Science.gov

Sample records for efficient chemoselective synthesis

  1. Efficient, chemoselective synthesis of immunomicelles using single-domain antibodies with a C-terminal thioester

    PubMed Central

    Reulen, Sanne WA; van Baal, Ingrid; Raats, Jos MH; Merkx, Maarten

    2009-01-01

    Background Classical bioconjugation strategies for generating antibody-functionalized nanoparticles are non-specific and typically result in heterogeneous compounds that can be compromised in activity. Expression systems based on self-cleavable intein domains allow the generation of recombinant proteins with a C-terminal thioester, providing a unique handle for site-specific conjugation using native chemical ligation (NCL). However, current methods to generate antibody fragments with C-terminal thioesters require cumbersome refolding procedures, effectively preventing application of NCL for antibody-mediated targeting and molecular imaging. Results Targeting to the periplasm of E. coli allowed efficient production of correctly-folded single-domain antibody (sdAb)-intein fusions proteins. On column purification and 2-mercapthoethanesulfonic acid (MESNA)-induced cleavage yielded single-domain antibodies with a reactive C-terminal MESNA thioester in good yields. These thioester-functionalized single-domain antibodies allowed synthesis of immunomicelles via native chemical ligation in a single step. Conclusion A novel procedure was developed to obtain soluble, well-folded single-domain antibodies with reactive C-terminal thioesters in good yields. These proteins are promising building blocks for the chemoselective functionalization via NCL of a broad range of nanoparticle scaffolds, including micelles, liposomes and dendrimers. PMID:19619333

  2. Chemoselective efficient synthesis of functionalized ?-oxonitriles through cyanomethylation of Weinreb amides.

    PubMed

    Mamuye, Ashenafi Damtew; Castoldi, Laura; Azzena, Ugo; Holzer, Wolfgang; Pace, Vittorio

    2015-02-21

    A synthesis of ?-oxonitriles is reported via the generation of R(1)R(2)CLiCN species followed by the trapping with variously decorated Weinreb amides. The optimization study revealed that lithiation of acetonitriles is best accomplished by deprotonation with MeLi-LiBr at low temperature. The protocol can be conveniently adapted to the synthesis of ?-mono or ?,?-disubstituted cyanoketones. (15)N- and (17)O-NMR data are reported for selected compounds. PMID:25535702

  3. An improved chemo-enzymatic synthesis of 1-beta-O-acyl glucuronides: highly chemoselective enzymatic removal of protecting groups from corresponding methyl acetyl derivatives.

    PubMed

    Baba, Akiko; Yoshioka, Tadao

    2007-12-01

    An improved and widely applicable chemo-enzymatic method for the synthesis of a series of 1-beta-O-acyl glucuronides 5a-f has been developed from the corresponding methyl acetyl derivatives 3a-f, which were stereospecifically synthesized from cesium salts of carboxylic acids 1a-f and methyl 2,3,4-tri-O-acetyl-1-bromo-1-deoxy-alpha-D-glucopyranuronate (2). Chemoselectivity of lipase AS Amano (LAS) in the hydrolytic removal of O-acetyl groups of 3a-f to provide methyl esters 4a-f was influenced by the nature of their 1-beta-O-acyl groups; high selectivity was evident only for 3b and 3f. Carboxylesterase from Streptomyces rochei (CSR), newly screened as an alternative to LAS, showed much greater chemoselectivity toward the O-acetyl groups than LAS; 3a, 3d, and 3e were chemoselectively hydrolyzed only by CSR. The combination of CSR with LAS yielded better results in the hydrolysis of 3c and 3f than did single usage of CSR. Final deprotection of the methyl ester groups of 4a-f to provide 5a-f was chemoselectively achieved by using lipase from Candida antarctica type B (CAL-B) as well as esterase from porcine liver (PLE), although CAL-B possessed higher chemoselectivity and catalytic efficiency than did PLE. CSR also exhibited high chemoselectivity in the synthesis of (S)-naproxen 1-beta-O-acyl glucopyranoside (7) from its 2,3,4,6-tetra-O-acetyl derivative 6. PMID:17985922

  4. Synthesis and reactivities of monofluoro acylboronates in chemoselective amide bond forming ligation with hydroxylamines.

    PubMed

    Noda, Hidetoshi; Bode, Jeffrey W

    2015-12-15

    The development of chemoselective reactions is a cornerstone of bioorganic chemistry and chemical ligation. Our contributions in this area include the development of two mechanistically distinct amide bond forming reactions, the ?-ketoacid-hydroxylamine (KAHA) ligation for the chemical synthesis of proteins and the potassium acyltrifluoroborate (KAT) ligation for bioconjugation. The remarkable stability and unique reactivity of KATs with hydroxylamines prompted us to explore other acylborons as a ligation partner, which have been unappreciated in synthetic organic chemistry. A new convenient synthetic route was devised from KATs and suitable bidentate ligands, allowing for the preparation of a wide range of new acylboronates that retain one fluoride ligand on the boron. Our results established that a ligand on the boron is responsible for their reactivity and stability and provide a firm basis for further development of the acylboron-hydroxylamine amide bond forming ligation. PMID:26566143

  5. An efficient chemoselective reduction of furan series unsaturated dinitriles.

    PubMed

    Bobal, Pavel; Bobalova, Janette

    2013-01-01

    An efficient reduction of double bonds conjugated with nitrile groups and acid or base sensitive furan rings with 2-phenylbenzimidazoline generated in situ has been successfully accomplished with high yields and excellent selectivity. The employed reducing agent was prepared in one step from ordinary chemicals. The other advantages of the presented method include mild and convenient reaction conditions, a benign and cost effective reagent, simple work-up and separation of the products. As this process does neither affect cyano and nitro groups nor furan rings, it is a valuable alternative when metal-catalyzed hydrogenations or borohydride reductions have failed. PMID:23434871

  6. Chemoselective ligation

    DOEpatents

    Saxon, Eliana (Albany, CA); Bertozzi, Carolyn R. (Berkeley, CA)

    2011-04-12

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  7. Chemoselective ligation

    DOEpatents

    Saxon, Eliana (Albany, CA); Bertozzi, Carolyn R. (Berkeley, CA)

    2011-05-10

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  8. Chemoselective ligation

    DOEpatents

    Saxon, Eliana (Albany, CA); Bertozzi, Carolyn Ruth (Berkeley, CA)

    2011-12-13

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  9. Chemoselective ligation

    DOEpatents

    Saxon, Eliana (Albany, CA); Bertozzi, Carolyn Ruth (Berkeley, CA)

    2010-11-23

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  10. Chemoselective ligation

    DOEpatents

    Saxon, Eliana (Albany, CA); Bertozzi, Carolyn R. (Berkeley, CA)

    2010-02-23

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g. on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  11. Chemoselective ligation

    DOEpatents

    Saxon, Eliana; Bertozzi, Carolyn

    2006-10-17

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  12. Chemoselective ligation

    DOEpatents

    Saxon, Eliana (Albany, CA); Bertozzi, Carolyn (Berkeley, CA)

    2003-05-27

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  13. Palladium-Catalyzed Domino Synthesis of 4-Amino-3-acyl-2- naphthols via Isocyanide Chemoselective Insertion.

    PubMed

    Chen, Zhong; Duan, Hua-Qing; Jiang, Xiao; Zhu, Yong-Ming; Ji, Shun-Jun; Yang, Shi-Lin

    2015-08-21

    A novel and efficient strategy for the synthesis of sterically hindered 4-amino-3-acyl-2-naphthols through a palladium-catalyzed coupling reaction involving isocyanide chemselective insertion and domino isomerization has been developed. The methodology, which is in accordance with the principle of "atom and step economy", efficiently constructs 4-amino-3-acyl-2-naphthols in moderate to good yields. PMID:26246028

  14. Synthesis of Hydrophilic Aminooxy Linkers and Multivalent Cores for Chemoselective Aldehyde/Ketone Conjugation

    PubMed Central

    McReynolds, Katherine D.; Dimas, Dustin; Le, Hoang

    2014-01-01

    A series of three linear and two trivalent aminooxy-containing hydrophilic linkers and cores were synthesized. The five molecules contain from one to three aminooxy groups, and all but one contain an ether for enhanced aqueous solubility. These unique and versatile molecules can be utilized in the chemoselective conjugation of aldehyde/ketone-containing molecules, including reducing sugars, under mild aqueous conditions, and give rise to oxime-containing conjugates useful in a wide variety of applications and studies. The value of these aminooxy-based molecules and the ease and speed of preparation of both monovalent and multivalent oxime-linked molecules is demonstrated in two examples using the disaccharide cellobiose; one with a linear linker, and the second with a trivalent core. PMID:25382876

  15. Combined preconditioning and in vivo chemoselection with 6-thioguanine alone achieves highly efficient reconstitution of normal hematopoiesis with HPRT-deficient bone marrow

    PubMed Central

    Hacke, Katrin; Szakmary, Akos; Cuddihy, Andrew R; Rozengurt, Nora; Lemp, Nathan A; Aubrecht, Jiri; Lawson, Gregory W; Rao, Nagesh P; Crooks, Gay M; Schiestl, Robert H.; Kasahara, Noriyuki

    2014-01-01

    Purine analogs such as 6-thioguanine (6TG) cause myelotoxicity upon conversion into nucleotides by hypoxanthine-guanine phosphoribosyltransferase (HPRT). Here we have developed a novel and highly efficient strategy employing 6TG as a single agent for both conditioning and in vivo chemoselection of HPRT-deficient HSC. The dose-response and time course of 6TG myelotoxicity were first compared in HPRT-wild type mice and HPRT-deficient transgenic mice. Dosage and schedule parameters were optimized to employ 6TG for myelo-suppressive conditioning, immediately followed by in vivo chemoselection of HPRT-deficient transgenic donor bone marrow (BM) transplanted into syngeneic HPRT-wild type recipients. At appropriate doses, 6TG induced selective myelotoxicity without any adverse effects on extra-hematopoietic tissues in HPRT-wild type mice, while HSC deficient in HPRT activity were highly resistant to its cytotoxic effects. Combined 6TG conditioning and post transplant chemoselection consistently achieved ~95% engraftment of HPRT-deficient donor BM, with low overall toxicity. Long-term reconstitution of immunophenotypically normal BM was achieved in both primary and secondary recipients. Our results provide proof-of-concept that single-agent 6TG can be used both for myelo-suppressive conditioning without requiring irradiation, and for in vivo chemoselection of HPRT-deficient donor cells. Our results show that by applying the myelosuppressive effects of 6TG both before (as conditioning) and after transplantation (as chemoselection), highly efficient engraftment of HPRT-deficient hematopoietic stem cells can be achieved. PMID:22001673

  16. A new efficient catalytic system for the chemoselective cobalt-catalyzed cross-coupling of aryl Grignard reagents with primary and secondary alkyl bromides.

    PubMed

    Cahiez, Gérard; Chaboche, Christophe; Duplais, Christophe; Moyeux, Alban

    2009-01-15

    The cobalt-catalyzed alkylation of aromatic Grignard reagents is performed in good yields by using a new simple and efficient catalytic system: CoCl(2)/TMEDA (1:1). Primary and secondary cyclic or acyclic alkyl bromides were used successfully. The reaction is highly chemoselective since ester, amide, and keto groups are tolerated. The procedure is inexpensive and very easy to carry out on a larger scale. PMID:19093805

  17. AN EFFICIENT AND CHEMOSELECTIVE CBZ-PROTECTION OF AMINES USING SILICA-SULFURIC ACID AT ROOM TEMPERATURE

    EPA Science Inventory

    A simple, facile, and chemoselective N-benzyloxycarbonylation of amines using silica-sulfuric acid that proceeds under solvent-free conditions at room temperature has been achieved. These reactions are applicable to a wide variety of primary (aliphatic, cyclic) secondary amines, ...

  18. Reaction of Corey ylide with ?,?-unsaturated ketones: tuning of chemoselectivity toward dihydrofuran synthesis.

    PubMed

    Chagarovsky, Alexey O; Budynina, Ekaterina M; Ivanova, Olga A; Villemson, Elena V; Rybakov, Victor B; Trushkov, Igor V; Melnikov, Mikhail Ya

    2014-06-01

    A straightforward, efficient, and reliable approach to synthetically valuable 2,3-dihydrofurans via a reaction between Corey ylide and ?,?-unsaturated ketones has been developed. The use of simple and widely spread starting materials as well as mild reaction conditions and scalability provide a broad scope of 2,3-dihydrofurans. PMID:24819312

  19. Chemoselective Hydroxyl Group Transformation: An Elusive Target‡

    PubMed Central

    Trader, Darci J.; Carlson, Erin E.

    2012-01-01

    The selective reaction of one functional group in the presence of others is not a trivial task. A noteworthy amount of research has been dedicated to the chemoselective reaction of the hydroxyl moiety. This group is prevalent in many biologically important molecules including natural products and proteins. However, targeting the hydroxyl group is difficult for many reasons including its relatively low nucleophilicity in comparison to other ubiquitous functional groups such as amines and thiols. Additionally, many of the developed chemoselective reactions cannot be used in the presence of water. Despite these complications, chemoselective transformation of the hydroxyl moiety has been utilized in the synthesis of complex natural product derivatives, the reaction of tyrosine residues in proteins, the isolation of natural products and is the mechanism of action of myriad drugs. Here, methods for selective targeting of this group, as well as applications of several devised methods, are described. PMID:22695722

  20. Chemoselective Attachment of Biologically Active Proteins to Surfaces by Native Chemical Ligation

    SciTech Connect

    Cheung, C L; de Yoreo, J J; Coleman, M; Camarero, J A

    2003-11-22

    The present work describes our ongoing efforts towards the creation of micro and nanoscaled ordered arrays of protein covalently attached to site-specific chemical linkers patterned by different microlithographic techniques. We present a new and efficient solid-phase approach for the synthesis of chemically modified long alkyl-thiols. These compounds can be used to introduce chemoselective reacting groups onto silicon-based surfaces. We show that these modified thiols can be used for creating nano- and micrometric chemical patterns by using different lithographic techniques. We show that these patterns can react chemoselectively with proteins which have been recombinantly modified to contain complementary chemical groups at specific positions thus resulting in the oriented attachment of the protein to the surface.

  1. One-Pot Synthesis of N-(?-Peroxy)Indole/Carbazole via Chemoselective Three-Component Condensation Reaction in Open Atmosphere.

    PubMed

    Wang, Xinbo; Pan, Yupeng; Huang, Kuo-Wei; Lai, Zhiping

    2015-11-20

    A facile one-pot synthesis of N-(?-peroxy)indole and N-(?-peroxy)carbazole has been developed using metal-free, organo-acid-catalyzed three-component condensation reactions of indole/carbazole, aldehyde, and peroxide. Based on the reaction discovered, a new synthetic proposal for Fumitremorgin A and Verruculogen is introduced. Such a protocol could be easily handled and scaled up in an open atmosphere with a wide substrate scope, enabling the construction of a new molecule library. PMID:26541059

  2. Aminocyanation by the addition of N-CN bonds to arynes: chemoselective synthesis of 1,2-bifunctional aminobenzonitriles.

    PubMed

    Rao, Bin; Zeng, Xiaoming

    2014-01-01

    An efficient aminocyanation by the direct addition of aryl cyanamides to arynes is described, enabling incorporation of highly useful amino and cyano groups synchronously via cleavage of inert N-CN bonds, affording synthetically useful 1,2-bifunctional aminobenzonitriles. The postsynthetic functionalization of the aminocyanation products allows diverse formation of synthetically important derivatives such as drug molecule Ponstan and fused heterocycles. PMID:24325782

  3. Chemoselective and Enantioselective Hydrogenations on Immobilized Complexes

    NASA Astrophysics Data System (ADS)

    Zsigmond, Agnes; Notheisz, Ferenc; Kluson, Petr; Floris, Tomas

    Homogeneous catalysts, which are mixed with the reactants at the molecular level, typically show the highest activity and selectivity as they offer chemically well-defined active sites and are not limited by heat and mass transport. However, an inherent disadvantage of the homogeneous catalysis is the need to separate the catalyst from a product after the reaction. Therefore, solid or immobilized homogeneous catalysts are preferred in industry. In this contribution we pay attention to chemoselectivity, regioselectivity and enantioselectivity in the synthesis of fine chemicals by means of hydrogenation reactions with immobilised homogeneous complexes. Preferential hydrogenation of one functional group in a molecule over another is the chemoselective process, while regioselective hydrogenation is the preferential formation of one constitutional isomer of the product in a reaction in which other isomers may also be formed, and the stereoselective hydrogenation is the formation of an excess of one stereoisomer over others. Homogeneous and heterogeneous catalytic transfer hydrogenations (CTH) were additionally introduced as alternative methods to the classical hydrogenation processes. They utilise a different hydrogen source from molecular hydrogen and can find their use for reduction of any type of groups.

  4. Prebiotically plausible oligoribonucleotide ligation facilitated by chemoselective acetylation.

    PubMed

    Bowler, Frank R; Chan, Christopher K W; Duffy, Colm D; Gerland, Béatrice; Islam, Saidul; Powner, Matthew W; Sutherland, John D; Xu, Jianfeng

    2013-05-01

    The recent synthesis of pyrimidine ribonucleoside-2',3'-cyclic phosphates under prebiotically plausible conditions has strengthened the case for the involvement of ribonucleic acid (RNA) at an early stage in the origin of life. However, a prebiotic conversion of these weakly activated monomers, and their purine counterparts, to the 3',5'-linked RNA polymers of extant biochemistry has been lacking (previous attempts led only to short oligomers with mixed linkages). Here we show that the 2'-hydroxyl group of oligoribonucleotide-3'-phosphates can be chemoselectively acetylated in water under prebiotically credible conditions, which allows rapid and efficient template-directed ligation. The 2'-O-acetyl group at the ligation junction of the product RNA strand can be removed under conditions that leave the internucleotide bonds intact. Remarkably, acetylation of mixed oligomers that possess either 2'- or 3'-terminal phosphates is selective for the 2'-hydroxyl group of the latter. This newly discovered chemistry thus suggests a prebiotic route from ribonucleoside-2',3'-cyclic phosphates to predominantly 3',5'-linked RNA via partially 2'-O-acetylated RNA. PMID:23609088

  5. Synthesis of a Sulfonated Two-Dimensional Covalent Organic Framework as an Efficient Solid Acid Catalyst for Biobased Chemical Conversion.

    PubMed

    Peng, Yongwu; Hu, Zhigang; Gao, Yongjun; Yuan, Daqiang; Kang, Zixi; Qian, Yuhong; Yan, Ning; Zhao, Dan

    2015-10-01

    Because of limited framework stability tolerance, de?novo synthesis of sulfonated covalent organic frameworks (COFs) remains challenging and unexplored. Herein, a sulfonated two-dimensional crystalline COF, termed TFP-DABA, was synthesized directly from 1,3,5-triformylphloroglucinol and 2,5-diaminobenzenesulfonic acid through a previously reported Schiff base condensation reaction, followed by irreversible enol-to-keto tautomerization, which strengthened its structural stability. TFP-DABA is a highly efficient solid acid catalyst for fructose conversion with remarkable yields (97?% for 5-hydroxymethylfurfural and 65?% for 2,5-diformylfuran), good chemoselectivity, and good recyclability. The present study sheds light on the de?novo synthesis of sulfonated COFs as novel solid acid catalysts for biobased chemical conversion. PMID:26448524

  6. Chemoselective Reactions of Citral: Green Syntheses of Natural Perfumes for the Undergraduate Organic Laboratory

    ERIC Educational Resources Information Center

    Cunningham, Anna D.; Ham, Eun Y.; Vosburg, David A.

    2011-01-01

    Chemoselectivity is a central concept in organic synthesis and may be readily appreciated in the context of the fragrant, polyfunctional natural product citral. We describe three single-step reactions students may perform on citral to synthesize other natural perfumes: citronellal, geraniol, nerol, or epoxycitral. Each of the reactions uses a…

  7. An Assessment of Chemoselective Neoglycosylation Methods Using Chlorambucil as a Model

    PubMed Central

    Goff, Randal D.; Thorson, Jon S.

    2010-01-01

    To systematically assess the impact of glycosylation and the corresponding chemoselective linker upon the anticancer activity/selectivity of the drug chlorambucil, herein we report the synthesis and anticancer activities of a 63-member library of chlorambucil-based neoglycosides. A comparison of N-alkoxyamine-, N-acyl hydrazine- and N-hydroxyamine-based chemoselective glycosylation of chlorambucil revealed sugar-and linker-dependent partitioning among open and closed-ring neoglycosides and corresponding sugar-dependent variant biological activity. Cumulatively, this study represents the first neoglycorandomization of a synthetic drug and expands our understanding of the impact of sugar structure upon product distribution/equilibria in the context of N-alkoxyamino-, N-hydroxyamino- and N-acyl hydrazine-based chemoselective glycosylation. This study also revealed several analogs with increased in vitro anticancer activity, most notably D-threoside 60 (NSC 748747), which displayed much broader tumor specificity and notably increased potency over the parent drug. PMID:20973561

  8. Dearomatization Strategies in the Synthesis of Complex Natural Products

    PubMed Central

    Roche, Stéphane P.; Porco, John A.

    2014-01-01

    Evolution in the field of the total synthesis of natural products has led to exciting developments over the last decade. Numerous chemo-selective and enantioselective methodologies have emerged from total syntheses, resulting in efficient access to many important natural product targets. This Review highlights recent developments concerning dearomatization, a powerful strategy for the total synthesis of architecturally complex natural products wherein planar, aromatic scaffolds are converted to three-dimensional molecular architectures. PMID:21506209

  9. Iron-catalyzed aerobic oxidative cleavage of the C-C ?-bond using air as the oxidant: chemoselective synthesis of carbon chain-shortened aldehydes, ketones and 1,2-dicarbonyl compounds.

    PubMed

    Xing, Qi; Lv, Hui; Xia, Chungu; Li, Fuwei

    2016-01-11

    A simple iron-catalyzed aerobic oxidative C-C ?-bond cleavage of ketones has been developed. Readily available and environmentally benign air is used as the oxidant. This reaction avoids the use of noble metal catalysts or specialized oxidants, chemoselectively yielding carbon chain-shortened aldehydes, ketones and 1,2-dicarbonyl compounds without overoxidation. PMID:26529597

  10. Phosphotungstic acid as a versatile catalyst for the synthesis of fragrance compounds by alpha-pinene oxide isomerization: solvent-induced chemoselectivity.

    PubMed

    da Silva Rocha, Kelly A; Hoehne, Juliana L; Gusevskaya, Elena V

    2008-01-01

    The remarkable effect of the solvent on the catalytic performance of H3PW12O40, the strongest heteropoly acid in the Keggin series, allows direction of the transformations of alpha-pinene oxide (1) to either campholenic aldehyde (2), trans-carveol (3), trans-sobrerol (4 a), or pinol (5). Each of these expensive fragrance compounds was obtained in good to excellent yields by using an appropriate solvent. Solvent polarity and basicity strongly affect the reaction pathways: nonpolar nonbasic solvents favor the formation of aldehyde 2; polar basic solvents favor the formation of alcohol 3; whereas in polar weakly basic solvents, the major products are compounds 4 a and 5. On the other hand, in 1,4-dioxane, which is a nonpolar basic solvent, both aldehyde 2 and alcohol 3 are formed in comparable amounts. The use of very low catalyst loading (0.005-1 mol %) and the possibility of catalyst recovery and recycling without neutralization are significant advantages of this simple, environmentally benign, and low-cost method. This method represents the first example of the synthesis of isomers from alpha-pinene oxide, other than campholenic aldehyde, with a selectivity that is sufficient for practical usage. PMID:18512831

  11. Hydroboration-oxidation: A chemoselective route to cellulose ?-hydroxyalkanoate esters.

    PubMed

    Meng, Xiangtao; York, Emily A; Liu, Shu; Edgar, Kevin J

    2015-11-20

    We describe the first synthesis of hydroxy-functionalized polysaccharide esters via chemoselective olefin hydroboration-oxidation in the presence of ester groups. Cellulose esters with terminally olefinic side chains were first synthesized by esterification of commercially available cellulose esters (e.g., cellulose acetate) with undec-10-enoyl chloride or pent-4-enoyl chloride. Subsequent two-step, one-pot hydroboration-oxidation reactions of the cellulose esters were performed, using 9-borabicyclo[3.3.1]nonane as hydroboration agent, followed by oxidizing the intermediate borane to a hydroxyl group using mildly alkaline H2O2. Sodium acetate was used as a weak base to catalyze the oxidation, thereby minimizing undesired ester hydrolysis. Characterization methods including FTIR, (1)H, and (13)C NMR proved the selectivity of the hydroboration-oxidation pathway, providing a family of novel cellulose ?-hydroxyalkanoyl esters that were previously difficult to access. PMID:26344280

  12. Approximation concepts for efficient structural synthesis

    NASA Technical Reports Server (NTRS)

    Schmit, L. A., Jr.; Miura, H.

    1976-01-01

    It is shown that efficient structural synthesis capabilities can be created by using approximation concepts to mesh finite element structural analysis methods with nonlinear mathematical programming techniques. The history of the application of mathematical programming techniques to structural design optimization problems is reviewed. Several rather general approximation concepts are described along with the technical foundations of the ACCESS 1 computer program, which implements several approximation concepts. A substantial collection of structural design problems involving truss and idealized wing structures is presented. It is concluded that since the basic ideas employed in creating the ACCESS 1 program are rather general, its successful development supports the contention that the introduction of approximation concepts will lead to the emergence of a new generation of practical and efficient, large scale, structural synthesis capabilities in which finite element analysis methods and mathematical programming algorithms will play a central role.

  13. Chemoselective hydrogenation of carbonyl compounds and acceptorless dehydrogenative coupling of alcohols.

    PubMed

    Spasyuk, Denis; Vicent, Cristian; Gusev, Dmitry G

    2015-03-25

    OsHCl(CO)[?(3)-PyCH2NHC2H4NHPtBu2] is the first efficient catalyst for chemoselective reduction of challenging unsaturated esters to enols and for acceptorless coupling of amines with MeOH and EtOH affording formamides and acetamides. The NMR, ESI-MS, and DFT data indicate a mechanism proceeding in the metal coordination sphere and producing no free organic intermediates. PMID:25741992

  14. Highly Efficient Asymmetric Synthesis of -Amino Acid Derivatives via

    E-print Network

    Zhang, Xumu

    Highly Efficient Asymmetric Synthesis of -Amino Acid Derivatives via Rhodium pure -amino acids and their deriva- tives are important building blocks for the synthesis of -peptides of -amino acids has attracted extensive interest. Although several stoichio- metric and catalytic methods

  15. Efficient synthesis of benzamide riboside, a potential anticancer agent.

    PubMed

    Bonnac, Laurent F; Gao, Guang-Yao; Chen, Liqiang; Patterson, Steven E; Jayaram, Hiremagalur N; Pankiewicz, Krzysztof W

    2007-01-01

    An efficient five step synthesis of benzamide riboside (BR) amenable for a large scale synthesis has been developed. It allows for extensive pre-clinical studies of BR as a potential anticancer agent. PMID:18066762

  16. Efficient Synthesis of Fluorescent Squaraine Rotaxane Dendrimers

    PubMed Central

    Xiao, Shuzhang; Fu, Na; Peckham, Kaitlin; Smith, Bradley D.

    2009-01-01

    A squaraine rotaxane scaffold with four alkynes groups is readily converted into a range of dendritic architectures using high yielding copper catalyzed alkyne azide cycloaddition (CuAAC) chemistry. A convergent synthesis approach is more efficient than a divergent pathway. Dendritic squaraine rotaxanes with peripheral amine groups can be further functionalized to produce multivalent deep-red fluorescent derivatives that exhibit high brightness and outstanding chemical stability in biological solution. The surface groups on these functionalized fluorescent dendrimers include guanidinium, mannose, and phosphatidylcholine. PMID:19957971

  17. Chemoselective conversion of biologically sourced polyols into chiral synthons.

    PubMed

    Adduci, Laura L; Bender, Trandon A; Dabrowski, Jennifer A; Gagné, Michel R

    2015-07-01

    Crude oil currently provides much of the world's energy, but it is also the source of many feedstock chemicals. Methodology for the conversion of biomass into useful chemicals has often focused on either complete deoxygenation or the production of high-volume platform chemicals. Here, we describe the chemoselective partial reduction of silyl-protected C6O6-derived polyols to produce a diverse set of oxygen-functionalized chiral synthons. The combination of B(C6F5)3 and a tertiary silane efficiently generates a reactive equivalent of an electrophilic silylium ion (R3Si(+)) and a hydride (H(-)) reducing agent. The mechanism of oxygen loss does not involve a dehydrative elimination and thus avoids ablation of stereochemistry. Neighbouring group participation and the formation of cyclic intermediates is key to achieving selectivity in these reactions and, where both primary and secondary C-O bonds are present, the mechanism allows further control. The method provides--in one or two synthetic steps--highly improved syntheses of many C6On synthons as well as several previously undescribed products. PMID:26100806

  18. Chemoselective conversion of biologically sourced polyols into chiral synthons

    NASA Astrophysics Data System (ADS)

    Adduci, Laura L.; Bender, Trandon A.; Dabrowski, Jennifer A.; Gagné, Michel R.

    2015-07-01

    Crude oil currently provides much of the world's energy, but it is also the source of many feedstock chemicals. Methodology for the conversion of biomass into useful chemicals has often focused on either complete deoxygenation or the production of high-volume platform chemicals. Here, we describe the chemoselective partial reduction of silyl-protected C6O6-derived polyols to produce a diverse set of oxygen-functionalized chiral synthons. The combination of B(C6F5)3 and a tertiary silane efficiently generates a reactive equivalent of an electrophilic silylium ion (R3Si+) and a hydride (H-) reducing agent. The mechanism of oxygen loss does not involve a dehydrative elimination and thus avoids ablation of stereochemistry. Neighbouring group participation and the formation of cyclic intermediates is key to achieving selectivity in these reactions and, where both primary and secondary C-O bonds are present, the mechanism allows further control. The method provides—in one or two synthetic steps—highly improved syntheses of many C6On synthons as well as several previously undescribed products.

  19. Safe and Efficient Tetrazole Synthesis in a Continuous Flow Microreactor

    E-print Network

    Palde, Prakash B.

    Safer flow: The synthesis of 5-substituted tetrazoles in flow (see scheme) is safe, efficient, scalable, requires no metal promoter, and uses a near-equimolar amount of NaN[subscript 3], yet nonetheless displays a broad ...

  20. A novel gold-catalyzed chemoselective reduction of alpha,beta-unsaturated aldehydes using CO and H2O as the hydrogen source.

    PubMed

    He, Lin; Yu, Feng-Jiao; Lou, Xia-Bing; Cao, Yong; He, He-Yong; Fan, Kang-Nian

    2010-03-01

    Chemoselective reduction of alpha,beta-unsaturated aldehydes in the presence of CO and H(2)O proceeds effectively over a ceria-supported gold catalyst system, providing a novel, efficient and clean approach to produce useful primary allyl alcohols with excellent activity and selectivity. PMID:20162179

  1. Highly Efficient Synthesis of Chiral -Amino Acid Derivatives via

    E-print Network

    Zhang, Xumu

    Highly Efficient Synthesis of Chiral -Amino Acid Derivatives via Asymmetric Hydrogenation Wenjun-TangPhos complex is an efficient hydrogenation catalyst for making chiral -amino acid derivatives. With the Rh -amino acids has drawn a great deal of attention due to its importance in biomedical research

  2. Chemoselective silicification of synthetic peptides and polyamines.

    PubMed

    Abacilar, Maryna; Daus, Fabian; Geyer, Armin

    2015-01-01

    Biosilicification sets the standard for the localized in vitro precipitation of silica at low orthosilicate concentrations in aqueous environment under ambient conditions. Numerous parameters must be controlled for the development of new technologies in designing inventive nanosilica structures, which are able to challenge the biological templates. A long neglected requirement that came into focus in the recent years are the cellular techniques of preventing unintentional lithification of cellular structures since numerous cellular components such as membranes, DNA, and proteins are known to precipitate nanosilica. The diatom metabolism makes use of techniques that restrict silicification to an armor of silica around the cell wall while avoiding the petrifying gaze of Medusa, which turns the whole cell into stone. Step by step, biochemistry unveils the hierarchical interplay of an arsenal of low-molecular weight molecules, proteins, and the cytoskeletal architecture and it becomes clearer why the organisms invest much metabolic effort for an obviously simple chemical reaction like the precipitation of amorphous silica. The discrimination between different soluble components in the silicification process (chemoselective silicification) is not only vitally important for the diatom but poses an interesting challenge for in vitro experiments. Until now, silica precipitation studies were mainly focused on the amount, the morphology, and composition of the precipitate while disregarding a quantitative analysis of the remaining soluble components. Here, we turn the tables and quantify the soluble components by (1)H NMR in the progress of precipitation and present experiments which quantify the additivity, and potential cooperativity of long chain polyamines (LCPAs) and cationic peptides in the silicification process. PMID:25671155

  3. An efficient synthesis of loline alkaloids

    NASA Astrophysics Data System (ADS)

    Cakmak, Mesut; Mayer, Peter; Trauner, Dirk

    2011-07-01

    Loline (1) is a small alkaloid that, in spite of its simple-looking structure, has posed surprising challenges to synthetic chemists. It has been known for more than a century and has been the subject of extensive biological investigations, but only two total syntheses have been achieved to date. Here, we report an asymmetric total synthesis of loline that, with less then ten steps, is remarkably short. Our synthesis incorporates a Sharpless epoxidation, a Grubbs olefin metathesis and an unprecedented transannular aminobromination, which converts an eight-membered cyclic carbamate into a bromopyrrolizidine. The synthesis is marked by a high degree of chemo- and stereoselectivity and gives access to several members of the loline alkaloid family. It delivers sufficient material to support a programme aimed at studying the complex interactions between plants, fungi, insects and bacteria brokered by loline alkaloids.

  4. Beta-methylcysteines: synthesis and application in native chemical ligation 

    E-print Network

    Lai, Zhi

    2000-01-01

    Native chemical ligation has emerged as a powerful method in peptide synthesis. In this method, an initial transthioesterification step involves a chemoselective reaction that occurs between a peptide fragment containing an amino-terminal cysteine...

  5. Chemoselective Transformation of Diarylethanones to Arylmethanoic Acids and Diarylmethanones and Mechanistic Insights.

    PubMed

    Wang, Xing; Chen, Rui-Xi; Wei, Zeng-Feng; Zhang, Chen-Yang; Tu, Hai-Yang; Zhang, Ai-Dong

    2016-01-01

    The chemoselective transformation of diarylethanones via either aerobic oxidative cleavage to give arylmethanoic acids or tandem aerobic oxidation/benzilic acid rearrangement/decarboxylation to give diarylmethanones has been developed. The transformation is controllable and applicable to a broad spectrum of substrates and affords the desired products in good to excellent yields. Mechanistic insights with control reactions, (1)H NMR tracking, and single-crystal X-ray diffraction reveal a complex mechanistic network in which two common intermediates, ?-ketohydroperoxide and diarylethanedione, and three plausible pathways are proposed and verified. These pathways are interlinked and can be switched reasonably by changing the reaction conditions. This method enables scalable synthesis and access to a number of valuable compounds, including vitamin B3, diphenic acid, and the nonsteroidal anti-inflammatory drug ketoprofen. The present protocol represents a step forward in exploiting complex mechanistic networks to control reaction pathways, achieving divergent syntheses from the same class of starting materials. PMID:26618373

  6. Efficient Synthesis of Enantiopure -Amino--Keto Acids from

    E-print Network

    Hergenrother, Paul J.

    Efficient Synthesis of Enantiopure -Amino--Keto Acids from L-Homoserine Anil K. Sharma and Paul J hergenro@uiuc.edu Received March 26, 2003 ABSTRACT A variety of -amino--keto acids were prepared in four-catalyzed Grignard addition to a N-protected derivative of L-homoserine. One of the -amino--keto acids was then used

  7. Noninvasive imaging of sialyltransferase activity in living cells by chemoselective recognition

    NASA Astrophysics Data System (ADS)

    Bao, Lei; Ding, Lin; Yang, Min; Ju, Huangxian

    2015-06-01

    To elucidate the biological and pathological functions of sialyltransferases (STs), intracellular ST activity evaluation is necessary. Focusing on the lack of noninvasive methods for obtaining the dynamic activity information, this work designs a sensing platform for in situ FRET imaging of intracellular ST activity and tracing of sialylation process. The system uses tetramethylrhodamine isothiocyanate labeled asialofetuin (TRITC-AF) as a ST substrate and fluorescein isothiocyanate labeled 3-aminophenylboronic acid (FITC-APBA) as the chemoselective recognition probe of sialylation product, both of which are encapsulated in a liposome vesicle for cellular delivery. The recognition of FITC-APBA to sialylated TRITC-AF leads to the FRET signal that is analyzed by FRET efficiency images. This strategy has been used to evaluate the correlation of ST activity with malignancy and cell surface sialylation, and the sialylation inhibition activity of inhibitors. This work provides a powerful noninvasive tool for glycan biosynthesis mechanism research, cancer diagnostics and drug development.

  8. Enantioselective preparation and chemoselective cross-coupling of 1,1-diboron compounds

    NASA Astrophysics Data System (ADS)

    Lee, Jack Chang Hung; McDonald, Robert; Hall, Dennis G.

    2011-11-01

    The simplicity, efficiency and generality of the transition-metal-catalysed Suzuki-Miyaura cross-coupling reaction has led to its application in the preparation of a wide variety of organic compounds. Cross-coupling of alkylboron derivatives, however, remains a major challenge, in particular with regard to stereochemical control. Here, we describe the preparation and reaction of highly optically enriched 1,1-diboron compounds. A catalytic asymmetric conjugate borylation of ?-boronylacrylates provided geminal diboronate products that feature two distinct boronyl units, in 99% enantiomeric excess. Chemoselective cross-coupling of one-boronyl unit, a trifluoroborate salt, occurred stereospecifically via inversion of its configuration to generate enantioenriched benzylic or allylic boronates. The difficult transmetallation in the Suzuki-Miyaura catalytic reaction cycle is believed to be facilitated by a stabilization effect from the second boronyl unit, and internal coordination by the oxygen of the proximal carboxyester. We also explored subsequent functionalization of the second boronyl unit.

  9. Noninvasive imaging of sialyltransferase activity in living cells by chemoselective recognition

    PubMed Central

    Bao, Lei; Ding, Lin; Yang, Min; Ju, Huangxian

    2015-01-01

    To elucidate the biological and pathological functions of sialyltransferases (STs), intracellular ST activity evaluation is necessary. Focusing on the lack of noninvasive methods for obtaining the dynamic activity information, this work designs a sensing platform for in situ FRET imaging of intracellular ST activity and tracing of sialylation process. The system uses tetramethylrhodamine isothiocyanate labeled asialofetuin (TRITC-AF) as a ST substrate and fluorescein isothiocyanate labeled 3-aminophenylboronic acid (FITC-APBA) as the chemoselective recognition probe of sialylation product, both of which are encapsulated in a liposome vesicle for cellular delivery. The recognition of FITC-APBA to sialylated TRITC-AF leads to the FRET signal that is analyzed by FRET efficiency images. This strategy has been used to evaluate the correlation of ST activity with malignancy and cell surface sialylation, and the sialylation inhibition activity of inhibitors. This work provides a powerful noninvasive tool for glycan biosynthesis mechanism research, cancer diagnostics and drug development. PMID:26046317

  10. Applied reaction dynamics: Efficient synthesis gas production via single collision partial oxidation of methane to CO on Rh,,111...

    E-print Network

    Sibener, Steven

    Applied reaction dynamics: Efficient synthesis gas production via single collision partial fuel production Fischer-Tropsch or methanol synthesis . Moreover, under the reaction conditions dissociation. These results demonstrate the efficient conversion of methane to synthesis gas, CO+2H2

  11. EFFICIENT AUTOMATED SYNTHESIS, PROGRAMING, AND IMPLEMENTATION OF MULTI-PROCESSOR PLATFORMS ON FPGA CHIPS

    E-print Network

    Stefanov, Todor Plamenov

    EFFICIENT AUTOMATED SYNTHESIS, PROGRAMING, AND IMPLEMENTATION OF MULTI-PROCESSOR PLATFORMS ON FPGA. Moreover, the EDK IP library supports very limited communication structures for connecting processors, e

  12. Chemoselective Amination of Propargylic C(sp3)–H Bonds via Co(II)-Based Metalloradical Catalysis**

    PubMed Central

    Li, Chaoqun; Jiang, Huiling; Lizardi, Christopher L.

    2014-01-01

    Highly chemoselective intramolecular amination of propargylic C(sp3)–H bonds has been demonstrated for N-bishomopropargylic sulfamoyl azides via Co(II)-based metalloradical catalysis. Supported by D2h-symmetric amidoporphyrin ligand 3,5-DitBu-IbuPhyrin, the Co(II)-catalyzed C–H amination process can proceed effectively under neutral and nonoxidative conditions without the need of any additives, generating N2 as the only byproduct. The metalloradical amination is suitable to both secondary and tertiary propargylic C–H substrates with an unusually high degree of functional group tolerance, providing a direct method for high-yielding synthesis of functionalized propargylamine derivatives. PMID:24840605

  13. A simple, universal, efficient PCR-based gene synthesis method: sequential OE-PCR gene synthesis.

    PubMed

    Zhang, Pingping; Ding, Yingying; Liao, Wenting; Chen, Qiuli; Zhang, Huaqun; Qi, Peipei; He, Ting; Wang, Jinhong; Deng, Songhua; Pan, Tianyue; Ren, Hao; Pan, Wei

    2013-07-25

    Herein we present a simple, universal, efficient gene synthesis method based on sequential overlap extension polymerase chain reactions (OE-PCRs). This method involves four key steps: (i) the design of paired complementary 54-mer oligonucleotides with 18 bp overlaps, (ii) the utilisation of sequential OE-PCR to synthesise full-length genes, (iii) the cloning and sequencing of four positive T-clones of the synthesised genes and (iv) the resynthesis of target genes by OE-PCR with correct templates. Mispriming and secondary structure were found to be the principal obstacles preventing successful gene synthesis and were easily identified and solved in this method. Compensating for the disadvantages of being laborious and time-consuming, this method has many attractive advantages, such as the ability to guarantee successful gene synthesis in most cases and good allowance for Taq polymerase, oligonucleotides, PCR conditions and a high error rate. Thus, this method provides an alternative tool for individual gene synthesis without strict needs of the high-specialised experience. PMID:23597923

  14. Chemoselective reduction and oxidation of ketones in water through control of the electron transfer pathway

    PubMed Central

    Kim, Sun Min; Yoo, Ho Sung; Hosono, Hideo; Yang, Jung Woon; Kim, Sung Wng

    2015-01-01

    The selective synthesis of different products from the same starting materials in water, which is the most abundant solvent in nature, is a crucial issue as it maximizes the utilization of materials. Realizing such reactions for ketones is of considerable importance because numerous organic functionalities can be obtained via nucleophilic addition reactions. Herein, we report chemoselective reduction and oxidation reactions of 1,2-diketones in water, which initiates anionic electron transfer from the inorganic electride [Ca24Al28O64]4+·4e?, through controlling the pathway of the electrons to substrates. The generation of different radical species for transient intermediates was the key process required to control the reaction selectivity, which was achieved by reacting the anionic electrons with either diketones or O2, leading to the formation of ketyl dianion and superoxide radicals in the reduction and oxidation reactions, respectively. This methodology that utilizes electrides may provide an alternative to the pulse radiolysis of water in synthetic chemistry. PMID:26020413

  15. Alkene Chemoselectivity in Ruthenium-Catalyzed Z-Selective Olefin Metathesis

    PubMed Central

    Cannon, Jeffrey S.

    2013-01-01

    Chelated ruthenium catalysts have achieved highly chemoselective olefin metathesis reactions. Terminal and internal Z olefins were selectively reacted in the presence of internal E olefins. Products were produced in good yield and high stereoselectivity for formation of a new Z olefin. No products of metathesis with the internal E olefin were observed. Chemoselectivity for terminal olefins was also observed over both sterically hindered and electronically deactivated alkenes. PMID:23832646

  16. Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

    PubMed Central

    Matthessen, Roman; Fransaer, Jan; Binnemans, Koen

    2014-01-01

    Summary The near-unlimited availability of CO2 has stimulated a growing research effort in creating value-added products from this greenhouse gas. This paper presents the trends on the most important methods used in the electrochemical synthesis of carboxylic acids from carbon dioxide. An overview is given of different substrate groups which form carboxylic acids upon CO2 fixation, including mechanistic considerations. While most work focuses on the electrocarboxylation of substrates with sacrificial anodes, this review considers the possibilities and challenges of implementing other synthetic methodologies. In view of potential industrial application, the choice of reactor setup, electrode type and reaction pathway has a large influence on the sustainability and efficiency of the process. PMID:25383120

  17. Glycoprotein Synthesis: An Update David P. Gamblin, Eoin M. Scanlan, and Benjamin G. Davis*

    E-print Network

    Davis, Ben G.

    in the `quality control' of protein synthesis.7-9 In the absence of correct glycosylation, many proteins foldGlycoprotein Synthesis: An Update David P. Gamblin, Eoin M. Scanlan, and Benjamin G. Davis Synthesis 143 3.1. Indiscriminate Convergent Glycosylation 143 3.2. Chemoselective and Site

  18. Short and highly efficient synthesis of lipid peroxidation inhibitor pyrrolostatin and some analogues thereof.

    PubMed

    Schmidt, Jens; Adrian, Juliane; Christian B W Stark

    2015-08-14

    A highly efficient and scalable synthesis of potent lipid peroxidation inhibitor pyrrolostatin is reported (4 steps, 48%). In addition to the synthesis of the natural product, strategies for the preparation of analogues differing in the three structural subunits, the polar head group, the N-substituent and the lipophilic tail are described. PMID:26154919

  19. Efficient synthesis of anacardic acid analogues and their antibacterial activities.

    PubMed

    Mamidyala, Sreeman K; Ramu, Soumya; Huang, Johnny X; Robertson, Avril A B; Cooper, Matthew A

    2013-03-15

    Anacardic acid derivatives exhibit a broad range of biological activities. In this report, an efficient method for the synthesis of anacardic acid derivatives was explored, and a small set of salicylic acid variants synthesised retaining a constant hydrophobic element (a naphthyl tail). The naphthyl side chain was introduced via Wittig reaction and the aldehyde installed using directed ortho-metalation reaction of the substituted o-anisic acids. The failure of ortho-metalation using unprotected carboxylic acid group compelled us to use directed ortho-metalation in which a tertiary amide was used as a strong ortho-directing group. In the initial route, tertiary amide cleavage during final step was challenging, but cleaving the tertiary amide before Wittig reaction was beneficial. The Wittig reaction with protected carboxylic group (methyl ester) resulted in side-products whereas using sodium salt resulted in higher yields. The novel compounds were screened for antibacterial activity and cytotoxicity. Although substitution on the salicylic head group enhanced antibacterial activities they also enhanced cytotoxicity. PMID:23416004

  20. A new and efficient procedure for the synthesis of hexahydropyrimidine-fused 1,4-naphthoquinones

    PubMed Central

    Reis, Marcelo Isidoro P; Campos, Vinícius R; Resende, Jackson A L C; Silva, Fernando C

    2015-01-01

    Summary A new and efficient method for the synthesis of hexahydropyrimidine-fused 1,4-naphthoquinones in one step with high yields from the reaction of lawsone with 1,3,5-triazinanes was developed. PMID:26425181

  1. Tandem Reactions for Streamlining Synthesis

    PubMed Central

    HUSSAIN, MAHMUD M.; WALSH, PATRICK J.

    2009-01-01

    CONSPECTUS In 1980 Sharpless and Katsuki introduced the asymmetric epoxidation of prochiral allylic alcohols (the Sharpless-Katsuki Asymmetric Epoxidation), which enabled the rapid synthesis of highly enantioenriched epoxy alcohols. This reaction was a milestone in the development of asymmetric catalysis because it was the first highly enantioselective oxidation reaction. Furthermore, it provided access to enantioenriched allylic alcohols that are now standard starting materials in natural product synthesis. In 1981 Sharpless and coworkers made another seminal contribution by describing the kinetic resolution (KR) of racemic allylic alcohols. This work demonstrated that small-molecule catalysts could compete with enzymatic catalysts in KRs. For these pioneering works, Sharpless was awarded the 2001 Nobel Prize with Knowles and Noyori. Despite these achievements, the Sharpless KR is not an efficient method to prepare epoxy alcohols with high enantiomeric excess (ee). First, the racemic allylic alcohol must be prepared and purified. KR of the racemic allylic alcohol must be stopped at low conversion, because the ee of the product epoxy alcohol decreases as the KR progresses. Thus, better methods to prepare epoxy alcohols containing stereogenic carbinol carbons are needed. This Account summarizes our efforts to develop one-pot methods for the synthesis of various epoxy alcohols and allylic epoxy alcohols with high enantio-, diastereo-, and chemoselectivity. Our laboratory developed titanium-based catalysts for use in the synthesis of epoxy alcohols with tertiary carbinols. The catalysts are involved in the first step, which is an asymmetric alkyl or allyl addition to enones. The resulting intermediates are then subjected to a titanium-directed diastereoselective epoxidation to provide tertiary epoxy alcohols. Similarly, the synthesis of acyclic epoxy alcohols begins with asymmetric additions to enals and subsequent epoxidation. The methods described here enable the synthesis of skeletally diverse epoxy alcohols. PMID:18710197

  2. Development of a Rhodium(II)-Catalyzed Chemoselective C(sp(3) )?H Oxygenation.

    PubMed

    Lin, Yun; Zhu, Lei; Lan, Yu; Rao, Yu

    2015-10-12

    We report the first example of Rh(II) -catalyzed chemoselective double C(sp(3) )?H oxygenation, which can directly transform various toluene derivatives into highly valuable aromatic aldehydes with great chemoselectivity and practicality. The critical combination of catalyst Rh(OAc)2 , oxidant Selectfluor, and solvents of TFA/TFAA promises the successful delivery of the oxidation with satisfactory yields. A possible mechanism involving a unique carbene-Rh complex is proposed, and has been supported by both experiments and theoretical calculations. PMID:26311544

  3. Synthesis of Normorphans through an Efficient Intramolecular Carbamoylation of Ketones.

    PubMed

    Diaba, Faïza; Montiel, Juan A; Serban, Georgeta; Bonjoch, Josep

    2015-08-01

    An unexpected C-C bond cleavage was observed in trichloroacetamide-tethered ketones under amine treatment and exploited to develop a new synthesis of normophans from 4-amidocyclohexanones. The reaction involves an unprecedented intramolecular haloform-type reaction of trichloroacetamides promoted by enamines (generated in situ from ketones) as counter-reagents. The methodology was applied to the synthesis of compounds embodying the 6-azabicyclo[3.2.1]octane framework. PMID:26197207

  4. Chemoselective C-benzylation of unprotected anilines with benzyl alcohols using Re2O7 catalyst.

    PubMed

    Nallagonda, Rajender; Rehan, Mohammad; Ghorai, Prasanta

    2014-04-01

    An unprecedented dehydrative C-C bond formation between unprotected anilines with benzyl alcohols is disclosed. Re2O7 catalyst (5 mol %) at elevated reaction temperature (80 °C) provided C-benzylanilines with high to excellent yields and with good chemoselectivities (over N-alkylation). A probable mechanism has been proposed based on mechanistic studies. PMID:24601671

  5. MgI2 -mediated chemoselective cleavage of protecting groups: an alternative to conventional deprotection methodologies.

