. In this context, organic micro- or nanocrystals have been developed as a very promising kind of building block in the construction of novel units for integrated nanophotonics, mainly due to the great versatility in organic molecular structures and their flexibility for the subsequent processing. Following the pioneering works on organic nanolasers and optical waveguides, the organic nanophotonic materials and devices have attracted increasing interest and developed rapidly during the past few years. In this Account, we review our research on the photonic performance of molecular micro- or nanostructures and the latest breakthroughs toward organic nanophotonic devices. Overall, the versatile features of organic materials are highlighted, because they brings tunable optical properties based on molecular design, size-dependent light confinement in low-dimensional structures, and various device geometries for nanophotonic integration. The molecular diversity enables abundant optical transitions in conjugated π-electron systems, and thus brings specific photonic functions into molecular aggregates. The morphology of these micro- or nanostructures can be further controlled based on the weak intermolecular interactions during molecular assembly process, making the aggregates show photon confinement or light guiding properties as nanophotonic materials. By adoption of some active processes in the composite of two or more

  12. Syngas Production from Catalytic CO2 Reforming of CH4 over CaFe2O4 Supported Ni and Co Catalysts: Full Factorial Design Screening

    Directory of Open Access Journals (Sweden)

    M. Anwar Hossain

    2018-01-01

    Full Text Available In this study, the potential of dry reforming reaction over CaFe2O4 supported Ni and Co catalysts were investigated. The Co/CaFe2O4 and Ni/CaFe2O4 catalysts were synthesized using wet impregnation method by varying the metal loading from 5-15 %. The synthesized catalysts were tested in methane dry reforming reaction at atmospheric pressure and reaction temperature ranged 700-800 oC. The catalytic performance of the catalysts based on the initial screening is ranked as 5%Co/CaFe2O4 < 10%Co/CaFe2O4 < 5%Ni/CaFe2O4 < 10%Ni/CaFe2O4 according to their performance. The Ni/CaFe2O4 catalyst was selected for further investigation using full factorial design of experiment. The interaction effects of three factors namely metal loading (5-15 %, feed ratio (0.4-1.0, and reaction temperature (700-800 oC were evaluated on the catalytic activity in terms of CH4 and CO2 conversion as well as H2 and CO yield. The interaction between the factors showed significant effects on the catalyst performance at metal loading, feed ratio and reaction temperature of 15 %, 1.0, and 800 oC. respectively. The 15 wt% Ni/CaFe2O4 was subsequently characterized by Thermogravimetric (TGA, X-ray Diffraction (XRD, Field Emission Scanning Electron Microscopy (FESEM, Energy Dispersive X-ray Spectroscopy (EDX, X-ray Photoelectron Spectroscopy (XPS, N2-physisorption, Temperature Programmed Desorption (TPD-NH3, TPD-CO2, and Fourier Transform Infra Red (FTIR to ascertain its physiochemical properties.  This study demonstrated that the CaFe2O4 supported Ni catalyst has a good potential to be used for syngas production via methane dry reforming. Copyright © 2018 BCREC Group. All rights reserved Received: 5th May 2017; Revised: 8th August 2017; Accepted: 9th August 2017; Available online: 22nd January 2018; Published regularly: 2nd April 2018 How to Cite: Hossain, M.A., Ayodele, B.V., Cheng, C.K., Khan, M.R. (2018. Syngas Production from Catalytic CO2 Reforming of CH4 over CaFe2O4 Supported

  13. Molecular design for nonpolar chiral-axial quadratic nonlinear optics

    Science.gov (United States)

    Wiggers, Gregory A.

    In this thesis the hyperpolarizability of various multi-dimensional molecules is studied theoretically/computationally, with particular focus on the second-rank Kleinman-disallowed (KD) component of the hyperpolarizability. This component, which transforms as a second-rank traceless symmetric tensor, could be utilized in certain chiral-axial molecular alignment schemes to produce a bulk response. Nonpolar chiral-axial systems have been proposed in contrast to polar media, which utilize the vector component of the molecular hyperpolarizability and require parallel alignment of the molecular dipoles. Such parallel alignment of dipoles must be "frozen in" in order to overcome the natural tendency for dipoles to align anti-parallel. This limits the density of chromophores that can be loaded into a polar material. Nonpolar materials do not have such limits in theory. The two geometric classes of molecules that can most easily be incorporated into nonpolar chiral-uniaxial materials are propeller-shaped (C3 or D3 symmetry) and Λ-shaped (C2v symmetry). This work describes efforts to design molecules within these classes that would be suitable for bulk NLO materials. The sum-over-states (SOS) expression is used to model the molecular hyperpolarizability, and quantum chemical calculations, along with linear absorption data (when available) provide the necessary parameters to evaluate truncated forms of the SOS expression. A host of chemical and geometric modifications will be considered in order to elucidate important structure/function relationships. Also, the SOS model will be tested in some cases when experimental measurements (via Kleinman-disallowed hyper-Rayleigh scattering) are available. While a majority of this work focuses on multi-dimensional molecules, a small section deals with the question of optimizing the hyperpolarizability of a one-dimensional system. It is suggested that the recently-proposed idea of "modulated conjugation" as a means for improving

  14. New synthetic thrombin inhibitors: molecular design and experimental verification.

    Science.gov (United States)

    Sinauridze, Elena I; Romanov, Alexey N; Gribkova, Irina V; Kondakova, Olga A; Surov, Stepan S; Gorbatenko, Aleksander S; Butylin, Andrey A; Monakov, Mikhail Yu; Bogolyubov, Alexey A; Kuznetsov, Yuryi V; Sulimov, Vladimir B; Ataullakhanov, Fazoyl I

    2011-01-01

    The development of new anticoagulants is an important goal for the improvement of thromboses treatments. The design, synthesis and experimental testing of new safe and effective small molecule direct thrombin inhibitors for intravenous administration. Computer-aided molecular design of new thrombin inhibitors was performed using our original docking program SOL, which is based on the genetic algorithm of global energy minimization in the framework of a Merck Molecular Force Field. This program takes into account the effects of solvent. The designed molecules with the best scoring functions (calculated binding energies) were synthesized and their thrombin inhibitory activity evaluated experimentally in vitro using a chromogenic substrate in a buffer system and using a thrombin generation test in isolated plasma and in vivo using the newly developed model of hemodilution-induced hypercoagulation in rats. The acute toxicities of the most promising new thrombin inhibitors were evaluated in mice, and their stabilities in aqueous solutions were measured. New compounds that are both effective direct thrombin inhibitors (the best K(I) was 50) in the thrombin generation assay of approximately 100 nM) were discovered. These compounds contain one of the following new residues as the basic fragment: isothiuronium, 4-aminopyridinium, or 2-aminothiazolinium. LD(50) values for the best new inhibitors ranged from 166.7 to >1111.1 mg/kg. A plasma-substituting solution supplemented with one of the new inhibitors prevented hypercoagulation in the rat model of hemodilution-induced hypercoagulation. Activities of the best new inhibitors in physiological saline (1 µM solutions) were stable after sterilization by autoclaving, and the inhibitors remained stable at long-term storage over more than 1.5 years at room temperature and at 4°C. The high efficacy, stability and low acute toxicity reveal that the inhibitors that were developed may be promising for potential medical applications.

  15. New synthetic thrombin inhibitors: molecular design and experimental verification.

    Directory of Open Access Journals (Sweden)

    Elena I Sinauridze

    Full Text Available BACKGROUND: The development of new anticoagulants is an important goal for the improvement of thromboses treatments. OBJECTIVES: The design, synthesis and experimental testing of new safe and effective small molecule direct thrombin inhibitors for intravenous administration. METHODS: Computer-aided molecular design of new thrombin inhibitors was performed using our original docking program SOL, which is based on the genetic algorithm of global energy minimization in the framework of a Merck Molecular Force Field. This program takes into account the effects of solvent. The designed molecules with the best scoring functions (calculated binding energies were synthesized and their thrombin inhibitory activity evaluated experimentally in vitro using a chromogenic substrate in a buffer system and using a thrombin generation test in isolated plasma and in vivo using the newly developed model of hemodilution-induced hypercoagulation in rats. The acute toxicities of the most promising new thrombin inhibitors were evaluated in mice, and their stabilities in aqueous solutions were measured. RESULTS: New compounds that are both effective direct thrombin inhibitors (the best K(I was 1111.1 mg/kg. A plasma-substituting solution supplemented with one of the new inhibitors prevented hypercoagulation in the rat model of hemodilution-induced hypercoagulation. Activities of the best new inhibitors in physiological saline (1 µM solutions were stable after sterilization by autoclaving, and the inhibitors remained stable at long-term storage over more than 1.5 years at room temperature and at 4°C. CONCLUSIONS: The high efficacy, stability and low acute toxicity reveal that the inhibitors that were developed may be promising for potential medical applications.

  16. 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...

  17. Catalysts for synthetic liquid fuels

    Energy Technology Data Exchange (ETDEWEB)

    Bruce, L.A.; Turney, T.W.

    1987-12-01

    Fischer-Tropsch catalysts have been designed, characterized and tested for the selective production of hydrocarbons suitable as synthetic liquid transport fuels from synthesis gas (i.e., by the reduction of carbon monoxide with hydrogen). It was found that hydrocarbons in the middle distillate range, or suitable for conversion to that range, could be produced over several of the new catalyst systems. The various catalysts examined included: (1) synthetic cobalt clays, mainly cobalt chlorites; (2) cobalt hydrotalcites; (3) ruthenium metal supported on rare earth oxides of high surface area; and (4) a novel promoted cobalt catalyst. Active and selective catalysts have been obtained, in each category. With the exception of the clays, reproducibility of catalyst performance has been good. Catalysts in groups 2 and 4 have exhibited very high activity, with long lifetimes and easy regeneration.

  18. Molecular Dynamics Approach in Designing Thermostable Aspergillus niger Xylanase

    Science.gov (United States)

    Malau, N. D.; Sianturi, M.

    2017-03-01

    Molecular dynamics methods we have applied as a tool in designing thermostable Aspergillus niger Xylanase, by examining Root Mean Square Deviation (RMSD) and The Stability of the Secondary Structure of enzymes structure at its optimum temperature and compare with its high temperature behavior. As RMSD represents structural fluctuation at a particular temperature, a better understanding of this factor will suggest approaches to bioengineer these enzymes to enhance their thermostability. In this work molecular dynamic simulations of Aspergillus niger xylanase (ANX) have been carried at 400K (optimum catalytic temperature) for 2.5 ns and 500K (ANX reported inactive temperature) for 2.5 ns. Analysis have shown that the Root Mean Square Deviation (RMSD) significant increase at higher temperatures compared at optimum temperature and some of the secondary structures of ANX that have been damaged at high temperature. Structural analysis revealed that the fluctuations of the α-helix and β-sheet regions are larger at higher temperatures compared to the fluctuations at optimum temperature.

  19. Tunable Molecular Logic Gates Designed for Imaging Released Neurotransmitters.

    Science.gov (United States)

    Klockow, Jessica L; Hettie, Kenneth S; Secor, Kristen E; Barman, Dipti N; Glass, Timothy E

    2015-08-03

    Tunable dual-analyte fluorescent molecular logic gates (ExoSensors) were designed for the purpose of imaging select vesicular primary-amine neurotransmitters that are released from secretory vesicles upon exocytosis. ExoSensors are based on the coumarin-3-aldehyde scaffold and rely on both neurotransmitter binding and the change in environmental pH associated with exocytosis to afford a unique turn-on fluorescence output. A pH-functionality was directly integrated into the fluorophore π-system of the scaffold, thereby allowing for an enhanced fluorescence output upon the release of labeled neurotransmitters. By altering the pH-sensitive unit with various electron-donating and -withdrawing sulfonamide substituents, we identified a correlation between the pKa of the pH-sensitive group and the fluorescence output from the activated fluorophore. In doing so, we achieved a twelvefold fluorescence enhancement upon evaluating the ExoSensors under conditions that mimic exocytosis. ExoSensors are aptly suited to serve as molecular imaging tools that allow for the direct visualization of only the neurotransmitters that are released from secretory vesicles upon exocytosis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Design of molecular imprinted polymers compatible with aqueous environment.

    Science.gov (United States)

    Piletska, Elena V; Guerreiro, Antonio R; Romero-Guerra, Maria; Chianella, Iva; Turner, Anthony P F; Piletsky, Sergey A

    2008-01-21

    The main problem of poor water compatibility of molecularly imprinted polymers (MIPs) was addressed in examples describing design of synthetic receptors with high affinity for drugs of abuse. An extensive potentiometric titration of 10 popular functional monomers and corresponding imprinted and blank polymers was conducted in order to evaluate the subtleties of functional groups ionisation under aqueous conditions. It was found that polymers prepared using 2-trifluoromethacrylic acid (TFMAA) in combination with toluene as porogen possess superior properties which make them suitable for effective template recognition in water. The potential impact of phase separation during polymerisation on formation of high quality imprints has been discussed. Three drugs of abuse such as cocaine, deoxyephedrine and methadone were used as template models in polymer preparation for the practical validation of obtained results. The polymer testing showed that synthesized molecularly imprinted polymers have high affinity and selectivity for corresponding templates in aqueous environment, with imprinting factors of 2.6 for cocaine and 1.4 for methadone and deoxyephedrine. Corresponding blank polymers were unable to differentiate between analytes, suggesting that imprinting phenomenon was responsible for the recognition properties.

  1. Heterogeneous Catalysis: Understanding for Designing, and Designing for Applications

    OpenAIRE

    Corma Canós, Avelino

    2016-01-01

    Despite the introduction of high-throughput and combinatorial methods that certainly can be useful in the process of catalysts optimization, it is recognized that the generation of fundamental knowledge at the molecular level is key for the development of new concepts and for reaching the final objective of solid catalysts by design … Corma Canós, A. (2016). Heterogeneous Catalysis: Understanding for Designing, and Designing for Applications. Angewandte Chemie International Edition. 55(21)...

  2. The use of pyro-polymeric catalysts and a new cylindrical cell design in oxygen-aluminum generators

    Science.gov (United States)

    Kiseleva, E. A.; Zhuk, A. Z.; Kleymenov, B. V.; Oudaltsov, V. G.

    2018-01-01

    The increase in energy consumption, the economic crisis, the development of certain areas of engineering and energy, as well as the related deterioration of the environmental situation, require the development of new electrochemical current sources with high specific characteristics. In the field of creating air-hydrogen fuel cells, the problems of safety and mobile storage of hydrogen have not been completely solved, stagnation in the development of lithium-ion, lithium-air and lithium-sulfur batteries has been outlined. All this requires searching for new technological solutions, ways to increase the energy and resource characteristics of electrochemical current sources (ECS), reducing their cost [1-2]. The use of metals (aluminum, zinc, magnesium) as an energy carrier is due to their high energy intensity (in combination with the lack of transport, storage and on-board storage problems) of the relatively low cost of metals, their availability, storage safety and the absence of harmful emissions when used. As in the chemical and electrochemical use of metals, safe products (oxides, hydroxides) are formed, which are reduced to metals within the framework of traditional production technologies. Thus, a closed cycle of energy use is organized. The task of this paper is to evaluate the possibility of reducing the cost and increasing the specific power of ECS using oxygen depolarization. The goal is achieved by using non-platinum catalysts and optimizing the design of the current source.

  3. Design of Novel Biosensors for Determination of Phenolic Compounds using Catalyst-Loaded Reduced Graphene Oxide Electrodes

    Directory of Open Access Journals (Sweden)

    Kathleen Morrisey

    2014-06-01

    Full Text Available Facile and inexpensive method for designing high performance sensors for H2O2 and polyphenols has been developed. The proposed sensors are based on high electrocatalytic activity of Prussian Blue (PB nanoparticles deposited in situ on high surface area graphene nanosheet-based thin films on a graphite electrode. The exfoliated graphene nanosheets were formed by attaching graphene oxide to the electrode surface followed by their electrochemical reduction to obtain the reduced graphene oxide (rGO, providing high surface area and excellent current-carrying capabilities to the sensory film. The PB catalyst nanoparticles were deposited electrochemically on rGO. This procedure is very time efficient as it reduces the time of sensor preparation from 3 days (according to recent literature to several hours. The proposed method provides simple means to obtain highly reliable and stable sensory films. The sensor shows a dynamic range of 1–500 µM H2O2 and a rapid response of 5 s to reach 95% of a steady-state response. When combined with immobilized enzymes (horseradish peroxidase or laccase oxidase, it can serve as a biosensor for polyphenols. As the proof of concept, the response of the enzymatic biosensors to polyphenol catechin has been presented delineating different mechanisms of horseradish peroxidase and laccase operation. The proposed sensors are low cost, reliable, and scalable.

  4. Synthetic Elucidation of Design Principles for Molecular Qubits

    Science.gov (United States)

    Graham, Michael James

    Quantum information processing (QIP) is an emerging computational paradigm with the potential to enable a vast increase in computational power, fundamentally transforming fields from structural biology to finance. QIP employs qubits, or quantum bits, as its fundamental units of information, which can exist in not just the classical states of 0 or 1, but in a superposition of the two. In order to successfully perform QIP, this superposition state must be sufficiently long-lived. One promising paradigm for the implementation of QIP involves employing unpaired electrons in coordination complexes as qubits. This architecture is highly tunable and scalable, however coordination complexes frequently suffer from short superposition lifetimes, or T2. In order to capitalize on the promise of molecular qubits, it is necessary to develop a set of design principles that allow the rational synthesis of complexes with sufficiently long values of T2. In this dissertation, I report efforts to use the synthesis of series of complexes to elucidate design principles for molecular qubits. Chapter 1 details previous work by our group and others in the field. Chapter 2 details the first efforts of our group to determine the impact of varying spin and spin-orbit coupling on T2. Chapter 3 examines the effect of removing nuclear spins on coherence time, and reports a series of vanadyl bis(dithiolene) complexes which exhibit extremely long coherence lifetimes, in excess of the 100 mus threshold for qubit viability. Chapters 4 and 5 form two complimentary halves of a study to determine the exact relationship between electronic spin-nuclear spin distance and the effect of the nuclear spins on T2. Finally, chapter 6 suggests next directions for the field as a whole, including the potential for work in this field to impact the development of other technologies as diverse as quantum sensors and magnetic resonance imaging contrast agents.

  5. Bayesian molecular design with a chemical language model

    Science.gov (United States)

    Ikebata, Hisaki; Hongo, Kenta; Isomura, Tetsu; Maezono, Ryo; Yoshida, Ryo

    2017-04-01

    The aim of computational molecular design is the identification of promising hypothetical molecules with a predefined set of desired properties. We address the issue of accelerating the material discovery with state-of-the-art machine learning techniques. The method involves two different types of prediction; the forward and backward predictions. The objective of the forward prediction is to create a set of machine learning models on various properties of a given molecule. Inverting the trained forward models through Bayes' law, we derive a posterior distribution for the backward prediction, which is conditioned by a desired property requirement. Exploring high-probability regions of the posterior with a sequential Monte Carlo technique, molecules that exhibit the desired properties can computationally be created. One major difficulty in the computational creation of molecules is the exclusion of the occurrence of chemically unfavorable structures. To circumvent this issue, we derive a chemical language model that acquires commonly occurring patterns of chemical fragments through natural language processing of ASCII strings of existing compounds, which follow the SMILES chemical language notation. In the backward prediction, the trained language model is used to refine chemical strings such that the properties of the resulting structures fall within the desired property region while chemically unfavorable structures are successfully removed. The present method is demonstrated through the design of small organic molecules with the property requirements on HOMO-LUMO gap and internal energy. The R package iqspr is available at the CRAN repository.

  6. Molecular dynamics in drug design: new generations of compstatin analogs.

    Science.gov (United States)

    Tamamis, Phanourios; López de Victoria, Aliana; Gorham, Ronald D; Bellows-Peterson, Meghan L; Pierou, Panayiota; Floudas, Christodoulos A; Morikis, Dimitrios; Archontis, Georgios

    2012-05-01

    We report the computational and rational design of new generations of potential peptide-based inhibitors of the complement protein C3 from the compstatin family. The binding efficacy of the peptides is tested by extensive molecular dynamics-based structural and physicochemical analysis, using 32 atomic detail trajectories in explicit water for 22 peptides bound to human, rat or mouse target protein C3, with a total of 257 ns. The criteria for the new design are: (i) optimization for C3 affinity and for the balance between hydrophobicity and polarity to improve solubility compared to known compstatin analogs; and (ii) development of dual specificity, human-rat/mouse C3 inhibitors, which could be used in animal disease models. Three of the new analogs are analyzed in more detail as they possess strong and novel binding characteristics and are promising candidates for further optimization. This work paves the way for the development of an improved therapeutic for age-related macular degeneration, and other complement system-mediated diseases, compared to known compstatin variants. © 2012 John Wiley & Sons A/S.

  7. Intelligent Design of Nano-Scale Molecular Imaging Agents

    Directory of Open Access Journals (Sweden)

    Takeaki Ozawa

    2012-12-01

    Full Text Available Visual representation and quantification of biological processes at the cellular and subcellular levels within living subjects are gaining great interest in life science to address frontier issues in pathology and physiology. As intact living subjects do not emit any optical signature, visual representation usually exploits nano-scale imaging agents as the source of image contrast. Many imaging agents have been developed for this purpose, some of which exert nonspecific, passive, and physical interaction with a target. Current research interest in molecular imaging has mainly shifted to fabrication of smartly integrated, specific, and versatile agents that emit fluorescence or luminescence as an optical readout. These agents include luminescent quantum dots (QDs, biofunctional antibodies, and multifunctional nanoparticles. Furthermore, genetically encoded nano-imaging agents embedding fluorescent proteins or luciferases are now gaining popularity. These agents are generated by integrative design of the components, such as luciferase, flexible linker, and receptor to exert a specific on–off switching in the complex context of living subjects. In the present review, we provide an overview of the basic concepts, smart design, and practical contribution of recent nano-scale imaging agents, especially with respect to genetically encoded imaging agents.

  8. Kinetic modelling of slurry polymerization of ethylene with a polymer supported Ziegler-Natta catalyst (hydrogen)

    Energy Technology Data Exchange (ETDEWEB)

    Shariati, A.

    1996-12-31

    The kinetics of polymerization of ethylene catalyzed by a polymer supported Ziegler-Natta catalyst were investigated in a semi-batch reactor system. The influences of six polymerization variables were investigated using a central composite design. The variables were monomer partial pressure, catalyst loading, co-catalyst loading, catalyst particle size and hydrogen to monomer ratio. The influence of temperature on rate and polymer properties were investigated. Empirical models were fitted to the experimental data to quantify the effects of the polymerization variables on the rate characteristics and polymer properties. The rate of polymerization exhibited a first order dependency with respect to monomer partial pressure, but a nonlinear relationship with respect to catalyst loading. In the absence of hydrogen, the polymerization rate showed a non-decaying profile at the centre point conditions for the other variables. Catalyst loading and catalyst particle size had a negligible effect on weight-and-number-average molecular weights, while increasing co-catalysts loading lowered the molecular weights, as did increased temperature and hydrogen concentration. refs., figs.

  9. Sabatier Catalyst Poisoning Investigation

    Science.gov (United States)

    Nallette, Tim; Perry, Jay; Abney, Morgan; Knox, Jim; Goldblatt, Loel

    2013-01-01

    The Carbon Dioxide Reduction Assembly (CRA) on the International Space Station (ISS) has been operational since 2010. The CRA uses a Sabatier reactor to produce water and methane by reaction of the metabolic CO2 scrubbed from the cabin air and the hydrogen byproduct from the water electrolysis system used for metabolic oxygen generation. Incorporating the CRA into the overall air revitalization system has facilitated life support system loop closure on the ISS reducing resupply logistics and thereby enhancing longer term missions. The CRA utilizes CO2 which has been adsorbed in a 5A molecular sieve within the Carbon Dioxide Removal Assembly, CDRA. There is a potential of compounds with molecular dimensions similar to, or less than CO2 to also be adsorbed. In this fashion trace contaminants may be concentrated within the CDRA and subsequently desorbed with the CO2 to the CRA. Currently, there is no provision to remove contaminants prior to entering the Sabatier catalyst bed. The risk associated with this is potential catalyst degradation due to trace organic contaminants in the CRA carbon dioxide feed acting as catalyst poisons. To better understand this risk, United Technologies Aerospace System (UTAS) has teamed with MSFC to investigate the impact of various trace contaminants on the CRA catalyst performance at relative ISS cabin air concentrations and at about 200/400 times of ISS concentrations, representative of the potential concentrating effect of the CDRA molecular sieve. This paper summarizes our initial assessment results.

  10. Communicating catalysts

    Science.gov (United States)

    Weckhuysen, Bert M.

    2018-06-01

    The beauty and activity of enzymes inspire chemists to tailor new and better non-biological catalysts. Now, a study reveals that the active sites within heterogeneous catalysts actively cooperate in a fashion phenomenologically similar to, but mechanistically distinct, from enzymes.

  11. Phytosterol Recognition via Rationally Designed Molecularly Imprinted Polymers

    Directory of Open Access Journals (Sweden)

    Lachlan J. Schwarz

    2018-02-01

    Full Text Available Molecularly imprinted polymers (MIPs prepared via a semi-covalent imprinting strategy using stigmasteryl methacrylate as a polymerisable template have been evaluated by static binding methods for their ability to selectively capture other valuable phytosterol targets, including campesterol and brassicasterol. Design criteria based on molecular modelling procedures and interaction energy calculations were employed to aid the selection of the co-monomer type, as well as the choice of co-monomer:template ratios for the formation of the pre-polymerisation complex. These novel hybrid semi-covalently imprinted polymers employed N,N′-dimethylacryl-amide (N,N′-DMAAM as the functional co-monomer and displayed specific binding capacities in the range 5.2–5.9 mg sterol/g MIP resin. Their binding attributes and selectivities towards phytosterol compounds were significantly different to the corresponding MIPs prepared via non-covalent procedures or when compared to non-imprinted polymers. Cross-reactivity studies using stigmasterol, ergosterol, cholesterol, campesterol, and brassicasterol as single analytes revealed the importance of the A-ring C-3-β-hydroxyl group and the orientational preferences of the D-ring alkyl chain structures in their interaction in the templated cavity with the N,N′-dimethylamide functional groups of the MIP. Finally, to obtain useful quantities of both campersterol and brassicasterol for these investigations, improved synthetic routes have been developed to permit the conversion of the more abundant, lower cost stigmasterol via a reactive aldehyde intermediate to these other sterols.

  12. Rational design of Mg-Al mixed oxide-supported bimetallic catalysts for dry reforming of methane

    Energy Technology Data Exchange (ETDEWEB)

    Tsyganok, Andrey I. [Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, D' Iorio Hall, 10 Marie Curie Street, Ottawa, Ont. (Canada); Inaba, Mieko [Natural Gas Technology Development Team, Teikoku Oil Co., 9-23-30 Kitakarasuyama, Setagaya-ku, Tokyo 157-0061 (Japan); Tsunoda, Tatsuo; Uchida, Kunio; Suzuki, Kunio; Hayakawa, Takashi [Institute for Materials and Chemical Process, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba 305-8565 (Japan); Takehira, Katsuomi [Department of Applied Chemistry, Faculty of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima 739-8527 (Japan)

    2005-09-18

    A novel synthetic strategy for preparing bimetallic Ru-M (M=Cr, Fe, Co, Ni and Cu) catalysts, supported on Mg-Al mixed oxide, has been introduced. It was based on a 'memory effect', i.e. on the ability of Mg-Al mixed oxide to reconstruct a layered structure upon rehydration with an aqueous solution. By repeated calcinations-rehydration cycles, layered double hydroxide (LDH) precursors of catalysts containing two different metals were synthesized. Bimetallic catalysts were then generated (1) in situ from LDH under methane reforming reaction conditions and (2) from mixed metal oxides obtained by preliminary LDH calcination. Among all the LDH-derived catalysts, a Ru{sup 0.1%}-Ni{sup 5.0%}/MgAlO{sub x} sample revealed the highest activity and selectivity to syngas, a suitable durability and a low coking capacity. A promoting effect of ruthenium on catalytic function of supported nickel was demonstrated. Preliminary LDH calcination was shown to markedly affect the catalytic activity of the derived catalysts and especially their coking properties.

  13. Ruthenium-modified MCM-41 mesoporous molecular sieve and Y zeolite catalysts for selective hydrogenation of cinnamaldehyde

    Czech Academy of Sciences Publication Activity Database

    Hájek, J.; Kumar, N.; Mäki-Arvela, P.; Salmi, T.; Murzin, D. Z.; Paseka, Ivo; Heikkilä, T.; Laine, E.; Laukkanen, P.; Väyrynen, J.

    2003-01-01

    Roč. 251, č. 2 (2003), s. 385-396 ISSN 0926-860X R&D Projects: GA ČR GA104/03/0409 Institutional research plan: CEZ:AV0Z4032918 Keywords : mesoporous molecular sieve * zeolites * ruthenium Subject RIV: CA - Inorganic Chemistry Impact factor: 2.825, year: 2003

  14. Statistical molecular design of balanced compound libraries for QSAR modeling.

    Science.gov (United States)

    Linusson, A; Elofsson, M; Andersson, I E; Dahlgren, M K

    2010-01-01

    A fundamental step in preclinical drug development is the computation of quantitative structure-activity relationship (QSAR) models, i.e. models that link chemical features of compounds with activities towards a target macromolecule associated with the initiation or progression of a disease. QSAR models are computed by combining information on the physicochemical and structural features of a library of congeneric compounds, typically assembled from two or more building blocks, and biological data from one or more in vitro assays. Since the models provide information on features affecting the compounds' biological activity they can be used as guides for further optimization. However, in order for a QSAR model to be relevant to the targeted disease, and drug development in general, the compound library used must contain molecules with balanced variation of the features spanning the chemical space believed to be important for interaction with the biological target. In addition, the assays used must be robust and deliver high quality data that are directly related to the function of the biological target and the associated disease state. In this review, we discuss and exemplify the concept of statistical molecular design (SMD) in the selection of building blocks and final synthetic targets (i.e. compounds to synthesize) to generate information-rich, balanced libraries for biological testing and computation of QSAR models.

  15. Atomic-Scale Design of Iron Fischer-Tropsch Catalysts; A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

    Energy Technology Data Exchange (ETDEWEB)

    Manos Mavrikakis; James Dumesic; Rahul Nabar; Calvin Bartholonew; Hu Zou; Uchenna Paul

    2008-09-29

    This work focuses on (1) searching/summarizing published Fischer-Tropsch synthesis (FTS) mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) preparation and characterization of unsupported iron catalysts with/without potassium/platinum promoters; (3) measurement of H{sub 2} and CO adsorption/dissociation kinetics on iron catalysts using transient methods; (3) analysis of the transient rate data to calculate kinetic parameters of early elementary steps in FTS; (4) construction of a microkinetic model of FTS on iron, and (5) validation of the model from collection of steady-state rate data for FTS on iron catalysts. Three unsupported iron catalysts and three alumina-supported iron catalysts were prepared by non-aqueous-evaporative deposition (NED) or aqueous impregnation (AI) and characterized by chemisorption, BET, temperature-programmed reduction (TPR), extent-of-reduction, XRD, and TEM methods. These catalysts, covering a wide range of dispersions and metal loadings, are well-reduced and relatively thermally stable up to 500-600 C in H{sub 2} and thus ideal for kinetic and mechanistic studies. Kinetic parameters for CO adsorption, CO dissociation, and surface carbon hydrogenation on these catalysts were determined from temperature-programmed desorption (TPD) of CO and temperature programmed surface hydrogenation (TPSR), temperature-programmed hydrogenation (TPH), and isothermal, transient hydrogenation (ITH). A microkinetic model was constructed for the early steps in FTS on polycrystalline iron from the kinetic parameters of elementary steps determined experimentally in this work and from literature values. Steady-state rate data were collected in a Berty reactor and used for validation of the microkinetic model. These rate data were fitted to 'smart' Langmuir-Hinshelwood rate expressions derived from a sequence of elementary steps and using a combination of fitted steady-state parameters and parameters specified from the transient

  16. Non-PGM cell catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Colon-Mercado, H. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Elvington, M. [Savannah River Consulting, Aiken, SC (United States); Ganesan, P. [Savannah River Consulting, Aiken, SC (United States)

    2017-09-27

    A unique approach has been developed to probe the non-PGM catalyst active site for the Oxygen Reduction Reaction (ORR) for PEMFCs. Iron based functionalities have been engineered into a variety of catalysts to evaluate their impact on activity for the ORR. A series of high surface area catalysts were synthesized and the impact of the chemical structure on the electrochemical and electrocatalytic properties was investigated. Elemental and surface analyses of the prepared catalysts reveal the incorporation of iron in a targeted and controlled manner. A high surface area framework catalyst was prepared that shows exceptional activity, comparable to state-of-the-art materials. The results of this research project provided critical seed data for the newly awarded ElectroCat project, which focuses on rationally designed framework catalysts for the oxygen reduction reaction.

  17. Lunar CATALYST

    Data.gov (United States)

    National Aeronautics and Space Administration — Lunar Cargo Transportation and Landing by Soft Touchdown (Lunar CATALYST) is a NASA initiative to encourage the development of U.S. private-sector robotic lunar...

  18. Catalytic Cracking of Palm Oil Over Zeolite Catalysts: Statistical Approach

    Directory of Open Access Journals (Sweden)

    F. A. A. Twaiq and S. Bhatia

    2012-08-01

    Full Text Available The catalytic cracking of palm oil was conducted in a fixed bed micro-reactor over HZSM-5, zeolite ? and ultrastable Y (USY zeolite catalysts. The objective of the present investigation was to study the effect of cracking reaction variables such as temperature, weight hourly space velocity, catalyst pore size and type of palm oil feed of different molecular weight on the conversion, yield of hydrocarbons in gasoline boiling range and BTX aromatics in the organic liquid product.  Statistical Design of Experiment (DOE with 24 full factorial design was used in experimentation at the first stage.  The nonlinear model and Response Surface Methodology (RSM were utilized in the second stage of experimentation to obtain the optimum values of the variables for maximum yields of hydrocarbons in gasoline boiling range and aromatics.  The HZSM-5 showed the best performance amongst the three catalysts tested.  At 623 K and WHSV of 1 h-1, the highest experimental yields of gasoline and aromatics were 28.3 wt.% and 27 wt.%, respectively over the HZSM-5 catalyst.  For the same catalyst, the statistical model predicted that the optimum yield of gasoline was 28.1 wt.% at WHSV of 1.75 h-1 and 623 K.  The predicted optimum yield of gasoline was 25.5 wt.% at 623 K and WHSV of 1 h-1.KEY WORDS: Catalytic Cracking, Palm Oil, Zeolite, Design Of Experiment, Response Surface Methodology.

  19. Design of supramolecular nanomaterials : from molecular recognition to hierarchical self-assembly

    OpenAIRE

    El Idrissi, Mohamed

    2017-01-01

    In the present thesis, are reported new strategies for the design of nanostructures to partly address environmental issues. The work carried out has been divided into three parts: the design of cyclodextrin (CD)-based polymeric materials, the molecular engineering of a pyrene derivative for the formation of self-assembled nanostructures and the design of smart nanocarriers. Considerable efforts have been devoted to the design of molecular receptors capable of specific recognition of a wid...

  20. Ga-assisted catalyst-free growth mechanism of GaAs nanowires by molecular beam epitaxy

    International Nuclear Information System (INIS)

    Colombo, C.; Spirkoska, D.; Frimmer, M.; Abstreiter, G.; Fontcuberta i Morral, A.

    2008-01-01

    The mechanisms of Ga-assisted GaAs nanowires grown by molecular beam epitaxy are addressed. The axial and radial growth rates as a function of the Ga rate and As pressure indicate that on the opposite of what is observed in thin film epitaxy, the growth rate of the nanowires is arsenic limited. As a consequence, the axial growth rate of the wires can be controlled by the As 4 pressure. Additionally, due to the small As 4 pressure leading to nanowire growth, the deposition on the facets is very slow, leading to a much lower radial growth rate. Finally, we present a model that is able to accurately describe the presented observations and predicts a maximum length of nontapered nanowires of 40 μm

  1. Biomass Conversion over Heteropoly Acid Catalysts

    KAUST Repository

    Zhang, Jizhe

    2015-04-01

    Biomass is a natural resource that is both abundant and sustainable. Its efficient utilization has long been the focus of research and development efforts with the aim to substitute it for fossil-based feedstock. In addition to the production of biofuels (e.g., ethanol) from biomass, which has been to some degree successful, its conversion to high value-added chemicals is equally important. Among various biomass conversion pathways, catalytic conversion is usually preferred, as it provides a cost-effective and eco-benign route to the desired products with high selectivities. The research of this thesis is focused on the conversion of biomass to various chemicals of commercial interest by selective catalytic oxidation. Molecular oxygen is chosen as the oxidant considering its low cost and environment friendly features in comparison with commonly used hydrogen peroxide. However, the activation of molecular oxygen usually requires high reaction temperatures, leading to over oxidation and thus lower selectivities. Therefore, it is highly desirable to develop effective catalysts for such conversion systems. We use kegging-type heteropoly acids (HPAs) as a platform for catalysts design because of their high catalytic activities and ease of medication. Using HPA catalysts allows the conversion taking place at relatively low temperature, which is beneficial to saving production cost as well as to improving the reaction selectivity. The strong acidity of HPA promotes the hydrolysis of biomass of giant molecules (e.g. cellulose), which is the first as well as the most difficult step in the conversion process. Under certain circumstances, a HPA combines the merits of homogeneous and heterogeneous catalysts, acting as an efficient homogeneous catalyst during the reaction while being easily separated as a heterogeneous catalyst after the reaction. We have successfully applied HPAs in several biomass conversion systems. Specially, we prepared a HPA-based bi-functional catalyst

  2. DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

    Energy Technology Data Exchange (ETDEWEB)

    Branko N. Popov

    2009-02-20

    The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst shows the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable

  3. DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)

    Energy Technology Data Exchange (ETDEWEB)

    Branko N. Popov

    2009-03-03

    The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst shows the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable

  4. Photodriven hydrogen evolution by molecular catalysts using Al2O3-protected perylene-3,4-dicarboximide on NiO electrodes† †Electronic supplementary information (ESI) available: Experimental details; additional electrochemical and photoelectrochemical characterization, UV-Vis spectra, and fsTA results; quantification of evolved hydrogen; and DFT-computed ground state structure of PMI diester. See DOI: 10.1039/c6sc02477g Click here for additional data file.

    Science.gov (United States)

    Kamire, Rebecca J.; Majewski, Marek B.; Hoffeditz, William L.; Phelan, Brian T.; Farha, Omar K.; Hupp, Joseph T.

    2017-01-01

    The design of efficient hydrogen-evolving photocathodes for dye-sensitized photoelectrochemical cells (DSPECs) requires the incorporation of molecular light absorbing chromophores that are capable of delivering reducing equivalents to molecular proton reduction catalysts at rates exceeding those of charge recombination events. Here, we report the functionalization and kinetic analysis of a nanostructured NiO electrode with a modified perylene-3,4-dicarboximide chromophore (PMI) that is stabilized against degradation by atomic layer deposition (ALD) of thick insulating Al2O3 layers. Following photoinduced charge injection into NiO in high yield, films with Al2O3 layers demonstrate longer charge separated lifetimes as characterized via femtosecond transient absorption spectroscopy and photoelectrochemical techniques. The photoelectrochemical behavior of the electrodes in the presence of Co(ii) and Ni(ii) molecular proton reduction catalysts is examined, revealing reduction of both catalysts. Under prolonged irradiation, evolved H2 is directly observed by gas chromatography supporting the applicability of PMI embedded in Al2O3 as a photocathode architecture in DSPECs. PMID:28616134

  5. A Multi-step and Multi-level approach for Computer Aided Molecular Design

    DEFF Research Database (Denmark)

    . The problem formulation step incorporates a knowledge base for the identification and setup of the design criteria. Candidate compounds are identified using a multi-level generate and test CAMD solution algorithm capable of designing molecules having a high level of molecular detail. A post solution step...... using an Integrated Computer Aided System (ICAS) for result analysis and verification is included in the methodology. Keywords: CAMD, separation processes, knowledge base, molecular design, solvent selection, substitution, group contribution, property prediction, ICAS Introduction The use of Computer...... Aided Molecular Design (CAMD) for the identification of compounds having specific physic...

  6. Highly dispersed metal catalyst

    Science.gov (United States)

    Xiao, Xin; West, William L.; Rhodes, William D.

    2016-11-08

    A supported catalyst having an atomic level single atom structure is provided such that substantially all the catalyst is available for catalytic function. A process of forming a single atom catalyst unto a porous catalyst support is also provided.

  7. Refrigeration Cycle Design for Refrigerant Mixtures by Molecular Simulation

    Czech Academy of Sciences Publication Activity Database

    Smith, W.R.; Francová, Magda; Kowalski, M.; Nezbeda, Ivo

    2010-01-01

    Roč. 75, č. 4 (2010), s. 383-391 ISSN 0010-0765 R&D Projects: GA AV ČR IAA400720710 Grant - others:NSERC(CA) OGP1041 Institutional research plan: CEZ:AV0Z40720504 Keywords : refrigerants * molecular simulation s * vapor–liquid equilibrium Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.853, year: 2010

  8. Designing molecular printboards: a photolithographic platform for recodable surfaces

    Czech Academy of Sciences Publication Activity Database

    Abt, D.; Schmidt, B. V. K. J.; Pop-Georgievski, Ognen; Quick, A. S.; Danilov, D.; Kostina, Nina Yu.; Bruns, M.; Wenzel, W.; Wegener, M.; Rodriguez-Emmenegger, Cesar; Barner-Kowollik, C.

    2015-01-01

    Roč. 21, č. 38 (2015), s. 13186-13190 ISSN 0947-6539 R&D Projects: GA ČR(CZ) GJ15-09368Y Institutional support: RVO:61389013 Keywords : cyclodextrin * molecular printboard * photoconjugation Subject RIV: BO - Biophysics Impact factor: 5.771, year: 2015

  9. Property Integration - A New Approach for Simultaneous Solution of Process and Molecular Design Problems

    DEFF Research Database (Denmark)

    The objective of this paper is to introduce the new concept of property integration. It is based on tracking and integrating properties throughout the process. This is made possible by exploiting the unique features at the interface of process and molecular design. Recently developed clustering...... concepts are employed to identify optimal properties without commitment to specific species. Subsequently, group contribution methods and molecular design techniques are employed to solve the reverse property prediction problem to design molecules possessing the optimal properties....

