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...

Switchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers

KAUST Repository

Della Sala, Giorgio

2017-05-31

The fluoride promoted vinylogous Mukaiyama-Michael reaction (VMMR) of 2-trimethylsilyloxyfuran with diverse α,β-unsaturated ketones is described. The TBAF catalyzed VMMR afforded high anti-diastereoselectivity irrespective of the solvents used. The KF/crown ethers catalytic systems proved to be highly efficient in terms of yields and resulted in a highly diastereoselective unprecedented solvent/catalyst switchable reaction. Anti-adducts were obtained as single diastereomers or with excellent diastereoselectivities when benzo-15-crown-5 in CH2Cl2 was employed. On the other hand, high syn-diastereoselectivities (from 76:24 to 96:4) were achieved by employing dicyclohexane-18-crown-6 in toluene. Based on DFT calculations, the catalysts/solvents-dependent switchable diastereoselectivities are proposed to be the result of loose or tight cation-dienolate ion pairs.

Gold-Catalyzed Enantio- and Diastereoselective Syntheses of Left Fragments of Azadirachtin/Meliacarpin-Type Limonoids.

Science.gov (United States)

Shi, Hang; Tan, Ceheng; Zhang, Weibin; Zhang, Zichun; Long, Rong; Gong, Jianxian; Luo, Tuoping; Yang, Zhen

2016-02-05

Meliacarpin-type limonoids are an important class of organic insecticides. Their syntheses are challenging due to their chemical complexity. Here, we report the highly enantio- and diastereoselective synthesis of the left fragments of azadirachtin I and 1-cinnamoylmelianolone, being two important family members of meliacarpin-type limonoids, via pairwise palladium- and gold-catalyzed cascade reactions. Gold-catalyzed reactions of 1,7-diynes were performed as model studies, and the efficient construction of tetracyclic late-stage intermediates was achieved on the basis of this key transformation. Our unique route gave both of the left fragments in 23 steps from the commercially available chiral starting material (-)-carvone. This study significantly advances research on the synthesis of the meliacarpin-type limonoids.

Diastereoselective and enantioselective reduction of tetralin-1,4-dione

OpenAIRE

Kündig, E Peter; Enriquez-Garcia, Alvaro

2008-01-01

Summary Background The chemistry of tetralin-1,4-dione, the stable tautomer of 1,4-dihydroxynaphthalene, has not been explored previously. It is readily accessible and offers interesting opportunities for synthesis. Results The title reactions were explored. L-Selectride reduced the diketone to give preferentially the cis-diol (d.r. 84 : 16). Red-Al gave preferentially the trans-diol (d.r. 13 : 87). NaBH4, LiAlH4, and BH3 gave lower diastereoselectivities (yields: 76–98%). Fractional crystall...

Stereoselective synthesis of the Halaven C14-C26 fragment from D-quinic acid: crystallization-induced diastereoselective transformation of an α-methyl nitrile.

Science.gov (United States)

Belanger, Francis; Chase, Charles E; Endo, Atsushi; Fang, Francis G; Li, Jing; Mathieu, Steven R; Wilcoxen, Annie Z; Zhang, Huiming

2015-04-20

Crystallization-induced diastereoselective transformation (CIDT) of an α-methyl nitrile completes an entirely non-chromatographic synthesis of the halichondrin B C14-C26 stereochemical array. The requisite α-methyl nitrile substrate is derived from D-quinic acid through a series of substrate-controlled stereoselective reactions via a number of crystalline intermediates that benefit from a rigid polycyclic template. Therefore, all four stereogenic centers in the Halaven C14-C26 fragment were derived from the single chiral source D-quinic acid. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

One-Pot Catalytic Enantio- and Diastereoselective Syntheses of anti-, syn-cis-Disubstituted, and syn-Vinyl Cyclopropyl Alcohols

Science.gov (United States)

Kim, Hun Young; Salvi, Luca; Carroll, Patrick J.; Walsh, Patrick J.

2009-01-01

Highly enantio- and diastereoselective methods for the synthesis of a variety of cyclopropyl alcohols are reported. These methods represent the first one-pot approaches to syn-vinyl cyclopropyl alcohols, syn-cis-disubstituted cyclopropyl alcohols, and anti-cyclopropyl alcohols from achiral precursors. The methods begin with enantioselective C–C bond formations promoted by a MIB-based zinc catalyst to generate allylic alkoxide intermediates. The intermediates are then subjected to in situ alkoxide-directed cyclopropanation to provide cyclopropyl alcohols. In the synthesis of vinyl cyclopropyl alcohols, hydroboration of enynes is followed by transmetalation of the resulting dienylborane to zinc to provide dienylzinc reagents. Enantioselective addition to aldehydes generates the requisite dienyl zinc alkoxides, which are then subjected to in situ cyclopropanation to furnish vinyl cyclopropyl alcohols. Cyclopropanation occurs at the double bond allylic to the alkoxide. Using this method, syn-vinylcyclopropyl alcohols are obtained in 65–85% yield, 76–93% ee, and >19:1 dr. To prepare anti-cyclopropanols, enantioselective addition of alkylzinc reagents to conjugated enals provides allylic zinc alkoxides. Because direct cyclopropanation provides syn-cyclopropyl alcohols, the intermediate allylic alkoxides were treated with TMSCl/Et3N to generate intermediate silyl ethers. In situ cyclopropanation of the allylic silyl ether resulted in cyclopropanation to form the anti-cyclopropyl silyl ether. Workup with TBAF affords the anti-cyclopropyl alcohols in one-pot in 60–82% yield, 89–99% ee, and ≥10:1 dr. For the synthesis of cis-disubstituted cyclopropyl alcohols, in situ generated (Z)-vinyl zinc reagents were employed in asymmetric addition to aldehydes to generate (Z)-allylic zinc alkoxides. In situ cyclopropanation provides syn-cis-disubstituted cyclopropyl alcohols in 42–70% yield, 88–97% ee, and >19:1 dr. These one-pot procedures enable the synthesis of a

A Microwave-Assisted Diastereoselective Multicomponent Reaction To Access Dibenzo[c,e]azepinones: Synthesis and Biological Evaluation

NARCIS (Netherlands)

Mehta, V.P.; Modha, S.G.; Ruijter, E.; van Hecke, K.; van Meervelt, L.; Pannecouque, C.; Balzarini, J.; Orru, R.V.A.; van der Eycken, E.

2011-01-01

An unprecedented microwave-assisted multicomponent strategy has been elaborated for the fast, efficient, and diastereoselective generation of the dibenzo[c,e]azepinone scaffold. The generated compounds were evaluated for their bioactivity. © 2011 American Chemical Society.

Switchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers

KAUST Repository

Della Sala, Giorgio; Sicignano, Marina; Schettini, Rosaria; De Riccardis, Francesco; Cavallo, Luigi; Minenkov, Yury; Batisse, Chloé ; Hanquet, Gilles; Leroux, Frederic; IZZO, Irene

2017-01-01

diastereoselectivities when benzo-15-crown-5 in CH2Cl2 was employed. On the other hand, high syn-diastereoselectivities (from 76:24 to 96:4) were achieved by employing dicyclohexane-18-crown-6 in toluene. Based on DFT calculations, the catalysts

Total Synthesis of Adunctin B.

Science.gov (United States)

Dethe, Dattatraya H; Dherange, Balu D

2018-03-16

Total synthesis of (±)-adunctin B, a natural product isolated from Piper aduncum (Piperaceae), has been achieved using two different strategies, in seven and three steps. The efficient approach features highly atom economical and diastereoselective Friedel-Crafts acylation, alkylation reaction and palladium catalyzed Wacker type oxidative cyclization.

Graphene oxide as a catalyst for the diastereoselective transfer hydrogenation in the synthesis of prostaglandin derivatives.

Science.gov (United States)

Coman, Simona M; Podolean, Iunia; Tudorache, Madalina; Cojocaru, Bogdan; Parvulescu, Vasile I; Puche, Marta; Garcia, Hermenegildo

2017-09-14

Modification of GO by organic molecules changes its catalytic activity in the hydrogen transfer from i-propanol to enones, affecting the selectivity to allyl alcohol and diastereoselectivity to the resulting stereoisomers. It is noteworthy the system does not contain metals and is recyclable.

Total synthesis of (±)-antroquinonol d.

Science.gov (United States)

Sulake, Rohidas S; Jiang, Yan-Feng; Lin, Hsiao-Han; Chen, Chinpiao

2014-11-21

Total synthesis of (±)-antroquinonol D, which is isolated from very expensive and rarely found Antrodia camphorata and which has potential anticancer properties, was achieved from 4-methoxyphenol. In addition, a Michael addition to dimethoxy cyclohexadienones was studied. The main step involved chelation and substrate-controlled diastereoselective reduction of cyclohexenone and lactonization. Lactone synthesis facilitated the diastereoselective reduction of ketone, which help control the desired stereochemistry at the crucial stereogenic center in the natural product. Other key reactions in the synthesis involved a Michael addition of dimethyl malonate on cyclohexadienone, dihydroxylation, and Wittig olefination. A sesquiterpene side chain was synthesized through coupling with geranyl phenyl sulfide and Bouveault-Blanc reduction.

IBX-mediated oxidation of unactivated cyclic amines: application in highly diastereoselective oxidative Ugi-type and aza-Friedel-Crafts reactions.

Science.gov (United States)

de Graaff, C; Bensch, L; van Lint, Matthijs J; Ruijter, E; Orru, R V A

2015-10-28

The first o-iodoxybenzoic acid (IBX) mediated oxidation of unactivated amines to imines is described. A range of meso-pyrrolidines were shown to be suitable substrates. The chemical space was further explored with one-pot oxidative Ugi-type and aza-Friedel-Crafts reactions, which proved to be highly diastereoselective.

Inverting the diastereoselectivity of the mukaiyama-michael addition with graphite-based catalysts

KAUST Repository

Acocella, Maria Rosaria; Mauro, Marco; Falivene, Laura; Cavallo, Luigi; Guerra, Gaetano

2014-01-01

, the graphite-based catalysts described here invert the diastereoselectivity relative to that observed with known catalysts, with the unprecedented large prevalence of the anti diastereoisomer. This inverted diastereoselectivity is increased when the catalyst

A Short Synthesis of (+)-Cyclophellitol

DEFF Research Database (Denmark)

Hansen, Flemming Gundorph; Bundgaard, Eva; Madsen, Robert

2005-01-01

A new synthesis of (+)-cyclophellitol, a potent b-glucosidase inhibitor, has been completed in nine steps from D-xylose. The key transformations involve a zinc-mediated fragmentation of benzyl-protected methyl 5-deoxy-5-iodo-xylofuranoside followed by a highly diastereoselective indium-mediated c......-mediated coupling with ethyl 4-bromocrotonate. Subsequent ring-closing olefin metathesis, ester reduction, olefin epoxidation, and deprotection then afford the natural product. This constitutes the shortest synthesis of (+)-cyclophellitol reported to date....

Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

Directory of Open Access Journals (Sweden)

Katherine M. Byrd

2015-04-01

Full Text Available The conjugate addition reaction has been a useful tool in the formation of carbon–carbon bonds. The utility of this reaction has been demonstrated in the synthesis of many natural products, materials, and pharmacological agents. In the last three decades, there has been a significant increase in the development of asymmetric variants of this reaction. Unfortunately, conjugate addition reactions using α,β-unsaturated amides and lactams remain underdeveloped due to their inherently low reactivity. This review highlights the work that has been done on both diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams.

Catalytic asymmetric synthesis of the alkaloid (+)-myrtine

NARCIS (Netherlands)

Pizzuti, Maria Gabriefla; Minnaard, Adriaan J.; Feringa, Ben L.

2008-01-01

A new protocol for the asymmetric synthesis of trans-2,6-disubstituted-4-piperidones has been developed using a catalytic enantioselective conjugate addition reaction in combination with a diastereoselective lithiation-substitution sequence; an efficient synthesis of (+)-myrtine has been achieved

Iridium-Catalyzed Dynamic Kinetic Isomerization: Expedient Synthesis of Carbohydrates from Achmatowicz Rearrangement Products.

Science.gov (United States)

Wang, Hao-Yuan; Yang, Ka; Bennett, Scott R; Guo, Sheng-rong; Tang, Weiping

2015-07-20

A highly stereoselective dynamic kinetic isomerization of Achmatowicz rearrangement products was discovered. This new internal redox isomerization provided ready access to key intermediates for the enantio- and diastereoselective synthesis of a series of naturally occurring sugars. The nature of the de novo synthesis also enables the preparation of both enantiomers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Inverting the diastereoselectivity of the mukaiyama-michael addition with graphite-based catalysts

KAUST Repository

Acocella, Maria Rosaria

2014-02-07

Here, we show that graphite-based catalysts, mainly graphite oxide (GO) and exfoliated GO, are effective recyclable catalysts for a relevant stereoselective Mukaiyama-Michael addition, outperforming currently available catalysts. Moreover, the graphite-based catalysts described here invert the diastereoselectivity relative to that observed with known catalysts, with the unprecedented large prevalence of the anti diastereoisomer. This inverted diastereoselectivity is increased when the catalyst concentration is reduced and after catalyst recycling. Density functional theory calculations suggest that the selectivity is determined by two types of supramolecular interactions operating between the catalyst and the substrates at the diastereoselectivity- determining transition state, specifically, the π-stacking of b-nitrostyrene with graphite and the van der Waals interaction between the SiMe3 group of the silyl ether and the graphite. © 2013 American Chemical Society.

Effect of uridine protecting groups on the diastereoselectivity of uridine-derived aldehyde 5’-alkynylation

Directory of Open Access Journals (Sweden)

Raja Ben Othman

2017-08-01

Full Text Available The 5’-alkynylation of uridine-derived aldehydes is described. The addition of alkynyl Grignard reagents on the carbonyl group is significantly influenced by the 2’,3’-di-O-protecting groups (R1: O-alkyl groups led to modest diastereoselectivities (65:35 in favor of the 5’R-isomer, whereas O-silyl groups promoted higher diastereoselectivities (up to 99:1 in favor of the 5’S-isomer. A study related to this protecting group effect on the diastereoselectivity is reported.

Highly efficient and diastereoselective gold(I)-catalyzed synthesis of tertiary amines from secondary amines and alkynes: substrate scope and mechanistic insights.

Science.gov (United States)

Liu, Xin-Yuan; Guo, Zhen; Dong, Sijia S; Li, Xiao-Hua; Che, Chi-Ming

2011-11-11

An efficient method for the synthesis of tertiary amines through a gold(I)-catalyzed tandem reaction of alkynes with secondary amines has been developed. In the presence of ethyl Hantzsch ester and [{(tBu)(2)(o-biphenyl)P}AuCl]/AgBF(4) (2 mol %), a variety of secondary amines bearing electron-deficient and electron-rich substituents and a wide range of alkynes, including terminal and internal aryl alkynes, aliphatic alkynes, and electron-deficient alkynes, underwent a tandem reaction to afford the corresponding tertiary amines in up to 99 % yield. For indolines bearing a preexisting chiral center, their reactions with alkynes in the presence of ethyl Hantzsch ester catalyzed by [{(tBu)(2)(o-biphenyl)P}AuCl]/AgBF(4) (2 mol %) afforded tertiary amines in excellent yields and with good to excellent diastereoselectivity. All of these organic transformations can be conducted as a one-pot reaction from simple and readily available starting materials without the need of isolation of air/moisture-sensitive enamine intermediates, and under mild reaction conditions (mostly room temperature and mild reducing agents). Mechanistic studies by NMR spectroscopy, ESI-MS, isotope labeling studies, and DFT calculations on this gold(I)-catalyzed tandem reaction reveal that the first step involving a monomeric cationic gold(I)-alkyne intermediate is more likely than a gold(I)-amine intermediate, a three-coordinate gold(I) intermediate, or a dinuclear gold(I)-alkyne intermediate. These studies also support the proposed reaction pathway, which involves a gold(I)-coordinated enamine complex as a key intermediate for the subsequent transfer hydrogenation with a hydride source, and reveal the intrinsic stereospecific nature of these transformations observed in the experiments. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cyclopropenes in Metallacycle-Mediated Cross-Coupling with Alkynes: Convergent Synthesis of Highly Substituted Vinylcyclopropanes.

Science.gov (United States)

O'Rourke, Natasha F; Micalizio, Glenn C

2016-03-18

Stereodivergent metallacycle-mediated cross-coupling reactions are described for the synthesis of densely functionalized vinylcyclopropanes from the union of alkynes with cyclopropenes. Strategies explored include hydroxyl-directed and nondirected processes, with the latter of these delivering vinylcyclopropanes with exquisite levels of regio- and stereoselectivity. Challenges inherent to these coupling reactions include diastereoselectivity (with respect to the cyclopropene) and regioselectivity (with respect to both coupling partners).

Stereoselective total synthesis of the potent anti-asthmatic compound CMI-977 (LDP-977)

Energy Technology Data Exchange (ETDEWEB)

Dias, Luiz Carlos; Farina, Lui Strambi; Ferreira, Marco Antonio Barbosa, E-mail: ldias@iqm.unicamp.br [Universidade de Campinas (UNICAMP), SP (Brazil). Instituto de Quimica

2013-02-15

A short and efficient stereoselective total synthesis of CMI-977 (LDP-977), a potent and orally active anti-asthmatic compound, was developed. The key steps involve a highly diastereoselective Mukaiyama oxidative cyclization, which provides the trans-THF (tetrahydrofuran) unit and a Seyferth-Gilbert homologation to construct the triple bond in the target molecule. The synthesis of the key chiral building block was performed using Jacobsen hydrolytic kinetic resolution. (author)

Stereoselective total synthesis of the potent anti-asthmatic compound CMI-977 (LDP-977)

International Nuclear Information System (INIS)

Dias, Luiz Carlos; Farina, Lui Strambi; Ferreira, Marco Antonio Barbosa

2013-01-01

A short and efficient stereoselective total synthesis of CMI-977 (LDP-977), a potent and orally active anti-asthmatic compound, was developed. The key steps involve a highly diastereoselective Mukaiyama oxidative cyclization, which provides the trans-THF (tetrahydrofuran) unit and a Seyferth-Gilbert homologation to construct the triple bond in the target molecule. The synthesis of the key chiral building block was performed using Jacobsen hydrolytic kinetic resolution. (author)

L-Selectride-Mediated Highly Diastereoselective Asymmetric Reductive Aldol Reaction: Access to an Important Subunit for Bioactive Molecules

OpenAIRE

Ghosh, Arun K.; Kass, Jorden; Anderson, David D.; Xu, Xiaoming; Marian, Christine

2008-01-01

L-Selectride reduction of a chiral or achiral enone followed by reaction of the resulting enolate with optically active α-alkoxy aldehydes proceeded with excellent diastereoselectivity. The resulting α,α-dimethyl-β-hydroxy ketones are inherent to a variety of biologically active natural products.

L-selectride-mediated highly diastereoselective asymmetric reductive aldol reaction: access to an important subunit for bioactive molecules.

Science.gov (United States)

Ghosh, Arun K; Kass, Jorden; Anderson, David D; Xu, Xiaoming; Marian, Christine

2008-11-06

L-selectride reduction of a chiral or achiral enone followed by reaction of the resulting enolate with optically active alpha-alkoxy aldehydes proceeded with excellent diastereoselectivity. The resulting alpha,alpha-dimethyl-beta-hydroxy ketones are inherent to a variety of biologically active natural products.

Efficient Asymmetric Synthesis of S,S-2-methylsulfanyl-2-methylsulfinyl-1-indanone

OpenAIRE

Derisvaldo Rosa Paiva; Roberto da Silva Gomes

2013-01-01

Diastereoselective synthesis of SS-2-methylsulfanyl-2-methylsulfinyl-1-indanol by reduction of SS-2-methylsulfanyl-2-methylsulfinyl-1-indanone optically enriched demonstrating to be highly efficiency using the sulfanyl group as asymmetric induction control agent during an addition reaction to carbonyl group.The 2-methylsulfinyl-1-indanone was obtained for the first time in one unique step without further oxidation steps. The synthesis of SR, SS of 2-methylsulphinyl-1-indanone optically enrich...

Total synthesis of broussonetine F: the orthoamide Overman rearrangement of an allylic diol.

Science.gov (United States)

Hama, Naoto; Aoki, Toshihiro; Miwa, Shohei; Yamazaki, Miki; Sato, Takaaki; Chida, Noritaka

2011-02-18

A first total synthesis of broussonetine F from diethyl L-tartrate was achieved. The cornerstone of our synthesis was an orthoamide Overman rearrangement, which provided an allylic amino alcohol with complete diastereoselectivity.

Nazarov cyclization initiated by peracid oxidation: the total synthesis of (+/-)-rocaglamide.

Science.gov (United States)

Malona, John A; Cariou, Kevin; Frontier, Alison J

2009-06-10

The total syntheses of aglafolin, rocagloic acid, and rocaglamide using Nazarov cyclization are described. Generation of the necessary oxyallyl cation intermediate was accomplished via peracid oxidation of an allenol ether to generate an unusual oxycarbenium ion species that undergoes cyclization. The synthesis is efficient, highly diastereoselective, and strategically distinct from previous syntheses of rocaglamide.

The Inverse Demand Oxa-Diels-Alder Reaction of Resorcinarenes: An Experimental and Theoretical Analysis of Regioselectivity and Diastereoselectivity.

Science.gov (United States)

Stefańska, Karolina; Jędrzejewska, Hanna; Wierzbicki, Michał; Szumna, Agnieszka; Iwanek, Waldemar

2016-07-15

The Diels-Alder reaction enables introduction of new functionalities onto the resorcinarene skeleton with simultaneous generation of new stereogenic centers and expansion of the internal cavity. We present highly regio- and diastereoselective inverse electron demand oxa-Diels-Alder reactions of resorcinarene ortho-quinone methide with benzofuran and indene, each generating 12 new stereogenic centers. The mechanism and reasons for regioselectivity and diastereoselectivity were analyzed using theoretical calculations (NBO charges, Fukui functions, transition state energies, and thermodynamic stability of the products). Enantiomers were separated, and their configurations were determined by comparison of experimental and theoretical electronic circular dichroism spectra.

N-Heterocyclic-Carbene-Catalysed Diastereoselective Vinylogous Mukaiyama/Michael Reaction of 2-(Trimethylsilyloxy)furan and Enones

KAUST Repository

Wang, Ying; Du, Guang Fen; Xing, Fen; Huang, Kuo-Wei; Dai, Bin; He, Lin

2015-01-01

N-heterocyclic carbenes have been utilised as highly efficient nucleophilic organocatalysts to mediate vinylogous Mukaiyama/Michael reactions of 2-(trimethylsilyloxy)furan with enones to afford γ-substituted butenolides in 44-99% yield with 3:1-32:1 diastereoselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

N-Heterocyclic-Carbene-Catalysed Diastereoselective Vinylogous Mukaiyama/Michael Reaction of 2-(Trimethylsilyloxy)furan and Enones

KAUST Repository

Wang, Ying

2015-10-15

N-heterocyclic carbenes have been utilised as highly efficient nucleophilic organocatalysts to mediate vinylogous Mukaiyama/Michael reactions of 2-(trimethylsilyloxy)furan with enones to afford γ-substituted butenolides in 44-99% yield with 3:1-32:1 diastereoselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalyst-Directed Diastereoselective Isomerization of Allylic Alcohols for the Stereoselective Construction of C(20) in Steroid Side Chains: Scope and Topological Diversification.

Science.gov (United States)

Li, Houhua; Mazet, Clément

2015-08-26

The stereoselective construction of C20 in steroidal derivatives by a highly diastereoselective Ir-catalyzed isomerization of primary allylic alcohols is reported. A key aspect of this strategy is a straightforward access to geometrically pure steroidal enol tosylate and enol triflate intermediates for subsequent high yielding stereoretentive Negishi cross-coupling reactions to allow structural diversity to be introduced. A range of allylic alcohols participates in the diastereoselective isomerization under the optimized reaction conditions. Electron-rich and electron-poor aryl or heteroaryl substituents are particularly well-tolerated, and the stereospecific nature of the reaction provides indifferently access to the natural C20-(R) and unnatural C20-(S) configurations. Alkyl containing substrates are more challenging as they affect regioselectivity of iridium-hydride insertion. A rationale for the high diastereoselectivities observed is proposed for aryl containing precursors. The scope of our method is further highlighted through topological diversification in the side chain and within the polycyclic domain of advanced and complex steroidal architectures. These findings have the potential to greatly simplify access to epimeric structural analogues of important steroid scaffolds for applications in biological, pharmaceutical, and medical sciences.

Diastereoselective and one-pot synthesis of trans-isoquinolonic acids via three-component condensation of homophthalic anhydride, aldehydes, and ammonium acetate catalyzed by aspartic acid

Czech Academy of Sciences Publication Activity Database

Ghorbani-Choghamarani, A.; Hajjami, M.; Norouzi, M.; Abbasityula, Y.; Eigner, Václav; Dušek, Michal

2013-01-01

Roč. 69, č. 32 (2013), s. 6541-6544 ISSN 0040-4020 Grant - others:AVČR(CZ) Praemium Academiae Institutional support: RVO:68378271 Keywords : isoquinolonic acid * diastereoselective * aldehyde * homophthalic anhydride * ammonium acetate Subject RIV: CC - Organic Chemistry Impact factor: 2.817, year: 2013

Diastereoselectivity in scalemic tartrate/titanium epoxidations.

Science.gov (United States)

Brown, J M; Leppard, S J; Oakes, J; Thornthwaite, D

2000-06-01

Nonlinearity in the diastereoselectivity of epoxidation of allylic alcohols with mixtures of titanium isopropoxide, tertbutyl hydroperoxide, and diethyl tartrate was observed. Racemic and enantiomerically pure alcohols E-2-methyl-4-hexen-3-ol and E-1-methoxy-5-(O-tertbutyldimethylsilyloxy)-2-penten-4-ol were prepared. Epoxidation reactions were carried out with Ti(OPri)4 and ButOOH accompanied by diethyl tartrate of varying enantiomeric purity. The simplest explanation of these results is that a dimeric epoxidation reagent is involved, with significantly different reactivity for the homochiral and racemic forms. Copyright 2000 Wiley-Liss, Inc.

Synthesis of the AB ring system of clifednamide utilizing Claisen rearrangement and Diels-Alder reaction as key steps.

Science.gov (United States)

Loke, Inga; Bentzinger, Guillaume; Holz, Julia; Raja, Aruna; Bhasin, Aman; Sasse, Florenz; Köhn, Andreas; Schobert, Rainer; Laschat, Sabine

2016-01-21

In order to construct the functionalized AB ring system of clifednamide, member of the class of macrocyclic tetramic acid lactams, a synthesis was developed which utilized an Ireland-Claisen rearrangement and an intramolecular Diels-Alder reaction. Starting from di-O-isopropylidene-d-mannitol the allyl carboxylate precursor for the sigmatropic rearrangement was prepared. This rearrangement proceeded diastereoselectively only in the presence of an allyl silyl ether instead of the parent enone in the side chain, as suggested by deuteration experiments. A subsequent Diels-Alder reaction yielded the target ethyl hexahydro-1H-indene-carboxylate with high diastereoselectivity. Quantum-chemical investigations of this intramolecular Diels-Alder reaction support the proposed configuration of the final product.

Catalytic Asymmetric Piancatelli Rearrangement: Brønsted Acid Catalyzed 4π Electrocyclization for the Synthesis of Multisubstituted Cyclopentenones

KAUST Repository

Cai, Yunfei

2016-10-13

The first catalytic asymmetric Piancatelli reaction is reported. Catalyzed by a chiral Brønsted acid, the rearrangement of a wide range of furylcarbinols with a series of aniline derivatives provides valuable aminocyclopentenones in high yields as well as excellent enantioselectivities and diastereoselectivities. The high value of the aza-Piancatelli rearrangement was demonstrated by the synthesis of a cyclopentane-based hNK1 antagonist analogue.

Efficient Asymmetric Synthesis of S,S-2-methylsulfanyl-2-methylsulfinyl-1-indanone

Directory of Open Access Journals (Sweden)

Derisvaldo Rosa Paiva

2013-05-01

Full Text Available Diastereoselective synthesis of SS-2-methylsulfanyl-2-methylsulfinyl-1-indanol by reduction of SS-2-methylsulfanyl-2-methylsulfinyl-1-indanone optically enriched demonstrating to be highly efficiency using the sulfanyl group as asymmetric induction control agent during an addition reaction to carbonyl group.The 2-methylsulfinyl-1-indanone was obtained for the first time in one unique step without further oxidation steps. The synthesis of SR, SS of 2-methylsulphinyl-1-indanone optically enriched in good yield and good enantiomeric excess determined by nuclear magnetic resonance technique employing the Kagan reagent as chiral shift agent.

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.

Diastereoselectivity in the reduction of bicyclic enones with hindered hydrides

OpenAIRE

Camozzato, Andreza C.; Tenius, Beatriz S. M.; Oliveira, Eduardo R. de; Viegas Jr., Cláudio; Victor, Maurício M.; Silveira, Leandro G. da

2008-01-01

Reduction of five substituted octalones employing lithium tri-sec-butylborohydride (L-selectride®) in THF and ethyl ether led to allylic alcohols with moderate diastereoselectivity. The stereoselectivity of addition of bulky hydrides showed to be different from most examples in the literature and was strongly influenced by substitution on the octalone ring.

Diastereoselectivity in the reduction of bicyclic enones with hindered hydrides

International Nuclear Information System (INIS)

Camozzato, Andreza C.; Tenius, Beatriz S. M.; Oliveira, Eduardo R. de; Viegas Junior, Claudio; Victor, Mauricio M.; Silveira, Leandro G. da

2008-01-01

Reduction of five substituted octalones employing lithium tri-sec-butylborohydride (L-selectride R ) in THF and ethyl ether led to allylic alcohols with moderate diastereoselectivity. The stereoselectivity of addition of bulky hydrides showed to be different from most examples in the literature and was strongly influenced by substitution on the octalone ring. (author)

Studies on the Total Synthesis of Amphidinolide O (II): A Stereoselective Synthesis of C1-C11 Fragment

Energy Technology Data Exchange (ETDEWEB)

Jang, Mi Yeon; Kim, Jong Woo; Lee, Duck Hyung [Sogang University, Seoul (Korea, Republic of)

2005-10-15

Two ketones and, the C1-C11 fragment of Amphidinolide O, were prepared stereoselectively via 14 and 16 step sequences in 8.7% and 2.0% overall yield, respectively. The amphidinolides were isolated from the marine dinoflagellate Amphidinium sp., which produces a host of secondary metabolites endowed with potent cytotoxicity against various cancer cell lines. Amphidinolide O displayed potent in vitro cytotoxicity against L1210 marine leukemia cells and human epidermoid carcinoma KB cells with 1.7 and 3.6 μg/mL of IC50s, respectively. In addition to our recent reports regarding to the synthesis of C12-C17 and C3-C11 fragments of amphidinolide O, we describe herein a new route to diastereoselective synthesis of C1-C11 fragment of. The retrosynthetic analysis of led to the C1-C11 fragment and C12-C17 fragment. The hemiketal was expected from acyclic precursor 4 which, in turn, would be derived by diastereoselective aldol reaction between ketone and aldehyde.

Cross-Aldol Reaction of Activated Carbonyls with Nitrosocarbonyl Intermediates: Stereoselective Synthesis toward α-Hydroxy-β-amino Esters and Amides.

Science.gov (United States)

Mallik, Sumitava; Bhajammanavar, Vinod; Ramakrishna, Isai; Baidya, Mahiuddin

2017-07-21

A practical and flexible strategy toward α-hydroxy-β-amino esters and amides, which are important biological motifs, based on an organocatalytic cross-aldol reaction of in situ-generated nitrosocarbonyl intermediates followed by hydrogenation is presented. The protocol features operational simplicity, high yields, a wide substrate scope, and high regio- and diastereoselectivity profiles. The utility of this method was showcased through the synthesis of bestatin analogues and indole formation.

Protecting-Group-Free Synthesis of 2-Deoxy-Aza-Sugars

Directory of Open Access Journals (Sweden)

Mattie Simon Maria Timmer

2009-12-01

Full Text Available The protecting-group-free asymmetric synthesis of 1,2,4-trideoxy-1,4-imino-L-xylitol is readily achieved in five steps from 2-deoxy-D-ribose and with an overall yield of 48%. Key in this synthesis is the application of our recently developed Vasella-reductive amination and carbamate annulation methodologies to the synthesis of 2-deoxy-aza-sugars. The carbamate annulation occurred with excellent yield and diastereoselectively (>20:1 d.r., in favour of the 3,4-cis isomer.

Highly selective sulfur ylide mediated asymmetric epoxidations and aziridinations using an inexpensive chiral sulfide and applications to the synthesis of quinine and quinidine (abstract)

International Nuclear Information System (INIS)

Arshad, M.; Illa, O.; Mcgarrigle, E.M.

2011-01-01

Asymmetric sulfur ylide mediated epoxidation, which is considered a complimentary method to asymmetric epoxidation of alkene has been utilized as a key step in the asymmetric total synthesis of complex cinchona alkaloids quinine and quinidine. Isothiocineole 1, which was readily available in one step from very inexpensive starting materials, is employed as a chiral sulfide to prepare the desired sulfonium salt 2. The semi-stabilised ylide derived from this salt on epoxidation with meroquinene aldehyde 3, afforded the required epoxide 4 in 81% yield and 89:11 diastereoselectivity (trans/cis). The epoxide was converted to the target quinine 5 in 73% yield over four steps in one pot. Similarly, the opposite enantiomer of isothiocineole was used to synthesise the corresponding sulfonium salt, which on reaction with meroquinene aldehyde gave epoxide in 73% yield and 84:16 diastereoselectivity (trans/cis). This epoxide was transformed to the target quinidine in 78% yield over four steps in one pot. The epoxidation reactions proceeded under reagent control with high trans selectivity. The effect of sulfide and ylide substituents on the stereochemical outcome of the epoxidation reaction is also prescribed. (author)

A 11-Steps Total Synthesis of Magellanine through a Gold(I)-Catalyzed Dehydro Diels-Alder Reaction.

Science.gov (United States)

McGee, Philippe; Bétournay, Geneviève; Barabé, Francis; Barriault, Louis

2017-05-22

We have developed an innovative strategy for the formation of angular carbocycles via a gold(I)-catalyzed dehydro Diels-Alder reaction. This transformation provides rapid access to a variety of complex angular cores in excellent diastereoselectivities and high yields. The usefulness of this Au I -catalyzed cycloaddition was further demonstrated by accomplishing a 11-steps total synthesis of (±)-magellanine. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Total synthesis of the proposed structure of trichodermatide A.

Science.gov (United States)

Myers, Eddie; Herrero-Gómez, Elena; Albrecht, Irina; Lachs, Jennifer; Mayer, Peter; Hanni, Matti; Ochsenfeld, Christian; Trauner, Dirk

2014-10-17

A short total synthesis of the published structure of racemic trichodermatide A is reported. Our synthesis involves a Knoevenagel condensation/Michael addition sequence, followed by the formation of tricyclic hexahydroxanthene-dione and a diastereoselective bis-hydroxylation. The final product, the structure of which was confirmed by X-ray crystallography, has NMR spectra that are very similar, but not identical, to those of the isolated natural product. Quantum chemically computed (13)C shifts agree well with the present NMR measurements.

(S)-1-Aminoindane : synthesis by chirality transfer using (R)-phenylglycine amide as chiral auxiliary

NARCIS (Netherlands)

Uiterweerd, Patrick G.H.; Sluis, Marcel van der; Kaptein, Bernard; Lange, Ben de; Kellogg, Richard M.; Broxterman, Quirinus B.

2003-01-01

A practical asymmetric synthesis of nearly enantiomerically pure (S)-1-aminoindane has been developed. The key step involves the diastereoselective heterogeneous metal-catalyzed reduction of the ketimine of 1-indanone with the chiral auxiliary (R)-phenylglycine amide. The selectivity of the

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

DEFF Research Database (Denmark)

Ascic, Erhad

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

A concise enantioselective synthesis of the guaiane sesquiterpene (−-oxyphyllol

Directory of Open Access Journals (Sweden)

Martin Zahel

2013-10-01

Full Text Available (−-Oxyphyllol was prepared in only 4 steps from an epoxy enone that already served as an intermediate for the total synthesis of the anticancer guaiane (−-englerin A. A regio- and diastereoselective Co(II-catalyzed hydration of the olefin and a transannular epoxide opening were used as the key reactions.

Studies Toward the Asymmetric Synthesis of the Right Part of the Mycalamides

OpenAIRE

Zhong, H. Marlon; Sohn, Jeong-Hun; Rawal, Viresh H.

2007-01-01

Described herein is the asymmetric synthesis of a functionalized, trioxadecalin unit that comprises the right-hand part of the mycalamides and related natural products. The synthetic route involves a 16-step sequence that accomplishes the formation of two heterocyclic rings and the generation of five stereocenters. The synthesis commenced with a C2 symmetric starting material, diethyl D-tartrate, and took advantage of a relay of diastereoselective reactions to extend this four-carbon chain an...

Total synthesis of a CD-ring: side-chain building block for preparing 17-epi-calcitriol derivatives from the Hajos-Parrish dione.

Science.gov (United States)

Michalak, Karol; Wicha, Jerzy

2011-08-19

An efficient synthesis of the key building block for 17-epi-calctriol from the Hajos-Parrish dione involving a sequence of diastereoselective transformation of the azulene core and the side-chain construction is presented.

Asymmetric synthesis of quaternary aryl amino acid derivatives via a three-component aryne coupling reaction

Directory of Open Access Journals (Sweden)

Elizabeth P. Jones

2011-11-01

Full Text Available A method was developed for the synthesis of α-alkyl, α-aryl-bislactim ethers in good to excellent yields and high diastereoselectivities, consisting of a facile one-pot procedure in which the aryl group is introduced by means of a nucleophilic addition to benzyne and the alkyl group by alkylation of a resultant benzylic anion. Hydrolysis of the sterically less hindered adducts gave the corresponding quaternary amino acids with no racemization, whereas hydrolytic ring opening gave the corresponding valine dipeptides from bulkier bislactims.

Acyclic diastereoselection in prochiral radical addition to prochiral olefins.

Science.gov (United States)

Sibi, Mukund P; Rheault, Tara R; Chandramouli, Sithamalli V; Jasperse, Craig P

2002-03-27

The stereochemical preference (syn or anti) when prochiral radicals add to prochiral acceptors is of fundamental interest. The primary focus of this research was to determine which factors influence the relative stereochemistry between the beta and gamma chiral centers when these are formed concurrently. While moderate diastereoselectivity was found for addition of alkyl (6a-d) and alpha-alkoxy radicals (16a-c) (15:1 anti). Steric influence in alkyl radical additions was difficult to evaluate due to decreased reactivity when using bulky reaction partners; however, more reactive alpha-alkoxy radicals, it was found that increasing steric bulk leads to moderate increases in selectivity. In addition, higher selectivity was observed when employing lanthanide Lewis acids whose environment (reactivity) was modified using achiral additives, suggesting a potentially simple means for selectivity enhancements in radical reactions. Overall these results indicate that significant stereoelectronic effects are necessary to achieve high levels of selectivity in prochiral radical additions to prochiral acceptors.

Advanced asymmetric synthesis of (1R,2S)-1-amino-2-vinylcyclopropanecarboxylic acid by alkylation/cyclization of newly designed axially chiral Ni(II) complex of glycine Schiff base.

Science.gov (United States)

Kawashima, Aki; Shu, Shuangjie; Takeda, Ryosuke; Kawamura, Akie; Sato, Tatsunori; Moriwaki, Hiroki; Wang, Jiang; Izawa, Kunisuke; Aceña, José Luis; Soloshonok, Vadim A; Liu, Hong

2016-04-01

Asymmetric synthesis of (1R,2S)-1-amino-2-vinylcyclopropanecarboxylic acid (vinyl-ACCA) is in extremely high demand due to the pharmaceutical importance of this tailor-made, sterically constrained α-amino acid. Here we report the development of an advanced procedure for preparation of the target amino acid via two-step SN2 and SN2' alkylation of novel axially chiral nucleophilic glycine equivalent. Excellent yields and diastereoselectivity coupled with reliable and easy scalability render this method of immediate use for practical synthesis of (1R,2S)-vinyl-ACCA.

Stereoselective Synthesis of Highly Functionalized α-Diazo-β-ketoalkanoates via Catalytic Onepot Mukaiyama-Aldol Reactions

Science.gov (United States)

Zhou, Lei; Doyle, Michael P.

2010-01-01

Methyl diazoacetoacetate undergoes zinc triflate catalyzed condensation with a broad selection of aldehydes to produce δ-siloxy-α-diazo-β-ketoalkanoates in good yield, and δ-hydroxy-α-diazo-β-ketoalkanoates are formed with high diastereoselectivity in reactions with α-diazo-β-ketopentanoate promoted by dibutylboron triflate. PMID:20102172

Catalytic stereoselective synthesis of highly substituted indanones via tandem Nazarov cyclization and electrophilic fluorination trapping.

Science.gov (United States)

Nie, Jing; Zhu, Hong-Wei; Cui, Han-Feng; Hua, Ming-Qing; Ma, Jun-An

2007-08-02

A new catalytic stereoselective tandem transformation via Nazarov cyclization/electrophilic fluorination has been accomplished. This sequence is efficiently catalyzed by a Cu(II) complex to afford fluorine-containing 1-indanone derivatives with two new stereocenters with high diastereoselectivity (trans/cis up to 49/1). Three examples of catalytic enantioselective tandem transformation are presented.

A divergent [5+2] cascade approach to bicyclo[3.2.1]octanes: facile synthesis of ent-kaurene and cedrene-type skeletons.

Science.gov (United States)

He, Chi; Bai, Zengbing; Hu, Jialei; Wang, Bingnan; Xie, Hujun; Yu, Lei; Ding, Hanfeng

2017-07-25

A solvent-dependent oxidative dearomatization-induced divergent [5+2] cascade approach to bicyclo[3.2.1]octanes was described. This novel protocol enables a facile synthesis of a series of diversely functionalized ent-kaurene and cedrene-type skeletons in good yields and excellent diastereoselectivities.

trans-2-Tritylcyclohexanol as a chiral auxiliary in permanganate-mediated oxidative cyclization of 2-methylenehept-5-enoates: application to the synthesis of trans-(+)-linalool oxide.

Science.gov (United States)

Al Hazmi, Ali M; Sheikh, Nadeem S; Bataille, Carole J R; Al-Hadedi, Azzam A M; Watkin, Sam V; Luker, Tim J; Camp, Nicholas P; Brown, Richard C D

2014-10-03

The permanganate-mediated oxidative cyclization of a series of 2-methylenehept-5-eneoates bearing different chiral auxiliaries was investigated, leading to the discovery of trans-2-tritylcyclohexanol (TTC) as a highly effective chiral controller for the formation of the 2,5-substituted THF diol product with high diastereoselectivity (dr ∼97:3). Chiral resolution of (±)-TTC, prepared in one step from cyclohexene oxide, afforded (-)-(1S,2R)-TTC (er >99:1), which was applied to the synthesis of (+)-trans-(2S,5S)-linalool oxide.

Diastereoselective formation of metallamacrocyclic (arene)Ru(II) and CpRh(III) complexes.

Science.gov (United States)

Lehaire, Marie-Line; Scopelliti, Rosario; Herdeis, Lorenz; Polborn, Kurt; Mayer, Peter; Severin, Kay

2004-03-08

The reaction of [(arene)RuCl(2)](2) (arene = cymene, 1,3,5-C(6)H(3)Me(3)) and [CpRhCl(2)](2) half-sandwich complexes with tridentate heterocyclic ligands in the presence of base has been investigated. In all cases, the chloro-ligands were substituted to give metallacyclic products with ring sizes between 4 and 18 atoms. The cyclization occurs in a highly diastereoselective fashion with chiral recognition between the different metal fragments. The complexes were comprehensively characterized by elemental analysis, NMR spectroscopy, and single crystal X-ray crystallography. For 2-hydroxy-nicotinic acid and 2-amino-nicotinic acid, dinuclear structures were obtained (15-17) whereas for 2,3-dihydroxyquinoline, 2,3-dihydroxyquinoxaline, and 6-methyl-2,3-phenazinediol, trimeric assemblies were found (19-22), and for 4-imidazolecarboxylic acid, a tetrameric assembly (18) was found.

Studies toward the asymmetric synthesis of the right part of the mycalamides.

Science.gov (United States)

Zhong, H Marlon; Sohn, Jeong-Hun; Rawal, Viresh H

2007-01-19

Described herein is the asymmetric synthesis of a functionalized, trioxadecalin unit that comprises the right-hand part of the mycalamides and related natural products. The synthetic route involves a 16-step sequence that accomplishes the formation of two heterocyclic rings and the generation of five stereocenters. The synthesis commenced with a C2-symmetric starting material, diethyl D-tartrate, and took advantage of a relay of diastereoselective reactions to extend this four-carbon chain and introduce new chiral centers. Subsequent electrophile-mediated cyclization afforded the desired pyran ring, which was then transformed into the desired, functionalized trioxadecalin skeleton.

Remote Stereoinductive Intramolecular Nitrile Oxide Cycloaddition: Asymmetric Total Synthesis and Structure Revision of (-)-11β-Hydroxycurvularin.

Science.gov (United States)

Choe, Hyeonjeong; Pham, Thuy Trang; Lee, Joo Yun; Latif, Muhammad; Park, Haeil; Kang, Young Kee; Lee, Jongkook

2016-03-18

The first total synthesis and structure revision of (-)-11β-hydroxycurvularin (1b), a macrolide possessing a β-hydroxyketone moiety, were accomplished. The β-hydroxyketone moiety in this natural product was introduced by cleavage of the N-O bond in an isoxazoline ring that was formed diastereoselectively in a 1,5-remote stereocontrolled fashion by employing intramolecular nitrile oxide cycloaddition.

The Brønsted Acid-Catalyzed, Enantioselective Aza-Diels-Alder Reaction for the Direct Synthesis of Chiral Piperidones.

Science.gov (United States)

Weilbeer, Claudia; Sickert, Marcel; Naumov, Sergei; Schneider, Christoph

2017-01-12

We disclose herein the first enantioselective aza-Diels-Alder reaction of β-alkyl-substituted vinylketene silyl-O,O-acetals and imines furnishing a broad range of optically highly enriched 4-alkyl-substituted 2-piperidones. As a catalyst for this one-pot reaction we employed a chiral phosphoric acid which effects a vinylogous Mannich reaction directly followed by ring-closure to the lactam. Subsequent fully diastereoselective transformations including hydrogenation, enolate alkylation, and lactam alkylation/reduction processes converted the cycloadducts into various highly substituted piperidines of great utility for the synthesis of natural products and medicinally active compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of (±)-amathaspiramide F and discovery of an unusual stereocontrolling element for the [2,3]-Stevens rearrangement.

Science.gov (United States)

Soheili, Arash; Tambar, Uttam K

2013-10-04

A formal total synthesis of (±)-amathaspiramide F through a tandem palladium-catalyzed allylic amination/[2,3]-Stevens rearrangement is reported. The unexpected diastereoselectivity of the [2,3]-Stevens rearrangement was controlled by the substitution patterns of an aromatic ring. This discovery represents a new stereocontrolling element for [2,3]-sigmatropic rearrangements in complex molecular settings.

NAA-modified DNA oligonucleotides with zwitterionic backbones: stereoselective synthesis of A-T phosphoramidite building blocks.

Science.gov (United States)

Schmidtgall, Boris; Höbartner, Claudia; Ducho, Christian

2015-01-01

Modifications of the nucleic acid backbone are essential for the development of oligonucleotide-derived bioactive agents. The NAA-modification represents a novel artificial internucleotide linkage which enables the site-specific introduction of positive charges into the otherwise polyanionic backbone of DNA oligonucleotides. Following initial studies with the introduction of the NAA-linkage at T-T sites, it is now envisioned to prepare NAA-modified oligonucleotides bearing the modification at X-T motifs (X = A, C, G). We have therefore developed the efficient and stereoselective synthesis of NAA-linked 'dimeric' A-T phosphoramidite building blocks for automated DNA synthesis. Both the (S)- and the (R)-configured NAA-motifs were constructed with high diastereoselectivities to furnish two different phosphoramidite reagents, which were employed for the solid phase-supported automated synthesis of two NAA-modified DNA oligonucleotides. This represents a significant step to further establish the NAA-linkage as a useful addition to the existing 'toolbox' of backbone modifications for the design of bioactive oligonucleotide analogues.

α-Haloaldehydes: versatile building blocks for natural product synthesis.

Science.gov (United States)

Britton, Robert; Kang, Baldip

2013-02-01

The diastereoselective addition of organometallic reagents to α-chloroaldehydes was first reported in 1959 and occupies a historically significant role as the prototypical reaction for Cornforth's model of stereoinduction. Despite clear synthetic potential for these reagents, difficulties associated with producing enantiomerically enriched α-haloaldehydes limited their use in natural product synthesis through the latter half of the 20th century. In recent years, however, a variety of robust, organocatalytic processes have been reported that now provide direct access to optically enriched α-haloaldehydes and have motivated renewed interest in their use as building blocks for natural product synthesis. This Highlight summarizes the methods available for the enantioselective preparation of α-haloaldehydes and their stereoselective conversion into natural products.

One-pot synthesis of enantiomerically pure N-protected allylic amines from N-protected α-amino esters

Directory of Open Access Journals (Sweden)

Gastón Silveira-Dorta

2016-05-01

Full Text Available An improved protocol for the synthesis of enantiomerically pure allylic amines is reported. N-Protected α-amino esters derived from natural amino acids were submitted to a one-pot tandem reduction–olefination process. The sequential reduction with DIBAL-H at −78 °C and subsequent in situ addition of organophosphorus reagents yielded the corresponding allylic amines without the need to isolate the intermediate aldehyde. This circumvents the problem of instability of the aldehydes. The method tolerates well both Wittig and Horner–Wadsworth–Emmons organophosphorus reagents. A better Z-(diastereoselectivity was observed when compared to the previous one-pot method. The (diastereoselectivity of the process was affected neither by the reaction solvent nor by the amount of DIBAL-H employed. The method is compatible with the presence of free hydroxy groups as shown with serine and threonine derivatives.

Stereoselective Catalytic Synthesis of Active Pharmaceutical Ingredients in Homemade 3D-Printed Mesoreactors.

Science.gov (United States)

Rossi, Sergio; Porta, Riccardo; Brenna, Davide; Puglisi, Alessandra; Benaglia, Maurizio

2017-04-03

3D-printed flow reactors were designed, fabricated from different materials (PLA, HIPS, nylon), and used for a catalytic stereoselective Henry reaction. The use of readily prepared and tunable 3D-printed reactors enabled the rapid screening of devices with different sizes, shapes, and channel dimensions, aimed at the identification of the best-performing reactor setup. The optimized process afforded the products in high yields, moderate diastereoselectivity, and up to 90 % ee. The method was applied to the continuous-flow synthesis of biologically active chiral 1,2-amino alcohols (norephedrine, metaraminol, and methoxamine) through a two-step sequence combining the nitroaldol reaction with a hydrogenation. To highlight potential industrial applications of this method, a multistep continuous synthesis of norephedrine has been realized. The product was isolated without any intermediate purifications or solvent switches. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

One-Pot Synthesis of 2-Acylindole-3-acetylketones via Domino Aza-alkylation/Michael Reaction Using o-Aminophenyl α,β-Unsaturated Ketones Followed by Desulfonative Dehydrogenation

Energy Technology Data Exchange (ETDEWEB)

Kim, A Reum; Yu, Mi Rim; Sim, Jong Tack; Kim, Sung Gon [Kyonggi Univ., Suwon (Korea, Republic of)

2016-09-15

The development of novel and practical synthetic methods with a minimum number of operations for the construction of bioactive structurally complex compounds is a major challenge in synthetic organic chemistry. Recently, we reported an efficient method for the stereoselective synthesis of 2,3-disubstituted indoline derivatives; cis-2,3-disubstituted indolines were obtained by the aza-alkylation/Michael cascade reaction of 2-(tosylamino)phenyl α,β-unsaturated ketones with α-bromoacetophenones in good yields and with excellent diastereoselectivities (Scheme 2, Eq. (1)). Among the available synthetic strategies, domino or cascade reactions have received wide acceptance as highly efficient and powerful methods for the synthesis of molecules with a high structural complexity. An efficient synthesis of 2,3-disubstituted indoles was developed by the domino aza-alkylation/intramolecular Michael reaction of 2-(tosylamino)phenyl α,β-unsaturated ketones with α-bromoacetophenones, followed by desulfonative dehydrogenation with DBU. The reaction afforded structurally diverse and highly functionalized 2,3-disubstituted indoles in moderate to excellent yields (up to 99%). The synthesis of 2,3-disubstituted indoles without desulfonation through DDQ-induced oxidative dehydrogenation was also achieved.

Nonradical Zinc-Barbier Reaction for Diastereoselective Synthesis of Vicinal Amino Alcohols

DEFF Research Database (Denmark)

Keinicke, Lise Edelmann; Fristrup, Peter; Norrby, Per-Ola

2005-01-01

A new protocol for the synthesis of vicinal amino alcohols is described. The method employs a Barbier-type reaction between an imine and 3-benzoyloxyallyl bromide in the presence of zinc metal. The addition products are debenzoylated to afford amino alcohols in good yields and with diastereomeric...

Concise Stereocontrolled Formal Synthesis of (±)-Quinine and Total Synthesis of (±)-7-Hydroxyquinine via Merged Morita-Baylis-Hillman-Tsuji-Trost Cyclization

Science.gov (United States)

Webber, Peter; Krische, Michael J.

2010-01-01

Concise stereoselective syntheses of (±)-quinine and (±)-7-hydroxyquinine are achieved using a catalytic enone cycloallylation that combines the nucleophilic features of the Morita-Baylis-Hillman reaction and the electrophilic features of the Tsuji-Trost reaction. Cyclization of enone-allyl carbonate 11 delivers the product of cycloallylation 13 in 68% yield. Diastereoselective conjugate reduction of the enone 13 (>20:1 dr) followed by exchange of N-protecting groups provides the saturated N-Boc-protected methyl ketone 19, which upon aldol dehydration provides quinoline containing enone 15, possessing all carbon atoms of quinine. Exposure of ketone 15 to L-selectride enables diastereoselective carbonyl reduction (>20:1 dr) to furnish the allylic alcohol 16. Stereoselective hydroxyl-directed epoxidation using an oxovanadium catalyst modified by N-hydroxy-N-Me-pivalamide delivers epoxide 17 (17:1 dr). Cyclization of the resulting amine-epoxide 17 provides (±)-7-hydroxyquinine in 13 steps and 11% overall yield from aminoacetaldehyde diethyl acetal. Notably, highly stereoselective formation of five contiguous stereocenters is achieved through a series of 1,2-asymmetric induction events. A formal synthesis of (±)-quinine is achieved upon deoxygenation of the N-Cbz-protected allylic acetate 22 to provide olefin 23, which previously has been converted to quinine. Thus, (±)-quinine is accessible in 16 steps and 4% overall yield from commercial aminoacetaldehyde diethyl acetal, making this route the most concise approach to quinine, to date. PMID:18989927

Diastereoselective Addition of α-Metalated Sulfoxides to Imines Revisited: Mechanism, Computational Studies, and the Effect of External Chiral Ligands

DEFF Research Database (Denmark)

Pedersen, Brian; Rein, Tobias; Søtofte, Inger

2003-01-01

six-membered "flat chair") was probed by quantum mechanical calculations, which underpinned the idea of using external chiral ligands to enhance the diastereoselectivity of otherwise moderately selective reactions. In this way, the diastereomeric ratio of the product 3a could be raised from (84 : 16...

Liquid-assisted grinding and ion pairing regulates percentage conversion and diastereoselectivity of the Wittig reaction under mechanochemical conditions.

Science.gov (United States)

Denlinger, Kendra Leahy; Ortiz-Trankina, Lianna; Carr, Preston; Benson, Kingsley; Waddell, Daniel C; Mack, James

2018-01-01

Mechanochemistry is maturing as a discipline and continuing to grow, so it is important to continue understanding the rules governing the system. In a mechanochemical reaction, the reactants are added into a vessel along with one or more grinding balls and the vessel is shaken at high speeds to facilitate a chemical reaction. The dielectric constant of the solvent used in liquid-assisted grinding (LAG) and properly chosen counter-ion pairing increases the percentage conversion of stilbenes in a mechanochemical Wittig reaction. Utilizing stepwise addition/evaporation of ethanol in liquid-assisted grinding also allows for the tuning of the diastereoselectivity in the Wittig reaction.

Regio- and stereoselective 1,2-dihydropyridine alkylation/addition sequence for the synthesis of piperidines with quaternary centers.

Science.gov (United States)

Duttwyler, Simon; Chen, Shuming; Lu, Colin; Mercado, Brandon Q; Bergman, Robert G; Ellman, Jonathan A

2014-04-07

The first example of C alkylation of 1,2-dihydropyridines with alkyl triflates and Michael acceptors was developed to introduce quaternary carbon centers with high regio- and diastereoselectivity. Hydride or carbon nucleophile addition to the resultant iminium ion also proceeded with high diastereoselectivity. Carbon nucleophile addition results in an unprecedented level of substitution to provide piperidine rings with adjacent tetrasubstituted carbon atoms. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A stereoselective, catalytic strategy for the in-flow synthesis of advanced precursors of rasagiline and tamsulosin.

Science.gov (United States)

Brenna, Davide; Pirola, Margherita; Raimondi, Laura; Burke, Anthony J; Benaglia, Maurizio

2017-12-01

The diastereoselective, trichlorosilane-mediate reduction of imines, bearing different and removable chiral auxiliaries, in combination either with achiral bases or catalytic amounts of chiral Lewis bases, was investigated to afford immediate precursors of chiral APIs (Active Pharmaceutical Ingredients). The carbon-nitrogen double bond reduction was successfully performed in batch and in flow mode, in high yields and almost complete stereocontrol. By this metal-free approach, the formal synthesis of rasagiline and tamsulosin was successfully accomplished in micro(meso) flow reactors, under continuous flow conditions. The results of these explorative studies represent a new, important step towards the development of automated processes for the preparation of enantiopure biologically active compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

Diastereoselective Synthesis of Novel Heterocyclic Scaffolds through Tandem Petasis 3-Component/Intramolecular Diels-Alder and ROM-RCM Reactions

DEFF Research Database (Denmark)

Ishøy, Mette; Petersen, Rico; Petersen, Michael Åxman

2017-01-01

A high-yielding, stereoselective and extraordinarily complexity generatingPetasis 3-component/intramolecular Diels-Alderreaction has been developed. In combination with ROM-RCM, rapid access to complex sp3-rich heterocyclic scaffolds amenableto subsequent functionalization and library synthesis...

