WorldWideScience

Sample records for triflate-catalyzed direct synthesis

  1. Direct dimethyl ether synthesis from synthesis gas: The influence of methanol dehydration on methanol synthesis reaction

    OpenAIRE

    Dadgar, Farbod; Myrstad, Rune; Pfeifer, Peter; Holmen, Anders; Venvik, Hilde Johnsen

    2016-01-01

    Direct dimethyl ether (DME) synthesis from synthesis gas is studied with regard to potential effects of methanol dehydration on methanol formation and copper-based catalyst performance. For this, the influence of the operating conditions (space velocity, temperature, pressure, time-on-stream and syngas composition) on activity, selectivity and stability of the catalyst was studied and compared for methanol synthesis and direct DME synthesis. The advantage of the direct over the two-step DME s...

  2. Direct synthesis of organic silicates

    International Nuclear Information System (INIS)

    Gismalla, Hana Hassan

    2000-06-01

    Tetraethoxysilane was prepared using the direct synthetic procedure in presence of magnesium ethoxide, tin tetrachloride and tin oxide as catalysts. Magnesium ethoxide was prepared firstly, identified by spectral analysis and then used in the preparation of tetraethoxysilane. The method adopted is reliable and significant as far as synthetic routes are concerned. The product obtained was analysed using infra-red spectroscopy and gas-liquid chromatography, these indicated that the final reaction product can be obtained in high yield and purity. Spectral analysis obtained are in good agreement with reported data for tetraethoxysilane. (Author)

  3. Synthesis of Siloxanes Directly from Amorphous Silica

    International Nuclear Information System (INIS)

    Myint Sandar Win

    2011-12-01

    A direct synthesis of oligomeric-siloxanes from amorphous silica has been achieved. The compound prepared was caedonal-siloxane. Cardonal is a mono hydroxyphenolic compound with a bulky group in the meta position. It was derived as a by-product from the renewable resources cashew nut shell liquid (CNSL). In the synthesis, one pot synthesis was carried out by using ethylene glycol (EG) as solvent. In the reaction ethylene glycol served as a primary precursor chelating ligand in the synthesised product. The one pot synthesis was enhanced by the strong base, triethylenetetramine (TETA) which served as the promoter catalyst. In the synthesis, optimal conditions were established on the basic of the yield percent of organo-siloxane compounds with respect to the variation of the weight fraction of TETA and to the variation of reaction time. Experimental runs were carried out at (ca 210 2c) which was nearly above the boiling point of the solvent. The substituted organo-silicon compounds obtained were characterized by FT- ir, Thermal analysis, XRD and SEM.

  4. Direct electrochemical synthesis of metal alcoholates

    International Nuclear Information System (INIS)

    Shrejder, V.A.; Turevskaya, E.P.; Kozlova, N.I.; Turova, N.Ya.

    1981-01-01

    Conditions of electrochemical synthesis of Ga, Sc, Y, Ge, Ti, Zr, Nb and Ta alcoholates during anodic metal dissolution in absolute alcohols in the presence of background electrolyte are studied. R 4 NBr and R 4 NBF 4 salts are optimum background electrolytes. Application limits of this synthetical method using different metals as anode are determined. It is supposed that alkoxyhalogenides the nature of which determines further direction of electrode process, are the primary products of anodic oxidation of metals [ru

  5. Direct synthesis of some significant metal alkoxides

    International Nuclear Information System (INIS)

    Emilio, Gule Buyu

    1998-11-01

    Investigations were carried out with an attempt to study direct synthesis of metal alkoxides from elemental metals and appropriate alcohols. These were done by reacting representative metals of group I, II, III 7 IV (which are Na, Mg, Al and Sn respectively) directly with dry ethanol and dry isopropanol. The products were then analysed by infrared spectrophotometer to meter to identify metal alkoxides formed. Ethanol was found to have more acidic character in reactions with these metals than isopropanol, thus its reactions with the metals were faster. Reduction in the acidic character of isopropanol, a secondary alcohol, could be due to the existence off more alkyl groups in the molecule which displays +1 inductive effect. For the same alcohol the metals reactions were found to decrease with increase in electronegativity of the metals. Sodium being the least electronegative metal reacted fasted while tin the more electronegative metal reacted slowest. Mg, Al and Sn required a catalyst,, mercury (II) chloride and heat in order to initiate and drive the reactions completion. The alkoxides formed were found to be soluble to a certain extent in the tow alcohols and the order of solubility is such that Sn≥ Al ≥ Mg ≥ Na.(Author)

  6. Enzymatic synthesis of ß-lactam antibiotics via direct condensation

    NARCIS (Netherlands)

    Ulijn, R.V.; Martin, de L.; Halling, P.J.; Moore, B.D.; Janssen, A.E.M.

    2002-01-01

    In this paper, the feasibility of precipitation driven synthesis of acidic and zwitterionic -lactam antibiotics is studied. As an example of the first type, penicillin G was produced in good yield (160 mmol kg-1) directly from the free acid and amine aqueous substrate suspension, where the synthesis

  7. Direct synthesis of macrodiolides via hafnium(IV) catalysis.

    Science.gov (United States)

    de Léséleuc, Mylène; Collins, Shawn K

    2015-07-04

    Efficient direct synthesis of macrodiolides via catalysis using Hf(OTf)4 is possible in high yields, forming water as the sole by-product. The first protocol for the direct synthesis of macrodiolides from equimolar mixtures of diols and dicarboxylic acids was developed (58-96%). In addition, modification of the reaction concentration allows for the synthesis of head-to-tail macrodiolides from the corresponding seco acids. The catalytic preparation of the macrodiolides using a commercially available catalyst without the need for slow addition or azeotropic condition provides an operationally simple alternative to protocols which employ toxic tin catalysts or stoichiometric activation strategies.

  8. Direct oligonucleotide synthesis onto super-paramagnetic beads

    Science.gov (United States)

    Jensen, Michael A; Akhras, Michael S.; Fukushima, Marilyn; Pourmand, Nader; Davis, Ron W.

    2013-01-01

    Super-paramagnetic beads (SPMB)s used for a variety of molecular diagnostic assays are prepared by attaching pre-synthesized oligonucleotides to the surface via a cumbersome and low efficient method of carbodiimide-mediated amide bond formation. To mainstream the process, we describe a novel procedure of direct oligonucleotide synthesis onto the surface of SPMBs (e.g. MyOne Dynabeads). With the many challenges surrounding containment of paramagnetic beads (≤ 1 μm) during automated oligonucleotide synthesis, we show that by applying a magnetic force directly to the SPMBs we prevent their loss caused by high-pressure drain steps during synthesis. To date we have synthesized 40mers using a Spacer 9 phosphoramidite (triethylene glycol) coupled to the surface of hydroxylated SPMBs. HPLC analysis shows successful product generation with an average yield of 200 pmoles per sample. Furthermore, because of the versatility of this powerful research tool, we envision its use in any laboratory working with conventional synthesis automation, as employed for single columns and for multi-well titer plates. In addition to direct synthesis of oligodeoxynucleotides (DNA) onto SPMBs, this platform also has the potential for RNA and peptide nucleic acid synthesis. PMID:23942380

  9. Effect of direction on loudness in individual binaural synthesis

    DEFF Research Database (Denmark)

    Sivonen, Ville Pekka; Minnaar, Pauli; Ellermeier, Wolfgang

    2005-01-01

    The effect of sound incidence angle on loudness is investigated in this study using binaural synthesis. Individual head-related transfer functions (HRTFs) and headphone equalization are used to present narrow-band noises from different directions to listeners. Their task is to match the loudness...

  10. Direct synthesis of catalyzed hydride compounds

    Science.gov (United States)

    Gross, Karl J.; Majzoub, Eric

    2004-09-21

    A method is disclosed for directly preparing alkali metal aluminum hydrides such as NaAlH.sub.4 and Na.sub.3 AlH.sub.6 from either the alkali metal or its hydride, and aluminum. The hydride thus prepared is doped with a small portion of a transition metal catalyst compound, such as TiCl.sub.3, TiF.sub.3, or a mixture of these materials, in order to render them reversibly hydridable. The process provides for mechanically mixing the dry reagents under an inert atmosphere followed by charging the mixed materials with high pressure hydrogen while heating the mixture to about 125.degree. C. The method is relatively simple and inexpensive and provides reversible hydride compounds which are free of the usual contamination introduced by prior art wet chemical methods.

  11. Synthesis of Directional Sources Using Wave Field Synthesis, Possibilities, and Limitations

    Directory of Open Access Journals (Sweden)

    Corteel E

    2007-01-01

    Full Text Available The synthesis of directional sources using wave field synthesis is described. The proposed formulation relies on an ensemble of elementary directivity functions based on a subset of spherical harmonics. These can be combined to create and manipulate directivity characteristics of the synthesized virtual sources. The WFS formulation introduces artifacts in the synthesized sound field for both ideal and real loudspeakers. These artifacts can be partly compensated for using dedicated equalization techniques. A multichannel equalization technique is shown to provide accurate results thus enabling for the manipulation of directional sources with limited reconstruction artifacts. Applications of directional sources to the control of the direct sound field and the interaction with the listening room are discussed.

  12. Search Directions for Direct H2O2 Synthesis Catalysts Starting from Au-12 Nanoclusters

    DEFF Research Database (Denmark)

    Grabow, Lars; Larsen, Britt Hvolbæk; Falsig, Hanne

    2012-01-01

    We present density functional theory calculations on the direct synthesis of H2O2 from H-2 and O-2 over an Au-12 corner model of a gold nanoparticle. We first show a simple route for the direct formation of H2O2 over a gold nanocatalyst, by studying the energetics of 20 possible elementary...... that the rate of H2O2 and H2O formation can be determined from a single descriptor, namely, the binding energy of oxygen (E-O). Our model predicts the search direction starting from an Au-12 nanocluster for an optimal catalyst in terms of activity and selectivity for direct H2O2 synthesis. Taking also stability...

  13. High-pressure direct synthesis of aluminium nitride

    CERN Document Server

    Bockowski, M; Grzegory, I; Krukowski, S; Wróblewski, M; Porowski, S

    2002-01-01

    We report the results of direct synthesis of aluminium nitride (AlN) under high nitrogen pressure up to 1 GPa and temperatures up to 2000 K. At pressure from 10 to 650 MPa we observe the combustion synthesis of AlN. As the result of the combustion process one can obtain the AlN sintered powder or AlN/Al metal matrix composites. For N sub 2 pressure higher than 650 MPa the crystal growth of AlN from the solution of atomic nitrogen in aluminium is possible. Both needle-like and bulk AlN single crystals, up to 1 cm and 1 mm, respectively, have been obtained.

  14. Hydrothermal Synthesis of Disulfide-Containing Uranyl Compounds. In Situ Ligand Synthesis versus Direct Assembly

    Energy Technology Data Exchange (ETDEWEB)

    Rowland, Clare E. [George Washington Univ., Washington, DC (United States); Belai, Nebebech [George Washington Univ., Washington, DC (United States); Knope, Karah E. [George Washington Univ., Washington, DC (United States); Cahill, Christopher L. [George Washington Univ., Washington, DC (United States)

    2010-01-29

    Three disulfide-containing uranyl compounds, [UO2(C7H4O2S)3]·H2O (1), [UO2(C7H4O2S)2(C7H5O2S)] (2), and [UO2(C7H4O2S)4] (3) have been hydrothermally synthesized. Both in situ disulfide bond formation from 3- and 4-mercaptobenzoic acid (C7H5O2S, MBA) to yield 3,3'- and 4,4'-dithiobisbenzoic acid (C14H8O4S2, DTBA) and direct assembly with the presynthesized dimeric ligands have been explored. While the starting materials 4-MBA and 4,4'-DTBA both yield 2 via in situ ligand synthesis and direct assembly, respectively, we observe the formation of 1 from the starting material 3-MBA via in situ ligand synthesis and of 3 from the direct assembly of the uranyl cation with 3,3'-DTBA. Concurrently with the synthesis of 1 and 2, we have observed the in situ formation of the crystalline dimeric organic species, 3,3'-DTBA, [(C7H5O2S)2] (4) and 4,4'-DTBA, [(C7H5O2S)2] (5). Herein we report the synthesis and crystallographic characterization of 1-5, as well as observations regarding the utility of product formation via direct assembly and in situ ligand synthesis.

  15. Analytical Devices Based on Direct Synthesis of DNA on Paper.

    Science.gov (United States)

    Glavan, Ana C; Niu, Jia; Chen, Zhen; Güder, Firat; Cheng, Chao-Min; Liu, David; Whitesides, George M

    2016-01-05

    This paper addresses a growing need in clinical diagnostics for parallel, multiplex analysis of biomarkers from small biological samples. It describes a new procedure for assembling arrays of ssDNA and proteins on paper. This method starts with the synthesis of DNA oligonucleotides covalently linked to paper and proceeds to assemble microzones of DNA-conjugated paper into arrays capable of simultaneously capturing DNA, DNA-conjugated protein antigens, and DNA-conjugated antibodies. The synthesis of ssDNA oligonucleotides on paper is convenient and effective with 32% of the oligonucleotides cleaved and eluted from the paper substrate being full-length by HPLC for a 32-mer. These ssDNA arrays can be used to detect fluorophore-linked DNA oligonucleotides in solution, and as the basis for DNA-directed assembly of arrays of DNA-conjugated capture antibodies on paper, detect protein antigens by sandwich ELISAs. Paper-anchored ssDNA arrays with different sequences can be used to assemble paper-based devices capable of detecting DNA and antibodies in the same device and enable simple microfluidic paper-based devices.

  16. A direct method for the synthesis of orthogonally protected furyl- and thienyl- amino acids.

    Science.gov (United States)

    Hudson, Alex S; Caron, Laurent; Colgin, Neil; Cobb, Steven L

    2015-04-01

    The synthesis of unnatural amino acids plays a key part in expanding the potential application of peptide-based drugs and in the total synthesis of peptide natural products. Herein, we report a direct method for the synthesis of orthogonally protected 5-membered heteroaromatic amino acids.

  17. Direct chemical vapour deposited grapheme synthesis on silicon oxide by controlled copper dewettting

    NARCIS (Netherlands)

    van den Beld, Wesley Theodorus Eduardus; van den Berg, Albert; Eijkel, Jan C.T.

    2015-01-01

    In this paper we present a novel method for direct uniform graphene synthesis onto silicon oxide in a controlled manner. On a grooved silicon oxide wafer is copper deposited under a slight angle and subsequently the substrate is treated by a typical graphene synthesis process. During this process

  18. Direct and Versatile Synthesis of Red-Shifted Azobenzenes

    NARCIS (Netherlands)

    Hansen, Mickel J.; Lerch, Michael M.; Szymanski, Wiktor; Feringa, Ben L.

    2016-01-01

    A straightforward synthesis of azobenzenes with bathochromically-shifted absorption bands is presented. It employs an ortho-lithiation of aromatic substrates, followed by a coupling reaction with aryldiazonium salts. The products are obtained with good to excellent yields after simple purification.

  19. Nuclear transport factor directs localization of protein synthesis during mitosis

    NARCIS (Netherlands)

    Bogaart, Geert van den; Meinema, Anne C.; Krasnikov, Viktor; Veenhoff, Liesbeth M.; Poolman, Bert

    Export of messenger RNA from the transcription site in the nucleus and mRNA targeting to the translation site in the cytoplasm are key regulatory processes in protein synthesis. In yeast, the mRNA-binding proteins Nab2p and Nab4p/Hrp1p accompany transcripts to their translation site, where the

  20. Direct Synthesis of ESBO Derivatives-18O Labelled with Dioxirane

    Directory of Open Access Journals (Sweden)

    Stefano La Tegola

    2013-01-01

    Full Text Available This work addresses a new approach developed in our laboratory, consisting in the application of isolated dimethyldioxirane (DDO, 1a labelled with 18O for synthesis of epoxidized glyceryl linoleate (Gly-LLL, 2. We expect that this work could contribute in improving analytical methods for the determination of epoxidized soybean oil (ESBO in complex food matrices by adopting an 18O-labelled-epoxidized triacylglycerol as an internal standard.

  1. Direct Synthesis of ESBO Derivatives-18O Labelled with Dioxirane

    Science.gov (United States)

    Tommasi, Immacolata; Fusco, Caterina

    2013-01-01

    This work addresses a new approach developed in our laboratory, consisting in the application of isolated dimethyldioxirane (DDO, 1a) labelled with 18O for synthesis of epoxidized glyceryl linoleate (Gly-LLL, 2). We expect that this work could contribute in improving analytical methods for the determination of epoxidized soybean oil (ESBO) in complex food matrices by adopting an 18O-labelled-epoxidized triacylglycerol as an internal standard. PMID:24163617

  2. Direct synthesis of nanocrystalline oxide powders by wet-chemical techniques

    Directory of Open Access Journals (Sweden)

    Vladimir V. Srdić

    2010-09-01

    Full Text Available In a recent period there is a great need for increasing the knowledge of tailoring the innovative procedures for the synthesis of electroceramic nanopowders and materials with improved quality for specific application. In order to produce electroceramics with desirable microstructure and properties, synthesis of stoichiometric, ultra-fine and agglomerate free powders with narrow size distributions is one of the most important steps. Within this scope, in the present paper we summarize our recent results on direct synthesis of some important perovskites and ferrites nanopowders by wet-chemical techniques.

  3. Protein synthesis directed by cowpea mosaic virus RNAs

    International Nuclear Information System (INIS)

    Stuik, E.

    1979-01-01

    The thesis concerns the proteins synthesized under direction of Cowpea mosaic virus RNAs. Sufficient radioactive labelling of proteins was achieved when 35 S as sulphate was administered to intact Vigna plants, cultivated in Hoagland solution. The large polypeptides synthesized under direction of B- and M-RNA are probably precursor molecules from which the coat proteins are generated by a mechanism of posttranslational cleavage. (Auth.)

  4. Taxation and foreign direct investment; a synthesis of empirical research

    OpenAIRE

    Ruud de Mooij; S. Ederveen

    2001-01-01

    This paper reviews the empirical literature on the impact of company taxes on the allocation of foreign direct investment. We make the outcomes of 25 empirical studies comparable by computing the tax rate elasticity under a uniform definition. Read also the accompanying press release . The mean value of the tax rate elasticity in the literature is around 3.3, i.e. a 1%-point reduction in the host-country tax rate raises foreign direct investment in that country by 3.3%. There exists substanti...

  5. Lyotropic liquid crystal directed synthesis of nanostructured materials

    Directory of Open Access Journals (Sweden)

    Cuiqing Wang, Dairong Chen and Xiuling Jiao

    2009-01-01

    Full Text Available This review introduces and summarizes lyotropic liquid crystal (LLC directed syntheses of nanostructured materials consisting of porous nanostructures and zero-dimensional (0-D, one-dimensional (1-D and two-dimensional (2-D nanostructures. After a brief introduction to the liquid crystals, the LLCs used to prepare mesoporous materials are discussed; in particular, recent advances in controlling mesostructures are summarized. The LLC templates directing the syntheses of nanoparticles, nanorods, nanowires and nanoplates are also presented. Finally, future development in this field is discussed.

  6. A decade of adaptive governance scholarship: synthesis and future directions

    Directory of Open Access Journals (Sweden)

    Brian C. Chaffin

    2014-09-01

    Full Text Available Adaptive governance is an emergent form of environmental governance that is increasingly called upon by scholars and practitioners to coordinate resource management regimes in the face of the complexity and uncertainty associated with rapid environmental change. Although the term "adaptive governance" is not exclusively applied to the governance of social-ecological systems, related research represents a significant outgrowth of literature on resilience, social-ecological systems, and environmental governance. We present a chronology of major scholarship on adaptive governance, synthesizing efforts to define the concept and identifying the array of governance concepts associated with transformation toward adaptive governance. Based on this synthesis, we define adaptive governance as a range of interactions between actors, networks, organizations, and institutions emerging in pursuit of a desired state for social-ecological systems. In addition, we identify and discuss ambiguities in adaptive governance scholarship such as the roles of adaptive management, crisis, and a desired state for governance of social-ecological systems. Finally, we outline a research agenda to examine whether an adaptive governance approach can become institutionalized under current legal frameworks and political contexts. We suggest a further investigation of the relationship between adaptive governance and the principles of good governance; the roles of power and politics in the emergence of adaptive governance; and potential interventions such as legal reform that may catalyze or enhance governance adaptations or transformation toward adaptive governance.

  7. Behavioral Synthesis of Asynchronous Circuits Using Syntax Directed Translation as Backend

    DEFF Research Database (Denmark)

    Nielsen, Sune Fallgaard; Sparsø, Jens; Madsen, Jan

    2009-01-01

    The current state-of-the art in high-level synthesis of asynchronous circuits is syntax directed translation, which performs a one-to-one mapping of a HDL-description into a corresponding circuit. This paper presents a method for behavioral synthesis of asynchronous circuits which builds on top...... of syntax directed translation, and which allows the designer to perform automatic design space exploration guided by area or speed constraints. The paper presents an asynchronous implementation template consisting of a data-path and a control unit and its implementation using the asynchronous hardware...

  8. Infants’ understanding of object-directed action: An interdisciplinary synthesis

    Directory of Open Access Journals (Sweden)

    Scott J. Robson

    2016-02-01

    Full Text Available Recognizing that the object-directed actions of others are governed by goals and intentions is a crucial component of human interaction. These actions often occur rapidly and without explanation, yet we learn from and predict the actions of others with remarkable speed and accuracy, even during the first year of life. This review paper will serve as a bridge between several disparate literatures that, we suggest, can each contribute to our understanding of how infants interpret action. Specifically, we provide a review not just of research on infant goal attribution per se, but also incorporate findings from studies on the mirror neuron system and infant object cognition. The integration of these various research approaches allows for a novel construal of the extents and limits of early goal attribution -- one in which the importance of the entire action context is considered -- and points to specific future research directions.

  9. Laser Direct Write Synthesis of Lead Halide Perovskites.

    Science.gov (United States)

    Chou, Stanley S; Swartzentruber, Brian S; Janish, Matthew T; Meyer, Kristin C; Biedermann, Laura B; Okur, Serdal; Burckel, D Bruce; Carter, C Barry; Kaehr, Bryan

    2016-10-06

    Lead halide perovskites are increasingly considered for applications beyond photovoltaics, for example, light emission and detection, where an ability to pattern and prototype microscale geometries can facilitate the incorporation of this class of materials into devices. Here we demonstrate laser direct write of lead halide perovskites, a remarkably simple procedure that takes advantage of the inverse dependence between perovskite solubility and temperature by using a laser to induce localized heating of an absorbing substrate. We demonstrate arbitrary pattern formation of crystalline CH 3 NH 3 PbBr 3 on a range of substrates and fabricate and characterize a microscale photodetector using this approach. This direct write methodology provides a path forward for the prototyping and production of perovskite-based devices.

  10. Synthesis and characterization of Al-TON zeolite using a dialkylimizadolium as structure-directing agent

    Energy Technology Data Exchange (ETDEWEB)

    Lopes, Christian Wittee; Pergher, Sibele Berenice Castella, E-mail: chriswittee@gmail.com [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil); Villarroel-Rocha, Jhonny [Laboratorio de Solidos Porosos, Instituto de Fisica Aplicada, Universidad Nacional de San Luis, Chacabuco, San Luis (Argentina); Silva, Bernardo Araldi Da; Mignoni, Marcelo Luis [Universidade Regional Integrada, Erechim, RS (Brazil)

    2016-11-15

    In this work, the synthesis of zeolites using 1-butyl-3-methylimidazolium chloride [C{sub 4}MI]Cl as a structure-directing agent was investigated. The organic cation shows effectiveness and selectivity for the syntheses of TON zeolites under different reaction conditions compared to the traditional structure directing agent, 1,8-diaminooctane. The 1-butyl-3-methylimidazolium cation lead to highly crystalline materials and its role as OSDA in our synthesis conditions has been confirmed by characterization techniques. ICP-OES confirms the presence of Al in the samples and {sup 27}Al MAS NMR analysis indicated that aluminum atoms were incorporated in tetrahedral coordination. Scanning electron microscopy indicated that changing the crystallization condition (static or stirring), zeolites with different crystal size were obtained, which consequently affects the textural properties of the zeolites. Moreover, varying some synthesis parameters MFI zeolite can also be obtained. (author)

  11. Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization

    KAUST Repository

    Jian, Zhongbao

    2016-10-14

    A single-step route to telechelic polyethylene (PE) is enabled by selective insertion polymerization. PdII-catalyzed copolymerization of ethylene and 2-vinylfuran (VF) generates α,ω-di-furan telechelic polyethylene. Orthogonally reactive exclusively in-chain anhydride groups are formed by terpolymerization with carbic anhydride. Combined experimental and theoretical DFT studies reveal the key for this direct approach to telechelics to be a match of the comonomers’ different electronics and bulk. Identified essential features of the comonomer are that it is an electron-rich olefin that forms an insertion product stabilized by an additional interaction, namely a π–η3 interaction for the case of VF.

  12. Glutathione synthesis rates after amino acid administration directly after birth in preterm infants

    NARCIS (Netherlands)

    te Braake, Frans W. J.; Schierbeek, Henk; de Groof, Karien; Vermes, Andras; Longini, Mariangela; Buonocore, Giuseppe; van Goudoever, Johannes B.

    2008-01-01

    The availability of glutathione, the main intracellular antioxidant, is compromised in preterm neonates. A possible explanation is the low availability of substrate for synthesis, because many neonatologists are reluctant to administer amino acids in the direct postnatal period for fear of

  13. Direct synthesis of dimethyl carbonate from CO 2 and methanol over ...

    Indian Academy of Sciences (India)

    The direct synthesis of dimethyl carbonate (DMC) from carbon dioxide CO2 and methanol is an attractive approach towards conversion of the greenhouse gas - CO2 into value-added chemicals and fuels.Ceria CeO2 catalyzes this reaction. But the conversion efficiency of CeO2 is enhanced when the byproductwater in the ...

  14. Ruthenium(II)-catalyzed synthesis of hydroxylated arenes with ester as an effective directing group.

    Science.gov (United States)

    Yang, Yiqing; Lin, Yun; Rao, Yu

    2012-06-01

    An unprecedented Ru(II) catalyzed ortho-hydroxylation has been developed for the facile synthesis of a variety of multifunctionalized arenes from easily accessible ethyl benzoates with ester as an efficient directing group. Both the TFA/TFAA cosolvent system and oxidants serve as the critical success factors in this transformation. The reaction demonstrates excellent reactivity, good functional group tolerance, and high yields.

  15. Direct synthesis and inkjetting of silver nanocrystals toward printed electronics

    Science.gov (United States)

    Jong Lee, Kwi; Jun, Byung Ho; Kim, Tae Hoon; Joung, Jaewoo

    2006-05-01

    Monolayer-protected silver nanoparticles were directly synthesized in a highly concentrated organic phase (>2 M) and then printed into conductive lines on polyimide by a drop-on-demand inkjet printer. The fully organic phase system contains silver nitrate as a silver precursor, n-butylamine as a media dissolving silver salt, dodecanoic acid as a capping molecule, toluene as a solvent, and sodium borohydride as a reducing reagent. Even using only generic chemicals, monodispersed silver nanocrystals with size of 7 nm were easily synthesized at the 100 g scale in a 1 litre reactor. Hydrocarbon monolayer-protected silver nanocrystal showed excellent dispersion stability even at metal content >70 wt%. The silver ink with metal content of 33 wt% had a viscosity of 5.4 cP and surface tension of 25 dyn cm-1. The silver ink was successfully inkjetted on variable substrates and then metallized at 250 °C. The metallized silver patterns exhibited very low specific electrical resistance (6 µΩ cm)

  16. Direct synthesis of silver nanoparticles in ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Corrêa, Cíntia M.; Bizeto, Marcos A.; Camilo, Fernanda F., E-mail: ffcamilo@unifesp.br [Universidade Federal de São Paulo, Laboratório de Materiais Híbridos, Departamento de Ciências Exatas e da Terra, Instituto de Ciências Ambientais, Químicas e Farmacêuticas (Brazil)

    2016-05-15

    Ionic liquids have structural organization at nanoscale that can trigger the spontaneous ordering of structures in nanoscopic range. Due to this characteristic, several metal nanoparticles have been prepared in this media. In this paper, we describe the direct preparation of silver nanoparticles in the following imidazolium ionic liquids: 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1,2-dimethyl-3-butylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, and in citrate tetrabutylammonium, that is an ionic liquid that acts as solvent and reducing agent at the same time. We also evaluated the morphology of the nanoparticles and the stability of the dispersions. Spherical silver nanoparticles with surface Plasmon bands in the range of 400–430 nm were produced in all the ionic liquids, with the only exception for the 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide that produced a black precipitate. The best results were obtained by using 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide and citrate tetrabutylammonium ionic liquids. The former resulted in concentrated spherical silver nanoparticles dispersion (ca. 1.0 mM of Ag) with diameters ranging from 6 to 12 nm and by adding polyvinylpyrrolidone (PVP) to the dispersions they became stable for at least 1 month. The citrate tetrabutylammonium ionic liquid produced even more concentrated dispersion of spherical silver nanoparticles with diameters ranging from 2 to 6 nm. These dispersions were quite stable without the need of PVP, since the Plasmon band in the electronic absorption spectra remained unaltered for months after the preparation. The citrate tetrabutylammonium ionic liquid offers a slow kinetic for the silver nanoparticle formation as the citrate is a milder reducing agent than borohydride.Graphical Abstract.

  17. Direct synthesis of silver nanoparticles in ionic liquid

    International Nuclear Information System (INIS)

    Corrêa, Cíntia M.; Bizeto, Marcos A.; Camilo, Fernanda F.

    2016-01-01

    Ionic liquids have structural organization at nanoscale that can trigger the spontaneous ordering of structures in nanoscopic range. Due to this characteristic, several metal nanoparticles have been prepared in this media. In this paper, we describe the direct preparation of silver nanoparticles in the following imidazolium ionic liquids: 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1,2-dimethyl-3-butylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, and in citrate tetrabutylammonium, that is an ionic liquid that acts as solvent and reducing agent at the same time. We also evaluated the morphology of the nanoparticles and the stability of the dispersions. Spherical silver nanoparticles with surface Plasmon bands in the range of 400–430 nm were produced in all the ionic liquids, with the only exception for the 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide that produced a black precipitate. The best results were obtained by using 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide and citrate tetrabutylammonium ionic liquids. The former resulted in concentrated spherical silver nanoparticles dispersion (ca. 1.0 mM of Ag) with diameters ranging from 6 to 12 nm and by adding polyvinylpyrrolidone (PVP) to the dispersions they became stable for at least 1 month. The citrate tetrabutylammonium ionic liquid produced even more concentrated dispersion of spherical silver nanoparticles with diameters ranging from 2 to 6 nm. These dispersions were quite stable without the need of PVP, since the Plasmon band in the electronic absorption spectra remained unaltered for months after the preparation. The citrate tetrabutylammonium ionic liquid offers a slow kinetic for the silver nanoparticle formation as the citrate is a milder reducing agent than borohydride.Graphical Abstract

  18. Amine-catalyzed direct aldol reactions of hydroxy- and dihydroxyacetone: biomimetic synthesis of carbohydrates.

    Science.gov (United States)

    Popik, Oskar; Pasternak-Suder, Monika; Leśniak, Katarzyna; Jawiczuk, Magdalena; Górecki, Marcin; Frelek, Jadwiga; Mlynarski, Jacek

    2014-06-20

    This article presents comprehensive studies on the application of primary, secondary, and tertiary amines as efficient organocatalysts for the de novo synthesis of ketoses and deoxyketoses. Mimicking the actions of aldolase enzymes, the synthesis of selected carbohydrates was accomplished in aqueous media by using proline- and serine-based organocatalysts. The presented methodology also provides direct access to unnatural L-carbohydrates from the (S)-glyceraldehyde precursor. Determination of the absolute configuration of all obtained sugars was feasible using a methodology consisting of concerted ECD and VCD spectroscopy.

  19. Synthesis and characterization of Cu-MFI catalyst for the direct medium temperature range NO decomposition

    Directory of Open Access Journals (Sweden)

    Valkaj Karolina Maduna

    2016-03-01

    Full Text Available In this study the physico-chemical and catalytic properties of copper bearing MFI zeolites (Cu-MFI with different Si/Al and Si/Cu ratios were investigated. Two different methods for incorporation of metal ions into the zeolite framework were used: the ion exchange from the solution of copper acetate and the direct hydrothermal synthesis. Direct synthesis of a zeolite in the presence of copper-phosphate complexes was expected to generate more active copper species necessary for the desired reaction than the conventional ion exchange method. Direct decomposition of NO was used as a model reaction, because this reaction still offers a very attractive approach to NOX removal. The catalytic properties of zeolite samples were studied using techniques, such as XRD, SEM, EPR and nitrogen adsorption/desorption measurements at 77 K. Results of the kinetic investigation revealed that both methods are applicable for the preparation of the catalysts with active sites capable of catalyzing the NO decomposition. It was found out that Cu-MFI zeolites obtained through direct synthesis are promising catalysts for NO decomposition, especially at lower reaction temperatures. The efficiency of the catalysts prepared by both methods is compared and discussed.

  20. Fabrication of spintronics device by direct synthesis of single-walled carbon nanotubes from ferromagnetic electrodes

    Directory of Open Access Journals (Sweden)

    Mohd Ambri Mohamed, Nobuhito Inami, Eiji Shikoh, Yoshiyuki Yamamoto, Hidenobu Hori and Akihiko Fujiwara

    2008-01-01

    Full Text Available We describe an alternative method for realizing a carbon nanotube spin field-effect transistor device by the direct synthesis of single-walled carbon nanotubes (SWNTs on substrates by alcohol catalytic chemical vapor deposition. We observed hysteretic magnetoresistance (MR at low temperatures due to spin-dependent transport. In these devices, the maximum ratio in resistance variation of MR was found to be 1.8%.

  1. Direct Synthesis of 7 nm Thick Zinc(II)-Benzimidazole-Acetate Metal-Organic Framework Nanosheets

    Energy Technology Data Exchange (ETDEWEB)

    Xue, Feng; Kumar, Prashant; Xu, Wenqian; Mkhoyan, K. Andre; Tsapatsis, Michael

    2018-01-09

    Two-dimensional metal-organic frameworks (MOFs) are promising candidates for high performance gas sepa-ration membranes. Currently, MOF nanosheets are mostly fabricated through delamination of layered MOFs, which often re-sults in a low yield of intact free-standing nanosheets. In this work, we present a direct synthesis method for zinc(II)-benzimidazole-acetate (Zn(Bim)OAc) MOF nanosheets. The obtained nanosheets have a lateral dimension of 600 nm when synthesized at room temperature. By adjusting the synthesis temperature, the morphology of obtained nanosheets can be readily tuned from nanosheets to nanobelts. A thickness of 7 nm is determined for Zn(Bim)OAc using high-angle annular dark-field scanning transmission electron microscopy, which makes these nanosheets promising building blocks of gas sepa-ration membranes.

  2. Laser direct synthesis and patterning of silver nano/microstructures on a polymer substrate.

    Science.gov (United States)

    Liu, Yi-Kai; Lee, Ming-Tsang

    2014-08-27

    This study presents a novel approach for the rapid fabrication of conductive nano/microscale metal structures on flexible polymer substrate (polyimide). Silver film is simultaneously synthesized and patterned on the polyimide substrate using an advanced continuous wave (CW) laser direct writing technology and a transparent, particle-free reactive silver ion ink. The location and shape of the resulting silver patterns are written by a laser beam from a digitally controlled micromirror array device. The silver patterns fabricated by this laser direct synthesis and patterning (LDSP) process exhibit the remarkably low electrical resistivity of 2.1 μΩ cm, which is compatible to the electrical resistivity of bulk silver. This novel LDSP process requires no vacuum chamber or photomasks, and the steps needed for preparation of the modified reactive silver ink are simple and straightforward. There is none of the complexity and instability associated with the synthesis of the nanoparticles that are encountered for the conventional laser direct writing technology which involves nanoparticle sintering process. This LDSP technology is an advanced method of nano/microscale selective metal patterning on flexible substrates that is fast and environmentally benign and shows potential as a feasible process for the roll-to-roll manufacturing of large area flexible electronic devices.

  3. Direct vs. indirect pathway of hepatic glycogen synthesis as a function of glucose infusion rate

    International Nuclear Information System (INIS)

    Bagby, G.J.; Lang, C.H.; Johnson, J.L.; Blakesly, H.L.; Spitzer, J.J.

    1986-01-01

    This study was initiated to determine the influence of the rate of exogenous glucose administration on liver glycogen synthesis by the direct (glucose uptake and incorporation into glycogen) vs the indirect pathway (glucose degradation to 3-carbon intermediates, e.g., lactate, prior to incorporation into glycogen). Catheterized rats were fasted 2 days prior to receiving a 3 hr infusion of glucose at rates of 0 to 230 μmol/min/kg containing tracer [6- 3 H]- and [U- 14 C]-glucose. Plasma glucose (r = 0.80), insulin (r = 0.90) and lactate (r = 0.84) were correlated with glucose infusion rate. The rate of liver glycogen deposition (0.46 +/- 0.03 μmol/min/g) did not differ between a glucose infusion rate of 20 and 230 μmol/min/kg. At the lowest and highest glucose infusion rates hepatic glycogenesis accounted for 87 +/- 6 and 9 +/- 1% of the total glucose load, respectively. The percent contribution of the direct pathways to glycogen deposition ([ 3 H] specific activity in hepatic glycogen/[ 3 H] specific activity in plasma glucose) increased from 16 +/- 3 to 83 +/- 5% from lowest to highest glucose infusion rates (prevailing plasma glucose concentrations: 9 +/- 1 and 21 +/- 2 mM, respectively). The results indicate that the relative contribution of the direct and indirect pathways of glucogen synthesis are dependent upon the glucose load or plasma glucose concentration

  4. Application of two direct C(sp3)-H functionalizations for total synthesis of (+)-lactacystin.

    Science.gov (United States)

    Yoshioka, Shun; Nagatomo, Masanori; Inoue, Masayuki

    2015-01-02

    Herein, we report a new synthetic route from (S)-pyroglutaminol to (+)-lactacystin, a potent inhibitor of the 20S proteasome. The photoinduced intermolecular C(sp(3))-H alkynylation and intramolecular C(sp(3))-H acylation chemo- and stereoselectively constructed the tetra- and trisubstituted carbon centers, respectively. The obtained bicycle was transformed into the target compound in a concise manner. The present total synthesis demonstrates the power of the direct C(sp(3))-H functionalizations for the assembly of multiple functionalized structures of natural products.

  5. In situ synthesis of nanocomposite membranes: comprehensive improvement strategy for direct methanol fuel cells.

    Science.gov (United States)

    Rao, Siyuan; Xiu, Ruijie; Si, Jiangju; Lu, Shanfu; Yang, Meng; Xiang, Yan

    2014-03-01

    In situ synthesis is a powerful approach to control nanoparticle formation and consequently confers extraordinary properties upon composite membranes relative to conventional doping methods. Herein, uniform nanoparticles of cesium hydrogen salts of phosphotungstic acid (CsPW) are controllably synthesized in situ in Nafion to form CsPW–Nafion nanocomposite membranes with both improved proton conductivity and methanol-crossover suppression. A 101.3% increase of maximum power density has been achieved relative to pristine Nafion in a direct methanol fuel cell (DMFC), indicating a potential pathway for large-scale fabrication of DMFC alternative membranes.

  6. Directing factors affecting the synthesis of a MFI-type zeolite

    International Nuclear Information System (INIS)

    Vinaches, P.; Pergher, S.B.C.; Lopes, C.W.; Gomez-Hortiguela, L.; Finger, P.H.; Silva, B.A. da; Dallago, R.M.; Mignoni, M.L.

    2016-01-01

    Full text: Zeolites are crystalline tectosilicates constituted by (TO4) tetrahedra connected through the oxygens of their vertices. The importance of these materials is that their properties differ, due to their variable compositions and structures, leading to the possibility of applying them into different industries, for example, as catalyst in petroleum industry or sensors in quality control. One of the big questions in this area is about the understanding of the chemistry that directs to one or another type of zeolite. Another important question is the search of new zeolitic structures for new applications. One approach to answer both is the study of the structure-directing agents, which are inorganic or organic molecules used in the synthesis of zeolites. New and already-used molecules have been studied within different synthesis conditions and different techniques, as characterization or computational studies. And several attempts of rationalization were and, still, will be performed. In this research, an imidazolium-based compound was studied in hydrothermal zeolite synthesis as organic structure-directing agent (OSDA). The products were obtained with Si/Al or Si/(Al+Zn) compositions, proved by ICP data. X-ray diffractograms showed two different zeolitic types: MFI and TON. It was observed that when Zn was present in the synthesis gel, pure MFI phases were able to appear. But in his absence, the products were all mixtures of MFI and TON zeolites. It was also possible to distinguish both phases by SEM micrographs, as MFI had brick-like shape and TON appeared as needles. The obtained zeolites were stable until 900°C minimum, as tested by a TG/DTG/DSC experiment. To prove that the chosen OSDA directed these structures, a CHN analysis was performed, resulting in integrity of the molecules inside the zeolitic pores and cavities. Finally, a rationale about the location and conformation of the OSDA was needed to understand these experimental results. So, it was

  7. Direct synthesis of lithium-intercalated graphene for electrochemical energy storage application.

    Science.gov (United States)

    Kumar, Ashavani; Reddy, Arava Leela Mohana; Mukherjee, Arnab; Dubey, Madan; Zhan, Xiaobo; Singh, Neelam; Ci, Lijie; Billups, W Edward; Nagurny, John; Mital, Gandhi; Ajayan, Pulickel M

    2011-06-28

    A novel approach for bulk synthesis of lithium-intercalated graphene sheets through the reduction of exfoliated graphene oxide in liquid ammonia and lithium metal is reported. It is demonstrated here that as-synthesized lithiated graphite oxide sheets (Li-RGO) can be directly used as an electrode material in lithium batteries. The electrochemical studies on Li-RGO electrodes show a significant enhancement in the specific capacity of the lithium battery over commercially available graphite electrodes. Partial intercalation of lithium ions in between graphene layers makes this material a good candidate for electrochemical energy storage applications.

  8. Recent progress in the direct synthesis of hierarchical zeolites: synthetic strategies and characterization methods

    KAUST Repository

    Liu, Zhaohui

    2017-06-16

    Hierarchically structured zeolites combine the merits of microporous zeolites and mesoporous materials to offer enhanced molecular diffusion and mass transfer without compromising the inherent catalytic activities and selectivity of zeolites. This short review gives an introduction to the synthesis strategies for hierarchically structured zeolites with emphasis on the latest progress in the route of ‘direct synthesis’ using various templates. Several characterization methods that allow us to evaluate the ‘quality’ of complex porous structures are also introduced. At the end of this review, an outlook is given to discuss some critical issues and challenges regarding the development of novel hierarchically structured zeolites as well as their applications.

  9. Directing factors affecting the synthesis of a MFI-type zeolite

    Energy Technology Data Exchange (ETDEWEB)

    Vinaches, P.; Pergher, S.B.C. [Universidade Federal de Rio Grande do Norte (UFRN), RN (Brazil); Lopes, C.W. [Institute of Chemical Technology, Mumbai (India); Gomez-Hortiguela, L. [Instituto de Catalisis y Petroleoquimica, Madrid (Spain); Finger, P.H.; Silva, B.A. da; Dallago, R.M.; Mignoni, M.L. [Universidade Regional Integrada do Alto Uruguai e das Missoes (URI), Erechim, RS (Brazil)

    2016-07-01

    Full text: Zeolites are crystalline tectosilicates constituted by (TO4) tetrahedra connected through the oxygens of their vertices. The importance of these materials is that their properties differ, due to their variable compositions and structures, leading to the possibility of applying them into different industries, for example, as catalyst in petroleum industry or sensors in quality control. One of the big questions in this area is about the understanding of the chemistry that directs to one or another type of zeolite. Another important question is the search of new zeolitic structures for new applications. One approach to answer both is the study of the structure-directing agents, which are inorganic or organic molecules used in the synthesis of zeolites. New and already-used molecules have been studied within different synthesis conditions and different techniques, as characterization or computational studies. And several attempts of rationalization were and, still, will be performed. In this research, an imidazolium-based compound was studied in hydrothermal zeolite synthesis as organic structure-directing agent (OSDA). The products were obtained with Si/Al or Si/(Al+Zn) compositions, proved by ICP data. X-ray diffractograms showed two different zeolitic types: MFI and TON. It was observed that when Zn was present in the synthesis gel, pure MFI phases were able to appear. But in his absence, the products were all mixtures of MFI and TON zeolites. It was also possible to distinguish both phases by SEM micrographs, as MFI had brick-like shape and TON appeared as needles. The obtained zeolites were stable until 900°C minimum, as tested by a TG/DTG/DSC experiment. To prove that the chosen OSDA directed these structures, a CHN analysis was performed, resulting in integrity of the molecules inside the zeolitic pores and cavities. Finally, a rationale about the location and conformation of the OSDA was needed to understand these experimental results. So, it was

  10. Direct on-chip DNA synthesis using electrochemically modified gold electrodes as solid support

    Science.gov (United States)

    Levrie, Karen; Jans, Karolien; Schepers, Guy; Vos, Rita; Van Dorpe, Pol; Lagae, Liesbet; Van Hoof, Chris; Van Aerschot, Arthur; Stakenborg, Tim

    2018-04-01

    DNA microarrays have propelled important advancements in the field of genomic research by enabling the monitoring of thousands of genes in parallel. The throughput can be increased even further by scaling down the microarray feature size. In this respect, microelectronics-based DNA arrays are promising as they can leverage semiconductor processing techniques with lithographic resolutions. We propose a method that enables the use of metal electrodes for de novo DNA synthesis without the need for an insulating support. By electrochemically functionalizing gold electrodes, these electrodes can act as solid support for phosphoramidite-based synthesis. The proposed method relies on the electrochemical reduction of diazonium salts, enabling site-specific incorporation of hydroxyl groups onto the metal electrodes. An automated DNA synthesizer was used to couple phosphoramidite moieties directly onto the OH-modified electrodes to obtain the desired oligonucleotide sequence. Characterization was done via cyclic voltammetry and fluorescence microscopy. Our results present a valuable proof-of-concept for the integration of solid-phase DNA synthesis with microelectronics.

  11. Facile Synthesis of Monodisperse ZnO Nanocrystals by Direct Liquid Phase Precipitation

    Directory of Open Access Journals (Sweden)

    Lan Chen

    2011-01-01

    Full Text Available ZnO nanocrystals can be synthesized by a variety of methods. Among them, only a few nonhydrolytic methods have been successful at low synthesis temperatures in terms of size, crystallinity, morphology and surface-defect control. These methods require very careful control of conditions and carefully engineered precursors. A new methodology—direct liquid phase precipitation—is reported here that can produce nanocrystals (NCs which are a little difficult to obtain for these complex synthesis techniques in a more facile and efficient way (i.e., at room temperature. This technique results in high quality ZnO nanocrystals of diameter 5–12 nm and different morphologies. Characterisation of ZnO products shows that both synthesis and ageing conditions have significant effects on the formation of the nanocrystals. Capping agents and ageing temperature/time can be used to control both size and crystallinity of the products. The use of in situ or ex situ ageing conditions can result in different particle morphologies. Both in situ and ex situ ageing shows that mild ageing conditions (e.g., 60–80∘C and 24–48 hours are required to produce the highest quality nanomaterials.

  12. Capability of the Direct Dimethyl Ether Synthesis Process for the Conversion of Carbon Dioxide

    Directory of Open Access Journals (Sweden)

    Ainara Ateka

    2018-04-01

    Full Text Available The direct synthesis of dimethyl ether (DME is an ideal process to achieve the environmental objective of CO2 conversion together with the economic objective of DME production. The effect of the reaction conditions (temperature, pressure, space time and feed composition (ternary mixtures of H2 + CO + CO2 with different CO2/CO and H2/COx molar ratios on the reaction indices (COx conversion, product yield and selectivity, CO2 conversion has been studied by means of experiments carried out in a fixed-bed reactor, with a CuO-ZnO-MnO/SAPO-18 catalyst, in order to establish suitable ranges of operating conditions for enhancing the individual objectives of CO2 conversion and DME yield. The optimums of these two objectives are achieved in opposite conditions, and for striking a good balance between both objectives, the following conditions are suitable: 275–300 °C; 20–30 bar; 2.5–5 gcat h (molC−1 and a H2/COx molar ratio in the feed of 3. CO2/CO molar ratio in the feed is of great importance. Ratios below 1/3 are suitable for enhancing DME production, whereas CO2/CO ratios above 1 improve the conversion of CO2. This conversion of CO2 in the overall process of DME synthesis is favored by the reverse water gas shift equation, since CO is more active than CO2 in the methanol synthesis reaction.

  13. Directed In Situ Shaping of Complex Nano- and Microstructures during Chemical Synthesis.

    Science.gov (United States)

    Artus, Georg R J; Olveira, Sandro; Patra, Debabrata; Seeger, Stefan

    2017-02-01

    Chemical composition and shape determine the basic properties of any object. Commonly, chemical synthesis and shaping follow each other in a sequence, although their combination into a single process would be an elegant simplification. Here, a pathway of simultaneous synthesis and shaping as applied to polysiloxanes on the micro- and nanoscale is presented. Complex structures such as stars, chalices, helices, volcanoes, rods, or combinations thereof are obtained. Varying the shape-controlling reaction parameters including temperature, water saturation, and the type of substrate allows to direct the reaction toward specific structures. A general mechanism of growth is suggested and analytical evidence and thermodynamic calculations to support it are provided. An aqueous droplet in either gaseous atmosphere or in a liquid organic solvent serves as a spatially confined polymerization volume. By substituting the starting materials, germanium-based nanostructures are also obtained. This transferability marks this approach as a major step toward a generally applicable method of chemical synthesis including in situ shaping. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Ultrasonic synthesis and evaluation of non-platinum catalysts for alkaline direct methanol fuel cells

    Science.gov (United States)

    Bunazawa, Hideaki; Yamazaki, Yohtaro

    Ultrasonic synthesis was investigated as a synthesis method of non-platinum catalysts for alkaline direct methanol fuel cells (alkaline DMFCs) such as 20% mass Pd/C, Au/C, and PdAu/C. Among four kinds of solvents, ethylene glycol was demonstrated to be the optimum solvent for the synthesis of those catalysts. When ethylene glycol was used, the synthesized metal nanoparticles were highly dispersed on carbon particles. The synthesized Pd/C and PdAu/C showed the high oxygen reduction reaction (ORR) activity in alkaline condition (0.5 M NaOH aqueous solution), which was comparable to conventional Pt/C. Moreover, they showed lower methanol oxidation reaction (MOR) activity. Membrane electrode assemblies (MEAs) containing the synthesized Pd/C cathode catalysts and alkaline ion exchange membranes were fabricated and evaluated by single cell tests. They showed high performance that was comparable to MEAs with Pt/C cathode. In addition, it was found that the synthesized Pd/C was relatively tolerant to methanol crossover.

  15. A Direction Finding Method with A 3-D Array Based on Aperture Synthesis

    Science.gov (United States)

    Li, Shiwen; Chen, Liangbing; Gao, Zhaozhao; Ma, Wenfeng

    2018-01-01

    Direction finding for electronic warfare application should provide a wider field of view as possible. But the maximum unambiguous field of view for conventional direction finding methods is a hemisphere. It cannot distinguish the direction of arrival of the signals from the back lobe of the array. In this paper, a full 3-D direction finding method based on aperture synthesis radiometry is proposed. The model of the direction finding system is illustrated, and the fundamentals are presented. The relationship between the outputs of the measurements of a 3-D array and the 3-D power distribution of the point sources can be represented by a 3-D Fourier transform, and then the 3-D power distribution of the point sources can be reconstructed by an inverse 3-D Fourier transform. And in order to display the 3-D power distribution of the point sources conveniently, the whole spherical distribution is represented by two 2-D circular distribution images, one of which is for the upper hemisphere, and the other is for the lower hemisphere. Then a numeric simulation is designed and conducted to demonstrate the feasibility of the method. The results show that the method can estimate the arbitrary direction of arrival of the signals in the 3-D space correctly.

  16. Studi Pendirian Pabrik Dietil Karbonat dari CO2 dan Etanol Melalui Proses Direct Synthesis

    Directory of Open Access Journals (Sweden)

    Fakhruzi Asrial Efransyah

    2017-01-01

    Full Text Available Salah satu penggerak utama perekonomian nasional merupakan energi. Bahan bakar minyak berbasis energi fosil merupakan salah satu energi yang kebutuhannya terus meningkat dari tahun ke tahun. Kebutuhan bahan bakar minyak mengikuti perkembangan sektor pembangunan khususnya sektor transportasi dan industri yang saat ini semakin pesat. Tidak dipungkiri lagi bahwa konsumsi bahan bakar fosil mempunyai dampak kepada lingkungan akibat senyawa-senyawa organik yang terkandung didalamnya. Salah satu upaya untuk mengurangi emisi yang dihasilkan dari konsumsi bahan bakar tersebut adalah dengan penambahan zat aditif pada bahan bakar minyak. Dietil Karbonat (DEC merupakan salah satu senyawa oxygenate yang menjadi alternatif zat aditif pada bahan bakar. Berdasarkan penelitian, DEC sebanyak 5 wt % dapat mengurangi materi partikulat pada mesin diesel sebanyak 50%. Sehingga penggunaan DEC mempunyai potensi tinggi dalam aspek ekonomi dan lingkungan. Setelah melewati beberapa dekade, produksi/manufaktur DEC semakin variatif dan semakin banyak penelitian yang berfokus pada sintesis DEC maupun penggunaan katalis yang terbaik. Pada studi ini, DEC disintesis dari CO2 dan Etanol melalui proses Direct Synthesis. Secara garis besar Pabrik DEC ini terdiri dari Synthesis Unit, Separation Unit, Purification Unit dan Recycle Unit. Produk yang dihasilkan adalah Dietil Karbonat, sedangkan produk samping yang dihasilkan adalah 1,2 Butanediol. Dari studi yang dilakukan untuk Pabrik DEC dengan kapasitas 90.000 ton per tahun dibutuhkan investasi sebesar USD 63.582.413. Dari analisa ekonomi diperoleh: Internal Rate of Return : 46,7%; POT: 3,05 tahun; BEP : 41,5 %; dan NPV: USD 109.327. Dari hasil tersebut dan beberapa parameter sensitifitas yaitu fluktuasi biaya investasi, harga bahan baku, kapasitas, dan harga jual dari produk, terlihat bahwa keempatnya tidak memberikan pengaruh cukup signifikan terhadap kenaikan atau penurunan nilai IRR pabrik. Sehingga Pabrik DEC dari CO2 dan

  17. DISY. The direct synthesis of hydrogen peroxide, a bridge for innovative applications

    Energy Technology Data Exchange (ETDEWEB)

    Buzzoni, R.; Perego, C. [Eni S.p.A., Novara (Italy). Research Center for Non-Conventional Energies

    2011-07-01

    Hydrogen peroxide is largely recognized as the green oxidant of choice for future sustainable processes. The current industrial production still goes through the old anthraquinone process, a complex, two-step process suffering from a low specific productivity. Following the development of TS-1/H{sub 2}O{sub 2} based selective oxidation processes e.g. propylene epoxidation, cyclohexanone ammoximation and the new benzene direct oxidation to phenol, there has been an incentive for the development of a new technology, simpler and with better economics. DISY process, based on direct synthesis of hydrogen peroxide from hydrogen and oxygen, is highly suitable to the design of integrated selective oxidation processes as well as for production of commercial-grade high concentration aqueous hydrogen peroxide solutions. Catalyst and process development up to pilot scale are described. (orig.)

  18. Block copolymer directed synthesis of mesoporous TiO 2 for dye-sensitized solar cells

    KAUST Repository

    Nedelcu, Mihaela

    2009-01-01

    The morphology of TiO2 plays an important role in the operation of solid-state dye-sensitized solar cells. By using polyisoprene-block- ethyleneoxide (PI-b-PEO) copolymers as structure directing agents for a sol-gel based synthesis of mesoporous TiO2, we demonstrate a strategy for the detailed control of the semiconductor morphology on the 10 nm length scale. The careful adjustment of polymer molecular weight and titania precursor content is used to systematically vary the material structure and its influence upon solar cell performance is investigated. Furthermore, the use of a partially sp 2 hybridized structure directing polymer enables the crystallization of porous TiO2 networks at high temperatures without pore collapse, improving its performance in solid-state dye-sensitized solar cells. © 2009 The Royal Society of Chemistry.

  19. Structure-directing effects of ionic liquids in the ionothermal synthesis of metal–organic frameworks

    Directory of Open Access Journals (Sweden)

    Thomas P. Vaid

    2017-07-01

    Full Text Available Traditional synthesis of metal–organic frameworks (MOFs involves the reaction of a metal-containing precursor with an organic linker in an organic solvent at an elevated temperature, in what is termed a `solvothermal' reaction. More recently, many examples have been reported of MOF synthesis in ionic liquids (ILs, rather than an organic solvent, in `ionothermal' reactions. The high concentration of both cations and anions in an ionic liquid allows for the formation of new MOF structures in which the IL cation or anion or both are incorporated into the MOF. Most commonly, the IL cation is included in the open cavities of the MOF, countering the anionic charge of the MOF framework itself and acting as a template around which the MOF structure forms. Ionic liquids can also serve other structure-directing roles, for example, when an IL containing a single enantiomer of a chiral anion leads to a homochiral MOF, even though the IL anion is not itself incorporated into the MOF. A comprehensive review of ionothermal syntheses of MOFs, and the structure-directing effects of the ILs, is given.

  20. DnaB gene product-independence of DNA polymerase III-directed repair synthesis in Escherichia coli K-12

    International Nuclear Information System (INIS)

    Billen, D.; Hellermann, G.R.

    1977-01-01

    An investigation has been carried out into the role of dnaB gene product in X-ray-induced repair synthesis carried out by DNA polymerase III in toluene-treated Escherichia coli K-12. A polAl polBlOO dnaB mutant deficient in both DNA polymerase I and II activities was used, and it was shown that the level of X-ray-induced, ATP-dependent, non-conservative DNA synthesis was, unlike semi-conservative DNA synthesis, unaffected by a temperature shift from 30 0 to 42 0 C. The dnaB gene product was not therefore necessary for DNA polymerase III-directed repair synthesis, which occurred in the absence of replicative synthesis. (U.K.)

  1. Direct Analysis in Real Time Mass Spectrometry of Potential By-Products from Homemade Nitrate Ester Explosive Synthesis

    OpenAIRE

    Sisco, Edward; Forbes, Thomas P.

    2015-01-01

    This work demonstrates the coupling of direct analysis in real time (DART) ionization with time-of-flight mass spectrometry (MS) in an off-axis configuration for the trace detection and analysis of potential partially nitrated and dimerized by-products of homemade nitrate ester explosive synthesis. Five compounds relating to the synthesis of nitroglycerin (NG) and pentaerythritol tetranitrate (PETN) were examined. Deprotonated ions and adducts with molecular oxygen, nitrite, and nitrate were ...

  2. Stereoselective, nitro-Mannich/lactamisation cascades for the direct synthesis of heavily decorated 5-nitropiperidin-2-ones and related heterocycles

    Directory of Open Access Journals (Sweden)

    Pavol Jakubec

    2012-04-01

    Full Text Available A versatile nitro-Mannich/lactamisation cascade for the direct stereoselective synthesis of heavily decorated 5-nitropiperidin-2-ones and related heterocycles has been developed. A highly enantioenriched substituted 5-nitropiperidin-2-one was synthesised in a four component one-pot reaction combining an enantioselective organocatalytic Michael addition with the diastereoselective nitro-Mannich/lactamisation cascade. Protodenitration and chemoselective reductive manipulation of the heterocycles was used to install contiguous and fully substituted stereocentres in the synthesis of substituted piperidines.

  3. Stereoselective, nitro-Mannich/lactamisation cascades for the direct synthesis of heavily decorated 5-nitropiperidin-2-ones and related heterocycles

    Science.gov (United States)

    Jakubec, Pavol; Cockfield, Dane M; Helliwell, Madeleine; Raftery, James

    2012-01-01

    Summary A versatile nitro-Mannich/lactamisation cascade for the direct stereoselective synthesis of heavily decorated 5-nitropiperidin-2-ones and related heterocycles has been developed. A highly enantioenriched substituted 5-nitropiperidin-2-one was synthesised in a four component one-pot reaction combining an enantioselective organocatalytic Michael addition with the diastereoselective nitro-Mannich/lactamisation cascade. Protodenitration and chemoselective reductive manipulation of the heterocycles was used to install contiguous and fully substituted stereocentres in the synthesis of substituted piperidines. PMID:22563355

  4. Stereoselective, nitro-Mannich/lactamisation cascades for the direct synthesis of heavily decorated 5-nitropiperidin-2-ones and related heterocycles.

    Science.gov (United States)

    Jakubec, Pavol; Cockfield, Dane M; Helliwell, Madeleine; Raftery, James; Dixon, Darren J

    2012-01-01

    A versatile nitro-Mannich/lactamisation cascade for the direct stereoselective synthesis of heavily decorated 5-nitropiperidin-2-ones and related heterocycles has been developed. A highly enantioenriched substituted 5-nitropiperidin-2-one was synthesised in a four component one-pot reaction combining an enantioselective organocatalytic Michael addition with the diastereoselective nitro-Mannich/lactamisation cascade. Protodenitration and chemoselective reductive manipulation of the heterocycles was used to install contiguous and fully substituted stereocentres in the synthesis of substituted piperidines.

  5. Catalytic enantioselective synthesis of atropisomeric biaryls by a cation-directed O-alkylation

    Science.gov (United States)

    Jolliffe, John D.; Armstrong, Roly J.; Smith, Martin D.

    2017-06-01

    Axially chiral biaryls, as exemplified by 1,1‧-bi-2-naphthol (BINOL), are key components of catalysts, natural products and medicines. These materials are synthesized conventionally in enantioenriched form through metal-mediated cross coupling, de novo construction of an aromatic ring, point-to-axial chirality transfer or an atropselective transformation of an existing biaryl. Here, we report a highly enantioselective organocatalytic method for the synthesis of atropisomeric biaryls by a cation-directed O-alkylation. Treatment of racemic 1-aryl-2-tetralones with a chiral quinidine-derived ammonium salt under basic conditions in the presence of an alkylating agent leads to atropselective O-alkylation with e.r. up to 98:2. Oxidation with DDQ gives access to C2-symmetric and non-symmetric BINOL derivatives without compromising e.r. We propose that the chiral ammonium counterion differentiates between rapidly equilibrating atropisomeric enolates, leading to highly atropselective O-alkylation. This dynamic kinetic resolution process offers a general approach to the synthesis of enantioenriched atropisomeric materials.

  6. Direct Arylation Strategies in the Synthesis of π-Extended Monomers for Organic Polymeric Solar Cells

    Directory of Open Access Journals (Sweden)

    Andrea Nitti

    2016-12-01

    Full Text Available π-conjugated macromolecules for organic polymeric solar cells can be rationally engineered at the molecular level in order to tune the optical, electrochemical and solid-state morphology characteristics, and thus to address requirements for the efficient solid state device implementation. The synthetic accessibility of monomers and polymers required for the device is getting increasing attention. Direct arylation reactions for the production of the π-extended scaffolds are gaining importance, bearing clear advantages over traditional carbon-carbon forming methodologies. Although their use in the final polymerization step is already established, there is a need for improving synthetic accessibility to implement them also in the monomer synthesis. In this review, we discuss recent examples highlighting this useful strategy.

  7. Mergers and acquisitions: A synthesis of theories and directions for future research

    Directory of Open Access Journals (Sweden)

    Wissal Ben Letaifa

    2017-02-01

    Full Text Available The purpose of this paper is to review a synthesis of theories and empirical studies dealing with the mergers and acquisitions in the recent decay in an attempt to provide directions for future research. The review focuses on four main streams including: first, the motives for mergers-acquisitions; which are the strategic profits, the overconfidence of managers and the desire to create a big empire resulting from merger. From second, corporate characteristics of firms that did merger or acquisition; third, the economic consequences of the operation of merger and acquisition and finally; fourth, the implication on the market with the impact of merger on the value of the firm. We think that this article can give another idea about the information disclosed by any company choosing to merge and can be analyzed by practitioners by giving them the theoretical background of the merger and acquisition problem.