  10. PRO_LIGAND: an approach to de novo molecular design. 2. Design of novel molecules from molecular field analysis (MFA) models and pharmacophores.

    Science.gov (United States)

    Waszkowycz, B; Clark, D E; Frenkel, D; Li, J; Murray, C W; Robson, B; Westhead, D R

    1994-11-11

    A computational approach for molecular design, PRO_LIGAND, has been developed within the PROMETHEUS molecular design and simulation system in order to provide a unified framework for the de novo generation of diverse molecules which are either similar or complementary to a specified target. In this instance, the target is a pharmacophore derived from a series of active structures either by a novel interpretation of molecular field analysis data or by a pharmacophore-mapping procedure based on clique detection. After a brief introduction to PRO_LIGAND, a detailed description is given of the two pharmacophore generation procedures and their abilities are demonstrated by the elucidation of pharmacophores for steroid binding and ACE inhibition, respectively. As a further indication of its efficacy in aiding the rational drug design process, PRO_LIGAND is then employed to build novel organic molecules to satisfy the physicochemical constraints implied by the pharmacophores.

  11. Solar-Driven Reduction of Aqueous Protons Coupled to Selective Alcohol Oxidation with a Carbon Nitride-Molecular Ni Catalyst System.

    Science.gov (United States)

    Kasap, Hatice; Caputo, Christine A; Martindale, Benjamin C M; Godin, Robert; Lau, Vincent Wing-Hei; Lotsch, Bettina V; Durrant, James R; Reisner, Erwin

    2016-07-27

    Solar water-splitting represents an important strategy toward production of the storable and renewable fuel hydrogen. The water oxidation half-reaction typically proceeds with poor efficiency and produces the unprofitable and often damaging product, O2. Herein, we demonstrate an alternative approach and couple solar H2 generation with value-added organic substrate oxidation. Solar irradiation of a cyanamide surface-functionalized melon-type carbon nitride ((NCN)CNx) and a molecular nickel(II) bis(diphosphine) H2-evolution catalyst (NiP) enabled the production of H2 with concomitant selective oxidation of benzylic alcohols to aldehydes in high yield under purely aqueous conditions, at room temperature and ambient pressure. This one-pot system maintained its activity over 24 h, generating products in 1:1 stoichiometry, separated in the gas and solution phases. The (NCN)CNx-NiP system showed an activity of 763 μmol (g CNx)(-1) h(-1) toward H2 and aldehyde production, a Ni-based turnover frequency of 76 h(-1), and an external quantum efficiency of 15% (λ = 360 ± 10 nm). This precious metal-free and nontoxic photocatalytic system displays better performance than an analogous system containing platinum instead of NiP. Transient absorption spectroscopy revealed that the photoactivity of (NCN)CNx is due to efficient substrate oxidation of the material, which outweighs possible charge recombination compared to the nonfunctionalized melon-type carbon nitride. Photoexcited (NCN)CNx in the presence of an organic substrate can accumulate ultralong-lived "trapped electrons", which allow for fuel generation in the dark. The artificial photosynthetic system thereby catalyzes a closed redox cycle showing 100% atom economy and generates two value-added products, a solar chemical, and solar fuel.

  12. Recent advances in the molecular design of synthetic vaccines

    Science.gov (United States)

    Jones, Lyn H.

    2015-12-01

    Vaccines have typically been prepared using whole organisms. These are normally either attenuated bacteria or viruses that are live but have been altered to reduce their virulence, or pathogens that have been inactivated and effectively killed through exposure to heat or formaldehyde. However, using whole organisms to elicit an immune response introduces the potential for infections arising from a reversion to a virulent form in live pathogens, unproductive reactions to vaccine components or batch-to-batch variability. Synthetic vaccines, in which a molecular antigen is conjugated to a carrier protein, offer the opportunity to circumvent these problems. This Perspective will highlight the progress that has been achieved in developing synthetic vaccines using a variety of molecular antigens. In particular, the different approaches used to develop conjugate vaccines using peptide/proteins, carbohydrates and other small molecule haptens as antigens are compared.

  13. Molecular Design of Soluble Biopolyimide with High Rigidity

    Directory of Open Access Journals (Sweden)

    Sumant Dwivedi

    2018-03-01

    Full Text Available New soluble biopolyimides were prepared from a diamine derived from an exotic amino acid (4-aminocinnamic acid with several kinds of tetracarboxylic dianhydride. The biopolyimide molecular structural flexibility was tailored by modifying the tetracarboxylic dianhydride moiety. The obtained polyimides were soluble in various solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, and even tetrahydrofuran. It was observed that the biopolyimide solubility was greatly dependent upon the structural flexibility (torsion energy. Flexible structure facilitated greater solubility. The synthesized biopolyimides were largely amorphous and had number-average molecular weight (Mn in the range (5–8 × 105. The glass transition temperatures (Tg of the polymers ranged from 259–294 °C. These polymers exhibited good thermal stability without significant weight loss up to 410 °C. The temperatures at 10% weight loss (Td10 for synthesized biopolyimide ranged from 375–397 °C.

  14. Molecular Assemblies of Finite Shapes: Design and Self-Assembly ...

    Indian Academy of Sciences (India)

    Assembly via Coordination · Slide 2 · Slide 3 · Slide 4 · Slide 5 · Slide 6 · Slide 7 · Slide 8 · Slide 9 · Slide 10 · Slide 11 · Slide 12 · Slide 13 · Slide 14 · Slide 15 · Slide 16 · Slide 17 · Slide 18 · Slide 19 · Slide 20 · Slide 21 · Molecular Box · Slide 23.

  15. Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High-Energy X-ray Scattering and EXAFS Spectroscopy.

    Science.gov (United States)

    Yang, Ke R; Matula, Adam J; Kwon, Gihan; Hong, Jiyun; Sheehan, Stafford W; Thomsen, Julianne M; Brudvig, Gary W; Crabtree, Robert H; Tiede, David M; Chen, Lin X; Batista, Victor S

    2016-05-04

    The solution structures of highly active Ir water-oxidation catalysts are elucidated by combining density functional theory, high-energy X-ray scattering (HEXS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. We find that the catalysts are Ir dimers with mono-μ-O cores and terminal anionic ligands, generated in situ through partial oxidation of a common catalyst precursor. The proposed structures are supported by (1)H and (17)O NMR, EPR, resonance Raman and UV-vis spectra, electrophoresis, etc. Our findings are particularly valuable to understand the mechanism of water oxidation by highly reactive Ir catalysts. Importantly, our DFT-EXAFS-HEXS methodology provides a new in situ technique for characterization of active species in catalytic systems.

  16. [Towards computer-aided catalyst design: Three effective core potential studies of C-H activation]. Final report

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-12-31

    Research in the initial grant period focused on computational studies relevant to the selective activation of methane, the prime component of natural gas. Reaction coordinates for methane activation by experimental models were delineated, as well as the bonding and structure of complexes that effect this important reaction. This research, highlighted in the following sections, also provided the impetus for further development, and application of methods for modeling metal-containing catalysts. Sections of the report describe the following: methane activation by multiple-bonded transition metal complexes; computational lanthanide chemistry; and methane activation by non-imido, multiple-bonded ligands.

  17. Catalyst Design Using Nanoporous Iron for the Chemical Vapor Deposition Synthesis of Single-Walled Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Tarek M. Abdel-Fattah

    2013-01-01

    Full Text Available Single-walled carbon nanotubes (SWNTs have been synthesized via a novel chemical vapor deposition (CVD approach utilizing nanoporous, iron-supported catalysts. Stable aqueous dispersions of the CVD-grown nanotubes using an anionic surfactant were also obtained. The properties of the as-produced SWNTs were characterized through atomic force microscopy and Raman spectroscopy and compared with purified SWNTs produced via the high-pressure CO (HiPCO method as a reference, and the nanotubes were observed with greater lengths than those of similarly processed HiPCO SWNTs.

  18. Spectroscopic investigation into the design of solid-acid catalysts for the low temperature dehydration of ethanol.

    Science.gov (United States)

    Potter, Matthew E; Aswegen, Sivan V; Gibson, Emma K; Silverwood, Ian P; Raja, Robert

    2016-07-14

    The increased demand for bulk hydrocarbons necessitates research into increasingly sustainable, energy-efficient catalytic processes. Owing to intricately designed structure-property correlations, SAPO-34 has become established as a promising material for the low temperature ethanol dehydration to produce ethylene. However, further optimization of this process requires a precise knowledge of the reaction mechanism at a molecular level. In order to achieve this a range of spectroscopic characterization techniques are required to probe both the interaction with the active site, and also the wider role of the framework. To this end we employ a combination of in situ infra-red and neutron scattering techniques to elucidate the influence of the surface ethoxy species in the activation of both diethyl ether and ethanol, towards the improved formation of ethylene at low temperatures. The combined conclusions of these studies is that the formation of ethylene is the rate determining step, which is of fundamental importance towards the development of this process and the introduction of bio-ethanol as a viable feedstock for ethylene production.

  19. Molecular Iodine: A Versatile Catalyst for the Synthesis of 4-Aryl-3-methyl-1-phenyl-1H-benzo[h]pyrazolo[3,4-b]quinoline-5,10-diones in Water

    International Nuclear Information System (INIS)

    Wu, Liqiang; Yang, Limin; Yan, Fulin; Yang, Chunguang; Fang, Lizhen

    2010-01-01

    An efficient methodology for the synthesis of 4-aryl-3-methyl-1-phenyl-1H-benzo[h]pyrazolo[3,4-b]quinoline-5,10-diones has been developed. To our best knowledge, this is the first report for the synthesis of these compounds by multicomponent condensation of 3-methyl-1-phenyl-1H-pyrazol-5-amine, aldehydes and 2-hydroxynaphthalene-1,4-dione in the presence of molecular iodine as a catalyst in water. The simple experimental procedure, utilization of an inexpensive and readily available catalyst, and excellent yields are the advantages of the present method. Multicomponent reactions (MCRs) have attracted considerable attention since they are performed without need to isolate any intermediate during their processes; may reduce time and save both energy and raw materials. They have merits over two-component reactions in several aspects including the simplicity of a one-pot procedure, possible structural variations and building up complex molecules

  20. Molecular design of 99Tcm labelled radiopharmaceuticals. Pt.2

    International Nuclear Information System (INIS)

    Wang Xuebin; Chu Jinfeng

    2003-01-01

    The structure-activity relationship of 99 Tc m labelled radiopharmaceuticals and the correlative contents of computer aided drug design are introduced. Of them, quantitative structure-activity relationship and its application to design 99 Tc m labelled radiopharmaceuticals are narrated on emphases

  1. The strange case of the "oscillating" catalysts

    NARCIS (Netherlands)

    Busico, [No Value; Cipullo, R; Kretschmer, W; Talarico, G; Vacatello, M; Castelli, VV

    The field of stereoselective propene polymerization has been dramatically innovated by the discovery of homogeneous metallocene-based catalysts with well-defined and tunable molecular structure. Of all, "oscillating" metallocenes are probably the most ingenious and challenging example of catalyst

  2. Digital learning material for experimental design and model building in molecular biology

    NARCIS (Netherlands)

    Aegerter-Wilmsen, T.

    2005-01-01

    Designing experimental approaches is a major cognitive skill in molecular biology research, and building models, including quantitative ones, is a cognitive skill which is rapidly gaining importance. Since molecular biology education at university level is aimed at educating future researchers, we

  3. Molecular Design of Semiconducting Polymers for High-Performance Organic Electrochemical Transistors

    KAUST Repository

    Nielsen, Christian B.; Giovannitti, Alexander; Sbircea, Dan-Tiberiu; Bandiello, Enrico; Niazi, Muhammad Rizwan; Hanifi, David A.; Sessolo, Michele; Amassian, Aram; Malliaras, George G.; Rivnay, Jonathan; McCulloch, Iain

    2016-01-01

    required for accumulation mode OECT operation. We discuss key aspects relating to OECT performance such as ion and hole transport, elec-trochromic properties, operational voltage and stability. The demonstration of our molecular design strategy

  4. Bifunctional cobalt F-T catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Miller, J.G.; Coughlin, P.K.; Yang, C.L.; Rabo, J.A.

    1986-03-01

    Results on the catalytic screening of Fischer-Tropsch catalysts containing shape selective components are reported. Catalysts consist of promoted cobalt intimately contacted with Union Carbide molecular sieves and were tested using a Berty type internally recycled reactor. Methods of preparation, promoters and shape selective components were varied and aimed at improving catalyst performance. Catalysts were developed demonstrating high C/sub 5/ + yields with high olefin content and low methane production while maintaining stability under both low and high H/sub 2/:CO ratio conditions.

  5. Sputtered catalysts

    International Nuclear Information System (INIS)

    Tyerman, W.J.R.

    1978-01-01

    A method is described for preparing a supported catalyst by a sputtering process. A material that is catalytic, or which is a component of a catalytic system, is sputtered on to the surface of refractory oxide particles that are compatible with the sputtered material and the sputtered particles are consolidated into aggregate form. The oxide particles before sputtering should have a diameter in the range 1000A to 50μ and a porosity less than 0.4 ml/g, and may comprise MgO, Al 2 O 3 or SiO 2 or mixtures of these oxides, including hydraulic cement. The particles may possess catalytic activity by themselves or in combination with the catalytic material deposited on them. Sputtering may be effected epitaxially and consolidation may be effected by compaction pelleting, extrusion or spray drying of a slurry. Examples of the use of such catalysts are given. (U.K.)

  6. Molecular dynamics explorations of active site structure in designed and evolved enzymes.

    Science.gov (United States)

    Osuna, Sílvia; Jiménez-Osés, Gonzalo; Noey, Elizabeth L; Houk, K N

    2015-04-21

    This Account describes the use of molecular dynamics (MD) simulations to reveal how mutations alter the structure and organization of enzyme active sites. As proposed by Pauling about 70 years ago and elaborated by many others since then, biocatalysis is efficient when functional groups in the active site of an enzyme are in optimal positions for transition state stabilization. Changes in mechanism and covalent interactions are often critical parts of enzyme catalysis. We describe our explorations of the dynamical preorganization of active sites using MD, studying the fluctuations between active and inactive conformations normally concealed to static crystallography. MD shows how the various arrangements of active site residues influence the free energy of the transition state and relates the populations of the catalytic conformational ensemble to the enzyme activity. This Account is organized around three case studies from our laboratory. We first describe the importance of dynamics in evaluating a series of computationally designed and experimentally evolved enzymes for the Kemp elimination, a popular subject in the enzyme design field. We find that the dynamics of the active site is influenced not only by the original sequence design and subsequent mutations but also by the nature of the ligand present in the active site. In the second example, we show how microsecond MD has been used to uncover the role of remote mutations in the active site dynamics and catalysis of a transesterase, LovD. This enzyme was evolved by Tang at UCLA and Codexis, Inc., and is a useful commercial catalyst for the production of the drug simvastatin. X-ray analysis of inactive and active mutants did not reveal differences in the active sites, but relatively long time scale MD in solution showed that the active site of the wild-type enzyme preorganizes only upon binding of the acyl carrier protein (ACP) that delivers the natural acyl group to the active site. In the absence of bound ACP

  7. Molecular design, synthesis and evaluation of chemical biology tools

    NARCIS (Netherlands)

    Hoogenboom, Jorin

    2017-01-01

    Chapter 1 provides a perspective of synthetic organic chemistry as a discipline involved in the design, synthesis and evaluation of complex molecules. The reader is introduced with a brief history of synthetic organic chemistry, all the while dealing with different aspects of

  8. Glucose-responsive insulin by molecular and physical design

    Science.gov (United States)

    Bakh, Naveed A.; Cortinas, Abel B.; Weiss, Michael A.; Langer, Robert S.; Anderson, Daniel G.; Gu, Zhen; Dutta, Sanjoy; Strano, Michael S.

    2017-10-01

    The concept of a glucose-responsive insulin (GRI) has been a recent objective of diabetes technology. The idea behind the GRI is to create a therapeutic that modulates its potency, concentration or dosing relative to a patient's dynamic glucose concentration, thereby approximating aspects of a normally functioning pancreas. From the perspective of the medicinal chemist, the GRI is also important as a generalized model of a potentially new generation of therapeutics that adjust potency in response to a critical therapeutic marker. The aim of this Perspective is to highlight emerging concepts, including mathematical modelling and the molecular engineering of insulin itself and its potency, towards a viable GRI. We briefly outline some of the most important recent progress toward this goal and also provide a forward-looking viewpoint, which asks if there are new approaches that could spur innovation in this area as well as to encourage synthetic chemists and chemical engineers to address the challenges and promises offered by this therapeutic approach.

  9. Bio-inspired CO2 reduction by a rhenium tricarbonyl bipyridine-based catalyst appended to amino acids and peptidic platforms: incorporating proton relays and hydrogen-bonding functional groups.

    Science.gov (United States)

    Chabolla, S A; Machan, C W; Yin, J; Dellamary, E A; Sahu, S; Gianneschi, N C; Gilson, M K; Tezcan, F A; Kubiak, C P

    2017-06-02

    Herein, we report a new approach to bio-inspired catalyst design. The molecular catalyst employed in these studies is based on the robust and selective Re(bpy)(CO) 3 Cl-type (bpy = 2,2'-bipyridine) homogeneous catalysts, which have been extensively studied for their ability to reduce CO 2 electrochemically or photochemically in the presence of a photosensitizer. These catalysts can be highly active photocatalysts in their own right. In this work, the bipyridine ligand was modified with amino acids and synthetic peptides. These results build on earlier findings wherein the bipyridine ligand was functionalized with amide groups to promote dimer formation and CO 2 reduction by an alternate bimolecular mechanism at lower overpotential (ca. 250 mV) than the more commonly observed unimolecular process. The bio-inspired catalysts were designed to allow for the incorporation of proton relays to support reduction of CO 2 to CO and H 2 O. The coupling of amino acids tyrosine and phenylalanine led to the formation of two structurally similar Re catalyst/peptide catalysts for comparison of proton transport during catalysis. This article reports the synthesis and characterization of novel catalyst/peptide hybrids by molecular dynamics (MD simulations of structural dynamics), NMR studies of solution phase structures, and electrochemical studies to measure the activities of new bio-inspired catalysts in the reduction of CO 2.

  10. Metal-halide lamp design: atomic and molecular data needed

    International Nuclear Information System (INIS)

    Lapatovich, Walter P

    2009-01-01

    Metal-halide lamps are a subset of high intensity discharge (HID) lamps so named because of their high radiance. These lamps are low temperature (∼0.5 eV), weakly ionized plasmas sustained in refractory but light transmissive envelopes by the passage of electric current through atomic and molecular vapors. For commercial applications, the conversion of electric power to light must occur with good efficiency and with sufficient spectral content throughout the visible (380-780 nm) to permit the light so generated to render colors comparable to natural sunlight. This is achieved by adding multiple metals to a basic mercury discharge. Because the vapor pressure of most metals is very much lower than mercury itself, metal-halide salts of the desired metals, having higher vapor pressures, are used to introduce the material into the basic discharge. The metal compounds are usually polyatomic iodides, which vaporize and subsequently dissociate as they diffuse into the bulk plasma. Metals with multiple visible transitions are necessary to achieve high photometric efficiency (efficacy) and good color. Compounds of Sc, Dy, Ho, Tm, Ce, Pr, Yb and Nd are commonly used. The electrons, atoms and radicals are in local thermodynamic equilibrium (LTE), but not with the radiation field. Strong thermal (10 6 K m -1 ) and density gradients are sustained in the discharge. Atomic radiation produced in the high-temperature core transits through colder gas regions where it interacts with cold atoms and un-dissociated molecules before exiting the lamp. Power balance and spectral output of the lamp are directly affected by the strength of atomic transitions. Attempts to simulate the radiative output of functional metal-halide lamps have been successful only in very simple cases. More data (e.g. the atomic transition probabilities of Ce i) are necessary to improve lamp performance, to select appropriate radiators and in scaling the lamp geometry to various wattages for specific applications.

  11. Molecular Entropy, Thermal Efficiency, and Designing of Working Fluids for Organic Rankine Cycles

    Science.gov (United States)

    Wang, Jingtao; Zhang, Jin; Chen, Zhiyou

    2012-06-01

    A shortage of fossil energy sources boosts the utilization of renewable energy. Among numerous novel techniques, recovering energy from low-grade heat sources through power generation via organic Rankine cycles (ORCs) is one of the focuses. Properties of working fluids are crucial for the ORC's performance. Many studies have been done to select proper working fluids or to design new working fluids. However, no researcher has systematically investigated the relationship between molecular structures and thermal efficiencies of various working fluids for an ideal ORC. This paper has investigated the interrelations of molecular structures, molecular entropies, and thermal efficiencies of various working fluids for an ideal ORC. By calculating thermal efficiencies and molecular entropies, we find that the molecular entropy is the most appropriate thermophysical property of a working fluid to determine how much energy can be converted into work and how much cannot in a system. Generally speaking, working fluids with low entropies will generally have high thermal efficiency for an ideal ORC. Based on this understanding, the direct interrelations of molecular structures and entropies provide an explicit interrelation between molecular structures and thermal efficiencies, and thus provide an insightful direction for molecular design of novel working fluids for ORCs.

  12. Molecular Orbital Based Design Guidelines for Hypergolic Energetic Ionic Liquids

    Science.gov (United States)

    2015-01-01

    energy content of the anion must also be taken into account in the design strategy ; substitution should be carried out in such a way that does not...substitution strategy . So far in the litera- ture, HP (with energy gap similar to DCA) is the lowest DHf anion (661.9 kJmol1) for which EIL hypergolicity...T. Nakajima, Y. Honda , O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts

  13. Molecular Cobalt Catalysts for O 2 Reduction: Low-Overpotential Production of H 2 O 2 and Comparison with Iron-Based Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yu-Heng [Department; Pegis, Michael L. [Department; Mayer, James M. [Department; Stahl, Shannon S. [Department

    2017-11-07

    A series of mononuclear pseudo-macrocyclic cobalt complexes have been investigated as catalysts for O2 reduction. Each of these complexes, with CoIII/II reduction potentials that span nearly 400 mV, mediate highly selective two- electron reduction of O2 to H2O2 (93–99%) using decamethylferrocene (Fc*) as the reductant and acetic acid as the proton source. Kinetic studies reveal that the rate exhibits a first- order dependence on [Co] and [AcOH], but no dependence on [O2] or [Fc*]. A linear correlation is observed between log(TOF) vs. E1/2(CoIII/II) for the different cobalt complexes (TOF = turnover frequency). The thermodynamic potential for+ O2 reduction to H2O2 was estimated by measuring the H /H2 open-circuit potential under the reaction conditions. This value provides the basis for direct assessment of the thermodynamic efficiency of the different catalysts and shows that H2O2 is formed with overpotentials as low as 90 mV. These results are compared with a recently reported series of Fe-porphyrin complexes, which catalyze four-electron reduction of O2 to H2O. The data show that the TOFs of the Co complexes exhibit a shallower dependence on E1/2(MIII/II) than the Fe complexes. This behavior, which underlies the low overpotential, is rationalized on the basis of the catalytic rate law.

  14. Design of bimetal catalysts Pt-Ni/CeO_2-1D for generation of H_2 by the reforming reaction of methanol

    International Nuclear Information System (INIS)

    Sarmiento F, I.

    2016-01-01

    CeO_2 nano rods were synthesized by hydrothermal method and were used as support for preparing catalysts bimetallic Pt Ni / CeO_2-1D. The catalysts were prepared by classical impregnation by the conventional wet method. The prepared catalysts are Pt (0.5 %) - Ni (5 %) / CeO_2 and Pt (0.5 %) - Ni (15 %) / CeO_2, which were characterized by different physico-chemical techniques: Bet, Sem, TPR and XRD, that were evaluated in the Auto thermal Steam reforming of Methanol for H_2 production. The Bet surface area results, show that the surface area of the catalysts decreases as the nominal load of Ni in the catalyst, increases. Sem shows, that the catalyst support (CeO_2-1D) and the bimetallic catalysts are conformed by nano rods. By XRD were identified the crystalline phases present, in the catalytic material: cerianite distinctive phase of cerium oxide and metallic Ni; however it was not possible to observe diffraction peaks of Platinum using this technique. The temperature-programmed reduction (TPR) analysis allowed to obtain the reduction profiles, of the different species present on the catalysts. The catalytic activity tests carried out, showed that the catalysts total 100% methanol conversion is achieved at 300 degrees Celsius, making them excellent, to be used in reactions at low temperature conditions. Selectivity towards H_2, is very similar in both catalysts, and it reaches a 50% yield per mole of methanol fed stoichiometrically. (Author)

  15. SMART design to control over conformation and molecular packing in blue luminescent oligofluorenes

    Science.gov (United States)

    Yu, Meng-Na; Ou, Chang-Jin; Liu, Bin; Xie, Ling-Hai; Lin, Jin-Yi; Wang, Sha-Sha; Wei, Ying; Huang, Wei

    2018-01-01

    The uncertainty evolution of conformation and molecular packing from solution to film is key challenge for the repeatability of procedures in organic optoelectronics. Herein, we observed the noncovalent force at the bulky groups to decode the supramolecular steric hindrance (SSH) effect and to propose synergistically molecular attractor-repulsor theory (SMART). The fine difference between ideal and real bulks were described and the SSH effect have been proved by two comparable stat-of-the-art models. The SMART design guide us to discover blue oligo/polydiarylfluorenes with beta phase as well as nanosheets with the paradigm of Interdigital Lipid Bilayer-like (ILB) mode. SMART address one kind of AR molecules with potential controllable behaviors. The design of bulk-withdraw and bulk-rich will exhibit the unreplaceable role in morphology-directed design that is just like the role of donor-acceptor molecular design of organic polymer semiconductors.

  16. Rational design of methicillin resistance staphylococcus aureus inhibitors through 3D-QSAR, molecular docking and molecular dynamics simulations.

    Science.gov (United States)

    Ballu, Srilata; Itteboina, Ramesh; Sivan, Sree Kanth; Manga, Vijjulatha

    2018-04-01

    Staphylococcus aureus is a gram positive bacterium. It is the leading cause of skin and respiratory infections, osteomyelitis, Ritter's disease, endocarditis, and bacteraemia in the developed world. We employed combined studies of 3D QSAR, molecular docking which are validated by molecular dynamics simulations and in silico ADME prediction have been performed on Isothiazoloquinolones inhibitors against methicillin resistance Staphylococcus aureus. Three-dimensional quantitative structure-activity relationship (3D-QSAR) study was applied using comparative molecular field analysis (CoMFA) with Q 2 of 0.578, R 2 of 0.988, and comparative molecular similarity indices analysis (CoMSIA) with Q 2 of 0.554, R 2 of 0.975. The predictive ability of these model was determined using a test set of molecules that gave acceptable predictive correlation (r 2 Pred) values 0.55 and 0.57 of CoMFA and CoMSIA respectively. Docking, simulations were employed to position the inhibitors into protein active site to find out the most probable binding mode and most reliable conformations. Developed models and Docking methods provide guidance to design molecules with enhanced activity. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Molecular design of sequence specific DNA alkylating agents.

    Science.gov (United States)

    Minoshima, Masafumi; Bando, Toshikazu; Shinohara, Ken-ichi; Sugiyama, Hiroshi

    2009-01-01

    Sequence-specific DNA alkylating agents have great interest for novel approach to cancer chemotherapy. We designed the conjugates between pyrrole (Py)-imidazole (Im) polyamides and DNA alkylating chlorambucil moiety possessing at different positions. The sequence-specific DNA alkylation by conjugates was investigated by using high-resolution denaturing polyacrylamide gel electrophoresis (PAGE). The results showed that polyamide chlorambucil conjugates alkylate DNA at flanking adenines in recognition sequences of Py-Im polyamides, however, the reactivities and alkylation sites were influenced by the positions of conjugation. In addition, we synthesized conjugate between Py-Im polyamide and another alkylating agent, 1-(chloromethyl)-5-hydroxy-1,2-dihydro-3H-benz[e]indole (seco-CBI). DNA alkylation reactivies by both alkylating polyamides were almost comparable. In contrast, cytotoxicities against cell lines differed greatly. These comparative studies would promote development of appropriate sequence-specific DNA alkylating polyamides against specific cancer cells.

  18. Metal-​based catalysts for controlled ring-​opening polymerization of macrolactones : high molecular weight and well-​defined copolymer architectures

    NARCIS (Netherlands)

    Bouyahyi, M.; Duchateau, R.

    2014-01-01

    This contribution describes our recent results regarding the metal-¿catalyzed ring-¿opening polymn. of pentadecalactone and its copolymn. with e-¿caprolactone involving single-¿site metal complexes based on aluminum, zinc, and calcium. Under the right conditions (i.e., monomer concn., catalyst type,

  19. Design, synthesis, α-glucosidase inhibitory activity, molecular docking and QSAR studies of benzimidazole derivatives

    Science.gov (United States)

    Dinparast, Leila; Valizadeh, Hassan; Bahadori, Mir Babak; Soltani, Somaieh; Asghari, Behvar; Rashidi, Mohammad-Reza

    2016-06-01

    In this study the green, one-pot, solvent-free and selective synthesis of benzimidazole derivatives is reported. The reactions were catalyzed by ZnO/MgO containing ZnO nanoparticles as a highly effective, non-toxic and environmentally friendly catalyst. The structure of synthesized benzimidazoles was characterized using spectroscopic technics (FT-IR, 1HNMR, 13CNMR). Synthesized compounds were evaluated for their α-glucosidase inhibitory potential. Compounds 3c, 3e, 3l and 4n were potent inhibitors with IC50 values ranging from 60.7 to 168.4 μM. In silico studies were performed to explore the binding modes and interactions between enzyme and synthesized benzimidazoles. Developed linear QSAR model based on density and molecular weight could predict bioactivity of newly synthesized compounds well. Molecular docking studies revealed the availability of some hydrophobic interactions. In addition, the bioactivity of most potent compounds had good correlation with estimated free energy of binding (ΔGbinding) which was calculated according to docked best conformations.

  20. Chapter 6 – Computer-Aided Molecular Design and Property Prediction

    DEFF Research Database (Denmark)

    Gani, Rafiqul; Zhang, L.; Kalakul, Sawitree

    2017-01-01

    for the initial stages of the design/development process. Therefore, computer-aided molecular design and property prediction techniques are two topics that play important roles in chemical product design, analysis, and application. In this chapter, an overview of the concepts, methods, and tools related......Today's society needs many chemical-based products for its survival, nutrition, health, transportation, agriculture, and the functioning of processes. Chemical-based products have to be designed/developed in order to meet these needs, while at the same time, they must be innovative and sustainable...... to these two topics are given. In addition, a generic computer-aided framework for the design of molecules, mixtures, and blends is presented. The application of the framework is highlighted for molecular products through two case studies involving the design of refrigerants and surfactants....

  1. A novel design for electric field deflectometry on extended molecular beams

    International Nuclear Information System (INIS)

    Stefanov, André; Berninger, Martin; Arndt, Markus

    2008-01-01

    We discuss the optimal shape of a beam deflector with applications in electric susceptibility measurements on wide molecular beams. In contrast to the well-established 'two-wire' concept, which is optimized for beams with a small lateral extension, our design realizes a compact element that provides a high and homogeneous force field at moderate voltage for molecular beams with a large extension in the direction of deflection

  2. Quick Guide to Flash Catalyst

    CERN Document Server

    Elmansy, Rafiq

    2011-01-01

    How do you transform user interface designs created in Photoshop or Illustrator into interactive web pages? It's easier than you think. This guide shows you how to use Adobe Flash Catalyst to create interactive UIs and website wireframes for Rich Internet Applications-without writing a single line of code. Ideal for web designers, this book introduces Flash Catalyst basics with detailed step-by-step instructions and screenshots that illustrate every part of the process. You'll learn hands-on how to turn your static design or artwork into working user interfaces that can be implemented in Fla

  3. Generic Mathematical Programming Formulation and Solution for Computer-Aided Molecular Design

    DEFF Research Database (Denmark)

    Zhang, Lei; Cignitti, Stefano; Gani, Rafiqul

    2015-01-01

    This short communication presents a generic mathematical programming formulation for Computer-Aided Molecular Design (CAMD). A given CAMD problem, based on target properties, is formulated as a Mixed Integer Linear/Non-Linear Program (MILP/MINLP). The mathematical programming model presented here......, which is formulated as an MILP/MINLP problem, considers first-order and second-order molecular groups for molecular structure representation and property estimation. It is shown that various CAMD problems can be formulated and solved through this model....

  4. 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.

  5. Industrial biotemplating saves precious metals in catalysts; Industrielles Biotemplating zur Einsparung von Edelmetallen in Katalysatoren

    Energy Technology Data Exchange (ETDEWEB)

    Hofinger, Juergen; Roos, Steffen; Zirpel, Kevin; Wengrzik, Stefanie [Namos GmbH, Dresden (Germany)

    2009-07-15

    Modern molecular biology provides the tools to design surfaces on the nanometer scale. This opens the way to a breakthrough innovation, which can optimize many industrial processes. In a proof-of-concept study, scientists were able to successfully reduce the amount of precious metals required for a diesel oxidation catalyst. This was the first successful application, and right now the biotemplating technology awaits further development for other applications involving catalytic processes or specifically designed surfaces for industrial processes. (orig.)

  6. Coking of residue hydroprocessing catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Gray, M.R.; Zhao, Y.X. [Alberta Univ., Edmonton, AB (Canada). Dept. of Chemical Engineering; McKnight, C.A. [Syncrude Canada Ltd., Edmonton, AB (Canada); Komar, D.A.; Carruthers, J.D. [Cytec Industries Inc., Stamford, CT (United States)

    1997-11-01

    One of the major causes of deactivation of Ni/Mo and Co/Mo sulfide catalysts for hydroprocessing of heavy petroleum and bitumen fractions is coke deposition. The composition and amount of coke deposited on residue hydroprocessing catalysts depends on the composition of the liquid phase of the reactor. In the Athabasca bitumen, the high molecular weight components encourage coke deposition at temperatures of 430 to 440 degrees C and at pressures of 10 to 20 MPa hydrogen pressure. A study was conducted to determine which components in the heavy residual oil fraction were responsible for coking of catalysts. Seven samples of Athabasca vacuum residue were prepared by supercritical fluid extraction with pentane before being placed in the reactor. Carbon content and hydrodesulfurization activity was measured. It was concluded that the deposition of coke depended on the presence of asphaltenes and not on other compositional variables such as content of nitrogen, aromatic carbon or vanadium.

  7. Molecular modeling for the design of novel performance chemicals and materials

    CERN Document Server

    Rai, Beena

    2012-01-01

    Molecular modeling (MM) tools offer significant benefits in the design of industrial chemical plants and material processing operations. While the role of MM in biological fields is well established, in most cases MM works as an accessory in novel products/materials development rather than a tool for direct innovation. As a result, MM engineers and practitioners are often seized with the question: ""How do I leverage these tools to develop novel materials or chemicals in my industry?"" Molecular Modeling for the Design of Novel Performance Chemicals and Materials answers this important questio

  8. Preparation of heterogeneous catalysts supported on mesoporous molecular sieves modified with various N-groups and their use in the Heck reaction

    Czech Academy of Sciences Publication Activity Database

    Demel, Jan; Sujandi, X.; Park, S.; Y.; Čejka, Jiří; Štěpnička, P.

    2009-01-01

    Roč. 302, 1-2 (2009), s. 28-35 ISSN 1381-1169 R&D Projects: GA MŠk(CZ) LC06070; GA ČR GA104/09/0561 Institutional research plan: CEZ:AV0Z40400503 Keywords : supported catalysis * palladium * bifunctional catalysts * nanoparticles Subject RIV: BL - Plasma and Gas Discharge Physics Impact factor: 3.135, year: 2009

  9. Highly recoverable pyridinium-tagged Hoveyda-Grubbs pre-catalyst for olefin metathesis. Design of the boomerang ligand toward the optimal compromise between activity and reusability.

    Science.gov (United States)

    Rix, Diane; Caïjo, Fréderic; Laurent, Isabelle; Gulajski, Lukasz; Grela, Karol; Mauduit, Marc

    2007-09-28

    Whereas the boomerang ligand of Hoveyda-Grubbs pre-catalysts can be modified by attachment of a pyridinium tag to its benzylidene moiety, a precise adjustment of the length of the spacer allows the optimum balance to be reached between the activity of the catalyst and its recoverability, exceeding 98% after 6 catalytic runs in the best case.

  10. Manganese oxide octahedral molecular sieve K-OMS-2 as catalyst in post plasma-catalysis for trichloroethylene degradation in humid air

    International Nuclear Information System (INIS)

    Nguyen Dinh, M.T.; Giraudon, J.-M.; Vandenbroucke, A.M.; Morent, R.; De Geyter, N.; Lamonier, J.-F.

    2016-01-01

    Highlights: • Post plasma catalysis: negative DC glow discharge combined with a cryptomelane. • The α-MnO_2 catalyst totally decomposes the NTP generated ozone. • Active oxygen oxidizes the end-up plasma VOC by-products. - Abstract: The total oxidation of trichloroethylene (TCE) in air at low relative humidity (RH = 10%) in the presence of CO_2 (520 ppmv) was investigated in function of energy density using an atmospheric pressure negative DC luminescent glow discharge combined with a cryptomelane catalyst positioned downstream of the plasma reactor at a temperature of 150 °C. When using Non-Thermal Plasma (NTP) alone, it is found a low COx (x = 1–2) yield in agreement with the detection of gaseous polychlorinated by-products in the outlet stream as well as ozone which is an harmful pollutant. Introduction of cryptomelane enhanced trichloroethylene removal, totally inhibited plasma ozone formation and increased significantly the COx yield. The improved performances of the hybrid system were mainly ascribed to the total destruction of plasma generated ozone on cryptomelane surface to produce active oxygen species. Consequently these active oxygen species greatly enhanced the abatement of the plasma non-reacted TCE and completely destroyed the hazardous plasma generated polychlorinated intermediates. The facile redox of Mn species associated with oxygen vacancies and mobility as well as the textural properties of the catalyst might also contribute as a whole to the efficiency of the process.

  11. Manganese oxide octahedral molecular sieve K-OMS-2 as catalyst in post plasma-catalysis for trichloroethylene degradation in humid air

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen Dinh, M.T. [Université Lille, Sciences et Technologies, Unité de Catalyse et Chimie du Solide UMR CNRS UCCS 8181, 59655 Villeneuve d’Ascq (France); The University of Da-Nang, University of Science and Technology, 54, Nguyen Luong Bang, Da-Nang (Viet Nam); Giraudon, J.-M., E-mail: jean-marc.giraudon@univ-lille1.fr [Université Lille, Sciences et Technologies, Unité de Catalyse et Chimie du Solide UMR CNRS UCCS 8181, 59655 Villeneuve d’Ascq (France); Vandenbroucke, A.M.; Morent, R.; De Geyter, N. [Ghent University, Faculty of Engineering and Architecture, Department of Applied Physics, Research Unit Plasma Technology, Sint-Pietersnieuwstraat 41, 9000 Ghent (Belgium); Lamonier, J.-F. [Université Lille, Sciences et Technologies, Unité de Catalyse et Chimie du Solide UMR CNRS UCCS 8181, 59655 Villeneuve d’Ascq (France)

    2016-08-15

    Highlights: • Post plasma catalysis: negative DC glow discharge combined with a cryptomelane. • The α-MnO{sub 2} catalyst totally decomposes the NTP generated ozone. • Active oxygen oxidizes the end-up plasma VOC by-products. - Abstract: The total oxidation of trichloroethylene (TCE) in air at low relative humidity (RH = 10%) in the presence of CO{sub 2} (520 ppmv) was investigated in function of energy density using an atmospheric pressure negative DC luminescent glow discharge combined with a cryptomelane catalyst positioned downstream of the plasma reactor at a temperature of 150 °C. When using Non-Thermal Plasma (NTP) alone, it is found a low COx (x = 1–2) yield in agreement with the detection of gaseous polychlorinated by-products in the outlet stream as well as ozone which is an harmful pollutant. Introduction of cryptomelane enhanced trichloroethylene removal, totally inhibited plasma ozone formation and increased significantly the COx yield. The improved performances of the hybrid system were mainly ascribed to the total destruction of plasma generated ozone on cryptomelane surface to produce active oxygen species. Consequently these active oxygen species greatly enhanced the abatement of the plasma non-reacted TCE and completely destroyed the hazardous plasma generated polychlorinated intermediates. The facile redox of Mn species associated with oxygen vacancies and mobility as well as the textural properties of the catalyst might also contribute as a whole to the efficiency of the process.

  12. Towards molecular design using 2D-molecular contour maps obtained from PLS regression coefficients

    Science.gov (United States)

    Borges, Cleber N.; Barigye, Stephen J.; Freitas, Matheus P.

    2017-12-01

    The multivariate image analysis descriptors used in quantitative structure-activity relationships are direct representations of chemical structures as they are simply numerical decodifications of pixels forming the 2D chemical images. These MDs have found great utility in the modeling of diverse properties of organic molecules. Given the multicollinearity and high dimensionality of the data matrices generated with the MIA-QSAR approach, modeling techniques that involve the projection of the data space onto orthogonal components e.g. Partial Least Squares (PLS) have been generally used. However, the chemical interpretation of the PLS-based MIA-QSAR models, in terms of the structural moieties affecting the modeled bioactivity has not been straightforward. This work describes the 2D-contour maps based on the PLS regression coefficients, as a means of assessing the relevance of single MIA predictors to the response variable, and thus allowing for the structural, electronic and physicochemical interpretation of the MIA-QSAR models. A sample study to demonstrate the utility of the 2D-contour maps to design novel drug-like molecules is performed using a dataset of some anti-HIV-1 2-amino-6-arylsulfonylbenzonitriles and derivatives, and the inferences obtained are consistent with other reports in the literature. In addition, the different schemes for encoding atomic properties in molecules are discussed and evaluated.