New chiral phosphinephosphinite ligands: Application to stereoselective synthesis of a key intermediate of 1{beta}-methyl carbapenems by Rh(I)-catalyzed asymmetric hydroformylation

Energy Technology Data Exchange (ETDEWEB)

Saito, Takao; Yoshida, Akifumi; Matsumura, Kazuhiko [Takasago International Corp., Kanagawa (Japan)] [and others

1995-12-31

Transition metal catalyzed asymmetric hydroformylation is an attractive and highly useful homologation process for organic synthesis. Recently, the authors reported that the Rh(I) complexes of phosphinephosphite BINAPHOS are highly efficient catalysts for enantioselective hydroformylation of a variety of olefins. This time, the authors have designed and synthesized new chiral phosphinephosphinite ligands having binaphthyl backbone, (R)-2-diarylphosphino-2{prime}-diarylphosphinoxy-1,1{prime}-binaphthy1 (hereafter abbreviated (R)-BIPNITE). The Rh(I) complexes of these ligands are effective catalysts for the asymmetric hydroformylation of 4-vinylazetidin-2-one to give the corresponding oxo-aldehyde 3{beta} as the major product in very high diastereoselectivities and in good regioselectivities. Interestingly, modifications of the aryl substituents in phosphine and phosphinite moieties afforded higher selectivities. Aldehyde 3{beta} was easily oxidized with NaClO{sub 2} to 4, a key intermediate of 1{beta}-methyl carbapenems. Thus, the present method provides a new practical route to a versatile key intermediate for the synthesis of carbapenem antibiotics.

N-Heterocyclic Carbene-Catalysed Diastereoselective Vinylogous Michael Addition Reaction of gamma-Substituted deconjugated Butenolides

KAUST Repository

Guo, Hao

2015-11-16

An efficient N-heterocyclic carbene (NHC)-catalysed vinylogous Michael addition of deconjugated butenolides was developed. In the presence of 5 mol% of the NHC catalyst, both γ-alkyl and aryl-substituted deconjugated butenolides undergo vinylogous Michael addition with various α, β-unsaturated ketones, esters, or nitriles to afford γ,γ-disubstituted butenolides containing adjacent quaternary and tertiary carbon centers in good to excellent yields with excellent diastereoselectivities. In this process, the free carbene is assumed to act as a strong Brønsted base to promote the conjugate addition.

N-Heterocyclic Carbene-Catalysed Diastereoselective Vinylogous Michael Addition Reaction of gamma-Substituted deconjugated Butenolides

KAUST Repository

Guo, Hao; Xing, Fen; Du, Guang-Fen; Huang, Kuo-Wei; Dai, Bin; He, Lin

2015-01-01

An efficient N-heterocyclic carbene (NHC)-catalysed vinylogous Michael addition of deconjugated butenolides was developed. In the presence of 5 mol% of the NHC catalyst, both γ-alkyl and aryl-substituted deconjugated butenolides undergo vinylogous Michael addition with various α, β-unsaturated ketones, esters, or nitriles to afford γ,γ-disubstituted butenolides containing adjacent quaternary and tertiary carbon centers in good to excellent yields with excellent diastereoselectivities. In this process, the free carbene is assumed to act as a strong Brønsted base to promote the conjugate addition.

Diastereoselectivity in the reduction of bicyclic enones with hindered hydrides; Diastereosseletividade na reducao de enonas biciclicas com hidretos volumosos

Energy Technology Data Exchange (ETDEWEB)

Camozzato, Andreza C.; Tenius, Beatriz S. M.; Oliveira, Eduardo R. de [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Inst. de Quimica. Dept. de Quimica Organica]. E-mail: eroliv@iq.ufrgs.br; Viegas Junior, Claudio [Universidade Federal de Alfenas (UFAL), MG (Brazil). Dept. de Farmacia; Victor, Mauricio M. [Universidade Federal da Bahia (UFBA), Salvador, BA (Brazil). Inst. de Quimica. Dept. de Quimica Organica; Silveira, Leandro G. da [Universidade Regional Integrada do Alto Uruguai e das Missoes, Frederico Westphalen, RS (Brazil). Curso de Quimica. Dept. de Ciencias Exatas e da Terra

2008-07-01

Reduction of five substituted octalones employing lithium tri-sec-butylborohydride (L-selectride{sup R}) in THF and ethyl ether led to allylic alcohols with moderate diastereoselectivity. The stereoselectivity of addition of bulky hydrides showed to be different from most examples in the literature and was strongly influenced by substitution on the octalone ring. (author)

The direct oxidative diene cyclization and related reactions in natural product synthesis

Directory of Open Access Journals (Sweden)

Juliane Adrian

2016-09-01

Full Text Available The direct oxidative cyclization of 1,5-dienes is a valuable synthetic method for the (diastereoselective preparation of substituted tetrahydrofurans. Closely related reactions start from 5,6-dihydroxy or 5-hydroxyalkenes to generate similar products in a mechanistically analogous manner. After a brief overview on the history of this group of transformations and a survey on mechanistic and stereochemical aspects, this review article provides a summary on applications in natural product synthesis. Moreover, current limitations and future directions in this area of chemistry are discussed.

An efficient method for synthesis of succinate-based MMP inhibitors.

Science.gov (United States)

Sibi, Mukund P; Hasegawa, Hikaru

2002-10-03

A differentially protected fumarate undergoes radical addition followed by allylstannane trapping to provide disubstituted succinates in good yields and high anti diastereoselectivity. The conversion of the succinate to a known MMP inhibitor has been accomplished. [reaction: see text

A practical synthesis of a gamma-secretase inhibitor.

Science.gov (United States)

Scott, Jeremy P; Lieberman, David R; Beureux, Olivier M; Brands, Karel M J; Davies, Antony J; Gibson, Andrew W; Hammond, Deborah C; McWilliams, Chris J; Stewart, Gavin W; Wilson, Robert D; Dolling, Ulf-H

2007-05-25

A practical and scaleable synthesis of the gamma-secretase inhibitor 1 is reported. The inhibitor consists of a central trisubstituted cyclohexane core with appended propionic acid, 2,5-difluorophenyl, and 4-chlorophenylsulfonyl moieties. Two alternative synthetic strategies, proceeding by way of a common disubstituted cyclohexanone derivative 5, were studied. In the preferred route, conjugate reduction of acrylonitrile derivative 4 with L-Selectride configures the desired relative stereochemistry of the cyclohexane core with >99.9:0.1 dr. A second strategy, based on catalyst-controlled hydrogenation of racemic cyclohexene derivative 2, is more convergent but less diastereoselective (up to 75:25 dr). The common cyclohexanone intermediate 5 was constructed by a regioselective Diels-Alder condensation of a 1,1-disubstituted vinyl sulfone 6 with 2-trimethylsiloxybutadiene.

Knorr-Rabe partial reduction of pyrroles: Application to the synthesis of indolizidine alkaloids

Directory of Open Access Journals (Sweden)

Ryan John H

2008-01-01

Full Text Available Abstract Background The Birch reduction of electron rich pyrroles does not occur readily. However, dissolving metal reduction with zinc under acidic conditions gives 3-pyrrolines (2,5-dihydropyrroles in reasonable yield. This dissolving metal reduction was first reported by Knorr and Rabe in 1901 but since then has only been reported for the reduction of electron rich pyrroles. Results The partial reduction of bicyclic α-ketopyrrole derivatives has been performed under dissolving metal conditions with zinc and hydrochloric acid to give excellent yields of hexahydroindolizidines. This reduction method has been utilised for the diastereoselective synthesis of 5-alkylindolizidines and the stereoselectivity obtained is opposite to that of catalytic hydrogenation. Conclusion An efficient stereoselective synthesis of indolizidine alkaloids has been developed from α-ketopyrrole intermediates using a modified version of Knorr and Rabe's pyrrole reduction.

Ready access to functionally embellished cis-hydrindanes and cis-decalins: protecting group-free total syntheses of (±)-Nootkatone and (±)-Noreremophilane.

Science.gov (United States)

Handore, Kishor L; Seetharamsingh, B; Reddy, D Srinivasa

2013-08-16

A simple and efficient synthesis of functionalized cis-hydrindanes and cis-decalins was achieved using a sequential Diels-Alder/aldol approach in a highly diastereoselective manner. The scope of this method was tested with a variety of substrates and was successfully applied to the synthesis of two natural products in racemic form. The highlights of the present work provide ready access to 13 new cis-hydrindanes/cis-decalins, a protecting group-free total synthesis of an insect repellent Nootkatone, and the first synthesis of a Noreremophilane using the shortest sequence.

Diastereosseletividade na redução de enonas bicíclicas com hidretos volumosos Diastereoselectivity in the reduction of bicyclic enones with hindered hydrides

Directory of Open Access Journals (Sweden)

Andreza C. Camozzato

2008-01-01

Full Text Available Reduction of five substituted octalones employing lithium tri-sec-butylborohydride (L-selectride® in THF and ethyl ether led to allylic alcohols with moderate diastereoselectivity. The stereoselectivity of addition of bulky hydrides showed to be different from most examples in the literature and was strongly influenced by substitution on the octalone ring.

Enantiopure Ferrocene-Based Planar-Chiral Iridacycles: Stereospecific Control of Iridium-Centred Chirality.

Science.gov (United States)

Arthurs, Ross A; Ismail, Muhammad; Prior, Christopher C; Oganesyan, Vasily S; Horton, Peter N; Coles, Simon J; Richards, Christopher J

2016-02-24

Reaction of [IrCp*Cl2 ]2 with ferrocenylimines (Fc=NAr, Ar=Ph, p-MeOC6 H4 ) results in ferrocene C-H activation and the diastereoselective synthesis of half-sandwich iridacycles of relative configuration Sp *,RIr *. Extension to (S)-2-ferrocenyl-4-(1-methylethyl)oxazoline gave highly diastereoselective control over the new elements of planar chirality and metal-based pseudo-tetrahedral chirality, to give both neutral and cationic half-sandwich iridacycles of absolute configuration Sc ,Sp ,RIr . Substitution reactions proceed with retention of configuration, with the planar chirality controlling the metal-centred chirality through an iron-iridium interaction in the coordinatively unsaturated cationic intermediate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aldolase catalyzed L-phenylserine synthesis in a slug-flow microfluidic system - Performance and diastereoselectivity studies

NARCIS (Netherlands)

Čech, J.; Hessel, V.; Přibyl, M.

2017-01-01

We study synthesis of . L-phenylserine catalyzed by the enzyme . L-threonine aldolase in a slug-flow microfluidic system. Slug-flow arrangement allows for the continuous refilling of sparingly soluble substrate (benzaldehyde) into an aqueous reaction mixture. We identified suitable composition of an

Catalytic diastereoselective tandem conjugate addition-elimination reaction of Morita-Baylis-Hillman C adducts by C-C bond cleavage

KAUST Repository

Yang, Wenguo

2012-02-08

Through the cleavage of the C-C bond, the first catalytic tandem conjugate addition-elimination reaction of Morita-Baylis-Hillman C adducts has been presented. Various S N2′-like C-, S-, and P-allylic compounds could be obtained with exclusive E configuration in good to excellent yields. The Michael product could also be easily prepared by tuning the β-C-substituent group of the α-methylene ester under the same reaction conditions. Calculated relative energies of various transition states by DFT methods strongly support the observed chemoselectivity and diastereoselectivity. © 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.

Stereoselective synthesis of 5-alkoxycarbonyl-4 alkyl-2-anino-3-cyano-6-methyl-4H-pyranes 3 via asymmetric Michael addition to aceptors-gamma-stereogenics; Sintesis esteroselective de 5-alcoxicarbonil-4-alquil-2-amino-3-ciano-6-metil-4H-piranos via adicion Michael sobre aceptores-gama-esterogenicos

Energy Technology Data Exchange (ETDEWEB)

Martinez-Grau, A.; Jimenez, B.; Martin, N.; Seoane, C.; Marco, J.L. [Departamento de Quimica Organica, Facultad de Quimica, Universidad Complutense, Madrid (Spain)

1994-12-31

The stereoselective synthesis of 5-alkoxycarbonyl-4-alkyl-2-amino-3-cyano-6-methyl-4H-pyrans 3 via asymmetric Michael addition of malononitrile to gamma-stereogenic alpha-acetylacrylates 2 obtained by Knoevenagel reaction of acetylacetates to quiral alpha-hydroxyaldehydes 1 is described. The resulting 2-amino-4H-pyrans 3 have been obtained in moderate yield and good diastereoselectivity. 15 refs.

Hydroxyl-substituted ladder polyethers via selective tandem epoxidation/cyclization sequence.

Science.gov (United States)

Czabaniuk, Lara C; Jamison, Timothy F

2015-02-20

A new and highly selective method for the synthesis of hydroxyl-substituted tetrahydropyrans is described. This method utilizes titanium(IV) isopropoxide and diethyl tartrate to perform a diastereoselective epoxidation followed by in situ epoxide activation and highly selective endo-cyclization to form the desired tetrahydropyran ring. The HIJ ring fragment of the marine ladder polyether yessotoxin was synthesized using this two-stage tactic that proceeds with high efficiency and excellent regioselectivity.

Concise Total Synthesis of (-)-Affinisine Oxindole, (+)-Isoalstonisine, (+)-Alstofoline, (-)-Macrogentine, (+)-Na -Demethylalstonisine, (-)-Alstonoxine A, and (+)-Alstonisine.

Science.gov (United States)

Stephen, Michael Rajesh; Rahman, M Toufiqur; Tiruveedhula, V V N Phani Babu; Fonseca, German O; Deschamps, Jeffrey R; Cook, James M

2017-11-07

A highly enantio- and diastereoselective strategy to access any member of the sarpagine/macroline family of oxindole alkaloids via internal asymmetric induction was developed from readily available d-(+)-tryptophan. At the center of this approach was the diastereospecific generation of the spiro[pyrrolidine-3,3'-oxindole] moiety at an early stage via a tert-butyl hypochlorite-promoted oxidative rearrangement of a chiral tetrahydro-β-carboline derivative. This key branching point determined the spatial configuration at the C-7 spiro center to be entirely 7R or 7S. Other key stereospecific processes were the asymmetric Pictet-Spengler reaction and Dieckmann cyclization, which were scalable to the 600 and 150 gram levels, respectively. Execution of this approach resulted in first enantiospecific total synthesis of (+)-isoalstonisine and (-)-macrogentine from the chitosenine series (7R), as well as (+)-alstonisine, (+)-alstofoline, (-)-alstonoxine A and (+)-N a -demethylalstonisine from the alstonisine series (7S). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enantioselective synthesis of alpha,beta-disubstituted-beta-amino acids.

Science.gov (United States)

Sibi, Mukund P; Prabagaran, Narayanasamy; Ghorpade, Sandeep G; Jasperse, Craig P

2003-10-01

Highly diastereoselective and enantioselective addition of N-benzylhydroxylamine to imides 17 and 20-30 produces alpha,beta-trans-disubstituted N-benzylisoxazolidinones 19 and 31-41. These reactions proceed in 60-96% ee with 93-99% de's using 5 mol % of Mg(NTf2)2 and ligand 18. The product isoxazolidinones can be hydrogenolyzed directly to provide alpha,beta-disubstituted-beta-amino acids.

Asymmetric synthesis of α-amino acids by reduction of N-tert-butanesulfinyl ketimine esters.

Science.gov (United States)

Reddy, Leleti Rajender; Gupta, Aditya P; Liu, Yugang

2011-05-06

A highly regio- and diastereoselective reduction of various N-tert-butanesulfinyl ketimine esters with L-Selectride resulting in the formation of α-amino acids is reported. This method is quite general and also practical for the preparation of both enantiomers of aryl or aliphatic α-amino acids in high yields. © 2011 American Chemical Society

Α-amino-β-fluorocyclopropanecarboxylic acids as a new tool for drug development: synthesis of glutamic acid analogs and agonist activity towards metabotropic glutamate receptor 4.

Science.gov (United States)

Lemonnier, Gérald; Lion, Cédric; Quirion, Jean-Charles; Pin, Jean-Philippe; Goudet, Cyril; Jubault, Philippe

2012-08-01

Herein we describe the diastereoselective synthesis of glutamic acid analogs and the evaluation of their agonist activity towards metabotropic glutamate receptor subtype 4 (mGluR4). These analogs are based on a monofluorinated cyclopropane core substituted with an α-aminoacid function. The potential of this new building block as a tool for the development of a novel class of drugs is demonstrated with racemic analog 11a that displayed the best agonist activity with an EC50 of 340 nM. Copyright © 2012 Elsevier Ltd. All rights reserved.

A new reactivity mode for the diazo group: diastereoselective 1,3-aminoalkylation reaction of β-amino-α-diazoesters to give triazolines.

Science.gov (United States)

Kuznetsov, Alexey; Gulevich, Anton V; Wink, Donald J; Gevorgyan, Vladimir

2014-08-18

A novel mode of reactivity for the diazo group, the 1,3-addition of a nucleophile and an electrophile to the diazo group, has been realized in the intramolecular aminoalkylation of β-amino-α-diazoesters to form tetrasubstituted 1,2,3-triazolines. The reaction exhibited a broad scope, good functional group tolerance, and excellent diastereoselectivity. In addition, a new Au-catalyzed intramolecular transannulation reaction of the obtained propargyl triazolines to give pyrroles has been discovered. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

N-Heterocyclic Carbene-Catalyzed Vinylogous Mukaiyama Aldol Reaction of α-Keto Esters and α-Trifluoromethyl Ketones

KAUST Repository

Du, Guang-Fen; Wang, Ying; Xing, Fen; Xue, Mei; Guo, Xu-Hong; Huang, Kuo-Wei; Dai, Bin

2015-01-01

© Georg Thieme Verlag Stuttgart · New York · Synthesis 2016. N-Heterocyclic carbene (NHC)-catalyzed vinylogous Mukaiyama aldol reaction of ketones was developed. Under the catalysis of 5 mol% NHC, α-keto esters and α-trifluoromethyl ketones reacted with 2-(trimethysilyloxy)furan efficiently to produce γ-substituted butenolides containing adjacent quaternary and tertiary carbon centers in high yields with good diastereoselectivities.

Asimetric synthesis of alpha-phenyl amino acids; Sintesis asimetrica de alfa-fenilaminoacidos

Energy Technology Data Exchange (ETDEWEB)

Caltiviela, C.; Diaz de Villegas, M.D.; Galvez, J.A.; Lapena, Y. [Departamento de Quimica Organica, Universidad de Zaragoza, Zaragoza (Spain)

1994-12-31

A new synthetic strategy to obtain alpha-phenyl amino acids in enantiomerically pure form is described. The new route is based on the highly diastereoselective alkylation of (1S,2R,4R)-10-dicyclohexylsulfamoylisobornyl 2-phenylcianoacetate and subsequent curtis type rearrangement of the alkylated compound with total retention of configuration. 17 refs

Diastereoselective synthesis of ethyl ( Z)-3-(8-methylimidazo-[1,2- a]pyrid-2-yl)-2-phenylthioacrylate. X-ray crystal structure and conformational analysis

Science.gov (United States)

Gautier, A.; Roche, D.; Métin, J.; Carpy, A.; Madesclaire, M.

1995-09-01

The title compound 2, a gem vinyl sulfide ester, has been obtained diastereoselectively (de > 98%) by action of the ethyl thiophenoxyacetate carbanion on the imidazo[1,2- a]pyridinecarbaldehyde 1 in a basic medium, at low temperature. The X-ray crystal structure of 2 (C 19H 19N 2O 2S: Mr = 338.43, triclinic, P 1¯, a = 8.193(3) Å, b = 10.090(2) Å, c = 10.981(4) Å, α = 88.12(2)°, β = 78.66(4)°, γ = 78.53(2)°, V = 872.3(6) Å3, Z = 2, Dcalc = 1.29 g cm -3, λ( Mo Kα) = 0.71069 Å, μ = 0.189 mm -1, F(000) = 356, T = 293 K, R = 0.043 for 3610 observed reflections) has been determined and confirmed the Z configuration. The molecule is almost planar except for the phenyl ring situated in an approximate perpendicular plane. Despite the presence of the conjugate double bonds of the vinyl ester group (acrylate), coplanar with the imidazopyridine heterocycle, there is no evidence of π-electron delocalization over the whole structure. The crystal cohesion is ensured by a dense network of van der Waals contacts. A conformational analysis of the Z and E isomers by means of a Monte Carlo search and a stochastic dynamics simulation in CHCl 3 has shown that according to the method the Z isomer is more stable than the E isomer by about 7 to 10 kJ mol -1.

Combining multi-catalysis and multi-component systems for the development of one-pot asymmetric reactions: stereoselective synthesis of highly functionalized bicyclo[4.4.0]decane-1,6-diones.

Science.gov (United States)

Ramachary, Dhevalapally B; Sakthidevi, Rajasekar

2008-07-21

We have developed a direct amine/acid-catalyzed stereoselective hydrogenation of a variety of Wieland-Miescher (W-M) ketones, Hajos-Parrish (H-P) ketones and their analogs with organic hydrides (Hantzsch esters) as the hydrogen source. This astonishingly simple and biomimetic approach was used to construct highly functionalized chiral bicyclo[4.4.0]decane-1,6-diones in a diastereoselective fashion. This is an example of the development of a new technology by the combination of multiple catalysts and components in one pot to deliver highly functionalized chiral molecules.

Synthesis of high luminescent carbon nanoparticles

Science.gov (United States)

Gvozdyuk, Alina A.; Petrova, Polina S.; Goryacheva, Irina Y.; Sukhorukov, Gleb B.

2017-03-01

In this article we report an effective and simple method for synthesis of high luminescent carbon nanodots (CDs). In our work as a carbon source sodium dextran sulfate (DS) was used because it is harmless, its analogs are used in medicine as antithrombotic compounds and blood substitutes after hemorrhage. was used as a substrate We investigated the influence of temperature parameters of hydrothermal synthesis on the photoluminescence (PL) intensity and position of emission maxima. We discovered that the PL intensity can be tuned by changing of synthesis temperature and CD concentration.

Synthesis of chiral N-phosphinyl α-imino esters and their application in asymmetric synthesis of α-amino esters by reduction

OpenAIRE

Xiong, Yiwen; Mei, Haibo; Wu, Lingmin; Han, Jianlin; Pan, Yi; Li, Guigen

2014-01-01

A variety of chiral N-phosphinyl α-imino esters have been synthesized for the first time from ketoesters and phosphinylamide, which were then reduced by L-selectride to give the corresponding N-phosphinyl-protected α-amino esters. The reduction proceeded very well with excellent chemical yields (88–98%) as well as high diastereoselectivities (96:4 to 99:1). Some of these products could be obtained without column chromatography and recrystallization. The chiral phosphinyl auxiliary could be ea...

RPython high-level synthesis

Science.gov (United States)

Cieszewski, Radoslaw; Linczuk, Maciej

2016-09-01

The development of FPGA technology and the increasing complexity of applications in recent decades have forced compilers to move to higher abstraction levels. Compilers interprets an algorithmic description of a desired behavior written in High-Level Languages (HLLs) and translate it to Hardware Description Languages (HDLs). This paper presents a RPython based High-Level synthesis (HLS) compiler. The compiler get the configuration parameters and map RPython program to VHDL. Then, VHDL code can be used to program FPGA chips. In comparison of other technologies usage, FPGAs have the potential to achieve far greater performance than software as a result of omitting the fetch-decode-execute operations of General Purpose Processors (GPUs), and introduce more parallel computation. This can be exploited by utilizing many resources at the same time. Creating parallel algorithms computed with FPGAs in pure HDL is difficult and time consuming. Implementation time can be greatly reduced with High-Level Synthesis compiler. This article describes design methodologies and tools, implementation and first results of created VHDL backend for RPython compiler.

Highly enantio- and diastereoselective synthesis of β-methyl-γ- monofluoromethyl-substituted alcohols

KAUST Repository

Yang, Wenguo

2011-06-07

Enanatiopure β-methyl-γ-monofluoromethyl alcohols were prepared from the allylic alkylation between fluorobis(phenylsulfonyl)methane with Morita-Baylis-Hillman carbonates. The reaction was catalyzed by using the Cinchona alkaloid derivative, (DHQD)2AQN. The origin of the stereoselectivity was verified by DFT methods. Calculated geometries and relative energies of various transition states strongly support the observed stereoselectivity. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diastereoselective Synthesis of 5-Hydroxy-8-methoxy-1-oxaspiro[5,5]undeca-7,10-diene-9-one

Directory of Open Access Journals (Sweden)

Thomas W. Scully

2013-01-01

Full Text Available A short five steps synthesis of the title compound from vanillin is described. The racemic spiroether 7 was obtained in 61% yield and in >99% diastereomeric excess (by 1H-NMR from the corresponding phenolic derivative 3 by oxidation with lead (IV acetate.

Synthesis of chiral N-phosphinyl α-imino esters and their application in asymmetric synthesis of α-amino esters by reduction.

Science.gov (United States)

Xiong, Yiwen; Mei, Haibo; Wu, Lingmin; Han, Jianlin; Pan, Yi; Li, Guigen

2014-01-01

A variety of chiral N-phosphinyl α-imino esters have been synthesized for the first time from ketoesters and phosphinylamide, which were then reduced by L-selectride to give the corresponding N-phosphinyl-protected α-amino esters. The reduction proceeded very well with excellent chemical yields (88-98%) as well as high diastereoselectivities (96:4 to 99:1). Some of these products could be obtained without column chromatography and recrystallization. The chiral phosphinyl auxiliary could be easily cleaved under acidic conditions.

Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases; Part 1: alkyl halide alkylations.

Science.gov (United States)

Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim A

2013-10-01

Alkylations of chiral or achiral Ni(II) complexes of glycine Schiff bases constitute a landmark in the development of practical methodology for asymmetric synthesis of α-amino acids. Straightforward, easy preparation as well as high reactivity of these Ni(II) complexes render them ready available and inexpensive glycine equivalents for preparing a wide variety of α-amino acids, in particular on a relatively large scale. In the case of Ni(II) complexes containing benzylproline moiety as a chiral auxiliary, their alkylation proceeds with high thermodynamically controlled diastereoselectivity. Similar type of Ni(II) complexes derived from alanine can also be used for alkylation providing convenient access to quaternary, α,α-disubstituted α-amino acids. Achiral type of Ni(II) complexes can be prepared from picolinic acid or via recently developed modular approach using simple secondary or primary amines. These Ni(II) complexes can be easily mono/bis-alkylated under homogeneous or phase-transfer catalysis conditions. Origin of diastereo-/enantioselectivity in the alkylations reactions, aspects of practicality, generality and limitations of this methodology is critically discussed.

Synthesis of chiral N-phosphinyl α-imino esters and their application in asymmetric synthesis of α-amino esters by reduction

Directory of Open Access Journals (Sweden)

Yiwen Xiong

2014-03-01

Full Text Available A variety of chiral N-phosphinyl α-imino esters have been synthesized for the first time from ketoesters and phosphinylamide, which were then reduced by L-selectride to give the corresponding N-phosphinyl-protected α-amino esters. The reduction proceeded very well with excellent chemical yields (88–98% as well as high diastereoselectivities (96:4 to 99:1. Some of these products could be obtained without column chromatography and recrystallization. The chiral phosphinyl auxiliary could be easily cleaved under acidic conditions.

Thermally Stable Dialkylzirconocenes with β-Hydrogens. Synthesis and Diastereoselectivity

OpenAIRE

Wendt, Ola F.; Bercaw, John E.

2001-01-01

Alkylation of Cp^r_2ZrCl_2 (Cpr = Cp (η^5-C_5H_5), Cp‘ (η^5-C_5H_4Me), Cp^* (η^5-C_5Me_5)) and CpCp^*Zr(CH_3)Cl with 1-lithio-2-methylpentane (R^1Li) gives the corresponding dialkylzirconocenes Cp^r_2ZrR^1_2 and CpCp^*Zr(CH_3)R^1, in high yields. Such alkyls have unprecedented thermal stabilities, especially for the CpCp^* ligand framework. The diastereomers of the Cp^r_2ZrR^1_2 complexes are formed in a statistical distribution, whereas the diastereomers of CpCp^*Zr(CH_3)R^1 form in a 2:3 ra...

Stereoselective synthesis and pharmacological evaluation of [4.3.3]propellan-8-amines as analogs of adamantanamines.

Science.gov (United States)

Torres-Gómez, Héctor; Lehmkuhl, Kirstin; Frehland, Bastian; Daniliuc, Constantin; Schepmann, Dirk; Ehrhardt, Christina; Wünsch, Bernhard

2015-08-01

Amantadine (1) exerts its anti-Parkinson effects by inhibition of the NMDA associated cation channel and its antiviral activity by inhibition of the M2 protein channel of influenza A viruses. Herein the synthesis, NMDA receptor affinity and anti-influenza activity of analogous propellanamines 3 are reported. The key steps in the synthesis of the diastereomeric propellanamines syn-3 and anti-3 are diastereoselective reduction of the ketone 7 with L-Selectride to give anti-11, Mitsunobu inversion of the alcohol anti-13 into syn-13, and SN2 substitution of diastereomeric mesylates syn-14 and anti-14 with NaN3. The affinity of the propellanamines syn-3 and anti-3 to the PCP binding site of the NMDA receptor is similar to that of amantadine (Ki=11 μM). However, both propellanamines syn-3 and anti-3 do not exhibit activity against influenza A viruses. Compared to amantadine (1), the structurally related propellanamines syn-3 and anti-3 retain the NMDA antagonistic activity but loose the antiviral activity. Copyright © 2015 Elsevier Ltd. All rights reserved.

Concise stereocontrolled formal synthesis of (+/-)-quinine and total synthesis of (+/-)-7- hydroxyquinine via merged Morita-Baylis-Hillman-Tsuji-Trost cyclization.

Science.gov (United States)

Webber, Peter; Krische, Michael J

2008-12-05

Concise stereoselective syntheses of (+/-)-quinine and (+/-)-7-hydroxyquinine are achieved using a catalytic enone cycloallylation that combines the nucleophilic features of the Morita-Baylis-Hillman reaction and the electrophilic features of the Tsuji-Trost reaction. Cyclization of enone-allyl carbonate 11 delivers the product of cycloallylation 13 in 68% yield. Diastereoselective conjugate reduction of the enone 13 (>20:1 dr) followed by exchange of the N-protecting group provides the saturated N-Boc-protected methyl ketone 19, which upon aldol dehydration provides quinoline containing enone 15, possessing all carbon atoms of quinine. Exposure of ketone 15 to L-selectride enables diastereoselective carbonyl reduction (>20:1 dr) to furnish the allylic alcohol 16. Stereoselective hydroxyl-directed epoxidation using an oxovanadium catalyst modified by N-hydroxy-N-Me-pivalamide delivers epoxide 17 (17:1 dr). Cyclization of the resulting amine-epoxide 17 provides (+/-)-7-hydroxyquinine in 13 steps and 11% overall yield from aminoacetaldehyde diethyl acetal. Notably, highly stereoselective formation of five contiguous stereocenters is achieved through a series of 1,2-asymmetric induction events. Deoxygenation of the N-Cbz-protected allylic acetate 22 provides olefin 23, which previously has been converted to quinine. Thus, (+/-)-quinine is accessible in 16 steps and 4% overall yield from commercial aminoacetaldehyde diethyl acetal.

Tailored Polymer-Supported Templates in Dynamic Combinatorial Libraries : Simultaneous Selection, Amplification and Isolation of Synthetic Receptors

NARCIS (Netherlands)

Besenius, Pol; Cormack, Peter A.G.; Liu, Jingyuan; Otto, Sijbren; Sanders, Jeremy K.M.; Sherrington, David C.

2008-01-01

The thermodynamically controlled synthesis and isolation of macrocyclic receptors from dynamic combinatorial libraries has been achieved in a single step using a polymer-supported template. The templates were cinchona alkaloids which show interesting enantio- and diastereoselective molecular

Stereoselective Synthesis of Tetrahydroindolizines through the Catalytic Formation of Pyridinium Ylides from Diazo Compounds.

Science.gov (United States)

Day, Jonathan; McKeever-Abbas, Ben; Dowden, James

2016-05-04

Commercially available iron(III) and copper(I) complexes catalyzed multicomponent cycloaddition reactions between diazo compounds, pyridines, and electrophilic alkenes to give alkaloid-inspired tetrahydroindolizidines in high yield with high diastereoselectivity. Hitherto, the catalytic formation of versatile pyridinium ylides from metal carbenes has been poorly developed; the broad utility demonstrated herein sets the stage for the invention of further multicomponent reactions in future. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High rate flame synthesis of highly crystalline iron oxide nanorods

International Nuclear Information System (INIS)

Merchan-Merchan, W; Taylor, A M; Saveliev, A V

2008-01-01

Single-step flame synthesis of iron oxide nanorods is performed using iron probes inserted into an opposed-flow methane oxy-flame. The high temperature reacting environment of the flame tends to convert elemental iron into a high density layer of iron oxide nanorods. The diameters of the iron oxide nanorods vary from 10 to 100 nm with a typical length of a few microns. The structural characterization performed shows that nanorods possess a highly ordered crystalline structure with parameters corresponding to cubic magnetite (Fe 3 O 4 ) with the [100] direction oriented along the nanorod axis. Structural variations of straight nanorods such as bends, and T-branched and Y-branched shapes are frequently observed within the nanomaterials formed, opening pathways for synthesis of multidimensional, interconnected networks

High chemoselectivity in the phenol synthesis

Directory of Open Access Journals (Sweden)

A. Stephen K. Hashmi

2011-06-01

Full Text Available Efforts to trap early intermediates of the gold-catalyzed phenol synthesis failed. Neither inter- nor intramolecularly offered vinyl groups, ketones or alcohols were able to intercept the gold carbenoid species. This indicates that the competing steps of the gold-catalyzed phenol synthesis are much faster than the steps of the interception reaction. In the latter the barrier of activation is higher. At the same time this explains the high tolerance of this very efficient and general reaction towards functional groups.

T3P- A Novel Catalyst for Aza-Diels-Alder Reaction: One-Pot Synthesis of Pyrano[3,2-c]quinolines and furano[3,2-c]quinolines

Directory of Open Access Journals (Sweden)

T. S. R. Prasanna

2011-01-01

Full Text Available T3P was found to be an efficient catalyst for the Aza-Diels–Alder reactions of aldimines with dihydropyran or dihydrofuran to afford the corresponding pyrano-and furo [3,2-c]quinolines in high yields with high diastereoselectivity in a short period of time.

Synthesis of nano-sized amorphous boron powders through active dilution self-propagating high-temperature synthesis method

Energy Technology Data Exchange (ETDEWEB)

Wang, Jilin [The State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China); Gu, Yunle [School of Material Science and Engineering, Wuhan Institute of Technology, Wuhan 430073 (China); Li, Zili [The State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China); Wang, Weimin, E-mail: wangwm@hotmail.com [The State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China); Fu, Zhengyi [The State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China)

2013-06-01

Graphical abstract: Nano-sized amorphous boron powders were synthesized by active dilution self-propagating high-temperature synthesis (SHS) method. The effects of endothermic reaction rate, the possible chemical reaction mechanism and active dilution model for synthesis of the product were also discussed. Highlights: ► Nano-sized amorphous boron powders were synthesized by active dilution self-propagating high-temperature synthesis method. ► The morphology, particle size and purity of the samples could be effectively controlled via changing the endothermic rate. ► The diluter KBH{sub 4} played an important role in active dilution synthesis of amorphous nano-sized boron powders. ► The active dilution method could be further popularized and become a common approach to prepare various inorganic materials. - Abstract: Nano-sized amorphous boron powders were synthesized by active dilution self-propagating high-temperature synthesis (SHS) method at temperatures ranging from 700 °C to 850 °C in a SHS furnace using Mg, B{sub 2}O{sub 3} and KBH{sub 4} as raw materials. Samples were characterized by X-ray powder diffraction (XRD), Laser particle size analyzer, Fourier transform infrared spectra (FTIR), X-ray energy dispersive spectroscopy (EDX), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high-resolution transmission TEM (HRTEM). The boron powders demonstrated an average particle size of 50 nm with a purity of 95.64 wt.%. The diluter KBH{sub 4} played an important role in the active dilution synthesis of amorphous nano-sized boron powders. The effects of endothermic reaction rate, the possible chemical reaction mechanism and active dilution model for synthesis of the product were also discussed.

Synthesis of nano-sized amorphous boron powders through active dilution self-propagating high-temperature synthesis method

International Nuclear Information System (INIS)

Wang, Jilin; Gu, Yunle; Li, Zili; Wang, Weimin; Fu, Zhengyi

2013-01-01

Graphical abstract: Nano-sized amorphous boron powders were synthesized by active dilution self-propagating high-temperature synthesis (SHS) method. The effects of endothermic reaction rate, the possible chemical reaction mechanism and active dilution model for synthesis of the product were also discussed. Highlights: ► Nano-sized amorphous boron powders were synthesized by active dilution self-propagating high-temperature synthesis method. ► The morphology, particle size and purity of the samples could be effectively controlled via changing the endothermic rate. ► The diluter KBH 4 played an important role in active dilution synthesis of amorphous nano-sized boron powders. ► The active dilution method could be further popularized and become a common approach to prepare various inorganic materials. - Abstract: Nano-sized amorphous boron powders were synthesized by active dilution self-propagating high-temperature synthesis (SHS) method at temperatures ranging from 700 °C to 850 °C in a SHS furnace using Mg, B 2 O 3 and KBH 4 as raw materials. Samples were characterized by X-ray powder diffraction (XRD), Laser particle size analyzer, Fourier transform infrared spectra (FTIR), X-ray energy dispersive spectroscopy (EDX), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high-resolution transmission TEM (HRTEM). The boron powders demonstrated an average particle size of 50 nm with a purity of 95.64 wt.%. The diluter KBH 4 played an important role in the active dilution synthesis of amorphous nano-sized boron powders. The effects of endothermic reaction rate, the possible chemical reaction mechanism and active dilution model for synthesis of the product were also discussed

Carbamoyl anion-initiated cascade reaction for stereoselective synthesis of substituted α-hydroxy-β-amino amides.

Science.gov (United States)

Lin, Chao-Yang; Ma, Peng-Ju; Sun, Zhao; Lu, Chong-Dao; Xu, Yan-Jun

2016-01-18

A carbamoyl anion-initiated cascade reaction with acylsilanes and imines has been used to rapidly construct substituted α-hydroxy-β-amino amides. The Brook rearrangement-mediated cascade allows the formation of two C-C bonds and one O-Si bond in a single pot. Using this approach, a range of α-aryl α-hydroxy-β-amino amides has been synthesized in high yields with excellent diastereoselectivities.

Self-sustained high-temperature reactions : Initiation, propagation and synthesis

NARCIS (Netherlands)

Martinez Pacheco, M.

2007-01-01

Self-Propagating High-Temperature Synthesis (SHS), also called combustion synthesis is an exothermic and self-sustained reaction between the constituents, which has assumed significance for the production of ceramics and ceramic-metallic materials (cermets), because it is a very rapid processing

High-deposition-rate ceramics synthesis

Energy Technology Data Exchange (ETDEWEB)

Allendorf, M.D.; Osterheld, T.H.; Outka, D.A. [Sandia National Laboratories, Livermore, CA (United States)] [and others

1995-05-01

Parallel experimental and computational investigations are conducted in this project to develop validated numerical models of ceramic synthesis processes. Experiments are conducted in the High-Temperature Materials Synthesis Laboratory in Sandia`s Combustion Research Facility. A high-temperature flow reactor that can accommodate small preforms (1-3 cm diameter) generates conditions under which deposition can be observed, with flexibility to vary both deposition temperature (up to 1500 K) and pressure (as low as 10 torr). Both mass spectrometric and laser diagnostic probes are available to provide measurements of gas-phase compositions. Experiments using surface analytical techniques are also applied to characterize important processes occuring on the deposit surface. Computational tools developed through extensive research in the combustion field are employed to simulate the chemically reacting flows present in typical industrial reactors. These include the CHEMKIN and Surface-CHEMKIN suites of codes, which permit facile development of complex reaction mechanisms and vastly simplify the implementation of multi-component transport and thermodynamics. Quantum chemistry codes are also used to estimate thermodynamic and kinetic data for species and reactions for which this information is unavailable.

Nanocrystalline Ni-Co Alloy Synthesis by High Speed Electrodeposition

OpenAIRE

Idris, Jamaliah; Christian, Chukwuekezie; Gaius, Eyu

2013-01-01

Electrodeposition of nanocrystals is economically and technologically viable production path for the synthesis of pure metals and alloys both in coatings and bulk form. The study presents nanocrystalline Ni-Co alloy synthesis by high speed electrodeposition. Nanocrystalline Ni-Co alloys coatings were prepared by direct current (DC) and deposited directly on steel and aluminum substrates without any pretreatment, using high speed electrodeposition method. The influence of the electrolysis par...

Diastereoselective Flexible Synthesis of Carbocyclic C-Nucleosides

Czech Academy of Sciences Publication Activity Database

Maier, L.; Khirsariya, P.; Hylse, O.; Adla, S.K.; Cernova, L.; Poljak, M.; Krajčovičová, S.; Weis, E.; Drápela, Stanislav; Souček, Karel; Paruch, K.

2017-01-01

Roč. 82, č. 7 (2017), s. 3382-3402 ISSN 0022-3263 Institutional support: RVO:68081707 Keywords : mitsunobu * catalysis * alcohols Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 4.849, year: 2016

Synthesis and Characterization of Highly Intercalated Graphite Bisulfate

OpenAIRE

Salvatore, Marcella; Carotenuto, Gianfranco; De Nicola, Sergio; Camerlingo, Carlo; Ambrogi, Veronica; Carfagna, Cosimo

2017-01-01

Different chemical formulations for the synthesis of highly intercalated graphite bisulfate have been tested. In particular, nitric acid, potassium nitrate, potassium dichromate, potassium permanganate, sodium periodate, sodium chlorate, and hydrogen peroxide have been used in this synthesis scheme as the auxiliary reagent (oxidizing agent). In order to evaluate the presence of delamination, and pre-expansion phenomena, and the achieved intercalation degree in the prepared samples, the obtain...

Synthesis of a novel chemotype via sequential metal-catalyzed cycloisomerizations

Directory of Open Access Journals (Sweden)

Bo Leng

2012-08-01

Full Text Available Sequential cycloisomerizations of diynyl o-benzaldehyde substrates to access novel polycyclic cyclopropanes are reported. The reaction sequence involves initial Cu(I-mediated cycloisomerization/nucleophilic addition to an isochromene followed by diastereoselective Pt(II-catalyzed enyne cycloisomerization.

One-Pot Two-Step Organocatalytic Asymmetric Synthesis of Spirocyclic Piperidones via Wolff Rearrangement–Amidation–Michael–Hemiaminalization Sequence

Directory of Open Access Journals (Sweden)

Yanqing Liu

2017-02-01

Full Text Available A highly enantioselective organocatalytic Wolff rearrangement–amidation–Michael–hemiaminalization stepwise reaction is described involving a cyclic 2-diazo-1,3-diketone, primary amine and α,β-unsaturated aldehyde. Product stereocontrol can be achieved by adjusting the sequence of steps in this one-pot multicomponent reaction. This approach was used to synthesize various optically active spirocyclic piperidones with three stereogenic centers and multiple functional groups in good yields up to 76%, moderate diastereoselectivities of up to 80:20 and high enantioselectivities up to 97%.

Self-propagating high temperature synthesis and magnetic

Indian Academy of Sciences (India)

Ni–Zn ferrite powders were synthesized by self-propagating high temperature synthesis (SHS) method. X-ray diffraction, TEM and vibrating sample magnetometry (VSM) were used to characterize the phase composition, microstructure and magnetic properties of the combustion products. The effect of the combustion ...

High Pressure Diels Alder Reactions of 1-Vinyl-2,2,6-trimethylcyclohexene Catalyzed by Chiral Lewis Acids; An Enantioselective Route to a Drimane Sesquiterpene Precursor.

NARCIS (Netherlands)

Knol, Joop; Meetsma, Auke; Feringa, Bernard

1995-01-01

The Diels Alder reaction of 1-vinyl-2,2,6-trimethylcyclohexene and 3-((E)-3-(methoxycarbonyl)propenoyl)-1,3-oxazolidin-2-one under high pressure, catalyzed by a chiral bis-imine copper(II) complex, yields a drimane sesquiterpene precursor in a highly regio- and diastereoselective manner with

Prodigious Effects of Concentration Intensification on Nanoparticle Synthesis: A High-Quality, Scalable Approach

KAUST Repository

Williamson, Curtis B.

2015-12-23

© 2015 American Chemical Society. Realizing the promise of nanoparticle-based technologies demands more efficient, robust synthesis methods (i.e., process intensification) that consistently produce large quantities of high-quality nanoparticles (NPs). We explored NP synthesis via the heat-up method in a regime of previously unexplored high concentrations near the solubility limit of the precursors. We discovered that in this highly concentrated and viscous regime the NP synthesis parameters are less sensitive to experimental variability and thereby provide a robust, scalable, and size-focusing NP synthesis. Specifically, we synthesize high-quality metal sulfide NPs (<7% relative standard deviation for Cu2-xS and CdS), and demonstrate a 10-1000-fold increase in Cu2-xS NP production (>200 g) relative to the current field of large-scale (0.1-5 g yields) and laboratory-scale (<0.1 g) efforts. Compared to conventional synthesis methods (hot injection with dilute precursor concentration) characterized by rapid growth and low yield, our highly concentrated NP system supplies remarkably controlled growth rates and a 10-fold increase in NP volumetric production capacity (86 g/L). The controlled growth, high yield, and robust nature of highly concentrated solutions can facilitate large-scale nanomanufacturing of NPs by relaxing the synthesis requirements to achieve monodisperse products. Mechanistically, our investigation of the thermal and rheological properties and growth rates reveals that this high concentration regime has reduced mass diffusion (a 5-fold increase in solution viscosity), is stable to thermal perturbations (64% increase in heat capacity), and is resistant to Ostwald ripening.

Stereoselective cathodic synthesis of 8-substituted (1R,3R,4S-menthylamines

Directory of Open Access Journals (Sweden)

Carolin Edinger

2015-02-01

Full Text Available The electrochemical generation of menthylamines from the corresponding menthone oximes equipped with an additional substituent in position 8 is described. Due to 1,3-diaxial interactions a pronounced diastereoselectivity for the menthylamines is found.

[Development of boomerang-type intramolecular cascade reactions and application to natural product synthesis].

Science.gov (United States)

Takasu, K

2001-12-01

Intramolecular cascade reaction has received much attention as a powerful methodology to construct a polycyclic framework in organic synthesis. We have been developing "boomerang-type cascade reaction" to construct a variety of polycyclic skeletons efficiently. In the above reactions, a nucleophilic function of substrates changes the character into an electrophile after the initial reaction, and the electrophilic group acts as a nucleophile in the second reaction. That is, the reaction center stepwise moves from one functional group back to the same one via other functional groups. The stream of the electron concerning the cascade reaction is like a locus of boomerang. We show here three different boomerang-type reactions via ionic species or free radicals. 1) Diastereoselective Michael-aldol reaction based on the chiral auxiliary method and enantioselective Michael-aldol reaction by the use of external chiral sources. 2) Short and efficient total syntheses of longifolane sesquiterpenes utilizing intramolecular double Michael addition as a key step. 3) Development of boomerang-type radical cascade reaction of halopolyenes to construct terpenoid skeletons and its regioselectivity.

Highly efficient and generalized asymmetric synthesis of quaternary stereogenic carbon-containing β-amino indanones/indanoles via Mannich-type additions between 1-indanones and N-tert-butanesulfinylketimines.

Science.gov (United States)

Wu, Lingmin; Xie, Chen; Mei, Haibo; Soloshonok, Vadim A; Han, Jianlin; Pan, Yi

2014-07-14

Here we report that, unlike other ketones, 1-indanone and acetophenone derived enolates undergo Mannich-type addition reactions with N-tert-butanesulfinyl ketimines with excellent yields (up to 98%) and diastereoselectivity (>99/1). The resulting compounds represent a new type of biologically relevant β-aminoketone derivative bearing quaternary stereogenic carbon, which could be further converted into the corresponding β-amino ketones and β-amino alcohols, possessing three consecutive stereogenic centres.

Alcohol synthesis in a high-temperature slurry reactor

Energy Technology Data Exchange (ETDEWEB)

Roberts, G.W.; Marquez, M.A.; McCutchen, M.S. [North Carolina State Univ., Raleigh, NC (United States)

1995-12-31

The overall objective of this contract is to develop improved process and catalyst technology for producing higher alcohols from synthesis gas or its derivatives. Recent research has been focused on developing a slurry reactor that can operate at temperatures up to about 400{degrees}C and on evaluating the so-called {open_quotes}high pressure{close_quotes} methanol synthesis catalyst using this reactor. A laboratory stirred autoclave reactor has been developed that is capable of operating at temperatures up to 400{degrees}C and pressures of at least 170 atm. The overhead system on the reactor is designed so that the temperature of the gas leaving the system can be closely controlled. An external liquid-level detector is installed on the gas/liquid separator and a pump is used to return condensed slurry liquid from the separator to the reactor. In order to ensure that gas/liquid mass transfer does not influence the observed reaction rate, it was necessary to feed the synthesis gas below the level of the agitator. The performance of a commercial {open_quotes}high pressure {close_quotes} methanol synthesis catalyst, the so-called {open_quotes}zinc chromite{close_quotes} catalyst, has been characterized over a range of temperature from 275 to 400{degrees}C, a range of pressure from 70 to 170 atm., a range of H{sub 2}/CO ratios from 0.5 to 2.0 and a range of space velocities from 2500 to 10,000 sL/kg.(catalyst),hr. Towards the lower end of the temperature range, methanol was the only significant product.

Low Power Design with High-Level Power Estimation and Power-Aware Synthesis

CERN Document Server

Ahuja, Sumit; Shukla, Sandeep Kumar

2012-01-01

Low-power ASIC/FPGA based designs are important due to the need for extended battery life, reduced form factor, and lower packaging and cooling costs for electronic devices. These products require fast turnaround time because of the increasing demand for handheld electronic devices such as cell-phones, PDAs and high performance machines for data centers. To achieve short time to market, design flows must facilitate a much shortened time-to-product requirement. High-level modeling, architectural exploration and direct synthesis of design from high level description enable this design process. This book presents novel research techniques, algorithms,methodologies and experimental results for high level power estimation and power aware high-level synthesis. Readers will learn to apply such techniques to enable design flows resulting in shorter time to market and successful low power ASIC/FPGA design. Integrates power estimation and reduction for high level synthesis, with low-power, high-level design; Shows spec...

Synthesis of (Arylamido)pyrrolidinone Libraries through Ritter-Type Cascade Reactions of Dihydroxylactams

DEFF Research Database (Denmark)

Wu, Peng; Petersen, Michael Åxman; Petersen, Rico

2015-01-01

diastereoselectivity. A combined one-step Ritter–hydrolysis procedure proved to be of equal efficiency. This versatile method, which was successfully used for the construction of a screening library containing 706 molecules within the European Lead Factory consortium, provides a simple way to access new compounds...

Synthesis of high specific activity tritium labelled compounds

International Nuclear Information System (INIS)

Parent, P.

1986-01-01

Tritiated methyl iodide of high specific activity is synthetized by Fischer-Tropsch reaction of tritium with carbon monoxide, tritiated methanol obtained is reacted with hydriodic acid. It is used for the synthesis of S-adenosyl L-methionine 3 H-methyl and of diazepam 3 H-methyl derivatives. Synthesis of 3-PPP 3 H: (hydroxy-3 phenyl)-3N-n propyl [ 3 H-2.3] piperidine [ 3 H-2.3] with a specific activity of 4.25 T Bq/mM (115 Ci/mM) and of baclofene 3 H with a specific activity of 0.925 TBq (25 Ci/mM) are also described [fr

Diastereoselective Au-Catalyzed Allene Cycloisomerizations to Highly Substituted Cyclopentenes.

Science.gov (United States)

Reeves, Ryan D; Phelps, Alicia M; Raimbach, William A T; Schomaker, Jennifer M

2017-07-07

Site- and regiocontrolled Au-catalyzed allene carbocyclizations furnish highly substituted cyclopentenes in >1:1 dr. Significant substitution on the substrate is tolerated, with potential to install five contiguous stereocenters after alkene functionalization. Major challenges include identifying a Au/Cu catalyst that controls both the relative rates of allene epimerization/cyclization and the facial selectivity in addition of a metal enolate to the allene. Experiments to achieve stereodivergent cyclizations and transform key cyclopentenes into useful synthetic building blocks are described.

Synthesis of Long Oxahelicenes by Polycyclization in a Flow Reactor

Czech Academy of Sciences Publication Activity Database

Nejedlý, Jindřich; Šámal, Michal; Rybáček, Jiří; Tobrmanová, Miroslava; Szydlo, Florence; Coudret, Christophe; Neumeier, Maria; Vacek, Jaroslav; Vacek Chocholoušová, Jana; Buděšínský, Miloš; Šaman, David; Bednárová, Lucie; Sieger, Ladislav; Stará, Irena G.; Starý, Ivo

2017-01-01

Roč. 56, č. 21 (2017), s. 5839-5843 ISSN 1433-7851 R&D Projects: GA ČR(CZ) GA16-08294S Institutional support: RVO:61388963 Keywords : oxahelicenes * diastereoselective [2+2+2] cycloisomerization * single-molecule conductivity by MCBJ method Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 11.994, year: 2016

Facile and green synthesis of highly stable L-cysteine functionalized copper nanoparticles

International Nuclear Information System (INIS)

Kumar, Nikhil; Upadhyay, Lata Sheo Bachan

2016-01-01

Highlights: • A facile and eco-friendly method for the synthesis of L-cysteine functionalized copper nanoparticles is reported. • Synthesis of Highly stable L-cysteine functionalized copper nanoparticles (∼40 nm) was done in an aqueous medium. • FTIR analysis shows that L-cysteine bound to the nanoparticle surface via thiol group. - Abstract: A simple eco-friendly method for L-cysteine capped copper nanoparticles (CCNPs) synthesis in aqueous solution has been developed. Glucose and L-cysteine were used as reducing agent and capping/functionalizing agent, respectively. Different parameters such as capping agent concentration, pH, reaction temperature, and reducing agent concentration were optimized during the synthesis. The L-cysteine capped copper nanoparticle were characterized by ultraviolet-visible spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, Particle size and zeta potential analyser, and high resolution transmission electron microscopy. Spherical shaped cysteine functionalized/capped copper nanoparticles with an average size of 40 nm were found to be highly stable at room temperature (RT) for a period of 1 month

Facile and green synthesis of highly stable L-cysteine functionalized copper nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Kumar, Nikhil, E-mail: nkumar.phd2011.bt@nitrr.ac.in; Upadhyay, Lata Sheo Bachan, E-mail: contactlataupadhyay@gmail.com

2016-11-01

Highlights: • A facile and eco-friendly method for the synthesis of L-cysteine functionalized copper nanoparticles is reported. • Synthesis of Highly stable L-cysteine functionalized copper nanoparticles (∼40 nm) was done in an aqueous medium. • FTIR analysis shows that L-cysteine bound to the nanoparticle surface via thiol group. - Abstract: A simple eco-friendly method for L-cysteine capped copper nanoparticles (CCNPs) synthesis in aqueous solution has been developed. Glucose and L-cysteine were used as reducing agent and capping/functionalizing agent, respectively. Different parameters such as capping agent concentration, pH, reaction temperature, and reducing agent concentration were optimized during the synthesis. The L-cysteine capped copper nanoparticle were characterized by ultraviolet-visible spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, Particle size and zeta potential analyser, and high resolution transmission electron microscopy. Spherical shaped cysteine functionalized/capped copper nanoparticles with an average size of 40 nm were found to be highly stable at room temperature (RT) for a period of 1 month.

Nanocrystalline Ni-Co Alloy Synthesis by High Speed Electrodeposition

Directory of Open Access Journals (Sweden)

Jamaliah Idris

2013-01-01

Full Text Available Electrodeposition of nanocrystals is economically and technologically viable production path for the synthesis of pure metals and alloys both in coatings and bulk form. The study presents nanocrystalline Ni-Co alloy synthesis by high speed electrodeposition. Nanocrystalline Ni-Co alloys coatings were prepared by direct current (DC and deposited directly on steel and aluminum substrates without any pretreatment, using high speed electrodeposition method. The influence of the electrolysis parameters, such as cathodic current density and temperature at constant pH, on electrodeposition and microstructure of Ni-Co alloys were examined. A homogeneous surface morphology was obtained at all current densities of the plated samples, and it was evident that the current density and temperature affect the coating thickness of Ni-Co alloy coatings.

High quality voice synthesis middle ware; Kohinshitsu onsei gosei middle war

Energy Technology Data Exchange (ETDEWEB)

NONE

2000-03-01

Toshiba Corp. newly developed a natural voice synthesis system, TOS Drive TTS (TOtally speaker Driven Text-To-Speech) system, in which natural high-quality read-aloud is greatly improved, and also developed as its application a voice synthesis middle ware. In the newly developed system, using as a model a narrator's voice recorded preliminarily, a metrical control dictionary is automatically learned that reproduces the characteristics of metrical patters such as intonation or rhythm of a human voice, as is a voice bases dictionary that reproduces the characteristics of a voice quality, enabling natural voice synthesis to be realized that picks up human voice characteristics. The system is high quality and also very compact, while the voice synthesis middle ware utilizing this technology is adaptable to various platforms such as MPU or OS. The system is very suitable for audio response in the ITS field having car navigation systems as the core; besides, expanded application is expected to an audio response system that used to employ a sound recording and reproducing system. (translated by NEDO)

Highly Stereoselective Intermolecular Haloetherification and Haloesterification of Allyl Amides

Science.gov (United States)

Soltanzadeh, Bardia; Jaganathan, Arvind; Staples, Richard J.

2016-01-01

An organocatalytic and highly regio-, diastereo-, and enantioselective intermolecular haloetherification and haloesterification reaction of allyl amides is reported. A variety of alkene substituents and substitution patterns are compatible with this chemistry. Notably, electronically unbiased alkene substrates exhibit exquisite regio- and diastereoselectivity for the title transformation. We also demonstrate that the same catalytic system can be used in both chlorination and bromination reactions of allyl amides with a variety of nucleophiles with little or no modification. PMID:26110812

A self-propagation high-temperature synthesis and annealing route to synthesis of wave-like boron nitride nanotubes

Energy Technology Data Exchange (ETDEWEB)

Wang, Jilin; Zhang, Laiping [School of Materials Science and Engineering, Wuhan Institute of Technology, Wuhan, Hubei, 430073 (China); Gu, Yunle, E-mail: ncm@mail.wit.edu.cn [School of Materials Science and Engineering, Wuhan Institute of Technology, Wuhan, Hubei, 430073 (China); Pan, Xinye; Zhao, Guowei; Zhang, Zhanhui [School of Materials Science and Engineering, Wuhan Institute of Technology, Wuhan, Hubei, 430073 (China)

2013-03-15

Highlights: ► Large quantities of wave-like BN nanotubes were synthesized by SHS-annealing method. ► The catalytic boron-containing porous precursor was produced by self-propagation high-temperature synthesis method. ► Three growth models were proposed to explain the growth mechanism of the wave-like BN nanotubes. - Abstract: Large quantities of boron nitride (BN) nanotubes were synthesized by annealing a catalytic boron-containing porous precursor in flowing NH{sub 3} gas at 1180 °C. The porous precursor was prepared by self-propagation high-temperature synthesis (SHS) method at 800 °C using Mg, B{sub 2}O{sub 3} and amorphous boron powder (α-B) as the starting materials. The porous precursor played an important role in large quantities synthesis of BN nanotubes. The as-synthesized product was characterized by X-ray diffractometer (XRD), Fourier transform infrared spectrometer (FTIR), Raman, Scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (EDS), Transmission electron microscopy (TEM) and High-resolution transmission electron microscopy (HRTEM). Characterization results indicated that the BN nanotubes displayed wave-like inner structures with diameters in the range of 50–300 nm and average lengths of more than 10 μm. The possible growth mechanism of the BN nanotubes was also discussed.