    PubMed

    Berthet, Mathéo; Davanier, Florian; Dujardin, Gilles; Martinez, Jean; Parrot, Isabelle

    2015-07-27

    The scope of MgI2 as a valuable tool for quantitative and mild chemoselective cleavage of protecting groups is described here. This novel synthetic approach expands the use of protecting groups, widens the concept of orthogonality in synthetic processes, and offers a facile opportunity to release compounds from solid supports. PMID:26121554

  6. The Use of pH to Influence Regio-and Chemoselectivity in the Asymmetric

    E-print Network

    Hergenrother, Paul J.

    - S1 - The Use of pH to Influence Regio- and Chemoselectivity in the Asymmetric Aminohydroxylation-Hoover Capillary Melting Point Apparatus and are uncorrected. The pH of solutions was measured by AquemetTM Research AR15 pH meter equipped with Corning semimicrocombo electrode (#476156), which was standardized

  7. The Use of pH to Influence Regio-and Chemoselectivity in the Asymmetric

    E-print Network

    Hergenrother, Paul J.

    The Use of pH to Influence Regio- and Chemoselectivity in the Asymmetric Aminohydroxylation, 2002 ABSTRACT The pH-controlled Sharpless asymmetric aminohydroxylation (AA) of styrenes provides 1 inversely correlated with enantiselectivity.3a We now report a method utilizing pH control to override other

  8. A concise and efficient total synthesis of ?-mangostin and ?-mangostin from Garcinia mangostana.

    PubMed

    Xu, Dandan; Nie, Ying; Liang, Xizhou; Ji, Ling; Hu, Songyuan; You, Qidong; Wang, Fan; Ye, Hongchun; Wang, Jinxin

    2013-08-01

    The concise, efficient synthesis of alpha-mangostin is described in eight simple steps with 8.3% overall yield. Highlights include a practical approach to construct the isopentene groups and other diverse groups at C-2 and C-8 of the xanthene skeleton through Claisen rearrangement and Wittig reaction. Meanwhile the first total synthesis of beta-mangostin is presented with a similar approach. PMID:24079178

  9. Surface-Functionalized Nanoparticles by Olefin Metathesis: A Chemoselective Approach for In Vivo Characterization of Atherosclerosis Plaque.

    PubMed

    Salinas, Beatriz; Ruiz-Cabello, Jesús; Lechuga-Vieco, Ana V; Benito, Marina; Herranz, Fernando

    2015-07-13

    The use of click chemistry reactions for the functionalization of nanoparticles is particularly useful to modify the surface in a well-defined manner and to enhance the targeting properties, thus facilitating clinical translation. Here it is demonstrated that olefin metathesis can be used for the chemoselective functionalization of iron oxide nanoparticles with three different examples. This approach enables, in one step, the synthesis and functionalization of different water-stable magnetite-based particles from oleic acid-coated counterparts. The surface of the nanoparticles was completely characterized showing how the metathesis approach introduces a large number of hydrophilic molecules on their coating layer. As an example of the possible applications of these new nanocomposites, a focus was taken on atherosclerosis plaques. It is also demonstrated how the in vitro properties of one of the probes, particularly its Ca(2+) -binding properties, mediate their final in vivo use; that is, the selective accumulation in atherosclerotic plaques. This opens promising new applications to detect possible microcalcifications associated with plaque vulnerability. The accumulation of the new imaging tracers is demonstrated by in vivo magnetic resonance imaging of carotids and aorta in the ApoE(-/-) mouse model and the results were confirmed by histology. PMID:26096657

  10. Chemoselective O-acylation of hydroxyamino acids and amino alcohols under acidic reaction conditions: History, scope and applications

    PubMed Central

    2015-01-01

    Summary Amino acids, whether natural, semisynthetic or synthetic, are among the most important and useful chiral building blocks available for organic chemical synthesis. In principle, they can function as inexpensive, chiral and densely functionalized starting materials. On the other hand, the use of amino acid starting materials routinely necessitates protective group chemistry, and in reality, large-scale preparations of even the simplest side-chain derivatives of many amino acids often become annoyingly strenuous due to the necessity of employing protecting groups, on one or more of the amino acid functionalities, during the synthetic sequence. However, in the case of hydroxyamino acids such as hydroxyproline, serine, threonine, tyrosine and 3,4-dihydroxyphenylalanine (DOPA), many O-acyl side-chain derivatives are directly accessible via a particularly expedient and scalable method not commonly applied until recently. Direct acylation of unprotected hydroxyamino acids with acyl halides or carboxylic anhydrides under appropriately acidic reaction conditions renders possible chemoselective O-acylation, furnishing the corresponding side-chain esters directly, on multigram-scale, in a single step, and without chromatographic purification. Assuming a certain degree of stability under acidic reaction conditions, the method is also applicable for a number of related compounds, such as various amino alcohols and the thiol-functional amino acid cysteine. While the basic methodology underlying this approach has been known for decades, it has evolved through recent developments connected to amino acid-derived chiral organocatalysts to become a more widely recognized procedure for large-scale preparation of many useful side-chain derivatives of hydroxyamino acids and related compounds. Such derivatives are useful in peptide chemistry and drug development, as amino acid amphiphiles for asymmetric catalysis, and as amino acid acrylic precursors for preparation of catalytically active macromolecular networks in the form of soluble polymers, crosslinked polymer beads or nanoparticulate systems. The objective of the present review is to increase awareness of the existence and convenience of this methodology, assess its competitiveness compared to newer and more elaborate procedures for chemoselective O-acylation reactions, spur its further development, and finally to chronicle the informative, but poorly documented history of its development. PMID:25977719

  11. Efficiency, error and yield in light-directed maskless synthesis of DNA microarrays

    PubMed Central

    2011-01-01

    Background Light-directed in situ synthesis of DNA microarrays using computer-controlled projection from a digital micromirror device--maskless array synthesis (MAS)--has proved to be successful at both commercial and laboratory scales. The chemical synthetic cycle in MAS is quite similar to that of conventional solid-phase synthesis of oligonucleotides, but the complexity of microarrays and unique synthesis kinetics on the glass substrate require a careful tuning of parameters and unique modifications to the synthesis cycle to obtain optimal deprotection and phosphoramidite coupling. In addition, unintended deprotection due to scattering and diffraction introduce insertion errors that contribute significantly to the overall error rate. Results Stepwise phosphoramidite coupling yields have been greatly improved and are now comparable to those obtained in solid phase synthesis of oligonucleotides. Extended chemical exposure in the synthesis of complex, long oligonucleotide arrays result in lower--but still high--final average yields which approach 99%. The new synthesis chemistry includes elimination of the standard oxidation until the final step, and improved coupling and light deprotection. Coupling Insertions due to stray light are the limiting factor in sequence quality for oligonucleotide synthesis for gene assembly. Diffraction and local flare are by far the largest contributors to loss of optical contrast. Conclusions Maskless array synthesis is an efficient and versatile method for synthesizing high density arrays of long oligonucleotides for hybridization- and other molecular binding-based experiments. For applications requiring high sequence purity, such as gene assembly, diffraction and flare remain significant obstacles, but can be significantly reduced with straightforward experimental strategies. PMID:22152062

  12. Regio- and stereoselective synthesis of aminoinositols and 1,2-diaminoinositols from conduritol B epoxide.

    PubMed

    Serrano, Pedro; Llebaria, Amadeu; Delgado, Antonio

    2005-09-30

    [Chemical reaction: See text] A systematic approach to the regio- and stereoselective synthesis of aminoinositols and 1,2-diaminoinositols arising from tetra-O-benzylconduritol B epoxide (9) and its aziridine analogue 22, respectively, is described. In all cases, the synthetic methodologies rely on the regio- and stereocontrolled azidolysis of the starting precursors to give the corresponding trans regioadducts. Subsequent functional group manipulation under strict configurational control affords the isomeric cis adducts. Chemoselective functionalization of the diamine moiety in 1,2-diaminoinositol derivatives can be achieved by the proper design of the reaction sequence and choice of reagents. The described protocols allow efficient access to each of the eight possible configurations of the 1,2-diamino and 1,2-amino alcohol moieties from chemical modifications of the epoxide moiety on the common precursor 9. PMID:16277302

  13. Assimilation efficiencies of chemical contaminants in aquatic invertebrates: A synthesis

    SciTech Connect

    Wang, W.X.; Fisher, N.S.

    1999-09-01

    Assimilation efficiencies of contaminants from ingested food are critical for understanding chemical accumulation and trophic transfer in aquatic invertebrates. Assimilation efficiency is a first-order physiological parameter that can be used to systematically compare the bioavailability of different contaminants from different foods. The various techniques used to measure contaminant assimilation efficiencies are reviewed. Pulse-chase feeding techniques and the application of gamma-emitting radiotracers have been invaluable in measuring metal assimilation efficiencies in aquatic animals. Uniform radiolabeling of food is required to measure assimilation, but this can be difficult when sediments are the food source. Biological factors that influence contaminant assimilation include food quantity and quality, partitioning of contaminants in the food particles, and digestive physiology of the animals. Other factors influencing assimilation include the behavior of the chemical within the animal's gut and its associations with different geochemical fractions of food particles. Assimilation efficiency is a critical parameter to determine (and to make predictions of) bioaccumulation of chemicals from dietary exposure. Robust estimates of assimilation efficiency coupled with estimates of aqueous uptake can be used to determine the relative importance of aqueous and dietary exposures. For bioaccumulation of metals from sediments, additional studies are required to test whether metals bound to the acid-volatile sulfide fraction of sediments can be available to benthic deposit-feeding inverterbrates. Most assimilation efficiency studies have focused on chemical transfer in organisms at the bottom of the food chain; additional studies are required to examine chemical transfer at higher trophic levels.

  14. Reliability-Aware and Energy-Efficient Synthesis of NoC based MPSoCs

    E-print Network

    Pasricha, Sudeep

    design-time framework (RESYN) to trade-off energy consumption and reliability in the NoC fabricReliability-Aware and Energy-Efficient Synthesis of NoC based MPSoCs Yong Zou, Sudeep Pasricha Electrical and Computer Engineering, Colorado State University yong.zou@colostate.edu, sudeep

  15. Synthesis and scintillating efficiencies of 2,5-diarylthiazoles with intramolecular hydrogen bond

    E-print Network

    Synthesis and scintillating efficiencies of 2,5-diarylthiazoles with intramolecular hydrogen bond. The search for novel organic luminophores possessing desired spectral properties is both fundamentally; Scintillation; Hydrogen bond. * Corresponding author. Tel.: +1-206-221-3931; fax: +1-206-685-8665; e

  16. ACCESS-2: Approximation Concepts Code for Efficient Structural Synthesis, user's guide

    NASA Technical Reports Server (NTRS)

    Miura, H.; Schmit, L. A., Jr.

    1978-01-01

    A user's guide is presented for the ACCESS-2 computer program. ACCESS-2 is a research oriented program which implements a collection of approximation concepts to achieve excellent efficiency in structural synthesis. The finite element method is used for structural analysis and general mathematical programming algorithms are applied in the design optimization procedure.

  17. Efficient enantiomeric synthesis of pyrrolidine and piperidine alkaloids from tobacco.

    PubMed

    Felpin, F X; Girard, S; Vo-Thanh, G; Robins, R J; Villiéras, J; Lebreton, J

    2001-09-21

    An enantiomeric synthesis of six piperidine and pyrrolidine alkaloids, (S)-nornicotine 1, (S)-nicotine 2, (S)-anatabine 3, (S)-N-methylanatabine 4, (S)-anabasine 5, and (S)-N-methylanabasine 6, known as natural products in tobacco, was established from a common chiral homoallylic (S)-3-(1-azido-but-3-enyl)-pyridine 15. An intramolecular hydroboration-cycloalkylation of the homoallylic azide intermediate 15 served as the key step in the pyrrolidine ring formation. A ring closing metathesis reaction (RCM) of a diethylenic amine intermediate (S)-allyl-(1-pyridin-3-yl-but-3-enyl)-carbamic acid benzyl ester 20 served as the key step in the piperidine ring formation. From the commercially available 3-pyridinecarboxaldehyde 13, a short and convenient enantiomeric synthesis of tobacco alkaloids is described: (S)-nornicotine 1 (5 steps, with an overall yield of 70%), (S)-nicotine 2 (6 steps, 65%), (S)-anatabine 3 (8 steps, 30%), (S)-N-methylanatabine 4 (8 steps, 25%), (S)-anabasine 5 (8 steps, 35%), and (S)-N-methylanabasine 6 (8 steps, 25%). PMID:11559179

  18. Chemoselective Strategies to Peptide and Protein Bioprobes Immobilization on Microarray Surfaces.

    PubMed

    Gori, Alessandro; Longhi, Renato

    2016-01-01

    Ordered and reproducible bioprobe immobilization onto sensor surfaces is a critical step in the development of reliable analytical devices. A growing awareness of the impact of the immobilization scheme on the consistency of the generated data is driving the demand for chemoselective approaches to immobilize biofunctional ligands, such as peptides, in a predetermined and uniform fashion. Herein, the most intriguing strategies to selective and oriented peptide immobilization are described and discussed. The aim of the current work is to provide the reader a general picture on recent advances made in this field, highlighting the potential associated with each chemoselective strategy. Case studies are described to provide illustrative examples, and cross-references to more topic-focused and exhaustive reviews are proposed throughout the text. PMID:26490473

  19. A chemical approach to immunoprotein engineering: chemoselective functionalization of thioester proteins in their native state.

    PubMed

    Cole, Michael A; Tully, Sarah E; Dodds, Alister W; Arnold, James N; Boldt, Grant E; Sim, Robert B; Offer, John; Wentworth, Paul

    2009-05-25

    Less than 6 feet under: Serum proteins C3, C4, and alpha(2)M each contain a thioester domain buried within a hydrophobic pocket, which is thought to shield the labile thioester from hydrolysis. Herein, we make use of the inherent reactivity of the hydrazide for thioester moieties to chemoselectively label these crucial serum regulators in their native conformation; this demonstrates that access to the thioester site is much greater than previously supposed. PMID:19402090

  20. Chemoselection of Allogeneic HSC After Murine Neonatal Transplantation Without Myeloablation or Post-transplant Immunosuppression

    PubMed Central

    Falahati, Rustom; Zhang, Jianqing; Flebbe-Rehwaldt, Linda; Shi, Yimin; Gerson, Stanton L; Gaensler, Karin ML

    2012-01-01

    The feasibility of allogeneic transplantation, without myeloablation or post-transplant immunosuppression, was tested using in vivo chemoselection of allogeneic hematopoietic stem cells (HSCs) after transduction with a novel tricistronic lentiviral vector (MGMTP140K-2A-GFP-IRES-TK (MAGIT)). This vector contains P140K-O6-methylguanine-methyltransferase (MGMTP140K), HSV-thymidine kinase (TKHSV), and enhanced green fluorescent protein (eGFP) enabling (i) in vivo chemoselection of HSC by conferring resistance to benzylguanine (BG), an inhibitor of endogenous MGMT, and to chloroethylating agents such as 1,3-bis(2-chloroethyl)nitrosourea (BCNU) and, (ii) depletion of proliferating cells such as malignant clones or transduced donor T cells mediating graft versus host disease (GVHD), by expression of the suicide gene TKHSV and Ganciclovir (GCV) administration. Non-myeloablative transplantation of transduced, syngeneic, lineage-depleted (Lin?) BM in neonates resulted in 0.67% GFP+ mononuclear cells in peripheral blood. BG/BCNU chemoselection, 4 and 8 weeks post-transplant, produced 50-fold donor cell enrichment. Transplantation and chemoselection of major histocompatibility complex (MHC)-mismatched MAGIT-transduced Lin? BM also produced similar expansion for >40 weeks. The efficacy of this allotransplant approach was validated in Hbbth3 heterozygous mice by correction of ?-thalassemia intermedia, without toxicity or GVHD. Negative selection, by administration of GCV resulted in donor cell depletion without graft ablation, as re-expansion of donor cells was achieved with BG/BCNU treatment. These studies show promise for developing non-ablative allotransplant approaches using in vivo positive/negative selection. PMID:22871662

  1. Improvement of efficiency in the enzymatic synthesis of lactulose palmitate.

    PubMed

    Bernal, Claudia; Illanes, Andres; Wilson, Lorena

    2015-04-15

    Sugar esters are considered as surfactants due to its amphiphilic balance that can lower the surface tension in oil/water mixtures. Enzymatic syntheses of these compounds are interesting both from economic and environmental considerations. A study was carried out to evaluate the effect of four solvents, temperature, substrate molar ratio, biocatalyst source, and immobilization methodology on the yield and specific productivity of lactulose palmitate monoester synthesis. Lipases from Pseudomonas stutzeri (PsL) and Alcaligenes sp. (AsL), immobilized in porous silica functionalized with octyl groups (adsorption immobilization, OS) and with glyoxyl-octyl groups (both adsorption and covalent immobilization, OGS), were used. The highest lactulose palmitate yields were obtained at 47 °C in acetone, for all biocatalysts, while the best lactulose:palmitic acid molar ratio differed according to the immobilization methodology, being 1:1 for AsL-OGS biocatalyst (20.7 ± 3%) and 1:3 for the others (30-50%). PMID:25797166

  2. A manganese catalyst for highly reactive yet chemoselective intramolecular C(sp(3))-H amination.

    PubMed

    Paradine, Shauna M; Griffin, Jennifer R; Zhao, Jinpeng; Petronico, Aaron L; Miller, Shannon M; Christina White, M

    2015-12-01

    C-H bond oxidation reactions underscore the existing paradigm wherein high reactivity and high selectivity are inversely correlated. The development of catalysts capable of oxidizing strong aliphatic C(sp(3))-H bonds while displaying chemoselectivity (that is, tolerance of more oxidizable functionality) remains an unsolved problem. Here, we describe a catalyst, manganese tert-butylphthalocyanine [Mn((t)BuPc)], that is an outlier to the reactivity-selectivity paradigm. It is unique in its capacity to functionalize all types of C(sp(3))-H bond intramolecularly, while displaying excellent chemoselectivity in the presence of ? functionality. Mechanistic studies indicate that [Mn((t)BuPc)] transfers bound nitrenes to C(sp(3))-H bonds via a pathway that lies between concerted C-H insertion, observed with reactive noble metals such as rhodium, and stepwise radical C-H abstraction/rebound, as observed with chemoselective base metals such as iron. Rather than achieving a blending of effects, [Mn((t)BuPc)] aminates even 1° aliphatic and propargylic C-H bonds, demonstrating reactivity and selectivity unusual for previously known catalysts. PMID:26587714

  3. Chemoselective tarantula toxins report voltage activation of wild-type ion channels in live cells.

    PubMed

    Tilley, Drew C; Eum, Kenneth S; Fletcher-Taylor, Sebastian; Austin, Daniel C; Dupré, Christophe; Patrón, Lilian A; Garcia, Rita L; Lam, Kit; Yarov-Yarovoy, Vladimir; Cohen, Bruce E; Sack, Jon T

    2014-11-01

    Electrically excitable cells, such as neurons, exhibit tremendous diversity in their firing patterns, a consequence of the complex collection of ion channels present in any specific cell. Although numerous methods are capable of measuring cellular electrical signals, understanding which types of ion channels give rise to these signals remains a significant challenge. Here, we describe exogenous probes which use a novel mechanism to report activity of voltage-gated channels. We have synthesized chemoselective derivatives of the tarantula toxin guangxitoxin-1E (GxTX), an inhibitory cystine knot peptide that binds selectively to Kv2-type voltage gated potassium channels. We find that voltage activation of Kv2.1 channels triggers GxTX dissociation, and thus GxTX binding dynamically marks Kv2 activation. We identify GxTX residues that can be replaced by thiol- or alkyne-bearing amino acids, without disrupting toxin folding or activity, and chemoselectively ligate fluorophores or affinity probes to these sites. We find that GxTX-fluorophore conjugates colocalize with Kv2.1 clusters in live cells and are released from channels activated by voltage stimuli. Kv2.1 activation can be detected with concentrations of probe that have a trivial impact on cellular currents. Chemoselective GxTX mutants conjugated to dendrimeric beads likewise bind live cells expressing Kv2.1, and the beads are released by channel activation. These optical sensors of conformational change are prototype probes that can indicate when ion channels contribute to electrical signaling. PMID:25331865

  4. Sulfonamide bearing oligonucleotides: simple synthesis and efficient RNA recognition.

    PubMed

    Kumar, Pawan; Chandak, Navneet; Nielsen, Poul; Sharma, Pawan K

    2012-06-15

    Four pyrimidine nucleosides wherein a benzensulfonamide group is linked to the C-5 position of the uracil nucleobase through a triazolyl or an alkynyl linker were prepared by Cu(I)-assisted azide-alkyne cycloadditions (CuAAC) or Sonogashira reactions, respectively, and incorporated into oligonucleotides. Efficient ?-?-stacking between two or more phenyltriazoles in the major groove was found to increase the thermal stability of a DNA:RNA duplex significantly. On the other hand, the alkynyl group was not as efficient in stacking as the triazolyl group. No effect of positional orientation of the sulfonamide group on the stacking efficiency was observed, and the most stable DNA:RNA duplex contained four consecutive sulfonamide substituted phenyltriazole moieties in the major groove. PMID:22579616

  5. An efficient prebiotic synthesis of cytosine and uracil

    NASA Technical Reports Server (NTRS)

    Robertson, M. P.; Miller, S. L.

    1995-01-01

    In contrast to the purines, the routes that have been proposed for the prebiotic synthesis of pyrimidines from simple precursors give only low yields. Cytosine can be synthesized from cyanoacetylene and cyanate; the former precursor is produced from a spark discharge in a CH4/N2 mixture and is an abundant interstellar molecule. But this reaction requires relatively high concentrations of cyanate (> 0.1 M), which are unlikely to occur in aqueous media as cyanate is hydrolysed rapidly to CO2 and NH3. An alternative route that has been explored is the reaction of cyanoacetaldehyde (formed by hydrolysis of cyanoacetylene) with urea. But at low concentrations of urea, this reaction produces no detectable quantities of cytosine. Here we show that in concentrated urea solution--such as might have been found in an evaporating lagoon or in pools on drying beaches on the early Earth--cyanoacetaldehyde reacts to form cytosine in yields of 30-50%, from which uracil can be formed by hydrolysis. These reactions provide a plausible route to the pyrimidine bases required in the RNA world.

  6. An efficient prebiotic synthesis of cytosine and uracil

    NASA Astrophysics Data System (ADS)

    Robertson, Michael P.; Miller, Stanley L.

    1995-06-01

    IN contrast to the purines1 3, the routes that have been proposed for the prebiotic synthesis of pyrimidines from simple precursors give only low yields. Cytosine can be synthesized from cyano-acetylene and cyanate4,5; the former precursor is produced from a spark discharge in a CH4/N2 mixture4,5 and is an abundant interstellar molecule6. But this reaction requires relatively high concentrations of cyanate (>0.1 M), which are unlikely to occur in aqueous media as cyanate is hydrolysed rapidly to CO2 and NH3. An alternative route that has been explored7 is the reaction of cyanoacetaldehyde (formed by hydrolysis of cyanoacetylene8) with urea. But at low concentrations of urea, this reaction produces no detectable quantities of cytosine7. Here we show that in concentrated urea solution-such as might have been found in an evaporating lagoon or in pools on drying beaches on the early Earth-cyanoacetaldehyde reacts to form cytosine in yields of 30-50%, from which uracil can be formed by hydrolysis. These reactions provide a plausible route to the pyrimidine bases required in the RNA world9.

  7. Efficient synthesis of probabilistic quantum circuits with fallback

    NASA Astrophysics Data System (ADS)

    Bocharov, Alex; Roetteler, Martin; Svore, Krysta M.

    2015-05-01

    Repeat-until-success (RUS) circuits can approximate a given single-qubit unitary with an expected number of T gates of about 1/3 of what is required by optimal, deterministic, ancilla-free decompositions over the Clifford + T gate set. In this work, we introduce a more general and conceptually simpler circuit decomposition method that allows for synthesis into protocols that probabilistically implement quantum circuits over several universal gate sets including, but not restricted to, the Clifford + T gate set. The protocol, which we call probabilistic quantum circuits with fallback (PQF), implements a walk on a discrete Markov chain in which the target unitary is an absorbing state and in which transitions are induced by multiqubit unitaries followed by measurements. In contrast to RUS protocols, the presented PQF protocols are guaranteed to terminate after a finite number of steps. Specifically, we apply our method to the Clifford + T , Clifford + V , and Clifford + ? /12 gate sets to achieve decompositions with expected gate counts of logb(1 /? ) +O {ln[ln(1 /? ) ] } , where b is a quantity related to the expansion property of the underlying universal gate set.

  8. Chemical synthesis approaches to the engineering of ion channels.

    PubMed

    Kochendoerfer, Gerd G; Clayton, Daniel; Becker, Christian

    2005-11-01

    Chemoselective ligation strategies have previously provided synthetic access to water-soluble proteins with novel properties, and more recently these strategies have been used to prepare ion channels. Examples of ion channels prepared by total chemical synthesis include bacterial mechanosensitive channels, and viral ion channels. Chemical protein synthesis allows for the generation of ion channel proteins with both native, and engineered structural or conductance properties. PMID:16305542

  9. An Efficient, Optimized Synthesis of Fentanyl and Related Analogs

    PubMed Central

    Valdez, Carlos A.; Leif, Roald N.; Mayer, Brian P.

    2014-01-01

    The alternate and optimized syntheses of the parent opioid fentanyl and its analogs are described. The routes presented exhibit high-yielding transformations leading to these powerful analgesics after optimization studies were carried out for each synthetic step. The general three-step strategy produced a panel of four fentanyls in excellent yields (73–78%) along with their more commonly encountered hydrochloride and citric acid salts. The following strategy offers the opportunity for the gram-scale, efficient production of this interesting class of opioid alkaloids. PMID:25233364

  10. Efficient ATP synthesis by thermophilic Bacillus FoF1-ATP synthase.

    PubMed

    Soga, Naoki; Kinosita, Kazuhiko; Yoshida, Masasuke; Suzuki, Toshiharu

    2011-08-01

    F(o)F(1)-ATP synthase (F(o)F(1)) synthesizes ATP in the F(1) portion when protons flow through F(o) to rotate the shaft common to F(1) and F(o). Rotary synthesis in isolated F(1) alone has been shown by applying external torque to F(1) of thermophilic origin. Proton-driven ATP synthesis by thermophilic Bacillus PS3 F(o)F(1) (TF(o)F(1)), however, has so far been poor in vitro, of the order of 1 s(-1) or less, hampering reliable characterization. Here, by using a mutant TF(o)F(1) lacking an inhibitory segment of the ?-subunit, we have developed highly reproducible, simple procedures for the preparation of active proteoliposomes and for kinetic analysis of ATP synthesis, which was driven by acid-base transition and K(+)-diffusion potential. The synthesis activity reached ? 16 s(-1) at 30 °C with a Q(10) temperature coefficient of 3-4 between 10 and 30 °C, suggesting a high level of activity at the physiological temperature of ? 60 °C. The Michaelis-Menten constants for the substrates ADP and inorganic phosphate were 13 ?M and 0.55 mM, respectively, which are an order of magnitude lower than previous estimates and are suited to efficient ATP synthesis. PMID:21605343

  11. Efficient ATP synthesis by thermophilic Bacillus FoF1-ATP synthase

    PubMed Central

    Soga, Naoki; Kinosita, Kazuhiko; Yoshida, Masasuke; Suzuki, Toshiharu

    2011-01-01

    FoF1-ATP synthase (FoF1) synthesizes ATP in the F1 portion when protons flow through Fo to rotate the shaft common to F1 and Fo. Rotary synthesis in isolated F1 alone has been shown by applying external torque to F1 of thermophilic origin. Proton-driven ATP synthesis by thermophilic Bacillus PS3 FoF1 (TFoF1), however, has so far been poor in vitro, of the order of 1 s?1 or less, hampering reliable characterization. Here, by using a mutant TFoF1 lacking an inhibitory segment of the ?-subunit, we have developed highly reproducible, simple procedures for the preparation of active proteoliposomes and for kinetic analysis of ATP synthesis, which was driven by acid–base transition and K+-diffusion potential. The synthesis activity reached ? 16 s?1 at 30 °C with a Q10 temperature coefficient of 3–4 between 10 and 30 °C, suggesting a high level of activity at the physiological temperature of ? 60 °C. The Michaelis–Menten constants for the substrates ADP and inorganic phosphate were 13 ?m and 0.55 mm, respectively, which are an order of magnitude lower than previous estimates and are suited to efficient ATP synthesis. PMID:21605343

  12. Simplified Application of Material Efficiency Green Metrics to Synthesis Plans: Pedagogical Case Studies Selected from "Organic Syntheses"

    ERIC Educational Resources Information Center

    Andraos, John

    2015-01-01

    This paper presents a simplified approach for the application of material efficiency metrics to linear and convergent synthesis plans encountered in organic synthesis courses. Computations are facilitated and automated using intuitively designed Microsoft Excel spreadsheets without invoking abstract mathematical formulas. The merits of this…

  13. Efficient synthesis of new fluorinated building blocks by means of hydroformylation.

    PubMed

    Fanfoni, Lidia; Diab, Lisa; Smejkal, Tomas; Breit, Bernhard

    2014-01-01

    Hydroformylation of fluorinated alkenes is an efficient method for the preparation of fluorinated functionalized building blocks for the synthesis of biologically active target structures. In this article we summarize known hydroformylation reactions of fluorinated olefins and we add new results from our research groups. Particular attention is paid to the remarkable influence of organofluorine substituents on catalyst activity, regio- and stereoselectivity of the hydroformylation reaction. PMID:25198747

  14. ACCESS 1: Approximation Concepts Code for Efficient Structural Synthesis program documentation and user's guide

    NASA Technical Reports Server (NTRS)

    Miura, H.; Schmit, L. A., Jr.

    1976-01-01

    The program documentation and user's guide for the ACCESS-1 computer program is presented. ACCESS-1 is a research oriented program which implements a collection of approximation concepts to achieve excellent efficiency in structural synthesis. The finite element method is used for structural analysis and general mathematical programming algorithms are applied in the design optimization procedure. Implementation of the computer program, preparation of input data and basic program structure are described, and three illustrative examples are given.

  15. H(3)PW(12)O(40)-catalyzed multicomponent reaction for efficient synthesis of highly substituted piperidines.

    PubMed

    Khaksar, Samad; Baghbanian, Seyed Meysam; Barsan, Nastaran

    2014-01-01

    A simple, diastereoselective, inexpensive, and efficient route for the synthesis of highly functionalized piperidines by the condensation of ?-keto-esters, aromatic aldehydes and anilines using H3PW12O40 as a catalyst is described. The catalyst could be easily recovered after completion of the reaction and reused without a considerable change in its activity. Furthermore, in most cases the piperidine precipitates out of solution. PMID:24372051

  16. Chemoselective biocatalytic reduction of conjugated nitroalkenes: new application for an Escherichia coli BL21(DE3) expression strain.

    PubMed

    Jovanovic, Predrag; Jeremic, Sanja; Djokic, Lidija; Savic, Vladimir; Radivojevic, Jelena; Maslak, Veselin; Ivkovic, Branka; Vasiljevic, Branka; Nikodinovic-Runic, Jasmina

    2014-06-10

    Chemoselective reduction of activated carbon-carbon double bond in conjugated nitroalkenes was achieved using Escherichia coli BL21(DE3) whole cells. Nine different substrates have been used furnishing the reduced products in moderate to good yields. 1-Nitro-4-phenyl-1,3-butadiene and (2-nitro-1-propenyl)benzene were successfully biotransformed with corresponding product yields of 54% and 45% respectively. Using this simple and environmentally friendly system 2-(2-nitropropyl)pyridine and 2-(2-nitropropyl)naphthalene were synthesized and characterized for the first time. High substrate conversion efficiency was coupled with low enantioselectivity, however 29% enantiomeric excess was detected in the case of 2-(2-nitropropyl)pyridine. It was shown that electronic properties of the aromatic ring, which affected polarity of the double bond, were not highly influential factors in the reduction process, but the presence of the nitro functionality was essential for the reaction to proceed. 1-Phenyl-4-nitro-1,3-butadiene could not be biotransformed by whole cells of Pseudomonas putida KT2440 or Bacillus subtilis 168 while it was successfully reduced by E. coli DH5? but with lower efficiency in comparison to E. coli BL21(DE3). Knockout mutant affected in nemA gene coding for N-ethylmaleimide reductase (BL21?nemA) could still catalyze bioreductions suggesting multiple active reductases within E. coli BL21(DE3) biocatalyst. The described biocatalytic reduction of substituted nitroalkenes provides an efficient route for the preparation of the corresponding nitroalkanes and introduces the new application of the strain traditionally utilized for recombinant protein expression. PMID:24835095

  17. Efficient three-component one-pot synthesis of steroidal polysubstituted anilines.

    PubMed

    Zhang, Yan-Ling; Li, Ya-Fei; Shi, Yun-Kai; Yu, Bin; Zhang, Guo-Chen; Qi, Ping-Ping; Fu, Dong-Jun; Shan, Li-Hong; Liu, Hong-Min

    2015-12-01

    An efficient and practical base-promoted cascade reaction has been developed to access steroidal polysubstituted anilines from simple precursors. The protocol reported herein achieved the formation of a benzene ring as well as three continuous C-C bonds in a single operation. The reaction mechanism was proposed on the basis of the key intermediate obtained. Besides, this method could be potentially employed for the synthesis of biphenyl compounds. The adjacent amine and nitrile groups existed in the final products have the potential for late stage functionalization, which would provide efficient access to steroidal compound collections with structural diversity and complexity. PMID:26209811

  18. Information and Efficiency in the Nervous System—A Synthesis

    PubMed Central

    Sengupta, Biswa; Stemmler, Martin B.; Friston, Karl J.

    2013-01-01

    In systems biology, questions concerning the molecular and cellular makeup of an organism are of utmost importance, especially when trying to understand how unreliable components—like genetic circuits, biochemical cascades, and ion channels, among others—enable reliable and adaptive behaviour. The repertoire and speed of biological computations are limited by thermodynamic or metabolic constraints: an example can be found in neurons, where fluctuations in biophysical states limit the information they can encode—with almost 20–60% of the total energy allocated for the brain used for signalling purposes, either via action potentials or by synaptic transmission. Here, we consider the imperatives for neurons to optimise computational and metabolic efficiency, wherein benefits and costs trade-off against each other in the context of self-organised and adaptive behaviour. In particular, we try to link information theoretic (variational) and thermodynamic (Helmholtz) free-energy formulations of neuronal processing and show how they are related in a fundamental way through a complexity minimisation lemma. PMID:23935475

  19. Efficient synthesis of hexahydroindenopyridines and their potential as melatoninergic ligands.

    PubMed

    Párraga, Javier; Moreno, Laura; Diaz, Amelia; El Aouad, Noureddine; Galán, Abraham; Sanz, María Jesús; Caignard, Daniel-Henri; Figadère, Bruno; Cabedo, Nuria; Cortes, Diego

    2014-10-30

    Hexahydroindenopyridine (HHIP) is an interesting tricyclic piperidine nucleus that is structurally related to melatonin, a serotonin-derived neurohormone. Melatonin receptor ligands have applications in several cellular, neuroendocrine and neurophysiological disorders, including depression and/or insomnia. We report herein an efficient two-step method to prepare new HHIP via enamine C-alkylation-cyclization. The influence of substituents on the benzene ring and the nitrogen atom on melatoninergic receptors has been studied. Among the 25 synthesized HHIPs, some of them containing methylenedioxy (series 2) and 8-chloro-7-methoxy substituents (series 4) on the benzene ring revealed affinity for the MT1 and/or the MT2 receptors within the nanomolar range or low micromolar. Similar activities were also encountered for those presenting urea (4g), N-aryl (2e) and N-alkyl (2f) acetamide functions. Therefore, new synthesized compounds with a HHIP nucleus have emerged as new promising leads towards the discovery of melatoninergic ligands which could provide new therapeutic agents. PMID:25232966

  20. Hangman corroles: efficient synthesis and oxygen reaction chemistry.

    PubMed

    Dogutan, Dilek K; Stoian, Sebastian A; McGuire, Robert; Schwalbe, Matthias; Teets, Thomas S; Nocera, Daniel G

    2011-01-12

    The construction of a new class of compounds--the hangman corroles--is provided efficiently by the modification of macrocyclic forming reactions from bilanes. Hangman cobalt corroles are furnished in good yields from a one-pot condensation of dipyrromethane with the aldehyde of a xanthene spacer followed by metal insertion using microwave irradiation. In high oxidation states, X-band EPR spectra and DFT calculations of cobalt corrole axially ligated by chloride are consistent with the description of a Co(III) center residing in the one-electron oxidized corrole macrocycle. These high oxidation states are likely accessed in the activation of O-O bonds. Along these lines, we show that the proton-donating group of the hangman platform works in concert with the redox properties of the corrole to enhance the catalytic activity of O-O bond activation. The hangman corroles show enhanced activity for the selective reduction of oxygen to water as compared to their unmodified counterparts. The oxygen adduct, prior to oxygen reduction, is characterized by EPR and absorption spectroscopy. PMID:21142043

  1. Efficient synthesis of [18F]trifluoromethane and its application in the synthesis of PET tracers.

    PubMed

    van der Born, Dion; Herscheid, J Koos D M; Orru, Romano V A; Vugts, Danielle J

    2013-05-11

    A new strategy towards [(18)F]trifluoromethyl-containing compounds is developed. [(18)F]trifluoromethane is synthesised in a fast and efficient manner and subsequently used in the reaction with aldehydes and ketones forming [(18)F]trifluoromethyl carbinols in good yields. PMID:23563284

  2. Chemoselective Silylative Reduction of Conjugated Nitriles under Metal-Free Catalytic Conditions: ?-Silyl Amines and Enamines.

    PubMed

    Gandhamsetty, Narasimhulu; Park, Juhyeon; Jeong, Jinseong; Park, Sung-Woo; Park, Sehoon; Chang, Sukbok

    2015-06-01

    The B(C6F5)3-catalyzed silylative reduction of conjugated nitriles has been developed to afford synthetically valuable ?-silyl amines. The reaction is chemoselective and proceeds under mild conditions. Mechanistic elucidation indicates that it proceeds by rapid double hydrosilylation of the conjugated nitrile to an enamine intermediate which is subsequently reduced to the ?-silyl amine, thus forming a new C(sp(3))-Si bond. Based on this mechanistic understanding, a preparative route to enamines was also established using bulky silanes. PMID:25907098

  3. Controllable Chemoselectivity in Visible-Light Photoredox Catalysis: Four Diverse Aerobic Radical Cascade Reactions.

    PubMed

    Liu, Xinfei; Ye, Xinyi; Bureš, Filip; Liu, Hongjun; Jiang, Zhiyong

    2015-09-21

    Reported is the controllable selectivity syntheses of four distinct products from the same starting materials by visible-light photoredox catalysis. By employing a dicyanopyrazine-derived chromophore (DPZ) as photoredox catalyst, an aerobic radical mechanism has been developed, and allows the reactions of N-tetrahydroisoquinolines (THIQs) with N-itaconimides to through four different pathways, including addition-cyclization, addition-elimination, addition-coupling, and addition-protonation, with satisfactory chemoselectivity. The current strategy provide straightforward access to four different but valuable N-heterocyclic adducts in moderate to excellent yields. PMID:26212794

  4. Dendronylation: Residue-specific chemoselective attachment of oligoglycerol dendrimers on proteins with noncanonical amino acids.

    PubMed

    Ma, Ying; Thota, Bala N S; Haag, Rainer; Budisa, Nediljko

    2015-11-15

    Polyglycerol dendrimers as an important class of polymeric materials especially attractive for covalent attachment to therapeutic proteins as a useful alternative to traditional PEGylation procedures. Herein, we combine in vivo noncanonical amino acid (ncAA) incorporation and chemoselective conjugation in vitro to produce novel hybrid protein-dendrimer conjugates with the defined architectures. We incorporated Azidohomoalanine (Aha) as methionine substitute in vivo into various protein scaffolds to allow non-invasive dendrimer conjugations (dendronylation). Our approach makes recombinant proteins accessible for the design of multivalent dendrimer conjugates since it enables the preparation of many sequences with various positions for regioselective dendronylation. PMID:26483199

  5. On the synthesis of multiple frequency tone burst stimuli for efficient high frequency auditory brainstem response.

    PubMed

    Ellingson, Roger M; Dille, Marilyn L; Leek, Marjorie R; Fausti, Stephen A

    2008-01-01

    The development and digital waveform synthesis of a multiple-frequency tone-burst (MFTB) stimulus is presented. The stimulus is designed to improve the efficiency of monitoring high-frequency auditory-brainstem-response (ABR) hearing thresholds. The pure-tone-based, fractional-octave-bandwidth MFTB supports frequency selective ABR audiometry with a bandwidth that falls between the conventional click and single-frequency tone-burst stimuli. The MFTB is being used to identify high frequency hearing threshold change due to ototoxic medication which most generally starts at the ultra-highest hearing frequencies and progresses downwards but could be useful in general limited-bandwidth testing applications. Included is a Mathcad implementation and analysis of our MFTB synthesis technique and sample performance measurements of the MFTB stimulus configuration used in a clinical research ABR system. PMID:19163628

  6. The role of carbon dioxide in chemoselective hydrogenation of halonitroaromatics over supported noble metal catalysts in supercritical carbon dioxide.

    PubMed

    Ichikawa, Shinichiro; Tada, Mizuki; Iwasawa, Yasuhiro; Ikariya, Takao

    2005-02-21

    Chemoselective hydrogenation of halogenated nitrobenzenes over Pt/C catalysts proceeds effectively in supercritical carbon dioxide (scCO2) to produce halogenated anilines with excellent selectivity; the rate of the hydrogenation of nitro groups is markedly enhanced in scCO2 compared to the neat reaction, and the dehalogenation reaction is significantly suppressed. PMID:15700083

  7. Reversing the Role of the Metal-Oxygen -Bond. Chemoselective Catalytic Reductions with a Rhenium(V)-Dioxo Complex

    E-print Network

    Toste, Dean

    Reversing the Role of the Metal-Oxygen -Bond. Chemoselective Catalytic Reductions with a Rhenium to begin our study by investigating rhenium(V)dioxo complexes as catalysts. Herein we describe an air- and moisture-tolerant catalytic one-step reduction-protection of carbonyl groups employing rhenium

  8. Chemoselective cross-linking and functionalization of alginate via Staudinger ligation

    PubMed Central

    Gattás-Asfura, Kerim M.; Stabler, Cherie L.

    2010-01-01

    In this study, we demonstrate the applicability of functionalized alginate to serve as a platform for the covalent cross-linking or immobilization of complimentary phosphine functionalized groups via the chemoselective Staudinger ligation scheme. Azide groups were covalently linked to alginate through a heterobifunctional polyethylene glycol (PEG) linker and carbodiimide. Degree of azide functionalization was varied as a function of carbodiimide concentration and determined by proton nuclear magnetic resonance (1H NMR) and infrared spectroscopy. Spontaneous and covalently cross-linked alginate-PEG gels were generated via the Staudinger ligation scheme upon incubation of the azide functionalized alginate with PEG chains having 1-methyl-2-diphenylphosphino-terephthalate (MDT) as end groups. Modulation of the MDT to N3 ratio resulted in variability of gel characteristics. In addition, azide functionalized alginate retained its capacity to instantaneously form hydrogels via electrostatic interaction with multivalent cations such as Ca2+ and Ba2+. Subsequently, covalent linkage of phosphine functionalized agents post-gelation of the alginate was feasible, as illustrated via linkage of MDT-PEG-carboxyfluorescein. Capitalization of the chemoselective and cell compatible Staudinger ligation scheme for covalent cross-linking of alginate hydrogels may enhance the utility of this polymer for the stable encapsulation of various cell types, in addition to their use in the immobilization of labeling agents, proteins, and other bioactive molecules. PMID:19848408

  9. Chemoselective Pd-catalyzed oxidation of polyols: synthetic scope and mechanistic studies.

    PubMed

    Chung, Kevin; Banik, Steven M; De Crisci, Antonio G; Pearson, David M; Blake, Timothy R; Olsson, Johan V; Ingram, Andrew J; Zare, Richard N; Waymouth, Robert M

    2013-05-22

    The regio- and chemoselective oxidation of unprotected vicinal polyols with [(neocuproine)Pd(OAc)]2(OTf)2 (1) (neocuproine = 2,9-dimethyl-1,10-phenanthroline) occurs readily under mild reaction conditions to generate ?-hydroxy ketones. The oxidation of vicinal diols is both faster and more selective than the oxidation of primary and secondary alcohols; vicinal 1,2-diols are oxidized selectively to hydroxy ketones, whereas primary alcohols are oxidized in preference to secondary alcohols. Oxidative lactonization of 1,5-diols yields cyclic lactones. Catalyst loadings as low as 0.12 mol % in oxidation reactions on a 10 g scale can be used. The exquisite selectivity of this catalyst system is evident in the chemoselective and stereospecific oxidation of the polyol (S,S)-1,2,3,4-tetrahydroxybutane [(S,S)-threitol] to (S)-erythrulose. Mechanistic, kinetic, and theoretical studies revealed that the rate laws for the oxidation of primary and secondary alcohols differ from those of diols. Density functional theory calculations support the conclusion that ?-hydride elimination to give hydroxy ketones is product-determining for the oxidation of vicinal diols, whereas for primary and secondary alcohols, pre-equilibria favoring primary alkoxides are product-determining. In situ desorption electrospray ionization mass spectrometry (DESI-MS) revealed several key intermediates in the proposed catalytic cycle. PMID:23659308

  10. A highly efficient green synthesis of 1, 8-dioxo-octahydroxanthenes

    PubMed Central

    2011-01-01

    SmCl3 (20 mol%) has been used as an efficient catalyst for reaction between aromatic aldehydes and 5,5-dimethyl-1,3-cyclohexanedione at 120°C to give 1,8-dioxo-octahydroxanthene derivatives in high yield. The same reaction in water, at room temperature gave only the open chain analogue of 1,8-dioxo-octahydroxanthene. Use of eco-friendly green Lewis acid, readily available catalyst and easy isolation of the product makes this a convenient method for the synthesis of either of the products. PMID:22152051

  11. Fungi as an efficient mycosystem for the synthesis of metal nanoparticles: progress and key aspects of research.

    PubMed

    Yadav, Alka; Kon, Kateryna; Kratosova, Gabriela; Duran, Nelson; Ingle, Avinash P; Rai, Mahendra

    2015-11-01

    Nanotechnology is an emerging cutting-edge technology, which involves interdisciplinary subjects, such as physics, chemistry, biology, material science and medicine. Different methods for the synthesis of nanoparticles have been discussed here. Although physical and chemical methods have been successfully used to synthesize nanoparticles, the use of hazardous chemicals and synthesis at high temperature is a matter of concern. Hence, there is a necessity to develop eco-friendly techniques for the synthesis of nanoparticles. Biosynthesis of nanoparticles by fungi, bacteria, actinomycetes, lichen and viruses have been reported eco-friendly. Moreover, the fungal system has emerged as an efficient system for nanoparticle synthesis as fungi possess distinctive characters including high wall binding capacity, easy to culture and simpler biomass handling, etc. In this review, we have discussed fungi as an important tool for the fabrication of nanoparticles. In addition, methods and mechanism for synthesis of nanoparticles and its potential applications have also been discussed. PMID:26164702

  12. Total synthesis of (+)-chinensiolide B via tandem allylboration/lactonization.

    PubMed

    Elford, Tim G; Hall, Dennis G

    2010-02-10

    The chinensiolides are a family of guaiane type alpha-methylene gamma-lactone natural products recently isolated from Ixeris chinensis Nakai, a plant used in Chinese folk medicine. The first enantioselective total synthesis of (+)-chinensiolide B was accomplished in 15 steps for the longest linear sequence with an overall yield of 6.7% starting from inexpensive and readily available (R)-carvone. A highly stereoselective and E/Z-selective tandem allylboration/lactonization reaction between two highly functionalized partners was exploited as a key step. The synthesis also highlights several solutions to chemoselectivity issues arising from the reactive alpha-methylene gamma-lactone. For instance, a ring-closing metathesis formed the requisite seven-membered ring in a chemoselective fashion while avoiding the reactivity of the conjugated alpha-methylene unit. PMID:20067261

  13. Population synthesis of s-process element enhanced stars: Constraining the 13C efficiency

    NASA Astrophysics Data System (ADS)

    Bona?i? Marinovi?, A.; Izzard, R. G.; Lugaro, M.; Pols, O. R.

    We study s-process element abundance ratios in stars by carrying out stellar population synthesis, using a rapid synthetic stellar evolution code which includes an up-to-date treatment of AGB nucleosynthesis and evolution. In contrast to other studies, we find that a large spread in the 13C efficiency parameter (13C_eff) is not needed to explain the observed spread in the ratios of heavy s-process to light s-process elements ([hs/ls]), but this comes naturally from the range of different initial stellar masses and their time evolution. As a result, the 13C efficiency needed for fitting most stars in the galactic disk is constrained to 1? 13C_eff? 2. In the same fashion we also study the [Pb/Ce] ratios of lead stars and find out that for low metallicities 13C_eff˜ 0.5.

  14. Synthesis and evaluation of tetramethylguanidinium-polyethylenimine polymers as efficient gene delivery vectors.

    PubMed

    Mahato, Manohar; Yadav, Santosh; Kumar, Pradeep; Sharma, Ashwani Kumar

    2014-01-01

    Previously, we demonstrated that 6-(N,N,N',N'-tetramethylguanidinium chloride)-hexanoyl-polyethylenimine (THP) polymers exhibited significantly enhanced transfection efficiency and cell viability. Here, in the present study, we have synthesized a series of N,N,N',N'-tetramethylguanidinium-polyethylenimine (TP1-TP5) polymers via a single-step reaction involving peripheral primary amines of bPEI and varying amounts of 2-(1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HBTU). These polymers were found to interact efficiently with negatively charged pDNA and formed stable complexes in the size range of ~240-450 nm. Acid-base titration profiles revealed improved buffering capacity of TP polymers as compared to bPEI. Transfection and cytotoxicity assays performed with TP/pDNA complexes on HEK293, CHO, and HeLa cells showed significantly higher transfection efficiency and cell viability with one of the complexes, TP2/pDNA complex, exhibited the highest transfection efficiency (~1.4-2.3-fold) outcompeting native bPEI and the commercially available transfection reagent, Lipofectamine 2000. Compared to previously reported THP polymers, the transfection efficiency of TP/pDNA complexes was found to be lower, as examined by flow cytometry. These results highlight the importance of the hydrophobic C-6 linker in THP polymers in forming compact nanostructures with pDNA, which might lead to efficient uptake and internalization of the complexes; however, the projected TP polymers offer an advantage of their rapid and economical one-step synthesis. PMID:24864245

  15. MDPSCL2: A New Protecting Group for Chemoselective Synthesis of 20

    E-print Network

    Theodorakis, Emmanuel

    -Br as the appropriate electrophiles. INTRODUCTION Antisense oligonucleotides constitute a promising class of therapeutic selected synthetic routes to 20 -O-methylated nucleosides, see Ref.[4] . For selected syn- thetic routes

  16. Chemoselective hydrogenation of functionalized nitroarenes and imines by using carbon nanofiber-supported iridium nanoparticles.