  13. Possibility designing half-wave and full-wave molecular rectifiers by using single benzene molecule

    Science.gov (United States)

    Abbas, Mohammed A.; Hanoon, Falah H.; Al-Badry, Lafy F.

    2018-02-01

    This work focused on possibility designing half-wave and full-wave molecular rectifiers by using single and two benzene rings, respectively. The benzene rings were threaded by a magnetic flux that changes over time. The quantum interference effect was considered as the basic idea in the rectification action, the para and meta configurations were investigated. All the calculations are performed by using steady-state theoretical model, which is based on the time-dependent Hamiltonian model. The electrical conductance and the electric current are considered as DC output signals of half-wave and full-wave molecular rectifiers. The finding in this work opens up the exciting potential to use these molecular rectifiers in molecular electronics.

  14. Molecular structure descriptors in the computer-aided design of biologically active compounds

    International Nuclear Information System (INIS)

    Raevsky, Oleg A

    1999-01-01

    The current state of description of molecular structure in computer-aided molecular design of biologically active compounds by means of descriptors is analysed. The information contents of descriptors increases in the following sequence: element-level descriptors-structural formulae descriptors-electronic structure descriptors-molecular shape descriptors-intermolecular interaction descriptors. Each subsequent class of descriptors normally covers information contained in the previous-level ones. It is emphasised that it is practically impossible to describe all the features of a molecular structure in terms of any single class of descriptors. It is recommended to optimise the number of descriptors used by means of appropriate statistical procedures and characteristics of structure-property models based on these descriptors. The bibliography includes 371 references.

  15. Interactive Multimodal Molecular Set – Designing Ludic Engaging Science Learning Content

    DEFF Research Database (Denmark)

    Thorsen, Tine Pinholt; Christiansen, Kasper Holm Bonde; Jakobsen Sillesen, Kristian

    2014-01-01

    This paper reports on an exploratory study investigating 10 primary school students’ interaction with an interactive multimodal molecular set fostering ludic engaging science learning content in primary schools (8th and 9th grade). The concept of the prototype design was to bridge the physical...... and virtual worlds with electronic tags and, through this, blend the familiarity of the computer and toys, to create a tool that provided a ludic approach to learning about atoms and molecules. The study was inspired by the participatory design and informant design methodologies and included design...

  16. Molecular Thermodynamic Modeling and Design of Microencapsulation Systems for Drug Delivery

    DEFF Research Database (Denmark)

    Abildskov, Jens; O’Connell, John P.

    2011-01-01

    is based on fundamental thermodynamic relations and group contributions to properties of pure species (solvent, active ingredient and polymer) and their mixtures. The method is intended for pharmaceuticals with complex molecular structures, for which limited experimental information is known. Case studies......A systematic design strategy is given for computer-aided design of microparticle drug-delivery systems produced by solvent evaporation. In particular, design of solvents, polymer material, and external phase composition are considered for the case when the active ingredient is known. The procedure...... of solvent design are given....

  17. Carbonaceous deposits on naptha reforming catalysts

    International Nuclear Information System (INIS)

    Redwan, D.S.

    1999-01-01

    Carbonaceous deposits on naphtha reforming catalysts play a decisive role in limiting process performance. The deposits negatively after catalyst activity, selectivity and the production cycle of a semi regenerative reformer. The magnitude of negative effect of those deposits is directly proportional to their amounts and complexity. Investigations on used reforming catalysts samples reveal that the amount and type (complexity of the chemical nature) of carbonaceous deposits are directly proportional to the catalysts life on stream and the severity of operating conditions. In addition, the combustibility behavior of carbonaceous deposits on the catalyst samples taken from different reformers are found to be different. Optimal carbon removal, for in situ catalyst regeneration, requires the specific conditions be developed, based on the results of well designed and properly performed investigations of the amount and type of carbonaceous deposits. (author)

  18. Adsorptive detoxification of fermentation inhibitors in acid pretreated liquor using functionalized polymer designed by molecular simulation.

    Science.gov (United States)

    Devendra, Leena P; Pandey, Ashok

    2017-11-01

    Acid pretreatment is the most common method employed in the lignocellulosic biorefinery leading to the separation of pentose and hexose sugar. The liquor obtained after pretreatment (acid pretreatment liquor or APL) needs to be detoxified prior to fermentation. The aim of this study was to design functional groups on a polymer matrix which are selective in their interaction to inhibitors with little or no specificity to sugars. Molecular modeling was used as a tool to design a suitable adsorbent for selective adsorption of inhibitors from a complex mixture of APL. Phenyl glycine-p-sulfonic acid loaded on chloromethylated polystyrene polymer was designed as an adsorbent for selective interaction with inhibitors. Experimental verification of the selectivity was successfully achieved. The current study provides insights on the adsorptive separation processes at the molecular level by design of specific adsorbent which can be tailor made for the better selectivity of the desired component.

  19. Designs of Plasmonic Metamasks for Photopatterning Molecular Orientations in Liquid Crystals

    Directory of Open Access Journals (Sweden)

    Yubing Guo

    2016-12-01

    Full Text Available Aligning liquid crystal (LC molecules into spatially non-uniform orientation patterns is central to the functionalities of many emerging LC devices. Recently, we developed a new projection photopatterning technique by using plasmonic metamasks (PMMs, and demonstrated high-resolution and high-throughput patterning of molecular orientations into arbitrary patterns. Here we present comparisons between two different types of metamask designs: one based on curvilinear nanoslits in metal films; the other based on rectangular nanoapertures in metal films. By using numerical simulations and experimental studies, we show that the PMMs based on curvilinear nanoslits exhibit advantages in their broadband and high optical transmission, while face challenges in mask designing for arbitrary molecular orientations. In contrast, the PMMs based on nanoapertures, though limited in optical transmission, present the great advantage of allowing for patterning arbitrary molecular orientation fields.

  20. FCC catalyst technologies expand limits of process capability

    International Nuclear Information System (INIS)

    Leiby, S.

    1992-01-01

    This paper reports that over the past 30 or so years, many improvements in fluid catalytic cracking (FCC) operation have been achieved as the result of innovations in catalyst formulation. During the 1990s, new environmental regulations on issues such as reformulated gasoline will place new demands on both the refining industry and catalyst suppliers. An overview of cracking catalyst technology therefore seems in order. Today, high-technology innovations by catalyst manufacturers are rapid, but profit margins are slim. Catalyst formulations are shrouded in secrecy and probably depend almost as much on art as on science. Special formulations for specific cracking applications get the greatest emphasis today. To illustrate this point, OGJ's Worldwide Catalyst Report lists over 200 FCC catalyst designations. Catalysts containing components to enhance gasoline octane now account for about 70% of total U.S. FCC catalyst usage

  1. Study on molecular modelling of the selectivity of catalysts for heavy petroleum fractions hydrocracking; Etude sur molecule modele des parametres regissant la selectivite des catalyseurs d'hydrocraquage des charges lourdes

    Energy Technology Data Exchange (ETDEWEB)

    Leite, L.

    2000-10-19

    Hydrocracking is a catalytic petroleum refining process that is commonly applied to upgrade the heavier fractions obtained from the distillation of crude oils. Nowadays the European demand for good quality middle distillates (kerosene and gas-oil) is high and one important goal for the refining is to transform selectively feedstocks into middle distillates. To understand how this transformation occurs, studies on model compounds have been investigated. Numerous studies have been devoted to paraffin hydrocracking. However theses molecules do not fully represent heavy petroleum fraction. Taking into account that the trend in the future will be to treat heavier feedstocks containing a large quantity of PNA (Polynuclear Aromatic hydrocarbons), the understanding of their transformation under hydrocracking conditions is a key point. In this study, we studied hydrocracking of phenanthrene over platinum on acid solids catalysts. Our main aim was to compare hydrocracking catalysts in term of catalytic activity and selectivity toward primary products thanks to our model reaction and to correlate these catalytic performances with acid solid properties and especially to rationalize the effects due to the acidity and the porosity of the acid solids. Catalytic experiments emphasised an effect of the porous structure on the selectivities. The acidity of the catalysts seemed to impose the catalytic activity but did not permit to explain the selectivities. This 'effect of the structure' has been clarified with the simulation of intermediate products adsorption and diffusion in the studied structures thanks to a molecular modelling study. Indeed, the selectivities obtained during phenanthrene hydrocracking have been linked up with the intermediate products adsorption energies in the structures. The results of this study permit to propose that the key-step for selectivities determination is the physical desorption of the primary products. (author)

  2. Design and synthesis of single-source molecular precursors to homogeneous multi-component oxide materials

    Science.gov (United States)

    Fujdala, Kyle Lee

    This dissertation describes the syntheses of single-source molecular precursors to multi-component oxide materials. These molecules possess a core metal or element with various combinations of -OSi(O tBu)3, -O2P(OtBu) 2, and -OB[OSi(OtBu)3] 2 ligands. Such molecules decompose under mild thermolytic conditions (models for oxide-supported metal species and multi-component oxides. Significantly, the first complexes to contain three or more heteroelements suitable for use in the TMP method have been synthesized. Compounds for use as single-source molecular precursors have been synthesized containing Al, B, Cr, Hf, Mo, V, W, and Zr, and their thermal transformations have been examined. Heterogeneous catalytic reactions have been examined for selected materials. Also, cothermolyses of molecular precursors and additional molecules (i.e., metal alkoxides) have been utilized to provide materials with several components for potential use as catalysts or catalyst supports. Reactions of one and two equivs of HOSi(OtBu) 3 with Cr(OtBu)4 afforded the first Cr(IV) alkoxysiloxy complexes (tBuO) 3CrOSi(OtBu)3 and ( tBuO)2Cr[OSi(OtBu) 3]2, respectively. The high-yielding, convenient synthesis of (tBuO)3CrOSi(O tBu)3 make this complex a useful single-source molecular precursor, via the TMP method, to Cr/Si/O materials. The thermal transformations of (tBuO)3CrOSi(O tBu)3 and (tBuO) 2Cr[OSi(OtBu)3]2 to chromia-silica materials occurr at low temperatures (≤180°C), to give isobutene as the major carbon-containing product. The material generated from the solid-state conversion of (tBuO) 3CrOSi(OtBu)3 (CrOS ss) has an unexpectedly high surface area of 315 m2 g-1 that is slightly reduced to 275 m2 g-1 after calcination at 500°C in O2. The xerogel obtained by the thermolysis of an n-octane solution of (tBuO)3CrOSi(O tBu)3 (CrOSixg) has a surface area of 315 m2 g-1 that is reduced to 205 m2 g-1 upon calcination at 500°C. Powder X-ray diffraction (PXRD) analysis revealed that Cr2O 3 is

  3. Cobaltoporphyrin-Catalyzed CO 2 /Epoxide Copolymerization: Selectivity Control by Molecular Design

    KAUST Repository

    Anderson, Carly E.; Vagin, Sergei I.; Xia, Wei; Jin, Hanpeng; Rieger, Bernhard

    2012-01-01

    A series of cobalt(III) chloride porphyrin complexes of the general formula 5,10,15,20-tetra(p-alkoxy)phenylporphyrin cobalt chloride (4b-e) and the related 5,10,15,20-tetra(p-nitro)phenylporphyrin cobalt chloride (4f) are presented and their reactivity toward propylene oxide (PO)/CO 2 coupling/copolymerization is explored. While the nitro-substituted complex (4f), in conjunction with an onium salt, shows moderate activity toward cyclization, the 4b-e/onium systems show superior copolymerization activity in comparison to tetraphenylporphyrin Co(III) chloride (4a) with high selectivity and conversion to poly(propylene carbonate) (PPC). A comprehensive copolymerization behavior study of the alkoxy-substituted porphyrin complexes 4b-e in terms of reaction temperature and CO 2 pressure is presented. Complexes bearing longer alkoxy-substituents demonstrate the highest polymerization activity and molecular weights, however all substituted catalyst systems display a reduced tolerance to increased temperature with respect to PPC formation. Studies of the resulting polymer microstructures show excellent head-to-tail epoxide incorporation and near perfectly alternating poly(carbonate) character at lower polymerization temperatures. © 2012 American Chemical Society.

  4. Cobaltoporphyrin-Catalyzed CO 2 /Epoxide Copolymerization: Selectivity Control by Molecular Design

    KAUST Repository

    Anderson, Carly E.

    2012-09-11

    A series of cobalt(III) chloride porphyrin complexes of the general formula 5,10,15,20-tetra(p-alkoxy)phenylporphyrin cobalt chloride (4b-e) and the related 5,10,15,20-tetra(p-nitro)phenylporphyrin cobalt chloride (4f) are presented and their reactivity toward propylene oxide (PO)/CO 2 coupling/copolymerization is explored. While the nitro-substituted complex (4f), in conjunction with an onium salt, shows moderate activity toward cyclization, the 4b-e/onium systems show superior copolymerization activity in comparison to tetraphenylporphyrin Co(III) chloride (4a) with high selectivity and conversion to poly(propylene carbonate) (PPC). A comprehensive copolymerization behavior study of the alkoxy-substituted porphyrin complexes 4b-e in terms of reaction temperature and CO 2 pressure is presented. Complexes bearing longer alkoxy-substituents demonstrate the highest polymerization activity and molecular weights, however all substituted catalyst systems display a reduced tolerance to increased temperature with respect to PPC formation. Studies of the resulting polymer microstructures show excellent head-to-tail epoxide incorporation and near perfectly alternating poly(carbonate) character at lower polymerization temperatures. © 2012 American Chemical Society.

  5. Large-scale theoretical calculations in molecular science - design of a large computer system for molecular science and necessary conditions for future computers

    Energy Technology Data Exchange (ETDEWEB)

    Kashiwagi, H [Institute for Molecular Science, Okazaki, Aichi (Japan)

    1982-06-01

    A large computer system was designed and established for molecular science under the leadership of molecular scientists. Features of the computer system are an automated operation system and an open self-service system. Large-scale theoretical calculations have been performed to solve many problems in molecular science, using the computer system. Necessary conditions for future computers are discussed on the basis of this experience.

  6. Large-scale theoretical calculations in molecular science - design of a large computer system for molecular science and necessary conditions for future computers

    International Nuclear Information System (INIS)

    Kashiwagi, H.

    1982-01-01

    A large computer system was designed and established for molecular science under the leadership of molecular scientists. Features of the computer system are an automated operation system and an open self-service system. Large-scale theoretical calculations have been performed to solve many problems in molecular science, using the computer system. Necessary conditions for future computers are discussed on the basis of this experience. (orig.)

  7. Walkable new urban LEED_Neighborhood-Development (LEED-ND community design and children's physical activity: selection, environmental, or catalyst effects?

    Directory of Open Access Journals (Sweden)

    Stevens, Robert B

    2011-12-01

    Full Text Available Abstract Background Interest is growing in physical activity-friendly community designs, but few tests exist of communities explicitly designed to be walkable. We test whether students living in a new urbanist community that is also a pilot LEED_ND (Leadership in Energy and Environmental Design-Neighborhood Development community have greater accelerometer-measured moderate-to-vigorous physical activity (MVPA across particular time periods compared to students from other communities. We test various time/place periods to see if the data best conform to one of three explanations for MVPA. Environmental effects suggest that MVPA occurs when individuals are exposed to activity-friendly settings; selection effects suggest that walkable community residents prefer MVPA, which leads to both their choice of a walkable community and their high levels of MVPA; catalyst effects occur when walking to school creates more MVPA, beyond the school commute, on schooldays but not weekends. Methods Fifth graders (n = 187 were sampled from two schools representing three communities: (1 a walkable community, Daybreak, designed with new urbanist and LEED-ND pilot design standards; (2 a mixed community (where students lived in a less walkable community but attended the walkable school so that part of the route to school was walkable, and (3 a less walkable community. Selection threats were addressed through controlling for parental preferences for their child to walk to school as well as comparing in-school MVPA for the walkable and mixed groups. Results Minutes of MVPA were tested with 3 × 2 (Community by Gender analyses of covariance (ANCOVAs. Community walkability related to more MVPA during the half hour before and after school and, among boys only, more MVPA after school. Boys were more active than girls, except during the half hour after school. Students from the mixed and walkable communities--who attended the same school--had similar in-school MVPA levels, and

  8. Walkable new urban LEED_Neighborhood-Development (LEED-ND) community design and children's physical activity: selection, environmental, or catalyst effects?

    Science.gov (United States)

    2011-01-01

    Background Interest is growing in physical activity-friendly community designs, but few tests exist of communities explicitly designed to be walkable. We test whether students living in a new urbanist community that is also a pilot LEED_ND (Leadership in Energy and Environmental Design-Neighborhood Development) community have greater accelerometer-measured moderate-to-vigorous physical activity (MVPA) across particular time periods compared to students from other communities. We test various time/place periods to see if the data best conform to one of three explanations for MVPA. Environmental effects suggest that MVPA occurs when individuals are exposed to activity-friendly settings; selection effects suggest that walkable community residents prefer MVPA, which leads to both their choice of a walkable community and their high levels of MVPA; catalyst effects occur when walking to school creates more MVPA, beyond the school commute, on schooldays but not weekends. Methods Fifth graders (n = 187) were sampled from two schools representing three communities: (1) a walkable community, Daybreak, designed with new urbanist and LEED-ND pilot design standards; (2) a mixed community (where students lived in a less walkable community but attended the walkable school so that part of the route to school was walkable), and (3) a less walkable community. Selection threats were addressed through controlling for parental preferences for their child to walk to school as well as comparing in-school MVPA for the walkable and mixed groups. Results Minutes of MVPA were tested with 3 × 2 (Community by Gender) analyses of covariance (ANCOVAs). Community walkability related to more MVPA during the half hour before and after school and, among boys only, more MVPA after school. Boys were more active than girls, except during the half hour after school. Students from the mixed and walkable communities--who attended the same school--had similar in-school MVPA levels, and community groups

  9. Molecular Cloning Designer Simulator (MCDS: All-in-one molecular cloning and genetic engineering design, simulation and management software for complex synthetic biology and metabolic engineering projects

    Directory of Open Access Journals (Sweden)

    Zhenyu Shi

    2016-12-01

    Full Text Available Molecular Cloning Designer Simulator (MCDS is a powerful new all-in-one cloning and genetic engineering design, simulation and management software platform developed for complex synthetic biology and metabolic engineering projects. In addition to standard functions, it has a number of features that are either unique, or are not found in combination in any one software package: (1 it has a novel interactive flow-chart user interface for complex multi-step processes, allowing an integrated overview of the whole project; (2 it can perform a user-defined workflow of cloning steps in a single execution of the software; (3 it can handle multiple types of genetic recombineering, a technique that is rapidly replacing classical cloning for many applications; (4 it includes experimental information to conveniently guide wet lab work; and (5 it can store results and comments to allow the tracking and management of the whole project in one platform. MCDS is freely available from https://mcds.codeplex.com. Keywords: BioCAD, Genetic engineering software, Molecular cloning software, Synthetic biology, Workflow simulation and management

  10. Characterization-Based Molecular Design of Bio-Fuel Additives Using Chemometric and Property Clustering Techniques

    International Nuclear Information System (INIS)

    Hada, Subin; Solvason, Charles C.; Eden, Mario R.

    2014-01-01

    In this work, multivariate characterization data such as infrared spectroscopy was used as a source of descriptor data involving information on molecular architecture for designing structured molecules with tailored properties. Application of multivariate statistical techniques such as principal component analysis allowed capturing important features of the molecular architecture from enormous amount of complex data to build appropriate latent variable models. Combining the property clustering techniques and group contribution methods based on characterization (cGCM) data in a reverse problem formulation enabled identifying candidate components by combining or mixing molecular fragments until the resulting properties match the targets. The developed methodology is demonstrated using molecular design of biodiesel additive, which when mixed with off-spec biodiesel produces biodiesel that meets the desired fuel specifications. The contribution of this work is that the complex structures and orientations of the molecule can be included in the design, thereby allowing enumeration of all feasible candidate molecules that matched the identified target but were not part of original training set of molecules.

  11. Characterization-Based Molecular Design of Bio-Fuel Additives Using Chemometric and Property Clustering Techniques

    Energy Technology Data Exchange (ETDEWEB)

    Hada, Subin; Solvason, Charles C.; Eden, Mario R., E-mail: edenmar@auburn.edu [Department of Chemical Engineering, Auburn University, Auburn, AL (United States)

    2014-06-10

    In this work, multivariate characterization data such as infrared spectroscopy was used as a source of descriptor data involving information on molecular architecture for designing structured molecules with tailored properties. Application of multivariate statistical techniques such as principal component analysis allowed capturing important features of the molecular architecture from enormous amount of complex data to build appropriate latent variable models. Combining the property clustering techniques and group contribution methods based on characterization (cGCM) data in a reverse problem formulation enabled identifying candidate components by combining or mixing molecular fragments until the resulting properties match the targets. The developed methodology is demonstrated using molecular design of biodiesel additive, which when mixed with off-spec biodiesel produces biodiesel that meets the desired fuel specifications. The contribution of this work is that the complex structures and orientations of the molecule can be included in the design, thereby allowing enumeration of all feasible candidate molecules that matched the identified target but were not part of original training set of molecules.

  12. Characterization-Based Molecular Design of Biofuel Additives Using Chemometric and Property Clustering Techniques

    Directory of Open Access Journals (Sweden)

    Subin eHada

    2014-06-01

    Full Text Available In this work, multivariate characterization data such as infrared (IR spectroscopy was used as a source of descriptor data involving information on molecular architecture for designing structured molecules with tailored properties. Application of multivariate statistical techniques such as principal component analysis (PCA allowed capturing important features of the molecular architecture from complex data to build appropriate latent variable models. Combining the property clustering techniques and group contribution methods (GCM based on characterization data in a reverse problem formulation enabled identifying candidate components by combining or mixing molecular fragments until the resulting properties match the targets. The developed methodology is demonstrated using molecular design of biodiesel additive which when mixed with off-spec biodiesel produces biodiesel that meets the desired fuel specifications. The contribution of this work is that the complex structures and orientations of the molecule can be included in the design, thereby allowing enumeration of all feasible candidate molecules that matched the identified target but were not part of original training set of molecules.

  13. Photosystem Inspired Peptide Hybrid Catalysts

    Science.gov (United States)

    2017-06-07

    materials defined at the molecular level. We propose a novel way to make hybrid catalyst composed of inorganic nanomaterials and peptides. The...Distribution approved for public release. AF Office Of Scientific Research (AFOSR)/ IOA Arlington, Virginia 22203 Air Force Research Laboratory Air...ORGANIZATION NAME(S) AND ADDRESS(ES) SEOUL NATIONAL UNIVERSITY SNUR&DB FOUNDATION RESEARCH PARK CENTER SEOUL, 151742 KR 8. PERFORMING ORGANIZATION REPORT

  14. Preliminary Design of Molecular Sieve for Removing Organic Iodide in Containment Filtered Venting System

    Energy Technology Data Exchange (ETDEWEB)

    Park, Tong Kyu; Shin, So Eun; Lee, Byung Chul [Heungdeok IT Valley Bldg., Yongin (Korea, Republic of); Kim, Hong Hyun; Lee, Kyung Jun [Gemvax and KAEL Inc., Daejeon (Korea, Republic of)

    2014-05-15

    In this paper, to increase the DF for gaseous iodine species, especially organic iodide, molecular sieve filled by silver exchanged zeolites is proposed and designed preliminarily. Its aerodynamic analysis is also performed and presented. In order to increase the DF for gaseous organic iodide, deep-bed type molecular sieve was proposed and designed preliminarily. Total 1,620kg of silver exchanged zeolites were filled evenly in 10 beds of the molecular sieve. The safety factor in the case of 20m{sup 3}/s will be smaller than the counterpart of the standard case (6m{sup 3}/s). However, if the adsorption capacity of the zeolites is larger than 3.09mg/g when the residence time is 0.09 second, the designed molecular sieve can be used at 20m3/s of volumetric flow rate. The removal efficiency for organic iodide should be considered as well as economical aspects in the design of molecular sieve. In the event of nuclear power plant (NPP) severe accident, the nuclear reactor containment might suffer damage resulting from overpressure caused by decay heat. In order to prevent this containment damage, containment venting has been considered as one of effective methods. However, since vented gases contain radioactive fission products, they should be filtered to be released to environment. Generally, containment filtered venting system (CFVS) is installed on NPP to achieve this aim. Even though great amount of efforts have been devoted to developing the CFVS using various filtering methods, the decontaminant factor (DF) for radioactive gaseous iodide is still unsatisfactory while DFs for radioactive aerosols and elemental iodine are very high.

  15. Methods of producing epoxides from alkenes using a two-component catalyst system

    Science.gov (United States)

    Kung, Mayfair C.; Kung, Harold H.; Jiang, Jian

    2013-07-09

    Methods for the epoxidation of alkenes are provided. The methods include the steps of exposing the alkene to a two-component catalyst system in an aqueous solution in the presence of carbon monoxide and molecular oxygen under conditions in which the alkene is epoxidized. The two-component catalyst system comprises a first catalyst that generates peroxides or peroxy intermediates during oxidation of CO with molecular oxygen and a second catalyst that catalyzes the epoxidation of the alkene using the peroxides or peroxy intermediates. A catalyst system composed of particles of suspended gold and titanium silicalite is one example of a suitable two-component catalyst system.

  16. Synthesis and physicochemical properties of Zr-MCM-41 mesoporous molecular sieves and Pt/H3PW12O40/Zr-MCM-41 catalysts

    International Nuclear Information System (INIS)

    Chen, L.F.; Wang, J.A.; Norena, L.E.; Aguilar, J.; Navarrete, J.; Salas, P.; Montoya, J.A.; Del Angel, P.

    2007-01-01

    For the first time, modifications of the surface and framework of Si-MCM-41 by depositing a heteropolyacid on the surface and by introducing foreign Zr 4+ ions into the framework are investigated. The Zr-modified Si-MCM-41 mesoporous materials (hereafter referred as WSZn, n=Si/Zr=25, 15, 8, 4) were synthesized through a surfactant-templated preparation approach, using low-cost fumed silica as the Si precursor. After impregnation with 25 wt% of H 3 PW 12 O 40 , the surface Broensted acidity of the Pt/H 3 PW 12 O 40 /WSZn catalysts was greatly enhanced by 2-10 times relative to the bare WSZn support. Two kinds of supported heteropolyacids were formed: (i) bulk-like heteropolyacid crystals with unchanged Keggin structures, and (ii) highly dispersed heteropolyacid with distorted Keggin units. The formation of various kinds of heteropolyacid structures is closely related to the interaction between the heteropolyanions and the hydroxyl groups in the host support. - Graphical abstract: Modifications of the surface and framework of Si-MCM-41 by depositing a heteropolyacid on the surface and by introducing foreign Zr 4+ ions into the framework are investigated. Broensted acidity of the Pt/H 3 PW 12 O 40 /Zr-MCM-41 catalysts was greatly enhanced by 2-10 times relative to the bare Zr-MCM-41 support

  17. Manganese oxide octahedral molecular sieve K-OMS-2 as catalyst in post plasma-catalysis for trichloroethylene degradation in humid air.

    Science.gov (United States)

    Nguyen Dinh, M T; Giraudon, J-M; Vandenbroucke, A M; Morent, R; De Geyter, N; Lamonier, J-F

    2016-08-15

    The total oxidation of trichloroethylene (TCE) in air at low relative humidity (RH=10%) in the presence of CO2 (520ppmv) was investigated in function of energy density using an atmospheric pressure negative DC luminescent glow discharge combined with a cryptomelane catalyst positioned downstream of the plasma reactor at a temperature of 150°C. When using Non-Thermal Plasma (NTP) alone, it is found a low COx (x=1-2) yield in agreement with the detection of gaseous polychlorinated by-products in the outlet stream as well as ozone which is an harmful pollutant. Introduction of cryptomelane enhanced trichloroethylene removal, totally inhibited plasma ozone formation and increased significantly the COx yield. The improved performances of the hybrid system were mainly ascribed to the total destruction of plasma generated ozone on cryptomelane surface to produce active oxygen species. Consequently these active oxygen species greatly enhanced the abatement of the plasma non-reacted TCE and completely destroyed the hazardous plasma generated polychlorinated intermediates. The facile redox of Mn species associated with oxygen vacancies and mobility as well as the textural properties of the catalyst might also contribute as a whole to the efficiency of the process. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Designing Efficient Solar-Driven Hydrogen Evolution Photocathodes Using Semitransparent MoQxCly(Q = S, Se) Catalysts on Si Micropyramids

    KAUST Repository

    Ding, Qi

    2015-09-21

    © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Silicon micropyramids with n+pp+ junctions are demonstrated to be efficient absorbers for integrated solar-driven hydrogen production systems enabling significant improvements in both photocurrent and onset potential. When conformally coated with MoSxCly, a catalyst that has excellent catalytic activity and high optical transparency, the highest photocurrent density for Si-based photocathodes with earth-abundant catalysts is achieved.

  19. Application of computational methods to the design and characterisation of porous molecular materials.

    Science.gov (United States)

    Evans, Jack D; Jelfs, Kim E; Day, Graeme M; Doonan, Christian J

    2017-06-06

    Composed from discrete units, porous molecular materials (PMMs) possess unique properties not observed for conventional, extended, solids, such as solution processibility and permanent porosity in the liquid phase. However, identifying the origin of porosity is not a trivial process, especially for amorphous or liquid phases. Furthermore, the assembly of molecular components is typically governed by a subtle balance of weak intermolecular forces that makes structure prediction challenging. Accordingly, in this review we canvass the crucial role of molecular simulations in the characterisation and design of PMMs. We will outline strategies for modelling porosity in crystalline, amorphous and liquid phases and also describe the state-of-the-art methods used for high-throughput screening of large datasets to identify materials that exhibit novel performance characteristics.

  20. Molecular design of highly efficient extractants for separation of lanthanides and actinides by computational chemistry

    International Nuclear Information System (INIS)

    Uezu, Kazuya; Yamagawa, Jun-ichiro; Goto, Masahiro

    2006-01-01

    Novel organophosphorus extractants, which have two functional moieties in the molecular structure, were developed for the recycle system of transuranium elements using liquid-liquid extraction. The synthesized extractants showed extremely high extractability to lanthanides elements compared to those of commercially available extractants. The results of extraction equilibrium suggested that the structural effect of extractants is one of the key factors to enhance the selectivity and extractability in lanthanides extractions. Furthermore, molecular modeling was carried out to evaluate the extraction properties for extraction of lanthanides by the synthesized extractants. Molecular modeling was shown to be very useful for designing new extractants. The new concept to connect some functional moieties with a spacer is very useful and is a promising method to develop novel extractants for treatment of nuclear fuel. (author)

  1. Design of hydroprocessing catalyst for the production of ultra clean fuels. Super clean nenryo wo mezashita jushitsu tanka suiso seisei shokubai no kokinoka

    Energy Technology Data Exchange (ETDEWEB)

    Shimada, Hiromichi (National Chemical Lab. for Industry,Tsukuba, (Japan))

    1990-02-01

    In order to develop high function catalyst for the ultra clean fuel refining and other purposes, the catalyst was studied in correlation between the function and structure. Hydrogenation power of aromatic ring and hydrogenolysis power of carbon-carbon bonding, which are principal functions of catalyst in the hydrogenation refining, were evaluated with model material. 30 kinds of catalyst were figure shown in classification result of evaluation. As for the mutual operation of molybdenum and carrier, it is necessary for molybdenum sulfide to be highly dispersed on carrier in order to heighten the hydrogenation activity. While the hydrogenolysis activity, as necessitating electrically negative molybdenum type to be formed on carrier, is manifested by the formation of Bronsted acidity point with hydrogen sulfide, adhering thereto. As for the molybdenum sulfide catalyst, mainly hydrogenation activity point, in case that structure, similar to molybdenum disulfide, is dispersed as a single layer on carrier, and hydrogenolysis activity point, in case that it forms a multi-layer structure thereon, are formed in edge part of respective crystal. The lowering in activity under a long time sevre condition, which mainly are carbonic material deposition, matallic adhesion, etc., is also influenced by the structural change in catalyst. 10 refs., 5 figs. 2 tabs.

  2. Reducing aquatic hazards of industrial chemicals: probabilistic assessment of sustainable molecular design guidelines.

    Science.gov (United States)

    Connors, Kristin A; Voutchkova-Kostal, Adelina M; Kostal, Jakub; Anastas, Paul; Zimmerman, Julie B; Brooks, Bryan W

    2014-08-01

    Basic toxicological information is lacking for the majority of industrial chemicals. In addition to increasing empirical toxicity data through additional testing, prospective computational approaches to drug development aim to serve as a rational basis for the design of chemicals with reduced toxicity. Recent work has resulted in the derivation of a "rule of 2," wherein chemicals with an octanol-water partition coefficient (log P) less than 2 and a difference between the lowest unoccupied molecular orbital and the highest occupied molecular orbital (ΔE) greater than 9 (log P9 eV) are predicted to be 4 to 5 times less likely to elicit acute or chronic toxicity to model aquatic organisms. The present study examines potential reduction of aquatic toxicity hazards from industrial chemicals if these 2 molecular design guidelines were employed. Probabilistic hazard assessment approaches were used to model the likelihood of encountering industrial chemicals exceeding toxicological categories of concern both with and without the rule of 2. Modeling predicted that utilization of these molecular design guidelines for log P and ΔE would appreciably decrease the number of chemicals that would be designated to be of "high" and "very high" concern for acute and chronic toxicity to standard model aquatic organisms and end points as defined by the US Environmental Protection Agency. For example, 14.5% of chemicals were categorized as having high and very high acute toxicity to the fathead minnow model, whereas only 3.3% of chemicals conforming to the design guidelines were predicted to be in these categories. Considerations of specific chemical classes (e.g., aldehydes), chemical attributes (e.g., ionization), and adverse outcome pathways in representative species (e.g., receptor-mediated responses) could be used to derive future property guidelines for broader classes of contaminants. © 2014 SETAC.

  3. Liquid-Phase Exfoliation of Phosphorene: Design Rules from Molecular Dynamics Simulations.

    Science.gov (United States)

    Sresht, Vishnu; Pádua, Agílio A H; Blankschtein, Daniel

    2015-08-25

    The liquid-phase exfoliation of phosphorene, the two-dimensional derivative of black phosphorus, in the solvents dimethyl sulfoxide (DMSO), dimethylformamide (DMF), isopropyl alcohol, N-methyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone is investigated using three molecular-scale "computer experiments". We modeled solvent-phosphorene interactions using an atomistic force field, based on ab initio calculations and lattice dynamics, that accurately reproduces experimental mechanical properties. We probed solvent molecule ordering at phosphorene/solvent interfaces and discovered that planar molecules such as N-methyl-2-pyrrolidone preferentially orient parallel to the interface. We subsequently measured the energy required to peel a single phosphorene monolayer from a stack of black phosphorus and analyzed the role of "wedges" of solvent molecules intercalating between phosphorene sheets in initiating exfoliation. The exfoliation efficacy of a solvent is enhanced when either molecular planarity "sharpens" this molecular wedge or strong phosphorene-solvent adhesion stabilizes the newly exposed phosphorene surfaces. Finally, we examined the colloidal stability of exfoliated flakes by simulating their aggregation and showed that dispersion is favored when the cohesive energy between the molecules in the solvent monolayer confined between the phosphorene sheets is high (as with DMSO) and is hindered when the adhesion between these molecules and phosphorene is strong; the molecular planarity in solvents like DMF enhances the cohesive energy. Our results are consistent with, and provide a molecular context for, experimental exfoliation studies of phosphorene and other layered solids, and our molecular insights into the significant role of solvent molecular geometry and ordering should complement prevalent solubility-parameter-based approaches in establishing design rules for effective nanomaterial exfoliation media.

  4. Monodisperse metal nanoparticle catalysts on silica mesoporous supports: synthesis, characterizations, and catalytic reactions

    Energy Technology Data Exchange (ETDEWEB)

    Somorjai, G.A.

    2009-09-14

    The design of high performance catalyst achieving near 100% product selectivity at maximum activity is one of the most important goals in the modern catalytic science research. To this end, the preparation of model catalysts whose catalytic performances can be predicted in a systematic and rational manner is of significant importance, which thereby allows understanding of the molecular ingredients affecting the catalytic performances. We have designed novel 3-dimensional (3D) high surface area model catalysts by the integration of colloidal metal nanoparticles and mesoporous silica supports. Monodisperse colloidal metal NPs with controllable size and shape were synthesized using dendrimers, polymers, or surfactants as the surface stabilizers. The size of Pt, and Rh nanoparticles can be varied from sub 1 nm to 15 nm, while the shape of Pt can be controlled to cube, cuboctahedron, and octahedron. The 3D model catalysts were generated by the incorporation of metal nanoparticles into the pores of mesoporous silica supports via two methods: capillary inclusion (CI) and nanoparticle encapsulation (NE). The former method relies on the sonication-induced inclusion of metal nanoparticles into the pores of mesoporous silica, whereas the latter is performed by the encapsulation of metal nanoparticles during the hydrothermal synthesis of mesoporous silica. The 3D model catalysts were comprehensively characterized by a variety of physical and chemical methods. These catalysts were found to show structure sensitivity in hydrocarbon conversion reactions. The Pt NPs supported on mesoporous SBA-15 silica (Pt/SBA-15) displayed significant particle size sensitivity in ethane hydrogenolysis over the size range of 1-7 nm. The Pt/SBA-15 catalysts also exhibited particle size dependent product selectivity in cyclohexene hydrogenation, crotonaldehyde hydrogenation, and pyrrole hydrogenation. The Rh loaded SBA-15 silica catalyst showed structure sensitivity in CO oxidation reaction. In

  5. Molecular design toward highly efficient photovoltaic polymers based on two-dimensional conjugated benzodithiophene.

    Science.gov (United States)

    Ye, Long; Zhang, Shaoqing; Huo, Lijun; Zhang, Maojie; Hou, Jianhui

    2014-05-20

    As researchers continue to develop new organic materials for solar cells, benzo[1,2-b:4,5-b']dithiophene (BDT)-based polymers have come to the fore. To improve the photovoltaic properties of BDT-based polymers, researchers have developed and applied various strategies leading to the successful molecular design of highly efficient photovoltaic polymers. Novel polymer materials composed of two-dimensional conjugated BDT (2D-conjugated BDT) have boosted the power conversion efficiency of polymer solar cells (PSCs) to levels that exceed 9%. In this Account, we summarize recent progress related to the design and synthesis of 2D-conjugated BDT-based polymers and discuss their applications in highly efficient photovoltaic devices. We introduce the basic considerations for the construction of 2D-conjugated BDT-based polymers and systematic molecular design guidelines. For example, simply modifying an alkoxyl-substituted BDT to form an alkylthienyl-substituted BDT can improve the polymer hole mobilities substantially with little effect on their molecular energy level. Secondly, the addition of a variety of chemical moieties to the polymer can produce a 2D-conjugated BDT unit with more functions. For example, the introduction of a conjugated side chain with electron deficient groups (such as para-alkyl-phenyl, meta-alkoxyl-phenyl, and 2-alkyl-3-fluoro-thienyl) allowed us to modulate the molecular energy levels of 2D-conjugated BDT-based polymers. Through the rational design of BDT analogues such as dithienobenzodithiophene (DTBDT) or the insertion of larger π bridges, we can tune the backbone conformations of these polymers and modulate their photovoltaic properties. We also discuss the influence of 2D-conjugated BDT on polymer morphology and the blends of these polymers with phenyl-C61 (or C71)-butyric acid methyl ester (PCBM). Finally, we summarize the various applications of the 2D-conjugated BDT-based polymers in highly efficient PSC devices. Overall, this Account

  6. From Computational Photobiology to the Design of Vibrationally Coherent Molecular Devices and Motors

    Science.gov (United States)

    Olivucci, Massimo

    2014-03-01

    In the past multi-configurational quantum chemical computations coupled with molecular mechanics force fields have been employed to investigate spectroscopic, thermal and photochemical properties of visual pigments. Here we show how the same computational technology can nowadays be used to design, characterize and ultimately, prepare light-driven molecular switches which mimics the photophysics of the visual pigment bovine rhodopsin (Rh). When embedded in the protein cavity the chromophore of Rh undergoes an ultrafast and coherent photoisomerization. In order to design a synthetic chromophore displaying similar properties in common solvents, we recently focused on indanylidene-pyrroline (NAIP) systems. We found that these systems display light-induced ground state coherent vibrational motion similar to the one detected in Rh. Semi-classical trajectories provide a mechanistic description of the structural changes associated to the observed coherent motion which is shown to be ultimately due to periodic changes in the π-conjugation.

  7. Drug design based on x-ray diffraction and steered molecular dynamics

    Czech Academy of Sciences Publication Activity Database

    Hašek, Jindřich; Skálová, Tereza; Dohnálek, Jan; Dušková, Jarmila; Petroková, Hana; Vondráčková, Eva; Zimmermann, K.

    2005-01-01

    Roč. 12, č. 3 (2005), s. 208-210 ISSN 1211-5894. [VUFB Conference on Modern Methods in Synthesis and Analysis of Active Pharmaceutical Substances /5./. Praha, 23.11.2005-24.11.2005] R&D Projects: GA AV ČR KJB4050312 Institutional research plan: CEZ:AV0Z40500505 Keywords : drug design * X-ray diffraction * steered molecular dynamics Subject RIV: CF - Physical ; Theoretical Chemistry

  8. Design, synthesis, conformational and molecular docking study of some novel acyl hydrazone based molecular hybrids as antimalarial and antimicrobial agents.