Rhodium-catalyzed [5 + 2 + 1] cycloaddition of ene-vinylcyclopropanes and CO: reaction design, development, application in natural product synthesis, and inspiration for developing new reactions for synthesis of eight-membered carbocycles.

Science.gov (United States)

Wang, Yi; Yu, Zhi-Xiang

2015-08-18

Practical syntheses of natural products and their analogues with eight-membered carbocyclic skeletons are important for medicinal and biological investigations. However, methods and strategies to construct the eight-membered carbocycles are limited. Therefore, developing new methods to synthesize the eight-membered carbocycles is highly desired. In this Account, we describe our development of three rhodium-catalyzed cycloadditions for the construction of the eight-membered carbocycles, which have great potential in addressing the challenges in the synthesis of medium-sized ring systems. The first reaction described in this Account is our computationally designed rhodium-catalyzed two-component [5 + 2 + 1] cycloaddition of ene-vinylcyclopropanes (ene-VCPs) and CO for the diastereoselective construction of bi- and tricyclic cyclooctenones. The design of this reaction is based on the hypothesis that the C(sp(3))-C(sp(3)) reductive elimination of the eight-membered rhodacycle intermediate generated from the rhodium-catalyzed cyclopropane cleavage and alkene insertion, giving Wender's [5 + 2] cycloadduct, is not easy. Under CO atmosphere, CO insertion may occur rapidly, converting the eight-membered rhodacycle into a nine-membered rhodacycle, which then undergoes an easy C(sp(2))-C(sp(3)) reductive elimination process and furnishes the [5 + 2 + 1] product. This hypothesis was supported by our preliminary DFT studies and also served as inspiration for the development of two [7 + 1] cycloadditions: the [7 + 1] cycloaddition of buta-1,3-dienylcyclopropanes (BDCPs) and CO for the construction of cyclooctadienones, and the benzo/[7 + 1] cycloaddition of cyclopropyl-benzocyclobutenes (CP-BCBs) and CO to synthesize the benzocyclooctenones. The efficiency of these rhodium-catalyzed cycloadditions can be revealed by the application in natural product synthesis. Two eight-membered ring-containing natural products, (±)-asterisca-3(15),6-diene and (+)-asteriscanolide, have been

Synthesis of highly faceted multiply twinned gold nanocrystals stabilized by polyoxometalates

International Nuclear Information System (INIS)

Yuan Junhua; Chen Yuanxian; Han Dongxue; Zhang Yuanjian; Shen Yanfei; Wang Zhijuan; Niu Li

2006-01-01

A novel and facile chemical synthesis of highly faceted multiply twinned gold nanocrystals is reported. The gold nanocrystals are hexagonal in transmission electron microscopy and icosahedral in scanning electron microscopy. Phosphotungstic acid (PTA), which was previously reduced, serves as a reductant and stabilizer for the synthesis of gold nanocrystals. The PTA-gold nanocomposites are quite stable in aqueous solutions, and electrochemically active towards the hydrogen evolution reaction

Development of coating technology for nuclear fuel by self-propagating high temperature synthesis

International Nuclear Information System (INIS)

Choi, Y.; Kim, Bong G.; Lee, Y. W.

1997-01-01

This paper presents experimental results of the preparation of silicon carbide and graphite layers on a nuclear fuel from silane and propane gases by a conventional chemical vapor deposition and combustion synthesis technologies. The direct reaction between silicon and pyrolytic carbon in a high temperature releases sufficient amount of energy to make a synthesis self-sustaining under the preheating of about 1200 deg C. During this high temperature process, lamellar structure with isotropic carbon synthesis. A full characterization of phase composition and final morphology of the coated layers by X-ray diffraction, SEM and AES is presented. (author). 6 refs., 1 tab., 11 figs

Studies toward the unique pederin family member psymberin: full structure elucidation, two alternative total syntheses, and analogs.

Science.gov (United States)

Feng, Yu; Jiang, Xin; De Brabander, Jef K

2012-10-17

Two synthetic approaches to psymberin have been accomplished. A highly convergent first generation synthesis led to the complete stereochemical assignment and demonstrated that psymberin and irciniastatin A are identical compounds. This synthesis featured a diastereoselective aldol coupling between the aryl fragment and a central tetrahydropyran core and a novel one-pot procedure to convert an amide, via intermediacy of a sensitive methyl imidate, to the N-acyl aminal reminiscent of psymberin. The highlights of the second generation synthesis include an efficient iridium-catalyzed enantioselective bisallylation of neopentyl glycol and a stepwise Sonogashira coupling/cycloisomerization/reduction sequence to construct the dihydroisocoumarin unit. The two synthetic avenues were achieved in 17-18 steps (longest linear sequence, ~14-15 isolations) from 3 fragments prepared in 7-8 (first generation) and 3-8 (second generation) steps each. This convergent approach allowed for the preparation of sufficient amounts of psymberin (~ 0.5 g) for follow-up biological studies. Meanwhile, our highly flexible strategy enabled the design and synthesis of multiple analogs, including a psymberin-pederin hybrid, termed psympederin, that proved crucial to a comprehensive understanding of the chemical biology of psymberin and related compounds that will be described in a subsequent manuscript.

Isoindolinones as Michael Donors under Phase Transfer Catalysis: Enantioselective Synthesis of Phthalimidines Containing a Tetrasubstituted Carbon Stereocenter

Directory of Open Access Journals (Sweden)

Francesco Scorzelli

2015-05-01

Full Text Available Readily available chiral ammonium salts derived from cinchona alkaloids have proven to be effective phase transfer catalysts in the asymmetric Michael reaction of 3-substituted isoindolinones. This protocol provides a convenient method for the construction of valuable asymmetric 3,3-disubstituted isoindolinones in high yields and  moderate to good enantioselectivity. Diastereoselectivity was also investigated in the construction of contiguous tertiary and quaternary stereocenters. The use of acrolein as Michael acceptor led to an interesting tricyclic derivative, a pyrroloisoindolinone analogue, via a tandem conjugated addition/cyclization reaction.

ACBC to Balcite: Bioinspired Synthesis of a Highly Substituted High-Temperature Phase from an Amorphous Precursor

Energy Technology Data Exchange (ETDEWEB)

Whittaker, Michael L.; Joester, Derk (NWU)

2017-04-28

Energy-efficient synthesis of materials locked in compositional and structural states far from equilibrium remains a challenging goal, yet biomineralizing organisms routinely assemble such materials with sophisticated designs and advanced functional properties, often using amorphous precursors. However, incorporation of organics limits the useful temperature range of these materials. Herein, the bioinspired synthesis of a highly supersaturated calcite (Ca0.5Ba0.5CO3) called balcite is reported, at mild conditions and using an amorphous calcium–barium carbonate (ACBC) (Ca1- x Ba x CO3·1.2H2O) precursor. Balcite not only contains 50 times more barium than the solubility limit in calcite but also displays the rotational disorder on carbonate sites that is typical for high-temperature calcite. It is significantly harder (30%) and less stiff than calcite, and retains these properties after heating to elevated temperatures. Analysis of balcite local order suggests that it may require the formation of the ACBC precursor and could therefore be an example of nonclassical nucleation. These findings demonstrate that amorphous precursor pathways are powerfully enabling and provide unprecedented access to materials far from equilibrium, including high-temperature modifications by room-temperature synthesis.

Sequential Multicomponent Strategy for the Diastereoselective Synthesis of Densely Functionalized Spirooxindole-Fused Thiazolidines

NARCIS (Netherlands)

Rainoldi, Giulia; Begnini, Fabio; De Munnik, Mariska; Lo Presti, Leonardo; Vande Velde, Christophe M.L.; Orru, Romano; Lesma, Giordano; Ruijter, Eelco; Silvani, Alessandra

2018-01-01

We developed two Ugi-type three-component reactions of spirooxindole-fused 3-thiazolines, isocyanides, and either carboxylic acids or trimethylsilyl azide, to give highly functionalized spirooxindole-fused thiazolidines. Two diverse libraries were generated using practical and robust procedures

Studies on synthesis of diamond at high pressure and temperature

Science.gov (United States)

Kailath, Ansu J.

Diamond is an essential material of modern industry and probably the most versatile abrasive available today. It also has many other industrial applications attributable to its unique mechanical, optical, thermal and electrical properties. Its usage has grown to the extent that there is hardly a production process in modern industry in which industrial diamond does not play a part. Bulk diamond production today is a major industry. Diamonds can be produced in its thermodynamically stable regions either by direct static conversion, or shock-wave conversion. The pressures and temperatures required for direct static conversion are very high. In the catalyst-solvent method, the material used establishes a reaction path with lower activation energy than for direct transformation. This helps in a quicker transformation under more benign conditions. Hence, catalyst-solvent synthesis is readily accomplished and is now a viable and successful industrial process. Diamonds produced by shock wave are very small (approximately 60mu). Therefore this diamond is limited to applications such as polishing compounds only. The quality, quantity, size and morphology of the crystals synthesized by catalyst-solvent process depend on different conditions employed for synthesis. These details, because of commercial reasons are not disclosed in published literature. Hence, systematic studies have been planned to investigate the effect of various growth parameters on the synthesized crystals. During the growth of synthetic diamond crystals, some catalyst-solvent is retained into the crystals in some form and behaves like an impurity. Several physico-mechanical properties of the crystals are found to depend on the total quantity and distribution of these inclusions. Thus, detailed investigation of the crystallization medium and inclusions in synthesized diamonds was also undertaken in the present work. The work incorporated in this thesis has been divided into seven chapters. The first

Stereocontrolled Synthesis of Methyl Silanediol Peptide Mimics

DEFF Research Database (Denmark)

Nielsen, Lone; Lindsay, Karl; Faber, Jesper

2007-01-01

 The treatment of chiral sulfinimines with (methyldiphenylsilyl)lithium gives R-(methyldiphenylsilyl)-sulfinamides with excellent diastereoselectivity, and in good yield. The presence of α-protons on the imines is also well tolerated. The sulfinamide auxiliary is easily removed via treatment with...... corresponding bis-TMS siloxane via protection with TMSCl, and converted back to the desired silanediol via hydrolysis with aqueous KOH. Efforts to apply this approach to biologically relevant silanediol peptide mimics, with a view to protease inhibition, are described....

Ammonia synthesis over multi-promoted iron catalysts obtained by high-energy ball-milling

DEFF Research Database (Denmark)

Jacobsen, C.J.H.; Jiang, Jianzhong; Mørup, Steen

1999-01-01

The feasibility of producing ammonia synthesis catalysts from high-energy ball-milling of a simple mixture of the constituent oxides has been investigated. The effect of ball-milling the fused oxidic precursor of the industrial KM1 ammonia synthesis catalyst has also been studied. The results show...

Direct catalytic asymmetric aldol-Tishchenko reaction.

Science.gov (United States)

Gnanadesikan, Vijay; Horiuchi, Yoshihiro; Ohshima, Takashi; Shibasaki, Masakatsu

2004-06-30

A direct catalytic asymmetric aldol reaction of propionate equivalent was achieved via the aldol-Tishchenko reaction. Coupling an irreversible Tishchenko reaction to a reversible aldol reaction overcame the retro-aldol reaction problem and thereby afforded the products in high enantio and diastereoselectivity using 10 mol % of the asymmetric catalyst. A variety of ketones and aldehydes, including propyl and butyl ketones, were coupled efficiently, yielding the corresponding aldol-Tishchenko products in up to 96% yield and 95% ee. Diastereoselectivity was generally below the detection limit of 1H NMR (>98:2). Preliminary studies performed to clarify the mechanism revealed that the aldol products were racemic with no diastereoselectivity. On the other hand, the Tishchenko products were obtained in a highly enantiocontrolled manner.

Stereoselective synthesis of functionalized cyclic amino acid derivatives via a [2,3]-Stevens rearrangement and ring-closing metathesis.

Science.gov (United States)

Nash, Aaron; Soheili, Arash; Tambar, Uttam K

2013-09-20

Unnatural cyclic amino acids are valuable tools in biomedical research and drug discovery. A two-step stereoselective strategy for converting simple glycine-derived aminoesters into unnatural cyclic amino acid derivatives has been developed. The process includes a palladium-catalyzed tandem allylic amination/[2,3]-Stevens rearrangement followed by a ruthenium-catalyzed ring-closing metathesis. The [2,3]-rearrangement proceeds with high diastereoselectivity through an exo transition state. Oppolzer's chiral auxiliary was utilized to access an enantiopure cyclic amino acid by this approach, which will enable future biological applications.

High pressure direct synthesis of adipic acid from cyclohexene and hydrogen peroxide via capillary microreactors

NARCIS (Netherlands)

Shang, M.; Noël, T.; Su, Y.; Hessel, V.

2016-01-01

The direct synthesis of adipic acid from hydrogen peroxide and cyclohexene was investigated in capillary microreactors at high temperature (up to 115°C ) and pressure (up to 70 bar). High temperature was already applied in micro-flow packed-bed reactors for the direct adipic acid synthesis. In our

Asymmetric syntheses of 3,4-disubstituted tetrahydroquinoline derivatives using (+)- sparteine-mediated electrophilic substitution

International Nuclear Information System (INIS)

Choi, Yun Soo; Kang, Kyoung Hee; Park, Yong Sun

2015-01-01

Tetrahydroquinolines bearing substituents are frequently found as a substructure in a number of alkaloids and natural products. Since their individual stereoisomers displays different biological activities, it is desirable to develop a highly stereoselective synthetic method for tetrahydroquinolines. While some progress has recently been made toward the development of asymmetric synthetic methods for tetrahydroquinolines, it is still a challenging topic in organic synthesis. In order to investigate the source of diastereoselection attained in the substitution reaction with a racemic epoxide, we examined the substitution of 2 with an excess amount of racemic p-chlorophenyl-substituted oxirane. We have developed a novel method for the asymmetric synthesis of trans-3,4-diaryl-substituted tetrahy- droquinolines from ortho-substituted N-pivaloyl anilines. The enantioselective process includes (+)-sparteine-mediated stereoselective lithiati on, kinetic resolution of epoxides in substitution, and stereospecific Mitsu nobu cyclization as the key reactions. The simple protocol can provide highly functionalized tetrahydroqu inoline rings and would allow their further functionalization to access more complex target molecules

Asymmetric syntheses of 3,4-disubstituted tetrahydroquinoline derivatives using (+)- sparteine-mediated electrophilic substitution

Energy Technology Data Exchange (ETDEWEB)

Choi, Yun Soo; Kang, Kyoung Hee; Park, Yong Sun [Dept. of Chemistry, Konkuk University, Seoul (Korea, Republic of)

2015-05-15

Tetrahydroquinolines bearing substituents are frequently found as a substructure in a number of alkaloids and natural products. Since their individual stereoisomers displays different biological activities, it is desirable to develop a highly stereoselective synthetic method for tetrahydroquinolines. While some progress has recently been made toward the development of asymmetric synthetic methods for tetrahydroquinolines, it is still a challenging topic in organic synthesis. In order to investigate the source of diastereoselection attained in the substitution reaction with a racemic epoxide, we examined the substitution of 2 with an excess amount of racemic p-chlorophenyl-substituted oxirane. We have developed a novel method for the asymmetric synthesis of trans-3,4-diaryl-substituted tetrahy- droquinolines from ortho-substituted N-pivaloyl anilines. The enantioselective process includes (+)-sparteine-mediated stereoselective lithiati on, kinetic resolution of epoxides in substitution, and stereospecific Mitsu nobu cyclization as the key reactions. The simple protocol can provide highly functionalized tetrahydroqu inoline rings and would allow their further functionalization to access more complex target molecules.

Electrochemical synthesis of highly crystalline copper nanowires

International Nuclear Information System (INIS)

Kaur, Amandeep; Gupta, Tanish; Kumar, Akshay; Kumar, Sanjeev; Singh, Karamjeet; Thakur, Anup

2015-01-01

Copper nanowires were fabricated within the pores of anodic alumina template (AAT) by template synthesis method at pH = 2.9. X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used to investigate the structure, morphology and composition of fabricated nanowires. These characterizations revealed that the deposited copper nanowires were highly crystalline in nature, dense and uniform. The crystalline copper nanowires are promising in application of future nanoelectronic devices and circuits

Approaches for introducing high molecular diversity in scaffolds: fast parallel synthesis of highly substituted 1H-quinolin-4-one libraries.

Science.gov (United States)

Kuznetsov, Vladimir; Gorohovsky, Sofia; Levy, Amalia; Meir, Simcha; Shkoulev, Vladimir; Menashe, Naim; Greenwald, Moshe; Aizikovich, Alexander; Ofer, Dror; Byk, Gerardo; Gellerman, Garry

2004-01-01

We have developed a two steps strategy for the parallel synthesis of highly diversified quinolin-ones. In the first step we have combined and improved different synthetic methods for generating quinolin-4-ones bearing four different substitutions at specific positions using round bottomed flasks. The synthesis was assessed for a large number of substituted quinolin-4-ones. In the second step, the improved method was adapted to a parallel array synthesis using a 12 positions carrousel as demonstrated for the synthesis of 42-variable quinolin-4-ones. The first combinatorial library set 14(a-x) was obtained with a chemical purity of more than 95% without purification, the second library set 15(a-r), which included two synthetic steps, needed combinatorial purification using an innovative parallel purifier. The proposed approach contributes to a more extensive diversification of molecular scaffolds in general and provides access to highly substituted quinolinones in particular.

Diastereoselective Synthesis of the Aminocyclitol Core of Jogyamycin via an Allene Aziridination Strategy.

Science.gov (United States)

Gerstner, Nels C; Adams, Christopher S; Grigg, R David; Tretbar, Maik; Rigoli, Jared W; Schomaker, Jennifer M

2016-01-15

Oxidative allene amination provides rapid access to densely functionalized amine-containing stereotriads through highly reactive bicyclic methyleneaziridine intermediates. This strategy has been demonstrated as a viable approach for the construction of the densely functionalized aminocyclitol core of jogyamycin, a natural product with potent antiprotozoal activity. Importantly, the flexibility of oxidative allene amination will enable the syntheses of modified aminocyclitol analogues of the jogyamycin core.

High yield polyol synthesis of round- and sharp-end silver nanowires with high aspect ratio

Energy Technology Data Exchange (ETDEWEB)

Nekahi, A.; Marashi, S.P.H., E-mail: pmarashi@aut.ac.ir; Fatmesari, D. Haghshenas

2016-12-01

Long silver nanowires (average length of 28 μm, average aspect ratio of 130) with uniform diameter along their length were produced by polyol synthesis of AgNO{sub 3} in ethylene glycol in the presence of PVP as preferential growth agent. Nanowires were produced with no addition of chloride salts such as NaCl or CuCl{sub 2} (or other additives such as Na{sub 2}S) which are usually used for lowering reduction rate of Ag ions by additional etchant of O{sub 2}/Cl{sup −}. Lower reduction rate was obtained by increasing the injection time of PVP and AgNO{sub 3} solutions, which was the significant factor in the formation of nanowires. Therefore, there was enough time for reduced Ag atoms to be deposited preferentially in the direction of PVP chains, resulting in high yield (the fraction of nanowires in the products) of nanowires (more than 95%) with high aspect ratio. The produced nanowires had both round- and sharp-ends with pentagonal cross section. Higher energy level of Ag atoms in borders of MTPs, which increases the dissolution rate of precipitated atoms, in addition to partial melting of MTPs at high synthesis temperatures, leads to the curving of the surfaces of exposed (111) crystalline planes in some MTPs and the formation of round-end silver nanowires. - Highlights: • Long silver nanowires with high aspect ratio of 130 were produced. • More than 95% nanowires were produced in products. • The produced nanowires had round- and sharp-ends with pentagonal cross section. • Additives were needed neither for high yield synthesis nor for round-end nanowires. • Melting and etching of MTPs in high energy borders resulted to round-end nanowires.

High-pressure-assisted synthesis of high-volume ZnGeP2 polycrystalline

Science.gov (United States)

Huang, Changbao; Wu, Haixin; Xiao, Ruichun; Chen, Shijing; Ma, Jiaren

2018-06-01

The pnictide and chalcogenide semiconductors are promising materials for the applications in the field of photoelectric. High-purity and high-volume polycrystalline required in the real-world applications is hard to be synthesized due to the high vapor pressure of phosphorus and sulfur components at high temperature. A new high-pressure-resisted method was used to investigate the synthesis of the nonlinear-optical semiconductor ZnGeP2. The high-purity ZnGeP2 polycrystalline material of approximately 500 g was synthesized in one run, which enables the preparation of nominally stoichiometric material. Since increasing internal pressure resistance of quartz crucible and reducing the reaction space, the high-pressure-resisted method can be used to rapidly synthesize other pnictide and chalcogenide semiconductors and control the components ratio.

Water-based synthesis of hydrophobic ionic liquids for high-energy electrochemical devices

International Nuclear Information System (INIS)

Montanino, Maria; Alessandrini, Fabrizio; Passerini, Stefano; Appetecchi, Giovanni Battista

2013-01-01

Highlights: ► Water-based synthesis of ionic liquids with high yield. ► Full recycling of reagents. ► High purity pyrrolidinium-based ionic liquids with exceptional electrochemical stability window. ► Lithium plating from pyrrolidinium-based ionic liquids. -- Abstract: In this work is described an innovative synthesis route for hydrophobic ionic liquids (ILs) composed of N-methyl-N-alkylpyrrolidinium (or piperidinium) or imidazolium or tetralkylammonium cations and (perfluoroalkylsulfonyl)imide, ((C n F 2n+1 SO 2 )(C m F 2m+1 SO 2 )N − ), anions. This synthesis does not require the use of any environmental unfriendly solvent such as acetone, acetonitrile or halogen-containing compounds, which is not welcome in industrial applications. Only water is used as the process solvent throughout the entire process. In addition, the commonly used iodine-containing reagents were replaced by the cheaper, more chemically stable and less toxic bromine-containing compounds. A particular care was devoted to the development of the purification route, which is especially important for ILs to be used in high-energy electrochemical devices such as high voltage supercapacitors and lithium batteries. The effect of the reaction temperature, the time and the stoichiometry in the various steps of the synthesis have been investigated in detail. This novel procedure allowed obtaining ultrapure (>99.9 wt.%), clear, colourless, inodorous ILs with an overall yield above 92 wt.% and moisture content below 1 ppm. NMR measurements were run to confirm the chemical structure whereas elemental analysis and electrochemical tests were performed to check the purity of the synthesized ILs

An Improved, Highly Efficient Method for the Synthesis of Bisphenols

Directory of Open Access Journals (Sweden)

L. S. Patil

2011-01-01

Full Text Available An efficient synthesis of bisphenols is described by condensation of substituted phenols with corresponding cyclic ketones in presence of cetyltrimethylammonium chloride and 3-mercaptopropionic acid as a catalyst in extremely high purity and yields.

Digital synthesis of pulse shapes in real time for high resolution radiation spectroscopy

International Nuclear Information System (INIS)

Jordanov, Valentin T.; Knoll, Glenn F.

1994-01-01

Techniques have been developed for the synthesis of pulse shapes using fast digital schemes in place of the traditional analog methods of pulse shaping. Efficient recursive algorithms have been developed that allow real time implementation of a shaper that can produce either trapezoidal or triangular pulse shapes. Other recursive techniques are presented which allow a synthesis of finite cusp-like shapes. Preliminary experimental tests show potential advantages of using these techniques in high resolution, high count rate pulse spectroscopy. ((orig.))

High-throughput synthesis equipment applied to polymer research

NARCIS (Netherlands)

Hoogenboom, R.; Schubert, U.S.

2005-01-01

To speed up synthetic polymer research, a workflow dedicated to automated polymer synthesis and characterization was developed. The workflow consists of several synthesis robots with online and offline analytical equipment. For screening of reaction parameters and for library synthesis, robots

Highly reproducible polyol synthesis for silver nanocubes

Science.gov (United States)

Han, Hye Ji; Yu, Taekyung; Kim, Woo-Sik; Im, Sang Hyuk

2017-07-01

We could synthesize the Ag nanocubes highly reproducibly by conducting the polyol synthesis using HCl etchant in dark condition because the photodecomposition/photoreduction of AgCl nanoparticles formed at initial reaction stage were greatly depressed and consequently the selective self-nucleation of Ag single crystals and their selective growth reaction could be promoted. Whereas the reproducibility of the formation of Ag nanocubes were very poor when we synthesize the Ag nanocubes in light condition due to the photoreduction of AgCl to Ag.

Diastereo- and regioselective addition of thioamide dianions to imines and aziridines: synthesis of N-thioacyl-1,2-diamines and N-thioacyl-1,3-diamines.

Science.gov (United States)

Shibahara, Fumitoshi; Kobayashi, Shun-ichiro; Maruyama, Toshifumi; Murai, Toshiaki

2013-01-02

Addition reactions of thioamide dianions that were derived from N-arylmethyl thioamides to imines and aziridines were carried out. The reactions of imines gave the addition products of N-thioacyl-1,2-diamines in a highly diastereoselective manner in good-to-excellent yields. The diastereomeric purity of these N-thioacyl-1,2-diamines could be enriched by simple recrystallization. The reduction of N-thioacyl-1,2-diamines with LiAlH(4) gave their corresponding 1,2-diamines in moderate-to-good yields with retention of their stereochemistry. The oxidative-desulfurization/cyclization of an N-thioacyl-1,2-diamine in CuCl(2)/O(2) and I(2)/pyridine systems gave the cyclized product in moderate yield and the trans isomer was obtained as the sole product. On the other hand, a similar cyclization reaction with antiformin (aq. NaClO) as an oxidant gave the cis isomer as the major product. The reactions of N-tosylaziridines gave the addition products of N-thioacyl-1,3-diamines with low diastereoselectivity but high regioselectivity and in good-to-excellent yields. The use of AlMe(3) as an additive improved the efficiency and regioselectivity of the reaction. The stereochemistry of the obtained products was determined by X-ray diffraction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of hydroxide type sorbents from industry high-iron wastes

International Nuclear Information System (INIS)

Stepanenko, E.K.; Smirnov, A.L.

1986-01-01

Article presents the results of studies on possibility of using of technological iron containing wastes for the obtaining of hydroxide type sorbents in granular form. The scheme of technology of synthesis of hydroxide type sorbents from high-iron wastes is elaborated.

Shock-induced synthesis of high temperature superconducting materials

Science.gov (United States)

Ginley, D.S.; Graham, R.A.; Morosin, B.; Venturini, E.L.

1987-06-18

It has now been determined that the unique features of the high pressure shock method, especially the shock-induced chemical synthesis technique, are fully applicable to high temperature superconducting materials. Extraordinarily high yields are achievable in accordance with this invention, e.g., generally in the range from about 20% to about 99%, often in the range from about 50% to about 90%, lower and higher yields, of course, also being possible. The method of this invention involves the application of a controlled high pressure shock compression pulse which can be produced in any conventional manner, e.g., by detonation of a high explosive material, the impact of a high speed projectile or the effect of intense pulsed radiation sources such as lasers or electron beams. Examples and a discussion are presented.

Rapid continuous flow synthesis of high-quality silver nanocubes and nanospheres

KAUST Repository

Mehenni, Hakim

2013-01-01

We report a biphasic-liquid segmented continuous flow method for the synthesis of high-quality plasmonic single crystal silver nanocubes and nanospheres. The nanocubes were synthesized with controllable edge lengths from 20 to 48 nm. Single crystal nanospheres with a mean size of 29 nm were obtained by in-line continuous-flow etching of as-produced 39 nm nanocubes with an aqueous solution of FeNO3. In comparison to batch synthesis, the demonstrated processes represent highly scalable reactions, in terms of both production rate and endurance. The reactions were conducted in a commercially available flow-reactor system that is easily adaptable to industrial-scale production, facilitating widespread utilization of the procedure and the resulting nanoparticles. This journal is © The Royal Society of Chemistry 2013.

A convenient access to thermodynamically nonstabilised spiroketal isomers: the first synthesis of (Z)-7-methyl-1,6-dioxaspiro[4.5]decane

Czech Academy of Sciences Publication Activity Database

Doubský, Jan; Šaman, David; Zedník, J.; Vašíčková, Soňa; Koutek, Bohumír

2005-01-01

Roč. 46, č. 46 (2005), s. 7923-7926 ISSN 0040-4039 Institutional research plan: CEZ:AV0Z4055905 Keywords : spiroketals * alpha-alkynones * diastereoselective Subject RIV: CC - Organic Chemistry Impact factor: 2.477, year: 2005

Python based high-level synthesis compiler

Science.gov (United States)

Cieszewski, Radosław; Pozniak, Krzysztof; Romaniuk, Ryszard

2014-11-01

This paper presents a python based High-Level synthesis (HLS) compiler. The compiler interprets an algorithmic description of a desired behavior written in Python and map it to VHDL. FPGA combines many benefits of both software and ASIC implementations. Like software, the mapped circuit is flexible, and can be reconfigured over the lifetime of the system. FPGAs therefore have the potential to achieve far greater performance than software as a result of bypassing the fetch-decode-execute operations of traditional processors, and possibly exploiting a greater level of parallelism. Creating parallel programs implemented in FPGAs is not trivial. This article describes design, implementation and first results of created Python based compiler.

High Throughput Synthesis and Screening for Agents Inhibiting Androgen Receptor Mediated Gene Transcription

National Research Council Canada - National Science Library

Boger, Dale L

2005-01-01

.... This entails the high throughput synthesis of DNA binding agents related to distamycin, their screening for binding to androgen response elements using a new high throughput DNA binding screen...

High Throughout Synthesis and Screening for Agents Inhibiting Androgen Receptor Mediated Gene Transcription

National Research Council Canada - National Science Library

Boger, Dale

2003-01-01

.... This entails the high throughput synthesis of DNA binding agents related to distamycin, their screening for binding to androgen response elements using a new high throughput DNA binding screen...

High Throughput Synthesis and Screening for Agents Inhibiting Androgen Receptor Mediated Gene Transcription

National Research Council Canada - National Science Library

Boger, Dale

2004-01-01

.... This entails the high throughput synthesis of DNA binding agents related to distamycin, their screening for binding to androgen response elements using a new high throughput DNA binding screen...

Synthesis and Characterization of Highly Intercalated Graphite Bisulfate

Science.gov (United States)

Salvatore, Marcella; Carotenuto, Gianfranco; De Nicola, Sergio; Camerlingo, Carlo; Ambrogi, Veronica; Carfagna, Cosimo

2017-03-01

Different chemical formulations for the synthesis of highly intercalated graphite bisulfate have been tested. In particular, nitric acid, potassium nitrate, potassium dichromate, potassium permanganate, sodium periodate, sodium chlorate, and hydrogen peroxide have been used in this synthesis scheme as the auxiliary reagent (oxidizing agent). In order to evaluate the presence of delamination, and pre-expansion phenomena, and the achieved intercalation degree in the prepared samples, the obtained graphite intercalation compounds have been characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray powder diffraction (XRD), infrared spectroscopy (FT-IR), micro-Raman spectroscopy ( μ-RS), and thermal analysis (TGA). Delamination and pre-expansion phenomena were observed only for nitric acid, sodium chlorate, and hydrogen peroxide, while the presence of strong oxidizers (KMnO4, K2Cr2O7) led to stable graphite intercalation compounds. The largest content of intercalated bisulfate is achieved in the intercalated compounds obtained from NaIO4 and NaClO3.

Multiple Word-Length High-Level Synthesis

Directory of Open Access Journals (Sweden)

Coussy Philippe

2008-01-01

Full Text Available Abstract Digital signal processing (DSP applications are nowadays widely used and their complexity is ever growing. The design of dedicated hardware accelerators is thus still needed in system-on-chip and embedded systems. Realistic hardware implementation requires first to convert the floating-point data of the initial specification into arbitrary length data (finite-precision while keeping an acceptable computation accuracy. Next, an optimized hardware architecture has to be designed. Considering uniform bit-width specification allows to use traditional automated design flow. However, it leads to oversized design. On the other hand, considering non uniform bit-width specification allows to get a smaller circuit but requires complex design tasks. In this paper, we propose an approach that inputs a C/C++ specification. The design flow, based on high-level synthesis (HLS techniques, automatically generates a potentially pipeline RTL architecture described in VHDL. Both bitaccurate integer and fixed-point data types can be used in the input specification. The generated architecture uses components (operator, register, etc. that have different widths. The design constraints are the clock period and the throughput of the application. The proposed approach considers data word-length information in all the synthesis steps by using dedicated algorithms. We show in this paper the effectiveness of the proposed approach through several design experiments in the DSP domain.

Multiple Word-Length High-Level Synthesis

Directory of Open Access Journals (Sweden)

Dominique Heller

2008-09-01

Full Text Available Digital signal processing (DSP applications are nowadays widely used and their complexity is ever growing. The design of dedicated hardware accelerators is thus still needed in system-on-chip and embedded systems. Realistic hardware implementation requires first to convert the floating-point data of the initial specification into arbitrary length data (finite-precision while keeping an acceptable computation accuracy. Next, an optimized hardware architecture has to be designed. Considering uniform bit-width specification allows to use traditional automated design flow. However, it leads to oversized design. On the other hand, considering non uniform bit-width specification allows to get a smaller circuit but requires complex design tasks. In this paper, we propose an approach that inputs a C/C++ specification. The design flow, based on high-level synthesis (HLS techniques, automatically generates a potentially pipeline RTL architecture described in VHDL. Both bitaccurate integer and fixed-point data types can be used in the input specification. The generated architecture uses components (operator, register, etc. that have different widths. The design constraints are the clock period and the throughput of the application. The proposed approach considers data word-length information in all the synthesis steps by using dedicated algorithms. We show in this paper the effectiveness of the proposed approach through several design experiments in the DSP domain.

Stereocontrolled synthesis of polyhydroxylated bicyclic azetidines as a new class of iminosugars.

Science.gov (United States)

Malinowski, Maciej; Hensienne, Raphaël; Kern, Nicolas; Tardieu, Damien; Bodlenner, Anne; Hazelard, Damien; Compain, Philippe

2018-06-12

We report herein the development of a stereodivergent route towards polyhydroxylated bicyclic azetidine scaffolds, namely 6-azabicyclo[3.2.0]heptane derivatives. The strategy hinges on a common bicyclic β-lactam precursor, which is forged by way of a rare example of a cationic Dieckmann-type reaction, followed by IBX-mediated desaturation. Substrate-controlled diastereoselective oxidations then allow the divergent preparation of novel iminosugar mimics.

Asymmetric Strecker Synthesis of α-Amino Acids via a Crystallization-Induced Asymmetric Transformation Using (R)-Phenylglycine Amide as Chiral Auxiliary

NARCIS (Netherlands)

Boesten, Wilhelmus H.J.; Seerden, Jean-Paul G.; Lange, Ben de; Dielemans, Hubertus J.A.; Elsenberg, Henk L.M.; Kaptein, Bernard; Moody, Harold M.; Kellogg, Richard M.; Broxterman, Quirinus B.

2001-01-01

Diastereoselective Strecker reactions based on (R)-phenylglycine amide as chiral auxiliary are reported. The Strecker reaction is accompanied by an in situ crystallization-induced asymmetric transformation, whereby one diastereomer selectively precipitates and can be isolated in 76-93% yield and dr

Large-Area Synthesis of High-Quality Uniform Few-Layer MoTe2.

Science.gov (United States)

Zhou, Lin; Xu, Kai; Zubair, Ahmad; Liao, Albert D; Fang, Wenjing; Ouyang, Fangping; Lee, Yi-Hsien; Ueno, Keiji; Saito, Riichiro; Palacios, Tomás; Kong, Jing; Dresselhaus, Mildred S

2015-09-23

The controlled synthesis of large-area, atomically thin molybdenum ditelluride (MoTe2) crystals is crucial for its various applications based on the attractive properties of this emerging material. In this work, we developed a chemical vapor deposition synthesis to produce large-area, uniform, and highly crystalline few-layer 2H and 1T' MoTe2 films. It was found that these two different phases of MoTe2 can be grown depending on the choice of Mo precursor. Because of the highly crystalline structure, the as-grown few-layer 2H MoTe2 films display electronic properties that are comparable to those of mechanically exfoliated MoTe2 flakes. Our growth method paves the way for the large-scale application of MoTe2 in high-performance nanoelectronics and optoelectronics.

Efficient Synthesis of Differentiated syn-1,2-Diol Derivatives by Asymmetric Transfer Hydrogenation-Dynamic Kinetic Resolution of α-Alkoxy-Substituted β-Ketoesters.

Science.gov (United States)

Monnereau, Laure; Cartigny, Damien; Scalone, Michelangelo; Ayad, Tahar; Ratovelomanana-Vidal, Virginie

2015-08-10

Asymmetric transfer hydrogenation was applied to a wide range of racemic aryl α-alkoxy-β-ketoesters in the presence of well-defined, commercially available, chiral catalyst Ru(II) -(N-p-toluenesulfonyl-1,2-diphenylethylenediamine) and a 5:2 mixture of formic acid and triethylamine as the hydrogen source. Under these conditions, dynamic kinetic resolution was efficiently promoted to provide the corresponding syn α-alkoxy-β-hydroxyesters derived from substituted aromatic and heteroaromatic aldehydes with a high level of diastereoselectivity (diastereomeric ratio (d.r.)>99:1) and an almost perfect enantioselectivity (enantiomeric excess (ee)>99 %). Additionally, after extensive screening of the reaction conditions, the use of Ru(II) - and Rh(III) -tethered precatalysts extended this process to more-challenging substrates that bore alkenyl-, alkynyl-, and alkyl substituents to provide the corresponding syn α-alkoxy-β-hydroxyesters with excellent enantiocontrol (up to 99 % ee) and good to perfect diastereocontrol (d.r.>99:1). Lastly, the synthetic utility of the present protocol was demonstrated by application to the asymmetric synthesis of chiral ester ethyl (2S)-2-ethoxy-3-(4-hydroxyphenyl)-propanoate, which is an important pharmacophore in a number of peroxisome proliferator-activated receptor α/γ dual agonist advanced drug candidates used for the treatment of type-II diabetes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and spectroscopic study of high quality alloy Cdx S ...

Indian Academy of Sciences (India)

Wintec

In the present study, we report the synthesis of high quality CdxZn1–xS nanocrystals alloy at. 150°C with .... (XRD) using a Siemens model D 500, powder X-ray ... decays were analysed using IBH DAS6 software. 3. ... This alloying process is.

Spray-combustion synthesis: efficient solution route to high-performance oxide transistors.

Science.gov (United States)

Yu, Xinge; Smith, Jeremy; Zhou, Nanjia; Zeng, Li; Guo, Peijun; Xia, Yu; Alvarez, Ana; Aghion, Stefano; Lin, Hui; Yu, Junsheng; Chang, Robert P H; Bedzyk, Michael J; Ferragut, Rafael; Marks, Tobin J; Facchetti, Antonio

2015-03-17

Metal-oxide (MO) semiconductors have emerged as enabling materials for next generation thin-film electronics owing to their high carrier mobilities, even in the amorphous state, large-area uniformity, low cost, and optical transparency, which are applicable to flat-panel displays, flexible circuitry, and photovoltaic cells. Impressive progress in solution-processed MO electronics has been achieved using methodologies such as sol gel, deep-UV irradiation, preformed nanostructures, and combustion synthesis. Nevertheless, because of incomplete lattice condensation and film densification, high-quality solution-processed MO films having technologically relevant thicknesses achievable in a single step have yet to be shown. Here, we report a low-temperature, thickness-controlled coating process to create high-performance, solution-processed MO electronics: spray-combustion synthesis (SCS). We also report for the first time, to our knowledge, indium-gallium-zinc-oxide (IGZO) transistors having densification, nanoporosity, electron mobility, trap densities, bias stability, and film transport approaching those of sputtered films and compatible with conventional fabrication (FAB) operations.

Synthesis of multi-wavelength temporal phase-shifting algorithms optimized for high signal-to-noise ratio and high detuning robustness using the frequency transfer function.

Science.gov (United States)

Servin, Manuel; Padilla, Moises; Garnica, Guillermo

2016-05-02

Synthesis of single-wavelength temporal phase-shifting algorithms (PSA) for interferometry is well-known and firmly based on the frequency transfer function (FTF) paradigm. Here we extend the single-wavelength FTF-theory to dual and multi-wavelength PSA-synthesis when several simultaneous laser-colors are present. The FTF-based synthesis for dual-wavelength (DW) PSA is optimized for high signal-to-noise ratio and minimum number of temporal phase-shifted interferograms. The DW-PSA synthesis herein presented may be used for interferometric contouring of discontinuous industrial objects. Also DW-PSA may be useful for DW shop-testing of deep free-form aspheres. As shown here, using the FTF-based synthesis one may easily find explicit DW-PSA formulae optimized for high signal-to-noise and high detuning robustness. To this date, no general synthesis and analysis for temporal DW-PSAs has been given; only ad hoc DW-PSAs formulas have been reported. Consequently, no explicit formulae for their spectra, their signal-to-noise, their detuning and harmonic robustness has been given. Here for the first time a fully general procedure for designing DW-PSAs (or triple-wavelengths PSAs) with desire spectrum, signal-to-noise ratio and detuning robustness is given. We finally generalize DW-PSA to higher number of wavelength temporal PSAs.

Facile and green synthesis of highly stable L-cysteine functionalized copper nanoparticles

Science.gov (United States)

Kumar, Nikhil; Upadhyay, Lata Sheo Bachan

2016-11-01

A simple eco-friendly method for L-cysteine capped copper nanoparticles (CCNPs) synthesis in aqueous solution has been developed. Glucose and L-cysteine were used as reducing agent and capping/functionalizing agent, respectively. Different parameters such as capping agent concentration, pH, reaction temperature, and reducing agent concentration were optimized during the synthesis. The L-cysteine capped copper nanoparticle were characterized by ultraviolet-visible spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, Particle size and zeta potential analyser, and high resolution transmission electron microscopy. Spherical shaped cysteine functionalized/capped copper nanoparticles with an average size of 40 nm were found to be highly stable at room temperature (RT) for a period of 1 month

High-Throughput Platform for Synthesis of Melamine-Formaldehyde Microcapsules.

Science.gov (United States)

Çakir, Seda; Bauters, Erwin; Rivero, Guadalupe; Parasote, Tom; Paul, Johan; Du Prez, Filip E

2017-07-10

The synthesis of microcapsules via in situ polymerization is a labor-intensive and time-consuming process, where many composition and process factors affect the microcapsule formation and its morphology. Herein, we report a novel combinatorial technique for the preparation of melamine-formaldehyde microcapsules, using a custom-made and automated high-throughput platform (HTP). After performing validation experiments for ensuring the accuracy and reproducibility of the novel platform, a design of experiment study was performed. The influence of different encapsulation parameters was investigated, such as the effect of the surfactant, surfactant type, surfactant concentration and core/shell ratio. As a result, this HTP-platform is suitable to be used for the synthesis of different types of microcapsules in an automated and controlled way, allowing the screening of different reaction parameters in a shorter time compared to the manual synthetic techniques.

Gel–sol synthesis and aging effect on highly crystalline anatase ...

Indian Academy of Sciences (India)

Gel–sol synthesis and aging effect on highly crystalline anatase nanopowder .... −1 in static air. To identify the gel-phase, it was mixed with D2O to form sample solution ... Ti(OH)4 chemical composition is produced this way: Ti3. [. (OC2H4)3 N. ].

Synthesis of multi-wavelength temporal phase-shifting algorithms optimized for high signal-to-noise ratio and high detuning robustness using the frequency transfer function

OpenAIRE

Servin, Manuel; Padilla, Moises; Garnica, Guillermo

2016-01-01

Synthesis of single-wavelength temporal phase-shifting algorithms (PSA) for interferometry is well-known and firmly based on the frequency transfer function (FTF) paradigm. Here we extend the single-wavelength FTF-theory to dual and multi-wavelength PSA-synthesis when several simultaneous laser-colors are present. The FTF-based synthesis for dual-wavelength PSA (DW-PSA) is optimized for high signal-to-noise ratio and minimum number of temporal phase-shifted interferograms. The DW-PSA synthesi...

Discovery and Synthesis of a Phosphoramidate Prodrug of a Pyrrolo[2,1-f][triazin-4-amino] Adenine C-Nucleoside (GS-5734) for the Treatment of Ebola and Emerging Viruses.

Science.gov (United States)

Siegel, Dustin; Hui, Hon C; Doerffler, Edward; Clarke, Michael O; Chun, Kwon; Zhang, Lijun; Neville, Sean; Carra, Ernest; Lew, Willard; Ross, Bruce; Wang, Queenie; Wolfe, Lydia; Jordan, Robert; Soloveva, Veronica; Knox, John; Perry, Jason; Perron, Michel; Stray, Kirsten M; Barauskas, Ona; Feng, Joy Y; Xu, Yili; Lee, Gary; Rheingold, Arnold L; Ray, Adrian S; Bannister, Roy; Strickley, Robert; Swaminathan, Swami; Lee, William A; Bavari, Sina; Cihlar, Tomas; Lo, Michael K; Warren, Travis K; Mackman, Richard L

2017-03-09

The recent Ebola virus (EBOV) outbreak in West Africa was the largest recorded in history with over 28,000 cases, resulting in >11,000 deaths including >500 healthcare workers. A focused screening and lead optimization effort identified 4b (GS-5734) with anti-EBOV EC 50 = 86 nM in macrophages as the clinical candidate. Structure activity relationships established that the 1'-CN group and C-linked nucleobase were critical for optimal anti-EBOV potency and selectivity against host polymerases. A robust diastereoselective synthesis provided sufficient quantities of 4b to enable preclinical efficacy in a non-human-primate EBOV challenge model. Once-daily 10 mg/kg iv treatment on days 3-14 postinfection had a significant effect on viremia and mortality, resulting in 100% survival of infected treated animals [ Nature 2016 , 531 , 381 - 385 ]. A phase 2 study (PREVAIL IV) is currently enrolling and will evaluate the effect of 4b on viral shedding from sanctuary sites in EBOV survivors.

Stereodivergent-at-metal synthesis of [60]fullerene hybrids

Energy Technology Data Exchange (ETDEWEB)

Marco-Martinez, Juan; Vidal, Sara; Fernandez, Israel; Filippone, Salvatore [Departamento de Quimica Organica I, Facultad de Ciencias Quimicas, Universidad Complutense de Madrid (Spain); Martin, Nazario [Departamento de Quimica Organica I, Facultad de Ciencias Quimicas, Universidad Complutense de Madrid (Spain); IMDEA-Nanociencia, C/Faraday, Universidad Autonoma de Madrid (Spain)

2017-02-13

Chiral fullerene-metal hybrids with complete control over the four stereogenic centers, including the absolute configuration of the metal atom, have been synthesized for the first time. The stereochemistry of the four chiral centers formed during [60]fullerene functionalization is the result of both the chiral catalysts employed and the diastereoselective addition of the metal complexes used (iridium, rhodium, or ruthenium). DFT calculations underpin the observed configurational stability at the metal center, which does not undergo an epimerization process. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

An efficient protocol for the synthesis of highly sensitive indole imines utilizing green chemistry: optimization of reaction conditions.

Science.gov (United States)

Nisar, Bushra; Rubab, Syeda Laila; Raza, Abdul Rauf; Tariq, Sobia; Sultan, Ayesha; Tahir, Muhammad Nawaz

2018-04-11

Novel and highly sensitive indole-based imines have been synthesized. Their synthesis has been compared employing a variety of protocols. Ultimately, a convenient, economical and high yielding set of conditions employing green chemistry have been designed for their synthesis.

Synthesis and Characterization of High Aluminum Zeolite X from Technical Grade Materials

Directory of Open Access Journals (Sweden)

Seyed Kamal Masoudian

2013-06-01

Full Text Available Zeolites are widely used as ion exchangers, adsorbents, separation materials and catalyst due to their well-tailored and highly-reproducible structures; therefore, the synthesis of zeolite from low grade resources can be interested. In the present work, high aluminum zeolite X was prepared from mixing technical grade sodium aluminate and sodium silicate solutions at temperatures between 70°C and 100°C. The synthesized zeolite X was characterized by SEM and X-ray methods according to ASTM standard procedures. The results showed that aging of the synthesis medium at the room temperature considerably increased the selectivity of zeolite X formation. On the other hand, high temperature of reaction mixture during crystallization formed zeolite A in the product; therefore, it decreased the purity of zeolite X. In addition, it was found that increasing H2O/Na2O and decreasing Na2O/SiO2 molar ratios in the reaction mixture resulted product with higher purity. © 2013 BCREC UNDIP. All rights reservedReceived: 7th January 2013; Revised: 7th April 2013; Accepted: 19th April 2013[How to Cite: Masoudian, S. K., Sadighi, S., Abbasi, A. (2013. Synthesis and Characterization of High Alu-minum Zeolite X from Technical Grade Materials. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (1: 54-60. (doi:10.9767/bcrec.8.1.4321.54-60][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.1.4321.54-60] | View in  |

Fast and inexpensive synthesis of pentacene with high yield using 6,13-pentacenequinone as precursor

Science.gov (United States)

Mota, María L.; Rodriguez, Bibiana; Carrillo, Amanda; Ambrosio, Roberto C.; Luque, Priscy A.; Mireles, Marcela; Vivaldo, Israel; Quevedo, Manuel A.

2018-02-01

Pentacene is an important semiconductor in the field of organic electronics. In this work is presented an alternative synthesis procedure to obtain pentacene from 6,13-pentacenequinone as a precursor. Synthesis of pentacene was performed in two reactions, Diels-Adler cycloaddition of 6,13-pentacenequinone followed by 6,13-pentacenequinone reduction to pentacene, employing LiAlH4 as reducing agent. The products were characterized by Fourier Transform Infrared Spectroscopy (FTIR), 1H-Nuclear Magnetic Resonance Spectroscopy (1H-NMR), X-Ray Diffraction (XRD), Thermogravimetric Analysis (TGA) and Ultraviolet-Visible Spectroscopy (UV-VIS). In this work, 6,13-pentacenequinone was synthetized with a high yield (55%) using an alternative method. The optimization process resulted in an overall reduction of reaction time while exhibiting high yield. The method presented here provides an affordable pentacene synthesis route with high purity, which can be further applied for research and development of organic electronic applications.

Multi-line split DNA synthesis: a novel combinatorial method to make high quality peptide libraries

Directory of Open Access Journals (Sweden)

Ueno Shingo

2004-09-01

Full Text Available Abstract Background We developed a method to make a various high quality random peptide libraries for evolutionary protein engineering based on a combinatorial DNA synthesis. Results A split synthesis in codon units was performed with mixtures of bases optimally designed by using a Genetic Algorithm program. It required only standard DNA synthetic reagents and standard DNA synthesizers in three lines. This multi-line split DNA synthesis (MLSDS is simply realized by adding a mix-and-split process to normal DNA synthesis protocol. Superiority of MLSDS method over other methods was shown. We demonstrated the synthesis of oligonucleotide libraries with 1016 diversity, and the construction of a library with random sequence coding 120 amino acids containing few stop codons. Conclusions Owing to the flexibility of the MLSDS method, it will be able to design various "rational" libraries by using bioinformatics databases.

The flavoprotein Tah18-dependent NO synthesis confers high-temperature stress tolerance on yeast cells

International Nuclear Information System (INIS)

Nishimura, Akira; Kawahara, Nobuhiro; Takagi, Hiroshi

2013-01-01

Highlights: ► NO is produced from L-arginine in response to elevated temperature in yeast. ► Tah18 was first identified as the yeast protein involved in NO synthesis. ► Tah18-dependent NO synthesis confers tolerance to high-temperature on yeast cells. -- Abstract: Nitric oxide (NO) is a ubiquitous signaling molecule involved in the regulation of a large number of cellular functions. In the unicellular eukaryote yeast, NO may be involved in stress response pathways, but its role is poorly understood due to the lack of mammalian NO synthase (NOS) orthologues. Previously, we have proposed the oxidative stress-induced L-arginine synthesis and its physiological role under stress conditions in yeast Saccharomyces cerevisiae. Here, our experimental results indicated that increased conversion of L-proline into L-arginine led to NO production in response to elevated temperature. We also showed that the flavoprotein Tah18, which was previously reported to transfer electrons to the Fe–S cluster protein Dre2, was involved in NO synthesis in yeast. Gene knockdown analysis demonstrated that Tah18-dependent NO synthesis confers high-temperature stress tolerance on yeast cells. As it appears that such a unique cell protection mechanism is specific to yeasts and fungi, it represents a promising target for antifungal activity.

Highly Efficient Procedure for the Synthesis of Fructone Fragrance Using a Novel Carbon based Acid

Directory of Open Access Journals (Sweden)

Xuezheng Liang

2010-08-01

Full Text Available The novel carbon based acid has been synthesized via one-step hydrothermal carbonization of furaldehyde and hydroxyethylsulfonic acid. A highly efficient procedure for the synthesis of fructone has been developed using the novel carbon based acid. The results showed that the catalyst possessed high activity for the reaction, giving a yield of over 95%. The advantages of high activity, stability, reusability and low cost for a simple synthesis procedure and wide applicability to various diols and β-keto esters make this novel carbon based acid one of the best choices for the reaction.

Tetrahydrofuran Calpha-tetrasubstituted amino acids: two consecutive beta-turns in a crystalline linear tripeptide.

Science.gov (United States)

Maity, Prantik; Zabel, Manfred; König, Burkhard

2007-10-12

The synthesis of tetrahydrofuran Calpha-tetrasubstituted amino acids (TAAs) and their effect on the conformation in small peptides are reported. The synthesis starts from the protein amino acid methionine, which is protected at the C and N terminus and converted into the corresponding sulfonium salt by alkylation. Simple base treatment in the presence of an aryl aldehyde leads to the formation of tetrahydrofuran tetrasubstituted Calpha-amino acids in a highly diastereoselective (trans/cis ratio up to 97:3) reaction with moderate to good yields (35-78%) depending on the aldehyde used. Palladium-catalyzed coupling reactions allow a subsequent further functionalization of the TAA. The R,S,S-TAA-Ala dipeptide amide adopts a beta-turn type I conformation, whereas its S,R,S isomer does not. The R,S,S-Gly-TAA-Ala tripeptide amide shows in the solid state and in solution a conformation of two consecutive beta-turn type III structures, stabilized by i+3-->i intramolecular hydrogen bonds.

Highly uniform up-converting nanoparticles: Why you should control your synthesis even more

International Nuclear Information System (INIS)

Palo, Emilia; Tuomisto, Minnea; Hyppänen, Iko; Swart, Hendrik C.; Hölsä, Jorma; Soukka, Tero; Lastusaari, Mika

2017-01-01

Luminescent β-NaYF 4 :Yb 3+ ,Er 3+ (x Yb : 0.17, x Er : 0.03) nanomaterials were synthesized for use as labels for biomedical applications with high temperature co-precipitation synthesis in 1-octadecene and oleic acid. The effect of the synthesis conditions (e.g. argon flow, cooling and stirring rates) on the products’ up-conversion luminescence intensity, particle size and morphology were studied. The factors contributing to these properties were analysed. It was observed that an efficient inert gas flow is essential to the formation of the preferred highly-luminescent hexagonal structure. Furthermore, the flow rate, together with the stirring rate, crucially affect the Er:Yb molar ratio of the products. The optimization of this ratio is essential when strong up-conversion emission is required from small particles, whereas the morphology and uniformity of the nanoparticles can be controlled with the cooling rate. These results emphasize the importance of controlling the synthesis conditions, especially when nanoparticles need to have a specific morphology because of their use e.g. as luminescent labels in medical diagnostics.

Highly uniform up-converting nanoparticles: Why you should control your synthesis even more

Energy Technology Data Exchange (ETDEWEB)

Palo, Emilia, E-mail: ekharj@utu.fi [University of Turku, Department of Chemistry, FI-20014 Turku (Finland); University of Turku Graduate School (UTUGS), Doctoral Programme in Physical and Chemical Sciences, Turku (Finland); Turku University Centre for Materials and Surfaces (MatSurf), Turku (Finland); Tuomisto, Minnea [University of Turku, Department of Chemistry, FI-20014 Turku (Finland); University of Turku Graduate School (UTUGS), Doctoral Programme in Physical and Chemical Sciences, Turku (Finland); Turku University Centre for Materials and Surfaces (MatSurf), Turku (Finland); Hyppänen, Iko [University of Turku, Department of Chemistry, FI-20014 Turku (Finland); Turku University Centre for Materials and Surfaces (MatSurf), Turku (Finland); Swart, Hendrik C.; Hölsä, Jorma [University of the Free State, Department of Physics, Bloemfontein ZA-9300 (South Africa); Soukka, Tero [University of Turku, Department of Biochemistry, FI-20014 Turku (Finland); Lastusaari, Mika [University of Turku, Department of Chemistry, FI-20014 Turku (Finland); Turku University Centre for Materials and Surfaces (MatSurf), Turku (Finland)

2017-05-15

Luminescent β-NaYF{sub 4}:Yb{sup 3+},Er{sup 3+} (x{sub Yb}: 0.17, x{sub Er}: 0.03) nanomaterials were synthesized for use as labels for biomedical applications with high temperature co-precipitation synthesis in 1-octadecene and oleic acid. The effect of the synthesis conditions (e.g. argon flow, cooling and stirring rates) on the products’ up-conversion luminescence intensity, particle size and morphology were studied. The factors contributing to these properties were analysed. It was observed that an efficient inert gas flow is essential to the formation of the preferred highly-luminescent hexagonal structure. Furthermore, the flow rate, together with the stirring rate, crucially affect the Er:Yb molar ratio of the products. The optimization of this ratio is essential when strong up-conversion emission is required from small particles, whereas the morphology and uniformity of the nanoparticles can be controlled with the cooling rate. These results emphasize the importance of controlling the synthesis conditions, especially when nanoparticles need to have a specific morphology because of their use e.g. as luminescent labels in medical diagnostics.

High-yield Synthesis of Multiwalled Carbon Nanotube by Mechanothermal Method

Directory of Open Access Journals (Sweden)

Manafi SA

2009-01-01

Full Text Available Abstract This study reports on the mechanothermal synthesis of multiwalled carbon nanotube (MWCNTs from elemental graphite powder. Initially, high ultra-active graphite powder can be obtained by mechanical milling under argon atmosphere. Finally, the mechanical activation product is heat-treated at 1350°C for 2–4 h under argon gas flow. After heat-treatment, active graphite powders were successfully changed into MWCNTs with high purity. The XRD analyses showed that in the duration 150 h of milling, all the raw materials were changed to the desired materials. From the broadening of the diffraction lines in the XRD patterns, it was concluded that the graphite crystallites were nanosized, and raising the milling duration resulted in the fineness of the particles and the increase of the strain. The structure and morphology of MWCNTs were investigated using scanning electron microscopy (SEM and high-resolution transmission electron microscopy (HRTEM. The yield of MWCNTs was estimated through SEM and TEM observations of the as-prepared samples was to be about 90%. Indeed, mechanothermal method is of interest for fundamental understanding and improvement of commercial synthesis of carbon nanotubes (CNTs. As a matter of fact, the method of mechanothermal guarantees the production of MWCNTs suitable for different applications.