    PubMed

    Motoyama, Yukihiro; Taguchi, Masahiro; Desmira, Nelfa; Yoon, Seong-Ho; Mochida, Isao; Nagashima, Hideo

    2014-01-01

    The reaction of three types of carbon nanofibers (CNFs; platelet: CNF-P, tubular: CNF-T, herringbone: CNF-H) with Ir4(CO)12 in mesitylene at 165 °C provided the corresponding CNF-supported iridium nanoparticles, Ir/CNFs (Ir content=2.3-2.6 wt.%). Transmission electron microscopy (TEM) studies of these Ir/CNF samples revealed that size-controlled Ir nanoparticles (average particle size of 1.1-1.5 nm) existed on the CNFs. Among the three Ir/CNF samples, Ir/CNF-T showed an excellent catalytic activity and chemoselectivity towards hydrogenation of functionalized nitroarenes and imines; the corresponding aniline derivatives were obtained with high turnover numbers at ambient temperature under 10 tm of H2 , and the catalyst is reusable. Ir/CNF-T was also effective for the reductive N-alkylation of anilines with carbonyl compounds. PMID:24347068

  17. Chemoselective Tryptophan Labeling with Rhodium Carbenoids at Mild pH

    PubMed Central

    Antos, John M.; McFarland, Jesse M.; Iavarone, Anthony T.; Francis, Matthew B.

    2009-01-01

    Significant improvements have been made to a previously reported tryptophan modification method using rhodium carbenoids in aqueous solution, allowing the reaction to proceed at pH 6–7. This technique is based on the discovery that tert-butylhydroxyl amine promotes indole modification with rhodium carbenoids over a broad pH range (2–7). This methodology was demonstrated on peptide and protein substrates, generally yielding 40–60% conversion with excellent tryptophan chemoselectivity. The solvent accessibility of the indole side chains was found to be a key factor in successful carbenoid addition, as demonstrated by conducting the reaction at temperatures high enough to cause thermal denaturation of the protein substrate. Progress toward the expression of proteins bearing solvent accessible tryptophan residues as reactive handles for modification with rhodium carbenoids is also reported. PMID:19366262

  18. Chemoselective Boron-Catalyzed Nucleophilic Activation of Carboxylic Acids for Mannich-Type Reactions.

    PubMed

    Morita, Yuya; Yamamoto, Tomohiro; Nagai, Hideoki; Shimizu, Yohei; Kanai, Motomu

    2015-06-10

    The carboxyl group (COOH) is an omnipresent functional group in organic molecules, and its direct catalytic activation represents an attractive synthetic method. Herein, we describe the first example of a direct catalytic nucleophilic activation of carboxylic acids with BH3·SMe2, after which the acids are able to act as carbon nucleophiles, i.e. enolates, in Mannich-type reactions. This reaction proceeds with a mild organic base (DBU) and exhibits high levels of functional group tolerance. The boron catalyst is highly chemoselective toward the COOH group, even in the presence of other carbonyl moieties, such as amides, esters, or ketones. Furthermore, this catalytic method can be extended to highly enantioselective Mannich-type reactions by using a (R)-3,3'-I2-BINOL-substituted boron catalyst. PMID:26011419

  19. Thermogelling and Chemoselectively Cross-Linked Hydrogels with Controlled Mechanical Properties and Degradation Behavior.

    PubMed

    Boere, Kristel W M; van den Dikkenberg, Joep; Gao, Yuan; Visser, Jetze; Hennink, Wim E; Vermonden, Tina

    2015-09-14

    Chemoselectively cross-linked hydrogels have recently gained increasing attention for the development of novel, injectable biomaterials given their limited side reactions. In this study, we compared the properties of hydrogels obtained by native chemical ligation (NCL) and its recently described variation termed oxo-ester-mediated native chemical ligation (OMNCL) in combination with temperature-induced physical gelation. Triblock copolymers consisting of cysteine functionalities, thermoresponsive N-isopropylacrylamide (NIPAAm) units and degradable moieties were mixed with functionalized poly(ethylene glycol) (PEG) cross-linkers. Thioester or N-hydroxysuccinimide (NHS) functionalities attached to PEG reacted with cysteine residues of the triblock copolymers via either an NCL or OMNCL pathway. The combined physical and chemical cross-linking resulted in rapid network formation and mechanically strong hydrogels. Stiffness of the hydrogels was highest for thermogels that were covalently linked via OMNCL. Specifically, the storage modulus after 4 h reached a value of 26 kPa, which was over a 100 times higher than hydrogels formed by solely thermal physical interactions. Endothelial cells showed high cell viability of 98 ± 2% in the presence of OMNCL cross-linked hydrogels after 16 h of incubation, in contrast to a low cell viability (13 ± 7%) for hydrogels obtained by NCL cross-linking. Lysozyme was loaded in the gels and after 2 days more than 90% was released, indicating that the cross-linking reaction was indeed chemoselective as the protein was not covalently grafted to the hydrogel network. Moreover, the degradation rates of these hydrogels under physiological conditions could be tailored from 12 days up to 6 months by incorporation of a monomer containing a hydrolyzable lactone ring in the thermosensitive triblock copolymer. These results demonstrate a high tunability of mechanical properties and degradation rates of these in situ forming hydrogels that could be used for a variety of biomedical applications. PMID:26237583

  20. Back Cover: Synthesis of a Sulfonated Two-Dimensional Covalent Organic Framework as an Efficient Solid Acid Catalyst for Biobased Chemical Conversion (ChemSusChem 19/2015).

    PubMed

    Peng, Yongwu; Hu, Zhigang; Gao, Yongjun; Yuan, Daqiang; Kang, Zixi; Qian, Yuhong; Yan, Ning; Zhao, Dan

    2015-10-01

    The Back Cover picture shows the crystal structure of a sulfonic acid-functionalized 2D covalent organic framework (COF) and its application as a highly effective solid acid catalyst with excellent catalytic activity and chemoselectivity for the conversion of fructose into 5-hydroxymethylfurfural (HMF) and 2,5-diformylfuran (DFF). A sulfonated 2D crystalline COF, termed TFP-DABA, is synthesized directly using 1,3,5-triformylphloroglucinol (TFP) and 2,5-diaminobenzenesulfonic acid (DABA) via a Schiff base condensation reaction followed by irreversible enol-to-keto tautomerization. This COF is highly efficient for fructose conversion with remarkable yields (97% for HMF and 65% for DFF). This study provides encouragement for further exploration of COFs as heterogeneous catalysts for bio-based chemical conversion and related applications. More details can be found in the Communication by D. Zhao et?al. on page?3208 in Issue 19, 2015 (DOI: 10.1002/cssc.201500755). PMID:26448529

  1. Design and Synthesis of Novel Block Copolymers for Efficient Opto-Electronic Applications

    NASA Technical Reports Server (NTRS)

    Sun, Sam-Shajing; Fan, Zhen; Wang, Yiqing; Taft, Charles; Haliburton, James; Maaref, Shahin

    2002-01-01

    It has been predicted that nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration in organic photovoltaic devices due to improved morphology in comparison to polymer blend system. This paper presents preliminary data describing the design and synthesis of a novel Donor-Bridge-Acceptor (D-B-A) block copolymer system for potential high efficient organic optoelectronic applications. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (PPV), and the bridge block contains an electronically neutral non-conjugated aliphatic hydrocarbon chain. The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block stabilizes and facilitates the transport of the holes, the acceptor block stabilizes and facilitates the transport of the electrons, the bridge block is designed to hinder the probability of electron-hole recombination. Thus, improved charge separation and stability are expected with this system. In addition, charge migration toward electrodes may also be facilitated due to the potential nano-phase separated and highly ordered block copolymer ultra-structure.

  2. Micelle-Template Synthesis of Nitrogen-Doped Mesoporous Graphene as an Efficient Metal-Free Electrocatalyst for Hydrogen Production

    PubMed Central

    Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

    2014-01-01

    Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications. PMID:25523276

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

    PubMed Central

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

    2012-01-01

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

  4. ACCESS 3. Approximation concepts code for efficient structural synthesis: User's guide

    NASA Technical Reports Server (NTRS)

    Fleury, C.; Schmit, L. A., Jr.

    1980-01-01

    A user's guide is presented for ACCESS-3, a research oriented program which combines dual methods and a collection of approximation concepts to achieve excellent efficiency in structural synthesis. The finite element method is used for structural analysis and dual algorithms of mathematical programming are applied in the design optimization procedure. This program retains all of the ACCESS-2 capabilities and the data preparation formats are fully compatible. Four distinct optimizer options were added: interior point penalty function method (NEWSUMT); second order primal projection method (PRIMAL2); second order Newton-type dual method (DUAL2); and first order gradient projection-type dual method (DUAL1). A pure discrete and mixed continuous-discrete design variable capability, and zero order approximation of the stress constraints are also included.

  5. Efficient catalytic synthesis of dendritic polymers having internal fluorescence labels for bioconjugation.

    PubMed

    Chen, Guanghui; Felgner, Philip L; Guan, Zhibin

    2008-07-01

    Here we present an efficient synthesis of functional dendritic polymers carrying internal fluorescence labels for bioconjugation. Specifically, dendritic polymers having pyrene as fluorescence label in the core and N-hydroxysuccinimide (NHS) functional groups at the periphery were synthesized by coupling heterobifunctional PEG to hydroxyl functionalized dendritic polyethylene core. The dendritic polyethylene cores containing one pyrene label per polymer molecule were prepared through a one-step transition-metal-catalyzed polymerization using a pyrene-labeled Pd(II)-alpha-diimine chain walking catalyst. A series of pyrene-labeled dendritic scaffolds were obtained with different molecular weights and sizes. NHS active end groups were introduced to the periphery of the dendritic scaffolds through end-group functionalization. Those NHS-functionalized dendritic scaffolds were successfully used to conjugate a model protein, ovalbumin, to yield protein-polymer conjugates carrying multiple copies of protein attached to each scaffold. PMID:18517245

  6. Phosphinoyl and thiophosphinoylcarbodithioates: synthesis, molecular structure, and application as new efficient mediators for RAFT polymerization.

    PubMed

    Mazières, Stéphane; Kulai, Ihor; Geagea, Roland; Ladeira, Sonia; Destarac, Mathias

    2015-01-19

    New phosphinoyl and thiophosphinoylcarbodithioates were synthesized in a one-pot reaction from the corresponding phosphinochalcogenides. Compounds of this new generation of thiocarbonylthio derivatives have been fully characterized by IR as well as (1)H, (31)P, and (13)C?NMR spectroscopy and by mass spectrometry. Their solid-state structures reveal that they are isostructural but crystallize in different space groups. These new compounds are highly efficient reversible chain-transfer agents for the reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene (St) and n-butyl acrylate (nBA), with controlled number-average molecular weights (Mn) and narrow dispersity values (Ð<1.3). The controlled character of the polymerization was further exemplified by MALDI-TOF mass spectrometry and the synthesis of PSt-P(nBA) diblock copolymers. PMID:25476265

  7. Cyanuric Chloride as an Efficient Catalyst for the Synthesis of 2,3-Unsaturated O-Glycosides by Ferrier Rearrangement

    PubMed Central

    Yang, Xiaojuan; Li, Na

    2014-01-01

    Cyanuric chloride has been found to be an efficient catalyst for the synthesis of 2,3-unsaturated O-glycosides from the reaction of 3,4,6-tri-O-acetyl-D-glucal and a wide range of alcohols in dichloromethane at room temperature. The experimental procedure is simple, and the products are obtained in high yields. PMID:24574881

  8. Solid-Phase Synthesis as a Platform for the Discovery of New Ruthenium Complexes for Efficient Release of Photocaged Ligands

    E-print Network

    Turro, Claudia

    Solid-Phase Synthesis as a Platform for the Discovery of New Ruthenium Complexes for Efficient Institute, Detroit, Michigan 48201, United States *S Supporting Information ABSTRACT: Ruthenium. A method was developed to rapidly synthesize, screen, and identify ruthenium-based caging groups

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

    EPA Science Inventory

    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...

  10. Efficient Synthesis of Peptide and Protein Functionalized Pyrrole-Imidazole Polyamides Using Native Chemical Ligation.

    PubMed

    Janssen, Brian M G; van Ommeren, Sven P F I; Merkx, Maarten

    2015-01-01

    The advancement of DNA-based bionanotechnology requires efficient strategies to functionalize DNA nanostructures in a specific manner with other biomolecules, most importantly peptides and proteins. Common DNA-functionalization methods rely on laborious and covalent conjugation between DNA and proteins or peptides. Pyrrole-imidazole (Py-Im) polyamides, based on natural minor groove DNA-binding small molecules, can bind to DNA in a sequence specific fashion. In this study, we explore the use of Py-Im polyamides for addressing proteins and peptides to DNA in a sequence specific and non-covalent manner. A generic synthetic approach based on native chemical ligation was established that allows efficient conjugation of both peptides and recombinant proteins to Py-Im polyamides. The effect of Py-Im polyamide conjugation on DNA binding was investigated by Surface Plasmon Resonance (SPR). Although the synthesis of different protein-Py-Im-polyamide conjugates was successful, attenuation of DNA affinity was observed, in particular for the protein-Py-Im-polyamide conjugates. The practical use of protein-Py-Im-polyamide conjugates for addressing DNA structures in an orthogonal but non-covalent manner, therefore, remains to be established. PMID:26053396

  11. Efficient Rhodium-Catalyzed Multicomponent Reaction for the Synthesis of Novel Propargylamines.

    PubMed

    Rubio-Pérez, Laura; Iglesias, Manuel; Munárriz, Julen; Polo, Victor; Pérez-Torrente, Jesús J; Oro, Luis A

    2015-12-01

    [{Rh(?-Cl)(H)2 (IPr)}2 ] (IPr = 1,3-bis-(2,6-diisopropylphenyl)imidazole-2-ylidene) was found to be an efficient catalyst for the synthesis of novel propargylamines by a one-pot three-component reaction between primary arylamines, aliphatic aldehydes, and triisopropylsilylacetylene. This methodology offers an efficient synthetic pathway for the preparation of secondary propargylamines derived from aliphatic aldehydes. The reactivity of [{Rh(?-Cl)(H)2 (IPr)}2 ] with amines and aldehydes was studied, leading to the identification of complexes [RhCl(CO)IPr(MesNH2 )] (MesNH2 = 2,4,6-trimethylaniline) and [RhCl(CO)2 IPr]. The latter shows a very low catalytic activity while the former brought about reaction rates similar to those obtained with [{Rh(?-Cl)(H)2 (IPr)}2 ]. Besides, complex [RhCl(CO)IPr(MesNH2 )] reacts with an excess of amine and aldehyde to give [RhCl(CO)IPr{MesN?CHCH2 CH(CH3 )2 }], which was postulated as the active species. A mechanism that clarifies the scarcely studied catalytic cycle of A3 -coupling reactions is proposed based on reactivity studies and DFT calculations. PMID:26490447

  12. Efficient Catalytic Activity BiFeO3 Nanoparticles Prepared by Novel Microwave-Assisted Synthesis.

    PubMed

    Zou, Jing; Gong, Wanyun; Ma, Jinai; Li, Lu; Jiang, Jizhou

    2015-02-01

    A novel microwave-assisted sol-gel method was applied to the synthesis of the single-phase perovskite bismuth ferrite nanoparticles (BFO NPs) with the mean diameter ca. 73.7 nm. The morphology was characterized by scanning electron microscope (SEM). The X-ray diffraction (XRD) revealed the rhombohedral phase with R3c space group. The weak ferromagnetic behavior at room temperature was affirmed by the vibrating sample magnetometer (VSM). According to the UV-vis diffuse reflectance spectrum (UV-DSR), the band gap energy of BFO NPs was determined to be 2.18 eV. The electrochemical activity was evaluated by BFO NPs-chitosan-glassy carbon electrode (BFO-CS-GCE) sensor for detection of p-nitrophenol contaminants. The material showed an efficient oxidation catalytic activity by degrading methylene blue (MB). It was found that the degradation efficiency of 10 mg L-1 MB at pH 6.0 was above 90.9% after ultrasound- and microwave-combined-assisted (US-MW) irradiation for 15 min with BFO NPs as catalyst and H202 as oxidant. A possible reaction mechanism of degradation of MB was also proposed. PMID:26353647

  13. Identification of a critical determinant that enables efficient fatty acid synthesis in oleaginous fungi

    PubMed Central

    Chen, Haiqin; Hao, Guangfei; Wang, Lei; Wang, Hongchao; Gu, Zhennan; Liu, Liming; Zhang, Hao; Chen, Wei; Chen, Yong Q.

    2015-01-01

    Microorganisms are valuable resources for lipid production. What makes one microbe but not the other able to efficiently synthesize and accumulate lipids is poorly understood. In the present study, global gene expression prior to and after the onset of lipogenesis was determined by transcriptomics using the oleaginous fungus Mortierella alpina as a model system. A core of 23 lipogenesis associated genes was identified and their expression patterns shared a high similarity among oleaginous microbes Chlamydomonas reinhardtii, Mucor circinelloides and Rhizopus oryzae but was dissimilar to the non-oleaginous Aspergillus nidulans. Unexpectedly, Glucose-6-phosphate dehydrogenase (G6PD) and 6-phosphogluconate dehydrogenase (PGD) in the pentose phosphate pathway (PPP) were found to be the NADPH producers responding to lipogenesis in the oleaginous microbes. Their role in lipogenesis was confirmed by a knockdown experiment. Our results demonstrate, for the first time, that the PPP plays a significant role during fungal lipogenesis. Up-regulation of NADPH production by the PPP, especially G6PD, may be one of the critical determinants that enables efficiently fatty acid synthesis in oleaginous microbes. PMID:26059272

  14. Efficient Synthesis of Peptide and Protein Functionalized Pyrrole-Imidazole Polyamides Using Native Chemical Ligation

    PubMed Central

    Janssen, Brian M. G.; van Ommeren, Sven P. F. I.; Merkx, Maarten

    2015-01-01

    The advancement of DNA-based bionanotechnology requires efficient strategies to functionalize DNA nanostructures in a specific manner with other biomolecules, most importantly peptides and proteins. Common DNA-functionalization methods rely on laborious and covalent conjugation between DNA and proteins or peptides. Pyrrole-imidazole (Py–Im) polyamides, based on natural minor groove DNA-binding small molecules, can bind to DNA in a sequence specific fashion. In this study, we explore the use of Py–Im polyamides for addressing proteins and peptides to DNA in a sequence specific and non-covalent manner. A generic synthetic approach based on native chemical ligation was established that allows efficient conjugation of both peptides and recombinant proteins to Py–Im polyamides. The effect of Py–Im polyamide conjugation on DNA binding was investigated by Surface Plasmon Resonance (SPR). Although the synthesis of different protein-Py–Im-polyamide conjugates was successful, attenuation of DNA affinity was observed, in particular for the protein-Py–Im-polyamide conjugates. The practical use of protein-Py–Im-polyamide conjugates for addressing DNA structures in an orthogonal but non-covalent manner, therefore, remains to be established. PMID:26053396

  15. Identification of a critical determinant that enables efficient fatty acid synthesis in oleaginous fungi.

    PubMed

    Chen, Haiqin; Hao, Guangfei; Wang, Lei; Wang, Hongchao; Gu, Zhennan; Liu, Liming; Zhang, Hao; Chen, Wei; Chen, Yong Q

    2015-01-01

    Microorganisms are valuable resources for lipid production. What makes one microbe but not the other able to efficiently synthesize and accumulate lipids is poorly understood. In the present study, global gene expression prior to and after the onset of lipogenesis was determined by transcriptomics using the oleaginous fungus Mortierella alpina as a model system. A core of 23 lipogenesis associated genes was identified and their expression patterns shared a high similarity among oleaginous microbes Chlamydomonas reinhardtii, Mucor circinelloides and Rhizopus oryzae but was dissimilar to the non-oleaginous Aspergillus nidulans. Unexpectedly, Glucose-6-phosphate dehydrogenase (G6PD) and 6-phosphogluconate dehydrogenase (PGD) in the pentose phosphate pathway (PPP) were found to be the NADPH producers responding to lipogenesis in the oleaginous microbes. Their role in lipogenesis was confirmed by a knockdown experiment. Our results demonstrate, for the first time, that the PPP plays a significant role during fungal lipogenesis. Up-regulation of NADPH production by the PPP, especially G6PD, may be one of the critical determinants that enables efficiently fatty acid synthesis in oleaginous microbes. PMID:26059272

  16. Nonlinear inverse synthesis for high spectral efficiency transmission in optical fibers.

    PubMed

    Le, Son Thai; Prilepsky, Jaroslaw E; Turitsyn, Sergei K

    2014-11-01

    In linear communication channels, spectral components (modes) defined by the Fourier transform of the signal propagate without interactions with each other. In certain nonlinear channels, such as the one modelled by the classical nonlinear Schrödinger equation, there are nonlinear modes (nonlinear signal spectrum) that also propagate without interacting with each other and without corresponding nonlinear cross talk, effectively, in a linear manner. Here, we describe in a constructive way how to introduce such nonlinear modes for a given input signal. We investigate the performance of the nonlinear inverse synthesis (NIS) method, in which the information is encoded directly onto the continuous part of the nonlinear signal spectrum. This transmission technique, combined with the appropriate distributed Raman amplification, can provide an effective eigenvalue division multiplexing with high spectral efficiency, thanks to highly suppressed channel cross talk. The proposed NIS approach can be integrated with any modulation formats. Here, we demonstrate numerically the feasibility of merging the NIS technique in a burst mode with high spectral efficiency methods, such as orthogonal frequency division multiplexing and Nyquist pulse shaping with advanced modulation formats (e.g., QPSK, 16QAM, and 64QAM), showing a performance improvement up to 4.5 dB, which is comparable to results achievable with multi-step per span digital back propagation. PMID:25401821

  17. Can oriented-attachment be an efficient growth mechanism for the synthesis of 1D nanocrystals via atomic layer deposition?

    PubMed

    Wen, Kechun; He, Weidong

    2015-09-25

    One-dimensional (1D) nanocrystals, such as nanorods and nanowires, have received extensive attention in the nanomaterials field due to their large surface areas and 1D confined transport properties. Oriented attachment (OA) is now recognized as a major growth mechanism for efficiently synthesizing 1D nanocrystals. Recently, atomic layer deposition (ALD) has been modified to be a powerful vapor-phase technique with which to synthesize 1D OA nanorods/nanowires with high efficiency and quality by increasing the temperature and purging time. In this invited mini-review, we look into the advantages of OA and high-temperature ALD, and investigate the potential of employing the OA growth mechanism for the synthesis of 1D nanocrystals via modified ALD, aiming to provide guidance to researchers in the fields of both OA and ALD for efficient synthesis of 1D nanocrystals. PMID:26334690

  18. Can oriented-attachment be an efficient growth mechanism for the synthesis of 1D nanocrystals via atomic layer deposition?

    NASA Astrophysics Data System (ADS)

    Wen, Kechun; He, Weidong

    2015-09-01

    One-dimensional (1D) nanocrystals, such as nanorods and nanowires, have received extensive attention in the nanomaterials field due to their large surface areas and 1D confined transport properties. Oriented attachment (OA) is now recognized as a major growth mechanism for efficiently synthesizing 1D nanocrystals. Recently, atomic layer deposition (ALD) has been modified to be a powerful vapor-phase technique with which to synthesize 1D OA nanorods/nanowires with high efficiency and quality by increasing the temperature and purging time. In this invited mini-review, we look into the advantages of OA and high-temperature ALD, and investigate the potential of employing the OA growth mechanism for the synthesis of 1D nanocrystals via modified ALD, aiming to provide guidance to researchers in the fields of both OA and ALD for efficient synthesis of 1D nanocrystals.

  19. Simultaneous sonication assistance for the synthesis of tetrahydropyridines and its efficient catalyst ZrP2O7 nanoparticles.

    PubMed

    Javidan, Abdollah; Ziarati, Abolfazl; Safaei-Ghomi, Javad

    2014-05-01

    In this research, a general synthetic method for the synthesis of tetrahydropyridines were developed using ZrP2O7 nanoparticles under ultrasonic irradiations. Firstly by a simple and green process, nano zirconium pyrophosphate was prepared via sonication. Subsequently, this nanoparticle was used as an efficient catalyst for the synthesis of highly functionalized tetrahydropyridines via five-component reaction of aromatic aldehyde, amine and ethyl acetoacetate in ethanol under ultrasound irradiation. The present approach offers several advantages such as high yields, environmentally benign, simple work-up, excellent yield of products, short reaction times as well as recoverability and reusability of the catalyst. PMID:24315669

  20. Efficient Synthesis of ?-Aryl-?-lactams and Their Resolution with (S)-Naproxen: Preparation of (R)- and (S)-Baclofen.

    PubMed

    Montoya-Balbás, Iris J; Valentín-Guevara, Berenice; López-Mendoza, Estefanía; Linzaga-Elizalde, Irma; Ordoñez, Mario; Román-Bravo, Perla

    2015-01-01

    An efficient synthesis of enantiomerically-pure ?-aryl-?-lactams is described. The principal feature of this synthesis is the practical resolution of ?-aryl-?-lactams with (S)-Naproxen. The procedure is based on the Michael addition of nitromethane to benzylidenemalonates, which was easily obtained, followed by the reduction of the ?-nitroester in the presence of Raney nickel and the subsequent saponification/decarboxylation reaction. The utility of this methodology was highlighted by the preparation of enantiomerically-pure (R)- and (S)-Baclofen hydrochloride. PMID:26690390

  1. Efficient microwave assisted synthesis of metal-organic framework UiO-66: optimization and scale up.

    PubMed

    Taddei, Marco; Dau, Phuong V; Cohen, Seth M; Ranocchiari, Marco; van Bokhoven, Jeroen A; Costantino, Ferdinando; Sabatini, Stefano; Vivani, Riccardo

    2015-08-21

    A highly efficient and scalable microwave assisted synthesis of zirconium-based metal-organic framework UiO-66 was developed. In order to identify the best conditions for optimizing the process, a wide range of parameters was investigated. The efficiency of the process was evaluated with the aid of four quantitative indicators. The properties of the materials prepared by microwave irradiation were compared with those synthesized by conventional heating, and no significant effects on morphology, crystal size, or defects were found from the use of microwave assisted heating. Scale up was performed maintaining the high efficiency of the process. PMID:26165508

  2. Simple and efficient synthesis of 2-[(18)F]fluoroethyl triflate for high yield (18)fluoroethylation.

    PubMed

    Peters, Tanja; Vogg, Andreas; Oppel, Iris M; Schmaljohann, Jörn

    2014-12-01

    The [(18)F]fluoroethyl moiety has been widely utilized in the synthesis of (18)F-labelled compounds. The aim of this work was the reliable synthesis of [(18)F]FEtOTf with a novel strategy to increase the reactivity of the commonly used [(18)F]FEB and [(18)F]FEtOTos. [(18)F]FEtOTf and the intermediate [(18)F]FEtOH were synthesized in high RCY (78% and 85%, respectively) and purified by SPE. The high potency of [(18)F]FEtOTf was shown by the efficient alkylation of the deactivated nucleophile aniline under mild conditions, as well as by the synthesis of [(18)F]FEC. PMID:25189703

  3. Intramolecular carbolithiation of N-allyl-ynamides: an efficient entry to 1,4-dihydropyridines and pyridines – application to a formal synthesis of sarizotan

    PubMed Central

    Gati, Wafa; Rammah, Mohamed M; Rammah, Mohamed B

    2012-01-01

    Summary We have developed a general synthesis of polysubstituted 1,4-dihydropyridines and pyridines based on a highly regioselective lithiation/6-endo-dig intramolecular carbolithiation from readily available N-allyl-ynamides. This reaction, which has been successfully applied to the formal synthesis of the anti-dyskinesia agent sarizotan, further extends the use of ynamides in organic synthesis and further demonstrates the synthetic efficiency of carbometallation reactions. PMID:23365632

  4. Scalable and chromatography-free synthesis of 2-(2-formylalkyl)arenecarboxylic acid derivatives through the supramolecularly controlled hydroformylation of vinylarene-2-carboxylic acids.

    PubMed

    Dydio, Pawe?; Reek, Joost N H

    2014-05-01

    This protocol describes how to prepare 2-(2-formylalkyl)-arenecarboxylic acid derivatives, common building blocks for the synthesis of various valuable chemicals (e.g., anti-obesity and Alzheimer's disease treatment pharmaceuticals), by using the fully regioselective hydroformylation of vinyl arene derivatives. This catalytic reaction proceeds cleanly with 100% regioselectivity and chemoselectivity. The procedure is reliably scalable and can be efficiently conducted on a multigram scale. The analytically pure product is easily isolated with a nearly quantitative yield by using a simple acid-base extraction workup and avoids any tedious chromatography. This protocol details the synthesis of a bisphosphite ligand (L1) that is a pivotal element of the catalytic system used, Rh(acac)(CO)2 with ligand L1, starting from commercial building blocks. The protocol also describes a general procedure for the preparative hydroformylation of vinylarene-2-carboxylic acid derivatives to 2-formylalkylarene products, providing a representative example for the hydroformylation of 2-vinylbenzoic acid (1a) to 2-(3-oxopropane)-benzoic acid (2a). The synthesis of L1 (six chemical reactions) uses 2-nitrophenylhydrazine, 4-benzyloxybenzoylchloride and (S)-binol, and takes 5-7 working days. The actual hydroformylation reaction of each vinyl arene derivative takes ?4 h of active effort over a period of 1-3 d. PMID:24762785

  5. Microscopic Investigation of Chemoselectivity in Ag-Pt-Fe3O4 Heterotrimer Formation: Mechanistic Insights and Implications for Controlling High-Order Hybrid Nanoparticle Morphology.

    PubMed

    Hodges, James M; Morse, James R; Williams, Mary Elizabeth; Schaak, Raymond E

    2015-12-16

    Three-component hybrid nanoparticle heterotrimers, which are important multifunctional constructs that underpin diverse applications, are commonly synthesized by growing a third domain off of a two-component heterodimer seed. However, because heterodimer seeds expose two distinct surfaces that often can both support nucleation and growth, selectively targeting one particular surface is critical for exclusively accessing a desired configuration. Understanding and controlling nucleation and growth therefore enables the rational formation of high-order hybrid nanoparticles. Here, we report an in-depth microscopic investigation that probes the chemoselective addition of Ag to Pt-Fe3O4 heterodimer seeds to form Ag-Pt-Fe3O4 heterotrimers. We find that the formation of the Ag-Pt-Fe3O4 heterotrimers initiates with indiscriminate Ag nucleation onto both the Pt and Fe3O4 surfaces of Pt-Fe3O4, followed by surface diffusion and coalescence of Ag onto the Pt surface to form the Ag-Pt-Fe3O4 product. Control experiments reveal that the size of the Ag domain of Ag-Pt-Fe3O4 correlates with the overall surface area of the Pt-Fe3O4 seeds, which is consistent with the coalescence of Ag through a surface-mediated process and can also be exploited to tune the size of the Ag domain. Additionally, we observe that small iron oxide islands on the Pt surface of the Pt-Fe3O4 seeds, deposited during the formation of Pt-Fe3O4, define the morphology of the Ag domain, which in turn influences its optical properties. These results provide unprecedented microscopic insights into the pathway by which Ag-Pt-Fe3O4 heterotrimer nanoparticles form and uncover new design guidelines for the synthesis of high-order hybrid nanoparticles with precisely targeted morphologies and properties. PMID:26599998

  6. Reactivity and Chemoselectivity of Allenes in Rh(I)-Catalyzed Intermolecular (5 + 2) Cycloadditions with Vinylcyclopropanes: Allene-Mediated Rhodacycle Formation Can Poison Rh(I)-Catalyzed Cycloadditions

    PubMed Central

    2015-01-01

    Allenes are important 2? building blocks in organic synthesis and engage as 2-carbon components in many metal-catalyzed reactions. Wender and co-workers discovered that methyl substituents on the terminal allene double bond counterintuitively change the reactivities of allenes in [Rh(CO)2Cl]2-catalyzed intermolecular (5 + 2) cycloadditions with vinylcyclopropanes (VCPs). More sterically encumbered allenes afford higher cycloadduct yields, and such effects are also observed in other Rh(I)-catalyzed intermolecular cycloadditions. Through density functional theory calculations (B3LYP and M06) and experiment, we explored this enigmatic reactivity and selectivity of allenes in [Rh(CO)2Cl]2-catalyzed intermolecular (5 + 2) cycloadditions with VCPs. The apparent low reactivity of terminally unsubstituted allenes is associated with a competing allene dimerization that irreversibly sequesters rhodium. With terminally substituted allenes, steric repulsion between the terminal substituents significantly increases the barrier of allene dimerization while the barrier of the (5 + 2) cycloaddition is not affected, and thus the cycloaddition prevails. Computation has also revealed the origin of chemoselectivity in (5 + 2) cycloadditions with allene-ynes. Although simple allene and acetylene have similar reaction barriers, intermolecular (5 + 2) cycloadditions of allene-ynes occur exclusively at the terminal allene double bond. The terminal double bond is more reactive due to the enhanced d??* backdonation. At the same time, insertion of the internal double bond of an allene-yne has a higher barrier as it would break ? conjugation. Substituted alkynes are more difficult to insert compared with acetylene, because of the steric repulsion from the additional substituents. This leads to the greater reactivity of the allene double bond relative to the alkynyl group in allene-ynes. PMID:25379606

  7. Efficient strategy for the stereoselective synthesis of 2,3-disubstituted benzo[a]quinolizidine alkaloids: concise synthesis

    E-print Network

    Suh, Young-Ger

    [a]quinolizidine alkaloids: concise synthesis of (À)-protoemetinol Hyunyoung Moon a , Hongchan An a , Jaehoon Sim a , Kyeojin 2014 Keywords: (À)-Protoemetinol Benzo[a]quinolizidine alkaloid Cross metathesis Aza reserved. Benzo[a]quinolizidine alkaloids,1 which are mainly isolated from the two different families

  8. An Efficient Solution-Phase Synthesis of 4,5,7-Trisubstituted Pyrrolo[3,2-d]pyrimidines

    PubMed Central

    Zhang, Weihe; Liu, Jing; Stashko, Michael A.; Wang, Xiaodong

    2013-01-01

    We have developed an efficient and robust route to synthesize 4,5,7-trisubstituted pyrrolo[3,2-d]pyrimidines as potent kinase inhibitors. This solution-phase synthesis features a SNAr substitution reaction, cross-coupling reaction, one-pot reduction/reductive amination and N-alkylation reaction. These reactions occur rapidly with high yields and have broad substrate scopes. A variety of groups can be selectively introduced into the N5 and C7 positions of 4,5,7-trisubstituted pyrrolopyrimidines at a late stage of the synthesis, thereby providing a highly efficient approach to explore the structure-activity relationships of pyrrolopyrimidine derivatives. Four synthetic analogs have been profiled against a panel of 48 kinases and a new and selective FLT3 inhibitor 9 is identified. PMID:23181516

  9. Time- and energy-efficient solution combustion synthesis of binary metal tungstate nanoparticles with enhanced photocatalytic activity.

    PubMed

    Thomas, Abegayl; Janáky, Csaba; Samu, Gergely F; Huda, Muhammad N; Sarker, Pranab; Liu, J Ping; van Nguyen, Vuong; Wang, Evelyn H; Schug, Kevin A; Rajeshwar, Krishnan

    2015-05-22

    In the search for stable and efficient photocatalysts beyond TiO2 , the tungsten-based oxide semiconductors silver tungstate (Ag2 WO4 ), copper tungstate (CuWO4 ), and zinc tungstate (ZnWO4 ) were prepared using solution combustion synthesis (SCS). The tungsten precursor's influence on the product was of particular relevance to this study, and the most significant effects are highlighted. Each sample's photocatalytic activity towards methyl orange degradation was studied and benchmarked against their respective commercial oxide sample obtained by solid-state ceramic synthesis. Based on the results herein, we conclude that SCS is a time- and energy-efficient method to synthesize crystalline binary tungstate nanomaterials even without additional excessive heat treatment. As many of these photocatalysts possess excellent photocatalytic activity, the discussed synthetic strategy may open sustainable materials chemistry avenues to solar energy conversion and environmental remediation. PMID:26018624

  10. Efficient Organocatalytic Construction of C4-Alkyl Substituted Piperidines and Their Application to the Synthesis of (+)-?-Skytanthine.

    PubMed

    Shiomi, Shinya; Sugahara, Erika; Ishikawa, Hayato

    2015-10-12

    Chiral piperidines which contain an alkyl group at C4 positions are one of the important architectures because it is appeared in several natural products. An efficient protocol for the preparation of C4-alkyl substituted chiral piperidines using secondary amine catalyzed formal aza [3+3] cycloaddition reaction with aliphatic ?,?-unsaturated aldehydes and thiomalonamate derivatives is reported. In our reaction system, thiomalonamate is an excellent nucleophile and the addition of suitable acid and its amount is an important factor for the acceleration effect in organocatalytic reaction. Furthermore, water and MeOH also have an acceleration effect. These efforts lead to only 0.1?mol?% catalyst loading in multigram scale synthesis for suitable reaction time. In addition, the efficient enantioselective total synthesis of (+)-?-skytanthine by using our developed reaction as key step was achieved in total 15?% yield. All carbon and nitrogen units were introduced by one step with high enantioselectivity. PMID:26333476

  11. Ultrasonic irradiation assisted efficient regioselective synthesis of CF3-containing pyrazoles catalyzed by Cu(OTf)2/Et3N

    PubMed Central

    2013-01-01

    Background Most of the known approaches to the synthesis of CF3-containing organic compounds suffer from serious drawbacks. For example the starting materials required for these methods are rather difficult to obtain, or they are fairly toxic and inconvenient to work with and methods for direct fluorination and trifluoromethylation do not always allow the introduction of the CF3-group at the required position of a molecule. Results An efficient and attractive regioselective synthesis of a series of novel pyrazoles containing the trifluromethyl moiety was achieved using Cu(OTf)2/Et3N as an efficient catalytic system under ultrasonic irradiation. Conclusions Cu(OTf)2/Et3N catalyst showed a great advantage over all the investigated catalysts, and the ultrasonic irradiation method offered high yields of pyrazoles in short reaction time compared with classical conditions. gHMBC spectra of the product were used to rationalize the observed regioselectivity. PMID:23764261

  12. Efficient synthesis of ?- and ?-carbolines by sequential Pd-catalyzed site-selective C-C and twofold C-N coupling reactions.

    PubMed

    Hung, Tran Quang; Dang, Tuan Thanh; Janke, Julia; Villinger, Alexander; Langer, Peter

    2015-02-01

    Two concise and efficient approaches were developed for the synthesis of ?- and ?-carboline derivatives. The success of the synthesis relies on site-selective Suzuki-Miyaura reactions of 1-chloro-2-bromopyridine or 2,3-dibromopyridine with 2-bromophenylboronic acid and subsequent cyclization with amines which proceeds by twofold Pd-catalyzed C-N coupling reactions. PMID:25464277

  13. Towards efficient chemical synthesis via engineering enzyme catalysis in biomimetic nanoreactors.

    PubMed

    Liu, Jia; Yang, Qihua; Li, Can

    2015-09-18

    Biocatalysis with immobilized enzymes as catalysts holds enormous promise in developing more efficient and sustainable processes for the synthesis of fine chemicals, chiral pharmaceuticals and biomass feedstocks. Despite the appealing potentials, nowadays the industrial-scale application of biocatalysts is still quite modest in comparison with that of traditional chemical catalysts. A critical issue is that the catalytic performance of enzymes, the sophisticated and vulnerable catalytic machineries, strongly depends on their intracellular working environment; however the working circumstances provided by the support matrix are radically different from those in cells. This often leads to various adverse consequences on enzyme conformation and dynamic properties, consequently decreasing the overall performance of immobilized enzymes with regard to their activity, selectivity and stability. Engineering enzyme catalysis in support nanopores by mimicking the physiological milieu of enzymes in vivo and investigating how the interior microenvironment of nanopores imposes an influence on enzyme behaviors in vitro are of paramount significance to modify and improve the catalytic functions of immobilized enzymes. In this feature article, we have summarized the recent advances in mimicking the working environment and working patterns of intracellular enzymes in nanopores of mesoporous silica-based supports. Especially, we have demonstrated that incorporation of polymers into silica nanopores could be a valuable approach to create the biomimetic microenvironment for enzymes in the immobilized state. PMID:26208044

  14. Phase and composition controllable synthesis of cobalt manganese spinel nanoparticles towards efficient oxygen electrocatalysis.

    PubMed

    Li, Chun; Han, Xiaopeng; Cheng, Fangyi; Hu, Yuxiang; Chen, Chengcheng; Chen, Jun

    2015-01-01

    Spinel-type oxides are technologically important in many fields, including electronics, magnetism, catalysis and electrochemical energy storage and conversion. Typically, these materials are prepared by conventional ceramic routes that are energy consuming and offer limited control over shape and size. Moreover, for mixed-metal oxide spinels (for example, Co(x)Mn(3-x)O4), the crystallographic phase sensitively correlates with the metal ratio, posing great challenges to synthesize active product with simultaneously tuned phase and composition. Here we report a general synthesis of ultrasmall cobalt manganese spinels with tailored structural symmetry and composition through facile solution-based oxidation-precipitation and insertion-crystallization process at modest condition. As an example application, the nanocrystalline spinels catalyse the oxygen reduction/evolution reactions, showing phase and composition co-dependent performance. Furthermore, the mild synthetic strategy allows the formation of homogeneous and strongly coupled spinel/carbon nanocomposites, which exhibit comparable activity but superior durability to Pt/C and serve as efficient catalysts to build rechargeable Zn-air and Li-air batteries. PMID:26040417

  15. Phase and composition controllable synthesis of cobalt manganese spinel nanoparticles towards efficient oxygen electrocatalysis

    PubMed Central

    Li, Chun; Han, Xiaopeng; Cheng, Fangyi; Hu, Yuxiang; Chen, Chengcheng; Chen, Jun

    2015-01-01

    Spinel-type oxides are technologically important in many fields, including electronics, magnetism, catalysis and electrochemical energy storage and conversion. Typically, these materials are prepared by conventional ceramic routes that are energy consuming and offer limited control over shape and size. Moreover, for mixed-metal oxide spinels (for example, CoxMn3?xO4), the crystallographic phase sensitively correlates with the metal ratio, posing great challenges to synthesize active product with simultaneously tuned phase and composition. Here we report a general synthesis of ultrasmall cobalt manganese spinels with tailored structural symmetry and composition through facile solution-based oxidation–precipitation and insertion–crystallization process at modest condition. As an example application, the nanocrystalline spinels catalyse the oxygen reduction/evolution reactions, showing phase and composition co-dependent performance. Furthermore, the mild synthetic strategy allows the formation of homogeneous and strongly coupled spinel/carbon nanocomposites, which exhibit comparable activity but superior durability to Pt/C and serve as efficient catalysts to build rechargeable Zn–air and Li–air batteries. PMID:26040417

  16. Phase and composition controllable synthesis of cobalt manganese spinel nanoparticles towards efficient oxygen electrocatalysis

    NASA Astrophysics Data System (ADS)

    Li, Chun; Han, Xiaopeng; Cheng, Fangyi; Hu, Yuxiang; Chen, Chengcheng; Chen, Jun

    2015-06-01

    Spinel-type oxides are technologically important in many fields, including electronics, magnetism, catalysis and electrochemical energy storage and conversion. Typically, these materials are prepared by conventional ceramic routes that are energy consuming and offer limited control over shape and size. Moreover, for mixed-metal oxide spinels (for example, CoxMn3-xO4), the crystallographic phase sensitively correlates with the metal ratio, posing great challenges to synthesize active product with simultaneously tuned phase and composition. Here we report a general synthesis of ultrasmall cobalt manganese spinels with tailored structural symmetry and composition through facile solution-based oxidation-precipitation and insertion-crystallization process at modest condition. As an example application, the nanocrystalline spinels catalyse the oxygen reduction/evolution reactions, showing phase and composition co-dependent performance. Furthermore, the mild synthetic strategy allows the formation of homogeneous and strongly coupled spinel/carbon nanocomposites, which exhibit comparable activity but superior durability to Pt/C and serve as efficient catalysts to build rechargeable Zn-air and Li-air batteries.

  17. Biochemical Characterization of a First Fungal Esterase from Rhizomucor miehei Showing High Efficiency of Ester Synthesis

    PubMed Central

    Liu, Yu; Xu, Haibo; Yan, Qiaojuan; Yang, Shaoqing; Duan, Xiaojie; Jiang, Zhengqiang

    2013-01-01

    Background Esterases with excellent merits suitable for commercial use in ester production field are still insufficient. The aim of this research is to advance our understanding by seeking for more unusual esterases and revealing their characterizations for ester synthesis. Methodology/Principal Findings A novel esterase-encoding gene from Rhizomucor miehei (RmEstA) was cloned and expressed in Escherichia coli. Sequence analysis revealed a 975-bp ORF encoding a 324-amino-acid polypeptide belonging to the hormone-sensitive lipase (HSL) family IV and showing highest similarity (44%) to the Paenibacillus mucilaginosus esterase/lipase. Recombinant RmEstA was purified to homogeneity: it was 34 kDa by SDS-PAGE and showed optimal pH and temperature of 6.5 and 45°C, respectively. The enzyme was stable to 50°C, under a broad pH range (5.0–10.6). RmEstA exhibited broad substrate specificity toward p-nitrophenol esters and short-acyl-chain triglycerols, with highest activities (1,480 U mg?1 and 228 U mg?1) for p-nitrophenyl hexanoate and tributyrin, respectively. RmEstA efficiently synthesized butyl butyrate (92% conversion yield) when immobilized on AOT-based organogel. Conclusion RmEstA has great potential for industrial applications. RmEstA is the first reported esterase from Rhizomucor miehei. PMID:24204998

  18. Hyperspectral data processing for chemoselective multiplex coherent anti-Stokes Raman scattering microscopy of unknown samples

    NASA Astrophysics Data System (ADS)

    Pohling, Christoph; Buckup, Tiago; Motzkus, Marcus

    2011-02-01

    Multiplex coherent anti-Stokes Raman scattering (MCARS) provides labeling free and fast characterization of materials and biological samples in nonlinear microscopy. In spite of its success, remaining challenges regarding the data analysis for chemoselective imaging still have to be solved. In general, image contrast has been realized by using only one spectral feature directly taken from the unprocessed raw data. This procedure is limited to strong and well separated Raman resonances like the saturated CH-stretching vibration of lipids in the case of biological samples. In order to overcome this limitation, we present a new method of MCARS data processing that exploits the whole measured spectrum to disentangle overlapping contributions of different (bio-) chemical components. Our ``two-step'' approach is based on the combination of imaginary part extraction followed by global fitting of the hyperspectral data set. Previous knowledge about the sample, e.g., pure spectra of the individual components is no longer necessary. The result is a highly contrasted image, where the patterns and differences between the sample components can be represented in different colors. We successfully applied this method to complex structured polymer samples and biological tissues.

  19. Concise Synthesis of the Tricyclic Core of Salimabromide.

    PubMed

    Schmalzbauer, Björn; Menche, Dirk

    2015-06-19

    A concise synthesis of the tricyclic core 2 of the structurally unique marine myxobacterial natural product salimabromide has been developed. Compound 2 contains the tetraline subunit including the two quaternary centers and the eight-membered ring of salimabromide. Major features for its synthesis include a Lewis base catalyzed Denmark-crotylation for stereoselective construction of the highly hindered quaternary stereocenter, an innovative iodine/selectfluor induced endo-carbocylization, and a unique chemoselective carbonylative lactonization of the eight-membered ring. PMID:26020357

  20. Efficient synthesis strategies by application of transition metal-catalyzed carbene/nitrene insertions into C-H bonds.

    PubMed

    Egger, Julian; Carreira, Erick M

    2014-04-01

    Transition metal-catalyzed insertion of carbenes and nitrenes into C-H bonds has become a powerful tool for the construction of C-C and C-N bonds in the synthesis of complex natural products. In this Highlight, a selection of syntheses are detailed involving the implementation of C-H insertion reactions leading to strategies marked by improved efficiency. PMID:24589531

  1. An approach to pancratistatins via ring-closing metathesis: efficient synthesis of novel 1-aryl-1-deoxyconduritols F. cv.

    PubMed

    Nadein, Oleg N; Kornienko, Alexander

    2004-03-01

    Structurally novel cyclitols, 1-aryl-1-deoxyconduritols F, were efficiently prepared from d-xylose, utilizing RCM as a key step. Various aromatic residues were incorporated in the cyclitol skeleton with total stereochemical control, utilizing a diastereoselective aryl cuprate addition to a gamma-alkoxy enoate. The synthetic route establishes a firm foundation for a practical synthesis of the antitumor alkaloid pancratistatin and its aryl analogues. [structure: see text] PMID:14986986

  2. One-Step Synthesis of 2-Chloropyrimidin-4-ol Derivatives: An Unusual Reactivity of Thiophosgene.

    PubMed

    Callingham, Michael; Blum, Francesca; Pavé, Grégoire

    2015-10-01

    A novel, high-yielding, one-step synthesis of 2-chloroquinazolin-4-ols and analogous bicycles from 2-aminoamides using thiophosgene is described. The scope of the reaction includes aminothioamides, amino acids, and fused heterocycle derivatives, furnishing quinazolines, oxazinones, and substituted fused pyrimidine bicycles, respectively. On the basis of observed results with substituted analogues, a mechanism for this transformation is thought to occur via an isothiocyanate intermediate followed by an unexpected chemoselective reaction of thiophosgene on the thiol intermediate. PMID:26360817

  3. I. Development of Metal-Mediated SPOT-Synthesis Methods for the Efficient Construction of Small-Molecule Macroarrays. II. Design and Synthesis of Novel Bacterial Biofilm Inhibitors

    NASA Astrophysics Data System (ADS)

    Frei, Reto

    I. The use of small molecule probes to explore biological phenomena has become a valuable tool in chemical biology. As a result, methods that permit the rapid synthesis and biological evaluation of such compounds are highly sought-after. The small molecule macroarray represents one such approach for the synthesis and identification of novel bioactive agents. Macroarrays are readily constructed via the SPOT-synthesis technique on planar cellulose membranes, yielding spatially addressed libraries of ˜10-1000 unique compounds. We sought to expand the arsenal of chemical reactions compatible with this solid-phase platform, and developed highly efficient SPOT-synthesis protocols for the Mizoroki-Heck, Suzuki-Miyaura, and copper-catalyzed azide-alkyne cycloaddition reaction. We demonstrated that these metal-mediated reactions can be implemented, either individually or sequentially, for the efficient construction of small molecules in high purity on rapid time scales. Utilizing these powerful C-C and C-N bond forming coupling reactions, we constructed a series of macroarrays based on novel stilbene, phenyl-naphthalene, and triazole scaliblds. Subsequent biological testing of the stilbene and phenyl-naphthalene libraries revealed several potent antagonists and agonists, respectively, of the quorum sensing (QS) receptor LuxR in Vibrio fischeri. II. Bacteria living within biofilms are notorious for their resistance to known antibiotic agents, and constitute a major human health threat. Methods to attenuate biofilm growth would have a significant impact on the management of bacterial infections. Despite intense research efforts, small molecules capable of either inhibiting or dispersing biolilms remain scarce. We utilized natural products with purported anti-biofilm or QS inhibitory activity as sources of structural insight to guide the synthesis of novel biofilm modulators with improved activities. These studies revealed 2-aminobenzimidazole derivatives as highly potent biofilm inhibitors and dispersers in the opportunistic pathogen Pseudomonas aeruginosa. Studies of second-generation 2-aminobenzimidazoles revealed important structure-activity relationships that guided the design of yet more potent analogs. These compounds are amongst the most potent inhibitors of biofilm formation in wild-type P. aeruginosa to be reported. Mechanistic studies of the most active compounds suggest that QS inhibition is one pathway by which 2-aminobenzimidazoles modulate biofilm growth.