    Science.gov (United States)

    Kumar, Parvin; Kadyan, Kulbir; Duhan, Meenakshi; Sindhu, Jayant; Singh, Vineeta; Saharan, Baljeet Singh

    2017-11-14

    Acyl hydrazones are an important class of heterocyclic compounds promising pharmacological characteristics. Malaria is a life-threatening mosquito-borne blood disease caused by a plasmodium parasite. In some places, malaria can be treated and controlled with early diagnosis. However, some countries lack the resources to do this effectively. The present work involves the design and synthesis of some novel acyl hydrazone based molecular hybrids of 1,4-dihydropyridine and pyrazole (5a-g). These molecular hybrids were synthesised by condensation of 1,4-dihydropyridin-4-yl-phenoxyacetohydrazides with differently substituted pyrazole carbaldehyde. The final compound (5) showed two conformations (the major, E, s-cis and the minor, E, s-trans) as revealed by NMR spectral data and further supported by the energy calculations (MOPAC2016 using PM7 method). All the synthesised compounds were screened for their in vitro antimalarial activities against chloroquine-sensitive malaria parasite Plasmodium falciparum (3D7) and antimicrobial activity against Gram positive bacteria i.e. Bacillus cereus, Gram negative bacteria i.e. Escherichia coli and antifungal activity against one yeast i.e. Aspergillus niger. All these compounds were found more potent than chloroquine and clotrimazole, the standard drugs. In vitro antiplasmodial IC 50 value of the most potent compound 5d was found to be 4.40 nM which is even less than all the three reference drugs chloroquine (18.7 nM), pyrimethamine (11 nM) and artimisinin (6 nM). In silico binding study of compound 5d with plasmodial cysteine protease falcipain-2 indicated the inhibition of falcipain-2 as the probable reason for the antimalarial potency of compound 5d. All the compounds had shown good to excellent antimicrobial and antifungal activities.

  9. Molecular design for recombinant adeno-associated virus (rAAV) vector production.

    Science.gov (United States)

    Aponte-Ubillus, Juan Jose; Barajas, Daniel; Peltier, Joseph; Bardliving, Cameron; Shamlou, Parviz; Gold, Daniel

    2018-02-01

    Recombinant adeno-associated virus (rAAV) vectors are increasingly popular tools for gene therapy applications. Their non-pathogenic status, low inflammatory potential, availability of viral serotypes with different tissue tropisms, and prospective long-lasting gene expression are important attributes that make rAAVs safe and efficient therapeutic options. Over the last three decades, several groups have engineered recombinant AAV-producing platforms, yielding high titers of transducing vector particles. Current specific productivity yields from different platforms range from 10 3 to 10 5 vector genomes (vg) per cell, and there is an ongoing effort to improve vector yields in order to satisfy high product demands required for clinical trials and future commercialization.Crucial aspects of vector production include the molecular design of the rAAV-producing host cell line along with the design of AAV genes, promoters, and regulatory elements. Appropriately, configuring and balancing the expression of these elements not only contributes toward high productivity, it also improves process robustness and product quality. In this mini-review, the rational design of rAAV-producing expression systems is discussed, with special attention to molecular strategies that contribute to high-yielding, biomanufacturing-amenable rAAV production processes. Details on molecular optimization from four rAAV expression systems are covered: adenovirus, herpesvirus, and baculovirus complementation systems, as well as a recently explored yeast expression system.

  10. Molecular docking as a popular tool in drug design, an in silico travel

    Directory of Open Access Journals (Sweden)

    de Ruyck J

    2016-06-01

    Full Text Available Jerome de Ruyck, Guillaume Brysbaert, Ralf Blossey, Marc F Lensink University Lille, CNRS UMR8576 UGSF, Lille, FranceAbstract: New molecular modeling approaches, driven by rapidly improving computational platforms, have allowed many success stories for the use of computer-assisted drug design in the discovery of new mechanism- or structure-based drugs. In this overview, we highlight three aspects of the use of molecular docking. First, we discuss the combination of molecular and quantum mechanics to investigate an unusual enzymatic mechanism of a flavoprotein. Second, we present recent advances in anti-infectious agents' synthesis driven by structural insights. At the end, we focus on larger biological complexes made by protein–protein interactions and discuss their relevance in drug design. This review provides information on how these large systems, even in the presence of the solvent, can be investigated with the outlook of drug discovery.Keywords: structure-based drug design, protein–protein docking, quaternary structure prediction, residue interaction networks, RINs, water position

  11. Combining Rosetta with molecular dynamics (MD): A benchmark of the MD-based ensemble protein design.

    Science.gov (United States)

    Ludwiczak, Jan; Jarmula, Adam; Dunin-Horkawicz, Stanislaw

    2018-07-01

    Computational protein design is a set of procedures for computing amino acid sequences that will fold into a specified structure. Rosetta Design, a commonly used software for protein design, allows for the effective identification of sequences compatible with a given backbone structure, while molecular dynamics (MD) simulations can thoroughly sample near-native conformations. We benchmarked a procedure in which Rosetta design is started on MD-derived structural ensembles and showed that such a combined approach generates 20-30% more diverse sequences than currently available methods with only a slight increase in computation time. Importantly, the increase in diversity is achieved without a loss in the quality of the designed sequences assessed by their resemblance to natural sequences. We demonstrate that the MD-based procedure is also applicable to de novo design tasks started from backbone structures without any sequence information. In addition, we implemented a protocol that can be used to assess the stability of designed models and to select the best candidates for experimental validation. In sum our results demonstrate that the MD ensemble-based flexible backbone design can be a viable method for protein design, especially for tasks that require a large pool of diverse sequences. Copyright © 2018 Elsevier Inc. All rights reserved.

  12. A New Optimization Model for Computer-Aided Molecular Design Problems

    DEFF Research Database (Denmark)

    Zhang, Lei; Cignitti, Stefano; Gani, Rafiqul

    Computer-Aided Molecular Design (CAMD) is a method to design molecules with desired properties. That is, through CAMD, it is possible to generate molecules that match a specified set of target properties. CAMD has attracted much attention in recent years due to its ability to design novel as well...... with structure information considered due to the increased size of the mathematical problem and number of alternatives. Thus, decomposition-based approach is proposed to solve the problem. In this approach, only first-order groups are considered in the first step to obtain the building block of the designed...... molecule, then the property model is refined with second-order groups based on the results of the first step. However, this may result in the possibility of an optimal solution being excluded. Samudra and Sahinidis [4] used property relaxation method in the first step to avoid this situation...

  13. Designing an educative curriculum unit for teaching molecular geometry in high school chemistry

    Science.gov (United States)

    Makarious, Nader N.

    Chemistry is a highly abstract discipline that is taught and learned with the aid of various models. Among the most challenging, yet a fundamental topic in general chemistry at the high school level, is molecular geometry. This study focused on developing exemplary educative curriculum materials pertaining to the topic of molecular geometry. The methodology used in this study consisted of several steps. First, a diverse set of models were analyzed to determine to what extent each model serves its purpose in teaching molecular geometry. Second, a number of high school teachers and college chemistry professors were asked to share their experiences on using models in teaching molecular geometry through an online questionnaire. Third, findings from the comparative analysis of models, teachers’ experiences, literature review on models and students’ misconceptions, the curriculum expectations of the Next Generation Science Standards and their emphasis on three-dimensional learning and nature of science (NOS) contributed to the development of the molecular geometry unit. Fourth, the developed unit was reviewed by fellow teachers and doctoral-level science education experts and was revised to further improve its coherence and clarity in support of teaching and learning of the molecular geometry concepts. The produced educative curriculum materials focus on the scientific practice of developing and using models as promoted in the Next Generations Science Standards (NGSS) while also addressing nature of science (NOS) goals. The educative features of the newly developed unit support teachers’ pedagogical knowledge (PK) and pedagogical content knowledge (PCK). The unit includes an overview, teacher’s guide, and eight detailed lesson plans with inquiry oriented modeling activities replete with models and suggestions for teachers, as well as formative and summative assessment tasks. The unit design process serves as a model for redesigning other instructional units in

  14. Molecular Cloning Designer Simulator (MCDS): All-in-one molecular cloning and genetic engineering design, simulation and management software for complex synthetic biology and metabolic engineering projects.

    Science.gov (United States)

    Shi, Zhenyu; Vickers, Claudia E

    2016-12-01

    Molecular Cloning Designer Simulator (MCDS) is a powerful new all-in-one cloning and genetic engineering design, simulation and management software platform developed for complex synthetic biology and metabolic engineering projects. In addition to standard functions, it has a number of features that are either unique, or are not found in combination in any one software package: (1) it has a novel interactive flow-chart user interface for complex multi-step processes, allowing an integrated overview of the whole project; (2) it can perform a user-defined workflow of cloning steps in a single execution of the software; (3) it can handle multiple types of genetic recombineering, a technique that is rapidly replacing classical cloning for many applications; (4) it includes experimental information to conveniently guide wet lab work; and (5) it can store results and comments to allow the tracking and management of the whole project in one platform. MCDS is freely available from https://mcds.codeplex.com.

  15. A new decomposition-based computer-aided molecular/mixture design methodology for the design of optimal solvents and solvent mixtures

    DEFF Research Database (Denmark)

    Karunanithi, A.T.; Achenie, L.E.K.; Gani, Rafiqul

    2005-01-01

    This paper presents a novel computer-aided molecular/mixture design (CAMD) methodology for the design of optimal solvents and solvent mixtures. The molecular/mixture design problem is formulated as a mixed integer nonlinear programming (MINLP) model in which a performance objective is to be optim......This paper presents a novel computer-aided molecular/mixture design (CAMD) methodology for the design of optimal solvents and solvent mixtures. The molecular/mixture design problem is formulated as a mixed integer nonlinear programming (MINLP) model in which a performance objective...... is to be optimized subject to structural, property, and process constraints. The general molecular/mixture design problem is divided into two parts. For optimal single-compound design, the first part is solved. For mixture design, the single-compound design is first carried out to identify candidates...... and then the second part is solved to determine the optimal mixture. The decomposition of the CAMD MINLP model into relatively easy to solve subproblems is essentially a partitioning of the constraints from the original set. This approach is illustrated through two case studies. The first case study involves...

  16. VHDL-AMS Simulation Framework for Molecular-FET Device-to-Circuit Modeling and Design

    Directory of Open Access Journals (Sweden)

    Mariagrazia Graziano

    2018-01-01

    Full Text Available We concentrate on Molecular-FET as a device and present a new modular framework based on VHDL-AMS. We have implemented different Molecular-FET models within the framework. The framework allows comparison between the models in terms of the capability to calculate accurate I-V characteristics. It also provides the option to analyze the impact of Molecular-FET and its implementation in the circuit with the extension of its use in an architecture based on the crossbar configuration. This analysis evidences the effect of choices of technological parameters, the ability of models to capture the impact of physical quantities, and the importance of considering defects at circuit fabrication level. The comparison tackles the computational efforts of different models and techniques and discusses the trade-off between accuracy and performance as a function of the circuit analysis final requirements. We prove this methodology using three different models and test them on a 16-bit tree adder included in Pentium 4 that, to the best of our knowledge, is the biggest circuits based on molecular device ever designed and analyzed.

  17. Mechanistic and quantitative insight into cell surface targeted molecular imaging agent design.

    Science.gov (United States)

    Zhang, Liang; Bhatnagar, Sumit; Deschenes, Emily; Thurber, Greg M

    2016-05-05

    Molecular imaging agent design involves simultaneously optimizing multiple probe properties. While several desired characteristics are straightforward, including high affinity and low non-specific background signal, in practice there are quantitative trade-offs between these properties. These include plasma clearance, where fast clearance lowers background signal but can reduce target uptake, and binding, where high affinity compounds sometimes suffer from lower stability or increased non-specific interactions. Further complicating probe development, many of the optimal parameters vary depending on both target tissue and imaging agent properties, making empirical approaches or previous experience difficult to translate. Here, we focus on low molecular weight compounds targeting extracellular receptors, which have some of the highest contrast values for imaging agents. We use a mechanistic approach to provide a quantitative framework for weighing trade-offs between molecules. Our results show that specific target uptake is well-described by quantitative simulations for a variety of targeting agents, whereas non-specific background signal is more difficult to predict. Two in vitro experimental methods for estimating background signal in vivo are compared - non-specific cellular uptake and plasma protein binding. Together, these data provide a quantitative method to guide probe design and focus animal work for more cost-effective and time-efficient development of molecular imaging agents.

  18. Molecular Design of Antifouling Polymer Brushes Using Sequence-Specific Peptoids.

    Science.gov (United States)

    Lau, King Hang Aaron; Sileika, Tadas S; Park, Sung Hyun; Sousa, Ana Maria Leal; Burch, Patrick; Szleifer, Igal; Messersmith, Phillip B

    2015-01-07

    Material systems that can be used to flexibly and precisely define the chemical nature and molecular arrangement of a surface would be invaluable for the control of complex biointerfacial interactions. For example, progress in antifouling polymer biointerfaces that prevent non-specific protein adsorption and cell attachment, which can significantly improve the performance of an array of biomedical and industrial applications, is hampered by a lack of chemical models to identify the molecular features conferring their properties. Poly(N-substituted glycine) "peptoids" are peptidomimetic polymers that can be conveniently synthesized with specific monomer sequences and chain lengths, and are presented as a versatile platform for investigating the molecular design of antifouling polymer brushes. Zwitterionic antifouling polymer brushes have captured significant recent attention, and a targeted library of zwitterionic peptoid brushes with a different charge densities, hydration, separations between charged groups, chain lengths, and grafted chain densities, is quantitatively evaluated for their antifouling properties through a range of protein adsorption and cell attachment assays. Specific zwitterionic brush designs were found to give rise to distinct but subtle differences in properties. The results also point to the dominant roles of the grafted chain density and chain length in determining the performance of antifouling polymer brushes.

  19. Modern drug design: the implication of using artificial neuronal networks and multiple molecular dynamic simulations

    Science.gov (United States)

    Yakovenko, Oleksandr; Jones, Steven J. M.

    2018-01-01

    We report the implementation of molecular modeling approaches developed as a part of the 2016 Grand Challenge 2, the blinded competition of computer aided drug design technologies held by the D3R Drug Design Data Resource (https://drugdesigndata.org/). The challenge was focused on the ligands of the farnesoid X receptor (FXR), a highly flexible nuclear receptor of the cholesterol derivative chenodeoxycholic acid. FXR is considered an important therapeutic target for metabolic, inflammatory, bowel and obesity related diseases (Expert Opin Drug Metab Toxicol 4:523-532, 2015), but in the context of this competition it is also interesting due to the significant ligand-induced conformational changes displayed by the protein. To deal with these conformational changes we employed multiple simulations of molecular dynamics (MD). Our MD-based protocols were top-ranked in estimating the free energy of binding of the ligands and FXR protein. Our approach was ranked second in the prediction of the binding poses where we also combined MD with molecular docking and artificial neural networks. Our approach showed mediocre results for high-throughput scoring of interactions.

  20. Nanosheet Supported Single-Metal Atom Bifunctional Catalyst for Overall Water Splitting.

    Science.gov (United States)

    Ling, Chongyi; Shi, Li; Ouyang, Yixin; Zeng, Xiao Cheng; Wang, Jinlan

    2017-08-09

    Nanosheet supported single-atom catalysts (SACs) can make full use of metal atoms and yet entail high selectivity and activity, and bifunctional catalysts can enable higher performance while lowering the cost than two separate unifunctional catalysts. Supported single-atom bifunctional catalysts are therefore of great economic interest and scientific importance. Here, on the basis of first-principles computations, we report a design of the first single-atom bifunctional eletrocatalyst, namely, isolated nickel atom supported on β 12 boron monolayer (Ni 1 /β 12 -BM), to achieve overall water splitting. This nanosheet supported SAC exhibits remarkable electrocatalytic performance with the computed overpotential for oxygen/hydrogen evolution reaction being just 0.40/0.06 V. The ab initio molecular dynamics simulation shows that the SAC can survive up to 800 K elevated temperature, while enacting a high energy barrier of 1.68 eV to prevent isolated Ni atoms from clustering. A viable experimental route for the synthesis of Ni 1 /β 12 -BM SAC is demonstrated from computer simulation. The desired nanosheet supported single-atom bifunctional catalysts not only show great potential for achieving overall water splitting but also offer cost-effective opportunities for advancing clean energy technology.

  1. Sensitivity analysis of molecular design problem for the development of novel working fluids for power cycles

    DEFF Research Database (Denmark)

    Frutiger, Jerome; Abildskov, Jens; Sin, Gürkan

    . Multi-criteria database search and Computer Aided Molecular Design (CAMD) can be applied to generate, test and evaluate promising pure component/mixture candidate as process fluids to help optimize cycle design and performance [1]. The problem formulation for the development of novel working fluids...... a certain working fluid property parameter on the performance of the power cycle, i.e. the net power output, can facilitate the identification key properties for working fluids. In that sense a sensitivity analysis of the different parameters is suggested in this work as a systematic method to efficiently...... technology to convert such waste heat sources into usable energy. So far the low-temperature heat is not utilized efficiently for electricity generation. To optimize the heat transfer process and the power generation, the influence of the working fluid, the cycle designs and the operating conditions is vital...

  2. Experimental mixture design as a tool for the synthesis of antimicrobial selective molecularly imprinted monodisperse microbeads.

    Science.gov (United States)

    Benito-Peña, Elena; Navarro-Villoslada, Fernando; Carrasco, Sergio; Jockusch, Steffen; Ottaviani, M Francesca; Moreno-Bondi, Maria C

    2015-05-27

    The effect of the cross-linker on the shape and size of molecular imprinted polymer (MIP) beads prepared by precipitation polymerization has been evaluated using a chemometric approach. Molecularly imprinted microspheres for the selective recognition of fluoroquinolone antimicrobials were prepared in a one-step precipitation polymerization procedure using enrofloxacin (ENR) as the template molecule, methacrylic acid as functional monomer, 2-hydroxyethyl methacrylate as hydrophilic comonomer, and acetonitrile as the porogen. The type and amount of cross-linker, namely ethylene glycol dimethacrylate, divinylbenzene or trimethylolpropane trimethacrylate, to obtain monodispersed MIP spherical beads in the micrometer range was optimized using a simplex lattice design. Particle size and morphology were assessed by scanning electron microscopy, dynamic light scattering, and nitrogen adsorption measurements. Electron paramagnetic resonance spectroscopy in conjunction with a nitroxide as spin probe revealed information about the microviscosity and polarity of the binding sites in imprinted and nonimprinted polymer beads.

  3. Designing molecular complexes using free-energy derivatives from liquid-state integral equation theory

    International Nuclear Information System (INIS)

    Mrugalla, Florian; Kast, Stefan M

    2016-01-01

    Complex formation between molecules in solution is the key process by which molecular interactions are translated into functional systems. These processes are governed by the binding or free energy of association which depends on both direct molecular interactions and the solvation contribution. A design goal frequently addressed in pharmaceutical sciences is the optimization of chemical properties of the complex partners in the sense of minimizing their binding free energy with respect to a change in chemical structure. Here, we demonstrate that liquid-state theory in the form of the solute–solute equation of the reference interaction site model provides all necessary information for such a task with high efficiency. In particular, computing derivatives of the potential of mean force (PMF), which defines the free-energy surface of complex formation, with respect to potential parameters can be viewed as a means to define a direction in chemical space toward better binders. We illustrate the methodology in the benchmark case of alkali ion binding to the crown ether 18-crown-6 in aqueous solution. In order to examine the validity of the underlying solute–solute theory, we first compare PMFs computed by different approaches, including explicit free-energy molecular dynamics simulations as a reference. Predictions of an optimally binding ion radius based on free-energy derivatives are then shown to yield consistent results for different ion parameter sets and to compare well with earlier, orders-of-magnitude more costly explicit simulation results. This proof-of-principle study, therefore, demonstrates the potential of liquid-state theory for molecular design problems. (paper)

  4. A Molecular Cobalt Catalyst Architected and TiO2 Modified p-GaInP2 Photoelectrode for Hydrogen Production

    Energy Technology Data Exchange (ETDEWEB)

    Gu, Jing; Yan, Yong; Young, James; Steirer, Kenneth; Neale, Nathan R.; Turner, John A.

    2017-05-01

    We demonstrate that by employing a hybrid molecular/semiconductor interface with atomic layer deposited (ALD) TiO2 as an intermediate layer, a robust and corrosion resistant GaInP2-TiO2-cobaltoxime-TiO2 photocathode can be operated in alkaline media (pH =13).

  5. Nano-nitride cathode catalysts of Ti, Ta, and Nb for polymer electrolyte fuel cells: Temperature-programmed desorption investigation of molecularly adsorbed oxygen at low temperature

    KAUST Repository

    Ohnishi, Ryohji; Takanabe, Kazuhiro; Katayama, Masao; Kubota, Jun; Domen, Kazunari

    2013-01-01

    -programmed desorption (TPD) of molecularly adsorbed O2 at 120-170 K from these nanoparticles was examined, and the resulting amount and temperature of desorption were key factors determining the ORR activity. The size-dependent TiN nanoparticles (5-8 and 100 nm) were

  6. Support effects on adsorption and catalytic activation of O2 in single atom iron catalysts with graphene-based substrates.

    Science.gov (United States)

    Gao, Zheng-Yang; Yang, Wei-Jie; Ding, Xun-Lei; Lv, Gang; Yan, Wei-Ping

    2018-03-07

    The adsorption and catalytic activation of O 2 on single atom iron catalysts with graphene-based substrates were investigated systematically by density functional theory calculation. It is found that the support effects of graphene-based substrates have a significant influence on the stability of the single atom catalysts, the adsorption configuration, the electron transfer mechanism, the adsorption energy and the energy barrier. The differences in the stable adsorption configuration of O 2 on single atom iron catalysts with different graphene-based substrates can be well understood by the symmetrical matching principle based on frontier molecular orbital analysis. There are two different mechanisms of electron transfer, in which the Fe atom acts as the electron donor in single vacancy graphene-based substrates while the Fe atom mainly acts as the bridge for electron transfer in double vacancy graphene-based substrates. The Fermi softness and work function are good descriptors of the adsorption energy and they can well reveal the relationship between electronic structure and adsorption energy. This single atom iron catalyst with single vacancy graphene modified by three nitrogen atoms is a promising non-noble metal single atom catalyst in the adsorption and catalytic oxidation of O 2 . Furthermore, the findings can lay the foundation for the further study of graphene-based support effects and provide a guideline for the development and design of new non-noble-metal single atom catalysts.

  7. Enhanced gasification of wood in the presence of mixed catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Weber, S. L.; Mudge, L. K.; Sealock, Jr., L. J.; Robertus, R. J.; Mitchell, D. E.

    Experimental results obtained in laboratory investigations of steam gasification of wood in the presence of mixed catalysts are presented. These studies are designed to test the technical feasibility of producing specific gaseous products from wood by enhancing its reactivity and product specificity through the use of combined catalysts. The desired products include substitute natural gas, hydrocarbon synthesis gas and ammonia synthesis gas. The gasification reactions are controlled through the use of specific catalyst combinations and operating parameters. A primary alkali carbonate gasification catalyst impregnated into the wood combined with specific commercially available secondary catalysts produced the desired products. A yield of 50 vol % methane was obtained with a randomly mixed combination of a commercial nickel methanation catalyst and silica-alumina cracking catalyst at a weight ratio of 3:1 respectively. Steam gasification of wood in the presence of a commercial Si-Al cracking catalyst produced the desired hydrocarbon synthesis gas. Hydrogen-to-carbon monoxide ratios needed for Fischer-Tropsch synthesis of hydrocarbons were obtained with this catalyst system. A hydrogen-to-nitrogen ratio of 3:1 for ammonia synthesis gas was achieved with steam-air gasification of wood in the presence of catalysts. The most effective secondary catalyst system employed to produce the ammonia synthesis gas included two commercially prepared catalysts formulated to promote the water-gas shift reaction.

  8. Catalyst Architecture

    DEFF Research Database (Denmark)

    Kiib, Hans; Marling, Gitte; Hansen, Peter Mandal

    2014-01-01

    of a more inclusive urban life, and development of environments of cultural diversity and learning The exhibition takes us to some of the fastest growing metropolises on four continents: New York, Copenhagen Tokyo, and Rio de Janeiro. The projects in the exhibition all have a powerful, social narrative...... meaningful for everyone. The exhibited works are designed by SANAA, Diller Scofidio + Renfro, James Corner Field Operation, JBMC Arquitetura e Urbanismo, Atelier Bow-Wow, Ateliers Jean Nouvel, COBE, Transform, BIG, Topotek1, Superflex, and by visual artist Jane Maria Petersen....

  9. The Folding of de Novo Designed Protein DS119 via Molecular Dynamics Simulations

    Directory of Open Access Journals (Sweden)

    Moye Wang

    2016-04-01

    Full Text Available As they are not subjected to natural selection process, de novo designed proteins usually fold in a manner different from natural proteins. Recently, a de novo designed mini-protein DS119, with a βαβ motif and 36 amino acids, has folded unusually slowly in experiments, and transient dimers have been detected in the folding process. Here, by means of all-atom replica exchange molecular dynamics (REMD simulations, several comparably stable intermediate states were observed on the folding free-energy landscape of DS119. Conventional molecular dynamics (CMD simulations showed that when two unfolded DS119 proteins bound together, most binding sites of dimeric aggregates were located at the N-terminal segment, especially residues 5–10, which were supposed to form β-sheet with its own C-terminal segment. Furthermore, a large percentage of individual proteins in the dimeric aggregates adopted conformations similar to those in the intermediate states observed in REMD simulations. These results indicate that, during the folding process, DS119 can easily become trapped in intermediate states. Then, with diffusion, a transient dimer would be formed and stabilized with the binding interface located at N-terminals. This means that it could not quickly fold to the native structure. The complicated folding manner of DS119 implies the important influence of natural selection on protein-folding kinetics, and more improvement should be achieved in rational protein design.

  10. Catalytic Hydrogenation and Hydrodeoxygenation of Furfural over Pt(111): A Model System for the Rational Design and Operation of Practical Biomass Conversion Catalysts

    OpenAIRE

    Taylor, Martin J.; Jiang, Li; Reichert, Joachim; Papageorgiou, Anthoula C.; Beaumont, Simon K.; Wilson, Karen; Lee, Adam F.; Barth, Johannes V.; Kyriakou, Georgios

    2017-01-01

    Furfural is a key bioderived platform chemical whose reactivity under hydrogen atmospheres affords diverse chemical intermediates. Here, temperature-programmed reaction spectrometry and complementary scanning tunneling microscopy (STM) are employed to investigate furfural adsorption and reactivity over a Pt(111) model catalyst. Furfural decarbonylation to furan is highly sensitive to reaction conditions, in particular, surface crowding and associated changes in the adsorption geometry: furfur...

  11. The innovation catalysts.

    Science.gov (United States)

    Martin, Roger L

    2011-06-01

    A few years ago the software development company Intuit realized that it needed a new approach to galvanizing customers. The company's Net Promoter Score was faltering, and customer recommendations of new products were especially disappointing. Intuit decided to hold a two-day, off-site meeting for the company's top 300 managers with a focus on the role of design in innovation. One of the days was dedicated to a program called Design for Delight. The centerpiece of the day was a PowerPoint presentation by Intuit founder Scott Cook, who realized midway through that he was no Steve Jobs: The managers listened dutifully, but there was little energy in the room. By contrast, a subsequent exercise in which the participants worked through a design challenge by creating prototypes, getting feedback, iterating, and refining, had them mesmerized. The eventual result was the creation of a team of nine design-thinking coaches--"innovation catalysts"--from across Intuit who were made available to help any work group create prototypes, run experiments, and learn from customers. The process includes a "painstorm" (to determine the customer's greatest pain point), a "soljam" (to generate and then winnow possible solutions), and a "code-jam" (to write code "good enough" to take to customers within two weeks). Design for Delight has enabled employees throughout Intuit to move from satisfying customers to delighting them.

  12. Silica-supported (nBuCp)2ZrCl2: Effect of catalyst active center distribution on ethylene-1-hexene copolymerization

    KAUST Repository

    Atiqullah, Muhammad

    2013-08-12

    Metallocenes are a modern innovation in polyolefin catalysis research. Therefore, two supported metallocene catalysts-silica/MAO/(nBuCp)2ZrCl2 (Catalyst 1) and silica/nBuSnCl3/MAO/(nBuCp)2ZrCl2 (Catalyst 2), where MAO is methylaluminoxane-were synthesized, and subsequently used to prepare, without separate feeding of MAO, ethylene-1-hexene Copolymer 1 and Copolymer 2, respectively. Fouling-free copolymerization, catalyst kinetic stability and production of free-flowing polymer particles (replicating the catalyst particle size distribution) confirmed the occurrence of heterogeneous catalysis. The catalyst active center distribution was modeled by deconvoluting the measured molecular weight distribution and copolymer composition distribution. Five different active center types were predicted for each catalyst, which was corroborated by successive self-nucleation and annealing experiments, as well as by an extended X-ray absorption fine structure spectroscopy report published in the literature. Hence, metallocenes impregnated particularly on an MAO-pretreated support may be rightly envisioned to comprise an ensemble of isolated single sites that have varying coordination environments. This study shows how the active center distribution and the design of supported MAO anions affect copolymerization activity, polymerization mechanism and the resulting polymer microstructures. Catalyst 2 showed less copolymerization activity than Catalyst 1. Strong chain transfer and positive co-monomer effect-both by 1-hexene-were common. Each copolymer demonstrated vinyl, vinylidene and trans-vinylene end groups, and compositional heterogeneity. All these findings were explained, as appropriate, considering the modeled active center distribution, MAO cage structure repeat units, proposed catalyst surface chemistry, segregation effects and the literature that concerns and supports this study. While doing so, new insights were obtained. Additionally, future research, along the direction

  13. Silica-supported (nBuCp)2ZrCl2: Effect of catalyst active center distribution on ethylene-1-hexene copolymerization

    KAUST Repository

    Atiqullah, Muhammad; Anantawaraskul, Siripon; Emwas, Abdul-Hamid M.; Al-Harthi, Mamdouh Ahmed; Hussain, Ikram; Ul-Hamid, Anwar; Hossaen, Anwar

    2013-01-01

    Metallocenes are a modern innovation in polyolefin catalysis research. Therefore, two supported metallocene catalysts-silica/MAO/(nBuCp)2ZrCl2 (Catalyst 1) and silica/nBuSnCl3/MAO/(nBuCp)2ZrCl2 (Catalyst 2), where MAO is methylaluminoxane-were synthesized, and subsequently used to prepare, without separate feeding of MAO, ethylene-1-hexene Copolymer 1 and Copolymer 2, respectively. Fouling-free copolymerization, catalyst kinetic stability and production of free-flowing polymer particles (replicating the catalyst particle size distribution) confirmed the occurrence of heterogeneous catalysis. The catalyst active center distribution was modeled by deconvoluting the measured molecular weight distribution and copolymer composition distribution. Five different active center types were predicted for each catalyst, which was corroborated by successive self-nucleation and annealing experiments, as well as by an extended X-ray absorption fine structure spectroscopy report published in the literature. Hence, metallocenes impregnated particularly on an MAO-pretreated support may be rightly envisioned to comprise an ensemble of isolated single sites that have varying coordination environments. This study shows how the active center distribution and the design of supported MAO anions affect copolymerization activity, polymerization mechanism and the resulting polymer microstructures. Catalyst 2 showed less copolymerization activity than Catalyst 1. Strong chain transfer and positive co-monomer effect-both by 1-hexene-were common. Each copolymer demonstrated vinyl, vinylidene and trans-vinylene end groups, and compositional heterogeneity. All these findings were explained, as appropriate, considering the modeled active center distribution, MAO cage structure repeat units, proposed catalyst surface chemistry, segregation effects and the literature that concerns and supports this study. While doing so, new insights were obtained. Additionally, future research, along the direction

  14. Polypropylene obtained through zeolite supported catalysts

    International Nuclear Information System (INIS)

    Bastos, Queli C.; Marques, Maria de Fatima V.

    2004-01-01

    Propylene polymerizations were carried out with φ 2 C(Flu)(Cp)ZrCl 2 and SiMe 2 (Ind)2ZrCl 2 catalysts supported on silica, zeolite sodic mordenite (NaM) and acid mordenite (HM). The polymerizations were performed at different temperatures and varying aluminium/zirconium molar ratios ([Al]/[Zr]). The effect of these reaction parameters on the catalyst activity was investigated using a proposed statistical experimental planning. In the case of f 2 C(Flu)(Cp)ZrCl 2 , SiO 2 and NaM were used as support and the catalyst performance evaluated using toluene and pentane as polymerization solvent. The molecular weight, molecular weight distribution, melting point and crystallinity of the polymers were examined. The results indicate very high activities for the syndiospecific heterogeneous system. Also, the polymers obtained had superior Mw and stereo regularity. (author)

  15. Polypropylene obtained through zeolite supported catalysts

    Directory of Open Access Journals (Sweden)

    Queli C. Bastos

    2004-01-01

    Full Text Available Propylene polymerizations were carried out with f2C(Flu(CpZrCl2 and SiMe2(Ind2ZrCl2 catalysts supported on silica, zeolite sodic mordenite (NaM and acid mordenite (HM. The polymerizations were performed at different temperatures and varying aluminium/zirconium molar ratios ([Al]/[Zr]. The effect of these reaction parameters on the catalyst activity was investigated using a proposed statistical experimental planning. In the case of f2C(Flu(CpZrCl2, SiO2 and NaM were used as support and the catalyst performance evaluated using toluene and pentane as polymerization solvent. The molecular weight, molecular weight distribution, melting point and crystallinity of the polymers were examined. The results indicate very high activities for the syndiospecific heterogeneous system. Also, the polymers obtained had superior Mw and stereoregularity.

  16. Nano-design of quantum dot-based photocatalysts for hydrogen generation using advanced surface molecular chemistry

    KAUST Repository

    Yu, Weili; Noureldine, Dalal; Isimjan, Tayirjan T.; Lin, Bin; Del Gobbo, Silvano; Abulikemu, Mutalifu; Hedhili, Mohamed N.; Anjum, Dalaver H.; Takanabe, Kazuhiro

    2015-01-01

    Efficient photocatalytic hydrogen generation in a suspension system requires a sophisticated nano-device that combines a photon absorber with effective redox catalysts. This study demonstrates an innovative molecular linking strategy for fabricating photocatalytic materials that allow effective charge separation of excited carriers, followed by efficient hydrogen evolution. The method for the sequential replacement of ligands with appropriate molecules developed in this study tethers both quantum dots (QDs), as photosensitizers, and metal nanoparticles, as hydrogen evolution catalysts, to TiO2 surfaces in a controlled manner at the nano-level. Combining hydrophobic and hydrophilic interactions on the surface, CdSe-ZnS core-shell QDs and an Au-Pt alloy were attached to TiO2 without overlapping during the synthesis. The resultant nano-photocatalysts achieved substantially high-performance visible-light-driven photocatalysis for hydrogen evolution. All syntheses were conducted at room temperature and in ambient air, providing a promising route for fabricating visible-light-responsive photocatalysts.

  17. Design of a Comprehensive Biochemistry and Molecular Biology Experiment: Phase Variation Caused by Recombinational Regulation of Bacterial Gene Expression

    Science.gov (United States)

    Sheng, Xiumei; Xu, Shungao; Lu, Renyun; Isaac, Dadzie; Zhang, Xueyi; Zhang, Haifang; Wang, Huifang; Qiao, Zheng; Huang, Xinxiang

    2014-01-01

    Scientific experiments are indispensable parts of Biochemistry and Molecular Biology. In this study, a comprehensive Biochemistry and Molecular Biology experiment about "Salmonella enterica" serovar Typhi Flagellar phase variation has been designed. It consisted of three parts, namely, inducement of bacterial Flagellar phase variation,…

  18. Molecular design chemical structure generation from the properties of pure organic compounds

    CERN Document Server

    Horvath, AL

    1992-01-01

    This book is a systematic presentation of the methods that have been developed for the interpretation of molecular modeling to the design of new chemicals. The main feature of the compilation is the co-ordination of the various scientific disciplines required for the generation of new compounds. The five chapters deal with such areas as structure and properties of organic compounds, relationships between structure and properties, and models for structure generation. The subject is covered in sufficient depth to provide readers with the necessary background to understand the modeling

  19. MECHANISTIC STUDIES AND DESIGN OF HIGHLY ACTIVE CUPRATE CATALYSTS FOR THE DIRECT DECOMPOSITION AND SELECTIVE REDUCTION OF NITRIC OXIDE AND HYDROCARBONS TO NITROGEN FOR ABATEMENT OF STACK EMISSIONS

    Energy Technology Data Exchange (ETDEWEB)

    None

    1998-04-30

    A flow trough type catalytic reactor system was adequately modified for NO related catalytic and adsorption measurements, including the on-line connection of a digital chemiluminescent NO-NO{sub x} analyzer to the reactor outlet system. Moreover, we have largely completed the installation of an FTIR coupled catalytic system containing a HTEC cell for high temperature DRIFT studies. Three different barium cuprate samples, Ba{sub 2}CuO{sub 3}, BaCuO{sub 2}, and Ba{sub 2}Cu{sub 3}O{sub 5} were synthesized and characterized by powder XRD for catalytic tests. Prior to catalytic studies over these cuprates, a new, liquid indium based supported molten metal catalyst (In-SMMC) was tested in the reduction of NO by various reductants. In the presence of excess O{sub 2} and H{sub 2}O, the In-SMMC proved to be more active for the selective catalytic reduction (SCR) of NO to N{sub 2} by ethanol than most other catalysts. Using C{sub 1}-C{sub 3} alcohols as reductants, self sustained periodic oscillations observed in the NO{sub x} concentrations of reactor effluents indicated the first time that radical intermediates can be involved in the SCR of NO by alcohols. Further, In-SMMC is the only effective and water tolerant SCR catalyst reported thus far which contains SiO{sub 2} support. Thus, this novel catalyst opens up a promising new alternative for developing an effective and durable catalyst for NO{sub x} abatement in stack emission.

  20. Catalyst Architecture

    DEFF Research Database (Denmark)

    with the wealthy district of Ipanema. The project, which consists of several public programs, addresses the need to open up districts in Rio and create access and connections in the socially divided city across the formal and informal areas, of which the latter counts for more than half of the population in Rio...... that it is not the intention to bring a debate on economic or more general political topics, how interesting it might seem to be. Among others, the issue of gentrification is very relevant in connection with urban renewal of urban interventions. We are very well aware of that. We mention the problem especially in the cases...... the specific challenges facing Rio de Janeiro - a divided city with the formal city and its wealthy neighborhoods on one side and on the other, the many favelas, which are not included in the regulations and public practices of the formal city. Then the case studies of the projects Cantagalo Elevator, designed...

  1. Molecular design of light-responsive hydrogels, for in situ generation of fast and reversible valves for microfluidic applications

    NARCIS (Netherlands)

    Schiphorst, ter J.; Coleman, S.; Stumpel, J.E.; Ben Azouz, A.; Diamond, D.; Schenning, A.P.H.J.

    2015-01-01

    Reversible light-responsive hydrogel valves with response characteristics compatible for microfluidics have been obtained by optimization of molecular design of spiropyran photoswitches and gel composition. Self-protonating gel formulations were exploited, wherein acrylic acid was copolymerized in

  2. Unconventional, Chemically Stable, and Soluble Two-Dimensional Angular Polycyclic Aromatic Hydrocarbons: From Molecular Design to Device Applications

    KAUST Repository

    Zhang, Lei; Cao, Yang; Colella, Nicholas S.; Liang, Yong; Bredas, Jean-Luc; Houk, Kendall N.; Briseñ o, Alejandro L.

    2015-01-01

    , longer acenes, which could exhibit even better performance, are susceptible to oxidation, photodegradation, and, in solar cells which contain fullerenes, Diels-Alder reactions. This Account highlights recent advances in the molecular design of two

  3. One-Pot Process for Hydrodeoxygenation of Lignin to Alkanes Using Ru-Based Bimetallic and Bifunctional Catalysts Supported on Zeolite Y

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hongliang [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Ruan, Hao [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Feng, Maoqi [Chemistry & Chemical Engineering Division, Southwest Research Institute, San Antonio TX 78238 USA; Qin, Yuling [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Job, Heather [Pacific Northwest National Laboratory, 902 Battelle Blvd Richland WA 99354 USA; Luo, Langli [Environmental Molecular Sciences Laboratory, 3335 Q Ave Richland WA 99354 USA; Wang, Chongmin [Environmental Molecular Sciences Laboratory, 3335 Q Ave Richland WA 99354 USA; Engelhard, Mark H. [Environmental Molecular Sciences Laboratory, 3335 Q Ave Richland WA 99354 USA; Kuhn, Erik [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO. 80401 USA; Chen, Xiaowen [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO. 80401 USA; Tucker, Melvin P. [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO. 80401 USA; Yang, Bin [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA

    2017-03-16

    The synthesis of high-efficiency and low-cost multifunctional catalysts for hydrodeoxygenation (HDO) of waste lignin into advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low molecular weight gaseous side-products. Among all the prepared catalysts, Ru-Cu/HY showed the best HDO performance, giving the highest selectivity to hydrocarbon products. The improved catalytic performance of Ru-Cu/HY was probably due to the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all the bifunctional catalysts were proven to be superior over the combination catalysts of Ru/Al2O3 and HY zeolite, and this could be attributed to the “intimacy criterion”. The practical use of the designed catalysts would be promising in lignin valorization.

  4. A multiscale simulation technique for molecular electronics: design of a directed self-assembled molecular n-bit shift register memory device.

    Science.gov (United States)

    Lambropoulos, Nicholas A; Reimers, Jeffrey R; Crossley, Maxwell J; Hush, Noel S; Silverbrook, Kia

    2013-12-20

    A general method useful in molecular electronics design is developed that integrates modelling on the nano-scale (using quantum-chemical software) and on the micro-scale (using finite-element methods). It is applied to the design of an n-bit shift register memory that could conceivably be built using accessible technologies. To achieve this, the entire complex structure of the device would be built to atomic precision using feedback-controlled lithography to provide atomic-level control of silicon devices, controlled wet-chemical synthesis of molecular insulating pillars above the silicon, and controlled wet-chemical self-assembly of modular molecular devices to these pillars that connect to external metal electrodes (leads). The shift register consists of n connected cells that read data from an input electrode, pass it sequentially between the cells under the control of two external clock electrodes, and deliver it finally to an output device. The proposed cells are trimeric oligoporphyrin units whose internal states are manipulated to provide functionality, covalently connected to other cells via dipeptide linkages. Signals from the clock electrodes are conveyed by oligoporphyrin molecular wires, and μ-oxo porphyrin insulating columns are used as the supporting pillars. The developed multiscale modelling technique is applied to determine the characteristics of this molecular device, with in particular utilization of the inverted region for molecular electron-transfer processes shown to facilitate latching and control using exceptionally low energy costs per logic operation compared to standard CMOS shift register technology.