Synthesis of molecules of biological interest labelled with high specific activity tritium

International Nuclear Information System (INIS)

Petillot, Yves

1975-01-01

Labelled molecules are artificial organic compounds possessing one or several radioactive or steady isotopic atoms. Using tritium to label molecules presents several benefits: a raw material easy to obtain with a high purity and at reasonable cost; synthesised labelled molecules displaying high specific activities very interesting in molecular biology; high resolution of radiographies; relatively simple and quick introduction of tritium atoms in complex molecules. Thus, this report for graduation in organic chemistry addresses the synthesis and study of new labelled molecules which belong to families of organic compounds which have fundamental activities in biology: uridine 3 H-5,6 and thymidine 3 H-methyl which are nucleotides which intervene under the form of phosphates in the synthesis of nucleic acids, oestradiol 3 H-2,4,6,7 which is a powerful estrogenic hormone which naturally secreted by the ovary; and noradrenaline 3 H-1,1' and dopamine 3 H-1,2 which are usually secreted by adrenal medulla and have multiple actions on the nervous system

Highly regio- and diastereoselective, acidic clay supported intramolecular nitrile oxide-alkene cycloaddition on D-ribose derived nitriles: an efficient synthetic route to isoxazoline fused five and six membered carbocycles.

Science.gov (United States)

Panda, Amarendra; Das, Sulagna; Pal, Shantanu

2014-10-29

An efficient synthetic route to isoxazoline fused carbocycles from carbohydrate scaffolds that comprise of free hydroxyl group(s) is described with high regio- and stereoselectivity. Montmorillonite K-10/chloramine T oxidation and in situ intramolecular nitrile oxide-alkene cycloaddition (INOC) of D-ribose derived oximes have been developed for the diversity oriented synthesis of isoxazoline fused five and six membered carbocycles. Copyright © 2014 Elsevier Ltd. All rights reserved.

Synthesis of high specific active tritiated Leu-enkephalin in the leucine residue

Energy Technology Data Exchange (ETDEWEB)

Baba, S.; Hasegawa, H.; Shinohara, Y. (Tokyo Coll. of Pharmacy (Japan))

1989-12-01

Leu-enkephalin labelled with tritium in the Leu residue has been prepared. Synthesis of the precursor peptide, (4,5-dehydroLeu{sup 5}-)Leu-enkephalin, was carried out by solid phase synthesis using Fmoc amino acid derivatives. The peptide was tritiated catalytically yielding {sup 3}H-Leu-enkephalin with a specific radioactivity of 4.39 TBq/mmol. The distribution of tritium label was investigated by reversed-phase high performance liquid chromatography with a synchronized accumulating radioisotope detector following acidic and enzymatic hydrolysis, which confirmed that the tritium label was entirely located at the Leu residue. (author).

High temperature bismuth cuprate superconductors synthesis and characterization

International Nuclear Information System (INIS)

Mansori, M.; Satre, P.; Breandon, C.; Roubin, M.; Sebaoun, A.

1993-01-01

High temperature superconductor phases synthesis by coprecipitation in alkaline solution is reported. (Bi 1.6 Pb 0.4 )Sr 2 Ca 1 Cu 2 O 8+x and (Bi 1.6 Pb 0.4 )Sr 2 Ca 2 Cu 3 O 10+y noted (2212) and (2223) have been prepared and studied. From aqueous nitrate solutions of Bi, Pb, Sr, Ca and Cu and oxalic acid aqueous solution as well as ethylene glycol, using an organic base (the triethylamine), the pH was increased up to the path of the precipitation zone (pH = 10.5-11.2). This method assures a good granulometric homogeneity of powders. Thermal analysis and characterization of the different components produced during the synthesis have been studied by DTA (differential thermal analysis)- TGA (thermogravimetric analysis), X-ray diffraction at different temperatures and by Infrared spectroscopy with a Fourier transformation. The measurements of magnetic susceptibility for the 2212 (with and without lead) and 2223 (with lead) phases have permitted us to observe the critical temperatures of 84 K, 87 K and 114 K. (author). 29 refs., 2 figs., 4 tabs

Synthesis of High Purity Nonsymmetric Dialkylphosphinic Acid Extractants.

Science.gov (United States)

Wang, Junlian; Xie, Meiying; Liu, Xinyu; Xu, Shengming

2017-10-19

We present the synthesis of (2,3-dimethylbutyl)(2,4,4'-trimethylpentyl)phosphinic acid as an example to demonstrate a method for the synthesis of high purity nonsymmetric dialkylphosphinic acid extractants. Low toxic sodium hypophosphite was chosen as the phosphorus source to react with olefin A (2,3-dimethyl-1-butene) to generate a monoalkylphosphinic acid intermediate. Amantadine was adopted to remove the dialkylphosphinic acid byproduct, as only the monoalkylphosphinic acid can react with amantadine to form an amantadine∙mono-alkylphosphinic acid salt, while the dialkylphosphinic acid cannot react with amantadine due to its large steric hindrance. The purified monoalkylphosphinic acid was then reacted with olefin B (diisobutylene) to yield nonsymmetric dialkylphosphinic acid (NSDAPA). The unreacted monoalkylphosphinic acid can be easily removed by a simple base-acid post-treatment and other organic impurities can be separated out through the precipitation of the cobalt salt. The structure of the (2,3-dimethylbutyl)(2,4,4'-trimethylpentyl)phosphinic acid was confirmed by 31 P NMR, 1 H NMR, ESI-MS, and FT-IR. The purity was determined by a potentiometric titration method, and the results indicate that the purity can exceed 96%.

High-gravity combustion synthesis and in situ melt infiltration: A new method for preparing cemented carbides

International Nuclear Information System (INIS)

Liu, Guanghua; Li, Jiangtao; Yang, Zengchao; Guo, Shibin; Chen, Yixiang

2013-01-01

A new method of high-gravity combustion synthesis and in situ melt infiltration is reported for preparing cemented carbides, where hot nickel melt is in situ synthesized from a highly exothermic combustion reaction and then infiltrated into tungsten carbide powder compacts. The as-prepared sample showed a homogeneous microstructure, and its relative density, hardness and flexural strength were 94.4%, 84 HRA and 1.49 GPa, respectively. Compared with conventional powder metallurgy approaches, high-gravity combustion synthesis offers a fast and furnace-free way to produce cemented carbides

The flavoprotein Tah18-dependent NO synthesis confers high-temperature stress tolerance on yeast cells

Energy Technology Data Exchange (ETDEWEB)

Nishimura, Akira; Kawahara, Nobuhiro [Graduate School of Biological Sciences, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma, Nara 630-0192 (Japan); Takagi, Hiroshi, E-mail: hiro@bs.naist.jp [Graduate School of Biological Sciences, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma, Nara 630-0192 (Japan)

2013-01-04

Highlights: Black-Right-Pointing-Pointer NO is produced from L-arginine in response to elevated temperature in yeast. Black-Right-Pointing-Pointer Tah18 was first identified as the yeast protein involved in NO synthesis. Black-Right-Pointing-Pointer Tah18-dependent NO synthesis confers tolerance to high-temperature on yeast cells. -- Abstract: Nitric oxide (NO) is a ubiquitous signaling molecule involved in the regulation of a large number of cellular functions. In the unicellular eukaryote yeast, NO may be involved in stress response pathways, but its role is poorly understood due to the lack of mammalian NO synthase (NOS) orthologues. Previously, we have proposed the oxidative stress-induced L-arginine synthesis and its physiological role under stress conditions in yeast Saccharomyces cerevisiae. Here, our experimental results indicated that increased conversion of L-proline into L-arginine led to NO production in response to elevated temperature. We also showed that the flavoprotein Tah18, which was previously reported to transfer electrons to the Fe-S cluster protein Dre2, was involved in NO synthesis in yeast. Gene knockdown analysis demonstrated that Tah18-dependent NO synthesis confers high-temperature stress tolerance on yeast cells. As it appears that such a unique cell protection mechanism is specific to yeasts and fungi, it represents a promising target for antifungal activity.

Synthesis of titanium carbide from wood by self-propagating high temperature synthesis

Directory of Open Access Journals (Sweden)

Sutham Niyomwas

2010-05-01

Full Text Available Titanium carbide (TiC particles were obtained in situ by a self-propagating high temperature synthesis (SHS of wooddust with TiO2 and Mg. The reaction was carried out in a SHS reactor under static argon gas at the pressure of 0.5 MPa. Thestandard Gibbs energy minimization method was used to calculate the equilibrium composition of the reacting species. Theeffects of increasing Mg mole ratio to the precursor mixture of TiO2 and wood dusts were investigated. XRD and SEManalyses indicate a complete reaction of the precursors to yield TiC-MgO as a product composite. The synthesized compositeswere leached with 0.1M HCl acid solution to obtain TiC particles as final products.

High pressure synthesis of BiS2

DEFF Research Database (Denmark)

Søndergaard-Pedersen, Simone; Nielsen, Morten Bormann; Bremholm, Martin

crystal structures and electrical properties.1,2 Up until now, the most sulfur rich phase in the Bi-S phase diagram was Bi2S3.3 For BiS2 the Bi atoms have anisotropic charge distribution and more complex structures are expected when comparing the layered structures of transition metal dichalcogenides....... The possibilities of using high pressure synthesis to discover new phases in the Bi-S binary system were investigated as early as the 1960’s.4 The research led to discovery of a compound with BiS2 stoichiometry, but no structure solution of BiS2 was reported. A reason behind making this new phase is to study...... the physical properties since the related compound Bi2S3 is known to be a thermoelectric material.5 In this research the BiS2 compound was synthesized by a high pressure and high temperature method using a multi-anvil large volume press and the structure was solved by single crystal diffraction. The structure...

Synthesis of novel 11-desmethyl analogues of laulimalide by Nozaki-Kishi coupling.

Science.gov (United States)

Paterson, Ian; Bergmann, Hermann; Menche, Dirk; Berkessel, Albrecht

2004-04-15

As a first entry into structurally simplified analogues of the anticancer agent laulimalide, 11-desmethyl compounds 2 and 3 were selected by molecular modeling. The unfavorable diastereoselectivity in the key synthetic step, a Nozaki-Kishi coupling between macrocyclic aldehyde 4 and vinyl iodide 5, was overcome either by use of catalytic amounts of DIANANE-type ligands or L-Selectride reduction of the derived enone. This methodology should allow modular introduction of other, unnatural, side chains. [reaction: see text

Fast nanostructured carbon microparticle synthesis by one-step high-flux plasma processing

NARCIS (Netherlands)

Aussems, D. U. B.; Bystrov, K.; Dogan, I.; Arnas, C.; Cabié, M.; Neisius, T.; Rasinski, M.; Zoethout, E.; Lipman, P.; van de Sanden, M. C. M.; Morgan, T. W.

2017-01-01

This study demonstrates a fast one-step synthesis method for nanostructured carbon microparticles on graphite samples using high-flux plasma exposure. These structures are considered as potential candidates for energy applications such as Li-ion batteries and supercapacitors. The samples were

Fast nanostructured carbon microparticle synthesis by one-step high-flux plasma processing

NARCIS (Netherlands)

Aussems, D.U.B.; Bystrov, K.E.; Doǧan, I.; Arnas, C.; Cabié, M.; Neisius, T.; Rasinski, M.; Lipman, P.J.L.; van de Sanden, M.C.M.; Morgan, T.W.

This study demonstrates a fast one-step synthesis method for nanostructured carbon microparticles on graphite samples using high-flux plasma exposure. These structures are considered as potential candidates for energy applications such as Li-ion batteries and supercapacitors. The samples were

Efficient One-Pot Synthesis of Colloidal Zirconium Oxide Nanoparticles for High-Refractive-Index Nanocomposites.

Science.gov (United States)

Liu, Chao; Hajagos, Tibor Jacob; Chen, Dustin; Chen, Yi; Kishpaugh, David; Pei, Qibing

2016-02-01

Zirconium oxide nanoparticles are promising candidates for optical engineering, photocatalysis, and high-κ dielectrics. However, reported synthetic methods for the colloidal zirconium oxide nanoparticles use unstable alkoxide precursors and have various other drawbacks, limiting their wide application. Here, we report a facile one-pot method for the synthesis of colloidally stable zirconium oxide nanoparticles. Using a simple solution of zirconium trifluoroacetate in oleylamine, highly stable zirconium oxide nanoparticles have been synthesized with high yield, following a proposed amidization-assisted sol-gel mechanism. The nanoparticles can be readily dispersed in nonpolar solvents, forming a long-term stable transparent solution, which can be further used to fabricate high-refractive-index nanocomposites in both monolith and thin-film forms. In addition, the same method has also been extended to the synthesis of titanium oxide nanoparticles, demonstrating its general applicability to all group IVB metal oxide nanoparticles.

Modular Stereoselective Synthesis of (1 -> 2)-C-Glycosides based on the sp(2)-sp(3) Suzuki-Miyaura Reaction

Czech Academy of Sciences Publication Activity Database

Oroszová, B.; Choutka, J.; Pohl, Radek; Parkan, K.

2015-01-01

Roč. 21, č. 19 (2015), s. 7043-7047 ISSN 0947-6539 Grant - others:GA ČR(CZ) GPP207/12/P713; GA ČR(CZ) GA15-17572S Institutional support: RVO:61388963 Keywords : C-disaccharides * C-glycosides * diastereoselectivity * Mitsunobu reaction * sp(2)-sp(3) coupling Subject RIV: CC - Organic Chemistry Impact factor: 5.771, year: 2015

One-pot multi-component green synthesis of highly substituted piperidines

Directory of Open Access Journals (Sweden)

Ravi Bansal

2017-05-01

Full Text Available An effective and expeditious method of the synthesis of a highly functionalized piperidines, catalyzed by nontoxic, recyclable and environment friendly sodium lauryl sulfate (SLS, via one-pot multi-component condensation of aldehydes, amines and β-ketoesters in water at room temperature, has been developed. This new protocol has advantages such as moderate to high yields of products obtained after simple post reaction workup. Structure of the synthesized compounds 4a–4j have been elucidated based on the 1H NMR, 13C NMR, FT-IR spectroscopy and elemental analysis.

Stereoselective synthesis of novel highly substituted isochromanone and isoquinolinone-containing exocyclic tetrasubstituted alkenes.

Science.gov (United States)

Arthuis, Martin; Pontikis, Renée; Florent, Jean-Claude

2009-03-06

An efficient synthetic route toward the synthesis of highly substituted arylethylidene-isoquinolinones/isochromanones is reported. The tandem carbopalladation/Suzuki-Miyaura coupling sequence stereoselectively provided various functionalized polycyclic compounds in moderate to excellent yields.

Synthesis and characterization of strontium carboxylates at room temperature and at high temperature in autoclave vessels

DEFF Research Database (Denmark)

Christgau, Stephan; Ståhl, Kenny; Andersen, Jens Enevold Thaulov

2006-01-01

A novel method was developed for synthesis of strontium coordination compounds in high yields. The synthesis proceeded along three pathways that provided strontium salts in high purity and high yields, close to 100%, as confirmed by flame atomic absorption spectroscopy (FAAS) and powder x......-ray crystallography. Optimum conditions were found at T = 120-1400C, a base-to-acid ratio of 1.2 and 15 min. of reaction-time in an autoclave vessel. Large crystals were readily obtained within a time period of hours. The crystal structures of strontium D-glutamate hexahydrate (I) and strontium di-(hydrogen L......-glutamate) pentahydrate (II) were confirmed by X-ray powder diffraction at 295 K and Rietveld refinements (I: Space group P212121, Z=4, a=7.3519(2), b=8.7616(2), c=20.2627(5) Å, and II: Space group P21, Z=2, a=8.7243(1), b=7.2635(1), c=14.6840(2) Å, β=100.5414(7) °). Synthesis at room temperature provided four additional...

Mechanically activated self-propagated high-temperature synthesis of nanometer-structured MgB2

International Nuclear Information System (INIS)

Radev, D.D.; Marinov, M.; Tumbalev, V.; Radev, I.; Konstantinov, L.

2005-01-01

Nanometer-sized MgB 2 was prepared via a two-step modification of the mechanically activated self-propagated high-temperature synthesis. The experimental conditions and some structural and phase characteristics of the synthesized product are reported. It is shown that a single-phase material can be prepared after 2 h of intense mechanical treatment of the starting magnesium and boron powders and a synthesis induced at a current-pulse density of 30 A cm -2 . The average size of MgB 2 particles synthesized in this way is 70-80 nm. It is also shown that using the same reagents and the 'classic' high-temperature interaction at 850 deg C with a protective atmosphere of pure Ar, mean particle size of the MgB 2 obtained is 50 μm

High-concentration copper nanoparticles synthesis process for screen-printing conductive paste on flexible substrate

International Nuclear Information System (INIS)

Tam, Sze Kee; Ng, Ka Ming

2015-01-01

This study presents a method for the synthesis of copper nanoparticles, which are poised to replace silver nanoparticles in some application areas of printed electronics. This method offers three advantages. Firstly, copper loading in the synthesis reaction can be as high as 1 M, offering high productivity in large-scale production. Secondly, the size of the copper nanoparticles can be controlled from 12 to 99 nm. Thirdly, the surface polarity of the particles can be modified. Thus, a tailor-made product can be synthesized. The synthesis of copper nanoparticles coated with various capping agents, including dodecanethiol, lauric acid, nonanoic acid, polyacrylic acid, and polyvinyl pyrrolidone, was demonstrated. The nonanoic acid-coated copper nanoparticles were formulated as a screen-printing conductive paste. The particles were readily dispersed in terpineol, and the paste could be screen printed onto flexible polyester. The electrical resistivity of patterns after a low-temperature (120 °C) sintering treatment was around 5.8 × 10 −5  Ω cm.Graphical Abstract

High-concentration copper nanoparticles synthesis process for screen-printing conductive paste on flexible substrate

Energy Technology Data Exchange (ETDEWEB)

Tam, Sze Kee; Ng, Ka Ming, E-mail: kekmng@ust.hk [The Hong Kong University of Science and Technology, Department of Chemical and Biomolecular Engineering (Hong Kong)

2015-12-15

This study presents a method for the synthesis of copper nanoparticles, which are poised to replace silver nanoparticles in some application areas of printed electronics. This method offers three advantages. Firstly, copper loading in the synthesis reaction can be as high as 1 M, offering high productivity in large-scale production. Secondly, the size of the copper nanoparticles can be controlled from 12 to 99 nm. Thirdly, the surface polarity of the particles can be modified. Thus, a tailor-made product can be synthesized. The synthesis of copper nanoparticles coated with various capping agents, including dodecanethiol, lauric acid, nonanoic acid, polyacrylic acid, and polyvinyl pyrrolidone, was demonstrated. The nonanoic acid-coated copper nanoparticles were formulated as a screen-printing conductive paste. The particles were readily dispersed in terpineol, and the paste could be screen printed onto flexible polyester. The electrical resistivity of patterns after a low-temperature (120 °C) sintering treatment was around 5.8 × 10{sup −5} Ω cm.Graphical Abstract.

On-Surface Pseudo-High-Dilution Synthesis of Macrocycles: Principle and Mechanism.

Science.gov (United States)

Fan, Qitang; Wang, Tao; Dai, Jingya; Kuttner, Julian; Hilt, Gerhard; Gottfried, J Michael; Zhu, Junfa

2017-05-23

Macrocycles have attracted much attention due to their specific "endless" topology, which results in extraordinary properties compared to related linear (open-chain) molecules. However, challenges still remain in their controlled synthesis with well-defined constitution and geometry. Here, we report the successful application of the (pseudo-)high-dilution method to the conditions of on-surface synthesis in ultrahigh vacuum. This approach leads to high yields (up to 84%) of cyclic hyperbenzene ([18]-honeycombene) via an Ullmann-type reaction from 4,4″-dibromo-meta-terphenyl (DMTP) as precursor on a Ag(111) surface. The mechanism of macrocycle formation was explored in detail using scanning tunneling microscopy and X-ray photoemission spectroscopy. We propose that the dominant pathway for hyperbenzene (MTP) 6 formation is the stepwise desilverization of an organometallic (MTP-Ag) 6 macrocycle, which forms via cyclization of (MTP-Ag) 6 chains under pseudo-high-dilution conditions. The high probability of cyclization on the stage of the organometallic phase results from the reversibility of the C-Ag bond. The case is different from that in solution, in which cyclization typically occurs on the stage of a covalently bonded open-chain precursor. This difference in the cyclization mechanism on a surface compared to that in solution stems mainly from the 2D confinement exerted by the surface template, which hinders the flipping of chain segments necessary for cyclization.

New Synthesis and Tritium Labeling of a Selective Ligand for Studying High-affinity γ-Hydroxybutyrate (GHB) Binding Sites

Science.gov (United States)

Vogensen, Stine B.; Marek, Aleš; Bay, Tina; Wellendorph, Petrine; Kehler, Jan; Bundgaard, Christoffer; Frølund, Bente; Pedersen, Martin H.F.; Clausen, Rasmus P.

2013-01-01

3-Hydroxycyclopent-1-enecarboxylic acid (HOCPCA, 1) is a potent ligand for the high-affinity GHB binding sites in the CNS. An improved synthesis of 1 together with a very efficient synthesis of [3H]-1 is described. The radiosynthesis employs in situ generated lithium trimethoxyborotritide. Screening of 1 against different CNS targets establishes a high selectivity and we demonstrate in vivo brain penetration. In vitro characterization of [3H]-1 binding shows high specificity to the high-affinity GHB binding sites. PMID:24053696

New labeling methods via organometallic species: new synthesis of a chiral methyl group

International Nuclear Information System (INIS)

Faucher, Nicolas

2000-01-01

Chapter 1: New labeling methods via organometallic species. In the first part of this work, we have developed a new labeling strategy based on the hydrogenolysis of organolithium compounds with tritium gas or deuterium gas. This reaction is catalyzed with palladium on charcoal and leads to the labelled compounds with direct replacement of the proton by its isotopes ("2H or "3H) without further chemical modification of the target molecule. Using this strategy, tritium or deuterium atoms can be introduced in a region but also in a stereoselective fashion with more than 90% ee. The former result was obtained using (-)-sparteine during the lithiation step. Chapter II: New synthesis of a chiral methyl group. In the second part of this work, we have developed a new synthetic method to prepare chiral ditosyl-methylamine using 4,5-disubstituted oxazolidines. Dia-stereoselective substitution of the methoxy group of a 2-alkoxy-oxazolidine by a deuteride in the presence of a Lewis acid leads to the 2-deutero-oxazolidine in a highly stereoselective fashion (de = 100%). Still using a lewis acid, a tritiated hydride open the former 2-deutero-oxazolidine to afford chiral methyl group borne by the nitrogen. Further de-protection and re-protection steps lead to the ditosyl-methylamine with an ee of 65% (RIS= 83/17). Nowadays, this is the best known synthetic method, not only in terms of enantioselectivity but also in terms of chemical yield and number of radioactive steps. As NTs_2 is a fairly good leaving group, the ditosyl-methylamine offers the possibility of introducing chiral methyl group in many substrates using a S_N2 reaction with various nucleophiles. This last point leads to many potential applications in the field of biochemistry or for mechanical studies. (author) [fr

A Convenient Route to Higher Sugars by Two-Carbon Chain Elongation Using Wittig/Dihydroxylation Reactions

DEFF Research Database (Denmark)

Jørgensen, Morten; Iversen, Erik Høgh; Madsen, Robert

2001-01-01

The combination of a Wittig olefination and a dihydroxylation reaction constitutes a facile synthetic protocol for the transformation of unprotected carbohydrates into higher sugars. The Wittig reaction is carried out with tert-butyl or diphenylmethyl ester stabilized phosphoranes to give (E......)-configured alpha,beta -unsaturated esters as the only products in most cases. These are dihydroxylated in a diastereoselective fashion using OsO4/NMO. The stereochemical outcome in the dihydroxylation follows Kishi's empirical rule and gives high diastereoselectivity (5:1-8:1) when starting from sugars with the 2......,3-threo configuration. When starting from sugars with the 2,3-erythro configuration, the diastereoselectivity in the dihydroxylation is low (2:1-2.5:1). As a result, the Wittig/dihydroxylation protocol is most effective for producing higher sugars with the galacto configuration at the reducing end...

Mechanical alloying and self-propagating high-temperature synthesis of stable icosahedral quasicrystals

International Nuclear Information System (INIS)

Bokhonov, B.B.

2008-01-01

The phase evolution of the mechanically alloyed ternary 63%Al + 25%Cu + 12%Fe and 65%Al + 20%Cu + 15%Fe powder mixtures with milling time has been studied by X-ray diffraction method. It was found that an icosahedral quasicrystalline phase was formed directly during high-energy ball milling of the Al-Cu-Fe mixtures. The X-ray and scanning electron microscopic investigations demonstrated the possibility to use self-propagating high-temperature synthesis (SHS) in combination with preliminary mechanical activation for the synthesis of stable icosahedral quasicrystals. The typical morphology of the Al 63 Cu 25 Fe 12 icosahedral quasicrystals formed in the SHS process is a pentagonal dodecahedron with a size of 3-5 mm. The phase composition of the SHS products depends on the time of preliminary mechanical activation. The content of cubic intermetallic phase in SHS products increases with the time of preliminary mechanical activation of the 63%Al + 25%Cu + 12%Fe powder mixtures

Fe-Catalyzed Synthesis of Porous Carbons Spheres with High Graphitization Degree for High-Performance Supercapacitors

Science.gov (United States)

Zhu, Jun; Shi, Hongwei; Zhuo, Xin; Hu, Yalin

2017-10-01

We have developed a facile and efficient Fe-catalyzed method for fabrication of porous carbons spheres with high graphitization degree (GNPCs) using glucose as carbon precursor at relatively low carbonization temperature. GNPCs not only have relatively large accessible ion surface area to accommodate greater capacity but also high graphitization degree to accelerate ion diffusion. As a typical application, we demonstrate that GNPCs exhibit excellent electrochemical performance for use in supercapacitors, with high specific capacity of 150.6 F g-1 at current density of 1 A g-1 and good rate capability and superior cycling stability over 10,000 cycles, confirming their potential application for energy storage. Moreover, it is believed that this method offers a new strategy for synthesis of porous carbons with high graphitization degree.

The course of protein synthesis during grain filling in normal and high lysine barley

International Nuclear Information System (INIS)

Giese, H.; Andersen, B.

1984-01-01

A study of the course of protein synthesis during grain filling in Bomi and the high lysine barleys Hily 82/3 and Risoe 56 showed that the four salt-soluble proteins, protein Z, β-amylase and the chymotrypsin inhibitors CI-1 and CI-2, are synthesized in greater amounts earlier in the high lysine lines than in Bomi. On the other hand, the hordeins are synthesized in greater amounts earlier during grain filling in Bomi than in Hily 82/3 and Risoe 56. There is no indication of a significant reduction of total protein synthesis in the high lysine lines compared with the standard lines Bomi and Pirrka. Hily 82/3 and Risoe 56 are very similar in protein composition in that they have a lower hordein content and higher levels, particularly of β-amylase and the chymotrypsin inhibitors, than Bomi. (author)

Fabrication of Titanium Diboride-Cu Composite by Self-High Temperature Synthesis plus Quick Press

Institute of Scientific and Technical Information of China (English)

Jinyong ZHANG; Zhengyi FU; Weimin WANG

2005-01-01

Titanium diboride based composites, good candidates for contact materials, have high hardness, Young's modulus,high temperature stability, and excellent electrical, thermal conductivity. However a good interface of TiB2/Cu is very difficult to achieve for oxidation of TiB2. To avoid this oxidation behavior, the in situ combusting synthesis technology, SHS, was used to prepare TiB2/Cu composite. Thecharacters of Ti-B-xCu SHS were studied in detail,such as combustion temperature, products phases and grain size. Based on the experimental results a proper technology way of self-high temperature synthesis plus quick press (SHS/QP) was determined and compact TiB2/Cu composites with relative density over than 97 pct of the theoretical were fabricated by this method. The properties and microstructures of these TiB2 based composites were also investigated.

High-Yield Synthesis of Zinc Oxide Nanoparticles from Bicontinuous Microemulsions

Directory of Open Access Journals (Sweden)

S. López-Cuenca

2011-01-01

Full Text Available The high-yield synthesis of zinc oxide (ZnO primary nanoparticles with high purity and with diameters between 6 and 22 nm using bicontinuous microemulsions is reported in this work. The ZnO nanoparticles were made by hydrolysis of Zn(NO32 with NaOH aqueous solution and precipitation, followed by calcination of the precipitate. Higher yields and productivities of ZnO nanoparticles were obtained compared to values produced with w/o micremulsions reported in the literature. Particles were characterized by transmission electronic microscopy (TEM, X-ray diffraction, and atomic absorption spectroscopy.

Tandem Michael addition/radical cyclizations for the construction of highly functionalized cyclopentanes

Czech Academy of Sciences Publication Activity Database

Holan, Martin; Pohl, Radek; Císarová, I.; Jahn, Ullrich

2012-01-01

Roč. 106, - (2012), s1298-s1298 ISSN 0009-2770. [EuCheMS Chemistry Congress /4./. 26.08.2012-30.08.2012, Prague] Institutional research plan: CEZ:AV0Z40550506 Keywords : cyclization * diastereoselectivity * Michael addiction * radical reactions * domino reactions Subject RIV: CC - Organic Chemistry

Bidirectional cross metathesis and ring-closing metathesis/ring opening of a C2-symmetric building block: a strategy for the synthesis of decanolide natural products

Directory of Open Access Journals (Sweden)

Bernd Schmidt

2013-11-01

Full Text Available Starting from the conveniently available ex-chiral pool building block (R,R-hexa-1,5-diene-3,4-diol, the ten-membered ring lactones stagonolide E and curvulide A were synthesized using a bidirectional olefin-metathesis functionalization of the terminal double bonds. Key steps are (i a site-selective cross metathesis, (ii a highly diastereoselective extended tethered RCM to furnish a (Z,E-configured dienyl carboxylic acid and (iii a Ru–lipase-catalyzed dynamic kinetic resolution to establish the desired configuration at C9. Ring closure was accomplished by macrolactonization. Curvulide A was synthesized from stagonolide E through Sharpless epoxidation.

Bidirectional cross metathesis and ring-closing metathesis/ring opening of a C 2-symmetric building block: a strategy for the synthesis of decanolide natural products.

Science.gov (United States)

Schmidt, Bernd; Kunz, Oliver

2013-01-01

Starting from the conveniently available ex-chiral pool building block (R,R)-hexa-1,5-diene-3,4-diol, the ten-membered ring lactones stagonolide E and curvulide A were synthesized using a bidirectional olefin-metathesis functionalization of the terminal double bonds. Key steps are (i) a site-selective cross metathesis, (ii) a highly diastereoselective extended tethered RCM to furnish a (Z,E)-configured dienyl carboxylic acid and (iii) a Ru-lipase-catalyzed dynamic kinetic resolution to establish the desired configuration at C9. Ring closure was accomplished by macrolactonization. Curvulide A was synthesized from stagonolide E through Sharpless epoxidation.

One-step synthesis of dimethyl ether from the gas mixture containing CO2 with high space velocity

International Nuclear Information System (INIS)

Chen, Wei-Hsin; Lin, Bo-Jhih; Lee, How-Ming; Huang, Men-Han

2012-01-01

Highlights: ► A bifunctional catalyst for DME synthesis is prepared using a coprecipitation method. ► The DME synthesis from syngas at a high space velocity of is investigated. ► The reaction is dominated by chemical kinetics at lower reaction temperatures. ► Thermodynamic equilibrium governs the reaction at higher temperatures. ► 0.2 g of ZSM5 is sufficient to be blended with 1 g of the catalyst for DME synthesis. -- Abstract: Dimethyl ether (DME) has been considered as a potential hydrogen carrier used in fuel cells; it can also be consumed as a diesel substitute or chemicals. To develop the technique of DME synthesis, a bifunctional Cu–ZnO–Al 2 O 3 /ZSM5 catalyst is prepared using a coprecipitation method. The reaction characteristics of DME synthesis from syngas at a high space velocity of 15,000 mL (g cat h) −1 are investigated and the effects of reaction temperature, pressure, CO 2 concentration and ZSM5 amount on the synthesis are taken into account. The results suggest that an increase in CO 2 concentration in the feed gas substantially decreases the DME formation. The optimum reaction temperature always occurs at 225 °C, regardless of what the pressure is. It is thus recognized that the DME synthesis is governed by two different mechanisms when the reaction temperature varies. At lower reaction temperatures ( 225 °C). For the CO 2 content of 5 vol.% and the pressure of 40 atm, the maximum DME yield is 1.89 g (g cat h) −1 . It is also found that 0.2 g of ZSM5 is sufficient to be blended with 1 g of the catalyst for DME synthesis.

STUDY OF GRINDING PROCESS OF TITANIUM CARBIDE PRODUCED WITH SELF-PROPAGATING HIGH TEMPERATURE SYNTHESIS (SPHTS)

International Nuclear Information System (INIS)

Kovziridze, Z.; Tabatadze, G.; Donadze, G.; Lezhava, A.; Gventsadze, D.

2006-01-01

It is stated that the specific character of SPHTS-preparations of TiC_x consists in crystal lattice strength reflecting the condition of synthesis in ''burning wave''. The use of roentgenographic and other methods of analysis allows to estimate the effect of the conditions of synthesis, causing carbon sublattice defect on grinding intensity of TiC_x phases. Study of the kinetics of vibro-grinding of TiC_x-phases in ethanol and benzene medium allows to establish high grinding intensity of the phases close to stoichiometry and the possibility of high depresion powderds (S_s_p H'' 4.5-6 m"2/g). (author)

Enantioselective synthesis of α-oxy amides via Umpolung amide synthesis.

Science.gov (United States)

Leighty, Matthew W; Shen, Bo; Johnston, Jeffrey N

2012-09-19

α-Oxy amides are prepared through enantioselective synthesis using a sequence beginning with a Henry addition of bromonitromethane to aldehydes and finishing with Umpolung Amide Synthesis (UmAS). Key to high enantioselection is the finding that ortho-iodo benzoic acid salts of the chiral copper(II) bis(oxazoline) catalyst deliver both diastereomers of the Henry adduct with high enantiomeric excess, homochiral at the oxygen-bearing carbon. Overall, this approach to α-oxy amides provides an innovative complement to alternatives that focus almost entirely on the enantioselective synthesis of α-oxy carboxylic acids.

Synthesis of polyaryl rigid-core carbosilane dendrimers for supported organic synthesis

NARCIS (Netherlands)

Wander, M.; Hausoul, P.J.C.; Sliedregt, L.A.J.M.; van Steen, B.J.; van Koten, G.; Klein Gebbink, R.J.M.

2009-01-01

Carbosilane dendrimers can be used as soluble supports for organic synthesis, since their structure allows separation of excess reagents from the supported products, eventually yielding products of high purity and in high yield, as in solid-phase organic synthesis (SPOS). In previous studies often

High-performance quantum-dot solids via elemental sulfur synthesis

KAUST Repository

Yuan, Mingjian

2014-03-21

An elemental-sulfur-based synthesis is reported, which, combined with processing to improve the size dispersion and passivation, results in a low-cost high-quality platform for small-bandgap PbS-CQD-based devices. Size-selective precipitation and cadmium chloride passivation are used to improve the power conversion efficiency of 1 eV bandgap CQD photovoltaic devices dramatically, which leads to record power conversion efficiency for a 1 eV PbS CQD solar cell of 5.4%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multi-granularity synthesis segmentation for high spatial resolution Remote sensing images

International Nuclear Information System (INIS)

Yi, Lina; Liu, Pengfei; Qiao, Xiaojun; Zhang, Xiaoning; Gao, Yuan; Feng, Boyan

2014-01-01

Traditional segmentation method can only partition an image in a single granularity space, with segmentation accuracy limited to the single granularity space. This paper proposes a multi-granularity synthesis segmentation method for high spatial resolution remote sensing images based on a quotient space model. Firstly, we divide the whole image area into multiple granules (regions), each region is consisted of ground objects that have similar optimal segmentation scale, and then select and synthesize the sub-optimal segmentations of each region to get the final segmentation result. To validate this method, the land cover category map is used to guide the scale synthesis of multi-scale image segmentations for Quickbird image land use classification. Firstly, the image is coarsely divided into multiple regions, each region belongs to a certain land cover category. Then multi-scale segmentation results are generated by the Mumford-Shah function based region merging method. For each land cover category, the optimal segmentation scale is selected by the supervised segmentation accuracy assessment method. Finally, the optimal scales of segmentation results are synthesized under the guide of land cover category. Experiments show that the multi-granularity synthesis segmentation can produce more accurate segmentation than that of a single granularity space and benefit the classification

Synthesis of new chiral amines with a cyclic 1,2-diacetal skeleton derived from (2R, 3R)-(+)-tartaric acid.

Science.gov (United States)

Barros, M Teresa; Phillips, Ana Maria Faísca

2006-03-17

The syntheses of new chiral cyclic 1,2-diacetals from (2R, 3R)-( )-tartaric acid are described. C(2)-symmetrical diamines were prepared via direct amidation of the tartrate or from the corresponding bismesylate via reaction with sodium azide. For C1-symmetrical compounds, the Appel reaction was used to form the key intermediate, a monochlorocarbinol, from the diol. Some of the new chiral compounds, produced in good to high yields, may be potentially useful as asymmetric organocatalysts or as nitrogen and sulfur chelating ligands for asymmetric metal catalyzed reactions. Thus, a bis-N-methyl-methanamine derivative, used in substoichiometric amounts, was found to catalyze the enantioselective addition of cyclohexanone to (E)-beta-nitrostyrene with high diastereoselectivity (syn / anti = 92:8), albeit giving moderate optical purity (syn: 30 %).

InSe monolayer: synthesis, structure and ultra-high second-harmonic generation

Science.gov (United States)

Zhou, Jiadong; Shi, Jia; Zeng, Qingsheng; Chen, Yu; Niu, Lin; Liu, Fucai; Yu, Ting; Suenaga, Kazu; Liu, Xinfeng; Lin, Junhao; Liu, Zheng

2018-04-01

III–IV layered materials such as indium selenide have excellent photoelectronic properties. However, synthesis of materials in such group, especially with a controlled thickness down to monolayer, still remains challenging. Herein, we demonstrate the successful synthesis of monolayer InSe by physical vapor deposition (PVD) method. The high quality of the sample was confirmed by complementary characterization techniques such as Raman spectroscopy, atomic force microscopy (AFM) and high resolution annular dark field scanning transmission electron microscopy (ADF-STEM). We found the co-existence of different stacking sequence (β- and γ-InSe) in the same flake with a sharp grain boundary in few-layered InSe. Edge reconstruction is also observed in monolayer InSe, which has a distinct atomic structure from the bulk lattice. Moreover, we discovered that the second-harmonic generation (SHG) signal from monolayer InSe shows large optical second-order susceptibility that is 1–2 orders of magnitude higher than MoS2, and even 3 times of the largest value reported in monolayer GaSe. These results make atom-thin InSe a promising candidate for optoelectronic and photosensitive device applications.

Ru-assisted synthesis of Pd/Ru nanodendrites with high activity for ethanol electrooxidation

Science.gov (United States)

Zhang, Ke; Bin, Duan; Yang, Beibei; Wang, Caiqin; Ren, Fangfang; Du, Yukou

2015-07-01

Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly enhanced cycling stability toward ethanol oxidation in alkaline medium, which are mainly ascribed to the synergetic effect between Pd and Ru. This indicates that the Pd7/Ru1 catalysts should have great potential applications in direct ethanol fuel cells.Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly

New Synthesis and Tritium Labeling of a Selective Ligand for Studying High-Affinity γ-Hydroxybutyrate (GHB) Binding Sites

DEFF Research Database (Denmark)

Vogensen, Stine B.; Marek, Ales; Bay, Tina

2013-01-01

3-Hydroxycyclopent-1-enecarboxylic acid (HOCPCA, 1) is a potent ligand for the high-affinity GHB binding sites in the CNS. An improved synthesis of 1 together with a very efficient synthesis of [3H]-1 is described. The radiosynthesis employs in situ generated lithium trimethoxyborotritide. Screen...

Rational synthesis of zerovalent iron/bamboo charcoal composites with high saturation magnetization

Science.gov (United States)

Mingshan Wu; Jianfeng Ma; Zhiyong Cai; Genlin Tian; Shumin Yang; Youhong Wang; Xing' e Liu

2015-01-01

The synthesis of magnetic biochar composites is a major new research area in advanced materials sciences. A series of magnetic bamboo charcoal composites (MBC800, MBC1000 and MBC1200) with high saturation magnetization (Ms) was fabricated in this work by mixing bamboo charcoal powder with an aqueous ferric chloride solution and subsequently...

Application of Self-Propagating High Temperature Synthesis to the Fabrication of Actinide Bearing Nitride and Other Ceramic Nuclear Fuels

International Nuclear Information System (INIS)

Moore, John J.; Reigel, Marissa M.; Donohoue, Collin D.

2009-01-01

The project uses an exothermic combustion synthesis reaction, termed self-propagating high-temperature synthesis (SHS), to produce high quality, reproducible nitride fuels and other ceramic type nuclear fuels (cercers and cermets, etc.) in conjunction with the fabrication of transmutation fuels. The major research objective of the project is determining the fundamental SHS processing parameters by first using manganese as a surrogate for americium to produce dense Zr-Mn-N ceramic compounds. These fundamental principles will then be transferred to the production of dense Zr-Am-N ceramic materials. A further research objective in the research program is generating fundamental SHS processing data to the synthesis of (i) Pu-Am-Zr-N and (ii) U-Pu-Am-N ceramic fuels. In this case, Ce will be used as the surrogate for Pu, Mn as the surrogate for Am, and depleted uranium as the surrogate for U. Once sufficient fundamental data has been determined for these surrogate systems, the information will be transferred to Idaho National Laboratory (INL) for synthesis of Zr-Am-N, Pu-Am-Zr-N and U-Pu-Am-N ceramic fuels. The high vapor pressures of americium (Am) and americium nitride (AmN) are cause for concern in producing nitride ceramic nuclear fuel that contains Am. Along with the problem of Am retention during the sintering phases of current processing methods, are additional concerns of producing a consistent product of desirable homogeneity, density and porosity. Similar difficulties have been experienced during the laboratory scale process development stage of producing metal alloys containing Am wherein compact powder sintering methods had to be abandoned. Therefore, there is an urgent need to develop a low-temperature or low-heat fuel fabrication process for the synthesis of Am-containing ceramic fuels. Self-propagating high temperature synthesis (SHS), also called combustion synthesis, offers such an alternative process for the synthesis of Am nitride fuels. Although SHS

Lewis base activation of Lewis acids: catalytic, enantioselective addition of glycolate-derived silyl ketene acetals to aldehydes.

Science.gov (United States)

Denmark, Scott E; Chung, Won-Jin

2008-06-20

A catalytic system involving silicon tetrachloride and a chiral, Lewis basic bisphosphoramide catalyst is effective for the addition of glycolate-derived silyl ketene acetals to aldehydes. It was found that the sense of diastereoselectivity could be modulated by changing the size of the substituents on the silyl ketene acetals. In general, the trimethylsilyl ketene acetals derived from methyl glycolates with a large protecting group on the alpha-oxygen provide enantiomerically enriched alpha,beta-dihydroxy esters with high syn-diastereoselectivity, whereas the tert-butyldimethylsilyl ketene acetals derived from bulky esters of alpha-methoxyacetic acid provide enantiomerically enriched alpha,beta-dihydroxy esters with high anti-diastereoselecitvity.

Stereodivergent Mannich reaction of bis(trimethylsilyl)ketene acetals with N-tert-butanesulfinyl imines by Lewis acid or Lewis base activation, a one-pot protocol to obtain chiral β-amino acids.

Science.gov (United States)

Cantú-Reyes, Margarita; Alvarado-Beltrán, Isabel; Ballinas-Indilí, Ricardo; Álvarez-Toledano, Cecilio; Hernández-Rodríguez, Marcos

2017-09-20

We report a one-pot synthesis of chiral β 2,2,3 -amino acids by the Mannich addition of bistrimethylsilyl ketene acetals to N-tert-butanesulfinyl imines followed by the removal of the chiral auxiliary. The synthesis and isolation of pure β-amino acid hydrochlorides were conducted under mild conditions, without strong bases and this method is operationally simple. The stereoselective reaction was promoted by two different activation methods that lead to different stereoisomers: (1) Lewis Acid (LA) catalysis with boron trifluoride diethyl etherate and (2) Lewis Base (LB) catalysis with tetrabutylammonium difluorotriphenylsilicate. The reaction presented good diastereoselectivity with LB activation and moderate to good dr with LA catalysis. The exceptions in both protocols were imines with electron donating groups in the aromatic ring.

Synthesis and morphological examination of high-purity Ca(OH)2 nanoparticles suitable to consolidate porous surfaces

Science.gov (United States)

Madrid, Juan Antonio; Lanzón, Marcos

2017-12-01

Adequate synthetic methods to obtain pure Ca(OH)2 nanoparticles are scarcely documented in the literature. This paper presents a complete methodology to obtain highly-pure Ca(OH)2 nanoparticles that are appropriate for strengthening heritage materials. The precipitation synthesis was operated in controlled atmosphere to avoid carbonation by atmospheric CO2. A complete purification method was developed to eliminate the sodium chloride generated in the reaction. Several analytical techniques, such as electrical conductivity, pH, ion chromatography, X-ray diffraction (XRD) and thermogravimetric analysis coupled to mass spectrometry (TGA-MS) were used to analyse both the aqueous medium and solid phase. The amount of material obtained in the synthesis (yield) was quantified throughout the purification procedure. The influence of temperature on the nanoparticles' size and stability was studied by transmission electron microscopy (HRTEM) and sedimentation tests (light scattering). It was found that the synthesis yielded high-purity nanoparticles, whose morphological features were greatly affected by the reaction temperature.

Short time synthesis of high quality carbon nanotubes with high rates by CVD of methane on continuously emerged iron nanoparticles

International Nuclear Information System (INIS)

Bahrami, Behnam; Khodadadi, Abasali; Mortazavi, Yadollah; Esmaieli, Mohamad

2011-01-01

We report the variation of yield and quality of carbon nanotubes (CNTs) grown by chemical vapor deposition (CVD) of methane on iron oxide-MgO at 900-1000 deg. C for 1-60 min. The catalyst was prepared by impregnation of MgO powder with iron nitrate, dried, and calcined at 300 deg. C. As calcined and unreduced catalyst in quartz reactor was brought to the synthesis temperature in helium flow in a few minutes, and then the flow was switched to methane. The iron oxide was reduced to iron nanoparticles in methane, while the CNTs were growing. TEM micrographs, in accordance with Raman RBM peaks, indicate the formation of mostly single wall carbon nanotubes of about 1.0 nm size. High quality CNTs with I G /I D Raman peak ratio of 14.5 are formed in the first minute of CNTs synthesis with the highest rate. Both the rate and quality of CNTs degrades with increasing CNTs synthesis time. Also CNTs quality sharply declines with temperature in the range of 900-1000 deg. C, while the CNTs yield passes through a maximum at 950 deg. C. About the same CNTs lengths are formed for the whole range of the synthesis times. A model of continuous emergence of iron nanoparticle seeds for CNTs synthesis may explain the data. The data can also provide information for continuous production of CNTs in a fluidized bed reactor.

Short time synthesis of high quality carbon nanotubes with high rates by CVD of methane on continuously emerged iron nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Bahrami, Behnam, E-mail: bahrami@email.sc.edu [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, Tehran (Iran, Islamic Republic of); Nanoelectronics Centre of Excellence, University of Tehran, Tehran (Iran, Islamic Republic of); Khodadadi, Abasali [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, Tehran (Iran, Islamic Republic of); Mortazavi, Yadollah, E-mail: mortazav@ut.ac.ir [Nanoelectronics Centre of Excellence, University of Tehran, Tehran (Iran, Islamic Republic of); Esmaieli, Mohamad [Nanoelectronics Centre of Excellence, University of Tehran, Tehran (Iran, Islamic Republic of)

2011-09-15

We report the variation of yield and quality of carbon nanotubes (CNTs) grown by chemical vapor deposition (CVD) of methane on iron oxide-MgO at 900-1000 deg. C for 1-60 min. The catalyst was prepared by impregnation of MgO powder with iron nitrate, dried, and calcined at 300 deg. C. As calcined and unreduced catalyst in quartz reactor was brought to the synthesis temperature in helium flow in a few minutes, and then the flow was switched to methane. The iron oxide was reduced to iron nanoparticles in methane, while the CNTs were growing. TEM micrographs, in accordance with Raman RBM peaks, indicate the formation of mostly single wall carbon nanotubes of about 1.0 nm size. High quality CNTs with I{sub G}/I{sub D} Raman peak ratio of 14.5 are formed in the first minute of CNTs synthesis with the highest rate. Both the rate and quality of CNTs degrades with increasing CNTs synthesis time. Also CNTs quality sharply declines with temperature in the range of 900-1000 deg. C, while the CNTs yield passes through a maximum at 950 deg. C. About the same CNTs lengths are formed for the whole range of the synthesis times. A model of continuous emergence of iron nanoparticle seeds for CNTs synthesis may explain the data. The data can also provide information for continuous production of CNTs in a fluidized bed reactor.

Synthesis of [diene-"1"4C] curcumin at high specific activity

International Nuclear Information System (INIS)

Filer, Crist N.; Lacy, James M.; Wright, Christopher

2016-01-01

An efficient method is described to label curcumin with "1"4C at high specific activity. - Highlights: • This paper describes the synthesis of ["1"4C] Curcumin at the highest specific activity and total activity amount yet reported. • The "1"4C label was installed in the diene framework of Curcumin. • This paper also describes the characterization of ["1"4C] Curcumin by HPLC and mass spectrometry.

1,2-Ferrocenediylazaphosphinines 3: a new class of planar chiral ligands for Cu-catalyzed cyclopropanation

Energy Technology Data Exchange (ETDEWEB)

Paek, Seung Hwan; Co, Thanh Thien; Lee, Dong Ho; Park, Yu Chul; Kim, Tae Jeong [Kyungpook National Univ., Daegu (Korea, Republic of)

2002-12-01

The synthesis and catalytic application of a new class of planar chiral ferrocenes, 1,2-ferrocenediylazaphos-phinines (1 and 2) are described. They are powerful ligands for the copper(I)-catalyzed asymmetric cyclopropanation of a range of alkenes with diazo esters to exhibit an exceptionally high degree of diastereoselectivity ({approx}100%) in favor of trans isomers, regardless the structure of the olefins and the diazo compounds. Comparative studies between 1 and 2 reveal that the former works better in terms of diastereocontrol. In contrast, however, enantioselectivity is low with both 1 and 2 as a whole although, in certain cases with a proper combination of the olefin and the diazo ester, high optical yields (up to 100% ee) can be achieved. Other reaction parameters such as the reaction temperature and the structure of the ligand do exhibit some influence, although infinitesimal, on both chemical and optical yields.

1,2-Ferrocenediylazaphosphinines 3: a new class of planar chiral ligands for Cu-catalyzed cyclopropanation

International Nuclear Information System (INIS)

Paek, Seung Hwan; Co, Thanh Thien; Lee, Dong Ho; Park, Yu Chul; Kim, Tae Jeong

2002-01-01

The synthesis and catalytic application of a new class of planar chiral ferrocenes, 1,2-ferrocenediylazaphos-phinines (1 and 2) are described. They are powerful ligands for the copper(I)-catalyzed asymmetric cyclopropanation of a range of alkenes with diazo esters to exhibit an exceptionally high degree of diastereoselectivity (∼100%) in favor of trans isomers, regardless the structure of the olefins and the diazo compounds. Comparative studies between 1 and 2 reveal that the former works better in terms of diastereocontrol. In contrast, however, enantioselectivity is low with both 1 and 2 as a whole although, in certain cases with a proper combination of the olefin and the diazo ester, high optical yields (up to 100% ee) can be achieved. Other reaction parameters such as the reaction temperature and the structure of the ligand do exhibit some influence, although infinitesimal, on both chemical and optical yields

Long-term rates of mitochondrial protein synthesis are increased in mouse skeletal muscle with high-fat feeding regardless of insulin-sensitizing treatment.

Science.gov (United States)

Newsom, Sean A; Miller, Benjamin F; Hamilton, Karyn L; Ehrlicher, Sarah E; Stierwalt, Harrison D; Robinson, Matthew M

2017-11-01

Skeletal muscle mitochondrial protein synthesis is regulated in part by insulin. The development of insulin resistance with diet-induced obesity may therefore contribute to impairments to protein synthesis and decreased mitochondrial respiration. Yet the impact of diet-induced obesity and insulin resistance on mitochondrial energetics is controversial, with reports varying from decreases to increases in mitochondrial respiration. We investigated the impact of changes in insulin sensitivity on long-term rates of mitochondrial protein synthesis as a mechanism for changes to mitochondrial respiration in skeletal muscle. Insulin resistance was induced in C57BL/6J mice using 4 wk of a high-fat compared with a low-fat diet. For 8 additional weeks, diets were enriched with pioglitazone to restore insulin sensitivity compared with nonenriched control low-fat or high-fat diets. Skeletal muscle mitochondrial protein synthesis was measured using deuterium oxide labeling during weeks 10-12 High-resolution respirometry was performed using palmitoyl-l-carnitine, glutamate+malate, and glutamate+malate+succinate as substrates for mitochondria isolated from quadriceps. Mitochondrial protein synthesis and palmitoyl- l-carnitine oxidation were increased in mice consuming a high-fat diet, regardless of differences in insulin sensitivity with pioglitazone treatment. There was no effect of diet or pioglitazone treatment on ADP-stimulated respiration or H 2 O 2 emission using glutamate+malate or glutamate+malate+succinate. The results demonstrate no impairments to mitochondrial protein synthesis or respiration following induction of insulin resistance. Instead, mitochondrial protein synthesis was increased with a high-fat diet and may contribute to remodeling of the mitochondria to increase lipid oxidation capacity. Mitochondrial adaptations with a high-fat diet appear driven by nutrient availability, not intrinsic defects that contribute to insulin resistance. Copyright © 2017 the

Synthesis of high quality single-walled carbon nanotubes via a catalytic layer reinforced by self-assembled monolayers

International Nuclear Information System (INIS)

Adhikari, Prashanta Dhoj; Song, Wooseok; Cha, Myoung-Jun; Park, Chong-Yun

2013-01-01

This work reports the synthesis of high quality single-walled carbon nanotubes (SWCNT) using a catalytic layer reinforced by self-assembled monolayers (SAM). Amine-SAM was introduced on a SiO 2 /Si substrate and then an iron nanoparticles solution was dropped on the substrate by spin-coating. This catalytic template was used to grow carbon nanotubes by chemical vapor deposition and the synthesized SWCNT were observed to be prominent, based on the size distribution. Highly dense SWCNT with a diameter of about 1.1-1.2 nm were produced at 800-850 °C. Moreover, the diameter distribution of the SWCNT was more selective at a growth temperature of 900 °C. These findings provide important insights for a SAM support layer that can play the role as a restriction for the agglomeration of iron catalyst and is promising for the synthesis of high quality SWCNT. - Highlights: • Fe nanoparticles on self-assembled monolayers (SAM) containing template is underlined. • Its catalytic behavior to synthesis single-walled carbon nanotubes is studied. • The role of SAM on catalytic template is explored

Green synthesis of highly fluorescent carbon quantum dots from sugarcane bagasse pulp

Energy Technology Data Exchange (ETDEWEB)

Thambiraj, S. [Nano-Bio Materials and Sensors Laboratory, PSG Institute of Advanced Studies, Coimbatore, 641 004, Tamil Nadu (India); Ravi Shankaran, D., E-mail: dravishankaran@hotmail.com [Nano-Bio Materials and Sensors Laboratory, PSG Institute of Advanced Studies, Coimbatore, 641 004, Tamil Nadu (India); National Centre for Nanoscience and Nanotechnology, University of Madras, Guindy Campus, Chennai, 600 025, Tamil Nadu (India)

2016-12-30

Graphical abstract: Schematic representation of CQDs from sugarcane bagasse carbon. - Highlights: • CQDs were synthesised from sugarcane bagasse waste with top down approaches. • Synthesis method is green, simple and efficient process. • CQDs possess high quantum yield, good stability and highly fluorescent in nature. • The morphological and topographical study of CQDs was done by HR-TEM and AFM and was observed that the average size is 4.1 ± 0.17 nm and surface thickness is 5 nm. - Abstract: Carbon quantum dots (CQDs) have great potential due to its advantageous characteristics of highly fluorescent nature and good stability. In this study, we aimed to develop a simple and efficient method for the green synthesis of fluorescent CQDs from sugarcane bagasse, a renewable and sustainable resource. The process involves the top down approach of chemical oxidation followed by exfoliation of sugarcane carbon. The synthesized CQDs was characterized by UV–vis absorption spectroscopy, Spectrofluorophotometry, Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Raman spectroscopy, X-ray photon spectroscopy (XPS), Atomic force microscopy (AFM) and High-resolution transmission electron microscopy (HR-TEM). The synthesized CQDs possess stable fluorescent properties, good bio-compatibility and high quantum yield. The CQDs are highly crystalline with longitudinal dimensions of 4.1 ± 0.17 nm with an average roughness of around 5 nm. The XRD and TEM analysis indicates that the synthesized CQDs possess face centred cubic crystal structure. The results suggest that the proposed CQDs could be utilized for bio-sensor, bio-imaging and drug delivery applications.

Habituation to low or high protein intake does not modulate basal or postprandial muscle protein synthesis rates: a randomized trial.