  8. Direct Digital Synthesis Chirped Pulse Microwave Spectrometers for the Classroom and Research

    Science.gov (United States)

    Blake, Geoffrey; Carroll, Brandon; Finneran, Ian A.

    2015-06-01

    By combining the rapid development in direct digital synthesis circuitry and Field Programmable Gate Arrays (FPGAs) coupled to fast A/D samplers, it is possible to construct high performance chirped pulse microwave spectrometers suitable for gas-phase rotational spectroscopy experiments in undergraduate physical chemistry labs as well as graduate level research. The technology is highly tailorable, and sufficiently robust that extensive experimentation is feasible in the teaching environment. The time domain nature of the experiment has strong ties to concepts in Nuclear Magnetic Resonance (NMR) widely discussed in undergraduate curricula, and the software environment for the instrument control and spectral assignment can be integrated with ab initio quantum chemistry predictions of molecular structure and dynamics.

  9. Direct Arylation Strategies in the Synthesis of π-Extended Monomers for Organic Polymeric Solar Cells.

    Science.gov (United States)

    Nitti, Andrea; Po, Riccardo; Bianchi, Gabriele; Pasini, Dario

    2016-12-26

    π-conjugated macromolecules for organic polymeric solar cells can be rationally engineered at the molecular level in order to tune the optical, electrochemical and solid-state morphology characteristics, and thus to address requirements for the efficient solid state device implementation. The synthetic accessibility of monomers and polymers required for the device is getting increasing attention. Direct arylation reactions for the production of the π-extended scaffolds are gaining importance, bearing clear advantages over traditional carbon-carbon forming methodologies. Although their use in the final polymerization step is already established, there is a need for improving synthetic accessibility to implement them also in the monomer synthesis. In this review, we discuss recent examples highlighting this useful strategy.

  10. Tuning of PID controllers for integrating systems using direct synthesis method.

    Science.gov (United States)

    Anil, Ch; Padma Sree, R

    2015-07-01

    A PID controller is designed for various forms of integrating systems with time delay using direct synthesis method. The method is based on comparing the characteristic equation of the integrating system and PID controller with a filter with the desired characteristic equation. The desired characteristic equation comprises of multiple poles which are placed at the same desired location. The tuning parameter is adjusted so as to achieve the desired robustness. Tuning rules in terms of process parameters are given for various forms of integrating systems. The tuning parameter can be selected for the desired robustness by specifying Ms value. The proposed controller design method is applied to various transfer function models and to the nonlinear model equations of jacketed CSTR to show its effectiveness and applicability. Copyright © 2015 ISA. Published by Elsevier Ltd. All rights reserved.

  11. Low-temperature direct synthesis of mesoporous vanadium nitrides for electrochemical capacitors

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Hae-Min [Institute of NT-IT Fusion Technology, Ajou University, 206 Worldcup-ro, Yeongtong-gu, Suwon 16499 (Korea, Republic of); Jeong, Gyoung Hwa [Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), Banyeon 100, Ulsan 44919 (Korea, Republic of); Kim, Sang-Wook [Department of Molecular Science and Technology, Ajou University, 206 Worldcup-ro, Yeongtong-gu, Suwon 16499 (Korea, Republic of); Kim, Chang-Koo, E-mail: changkoo@ajou.ac.kr [Department of Chemical Engineering and Department of Energy Systems Research, Ajou University, 206 Worldcup-ro, Yeongtong-gu, Suwon 16499 (Korea, Republic of)

    2017-04-01

    Highlights: • Vanadium nitrides were directly synthesized by a one-step chemical precipitation method. • This method was carried out at a low temperature of 70 °C. • Vanadium nitrides had a specific capacitance of 598 F/g. • The equivalent series resistance of the vanadium nitride electrode was 1.42 Ω after 5000 cycles. - Abstract: Mesoporous vanadium nitrides are directly synthesized by a one-step chemical precipitation method at a low temperature (70 °C). Structural and morphological analyses reveal that vanadium nitride consist of long and slender nanowhiskers, and mesopores with diameters of 2–5 nm. Compositional analysis confirms the presence of vanadium in the VN structure, along with oxidized vanadium. The cyclic voltammetry and charge-discharge tests indicate that the obtained material stores charges via a combination of electric double-layer capacitance and pseudocapacitance mechanisms. The vanadium nitride electrode exhibits a specific capacitance of 598 F/g at a current density of 4 A/g. After 5000 charge-discharge cycles, the electrode has an equivalent series resistance of 1.42 Ω and retains 83% of its initial specific capacitance. This direct low-temperature synthesis of mesoporous vanadium nitrides is a simple and promising method to achieve high specific capacitance and low equivalent series resistance for electrochemical capacitor applications.

  12. Synthesis and crystal structures of gold nanowires with Gemini surfactants as directing agents.

    Science.gov (United States)

    Xu, Feng; Hou, Hao; Gao, Zhinong

    2014-12-15

    The preparation of crystalline gold nanowires (NWs) by using gemini surfactants as directing agents through a three-step seed-mediated method is reported. Unlike the nanorods with relatively low aspect ratios (typically below 20) obtained by using cetyltrimethylammonium bromide as a directing agent, the NWs obtained in this investigation can reach up to 4.4 μm, and the largest aspect ratio is calculated to be 210. For this, each of seven different gemini surfactants are utilized as directing agents, and the length and/or aspect ratio of the NWs can be tuned by varying the hydrocarbon chain lengths of the gemini surfactants. Both single and twinned crystalline structures are elucidated by selected-area electron diffraction and high-resolution transmission electron microscopy studies. The use of gemini surfactants not only advances the synthesis of gold nanostructures, but improves the understanding of the growth mechanism for seed-mediated growth. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. An efficient and green synthesis of 1-indanone and 1-tetralone via intramolecular Friedel-Crafts acylation reaction

    DEFF Research Database (Denmark)

    Tran, Phuong Hoang; Huynh, Vy Hieu; Hansen, Poul Erik

    2015-01-01

    Metal-triflate-catalyzed intramolecular Friedel–Crafts acylation of 3-arylpropanoic and 4-arylbutanoic acids in triflate-anion ionic liquids under monomodal microwave irradiation is reported. The environmentally benign synthetic procedure allows the formation of cyclic ketones in good yields with...... a short reaction time. The catalytic metal triflate in triflate-anion ionic liquids can be easily recovered and reused several times without significant loss of the catalytic performance....

  14. Towards behavioral synthesis of asynchronous circuits - an implementation template targeting syntax directed compilation

    DEFF Research Database (Denmark)

    Nielsen, Sune Fallgaard; Sparsø, Jens; Madsen, Jan

    2004-01-01

    This paper presents a method for behavioral synthesis of asynchronous circuits. Our approach aims at providing a synthesis flow which is very similar to what is found in existing synchronous design tools. We adapt the synchronous behavioral synthesis abstraction into the asynchronous handshake...

  15. Biodiesel synthesis by direct transesterification of microalga Botryococcus braunii with continuous methanol reflux.

    Science.gov (United States)

    Hidalgo, Pamela; Ciudad, Gustavo; Schober, Sigurd; Mittelbach, Martin; Navia, Rodrigo

    2015-04-01

    Direct transesterification of Botryococcus braunii with continuous acyl acceptor reflux was evaluated. This method combines in one step lipid extraction and esterification/transesterification. Fatty acid methyl esters (FAME) synthesis by direct conversion of microalgal biomass was carried out using sulfuric acid as catalyst and methanol as acyl acceptor. In this system, once lipids are extracted, they are contacted with the catalyst and methanol reaching 82%wt of FAME yield. To optimize the reaction conditions, a factorial design using surface response methodology was applied. The effects of catalyst concentration and co-solvent concentration were studied. Hexane was used as co-solvent for increasing lipid extraction performance. The incorporation of hexane in the reaction provoked an increase in FAME yield from 82% (pure methanol) to 95% when a 47%v/v of hexane was incorporated in the reaction. However, the selectivity towards non-saponifiable lipids such as sterols was increased, negatively affecting biodiesel quality. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. Nanofluid Types, Their Synthesis, Properties and Incorporation in Direct Solar Thermal Collectors: A Review.

    Science.gov (United States)

    Chamsa-Ard, Wisut; Brundavanam, Sridevi; Fung, Chun Che; Fawcett, Derek; Poinern, Gerrard

    2017-05-31

    The global demand for energy is increasing and the detrimental consequences of rising greenhouse gas emissions, global warming and environmental degradation present major challenges. Solar energy offers a clean and viable renewable energy source with the potential to alleviate the detrimental consequences normally associated with fossil fuel-based energy generation. However, there are two inherent problems associated with conventional solar thermal energy conversion systems. The first involves low thermal conductivity values of heat transfer fluids, and the second involves the poor optical properties of many absorbers and their coating. Hence, there is an imperative need to improve both thermal and optical properties of current solar conversion systems. Direct solar thermal absorption collectors incorporating a nanofluid offers the opportunity to achieve significant improvements in both optical and thermal performance. Since nanofluids offer much greater heat absorbing and heat transfer properties compared to traditional working fluids. The review summarizes current research in this innovative field. It discusses direct solar absorber collectors and methods for improving their performance. This is followed by a discussion of the various types of nanofluids available and the synthesis techniques used to manufacture them. In closing, a brief discussion of nanofluid property modelling is also presented.

  17. Nanofluid Types, Their Synthesis, Properties and Incorporation in Direct Solar Thermal Collectors: A Review

    Directory of Open Access Journals (Sweden)

    Wisut Chamsa-ard

    2017-05-01

    Full Text Available The global demand for energy is increasing and the detrimental consequences of rising greenhouse gas emissions, global warming and environmental degradation present major challenges. Solar energy offers a clean and viable renewable energy source with the potential to alleviate the detrimental consequences normally associated with fossil fuel-based energy generation. However, there are two inherent problems associated with conventional solar thermal energy conversion systems. The first involves low thermal conductivity values of heat transfer fluids, and the second involves the poor optical properties of many absorbers and their coating. Hence, there is an imperative need to improve both thermal and optical properties of current solar conversion systems. Direct solar thermal absorption collectors incorporating a nanofluid offers the opportunity to achieve significant improvements in both optical and thermal performance. Since nanofluids offer much greater heat absorbing and heat transfer properties compared to traditional working fluids. The review summarizes current research in this innovative field. It discusses direct solar absorber collectors and methods for improving their performance. This is followed by a discussion of the various types of nanofluids available and the synthesis techniques used to manufacture them. In closing, a brief discussion of nanofluid property modelling is also presented.

  18. Combustion synthesized TiO2 for enhanced photocatalytic activity under the direct sunlight-optimization of titanylnitrate synthesis

    International Nuclear Information System (INIS)

    Daya Mani, A.; Laporte, V.; Ghosal, P.; Subrahmanyam, Ch.

    2012-01-01

    Graphical abstract: Effect of oxidant on the combustion synthesis of TiO 2 has been studied by preparing titanylnitrate in four different ways from Ti(IV) iso-propoxide. It is observed that oxidant preparation method has a significant effect on physico-chemical as well as photocatalytic properties of TiO 2 . All the catalysts showed excellent photocatalytic activity than Degussa P-25 under direct sunlight for the degradation of a textile dye (methylene blue), without the need of external light sources, oxygen supply and reactor systems. Highlights: ► Optimized synthesis of titanylnitrate. ► Influence of titanylnitrate synthesis on the physico-chemical properties of TiO 2 prepared by combustion synthesis. ► Development of highly efficient TiO 2 photocatalysts those are active under the direct sunlight in open atmosphere. ► Degradation of the textile dye (methylene blue) under direct sunlight. -- Abstract: Optimized synthesis of Ti-precursor ‘titanylnitrate’ for one step combustion synthesis of N- and C-doped TiO 2 catalysts were reported and characterized by using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), diffused reflectance UV–vis spectroscopy, N 2 adsorption and X-ray photoelectron spectroscopy (XPS). XRD confirmed the formation of TiO 2 anatase and nano-crystallite size which was further confirmed by TEM. UV-DRS confirmed the decrease in the band gap to less than 3.0 eV, which was assigned due to the presence of C and N in the framework of TiO 2 as confirmed by X-ray photoelectron spectroscopy. Degradation of methylene blue in aqueous solution under the direct sunlight was carried out and typical results indicated the better performance of the synthesized catalysts than Degussa P-25.

  19. Template-directed synthesis of kinetically and thermodynamically stable molecular necklace using ring closing metathesis.

    Science.gov (United States)

    Dasgupta, Suvankar; Wu, Jishan

    2011-05-07

    We report the template-directed synthesis of a well-defined, kinetically stable [5]molecular necklace with dialkylammonium ion (R(2)NH(2)(+)) as recognition site and DB24C8 as macrocycle. A thread containing four dialkylammonium ions with olefin at both ends was first synthesized and then subjected to threading with an excess amount of DB24C8 to form pseudo[5]rotaxane, which in situ undergoes ring closing metathesis at the termini with second generation Grubbs catalyst to yield the desired [5]molecular necklace. The successful synthesis of [5]molecular necklace is mainly attributed to the self-assembly and dynamic covalent chemistry which allows the formation of thermodynamically most stable product. The self-assembly of the DB24C8 ring onto the recognition site known as templating effect was driven by noncovalent stabilizing interactions like [N(+)-H···O], [C-H···O] hydrogen bonds as well as [π···π] interactions which is facilitated in non-polar solvents. The reversible nature of olefin metathesis reaction makes it suitable for dynamic covalent chemistry since proof-reading and error-checking operates until it generates thermodynamically the most stable interlocked molecule. Riding on the success of [5]molecular necklace, we went a step further and attempted to synthesize [7]molecular necklace using the same protocol. This led to the synthesis of another thread with olefin at both ends but having six dibenzylammonium ions along the thread. However, the extremely poor solubility of this thread containing six secondary ammonium ions limits the self-assembly process even after we replaced the typical PF(6)(-) counter anion with a more lipophilic BPh(4)(-) anion. Although the poor solubility of the thread remains the bottleneck for making higher order molecular necklaces yet this approach of "threading-followed-by-ring-closing-metathesis" for the first time produces kinetically and thermodynamically stable, well-defined, homogeneous molecular necklace which

  20. Tuning of acyl-ACP thioesterase activity directed for tailored fatty acid synthesis.

    Science.gov (United States)

    Feng, Yanbin; Zhang, Yunxiu; Wang, Yayue; Liu, Jiao; Liu, Yinghui; Cao, Xupeng; Xue, Song

    2018-04-01

    Medium-chain fatty acids have attracted significant attention as sources of biofuels in recent years. Acyl-ACP thioesterase, which is considered as the key enzyme to determine the carbon chain length, catalyzes the termination of de novo fatty acid synthesis. Although recombinant medium-chain acyl-ACP thioesterase (TE) affects the fatty acid profile in heterologous cells, tailoring of the fatty acid composition merely by engineering a specific TE is still intractable. In this study, the activity of a C8-C10-specific thioesterase FatB2 from Cuphea hookeriana on C10-ACP was quantified twice as high as that on C8-ACP based on a synthetic C8-C16 acyl-ACP pool in vitro. Whereas in vivo, it was demonstrated that ChFatB2 preferred to accumulate C8 fatty acids with 84.9% composition in the ChFatB2-engineered E. coli strain. To achieve C10 fatty acid production, ChFatB2 was rationally tuned based on structural investigation and enzymatic analysis. An I198E mutant was identified to redistribute the C8-ACP flow, resulting in C10 fatty acid being produced as the principal component at 57.6% of total fatty acids in vivo. It was demonstrated that the activity of TE relative to β-ketoacyl-ACP synthases (KAS) directly determined the fatty acid composition. Our results provide a prospective strategy in tailoring fatty acid synthesis by tuning of TE activities based on TE-ACP interaction.

  1. A Novel Approach in Cinnamic Acid Synthesis: Direct Synthesis of Cinnamic Acids from Aromatic Aldehydes and Aliphatic Carboxylic Acids in the Presence of Boron Tribromide

    Directory of Open Access Journals (Sweden)

    M. Onciu

    2005-02-01

    Full Text Available Cinnamic acids have been prepared in moderate to high yields by a new direct synthesis using aromatic aldehydes and aliphatic carboxylic acids, in the presence of boron tribromide as reagent, 4-dimethylaminopyridine (4-DMAP and pyridine (Py as bases and N-methyl-2-pyrolidinone (NMP as solvent, at reflux (180-190°C for 8-12 hours.

  2. Microwave synthesis of polymer-embedded Pt-Ru catalyst for direct methanol fuel cell.

    Science.gov (United States)

    Bensebaa, Farid; Farah, Abdiaziz A; Wang, Dashan; Bock, Christina; Du, Xiaomei; Kung, Judy; Le Page, Yvon

    2005-08-18

    Platinum-ruthenium nanoparticles stabilized within a conductive polymer matrix are prepared using microwave heating. Polypyrrole di(2-ethylhexyl) sulfosuccinate, or PPyDEHS, has been chosen for its known electrical conductivity, thermal stability, and solubility in polar organic solvents. A scalable and quick two-step process is proposed to fabricate alloyed nanoparticles dispersed in PPyDEHS. First a mixture of PPyDEHS and metallic precursors is heated in a microwave under reflux conditions. Then the nanoparticles are extracted by centrifugation. Physical characterization by TEM shows that crystalline and monodisperse alloyed nanoparticles with an average size of 2.8 nm are obtained. Diffraction data show that crystallite size is around 2.0 nm. Methanol electro-oxidation data allow us to propose these novel materials as potential candidates for direct methanol fuel cells (DMFC) application. The observed decrease in sulfur content in the polymer upon incorporation of PtRu nanoparticles may have adversely affected the measured catalytic activity by decreasing the conductivity of PPyDEHS. Higher concentration of polymer leads to lower catalyst activity. Design and synthesis of novel conductive polymers is needed at this point to enhance the catalytic properties of these hybrid materials.

  3. The Synthesis of Nanostructured WC-Based Hardmetals Using Mechanical Alloying and Their Direct Consolidation

    Directory of Open Access Journals (Sweden)

    N. Al-Aqeeli

    2014-01-01

    Full Text Available Tungsten carbide- (WC- based hardmetals or cemented carbides represent an important class of materials used in a wide range of industrial applications which primarily include cutting/drilling tools and wear resistant components. The introduction and processing of nanostructured WC-based cemented carbides and their subsequent consolidation to produce dense components have been the subject of several investigations. One of the attractive means of producing this class of materials is by mechanical alloying technique. However, one of the challenging issues in obtaining the right end-product is the possible loss of the nanocrystallite sizes due to the undesirable grain growth during powder sintering step. Many research groups have engaged in multiple projects aiming at exploring the right path of consolidating the nanostructured WC-based powders without substantially loosing the attained nanostructure. The present paper highlights some key issues related to powder synthesis and sintering of WC-based nanostructured materials using mechanical alloying. The path of directly consolidating the powders using nonconventional consolidation techniques will be addressed and some light will be shed on the advantageous use of such techniques. Cobalt-bonded hardmetals will be principally covered in this work along with an additional exposure of the use of other binders in the WC-based hardmetals.

  4. Direct chemical synthesis of MnO2 nanowhiskers on MXene surfaces for supercapacitor applications

    KAUST Repository

    Rakhi, Raghavan Baby

    2016-07-05

    Transition metal carbides (MXenes) are an emerging class of two dimensional (2D) materials with promising electrochemical energy storage performance. Herein, for the first time, by direct chemical synthesis, nanocrystalline ε-MnO2 whiskers were formed on MXene nanosheet surfaces (ε-MnO2/Ti2CTx and ε-MnO2/Ti3C2Tx) to make nanocomposite electrodes for aqueous pseudocapacitors. The ε-MnO2 nanowhiskers increase the surface area of the composite electrode and enhance the specific capacitance by nearly three orders of magnitude compared to pure MXene based symmetric supercapacitors. Combined with enhanced pseudocapacitance, the fabricated ε-MnO2/MXene supercapacitors exhibited excellent cycling stability with ~88% of the initial specific capacitance retained after 10000 cycles which is much higher than pure ε-MnO2 based supercapacitors (~74%). The proposed electrode structure capitalizes on the high specific capacitance of MnO2 and the ability of MXenes to improve conductivity and cycling stability.

  5. Direct synthesis of water dispersible superparamagnetic TGA capped FePt nanoparticles: One pot, one shot

    Energy Technology Data Exchange (ETDEWEB)

    Jha, Deepak K. [Department of Physics, Tezpur University (Central University), Tezpur 784028 (India); Varadarajan, Komanduri S.; Patel, Anant B. [Center for Cellular and Molecular Biology, Uppal Road, Hyderabad 500007 (India); Deb, Pritam, E-mail: pdeb@tezu.ernet.in [Department of Physics, Tezpur University (Central University), Tezpur 784028 (India)

    2015-04-15

    Thioglycolic acid (TGA) capped hydrophilic fcc-FePt magnetic nanoparticles (MNPs) were directly synthesized by a facile one pot polyol method. Thioglycolic acid (TGA) was used to functionalize the nanoparticles by incorporating thiol group onto the surface. It helped in the preparation of highly stable dispersions of nanoparticles with spherical morphology. A possible formation mechanism for these FePt MNPs, depending on the role of TGA, was proposed. The as-prepared FePt MNPs possessed a face centered cubic structure with an average size of 6 ± 1 nm and superparamagnetic property at room temperature. MRI study showed that these MNPs exhibited a transverse relaxivity of ∼600 mg{sup −1} ml s{sup −1}, superior to that of reported iron oxide nanoparticles. - Highlights: • One pot synthesis of TGA capped hydrophilic FePt superparamagnetic nanoparticles. • Role of TGA molecules in the formation of FePt nanoparticles. • EDX reveals the equiatomic ratio of Fe and Pt atoms in FePt nanoparticles. • The HR-TEM exhibits spherical nanoparticles with a narrow size distribution. • High transverse relaxivity suggesting as potential MRI contrast agent.

  6. Hydrothermal synthesis of zeolite T from kaolin using two different structure-directing agents

    Science.gov (United States)

    Arshad, Sazmal E.; Lutfor Rahman, M.; Sarkar, Shaheen M.; Yusslee, Eddy F.; Patuwan, Siti Z.

    2018-01-01

    Zeolite T was synthesized from the molar chemical composition of 1SiO2:0.04Al2O3:0.26Na2O:0.09K2O:14H2O in the form of a homogenous milky solution in the presence of the two different structure-directing agents TMAOH and TEAOH respectively. Modification of the composition of silica was undertaken using metakaolin from calcined kaolin at 750 °C for 4 h, while the molar composition of each different SDA was variated from 0.05, 0.10, 0.15, 0.20 and 0.25. The homogenous mixture was left at room temperature for 24 h before undergoing hydrothermal synthesis at 100 °C for 168 h. The synthesized samples were filtered and aged at 120 °C for 2 h and each sample was calcined at high temperatures (545 °C for TMAOH and 520 °C for TEAOH) for template removal before characterization using XRD and SEM. Crystallization of the zeolite T in its major form only took place at a molar ratio of 0.10 of TMAOH, while TEAOH showed the species evolution of zeolite T into zeolite L and W for other molar ratios.

  7. Direct Silver Micro Circuit Patterning on Transparent Polyethylene Terephthalate Film Using Laser-Induced Photothermochemical Synthesis

    Directory of Open Access Journals (Sweden)

    Chen-Jui Lan

    2017-02-01

    Full Text Available This study presents a new and improved approach to the rapid and green fabrication of highly conductive microscale silver structures on low-cost transparent polyethylene terephthalate (PET flexible substrate. In this new laser direct synthesis and pattering (LDSP process, silver microstructures are simultaneously synthesized and laid down in a predetermined pattern using a low power continuous wave (CW laser. The silver ion processing solution, which is transparent and reactive, contains a red azo dye as the absorbing material. The silver pattern is formed by photothermochemical reduction of the silver ions induced by the focused CW laser beam. In this improved LDSP process, the non-toxic additive in the transparent ionic solution absorbs energy from a low cost CW visible laser without the need for the introduction of any hazardous chemical process. Tests were carried out to determine the durability of the conductive patterns, and numerical analyses of the thermal and fluid transport were performed to investigate the morphology of the deposited patterns. This technology is an advanced method for preparing micro-scale circuitry on an inexpensive, flexible, and transparent polymer substrate that is fast, environmentally benign, and shows potential for Roll-to-Roll manufacture.

  8. A single gene directs synthesis of a precursor protein with beta- and alpha-amylase activities in Bacillus polymyxa.

    OpenAIRE

    Uozumi, N; Sakurai, K; Sasaki, T; Takekawa, S; Yamagata, H; Tsukagoshi, N; Udaka, S

    1989-01-01

    The Bacillus polymyxa amylase gene comprises 3,588 nucleotides. The mature amylase comprises 1,161 amino acids with a molecular weight of 127,314. The gene appeared to be divided into two portions by the direct-repeat sequence located at almost the middle of the gene. The 5' region upstream of the direct-repeat sequence was shown to be responsible for the synthesis of beta-amylase. The 3' region downstream of the direct-repeat sequence contained four sequences homologous with those in other a...

  9. Optimal conditions in direct dimethyl ether synthesis from syngas utilizing a dual-type fluidized bed reactor

    International Nuclear Information System (INIS)

    Yousefi, Ahmad; Eslamloueyan, Reza; Kazerooni, Nooshin Moradi

    2017-01-01

    Concerns over environmental pollution and ever-increasing energy demand have urged the global community to tap clean-burning fuels among which dimethyl ether is a promising candidate for contribution in the transportation sector. Direct dimethyl ether synthesis from syngas, in which methanol production and dehydration take place simultaneously, is arguably the preferred route for large scale production. In this study, direct dimethyl ether synthesis is proposed in an industrial dual-type fluidized bed reactor. This configuration involves two fluidized bed reactors operating in different conditions. In the first catalytic reactor (water-cooled reactor), the synthesis gas is partly converted to methanol after being preheated by the reaction heat in the second reactor (gas-cooled reactor). A two-phase generalized comprehensive reactor model, comprised of the flow in three different regimes is applied and a smooth transition between flow regimes is provided based on the probabilistic averaging approach. The optimal operating conditions are sought by employing differential evolution algorithm as a robust optimization strategy. The dimethyl ether mole fraction is considered as the objective function during the optimization. The results show considerable dimethyl ether enhancement by 16% and 14% compared to the conventional direct dimethyl ether synthesis reactor and dual-type fixed bed dimethyl ether reactor arrangements, respectively. - Highlights: • Dual-type catalytic fluidized bed reactors for dimethyl ether synthesis is studied. • A two-phase comprehensive model comprised of flow in three regimes is used. • Probabilistic averaging approach is applied for smooth transitions between regimes. • Differential evolution method is employed to determine optimal operating conditions. • Production capacity is remarkably enhanced compared to conventional reactor.

  10. Directed evolution of promoters and tandem gene arrays for customizing RNA synthesis rates and regulation.

    Science.gov (United States)

    Tyo, Keith E J; Nevoigt, Elke; Stephanopoulos, Gregory

    2011-01-01

    Manipulating RNA synthesis rates is a primary method the cell uses to adjust its physiological state. Therefore to design synthetic genetic networks and circuits, precise control of RNA synthesis rates is of the utmost importance. Often, however, a native promoter does not exist that has the precise characteristics required for a given application. Here, we describe two methods to change the rates and regulation of RNA synthesis in cells to create RNA synthesis of a desired specification. First, error-prone PCR is discussed for diversifying the properties of native promoters, that is, changing the rate of synthesis in constitutive promoters and the induction properties for an inducible promoter. Specifically, we describe techniques for generating diversified promoter libraries of the constitutive promoters P(L)tetO-1 in Escherichia coli and TEF1 in Saccharomyces cerevisiae as well as the inducible, oxygen-repressed promoter DAN1 in S. cerevisiae. Beyond generating promoter libraries, we discuss techniques to quantify the parameters of each new promoter. Promoter characteristics for each promoter in hand, the designer can then pick and choose the promoters needed for the specific genetic circuit described in silico. Second, Chemically Induced Chromosomal Evolution (CIChE) is presented as an alternative method to finely adjust RNA synthesis rates in E. coli by variation of gene cassette copy numbers in tandem gene arrays. Both techniques result in precisely defined RNA synthesis and should be of great utility in synthetic biology. Copyright © 2011 Elsevier Inc. All rights reserved.

  11. Direct formation of small Cu2O nanocubes, octahedra, and octapods for efficient synthesis of triazoles

    Science.gov (United States)

    Tsai, Ya-Huei; Chanda, Kaushik; Chu, Yi-Ting; Chiu, Chun-Ya; Huang, Michael H.

    2014-07-01

    In most studies describing the preparation of Cu2O crystals of various morphologies, the particle sizes are normally hundreds of nanometers to micrometers due to rapid particle growth, so they are not exactly nanocrystals. Here we report surfactant-free formation of sub-100 nm Cu2O nanocrystals with systematic shape evolution from cubic to octahedral structures by preparing an aqueous mixture of Cu(OAc)2, NaOH, and N2H4 solution. Adjustment of the hydrazine volume enables the particle shape control. Uniform nanocubes and octahedra were synthesized with edge lengths of 37 and 67 nm, respectively. Novel Cu2O octapods with an edge length of 135 nm were also produced by mixing CuCl2 solution, SDS surfactant, NaOH solution, and NH2OH.HCl reductant solution. All of them are nearly the smallest Cu2O nanocrystals of the same shapes ever reported. These small cubes, octahedra, and octapods were employed as catalysts in the direct synthesis of 1,2,3-triazoles from the reaction of alkynes, organic halides, and NaN3 at 55 °C. All of them displayed high product yields in short reaction times. The octahedra enclosed by the {111} facets are the best catalysts, and can catalyze this cycloaddition reaction with high yields in just 2 h when different alkynes were used to make diverse triazole products. Hence, the small Cu2O particles provide time-saving, energy-efficient, and high product yield benefits to organocatalysis.In most studies describing the preparation of Cu2O crystals of various morphologies, the particle sizes are normally hundreds of nanometers to micrometers due to rapid particle growth, so they are not exactly nanocrystals. Here we report surfactant-free formation of sub-100 nm Cu2O nanocrystals with systematic shape evolution from cubic to octahedral structures by preparing an aqueous mixture of Cu(OAc)2, NaOH, and N2H4 solution. Adjustment of the hydrazine volume enables the particle shape control. Uniform nanocubes and octahedra were synthesized with edge

  12. Stereoselective, nitro-Mannich/lactamisation cascades for the direct synthesis of heavily decorated 5-nitropiperidin-2-ones and related heterocycles

    OpenAIRE

    Pavol Jakubec; Dane M. Cockfield; Madeleine Helliwell; James Raftery; Darren J. Dixon

    2012-01-01

    Summary A versatile nitro-Mannich/lactamisation cascade for the direct stereoselective synthesis of heavily decorated 5-nitropiperidin-2-ones and related heterocycles has been developed. A highly enantioenriched substituted 5-nitropiperidin-2-one was synthesised in a four component one-pot reaction combining an enantioselective organocatalytic Michael addition with the diastereoselective nitro-Mannich/lactamisation cascade. Protodenitration and chemoselective reductive manipulation of the het...

  13. Synthesis of ammonia directly from air and water at ambient temperature and pressure

    Science.gov (United States)

    Lan, Rong; Irvine, John T. S.; Tao, Shanwen

    2013-01-01

    The N≡N bond (225 kcal mol−1) in dinitrogen is one of the strongest bonds in chemistry therefore artificial synthesis of ammonia under mild conditions is a significant challenge. Based on current knowledge, only bacteria and some plants can synthesise ammonia from air and water at ambient temperature and pressure. Here, for the first time, we report artificial ammonia synthesis bypassing N2 separation and H2 production stages. A maximum ammonia production rate of 1.14 × 10−5 mol m−2 s−1 has been achieved when a voltage of 1.6 V was applied. Potentially this can provide an alternative route for the mass production of the basic chemical ammonia under mild conditions. Considering climate change and the depletion of fossil fuels used for synthesis of ammonia by conventional methods, this is a renewable and sustainable chemical synthesis process for future. PMID:23362454

  14. Collapsed polymer-directed synthesis of multicomponent coaxial-like nanostructures

    KAUST Repository

    Huang, Zhiqi

    2016-07-19

    Multicomponent colloidal nanostructures (MCNs) exhibit intriguing topologically dependent chemical and physical properties. However, there remain significant challenges in the synthesis of MCNs with high-order complexity. Here we show the development of a general yet scalable approach for the rational design and synthesis of MCNs with unique coaxial-like construction. The site-preferential growth in this synthesis relies on the selective protection of seed nanoparticle surfaces with locally defined domains of collapsed polymers. By using this approach, we produce a gallery of coaxial-like MCNs comprising a shaped Au core surrounded by a tubular metal or metal oxide shell. This synthesis is robust and not prone to variations in kinetic factors of the synthetic process. The essential role of collapsed polymers in achieving anisotropic growth makes our approach fundamentally distinct from others. We further demonstrate that this coaxial-like construction can lead to excellent photocatalytic performance over conventional core–shell-type MCNs.

  15. Synthesis of ammonia directly from air and water at ambient temperature and pressure.

    Science.gov (United States)

    Lan, Rong; Irvine, John T S; Tao, Shanwen

    2013-01-01

    The N≡N bond (225 kcal mol⁻¹) in dinitrogen is one of the strongest bonds in chemistry therefore artificial synthesis of ammonia under mild conditions is a significant challenge. Based on current knowledge, only bacteria and some plants can synthesise ammonia from air and water at ambient temperature and pressure. Here, for the first time, we report artificial ammonia synthesis bypassing N₂ separation and H₂ production stages. A maximum ammonia production rate of 1.14 × 10⁻⁵ mol m⁻² s⁻¹ has been achieved when a voltage of 1.6 V was applied. Potentially this can provide an alternative route for the mass production of the basic chemical ammonia under mild conditions. Considering climate change and the depletion of fossil fuels used for synthesis of ammonia by conventional methods, this is a renewable and sustainable chemical synthesis process for future.

  16. Microwave-assisted synthesis of poly(3-hexylthiophene) via direct oxidation with FeCl{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Nicho, M.E., E-mail: menicho@uaem.mx [Centro de Investigacion en Ingenieria y Ciencias Aplicadas, Universidad Autonoma del Estado de Morelos (UAEM), Av. Universidad 1001, Col. Chamilpa, C.P. 62210 Cuernavaca, Morelos (Mexico); Garcia-Escobar, C.H.; Hernandez-Martinez, D. [Centro de Investigacion en Ingenieria y Ciencias Aplicadas, Universidad Autonoma del Estado de Morelos (UAEM), Av. Universidad 1001, Col. Chamilpa, C.P. 62210 Cuernavaca, Morelos (Mexico); Linzaga-Elizalde, I. [Centro de Investigaciones Quimicas (CIQ) de la UAEM (Mexico); Cadenas-Pliego, G. [Centro de Investigacion en Quimica Aplicada, Saltillo, Coahuila (Mexico)

    2012-09-20

    In this work, CoolMate microwave synthesis system was employed to synthesize soluble poly(3-hexylthiophene) by direct oxidation of 3-hexylthiophene monomer with FeCl{sub 3} as oxidant. P3HT was synthesized varying reaction time by 2 h, 1 h and 0.5 h. According to the results optimal microwave radiation time for synthesis was 1 h. On the other hand, P3HT was synthesized in two different solvents: chloroform (CHCl{sub 3}) and dichloromethane (CH{sub 2}Cl{sub 2}). The obtained yields depend on the solvent and the reaction time used in the synthesis, microwave-assisted synthesis leads to outstanding increase in yield (with dichloromethane solvent). Homogeneous thin films were prepared by spin-coating technique from toluene. Physicochemical characterization of P3HT polymers was carried out: changes in weight molecular distribution and polydispersity were obtained by HPLC (high-performance liquid chromatography); dyads and triads percent were analyzed by NMR (nuclear magnetic resonance). Surface topographical changes were obtained by atomic force microscopy (AFM). AFM images revealed that the surface morphology depends on synthesis method, reaction time and solvent used. Finally the samples were characterized by thermogravimetric analysis (TGA) and ultraviolet-visible analysis (UV-vis). Compared with the traditional method (without microwave), this method provided considerable decrease in the reaction time, both lower polydispersity and molecular weight, less volume of solvents for the synthesis, as well as more alternatives for solvent choice. The results confirmed the versatility of the procedure by microwave, which yields polymeric materials in 1 h and has no adverse effects on the polymers quality.

  17. Structural archetypes in nickel(II) hybrid vanadates. Towards a directed hydrothermal synthesis

    International Nuclear Information System (INIS)

    Luis, R. Fernandez de; Urtiaga, M.K.; Mesa, J.L.; Rojo, T.; Arriortua, M.I.

    2009-01-01

    In the present work, we relate the modifications of the initial synthesis parameters (pH value, stoichiometry and concentration) with the different structural archetypes obtained in the {Ni/Bpy/VO} and {Ni/Bpe/VO} systems (4,4'-bipyridine (Bpy), 1,2-di(4-pyridyl) ethylene (Bpe)). The vanadium coordination is partially controlled by the hydrothermal synthesis conditions, and the final crystal structures depend on the synergetic interaction between the metal-organic subnets and the vanadium oxide subunits.

  18. Direct Energy Supply to the Reaction Mixture during Microwave-Assisted Hydrothermal and Combustion Synthesis of Inorganic Materials

    Directory of Open Access Journals (Sweden)

    Roberto Rosa

    2014-05-01

    Full Text Available The use of microwaves to perform inorganic synthesis allows the direct transfer of electromagnetic energy inside the reaction mixture, independently of the temperature manifested therein. The conversion of microwave (MW radiation into heat is useful in overcoming the activation energy barriers associated with chemical transformations, but the use of microwaves can be further extended to higher temperatures, thus creating unusual high-energy environments. In devising synthetic methodologies to engineered nanomaterials, hydrothermal synthesis and solution combustion synthesis can be used as reference systems to illustrate effects related to microwave irradiation. In the first case, energy is transferred to the entire reaction volume, causing a homogeneous temperature rise within a closed vessel in a few minutes, hence assuring uniform crystal growth at the nanometer scale. In the second case, strong exothermic combustion syntheses can benefit from the application of microwaves to convey energy to the reaction not only during the ignition step, but also while it is occurring and even after its completion. In both approaches, however, the direct interaction of microwaves with the reaction mixture can lead to practically gradient-less heating profiles, on the basis of which the main observed characteristics and properties of the aforementioned reactions and products can be explained.

  19. Synthesis of Nanocrystalline Boron Carbide by Direct Microwave Carbothermal Reduction of Boric Acid

    Directory of Open Access Journals (Sweden)

    Rodolfo F. K. Gunnewiek

    2017-01-01

    Full Text Available The excellent physical and chemical properties of boron carbide make it suitable for many applications. However, its synthesis requires a large amount of energy and is time-consuming. Microwave carbothermal reduction is a fast technique for producing well crystallized equiaxial boron carbide nanoparticles of about 50 nm and very few amounts of elongated nanoparticles were also synthesized. They presented an average length of 82 nm and a high aspect ratio (5.5. The total reaction time was only 20 minutes, which disfavor the growing process, leading to the synthesis of nanoparticles. Microwave-assisted synthesis leaded to producing boron-rich boron carbide. Increasing the forward power increases the boron content and enhances the efficiency of the reaction, resulting in better crystallized boron carbide.

  20. Structural archetypes in nickel(II) hybrid vanadates. Towards a directed hydrothermal synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Luis, R. Fernandez de; Urtiaga, M.K. [Dpto. Mineralogia y Petrologia, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/UPV/EHU, Apdo. 644, 48080 Bilbao (Spain); Mesa, J.L.; Rojo, T. [Dpto. Quimica Inorganica, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco UPV/EHU, Apdo. 644, 48080 Bilbao (Spain); Arriortua, M.I. [Dpto. Mineralogia y Petrologia, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/UPV/EHU, Apdo. 644, 48080 Bilbao (Spain)], E-mail: maribel.arriortua@ehu.es

    2009-07-01

    In the present work, we relate the modifications of the initial synthesis parameters (pH value, stoichiometry and concentration) with the different structural archetypes obtained in the {l_brace}Ni/Bpy/VO{r_brace} and {l_brace}Ni/Bpe/VO{r_brace} systems (4,4'-bipyridine (Bpy), 1,2-di(4-pyridyl) ethylene (Bpe)). The vanadium coordination is partially controlled by the hydrothermal synthesis conditions, and the final crystal structures depend on the synergetic interaction between the metal-organic subnets and the vanadium oxide subunits.

  1. The direct conversion of synthesis gas to chemicals / Ernest du Toit

    OpenAIRE

    Du Toit, Ernest

    2002-01-01

    The catalytic conversion of synthesis gas, obtainable from the processing of coal, biomass or natural gas, to a complex hydrocarbon product stream can be achieved via the Fischer-Tropsch process. The Fischer-Tropsch synthesis process has evolved from being mainly a fuel producing process in the early 1950's to that of a solvent and speciality wax production process towards the end of the 1970's. From the early 1980's there has been a clear shift towards the production of commod...

  2. Correction: An unsymmetrical non-fullerene acceptor: synthesis via direct heteroarylation, self-assembly, and utility as a low energy absorber in organic photovoltaic cells.

    Science.gov (United States)

    Payne, Abby-Jo; Li, Shi; Dayneko, Sergey V; Risko, Chad; Welch, Gregory C

    2017-09-21

    Correction for 'An unsymmetrical non-fullerene acceptor: synthesis via direct heteroarylation, self-assembly, and utility as a low energy absorber in organic photovoltaic cells' by Abby-Jo Payne et al., Chem. Commun., 2017, 53, 10168-10171.

  3. Direct synthesis of magnetite nanoparticles from iron(II) carboxymethylcellulose and their performance as NMR contrast agents

    Energy Technology Data Exchange (ETDEWEB)

    Gomes da Silva, Delmarcio; Hiroshi Toma, Sergio; Menegatti de Melo, Fernando [Instituto de Química, Universidade de São Paulo, São Paulo, SP (Brazil); Carvalho, Larissa Vieira C.; Magalhães, Alvicler; Sabadini, Edvaldo [Instituto de Química, Universidade Estadual de Campinas – UNICAMP, Campinas, SP (Brazil); Domingues dos Santos, Antônio [Instituto de Física, Universidade de São Paulo, São Paulo, SP (Brazil); Araki, Koiti [Instituto de Química, Universidade de São Paulo, São Paulo, SP (Brazil); Toma, Henrique E., E-mail: henetoma@iq.usp.br [Instituto de Química, Universidade de São Paulo, São Paulo, SP (Brazil)

    2016-01-01

    Iron(II) carboxymethylcellulose (CMC) has been successfully employed in the synthesis of hydrophylic magnetite nanoparticles stabilized with a biopolymer coating, aiming applications in NMR imaging. The new method encompasses a convenient one-step synthetic procedure, allowing a good size control and yielding particles of about 10 nm (core size). In addition to the biocompatibility, the nanoparticles have promoted a drastic reduction in the transverse relaxation time (T{sub 2}) of the water protons. The relaxivity rates have been investigated as a function of the nanoparticles concentration, showing a better performance in relation to the common NMR contrast agents available in the market. - Highlights: • Stable, hydrophylic magnetic nanoparticles have been obtained. • Direct use of iron(II) carboxymethylcellulose improves the synthesis. • The magnetic nanoparticles exhibit high spin–spin relaxivity. • The particles promote dark contrast by decreasing the T{sub 2} relaxation time.

  4. Direct synthesis of dimethyl carbonate from CO2 and methanol over ...

    Indian Academy of Sciences (India)

    traditional methods for DMC synthesis (phosgenation and oxidative .... CeO2 samples were recorded on a Philips X'pert Pro ..... A: Gen. 404 39. 11. Tomishige K and Kunimori K 2002 Appl. Catal. A: Gen. 237 103. 12. Jung K T and Bell A T 2001 J. Catal. 204 339. 13. Ikeda Y, Asadullha M, Fujimoto K and Tomishige K.

  5. Studies directed toward the exploitation of vicinal diols in the synthesis of (+-nebivolol intermediates

    Directory of Open Access Journals (Sweden)

    Runjun Devi

    2017-03-01

    Full Text Available While the exploitation of the Sharpless asymmetric dihydroxylation as the source of chirality in the synthesis of acyclic molecules and saturated heterocycles has been tremendous, its synthetic utility toward chiral benzo-annulated heterocycles is relatively limited. Thus, in the search for wider applications of Sharpless asymmetric dihydroxylation-derived diols for the synthesis of benzo-annulated heterocycles, we report herein our studies in the asymmetric synthesis of (R-1-((R-6-fluorochroman-2-ylethane-1,2-diol, (R-1-((S-6-fluorochroman-2-ylethane-1,2-diol and (S-6-fluoro-2-((R-oxiran-2-ylchroman, which have been used as late-stage intermediates for the asymmetric synthesis of the antihypertensive drug (S,R,R,R-nebivolol. Noteworthy is that a large number of racemic and asymmetric syntheses of nebivolol and their intermediates have been described in the literature, however, the Sharpless asymmetric dihydroxylation has never been employed as the sole source of chirality for this purpose.

  6. A practical one-pot synthesis of azides directly from alcohols

    Indian Academy of Sciences (India)

    Azide is one of the most versatile functional groups in organic synthesis owing to the fact that it is the most convenient source of amines, which are very common in natural products as well as pharmaceutical hete- rocycles.1 Additionally, the stability of azides under physiological conditions and their inimitable reacti-.

  7. Iron Particle Size Effects for Direct Production of Lower Olefins from Synthesis Gas

    NARCIS (Netherlands)

    Torres Galvis, H.M.|info:eu-repo/dai/nl/314116249; Bitter, J.H.|info:eu-repo/dai/nl/160581435; Davidian, T.; Ruitenbeek, M.; Dugulan, A.I.; de Jong, K.P.|info:eu-repo/dai/nl/06885580X

    2012-01-01

    The Fischer–Tropsch synthesis of lower olefins (FTO) is an alternative process for the production of key chemical building blocks from non-petroleum-based sources such as natural gas, coal, or biomass. The influence of the iron carbide particle size of promoted and unpromoted carbon nanofiber

  8. Synthesis of Chiral Tertiary Boronic Esters: Phosphonate-Directed Catalytic Asymmetric Hydroboration of Trisubstituted Alkenes.

    Science.gov (United States)

    Chakrabarty, Suman; Takacs, James M

    2017-05-03

    Highly enantioselective rhodium-catalyzed hydroboration of allylic phosphonates by pinacolborane affords chiral tertiary boronic esters. The β-borylated phosphonates are readily converted to chiral β- and γ-hydroxyphosphonates and aminophosphonates and to phosphonates bearing a quaternary carbon stereocenter. The utility of the latter is illustrated by the synthesis of (S)-(+)-bakuchiol methyl ether.

  9. Experimental determination and modeling of the phase behavior for the direct synthesis of dimethyl carbonate from methanol and carbon dioxide

    DEFF Research Database (Denmark)

    Tsivintzelis, Ioannis; Musko, Nikolai E.; Baiker, Alfons

    2013-01-01

    -Plus-Association (CPA) equation of state was applied to model the phase behavior of the experimentally studied systems. In this regard, the CPA binary interaction parameters were estimated based on experimental data for the corresponding binary systems available in the literature, and subsequently the model was applied......This study focuses on the investigation of the phase behavior of mixtures relevant to the direct synthesis of dimethyl carbonate from methanol and carbon dioxide. The bubble points of corresponding quaternary mixtures of varying composition were experimentally determined. The Cubic...

  10. Merging Photoredox and Nickel Catalysis: The Direct Synthesis of Ketones by the Decarboxylative Arylation of α-Oxo Acids.

    Science.gov (United States)

    Chu, Lingling; Lipshultz, Jeffrey M; MacMillan, David W C

    2015-06-26

    The direct decarboxylative arylation of α-oxo acids has been achieved by synergistic visible-light-mediated photoredox and nickel catalysis. This method offers rapid entry to aryl and alkyl ketone architectures from simple α-oxo acid precursors via an acyl radical intermediate. Significant substrate scope is observed with respect to both the oxo acid and arene coupling partners. This mild decarboxylative arylation can also be utilized to efficiently access medicinal agents, as demonstrated by the rapid synthesis of fenofibrate. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Direct analysis in real time mass spectrometry of potential by-products from homemade nitrate ester explosive synthesis.

    Science.gov (United States)

    Sisco, Edward; Forbes, Thomas P

    2016-04-01

    This work demonstrates the coupling of direct analysis in real time (DART) ionization with time-of-flight mass spectrometry (MS) in an off-axis configuration for the trace detection and analysis of potential partially nitrated and dimerized by-products of homemade nitrate ester explosive synthesis. Five compounds relating to the synthesis of nitroglycerin (NG) and pentaerythritol tetranitrate (PETN) were examined. Deprotonated ions and adducts with molecular oxygen, nitrite, and nitrate were observed in the mass spectral responses of these compounds. A global optimum temperature of 350 °C for the by-products investigated here enabled single nanogram to sub nanogram trace detection. Matrix effects were examined through a series of mixtures containing one or more compounds (sugar alcohol precursors, by-products, and/or explosives) across a range of mass loadings. The explosives MS responses experienced competitive ionization in the presence of all by-products. The magnitude of this influence corresponded to both the degree of by-product nitration and the relative mass loading of the by-product to the explosive. This work provides a characterization of potential by-products from homemade nitrate ester synthesis, including matrix effects and potential challenges that might arise from the trace detection of homemade explosives (HMEs) containing impurities. Detection and understanding of HME impurities and complex mixtures may provide valuable information for the screening and sourcing of homemade nitrate ester explosives. Published by Elsevier B.V.

  12. Gold/acid-co-catalyzed direct microwave-assisted synthesis of fused azaheterocycles from propargylic hydroperoxides.

    Science.gov (United States)

    Alcaide, Benito; Almendros, Pedro; Quirós, M Teresa

    2014-03-17

    The gold-acid-co-catalyzed synthesis of nine series of fused azaheterocycles with structural diversity starting from the same synthons as readily available propargylic hydroperoxides and aromatic amines has been achieved. The overall tandem process consists in a gold-catalyzed hydroperoxide rearrangement/Michael reaction followed by a final acid-catalyzed cyclization. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Direct synthesis of 1,5-disubstituted-4-magnesio-1,2,3-triazoles, revisited.

    Science.gov (United States)

    Krasiński, Antoni; Fokin, Valery V; Sharpless, K Barry

    2004-04-15

    After revisiting earlier works reporting the regioselective synthesis of 1,5-disubstituted-1,2,3-triazoles via the addition of bromomagnesium acetylides to azides, much improved yields of the products were obtained for a wide array of azides and alkynes. The intermediates of that reaction can be trapped with different electrophiles to regioselectively form 1,4,5-trisubstituted 1,2,3-triazoles. [reaction: see text

  14. Self-assembled peptide template directed synthesis of one-dimensional inorganic nanostructures and their applications

    OpenAIRE

    Acar, Handan

    2012-01-01

    Ankara : The Materials Science and Nanotechnology Program of the Graduate School of Engineering and Sciences of Bilkent University, 2012. Thesis (Ph. D.) -- Bilkent University, 2012. Includes bibliographical references. Engineering at the nano scale has been an active area of science and technology over the last decade. Inspired by nature, synthesis of functional inorganic materials using synthetic organic templates constitutes the theme of this thesis. Developing organic te...

  15. Template-directed synthesis of nets based upon octahemioctahedral cages that encapsulate catalytically active metalloporphyrins

    KAUST Repository

    Zhang, ZhenJie

    2012-01-18

    meso-Tetra(N-methyl-4-pyridyl)porphine tetratosylate (TMPyP) templates the synthesis of six new metal-organic materials by the reaction of benzene-1,3,5-tricarboxylate with transition metals, five of which exhibit HKUST-1 or tbo topology (M = Fe, Mn, Co, Ni, Mg). The resulting materials, porph@MOMs, selectively encapsulate the corresponding metalloporphyrins in octahemioctahedral cages and can serve as size-selective heterogeneous catalysts for oxidation of olefins. © 2011 American Chemical Society.

  16. Understanding fluxes as media for directed synthesis: in situ local structure of molten potassium polysulfides.

    Science.gov (United States)

    Shoemaker, Daniel P; Chung, Duck Young; Mitchell, J F; Bray, Travis H; Soderholm, L; Chupas, Peter J; Kanatzidis, Mercouri G

    2012-06-06

    Rational exploratory synthesis of new materials requires routes to discover novel phases and systematic methods to tailor their structures and properties. Synthetic reactions in molten fluxes have proven to be an excellent route to new inorganic materials because they promote diffusion and can serve as an additional reactant, but little is known about the mechanisms of compound formation, crystal precipitation, or behavior of fluxes themselves at conditions relevant to synthesis. In this study we examine the properties of a salt flux system that has proven extremely fertile for growth of new materials: the potassium polysulfides spanning K(2)S(3) and K(2)S(5), which melt between 302 and 206 °C. We present in situ Raman spectroscopy of melts between K(2)S(3) and K(2)S(5) and find strong coupling between n in K(2)S(n) and the molten local structure, implying that the S(n)(2-) chains in the crystalline state are mirrored in the melt. In any reactive flux system, K(2)S(n) included, a signature of changing species in the melt implies that their evolution during a reaction can be characterized and eventually controlled for selective formation of compounds. We use in situ X-ray total scattering to obtain the pair distribution function of molten K(2)S(5) and model the length of S(n)(2-) chains in the melt using reverse Monte Carlo simulations. Combining in situ Raman and total scattering provides a path to understanding the behavior of reactive media and should be broadly applied for more informed, targeted synthesis of compounds in a wide variety of inorganic fluxes.

  17. Stereocontrolled synthesis of syn-β-Hydroxy-α-amino acids by direct aldolization of pseudoephenamine glycinamide.

    Science.gov (United States)

    Seiple, Ian B; Mercer, Jaron A M; Sussman, Robin J; Zhang, Ziyang; Myers, Andrew G

    2014-04-25

    β-Hydroxy-α-amino acids figure prominently as chiral building blocks in chemical synthesis and serve as precursors to numerous important medicines. Reported herein is a method for the synthesis of β-hydroxy-α-amino acid derivatives by aldolization of pseudoephenamine glycinamide, which can be prepared from pseudoephenamine in a one-flask protocol. Enolization of (R,R)- or (S,S)-pseudoephenamine glycinamide with lithium hexamethyldisilazide in the presence of LiCl followed by addition of an aldehyde or ketone substrate affords aldol addition products that are stereochemically homologous with L- or D-threonine, respectively. These products, which are typically solids, can be obtained in stereoisomerically pure form in yields of 55-98 %, and are readily transformed into β-hydroxy-α-amino acids by mild hydrolysis or into 2-amino-1,3-diols by reduction with sodium borohydride. This new chemistry greatly facilitates the construction of novel antibiotics of several different classes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Protein coated gold nanoparticles as template for the directed synthesis of highly fluorescent gold nanoclusters

    Science.gov (United States)

    Zhang, Lingyan; Han, Fei

    2018-04-01

    Bovine serum albumin (BSA) modified gold nanoparticles (AuNPs) was selected as template for the synthesis of AuNPs@gold nanoclusters (AuNCs) core/shell nanoparticles, in which BSA not only acted as dual functions agent for both anchoring and reducing Au3+ ions, but also was employed as a bridge between the AuNPs and AuNCs. Optical properties of AuNPs@AuNCs core/shell nanoparticles were studied using UV-visible and fluorescence spectroscopy. The prepared AuNPs@AuNCs core/shell nanoparticles exhibited sphere size uniformity with improved monodispersity, excellent fluorescence and fluorescent stability. Compared with AuNCs, AuNPs@AuNCs core/shell nanoparticles possessed large size and strong fluorescence intensity due to the effect of AuNPs as core. Moreover, the mechanism of the AuNPs induced fluorescence changes of the core/shell nanoparticles was first explored.

  19. The integral Music controller: Introducing a Direct Emotional Interface to gestural control of sound synthesis.

    OpenAIRE

    Knapp, R. Benjamin; Cook, Perry R.

    2005-01-01

    This paper describes the concept of the integral music controller (IMC), a controller that combines gestural interface with direct emotional control of a digital musical instrument. This new controller enables the performer to move smoothly between direct physical interaction with an acoustical musical instrument, and gestural/emotional control of the instrument’s physical model. The use of physiological signals to determine gesture and emotion is an important component of the IMC. The design...

  20. Mixed phase Pt-Ru catalyst for direct methanol fuel cell anode by flame aerosol synthesis

    DEFF Research Database (Denmark)

    Chakraborty, Debasish; Bischoff, H.; Chorkendorff, Ib

    2005-01-01

    A spray-flame aerosol catalyzation technique was studied for producing Pt-Ru anode electrodes for the direct methanol fuel cell. Catalysts were produced as aerosol nanoparticles in a spray-flame reactor and deposited directly as a thin layer on the gas diffusion layer. The as-prepared catalyst......Ru1/Vulcan carbon. The kinetics of methanol oxidation on the mixed phase catalyst was also explored by electrochemical impedance spectroscopy. (c) 2005 The Electrochemical Society....

  1. Mechanisms of direct hydrogen peroxide synthesis on silicon and phosphorus dual-doped graphene: a DFT-D study.

    Science.gov (United States)

    Li, Shuo; Lu, Zhansheng; Zhang, Yi; Ma, Dongwei; Yang, Zongxian

    2017-03-29

    Hydrogen peroxide (H 2 O 2 ) is an important chemical commodity, with demand growing significantly in chemical synthesis due to its green characteristics. The mechanisms of the direct synthesis of hydrogen peroxide (DSHP) on metal-free silicon and phosphorus dual-doped graphene (Si-P-G) catalyst, based on a dispersion-corrected density functional theory (DFT-D) method, are systematically investigated. The most stable Si-P-G catalyst is presented, with the local region of dopants shown to play an important role in the adsorption and reduction of oxygen. A two-electron pathway is probable for DSHP on Si-P-G according to kinetic and thermodynamic analyses. The hydrogenation of O 2 to OOH is the rate-limiting step, with a small barrier energy of 0.66 eV, and the potential energy surface is downhill by Gibbs free energy calculations. All results indicate that Si-P-G is a novel catalyst with high activity and good selectivity for DSHP.

  2. On the direct synthesis of Cu(BDC) MOF nanosheets and their performance in mixed matrix membranes

    Energy Technology Data Exchange (ETDEWEB)

    Shete, Meera; Kumar, Prashant; Bachman, Jonathan E.; Ma, Xiaoli; Smith, Zachary P.; Xu, Wenqian; Mkhoyan, K. Andre; Long, Jeffrey R.; Tsapatsis, Michael

    2018-03-01

    High aspect-ratio nanosheets of metal-organic frameworks (MOFs) hold promise for use as selective flakes in gas separation membranes. However, simple and scalable methods for the synthesis of MOF nanosheets have thus far remained elusive. Here, we describe the direct synthesis of Cu(BDC) (BDC2-= 1,4-benzenedicarboxylate) nanosheets with an average lateral size of 2.5 mu m and a thickness of 25 nm from a well-mixed solution. Characterization of the nanosheets by powder and thin film X-ray diffraction, electron microscopy, and electron diffraction reveals pronounced structural disorder that may affect their pore structure. Incorporation of the Cu (BDC) nanosheets into a Matrimid polymer matrix results in mixed matrix membranes (MMMs) that exhibit a 70% increase in the CO2/CH4 selectivity compared with that of Matrimid. Analysis of new and previously reported permeation data for Cu(BDC) MMMs using a mathematical model for selective flake composites indicates that further performance improvements could be achieved with the selection of different polymers for use in the continuous phase.

  3. Zirconocene and Si-tethered diynes: a happy match directed toward organometallic chemistry and organic synthesis.

    Science.gov (United States)

    Zhang, Wen-Xiong; Zhang, Shaoguang; Xi, Zhenfeng

    2011-07-19

    Characterizing reactive organometallic intermediates is critical for understanding the mechanistic aspects of metal-mediated organic reactions. Moreover, the isolation of reactive organometallic intermediates can often result in the ability to design new synthetic methods. In this Account, we outline synthetic methods that we developed for a variety of diverse Zr/Si organo-bimetallic compounds and Si/N heteroatom-organic compounds through the detailed study of zirconacyclobutene-silacyclobutene fused compounds. Two basic components are involved in this chemistry. The first is the Si-tethered diyne, which owes its rich reactive palette to the combination of the Si-C bond and the C≡C triple bond. The second is the low-valent zirconocene species Cp(2)Zr(II), which has proven very useful in organic synthesis. The reaction of these two components affords the zirconacyclobutene-silacyclobutene fused compound, which is the key reactive Zr/Si organo-bimetallic intermediate discussed here. We discuss the three types of reactions that have been developed for the zirconacyclobutene-silacyclobutene fused intermediate. The reaction with nitriles (the C≡N triple bond) is introduced in the first section. In this one-pot reaction, up to four different components can be combined: the Si-tethered diyne can be reacted with three identical nitriles, with differing nitriles, or with a nitrile and other unsaturated organic substrates such as formamides, isocyanides, acid chlorides, aldehydes, carbodiimides, and azides. Several unexpected multiring, fused Zr/Si organo-bimetallic intermediates were isolated and characterized. A wide variety of N-heterocycles, such as 5-azaindole, pyrrole, and pyrroloazepine derivatives, were obtained. We then discuss the reaction with alkynes (the C≡C triple bond). A consecutive skeletal rearrangement, differing from that observed in the reactions with nitriles, takes place in this reaction. Finally, we discuss the reaction with the C═X substrates

  4. [1+1+3] Annulation of Diazoenals and Vinyl Azides: Direct Synthesis of Functionalized 1-Pyrrolines through Olefination.

    Science.gov (United States)

    Kanchupalli, Vinaykumar; Katukojvala, Sreenivas

    2018-05-04

    A dirhodium carboxylate catalyzed [1+1+3] annulation reaction of diazoenals and vinyl azides that gives synthetically important enal-functionalized 1-pyrroline derivatives was developed. The reaction involves a novel rhodium-catalyzed olefination of diazoenals with vinyl azides via electrophilic enal carbenoids, resulting in a new class of enal acrylates. The annulation reaction was used for the direct synthesis of valuable deuterated 1-pyrrolines. Structural diversification of the enal-functionalized 1-pyrrolines resulted in the biologically important pyrrolidine-fused oxaziridine, amino acid derivatives, and a 6-azabicyclo[3.2.1]octane motif present in polycyclic alkaloids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Studies of the chemical basis of the origin of protein synthesis Initiation and direction of peptide growth

    Science.gov (United States)

    Mullins, D. W., Jr.; Lacey, J. C., Jr.

    1980-01-01

    The data presented in this paper show that the ease of nonenzymatic activation of carboxylic acids by ATP at pH 5 varies directly with the pKa of the carboxyl group, and is consistent with the idea that it is the protonated form of the carboxyl group which participates in the activation reaction. Consequently, since most N-blocked amino acids have higher pKas than do their unblocked forms, they are activated more readily, and it has been demonstrated that this principle applies to peptides as well, which are activated more rapidly than single amino acids. It is proposed that this fact may be partly responsible for the origin of two important features still observed in contemporary protein synthesis: (1) initiation in prokaryotes is accomplished with an N-blocked amino acid, and (2) elongation in all living systems occurs at the carboxyl end of the growing peptide.

  6. High temperature synthesis of ceramic composition by directed reaction of molten titanium or zirconium with boron carbide

    International Nuclear Information System (INIS)

    Johnson, W.B.

    1990-01-01

    Alternative methods of producing ceramics and ceramic composites include sintering, hot pressing and more recently hot isostatic pressing (HIP) and self-propagating high temperature synthesis (SHS). Though each of these techniques has its advantages, each suffers from several restrictions as well. Sintering may require long times at high temperatures and for most materials requires sintering aids to get full density. These additives can, and generally do, change (often degrade) the properties of the ceramic. Hot pressing and hot isostatic pressing are convenient methods to quickly prepare samples of some materials to full density, but generally are expensive and may damage some types of reinforcements during densification. This paper focuses on the preparation and processing of composites prepared by the directed reaction of molten titanium or zirconium with boron carbide. Advantages and disadvantages of this approach when compared to traditional methods are discussed, with reference to specific examples. Examples of microstructure are properties of these materials are reported

  7. Direct synthesis of antimicrobial coatings based on tailored bi-elemental nanoparticles

    Directory of Open Access Journals (Sweden)

    Giulio Benetti

    2017-03-01

    Full Text Available Ultrathin coatings based on bi-elemental nanoparticles (NPs are very promising to limit the surface-related spread of bacterial pathogens, particularly in nosocomial environments. However, tailoring the synthesis, composition, adhesion to substrate, and antimicrobial spectrum of the coating is an open challenge. Herein, we report on a radically new nanostructured coating, obtained by a one-step gas-phase deposition technique, and composed of bi-elemental Janus type Ag/Ti NPs. The NPs are characterized by a cluster-in-cluster mixing phase with metallic Ag nano-crystals embedded in amorphous TiO2 and present a promising antimicrobial activity including also multidrug resistant strains. We demonstrate the flexibility of the method to tune the embedded Ag nano-crystals dimension, the total relative composition of the coating, and the substrate type, opening the possibility of tailoring the dimension, composition, antimicrobial spectrum, and other physical/chemical properties of such multi-elemental systems. This work is expected to significantly spread the range of applications of NPs coatings, not only as an effective tool in the prevention of healthcare-associated infections but also in other technologically relevant fields like sensors or nano-/micro joining.