  5. A multiscale simulation technique for molecular electronics: design of a directed self-assembled molecular n-bit shift register memory device

    International Nuclear Information System (INIS)

    Lambropoulos, Nicholas A; Reimers, Jeffrey R; Crossley, Maxwell J; Hush, Noel S; Silverbrook, Kia

    2013-01-01

    A general method useful in molecular electronics design is developed that integrates modelling on the nano-scale (using quantum-chemical software) and on the micro-scale (using finite-element methods). It is applied to the design of an n-bit shift register memory that could conceivably be built using accessible technologies. To achieve this, the entire complex structure of the device would be built to atomic precision using feedback-controlled lithography to provide atomic-level control of silicon devices, controlled wet-chemical synthesis of molecular insulating pillars above the silicon, and controlled wet-chemical self-assembly of modular molecular devices to these pillars that connect to external metal electrodes (leads). The shift register consists of n connected cells that read data from an input electrode, pass it sequentially between the cells under the control of two external clock electrodes, and deliver it finally to an output device. The proposed cells are trimeric oligoporphyrin units whose internal states are manipulated to provide functionality, covalently connected to other cells via dipeptide linkages. Signals from the clock electrodes are conveyed by oligoporphyrin molecular wires, and μ-oxo porphyrin insulating columns are used as the supporting pillars. The developed multiscale modelling technique is applied to determine the characteristics of this molecular device, with in particular utilization of the inverted region for molecular electron-transfer processes shown to facilitate latching and control using exceptionally low energy costs per logic operation compared to standard CMOS shift register technology. (paper)

  6. A multiscale simulation technique for molecular electronics: design of a directed self-assembled molecular n-bit shift register memory device

    Science.gov (United States)

    Lambropoulos, Nicholas A.; Reimers, Jeffrey R.; Crossley, Maxwell J.; Hush, Noel S.; Silverbrook, Kia

    2013-12-01

    A general method useful in molecular electronics design is developed that integrates modelling on the nano-scale (using quantum-chemical software) and on the micro-scale (using finite-element methods). It is applied to the design of an n-bit shift register memory that could conceivably be built using accessible technologies. To achieve this, the entire complex structure of the device would be built to atomic precision using feedback-controlled lithography to provide atomic-level control of silicon devices, controlled wet-chemical synthesis of molecular insulating pillars above the silicon, and controlled wet-chemical self-assembly of modular molecular devices to these pillars that connect to external metal electrodes (leads). The shift register consists of n connected cells that read data from an input electrode, pass it sequentially between the cells under the control of two external clock electrodes, and deliver it finally to an output device. The proposed cells are trimeric oligoporphyrin units whose internal states are manipulated to provide functionality, covalently connected to other cells via dipeptide linkages. Signals from the clock electrodes are conveyed by oligoporphyrin molecular wires, and μ-oxo porphyrin insulating columns are used as the supporting pillars. The developed multiscale modelling technique is applied to determine the characteristics of this molecular device, with in particular utilization of the inverted region for molecular electron-transfer processes shown to facilitate latching and control using exceptionally low energy costs per logic operation compared to standard CMOS shift register technology.

  7. Heterogeneous Pd catalysts supported on silica matrices

    Czech Academy of Sciences Publication Activity Database

    Opanasenko, Maksym; Štěpnička, P.; Čejka, Jiří

    2014-01-01

    Roč. 4, č. 110 (2014), s. 65137-65162 ISSN 2046-2069 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : catalysts * molecular sieves * palladium Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.840, year: 2014

  8. Residualization Rates of Near Infrared Dyes for the Rational Design of Molecular Imaging Agents

    Science.gov (United States)

    Cilliers, Cornelius; Liao, Jianshan; Atangcho, Lydia; Thurber, Greg M.

    2016-01-01

    Purpose Near infrared (NIR) fluorescence imaging is widely used for tracking antibodies and biomolecules in vivo. Clinical and preclinical applications include intraoperative imaging, tracking therapeutics, and fluorescent labeling as a surrogate for subsequent radiolabeling. Despite their extensive use, one of the fundamental properties of NIR dyes, the residualization rate within cells following internalization, has not been systematically studied. This rate is required for the rational design of probes and proper interpretation of in vivo results. Procedures In this brief report, we measure the cellular residualization rate of eight commonly used dyes encompassing three core structures (cyanine, BODIPY, and oxazine/thiazine/carbopyronin). Results We identify residualizing (half-life > 24 hrs) and non-residualizing dyes (half-life < 24 hrs) in both the far red (~650-680 nm) and near infrared (~740-800 nm) regions. Conclusions This data will allow researchers to independently and rationally select the wavelength and residualizing nature of dyes for molecular imaging agent design. PMID:25869081

  9. Precise Design of Phosphorescent Molecular Butterflies with Tunable Photoinduced Structural Change and Dual Emission.

    Science.gov (United States)

    Zhou, Chenkun; Tian, Yu; Yuan, Zhao; Han, Mingu; Wang, Jamie; Zhu, Lei; Tameh, Maliheh Shaban; Huang, Chen; Ma, Biwu

    2015-08-10

    Photoinduced structural change (PSC) is a fundamental excited-state dynamic process in chemical and biological systems. However, precise control of PSC processes is very challenging, owing to the lack of guidelines for designing excited-state potential energy surfaces (PESs). A series of rationally designed butterfly-like phosphorescent binuclear platinum complexes that undergo controlled PSC by Pt-Pt distance shortening and exhibit tunable dual (greenish-blue and red) emission are herein reported. Based on the Bell-Evans-Polanyi principle, it is demonstrated how the energy barrier of the PSC, which can be described as a chemical-reaction-like process between the two energy minima on the first triplet excited-state PES, can be controlled by synthetic means. These results reveal a simple method to engineer the dual emission of molecular systems by manipulating PES to control PSC. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Molecular Design of Semiconducting Polymers for High-Performance Organic Electrochemical Transistors

    KAUST Repository

    Nielsen, Christian B.

    2016-07-22

    The organic electrochemical transistor (OECT), capable of transducing small ionic fluxes into electronic signals in an aqueous envi-ronment, is an ideal device to utilize in bioelectronic applications. Currently, most OECTs are fabricated with commercially availa-ble conducting poly(3,4-ethylenedioxythiophene) (PEDOT)-based suspensions and are therefore operated in depletion mode. Here, we present a series of semiconducting polymers designed to elucidate important structure-property guidelines required for accumulation mode OECT operation. We discuss key aspects relating to OECT performance such as ion and hole transport, elec-trochromic properties, operational voltage and stability. The demonstration of our molecular design strategy is the fabrication of accumulation mode OECTs that clearly outperform state-of-the-art PEDOT based devices, and show stability under aqueous oper-ation without the need for formulation additives and cross-linkers.

  11. Oxytetracycline recovery from aqueous media using computationally designed molecularly imprinted polymers.

    Science.gov (United States)

    Rodríguez-Dorado, Rosalía; Carro, Antonia M; Chianella, Iva; Karim, Kal; Concheiro, Angel; Lorenzo, Rosa A; Piletsky, Sergey; Alvarez-Lorenzo, Carmen

    2016-09-01

    Polymers for recovery/removal of the antimicrobial agent oxytetracycline (OTC) from aqueous media were developed with use of computational design and molecular imprinting. 2-Hydroxyethyl methacrylate, 2-acrylamide-2-methylpropane sulfonic acid (AMPS), and mixtures of the two were chosen according to their predicted affinity for OTC and evaluated as functional monomers in molecularly imprinted polymers and nonimprinted polymers. Two levels of AMPS were tested. After bulk polymerization, the polymers were crushed into particles (200-1000 μm). Pressurized liquid extraction was implemented for template removal with a low amount of methanol (less than 20 mL in each extraction) and a few extractions (12-18 for each polymer) in a short period (20 min per extraction). Particle size distribution, microporous structure, and capacity to rebind OTC from aqueous media were evaluated. Adsorption isotherms obtained from OTC solutions (30-110 mg L(-1)) revealed that the polymers prepared with AMPS had the highest affinity for OTC. The uptake capacity depended on the ionic strength as follows: purified water > saline solution (0.9 % NaCl) > seawater (3.5 % NaCl). Polymer particles containing AMPS as a functional monomer showed a remarkable ability to clean water contaminated with OTC. The usefulness of the stationary phase developed for molecularly imprinted solid-phase extraction was also demonstrated. Graphical Abstract Selection of functional monomers by molecular modeling renders polymer networks suitable for removal of pollutants from contaminated aqueous environments, under either dynamic or static conditions.

  12. Methods of making textured catalysts

    Science.gov (United States)

    Werpy, Todd [West Richland, WA; Frye, Jr., John G.; Wang, Yong [Richland, WA; Zacher, Alan H [Kennewick, WA

    2010-08-17

    A textured catalyst having a hydrothermally-stable support, a metal oxide and a catalyst component is described. Methods of conducting aqueous phase reactions that are catalyzed by a textured catalyst are also described. The invention also provides methods of making textured catalysts and methods of making chemical products using a textured catalyst.

  13. A distance-dependent metal-enhanced fluorescence sensing platform based on molecular beacon design.

    Science.gov (United States)

    Zhou, Zhenpeng; Huang, Hongduan; Chen, Yang; Liu, Feng; Huang, Cheng Zhi; Li, Na

    2014-02-15

    A new metal-enhanced fluorescence (MEF) based platform was developed on the basis of distance-dependent fluorescence quenching-enhancement effect, which combined the easiness of Ag-thiol chemistry with the MEF property of noble-metal structures as well as the molecular beacon design. For the given sized AgNPs, the fluorescence enhancement factor was found to increase with a d(6) dependency in agreement with fluorescence resonance energy transfer mechanism at shorter distance and decrease with a d(-3) dependency in agreement with plasmonic enhancement mechanism at longer distance between the fluorophore and the AgNP surface. As a proof of concept, the platform was demonstrated by a sensitive detection of mercuric ions, using thymine-containing molecular beacon to tune silver nanoparticle (AgNP)-enhanced fluorescence. Mercuric ions were detected via formation of a thymine-mercuric-thymine structure to open the hairpin, facilitating fluorescence recovery and AgNP enhancement to yield a limit of detection of 1 nM, which is well below the U.S. Environmental Protection Agency regulation of the Maximum Contaminant Level Goal (10nM) in drinking water. Since the AgNP functioned as not only a quencher to reduce the reagent blank signal but also an enhancement substrate to increase fluorescence of the open hairpin when target mercuric ions were present, the quenching-enhancement strategy can greatly improve the detection sensitivity and can in principle be a universal approach for various targets when combined with molecular beacon design. © 2013 Elsevier B.V. All rights reserved.

  14. Molecular interactions in biomineralized hydroxyapatite amino acid modified nanoclay: In silico design of bone biomaterials

    International Nuclear Information System (INIS)

    Katti, Dinesh R.; Sharma, Anurag; Ambre, Avinash H.; Katti, Kalpana S.

    2015-01-01

    A simulations driven approach to design of a novel biomaterial nanocomposite system is described in this study. Nanoclays modified with amino acids (OMMT) were used to mineralize hydroxyapatite (HAP), mimicking biomineralization. Representative models of organically modified montmorillonite clay (OMMT) and OMMT-hydroxyapatite (OMMT-HAP) were constructed using molecular dynamics and validated using X-ray Diffraction (XRD), Fourier Transforms Infrared (FTIR) spectroscopy and Transmission Electron Microscopy (TEM). Attractive interactions exist between Ca atoms of HAP and C=O group of aminovaleric acid, indicating chelate formation in OMMT-HAP. Interaction energy maps describe molecular interactions among different constituents and their quantitative contributions in the OMMT and OMMT-HAP systems at both parallel and perpendicular orientations. High attractive and high repulsive interactions were found between PO 4 3− and MMT clay as well as aminovaleric molecules in OMMT-HAP perpendicular and parallel models. Large non-bonded interactions in OMMT-HAP indicate influence of neighboring environment on PO 4 3− in in situ HAPclay. Extensive hydrogen bonds were observed between functional hydrogen atoms of modifier and MMT clay in OMMT-HAP as compared to OMMT. Thus, HAP interacts with clay through the aminovaleric acid. This computational study provides a framework for materials design and selection for biomaterials used in tissue engineering and other areas of regenerative medicine. - Highlights: • Representative models of a hybrid nanoclay-hydroxyapatite biomaterial are built. • Interaction energy maps are constructed using a molecular dynamics. • Quantitative interactions between the three components of the biomaterial are found. • The modeling and experimental approach provides insight into the complex nanomaterial

  15. Onboard functional and molecular imaging: A design investigation for robotic multipinhole SPECT

    International Nuclear Information System (INIS)

    Bowsher, James; Giles, William; Yin, Fang-Fang; Yan, Susu; Roper, Justin

    2014-01-01

    Purpose: Onboard imaging—currently performed primarily by x-ray transmission modalities—is essential in modern radiation therapy. As radiation therapy moves toward personalized medicine, molecular imaging, which views individual gene expression, may also be important onboard. Nuclear medicine methods, such as single photon emission computed tomography (SPECT), are premier modalities for molecular imaging. The purpose of this study is to investigate a robotic multipinhole approach to onboard SPECT. Methods: Computer-aided design (CAD) studies were performed to assess the feasibility of maneuvering a robotic SPECT system about a patient in position for radiation therapy. In order to obtain fast, high-quality SPECT images, a 49-pinhole SPECT camera was designed which provides high sensitivity to photons emitted from an imaging region of interest. This multipinhole system was investigated by computer-simulation studies. Seventeen hot spots 10 and 7 mm in diameter were placed in the breast region of a supine female phantom. Hot spot activity concentration was six times that of background. For the 49-pinhole camera and a reference, more conventional, broad field-of-view (FOV) SPECT system, projection data were computer simulated for 4-min scans and SPECT images were reconstructed. Hot-spot localization was evaluated using a nonprewhitening forced-choice numerical observer. Results: The CAD simulation studies found that robots could maneuver SPECT cameras about patients in position for radiation therapy. In the imaging studies, most hot spots were apparent in the 49-pinhole images. Average localization errors for 10-mm- and 7-mm-diameter hot spots were 0.4 and 1.7 mm, respectively, for the 49-pinhole system, and 3.1 and 5.7 mm, respectively, for the reference broad-FOV system. Conclusions: A robot could maneuver a multipinhole SPECT system about a patient in position for radiation therapy. The system could provide onboard functional and molecular imaging with 4-min

  16. Onboard functional and molecular imaging: A design investigation for robotic multipinhole SPECT

    Energy Technology Data Exchange (ETDEWEB)

    Bowsher, James, E-mail: james.bowsher@duke.edu; Giles, William; Yin, Fang-Fang [Department of Radiation Oncology, Duke University Medical Center, Durham, North Carolina 27710 and Medical Physics Graduate Program, Duke University, Durham, North Carolina 27710 (United States); Yan, Susu [Medical Physics Graduate Program, Duke University, Durham, North Carolina 27710 (United States); Roper, Justin [Department of Radiation Oncology, Duke University Medical Center, Durham, North Carolina 27710 (United States)

    2014-01-15

    Purpose: Onboard imaging—currently performed primarily by x-ray transmission modalities—is essential in modern radiation therapy. As radiation therapy moves toward personalized medicine, molecular imaging, which views individual gene expression, may also be important onboard. Nuclear medicine methods, such as single photon emission computed tomography (SPECT), are premier modalities for molecular imaging. The purpose of this study is to investigate a robotic multipinhole approach to onboard SPECT. Methods: Computer-aided design (CAD) studies were performed to assess the feasibility of maneuvering a robotic SPECT system about a patient in position for radiation therapy. In order to obtain fast, high-quality SPECT images, a 49-pinhole SPECT camera was designed which provides high sensitivity to photons emitted from an imaging region of interest. This multipinhole system was investigated by computer-simulation studies. Seventeen hot spots 10 and 7 mm in diameter were placed in the breast region of a supine female phantom. Hot spot activity concentration was six times that of background. For the 49-pinhole camera and a reference, more conventional, broad field-of-view (FOV) SPECT system, projection data were computer simulated for 4-min scans and SPECT images were reconstructed. Hot-spot localization was evaluated using a nonprewhitening forced-choice numerical observer. Results: The CAD simulation studies found that robots could maneuver SPECT cameras about patients in position for radiation therapy. In the imaging studies, most hot spots were apparent in the 49-pinhole images. Average localization errors for 10-mm- and 7-mm-diameter hot spots were 0.4 and 1.7 mm, respectively, for the 49-pinhole system, and 3.1 and 5.7 mm, respectively, for the reference broad-FOV system. Conclusions: A robot could maneuver a multipinhole SPECT system about a patient in position for radiation therapy. The system could provide onboard functional and molecular imaging with 4-min

  17. Computer-aided Molecular Design of Compounds Targeting Histone Modifying Enzymes

    Science.gov (United States)

    Andreoli, Federico; Del Rio, Alberto

    2015-01-01

    Growing evidences show that epigenetic mechanisms play crucial roles in the genesis and progression of many physiopathological processes. As a result, research in epigenetic grew at a fast pace in the last decade. In particular, the study of histone post-translational modifications encountered an extraordinary progression and many modifications have been characterized and associated to fundamental biological processes and pathological conditions. Histone modifications are the catalytic result of a large set of enzyme families that operate covalent modifications on specific residues at the histone tails. Taken together, these modifications elicit a complex and concerted processing that greatly contribute to the chromatin remodeling and may drive different pathological conditions, especially cancer. For this reason, several epigenetic targets are currently under validation for drug discovery purposes and different academic and industrial programs have been already launched to produce the first pre-clinical and clinical outcomes. In this scenario, computer-aided molecular design techniques are offering important tools, mainly as a consequence of the increasing structural information available for these targets. In this mini-review we will briefly discuss the most common types of known histone modifications and the corresponding operating enzymes by emphasizing the computer-aided molecular design approaches that can be of use to speed-up the efforts to generate new pharmaceutically relevant compounds. PMID:26082827

  18. Molecular Dynamics Driven Design of pH-Stabilized Mutants of MNEI, a Sweet Protein.

    Directory of Open Access Journals (Sweden)

    Serena Leone

    Full Text Available MNEI is a single chain derivative of monellin, a plant protein that can interact with the human sweet taste receptor, being therefore perceived as sweet. This unusual physiological activity makes MNEI a potential template for the design of new sugar replacers for the food and beverage industry. Unfortunately, applications of MNEI have been so far limited by its intrinsic sensitivity to some pH and temperature conditions, which could occur in industrial processes. Changes in physical parameters can, in fact, lead to irreversible protein denaturation, as well as aggregation and precipitation. It has been previously shown that the correlation between pH and stability in MNEI derives from the presence of a single glutamic residue in a hydrophobic pocket of the protein. We have used molecular dynamics to study the consequences, at the atomic level, of the protonation state of such residue and have identified the network of intramolecular interactions responsible for MNEI stability at acidic pH. Based on this information, we have designed a pH-independent, stabilized mutant of MNEI and confirmed its increased stability by both molecular modeling and experimental techniques.

  19. Molecular Dynamics Driven Design of pH-Stabilized Mutants of MNEI, a Sweet Protein.

    Science.gov (United States)

    Leone, Serena; Picone, Delia

    2016-01-01

    MNEI is a single chain derivative of monellin, a plant protein that can interact with the human sweet taste receptor, being therefore perceived as sweet. This unusual physiological activity makes MNEI a potential template for the design of new sugar replacers for the food and beverage industry. Unfortunately, applications of MNEI have been so far limited by its intrinsic sensitivity to some pH and temperature conditions, which could occur in industrial processes. Changes in physical parameters can, in fact, lead to irreversible protein denaturation, as well as aggregation and precipitation. It has been previously shown that the correlation between pH and stability in MNEI derives from the presence of a single glutamic residue in a hydrophobic pocket of the protein. We have used molecular dynamics to study the consequences, at the atomic level, of the protonation state of such residue and have identified the network of intramolecular interactions responsible for MNEI stability at acidic pH. Based on this information, we have designed a pH-independent, stabilized mutant of MNEI and confirmed its increased stability by both molecular modeling and experimental techniques.

  20. Rational computational design for the development of andrographolide molecularly imprinted polymer

    Science.gov (United States)

    Krishnan, Hemavathi; Islam, K. M. Shafiqul; Hamzah, Zainab; Ahmad, Mohd Noor

    2017-10-01

    Andrographolide is a popular medicinal compound derived from Andrographis Paniculata (AP). Molecularly Imprint Polymer (MIP) is a "Lock and Key" approach, where MIP is the lock and Andrographolide is the key which fits to the MIP lock by both physically and chemically. MIP will be used as selective extraction tool to enrich Andrographolide bioactive compound. Pre-polymerization step is crucial to design MIP. This work investigates molecular interactions and the Gibbs free binding energies on the development of MIP. The structure of Andrographolide (template) and functional monomers were drawn in HyperChem 8.0.10. A hybrid quantum chemical model was used with a few functional monomers. Possible conformations of template and functional monomer as 1:n (n < 4) were designed and simulated to geometrically optimize the complex to the lowest energy in gas phase. The Gibbs free binding energies of each conformation were calculated using semi-empirical PM3 simulation method. Results proved that functional monomers that contain carboxylic group shows higher binding energy compared to those with amine functional group. Itaconic acid (IA) chosen as the best functional monomer at optimum ratio (1:3) of template: monomer to prepare andrographolide MIP. This study demonstrates the importance of studying intermolecular interaction among template, functional monomer and template-monomer ratio in developing MIP.

  1. Effect of catalyst on melamine-formaldehyde organic aerogel

    International Nuclear Information System (INIS)

    Sun Zhipeng; Yang Xi; Fu Zhibing; Zhong Minglong; Wang Chaoyang; Ma Kangfu; Huang Xiaoli; Chang Lijuan

    2013-01-01

    A series of melamine-formaldehyde(MF) organic aerogel templates were prepared with different categories and concentration of catalyst. Their molecular structure, thermal stability and pore structure were tested by Fourier transform infrared spectroscopy, thermogravimetric analysis and nitrogen adsorption. It is indicated that the type and concentration of catalyst do not affect molecular structure and thermal stability of the MF organic aerogel template. The specific surface area and pore volume of the MF organic aerogel template using Na 2 CO 3 as catalyst are higher than those using NaOH, NaHCO 3 as catalyst. When the ratio of the concentration of melamine to that of catalyst is 500, the specific surface area is maximized. (authors)

  2. Understanding of catalysis on early transition metal oxide-based catalysts through exploration of surface structure and chemistry during catalysis using in-situ approaches

    Energy Technology Data Exchange (ETDEWEB)

    Tao, Franklin [Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering. Dept. of Chemistry

    2015-09-14

    Two main categories of heterogeneous catalysts are metal and metal oxide which catalyze 80% chemical reactions at solid-gas and solid-liquid interfaces. Metal oxide catalysts are much more complicated than metal catalysts. The reason is that the cations of the metal atoms could exhibit a few different oxidation states on surface of the same catalyst particle such as Co3O4 or change of their oxidation states under different reactive environments. For a metal catalyst, there is only one oxidation state typically. In addition, surface of a metal oxide can be terminated with multiple surface functionalities including O atoms with different binding configurations and OH group. For metal, only metal atoms are exposed typically. Obviously, the complication of surface chemistry and structure of a metal oxide makes studies of surface of an oxide catalyst very challenging. Due to the complication of surface of a meal oxide, the electronic and geometric structures of surface of a metal oxide and the exposed species have received enormous attention since oxide catalysts catalyze at least 1/3 chemical reactions in chemical and energy industries. Understanding of catalytic reactions on early transition metal oxide-based catalysts is fundamentally intriguing and of great practical interest in energy- and environment-related catalysis. Exploration of surface chemistry of oxide-based catalysts at molecular level during catalysis has remained challenging though it is critical in deeply understanding catalysis on oxide-based catalysts and developing oxide-based catalysts with high activity and selectivity. Thus, the overall objective of this project is to explore surface chemistry and structure of early transition metal oxide-based catalysts through in-situ characterization of surface of catalysts, measurements of catalytic performances, and then build an intrinsic correlation of surface chemistry and structure with their catalytic performances in a few

  3. Alloy catalyst material

    DEFF Research Database (Denmark)

    2014-01-01

    The present invention relates to a novel alloy catalyst material for use in the synthesis of hydrogen peroxide from oxygen and hydrogen, or from oxygen and water. The present invention also relates to a cathode and an electrochemical cell comprising the novel catalyst material, and the process use...... of the novel catalyst material for synthesising hydrogen peroxide from oxygen and hydrogen, or from oxygen and water....

  4. Metal catalysts fight back

    OpenAIRE

    George Marsh

    1998-01-01

    In recent years organometallic catalysts, especially metallocenes, have been a major focus of attention in terms of polymerisation chemistry. But the news earlier this year of a family of iron-based catalysts able to rival the effectiveness of both conventional and metallocene catalysts in the polymerisation of ethylene has excited the plastics industry. Because of the impact of this discovery and its potential as a route to lower-priced commodity plastics in the future, it may be useful at t...

  5. Design of Molecular Solar Cells via Feedback from Soft X-ray Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Himpsel, Franz J. [Univ. of Wisconsin, Madison, WI (United States)

    2015-06-12

    Spectroscopy with soft X-rays was used to develop new materials and novel designs for solar cells and artificial photosynthesis. In order to go beyond the widely-used trial-and-error approach of gradually improving a particular design, we started from the most general layout of a solar cell (or a photo-electrochemical device) and asked which classes of materials are promising for best performance. For example, the most general design of a solar cell consists of a light absorber, an electron donor, and an electron acceptor. These are characterized by four energy levels, which were measured by a combination of spectroscopic X-ray techniques. Tuning synchrotron radiation to the absorption edges of specific elements provided element- and bond-selectivity. The spectroscopic results were complemented by state-of-the-art calculations of the electronic states. These helped explaining the observed energy levels and the orbitals associated with them. The calculations were extended to a large class of materials (for example thousands of porphyrin dye complexes) in order to survey trends in the energy level structure. A few highlights serve as examples: 1) Organic molecules combining absorber, donor, and acceptor with atomic precision. 2) Exploration of highly p-doped diamond films as inert, transparent electron donors. 3) Surface-sensitive characterization of nanorod arrays used as photoanodes in water splitting. 4) Computational design of molecular complexes for efficient solar cells using two photons.

  6. Pharmacogenomics of the human ABC transporter ABCG2: from functional evaluation to drug molecular design

    Science.gov (United States)

    Ishikawa, Toshihisa; Tamura, Ai; Saito, Hikaru; Wakabayashi, Kanako; Nakagawa, Hiroshi

    2005-10-01

    In the post-genome-sequencing era, emerging genomic technologies are shifting the paradigm for drug discovery and development. Nevertheless, drug discovery and development still remain high-risk and high-stakes ventures with long and costly timelines. Indeed, the attrition of drug candidates in preclinical and development stages is a major problem in drug design. For at least 30% of the candidates, this attrition is due to poor pharmacokinetics and toxicity. Thus, pharmaceutical companies have begun to seriously re-evaluate their current strategies of drug discovery and development. In that light, we propose that a transport mechanism-based design might help to create new, pharmacokinetically advantageous drugs, and as such should be considered an important component of drug design strategy. Performing enzyme- and/or cell-based drug transporter, interaction tests may greatly facilitate drug development and allow the prediction of drug-drug interactions. We recently developed methods for high-speed functional screening and quantitative structure-activity relationship analysis to study the substrate specificity of ABC transporters and to evaluate the effect of genetic polymorphisms on their function. These methods would provide a practical tool to screen synthetic and natural compounds, and these data can be applied to the molecular design of new drugs. In this review article, we present an overview on the genetic polymorphisms of human ABC transporter ABCG2 and new camptothecin analogues that can circumvent AGCG2-associated multidrug resistance of cancer.

  7. Rational design of DNA sequences for nanotechnology, microarrays and molecular computers using Eulerian graphs.

    Science.gov (United States)

    Pancoska, Petr; Moravek, Zdenek; Moll, Ute M

    2004-01-01

    Nucleic acids are molecules of choice for both established and emerging nanoscale technologies. These technologies benefit from large functional densities of 'DNA processing elements' that can be readily manufactured. To achieve the desired functionality, polynucleotide sequences are currently designed by a process that involves tedious and laborious filtering of potential candidates against a series of requirements and parameters. Here, we present a complete novel methodology for the rapid rational design of large sets of DNA sequences. This method allows for the direct implementation of very complex and detailed requirements for the generated sequences, thus avoiding 'brute force' filtering. At the same time, these sequences have narrow distributions of melting temperatures. The molecular part of the design process can be done without computer assistance, using an efficient 'human engineering' approach by drawing a single blueprint graph that represents all generated sequences. Moreover, the method eliminates the necessity for extensive thermodynamic calculations. Melting temperature can be calculated only once (or not at all). In addition, the isostability of the sequences is independent of the selection of a particular set of thermodynamic parameters. Applications are presented for DNA sequence designs for microarrays, universal microarray zip sequences and electron transfer experiments.

  8. Hydroxide catalysts for lignin depolymerization

    Energy Technology Data Exchange (ETDEWEB)

    Beckham, Gregg T.; Biddy, Mary J.; Chmely, Stephen C.; Sturgeon, Matthew

    2017-04-25

    Solid base catalysts and their use for the base-catalyzed depolymerization (BCD) of lignin to compounds such as aromatics are presented herein. Exemplary catalysts include layered double hydroxides (LDHs) as recyclable, heterogeneous catalysts for BCD of lignin.

  9. Hydroxide catalysts for lignin depolymerization

    Science.gov (United States)

    Beckham, Gregg T; Biddy, Mary J.; Kruger, Jacob S.; Chmely, Stephen C.; Sturgeon, Matthew

    2017-10-17

    Solid base catalysts and their use for the base-catalyzed depolymerization (BCD) of lignin to compounds such as aromatics are presented herein. Exemplary catalysts include layered double hydroxides (LDHs) as recyclable, heterogeneous catalysts for BCD of lignin.

  10. Experimental and Computational Mechanistic Studies Guiding the Rational Design of Molecular Electrocatalysts for Production and Oxidation of Hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Raugei, Simone [Center for Molecular Electrocatalysis,; Helm, Monte L. [Center for Molecular Electrocatalysis,; Hammes-Schiffer, Sharon [Department of Chemistry, University of Illinois at Urbana—Champaign, 600 South Mathews Avenue, Urbana, Illinois 61801, United States; Appel, Aaron M. [Center for Molecular Electrocatalysis,; O’Hagan, Molly [Center for Molecular Electrocatalysis,; Wiedner, Eric S. [Center for Molecular Electrocatalysis,; Bullock, R. Morris [Center for Molecular Electrocatalysis,

    2015-11-25

    Understanding how to control the movement of protons and electrons is crucial to the design of fast, efficient electrocatalysts for H2 production and oxidation based on earth-abundant metals. Our work seeks to address fundamental questions about proton movement. We have demonstrated that incorporating a pendant amine functioning as a proton relay in the second coordination sphere of a metal complex helps proton mobility, resulting in faster and more energy-efficient catalysts. Proton-transfer reactions can be rate-limiting and are influenced by several factors, such as pKa values, steric effects, hydrogen bonding, and solvation/desolvation of the exogenous base and acid employed. The presence of multiple protonation sites introduces branching points along the catalytic cycle, making less productive pathways accessible or leading to the formation of stable off-cycle species. Using ligands with only one pendant amine mitigates this problem and results in catalysts with high rates for production of H2, although generally at higher overpotentials. For H2 oxidation catalysts, iron complexes with a high H2 binding affinity were developed. However, these iron complexes had a pKa mismatch between the protonated metal center and the protonated pendant amine, and consequently intramolecular proton movement was slow. Taken altogether, our results demonstrate the necessity of optimizing the entire catalytic cycle because optimization of a specific catalytic step can negatively influence another step and not necessarily lead to a better catalytic performance. We discuss a general procedure, based on thermodynamic arguments, which allows the simultaneous minimization of the free-energy change of each catalytic step, yielding a nearly flat free-energy surface, with no large barriers due to energy mismatches from either high- or low-energy intermediates.

  11. Experimental and Computational Mechanistic Studies Guiding the Rational Design of Molecular Electrocatalysts for Production and Oxidation of Hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Raugei, Simone; Helm, Monte L.; Hammes-Schiffer, Sharon; Appel, Aaron M.; O’Hagan, Molly; Wiedner, Eric S.; Bullock, R. Morris

    2016-01-19

    Understanding how to control the movement of protons and electrons is crucial to the design of fast, efficient electrocatalysts for H2 production and oxidation based on earth-abundant metals. Our work seeks to address fundamental questions about proton movement. We have demonstrated that incorporating a pendant amine functioning as a proton relay in the second coordination sphere of a metal complex helps proton mobility, resulting in faster and more energy-efficient catalysts. Proton-transfer reactions can be rate-limiting and are influenced by several factors, such as pKa values, steric effects, hydrogen bonding, and solvation/desolvation of the exogenous base and acid employed. The presence of multiple protonation sites introduces branching points along the catalytic cycle, making less productive pathways accessible or leading to the formation of stable off-cycle species. Using ligands with only one pendant amine mitigates this problem and results in catalysts with high rates for production of H2, although generally at higher overpotentials. For H2 oxidation catalysts, iron complexes with a high H2 binding affinity were developed. However, these iron complexes had a pKa mismatch between the protonated metal center and the protonated pendant amine, and consequently intramolecular proton movement was slow. Taken altogether, our results demonstrate the necessity of optimizing the entire catalytic cycle because optimization of a specific catalytic step can negatively influence another step and not necessarily lead to a better catalytic performance. We discuss a general procedure, based on thermodynamic arguments, which allows the simultaneous minimization of the free-energy change of each catalytic step, yielding a nearly flat free-energy surface, with no large barriers due to energy mismatches from either high- or low-energy intermediates.

  12. Highly sensitive silicon microreactor for catalyst testing

    DEFF Research Database (Denmark)

    Henriksen, Toke Riishøj; Olsen, Jakob Lind; Vesborg, Peter Christian Kjærgaard

    2009-01-01

    by directing the entire gas flow through the catalyst bed to a mass spectrometer, thus ensuring that nearly all reaction products are present in the analyzed gas flow. Although the device can be employed for testing a wide range of catalysts, the primary aim of the design is to allow characterization of model...... catalysts which can only be obtained in small quantities. Such measurements are of significant fundamental interest but are challenging because of the low surface areas involved. The relationship between the reaction zone gas flow and the pressure in the reaction zone is investigated experimentally......, it is found that platinum catalysts with areas as small as 15 mu m(2) are conveniently characterized with the device. (C) 2009 American Institute of Physics. [doi:10.1063/1.3270191]...

  13. Development and evaluation of a bioinformatics approach for designing molecular assays for viral detection.

    Directory of Open Access Journals (Sweden)

    Pierre H H Schneeberger

    Full Text Available Viruses belonging to the Flaviviridae and Bunyaviridae families show considerable genetic diversity. However, this diversity is not necessarily taken into account when developing diagnostic assays, which are often based on the pairwise alignment of a limited number of sequences. Our objective was to develop and evaluate a bioinformatics workflow addressing two recurrent issues of molecular assay design: (i the high intraspecies genetic diversity in viruses and (ii the potential for cross-reactivity with close relatives.The workflow developed herein was based on two consecutive BLASTn steps; the first was utilized to select highly conserved regions among the viral taxon of interest, and the second was employed to assess the degree of similarity of these highly-conserved regions to close relatives. Subsequently, the workflow was tested on a set of eight viral species, including various strains from the Flaviviridae and Bunyaviridae families.The genetic diversity ranges from as low as 0.45% variable sites over the complete genome of the Japanese encephalitis virus to more than 16% of variable sites on segment L of the Crimean-Congo hemorrhagic fever virus. Our proposed bioinformatics workflow allowed the selection-based on computing scores-of the best target for a diagnostic molecular assay for the eight viral species investigated.Our bioinformatics workflow allowed rapid selection of highly conserved and specific genomic fragments among the investigated viruses, while considering up to several hundred complete genomic sequences. The pertinence of this workflow will increase in parallel to the number of sequences made publicly available. We hypothesize that our workflow might be utilized to select diagnostic molecular markers for higher organisms with more complex genomes, provided the sequences are made available.

  14. The Design and Transformation of Biofundamentals: A Nonsurvey Introductory Evolutionary and Molecular Biology Course.

    Science.gov (United States)

    Klymkowsky, Michael W; Rentsch, Jeremy D; Begovic, Emina; Cooper, Melanie M

    2016-01-01

    Many introductory biology courses amount to superficial surveys of disconnected topics. Often, foundational observations and the concepts derived from them and students' ability to use these ideas appropriately are overlooked, leading to unrealistic expectations and unrecognized learning obstacles. The result can be a focus on memorization at the expense of the development of a meaningful framework within which to consider biological phenomena. About a decade ago, we began a reconsideration of what an introductory course should present to students and the skills they need to master. The original Web-based course's design presaged many of the recommendations of the Vision and Change report; in particular, a focus on social evolutionary mechanisms, stochastic (evolutionary and molecular) processes, and core ideas (cellular continuity, evolutionary homology, molecular interactions, coupled chemical reactions, and molecular machines). Inspired by insights from the Chemistry, Life, the Universe & Everything general chemistry project, we transformed the original Web version into a (freely available) book with a more unified narrative flow and a set of formative assessments delivered through the beSocratic system. We outline how student responses to course materials are guiding future course modifications, in particular a more concerted effort at helping students to construct logical, empirically based arguments, explanations, and models. © 2016 M. W. Klymkowsky et al. CBE—Life Sciences Education © 2016 The American Society for Cell Biology. This article is distributed by The American Society for Cell Biology under license from the author(s). It is available to the public under an Attribution–Noncommercial–Share Alike 3.0 Unported Creative Commons License (http://creativecommons.org/licenses/by-nc-sa/3.0).

  15. Hydroprocessing catalyst development

    Energy Technology Data Exchange (ETDEWEB)

    Boorman, P.M.; Kydd, R.A.; Sorensen, T.S.; Chong, K.; Lewis, J.

    1992-08-01

    Co-Mo and Ni-Mo hydroprocessing catalysts were examined for their activity in removal of sulfur from thiophene in model compounds, and in the cracking and hydrocracking of cumene. Three types of support materials were examined: carbon, modified carbon, and carbon covered alumina. The objective of the study was to examine the correlation between catalyst activity in the hydrodenitrogenation of model compounds, and the resistance of the catalyst to nitrogen poisoning during use in the hydroprocessing of gas oils. The use of model compound testing provided information on the individual catalytic reactions promoted by those materials. Infrared spectroscopy was used to study surface species on the catalysts and to explain many of the trends in activity observed, revealing the role of fluoride and phosphorus as a secondary promoter. Testing of the catalysts in hydrotreating of gas oils allowed comparison of model compound results with those from a real feedstock. The gas oil was also spiked with a model nitrogen compound and the results from catalytic hydrotreating of this material were compared with those from unspiked material. A key finding was that the carbon supported catalysts were the most effective in treating high-nitrogen feeds. The very favorable deactivation properties of carbon and carbon-covered alumina supported catalysts make these promising from an industrial point of view where catalyst deactivation is a limiting factor. 171 refs., 25 figs., 43 tabs.

  16. Catalyst for hydrocarbon conversion

    International Nuclear Information System (INIS)

    Duhaut, P.; Miquel, J.

    1975-01-01

    A description is given for a catalyst and process for hydrocarbon conversions, e.g., reforming. The catalyst contains an alumina carrier, platinum, iridium, at least one metal selected from uranium, vanadium, and gallium, and optionally halogen in the form of metal halide of one of the aforesaid components. (U.S.)

  17. Catalyst for Ammonia Oxidation

    DEFF Research Database (Denmark)

    2015-01-01

    The present invention relates to a bimetallic catalyst for ammonia oxidation, a method for producing a bimetallic catalyst for ammonia oxidation and a method for tuning the catalytic activity of a transition metal. By depositing an overlayer of less catalytic active metal onto a more catalytic...

  18. Magnetic catalyst bodies

    NARCIS (Netherlands)

    Teunissen, Wendy; Bol, A.A.; Geus, John W.

    1999-01-01

    After a discussion about the importance of the size of the catalyst bodies with reactions in the liquid-phase with a suspended catalyst, the possibilities of magnetic separation are dealt with. Deficiencies of the usual ferromagnetic particles are the reactivity and the clustering of the

  19. Reducible oxide based catalysts

    Science.gov (United States)

    Thompson, Levi T.; Kim, Chang Hwan; Bej, Shyamal K.

    2010-04-06

    A catalyst is disclosed herein. The catalyst includes a reducible oxide support and at least one noble metal fixed on the reducible oxide support. The noble metal(s) is loaded on the support at a substantially constant temperature and pH.

  20. Custom-Designed Molecular Scissors for Site-Specific Manipulation of the Plant and Mammalian Genomes

    Science.gov (United States)

    Kandavelou, Karthikeyan; Chandrasegaran, Srinivasan

    Zinc finger nucleases (ZFNs) are custom-designed molecular scissors, engineered to cut at specific DNA sequences. ZFNs combine the zinc finger proteins (ZFPs) with the nonspecific cleavage domain of the FokI restriction enzyme. The DNA-binding specificity of ZFNs can be easily altered experimentally. This easy manipulation of the ZFN recognition specificity enables one to deliver a targeted double-strand break (DSB) to a genome. The targeted DSB stimulates local gene targeting by several orders of magnitude at that specific cut site via homologous recombination (HR). Thus, ZFNs have become an important experimental tool to make site-specific and permanent alterations to genomes of not only plants and mammals but also of many other organisms. Engineering of custom ZFNs involves many steps. The first step is to identify a ZFN site at or near the chosen chromosomal target within the genome to which ZFNs will bind and cut. The second step is to design and/or select various ZFP combinations that will bind to the chosen target site with high specificity and affinity. The DNA coding sequence for the designed ZFPs are then assembled by polymerase chain reaction (PCR) using oligonucleotides. The third step is to fuse the ZFP constructs to the FokI cleavage domain. The ZFNs are then expressed as proteins by using the rabbit reticulocyte in vitro transcription/translation system and the protein products assayed for their DNA cleavage specificity.