  4. Metal-free, efficient oxyfluorination of olefins for the synthesis of ?-fluoroketones.

    PubMed

    Yang, Qiang; Mao, Liu-Liang; Yang, Bin; Yang, Shang-Dong

    2014-07-01

    A novel oxyfluorination of olefin reactions has been developed. The reactions involve a metal-free and green catalytic system for the synthesis of ?-fluoroketones which is an important building block for organic synthesis. Moreover, this reaction system exhibits great functional group tolerance. PMID:24901370

  5. A green and efficient protocol for the synthesis of quinoxaline, benzoxazole and benzimidazole derivatives using heteropolyanion-based ionic liquids: as a recyclable solid catalyst.

    PubMed

    Vahdat, Seyed Mohammad; Baghery, Saeed

    2013-09-01

    In this paper, we introduce two nonconventional ionic liquid compounds which are composed of propane sulfonate functionalized organic cations and heteropolyanions as green solid acid catalysts for the highly efficient and green synthesis of 2,3-disubstitutedquinoxaline derivatives. These ionic liquids are in the solid state at room temperature and the synthesis is carried out via the one-pot condensation reaction of various o-phenylenediamine with 1,2-diketone derivatives. Benzoxazole and benzimidazole derivatives were also synthesized by these novel catalysts via the one-pot condensation from reaction orthoester with o-aminophenol (synthesis of benzoxazole derivatives) and ophenylenediamine (synthesis of benzimidazole derivatives). All experiments successfully resulted in the desired products. The described novel synthesis method has several advantages of safety, mild condition, high yields, short reaction times, simplicity and easy workup compared to the traditional method of synthesis. PMID:23547570

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

    In most studies describing the preparation of Cu2O crystals of various morphologies, the particle sizes are normally hundreds of nanometers to micrometers due to rapid particle growth, so they are not exactly nanocrystals. Here we report surfactant-free formation of sub-100 nm Cu2O nanocrystals with systematic shape evolution from cubic to octahedral structures by preparing an aqueous mixture of Cu(OAc)2, NaOH, and N2H4 solution. Adjustment of the hydrazine volume enables the particle shape control. Uniform nanocubes and octahedra were synthesized with edge lengths of 37 and 67 nm, respectively. Novel Cu2O octapods with an edge length of 135 nm were also produced by mixing CuCl2 solution, SDS surfactant, NaOH solution, and NH2OH.HCl reductant solution. All of them are nearly the smallest Cu2O nanocrystals of the same shapes ever reported. These small cubes, octahedra, and octapods were employed as catalysts in the direct synthesis of 1,2,3-triazoles from the reaction of alkynes, organic halides, and NaN3 at 55 °C. All of them displayed high product yields in short reaction times. The octahedra enclosed by the {111} facets are the best catalysts, and can catalyze this cycloaddition reaction with high yields in just 2 h when different alkynes were used to make diverse triazole products. Hence, the small Cu2O particles provide time-saving, energy-efficient, and high product yield benefits to organocatalysis.In most studies describing the preparation of Cu2O crystals of various morphologies, the particle sizes are normally hundreds of nanometers to micrometers due to rapid particle growth, so they are not exactly nanocrystals. Here we report surfactant-free formation of sub-100 nm Cu2O nanocrystals with systematic shape evolution from cubic to octahedral structures by preparing an aqueous mixture of Cu(OAc)2, NaOH, and N2H4 solution. Adjustment of the hydrazine volume enables the particle shape control. Uniform nanocubes and octahedra were synthesized with edge lengths of 37 and 67 nm, respectively. Novel Cu2O octapods with an edge length of 135 nm were also produced by mixing CuCl2 solution, SDS surfactant, NaOH solution, and NH2OH.HCl reductant solution. All of them are nearly the smallest Cu2O nanocrystals of the same shapes ever reported. These small cubes, octahedra, and octapods were employed as catalysts in the direct synthesis of 1,2,3-triazoles from the reaction of alkynes, organic halides, and NaN3 at 55 °C. All of them displayed high product yields in short reaction times. The octahedra enclosed by the {111} facets are the best catalysts, and can catalyze this cycloaddition reaction with high yields in just 2 h when different alkynes were used to make diverse triazole products. Hence, the small Cu2O particles provide time-saving, energy-efficient, and high product yield benefits to organocatalysis. Electronic supplementary information (ESI) available: SEM images of Cu2O nanocrystals with shape evolution, XRD patterns, calculations for the determination of volumes needed for the catalysis experiment, spectral characterization of the triazole products synthesized and their NMR spectra. See DOI: 10.1039/c4nr02076f

  7. Green synthesis of copper nanoparticles for the efficient removal (degradation) of dye from aqueous phase.

    PubMed

    Sinha, Tanur; Ahmaruzzaman, M

    2015-12-01

    The present work reports the utilization of a common household waste material (fish scales of Labeo rohita) for the synthesis of copper nanoparticles. The method so developed was found to be green, environment-friendly, and economic. The fish scale extracts were acting as a stabilizing and reducing agents. This method avoids the use of external reducing and stabilizing agents, templates, and solvents. The compositional abundance of gelatin may be envisaged for the effective reductive as well as stabilizing potency. The mechanisms for the formation of nanoparticles have also been presented. The synthesized copper nanoparticles formed were predominantly spherical in nature with an average size of nanoparticles in the range of 25-37 nm. The copper nanoparticles showed characteristic Bragg's reflection planes of fcc which was supported by both selected area electron diffraction and X-ray diffraction pattern and showed surface plasmon resonance at 580 nm. Moreover, the energy dispersive spectroscopy pattern also revealed the presence of only elemental copper in the copper nanoparticles. The prepared nanoparticles were used for the remediation of a carcinogenic and noxious textile dye, Methylene blue, from aqueous solution. Approximately, 96 % degradation of Methylene blue dye was observed within 135 min using copper nanoparticles. The probable mechanism for the degradation of the dye has been presented, and the degraded intermediates have been identified using the liquid chromatography-mass spectroscopy technique. The high efficiency of nanoparticles as photocatalysts has opened a promising application for the removal of hazardous dye from industrial effluents contributing indirectly to environmental cleanup process. PMID:26300362

  8. Size Dependence of Atomically Precise Gold Nanoclusters in Chemoselective Hydrogenation and Active Site Structure

    SciTech Connect

    Li, Gao; Jiang, Deen; Kumar, Santosh; Chen, Yuxiang; Jin, Rongchao

    2014-01-01

    We here investigate the catalytic properties of water-soluble Aun(SG)m nanocluster catalysts (H-SG = glutathione) of different sizes, including Au15(SG)13, Au18(SG)14, Au25(SG)18, Au38(SG)24, and captopril-capped Au25(Capt)18 nanoclusters. These Aun(SR)m nanoclusters (-SR represents thiolate generally) are used as homogeneous catalysts (i.e., without supports) in the chemoselective hydrogenation of 4-nitrobenzaldehyde (4-NO2PhCHO) to 4-nitrobenzyl alcohol (4-NO2PhCH2OH) in water with H2 gas (20 bar) as the hydrogen source. These nanocluster catalysts, except Au18(SG)14, remain intact after the catalytic reaction, evidenced by UV-vis spectra which are characteristic of each sized nanoclusters and thus serve as spectroscopic fingerprints . We observe a drastic size-dependence and steric effect of protecting ligands on the gold nanocluster catalysts in the hydrogenation reaction. Density functional theory (DFT) modeling of the 4-nitrobenzaldehyde adsorption shows that both the CHO and NO2 groups are in close interact with the S-Au-S staples on the gold nanocluster surface; the adsorption of the 4-nitrobenzaldehyde molecule on the four different sized Aun(SR)m nanoclusters are moderately strong and similar in strength. The DFT results suggest that the catalytic activity of the Aun(SR)m nanoclusters is primarily determined by the surface area of the Au nanocluster, consistent with the observed trend of the conversion of 4-nitrobenzaldehyde versus the cluster size. Overall, this work offers the molecular insight into the hydrogenation of 4-nitrobenzaldehyde and the catalytically active site structure on gold nanocluster catalysts.

  9. Air- and moisture-stable amphoteric molecules: enabling reagents in synthesis.

    PubMed

    He, Zhi; Zajdlik, Adam; Yudin, Andrei K

    2014-04-15

    Researchers continue to develop chemoselective synthesis strategies with the goal of rapidly assembling complex molecules. As one appealing approach, chemists are searching for new building blocks that include multiple functional groups with orthogonal chemical reactivity. Amphoteric molecules that possess nucleophilic and electrophilic sites offer a versatile platform for the development of chemoselective transformations. As part of a program focused on new methods of synthesis, we have been developing this type of reagents. This Account highlights examples of amphoteric molecules developed by our lab since 2006. We have prepared and evaluated aziridine aldehydes, a class of stable unprotected ?-amino aldehydes. Structurally, aziridine aldehydes include both a nucleophilic amine nitrogen and an electrophilic aldehyde carbon over the span of three atoms. Under ambient conditions, these compounds exist as homochiral dimers with an aziridine-fused five-membered cyclic hemiaminal structure. We have investigated chemoselective reactions of aziridine aldehydes that involve both the aziridine and aldehyde functionalities. These transformations have produced a variety of densely functionalized nitrogen-containing compounds, including amino aldehydes, 1,2-diamines, reduced hydantoins, C-vinyl or alkynyl aziridines, and macrocyclic peptides. We have also developed air- and moisture-stable ?-boryl aldehydes, another class of molecules that are kinetically amphoteric. The ?-boryl aldehydes contain a tetracoordinated N-methyliminodiacetyl (MIDA) boryl substituent, which stabilizes the ?-metalloid carbonyl system and prevents isomerization to its O-bond enolate form. Primarily taking advantage of chemoselective transformations at the aldehyde functionality, these ?-boryl aldehydes have allowed us to synthesize a series of new functionalized boron-containing compounds that are difficult or impossible to prepare using established protocols, such as ?-borylcarboxylic acids, boryl alcohols, enol ethers, and enamides. Using ?-borylcarboxylic acids as starting materials, we have also prepared several new amphoteric borylated reagents, such as ?-boryl isocyanates, isocyanides, and acylboronates. These compounds are versatile building blocks in their own right, enabling the rapid synthesis of other boron-containing molecules. PMID:24495255

  10. Synthesis and Characterization of Iron-Nitrogen-Doped Graphene/Core-Shell Catalysts: Efficient Oxidative Dehydrogenation of N-Heterocycles.

    PubMed

    Cui, Xinjiang; Li, Yuehui; Bachmann, Stephan; Scalone, Michelangelo; Surkus, Annette-Enrica; Junge, Kathrin; Topf, Christoph; Beller, Matthias

    2015-08-26

    An important goal for nanocatalysis is the development of flexible and efficient methods for preparing active and stable core-shell catalysts. In this respect, we present the synthesis and characterization of iron oxides surrounded by nitrogen-doped-graphene shells immobilized on carbon support (labeled FeOx@NGr-C). Active catalytic materials are obtained in a simple, scalable and two-step method via pyrolysis of iron acetate and phenanthroline and subsequent selective leaching. The optimized FeOx@NGr-C catalyst showed high activity in oxidative dehydrogenations of several N-heterocycles. The utility of this benign methodology is demonstrated by the synthesis of pharmaceutically relevant quinolines. In addition, mechanistic studies prove that the reaction progresses via superoxide radical anions (·O2(-)). PMID:26230874

  11. Protease-catalyzed peptide synthesis using inverse substrates: the influence of reaction conditions on the trypsin acyl transfer efficiency.

    PubMed

    Schellenberger, V; Jakubke, H D; Zapevalova, N P; Mitin, Y V

    1991-06-01

    Benzyloxycarbonyl-L-alanine p-guanidinophenyl ester behaves as a trypsin "inverse substrate," i.e., a cationic center is included in the leaving group instead of being in the acyl moiety. Using this substrate as an acyl donor, trypsin catalyzes the synthesis of peptide bonds that cannot be split by this enzyme. An optimal acyl transfer efficiency was achieved between pH 8 and 9 at 30 degrees C.The addition of as much as 50% cosolvent was shown to be of minor influence on the acyl transfer efficiency, whereas the reaction velocity decreases by more than one order of magnitude. The efficiency of H-Leu-NH(2) and H-Val-NH(2) in deacylation is almost the same for "inverse" and normal type substrates. PMID:18600704

  12. Structural control of chemoselectivity, stereoselectivity, and substrate specificity in membrane-bound fatty acid acetylenases and desaturases.

    PubMed

    Gagné, Steve J; Reed, Darwin W; Gray, Gordon R; Covello, Patrick S

    2009-12-29

    The FAD2-like desaturases comprise a group of membrane-bound oxygenases involved in the modification of fatty acyl groups in plants and fungi. This group includes typical oleate desaturases which introduce a Delta12 cis double bond and more unusual enzymes such as Crep1, an acetylenase from the plant Crepis alpina, which introduces a triple bond in linoleate at the Delta12 position. In this study, the structure-function relationship between FAD2-like acetylenases and desaturases was examined through site-directed mutagenesis and heterologous expression. Eleven amino acid positions were identified that show complete evolutionary conservation within acetylenases or desaturases but have different amino acids in the other class of enzyme. Point mutants in Crep1 were constructed and expressed in yeast to test the role in fatty acid modification of the amino acids at the 11 positions. Results indicate the importance of five amino acid positions within Crep1 with regard to desaturase and acetylenase chemoselectivity, stereoselectivity, and substrate recognition. For example, relative to wild-type Crep1, the Y150F, F259L, and H266Q mutations all favored desaturation over acetylenation. The data indicate that small changes in primary sequence, particularly in the vicinity of the active site, can have profound changes on chemoselectivity and other aspects of the function of membrane-bound desaturase-like enzymes. PMID:19950909

  13. Metal-free synthesis of ortho-CHO diaryl ethers by a three-component sequential coupling.

    PubMed

    Liu, Fangliang; Yang, Huameng; Hu, Xinquan; Jiang, Gaoxi

    2014-12-19

    A practical, metal-free, and highly chemoselective approach was developed for the synthesis of ortho-CHO diaryl ethers by a three-component sequential coupling of arynes, N,N-dimethylformamide (DMF), and diaryliodonium salts. Diverse functional groups including halo, nitryl, and bulky substituents and heteroaromatics are well tolerated. Mechanistically, isotopic tracer experiments reveal that the diaryliodonium salt serves as an electrophile to trap the transient intermediates generated from the [2 + 2] cyclization of an aryne and DMF. PMID:25473728

  14. One-Pot Synthesis of 5-Amino-2,5-dihydro-1-benzoxepines: Access to Pharmacologically Active Heterocyclic Scaffolds.

    PubMed

    Calder, Ewen D D; Sharif, Salaheddin A I; McGonagle, Fiona I; Sutherland, Andrew

    2015-05-01

    A one-pot multibond-forming process involving a thermally mediated Overman rearrangement and a ring closing metathesis reaction of allylic trichloroacetimidates bearing a 2-allyloxyaryl group has been developed for the synthesis of 5-amino-substituted 2,5-dihydro-1-benzoxepines. Chemoselective reduction and functionalization of these compounds allowed access to a range of pharmacologically active 5-amino-2,3,4,5-tetrahydro-1-benzoxepine scaffolds. PMID:25847814

  15. VERVE: A Framework for Variation-Aware Energy Efficient Synthesis of NoC-based MPSoCs with Voltage islands

    E-print Network

    Pasricha, Sudeep

    per watt (energy-efficiency) is a key metric to be optimized. The total energy consumption requiredVERVE: A Framework for Variation-Aware Energy Efficient Synthesis of NoC-based MPSoCs with Voltage islands Nishit Kapadia, Sudeep Pasricha Department of Electrical and Computer Engineering Colorado State

  16. Collagen synthesis promoting pullulan-PEI-ascorbic acid conjugate as an efficient anti-cancer gene delivery vector.

    PubMed

    Ambattu, Lizebona August; Rekha, M R

    2015-08-01

    Cationized pullulan (pullulan-PEI; PP) was synthesized and further modified with an anti-oxidant molecule, ascorbic acid (PPAA) at various ratios. The nanoplexes formed at an optimum ratio of 4:1 was within a size of 150nm and had a zeta potential of 9-14mV. The nanoplexes at this ratio was used for further investigations. The cell internalization and transfection efficiency of these nanoplexes were determined in presence of serum. The internalization and transfection efficiency were found to be unaffected by the presence of fetal bovine serum. Another interesting observation was that this polymer was found to have collagen synthesis promoting property. The collagen synthesis effect of these polymers was quantified and observed that PPAA3 promoted the highest. Transfection efficiency was evaluated by assessing the p53 gene expression in C6 rat glioma cells and cell death was quantified to be 96% by flow cytometry, thus establishing the high efficacy of this polymer. PMID:25933522

  17. Efficient Microwave-assisted One-pot Three-component Synthesis of 2,3-Disubstituted Benzofurans under Sonogashira Conditions

    PubMed Central

    Markina, Nataliya A.; Chen, Yu; Larock, Richard C.

    2013-01-01

    An efficient one-pot method for the synthesis of 2,3-disubstituted benzo[b]furans from commercially available 2-iodophenols, terminal acetylenes and aryl iodides has been developed utilizing Sonogashira reaction conditions. After an initial Sonogashira coupling of the 2-iodophenol with the terminal alkyne, cyclization involving the aryl iodide provides the 2,3-disubstituted benzo[b]furan in good to excellent yields. The use of microwave irradiation shortens the reaction times and minimizes the side products. This methodology is especially useful for the construction of libraries of highly substituted benzo[b]furans and their analogues. PMID:23504237

  18. Synthesis and SAR of novel imidazoles as potent and selective cannabinoid CB2 receptor antagonists with high binding efficiencies.

    PubMed

    Lange, Jos H M; van der Neut, Martina A W; Wals, Henri C; Kuil, Gijs D; Borst, Alice J M; Mulder, Arie; den Hartog, Arnold P; Zilaout, Hicham; Goutier, Wouter; van Stuivenberg, Herman H; van Vliet, Bernard J

    2010-02-01

    The synthesis and structure-activity relationship studies of imidazoles are described. The target compounds 6-20 represent a novel chemotype of potent and CB(2)/CB(1) selective cannabinoid CB(2) receptor antagonists/inverse agonists with very high binding efficiencies in combination with favourable logP and calculated polar surface area values. Compound 12 exhibited the highest CB(2) receptor affinity (K(i)=1.03 nM) in this series, as well as the highest CB(2)/CB(1) subtype selectivity (>9708-fold). PMID:20031412

  19. Efficient Automated Solid-Phase Synthesis of DNA and RNA 5'-Triphosphates.

    PubMed

    Sarac, Ivo; Meier, Chris

    2015-11-01

    A fast, high-yielding and reliable method for the synthesis of DNA- and RNA 5'-triphosphates is reported. After synthesizing DNA or RNA oligonucleotides by automated oligonucleotide synthesis, 5-chloro-saligenyl-N,N-diisopropylphosphoramidite was coupled to the 5'-end. Oxidation of the formed 5'-phosphite using the same oxidizing reagent used in standard oligonucleotide synthesis led to 5'-cycloSal-oligonucleotides. Reaction of the support-bonded 5'-cycloSal-oligonucleotide with pyrophosphate yielded the corresponding 5'-triphosphates. The 5'-triphosphorylated DNA and RNA oligonucleotides were obtained after cleavage from the support in high purity and excellent yields. The whole reaction sequence was adapted to be used on a standard oligonucleotide synthesizer. PMID:26517040

  20. Synthesis of a new class of Betti bases by the Mannich-type reaction: efficient, facile, solvent-free and one-pot protocol.

    PubMed

    Shahrisa, Aziz; Teimuri-Mofrad, Reza; Gholamhosseini-Nazari, Mahdi

    2015-02-01

    A variety of organocatalysts has been screened for the synthesis of arylaminonaphthols. It has been shown that (N,N-dimethylethanolamine) is a highly efficient organocatalyst for the direct synthesis of a novel class of arylaminonaphthols via three-component condensation of 2-naphthol, aldehydes, and arylamines under solvent-free conditions. Mild, one-pot, and green reaction conditions, relatively short reaction times and good yields make this protocol highly significant. 25 new compounds have been synthesized by this method. PMID:25528441

  1. An organocatalytic highly efficient approach to the direct synthesis of substituted carbazoles in water.

    PubMed

    Jaiswal, Pradeep Kumar; Biswas, Soumen; Singh, Shivendra; Samanta, Sampak

    2013-12-28

    A simple, mild, green, catalytic and general procedure for the direct synthesis of highly functionalized 1-methoxycarbonyl-2-aryl/alkyl-3-nitro-9H-carbazoles has been achieved in water medium via a one-pot domino Michael-Henry/aromatization reaction of methyl 2-(3-formyl-1H-indol-2-yl)acetates with aryl/alky-substituted ?-nitroolefins under air using DABCO (30 mol%) as an organocatalyst. In addition, the bench scale synthesis can be performed without using toxic organic solvents and a biologically important new fused carbazole has been prepared. PMID:24189837

  2. The methyltransferase domain of dengue virus protein NS5 ensures efficient RNA synthesis initiation and elongation by the polymerase domain

    PubMed Central

    Potisopon, Supanee; Priet, Stéphane; Collet, Axelle; Decroly, Etienne; Canard, Bruno; Selisko, Barbara

    2014-01-01

    Viral RNA-dependent RNA polymerases (RdRps) responsible for the replication of single-strand RNA virus genomes exert their function in the context of complex replication machineries. Within these replication complexes the polymerase activity is often highly regulated by RNA elements, proteins or other domains of multi-domain polymerases. Here, we present data of the influence of the methyltransferase domain (NS5-MTase) of dengue virus (DENV) protein NS5 on the RdRp activity of the polymerase domain (NS5-Pol). The steady-state polymerase activities of DENV-2 recombinant NS5 and NS5-Pol are compared using different biochemical assays allowing the dissection of the de novo initiation, transition and elongation steps of RNA synthesis. We show that NS5-MTase ensures efficient RdRp activity by stimulating the de novo initiation and the elongation phase. This stimulation is related to a higher affinity of NS5 toward the single-strand RNA template indicating NS5-MTase either completes a high-affinity RNA binding site and/or promotes the correct formation of the template tunnel. Furthermore, the NS5-MTase increases the affinity of the priming nucleotide ATP upon de novo initiation and causes a higher catalytic efficiency of the polymerase upon elongation. The complex stimulation pattern is discussed under the perspective that NS5 adopts several conformations during RNA synthesis. PMID:25209234

  3. Efficient Texture Synthesis Using Strict Wang Tiles Xinyu Zhang and Young J. Kim

    E-print Network

    images with similar visual characteristics. It is used in video games, flight simulators and scientific in the graphics processors (GPUs). There are a number of algorithms for example-based texture synthesis. In general, they can be divided into three categories: pixel-based methods, patch-based methods and tiling

  4. An efficient and green synthesis of novel benzoxazole under ultrasound irradiation.

    PubMed

    Nikpassand, Mohammad; Fekri, Leila Zare; Farokhian, Pegah

    2016-01-01

    Ultrasound as green process and an alternative energy source was investigated for the environmentally benign synthesis of novel benzoxazoles from different azo-linked salicylic acid derivatives and 2-amino-4-chlorophenol in short reaction time and high yield. These benzoxazole compounds have been characterized by elemental analysis, FT-IR, (1)H NMR and (13)C NMR spectroscopy. PMID:26384917

  5. Efficient room temperature aqueous Sb2S3 synthesis for inorganic-organic sensitized solar cells with 5.1% efficiencies.

    PubMed

    Gödel, Karl C; Choi, Yong Chan; Roose, Bart; Sadhanala, Aditya; Snaith, Henry J; Seok, Sang Il; Steiner, Ullrich; Pathak, Sandeep K

    2015-05-21

    Sb2S3 sensitized solar cells are a promising alternative to devices employing organic dyes. The manufacture of Sb2S3 absorber layers is however slow and cumbersome. Here, we report the modified aqueous chemical bath synthesis of Sb2S3 absorber layers for sensitized solar cells. Our method is based on the hydrolysis of SbCl3 to complex antimony ions decelerating the reaction at ambient conditions, in contrast to the usual low temperature deposition protocol. This simplified deposition route allows the manufacture of sensitized mesoporous-TiO2 solar cells with power conversion efficiencies up to ? = 5.1%. Photothermal deflection spectroscopy shows that the sub-bandgap trap-state density is lower in Sb2S3 films deposited with this method, compared to standard deposition protocols. PMID:25900075

  6. Enantio- and chemoselective differentiation of protected ?-amino acids and ?-homoamino acids with a single copper(II) host.

    PubMed

    Joyce, Leo A; Canary, James W; Anslyn, Eric V

    2012-06-25

    The association between an achiral copper(II)-containing host 1 and chiral carboxylates has been expanded beyond previous studies to new chiral carboxylate guests, both ?-amino acids and ?-homoamino acids. The observed exciton-coupled circular dichroism (ECCD) signals for the enantiomers of each carboxylate were equal and opposite, and these signals differed in size and shape between the individual amino acids. Linear discriminant analysis (LDA) was applied as a statistical analysis technique to differentiate the amino acids, both enantioselectively and chemoselectively, giving the absolute configuration and identity of the amino acid. The identity of each of the ?-amino acids and ?-homoamino acids were determined independently by LDA, and then the two were considered together. Each of these analyses showed good differentiation of the amino acid guests with the use of only one host molecule. PMID:22592912

  7. Guiding efficient microbial synthesis of non-natural chemicals by physicochemical properties of reactants.

    PubMed

    Willrodt, Christian; Karande, Rohan; Schmid, Andreas; Julsing, Mattijs K

    2015-12-01

    The recent progress in sustainable chemistry and in synthetic biology increased the interest of chemical and pharmaceutical industries to implement microbial processes for chemical synthesis. However, most organisms used in biotechnological applications are not evolved by Nature for the production of hydrophobic, non-charged, volatile, or toxic compounds. In order to overcome this discrepancy, bioprocess design should consist of an integrated approach addressing pathway, cellular, reaction, and process engineering. Highlighting selected examples, we show that surprisingly often Nature provides conceptual solutions to enable chemical synthesis. Complemented by established methods from (bio)chemical and metabolic engineering, these concepts offer potential strategies yet to be explored and translated into innovative technical solutions enabling sustainable microbial production of non-natural chemicals. PMID:25835779

  8. An efficient synthesis of N-substituted 3-nitrothiophen-2-amines

    PubMed Central

    Vivek Kumar, Sundaravel; Muthusubramanian, Shanmugam

    2015-01-01

    Summary A novel protocol for the synthesis of 3-nitro-N-aryl/alkylthiophen-2-amines in good yields from the reaction of ?-nitroketene N,S-aryl/alkylaminoacetals and 1,4-dithiane-2,5-diol in the presence of K2CO3 in refluxing ethanol is described. This transformation generates two C–C bonds in a single operation and presumably proceeds through a reaction sequence comprising 2-mercaptoacetaldehyde generation, nucleophilic carbonyl addition, annelation and elimination steps. PMID:26664589

  9. Efficient synthesis of phenylene-ethynylene rods and their use as rigid spacers in divalent inhibitors

    PubMed Central

    Pertici, Francesca; Varga, Norbert; van Duijn, Arnoud; Rey-Carrizo, Matias; Bernardi, Anna

    2013-01-01

    Summary The synthesis of phenylene-ethynylene rods and their use as rigid spacers is described. Alternation of a Sonogashira reaction and silyl group cleavage was used to obtain rigid spacers with even and odd numbers of phenylene units. Preliminary applications of these rods in divalent systems are shown. Inhibition studies with Pseudomonas Aeruginosa lectin LecA showed that the rigid spacer proved greatly beneficial for the inhibitory potency. PMID:23400701

  10. Silica: An efficient catalyst for one-pot regioselective synthesis of dithioethers

    PubMed Central

    Kundu, Samir; Roy, Babli

    2014-01-01

    Summary The development of a silica-promoted highly selective synthesis of 1,2 or 1,3-dithioethers via solvent-free one-pot tandem reactions of an allyl bromide with excess thiol at room temperature is described. The choice of silica gel, either pre-calcined or moistened with water, exhibited notable regioselectivity in the formation of dithioethers. Plausible mechanistic routes were explored and postulated. PMID:24454561

  11. Templated synthesis of nickel nanoparticles: Toward heterostructured nanocomposites for efficient hydrogen storage

    SciTech Connect

    Nelson, Nicholas Cole

    2013-05-07

    The world is currently facing an energy and environmental crisis for which new technologies are needed. Development of cost-competitive materials for catalysis and hydrogen storage on-board motor vehicles is crucial to lead subsequent generations into a more sustainable and energy independent future. This thesis presents work toward the scalable synthesis of bimetallic heterostructures that can enable hydrogen to compete with carbonaceous fuels by meeting the necessary gravimetric and volumetric energy densities and by enhancing hydrogen sorption/desorption kinetics near ambient temperatures and pressures. Utilizing the well-known phenomenon of hydrogen spillover, these bimetallic heterostructures could work by lowering the activation energy for hydrogenation and dehydrogenation of metals. Herein, we report a novel method for the scalable synthesis of silica templated zero-valent nickel particles (Ni?SiO{sub 2}) that hold promise for the synthesis of nickel nanorods for use in bimetallic heterostructures for hydrogen storage. Our synthesis proceeds by chemical reduction of a nickel-hydrazine complex with sodium borohydride followed by calcination under hydrogen gas to yield silica encapsulated nickel particles. Transmission electron microscopy and powder X-ray diffraction were used to characterize the general morphology of the resultant nanocapsules as well as the crystalline phases of the incorporated Ni{sup 0} nanocrystals. The structures display strong magnetic behavior at room temperature and preliminary data suggests nickel particle size can be controlled by varying the amount of nickel precursor used in the synthesis. Calcination under different environments and TEM analysis provides evidence for an atomic migration mechanism of particle formation. Ni?SiO{sub 2} nanocapsules were used as seeds to induce heterogeneous nucleation and subsequent growth within the nanocapsule via electroless nickel plating. Nickel nanoparticle growth occurs under high temperature alkaline conditions, however silica nanocapsule integrity is not maintained due to the incompatibility of silica with the growth conditions. Silica nanocapsule integrity is maintained under low temperature neutral conditions, but nickel particle growth is not observed. Through FTIR and UV/Vis analysis, we show the degree of crosslinking and condensation increases in calcined silica compared to as-synthesized silica. We propose the increased density of the silica nanocapsule hinders mass transfer of the bulky nickel precursor complex from solution and onto the surface of the “catalytic” zero-valent nickel seed within the nanocapsule cavity. Decreasing the density of the silica nanocapsule can be achieved through co-condensation of tetraethylorthosilicate with an alkyl functionalized silane followed by calcination to remove the organic component or by chemical etching in alkaline solution, but will not be addressed in this thesis.

  12. Templated synthesis of nickel nanoparticles: Toward heterostructured nanocomposites for efficient hydrogen storage

    NASA Astrophysics Data System (ADS)

    Nelson, Nicholas Cole

    The world is currently facing an energy and environmental crisis for which new technologies are needed. Development of cost-competitive materials for catalysis and hydrogen storage on-board motor vehicles is crucial to lead subsequent generations into a more sustainable and energy independent future. This thesis presents work toward the scalable synthesis of bimetallic heterostructures that can enable hydrogen to compete with carbonaceous fuels by meeting the necessary gravimetric and volumetric energy densities and by enhancing hydrogen sorption/desorption kinetics near ambient temperatures and pressures. Utilizing the well-known phenomenon of hydrogen spillover, these bimetallic heterostructures could work by lowering the activation energy for hydrogenation and dehydrogenation of metals. Herein, we report a novel method for the scalable synthesis of silica templated zero-valent nickel particles (Ni?SiO2) that hold promise for the synthesis of nickel nanorods for use in bimetallic heterostructures for hydrogen storage. Our synthesis proceeds by chemical reduction of a nickel-hydrazine complex with sodium borohydride followed by calcination under hydrogen gas to yield silica encapsulated nickel particles. Transmission electron microscopy and powder X-ray diffraction were used to characterize the general morphology of the resultant nanocapsules as well as the crystalline phases of the incorporated Ni0 nanocrystals. The structures display strong magnetic behavior at room temperature and preliminary data suggests nickel particle size can be controlled by varying the amount of nickel precursor used in the synthesis. Calcination under different environments and TEM analysis provides evidence for an atomic migration mechanism of particle formation. Ni?SiO2 nanocapsules were used as seeds to induce heterogeneous nucleation and subsequent growth within the nanocapsule via electroless nickel plating. Nickel nanoparticle growth occurs under high temperature alkaline conditions, however silica nanocapsule integrity is not maintained due to the incompatibility of silica with the growth conditions. Silica nanocapsule integrity is maintained under low temperature neutral conditions, but nickel particle growth is not observed. Through FTIR and UV/Vis analysis, we show the degree of crosslinking and condensation increases in calcined silica compared to as-synthesized silica. We propose the increased density of the silica nanocapsule hinders mass transfer of the bulky nickel precursor complex from solution and onto the surface of the "catalytic" zero-valent nickel seed within the nanocapsule cavity. Decreasing the density of the silica nanocapsule can be achieved through co-condensation of tetraethylorthosilicate with an alkyl functionalized silane followed by calcination to remove the organic component or by chemical etching in alkaline solution, but will not be addressed in this thesis.

  13. Palladium-catalyzed direct coupling of 2-vinylanilines and isocyanides: an efficient synthesis of 2-aminoquinolines.

    PubMed

    Wang, Lijie; Ferguson, Jamie; Zeng, Fanlong

    2015-12-21

    Palladium-catalyzed oxidative coupling of 2-vinylanilines and isocyanides constitutes a direct, facile, and efficient approach to 2-aminoquinolines. The procedure, employing palladium acetate and silver carbonate, is attractive in terms of assembly efficiency, functional group tolerance, and operational simplicity. A variety of 2-aminoquinolines were prepared in good to excellent yields. PMID:26455948

  14. Efficient synthesis of dithienogermole (DTG) derivatives via olefin cross-metathesis.

    PubMed

    Zong, Kyukwan; Deininger, James J; Reynolds, John R

    2013-03-01

    4,4'-Bis-(4-pentenyl)-dithieno[3,2-b:2',3'-d]germole was synthesized as a functional building block for the efficient preparation of dithienogermole (DTG) derivatives with varying alkyl chain lengths and pendant functionalities in excellent yields. These derivatives were efficiently isolated via olefin cross-metathesis followed by hydrogenation. PMID:23421956

  15. Efficient synthesis of ammonia from N2 and H2 alone in a ferroelectric packed-bed DBD reactor

    NASA Astrophysics Data System (ADS)

    Gómez-Ramírez, A.; Cotrino, J.; Lambert, R. M.; González-Elipe, A. R.

    2015-12-01

    A detailed study of ammonia synthesis from hydrogen and nitrogen in a planar dielectric barrier discharge (DBD) reactor was carried out. Electrical parameters were systematically varied, including applied voltage and frequency, electrode gap, and type of ferroelectric material (BaTiO3 versus PZT). For selected operating conditions, power consumption and plasma electron density were estimated from Lissajous diagrams and by application of the Bolsig??+??model, respectively. Optical emission spectroscopy was used to follow the evolution of plasma species (\\text{N}{{\\text{H}}*},{{\\text{N}}*},~{N}2+~\\text{and} ~{N}2* ) as a function of applied voltage with both types of ferroelectric material. PZT gave both greater energy efficiency and higher ammonia yield than BaTiO3: 0.9?g NH3 kWh?1 and 2.7% single pass N2 conversion, respectively. This performance is substantially superior to previously published findings on DBD synthesis of NH3 from N2 and H2 alone. The influence of electrical working parameters, the beneficial effect of PZT and the importance of controlling reactant residence time are rationalized in a reaction model that takes account of the principal process variables

  16. Scalable Synthesis of Efficient Water Oxidation Catalysts: Insights into the Activity of Flame-Made Manganese Oxide Nanocrystals.

    PubMed

    Liu, Guanyu; Hall, Jeremy; Nasiri, Noushin; Gengenbach, Thomas; Spiccia, Leone; Cheah, Mun Hon; Tricoli, Antonio

    2015-12-01

    Chemical energy storage by water splitting is a promising solution for the utilization of renewable energy in numerous currently impracticable needs, such as transportation and high temperature processing. Here, the synthesis of efficient ultra-fine Mn3 O4 water oxidation catalysts with tunable specific surface area is demonstrated by a scalable one-step flame-synthesis process. The water oxidation performance of these flame-made structures is compared with pure Mn2 O3 and Mn5 O8 , obtained by post-calcination of as-prepared Mn3 O4 (115?m(2) ?g(-1) ), and commercial iso-structural polymorphs, probing the effect of the manganese oxidation state and synthetic route. The structural properties of the manganese oxide nanoparticles were investigated by XRD, FTIR, high-resolution TEM, and XPS. It is found that these flame-made nanostructures have substantially higher activity, reaching up to 350?% higher surface-specific turnover frequency (0.07??molO2 ?m(-2) ?s(-1) ) than commercial nanocrystals (0.02??molO2 ?m(-2) ?s(-1) ), and production of up to 0.33?mmolO2 ?molMn (-1) ?s(-1) . Electrochemical characterization confirmed the high water oxidation activity of these catalysts with an initial current density of 10?mA?cm(-2) achieved with overpotentials between 0.35 and 0.50?V in 1?m NaOH electrolyte. PMID:26601653

  17. A highly efficient magnetic solid acid catalyst for synthesis of 2,4,5-trisubstituted imidazoles under ultrasound irradiation.

    PubMed

    Safari, Javad; Zarnegar, Zohre

    2013-03-01

    Fe(3)O(4) nanoparticles were prepared by chemical coprecipitation method and subsequently coated with 3-aminopropyltriethoxysilane (APTES) via silanization reaction. Grafting of chlorosulfuric acid on the amino-functionalized Fe(3)O(4) nanoparticles afforded sulfamic acid-functionalized magnetic nanoparticles (SA-MNPs). SA-MNPs was found to be a mild and effective solid acid catalyst for the efficient, one-pot, three-component synthesis of 2,4,5-trisubstituted imidazoles under ultrasound irradiation. This protocol afforded corresponding imidazoles in shorter reaction durations, and in high yields. This green procedure has many obvious advantages compared to those reported in the previous literatures, including avoiding the use of harmful catalysts, easy and quick isolation of the products, excellent yields, short routine, and simplicity of the methodology. PMID:23137656

  18. Facile and efficient one-pot synthesis of 2-arylbenzoxazoles using hydrogen tetrachloroaurate as catalyst under oxygen atmosphere*

    PubMed Central

    Liu, Yun-kui; Mao, Da-jie; Lou, Shao-jie; Qian, Jian-qiang; Xu, Zhen-yuan

    2009-01-01

    In this paper, we presented a novel method for the facile and efficient one-pot synthesis of 2-arylbenzoxazoles, which were directly synthesized from 2-aminophenol and aldehydes catalyzed by hydrogen tetrachloroaurate (HAuCl4·4H2O) under an oxygen atmosphere with anhydrous tetrahydrofuran (THF) as solvent or in solvent-free condition. The results show that this method could bring excellent yields as high as 96%. THF was proven to be the best choice among several solvents screened and the reaction was tolerated with a variety of aromatic aldehydes possessing electron-donating or withdrawing groups. The advantages of the present method lie in catalytic process using economic and environmentally benign dioxygen as oxidant. PMID:19489113

  19. Surfactant-Directed Synthesis of Mesoporous Pd Films with Perpendicular Mesochannels as Efficient Electrocatalysts.

    PubMed

    Li, Cuiling; Jiang, Bo; Miyamoto, Nobuyoshi; Kim, Jung Ho; Malgras, Victor; Yamauchi, Yusuke

    2015-09-16

    Palladium (Pd) films with perpendicularly aligned mesochannels are expected to provide fascinating electrocatalytic properties due to their low diffusion resistance and the full utilization of their large surface area. There have been no studies on such mesoporous metal films, because of the difficulties in controlling both the vertical alignment of the molecular template and the crystal growth in the metallic pore walls. Here we report an effective approach for the synthesis of mesoporous Pd films with mesochannels perpendicularly aligned to the substrate by an elaborated electrochemical deposition. The films show a superior electrocatalytic activity by taking full advantage of the perpendicularly aligned mesochannels. PMID:26307655

  20. Chemistry of polyhalogenated nitrobutadienes, 14: Efficient synthesis of functionalized (Z)-2-allylidenethiazolidin-4-ones

    PubMed Central

    Zapol’skii, Viktor A; Namyslo, Jan C; Gjikaj, Mimoza

    2014-01-01

    Summary The reaction of mercaptoacetic acid esters with pentachloro-2-nitro-1,3-butadiene (1) provides an appropriate precursor for the synthesis of special thiazolidin-4-ones. Applying different anilines as the second constituent for the requisite cyclization step, a series of (Z)-2-allylidenethiazolidin-4-ones was obtained in yields up to 81%. Some subsequent reactions have been examined too, such as the formation of perfunctionalized 1H-pyrazoles upon treatment with hydrazine. Thiazolidinones are as well known for their physiological activities as for their application in optoelectronics. PMID:25161721

  1. A novel and efficient samarium iodide-mediated synthesis of neoflavonoids (4-arycloumarins)

    SciTech Connect

    Nagasawa, Kazuo; Ryohke, Hirosi; Ohnishi, Makoto; Ito, Keiichi

    1995-12-31

    Bioactive 4-arylcoumarins (4-aryl-2H-1-benzopyran-2-ones) have been recently isolated from the plants belonging to the families like Leguminosae, Guttiferae, and Compositae, some of which are still used as the traditional folk medicine. Despite many methods reported so far, there appears to be of limited success or of no success in some cases (II{sub b-g}) and, therefore, a simpler and more reliable one remains to be highly desired. Thus, a new and sterling protocol is now presented for the synthesis of neoflavonoids, which involves the intramolecular Reformatsky-type reaction via a one electron transfer process with samarium diiodide as a key step.

  2. One pot, rapid and efficient synthesis of water dispersible gold nanoparticles using alpha-amino acids

    NASA Astrophysics Data System (ADS)

    Wangoo, Nishima; Kaur, Sarabjit; Bajaj, Manish; Jain, D. V. S.; Sharma, Rohit K.

    2014-10-01

    A detailed study on the synthesis of spherical and monodispersed gold nanoparticles (AuNPs) using all of the 20 naturally occurring ?-amino acids has been reported. The synthesized nanoparticles have been further characterized using various techniques such as absorbance spectroscopy, transmission electron microscopy, dynamic light scattering and nuclear magnetic resonance. Size control of the nanoparticles has been achieved by varying the ratio of the gold ion to the amino acid. These monodispersed water soluble AuNPs synthesized using non-toxic, naturally occurring ?-amino acids as reducing and capping/stabilizing agents serve as a remarkable example of green chemistry.

  3. Simple, general, and efficient synthesis of meso-substituted borondipyrromethenes from a single platform.

    PubMed

    Peña-Cabrera, Eduardo; Aguilar-Aguilar, Angélica; Gonzalez-Domínguez, Martha; Lager, Erik; Zamudio-Vazquez, Rubí; Godoy-Vargas, Jazmín; Villanueva-García, Fabian

    2007-09-27

    An unprecedented synthesis of 8-substituted-borondipyrromethenes is described starting from 8-thiomethylbodipy 1. Aryl, heteroaryl, alkenyl, and organometallic boronic acids smoothly reacted with 1 in the presence of a catalytic amount of Pd(0) and a stoichiometric amount of Cu(I)-2-thienylcarboxylate under neutral conditions to give the corresponding Bodipy analogues in good to quantitative yields (20 examples). A remarkable reactivity was observed in some cases, e.g., ferrocenylboronic acid gave the product in 98% isolated yield after only 10 min at 55 degrees C. PMID:17764191

  4. A green and efficient protocol for the synthesis of dihydropyrano[2,3-c]pyrazole derivatives via a one-pot, four component reaction by grinding method.

    PubMed

    Ambethkar, Sethurajan; Padmini, Vediappen; Bhuvanesh, Nattamai

    2015-11-01

    An efficient grinding protocol for the synthesis of dihydropyrano[2,3-c]pyrazole derivatives from acetylene ester, hydrazine hydrate, aryl aldehydes and malononitrile under solvent free conditions has been achieved with excellent yields. The structures of the synthesized compounds were deduced by spectroscopic techniques and the compounds were further evaluated for their in vitro antioxidant and antimicrobial activities. PMID:26644936

  5. A green and efficient protocol for the synthesis of dihydropyrano[2,3-c]pyrazole derivatives via a one-pot, four component reaction by grinding method

    PubMed Central

    Ambethkar, Sethurajan; Padmini, Vediappen; Bhuvanesh, Nattamai

    2014-01-01

    An efficient grinding protocol for the synthesis of dihydropyrano[2,3-c]pyrazole derivatives from acetylene ester, hydrazine hydrate, aryl aldehydes and malononitrile under solvent free conditions has been achieved with excellent yields. The structures of the synthesized compounds were deduced by spectroscopic techniques and the compounds were further evaluated for their in vitro antioxidant and antimicrobial activities.

  6. Facile aqueous synthesis of ?-AgI nanoplates as efficient visible-light-responsive photocatalyst.

    PubMed

    Jiang, Wen; An, Changhua; Liu, Junxue; Wang, Shutao; Zhao, Lianming; Guo, Wenyue; Liu, Jinxiang

    2014-01-01

    Owing to far-ranging industrial applications and theoretical researches, tailored synthesis of well-defined nanocrystals has attracted substantial research interest. Herein, ?-AgI nanoplates have been synthesized through a facile polyvinylpyrrolidone (PVP)-assisted-aqueous-solution (PAAS) method under mild conditions. The parametric studies on the effect of ratio of reactants, solvents and surfactants were performed, revealing that a molar ratio of I(-) to Ag(+) of 1.2 in deionized water and the presence of appropriate PVP as stabilizing agent can stimulate the preferred orientation growth of AgI nanoplates. The as-synthesized AgI nanoplates exhibit excellent photocatalytic activity and enhanced durability towards the degradation of organics, i.e., rhodamine B (RhB), under visible light illumination in comparison with corresponding bulk nanoparticles. A possible photocatalytic reaction mechanism was discussed, revealing O2?(-) and h(+) are main reactive species and free ?OH radicals in solution also contribute to the degradation reaction. The superior photocatalytic performance renders the as-achieved AgI nanoplates promising candidates for applications in the fields of environmental purification or water disinfection. The present work opens an avenue to the synthesis of other shaped silver halide nanophotocatalysts. PMID:24101116

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

    PubMed Central

    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

    2015-01-01

    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. PMID:25733848

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

    PubMed

    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. PMID:25733848

  9. Rational Design and Synthesis of Freestanding Photoelectric Nanodevices as Highly Efficient Photocatalysts

    PubMed Central

    Qu, Yongquan; Liao, Lei; Cheng, Rui; Wang, Yue; Lin, Yung-chen; Huang, Yu; Duan, Xiangfeng

    2010-01-01

    Photocatalysts are of significant interest for solar energy harvesting and conversion into chemical energy. However, the photocatalysts available to date are limited by either poor efficiency in the visible light range or insufficient photoelectrochemical stability. Here we report the rational design of a new generation of freestanding photoelectric nanodevices as highly efficient and stable photocatalysts by integrating a nanoscale photodiode with two redox catalysts in a single nanowire heterostructure. We show that a platinum-silicon-silver nanowire heterostructure can be synthesized to integrate a nanoscale metal-semiconductor Schottky diode encased in a protective insulating shell with two exposed metal catalysts. We further demonstrated that the Schottky diodes exhibited pronounced photovoltaic effect with nearly unity internal quantum efficiency, and that the integrated nanowire heterostructures could be used as highly efficient photocatalysts for a wide range of thermodynamically downhill and uphill reactions including photocatalytic degradation of organic dyes, reduction of metal ions and carbon dioxide using visible light. Our studies for the first time demonstrated the integration of multiple distinct functional components into a single nanostructure to form a standalone active nanosystem, and for the first time successfully realized a photoelectric nanodevice that is both highly efficient and highly stable throughout the entire solar spectrum. It thus opens a rational avenue to design and synthesize a new generation of photoelectric nanosystems with unprecedented efficiency and stability, and will impact broadly in areas including environmental remediation and solar fuel production. PMID:20373781

  10. Efficient synthesis and biological activity of Psammaplin A and its analogues as antitumor agents.

    PubMed

    Hong, Suckchang; Shin, Yoonho; Jung, Myunggi; Ha, Min Woo; Park, Yohan; Lee, Yeon-Ju; Shin, Jongheon; Oh, Ki Bong; Lee, Sang Kook; Park, Hyeung-geun

    2015-01-01

    We describe a new concise method for the synthesis of psammaplin A and its analogues, and antitumor activity of psammaplin A analogues. Psammaplin A was obtained with 41% yield in 5 steps from 3-bromo-4-hydroxybenzaldahyde and ethyl acetoacetate via Knoevenagel condensation and ?-nitrosation as key steps. Twenty eight analogues of psammaplin A were prepared employing the new synthetic approach. Structure-activity relationship study against cytotoxicity reveal that the free oxime group and disulfide functional group were responsible for high cytotoxicity. Also the bromotyrosine component was relatively tolerable and hydrophobic aromatic groups preserved the cytotoxicity. The cytotoxicity of aromatic group is dependent on the size and spatial geometry. Among them, five compounds showed comparable cytotoxicity to psammaplin A. Compound 30 exhibited potential HDAC inhibitory activity and in vivo antitumor activity. PMID:25884112

  11. Synthesis of taurine–fluorescein conjugate and evaluation of its retina-targeted efficiency in vitro

    PubMed Central

    Huang, Meihong; Song, Jiaqi; Lu, Bingzheng; Huang, Huizhi; Chen, Yizhen; Yin, Wei; Zhu, Wenbo; Su, Xinwen; Wu, Chuanbin; Hu, Haiyan

    2014-01-01

    In this work, retinal penetration of fluorescein was achieved in vitro by covalent attachment of taurine to fluorescein, yielding the F–Tau conjugate. Nuclear magnetic resonance (NMR) and high resolution mass spectrometry (HRMS) were used to confirm the successful synthesis of F–Tau. The cellular uptake of F–Tau in adult retinal pigment epithelial cells (ARPE-19) and human retinal microvascular endothelial cells (hRMECs) was visualized via confocal scanning microscopy. The results indicated an improvement of solubility and a reduction of logP of F–Tau compared with fluorescein. As compared with fluorescein, F–Tau showed little toxicity, and was retained longer by cells in uptake experiments. F–Tau also displayed higher transepithelial permeabilities than fluorescein in ARPE-19 and hRMECs monolayer cells (P<0.05). These results showed that taurine may be a useful ligand for targeting small-molecule hydrophobic pharmaceuticals into the retina. PMID:26579416

  12. An efficient green synthesis of 2-arylbenzothiazole analogues as potent antibacterial and anticancer agents.

    PubMed

    Chhabra, Mohit; Sinha, Sohini; Banerjee, Swagata; Paira, Priyankar

    2016-01-01

    We have demonstrated a novel and green approach for the synthesis of 2-substituted benzothiazole analogues. A number of 2-aryl and heteroaryl benzothiazole scaffolds were synthesized using Amberlite IR-120 resin under microwave irradiation. The catalytic role and reusability of the resin was well established here. 2-Substituted benzothiazole analogues (3a-l) were also tested against several bacterial strains (Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Salmonella) and cancer cell lines (MCF-7 and HeLa). The stability of compound 2-phenyl benzothiazole (3a) and 2-pyridin-2-yl-benzothiazole (3k) in GSH (0.01mM dissolved in DMSO) was measured by UV-Vis spectroscopy. Compound 3k also shows remarkable fluorescence in MeOH. PMID:26590102

  13. Growth rate hypothesis and efficiency of protein synthesis under different sulphate concentrations in two green algae.