  8. Narrative synthesis of equine-assisted psychotherapy literature: Current knowledge and future research directions.

    Science.gov (United States)

    Lee, Ping-Tzu; Dakin, Emily; McLure, Merinda

    2016-05-01

    Equine-assisted psychotherapy (EAP) is an innovative emerging approach to mental health treatment. This narrative synthesis explores the current state of knowledge and areas for future research in EAP. Specifically reviewed are qualitative and quantitative empirical studies, including both articles published in peer-reviewed journals and research presented in theses and dissertations. We selected 24 studies for final inclusion in this study, dating between 2005 and 2013, and including the first EAP empirical research completed in 2005. Four of these studies are peer-reviewed journal articles, while 20 are master's theses or doctoral dissertations. The reviewed qualitative research provides initial evidence for the value of EAP for enhancing adolescents' communication and relationship skills. The reviewed experimental and quasi-experimental research provides initial evidence for the value of EAP for enhancing children's and adolescents' emotional, social and behavioural functioning. Yet, conclusions about the effectiveness of EAP must still be considered preliminary due to various methodological limitations in the reviewed research. The narrative review describes these methodological limitations and concludes with recommendations for future research. © 2015 John Wiley & Sons Ltd.

  9. Phage-Directed Synthesis of Photoluminescent Zinc Oxide Nanoparticles under Benign Conditions.

    Science.gov (United States)

    Żelechowska, Kamila; Karczewska-Golec, Joanna; Karczewski, Jakub; Łoś, Marcin; Kłonkowski, Andrzej M; Węgrzyn, Grzegorz; Golec, Piotr

    2016-09-21

    Biological systems, especially bacteriophages and peptides, are an attractive green alternative to other known methods of nanoparticle synthesis. In this work, for the first time, bacteriophages were employed to synthesize a specific peptide, capable of producing nanoparticles (NPs). Derivatives of M13 bacteriophage exposing a ZnO-binding peptide (TMGANLGLKWPV) on either pIII or pVIII phage coat protein were constructed and used as a biotemplate. The exposition of the ZnO-binding peptide, synthesized by phages during their propagation in bacteria, on M13 virions provided a groundwork for growing ZnO nanostructures. Depending on the recombinant phage type used (M13-pIII-ZnO or M13-pVIII-ZnO), well separated ZnO NPs or complex 3D structures of ZnO NPs of ca. 20-40 nm were synthesized at room temperature. The synthesized ZnO nanoparticles served as a luminescent material that emitted light near the short wavelength end of the visible region (at ca. 400 nm). The next very low intensity emission band at 530 nm demonstrated that the ZnO material obtained is characterized by a low concentration of surface defects.

  10. Direct synthesis of antimicrobial coatings based on tailored bi-elemental nanoparticles

    Science.gov (United States)

    Benetti, Giulio; Cavaliere, Emanuele; Canteri, Adalberto; Landini, Giulia; Rossolini, Gian Maria; Pallecchi, Lucia; Chiodi, Mirco; Van Bael, Margriet J.; Winckelmans, Naomi; Bals, Sara; Gavioli, Luca

    2017-03-01

    Ultrathin coatings based on bi-elemental nanoparticles (NPs) are very promising to limit the surface-related spread of bacterial pathogens, particularly in nosocomial environments. However, tailoring the synthesis, composition, adhesion to substrate, and antimicrobial spectrum of the coating is an open challenge. Herein, we report on a radically new nanostructured coating, obtained by a one-step gas-phase deposition technique, and composed of bi-elemental Janus type Ag/Ti NPs. The NPs are characterized by a cluster-in-cluster mixing phase with metallic Ag nano-crystals embedded in amorphous TiO2 and present a promising antimicrobial activity including also multidrug resistant strains. We demonstrate the flexibility of the method to tune the embedded Ag nano-crystals dimension, the total relative composition of the coating, and the substrate type, opening the possibility of tailoring the dimension, composition, antimicrobial spectrum, and other physical/chemical properties of such multi-elemental systems. This work is expected to significantly spread the range of applications of NPs coatings, not only as an effective tool in the prevention of healthcare-associated infections but also in other technologically relevant fields like sensors or nano-/micro joining.

  11. Science for a wilder Anthropocene: Synthesis and future directions for trophic rewilding research.

    Science.gov (United States)

    Svenning, Jens-Christian; Pedersen, Pil B M; Donlan, C Josh; Ejrnæs, Rasmus; Faurby, Søren; Galetti, Mauro; Hansen, Dennis M; Sandel, Brody; Sandom, Christopher J; Terborgh, John W; Vera, Frans W M

    2016-01-26

    Trophic rewilding is an ecological restoration strategy that uses species introductions to restore top-down trophic interactions and associated trophic cascades to promote self-regulating biodiverse ecosystems. Given the importance of large animals in trophic cascades and their widespread losses and resulting trophic downgrading, it often focuses on restoring functional megafaunas. Trophic rewilding is increasingly being implemented for conservation, but remains controversial. Here, we provide a synthesis of its current scientific basis, highlighting trophic cascades as the key conceptual framework, discussing the main lessons learned from ongoing rewilding projects, systematically reviewing the current literature, and highlighting unintentional rewilding and spontaneous wildlife comebacks as underused sources of information. Together, these lines of evidence show that trophic cascades may be restored via species reintroductions and ecological replacements. It is clear, however, that megafauna effects may be affected by poorly understood trophic complexity effects and interactions with landscape settings, human activities, and other factors. Unfortunately, empirical research on trophic rewilding is still rare, fragmented, and geographically biased, with the literature dominated by essays and opinion pieces. We highlight the need for applied programs to include hypothesis testing and science-based monitoring, and outline priorities for future research, notably assessing the role of trophic complexity, interplay with landscape settings, land use, and climate change, as well as developing the global scope for rewilding and tools to optimize benefits and reduce human-wildlife conflicts. Finally, we recommend developing a decision framework for species selection, building on functional and phylogenetic information and with attention to the potential contribution from synthetic biology.

  12. Ultrathin ultrananocrystalline diamond film synthesis by direct current plasma-assisted chemical vapor deposition

    Science.gov (United States)

    Lee, Hak-Joo; Jeon, Hyeongtag; Lee, Wook-Seong

    2011-10-01

    The synthesis of ultrathin, mirror-smooth, and void-free ultra-nanocrystalline diamond (UNCD) film was investigated using DC-PACVD. The seeding process was investigated in the previously reported "two-step" seeding scheme, where the substrate was pretreated in microwave hydrocarbon plasma prior to the ultrasonic seeding to enhance seed density; in the present study, DC plasma and hot filament process were adopted for the pretreatment, instead of the conventional microwave plasma. Two types of nano-diamond seed powders of similar grain sizes but with different zeta potentials were also compared. The pretreated substrate surface and the synthesized UNCD film were characterized by near edge x-ray absorption fine structure, FTIR, AFM, high-resolution scanning electron microscope, HR-TEM, and Raman spectroscopy. The electrophoretic light scattering spectroscopy was adopted to characterize the zeta potentials of the seeding suspensions and that of the substrates, respectively. Contrary to the previous report, the pretreatments deteriorated the seed density relative to that of the non-treated substrate. By contrast, the seed density was drastically improved by using a proper type of the nano-diamond seed powder. The seed density variation according to the substrate pretreatments and the type of the seed powders was attributed to the relative values of the zeta potentials of the substrates and that of the seed powders, which indicated the electrostatic nature of the seeding process. The variation of the substrate surface zeta potentials was attributed to the variation in the surface terminations induced by the respective pretreatments. The present DC-PACVD environment ensured that the secondary nucleation was also active enough to generate the densely packed UNCD grains in the growth stage. Consequently, the ultrathin, mirror-smooth and void-free UNCD film of 30 nm in thickness was enabled.

  13. Direct benefit of vaccinating boys along with girls against oncogenic human papillomavirus: bayesian evidence synthesis.

    Science.gov (United States)

    Bogaards, Johannes A; Wallinga, Jacco; Brakenhoff, Ruud H; Meijer, Chris J L M; Berkhof, Johannes

    2015-05-12

    To assess the reduction in the vaccine preventable burden of cancer in men if boys are vaccinated along with girls against oncogenic human papillomavirus (HPV). Bayesian evidence synthesis approach used to evaluate the impact of vaccination against HPV types 16 and 18 on the burden of anal, penile, and oropharyngeal carcinomas among heterosexual men and men who have sex with men. The reduced transmission of vaccine-type HPV from vaccination of girls was assumed to lower the risk of HPV associated cancer in all men but not to affect the excess risk of HPV associated cancers among men who have sex with men. General population in the Netherlands. Inclusion of boys aged 12 into HPV vaccination programmes. Quality adjusted life years (QALYs) and numbers needed to vaccinate. Before HPV vaccination, 14.9 (95% credible interval 12.2 to 18.1) QALYs per thousand men were lost to vaccine preventable cancers associated with HPV in the Netherlands. This burden would be reduced by 37% (28% to 48%) if the vaccine uptake among girls remains at the current level of 60%. To prevent one additional case of cancer among men, 795 boys (660 to 987) would need to be vaccinated; with tumour specific numbers for anal, penile, and oropharyngeal cancer of 2162, 3486, and 1975, respectively. The burden of HPV related cancer in men would be reduced by 66% (53% to 805) if vaccine uptake among girls increases to 90%. In that case, 1735 boys (1240 to 2900) would need to be vaccinated to prevent an additional case; with tumour specific numbers for anal, penile, and oropharyngeal cancer of 2593, 29107, and 6484, respectively. Men will benefit indirectly from vaccination of girls but remain at risk of cancers associated with HPV. The incremental benefit of vaccinating boys when vaccine uptake among girls is high is driven by the prevention of anal carcinomas, which underscores the relevance of HPV prevention efforts for men who have sex with men. © Bogaards et al 2015.

  14. Directed synthesis of bio-inorganic vanadium oxide composites using genetically modified filamentous phage

    International Nuclear Information System (INIS)

    Mueller, Michael; Baik, Seungyun; Jeon, Hojeong; Kim, Yuchan; Kim, Jungtae; Kim, Young Jun

    2015-01-01

    Highlights: • Phage is an excellent seeding for bio-templates for environmentally benign vanadium oxide nanocomposite synthesis. • The synthesized bio-inorganic vanadium oxide showed photodegradation activities. • The fabricated wt phage/vanadium oxide composite exhibited bundle-like structure. • The fabricated RSTB-phage/vanadium oxide composite exhibited a ball with a fiber-like nanostructure. • The virus/vanadium oxide composite could be applied in photocatalysts, sensors and nanoelectronic applications. - Abstract: The growth of crystalline vanadium oxide using a filamentous bacteriophage template was investigated using sequential incubation in a V 2 O 5 precursor. Using the genetic modification of the bacteriophage, we displayed two cysteines that constrained the RSTB-1 peptide on the major coat protein P8, resulting in vanadium oxide crystallization. The phage-driven vanadium oxide crystals with different topologies, microstructures, photodegradation and vanadium oxide composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), quartz microbalance and dissipation (QCM-D) and X-ray photoelectron spectroscopy (XPS). Non-specific electrostatic attraction between a wild-type phage (wt-phage) and vanadium cations in the V 2 O 5 precursor caused phage agglomeration and fiber formation along the length of the viral scaffold. As a result, the addition of recombinant phage (re-phage) in V 2 O 5 precursors formed heterogeneous structures, which led to efficient condensation of vanadium oxide crystal formation in lines, shown by QCM-D analysis. Furthermore, re-phage/V x O x composites showed significantly enhanced photodegradation activities compared with the synthesized wt-phage-V 2 O 5 composite under illumination. This study demonstrates that peptide-mediated vanadium oxide mineralization is governed by a complicated interplay of peptide sequence, local structure, kinetics and the presence of a mineralizing

  15. Direct synthesis of formic acid from carbon dioxide by hydrogenation in acidic media.

    Science.gov (United States)

    Moret, Séverine; Dyson, Paul J; Laurenczy, Gábor

    2014-06-02

    The chemical transformation of carbon dioxide into useful products becomes increasingly important as CO2 levels in the atmosphere continue to rise as a consequence of human activities. In this article we describe the direct hydrogenation of CO2 into formic acid using a homogeneous ruthenium catalyst, in aqueous solution and in dimethyl sulphoxide (DMSO), without any additives. In water, at 40 °C, 0.2 M formic acid can be obtained under 200 bar, however, in DMSO the same catalyst affords 1.9 M formic acid. In both solvents the catalysts can be reused multiple times without a decrease in activity. Worldwide demand for formic acid continues to grow, especially in the context of a renewable energy hydrogen carrier, and its production from CO2 without base, via the direct catalytic carbon dioxide hydrogenation, is considerably more sustainable than the existing routes.

  16. Direct synthesis of formic acid from carbon dioxide by hydrogenation in acidic media

    Science.gov (United States)

    Moret, Séverine; Dyson, Paul J.; Laurenczy, Gábor

    2014-01-01

    The chemical transformation of carbon dioxide into useful products becomes increasingly important as CO2 levels in the atmosphere continue to rise as a consequence of human activities. In this article we describe the direct hydrogenation of CO2 into formic acid using a homogeneous ruthenium catalyst, in aqueous solution and in dimethyl sulphoxide (DMSO), without any additives. In water, at 40 °C, 0.2 M formic acid can be obtained under 200 bar, however, in DMSO the same catalyst affords 1.9 M formic acid. In both solvents the catalysts can be reused multiple times without a decrease in activity. Worldwide demand for formic acid continues to grow, especially in the context of a renewable energy hydrogen carrier, and its production from CO2 without base, via the direct catalytic carbon dioxide hydrogenation, is considerably more sustainable than the existing routes. PMID:24886955

  17. Synthesis of metalloporphyrin-based conjugated microporous polymer spheres directed by bipyridine-type ligands.

    Science.gov (United States)

    Ji, Guipeng; Yang, Zhenzhen; Zhao, Yanfei; Zhang, Hongye; Yu, Bo; Xu, Jilei; Xu, Huanjun; Liu, Zhimin

    2015-04-30

    Zinc porphyrin (TP-Zn)-based conjugated microporous polymer (Zn-CMP) spheres were obtained via Sonagashira-Hagihara cross coupling reactions between 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin-Zn(II) and brominated monomers directed by bidentate bipyridine (BP)-type ligands for the first time, and the sphere diameters could be adjusted from 320 to 740 nm. The coordination between BP and TP-Zn was proved to be the key to forming spheres.

  18. Highly integrated CO2 capture and conversion: Direct synthesis of cyclic carbonates from industrial flue gas

    KAUST Repository

    Barthel, Alexander

    2016-02-08

    Robust and selective catalytic systems based on early transition metal halides (Y, Sc, Zr) and organic nucleophiles were found able to quantitatively capture CO2 from diluted streams via formation of hemicarbonate species and to convert it to cyclic organic carbonates under ambient conditions. This observation was exploited in the direct and selective chemical fixation of flue gas CO2 collected from an industrial exhaust, affording high degrees of CO2 capture and conversion.

  19. Total asymmetric synthesis of the putative structure of the cytotoxic diterpenoid (-)-sclerophytin a and of the authentic natural sclerophytins A and B.

    Science.gov (United States)

    Bernardelli, P; Moradei, O M; Friedrich, D; Yang, J; Gallou, F; Dyck, B P; Doskotch, R W; Lange, T; Paquette, L A

    2001-09-19

    An enantioselective synthetic route to the thermodynamically most stable diastereomer of the structure assigned to sclerophytin A (5) has been realized. The required tricyclic ketone 33 was prepared by sequential Tebbe-Claisen rearrangement of lactones 29 and 30, which originated from the Diels-Alder cycloaddition of Danishefsky's diene to (5S)-5-(d-menthyloxy)-2(5H)-furanone (14). An allyl and a cyano group were introduced into the resulting adduct by means of stereocontrolled allylindation under aqueous Barbier-like conditions and by way of cyanotrimethylsilane, respectively. Following stereocontrolled nucleophilic addition of a methyl group to 33, ring A was elaborated by formation of the silyl enol ether, ytterbium triflate-catalyzed condensation with formaldehyde, O-silylation, and Cu(I)-promoted 1,4-addition of isopropylmagnesium chloride. The superfluous ketone carbonyl was subsequently removed and the second ether bridge introduced by means of oxymercuration chemistry. Only then was the exocyclic methylene group unmasked via elimination. An alternative approach to the alpha-carbinol diastereomer proceeds by initial alpha-oxygenation of 37 and ensuing 1,2-carbonyl transposition. Neither this series of steps nor the Wittig olefination to follow induced epimerization at C10. Through deployment of oxymercuration chemistry, it was again possible to elaborate the dual oxygen-bridge network of the target ring system. Oxidation of the organomercurial products with O(2) in the presence of sodium borohydride furnished 72, which was readily separated from its isomer 73 after oxidation to 61. Hydride attack on this ketone proceeded with high selectivity from the beta-direction to deliver (-)-60. Comparison of the high-field (1)H and (13)C NMR properties and polarity of synthetic 5 with natural material required that structural revision be made. Following a complete spectral reassessment of the structural assignments to many sclerophytin diterpenes, a general approach

  20. Directed synthesis of bio-inorganic vanadium oxide composites using genetically modified filamentous phage

    Energy Technology Data Exchange (ETDEWEB)

    Mueller, Michael; Baik, Seungyun [Environmental Safety Group, Korea Institute of Science and Technology Europe (KIST-Europe) Forschungsgesellschaft mbH, Campus E 7 1, Saarbruecken (Germany); Jeon, Hojeong; Kim, Yuchan [Center for Biomaterials, Biomedical Research Institute Korea Institute of Science and Technology (KIST), Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Kim, Jungtae [Environmental Safety Group, Korea Institute of Science and Technology Europe (KIST-Europe) Forschungsgesellschaft mbH, Campus E 7 1, Saarbruecken (Germany); Kim, Young Jun, E-mail: youngjunkim@kist-europe.de [Environmental Safety Group, Korea Institute of Science and Technology Europe (KIST-Europe) Forschungsgesellschaft mbH, Campus E 7 1, Saarbruecken (Germany)

    2015-05-15

    Highlights: • Phage is an excellent seeding for bio-templates for environmentally benign vanadium oxide nanocomposite synthesis. • The synthesized bio-inorganic vanadium oxide showed photodegradation activities. • The fabricated wt phage/vanadium oxide composite exhibited bundle-like structure. • The fabricated RSTB-phage/vanadium oxide composite exhibited a ball with a fiber-like nanostructure. • The virus/vanadium oxide composite could be applied in photocatalysts, sensors and nanoelectronic applications. - Abstract: The growth of crystalline vanadium oxide using a filamentous bacteriophage template was investigated using sequential incubation in a V{sub 2}O{sub 5} precursor. Using the genetic modification of the bacteriophage, we displayed two cysteines that constrained the RSTB-1 peptide on the major coat protein P8, resulting in vanadium oxide crystallization. The phage-driven vanadium oxide crystals with different topologies, microstructures, photodegradation and vanadium oxide composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), quartz microbalance and dissipation (QCM-D) and X-ray photoelectron spectroscopy (XPS). Non-specific electrostatic attraction between a wild-type phage (wt-phage) and vanadium cations in the V{sub 2}O{sub 5} precursor caused phage agglomeration and fiber formation along the length of the viral scaffold. As a result, the addition of recombinant phage (re-phage) in V{sub 2}O{sub 5} precursors formed heterogeneous structures, which led to efficient condensation of vanadium oxide crystal formation in lines, shown by QCM-D analysis. Furthermore, re-phage/V{sub x}O{sub x} composites showed significantly enhanced photodegradation activities compared with the synthesized wt-phage-V{sub 2}O{sub 5} composite under illumination. This study demonstrates that peptide-mediated vanadium oxide mineralization is governed by a complicated interplay of peptide sequence, local structure

  1. Recent Advance in Heterocyclic Organozinc and Organomanganese Compounds; Direct Synthetic Routes and Application in Organic Synthesis

    Directory of Open Access Journals (Sweden)

    Reuben D. Rieke

    2010-11-01

    Full Text Available A practical synthetic route for the preparation of 2-pyridyl and 3-pyridyl derivatives has been accomplished by utilizing a simple coupling reaction of stable 2-pyridylzinc bromides and 3-pyridylzinc bromides. The organozincs used in this study were easily prepared via the direct insertion of active zinc into the corresponding bromopyridines. The subsequent coupling reactions with a variety of different electrophiles have afforded the corresponding coupling products. Using highly active manganese, a variety of Grignard-type organomanganese reagents have been obtained. The subsequent coupling reactions of the resulting organomanganese reagents with several electrophiles have also been accomplished under mild conditions.

  2. Direct Synthesis of Phenol from Benzene on an Activated Carbon Catalyst Treated with Nitric Acid

    Science.gov (United States)

    Chen, Cui-hong; Xu, Jia-quan; Jin, Ming-ming; Li, Gui-ying; Hu, Chang-wei

    2011-06-01

    Commercially available coal-based activated carbon was treated by nitric acid with different concentrations and the resultant samples were used as catalysts for the direct hydroxylation of benzene to phenol in acetonitrile. Boehm titration, X-ray photoelectron spectroscopy, scanning electron microscope coupled with an energy dispersive X-ray microanalyzer, and Brunauer-Emmett-Teller method were used to characterize the samples. The number of carboxyl groups on the surface was found to be the main factor affecting the catalytic activity. An optimum catalytic performance with a yield of 15.7% and a selectivity of 87.2% to phenol was obtained.

  3. Template-directed synthesis of flexible porphyrin nanocage and nanorings via one-step olefin metathesis.

    Science.gov (United States)

    Zhu, Bin; Chen, Huanxin; Lin, Wei; Ye, Yang; Wu, Jing; Li, Shijun

    2014-10-29

    We describe the fabrication of a suite of flexible porphyrin cages and nanorings from a simple tetraalkene-derived zinc porphyrin monomer via a highly efficient template-directed strategy. The zinc porphyrin monomers were preorganized together by coordination with N atoms of multidentate ligands. Subsequent one-step olefin metathesis furnished a bisporphyrin cage, a triporphyrin nanoring, and a hexaporphyrin nanoring. In the case of the hexaporphyrin nanoring, 24 terminal olefins from six porphyrin monomers reacted with each other to form 12 new double bonds, delivering the final product. The triporphyrin and hexaporphyrin nanorings were further employed as hosts to encapsulate C60 and C70.

  4. Recent advance in heterocyclic organozinc and organomanganese compounds; direct synthetic routes and application in organic synthesis.

    Science.gov (United States)

    Kim, Seung-Hoi; Rieke, Reuben D

    2010-11-08

    A practical synthetic route for the preparation of 2-pyridyl and 3-pyridyl derivatives has been accomplished by utilizing a simple coupling reaction of stable 2-pyridylzinc bromides and 3-pyridylzinc bromides. The organozincs used in this study were easily prepared via the direct insertion of active zinc into the corresponding bromopyridines. The subsequent coupling reactions with a variety of different electrophiles have afforded the corresponding coupling products. Using highly active manganese, a variety of Grignard-type organomanganese reagents have been obtained. The subsequent coupling reactions of the resulting organomanganese reagents with several electrophiles have also been accomplished under mild conditions.

  5. Direct synthesis of formic acid from carbon dioxide by hydrogenation in acidic media

    OpenAIRE

    Moret Severine; Dyson Paul J.; Laurenczy Gabor

    2014-01-01

    The chemical transformation of carbon dioxide into useful products becomes increasingly important as CO2 levels in the atmosphere continue to rise as a consequence of human activities. In this article we describe the direct hydrogenation of CO2 into formic acid using a homogeneous ruthenium catalyst, in aqueous solution and in dimethyl sulphoxide (DMSO), without any additives. In water, at 40 °C, 0.2 M formic acid can be obtained under 200 bar, however, in DMSO the same catalyst affords 1.9 M...

  6. Direct synthesis of ultrafine tetragonal BaTiO3 nanoparticles at room temperature

    Directory of Open Access Journals (Sweden)

    Hu Yong

    2011-01-01

    Full Text Available Abstract A large quantity of ultrafine tetragonal barium titanate (BaTiO3 nanoparticles is directly synthesized at room temperature. The crystalline form and grain size are checked by both X-ray diffraction and transmission electron microscopy. The results revealed that the perovskite nanoparticles as fine as 7 nm have been synthesized. The phase transition of the as-prepared nanoparticles is investigated by the temperature-dependent Raman spectrum and shows the similar tendency to that of bulk BaTiO3 materials. It is confirmed that the nanoparticles have tetragonal phase at room temperature.

  7. Direct solution-phase synthesis of Se submicrotubes using Se powder as selenium source

    International Nuclear Information System (INIS)

    Yan Shancheng; Wang Haitao; Zhang Yuping; Li Shuchun; Xiao Zhongdang

    2009-01-01

    The selenium submicrotubes were directly prepared using Se powder as selenium source by microwave-assisted method. Field-emission scan electron microscopy (FESEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) were adopted to characterize the as-prepared products. The results of high-resolution transmission electron microscopy (HRTEM) and XRD pattern proved that the selenium submicrotubes were single crystalline in nature and [0 0 1] oriented. A possible growth mechanism of the selenium submicrotubes was proposed. The effects of the experimental conditions, such as alkaline concentration and solvent properties, on the morphology and dimension of the products have also been discussed

  8. Radiolytic Synthesis of Vinyl Polymer-Clay Nanocomposite Membranes for Direct Methanol Fuel Cell

    OpenAIRE

    Kim, Yoon-Seob; Kang, Yun Ok; Choi, Seong-Ho

    2014-01-01

    The three-type vinyl polymer-clay nanocomposite membranes with sulfonate (–SO3Na) are prepared by the solvent casting method after radiation-induced copolymerization for application of the direct methanol fuel cell (DMFC) membrane. The three-type vinyl polymers in polymer-clay nanocomposite membranes are included in poly(styrene-co-sodium styrene sulfonate), poly(St-co-NaSS), poly(2-hydroxyethyl methacrylate-co-NaSS), poly(HEMA-co-NaSS), and poly(acrylic acid-co-NaSS), and poly(AAc-co-NaSS). ...

  9. Black carbon semi-direct effects on cloud cover: review and synthesis

    Directory of Open Access Journals (Sweden)

    D. Koch

    2010-08-01

    Full Text Available Absorbing aerosols (AAs such as black carbon (BC or dust absorb incoming solar radiation, perturb the temperature structure of the atmosphere, and influence cloud cover. Previous studies have described conditions under which AAs either increase or decrease cloud cover. The effect depends on several factors, including the altitude of the AA relative to the cloud and the cloud type. We attempt to categorize the effects into several likely regimes. Cloud cover is decreased if the AAs are embedded in the cloud layer. AAs below cloud may enhance convection and cloud cover. AAs above cloud top stabilize the underlying layer and tend to enhance stratocumulus clouds but may reduce cumulus clouds. AAs can also promote cloud cover in convergent regions as they enhance deep convection and low level convergence as it draws in moisture from ocean to land regions. Most global model studies indicate a regional variation in the cloud response but generally increased cloud cover over oceans and some land regions, with net increased low-level and/or reduced upper level cloud cover. The result is a net negative semi-direct effect feedback from the cloud response to AAs. In some of these climate model studies, the cooling effect of BC due to cloud changes is strong enough to essentially cancel the warming direct effects.

  10. Synthesis, characterization and analysis of platinum-based multiphase catalysts for direct ethanol fuel cells

    Science.gov (United States)

    Mann, Jonathan R.

    Platinum-based particles are synthesized via the polyol process in an effort to include various metal oxides in a multi-phase catalyst for the direct ethanol fuel cell anode. Among Eu, In, La and Nb, no single metal oxide with platinum yields open circuit potentials or maximum current densities as high as tin oxide with platinum. For this reason, particles with platinum, tin oxide and the oxide of a third metal were developed. Platinum tin/indium oxide slightly outperforms platinum tin oxide. The particles are characterized by TEM, EDX, XRD and ICP. The metal oxides and the platinum are located together in one particle, uniformly 5.3 nm in diameter. ICP analysis indicates that the catalysts are 20% platinum on carbon and the metals of the oxides are on the order of 1-2% by mass. The catalytic abilities of the particles were evaluated in a single cell direct ethanol fuel cell where polarization curves were taken up to 130°C, and oxidation products were analyzed by gas chromatography. Open circuit voltages of as high as 0.82 V were obtained for platinum tin/indium oxide catalysts and current densities as high as 0.4 A cm-2 were seen. The cells produced large amounts of acetaldehyde and acetic acid, as well as small amounts of methanol and carbon dioxide. A spillover mechanism is proposed for the oxidation of ethanol to CO2 on these platinum/metal oxide catalysts.

  11. Direct transfer of starter substrates from type I fatty acid synthase to type III polyketide synthases in phenolic lipid synthesis.

    Science.gov (United States)

    Miyanaga, Akimasa; Funa, Nobutaka; Awakawa, Takayoshi; Horinouchi, Sueharu

    2008-01-22

    Alkylresorcinols and alkylpyrones, which have a polar aromatic ring and a hydrophobic alkyl chain, are phenolic lipids found in plants, fungi, and bacteria. In the Gram-negative bacterium Azotobacter vinelandii, phenolic lipids in the membrane of dormant cysts are essential for encystment. The aromatic moieties of the phenolic lipids in A. vinelandii are synthesized by two type III polyketide synthases (PKSs), ArsB and ArsC, which are encoded by the ars operon. However, details of the synthesis of hydrophobic acyl chains, which might serve as starter substrates for the type III polyketide synthases (PKSs), were unknown. Here, we show that two type I fatty acid synthases (FASs), ArsA and ArsD, which are members of the ars operon, are responsible for the biosynthesis of C(22)-C(26) fatty acids from malonyl-CoA. In vivo and in vitro reconstitution of phenolic lipid synthesis systems with the Ars enzymes suggested that the C(22)-C(26) fatty acids produced by ArsA and ArsD remained attached to the ACP domain of ArsA and were transferred hand-to-hand to the active-site cysteine residues of ArsB and ArsC. The type III PKSs then used the fatty acids as starter substrates and carried out two or three extensions with malonyl-CoA to yield the phenolic lipids. The phenolic lipids in A. vinelandii were thus found to be synthesized solely from malonyl-CoA by the four members of the ars operon. This is the first demonstration that a type I FAS interacts directly with a type III PKS through substrate transfer.

  12. An azobenzene-containing metal-organic framework as an efficient heterogeneous catalyst for direct amidation of benzoic acids: synthesis of bioactive compounds.

    Science.gov (United States)

    Hoang, Linh T M; Ngo, Long H; Nguyen, Ha L; Nguyen, Hanh T H; Nguyen, Chung K; Nguyen, Binh T; Ton, Quang T; Nguyen, Hong K D; Cordova, Kyle E; Truong, Thanh

    2015-12-14

    An azobenzene-containing zirconium metal-organic framework was demonstrated to be an effective heterogeneous catalyst for the direct amidation of benzoic acids in tetrahydrofuran at 70 °C. This finding was applied to the synthesis of several important, representative bioactive compounds.

  13. Synthesis-based approach toward direct sandwich immunoassay for ciguatoxin CTX3C.

    Science.gov (United States)

    Oguri, Hiroki; Hirama, Masahiro; Tsumuraya, Takeshi; Fujii, Ikuo; Maruyama, Megumi; Uehara, Hisatoshi; Nagumo, Yoko

    2003-06-25

    Ciguatoxins are the major causative toxins of ciguatera seafood poisoning. Limited availability of ciguatoxins has hampered the development of a reliable and specific immunoassay for detecting these toxins in contaminated fish. Monoclonal antibodies (mAbs) specific against both ends of ciguatoxin CTX3C were prepared by immunization of mice with protein conjugates of rationally designed synthetic haptens, 3 and 4, in place of the natural toxin. Haptenic groups that possess a surface area larger than 400 A(2) were required to produce mAbs that can bind strongly to CTX3C itself. A direct sandwich enzyme-linked immunosorbent assay (ELISA) using these mAbs was established to detect CTX3C at the ppb level with no cross-reactivity against other related marine toxins, including brevetoxin A, brevetoxin B, okadaic acid, or maitotoxin.

  14. Synthesis of silicon containing materials using liquid hydrosilane compositions through direct injection

    Energy Technology Data Exchange (ETDEWEB)

    Srinivasan, Guruvenket; Sailer, Robert A.; Hoey, Justin

    2018-03-13

    An apparatus and a non-vapor-pressure dependent method of chemical vapor deposition of Si based materials using direct injection of liquid hydrosilane(s) are presented. Liquid silane precursor solutions may also include metal, non-metal or metalloid dopants, nanomaterials and solvents. An illustrative apparatus has a precursor solution and carrier gas system, atomizer and deposit head with interior chamber and a hot plate supporting the substrate. Atomized liquid silane precursor solutions and carrier gas moves through a confined reaction zone that may be heated and the aerosol and vapor are deposited on a substrate to form a thin film. The substrate may be heated prior to deposition. The deposited film may be processed further with thermal or laser processing.

  15. Microwave-assisted direct synthesis of butene from high-selectivity methane

    Science.gov (United States)

    Lu, Yi-heng; Li, Kang; Lu, Yu-wei

    2017-12-01

    Methane was directly converted to butene liquid fuel by microwave-induced non-oxidative catalytic dehydrogenation under 0.1-0.2 MPa. The results show that, under microwave heating in a two-stage fixed-bed reactor, in which nickel powder and NiOx-MoOy/SiO2 are used as the catalyst, the methane-hydrogen mixture is used as the raw material, with no acetylene detected. The methane conversion is more than 73.2%, and the selectivity of methane to butene is 99.0%. Increasing the hydrogen/methane feed volume ratio increases methane conversion and selectivity. Gas chromatography/electron impact ionization/mass spectrometry chromatographic analysis showed that the liquid fuel produced by methane dehydrogenation oligomerization contained 89.44% of butene, and the rest was acetic acid, ethanol, butenol and butyric acid, and the content was 1.0-3.0 wt%.

  16. Direct synthesis of few-layer graphene supported platinum nanocatalyst for methanol oxidation

    Science.gov (United States)

    Tan, Hong; Ma, Xiaohui; Sheng, Leimei; An, Kang; Yu, Liming; Zhao, Hongbin; Xu, Jiaqiang; Ren, Wei; Zhao, Xinluo

    2014-11-01

    High-crystalline few-layer graphene supported Pt nanoparticles have been synthesized by arc discharge evaporation of carbon electrodes containing Pt element. A high-temperature treatment under hydrogen atmosphere has been carried out to obtain a new type of Pt/graphene catalyst for methanol oxidation in direct methanol fuel cell. The morphology and structure characterizations of as-grown few-layer graphene supported Pt nanoparticles and Pt/graphene catalysts have been studied by Raman spectroscopy, scanning electron microscopy with energy-dispersive spectroscopy, and high-resolution transmission electron microscopy. Cyclic voltammograms and chronoamperometric curves show that our present Pt/graphene catalysts have larger current density for methanol oxidation, higher tolerance to carbon monoxide poisoning, and better stability during the operating procedure, compared to commercial Pt/C catalysts.

  17. Synthesis of Findings, Current Investigations, and Future Directions: Operation Brain Trauma Therapy.

    Science.gov (United States)

    Kochanek, Patrick M; Bramlett, Helen M; Shear, Deborah A; Dixon, C Edward; Mondello, Stefania; Dietrich, W Dalton; Hayes, Ronald L; Wang, Kevin K W; Poloyac, Samuel M; Empey, Philip E; Povlishock, John T; Mountney, Andrea; Browning, Megan; Deng-Bryant, Ying; Yan, Hong Q; Jackson, Travis C; Catania, Michael; Glushakova, Olena; Richieri, Steven P; Tortella, Frank C

    2016-03-15

    Operation Brain Trauma Therapy (OBTT) is a fully operational, rigorous, and productive multicenter, pre-clinical drug and circulating biomarker screening consortium for the field of traumatic brain injury (TBI). In this article, we synthesize the findings from the first five therapies tested by OBTT and discuss both the current work that is ongoing and potential future directions. Based on the results generated from the first five therapies tested within the exacting approach used by OBTT, four (nicotinamide, erythropoietin, cyclosporine A, and simvastatin) performed below or well below what was expected based on the published literature. OBTT has identified, however, the early post-TBI administration of levetiracetam as a promising agent and has advanced it to a gyrencephalic large animal model--fluid percussion injury in micropigs. The sixth and seventh therapies have just completed testing (glibenclamide and Kollidon VA 64), and an eighth drug (AER 271) is in testing. Incorporation of circulating brain injury biomarker assessments into these pre-clinical studies suggests considerable potential for diagnostic and theranostic utility of glial fibrillary acidic protein in pre-clinical studies. Given the failures in clinical translation of therapies in TBI, rigorous multicenter, pre-clinical approaches to therapeutic screening such as OBTT may be important for the ultimate translation of therapies to the human condition.

  18. Direct Synthesis of MnO2 Nanorods on Carbon Cloth as Flexible Supercapacitor Electrode

    Directory of Open Access Journals (Sweden)

    Shuang Xi

    2017-01-01

    Full Text Available MnO2 nanorod/carbon cloth (MnO2/CC composites were prepared through in situ redox deposition as freestanding electrodes for flexible supercapacitors. The CC substrates possessing porous and interconnecting structures enable the uniform decoration of MnO2 nanorods on each fiber, thus forming conformal coaxial micro/nanocomposites. Three-dimensional CC can provide considerable specific surface area for high mass loading of MnO2, and the direct deposition process without using polymeric binders enables reliable electrical connection of MnO2 with CC. The effect of MnO2 decoration on the electrochemical performances was further investigated, indicating that the electrode prepared with 40 min deposition time shows high specific capacitance (220 F/g at a scan rate of 5 mV/s and good cycling property (90% of the initial specific capacitance was maintained after 2500 cycles in 1 M Na2SO4 aqueous solution. This enhanced electrochemical performance is ascribed to the synergistic effect of good conductivity of carbon substrates as well as outstanding pseudocapacitance of MnO2 nanorods. The obtained MnO2/CC compositing electrode with the advantages of low cost and easy fabrication is promising in applications of flexible supercapacitors.

  19. Direct synthesis of carbon nanofibers from South African coal fly ash

    Science.gov (United States)

    Hintsho, Nomso; Shaikjee, Ahmed; Masenda, Hilary; Naidoo, Deena; Billing, Dave; Franklyn, Paul; Durbach, Shane

    2014-08-01

    Carbon nanofibers (CNFs), cylindrical nanostructures containing graphene, were synthesized directly from South African fly ash (a waste product formed during the combustion of coal). The CNFs (as well as other carbonaceous materials like carbon nanotubes (CNTs)) were produced by the catalytic chemical vapour deposition method (CCVD) in the presence of acetylene gas at temperatures ranging from 400°C to 700°C. The fly ash and its carbonaceous products were characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), laser Raman spectroscopy and Brunauer-Emmett-Teller (BET) surface area measurements. It was observed that as-received fly ash was capable of producing CNFs in high yield by CCVD, starting at a relatively low temperature of 400°C. Laser Raman spectra and TGA thermograms showed that the carbonaceous products which formed were mostly disordered. Small bundles of CNTs and CNFs observed by TEM and energy-dispersive spectroscopy (EDS) showed that the catalyst most likely responsible for CNF formation was iron in the form of cementite; X-ray diffraction (XRD) and Mössbauer spectroscopy confirmed these findings.

  20. Direct synthesis of chromium perovskite oxyhydride with a high magnetic-transition temperature.

    Science.gov (United States)

    Tassel, Cédric; Goto, Yoshihiro; Kuno, Yoshinori; Hester, James; Green, Mark; Kobayashi, Yoji; Kageyama, Hiroshi

    2014-09-22

    We report a novel oxyhydride SrCrO2H directly synthesized by a high-pressure high-temperature method. Powder neutron and synchrotron X-ray diffraction revealed that this compound adopts the ideal cubic perovskite structure (Pm3̄m) with O(2-)/H(-) disorder. Surprisingly, despite the non-bonding nature between Cr 3d t(2g) orbitals and the H 1s orbital, it exhibits G-type spin ordering at T(N)≈380 K, which is higher than that of RCrO3 (R=rare earth) and any chromium oxides. The enhanced T(N) in SrCrO2H with four Cr-O-Cr bonds in comparison with RCr(3+)O3 with six Cr-O-Cr bonds is reasonably explained by the tolerance factor. The present result offers an effective strategy to tune octahedral tilting in perovskites and to improve physical and chemical properties through mixed anion chemistry. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Synthesis and Characterization of Large-Area Graphene Directly CVD-Grown on h-BN

    Science.gov (United States)

    Kim, Minwoo; Song, Young; Wang, Min; Jang, Seong-Kyu; Lee, Sungjoo; Jang, Won-Jun; Kahng, Se-Jong; Graphene synthesis Collaboration; Characterization Collaboration

    2013-03-01

    As an ideal substrate for graphene, hexagonal boron nitride (h-BN) has been utilized and studied extensively by transfer technique, which still has a high chance to have impurities at the graphene/h-BN interface. Here we report direct CVD growth of graphene on large area h-BN film. AFM and Raman spectroscopy measurements show that there is only one monolayer of graphene, and whose unperturbed electronic structures are also confirmed by electron transport measurements and scanning tunneling spectroscopy. High resolution TEM images for cross-section taken before and after transferring graphene/h-BN on to SiO2 indicate this CVD-grown hybrid structure is robust enough. Based on this new method, high quality and large area graphene on h-BN film with a clean interface can be synthesized for the application of electronic devices, and can fill the missing steps to grow fully CVD-grown super-structure of graphene and h-BN. This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (Grant Numbers: 2009-0083540, 2012R1A1A2020089 and 2012R1A1A1041416).

  2. Enteric methane mitigation technologies for ruminant livestock: a synthesis of current research and future directions.

    Science.gov (United States)

    Patra, Amlan Kumar

    2012-04-01

    Enteric methane (CH(4)) emission in ruminants, which is produced via fermentation of feeds in the rumen and lower digestive tract by methanogenic archaea, represents a loss of 2% to 12% of gross energy of feeds and contributes to global greenhouse effects. Globally, about 80 million tonnes of CH(4) is produced annually from enteric fermentation mainly from ruminants. Therefore, CH(4) mitigation strategies in ruminants have focused to obtain economic as well as environmental benefits. Some mitigation options such as chemical inhibitors, defaunation, and ionophores inhibit methanogenesis directly or indirectly in the rumen, but they have not confirmed consistent effects for practical use. A variety of nutritional amendments such as increasing the amount of grains, inclusion of some leguminous forages containing condensed tannins and ionophore compounds in diets, supplementation of low-quality roughages with protein and readily fermentable carbohydrates, and addition of fats show promise for CH(4) mitigation. These nutritional amendments also increase the efficiency of feed utilization and, therefore, are most likely to be adopted by farmers. Several new potential technologies such as use of plant secondary metabolites, probiotics and propionate enhancers, stimulation of acetogens, immunization, CH(4) oxidation by methylotrophs, and genetic selection of low CH(4)-producing animals have emerged to decrease CH(4) production, but these require extensive research before they can be recommended to livestock producers. The use of bacteriocins, bacteriophages, and development of recombinant vaccines targeting archaeal-specific genes and cell surface proteins may be areas worthy of investigation for CH(4) mitigation as well. A combination of different CH(4) mitigation strategies should be adopted in farm levels to substantially decrease methane emission from ruminants. Evidently, comprehensive research is needed to explore proven and reliable CH(4) mitigation technologies

  3. Synthesis and characterization of CuGeO3 photocatalyst using Green Chemistry and its application for the degradation of direct black dye

    Directory of Open Access Journals (Sweden)

    Ashok. V. Borhade

    2013-03-01

    Full Text Available In this paper, we report synthesis of CuGeO3 photocatalyst by mechanochemical, solid state synthesis, method with green chemistry approach. The product obtained was characterized by various investigative techniques like UV-Diffuse Reflectance Spectroscopy, Fourier Transform Infrared Spectroscopy, X-ray Diffraction, Scanning Electron Microscopy, with Energy Dispersive X-ray Spectroscopy, and BET Surface area. The study confirm orthorhombic pervoskite crystal structure of photocatalyst with band gap 3.7 eV. The photocatalytic activity of the catalysts CuGeO3 was evaluated by photochemical bleaching of Direct black dye, under sun light.

  4. Amino-acid- and peptide-directed synthesis of chiral plasmonic gold nanoparticles.

    Science.gov (United States)

    Lee, Hye-Eun; Ahn, Hyo-Yong; Mun, Jungho; Lee, Yoon Young; Kim, Minkyung; Cho, Nam Heon; Chang, Kiseok; Kim, Wook Sung; Rho, Junsuk; Nam, Ki Tae

    2018-04-01

    Understanding chirality, or handedness, in molecules is important because of the enantioselectivity that is observed in many biochemical reactions 1 , and because of the recent development of chiral metamaterials with exceptional light-manipulating capabilities, such as polarization control 2-4 , a negative refractive index 5 and chiral sensing 6 . Chiral nanostructures have been produced using nanofabrication techniques such as lithography 7 and molecular self-assembly 8-11 , but large-scale and simple fabrication methods for three-dimensional chiral structures remain a challenge. In this regard, chirality transfer represents a simpler and more efficient method for controlling chiral morphology 12-18 . Although a few studies 18,19 have described the transfer of molecular chirality into micrometre-sized helical ceramic crystals, this technique has yet to be implemented for metal nanoparticles with sizes of hundreds of nanometres. Here we develop a strategy for synthesizing chiral gold nanoparticles that involves using amino acids and peptides to control the optical activity, handedness and chiral plasmonic resonance of the nanoparticles. The key requirement for achieving such chiral structures is the formation of high-Miller-index surfaces ({hkl}, h ≠ k ≠ l ≠ 0) that are intrinsically chiral, owing to the presence of 'kink' sites 20-22 in the nanoparticles during growth. The presence of chiral components at the inorganic surface of the nanoparticles and in the amino acids and peptides results in enantioselective interactions at the interface between these elements; these interactions lead to asymmetric evolution of the nanoparticles and the formation of helicoid morphologies that consist of highly twisted chiral elements. The gold nanoparticles that we grow display strong chiral plasmonic optical activity (a dis-symmetry factor of 0.2), even when dispersed randomly in solution; this observation is supported by theoretical calculations and direct

  5. Synthesis and Characterization of Molybdenum Back Contact Using Direct Current-Magnetron Sputtering for Thin Film Solar Cells

    Directory of Open Access Journals (Sweden)

    Subhash M. Pandharkar

    2018-03-01

    Full Text Available In present work, we report synthesis of molybdenum (Mo thin films by direct current (DC-magnetron sputtering method. The structural, optical, morphological, and electrical properties were investigated as a function of target-to-substrate distance. From the results, it is evident that with increase in target-to-substrate distance the thickness of films decreases while its sheet resistance and electrical resistivity increases, which is confirmed by van der Pauw method. Low angle XRD analysis revealed that with increase in target-to-substrate distance preferred orientation of Mo crystallites changes from (211 to (110 and its size decreases. The field emission scanning electron microscope (FE-SEM analysis revealed a significant change in surface morphology with increase in target-to-substrate distance. UV-Visible spectroscopy analysis showed that Mo films deposited at higher target-to-substrate distance have more reflection than those deposited at lower target-to-substrate. Finally, adhesion test was performed using scotch hatch tape adhesion test which show all Mo films have excellent adhesion over the entire range of target-to-substrate distance studied. The employment of such Mo films as back contact can be useful to improve efficiency of CZTS solar cells.

  6. Controlled synthesis of Pt/CS/PW{sub 12}-GNs composite as an anodic electrocatalyst for direct methanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Li, Zhongshui; Lei, Fengling; Ye, Lingting; Zhang, Xiaofeng; Lin, Shen, E-mail: shenlin@fjnu.edu.cn [Fujian Normal University, College of Chemistry & Chemical Engineering (China)

    2015-04-15

    Controlled assembly in aqueous solution was used to synthesize the well-organized Pt/CS/PW{sub 12}-GNs composite. By the aid of linear cationic polysaccharide chitosan, 2-D distribution worm-like Pt nanoparticles with their length and width of 15–20 and 3–4 nm, respectively, were formed on the surface of CS/PW{sub 12}-GNs using HCOOH as a reducing agent at room temperature. The introduction of CS leads to well dispersion of worm-like Pt nanoparticles, the electroactivity of H{sub 3}PW{sub 12}O{sub 40} (PW{sub 12}) alleviates CO poisoning toward Pt particles, and graphene nanosheets (GNs) ensure excellent electrical conductivity of the composites. The combined action among different components results in significantly enhanced catalytic activity of Pt/CS/PW{sub 12}-GNs toward methanol oxidation and better tolerance of CO. The as-synthesized Pt/CS/PW{sub 12}-GNs exhibit the forward peak current density of 445 mA mg{sup −1}, which is much higher than that (220 mA mg{sup −1}) for Pt/C-JM (the commercially available Johnson Matthey Hispec4000 catalyst, simplified as Pt/C-JM) and some recently reported Pt/graphene-based nanomaterials. The construction of 2-D distribution worm-like Pt nanoparticles and facile wet chemical synthesis strategy provide a promising way to develop superior performance electrocatalysts for direct methanol fuel cells applications.

  7. A High Performance Platform Based on cDNA Display for Efficient Synthesis of Protein Fusions and Accelerated Directed Evolution.

    Science.gov (United States)

    Naimuddin, Mohammed; Kubo, Tai

    2016-02-08

    We describe a high performance platform based on cDNA display technology by developing a new modified puromycin linker-oligonucleotide. The linker consists of four major characteristics: a "ligation site" for hybridization and ligation of mRNA by T4 RNA ligase, a "puromycin arm" for covalent linkage of the protein, a "polyadenosine site" for a longer puromycin arm and purification of protein fusions (optional) using oligo-dT matrices, and a "reverse transcription site" for the formation of stable cDNA protein fusions whose cDNA is covalently linked to its encoded protein. The linker was synthesized by a novel branching strategy and provided >8-fold higher yield than previous linkers. This linker enables rapid and highly efficient ligation of mRNA (>90%) and synthesis of protein fusions (∼ 50-95%) in various cell-free expression systems. Overall, this new cDNA display method provides 10-200 fold higher end-usage fusions than previous methods and benefits higher diversity libraries crucial for directed protein/peptide evolution. With the increased efficiency, this system was able to reduce the time for one selection cycle to cDNA display method. A three-finger protein library was evolved to isolate superior nanomolar range binding candidates for vascular endothelial growth factor. This method is expected to provide a beneficial impact to accelerated drug discovery and proteome analysis.

  8. Direct synthesis of L1{sub 0} FePt nanoparticles within carbon nanotubes by wet chemical procedure

    Energy Technology Data Exchange (ETDEWEB)

    Capobianchi, A; Laureti, S; Fiorani, D [Consiglio Nazionale delle Ricerche (CNR), Istituto di Struttura della Materia (ISM), Rome (Italy); Foglia, S [Consiglio Nazionale delle Ricerche (CNR), Istituto di Fotonica e Nanotecnologie, Rome (Italy); Palange, E, E-mail: aldo.capobianchi@ism.cnr.i [Universita degli Studi dell' Aquila, Dipartimento di Ingegneria Elettrica e dell' Informazione, L' Aquila (Italy)

    2010-12-01

    This paper reports on the low temperature synthesis of L1{sub 0} iron-platinum (FePt) particles within multiwall carbon nanotubes using a novel wet chemical method that allows the filling of the nanotube cavity keeping clean its external wall. In the proposed procedure, nanotubes are filled with a precursor salt of hexaaquairon(II) hexachloroplatinate, ([Fe(H{sub 2}O){sub 6}][PtCl{sub 6}]) and nanoparticles of the magnetically hard phase are directly obtained by heating at 400 {sup 0}C in a reductive atmosphere. The advantage of such a precursor, allowing one to obtain at low temperature the L1{sub 0} phase without passing through the soft fcc phase, is due to its structure, where the Fe and Pt atoms are arranged in alternating planes, as in the fct FePt structure. Morphological, structural and magnetic properties of the filled nanotubes have been investigated by transmission electron microscopy, x-ray diffraction and magnetization measurements. The results show the coexistence of nanoparticles in the superparamagnetic and blocked state, depending on the temperature, due to the particle size distribution.

  9. Hydrothermal synthesis of one-dimensional tungsten oxide nanostructures using cobalt ammonium sulfate as a structure-directing agent

    International Nuclear Information System (INIS)

    Rajagopal, Shanmugasundaram; Lee, Hae-Min; Kim, Chang-Koo; Lee, Kangtaek

    2013-01-01

    Hydrothermal synthesis of one-dimensional tungsten oxide nanostructures was performed using cobalt ammonium sulfate as a structure-directing agent, and the effect of the concentration of cobalt ammonium sulfate on the characteristics of the tungsten oxide nanostructures was investigated. XRD measurements showed that hexagonal tungsten oxide (h-WO 3 ) structures were obtained at a higher concentration of cobalt ammonium sulfate (0.2 M), while cubic tungsten oxide (c-WO 3 ) structures were obtained at a lower concentration of cobalt ammonium sulfate (0.01M). Mixed structures of h-WO 3 and c-WO 3 were observed at an intermediate concentration of cobalt ammonium sulfate. Morphological studies revealed that h-WO 3 appeared as nanowires with a diameter of about 40 nm and an average length of 1 µm. c-WO 3 was shaped in pillar-like nanorods with a diameter of about 30 nm. A red-shift in the UV/Vis absorption peak was observed with different phases of tungsten oxide nanostructures

  10. Solvent-free enzymatic synthesis of 1, 3-Diacylglycerols by direct esterification of glycerol with saturated fatty acids

    Science.gov (United States)

    2013-01-01

    Background Pure 1, 3-diacylglycerols (1, 3-DAG) have been considered to be significant surfactants in food, cosmetics and pharmaceutical industries, as well as the effect on obesity prevention. Methods In this study, a vacuum-driven air bubbling operation mode was developed and evaluated for the enzymatic synthesis of 1, 3-DAG of saturated fatty acids, by direct esterification of glycerol with fatty acids in a solvent-free system. The employed vacuum-driven air bubbling operation mode was comparable to vacuum-driven N2 bubbling protocol, in terms of lauric acid conversion and 1, 3-dilaurin content. Results Some operation parameters were optimized, and 95.3% of lauric acid conversion and 80.3% of 1, 3-dilaurin content was obtained after 3-h reaction at 50°C, with 5 wt% of Lipozyme RM IM (based on reactants) amount. Of the lipases studied, both Lipozyme RM IM and Novozym 435 exhibited good performance in terms of lauric acid conversion. Lipozyme TL IM, however, showed low activity. Lipozyme RM IM showed good operational stability in this operation protocol, 80.2% of the original catalytic activity remained after 10 consecutive batch applications. Some other 1, 3-DAG were prepared and high content was obtained after purification: 98.5% for 1, 3-dicaprylin, 99.2% for 1, 3-dicaprin, 99.1% for 1, 3-dilaurin, 99.5 for 1, 3-dipalmitin and 99.4% for 1, 3-disterin. Conclusion The established vacuum-driven air bubbling operation protocol had been demonstrated to be a simple-operating, cost-effective, application practical and efficient methodology for 1, 3-DAG preparation. PMID:23656739

  11. An unsymmetrical non-fullerene acceptor: synthesis via direct heteroarylation, self-assembly, and utility as a low energy absorber in organic photovoltaic cells.

    Science.gov (United States)

    Payne, Abby-Jo; Li, Shi; Dayneko, Sergey V; Risko, Chad; Welch, Gregory C

    2017-09-12

    This study reports on the design and synthesis of an unsymmetrical π-conjugated organic molecule composed of perylene diimide, thienyl diketopyrrolopyrrole, and indoloquinoxaline pieced together using direct heteroarylation. This material demonstrates unprecedented response in the thin-film upon post-deposition solvent vapor annealing, resulting in dramatic red-shifts in optical absorption. Such changes were utilized to enhance photocurrent generation in P3HT based organic solar cells.

  12. N-oxide as a traceless oxidizing directing group: mild rhodium(III)-catalyzed C-H olefination for the synthesis of ortho-alkenylated tertiary anilines.

    Science.gov (United States)

    Huang, Xiaolei; Huang, Jingsheng; Du, Chenglong; Zhang, Xingyi; Song, Feijie; You, Jingsong

    2013-12-02

    Double role: A traceless directing group also acts as an internal oxidant in a novel Rh(III) -catalyzed protocol developed for the synthesis of ortho-alkenylated tertiary anilines. A five-membered cyclometalated Rh(III) complex is proposed as a plausible intermediate and confirmed by X-ray crystallographic analysis. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Direct synthesis of polyfunctionalized unsaturated delta-lactones and delta-lactams from alpha-alkenoyl alpha-carboxyl/carbamoyl ketene S,S-acetals under Vilsmeier conditions.

    Science.gov (United States)

    Liu, Jun; Wang, Mang; Han, Feng; Liu, Yingjie; Liu, Qun

    2009-07-17

    An efficient method for direct synthesis of polyfunctionalized unsaturated delta-lactones 2 and delta-lactams 4 has been developed from the reaction of the easily available alpha-alkenoyl alpha-carboxyl/carbamoyl ketene S,S-acetals 1/3 and Vilsmeier reagents (DMF/POCl(3) or DMF/PBr(3)) via a cyclization followed by a halovinylation or haloformylation sequence.

  14. Reverse-direction (5'-->3') synthesis of oligonucleotides containing a 3'-S-phosphorothiolate linkage and 3'-terminal 3'-thionucleosides.

    Science.gov (United States)

    Gaynor, James W; Piperakis, Michael M; Fisher, Julie; Cosstick, Richard

    2010-03-21

    The synthesis of oligodeoxynucleotides containing 3'-thionucleosides has been explored using a reverse-direction (5'-->3') approach, based on nucleoside monomers which contain a trityl- or dimethoxytrityl-protected 3'-thiol and a 5'-O-phosphoramidite. These monomers are relatively simple to prepare as trityl-based protecting groups were introduced selectively at a 3'-thiol in preference to a 5'-hydroxyl group. As an alternative approach, trityl group migration could be induced from the 5'-oxygen to the 3'-thiol function. 5'-->3' Synthesis of oligonucleotides gave relatively poor yields for the internal incorporation of 3'-thionucleosides [to give a 3'-S-phosphorothiolate (3'-SP) linkage] and multiple 3'-SP modifications could not be introduced by this method. However, the reverse direction approach provided an efficient route to oligonucleotides terminating with a 3'-thionucleoside. The direct synthesis of these thio-terminating oligomers has not previously been reported and the methods described are applicable to 2'-deoxy-3'-thionucleosides derived from thymine, cytosine and adenine.

  15. Direct observation of the effects of cellulose synthesis inhibitors using live cell imaging of Cellulose Synthase (CESA) in Physcomitrella patens

    OpenAIRE

    Tran, Mai L.; McCarthy, Thomas W.; Sun, Hao; Wu, Shu-Zon; Norris, Joanna H.; Bezanilla, Magdalena; Vidali, Luis; Anderson, Charles T.; Roberts, Alison W.

    2018-01-01

    Results from live cell imaging of fluorescently tagged Cellulose Synthase (CESA) proteins in Cellulose Synthesis Complexes (CSCs) have enhanced our understanding of cellulose biosynthesis, including the mechanisms of action of cellulose synthesis inhibitors. However, this method has been applied only in Arabidopsis thaliana and Brachypodium distachyon thus far. Results from freeze fracture electron microscopy of protonemal filaments of the moss Funaria hygrometrica indicate that a cellulose s...

  16. Multicomponent Synthesis of Isoindolinone Frameworks via RhIII -Catalysed in situ Directing Group-Assisted Tandem Oxidative Olefination/Michael Addition.

    Science.gov (United States)

    Wang, Liang; Liu, Xi; Liu, Jian-Biao; Shen, Jun; Chen, Qun; He, Ming-Yang

    2018-04-04

    A Rh III -catalysed three-component synthesis of isoindolinone frameworks via direct assembly of benzoyl chlorides, o-aminophenols and activated alkenes has been developed. The process involves in situ generation of o-aminophenol (OAP)-based bidentate directing group (DG), Rh III -catalysed tandem ortho C-H olefination and subsequent cyclization via aza-Michael addition. This protocol exhibits good chemoselectivity and functional group tolerance. Computational studies showed that the presence of hydroxyl group on the N-aryl ring could enhance the chemoselectivity of the reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Kinetic dissection of individual steps in the poly(C)-directed oligoguanylate synthesis from guanosine 5'-monophosphate 2-methylimidazolide

    Science.gov (United States)

    Kanavarioti, A.; Bernasconi, C. F.; Alberas, D. J.; Baird, E. E.

    1993-01-01

    A kinetic study of oligoguanylate synthesis on a polycytidylate template, poly(C), as a function of the concentration of the activated monomer, guanosine 5'-monophosphate 2-methylimidazolide, 2-MeImpG, is reported. Reactions were run with 0.005-0.045 M 2-MeImpG in the presence of 0.05 M poly(C) at 23 degrees C. The kinetic results are consistent with a reaction scheme (eq 1) that consists of a series of consecutive steps, each step representing the addition of one molecule of 2-MeImpG to the growing oligomer. This scheme allows the calculation of second-order rate constants for every step by analyzing the time-dependent growth of each oligomer. Computer simulations of the course of reaction based on the determined rate constants and eq 1 are in excellent agreement with the product distributions seen in the HPLC profiles. In accord with an earlier study (Fakhrai, H.; Inoue, T.; Orgel, L. E. Tetrahedron 1984, 40, 39), rate constants, ki, for the formation of the tetramer and longer oligomers up to the 16-mer were found to be independent of length and somewhat higher than k3 (formation of trimer), which in turn is much higher than k2 (formation of dimer). The ki (i > or = 4), k3, and k2 values are not true second-order rate constants but vary with monomer concentration. Mechanistic models for the dimerization (Scheme I) and elongation reactions (Scheme II) are proposed that are consistent with our results. These models take into account that the monomer associates with the template in a cooperative manner. Our kinetic analysis allowed the determination of rate constants for the elementary processes of covalent bond formation between two monomers (dimerization) and between an oligomer and a monomer (elongation) on the template. A major conclusion from our study is that bond formation between two monomer units or between a primer and a monomer is assisted by the presence of additional next-neighbor monomer units. This is consistent with recent findings with hairpin

  18. Direct synthesis of β-N-glycosides by the reductive glycosylation of azides with protected and native carbohydrate donors.

    Science.gov (United States)

    Zheng, Jianbin; Urkalan, Kaveri Balan; Herzon, Seth B

    2013-06-03

    A simple and straightforward method for the stereocontrolled synthesis of β-linked N-glycosides uses alkyl and aryl azides as the nitrogen source. The N-glycosides are formed in high yields and with high β selectivities (typically >70% yield, >15:1 β:α selectivity). This approach is also amenable to the synthesis of N-glycosylated amino acids and peptides (see example, Fmoc=9-fluorenylmethoxycarbonyl). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. 2-nitroveratryl as a photocleavable thiol-protecting group for directed disulfide bond formation in the chemical synthesis of insulin.

    Science.gov (United States)

    Karas, John A; Scanlon, Denis B; Forbes, Briony E; Vetter, Irina; Lewis, Richard J; Gardiner, James; Separovic, Frances; Wade, John D; Hossain, Mohammed A

    2014-07-28

    Chemical synthesis of peptides can allow the option of sequential formation of multiple cysteines through exploitation of judiciously chosen regioselective thiol-protecting groups. We report the use of 2-nitroveratryl (oNv) as a new orthogonal group that can be cleaved by photolysis under ambient conditions. In combination with complementary S-pyridinesulfenyl activation, disulfide bonds are formed rapidly in situ. The preparation of Fmoc-Cys(oNv)-OH is described together with its use for the solid-phase synthesis of complex cystine-rich peptides, such as insulin. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Direct Synthesis of Dimethyl Carbonate from Carbon Dioxide and Methanol at Room Temperature Using Imidazolium Hydrogen Carbonate Ionic Liquid as a Recyclable Catalyst and Dehydrant.