  1. Design considerations for highly effective fluorescence excitation and detection optical systems for molecular diagnostics

    Science.gov (United States)

    Kasper, Axel; Van Hille, Herbert; Kuk, Sola

    2018-02-01

    Modern instruments for molecular diagnostics are continuously optimized for diagnostic accuracy, versatility and throughput. The latest progress in LED technology together with tailored optics solutions allows developing highly efficient photonics engines perfectly adapted to the sample under test. Super-bright chip-on-board LED light sources are a key component for such instruments providing maximum luminous intensities in a multitude of narrow spectral bands. In particular the combination of white LEDs with other narrow band LEDs allows achieving optimum efficiency outperforming traditional Xenon light sources in terms of energy consumption, heat dissipation in the system, and switching time between spectral channels. Maximum sensitivity of the diagnostic system can only be achieved with an optimized optics system for the illumination and imaging of the sample. The illumination beam path must be designed for optimum homogeneity across the field while precisely limiting the angular distribution of the excitation light. This is a necessity for avoiding spill-over to the detection beam path and guaranteeing the efficiency of the spectral filtering. The imaging optics must combine high spatial resolution, high light collection efficiency and optimized suppression of excitation light for good signal-to-noise ratio. In order to achieve minimum cross-talk between individual wells in the sample, the optics design must also consider the generation of stray light and the formation of ghost images. We discuss what parameters and limitations have to be considered in an integrated system design approach covering the full path from the light source to the detector.

  2. Molecular Understanding and Structural-Based Design of Polyacrylamides and Polyacrylates as Antifouling Materials.

    Science.gov (United States)

    Chen, Hong; Zhao, Chao; Zhang, Mingzhen; Chen, Qiang; Ma, Jie; Zheng, Jie

    2016-04-12

    Design and synthesis of highly bioinert and biocompatible antifouling materials are crucial for a broad range of biomedical and engineering applications. Among antifouling materials, polyacrylamides and polyacrylates have proved so promising because of cheap raw materials, ease of synthesis and applicability, and abundant functional groups. The strong surface hydration and the high surface packing density of polyacrylamides and polyacrylates are considered to be the key contributors to their antifouling property. In this article, we review our studies on the design and synthesis of a series of polyacrylamides and polyacrylates with different molecular structures. These polymers can be fabricated into different architectural forms (brushes, nanoparticles, nanogels, and hydrogels), all of which are highly resistant to the attachment of proteins, cells, and bacteria. We find that small structural changes in the polymers can lead to large enhancement in surface hydration and antifouling performance, both showing a positive correlation. This reveals a general design rule for effective antifouling materials. Furthermore, polyacrylamides and polyacrylates are readily functionalized with other bioactive compounds to achieve different new multifunctionalities.

  3. Evaluation of peptide designing strategy against subunit reassociation in mucin 1: A steered molecular dynamics approach.

    Directory of Open Access Journals (Sweden)

    J Lesitha Jeeva Kumari

    Full Text Available Subunit reassociation in mucin 1, a breast cancer tumor marker, is reported as one of the critical factors for its cytoplasmic activation. Inhibition of its heterodimeric association would therefore result in loss of its function and alter disease progression. The present study aimed at evaluating peptide inhibitor designing strategies that may serve as antagonist against this receptor-ligand alliance. Several peptides and their derivatives were designed based on native residues, subunit interface, hydrogen bonding and secondary structure. Docking studies with the peptides were carried on the receptor subunit and their binding affinities were evaluated using steered molecular dynamics simulation and umbrella sampling. Our results showed that among all the different classes of peptides evaluated, the receptor based peptide showed the highest binding affinity. This result was concurrent with the experimental observation that the receptor-ligand alliance in mucin 1 is highly specific. Our results also show that peptide ligand against this subunit association is only stabilized through native residue inter-protein interaction irrespective of the peptide structure, peptide length and number of hydrogen bonds. Consistency in binding affinity, pull force and free energy barrier was observed with only the receptor derived peptides which resulted in favorable interprotein interactions at the interface. Several observations were made and discussed which will eventually lead to designing efficient peptide inhibitors against mucin 1 heterodimeric subunit reassociation.

  4. EXPLORING THE DESIGN AND USE OF MOLECULAR ANIMATIONS THAT CONFLICT FOR UNDERSTANDING CHEMICAL REACTIONS

    Directory of Open Access Journals (Sweden)

    Resa M. Kelly

    Full Text Available Understanding chemical reactions conceptually involves recognizing characteristics of observable phenomena and envisioning how atoms, ions and molecules move and interact to cause the macroscopic changes. Our research focuses on the development of effective strategies for designing and presenting visualizations (videos and animations to assist students with making connections between macroscopic and molecular level behaviors of chemical reactions. Specifically, we study how students, who view videos of a redox reaction that exhibits obvious signs of macroscopic chemical change, can determine which molecular animation of a set of contrasting animations is best supported by its fit with experimental evidence. Herein we describe how we develop our videos and animations, and how students are learning from this animation task. Students who select inaccurate animation models are often enticed by a model that is easier to explain and fits with their understanding of reaction equations. We note that even though students indicate a preference for one animation over another, they often revise their drawn representations to fit with features from multiple animations. With the assistance of eye tracking research, we are gaining a better understanding of what students view and how they make sense of it.

  5. Molecular design, synthesis and physical properties of novel Cytisine-derivatives - Experimental and theoretical study

    Science.gov (United States)

    Ivanova, Bojidarka; Spiteller, Michael

    2013-02-01

    The paper presented a comprehensive theoretical and experimental study on the molecular drugs-design, synthesis, isolation, physical spectroscopic and mass spectrometric elucidation of novel functionalization derivatives of Cytisine (Cyt), using nucleosidic residues. Since these alkaloids have established biochemical profile, related the binding affinity of the nicotinic acetylcholine receptors (nAChRs), particularly α7 sub-type, the presented correlation between the molecular structure and properties allowed to evaluated the highlights of the biochemical hypothesises related the Schizophrenia. The anticancer activity of α7 subtype agonists and the crucial role of the nucleoside-based medications in the cancer therapy provided opportunity for further study on the biochemical relationship between Schizophrenia and few kinds of cancers, which has been hypothesized recently. The physical electronic absorptions (EAs), circular dichroic (CD) and Raman spectroscopic (RS) properties as well as mass spectrometric (MS) data, obtained using electrospray ionization (ESI) and atmospheric-pressure chemical ionization (APCI) methods under the positive single (MS) and tandem (MS/MS) modes of operation are discussed. Taking into account reports on a fatal intoxication of Cyt, the presented data would be of interest in the field of forensic chemistry, through development of highly selective and sensitive analytical protocols. Quantum chemical method is used to predict the physical properties of the isolated alkaloids, their affinity to the receptor loop and gas-phase stabilized species, observed mass spectrometrically.

  6. Design of potentially active ligands for SH2 domains by molecular modeling methods

    Directory of Open Access Journals (Sweden)

    Hurmach V. V.

    2014-07-01

    Full Text Available Search for new chemical structures possessing specific biological activity is a complex problem that needs the use of the latest achievements of molecular modeling technologies. It is well known that SH2 domains play a major role in ontogenesis as intermediaries of specific protein-protein interactions. Aim. Developing an algorithm to investigate the properties of SH2 domain binding, search for new potential active compounds for the whole SH2 domains class. Methods. In this paper, we utilize a complex of computer modeling methods to create a generic set of potentially active compounds targeting universally at the whole class of SH2 domains. A cluster analysis of all available three-dimensional structures of SH2 domains was performed and general pharmacophore models were formulated. The models were used for virtual screening of collection of drug-like compounds provided by Enamine Ltd. Results. The design technique for library of potentially active compounds for SH2 domains class was proposed. Conclusions. The original algorithm of SH2 domains research with molecular docking method was developed. Using our algorithm, the active compounds for SH2 domains were found.

  7. Towards the design of new and improved drilling fluid additives using molecular dynamics simulations

    International Nuclear Information System (INIS)

    Anderson, Richard L.; Greenwel, H. Christopher; Suter, James L.; Coveney, Peter V.; Jarvis, Rebecca M.

    2010-01-01

    During exploration for oil and gas, a technical drilling fluid is used to lubricate the drill bit, maintain hydrostatic pressure, transmit sensor readings, remove rock cuttings and inhibit swelling of unstable clay based reactive shale formations. Increasing environmental awareness and resulting legislation has led to the search for new, improved biodegradable drilling fluid components. In the case of additives for clay swelling inhibition, an understanding of how existing effective additives interact with clays must be gained to allow the design of improved molecules. Owing to the disordered nature and nano scope dimension of the interlayer pores of clay minerals, computer simulations have become an increasingly useful tool for studying clay-swelling inhibitor interactions. In this work we briefly review the history of the development of technical drilling fluids, the environmental impact of drilling fluids and the use of computer simulations to study the interactions between clay minerals and swelling inhibitors. We report on results from some recent large-scale molecular dynamics simulation studies on low molecular weight water-soluble macromolecular inhibitor molecules. The structure and interactions of poly(propylene oxide)-diamine, poly(ethylene glycol) and poly(ethylene oxide)-diacrylate inhibitor molecules with montmorillonite clay are studied. (author)

  8. When biomolecules meet graphene: from molecular level interactions to material design and applications.

    Science.gov (United States)

    Li, Dapeng; Zhang, Wensi; Yu, Xiaoqing; Wang, Zhenping; Su, Zhiqiang; Wei, Gang

    2016-12-01

    Graphene-based materials have attracted increasing attention due to their atomically-thick two-dimensional structures, high conductivity, excellent mechanical properties, and large specific surface areas. The combination of biomolecules with graphene-based materials offers a promising method to fabricate novel graphene-biomolecule hybrid nanomaterials with unique functions in biology, medicine, nanotechnology, and materials science. In this review, we focus on a summarization of the recent studies in functionalizing graphene-based materials using different biomolecules, such as DNA, peptides, proteins, enzymes, carbohydrates, and viruses. The different interactions between graphene and biomolecules at the molecular level are demonstrated and discussed in detail. In addition, the potential applications of the created graphene-biomolecule nanohybrids in drug delivery, cancer treatment, tissue engineering, biosensors, bioimaging, energy materials, and other nanotechnological applications are presented. This review will be helpful to know the modification of graphene with biomolecules, understand the interactions between graphene and biomolecules at the molecular level, and design functional graphene-based nanomaterials with unique properties for various applications.

  9. Modern dose-finding designs for cancer phase I trials drug combinations and molecularly targeted agents

    CERN Document Server

    Hirakawa, Akihiro; Daimon, Takashi; Matsui, Shigeyuki

    2018-01-01

    This book deals with advanced methods for adaptive phase I dose-finding clinical trials for combination of two agents and molecularly targeted agents (MTAs) in oncology. It provides not only methodological aspects of the dose-finding methods, but also software implementations and practical considerations in applying these complex methods to real cancer clinical trials. Thus, the book aims to furnish researchers in biostatistics and statistical science with a good summary of recent developments of adaptive dose-finding methods as well as providing practitioners in biostatistics and clinical investigators with advanced materials for designing, conducting, monitoring, and analyzing adaptive dose-finding trials. The topics in the book are mainly related to cancer clinical trials, but many of those topics are potentially applicable or can be extended to trials for other diseases. The focus is mainly on model-based dose-finding methods for two kinds of phase I trials. One is clinical trials with combinations of tw...

  10. Molecular design and ordering effects in π-functional materials for transistor and solar cell applications

    KAUST Repository

    Beaujuge, Pierre

    2011-12-21

    Organic electronics are broadly anticipated to impact the development of flexible thin-film device technologies. Among these, solution-processable π-conjugated polymers and small molecules are proving particularly promising in field-effect transistors and bulk heterojunction solar cells. This Perspective analyzes some of the most exciting strategies recently suggested in the design and structural organization of π-functional materials for transistor and solar cell applications. Emphasis is placed on the interplay between molecular structure, self-assembling properties, nanoscale and mesoscale ordering, and device efficiency parameters. A critical look at the various approaches used to optimize both materials and device performance is provided to assist in the identification of new directions and further advances. © 2011 American Chemical Society.

  11. Novel α, β-Unsaturated Sophoridinic Derivatives: Design, Synthesis, Molecular Docking and Anti-Cancer Activities

    Directory of Open Access Journals (Sweden)

    Yiming Xu

    2017-11-01

    Full Text Available Using sophoridine 1 and chalcone 3 as the lead compounds, a series of novel α, β-unsaturated sophoridinic derivatives were designed, synthesized, and evaluated for their in vitro cytotoxicity. Structure-activity relationship (SAR analysis indicated that introduction of α, β-unsaturated ketone moiety and heterocyclic group might significantly enhance anticancer activity. Among the compounds, 2f and 2m exhibited potential effects against HepG-2 and CNE-2 human cancer cell lines. Furthermore, molecular docking studies were performed to understand possible docking sites of the molecules on the target proteins and the mode of binding. This work provides a theoretical basis for structural optimizations and exploring anticancer pathways of this kind of compound.

  12. Multilevel Molecular Modeling Approach for a Rational Design of Ionic Current Sensors for Nanofluidics.

    Science.gov (United States)

    Kirch, Alexsandro; de Almeida, James M; Miranda, Caetano R

    2018-05-10

    The complexity displayed by nanofluidic-based systems involves electronic and dynamic aspects occurring across different size and time scales. To properly model such kind of system, we introduced a top-down multilevel approach, combining molecular dynamics simulations (MD) with first-principles electronic transport calculations. The potential of this technique was demonstrated by investigating how the water and ionic flow through a (6,6) carbon nanotube (CNT) influences its electronic transport properties. We showed that the confinement on the CNT favors the partially hydrated Na, Cl, and Li ions to exchange charge with the nanotube. This leads to a change in the electronic transmittance, allowing for the distinguishing of cations from anions. Such an ionic trace may handle an indirect measurement of the ionic current that is recorded as a sensing output. With this case study, we are able to show the potential of this top-down multilevel approach, to be applied on the design of novel nanofluidic devices.

  13. Fragment-based drug discovery and molecular docking in drug design.

    Science.gov (United States)

    Wang, Tao; Wu, Mian-Bin; Chen, Zheng-Jie; Chen, Hua; Lin, Jian-Ping; Yang, Li-Rong

    2015-01-01

    Fragment-based drug discovery (FBDD) has caused a revolution in the process of drug discovery and design, with many FBDD leads being developed into clinical trials or approved in the past few years. Compared with traditional high-throughput screening, it displays obvious advantages such as efficiently covering chemical space, achieving higher hit rates, and so forth. In this review, we focus on the most recent developments of FBDD for improving drug discovery, illustrating the process and the importance of FBDD. In particular, the computational strategies applied in the process of FBDD and molecular-docking programs are highlighted elaborately. In most cases, docking is used for predicting the ligand-receptor interaction modes and hit identification by structurebased virtual screening. The successful cases of typical significance and the hits identified most recently are discussed.

  14. Design, preparation, surface recognition properties, and characteristics of icariin molecularly imprinted polymers

    Directory of Open Access Journals (Sweden)

    Xiaohe Jia

    2015-12-01

    Full Text Available Icariin molecularly imprinted polymers (MIPs were prepared by precipitation polymerization. Prior to the polymerization, computer simulation was performed to sketchily choose the suitable functional monomer and the corresponding polymerization solvent. The optimized synthesis parameters, including the functional monomer acrylamide, the mixture of methanol and acetonitrile (V:V = 3:1 as the polymerization solvent, and the reaction molar ratio (1:6:80 of template molecule, functional monomer and cross-linker, were respectively obtained by single factor analysis and orthogonal design methods. The results of the adsorption experiments showed that the resultant MIPs exhibited good adsorption and recognition abilities to icariin. Scatchard analysis illustrated that the homogeneous binding sites only for icariin molecules were formed in the prepared MIPs.

  15. Molecular design and theoretical characterization of benzodithiophene based organic photovoltaic materials

    Science.gov (United States)

    Bhattacharya, Labanya; Sahu, Sridhar

    2018-05-01

    Two different oligomers, containing methyl substituted Benzodithiophene (BDT) as donor unit, fluorinated thiophene as the π-bridge unit and two different kinds of acceptors based on fluorinated benzothiadiazole, fluorinated benzoselenadiazole units are designed for bulk heterojunction (BHJ) organic solar cell (OSC). The ground and excited state properties of those donor-π-acceptor-π-donor (D-π-A-π-D) oligomeric configurations are characterized via density functional (DFT) and time dependent density functional theory (TD-DFT). The parameters such as dipole moment (ρ), chemical potential (µ), electronegativity (χ), frontier molecular orbital (FMO) analysis, HOMO-LUMO gap, open circuit voltage (Voc) and driving force (ΔE) are calculated to analyze geometrical, electronic structural, quantum chemical and photovoltaic properties of the compounds. In addition, optical absorption spectra are also presented for the optical characterization of the compounds.

  16. Structural Biology and Molecular Modeling in the Design of Novel DPP-4 Inhibitors

    Science.gov (United States)

    Scapin, Giovanna

    Inhibition of dipeptidyl peptidase IV (DPP-4) is a promising new approach for the treatment of type 2 diabetes. DPP-4 is the enzyme responsible for inactivating the incretin hormones glucagon-like peptide 1 (GLP-1) and glucose dependent insulinotropic polypeptide (GIP), two hormones that play important roles in glucose homeostasis. The potent, orally bioavailable and highly selective small molecule DPP-4 inhibitor sitagliptin has been approved by the FDA as novel drug for the treatment of type 2 diabetes. The comparison between the binding mode of sitagliptin (a β-amino acid) and that of a second class of inhibitors (α-amino acid-based) initially led to the successful identification and design of structurally diverse and highly potent DPP-4 inhibitors. Further analysis of the crystal structure of sitagliptin bound to DPP-4 suggested that the central β-amino butanoyl moiety could be replaced by a rigid group. This was confirmed by molecular modeling, and the resulting cyclohexylamine analogs were synthesized and found to be potent DPP-4 inhibitors. However, the triazolopyrazine was predicted to be distorted in order to fit in the binding pocket, and the crystal structure showed that multiple conformations exist for this moiety. Additional molecular modeling studies were then used to improve potency of the cyclohexylamine series. In addition, a 3-D QSAR method was used to gain insight for reducing off-target DPP-8/9 activities. Novel compounds were thus synthesized and found to be potent DPP-4 inhibitors. Two compounds in particular were designed to be highly selective against off-target "DPP-4 Activity- and/or Structure Homologues" (DASH) enzymes while maintaining potency against DPP-4.

  17. Biomimetic catalysts responsive to specific chemical signals

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Yan [Iowa State Univ., Ames, IA (United States)

    2015-03-04

    Part 1. Design of Biomimetic Catalysts Based on Amphiphilic Systems The overall objective of our research is to create biomimetic catalysts from amphiphilic molecules. More specifically, we aim to create supramolecular systems that can be used to control the microenvironment around a catalytic center in a biomimetic fashion and apply the learning to construct supramolecular catalysts with novel functions found in enzymatic catalysts. We have prepared synthetic molecules (i.e., foldamers) that could fold into helical structures with nanometer-sized internal hydrophilic cavities. Cavities of this size are typically observed only in the tertiary and quaternary structures of proteins but were formed in our foldamer prepared in just a few steps from the monomer. Similar to many proteins, our foldamers displayed cooperativity in the folding/unfolding equilibrium and followed a two-state conformational transition. In addition, their conformational change could be triggered by solvent polarity, pH, or presence of metal ions and certain organic molecules. We studied their environmentally dependent conformational changes in solutions, surfactant micelles, and lipid bilayer membranes. Unlike conventional rigid supramolecular host, a foldamer undergoes conformational change during guest binding. Our study in the molecular recognition of an oligocholate host yielded some extremely exciting results. Cooperativity between host conformation and host–guest interactions was found to “magnify” weak binding interactions. In other words, since binding affinity is determined by the overall change of free energy during the binding, guest-induced conformational change of the host, whether near or far from the binding site, affects the binding. This study has strong implications in catalysis because enzymes have been hypothesized to harvest similar intramolecular forces to strengthen their binding with the transition state of an enzyme-catalyzed reaction. The supramolecular and

  18. Preparation of alveolate hydrophobic catalyst for tritium waste gas treatment

    International Nuclear Information System (INIS)

    Yang, Yong; Peng, Shuming; Wang, Heyi; Du, Yang; Li, Jiamao

    2016-01-01

    Highlights: • The catalyst is hydrophobic, it will not be poisoned by steam in room air at room temperature which is better than Pt-Al 2 O 3 . • At room temperature, the conversion of low concentration of H2 and tritium gas in room air over the catalyst is high. • The air resistance of catalyst is much lower than graininess Pt-Al 2 O 3 . • It is inorganic and will not burn. - Abstract: To prepare a catalyst for the detritiation of waste gases at high flow rates, a heat-resistant hydrophobic zeolitic molecular sieve coating was synthesized on the surface of alveolate cordierite by hydrothermal processing. The alveolate hydrophobic catalyst prepared from the support was essentially waterproof and not easily poisoned by moisture. At room temperature, the conversion of low concentrations of H 2 in humid air over the catalyst was higher than 95% at different space velocities (0–16,000 h −1 ) and different relative humidities. The reaction rate constant of the oxidation of tritium over alveolate hydrophobic catalyst is 0.182 s −1 at 293.3 K–293.7 K and 59%–60% RH, it is much higher than the catalyst of reference honeycomb catalyst.

  19. Molecular and macro-scale analysis of enzyme-crosslinked silk hydrogels for rational biomaterial design.

    Science.gov (United States)

    McGill, Meghan; Coburn, Jeannine M; Partlow, Benjamin P; Mu, Xuan; Kaplan, David L

    2017-11-01

    Silk fibroin-based hydrogels have exciting applications in tissue engineering and therapeutic molecule delivery; however, their utility is dependent on their diffusive properties. The present study describes a molecular and macro-scale investigation of enzymatically-crosslinked silk fibroin hydrogels, and demonstrates that these systems have tunable crosslink density and diffusivity. We developed a liquid chromatography tandem mass spectroscopy (LC-MS/MS) method to assess the quantity and order of covalent tyrosine crosslinks in the hydrogels. This analysis revealed between 28 and 56% conversion of tyrosine to dityrosine, which was dependent on the silk concentration and reactant concentration. The crosslink density was then correlated with storage modulus, revealing that both crosslinking and protein concentration influenced the mechanical properties of the hydrogels. The diffusive properties of the bulk material were studied by fluorescence recovery after photobleaching (FRAP), which revealed a non-linear relationship between silk concentration and diffusivity. As a result of this work, a model for synthesizing hydrogels with known crosslink densities and diffusive properties has been established, enabling the rational design of silk hydrogels for biomedical applications. Hydrogels from naturally-derived silk polymers offer versitile opportunities in the biomedical field, however, their design has largely been an empirical process. We present a fundamental study of the crosslink density, storage modulus, and diffusion behavior of enzymatically-crosslinked silk hydrogels to better inform scaffold design. These studies revealed unexpected non-linear trends in the crosslink density and diffusivity of silk hydrogels with respect to protein concentration and crosslink reagent concentration. This work demonstrates the tunable diffusivity and crosslinking in silk fibroin hydrogels, and enables the rational design of biomaterials. Further, the characterization methods

  20. Highly active self-immobilized FI-Zr catalysts in a PCP framework for ethylene polymerization.

    Science.gov (United States)

    Li, He; Xu, Bo; He, Jianghao; Liu, Xiaoming; Gao, Wei; Mu, Ying

    2015-12-04

    A series of zirconium-based porous coordination polymers (PCPs) containing FI catalysts in the frameworks have been developed and studied as catalysts for ethylene polymerization. These PCPs exhibit good catalytic activities and long life times, producing polyethylenes with high molecular weights and bimodal molecular weight distribution in the form of particles.

  1. Design of two and three input molecular logic gates using non-Watson-Crick base pairing-based molecular beacons.

    Science.gov (United States)

    Lin, Jia-Hui; Tseng, Wei-Lung

    2014-03-21

    This study presents a single, resettable, and sensitive molecular beacon (MB) used to operate molecular-scale logic gates. The MB consists of a random DNA sequence, a fluorophore at the 5'-end, and a quencher at the 3'-end. The presence of Hg(2+), Ag(+), and coralyne promoted the formation of stable T-Hg(2+)-T, C-Ag(+)-C, and A2-coralyne-A2 coordination in the MB probe, respectively, thereby driving its conformational change. The metal ion or small molecule-mediated coordination of mismatched DNA brought the fluorophore and the quencher into close proximity, resulting in collisional quenching of fluorescence between the two organic dyes. Because thiol can bind Hg(2+) and remove it from the T-Hg(2+)-T-based MB, adding thiol to a solution of the T-Hg(2+)-T-based MB allowed the fluorophore and the quencher to be widely separated. A similar phenomenon was observed when replacing Hg(2+) with Ag(+). Because Ag(+) strongly binds to iodide, cyanide, and cysteine, they were capable of removing Ag(+) from the C-Ag(+)-C-based MB, restoring the fluorescence of the MB. Moreover, the fluorescence of the A2-coralyne-A2-based MB could be switched on by adding polyadenosine. Using these analytes as inputs and the MB as a signal transducer, we successfully developed a series of two-input, three-input, and set-reset logic gates at the molecular level.

  2. Multiphase catalysts for selective reduction of NOx with hydrocarbons

    International Nuclear Information System (INIS)

    Maisuls, S.E.

    2000-01-01

    catalyst with Rh was studied and the results are summarized in Chapter 6. Chapter 7 presents a comparison between the Co-Pt and Co-Rh systems. Finally, we evaluate the results of this study and general conclusions with suggestions for the design of an optimal deNOx catalyst. refs

  3. Reaction selectivity studies on nanolithographically-fabricated platinum model catalyst arrays

    Energy Technology Data Exchange (ETDEWEB)

    Grunes, Jeffrey Benjamin [Univ. of California, Berkeley, CA (United States)

    2004-05-01

    In an effort to understand the molecular ingredients of catalytic activity and selectivity toward the end of tuning a catalyst for 100% selectivity, advanced nanolithography techniques were developed and utilized to fabricate well-ordered two-dimensional model catalyst arrays of metal nanostructures on an oxide support for the investigation of reaction selectivity. In-situ and ex-situ surface science techniques were coupled with catalytic reaction data to characterize the molecular structure of the catalyst systems and gain insight into hydrocarbon conversion in heterogeneous catalysis. Through systematic variation of catalyst parameters (size, spacing, structure, and oxide support) and catalytic reaction conditions (hydrocarbon chain length, temperature, pressures, and gas composition), the data presented in this dissertation demonstrate the ability to direct a reaction by rationally adjusting, through precise control, the design of the catalyst system. Electron beam lithography (EBL) was employed to create platinum nanoparticles on an alumina (Al2O3) support. The Pt nanoparticle spacing (100-150-nm interparticle distance) was varied in these samples, and they were characterized using x-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM), both before and after reactions. The TEM studies showed the 28-nm Pt nanoparticles with 100 and 150-nm interparticle spacing on alumina to be polycrystalline in nature, with crystalline sizes of 3-5 nm. The nanoparticle crystallites increased significantly after heat treatment. The nanoparticles were still mostly polycrystalline in nature, with 2-3 domains. The 28-nm Pt nanoparticles deposited on alumina were removed by the AFM tip in contact mode with a normal force of approximately 30 nN. After heat treatment at 500 C in vacuum for 3 hours, the AFM tip, even at 4000 nN, could not remove the platinum

  4. Process for the regeneration of metallic catalysts

    Science.gov (United States)

    Katzer, James R.; Windawi, Hassan

    1981-01-01

    A method for the regeneration of metallic hydrogenation catalysts from the class consisting of Ni, Rh, Pd, Ir, Pt and Ru poisoned with sulfur, with or without accompanying carbon deposition, comprising subjecting the catalyst to exposure to oxygen gas in a concentration of about 1-10 ppm. intermixed with an inert gas of the group consisting of He, A, Xe, Kr, N.sub.2 and air substantially free of oxygen to an extent such that the total oxygen molecule throughout is in the range of about 10 to 20 times that of the hydrogen sulfide molecular exposure producing the catalyst poisoning while maintaining the temperature in the range of about 300.degree. to 500.degree. C.

  5. Catalysts, methods of making catalysts, and methods of use

    KAUST Repository

    Renard, Laetitia; El Eter, Mohamad; Caps, Valerie; Basset, Jean-Marie

    2014-01-01

    Embodiments of the present disclosure provide for catalysts, methods of making catalysts, methods of using catalysts, and the like. In an embodiment, the method of making the catalysts can be performed in a single step with a metal nanoparticle precursor and a metal oxide precursor, where a separate stabilizing agent is not needed.

  6. Catalysts, methods of making catalysts, and methods of use

    KAUST Repository

    Renard, Laetitia

    2014-03-06

    Embodiments of the present disclosure provide for catalysts, methods of making catalysts, methods of using catalysts, and the like. In an embodiment, the method of making the catalysts can be performed in a single step with a metal nanoparticle precursor and a metal oxide precursor, where a separate stabilizing agent is not needed.

  7. Residualization Rates of Near-Infrared Dyes for the Rational Design of Molecular Imaging Agents.

    Science.gov (United States)

    Cilliers, Cornelius; Liao, Jianshan; Atangcho, Lydia; Thurber, Greg M

    2015-12-01

    Near-infrared (NIR) fluorescence imaging is widely used for tracking antibodies and biomolecules in vivo. Clinical and preclinical applications include intraoperative imaging, tracking therapeutics, and fluorescent labeling as a surrogate for subsequent radiolabeling. Despite their extensive use, one of the fundamental properties of NIR dyes, the residualization rate within cells following internalization, has not been systematically studied. This rate is required for the rational design of probes and proper interpretation of in vivo results. In this brief report, we measure the cellular residualization rate of eight commonly used dyes encompassing three core structures (cyanine, boron-dipyrromethene (BODIPY), and oxazine/thiazine/carbopyronin). We identify residualizing (half-life >24 h) and non-residualizing (half-life <24 h) dyes in both the far-red (~650-680 nm) and near-infrared (~740-800 nm) regions. This data will allow researchers to independently and rationally select the wavelength and residualizing nature of dyes for molecular imaging agent design.

  8. Characterization of dipeptidylcarboxypeptidase of Leishmania donovani: a molecular model for structure based design of antileishmanials

    Science.gov (United States)

    Baig, Mirza Saqib; Kumar, Ashutosh; Siddiqi, Mohammad Imran; Goyal, Neena

    2010-01-01

    Leishmania donovani dipeptidylcarboxypeptidsae (LdDCP), an angiotensin converting enzyme (ACE) related metallopeptidase has been identified and characterized as a putative drug target for antileishmanial chemotherapy. The kinetic parameters for LdDCP with substrate, Hip-His-Leu were determined as, Km, 4 mM and Vmax, 1.173 μmole/ml/min. Inhibition studies revealed that known ACE inhibitors (captopril and bradykinin potentiating peptide; BPP1) were weak inhibitors for LdDCP as compared to human testicular ACE (htACE) with Ki values of 35.8 nM and 3.9 μM, respectively. Three dimensional model of LdDCP was generated based on crystal structure of Escherichia coli DCP (EcDCP) by means of comparative modeling and assessed using PROSAII, PROCHECK and WHATIF. Captopril docking with htACE, LdDCP and EcDCP and analysis of molecular electrostatic potentials (MEP) suggested that the active site domain of three enzymes has several minor but potentially important structural differences. These differences could be exploited for designing selective inhibitor of LdDCP thereby antileishmanial compounds either by denovo drug design or virtual screening of small molecule databases.

  9. Design principles and optimal performance for molecular motors under realistic constraints

    Science.gov (United States)

    Tu, Yuhai; Cao, Yuansheng

    2018-02-01

    The performance of a molecular motor, characterized by its power output and energy efficiency, is investigated in the motor design space spanned by the stepping rate function and the motor-track interaction potential. Analytic results and simulations show that a gating mechanism that restricts forward stepping in a narrow window in configuration space is needed for generating high power at physiologically relevant loads. By deriving general thermodynamics laws for nonequilibrium motors, we find that the maximum torque (force) at stall is less than its theoretical limit for any realistic motor-track interactions due to speed fluctuations. Our study reveals a tradeoff for the motor-track interaction: while a strong interaction generates a high power output for forward steps, it also leads to a higher probability of wasteful spontaneous back steps. Our analysis and simulations show that this tradeoff sets a fundamental limit to the maximum motor efficiency in the presence of spontaneous back steps, i.e., loose-coupling. Balancing this tradeoff leads to an optimal design of the motor-track interaction for achieving a maximum efficiency close to 1 for realistic motors that are not perfectly coupled with the energy source. Comparison with existing data and suggestions for future experiments are discussed.

  10. Design of Pd/PANI/Pd sandwich-structured nanotube array catalysts with special shape effects and synergistic effects for ethanol electrooxidation.

    Science.gov (United States)

    Wang, An-Liang; Xu, Han; Feng, Jin-Xian; Ding, Liang-Xin; Tong, Ye-Xiang; Li, Gao-Ren

    2013-07-24

    Low cost, high activity, and long-term durability are the main requirements for commercializing fuel cell electrocatalysts. Despite tremendous efforts, developing non-Pt anode electrocatalysts with high activity and long-term durability at low cost remains a significant technical challenge. Here we report a new type of hybrid Pd/PANI/Pd sandwich-structured nanotube array (SNTA) to exploit shape effects and synergistic effects of Pd-PANI composites for the oxidation of small organic molecules for direct alcohol fuel cells. These synthesized Pd/PANI/Pd SNTAs exhibit significantly improved electrocatalytic activity and durability compared with Pd NTAs and commercial Pd/C catalysts. The unique SNTAs provide fast transport and short diffusion paths for electroactive species and high utilization rate of catalysts. Besides the merits of nanotube arrays, the improved electrocatalytic activity and durability are especially attributed to the special Pd/PANI/Pd sandwich-like nanostructures, which results in electron delocalization between Pd d orbitals and PANI π-conjugated ligands and in electron transfer from Pd to PANI.

  11. Catalyst in Basic Oleochemicals

    Directory of Open Access Journals (Sweden)

    Eva Suyenty

    2007-10-01

    Full Text Available Currently Indonesia is the world largest palm oil producer with production volume reaching 16 million tones per annum. The high crude oil and ethylene prices in the last 3 – 4 years contribute to the healthy demand growth for basic oleochemicals: fatty acids and fatty alcohols. Oleochemicals are starting to replace crude oil derived products in various applications. As widely practiced in petrochemical industry, catalyst plays a very important role in the production of basic oleochemicals. Catalytic reactions are abound in the production of oleochemicals: Nickel based catalysts are used in the hydrogenation of unsaturated fatty acids; sodium methylate catalyst in the transesterification of triglycerides; sulfonic based polystyrene resin catalyst in esterification of fatty acids; and copper chromite/copper zinc catalyst in the high pressure hydrogenation of methyl esters or fatty acids to produce fatty alcohols. To maintain long catalyst life, it is crucial to ensure the absence of catalyst poisons and inhibitors in the feed. The preparation methods of nickel and copper chromite catalysts are as follows: precipitation, filtration, drying, and calcinations. Sodium methylate is derived from direct reaction of sodium metal and methanol under inert gas. The sulfonic based polystyrene resin is derived from sulfonation of polystyrene crosslinked with di-vinyl-benzene. © 2007 BCREC UNDIP. All rights reserved.[Presented at Symposium and Congress of MKICS 2007, 18-19 April 2007, Semarang, Indonesia][How to Cite: E. Suyenty, H. Sentosa, M. Agustine, S. Anwar, A. Lie, E. Sutanto. (2007. Catalyst in Basic Oleochemicals. Bulletin of Chemical Reaction Engineering and Catalysis, 2 (2-3: 22-31.  doi:10.9767/bcrec.2.2-3.6.22-31][How to Link/DOI: http://dx.doi.org/10.9767/bcrec.2.2-3.6.22-31 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/6

  12. Finding Furfural Hydrogenation Catalysts via Predictive Modelling.

    Science.gov (United States)

    Strassberger, Zea; Mooijman, Maurice; Ruijter, Eelco; Alberts, Albert H; Maldonado, Ana G; Orru, Romano V A; Rothenberg, Gadi

    2010-09-10

    We combine multicomponent reactions, catalytic performance studies and predictive modelling to find transfer hydrogenation catalysts. An initial set of 18 ruthenium-carbene complexes were synthesized and screened in the transfer hydrogenation of furfural to furfurol with isopropyl alcohol complexes gave varied yields, from 62% up to >99.9%, with no obvious structure/activity correlations. Control experiments proved that the carbene ligand remains coordinated to the ruthenium centre throughout the reaction. Deuterium-labelling studies showed a secondary isotope effect (k(H):k(D)=1.5). Further mechanistic studies showed that this transfer hydrogenation follows the so-called monohydride pathway. Using these data, we built a predictive model for 13 of the catalysts, based on 2D and 3D molecular descriptors. We tested and validated the model using the remaining five catalysts (cross-validation, R(2)=0.913). Then, with this model, the conversion and selectivity were predicted for four completely new ruthenium-carbene complexes. These four catalysts were then synthesized and tested. The results were within 3% of the model's predictions, demonstrating the validity and value of predictive modelling in catalyst optimization.

  13. Finding Furfural Hydrogenation Catalysts via Predictive Modelling

    Science.gov (United States)

    Strassberger, Zea; Mooijman, Maurice; Ruijter, Eelco; Alberts, Albert H; Maldonado, Ana G; Orru, Romano V A; Rothenberg, Gadi

    2010-01-01

    Abstract We combine multicomponent reactions, catalytic performance studies and predictive modelling to find transfer hydrogenation catalysts. An initial set of 18 ruthenium-carbene complexes were synthesized and screened in the transfer hydrogenation of furfural to furfurol with isopropyl alcohol complexes gave varied yields, from 62% up to >99.9%, with no obvious structure/activity correlations. Control experiments proved that the carbene ligand remains coordinated to the ruthenium centre throughout the reaction. Deuterium-labelling studies showed a secondary isotope effect (kH:kD=1.5). Further mechanistic studies showed that this transfer hydrogenation follows the so-called monohydride pathway. Using these data, we built a predictive model for 13 of the catalysts, based on 2D and 3D molecular descriptors. We tested and validated the model using the remaining five catalysts (cross-validation, R2=0.913). Then, with this model, the conversion and selectivity were predicted for four completely new ruthenium-carbene complexes. These four catalysts were then synthesized and tested. The results were within 3% of the model’s predictions, demonstrating the validity and value of predictive modelling in catalyst optimization. PMID:23193388

  14. ALKALI RESISTANT CATALYST

    DEFF Research Database (Denmark)

    2008-01-01

    The present invention concerns the selective removal of nitrogen oxides (NOx) from gasses. In particular, the invention concerns a process, a catalyst and the use of a catalyst for the selective removal of nitrogen oxides in the presence of ammonia from gases containing a significant amount...... of alkali metal and/or alkali-earth compounds which process comprises using a catalyst combined of (i) a formed porous superacidic support, said superacidic support having an Hammett acidity stronger than Ho=-12, and (ii) a metal oxide catalytic component deposited on said superacidic support selected from...

  15. Rational design of molecularly imprinted polymer: the choice of cross-linker.

    Science.gov (United States)

    Muhammad, Turghun; Nur, Zohre; Piletska, Elena V; Yimit, Osmanjan; Piletsky, Sergey A

    2012-06-07

    The paper describes a rational approach for the selection of cross-linkers during the development of molecularly imprinted polymers (MIPs). As a model system for this research MIPs specific for the drug zidovudine (AZT) were designed and tested. Three cross-linkers trimethylolpropane trimethacrylate (TRIM), ethylene glycol dimethacrylate (EGDMA) and divinylbenzene (DVB) were studied. The analogue of zidovudine (AZT) ester (AZT-ES) was used as a dummy template. The imprinting factors for all of the polymers in the static adsorption experiments were calculated. The data on the AZT adsorption by control polymers (CP), which were prepared with different cross-linkers without a functional monomer, was also analyzed. DVB was found to be more inert towards zidovudine than EGDMA and TRIM, which was confirmed by both molecular modelling and adsorption experiments. It was demonstrated that DVB-based polymers had a higher imprinting factor (I = 1.85) compared with other tested cross-linked polymers. It was suggested that the selection of the cross-linker should be based on the strength of the interaction with the template: the cross-linker which displays lower binding of the template should be preferential because it generates MIPs with lower non-specific binding and a higher imprinting factor, and therefore specificity. Which cross-linker to use for the preparation of any particular MIP can be determined by analysis of the interactions between the cross-linker and template. This could be done either virtually using computational modelling or by template adsorption using a small library of polymers prepared using different cross-linkers.

  16. TECHNOLOGY DEVELOPMENT FOR IRON FISCHER-TROPSCH CATALYSTS

    Energy Technology Data Exchange (ETDEWEB)

    Davis, B.H.

    1998-07-22

    The goal of the proposed work described in this Final Report was the development of iron-based Fischer-Tropsch catalysts that combined high activity, selectivity and life with physical robustness for slurry phase reactors that will produce either low-alpha or high-alpha products. The work described here has optimized the catalyst composition and pretreatment operation for a low-alpha catalyst. In parallel, work has been conducted to design a high-alpha iron catalyst that is suitable for slurry phase synthesis. Studies have been conducted to define the chemical phases present at various stages of the pretreatment and synthesis stages and to define the course of these changes. The oxidation/reduction cycles that are anticipated to occur in large, commercial reactors have been studied at the laboratory scale. Catalyst performance has been determined for catalysts synthesized in this program for activity, selectivity and aging characteristics.