    PubMed

    Giordano, Mario; Palmucci, Matteo; Raven, John A

    2015-11-01

    The growth rate hypothesis (GRH) predicts a positive correlation between growth rate and RNA content because growth depends upon the protein synthesis machinery. The application of this hypothesis to photoautotrophic organisms has been questioned. We tested the GRH on one prasinophycean, Tetraselmis suecica, and one chlorophycean, Dunaliella salina, grown at three sulphate concentrations. Sulphate was chosen because its concentration in the oceans increased through geological time and apparently had a role in the evolutionary trajectories of phytoplankton. Cell protein content and P quota were positively related to the RNA content (r?=?0.62 and r?=?0.74, respectively). The correlation of the RNA content with growth rates (r?=?0.95) indicates that the GRH was valid for these species when growth rates were below 0.82?d(-1) . PMID:25851030

  14. Green synthesis of highly efficient CdSe quantum dots for quantum-dots-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Gao, Bing; Shen, Chao; Zhang, Bo; Zhang, Mengya; Yuan, Shuanglong; Yang, Yunxia; Chen, Guorong

    2014-05-01

    Green synthesis of CdSe quantum dots for application in the quantum-dots-sensitized solar cells (QDSCs) is investigated in this work. The CdSe QDs were prepared with glycerol as the solvent, with sharp emission peak, full width at half maximum around 30 nm, and absorption peak from 475 nm to 510 nm. The reaction is environmental friendly and energy saving. What's more, the green synthesized CdSe QDs are coherence to the maximum remittance region of the solar spectrum and suitable as sensitizers to assemble onto TiO2 electrodes for cell devices application. What's more, the dynamic procedure of the carriers' excitation, transportation, and recombination in the QDSCs are discussed. Because the recombination of the electrons from the conduction band of TiO2's to the electrolyte affects the efficiency of the solar cells greatly, 3-Mercaptopropionic acid capped water-dispersible QDs were used to cover the surface of TiO2. The resulting green synthesized CdSe QDSCs with Cu2S as the electrode show a photovoltaic performance with a conversion efficiency of 3.39%.

  15. Green synthesis of highly efficient CdSe quantum dots for quantum-dots-sensitized solar cells

    SciTech Connect

    Gao, Bing; Shen, Chao; Zhang, Mengya; Yuan, Shuanglong; Yang, Yunxia E-mail: grchen@ecust.edu.cn; Chen, Guorong E-mail: grchen@ecust.edu.cn; Zhang, Bo

    2014-05-21

    Green synthesis of CdSe quantum dots for application in the quantum-dots-sensitized solar cells (QDSCs) is investigated in this work. The CdSe QDs were prepared with glycerol as the solvent, with sharp emission peak, full width at half maximum around 30?nm, and absorption peak from 475?nm to 510?nm. The reaction is environmental friendly and energy saving. What's more, the green synthesized CdSe QDs are coherence to the maximum remittance region of the solar spectrum and suitable as sensitizers to assemble onto TiO{sub 2} electrodes for cell devices application. What's more, the dynamic procedure of the carriers' excitation, transportation, and recombination in the QDSCs are discussed. Because the recombination of the electrons from the conduction band of TiO{sub 2}'s to the electrolyte affects the efficiency of the solar cells greatly, 3-Mercaptopropionic acid capped water-dispersible QDs were used to cover the surface of TiO{sub 2}. The resulting green synthesized CdSe QDSCs with Cu{sub 2}S as the electrode show a photovoltaic performance with a conversion efficiency of 3.39%.

  16. Efficient approach to 2-hydroxy-2,3-dihydrofuran derivatives and its application for the synthesis of novel 4-(1H-pyrazol-4-yl)pyridazines.

    PubMed

    Ma, Jun-Rui; Shu, Wen-Ming; Zheng, Kai-Lu; Ni, Fan; Yin, Guo-Dong; Wu, An-Xin

    2015-05-01

    A highly efficient method for the synthesis of 2-hydroxy-2,3-dihydrofuran derivatives from 1,4-enediones and phenacyl pyridinium halides via a domino reaction has been developed. This is a simple and beneficial strategy for the construction of 2-hydroxy-2,3-dihydrofuran compounds from readily available starting materials under mild conditions. Moreover, the application of this reaction provides a straightforward and practical route for the synthesis of the novel 4-(1H-pyrazol-4-yl)pyridazine skeleton. PMID:25821120

  17. Looking glass inhibitors: efficient synthesis and biological evaluation of DD-deoxyfuconojirimycin

    E-print Network

    -LL-fuconojirimycin, was efficiently prepared from 2,3-O-isopropy- lidene-LL-lyxonolactone in four steps and evaluated as a glycosidase inhibitor. Ó 2005 Elsevier Ltd. All rights reserved. Keywords: Galactostatin; Glycosidase inhibitor; 1 viral infections5 or cancer.6 They have also been used as chemical probes, in combination with protein

  18. Efficient utilization of crude glycerol as fermentation substrate in the synthesis of poly(3-hydroxybutyrate) biopolymers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    One refined and 2 crude glycerol samples were utilized to produce poly(3-hydroxybutyrate) (PHB) by Pseudomonas oleovorans NRRL B-14682. Fermentation conditions were determined to efficiently utilize glycerol while maintaining PHB yields. A batch culture protocol including 1% glycerol and an aerati...

  19. An efficient synthesis of quinolines via copper-catalyzed C-N cleavage.

    PubMed

    Xi, Long-Yi; Zhang, Ruo-Yi; Zhang, Lei; Chen, Shan-Yong; Yu, Xiao-Qi

    2015-04-01

    An efficient method to synthesize substituted quinolines from ketones and 2-amino benzylamines is described. Copper-catalyzed C-N cleavage of amines followed by condensation with ketones deliver quinolines in moderate to high yields. The broad scope of substrates and the use of air as the sole oxidant make this transformation very attractive. PMID:25712024

  20. Efficient enzymatic systems for synthesis of novel ?-mangostin glycosides exhibiting antibacterial activity against Gram-positive bacteria.

    PubMed

    Le, Tuoi Thi; Pandey, Ramesh Prasad; Gurung, Rit Bahadur; Dhakal, Dipesh; Sohng, Jae Kyung

    2014-10-01

    Two enzymatic systems were developed for the efficient synthesis of glycoside products of ?-mangostin, a natural xanthonoid exhibiting anti-oxidant, antibacterial, anti-inflammatory, and anticancer activities. In these systems, one-pot reactions for the synthesis of UDP-?-D-glucose and UDP-?-D-2-deoxyglucose were modified and combined with a glycosyltransferase (GT) from Bacillus licheniformis DSM-13 to afford C-3 and C-6 position modified glucose and 2-deoxyglucose conjugated novel ?-mangostin derivatives. ?-Mangostin 3-O-?-D-glucopyranoside, ?-mangostin 6-O-?-D-glucopyranoside, ?-mangostin 3,6-di-O-?-D-glucopyranoside, ?-mangostin 3-O-?-D-2-deoxyglucopyranoside, ?-mangostin 6-O-?-D-2-deoxyglucopyranoside, and ?-mangostin 3,6-di-O-?-D-2-deoxyglucopyranoside were successfully produced in practical quantities and characterized by high-resolution quadruple time-of-flight electrospray ionization-mass spectrometry (HR-QTOF ESI/MS), (1)H and (13)C NMR analyses. In excess of the substrate, the maximum productions of three ?-mangostin glucopyranosides (4.8 mg/mL, 86.5 % overall conversion of ?-mangostin) and three ?-mangostin 2-deoxyglucopyronosides (4.0 mg/mL, 79 % overall conversion of ?-mangostin) were achieved at 4-h incubation period. All the ?-mangostin glycosides exhibited improved water solubility, and their antibacterial activity against three Gram-positive bacteria Micrococcus luteus, Bacillus subtilis, and Staphylococcus aureus was drastically enhanced by the glucosylation at C-3 position. In this study, diverse glycosylated ?-mangostin were produced in significant quantities by using inexpensive starting materials and recycling co-factors within a reaction vessel without use of expensive NDP-sugars in the glycosylation reactions. PMID:25038930

  1. Autoregressive HMMs for speech synthesis

    E-print Network

    Shannon, Matt; Byrne, William

    2009-09-07

    We propose the autoregressive HMM for speech synthesis. We show that the autoregressive HMM supports efficient EM parameter estimation and that we can use established effective synthesis techniques such as synthesis considering global variance...

  2. Efficient synthesis of core@shell Fe3O4@Au nanoparticles

    NASA Astrophysics Data System (ADS)

    Alonso-Cristobal, Paulino; Laurenti, Marco; Lopez-Cabarcos, Enrique; Rubio-Retama, Jorge

    2015-07-01

    The synthesis of Fe3O4@Au nanoparticles has received much attention due to promising applications in the biomedical field. In this work, we produced Fe3O4@Au nanoparticles by using a two-step solvothermal route that employed Fe3O4 nanoparticles as seeds for the Au deposition. Although this protocol leads to highly monodisperse and reproducible Fe3O4@Au nanoparticles it was necessary to perform a systematic study to have a better understanding, improve the yield and allow us to obtain a tunable result. We demonstrated that the Au:Fe3O4 ratio is a key parameter that, contrary to what could be expected, does not influence the Au shell thickness. However, this parameter should be optimized because it strongly influences the yield. When the Au:Fe3O4 ratio was low there were plenty of uncoated Fe3O4 nanoparticles, whereas when the Au:Fe3O4 ratio was high there could be some pure Au nanoparticles together with the desired Fe3O4@Au nanoparticles. Furthermore we demonstrated that the Au shell thickness can be tuned by varying the reaction temperature. This paper describes the influence of both parameters and proposes a mechanism of the synthetic process by studying parametrically the morphological and structural evolution of the nanoparticles by TEM, DLS, SQUID and UV-vis spectroscopy.

  3. An efficient synthesis of porphyrins with different meso substituents that avoids scrambling in aqueous media.

    PubMed

    Nowak-Król, Agnieszka; Plamont, Rémi; Canard, Gabriel; Edzang, Judicaelle Andeme; Gryko, Daniel T; Balaban, Teodor Silviu

    2015-01-19

    We have developed new conditions that afford regioisomerically pure trans-A2B2-, A3B-, and trans-AB2C-porphyrins bearing aryl and arylethynyl substituents. The porphyrins were prepared by the acid-catalyzed condensation of dipyrromethanes with aldehydes followed by oxidation with p-chloranil or 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). Optimal conditions for the condensation were identified after examining various reaction parameters such as solvent composition, acid concentration, and reaction time. The conditions identified (for aromatic aldehydes: EtOH/H2O 4:1, [DPM] = 4?mM, [aldehyde] = 4?mM, [HCl] = 38?mM, 16?h; for arylethynyl aldehydes: THF/H2O 2:1, [DPM] = 13?mM, [aldehyde] = 13?mM, [HCl] = 150?mM, 3?h) resulted in the formation of porphyrins in yields of 9-38% without detectable scrambling. This synthesis is compatible with diverse functionalities such as ester or nitrile. In total, 20 new trans-A2B2-, A3B-, and trans-AB2C-porphyrins were prepared. The scope and limitations of the two sets of reaction conditions have been explored. The methodological advantage of this approach is its straightforward access to building blocks and the formation of the porphyrin core in higher yields than by any other methodology and by using environmentally benign and nonhazardous chemicals. PMID:25417808

  4. Energy Efficient and Size Tunable Synthesis of `Colloidal' Zinc Oxide Nanoparticles by Simple Beaker Chemistry

    NASA Astrophysics Data System (ADS)

    Kushwaha, Ajay; Singh, Vijay; Aslam, M.

    2011-07-01

    A facile approach to synthesize `colloidal' ZnO nanoparticles with control over the size is presented here. All the synthesis was carried out at room temperature and simple beaker chemistry was utilized. The approach leads to slow growth of colloidal nanoparticles with saving of energy because no heating (room temperature) is required during reaction. To verify the nucleation and growth of the nanoparticles, time dependent UV-Vis absorption spectroscopy has been studied and found that growth of nanoparticles start within minute. Transmission electron microscopy and UV-Vis absorption spectroscopy concludes that as reaction time increases particle size get larger and varies from 3-20 nm for 1 hour reaction time to 6 hour reaction time. XRD pattern of the ZnO nanoparticles shows a wurtzite crystalline nature which is supported by selected area electron diffraction measurement (SEAD), SEAD also confirms the polycrystalline nature of the ZnO nanoparticles. Photoluminescence of the colloidal solution of the ZnO particle show an excitonic band at 377 nm.

  5. Efficient synthesis of Hsp90 inhibitor dimers as potential antitumor agents.

    PubMed

    Sekiguchi, Hironori; Muranaka, Kazuhiro; Osada, Akiko; Ichikawa, Satoshi; Matsuda, Akira

    2010-08-01

    The PU-H58-dimers 13a-15b were efficiently synthesized and their biological properties were evaluated. The copper-catalyzed alkyne azide coupling was effective in simultaneously linking three components via a triazole formation to afford the target dimers. These synthesized dimers exhibited binding affinity to the N-terminal domain of Hsp90, cytotoxicity, and client degradation activity although these activities were comparative or weak comparable with that of the parent compound. PMID:20609590

  6. Facile synthesis of nanostructured vanadium oxide as cathode materials for efficient Li-ion batteries

    E-print Network

    Cao, Guozhong

    -ion batteries Yanyi Liu,a Evan Uchaker,a Nan Zhou,ab Jiangang Li,ac Qifeng Zhanga and Guozhong Cao*a Received 23 and VO2 (B) nanorods were tested as active cathode materials for Li-ion batteries. The V2O5 sheet for efficient Li-ion batteries. Introduction The expansion and demands for energy use in the past several

  7. Dispersion-precipitation synthesis of nanosized magnetic iron oxide for efficient removal of arsenite in water.

    PubMed

    Cheng, Wei; Xu, Jing; Wang, Yajie; Wu, Feng; Xu, Xiuyan; Li, Jinjun

    2015-05-01

    Nanosized magnetic iron oxide was facilely synthesized by a dispersion-precipitation method, which involved acetone-promoted precipitation of colloidal hydrous iron oxide nanoparticles and subsequent calcination of the precipitate at 250°C. Characterization by X-ray diffraction, transmission electron microscopy, Raman spectroscopy, nitrogen sorption, and vibrating-sample magnetometry revealed that the material was a composite of ?-Fe2O3 and ?-Fe2O3 with primary particle size of 15-25 nm and specific surface area of 121 m(2)/g, as well as superparamagnetic property. The material was used as adsorbent for the removal of arsenite in water. Batch experiments showed that the adsorption isotherms at pH 3.0-11.0 fit the Langmuir equation and the adsorption obeys pseudo-second-order kinetics. Its maximum sorption capability for arsenite is 46.5 mg/g at pH 7.0. Coexisting nitrate, carbonate, sulfate, chloride, and fluoride have no significant effect on the removal efficiency of arsenite, while phosphate and silicate reduce the removal efficiency to some extent. The As(III) removal mechanism is chemisorption through forming inner-sphere surface complexes. The efficiency of arsenic removal is still maintained after five cycles of regeneration-reuse. PMID:25612934

  8. Determining the microwave coupling and operational efficiencies of a microwave plasma assisted chemical vapor deposition reactor under high pressure diamond synthesis operating conditions

    NASA Astrophysics Data System (ADS)

    Nad, Shreya; Gu, Yajun; Asmussen, Jes

    2015-07-01

    The microwave coupling efficiency of the 2.45 GHz, microwave plasma assisted diamond synthesis process is investigated by experimentally measuring the performance of a specific single mode excited, internally tuned microwave plasma reactor. Plasma reactor coupling efficiencies (?) > 90% are achieved over the entire 100-260 Torr pressure range and 1.5-2.4 kW input power diamond synthesis regime. When operating at a specific experimental operating condition, small additional internal tuning adjustments can be made to achieve ? > 98%. When the plasma reactor has low empty cavity losses, i.e., the empty cavity quality factor is >1500, then overall microwave discharge coupling efficiencies (?coup) of >94% can be achieved. A large, safe, and efficient experimental operating regime is identified. Both substrate hot spots and the formation of microwave plasmoids are eliminated when operating within this regime. This investigation suggests that both the reactor design and the reactor process operation must be considered when attempting to lower diamond synthesis electrical energy costs while still enabling a very versatile and flexible operation performance.

  9. Determining the microwave coupling and operational efficiencies of a microwave plasma assisted chemical vapor deposition reactor under high pressure diamond synthesis operating conditions.

    PubMed

    Nad, Shreya; Gu, Yajun; Asmussen, Jes

    2015-07-01

    The microwave coupling efficiency of the 2.45 GHz, microwave plasma assisted diamond synthesis process is investigated by experimentally measuring the performance of a specific single mode excited, internally tuned microwave plasma reactor. Plasma reactor coupling efficiencies (?) > 90% are achieved over the entire 100-260 Torr pressure range and 1.5-2.4 kW input power diamond synthesis regime. When operating at a specific experimental operating condition, small additional internal tuning adjustments can be made to achieve ? > 98%. When the plasma reactor has low empty cavity losses, i.e., the empty cavity quality factor is >1500, then overall microwave discharge coupling efficiencies (?(coup)) of >94% can be achieved. A large, safe, and efficient experimental operating regime is identified. Both substrate hot spots and the formation of microwave plasmoids are eliminated when operating within this regime. This investigation suggests that both the reactor design and the reactor process operation must be considered when attempting to lower diamond synthesis electrical energy costs while still enabling a very versatile and flexible operation performance. PMID:26233399

  10. Emulsion Synthesis of Size-Tunable CH3NH3PbBr3 Quantum Dots: An Alternative Route toward Efficient Light-Emitting Diodes.

    PubMed

    Huang, Hailong; Zhao, Fangchao; Liu, Lige; Zhang, Feng; Wu, Xian-Gang; Shi, Lijie; Zou, Bingsuo; Pei, Qibing; Zhong, Haizheng

    2015-12-30

    We report a facile nonaqueous emulsion synthesis of colloidal halide perovskite quantum dots by controlled addition of a demulsifier into an emulsion of precursors. The size of resulting CH3NH3PbBr3 quantum dots can be tuned from 2 to 8 nm by varying the amount of demulsifier. Moreover, this emulsion synthesis also allows the purification of these quantum dots by precipitation from the colloidal solution and obtains solid-state powder which can be redissolved for thin film coating and device fabrication. The photoluminescence quantum yields of the quantum dots is generally in the range of 80-92%, and can be well-preserved after purification (?80%). Green light-emitting diodes fabricated comprising a spin-cast layer of the colloidal CH3NH3PbBr3 quantum dots exhibited maximum current efficiency of 4.5 cd/A, power efficiency of 3.5 lm/W, and external quantum efficiency of 1.1%. This provides an alternative route toward high efficient solution-processed perovskite-based light-emitting diodes. In addition, the emulsion synthesis is versatile and can be extended for the fabrication of inorganic halide perovskite colloidal CsPbBr3 nanocrystals. PMID:26652661

  11. Marine Sponge/CuO Nanocrystal: A Natural and Efficient Catalyst for Sulfonamides Synthesis

    PubMed Central

    Shushizadeh, Mohamad Reza; Mostoufi, Azar; Fakhrian, Marjan

    2012-01-01

    Background Marine sponge/nano-CuO as a natural catalyst efficiently catalyzed the Sulfonylation reaction of p-chlorobenzene sulfonyl chlorides with amines in order to prepare sulfonamides. The advantages included use of a natural catalyst, ease of handling, requirement of a very small amount of catalyst, mild reaction condition and appropriateness to high yield. Objectives The current study aimed to look for a solid support reaction and to develop a general, mild and novel method in order to synthesize sulfonamides in the absence of a strong base, it was found that marine sponge/nano-CuO is a natural and efficient catalyst for this method at room temperature. Materials and Methods The reaction was carried out simply by addition of amine and p -chlorobenzene sulfonyl chloride to the mixture of Marine sponge powder/nano-CuO in acetonitrile at room temperature. Then the reaction mixture was extracted by CH2Cl2 and was dried over anhydrous magnesium sulfate. Evaporation of the solvent afforded the products. Results In this method several derivatives of sulfonamide underwent the reaction of different amines with p-chlorobenzene sulfonyl chloride in the presence of marine sponge/nano-CuO in CH3CN are synthesized. Conclusions In conclusion, a new, natural and efficient marine catalyst, and a marine sponge/nano-CuO were developed to synthesize sulfonamide derivatives in CH3CN in 75–93% yields. This method was applied to a wide range of aromatic and aliphatic amines under mild conditions. PMID:24624171

  12. Efficient synthesis and reaction kinetics of readily water soluble esters containing sulfonic groups.

    PubMed

    Idzik, Krzysztof R; Nödler, Karsten; Maier, Friedrich; Licha, Tobias

    2014-01-01

    A series of various readily water soluble esters were synthesized by a very efficient procedure. These compounds can be useful as thermosensitive tracers for studying the cooling progress in a low enthalpy georeservoir exploitable by double flash geothermal power plant systems. The kinetics of their hydrolysis was investigated. Acylation of primary alcohols or phenols was carried out by a method based on a single-phase solvent system consisting of ethyl acetate acting as an organic solvent and triethylamine acting as a catalyst. Products were characterized by 1H-NMR, and 13C-NMR. PMID:25517341

  13. Design and synthesis of molecular donors for solution-processed high-efficiency organic solar cells.

    PubMed

    Coughlin, Jessica E; Henson, Zachary B; Welch, Gregory C; Bazan, Guillermo C

    2014-01-21

    Organic semiconductors incorporated into solar cells using a bulk heterojunction (BHJ) construction show promise as a cleaner answer to increasing energy needs throughout the world. Organic solar cells based on the BHJ architecture have steadily increased in their device performance over the past two decades, with power conversion efficiencies reaching 10%. Much of this success has come with conjugated polymer/fullerene combinations, where optimized polymer design strategies, synthetic protocols, device fabrication procedures, and characterization methods have provided significant advancements in the technology. More recently, chemists have been paying particular attention to well-defined molecular donor systems due to their ease of functionalization, amenability to standard organic purification and characterization methods, and reduced batch-to-batch variability compared to polymer counterparts. There are several critical properties for efficient small molecule donors. First, broad optical absorption needs to extend towards the near-IR region to achieve spectral overlap with the solar spectrum. Second, the low lying highest occupied molecular orbital (HOMO) energy levels need to be between -5.2 and -5.5 eV to ensure acceptable device open circuit voltages. Third, the structures need to be relatively planar to ensure close intermolecular contacts and high charge carrier mobilities. And last, the small molecule donors need to be sufficiently soluble in organic solvents (?10 mg/mL) to facilitate solution deposition of thin films of appropriate uniformity and thickness. Ideally, these molecules should be constructed from cost-effective, sustainable building blocks using established, high yielding reactions in as few steps as possible. The structures should also be easy to functionalize to maximize tunability for desired properties. In this Account, we present a chronological description of our thought process and design strategies used in the development of highly efficient molecular donors that achieve power conversion efficiencies greater than 7%. The molecules are based on a modular D(1)-A-D(2)-A-D(1) architecture, where A is an asymmetric electron deficient heterocycle, which allowed us to quickly access a library of compounds and develop structure-property-performance relationships. Modifications to the D1 and D2 units enable spectral coverage throughout the entire visible region and control of HOMO energy levels, while adjustments to the pendant alkyl substituents dictate molecular solubility, thermal transition temperatures, and solid-state organizational tendencies. Additionally, we discuss regiochemical considerations that highlight how individual atom placements can significantly influence molecular and subsequently device characteristics. Our results demonstrate the utility of this architecture for generating promising materials to be integrated into organic photovoltaic devices, call attention to areas for improvement, and provide guiding principles to sustain the steady increases necessary to move this technology forward. PMID:23984626

  14. Design synthesis and optimization of permanent magnet synchronous machines based on computationally-efficient finite element analysis

    NASA Astrophysics Data System (ADS)

    Sizov, Gennadi Y.

    In this dissertation, a model-based multi-objective optimal design of permanent magnet ac machines, supplied by sine-wave current regulated drives, is developed and implemented. The design procedure uses an efficient electromagnetic finite element-based solver to accurately model nonlinear material properties and complex geometric shapes associated with magnetic circuit design. Application of an electromagnetic finite element-based solver allows for accurate computation of intricate performance parameters and characteristics. The first contribution of this dissertation is the development of a rapid computational method that allows accurate and efficient exploration of large multi-dimensional design spaces in search of optimum design(s). The computationally efficient finite element-based approach developed in this work provides a framework of tools that allow rapid analysis of synchronous electric machines operating under steady-state conditions. In the developed modeling approach, major steady-state performance parameters such as, winding flux linkages and voltages, average, cogging and ripple torques, stator core flux densities, core losses, efficiencies and saturated machine winding inductances, are calculated with minimum computational effort. In addition, the method includes means for rapid estimation of distributed stator forces and three-dimensional effects of stator and/or rotor skew on the performance of the machine. The second contribution of this dissertation is the development of the design synthesis and optimization method based on a differential evolution algorithm. The approach relies on the developed finite element-based modeling method for electromagnetic analysis and is able to tackle large-scale multi-objective design problems using modest computational resources. Overall, computational time savings of up to two orders of magnitude are achievable, when compared to current and prevalent state-of-the-art methods. These computational savings allow one to expand the optimization problem to achieve more complex and comprehensive design objectives. The method is used in the design process of several interior permanent magnet industrial motors. The presented case studies demonstrate that the developed finite element-based approach practically eliminates the need for using less accurate analytical and lumped parameter equivalent circuit models for electric machine design optimization. The design process and experimental validation of the case-study machines are detailed in the dissertation.

  15. Synthesis and characterization of VO2-based thermochromic thin films for energy-efficient windows.

    PubMed

    Batista, Carlos; Ribeiro, Ricardo M; Teixeira, Vasco

    2011-01-01

    Thermochromic VO2 thin films have successfully been grown on SiO2-coated float glass by reactive DC and pulsed-DC magnetron sputtering. The influence of substitutional doping of V by higher valence cations, such as W, Mo, and Nb, and respective contents on the crystal structure of VO2 is evaluated. Moreover, the effectiveness of each dopant element on the reduction of the intrinsic transition temperature and infrared modulation efficiency of VO2 is discussed. In summary, all the dopant elements--regardless of the concentration, within the studied range-- formed a solid solution with VO2, which was the only compound observed by X-ray diffractometry. Nb showed a clear detrimental effect on the crystal structure of VO2. The undoped films presented a marked thermochromic behavior, specially the one prepared by pulsed-DC sputtering. The dopants effectively decreased the transition of VO2 to the proximity of room temperature. However, the IR modulation efficiency is markedly affected as a consequence of the increased metallic character of the semiconducting phase. Tungsten proved to be the most effective element on the reduction of the semiconducting-metal transition temperature, while Mo and Nb showed similar results with the latter being detrimental to the thermochromism. PMID:21711813

  16. Synthesis and characterization of VO2-based thermochromic thin films for energy-efficient windows

    PubMed Central

    2011-01-01

    Thermochromic VO2 thin films have successfully been grown on SiO2-coated float glass by reactive DC and pulsed-DC magnetron sputtering. The influence of substitutional doping of V by higher valence cations, such as W, Mo, and Nb, and respective contents on the crystal structure of VO2 is evaluated. Moreover, the effectiveness of each dopant element on the reduction of the intrinsic transition temperature and infrared modulation efficiency of VO2 is discussed. In summary, all the dopant elements--regardless of the concentration, within the studied range-- formed a solid solution with VO2, which was the only compound observed by X-ray diffractometry. Nb showed a clear detrimental effect on the crystal structure of VO2. The undoped films presented a marked thermochromic behavior, specially the one prepared by pulsed-DC sputtering. The dopants effectively decreased the transition of VO2 to the proximity of room temperature. However, the IR modulation efficiency is markedly affected as a consequence of the increased metallic character of the semiconducting phase. Tungsten proved to be the most effective element on the reduction of the semiconducting-metal transition temperature, while Mo and Nb showed similar results with the latter being detrimental to the thermochromism. PMID:21711813

  17. Manganese powder promoted highly efficient and selective synthesis of fullerene mono- and biscycloadducts at room temperature

    NASA Astrophysics Data System (ADS)

    Si, Weili; Zhang, Xuan; Lu, Shirong; Yasuda, Takeshi; Asao, Naoki; Han, Liyuan; Yamamoto, Yoshinori; Jin, Tienan

    2015-09-01

    Discovery of an efficient, practical, and flexible synthetic method to produce various important electron acceptors for low-cost organic photovoltaics (OPVs) is highly desirable. Although the most commonly used acceptor materials, such as PC61BM, PC71BM, IC60BA, bisPC61BM have been proved to be promising for the OPVs, they are still very expensive mainly due to their low production yields and limited synthetic methods. Herein, we report an unprecedented and innovative synthetic method of a variety of fullerene mono- and biscycloadducts by using manganese powder as a promotor. The reaction of fullerenes with various dibromides proceeds efficiently and selectively under very mild conditions to give the corresponding cycloadducts in good to excellent yields. The combination of manganese power with DMSO additive is crucial for the successful implementation of the present cycloaddition. Notably, the standard OPV acceptors, such as PCBMs, have been obtained in extraordinarily high yields, which cannot be achieved under the previously reported methods.

  18. Manganese powder promoted highly efficient and selective synthesis of fullerene mono- and biscycloadducts at room temperature

    PubMed Central

    Si, Weili; Zhang, Xuan; Lu, Shirong; Yasuda, Takeshi; Asao, Naoki; Han, Liyuan; Yamamoto, Yoshinori; Jin, Tienan

    2015-01-01

    Discovery of an efficient, practical, and flexible synthetic method to produce various important electron acceptors for low-cost organic photovoltaics (OPVs) is highly desirable. Although the most commonly used acceptor materials, such as PC61BM, PC71BM, IC60BA, bisPC61BM have been proved to be promising for the OPVs, they are still very expensive mainly due to their low production yields and limited synthetic methods. Herein, we report an unprecedented and innovative synthetic method of a variety of fullerene mono- and biscycloadducts by using manganese powder as a promotor. The reaction of fullerenes with various dibromides proceeds efficiently and selectively under very mild conditions to give the corresponding cycloadducts in good to excellent yields. The combination of manganese power with DMSO additive is crucial for the successful implementation of the present cycloaddition. Notably, the standard OPV acceptors, such as PCBMs, have been obtained in extraordinarily high yields, which cannot be achieved under the previously reported methods. PMID:26349427

  19. Synthesis of ZnO/Ag/graphene composite and its enhanced photocatalytic efficiency

    SciTech Connect

    Xu, Fang; Yuan, Yafei; Wu, Dapeng; Zhao, Mei; Gao, Zhiyong; Jiang, Kai

    2013-06-01

    Highlights: ? ZnO/Ag/graphene composite was synthesized via a facile aqueous reaction. ? ZnO/Ag composite nanoparticles are anchored on a two-dimensional graphene sheet. ? Enhanced photocatalytic efficiency was obtained compared to ZnO/Ag composite. ? The composite shows excellent stability after four photodegradation cycling runs. - Abstract: ZnO/Ag/graphene composite was synthesized via a facile low-temperature aqueous solution reaction. The morphology and crystal phase of the obtained samples were well characterized by SEM, TEM, and XRD. The results indicated that ZnO/Ag nanoparticles (NPs) are anchored on the two-dimensional graphene sheet. The photocatalytic trials confirmed that the ZnO/Ag/graphene composite exhibited improved photocatalytic efficiency compared with the ZnO/Ag NPs and pristine ZnO NPs. The increased photocatalytic activity of ZnO/Ag/graphene was attributed to the effective charge separation and the suppressed recombination of photogenerated electron–hole pairs. Moreover, the ZnO/Ag/graphene sample showed excellent stability after four photodegradation cycling runs.

  20. Efficient chemoenzymatic oligosaccharide synthesis by reverse phosphorolysis using cellobiose phosphorylase and cellodextrin phosphorylase from Clostridium thermocellum.

    PubMed

    Nakai, Hiroyuki; Hachem, Maher Abou; Petersen, Bent O; Westphal, Yvonne; Mannerstedt, Karin; Baumann, Martin J; Dilokpimol, Adiphol; Schols, Henk A; Duus, Jens Ø; Svensson, Birte

    2010-12-01

    Inverting cellobiose phosphorylase (CtCBP) and cellodextrin phosphorylase (CtCDP) from Clostridium thermocellum ATCC27405 of glycoside hydrolase family 94 catalysed reverse phosphorolysis to produce cellobiose and cellodextrins in 57% and 48% yield from ?-d-glucose 1-phosphate as donor with glucose and cellobiose as acceptor, respectively. Use of ?-d-glucosyl 1-fluoride as donor increased product yields to 98% for CtCBP and 68% for CtCDP. CtCBP showed broad acceptor specificity forming ?-glucosyl disaccharides with ?-(1?4)- regioselectivity from five monosaccharides as well as branched ?-glucosyl trisaccharides with ?-(1?4)-regioselectivity from three (1?6)-linked disaccharides. CtCDP showed strict ?-(1?4)-regioselectivity and catalysed linear chain extension of the three ?-linked glucosyl disaccharides, cellobiose, sophorose, and laminaribiose, whereas 12 tested monosaccharides were not acceptors. Structure analysis by NMR and ESI-MS confirmed two ?-glucosyl oligosaccharide product series to represent novel compounds, i.e. ?-D-glucopyranosyl-[(1?4)-?-D-glucopyranosyl](n)-(1?2)-D-glucopyranose, and ?-D-glucopyranosyl-[(1?4)-?-D-glucopyranosyl](n)-(1?3)-D-glucopyranose (n = 1-7). Multiple sequence alignment together with a modelled CtCBP structure, obtained using the crystal structure of Cellvibrio gilvus CBP in complex with glucose as a template, indicated differences in the subsite +1 region that elicit the distinct acceptor specificities of CtCBP and CtCDP. Thus Glu636 of CtCBP recognized the C1 hydroxyl of ?-glucose at subsite +1, while in CtCDP the presence of Ala800 conferred more space, which allowed accommodation of C1 substituted disaccharide acceptors at the corresponding subsites +1 and +2. Furthermore, CtCBP has a short Glu496-Thr500 loop that permitted the C6 hydroxyl of glucose at subsite +1 to be exposed to solvent, whereas the corresponding longer loop Thr637-Lys648 in CtCDP blocks binding of C6-linked disaccharides as acceptors at subsite +1. High yields in chemoenzymatic synthesis, a novel regioselectivity, and novel oligosaccharides including products of CtCDP catalysed oligosaccharide oligomerisation using ?-d-glucosyl 1-fluoride, all together contribute to the formation of an excellent basis for rational engineering of CBP and CDP to produce desired oligosaccharides. PMID:20678539

  1. Efficient solvent-free synthesis of phytostanyl esters in the presence of acid-surfactant-combined catalyst.

    PubMed

    He, Wen-Sen; Ma, Yuan; Pan, Xiao-Xia; Li, Jing-Jing; Wang, Mei-Gui; Yang, Ye-Bo; Jia, Cheng-Sheng; Zhang, Xiao-Ming; Feng, Biao

    2012-09-26

    An efficient approach based on the synthesis of phytostanyl esters with an acid-surfactant-combined catalyst in a solvent-free system was developed. The effect of catalyst dose, substrate molar ratio, reaction temperature, and acyl donor was considered. The reaction conditions were further optimized by response surface methodology, and a high yield of phytostanyl laurate (>92%) was obtained under optimum conditions: 3.17:1 molar ratio of lauric acid to plant stanols, 4.01% catalyst dose (w/w), 119 °C, and 4.1 h. FT-IR, MS, and NMR were adopted to confirm the chemical structure of phytostanyl laurate. Meanwhile, the physiochemical properties of different phytostanyl esters were investigated. Compared with phytostanols, the prepared phytostanyl esters had much lower melting temperature and higher oil solubility. There was no obvious difference in melting and solidification properties between sunflower oil with phytostanyl laurate (<5%) or oleate (<10%) and the original sunflower oil, suggesting that the esterification of phytostanols greatly facilitated their corporation into oil-based foods. PMID:22920263

  2. Facile Synthesis of a Furan-Arylamine Hole-Transporting Material for High-Efficiency, Mesoscopic Perovskite Solar Cells.

    PubMed

    Krishna, Anurag; Sabba, Dharani; Yin, Jun; Bruno, Annalisa; Boix, Pablo P; Gao, Yang; Dewi, Herlina A; Gurzadyan, Gagik G; Soci, Cesare; Mhaisalkar, Subodh G; Grimsdale, Andrew C

    2015-10-19

    A novel hole-transporting molecule (F101) based on a furan core has been synthesized by means of a short, high-yielding route. When used as the hole-transporting material (HTM) in mesoporous methylammonium lead halide perovskite solar cells (PSCs) it produced better device performance than the current state-of-the-art HTM 2,2',7,7'-tetrakis-(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD). The F101-HTM-based device exhibited both slightly higher Jsc (19.63 vs. 18.41?mA?cm(-2) ) and Voc (1.1 vs. 1.05?V) resulting in a marginally higher power conversion efficiency (PCE) (13.1 vs. 13?%). The steady-state and time-resolved photoluminescence show that F101 has significant charge extraction ability. The simple molecular structure, short synthesis route with high yield and better performance in devices makes F101 an excellent candidate for replacing the expensive spiro-OMeTAD as HTM in PSCs. PMID:26333387

  3. Synthesis of Porous ?-MnO2 Submicron Tubes as Highly Efficient Electrocatalyst for Rechargeable Li-O2 Batteries.

    PubMed

    Zhang, Peng; Sun, Dongfei; He, Mu; Lang, Junwei; Xu, Shan; Yan, Xingbin

    2015-06-01

    Lithium-oxygen (Li-O2 ) batteries are receiving intense interest because of their high energy density. A new tubular ?-MnO2 material prepared by a simple hydrothermal synthesis is an efficient electrocatalyst for Li-O2 batteries. The synthesized ?-MnO2 exhibits a unique tubular structure, in which the porous walls are composed of highly dispersed ultrathin ?-MnO2 nanosheets. Such a unique structure and its intrinsic catalytic activity provide the right electrocatalyst characteristics for high-performance Li-O2 batteries. As a consequence, suppressed overpotentials-especially the oxygen evolution reaction overpotential-superior rate capability, and desirable cycle life are achieved with these submicron ?-MnO2 tubes as the electrocatalyst. Remarkably, the discharge product Li2 O2 of the Li-O2 battery exhibits a uniform nanosheet-like morphology, which indicates the critical role of the ?-MnO2 in the electrochemical process, and a mechanism is proposed to analyze the catalysis of ?-MnO2 . PMID:25944388

  4. The synthesis of n-caproate from lactate: a new efficient process for medium-chain carboxylates production

    PubMed Central

    Zhu, Xiaoyu; Tao, Yong; Liang, Cheng; Li, Xiangzhen; Wei, Na; Zhang, Wenjie; Zhou, Yan; Yang, Yanfei; Bo, Tao

    2015-01-01

    A unique microbiome that metabolizes lactate rather than ethanol for n-caproate production was obtained from a fermentation pit used for the production of Chinese strong-flavour liquor (CSFL). The microbiome was able to produce n-caproate at concentrations as high as 23.41?g/L at a maximum rate of 2.97?g/L/d in batch trials without in-line extraction. Compared with previous work using ethanol as the electron donor, the n-caproate concentration increased by 82.89%. High-throughput sequencing analysis showed that the microbiome was dominated by a Clostridium cluster IV, which accounted for 79.07% of total reads. A new process for n-caproate production was proposed, lactate oxidation coupled to chain elongation, which revealed new insight into the well-studied lactate conversion and carbon chain elongation. In addition, these findings indicated a new synthesis mechanism of n-caproate in CSFL. We believe that this efficient process will provide a promising opportunity for the innovation of waste recovery as well as for n-caproate biosynthesis. PMID:26403516

  5. Solution-Phase Perfluoroalkylation of C60 Leads to Efficient and Selective Synthesis of Bis-Perfluoroalkylated Fullerenes

    PubMed Central

    Kuvychko, Igor V.; Strauss, Steven H.; Boltalina, Olga V.

    2012-01-01

    A solution-phase perfluoroalkylation of C60 with a series of RFI reagents was studied. The effects of molar ratio of the reagents, reaction time, and presence of copper metal promoter on fullerene conversion and product composition were evaluated. Ten aliphatic and aromatic RFI reagents were investigated (CF3I, C2F5I, n-C3F7I, i-C3F7I, n-C4F9I, (CF3)(C2F5)CFI, n-C8F17I, C6F5CF2I, C6F5I, and 1,3-(CF3)2C6F3I) and eight of them (except for C6F5I and 1,3-(CF3)2C6F3I) were found to add the respective RF groups to C60 in solution. Efficient and selective synthesis of C60(RF)2 derivatives was developed. PMID:25843973

  6. Synthesis of mesoporous NH2-SBA-15 by a simple and efficient strategy

    NASA Astrophysics Data System (ADS)

    You, Long; Yuan, Fang; Ma, Feng

    2015-12-01

    Amine modified SBA-15 (NH2-SBA-15) was synthesized by a simple and efficient strategy, that is, activation at first and followed by amination. The samples were characterized by fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), environmental scanning electron microscopy (ESEM), thermo gravimetric (TG) analysis, and nitrogen adsorption. Results show that the as-prepared NH2-SBA-15 possessed a large surface area, stable skeleton structure, and high amino contents. Moreover, the CO2 temperature programmed desorption (CO2-TPD) experiments of the as-prepared NH2-SBA-15 were studied, and the results show that the introduction of amino groups results in the increase of the basic sites of SBA-15, which is beneficial to the adsorption of CO2.

  7. Pullulan-protamine as efficient haemocompatible gene delivery vector: synthesis and in vitro characterization.

    PubMed

    Priya, S S; Rekha, M R; Sharma, Chandra P

    2014-02-15

    Biodegradable non-viral vectors with good transfection efficiency is essential for successful gene delivery. The purpose of this study was to design a non-viral vector by conjugating protamine to pullulan and elucidate the potential use of pullulan protamine conjugate (PPA) as an effective, non toxic and haemocompatible gene delivery system. The particle size and surface charge were measured using Nanosizer. Derivatization was confirmed by NMR, FTIR and DSC analyses. Acid base titration revealed the buffering behaviour of the conjugate. The protection of DNA from nuclease enzyme and interaction of plasma components on the stability of nanoplexes were also analysed. The uptake studies confirmed the plasmid delivery into the nucleus and the inhibitor studies determined the uptake mechanism. Transfection experiments revealed the capability of PPA to cellular uptake in C6 cells and facilitate high gene expression. Thus, PPA proves to be a promising non-viral vector. PMID:24507274

  8. Renewable rigid diamines: efficient, stereospecific synthesis of high purity isohexide diamines.

    PubMed

    Thiyagarajan, Shanmugam; Gootjes, Linda; Vogelzang, Willem; van Haveren, Jacco; Lutz, Martin; van Es, Daan S

    2011-12-16

    We report an efficient three-step strategy for synthesizing rigid, chiral isohexide diamines derived from 1,4:3,6-dianhydrohexitols. These biobased chiral building blocks are presently the subject of several investigations (in our and several other groups) because of their application in high-performance biobased polymers, such as polyamides and polyurethanes. Among the three possible stereo-isomers, dideoxy-diamino isoidide and dideoxy-diamino isosorbide can be synthesized from isomannide and isosorbide respectively in high yield with absolute stereo control. Furthermore, by using this methodology dideoxy-amino isomannide-a tricyclic adduct-was obtained starting from isoidide in high yield. Our improved synthetic route is a valuable advance towards meeting scale and purity demands for evaluating the properties of new biobased performance materials, which will benefit the development of these plastics. PMID:22121062

  9. Pd-catalyzed cross-coupling of aryllithium reagents with 2-alkoxy-substituted aryl chlorides: mild and efficient synthesis of 3,3'-diaryl BINOLs.

    PubMed

    Castelló, Luis M; Hornillos, Valentín; Vila, Carlos; Giannerini, Massimo; Fañanás-Mastral, Martín; Feringa, Ben L

    2015-01-01

    Palladium-catalyzed cross-coupling of aryllithium reagents with 2-alkoxy-substituted aryl chlorides is described. The reactions proceed under mild conditions with short reaction times and provide a wide range of 2-alkoxy-substituted biaryls. This new methodology is applied to the efficient preparation of 3,3'-diaryl BINOLs and represents the first synthesis of this important class of chiral compounds from the corresponding 3,3'-dichloro BINOLs. PMID:25514438

  10. A simple, efficient and environmentally benign synthetic protocol for the synthesis of spirooxindoles using choline chloride-oxalic acid eutectic mixture as catalyst/solvent system.

    PubMed

    Khandelwal, Sarita; Rajawat, Anshu; Tailor, Yogesh Kumar; Kumar, Mahendra

    2014-01-01

    An efficient and environmentally benign domino protocol has been presented for the synthesis of structurally diverse spirooxindoles spiroannulated with pyranopyridopyrimidines, indenopyridopyrimidines, and chromenopyridopyrimidines involving three-component reaction of aminouracils, isatins and cyclic carbonyl compounds in deep eutectic solvent (choline chloride-oxalic acid: 1:1) which acts as efficient catalyst and environmentally benign reaction medium. The present protocol offers several advantages such as operational simplicity with easy workup, shorter reaction times excellent yields with superior atom economy and environmentally benign reaction conditions with the use of cost-effective, recyclable, non-toxic and bio-degradable DES as catalyst/solvent. PMID:25329839

  11. Efficient synthesis and characterization of ergosterol laurate in a solvent-free system.

    PubMed

    He, Wen-Sen; Yin, Ji; Xu, Han-Shan; Qian, Qiu-Ying; Jia, Cheng-Sheng; Ma, Hai-Le; Feng, Biao

    2014-12-01

    Ergosterol and its derivatives have attracted much attention for a variety of health benefits, such as anti-inflammatory and antioxidant activities. However, ergosterol esters are advantageous because this compound has better solubility than the free ergosterol. In this work, ergosterol laurate was efficiently synthesized for the first time by direct esterification in a solvent-free system. The desired product was purified, characterized by Fourier transform infrared spectroscopy, mass spectrometry, and nuclear magnetic resonance, and finally confirmed to be ergosterol laurate. Meanwhile, the effect of various catalysts, catalyst dose, reaction temperature, substrate molar ratio, and reaction time were studied. Both the conversion of ergosterol and the selectivity of the desired product can reach above 89% under the selected conditions: sodium dodecyl sulfate + hydrochloric acid as the catalyst, 2:1 molar ratio of lauric acid/ergosterol, catalyst dose of 4% (w/w), 120 °C, and 2 h. The oil solubility of ergosterol and its laurate was also compared. The results showed that the solubility of ergosterol in oil was significantly improved by direct esterification with lauric acid, thus greatly facilitating the incorporation into a variety of oil-based systems. PMID:25405492

  12. Synthesis of Efficiently Green Luminescent CdSe/ZnS Nanocrystals Via Microfluidic Reaction

    NASA Astrophysics Data System (ADS)

    Luan, Weiling; Yang, Hongwei; Fan, Ningning; Tu, Shan-Tung

    2008-04-01

    Quantum dots with emission in the spectral region from 525 to 535 nm are of special interest for their application in green LEDs and white-light generation, where CdSe/ZnS core-shell structured nanocrystals (NCs) are among promising candidates. In this study, triple-ligand system (trioctylphosphine oxide oleic acid oleylamine) was designed to improve the stability of CdSe NCs during the early reaction stage. With the precisely controlled reaction temperature (285 °C) and residence time (10 s) by the recently introduced microfluidic reaction technology, green luminescent CdSe NCs (? = 522 nm) exhibiting narrow FWHM of PL (30 nm) was reproducibly obtained. After that, CdSe/ZnS core-shell NCs were achieved with efficient luminescence in the pure green spectral region, which demonstrated high PL QY up to 70% and narrow PL FWHM as 30 nm. The strengthened mass and heat transfer in the microchannel allowed the formation of highly luminescent CdSe/ZnS NCs under low reaction temperature and short residence time ( T = 120 °C, t = 10 s). The successful formation of ZnS layer was evidence of the substantial improvement of PL intensity, being further confirmed by XRD, HRTEM, and EDS study.

  13. Synthesis of magnetic metal-organic framework (MOF) for efficient removal of organic dyes from water

    NASA Astrophysics Data System (ADS)

    Zhao, Xiaoli; Liu, Shuangliu; Tang, Zhi; Niu, Hongyun; Cai, Yaqi; Meng, Wei; Wu, Fengchang; Giesy, John P.

    2015-07-01

    A novel, simple and efficient strategy for fabricating a magnetic metal-organic framework (MOF) as sorbent to remove organic compounds from simulated water samples is presented and tested for removal of methylene blue (MB) as an example. The novel adsorbents combine advantages of MOFs and magnetic nanoparticles and possess large capacity, low cost, rapid removal and easy separation of the solid phase, which makes it an excellent sorbent for treatment of wastewaters. The resulting magnetic MOFs composites (also known as MFCs) have large surface areas (79.52?m2 g-1), excellent magnetic response (14.89?emu g-1), and large mesopore volume (0.09?cm3 g-1), as well as good chemical inertness and mechanical stability. Adsorption was not drastically affected by pH, suggesting ?-? stacking interaction and/or hydrophobic interactions between MB and MFCs. Kinetic parameters followed pseudo-second-order kinetics and adsorption was described by the Freundlich isotherm. Adsorption capacity was 84?mg MB g-1 at an initial MB concentration of 30?mg L-1, which increased to 245?mg g-1 when the initial MB concentration was 300?mg L-1. This capacity was much greater than most other adsorbents reported in the literature. In addition, MFC adsorbents possess excellent reusability, being effective after at least five consecutive cycles.