    Science.gov (United States)

    Zhao, Tianxiang; Hu, Xingbang; Wu, Dongsheng; Li, Rui; Yang, Guoqiang; Wu, Youting

    2017-05-09

    The direct synthesis of dimethyl carbonate (DMC) from CO 2 and CH 3 OH was achieved at room temperature with 74 % CH 3 OH conversion in the presence of an imidazolium hydrogen carbonate ionic liquid ([C n C m Im][HCO 3 ]). Experimental and theoretical results reveal that [C n C m Im][HCO 3 ] can transform quickly into a CO 2 adduct, which serves as an effective catalyst and dehydrant. Its dehydration ability is reversible. The energy barrier of the rate-determining step for the DMC synthesis is only 21.7 kcal mol -1 . The ionic liquid can be reused easily without a significant loss of its catalytic and dehydrating ability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. New apparatus for direct counting of β particles from two-dimensional gels and an application to changes in protein synthesis due to cell density

    International Nuclear Information System (INIS)

    Anderson, H.L.; Puck, T.T.; Shera, E.B.

    1987-07-01

    A new method is described for scanning two-dimensional gels by the direct counting of β particles instead of autoradiography. The methodology is described; results are compared with autoradiographic results; and data are presented demonstrating changed patterns of protein synthesis accompanying changes in cell density. The method is rapid and permits identification of differences in protein abundance of approximately 10% for a substantial fraction of the more prominent proteins. A modulation effect of more than 5 standard deviations, accompanying contact inhibition of cell growth, is shown to occur for an appreciable number of these proteins. The method promises to be applicable to a variety of biochemical and genetic experiments designed to delineate changes in protein synthesis accompanying changes in genome, molecular environment, history, and state of differentiation of the cell populations studied. 13 refs., 8 figs., 4 tabs

  2. Direct observation of the effects of cellulose synthesis inhibitors using live cell imaging of Cellulose Synthase (CESA) in Physcomitrella patens.

    Science.gov (United States)

    Tran, Mai L; McCarthy, Thomas W; Sun, Hao; Wu, Shu-Zon; Norris, Joanna H; Bezanilla, Magdalena; Vidali, Luis; Anderson, Charles T; Roberts, Alison W

    2018-01-15

    Results from live cell imaging of fluorescently tagged Cellulose Synthase (CESA) proteins in Cellulose Synthesis Complexes (CSCs) have enhanced our understanding of cellulose biosynthesis, including the mechanisms of action of cellulose synthesis inhibitors. However, this method has been applied only in Arabidopsis thaliana and Brachypodium distachyon thus far. Results from freeze fracture electron microscopy of protonemal filaments of the moss Funaria hygrometrica indicate that a cellulose synthesis inhibitor, 2,6-dichlorobenzonitrile (DCB), fragments CSCs and clears them from the plasma membrane. This differs from Arabidopsis, in which DCB causes CSC accumulation in the plasma membrane and a different cellulose synthesis inhibitor, isoxaben, clears CSCs from the plasma membrane. In this study, live cell imaging of the moss Physcomitrella patens indicated that DCB and isoxaben have little effect on protonemal growth rates, and that only DCB causes tip rupture. Live cell imaging of mEGFP-PpCESA5 and mEGFP-PpCESA8 showed that DCB and isoxaben substantially reduced CSC movement, but had no measureable effect on CSC density in the plasma membrane. These results suggest that DCB and isoxaben have similar effects on CSC movement in P. patens and Arabidopsis, but have different effects on CSC intracellular trafficking, cell growth and cell integrity in these divergent plant lineages.

  3. Synthesis and characterization of (zinc-layered hydroxide-hippurate) nano hybrid by direct reaction of zinc oxide under aqueous environment

    International Nuclear Information System (INIS)

    Mohd Zobir Hussein; Samer Hasan Al Ali; Zulkarnain Zainal

    2011-01-01

    A new method for synthesis of hippurate nano hybrid has been developed. In this method, zinc oxide was added directly into aqueous solution of hippurate anions (A - ). The resulting hippurate nano hybrid (HAN) is composed of the organic moieties sandwiched between zinc layered hydroxide (ZLH) inorganic interlayers. HAN synthesized using 0.2 M hippuric acid showed the best crystallinity compared to other samples synthesized in this work. X-ray powder diffraction shows the basal spacing of the HAN was 21.3 Angstrom indicating that the monolayer of A - was arranged vertically to the ZLH interlayers. (author)

  4. A simple approach to the synthesis of Cu1.8S dendrites with thiamine hydrochloride as a sulfur source and structure-directing agent

    Directory of Open Access Journals (Sweden)

    Xiaoliang Yan

    2015-04-01

    Full Text Available A facile, green and environmental-friendly method for preparing Cu1.8S dendrites was developed. Copper nitrate and thiamine hydrochloride were selected as the starting materials in the water phase under hydrothermal conditions. No addition of a surfactant or a complex reagent was required for the synthesis of the Cu1.8S dendrite structures. Thiamine hydrochloride was employed as a sulfur source and structure-directing agent. The growth mechanism of Cu1.8S is tentatively discussed based on the experimental and computational results.

  5. Thiocarbamate-Directed Tandem Olefination-Intramolecular Sulfuration of Two Ortho C-H Bonds: Application to Synthesis of a COX-2 Inhibitor.

    Science.gov (United States)

    Li, Wendong; Zhao, Yingwei; Mai, Shaoyu; Song, Qiuling

    2018-02-16

    A palladium-catalyzed dual ortho C-H bond activation of aryl thiocarbamates is developed. This tandem reaction initiates by thiocarbamate-directed ortho C-H palladation, which leads to favorable olefin insertion rather than reductive elimination. The oxidative Heck reaction followed by another C-H activation and sulfuration affords the dual-functionalized products. This reaction provides a concise route to the S,O,C multisubstituted benzene skeleton which could be successfully applied for the synthesis of a COX-2 inhibitor.

  6. DNA Binding Peptide Directed Synthesis of Continuous DNA Nanowires for Analysis of Large DNA Molecules by Scanning Electron Microscope.

    Science.gov (United States)

    Kim, Kyung-Il; Lee, Seonghyun; Jin, Xuelin; Kim, Su Ji; Jo, Kyubong; Lee, Jung Heon

    2017-01-01

    Synthesis of smooth and continuous DNA nanowires, preserving the original structure of native DNA, and allowing its analysis by scanning electron microscope (SEM), is demonstrated. Gold nanoparticles densely assembled on the DNA backbone via thiol-tagged DNA binding peptides work as seeds for metallization of DNA. This method allows whole analysis of DNA molecules with entangled 3D features. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. The Role of Template Structure and Synergism between Inorganic and Organic Structure Directing Agents in the Synthesis of UTL Zeolite

    Czech Academy of Sciences Publication Activity Database

    Shvets, O. V.; Kasian, N.; Zukal, Arnošt; Pinkas, Jiří; Čejka, Jiří

    2010-01-01

    Roč. 22, č. 11 (2010), s. 3482-3495 ISSN 0897-4756 R&D Projects: GA ČR GA203/08/0604; GA ČR GA104/07/0383 Institutional research plan: CEZ:AV0Z40400503 Keywords : UTL zeolite * synthesis * zeolite molecular sietes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.400, year: 2010

  8. ATP synthase in slow- and fast-growing mycobacteria is active in ATP synthesis and blocked in ATP hydrolysis direction.

    Science.gov (United States)

    Haagsma, Anna C; Driessen, Nicole N; Hahn, Marc-Manuel; Lill, Holger; Bald, Dirk

    2010-12-01

    ATP synthase is a validated drug target for the treatment of tuberculosis, and ATP synthase inhibitors are promising candidate drugs for the treatment of infections caused by other slow-growing mycobacteria, such as Mycobacterium leprae and Mycobacterium ulcerans. ATP synthase is an essential enzyme in the energy metabolism of Mycobacterium tuberculosis; however, no biochemical data are available to characterize the role of ATP synthase in slow-growing mycobacterial strains. Here, we show that inverted membrane vesicles from the slow-growing model strain Mycobacterium bovis BCG are active in ATP synthesis, but ATP synthase displays no detectable ATP hydrolysis activity and does not set up a proton-motive force (PMF) using ATP as a substrate. Treatment with methanol as well as PMF activation unmasked the ATP hydrolysis activity, indicating that the intrinsic subunit ɛ and inhibitory ADP are responsible for the suppression of hydrolytic activity. These results suggest that the enzyme is needed for the synthesis of ATP, not for the maintenance of the PMF. For the development of new antimycobacterial drugs acting on ATP synthase, screening for ATP synthesis inhibitors, but not for ATP hydrolysis blockers, can be regarded as a promising strategy. © 2010 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

  9. Simultaneous light-directed synthesis of mirror-image microarrays in a photochemical reaction cell with flare suppression.

    Science.gov (United States)

    Sack, Matej; Kretschy, Nicole; Rohm, Barbara; Somoza, Veronika; Somoza, Mark M

    2013-09-17

    The use of photolabile protecting groups is a versatile and well-established means of synthesizing high complexity microarrays of biopolymers, such as nucleic acids and peptides, for high-throughput analysis. The synthesis takes place in a photochemical reaction cell which positions the microarray substrate at the focus of the optical system delivering the light and which can be connected to a fluidics system which delivers appropriate reagents to the surface in synchrony with the light exposure. Here we describe a novel photochemical reaction cell which allows for the simultaneous synthesis of microarrays on two substrates. The reaction cell positions both substrates within the limited depth-of-focus of the optical system while maintaining the necessary reagent flow conditions. The resulting microarrays are mirror images of each other but otherwise essentially identical. The new reaction cell doubles the throughput of microarray synthesis without increasing the consumption of reagents. In addition, a secondary flow chamber behind the reaction cell can be filled with an absorbent and index-matching fluid to eliminate reflections from light exiting the reaction cell assembly, greatly reducing unintended light exposure that reduces the sequence fidelity of the microarray probes.

  10. Direct synthesis of dimethyl carbonate from methanol and carbon dioxide over CeO2(X)-ZnO(1-X) nano-catalysts.

    Science.gov (United States)

    Kang, Ki Hyuk; Joe, Wangrae; Lee, Chang Hoon; Kim, Mieock; Kim, Dong Baek; Jang, Boknam; Song, In Kyu

    2013-12-01

    CeO2(X)-ZnO(1-X) (X = 0, 0.1, 0.3, 0.5, 0.7, 0.9, and 1.0) nano-catalysts were prepared by a co-precipitation method with a variation of CeO2 content (X, mol%), and they were applied to the direct synthesis of dimethyl carbonate from methanol and carbon dioxide. Successful formation of CeO2(X)-ZnO(1-X) nano-catalysts was well confirmed by XRD analysis. The amount of DMC produced over CeO2(X)-ZnO(1-X) catalysts exhibited a volcano-shaped curve with respect to CeO2 content. Acidity and basicity of CeO2(X)-ZnO(1-X) nano-catalysts were measured by NH3-TPD and CO2-TPD experiments, respectively, to elucidate the effect of acidity and basicity on the catalytic performance in the reaction. It was revealed that the catalytic performance of CeO2(X)-ZnO(1-X) nano-catalysts was closely related to the acidity and basicity of the catalysts. Amount of dimethyl carbonate increased with increasing both acidity and basicity of the catalysts. Among the catalysts tested, CeO2(0.7)-ZnO(0.3) with the largest acidity and basicity showed the best catalytic performance in the direct synthesis of dimethyl carbonate from methanol and carbon dioxide.

  11. Upgrading oxygenated Fischer-Tropsch derivatives and one-step direct synthesis of ethyl acetate from ethanol - examples of the desirability of research on simple chemical compounds transformations.

    Science.gov (United States)

    Klimkiewicz, Roman

    2014-01-01

    Oxygenates formed as by-products of Fischer-Tropsch syntheses can be transformed into other Fischer-Tropsch derived oxygenates instead of treating them as unwanted chemicals. One-step direct synthesis of ethyl acetate from ethanol is feasible with the use of some heterogeneous catalysts. Despite their apparent simplicity, both transformations are discussed as targeted fields of research. Furthermore, the two concepts are justified due to the environmental protection. Arguments regarding the Fischer-Tropsch process are focused on the opportunities of the utilization of undesirable by-products. The effective striving for their utilization can make the oxygenates the targeted products of this process. Arguments regarding the one-step direct synthesis of ethyl acetate underline the environmental protection and sustainability as a less waste-generating method but, above all, highlight the possibility of reducing the glycerol overproduction problem. The production of ethyl acetate from bioethanol and then transesterification of fats and oils with the use of ethyl acetate allows managing all the renewable raw materials. Thus, the process enables the biosynthesis of biodiesel without glycerine by-product and potentially would result in the increase in the demand for ethyl acetate. Graphical Abstract.

  12. Direct synthesis of pure single-crystalline Magnéli phase Ti8O15 nanowires as conductive carbon-free materials for electrocatalysis

    Science.gov (United States)

    He, Chunyong; Chang, Shiyong; Huang, Xiangdong; Wang, Qingquan; Mei, Ao; Shen, Pei Kang

    2015-02-01

    The Magnéli phase Ti8O15 nanowires (NWs) have been grown directly on a Ti substrate by a facile one-step evaporation-deposition synthesis method under a hydrogen atmosphere. The Ti8O15 NWs exhibit an outstanding electrical conductivity at room temperature. The electrical conductivity of a single Ti8O15 nanowire is 20.6 S cm-1 at 300 K. Theoretical calculations manifest that the existence of a large number of oxygen vacancies changes the band structure, resulting in the reduction of the electronic resistance. The Magnéli phase Ti8O15 nanowires have been used as conductive carbon-free supports to load Pt nanoparticles for direct methanol oxidation reaction (MOR). The Pt/Ti8O15 NWs show an enhanced activity and extremely high durability compared with commercial Pt/C catalysts.The Magnéli phase Ti8O15 nanowires (NWs) have been grown directly on a Ti substrate by a facile one-step evaporation-deposition synthesis method under a hydrogen atmosphere. The Ti8O15 NWs exhibit an outstanding electrical conductivity at room temperature. The electrical conductivity of a single Ti8O15 nanowire is 20.6 S cm-1 at 300 K. Theoretical calculations manifest that the existence of a large number of oxygen vacancies changes the band structure, resulting in the reduction of the electronic resistance. The Magnéli phase Ti8O15 nanowires have been used as conductive carbon-free supports to load Pt nanoparticles for direct methanol oxidation reaction (MOR). The Pt/Ti8O15 NWs show an enhanced activity and extremely high durability compared with commercial Pt/C catalysts. Electronic supplementary information (ESI) available: Additional data for the characterization and experimental details see DOI: 10.1039/c4nr05806b

  13. Direct synthesis of magnetite nanoparticles from iron(II) carboxymethylcellulose and their performance as NMR contrast agents

    Science.gov (United States)

    da Silva, Delmarcio Gomes; Hiroshi Toma, Sergio; de Melo, Fernando Menegatti; Carvalho, Larissa Vieira C.; Magalhães, Alvicler; Sabadini, Edvaldo; dos Santos, Antônio Domingues; Araki, Koiti; Toma, e. Henrique E.

    2016-01-01

    Iron(II) carboxymethylcellulose (CMC) has been successfully employed in the synthesis of hydrophylic magnetite nanoparticles stabilized with a biopolymer coating, aiming applications in NMR imaging. The new method encompasses a convenient one-step synthetic procedure, allowing a good size control and yielding particles of about 10 nm (core size). In addition to the biocompatibility, the nanoparticles have promoted a drastic reduction in the transverse relaxation time (T2) of the water protons. The relaxivity rates have been investigated as a function of the nanoparticles concentration, showing a better performance in relation to the common NMR contrast agents available in the market.

  14. Direct asymmetric vinylogous aldol reaction of allyl ketones with isatins: Divergent synthesis of 3-hydroxy-2-oxindole derivatives

    KAUST Repository

    Zhu, Bo

    2013-05-03

    6 in 1: The highly enantioselective title reaction is mediated by a bifunctional catalyst and leads to E-configured vinylogous aldol products (see scheme). These products are used as common intermediates in the synthesis of six biologically active 3-hydroxy-2-oxindole derivatives (e.g., CPC-1). Computational studies indicated that the observed stereoselectivity is a result of favorable secondary π-π* and H-bonding interactions in the transition state. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Poly(acrylic acid)-directed synthesis of colloidally stable single domain magnetite nanoparticles via partial oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Altan, Cem L. [Department of Chemical Engineering, Yeditepe University, Istanbul 34755 (Turkey); Laboratory of Materials and Interface Chemistry & Soft Matter cryoTEM Research Unit, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven 5600 MB (Netherlands); Gurten, Berna [Department of Chemical Engineering, Yeditepe University, Istanbul 34755 (Turkey); Sadza, Roel [Laboratory of Materials and Interface Chemistry & Soft Matter cryoTEM Research Unit, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven 5600 MB (Netherlands); Yenigul, Elcin [Department of Chemical Engineering, Yeditepe University, Istanbul 34755 (Turkey); Sommerdijk, Nico A.J.M., E-mail: n.sommerdijk@tue.nl [Laboratory of Materials and Interface Chemistry & Soft Matter cryoTEM Research Unit, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven 5600 MB (Netherlands); Institute for Complex Molecular Systems, Eindhoven University of Technology, Eindhoven 5600 MB (Netherlands); Bucak, Seyda, E-mail: seyda@yeditepe.edu.tr [Department of Chemical Engineering, Yeditepe University, Istanbul 34755 (Turkey)

    2016-10-15

    Octahedral, single domain magnetite nanoparticles with average size of ~55 nm were synthesized through oxidative aging of a ferrous hydroxide (Fe(OH){sub 2}) precursor at high pH in water. The synthesis was also carried out in the presence of the hydrophilic polymer poly(acrylic acid). Presence of the polymer changed the particle morphology from octahedral to spherical while average size decreased to 40–50 nm. Although these particles have a tendency to precipitate due to their high magnetic moment, dispersions of these particles were obtained in the presence of this particular polymer which made the particles stable in water for several days making them suitable for various biotechnological applications such as cell separation owing to their low toxicity. - Highlights: • Stable, single domain magnetite nanoparticles are synthesized via partial oxidation. • Particles are readily stabilized in water by a biocompatible polymer. • Steric barrier is essential for the stabilization of large magnetite nanoparticles.

  16. Direct synthesis of mesostructured carbon nanofibers decorated with silver-nanoparticles as a multifunctional membrane for water treatment

    International Nuclear Information System (INIS)

    Taha, Ahmed Aboueloyoun

    2015-01-01

    One-dimensional (1D) porous carbon nanofibers (CNFs) decorated by silver (Ag) nanoparticles (NPs) were prepared using a one-pot/self-template synthesis strategy by combining electrospinning and carbonization methods. The characterization results revealed that AgNPs were homogenously distributed along the CNFs and possessed a relatively uniform nano-size of about 12 nm. The novel membrane distinctively displayed enhanced photocatalytic activity under visible-light irradiation. The membrane exhibited excellent dye degradation and bacteria disinfection in batch experiments. The high photocatalytic activity can be attributed to the highly accessible surface areas, good light absorption capability, and high separation efficiency of photogenerated electron–hole pairs. The as-prepared membranes can be easily recycled because of their 1D property. (paper)

  17. Synthesis of Framework Isomer MOFs Containing Zinc and 4-Tetrazolyl Benzenecarboxylic Acid via a Structure Directing Solvothermal Approach

    Directory of Open Access Journals (Sweden)

    Carlos Ordonez

    2015-04-01

    Full Text Available The solvothermal synthesis of framework isomers was carried out using the hybrid carboxylate and tetrazolate functional ligand, 4-tetrazolyl benzenecarboxylic acid (H2TBC, TBC = 4-tetrazolyl benzenecarboxylate and zinc. H2TBC was also synthesized with the solvothermal approach, and is referred herein as structure 1. Using single-crystal X-ray diffraction, we found that the tetrazolate groups of TBC show an unusual “opposite-on” coordination mode with zinc. Three previously characterized metal-organic frameworks (MOFs were obtained by systematically changing the solvents of the H2TBC-Zn reaction, (1 ZnTBC, 2, which has a non-porous structure; (2 Zn2(TBC2(H2O, 3, which has an amphiphilic pore structure and (3 Zn2(TBC2{guest}, 4, which is porous and has channels containing uncoordinated N heteroatoms. Fluorescence spectra of 4 reveal a strong blue emission mainly from the TBC ligands.

  18. Synthesis and characterization of diamond microcrystals and nanorods deposited by hot cathode direct current plasma chemical vapor deposition method

    NARCIS (Netherlands)

    Zeng, L.; Peng, H.; Wang, W.; Chen, Y.; Lei, D.; Qi, W.; Liang, J.; Zhao, J.; Kong, X.; Zhang, H.

    2008-01-01

    (111) diamond microcrystals and (100) diamond microcrystals and nanorods were synthesized on Si substrate by hot cathode direct current plasma chemical vapor deposition method. The morphology, structure, and optical properties of the diamond films were characterized by scanning electron microscopy,

  19. A solvent approach to the size-controllable synthesis of ultrafine Pt catalysts for methanol oxidation in direct methanol fuel cells

    International Nuclear Information System (INIS)

    Ye, Feng; Liu, Hui; Feng, Yan; Li, Jianling; Wang, Xindong; Yang, Jun

    2014-01-01

    Graphical abstract: - Highlights: • An ethylene glycol-based approach for the synthesis of Pt/C catalysts with uniform Pt nanoparticles. • Superior catalytic activity of Pt/C catalysts synthesized at EG/water volume ratio of 1/1 for methanol oxidation reaction. • High performance of MEA for DMFC using Pt/C catalysts synthesized at EG/water volume ratio of 1/1 at anode. - Abstract: An ethylene glycol (EG)-based approach has been developed for the synthesis of Pt/C catalysts with uniform Pt nanoparticles. A number of characterization techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electrochemical measurements are used to characterize the as-prepared Pt catalysts. The well-dispersed Pt nanoparticles with average size of approximate 2 nm could be obtained in the EG/water mixture with volume ratio of 1/1, which display higher activity for methanol oxidation than that of the Pt/C products prepared at other EG/water volume ratios (0:1, 2:1, and 1:0). In particular, the performance of the Pt nanoparticles prepared at EG/water volume ratio of 1/1 in the membrane electrode assembly for direct methanol fuel cells has also been evaluated and benchmarked by commercial Pt/C catalysts. This study offers a vivid example to synthesize Pt nanoparticles with fine size and good catalytic activity by simply tuning the solvent ratio in colloidal chemistry methods

  20. Direct synthesis of B-allyl and B-allenyldiisopinocampheylborane reagents using allyl or propargyl halides and indium metal under Barbier-type conditions.

    Science.gov (United States)

    Hirayama, Lacie C; Haddad, Terra D; Oliver, Allen G; Singaram, Bakthan

    2012-05-04

    We report the first one-pot process for the asymmetric addition of allyl, methallyl, and propargyl groups to aldehydes and ketones using B-chlorodiisopinocampheylborane ((d)DIP-Cl) and indium metal. Under Barbier-type conditions, indium metal was used to generate allyl- and allenylindium intermediates, and subsequent reaction with (d)DIP-Cl successfully promoted the transfer of these groups to boron forming the corresponding chiral borane reagents. The newly formed borane reagents were reacted with aldehydes and ketones to produce the corresponding alcohol products in high yields and up to excellent enantioselectivity (98% ee). This method produced excellent enantioenriched secondary homoallylic alcohols from the allylation and methallylation of benzaldehyde. Using this method, the methallylation and cinnamylation of ketones afforded the highest enantioselectivities, while the propargylation of both aldehydes and ketones provided low enantiomeric excesses. In addition, this procedure provided the first synthesis of B-allenyldiisopinocampheylborane, which was characterized by (1)H and (11)B NMR spectroscopy. This is the first example of the direct synthesis of allylboranes that contained substitutions from the corresponding allyl bromide and indium, thereby expanding the utility of the DIP-Cl reagent. Hence, a general and straightforward route to these chiral organoborane reagents in one-pot has been developed along with the asymmetric Barbier-type allylation and propargylation of aldehyde and ketone substrates using these chiral organoborane reagents in subsequent coupling reactions.

  1. Carbon-Modified Mesoporous Anatase/TiO2(B Whisker for Enhanced Activity in Direct Synthesis of Hydrogen Peroxide by Palladium

    Directory of Open Access Journals (Sweden)

    Rui Tu

    2017-06-01

    Full Text Available The regulation of the interaction between H2O2 and its catalysts is a promising route to achieve high productivity and selectivity towards H2O2. Herein, mesoporous anatase/TiO2(B whisker (mb-TiO2 modified with heterogeneous carbon was prepared as the support of Pd-based catalysts for the direct synthesis of H2O2. The morphology and structure of the catalyst were investigated by transmission electron microscopy, X-ray diffraction, Raman spectroscopy, Brunner-Emmet-Teller measurements, and X-ray photoelectron spectroscopy. The interaction between H2O2 and the support was studied by isothermal calorimeter. The carbon heterogeneous modification can weaken the interaction between H2O2 and the support, then accelerate the desorption of H2O2 and reduce the re-adsorption of H2O2 in the reaction medium. Meanwhile, the synergistic effects between TiO2 and Pd nanoparticles are not influenced by the heterogeneous carbon distribution. The catalyst exhibits better performance for the synthesis of H2O2 compared with the corresponding unmodified catalyst; the productivity of H2O2 increases more than 40%, which can be ascribed to the decrease of further H2O2 conversion under the weakened interaction.

  2. First DMAP-mediated direct conversion of Morita–Baylis–Hillman alcohols into γ-ketoallylphosphonates: Synthesis of γ-aminoallylphosphonates

    Directory of Open Access Journals (Sweden)

    Marwa Ayadi

    2016-12-01

    Full Text Available An efficient synthesis of a series of γ-ketoallylphosphonates through a direct conversion of both primary and secondary Morita–Baylis–Hillman (MBH alcohols by trialkyl phosphites with or without DMAP, used as additive, and under solvent-free conditions, is described herein for the first time. Subsequently, a highly regioselective Luche reduction of the primary phosphonate 2a (R = H gave the corresponding γ-hydroxyallylphosphonate 5 that further reacted with tosylamines in the presence of diiodine (15 mol % as a catalyst, affording the corresponding SN2-type products 6a–d in 63 to 70% isolated yields. Alternatively, the alcohol 5 produced the corresponding acetate 7 which, mediated by Ce(III, was successfully converted into the corresponding γ-aminoallylphosphonates 8a–d.

  3. First DMAP-mediated direct conversion of Morita-Baylis-Hillman alcohols into γ-ketoallylphosphonates: Synthesis of γ-aminoallylphosphonates.

    Science.gov (United States)

    Ayadi, Marwa; Elleuch, Haitham; Vrancken, Emmanuel; Rezgui, Farhat

    2016-01-01

    An efficient synthesis of a series of γ-ketoallylphosphonates through a direct conversion of both primary and secondary Morita-Baylis-Hillman (MBH) alcohols by trialkyl phosphites with or without DMAP, used as additive, and under solvent-free conditions, is described herein for the first time. Subsequently, a highly regioselective Luche reduction of the primary phosphonate 2a (R = H) gave the corresponding γ-hydroxyallylphosphonate 5 that further reacted with tosylamines in the presence of diiodine (15 mol %) as a catalyst, affording the corresponding S N 2-type products 6a-d in 63 to 70% isolated yields. Alternatively, the alcohol 5 produced the corresponding acetate 7 which, mediated by Ce(III), was successfully converted into the corresponding γ-aminoallylphosphonates 8a-d .

  4. Microwave-assisted synthesis of palladium nanoparticles intercalated nitrogen doped reduced graphene oxide and their electrocatalytic activity for direct-ethanol fuel cells.

    Science.gov (United States)

    Kumar, Rajesh; da Silva, Everson T S G; Singh, Rajesh K; Savu, Raluca; Alaferdov, Andrei V; Fonseca, Leandro C; Carossi, Lory C; Singh, Arvind; Khandka, Sarita; Kar, Kamal K; Alves, Oswaldo L; Kubota, Lauro T; Moshkalev, Stanislav A

    2018-04-01

    Palladium nanoparticles decorated reduced graphene oxide (Pd-rGO) and palladium nanoparticles intercalated inside nitrogen doped reduced graphene oxide (Pd-NrGO) hybrids have been synthesized by applying a very simple, fast and economic route using microwave-assisted in-situ reduction and exfoliation method. The Pd-NrGO hybrids materials show good activity as catalyst for ethanol electro oxidation for direct ethanol fuel cells (DEFCs) as compared to Pd-rGO hybrids. The enhanced direct ethanol fuel cell can serve as alternative to fossil fuels because it is renewable and environmentally-friendly with a high energy conversion efficiency and low pollutant emission. As proof of concept, the electrocatalytic activity of Pd-NrGO hybrid material was accessed by cyclic voltammetry in presence of ethanol to evaluate its applicability in direct-ethanol fuel cells (DEFCs). The Pd-NrGO catalyst presented higher electro active surface area (∼6.3 m 2  g -1 ) for ethanol electro-oxidation when compared to Pd-rGO hybrids (∼3.7 m 2  g -1 ). Despite the smaller catalytic activity of Pd-NrGO, which was attributed to the lower exfoliation rate of this material in relation to the Pd-rGO, Pd-NrGO showed to be very promising and its catalytic activity can be further improved by tuning the synthesis parameters to increase the exfoliation rate. Copyright © 2018 Elsevier Inc. All rights reserved.

  5. Direct Synthesis of Fe3C-Functionalized Graphene by High Temperature Autoclave Pyrolysis for Oxygen Reduction

    DEFF Research Database (Denmark)

    Hu, Yang; Jensen, Jens Oluf; Zhang, Wei

    2014-01-01

    We present a novel approach to direct fabrication of few-layer graphene sheets with encapsulated Fe3C nanoparticles from pyrolysis of volatile non-graphitic precursors without any substrate. This one-step autoclave approach is facile and potentially scalable for production. Tested as an electroca......We present a novel approach to direct fabrication of few-layer graphene sheets with encapsulated Fe3C nanoparticles from pyrolysis of volatile non-graphitic precursors without any substrate. This one-step autoclave approach is facile and potentially scalable for production. Tested...

  6. Direct synthesis of graphitic mesoporous carbon from green phenolic resins exposed to subsequent UV and IR laser irradiations

    Science.gov (United States)

    Sopronyi, Mihai; Sima, Felix; Vaulot, Cyril; Delmotte, Luc; Bahouka, Armel; Matei Ghimbeu, Camelia

    2016-12-01

    The design of mesoporous carbon materials with controlled textural and structural features by rapid, cost-effective and eco-friendly means is highly demanded for many fields of applications. We report herein on the fast and tailored synthesis of mesoporous carbon by UV and IR laser assisted irradiations of a solution consisting of green phenolic resins and surfactant agent. By tailoring the UV laser parameters such as energy, pulse repetition rate or exposure time carbon materials with different pore size, architecture and wall thickness were obtained. By increasing irradiation dose, the mesopore size diminishes in the favor of wall thickness while the morphology shifts from worm-like to an ordered hexagonal one. This was related to the intensification of phenolic resin cross-linking which induces the reduction of H-bonding with the template as highlighted by 13C and 1H NMR. In addition, mesoporous carbon with graphitic structure was obtained by IR laser irradiation at room temperature and in very short time periods compared to the classical long thermal treatment at very high temperatures. Therefore, the carbon texture and structure can be tuned only by playing with laser parameters, without extra chemicals, as usually required.

  7. Direct Catalytic Asymmetric Mannich Reaction with Dithiomalonates as Excellent Mannich Donors: Organocatalytic Synthesis of (R)-Sitagliptin.

    Science.gov (United States)

    Bae, Han Yong; Kim, Mun Jong; Sim, Jae Hun; Song, Choong Eui

    2016-08-26

    In this study, dithiomalonates (DTMs) were demonstrated to be exceptionally efficient Mannich donors in terms of reactivity and stereoselectivity in cinchona-based-squaramide-catalyzed enantioselective Mannich reactions of diverse imines or α-amidosulfones as imine surrogates. Owing to the superior reactivity of DTMs as compared to conventional malonates, the catalyst loading could be reduced to 0.1 mol % without the erosion of enantioselectivity (up to 99 % ee). Furthermore, by the use of a DTM, even some highly challenging primary alkyl α-amidosulfones were smoothly converted into the desired adducts with excellent enantioselectivity (up to 97 % ee), whereas the use of a malonate or monothiomalonate resulted in no reaction under identical conditions. The synthetic utility of the chiral Mannich adducts obtained from primary alkyl substrates was highlighted by the organocatalytic, coupling-reagent-free synthesis of the antidiabetic drug (-)-(R)-sitagliptin. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Dual platinum and pyrrolidine catalysis in the direct alkylation of allylic alcohols: selective synthesis of monoallylation products.

    Science.gov (United States)

    Shibuya, Ryozo; Lin, Lu; Nakahara, Yasuhito; Mashima, Kazushi; Ohshima, Takashi

    2014-04-22

    A dual platinum- and pyrrolidine-catalyzed direct allylic alkylation of allylic alcohols with various active methylene compounds to produce products with high monoallylation selectivity was developed. The use of pyrrolidine and acetic acid was essential, not only for preventing undesirable side reactions, but also for obtaining high monoallylation selectivity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Facile synthesis of Ni-decorated multi-layers graphene sheets as effective anode for direct urea fuel cells

    Directory of Open Access Journals (Sweden)

    Ahmed Yousef

    2017-09-01

    Full Text Available A large amount of urea-containing wastewater is produced as a by-product in the fertilizer industry, requiring costly and complicated treatment strategies. Considering that urea can be exploited as fuel, this wastewater can be treated and simultaneously exploited as a renewable energy source in a direct urea fuel cell. In this study, multi-layers graphene/nickel nanocomposites were prepared by a one-step green method for use as an anode in the direct urea fuel cell. Typically, commercial sugar was mixed with nickel(II acetate tetrahydrate in distilled water and then calcined at 800 °C for 1 h. Raman spectroscopy, X-ray diffraction (XRD, scanning electron microscope (SEM, transmission electron microscope (TEM and energy dispersive spectroscopy (EDS were employed to characterize the final product. The results confirmed the formation of multi-layers graphene sheets decorated by nickel nanoparticles. To investigate the influence of metal nanoparticles content, samples were prepared using different amounts of the metal precursor; nickel acetate content was changed from 0 to 5 wt.%. Investigation of the electrochemical characterizations indicated that the sample prepared using the original solution with 3 wt.% nickel acetate had the best current density, 81.65 mA/cm2 in a 0.33 M urea solution (in 1 M KOH at an applied voltage 0.9 V vs Ag/AgCl. In a passive direct urea fuel cell based on the optimal composition, the observed maximum power density was 4.06 × 10−3 mW/cm2 with an open circuit voltage of 0.197 V at room temperature in an actual electric circuit. Overall, this study introduces a cheap and beneficial methodology to prepare effective anode materials for direct urea fuel cells.

  10. Hydrothermal synthesis of size-controllable Yttrium Orthovanadate (YVO4) nanoparticles and its application in photocatalytic degradation of direct blue dye

    International Nuclear Information System (INIS)

    Mohamed, R.M.; Harraz, F.A.; Mkhalid, I.A.

    2012-01-01

    Graphical abstract: XRD patterns of YVO 4 nanopowders prepared at different hydrothermal times; where Y 1 = 4 h, Y 2 = 8 h, Y 3 = 12 h and Y 4 = 24 h. Highlights: ► Size control of Yttrium Orthovanadate. ► Hydrothermal synthesis. ► Removal of direct blue dye. - Abstract: Sized-controlled YVO 4 nanoparticles have been synthesized by a simple hydrothermal method by changing hydrothermal time from 4 to 24 h. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), specific surface area (Brunauer–Emmett–Teller (BET)), and ultraviolet–visible spectroscopy (UV–vis) measurements. The results showed that the size of as-synthesized YVO 4 nanoparticles was in the range of 11–40 nm and was extremely dependent on the hydrothermal time. Photocatalytic measurement showed that the YVO 4 nanoparticles with particle size of about 11 nm (prepared by 4 h hydrothermal time) possess superior photocatalytic properties in the decolorization of direct blue dye. Due to simple preparation, high photocatalytic oxidation of direct blue dye and low cost, the YVO 4 photocatalyst is a potential candidate for pollutants removal and will find wide application in the coming future in photocatalytic oxidation processes. The overall kinetics of photodegradation of direct blue dye using YVO 4 nanopowders photocatalyst was found to be of first order. The photocatalyst could be easily removed from the reaction mixture and its recyclability with no loss of activity was possible for six times. The catalytic performance was found to decrease by 5% after run number six.

  11. Synthesis and Characterization of Titanium Supported on High Order Nanoporous Silica and Application for Direct Oxidation of Benzene to Phenol

    Directory of Open Access Journals (Sweden)

    Alireza Badiei

    2009-01-01

    Full Text Available Direct oxidation of benzene to phenol in liquid phase by H2O2 peroxide was examined over Ti/ LUS-1 catalyst in methanol and acetic acid as solvents. The maximum yield and selectivity of the phenol produced was obtained in the presence of acetic acid. It can be attributed to the stabilization of H2O2 as peroxy acetic acid species in the radical mechanism for this reaction. Acetic acid interacts with hydrogen peroxide over Ti/LUS-1 and produces acetoxy radicals.

  12. Synthesis of free-standing carbon nanohybrid by directly growing carbon nanotubes on air-sprayed graphene oxide paper and its application in supercapacitor

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Li; Jiang, Wenchao; Yuan, Yang; Goh, Kunli; Yu, Dingshan [School of Chemical and Biomedical Engineering, Nanyang Technological University, 62 Nanyang Drive, Singapore 637459 (Singapore); Wang, Liang [School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300384 (China); Chen, Yuan, E-mail: chenyuan@ntu.edu.sg [School of Chemical and Biomedical Engineering, Nanyang Technological University, 62 Nanyang Drive, Singapore 637459 (Singapore)

    2015-04-15

    We report the synthesis of a free-standing two dimensional carbon nanotube (CNT)-reduced graphene oxide (rGO) hybrid by directly growing CNTs on air-sprayed GO paper. As a result of the good integration between CNTs and thermally reduced GO film during chemical vapor deposition, excellent electrical conductivity (2.6×10{sup 4} S/m), mechanical flexibility (electrical resistance only increases 1.1% after bent to 90° for 500 times) and a relatively large surface area (335.3 m{sup 2}/g) are achieved. Two-electrode supercapacitor assembled using the CNT–rGO hybrids in ionic liquid electrolyte (1-ethyl-3-methylimidazolium tetrafluoroborate) shows excellent stability upon 500 bending cycles with the gravimetric energy density measuring 23.7 Wh/kg and a power density of 2.0 kW/kg. Furthermore, it shows an impedance phase angle of −64.4° at a frequency of 120 Hz, suggesting good potentials for 120 Hz alternating current line filtering applications. - Graphical abstract: Flexible and highly conductive carbon nanotube-reduced graphene oxide nanohybrid. - Highlights: • Direct growth of carbon nanotubes by chemical vapor deposition on air-sprayed graphene oxide paper. • Two-dimensional carbon nanohybrid with excellent conductivity and mechanical flexibility. • Supercapacitor with excellent performance stability upon mechanical deformation for flexible electronics applications. • Supercapacitor with high impedance phase angle for 120 Hz alternating current line filtering applications.

  13. Beating Bias in the Directed Evolution of Proteins: Combining High-Fidelity on-Chip Solid-Phase Gene Synthesis with Efficient Gene Assembly for Combinatorial Library Construction.

    Science.gov (United States)

    Li, Aitao; Acevedo-Rocha, Carlos G; Sun, Zhoutong; Cox, Tony; Xu, Jia Lucy; Reetz, Manfred T

    2018-02-02

    Saturation mutagenesis (SM) constitutes a widely used technique in the directed evolution of selective enzymes as catalysts in organic chemistry and in the manipulation of metabolic paths and genomes, but the quality of the libraries is far from optimal due to the inherent amino acid bias. Herein, it is shown how this fundamental problem can be solved by applying high-fidelity solid-phase chemical gene synthesis on silicon chips followed by efficient gene assembly. Limonene epoxide hydrolase was chosen as the catalyst in the model desymmetrization of cyclohexene oxide with the stereoselective formation of (R,R)- and (S,S)-cyclohexane-1,2-diol. A traditional combinatorial PCR-based SM library, produced by simultaneous randomization at several residues by using a reduced amino acid alphabet, and the respective synthetic library were constructed and compared. Statistical analysis at the DNA level with massive sequencing demonstrates that, in the synthetic approach, 97 % of the theoretically possible DNA mutants are formed, whereas the traditional SM library contained only about 50 %. Screening at the protein level also showed the superiority of the synthetic library; many highly (R,R)- and (S,S)-selective variants being discovered are not found in the traditional SM library. With the prices of synthetic genes decreasing, this approach may point the way to future directed evolution. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Efficient and clean synthesis of graphene supported platinum nanoclusters and its application in direct methanol fuel cell

    International Nuclear Information System (INIS)

    Ji Kai; Chang Gang; Oyama, Munetaka; Shang Xunzhong; Liu Xiong; He Yunbin

    2012-01-01

    Highlights: ► Pt nanoclusters/graphene (PtNCs/graphene) was synthesized within one-step process. ► Environment friendly ascorbic acid was chosen as the reductant. ► The synthesized PtNCs/graphene show superior electrocatalytic activity to methanol. ► PtNCs/graphene show superior electrocatalytic stability in methanol electrooxidation. - Abstract: The graphene supported platinum nanoclusters was synthesized by an efficient and clean method, in which graphene oxide and Pt ion precursor were reduced by ascorbic acid within one-step process. The obtained Pt nanoclusters attached graphene composite (PtNCs/graphene) was characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS), which can directly show that Pt nanoclusters successfully formed on graphene and well distributed on the edges and wrinkles of graphene sheets. The further electrochemical characterizations including cyclic voltammograms (CV), current–time methods indicated that PtNCs/graphene has significantly higher electrocatalytic activity and stability for methanol electrooxidation compared to the normal Vulcan XC-72 and graphite supported Pt nanoclusters, which will lead a further application as a new electrode material in direct methanol fuel cell (DMFC).

  15. Direct synthesis of solid and hollow carbon nanospheres over NaCl crystals using acetylene by chemical vapour deposition

    Energy Technology Data Exchange (ETDEWEB)

    Chandra Kishore, S.; Anandhakumar, S.; Sasidharan, M., E-mail: sasidharan.m@res.srmuniv.ac.in

    2017-04-01

    Highlights: • Hollow and solid carbon nanospheres were synthesized by CVD method. • NaCl was used as template for direct growth of carbon nanospheres. • Separation of NaCl from the mixture is made easy by dissolving in water. • The hollow carbon nanospheres exhibit high specific capacity in Li-ion batteries than the graphite anodes. - Abstract: Carbon nanospheres (CNS) with hollow and solid morphologies have been synthesised by a simple chemical vapour deposition method using acetylene as a carbon precursor. Sodium chloride (NaCl) powder as a template was used for the direct growth of CNS via facile and low-cost approach. The effect of various temperatures (500 °C, 600 °C and 700 °C) and acetylene flow rates were investigated to study the structural evolution on the carbon products. The purified CNS thus obtained was characterized by various physicochemical techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), Raman spectroscopy, and cyclicvoltametry. The synthesised hollow nanospheres were investigated as anode materials for Li-ion batteries. After 25 cycles of repeated charge/discharge cycles, the discharge and charge capacities were found to be 574 mAh/g and 570 mAh/g, respectively which are significantly higher than the commercial graphite samples.

  16. PS-b-PHEMA: synthesis, characterization, and processing of a high χ polymer for directed self-assembly lithography

    Science.gov (United States)

    Cheng, Jing; Lawson, Richard A.; Yeh, Wei-Ming; Jarnagin, Nathan D.; Tolbert, Laren M.; Henderson, Clifford L.

    2013-03-01

    As an alternative lithography technique, directed self-assembly (DSA) of block copolymers has shown to be promising for next generation high resolution patterning. PS-b-PMMA has been widely studied for its use as a block copolymer in directed self-assembly and has demonstrated patterned features down to size scales on the order of 20 nm pitch. However, due to the modest χ value for PS-b-PMMA (χ=0.038), this 20 nm feature pitch representes roughly the limiting capability of PS-b-PMMA. To achieve smaller pitch features, new block copolymers with higher χ values must be developed for use in DSA lithography. Here, poly(styrene)-b-poly(hydroxyehtylmethacrylate) or PS-b-PHEMS is introduced as one possible such high χ polymer. PS-b-PHEMA with controlled Mw and PDI was successfully synthesized via ATRP and fully characterized by NMR, GPC and FTIR. As a first demonstration of sub-20 nm pitch capability in PS-b-PHEMA, a 15 nm pitch size lamella structure in PS-b-PHEMA is shown. PS-b-PHEMA has good thermal stability, allowing it to be rapidly annealed thermally. PS-b-PHEMA also is shown to have improved etch contrast between the two blocks as compared to PS-b-PMMA. The χ value for PS-b-PHEMA is estimated to be 0.37 based on experimental pitch scaling studies, which is almost 10 times of the χ value for PS-b-PMMA.

  17. Evaluation and Selection of Bacillus Species Based on Enzyme Production, Antimicrobial Activity, and Biofilm Synthesis as Direct-Fed Microbial Candidates for Poultry

    Science.gov (United States)

    Latorre, Juan D.; Hernandez-Velasco, Xochitl; Wolfenden, Ross E.; Vicente, Jose L.; Wolfenden, Amanda D.; Menconi, Anita; Bielke, Lisa R.; Hargis, Billy M.; Tellez, Guillermo

    2016-01-01

    Social concern about misuse of antibiotics as growth promoters (AGP) and generation of multidrug-resistant bacteria have restricted the dietary inclusion of antibiotics in livestock feed in several countries. Direct-fed microbials (DFM) are one of the multiple alternatives commonly evaluated as substitutes of AGP. Sporeformer bacteria from the genus Bacillus have been extensively investigated because of their extraordinary properties to form highly resistant endospores, produce antimicrobial compounds, and synthesize different exogenous enzymes. The purpose of the present study was to evaluate and select Bacillus spp. from environmental and poultry sources as DFM candidates, considering their enzyme production profile, biofilm synthesis capacity, and pathogen-inhibition activity. Thirty-one Bacillus isolates were screened for in vitro relative enzyme activity of amylase, protease, lipase, and phytase using a selective media for each enzyme, with 3/31 strains selected as superior enzyme producers. These three isolates were identified as Bacillus subtilis (1/3), and Bacillus amyloliquefaciens (2/3), based on biochemical tests and 16S rRNA sequence analysis. For evaluation of biofilm synthesis, the generation of an adherent crystal violet-stained ring was determined in polypropylene tubes, resulting in 11/31 strains showing a strong biofilm formation. Moreover, all Bacillus strains were evaluated for growth inhibition activity against Salmonella enterica serovar Enteritidis (26/31), Escherichia coli (28/31), and Clostridioides difficile (29/31). Additionally, in previous in vitro and in vivo studies, these selected Bacillus strains have shown to be resistant to different biochemical conditions of the gastrointestinal tract of poultry. Results of the present study suggest that the selection and consumption of Bacillus-DFM, producing a variable set of enzymes and antimicrobial compounds, may contribute to enhanced performance through improving nutrient digestibility

  18. Evaluation and selection of Bacillus species based on enzyme production, antimicrobial activity and biofilm synthesis as direct-fed microbials candidates for poultry

    Directory of Open Access Journals (Sweden)

    Juan D Latorre

    2016-10-01

    Full Text Available Social concern about misuse of antibiotics as growth promoters (AGP and generation of multidrug-resistant bacteria have restricted the dietary inclusion of antibiotics in livestock feed in several countries. Direct-fed microbials (DFM are one of the multiple alternatives commonly evaluated as substitutes of AGP. Sporeformer bacteria from the genus Bacillus have been extensively investigated because of their extraordinary properties to form highly-resistant endospores, production of antimicrobial compounds and synthesize different exogenous enzymes. The purpose of the present study was to evaluate and select Bacillus spp. from environmental and poultry sources as DFM candidates, considering their enzyme production profile, biofilm synthesis capacity and pathogen-inhibition activity. Thirty one Bacillus isolates were screened for in vitro relative enzyme activity of amylase, protease, lipase and phytase using a selective media for each enzyme, with 3/31 strains selected as superior enzyme producers. These three isolates were identified as B. subtilis (1/3, and B. amyloliquefaciens (2/3 based on biochemical tests and 16S rRNA sequence analysis. For evaluation of biofilm synthesis, the generation of an adherent crystal violet-stained ring was determined in polypropylene tubes, resulting in 11/31 strains showing a strong biofilm formation. Moreover, all Bacillus strains were evaluated for growth inhibition activity against Salmonella enterica serovar Enteritidis (26/31, Escherichia coli (28/31 and Clostridioides difficile (29/31. Additionally, in previous in vitro and in vivo studies, these selected Bacillus strains have shown to be resistant to different biochemical conditions of the gastrointestinal tract of poultry. Results of the present study suggest that the selection and consumption of Bacillus-DFM, producing a variable set of enzymes and antimicrobial compounds may contribute to enhanced performance through improving nutrient digestibility

  19. Fluorine-Directed Glycosylation Enables the Stereocontrolled Synthesis of Selective SGLT2 Inhibitors for Type II Diabetes.

    Science.gov (United States)

    Sadurní, Anna; Kehr, Gerald; Ahlqvist, Marie; Wernevik, Johan; Sjögren, Helena Peilot; Kankkonen, Cecilia; Knerr, Laurent; Gilmour, Ryan

    2018-02-26

    Inhibition of the sodium-glucose co-transporters (SGLT1 and SGLT2) is a validated strategy to address the increasing prevalence of type II diabetes mellitus. However, achieving selective inhibition of human SGLT1 or SGLT2 remains challenging. Orally available small molecule drugs based on the d-glucose core of the natural product Gliflozin have proven to be clinically effective in this regard, effectively impeding glucose reabsorption. Herein, we disclose the influence of molecular editing with fluorine at the C2 position of the pyranose ring of Phlorizin analogues Remogliflozin Etabonate and Dapagliflozin (Farxiga ® ) to concurrently direct β-selective glycosylation, as is required for biological efficacy, and enhance aspects of the physicochemical profile. Given the abundance of glycosylated pharmaceuticals in diabetes therapy that contain a β-configured d-glucose nucleus, it is envisaged that this strategy may prove to be expansive. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Simple synthesis of P(Cbz-alt-TBT) and PCDTBT by combining direct arylation with suzuki polycondensation of heteroaryl chlorides.

    Science.gov (United States)

    Lombeck, Florian; Matsidik, Rukiya; Komber, Hartmut; Sommer, Michael

    2015-01-01

    Direct arylation (DA) of 2-chlorothiophene and 2-chloro-3-hexylthiophene with 4,7-dibromo-2,1,3-benzothiadiazole is used to synthesize 4,7-bis(5-chloro-2-thienyl)-2,1,3-benzothiadiazole (TBTCl2) and 4,7-bis(5-chloro-4-hexyl-2-thienyl)-2,1,3-benzothiadiazole (DH-TBTCl2) in one step. Suitable conditions of the Suzuki polycondensations (SPC) of TBTCl2 and DH-TBTCl2 with the carbazole comonomer CbzPBE2 are established, furnishing PCDTBT and P(Cbz-alt-TBT) with high molecular weight and yield. Compared with control samples made from the corresponding dibromides, high-temperature NMR and UV-vis spectroscopy indicate similar properties for PCDTBT but an increased content of Cbz-Cbz homocouplings for P(Cbz-alt-TBT). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Design, synthesis, and evaluation of multitarget-directed ligands against Alzheimer's disease based on the fusion of donepezil and curcumin.

    Science.gov (United States)

    Yan, Jun; Hu, Jinhui; Liu, Anqiu; He, Lin; Li, Xingshu; Wei, Hui

    2017-06-15

    By fusing donepezil and curcumin, a novel series of compounds were obtained as multitarget-directed ligands against Alzheimer's disease. Among them, compound 11b displayed potent acetylcholinesterase (AChE) inhibition (IC 50 =187nM) and the highest BuChE/AChE selectivity (66.3). Compound 11b also inhibited 45.3% Aβ 1-42 self-aggregation at 20μM and displayed remarkable antioxidant effects. The metal-chelating property of compound 11b was elucidated by determining the 1:1 stoichiometry for the 11b-Cu(II) complex. The excellent blood-brain barrier permeability of 11b also indicated the potential for the compound to penetrate the central nervous system. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Synthesis and characterization of ZSM-5 and calcined kaolin evaluation using the content of structure-directing

    International Nuclear Information System (INIS)

    Rodrigues, J.J.; Silva, V.J. da; Rodrigues, M.G.F.

    2012-01-01

    This study aims to evaluate the effect of the structure-directing content, tetrapropylammonium bromide, on the structural and morphological characteristics of ZSM-5 zeolite obtained using calcined kaolin as silicon and aluminum. The samples were characterized by XRD, EDX, SEM and Physics Adsorption N 2 . Trough X ray diffraction patterns was possible to observed the formation of the structure of ZSM-5 with intense peaks and well-defined characteristic of crystalline. The micrographs showed that the samples consist of agglomerates and/or aggregates of particles characteristic of the MFI structure typical of ZSM-5 zeolite. And through the adsorption-desorption isotherms physical N2 was possible to observe that the samples show hysteresis type I typical of microporous materials with specific surface areas of 218 and 222 m 2 /g. Therefore, the use of calcined kaolin to obtain ZSM-5 zeolite was effective. (author)

  3. Pt-Fe catalyst nanoparticles supported on single-wall carbon nanotubes: Direct synthesis and electrochemical performance for methanol oxidation

    Science.gov (United States)

    Ma, Xiaohui; Luo, Liqiang; Zhu, Limei; Yu, Liming; Sheng, Leimei; An, Kang; Ando, Yoshinori; Zhao, Xinluo

    2013-11-01

    Single-wall carbon nanotubes (SWCNTs) supported Pt-Fe nanoparticles have been prepared by one-step hydrogen arc discharge evaporation of carbon electrode containing both Pt and Fe metal elements. The formation of SWCNTs and Pt-Fe nanoparticles occur simultaneously during the evaporation process. High-temperature hydrogen treatment and hydrochloric acid soaking have been carried out to purify and activate those materials in order to obtain a new type of Pt-Fe/SWCNTs catalyst for methanol oxidation. The Pt-Fe/SWCNTs catalyst performs much higher electrocatalytic activity for methanol oxidation, better stability and better durability than a commercial Pt/C catalyst according to the electrochemical measurements, indicating that it has a great potential for applications in direct methanol fuel cells.

  4. Direct synthesis of highly substituted 2-cyclohexenones and sterically hindered benzophenones based on a [5C + 1C] annulation.

    Science.gov (United States)

    Fu, Zhenqian; Wang, Mang; Dong, Ying; Liu, Jun; Liu, Qun

    2009-08-21

    The regiospecific [5C + 1C] annulation of readily available alpha-alkenoyl ketene (S,S)-acetals 1 with aryl methyl ketones 2, the less active methylene compounds, has been developed. Upon treatment of 1 with 2 in the presence of t-BuOK in DMF at room temperature, highly substituted 2-cyclohexenones 3 were synthesized in high to excellent diastereoselectivities with high yields. On the basis of this strategy, sterically hindered benzophenones 4 were conveniently prepared via the iodonation-aromatization of 2-cyclohexenones 3 with I(2) in MeONa/MeOH basic medium. Furthermore, benzophenones 4 were also obtained directly from 1 and 2 following a sequential [5 + 1] annulation-iodonation-aromatization procedure in a one-pot operation.

  5. Direct synthesis of Fe3 C-functionalized graphene by high temperature autoclave pyrolysis for oxygen reduction.

    Science.gov (United States)

    Hu, Yang; Jensen, Jens Oluf; Zhang, Wei; Huang, Yunjie; Cleemann, Lars N; Xing, Wei; Bjerrum, Niels J; Li, Qingfeng

    2014-08-01

    We present a novel approach to direct fabrication of few-layer graphene sheets with encapsulated Fe3 C nanoparticles from pyrolysis of volatile non-graphitic precursors without any substrate. This one-step autoclave approach is facile and potentially scalable for production. Tested as an electrocatalyst, the graphene-based composite exhibited excellent catalytic activity towards the oxygen reduction reaction in alkaline solution with an onset potential of ca. 1.05 V (vs. the reversible hydrogen electrode) and a half-wave potential of 0.83 V, which is comparable to the commercial Pt/C catalyst. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Direct in situ activation of Ag0 nanoparticles in synthesis of Ag/TiO2 and its photoactivity

    International Nuclear Information System (INIS)

    Jaafar, N.F.; Jalil, A.A.; Triwahyono, S.; Efendi, J.; Mukti, R.R.; Jusoh, R.; Jusoh, N.W.C.; Karim, A.H.; Salleh, N.F.M.; Suendo, V.

    2015-01-01

    Graphical abstract: - Highlights: • Ag 0 loaded on TiO 2 was prepared by a direct in situ electrochemical method. • 5 wt% Ag–TiO 2 demonstrated the best photocatalytic degradation of 2-CP. • Isomorphous substitution of Ag with Ti occurred to form Ti−O−Ag bonds. • Ag 0 and oxygen vacancies trapped electrons to enhance e–H + separation. • Substitution of Ag in the TiO 2 structure decreased the number of oxygen vacancies. - Abstract: Metallic Ag nanoparticles (Ag 0 ) were successfully activated using a direct in situ electrochemical method before being supported on TiO 2 . Catalytic testing showed that 5 wt% Ag–TiO 2 gave the highest photodegradation (94%) of 50 mg L −1 2-chlorophenol (2-CP) at pH 5 using 0.375 g L −1 catalyst within 6 h, while under similar conditions, 1 wt% and 10 wt% Ag–TiO 2 only gave 75% and 78% degradation, respectively. Characterization results illustrated that the photoactivity was affected by the amount of Ag 0 and oxygen vacancies which act as an electrons trap to enhance the electron–hole separation. While, the Ag−O−Ti bonds formation reduced the photoactivity. The degradation followed a pseudo-first order Langmuir–Hinshelwood model where adsorption was the controlling step. Study on the effect of scavengers showed that the hole (H + ) and hydroxyl radical (OH·) play important roles in the photodegradation. The regenerated photocatalyst was still stable after five cycling runs

  7. Genistein: a novel anthocyanin synthesis promoter that directly regulates biosynthetic genes in red cabbage in a light-dependent way

    Directory of Open Access Journals (Sweden)

    Na Zhang

    2016-12-01

    Full Text Available Genistein (GNT, an isoflavone, is used in the clinical treatment of various health disorders. GNT is found in primary food source plants and some medical plants. However, studies on the functions of GNT in plants are rarely reported. In this study, we demonstrated that GNT plays an important role in promoting anthocyanin accumulation in red cabbage. GNT solutions (10, 20, 30, 40, and 50 mg/L as foliar fertilizers were applied to red cabbage. Consequently, anthocyanin accumulation in red cabbage increased in a light-dependent manner. GNT solution at 30 mg/L exhibited the optimal effect on anthocyanin accumulation, which was twice that of the control. Quantitative real-time PCR analysis indicated that GNT application upregulated the expression of all structural genes, contributing to anthocyanin biosynthesis under light conditions. Under dark conditions, GNT exerted no significant promotive effect on anthocyanin accumulation; only early biosynthetic genes of anthocyanin biosynthesis responded to GNT. The promotive effect of GNT on anthocyanin biosynthesis is directly attributable to the regulation of structural gene expression. Transcription factors exhibited no response to GNT. The levels of anthocyanin in red cabbage positively correlated with the enzyme activities of antioxidant systems. This finding correlation suggested that the promotive effect of GNT on anthocyanin levels was correlated with improved antioxidant activity in the red cabbage.

  8. Synthesis and characterization of Pt-MoO x -TiO2 electrodes for direct ethanol fuel cells

    Science.gov (United States)

    Wang, Xiu-Yu; Zhang, Jing-Chang; Cao, Xu-Dong; Jiang, Yuan-Sheng; Zhu, Hong

    2011-10-01

    To enhance the CO-tolerance performance of anode catalysts for direct ethanol fuel cells, carbon nanotubes were modified by titanium dioxide (donated as CNTs@TiO2) and subsequently served as the support for the preparation of Pt/CNTs@TiO2 and Pt-Mo/CNTs@TiO2 electrocatalysts via a UV-photoreduction method. The physicochemical characterizations of the catalysts were carried out by using X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and infrared spectroscopy of adsorbed probe ammonia molecules. The electrocatalytic properties of the catalysts for methanol oxidation were investigated by the cyclic voltammetry technique. The results show that Pt-Mo/CNTs@TiO2 electrode exhibits the highest performance in all the electrodes. It is explained that, the structure, the oxidation states, and the acid-base properties of the catalysts are influenced due to the strong interaction between Ti and Mo species by adding TiO2 and MoO x to the Pt-based catalysts.

  9. Ice as a Green-Structure-Directing Agent in the Synthesis of Macroporous MWCNTs and Chondroitin Sulphate Composites

    Science.gov (United States)

    Nardecchia, Stefania; Serrano, María Concepción; García-Argüelles, Sara; Maia Da Costa, Marcelo E. H.; Ferrer, María Luisa; Gutiérrez, María C.

    2017-01-01

    The incorporation of multi-walled carbon nanotubes (MWCNTs) into chondroitin sulphate-based scaffolds and the effect on the structural, mechanical, conductive, and thermal properties of the resulting scaffolds is investigated. Three-dimensional hierarchical materials are prepared upon the application of the ice segregation-induced self-assembly (ISISA) process. The use of ice as structure-directing agents avoids chemicals typically used for this purpose (e.g., surfactants, block copolymers, etc.), hence, emphasising the green features of this soft-templating approach. We determine the critical parameters that control the morphology of the scaffolds formed upon ice-templating (i.e., MWCNTs type, freezing conditions, polymer and MWCNT concentration). MWCNTs are surface functionalized by acidic treatment. MWCNT functionalization is characterized by Raman, Fourier transfer infrared (FTIR) and X-ray Photoelectron (XPS) spectroscopies. Scanning electron microscopy (SEM) analysis and porosity studies reveal that MWCNT content modifies the morphology of the macroporous structure, which decreases by increasing MWCNT concentration. Differences in scaffold morphology should be translated into their conductivity and mechanical properties. As a general trend, the Young’s modulus and the electrical conductivity of the scaffolds increase with the MWCNT content. Preliminary biocompatibility tests with human osteoblast-like cells also reveal the capability of these structures to support cell growth. PMID:28772715

  10. Microwave assisted synthesis of surfactant stabilized platinum/carbon nanotube electrocatalysts for direct methanol fuel cell applications

    Science.gov (United States)

    Sakthivel, M.; Schlange, A.; Kunz, U.; Turek, T.

    Platinum electrocatalysts deposited on multi-walled carbon nanotubes (CNT) with high loading were prepared using a microwave-assisted polyol reduction method and employed for direct methanol fuel cells (DMFC). A zwitterionic surfactant was used as a stabilizing agent for the formation of Pt nanoparticles. A uniform and narrow size distribution of highly dispersed Pt nanoparticles could be achieved by adjusting the weight ratio of surfactant to Pt precursor allowing for Pt loadings of up to 60 wt%. The heating time and the temperature for the ethylene glycol (EG) oxidation were found to be the key factors for depositing Pt nanoparticles homogeneously on carbon nanotubes. The smallest average particle diameter of 1.8 nm was obtained through microwave heating to 140 °C in 50 s. The structure, amount and morphology of the electrocatalysts were characterized with XRD, TGA, and TEM, respectively. Single cell DMFC measurements were performed in a membrane-electrode assembly (MEA) with 5 cm 2 active area and very low catalyst loading (0.25 mg cm -2 of noble metal on both anode and cathode). The DMFC performance of the surfactant stabilized cathode catalyst obtained by the new method described here revealed that the power density was three times higher than for a commercial catalyst used for comparison and two times higher than for an unstabilized CNT supported catalyst.