Science.gov (United States)

Gorissen, Stefan Hm; Horstman, Astrid Mh; Franssen, Rinske; Kouw, Imre Wk; Wall, Benjamin T; Burd, Nicholas A; de Groot, Lisette Cpgm; van Loon, Luc Jc

2017-02-01

Muscle mass maintenance is largely regulated by basal muscle protein synthesis rates and the ability to increase muscle protein synthesis after protein ingestion. To our knowledge, no previous studies have evaluated the impact of habituation to either low protein intake (LOW PRO) or high protein intake (HIGH PRO) on the postprandial muscle protein synthetic response. We assessed the impact of LOW PRO compared with HIGH PRO on basal and postprandial muscle protein synthesis rates after the ingestion of 25 g whey protein. Twenty-four healthy, older men [age: 62 ± 1 y; body mass index (in kg/m 2 ): 25.9 ± 0.4 (mean ± SEM)] participated in a parallel-group randomized trial in which they adapted to either a LOW PRO diet (0.7 g · kg -1 · d -1 ; n = 12) or a HIGH PRO diet (1.5 g · kg -1 · d -1 ; n = 12) for 14 d. On day 15, participants received primed continuous l-[ring- 2 H 5 ]-phenylalanine and l-[1- 13 C]-leucine infusions and ingested 25 g intrinsically l-[1- 13 C]-phenylalanine- and l-[1- 13 C]-leucine-labeled whey protein. Muscle biopsies and blood samples were collected to assess muscle protein synthesis rates as well as dietary protein digestion and absorption kinetics. Plasma leucine concentrations and exogenous phenylalanine appearance rates increased after protein ingestion (P 0.05). Plasma exogenous phenylalanine availability over the 5-h postprandial period was greater after LOW PRO than after HIGH PRO (61% ± 1% compared with 56% ± 2%, respectively; P protein synthesis rates increased from 0.031% ± 0.004% compared with 0.039% ± 0.007%/h in the fasted state to 0.062% ± 0.005% compared with 0.057% ± 0.005%/h in the postprandial state after LOW PRO compared with HIGH PRO, respectively (P protein-derived amino acids in the circulation and does not lower basal muscle protein synthesis rates or increase postprandial muscle protein synthesis rates after ingestion of 25 g protein in older men. This trial was registered at clinicaltrials.gov as NCT

Synthesis and reforming of high molecular-weigth compounds by the utilization of radiation

International Nuclear Information System (INIS)

Machi, Sueo

1976-01-01

Radiation effects on the synthesis are reforming of high molecular-weight compounds are reviewed. The report is divided into four main parts. The first part deals with the characteristics of the radiation processing. The reaction can be started in a wide range of temperature including very low temperature. Catalysts are unnecessary. The reaction velocity is fast, and the reaction in solid phase can be started uniformly. And the quality of products is well controllable. The second part deals with the synthesis of high molecular-weight compounds by radiation polymerization. Radical polymerization and ionizing polymerization, gas phase and liquid phase polymerization, the polymerization and copolymerization of fluorine-containing monomers, and solid phase polymerization and low temperature polymerization are included in this part. Attention is directed to the continuous production system for the radiation polymerization of ethylene developed by Japan Atomic Energy Research Institute. The third part deals with the reforming of high molecular-weight compounds by radiation graft polymerization. The combination of backbone polymers and monomers for reforming plastics and fibers, the membranes for reverse osmosis, porous membranes, and ion exchange membranes are included. The fourth part deals with the reforming of high molecular-weight compounds by the cross-linking. Polyethylene, PVC, ethyl acrylate copolymer and the like are included. (Iwakiri, K.)

Controlled synthesis of high-quality crystals of monolayer MoS2 for nanoelectronic device application

DEFF Research Database (Denmark)

Yang, Xiaonian; Li, Qiang; Hu, Guofeng

2016-01-01

. Monolayer MoS2 so far can be obtained by mechanical exfoliation or chemical vapor deposition (CVD). However, controllable synthesis of large area monolayer MoS2 with high quality needs to be improved and their growth mechanism requires more studies. Here we report a systematical study on controlled...... synthesis of high-quality monolayer MoS2 single crystals using low pressure CVD. Large-size monolayer MoS2 triangles with an edge length up to 405 mu m were successfully synthesized. The Raman and photoluminescence spectroscopy studies indicate high homogenous optical characteristic of the synthesized...... monolayer MoS2 triangles. The transmission electron microscopy results demonstrate that monolayer MoS2 triangles are single crystals. The back-gated field effect transistors (FETs) fabricated using the as-grown monolayer MoS2 show typical n-type semiconductor behaviors with carrier mobility up to 21.8 cm(2...

Study of composite adsorbent synthesis and characterization for the removal of Cs in the high-salt and high-radioactive wastewater

Energy Technology Data Exchange (ETDEWEB)

Kim, Jimin; Lee, Keun Young; Kim, Kwang Wook; Lee, Eil Hee; Chung, Dong Yong; Moon, Jei Kwon [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Hyun, Jae Hyuk [Chungnam National University, Daejeon (Korea, Republic of)

2017-03-15

For the removal of cesium (Cs) from high radioactive/high salt-laden liquid waste, this study synthesized a highly efficient composite adsorbent (potassium cobalt ferrocyanide (PCFC)-loaded chabazite (CHA)) and evaluated its applicability. The composite adsorbent used CHA, which could accommodate Cs as well as other molecules, as a supporting material and was synthesized by immobilizing the PCFC in the pores of CHA through stepwise impregnation/precipitation with CoCl{sub 2} and K{sub 4}Fe (CN){sub 6} solutions. When CHA, with average particle size of more than 10 μm, is used in synthesizing the composite adsorbent, the PCFC particles were immobilized in a stable form. Also, the physical stability of the composite adsorbent was improved by optimizing the washing methodology to increase the purity of the composite adsorbent during the synthesis. The composite adsorbent obtained from the optimal synthesis showed a high adsorption rate of Cs in both fresh water (salt-free condition) and seawater (high-salt condition), and had a relatively high value of distribution coefficient (larger than 10{sup 4} mL·g{sup -1}) regardless of the salt concentration. Therefore, the composite adsorbent synthesized in this study is an optimized material considering both the high selectivity of PCFC on Cs and the physical stability of CHA. It is proved that this composite adsorbent can remove rapidly Cs contained in high radioactive/high salt-laden liquid waste with high efficiency.

Flow Asymmetric Propargylation: Development of Continuous Processes for the Preparation of a Chiral β-Amino Alcohol.

Science.gov (United States)

Li, Hui; Sheeran, Jillian W; Clausen, Andrew M; Fang, Yuan-Qing; Bio, Matthew M; Bader, Scott

2017-08-01

The development of a flow chemistry process for asymmetric propargylation using allene gas as a reagent is reported. The connected continuous process of allene dissolution, lithiation, Li-Zn transmetallation, and asymmetric propargylation provides homopropargyl β-amino alcohol 1 with high regio- and diastereoselectivity in high yield. This flow process enables practical use of an unstable allenyllithium intermediate. The process uses the commercially available and recyclable (1S,2R)-N-pyrrolidinyl norephedrine as a ligand to promote the highly diastereoselective (32:1) propargylation. Judicious selection of mixers based on the chemistry requirement and real-time monitoring of the process using process analytical technology (PAT) enabled stable and scalable flow chemistry runs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Environmentally friendly synthesis of highly monodisperse biocompatible gold nanoparticles with urchin-like shape.

Science.gov (United States)

Lu, Lehui; Ai, Kelong; Ozaki, Yukihiro

2008-02-05

We report a facile and environmentally friendly strategy for high-yield synthesis of highly monodisperse gold nanoparticles with urchin-like shape. A simple protein, gelatin, was first used for the control over shape and orientation of the gold nanoparticles. These nanoparticles, ready to use for biological systems, are promising in the optical imaging-based disease diagnostics and therapy because of their tunable surface plasmon resonance (SPR) and excellent surface-enhanced Raman scattering (SERS) activity.

Synthesis of high specific activity tritium labelled [2-3H]-adenosine-5'-triphosphate

International Nuclear Information System (INIS)

Jaiswal, D.K.; Morimoto, H.; Trump, E.L.; Williams, P.G.; Wemmer, D.E.

1996-01-01

A procedure for high level tritium labelling at the C2-H position of adenosine 5'-triphosphate ([2- 3 H]-ATP, 1), based on the tritiodehalogenation reaction of 2-bromoadenosine 5'-triphosphate (2) has been elaborated. This precursor was prepared in a six-step synthesis from guanosine. The tritiodehalogenation of (2) for three hours over palladium oxide in phosphate buffer yielded tritium labelled ATP with high specific activity, in good chemical yield. (author)

Power Constrained High-Level Synthesis of Battery Powered Digital Systems

DEFF Research Database (Denmark)

Nielsen, Sune Fallgaard; Madsen, Jan

2003-01-01

We present a high-level synthesis algorithm solving the combined scheduling, allocation and binding problem minimizing area under both latency and maximum power per clock-cycle constraints. Our approach eliminates the large power spikes, resulting in an increased battery lifetime, a property...... of utmost importance for battery powered embedded systems. Our approach extends the partial-clique partitioning algorithm by introducing power awareness through a heuristic algorithm which bounds the design space to those of power feasible schedules. We have applied our algorithm on a set of dataflow graphs...

Evaluation of the FIR Example using Xilinx Vivado High-Level Synthesis Compiler

Energy Technology Data Exchange (ETDEWEB)

Jin, Zheming [Argonne National Lab. (ANL), Argonne, IL (United States); Finkel, Hal [Argonne National Lab. (ANL), Argonne, IL (United States); Yoshii, Kazutomo [Argonne National Lab. (ANL), Argonne, IL (United States); Cappello, Franck [Argonne National Lab. (ANL), Argonne, IL (United States)

2017-07-28

Compared to central processing units (CPUs) and graphics processing units (GPUs), field programmable gate arrays (FPGAs) have major advantages in reconfigurability and performance achieved per watt. This development flow has been augmented with high-level synthesis (HLS) flow that can convert programs written in a high-level programming language to Hardware Description Language (HDL). Using high-level programming languages such as C, C++, and OpenCL for FPGA-based development could allow software developers, who have little FPGA knowledge, to take advantage of the FPGA-based application acceleration. This improves developer productivity and makes the FPGA-based acceleration accessible to hardware and software developers. Xilinx Vivado HLS compiler is a high-level synthesis tool that enables C, C++ and System C specification to be directly targeted into Xilinx FPGAs without the need to create RTL manually. The white paper [1] published recently by Xilinx uses a finite impulse response (FIR) example to demonstrate the variable-precision features in the Vivado HLS compiler and the resource and power benefits of converting floating point to fixed point for a design. To get a better understanding of variable-precision features in terms of resource usage and performance, this report presents the experimental results of evaluating the FIR example using Vivado HLS 2017.1 and a Kintex Ultrascale FPGA. In addition, we evaluated the half-precision floating-point data type against the double-precision and single-precision data type and present the detailed results.

Room temperature synthesis and high temperature frictional study of silver vanadate nanorods

Energy Technology Data Exchange (ETDEWEB)

Singh, D P; Aouadi, S M [Department of Physics, Southern Illinois University, Carbondale-62901 (United States); Polychronopoulou, K [Department of Chemistry, University of Cyprus, Nicosia, 1678 (Cyprus); Rebholz, C, E-mail: dineshpsingh@gmail.com, E-mail: saouadi@physics.siu.edu [Department of Mechanical and Manufacturing Engineering, University of Cyprus, Nicosia, 1678 (Cyprus)

2010-08-13

We report the room temperature (RT) synthesis of silver vanadate nanorods (consisting of mainly {beta}-AgV O{sub 3}) by a simple wet chemical route and their frictional study at high temperatures (HT). The sudden mixing of ammonium vanadate with silver nitrate solution under constant magnetic stirring resulted in a pale yellow coloured precipitate. Structural/microstructural characterization of the precipitate through x-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed the high yield and homogeneous formation of silver vanadate nanorods. The length of the nanorods was 20-40 {mu}m and the thickness 100-600 nm. The pH variation with respect to time was thoroughly studied to understand the formation mechanism of the silver vanadate nanorods. This synthesis process neither demands HT, surfactants nor long reaction time. The silver vanadate nanomaterial showed good lubrication behaviour at HT (700 deg. C) and the friction coefficient was between 0.2 and 0.3. HT-XRD revealed that AgV O{sub 3} completely transformed into silver vanadium oxide (Ag{sub 2}V{sub 4}O{sub 11}) and silver with an increase in temperature from RT to 700 deg. C.

Room temperature synthesis and high temperature frictional study of silver vanadate nanorods.

Science.gov (United States)

Singh, D P; Polychronopoulou, K; Rebholz, C; Aouadi, S M

2010-08-13

We report the room temperature (RT) synthesis of silver vanadate nanorods (consisting of mainly beta-AgV O(3)) by a simple wet chemical route and their frictional study at high temperatures (HT). The sudden mixing of ammonium vanadate with silver nitrate solution under constant magnetic stirring resulted in a pale yellow coloured precipitate. Structural/microstructural characterization of the precipitate through x-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed the high yield and homogeneous formation of silver vanadate nanorods. The length of the nanorods was 20-40 microm and the thickness 100-600 nm. The pH variation with respect to time was thoroughly studied to understand the formation mechanism of the silver vanadate nanorods. This synthesis process neither demands HT, surfactants nor long reaction time. The silver vanadate nanomaterial showed good lubrication behaviour at HT (700 degrees C) and the friction coefficient was between 0.2 and 0.3. HT-XRD revealed that AgV O(3) completely transformed into silver vanadium oxide (Ag(2)V(4)O(11)) and silver with an increase in temperature from RT to 700 degrees C.

Synthesis and Characterization of High-Dielectric-Constant Nanographite-Polyurethane Composite

Science.gov (United States)

Mishra, Praveen; Bhat, Badekai Ramachandra; Bhattacharya, B.; Mehra, R. M.

2018-05-01

In the face of ever-growing demand for capacitors and energy storage devices, development of high-dielectric-constant materials is of paramount importance. Among various dielectric materials available, polymer dielectrics are preferred for their good processability. We report herein synthesis and characterization of nanographite-polyurethane composite with high dielectric constant. Nanographite showed good dispersibility in the polyurethane matrix. The thermosetting nature of polyurethane gives the composite the ability to withstand higher temperature without melting. The resultant composite was studied for its dielectric constant (ɛ) as a function of frequency. The composite exhibited logarithmic variation of ɛ from 3000 at 100 Hz to 225 at 60 kHz. The material also exhibited stable dissipation factor (tan δ) across the applied frequencies, suggesting its ability to resist current leakage.

Honeycomb supports with high thermal conductivity for the Tischer-Tropsch synthesis

Energy Technology Data Exchange (ETDEWEB)

Visconti, C.G.; Rronconi, E.; Groppi, G.; Lietti, L. [Politecnico di Milano (Italy). Dipt. di Energia; Iovane, M.; Rossini, S.; Zennaro, R. [Eni S.p.A., San Donato Milanese (Italy). Div. Exploration and Production

2011-07-01

The potential of multitubular reactors loaded with washcoated structured catalysts having highly conductive honeycomb supports is investigated herein in the low temperature Fischer- Tropsch synthesis by means of a theoretical investigation. Simulation results indicate that extruded aluminum honeycomb monoliths, washcoated with a Co-based catalyst, are promising for the application at the industrial scale, in particular when adopting supports with high cell densities and catalysts with high activity. Limited temperature gradients within the reactor are in fact possible even at extreme process conditions, thus leading to interesting volumetric reactor yields with negligible pressure drop. This result is achieved without the need of cofeeding to the reactor large amounts of liquid hydrocarbons to remove the reaction heat, as opposite to existing industrial Fischer-Tropsch packed-bed reactors. (orig.)

Synthesis of high-oxidation Y-Ba-Cu-O phases in superoxygenated thin films

Science.gov (United States)

Zhang, H.; Gauquelin, N.; McMahon, C.; Hawthorn, D. G.; Botton, G. A.; Wei, J. Y. T.

2018-03-01

It is known that solid-state reaction in high-pressure oxygen can stabilize high-oxidation phases of Y-Ba-Cu-O superconductors in powder form. We extend this superoxygenation concept of synthesis to thin films which, due to their large surface-to-volume ratio, are more reactive thermodynamically. Epitaxial thin films of YBa2Cu3O7 -δ grown by pulsed laser deposition are annealed at up to 700 atm O2 and 900 ∘C , in conjunction with Cu enrichment by solid-state diffusion. The films show the clear formation of Y2Ba4Cu7O15 -δ and Y2Ba4Cu8O16 as well as regions of YBa2Cu5O9 -δ and YBa2Cu6O10 -δ phases, according to scanning transmission electron microscopy, x-ray diffraction, and x-ray absorption spectroscopy. Similarly annealed YBa2Cu3O7 -δ powders show no phase conversion. Our results demonstrate a route of synthesis towards discovering more complex phases of cuprates and other superconducting oxides.

Production of advanced materials by methods of self-propagating high-temperature synthesis

CERN Document Server

Tavadze, Giorgi F

2013-01-01

This translation from the original Russian book outlines the production of a variety of materials by methods of self-propagating high-temperature synthesis (SHS). The types of materials discussed include: hard, refractory, corrosion and wear-resistant materials, as well as other advanced and speciality materials. The authors address the issue of optimal parameters for SHS reactions occurring during processes involving a preliminary metallothermic reduction stage, and they calculate this using thermodynamic approaches. In order to confirm the effectiveness of this approach, the authors describe experiments focussing on the synthesis of elemental crysalline boron, boron carbides and nitrides. Other parts of this brief include theoretical and experimental results on single-stage production of hard alloys on the basis of titanium and zirconium borides, as well as macrokinetics of degassing and compaciton of SHS-products.This brief is suitable for academics, as well as those working in industrial manufacturing com...

One-Step Synthesis of Microporous Carbon Monoliths Derived from Biomass with High Nitrogen Doping Content for Highly Selective CO2 Capture

OpenAIRE

Geng, Zhen; Xiao, Qiangfeng; Lv, Hong; Li, Bing; Wu, Haobin; Lu, Yunfeng; Zhang, Cunman

2016-01-01

The one-step synthesis method of nitrogen doped microporous carbon monoliths derived from biomass with high-efficiency is developed using a novel ammonia (NH3)-assisted activation process, where NH3 serves as both activating agent and nitrogen source. Both pore forming and nitrogen doping simultaneously proceed during the process, obviously superior to conventional chemical activation. The as-prepared nitrogen-doped active carbons exhibit rich micropores with high surface area and high nitrog...

Hydrothermal synthesis of polyethylenimine-protected high luminescent Pt-nanoclusters and their application to the detection of nitroimidazoles

International Nuclear Information System (INIS)

Xu, Na; Li, Hong-Wei; Wu, Yuqing

2017-01-01

A novel one-step hydrothermal synthesis of highly fluorescent platinum nanoclusters protected by polyethylenimine (Pt-NCs@PEI) is described. The products are characterized well by UV–vis absorption, fluorescence spectra, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) imaging. The Pt-NCs@PEI possess high quantum yield at 28%, which is the relatively high one among the reported Pt-NCs; especially, the synthesis is in one-step and the reaction time is much shorter (<1 h) than the related methods. In addition, the Pt-NCs@PEI have large Stocks-shift (∼150 nm), high tolerability to the extreme pH and high ionic strengths, and excellent photo-stability under UV–vis irradiation, lay the foundation for the practical bio-applications. Finally, the obtained Pt-NCs@PEI are used to determine trace amount of metronidazole (MTZ) in buffer solution in showing a linear response over a concentration range of 0.25–300 μM and a low detection limit of 0.1 μM. Furthermore, the related investigation on response mechanism will be helpful to design and synthesize new metal nanoclusters as fluorescent probe to detect the trace amount of harmful medicine residuum as nitroimidazoles in human body. - Highlights: • This paper provides the first hydrothermal synthesis of platinum nanoclusters. • The prepared polyethylenimine-protected platinum nanoclusters possess high quantum yield of 28%. • A new method to detect trace amount of metronidazole in urine is proposed.

Hydrothermal synthesis of polyethylenimine-protected high luminescent Pt-nanoclusters and their application to the detection of nitroimidazoles

Energy Technology Data Exchange (ETDEWEB)

Xu, Na [State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, 130012 (China); College of Materials Science and Engineering, Jilin Institute of Chemical Technology, Jilin, 132022 (China); Li, Hong-Wei, E-mail: lihongwei@jlu.edu.cn [State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, 130012 (China); Wu, Yuqing, E-mail: yqwu@jlu.edu.cn [State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, 130012 (China)

2017-03-15

A novel one-step hydrothermal synthesis of highly fluorescent platinum nanoclusters protected by polyethylenimine (Pt-NCs@PEI) is described. The products are characterized well by UV–vis absorption, fluorescence spectra, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) imaging. The Pt-NCs@PEI possess high quantum yield at 28%, which is the relatively high one among the reported Pt-NCs; especially, the synthesis is in one-step and the reaction time is much shorter (<1 h) than the related methods. In addition, the Pt-NCs@PEI have large Stocks-shift (∼150 nm), high tolerability to the extreme pH and high ionic strengths, and excellent photo-stability under UV–vis irradiation, lay the foundation for the practical bio-applications. Finally, the obtained Pt-NCs@PEI are used to determine trace amount of metronidazole (MTZ) in buffer solution in showing a linear response over a concentration range of 0.25–300 μM and a low detection limit of 0.1 μM. Furthermore, the related investigation on response mechanism will be helpful to design and synthesize new metal nanoclusters as fluorescent probe to detect the trace amount of harmful medicine residuum as nitroimidazoles in human body. - Highlights: • This paper provides the first hydrothermal synthesis of platinum nanoclusters. • The prepared polyethylenimine-protected platinum nanoclusters possess high quantum yield of 28%. • A new method to detect trace amount of metronidazole in urine is proposed.

Multi-exposure high dynamic range image synthesis with camera shake correction

Science.gov (United States)

Li, Xudong; Chen, Yongfu; Jiang, Hongzhi; Zhao, Huijie

2017-10-01

Machine vision plays an important part in industrial online inspection. Owing to the nonuniform illuminance conditions and variable working distances, the captured image tends to be over-exposed or under-exposed. As a result, when processing the image such as crack inspection, the algorithm complexity and computing time increase. Multiexposure high dynamic range (HDR) image synthesis is used to improve the quality of the captured image, whose dynamic range is limited. Inevitably, camera shake will result in ghost effect, which blurs the synthesis image to some extent. However, existed exposure fusion algorithms assume that the input images are either perfectly aligned or captured in the same scene. These assumptions limit the application. At present, widely used registration based on Scale Invariant Feature Transform (SIFT) is usually time consuming. In order to rapidly obtain a high quality HDR image without ghost effect, we come up with an efficient Low Dynamic Range (LDR) images capturing approach and propose a registration method based on ORiented Brief (ORB) and histogram equalization which can eliminate the illumination differences between the LDR images. The fusion is performed after alignment. The experiment results demonstrate that the proposed method is robust to illumination changes and local geometric distortion. Comparing with other exposure fusion methods, our method is more efficient and can produce HDR images without ghost effect by registering and fusing four multi-exposure images.

Synthesis of (1R,2S)-1-amino-2-vinylcyclopropanecarboxylic acid vinyl-ACCA) derivatives: key intermediates for the preparation of inhibitors of the hepatitis C virus NS3 protease.

Science.gov (United States)

Beaulieu, Pierre L; Gillard, James; Bailey, Murray D; Boucher, Colette; Duceppe, Jean-Simon; Simoneau, Bruno; Wang, Xiao-Jun; Zhang, Li; Grozinger, Karl; Houpis, Ioannis; Farina, Vittorio; Heimroth, Heidi; Krueger, Thomas; Schnaubelt, Jürgen

2005-07-22

(1R,2S)-1-Amino-2-vinylcyclopropanecarboxylic acid (vinyl-ACCA) is a key building block in the synthesis of potent inhibitors of the hepatitis C virus NS3 protease such as BILN 2061, which was recently shown to dramatically reduce viral load after administration to patients infected with HCV genotype 1. We have developed a scalable process that delivers derivatives of this unusual amino acid in >99% ee. The strategy was based on the dialkylation of a glycine Schiff base using trans-1,4-dibromo-2-butene as an electrophile to produce racemic vinyl-ACCA, which was subsequently resolved using a readily available, inexpensive esterase enzyme (Alcalase 2.4L). Factors that affect diastereoselection in the initial dialkylation steps were examined and the conditions optimized to deliver the desired diastereomer selectively. Product inhibition, which was encountered during the enzymatic resolution step, initially resulted in prolonged cycle times. Enrichment of racemic vinyl-ACCA through a chemical resolution via diastereomeric salt formation or the use of forcing conditions in the enzymatic reaction both led to improvements in throughput and the development of a viable process. The chemistry described herein was scaled up to produce multikilogram quantities of this building block.

Engineering high power induction plasma unit at BARC for mass synthesis of refractory nano-ceramics

International Nuclear Information System (INIS)

Ghorui, S.; Sahasrabudhe, S.N.; Dhamale, G.; Das, A.K.

2013-01-01

Atmospheric pressure RF thermal plasma sources are gaining increasing importance for production of high purity novel nano-materials in different high-end technological applications. Inherent electrode-less features of the discharge together with the large volume and high energy density of the produced plasma ensures contamination free process environment and mass production ability. Reported herewith is the development of an indigenous induction plasma system for mass synthesis of nanopowders of refractory ceramic materials. The system has been tested for continuous synthesis of Al 2 O 3 nano-powder at a rate of more than 600 gm per hour and checked for its viability for bulk production of nano-particles of other refractory ceramics like Yttrium oxide and Neodymium Oxide. From collected evidences, the process of formation of the nano-particles is identified as the evaporation and subsequent homogeneous nucleation. Major features observed for alumina are complete conversion into highly spherical nano-sized particles, small particle sizes, very narrow size distribution, highly crystallite nature and mixed phases depending on the zone of collection. For alumina, the particles are found to exhibit a uni-modal distribution with peak near 15 nm

High pressure and microwave based synthesis of transition metal pnictides

Energy Technology Data Exchange (ETDEWEB)

Pobel, Roman Rupert

2016-04-11

The goal of this thesis was to explore the possibilities of synthetic methods that are not very common in current transition metal pnictide research. The substitution of the Ca-site in CaFe{sub 2}As{sub 2} with rare earth elements such as Pr the has been reported to induce superconductivity. However, some inconsistencies in the data suggested a non-intrinsic origin of the observed diamagnetic signal. Furthermore a solubility limit of 13% was found when prepared in an electrical furnace thus leaving a huge part of the physical phase diagram inaccessible. A high pressure/high temperature synthesis was developed to allow access to the whole doping range and an in-depth characterization of this compound was carried out. During the experiments concerning the high pressure synthesis of Ca{sub 1-x}Pr{sub x}Fe{sub 2}As{sub 2} the new ternary iron arsenide CaFe{sub 5}As{sub 3} was identified and classified as a member of the Ca{sub n(n+1)/2}(Fe{sub 1-x}M{sub x}){sub (2+3n)}M'{sub n(n-1)/2}As{sub (n+1)(n+2)/2} (n = 1-3; M =Nb, Pd, Pt; M' = □, Pd, Pt) family. The complete solid solution Ca{sub 1-x}Pr{sub x}Fe{sub 5}As{sub 3} (O ≤ x ≤ 1) was prepared and physically characterized. Furthermore, several useful techniques were developed to aid in future high pressure based investigations of transition metal pnictides. The second part of this thesis concerns a completely different, but equally promising synthetic approach. Microwave based synthesis is a well-established technique in many solution based fields, such as organic, medicinal or nano chemistry. For solid state and materials research several parameters and particularities have to be considered. But when successful, it allows for the reduction of reaction time by several orders of magnitude. It has very rarely been applied in the preparation of pnictides and on1y once in the context of pnictide superconductor research. The possibilities of this method were explored and employed in the preparation of several

Prolonged Adaptation to a Low or High Protein Diet Does Not Modulate Basal Muscle Protein Synthesis Rates - A Substudy.

Directory of Open Access Journals (Sweden)

Rick Hursel

Full Text Available Based on controlled 36 h experiments a higher dietary protein intake causes a positive protein balance and a negative fat balance. A positive net protein balance may support fat free mass accrual. However, few data are available on the impact of more prolonged changes in habitual protein intake on whole-body protein metabolism and basal muscle protein synthesis rates.To assess changes in whole-body protein turnover and basal muscle protein synthesis rates following 12 weeks of adaptation to a low versus high dietary protein intake.A randomized parallel study was performed in 40 subjects who followed either a high protein (2.4 g protein/kg/d or low protein (0.4 g protein/kg/d energy-balanced diet (30/35/35% or 5/60/35% energy from protein/carbohydrate/fat for a period of 12 weeks. A subgroup of 7 men and 8 women (body mass index: 22.8±2.3 kg/m2, age: 24.3±4.9 y were selected to evaluate the impact of prolonged adaptation to either a high or low protein intake on whole body protein metabolism and basal muscle protein synthesis rates. After the diet, subjects received continuous infusions with L-[ring-2H5]phenylalanine and L-[ring-2H2]tyrosine in an overnight fasted state, with blood samples and muscle biopsies being collected to assess post-absorptive whole-body protein turnover and muscle protein synthesis rates in vivo in humans.After 12 weeks of intervention, whole-body protein balance in the fasted state was more negative in the high protein treatment when compared with the low protein treatment (-4.1±0.5 vs -2.7±0.6 μmol phenylalanine/kg/h;P<0.001. Whole-body protein breakdown (43.0±4.4 vs 37.8±3.8 μmol phenylalanine/kg/h;P<0.03, synthesis (38.9±4.2 vs 35.1±3.6 μmol phenylalanine/kg/h;P<0.01 and phenylalanine hydroxylation rates (4.1±0.6 vs 2.7±0.6 μmol phenylalanine/kg/h;P<0.001 were significantly higher in the high vs low protein group. Basal muscle protein synthesis rates were maintained on a low vs high protein diet (0.042�

Highly efficient one-pot three-component synthesis of naphthopyran derivatives in water catalyzed by hydroxyapatite

Science.gov (United States)

An expeditious and efficient protocol for the synthesis of naphthopyrans has been developed that proceeds via one-pot three-component sequential reaction in water catalyzed by hydroxyapatite or sodium-modified-hydroxyapatite. The title compounds have been obtained in high yield a...

Prolonged Adaptation to a Low or High Protein Diet Does Not Modulate Basal Muscle Protein Synthesis Rates - A Substudy.

Science.gov (United States)

Hursel, Rick; Martens, Eveline A P; Gonnissen, Hanne K J; Hamer, Henrike M; Senden, Joan M G; van Loon, Luc J C; Westerterp-Plantenga, Margriet S

2015-01-01

Based on controlled 36 h experiments a higher dietary protein intake causes a positive protein balance and a negative fat balance. A positive net protein balance may support fat free mass accrual. However, few data are available on the impact of more prolonged changes in habitual protein intake on whole-body protein metabolism and basal muscle protein synthesis rates. To assess changes in whole-body protein turnover and basal muscle protein synthesis rates following 12 weeks of adaptation to a low versus high dietary protein intake. A randomized parallel study was performed in 40 subjects who followed either a high protein (2.4 g protein/kg/d) or low protein (0.4 g protein/kg/d) energy-balanced diet (30/35/35% or 5/60/35% energy from protein/carbohydrate/fat) for a period of 12 weeks. A subgroup of 7 men and 8 women (body mass index: 22.8±2.3 kg/m2, age: 24.3±4.9 y) were selected to evaluate the impact of prolonged adaptation to either a high or low protein intake on whole body protein metabolism and basal muscle protein synthesis rates. After the diet, subjects received continuous infusions with L-[ring-2H5]phenylalanine and L-[ring-2H2]tyrosine in an overnight fasted state, with blood samples and muscle biopsies being collected to assess post-absorptive whole-body protein turnover and muscle protein synthesis rates in vivo in humans. After 12 weeks of intervention, whole-body protein balance in the fasted state was more negative in the high protein treatment when compared with the low protein treatment (-4.1±0.5 vs -2.7±0.6 μmol phenylalanine/kg/h;Pprotein breakdown (43.0±4.4 vs 37.8±3.8 μmol phenylalanine/kg/h;Psynthesis (38.9±4.2 vs 35.1±3.6 μmol phenylalanine/kg/h;Pprotein group. Basal muscle protein synthesis rates were maintained on a low vs high protein diet (0.042±0.01 vs 0.045±0.01%/h;P = 0.620). In the overnight fasted state, adaptation to a low-protein intake (0.4 g/kg/d) does not result in a more negative whole-body protein balance and

Synthesis of all-silica zeolites from highly concentrated gels containing hexamethonium cations

KAUST Repository

Liu, Xiaolong

2012-07-01

A pure and highly crystalline all-silica EU-1 zeolite has been obtained from the crystallization of gels containing very low water contents in the presence of hexamethonium cations. Decreasing the water content in the gel down to H 2O/Si < 1 inhibited the formation of ZSM-48, which is usually observed under more diluted standard crystallization conditions. Moreover, addition of NH 4F to the synthesis led to the formation of "half-fluorinated" ITQ-13 in which fluoride anions occupied only the center of D4R cages. In larger cages, the charge of the template was compensated by framework connectivity defects, clearly demonstrating once more the essential role of F - in the formation of D4R units. The formation of such hybrid (F,OH) is particularly interesting from a synthesis point of view, particularly for understanding the respective roles of fluoride and hydroxide anions in the crystallization process. © 2012 Elsevier Inc. All rights reserved.

Synthesis of belt-like BiOBr hierarchical nanostructure with high photocatalytic performance

Energy Technology Data Exchange (ETDEWEB)

Li, Haiping [National Engineering Technology Research Center for Colloidal Materials, Shandong University, Jinan 250100 (China); Liu, Jingyi; Hu, Tingxia [Environment Research Institute, Shandong University, Jinan 250100 (China); Du, Na; Song, Shue [Key Laboratory of Colloid and Interface Chemistry (Ministry of Education), Shandong University, Jinan 250100 (China); Hou, Wanguo, E-mail: wghou@sdu.edu.cn [Key Laboratory of Colloid and Interface Chemistry (Ministry of Education), Shandong University, Jinan 250100 (China)

2016-05-15

Highlights: • BiOBr hierarchical nanobelts (NBs) were solvothermally prepared. • NBs show higher specific surface area and photoabsorption than BiOBr nanosheets. • NBs exhibit higher photoactivity than the nanosheets. - Abstract: One-dimensional (1D) bismuth oxyhalide (BiOX) hierarchical nanostructures are always difficult to prepare. Herein, we report, for the first time, a simple synthesis of BiOBr nanobelts (NBs) via a facile solvothermal route, using bismuth subsalicylate as the template and bismuth source. The BiOBr nanobelts are composed of irregular single crystal nanoparticles with highly exposed (0 1 0) facets. Compared with the BiOBr nanosheets (NSs) with dominant exposed (0 0 1) facets, they exhibit higher photocatalytic activity toward degradation of Rhodamine B and Methylene Blue under visible light irradiation. The higher photocatalytic performance of BiOBr NBs arises from their larger specific surface area and higher photoabsorption capability. This study provides a simple route for synthesis of belt-like Bi-based hierarchical nanostructures.

NaCl as a solid solvent to assist the mechanochemical synthesis and post-synthesis of hierarchical porous MOFs with high I2 vapour uptake.

Science.gov (United States)

Yang, Junyi; Feng, Xiao; Lu, Guangnong; Li, Yulin; Mao, Chaochao; Wen, Zhongliang; Yuan, Wenbing

2018-04-03

The use of salts as grinding media to assist the mechanosynthesis, and the following one-pot mechanochemical post-synthesis, of hierarchically porous MOFs was carried out efficiently by ball milling. NaCl or KCl were used as a solid solvent to initially pre-grind with 1,3,5-benzenetricarboxylic acid (H3BTC) and copper acetate monhydrate, respectively, for 1 minute, then both mixtures were combined together for a further 20 minutes of grinding, and the resultant mixture was finally washed with ethanol and water to obtain the hierarchically micro-, meso- and macroporous HKUST-1 with a high yield. Moreover, the post-synthesis of these as-obtained hierarchically porous HKUST-1 was easily performed via grinding triethylenediamine (TED) with the above unwashed crude-products for 20 minutes. By adjusting the amount of NaCl and TED added, we simply fabricated the pore- and function-adjustable hierarchically porous HKUST-1. Furthermore, these as-obtained HKUST-1 products showed high performance in the capture of volatile iodine.

Click synthesis of PET radiopharmaceuticals

International Nuclear Information System (INIS)

Xu Mei; Kuang Chunxiang

2009-01-01

Increasing attention has been focused on synthesis radiopharmaceuticals for positron emission tomography (PET). The recent years witnessed applications of click chemistry to PET radiopharmaceutical synthesis,because of its distinctive advantages including high speed,yield and stereospecificity under mild conditions. Synthesis of 18 F-labeled and 11 C-labeled radiopharmaceuticals and intermediates via click chemistry are reviewed. The future trend of click chemistry for the synthesis of PET radiopharmaceutical is prospected. (authors)

Synthesis of the reported structure of piperazirum using a nitro-Mannich reaction as the key stereochemical determining step

Directory of Open Access Journals (Sweden)

James C. Anderson

2013-08-01

Full Text Available Piperazirum, isolated from Arum palaestinum Boiss, was originally assigned as r-3,c-5-diisobutyl-c-6-isopropylpiperazin-2-one. The reported structure was synthesised diastereoselectively using a key nitro-Mannich reaction to set up the C5/C6 relative stereochemistry. The structure was unambiguously assigned by single crystal X-ray diffraction but the spectroscopic data did not match those reported for the natural product. The structure of the natural product must therefore be revised.

High power Nb-doped LiFePO4 Li-ion battery cathodes; pilot-scale synthesis and electrochemical properties

Science.gov (United States)

Johnson, Ian D.; Blagovidova, Ekaterina; Dingwall, Paul A.; Brett, Dan J. L.; Shearing, Paul R.; Darr, Jawwad A.

2016-09-01

High power, phase-pure Nb-doped LiFePO4 (LFP) nanoparticles are synthesised using a pilot-scale continuous hydrothermal flow synthesis process (production rate of 6 kg per day) in the range 0.01-2.00 at% Nb with respect to total transition metal content. EDS analysis suggests that Nb is homogeneously distributed throughout the structure. The addition of fructose as a reagent in the hydrothermal flow process, followed by a post synthesis heat-treatment, affords a continuous graphitic carbon coating on the particle surfaces. Electrochemical testing reveals that cycling performance improves with increasing dopant concentration, up to a maximum of 1.0 at% Nb, for which point a specific capacity of 110 mAh g-1 is obtained at 10 C (6 min for the charge or discharge). This is an excellent result for a high power cathode LFP based material, particularly when considering the synthesis was performed on a large pilot-scale apparatus.

High pressure synthesis of ThB/sub 12/ and HfB/sub 12/

Energy Technology Data Exchange (ETDEWEB)

Cannon, J F; Farnsworth, P B [Brigham Young Univ., Provo, UT (USA). Dept. of Chemistry

1938-08-01

High pressure synthesis techniques were used to prepare ThB/sub 12/ and HfB/sub 12/. These compounds have the cubic UB/sub 12/-type structure with lattice parameters 7.612(1) A and 7.377(2) A respectively. The relationship between the lattice parameter for UB/sub 12/-type dodecaborides and the coordination number 12 radius of the metal atom differs for lanthanide, actinide and transition metal atoms. The prediction is made that it is possible to prepare AmB/sub 12/ at high pressures.

Synthesis and Purification of Iodoaziridines Involving Quantitative Selection of the Optimal Stationary Phase for Chromatography

Science.gov (United States)

Boultwood, Tom; Affron, Dominic P.; Bull, James A.

2014-01-01

The highly diastereoselective preparation of cis-N-Ts-iodoaziridines through reaction of diiodomethyllithium with N-Ts aldimines is described. Diiodomethyllithium is prepared by the deprotonation of diiodomethane with LiHMDS, in a THF/diethyl ether mixture, at -78 °Cin the dark. These conditions are essential for the stability of the LiCHI2 reagent generated. The subsequent dropwise addition of N-Ts aldimines to the preformed diiodomethyllithium solution affords an amino-diiodide intermediate, which is not isolated. Rapid warming of the reaction mixture to 0 °C promotes cyclization to afford iodoaziridines with exclusive cis-diastereoselectivity. The addition and cyclization stages of the reaction are mediated in one reaction flask by careful temperature control. Due to the sensitivity of the iodoaziridines to purification, assessment of suitable methods of purification is required. A protocol to assess the stability of sensitive compounds to stationary phases for column chromatography is described. This method is suitable to apply to new iodoaziridines, or other potentially sensitive novel compounds. Consequently this method may find application in range of synthetic projects. The procedure involves firstly the assessment of the reaction yield, prior to purification, by 1H NMR spectroscopy with comparison to an internal standard. Portions of impure product mixture are then exposed to slurries of various stationary phases appropriate for chromatography, in a solvent system suitable as the eluent in flash chromatography. After stirring for 30 min to mimic chromatography, followed by filtering, the samples are analyzed by 1H NMR spectroscopy. Calculated yields for each stationary phase are then compared to that initially obtained from the crude reaction mixture. The results obtained provide a quantitative assessment of the stability of the compound to the different stationary phases; hence the optimal can be selected. The choice of basic alumina, modified to

N-Boc Amines to Oxazolidinones via Pd(II)/Bis-sulfoxide/Brønsted Acid Co-Catalyzed Allylic C–H Oxidation

Science.gov (United States)

2015-01-01

A Pd(II)/bis-sulfoxide/Brønsted acid catalyzed allylic C–H oxidation reaction for the synthesis of oxazolidinones from simple N-Boc amines is reported. A range of oxazolidinones are furnished in good yields (avg 63%) and excellent diastereoselectivities (avg 15:1) to furnish products regioisomeric from those previously obtained using allylic C–H amination reactions. Mechanistic studies suggest the role of the phosphoric acid is to furnish a Pd(II)bis-sulfoxide phosphate catalyst that promotes allylic C–H cleavage and π-allylPd functionalization with a weak, aprotic oxygen nucleophile and to assist in catalyst regeneration. PMID:24999765

N-Boc amines to oxazolidinones via Pd(II)/bis-sulfoxide/Brønsted acid co-catalyzed allylic C-H oxidation.

Science.gov (United States)

Osberger, Thomas J; White, M Christina

2014-08-06

A Pd(II)/bis-sulfoxide/Brønsted acid catalyzed allylic C-H oxidation reaction for the synthesis of oxazolidinones from simple N-Boc amines is reported. A range of oxazolidinones are furnished in good yields (avg 63%) and excellent diastereoselectivities (avg 15:1) to furnish products regioisomeric from those previously obtained using allylic C-H amination reactions. Mechanistic studies suggest the role of the phosphoric acid is to furnish a Pd(II)bis-sulfoxide phosphate catalyst that promotes allylic C-H cleavage and π-allylPd functionalization with a weak, aprotic oxygen nucleophile and to assist in catalyst regeneration.

Silver-Catalyzed Aldehyde Olefination Using Siloxy Alkynes.

Science.gov (United States)

Sun, Jianwei; Keller, Valerie A; Meyer, S Todd; Kozmin, Sergey A

2010-03-20

We describe the development of a silver-catalyzed carbonyl olefination employing electron rich siloxy alkynes. This process constitutes an efficient synthesis of trisubstituted unsaturated esters, and represents an alternative to the widely utilized Horner-Wadsworth-Emmons reaction. Excellent diastereoselectivities are observed for a range of aldehydes using either 1-siloxy-1-propyne or 1-siloxy-1-hexyne. This mild catalytic process also enables chemoselective olefination of aldehydes in the presence of either ester or ketone functionality. Furthermore, since no by-products are generated, this catalytic process is perfectly suited for development of sequential reactions that can be carried out in a single flask.

An enantiomerically pure siderophore type ligand for the diastereoselective 1 : 1 complexation of lanthanide(III ions

Directory of Open Access Journals (Sweden)

Markus Albrecht

2009-12-01

Full Text Available A facile synthesis of a highly preorganized tripodal enterobactine-type ligand 1a-H3 consisting of a chiral C3-symmetric macrocyclic peptide and three tridentate 2-amido-8-hydroxyquinoline coordinating units is presented. Complex formation with various metal ions (Al3+, Ga3+, Fe3+, La3+ and Eu3+ was investigated by spectrophotometric methods. Only in the case of La3+ and Eu3+ were well defined 1 : 1 complexes formed. On the basis of CD spectroscopy and DFT calculations the configuration at the metal centre of the La3+ complex was determined to show Λ helicity. The coordination compounds [(1aLn] presented should be prototypes for further lanthanide(III complexes with an enterobactine analogue binding situation.

Acute high-caffeine exposure increases autophagic flux and reduces protein synthesis in C2C12 skeletal myotubes.

Science.gov (United States)

Hughes, M A; Downs, R M; Webb, G W; Crocker, C L; Kinsey, S T; Baumgarner, Bradley L

2017-04-01

Caffeine is a highly catabolic dietary stimulant. High caffeine concentrations (1-10 mM) have previously been shown to inhibit protein synthesis and increase protein degradation in various mammalian cell lines. The purpose of this study was to examine the effect of short-term caffeine exposure on cell signaling pathways that regulate protein metabolism in mammalian skeletal muscle cells. Fully differentiated C2C12 skeletal myotubes either received vehicle (DMSO) or 5 mM caffeine for 6 h. Our analysis revealed that caffeine promoted a 40% increase in autolysosome formation and a 25% increase in autophagic flux. In contrast, caffeine treatment did not significantly increase the expression of the skeletal muscle specific ubiquitin ligases MAFbx and MuRF1 or 20S proteasome activity. Caffeine treatment significantly reduced mTORC1 signaling, total protein synthesis and myotube diameter in a CaMKKβ/AMPK-dependent manner. Further, caffeine promoted a CaMKII-dependent increase in myostatin mRNA expression that did not significantly contribute to the caffeine-dependent reduction in protein synthesis. Our results indicate that short-term caffeine exposure significantly reduced skeletal myotube diameter by increasing autophagic flux and promoting a CaMKKβ/AMPK-dependent reduction in protein synthesis.

Asymmetric Synthesis of Hydrocarbazoles Catalyzed by an Octahedral Chiral-at-Rhodium Lewis Acid.

Science.gov (United States)

Huang, Yong; Song, Liangliang; Gong, Lei; Meggers, Eric

2015-12-01

A bis-cyclometalated chiral-at-metal rhodium complex catalyzes the Diels-Alder reaction between N-Boc-protected 3-vinylindoles (Boc = tert-butyloxycarbonyl) and β-carboxylic ester-substituted α,β-unsaturated 2-acyl imidazoles with good-to-excellent regioselectivity (up to 99:1) and excellent diastereoselectivity (>50:1 d.r.) as well as enantioselectivity (92-99% ee) under optimized conditions. The rhodium catalyst serves as a chiral Lewis acid to activate the 2-acyl imidazole dienophile by two-point binding and overrules the preferred regioselectivity of the uncatalyzed reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental synthesis of crystalline matrices based on Ce, Ba, Sr zirconates for immobilization of high-level radioactive actinides

International Nuclear Information System (INIS)

Anderson, E.B.; Burakov, B.E.; Vasiliev, V.G.; Starchenko, V.A.

1993-01-01

In geological disposal of high-level radioactive waste the main storage barriers, in the first place the matrix containing radionuclides, must remain undestructible over a long period of time. Very high requirements are imposed for the matrices from the viewpoint of their chemical stability and mechanical strength. Zirconates may be classified among compounds potentially suitable for the creation of crystalline matrices incorporating radionuclides in their structure. The paper considers results of laboratory experiments on the synthesis of crystalline matrices based on various zirconates by the methods of gas-static and axial pressing. Problems are discussed concerning the crystalline matrix industrial synthesis technology developed at the Radium Institute. One of the most promising directions in solving the problem of high-level waste (HLW) removal from the sphere of human activity is disposal in deep geological formations. The realization of this direction envisages creation of multibarrier compositions. Special attention is paid to the technology for the synthesis of the first, the most crucial, engineering barrier: the matrix into which radionuclides are incorporated. It is assumed that crystalline compounds best satisfy all the requirements as the most thermodynamically stable

Measurement of cross-linked elastin synthesis in bleomycin-induced pulmonary fibrosis using a highly sensitive assay for desmosine and isodesmosine

International Nuclear Information System (INIS)

Cantor, J.O.; Osman, M.; Keller, S.; Cerreta, J.M.; Mandl, I.; Turino, G.M.

1984-01-01

Cross-linked elastin synthesis was measured in the intratracheal bleomycin model of interstitial pulmonary fibrosis by incorporation of 14C-lysine into the elastin-specific crosslinks, desmosine and isodesmosine. Detection of the labeled crosslinks was facilitated by development of a highly sensitive assay utilizing thin-layer electrophoresis. The results indicate that crosslinked elastin synthesis is significantly elevated from controls (p less than 0.05) at 1 to 3 weeks after exposure to bleomycin and returns to normal by 5 weeks. The increases in labeled elastin synthesis are not directly related to changes in either total lung protein synthesis or the pool size of the 14C-lysine. In comparison with collagen and glycosaminoglycan synthesis in this model of lung injury, maximal increases in cross-linked elastin formation occur later, but overlap with the elevated synthesis of these other connective tissue components. The marked increase from normal in cross-linked elastin synthesis in this model suggests that this tissue component is an important part of the fibrotic response of the pulmonary parenchyma and may play a role in the observed alterations in lung structure and function

High-rate synthesis of microcrystalline silicon films using high-density SiH4/H2 microwave plasma

International Nuclear Information System (INIS)

Jia, Haijun; Saha, Jhantu K.; Ohse, Naoyuki; Shirai, Hajime

2007-01-01

A high electron density (> 10 11 cm -3 ) and low electron temperature (1-2 eV) plasma is produced by using a microwave plasma source utilizing a spoke antenna, and is applied for the high-rate synthesis of high quality microcrystalline silicon (μc-Si) films. A very fast deposition rate of ∼ 65 A/s is achieved at a substrate temperature of 150 deg. C with a high Raman crystallinity and a low defect density of (1-2) x 10 16 cm -3 . Optical emission spectroscopy measurements reveal that emission intensity of SiH and intensity ratio of H α /SiH are good monitors for film deposition rate and film crystallinity, respectively. A high flux of film deposition precursor and atomic hydrogen under a moderate substrate temperature condition is effective for the fast deposition of highly crystallized μc-Si films without creating additional defects as well as for the improvement of film homogeneity

Low-protein, high-carbohydrate diet increases glucose uptake and fatty acid synthesis in brown adipose tissue of rats.

Science.gov (United States)

Aparecida de França, Suélem; Pavani Dos Santos, Maísa; Nunes Queiroz da Costa, Roger Vinícius; Froelich, Mendalli; Buzelle, Samyra Lopes; Chaves, Valéria Ernestânia; Giordani, Morenna Alana; Pereira, Mayara Peron; Colodel, Edson Moleta; Marlise Balbinotti Andrade, Cláudia; Kawashita, Nair Honda

2014-04-01

The aim of this study was to evaluate glucose uptake and the contribution of glucose to fatty acid (FA) synthesis and the glycerol-3-phosphate (G3P) of triacylglycerol synthesis by interscapular brown adipose tissue (IBAT) of low-protein, high-carbohydrate (LPHC) diet-fed rats. LPHC (6% protein; 74% carbohydrate) or control (17% protein; 63% carbohydrate) diets were administered to rats (∼ 100 g) for 15 d. Total FA and G3P synthesis and the synthesis of FA and G3P from glucose were evaluated in vivo by (3)H2O and (14)C-glucose. Sympathetic neural contribution for FA synthesis was evaluated by comparing the synthesis in denervated (7 d before) IBAT with that of the contralateral innervated side. The insulin signaling and β3 adrenergic receptor (β3-AR) contents, as well as others, were determined by Western blot (Student's t test or analysis of variance; P ≤ 0.05). Total FA synthesis in IBAT was 133% higher in the LPHC group and was reduced 85% and 70% by denervation for the LPHC and control groups, respectively. Glucose uptake was 3.5-fold higher in the IBAT of LPHC rats than in that of the control rats, and the contribution of glucose to the total FA synthesis increased by 12% in control rats compared with 18% in LPHC rats. The LPHC diet increased the G3P generation from glucose by 270% and the insulin receptor content and the p-AKT insulin stimulation in IBAT by 120% and reduced the β3-AR content by 50%. The LPHC diet stimulated glucose uptake, both the total rates and the rates derived from glucose-dependent FA and G3P synthesis, by increasing the insulin sensitivity and the sympathetic flux, despite a reduction in the β3-AR content. Copyright © 2014 Elsevier Inc. All rights reserved.

trans-2-Phenyl-4-thiophenoxy-3,4-dihydro-2H-1-benzothiopyran

Directory of Open Access Journals (Sweden)

Rammohan Pal

2011-02-01

Full Text Available Iodine-catalyzed cyclocondensation of cinnamaldehyde and thiophenol yields rapidly trans-2-phenyl-4-thiophenoxy-3,4-dihydro-2H-1-benzothiopyran in excellent yield with very high diastereoselectivity.

Facile room-temperature solution-phase synthesis of a spherical covalent organic framework for high-resolution chromatographic separation.

Science.gov (United States)

Yang, Cheng-Xiong; Liu, Chang; Cao, Yi-Meng; Yan, Xiu-Ping

2015-08-07

A simple and facile room-temperature solution-phase synthesis was developed to fabricate a spherical covalent organic framework with large surface area, good solvent stability and high thermostability for high-resolution chromatographic separation of diverse important industrial analytes including alkanes, cyclohexane and benzene, α-pinene and β-pinene, and alcohols with high column efficiency and good precision.

High-Level Synthesis of DSP Applications Using Adaptive Negative Cycle Detection

Directory of Open Access Journals (Sweden)

Nitin Chandrachoodan

2002-09-01

Full Text Available The problem of detecting negative weight cycles in a graph is examined in the context of the dynamic graph structures that arise in the process of high level synthesis (HLS. The concept of adaptive negative cycle detection is introduced, in which a graph changes over time and negative cycle detection needs to be done periodically, but not necessarily after every individual change. We present an algorithm for this problem, based on a novel extension of the well-known Bellman-Ford algorithm that allows us to adapt existing cycle information to the modified graph, and show by experiments that our algorithm significantly outperforms previous incremental approaches for dynamic graphs. In terms of applications, the adaptive technique leads to a very fast implementation of Lawlers algorithm for the computation of the maximum cycle mean (MCM of a graph, especially for a certain form of sparse graph. Such sparseness often occurs in practical circuits and systems, as demonstrated, for example, by the ISCAS 89/93 benchmarks. The application of the adaptive technique to design-space exploration (synthesis is also demonstrated by developing automated search techniques for scheduling iterative data-flow graphs.

Combinatorial chemoenzymatic synthesis and high-throughput screening of sialosides.

Science.gov (United States)

Chokhawala, Harshal A; Huang, Shengshu; Lau, Kam; Yu, Hai; Cheng, Jiansong; Thon, Vireak; Hurtado-Ziola, Nancy; Guerrero, Juan A; Varki, Ajit; Chen, Xi

2008-09-19

Although the vital roles of structures containing sialic acid in biomolecular recognition are well documented, limited information is available on how sialic acid structural modifications, sialyl linkages, and the underlying glycan structures affect the binding or the activity of sialic acid-recognizing proteins and related downstream biological processes. A novel combinatorial chemoenzymatic method has been developed for the highly efficient synthesis of biotinylated sialosides containing different sialic acid structures and different underlying glycans in 96-well plates from biotinylated sialyltransferase acceptors and sialic acid precursors. By transferring the reaction mixtures to NeutrAvidin-coated plates and assaying for the yields of enzymatic reactions using lectins recognizing sialyltransferase acceptors but not the sialylated products, the biotinylated sialoside products can be directly used, without purification, for high-throughput screening to quickly identify the ligand specificity of sialic acid-binding proteins. For a proof-of-principle experiment, 72 biotinylated alpha2,6-linked sialosides were synthesized in 96-well plates from 4 biotinylated sialyltransferase acceptors and 18 sialic acid precursors using a one-pot three-enzyme system. High-throughput screening assays performed in NeutrAvidin-coated microtiter plates show that whereas Sambucus nigra Lectin binds to alpha2,6-linked sialosides with high promiscuity, human Siglec-2 (CD22) is highly selective for a number of sialic acid structures and the underlying glycans in its sialoside ligands.

Synthesis imaging in radio astronomy

International Nuclear Information System (INIS)

Perley, R.A.; Schwab, F.R.; Bridle, A.H.

1989-01-01

Recent advances in techniques and instrumentation for radio synthesis imaging in astronomy are discussed in a collection of review essays. Topics addressed include coherence in radio astronomy, the interferometer in practice, primary antenna elements, cross correlators, calibration and editing, sensitivity, deconvolution, self-calibration, error recognition, and image analysis. Consideration is given to wide-field imaging (bandwidth and time-average smearing, noncoplanar arrays, and mosaicking), high-dynamic-range imaging, spectral-line imaging, VLBI, solar imaging with a synthesis telescope, synthesis imaging of spatially coherent objects, noise in images of very bright sources, synthesis observing strategies, and the design of aperture-synthesis arrays

Size Tunable Synthesis of Highly Crystalline BaTiO3 Nanoparticles using Salt-Assisted Spray Pyrolysis

International Nuclear Information System (INIS)

Itoh, Yoshifumi; Lenggoro, I. Wuled; Okuyama, Kikuo; Maedler, Lutz; Pratsinis, Sotiris E.

2003-01-01

Highly crystalline, dense BaTiO 3 nanoparticles in a size range from 30 to 360nm with a narrow size distribution (σ g = 1.2-1.4) were prepared at various synthesis temperatures using a salt-assisted spray pyrolysis (SASP) method without the need for post-annealing. The effect of synthesis temperature on particle size, crystallinity and surface morphology of the nanoparticles were characterized by X-ray diffraction and scanning/transmission electron microscopy. The nature of the crystalline structure was analyzed by Rietveld refinement and Raman spectroscopy. The particle size decreased with decreasing operation temperature. The crystal phase was transformed from tetragonal to cubic at a particles size of about 50nm at room temperature. SASP can be used to produce high weight fraction of tetragonal BaTiO 3 nanoparticles down to 64nm in a single step

Molecular catalysis and high-volume organic synthesis

Energy Technology Data Exchange (ETDEWEB)

Khidekel, M L; Vasserberg, V E

1977-01-01

The field of catalysis is very wide. The properties of catalysts are briefly reviewed and compared with the properties of enzymes. Various uses of enxymes in industry (sugar from corn, cellulose breakdown, etc.) are pointed out. The types of homogeneous and heterogeneous catalysts for use in organic synthesis are discussed. 48 refs. (SJR)

Solid-phase submonomer synthesis of peptoid polymers and their self-assembly into highly-ordered nanosheets.

Science.gov (United States)

Tran, Helen; Gael, Sarah L; Connolly, Michael D; Zuckermann, Ronald N

2011-11-02

Peptoids are a novel class of biomimetic, non-natural, sequence-specific heteropolymers that resist proteolysis, exhibit potent biological activity, and fold into higher order nanostructures. Structurally similar to peptides, peptoids are poly N-substituted glycines, where the side chains are attached to the nitrogen rather than the alpha-carbon. Their ease of synthesis and structural diversity allows testing of basic design principles to drive de novo design and engineering of new biologically-active and nanostructured materials. Here, a simple manual peptoid synthesis protocol is presented that allows the synthesis of long chain polypeptoids (up to 50mers) in excellent yields. Only basic equipment, simple techniques (e.g. liquid transfer, filtration), and commercially available reagents are required, making peptoids an accessible addition to many researchers' toolkits. The peptoid backbone is grown one monomer at a time via the submonomer method which consists of a two-step monomer addition cycle: acylation and displacement. First, bromoacetic acid activated in situ with N,N'-diisopropylcarbodiimide acylates a resin-bound secondary amine. Second, nucleophilic displacement of the bromide by a primary amine follows to introduce the side chain. The two-step cycle is iterated until the desired chain length is reached. The coupling efficiency of this two-step cycle routinely exceeds 98% and enables the synthesis of peptoids as long as 50 residues. Highly tunable, precise and chemically diverse sequences are achievable with the submonomer method as hundreds of readily available primary amines can be directly incorporated. Peptoids are emerging as a versatile biomimetic material for nanobioscience research because of their synthetic flexibility, robustness, and ordering at the atomic level. The folding of a single-chain, amphiphilic, information-rich polypeptoid into a highly-ordered nanosheet was recently demonstrated. This peptoid is a 36-mer that consists of only

Surface-Casting Synthesis of Mesoporous Zirconia with a CMK-5-Like Structure and High Surface Area.