  14. Group?2 Catalysis for the Atom-Efficient Synthesis of Imidazolidine and Thiazolidine Derivatives.

    PubMed

    Arrowsmith, Merle; Hill, Michael S; Kociok-Köhn, Gabriele

    2015-07-13

    A wide variety of functionalised imidazolidine-2-ones and -thiones, 2-imino-imidazolidines and thiazolidine-2-thiones have been synthesised under very mild reaction conditions by using simple and cost-effective alkaline earth bis(amide) precatalysts, [Ae{N(SiMe3 )2 }2 (THF)2 ] (Ae=Mg, Ca, Sr). The reactions ensue with 100?% atom efficiency as one-pot cascades from simple, commercially available terminal alkyne and heterocumulene reagents. The reactions take place through the initial assembly of propargylamidines, which are utilised in subsequent cyclisation reactions through addition of the isocyanate, isothiocyanate and, in one case, carbon disulfide reagents. This reactivity is deduced to take place through a well-defined sequence of heterocumulene hydroacetylenation and alkyne hydroamidation steps, which are all mediated at the alkaline earth centre. The rate and regioselectivity of the cyclisation reactions are, thus, found to be heavily dependent upon the identity of the catalytic alkaline earth centre employed. Similarly, the selectivity of the reactions was observed to be profoundly affected by stereoelectronic variations in the individual substrates, albeit by a similar Group?2-centred reaction mechanism in all cases studied. PMID:26094593

  15. Synthesis, spectral, SHG efficiency and computational studies of some newly synthesized unsymmetrical azines of 4-biphenylcarboxaldehyde.

    PubMed

    Arulmani, R; Sankaran, K R

    2014-08-14

    A series of novel unsymmetrical azines 2-8 are prepared and characterized by FT-IR, (1)H, (13)C NMR, Mass and UV spectral studies. The Gaussian-03 B3LYP/6-311+G(d,p) calculations on these azines are used to evaluate the heat of formation of the different conformers, identify the stable conformation, to determine dipole moment (?), polarizability (?0), first hyperpolarizability (?tot), selected geometrical parameters, MEP surface, frontier molecular orbital energies (HOMO-LUMO) and their energy gap. The ?, ?0, ?tot values clearly depict that the unsymmetrical azine 8 is found to have a good NLO property compared to other azines 1-7. The SHG measurement of unsymmetrical azine 8 was performed by Kurtz and Perry powder method and the results indicated that the azine 8 is having comparable efficiency as that of potassium dihydrogen phosphate (KDP) crystal. The natural bond orbital (NBO) analysis of the unsymmetrical azines 2-8 are also made using B3LYP/6-31G(d,p) basis set. PMID:24755639

  16. Synthesis of magnetic metal-organic framework (MOF) for efficient removal of organic dyes from water

    PubMed Central

    Zhao, Xiaoli; Liu, Shuangliu; Tang, Zhi; Niu, Hongyun; Cai, Yaqi; Meng, Wei; Wu, Fengchang; Giesy, John P.

    2015-01-01

    A novel, simple and efficient strategy for fabricating a magnetic metal-organic framework (MOF) as sorbent to remove organic compounds from simulated water samples is presented and tested for removal of methylene blue (MB) as an example. The novel adsorbents combine advantages of MOFs and magnetic nanoparticles and possess large capacity, low cost, rapid removal and easy separation of the solid phase, which makes it an excellent sorbent for treatment of wastewaters. The resulting magnetic MOFs composites (also known as MFCs) have large surface areas (79.52?m2 g?1), excellent magnetic response (14.89?emu g?1), and large mesopore volume (0.09?cm3 g?1), as well as good chemical inertness and mechanical stability. Adsorption was not drastically affected by pH, suggesting ?–? stacking interaction and/or hydrophobic interactions between MB and MFCs. Kinetic parameters followed pseudo-second-order kinetics and adsorption was described by the Freundlich isotherm. Adsorption capacity was 84?mg MB g?1 at an initial MB concentration of 30?mg L?1, which increased to 245?mg g?1 when the initial MB concentration was 300?mg L?1. This capacity was much greater than most other adsorbents reported in the literature. In addition, MFC adsorbents possess excellent reusability, being effective after at least five consecutive cycles. PMID:26149818

  17. Synthesis of graphene-ZnO-Au nanocomposites for efficient photocatalytic reduction of nitrobenzene.

    PubMed

    Roy, Prathik; Periasamy, Arun Prakash; Liang, Chi-Te; Chang, Huan-Tsung

    2013-06-18

    A simple hydrothermal method of preparing highly photocatalytic graphene-ZnO-Au nanocomposites (G-ZnO-Au NCs) has been developed. Zinc acetate and graphene oxide are reduced by catechin to form graphene-zinc oxide nanospheres (G-ZnO NSs; average diameter of (45.3 ± 3.7) nm) in the presence of ethylenediamine (EDA) as a stabilizing agent and gold nanorods (Au NRs) at 300 °C for 2 h. Then Au NRs are deposited onto as-formed G-ZnO NSs to form G-ZnO-Au NCs. Upon ultraviolet light activation, G-ZnO-Au NCs (4 mg mL(-1)) in methanol generates electron-hole pairs. Methanol (hydroxyl group) assists in trapping holes, enabling photogenerated electrons to catalyze reduction of nitrobenzene (NB) to aniline with a yield of 97.8% during a reaction course of 140 min. The efficiency of G-ZnO-Au NCs is 3.5- and 4.5-fold higher than those provided by commercial TiO2 and ZnO NSs, respectively. Surface assisted laser desorption/ionization mass spectrometry has been for the first time applied to detect the intermediates (nitrosobenzene and phenylhydroxylamine) and major product (aniline) of NB through photoelectrocatalytic or photocatalytic reactions. The result reveals that the reduction of NB to aniline is through nitrosobenzene to phenylhydroxylamine in the photoelectrocatalytic reaction, while via nitrosobenzene directly in the photocatalytic reaction. G-ZnO-Au NC photocatalyst holds great potential in removal of organic pollutants like NB and in the production of aniline. PMID:23701390

  18. Rational design and synthesis of efficient Carbon and/or Silica functional nanomaterials for electrocatalysis and nanomedicine

    NASA Astrophysics Data System (ADS)

    Da Silva, Rafael

    In nanomaterials there is a strong correlation between structure and properties. Thus, the design and synthesis of nanomaterials with well-defined structures and morphology is essential in order to produce materials with not only unique but also tailorable properties. The unique properties of nanomaterials in turn can be taken advantage of to create materials and nanoscale devices that can help address important societal issues, such as meeting renewable energy sources and efficient therapeutic and diagnostic methods to cure a range of diseases. In this thesis, the different synthetic approaches I have developed to produce functional nanomaterials composed of earth-abundant elements (mainly carbon and silica) at low cost in a very sustainable manner are discussed. In Chapter 1, the fundamental properties of nanomaterials and their properties and potential applications in many areas are introduced. In chapter 2, a novel synthetic method that allows polymerization of polyaniline (PANI), a conducting polymer, inside cylindrical channel pores of nanoporous silica (SBA-15) is discussed. In addition, the properties of the III resulting conducting polymer in the confined nanochannel spaces of SBA-15, and more importantly, experimental demonstration of the use of the resulting hybrid material (PANI/SBA-15 material) as electocatalyst for electrooxidation reactions with good overpotential, close to zero, are detailed. In chapter 3, the synthetic approach discussed in Chapter 2 is further extended to afford nitrogen- and oxygen-doped mesoporous carbons. This is possible by pyrolysis of the PANI/SBA-15 composite materials under inert atmosphere, followed by etching away their silica framework. The high catalytic activity of resulting carbon-based materials towards oxygen reduction reaction despite they do not possess any metal dopants is also included. The potential uses of nanomaterials in areas such as nanomedicine need deep understanding of the biocompatibility/ toxicity of the materials. In Chapter 4, comparative in vitro and in vivo assessments of the biological properties and murine lung toxicity (biocompatibility) of the carbon-based nanomaterials synthesized above and in core-shell architectures containing carbon, silica and cobalt is presented. The results indicate that silica shell is essential for biocompatibility. Furthermore, cobalt oxide is the preferred phase over the zero valent Co(0) phase to impart biocompatibility to cobalt-based nanoparticles. This study is a result of collaboration between Asefa's research group at Rutgers University and Souid's research group at United Arab Emirates University. In Chapter 5, a new synthetic method to carbon nanoneedles (or a new class of carbon nanomaterials with high aspect ratios) is presented. In the work, cellulose nanocrystals are prepared and used as precursor for carbon nanostructures. Unlike other types of carbon nanomaterials, carbon IV nanoneedles possess high surface area and large proportion of edge planes, which have outstanding charge transfer and catalytic properties. The resulting metal-free, carbon nanoneedles are shown to serve as effective electrocatalysts for oxidation of hydrazine. In Chapter 6, the synthesis of amorphous carbon nanoneedles containing cobalt and their catalytic activities for oxygen reduction reaction is discussed. Even though the activity of the materials is lower than the one discussed in Chapter 3 for polyaniline-derived mesoporous carbons, the result and discussion in this chapter provides new insights on the effects and advantages of carbon nanoneedles on the electrocatalytic activity of the materials. In addition, the effects of cobalt content and nanoneedles' structures on the catalytic activity of the materials are described. In chapter 7, the synthesis of very small Au nanoparticles within SBA-15 mesoporous silica host materials by galvanic exchange reactions is described. The resulting Au/SBA-15 materials with different size Au nanoparticles are shown to have very interesting surface plasmon resonance (SPR) activity as a result of

  19. Enzymatic Chemoselective Aldehyde-Ketone Cross-Couplings through the Polarity Reversal of Methylacetoin.

    PubMed

    Bernacchia, Giovanni; Bortolini, Olga; De Bastiani, Morena; Lerin, Lindomar Alberto; Loschonsky, Sabrina; Massi, Alessandro; Müller, Michael; Giovannini, Pier Paolo

    2015-06-01

    The thiamine diphosphate (ThDP) dependent enzyme acetoin:dichlorophenolindophenol oxidoreductase (Ao:DCPIP?OR) from Bacillus licheniformis was cloned and overexpressed in Escherichia coli. The recombinant enzyme shared close similarities with the acetylacetoin synthase (AAS) partially purified from Bacillus licheniformis suggesting that they could be the same enzyme. The product scope of the recombinant Ao:DCPIP?OR was expanded to chiral tertiary ?-hydroxy ketones through the rare aldehyde-ketone cross-carboligation reaction. Unprecedented is the use of methylacetoin as the acetyl anion donor in combination with a range of strongly to weakly activated ketones. In some cases, Ao:DCPIP?OR produced the desired tertiary alcohols with stereochemistry opposite to that obtained with other ThDP-dependent enzymes. The combination of methylacetoin as acyl anion synthon and novel ThDP-dependent enzymes considerably expands the available range of C-C bond formations in asymmetric synthesis. PMID:25914187

  20. Witting Reaction Using a Stabilized Phosphorus Ylid: An Efficient and Stereoselective Synthesis of Ethyl Trans-Cinnamate

    ERIC Educational Resources Information Center

    Speed, Traci J.; Mclntyre, Jean P.; Thamattoor, Dasan M.

    2004-01-01

    An instructive experiment for the synthesis of ethyl trans-cinnamate, a pleasant smelling ester used in perfumery and flavoring by the reaction of benzaldehyde with the stable ylid triphenylphosphorane is described. The synthesis, workup and characterization of trans-cinnamate may be accomplished in a single laboratory session with commonly…

  1. Key Building Blocks via Enzyme-Mediated Synthesis

    NASA Astrophysics Data System (ADS)

    Fischer, Thomas; Pietruszka, Jörg

    Biocatalytic approaches to valuable building blocks in organic synthesis have emerged as an important tool in the last few years. While first applications were mainly based on hydrolases, other enzyme classes such as oxidoreductases or lyases moved into the focus of research. Nowadays, a vast number of biotransformations can be found in the chemical and pharmaceutical industries delivering fine chemicals or drugs. The mild reaction conditions, high stereo-, regio-, and chemoselectivities, and the often shortened reaction pathways lead to economical and ecological advantages of enzymatic conversions. Due to the enormous number of enzyme-mediated syntheses, the present chapter is not meant to be a complete review, but to deliver comprehensive insights into well established enzymatic systems and recent advances in the application of enzymes in natural product synthesis. Furthermore, it is focused on the most frequently used enzymes or enzyme classes not covered elsewhere in the present volume.

  2. Near-Infrared Light Manipulated Chemoselective Reductions Enabled by an Upconversional Supersandwich Nanostructure.

    PubMed

    Liu, Zi-en; Wang, Jie; Li, Yan; Hu, Xiaoxia; Yin, Junwen; Peng, Yeqing; Li, Zhihao; Li, Yawen; Li, Baomin; Yuan, Quan

    2015-09-01

    Core-satellite is one of the most powerful superstructures since it leads to enhanced or completely new properties through compatible combination of each component. Here we create a novel ceria-based core-shell-satellite supersandwich structure with near-infrared (NIR) light manipulated catalytic activity by integrating the upconversion luminescent and catalytic functionality of CeO2 nanoparticles. Specifically, lanthanide-doped octahedral CeO2 nanoparticles (o-CeO2) are coated with silica layer (o-CeO2@SiO2) to enhance their luminescence intensity. The pH-dependent catalytic active cubic CeO2 nanoparticles (c-CeO2) are then assembled on the surface of o-CeO2@SiO2 to form the supersandwich structure (o-CeO2@SiO2@c-CeO2) following a classic chemical reaction. The upconversion quantum yield of o-CeO2 in this nanostructure can be nearly doubled. Furthermore, under NIR light irradiation, the o-CeO2@SiO2@c-CeO2 supersandwich structure based composite catalyst displays superior catalytic activity in selective reduction of aromatic nitro compounds to corresponding azo compounds, and the composite photocatalyst can be easily recycled for several times without significant loss of catalytic activity. This strategy may serve as a universal method for the construction of multifunctional nanostructures and shed light on the green chemistry for chemical synthesis. PMID:26270621

  3. Synthesis and characterization of low molecular weight polyethyleneimine-terminated Poly(?-amino ester) for highly efficient gene delivery of minicircle DNA.

    PubMed

    Zhao, Jing; Yang, Lei; Huang, Ping; Wang, ZhiYong; Tan, Yan; Liu, Hong; Pan, JiaJia; He, Cheng-Yi; Chen, Zhi-Ying

    2016-02-01

    Gene therapy has held great promise for treating specific acquired and inherited diseases. However, the lack of safe and efficient gene delivery systems remains as the major challenge. Poly(?-amino ester)s (PBAEs) have attracted much attention due to their outstanding properties in biosafety, DNA delivery efficiency and convenience in synthesis. In this paper, we reported the further enhancement of the PBAE functions by increasing its positive charge through conjugating with low molecular weight polyethylenimine (LPEI). The resulted LPEI-PBAE polymer was able to condense minicircle DNA (mcDNA) forming nanoparticles with a diameter of 50-200nm. Furthermore, as compared to parental PBAE and a commercial transfection reagent very common in laboratory application, the LPEI-PBAE demonstrated significantly higher transfection efficiency with little cytotoxicity. These results suggested LPEI-PBAEs are worthy of further optimization for gene therapy applications. PMID:26520815

  4. TiO2 synthesis inspired by biomineralization: control of morphology, crystal phase, and light-use efficiency in a single process.

    PubMed

    Nonoyama, Takayuki; Kinoshita, Takatoshi; Higuchi, Masahiro; Nagata, Kenji; Tanaka, Masayoshi; Sato, Kimiyasu; Kato, Katsuya

    2012-05-30

    Hydroxyapatite is mineralized along the long axis of collagen fiber during osteogenesis. Mimicking such biomineralization has great potential to control inorganic structures and is fast becoming an important next-generation inorganic synthesis method. Inorganic matter synthesized by biomineralization can have beautiful and functional structures that cannot be created artificially. In this study, we applied biomineralization to the synthesis of the only photocatalyst in practical use today, titanium dioxide (TiO(2)). The photocatalytic activity of TiO(2) mainly relates to three properties: morphology, crystal phase, and light-use efficiency. To optimize TiO(2) morphology, we used a simple sequential peptide as an organic template. TiO(2) mineralized by a ?-sheet peptide nanofiber template forms fiber-like shapes that are not observed for mineralization by peptides in the shape of random coils. To optimize TiO(2) crystal phase, we mineralized TiO(2) with the template at 400 °C to transform it into the rutile phase and at 700 °C to transform it into a mixed phase of anatase and rutile. To optimize light-use efficiency, we introduced nitrogen atoms of the peptide into the TiO(2) structure as doped elemental material during sintering. Thus, this biomineralization method enables control of inorganic morphology, crystal phase, and light-use efficiency in a single process. PMID:22578231

  5. An efficient synthesis of an exo-enone analogue of LL-Z1640-2 and evaluation of its protein kinase inhibitory activities.

    PubMed

    Wang, Stephanie Q; Goh, Shermin S; Chai, Christina L L; Chen, Anqi

    2015-12-23

    An efficient synthesis of an exo-enone analogue () of resorcylic acid lactone (RAL), natural product LL-Z1640-2 (), has been achieved using a Ni-catalysed regioselective reductive coupling macrocyclisation of an alkyne-aldehyde as a key step. The synthetic route is significantly shorter than those for the natural product and avoids the isomerisation problem of the cis-double bond in the molecule. The preliminary biological evaluation showed that the exo-enone analogue is a potent inhibitor of several important kinases relevant to cancer drug development. PMID:26541872

  6. Schwertmannite Synthesis through Ferrous Ion Chemical Oxidation under Different H2O2 Supply Rates and Its Removal Efficiency for Arsenic from Contaminated Groundwater

    PubMed Central

    Zhang, Shasha; Liu, Lanlan; Zhou, Lixiang; Fan, Wenhua

    2015-01-01

    Schwertmannite-mediated removal of arsenic from contaminated water has attracted increasing attention. However, schwertmannite chemical synthesis behavior under different H2O2 supply rates for ferrous ions oxidation is unclear. This study investigated pH, ferrous ions oxidation efficiency, and total iron precipitation efficiency during schwertmannite synthesis by adding H2O2 into FeSO4·7H2O solution at different supply rates. Specific surface area and arsenic (III) removal capacity of schwertmannite have also been studied. Results showed that pH decreased from ~3.48 to ~1.96, ~2.06, ~2.12, ~2.14, or ~2.17 after 60 h reaction when the ferrous ions solution received the following corresponding amounts of H2O2: 1.80 mL at 2 h (treatment 1); 0.90 mL at 2 h and 14 h (treatment 2); 0.60 mL at 2, 14, and 26 h (treatment 3); 0.45 mL at 2, 14, 26, and 38 h (treatment 4), or 0.36 mL at 2, 14, 26, 38, and 50 h (treatment 5). Slow H2O2 supply significantly inhibited the total iron precipitation efficiency but improved the specific surface area or arsenic (III) removal capacity of schwertmannite. For the initial 50.0 ?g/L arsenic (III)-contaminated water under pH ~7.0 and using 0.25 g/L schwertmannite as an adsorbent, the total iron precipitation efficiency, specific surface area of the harvested schwertmannite, and schwertmannite arsenic(III) removal efficiency were 29.3%, 2.06 m2/g, and 81.1%, respectively, in treatment 1. However, the above parameters correspondingly changed to 17.3%, 16.30 m2/g, and 96.5%, respectively, in treatment 5. PMID:26398214

  7. Microwave-assisted synthesis: A fast and efficient route to produce LaMO{sub 3} (M = Al, Cr, Mn, Fe, Co) perovskite materials

    SciTech Connect

    Prado-Gonjal, J.; Arevalo-Lopez, A.M.; Moran, E.

    2011-02-15

    Research highlights: {yields} Lanthanum perovskites can be prepared by microwave irradiation in a domestic set-up. {yields} Microwave-assisted synthesis yields well crystallized and pure materials, sometimes nanosized. {yields} Rietveld analysis has been performed to refine the structures. {yields} Magnetic and electric measurements are similar to those previously reported. {yields} Microwave-assisted synthesis is a fast and efficient method for the synthesis of lanthanum perovskites. -- Abstract: A series of lanthanum perovskites, LaMO{sub 3} (M = Al, Cr, Mn, Fe, Co), having important technological applications, have been successfully prepared by a very fast, inexpensive, reproducible, environment-friendly method: the microwave irradiation of the corresponding mixtures of nitrates. Worth to note, the microwave source is a domestic microwave oven. In some cases the reaction takes place in a single step, while sometimes further annealings are necessary. For doped materials the method has to be combined with others such as sol-gel. Usually, nanopowders are produced which yield high density pellets after sintering. Rietveld analysis, oxygen stoichiometry, microstructure and magnetic measurements are presented.

  8. An efficient method for solution-phase parallel synthesis of 2-quinoxalinol salen Schiff-base ligands.

    PubMed

    Wu, Xianghong; Gorden, Anne E V

    2007-01-01

    A solution-phase parallel method for the synthesis of 2-quinoxalinol salen ligands was designed and optimized. The synthesis begins with commercially available 1,5-difluoro-2, 4-dinitrobenzene (DFDNB) and employs a sequence of five straightforward and high-yielding reaction steps. Simple laboratory techniques with low sensitivity to water or air for solution-phase parallel reactions were coupled with convenient workup and purification procedures to give high-purity and yield a small ligand library of 20 compounds. The final step, a Schiff-base condensation of an aldehyde with the diaminoquinoxaline results in a new category of ligands for metal coordination or of potential bioactivity, based on the skeleton 2,2'-(1E,1'E)-(quinoxaline-6,7-diylbis(azan-1-yl-1-ylidene))bis(methan-1-yl-1-ylidene)diphenol. The approach described here is easily adaptable for parallel synthesis of a larger library. PMID:17497932

  9. Simple and efficient biomimetic synthesis of Mn3O4 hierarchical structures and their application in water treatment.

    PubMed

    Mallampati, Ramakrishna; Valiyaveettil, Suresh

    2012-01-01

    Biotemplate synthesis of functional materials is interesting owing to low cost, high yield and easy way of preparation. Recently, we have developed a simple and cost effective biomimetic synthesis of hierarchical network like nanostructures of manganese oxide (Mn3O4). Readily available eggshell membrane with nucleating and capping sites were used as a template in our synthesis. The prepared material was characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis and X-ray Diffraction (XRD). The surface area was calculated using the Brunauer-Emmett-Teller (BET) theory, and pore size distribution was obtained by Barrett-Joyner-Helenda (BJH) method. The prepared Mn3O4 showed good ability to remove organic pollutants from water and expected to be useful in effluent treatment in textile industry. PMID:22524029

  10. Controllable synthesis of mesoporous carbon nanospheres and Fe-N/carbon nanospheres as efficient oxygen reduction electrocatalysts

    NASA Astrophysics Data System (ADS)

    Wei, Jing; Liang, Yan; Zhang, Xinyi; Simon, George P.; Zhao, Dongyuan; Zhang, Jin; Jiang, Sanping; Wang, Huanting

    2015-03-01

    The synthesis of mesoporous carbon nanospheres (MCNs), especially with diameters below 200 nm remains a great challenge due to weak interactions between the carbon precursors and soft templates, as well as the uncontrollable cross-linking rate of carbon precursors. Herein, we demonstrate a simple acid-assisted, hydrothermal synthesis approach to synthesizing such uniform MCNs with well controlled diameters ranging from 20 to 150 nm under highly acidic conditions (2 M HCl). Both the carbon precursor and the template are partly protonated under such conditions and show additional Coulombic interactions with chloride ions (acts as mediators). This kind of enhanced interaction is similar to that of the ``I+X-S+'' mechanism in the synthesis of mesoporous metal oxide, which can effectively retard the cross-linking rate of resol molecules and avoid macroscopic phase separation during the hydrothermal synthesis. Due to their uniform spherical morphology, small diameter, and high surface areas, MCNs can be modified with Fe and N species via impregnation of cheap precursors (ferric nitrate and dicyandiamide), which are further converted into nonprecious electrocatalysts for oxygen reduction reactions. The resulting Fe-N/MCNs exhibit high catalytic activities, long-term stability and improved methanol tolerance under alkaline conditions, which can be potentially used in direct methanol fuel cells and metal-air batteries.The synthesis of mesoporous carbon nanospheres (MCNs), especially with diameters below 200 nm remains a great challenge due to weak interactions between the carbon precursors and soft templates, as well as the uncontrollable cross-linking rate of carbon precursors. Herein, we demonstrate a simple acid-assisted, hydrothermal synthesis approach to synthesizing such uniform MCNs with well controlled diameters ranging from 20 to 150 nm under highly acidic conditions (2 M HCl). Both the carbon precursor and the template are partly protonated under such conditions and show additional Coulombic interactions with chloride ions (acts as mediators). This kind of enhanced interaction is similar to that of the ``I+X-S+'' mechanism in the synthesis of mesoporous metal oxide, which can effectively retard the cross-linking rate of resol molecules and avoid macroscopic phase separation during the hydrothermal synthesis. Due to their uniform spherical morphology, small diameter, and high surface areas, MCNs can be modified with Fe and N species via impregnation of cheap precursors (ferric nitrate and dicyandiamide), which are further converted into nonprecious electrocatalysts for oxygen reduction reactions. The resulting Fe-N/MCNs exhibit high catalytic activities, long-term stability and improved methanol tolerance under alkaline conditions, which can be potentially used in direct methanol fuel cells and metal-air batteries. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr00331h

  11. Silver-catalyzed oxidative coupling of aniline and ene carbonyl/acetylenic carbonyl compounds: an efficient route for the synthesis of quinolines.

    PubMed

    Zhang, Xu; Xu, Xuefeng

    2014-11-01

    An efficient silver-mediated coupling of aniline with ene carbonyl/acetylenic carbonyl compounds for the synthesis of quinolines is reported. The transformation is effective for a broad range of substrates, thus enabling the expansion of substituent architectures on the heterocyclic framework. The electronic properties of the substituents on the amine have been investigated. It was found that molecules with both electron-donating and electron-withdrawing substituents were suitable substrates for this transformation, and the expected products were obtained in moderate to excellent yields. The use of a single catalytic system to mediate chemical transformations in a synthetic operation is important for the development of new atom-economic strategies and this strategy is efficient in building complex structures from simple starting materials in an environmentally benign fashion. PMID:25195503

  12. Efficient enantioselective synthesis of (R)-[3,5-bis(trifluoromethyl)phenyl] ethanol by Leifsonia xyli CCTCC M 2010241 using isopropanol as co-substrate.

    PubMed

    Ouyang, Qi; Wang, Pu; Huang, Jin; Cai, Jinbo; He, Junyao

    2013-03-01

    (R)-[3,5-Bis(trifluoromethyl)phenyl] ethanol is a key chiral intermediate for the synthesis of aprepitant. In this paper, an efficient synthetic process for (R)-[3,5- bis(trifluoromethyl)phenyl] ethanol was developed via the asymmetric reduction of 3,5-bis(trifluoromethyl) acetophenone, catalyzed by Leifsonia xyli CCTCC M 2010241 cells using isopropanol as the co-substrate for cofactor recycling. Firstly, the substrate and product solubility and cell membrane permeability of biocatalysts were evaluated with different co-substrate additions into the reaction system, in which isopropanol manifested as the best hydrogen donor of coupled NADH regeneration during the bioreduction of 3,5-bis(trifluoromethyl) acetophenone. Subsequently, the optimization of parameters for the bioreduction were undertaken to improve the effectiveness of the process. The determined efficient reaction system contained 200 mM of 3,5-bis(trifluoromethyl) acetophenone, 20% (v/v) of isopropanol, and 300 g/l of wet cells. The bioreduction was executed at 30°C and 200 rpm for 30 h, and 91.8% of product yield with 99.9% of enantiometric excess (e.e.) was obtained. The established bioreduction reaction system could tolerate higher substrate concentrations of 3,5- bis(trifluoromethyl) acetophenone, and afforded a satisfactory yield and excellent product e.e. for the desired (R)-chiral alcohol, thus providing an alternative to the chemical synthesis of (R)-[3,5-bis(trifluoromethyl)phenyl] ethanol. PMID:23462007

  13. Organocatalysis in heterocyclic synthesis: DABCO as a mild and efficient catalytic system for the synthesis of a novel class of quinazoline, thiazolo [3,2-a]quinazoline and thiazolo[2,3-b] quinazoline derivatives

    PubMed Central

    2013-01-01

    Background There are only limited publications devoted to the synthesis of especially thiazolo[3,2-a]quinazoline which involved reaction of 2-mercaptopropargyl quinazolin-4-one with various aryl iodides catalyzed by Pd-Cu or by condensation of 2-mercapto-4-oxoquinazoline with chloroacetic acid, inspite of this procedure was also reported in the literature to afford the thiazolo [2,3-b] quinazoline. So the multistep synthesis of the thiazolo[3,2-a]- quinazoline suffered from some flaws and in this study we have synthesized a novel class of thiazoloquinazolines by a simple and convenient method involving catalysis by 1,4-diazabicyclo[2.2.2]octane (DABCO). Results A new and convenient one-pot synthesis of a novel class of 2-arylidene-2H-thiazolo[3,2-a]quinazoline-1,5-diones 9a-i was established through the reaction between methyl-2-(2-thio-cyanatoacetamido)benzoate (4) and a variety of arylidene malononitriles 8a-i in the presence of DABCO as a mild and efficient catalytic system via a Michael type addition reaction and a mechanism for formation of the products observed is proposed. Moreover 4 was converted to ethyl-2-[(4-oxo-3,4-dihydroquinazolin-2-yl)thio]acetate (10) upon reflux in ethanol containing DABCO as catalyst. The latter was reacted with aromatic aldehydes and dimethylformamide dimethylacetal (DMF-DMA) to afford a mixture of two regioselectively products with identical percentage yield, these two products were identified as thiazolo[3,2-a]quinazoline 9,13 and thiazolo[2,3-b]quinazoline 11,12 derivatives respectively. The structure of the compounds prepared in this study was elucidated by different spectroscopic tools of analyses also the X-ray single crystal technique was employed in this study for structure elucidation, Z/E potential isomerism configuration determination and to determine the regioselectivity of the reactions. Conclusion A simple and efficient one-pot synthesis of a novel class of 2-arylidene-2H-thiazolo[3,2-a]quinazoline-1,5-diones 9a-i was established through DABCO catalyzed Michael type addition reaction. In addition many fused quinazoline and quinazoline derivatives were synthesized which appeared as valuable precursors in synthetic and medicinal chemistry. PMID:23651877

  14. CTAB-assisted synthesis of monoclinic BiVO4 photocatalyst and its highly efficient degradation of organic dye under visible-light irradiation.

    PubMed

    Yin, Wenzong; Wang, Wenzhong; Zhou, Lin; Sun, Songmei; Zhang, Ling

    2010-01-15

    A highly efficient monoclinic BiVO(4) photocatalyst (C-BVO) was synthesized by an aqueous method with the assistance of cetyltrimethylammonium bromide (CTAB). The structure, morphology and photophysical properties of the C-BVO were characterized by XRD, FE-SEM and diffuse reflectance spectroscopy, respectively. The photocatalytic efficiencies were evaluated by the degradation of rhodamine B (RhB) under visible-light irradiation, revealing that the degradation rate over the C-BVO was much higher than that over the reference BiVO(4) prepared by aqueous method and over the one prepared by solid-state reaction. The efficiency of de-ethylation and that of the cleavage of conjugated chromophore structure were investigated, respectively. The chemical oxygen demand (COD) values of the RhB were measured after the photocatalytic degradation over the C-BVO and demonstrated a 53% decrease in COD. The effects of CTAB on the synthesis of C-BVO were investigated, which revealed that CTAB not only changed the reaction process via the formation of BiOBr as an intermediate, but also facilitated the transition from BiOBr to BiVO(4). Comparison experiments were carried out and showed that the existence of impurity level makes significant contribution to the high photocatalytic efficiency of the C-BVO. PMID:19733435

  15. Chemical Synthesis of Circular Proteins*

    PubMed Central

    Tam, James P.; Wong, Clarence T. T.

    2012-01-01

    Circular proteins, once thought to be rare, are now commonly found in plants. Their chemical synthesis, once thought to be difficult, is now readily achievable. The enabling methodology is largely due to the advances in entropic chemical ligation to overcome the entropy barrier in coupling the N- and C-terminal ends of large peptide segments for either intermolecular ligation or intramolecular ligation in end-to-end cyclization. Key elements of an entropic chemical ligation consist of a chemoselective capture step merging the N and C termini as a covalently linked O/S-ester intermediate to permit the subsequent step of an intramolecular O/S-N acyl shift to form an amide. Many ligation methods exploit the supernucleophilicity of a thiol side chain at the N terminus for the capture reaction, which makes cysteine-rich peptides ideal candidates for the entropy-driven macrocyclization. Advances in desulfurization and modification of the thiol-containing amino acids at the ligation sites to other amino acids add extra dimensions to the entropy-driven ligation methods. This minireview describes recent advances of entropy-driven ligation to prepare circular proteins with or without a cysteinyl side chain. PMID:22700959

  16. Efficient synthesis of dihydropyrimidinones via a three-component Biginelli-type reaction of urea, alkylaldehyde and arylaldehyde

    PubMed Central

    Qu, Haijun; Li, Xuejian; Mo, Fan

    2013-01-01

    Summary A one-pot three-component synthesis of dihydropyrimidinones via a molecular iodine-catalyzed tandem reaction of simple readily available mono-substituted urea, alkylaldehyde, and arylaldehyde has been developed. The reaction proceeds with high chemo- and regioselectivity to give highly diverse dihydropyrimidinones in reasonable yields under mild reaction conditions. Moreover, the first catalytic enantioselective version of this reaction was also realized by using chiral spirocyclic SPINOL-phosphoric acids. PMID:24367449

  17. Alkyne elementometalation-Pd-catalyzed cross-coupling. Toward synthesis of all conceivable types of acyclic alkenes in high yields, efficiently, selectively, economically, and safely: "green" way.

    PubMed

    Negishi, Ei-Ichi; Wang, Guangwei; Rao, Honghua; Xu, Zhaoqing

    2010-05-21

    Palladium-catalyzed cross-coupling reactions, especially those involving Zn, Al, Zr (Negishi coupling), and B (Suzuki coupling), collectively have brought about "revolutionary" changes in organic synthesis. Thus, two regio- and stereodefined carbon groups generated as R(1)M (M = Zn, Al, B, Cu, Zr, etc.) and R(2)X (X = I, Br, OTs, etc.) may now be cross-coupled to give R(1)-R(2) with essentially full retention of all structural features. For alkene syntheses, alkyne elementometalation reactions including hydrometalation (B, Al, Zr, etc.), carbometalation (Cu, Al-Zr, etc.), and haloboration (BX(3) where X is Cl, Br, and I) have proven to be critically important. Some representative examples of highly efficient and selective (>or=98%) syntheses of di-, tri-, and oligoenes containing regio- and stereodefined di- and trisubstituted alkenes of all conceivable types will be discussed with emphasis on those of natural products. Some interesting but undesirable cases involving loss of the initial structural identities of the alkenyl groups are attributable to the formation of allylpalladium species, which must be either tamed or avoided. Some such examples involving the synthesis of 1,3-, 1,4-, and 1,5-dienes will also be discussed. PMID:20465291

  18. Efficient Synthesis and In Vivo Incorporation of Acridon-2-ylalanine, a Fluorescent Amino Acid for Lifetime and FRET/LRET Studies

    PubMed Central

    Speight, Lee C.; Muthusamy, Anand K.; Goldberg, Jacob M.; Warner, John B.; Wissner, Rebecca F.; Willi, Taylor S.; Woodman, Bradley F.; Mehl, Ryan A.; Petersson, E. James

    2014-01-01

    The amino acid acridon-2-ylalanine (Acd) can be a valuable probe of protein conformational change because it is a long lifetime, visible wavelength fluorophore that is small enough to be incorporated during ribosomal biosynthesis. Incorporation of Acd into proteins expressed in E. coli requires efficient chemical synthesis to produce large quantities of the amino acid and the generation of a mutant aminoacyl tRNA synthetase that can selectively charge the amino acid onto a tRNA. Here, we report the synthesis of Acd in 87 % yield over five steps from Tyr, and the identification of an Acd synthetase by screening candidate enzymes previously evolved from M. janaschii Tyr synthetase for unnatural amino acid incorporation. Furthermore, we characterize the photophysical properties of Acd, including quenching interactions with select natural amino acids and Förster resonance energy transfer (FRET) interactions with common fluorophores such as methoxycoumarin (Mcm). Finally, we demonstrate the value of incorporation of Acd into proteins, using changes in Acd fluorescence lifetimes, Mcm/Acd FRET, or energy transfer to Eu3+ to monitor protein folding and binding interactions. PMID:24303933

  19. Ultrasonic-assisted sol-gel synthesis of samarium, cerium co-doped TiO2 nanoparticles with enhanced sonocatalytic efficiency.

    PubMed

    Eskandarloo, Hamed; Badiei, Alireza; Behnajady, Mohammad A; Ziarani, Ghodsi Mohammadi

    2015-09-01

    In this work, pure TiO2 and samarium, cerium mono-doped and co-doped TiO2 catalysts were synthesized by an ultrasonic-assisted sol-gel method and their sonocatalytic efficiency studied toward removal of Methyl Orange as a model organic pollutant from the textile industry. The relationship of structure and sonocatalytic performance of catalysts was established by using various techniques, such as XRD, TEM, SEM, EDX, DRS, and PL. A comparison on the removal efficiency of sonolysis alone and sonocatalytic processes was performed. The results showed that the samarium, cerium co-doped TiO2 catalyst with narrower band gap energy and smaller particle size leads to a rapid removal of pollutant. It was believed that Sm(3+) and Ce(4+) ions can serve as superficial trapping for electrons at conduction band of TiO2 and prolonged the lifetime of electron-hole pairs. Finally, the effect of synthesis and operational variables on the sonocatalytic activity of co-doped TiO2 catalyst was studied and optimized using response surface methodology as a statistical technique. The results showed that the maximum removal efficiency (96.33%) was achieved at the optimum conditions: samarium content of 0.6 wt%, cerium content of 0.82 wt%, initial pollutant concentration of 4.31 mg L(-1), catalyst dosage of 0.84 mg L(-1), ultrasonic irradiation power of 700 W, and irradiation time of 50 min. PMID:25682738

  20. Phosphatidylethanolamine Synthesis in the Parasite Mitochondrion Is Required for Efficient Growth but Dispensable for Survival of Toxoplasma gondii*

    PubMed Central

    Hartmann, Anne; Hellmund, Maria; Lucius, Richard; Voelker, Dennis R.; Gupta, Nishith

    2014-01-01

    Toxoplasma gondii is a highly prevalent obligate intracellular parasite of the phylum Apicomplexa, which also includes other parasites of clinical and/or veterinary importance, such as Plasmodium, Cryptosporidium, and Eimeria. Acute infection by Toxoplasma is hallmarked by rapid proliferation in its host cells and requires a significant synthesis of parasite membranes. Phosphatidylethanolamine (PtdEtn) is the second major phospholipid class in T. gondii. Here, we reveal that PtdEtn is produced in the parasite mitochondrion and parasitophorous vacuole by decarboxylation of phosphatidylserine (PtdSer) and in the endoplasmic reticulum by fusion of CDP-ethanolamine and diacylglycerol. PtdEtn in the mitochondrion is synthesized by a phosphatidylserine decarboxylase (TgPSD1mt) of the type I class. TgPSD1mt harbors a targeting peptide at its N terminus that is required for the mitochondrial localization but not for the catalytic activity. Ablation of TgPSD1mt expression caused up to 45% growth impairment in the parasite mutant. The PtdEtn content of the mutant was unaffected, however, suggesting the presence of compensatory mechanisms. Indeed, metabolic labeling revealed an increased usage of ethanolamine for PtdEtn synthesis by the mutant. Likewise, depletion of nutrients exacerbated the growth defect (?56%), which was partially restored by ethanolamine. Besides, the survival and residual growth of the TgPSD1mt mutant in the nutrient-depleted medium also indicated additional routes of PtdEtn biogenesis, such as acquisition of host-derived lipid. Collectively, the work demonstrates a metabolic cooperativity between the parasite organelles, which ensures a sustained lipid synthesis, survival and growth of T. gondii in varying nutritional milieus. PMID:24429285

  1. [11C]PR04.MZ, a promising DAT ligand for low concentration imaging: synthesis, efficient 11C-0-methylation and initial small animal PET studies

    SciTech Connect

    Riss, P.J.; Hooker, J.; Alexoff, D.; Kim, Sung-Won; Fowler, J.S.; Roesch, F.

    2009-05-01

    PR04.MZ was designed as a highly selective dopamine transporter inhibitor, derived from natural cocaine. Its binding profile indicates that [{sup 11}C]PR04.MZ may be suited as a PET radioligand for the non-invasive exploration of striatal and extrastriatal DAT populations. As a key feature, its structural design facilitates both, labelling with fluorine-18 at its terminally fluorinated butynyl moiety and carbon-11 at its methyl ester function. The present report concerns the efficient [{sup 11}C]MeI mediated synthesis of [{sup 11}C]PR04.MZ from an O-desmethyl precursor trifluoroacetic acid salt with Rb{sub 2}CO{sub 3} in DMF in up to 95 {+-} 5% labelling yield. A preliminary {mu}PET-experiment demonstrates the reversible, highly specific binding of [{sup 11}C]PR04.MZ in the brain of a male Sprague-Dawley rat.

  2. Efficient one-pot synthesis of pyrido[2,3-d]pyrimidines catalyzed by nanocrystalline MgO in water

    NASA Astrophysics Data System (ADS)

    Rad, Amaneh Mossafaii; Mokhtary, Masoud

    2015-04-01

    The direct three-component condensation of 6-aminouracil, 6-amino-2-thiouracil or 6-amino-1,3-dimethyluracil, with arylaldehydes and malononitrile to generate a series of pyrido[2,3-d]pyrimidine derivatives has been carried out over nanocrystalline MgO with high efficiency in water as a green solvent at 80 °C. The morphology and structure of the nanocrystalline MgO were characterized by scanning electron microscopy, transmission electron microscopy and X-ray diffraction. The results confirmed the nanocrystalline MgO particle size is approximately 50 nm. This methodology offers significant improvements for the synthesis of pyrido[2,3-d]pyrimidine derivatives with regard to the yield of products, simplicity in operation, and green aspects by avoiding toxic catalysts and solvents.

  3. Efficient biocatalytic synthesis of (R)-[3,5-bis(trifluoromethyl)phenyl] ethanol by a newly isolated Trichoderma asperellum ZJPH0810 using dual cosubstrate: ethanol and glycerol.

    PubMed

    Li, Jun; Wang, Pu; He, Jun-Yao; Huang, Jin; Tang, Jun

    2013-08-01

    (R)-[3,5-bis(trifluoromethyl)phenyl] ethanol is a crucial intermediate for the synthesis of Aprepitant. An efficient biocatalytic process for (R)-[3,5-bis(trifluoromethyl)phenyl] ethanol was developed via the asymmetric reduction of 3,5-bis(trifluoromethyl) acetophenone, catalyzed by whole cells of newly isolated Trichoderma asperellum ZJPH0810 using ethanol and glycerol as dual cosubstrate for cofactor recycling. A fungal strain ZJPH0810, showing asymmetric biocatalytic activity of 3,5-bis(trifluoromethyl) acetophenone to its corresponding (R)-[3,5-bis(trifluoromethyl)phenyl] ethanol, was isolated from a soil sample. Based on its morphological and physiological characteristics and internal transcribed spacer sequence, this isolate was identified as T. asperellum ZJPH0810, which afforded an NADH-dependent (R)-stereospecific carbonyl reductase and was a promising biocatalyst for the synthesis of (R)-[3,5-bis(trifluoromethyl)phenyl] ethanol. Some key reaction parameters involved in the bioreduction catalyzed by T. asperellum ZJPH0810 were subsequently optimized. The effectiveness of (R)-[3,5-bis(trifluoromethyl)phenyl] ethanol production was significantly enhanced by employing a novel dual cosubstrate-coupled system for cofactor recycling. The established efficient bioreduction system contained 50 mM of 3,5-bis(trifluoromethyl) acetophenone and 60 g l(-1) of resting cells, employing ethanol (6.0 %, v/v) and glycerol (0.5 %, v/v) as dual cosubstrate. The bioreduction was performed in distilled water medium, at 30 °C and 200 rpm. Under the above conditions, a best yield of 93.4 % was obtained, which is nearly a 3.5-fold increase in contrast to no addition of cosubstrate. The ee value of the product reached above 98 %. This biocatalytic process shows great potential in the production of (R)-[3,5-bis(trifluoromethyl)phenyl] ethanol, a valuable chiral building block in the pharmaceutical industry. PMID:23700239

  4. An Eco-Friendly Improved Protocol for the Synthesis of Bis(3-indolyl)methanes Using Poly(4-vinylpyridinium)hydrogen Sulfate as Efficient, Heterogeneous, and Recyclable Solid Acid Catalyst

    PubMed Central

    Banothu, Janardhan; Gali, Rajitha; Velpula, Ravibabu; Bavantula, Rajitha; Crooks, Peter A.

    2013-01-01

    Highly efficient and eco-friendly protocol for the synthesis of bis(3-indolyl)methanes by the electrophilic substitution reaction of indole with aldehydes catalyzed by poly(4-vinylpyridinium)hydrogen sulfate was described. Excellent yields, shorter reaction times, simple work-up procedure, avoiding hazardous organic solvents, and reusability of the catalyst are the most obvious advantages of this method. PMID:24052864

  5. Methanobactin-mediated synthesis of gold nanoparticles supported over Al2O3 toward an efficient catalyst for glucose oxidation.

    PubMed

    Xin, Jia-Ying; Lin, Kai; Wang, Yan; Xia, Chun-Gu

    2014-01-01

    Methanobactin (Mb) is a copper-binding peptide that appears to function as an agent for copper sequestration and uptake in methanotrophs. Mb can also bind and reduce Au(III) to Au(0). In this paper, Au/Al2O3 catalysts prepared by a novel incipient wetness-Mb-mediated bioreduction method were used for glucose oxidation. The catalysts were characterized, and the analysis revealed that very small gold nanoparticles with a particle size <4 nm were prepared by the incipient wetness-Mb-mediated bioreduction method, even at 1.0% Au loading (w/w). The influence of Au loading, calcination temperature and calcination time on the specific activity of Au/Al2O3 catalysts was systematically investigated. Experimental results showed that decomposing the Mb molecules properly by calcinations can enhance the specific activity of Au/Al2O3 catalysts, though they acted as reductant and protective agents during the catalyst preparation. Au/Al2O3 catalysts synthesized by the method exhibited optimum specific activity under operational synthesis conditions of Au loading of 1.0 wt % and calcined at 450 °C for 2 h. The catalysts were reused eight times, without a significant decrease in specific activity. To our knowledge, this is the first attempt at the preparation of Au/Al2O3 catalysts by Mb-mediated in situ synthesis of gold nanoparticles. PMID:25429424

  6. Methanobactin-Mediated Synthesis of Gold Nanoparticles Supported over Al2O3 toward an Efficient Catalyst for Glucose Oxidation

    PubMed Central

    Xin, Jia-Ying; Lin, Kai; Wang, Yan; Xia, Chun-Gu

    2014-01-01

    Methanobactin (Mb) is a copper-binding peptide that appears to function as an agent for copper sequestration and uptake in methanotrophs. Mb can also bind and reduce Au(III) to Au(0). In this paper, Au/Al2O3 catalysts prepared by a novel incipient wetness-Mb-mediated bioreduction method were used for glucose oxidation. The catalysts were characterized, and the analysis revealed that very small gold nanoparticles with a particle size <4 nm were prepared by the incipient wetness-Mb-mediated bioreduction method, even at 1.0% Au loading (w/w). The influence of Au loading, calcination temperature and calcination time on the specific activity of Au/Al2O3 catalysts was systematically investigated. Experimental results showed that decomposing the Mb molecules properly by calcinations can enhance the specific activity of Au/Al2O3 catalysts, though they acted as reductant and protective agents during the catalyst preparation. Au/Al2O3 catalysts synthesized by the method exhibited optimum specific activity under operational synthesis conditions of Au loading of 1.0 wt % and calcined at 450 °C for 2 h. The catalysts were reused eight times, without a significant decrease in specific activity. To our knowledge, this is the first attempt at the preparation of Au/Al2O3 catalysts by Mb-mediated in situ synthesis of gold nanoparticles. PMID:25429424

  7. Efficient solar-driven synthesis, carbon capture, and desalinization, STEP: solar thermal electrochemical production of fuels, metals, bleach.

    PubMed

    Licht, S

    2011-12-15

    STEP (solar thermal electrochemical production) theory is derived and experimentally verified for the electrosynthesis of energetic molecules at solar energy efficiency greater than any photovoltaic conversion efficiency. In STEP the efficient formation of metals, fuels, chlorine, and carbon capture is driven by solar thermal heated endothermic electrolyses of concentrated reactants occuring at a voltage below that of the room temperature energy stored in the products. One example is CO(2) , which is reduced to either fuels or storable carbon at a solar efficiency of over 50% due to a synergy of efficient solar thermal absorption and electrochemical conversion at high temperature and reactant concentration. CO(2) -free production of iron by STEP, from iron ore, occurs via Fe(III) in molten carbonate. Water is efficiently split to hydrogen by molten hydroxide electrolysis, and chlorine, sodium, and magnesium from molten chlorides. A pathway is provided for the STEP decrease of atmospheric carbon dioxide levels to pre-industial age levels in 10 years. PMID:22025216

  8. Somatic synthesis Dendritic synthesis

    E-print Network

    Schuman, Erin M.

    Spine apparatus Polysome RNP Kinesin Protein synthesis machinery mRNA transport Turnover of local protein synthesis Impact of protein × synthesis Low High Neuron size and the benefits of localRNA deep sequencing · nanostring Synaptic input patterns Control of protein translation Protein synthesis

  9. A Herpesvirus Specific Motif of Epstein-Barr Virus DNA Polymerase Is Required for the Efficient Lytic Genome Synthesis

    PubMed Central

    Narita, Yohei; Sugimoto, Atsuko; Kawashima, Daisuke; Watanabe, Takahiro; Kanda, Teru; Kimura, Hiroshi; Tsurumi, Tatsuya; Murata, Takayuki

    2015-01-01

    Epstein-Barr virus (EBV) is associated with several malignancies, including Burkitt lymphoma and nasopharyngeal carcinoma. To overcome such disorders, understanding the molecular mechanisms of the EBV replication is important. The EBV DNA polymerase (Pol) is one of the essential factors for viral lytic DNA replication. Although it is well known that its C-terminal half, possessing DNA polymerase and 3’-5’ exonuclease activity, is highly conserved among Family B Pols, the NH2-terminal half has yet to be characterized in detail. In this study, we show that a stretch of hydrophobic amino acids within the pre-NH2-terminal domain of EBV Pol plays important role. In addition, we could identify the most essential residue for replication in the motif. These findings will shed light on molecular mechanisms of viral DNA synthesis and will help to develop new herpesviruses treatments. PMID:26123572

  10. Synthesis of ?-Ga2O3 microstructures with efficient photocatalytic activity by annealing of GaSe single crystal

    NASA Astrophysics Data System (ADS)

    Filippo, Emanuela; Tepore, Marco; Baldassarre, Francesca; Siciliano, Tiziana; Micocci, Goacchino; Quarta, Gianluca; Calcagnile, Lucio; Tepore, Antonio

    2015-05-01

    The synthesis of new ?-Ga2O3 microstructures was achieved through rapid annealing of GaSe single crystal at 850 °C in oxygen-ammonia co-flow for 30-120 min duration. The obtained micro-flowers and micro-leaves were carefully characterized through X-ray diffraction, scanning electron microscopy and Raman spectroscopy. SEM images demonstrated that the product consisted of flower-shaped microstructures, which as time elapsed evolved into leaves-like dendritic microstructures. These microstructures started off directly from oxidized single crystal. A possible growth mechanism was also proposed. Experimental results evidenced that synthesized microstructures exhibited good photocatalytic activity, better than commercial TiO2 powder (Degussa P25).