  11. Synthesis and Bioevaluation of Iodine-131 Directly Labeled Cyclic RGD-PEGylated Gold Nanorods for Tumor-Targeted Imaging

    Directory of Open Access Journals (Sweden)

    Yingying Zhang

    2017-01-01

    Full Text Available Introduction. Radiolabeled gold nanoparticles play an important role in biomedical application. The aim of this study was to prepare iodine-131 (131I-labeled gold nanorods (GNRs conjugated with cyclic RGD and evaluate its biological characteristics for targeted imaging of integrin αvβ3-expressing tumors. Methods. HS-PEG(5000-COOH molecules were applied to replace CTAB covering the surface of bare GNRs for better biocompatibility, and c(RGDfK peptides were conjugated onto the carboxyl terminal of GNR-PEG-COOH via EDC/NHS coupling reactions. The nanoconjugate was characterized, and 131I was directly tagged on the surface of GNRs via AuI bonds for SPECT/CT imaging. We preliminarily studied the characteristics of the probe and its feasibility for tumor-targeting SPECT/CT imaging. Results. The [131I]GNR-PEG-cRGD probe was prepared in a simple and rapid manner and was stable in both PBS and fetal bovine serum. It targeted selectively and could be taken up by tumor cells mainly via integrin αvβ3-receptor-mediated endocytosis. In vivo imaging, biodistribution, and autoradiography results showed evident tumor uptake in integrin αvβ3-expressing tumors. Conclusions. These promising results showed that this smart nanoprobe can be used for angiogenesis-targeted SPECT/CT imaging. Furthermore, the nanoprobe possesses a remarkable capacity for highly efficient photothermal conversion in the near-infrared region, suggesting its potential as a multifunctional theranostic agent.

  12. Mixed sulfoisophthalate and 1,2,4-triazole directed d10 metal coordination polymers: Synthesis, property and structural diversity

    Science.gov (United States)

    Liu, Bing; Guo, Kai; Feng, Hui-Jun; Miao, Wei-Ni; He, Ting-Ting; Xu, Ling

    2017-10-01

    This work presents six d10-metal coordination polymers based on mixed ligands of 5-sulfoisophthalate (H2SIP-) and 1,2,4-triazoles (1H-1,2,4-triazole (Htr), 3-amino-1H-1,2,4-triazole (Hatr)), 3D [Zn7(SIP)2(tr)8(H2O)4]·4H2O (1), 3D [Zn4(SIP)(atr)5(H2O)2]·3H2O (2), 2D [Zn2(SIP)(atr)(H2O)3]·2H2O (3), 2D [Ag(H2SIP)(Hatr)] (4 and 5), and 3D [Cd3(SIP)(tr)2(OH)]·H2O (6) under hydrothermal conditions. The structural analysis indicates a ligand directed structural diversity in the metal-(H)SIP-triazole system. The characterizations of 1-6 indicate that the bulk samples are pure phases, the thermal decomposition temperatures are beyond 300 °C, and the fluorescence are blue. The maximum emissions of 1-3 and 6 at around 410 nm are related with the intraligand π→π* transitions of 1,2,4-triazole moieties, and those at ca. 350 nm in 4 and 5 are assigned to intraligand transitions of (H)SIP ligands. The temperature-dependent fluorescence of 1-6 show thermal quenchings with fluorescence quenching rates ranging 22.9-74.2%, and the fluorescence cannot recover fully when it is back to ambient temperature.

  13. Synthesis of diketopyrrolopyrrole based copolymers via the direct arylation method for p-channel and ambipolar OFETs.

    Science.gov (United States)

    Sonar, Prashant; Foong, Thelese Ru Bao; Dodabalapur, Ananth

    2014-03-07

    In this paper, we have synthesized two novel diketopyrrolopyrrole (DPP) based donor–acceptor (D–A) copolymers poly{3,6-dithiophene-2-yl-2,5-di(2-octyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-1,5-bis(dodecyloxy)naphthalene} (PDPPT-NAP) and poly{3,6-dithiophene-2-yl-2,5-di(2-butyldecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-2-dodecyl-2H-benzo[d][1,2,3]triazole} (PDPPT-BTRZ) via direct arylation organometallic coupling. Both copolymers contain a common electron withdrawing DPP building block which is combined with electron donating alkoxy naphthalene and electron withdrawing alkyl-triazole comonomers. The number average molecular weight (M(n)) determined by gel permeation chromatography (GPC) for polymer PDPPT-NAP is around 23400 g mol(−1) whereas for polymer PDPPT-BTRZ it is 18600 g mol(−1). The solid state absorption spectra of these copolymers show a wide range of absorption from 400 nm to 1000 nm with optical band gaps calculated from absorption cut off values in the range of 1.45–1.30 eV. The HOMO values determined for PDPPT-NAP and PDPPT-BTRZ copolymers from photoelectron spectroscopy in air (PESA) data are 5.15 eV and 5.25 eV respectively. These polymers exhibit promising p-channel and ambipolar behaviour when used as an active layer in organic thin-film transistor (OTFT) devices. The highest hole mobility measured for polymer PDPPT-NAP is around 0.0046 cm(2) V(−1) s(−1) whereas the best ambipolar performance was calculated for PDPPT-BTRZ with a hole and electron mobility of 0.01 cm(2) V(−1) s(−1) and 0.006 cm(2) V(−1) s(−1) .

  14. One-pot solvothermal synthesis of ordered intermetallic Pt2In3 as stable and efficient electrocatalyst towards direct alcohol fuel cell application

    Science.gov (United States)

    Jana, Rajkumar; Peter, Sebastian C.

    2016-10-01

    Ordered intermetallic Pt2In3 nanoparticles have been synthesized by superhydride reduction of K2PtCl4 and InCl3.xH2O precursors using facile, one-pot solvothermal method. We report surfactant free solvothermal synthesis of a novel ordered Pt2In3 intermetallic nanoparticles for the first time. The structure and morphology of the catalyst has been confirmed by powder X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, energy-dispersive spectrometry and X-ray photoelectron spectroscopy. The electrocatalytic properties of the catalysts have been investigated by cyclic voltammetry and chronoamperometry. The as prepared Pt2In3 catalyst exhibit far superior electrocatalytic activity and stability towards alcohol oxidation over commercial Pt/C. The specific activity of as synthesized catalyst was found to be 3.2 and 2.3 times higher than commercial Pt/C for methanol and ethanol oxidation, respectively. This improved activity and durability of the Pt2In3 nanoparticles can make the catalyst an ideal catalyst candidate for direct alcohol fuel cell.

  15. Synthesis of a Hoechst 32258 analogue amino acid building block for direct incorporation of a fluorescent, high-affinity DNA binding motif into peptides

    DEFF Research Database (Denmark)

    Behrens, C; Harrit, N; Nielsen, P E

    2001-01-01

    The synthesis of a new versatile "Hoechst 33258-like" Boc-protected amino acid building block for peptide synthesis is described. It is demonstrated that this new ligand is an effective mimic of Hoechst 33258 in terms of DNA affinity and sequence specificity. Furthermore, this minor groove binder...

  16. Synthesis, characterization of organo-modified zeolitic nanomaterial from coal ash and application as adsorbent on remediation of contaminated water by rhodamine B and direct blue 71

    International Nuclear Information System (INIS)

    Alcântara, Raquel Reis

    2016-01-01

    The synthesis of zeolites from mineral coal fly and bottom ash was performed by alkaline hydrothermal treatment, which were named ZFA and ZBA, respectively. Organo-modified zeolites, SMZF and SMZB, were obtained from surface modification of ZFA and ZBA, respectively, using the cationic surfactant hexadecyltrimethylammonium bromide. From the remaining solutions generated in ZFA and ZBA synthesis it was possible to synthesis two new zeolites. The physicochemical characteristics of the synthesized nanomaterials zeolite as well as their respective raw materials, such as cation exchange capacity, density, specific area, chemical composition, mineralogical and morphological, among others, were determined. The adsorbents SMZF and SMZB were used to remove the dyes, Direct Blue 71 (DB71) and Rhodamine B (RB) from aqueous solutions in batch system. Thus, four systems DB71/SMZF, RB/SMZF, DB71/SMZB, RB/SMZB were investigated. The models of pseudo-first order and pseudo-second order were applied to the experimental data for the study the adsorption kinetics. The model of pseudo-second order was the one that best described the adsorption of all dye/organomodified-zeolites systems. The equilibrium adsorption was analyzed from four models isotherm, namely: Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-B). The results show that the model Freundlich and Langmuir best described the experimental data systems DB71/SMZF and DB71/SMZB, respectively. For systems with RB, the model D-R was the best fit for both adsorbents (SMZF and SMZB). The factorial design 2 4 was applied to the analysis of the following factors influencing the adsorption process: initial concentration of dye (C o ), pH, amount of adsorbent (M) and temperature (T). Under the conditions studied it concludes with the confidence interval of 95%, which for the DB71/SMZF system, the factors and their interactions that influence more were C 0 , M, pH, pH∗M, pH∗C 0 , M∗C 0 , pH∗M∗C 0 , in that order. In DB

  17. One-pot solvothermal synthesis of ordered intermetallic Pt{sub 2}In{sub 3} as stable and efficient electrocatalyst towards direct alcohol fuel cell application

    Energy Technology Data Exchange (ETDEWEB)

    Jana, Rajkumar; Peter, Sebastian C., E-mail: sebastiancp@jncasr.ac.in

    2016-10-15

    Ordered intermetallic Pt{sub 2}In{sub 3} nanoparticles have been synthesized by superhydride reduction of K{sub 2}PtCl{sub 4} and InCl{sub 3}.xH{sub 2}O precursors using facile, one-pot solvothermal method. We report surfactant free solvothermal synthesis of a novel ordered Pt{sub 2}In{sub 3} intermetallic nanoparticles for the first time. The structure and morphology of the catalyst has been confirmed by powder X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, energy-dispersive spectrometry and X-ray photoelectron spectroscopy. The electrocatalytic properties of the catalysts have been investigated by cyclic voltammetry and chronoamperometry. The as prepared Pt{sub 2}In{sub 3} catalyst exhibit far superior electrocatalytic activity and stability towards alcohol oxidation over commercial Pt/C. The specific activity of as synthesized catalyst was found to be ~3.2 and ~2.3 times higher than commercial Pt/C for methanol and ethanol oxidation, respectively. This improved activity and durability of the Pt{sub 2}In{sub 3} nanoparticles can make the catalyst an ideal catalyst candidate for direct alcohol fuel cell. - Graphical abstract: The ordered structure of Pt{sub 2}In{sub 3} nanoparticles synthesized by solvothermal method has confirmed through XRD and TEM. Cyclic voltametry and chronoamperometry showed improved catalytic activity and stability compared to commercial Pt/C. - Highlights: • Ordered Pt{sub 2}In{sub 3} nanoparticles were synthesized by solvothermal method. • Electrooxidation of alcohols on Pt{sub 2}In{sub 3} catalyst was investigated in acidic medium. • Pt{sub 2}In{sub 3} catalyst has superior catalytic activity compared to commercial Pt/C. • Pt{sub 2}In{sub 3} catalyst exhibited much higher stability than commercial Pt/C.

  18. Seed-mediated synthesis of acanthosphere-like gold microstructures with tunable LSPR in the NIR region using gemini surfactants as directing agents for SERS applications

    Science.gov (United States)

    Xia, Yan; Gao, Zhinong; Liao, Xueming; Wei, Wanying; Pan, Chenchen

    2017-08-01

    Acanthosphere-like gold microstructures (AGMs) were synthesized using a facile, two-step, seed-mediated method and butanediyl-1,4- bis(dimethylhexadecylammonium bromide) (16-4-16) as a structure-directing agent. The morphologies and sizes of the products were controlled during the synthesis process by adjusting the concentrations of 16-4-16, the AgNO3 feed, HAuCl4, ascorbic acid, the amount of Ag seeds and the types of gemini surfactants used through systematic inquiry; particle sizes ranging from 130 to 800 nm were well prepared. Correspondingly, the morphology of the products changed between regular and irregular AGMs, and the products presented a number of new morphologies, such as open-mouthed submicrostructures and ribbon nanowires. In particular, with the increase in the 16-4-16 concentration, the structural morphology of the thorns clearly changed from a tip to a lamellar structure. A UV-vis spectroscopic analysis indicated that the localized surface plasmon resonance (LSPR) peak of the AGMs could be adjusted by changing the above factors, which extended from 500 to 1350 nm in the near-infrared (NIR) region, enabling a tremendous potential for using the AGMs as platforms for various biomedical applications. Based on the intermediate products, we propose a two-stage growth mechanism for the AGMs in which their solid cores and tips are generated successively. Surface-enhanced Raman scattering (SERS) measurements indicate that the AGMs can serve as sensitive SERS substrates; a SERS detection limit of 5 × 10-7 M is presented for rhodamine B molecules. [Figure not available: see fulltext.

  19. Kinetics of template-directed pyrophosphate-linked dideoxyguanylate synthesis as a function of 2-MeImpdG and poly(C) concentration: insights into the mechanism

    Science.gov (United States)

    Kanavarioti, A.; Gangopadhyay, S.

    1999-01-01

    Aqueous solutions of deoxyguanosine 5'-monophosphate 2-methylimidazolide, 2-MeImpdG, yield primarily deoxyguanosine 5'-monophosphate, 5'dGMP, and pyrophosphate-linked dideoxyguanylate, dG5'ppdG, abbreviated G2p (see Chart 1). The initial rate of G2p formation, d[G2p]/dt in M h-1, determined at 23 degrees C, pH 7.8, 1.0 M NaCl and 0.2 M Mg2+ by timed high-performance liquid chromatography (HPLC) analysis, exhibits a second-order dependence on 2-MeImpdG concentration, [G]o, indicating a bimolecular mechanism of dimerization in the range 0.02 M kinetics of G2p formation as a function of both monomer and polymer concentration, expressed in C equivalents, were also determined under the above conditions and exhibited a complex behavior. Specifically, at a constant [poly(C)], values of d[G2p]/dt typically increased with [G]o with a parabolic upward curvature. At a constant [G]o, values of d[G2p]/dt increase with [poly(C)], but level off at the higher poly(C) concentrations. As [G]o increases this saturation occurs at a higher poly(C) concentration, a result opposite to expectation for a simple complexation of two reacting monomers with the catalyst prior to reaction. Nevertheless, these results are shown to be quantitatively consistent with a template-directed (TD) mechanism of dimerization where poly(C) acts as the template to bind 2-MeImpdG in a cooperative manner and lead, for the first time, to the formulation of principles that govern template-directed chemistry. Analysis of the kinetic data via a proposed TD cooperative model provides association constants for the affinity between polymer and monomer and the intrinsic reactivity of 2-MeImpdG toward pyrophosphate synthesis. To the best of our knowledge, poly(C)/2-MeImpdG is the first system that could serve as a textbook example of a TD reaction under conditions such that the template is fully saturated by monomers and under conditions that it is not.

  20. Nanocrystalline TiO{sub 2} films containing sulfur and gold: Synthesis, characterization and application to immobilize and direct electrochemistry of cytochrome c

    Energy Technology Data Exchange (ETDEWEB)

    Rafiee-Pour, Hossain-Ali, E-mail: rafieepour@kashanu.ac.ir [Biotechnology Division, Department of Molecular and Cell Biology, Faculty of Chemistry, University of Kashan, Kashan, Islamic Republic of Iran (Iran, Islamic Republic of); Hamadanian, Masood [Institute of Nanoscience and Nanotechnology, University of Kashan, Kashan , Islamic Republic of Iran (Iran, Islamic Republic of); Department of Physical Chemistry, Faculty of Chemistry, University of Kashan, Kashan, Islamic Republic of Iran (Iran, Islamic Republic of); Koushali, Samaneh Katebi [Department of Physical Chemistry, Faculty of Chemistry, University of Kashan, Kashan, Islamic Republic of Iran (Iran, Islamic Republic of)

    2016-02-15

    Graphical abstract: - Highlights: • Promoting efficiency of TiO{sub 2} in cyt c immobilization by metal and nonmetal doping. • Synthesis of Au/S-TiO{sub 2} as a novel and efficient for cyt c immobilization. • Investigating structural, chemical and morphological characteristics of prepared TiO{sub 2}, S-TiO{sub 2} and Au/S-TiO{sub 2} nanoparticles. • 4%Au/S-TiO{sub 2} showed high surface area, nanometer size, strong absorbance, high efficiency in cyt c immobilization. • Promoting immobilization efficiency by addition of a small amount of gold at the surface of TiO{sub 2} by photochemistry method. - Abstract: In this paper, nanoporous titanium dioxide (TiO{sub 2}) film was used for cytochrome c (cyt c) immobilization as an electrode substrate for electrochemical redox activity of the adsorbed cyt c. The result of cyclic voltammetry exhibited a pair of well-defined and quasi-reversible peaks for direct electron transfer of cyt c (formal potential [E{sup 0}′ = (E{sub pa} + E{sub pc})/2] of 53 mV versus Ag/AgCl). In addition the effect of metal and nonmetal ions (Au, S) co-doping on the efficiency of TiO{sub 2} nanoparticles (prepared by combining sol–gel and photo-deposition methods) on the cyt c immobilization process was investigated. The results exhibited that the Au, S-co-doped TiO{sub 2} (Au/S-TiO{sub 2}) with a spheroidal shape demonstrates a smaller grain size than the pure TiO{sub 2}. Meanwhile, the UV–vis DRS of Au/S-TiO{sub 2} showed a considerable red shift to the visible region. As a result, it was found that 4% Au/0.1% S-TiO{sub 2} had the highest efficiency for cytochrome c immobilization. The results showed that the peak currents were higher after the annealing of the TiO{sub 2} film. This observation suggests that the use of TiO{sub 2} films may be advantageous for the development of nanoporous biosensors employing reductive electrochemistry.

  1. Emulsion droplets as a dynamic interface for the direct and large-scale synthesis of ultrathin free-standing mesoporous silica films as well as 2D polymeric and carbon nanomaterials

    Science.gov (United States)

    Li, Jian; Zhu, Wei; Ji, Jingwei; Wang, Peng; Wang, Chen; Yin, Xianpeng; Wang, Hui; Lan, Yue; Gao, Ning; Li, Guangtao

    2016-01-01

    The efficient synthesis of free-standing mesostructured two-dimensional (2D) nanofilms with high-yield as well as good control of composite, mesophase structure, orientation of the pore channel and thickness represents a big challenge. In this work, it was serendipitously found that microemulsion droplets of tetraethylorthosilicate (TEOS) could serve as a novel dynamic interface for continuous growth of nanofilms. Based on this finding, a general, efficient strategy for the direct and large-scale synthesis of free-standing mesoporous silica films (FSMSFs) was developed. Remarkably, with the careful control of the synthesis conditions, the FSMSFs with high-yield as well as good control of composite, mesophase structure, orientation of the pore channel and thickness could be efficiently achievable. More importantly, by using polymerizable surfactants the preorganized monomers in the nanochannels of the resultant silica films could be further converted into 2D polymers and carbon nanomaterials as well as metal particle-decorated forms, as exemplified by using pyrrole-terminated surfactants, demonstrating a powerful method to create 2D inorganic, organic or hybrid functional nanomaterials.The efficient synthesis of free-standing mesostructured two-dimensional (2D) nanofilms with high-yield as well as good control of composite, mesophase structure, orientation of the pore channel and thickness represents a big challenge. In this work, it was serendipitously found that microemulsion droplets of tetraethylorthosilicate (TEOS) could serve as a novel dynamic interface for continuous growth of nanofilms. Based on this finding, a general, efficient strategy for the direct and large-scale synthesis of free-standing mesoporous silica films (FSMSFs) was developed. Remarkably, with the careful control of the synthesis conditions, the FSMSFs with high-yield as well as good control of composite, mesophase structure, orientation of the pore channel and thickness could be efficiently

  2. A facile approach to the synthesis of highly electroactive Pt nanoparticles on graphene as an anode catalyst for direct methanol fuel cells.

    Science.gov (United States)

    Zhou, Yi-Ge; Chen, Jing-Jing; Wang, Feng-bin; Sheng, Zhen-Huan; Xia, Xing-Hua

    2010-08-28

    A one-step electrochemical approach to the synthesis of highly dispersed Pt nanoparticles on graphene has been proposed. The resultant Pt NPs@G nanocomposite shows higher electrocatalytic activity and long-term stability towards methanol electrooxidation than the Pt NPs@Vulcan.

  3. Synthesis of Nucleosides through Direct Glycosylation of Nucleobases with 5-O-Monoprotected or 5-Modified Ribose: Improved Protocol, Scope, and Mechanism

    Czech Academy of Sciences Publication Activity Database

    Downey, Alan Michael; Pohl, Radek; Roithová, J.; Hocek, Michal

    2017-01-01

    Roč. 23, č. 16 (2017), s. 3910-3917 ISSN 0947-6539 R&D Projects: GA TA ČR(CZ) TE01020028; GA ČR(CZ) GA16-00178S Institutional support: RVO:61388963 Keywords : epoxides * glycosylation * nucleosides * riboses * synthesis design Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 5.317, year: 2016

  4. Direct versus ligand-exchange synthesis of [PtAg28(BDT)12(TPP)4]4-nanoclusters: effect of a single-atom dopant on the optoelectronic and chemical properties.

    Science.gov (United States)

    Bootharaju, Megalamane S; Kozlov, Sergey M; Cao, Zhen; Harb, Moussab; Parida, Manas R; Hedhili, Mohamed N; Mohammed, Omar F; Bakr, Osman M; Cavallo, Luigi; Basset, Jean-Marie

    2017-07-13

    Heteroatom doping of atomically precise nanoclusters (NCs) often yields a mixture of doped and undoped products of single-atom difference, whose separation is extremely difficult. To overcome this challenge, novel synthesis methods are required to offer monodisperse doped NCs. For instance, the direct synthesis of PtAg 28 NCs produces a mixture of [Ag 29 (BDT) 12 (TPP) 4 ] 3- and [PtAg 28 (BDT) 12 (TPP) 4 ] 4- NCs (TPP: triphenylphosphine; BDT: 1,3-benzenedithiolate). Here, we designed a ligand-exchange (LE) strategy to synthesize single-sized, Pt-doped, superatomic Ag NCs [PtAg 28 (BDT) 12 (TPP) 4 ] 4- by LE of [Pt 2 Ag 23 Cl 7 (TPP) 10 ] NCs with BDTH 2 (1,3-benzenedithiol). The doped NCs were thoroughly characterized by optical and photoelectron spectroscopy, mass spectrometry, total electron count, and time-dependent density functional theory (TDDFT). We show that the Pt dopant occupies the center of the PtAg 28 cluster, modulates its electronic structure and enhances its photoluminescence intensity and excited-state lifetime, and also enables solvent interactions with the NC surface. Furthermore, doped NCs showed unique reactivity with metal ions - the central Pt atom of PtAg 28 could not be replaced by Au, unlike the central Ag of Ag 29 NCs. The achieved synthesis of single-sized PtAg 28 clusters will facilitate further applications of the LE strategy for the exploration of novel multimetallic NCs.

  5. Direct Synthesis of H2O2 over Ti-Containing Molecular Sieves Supported Gold Catalysts: A Comparative Study for In-situ-H2O2-ODS of Fuel

    International Nuclear Information System (INIS)

    Zhang, Han; Song, Haiyan; Chen, Chunxia; Han, Fuqin; Hu, Shaozheng; Liu, Guangliang; Chen, Ping; Zhao, Zhixi

    2013-01-01

    Direct synthesis of H 2 O 2 and in situ oxidative desulfurization of model fuel over Au/Ti-HMS and Au/TS-1 catalysts has been comparatively investigated in water or methanol. Maximum amount (82%) of active Au 0 species for H 2 O 2 synthesis was obtained. Au/Ti-HMS and Au/TS-1 exhibited the contrary performances in H 2 O 2 synthesis as CH 3 OH/H 2 O ratio of solvent changed. H 2 O 2 decomposition and hydrogenation in water was inhibited by the introduction of methanol. Effect of O 2 /H 2 ratio on H 2 O 2 concentration, H 2 conversion and H 2 O 2 selectivity revealed a relationship between H 2 O 2 generation and H2 consumption. The highest dibenzothiophene removal rate (83.2%) was obtained over Au/Ti-HMS in methanol at 1.5 of O 2 /H 2 ratio and 60 .deg. C. But removal of thiophene over Au/TS-1 should be performed in water without heating to obtain a high removal rate (61.3%). Meanwhile, H 2 conversion and oxidative desulfurization selectivity of H 2 were presented

  6. Direct versus ligand-exchange synthesis of [PtAg28(BDT)12(TPP)4]4− nanoclusters: effect of a single-atom dopant on the optoelectronic and chemical properties

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa

    2017-06-07

    Heteroatom doping of atomically precise nanoclusters (NCs) often yields a mixture of doped and undoped products of single-atom difference, whose separation is extremely difficult. To overcome this challenge, novel synthesis methods are required to offer monodisperse doped NCs. For instance, the direct synthesis of PtAg28 NCs produces a mixture of [Ag29(BDT)12(TPP)4]3- and [PtAg28(BDT)12(TPP)4]4- NCs (TPP: triphenylphosphine; BDT: 1,3-benzenedithiolate). Here, we designed a ligand-exchange (LE) strategy to synthesize single-sized, Pt-doped, superatomic Ag NCs [PtAg28(BDT)12(TPP)4]4- by LE of [Pt2Ag23Cl7(TPP)10] NCs with BDTH2 (1,3-benzenedithiol). The doped NCs were thoroughly characterized by optical and photoelectron spectroscopy, mass spectrometry, total electron count, and time-dependent density functional theory (TDDFT). We show that the Pt dopant occupies the center of the PtAg28 cluster, modulates its electronic structure and enhances its photoluminescence intensity and excited-state lifetime, and also enables solvent interactions with the NC surface. Furthermore, doped NCs showed unique reactivity with metal ions - the central Pt atom of PtAg28 could not be replaced by Au, unlike the central Ag of Ag29 NCs. The achieved synthesis of single-sized PtAg28 clusters will facilitate further applications of the LE strategy for the exploration of novel multimetallic NCs.

  7. Total Synthesis and Stereochemical Assignment of Delavatine A: Rh-Catalyzed Asymmetric Hydrogenation of Indene-Type Tetrasubstituted Olefins and Kinetic Resolution through Pd-Catalyzed Triflamide-Directed C-H Olefination.

    Science.gov (United States)

    Zhang, Zhongyin; Wang, Jinxin; Li, Jian; Yang, Fan; Liu, Guodu; Tang, Wenjun; He, Weiwei; Fu, Jian-Jun; Shen, Yun-Heng; Li, Ang; Zhang, Wei-Dong

    2017-04-19

    Delavatine A (1) is a structurally unusual isoquinoline alkaloid isolated from Incarvillea delavayi. The first and gram-scale total synthesis of 1 was accomplished in 13 steps (the longest linear sequence) from commercially available starting materials. We exploited an isoquinoline construction strategy and developed two reactions, namely Rh-catalyzed asymmetric hydrogenation of indene-type tetrasubstituted olefins and kinetic resolution of β-alkyl phenylethylamine derivatives through Pd-catalyzed triflamide-directed C-H olefination. The substrate scope of the first reaction covered unfunctionalized olefins and those containing polar functionalities such as sulfonamides. The kinetic resolution provided a collection of enantioenriched indane- and tetralin-based triflamides, including those bearing quaternary chiral centers. The selectivity factor (s) exceeded 100 for a number of substrates. These reactions enabled two different yet related approaches to a key intermediate 28 in excellent enantiopurity. In the synthesis, the triflamide served as not only an effective directing group for C-H bond activation but also a versatile functional group for further elaborations. The relative and absolute configurations of delavatine A were unambiguously assigned by the syntheses of the natural product and its three stereoisomers. Their cytotoxicity against a series of cancer cell lines was evaluated.

  8. Direct Synthesis and Morphological Characterization of Gold-Dendrimer Nanocomposites Prepared Using PAMAM Succinamic Acid Dendrimers: Preliminary Study of the Calcification Potential

    Science.gov (United States)

    Vasile, E.; Serafim, A.; Petre, D.; Giol, D.; Dubruel, P.; Iovu, H.; Stancu, I. C.

    2014-01-01

    Gold-dendrimer nanocomposites were obtained for the first time by a simple colloidal approach based on the use of polyamidoamine dendrimers with succinamic acid terminal groups and dodecanediamine core. Spherical and highly crystalline nanoparticles with dimensions between 3 nm and 60 nm, and size-polydispersity depending on the synthesis conditions, have been generated. The influence of the stoichiometric ratio and the structural and architectural features of the dendrimers on the properties of the nanocomposites has been described. The self-assembling behaviour of these materials produces gold-dendrimer nanostructured porous networks with variable density, porosity, and composition. The investigations of the reaction systems, by TEM, at two postsynthesis moments, allowed to preliminary establish the control over the properties of the nanocomposite products. Furthermore, this study allowed better understanding of the mechanism of nanocomposite generation. Impressively, in the early stages of the synthesis, the organization of gold inside the dendrimer molecules has been evidenced by micrographs. Growth and ripening mechanisms further lead to nanoparticles with typical characteristics. The potential of such nanocomposite particles to induce calcification when coating a polymer substrate was also investigated. PMID:24600316

  9. An investigation into the effects of different existing states of aluminum isopropoxide on copper-based catalysts for direct synthesis of dimethyl ether from syngas

    Science.gov (United States)

    Sun, Kai; Wang, Peng; Bian, Zhongkai; Huang, Wei

    2018-01-01

    Aluminum isopropoxide (AIP) is a vital raw material to produce high surface area alumina catalyst, which is used for catalytic applications, such as hydrocracking, Fischer-Tropsch and STD (syngas to dimethyl ether) reactions. However, the different existing states have an effect on hydrolysis and condensation in the process of precursor preparation. The Cu/Zn/Al slurry catalysts were prepared by aluminum isopropoxide, which were liquid state, crystalline state and solid state, utilizing a complete liquid phase preparation technology. In the dimethyl ether (DME) synthesis reaction, the aluminum resource of crystalline state was prepared for slurry catalyst, which presented high CO conversion and DME selectivity of 54.32% and 69.74%, respectively. Characterization results indicated that different forms of AIP have the variant coordination numbers of Al-O and polymerization degrees, and the catalyst prepared by crystalline state consists amount of tetra-coordinated Al and few hexa-coordinated Al, which can exert different hydrolysis and condensation process compared with other aluminum sources, and finally it contributes to the strong interaction between active site copper species and Zn/Al species, confirming more Cu+ is responsible for the synthesis of DME in the slurry reactor.

  10. Effect of solvents and oil content on direct transesterification of wet oil-bearing microalgal biomass of Chlorella vulgaris ESP-31 for biodiesel synthesis using immobilized lipase as the biocatalyst.

    Science.gov (United States)

    Tran, Dang-Thuan; Chen, Ching-Lung; Chang, Jo-Shu

    2013-05-01

    In this work, a one-step extraction/transesterification process was developed to directly convert wet oil-bearing microalgal biomass of Chlorella vulgaris ESP-31 into biodiesel using immobilized Burkholderia lipase as the catalyst. The microalgal biomass (water content of 86-91%; oil content 14-63%) was pre-treated by sonication to disrupt the cell walls and then directly mixed with methanol and solvent to carry out the enzymatic transesterification. Addition of a sufficient amount of solvent (hexane is most preferable) is required for the direct transesterification of wet microalgal biomass, as a hexane-to-methanol mass ratio of 1.65 was found optimal for the biodiesel conversion. The amount of methanol and hexane required for the direct transesterification process was also found to correlate with the lipid content of the microalga. The biodiesel synthesis process was more efficient and economic when the lipid content of the microalgal biomass was higher. Therefore, using high-lipid-content microalgae as feedstock appears to be desirable. Copyright © 2012 Elsevier Ltd. All rights reserved.

  11. Protein-directed synthesis of Mn-doped ZnS quantum dots: a dual-channel biosensor for two proteins.

    Science.gov (United States)

    Wu, Peng; Zhao, Ting; Tian, Yunfei; Wu, Lan; Hou, Xiandeng

    2013-06-03

    Proteins typically have nanoscale dimensions and multiple binding sites with inorganic ions, which facilitates the templated synthesis of nanoparticles to yield nanoparticle-protein hybrids with tailored functionality, water solubility, and tunable frameworks with well-defined structure. In this work, we report a protein-templated synthesis of Mn-doped ZnS quantum dots (QDs) by exploring bovine serum albumin (BSA) as the template. The obtained Mn-doped ZnS QDs give phosphorescence emission centered at 590 nm, with a decay time of about 1.9 ms. A dual-channel sensing system for two different proteins was developed through integration of the optical responses (phosphorescence emission and resonant light scattering (RLS)) of Mn-doped ZnS QDs and recognition of them by surface BSA phosphorescent sensing of trypsin and RLS sensing of lysozyme. Trypsin can digest BSA and remove BSA from the surface of Mn-doped ZnS QDs, thus quenching the phosphorescence of QDs, whereas lysozyme can assemble with BSA to lead to aggregation of QDs and enhanced RLS intensity. The detection limits for trypsin and lysozyme were 40 and 3 nM, respectively. The selectivity of the respective channel for trypsin and lysozyme was evaluated with a series of other proteins. Unlike other protein sensors based on nanobioconjugates, the proposed dual-channel sensor employs only one type of QDs but can detect two different proteins. Further, we found the RLS of QDs can also be useful for studying the BSA-lysozyme binding stoichiometry, which has not been reported in the literature. These successful biosensor applications clearly demonstrate that BSA not only serves as a template for growth of Mn-doped ZnS QDs, but also impacts the QDs for selective recognition of analyte proteins. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Instrument Modeling and Synthesis

    Science.gov (United States)

    Horner, Andrew B.; Beauchamp, James W.

    During the 1970s and 1980s, before synthesizers based on direct sampling of musical sounds became popular, replicating musical instruments using frequency modulation (FM) or wavetable synthesis was one of the “holy grails” of music synthesis. Synthesizers such as the Yamaha DX7 allowed users great flexibility in mixing and matching sounds, but were notoriously difficult to coerce into producing sounds like those of a given instrument. Instrument design wizards practiced the mysteries of FM instrument design.

  13. Synthesis of a CdSe-graphene hybrid composed of CdSe quantum dot arrays directly grown on CVD-graphene and its ultrafast carrier dynamics.

    Science.gov (United States)

    Kim, Yong-Tae; Shin, Hee-Won; Ko, Young-Seon; Ahn, Tae Kyu; Kwon, Young-Uk

    2013-02-21

    We report the original fabrication and performance of a photocurrent device that uses directly grown CdSe quantum dots (QDs) on a graphene basal plane. The direct junction between the QDs and graphene and the high quality of the graphene grown by chemical vapor deposition enables highly efficient electron transfer from the QDs to the graphene. Therefore, the hybrids show large photocurrent effects with a fast response time and shortened photoluminescence (PL) lifetime. The PL lifetime quenching can be explained as being due to the efficient electron transfer as evidenced by femtosecond transient absorption spectroscopy. These hybrids are expected to find applications in flexible electronics and optoelectronic devices.

  14. Waste-Glycerol-Directed Synthesis of Mesoporous Silica and Carbon with Superior Performance in Room-Temperature Hydrogen Production from Formic Acid

    Science.gov (United States)

    Lee, Dong-Wook; Jin, Min-Ho; Park, Ji Chan; Lee, Chun-Boo; Oh, Duckkyu; Lee, Sung-Wook; Park, Jin-Woo; Park, Jong-Soo

    2015-10-01

    The development of easier, cheaper, and more ecofriendly synthetic methods for mesoporous materials remains a challenging topic to commercialize them, and the transformation of waste glycerol, as a biodiesel byproduct, into something useful and salable is one of the pending issues to be resolved. Here we first report that mesoporous silica (KIE-6) and carbon (KIE-7) can be simultaneously synthesized by using cheap and ecofriendly crude-waste-glycerol of biodiesel with or without glycerol purification, and we demonstrated the excellent performance of the mesoporous material as a catalyst support for formic acid decomposition. As a result, Pd-MnOx catalysts supported on NH2-functionalized KIE-6 showed the highest catalytic activity (TOF: 540.6 h-1) ever reported for room-temperature formic acid decomposition without additives. Moreover, we conducted life-cycle assessment (LCA) from biomass cultivation through biodiesel production to KIE-6 and KIE-7 preparation, and it was confirmed that CO2 emission during synthesis of KIE-6 and KIE-7 could be reduced by 87.1% and 85.7%, respectively. We believe that our study suggested more ecofriendly and industry-friendly approaches for preparation of mesoporous materials, and utilization of waste glycerol.

  15. SYNTHESIS AND MUTAGENICITY OF DIRECT DYES FROM 4,4'-DIAMINO-PARA-TERPHENYL AND 4,4'-DIAMINO-PARA-QUATERPHENYL

    Science.gov (United States)

    DBPs in drinking water can be controlled by the type of treatment and by knowing and controlling major sources of DBP toxicant precursors and toxicants that "evade" treatment processes. Efforts are being directed at one category at a time. The initial precursor categories to be c...

  16. A One-Pot Selective Synthesis of N-Boc Protected Secondary Amines: Tandem Direct Reductive Amination/N-Boc Protection

    OpenAIRE

    Neelarapu, Raghupathi; Petukhov, Pavel A.

    2012-01-01

    A one-pot tandem direct reductive amination of aldehydes with primary amines resulting in N-Boc secondary amines using a (Boc)2O/sodium triacetoxyborohydride (STAB) system is reported. The tandem procedure is efficient, selective, and versatile, giving excellent yields of N-Boc protected secondary amines even in those cases where the products are prone to intramolecular lactamization

  17. A One-Pot Selective Synthesis of N-Boc Protected Secondary Amines: Tandem Direct Reductive Amination/N-Boc Protection.

    Science.gov (United States)

    Neelarapu, Raghupathi; Petukhov, Pavel A

    2012-09-02

    A one-pot tandem direct reductive amination of aldehydes with primary amines resulting in N-Boc secondary amines using a (Boc)(2)O/sodium triacetoxyborohydride (STAB) system is reported. The tandem procedure is efficient, selective, and versatile, giving excellent yields of N-Boc protected secondary amines even in those cases where the products are prone to intramolecular lactamization.

  18. Mass-Controlled Direct Synthesis of Graphene-like Carbon Nitride Nanosheets with Exceptional High Visible Light Activity. Less is Better

    Science.gov (United States)

    Zhao, Zaiwang; Sun, Yanjuan; Luo, Qian; Dong, Fan; Li, Hui; Ho, Wing-Kei

    2015-01-01

    In the present work, it is very surprising to find that the precursors mass, a long overlooked factor for synthesis of 2D g-C3N4, exerts unexpected impact on g-C3N4 fabrication. The nanoarchitecture and photocatalytic capability of g-C3N4 can be well-tailored only by altering the precursors mass. As thiourea mass decreases, thin g-C3N4 nanosheets with higher surface area, elevated conduction band position and enhanced photocatalytic capability was triumphantly achieved. The optimized 2D g-C3N4 (CN-2T) exhibited exceptional high photocatalytic performance with a NO removal ratio of 48.3%, superior to that of BiOBr (21.3%), (BiO)2CO3 (18.6%) and Au/(BiO)2CO3 (33.8%). The excellent activity of CN-2T can be ascribed to the co-contribution of enlarged surface areas, strengthened electron-hole separation efficiency, enhanced electrons reduction capability and prolonged charge carriers lifetime. The DMPO ESR-spin trapping and hole trapping results demonstrate that the superoxide radicals (•O2−) and photogenerated holes are the main reactive species, while hydroxyl radicals (•OH) play a minor role in photocatalysis reaction. By monitoring the reaction intermediate and active species, the reaction mechanism for photocatalytic oxidation of NO by g-C3N4 was proposed. This strategy is novel and facile, which could stimulate numerous attentions in development of high-performance g-C3N4 based functional nanomaterials. PMID:26411534

  19. Analysis of diverse direct arylation polymerization (DArP) conditions toward the efficient synthesis of polymers converging with stille polymers in organic solar cells

    DEFF Research Database (Denmark)

    Livi, Francesco; Gobalasingham, Nemal S.; Thompson, Barry C.

    2016-01-01

    Despite the emergence of direct arylation polymerization (DArP) as an alternative method to traditional cross-coupling routes like Stille polymerization, the exploration of DArP polymers in practical applications like polymer solar cells (PSCs) is limited. DArP polymers tend to have a reputation...... for being marginally inferior to Stille counterparts due to the increased presence of defects that result from unwanted side reactions in direct arylation, such as unselective C-H bond activation and homocoupling. We report ten DArP protocols across the three major classes of DArP to generate poly[(2,5-bis...... was synthesized in superheated THF with Cs2CO3, neodecanoic acid, and P(o-anisyl)3, it generated polymers of exceptional quality that performed comparably to Stille counterparts in both roll coated ITO-free and spin-coated ITO devices....

  20. Synthesis of a CdSe-graphene hybrid composed of CdSe quantum dot arrays directly grown on CVD-graphene and its ultrafast carrier dynamics

    Science.gov (United States)

    Kim, Yong-Tae; Shin, Hee-Won; Ko, Young-Seon; Ahn, Tae Kyu; Kwon, Young-Uk

    2013-01-01

    We report the original fabrication and performance of a photocurrent device that uses directly grown CdSe quantum dots (QDs) on a graphene basal plane. The direct junction between the QDs and graphene and the high quality of the graphene grown by chemical vapor deposition enables highly efficient electron transfer from the QDs to the graphene. Therefore, the hybrids show large photocurrent effects with a fast response time and shortened photoluminescence (PL) lifetime. The PL lifetime quenching can be explained as being due to the efficient electron transfer as evidenced by femtosecond transient absorption spectroscopy. These hybrids are expected to find applications in flexible electronics and optoelectronic devices.We report the original fabrication and performance of a photocurrent device that uses directly grown CdSe quantum dots (QDs) on a graphene basal plane. The direct junction between the QDs and graphene and the high quality of the graphene grown by chemical vapor deposition enables highly efficient electron transfer from the QDs to the graphene. Therefore, the hybrids show large photocurrent effects with a fast response time and shortened photoluminescence (PL) lifetime. The PL lifetime quenching can be explained as being due to the efficient electron transfer as evidenced by femtosecond transient absorption spectroscopy. These hybrids are expected to find applications in flexible electronics and optoelectronic devices. Electronic supplementary information (ESI) available: TEM data of MSTF, AFM data of T-QD-G samples, PL decay fitting results to the multiexponential decay equation, photoconductivity data of T-QD-2LG with two different illumination wavelengths, photocurrent efficiencies of QD-G hybrids prepared in various ways, photoconductivity and photoresponse data of T-QD-2LG and T-QD-3LG, and the bending stress on a PET film. See DOI: 10.1039/c2nr33294a

  1. Flower-like Bi2Se3 nanostructures: Synthesis and their application for the direct electrochemistry of hemoglobin and H2O2 detection

    International Nuclear Information System (INIS)

    Fan Hai; Zhang Shenxiang; Ju Peng; Su Haichao; Ai Shiyun

    2012-01-01

    Highlights: ► Flower-like Bi 2 Se 3 nanostructures were prepared via a hydrothermal technique. ► Bi 2 Se 3 nanostructures significantly improve the direct electron-transfer of Hb. ► The immobilized Hb shows high catalytic activity to the reduction of H 2 O 2 . - Abstract: In this paper, flower-like Bi 2 Se 3 nanostructures consisting of intercrossed nanosheets networks have been synthesized via a facile hydrothermal technique and applied to the protein electrochemistry for the first time. The prepared Bi 2 Se 3 nanostructures were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM). The direct electrochemistry of hemoglobin (Hb) has been achieved by immobilizing Hb on the prepared Bi 2 Se 3 nanostructures and Nafion (Nf) modified glassy carbon electrode. Bi 2 Se 3 nanostructures show significant promotion to the direct electron-transfer of Hb. The immobilized Hb retained its biological activity well and shows high catalytic activity to the reduction of hydrogen peroxide (H 2 O 2 ). Under the optimal experimental conditions, the catalytic currents are linear to the concentrations of H 2 O 2 in the range of 2.0 × 10 −6 to 1.0 × 10 −4 M. The corresponding detection limits are 6.3 × 10 −7 M. The prepared flower-like Bi 2 Se 3 nanostructures provide an alternative matrix for protein immobilization and biosensor preparation.

  2. Reverse micelles directed synthesis of TiO{sub 2}-CeO{sub 2} mixed oxides and investigation of their crystal structure and morphology

    Energy Technology Data Exchange (ETDEWEB)

    Matejova, Lenka, E-mail: matejova@icpf.cas.cz [Institute of Chemical Process Fundamentals of the ASCR, v. v. i., Department of Catalysis and Reaction Engineering, Rozvojova 135, 165 02 Prague 6 (Czech Republic); Vales, Vaclav [Charles University in Prague, Faculty of Mathematics and Physics, Department of Condensed Matter Physics, Ke Karlovu 5, 121 16 Prague 2 (Czech Republic); Fajgar, Radek [Institute of Chemical Process Fundamentals of the ASCR, v. v. i., Department of Aerosols and Laser Studies, Rozvojova 135, 165 02 Prague 6 (Czech Republic); Matej, Zdenek; Holy, Vaclav [Charles University in Prague, Faculty of Mathematics and Physics, Department of Condensed Matter Physics, Ke Karlovu 5, 121 16 Prague 2 (Czech Republic); Solcova, Olga [Institute of Chemical Process Fundamentals of the ASCR, v. v. i., Department of Catalysis and Reaction Engineering, Rozvojova 135, 165 02 Prague 6 (Czech Republic)

    2013-02-15

    The synthesis of TiO{sub 2}-CeO{sub 2} mixed oxides based on the sol-gel process controlled within reverse micelles of non-ionic surfactant Triton X-114 in cyclohexane is reported. The crystallization, phase composition, trends in nanoparticles growth and porous structure properties are studied as a function of Ti:Ce molar composition and annealing temperature by in-situ X-ray diffraction, Raman spectroscopy and physisorption. The brannerite-type CeTi{sub 2}O{sub 6} crystallizes as a single crystalline phase at Ti:Ce molar composition of 70:30 and in the mixture with cubic CeO{sub 2} and anatase TiO{sub 2} for composition 50:50. At Ti:Ce molar ratios 90:10 and 30:70 the mixtures of TiO{sub 2} anatase, rutile and cubic CeO{sub 2} appear. In these mixtures TiO{sub 2} rutile is formed at higher temperatures than conventionally. Additionally, the amount of a present amorphous phase in individual mixtures was estimated from diffraction data. The porous structure morphology depends both on molar composition and annealing temperature. This is correlated with the presence of carbon impurities of different character. - Graphical abstract: The phase composition of Ti90--Ce10 and Ti50--Ce50 oxide mixtures as a function of annealing temperature. The amount of the amorphous phase was estimated and attributed to TiO{sub 2}. Highlights: Black-Right-Pointing-Pointer Ti/Ce oxides were prepared using reverse micelles of Triton X-114. Black-Right-Pointing-Pointer Crystallization of TiO{sub 2}, CeO{sub 2} or CeTi{sub 2}O{sub 6} depends on Ti:Ce molar ratio. Black-Right-Pointing-Pointer Amorphous phase attributed to TiO{sub 2} was identified. Black-Right-Pointing-Pointer Metal oxides surface area is influenced by the character of present carbon impurities.

  3. DNA-Directed alkylating agents. 7. Synthesis, DNA interaction, and antitumor activity of bis(hydroxymethyl)- and bis(carbamate)-substituted pyrrolizines and imidazoles.

    Science.gov (United States)

    Atwell, G J; Fan, J Y; Tan, K; Denny, W A

    1998-11-19

    A series of bis(hydroxymethyl)-substituted imidazoles, thioimidazoles, and pyrrolizines and related bis(carbamates), linked to either 9-anilinoacridine (intercalating) or 4-(4-quinolinylamino)benzamide (minor groove binding) carriers, were synthesized and evaluated for sequence-specific DNA alkylation and cytotoxicity. The imidazole and thioimidazole analogues were prepared by initial synthesis of [(4-aminophenyl)alkyl]imidazole-, thioimidazole-, or pyrrolizine dicarboxylates, coupling of these with the desired carrier, and reduction to give the required bis(hydroxymethyl) alkylating moiety. The pyrrolizines were the most reactive alkylators, followed by the thioimidazoles, while the imidazoles were unreactive. The pyrrolizines and some of the thioimidazoles cross-linked DNA, as measured by agarose gel electrophoresis. Strand cleavage assays showed that none of the compounds reacted at purine N7 or N3 sites in the gpt region of the plasmid gpt2Eco, but the polymerase stop assay showed patterns of G-alkylation in C-rich regions. The corresponding thioimidazole bis(carbamates) were more selective than the bis(hydroxymethyl) pyrrolizines, with high-intensity bands at 5'-NCCN, 5'-NGCN and 5'-NCGN sequences in the PCR stopping assay ( indicates block sites). The data suggest that these targeted compounds, like the known thioimidazole bis(carbamate) carmethizole, alkylate exclusively at guanine residues via the 2-amino group, with little or no alkylation at N3 and N7 guanine or adenine sites. The cytotoxicities of the compounds correlated broadly with their reactivities, with the bis(hydroxymethyl)imidazoles being the least cytotoxic (IC50s >1 microM; P388 leukemia) and with the intercalator-linked analogues being more cytotoxic than the corresponding minor-groove-targeted ones. This was true also for the more reactive thioimidazole bis(carbamates) (IC50s 0.8 and 11 microM, respectively), but both were more active than the analogous "untargeted" carmethizole (IC50 20

  4. CLEAN CHEMICAL SYNTHESIS IN WATER

    Science.gov (United States)

    Newer green chemistry approach to accomplish chemical synthesis in water is summarized. Recent global developments pertaining to C-C bond forming reactions using metallic reagents and direct use of the renewable materials such as carbohydrates without derivatization are described...

  5. Quasi-analytical synthesis of continuous phase correcting structures to increase the directivity of circularly polarized Fabry-Perot resonator antennas

    International Nuclear Information System (INIS)

    Afzal, Muhammad U.; Esselle, Karu P.

    2015-01-01

    This paper presents a quasi-analytical technique to design a continuous, all-dielectric phase correcting structures (PCSs) for circularly polarized Fabry-Perot resonator antennas (FPRAs). The PCS has been realized by varying the thickness of a rotationally symmetric dielectric block placed above the antenna. A global analytical expression is derived for the PCS thickness profile, which is required to achieve nearly uniform phase distribution at the output of the PCS, despite the non-uniform phase distribution at its input. An alternative piecewise technique based on spline interpolation is also explored to design a PCS. It is shown from both far- and near-field results that a PCS tremendously improves the radiation performance of the FPRA. These improvements include an increase in peak directivity from 22 to 120 (from 13.4 dBic to 20.8 dBic) and a decrease of 3 dB beamwidth from 41.5° to 15°. The phase-corrected antenna also has a good directivity bandwidth of 1.3 GHz, which is 11% of the center frequency

  6. Direct synthesis of bimetallic PtCo mesoporous nanospheres as efficient bifunctional electrocatalysts for both oxygen reduction reaction and methanol oxidation reaction

    Science.gov (United States)

    Wang, Hongjing; Yu, Hongjie; Li, Yinghao; Yin, Shuli; Xue, Hairong; Li, Xiaonian; Xu, You; Wang, Liang

    2018-04-01

    The engineering of electrocatalysts with high performance for cathodic and/or anodic catalytic reactions is of great urgency for the development of direct methanol fuel cells. Pt-based bimetallic alloys have recently received considerable attention in the field of fuel cells because of their superior catalytic performance towards both fuel molecule electro-oxidation and oxygen reduction. In this work, bimetallic PtCo mesoporous nanospheres (PtCo MNs) with uniform size and morphology have been prepared by a one-step method with a high yield. The as-made PtCo MNs show superior catalytic activities for both oxygen reduction reaction and methanol oxidation reaction relative to Pt MNs and commercial Pt/C catalyst, attributed to their mesoporous structure and bimetallic composition.

  7. Synthesis of Pd₃Co₁@Pt/C core-shell catalysts for methanol-tolerant cathodes of direct methanol fuel cells.

    Science.gov (United States)

    Aricò, Antonino S; Stassi, Alessandro; D'Urso, Claudia; Sebastián, David; Baglio, Vincenzo

    2014-08-18

    A composite Pd-based electrocatalyst consisting of a surface layer of Pt (5 wt.%) supported on a core Pd3Co1 alloy (95 wt.%) and dispersed as nanoparticles on a carbon black support (50 wt.% metal content) was prepared by using a sulphite-complex route. The structure, composition, morphology, and surface properties of the catalyst were investigated by XRD, XRF, TEM, XPS and low-energy ion scattering spectroscopy (LE-ISS). The catalyst showed an enrichment of Pt on the surface and a smaller content of Co in the outermost layers. These characteristics allow a decrease the Pt content in direct methanol fuel cell cathode electrodes (from 1 to 0.06 mg cm(-2)) without significant decay in performance, due also to a better tolerance to methanol permeated through the polymer electrolyte membrane. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Template-directed synthesis of dually porous periodic organosilicas with 1,5-bis-(2'-ethyl)-xylene bridging groups

    Energy Technology Data Exchange (ETDEWEB)

    Gryn, Svetlana V. [L.V. Pisarzhevsky Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 34 Prospekt Nauki, Kiev 03039 (Ukraine)], E-mail: catgsv@gmail.com; Tsyrina, Valentina V.; Kovalenko, Aleksandr S. [L.V. Pisarzhevsky Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 34 Prospekt Nauki, Kiev 03039 (Ukraine); Alekseev, Sergei A. [Department of Chemistry, Kiev National Taras Shevchenko University, 64 Volodymyrska Street, Kiev 01033 (Ukraine); Lisnyak, Vladyslav V. [Department of Chemistry, Kiev National Taras Shevchenko University, 64 Volodymyrska Street, Kiev 01033 (Ukraine)], E-mail: lisnyak@chem.univ.kiev.ua; Ilyin, Vladimir G. [L.V. Pisarzhevsky Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 34 Prospekt Nauki, Kiev 03039 (Ukraine)

    2009-03-15

    Porous organosilicas with 1.5-100 mol.% of bridging 1,5-bis-(2'-ethyl)-xylene (BDEX) groups were synthesized by a template-directed procedure and characterized using FTIR spectroscopy, temperature programmed desorption mass-spectrometry, X-ray diffraction and methanol adsorption. The formation of dually porous structure, consisted in small low-ordered mesoporous (2-3 nm) MCM-41 type particles united in aggregates with wide interparticle pores (8-20 nm), was found. If the concentration of the BDEX groups is smaller than 10 mol.%, the BDEX groups can be thermally oxidized without dually porous structure damage. The aggregation of the primary particles by chemical cross-linking is an alternative way to form a network of large so-called 'transport' pores in the mesoporous material.

  9. Mango core inner shell membrane template-directed synthesis of porous ZnO films and their application for enzymatic glucose biosensor

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Yu; Wang, Lei [Department of Materials Science and Engineering, State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou, 310027 (China); Ye, Zhizhen [Department of Materials Science and Engineering, State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou, 310027 (China); Cyrus Tang Center for Sensor Materials and Applications, Zhejiang University (China); Zhao, Minggang; Cai, Hui [Department of Materials Science and Engineering, State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou, 310027 (China); Huang, Jingyun, E-mail: huangjy@zju.edu.cn [Department of Materials Science and Engineering, State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou, 310027 (China); Cyrus Tang Center for Sensor Materials and Applications, Zhejiang University (China)

    2013-11-15

    Micro/nano-porous ZnO films were synthesized through a simple biotemplate-directed method using mango core inner shell membranes as templates. The achieved ZnO films with wrinkles on the surface are combined of large holes and small pores in the bulk. High specific surface area, numerous microspaces, and small channels for fluid circulation provided by this unique structure along with the good biocompatibility and electron communication features of ZnO material make the product an ideal platform for the immobilization of enzymes The fabricated glucose biosensor based on the porous ZnO films exhibits good selective detection ability of analyte with good stability, high sensitivity of 50.58 μA cm{sup −2} mM{sup −1} and a wide linear range of 0.2–5.6 mM along with a low detection limit of 10 μM.

  10. Mango core inner shell membrane template-directed synthesis of porous ZnO films and their application for enzymatic glucose biosensor

    Science.gov (United States)

    Zhou, Yu; Wang, Lei; Ye, Zhizhen; Zhao, Minggang; Cai, Hui; Huang, Jingyun

    2013-11-01

    Micro/nano-porous ZnO films were synthesized through a simple biotemplate-directed method using mango core inner shell membranes as templates. The achieved ZnO films with wrinkles on the surface are combined of large holes and small pores in the bulk. High specific surface area, numerous microspaces, and small channels for fluid circulation provided by this unique structure along with the good biocompatibility and electron communication features of ZnO material make the product an ideal platform for the immobilization of enzymes The fabricated glucose biosensor based on the porous ZnO films exhibits good selective detection ability of analyte with good stability, high sensitivity of 50.58 μA cm-2 mM-1 and a wide linear range of 0.2-5.6 mM along with a low detection limit of 10 μM.

  11. Palladium-catalyzed microwave-assisted direct arylation of imidazo[2,1-b]thiazoles with aryl bromides: synthesis and mechanistic study.

    Science.gov (United States)

    Zhu, Yi-Shuo; Shi, Benyi; Fang, Ran; Wang, Xiaoxuan; Jing, Huanwang

    2014-08-14

    A palladium-catalyzed direct C-H arylation of various imidazo[2,1-b]thiazoles with a range of aryl bromides under microwave irradiation is described. 6-Phenyl substituted imidazo[2,1-b]thiazoles could be regioselectively C-5 arylated using the developed protocol. The utility of this method enables the representative coupling product to be achieved by a sequential one-pot reaction. Density functional theory (DFT) calculations show that this arylation proceeds via a concerted metalation-deprotonation (CMD) pathway, which is in agreement with our experimental results. This work provides a convenient access to a variety of biologically active imidazo[2,1-b]thiazole derivatives. Also, it enriches the mechanism study of site-selective C-H arylation in fused heterocycles, and offers a valuable guide to design highly efficient catalytic systems for the preparation of similar compounds.

  12. Protein-directed in situ synthesis of platinum nanoparticles with superior peroxidase-like activity, and their use for photometric determination of hydrogen peroxide

    International Nuclear Information System (INIS)

    Chen, Lijian; Wang, Nan; Wang, Xindong; Ai, Shiyun

    2013-01-01

    Platinum nanoparticles (Pt-NPs) with sizes in the range from 10 to 30 nm were synthesized using protein-directed one-pot reduction. The model globular protein bovine serum albumin (BSA) was exploited as the template, and the resulting BSA/Pt-NPs were studied by transmission electron microscopy, energy dispersive X-ray spectroscopy, and resonance Rayleigh scattering spectroscopy. The modified nanoparticles display a peroxidase-like activity that was exploited in a rapid method for the colorimetric determination of hydrogen peroxide which can be detected in the 50 μM to 3 mM concentration range. The limit of detection is 7.9 μM, and the lowest concentration that can be visually detected is 200 μM. (author)

  13. Hydrothermal–galvanic couple synthesis of directionally oriented BaTiO3 thin films on TiN-coated substrates

    International Nuclear Information System (INIS)

    Yang, Chia-Jung; Tsai, Di-You; Chan, Pei-Hsuan; Wu, Chu-Tsun; Lu, Fu-Hsing

    2013-01-01

    BaTiO 3 films were synthesized on TiN-coated Si substrate below 100 °C by a hydrothermal–galvanic couple technique in barium contained alkaline solutions. X-ray diffraction and electron backscatter diffraction results show that the BaTiO 3 thin films were directionally oriented grown on the TiN/Si substrates, i.e., (111) BaTiO 3 over (111) TiN. The surface morphologies revealed that BaTiO 3 nucleated and grew over the TiN surface with a single layer. From kinetic analyses, the growth rates of BaTiO 3 films prepared by the hydrothermal–galvanic couple technique were faster than a hydrothermal method. The galvanic effects were confirmed by investigating the induced currents and energies. The galvanic currents were generated and controlled by both the dissolution of TiN and the formation of BaTiO 3 . The output electric energies increased rapidly with the reaction time and leveled off at the full coverage of BaTiO 3 . - Highlights: • Cubic BaTiO 3 films are synthesized by a hydrothermal–galvanic couple method (HT–GC). • Growth rates of BaTiO 3 films made by HT–GC are faster than a hydrothermal method. • BaTiO 3 films are directionally oriented grown on the TiN/Si substrates. • Galvanic currents are controlled by dissolution of TiN and formation of BaTiO 3

  14. Direct in situ activation of Ag{sup 0} nanoparticles in synthesis of Ag/TiO{sub 2} and its photoactivity

    Energy Technology Data Exchange (ETDEWEB)

    Jaafar, N.F. [Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor (Malaysia); Jalil, A.A., E-mail: aishah@cheme.utm.my [Institute of Hydrogen Economy, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor (Malaysia); Department of Chemical Engineering, Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor (Malaysia); Triwahyono, S. [Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor (Malaysia); Ibnu Sina Institute for Fundamental Science Studies, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor (Malaysia); Efendi, J. [Department of Chemistry, Universitas Negeri Padang, Jl. Prof. Hamka, Air Tawar, Padang, West Sumatera (Indonesia); Mukti, R.R. [Division of Inorganic and Physical Chemistry, Faculty of Mathematics and Natural Science, Institut Teknologi Bandung, Jl Ganesha No. 10, Bandung 40132 (Indonesia); Jusoh, R.; Jusoh, N.W.C. [Department of Chemical Engineering, Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor (Malaysia); Karim, A.H. [Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor (Malaysia); Salleh, N.F.M. [Department of Chemical Engineering, Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor (Malaysia); Suendo, V. [Division of Inorganic and Physical Chemistry, Faculty of Mathematics and Natural Science, Institut Teknologi Bandung, Jl Ganesha No. 10, Bandung 40132 (Indonesia)

    2015-05-30

    Graphical abstract: - Highlights: • Ag{sup 0} loaded on TiO{sub 2} was prepared by a direct in situ electrochemical method. • 5 wt% Ag–TiO{sub 2} demonstrated the best photocatalytic degradation of 2-CP. • Isomorphous substitution of Ag with Ti occurred to form Ti−O−Ag bonds. • Ag{sup 0} and oxygen vacancies trapped electrons to enhance e–H{sup +} separation. • Substitution of Ag in the TiO{sub 2} structure decreased the number of oxygen vacancies. - Abstract: Metallic Ag nanoparticles (Ag{sup 0}) were successfully activated using a direct in situ electrochemical method before being supported on TiO{sub 2}. Catalytic testing showed that 5 wt% Ag–TiO{sub 2} gave the highest photodegradation (94%) of 50 mg L{sup −1} 2-chlorophenol (2-CP) at pH 5 using 0.375 g L{sup −1} catalyst within 6 h, while under similar conditions, 1 wt% and 10 wt% Ag–TiO{sub 2} only gave 75% and 78% degradation, respectively. Characterization results illustrated that the photoactivity was affected by the amount of Ag{sup 0} and oxygen vacancies which act as an electrons trap to enhance the electron–hole separation. While, the Ag−O−Ti bonds formation reduced the photoactivity. The degradation followed a pseudo-first order Langmuir–Hinshelwood model where adsorption was the controlling step. Study on the effect of scavengers showed that the hole (H{sup +}) and hydroxyl radical (OH·) play important roles in the photodegradation. The regenerated photocatalyst was still stable after five cycling runs.