Science.gov (United States)

Gu, Dong; Schmidt, Wolfgang; Pichler, Christian M; Bongard, Hans-Josef; Spliethoff, Bernd; Asahina, Shunsuke; Cao, Zhengwen; Terasaki, Osamu; Schüth, Ferdi

2017-09-04

About 15 years ago, the Ryoo group described the synthesis of CMK-5, a material consisting of a hexagonal arrangement of carbon nanotubes. Extension of the surface casting synthesis to oxide compositions, however, was not possible so far, in spite of many attempts. Here it is demonstrated, that crystalline mesoporous hollow zirconia materials with very high surface areas up to 400 m 2  g -1 , and in selected cases in the form of CMK-5-like, are indeed accessible via such a surface casting process. The key for the successful synthesis is an increased interaction between the silica hard template surface and the zirconia precursor species by using silanol group-rich mesoporous silica as a hard template. The surface areas of the obtained zirconias exceed those of conventionally hard-templated ones by a factor of two to three. The surface casting process seems to be applicable also to other oxide materials. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Palladium-catalysed cyclisation of alkenols: Synthesis of oxaheterocycles as core intermediates of natural compounds

Directory of Open Access Journals (Sweden)

Miroslav Palík

2014-09-01

Full Text Available The study of Pd-catalysed cyclisation reactions of alkenols using different catalytic systems is reported. These transformations affect the stereoselective construction of mono- and/or bicyclic oxaheterocyclic derivatives depending on a starting alkenol. The substrate scope and proposed mechanism of Pd-catalysed cyclisation reactions are also discussed. Moreover, the diastereoselective Pd-catalysed cyclisation of appropriate alkenols to tetrahydrofurans and subsequent cyclisation provided properly substituted 2,5-dioxabicyclo[2.2.1]heptane and 2,6-dioxabicyclo[3.2.1]octane, respectively. Such bicyclic ring subunits are found in many natural products including ocellenynes and aurovertines.

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

Science.gov (United States)

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

2016-01-04

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

Bromide (Br) - Based Synthesis of Ag Nanocubes with High-Yield

OpenAIRE

Wu, Fan; Wang, Wenhui; Xu, Zhongfeng; Li, Fuli

2015-01-01

The geometry of metal nanoparticles greatly affects the properties of the localized surface plasmon resonance and surface-enhanced Raman scattering. The synthesis of metal nanoparticles with controllable geometry has thus attracted extensive attentions. In this work, we report a modified polyol synthesis approach of silver (Ag) nanocubes through tuning the concentration of bromide ions (Br? ions). We have systematically investigated the effect of Br? ions in the polyol process, and find that ...

Synthesis of high-surface-area spinel-type MgAl2O4 nanoparticles ...

Indian Academy of Sciences (India)

Home; Journals; Bulletin of Materials Science; Volume 40; Issue 1. Synthesis of high-surface-area spinel-type MgAl 2 O 4 nanoparticles by [Al(sal) 2 (H 2 O) 2 ] 2 [Mg(dipic) 2 ] and [Mg(H 2 O) 6 ][Al(ox) 2 (H 2 O) 2 ] 2 ·5H 2 O: influence of inorganic precursor type. Volume 40 Issue 1 February 2017 pp 45-53 ...

Final Report on XStack: Software Synthesis for High Productivity ExaScale Computing

Energy Technology Data Exchange (ETDEWEB)

Solar-Lezama, Armando [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Computer Science and Artificial Intelligence Lab.

2016-07-12

The goal of the project was to develop a programming model that would significantly improve productivity in the high-performance computing domain by bringing together three components: a) Automated equivalence checking, b) Sketch-based program synthesis, and c) Autotuning. The report provides an executive summary of the research accomplished through this project. At the end of the report is appended a paper that describes in more detail the key technical accomplishments from this project, and which was published in SC 2014.

Synthesis of High-Molecular-Weight Multifunctional Glycerol Polyhydroxyurethanes PHUs

Directory of Open Access Journals (Sweden)

Bassam Nohra

2016-09-01

Full Text Available Glycerol carbonate acrylate is a 5-membered cyclic carbonate synthesized from glycerol that is used as a chemical coupling agent and has proven highly suitable for use in the synthesis of multifunctional polyhydroxyurethanes (PHUs. The multifunctionality of the structure of PHUs is determined by the density of the carbon-amine groups generated by the Aza-Michael reaction and that of the urethane groups and adjacent primary and secondary hydroxyl groups generated by aminolysis. Glycerol carbonate acrylate is polymerized with polyfunctional mono-, di-, tri, and tetra-amines, by type-AB polyaddition, either in bulk or in solution, through stepwise or one-pot reaction strategies in the absence of added catalysts. These approaches result in the generation of linear, interchain, and crosslinked structures, through the polyaddition of linear and branched amines to the ethylene and cyclic carbonate sites of glycerol carbonate acrylate. The resulting collection of organic molecules gives rise to polyethylene amino ester PHUs with a high molar mass, exceeding 20,000 g·mol−1, with uniform dispersity.

High-purity Cu nanocrystal synthesis by a dynamic decomposition method

Science.gov (United States)

Jian, Xian; Cao, Yu; Chen, Guozhang; Wang, Chao; Tang, Hui; Yin, Liangjun; Luan, Chunhong; Liang, Yinglin; Jiang, Jing; Wu, Sixin; Zeng, Qing; Wang, Fei; Zhang, Chengui

2014-12-01

Cu nanocrystals are applied extensively in several fields, particularly in the microelectron, sensor, and catalysis. The catalytic behavior of Cu nanocrystals depends mainly on the structure and particle size. In this work, formation of high-purity Cu nanocrystals is studied using a common chemical vapor deposition precursor of cupric tartrate. This process is investigated through a combined experimental and computational approach. The decomposition kinetics is researched via differential scanning calorimetry and thermogravimetric analysis using Flynn-Wall-Ozawa, Kissinger, and Starink methods. The growth was found to be influenced by the factors of reaction temperature, protective gas, and time. And microstructural and thermal characterizations were performed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and differential scanning calorimetry. Decomposition of cupric tartrate at different temperatures was simulated by density functional theory calculations under the generalized gradient approximation. High crystalline Cu nanocrystals without floccules were obtained from thermal decomposition of cupric tartrate at 271°C for 8 h under Ar. This general approach paves a way to controllable synthesis of Cu nanocrystals with high purity.

Mineralizer-assisted high-pressure high-temperature synthesis and characterization of novel phosphorus nitride imides and luminescent alkaline earth metal (oxo)nitridophosphates

International Nuclear Information System (INIS)

Marchuk, Alexey

2016-01-01

The main objectives of this thesis were the synthesis, identification and structural characterization of new alkaline earth metal (oxo)nitridophopshates and phosphorus nitrides. Furthermore, luminescence properties of the resulting materials should be investigated and a connection between these properties and the respective structures should be established. For this purpose, a range of synthesis strategies was employed, including conventional solid-state syntheses in silica ampoules and high-pressure high-temperature syntheses using the multianvil technique. The emphasis of the synthetic part of this thesis lies on the development of new synthetic strategies in order to increase crystallinity of alkaline earth metal (oxo)nitridophosphates and thus accelerate their structure determination. This involves the selection of a suitable mineralizer and the investigation of its interaction with the respective starting materials. In addition, the analytical methods applied in this thesis in order to identify and characterize the compounds are just as essential as the synthesis strategies. X-ray diffraction on single crystals and on powders was carried out as the main analytical method while being supported by quantitative and qualitative 1 H and 31 P solid-state NMR measurements, FTIR and energy-dispersive X-ray (EDX) spectroscopy, as well as electron microscopy methods including both imaging and diffraction techniques. Implied by the large number of novel structures investigated, theoretical studies including topological analysis, calculations of lattice energies and bond-valence sums also played a major role in this thesis. Optical analysis methods such as reflectance spectroscopy, luminescence microscopy and photoluminescence measurements helped to determine the luminescence properties of some of the presented compounds.

ZrC Ceramics Prepared by Self-propagating High-temperature Synthesis/Single Action Pressing

Directory of Open Access Journals (Sweden)

CHENG Yong

2017-01-01

Full Text Available ZrC ceramics were prepared by mechanical axial compression of self-propagating high-temperature synthesis/single action pressing (SHS/SAP.The effects of pressure on microstructure and densification of the products,as well as the relationship between displacement/variation of the load curve and SHS reaction,were studied.The structure and properties of the products were investigated by XRD and SEM.In addition,the density was measured by the drain away liquid method.Meanwhile,universal testing machine was used to record the displacement and load curve alternations.The results indicate that products are mainly composed of ZrC phase,the process of exhaust are accelerated as the increasing of pressure as well,leading to the smaller size of porosity and crystal particles.Density manifested as an increasing pattern by the elevated pressure with no longer change at 80MPa.Due to the strong attenuation of pressure at the peak of temperature,the density of the production is only 65.7% in 120MPa.The end point of the SHS reaction and the plastic time of the products can be monitored by displacement and load curve.The results provide evidence for the application of self-propagating high-temperature synthesis/pseudo-hot isostatic pressing to further improve the density of ceramics.

One-step Synthesis of Pt Nanoparticles Highly Loaded on Graphene Aerogel as Durable Oxygen Reduction Electrocatalyst

International Nuclear Information System (INIS)

Huang, Qinghong; Tao, Feifei; Zou, Liangliang; Yuan, Ting; Zou, Zhiqing; Zhang, Haifeng; Zhang, Xiaogang; Yang, Hui

2015-01-01

Synthesis of highly active and durable Pt based catalysts with a high metal loading for fuel cells’ applications still remains a big challenge. The three-dimensional (3D) graphene aerogel (GA) not only possess the intrinsic property of graphene, but also have abundant pore architecture for anchoring metal nanoparticles, thus would be suitable as metal catalysts’ support. This work reports a simple and mild one-step co-reduction synthesis of Pt nanoparticles highly loaded on 3D GA and the use as durable oxygen reduction catalyst. Both X-ray diffraction and TEM measurements confirm that Pt nanoparticles (ca. 60 wt.% Pt loading) with an average diameter of ca. 3.2 nm are uniformly decorated on the homogeneously interconnected pores of 3D GA even after a heat treatment at 300 °C. Such a Pt/GA catalyst exhibits significantly enhanced electrocatalytic activity and improved durability for the oxygen reduction reaction. The enhancement in both catalytic activity and durability may result from the unique 3-D architecture structure of GA, the uniform dispersion of Pt nanoparticles, and the interaction between the Pt nanoparticles and GA. The GA-supported Pt can serve as a highly active catalyst for fuel cell applications

Carbohydrate-Assisted Combustion Synthesis To Realize High-Performance Oxide Transistors.

Science.gov (United States)

Wang, Binghao; Zeng, Li; Huang, Wei; Melkonyan, Ferdinand S; Sheets, William C; Chi, Lifeng; Bedzyk, Michael J; Marks, Tobin J; Facchetti, Antonio

2016-06-08

Owing to high carrier mobilities, good environmental/thermal stability, excellent optical transparency, and compatibility with solution processing, thin-film transistors (TFTs) based on amorphous metal oxide semiconductors (AOSs) are promising alternatives to those based on amorphous silicon (a-Si:H) and low-temperature (IGZO) TFTs suffer from low carrier mobilities and/or inferior bias-stress stability versus their sputtered counterparts. Here we report that three types of environmentally benign carbohydrates (sorbitol, sucrose, and glucose) serve as especially efficient fuels for IGZO film combustion synthesis to yield high-performance TFTs. The results indicate that these carbohydrates assist the combustion process by lowering the ignition threshold temperature and, for optimal stoichiometries, enhancing the reaction enthalpy. IGZO TFT mobilities are increased to >8 cm(2) V(-1) s(-1) on SiO2/Si gate dielectrics with significantly improved bias-stress stability. The first correlations between precursor combustion enthalpy and a-MO densification/charge transport are established.

One-pot synthesis of well-defined polyether/polyester block copolymers and terpolymers by a highly efficient catalyst switch approach

KAUST Repository

Alamri, Haleema

2016-04-20

A highly efficient methodology, based on a novel catalyst switch approach with rapid crossover characteristics, was developed for the one-pot synthesis of block co/terpolymers of cyclic ethers and esters. This new approach, which takes advantage of one of the best catalysts for epoxide (t-BuP4) and cyclic ester (t-BuP2) polymerization, opens new horizons toward the synthesis of cyclic ether/ester complex macromolecular architectures. © The Royal Society of Chemistry 2016.

One-pot synthesis of well-defined polyether/polyester block copolymers and terpolymers by a highly efficient catalyst switch approach

KAUST Repository

Alamri, Haleema; Hadjichristidis, Nikolaos

2016-01-01

A highly efficient methodology, based on a novel catalyst switch approach with rapid crossover characteristics, was developed for the one-pot synthesis of block co/terpolymers of cyclic ethers and esters. This new approach, which takes advantage of one of the best catalysts for epoxide (t-BuP4) and cyclic ester (t-BuP2) polymerization, opens new horizons toward the synthesis of cyclic ether/ester complex macromolecular architectures. © The Royal Society of Chemistry 2016.

Effects of Fuel to Synthesis of CaTiO3 by Solution Combustion Synthesis for High-Level Nuclear Waste Ceramics.

Science.gov (United States)

Jung, Choong-Hwan; Kim, Yeon-Ku; Han, Young-Min; Lee, Sang-Jin

2016-02-01

A solution combustion process for the synthesis of perovskite (CaTiO3) powders is described. Perovskite is one of the crystalline host matrics for the disposal of high-level radioactive wastes (HLW) because it immobilizes Sr and Lns elements by forming solid solutions. Solution combustion synthesis, which is a self-sustaining oxi-reduction reaction between nitrate and organic fuel, the exothermic reaction, and the heat evolved convert the precursors into their corresponding oxide products above 1100 degrees C in air. To investigate the effects of amino acid on the combustion reaction, various types of fuels were used; a glycine, amine and carboxylic ligand mixture. Sr, La and Gd-nitrate with equivalent amounts of up to 20% of CaTiO3 were mixed with Ca and Ti nitrate and amino acid. X-ray diffraction analysis, SEM and TEM were conducted to confirm the formed phases and morphologies. While powders with an uncontrolled shape are obtained through a general oxide-route process, Ca(Sr, Lns)TiO3 powders with micro-sized soft agglomerates consisting of nano-sized primary particles can be prepared using this method.

Noncovalent synthesis of protein dendrimers

NARCIS (Netherlands)

Lempens, E.H.M.; Baal, van I.; Dongen, van J.L.J.; Hackeng, T.M.; Merkx, M.; Meijer, E.W.

2009-01-01

The covalent synthesis of complex biomolecular systems such as multivalent protein dendrimers often proceeds with low efficiency, thereby making alternative strategies based on noncovalent chemistry of high interest. Here, the synthesis of protein dendrimers using a strong but noncovalent

Metal-organic framework based on copper(I) sulfate and 4,4'-bipyridine catalyzes the cyclopropanation of styrene

International Nuclear Information System (INIS)

Shi Fanian; Silva, Ana Rosa; Rocha, Joao

2011-01-01

The hydrothermal synthesis of a new metal-organic framework (MOF) formulated as Cu 2 (4,4'-bpy) 2 SO 4 .6(H 2 O), [abbreviation: (1); bpy or 4,4'-bpy=4,4'-bipyridine; SO 4 2- =sulfate group] has been reported. The structure of this MOF consists of Cu + nodes connected via 4,4'-bpy to form infinite chains, with two neighboring chains further bridged on the nodes by SO 4 2- , resulting in a 1-D double chain network. Guest water molecules reside in between the chains and are hydrogen-bonded to the O and S atoms from the nearest sulfate groups, leading to the formation of a 3-D supramolecular framework. This MOF is good heterogeneous catalyst for the cyclopropanation of styrene, with high trans cyclopropane diastereoselectivity and was recycled and reused for three consecutive cycles without a significant loss of catalytic activity. - Graphical Abstract: A new MOF structure built up of 4,4 ' -bipyridine, sulphate and Cu(I), is an active heterogeneous catalyst for cyclopropanation of styrene with ethyldiazoacetate. Highlights: → The synthesis is different from solvothermal synthesis for other Cu(I) compounds. → The compound and the structure are new. → H bonds form infinite planes among water molecules and sulphate species. → H bonding interaction makes the structure into a 3D supramolecular framework. → Active catalytic property as heterogeneous catalyst for cyclopropanation of styrene.

Solid-phase synthesis and structural characterization of highly substituted hydroxyproline-based 2,5-diketopiperazines

DEFF Research Database (Denmark)

Bianco; Sonksen; Roepstorff

2000-01-01

. The synthesis procedures were conceived to enable a sequence of Hyp alkylation, Hyp N-acylation, cyclization, and amide bond alkylation. Up to three different centers of molecular diversity were introduced around the DKP scaffold. Highly functionalized bicyclic compounds were obtained in good yield and purity...... with multidimensional NMR experiments. The described reaction pathways can be applied to the identification of heterocyclic molecule inhibitors to diverse enzyme targets....

Synthesis of alumina nano-sheets via supercritical fluid technology with high uranyl adsorptive capacity

International Nuclear Information System (INIS)

Jing Yu; Jun Wang; Zhanshuang Li; Qi Liu; Milin Zhang; Hongbin Bai; Caishan Jiao; Jun Wang; Lianhe Liu

2012-01-01

Supercritical carbon dioxide is beneficial to the synthesis of superior ultrafine and uniform materials due to its high chemical stability, low viscosity, high diffusivity, and 'zero' surface tension. γ-Alumina nano-sheets were obtained by a simple hydrothermal route in the presence of supercritical carbon dioxide. XRD, FTIR, SEM, TEM and nitrogen sorption isotherm were employed to characterize the samples. Alumina as-prepared has a high specific surface area of up to 200 ± 6 m 2 g -1 , which presents a high adsorption capacity (4.66 ± 0.02 mg g -1 ) for uranyl ions from aqueous solution. Furthermore, the adsorption process was found to be endothermic and spontaneous in nature. (authors)

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...

Synthesis and chemical recycling of high polymers using C1 compounds; C1 kagobutsu ni yoru kobunshi no chemical recycle

Energy Technology Data Exchange (ETDEWEB)

Masuda, T. [National Institute of Materials and Chemical Research, Tsukuba (Japan)

1997-09-01

The paper outlined a study of the synthesis of high polymers using C1 compounds which are continuously usable chemical materials and the related compounds such as the derivatives, and also the chemical recycle. In the case of waste plastics mixed in urban refuse, effective is the chemical recycle where C1 compounds obtained by gasifying the mixed waste are used as high polymer material. For the synthesis and recycle of high polymers using C1 compounds, there are three routes: Route A (recycle via high polymer materials), Route B (recycle via C1 compounds and high polymer materials), and Route C including global-scale carbon recycle (recycle via carbon dioxide from biodegradable plastics using microorganism). Among high polymers, those that can be synthesized from C1 compounds, for example, polymethylene, polyacetal and polyketone can be chemically recycled by Route B. 30 refs., 2 figs., 1 tab.

Highly efficient water-mediated approach to access benzazoles: metal catalyst and base-free synthesis of 2-substituted benzimidazoles, benzoxazoles, and benzothiazoles.

Science.gov (United States)

Bala, Manju; Verma, Praveen Kumar; Sharma, Deepika; Kumar, Neeraj; Singh, Bikram

2015-05-01

An efficient water-catalyzed method has been developed for the synthesis of 2-substituted benzimidazoles, benzoxazoles, and benzothiazoles in one step. The present method excludes the usage of toxic metal catalysts and bases to produce benzazoles in good to excellent yields. An efficient and versatile water-mediated method has been established for the synthesis of various 2-arylbenzazoles. The present protocol excludes the usage of any catalyst and additive provided excellent selectivities and yields with high functional group tolerance for the synthesis of 2-arylated benzimidazoles, benzoxazoles, and benzothiazoles. Benzazolones were also synthesized using similar reaction protocol.

Chelation-Assisted Substrate-Controlled Asymmetric Lithiation-Allylboration of Chiral Carbamate 1,2,4-Butanetriol Acetonide

Directory of Open Access Journals (Sweden)

Adeem Mahmood

2015-05-01

Full Text Available The lithiation of 2-(2,2-dimethyl-1,3-dioxolan-4-ylethyl diisopropylcarbamate (1 is achieved freely by sec-butyllithium in diethylether with high lk-diastereoselectivity: the bicyclic chelate complexes 3a and 3b are reacted with electrophiles to form optically active precursors 4a and 4b with >95% diastereoselectivity. In addition, tertiary diamines can undergo an external complexation in contest with the internal oxygen ligand, leading to improved stereoselectivities. The further reactions of lithiated carbamates with trans alkenyl-9-BBN derivatives after 1,2 metallate rearrangements, gave the key intermediate α-substituted allylic boranes 7. Subsequent allylboration of aldehydes gave (Z-anti-homoallylic alcohols 8 in good yield and excellent d.r.

Scalable synthesis of interconnected porous silicon/carbon composites by the Rochow reaction as high-performance anodes of lithium ion batteries.

Science.gov (United States)

Zhang, Zailei; Wang, Yanhong; Ren, Wenfeng; Tan, Qiangqiang; Chen, Yunfa; Li, Hong; Zhong, Ziyi; Su, Fabing

2014-05-12

Despite the promising application of porous Si-based anodes in future Li ion batteries, the large-scale synthesis of these materials is still a great challenge. A scalable synthesis of porous Si materials is presented by the Rochow reaction, which is commonly used to produce organosilane monomers for synthesizing organosilane products in chemical industry. Commercial Si microparticles reacted with gas CH3 Cl over various Cu-based catalyst particles to substantially create macropores within the unreacted Si accompanying with carbon deposition to generate porous Si/C composites. Taking advantage of the interconnected porous structure and conductive carbon-coated layer after simple post treatment, these composites as anodes exhibit high reversible capacity and long cycle life. It is expected that by integrating the organosilane synthesis process and controlling reaction conditions, the manufacture of porous Si-based anodes on an industrial scale is highly possible. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

2-Phenyl-tetrahydropyrimidine-4(1H-ones – cyclic benzaldehyde aminals as precursors for functionalised β2-amino acids

Directory of Open Access Journals (Sweden)

Markus Nahrwold

2009-09-01

Full Text Available Novel procedures have been developed to condense benzaldehyde effectively with β-amino acid amides to cyclic benzyl aminals. Double carbamate protection of the heterocycle resulted in fully protected chiral β-alanine derivatives. These serve as universal precursors for the asymmetric synthesis of functionalised β2-amino acids containing acid-labile protected side chains. Diastereoselective alkylation of the tetrahydropyrimidinone is followed by a chemoselective two step degradation of the heterocycle to release the free β2-amino acid. In the course of this study, an L-asparagine derivative was condensed with benzaldehyde and subsequently converted to orthogonally protected (R-β2-homoaspartate.

Controlled soft-template synthesis of ultrathin C@FeS nanosheets with high-Li-storage performance.

Science.gov (United States)

Xu, Chen; Zeng, Yi; Rui, Xianhong; Xiao, Ni; Zhu, Jixin; Zhang, Wenyu; Chen, Jing; Liu, Weiling; Tan, Huiteng; Hng, Huey Hoon; Yan, Qingyu

2012-06-26

We report a facile approach to prepare carbon-coated troilite FeS (C@FeS) nanosheets via surfactant-assisted solution-based synthesis. 1-Dodecanethiol is used as both the sulfur source and the surfactant, which may form different-shaped micelles to direct the growth of nanostructures. Under appropriate growth conditions, the iron and sulfur atoms react to form thin layers of FeS while the hydrocarbon tails of 1-dodecanethiol separate the thin FeS layers, which turn to carbon after annealing in Ar. Such an approach can be extended to grow C@FeS nanospheres and nanoplates by modifying the synthesis parameters. The C@FeS nanosheets display excellent Li storage properties with high specific capacities and stable charge/discharge cyclability, especially at fast charge/discharge rates.

STICS: surface-tethered iterative carbohydrate synthesis.

Science.gov (United States)

Pornsuriyasak, Papapida; Ranade, Sneha C; Li, Aixiao; Parlato, M Cristina; Sims, Charles R; Shulga, Olga V; Stine, Keith J; Demchenko, Alexei V

2009-04-14

A new surface-tethered iterative carbohydrate synthesis (STICS) technology is presented in which a surface functionalized 'stick' made of chemically stable high surface area porous gold allows one to perform cost efficient and simple synthesis of oligosaccharide chains; at the end of the synthesis, the oligosaccharide can be cleaved off and the stick reused for subsequent syntheses.

High-Level Synthesis: Productivity, Performance, and Software Constraints

Directory of Open Access Journals (Sweden)

Yun Liang

2012-01-01

Full Text Available FPGAs are an attractive platform for applications with high computation demand and low energy consumption requirements. However, design effort for FPGA implementations remains high—often an order of magnitude larger than design effort using high-level languages. Instead of this time-consuming process, high-level synthesis (HLS tools generate hardware implementations from algorithm descriptions in languages such as C/C++ and SystemC. Such tools reduce design effort: high-level descriptions are more compact and less error prone. HLS tools promise hardware development abstracted from software designer knowledge of the implementation platform. In this paper, we present an unbiased study of the performance, usability and productivity of HLS using AutoPilot (a state-of-the-art HLS tool. In particular, we first evaluate AutoPilot using the popular embedded benchmark kernels. Then, to evaluate the suitability of HLS on real-world applications, we perform a case study of stereo matching, an active area of computer vision research that uses techniques also common for image denoising, image retrieval, feature matching, and face recognition. Based on our study, we provide insights on current limitations of mapping general-purpose software to hardware using HLS and some future directions for HLS tool development. We also offer several guidelines for hardware-friendly software design. For popular embedded benchmark kernels, the designs produced by HLS achieve 4X to 126X speedup over the software version. The stereo matching algorithms achieve between 3.5X and 67.9X speedup over software (but still less than manual RTL design with a fivefold reduction in design effort versus manual RTL design.

Gram-Scale Synthesis of Highly Active and Durable Octahedral PtNi Nanoparticle Catalysts for Proton Exchange Membrane Fuel Cell

DEFF Research Database (Denmark)

Choi, Juhyuk; Jang, Jue-Hyuk; Roh, Chi-Woo

2018-01-01

for the commercialization of PEMFCs. In this study, we focus on gram-scale synthesis of octahedral PtNi nanoparticles with Pt overlayers (PtNi@Pt) supported on the carbon, resulting in enhanced catalytic activity and durability. Such PtNi@Pt catalysts show high mass activity (1.24 A mgPt−1) at 0.9 V (vs RHE) for the ORR......Proton exchange membrane fuel cells (PEMFC) are regarded as a promising renewable energy source for a future hydrogen energy society. However, highly active and durable catalysts are required for the PEMFCs because of their intrinsic high overpotential at the cathode and operation under the acidic...... condition for oxygen reduction reaction (ORR). Since the discovery of the exceptionally high surface activity of Pt3Ni(111), the octahedral PtNi nanoparticles have been synthesized and tested. Nonetheless, their milligram-scale synthesis method and poor durability make them unsuitable...

Synthesis and characterization of highly triboluminescent doped europium tetrakis compounds

International Nuclear Information System (INIS)

Fontenot, Ross S.; Hollerman, William A.; Bhat, Kamala N.; Aggarwal, Mohan D.

2012-01-01

One of the most intriguing properties involving crystals is their ability to emit light when fractured. While this property was discovered over 200 years ago, no one has ever been able to come up with a complete theory that can predict the physical principles associated with triboluminescence. However, this has not stopped scientists from coming up with various uses for these materials. One such application is to use these materials as the active element for smart impact sensors that can warn of catastrophic impacts. If these sensors are to become a reality however, the material must emit a bright light when fractured. One of the brightest triboluminescent materials found thus far is europium dibenzoylmethide triethylammonium (EuD 4 TEA). This material was discovered by Hurt in 1966 and is bright enough to be seen in daylight. In 2011, the authors discovered that synthesizing EuD 4 TEA using europium nitrate instead of chloride significantly increased the triboluminescence yield and made the synthesis much easier and more consistent. However, to date, there are few investigations into the effects of dopants on the triboluminescence of EuD 4 TEA. This paper reports the investigation of the effects of various dopants on: (1) The triboluminescent light yield, (2) Crystal size and structure, (3) Synthesis time, and (4) Prompt decay time. Results show that inclusion of dopants during synthesis increases the triboluminescence emission of EuD 4 TEA by 55%, significantly reduces the synthesis time, and controls the decay time. All of these properties can be useful for constructing the first prototype of a customized impact sensor. - Highlights: ► Doped europium dibenzoylmethide triethylammonium (EuD 4 TEA) was synthesized. ► Effects of dopants was studied from EuD 4 TEA during low velocity (<10 m/s) impacts. ► The triboluminescent light yield, decay time, and synthesis time were measured. ► A specially-built drop tower was developed to measure triboluminescence

Increased synthesis of high-molecular-weight cPLA2 mediates early UV-induced PGE2 in human skin.

Science.gov (United States)

Gresham, A; Masferrer, J; Chen, X; Leal-Khouri, S; Pentland, A P

1996-04-01

Ultraviolet light (UV) B-induced inflammation is characterized by dramatic increases in prostaglandin E2 (PGE2) synthesis due to enhanced arachidonate deacylation from the membrane. Therefore, the effect of UV on sythesis, mass, and distribution of the high-molecular-weight phospholipase A2 (cPLA2) in cultured human keratinocytes and human skin was studied. The 105-kDa cPLA2 was demonstrated to be the critical enzyme in UV-induced PGE2 synthesis and erythema in the first 6 h postirradiation. Immunoprecipitation of 35S-labeled protein showed cPLA2 synthesis increased three- to fourfold 6 h after irradiation. Immunoprecipitated 32P-labeled cPLA2 demonstrated phosphorylation of cPLA2 was concurrently induced, suggesting that UV also activates cPLA2. This increase in cPLA2 synthesis and activation also closely correlated with increased PGE2 synthesis and [3H]arachidonic acid release and was effectively blocked by both an S-oligonucleotide antisense to cPLA2 and methyl arachidonate fluorophosphate, a specific inhibitor of cPLA2. Biopsy and histochemical examination of erythematous sites expressed increased amounts of cPLA2 whereas nonerythematous irradiated sites did not. In contrast, cyclooxygenase-1 and -2 in cultures and skin explants were unaffected 6 h post-UV, and no change in cyclooxygenase activity was observed at this time. These results suggest that increased cPLA2 synthesis occurs only when skin is exposed to UV doses that are sufficient to cause erythema and indicate expression of cPLA2 participates in acute UV inflammation.

Synthesis and properties of regenerated cellulose-based hydrogels with high strength and transparency for potential use as an ocular bandage

International Nuclear Information System (INIS)

Patchan, M.; Graham, J.L.; Xia, Z.; Maranchi, J.P.; McCally, R.; Schein, O.; Elisseeff, J.H.; Trexler, M.M.

2013-01-01

Cellulose is a biologically derived material with excellent wound-healing properties. The high strength of cellulose fibers and the ability to synthesize gels with high optical transparency make these materials suitable for ocular applications. In this study, cellulose materials derived from wood pulp, cotton, and bacterial sources were dissolved in lithium chloride/N,N-dimethylacetamide to form regenerated cellulose hydrogels. Material properties of the resulting hydrogels, including water content, optical transparency, and tensile and tear strengths, were evaluated. Synthesis parameters, including activation time, dissolution time, relative humidity, and cellulose concentration, were found to impact the material properties of the resulting hydrogels. Overnight activation time improves the optical transparency of the hydrogels from 77% to 97% at 550 nm, whereas controlling cellulose concentration improves their tear strength by as much as 200%. On the basis of the measured transmittance and strength values of the regenerated hydrogels prepared via the optimized synthesis parameters, Avicel PH 101, Sigma-Aldrich microcrystalline cellulose 435236, and bacterial cellulose types were prioritized for future biocompatibility testing and potential clinical investigation. - Highlights: • Hydrogels were prepared (via LiCl/DMAc) from 7 different types of cellulose. • Synthesis parameters (activation, gelation, and concentration) were optimized. • Impact of synthesis parameters on transparency and strength was explored

Synthesis and properties of regenerated cellulose-based hydrogels with high strength and transparency for potential use as an ocular bandage

Energy Technology Data Exchange (ETDEWEB)

Patchan, M. [Research and Exploratory Development Department, The Johns Hopkins University Applied Physics Laboratory, 11100 Johns Hopkins Road, Laurel, MD 20723 (United States); Graham, J.L. [Department of Biomedical Engineering, Johns Hopkins University, School of Medicine, 720 Rutland Avenue/Ross 720, Baltimore, MD 21205 (United States); Xia, Z.; Maranchi, J.P. [Research and Exploratory Development Department, The Johns Hopkins University Applied Physics Laboratory, 11100 Johns Hopkins Road, Laurel, MD 20723 (United States); McCally, R. [Research and Exploratory Development Department, The Johns Hopkins University Applied Physics Laboratory, 11100 Johns Hopkins Road, Laurel, MD 20723 (United States); Wilmer Eye Institute, Johns Hopkins Medical Institutions, 600 N. Wolfe Street, Baltimore, MD 21287 (United States); Schein, O. [Wilmer Eye Institute, Johns Hopkins Medical Institutions, 600 N. Wolfe Street, Baltimore, MD 21287 (United States); Elisseeff, J.H. [Department of Biomedical Engineering, Johns Hopkins University, School of Medicine, 720 Rutland Avenue/Ross 720, Baltimore, MD 21205 (United States); Trexler, M.M., E-mail: morgana.trexler@jhuapl.edu [Research and Exploratory Development Department, The Johns Hopkins University Applied Physics Laboratory, 11100 Johns Hopkins Road, Laurel, MD 20723 (United States)

2013-07-01

Cellulose is a biologically derived material with excellent wound-healing properties. The high strength of cellulose fibers and the ability to synthesize gels with high optical transparency make these materials suitable for ocular applications. In this study, cellulose materials derived from wood pulp, cotton, and bacterial sources were dissolved in lithium chloride/N,N-dimethylacetamide to form regenerated cellulose hydrogels. Material properties of the resulting hydrogels, including water content, optical transparency, and tensile and tear strengths, were evaluated. Synthesis parameters, including activation time, dissolution time, relative humidity, and cellulose concentration, were found to impact the material properties of the resulting hydrogels. Overnight activation time improves the optical transparency of the hydrogels from 77% to 97% at 550 nm, whereas controlling cellulose concentration improves their tear strength by as much as 200%. On the basis of the measured transmittance and strength values of the regenerated hydrogels prepared via the optimized synthesis parameters, Avicel PH 101, Sigma-Aldrich microcrystalline cellulose 435236, and bacterial cellulose types were prioritized for future biocompatibility testing and potential clinical investigation. - Highlights: • Hydrogels were prepared (via LiCl/DMAc) from 7 different types of cellulose. • Synthesis parameters (activation, gelation, and concentration) were optimized. • Impact of synthesis parameters on transparency and strength was explored.

A concise route to pyrrolizidine alkaloids bearing the 1,2-amino alcohol functionality

Energy Technology Data Exchange (ETDEWEB)

Palomo, C.; Aizpurua, J.M.; Roman, P.; Luque, A.; Martinez-Ripoll, M. [Facultad de Quimica, Departamento de Quimica Organica, Universidad del Pais Vascom San Sebastian (Spain)

1996-10-01

The first entry to optically pure 4-amino-3-hydroxy-pyrrolizidine and 4-amino-pyrrolizidine alkaloid frameworks is provided by a highly diastereoselective [2+2] cycloaddition of alkoxyketenes to N-Boc-prolinal imines as the key reaction.

High pressure synthesis and investigations of properties of boron allotropes and boron carbide

International Nuclear Information System (INIS)

Chuvashova, Irina

2017-01-01

This work aimed at the development of the high-pressure high-temperature (HPHT) synthesis of single crystals of boron allotropes and boron-rich compounds, which could be used further for precise investigations of their structures, properties, and behavior at extreme conditions. To summarize, the present work resulted in the HPHT synthesis of the first previously unknown non-icosahedral boron allotrope ζ-B. This finding confirmed earlier theoretical predictions, which stayed unproven for decades because of experimental challenges which couldn't be overcome until recently. Structural stability of α-B and β-B in the Mbar pressure range and B 13 C 2 up to 68 GPa was experimentally proven. Accurate measurements of the unit cell and B 12 icosahedra volumes of the stoichiometric boron carbide B 13 C 2 as a function of pressure led to conclusion that they undergo a similar reduction upon compression that is typical for covalently bonded solids. Neither 'molecular-like' nor 'inversed molecular-like' solid behavior upon compression was detected that has closed a long-standing scientific dispute. A comparison of the compressional behavior of B 13 C 2 with that of α-B and γ-B allotropes and B 4 C showed that it is determined by the types of bonding involved in the course of compression.

High pressure synthesis and investigations of properties of boron allotropes and boron carbide

Energy Technology Data Exchange (ETDEWEB)

Chuvashova, Irina

2017-06-12

This work aimed at the development of the high-pressure high-temperature (HPHT) synthesis of single crystals of boron allotropes and boron-rich compounds, which could be used further for precise investigations of their structures, properties, and behavior at extreme conditions. To summarize, the present work resulted in the HPHT synthesis of the first previously unknown non-icosahedral boron allotrope ζ-B. This finding confirmed earlier theoretical predictions, which stayed unproven for decades because of experimental challenges which couldn't be overcome until recently. Structural stability of α-B and β-B in the Mbar pressure range and B{sub 13}C{sub 2} up to 68 GPa was experimentally proven. Accurate measurements of the unit cell and B{sub 12} icosahedra volumes of the stoichiometric boron carbide B{sub 13}C{sub 2} as a function of pressure led to conclusion that they undergo a similar reduction upon compression that is typical for covalently bonded solids. Neither 'molecular-like' nor 'inversed molecular-like' solid behavior upon compression was detected that has closed a long-standing scientific dispute. A comparison of the compressional behavior of B{sub 13}C{sub 2} with that of α-B and γ-B allotropes and B{sub 4}C showed that it is determined by the types of bonding involved in the course of compression.

Divergent solid-phase synthesis of natural product-inspired bipartite cyclodepsipeptides : total synthesis of seragamide A

NARCIS (Netherlands)

Arndt, H.-D.; Rizzo, S.; Nöcker, Chr.; Wackchaure, V.N.; Milroy, L.G.; Bieker, V.; Calderon, A.; Tran, T.T.N.; Brand, S.; Dehmelt, L.; Waldmann, H.

2015-01-01

Macrocyclic natural products (NPs) and analogues thereof often show high affinity, selectivity, and metabolic stability, and methods for the synthesis of NP-like macrocycle collections are of major current interest. We report an efficient solid-phase/cyclorelease method for the synthesis of a

Low-load high volume resistance exercise stimulates muscle protein synthesis more than high-load low volume resistance exercise in young men.

Directory of Open Access Journals (Sweden)

Nicholas A Burd

Full Text Available BACKGROUND: We aimed to determine the effect of resistance exercise intensity (%1 repetition maximum-1RM and volume on muscle protein synthesis, anabolic signaling, and myogenic gene expression. METHODOLOGY/PRINCIPAL FINDINGS: Fifteen men (21+/-1 years; BMI=24.1+/-0.8 kg/m2 performed 4 sets of unilateral leg extension exercise at different exercise loads and/or volumes: 90% of repetition maximum (1RM until volitional failure (90FAIL, 30% 1RM work-matched to 90%FAIL (30WM, or 30% 1RM performed until volitional failure (30FAIL. Infusion of [ring-13C6] phenylalanine with biopsies was used to measure rates of mixed (MIX, myofibrillar (MYO, and sarcoplasmic (SARC protein synthesis at rest, and 4 h and 24 h after exercise. Exercise at 30WM induced a significant increase above rest in MIX (121% and MYO (87% protein synthesis at 4 h post-exercise and but at 24 h in the MIX only. The increase in the rate of protein synthesis in MIX and MYO at 4 h post-exercise with 90FAIL and 30FAIL was greater than 30WM, with no difference between these conditions; however, MYO remained elevated (199% above rest at 24 h only in 30FAIL. There was a significant increase in AktSer473 at 24h in all conditions (P=0.023 and mTORSer2448 phosphorylation at 4 h post-exercise (P=0.025. Phosporylation of Erk1/2Tyr202/204, p70S6KThr389, and 4E-BP1Thr37/46 increased significantly (P<0.05 only in the 30FAIL condition at 4 h post-exercise, whereas, 4E-BP1Thr37/46 phosphorylation was greater 24 h after exercise than at rest in both 90FAIL (237% and 30FAIL (312% conditions. Pax7 mRNA expression increased at 24 h post-exercise (P=0.02 regardless of condition. The mRNA expression of MyoD and myogenin were consistently elevated in the 30FAIL condition. CONCLUSIONS/SIGNIFICANCE: These results suggest that low-load high volume resistance exercise is more effective in inducing acute muscle anabolism than high-load low volume or work matched resistance exercise modes.

Synthesis and high (pressure, temperature) stability of ZnTiO3 polymorphs studied by Raman spectroscopy

Science.gov (United States)

Bernert, T.; Ruiz-Fuertes, J.; Bayarjargal, L.; Winkler, B.

2015-05-01

The phase-purity of ilmenite-type ZnTiO3 prepared by the ceramic method was investigated in dependence of the conditions during ball milling. The previously proposed addition of 2 ml ethanol to the starting materials led to a significant contamination of the product phase after a subsequent sintering process at 1073 K. However, by omitting ethanol this synthesis route led to a phase-pure sample of ZnTiO3 as confirmed by X-ray powder diffraction and Raman spectroscopy. High-temperature high-pressure experiments gave an ilmenite-type to perovskite-type phase boundary with a slope of dT/dP∼-135 K GPa-1 crossing ambient temperature conditions at ∼ 24 GPa in good agreement with previous calculations. Room-temperature high-pressure Raman spectroscopy experiments have shown the stability of the ilmenite-type phase up to a pressure of at least 38.5 GPa, the highest pressure applied in this study, indicating the presence of a kinetic barrier in this phase transition. The synthesis of ferroelectric LiNbO3-type ZnTiO3 was confirmed by second harmonic generation.

Synthesis of Zeolite NaA from Low Grade (High Impurities) Indonesian Natural Zeolite

OpenAIRE

Mustain, Asalil; Wibawa, Gede; Nais, Mukhammad Furoiddun; Falah, Miftakhul

2014-01-01

The zeolite NaA has been successfully synthesized from the low grade natural zeolite with high impurities. The synthesis method was started by mixing natural zeolite powder with NH4Cl aqueous solution in the reactor as pretreatment. The use of pretreatment was to reduce the impurities contents in the zeolite. The process was followed by alkaline fusion hydrothermal treatment to modify the framework structure of natural zeolite and reduce the SiO2/Al2O3 ratio. Finally, the synthesized zeolite ...

Synthesis of niobium carbide by a high energy milling technique of powder metallurgy

International Nuclear Information System (INIS)

Antonello, Rodrigo Tecchio; Gonzalez, Cezar Henrique; Urtiga Filho, Severino Leopoldino; Araujo Filho, Oscar Olimpio de; Ambrozio Filho, Francisco

2010-01-01

The aim of this work is to obtain and characterize the Niobium Carbide (NbC) by a suitable high energy milling technique using a SPEX Mill vibratory type and niobium and carbon (graphite) powders. Since this carbide is scarced in the national market and it's necessary to apply this NbC as a reinforcement in two molybdenum high speed steels (AISI M2 and AISI M3:2) object of another work motivated this research. The powders were submitted to a high energy milling procedure for suitable times and conditions and then were characterized by means of Scanning Electronic Microscopy (SEM), Energy Dispersive Spectroscopy (EDS) and X-ray diffraction (DRX) techniques. The ball-to-powder weight ratio was 10:1. The analysed samples showed that the high-energy milling is an alternative route of the NbC synthesis. (author)

Synthesis of niobium carbide (NbC) by powder metallurgy high energy milling technique

International Nuclear Information System (INIS)

Antonello, Rodrigo Tecchio; Urtiga Filho, Severino Leopoldino; Araujo Filho, Oscar Olimpio de; Ambrozio Filho, Francisco; Gonzalez, Cezar Henrique

2009-01-01

The aim of this work is to obtain and characterize the Niobium Carbide (NbC) by a suitable high energy milling technique using a SPEX Mill vibratory type and niobium and carbon (graphite) powders. Since this carbide is scarce in the national market and it's necessary to apply this NbC as a reinforcement in two molybdenum high speed steels (AISI M2 and AISI M3:2) object of another work motivated this research. The powders were submitted to a high energy milling procedure for suitable times and conditions and then were characterized by means of Scanning Electronic Microscopy (SEM) and X-ray diffraction (DRX) techniques. The ball-to-powder weight ratio was 10:1. The analysed samples showed that the high-energy milling is an alternative route of the NbC synthesis. (author)

Methanesulfonic acid-assisted synthesis of N/S co-doped hierarchically porous carbon for high performance supercapacitors

Science.gov (United States)

Huo, Silu; Liu, Mingquan; Wu, Linlin; Liu, Mingjie; Xu, Min; Ni, Wei; Yan, Yi-Ming

2018-05-01

Nitrogen and sulfur co-doped carbons are considered as electrode materials for high performance supercapacitors, while their further development is still limited by complicated synthesis procedure, unsatisfied structure and low energy density. Developing a simple synthetic strategy to obtain rationally structured carbon materials and high supercapacitor performance is remaining a grand challenge. Herein, we describe the synthesis of nitrogen and sulfur co-doped hierarchical porous carbons as high performance supercapacitors electrode by a methanesulfonic acid-assisted one-step carbonization and activation of the freeze-dried precursors mixture. The as-prepared carbon material not only exhibits ideally hierarchical pores, but also realizes uniform nitrogen and sulfur co-doping. In 6.0 M KOH electrolyte, the material can achieve a high specific capacitance of 272 F g-1 at 1.0 A g-1 and a promising rate performance retaining 172 F g-1 even at 100 A g-1. Moreover, a fabricated symmetric supercapacitor based on as-prepared nitrogen and sulfur co-doped hierarchical porous carbon delivers high energy densities of 12.4 W h kg-1 and 8.0 W h kg-1 in 6.0 M KOH liquid and KOH/PVA solid-state electrolytes, respectively. This work presents a simple and effective methanesulfonic acid-assisted approach for mass production of heteroatomic doping hierarchical porous carbons for future energy storage applications.

Seedless Synthesis of Monodispersed Gold Nanorods with Remarkably High Yield: Synergistic Effect of Template Modification and Growth Kinetics Regulation.

Science.gov (United States)

Liu, Kang; Bu, Yanru; Zheng, Yuanhui; Jiang, Xuchuan; Yu, Aibing; Wang, Huanting

2017-03-08

Gold nanorods (AuNRs) are versatile materials due to their broadly tunable optical properties associated with their anisotropic feature. Conventional seed-mediated synthesis is, however, not only limited by the operational complexity and over-sensitivity towards subtle changes of experimental conditions but also suffers from low yield (≈15 %). A facile seedless method is reported to overcome these challenges. Monodispersed AuNRs with high yield (≈100 %) and highly adjustable longitudinal surface plasmon resonance (LSPR) are reproducibly synthesized. The parameters that influence the AuNRs growth were thoroughly investigated in terms of growth kinetics and soft-template regulation, offering a better understanding of the template-based mechanism. The facile synthesis, broad tunability of LSRP, high reproducibility, high yield, and ease of scale-up make this method promising for the future mass production of monodispersed AuNRs for applications in catalysis, sensing, and biomedicine. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Convergent Total Synthesis of (+)-Lithospermic Acid via a Late-Stage Intermolecular C–H Olefination

Science.gov (United States)

Wang, Dong-Hui; Yu, Jin-Quan

2011-01-01

The total synthesis of (+)-lithospermic acid is reported, which exploits two successive C–H activation reactions as the key steps. Rh-catalyzed carbene C–H insertion reaction using Davies’ catalyst built the dihydrobenzofuran core, and a late-stage intermolecular C–H olefination coupled the olefin unit with the dihydrobenzofuran core to construct the molecule in a highly convergent manner. PMID:21443224

Highly Enantioselective Rhodium-Catalyzed Addition of Arylboroxines to Simple Aryl Ketones: Efficient Synthesis of Escitalopram.

Science.gov (United States)

Huang, Linwei; Zhu, Jinbin; Jiao, Guangjun; Wang, Zheng; Yu, Xingxin; Deng, Wei-Ping; Tang, Wenjun

2016-03-24

Highly enantioselective additions of arylboroxines to simple aryl ketones have been achieved for the first time with a Rh/(R,R,R,R)-WingPhos catalyst, thus providing a range of chiral diaryl alkyl carbinols with excellent ee values and yields. (R,R,R,R)-WingPhos has been proven to be crucial for the high reactivity and enantioselectivity. The method has enabled a new, concise, and enantioselective synthesis of the antidepressant drug escitalopram. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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...

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

Science.gov (United States)

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

2016-03-01

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

Bacillus megaterium sporal peptidoglycan synthesis studied by high-resolution autoradiography.

Science.gov (United States)

Frehel, C; Ryter, A

1980-11-01

Cells of a Dap- Lys- mutant strain of Bacillus megaterium were pulse labeled with [3H]diaminopimelic acid at different times of growth and sporulation. They were processed for radioactivity measurements and high-resolution autoradiography either just after the pulse or after a chase in a nonradioactive medium until refractile forespores started to appear at time (t)4,5. In the pulse-labeled cells, autoradiographs and radioactivity measurements showed that the radioactivity incorporated during a pulse decreased abruptly after t0 and stayed at a low level until t5, although the forespore wall and cortex were formed between t4 and t5. In the pulse-chased bacteria, the acid-insoluble radioactivity, as well as the number of silver grains on autoradiographs, increased during the chase in cells labeled at t1 to t2, whereas it decreased in those labeled before t0. Furthermore, analysis of silver grain distribution showed that, in stage IV bacteria, grains were distributed at the outside of the forespore, mostly on the sporangium cell wall, when pulse-labeling occurred before or at t0; they were located along the cortex and in the forespore cytoplasm when labeling was made at t1 or t2. These facts show that [3H]diaminopimelic acid necessary for spore envelope synthesis was incorporated before their morphological appearance. Free or small diaminopimelic acid precursors entered the sporangium between t1 and t2. The appearance of silver grains in the forespore cytoplasm suggests that the forespore is implicated in sporal peptidoglycan synthesis.

Rapid Induction of Aldosterone Synthesis in Cultured Neonatal Rat Cardiomyocytes under High Glucose Conditions

Directory of Open Access Journals (Sweden)

Masami Fujisaki

2013-01-01

Full Text Available In addition to classical adrenal cortical biosynthetic pathway, there is increasing evidence that aldosterone is produced in extra-adrenal tissues. Although we previously reported aldosterone production in the heart, the concept of cardiac aldosterone synthesis remains controversial. This is partly due to lack of established experimental models representing aldosterone synthase (CYP11B2 expression in robustly reproducible fashion. We herein investigated suitable conditions in neonatal rat cardiomyocytes (NRCMs culture system producing CYP11B2 with considerable efficacy. NRCMs were cultured with various glucose doses for 2–24 hours. CYP11B2 mRNA expression and aldosterone concentrations secreted from NRCMs were determined using real-time PCR and enzyme immunoassay, respectively. We found that suitable conditions for CYP11B2 induction included four-hour incubation with high glucose conditions. Under these particular conditions, CYP11B2 expression, in accordance with aldosterone secretion, was significantly increased compared to those observed in the cells cultured under standard-glucose condition. Angiotensin II receptor blocker partially inhibited this CYP11B2 induction, suggesting that there is local renin-angiotensin-aldosterone system activation under high glucose conditions. The suitable conditions for CYP11B2 induction in NRCMs culture system are now clarified: high-glucose conditions with relatively brief period of culture promote CYP11B2 expression in cardiomyocytes. The current system will help to accelerate further progress in research on cardiac tissue aldosterone synthesis.

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.

Synthesis, characterization, and cytotoxicity evaluation of high-magnetization multifunctional nanoclusters

Energy Technology Data Exchange (ETDEWEB)

Petran, Anca; Radu, Teodora; Nan, Alexandrina [National Institute for Research and Development of Isotopic and Molecular Technologies (Romania); Olteanu, Diana; Filip, Adriana, E-mail: adrianafilip33@yahoo.com; Clichici, Simona; Baldea, Ioana [Iuliu Hatieganu University of Medicine and Pharmacy, Department of Physiology (Romania); Suciu, Maria; Turcu, Rodica, E-mail: rodica.turcu@itim-cj.ro [National Institute for Research and Development of Isotopic and Molecular Technologies (Romania)

2017-01-15

The paper presents the synthesis, characterization, and in vitro cytotoxicity tests of Fe{sub 3}O{sub 4} magnetic nanoclusters coated with ethylenediaminetetraacetic acid disodium salt (EDTA). Electron microscopy analysis (SEM) evidences that magnetite nanoparticles are closely packed into the clusters stabilized with EDTA with well-defined near spherical shapes and sizes in the range 100–200 nm. From XRD measurements, we determined the mean size of the crystallites inside the magnetic cluster about 36 nm. The saturation magnetization determined for the magnetic clusters stabilized with EDTA has high value, about 81.7 emu/g at 300 K. X-ray photoelectron spectroscopy has been used to determine both the elemental and chemical structure of the magnetic cluster surface. In vitro studies have shown that the magnetic clusters at low doses did not induce toxicity on human umbilical vein endothelial cells or lesions of the cell membrane. In contrast, at high doses, the magnetic clusters increased the lipid peroxidation and reduced the leakage of a cytoplasmic enzyme, lactate dehydrogenase (LDH), in parallel with increasing the antioxidant defense.

Synthesis of highly fluorescent hydrophobic carbon dots by hot injection method using Paraplast as precursor

International Nuclear Information System (INIS)

Talib, Abou; Pandey, Sunil; Thakur, Mukeshchand; Wu, Hui-Fen

2015-01-01

We have reported synthesis of bright blue colored hydrophobic carbon dots (hC-dots) using highly pure blend of polymers called Paraplast. We developed a hot injection method for making nearly monodispersed hC-dots with a diameter in a range: 5–30 nm as confirmed by high resolution transmission electron microscopy (HRTEM). The involvement of various functional groups was confirmed by Fourier transform infra-red (FTIR) spectroscopy. These hC-dots were incubated with breast cancer stem cells in order to check the entry as well as biological imaging. The cells were analyzed using epifluorescent microscopy. hC-dots showed concentration dependent cytotoxicity (LD 50 : 50 mg/ml) and could be used for bioimaging even at lower concentration (0.5 mg/ml). hC-dots were found to be versatile agents for peeping inside the cells which could also be used for delivery of water insoluble chemotherapeutic agents to variety of solid tumors. - Highlights: • Synthesis of hydrophobic carbon dots from polymer based Paraplast • Deep blue color under the influence of UV light • Typical optical properties used for biological imaging • Biological imaging of breast cancer stem cells revealing potential of carbon dots

Synthesis of highly fluorescent hydrophobic carbon dots by hot injection method using Paraplast as precursor

Energy Technology Data Exchange (ETDEWEB)

Talib, Abou [Doctoral Degree Program in Marine Biotechnology, National Sun Yat-Sen University, Kaohsiung 80424, Taiwan (China); Pandey, Sunil [Department of Chemistry, National Sun Yat-Sen University, 70, Lien-Hai Road, Kaohsiung 80424, Taiwan (China); Center for Nanoscience and Nanotechnology, National Sun Yat-Sen University, 70, Lien-Hai Road, Kaohsiung 80424, Taiwan (China); Thakur, Mukeshchand [Department of Chemistry, National Sun Yat-Sen University, 70, Lien-Hai Road, Kaohsiung 80424, Taiwan (China); Wu, Hui-Fen, E-mail: hui@faculty.nsysu.edu.tw [Department of Chemistry, National Sun Yat-Sen University, 70, Lien-Hai Road, Kaohsiung 80424, Taiwan (China); Center for Nanoscience and Nanotechnology, National Sun Yat-Sen University, 70, Lien-Hai Road, Kaohsiung 80424, Taiwan (China); Doctoral Degree Program in Marine Biotechnology, National Sun Yat-Sen University, Kaohsiung 80424, Taiwan (China); School of Pharmacy, College of Pharmacy, Kaohsiung Medical University, Kaohsiung 800, Taiwan (China); Institute of Medical Science and Technology, National Sun Yat-Sen University, Kaohsiung, 80424, Taiwan (China)

2015-03-01

We have reported synthesis of bright blue colored hydrophobic carbon dots (hC-dots) using highly pure blend of polymers called Paraplast. We developed a hot injection method for making nearly monodispersed hC-dots with a diameter in a range: 5–30 nm as confirmed by high resolution transmission electron microscopy (HRTEM). The involvement of various functional groups was confirmed by Fourier transform infra-red (FTIR) spectroscopy. These hC-dots were incubated with breast cancer stem cells in order to check the entry as well as biological imaging. The cells were analyzed using epifluorescent microscopy. hC-dots showed concentration dependent cytotoxicity (LD{sub 50}: 50 mg/ml) and could be used for bioimaging even at lower concentration (0.5 mg/ml). hC-dots were found to be versatile agents for peeping inside the cells which could also be used for delivery of water insoluble chemotherapeutic agents to variety of solid tumors. - Highlights: • Synthesis of hydrophobic carbon dots from polymer based Paraplast • Deep blue color under the influence of UV light • Typical optical properties used for biological imaging • Biological imaging of breast cancer stem cells revealing potential of carbon dots.

Straightforward high-pressure synthesis and characterization of indium-based thiospinels: photocatalytic potential for hydrogen production

Energy Technology Data Exchange (ETDEWEB)

Falcon, Horacio [Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco (Spain); NANOTEC (Centro de Investigacion en Nanociencia y Nanotecnologia), Universidad Tecnologica Nacional-Facultad Regional Cordoba, Cordoba (Argentina); Tartaj, Pedro; Alonso, Jose Antonio [Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco (Spain); Vaquero, Fernando; Navarro, Rufino M.; Fierro, Jose Luis G. [Instituto de Catalisis y Petroleoquimica, CSIC, Cantoblanco, Madrid (Spain); Bolletta, Juan P.; Paoli, Juan M. de; Carbonio, Raul E. [INFIQC - CONICET, Departamento de Fisicoquimica, Facultad de Ciencias Quimicas, Universidad Nacional de Cordoba (Argentina); Fernandez-Diaz, Maria Teresa [Institut Laue Langevin, Grenoble (France)

2016-04-15

Ternary chalcogenides (AB{sub 2}X{sub 4}) based on the spinel structure are gaining a great deal of attention because of the possibility of tuning their magnetic and optoelectronic properties not only by changing chemical composition but also by altering their degree of inversion. Here we report a rapid high-pressure synthetic method for the synthesis of MIn{sub 2}S{sub 4} powders starting from commercially available solid sulfides. We prove the versatility of our method by reporting the synthesis of six members of the MIn{sub 2}S{sub 4} family (M = Mn, Fe, Co, Ni, Zn, and Cd) under high-pressure conditions (3.5 GPa); these compounds show complete to moderate degrees of inversion. Furthermore, this family covers a spectral region that includes visible band gaps. Interestingly, the structural refinement carried out by X-ray and neutron diffraction allows one to establish positive correlations between the gap and different parameters, including the degree of inversion. Finally, as a proof-of-concept, these ternary chalcogenides show moderate photocatalytic hydrogen production from aqueous solutions. (Copyright copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Highly Selective Synthesis of Catalytically Active Monodisperse Rhodium Nanocubes

Energy Technology Data Exchange (ETDEWEB)

Zhang, Y.; Grass, M.E.; Kuhn, J.N.; Tao, F.; Habas, S.E.; Huang, W.; Yang, P.; Somorjai, G.A.