  11. One-pot synthesis of gold-palladium@palladium core-shell nanoflowers as efficient electrocatalyst for ethanol electrooxidation

    NASA Astrophysics Data System (ADS)

    Qiu, Xiaoyu; Dai, Yuxuan; Tang, Yawen; Lu, Tianhong; Wei, Shaohua; Chen, Yu

    2015-03-01

    In this work, a simple polyallylamine-assisted water-based synthesis is successfully used to synthesize high-quality gold-palladium@palladium (Au-Pd@Pd) core-shell nanoflowers. Transmission electron microscopy, X-ray powder diffraction, element mapping, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy techniques are used to characterize the morphology, structure and composition of Au-Pd@Pd core-shell nanoflowers. The as-prepared Au-Pd@Pd core-shell nanoflowers exhibit significantly enhanced electrocatalytic activity for the ethanol oxidation reaction (EOR) in basic medium compared with commercial Pd black. In addition, Au-Pd@Pd core-shell nanoflowers also show higher durability for the EOR than commercial Pd black.

  12. Gold Nanoparticles Supported on a Layered Double Hydroxide as Efficient Catalysts for the One-Pot Synthesis of Flavones.

    PubMed

    Yatabe, Takafumi; Jin, Xiongjie; Yamaguchi, Kazuya; Mizuno, Noritaka

    2015-11-01

    Flavones are a class of natural products with diverse biological activities and have frequently been synthesized by step-by-step procedures using stoichiometric amounts of reagents. Herein, a catalytic one-pot procedure for the synthesis of flavone and its derivatives is developed. In the presence of gold nanoparticles supported on a Mg-Al layered double hydroxide (Au/LDH), various kinds of flavones can be synthesized starting from 2'-hydroxyacetophenones and benzaldehydes (or benzyl alcohols). The present one-pot procedure consists of a sequence of several reactions, and Au/LDH can catalyze all these different types of reactions. The catalysis is shown to be truly heterogeneous, and Au/LDH can be readily recovered and reused. PMID:26367015

  13. Rapid Synthesis and Efficient Electrocatalytic Oxygen Reduction/Evolution Reaction of CoMn2O4 Nanodots Supported on Graphene.

    PubMed

    Du, Jing; Chen, Chengcheng; Cheng, Fangyi; Chen, Jun

    2015-06-01

    Transition-metal oxides have attracted extensive interest as oxygen-reduction/evolution reaction (ORR/OER) catalyst alternatives to precious Pt-based materials but generally exhibit limited electrocatalytic performance due to their large overpotential and low specific activity. We here report a rapid synthesis of spinel-type CoMn2O4 nanodots (NDs, below 3 nm) monodispersed on graphene for highly efficient electrocatalytic ORR/OER in 0.1 M KOH solution. The preparation of the composite involves the reaction of manganese and cobalt salts in mixed surfactant-solvent-water solution at mild temperature (120 °C) and air. CoMn2O4 NDs homogeneously distributed on carbonaceous substrates show strong coupling and facile charge transfer. Remarkably, graphene-supported CoMn2O4 NDs showed 20 mV higher ORR half-wave potential, twice the kinetic current, and better catalytic durability compared to the benchmark carbon-supported Pt nanoparticles (Pt/C). Moreover, CoMn2O4/reduced graphene oxide afforded electrocatalytic OER with a current density of 10 mA cm(-2) at a low potential of 1.54 V and a small Tafel slope of ?56 mV/dec. This indicates that the composite of CoMn2O4 nanodots monodispersed on graphene is promising as highly efficient bifunctional electrocatalysts of ORR and OER that can be used in the areas of fuel cells and rechargeable metal-air batteries. PMID:25989252

  14. Graphite oxide-mediated synthesis of porous CeO{sub 2} quadrangular prisms and their high-efficiency adsorptive performance

    SciTech Connect

    Chang, Ling; Wang, Fengxian; Xie, Dong; Zhang, Jun; Du, Gaohui

    2013-10-15

    Graphical abstract: - Highlights: • Porous CeO{sub 2} quadrangular prisms have been prepared via graphite oxide-mediated synthesis. • Dual-pore hierarchical systems are formed with the pore distributions around 4 nm and 30 nm. • Porous CeO{sub 2} exhibits a rapid adsorption to Rhodamine B with a removal efficiency of ?99%. • Porous CeO{sub 2} retains the same performances in different pH solutions. - Abstract: We report a graphite oxide-mediated approach for synthesizing porous CeO{sub 2} through a facile hydrothermal process followed by thermal annealing in air. The phase structure, morphology, microstructure and porosity of the products have been revealed by a combination of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and N{sub 2} adsorption. The as-prepared CeO{sub 2} products show well-defined quadrangular prism morphology, and they are composed of interconnected nanoparticles with diameters around 30–100 nm. In particular, the dual-pore hierarchical systems are created in the CeO{sub 2} quadrangular prisms with the pore distributions around 4 nm and 30 nm. The dye sorption capacity of the porous CeO{sub 2} is investigated, which exhibits a rapid adsorption to rhodamine B with a high removal efficiency of ?99%. Moreover, the CeO{sub 2} absorbent retains the same performances in different pH solutions.

  15. Design, synthesis and gene delivery efficiency of novel oligo-arginine-linked PEG-lipids: effect of oligo-arginine length.

    PubMed

    Furuhata, Masahiko; Kawakami, Hiroko; Toma, Kazunori; Hattori, Yoshiyuki; Maitani, Yoshie

    2006-06-19

    The design, synthesis, and evaluation of in vitro gene delivery efficacy of a novel series of oligo-Arg-lipid conjugates are described. 3,5-Bis(dodecyloxy)benzamide (BDB) was employed as the lipid component, and a poly(ethylene glycol) (PEG) spacer was introduced between the C-terminal of oligo-Arg and the amide group of BDB. Four derivatives with various oligo-Arg lengths (ArgN-PEG-BDB; N = 4, 6, 8, 10: the number of arginine residues) were prepared, and the effect of oligo-Arg length on the gene transfection was investigated in HeLa cells. Transfection efficiency increased as the number of arginine residues increased. Arg10-PEG-BDB showed the highest transfection efficiency, without severe toxicity to cells. These findings well corresponded to the cellular association of the Arg-PEG-BDB/DNA complex determined by flow cytometry. Even in the presence of serum, Arg10-PEG-BDB achieved appreciable cellular association and attained high gene expression. Thus, Arg10-PEG-BDB is potentially a simple and useful gene delivery tool, because one need only to mix it with plasmid DNA and apply the complexes to the cells even in a serum-containing medium. PMID:16600534

  16. Highly efficient enzymatic synthesis of tert-butyl (S)-6-chloro-5-hydroxy-3-oxohexanoate with a mutant alcohol dehydrogenase of Lactobacillus kefir.

    PubMed

    He, Xiu-Juan; Chen, Shao-Yun; Wu, Jian-Ping; Yang, Li-Rong; Xu, Gang

    2015-11-01

    tert-Butyl (S)-6-chloro-5-hydroxy-3-oxohexanoate ((S)-CHOH) is a valuable chiral synthon, which is used for the synthesis of the cholesterol-lowering drugs atorvastatin and rosuvastatin. To date, only the alcohol dehydrogenases from Lactobacillus brevis (LbADH) and Lactobacillus kefir (LkADH) have demonstrated catalytic activity toward the asymmetric reduction of tert-butyl 6-chloro-3,5-dioxohexanoate (CDOH) to (S)-CHOH. Herein, a tetrad mutant of LkADH (LkTADH), A94T/F147L/L199H/A202L, was screened to be more efficient in this bioreduction process, exhibiting a 3.7- and 42-fold improvement in specific activity toward CDOH (1.27 U/mg) over LbADH (0.34 U/mg) and wild-type LkADH (0.03 U/mg), respectively. The molecular basis for the improved catalytic activity of LkTADH toward CDOH was investigated using homology modeling and docking analysis. Two major issues had a significant impact on the biocatalytic efficiency of this process, including (i) the poor aqueous stability of the substrate and (ii) partial substrate inhibition. A fed-batch strategy was successfully developed to address these issues and maintain a suitably low substrate concentration throughout the entire process. Several other parameters were also optimized, including the pH, temperature, NADP(+) concentration and cell loading. A final CDOH concentration of 427 mM (100 g/L) gave (S)-CHOH in 94 % yield and 99.5 % e.e. after a reaction time of 38 h with whole cells expressing LkTADH. The space-time yield and turnover number of NADP(+) in this process were 10.6 mmol/L/h and 16,060 mol/mol, respectively, which were the highest values ever reported. This new approach therefore represents a promising alternative for the efficient synthesis of (S)-CHOH. PMID:26004803

  17. Modeling, synthesis and study of highly efficient solar cells based on III-nitride nanowire arrays grown on Si substrates

    NASA Astrophysics Data System (ADS)

    Mozharov, A. M.; Bolshakov, A. D.; Kudryashov, D. A.; Kryzhanovskaya, N. V.; Cirlin, G. E.; Mukhin, I. S.; Harmand, J. C.; Tchernysheva, M.

    2015-11-01

    In this letter we investigate photovoltaic properties of GaN nanowires (NWs) – Si substrate heterostructure obtained by molecular beam epitaxy (MBE). Antireflection properties of the NW array were studied theoretically and experimentally to show an order of magnitude enhancement in antireflection comparing to the pure Si surface (2.5% vs. 33.8%). In order to determine optimal morphology and doping levels of the structure with maximum possible efficiency we simulated it's properties using a finite difference method. The carried out simulation showed that a maximum efficiency should be 20%.

  18. Highly Efficient Chemoenzymatic Synthesis of R-Galactosyl Epitopes with a Recombinant R(1f3)-Galactosyltransferase

    E-print Network

    Chen, Xi

    in antibody-mediated hyperacute rejection in xenotransplantation. This report describes an efficient of xenotransplantation and immunotherapy. A truncated bovine R1,3-GalT (80-368) was cloned into the pET15b vector-Gal epitopes binding specifically to human anti-Gal antibodies during the xenotransplantation.2 Such epitopes

  19. Facile synthesis of biocompatible cysteine-coated CuS nanoparticles with high photothermal conversion efficiency for cancer therapy.

    PubMed

    Liu, Xijian; Li, Bo; Fu, Fanfan; Xu, Kaibing; Zou, Rujia; Wang, Qian; Zhang, Bingjie; Chen, Zhigang; Hu, Junqing

    2014-08-14

    The semiconductor compounds have been proven to be promising candidates as a new type of photothermal therapy agent, but unsatisfactory photothermal conversion efficiencies limit their widespread application in photothermal therapy (PTT). Herein, we synthesized cysteine-coated CuS nanoparticles (Cys-CuS NPs) as highly efficient PTT agents by a simple aqueous solution method. The Cys-CuS NPs have a good biocompatibility owing to their biocompatible cysteine coating and exhibit a strong absorption in the near-infrared region due to the localized surface plasma resonances of valence-band free carriers. The photothermal conversion efficiency of Cys-CuS NPs reaches 38.0%, which is much higher than that of the recently reported Cu9S5 and Cu(2-x)Se nanocrystals. More importantly, tumor growth can be efficiently inhibited in vivo by the fatal heat arising from the excellent photothermal effect of Cys-CuS NPs at a low concentration under the irradiation of a 980 nm laser with a safe power density of 0.72 W cm(-2). Therefore, the Cys-CuS NPs have great potential as ideal photothermal agents for cancer therapy. PMID:24950757

  20. AN EFFICIENT AQUEOUS N-HETEROCYCLIZATION OF ANILINE DERIVATIVES: MICROWAVE-ASSISTED SYNTHESIS OF N-ARYL AZACYCLOALKANES

    EPA Science Inventory

    N-aryl azacycloalkanes, an important class of building blocks in natural product and pharmaceuticals, are synthesized via an efficient and simple eco-friendly protocol that involves double N-alkylation of aniline derivatives. The reaction is accelerated by exposure to microwaves ...

  1. An efficient and practical synthesis of [2-(11)C]indole via superfast nucleophilic [(11)C]cyanation and RANEY® Nickel catalyzed reductive cyclization.

    PubMed

    Lee, So Jeong; Fowler, Joanna S; Alexoff, David; Schueller, Michael; Kim, Dohyun; Nauth, Alexander; Weber, Carina; Kim, Sung Won; Hooker, Jacob M; Ma, Ling; Qu, Wenchao

    2015-12-14

    A rapid method for the synthesis of carbon-11 radiolabeled indole was developed using a sub-nanomolar quantity of no-carrier-added [(11)C]cyanide as radio-precursor. Based upon a reported synthesis of 2-(2-nitrophenyl)acetonitrile (), a highly reactive substrate 2-nitrobenzyl bromide () was evaluated for nucleophilic [(11)C]cyanation. Additionally, related reaction conditions were explored with the goal of obtaining of highly reactive 2-(2-nitrophenyl)-[1-(11)C]acetonitrile () while inhibiting its rapid conversion to 2,3-bis(2-nitrophenyl)-[1-(11)C]propanenitrile (). Next, a RANEY® Nickel catalyzed reductive cyclization method was utilized for synthesizing the desired [2-(11)C]indole with hydrazinium monoformate as the active reducing agent. Extensive and iterative screening of basicity, temperature and stoichiometry was required to overcome the large stoichiometry bias that favored 2-nitrobenzylbromide () over [(11)C]cyanide, which both caused further alkylation of the desired nitrile and poisoned the RANEY® Nickel catalyst. The result is an efficient two-step, streamlined method to reliably synthesize [2-(11)C]indole with an entire radiochemical yield of 21 ± 2.2% (n = 5, ranging from 18-24%). The radiochemical purity of the final product was >98% and specific activity was 176 ± 24.8 GBq ?mol(-1) (n = 5, ranging from 141-204 GBq ?mol(-1)). The total radiosynthesis time including product purification by semi-preparative HPLC was 50-55 min from end of cyclotron bombardment. PMID:26411301

  2. Synthesis of highly efficient antibacterial agent Ag doped ZnO nanorods: Structural, Raman and optical properties

    SciTech Connect

    Jan, Tariq; Iqbal, Javed; Ismail, Muhammad; Mahmood, Arshad

    2014-04-21

    Here, synthesis, structural, morphological, Raman, optical properties and antibacterial activity of undoped and Ag doped ZnO nanorods by chemical co-precipitation technique have been reported. Structural analysis has revealed that Ag doping cannot deteriorate the structure of ZnO and wurtzite phase is maintained. Lattice constants are found to be decreased with the Ag doping. Fourier transform infrared and Raman spectroscopy also confirm the X-ray diffraction results. Scanning electron microscopy results have demonstrated the formation of ZnO nanorods with average diameter and length of 96?nm and 700?nm, respectively. Raman spectroscopy results suggest that the Ag doping enhances the number of defects in ZnO crystal. It has been found from optical study that Ag doping results in positional shift of band edge absorption peak. This is attributed to the successful incorporation of Ag dopant into ZnO host matrix. The antibacterial activity of prepared nanorods has been determined by two different methods and compared to that of undoped ZnO nanorods. Ag doped ZnO nanorods exhibit excellent antibacterial activity as compared to that of undoped ZnO nanorods. This excellent antibacterial activity may be attributed to the presence of oxygen vacancies and Zn{sup 2+} interstitial defects. Our preliminary findings suggest that Ag doped ZnO nanorods can be used externally to control the spreading of infections related with tested bacterial strains.

  3. Efficient phyto-synthesis and structural characterization of rutile TiO2 nanoparticles using Annona squamosa peel extract

    NASA Astrophysics Data System (ADS)

    Roopan, Selvaraj Mohana; Bharathi, A.; Prabhakarn, A.; Abdul Rahuman, A.; Velayutham, K.; Rajakumar, G.; Padmaja, R. D.; Lekshmi, Mohan; Madhumitha, G.

    2012-12-01

    In the present study, the biosynthesis of rutile TiO2 nanoparticles (TiO2 NPs) was achieved by a novel, biodegradable and convenient procedure using fruit peel Annona squamosa aqueous extract. This is the first report on the new, simple, rapid, eco-friendly and cheaper methods for the synthesis of rutile TiO2 NPs at lower temperature using agricultural waste. Rutile TiO2 NPs were characterized by UV, XRD, SEM, TEM and EDS studies. The UV-Vis spectrophotometer results were promising and showed a rapid production of TiO2 NPs with a surface plasmon resonance occurring at 284 nm. The formation of the TiO2 NPs as observed from the XRD spectrum is confirmed to be TiO2 particles in the rutile form as evidenced by the peaks at 2? = 27.42°, 36.10°, 41.30° and 54.33° when compared with the literature. The TEM images showed polydisperse nanoparticles with spherical shapes and size 23 ± 2 nm ranges.

  4. Highly efficient synthesis of exopolysaccharides by Lactobacillus curvatus DPPMA10 during growth in hydrolyzed wheat flour agar.

    PubMed

    Minervini, F; De Angelis, M; Surico, R F; Di Cagno, R; Gänzle, M; Gobbetti, M

    2010-06-30

    The aim of this study was to optimize the production of exopolysaccharides (EPS) by sourdough Lactobacillus curvatus DPPMA10 for industrial application. The effects of pH, temperature, planktonic or attached cells and of some food matrices as substrates were studied. Wheat flour hydrolysate (WFH), reconstituted skimmed milk (RSM) and whey milk were supplemented with fresh yeast extract, mineral salts, and/or molasses. Non-controlled pH, starting from 5.6 to 3.5, was the optimal condition for L. curvatus DPPMA10. Temperature of 30 degrees C was also found to be optimal. Solid surfaces (agar culture media) stimulated attached bacteria to synthesize EPS (> or = of two-fold, P<0.05) with respect to planktonic cells (broth media). The highest production of EPS (ca. 46-50 g/kg of wet medium) was found during growth as attached cells in WFH agar supplemented with glucose, sucrose or molasses, mineral salts and fresh yeast extract at 30 degrees C for 48 h. As shown by high-performance liquid chromatography analysis, glucose was the only hydrolysis end-product for EPS synthesized during 48 h of incubation. The EPS synthesized by L. curvatus DPPMA10 improved the quality of bread and was utilized as carbon course by intestinal strains of lactobacilli and bifidobacteria. The synthesis of EPS by L. curvatus DPPMA10 under the conditions of this study may open new perspectives for their industrial applications. PMID:20398955

  5. Controlled in-situ synthesis of silver nanoparticles in natural cellulose fibers toward highly efficient antimicrobial materials.

    PubMed

    Zhu, Chunyang; Xue, Jianfeng; He, Junhui

    2009-05-01

    In this report, we presented in-situ synthesis of silver nanoparticles in natural cellulose fibers which embody high oxygen (ether and hydroxyl) density and could be considered as aggregated nanoreactors and stabilizers for the nucleation and growth of silver nanoparticles. The morphologies of natural cellulose fibers and silver nanoparticles were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV-visible spectroscopy. The content of silver nanoparticles in cellulose fibers was measured by inductive coupled plasma-mass spectrometry (ICP-ms). Experimental results revealed that sodium borohydride (NaBH4) played dual effects in the formation of silver nanoparticles. The mean size (d) and size distribution (sigma) of silver nanoparticles could be adjusted by changing the concentration of NaBH4. Monodisperse silver nanoparticles (d = 2.7 nm, sigma = 0.6 nm) in cellulose fibers were successfully prepared under optimized conditions. When the NaBH4 concentration was very low (0.1 mM), a stable colloidal solution (storage stability > 1 month) of silver nanoparticles was produced, which provides a novel, mild approach to the preparation of stable colloidal solutions of metal nanoparticles. The ability of silver nanoparticle-loaded cellulose fibers to prohibit the propagation of Escherichia coli was estimated by the Minimum Inhibitory Concentration (MIC). Based on the experimental observations, the antibacterial mode of silver nanoparticle-loaded cellulose fibers was discussed in details. PMID:19452971

  6. High surface area zincosilicates as efficient catalysts for the synthesis of ethyl lactate: an in-depth structural investigation.

    PubMed

    Collard, Xavier; Louette, Pierre; Fiorilli, Sonia; Aprile, Carmela

    2015-10-28

    Novel Zn-MCM-41 mesoporous materials with particle diameters ranging from 20 to 120 nm were successfully prepared following a straightforward synthesis route. The structural and textural properties of the solids were characterized by N2-physisorption, X-ray diffraction, (29)Si MAS-NMR, TEM and EDX. These results allow evidencing the presence of an ordered mesoporous structure with a very high specific surface area. The insertion of zinc as single site species within the silica framework was investigated using XPS via the Auger parameter in a Wagner plot representation. This is the first time that an in-depth investigation of these types of solids using XPS techniques was performed. The presence of Brønsted and Lewis acidity was elucidated by following in the IR the interaction with ammonia and carbon monoxide. The materials were tested for the conversion of dihydroxyacetone into ethyl lactate with good results both in terms of yield and selectivity and the catalytic activity resulted in excellent agreement with IR and XPS analysis. PMID:26394539

  7. Continuous Flow Polymer Synthesis toward Reproducible Large-Scale Production for Efficient Bulk Heterojunction Organic Solar Cells.

    PubMed

    Pirotte, Geert; Kesters, Jurgen; Verstappen, Pieter; Govaerts, Sanne; Manca, Jean; Lutsen, Laurence; Vanderzande, Dirk; Maes, Wouter

    2015-10-01

    Organic photovoltaics (OPV) have attracted great interest as a solar cell technology with appealing mechanical, aesthetical, and economies-of-scale features. To drive OPV toward economic viability, low-cost, large-scale module production has to be realized in combination with increased top-quality material availability and minimal batch-to-batch variation. To this extent, continuous flow chemistry can serve as a powerful tool. In this contribution, a flow protocol is optimized for the high performance benzodithiophene-thienopyrroledione copolymer PBDTTPD and the material quality is probed through systematic solar-cell evaluation. A stepwise approach is adopted to turn the batch process into a reproducible and scalable continuous flow procedure. Solar cell devices fabricated using the obtained polymer batches deliver an average power conversion efficiency of 7.2?%. Upon incorporation of an ionic polythiophene-based cathodic interlayer, the photovoltaic performance could be enhanced to a maximum efficiency of 9.1?%. PMID:26388210

  8. Bioinspired synthesis of nitrogen/sulfur co-doped graphene as an efficient electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Zhang, Huanhuan; Liu, Xiangqian; He, Guangli; Zhang, Xiaoxing; Bao, Shujuan; Hu, Weihua

    2015-04-01

    Efficient electrocatalyst of oxygen reduction reaction (ORR) is crucial for a variety of renewable energy applications and heteroatom-doped carbon materials have demonstrated promising catalytic performance towards ORR. In this paper we report a bioinspired method to synthesize nitrogen/sulfur (N/S) co-doped graphene as an efficient ORR electrocatalyst via self-polymerization of polydopamine (PDA) thin layer on graphene oxide sheets, followed by reacting with cysteine and finally thermal annealing in Argon (Ar) atmosphere. As-prepared N/S co-doped graphene exhibits significantly enhanced ORR catalytic activity in alkaline solution compared with pristine graphene or N-doped graphene. It also displays long-term operation stability and strong tolerance to methanol poison effect, indicating it a promising ORR electrocatalyst.

  9. Efficient synthesis of stably adenylated DNA and RNA adapters for microRNA capture using T4 RNA ligase 1

    PubMed Central

    Song, Yunke; Liu, Kelvin J; Wang, Tza-Huei

    2015-01-01

    MicroRNA profiling methods have become increasingly important due to the rapid rise of microRNA in both basic and translational sciences. A critical step in many microRNA profiling assays is adapter ligation using pre-adenylated adapters. While pre-adenylated adapters can be chemically or enzymatically prepared, enzymatic adenylation is preferred due to its ease and high yield. However, previously reported enzymatic methods either require tedious purification steps or use thermostable ligases that can generate side products during the subsequent ligation step. We have developed a highly efficient, template- and purification-free, adapter adenylation method using T4 RNA ligase 1. This method is capable of adenylating large amounts of adapter at ~100% efficiency and can efficiently adenylate both DNA and RNA bases. We find that the adenylation reaction speed can differ between DNA and RNA and between terminal nucleotides, leading to bias if reactions are not allowed to run to completion. We further find that the addition of high PEG levels can effectively suppress these differences. PMID:26500066

  10. Total Synthesis of Laulimalide: Synthesis of the Northern and Southern Fragments

    PubMed Central

    Seganish, W. Michael; Chung, Cheol K.; Amans, Dominique

    2012-01-01

    The first stage of the development of a synthetic route for the total synthesis of laulimalide (1) is described. Our retrosynthetic analysis envisioned a novel macrocyclization route to the natural product using a Ru-catalyzed alkene-alkyne coupling. This would be preceded by an esterification of the C19 hydroxyl group, joining together two equally sized synthons, the northern fragment 7 and the southern fragment 8. Our first generation approach to the northern fragment entailed a key sequential Ru-Pd coupling sequence to assemble the dihydropyran. The key reactions proceeded smoothly, however, the inability to effect a key olefin migration led to the development of an alternative route based on an asymmetric dinuclear Zn-catalyzed aldol reaction of a hydroxyl acylpyrrole. This key reaction led to the desired diol adduct 66 with excellent syn:anti selectivity (10:1), and allowed for the successful completion of the northern fragment 7. The key step for the synthesis of the southern fragment was a chemoselective Rh-catalyzed cycloisomerization reaction to form the dihydropyran ring from a diyne precursor. This reaction proved to be selective for the formation of a six-membered ring, over a seven. The use of an electron-deficient bidentate phosphine allowed for the reaction to proceed with a reduced catalyst loading. PMID:22307837

  11. Integrated lipase production and in situ biodiesel synthesis in a recombinant Pichia pastoris yeast: an efficient dual biocatalytic system composed of cell free enzymes and whole cell catalysts

    PubMed Central

    2014-01-01

    Background Lipase-catalyzed biotransformation of acylglycerides or fatty acids into biodiesel via immobilized enzymes or whole cell catalysts has been considered as one of the most promising methods to produce renewable and environmentally friendly alternative liquid fuels, thus being extensively studied so far. In all previously pursued approaches, however, lipase enzymes are prepared in an independent process separated from enzymatic biodiesel production, which would unavoidably increase the cost and energy consumption during industrial manufacture of this cost-sensitive energy product. Therefore, there is an urgent need to develop novel cost-effective biocatalysts and biocatalytic processes with genuine industrial feasibility. Result Inspired by the consolidated bioprocessing of lignocellulose to generate bioethanol, an integrated process with coupled lipase production and in situ biodiesel synthesis in a recombinant P. pastoris yeast was developed in this study. The novel and efficient dual biocatalytic system based on Thermomyces lanuginosus lipase took advantage of both cell free enzymes and whole cell catalysts. The extracellular and intracellular lipases of growing yeast cells were simultaneously utilized to produce biodiesel from waste cooking oils in situ and in one pot. This integrated system effectively achieved 58% and 72% biodiesel yield via concurrent esterified-transesterified methanolysis and stepwise hydrolysis-esterification at 3:1 molar ratio between methanol and waste cooking oils, respectively. Further increasing the molar ratio of methanol to waste cooking oils to 6:1 led to an 87% biodiesel yield using the stepwise strategy. Both water tolerance and methanol tolerance of this novel system were found to be significantly improved compared to previous non-integrated biodiesel production processes using separately prepared immobilized enzymes or whole cell catalysts. Conclusion We have proposed a new concept of integrated biodiesel production. This integrated system couples lipase production to lipase-catalyzed biodiesel synthesis in one pot. The proof-of-concept was established through construction of a recombinant P. pastoris yeast strain that was able to grow, overexpress T. lanuginosus lipase, and efficiently catalyze biodiesel production from fed waste cooking oils and methanol simultaneously. This simplified single-step process represents a significant advance toward achieving economical production of biodiesel at industrial scale via a ‘green’ biocatalytic route. PMID:24713071

  12. A novel method of synthesis of small band gap SnS nanorods and its efficient photocatalytic dye degradation.

    PubMed

    Das, Dipika; Dutta, Raj Kumar

    2015-11-01

    A facile one pot method has been developed for synthesis of stable (?=-37.5 mV), orthorhombic structured SnS nanorods capped with mercaptoacetic acid by precipitation method. The SnS nanorods were measured to be about 45 nm long with a diameter of 20 nm, as studied by transmission electron microscopy (TEM). The band gap of the MAA capped SnS nanorods was 1.81 eV, measured by diffused reflectance spectroscopy and was larger than the bulk SnS. The relative positions of highest valence band and lowest conduction band were determined from theoretical band structure calculation as 1.58 eV and -0.23 eV, respectively. The UV-Visible-NIR fluorescence emission spectrum of the SnS nanorods revealed intense emission peak at 1000 nm (1.239 eV) and weaker peaks at 935 nm, 1080 nm, 1160 nm which is likely to be due to Sn(2+) vacancies. The as-synthesized SnS nanorods exhibited more than 95% sunlight induced photocatalytic degradation of trypan blue in 4 h, following first order kinetics with high rate of degradation (k) (0.0124 min(-1)). The observed dye degradation is attributable to generation of reactive oxygen species (ROS), confirmed from terephthalic acid assay. The ROS generation has been explained on the basis of interaction between photoexcited electrons from conduction band with molecular oxygen adhered to the surface of nanorods owing to favourable redox potentials of O2/O2(-) (-0.20 eV) in normal hydrogen electrode (NHE) scale. PMID:26196717

  13. The economies of synthesis

    PubMed Central

    Newhouse, Timothy

    2010-01-01

    In this tutorial review the economies of synthesis are analysed from both detailed and macroscopic perspectives, using case-studies from complex molecule synthesis. Atom, step, and redox economy are more than philosophical constructs, but rather guidelines, which enable the synthetic chemist to design and execute an efficient synthesis. Students entering the field of synthesis might find this tutorial helpful for understanding the subtle differences between these economic principles and also see real-world situations where such principles are put into practice. PMID:19847337

  14. Synthesis of hierarchical porous ?-MnO2 nanoboxes as an efficient catalyst for rechargeable Li-O2 batteries

    NASA Astrophysics Data System (ADS)

    Zhang, Jian; Luan, Yanping; Lyu, Zhiyang; Wang, Liangjun; Xu, Leilei; Yuan, Kaidi; Pan, Feng; Lai, Min; Liu, Zhaolin; Chen, Wei

    2015-09-01

    A rechargeable lithium-oxygen (Li-O2) battery with a remarkably high theoretical energy storage capacity has attracted enormous research attention. However, the poor oxygen reduction and oxygen evolution reaction (ORR and OER) activities in discharge and charge processes cause low energy efficiency, poor electrolyte stability and short cycle life. This requires the development of efficient cathode catalysts to dramatically improve the Li-O2 battery performances. MnO2-based materials are recognized as efficient and low-cost catalysts for a Li-O2 battery cathode. Here, we report a controllable approach to synthesize hierarchical porous ?-MnO2 nanoboxes by using Prussian blue analogues as the precursors. The obtained products possess hierarchical pore size and an extremely large surface area (249.3 m2 g-1), which would favour oxygen transportation and provide more catalytically active sites to promote ORR and OER as the Li-O2 battery cathode. The battery shows enhanced discharge capacity (4368 mA h g-1@0.08 mA cm-2), reduced overpotential (270 mV), improved rate performance and excellent cycle stability (248 cycles@500 mA h g-1 and 112 cycles@1000 mA h g-1), in comparison with the battery with a VX-72 carbon cathode. The superb performance of the hierarchical porous ?-MnO2 nanoboxes, together with a convenient fabrication method, presents an alternative to develop advanced cathode catalysts for the Li-O2 battery.A rechargeable lithium-oxygen (Li-O2) battery with a remarkably high theoretical energy storage capacity has attracted enormous research attention. However, the poor oxygen reduction and oxygen evolution reaction (ORR and OER) activities in discharge and charge processes cause low energy efficiency, poor electrolyte stability and short cycle life. This requires the development of efficient cathode catalysts to dramatically improve the Li-O2 battery performances. MnO2-based materials are recognized as efficient and low-cost catalysts for a Li-O2 battery cathode. Here, we report a controllable approach to synthesize hierarchical porous ?-MnO2 nanoboxes by using Prussian blue analogues as the precursors. The obtained products possess hierarchical pore size and an extremely large surface area (249.3 m2 g-1), which would favour oxygen transportation and provide more catalytically active sites to promote ORR and OER as the Li-O2 battery cathode. The battery shows enhanced discharge capacity (4368 mA h g-1@0.08 mA cm-2), reduced overpotential (270 mV), improved rate performance and excellent cycle stability (248 cycles@500 mA h g-1 and 112 cycles@1000 mA h g-1), in comparison with the battery with a VX-72 carbon cathode. The superb performance of the hierarchical porous ?-MnO2 nanoboxes, together with a convenient fabrication method, presents an alternative to develop advanced cathode catalysts for the Li-O2 battery. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02983j

  15. Synthesis of hierarchical porous ?-MnO2 nanoboxes as an efficient catalyst for rechargeable Li-O2 batteries.

    PubMed

    Zhang, Jian; Luan, Yanping; Lyu, Zhiyang; Wang, Liangjun; Xu, Leilei; Yuan, Kaidi; Pan, Feng; Lai, Min; Liu, Zhaolin; Chen, Wei

    2015-09-28

    A rechargeable lithium-oxygen (Li-O2) battery with a remarkably high theoretical energy storage capacity has attracted enormous research attention. However, the poor oxygen reduction and oxygen evolution reaction (ORR and OER) activities in discharge and charge processes cause low energy efficiency, poor electrolyte stability and short cycle life. This requires the development of efficient cathode catalysts to dramatically improve the Li-O2 battery performances. MnO2-based materials are recognized as efficient and low-cost catalysts for a Li-O2 battery cathode. Here, we report a controllable approach to synthesize hierarchical porous ?-MnO2 nanoboxes by using Prussian blue analogues as the precursors. The obtained products possess hierarchical pore size and an extremely large surface area (249.3 m(2) g(-1)), which would favour oxygen transportation and provide more catalytically active sites to promote ORR and OER as the Li-O2 battery cathode. The battery shows enhanced discharge capacity (4368 mA h g(-1)@0.08 mA cm(-2)), reduced overpotential (270 mV), improved rate performance and excellent cycle stability (248 cycles@500 mA h g(-1) and 112 cycles@1000 mA h g(-1)), in comparison with the battery with a VX-72 carbon cathode. The superb performance of the hierarchical porous ?-MnO2 nanoboxes, together with a convenient fabrication method, presents an alternative to develop advanced cathode catalysts for the Li-O2 battery. PMID:26290962

  16. Metal-organic framework-templated synthesis of magnetic nanoporous carbon as an efficient absorbent for enrichment of phenylurea herbicides.

    PubMed

    Liu, Xingli; Wang, Chun; Wu, Qiuhua; Wang, Zhi

    2015-04-22

    Nanoporous carbon with a high specific surface area and unique porous structure represents an attractive material as an adsorbent in analytical chemistry. In this study, a magnetic nanoporous carbon (MNC) was fabricated by direct carbonization of Co-based metal-organic framework in nitrogen atmosphere without using any additional carbon precursors. The MNC was used as an effective magnetic adsorbent for the extraction and enrichment of some phenylurea herbicides (monuron, isoproturon, diuron and buturon) in grape and bitter gourd samples prior to their determination by high performance liquid chromatography with ultraviolet detection. Several important experimental parameters that could influence the extraction efficiency were investigated and optimized. Under the optimum conditions, a good linearity was achieved in the concentration range of 1.0-100.0 ng g(-1) for monuron, diuron and buturon and 1.5-100.0 ng g(-1) for isoproturon with the correlation coefficients (r) larger than 0.9964. The limits of detection (S/N=3) of the method were in the range from 0.17 to 0.46 ng g(-1). The results indicated that the MNC material was stable and efficient adsorbent for the magnetic solid-phase extraction of phenylurea herbicides and would have a great application potential for the extraction and preconcentration of more organic pollutants from real samples. PMID:25819788

  17. Facile synthesis of TiO2/trititanate heterostructure with enhanced photoelectric efficiency for an improved photocatalysis

    NASA Astrophysics Data System (ADS)

    Chen, Feitai; Li, Youji; Liu, Zhi; Fang, Pengfei

    2015-06-01

    TiO2/trititanate photocatalyst was prepared by alkaline hydrothermal treatment of TiO2, and characterized by transmission electron microscopy, X-ray diffraction, and Raman etc. The photocatalytic activities of catalysts were evaluated by the photocatalytic degradation of rhodamine B (RhB). It is found that the heterostructure can be directly formed via the conversion of surface TiO2 into trititanate. The coupled nanostructure possesses enhanced adsorption ability for RhB as compared with the raw TiO2, owing to the formation of an increased amount of hydroxyl groups on the prepared catalyst surface. Besides, the generated trititanate can successfully introduce a shallow energy level in the coupled composite, which results in the improvement of separation efficiency of photoinduced electron-hole pairs. In the degradation experiments, TiO2/trititanate exhibits much higher photocatalytic activity than the bare TiO2. These advantages of the coupled nanostructure in adsorption capacity and photoelectric efficiency may make it a wider application for the removal of organic pollutants.

  18. Characterization of Halomonas sp. Strain H11 ?-Glucosidase Activated by Monovalent Cations and Its Application for Efficient Synthesis of ?-d-Glucosylglycerol

    PubMed Central

    Saburi, Wataru; Yamamoto, Takeshi; Kudo, Toshiaki

    2012-01-01

    An ?-glucosidase (HaG) with the following unique properties was isolated from Halomonas sp. strain H11: (i) high transglucosylation activity, (ii) activation by monovalent cations, and (iii) very narrow substrate specificity. The molecular mass of the purified HaG was estimated to be 58 kDa by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). HaG showed high hydrolytic activities toward maltose, sucrose, and p-nitrophenyl ?-d-glucoside (pNPG) but to almost no other disaccharides or malto-oligosaccharides higher than trisaccharides. HaG showed optimum activity to maltose at 30°C and pH 6.5. Monovalent cations such as K+, Rb+, Cs+, and NH4+ increased the enzymatic activity to 2- to 9-fold of the original activity. These ions shifted the activity-pH profile to the alkaline side. The optimum temperature rose to 40°C in the presence of 10 mM NH4+, although temperature stability was not affected. The apparent Km and kcat values for maltose and pNPG were significantly improved by monovalent cations. Surprisingly, kcat/Km for pNPG increased 372- to 969-fold in their presence. HaG used some alcohols as acceptor substrates in transglucosylation and was useful for efficient synthesis of ?-d-glucosylglycerol. The efficiency of the production level was superior to that of the previously reported enzyme Aspergillus niger ?-glucosidase in terms of small amounts of by-products. Sequence analysis of HaG revealed that it was classified in glycoside hydrolase family 13. Its amino acid sequence showed high identities, 60%, 58%, 57%, and 56%, to Xanthomonas campestris WU-9701 ?-glucosidase, Xanthomonas campestris pv. raphani 756C oligo-1,6-glucosidase, Pseudomonas stutzeri DSM 4166 oligo-1,6-glucosidase, and Agrobacterium tumefaciens F2 ?-glucosidase, respectively. PMID:22226947

  19. Efficient one-pot synthesis of hydrophilic and fluorescent molecularly imprinted polymer nanoparticles for direct drug quantification in real biological samples.

    PubMed

    Niu, Hui; Yang, Yaqiong; Zhang, Huiqi

    2015-12-15

    Efficient one-pot synthesis of hydrophilic and fluorescent molecularly imprinted polymer (MIP) nanoparticles and their application as optical chemosensor for direct drug quantification in real, undiluted biological samples are described. The general principle was demonstrated by preparing tetracycline (Tc, a broad-spectrum antibiotic)-imprinted fluorescent polymer nanoparticles bearing hydrophilic polymer brushes via poly(2-hydroxyethyl methacrylate) (PHEMA) macromolecular chain transfer agent-mediated reversible addition-fragmentation chain transfer (RAFT) precipitation polymerization in the presence of a fluorescent monomer. The introduction of hydrophilic PHEMA brushes and fluorescence labeling onto/into the MIP nanoparticles proved to not only significantly improve their surface hydrophilicity and lead to their obvious specific binding and high selectivity toward Tc in the undiluted bovine serum, but also impart them with strong fluorescent properties. In particular, significant fluorescence quenching was observed upon their binding with Tc in such complex biological milieu, which makes these Tc-MIP nanoparticles useful optical chemosensor with a detection limit of 0.26 ?M. Furthermore, such advanced functional MIP nanoparticles-based chemosensor was also successfully utilized for the direct, sensitive, and accurate determination of Tc in another biological medium (i.e., the undiluted pig serum) with average recoveries ranging from 98% to 102%, even in the presence of several interfering drugs. PMID:26164489

  20. Efficient two-step chemo-enzymatic synthesis of all-trans-retinyl palmitate with high substrate concentration and product yield.

    PubMed

    Liu, Zhi-Qiang; Zhou, Ling-Mei; Liu, Peng; Baker, Peter James; Liu, Shan-Shan; Xue, Ya-Ping; Xu, Ming; Zheng, Yu-Guo

    2015-11-01

    A new two-step chemo-enzymatic approach for highly efficient synthesis of all-trans-retinyl palmitate is constructed in this study. In the first step, retinyl acetate as starting material was fully hydrolyzed to retinol by potassium hydroxide. In the hydrolysis system, anhydrous ethanol was the best co-solvent to increase the solubility of retinyl acetate. The addition amounts of 5 M potassium hydroxide and anhydrous ethanol were 8 and 10 mL against 10 g retinyl acetate, respectively, and 100 % hydrolysis rate was obtained. In the second step, esterification was catalyzed by immobilized lipase on macroporous acrylic resin AB-8 using the extracted retinol and palmitic acid as substrates in non-aqueous system. After optimization, the parameters of esterification reaction were confirmed as follows: non-aqueous solvent was selected as n-hexane, washing times of extraction solution was four times, retinol concentration was 300 g/L, substrate molar ratio of retinol to palmitic acid was 1:1.1, the amount of immobilized enzyme was 10 g/L, and the esterification temperature was 30 °C. Under the optimal conditions, this protocol resulted in a 97.5 % yield of all-trans-retinyl palmitate in 700-L reactor. After purification, all-trans-retinyl palmitate was obtained with above 99 % of purity and 88 % of total recovery rate. This methodology provides a promising strategy for the large-scale production of all-trans-retinyl palmitate. PMID:26224426

  1. Tris(2-aminoethyl)amine-based ?-branched fatty acid amides - Synthesis of lipids and comparative study of transfection efficiency of their lipid formulations.

    PubMed

    Erdmann, Nicole; Wölk, Christian; Schulze, Ingo; Janich, Christopher; Folz, Manuela; Drescher, Simon; Dittrich, Matthias; Meister, Annette; Vogel, Jürgen; Groth, Thomas; Dobner, Bodo; Langner, Andreas

    2015-10-01

    The synthesis of a new class of cationic lipids, tris(2-aminoethyl)amine-based ?-branched fatty acid amides, is described resulting in a series of lipids with specific variations in the lipophilic as well as the hydrophilic part of the lipids. In-vitro structure/transfection relationships were established by application of complexes of these lipids with plasmid DNA (pDNA) to different cell lines. The ?-branched fatty acid amide bearing two tetradecyl chains and two lysine molecules (T14diLys) in mixture with the co-lipid 1,2-di-[(9Z)-octadec-9-enoyl]-sn-glycero-3-phosphoethanolamine (DOPE) (1/2, n/n) exhibits effective pDNA transfer in three different cell lines, namely Hep-G2, A549, and COS-7. The presence of 10% serum during lipoplex incubation of the cells did not affect the transfection efficiency. Based on that, detailed investigations of the complexation of pDNA with the lipid formulation T14diLys/DOPE 1/2 (n/n) were carried out with respect to particle size and charge using dynamic light scattering (DLS), ?-potential measurements, and transmission electron microscopy (TEM). Additionally, the lipoplex uptake was investigated by confocal laser scanning microscopy (CLSM). Overall, lipoplexes prepared from T14diLys/DOPE 1/2 (n/n) offer large potential as lipid-based polynucleotide carriers and further justify advanced examinations. PMID:26325061

  2. Facile one-step synthesis of N-doped ZnO micropolyhedrons for efficient photocatalytic degradation of formaldehyde under visible-light irradiation

    NASA Astrophysics Data System (ADS)

    Wu, Changle

    2014-11-01

    N-doped ZnO micropolyhedrons were fabricated by calcining the mixture of commercial ZnO (analytical grade) and NH4NO3 at 600 °C for 1.5 h, in which NH4NO3 was utilized as the nitrogen source. The structure, composition, BET specific surface area and optical properties of N-doped ZnO sample were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, wavelength dispersive X-ray fluorescence spectroscopy, field emission scanning electron microscopy, high resolution transmission electron microscopy, N2 adsorption-desorption isotherms, and UV-vis diffuse reflectance spectroscopy. The photocatalytic results demonstrated that the as-synthesized N-doped ZnO microcrystals possessed much higher photocatalytic activity than N-doped TiO2 (which was synthesized by calcining the mixture of P25 TiO2 and NH4NO3 at 600 °C for 1.5 h) and commercial pure ZnO in the decomposition of formaldehyde under visible-light (? > 420 nm) irradiation. The present work suggests that NH4NO3 is a promising nitrogen source for one-step calcination synthesis of microcrystalline N-doped ZnO, which can be applied as a visible-light-activated photocatalyst in efficient utilization of solar energy for treating formaldehyde wastewater.

  3. Designed synthesis of multi-walled carbon nanotubes@Cu@MoS2 hybrid as advanced electrocatalyst for highly efficient hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Li, Feng; Li, Jing; Lin, Xiaoqing; Li, Xinzhe; Fang, Yiyun; Jiao, Lixin; An, Xincai; Fu, Yan; Jin, Jun; Li, Rong

    2015-12-01

    Design and synthesis of non-precious-metal catalyst for efficient electrochemical transformation of water to molecular hydrogen in acid environments is of paramount importance in reducing energy losses during the water splitting process. Here, the hybrid material of MoS2-coated Cu loaded on the multi-walled carbon nanotubes (MWCNTs@Cu@MoS2) was synthesized using chemical process and hydrothermal method. It was found that the participation of MWCNTs and Cu nanoparticles not only improved the electrical conductivity of the catalyst, but also further enhanced the catalytic activity by synergistic effect with edge-exposed MoS2-coating. Electrochemical experiments demonstrated that the catalyst exhibited excellent hydrogen evolution reaction (HER) activity with large cathode currents (small overpotential of 184 mV for 10 mA cm-2 current density) and a Tafel slope as small as 62 mV per decade. Furthermore, it was discovered that the current density of this composite catalyst had a little decrease after the continual 1000 cycling, which showed the catalyst had a high stability in the recycling process. These findings confirmed that this catalyst was a useful and earth-abundant material for water splitting.

  4. Fast and Highly Chemoselective Alkynylation of Thiols with Hypervalent Iodine Reagents Enabled through a Low Energy Barrier Concerted Mechanism

    PubMed Central

    2014-01-01

    Among all functional groups, alkynes occupy a privileged position in synthetic and medicinal chemistry, chemical biology, and materials science. Thioalkynes, in particular, are highly useful, as they combine the enhanced reactivity of the triple bond with a sulfur atom frequently encountered in bioactive compounds and materials. Nevertheless, general methods to access these compounds are lacking. In this article, we describe the mechanism and full scope of the alkynylation of thiols using ethynyl benziodoxolone (EBX) hypervalent iodine reagents. Computations led to the discovery of a new, three-atom concerted transition state with a very low energy barrier, which rationalizes the high reaction rate. On the basis of this result, the scope of the reaction was extended to the synthesis of aryl- and alkyl-substituted alkynes containing a broad range of functional groups. New sulfur nucleophiles such as thioglycosides, thioacids, and sodium hydrogen sulfide were also alkynylated successfully to lead to the most general and practical method yet reported for the synthesis of thioalkynes. PMID:25365776

  5. Controlled synthesis of CuInS2/reduced graphene oxide nanocomposites for efficient dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Zhou, Lei; Yang, Xiao; Yang, Bo; Zuo, Xueqin; Li, Guang; Feng, Ali; Tang, Huaibao; Zhang, Haijun; Wu, Mingzai; Ma, Yongqing; Jin, Shaowei; Sun, Zhaoqi; Chen, Xiaoshuang

    2014-12-01

    A nanocomposite comprised CuInS2 and reduced graphene oxide have been successfully synthesized via a facile two-step hydrothermal route using graphene oxide, thiourea, Indium chloride tetrahydrate and cuprous chloride as the raw materials, and L-Ascorbic acid as the reductant. Compared with pristine CuInS2, CuInS2 and reduced graphene oxide nanocomposites exploited as counter electrodes have exhibited outstanding electrocatalytic activity for the reduction of triiodide and excellent chemical stability due to the introduction of reduced graphene oxide. The characterization measurements indicate that the power conversion efficiency of dye-sensitized solar cell fabricated with CuInS2 and reduced graphene oxide nanocomposites counter electrode achieves 6.96%, which is higher than that of device using pristine CuInS2 counter electrode (5.49%), and comparable to the conventional platinum counter electrode (6.92%) under the same test conditions.

  6. Confined-space alloying of nanoparticles for the synthesis of efficient PtNi fuel-cell catalysts.

    PubMed

    Baldizzone, Claudio; Mezzavilla, Stefano; Carvalho, Hudson W P; Meier, Josef Christian; Schuppert, Anna K; Heggen, Marc; Galeano, Carolina; Grunwaldt, Jan-Dierk; Schüth, Ferdi; Mayrhofer, Karl J J

    2014-12-15

    The efficiency of polymer electrolyte membrane fuel cells is strongly depending on the electrocatalyst performance, that is, its activity and stability. We have designed a catalyst material that combines both, the high activity for the decisive cathodic oxygen reduction reaction associated with nanoscale Pt alloys, and the excellent durability of an advanced nanostructured support. Owing to the high specific activity and large active surface area, the catalyst shows extraordinary mass activity values of 1.0?A?mgPt(-1). Moreover, the material retains its initial active surface area and intrinsic activity during an extended accelerated aging test within the typical operation range. This excellent performance is achieved by confined-space alloying of the nanoparticles in a controlled manner in the pores of the support. PMID:25354360

  7. New tetracyclic tacrine analogs containing pyrano[2,3-c]pyrazole: efficient synthesis, biological assessment and docking simulation study.