  15. Synthesis of 1,3-di(4-amino-1-pyridinium)propane ionic liquid functionalized graphene nanosheets and its application in direct electrochemistry of hemoglobin

    International Nuclear Information System (INIS)

    Li, Rui; Liu, Changxian; Ma, Ming; Wang, Zhengguo; Zhan, Guoqing; Li, Buhai; Wang, Xian; Fang, Huaifang; Zhang, Huijuan; Li, Chunya

    2013-01-01

    Highlights: ► 1,3-Di(4-amino-1-pyridinium)propane tetrafluoroborate ionic liquid was successfully synthesized. ► Ionic liquid modified graphene nanosheets were successfully prepared and fully characterized. ► Hb was immobilized on the as-prepared graphene–ionic liquid nanosheets. ► Direct electrochemistry of Hb was succeeded. ► Biocatalysis of Hb towards H 2 O 2 was demonstrated, and was used in H 2 O 2 determination. -- Abstract: 1,3-Di(4-amino-1-pyridinium)propane tetrafluoroborate (DAPPT) ionic liquid was successfully synthesized, and was used as a modifier to functionalize graphene nanosheets through covalent binding of amino groups and epoxy groups in an alkaline solution. The as-prepared graphene-DAPPT nanosheets (Gr-DAPPT) were confirmed with transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV/vis and FTIR spectroscopy. A biocompatible platform based on Gr-DAPPT was constructed for the immobilization of hemoglobin (Hb) through a cross-linking step with chitosan and glutaraldehyde. The direct electron transfer and bioelectrocatalytic reaction of Hb immobilized on Gr-DAPPT surface were achieved. A pair of reversible redox peaks of hemoglobin was observed, and bioelectrocatalytic activity toward the reduction of H 2 O 2 was also demonstrated, displaying a potential application for the fabrication of novel biosensors to sense H 2 O 2 . Such results indicated that Gr-DAPPT based interface would be a promising platform for biomacromolecular immobilization and biosensor preparation

  16. HTLV-1 Tax Functions as a Ubiquitin E3 Ligase for Direct IKK Activation via Synthesis of Mixed-Linkage Polyubiquitin Chains.

    Science.gov (United States)

    Wang, Chong; Long, Wenying; Peng, Chao; Hu, Lin; Zhang, Qiong; Wu, Ailing; Zhang, Xiaoqing; Duan, Xiaotao; Wong, Catherine C L; Tanaka, Yuetsu; Xia, Zongping

    2016-04-01

    The HTLV-1 oncoprotein Tax plays a key role in CD4+ T cell transformation by promoting cell proliferation and survival, mainly through permanent activation of the NK-κB pathway and induction of many NF-κB target genes. Elucidating the underlying molecular mechanism is therefore critical in understanding HTLV-1-mediated transformation. Current studies have suggested multiple but controversial mechanisms regarding Tax-induced IKK activation mainly due to blending of primary Tax-induced IKK activation events and secondary IKK activation events induced by cytokines secreted by the primary Tax-induced IKK-NF-κB activation events. We reconstituted Tax-stimulated IKK activation in a cell-free system to dissect the essential cellular components for primary IKK activation by Tax and studied the underlying biochemical mechanism. We found that Tax is a putative E3 ubiquitin ligase, which, together with UbcH2, UhcH5c, or UbcH7, catalyzes the assembly of free mixed-linkage polyubiquitin chains. These free mixed-linkage polyubiquitin chains are then responsible for direct IKK activation by binding to the NEMO subunit of IKK. Our studies revealed the biochemical function of Tax in the process of IKK activation, which utilizes the minimal cellular ubiquitination components for NF-κB activation.

  17. Direct Synthesis of Carbon Nanotube Field Emitters on Metal Substrate for Open-Type X-ray Source in Medical Imaging

    Directory of Open Access Journals (Sweden)

    Amar Prasad Gupta

    2017-07-01

    Full Text Available We report the design, fabrication and characterization of a carbon nanotube enabled open-type X-ray system for medical imaging. We directly grew the carbon nanotubes used as electron emitter for electron gun on a non-polished raw metallic rectangular-rounded substrate with an area of 0.1377 cm2 through a plasma enhanced chemical vapor deposition system. The stable field emission properties with triode electrodes after electrical aging treatment showed an anode emission current of 0.63 mA at a gate field of 7.51 V/μm. The 4.5-inch cubic shape open type X-ray system was developed consisting of an X-ray aperture, a vacuum part, an anode high voltage part, and a field emission electron gun including three electrodes with focusing, gate and cathode electrodes. Using this system, we obtained high-resolution X-ray images accelerated at 42–70 kV voltage by digital switching control between emitter and ground electrode.

  18. Application of Mössbauer spectroscopy in industrial heterogeneous catalysis: effect of oxidant on FePO4 material phase transformations in direct methanol synthesis from methane

    Science.gov (United States)

    Dasireddy, Venkata D. B. C.; Khan, Faiza B.; Hanzel, Darko; Bharuth-Ram, Krish; Likozar, Blaž

    2017-11-01

    The effect of the FePO4 material phase transformation in the direct selective oxidation of methane to methanol was studied using various oxidants, i.e. O2, H2O and N2O. The phases of the heterogeneous catalyst applied, before and after the reactions, were characterized by M¨ossbauer spectroscopy. The main reaction products were methanol, carbon monoxide and carbon dioxide, whereas formaldehyde was produced in rather minute amounts. The Mössbauer spectra showed the change of the initial catalyst material, FePO4 (tridymite-like phase (tdm)), to the reduced metal form, iron(II) pyrophosphate, Fe2P2O7, and thereafter, the material phase change was governed by the oxidation with individual oxidizing species.Mössbauer spectroscopy measurements applied along with X-ray diffraction (XRD) studies on fresh, reduced and spent catalytic materials demonstrated a transformation of the catalyst to a mixture of phases which depended on operating process conditions. Generally, activity was low and should be a subject of further material optimization and engineering, while the selectivity towards methanol at low temperatures applied was adequate. The proceeding redox mechanism should thus play a key role in catalytic material design, while the advantage of iron-based heterogeneous catalysts primarily lies in them being comparably inexpensive and comprising non-critical raw materials only.

  19. Application of Mössbauer spectroscopy in industrial heterogeneous catalysis: effect of oxidant on FePO{sub 4} material phase transformations in direct methanol synthesis from methane

    Energy Technology Data Exchange (ETDEWEB)

    Dasireddy, Venkata D. B. C., E-mail: dasireddy@ki.si [National Institute of Chemistry, Department of Catalysis and Chemical Reaction Engineering (Slovenia); Khan, Faiza B. [Energy Technology (South Africa); Hanzel, Darko [Jozef Stefan Institute (Slovenia); Bharuth-Ram, Krish [Durban University of Technology, Physics Department (South Africa); Likozar, Blaž [National Institute of Chemistry, Department of Catalysis and Chemical Reaction Engineering (Slovenia)

    2017-11-15

    The effect of the FePO{sub 4} material phase transformation in the direct selective oxidation of methane to methanol was studied using various oxidants, i.e. O{sub 2}, H{sub 2}O and N{sub 2}O. The phases of the heterogeneous catalyst applied, before and after the reactions, were characterized by M¨ossbauer spectroscopy. The main reaction products were methanol, carbon monoxide and carbon dioxide, whereas formaldehyde was produced in rather minute amounts. The Mössbauer spectra showed the change of the initial catalyst material, FePO{sub 4} (tridymite-like phase (tdm)), to the reduced metal form, iron(II) pyrophosphate, Fe{sub 2}P{sub 2}O{sub 7}, and thereafter, the material phase change was governed by the oxidation with individual oxidizing species.Mössbauer spectroscopy measurements applied along with X-ray diffraction (XRD) studies on fresh, reduced and spent catalytic materials demonstrated a transformation of the catalyst to a mixture of phases which depended on operating process conditions. Generally, activity was low and should be a subject of further material optimization and engineering, while the selectivity towards methanol at low temperatures applied was adequate. The proceeding redox mechanism should thus play a key role in catalytic material design, while the advantage of iron-based heterogeneous catalysts primarily lies in them being comparably inexpensive and comprising non-critical raw materials only.

  20. Titanium(IV) in the organic-structure-directing-agent-free synthesis of hydrophobic and large-pore molecular sieves as redox catalysts.

    Science.gov (United States)

    Wang, Jingui; Yokoi, Toshiyuki; Kondo, Junko N; Tatsumi, Takashi; Zhao, Yanli

    2015-08-10

    Titanium(IV) incorporated into the framework of molecular sieves can be used as a highly active and sustainable catalyst for the oxidation of industrially important organic molecules. Unfortunately, the current process for the incorporation of titanium(IV) requires a large amount of expensive organic molecules used as organic-structure-directing agents (OSDAs), and this significantly increases the production costs and causes environmental problems owing to the removal of OSDAs by pyrolysis. Herein, an OSDA-free process was developed to incorporate titanium(IV) into BEA-type molecular sieves for the first time. More importantly, the hydrophobic environment and the robust, 3 D, and large pore structure of the titanium(IV)-incorporated molecular sieves fabricated from the OSDA-free process created a catalyst that was extremely active and selective for the epoxidation of bulky cyclooctene in comparison to Ti-incorporated BEA-type molecular sieves synthesized with OSDAs and commercial titanosilicate TS-1. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Micelle-Directing Synthesis of Ag-Doped WO3and MoO3Composites for Photocatalytic Water Oxidation and Organic-Dye Adsorption.

    Science.gov (United States)

    Bate, Nasen; Shi, Hongfei; Chen, Li; Wang, Jiabo; Xu, Shasha; Chen, Weilin; Li, Jianping; Wang, Enbo

    2017-10-05

    In this paper, an Ag-doped WO 3 (and MoO 3 ) composite has been prepared by following a simple micelle-directed method and high-temperature sintering route. The as-prepared samples were characterized by X-ray diffraction, inductively coupled plasma, transmission electron microscopy, X-ray photoelectron spectroscopy, UV/Vis diffuse reflectance spectroscopy, Brunauer-Emmett-Teller, photoluminescence spectroscopy, and electrochemical impedance spectroscopy techniques. The photocatalytic experiments reveal that their oxygen-production rates are up to 95.43 μmol (75.45 μmol) for Ag-doped WO 3 (MoO 3 ), which is 9.5 (7.3) times higher than that of pure WO 3 : 9.012 μmol (MoO 3 : 9.00 μmol) under visible-light illumination (λ≥420 nm), respectively. The improvement of their photocatalytic activity is attributed to the enhancement of their visible-light absorption and the separation efficiency of photogenerated carriers by Ag doping. Moreover, Ag-doped WO 3 (MoO 3 ) also shows excellent adsorption of rhodamine B (RhB) and methylene blue (MB) in aqueous solution, with maximum adsorption capacities towards RhB and MB of 822 and 820 mg g -1 for Ag-doped WO 3 , and 642 and 805 mg g -1 for Ag-doped MoO 3 , respectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Synthesis and pharmacology of novel analogues of oxytocin and deaminooxytocin: directed methods for the construction of disulfide and trisulfide bridges in peptides.

    Science.gov (United States)

    Chen, L; Zoulíková, I; Slaninová, J; Barany, G

    1997-03-14

    Using as models the neurohypophyseal nonapeptide hormone oxytocin and its analogue deaminooxytocin, several directed routes to formation of sulfur-sulfur bridges have been developed and evaluated. The linear sequences (through common octapeptide-resin intermediates) were assembled smoothly on tris(alkoxy)benzylamide (PAL) poly(ethylene glycol)-polystyrene (PEG-PS) graft supports, using stepwise Fmoc solid-phase chemistry. Side-chain protection of beta-mercaptopropionic acid (Mpa) and/or cysteine (Cys) was provided by S-2,4,6-trimethoxybenzyl (Tmob), S-acetamidomethyl (Acm), and/or a series of sulfenyl thiocarbonate and carbamoylsulfenyl protecting/activating groups: S-(methoxycarbonyl)sulfenyl (Scm), S-(methoxycarbonyl)disulfanyl (Sscm), S-(N-methyl-N-phenylcarbamoyl)sulfenyl (Snm), and S-(N-methyl-N-phenylcarbamoyl)disulfanyl (Ssnm). Thiolytic displacement of S-Snm (preferred) or S-Scm provided intramolecular cyclized peptide disulfides, and homologation of the chemistry with S-Ssnm (again preferred) and S-Sscm provided the corresponding trisulfides along with smaller amounts of disulfides and tetrasulfides. These chemistries could be implemented both in solution and in solid-phase modes. Various parameters were studied systematically and optimized, and the novel trisulfides of oxytocin and deaminooxytocin were synthesized and purified to homogeneity. The trisulfide compounds were evaluated in three assays: uterotonic in vitro, uterotonic in vivo, and pressor tests, and they showed substantial potencies, ranging from 5% to 40% of the parent (disulfide) activities, as well as protracted actions. The affinities of the peptide trisulfides to uterine membrane receptors were only 3.3-3.6-fold lower than those of the parent disulfides. Possible explanations of the biological results are discussed.

  3. Novel sulfonated poly(ether ether ketone ketone)s for direct methanol fuel cells usage: Synthesis, water uptake, methanol diffusion coefficient and proton conductivity

    Science.gov (United States)

    Zhang, Gang; Fu, Tiezhu; Shao, Ke; Li, Xianfeng; Zhao, Chengji; Na, Hui; Zhang, Hong

    A novel series of sulfonated poly(ether ether ketone ketone)s (SPEEKKs) with different degrees of sulfonation (Ds) were synthesized from 1,3-bis(3-sodium sulfonate-4-fluorobenzoyl)benzene (1,3-SFBB-Na), 1,3-bis(4-fluorobenzoyl)benzene (1,3-FBB) and 3,3‧,5,5‧-tetramethyl-4,4‧-biphenol (TMBP) by aromatic nucleophilic polycondensation. The chemical structures of SPEEKKs were confirmed by FT-IR spectroscopy and the Ds values of the polymers were calculated by 1H NMR and titration methods, respectively. The thermal stabilities of the SPEEKKs in acid and sodium forms were characterized by thermogravimetric analysis (TGA), which showed that SPEEKKs had excellent thermal properties at high temperatures. All the SPEEKK polymers were easily solution cast into tough membranes. Water uptakes, proton conductivities and methanol diffusion coefficients of the SPEEKK membranes were measured. Water uptake increased with Ds and temperature. Compared to Nafion, the SPEEKK-60, -70 and -80 membranes showed higher proton conductivities at 80 °C, while the other SPEEKK membranes showed relatively lower proton conductivities. This may be due to the different distribution of ion-conducting domains in membrane. However, these membranes showed lower methanol diffusions in the range of 8.32 × 10 -9 to 1.14 × 10 -7 cm 2 s -1 compared with that of Nafion (2 × 10 -6 cm 2 s -1) at the same temperature. The membranes also showed excellent mechanical properties (with a Young's modulus > 1 GPa and a tensile strength > 40 MPa). These results indicate that the SPEEKK membranes are promising materials for use in direct methanol fuel cell (DMFC) applications.

  4. Novel sulfonated poly(ether ether ketone ketone)s for direct methanol fuel cells usage: Synthesis, water uptake, methanol diffusion coefficient and proton conductivity

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Gang; Fu, Tiezhu; Shao, Ke; Zhao, Chengji; Na, Hui [Alan G. MacDiarmid Institute, College of Chemistry, Jilin University, Changchun 130012 (China); Li, Xianfeng [Centre for Surface Chemistry and Catalysis, Faculty of Bioengineering Sciences, Katholieke Universiteit Leuven Kasteelpark Arenberg 23, 3001 Leuven (Belgium); Zhang, Hong [Department of Chemistry, Northeast Normal University, Changchun 130024 (China)

    2009-04-15

    A novel series of sulfonated poly(ether ether ketone ketone)s (SPEEKKs) with different degrees of sulfonation (Ds) were synthesized from 1,3-bis(3-sodium sulfonate-4-fluorobenzoyl)benzene (1,3-SFBB-Na), 1,3-bis(4-fluorobenzoyl)benzene (1,3-FBB) and 3,3',5,5'-tetramethyl-4,4'-biphenol (TMBP) by aromatic nucleophilic polycondensation. The chemical structures of SPEEKKs were confirmed by FT-IR spectroscopy and the Ds values of the polymers were calculated by {sup 1}H NMR and titration methods, respectively. The thermal stabilities of the SPEEKKs in acid and sodium forms were characterized by thermogravimetric analysis (TGA), which showed that SPEEKKs had excellent thermal properties at high temperatures. All the SPEEKK polymers were easily solution cast into tough membranes. Water uptakes, proton conductivities and methanol diffusion coefficients of the SPEEKK membranes were measured. Water uptake increased with Ds and temperature. Compared to Nafion, the SPEEKK-60, -70 and -80 membranes showed higher proton conductivities at 80 C, while the other SPEEKK membranes showed relatively lower proton conductivities. This may be due to the different distribution of ion-conducting domains in membrane. However, these membranes showed lower methanol diffusions in the range of 8.32 x 10{sup -9} to 1.14 x 10{sup -7} cm{sup 2} s{sup -1} compared with that of Nafion (2 x 10{sup -6} cm{sup 2} s{sup -1}) at the same temperature. The membranes also showed excellent mechanical properties (with a Young's modulus > 1 GPa and a tensile strength > 40 MPa). These results indicate that the SPEEKK membranes are promising materials for use in direct methanol fuel cell (DMFC) applications. (author)

  5. Synthesis and properties of a novel sulfonated poly(arylene ether ketone sulfone) membrane with a high β-value for direct methanol fuel cell applications

    International Nuclear Information System (INIS)

    Xu, Jingmei; Ma, Li; Han, Hailan; Ni, Hongzhe; Wang, Zhe; Zhang, Huixuan

    2014-01-01

    Highlights: • Introduction of carboxyl groups into copolymers resulted in extensive hydrogen bond. • The C-SPAEKS membranes had obviously hydrophilic/hydrophobic phase separation. • The membranes showed low methanol permeability and high β values. • The membranes exhibited good thermal property and desirable mechanical performance. - Abstract: Sulfonated poly(arylene ether ketone sulfone) membranes containing carboxylic acid groups (C-SPAEKS) with different degrees of sulfonation were synthesized by the nucleophilic aromatic substitution reactions of 4-carboxylphenyl hydroquinone (4C-PH), bisphenol A, 3,3′-disulfonated 4,4′-dichlorodiphenyl sulfone, and 4,4′-difluorobenzophenone. The Fourier transform infrared and 1 H NMR analyses of C-SPAEKS revealed the presence of carboxylic acid groups in the C-SPAEKS membranes. The membranes exhibited a low swelling degree and methanol crossover level. The effects of different degrees of sulfonation on the water uptake, proton conductivity, and methanol permeability coefficient of the membranes were studied. The maximum proton conductivity of C-SPAEKS-80 membrane at room temperature was 0.069 S cm −1 , which was higher than that of Nafion ® 117 membrane. The methanol permeability coefficient of C-SPAEKS-80 membrane was 9.15 × 10 −7 cm 2 s −1 at 20 °C, much lower than that of Nafion 117 membrane (22.9 × 10 −7 cm 2 s −1 ). Furthermore, the carboxyl group-containing membranes exhibited a high β-value, further confirming that this series of membranes possess excellent comprehensive performance and can be applied in direct methanol fuel cells

  6. Fundamentals, progress, and future directions of nitride-based semiconductors and their composites in two-dimensional limit: A first-principles perspective to recent synthesis

    Science.gov (United States)

    Kecik, D.; Onen, A.; Konuk, M.; Gürbüz, E.; Ersan, F.; Cahangirov, S.; Aktürk, E.; Durgun, E.; Ciraci, S.

    2018-03-01

    on a substrate is addressed. We also examine recent works treating the composite structures of GaN and AlN joined commensurately along their zigzag and armchair edges and forming heterostructures, δ-doping, single, and multiple quantum wells, as well as core/shell structures. Finally, outlooks and possible new research directions are briefly discussed.

  7. Total Synthesis of Strychnine.

    Science.gov (United States)

    Lee, Geun Seok; Namkoong, Gil; Park, Jisook; Chen, David Y-K

    2017-11-16

    The total synthesis of the flagship Strychnos indole alkaloid, strychnine, has been accomplished. The developed synthetic sequence features a novel vinylogous 1,4-addition, a challenging iodinium salt mediated silyl enol ether arylation, a palladium-catalyzed Heck reaction, and a streamlined late-stage conversion to strychnine. Furthermore, an application of asymmetric counterion-directed catalysis (ACDC) in the context of target-oriented organic synthesis has been rendered access to an optically active material. The synthetic sequence described herein represents the most concise entry to optically active strychnine to date. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Organic synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, S.E.

    1991-01-01

    This paper reports on reactions of organoboranes. Organoboron routes to unsaturated hydrocarbons. Boronic ester homologation. Properties of organosilicon compounds. Alkene synthesis (Peterson olefination). Allylsilanes and acylsilanes.

  9. Fire Synthesis

    Indian Academy of Sciences (India)

    1000ºC or special infrastructure which require careful maintenance. In such a situation fire synthesis is a simpler method that can be adopted for the bulk production of high purity alumina and related oxides. Fire Synthesis. Preparation of Alumina ...

  10. Direct hydrothermal synthesis of metal intercalated hexagonal ...

    Indian Academy of Sciences (India)

    Unknown

    Increasing reaction time, temperature or decreasing pH of the initial solution with concentrated HCl or HNO3 or change in molar ratio of the reactants did not result in a single phase. The reaction of α-MoO3 with thallium chloride under hydrothermal condition yielded a new unidentified phase. In the case of silver we ended ...

  11. Organic synthesis

    International Nuclear Information System (INIS)

    Lallemand, J.Y.; Fetizon, M.

    1988-01-01

    The 1988 progress report of the Organic Synthesis Chemistry laboratory (Polytechnic School, France), is presented. The laboratory activities are centered on the chemistry of natural products, which have a biological activity and on the development of new reactions, useful in the organic synthesis. The research works involve the following domains: the natural products chemistry which are applied in pharmacology, the plants and insects chemistry, the organic synthesis, the radical chemistry new reactions and the bio-organic physicochemistry. The published papers, the congress communications and the thesis are listed [fr

  12. Phase contrast image synthesis

    DEFF Research Database (Denmark)

    Glückstad, J.

    1996-01-01

    A new method is presented for synthesizing arbitrary intensity patterns based on phase contrast imaging. The concept is grounded on an extension of the Zernike phase contrast method into the domain of full range [0; 2 pi] phase modulation. By controlling the average value of the input phase funct...... function and by choosing appropriate phase retardation at the phase contrast filter, a pure phase to intensity imaging is accomplished. The method presented is also directly applicable in dark field image synthesis....

  13. Síntese e caracterização de espinélios à base de ferritas com gelatina como agente direcionador Synthesis and characterization of ferrite-base spinels with gelatin as directing agent

    Directory of Open Access Journals (Sweden)

    A. F. Costa

    2011-09-01

    Full Text Available As ferritas com estrutura tipo espinélio compreendem um grupo de materiais magnéticos muito bem estabelecidos. Contudo, melhoramentos e inovações continuam acontecendo visando novas aplicações e otimização das técnicas de preparação. Dentre os materiais com estrutura espinélio, as ferritas se destacam por possuírem ampla importância tecnológica na área de materiais, com aplicabilidades em sensores de umidade e de oxigênio, materiais de microondas, pigmentos, materiais magnéticos e elétricos, catálise de hidrogenação, filmes finos, revestimentos cerâmicos, dentre outros. Neste trabalho espinélios tipo CuFe2O4 e CuFeCr2O4 foram sintetizadas usando gelatina como agente direcionador, com a finalidade de produzir partículas nanométricas e homogêneas através de um método simples, rápido e economicamente viável. Os pós foram caracterizados por difração de raios X, espectroscopia de absorção no infravermelho e microscopia eletrônica de varredura. Os resultados confirmaram a viabilidade da rota de síntese utilizada.The ferrites with spinel type structure comprise a group of magnetic materials very well established. However, improvements and innovations are still happening seeking new applications and optimization of preparation techniques. Among the materials with spinel structure, the ferrite stand out because they have a broad technological importance in the area of materials, with applications in humidity and oxygen sensors, microwave materials, pigments, magnetic materials and electrical, catalytic hydrogenation, thin films ceramic tiles, among others. In this work spinel-type CuFe2O4 and CuFeCr2O4 were synthesized using gelatin as directing agent with the purpose of producing nanosized homogeneous particles through a simple, fast and affordable method. The ferrites were characterized by thermal analysis, X-ray diffraction, infrared spectroscopy and scanning electron microscopy. The results confirmed the

  14. An environmentally benign one pot synthesis of substituted ...

    Indian Academy of Sciences (India)

    Organic synthesis generally required large amount of solvent, avoiding the use of organic solvents in synthesis is a paradigm shift directed at developing more benign chemistry, and with ionic liquids surprisingly can lead to access to new compounds. An elegant one-pot synthesis of quinoline derivatives has been achieved ...

  15. Fire Synthesis

    Indian Academy of Sciences (India)

    her PhD degree from. Bangalore University. She is currently working as a Research Associate at the Department of. Inorganic and Physical. Chemistry, Indian. Institute of Science,. Bangalore, on the synthesis of .... This method uses the experiences of propellant chemistry in making the redox mixture. The . stoichiometry or ...

  16. Fire Synthesis

    Indian Academy of Sciences (India)

    special infrastructure which require careful maintenance. In such situation fire synthesis is a simpler method that can be adopted for the bulk production of high purity .... reaction between Ti and B to form titanium boride. The reaction between titanium (fuel- electron donor) and boron (oxidiser-electron acceptor) once initiated ...

  17. Fire Synthesis

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 16; Issue 12. Fire Synthesis - Preparation of Alumina Products. Tanu Mimani. Volume 16 Issue 12 December 2011 pp 1324-1332. Fulltext. Click here to view fulltext PDF. Permanent link: http://www.ias.ac.in/article/fulltext/reso/016/12/1324-1332 ...

  18. Fire Synthesis

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 5; Issue 2. Fire Synthesis - Preparation of Alumina Products. Tanu Mimani. General Article Volume 5 Issue 2 February 2000 pp 50-57. Fulltext. Click here to view fulltext PDF. Permanent link: http://www.ias.ac.in/article/fulltext/reso/005/02/0050-0057 ...

  19. Directed homology

    DEFF Research Database (Denmark)

    Fahrenberg, Uli

    2004-01-01

    We introduce a new notion of directed homology for semicubical sets. We show that it respects directed homotopy and is functorial, and that it appears to enjoy some good algebraic properties. Our work has applications to higher-dimensional automata.......We introduce a new notion of directed homology for semicubical sets. We show that it respects directed homotopy and is functorial, and that it appears to enjoy some good algebraic properties. Our work has applications to higher-dimensional automata....

  20. Direct Democracy

    DEFF Research Database (Denmark)

    Beramendi, Virginia; Ellis, Andrew; Kaufman, Bruno

    of direct democracy mechanisms in specific contexts. These country case studies allow for in depth discussion of particular issues, including signature collection and voter participation, campaign financing, media coverage, national variations in the usage of direct democracy procedures and national lessons...

  1. Structural synthesis of parallel robots

    CERN Document Server

    Gogu, Grigore

    This book represents the fifth part of a larger work dedicated to the structural synthesis of parallel robots. The originality of this work resides in the fact that it combines new formulae for mobility, connectivity, redundancy and overconstraints with evolutionary morphology in a unified structural synthesis approach that yields interesting and innovative solutions for parallel robotic manipulators.  This is the first book on robotics that presents solutions for coupled, decoupled, uncoupled, fully-isotropic and maximally regular robotic manipulators with Schönflies motions systematically generated by using the structural synthesis approach proposed in Part 1.  Overconstrained non-redundant/overactuated/redundantly actuated solutions with simple/complex limbs are proposed. Many solutions are presented here for the first time in the literature. The author had to make a difficult and challenging choice between protecting these solutions through patents and releasing them directly into the public domain. T...

  2. Protein chemical synthesis in drug discovery.

    Science.gov (United States)

    Liu, Fa; Mayer, John P

    2015-01-01

    The discovery of novel therapeutics to combat human disease has traditionally been among the most important goals of research chemists. After a century of innovation, state-of-the-art chemical protein synthesis is now capable of efficiently assembling proteins of up to several hundred residues in length from individual amino acids. By virtue of its unique ability to incorporate non-native structural elements, chemical protein synthesis has been seminal in the recent development of several novel drug discovery technologies. In this chapter, we review the key advances in peptide and protein chemistry which have enabled our current synthetic capabilities. We also discuss the synthesis of D-proteins and their applications in mirror image phage-display and racemic protein crystallography, the synthesis of enzymes for structure-based drug discovery, and the direct synthesis of homogenous protein pharmaceuticals.

  3. Advance Directives

    Science.gov (United States)

    ... Types Bladder Cancer Breast Cancer Colorectal Cancer Kidney (Renal Cell) Cancer Leukemia Liver Cancer Lung Cancer Lymphoma ... about advance directives. Two well-known ones are: Aging With Dignity Aging with Dignity is a national ...

  4. Directing Creativity

    DEFF Research Database (Denmark)

    Darsø, Lotte; Ibbotson, Piers

    2008-01-01

    . Like leaders, who are caught in paradoxical situations where they have to manage production and logistics simultaneously with making space for creativity and innovation, theatre directors need to find the delicate balance between on one hand renewal of perceptions, acting and interaction......In this article we argue that leaders facing complex challenges can learn from the arts, specifically that leaders can learn by examining how theatre directors direct creativity through creative constraints. We suggest that perceiving creativity as a boundary phenomenon is helpful for directing it...... and on the other hand getting ready for the opening night. We conclude that the art of directing creativity is linked to developing competencies of conscious presence, attention and vigilance, whereas the craft of directing creativity concerns communication, framing and choice....

  5. Direct Heat

    Energy Technology Data Exchange (ETDEWEB)

    Lienau, P.J.

    1990-01-01

    Potential resources and applications of earth heat in the form of geothermal energy are large. United States direct uses amount to 2,100 MWt thermal and worldwide 8,850 MWt above a reference temperature of 35 degrees Celsius. Space and district heating are the major direct uses of geothermal energy. Equipment employed in direct use projects is of standard manufacture and includes downhole and circulation pumps, transmission and distribution pipelines, heat exchangers and convectors, heat pumps and chillers. Direct uses of earth heat discussed are space and district heating, greenhouse heating and fish farming, process and industrial applications. The economic feasibility of direct use projects is governed by site specific factors such as location of user and resource, resource quality, system load factor and load density, as well as financing. Examples are presented of district heating in Klamath Falls, and Elko. Further developments of direct uses of geothermal energy will depend on matching user needs to the resource, and improving load factors and load density.

  6. Template-directed synthesis of linear porphyrin oligomers: classical, Vernier and mutual Vernier† †Electronic supplementary information (ESI) available: Synthesis and characterization of new compounds, ladder complexes, UV-vis-NIR titrations and binding data for reference compounds and for the formation of linear oligomer complexes, calculation of effective molarities, analytical GPC calibration and molar absorption coefficients. See DOI: 10.1039/c6sc05355f Click here for additional data file.

    Science.gov (United States)

    Kamonsutthipaijit, Nuntaporn

    2017-01-01

    Three different types of template-directed syntheses of linear porphyrin oligomers are presented. In the classical approach the product has the same number of binding sites as the template, whereas in Vernier reactions the product has the lowest common multiple of the numbers of binding sites in the template and the building block. Mutual Vernier templating is like Vernier templating except that both strands of the Vernier complex undergo coupling simultaneously, so that it becomes impossible to say which is the ‘template’ and which is the ‘building block’. The template-directed synthesis of monodisperse linear oligomers is more difficult than that of cyclic oligomers, because the products of linear templating have reactive ends. All three types of templating are demonstrated here, and used to prepare a nickel(ii) porphyrin dodecamer with 4-pyridyl substituents on all twelve porphyrin units. The stabilities and cooperativities of the double-strand complexes involved in these reactions were investigated by UV-vis-NIR titration. The four-rung ladder duplex has a stability constant of about 2 × 1018 M–1 in dichloromethane at 298 K. PMID:28553508

  7. Recent advances in microwave initiated synthesis of nanocarbon materials

    Science.gov (United States)

    Zhang, Xinyu; Liu, Zhen

    2012-01-01

    This Feature Article focuses on the recent advances in synthesis of nanostructured carbon materials using microwave irradiation as the heating source. Although the microwave approach to chemical synthesis is relatively mature in organic synthesis, it is still in the early stage for nanomaterials synthesis, especially nanocarbons. Due to the energy efficient nature of microwave heating, there is a great opportunity to apply microwave irradiation to nanocarbon production, which normally requires high temperature, high vacuum or inert gas protections. Using microwave irradiation will give a green feature to the nanocarbon synthesis, since it offers high efficiency heating and fast carbonization. With our recent discovery, multi-walled carbon nanotubes can be synthesized through the microwave process even in air. Background about nanocarbons and microwave chemistry are introduced, the application of microwaves in synthesis of different types of nanocarbons is discussed and finally, the perspectives in the future research directions of microwave assisted nanocarbon synthesis are deliberated as well.

  8. Direct marketing

    Directory of Open Access Journals (Sweden)

    Čičić Muris

    2002-01-01

    Full Text Available Direct Marketing (DM is usually treated as unworthy activity, with actions at the edge of legality and activities minded cheating. Despite obvious problems regarding ethics and privacy threat, DM with its size, importance and role in a concept of integrated marketing communication deserves respect and sufficient analysis and review

  9. Environment and hydroelectricity colloquium - Synthesis

    International Nuclear Information System (INIS)

    Aelbrecht, Denis; Abadie, Marc; Baril, Dominique; Delacoux, Jean-Yves; Delaunay, Alexis; Loudiere, Daniel; Penalba, Anne; Pont, Didier; Rocq, Sylvie; Roult, Didier; Sheibani, Neda; Thevenet, Regis; Weisrock, Ghislain

    2010-10-01

    This document proposes a synthesis of a colloquium dedicated to the interactions between hydroelectric installations and the environment. The four sessions respectively addressed the impacts of hydroelectric installations on ecosystems and more particularly on pisciculture populations (strategies for migration restoration, development of fish-friendly turbines), the sedimentary management of hydroelectric installations, the implementation of the Water Framework European Directive (Austrian experience, biological assessment criteria), and examples of environmental integration of existing or projected installations

  10. Direct ELISA.

    Science.gov (United States)

    Lin, Alice V

    2015-01-01

    First described by Engvall and Perlmann, the enzyme-linked immunosorbent assay (ELISA) is a rapid and sensitive method for detection and quantitation of an antigen using an enzyme-labeled antibody. Besides routine laboratory usage, ELISA has been utilized in medical field and food industry as diagnostic and quality control tools. Traditionally performed in 96-well or 384-well polystyrene plates, the technology has expanded to other platforms with increase in automation. Depending on the antigen epitope and availability of specific antibody, there are variations in ELISA setup. The four basic formats are direct, indirect, sandwich, and competitive ELISAs. Direct ELISA is the simplest format requiring an antigen and an enzyme-conjugated antibody specific to the antigen. This chapter describes the individual steps for detection of a plate-bound antigen using a horseradish peroxidase (HRP)-conjugated antibody and luminol-based enhanced chemiluminescence (ECL) substrate. The methodological approach to optimize the assay by chessboard titration is also provided.

  11. Electrostatic immobilisation of copper(I) and copper(II) bis(oxazolinyl)pyridine catalysts on silica: application to the synthesis of propargylamines via direct addition of terminal alkynes to imines

    NARCIS (Netherlands)

    McDonagh, C.; O'Conghaile, P.; Klein Gebbink, R.J.M.; O'Leary, P.F.

    2007-01-01

    Copper(I) and copper(II) complexes of two bis(oxazolinyl)pyridines were immobilized on silica via electrostatic interactions. The catalytic activity of the immobilized catalysts in the direct addition of terminal alkynes to imines leading to propargylamines was investigated under a variety of

  12. Microemulsion Synthesis of Nanoparticles

    Directory of Open Access Journals (Sweden)

    Gotić, M.

    2013-11-01

    Full Text Available Nanoparticles and nanomaterials have wide applications in electronics, physics, material design, being also utilized as sensors, catalysts, and more and more in biomedicine. Microemulsions are an exceptionally suitable medium for the synthesis of nanoparticles due to their thermodynamical stability, great solubility of both polar and nonpolar components, as well as their ability to control the size, dispersity and shape of the particles. This review presents microemulsion techniques for the synthesis of inorganic nanoparticles. It takes place in water-in-oil microemulsions by mixing one microemulsion with a cationic precursor, and the other with a precipitating or reducing agent, or by direct addition of reducing agents or gas (O2, NH3 ili CO2 into microemul sion (Fig. 1. Metal nanoparticles are used as catalysts, sensors, ferrofluids etc. They are produced by reducing the metal cation with a suitable reducing agent. In a similar way, one can prepare nanoparticles of alloys from the metal salts, provided that the metals are mutually soluble. The microemulsion technique is also suitable for depositing nanoparticles onto various surfaces. Highly active catalysts made from nanoparticles of Pt, Pd, Rh and other noble metals may be obtained in this way. Metal oxides and hydroxides may be prepared by hydrolysis or precipitation in the water core of microemulsion. Precipitation can be initiated by adding the base or precipitating agent into the microemulsion with water solution of metal ions. Similarly, nanoparticles may be prepared of sulphides, halogenides, cyanides, carbonates, sulphates and other insoluble metal salts. To prevent oxidation of nanoparticles, especially Fe, the particles are coated with inert metals, oxides, various polymers etc. Coating may provide additional functionality; e.g. coating with gold allows subsequent functionalization with organic compounds containing sulphur, due to the strong Au–S bond. Polymer coatings decrease

  13. Influence of synthesis conditions on particle morphology of ...

    Indian Academy of Sciences (India)

    Wintec

    cyclohexanol (Fridman et al 2004) and liquid phase direct oxidation of benzene to phenol (Kanzaki et al 2004). Best known usage of these catalysts is, perhaps, the synthesis of methanol from synthesis gas. A number of chemical and physical ... Solution based synthetic strategies like polyol process offer several important ...

  14. Sustainable DME synthesis-design with CO2 utilization

    DEFF Research Database (Denmark)

    Prasertsri, Weeranut; Frauzem, Rebecca; Suriyapraphadilok, Uthaiporn

    2016-01-01

    : (A) dry reforming step, methanol synthesis step, and methanol dehydration step; (B) CO2 hydrogenation step followed by methanol dehydration step; and (C) dry reforming step followed by direct DME synthesis step. Starting with a base-case design, the process flow sheets for the three routes...

  15. Neurotensin enhances estradiol induced DNA synthesis in immature rat uterus

    Energy Technology Data Exchange (ETDEWEB)

    Mistry, A.; Vijayan, E.

    1985-05-27

    Systemic administration of Neurotensin, a tridecapeptide, in immature rats treated with estradiol benzoate significantly enhances uterine DNA synthesis as reflected by the incorporation of /sup 3/H-thymidine. The peptide may have a direct action on the uterus. Substance P, a related peptide, had no effect on uterine DNA synthesis. 18 references, 4 tables.

  16. Phytochelatin synthesis in tomato cells

    International Nuclear Information System (INIS)

    Goldsbrough, P.; Gupta, S.; Huang, B.; Scheller, H.

    1987-01-01

    Tomato cells that are exposed to cadmium and other heavy metals synthesize phytochelatins (PCs), a family of peptides that bind heavy metals and are structurally related to glutathione (GSH). PCs have the structure (γ-glutamyl-cysteinyl) glycine; for PCs, n=2-10; GSH, n=1. GSH levels decline rapidly in tomato cells exposed to Cd 2+ . Buthionine sulfoximine (BSO), an inhibitor of GSH synthesis, prevents sustained synthesis of PC. However the addition of GSH to the medium of BSO-treated cells restores PC production. In vivo labeling studies indicate that 35 [S]-cysteine is incorporated into PC via GSH, rather than being added directly to GSH or pre-formed PC. Initial synthesis of PCs is not inhibited by cycloheximide. Tomato cell cultures that are tolerant of high levels of Cd 2+ contain large amounts of PCs. However, when sensitive and tolerant cells that have been grown in the absence of Cd 2+ are exposed to relatively low concentrations of Cd 2+ , they synthesize PCs at similar rates. These and other results suggest that, although PCs are necessary, increased PC synthesis is not sufficient for expression of the Cd 2+ tolerant phenotype

  17. Promising Practices and Programs: Current Efforts and Future Directions

    Science.gov (United States)

    Crisp, Gloria

    2016-01-01

    The final chapter of the issue provides a synthesis of the first eight chapters, offers conclusions and recommendations, and considers future directions regarding practices and programs with promise for high impact at community colleges around the country.

  18. Nickel-Catalyzed Diaryl Ketone Synthesis by N-C Cleavage: Direct Negishi Cross-Coupling of Primary Amides by Site-Selective N,N-Di-Boc Activation.

    Science.gov (United States)

    Shi, Shicheng; Szostak, Michal

    2016-11-18

    A general Negishi acylation of primary amides enabled by a combination of site-selective N,N-di-Boc activation and nickel catalysis is reported for the first time. The reaction is promoted by a bench-stable, inexpensive Ni catalyst. The reaction shows excellent functional group compatibility, affording functionalized diaryl ketones by selective N-C cleavage. Most notably, this protocol represents the first amide cross-coupling by direct metal insertion of simple and readily available primary amides. The overall strategy by N,N-di-Boc activation/metal insertion is suitable for a broad range of coupling protocols via acylmetals. Mechanistic experiments suggest high reactivity of N,N-di-Boc activated 1° amides in direct amide C-N cross-couplings.

  19. Synthesis Report

    DEFF Research Database (Denmark)

    Attila, Károly; Gács, János; Hunya, Gabor

    From the beginning of transition in 1989/90, the CEECs switched towards an ‘open economy’ model of economic development, and the evolving patterns of trade, industrial specialization and integration into cross-border production networks through foreign direct investment (FDI) have played a crucia...

  20. Total synthesis of ciguatoxin.

    Science.gov (United States)

    Hamajima, Akinari; Isobe, Minoru

    2009-01-01

    Something fishy: Ciguatoxin (see structure) is one of the principal toxins involved in ciguatera poisoning and the target of a total synthesis involving the coupling of three segments. The key transformations in this synthesis feature acetylene-dicobalthexacarbonyl complexation.

  1. Synthesis of novel azaxanthones derived from N-hydroxyazoles

    DEFF Research Database (Denmark)

    Kristensen, Jesper Langgaard; Vedsø, P.; Begtrup, M.

    2002-01-01

    The synthesis of a new class of azaxanthones is presented. The N-O functionality of 1-hydroxypyrazole and 1-hydroxy-1,2,3-triazole was used to direct metalation and subsequently in the new ring systems....

  2. Palladium-Catalyzed Synthesis of N-Aryl Carbamates

    Science.gov (United States)

    Vinogradova, Ekaterina V.; Park, Nathaniel H.; Fors, Brett P.; Buchwald, Stephen L.

    2013-01-01

    An efficient synthesis of aryl carbamates was achieved by introducing alcohols into the reaction of palladium-catalyzed cross-coupling of ArX (X = Cl, OTf) with sodium cyanate. The use of aryl triflates as electrophilic components in this transformation allowed for an expanded substrate scope for direct synthesis of aryl isocyanates. This methodology provides direct access to major carbamate protecting groups, S-thiocarbamates, and diisocyanate precursors to polyurethane materials. PMID:23441814

  3. Synthesis of novel azaxanthones derived from N-hydroxyazoles

    DEFF Research Database (Denmark)

    Kristensen, Jesper Langgaard; Vedsø, P.; Begtrup, M.

    2002-01-01

    The synthesis of a new class of azaxanthones is presented. The N-O functionality of 1-hydroxypyrazole and 1-hydroxy-1,2,3-triazole was used to direct metalation and subsequently in the new ring systems.......The synthesis of a new class of azaxanthones is presented. The N-O functionality of 1-hydroxypyrazole and 1-hydroxy-1,2,3-triazole was used to direct metalation and subsequently in the new ring systems....

  4. Synthesis and characterization of Pt-Sn-Ni alloys to application as catalysts for direct ethanol fuel cells; Sintese e caracterizacao de ligas de Pt-Sn-Ni para aplicacao como caztalisadores em celulas a combustivel do tipo DEFC

    Energy Technology Data Exchange (ETDEWEB)

    Silva, E.L. da; Correa, P.S.; Oliveira, E.L. de; Takimi, A.S.; Malfatti, C.F., E-mail: celia.malfatti@ufrgs.b [Universidade Federal do Rio Grande do Sul (LAPEC/UFRGS), Porto Alegre, RS (Brazil). Programa de Pos-Graduacao em Engenharia Mecanica. Lab. de Pesquisa em Corrosao; Radtke, C. [Universidade Federal do Rio Grande do Sul (IQ/UFRGS), Porto Alegre, RS (Brazil). Inst. de Quimica

    2010-07-01

    Direct ethanol fuel cells (DEFCs) have been the focus of recent research due its application in mobile energy sources. In order to obtain the maximum efficiency from these systems, it is necessary the total ethanol oxidation, which implies in C-C bond break. Different catalysts described in literature are employed with this intent. This work consists in studying PtSnNi catalysts supported on carbon Vulcan XC72R, to application in DEFCs. Thus, it was used the impregnation/reduction method, varying the atomic proportion among Pt, Sn and Ni. The alloys were characterized by X-Ray Diffraction, Cyclic Voltammetry and Transmission Microscopy. Preliminary results show that predominant structure on the catalysts is the face centered cubic platinum and the densities currents are dependent on the platinum amount. (author)

  5. Highly regioselective synthesis of 3-alkenyl-oxindole ring-fused 3,3'-disubstituted oxindoles via direct gamma-substitution of Morita-Baylis-Hillman carbonates of isatins with 3-substituted oxindoles.

    Science.gov (United States)

    Feng, Ting-Ting; Huang, Xuan; Liu, Xiong-Li; Jing, De-Hong; Liu, Xiong-Wei; Guo, Feng-Ming; Zhou, Ying; Yuan, Wei-Cheng

    2014-12-14

    The first phase transfer-catalysed direct γ-substitution of Morita-Baylis-Hillman carbonates of isatins with 3-substituted oxindoles has been developed, which affords 3-alkenyl-oxindole ring-fused 3,3'-disubstituted oxindoles in up to 83% yield under mild reaction conditions. Furthermore, their biological activity has been preliminarily demonstrated by in vitro evaluation against human prostate cancer cells PC-3 and human leukemia cells K562, using MTT-based assays with the commercially available standard drug Cisplatin as a positive control. Gratifyingly, compounds 3aa, 3ba and 3ca exhibited comparable in vitro inhibitory activities against human prostate cancer cells (PC-3) to Cisplatin. What's more, 3ba also had a good inhibition ability against human leukemia cells K562. These results indicate that 3-alkenyl-oxindole ring-fused 3,3'-disubstituted oxindole analogs may be potential lead compounds for further biological screening.

  6. Electrifying Organic Synthesis.

    Science.gov (United States)

    Wiebe, Anton; Gieshoff, Tile; Möhle, Sabine; Rodrigo, Eduardo; Zirbes, Michael; Waldvogel, Siegfried R

    2018-01-02

    The direct synthetic organic use of electricity is currently experiencing a renaissance. More synthetically oriented laboratories working in this area are exploiting both novel and more traditional concepts, paving the way to broader applications of this niche technology. As only electrons serve as reagents, the generation of reagent waste is efficiently avoided. Moreover, stoichiometric reagents can be regenerated and allow a transformation to be conducted in an electrocatalytic fashion. However, the application of electroorganic transformations is more than minimizing the waste footprint, it rather gives rise to inherently safe processes, reduces the number of steps of many syntheses, allows for milder reaction conditions, provides alternative means to access desired structural entities, and creates intellectual property (IP) space. When the electricity originates from renewable resources, this surplus might be directly employed as a terminal oxidizing or reducing agent, providing an ultra-sustainable and therefore highly attractive technique. This Review surveys recent developments in electrochemical synthesis that will influence the future of this area. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  7. Speech Synthesis Applied to Language Teaching.

    Science.gov (United States)

    Sherwood, Bruce

    1981-01-01

    The experimental addition of speech output to computer-based Esperanto lessons using speech synthesized from text is described. Because of Esperanto's phonetic spelling and simple rhythm, it is particularly easy to describe the mechanisms of Esperanto synthesis. Attention is directed to how the text-to-speech conversion is performed and the ways…

  8. Ammonia synthesis from first principles calculations

    DEFF Research Database (Denmark)

    Honkala, Johanna Karoliina; Hellman, Anders; Remediakis, Ioannis

    2005-01-01

    The rate of ammonia synthesis over a nanoparticle ruthenium catalyst can be calculated directly on the basis of a quantum chemical treatment of the problem using density functional theory. We compared the results to measured rates over a ruthenium catalyst supported on magnesium aluminum spinet...

  9. The Interpretation of Cholesterol Balance Derived Synthesis Data and Surrogate Noncholesterol Plasma Markers for Cholesterol Synthesis under Lipid Lowering Therapies

    Directory of Open Access Journals (Sweden)

    Frans Stellaard

    2017-01-01

    Full Text Available The cholesterol balance procedure allows the calculation of cholesterol synthesis based on the assumption that loss of endogenous cholesterol via fecal excretion and bile acid synthesis is compensated by de novo synthesis. Under ezetimibe therapy hepatic cholesterol is diminished which can be compensated by hepatic de novo synthesis and hepatic extraction of plasma cholesterol. The plasma lathosterol concentration corrected for total cholesterol concentration (R_Lath as a marker of de novo cholesterol synthesis is increased during ezetimibe treatment but unchanged under treatment with ezetimibe and simvastatin. Cholesterol balance derived synthesis data increase during both therapies. We hypothesize the following. (1 The cholesterol balance data must be applied to the hepatobiliary cholesterol pool. (2 The calculated cholesterol synthesis value is the sum of hepatic de novo synthesis and the net plasma—liver cholesterol exchange rate. (3 The reduced rate of biliary cholesterol absorption is the major trigger for the regulation of hepatic cholesterol metabolism under ezetimibe treatment. Supportive experimental and literature data are presented that describe changes of cholesterol fluxes under ezetimibe, statin, and combined treatments in omnivores and vegans, link plasma R_Lath to liver function, and define hepatic de novo synthesis as target for regulation of synthesis. An ezetimibe dependent direct hepatic drug effect cannot be excluded.

  10. Stereodivergent synthesis with a programmable molecular machine

    Science.gov (United States)

    Kassem, Salma; Lee, Alan T. L.; Leigh, David A.; Marcos, Vanesa; Palmer, Leoni I.; Pisano, Simone

    2017-09-01

    It has been convincingly argued that molecular machines that manipulate individual atoms, or highly reactive clusters of atoms, with Ångström precision are unlikely to be realized. However, biological molecular machines routinely position rather less reactive substrates in order to direct chemical reaction sequences, from sequence-specific synthesis by the ribosome to polyketide synthases, where tethered molecules are passed from active site to active site in multi-enzyme complexes. Artificial molecular machines have been developed for tasks that include sequence-specific oligomer synthesis and the switching of product chirality, a photo-responsive host molecule has been described that is able to mechanically twist a bound molecular guest, and molecular fragments have been selectively transported in either direction between sites on a molecular platform through a ratchet mechanism. Here we detail an artificial molecular machine that moves a substrate between different activating sites to achieve different product outcomes from chemical synthesis. This molecular robot can be programmed to stereoselectively produce, in a sequential one-pot operation, an excess of any one of four possible diastereoisomers from the addition of a thiol and an alkene to an α,β-unsaturated aldehyde in a tandem reaction process. The stereodivergent synthesis includes diastereoisomers that cannot be selectively synthesized through conventional iminium-enamine organocatalysis. We anticipate that future generations of programmable molecular machines may have significant roles in chemical synthesis and molecular manufacturing.

  11. Direct synthesis of cis-dihalido-bis(NHC) complex of nickel(II) and catalytic application in olefin addition polymerization: effect of halogen co-ligands and density functional theory study.

    Science.gov (United States)

    Zhang, Dao; Zhou, Sen; Li, Zhiming; Wang, Quanrui; Weng, Linhong

    2013-09-07

    Two novel amine-containing N-heterocyclic carbene ligand precursors [H(1a-b)]Br have been prepared in good yield and fully characterized. Direct syntheses of cis- and trans-dihalido-bis(NHC) nickel complexes [Ni(NHC)2X2] (X = Cl, Br) are reported. The solid structures of trans-[Ni(1a-b)2Br2] (2a-b) and cis-[Ni(1a)2Cl2] (3) were determined by single-crystal X-ray analysis and 3 was found to be the first example of cis-configuration coordination of monodentate NHC ligands to a metal center for dihalido-bis(NHC) nickel complexes. DFT calculations were conducted to determine the energy difference between cis- and trans-isomers of complexes 2a and 3 bearing bromide and chloride co-ligands. The cis-[Ni(1a)2Cl2] (cis-3) is 1.77-1.55 kcal mol(-1) lower in energy than its trans-isomer in polar solvents including CH2Cl2 and THF, while the trans-[Ni(1a)2Br2] (trans-2a) is more stable than the cis-isomer similarly in the gas phase. The cis nickel complex 3 with two coordinated monodentate NHCs was tested for olefin addition polymerization at standard conditions. It was found that cis-3 was inactive in ethylene polymerization but showed moderate catalytic activities (0.5-3.0 × 10(6) g of PNB (mol of Ni)(-1) h(-1)) in the addition polymerization of norbornene in the presence of methylaluminoxane (MAO) as cocatalyst.

  12. Synthesis and properties of optically active nanostructured polymers bearing amino acid moieties by direct polycondensation of 4,4'-thiobis(2-tert-butyl-5-methylphenol) with chiral diacids.

    Science.gov (United States)

    Mallakpour, Shadpour; Soltanian, Samaneh

    2012-06-01

    Four derivatives of N-trimellitylimido-L-amino acid (4a-4d) were prepared by the reaction of trimellitic anhydride (1) with the L-amino acids (2a-2d) in acetic acid as diacid monomers and were used with the aim to obtain a new family of amino acid based poly(ester-imide)s (PEI)s. The polymerization was performed by direct polycondensation of chiral diacids (4a-4d) with 4,4'-thiobis(2-tert-butyl-5-methylphenol) (5) in the presence of tosyl chloride (TsCl), pyridine and N,N-dimethyl formamide (DMF). Step-growth polymerization was carried out by varying the time of heating and the molar ratio of TsCl/diacid and the optimum conditions were achieved. The synthesized polymers were characterized by means of specific rotation experiments, FT-IR, 1H-NMR, X-ray diffraction techniques and elemental analysis. The surface morphology of the obtained polymers was studied by field emission scanning electron microscopy. The result showed nanostructure morphology of the resulting polymers. The obtained PEIs were soluble in polar aprotic solvents such as DMF, N,N-dimethyl acetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and protic solvents such as sulfuric acid. Thermal stability and the weight-loss behavior of the PEIs were studied by thermal gravimetric analysis (TGA) techniques. TGA showed that the 10% weight loss temperature in a nitrogen atmosphere was more than 402°C, therefore they had useful levels of thermal stability associated with excellent solubility.

  13. Directed synthesis of a heterobimetallic complex based on a novel unsymmetric double-Schiff-base ligand: preparation, characterization, reactivity and structures of hetero- and homobimetallic nickel(II) and zinc(II) complexes.

    Science.gov (United States)

    Roth, Arne; Buchholz, Axel; Rudolph, Manfred; Schütze, Eileen; Kothe, Erika; Plass, Winfried

    2008-01-01

    A series of bimetallic zinc(II) and nickel(II) complexes based on the novel dinucleating unsymmetric double-Schiff-base ligand benzoic acid [1-(3-{[2-(bispyridin-2-ylmethylamino)ethylimino]methyl}-2-hydroxy-5-methylphenyl)methylidene]hydrazide (H(2)bpampbh) has been synthesized and structurally characterized. The metal centers reside in two entirely different binding pockets provided by the ligand H(2)bpampbh, a planar tridentate [ONO] and a pentadentate [ON(4)] compartment. The utilized ligand H(2)bpampbh has been synthesized by condensation of the single-Schiff-base proligand Hbpahmb with benzoic acid hydrazide. The reaction of H(2)bpampbh with two equivalents of either zinc(II) or nickel(II) acetate yields the homobimetallic complexes [Zn(2)(bpampbh)(mu,eta(1)-OAc)(eta(1)-OAc)] (ZnZn) and [Ni(2)(bpampbh)(mu-H(2)O)(eta(1)-OAc)(H(2)O)](OAc) (NiNi), respectively. Simultaneous presence of one equivalent zinc(II) and one equivalent nickel(II) acetate results in the directed formation of the heterobimetallic complex [NiZn(bpampbh)(mu,eta(1)-OAc)(eta(1)-OAc)] (NiZn) with a selective binding of the nickel ions in the pentadentate ligand compartment. In addition, two homobimetallic azide-bridged complexes [Ni(2)(bpampbh)(mu,eta(1)-N(3))]ClO(4) (NiNi(N(3))) and [Ni(2)(bpampbh)(mu,eta(1)-N(3))(MeOH)(2)](ClO(4))(0.5)(N(3))(0.5) (NiNi(N(3))(MeOH)(2)) were synthesized. In all complexes, the metal ions residing in the pentadentate compartment adopt a distorted octahedral coordination geometry, whereas the metal centers placed in the tridentate compartment vary in coordination number and geometry from square-planar (NiNi(N(3))) and square-pyramidal (ZnZn and NiZn), to octahedral (NiNi and NiNi(N(3))(MeOH)(2)). In the case of complex NiNi(N(3)) this leads to a mixed-spin homodinuclear nickel(II) complex. All compounds have been characterized by means of mass spectrometry as well as IR and UV/Vis spectroscopies. Magnetic susceptibility measurements show significant zero

  14. Diamond synthesis by lasers: recent progress

    Directory of Open Access Journals (Sweden)

    Gordana S. Ristić

    2012-01-01

    Full Text Available This paper provides an up-to-date critical review of methods for diamond synthesis by lasers. A provisional classification of synthesizing methods is carried out, in order to present a varied and heterogeneous experimental work that is as clear as possible. Laser diamond CVD methods involve chemical processes in a carbon-containing system induced by specific absorption of laser radiation, while diamond PVD methods involve physical processes induced by an intense, highly-directed laser beam. Different methods involving coupled, simultaneous action of lasers and classic CVD agents are suggested and discussed as prospective approaches for diamond synthesis.

  15. Biomimetic and Bioinspired Synthesis of Nanomaterials/Nanostructures.

    Science.gov (United States)

    Zan, Guangtao; Wu, Qingsheng

    2016-03-16

    In recent years, due to its unparalleled advantages, the biomimetic and bioinspired synthesis of nanomaterials/nanostructures has drawn increasing interest and attention. Generally, biomimetic synthesis can be conducted either by mimicking the functions of natural materials/structures or by mimicking the biological processes that organisms employ to produce substances or materials. Biomimetic synthesis is therefore divided here into "functional biomimetic synthesis" and "process biomimetic synthesis". Process biomimetic synthesis is the focus of this review. First, the above two terms are defined and their relationship is discussed. Next different levels of biological processes that can be used for process biomimetic synthesis are compiled. Then the current progress of process biomimetic synthesis is systematically summarized and reviewed from the following five perspectives: i) elementary biomimetic system via biomass templates, ii) high-level biomimetic system via soft/hard-combined films, iii) intelligent biomimetic systems via liquid membranes, iv) living-organism biomimetic systems, and v) macromolecular bioinspired systems. Moreover, for these five biomimetic systems, the synthesis procedures, basic principles, and relationships are discussed, and the challenges that are encountered and directions for further development are considered. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Synthesis of Mechanisms

    DEFF Research Database (Denmark)

    Hansen, John Michael

    1999-01-01

    These notes describe an automated procedure for analysis and synthesis of mechanisms. The analysis method is based on the body coordinate formulation, and the synthesis is based on applying optimization methods, used to minimize the difference between an actual and a desired behaviour......These notes describe an automated procedure for analysis and synthesis of mechanisms. The analysis method is based on the body coordinate formulation, and the synthesis is based on applying optimization methods, used to minimize the difference between an actual and a desired behaviour...

  17. Automatic Quality Measurement and Parameter Selection for Example-based Texture Synthesis

    DEFF Research Database (Denmark)

    Laursen, Lasse Farnung; Clemmensen, Line Katrine Harder; Bærentzen, Jakob Andreas

    synthesis compares to the original input. A good similarity measure will enable the search for the optimal texture synthesis parameters by maximizing the quality of the synthesis as a function of parameters. We apply presented methods to a state of the art texture synthesis algorithm, namely the one...... cover research to directly estimate specific texture synthesis parameters, such as patch size and iteration convergence, based on input textures. We also examine various similarity measures and evaluate their effectiveness. The goal for each measure is to properly evaluate how well the resulting...

  18. Total Synthesis of Avrainvilleol.

    Science.gov (United States)

    Wegener, Aaron; Miller, Kenneth A

    2017-11-03

    The first total synthesis of the marine natural product avrainvilleol is reported. The total synthesis features the first application of the transition-metal-free coupling of a tosyl hydrazone and a boronic acid to the preparation of a complex natural product, and the first example of this coupling with a hindered diortho substituted hydrazone substrate.

  19. Difluoromethylenephosphonates: synthesis and transformations

    International Nuclear Information System (INIS)

    Chunikhin, Konstantin S; Kadyrov, A A; Pasternak, P V; Chkanikov, Nikolai D

    2010-01-01

    The data on the synthesis of organic compounds containing the difluoromethylenephosphonate group are analyzed and generalized. The attention is focused on the introduction of this group into various organic molecules and subsequent transformations of the compounds thus formed. Individual sections are devoted to the synthesis of heterocyclic compounds and analogues of natural substances containing difluoromethylenephosphonate groups.

  20. Synthesis of Isoiminosugars

    DEFF Research Database (Denmark)

    Hyldtoft, Lene; Godskesen, Michael Anders; Lundt, Inge

    1998-01-01

    A short synthesis of isoiminosugars have been developed. Bromolactones are diastereoselectively alkylated at C-2 followed by ring closure to the corresponding lactams. Reduction of these then gives isoiminosugars......A short synthesis of isoiminosugars have been developed. Bromolactones are diastereoselectively alkylated at C-2 followed by ring closure to the corresponding lactams. Reduction of these then gives isoiminosugars...

  1. Synthesis of oligonucleotide phosphorodithioates

    DEFF Research Database (Denmark)

    Beaton, G.; Brill, W. K D; Grandas, A.

    1991-01-01

    The synthesis of DNA containing sulfur at the two nonbonding internucleotide valencies is reported. Several different routes using either tervalent or pentavalent mononucleotide synthons are described.......The synthesis of DNA containing sulfur at the two nonbonding internucleotide valencies is reported. Several different routes using either tervalent or pentavalent mononucleotide synthons are described....

  2. Microwave mediated synthesis of semiconductor quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Afrasiabi, Roodabeh; Sugunan, Abhilash; Shahid, Robina; Toprak, Muhammet S.; Muhammed, Mamoun [Division of Functional Materials, Royal Institute of Technology (KTH), Stockholm (Sweden)

    2012-07-15

    Colloidal quantum dots (QD) have tuneable optoelectronic properties and can be easily handled by simple solution processing techniques, making them very attractive for a wide range of applications. Over the past decade synthesis of morphology controlled high quality (crystalline, monodisperse) colloidal QDs by thermal decomposition of organometallic precursors has matured and is well studied. Recently, synthesis of colloidal QDs by microwave irradiation as heating source is being studied due to the inherently different mechanisms of heat transfer, when compared to solvent convection based heating. Under microwave irradiation, polar precursor molecules directly absorb the microwave energy and heat up more efficiently. Here we report synthesis of colloidal II-VI semiconductor QDs (CdS, CdSe, CdTe) by microwave irradiation and compare it with conventional synthesis based on convection heating. Our findings show that QD synthesis by microwave heating is more efficient and the chalcogenide precursor strongly absorbs the microwave radiation shortening the reaction time and giving a high reaction yield (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  3. Gold nanocrystals with DNA-directed morphologies.

    Science.gov (United States)

    Ma, Xingyi; Huh, June; Park, Wounjhang; Lee, Luke P; Kwon, Young Jik; Sim, Sang Jun

    2016-09-16

    Precise control over the structure of metal nanomaterials is important for developing advanced nanobiotechnology. Assembly methods of nanoparticles into structured blocks have been widely demonstrated recently. However, synthesis of nanocrystals with controlled, three-dimensional structures remains challenging. Here we show a directed crystallization of gold by a single DNA molecular regulator in a sequence-independent manner and its applications in three-dimensional topological controls of crystalline nanostructures. We anchor DNA onto gold nanoseed with various alignments to form gold nanocrystals with defined topologies. Some topologies are asymmetric including pushpin-, star- and biconcave disk-like structures, as well as more complex jellyfish- and flower-like structures. The approach of employing DNA enables the solution-based synthesis of nanocrystals with controlled, three-dimensional structures in a desired direction, and expands the current tools available for designing and synthesizing feature-rich nanomaterials for future translational biotechnology.