2009-02-21

Synthesis of monodisperse and shape-controlled colloidal inorganic nanocrystals (NCs) is of increasing scientific interest and technological significance. Recently, shape control of Pt, Pd, Ag, Au, and Rh NCs has been obtained by tuning growth kinetics in various solution-phase approaches, including modified polyol methods, seeded growth by polyol reduction, thermolysis of organometallics, and micelle techniques. Control of reduction kinetics of the noble metal precursors and regulation of the relative growth rates of low-index planes (i.e. {l_brace}100{r_brace} and {l_brace}111{r_brace}) via selective adsorption of selected chemical species are two keys for achieving shape modification of noble metal NCs. One application for noble metal NCs of well-defined shape is in understanding how NC faceting (determines which crystallographic planes are exposed) affects catalytic performance. Rh NCs are used in many catalytic reactions, including hydrogenation, hydroformylation, hydrocarbonylation, and combustion reactions. Shape manipulation of Rh NCs may be important in understanding how faceting on the nanoscale affects catalytic properties, but such control is challenging and there are fewer reports on the shape control of Rh NCs compared to other noble metals. Xia and coworkers obtained Rh multipods exhibiting interesting surface plasmonic properties by a polyol approach. The Somorjai and Tilley groups synthesized crystalline Rh multipods, cubes, horns and cuboctahedra, via polyol seeded growth. Son and colleagues prepared catalytically active monodisperse oleylamine-capped tetrahedral Rh NCs for the hydrogenation of arenes via an organometallic route. More recently, the Somorjai group synthesized sizetunable monodisperse Rh NCs using a one-step polyol technique. In this Communication, we report the highly selective synthesis of catalytically active, monodisperse Rh nanocubes of < 10 nm by a seedless polyol method. In this approach, Br{sup -} ions from trimethyl

The growth of high density network of MOF nano-crystals across macroporous metal substrates - Solvothermal synthesis versus rapid thermal deposition

Science.gov (United States)

Maina, James W.; Gonzalo, Cristina Pozo; Merenda, Andrea; Kong, Lingxue; Schütz, Jürg A.; Dumée, Ludovic F.

2018-01-01

Fabrication of metal organic framework (MOF) films and membranes across macro-porous metal substrates is extremely challenging, due to the large pore sizes across the substrates, poor wettability, and the lack of sufficient reactive functional groups on the surface, which prevent high density nucleation of MOF crystals. Herein, macroporous stainless steel substrates (pore size 44 × 40 μm) are functionalized with amine functional groups, and the growth of ZIF-8 crystals investigated through both solvothermal synthesis and rapid thermal deposition (RTD), to assess the role of synthesis routes in the resultant membranes microstructure, and subsequently their performance. Although a high density of well interconnected MOF crystals was observed across the modified substrates following both techniques, RTD was found to be a much more efficient route, yielding high quality membranes under 1 h, as opposed to the 24 h required for solvothermal synthesis. The RTD membranes also exhibited high gas permeance, with He permeance of up to 2.954 ± 0.119 × 10-6 mol m-2 s-1 Pa-1, and Knudsen selectivities for He/N2, Ar/N2 and CO2/N2, suggesting the membranes were almost defect free. This work opens up route for efficient fabrication of MOF films and membranes across macro-porous metal supports, with potential application in electrically mediated separation applications.

Highly Efficient Method for Solvent-Free Synthesis of Diarylmethane ...

African Journals Online (AJOL)

NICO

2011-02-25

Feb 25, 2011 ... aFaculty of Chemistry, Bu-Ali Sina University, P.O. Box 651783868, Hamedan, Iran. ... Arylmethanes are useful compounds in organic synthesis and industry1 ... ketones,9,10 catalytic condensation of the Grignard reagent with.

Copper(II)-catalyzed exo and enantioselective cycloadditions of azomethine imines.

Science.gov (United States)

Sibi, Mukund P; Rane, Digamber; Stanley, Levi M; Soeta, Takahiro

2008-07-17

A strategy for exo and enantioselective 1,3-dipolar cycloaddition of azomethine imines to 2-acryloyl-3-pyrazolidinone is described. The corresponding cycloadducts are isolated with high diastereoselectivities (up to >96:4 exo/endo) and enantioselectivities (up to 98% ee).

Recent development on the synthesis of calixcrowns and their application for cesium removal from high-level liquid waste

International Nuclear Information System (INIS)

Zhu Xiaowen; Gao Jianxun; Wang Jianchen; Yu Bo; Song Chongli

2002-01-01

The synthesis, extraction properties and molecular modeling of calixcrowns in concern of cesium removal is reviewed briefly. In particular, calix [4] crown-6 and some of its derivatives have been shown to be highly selective extractants for cesium ions

Synthesis of high-purity Li{sub 8}ZrO{sub 6} powder by solid state reaction under hydrogen atmosphere

Energy Technology Data Exchange (ETDEWEB)

Shin-mura, Kiyoto; Otani, Yu; Ogawa, Seiya [Course of Mechanical Engineering, Graduate School of Engineering, Tokai University, 4-1-1 Kitakaname, Hiratsuka, Kanagawa 259-1292 (Japan); Niwa, Eiki; Hashimoto, Takuya [Department of Physics, College of Humanities and Sciences, Nihon University, 3-8-1 Sakurajousui, Setagaya-ku, Tokyo 156-8550 (Japan); Hoshino, Tsuyoshi [Breeding Functional Materials Development Group, Department of Blanket Systems Research, Rokkasho Fusion Institute, Sector of Fusion Research and Development, Japan Atomic Energy Agency, 2-166 Obuchi, Omotedate, Rokkasho-mura, Kamikita-gun, Aomori 039-3212 (Japan); Sasaki, Kazuya, E-mail: k_sasaki@tokai-u.ac.jp [Course of Mechanical Engineering, Graduate School of Engineering, Tokai University, 4-1-1 Kitakaname, Hiratsuka, Kanagawa 259-1292 (Japan); Department of Prime Mover Engineering, School of Engineering, Tokai University, 4-1-1 Kitakaname, Hiratsuka, Kanagawa 259-1292 (Japan)

2016-11-01

Highlights: • A fine pure Li{sub 8}ZrO{sub 6} powder was synthesized by using Li{sub 2}CO{sub 3} and ZrO{sub 2} via a solid state reaction. • Influences on the purity of product powder, lattice defect, and crystal orientation were revealed. • The suitable synthesis conditions of the fine and high purity Li{sub 8}ZrO{sub 6} powder were found. • The reaction process of the synthesis of Li{sub 8}ZrO{sub 6} was estimated. - Abstract: Li{sub 8}ZrO{sub 6} contains a large amount of Li and has a significant potential as a tritium breeder. However, few syntheses of fine-grain, high-purity Li{sub 8}ZrO{sub 6} powder have been reported. In this study, a high-purity powder of Li{sub 8}ZrO{sub 6} was synthesized by solid state reaction under hydrogen atmosphere combined with an effective lithium source and a suitable initial Li:Zr molar ratio. Mixed powders of Li{sub 2}CO{sub 3} and ZrO{sub 2} were fired at around 630 °C in H{sub 2} for several hours and several firing cycles. The low firing temperature inhibited the vaporization of Li during the heating, so that excessive amounts of Li were not needed for the synthesis, and the Li:Zr ratio in the starting material was 10:1 (mol:mol). In this synthesis, Li{sub 2}O was generated via the decomposition of Li{sub 2}CO{sub 3} during firing in H{sub 2}, and reacted with ZrO{sub 2} to form Li{sub 6}Zr{sub 2}O{sub 7}, which reacted with itself to form Li{sub 8}ZrO{sub 6}.

Fabrication of intermetallic NiAl by self-propagating high-temperature synthesis reaction using aluminium nanopowder under high pressure

CERN Document Server

Dong Shu Shan; Cheng Hai Yong; Yang Hai Bin; Zou Guang Tian

2002-01-01

By using aluminium nanopowder prepared by wire electrical explosion, pure monophase NiAl compound with fine crystallites (<=10 mu m) and good densification (98% of the theoretical green density) was successfully fabricated by means of self-propagating high-temperature synthesis (SHS) under a high pressure of 50 MPa. Investigation shows that, due to the physical and chemical characteristics of the nanoparticles, the SHS reaction mode and mechanism are distinct from those when using conventional coarse-grained reactants. The SHS reaction process depends on the thermal conditions related to pressure and can occur at a dramatically low temperature of 308 sup o C, which cannot be expected in conventional SHS reaction. With increasing pressure, the SHS explosive ignition temperature (T sub i sub g) of forming NiAl decreases due to thermal and kinetic effects.

Fluidized bed gasification of high tonnage sorghum, cotton gin trash and beef cattle manure: Evaluation of synthesis gas production

International Nuclear Information System (INIS)

Maglinao, Amado L.; Capareda, Sergio C.; Nam, Hyungseok

2015-01-01

Highlights: • High tonnage sorghum, cotton gin trash and beef cattle manure were characterized and gasified in a fluidized bed reactor. • Biomass gasification at 730 °C and ER = 0.35 produced synthesis gas with an average energy content of 4.19 MJ Nm −3 . • Synthesis gas heating value and yield were relatively constant at reaction temperatures from 730 °C to 800 °C. • Optimum hydrogen production on HTS gasification was achieved at 780 °C temperature and ER of 0.4. - Abstract: Fluidized bed gasification using high-tonnage sorghum, cotton gin trash and beef cattle manure was performed in a pilot scale bubbling fluidized bed reactor equipped with the necessary feedback control system. Characterization of biomass showed that the high-tonnage sorghum had the highest energy and carbon content of 19.58 MJ kg −1 and 42.29% wt , respectively among the three feed stocks. At 730 °C reaction temperature and equivalence ratio of 0.35, comparable yields of methane, nitrogen and carbon dioxide (within ± 1.4% vol ) were observed in all three feed stocks. The gasification system produced synthesis gas with an average heating value of 4.19 ± 0.09 MJ Nm −3 and an average yield of 1.98 ± 0.1 Nm 3 kg −1 of biomass. Carbon conversion and gasification efficiencies indicated that most of the carbon was converted to gaseous products (85% average ) while 48% average of the energy from the biomass was converted into combustible gas. The production of hydrogen was significantly affected by the biomass used during gasification. The synthesis gas heating value and yield were relatively constant at reaction temperatures from 730 °C to 800 °C. Utilizing high-tonnage sorghum, the optimum hydrogen production during gasification was achieved at a reaction temperature of 780 °C and an equivalence ratio of 0.40.

Robust image registration for multiple exposure high dynamic range image synthesis

Science.gov (United States)

Yao, Susu

2011-03-01

Image registration is an important preprocessing technique in high dynamic range (HDR) image synthesis. This paper proposed a robust image registration method for aligning a group of low dynamic range images (LDR) that are captured with different exposure times. Illumination change and photometric distortion between two images would result in inaccurate registration. We propose to transform intensity image data into phase congruency to eliminate the effect of the changes in image brightness and use phase cross correlation in the Fourier transform domain to perform image registration. Considering the presence of non-overlapped regions due to photometric distortion, evolutionary programming is applied to search for the accurate translation parameters so that the accuracy of registration is able to be achieved at a hundredth of a pixel level. The proposed algorithm works well for under and over-exposed image registration. It has been applied to align LDR images for synthesizing high quality HDR images..

Electrochemical synthesis of highly ordered polypyrrole on copper modified aluminium substrates

International Nuclear Information System (INIS)

Siddaramanna, Ashoka; Saleema, N.; Sarkar, D.K.

2014-01-01

Fabrication of highly ordered conducting polymers on metal surfaces has received a significant interest owing to their potential applications in organic electronic devices. In this context, we have developed a simple method for the synthesis of highly ordered polypyrrole (PPy) on copper modified aluminium surfaces via electrochemical polymerization process. A series of characteristic peaks of PPy evidenced on the infrared spectra of these surfaces confirm the formation of PPy. The X-ray diffraction (XRD) pattern of PPy deposited on copper modified aluminium surfaces also confirmed the deposition of PPy as a sharp and intense peak at 2θ angle of 23° attributable to PPy is observed while this peak is absent on PPy deposited on as-received aluminium surfaces. An atomic model of the interface of PPy/Cu has been presented based on the inter-atomic distance of copper–copper of (1 0 0) plane and the inter-monomer distance of PPy, to describe the ordering of PPy on Cu modified Al surfaces.

Synthesis of graphene by MEVVA source ion implantation

International Nuclear Information System (INIS)

Ying, J.J.; Xiao, X.H.; Dai, Z.G.; Wu, W.; Li, W.Q.; Mei, F.; Cai, G.X.; Ren, F.; Jiang, C.Z.

2013-01-01

Ion implantation provides a new synthesis route for graphene, and few-layered graphene synthesis by ion implantation has been reported. Here we show the synthesis of a single layer of high-quality graphene by Metal Vapor Vacuum Arc (MEVVA) source ion implantation. Polycrystalline nickel and copper thin films are implanted with MEVVA source carbon ions at 40 kV, followed by high-temperature thermal annealing and quenching. A Raman spectrum is applied to probe the quality and thickness of the prepared graphene. A single layer of high-quality graphene is grown on the nickel films, but not on the copper films. The growth mechanisms on the nickel and copper films are explained. MEVVA source ion implantation has been widely applied in industrial applications, demonstrating that this synthesis method can be generalized for industrial production

The synthesis of amphipathic prodrugs of 1,2-diol drugs with saccharide conjugates by high regioselective enzymatic protocol.

Science.gov (United States)

Quan, Jing; Chen, Zhichun; Han, Chengyou; Lin, Xianfu

2007-02-15

A facile, high regioselective enzymatic synthesis approach for the preparation of amphipathic prodrugs with saccharides of mephenesin and chlorphenesin was developed. Firstly, transesterification of two drugs with divinyl dicarboxylates with different carbon chain length was performed under the catalysis of Candida antarctica lipase acrylic resin and Lipozyme in anhydrous acetone at 50 degrees C, respectively. A series of lipophilic derivatives with vinyl groups of mephenesin and chlorphenesin were prepared. The influences of different organic solvents, enzyme sources, reaction time, and the acylation reagents on the synthesis of vinyl esters were investigated. And then, protease-catalyzed high regioselective acylation of D-glucose and D-mannose with vinyl esters of mephenesin and chlorphenesin gave drug-saccharide derivatives in good yields. The studies of lipophilicity and hydrolysis in vitro of prodrugs verified that drug-saccharide derivatives had amphipathic properties, and both lipophilic and amphipathic drug derivatives had obvious controlled release characteristics.

The rapid synthesis of high purity [{sup 18}F]butyrophenone neuroleptics from nitro precursors for PET study

Energy Technology Data Exchange (ETDEWEB)

Hashizume, Kazunari; Hashimoto, Naoto; Kato, Hiroo; Cork, D G; Miyake, Yoshihiro [National Cardiovascular Center, Suita, Osaka (Japan)

1995-04-01

We have completed rapid syntheses of [{sup 18}F]butyrophenone neuroleptics ([{sup 18}F]haloperidol and [{sup 18}F]spiperone) from their nitro precursors in high radiochemical yields (up to 21%) by combining a one-step nitro-fluoro exchange reaction and a novel high performance liquid chromatography (HPLC) separation method. The synthesis time was ca. 95 min and both the radiochemical and chemical purities of the labeled products were over 99%. (author).

Template synthesis of highly crystalline and monodisperse iron oxide pigments of nanosize

International Nuclear Information System (INIS)

Sreeram, Kalarical Janardhanan; Indumathy, Ramasamy; Rajaram, Ananthanarayanan; Nair, Balachandran Unni; Ramasami, Thirumalachari

2006-01-01

Synthesis of highly crystalline and monodisperse iron oxide nanoparticles is reported. The separation of Fe centers through site-specific binding to a polysaccharide-alginate matrix enables the generation of particles with a monodisperse or narrow size distribution character, resulting in transparent pigments. Site-specific interactions coupled with gel like character of alginate is proposed as the mechanism behind generation of lower particle sizes. Alginate-Fe complexes developed were subjected to heat treatment to provide for crystalline character and development of hematite (α-Fe 2 O 3 ). Conditions most ideal for achieving monodispersity and lower sizes have been optimized and confirmed through microscopic and photon correlation spectroscopic measurements

Synthesis of high specific activity carbon-11 labeled tracers for neuroreceptor studies

International Nuclear Information System (INIS)

Dannals, R.F.; Ravert, H.T.; Wilson, A.A.; Wagner, H.N. Jr; Johns Hopkins Medical Institutions, Baltimore, MD

1989-01-01

The use of short-lived positron-emitting radiotracers together with positron emission tomography (PET) has allowed scientists to acquire previously inaccessible information regarding problems in physiology, biochemistry, and pharmacology in the living human body. In the past five years, successes in the application of PET to the non-invasive determination of the spatial distribution and regional concentration of a variety of neurotransmitter binding sites within the living brain often followed the successful selections and syntheses of appropriately radiolabeled ligands. This presentation concentrates on the synthesis of these high specific activity radiotracers for neuroreceptor PET studies labeled specifically with carbon-11. (author). 15 refs.; 1 fig

Synthesis of high-quality mesoporous silicon particles for enhanced lithium storage performance

Energy Technology Data Exchange (ETDEWEB)

Wang, Chundong, E-mail: apcdwang@hust.edu.cn [School of Optical and Electronic Information, Huazhong University of Science and Technology, Wuhan 430074 (China); Center of Super-Diamond and Advanced Films (COSDAF), Department of Physics and Materials Science, City University of Hong Kong, Kowloon, Hong Kong SAR (China); Ren, Jianguo [Center of Super-Diamond and Advanced Films (COSDAF), Department of Physics and Materials Science, City University of Hong Kong, Kowloon, Hong Kong SAR (China); Chen, Hao [Department of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou (China); Zhang, Yi [School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan, 430073 (China); Ostrikov, Kostya [School of Chemistry, Physics, and Mechanical Engineering, Queensland University of Technology, Brisbane 4000, QLD (Australia); Manufacturing Flagship, CSIRO, P. O. Box 218, Lindfield, NSW 2070 (Australia); Zhang, Wenjun [Center of Super-Diamond and Advanced Films (COSDAF), Department of Physics and Materials Science, City University of Hong Kong, Kowloon, Hong Kong SAR (China); Li, Yi, E-mail: liyi@suda.edu.cn [Department of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou (China); Center of Super-Diamond and Advanced Films (COSDAF), Department of Physics and Materials Science, City University of Hong Kong, Kowloon, Hong Kong SAR (China)

2016-04-15

Silicon has been considered as one of the most promising anode materials for high-capacity lithium-ion batteries (LIBs) due to its ultrahigh theoretical capacity, abundance, and environmentally benign nature. Nonetheless, the severe break during the prolonged cycling results in poor electrochemical performance, which hinders its practical application. Herein, we report the synthesis of novel mesoporous silicon particles with a facile template method by using a magnesiothermic reduction for LIBs. The obtained silicon nanoparticles are highly porous with densely porous cavities (20–40 nm) on the wall, of which it presents good crystallization. Electrochemical measurements showed that the mesoporous silicon nanoparticles delivered a high reversible specific capacity of 910 mA h g{sup −1} at a high current density of 1200 mA g{sup −1} over 50 cycles. The specific capacity at such high current density is still over twofold than that of commercial graphite anode, suggesting that the nanoporous Si architectures is suitable for high-performance Si-based anodes for lithium ion batteries in terms of capacity, cycle life, and rate capacity. - Highlights: • Silica nanotubes were prepared with a facile template method. • Novel mesoporous silicon particles were obtained by magnesiothermic reduction. • High-Performance LIBs were achieved by using mesoporous Si particle Electrodes.

Self-propagating high-temperature synthesis of TiC-WC composite materials

International Nuclear Information System (INIS)

Mas-Guindal, M.J.; Contreras, L.; Turrillas, X.; Vaughan, G.B.M.; Kvick, A.; Rodriguez, M.A.

2006-01-01

TiC-WC composites have been obtained in situ by self-propagating high-temperature synthesis (SHS) from a mixture of compacted powders of elemental titanium, tungsten and graphite. The Rietveld method has proved to be a useful tool to quantify the different phases in the reaction and calculate the cell parameters of the solid solution found in the products. The reaction has also been followed in real time by X-ray diffraction at the European Synchrotron Radiation Facility (ESRF ID-11 Materials Science Beamline). The mechanism of the reaction is discussed in terms of the diffusion of liquid titanium to yield titanium carbide with a solid solution of tungsten. The microstructures of the materials obtained by this method are presented

Facile high-yield synthesis of polyaniline nanosticks with intrinsic stability and electrical conductivity.

Science.gov (United States)

Li, Xin-Gui; Li, Ang; Huang, Mei-Rong

2008-01-01

Chemical oxidative polymerization at 15 degrees C was used for the simple and productive synthesis of polyaniline (PAN) nanosticks. The effect of polymerization media on the yield, size, stability, and electrical conductivity of the PAN nanosticks was studied by changing the concentration and nature of the acid medium and oxidant and by introducing organic solvent. Molecular and supramolecular structure, size, and size distribution of the PAN nanosticks were characterized by UV/Vis and IR spectroscopy, X-ray diffraction, laser particle-size analysis, and transmission electron microscopy. Introduction of organic solvent is advantageous for enhancing the yield of PAN nanosticks but disadvantageous for formation of PAN nanosticks with small size and high conductivity. The concentration and nature of the acid medium have a major influence on the polymerization yield and conductivity of the nanosized PAN. The average diameter and length of PAN nanosticks produced with 2 M HNO(3) and 0.5 M H(2)SO(4) as acid media are about 40 and 300 nm, respectively. The PAN nanosticks obtained in an optimal medium (i.e., 2 M HNO(3)) exhibit the highest conductivity of 2.23 S cm(-1) and the highest yield of 80.7 %. A mechanism of formation of nanosticks instead of nanoparticles is proposed. Nanocomposite films of the PAN nanosticks with poly(vinyl alcohol) show a low percolation threshold of 0.2 wt %, at which the film retains almost the same transparency and strength as pure poly(vinyl alcohol) but 262 000 times the conductivity of pure poly(vinyl alcohol) film. The present synthesis of PAN nanosticks requires no external stabilizer and provides a facile and direct route for fabrication of PAN nanosticks with high yield, controllable size, intrinsic self-stability, strong redispersibility, high purity, and optimizable conductivity.

Method of preparing uridine-diphospho-/sup 14/C-D-glucose of high molar activity and radiochemical purity by enzyme synthesis

Energy Technology Data Exchange (ETDEWEB)

Farkas, V; Biely, P; Koelbl, J

1980-06-15

A new method is described of enzyme synthesis of uridine-diphospho-/sup 14/C-D-glucose of high molar activity. After conversion of the initial /sup 14/C-D-glucose, the accompanying sugar phosphates and nucleoside-5'-phosphates are selectively hydrolyzed by the action of alkaline phosphatase in the presence of phenolphthalein as an indicator. Uridine-diphospho-/sup 14/C-D-glucose is separated by paper chromatography from the reaction mixture thus modified. Synthesis yields range within 75% and 85% relative to the starting /sup 14/C-D-glucose.

Synthesis of highly stable silver nanoparticles through a novel green method using Mirabillis jalapa for antibacterial, nonlinear optical applications

Science.gov (United States)

Pugazhendhi, S.; Palanisamy, P. K.; Jayavel, R.

2018-05-01

Green synthesis techniques are developing as more simplistic and eco-friendly approach for the synthesis of metal nanoparticles compared to chemical reduction methods. Herein we report Synthesis of highly stable silver nanoparticles using Mirabillis jalapa seed extract as a reducing and capping agent. The as-prepared silver nanoparticles were characterized by UV-vis spectroscopy (UV-vis) to confirm the formation of silver nanoparticles by its characteristic surface plasmon resonance peak observed at 420 nm. The Powder X-ray diffraction (P-XRD) revealed the structure and crystalline nature of synthesized silver nanoparticles, The Fourier transform infra-red spectroscopic (FT-IR) revealed the presence of the biomolecules in the extract that acted as reducing as well stabilizing agent. The high resolution transmission electron microscopic (HRTEM) images divulged that the synthesized silver nanoparticles were spherical in shape and poly dispersed. The energy dispersive X-ray diffraction (EDX) profile revealed the elements present in the as-synthesized colloidal silver nanoparticles and its percentages. The Zeta potential measured for silver nanoparticles evidenced that the prepared silver nanoparticles owned high stability in room temperature itself. The as-synthesized silver nanoparticles (AgNPs) in colloidal form were showed good antimicrobial effects and it's were found to exhibit third order optical nonlinearity as studied by Z-scan technique using 532 nm Nd:YAG (SHG) CW laser beam (COHERENT-Compass 215 M-50 diode pumped) output as source. The negative nonlinearity observed was well utilized for the study of optical limiting behavior of the silver nanoparticles.

Facile Synthesis Polyethylene Glycol Coated Magnetite Nanoparticles for High Colloidal Stability

Directory of Open Access Journals (Sweden)

Mun Foong Tai

2016-01-01

Full Text Available Polyethylene glycol (PEG is one of the most frequently used synthetic polymers for surface modifications of magnetite nanoparticles (MNPs to provide a new opportunity for constructing high colloidal stability. Herein, a facile in situ coprecipitation technique is described for the synthesis of PEG coated MNPs using ammonium hydroxide as the precipitating agent. The structure and morphology of the prepared PEG coated MNPs samples were characterized by Fourier transform infrared (FTIR spectroscopy, X-ray spectroscopy, thermogravimetric analysis (TGA, and the high resolution transmission electron microscopy (HRTEM. In this study, all samples demonstrated hydrodynamic size in the range of 32 to 43 nm with narrow size distribution. In addition, the magnetic properties of resultant samples were investigated using a vibrating sample magnetometer (VSM to reveal the superparamagnetic behaviour with saturation magnetization. The saturation magnetization of PEG coated MNPs samples was in the range of 63 to 66 emu/g at 300 K. Interestingly, it was found that 1.0 g of PEG coated MNPs exhibited high colloidal stability in a basic solution (pH = 10 and nitrile (NBR latex up to 21 days as compared to the unmodified MNPs during the sedimentation test.

On-Surface Synthesis by Click Chemistry Investigated by STM and XPS

DEFF Research Database (Denmark)

Vadapoo, Sundar Raja

2014-01-01

Molecular synthesis is essential in the bottom-up approach of achieving highly stable nanostructures. On-surface synthesis is highly interesting from the basic science of view to improve the understanding of molecular behavior adsorbed on metal surfaces, and has potential applications such as mol......Molecular synthesis is essential in the bottom-up approach of achieving highly stable nanostructures. On-surface synthesis is highly interesting from the basic science of view to improve the understanding of molecular behavior adsorbed on metal surfaces, and has potential applications...... such as molecular electronics and surface functionalization. In this thesis, a well-defined click chemistry approach is followed, with the study of azide-alkyne cycloaddition on Cu(111) surface in UHV environment. A successful achievement of the click reaction product via on-surface synthesis has been shown, which...

The synthesis of nanostructured, phase pure catalysts by hydrodynamic cavitation

Energy Technology Data Exchange (ETDEWEB)

Moser, W.R.; Sunstrom, J.E.; Marshik-Geurts, B.J. [Worcester Polytechnic Institute, Worcester, MA (United States)

1995-12-01

A new process for the synthesis of advanced catalytic materials based on performing the synthesis under hydrodynamic cavitation conditions has been discovered. This continuous process for catalyst synthesis resulted in the formation of both supported and unsupported catalysts. The advantage of the process over classical methods of synthesis is that it permits the formation of a wide variety of nanostructured catalysts in exceptionally high phase purities. The synthesis of platinum and palladium catalysts supported on alumina and other supports resulted in high dispersions of the noble metals. The synthesis of alpha, beta- and gamma-bismuth molybdates resulted in catalysts having superior phase purities as compared to several other classical methods of synthesis. The beta-bismuth molybdate was synthesized directly onto Cabosil. These studies showed that the particle size of the active component could be varied from a few manometers to much larger grains. The process enabled the synthesis of other complex metal oxides like perovskites as pure phases. The process uses a commercially available Microfluidizer.

Microwave-Hydrothermal Synthesis and Characterization of High-Purity Nb Doped BaTiO3 Nanocrystals

Directory of Open Access Journals (Sweden)

A. Khanfekr

2014-01-01

Full Text Available The synthesis of Nb doped BaTiO3 has been investigated under Microwave-Hydrothermal (MH conditions in the temperature of 150°C for only 2 h using C16H36O4Ti, BaH2O2.8H2O and NbCl5 as Ba, Ti and  Nb sources, respectively.  Typical experiments performed on MH processing have not yet reported for Nb doped BaTiO3.  In the MH process, the formation of high purity nano tetragonal Nb-BaTiO3 was strongly enhanced. New hydrothermal method was used instead of the previous solid state reaction for the BaTiO3±Nb2O3 system. The new method uses high pressure to create nano dimension particles in a lower time and temperature. In case of the phase evolution studies, the XRD pattern measurements and Raman spectroscopy were performed. TEM and FE-SEM images were taken for the detailed analysis of the particle size, surface and morphology.  Synthesis of Nb doped BaTiO3 with the Microwave-hydrothermal provides an advantage of fast crystallization and reduced crystal size when compared to existing methods.

Product engineering by high-temperature flame synthesis

DEFF Research Database (Denmark)

Johannessen, Tue; Johansen, Johnny; Mosleh, Majid

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...... hardware by direct deposition of catalysts on process equipment • Modifications of the substrate surfaces to obtain good adhesion during flame-coating • Formation of membrane layers by gas-phase deposition of nano-particles • Catalyst deposition in micro-reactors for rapid catalyst screening...

Bromide (Br)--Based Synthesis of Ag Nanocubes with High-Yield.

Science.gov (United States)

Wu, Fan; Wang, Wenhui; Xu, Zhongfeng; Li, Fuli

2015-06-09

The geometry of metal nanoparticles greatly affects the properties of the localized surface plasmon resonance and surface-enhanced Raman scattering. The synthesis of metal nanoparticles with controllable geometry has thus attracted extensive attentions. In this work, we report a modified polyol synthesis approach of silver (Ag) nanocubes through tuning the concentration of bromide ions (Br(-) ions). We have systematically investigated the effect of Br(-) ions in the polyol process, and find that higher concentration of Br(-) ions can enhance oxidative etching effect, which is the dominative factor in determining nanostructure geometry. Therefore, one can realize control over nanostructure geometry by manipulating the concentration of Br(-) ions. Our work provides an effective approach to control the shape of metallic nanostructures for potential applications.

Bromide (Br) - Based Synthesis of Ag Nanocubes with High-Yield

Science.gov (United States)

Wu, Fan; Wang, Wenhui; Xu, Zhongfeng; Li, Fuli

2015-01-01

The geometry of metal nanoparticles greatly affects the properties of the localized surface plasmon resonance and surface-enhanced Raman scattering. The synthesis of metal nanoparticles with controllable geometry has thus attracted extensive attentions. In this work, we report a modified polyol synthesis approach of silver (Ag) nanocubes through tuning the concentration of bromide ions (Br− ions). We have systematically investigated the effect of Br− ions in the polyol process, and find that higher concentration of Br− ions can enhance oxidative etching effect, which is the dominative factor in determining nanostructure geometry. Therefore, one can realize control over nanostructure geometry by manipulating the concentration of Br− ions. Our work provides an effective approach to control the shape of metallic nanostructures for potential applications. PMID:26058050

Method of synthesis of abstract images with high self-similarity

Science.gov (United States)

Matveev, Nikolay V.; Shcheglov, Sergey A.; Romanova, Galina E.; Koneva, Ð.¢atiana A.

2017-06-01

Abstract images with high self-similarity could be used for drug-free stress therapy. This based on the fact that a complex visual environment has a high affective appraisal. To create such an image we can use the setup based on the three laser sources of small power and different colors (Red, Green, Blue), the image is the pattern resulting from the reflecting and refracting by the complicated form object placed into the laser ray paths. The images were obtained experimentally which showed the good therapy effect. However, to find and to choose the object which gives needed image structure is very difficult and requires many trials. The goal of the work is to develop a method and a procedure of finding the object form which if placed into the ray paths can provide the necessary structure of the image In fact the task means obtaining the necessary irradiance distribution on the given surface. Traditionally such problems are solved using the non-imaging optics methods. In the given case this task is very complicated because of the complicated structure of the illuminance distribution and its high non-linearity. Alternative way is to use the projected image of a mask with a given structure. We consider both ways and discuss how they can help to speed up the synthesis procedure for the given abstract image of the high self-similarity for the setups of drug-free therapy.

High pressure synthesis of a hexagonal close-packed phase of the high-entropy alloy CrMnFeCoNi

Energy Technology Data Exchange (ETDEWEB)

Tracy, Cameron L.; Park, Sulgiye; Rittman, Dylan R.; Zinkle, Steven J.; Bei, Hongbin; Lang, Maik; Ewing, Rodney C.; Mao, Wendy L.

2017-05-25

High-entropy alloys, near-equiatomic solid solutions of five or more elements, represent a new strategy for the design of materials with properties superior to those of conventional alloys. However, their phase space remains constrained, with transition metal high-entropy alloys exhibiting only face- or body-centered cubic structures. Here, we report the high-pressure synthesis of a hexagonal close-packed phase of the prototypical high-entropy alloy CrMnFeCoNi. This martensitic transformation begins at 14 GPa and is attributed to suppression of the local magnetic moments, destabilizing the initial fcc structure. Similar to fcc-to-hcp transformations in Al and the noble gases, the transformation is sluggish, occurring over a range of >40 GPa. However, the behaviour of CrMnFeCoNi is unique in that the hcp phase is retained following decompression to ambient pressure, yielding metastable fcc-hcp mixtures. This demonstrates a means of tuning the structures and properties of high-entropy alloys in a manner not achievable by conventional processing techniques.

Influence of a pulse duration of high-voltage supply on the efficiency of ozone synthesis in the 'needle-plane' electrode system

International Nuclear Information System (INIS)

Golota, V.I.; Zavada, L.M.; Karas, V.I.; Kotjukov, O.V.; Poliakov, O.V.; Pugach, S.G.

2007-01-01

We present the results of studies of the electrodynamic characteristics of a barrier less discharge with electrodes of the 'needle-plane' type and a high-voltage pulse of positive polarity, being applied to the edge electrode. The efficiency of ozone synthesis is determined as a function of the pulse duration and repetition rate. It is shown that the electrodynamic characteristics of the discharge and the effectiveness of ozone synthesis in oxygen-containing gas mixtures essentially depend on the parameters of the pulse supply

Energy efficient methane tri-reforming for synthesis gas production over highly coke resistant nanocrystalline Ni–ZrO_2 catalyst

International Nuclear Information System (INIS)

Singha, Rajib Kumar; Shukla, Astha; Yadav, Aditya; Adak, Shubhadeep; Iqbal, Zafar; Siddiqui, Nazia; Bal, Rajaram

2016-01-01

Highlights: • Tri-reforming of methane is an energy efficient process to produce synthesis gas. • Nanocrystalline Ni–ZrO_2 catalyst is prepared for tri-reforming of methane. • Strong metal-support interaction is the driving force for high activity. • The process produces synthesis gas with H_2/CO ratio of around 2. • The produced synthesis gas can be used to synthesize methanol. - Abstract: We report the synthesis of nanocrystalline Ni–ZrO_2 catalyst for tri-reforming of methane (5CH_4 + O_2 + CO_2 + 2H_2O → 6CO + 12H_2) to produce synthesis gas with H_2/CO mole ratio ∼2. Nanocrystalline Ni–ZrO_2 catalyst of size between 10 and 40 nm was prepared by hydrothermal method using cetyltrimethylammonium bromide (CTAB) as a surfactant. The prepared catalysts were characterized by N_2-physisorption studies, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), temperature programmed reduction (TPR), H_2-chemisorpton, thermo-gravimetric analysis (TGA), Inductively coupled plasma atomic emission spectroscopy (ICP-AES) and X-ray photoelectron spectroscopy (XPS). The catalytic activity was monitored over temperature range between 500 and 800 °C. Different reaction parameters like temperature, Ni-loading, gas hourly space velocity (GHSV) and time on stream (TOS) were studied in detail. 4.8 wt% Ni loading for Ni–ZrO_2 catalyst was found to be the optimum Ni loading which showed the superior catalytic activity for methane tri-reforming. The catalyst was found to be stable for more than 100 h on time on stream with methane, carbon dioxide and steam conversion of ∼95% at 800 °C. The H_2/CO ratio was almost constant to 1.9 throughout the time on stream experiment. Highly dispersed nickel and the presence of strong metal support interaction were found to be the key factor for the superior activity of the catalyst. The effect of O_2 and H_2O concentration on reactant conversions and H_2/CO ratios were also

DETECTING LOW-LEVEL SYNTHESIS IMPURITIES IN MODIFIED PHOSPHOROTHIOATE OLIGONUCLEOTIDES USING LIQUID CHROMATOGRAPHY – HIGH RESOLUTION MASS SPECTROMETRY

Science.gov (United States)

Nikcevic, Irena; Wyrzykiewicz, Tadeusz K.; Limbach, Patrick A.

2010-01-01

Summary An LC-MS method based on the use of high resolution Fourier transform ion cyclotron resonance mass spectrometry (FTIRCMS) for profiling oligonucleotides synthesis impurities is described. Oligonucleotide phosphorothioatediesters (phosphorothioate oligonucleotides), in which one of the non-bridging oxygen atoms at each phosphorus center is replaced by a sulfur atom, are now one of the most popular oligonucleotide modifications due to their ease of chemical synthesis and advantageous pharmacokinetic properties. Despite significant progress in the solid-phase oligomerization chemistry used in the manufacturing of these oligonucleotides, multiple classes of low-level impurities always accompany synthetic oligonucleotides. Liquid chromatography-mass spectrometry has emerged as a powerful technique for the identification of these synthesis impurities. However, impurity profiling, where the entire complement of low-level synthetic impurities is identified in a single analysis, is more challenging. Here we present an LC-MS method based the use of high resolution-mass spectrometry, specifically Fourier transform ion cyclotron resonance mass spectrometry (FTIRCMS or FTMS). The optimal LC-FTMS conditions, including the stationary phase and mobile phases for the separation and identification of phosphorothioate oligonucleotides, were found. The characteristics of FTMS enable charge state determination from single m/z values of low-level impurities. Charge state information then enables more accurate modeling of the detected isotopic distribution for identification of the chemical composition of the detected impurity. Using this approach, a number of phosphorothioate impurities can be detected by LC-FTMS including failure sequences carrying 3′-terminal phosphate monoester and 3′-terminal phosphorothioate monoester, incomplete backbone sulfurization and desulfurization products, high molecular weight impurities, and chloral, isobutyryl, and N3 (2-cyanoethyl) adducts

Phase-controlled synthesis of α-NiS nanoparticles confined in carbon nanorods for High Performance Supercapacitors

Science.gov (United States)

Sun, Chencheng; Ma, Mingze; Yang, Jun; Zhang, Yufei; Chen, Peng; Huang, Wei; Dong, Xiaochen

2014-11-01

A facile and phase-controlled synthesis of α-NiS nanoparticles (NPs) embedded in carbon nanorods (CRs) is reported by in-situ sulfurating the preformed Ni/CRs. The nanopore confinement by the carbon matrix is essential for the formation of α-NiS and preventing its transition to β-phase, which is in strong contrast to large aggregated β-NiS particles grown freely without the confinement of CRs. When used as electrochemical electrode, the hybrid electrochemical charge storage of the ultrasmall α-NiS nanoparticels dispersed in CRs is benefit for the high capacitor (1092, 946, 835, 740 F g-1 at current densities of 1, 2, 5, 10 A g-1, respectively.). While the high electrochemical stability (approximately 100% retention of specific capacitance after 2000 charge/discharge cycles) is attributed to the supercapacitor-battery electrode, which makes synergistic effect of capacitor (CRs) and battery (NiS NPs) components rather than a merely additive composite. This work not only suggests a general approach for phase-controlled synthesis of nickel sulfide but also opens the door to the rational design and fabrication of novel nickel-based/carbon hybrid supercapacitor-battery electrode materials.

alpha,beta-unsaturated 2-acyl imidazoles as a practical class of dienophiles for the DNA-Based catalytic asymmetric diels-alder reaction in water

NARCIS (Netherlands)

Boersma, A.J.; Feringa, B.L.; Roelfes, G.

2007-01-01

alpha,beta-Unsaturated 2-acyl imidazoles are a novel and practical class of dienophiles for the DNA-based catalytic asymmetric Diels-Alder reaction in water. The Diels-Alder products are obtained with very high diastereoselectivities and enantioselectivities in the range of 83-98%. The catalytic

Nickel nanoparticles: A highly efficient catalyst for one pot synthesis ...

Indian Academy of Sciences (India)

and KANIKA VIJ. Department of Chemistry, University of Delhi, Delhi 110 007, India ... Keywords. PVP-stabilized Ni nanoparticles; ethylene glycol; tetraketones; biscoumarins; ... ing interest in using nickel nanoparticles in organic synthesis ...

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.

Highly Efficient Synthesis of 2-Aryl-3-methoxyacrylates via Suzuki-Miyaura Coupling Reaction

Energy Technology Data Exchange (ETDEWEB)

Kim, Hyung Ho; Lee, Chun Ho; Song, Young Seob; Park, No Kyun; Kim, Bum Tae; Heo, Jung Nyoung [Korea Research Institute of Chemical Technology, Daejeon (Korea, Republic of)

2006-02-15

We have developed a highly efficient and convergent synthesis of 2-aryl-3-methoxyacrylates via the Suzuki-Miyaura coupling reaction of α-iodo-β-methoxy-acrylate with arylboronic acids. The biological activities of 2-aryl-3-methoxyacrylate derivatives will be reported in due course. The Suzuki-Miyaura coupling reaction provides a convenient access to the carbon-carbon bond formation with high efficiency. Recently, a number of 2-aryl-3-methoxy-acrylates served as a key scaffold for the development of biologically active pharmaceuticals and agrochemicals. Especially, the discovery of the naturally-occurring fungicides, such as strobilurin A and oudemansin A, possessing a β-methoxyacrylate moiety was immediately seized great attention by industrial research groups to open a new era of the strobilurin family including azoxy-strobin and picoxystrobin.

Automated synthesis of an {sup 18}F-labelled pyridine-based alkylating agent for high yield oligonucleotide conjugation

Energy Technology Data Exchange (ETDEWEB)

Guggenberg, Elisabeth von; Sader, Jayden A.; Wilson, John S.; Shahhosseini, Soraya; Koslowsky, Ingrid; Wuest, Frank [Edmonton PET Centre, Division of Oncologic Imaging, Department of Oncology, Cross Cancer Institute, 11560 University Ave, Edmonton, AB, T6G 1Z2 (Canada); Mercer, John R. [Edmonton PET Centre, Division of Oncologic Imaging, Department of Oncology, Cross Cancer Institute, 11560 University Ave, Edmonton, AB, T6G 1Z2 (Canada)], E-mail: johnmerc@cancerboard.ab.ca

2009-09-15

Alkylating agents have been shown to be very promising for the radiolabelling of oligonucleotides with fluorine-18. In this report we describe the fully automated synthesis of 2-bromo-N-[3-(2-[{sup 18}F]fluoropyridin-3-yloxy)propyl]acetamide ([{sup 18}F]FPyBrA) utilizing a modular synthesis unit. Reaction conditions for the coupling of this pyridine-based alkylating agent at the 5' end of a fully phosphorothioated random 20-mer DNA sequence were optimized to achieve very high radiochemical yields (>90%) and a maximum specific activity of 5-6 GBq/{mu}moL. The potential for rapid purification by solid phase extraction without need of chromatographic isolation of the radiolabelled oligonucleotide presents an overall benefit for the application of oligonucleotides in preclinical studies and potential clinical applications.

Synthesis of nanoparticles using high-pressure sputtering for magnetic domain imaging

International Nuclear Information System (INIS)

Shah, Prasanna; Gavrin, A.

2006-01-01

We have developed a modified sputtering gun for direct synthesis of metallic nanoparticles, and used this system to produce magnetic domain images using high-resolution Bitter microscopy (HRBM). The nanoparticles are produced at 900 mTorr inside the gun and transported to the main vacuum chamber by the pressure difference between the chamber and the gun interior. Fe particles synthesized using the particle gun have been characterized using X-ray diffraction, atomic force microscopy, and transmission electron microscopy techniques. The particles are 15-30 nm in size with a pure BCC phase. Further, we have deposited these Fe nanoparticles on magnetic recording media and observed the domain patterns using optical microscopy, scanning electron microscopy, and atomic force microscopy. We achieve a spatial resolution of at most 80 nm

Two-directional synthesis as a tool for diversity-oriented synthesis: Synthesis of alkaloid scaffolds

Directory of Open Access Journals (Sweden)

Kieron M. G. O’Connell

2012-06-01

Full Text Available Two-directional synthesis represents an ideal strategy for the rapid elaboration of simple starting materials and their subsequent transformation into complex molecular architectures. As such, it is becoming recognised as an enabling technology for diversity-oriented synthesis. Herein, we provide a thorough account of our work combining two-directional synthesis with diversity-oriented synthesis, with particular reference to the synthesis of polycyclic alkaloid scaffolds.

High-throughput continuous hydrothermal synthesis of an entire nanoceramic phase diagram.

Science.gov (United States)

Weng, Xiaole; Cockcroft, Jeremy K; Hyett, Geoffrey; Vickers, Martin; Boldrin, Paul; Tang, Chiu C; Thompson, Stephen P; Parker, Julia E; Knowles, Jonathan C; Rehman, Ihtesham; Parkin, Ivan; Evans, Julian R G; Darr, Jawwad A

2009-01-01

A novel High-Throughput Continuous Hydrothermal (HiTCH) flow synthesis reactor was used to make directly and rapidly a 66-sample nanoparticle library (entire phase diagram) of nanocrystalline Ce(x)Zr(y)Y(z)O(2-delta) in less than 12 h. High resolution PXRD data were obtained for the entire heat-treated library (at 1000 degrees C/1 h) in less than a day using the new robotic beamline I11, located at Diamond Light Source (DLS). This allowed Rietveld-quality powder X-ray diffraction (PXRD) data collection of the entire 66-sample library in <1 day. Consequently, the authors rapidly mapped out phase behavior and sintering behaviors for the entire library. Out of the entire 66-sample heat-treated library, the PXRD data suggests that 43 possess the fluorite structure, of which 30 (out of 36) are ternary compositions. The speed, quantity and quality of data obtained by our new approach, offers an exciting new development which will allow structure-property relationships to be accessed for nanoceramics in much shorter time periods.

Facile Synthesis and High performance of a New Carbazole-Based Hole Transporting Material for Hybrid Perovskite Solar Cells

KAUST Repository

Wang, Hong

2015-06-26

Perovskite solar cells are very promising for practical applications owing to their rapidly rising power conversion efficiency and low cost of solution-based processing. 2,2’,7,7’-tetrakis-(N,N-di-p-methoxyphenylamine) 9,9’-spirobifluorene (Spiro-OMeTAD) is most widely used as hole transporting material (HTM) in perovskite solar cells. However, the tedious synthesis and high cost of Spiro-OMeTAD inhibit its commercial-scale application in the photovoltaic industry. In this article, we report a carbazole-based compound (R01) as a new HTM in efficient perovskite solar cells. R01 is synthesized via a facile route consisting of only two steps from inexpensive commercially available materials. Furthermore, R01 exhibits higher hole mobility and conductivity than the state-of-the-art Spiro-OMeTAD. Perovskite solar cells fabricated with R01 produce a power conversion efficiency of 12.03%, comparable to that obtained in devices using Spiro-OMeTAD in this study. Our findings underscore R01 as a highly promising HTM with high performance, and its facile synthesis and low cost may facilitate the large-scale applications of perovskite solar cells.

Facile Synthesis and High performance of a New Carbazole-Based Hole Transporting Material for Hybrid Perovskite Solar Cells

KAUST Repository

Wang, Hong; Sheikh, Arif D.; Feng, Quanyou; Li, Feng; Chen, Yin; Yu, Weili; Alarousu, Erkki; Ma, Chun; Haque, Mohammed; Shi, Dong; Wang, Zhong-Sheng; Mohammed, Omar F.; Bakr, Osman; Wu, Tao

2015-01-01

Perovskite solar cells are very promising for practical applications owing to their rapidly rising power conversion efficiency and low cost of solution-based processing. 2,2’,7,7’-tetrakis-(N,N-di-p-methoxyphenylamine) 9,9’-spirobifluorene (Spiro-OMeTAD) is most widely used as hole transporting material (HTM) in perovskite solar cells. However, the tedious synthesis and high cost of Spiro-OMeTAD inhibit its commercial-scale application in the photovoltaic industry. In this article, we report a carbazole-based compound (R01) as a new HTM in efficient perovskite solar cells. R01 is synthesized via a facile route consisting of only two steps from inexpensive commercially available materials. Furthermore, R01 exhibits higher hole mobility and conductivity than the state-of-the-art Spiro-OMeTAD. Perovskite solar cells fabricated with R01 produce a power conversion efficiency of 12.03%, comparable to that obtained in devices using Spiro-OMeTAD in this study. Our findings underscore R01 as a highly promising HTM with high performance, and its facile synthesis and low cost may facilitate the large-scale applications of perovskite solar cells.

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.

In Situ One-Step Synthesis of Hierarchical Nitrogen-Doped Porous Carbon for High Performance Supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Jeon, Ju Won [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Texas A & M Univ., College Station, TX (United States); Sharma, Ronish [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Meduri, Praveen [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Arey, Bruce W. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Schaef, Herbert T. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lutkenhaus, Jodie [Texas A & M Univ., College Station, TX (United States); Lemmon, John P. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Thallapally, Praveen K. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Nandasiri, Manjula I. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); McGrail, B. Peter [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Nune, Satish K. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2014-04-30

Electrochemical performance of the existing state-of-the art capacitors is not very high, key scientific barrier is that its charge storage mechanism wholly depends on adsorption of electrolyte on electrode. We present a novel method for the synthesis of nitrogen -doped porous carbons and address the drawback by precisely controlling composition and surface area. Nitrogen-doped porous carbon was synthesized using a self-sacrificial template technique without any additional nitrogen and carbon sources. They exhibited exceptionally high capacitance (239 Fg-1) due to additional pseudocapacitance originating from doped nitrogen. Cycling tests showed no obvious capacitance decay even after 10,000 cycles, which meets the requirement of commercial supercapacitors. Our method is simple and highly efficient for the production of large quantities of nitrogen-doped porous carbons.

Cyclopropanes and hypervalent iodine reagents: high energy compounds for applications in synthesis and catalysis.

Science.gov (United States)

Fernández González, Davinia; De Simone, Filippo; Brand, Jonathan P; Nicolai, Stefano; Waser, Jérôme

2011-01-01

One of the major challenges faced by organic chemistry is the efficient synthesis of increasingly complex molecules. Since October 2007, the Laboratory of Catalysis and Organic Synthesis (LCSO) at EPFL has been working on the development of catalytic reactions based on the Umpolung of the innate reactivity of functional groups. Electrophilic acetylene synthons have been developed using the exceptional properties of ethynyl benziodoxolone (EBX) hypervalent iodine reagents for the alkynylation of heterocycles and olefins. The obtained acetylenes are important building blocks for organic chemistry, material sciences and chemical biology. The ring-strain energy of donor-acceptor cyclopropanes was then used in the first catalytic formal homo-Nazarov cyclization. In the case of aminocyclopropanes, the method could be applied in the synthesis of the alkaloids aspidospermidine and goniomitine. The developed methods are expected to have a broad potential for the synthesis and functionalization of complex organic molecules, including carbocycles and heterocycles.

Sequential C-Si Bond Formations from Diphenylsilane: Application to Silanediol Peptide Isostere Precursors

DEFF Research Database (Denmark)

Nielsen, Lone; Skrydstrup, Troels

2008-01-01

and the first new carbon-silicon bond. The next step is the reduction of this hydridosilane with lithium metal providing a silyl lithium reagent, which undergoes a highly diastereoselective addition to an optically active tert-butanesulfinimine, thus generating the second C-Si bond. This method allows...

Synthesis of beta-sialon from coal gangue

Energy Technology Data Exchange (ETDEWEB)

Luo, X.Y.; Sun, J.L.; Deng, C.J.; Hong, Y.R. [Beijing University Science & Technology, Beijing (China)

2003-01-01

It is worth studying the synthesis of beta-Sialon from coal gangue, because coal gangue is a waste of coal production and is a high quality kaolin contained carbon which is a perfect raw material of contained reducer itself for synthesis of beta-sialon. The study showed that a high conversion rate of 95% from coal gangue to beta-Sialon could be obtained by using process of carbothermal reduction nitridation when strictly controlling the thermodynamic conditions of synthesis. For controlling the synthesis conditions, the details of the effects of p(CO), P-O{sub 2} and T on the conversion rate of beta-sialon are discussed and the phase diagrams of oxygen pressure vs composition for Si{sub 3}N{sub 4}-A{sub l}N-Al{sub 2}O{sub 3}-SiO{sub 2} system at 1350, 1500, and 1600{sup o}C are constructed.

Development of Highly Efficient Grafting Technique and Synthesis of Natural Polymer-Based Graft Adsorbent

Energy Technology Data Exchange (ETDEWEB)

Ueki, Y; Seko, N; Tamada, M [Japan Atomic Energy Agency, Quantum Beam Science Directorate, Takasaki (Japan)

2012-09-15

In the framework of the CRP, Japan has focused on the development of fibrous adsorbents for removal of toxic metal ions and recovery of significant metal ions from industrial wastewater and streaming water. Graft polymerization was carried out by using gamma irradiation facility and electron beam accelerator. Emulsion grafting is a novel topic for synthesis of metal ion adsorbents which are prepared from fibrous trunk polymers such as polyethylene fibre and biodegradable nonwoven fabrics. The emulsion grafting, where monomer micelles are dispersed in water in the presence of surfactant, is a highly efficient and economic grafting technique as compared to general organic solvent system. The resultant cotton-based adsorbent has high adsorption efficiency and high adsorption capacity for Hg, besides, it is biodegradable. Polylactic acid can also be used as a trunk material for the grafting. (author)

Thermodynamically Controlled High-Pressure High-Temperature Synthesis of Crystalline Fluorinated sp ³ -Carbon Networks

Energy Technology Data Exchange (ETDEWEB)

Klier, Kamil; Landskron, Kai

2015-11-19

We report the feasibility of the thermodynamically controlled synthesis of crystalline sp3-carbon networks. We show that there is a critical pressure below which decomposition of the carbon network is favored and above which the carbon network is stable. Based on advanced, highly accurate quantum mechanical calculations using the all-electron full-potential linearized augmented plane-wave method (FP-LAPW) and the Birch–Murnaghan equation of state, this critical pressure is 26.5 GPa (viz. table of contents graphic). Such pressures are experimentally readily accessible and afford thermodynamic control for suppression of decomposition reactions. The present results further suggest that a general pattern of pressure-directed control exists for many isolobal conversions of sp2 to sp3 allotropes, relating not only to fluorocarbon chemistry but also extending to inorganic and solid-state materials science.

MW-assisted synthesis of LiFePO 4 for high power applications

Science.gov (United States)

Beninati, Sabina; Damen, Libero; Mastragostino, Marina

LiFePO 4/C was prepared by solid-state reaction from Li 3PO 4, Fe 3(PO 4) 2·8H 2O, carbon and glucose in a few minutes in a scientific MW (microwave) oven with temperature and power control. The material was characterized by X-ray diffraction, scanning electron microscopy and by TGA analysis to evaluate carbon content. The electrochemical characterization as positive electrode in EC (ethylene carbonate)-DMC (dimethylcarbonate) 1 M LiPF 6 was performed by galvanostatic charge-discharge cycles at C/10 to evaluate specific capacity and by sequences of 10 s discharge-charge pulses, at different high C-rates (5-45C) to evaluate pulse-specific power in simulate operative conditions for full-HEV application. The maximum pulse-specific power and, particularly, pulse efficiency values are quite high and make MW synthesis a very promising route for mass production of LiFePO 4/C for full-HEV batteries at low energy costs.

High-pressure synthesis of rhombohedral α-AgGaO{sub 2} via direct solid state reaction

Energy Technology Data Exchange (ETDEWEB)

Akhtar, Meysam [Department of Physics and Astronomy, University of Louisville, 102 Natural Science Building, Louisville, KY 40292 (United States); Menon, Madhu [Center for Computational Sciences, University of Kentucky, 325 McVey Hall, Lexington, KY 40506 (United States); Sunkara, Mahendra [Conn Center for Renewable Energy Research, University of Louisville, Ernst Hall Room 102A, Louisville, KY 40292 (United States); Sumanasekera, Gamini [Department of Physics and Astronomy, University of Louisville, 102 Natural Science Building, Louisville, KY 40292 (United States); Conn Center for Renewable Energy Research, University of Louisville, Ernst Hall Room 102A, Louisville, KY 40292 (United States); Durygin, Andriy [Center for the Study of Matter at Extreme Conditions, Florida International University, VH 140, University Park, Miami, FL 33199 (United States); Jasinski, Jacek B., E-mail: jacek.jasinski@louisville.edu [Conn Center for Renewable Energy Research, University of Louisville, Ernst Hall Room 102A, Louisville, KY 40292 (United States)

2015-08-25

Highlights: • Direct synthesis of α-AgGaO{sub 2} via a solid state reaction of Ag{sub 2}O and Ga{sub 2}O{sub 3} powders. • Utilizing high pressure diamond anvil cell to facilitate solid state reaction. • Experimental and theoretical study of vibrational modes for α-AgGaO{sub 2}. • Extensive characterization of synthesized α-AgGaO{sub 2} samples. • GGA + U formalism-based DFT calculations of electronic structure and band gap in α-AgGaO{sub 2}. - Abstract: In this work, we demonstrate the application of high pressure conditions to enable the direct synthesis of α-AgGaO{sub 2} via a solid state reaction of Ag{sub 2}O and Ga{sub 2}O{sub 3}. Synthesis experiments were carried out at pressures and temperatures up to ∼10 GPa and ∼600 °C, respectively, using a resistively-heated diamond anvil cell. Thus synthesized α-AgGaO{sub 2} samples were characterized and their chemical composition and crystal structure were confirmed. In particular, electron diffraction confirmed the rhombohedral delafossite crystal structure of the synthesized AgGaO{sub 2} and its corresponding lattice parameters of a = 2.99 Å and c = 18.43 Å. The vibrational modes analysis was also conducted using a combination of ab initio density functional theory (DFT) and Raman spectroscopy. This analysis yielded good agreement between the calculated Raman-active modes and experimental Raman data. Finally, the application of the GGA + U formalism-based on DFT to calculate the electronic band structure of α-AgGaO{sub 2} provided a more realistic theoretical band gap value than those reported previously.