  17. Theoretical studies of homogeneous catalysts mimicking nitrogenase.

    Science.gov (United States)

    Sgrignani, Jacopo; Franco, Duvan; Magistrato, Alessandra

    2011-01-10

    The conversion of molecular nitrogen to ammonia is a key biological and chemical process and represents one of the most challenging topics in chemistry and biology. In Nature the Mo-containing nitrogenase enzymes perform nitrogen 'fixation' via an iron molybdenum cofactor (FeMo-co) under ambient conditions. In contrast, industrially, the Haber-Bosch process reduces molecular nitrogen and hydrogen to ammonia with a heterogeneous iron catalyst under drastic conditions of temperature and pressure. This process accounts for the production of millions of tons of nitrogen compounds used for agricultural and industrial purposes, but the high temperature and pressure required result in a large energy loss, leading to several economic and environmental issues. During the last 40 years many attempts have been made to synthesize simple homogeneous catalysts that can activate dinitrogen under the same mild conditions of the nitrogenase enzymes. Several compounds, almost all containing transition metals, have been shown to bind and activate N₂ to various degrees. However, to date Mo(N₂)(HIPTN)₃N with (HIPTN)₃N= hexaisopropyl-terphenyl-triamidoamine is the only compound performing this process catalytically. In this review we describe how Density Functional Theory calculations have been of help in elucidating the reaction mechanisms of the inorganic compounds that activate or fix N₂. These studies provided important insights that rationalize and complement the experimental findings about the reaction mechanisms of known catalysts, predicting the reactivity of new potential catalysts and helping in tailoring new efficient catalytic compounds.

  18. Theoretical Studies of Homogeneous Catalysts Mimicking Nitrogenase

    Directory of Open Access Journals (Sweden)

    Alessandra Magistrato

    2011-01-01

    Full Text Available The conversion of molecular nitrogen to ammonia is a key biological and chemical process and represents one of the most challenging topics in chemistry and biology. In Nature the Mo-containing nitrogenase enzymes perform nitrogen ‘fixation’ via an iron molybdenum cofactor (FeMo-co under ambient conditions. In contrast, industrially, the Haber-Bosch process reduces molecular nitrogen and hydrogen to ammonia with a heterogeneous iron catalyst under drastic conditions of temperature and pressure. This process accounts for the production of millions of tons of nitrogen compounds used for agricultural and industrial purposes, but the high temperature and pressure required result in a large energy loss, leading to several economic and environmental issues. During the last 40 years many attempts have been made to synthesize simple homogeneous catalysts that can activate dinitrogen under the same mild conditions of the nitrogenase enzymes. Several compounds, almost all containing transition metals, have been shown to bind and activate N2 to various degrees. However, to date Mo(N2(HIPTN3N with (HIPTN3N= hexaisopropyl-terphenyl-triamidoamine is the only compound performing this process catalytically. In this review we describe how Density Functional Theory calculations have been of help in elucidating the reaction mechanisms of the inorganic compounds that activate or fix N2. These studies provided important insights that rationalize and complement the experimental findings about the reaction mechanisms of known catalysts, predicting the reactivity of new potential catalysts and helping in tailoring new efficient catalytic compounds.

  19. Catalyst for microelectromechanical systems microreactors

    Science.gov (United States)

    Morse, Jeffrey D [Martinez, CA; Sopchak, David A [Livermore, CA; Upadhye, Ravindra S [Pleasanton, CA; Reynolds, John G [San Ramon, CA; Satcher, Joseph H [Patterson, CA; Gash, Alex E [Brentwood, CA

    2010-06-29

    A microreactor comprising a silicon wafer, a multiplicity of microchannels in the silicon wafer, and a catalyst coating the microchannels. In one embodiment the catalyst coating the microchannels comprises a nanostructured material. In another embodiment the catalyst coating the microchannels comprises an aerogel. In another embodiment the catalyst coating the microchannels comprises a solgel. In another embodiment the catalyst coating the microchannels comprises carbon nanotubes.

  20. Solid, double-metal cyanide catalysts for synthesis of ...

    Indian Academy of Sciences (India)

    Sci. Vol. 126, No. 2, March 2014, pp. 499–509. c Indian Academy of Sciences. Solid, double-metal cyanide catalysts for ... drimers, HPs have a highly branched structural design ... geneous catalysts and corrosion of the reactor lin- ... Carbon dioxide is a greenhouse gas. .... polymer product was reprecipitated from the liquid.

  1. Epoxidation catalyst and process

    Science.gov (United States)

    Linic, Suljo; Christopher, Phillip

    2010-10-26

    Disclosed herein is a catalytic method of converting alkenes to epoxides. This method generally includes reacting alkenes with oxygen in the presence of a specific silver catalyst under conditions suitable to produce a yield of the epoxides. The specific silver catalyst is a silver nanocrystal having a plurality of surface planes, a substantial portion of which is defined by Miller indices of (100). The reaction is performed by charging a suitable reactor with this silver catalyst and then feeding the reactants to the reactor under conditions to carry out the reaction. The reaction may be performed in batch, or as a continuous process that employs a recycle of any unreacted alkenes. The specific silver catalyst has unexpectedly high selectivity for epoxide products. Consequently, this general method (and its various embodiments) will result in extraordinarily high epoxide yields heretofore unattainable.

  2. Towards the design of new and improved drilling fluid additives using molecular dynamics simulations

    Directory of Open Access Journals (Sweden)

    Richard L. Anderson

    2010-03-01

    Full Text Available During exploration for oil and gas, a technical drilling fluid is used to lubricate the drill bit, maintain hydrostatic pressure, transmit sensor readings, remove rock cuttings and inhibit swelling of unstable clay based reactive shale formations. Increasing environmental awareness and resulting legislation has led to the search for new, improved biodegradable drilling fluid components. In the case of additives for clay swelling inhibition, an understanding of how existing effective additives interact with clays must be gained to allow the design of improved molecules. Owing to the disordered nature and nanoscopic dimension of the interlayer pores of clay minerals, computer simulations have become an increasingly useful tool for studying clay-swelling inhibitor interactions. In this work we briefly review the history of the development of technical drilling fluids, the environmental impact of drilling fluids and the use of computer simulations to study the interactions between clay minerals and swelling inhibitors. We report on results from some recent large-scale molecular dynamics simulation studies on low molecular weight water-soluble macromolecular inhibitor molecules. The structure and interactions of poly(propylene oxide-diamine, poly(ethylene glycol and poly(ethylene oxide-diacrylate inhibitor molecules with montmorillonite clay are studied.Durante a exploração de óleo e gás um fluido de perfuração é usado para lubrificar 'bit' da perfuradora, manter a pressão hidrostática, transmitir sensores de leitura, remover resíduos da rocha e inibir o inchamento da argila instável baseada nas formações dos folhelhos. O aumento das preocupações ambientais bem como a legislação resultante levou à procura de novos fluidos de perfuração com componentes biodegradáveis. No caso dos aditivos para inibir o inchamento das argilas o entendimento das interações entre os aditivos e as argilas tem que ser adquirido para permitir o

  3. Molecular Electrical Doping of Organic Semiconductors: Fundamental Mechanisms and Emerging Dopant Design Rules.

    Science.gov (United States)

    Salzmann, Ingo; Heimel, Georg; Oehzelt, Martin; Winkler, Stefanie; Koch, Norbert

    2016-03-15

    Today's information society depends on our ability to controllably dope inorganic semiconductors, such as silicon, thereby tuning their electrical properties to application-specific demands. For optoelectronic devices, organic semiconductors, that is, conjugated polymers and molecules, have emerged as superior alternative owing to the ease of tuning their optical gap through chemical variability and their potential for low-cost, large-area processing on flexible substrates. There, the potential of molecular electrical doping for improving the performance of, for example, organic light-emitting devices or organic solar cells has only recently been established. The doping efficiency, however, remains conspicuously low, highlighting the fact that the underlying mechanisms of molecular doping in organic semiconductors are only little understood compared with their inorganic counterparts. Here, we review the broad range of phenomena observed upon molecularly doping organic semiconductors and identify two distinctly different scenarios: the pairwise formation of both organic semiconductor and dopant ions on one hand and the emergence of ground state charge transfer complexes between organic semiconductor and dopant through supramolecular hybridization of their respective frontier molecular orbitals on the other hand. Evidence for the occurrence of these two scenarios is subsequently discussed on the basis of the characteristic and strikingly different signatures of the individual species involved in the respective doping processes in a variety of spectroscopic techniques. The critical importance of a statistical view of doping, rather than a bimolecular picture, is then highlighted by employing numerical simulations, which reveal one of the main differences between inorganic and organic semiconductors to be their respective density of electronic states and the doping induced changes thereof. Engineering the density of states of doped organic semiconductors, the Fermi

  4. Chemomimetic biocatalysis: exploiting the synthetic potential of cofactor-dependent enzymes to create new catalysts.

    Science.gov (United States)

    Prier, Christopher K; Arnold, Frances H

    2015-11-11

    Despite the astonishing breadth of enzymes in nature, no enzymes are known for many of the valuable catalytic transformations discovered by chemists. Recent work in enzyme design and evolution, however, gives us good reason to think that this will change. We describe a chemomimetic biocatalysis approach that draws from small-molecule catalysis and synthetic chemistry, enzymology, and molecular evolution to discover or create enzymes with non-natural reactivities. We illustrate how cofactor-dependent enzymes can be exploited to promote reactions first established with related chemical catalysts. The cofactors can be biological, or they can be non-biological to further expand catalytic possibilities. The ability of enzymes to amplify and precisely control the reactivity of their cofactors together with the ability to optimize non-natural reactivity by directed evolution promises to yield exceptional catalysts for challenging transformations that have no biological counterparts.

  5. Development of a model for the rational design of molecular imprinted polymer: Computational approach for combined molecular dynamics/quantum mechanics calculations

    International Nuclear Information System (INIS)

    Dong Cunku; Li Xin; Guo Zechong; Qi Jingyao

    2009-01-01

    A new rational approach for the preparation of molecularly imprinted polymer (MIP) based on the combination of molecular dynamics (MD) simulations and quantum mechanics (QM) calculations is described in this work. Before performing molecular modeling, a virtual library of functional monomers was created containing forty frequently used monomers. The MD simulations were first conducted to screen the top three monomers from virtual library in each porogen-acetonitrile, chloroform and carbon tetrachloride. QM simulations were then performed with an aim to select the optimum monomer and progen solvent in which the QM simulations were carried out; the monomers giving the highest binding energies were chosen as the candidate to prepare MIP in its corresponding solvent. The acetochlor, a widely used herbicide, was chosen as the target analyte. According to the theoretical calculation results, the MIP with acetochlor as template was prepared by emulsion polymerization method using N,N-methylene bisacrylamide (MBAAM) as functional monomer and divinylbenzene (DVB) as cross-linker in chloroform. The synthesized MIP was then tested by equilibrium-adsorption method, and the MIP demonstrated high removal efficiency to the acetochlor. Mulliken charge distribution and 1 H NMR spectroscopy of the synthesized MIP provided insight on the nature of recognition during the imprinting process probing the governing interactions for selective binding site formation at a molecular level. We think the computer simulation method first proposed in this paper is a novel and reliable method for the design and synthesis of MIP.

  6. Tumor Heterogeneity: Mechanisms and Bases for a Reliable Application of Molecular Marker Design

    Science.gov (United States)

    Diaz-Cano, Salvador J.

    2012-01-01

    Tumor heterogeneity is a confusing finding in the assessment of neoplasms, potentially resulting in inaccurate diagnostic, prognostic and predictive tests. This tumor heterogeneity is not always a random and unpredictable phenomenon, whose knowledge helps designing better tests. The biologic reasons for this intratumoral heterogeneity would then be important to understand both the natural history of neoplasms and the selection of test samples for reliable analysis. The main factors contributing to intratumoral heterogeneity inducing gene abnormalities or modifying its expression include: the gradient ischemic level within neoplasms, the action of tumor microenvironment (bidirectional interaction between tumor cells and stroma), mechanisms of intercellular transference of genetic information (exosomes), and differential mechanisms of sequence-independent modifications of genetic material and proteins. The intratumoral heterogeneity is at the origin of tumor progression and it is also the byproduct of the selection process during progression. Any analysis of heterogeneity mechanisms must be integrated within the process of segregation of genetic changes in tumor cells during the clonal expansion and progression of neoplasms. The evaluation of these mechanisms must also consider the redundancy and pleiotropism of molecular pathways, for which appropriate surrogate markers would support the presence or not of heterogeneous genetics and the main mechanisms responsible. This knowledge would constitute a solid scientific background for future therapeutic planning. PMID:22408433

  7. RNAiFold: a web server for RNA inverse folding and molecular design.

    Science.gov (United States)

    Garcia-Martin, Juan Antonio; Clote, Peter; Dotu, Ivan

    2013-07-01

    Synthetic biology and nanotechnology are poised to make revolutionary contributions to the 21st century. In this article, we describe a new web server to support in silico RNA molecular design. Given an input target RNA secondary structure, together with optional constraints, such as requiring GC-content to lie within a certain range, requiring the number of strong (GC), weak (AU) and wobble (GU) base pairs to lie in a certain range, the RNAiFold web server determines one or more RNA sequences, whose minimum free-energy secondary structure is the target structure. RNAiFold provides access to two servers: RNA-CPdesign, which applies constraint programming, and RNA-LNSdesign, which applies the large neighborhood search heuristic; hence, it is suitable for larger input structures. Both servers can also solve the RNA inverse hybridization problem, i.e. given a representation of the desired hybridization structure, RNAiFold returns two sequences, whose minimum free-energy hybridization is the input target structure. The web server is publicly accessible at http://bioinformatics.bc.edu/clotelab/RNAiFold, which provides access to two specialized servers: RNA-CPdesign and RNA-LNSdesign. Source code for the underlying algorithms, implemented in COMET and supported on linux, can be downloaded at the server website.

  8. Design of a multi-purpose fragment screening library using molecular complexity and orthogonal diversity metrics

    Science.gov (United States)

    Lau, Wan F.; Withka, Jane M.; Hepworth, David; Magee, Thomas V.; Du, Yuhua J.; Bakken, Gregory A.; Miller, Michael D.; Hendsch, Zachary S.; Thanabal, Venkataraman; Kolodziej, Steve A.; Xing, Li; Hu, Qiyue; Narasimhan, Lakshmi S.; Love, Robert; Charlton, Maura E.; Hughes, Samantha; van Hoorn, Willem P.; Mills, James E.

    2011-07-01

    Fragment Based Drug Discovery (FBDD) continues to advance as an efficient and alternative screening paradigm for the identification and optimization of novel chemical matter. To enable FBDD across a wide range of pharmaceutical targets, a fragment screening library is required to be chemically diverse and synthetically expandable to enable critical decision making for chemical follow-up and assessing new target druggability. In this manuscript, the Pfizer fragment library design strategy which utilized multiple and orthogonal metrics to incorporate structure, pharmacophore and pharmacological space diversity is described. Appropriate measures of molecular complexity were also employed to maximize the probability of detection of fragment hits using a variety of biophysical and biochemical screening methods. In addition, structural integrity, purity, solubility, fragment and analog availability as well as cost were important considerations in the selection process. Preliminary analysis of primary screening results for 13 targets using NMR Saturation Transfer Difference (STD) indicates the identification of uM-mM hits and the uniqueness of hits at weak binding affinities for these targets.

  9. Tumor Heterogeneity: Mechanisms and Bases for a Reliable Application of Molecular Marker Design

    Directory of Open Access Journals (Sweden)

    Salvador J. Diaz-Cano

    2012-02-01

    Full Text Available Tumor heterogeneity is a confusing finding in the assessment of neoplasms, potentially resulting in inaccurate diagnostic, prognostic and predictive tests. This tumor heterogeneity is not always a random and unpredictable phenomenon, whose knowledge helps designing better tests. The biologic reasons for this intratumoral heterogeneity would then be important to understand both the natural history of neoplasms and the selection of test samples for reliable analysis. The main factors contributing to intratumoral heterogeneity inducing gene abnormalities or modifying its expression include: the gradient ischemic level within neoplasms, the action of tumor microenvironment (bidirectional interaction between tumor cells and stroma, mechanisms of intercellular transference of genetic information (exosomes, and differential mechanisms of sequence-independent modifications of genetic material and proteins. The intratumoral heterogeneity is at the origin of tumor progression and it is also the byproduct of the selection process during progression. Any analysis of heterogeneity mechanisms must be integrated within the process of segregation of genetic changes in tumor cells during the clonal expansion and progression of neoplasms. The evaluation of these mechanisms must also consider the redundancy and pleiotropism of molecular pathways, for which appropriate surrogate markers would support the presence or not of heterogeneous genetics and the main mechanisms responsible. This knowledge would constitute a solid scientific background for future therapeutic planning.

  10. Molecular Design of Bioinspired Nanostructures for Biomedical Applications: Synthesis, Self-Assembly and Functional Properties

    Science.gov (United States)

    Xu, Hesheng Victor; Zheng, Xin Ting; Mok, Beverly Yin Leng; Ibrahim, Salwa Ali; Yu, Yong; Tan, Yen Nee

    2016-08-01

    Biomolecules are the nanoscale building blocks of cells, which play multifaceted roles in the critical biological processes such as biomineralization in a living organism. In these processes, the biological molecules such as protein and nucleic acids use their exclusive biorecognition properties enabled from their unique chemical composition, shape and function to initiate a cascade of cellular events. The exceptional features of these biomolecules, coupled with the recent advancement in nanotechnology, have led to the emergence of a new research field that focuses on the molecular design of bioinspired nanostructures that inherit the extraordinary function of natural biomaterials. These “bioinspired” nanostructures could be formulated by biomimetic approaches through either self-assembling of biomolecules or acting as a biomolecular template/precursor to direct the synthesis of nanocomposite. In either situation, the resulting nanomaterials exhibit phenomenal biocompatibility, superb aqueous solubility and excellent colloidal stability, branding them exceptionally desirable for both in vitro and in vivo biomedical applications. In this review, we will present the recent developments in the preparation of “bioinspired” nanostructures through biomimetic self-assembly and biotemplating synthesis, as well as highlight their functional properties and potential applications in biomedical diagnostics and therapeutic delivery. Lastly, we will conclude this topic with some personal perspective on the challenges and future outlooks of the “bioinspired” nanostructures for nanomedicine.

  11. New catalysts for exhaust gas cleaning

    Energy Technology Data Exchange (ETDEWEB)

    Haerkoenen, M [Kemira Metalkat Oy, Oulu (Finland)

    1997-12-31

    Major challenge for future catalyst systems was to develop thermally more stable washcoats for close coupled operating conditions and for engines operating under high speed and load conditions. To design these future emission systems extensive research and development was undertaken to develop methods to disperse and stabilize the key catalytic materials for operation at much higher temperatures. Second priority was to design catalysts that are more effective under low temperature exhaust conditions and have improved oxygen storage properties in the washcoats. Incorporating new materials and modified preparation technology a new generation of metallic catalyst formulations emerged, those being trimetallic K6 (Pt:Pd:Rh and bimetallic K7) (Pd+Pd:Rh). The target was to combine the best property of Pt:Rh (good NO{sub x} reduction) with that of the good HC oxidation activity of Pd and to ensure that precious metal/support interactions were positively maintained. Both K6 and K7 concepts contain special catalyst structures with optimized washcoat performance which can be brick converter configuration. Improvement in light-off, thermal stability and transient performance with these new catalyst formulations have clearly been shown in both laboratory and vehicle testing. (author) (20 refs.)

  12. New catalysts for exhaust gas cleaning

    Energy Technology Data Exchange (ETDEWEB)

    Haerkoenen, M. [Kemira Metalkat Oy, Oulu (Finland)

    1996-12-31

    Major challenge for future catalyst systems was to develop thermally more stable washcoats for close coupled operating conditions and for engines operating under high speed and load conditions. To design these future emission systems extensive research and development was undertaken to develop methods to disperse and stabilize the key catalytic materials for operation at much higher temperatures. Second priority was to design catalysts that are more effective under low temperature exhaust conditions and have improved oxygen storage properties in the washcoats. Incorporating new materials and modified preparation technology a new generation of metallic catalyst formulations emerged, those being trimetallic K6 (Pt:Pd:Rh and bimetallic K7) (Pd+Pd:Rh). The target was to combine the best property of Pt:Rh (good NO{sub x} reduction) with that of the good HC oxidation activity of Pd and to ensure that precious metal/support interactions were positively maintained. Both K6 and K7 concepts contain special catalyst structures with optimized washcoat performance which can be brick converter configuration. Improvement in light-off, thermal stability and transient performance with these new catalyst formulations have clearly been shown in both laboratory and vehicle testing. (author) (20 refs.)

  13. Estimation and Uncertainty Analysis of Flammability Properties for Computer-aided molecular design of working fluids for thermodynamic cycles

    DEFF Research Database (Denmark)

    Frutiger, Jerome; Abildskov, Jens; Sin, Gürkan

    Computer Aided Molecular Design (CAMD) is an important tool to generate, test and evaluate promising chemical products. CAMD can be used in thermodynamic cycle for the design of pure component or mixture working fluids in order to improve the heat transfer capacity of the system. The safety......, there is no information about the reliability of the data. Furthermore, the global optimality of the GC parameters estimation is often not ensured....

  14. Global sensitivity analysis of computer-aided molecular design problem for the development of novel working fluids for power cycles

    DEFF Research Database (Denmark)

    Frutiger, Jerome; Abildskov, Jens; Sin, Gürkan

    2016-01-01

    This study compares two methods for global sensitivity analysis as a new approach for the identification and ranking of target properties in molecular design problems: A modified Morris Screening technique and Monte Carlo based standard regression. The two methodologies are highlighted in a case ...

  15. Design of a reflex time-of-flight mass spectrometer for the study of the desorption of molecular ions

    International Nuclear Information System (INIS)

    Riggi, F.

    1991-01-01

    A reflex time-of-flight mass spectrometer for the study of the desorption and dissociation of molecular ions has been designed. A general overview of the instrument is reported, together with the different experimental aspects of the technique. These include mechanical and vacuum solutions, secondary ion optics in the electrostatic mirror, electronics, data acquisition and analysis

  16. Tritium labelling of molecules constrained in microporous catalysts

    International Nuclear Information System (INIS)

    Long, M.A.; Garnett, J.L.; Than, Chit

    1989-01-01

    The use of microporous aluminophosphate catalysts for exchange between tritium gas or tritiated water and organic substrates is described. The results are compared with those of microporous zeolites. Results are interpreted in terms of the influence of the constraints imposed on molecular configuration by the catalyst pore geometry. The use of these porous structures for minimising byproduct formation in radiation induced labelling processes with tritium gas is described. (author). 10 refs.; 3 tabs

  17. Bifunctional catalysts for the direct production of liquid fuels from syngas

    NARCIS (Netherlands)

    Sartipi, S.

    2014-01-01

    Design and development of catalyst formulations that maximize the direct production of liquid fuels by combining Fischer-Tropsch synthesis (FTS), hydrocarbon cracking, and isomerization into one single catalyst particle (bifunctional FTS catalyst) have been investigated in this thesis. To achieve

  18. Development of Sulfur and Carbon Tolerant Reforming Alloy Catalysts Aided Fundamental Atomistic Insights

    Energy Technology Data Exchange (ETDEWEB)

    Suljo Linic

    2008-12-31

    Current hydrocarbon reforming catalysts suffer from rapid carbon and sulfur poisoning. Even though there is a tremendous incentive to develop more efficient catalysts, these materials are currently formulated using inefficient trial and error experimental approaches. We have utilized a hybrid experimental/theoretical approach, combining quantum Density Functional Theory (DFT) calculations and various state-of-the-art experimental tools, to formulate carbon tolerant reforming catalysts. We have employed DFT calculations to develop molecular insights into the elementary chemical transformations that lead to carbon poisoning of Ni catalysts. Based on the obtained molecular insights, we have identified, using DFT quantum calculation, various Ni alloy catalysts as potential carbon tolerant reforming catalysts. The alloy catalysts were synthesized and tested in steam reforming and partial oxidation of methane, propane, and isooctane. We demonstrated that the alloy catalysts are much more carbon-tolerant than monometallic Ni catalysts under nearly stoichiometric steam-to-carbon ratios. Under these conditions, monometallic Ni is rapidly poisoned by sp2 carbon deposits. The research approach is distinguished by two characteristics: (a) knowledge-based, bottomup approach, compared to the traditional trial and error approach, allows for a more efficient and systematic discovery of improved catalysts. (b) the focus is on exploring alloy materials which have been largely unexplored as potential reforming catalysts.

  19. Photoinduced self-assembly to lanthanide-containing molybdenum-blue superclusters and molecular design

    Energy Technology Data Exchange (ETDEWEB)

    Yamase, Toshihiro [Chemical Resources Laboratory, Tokyo Institute of Technology, R1-21, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan) and Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi 332-0012 (Japan)]. E-mail: tyamase@res.titech.ac.jp; Ishikawa, Eri [Chemical Resources Laboratory, Tokyo Institute of Technology, R1-21, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan); Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi 332-0012 (Japan); Abe, Yohko [Chemical Resources Laboratory, Tokyo Institute of Technology, R1-21, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan); Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi 332-0012 (Japan); Yano, Yutaka [Chemical Resources Laboratory, Tokyo Institute of Technology, R1-21, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan); Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi 332-0012 (Japan)

    2006-02-09

    }. Number of the {l_brace}Mo{sub 1}(La){r_brace}and {l_brace}Mo{sub 11}(La){r_brace} sub-building-blocks in the building-block sequence for the ring is important for both shape and size of nano-rings, which is governed by the manipulation of Ln{sup 3+} (with a variety of ionic radius) and electron donors. It is indicated that a variety of the combination of sub-building-blocks with different molecular curvatures among {l_brace}Mo{sub 1}(La){r_brace}, {l_brace}Mo{sub 11}(La){r_brace}, {l_brace}Mo{sub 1}{r_brace}, and {l_brace}Mo{sub 11}{r_brace} is a promising method for the molecular design of nano-rings in both the chemical versatility and the functionality.

  20. Sulfur Deactivation of NOx Storage Catalysts: A Multiscale Modeling Approach

    Directory of Open Access Journals (Sweden)

    Rankovic N.

    2013-09-01

    Full Text Available Lean NOx Trap (LNT catalysts, a promising solution for reducing the noxious nitrogen oxide emissions from the lean burn and Diesel engines, are technologically limited by the presence of sulfur in the exhaust gas stream. Sulfur stemming from both fuels and lubricating oils is oxidized during the combustion event and mainly exists as SOx (SO2 and SO3 in the exhaust. Sulfur oxides interact strongly with the NOx trapping material of a LNT to form thermodynamically favored sulfate species, consequently leading to the blockage of NOx sorption sites and altering the catalyst operation. Molecular and kinetic modeling represent a valuable tool for predicting system behavior and evaluating catalytic performances. The present paper demonstrates how fundamental ab initio calculations can be used as a valuable source for designing kinetic models developed in the IFP Exhaust library, intended for vehicle simulations. The concrete example we chose to illustrate our approach was SO3 adsorption on the model NOx storage material, BaO. SO3 adsorption was described for various sites (terraces, surface steps and kinks and bulk for a closer description of a real storage material. Additional rate and sensitivity analyses provided a deeper understanding of the poisoning phenomena.

  1. Designing molecular dynamics simulations to shift populations of the conformational states of calmodulin.

    Directory of Open Access Journals (Sweden)

    Ayse Ozlem Aykut

    Full Text Available We elucidate the mechanisms that lead to population shifts in the conformational states of calcium-loaded calmodulin (Ca(2+-CaM. We design extensive molecular dynamics simulations to classify the effects that are responsible for adopting occupied conformations available in the ensemble of NMR structures. Electrostatic interactions amongst the different regions of the protein and with its vicinal water are herein mediated by lowering the ionic strength or the pH. Amino acid E31, which is one of the few charged residues whose ionization state is highly sensitive to pH differences in the physiological range, proves to be distinctive in its control of population shifts. E31A mutation at low ionic strength results in a distinct change from an extended to a compact Ca(2+-CaM conformation within tens of nanoseconds, that otherwise occur on the time scales of microseconds. The kinked linker found in this particular compact form is observed in many of the target-bound forms of Ca(2+-CaM, increasing the binding affinity. This mutation is unique in controlling C-lobe dynamics by affecting the fluctuations between the EF-hand motif helices. We also monitor the effect of the ionic strength on the conformational multiplicity of Ca(2+-CaM. By lowering the ionic strength, the tendency of nonspecific anions in water to accumulate near the protein surface increases, especially in the vicinity of the linker. The change in the distribution of ions in the vicinal layer of water allows N- and C- lobes to span a wide variety of relative orientations that are otherwise not observed at physiological ionic strength. E31 protonation restores the conformations associated with physiological environmental conditions even at low ionic strength.

  2. Synthesis and Evaluation of CO2 Thickeners Designed with Molecular Modeling

    Energy Technology Data Exchange (ETDEWEB)

    Robert Enick; Erick Beckman; J. Karl Johnson

    2009-08-31

    The objective of this research was to use molecular modeling techniques, coupled with our prior experimental results, to design, synthesize and evaluate inexpensive, non-fluorous carbon dioxide thickening agents. The first type of thickener that was considered was associating polymers. Typically, these thickeners are copolymers that contain a highly CO{sub 2}-philic monomer, and a small concentration of a CO{sub 2}-phobic associating monomer. Yale University was solely responsible for the synthesis of a second type of thickener; small, hydrogen bonding compounds. These molecules have a core that contains one or more hydrogen-bonding groups, such as urea or amide groups. Non-fluorous, CO{sub 2}-philic functional groups were attached to the hydrogen bonding core of the compound to impart CO{sub 2} stability and macromolecular stability to the linear 'stack' of these compounds. The third type of compound initially considered for this investigation was CO{sub 2}-soluble surfactants. These surfactants contain conventional ionic head groups and composed of CO{sub 2}-philic oligomers (short polymers) or small compounds (sugar acetates) previously identified by our research team. Mobility reduction could occur as these surfactant solutions contacted reservoir brine and formed mobility control foams in-situ. The vast majority of the work conducted in this study was devoted to the copolymeric thickeners and the small hydrogen-bonding thickeners; these thickeners were intended to dissolve completely in CO{sub 2} and increase the fluid viscosity. A small but important amount of work was done establishing the groundwork for CO{sub 2}-soluble surfactants that reduced mobility by generating foams in-situ as the CO{sub 2}+surfactant solution mixed with in-situ brine.

  3. Design and evaluation of basic standard encryption algorithm modules using nanosized complementary metal oxide semiconductor molecular circuits

    Science.gov (United States)

    Masoumi, Massoud; Raissi, Farshid; Ahmadian, Mahmoud; Keshavarzi, Parviz

    2006-01-01

    We are proposing that the recently proposed semiconductor-nanowire-molecular architecture (CMOL) is an optimum platform to realize encryption algorithms. The basic modules for the advanced encryption standard algorithm (Rijndael) have been designed using CMOL architecture. The performance of this design has been evaluated with respect to chip area and speed. It is observed that CMOL provides considerable improvement over implementation with regular CMOS architecture even with a 20% defect rate. Pseudo-optimum gate placement and routing are provided for Rijndael building blocks and the possibility of designing high speed, attack tolerant and long key encryptions are discussed.

  4. Design of a core–shell Pt–SiO2 catalyst in a reverse microemulsion system: Distinctive kinetics on CO oxidation at low temperature

    KAUST Repository

    Al Mana, Noor

    2016-06-28

    The mechanism of formation of Pt@SiO2 as a model of core–shell nanoparticles via water-in-oil reverse microemulsions was studied in detail. By controlling the time of growth of Pt precursors, Pt(OH)x, after hydrolysis in NH3 aq. before adding SiO2 precursor (TEOS), Pt nanoparticles with a narrow size distribution were produced, from ultrafine metal nanoparticles (<1 nm) to 6 nm nanocrystals. Separately, the thickness of SiO2 was controllably synthesized from 1 to 15 nm to yield different Pt@SiO2 materials. The Pt@SiO2 core–shell catalysts exhibited a higher rate of CO oxidation by one order of magnitude with a positive order regarding CO pressure. The SiO2 shell did not perturb the Pt chemical nature, but it provided different coverage of CO in steady-state CO oxidation. © 2016 Elsevier Inc.

  5. Niobium, catalyst repair kit

    International Nuclear Information System (INIS)

    Tanabe, K.

    1991-01-01

    This paper reports that niobium oxides, when small amounts are added to known catalysts, enhance catalytic activity and selectivity and prolong catalyst life. Moreover, niobium oxides exhibit a pronounced effect as supports of metal or metal oxide catalysts. Recently we found that the surface acidity of hydrated niobium pentoxide, niobic acid (Nb 2 O 5 · nH 2 O), corresponds to the acidity of 70% sulfuric acid and exhibits high catalytic activity, selectivity, and stability for acid-catalyzed reactions in which water molecules participate. Although there are few differences in electronegativity and ionic radius between niobium and its neighbors in the periodic table, it is interesting that the promoter effect, support effect, and acidic nature of niobium compounds are quite different from those of compounds of the surrounding elements. Here we review what's known of niobium compounds from the viewpoint of their pronounced catalytic behavior

  6. Applications of the NRGsuite and the Molecular Docking Software FlexAID in Computational Drug Discovery and Design.

    Science.gov (United States)

    Morency, Louis-Philippe; Gaudreault, Francis; Najmanovich, Rafael

    2018-01-01

    Docking simulations help us understand molecular interactions. Here we present a hands-on tutorial to utilize FlexAID (Flexible Artificial Intelligence Docking), an open source molecular docking software between ligands such as small molecules or peptides and macromolecules such as proteins and nucleic acids. The tutorial uses the NRGsuite PyMOL plugin graphical user interface to set up and visualize docking simulations in real time as well as detect and refine target cavities. The ease of use of FlexAID and the NRGsuite combined with its superior performance relative to widely used docking software provides nonexperts with an important tool to understand molecular interactions with direct applications in structure-based drug design and virtual high-throughput screening.

  7. Dynamics of Catalyst Nanoparticles

    DEFF Research Database (Denmark)

    Hansen, Thomas Willum; Cavalca, Filippo; Wagner, Jakob Birkedal

    and pharmaceuticals, and the cleanup of exhaust from automobiles and stationary power plants. Sintering, or thermal deactivation, is an important mechanism for the loss of catalyst activity. In order to initiate a systematic study of the dynamics and sintering of nanoparticles, various catalytic systems have been...... under gas exposure, dynamic phenomena such as sintering and growth can be observed with sub-Ångstrøm resolution. Metal nanoparticles contain the active sites in heterogeneous catalysts, which are important for many industrial applications including the production of clean fuels, chemicals...

  8. Fuel cell catalyst degradation

    DEFF Research Database (Denmark)

    Arenz, Matthias; Zana, Alessandro

    2016-01-01

    Fuel cells are an important piece in our quest for a sustainable energy supply. Although there are several different types of fuel cells, the by far most popular is the proton exchange membrane fuel cell (PEMFC). Among its many favorable properties are a short start up time and a high power density...... increasing focus. Activity of the catalyst is important, but stability is essential. In the presented perspective paper, we review recent efforts to investigate fuel cell catalysts ex-situ in electrochemical half-cell measurements. Due to the amount of different studies, this review has no intention to give...

  9. Ordered meso- and macroporous perovskite oxide catalysts for emerging applications

    DEFF Research Database (Denmark)

    Arandiyan, Hamidreza; Wang, Yuan; Sun, Hongyu

    2018-01-01

    This feature article summarizes the recent progress in porous perovskite oxides as advanced catalysts for both energy conversion applications and various heterogeneous reactions. Recently, research has been focused on specifically designing porous perovskite materials so that large surface areas ...

  10. Application of 3D-QSAR, Pharmacophore, and Molecular Docking in the Molecular Design of Diarylpyrimidine Derivatives as HIV-1 Nonnucleoside Reverse Transcriptase Inhibitors.

    Science.gov (United States)

    Liu, Genyan; Wang, Wenjie; Wan, Youlan; Ju, Xiulian; Gu, Shuangxi

    2018-05-11

    Diarylpyrimidines (DAPYs), acting as HIV-1 nonnucleoside reverse transcriptase inhibitors (NNRTIs), have been considered to be one of the most potent drug families in the fight against acquired immunodeficiency syndrome (AIDS). To better understand the structural requirements of HIV-1 NNRTIs, three-dimensional quantitative structure⁻activity relationship (3D-QSAR), pharmacophore, and molecular docking studies were performed on 52 DAPY analogues that were synthesized in our previous studies. The internal and external validation parameters indicated that the generated 3D-QSAR models, including comparative molecular field analysis (CoMFA, q 2 = 0.679, R 2 = 0.983, and r pred 2 = 0.884) and comparative molecular similarity indices analysis (CoMSIA, q 2 = 0.734, R 2 = 0.985, and r pred 2 = 0.891), exhibited good predictive abilities and significant statistical reliability. The docking results demonstrated that the phenyl ring at the C₄-position of the pyrimidine ring was better than the cycloalkanes for the activity, as the phenyl group was able to participate in π⁻π stacking interactions with the aromatic residues of the binding site, whereas the cycloalkanes were not. The pharmacophore model and 3D-QSAR contour maps provided significant insights into the key structural features of DAPYs that were responsible for the activity. On the basis of the obtained information, a series of novel DAPY analogues of HIV-1 NNRTIs with potentially higher predicted activity was designed. This work might provide useful information for guiding the rational design of potential HIV-1 NNRTI DAPYs.

  11. Deactivation-resistant catalyst for selective catalyst reduction of NOx

    DEFF Research Database (Denmark)

    2011-01-01

    The present invention relates to a catalyst for selective catalytic reduction of NOx in alkali metal containing flue gas using ammonia as reductant, the catalyst comprising a surface with catalytically active sites, wherein the surface is at least partly coated with a coating comprising at least...... one metal oxide. In another aspect the present invention relates to the use of said catalyst and to a method of producing said catalyst. In addition, the present invention relates to a method of treating an catalyst for conferring thereon an improved resistance to alkali poisoning....

  12. Magnetic nanoparticles conjugated to chiral imidazolidinone as recoverable catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Mondini, Sara [Consiglio Nazionale delle Ricerche, Laboratorio di Nanotecnologie, Istituto di Scienze e Tecnologie Molecolari (Italy); Puglisi, Alessandra; Benaglia, Maurizio, E-mail: maurizio.benaglia@unimi.it; Ramella, Daniela [Università degli Studi di Milano, Dipartimento di Chimica (Italy); Drago, Carmelo [Consiglio Nazionale delle Ricerche, Istituto di Chimica Biomolecolare (Italy); Ferretti, Anna M.; Ponti, Alessandro, E-mail: alessandro.ponti@istm.cnr.it [Consiglio Nazionale delle Ricerche, Laboratorio di Nanotecnologie, Istituto di Scienze e Tecnologie Molecolari (Italy)

    2013-11-15

    The immobilization of an ad hoc designed chiral imidazolidin-4-one onto iron oxide magnetic nanoparticles (MNPs) is described, to afford MNP-supported MacMillan’s catalyst. Morphological and structural analysis of the materials, during preparation, use, and recycle, has been carried out by transmission electron microscopy. The supported catalyst was tested in the Diels–Alder reaction of cyclopentadiene with cinnamic aldehyde, affording the products in good yields and enantiomeric excesses up to 93 %, comparable to those observed with the non-supported catalyst. Recovery of the chiral catalyst has been successfully performed by simply applying an external magnet to achieve a perfect separation of the MNPs from the reaction product. The recycle of the catalytic system has been also investigated. Noteworthy, this immobilized MacMillan’s catalyst proved to be able to efficiently promote the reaction in pure water.

  13. Magnetic nanoparticles conjugated to chiral imidazolidinone as recoverable catalyst

    International Nuclear Information System (INIS)

    Mondini, Sara; Puglisi, Alessandra; Benaglia, Maurizio; Ramella, Daniela; Drago, Carmelo; Ferretti, Anna M.; Ponti, Alessandro

    2013-01-01

    The immobilization of an ad hoc designed chiral imidazolidin-4-one onto iron oxide magnetic nanoparticles (MNPs) is described, to afford MNP-supported MacMillan’s catalyst. Morphological and structural analysis of the materials, during preparation, use, and recycle, has been carried out by transmission electron microscopy. The supported catalyst was tested in the Diels–Alder reaction of cyclopentadiene with cinnamic aldehyde, affording the products in good yields and enantiomeric excesses up to 93 %, comparable to those observed with the non-supported catalyst. Recovery of the chiral catalyst has been successfully performed by simply applying an external magnet to achieve a perfect separation of the MNPs from the reaction product. The recycle of the catalytic system has been also investigated. Noteworthy, this immobilized MacMillan’s catalyst proved to be able to efficiently promote the reaction in pure water

  14. Design of two molecular methodologies for the rapid identification of Colombian community-acquired methicillin-resistant Staphylococcus aureus isolates

    OpenAIRE

    Escobar, Javier Antonio; Gómez, Ingrid Tatiana; Murillo, Martha Johanna; Castro, Betsy Esperanza; Chavarro, Bibiana; Márquez, Ricaurte Alejandro; Vanegas, Natasha

    2012-01-01

    Introduction. Community-acquired methicillin-resistant Staphylococcus aureus (CA-MRSA) infections are found with increasing the frequency, both in healthy individuals in the community and in hospitalized patients. In Colombia and the Andean region, CA-MRSA isolates have a genetic background that is related to the pandemic USA300 clone. Objective. Two molecular methods are designed and standardized for the rapid differentiation of Colombian community-acquired and hospital-acquired methicillin-...

  15. Hydrogen evolution reaction catalyst

    Science.gov (United States)

    Subbaraman, Ram; Stamenkovic, Vojislav; Markovic, Nenad; Tripkovic, Dusan

    2016-02-09

    Systems and methods for a hydrogen evolution reaction catalyst are provided. Electrode material includes a plurality of clusters. The electrode exhibits bifunctionality with respect to the hydrogen evolution reaction. The electrode with clusters exhibits improved performance with respect to the intrinsic material of the electrode absent the clusters.

  16. Heterogeneous chromium catalysts

    NARCIS (Netherlands)

    2005-01-01

    The present invention relates to a heterogeneous chromium catalyst system for the polymerisation of ethylene and/or alpha olefins prepared by the steps of: (a) providing a silica-containing support, (b) treating the silica-containing support with a chromium compound to form a chromium-based

  17. Catalysts for Environmental Remediation

    DEFF Research Database (Denmark)

    Abrams, B. L.; Vesborg, Peter Christian Kjærgaard

    2013-01-01

    The properties of catalysts used in environmental remediation are described here through specific examples in heterogeneous catalysis and photocatalysis. In the area of heterogeneous catalysis, selective catalytic reduction (SCR) of NOx was used as an example reaction with vanadia and tungsta...