  4. VHDL for logic synthesis

    CERN Document Server

    Rushton, Andrew

    2011-01-01

    Many engineers encountering VHDL (very high speed integrated circuits hardware description language) for the first time can feel overwhelmed by it. This book bridges the gap between the VHDL language and the hardware that results from logic synthesis with clear organisation, progressing from the basics of combinational logic, types, and operators; through special structures such as tristate buses, register banks and memories, to advanced themes such as developing your own packages, writing test benches and using the full range of synthesis types. This third edition has been substantially rewritten to include the new VHDL-2008 features that enable synthesis of fixed-point and floating-point hardware. Extensively updated throughout to reflect modern logic synthesis usage, it also contains a complete case study to demonstrate the updated features. Features to this edition include: * a common VHDL subset which will work across a range of different synthesis systems, targeting a very wide range of technologies...

  5. Direct synthesis of acetylketene N,S-acetals with benzoylcyanamide

    International Nuclear Information System (INIS)

    Kolomnikova, G.D.; Sorokin, P.V.; Chizhevskij, I.T.; Petrovskij, P.V.; Bregadze, V.I.; Dolgushin, F.M.; Yanovskij, A.I.

    1997-01-01

    The reaction of the OsCl 2 (PPh 3 ) 3 with K + -salts of the [nido-7,8-R 2 -7,8-C 2 B 9 H 10 ] - afforded novel exo-nido-osmacarborane complexes, exo-nido-5,6,10-[Cl(PPh 3 ) 2 Os]-5,6,1-μ-(H) 3 -10-H-7,8-R 2 C 2 B 9 H 6 (2, R = H; 3, R = Me) in 78 and 85% yields, respectively. Complex 2 is transformed quantitatively in to know closo-3-Cl-3-H-3,3-(PPh 3 ) 2 -3,1,2-OsC 2 B 9 H 11 upon heating in benzene. The structure of exo-nido-osmacarboranes have been confirmed by 1 H and 31 P NMR spectral data and by single crystal X-ray diffraction study of 3

  6. Nickel-catalyzed direct synthesis of dialkoxymethane ethers

    Indian Academy of Sciences (India)

    MURUGAN SUBARAMANIAN

    1997 5-Aminocoumarans: Dual Inhibitors of Lipid Per- oxidation and Dopamine Release with Protective Effects. Against Central Nervous System Trauma and Ischemia. J. Med. Chem. 40 559; (c) Esteki M and Khayamian T. 2008 Mechanistic-based Descriptors for QSAR Study of. Psychotropic Drug Toxicity Chem. Biol.

  7. Decomposition synthesis strategy directed to FPGA with special MTBDD representation

    Science.gov (United States)

    Opara, Adam; Kubica, Marcin

    2016-12-01

    This paper presents the decompositional techniques to obtain partial logical resource sharing between logical structures associated with the respective single functions belonging to a multioutput function. In the case of the BDD function representation the decomposition is associated with the problem of single or multiple cutting diagram. In the paper, the authors focus on the problem of searching for functions for the joint implementation of the decomposition implemented by multiple cutting of SMTBDD diagrams. During the decomposition process the key is to develop effective methods of splitting and merging MTBDD diagrams. This problem was solved by introducing a new type of diagrams PMTBDD. The effectiveness of the developed methods has been confirmed experimentally.

  8. Conclusions, synthesis, and future directions: understanding sources of population change

    Science.gov (United States)

    Esler, Daniel N.; Flint, Paul L.; Derksen, Dirk V.; Savard, Jean-Pierre L.; Eadie, John M.

    2015-01-01

    The material in this volume reflects the burgeoning interest in sea ducks, both as study species with compelling and unique ecological attributes and as taxa of conservation concern. In this review, we provide perspective on the current state of sea duck knowledge by highlighting key findings in the preceding chapters that are of particular value for understanding or influencing population change. We also introduce a conceptual model that characterizes links among topics covered by individual chapters and places them in the context of demographic responses. Finally, we offer recommendations for areas of future research that we suggest will have importance for understanding and managing sea duck population dynamics.

  9. Nickel-catalyzed direct synthesis of dialkoxymethane ethers

    Indian Academy of Sciences (India)

    oxymethylene ethers) from alcohols and paraformaldehyde in the presence of commercially available nickel(II) salt is described. The reaction proceeds readily under neutral, solvent-free conditions using paraformaldehyde as a C1 source.

  10. Nickel-catalyzed direct synthesis of dialkoxymethane ethers

    Indian Academy of Sciences (India)

    MURUGAN SUBARAMANIAN

    free condition. 1. Introduction. Ethers constitute the most diverse family of organic compounds and are ubiquitous in many natural prod- ucts and pharmaceuticals.1 The extent to which they can be utilized as an organic intermediate in contempo-.

  11. Direct catalytic olefination of alcohols with sulfones.

    Science.gov (United States)

    Srimani, Dipankar; Leitus, Gregory; Ben-David, Yehoshoa; Milstein, David

    2014-10-06

    The synthesis of terminal, as well as internal, olefins was achieved by the one-step olefination of alcohols with sulfones catalyzed by a ruthenium pincer complex. Furthermore, performing the reaction with dimethyl sulfone under mild hydrogen pressure provides a direct route for the replacement of alcohol hydroxy groups by methyl groups in one step. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Patterns of urease synthesis in developing soybeans.

    Science.gov (United States)

    Polacco, J C; Sparks, R B

    1982-07-01

    An examination of in vivo polysome-bound activity indicates that soybean (Glycine max, cv. Prize) seed urease is synthesized on large polysomes (n >/= 15). In vitro urease synthesis is directed by a large RNA (3,000-3,300 nucleotides). Urease synthesis occurs throughout the normal protein biosynthetic phase of the developing seed. Surprisingly, the activity/antigen ratios of urease increase throughout development. Urease appears to be in a more highly polymerized state in mature beans versus beans in early development.During the 55 days from pollination to maturity, urease specific antigen (antigen versus total seed protein) is greatest on the 20th day, representing 0.6% of total extractable protein. Its synthesis proceeds until the end of the protein biosynthetic phase, approximately day 40. In contrast, the appearance of urease enzyme activity lags that of antigen during early development (11-20 days) and plateaus in late development. Mixing experiments suggest no role for putative urease inhibitors or activators during development. However, several electrophoretically slow migrating forms are unique to the urease of mature beans. It is not known if these are more active species.An active urease species exhibits an RNAse-sensitive cosedimentation with a heavy polyribosome class (n >/= 15). Polyadenylated RNA, size-fractionated to 3,000 to 3,300 bases, directed the synthesis in vitro of a major translational product electrophoretically and immunologically similar to the in vivo-synthesized urease subunit.

  13. Synthesis of ferroelectric nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Roervik, Per Martin

    2008-12-15

    respectively BaTi2O5/BaTi5O11 and Na2Ti6O13 for the two different systems, in contradiction to the previous studies. It was shown that NaCl reacted with BaO(PbO) resulting in loss of volatile BaCl2 (PbCl2 ) and formation and preferential growth of titanium oxide-rich nanorods instead of the target phase BaTiO3 (or PbTiO3 ). The molten salt synthesis route may therefore not necessarily yield nanorods of the target ternary oxide as reported previously. In addition, the importance of NaCl(g) for the growth of nanorods below the melting point of NaCl was demonstrated in a special experimental setup, where NaCl and the precursors were physically separated. In Paper II and III, a hydrothermal synthesis method to grow arrays and hierarchical nanostructures of PbTiO3 nanorods and platelets on substrates is presented. Hydrothermal treatment of an amorphous PbTiO3 precursor in the presence of a surfactant and PbTiO3 or SrTiO3 substrates resulted in the growth of PbTiO3 nanorods and platelets aligned in the crystallographic <100> orientations of the SrTiO3 substrates. PbTiO3 nanorods oriented perpendicular to the substrate surface could also be grown directly on the substrate by a modified synthesis method. The hydrothermal method described in Paper II and III was developed on the basis of the method described in Appendices I and II. In Paper IV, a template-assisted method to make PbTiO3 nanotubes is presented. An equimolar Pb-Ti sol was dropped onto porous alumina membranes and penetrated into the channels of the template. Single-phase PbTiO3 perovskite nanotubes were obtained by annealing at 700 degrees Celsius for 6 h. The nanotubes had diameters of 200 - 400 nm with a wall thickness of approximately 20 nm. Excess PbO or annealing in a Pb-containing atmosphere was not necessary in order to achieve single phase PbTiO3 nanotubes. The influence of the heating procedure and the sol concentration is discussed. In Paper V, a piezoresponse force microscopy study of single PbTiO3 nanorods is

  14. Chemoselective Synthesis of Carbamates using CO2 as Carbon Source.

    Science.gov (United States)

    Riemer, Daniel; Hirapara, Pradipbhai; Das, Shoubhik

    2016-08-09

    Synthesis of carbamates directly from amines using CO2 as the carbon source is a straightforward and sustainable approach. Herein, we describe a highly effective and chemoselective methodology for the synthesis of carbamates at room temperature and atmospheric pressure. This methodology can also be applied to protect the amino group in amino acids and peptides, and also to synthesize important pharmaceuticals. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Direct Wittig Olefination of Alcohols.

    Science.gov (United States)

    Li, Qiang-Qiang; Shah, Zaher; Qu, Jian-Ping; Kang, Yan-Biao

    2018-01-05

    A base-promoted transition metal-free approach to substituted alkenes using alcohols under aerobic conditions using air as the inexpensive and clean oxidant is described. Aldehydes are relatively difficult to handle compared to corresponding alcohols due to their volatility and penchant to polymerize and autoxidize. Wittig ylides are easily oxidized to aldehydes and consequently form homo-olefination products. By the strategy of simultaneously in situ generation of ylides and aldehydes, for the first time, alcohols are directly transferred to olefins with no need of prepreparation of either aldehydes or ylides. Thus, the di/monocontrollable olefination of diols is accomplished. This synthetically practical method has been applied in the gram-scale synthesis of pharmaceuticals, such as DMU-212 and resveratrol from alcohols.

  16. Asymmetric synthesis v.4

    CERN Document Server

    Morrison, James

    1984-01-01

    Asymmetric Synthesis, Volume 4: The Chiral Carbon Pool and Chiral Sulfur, Nitrogen, Phosphorus, and Silicon Centers describes the practical methods of obtaining chiral fragments. Divided into five chapters, this book specifically examines initial chiral transmission and extension. The opening chapter describes the so-called chiral carbon pool, the readily available chiral carbon fragments used as building blocks in synthesis. This chapter also provides a list of 375 chiral building blocks, along with their commercial sources, approximate prices, and methods of synthesis. Schemes involving

  17. A Traceless Aryl-Triazene Linker for DNA-Directed Chemistry

    DEFF Research Database (Denmark)

    Hejesen, Christian; Pedersen, Lars Kolster; Gothelf, Kurt Vesterager

    2013-01-01

    DNA-directed synthesis of encoded combinatorial libraries of small organic compounds most often involves transfer of organic building blocks from one DNA strand to another. This requires cleavable linkers to enable cleavage of the link to the original DNA strand from which the building block...... is transferred. Relatively few cleavable linkers are available for DNA-directed synthesis and most often they leave an amino group at the organic molecule. Here we have extended the application of 10 aryltriazenes as traceless linkers for DNA-directed synthesis. After reaction of one building block...

  18. Coupling of glycerol processing with Fischer-Tropsch synthesis for production of liquid fuels

    DEFF Research Database (Denmark)

    Simonetti, D.A.; Rass-Hansen, Jeppe; Kunkes, E.L.

    2007-01-01

    Liquid alkanes can be produced directly from glycerol by an integrated process involving catalytic conversion to H-2/CO gas mixtures (synthesis gas) combined with Fischer-Tropsch synthesis. Synthesis gas can be produced at high rates and selectivities suitable for Fischer-Tropsch synthesis (H-2/CO......, acetone, and acetol. Fischer -Tropsch synthesis experiments at 548 K and 5 bar over a Ru-based catalyst reveal that water, ethanol, and acetone in the synthesis gas feed have only small effects, whereas acetol can participate in Fischer -Tropsch chain growth, forming pentanones, hexanones, and heptanones...... in the liquid organic effluent stream and increasing the selectivity to C5+ alkanes by a factor of 2 ( from 0.30 to 0.60). Catalytic conversion of glycerol and Fischer-Tropsch synthesis were coupled in a two-bed reactor system consisting of a Pt-Re/C catalyst bed followed by a Ru/TiO2 catalyst bed...

  19. Diamond synthesis by lasers: recent progress

    OpenAIRE

    Ristić,Gordana S.; Trtica,Milan S.; Miljanić,Šćepan S.

    2012-01-01

    This paper provides an up-to-date critical review of methods for diamond synthesis by lasers. A provisional classification of synthesizing methods is carried out, in order to present a varied and heterogeneous experimental work that is as clear as possible. Laser diamond CVD methods involve chemical processes in a carbon-containing system induced by specific absorption of laser radiation, while diamond PVD methods involve physical processes induced by an intense, highly-directed laser beam. D...

  20. Organocatalyzed Enantioselective Direct Mannich Reaction of α-Styrylacetates.

    Science.gov (United States)

    Guang, Jie; Rout, Saroj; Bihani, Manisha; Larson, Ariel J; Arman, Hadi D; Zhao, John C-G

    2016-06-03

    An organocatalyzed direct Mannich reaction of unactivated α-styrylacetates was realized for the first time. By using a quinidine-derived C6'-urea catalyst, the direct Mannich reaction of α-styrylacetates and N-tosylimines gave the desired β-amino esters in high yields, diastereoselectivities, and ee values. The reaction provides a highly stereoselective (up to 96:4 dr and 97% ee) and the most straightforward synthesis of functionalized N-tosylated β-amino esters. The products can be used as precursors for the highly selective synthesis of tetrahydrofuran derivatives.

  1. SYNTHESIS, CHARACTERIZATION AND ANTIBACTERIAL ...

    African Journals Online (AJOL)

    Preferred Customer

    E-mail: a-ahmadi@kiau.ac.ir; ahmadikiau@yahoo.com. SYNTHESIS, CHARACTERIZATION AND ANTIBACTERIAL EVALUATION OF. SOME NOVEL DERIVATIVES OF 2-BROMOMETHYL-BENZIMIDAZOLE. Abbas Ahmadi*. Department of Medicinal Chemistry, Pharmaceutical Sciences Branch, Islamic Azad University,.

  2. 2002 Annual report: synthesis

    International Nuclear Information System (INIS)

    2003-01-01

    This synthesis of the Annual Report 2002 presents information of the main activities on the scope of the radiation protection and nuclear safety of the Nuclear Regulatory Authority (ARN) of the Argentina during 2002

  3. 2001 Annual report: synthesis

    International Nuclear Information System (INIS)

    2001-01-01

    This synthesis of the Annual Report 2001 presents information of the main activities on the scope of the radiation protection and nuclear safety of the Nuclear Regulatory Authority (ARN) of the Argentina during 2001

  4. 2000 Annual report: synthesis

    International Nuclear Information System (INIS)

    2001-01-01

    This synthesis of the Annual Report 2000 present information of the main activities on the scope of the radiation protection and nuclear safety of the Nuclear Regulatory Authority (NRA) of the Argentina during 2000

  5. Synthesis of Acetylhomoagmatine

    Directory of Open Access Journals (Sweden)

    Carmenza Duque

    2006-08-01

    Full Text Available Abstract: The first total synthesis of acetylhomoagmatine, a natural product isolated form the methanolic extracts from the sponge Cliona celata, is performed in four steps in a very high yield.

  6. Synthesis and Activation of Catalysts for Biofuel Synthesis in an Environmental Transmission Electron Microscope

    DEFF Research Database (Denmark)

    Duchstein, Linus Daniel Leonhard; Wu, Qiongxiao; Elkjær, Christian Fink

    of CuNi and NiGa catalysts for alcohol synthesis using High-Resolution TEM (HRTEM), energy electron-loss spectroscopy (EELS), Energy-Dispersive X-ray Spectroscopy (EDX). Complementary observations have been done using in-situ X-Ray Diffraction (XRD). We focus on structural changes during the catalysts...... synthesis and activation in a reducing atmosphere at elevated temperature. Changes in phase and particle size distribution with respect to the temperature can be directly observed and correlated to catalytic activity and integral phase information from the in-situ XRD....... promising candidates experimentally. Transmission electron microscopy (TEM) is used for microstructural characterization and provides feedback for both theory and synthesis. We have studied the catalysts close to their working conditions in an environmental transmission electron microscope (ETEM) equipped...

  7. Synthèse directe du 1,1-diméthoxyméthane à partir de méthanol moyennant une modification mineure du procédé de production de formaldéhyde sur catalyseurs FeMo Direct Synthesis of 1,1-dimethoxymethane from Methanol by Minor Modification of the Formaldehyde Production Process over FeMo Catalysts

    Directory of Open Access Journals (Sweden)

    Gornay J.

    2010-09-01

    éthanol de l’ordre de 56 % et une sélectivité en DMM d’environ 90 %. Ces travaux ouvrent d’intéressantes perspectives de reconversion d’unités de production de formaldéhyde (catalyseur FeMo en réacteur multitubulaire en unités de production de DMM, en ne modifiant pratiquement que la pression partielle de méthanol dans la charge, tout entravaillant avec de l’air comme diluant/oxydant. The partial oxidation reaction of methanol over redox catalysts mainly leads to the formation of formaldehyde. Over optimized FeMo-based catalysts, small quantities of products like formic acid or COx are also detected. When the catalysts have also acidic properties, condensation/dehydration reactions take place in addition to the consecutive oxidation reactions, which leads to the formation of 1,1-dimethoxymethane (DMM or methylal, dimethylether and methyl formate. Among the aforementioned products, DMM is especially interesting for industrial applications owing to its good physical properties (very good solvent, low viscosity, low superficial pressure, etc.. The main industrial applications are a use as a green solvent or a chemical intermediate; it is further suitable as a fuel additive in replacement of the petro-chemistry-derived products. At the industrial scale, DMM is conventionally produced in two steps: – formaldehyde synthesis followed by; – reaction between formaldehyde and methanol over an acid catalyst to finally obtain DMM. However, in order to reduce the DMM production costs, the development of a catalyst and of the associated process enabling the direct conversion of methanol to DMM are necessary. As aforementioned, over a FeMo-based catalyst, the main product obtained by methanol partial oxidation is formaldehyde. This process is carried out at a low methanol partial pressure, the rich methanol composition area – over the explosivity zone – being not industrially operated. Using a rich methanol composition, we observed over the same Fe

  8. Electrochemical synthesis of multisegmented nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Kok, Kuan-Ying; Ng, Inn-Khuan; Saidin, Nur Ubaidah [Malaysian Nuclear Agency, Bangi, 43000 Kajang (Malaysia)

    2012-11-27

    Electrochemical deposition has emerged as a promising route for nanostructure fabrication in recent years due to the many inherent advantages it possesses. This study focuses on the synthesis of high-aspect-ratio multisegmented Au/Ni nanowires using template-directed sequential electrochemical deposition techniques. By selectively removing the Ni segments in the nanowires, high-yield of pure gold nanorods of predetermined lengths was obtained. Alternatively, the sacrificial Ni segments in the nanowires can be galvanically displaced with Bi and Te to form barbells structures with Bi{sub x}Te{sub y} nanotubes attached to neighbouring gold segments. Detailed studies on the nanostructures obtained were carried out using various microscopy, diffraction and probebased techniques for structural, morphological and chemical characterizations.

  9. Directed vapor deposition

    Science.gov (United States)

    Groves, James Frederick

    This dissertation describes the invention, design, construction, experimental evaluation and modeling of a new physical vapor deposition technique (U.S. Patent #5,534,314) for high rate, efficient deposition of refractory elements, alloys, and compounds onto flat or curved surfaces. The new Directed Vapor Deposition (DVD) technique examined in this dissertation was distinct from previous physical vapor deposition techniques because it used low vacuum electron beam (e-beam) evaporation in combination with a carrier gas stream to transport and vapor spray deposit metals, ceramics, and semiconducting materials. Because of the system's unique approach to vapor phase materials processing, detailed analyses of critical concepts (e.g. the e-beam accelerating voltage and power required for evaporation, the vacuum pumping capacity necessary to generate specific gas flow velocities exiting a nozzle) were used to reduce to practice a functioning materials synthesis tool. After construction, the ability to create low contamination films of pure metals, semi-conducting materials, and compounds via this new method was demonstrated, and oxide deposition using an oxygen-doped gas stream in combination with a pure metal evaporant source was shown to be feasible. DVD vapor transport characteristics were experimentally investigated with deposition chamber pressure, carrier gas type, and e-beam power being identified as major processing parameters which affected vapor atom trajectories. The low vacuum carrier gas streams employed in DVD showed a dramatic ability to focus the vapor stream during transport to the substrate and thereby enhance material deposition rates and efficiencies significantly under certain process conditions. Conditions for maximum deposition efficiency onto flat substrates and continuous fibers were experimentally identified by varying chamber pressure, carrier gas velocity (Mach number), and e-beam power. Deposition efficiencies peaked at about 0.5 Torr when

  10. "Professionalism" in Second and Foreign Language Teaching: A Qualitative Research Synthesis

    Science.gov (United States)

    Jansem, Anchalee

    2018-01-01

    This qualitative research synthesis concludes and displays pictures of professionalism in second/foreign language education. Adopting Weed's processes as the methodological framework for doing qualitative research synthesis, the researcher employed seven steps, from retrieving to selecting studies directly associated with professionalism. The…

  11. Biological synthesis of nanoparticles in biofilms.

    Science.gov (United States)

    Tanzil, Abid H; Sultana, Sujala T; Saunders, Steven R; Shi, Liang; Marsili, Enrico; Beyenal, Haluk

    2016-12-01

    The biological synthesis of nanoparticles (NPs) by bacteria and biofilms via extracellular redox reactions has received attention because of the minimization of harmful chemicals, low cost, and ease of culturing and downstream processing. Bioreduction mechanisms vary across bacteria and growth conditions, which leads to various sizes and shapes of biosynthesized NPs. NP synthesis in biofilms offers additional advantages, such as higher biomass concentrations and larger surface areas, which can lead to more efficient and scalable biosynthesis. Although biofilms have been used to produce NPs, the mechanistic details of NP formation are not well understood. In this review, we identify three critical areas of research and development needed to advance our understanding of NP production by biofilms: 1) synthesis, 2) mechanism and 3) stabilization. Advancement in these areas could result in the biosynthesis of NPs that are suitable for practical applications, especially in drug delivery and biocatalysis. Specifically, the current status of methods and mechanisms of nanoparticle synthesis and surface stabilization using planktonic bacteria and biofilms is discussed. We conclude that the use of biofilms to synthesize and stabilize NPs is underappreciated and could provide a new direction in biofilm-based NP production. Copyright © 2016 Elsevier Inc. All rights reserved.

  12. Synthesis, stabilization, and characterization of metal nanoparticles

    Science.gov (United States)

    White, Gregory Von, II

    Wet chemical synthesis techniques offer the ability to control various nanoparticle characteristics including size, shape, dispersibility in both aqueous and organic solvents, and tailored surface chemistries appropriate for different applications. Large quantities of stabilizing ligands or surfactants are often required during synthesis to achieve these nanoparticle characteristics. Unfortunately, excess reaction byproducts, surfactants, and ligands remaining in solution after nanoparticle synthesis can impede application, and therefore post-synthesis purification must be employed. A liquid-liquid solvent/antisolvent pair (typically ethanol/toluene or ethanol/hexane for gold nanoparticles, GNPs) can be used to both purify and size-selectively fractionate hydrophobically modified nanoparticles. Alternatively, carbon dioxide may be used in place of a liquid antisolvent, a "green" approach, enabling both nanoparticle purification and size-selective fractionation while simultaneously eliminating mixed solvent waste and allowing solvent recycle. We have used small-angle neutron scattering (SANS) to investigate the ligand structure and composition response of alkanethiol modified gold and silver nanoparticles at varying anti-solvent conditions (CO2 or ethanol). The ligand lengths and ligand solvation for alkanethiol gold and silver NPs were found to decrease with increased antisolvent concentrations directly impacting their dispersibility in solution. Calculated Flory-Huggins interaction parameters support our SANS study for dodecanethiol dispersibility in the mixed organic solvents. This research has led to a greater understanding of the liquid-liquid precipitation process for metal nanoparticles, and provides critical results for future interaction energy modeling.

  13. Virtual screening of inorganic materials synthesis parameters with deep learning

    Science.gov (United States)

    Kim, Edward; Huang, Kevin; Jegelka, Stefanie; Olivetti, Elsa

    2017-12-01

    Virtual materials screening approaches have proliferated in the past decade, driven by rapid advances in first-principles computational techniques, and machine-learning algorithms. By comparison, computationally driven materials synthesis screening is still in its infancy, and is mired by the challenges of data sparsity and data scarcity: Synthesis routes exist in a sparse, high-dimensional parameter space that is difficult to optimize over directly, and, for some materials of interest, only scarce volumes of literature-reported syntheses are available. In this article, we present a framework for suggesting quantitative synthesis parameters and potential driving factors for synthesis outcomes. We use a variational autoencoder to compress sparse synthesis representations into a lower dimensional space, which is found to improve the performance of machine-learning tasks. To realize this screening framework even in cases where there are few literature data, we devise a novel data augmentation methodology that incorporates literature synthesis data from related materials systems. We apply this variational autoencoder framework to generate potential SrTiO3 synthesis parameter sets, propose driving factors for brookite TiO2 formation, and identify correlations between alkali-ion intercalation and MnO2 polymorph selection.

  14. Directed evolution strategies for improved enzymatic performance

    Directory of Open Access Journals (Sweden)

    Dalby Paul A

    2005-10-01

    Full Text Available Abstract The engineering of enzymes with altered activity, specificity and stability, using directed evolution techniques that mimic evolution on a laboratory timescale, is now well established. However, the general acceptance of these methods as a route to new biocatalysts for organic synthesis requires further improvement of the methods for both ease-of-use and also for obtaining more significant changes in enzyme properties than is currently possible. Recent advances in library design, and methods of random mutagenesis, combined with new screening and selection tools, continue to push forward the potential of directed evolution. For example, protein engineers are now beginning to apply the vast body of knowledge and understanding of protein structure and function, to the design of focussed directed evolution libraries, with striking results compared to the previously favoured random mutagenesis and recombination of entire genes. Significant progress in computational design techniques which mimic the experimental process of library screening is also now enabling searches of much greater regions of sequence-space for those catalytic reactions that are broadly understood and, therefore, possible to model. Biocatalysis for organic synthesis frequently makes use of whole-cells, in addition to isolated enzymes, either for a single reaction or for transformations via entire metabolic pathways. As many new whole-cell biocatalysts are being developed by metabolic engineering, the potential of directed evolution to improve these initial designs is also beginning to be realised.

  15. Detonation-synthesis nanodiamonds: synthesis, structure, properties and applications

    International Nuclear Information System (INIS)

    Dolmatov, Valerii Yu

    2007-01-01

    The review outlines the theoretical foundations and industrial implementations of modern detonation synthesis of nanodiamonds and chemical purification of the nanodiamonds thus obtained. The structure, key properties and promising fields of application of detonation-synthesis nanodiamonds are considered.

  16. Synthesis of phenanthrenes

    International Nuclear Information System (INIS)

    Clarke, C.

    1983-01-01

    A new and improved synthesis of 7-methoxy-12-methyl-2-oxo-2,3,4,9,10,12-hexahydrophenanthrene has been described. The compound is an important intermediate for the synthesis of many di- and tri-terpenes, and was required in this work for the synthesis of 17-acetyl-5α-etiojerva-12,14,16-trien-3β-ol. This compound is a known starting material for the synthesis of the veratrum alkaloids jervine, veratramine and verarine. Two synthetic routes to the synthesis of 7-methoxy-12-methyl-2-oxo-2,3,4,9,10,12-hexahydrophenanthrene were investigated. The first route required preparation of the intermediate 1-(5-methyl-2-furyl)-3-(3'-methoxyphenyl)propane which, by simple manipulation involving mainly the furan ring, gave the desired compound in 33% yield. All of the reactions involved are suitable for both large and small scale preparations. The synthesis of 17-acetyl-5α-etiojerva-12,14,16-trien-3B-ol can be achieved by the hyde and 3-methoxyacetophenone, followed by hydrogeneration and Wolff-Kishner reduction. A less successful synthesis of the above compound was achieved by condensing the Grignard derivative of 2-(3'-methoxyphenyl)ethyl bromide with 5-methylfurfuraldehyde to form a furyl alcohol, which was oxidized and reduced to give 1-(5-methyl-2-furyl)-3-(3'-methoxyphenyl)propane in only 7% overall yield, but the starting materials are inexpensive and readily available. The compound was also prepared in 40% yield by condensing 2-lithio-5-methylfuran with 3-(3'methoxyphenyl)propyl bromide. An appendix describes the reaction of 3-ethoxy-cyclohex-2-en-1-one with ethylmagnesium bromide, followed by aromatization. A second appendix describes the reductive alkylation of 8-methoxy-12-methyl-2-oxo-2,3,4,9,10,12-hexahydrophenanthrene

  17. Behavioral synthesis of asynchronous circuits

    DEFF Research Database (Denmark)

    Nielsen, Sune Fallgaard

    2005-01-01

    This thesis presents a method for behavioral synthesis of asynchronous circuits, which aims at providing a synthesis flow which uses and tranfers methods from synchronous circuits to asynchronous circuits. We move the synchronous behavioral synthesis abstraction into the asynchronous handshake...... is idle. This reduces unnecessary switching activity in the individual functional units and therefore the energy consumption of the entire circuit. A collection of behavioral synthesis algorithms have been developed allowing the designer to perform time and power constrained design space exploration...

  18. Synthesis of organosilicon compounds

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, G. [Iowa State Univ., Ames, IA (United States)

    1996-01-01

    Silicon-containing polymers have been a focus of synthesis and study in Dr. Barton`s group because of their chemistry and properties which are not offered by other systems or materials. For example, the polymer -[-SiMe2C≡C-]n-can be easily processed to films or fibers from melt or solution, and thermally converted to a SiC-containing ceramic in high yield at high temperature. In recent years, carbosilane dendritic polymers have been of great interests in many research groups. However, no synthesis of carbosilane dendrimers with functionalties both inside and outside the dendrimer has been reported. Functionality is very important in the synthesis of preceramic polymers. This thesis will be devoted to exploring several new organosilicon polymer systems.

  19. Effect of direction on loudness for wideband and reverberant sounds

    DEFF Research Database (Denmark)

    Sivonen, Ville Pekka; Ellermeier, Wolfgang

    2006-01-01

    presented to the listeners via individual binaural synthesis. The results confirm that loudness depends on sound incidence angle, as it does for narrow-band, anechoic sounds. The directional effects, however, were attenuated with the wideband and reverberant stimuli used in the present investigation....

  20. Fatty acid synthesis by spinach chloroplasts, 2

    International Nuclear Information System (INIS)

    Yamada, Mitsuhiro; Nakamura, Yasunori

    1975-01-01

    By incorporation of 3 H 2 O into the fatty acid chain in the presence of unlabelled precursor, we showed that fatty acids are synthesized from PGA, PEP and pyruvate by intact spinach chloroplasts in the light. 13 C-tracer experiments confirmed that 1-C of pyruvate is decarboxylated and 2-C is incorporated into fatty acids by the chloroplasts. The patterns of fatty acids synthesized from PGA and pyruvate were the same as that from acetate. The highest rate of fatty acid synthesis was reached at the physiological concentration of PGA (3 mM) and pyruvate (1 mM). These results indicate the operation of the following path in the chloroplasts in light: PGA→PEP→pyruvate→acetylCoA→fatty acids. Since citrate and OAA were much less active and malate and glyoxylate were inert as precursors for fatty acid synthesis, PEP or pyruvate carboxylation, citrate lyase reaction and malate synthetase reaction are not involved in the formation of acetylCoA and fatty acids. Since pyruvate was much more effective as a substrate for fatty acid synthesis than lactate, acetaldehyde or acetate, direct decarboxylation path is considered to be the primary path from pyruvate to acetylCoA. The insignificant effect of chloroplast-washing on fatty acid synthesis from PGA and pyruvate indicates that the glycolytic path from PGA to pyruvate is associated with the chloroplasts. Since pyruvate was more effectively incorporated into fatty acids than acetylCoA, it is unlikely that pyruvate decarboxylation to acetylCoA is due to mitochondria contaminating the chloroplast preparation. On the basis of measurements of 3 H 2 O incorporation in the light and dark, the activity of fatty acid synthesis in spincah leaves appears to be shared by the activities in chloroplasts (87%) and other organelles (13%). (author)

  1. Game-based verification and synthesis

    DEFF Research Database (Denmark)

    Vester, Steen

    and the environment behaves. Synthesis of strategies in games can thus be used for automatic generation of correct-by-construction programs from specifications. We consider verification and synthesis problems for several well-known game-based models. This includes both model-checking problems and satisfiability...... problems for logics capable of expressing strategic abilities of players in games with both qualitative and quantitative objectives. A number of computational complexity results for model-checking and satisfiability problems in this domain are obtained. We also show how the technique of symmetry reduction...... corresponds directly to a program for the corresponding entity of the system. A strategy for a player which ensures that the player wins no matter how the other players behave then corresponds to a program ensuring that the specification of the entity is satisfied no matter how the other entities...

  2. Current directions in radiopharmaceutical research

    International Nuclear Information System (INIS)

    Mather, S.J.

    1998-01-01

    Much of current radiopharmaceutical research is directed towards the development of receptor-binding tracers which are targeted towards biochemical processes. These may be extra or intracellular in nature and hold promise for an imaging approach to tissue characterisation in-vivo. Many of these products are based on proteins which range in size from large monoclonal antibodies to small neuropeptides and share a radiolabelling chemistry based on the use of bifunctional chelating agents. Although developed initially for use with indium-111, considerations of cost and isotope availability have continued to direct the efforts of many researchers towards the use of technetium-99m. While polypeptide-based radiopharmaceuticals may be useful for imaging peripheral cell-surface receptors, access to sites of interest within the cell, or in the brain, requires the development of small lipophilic molecules with retained ability to interact with intracellular targets. The design and synthesis of these compounds presents a particular challenge to the radiopharmaceutical chemist which is being met through either a pendant or integrated approach to the use of technetium coordination with particular emphasis on technetium (v) cores. Progress continues to be made in the application of targeted radionuclide therapy particularly in the development of radiopharmaceuticals for the treatment of malignant bone disease. methods for labelling antibodies with a great variety of cytotoxic radionuclides have now been refined and their use for radioimmunotherapy in the treatment of haematological malignancies shows great promise. The major medical areas for application of these new radiopharmaceuticals will be in oncology, neurology and inflammation but the increasingly difficult regulatory climate in which drug development and health-care now operate will make it essential for researchers to direct their products toward specific clinical problems as well as biological targets. (author)

  3. Supercritical Synthesis of Biodiesel

    Directory of Open Access Journals (Sweden)

    Michel Vaultier

    2012-07-01

    Full Text Available The synthesis of biodiesel fuel from lipids (vegetable oils and animal fats has gained in importance as a possible source of renewable non-fossil energy in an attempt to reduce our dependence on petroleum-based fuels. The catalytic processes commonly used for the production of biodiesel fuel present a series of limitations and drawbacks, among them the high energy consumption required for complex purification operations and undesirable side reactions. Supercritical fluid (SCF technologies offer an interesting alternative to conventional processes for preparing biodiesel. This review highlights the advances, advantages, drawbacks and new tendencies involved in the use of supercritical fluids (SCFs for biodiesel synthesis.

  4. Earthworm Is a Versatile and Sustainable Biocatalyst for Organic Synthesis

    Science.gov (United States)

    Guan, Zhi; Chen, Yan-Li; Yuan, Yi; Song, Jian; Yang, Da-Cheng; Xue, Yang; He, Yan-Hong

    2014-01-01

    A crude extract of earthworms was used as an eco-friendly, environmentally benign, and easily accessible biocatalyst for various organic synthesis including the asymmetric direct aldol and Mannich reactions, Henry and Biginelli reactions, direct three-component aza-Diels-Alder reactions for the synthesis of isoquinuclidines, and domino reactions for the synthesis of coumarins. Most of these reactions have never before seen in nature, and moderate to good enantioselectivities in aldol and Mannich reactions were obtained with this earthworm catalyst. The products can be obtained in preparatively useful yields, and the procedure does not require any additional cofactors or special equipment. This work provides an example of a practical way to use sustainable catalysts from nature. PMID:25148527

  5. Rapid Synthesis of Silver Nanoparticles from Fusarium oxysporum by Optimizing Physicocultural Conditions

    Directory of Open Access Journals (Sweden)

    Sonal S. Birla

    2013-01-01

    Full Text Available Synthesis of silver nanoparticles (SNPs by fungi is emerging as an important branch of nanotechnology due to its ecofriendly, safe, and cost-effective nature. In order to increase the yield of biosynthesized SNPs of desired shape and size, it is necessary to control the cultural and physical parameters during the synthesis. We report optimum synthesis of SNPs on malt extract glucose yeast extract peptone (MGYP medium at pH 9–11, 40–60°C, and 190.7 Lux and in sun light. The salt concentrations, volume of filtrate and biomass quantity were found to be directly proportional to the yield. The optimized conditions for the stable and rapid synthesis will help in large scale synthesis of monodispersed SNPs. The main aim of the present study was to optimize different media, temperature, pH, light intensity, salt concentration, volume of filtrate, and biomass quantity for the synthesis of SNPs by Fusarium oxysporum.

  6. Space travel directly induces skeletal muscle atrophy

    Science.gov (United States)

    Vandenburgh, H.; Chromiak, J.; Shansky, J.; Del Tatto, M.; Lemaire, J.

    1999-01-01

    Space travel causes rapid and pronounced skeletal muscle wasting in humans that reduces their long-term flight capabilities. To develop effective countermeasures, the basis of this atrophy needs to be better understood. Space travel may cause muscle atrophy indirectly by altering circulating levels of factors such as growth hormone, glucocorticoids, and anabolic steroids and/or by a direct effect on the muscle fibers themselves. To determine whether skeletal muscle cells are directly affected by space travel, tissue-cultured avian skeletal muscle cells were tissue engineered into bioartificial muscles and flown in perfusion bioreactors for 9 to 10 days aboard the Space Transportation System (STS, i.e., Space Shuttle). Significant muscle fiber atrophy occurred due to a decrease in protein synthesis rates without alterations in protein degradation. Return of the muscle cells to Earth stimulated protein synthesis rates of both muscle-specific and extracellular matrix proteins relative to ground controls. These results show for the first time that skeletal muscle fibers are directly responsive to space travel and should be a target for countermeasure development.

  7. Invariants of directed spaces

    DEFF Research Database (Denmark)

    Raussen, Martin

    2007-01-01

    Directed spaces are the objects of study within directed algebraic topology. They are characterised by spaces of directed paths associated to a source and a target, both elements of an underlying topological space. The algebraic topology of these path spaces and their connections are studied from...... a categorical perspective. In particular, we study the preorder category associated to a directed space and various "quotient" categories arising from algebraic topological functors. Furthermore, we propose and study a new notion of directed homotopy equivalence between directed spaces....

  8. Agarwal N Synthesis, photophysical and electrochemical proper-ties ...

    Indian Academy of Sciences (India)

    Administrator

    A solid-polymer-electrolyte direct methanol fuel cell. (DMFC) with Pt–Ru nanoparticles supported onto poly(3,4-ethylenedioxythiophene) and polystyrene sulphonic acid polymer composite as anode. 381. Silva M M S see Dutra R F. 911. Singh A see Venugopalan P. 739. Singh A P see Gupta R. 311. Singh D. Synthesis and ...

  9. Supporting information A practical one-pot synthesis of azides ...

    Indian Academy of Sciences (India)

    user

    1. Supporting information. A practical one-pot synthesis of azides directly from alcohols. Lalthazuala Rokhum and Ghanashyam Bez*. Department of Chemistry, North Eastern Hill University, Shillong-793022, India bez@nehu.ac.in ; ghanashyambez@yahoo.com. Page 2-16. 1HNMR & 13CNMR spectra of new compounds ...

  10. ROOM TEMPERATURE BULK SYNTHESIS OF SILVER NANOCABLES WRAPPED WITH POLYPYRROLE

    Science.gov (United States)

    Wet chemical synthesis of silver cables wrapped with polypyrrole is reported in aqueous media without use of any surfactant/capping agent and/or template. The method employs direct polymerization of pyrrole of an aqueous solution with AgNO3 as an oxidizing agent. The four probe c...

  11. Synthesis of an Orthogonal Topological Analogue of Helicene

    DEFF Research Database (Denmark)

    Wixe, Torbjörn; Wallentin, Carl‐Johan; Johnson, Magnus T.

    2013-01-01

    The synthesis of an orthogonal topological pentamer analogue of helicene is presented. This analogue forms a tubular structure with its aromatic systems directed parallel to the axis of propagation, which creates a cavity with the potential to function as a host molecule. The synthetic strategy...

  12. Accelerated synthesis of Sn-BEA in fluoride media

    DEFF Research Database (Denmark)

    Yakimov, Alexander V.; Kolyagin, Yury G.; Tolborg, Søren

    2016-01-01

    Tin-containing zeotypes, particularly Sn-BEA, are promising heterogeneous catalysts for a number of important industrially relevant reactions. However, the direct hydrothermal synthesis of these materials requires unfavourably long times, which is an obstacle for their industrial application. In ...

  13. Microwave-Assisted Synthesis – Catalytic Applications in Aqueous Media

    Science.gov (United States)

    The development of sustainable methods directed towards the synthesis of molecules is due to the heightened awareness and recognition of alternative eco-friendly and economical protocols that have minimum impact on environment. Among others, microwave (MW)-assisted methodology ha...

  14. Synthesis of unequally spaced linear antenna arrays | Hassen ...

    African Journals Online (AJOL)

    Synthesis of unequally spaced linear antenna arrays. MR Hassen, W Woldemariam ... Also the method needs fewer number of array elements to synthesize an array exhibiting the same (or better) level of directivity and sidelobe level in comparison with uniform arrays. Reduction in number of array elements has a positive ...

  15. Synthesis of New Benzocoumaryl Oxadiazolyls as Strong Blue ...

    African Journals Online (AJOL)

    NICO

    The benzocoumarin-3-ethylcarboxylate 2 on treatment with hydrazine hydrate at room temperature afforded benzo- coumarin-3-carbohydrazide 3. The compound 3 served as key intermediate in the synthesis of the title compounds. Thus, benzocoumarin-1,3,4-oxadiazolyls 6a–e were obtained in two ways, i.e. one by direct ...

  16. Insights into the ammonia synthesis from first-principles

    DEFF Research Database (Denmark)

    Hellmann, A.; Honkala, Johanna Karoliina; Remediakis, Ioannis

    2006-01-01

    A new set of measurements is used to further test a recently published first-principles model for the ammonia (NH3) synthesis on an unpromoted Ru-based catalyst. A direct comparison shows an overall good agreement in NH3 productivity between the model and the experiment. In addition, macro...

  17. organic template free synthesis of zsm11 from kaolinite clay

    African Journals Online (AJOL)

    user

    Synthesis of zeolitic materials from mineral ores, encounter serious challenges due to the presence of inherent impurities with the tendencies of inhibiting formation of desired products. Structure directing agent (SDA) though helps to mitigate this effect, but impact negatively on the environment. Zeolite ZSM11 is a promising ...

  18. An Approach to Interface Synthesis

    DEFF Research Database (Denmark)

    Madsen, Jan; Hald, Bjarne

    1995-01-01

    Presents a novel interface synthesis approach based on a one-sided interface description. Whereas most other approaches consider interface synthesis as optimizing a channel to existing client/server modules, we consider the interface synthesis as part of the client/server module synthesis (which...... may contain the re-use of existing modules). The interface synthesis approach describes the basic transformations needed to transform the server interface description into an interface description on the client side of the communication medium. The synthesis approach is illustrated through a point......-to-point communication, but is applicable to synthesis of a multiple client/server environment. The interface description is based on a formalization of communication events....

  19. Enzymatic synthesis of vanillin

    NARCIS (Netherlands)

    van den Heuvel, RHH; Fraaije, MW; Laane, C; van Berkel, WJH; Heuvel, Robert H.H. van den; Berkel, Willem J.H. van

    Due to increasing interest in natural vanillin, two enzymatic routes for the synthesis of vanillin were developed. The flavoprotein vanillyl alcohol oxidase (VAO) acts on a wide range of phenolic compounds and converts both creosol and vanillylamine to vanillin with high yield. The VAO-mediated

  20. Enzymatic synthesis of vanillin

    NARCIS (Netherlands)

    Heuvel, van den R.H.H.; Fraaije, M.W.; Laane, C.; Berkel, van W.J.H.

    2001-01-01

    Due to increasing interest in natural vanillin, two enzymatic routes for the synthesis of vanillin were developed. The flavoprotein vanillyl alcohol oxidase (VAO) acts on a wide range of phenolic compounds and converts both creosol and vanillylamine to vanillin with high yield. The VAO-mediated

  1. Design synthesis exercise 2012

    NARCIS (Netherlands)

    Melkert, J.A.

    2013-01-01

    The design synthesis exercise forms the closing piece of the third year of the Bachelor degree curriculum of the Faculty of Aerospace Engineering at TU Delft. In this exercise the students learn to apply their acquired knowledge from all aerospace disciplines in one complete design. The object of

  2. Asymmetric synthesis of acetomycin

    NARCIS (Netherlands)

    Kinderman, S.S.; Feringa, B.L.

    1998-01-01

    The synthesis of (-)-acetomycin, a highly functionalized γ-lactone with antitumor activity, was achieved in five steps with nearly complete enantioselectivity. The key step was realized by a large scale lipase R catalyzed esterification of 5-hydroxy-4-methyl-2(5H)-furanone providing

  3. Synthesis de 1-dotriacotanol

    International Nuclear Information System (INIS)

    Hernandez, L.; Gonzalez, J.C.

    1996-01-01

    In order to prepare isotopic labeled long chain aliphatic primary alcohol's, the synthesis overall yielding and chemical purity of 1-dotriacotanol were 41% and 98%, respectively. This procedure is very useful for carbon-14 and tritium labeling at Beta position of saturated fatty alcohol's

  4. Synthesis of Camalexin

    Directory of Open Access Journals (Sweden)

    V. Kovacik

    2001-08-01

    Full Text Available In this paper we describe a new method for the synthesis of camalexin (1 based on the reaction of 1-(tert-butoxycarbonylindole-3-carboxaldehyde with methyl Lcysteinate hydrochloride, followed by oxidation and decarboxylation. Compounds 1, and intermediates 5-7 were identified by elemental analysis, 1H NMR, 13C NMR and mass spectroscopy.

  5. Synthesis of Camalexin

    OpenAIRE

    Dzurilla, M.; Kutschy, P.; Zaletova, J.; Ruzinsky, M.; Kovacik, V.

    2001-01-01

    In this paper we describe a new method for the synthesis of camalexin (1) based on the reaction of 1-(tert-butoxycarbonyl)indole-3-carboxaldehyde with methyl Lcysteinate hydrochloride, followed by oxidation and decarboxylation. Compounds 1, and intermediates 5-7 were identified by elemental analysis, 1H NMR, 13C NMR and mass spectroscopy.

  6. Synthesis of acrylic prepolymer

    International Nuclear Information System (INIS)

    Hussin bin Mohd Nor; Dahlan bin Haji Mohd; Mohamad Hilmi bin Mahmood.

    1988-04-01

    An acrylic prepolymer was synthesized from glycidyl methacrylate (GMA), butyl methacrylate (BMA), methyl methacrylate (MMA) and acrylic acid (AA). Butyl acetate (BAc), benzoyl peroxide (BzO), 4-methoxyphenol (MPh) and triethylamine (TEA) were used as solvent, initiator, inhibitor and catalyst respectively. Observations of the synthesis leading to the formation of acrylic prepolymer are described. (author)

  7. Synthesis, characterization and properties

    Indian Academy of Sciences (India)

    Unknown

    C−H⋅⋅⋅O bonds leading to an intricate hydrogen bonding network. Keywords. Synthesis .... in the refinement riding on their respective parent atoms. ..... nent peaks at 326 and 255 nm which can be assigned to transitions of the intramolecularly hydrogen-bon- ded salicylidenimino chromophore. Cotton effects of negative ...

  8. Synthesis of new radiotracers

    International Nuclear Information System (INIS)

    Chahed, Ahlem

    2008-01-01

    The brain's sensibility besides to the rigorous selectivity of changes taking place on brain's barriers leads us to synthesis specifics radiotracers based on diamine ethylene and marked with technetium radioisotope to form a radiotracer able to pass these barriers and diagnose illnesses in an early stage. These radiotracers are tested by a biodistribution on a small animal to be ratified. (Author)

  9. Synthesis of arabinoxylan fragments

    DEFF Research Database (Denmark)

    Underlin, Emilie Nørmølle; Böhm, Maximilian F.; Madsen, Robert

    , or production of commercial chemicals which are mainly obtained from fossil fuels today.The arbinoxylan fragments have a backbone of β-1,4-linked xylans with α-L-arabinose units attached at specific positions. The synthesis ultilises an efficient synthetic route, where all the xylan units can be derived from D...

  10. Total synthesis of aquatolide

    NARCIS (Netherlands)

    Saya, J.M.; Vos, K.; Klein Nijenhuis, R.A.; van Maarseveen, J.H.; Ingemann, S.; Hiemstra, H.

    2015-01-01

    A total synthesis of the sesquiterpene lactone aquatolide has been accomplished. The central step is an intramolecular [2 + 2]-photocycloaddition of an allene onto an alpha,beta-unsaturated delta-lactone. Other key steps are an intramolecular Horner-Wadsworth-Emmons reaction to close the lactone and

  11. The synthesis of gemcitabine.

    Science.gov (United States)

    Brown, Kylie; Dixey, Michael; Weymouth-Wilson, Alex; Linclau, Bruno

    2014-03-31

    Gemcitabine is a fluorinated nucleoside currently administered against a number of cancers. It consists of a cytosine base and a 2-deoxy-2,2-difluororibose sugar. The synthetic challenges associated with the introduction of the fluorine atoms, as well as with nucleobase introduction of 2,2-difluorinated sugars, combined with the requirement to have an efficient process suitable for large scale synthesis, have spurred significant activity towards the synthesis of gemcitabine exploring a wide variety of synthetic approaches. In addition, many methods have been developed for selective crystallisation of diastereomeric (including anomeric) mixtures. In that regard, the 2-deoxy-2,2-difluororibose sugar is one of the most investigated fluorinated carbohydrates in terms of its synthesis. The versatility of synthetic methods employed is illustrative of the current state of the art of fluorination methodology for the synthesis of CF2-containing carbohydrates, and involves the use of fluorinated building blocks, as well as nucleophilic and electrophilic fluorination of sugar precursors. Copyright © 2014. Published by Elsevier Ltd.

  12. Synthesis of the catalyst

    Indian Academy of Sciences (India)

    Admin

    62 11; Palhagen S, Canger R, Henriksen O, Van Parys J A, Riviere M E and Karolchyk M A 2001 Rufinamide: a double-blind, placebo-controlled proof of principle trial in patients with epilepsy; Epilepsy Res. 43, 115; Bakunov S A, Bakunova S M, Wenzler T, Ghebru M, Werbovetz K A, Brun R and Tidwell R R 2010 Synthesis ...

  13. Industrial scale gene synthesis.

    Science.gov (United States)

    Notka, Frank; Liss, Michael; Wagner, Ralf

    2011-01-01

    The most recent developments in the area of deep DNA sequencing and downstream quantitative and functional analysis are rapidly adding a new dimension to understanding biochemical pathways and metabolic interdependencies. These increasing insights pave the way to designing new strategies that address public needs, including environmental applications and therapeutic inventions, or novel cell factories for sustainable and reconcilable energy or chemicals sources. Adding yet another level is building upon nonnaturally occurring networks and pathways. Recent developments in synthetic biology have created economic and reliable options for designing and synthesizing genes, operons, and eventually complete genomes. Meanwhile, high-throughput design and synthesis of extremely comprehensive DNA sequences have evolved into an enabling technology already indispensable in various life science sectors today. Here, we describe the industrial perspective of modern gene synthesis and its relationship with synthetic biology. Gene synthesis contributed significantly to the emergence of synthetic biology by not only providing the genetic material in high quality and quantity but also enabling its assembly, according to engineering design principles, in a standardized format. Synthetic biology on the other hand, added the need for assembling complex circuits and large complexes, thus fostering the development of appropriate methods and expanding the scope of applications. Synthetic biology has also stimulated interdisciplinary collaboration as well as integration of the broader public by addressing socioeconomic, philosophical, ethical, political, and legal opportunities and concerns. The demand-driven technological achievements of gene synthesis and the implemented processes are exemplified by an industrial setting of large-scale gene synthesis, describing production from order to delivery. Copyright © 2011 Elsevier Inc. All rights reserved.

  14. Synaptosomal protein synthesis is selectively modulated by learning.

    Science.gov (United States)

    Eyman, Maria; Cefaliello, Carolina; Ferrara, Eugenia; De Stefano, Rosanna; Crispino, Marianna; Giuditta, Antonio

    2007-02-09

    Synaptosomes from rat brain have long been used to investigate the properties of synaptic protein synthesis. Comparable analyses have now been made in adult male rats trained for a two-way active avoidance task to examine the hypothesis of its direct participation in brain plastic events. Using Ficoll-purified synaptosomes from neocortex, hippocampus and cerebellum, our data indicate that the capacity of synaptosomal protein synthesis and the specific activity of newly synthesized proteins were not different in trained rats in comparison with home-caged control rats. On the other hand, the synthesis of two proteins of 66.5 kDa and 87.6 kDa separated by SDS-PAGE and analyzed by quantitative densitometry was selectively enhanced in trained rats. In addition, the synthesis of the 66.5 kDa protein, but not of the 87.6 kDa protein, correlated with avoidances and escapes and inversely correlated with freezings in the neocortex, while in the cerebellum it correlated with avoidances and escapes. The data demonstrate the participation of synaptic protein synthesis in plastic events of behaving rats, and the selective, region-specific modulation of the synthesis of a synaptic 66.5 kDa protein by the newly acquired avoidance response and by the reprogramming of innate neural circuits subserving escape and freezing responses.

  15. Direct selling particularities

    OpenAIRE

    Greifová, Daniela

    2009-01-01

    Bachelor thesis is focused on the parcularities of direct selling, self regulation of this industry, multi-level marketing which is the most used sales method in the field of direct selling. The part of the thesis is dedicated to the issue of customer psychology that is very important for achieving success in direct selling. Main goals are to provide readers with the general view of direct selling and analysis of growing possibilities of the industry in the future.

  16. Direct immunofluorescence microscopy

    NARCIS (Netherlands)

    Diercks, G.F.H.; Pas, Hendrikus; Jonkman, Marcel

    2016-01-01

    Direct immunofluorescence plays an important role in the diagnosis of autoimmune bullous diseases. The purpose of direct immunofluorescence microscopy is to detect in vivo antibodies in patient's skin or mucosa. Direct immunofluorescence of pemphigus shows depositions of immunoglobulins and/or

  17. Suppression of glycosaminoglycan synthesis by articular cartilage, but not of hyaluronic acid synthesis by synovium, after exposure to radiation

    International Nuclear Information System (INIS)

    Hugenberg, S.T.; Myers, S.L.; Brandt, K.D.

    1989-01-01

    We recently found that injection of 2 mCi of yttrium 90 (90Y; approximately 23,000 rads) into normal canine knees stimulated glycosaminoglycan (GAG) synthesis by femoral condylar cartilage. The present investigation was conducted to determine whether radiation affects cartilage metabolism directly. Rates of GAG synthesis and degradation in normal canine articular cartilage were studied following irradiation. Cultured synovium from the same knees was treated similarly, to determine the effects of irradiation on hyaluronic acid synthesis. Twenty-four hours after exposure to 1,000 rads, 10,000 rads, or 50,000 rads, 35S-GAG synthesis by the cartilage was 93%, 69%, and 37%, respectively, of that in control, nonirradiated cartilage. The effect was not rapidly reversible: 120 hours after exposure to 50,000 rads, GAG synthesis remained at only 28% of the control level. Autoradiography showed marked suppression of 35S uptake by chondrocytes after irradiation. Cartilage GAG degradation was also increased following irradiation: 4 hours and 8 hours after exposure to 50,000 rads, the cartilage GAG concentration was only 66% and 54%, respectively, of that at time 0, while corresponding values for control, nonirradiated cartilage were 90% and 87%. In contrast to its effects on cartilage GAG metabolism, radiation at these levels had no effect on synovial hyaluronic acid synthesis

  18. Suppression of glycosaminoglycan synthesis by articular cartilage, but not of hyaluronic acid synthesis by synovium, after exposure to radiation

    Energy Technology Data Exchange (ETDEWEB)

    Hugenberg, S.T.; Myers, S.L.; Brandt, K.D.

    1989-04-01

    We recently found that injection of 2 mCi of yttrium 90 (90Y; approximately 23,000 rads) into normal canine knees stimulated glycosaminoglycan (GAG) synthesis by femoral condylar cartilage. The present investigation was conducted to determine whether radiation affects cartilage metabolism directly. Rates of GAG synthesis and degradation in normal canine articular cartilage were studied following irradiation. Cultured synovium from the same knees was treated similarly, to determine the effects of irradiation on hyaluronic acid synthesis. Twenty-four hours after exposure to 1,000 rads, 10,000 rads, or 50,000 rads, 35S-GAG synthesis by the cartilage was 93%, 69%, and 37%, respectively, of that in control, nonirradiated cartilage. The effect was not rapidly reversible: 120 hours after exposure to 50,000 rads, GAG synthesis remained at only 28% of the control level. Autoradiography showed marked suppression of 35S uptake by chondrocytes after irradiation. Cartilage GAG degradation was also increased following irradiation: 4 hours and 8 hours after exposure to 50,000 rads, the cartilage GAG concentration was only 66% and 54%, respectively, of that at time 0, while corresponding values for control, nonirradiated cartilage were 90% and 87%. In contrast to its effects on cartilage GAG metabolism, radiation at these levels had no effect on synovial hyaluronic acid synthesis.

  19. [Acupuncture direction and analgesia].

    Science.gov (United States)

    Sun, Lu; Kou, Renzhong; Liu, Lanqing; Fan, Gangqi

    2017-03-12

    The acupuncture direction is closely related with the efficacy of acupuncture analgesia. In this article, the relationship between efficacy of acupuncture analgesia and factors, such as whether the needle towards disease location, whether the needle towards meridian direction, whether the needle following spinal cord direction and whether the needle following muscle direction, were analyzed. The previous clinical and literature research indicated that the needle towards disease location was superior to reverse direction, however, the efficacy of analgesia between needle following and reversing meridian, needle towards and at disease location, needles following and reversing spinal cord direction, needles following and reversing muscle direction was controversial. Therefore, the solutions to these problems will benefit the optimized acupuncture treatment plan for pain disorders.

  20. Appreciation of symmetry in natural product synthesis.

    Science.gov (United States)

    Bai, Wen-Ju; Wang, Xiqing

    2017-12-13

    Covering: 2012 to June 2017This review aims to show that complex natural product synthesis can be streamlined by taking advantage of molecular symmetry. Various strategies to construct molecules with either evident or hidden symmetry are illustrated. Insights regarding the origins and adjustments of these strategies as well as inspiring new methodological developments are deliberated. When a symmetric strategy fails, the corresponding reason is analysed and an alternative approach is briefly provided. Finally, the importance of exploiting molecular symmetry and future research directions are discussed.

  1. Cyclodextrins in Asymmetric and Stereospecific Synthesis

    Directory of Open Access Journals (Sweden)

    Fliur Macaev

    2015-09-01

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

  2. Influence of anabolic agents on protein synthesis and degradation in muscle cells grown in culture

    Energy Technology Data Exchange (ETDEWEB)

    Roeder, R.A.; Thorpe, S.D.; Byers, F.M.; Schelling, G.T.; Gunn, J.M.

    Muscle cell culture (L/sub 6/) studies were conducted to determine whether anabolic agents have a direct effect on the muscle cell. The effect of zeranol, testosterone propionate, estradiol benzoate, progesterone, dexamethasone and anabolic agent-dexamethasone combinations on protein synthesis and degradation were measured. Myoblast and myotube cultures were pretreated with 1 ..mu..M compounds for 12, 24 and 48 h before a 6-h synthesis or degradation measuring period. Protein synthesis was determined as cpm of (/sup 3/H) leucine incorporated per mg cell protein. Protein degradation was measured by a pulse-chase procedure using (/sup 3/H) leucine and expressed as the percentage labeled protein degraded in 6 h. Progesterone slightly increased protein synthesis in myoblast cultures. Testosterone propionate had no effect on synthesis. Protein synthesis was decreased by estradiol benzoate in myotube cultures. Protein degradation was not altered appreciably by anabolic agents. Protein synthesis was initially inhibited in myotubes by dexamethasone, but increased in myoblasts and myotubes in the extended incubation time. Dexamethasone also consistently increased protein degradation, but this required several hours to be expressed. Anabolic agents did not interfere with dexamethasone-induced increases in protein synthesis and degradation. The magnitude of response and sensitivity were similar for both the myoblast and the more fully differentiated myotube for all compounds tested. These results indicate that anabolic agents at the 1 ..mu..M level do not have a direct anabolic effect on muscle or alter glucocorticoid-induced catabolic response in muscle.

  3. Influence of anabolic agents on protein synthesis and degradation in muscle cells grown in culture

    International Nuclear Information System (INIS)

    Roeder, R.A.; Thorpe, S.D.; Byers, F.M.; Schelling, G.T.; Gunn, J.M.

    1986-01-01

    Muscle cell culture (L 6 ) studies were conducted to determine whether anabolic agents have a direct effect on the muscle cell. The effect of zeranol, testosterone propionate, estradiol benzoate, progesterone, dexamethasone and anabolic agent-dexamethasone combinations on protein synthesis and degradation were measured. Myoblast and myotube cultures were pretreated with 1 μM compounds for 12, 24 and 48 h before a 6-h synthesis or degradation measuring period. Protein synthesis was determined as cpm of [ 3 H] leucine incorporated per mg cell protein. Protein degradation was measured by a pulse-chase procedure using [ 3 H] leucine and expressed as the percentage labeled protein degraded in 6 h. Progesterone slightly increased protein synthesis in myoblast cultures. Testosterone propionate had no effect on synthesis. Protein synthesis was decreased by estradiol benzoate in myotube cultures. Protein degradation was not altered appreciably by anabolic agents. Protein synthesis was initially inhibited in myotubes by dexamethasone, but increased in myoblasts and myotubes in the extended incubation time. Dexamethasone also consistently increased protein degradation, but this required several hours to be expressed. Anabolic agents did not interfere with dexamethasone-induced increases in protein synthesis and degradation. The magnitude of response and sensitivity were similar for both the myoblast and the more fully differentiated myotube for all compounds tested. These results indicate that anabolic agents at the 1 μM level do not have a direct anabolic effect on muscle or alter glucocorticoid-induced catabolic response in muscle

  4. Directional depletion interactions in shaped particles

    Directory of Open Access Journals (Sweden)

    A. Scala

    2014-09-01

    Full Text Available Entropic forces in colloidal suspensions and in polymer-colloid systems are of long-standing and continuing interest. Experiments show how entropic forces can be used to control the self-assembly of colloidal particles. Significant advances in colloidal synthesis made in the past two decades have enabled the preparation of high quality nano-particles with well-controlled sizes, shapes, and compositions, indicating that such particles can be utilized as "artificial atoms" to build new materials. To elucidate the effects of the shape of particles upon the magnitude of entropic interaction, we analyse the entropic interactions of two cut-spheres. We show that the solvent induces a strong directional depletion attraction among flat faces of the cut-spheres. Such an effect highlights the possibility of using the shape of particles to control directionality and strength of interaction.

  5. Graphene directed architecture of fine engineered nanostructures with electrochemical applications

    DEFF Research Database (Denmark)

    Hou, Chengyi; Zhang, Minwei; Halder, Arnab

    2017-01-01

    . In this review, we aim to highlight some recent efforts devoted to rational design, assembly and fine engineering of electrochemically active nanostructures using graphene or/and its derivatives as soft templates for controlled synthesis and directed growth. We organize the contents according to the chemically...... classified nanostructures, including metallic nanostructures, self-assembled organic and supramolecular structures, and fine engineered metal oxides. In these cases, graphene templates either sacrificed during templating synthesis or retained as support for final products. We also discuss remained challenges...... and future perspective in the graphene-templating design and synthesis of various materials. Overall, this review could offer crucial insights into the nanoscale engineering of new nanostructures using graphene as a soft template and their potential applications in electrochemical science and technology. We...