Single Crystal Synthesis and STM Studies of High Temperature Superconductors

Science.gov (United States)

Barrientos, Alfonso

1997-01-01

This is a final report for the work initiated in September of 1994 under the grant NAG8-1085 - NASA/OMU, on the fabrication of bulk and single crystal synthesis, specific heat measuring and STM studies of high temperature superconductors. Efforts were made to fabricate bulk and single crystals of mercury based superconducting material. A systematic thermal analysis on the precursors for the corresponding oxides and carbonates were carried out to synthesized bulk samples. Bulk material was used as seed in an attempt to grow single crystals by a two-step self flux process. On the other hand bulk samples were characterized by x-ray diffraction, electrical resistivity and magnetic susceptibility, We studied the specific heat behavior in the range from 80 to 300 K. Some preliminary attempts were made to study the atomic morphology of our samples. As part of our efforts we built an ac susceptibility apparatus for measuring the transition temperature of our sintered samples.

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.

Minute-made and low carbon fingerprint microwave synthesis of high quality templated mesoporous silica

KAUST Repository

Chaignon, J.; Bouizi, Y.; Davin, L.; Calin, N.; Albela, B.; Bonneviot, L.

2015-01-01

© The Royal Society of Chemistry 2015. Hexagonal mesostructured templated silicas were produced in less than 10 minutes using an ultra-fast microwave assisted hydrothermal synthesis. Typically, 10 g can be prepared at once in a commercial microwave device usually devoted to analytical digestion. Undesired alcohol side-products were avoided using inexpensive water colloidal silica instead of silicon alkoxides as the silicon source. In comparison with classical heating activation, the absence of pore expansion and pore wall thickening even for synthesis temperatures as high as 190 °C evidenced that heat transfer and diffusion of matter had no time to take place. Comparison between the chemically extracted and calcined samples shows that the structure was better stabilized for autoclaving above 150 °C. However, a fast temperature ramping and final temperatures above 180 °C were required to sear structures of the highest quality comparable to that of the best conventional methods. This is rationalized by assuming a sequential flake-by-flake assembly of the pore-wall at the micelle palisade. Notably, tosylate counterions yielded better structural characteristics than bromide counterions and allowed better opportunities for surfactant recycling.

N-Acyliminium Intermediates in Solid-Phase Synthesis

DEFF Research Database (Denmark)

Quement, Sebastian Thordal le; Petersen, Rico; Meldal, M.

2010-01-01

N-Acyliminium ions are powerful intermediates in synthetic organic chemistry. Examples of their use are numerous in solution-phase synthesis, but there are unmerited few reports on these highly reactive electrophiles in solid-phase synthesis. The present review covers the literature to date and i...

Highly Efficient Catalytic Synthesis of α-Amino Acids under Phase-Transfer Conditions with a Novel Catalyst/Substrate Pair

NARCIS (Netherlands)

Belokon, Yuri N.; Kochetkov, Konstantin A.; Churkina, Tatiana D.; Ikonnikov, Nikolai S.; Larionov, Oleg V.; Harutyunyan, Syuzanna R.; Vyskočil, Štepán; North, Michael; Kagan, Henri B.

2001-01-01

A facile and fast enantioselective synthesis of α-amino acids with high ee values was achieved by the asymmetric alkylation of the glycine derivative under phase-transfer conditions with (R)- or (S)-2-amino-2'-hydroxy-1,1'-binaphthyl (NOBIN). The ee value of the catalyst can be as little as 40 %

Synthesis gas generation by high pressure partial oxidation (HP POX {sup registered}); Synthesegaserzeugung durch Hochdruck-Partialoxidation (HP POX {sup registered})

Energy Technology Data Exchange (ETDEWEB)

Meyer, B.; Seifert, P.; Zeissler, R. [Technische Univ. Bergakademie Freiberg (Germany). Inst. fuer Energieverfahrenstechnik und Chemieingenieurwesen; Walter, St. [Lurgi AG, Frankfurt/Main (Germany)

2005-05-01

The high pressure synthesis gas process HP POX (High Pressure Partial Oxidation) is a thermal conversion process, which converts e.g. natural gas or heavy residue oil with oxygen to fuel or synthesis gas. Innovative burner technologies allow autothermal catalytic or non-catalytic reforming of gaseous feedstock and gasification of liquid feed streams. Hydrogen and carbon monoxide rich synthesis gases with low methane content (particularly suitable as feed gas for methanol synthesis) can be generated. The technology represents a new generation of entrained flow gasification characterized by the new developed equipment and a design pressure of 100 bar. According to the feeds, the HP POX gasification process is the link between the downstream synthesis chemistry (use of gaseous and liquid feeds) and the power plant process (liquid or solid fuels as suspension or slurry). The HP POX development is carried out together with the Lurgi AG at the Institute for Energy Process Engineering and Chemical Engineering (IEC). The 5 MW HP POX test plant built in Freiberg by Lurgi is core of the joint research project, which is supported by the German Federal Ministry of Economics and Labour (BMWA), the Saxon Ministry of Science and the Fine Arts (SMWK), and the mg technologies ag (parent company of Lurgi). The conducted sets of experiments indicate that the unit can be operated in a safe, smooth and stable manner. During this periods of operation, which included nine test campaigns for autothermal reforming (ATR), the maximum pressure for ATR amounted to 70 bar which exceeds the current benchmark in industry for 30 bar. Main objective of R and D work is the development of modelling tools for extreme gasification conditions and different gasification principles of up to 100 bar. These tools are supposed to improve the understanding of the entire gasification process. Their development requires a systematic investigation of the reaction mechanisms and the interactions with the process

Synthesis of graphene using gamma radiations

Indian Academy of Sciences (India)

Considering the advantages of radiolytic synthesis such as the absence of toxic chemical as a reducing agent, uniform distribution of reducing agent and high purity of product, the synthesis of graphene (rGO) from graphene oxide (GO) by the gamma irradiation technique using a relatively low dose rate of 0.24 kGy h−1 has ...

Experimental and Numerical Studies on Self-Propagating High-Temperature Synthesis of Ta5Si3 Intermetallics

Directory of Open Access Journals (Sweden)

Chun-Liang Yeh

2015-09-01

Full Text Available Formation of Ta5Si3 by self-propagating high-temperature synthesis (SHS from elemental powder compacts of Ta:Si = 5:3 was experimentally and numerically studied. Experimental evidence showed that the increase of either sample density or preheating temperature led to the increase of combustion wave velocity and reaction temperature. The apparent activation energy, Ea ≈ 108 kJ/mol, was determined for the synthesis reaction. Based upon numerical simulation, the Arrhenius factor of the rate function, K0 = 2.5 × 107 s−1, was obtained for the 5Ta + 3Si combustion system. In addition, the influence of sample density on combustion wave kinetics was correlated with the effective thermal conductivity (keff of the powder compact. By adopting 0.005 ≤ keff/kbulk ≤ 0.016 in the computation model, the calculated combustion velocity and temperature were in good agreement with experimental data of the samples with compaction densities between 35% and 45% theoretical maximum density (TMD.

Impact of high altitude on the hepatic fatty acid oxidation and synthesis in rats

Energy Technology Data Exchange (ETDEWEB)

Ni, Qian [Department of General Surgery, Hepatic-biliary-pancreatic Institute, Lanzhou University Second Hospital, Lanzhou (China); Department of Pediatrics, Lanzhou University Second Hospital, Lanzhou (China); Shao, Yuan; Wang, Ying Zhen [Department of General Surgery, Hepatic-biliary-pancreatic Institute, Lanzhou University Second Hospital, Lanzhou (China); Jing, Yu Hong [Institute of Anatomy, School of Basic Medicine, Lanzhou University, Lanzhou (China); Zhang, You Cheng, E-mail: zhangychmd@126.com [Department of General Surgery, Hepatic-biliary-pancreatic Institute, Lanzhou University Second Hospital, Lanzhou (China)

2014-04-04

Highlights: • Acute exposure to high altitude (HA) increased hepatic fatty acid (FA) β-oxidation. • Acute exposure of rats to HA increased hepatic FA synthesis. • PPARα and AMPK can regulate the FA metabolism. • FA may be a key energy fuel and a compensation for CHO during acute exposure to HA. • The acute changes of FA metabolism may be a mechanism of acclimatization. - Abstract: High altitude (HA) affects energy metabolism. The impact of acute and chronic HA acclimatization on the major metabolic pathways is still controversial. In this study, we aimed to unveil the impact of HA on the key enzymes involved in the fatty acid (FA) metabolism in liver. Rats were exposed to an altitude of 4300 m for 30 days and the expressions of two key proteins involved in FA β-oxidation (carnitine palmitoyl transferase I, CPT-I; and peroxisome proliferator-activated receptor alpha, PPARα), two proteins involved in FA synthesis (acetyl CoA carboxylase-1, ACC-1; and AMP-activated protein kinase, AMPK), as well as the total ketone body in the liver and the plasma FFAs were examined. Rats without HA exposure were used as controls. We observed that the acute exposure of rats to HA (3 days) led to a significant increase in the expressions of CPT-I and PPARα and in the total hepatic ketone body. Longer exposure (15 days) caused a marked decrease in the expression of CPT-I and PPARα. By 30 days after HA exposure, the expression levels of CPT-I and PPARα returned to the control level. The hepatic ACC-1 level showed a significant increase in rats exposed to HA for 1 and 3 days. In contrast, the hepatic level of AMPK showed a significant reduction throughout the experimental period. Plasma FFA concentrations did not show any significant changes following HA exposure. Thus, increased hepatic FA oxidation and synthesis in the early phase of HA exposure may be among the important mechanisms for the rats to respond to the hypoxic stress in order to acclimatize themselves to the

Impact of high altitude on the hepatic fatty acid oxidation and synthesis in rats

International Nuclear Information System (INIS)

Ni, Qian; Shao, Yuan; Wang, Ying Zhen; Jing, Yu Hong; Zhang, You Cheng

2014-01-01

Highlights: • Acute exposure to high altitude (HA) increased hepatic fatty acid (FA) β-oxidation. • Acute exposure of rats to HA increased hepatic FA synthesis. • PPARα and AMPK can regulate the FA metabolism. • FA may be a key energy fuel and a compensation for CHO during acute exposure to HA. • The acute changes of FA metabolism may be a mechanism of acclimatization. - Abstract: High altitude (HA) affects energy metabolism. The impact of acute and chronic HA acclimatization on the major metabolic pathways is still controversial. In this study, we aimed to unveil the impact of HA on the key enzymes involved in the fatty acid (FA) metabolism in liver. Rats were exposed to an altitude of 4300 m for 30 days and the expressions of two key proteins involved in FA β-oxidation (carnitine palmitoyl transferase I, CPT-I; and peroxisome proliferator-activated receptor alpha, PPARα), two proteins involved in FA synthesis (acetyl CoA carboxylase-1, ACC-1; and AMP-activated protein kinase, AMPK), as well as the total ketone body in the liver and the plasma FFAs were examined. Rats without HA exposure were used as controls. We observed that the acute exposure of rats to HA (3 days) led to a significant increase in the expressions of CPT-I and PPARα and in the total hepatic ketone body. Longer exposure (15 days) caused a marked decrease in the expression of CPT-I and PPARα. By 30 days after HA exposure, the expression levels of CPT-I and PPARα returned to the control level. The hepatic ACC-1 level showed a significant increase in rats exposed to HA for 1 and 3 days. In contrast, the hepatic level of AMPK showed a significant reduction throughout the experimental period. Plasma FFA concentrations did not show any significant changes following HA exposure. Thus, increased hepatic FA oxidation and synthesis in the early phase of HA exposure may be among the important mechanisms for the rats to respond to the hypoxic stress in order to acclimatize themselves to the

Facile synthesis of uniform MWCNT@Si nanocomposites as high-performance anode materials for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Chen, Yifan; Du, Ning, E-mail: dna1122@zju.edu.cn; Zhang, Hui; Yang, Deren

2015-02-15

Highlights: • A uniform SiO{sub 2} layer was deposited on multi-walled carbon nanotube. • Synthesis of uniform (MWCNT)@Si nanocomposites via the magnesiothermic reduction. • The MWCNT@Si nanocomposites show high reversible capacity and good cyclability. • Enhanced performance is attributed to porous nanostructure, introduction of MWCNTs. - Abstract: We demonstrate the synthesis of uniform multi-walled carbon nanotube (MWCNT)@Si nanocomposites via the magnesiothermic reduction of pre-synthesized MWCNT@SiO{sub 2} nanocables. At first, the acid vapor steaming is used to treat the surface, which can facilitate the uniform deposition of SiO{sub 2} layer via the TEOS hydrolysis. Then, the uniform MWCNT@Si nanocomposites are obtained on the basis of MWCNT@SiO{sub 2} nanocables via a simple magnesiothermic reduction. When used as an anode material for lithium-ion batteries, the as-synthesized MWCNT@Si nanocomposites show high reversible capacity and good cycling performance, which is better than bulk Si and bare MWCNTs. It is believed that the good electrochemical performance can be attributed to the novel porous nanostructure and the introduction of MWCNTs that can buffer the volume change, maintain the electrical conductive network, and enhance the electronic conductivity and lithium-ion transport.

Laser-induced incandescence (LII) diagnostic for in situ monitoring of nanoparticle synthesis in a high-pressure arc discharge

Science.gov (United States)

Yatom, Shurik; Vekselman, Vladislav; Mitrani, James; Stratton, Brentley; Raitses, Yevgeny; LaboratoryPlasma Nanosynthesis Team

2016-10-01

A DC arc discharge is commonly used for synthesis of carbon nanoparticles, including buckyballs, carbon nanotubes, and graphene flakes. In this work we show the first results of nanoparticles monitored during the arc discharge. The graphite electrode is vaporized by high current (60 A) in a buffer Helium gas leading to nanoparticle synthesis in a low temperature plasma. The arc was shown to oscillate, which can possibly influence the nano-synthesis. To visualize the nanoparticles in-situ we employ the LII technique. The nanoparticles with radii >50 nm, emerging from the arc area are heated with a short laser pulse and incandesce. The resulting radiation is captured with an ICCD camera, showing the location of the generated nanoparticles. The images of incandescence are studied together with temporally synchronized fast-framing imaging of C2 emission, to connect the dynamics of arc instabilities, C2 molecules concentration and nanoparticles. The time-resolved incandescence signal is analyzed with combination of ex-situ measurements of the synthesized nanoparticles and LII modeling, to provide the size distribution of produced nanoparticles. This work was supported by US Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.

Methods of synthesis and performance improvement of lithium iron phosphate for high rate Li-ion batteries: A review

Directory of Open Access Journals (Sweden)

T.V.S.L. Satyavani

2016-03-01

Full Text Available Lithium ion battery technology has the potential to meet the requirements of high energy density and high power density applications. A continuous search for novel materials is pursued continually to exploit the latent potential of this technology. In this review paper, methods for preparation of Lithium Iron Phosphate are discussed which include solid state and solution based synthesis routes. The methods to improve the electrochemical performance of lithium iron phosphate are presented in detail.

Facile and High-Yielding Synthesis of TAM Biradicals and Monofunctional TAM Radicals.

Science.gov (United States)

Trukhin, Dmitry V; Rogozhnikova, Olga Yu; Troitskaya, Tatiana I; Vasiliev, Vladimir G; Bowman, Michael K; Tormyshev, Victor M

2016-04-01

Facile and high-yielding procedures for synthesis of monocarboxylic acid derivatives of triarylmethyl radicals (TAMs) were developed. Reaction of methyl thioglycolate with tris(2,3,5,6-tetrathiaaryl)methyl cation smoothly afforded the monosubstituted TAM derivative, which was hydrolyzed to a monocarboxylic acid, with the TAM moiety attached to thioglycolic acid via the sulfur atom. Alternatively, the diamagnetic tricarboxylic acid precursor of Finland trityl was transformed to a trimethyl ester and partially hydrolyzed under controlled conditions. The diester product was isolated and the remaining fractions were converted back to the trimethyl ester for production of more diester. The first representatives of TAM biradicals with different TAM cores and interspin distances were obtained by reaction of these new TAM monocaboxylic acids with N,N'-dimethylethylenediamine.

Ni foam assisted synthesis of high quality hexagonal boron nitride with large domain size and controllable thickness

Science.gov (United States)

Ying, Hao; Li, Xiuting; Li, Deshuai; Huang, Mingqiang; Wan, Wen; Yao, Qian; Chen, Xiangping; Wang, Zhiwei; Wu, Yanqing; Wang, Le; Chen, Shanshan

2018-04-01

The scalable synthesis of two-dimensional (2D) hexagonal boron nitride (h-BN) is of great interest for its numerous applications in novel electronic devices. Highly-crystalline h-BN films, with single-crystal sizes up to hundreds of microns, are demonstrated via a novel Ni foam assisted technique reported here for the first time. The nucleation density of h-BN domains can be significantly reduced due to the high boron solubility, as well as the large specific surface area of the Ni foam. The crystalline structure of the h-BN domains is found to be well aligned with, and therefore strongly dependent upon, the underlying Pt lattice orientation. Growth-time dependent experiments confirm the presence of a surface mediated self-limiting growth mechanism for monolayer h-BN on the Pt substrate. However, utilizing remote catalysis from the Ni foam, bilayer h-BN films can be synthesized breaking the self-limiting effect. This work provides further understanding of the mechanisms involved in the growth of h-BN and proposes a facile synthesis technique that may be applied to further applications in which control over the crystal alignment, and the numbers of layers is crucial.

Detonation Synthesis of Alpha-Variant Silicon Carbide

Science.gov (United States)

Langenderfer, Martin; Johnson, Catherine; Fahrenholtz, William; Mochalin, Vadym

2017-06-01

A recent research study has been undertaken to develop facilities for conducting detonation synthesis of nanomaterials. This process involves a familiar technique that has been utilized for the industrial synthesis of nanodiamonds. Developments through this study have allowed for experimentation with the concept of modifying explosive compositions to induce synthesis of new nanomaterials. Initial experimentation has been conducted with the end goal being synthesis of alpha variant silicon carbide (α-SiC) in the nano-scale. The α-SiC that can be produced through detonation synthesis methods is critical to the ceramics industry because of a number of unique properties of the material. Conventional synthesis of α-SiC results in formation of crystals greater than 100 nm in diameter, outside nano-scale. It has been theorized that the high temperature and pressure of an explosive detonation can be used for the formation of α-SiC in the sub 100 nm range. This paper will discuss in detail the process development for detonation nanomaterial synthesis facilities, optimization of explosive charge parameters to maximize nanomaterial yield, and introduction of silicon to the detonation reaction environment to achieve first synthesis of nano-sized alpha variant silicon carbide.

Total synthesis of solanoeclepin A

Science.gov (United States)

Tanino, Keiji; Takahashi, Motomasa; Tomata, Yoshihide; Tokura, Hiroshi; Uehara, Taketo; Narabu, Takashi; Miyashita, Masaaki

2011-06-01

Cyst nematodes are troublesome parasites that live on, and destroy, a range of important host vegetable plants. Damage caused by the potato cyst nematode has now been reported in over 50 countries. One approach to eliminating the problem is to stimulate early hatching of the nematodes, but key hatching stimuli are not naturally available in sufficient quantities to do so. Here, we report the first chemical synthesis of solanoeclepin A, the key hatch-stimulating substance for potato cyst nematode. The crucial steps in our synthesis are an intramolecular cyclization reaction for construction of the highly strained tricyclo[5.2.1.01,6]decane skeleton (DEF ring system) and an intramolecular Diels-Alder reaction of a furan derivative for the synthesis of the ABC carbon framework. The present synthesis has the potential to contribute to addressing one of the critical food issues of the twenty-first century.

“Synthesis-on” and “synthesis-off” modes of carbon arc operation during synthesis of carbon nanotubes

International Nuclear Information System (INIS)

Yatom, Shurik; Selinsky, Rachel S.

2017-01-01

Arc discharge synthesis of single-walled carbon nanotubes (SWCNTs) remains largely uncontrollable, due to incomplete understanding of the synthetic process itself. Here, we show that synthesis of SWCNTs by a carbon arc may not constitute a single continuous process, but may instead consist of two distinct modes. One of these, a “synthesis-on” mode, produces the majority of the nanomaterials. During the synthesis-on mode, proportionally more carbon nanotubes are collected than in another mode, a “synthesis-off” mode. Both synthesis-on and synthesis-off modes for a typical arc configuration, employing a hollow anode filled with a mixture of powdered metal catalyst and graphite, were characterized by using in situ electrical, imaging, and spectroscopic diagnostics, along with ex situ imaging and spectroscopy. The synthesis-on mode duration is rare compared to the total arc run-time, helping to explain the poor selectivity found in the final collected products, a known inadequacy of arc synthesis. Finally, the rarity of the synthesis on mode occurence may be due to the synthesis off mode being more favorable energetically.

Methylcellulose-Directed Synthesis of Nanocrystalline Zeolite NaA with High CO₂ Uptake.

Science.gov (United States)

Shakarova, Dilshod; Ojuva, Arto; Bergström, Lennart; Akhtar, Farid

2014-07-28

Zeolite NaA nanocrystals with a narrow particle size distribution were prepared by template-free hydrothermal synthesis in thermo-reversible methylcellulose gels. The effects of the amount of methylcellulose, crystallization time and hydrothermal treatment temperature on the crystallinity and particle size distribution of the zeolite NaA nanocrystals were investigated. We found that the thermogelation of methylcellulose in the alkaline Na₂O-SiO₂-Al₂O₃-H₂O system played an important role in controlling the particle size. The synthesized zeolite nanocrystals are highly crystalline, as demonstrated by X-ray diffraction (XRD), and scanning electron microscopy (SEM) shows that the nanocrystals can also display a well-defined facetted morphology. Gas adsorption studies on the synthesized nanocrystalline zeolite NaA showed that nanocrystals with a size of 100 nm displayed a high CO₂ uptake capacity (4.9 mmol/g at 293 K at 100 kPa) and a relatively rapid uptake rate compared to commercially available, micron-sized particles. Low-cost nanosized zeolite adsorbents with a high and rapid uptake are important for large scale gas separation processes, e.g., carbon capture from flue gas.

Synthetic Methods for Ester Bond Formation and Conformational Analysis of Ester-Containing Carbohydrates

Science.gov (United States)

Hackbusch, Sven

This dissertation encompasses work related to synthetic methods for the formation of ester linkages in organic compounds, as well as the investigation of the conformational influence of the ester functional group on the flexibility of inter-saccharide linkages, specifically, and the solution phase structure of ester-containing carbohydrate derivatives, in general. Stereoselective reactions are an important part of the field of asymmetric synthesis and an understanding of their underlying mechanistic principles is essential for rational method development. Here, the exploration of a diastereoselective O-acylation reaction on a trans-2-substituted cyclohexanol scaffold is presented, along with possible reasons for the observed reversal of stereoselectivity dependent on the presence or absence of an achiral amine catalyst. In particular, this work establishes a structure-activity relationship with regard to the trans-2-substituent and its role as a chiral auxiliary in the reversal of diastereoselectivity. In the second part, the synthesis of various ester-linked carbohydrate derivatives, and their conformational analysis is presented. Using multidimensional NMR experiments and computational methods, the compounds' solution-phase structures were established and the effect of the ester functional group on the molecules' flexibility and three-dimensional (3D) structure was investigated and compared to ether or glycosidic linkages. To aid in this, a novel Karplus equation for the C(sp2)OCH angle in ester-linked carbohydrates was developed on the basis of a model ester-linked carbohydrate. This equation describes the sinusoidal relationship between the C(sp2)OCH dihedral angle and the corresponding 3JCH coupling constant that can be determined from a J-HMBC NMR experiment. The insights from this research will be useful in describing the 3D structure of naturally occurring and lab-made ester-linked derivatives of carbohydrates, as well as guiding the de novo-design of

Sample preparation of environmental samples using benzene synthesis followed by high-performance LSC

International Nuclear Information System (INIS)

Filippis, S. De; Noakes, J.E.

1991-01-01

Liquid scintillation counting (LSC) techniques have been widely employed as the detection method for determining environmental levels of tritium and 14 C. Since anthropogenic and nonanthropogenic inputs to the environment are a concern, sampling the environment surrounding a nuclear power facility or fuel reprocessing operation requires the collection of many different sample types, including agriculture products, water, biota, aquatic life, soil, and vegetation. These sample types are not suitable for the direct detection of tritium of 14 C for liquid scintillation techniques. Each sample type must be initially prepared in order to obtain the carbon or hydrogen component of interest and present this in a chemical form that is compatible with common chemicals used in scintillation counting applications. Converting the sample of interest to chemically pure benzene as a sample preparation technique has been widely accepted for processing samples for radiocarbon age-dating applications. The synthesized benzene is composed of the carbon or hydrogen atoms from the original sample and is ideal as a solvent for LSC with excellent photo-optical properties. Benzene synthesis followed by low-background scintillation counting can be applied to the preparation and measurement of environmental samples yielding good detection sensitivities, high radionuclide counting efficiency, and shorter preparation time. The method of benzene synthesis provides a unique approach to the preparation of a wide variety of environmental sample types using similar chemistry for all samples

Synthesis of ammonia using sodium melt.

Science.gov (United States)

Kawamura, Fumio; Taniguchi, Takashi

2017-09-14

Research into inexpensive ammonia synthesis has increased recently because ammonia can be used as a hydrogen carrier or as a next generation fuel which does not emit CO 2 . Furthermore, improving the efficiency of ammonia synthesis is necessary, because current synthesis methods emit significant amounts of CO 2 . To achieve these goals, catalysts that can effectively reduce the synthesis temperature and pressure, relative to those required in the Haber-Bosch process, are required. Although several catalysts and novel ammonia synthesis methods have been developed previously, expensive materials or low conversion efficiency have prevented the displacement of the Haber-Bosch process. Herein, we present novel ammonia synthesis route using a Na-melt as a catalyst. Using this route, ammonia can be synthesized using a simple process in which H 2 -N 2 mixed gas passes through the Na-melt at 500-590 °C under atmospheric pressure. Nitrogen molecules dissociated by reaction with sodium then react with hydrogen, resulting in the formation of ammonia. Because of the high catalytic efficiency and low-cost of this molten-Na catalyst, it provides new opportunities for the inexpensive synthesis of ammonia and the utilization of ammonia as an energy carrier and next generation fuel.

Efficient synthesis of highly fluorescent nitrogen-doped carbon dots for cell imaging using unripe fruit extract of Prunus mume

International Nuclear Information System (INIS)

Atchudan, Raji; Edison, Thomas Nesakumar Jebakumar Immanuel; Sethuraman, Mathur Gopalakrishnan; Lee, Yong Rok

2016-01-01

Graphical abstract: The green synthesis of highly fluorescent N-CDs was achieved using the extract of unripe P. mume fruit as a carbon precursor by a one-pot simple hydrothermal-carbonization method. The resulting N-CDs were used as a staining agent for the fluorescence imaging of MDA-MB-231 cells. Display Omitted - Highlights: • The green synthesis of highly fluorescent N-CDs using the extract of unripe P. mume. • The N-CDs were synthesized by one-pot hydrothermal-carbonization method. • This method of synthesis is a simple, cost effective and eco-friendly route. • N-CDs will be a good alternative for fluorescent dyes and SQDs for bio-applications. - Abstract: Highly fluorescent nitrogen-doped carbon dots (N-CDs) were synthesized using the extract of unripe Prunus mume (P. mume) fruit by a simple one step hydrothermal-carbonization method. The N-CDs were synthesized at different pH ranges, 2.3, 5, 7, and 9. The pH of the P. mume extract was adjusted using an aqueous ammonia solution (25%). The optical properties of N-CDs were examined by UV–vis and fluorescence spectroscopy. The N-CDs synthesized at pH 9 emitted high fluorescence intensity compared to other obtained N-CDs. The N-CDs synthesized at pH 9 was further characterized by high resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and Fourier transform-infra red (FT-IR) spectroscopy. HR-TEM showed that the average size of the synthesized N-CDs was approximately 9 nm and the interlayer distance was 0.21 nm, which was validated by XRD. The graphitic nature of the synthesized N-CDs were confirmed by Raman spectroscopy. XPS and FT-IR spectroscopy confirmed the doping of the nitrogen moiety over the synthesized CDs. The synthesized nitrogen doped CDs (N-CDs) were low toxicity and were used as a staining probe for fluorescence cell imaging.

Efficient synthesis of highly fluorescent nitrogen-doped carbon dots for cell imaging using unripe fruit extract of Prunus mume

Energy Technology Data Exchange (ETDEWEB)

Atchudan, Raji; Edison, Thomas Nesakumar Jebakumar Immanuel [School of Chemical Engineering, Yeungnam University, Gyeongsan 38541 (Korea, Republic of); Sethuraman, Mathur Gopalakrishnan, E-mail: mgsethu@gmail.com [Department of Chemistry, Gandhigram Rural Institute-Deemed University, Gandhigram 624 302, Tamilnadu (India); Lee, Yong Rok, E-mail: yrlee@yu.ac.kr [School of Chemical Engineering, Yeungnam University, Gyeongsan 38541 (Korea, Republic of)

2016-10-30

Graphical abstract: The green synthesis of highly fluorescent N-CDs was achieved using the extract of unripe P. mume fruit as a carbon precursor by a one-pot simple hydrothermal-carbonization method. The resulting N-CDs were used as a staining agent for the fluorescence imaging of MDA-MB-231 cells. Display Omitted - Highlights: • The green synthesis of highly fluorescent N-CDs using the extract of unripe P. mume. • The N-CDs were synthesized by one-pot hydrothermal-carbonization method. • This method of synthesis is a simple, cost effective and eco-friendly route. • N-CDs will be a good alternative for fluorescent dyes and SQDs for bio-applications. - Abstract: Highly fluorescent nitrogen-doped carbon dots (N-CDs) were synthesized using the extract of unripe Prunus mume (P. mume) fruit by a simple one step hydrothermal-carbonization method. The N-CDs were synthesized at different pH ranges, 2.3, 5, 7, and 9. The pH of the P. mume extract was adjusted using an aqueous ammonia solution (25%). The optical properties of N-CDs were examined by UV–vis and fluorescence spectroscopy. The N-CDs synthesized at pH 9 emitted high fluorescence intensity compared to other obtained N-CDs. The N-CDs synthesized at pH 9 was further characterized by high resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and Fourier transform-infra red (FT-IR) spectroscopy. HR-TEM showed that the average size of the synthesized N-CDs was approximately 9 nm and the interlayer distance was 0.21 nm, which was validated by XRD. The graphitic nature of the synthesized N-CDs were confirmed by Raman spectroscopy. XPS and FT-IR spectroscopy confirmed the doping of the nitrogen moiety over the synthesized CDs. The synthesized nitrogen doped CDs (N-CDs) were low toxicity and were used as a staining probe for fluorescence cell imaging.

Carbon-11 labelled phosgene new synthesis - medical interest

International Nuclear Information System (INIS)

Landais, P.

1985-09-01

This thesis describes a new synthesis of high specific radioactivity carbon-11 labelled phosgene. The latter is an important precursor for the labelling of radiopharmaceuticals used in Positron Emission Tomography. The synthesis is carried out in 10 minutes. First, the carbon-11 labelled methane ( 11 CH 4 ) is chlorinated into carbon tetrachloride on pumice impregnated with copper (II) chloride. A photochemical process had previously been studied but this reaction was strongly inhibited. Then the 11 C-carbon tetrachloride is oxidized into 11 C-phosgene on hot stainless. The 11 C-CGP 12177 has been labelled from this new 11 C-Phosgene synthesis for receptor studies which require high specific radioactivity [fr

Reversal of diastereofacial selectivity in hydride reductions of N-tert-butanesulfinyl imines.

Science.gov (United States)

Colyer, John T; Andersen, Neil G; Tedrow, Jason S; Soukup, Troy S; Faul, Margaret M

2006-09-01

A variety of N-tert-butanesulfinyl imines were reduced with NaBH4 in THF containing 2% water to provide the corresponding secondary sulfinamides in high yield and diastereoselectivity. By using the same sulfinyl imine starting materials and changing the reductant to L-Selectride, the stereoselectivity could be efficiently reversed to afford the opposite product diastereomer in high yield and selectivity.

Nacre-Templated Synthesis of Highly Dispersible Carbon Nanomeshes for Layered Membranes with High-Flux Filtration and Sensing Properties.

Science.gov (United States)

Kong, Meng; Li, Mingjie; Shang, Ruoxu; Wu, Jingyu; Yan, Peisong; Xu, Dongmei; Li, Chaoxu

2018-01-24

Marine shells not only represent a rapidly accumulating type of fishery wastes but also offer a unique sort of hybrid nanomaterials produced greenly and massively in nature. The elaborate "brick and mortar" structures of nacre enabled the synthesis of carbon nanomeshes with <1 nm thickness, hierarchical porosity, and high specific surface area through pyrolysis, in which two-dimensional (2D) organic layers served as the carbonaceous precursor and aragonite platelets as the hard template. Mineral bridges within 2D organic layers templated the formation of mesh pores of 20-70 nm. In contrast to other hydrophobic carbon nanomaterials, these carbon nanomeshes showed super dispersibility in diverse solvents and thus processability for membranes through filtration, patterning, spray-coating, and ink-writing. The carbon membranes with layered structures were capable of serving not only for high-flux filtration and continuous flow absorption but also for electrochemical and strain sensing with high sensitivity. Thus, utilization of marine shells, on one hand, relieves the environmental concern of shellfish waste, on the other hand, offers a facile, green, low-cost, and massive approach to synthesize unique carbon nanomeshes alternative to graphene nanomeshes and applicable in environmental adsorption, filtration, wearable sensors, and flexible microelectronics.

Finite element design for the HPHT synthesis of diamond

Science.gov (United States)

Li, Rui; Ding, Mingming; Shi, Tongfei

2018-06-01

The finite element method is used to simulate the steady-state temperature field in diamond synthesis cell. The 2D and 3D models of the China-type cubic press with large deformation of the synthesis cell was established successfully, which has been verified by situ measurements of synthesis cell. The assembly design, component design and process design for the HPHT synthesis of diamond based on the finite element simulation were presented one by one. The temperature field in a high-pressure synthetic cavity for diamond production is optimized by adjusting the cavity assembly. A series of analysis about the influence of the pressure media parameters on the temperature field are examined through adjusting the model parameters. Furthermore, the formation mechanism of wasteland was studied in detail. It indicates that the wasteland is inevitably exists in the synthesis sample, the distribution of growth region of the diamond with hex-octahedral is move to the center of the synthesis sample from near the heater as the power increasing, and the growth conditions of high quality diamond is locating at the center of the synthesis sample. These works can offer suggestion and advice to the development and optimization of a diamond production process.

A hardware acceleration based on high-level synthesis approach for glucose-insulin analysis

Science.gov (United States)

Daud, Nur Atikah Mohd; Mahmud, Farhanahani; Jabbar, Muhamad Hairol

2017-01-01

In this paper, the research is focusing on Type 1 Diabetes Mellitus (T1DM). Since this disease requires a full attention on the blood glucose concentration with the help of insulin injection, it is important to have a tool that able to predict that level when consume a certain amount of carbohydrate during meal time. Therefore, to make it realizable, a Hovorka model which is aiming towards T1DM is chosen in this research. A high-level language is chosen that is C++ to construct the mathematical model of the Hovorka model. Later, this constructed code is converted into intellectual property (IP) which is also known as a hardware accelerator by using of high-level synthesis (HLS) approach which able to improve in terms of design and performance for glucose-insulin analysis tool later as will be explained further in this paper. This is the first step in this research before implementing the design into system-on-chip (SoC) to achieve a high-performance system for the glucose-insulin analysis tool.

Synthesis, characterization and spectral properties of new, highly fluorescent, 4-hydroxythiazoles

Czech Academy of Sciences Publication Activity Database

Kammel, R.; Tarabová, D.; Machalický, O.; Nepraš, M.; Frumarová, Božena; Hanusek, J.

2016-01-01

Roč. 128, May (2016), s. 101-110 ISSN 0143-7208 Institutional support: RVO:61389013 Keywords : 4-hydroxythiazoles * synthesis * absorption spectra Subject RIV: CC - Organic Chemistry Impact factor: 3.473, year: 2016

Highly Efficient Method for the Synthesis of Activated Mesoporous Biocarbons with Extremely High Surface Area for High-Pressure CO2 Adsorption.

Science.gov (United States)

Singh, Gurwinder; Lakhi, Kripal S; Kim, In Young; Kim, Sungho; Srivastava, Prashant; Naidu, Ravi; Vinu, Ajayan

2017-09-06

A simple and efficient way to synthesize activated mesoporous biocarbons (AMBs) with extremely high BET surface area and large pore volume has been achieved for the first time through a simple solid state activation of freely available biomass, Arundo donax, with zinc chloride. The textural parameters of the AMB can easily be controlled by varying the activation temperature. It is demonstrated that the mesoporosity of AMB can be finely tuned with a simple adjustment of the amount of activating agent. AMB with almost 100% mesoporosity can be achieved using the activating agent and the biomass ratio of 5 and carbonization at 500 °C. Under the optimized conditions, AMB with a BET surface area of 3298 m 2 g -1 and a pore volume of 1.9 cm 3 g -1 can be prepared. While being used as an adsorbent for CO 2 capture, AMB registers an impressively high pressure CO 2 adsorption capacity of 30.2 mmol g -1 at 30 bar which is much higher than that of activated carbon (AC), multiwalled carbon nanotubes (MWCNTs), highly ordered mesoporous carbons, and mesoporous carbon nitrides. AMB also shows high stability with excellent regeneration properties under vacuum and temperatures of up to 250 °C. These impressive textural parameters and high CO 2 adsorption capacity of AMB clearly reveal its potential as a promising adsorbent for high-pressure CO 2 capture and storage application. Also, the simple one-step synthesis strategy outlined in this work would provide a pathway to generate a series of novel mesoporous activated biocarbons from different biomasses.

Rh(III-catalyzed directed C–H bond amidation of ferrocenes with isocyanates

Directory of Open Access Journals (Sweden)

Satoshi Takebayashi

2012-10-01

Full Text Available [RhCp*(OAc2(H2O] [Cp* = pentamethylcyclopentadienyl] catalyzed the C–H bond amidation of ferrocenes possessing directing groups with isocyanates in the presence of 2 equiv/Rh of HBF4·OEt2. A variety of disubstituted ferrocenes were prepared in high yields, or excellent diastereoselectivities.

Optimization of self-propagating high-temperature synthesis using a halogen fluoride as an igniter for reagents

Science.gov (United States)

Gaidar, S. M.; Karelina, M. Yu.; Zhigarev, V. D.

2016-12-01

The minimum quantity of the high-activity chemical reagent (HACR) that is required for the initiation of self-propagating high-temperature synthesis (SHS) is determined. The experimental results show that 1-1.3 mg ClF3 (gravity flow from a dosing device), BrF3 on the end of a filling knife, or a few ClF2 + SbF6 - crystals are sufficient for the initiation of titanium-boron or titanium-carbon high-energy powder charge compositions. Since the quantity of HACR required for SHS initiation is very small, the chemical method of initiation can be used for the development of a mobile ignition device for estimating the ignition of various SHS charge compositions under laboratory conditions and for application in standard reactors.

Photolithographic Synthesis of High-Density DNA and RNA Arrays on Flexible, Transparent, and Easily Subdivided Plastic Substrates.

Science.gov (United States)

Holden, Matthew T; Carter, Matthew C D; Wu, Cheng-Hsien; Wolfer, Jamison; Codner, Eric; Sussman, Michael R; Lynn, David M; Smith, Lloyd M

2015-11-17

The photolithographic fabrication of high-density DNA and RNA arrays on flexible and transparent plastic substrates is reported. The substrates are thin sheets of poly(ethylene terephthalate) (PET) coated with cross-linked polymer multilayers that present hydroxyl groups suitable for conventional phosphoramidite-based nucleic acid synthesis. We demonstrate that by modifying array synthesis procedures to accommodate the physical and chemical properties of these materials, it is possible to synthesize plastic-backed oligonucleotide arrays with feature sizes as small as 14 μm × 14 μm and feature densities in excess of 125 000/cm(2), similar to specifications attainable using rigid substrates such as glass or glassy carbon. These plastic-backed arrays are tolerant to a wide range of hybridization temperatures, and improved synthetic procedures are described that enable the fabrication of arrays with sequences up to 50 nucleotides in length. These arrays hybridize with S/N ratios comparable to those fabricated on otherwise identical arrays prepared on glass or glassy carbon. This platform supports the enzymatic synthesis of RNA arrays and proof-of-concept experiments are presented showing that the arrays can be readily subdivided into smaller arrays (or "millichips") using common laboratory-scale laser cutting tools. These results expand the utility of oligonucleotide arrays fabricated on plastic substrates and open the door to new applications for these important bioanalytical tools.

Development of a poly(dimethylacrylamide) based matrix material for solid phase high density peptide array synthesis employing a laser based material transfer

International Nuclear Information System (INIS)

Ridder, Barbara; Foertsch, Tobias C.; Welle, Alexander; Mattes, Daniela S.; Bojnicic-Kninski, Clemens M. von; Loeffler, Felix F.; Nesterov-Mueller, Alexander; Meier, Michael A.R.; Breitling, Frank

2016-01-01

Highlights: • New matrix material for peptide array synthesis from a ‘solid solvent’. • Resolution was increased with possible spot densities of up to 20.000 spots per cm"2. • The coupling depth and the effectiveness of washing steps analyzed by ToF-SIMS. • Adaptations and custom changes of the matrix material are possible. - Abstract: Poly(dimethylacrylamide) (PDMA) based matrix materials were developed for laser-based in situ solid phase peptide synthesis to produce high density arrays. In this specific array synthesis approach, amino acid derivatives are embedded into a matrix material, serving as a “solid” solvent material at room temperature. Then, a laser pulse transfers this mixture to the target position on a synthesis slide, where the peptide array is synthesized. Upon heating above the glass transition temperature of the matrix material, it softens, allowing diffusion of the amino acid derivatives to the synthesis surface and serving as a solvent for peptide bond formation. Here, we synthesized PDMA six-arm star polymers, offering the desired matrix material properties, using atom transfer radical polymerization. With the synthesized polymers as matrix material, we structured and synthesized arrays with combinatorial laser transfer. With densities of up to 20,000 peptide spots per cm"2, the resolution could be increased compared to the commercially available standard matrix material. Time-of-Flight Secondary Ion Mass Spectrometry experiments revealed the penetration behavior of an amino acid derivative into the prepared acceptor synthesis surface and the effectiveness of the washing protocols.

Development of a poly(dimethylacrylamide) based matrix material for solid phase high density peptide array synthesis employing a laser based material transfer

Energy Technology Data Exchange (ETDEWEB)

Ridder, Barbara [Institute of Microstructure Technology (IMT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Institute of Organic Chemistry (IOC), Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe (Germany); Foertsch, Tobias C. [Institute of Microstructure Technology (IMT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Welle, Alexander [Karlsruhe Nano Micro Facility (KNMF), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Mattes, Daniela S. [Institute of Microstructure Technology (IMT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Institute of Organic Chemistry (IOC), Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe (Germany); Bojnicic-Kninski, Clemens M. von; Loeffler, Felix F.; Nesterov-Mueller, Alexander [Institute of Microstructure Technology (IMT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Meier, Michael A.R., E-mail: m.a.r.meier@kit.edu [Institute of Organic Chemistry (IOC), Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe (Germany); Breitling, Frank, E-mail: frank.breitling@kit.edu [Institute of Microstructure Technology (IMT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany)

2016-12-15

Highlights: • New matrix material for peptide array synthesis from a ‘solid solvent’. • Resolution was increased with possible spot densities of up to 20.000 spots per cm{sup 2}. • The coupling depth and the effectiveness of washing steps analyzed by ToF-SIMS. • Adaptations and custom changes of the matrix material are possible. - Abstract: Poly(dimethylacrylamide) (PDMA) based matrix materials were developed for laser-based in situ solid phase peptide synthesis to produce high density arrays. In this specific array synthesis approach, amino acid derivatives are embedded into a matrix material, serving as a “solid” solvent material at room temperature. Then, a laser pulse transfers this mixture to the target position on a synthesis slide, where the peptide array is synthesized. Upon heating above the glass transition temperature of the matrix material, it softens, allowing diffusion of the amino acid derivatives to the synthesis surface and serving as a solvent for peptide bond formation. Here, we synthesized PDMA six-arm star polymers, offering the desired matrix material properties, using atom transfer radical polymerization. With the synthesized polymers as matrix material, we structured and synthesized arrays with combinatorial laser transfer. With densities of up to 20,000 peptide spots per cm{sup 2}, the resolution could be increased compared to the commercially available standard matrix material. Time-of-Flight Secondary Ion Mass Spectrometry experiments revealed the penetration behavior of an amino acid derivative into the prepared acceptor synthesis surface and the effectiveness of the washing protocols.

Tension-controlled single-crystallization of copper foils for roll-to-roll synthesis of high-quality graphene films

Science.gov (United States)

Jo, Insu; Park, Subeom; Kim, Dongjin; San Moon, Jin; Park, Won Bae; Kim, Tae Hyeong; Hyoun Kang, Jin; Lee, Wonbae; Kim, Youngsoo; Lee, Dong Nyung; Cho, Sung-Pyo; Choi, Hyunchul; Kang, Inbyeong; Park, Jong Hyun; Lee, Jeong Soo; Hong, Byung Hee

2018-04-01

It has been known that the crystalline orientation of Cu substrates plays a crucial role in chemical vapor deposition (CVD) synthesis of high-quality graphene. In particular, Cu (1 1 1) surface showing the minimum lattice mismatch with graphene is expected to provide an ideal catalytic reactivity that can minimize the formation of defects, which also induces larger single-crystalline domain sizes of graphene. Usually, the Cu (1 1 1) substrates can be epitaxially grown on single-crystalline inorganic substrates or can be recrystallized by annealing for more than 12 h, which limits the cost and time-effective synthesis of graphene. Here, we demonstrate a new method to optimize the crystalline orientations of vertically suspended Cu foils by tension control during graphene growth, resulting in large-area recrystallization into Cu (1 1 1) surface as the applied tension activates the grain boundary energy of Cu and promotes its abnormal grain growth to single crystals. In addition, we found a clue that the formation of graphene cooperatively assists the recrystallization into Cu (1 1 1) by minimizing the surface energy of Cu. The domain sizes and charge carrier mobility of graphene grown on the single-crystalline Cu (1 1 1) are 5 times and ~50% increased, respectively, in comparison with those of graphene from Cu (1 0 0), indicating that the less lattice mismatch and the lower interaction energy between Cu (1 1 1) and graphene allows the growth of larger single-crystalline graphene with higher charge carrier mobility. Thus, we believe that our finding provides a crucial idea to design a roll-to-roll (R2R) graphene synthesis system where the tension control is inevitably involved, which would be of great importance for the continuous production of high-quality graphene in the future.

Plasma synthesis of nanostructures for improved thermoelectric properties

International Nuclear Information System (INIS)

Petermann, Nils; Hecht, Christian; Schulz, Christof; Wiggers, Hartmut; Stein, Niklas; Schierning, Gabi; Theissmann, Ralf; Stoib, Benedikt; Brandt, Martin S

2011-01-01

The utilization of silicon-based materials for thermoelectrics is studied with respect to the synthesis and processing of doped silicon nanoparticles from gas phase plasma synthesis. It is found that plasma synthesis enables the formation of spherical, highly crystalline and soft-agglomerated materials. We discuss the requirements for the formation of dense sintered bodies, while keeping the crystallite size small. Small particles a few tens of nanometres and below that are easily achievable from plasma synthesis, and a weak surface oxidation, both lead to a pronounced sinter activity about 350 K below the temperature usually needed for the successful densification of silicon. The thermoelectric properties of our sintered materials are comparable to the best results found for nanocrystalline silicon prepared by methods other than plasma synthesis.

Effect of heat stress on the pattern of protein synthesis in wheat endosperm

International Nuclear Information System (INIS)

Inwood, W.; Bernardin, J.

1990-01-01

The exposure of detached wheat heads (T. aestivum L. cv Cheyenne) to elevated temperatures resulted not only in the induction of a typical set of high and low molecular weight heat shock proteins (hsps), but also in a differential effect on the synthesis of wheat storage proteins in endosperm tissue when monitored by SDS PAGE of 35 S-labeled polypeptides. The synthesis of hsps in the endosperm had a rapid onset, reached a maximum rate within the first 2 hours at 40 degree C, and then steadily decreased during the next four hours. When heads were returned to 25 degree C after 3 hours at 40 degree C, hsp synthesis did not cease abruptly, but gradually declined over the next several hours. High molecular weight glutenin protein synthesis was drastically reduced with the same time course as heat shock protein synthesis was induced at 40 degree C. Conversely, the synthesis of gliadin proteins remained at a high level at 40 degree C. The synthesis rates for glutenin and gliadin proteins remained at low and high levels, respectively, for as long as the elevated temperature was maintained up to 7 hours

Delphinidin prevents high glucose-induced cell proliferation and collagen synthesis by inhibition of NOX-1 and mitochondrial superoxide in mesangial cells

Directory of Open Access Journals (Sweden)

Seung Eun Song

2016-04-01

Full Text Available This study examined the effect of delphinidin on high glucose-induced cell proliferation and collagen synthesis in mesangial cells. Glucose dose-dependently (5.6–25 mM increased cell proliferation and collagen I and IV mRNA levels, whereas pretreatment with delphinidin (50 μM prevented cell proliferation and the increased collagen mRNA levels induced by high glucose (25 mM. High glucose increased reactive oxygen species (ROS generation, and this was suppressed by pretreating delphinidin or the antioxidant N-acetyl cysteine. NADPH oxidase (NOX 1 was upregulated by high glucose, but pretreatment with delphinidin abrogated this upregulation. Increased mitochondrial superoxide by 25 mM glucose was also suppressed by delphinidin. The NOX inhibitor apocynin and mitochondria-targeted antioxidant Mito TEMPO inhibited ROS generation and cell proliferation induced by high glucose. Phosphorylation of extracellular signal regulated kinase (ERK1/2 was increased by high glucose, which was suppressed by delphinidin, apocynin or Mito TEMPO. Furthermore, PD98059 (an ERK1/2 inhibitor prevented the high glucose-induced cell proliferation and increased collagen mRNA levels. Transforming growth factor (TGF-β protein levels were elevated by high glucose, and pretreatment with delphinidin or PD98059 prevented this augmentation. These results suggest that delphinidin prevents high glucose-induced cell proliferation and collagen synthesis by inhibition of NOX-1 and mitochondrial superoxide in mesangial cells.

Abridged acid-base wet-milling synthesis of high purity hydroyapatite

Directory of Open Access Journals (Sweden)

Sandi Carolina Ruiz-Mendoza

2008-06-01

Full Text Available There is a plethora of routes to produce hydroxyapatite(HA and in general calcium phosphates(CP but production usually leads to a mixture of several phases. Besides ionic contamination, most of these methods are cumbersome, restricted to small volumes of product and require a lot of thermal energy. The acid-base route eliminates foreign ions or additives and its only byproduct is water. Heterogeneous reaction drawback is that solid reactants do not easily come in contact with each other and therefore addition and stirring times become very lengthy and still the product is a mixture. The synthesis started from calcium hydroxide and phosphoric acid (PA. Ball milling was used to favor kinetics and stoichiometry. Six sets of PA addition, paddle stirring and ball milling times were used. Products were evaluated by X ray diffraction (XRD, Fourier Transform Infrared (FTIR, scanning electron microscopy (SEM, X ray fluorescence (XRF and Ca/P ratio. Chemical analysis for calcium proceeded through oxalate precipitate and phosphorus by the phosphomolibdate technique. A set of conditions yielding high purity HA was established.

Photometric Characterization of the Reductive Amination Scope of the Imine Reductases from Streptomyces tsukubaensis and Streptomyces ipomoeae.

Science.gov (United States)

Matzel, Philipp; Krautschick, Lukas; Höhne, Matthias

2017-10-18

Imine reductases (IREDs) have emerged as promising enzymes for the asymmetric synthesis of secondary and tertiary amines starting from carbonyl substrates. Screening the substrate specificity of the reductive amination reaction is usually performed by time-consuming GC analytics. We found two highly active IREDs in our enzyme collection, IR-20 from Streptomyces tsukubaensis and IR-Sip from Streptomyces ipomoeae, that allowed a comprehensive substrate screening with a photometric NADPH assay. We screened 39 carbonyl substrates combined with 17 amines as nucleophiles. Activity data from 663 combinations provided a clear picture about substrate specificity and capabilities in the reductive amination of these enzymes. Besides aliphatic aldehydes, the IREDs accepted various cyclic (C 4 -C 8 ) and acyclic ketones, preferentially with methylamine. IR-Sip also accepted a range of primary and secondary amines as nucleophiles. In biocatalytic reactions, IR-Sip converted (R)-3-methylcyclohexanone with dimethylamine or pyrrolidine with high diastereoselectivity (>94-96 % de). The nucleophile acceptor spectrum depended on the carbonyl substrate employed. The conversion of well-accepted substrates could also be detected if crude lysates were employed as the enzyme source. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of [11C]-ohmefentanyl, a novel, highly potent and selective agonist for opiate μ-receptors

International Nuclear Information System (INIS)

Zhu, Y.C.; Academia Sinica, Shangha, SH; Prenant, C.; Crouzel, C.; Comar, D.; Chi, Z.Q.

1992-01-01

We describe the synthesis of 11 C-ohmefentanyl, a novel, highly potent and selective agonist for opiate μ-receptors, to be visualized by Positron Emission Tomography (PET). The unlabelled cis-A-ohmefentanyl was prepared in a nine-step synthesis and two-step fractional crystallization, and the OH-precursor for [ 11 C]-ohmefentanyl labelling was obtained by hydrolysis of the 4-N-propionyl group of cis-A-ohmefentanyl in 6 N hydrochloric acid. The [ 11 C]-propionyl chloride was prepared by carbonation of ethylmagnesium bromide with cyclotron-produced [ 11 C]-carbon dioxide followed by direct treatment of the intermediate complex with phthaloyl dichloride and 2,6-di-t-butylpyridine. Reaction of the OH-precursor with [ 11 C]-propionyl chloride yields [ 11 C]-ohmefentanyl separated by HPLC, with a high specific activity of 300-400 mCi μmol -1 . The keto-precursor prepared by hydrolysis of the 4-N-propionyl group of cis-10 in 8 N hydrochloric acid, was also used for [ 11 C]-ohmefentanyl labelling. Reaction of the [ 11 C]-propionyl chloride with keto-precursor, followed by addition of sodium borohydride, yields [ 11 C]-ohmefentanyl. The [ 11 C]-labelled ohmefentanyl obtained using the OH-precursor is a cis-A form, while that obtained using the keto-precursor is a mixture of cis-A and cis-B forms. (author)

Metal-free, mild, nonepimerizing, chemo- and enantio- or diastereoselective N-alkylation of amines by alcohols via oxidation/imine-iminium formation/reductive amination: a pragmatic synthesis of octahydropyrazinopyridoindoles and higher ring analogues.

Science.gov (United States)

Khan, Imran A; Saxena, Anil K

2013-12-06

A mild step and atom-economical nonepimerizing chemo- and enantioselective N-alkylating procedure has been developed via oxidation/imine-iminium formation/reduction cascade using TEMPO-BAIB-HEH-Brønsted acid catalysis in DMPU as solvent and a stoichiometric amount of amine. The optimized conditions were further extended for the nonenzymatic kinetic resolution of the chiral amine thus formed under nonenzymatic in situ hydrogen-transfer conditions using VAPOL-derived phosphoric acid (VAPOL-PA) as the Brønsted acid catalyst. The enantioselective cascade of the presented reaction was successfully utilized in the synthesis of octahydropyrazinopyridoindole and its higher ring analogues.

Carbon Isotope Systematics in Mineral-Catalyzed Hydrothermal Organic Synthesis Processes at High Temperature and Pressures

Science.gov (United States)

Fu, Qi; Socki, R. A.; Niles, Paul B.

2011-01-01

Observation of methane in the Martian atmosphere has been reported by different detection techniques. Reduction of CO2 and/or CO during serpentization by mineral surface catalyzed Fischer-Tropsch Type (FTT) synthesis may be one possible process responsible for methane generation on Mars. With the evidence a recent study has discovered for serpentinization in deeply buried carbon rich sediments, and more showing extensive water-rock interaction in Martian history, it seems likely that abiotic methane generation via serpentinization reactions may have been common on Mars. Experiments involving mineral-catalyzed hydrothermal organic synthesis processes were conducted at 750 C and 5.5 Kbars. Alkanes, alcohols and carboxylic acids were identified as organic compounds. No "isotopic reversal" of delta C-13 values was observed for alkanes or carboxylic acids, suggesting a different reaction pathway than polymerization. Alcohols were proposed as intermediaries formed on mineral surfaces at experimental conditions. Carbon isotope data were used in this study to unravel the reaction pathways of abiotic formation of organic compounds in hydrothermal systems at high temperatures and pressures. They are instrumental in constraining the origin and evolution history of organic compounds on Mars and other planets.

Optimization of components in high-yield synthesis of block copolymer-mediated gold nanoparticles

International Nuclear Information System (INIS)

Ray, Debes; Aswal, Vinod Kumar

2012-01-01

The optimization to achieve stable and high-yield gold nanoparticles in block copolymer-mediated synthesis has been examined. Gold nanoparticles are synthesized using block copolymer P85 in gold salt HAuCl 4 ·3H 2 O solution. This method usually has a very limited yield which does not simply increase with the increase in the gold salt concentration. We show that the yield can be enhanced by increasing the block copolymer concentration but is limited to the factor by which the concentration is increased. On the other hand, the presence of an additional reductant (trisodium citrate) in 1:1 molar ratio with gold salt enhances the yield by manyfold. In this case (with additional reductant), the stable and high-yield nanoparticles having size about 14 nm can be synthesized at very low block copolymer concentrations. These nanoparticles thus can be efficiently used for their application such as for adsorption of proteins.

Synthesis of tracers using automated radiochemistry and robotics

International Nuclear Information System (INIS)

Dannals, R.F.

1992-07-01

Synthesis of high specific activity radiotracers labeled with short-lived positron-emitting radionuclides for positron emission tomography (PET) often requires handling large initial quantities of radioactivity. High specific activities are required when preparing tracers for use in PET studies of neuroreceptors. A fully automated approach for tracer synthesis is highly desirable. This proposal involves the development of a system for the Synthesis of Tracers using Automated Radiochemistry and Robotics (STARR) for this purpose. While the long range objective of the proposed research is the development of a totally automated radiochemistry system for the production of major high specific activity 11 C-radiotracers for use in PET, the specific short range objectives are the automation of 11 C-methyl iodide ( 11 CH 3 I) production via an integrated approach using both radiochemistry modular labstations and robotics, and the extension of this automated capability to the production of several radiotracers for PET (initially, 11 C-methionine, 3-N-[ 11 C-methyl]spiperone, and [ 11 C]-carfentanil)