  18. Rational Design of Molecular Gelator - Solvent Systems Guided by Solubility Parameters

    Science.gov (United States)

    Lan, Yaqi

    Self-assembled architectures, such as molecular gels, have attracted wide interest among chemists, physicists and engineers during the past decade. However, the mechanism behind self-assembly remains largely unknown and no capability exists to predict a priori whether a small molecule will gelate a specific solvent or not. The process of self-assembly, in molecular gels, is intricate and must balance parameters influencing solubility and those contrasting forces that govern epitaxial growth into axially symmetric elongated aggregates. Although the gelator-gelator interactions are of paramount importance in understanding gelation, the solvent-gelator specific (i.e., H-bonding) and nonspecific (dipole-dipole, dipole-induced and instantaneous dipole induced forces) intermolecular interactions are equally important. Solvent properties mediate the self-assembly of molecular gelators into their self-assembled fibrillar networks. Herein, solubility parameters of solvents, ranging from partition coefficients (logP), to Henry's law constants (HLC), to solvatochromic ET(30) parameters, to Kamlet-Taft parameters (beta, alpha and pi), to Hansen solubility parameters (deltap, deltad, deltah), etc., are correlated with the gelation ability of numerous classes of molecular gelators. Advanced solvent clustering techniques have led to the development of a priori tools that can identify the solvents that will be gelled and not gelled by molecular gelators. These tools will greatly aid in the development of novel gelators without solely relying on serendipitous discoveries.

  19. Modified silica-based heterogeneous catalysts for etherification of glycerol

    Energy Technology Data Exchange (ETDEWEB)

    Gholami, Zahra, E-mail: zahra.gholami@petronas.com.my [Centralized Analytical Laboratory, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Abdullah, Ahmad Zuhairi, E-mail: chzuhairi@usm.my; Gholami, Fatemeh, E-mail: fgholami59@gmail.com [School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus,14300 Nibong Tebal, Penang (Malaysia); Vakili, Mohammadtaghi, E-mail: farshid3601@gmail.com [School of Industrial Technology, Universiti Sains Malaysia, 11800 Penang (Malaysia)

    2015-07-22

    The advent of mesoporous silicas such as MCM-41 has provided new opportunities for research into supported metal catalysis. The loading of metals into framework structures and particularly into the pores of porous molecular sieves, has long been of interest because of their potential catalytic activity. Stable heterogeneous mesoporous basic catalysts were synthesized by wet impregnation of MCM-41 with calcium nitrate and lanthanum nitrate. The surface and structural properties of the prepared catalysts were characterized using BET surface analysis, SEM and TEM. MCM-41 and modified MCM-41 were used in the solventless etherification of glycerol to produce diglycerol as the desired product. The reaction was performed at 250 °C for 8 h, and catalyst activity was evaluated. Catalytic etherification over the 20%Ca{sub 1.6}La{sub 0.6}/MCM-41 catalyst resulted in the highest glycerol conversion of 91% and diglycerol yield of 43%.

  20. Modified silica-based heterogeneous catalysts for etherification of glycerol

    International Nuclear Information System (INIS)

    Gholami, Zahra; Abdullah, Ahmad Zuhairi; Gholami, Fatemeh; Vakili, Mohammadtaghi

    2015-01-01

    The advent of mesoporous silicas such as MCM-41 has provided new opportunities for research into supported metal catalysis. The loading of metals into framework structures and particularly into the pores of porous molecular sieves, has long been of interest because of their potential catalytic activity. Stable heterogeneous mesoporous basic catalysts were synthesized by wet impregnation of MCM-41 with calcium nitrate and lanthanum nitrate. The surface and structural properties of the prepared catalysts were characterized using BET surface analysis, SEM and TEM. MCM-41 and modified MCM-41 were used in the solventless etherification of glycerol to produce diglycerol as the desired product. The reaction was performed at 250 °C for 8 h, and catalyst activity was evaluated. Catalytic etherification over the 20%Ca 1.6 La 0.6 /MCM-41 catalyst resulted in the highest glycerol conversion of 91% and diglycerol yield of 43%

  1. Catalyst support structure, catalyst including the structure, reactor including a catalyst, and methods of forming same

    Science.gov (United States)

    Van Norman, Staci A.; Aston, Victoria J.; Weimer, Alan W.

    2017-05-09

    Structures, catalysts, and reactors suitable for use for a variety of applications, including gas-to-liquid and coal-to-liquid processes and methods of forming the structures, catalysts, and reactors are disclosed. The catalyst material can be deposited onto an inner wall of a microtubular reactor and/or onto porous tungsten support structures using atomic layer deposition techniques.

  2. Polyethers for biomedical applications. Polymerization of propylene oxide by organozinc/organotin catalysts

    NARCIS (Netherlands)

    Bots, Jan Gert; van der Does, L.; Bantjes, Adriaan; Broersma, Jaap

    1987-01-01

    The polymerization of propylene oxide to obtain a high-molecular-weight polymer with an atactic structure required for the application as artificial blood vessels was investigated using combinations of organozinc and organotin compounds as catalyst. The composition of the most active catalyst,

  3. A NEW TYPE OF HIGHLY-ACTIVE POLYMER-BOUND RHODIUM HYDROFORMYLATION CATALYST

    NARCIS (Netherlands)

    JONGSMA, T; KIMKES, P; CHALLA, G; VANLEEUWEN, PWNM

    1992-01-01

    A new route of attaching phosphites to a (co)polymer chain is described. These copolymers are used for the preparation of a rhodium phosphite hydroformylation catalyst. The catalytic activity of this polymer-bound system is identical to that of the low molecular weight analogue. The catalysts show a

  4. DEVELOPMENT OF PRECIPITATED IRON FISCHER-TROPSCH CATALYSTS

    International Nuclear Information System (INIS)

    Bukur, Dragomir B.; Lang, X.; Chokkaram, S.; Nowicki, L.; Wei, G.; Ding, Y.; Reddy, B.; Xiao, S.

    1999-01-01

    Despite the current worldwide oil glut, the US will ultimately require large-scale production of liquid (transportation) fuels from coal. Slurry phase Fischer-Tropsch (F-T) technology, with its versatile product slate, may be expected to play a major role in production of transportation fuels via indirect coal liquefaction. Some of the F-T catalysts synthesized and tested at Texas A and M University under DOE Contract No. DE-AC22-89PC89868 were more active than any other known catalysts developed for maximizing production of high molecular weight hydrocarbons (waxes). The objectives of the present contract were to demonstrate repeatability of catalyst performance and reproducibility of preparation procedures of two of these catalysts on a laboratory scale. Improvements in the catalyst performance were attempted through the use of: (a) higher reaction pressure and gas space velocity to maximize the reactor productivity; (b) modifications in catalyst preparation steps; and (c) different pretreatment procedures. Repeatability of catalyst performance and reproducibility of catalyst synthesis procedure have been successfully demonstrated in stirred tank slurry reactor tests. Reactor space-time-yield was increased up to 48% by increasing reaction pressure from 1.48 MPa to 2.17 MPa, while maintaining the gas contact time and synthesis gas conversion at a constant value. Use of calcination temperatures above 300 C, additional CaO promoter, and/or potassium silicate as the source of potassium promoter, instead of potassium bicarbonate, did not result in improved catalyst performance. By using different catalyst activation procedures they were able to increase substantially the catalyst activity, while maintaining low methane and gaseous hydrocarbon selectivities. Catalyst productivity in runs SA-0946 and SA-2186 was 0.71 and 0.86 gHC/g-Fe/h, respectively, and this represents 45-75% improvement in productivity relative to that achieved in Rheinpreussen's demonstration plant

  5. Lipid-based nanoparticles for magnetic resonance molecular imaging : design, characterization, and application

    NARCIS (Netherlands)

    Mulder, W.J.M.

    2006-01-01

    In this thesis research is described which was aimed to develop lipidic nanoparticles for the investigation and visualization of atherosclerosis and angiogenesis with both magnetic resonance molecular imaging and optical techniques. The underlying rationale for this is that conventional MR imaging

  6. MaMiCo: Software design for parallel molecular-continuum flow simulations

    KAUST Repository

    Neumann, Philipp; Flohr, Hanno; Arora, Rahul; Jarmatz, Piet; Tchipev, Nikola; Bungartz, Hans-Joachim

    2015-01-01

    The macro-micro-coupling tool (MaMiCo) was developed to ease the development of and modularize molecular-continuum simulations, retaining sequential and parallel performance. We demonstrate the functionality and performance of MaMiCo by coupling

  7. Molecular quantum cellular automata cell design trade-offs: latching vs. power dissipation.

    Science.gov (United States)

    Rahimi, Ehsan; Reimers, Jeffrey R

    2018-06-20

    The use of molecules to enact quantum cellular automata (QCA) cells has been proposed as a new way for performing electronic logic operations at sub-nm dimensions. A key question that arises concerns whether chemical or physical processes are to be exploited. The use of chemical reactions allows the state of a switch element to be latched in molecular form, making the output of a cell independent of its inputs, but costs energy to do the reaction. Alternatively, if purely electronic polarization is manipulated then no internal latching occurs, but no power is dissipated provided the fields from the inputs change slowly compared to the molecular response times. How these scenarios pan out is discussed by considering calculated properties of the 1,4-diallylbutane cation, a species often used as a paradigm for molecular electronic switching. Utilized are results from different calculation approaches that depict the ion either as a charge-localized mixed-valence compound functioning as a bistable switch, or else as an extremely polarizable molecule with a delocalized electronic structure. Practical schemes for using molecular cells in QCA and other devices emerge.

  8. Vibration measurements of automobile catalyst

    Science.gov (United States)

    Aatola, Seppo

    1994-09-01

    Vibration of catalyst cell, which is inside the casing of the catalyst, is difficult to measure with usual measuring instrumentation. When catalyst is in use, there is hot exhaust gas flow though the catalyst cell and temperature of the cell is approximately +900 degree(s)C. Therefore non-contact Laser- Doppler-Vibrometer was used to measure vibration velocity of the catalyst cell. The laser beam was directed towards the cell through pipe which was put through and welded to the casing of the catalyst. The outer end of the pipe was screw down with a tempered class to prevent exhaust gas flow from the pipe. The inner end of the pipe was open and few millimeters away from the measuring point. Catalyst was attached to the engine with two ways, rigidly close to the engine and flexible under the engine. The engine was running in test bench under controlled conditions. Vibration measurements were carried out during constant running speeds of the engine. Vibration signals were captured and analyzed with FFT-analyzer. Vibration of catalyst cell was strongest at running speed of 5000 rpm, from 10 to 20 g (1 g equals 9.81 ms-2), when catalyst was attached rigidly close to the engine. At running speed of 3000 rpm, vibration of catalyst cell was from 2 to 3 g in most cases, when catalyst was attached either rigidly or flexible to the engine. It is estimated that in real life, i.e. when catalyst is attached to car with same engine, vibration of catalyst cell at running speed of 5000 rpm is somewhere between 1 and 10 g. At running speed of 3000 rpm, which may be more often used when driving car (car speed approximately 100 kmh-1), vibration of catalyst cell is probably few g's.

  9. Discovery of fuel cell anode electrocatalysts and dehydrogenation catalysts using combinatorial techniques

    Science.gov (United States)

    Chan, Benny Chun Wai

    A gas diffusion optical screening method was developed for the discovery of catalysts for the electro-oxidation of reformate gas (H2 with 100 ppm CO). The screening cell was designed to accommodate a gas diffusion layer, 715 member catalyst array, and an electrolyte container. Since protons are generated during H2 oxidation, a pH sensitive fluorphore was used to identify active compositions. The cell showed no detectable iR drop across the array and ranked activity of two commercial PtRu and one Pt catalysts. Over 95% of a given catalyst fluoresced at the initial onset potential and a 5 mV difference in onset potential of two different catalysts was statistically different. A gas diffusion half cell was designed similar to the optical screening cell to obtain current-potential curves of bulk catalysts. The screening results correlated with half cell and fuel cell data, internally validating the method. The combinatorial method was then applied to search for catalysts in the PtRuMoIrRh composition space. The catalysts on the array were prepared by hydrogen reduction of the metals salts on carbon. The most active catalysts were from the Pt enriched regions of the PtRuMoRh quaternary. Bulk catalysts were prepared from the active regions and tested in the gas diffusion half cell. The most active catalysts in the optical screening were also the most active catalysts in the half cell. When any homemade catalysts were compared to commercial PtRu, however, the performance was worse. A high surface area, high catalyst activity synthetic method is the most important factor to reliably screen catalysts for "real world" fuel cell application. High surface area catalysts were tested for direct methanol oxidation activity. The optical screening method was compared with disk electrode, high throughput fuel cell testing, and fuel cell testing. Six catalysts examined included two commercial PtRu catalysts, a Pt catalyst, and three homemade PtRu catalysts of varying activity

  10. Molecular design of donor-acceptor dyes for efficient dye-sensitized solar cells I: a DFT study.

    Science.gov (United States)

    El-Shishtawy, Reda M; Asiri, Abdullah M; Aziz, Saadullah G; Elroby, Shaaban A K

    2014-06-01

    Dye-sensitized solar cells (DSSCs) have drawn great attention as low cost and high performance alternatives to conventional photovoltaic devices. The molecular design presented in this work is based on the use of pyran type dyes as donor based on frontier molecular orbitals (FMO) and theoretical UV-visible spectra in combination with squaraine type dyes as an acceptor. Density functional theory has been used to investigate several derivatives of pyran type dyes for a better dye design based on optimization of absorption, regeneration, and recombination processes in gas phase. The frontier molecular orbital (FMO) of the HOMO and LUMO energy levels plays an important role in the efficiency of DSSCs. These energies contribute to the generation of exciton, charge transfer, dissociation and exciton recombination. The computations of the geometries and electronic structures for the predicted dyes were performed using the B3LYP/6-31+G** level of theory. The FMO energies (EHOMO, ELUMO) of the studied dyes are calculated and analyzed in the terms of the UV-visible absorption spectra, which have been examined using time-dependent density functional theory (TD-DFT) techniques. This study examined absorption properties of pyran based on theoretical UV-visible absorption spectra, with comparisons between TD-DFT using B3LYP, PBE, and TPSSH functionals with 6-31+G (d) and 6-311++G** basis sets. The results provide a valuable guide for the design of donor-acceptor (D-A) dyes with high molar absorptivity and current conversion in DSSCs. The theoretical results indicated 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran dye (D2-Me) can be effectively used as a donor dye for DSSCs. This dye has a low energy gap by itself and a high energy gap with squaraine acceptor type dye, the design that reduces the recombination and improves the photocurrent generation in solar cell.

  11. Selective Transformation of Various Nitrogen-Containing Exhaust Gases toward N2 over Zeolite Catalysts.

    Science.gov (United States)

    Zhang, Runduo; Liu, Ning; Lei, Zhigang; Chen, Biaohua

    2016-03-23

    In this review we focus on the catalytic removal of a series of N-containing exhaust gases with various valences, including nitriles (HCN, CH3CN, and C2H3CN), ammonia (NH3), nitrous oxide (N2O), and nitric oxides (NO(x)), which can cause some serious environmental problems, such as acid rain, haze weather, global warming, and even death. The zeolite catalysts with high internal surface areas, uniform pore systems, considerable ion-exchange capabilities, and satisfactory thermal stabilities are herein addressed for the corresponding depollution processes. The sources and toxicities of these pollutants are introduced. The important physicochemical properties of zeolite catalysts, including shape selectivity, surface area, acidity, and redox ability, are described in detail. The catalytic combustion of nitriles and ammonia, the direct catalytic decomposition of N2O, and the selective catalytic reduction and direct catalytic decomposition of NO are systematically discussed, involving the catalytic behaviors as well as mechanism studies based on spectroscopic and kinetic approaches and molecular simulations. Finally, concluding remarks and perspectives are given. In the present work, emphasis is placed on the structure-performance relationship with an aim to design an ideal zeolite-based catalyst for the effective elimination of harmful N-containing compounds.

  12. Method of Heating a Foam-Based Catalyst Bed

    Science.gov (United States)

    Fortini, Arthur J.; Williams, Brian E.; McNeal, Shawn R.

    2009-01-01

    A method of heating a foam-based catalyst bed has been developed using silicon carbide as the catalyst support due to its readily accessible, high surface area that is oxidation-resistant and is electrically conductive. The foam support may be resistively heated by passing an electric current through it. This allows the catalyst bed to be heated directly, requiring less power to reach the desired temperature more quickly. Designed for heterogeneous catalysis, the method can be used by the petrochemical, chemical processing, and power-generating industries, as well as automotive catalytic converters. Catalyst beds must be heated to a light-off temperature before they catalyze the desired reactions. This typically is done by heating the assembly that contains the catalyst bed, which results in much of the power being wasted and/or lost to the surrounding environment. The catalyst bed is heated indirectly, thus requiring excessive power. With the electrically heated catalyst bed, virtually all of the power is used to heat the support, and only a small fraction is lost to the surroundings. Although the light-off temperature of most catalysts is only a few hundred degrees Celsius, the electrically heated foam is able to achieve temperatures of 1,200 C. Lower temperatures are achievable by supplying less electrical power to the foam. Furthermore, because of the foam s open-cell structure, the catalyst can be applied either directly to the foam ligaments or in the form of a catalyst- containing washcoat. This innovation would be very useful for heterogeneous catalysis where elevated temperatures are needed to drive the reaction.

  13. A Catalyst for Change

    DEFF Research Database (Denmark)

    Lønsmann, Dorte

    2017-01-01

    This case study of a team in an international workplace investigates processes of language socialization in a transient multilingual setting. Using interview and observational data, the analysis shows how social and linguistic norms are negotiated, with the newcomer positioned as a catalyst...... for changing language practices toward more English, with the ultimate aim of creating a 'global mindset' in the organization. Language socialization in a transient multilingual setting is shown to focus on and assign positive value to new linguistic norms that experienced members are socialized...... into in a process that hinges on new members functioning as tools for management to bring about the desired change. The article shows that while the newcomer is used as a catalyst for increased use of English and for the creation of a 'global mindset,' she is at the same time socialized into the existing Danish...

  14. Photo catalyst; Ko shokubai

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1999-07-01

    While titanium oxide is excited by the light, electrons of titanium oxide are taken away by the light energy to form positive holes. Water will be decomposed into hydrogen ion and hydroxy radical (OH) by these positive holes. This hydroxy radical is a strong reactive substance called active oxygen, it decomposes organisms. Besides this photo- catalyst function, the titanium oxide can also make surface of a substance superhydrophilic. The super hydrophilicity results in not forming water drops on the glass surface but spreading all over the surface to prevent a covering of fog on the glass surface. The published patents concerning the photo catalysts were 593 from Jan. 1998 to Jan. 1999. The applicant order is the first TOTO 143, the second Daikin Industry 19, the third Toshiba Raitech, Nitto Denko, Hitachi 17 respectively. (NEDO)

  15. Sensitivity analysis of Computer-aided molecular design problem for the development of novel working fluids for power cycles

    DEFF Research Database (Denmark)

    Frutiger, Jerome; Abildskov, Jens; Sin, Gürkan

    is vital. Multi-criteria database search and Computer Aided Molecular Design(CAMD) can be applied to generate, test and evaluate promising pure component/mixture candidate as process fluids to help optimize cycle design and performance. The problem formulation for the development of novel working fluids...... is anadvanced CAMD challenge both in terms of data and computational demand, because includes process related as wellas property related equations.In CAMD problems the identification of target properties is often based on expert knowledge. To support identification of relevant target properties, in this study...... allows the ranking ofsignificance of properties and also the identification of a set of properties which are relevant for the design of a workingfluids.In this study the CAMD problem for the development of novel working fluids for organic Rankine cycles (ORC) isformulated as a mathematical optimization...

  16. Microscopic cascading of second-order molecular nonlinearity: New design principles for enhancing third-order nonlinearity.

    Science.gov (United States)

    Baev, Alexander; Autschbach, Jochen; Boyd, Robert W; Prasad, Paras N

    2010-04-12

    Herein, we develop a phenomenological model for microscopic cascading and substantiate it with ab initio calculations. It is shown that the concept of local microscopic cascading of a second-order nonlinearity can lead to a third-order nonlinearity, without introducing any new loss mechanisms that could limit the usefulness of our approach. This approach provides a new molecular design protocol, in which the current great successes achieved in producing molecules with extremely large second-order nonlinearity can be used in a supra molecular organization in a preferred orientation to generate very large third-order response magnitudes. The results of density functional calculations for a well-known second-order molecule, (para)nitroaniline, show that a head-to-tail dimer configuration exhibits enhanced third-order nonlinearity, in agreement with the phenomenological model which suggests that such an arrangement will produce cascading due to local field effects.

  17. Design of efficient molecular organic light-emitting diodes by a high-throughput virtual screening and experimental approach

    Science.gov (United States)

    Gómez-Bombarelli, Rafael; Aguilera-Iparraguirre, Jorge; Hirzel, Timothy D.; Duvenaud, David; MacLaurin, Dougal; Blood-Forsythe, Martin A.; Chae, Hyun Sik; Einzinger, Markus; Ha, Dong-Gwang; Wu, Tony; Markopoulos, Georgios; Jeon, Soonok; Kang, Hosuk; Miyazaki, Hiroshi; Numata, Masaki; Kim, Sunghan; Huang, Wenliang; Hong, Seong Ik; Baldo, Marc; Adams, Ryan P.; Aspuru-Guzik, Alán

    2016-10-01

    Virtual screening is becoming a ground-breaking tool for molecular discovery due to the exponential growth of available computer time and constant improvement of simulation and machine learning techniques. We report an integrated organic functional material design process that incorporates theoretical insight, quantum chemistry, cheminformatics, machine learning, industrial expertise, organic synthesis, molecular characterization, device fabrication and optoelectronic testing. After exploring a search space of 1.6 million molecules and screening over 400,000 of them using time-dependent density functional theory, we identified thousands of promising novel organic light-emitting diode molecules across the visible spectrum. Our team collaboratively selected the best candidates from this set. The experimentally determined external quantum efficiencies for these synthesized candidates were as large as 22%.

  18. Designing of phenol-based β-carbonic anhydrase1 inhibitors through QSAR, molecular docking, and MD simulation approach.

    Science.gov (United States)

    Ahamad, Shahzaib; Hassan, Md Imtaiyaz; Dwivedi, Neeraja

    2018-05-01

    Tuberculosis (Tb) is an airborne infectious disease caused by Mycobacterium tuberculosis. Beta-carbonic anhydrase 1 ( β-CA1 ) has emerged as one of the potential targets for new antitubercular drug development. In this work, three-dimensional quantitative structure-activity relationships (3D-QSAR), molecular docking, and molecular dynamics (MD) simulation approaches were performed on a series of natural and synthetic phenol-based β-CA1 inhibitors. The developed 3D-QSAR model ( r 2  = 0.94, q 2  = 0.86, and pred_r 2  = 0.74) indicated that the steric and electrostatic factors are important parameters to modulate the bioactivity of phenolic compounds. Based on this indication, we designed 72 new phenolic inhibitors, out of which two compounds (D25 and D50) effectively stabilized β-CA1 receptor and, thus, are potential candidates for new generation antitubercular drug discovery program.

  19. Synthetic Molecular Machines for Active Self-Assembly: Prototype Algorithms, Designs, and Experimental Study

    Science.gov (United States)

    Dabby, Nadine L.

    Computer science and electrical engineering have been the great success story of the twentieth century. The neat modularity and mapping of a language onto circuits has led to robots on Mars, desktop computers and smartphones. But these devices are not yet able to do some of the things that life takes for granted: repair a scratch, reproduce, regenerate, or grow exponentially fast--all while remaining functional. This thesis explores and develops algorithms, molecular implementations, and theoretical proofs in the context of "active self-assembly" of molecular systems. The long-term vision of active self-assembly is the theoretical and physical implementation of materials that are composed of reconfigurable units with the programmability and adaptability of biology's numerous molecular machines. En route to this goal, we must first find a way to overcome the memory limitations of molecular systems, and to discover the limits of complexity that can be achieved with individual molecules. One of the main thrusts in molecular programming is to use computer science as a tool for figuring out what can be achieved. While molecular systems that are Turing-complete have been demonstrated [Winfree, 1996], these systems still cannot achieve some of the feats biology has achieved. One might think that because a system is Turing-complete, capable of computing "anything," that it can do any arbitrary task. But while it can simulate any digital computational problem, there are many behaviors that are not "computations" in a classical sense, and cannot be directly implemented. Examples include exponential growth and molecular motion relative to a surface. Passive self-assembly systems cannot implement these behaviors because (a) molecular motion relative to a surface requires a source of fuel that is external to the system, and (b) passive systems are too slow to assemble exponentially-fast-growing structures. We call these behaviors "energetically incomplete" programmable

  20. High-Activity Dealloyed Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kongkanand, Anusorn [General Motors LLC, Pontiac, MI (United States)

    2014-09-30

    Reduction of costly Pt usage in proton exchange membrane fuel cell electrodes is one of the major challenges towards development and commercialization of fuel cell vehicles. Although few have met the initial-kinetic activity requirements in a realistic fuel cell device, no catalyst material has ever met the demanding fuel cell durability targets set by DOE. In this project, a team of 4 universities and 2 companies came together to investigate a concept that appeared promising in preliminary non-fuel cell tests then to further develop the catalyst to a mature level ready for vehicle implementation. The team consists of academia with technical leadership in their respective areas, a catalyst supplier, and a fuel cell system integrator.The tightly collaborative project enabled development of a highly active and durable catalyst with performance that significantly exceeds that of previous catalysts and meets the DOE targets for the first time (Figure 1A). The catalyst was then further evaluated in full-active-area stack in a realistic vehicle operating condition (Figure 1B). This is the first public demonstration that one can realize the performance benefit and Pt cost reduction over a conventional pure Pt catalyst in a long-term realistic PEMFC system. Furthermore, systematic analyses of a range of catalysts with different performance after fuel cell testing allowed for correlation between catalyst microstructure and its electrocatalytic activity and durability. This will in turn aid future catalyst development.

  1. Exploring electronic and steric effects on the insertion and polymerization reactivity of phosphinesulfonato pdii catalysts

    KAUST Repository

    Neuwald, Boris; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Mecking, Stefan

    2013-01-01

    incorporation at low MA concentrations in the copolymerization; and 3) steric shielding leads to a pronounced increase in polymer molecular weight in the copolymerization. The catalyst properties induced by a given P-aryl (alkyl) moiety were combined effectively

  2. Study of the effect of ionizing radiation for utilization of spent cracking catalysts

    International Nuclear Information System (INIS)

    Kondo, Fernando Mantovani

    2014-01-01

    Catalyst is a substance that changes the rate of a reaction. In the petroleum industry the commonly catalysts are used for Fluid Catalytic Cracking (FCC) and Hydrocatalytic Cracking (HCC), which one applied in a specific stage. These catalysts are used to facilitate the molecular chains cracking which will generate a mixture of hydrocarbons. However, the catalyst gradually loses its activity, either by changing its original molecular structure or by its contamination from other petroleum molecules. The application of ionizing radiation (electron beam and gamma rays) over these spent catalysts was studied to contribute with the extraction of metals or rare-earths of high added-value. Tests carried out with FCC catalysts were used the techniques of 60 Co irradiation and electron beam (EB) and had as a subject the extraction of lanthanum (La 2 O 3 ), regeneration and utilization of these catalysts. However, the use of ionizing radiation has not contributed in these processes. Meanwhile with HCC catalysts the irradiation used was electron beam and had as a subject the extraction of molybdenum (MoO 3 ). In temperature around 750°C, these irradiated catalysts of the lower region have an extraction yield twice higher compared to non-irradiated ones, in other words 57.65% and 26.24% respectively. (author)

  3. Solid state photochemistry. Subpanel A-2(a): Design of molecular precursors for electronic materials

    Energy Technology Data Exchange (ETDEWEB)

    Wells, R.L. [Duke Univ., Durham, NC (United States)

    1996-09-01

    Recent achievements of synthetic chemistry in the field of electronic materials are presented in three categories; viz, precursor design for improved processing, new chemistry for selective growth, and new growth techniques. This is followed by a discussion of challenges and opportunities in two general areas designated as composition and structure, and growth and processing.

  4. Alkylation of toluene with isopropyl alcohol over SAPO-5 catalyst

    Indian Academy of Sciences (India)

    Administrator

    Abstract. Isopropylation of toluene with isopropyl alcohol was studied over the large pore silicon alu- mino phosphate molecular sieves (SAPO-5) with varying Si content. Toluene conversion was found to increase with increase in the Si of the catalysts. The effect of temperature on yields of cymene was studied in the range ...

  5. Morphology-controlled Pd nanocrystals as catalysts in tandem ...

    Indian Academy of Sciences (India)

    MIRIAM NAVLANI-GARCÍA

    2017-09-22

    Sep 22, 2017 ... aDivision of Materials and Manufacturing Science, Graduate School of Engineering, Osaka University, .... 5. 0.390. 0.680. 5.0. –. Note: S, M and L are referred to small, medium and large average nanocrystals size. [a] Considering the molecular weight (MW ) of one ... In this case, 10 mg of catalyst and 5 mL.

  6. Supported Catalysts Useful in Ring-Closing Metathesis, Cross Metathesis, and Ring-Opening Metathesis Polymerization

    Directory of Open Access Journals (Sweden)

    Jakkrit Suriboot

    2016-04-01

    Full Text Available Ruthenium and molybdenum catalysts are widely used in synthesis of both small molecules and macromolecules. While major developments have led to new increasingly active catalysts that have high functional group compatibility and stereoselectivity, catalyst/product separation, catalyst recycling, and/or catalyst residue/product separation remain an issue in some applications of these catalysts. This review highlights some of the history of efforts to address these problems, first discussing the problem in the context of reactions like ring-closing metathesis and cross metathesis catalysis used in the synthesis of low molecular weight compounds. It then discusses in more detail progress in dealing with these issues in ring opening metathesis polymerization chemistry. Such approaches depend on a biphasic solid/liquid or liquid separation and can use either always biphasic or sometimes biphasic systems and approaches to this problem using insoluble inorganic supports, insoluble crosslinked polymeric organic supports, soluble polymeric supports, ionic liquids and fluorous phases are discussed.

  7. A Systematic Modelling Framework for Phase Transfer Catalyst Systems

    DEFF Research Database (Denmark)

    Anantpinijwatna, Amata; Sales-Cruz, Mauricio; Hyung Kim, Sun

    2016-01-01

    Phase-transfer catalyst systems contain two liquid phases, with a catalyst (PTC) that transfers between the phases, driving product formation in one phase and being regenerated in the other phase. Typically the reaction involves neutral species in an organic phase and regeneration involves ions i....... The application of the framework is made to two cases in order to highlight the performance and issues of activity coefficient models for predicting design and operation and the effects when different organic solvents are employed....

  8. A BGO detector for Positron Emission Profiling in catalysts

    International Nuclear Information System (INIS)

    Mangnus, A.V.G.; Cunningham, R.H.; Santen, R.A. van; Voigt, M.J.A. de

    1995-01-01

    As part of a project to study the reaction kinetics in catalysts, a detector system has been designed and built. The detector will measure in one dimension the activity distribution of positron emitters in catalyst reactors under operational conditions as a function of time. The detector consists of two arrays of ten BGO crystals each and has the flexibility to measure with high sensitivity the activity profile in various reactor sizes; the position resolution that can be reached is 3 mm. (orig.)

  9. The Design of a Molecular Assembly Line Based on Biological Molecules

    Science.gov (United States)

    2003-06-01

    parenthesis in figure 1.8 is a bi-stable toggle switch. Introduction: Molecular assembly lines O=P-O- O O HOH H0P-0- O -O- 4 Polymerase HO H--- O HHO ...sample. Therefore, the samples are self-consistent. From here on, the calculated temperature based on FAM emission MNSowmm" RF Biology: Results and...irradiation for one hour. Figure 2.11 shows the fluorescence spectra of FAM emission (4 scans averaged over 200 seconds) in a 300MHz field. The increased

  10. Analog series-based scaffolds: computational design and exploration of a new type of molecular scaffolds for medicinal chemistry

    Science.gov (United States)

    Dimova, Dilyana; Stumpfe, Dagmar; Hu, Ye; Bajorath, Jürgen

    2016-01-01

    Aim: Computational design of and systematic search for a new type of molecular scaffolds termed analog series-based scaffolds. Materials & methods: From currently available bioactive compounds, analog series were systematically extracted, key compounds identified and new scaffolds isolated from them. Results: Using our computational approach, more than 12,000 scaffolds were extracted from bioactive compounds. Conclusion: A new scaffold definition is introduced and a computational methodology developed to systematically identify such scaffolds, yielding a large freely available scaffold knowledge base. PMID:28116132

  11. Design and synthesis of a fluorescent molecular imprinted polymer for use in an optical fibre-based cocaine sensor

    Science.gov (United States)

    Wren, Stephen P.; Piletsky, Sergey A.; Karim, Kal; Gascoine, Paul; Lacey, Richard; Sun, Tong; Grattan, Kenneth T. V.

    2014-05-01

    Previously, we have developed chemical sensors using fibre optic-based techniques for the detection of Cocaine, utilising molecularly imprinted polymers (MIPs) containing fluorescein moieties as the signalling groups. Here, we report the computational design of a fluorophore which was incorporated into a MIP for the generation of a novel sensor that offers improved sensitivity for Cocaine with a detection range of 1-100μM. High selectivity for Cocaine over a suite of known Cocaine interferants (25μM) was also demonstrated by measuring changes in the intensity of fluorescence signals received from the sensor.

  12. Design of supramolecular ordered systems for mesoscopic colloids and molecular composites. Progress report, November 10, 1993--June 10, 1994

    Energy Technology Data Exchange (ETDEWEB)

    1995-01-01

    During this reporting period, the authors group has been active in five areas of research: (1) improvements on their x-ray instrumentation at the SUNY Beamline, National Synchrotron Light Source (NSLS) so that they can perform new experiments which are not accessible otherwise; (2) characterization of functionalized hairy rod polymers designed for studying the macromolecular structures in molecular composites; (3) investigation of supramolecular ordered systems composed mainly of block copolymers from dilute to concentrated solutions, including the gel state; (4) evolution of crystalline structures in polymer blends and melts; and (5) multiphase structure of segment polyurethanes.

  13. Fuel cell development for transportation: Catalyst development

    Energy Technology Data Exchange (ETDEWEB)

    Doddapaneni, N. [Sandia National Lab., Albuquerque, NM (United States)

    1996-04-01

    Fuel cells are being considered as alternate power sources for transportation and stationary applications. With proton exchange membrane (PEM) fuel cells the fuel crossover to cathodes causes severe thermal management and cell voltage drop due to oxidation of fuel at the platinized cathodes. The main goal of this project was to design, synthesize, and evaluate stable and inexpensive transition metal macrocyclic catalysts for the reduction of oxygen and be electrochemically inert towards anode fuels such as hydrogen and methanol.

  14. Oxygen-reducing catalyst layer

    Science.gov (United States)

    O'Brien, Dennis P [Maplewood, MN; Schmoeckel, Alison K [Stillwater, MN; Vernstrom, George D [Cottage Grove, MN; Atanasoski, Radoslav [Edina, MN; Wood, Thomas E [Stillwater, MN; Yang, Ruizhi [Halifax, CA; Easton, E Bradley [Halifax, CA; Dahn, Jeffrey R [Hubley, CA; O'Neill, David G [Lake Elmo, MN

    2011-03-22

    An oxygen-reducing catalyst layer, and a method of making the oxygen-reducing catalyst layer, where the oxygen-reducing catalyst layer includes a catalytic material film disposed on a substrate with the use of physical vapor deposition and thermal treatment. The catalytic material film includes a transition metal that is substantially free of platinum. At least one of the physical vapor deposition and the thermal treatment is performed in a processing environment comprising a nitrogen-containing gas.

  15. Catalyst systems and uses thereof

    Science.gov (United States)

    Ozkan, Umit S [Worthington, OH; Holmgreen, Erik M [Columbus, OH; Yung, Matthew M [Columbus, OH

    2012-07-24

    A method of carbon monoxide (CO) removal comprises providing an oxidation catalyst comprising cobalt supported on an inorganic oxide. The method further comprises feeding a gaseous stream comprising CO, and oxygen (O.sub.2) to the catalyst system, and removing CO from the gaseous stream by oxidizing the CO to carbon dioxide (CO.sub.2) in the presence of the oxidation catalyst at a temperature between about 20 to about 200.degree. C.

  16. Development of GREET Catalyst Module

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhichao [Argonne National Lab. (ANL), Argonne, IL (United States); Benavides, Pahola T. [Argonne National Lab. (ANL), Argonne, IL (United States); Dunn, Jennifer B. [Argonne National Lab. (ANL), Argonne, IL (United States); Cronauer, Donald C. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2015-09-01

    In this report, we develop energy and material flows for the production of five different catalysts (tar reforming, alcohol synthesis, Zeolite Socony Mobil-5 [ZSM-5], Mo/Co/ γ-Al2O3, and Pt/ γ-Al2O3) and two chemicals (olivine, dimethyl ether of polyethylene glycol [DEPG]). These compounds and catalysts are now included in the Greenhouse Gases, Regulated Emissions and Energy Use in Transportation (GREET™) catalyst module.

  17. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Chunshan, Song; Kirby, S.; Schmidt, E. [Pennsylvania State Univ., University Park, PA (United States)] [and others

    1995-12-31

    The objective of this project is to explore bimetallic dispersed catalysts for more efficient coal liquefaction. Coal liquefaction involves cleavage of methylene, dimethylene and ether bridges connecting various aromatic units and the reactions of various oxygen functional groups. This paper describes recent results on (1) hydrodeoxygenation of O-containing polycyclic model compounds using novel organometallic catalyst precursors; and (2) activity and selectivity of dispersed Fe catalysts from organometallic and inorganic precursors for hydrocracking of 4-(1-naphthylmethyl) bibenzyl. The results showed that some iron containing catalysts have higher activity in the sulfur-free form, contrary to conventional wisdom. Adding sulfur to Fe precursors with Cp-ligands decreased the activity of the resulting catalyst. This is in distinct contrast to the cases with iron pentacarbonyl and superfine Fe{sub 2}O{sub 3}, where S addition increased their catalytic activity substantially. A positive correlation between sulfur addition and increased activity can be seen, but a reversed trend between Fe cluster size and hydrocracking conversion could be observed, for carbonyl-type Fe precursors. It is apparent that the activity and selectivity of Fe catalysts for NMBB conversion depends strongly on both the type of ligand environment, the oxidation state and the number of intermetal bonds in the molecular precursor.

  18. Catalyst for disproportionation/double-bond isomerization of olefins

    International Nuclear Information System (INIS)

    Hughes, W.; Reusser, R.

    1980-01-01

    An activated calcined homogenous catalyst composition consists essentially of a support uranium and at least one of tungsten and rhenium, wherein said composition contains about 0.1 to 25 weight percent total uranium, tungsten, and rhenium, each calculated as the metal; and a weight ratio of uranium:at least one of tungsten and rhenium of about 2:1 to 1:1. The activated catalyst composition is prepared by steps which comprise forming a homogenous composite, calcining said homogenous composite in a molecular oxygen-containing atmosphere at elevated temperatures, and subsequently activating said calcined homogenous composite under reducing conditions at elevated temperatures. The catalyst composition according to claim 1 is one in which the total of uranium, tungsten, and rhenium is about 1 to 15 weight percent. The catalyst composition according to claim 2 is one in which the ratio of uranium to at least one of tungsten and rhenium is about 2:1 to 0.5:1. The catalyst composition according to claim 3 is one in which the support is alumina, silica, silica-alumina, zirconia, titania, thoria, aluminum phosphate, magnisium silicate, zinc aluminate, or mixture. The catalyst composition according to claim 4is one in which support is silica

  19. Molecular-level architectural design using benzothiadiazole-based polymers for photovoltaic applications.

    Science.gov (United States)

    Viswanathan, Vinila N; Rao, Arun D; Pandey, Upendra K; Kesavan, Arul Varman; Ramamurthy, Praveen C

    2017-01-01

    A series of low band gap, planar conjugated polymers, P1 (PFDTBT), P2 (PFDTDFBT) and P3 (PFDTTBT), based on fluorene and benzothiadiazole, was synthesized. The effect of fluorine substitution and fused aromatic spacers on the optoelectronic and photovoltaic performance was studied. The polymer, derived from dithienylated benzothiodiazole and fluorene, P1 , exhibited a highest occupied molecular orbital (HOMO) energy level at -5.48 eV. Density functional theory (DFT) studies as well as experimental measurements suggested that upon substitution of the acceptor with fluorine, both the HOMO and lowest unoccupied molecular orbital (LUMO) energy levels of the resulting polymer, P2 , were lowered, leading to a higher open circuit voltage and short circuit current with an overall improvement of more than 110% for the photovoltaic devices. Moreover, a decrease in the torsion angle between the units was also observed for the fluorinated polymer P2 due to the enhanced electrostatic interaction between the fluorine substituents and sulfur atoms, leading to a high hole mobility. The use of a fused π-bridge in polymer P3 for the enhancement of the planarity as compared to the P1 backbone was also studied. This enhanced planarity led to the highest observed mobility among the reported three polymers as well as to an improvement in the device efficiency by more than 40% for P3 .

  20. Molecular engineering with artificial atoms: designing a material platform for scalable quantum spintronics and photonics

    Science.gov (United States)

    Doty, Matthew F.; Ma, Xiangyu; Zide, Joshua M. O.; Bryant, Garnett W.

    2017-09-01

    Self-assembled InAs Quantum Dots (QDs) are often called "artificial atoms" and have long been of interest as components of quantum photonic and spintronic devices. Although there has been substantial progress in demonstrating optical control of both single spins confined to a single QD and entanglement between two separated QDs, the path toward scalable quantum photonic devices based on spins remains challenging. Quantum Dot Molecules, which consist of two closely-spaced InAs QDs, have unique properties that can be engineered with the solid state analog of molecular engineering in which the composition, size, and location of both the QDs and the intervening barrier are controlled during growth. Moreover, applied electric, magnetic, and optical fields can be used to modulate, in situ, both the spin and optical properties of the molecular states. We describe how the unique photonic properties of engineered Quantum Dot Molecules can be leveraged to overcome long-standing challenges to the creation of scalable quantum devices that manipulate single spins via photonics.