  6. Voice synthesis application

    Science.gov (United States)

    Lightstone, P. C.; Davidson, W. M.

    1982-04-01

    The military detection assessment laboratory houses an experimental field system which assesses different alarm indicators such as fence disturbance sensors, MILES cables, and microwave Racons. A speech synthesis board which could be interfaced, by means of a computer, to an alarm logger making verbal acknowledgement of alarms possible was purchased. Different products and different types of voice synthesis were analyzed before a linear predictive code device produced by Telesensory Speech Systems of Palo Alto, California was chosen. This device is called the Speech 1000 Board and has a dedicated 8085 processor. A multiplexer card was designed and the Sp 1000 interfaced through the card into a TMS 990/100M Texas Instrument microcomputer. It was also necessary to design the software with the capability of recognizing and flagging an alarm on any 1 of 32 possible lines. The experimental field system was then packaged with a dc power supply, LED indicators, speakers, and switches, and deployed in the field performing reliably.

  7. Synthesis of quantum dots

    Science.gov (United States)

    McDaniel, Hunter

    2017-10-17

    Common approaches to synthesizing alloyed quantum dots employ high-cost, air-sensitive phosphine complexes as the selenium precursor. Disclosed quantum dot synthesis embodiments avoid these hazardous and air-sensitive selenium precursors. Certain embodiments utilize a combination comprising a thiol and an amine that together reduce and complex the elemental selenium to form a highly reactive selenium precursor at room temperature. The same combination of thiol and amine acts as the reaction solvent, stabilizing ligand, and sulfur source in the synthesis of quantum dot cores. A non-injection approach may also be used. The optical properties of the quantum dots synthesized by this new approach can be finely tuned for a variety of applications by controlling size and/or composition of size and composition. Further, using the same approach, a shell can be grown around a quantum dot core that improves stability, luminescence efficiency, and may reduce toxicity.

  8. Prebiotic synthesis of histidine

    Science.gov (United States)

    Shen, C.; Yang, L.; Miller, S. L.; Oro, J.

    1990-01-01

    The prebiotic formation of histidine (His) has been accomplished experimentally by the reaction of erythrose with formamidine followed by a Strecker synthesis. In the first step of this reaction sequence, the formation of imidazole-4-acetaldehyde took place by the condensation of erythrose and formamidine, two compounds that are known to be formed under prebiotic conditions. In a second step, the imidazole-4-acetaldehyde was converted to His, without isolation of the reaction products by adding HCN and ammonia to the reaction mixture. LC, HPLC, thermospray liquid chromatography-mass spectrometry, and tandem mass spectrometry were used to identify the product, which was obtained in a yield of 3.5% based on the ratio of His/erythrose. This is a new chemical synthesis of one of the basic amino acids which had not been synthesized prebiotically until now.

  9. Collagen synthesis in human musculoskeletal tissues and skin

    DEFF Research Database (Denmark)

    Babraj, J A; Cuthbertson, D J R; Smith, K

    2005-01-01

    . In postabsorptive, healthy young men (28 +/- 6 yr) synthetic rates for tendon, ligament, muscle, and skin collagen were 0.046 +/- 0.005, 0.040 +/- 0.006, 0.016 +/- 0.002, and 0.037 +/- 0.003%/h, respectively (means +/- SD). In postabsorptive, healthy elderly men (70 +/- 6 yr) the rate of skeletal muscle collagen......We have developed a direct method for the measurement of human musculoskeletal collagen synthesis on the basis of the incorporation of stable isotope-labeled proline or leucine into protein and have used it to measure the rate of synthesis of collagen in tendon, ligament, muscle, and skin...

  10. Distributed PROMPT-LTL Synthesis

    Directory of Open Access Journals (Sweden)

    Swen Jacobs

    2016-09-01

    Full Text Available We consider the synthesis of distributed implementations for specifications in Prompt Linear Temporal Logic (PROMPT-LTL, which extends LTL by temporal operators equipped with parameters that bound their scope. For single process synthesis it is well-established that such parametric extensions do not increase worst-case complexities. For synchronous systems, we show that, despite being more powerful, the distributed realizability problem for PROMPT-LTL is not harder than its LTL counterpart. For asynchronous systems we have to consider an assume-guarantee synthesis problem, as we have to express scheduling assumptions. As asynchronous distributed synthesis is already undecidable for LTL, we give a semi-decision procedure for the PROMPT-LTL assume-guarantee synthesis problem based on bounded synthesis.

  11. Microwave multicomponent synthesis.

    Science.gov (United States)

    Hügel, Helmut M

    2009-12-01

    In the manner that very important research is often performed by multidisciplinary research teams, the applications of multicomponent reactions involving the combination of multiple starting materials with different functional groups leading to the higher efficiency and environmentally friendly construction of multifunctional/complex target molecules is growing in importance. This review will explore the advances and advantages in microwave multicomponent synthesis (MMS) that have been achieved over the last five years.

  12. Microwave Multicomponent Synthesis

    Directory of Open Access Journals (Sweden)

    Helmut M. Hügel

    2009-12-01

    Full Text Available In the manner that very important research is often performed by multidisciplinary research teams, the applications of multicomponent reactions involving the combination of multiple starting materials with different functional groups leading to the higher efficiency and environmentally friendly construction of multifunctional/complex target molecules is growing in importance. This review will explore the advances and advantages in microwave multicomponent synthesis (MMS that have been achieved over the last five years.

  13. Microwave Multicomponent Synthesis

    OpenAIRE

    Helmut M. Hügel

    2009-01-01

    In the manner that very important research is often performed by multidisciplinary research teams, the applications of multicomponent reactions involving the combination of multiple starting materials with different functional groups leading to the higher efficiency and environmentally friendly construction of multifunctional/complex target molecules is growing in importance. This review will explore the advances and advantages in microwave multicomponent synthesis (MMS) that have been achiev...

  14. Synthesis of functionalised sulfonamides

    OpenAIRE

    Mok, B. L.

    2008-01-01

    Sulfonamides are important therapeutic agents and have a diverse array of biological functions in biology and medicine. Their means of synthesis has often involved the use of unstable sulfonyl chloride species; however, recent research has established pentafluorophenyl (PFP) sulfonate esters as a useful stable alternative to such species. This thesis describes the use of PFP vinyl sulfonate in a [3+2] cycloaddition with a variety of N-methyl-nitrones, providing access to the corresponding...

  15. Break-induced telomere synthesis underlies alternative telomere maintenance.

    Science.gov (United States)

    Dilley, Robert L; Verma, Priyanka; Cho, Nam Woo; Winters, Harrison D; Wondisford, Anne R; Greenberg, Roger A

    2016-11-03

    Homology-directed DNA repair is essential for genome maintenance through templated DNA synthesis. Alternative lengthening of telomeres (ALT) necessitates homology-directed DNA repair to maintain telomeres in about 10-15% of human cancers. How DNA damage induces assembly and execution of a DNA replication complex (break-induced replisome) at telomeres or elsewhere in the mammalian genome is poorly understood. Here we define break-induced telomere synthesis and demonstrate that it utilizes a specialized replisome, which underlies ALT telomere maintenance. DNA double-strand breaks enact nascent telomere synthesis by long-tract unidirectional replication. Proliferating cell nuclear antigen (PCNA) loading by replication factor C (RFC) acts as the initial sensor of telomere damage to establish predominance of DNA polymerase δ (Pol δ) through its POLD3 subunit. Break-induced telomere synthesis requires the RFC-PCNA-Pol δ axis, but is independent of other canonical replisome components, ATM and ATR, or the homologous recombination protein Rad51. Thus, the inception of telomere damage recognition by the break-induced replisome orchestrates homology-directed telomere maintenance.

  16. The Advanced Aluminum Nitride Synthesis Methods and Its Applications: Patent Review.

    Science.gov (United States)

    Shishkin, Roman A; Elagin, Andrey A; Mayorova, Ekaterina S; Beketov, Askold R

    2016-01-01

    High purity nanosized aluminum nitride synthesis is a current issue for both industry and science. However, there is no up-to-date review considering the major issues and the technical solutions for different methods. This review aims to investigate the advanced methods of aluminum nitride synthesis and its development tendencies. Also the aluminum nitride application patents and prospects for development of the branch have been considered. The patent search on "aluminum nitride synthesis" has been carried out. The research activity has been analyzed. Special attention has been paid to the patenting geography and the leading researchers in aluminum nitride synthesis. Aluminum nitride synthesis methods have been divided into 6 main groups, the most studied approaches are carbothermal reduction (88 patents) and direct nitridation (107 patents). The current issues for each group have been analyzed; the main trends are purification of the final product and nanopowder synthesis. The leading researchers in aluminum nitride synthesis have represented 5 countries, namely: Japan, China, Russia, South Korea and USA. The main aluminum nitride application spheres are electronics (59,1 percent of applications) and new materials manufacturing (30,9 percent). The review deals with the state of the art data in nanosized aluminum nitride synthesis, the major issues and the technical solutions for different synthesis methods. It gives a full understanding of the development tendencies and of the current leaders in the sphere.

  17. Integrated methanol synthesis

    International Nuclear Information System (INIS)

    Jaeger, W.

    1982-01-01

    This invention concerns a plant for methanol manufacture from gasified coal, particularly using nuclear power. In order to reduce the cost of the hydrogen circuits, the methanol synthesis is integrated in the coal gasification plant. The coal used is gasified with hydration by means of hydrogen and the crude gas emerging, after cooling and separating the carbon dioxide and hydrogen sulphide, is mixed with the synthetic gas leaving the methane cracking furnace. This mixture is taken to the methanol synthesis and more than 90% is converted into methanol in one pass. The gas mixture remaning after condensation and separation of methanol is decomposed into three fractions in low temperature gas decomposition with a high proportion of unconverted carbon monoxide. The flow of methane is taken to the cracking furnace with steam, the flow of hydrogen is taken to the hydrating coal gasifier, and the flow of carbon monoxide is taken to the methanol synthesis. The heat required for cracking the methane can either be provided by a nuclear reactor or by the coke left after hydrating gasification. (orig./RB) [de

  18. Gold Nanoparticle Microwave Synthesis

    International Nuclear Information System (INIS)

    Krantz, Kelsie E.; Christian, Jonathan H.; Coopersmith, Kaitlin; Washington II, Aaron L.; Murph, Simona H.

    2016-01-01

    At the nanometer scale, numerous compounds display different properties than those found in bulk material that can prove useful in areas such as medicinal chemistry. Gold nanoparticles, for example, display promise in newly developed hyperthermia therapies for cancer treatment. Currently, gold nanoparticle synthesis is performed via the hot injection technique which has large variability in final particle size and a longer reaction time. One underdeveloped area by which these particles could be produced is through microwave synthesis. To initiate heating, microwaves agitate polar molecules creating a vibration that gives off the heat energy needed. Previous studies have used microwaves for gold nanoparticle synthesis; however, polar solvents were used that partially absorbed incident microwaves, leading to partial thermal heating of the sample rather than taking full advantage of the microwave to solely heat the gold nanoparticle precursors in a non-polar solution. Through this project, microwaves were utilized as the sole heat source, and non-polar solvents were used to explore the effects of microwave heating only as pertains to the precursor material. Our findings show that the use of non-polar solvents allows for more rapid heating as compared to polar solvents, and a reduction in reaction time from 10 minutes to 1 minute; this maximizes the efficiency of the reaction, and allows for reproducibility in the size/shape of the fabricated nanoparticles.

  19. Gold Nanoparticle Microwave Synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Krantz, Kelsie E. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Christian, Jonathan H. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Coopersmith, Kaitlin [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Washington, II, Aaron L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Murph, Simona H. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2016-07-27

    At the nanometer scale, numerous compounds display different properties than those found in bulk material that can prove useful in areas such as medicinal chemistry. Gold nanoparticles, for example, display promise in newly developed hyperthermia therapies for cancer treatment. Currently, gold nanoparticle synthesis is performed via the hot injection technique which has large variability in final particle size and a longer reaction time. One underdeveloped area by which these particles could be produced is through microwave synthesis. To initiate heating, microwaves agitate polar molecules creating a vibration that gives off the heat energy needed. Previous studies have used microwaves for gold nanoparticle synthesis; however, polar solvents were used that partially absorbed incident microwaves, leading to partial thermal heating of the sample rather than taking full advantage of the microwave to solely heat the gold nanoparticle precursors in a non-polar solution. Through this project, microwaves were utilized as the sole heat source, and non-polar solvents were used to explore the effects of microwave heating only as pertains to the precursor material. Our findings show that the use of non-polar solvents allows for more rapid heating as compared to polar solvents, and a reduction in reaction time from 10 minutes to 1 minute; this maximizes the efficiency of the reaction, and allows for reproducibility in the size/shape of the fabricated nanoparticles.

  20. Descendants and advance directives.

    Science.gov (United States)

    Buford, Christopher

    2014-01-01

    Some of the concerns that have been raised in connection to the use of advance directives are of the epistemic variety. Such concerns highlight the possibility that adhering to an advance directive may conflict with what the author of the directive actually wants (or would want) at the time of treatment. However, at least one objection to the employment of advance directives is metaphysical in nature. The objection to be discussed here, first formulated by Rebecca Dresser and labeled by Allen Buchanan as the slavery argument and David DeGrazia the someone else problem, aims to undermine the legitimacy of certain uses of advance directives by concluding that such uses rest upon an incorrect assumption about the identity over time of those ostensibly governed by the directives. There have been numerous attempts to respond to this objection. This paper aims to assess two strategies that have been pursued to cope with the problem.

  1. Indium mediated isoprenylation of carbonyl compounds with 2-bromomethyl-1,3-butadiene: a short synthesis of (±-ipsenol

    Directory of Open Access Journals (Sweden)

    Ceschi Marco A.

    2003-01-01

    Full Text Available Isoprenylation of aldehydes and ketones was directly performed by selective indium insertion on a mixture of 2-bromomethyl-1,3-butadiene and its vinylic isomers in good yields. A short synthesis of (±-ipsenol, an aggregation pheromone of the Ips paraconfusus bark beetle, demonstrates the utility of this method in organic synthesis.

  2. Directional radiation detectors

    Science.gov (United States)

    Dowell, Jonathan L.

    2017-09-12

    Directional radiation detectors and systems, methods, and computer-readable media for using directional radiation detectors to locate a radiation source are provided herein. A directional radiation detector includes a radiation sensor. A radiation attenuator partially surrounds the radiation sensor and defines an aperture through which incident radiation is received by the radiation sensor. The aperture is positioned such that when incident radiation is received directly through the aperture and by the radiation sensor, a source of the incident radiation is located within a solid angle defined by the aperture. The radiation sensor senses at least one of alpha particles, beta particles, gamma particles, or neutrons.

  3. Directed Energy Anechoic Chamber

    Data.gov (United States)

    Federal Laboratory Consortium — The Directed Energy Anechoic Chamber comprises a power anechoic chamber and one transverse electromagnetic cell for characterizing radiofrequency (RF) responses of...

  4. In vitro synthesis of a lipid-linked trisaccharide involved in synthesis of enterobacterial common antigen

    International Nuclear Information System (INIS)

    Barr, K.; Nunes-Edwards, P.; Rick, P.D.

    1989-01-01

    The heteropolysaccharide chains of enterobacterial common antigen (ECA) are made up of linear trisaccharide repeat units with the structure----3)-alpha-D-Fuc4NAc-(1----4)- beta-D-ManNAcA-(1----4)-alpha-D-GlcNAc-(1----, where Fuc4NAc is 4-acetamido-4,6-dideoxy-D-galactose, ManNAcA is N-acetyl-D-mannosaminuronic acid, and GlcNAc is N-acetyl-D-glucosamine. The assembly of these chains involves lipid-linked intermediates, and both GlcNAc-pyrophosphorylundecaprenol (lipid I) and ManNAcA-GlcNAc-pyrophosphorylundecaprenol (lipid II) are intermediates in ECA biosynthesis. In this study we demonstrated that lipid II serves as the acceptor of Fuc4NAc residues in the assembly of the trisaccharide repeat unit of ECA chains. Incubation of Escherichia coli membranes with UDP-GlcNAc, UDP-[14C]ManNAcA, and TDP-[3H]Fuc4NAc resulted in the synthesis of a radioactive glycolipid (lipid III) that contained both [14C]ManNAcA and [3H]Fuc4NAc. The oligosaccharide moiety of lipid III was identified as a trisaccharide by gel-permeation chromatography, and the in vitro synthesis of lipid III was dependent on prior synthesis of lipids I and II. Accordingly, the incorporation of [3H]Fuc4NAc into lipid III from the donor TDP-[3H]Fuc4NAc was dependent on the presence of both UDP-GlcNAc and UDP-ManNAcA in the reaction mixtures. In addition, the in vitro synthesis of lipid III was abolished by tunicamycin. Direct conversion of lipid II to lipid III was demonstrated in two-stage reactions in which membranes were initially incubated with UDP-GlcNAc and UDP-[14C]ManNAcA to allow the synthesis of radioactive lipid II

  5. Ammonia Synthesis at Low Pressure.

    Science.gov (United States)

    Cussler, Edward; McCormick, Alon; Reese, Michael; Malmali, Mahdi

    2017-08-23

    Ammonia can be synthesized at low pressure by the use of an ammonia selective absorbent. The process can be driven with wind energy, available locally in areas requiring ammonia for synthetic fertilizer. Such wind energy is often called "stranded," because it is only available far from population centers where it can be directly used. In the proposed low pressure process, nitrogen is made from air using pressure swing absorption, and hydrogen is produced by electrolysis of water. While these gases can react at approximately 400 °C in the presence of a promoted conventional catalyst, the conversion is often limited by the reverse reaction, which makes this reaction only feasible at high pressures. This limitation can be removed by absorption on an ammine-like calcium or magnesium chloride. Such alkaline metal halides can effectively remove ammonia, thus suppressing the equilibrium constraints of the reaction. In the proposed absorption-enhanced ammonia synthesis process, the rate of reaction may then be controlled not by the chemical kinetics nor the absorption rates, but by the rate of the recycle of unreacted gases. The results compare favorably with ammonia made from a conventional small scale Haber-Bosch process.

  6. Asymmetric catalysis in organic synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Reilly, S.D.; Click, D.R.; Grumbine, S.K.; Scott, B.L.; Watkins, J.G.

    1998-11-01

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The goal of the project was to prepare new catalyst systems, which would perform chemical reactions in an enantioselective manner so as to produce only one of the possible optical isomers of the product molecule. The authors have investigated the use of lanthanide metals bearing both diolate and Schiff-base ligands as catalysts for the enantioselective reduction of prochiral ketones to secondary alcohols. The ligands were prepared from cheap, readily available starting materials, and their synthesis was performed in a ''modular'' manner such that tailoring of specific groups within the ligand could be carried out without repeating the entire synthetic procedure. In addition, they have developed a new ligand system for Group IV and lanthanide-based olefin polymerization catalysts. The ligand system is easily prepared from readily available starting materials and offers the opportunity to rapidly prepare a wide range of closely related ligands that differ only in their substitution patterns at an aromatic ring. When attached to a metal center, the ligand system has the potential to carry out polymerization reactions in a stereocontrolled manner.

  7. Patterning hierarchy in direct and inverse opal crystals.

    Science.gov (United States)

    Mishchenko, Lidiya; Hatton, Benjamin; Kolle, Mathias; Aizenberg, Joanna

    2012-06-25

    Biological strategies for bottom-up synthesis of inorganic crystalline and amorphous materials within topographic templates have recently become an attractive approach for fabricating complex synthetic structures. Inspired by these strategies, herein the synthesis of multi-layered, hierarchical inverse colloidal crystal films formed directly on topographically patterned substrates via evaporative deposition, or "co-assembly", of polymeric spheres with a silicate sol-gel precursor solution and subsequent removal of the colloidal template, is described. The response of this growing composite colloid-silica system to artificially imposed 3D spatial constraints of various geometries is systematically studied, and compared with that of direct colloidal crystal assembly on the same template. Substrates designed with arrays of rectangular, triangular, and hexagonal prisms and cylinders are shown to control crystallographic domain nucleation and orientation of the direct and inverse opals. With this bottom-up topographical approach, it is demonstrated that the system can be manipulated to either form large patterned single crystals, or crystals with a fine-tuned extent of disorder, and to nucleate distinct colloidal domains of a defined size, location, and orientation in a wide range of length-scales. The resulting ordered, quasi-ordered, and disordered colloidal crystal films show distinct optical properties. Therefore, this method provides a means of controlling bottom-up synthesis of complex, hierarchical direct and inverse opal structures designed for altering optical properties and increased functionality. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Application of chalcones in heterocycles synthesis: Synthesis of 2 ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 125; Issue 3. Application of chalcones in heterocycles synthesis: Synthesis of 2-(isoxazolo, pyrazolo and pyrimido) substituted analogues of 1,4-benzodiazepin-5-carboxamides linked through an oxyphenyl bridge. N Kaur D Kishore. Volume 125 Issue 3 May 2013 pp ...

  9. The Consumer Rights Directive

    NARCIS (Netherlands)

    Luzak, J.A.; Mak, V.; Hartkamp, A.S.; Sieburgh, C.H.; Keus, L.A.D.; Kortmann, J.S.; Wissink, M.H.

    2014-01-01

    This contribution discusses the impact of the CRD on Dutch private law. How will the new directive influence consumer rights and how does this fit with existing law? Considering the background of the directive and its importance for European consumer law, however, we discuss these questions in the

  10. Direct RF modulation transmitter

    NARCIS (Netherlands)

    Fukuda, Shuichi; Nauta, Bram

    2013-01-01

    PROBLEM TO BE SOLVED: To provide a direct RF modulation transmitter capable of saving more power consumption. SOLUTION: The direct RF modulation transmitter comprises: a passive mixer circuit 100 which inputs digital baseband data D of 1 bit, inverted data DN, a first RF signal, and a second RF

  11. TNF suppresses acute intestinal inflammation by inducing local glucocorticoid synthesis

    Science.gov (United States)

    Noti, Mario; Corazza, Nadia; Mueller, Christoph; Berger, Barbara

    2010-01-01

    Although tumor necrosis factor (α) (TNF) exerts proinflammatory activities in a variety of diseases, including inflammatory bowel disease, there is increasing evidence for antiinflammatory actions of TNF. In contrast, glucocorticoids (GCs) are steroid hormones that suppress inflammation, at least in part by regulating the expression and action of TNF. We report that TNF induces extraadrenal production of immunoregulatory GCs in the intestinal mucosa during acute intestinal inflammation. The absence of TNF results in a lack of colonic GC synthesis and exacerbation of dextran sodium sulfate–induced colitis. TNF seems to promote local steroidogenesis by directly inducing steroidogenic enzymes in intestinal epithelial cells. Therapeutic administration of TNF induces GC synthesis in oxazolone-induced colitis and ameliorates intestinal inflammation, whereas inhibition of intestinal GC synthesis abrogates the therapeutic effect of TNF. These data show that TNF suppresses the pathogenesis of acute intestinal inflammation by promoting local steroidogenesis. PMID:20439544

  12. Synthesis and Functionalization of Porphyrins through Organometallic Methodologies.

    Science.gov (United States)

    Hiroto, Satoru; Miyake, Yoshihiro; Shinokubo, Hiroshi

    2017-02-22

    This review focuses on the postfunctionalization of porphyrins and related compounds through catalytic and stoichiometric organometallic methodologies. The employment of organometallic reactions has become common in porphyrin synthesis. Palladium-catalyzed cross-coupling reactions are now standard techniques for constructing carbon-carbon bonds in porphyrin synthesis. In addition, iridium- or palladium-catalyzed direct C-H functionalization of porphyrins is emerging as an efficient way to install various substituents onto porphyrins. Furthermore, the copper-mediated Huisgen cycloaddition reaction has become a frequent strategy to incorporate porphyrin units into functional molecules. The use of these organometallic techniques, along with the traditional porphyrin synthesis, now allows chemists to construct a wide range of highly elaborated and complex porphyrin architectures.

  13. Plasma-assisted synthesis of MoS2

    Science.gov (United States)

    Campbell, Philip M.; Perini, Christopher J.; Chiu, Johannes; Gupta, Atul; Ray, Hunter S.; Chen, Hang; Wenzel, Kevin; Snyder, Eric; Wagner, Brent K.; Ready, Jud; Vogel, Eric M.

    2018-03-01

    There has been significant interest in transition metal dichalcogenides (TMDs), including MoS2, in recent years due to their potential application in novel electronic and optical devices. While synthesis methods have been developed for large-area films of MoS2, many of these techniques require synthesis temperatures of 800 °C or higher. As a result of the thermal budget, direct synthesis requiring high temperatures is incompatible with many integrated circuit processes as well as flexible substrates. This work explores several methods of plasma-assisted synthesis of MoS2 as a way to lower the synthesis temperature. The first approach used is conversion of a naturally oxidized molybdenum thin film to MoS2 using H2S plasma. Conversion is demonstrated at temperatures as low as 400 °C, and the conversion is enabled by hydrogen radicals which reduce the oxidized molybdenum films. The second method is a vapor phase reaction incorporating thermally evaporated MoO3 exposed to a direct H2S plasma, similar to chemical vapor deposition (CVD) synthesis of MoS2. Synthesis at 400 °C results in formation of super-stoichiometric MoS2 in a beam-interrupted growth process. A final growth method relies on a cyclical process in which a small amount of Mo is sputtered onto the substrate and is subsequently sulfurized in a H2S plasma. Similar results could be realized using an atomic layer deposition (ALD) process to deposit the Mo film. Compared to high temperature synthesis methods, the lower temperature samples are lower quality, potentially due to poor crystallinity or higher defect density in the films. Temperature-dependent conductivity measurements are consistent with hopping conduction in the plasma-assisted synthetic MoS2, suggesting a high degree of disorder in the low-temperature films. Optimization of the plasma-assisted synthesis process for slower growth rate and better stoichiometry is expected to lead to high quality films at low growth temperature.

  14. Directionality effects in percolation

    Science.gov (United States)

    Redner, Sidney

    The percolation properties of random networks containing resistors (two-way streets) and/or diodes (one-way streets) are considered. The directionality constraints of the diodes are found to lead to novel geometrical behavior. As a simple example, various random cluster models with a preferred direction, such as directed random walks or directed lattice animals, are shown to be anisotropic in character. The critical behavior of directed percolation is then treated and its connection with branching Markov processes is explained. A closely related "reverse" percolation problem, a transition from one-way percolation to isotropic percolation, is introduced. Finally, the geometrical properties of a network containing arbitrarily oriented diodes are treated. Symmetry and duality arguments are applied to yield exact results for certain aspects of its critical behavior.

  15. Free Electron Laser Synthesis of Functional Coatings

    Science.gov (United States)

    Schaaf, Peter; Höche, Daniel

    Functional and smart surfaces and coatings play an increasingly decisive role in the applicability and performance of modern materials. From an industrial point of view, there is a great interest with respect to friction, wear, corrosion, and further properties. Many methods have been developed for the improvement of the respective surface and material properties. Traditionally, these treatments range from simple PVD and CVD processes to complicated plasma and hybrid methods. Recently, it has been established that short laser pulses of high energy can induce a direct laser synthesis of functional coatings if the material's surface is irradiated in a reactive atmosphere. The process is based on a complicated combination of laser plasma - gas - material surface interactions. Tests for steel, aluminum, magnesium, titanium, and silicon in nitrogen, methane, and hydrogen atmospheres have been carried out successfully; with these materials, interesting coatings can be produced by direct laser synthesis, for example, AlN and SiC. Various laser types can be used for this purpose: Excimer, Nd:YAG, CO2 Laser, and even the free electron laser (FEL).

  16. Synthesis, characterization of organo-modified zeolitic nanomaterial from coal ash and application as adsorbent on remediation of contaminated water by rhodamine B and direct blue 71; Síntese, caracterização de nanomaterial zeolítico de cinzas de carvão organomodificado e aplicação como adsorvente na remediação de água contaminada por Rodamina B e Azul Direto 71

    Energy Technology Data Exchange (ETDEWEB)

    Alcântara, Raquel Reis

    2016-07-01

    The synthesis of zeolites from mineral coal fly and bottom ash was performed by alkaline hydrothermal treatment, which were named ZFA and ZBA, respectively. Organo-modified zeolites, SMZF and SMZB, were obtained from surface modification of ZFA and ZBA, respectively, using the cationic surfactant hexadecyltrimethylammonium bromide. From the remaining solutions generated in ZFA and ZBA synthesis it was possible to synthesis two new zeolites. The physicochemical characteristics of the synthesized nanomaterials zeolite as well as their respective raw materials, such as cation exchange capacity, density, specific area, chemical composition, mineralogical and morphological, among others, were determined. The adsorbents SMZF and SMZB were used to remove the dyes, Direct Blue 71 (DB71) and Rhodamine B (RB) from aqueous solutions in batch system. Thus, four systems DB71/SMZF, RB/SMZF, DB71/SMZB, RB/SMZB were investigated. The models of pseudo-first order and pseudo-second order were applied to the experimental data for the study the adsorption kinetics. The model of pseudo-second order was the one that best described the adsorption of all dye/organomodified-zeolites systems. The equilibrium adsorption was analyzed from four models isotherm, namely: Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-B). The results show that the model Freundlich and Langmuir best described the experimental data systems DB71/SMZF and DB71/SMZB, respectively. For systems with RB, the model D-R was the best fit for both adsorbents (SMZF and SMZB). The factorial design 2{sup 4} was applied to the analysis of the following factors influencing the adsorption process: initial concentration of dye (C{sub o}), pH, amount of adsorbent (M) and temperature (T). Under the conditions studied it concludes with the confidence interval of 95%, which for the DB71/SMZF system, the factors and their interactions that influence more were C{sub 0}, M, pH, pH∗M, pH∗C{sub 0}, M∗C{sub 0}, p

  17. Controlled synthesis of titania using water-soluble titanium complexes: A review

    Science.gov (United States)

    Truong, Quang Duc; Dien, Luong Xuan; Vo, Dai-Viet N.; Le, Thanh Son

    2017-07-01

    The development of human society has led to the increase in energy and resources consumption as well as the arising problems of environmental damage and the toxicity to the human health. The development of novel synthesis method which tolerates utilization of toxic solvents and chemicals would fulfill the demand of the society for safer, softer, and environmental friendly technologies. For the past decades, a remarkable progress has been attained in the development of new water-soluble titanium complexes (WSTC) and their use for the synthesis of nanocrystalline titanium dioxide materials by aqueous solution-based approaches. The progress of synthesis of nanocrystalline titanium dioxide using such WSTCs is reviewed in this work. The key structural features responsible for the successfully controlled synthesis of TiO2 are discussed to provide guidelines for the morphology-controlled synthesis. Finally, this review ends with a summary and some perspectives on the challenges as well as new directions in this fascinating research.

  18. Gene Synthesis with HG Khorana

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 17; Issue 12. Gene Synthesis with H G Khorana. Marvin H Caruthers. General Article Volume 17 Issue 12 December 2012 pp ... Keywords. Chemical synthesis of genes for yeast alanine tRNA and E. coli supressor tRNA; Khorana's philosophy on science.

  19. Organic synthesis with stable isotopes

    International Nuclear Information System (INIS)

    Blazer, R.M.; Daub, G.H.; Kerr, V.N.; Williams, D.L.; Whaley, T.W.

    1982-01-01

    Described is a scheme for the synthesis of L-arginine-1- 13 C utilizing methods developed for the synthesis of L-ornithine-1- 13 C from L-ornithine-2- 13 C and then converting ornithine into arginine with the enzyme acylase

  20. Chemical synthesis on SU-8

    DEFF Research Database (Denmark)

    Qvortrup, Katrine; Taveras, Kennedy; Thastrup, Ole

    2011-01-01

    In this paper we describe a highly effective surface modification of SU-8 microparticles, the attachment of appropriate linkers for solid-supported synthesis, and the successful chemical modification of these particles via controlled multi-step organic synthesis leading to molecules attached...

  1. Organic Synthesis using Clay Catalysts

    Indian Academy of Sciences (India)

    His work includes organic synthesis and reaction mechanisms mainly in the area of organosilicon chemistry. Presently he is also working on organic synthesis under solvent- free conditions and using clay-catalyses. Keywords. Montmorillonite, ion-exchange, clay-nanomaterials, dehydration pyrolysis, rearrangement, steric.

  2. First total synthesis of Boehmenan

    Indian Academy of Sciences (India)

    The first total synthesis of dilignan Boehmenan has been achieved. A biomimetic oxidative coupling of the ferulic acid methyl ester in the presence of silver oxide is the crucial step in the synthesis sequence, generating the dihydrobenzofuran skeleton. Hydroxyl group was protected with DHP and reducted with LiAlH4 to ...

  3. SHORT COMMUNICATION SYNTHESIS AND ANTIBACTERIAL ...

    African Journals Online (AJOL)

    Admin

    a. sodium nitrite, b. ethylacetoacetate, c. phenyl hydrazine, d. hydrazine hydrate, e. hydroxyl- amine hydrochloride, f. Salycylaldehye, g. chloroacetyl chloride, h. thioglycollic acid. Scheme 1. Synthesis of heterocyclic derivatives of sulfanilamide. Synthesis of compound 1 and 2a-e were done as per the reported method [7-8] ...

  4. Total synthesis of proposed auranthine.

    Science.gov (United States)

    Kshirsagar, Umesh A; Puranik, Vedavati G; Argade, Narshinha P

    2010-04-16

    Starting from CBz-protected glutamic anhydride and Boc-protected o-aminobenzyl amine, the first total synthesis of proposed structure of auranthine has been reported. An intramolecular aza-Wittig reaction involving a lactam carbonyl group that delivered the diazepine core unit was the key step in the synthesis.

  5. First total synthesis of Boehmenan

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 126; Issue 3 ... The first total synthesis of dilignan Boehmenan has been achieved. A biomimetic oxidative coupling of the ferulic acid methyl ester in the presence of silver oxide is the crucial step in the synthesis sequence, generating the dihydrobenzofuran skeleton.

  6. Stereoselective total synthesis of sphingolipids

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 128; Issue 11. Stereoselective total synthesis of sphingolipids. PARAMESH JANGILI PERLA ... Keywords. 1,2-Diacetyl D-erythro-sphinganine; 1,2-diacetyl L-threo-sphinganine; D-erythro-sphinganine triacetate; sphingolipids; total synthesis; Garner aldehyde.

  7. Chemical Synthesis of Antimicrobial Peptides.

    Science.gov (United States)

    Münzker, Lena; Oddo, Alberto; Hansen, Paul R

    2017-01-01

    Solid-phase peptide synthesis (SPPS) is the method of choice for chemical synthesis of peptides. In this nonspecialist review, we describe commonly used resins, linkers, protecting groups, and coupling reagents in 9-fluorenylmethyloxycarbonyl (Fmoc) SPPS. Finally, a detailed protocol for manual Fmoc SPPS is presented.

  8. Methyltrioctylammonium chloride catalysed sonochemical synthesis ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 125; Issue 5. Methyltrioctylammonium chloride catalysed sonochemical synthesis of acridine diones ... The greener, clean and efficient protocol for the synthesis of acridine diones derivatives has been achieved by reacting aromatic aldehyde, dimedone and amines ...

  9. Lactobacillusassisted synthesis of titanium nanoparticles

    Directory of Open Access Journals (Sweden)

    Jha Anal

    2007-01-01

    Full Text Available AbstractAn eco-friendlylactobacillussp. (microbe assisted synthesis of titanium nanoparticles is reported. The synthesis is performed at room temperature. X-ray and transmission electron microscopy analyses are performed to ascertain the formation of Ti nanoparticles. Individual nanoparticles as well as a number of aggregates almost spherical in shape having a size of 40–60 nm are found.

  10. High-Yield Synthesis and Applications of Anisotropic Gold Nanoparticles

    Science.gov (United States)

    Vigderman, Leonid

    This work will describe research directed towards the synthesis of anisotropic gold nanoparticles as well as their functionalization and biological applications. The thesis will begin by describing a new technique for the high-yield synthesis of gold nanorods using hydroquinone as a reducing agent. This addresses important limitations of the traditional nanorod synthesis including low yield of gold ions conversion to metallic form and inability to produce rods with longitudinal surface plasmon peak above 850 nm. The use of hydroquinone was also found to improve the synthesis of gold nanowires via the nanorod-seed mediated procedure developed in our lab. The thesis will next present the synthesis of novel starfruitshaped nanorods, mesorods, and nanowires using a modified nanorod-seed mediated procedure. The starfruit particles displayed increased activity as surfaceenhanced Raman spectroscopy (SERS) substrates as compared to smooth structures. Next, a method for the functionalization of gold nanorods using a cationic thiol, 16-mercaptohexadecyltrimethylammonium bromide (MTAB), will be described. By using this thiol, we were able to demonstrate the complete removal of toxic surfactant from the nanorods and were also able to precisely quantify the grafting density of thiol molecules on the nanorod surface through a combination of several analytical techniques. Finally, this thesis will show that MTABfunctionalized nanorods are nontoxic and can be taken up in extremely high numbers into cancer cells. The thesis will conclude by describing the surprising uptake of larger mesorods and nanowires functionalized with MTAB into cells in high quantities.

  11. Direction of time

    International Nuclear Information System (INIS)

    Mirman, R.

    1975-01-01

    The meaning of the phrase ''the direction of time'' and the physical problems involved are considered. These problems are discussed, and plausibility arguments are given to show that all clocks run in the same direction (almost always), that the most probable development of the universe during the early stages of the expansion would result in the introduction of some internal organization, and that the expansion of the universe and the increase in entropy define time directions that have the same sense. The question of what properties of the laws governing the universe lead to these results is studied

  12. Total Synthesis of Hyperforin.

    Science.gov (United States)

    Ting, Chi P; Maimone, Thomas J

    2015-08-26

    A 10-step total synthesis of the polycyclic polyprenylated acylphloroglucinol (PPAP) natural product hyperforin from 2-methylcyclopent-2-en-1-one is reported. This route was enabled by a diketene annulation reaction and an oxidative ring expansion strategy designed to complement the presumed biosynthesis of this complex meroterpene. The described work enables the preparation of a highly substituted bicyclo[3.3.1]nonane-1,3,5-trione motif in only six steps and thus serves as a platform for the construction of easily synthesized, highly diverse PPAPs modifiable at every position.

  13. Dibutylphosphoric acid synthesis

    International Nuclear Information System (INIS)

    Elias, H.; Boumaout, R.; Kellou, N.; Amedjkouh, A.; Hamidi, A.

    1995-09-01

    This work consists on the synthesis of dibutylphosphoric acis (DBP) by reaction of butanol with phosphorus pentoxid and on its separation by liquid-liquid extraction. It also deals with the characterization of DBP by some physicochemical analysis methods such as : chromatography, pH-metry and infrared and ultraviolet spectrophotometries. this study showed essentialy, that DBP can be formed in an appreciable amount (55%) when the reaction is realised with butanol/pentoxid molar ratio upper than 3 at temperature of 95 C

  14. Catalytic Oligopeptide Synthesis.

    Science.gov (United States)

    Liu, Zijian; Noda, Hidetoshi; Shibasaki, Masakatsu; Kumagai, Naoya

    2018-02-02

    Waste-free catalytic assembly of α-amino acids is fueled by a multiboron catalyst that features a characteristic B 3 NO 2 heterocycle, providing a versatile catalytic protocol wherein functionalized natural α-amino acid units are accommodated and commonly used protecting groups are tolerated. The facile dehydrative conditions eliminate the use of engineered peptide coupling reagents, exemplifying a greener catalytic alternative for peptide coupling. The catalysis is sufficiently robust to enable pentapeptide synthesis, constructing all four amide bond linkages in a catalytic fashion.

  15. Learning via Query Synthesis

    KAUST Repository

    Alabdulmohsin, Ibrahim Mansour

    2017-05-07

    Active learning is a subfield of machine learning that has been successfully used in many applications. One of the main branches of active learning is query synthe- sis, where the learning agent constructs artificial queries from scratch in order to reveal sensitive information about the underlying decision boundary. It has found applications in areas, such as adversarial reverse engineering, automated science, and computational chemistry. Nevertheless, the existing literature on membership query synthesis has, generally, focused on finite concept classes or toy problems, with a limited extension to real-world applications. In this thesis, I develop two spectral algorithms for learning halfspaces via query synthesis. The first algorithm is a maximum-determinant convex optimization method while the second algorithm is a Markovian method that relies on Khachiyan’s classical update formulas for solving linear programs. The general theme of these methods is to construct an ellipsoidal approximation of the version space and to synthesize queries, afterward, via spectral decomposition. Moreover, I also describe how these algorithms can be extended to other settings as well, such as pool-based active learning. Having demonstrated that halfspaces can be learned quite efficiently via query synthesis, the second part of this thesis proposes strategies for mitigating the risk of reverse engineering in adversarial environments. One approach that can be used to render query synthesis algorithms ineffective is to implement a randomized response. In this thesis, I propose a semidefinite program (SDP) for learning a distribution of classifiers, subject to the constraint that any individual classifier picked at random from this distributions provides reliable predictions with a high probability. This algorithm is, then, justified both theoretically and empirically. A second approach is to use a non-parametric classification method, such as similarity-based classification. In this

  16. Synthesis of deuterated clenbuterol

    Energy Technology Data Exchange (ETDEWEB)

    Joergensen, Ole [Risoe National Lab., Roskilde (Denmark). Solid State Physics Dept.; Egsgaard, Helge; Larsen, Elfinn [Risoe National Lab., Roskilde (Denmark). Science and Technology Dept.

    1996-11-01

    The synthesis of D{sub 9}-clenbuterol (I) and D{sub 3}-clenbuterol (II) is described. D{sub 9}-clenbuterol (I) was prepared from 4-amino-{alpha}-bromo-3, 5-dichloroacetophenone by reaction with D{sub 9}-tert-butylamine followed by reduction of the keto group with NaBH{sub 4}. D{sub 3}-clenbuterol (II) was prepared from 4-amino-{alpha}-tert-butylamino-3, 5-dichloroacetophenone by an exchange reaction of the {alpha}-hydrogens with deuterium followed by reduction of the keto group with NaBD{sub 4}. The eventual products were characterized by mass spectrometry and NMR. (author).

  17. Substrate-Directed Catalytic Selective Chemical Reactions.

    Science.gov (United States)

    Sawano, Takahiro; Yamamoto, Hisashi

    2018-03-06

    The development of highly efficient reactions at only the desired position is one of the most important subjects in organic chemistry. Most of the reactions in current organic chemistry are reagent- or catalyst-controlled reactions, and the regio- and stereoselectivity of the reactions are determined by the inherent nature of the reagent or catalyst. In sharp contrast, substrate-directed reaction determines the selectivity of the reactions by the functional group on the substrate and can strictly distinguish sterically and electronically similar multiple reaction sites in the substrate. In this Perspective, three topics of substrate-directed reaction are mainly reviewed: (1) directing group-assisted epoxidation of alkenes, (2) ring-opening reactions of epoxides by various nucleophiles, and (3) catalytic peptide synthesis. Our newly developed synthetic methods with new ligands including hydroxamic acid derived ligands realized not only highly efficient reactions but also pinpointed reactions at the expected position, demonstrating the substrate-directed reaction as a powerful method to achieve the desired regio- and stereoselective functionalization of molecules from different viewpoints of reagent- or catalyst-controlled reactions.

  18. Synthesis in land change science

    DEFF Research Database (Denmark)

    Magliocca, Nicholas R.; Rudel, Thomas K.; Verburg, Peter H.

    2015-01-01

    of these changes, land change science (LCS) draws on a wide array synthetic and meta-study techniques to generate global and regional knowledge from local case studies of land change. Here, we review the characteristics and applications of synthesis methods in LCS and assess the current state of synthetic research...... based on a meta-analysis of synthesis studies from 1995 to 2012. Publication of synthesis research is accelerating, with a clear trend toward increasingly sophisticated and quantitative methods, including meta-analysis. Detailed trends in synthesis objectives, methods, and land change phenomena......, synthesis methods based on local case studies will remain essential for generating systematic global and regional understanding of local land change for the foreseeable future, and multiple opportunities exist to accelerate and enhance the reliability of synthetic LCS research in the future. Demand...

  19. HF-Free Boc Synthesis of Peptide Thioesters for Ligation and Cyclization.

    Science.gov (United States)

    Raz, Richard; Burlina, Fabienne; Ismail, Mohamed; Downward, Julian; Li, Jiejin; Smerdon, Stephen J; Quibell, Martin; White, Peter D; Offer, John

    2016-10-10

    We have developed a convenient method for the direct synthesis of peptide thioesters, versatile intermediates for peptide ligation and cyclic peptide synthesis. The technology uses a modified Boc SPPS strategy that avoids the use of anhydrous HF. Boc in situ neutralization protocols are used in combination with Merrifield hydroxymethyl resin and TFA/TMSBr cleavage. Avoiding HF extends the scope of Boc SPPS to post-translational modifications that are compatible with the milder cleavage conditions, demonstrated here with the synthesis of the phosphorylated protein CHK2. Peptide thioesters give easy, direct, access to cyclic peptides, illustrated by the synthesis of cyclorasin, a KRAS inhibitor. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  20. Silica Synthesis by Sponges: Unanticipated Molecular Mechanism

    Science.gov (United States)

    Morse, D. E.; Weaver, J. C.

    2001-12-01

    Oceanic diatoms, sponges and other organisms synthesize gigatons per year of silica from silicic acid, ultimately obtained from the weathering of rock. This biogenic silica exhibits a remarkable diversity of structures, many of which reveal a precision of nanoarchitectural control that exceeds the capabilities of human engineering. In contrast to the conditions of anthropogenic and industrial manufacture, the biological synthesis of silica occurs under mild physiological conditions of low temperatures and pressures and near-neutral pH. In addition to the differentiation between biological and abiotic processes governing silica formation, the biomolecular mechanisms controlling synthesis of these materials may offer insights for the development of new, environmentally benign routes for synthesis of nanostructurally controlled silicas and high-performance polysiloxane composites. We found that the needle-like silica spicules made by the marine sponge, Tethya aurantia, each contain an occluded axial filament of protein composed predominantly of repeating assemblies of three similar subunits we named "silicateins." To our surprise, analysis of the purified protein subunits and the cloned silicatein DNAs revealed that the silicateins are highly homologous to a family of hydrolytic enzymes. As predicted from this finding, we discovered that the silicatein filaments are more than simple, passive templates; they actively catalyze and spatially direct polycondensation to form silica, (as well as the phenyl- and methyl-silsesquioxane) from the corresponding silicon alkoxides at neutral pH and low temperature. Catalytic activity also is exhibited by the silicatein subunits obtained by disaggregation of the protein filaments and those produced from recombinant DNA templates cloned in bacteria. This catalytic activity accelerates the rate-limiting hydrolysis of the silicon alkoxide precursors. Genetic engineering, used to produce variants of the silicatein molecule with

  1. Advance Directives - Multiple Languages

    Science.gov (United States)

    ... Expand Section Advance Directives - 简体中文 (Chinese, Simplified (Mandarin dialect)) Bilingual PDF Health Information Translations Chinese, Traditional (Cantonese dialect) (繁體中文) Expand Section Advance ...

  2. Direct Conversion of Energy

    Energy Technology Data Exchange (ETDEWEB)

    Corliss, William R

    1964-01-01

    Topics include: direct versus dynamic energy conversion; laws governing energy conversion; thermoelectricity; thermionic conversion; magnetohydrodynamic conversion; chemical batteries; the fuel cell; solar cells; nuclear batteries; and advanced concepts including ferroelectric conversion and thermomagnetic conversion.

  3. Directed GF-spaces

    Directory of Open Access Journals (Sweden)

    F.G. Arenas

    2001-10-01

    Full Text Available In this paper we introduce the concept of directed fractal structure, which is a generalization of the concept of fractal structure (introduced by the authors. We study the relation with transitive quasiuniformities and inverse limits of posets. We define the concept of GF-compactification and apply it to prove that the Stone-Cech compactification can be obtained as the GF-compactification of the directed fractal structure associated to the Pervin quasi-uniformity.

  4. Directional gear ratio transmissions

    Science.gov (United States)

    Lafever, A. E. (Inventor)

    1984-01-01

    Epicyclic gear transmissions which transmit output at a gear ratio dependent only upon the input's direction are considered. A transmission housing envelops two epicyclic gear assemblies, and has shafts extending from it. One shaft is attached to a sun gear within the first epicyclic gear assembly. Planet gears are held symmetrically about the sun gear by a planet gear carrier and are in mesh with both the sun gear and a ring gear. Two unidirectional clutches restrict rotation of the first planet gear carrier and ring gear to one direction. A connecting shaft drives a second sun gear at the same speed and direction as the first planet gear carrier while a connecting portion drives a second planet gear carrier at the same speed and direction as the first ring gear. The transmission's output is then transmitted by the second ring gear to the second shaft. Input is transmitted at a higher gear ratio and lower speed for all inputs in the first direction than in the opposite direction.

  5. The 1989 progress report: Polytechnic school laboratories' Direction

    International Nuclear Information System (INIS)

    1989-01-01

    The 1989 progress report of the laboratories' Direction of the Polytechnic School (France) is presented. The research activities carried out in each laboratory are summarized. Scientific and technical cooperation, financial and employement aspects are included. The main fields of research are: biochemistry, chemistry, reaction mechanisms, organic synthesis, mechanics of solids, meteorology, irradiated solids, optics, physics, biophysics, lasers, mathematics, econometrics, epistemology, management and computer science [fr

  6. Reevaluating synthesis by biology.

    Science.gov (United States)

    Yadav, Vikramaditya G; Stephanopoulos, Gregory

    2010-06-01

    The two cornerstones of synthetic biology are the introduction of the new technology of chemical DNA synthesis and its subsequent emphasis on the use of standardized biological parts in the construction of genetic systems aimed at eliciting of desired cellular behavior. A number of high-impact applications have been proposed for this technology, notable among them being the biological synthesis of valuable compounds for chemical or pharmaceutical use. To this end, synthetic biologists propose assembling metabolic pathways in toto by combining genes isolated from a variety of sources. While pathway construction is similar to approaches established long ago by Metabolic Engineering, the two methods deviate significantly when it comes to pathway optimization. Synthetic biologists opt for gene-combinatorial methods whereby large numbers of pathways, comprising several combinations of genes from different sources, and their mutants, are evaluated in search for an optimal pathway configuration. Metabolic engineering, on the contrary, aims to optimize pathways by tuning the activity of the intermediate reaction steps. Both, rational methods based on kinetics and regulation, as well as combinatorial methods, typically in this order, are used to this end. We argue that a systematic approach consisting of fine-tuning the properties of individual pathway components, prominently enzymes, is a superior strategy to searches spanning large genetic spaces in engineering optimal microbes for the production of chemical and pharmaceutical products. Copyright 2010 Elsevier Ltd. All rights reserved.

  7. Synthesis of Lysophospholipids

    Directory of Open Access Journals (Sweden)

    Paola D’Arrigo

    2010-03-01

    Full Text Available New synthetic methods for the preparation of biologically active phospholipids and lysophospholipids (LPLs are very important in solving problems of membrane–chemistry and biochemistry. Traditionally considered just as second-messenger molecules regulating intracellular signalling pathways, LPLs have recently shown to be involved in many physiological and pathological processes such as inflammation, reproduction, angiogenesis, tumorogenesis, atherosclerosis and nervous system regulation. Elucidation of the mechanistic details involved in the enzymological, cell-biological and membrane-biophysical roles of LPLs relies obviously on the availability of structurally diverse compounds. A variety of chemical and enzymatic routes have been reported in the literature for the synthesis of LPLs: the enzymatic transformation of natural glycerophospholipids (GPLs using regiospecific enzymes such as phospholipases A1 (PLA1, A2 (PLA2 phospholipase D (PLD and different lipases, the coupling of enzymatic processes with chemical transformations, the complete chemical synthesis of LPLs starting from glycerol or derivatives. In this review, chemo-enzymatic procedures leading to 1- and 2-LPLs will be described.

  8. Oxygenates vs. synthesis gas

    Energy Technology Data Exchange (ETDEWEB)

    Kamil Klier; Richard G. Herman; Alessandra Beretta; Maria A. Burcham; Qun Sun; Yeping Cai; Biswanath Roy

    1999-04-01

    Methanol synthesis from H{sub 2}/CO has been carried out at 7.6 MPa over zirconia-supported copper catalysts. Catalysts with nominal compositions of 10/90 mol% and 30/70 mol% Cu/ZrO{sub 2} were used in this study. Additionally, a 3 mol% cesium-doped 10/90 catalyst was prepared to study the effect of doping with heavy alkali, and this promoter greatly increased the methanol productivity. The effects of CO{sub 2} addition, water injection, reaction temperature, and H{sub 2}/C0 ratio have been investigated. Both CO{sub 2} addition to the synthesis gas and cesium doping of the catalyst promoted methanol synthesis, while inhibiting the synthesis of dimethyl ether. Injection of water, however, was found to slightly suppress methanol and dimethyl ether formation while being converted to CO{sub 2} via the water gas shift reaction over these catalysts. There was no clear correlation between copper surface area and catalyst activity. Surface analysis of the tested samples revealed that copper tended to migrate and enrich the catalyst surface. The concept of employing a double-bed reactor with a pronounced temperature gradient to enhance higher alcohol synthesis was explored, and it was found that utilization of a Cs-promoted Cu/ZnO/Cr{sub 2}O{sub 3} catalyst as a first lower temperature bed and a Cs-promoted ZnO/Cr{sub 2}O{sub 3} catalyst as a second high-temperature bed significantly promoted the productivity of 2-methyl-1-propanol (isobutanol) from H{sub 2}/CO synthesis gas mixtures. While the conversion of CO to C{sub 2+} oxygenates over the double-bed configuration was comparable to that observed over the single Cu-based catalyst, major changes in the product distribution occurred by the coupling to the zinc chromite catalyst; that is, the productivity of the C{sub 1}-C{sub 3} alcohols decreased dramatically, and 2-methyl branched alcohols were selectively formed. The desirable methanol/2-methyl oxygenate molar ratios close to 1 were obtained in the present double

  9. GH receptor blocker administration and muscle-tendon collagen synthesis in humans

    DEFF Research Database (Denmark)

    Nielsen, Rie H; Doessing, Simon; Goto, K.

    2011-01-01

    , but the effect of local IGF-I administration on tendon collagen synthesis in human has not been studied. The purpose of this study was to study whether local injections of IGF-I would have a stimulating effect on tendon collagen synthesis. Twelve healthy nonsmoking men [age 62 ± 1 years (mean ± SEM), BMI 27 ± 1.......05). In conclusion, local IGF-I administration can directly enhance tendon collagen synthesis both within and around the human tendon tissue....

  10. Mitochondrial Fatty Acid Synthesis Type II: More than Just Fatty Acids*

    OpenAIRE

    Hiltunen, J. Kalervo; Schonauer, Melissa S.; Autio, Kaija J.; Mittelmeier, Telsa M.; Kastaniotis, Alexander J.; Dieckmann, Carol L.

    2009-01-01

    Eukaryotes harbor a highly conserved mitochondrial pathway for fatty acid synthesis (FAS), which is completely independent of the eukaryotic cytosolic FAS apparatus. The activities of the mitochondrial FAS system are catalyzed by soluble enzymes, and the pathway thus resembles its prokaryotic counterparts. Except for octanoic acid, which is the direct precursor for lipoic acid synthesis, other end products and functions of the mitochondrial FAS pathway are still largel...

  11. Directed network modules

    International Nuclear Information System (INIS)

    Palla, Gergely; Farkas, Illes J; Pollner, Peter; Derenyi, Imre; Vicsek, Tamas

    2007-01-01

    A search technique locating network modules, i.e. internally densely connected groups of nodes in directed networks is introduced by extending the clique percolation method originally proposed for undirected networks. After giving a suitable definition for directed modules we investigate their percolation transition in the Erdos-Renyi graph both analytically and numerically. We also analyse four real-world directed networks, including Google's own web-pages, an email network, a word association graph and the transcriptional regulatory network of the yeast Saccharomyces cerevisiae. The obtained directed modules are validated by additional information available for the nodes. We find that directed modules of real-world graphs inherently overlap and the investigated networks can be classified into two major groups in terms of the overlaps between the modules. Accordingly, in the word-association network and Google's web-pages, overlaps are likely to contain in-hubs, whereas the modules in the email and transcriptional regulatory network tend to overlap via out-hubs

  12. Synthesis and Self-Assembly of Triangulenium Salts

    DEFF Research Database (Denmark)

    Shi, Dong

    This thesis describes the design and synthesis of asymmetrically substituted amphiphilic tis(dialkylamino)trioxiatriangulenium (ATOTA+) salts with different counter ions. Attention was focused on exploring the assembling properties of the ATOTA+ salts in aqueous media. A direct vortexing......-processed self-assembling method was developed to make aggregates with uniform morphologies and excellent stabilities in an equilibrium state either with pure ATOTA+ salts or with mixed systems of ATOTA+ salts and lipid molecules in aqueous media. Special emphasis was given to effects of the counterions......-assembly and triangulenium salts. Chapters 3 to 6 are mainly focused on the synthesis and self-assembly of trioxatriangulenium salts in aqueous media. In particular, chapter 3 reports a direct selfassembly of a synthetic triangulenium salt mixed with DMPC lipid (5/95 by molar ratio) to make mono disperse bilayer vesicles...

  13. Product engineering by high-temperature flame synthesis

    DEFF Research Database (Denmark)

    Johannessen, Tue; Johansen, Johnny; Mosleh, Majid

    also - coalescence of aggregated metal oxide nano-particles. As an example, it is possible produce well-defined spinel structures, e.g. zinc-aluminate (ZnAl2O4), with high specific surface area because the desired phase is formed directly without any need for post calcination. The production of other...... product gas can be applied directly in additional product engineering concepts. A brief overview of on-going product developments and product engineering projects is outlined below. These projects, which are all founded on flame synthesis of nano-structured materials, include: • Preparation of catalyzed......High-temperature flame processes can be applied as a tool for chemical product engineering. The general principle behind flame synthesis is the decomposition/oxidation of evaporated metal-precursors in a flame, thereby forming metal oxide monomers which nucleate, aggregate, and - to some extent...

  14. Chemical Protein Synthesis with the α-Ketoacid-Hydroxylamine Ligation.

    Science.gov (United States)

    Bode, Jeffrey W

    2017-09-19

    synthesis of new hydroxylamine monomers affording either natural or unnatural residues at the ligation site are discussed. By operation under acidic conditions and with a distinct preference for the ligation site, these efforts establish KAHA ligation as a complementary method to the venerable native chemical ligation (NCL) for chemical protein synthesis. This Account documents both the state of the KAHA ligation and the challenges in identifying, inventing, and optimizing new reactions and building blocks needed to interface KAHA ligation with Fmoc solid-phase peptide chemistry. With these challenges largely addressed, peptide segments ready for ligation are formed directly upon resin cleavage, facilitating rapid assembly of four to five segments into proteins. This work sets the stage for applications of the KAHA ligation to chemical biology and protein therapeutics.

  15. Direct reading dosimeter

    International Nuclear Information System (INIS)

    Thomson, I.

    1985-01-01

    This invention is a direct reading dosimeter which is light, small enough to be worn on a person, and measures both dose rates and total dose. It is based on a semiconductor sensor. The gate threshold voltage change rather than absolute value is measured and displayed as a direct reading of the dose rate. This is effected by continuously switching the gate of an MOS transistor from positive to negative bias. The output can directly drive a digital readout or trigger an audible alarm. The sensor device can be a MOSFET, bipolar transistor, or MOSFET capacitor which has its electrical characteristics change due to the trapped charge in the insulating layer of the device

  16. Synthesis of 2-phosphaadamantane derivatives

    International Nuclear Information System (INIS)

    Zemlyanoi, V.N.; Aleksandrov, A.M.; Kukhar', V.P.

    1986-01-01

    The authors describe the synthesis and properties of 2-phosphadamantane derivatives. For the synthesis of 2-phosphaadamantane derivatives they decided to use the methodology of the synthesis of 2-thiaadamantane. The IR spectra were determined on CHCl 3 solutions with a Specord 711R spectrometer, the PMR spectra were determined on Tesla BS-467 (60 MHz) and Bruker WP-200 (200 MHz) spectrometers, external standard hexamethyldisiloxane, the 31 P NMR spectra were determined on Tesla BS-487 C (30 MHz) and Bruker WP-200 (81 MHz) spectrometers, external standard 85% phosphoric acid, and the mass spectra were determined on an MS-1302 spectrometer

  17. Synthesis of C-vinylpyrroles

    International Nuclear Information System (INIS)

    Sobenina, Lyubov N; Demenev, Andrei P; Mikhaleva, Albina I; Trofimov, Boris A

    2002-01-01

    The latest advances in the synthesis of C-vinylpyrroles are generalised and systematised. Methods for the synthesis based on reactions of acylpyrroles and dicarbonyl compounds or their synthetic equivalents are still of most importance. New promising methods for the synthesis of C-vinylpyrroles are considered, among them the reactions of alkenyl ketone oximes with acetylene in the KOH-DMSO system and base-catalysed condensation of pyrrolecarbodithioates, which have recently become available, with CH-acids. The bibliography includes 195 references.

  18. Hypericin: chemical synthesis and biosynthesis.

    Science.gov (United States)

    Huang, Lin-Fang; Wang, Zeng-Hui; Chen, Shi-Lin

    2014-02-01

    Hypericin is one of the most important phenanthoperylene quinones extracted mainly from plants of the genus Hypericum belonging to the sections Euhypericum and Campylosporus of Keller's classification. Widespread attention to the antiviral and anti-tumor properties of hypericin has spurred investigations of the chemical synthesis and biosynthesis of this unique compound. However, the synthetic strategies are challenging for organic and biological chemists. In this review, specific significant advances in total synthesis, semi-synthesis, and biosynthesis in the past decades are summarized. Copyright © 2014 China Pharmaceutical University. Published by Elsevier B.V. All rights reserved.

  19. DIRECT KICKS IN BOXING

    Directory of Open Access Journals (Sweden)

    Izet Kahrović

    2009-11-01

    Full Text Available Hit directly, giving any impact maximum muscle strength is skill, and it is neces- sary to the exercise and learning to make it perfect. Training begins with oral statement, so that students get to know with the techni- que that works. After oral exposure, it is necessary to create a good notion on technology that is adopted. The best way for the creation of good notion is a good demonstration. In direct training kicks in the box, you need patience and gradualness and there- fore uses a large number of additional exercises. In their work with beginners, in the first class, individual elements of technology, and also direct blow, it is necessary to separate the parts and run them on multiple commands, to later come to the confluence in one command. Direct wounds, with left and right hand, can be run from the towns, on the head and body, from the movement, to step forward, step back and step aside, the remedy to the left and right side. Left direct is taking out from a running protrusion hands, but kick, which is a pro- duct of the system, ankle-knee-pelvis and shoulder forward horizontaly. Set at the time of stripes, body weight over the left leg. Right direct from the place, starting ekscentrical reflecsive impuls of a extensor muscle in ankle, knee and joint of a hip.This kind of a sud- den movement is running simultaneously with the rotation of the body around vertical (longitudinal axis, with the transfer body weight on the left leg. Further movement to the hand which serves as a lever, which is transmitted through the power stroke

  20. Direct Production of Silicones From Sand

    Energy Technology Data Exchange (ETDEWEB)

    Larry N. Lewis; F.J. Schattenmann: J.P. Lemmon

    2001-09-30

    Silicon, in the form of silica and silicates, is the second most abundant element in the earth's crust. However the synthesis of silicones (scheme 1) and almost all organosilicon chemistry is only accessible through elemental silicon. Silicon dioxide (sand or quartz) is converted to chemical-grade elemental silicon in an energy intensive reduction process, a result of the exceptional thermodynamic stability of silica. Then, the silicon is reacted with methyl chloride to give a mixture of methylchlorosilanes catalyzed by cooper containing a variety of tract metals such as tin, zinc etc. The so-called direct process was first discovered at GE in 1940. The methylchlorosilanes are distilled to purify and separate the major reaction components, the most important of which is dimethyldichlorosilane. Polymerization of dimethyldichlorosilane by controlled hydrolysis results in the formation of silicone polymers. Worldwide, the silicones industry produces about 1.3 billion pounds of the basic silicon polymer, polydimethylsiloxane.