    PubMed

    Khoobi, Mehdi; Ghanoni, Farzaneh; Nadri, Hamid; Moradi, Alireza; Pirali Hamedani, Morteza; Homayouni Moghadam, Farshad; Emami, Saeed; Vosooghi, Mohsen; Zadmard, Reza; Foroumadi, Alireza; Shafiee, Abbas

    2015-01-01

    A new series of tacrine-based acetylcholinesterase (AChE) inhibitors 7a-l were designed by replacing the benzene ring of tacrine with aryl-dihydropyrano[2,3-c]pyrazole. The poly-functionalized hybrid molecules 7a-l were efficiently synthesized through multi-component reaction and subsequent Friedländer reaction between the obtained pyrano[2,3-c]pyrazoles and cyclohexanone. Most of target compounds showed potent and selective anti-AChE activity at sub-micromolar range. The most potent compound 7h bearing a 3,4-dimethoxyphenyl group was more active than reference drug tacrine. The representative compound 7h could significantly protect neurons against oxidative stress as potent as quercetin at low concentrations. The docking study of compound 7h with AChE enzyme revealed that the (R)-enantiomer binds preferably to CAS while the (S)-enantiomer prone to be a PAS binder. PMID:25462245

  8. Assessment of production conditions for efficient use of Escherichia coli in high-yield heterologous recombinant selenoprotein synthesis.

    PubMed

    Rengby, Olle; Johansson, Linda; Carlson, Lars A; Serini, Elena; Vlamis-Gardikas, Alexios; Kårsnäs, Per; Arnér, Elias S J

    2004-09-01

    The production of heterologous selenoproteins in Escherichia coli necessitates the design of a secondary structure in the mRNA forming a selenocysteine insertion sequence (SECIS) element compatible with SelB, the elongation factor for selenocysteine insertion at a predefined UGA codon. SelB competes with release factor 2 (RF2) catalyzing translational termination at UGA. Stoichiometry between mRNA, the SelB elongation factor, and RF2 is thereby important, whereas other expression conditions affecting the yield of recombinant selenoproteins have been poorly assessed. Here we expressed the rat selenoprotein thioredoxin reductase, with titrated levels of the selenoprotein mRNA under diverse growth conditions, with or without cotransformation of the accessory bacterial selA, selB, and selC genes. Titration of the selenoprotein mRNA with a pBAD promoter was performed in both TOP10 and BW27783 cells, which unexpectedly could not improve yield or specific activity compared to that achieved in our prior studies. Guided by principal component analysis, we instead discovered that the most efficient bacterial selenoprotein production conditions were obtained with the high-transcription T7lac-driven pET vector system in presence of the selA, selB, and selC genes, with induction of production at late exponential phase. About 40 mg of rat thioredoxin reductase with 50% selenocysteine content could thereby be produced per liter bacterial culture. These findings clearly illustrate the ability of E. coli to upregulate the selenocysteine incorporation machinery on demand and that this is furthermore strongly augmented in late exponential phase. This study also demonstrates that E. coli can indeed be utilized as cell factories for highly efficient production of heterologous selenoproteins such as rat thioredoxin reductase. PMID:15345395

  9. ?-Keto esters from ketones and ethyl chloroformate: a rapid, general, efficient synthesis of pyrazolones and their antimicrobial, in silico and in vitro cytotoxicity studies

    PubMed Central

    2013-01-01

    Background Pyrazolones are traditionally synthesized by the reaction of ?-keto esters with hydrazine and its derivatives. There are methods to synthesize ?-keto esters from esters and aldehydes, but these methods have main limitation in varying the substituents. Often, there are a number of methods such as acylation of enolates in which a chelating effect has been employed to lock the enolate anion using lithium and magnesium salts; however, these methods suffer from inconsistent yields in the case of aliphatic acylation. There are methods to synthesize ?-keto esters from ketones like caboxylation of ketone enolates using carbon dioxide and carbon monoxide sources in the presence of palladium or transition metal catalysts. Currently, the most general and simple method to synthesize ?-keto ester is the reaction of dimethyl or ethyl carbonate with ketone in the presence of strong bases which also requires long reaction time, use of excessive amount of reagent and inconsistent yield. These factors lead us to develop a simple method to synthesize ?-keto esters by changing the base and reagent. Results A series of ?-keto esters were synthesized from ketones and ethyl chloroformate in the presence of base which in turn are converted to pyrazolones and then subjected to cytotoxicity studies towards various cancer cell lines and antimicrobial activity studies towards various bacterial and fungal strains. Conclusion The ?-keto esters from ethyl chloroformate was successfully attempted, and the developed method is simple, fast and applicable to the ketones having the alkyl halogens, protecting groups like Boc and Cbz that were tolerated and proved to be useful in the synthesis of fused bicyclic and tricyclic pyrazolones efficiently using cyclic ketones. Since this method is successful for different ketones, it can be useful for the synthesis of pharmaceutically important pyrazolones also. The synthesized pyrazolones were subjected to antimicrobial, docking and cytotoxicity assay against ACHN (human renal cell carcinoma), Panc-1 (human pancreatic adenocarcinoma) and HCT-116 (human colon cancer) cell line, and lead molecules have been identified. Some of the compounds are found to have promising activity against different bacterial and fungal strains tested. PMID:23870758

  10. Synthesis of halogen-doped reduced graphene oxide nanosheets as highly efficient metal-free electrocatalyst for oxygen reduction reaction.

    PubMed

    Kakaei, Karim; Balavandi, Amin

    2016-02-01

    We demonstrate F-, Cl-, Br- and I-doped reduced graphene oxide (XRGO) as metal-free graphene electro-catalysts for oxygen reduction reaction (ORR) in alkaline media. Reduced graphene oxide (GO) is prepared from graphite electrode using electrochemical exfoliation. In situ doping of halide in a graphene film has many problems. In this technique, different halides individually or all of them were mixed with the RGO and ionic liquids precursor at H2SO4 solution. Then we have evaluated the effectiveness of doping and performed electrochemical measurements of the ORR activity on XRGO. Fourier-transform infrared spectroscopy spectra show a variety of the halogen-containing functional groups. Energy-dispersive X-ray spectroscopy analysis confirmed the presence of doped halogens in RGO. Raman spectroscopy shows a high density of defects in the RGO layer. The electrochemical properties of the XRGO catalysts on carbon paper as a gas diffusion electrode (GDE) are investigated by several electrochemical methods in oxygen saturated alkaline solutions. The catalytic activity of the XRGO and Pt-C electrodes for ORR is 50 and 30mAcm(-2) at -1V in GDEs. This enhanced efficiency is the result of the influence of the nature and percentage of the halogen, especially fluorine presence in the graphene layer. PMID:26513736

  11. Synthesis of highly phosphonic acid functionalized benzene-bridged periodic mesoporous organosilicas for use as efficient dye adsorbents.

    PubMed

    Deka, Juti Rani; Liu, Chia-Ling; Wang, Tzu-Hua; Chang, Wei-Chieh; Kao, Hsien-Ming

    2014-08-15

    Periodic mesoporous organosilicas (PMOs) with benzene bridging groups in the silica wall were functionalized with a tunable content of phosphonic acid groups. These bifunctional materials were synthesized by co-condensation of two different organosilane precursors, that is, 1,4-bis(triethoxysilyl)benzene (BTEB) and sodium 3-(trihydroxysilyl)propyl methyl phosphate (SPMP), under acidic conditions using nonionic surfactant Brij-S10 as template. The materials exhibited well-ordered mesostructures and were characterized by X-ray diffraction, nitrogen sorption, TEM, TGA, FTIR, and solid-state NMR measurements. The materials thus obtained were employed as adsorbents to remove different types of dyes, for example, cationic dyes methylene blue and phenosafranine, anionic orange II, and amphoteric rhodamine B, from aqueous solutions. The materials exhibited a remarkably high adsorption capacity than activated carbon due to their ordered mesostructures, a large number of phosphonic acid groups, and high surface areas. The adsorption was mainly governed by electrostatic interaction, but also involved ?-? stacking interaction as well as hydrogen bonding. The adsorption kinetics can be better fitted by the pseudo-second order model. The adsorption process was controlled by the mechanisms of external mass transfer and intraparticle diffusion. The materials retained more than 97% dye removal efficiency after use for five consecutive cycles. PMID:25010459

  12. Magnesiothermic synthesis of sulfur-doped graphene as an efficient metal-free electrocatalyst for oxygen reduction.

    PubMed

    Wang, Jiacheng; Ma, Ruguang; Zhou, Zhenzhen; Liu, Guanghui; Liu, Qian

    2015-01-01

    Efficient metal-free electrocatalysts for oxygen reduction reaction (ORR) are highly expected in future low-cost energy systems. We have successfully prepared crumpled, sheet-like, sulfur-doped graphene by magnesiothermic reduction of easily available, low-cost, nontoxic CO2 (in the form of Na2CO3) and Na2SO4 as the carbon and sulfur sources, respectively. At high temperature, Mg can reduce not only carbon in the oxidation state of +4 in CO3(2-) to form graphene, but also sulfur in SO4(2-) from its highest (+6) to lowest valence which was hybridized into the carbon sp(2) framework. Various characterization results show that sulfur-doped graphene with only few layers has an appropriate sulfur content, hierarchically robust porous structure, large surface area/pore volume, and highly graphitized textures. The S-doped graphene samples exhibit not only a high activity for ORR with a four-electron pathway, but also superior durability and tolerance to MeOH crossover to 40% Pt/C. This is mainly ascribed to the combination of sulfur-related active sites and hierarchical porous textures, facilitating fast diffusion of oxygen molecules and electrolyte to catalytic sites and release of products from the sites. PMID:25790856

  13. Magnesiothermic synthesis of sulfur-doped graphene as an efficient metal-free electrocatalyst for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Wang, Jiacheng; Ma, Ruguang; Zhou, Zhenzhen; Liu, Guanghui; Liu, Qian

    2015-03-01

    Efficient metal-free electrocatalysts for oxygen reduction reaction (ORR) are highly expected in future low-cost energy systems. We have successfully prepared crumpled, sheet-like, sulfur-doped graphene by magnesiothermic reduction of easily available, low-cost, nontoxic CO2 (in the form of Na2CO3) and Na2SO4 as the carbon and sulfur sources, respectively. At high temperature, Mg can reduce not only carbon in the oxidation state of +4 in CO32- to form graphene, but also sulfur in SO42- from its highest (+6) to lowest valence which was hybridized into the carbon sp2 framework. Various characterization results show that sulfur-doped graphene with only few layers has an appropriate sulfur content, hierarchically robust porous structure, large surface area/pore volume, and highly graphitized textures. The S-doped graphene samples exhibit not only a high activity for ORR with a four-electron pathway, but also superior durability and tolerance to MeOH crossover to 40% Pt/C. This is mainly ascribed to the combination of sulfur-related active sites and hierarchical porous textures, facilitating fast diffusion of oxygen molecules and electrolyte to catalytic sites and release of products from the sites.

  14. Synthesis of ?-Cyclodextrin-Based Electrospun Nanofiber Membranes for Highly Efficient Adsorption and Separation of Methylene Blue.

    PubMed

    Zhao, Rui; Wang, Yong; Li, Xiang; Sun, Bolun; Wang, Ce

    2015-12-01

    Water-insoluble ?-cyclodextrin-based fibers were synthesized by electrospinining followed by thermal cross-linking. The fibers were characterized by field-emission scanning electron microscopic (FE-SEM) and Fourier transformed infrared spectrometer (FT-IR). The highly insoluble fraction obtained from different pH values (3-11) indicates successful cross-linking reactions and their usability in aqueous solution. After the cross-linking reaction, the fibers' tensile strength increases significantly and the BET surface area is 19.49 m(2)/g. The cross-linked fibers exhibited high adsorption capacity for cationic dye methylene blue (MB) with good recyclability. The adsorption performance can be fitted well with pseudo-second-order model and Langmuir isotherm model. The maximum adsorption capacity is 826.45 mg/g according to Langmuir fitting. Due to electrostatic repulsion, the fibers show weak adsorption toward negatively charged anionic dye methyl orange (MO). On the basis of the selective adsorption, the fiber membrane can separate the MB/MO mixture solution by dynamic filtration at a high flow rate of 150 mL/min. The fibers can maintain good fibrous morphology and high separation efficiency even after five filtration-regeneration cycles. The obtained results suggested potential applications of ?-cyclodextrin-based electrospun fibers in the dye wastewater treatment field. PMID:26572223

  15. Research Update: Facile synthesis of CoFe2O4 nano-hollow spheres for efficient bilirubin adsorption

    NASA Astrophysics Data System (ADS)

    Rakshit, Rupali; Pal, Monalisa; Chaudhuri, Arka; Mandal, Madhuri; Mandal, Kalyan

    2015-11-01

    Herein, we report an unprecedented bilirubin (BR) adsorption efficiency of CoFe2O4 (CFO) nanostructures in contrast to the commercially available activated carbon and resin which are generally used for haemoperfusion and haemodialysis. We have synthesized CFO nanoparticles of diameter 100 nm and a series of nano-hollow spheres of diameter 100, 160, 250, and 350 nm using a simple template free solvothermal technique through proper variation of reaction time and capping agent, oleylamine (OLA), respectively, and carried out SiO2 coating by employing Stöber method. The comparative BR adsorption study of CFO and SiO2 coated CFO nanostructures indicates that apart from porosity and hollow configuration of nanostructures, the electrostatic affinity between anionic carboxyl group of BR and cationic amine group of OLA plays a significant role in adsorbing BR. Finally, we demonstrate that the BR adsorption capacity of the nanostructures can be tailored by varying the morphology as well as size of the nanostructures. We believe that our developed magnetic nanostructures could be considered as a potential material towards therapeutic applications against hyperbilirubinemia.

  16. Synthesis and high-efficiency methylene blue adsorption of magnetic PAA/MnFe2O4 nanocomposites

    NASA Astrophysics Data System (ADS)

    Wang, Wei; Ding, Zui; Cai, Minhan; Jian, Haitao; Zeng, Zhiqiao; Li, Feng; Liu, J. Ping

    2015-08-01

    MnFe2O4 nanoparticles and polyacrylic acid PAA/MnFe2O4 nanocomposites were synthesized by a hydrothermal method and ultrasonic mixing process. The obtained materials were characterized by XRD, FTIR, SEM, TEM, and VSM. XRD patterns indicate that the synthesized MnFe2O4 nanoparticles have a single cubic spinel phase. SEM images confirm the existence of three types of basic morphology of MnFe2O4 nanoparticles: octahedral, flower-like, and plate-like particles. High saturation magnetization Ms (up to 74.6 emu/g) of the as-synthesized MnFe2O4 nanoparticles was obtained. Experiments demonstrate that the variation of the hydrothermal reaction time does not remarkably affect the magnetic properties of MnFe2O4 nanoparticles. In PAA/MnFe2O4 nanocomposites, the coating of PAA leads to a slight decrease in magnetization of MnFe2O4 nanoparticles. Additionally, PAA coating greatly enhances the adsorption properties of MnFe2O4 nanoparticles for Methylene Blue (MB) dye. Especially, the removal efficiency reaches 96.3%. This research indicates that the as-synthesized PAA/MnFe2O4 nanocomposites exhibit excellent magnetic properties and can be taken as a promising adsorbent for removal of MB dye in industrial scale.

  17. Efficient one-pot synthesis of peapod-like hollow carbon nanomaterials for utrahigh drug loading capacity.

    PubMed

    Guo, Jingxin; Zhang, Haijiao; Geng, Hongya; Mi, Xianqiang; Ding, Guoji; Jiao, Zheng

    2015-01-01

    In this paper, peapod-like hollow carbon nanomaterial was fabricated via an efficient one-pot hydrothermal route. The carbon-silica composite was employed as the precursor and cetyltrimethylammonium bromide (CTAB) as the morphology-controlled agent. SEM and TEM results indicated that the carbon shell and the silica core in the precursor were not closely linked but rattle-type structure. After removing the silica template, the obtained carbon product had uniform peapod-like morphology, interconnected pores and high specific surface areas (above 800.0 m(2)/g). We found that CTAB played an important role in the formation of the products with peapod-like morphology. The particle sizes of the hollow carbon nanospheres were readily adjusted by varying the dosage of tetraethoxysilane (TEOS) and the volume ratio of ethanol and water. Based on the experimental results, the formation mechanism of the hollow carbon nanomaterial was also discussed. By virtue of their unique nanostructure and porous properties, the peapod-like hollow carbon nanomaterial exhibited ultrahigh drug loading capacity above 98.4% for doxorubicin hydrochloride (DOX). PMID:25313471

  18. Surface modified magnetic nanoparticles as efficient and green sorbents: Synthesis, characterization, and application for the removal of anionic dye

    NASA Astrophysics Data System (ADS)

    Rajabi, Hamid Reza; Arjmand, Hooman; Hoseini, S. Jafar; Nasrabadi, Hasan

    2015-11-01

    The object of this study was to evaluate the removal efficiency of sunset yellow (SY) anionic dye from aqueous solutions by using new surface modified iron oxide magnetic nanoparticles (MNPs). Pure Fe3O4 MNPs were synthesized and then functionalized by aminopropyltriethoxysilane (APTES), through a chemical precipitation method. Characterization of the prepared MNP adsorbents was performed by furrier transform infrared (FT-IR), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), and transmission electron microscopy (TEM). According to XRD and TEM results, average size of the magnetic Fe3O4/APTES NPs was estimated to be around 12 nm. The prepared magnetic adsorbent can be well dispersed in the water and easily separated magnetically from the medium after loaded with adsorbate. In the adsorption process, the effect of main experimental parameters such as pH of dye solution, initial concentration of SY dye, reaction time, and amount of MNP adsorbent on the removal of SY were studied and optimized. The small amount of this adsorbent (10 mg) is applicable for the removal of high concentrations of SY dye in reasonable time (17 min), at pH 3.1. Additionally, the adsorption studies show that the Langmuir model is a suitable model to explain the experimental data with high correlation coefficient.

  19. Hexahedron Prism-Anchored Octahedronal CeO2: Crystal Facet-Based Homojunction Promoting Efficient Solar Fuel Synthesis.

    PubMed

    Li, Ping; Zhou, Yong; Zhao, Zongyan; Xu, Qinfeng; Wang, Xiaoyong; Xiao, Min; Zou, Zhigang

    2015-08-01

    An unprecedented, crystal facet-based CeO2 homojunction consisting of hexahedron prism-anchored octahedron with exposed prism surface of {100} facets and octahedron surface of {111} facets was fabricated through solution-based crystallographic-oriented epitaxial growth. The photocatalysis experiment reveals that growth of the prism arm on octahedron allows to activate inert CeO2 octahedron for an increase in phototocatalytic reduction of CO2 into methane. The pronounced photocatalytic performance is attributed to a synergistic effect of the following three factors: (1) band alignment of the {100} and {111} drives electrons and holes to octahedron and prism surfaces, respectively, aiming to reach the most stable energy configuration and leading to a spatial charge separation for long duration; (2) crystallographic-oriented epitaxial growth of the CeO2 hexahedron prism arm on the octahedron verified by the interfacial lattice fringe provides convenient and fast channels for the photogenerated carrier transportation between two units of homojuntion; (3) different effective mass of electrons and holes on {100} and {111} faces leads to high charge carrier mobility, more facilitating the charge separation. The proposed facet-based homojunction in this work may provide a new concept for the efficient separation and fast transfer of photoinduced charge carriers and enhancement of the photocatalytic performance. PMID:26194000

  20. Efficient bifunctional catalyst lipase/organophosphonic acid-functionalized silica for biodiesel synthesis by esterification of oleic acid with ethanol.

    PubMed

    Yin, Ping; Chen, Wen; Liu, Wei; Chen, Hou; Qu, Rongjun; Liu, Xiguang; Tang, Qinghua; Xu, Qiang

    2013-07-01

    An efficient bifunctional catalyst lipase/organophosphonic acid-functionalized silica (SG-T-P-LS) has been successfully developed, and biodiesel production of fatty acid ethyl ester (FAEE) from free fatty acid (FFA) oleic acid with short-chain alcohol ethanol catalyzed by SG-T-P-LS was investigated. The process optimization using response surface methodology (RSM) was performed and the interactions between the operational variables were elucidated, and it was found that the molar ratio of alcohol to acid was the most significant factor. The optimum values for maximum conversion ratio can be obtained by using a Box-Behnken center-united design, and the conversion ratio could reach 89.94 ± 0.42% under the conditions that ethanol/acid molar ratio was 1.05:1 and SG-T-P-LS to FFA weight ratio was 14.9 wt.% at 28.6°C. The research results show that SG-T-P and LS-20 could work cooperatively to promote the esterification reaction, and the bifunctional catalyst SG-T-P-LS is a potential catalyst for biodiesel production. PMID:23688666

  1. Ultrasonic-assisted synthesis of Ce doped cubic-hexagonal ZnTiO3 with highly efficient sonocatalytic activity.

    PubMed

    Eskandarloo, Hamed; Badiei, Alireza; Behnajady, Mohammad A; Tavakoli, Amirrasoul; Ziarani, Ghodsi Mohammadi

    2016-03-01

    Ce doped ZnTiO3 as a novel catalyst with highly efficient and stable sonocatalytic activity was synthesized via an ultrasound-assisted sol-gel method using non-ionic surfactant Pluronic F127 as structure directing agent. Synthesized samples were characterized by using various techniques, such as XRD, TEM, SEM, EDX, ?XRF, BET, DRS, and PL, and their sonocatalytic activity studied toward degradation of p-Nitrophenol as a model organic compound. The synthesized mesoporous Ce/ZnTiO3 had mixed cubic-hexagonal phase with large surface area (118.2 m(2) g(-1)) and narrow pore size distribution (4.9nm). The effects of cerium concentration, calcination temperature, and calcination time on the structure and the sonocatalytic activity of Ce/ZnTiO3 were studied in detail. XRD results were suggested that the relation between the phase structure and the catalytic activity is considerable. Significant decrease in band-gap and PL intensity was observed with increasing the cerium concentration in the ZnTiO3. It became clear that the Ce/ZnTiO3 (0.81mol%) shows high sonocatalytic activity compared with pure ZnTiO3 and other Ce/ZnTiO3 samples as well as commercial TiO2-P25. The possible mechanism for the enhanced sonocatalytic activity of Ce/ZnTiO3 was discussed in details. The electrical energy consumption was also considered during sonocatalytic experiments. PMID:26585006

  2. Facile and economical synthesis of porous activated semi-cokes for highly efficient and fast removal of microcystin-LR.

    PubMed

    Chen, Yan; Zhang, Xiangmei; Liu, Qianyi; Wang, Xidong; Xu, Ling; Zhang, Zuotai

    2015-12-15

    To mitigate the threat of microcystins on the environment and human health, we demonstrate for the first time that porous activated semi-cokes (ASCs) with average pore diameters of 2-20nm could be used as adsorbents for the fast and efficient removal of microcystin-LR (MC-LR). The surface physicochemical properties of ASCs were carefully investigated and their relations with the adsorption performance were discussed. The results showed that ASCs activated by HNO3 and KOH exhibited excellent adsorption capacities of 4276 and 8430?g/g, respectively, which were nearly 5 times and 10 times higher than that of activated carbon (AC). ASCs also showed a fast adsorption property by over 95% recovery of MC-LR in the initial 10min. The overall adsorption of MC-LR on ASCs might be dominated by both external diffusion and intra-particle diffusion. In addition, ASCs manifested an outstanding reusability and the adsorption of MC-LR was hardly influenced by the coexisting fulvic acid at low concentration. Given the remarkable performance and low cost, activated semi-cokes are expected to present promising potentials for the practical application in removing microcystins from aqueous solutions. PMID:26143195

  3. Numerical Optimization of Quenching Efficiency and Particle Size Control in Flame Synthesis of ZrO2 Nanoparticles

    NASA Astrophysics Data System (ADS)

    Torabmostaedi, Hosein; Zhang, Tao

    2014-12-01

    The development of a new quenching design combining rapid cooling with an expansion for controlling the size of nanoparticles synthesized at industrial scale by flame spray pyrolysis was investigated. The design of the quenching device was supported by simulations using a coupled computational fluid dynamics-monodisperse aerosol model to reduce the size of the primary particles and their agglomerate diameters while conserving the production yield at the filter above the burner. The results showed that quenching the spray flame in an open environment led to lower production yield due to the negative velocity of quenching gas which diverted the particles to the bottom of reactor. An additional upstream air flow could help to increase the particle production yield at high air flow rates, while it had a negative effect on the penetration depth of quenching gas inside the main flame which resulted in higher flame heights. The new design showed that adding an enclosure around the burner and quenching ring can significantly increase the quenching efficiency and reduce the particle size. The technique to control the particle size was also studied in this paper.

  4. Numerical Optimization of Quenching Efficiency and Particle Size Control in Flame Synthesis of ZrO2 Nanoparticles

    NASA Astrophysics Data System (ADS)

    Torabmostaedi, Hosein; Zhang, Tao

    2014-09-01

    The development of a new quenching design combining rapid cooling with an expansion for controlling the size of nanoparticles synthesized at industrial scale by flame spray pyrolysis was investigated. The design of the quenching device was supported by simulations using a coupled computational fluid dynamics-monodisperse aerosol model to reduce the size of the primary particles and their agglomerate diameters while conserving the production yield at the filter above the burner. The results showed that quenching the spray flame in an open environment led to lower production yield due to the negative velocity of quenching gas which diverted the particles to the bottom of reactor. An additional upstream air flow could help to increase the particle production yield at high air flow rates, while it had a negative effect on the penetration depth of quenching gas inside the main flame which resulted in higher flame heights. The new design showed that adding an enclosure around the burner and quenching ring can significantly increase the quenching efficiency and reduce the particle size. The technique to control the particle size was also studied in this paper.

  5. Magnesiothermic synthesis of sulfur-doped graphene as an efficient metal-free electrocatalyst for oxygen reduction

    PubMed Central

    Wang, Jiacheng; Ma, Ruguang; Zhou, Zhenzhen; Liu, Guanghui; Liu, Qian

    2015-01-01

    Efficient metal-free electrocatalysts for oxygen reduction reaction (ORR) are highly expected in future low-cost energy systems. We have successfully prepared crumpled, sheet-like, sulfur-doped graphene by magnesiothermic reduction of easily available, low-cost, nontoxic CO2 (in the form of Na2CO3) and Na2SO4 as the carbon and sulfur sources, respectively. At high temperature, Mg can reduce not only carbon in the oxidation state of +4 in CO32? to form graphene, but also sulfur in SO42? from its highest (+6) to lowest valence which was hybridized into the carbon sp2 framework. Various characterization results show that sulfur-doped graphene with only few layers has an appropriate sulfur content, hierarchically robust porous structure, large surface area/pore volume, and highly graphitized textures. The S-doped graphene samples exhibit not only a high activity for ORR with a four-electron pathway, but also superior durability and tolerance to MeOH crossover to 40% Pt/C. This is mainly ascribed to the combination of sulfur-related active sites and hierarchical porous textures, facilitating fast diffusion of oxygen molecules and electrolyte to catalytic sites and release of products from the sites. PMID:25790856

  6. Cyclopropene cycloadditions with annulated furans: total synthesis of (+)- and (-)-frondosin B and (+)-frondosin A.

    PubMed

    Oblak, E Zachary; VanHeyst, Michael D; Li, Jin; Wiemer, Andrew J; Wright, Dennis L

    2014-03-19

    The asymmetric total syntheses of the natural products (+)- and (-)-frondosin B and (+)-frondosin A are reported based on a diastereoselective cycloaddition between tetrabromocyclopropene and an annulated furan to provide a highly functionalized common building block. The bridged bicyclic intermediate could be stereo- and chemoselectively manipulated to produce the two structurally distinct members of the frondosins. Both syntheses feature regioselective palladium-coupling reactions and an unprecedented phosphine-mediated ether bridge cleavage. Surprisingly, the planned enantioselective synthesis of frondosin B led to the opposite epimer of the natural product, suggesting an unusual late stage stereoinversion at C8. Frondosin A, but not frondosin B, was shown to have selective antiproliferative activity against several B-cell lines. PMID:24575795

  7. Total synthesis of marinomycin A using salicylate as a molecular switch to mediate dimerization

    NASA Astrophysics Data System (ADS)

    Evans, P. Andrew; Huang, Mu-Hua; Lawler, Michael J.; Maroto, Sergio

    2012-08-01

    Antibiotics play a significant role in human health because of their ability to treat life-threatening bacterial infections. The growing problems with antibiotic resistance have made the development of new antibiotics a World Health Organization priority. Marinomycin A is a member of a new class of bis-salicylate-containing polyene macrodiolides, which have potent antibiotic activity against methicillin-resistant Staphylococcus aureus and vancomycin-resistant Enterococcus faecium. Herein, we describe a triply convergent synthesis of this agent using the salicylate as a novel molecular switch for the chemoselective construction of the macrodiolide. This strategy raises new questions regarding the biosynthetic role of the salicylate and its potential impact on the mechanism of action of these types of agents. For instance, in contrast to penicillin, which enhances the electrophilicity of the cyclic amide through ring strain, salicylates reduce the electrophilicity of the aryl ester through an intramolecular resonance-assisted hydrogen bond to provide an amide surrogate.

  8. Interactions at the Dimer Interface Influence the Relative Efficiencies for Purine Nucleotide Synthesis and Pyrophosphorolysis in a Phosphoribosyltransferase

    SciTech Connect

    Canyuk, Bhutorn; Medrano, Francisco J.; Wenck, MaryAnne; Focia, Pamela J.; Eakin, Ann E.; Craig III, Sydney P.

    2010-03-05

    Enzymes that salvage 6-oxopurines, including hypoxanthine phosphoribosyltransferases (HPRTs), are potential targets for drugs in the treatment of diseases caused by protozoan parasites. For this reason, a number of high-resolution X-ray crystal structures of the HPRTs from protozoa have been reported. Although these structures did not reveal why HPRTs need to form dimers for catalysis, they revealed the existence of potentially relevant interactions involving residues in a loop of amino acid residues adjacent to the dimer interface, but the contributions of these interactions to catalysis remained poorly understood. The loop, referred to as active-site loop I, contains an unusual non-proline cis-peptide and is composed of residues that are structurally analogous with Leu67, Lys68, and Gly69 in the human HPRT. Functional analyses of site-directed mutations (K68D, K68E, K68N, K68P, and K68R) in the HPRT from Trypanosoma cruzi, etiologic agent of Chagas disease, show that the side-chain at position 68 can differentially influence the K{sub m} values for all four substrates as well as the k{sub cat} values for both IMP formation and pyrophosphorolysis. Also, the results for the K68P mutant are inconsistent with a cis-trans peptide isomerization-assisted catalytic mechanism. These data, together with the results of structural studies of the K68R mutant, reveal that the side-chain of residue 68 does not participate directly in reaction chemistry, but it strongly influences the relative efficiencies for IMP formation and pyrophosphorolysis, and the prevalence of lysine at position 68 in the HPRT of the majority of eukaryotes is consistent with there being a biological role for nucleotide pyrophosphorolysis.

  9. Rapid efficient synthesis and characterization of silver, gold, and bimetallic nanoparticles from the medicinal plant Plumbago zeylanica and their application in biofilm control

    PubMed Central

    Salunke, Gayatri R; Ghosh, Sougata; Santosh Kumar, RJ; Khade, Samiksha; Vashisth, Priya; Kale, Trupti; Chopade, Snehal; Pruthi, Vikas; Kundu, Gopal; Bellare, Jayesh R; Chopade, Balu A

    2014-01-01

    Background Nanoparticles (NPs) have gained significance in medical fields due to their high surface-area-to-volume ratio. In this study, we synthesized NPs from a medicinally important plant – Plumbago zeylanica. Materials and methods Aqueous root extract of P. zeylanica (PZRE) was analyzed for the presence of flavonoids, sugars, and organic acids using high-performance thin-layer chromatography (HPTLC), gas chromatography-time of flight-mass spectrometry (GC-TOF-MS), and biochemical methods. The silver NPs (AgNPs), gold NPs (AuNPs), and bimetallic NPs (AgAuNPs) were synthesized from root extract and characterized using ultraviolet-visible spectra, X-ray diffraction (XRD), energy-dispersive spectrometry (EDS), transmission electron microscopy (TEM), and dynamic light scattering (DLS). The effects of these NPs on Acinetobacter baumannii, Staphylococcus aureus, and Escherichia coli biofilms were studied using quantitative biofilm inhibition and disruption assays, as well as using fluorescence, scanning electron microscopy, and atomic force microscopy. Results PZRE showed the presence of phenolics, such as plumbagin, and flavonoids, in addition to citric acid, sucrose, glucose, fructose, and starch, using HPTLC, GC-TOF-MS, and quantitative analysis. Bioreduction of silver nitrate (AgNO3) and chloroauric acid (HAuCl4) were confirmed at absorbances of 440 nm (AgNPs), 570 nm (AuNPs), and 540 nm (AgAuNPs), respectively. The maximum rate of synthesis at 50°C was achieved with 5 mM AgNO3 within 4.5 hours for AgNPs; and with 0.7 mM HAuCl4 within 5 hours for AuNPs. The synthesis of AgAuNPs, which completed within 90 minutes with 0.7 mM AgNO3 and HAuCl4, was found to be the fastest. Fourier-transform infrared spectroscopy confirmed bioreduction, while EDS and XRD patterns confirmed purity and the crystalline nature of the NPs, respectively. TEM micrographs and DLS showed about 60 nm monodispersed Ag nanospheres, 20–30 nm Au nanospheres adhering to form Au nanotriangles, and about 90 nm hexagonal blunt-ended AgAuNPs. These NPs also showed antimicrobial and antibiofilm activity against E. coli, A. baumannii, S. aureus, and a mixed culture of A. baumannii and S. aureus. AgNPs inhibited biofilm in the range of 96%–99% and AgAuNPs from 93% to 98% in single-culture biofilms. AuNPs also showed biofilm inhibition, with the highest of 98% in S. aureus. AgNPs also showed good biofilm disruption, with the highest of 88% in A. baumannii. Conclusion This is the first report on rapid and efficient synthesis of AgNPs, AuNPs and AgAuNPs from P. zeylanica and their effect on quantitative inhibition and disruption of bacterial biofilms. PMID:24920901

  10. Scope and Mechanistic Analysis for Chemoselective Hydrogenolysis of Carbonyl Compounds Catalyzed by a Cationic Ruthenium Hydride Complex with a Tunable Phenol Ligand.

    PubMed

    Kalutharage, Nishantha; Yi, Chae S

    2015-09-01

    A cationic ruthenium hydride complex, [(C6H6)(PCy3)(CO)RuH](+)BF4(-) (1), with a phenol ligand was found to exhibit high catalytic activity for the hydrogenolysis of carbonyl compounds to yield the corresponding aliphatic products. The catalytic method showed exceptionally high chemoselectivity toward the carbonyl reduction over alkene hydrogenation. Kinetic and spectroscopic studies revealed a strong electronic influence of the phenol ligand on the catalyst activity. The Hammett plot of the hydrogenolysis of 4-methoxyacetophenone displayed two opposite linear slopes for the catalytic system 1/p-X-C6H4OH (? = -3.3 for X = OMe, t-Bu, Et, and Me; ? = +1.5 for X = F, Cl, and CF3). A normal deuterium isotope effect was observed for the hydrogenolysis reaction catalyzed by 1/p-X-C6H4OH with an electron-releasing group (kH/kD = 1.7-2.5; X = OMe, Et), whereas an inverse isotope effect was measured for 1/p-X-C6H4OH with an electron-withdrawing group (kH/kD = 0.6-0.7; X = Cl, CF3). The empirical rate law was determined from the hydrogenolysis of 4-methoxyacetophenone: rate = kobsd[Ru][ketone][H2](-1) for the reaction catalyzed by 1/p-OMe-C6H4OH, and rate = kobsd[Ru][ketone][H2](0) for the reaction catalyzed by 1/p-CF3-C6H4OH. Catalytically relevant dinuclear ruthenium hydride and hydroxo complexes were synthesized, and their structures were established by X-ray crystallography. Two distinct mechanistic pathways are presented for the hydrogenolysis reaction on the basis of these kinetic and spectroscopic data. PMID:26235841

  11. Matrix Effect of Human Reconstructed Epidermis on the Chemoselectivity of a Skin Sensitizing ?-Methylene-?-Butyrolactone: Consequences for the Development of in Chemico Alternative Methods.

    PubMed

    Debeuckelaere, Camille; Berl, Valérie; Elbayed, Karim; Moussallieh, François-Marie; Namer, Izzie-Jacques; Lepoittevin, J-P

    2015-11-16

    Adoption of new legislations and social pressure are pushing toward the development of alternative methods to the use of animals for the assessment of most toxicological end-points including skin sensitization. To that respect, much efforts have been put in the first step of the adverse outcome pathway focusing on chemical interactions taking place between sensitizing chemicals or haptens and epidermal proteins. However, these in chemico approaches have been so far only based on the use of model nucleophiles, amino acids, peptides, or proteins in water/buffer solution and focused mainly on thiol reactivity. These studies even if bringing a valuable set of information are very far from reflecting chemical interactions that may happen between a xenobiotic and nucleophiles present in a complex heterogeneous tissue such as the epidermis. Recently, we have shown that using a high-resolution magic angle spinning (HRMAS) nuclear magnetic resonance (NMR) technique it was possible to characterize chemical interactions taking place between a skin sensitizer and nucleophilic amino acids present in a 3-D reconstructed human epidermis (RHE). We have now compared the chemical reactivity and chemoselectivity of a sensitizing ?-methylene-?-butyrolactone toward human serum albumin used as a model protein and RHE. Using this technique, we showed that amino acid modifications by this hapten was different according to the model used and that in RHE histidine residues seem to have an important role in the formation of adducts. Obviously, the role of histidine in the induction of skin sensitization has been so far neglected and should probably be taken into account for the refinement of in chemico approaches for the detection and potency classification of skin sensitizers. PMID:26496248

  12. A Stilbene that Binds Selectively to Transthyretin in Cells and Remains Dark Until it Undergoes a Chemoselective Reaction to Create a Bright Blue Fluorescent Conjugate

    PubMed Central

    Choi, Sungwook; Ong, Derrick Sek Tong; Kelly, Jeffery W.

    2010-01-01

    We describe a non-fluorescent, second generation stilbene that very selectively binds to transthyretin in complex biological environments and remains dark until it chemoselectively reacts with the pKa perturbed Lys-15 ?-amino group of transthyretin to form a bright blue fluorescent conjugate. Stilbene A2 is mechanistically unusual in that it remains non-fluorescent in cell lysates lacking transthyretin, even though there is likely some proteome binding. Thus, it is especially useful for cellular imaging, as background fluorescence is undetectable until A2 reacts with transthyretin. The mechanistic basis for the effective lack of environment-sensitive fluorescence of A2 when bound to, but before reacting with, transthyretin is reported. Stilbene A2 exhibits sufficiently rapid transthyretin conjugation kinetics at 37 °C to enable pulse-chase experiments to be performed, in this case demonstrating that transthyretin is secreted from HeLa cells. As the chase compound, we employed C1–a cell permeable, highly selective, non-covalent, transthyretin binding dihydrostilbene that cannot become fluorescent. The progress reported is viewed as a first and necessary step toward our long-term goal of creating a one-chain, one-binding-site transthyretin tag, whose fluorescence can be regulated by adding A2, or an analogous molecule. Fusing proteins of interest to a one-chain, one-binding-site transthyretin tag regulated by A2 should be useful for studying folding, trafficking and degradation in the cellular secretory pathway, utilizing pulse-chase experiments. Immediate applications of A2 include utilizing its conjugate fluorescence to quantify transthyretin concentration in human plasma, reflecting nutritional status, and determining the binding stoichiometry of kinetic stabilizer drugs to transthyretin in plasma. PMID:20964336

  13. Large-scale and highly efficient synthesis of micro- and nano-fibers with controlled fiber morphology by centrifugal jet spinning for tissue regeneration

    NASA Astrophysics Data System (ADS)

    Ren, Liyun; Pandit, Vaibhav; Elkin, Joshua; Denman, Tyler; Cooper, James A.; Kotha, Shiva P.

    2013-02-01

    PLLA fibrous tissue scaffolds with controlled fiber nanoscale surface roughness are fabricated with a novel centrifugal jet spinning process. The centrifugal jet spinning technique is a highly efficient synthesis method for micron- to nano-sized fibers with a production rate up to 0.5 g min-1. During the centrifugal jet spinning process, a polymer solution jet is stretched by the centrifugal force of a rotating chamber. By engineering the rheological properties of the polymer solution, solvent evaporation rate and centrifugal force that are applied on the solution jet, polyvinylpyrrolidone (PVP) and poly(l-lactic acid) (PLLA) composite fibers with various diameters are fabricated. Viscosity measurements of polymer solutions allowed us to determine critical polymer chain entanglement limits that allow the generation of continuous fiber as opposed to beads or beaded fibers. Above a critical concentration at which polymer chains are partially or fully entangled, lower polymer concentrations and higher centrifugal forces resulted in thinner fibers. Etching of PVP from the PLLA-PVP composite fibers doped with increasing PVP concentrations yielded PLLA fibers with increasing nano-scale surface roughness and porosity, which increased the fiber hydrophilicity dramatically. Scanning electron micrographs of the etched composite fibers suggest that PVP and PLLA were co-contiguously phase separated within the composite fibers during spinning and nano-scale roughness features were created after the partial etching of PVP. To study the tissue regeneration efficacy of the engineered PLLA fiber matrix, human dermal fibroblasts are used to simulate partial skin graft. Fibers with increased PLLA surface roughness and porosity demonstrated a trend towards higher cell attachment and proliferation.PLLA fibrous tissue scaffolds with controlled fiber nanoscale surface roughness are fabricated with a novel centrifugal jet spinning process. The centrifugal jet spinning technique is a highly efficient synthesis method for micron- to nano-sized fibers with a production rate up to 0.5 g min-1. During the centrifugal jet spinning process, a polymer solution jet is stretched by the centrifugal force of a rotating chamber. By engineering the rheological properties of the polymer solution, solvent evaporation rate and centrifugal force that are applied on the solution jet, polyvinylpyrrolidone (PVP) and poly(l-lactic acid) (PLLA) composite fibers with various diameters are fabricated. Viscosity measurements of polymer solutions allowed us to determine critical polymer chain entanglement limits that allow the generation of continuous fiber as opposed to beads or beaded fibers. Above a critical concentration at which polymer chains are partially or fully entangled, lower polymer concentrations and higher centrifugal forces resulted in thinner fibers. Etching of PVP from the PLLA-PVP composite fibers doped with increasing PVP concentrations yielded PLLA fibers with increasing nano-scale surface roughness and porosity, which increased the fiber hydrophilicity dramatically. Scanning electron micrographs of the etched composite fibers suggest that PVP and PLLA were co-contiguously phase separated within the composite fibers during spinning and nano-scale roughness features were created after the partial etching of PVP. To study the tissue regeneration efficacy of the engineered PLLA fiber matrix, human dermal fibroblasts are used to simulate partial skin graft. Fibers with increased PLLA surface roughness and porosity demonstrated a trend towards higher cell attachment and proliferation. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr33423f

  14. Homogeneous deposition-assisted synthesis of iron-nitrogen composites on graphene as highly efficient non-precious metal electrocatalysts for microbial fuel cell power generation

    NASA Astrophysics Data System (ADS)

    Liu, Yuan; Jin, Xiao-Jun; Dionysiou, Dionysios D.; Liu, Hong; Huang, Yu-Ming

    2015-03-01

    This work proposed a novel strategy for synthesizing highly efficient non-precious metal oxygen reduction reaction (ORR) electrocatalysts. Fe complexes were homogeneously deposited (HD) on graphene oxide through in situ hydrolysis of urea, followed by two-step pyrolysis under Ar and NH3 atmospheres, resulting in formation of Fe- and N-functionalized graphene (HD-FeN/G). The morphology, crystalline structure and elemental composition of HD-FeN/G were characterized. ORR activity was evaluated by using a rotary disk electrode (RDE) electrochemical system. HD improved the loading and distribution of the Fe-Nx composites on graphene. The ORR activity of the as-prepared HD-FeN/G in neutral medium was comparable to that of the state-of-the-art commercial Pt/C and significantly superior to a FeN/G counterpart produced via traditional approach. The ORR electron transfer number of HD-FeN/G was as high as 3.83 ± 0.08, which suggested that ORR catalysis proceeds through a four-electron pathway. HD-FeN/G was used as a cathodic electrocatalyst in microbial fuel cells (MFCs), and the resultant HD-FeN/G-MFC showed comparable voltage output and maximum power density to those of Pt/C-MFC. The HD-FeN/G-MFC achieved a maximum power density of 885 mW m-2, which was much higher than that of FeN/G-MFC (708 mW m-2). These findings demonstrate that HD-FeN/G produced through the novel synthesis strategy proposed in this work would be a good candidate as cathodic electrocatalyst in MFCs.

  15. Towards novel efficient and stable nuclear import signals: synthesis and properties of trimethylguanosine cap analogs modified within the 5',5'-triphosphate bridge.

    PubMed

    Zytek, Malgorzata; Kowalska, Joanna; Lukaszewicz, Maciej; Wojtczak, Blazej A; Zuberek, Joanna; Ferenc-Mrozek, Aleksandra; Darzynkiewicz, Edward; Niedzwiecka, Anna; Jemielity, Jacek

    2014-12-01

    A trimethylguanosine (TMG) cap is present at the 5' end of several small nuclear and nucleolar RNAs. Recently, it has been reported that the TMG cap is a potential nuclear import signal for nucleus-targeting therapeutic nucleic acids and proteins. The import is mediated by recognition of the TMG cap by the snRNA transporting protein, snurportin1. This work describes the synthesis and properties of a series of dinucleotide TMG cap (m3(2,2,7)GpppG) analogs modified in the 5',5'-triphosphate bridge as tools to study TMG cap-dependent biological processes. The bridge was altered at different positions by introducing either bridging (imidodiphosphate, O to NH and methylenebisphosphonate, O to CH2) or non-bridging (phosphorothioate, O to S and boranophosphate, O to BH3) modifications, or by elongation to tetraphosphate. The stability of novel analogs in blood serum was studied to reveal that the ?,?-bridging O to NH substitution (m3(2,2,7)GppNHpG) confers the highest resistance. Short RNAs capped with analogs containing ?,?-bridging (m3(2,2,7)GppNHpG) or ?-non-bridging (m3(2,2,7)GppSpG D2) modifications were resistant to decapping pyrophosphatase, hNudt16. Preliminary studies on binding by human snurportin1 revealed that both O to NH and O to S substitutions support this binding. Due to favorable properties in all three assays, m3(2,2,7)GppNHpG was selected as a promising candidate for further studies on the efficiency of the TMG cap as a nuclear import signal. PMID:25296894

  16. Efficient synthesis of ?-conjugated molecules incorporating fluorinated phenylene units through palladium-catalyzed iterative C(sp2)–H bond arylations

    PubMed Central

    Abdelmalek, Fatiha; Derridj, Fazia; Djebbar, Safia

    2015-01-01

    Summary We report herein a two or three step synthesis of fluorinated ?-conjugated oligomers through iterative C–H bond arylations. Palladium-catalyzed desulfitative arylation of heteroarenes allowed in a first step the synthesis of fluoroaryl-heteroarene units in high yields. Then, the next steps involve direct arylation with aryl bromides catalyzed by PdCl(C3H5)(dppb) to afford triad or tetrad heteroaromatic compounds via regioselective activation of C(sp2)–H bonds. PMID:26664622

  17. EFFICIENT CHEMICAL SYNTHESIS USING MICROWAVES

    EPA Science Inventory

    Synthetic organic transformations performed under non-traditional conditions are becoming popular primarily to circumvent the growing environmental concerns. A solvent-free approach that involves microwave (MW) exposure of neat reactants catalyzed by the surfaces of less-expensiv...

  18. Energy efficient synthesis of boranes

    DOEpatents

    Thorn, David L (Los Alamos, NM); Tumas, William (Los Alamos, NM); Schwarz, Daniel E (Los Alamos, NM); Burrell, Anthony K (Los Alamos, NM)

    2012-01-24

    The reaction of halo-boron compounds (B--X compounds, compounds having one or more boron-halogen bonds) with silanes provides boranes (B--H compounds, compounds having one or more B--H bonds) and halosilanes. Inorganic hydrides, such as surface-bound silane hydrides (Si--H) react with B--X compounds to form B--H compounds and surface-bound halosilanes. The surface bound halosilanes are converted back to surface-bound silanes electrochemically. Halo-boron compounds react with stannanes (tin compounds having a Sn--H bond) to form boranes and halostannanes (tin compounds having a Sn--X bond). The halostannanes are converted back to stannanes electrochemically or by the thermolysis of Sn-formate compounds. When the halo-boron compound is BCl.sub.3, the B--H compound is B.sub.2H.sub.6, and where the reducing potential is provided electrochemically or by the thermolysis of formate.

  19. Energy efficient synthesis of boranes

    DOEpatents

    Thorn, David L. (Los Alamos, NM); Tumas, William (Los Alamos, NM); Schwarz, Daniel E. (Los Alamos, NM); Burrell, Anthony K. (Los Alamos, NM)

    2010-11-23

    The reaction of halo-boron compounds (B--X compounds, compounds having one or more boron-halogen bonds) with silanes provides boranes (B--H compounds, compounds having one or more B--H bonds) and halosilanes. Inorganic hydrides, such as surface-bound silane hydrides (Si--H) react with B--X compounds to form B--H compounds and surface-bound halosilanes. The surface bound halosilanes are converted back to surface-bound silanes electrochemically. Halo-boron compounds react with stannanes (tin compounds having a Sn--H bond) to form boranes and halostannanes (tin compounds having a Sn--X bond). The halostannanes are converted back to stannanes electrochemically or by the thermolysis of Sn-formate compounds. When the halo-boron compound is BCl.sub.3, the B--H compound is B.sub.2H.sub.6, and where the reducing potential is provided electrochemically or by the thermolysis of formate.

  20. Divergent Oriented Synthesis For the Design of Reagents for Protein Conjugation

    PubMed Central

    Garanger, Elisabeth; Blois, Joseph; Hilderbrand, Scott A.; Shao, Fangwei; Josephson, Lee

    2010-01-01

    Instead of using diversity oriented syntheses (DOS) to obtain compounds with biological activities, we employed the DOS method to efficiently obtain multifunctional single attachment point (MSAP) reagents for the conjugation to proteins. Acid insensitive functional groups (chelators, fluorochromes) were attached to Lys-Cys-NH2 or Lys-Lys-?Ala-Cys-NH2 peptide scaffolds. After cleavage from solid supports, the modified peptide intermediates were split and further modified by two solution phase, chemoselective reactions employing the single amine and single thiol presented on the intermediates. MSAP-based fluorochrome–chelates were obtained, some possessing a third functional group like a polyethylene glycol (PEG) polymer or “click chemistry” reactive alkynes and azides. The DOS of MSAP reagents permitted the efficient generation of panels of MSAP reagents that can be used to obtain multifunctional proteins with a single modified amino acid (a single attachment point). PMID:19928910

  1. A green, efficient and recyclable Fe+3@K10 catalyst for the synthesis of bioactive pyrazolo[3,4-b]pyridin-6(7H)-ones under "on water" conditions

    NASA Astrophysics Data System (ADS)

    Mamaghani, Manouchehr; Shirini, Farhad; Mahmoodi, Nosrat O.; Azimi-Roshan, Abbas; Hashemlou, Hussein

    2013-11-01

    An efficient regioselective one-pot three-component synthesis of 4-aryl-3-methyl-4,5-dihydro-1H-pyrazolo[3,4-b]pyridin-6(7H)-ones and their bis-derivatives (Table 3 and Fig. 2) catalyzed by Fe+3-K10 montmorillonite (Fe+3@K10) under the Sharpless conditions ("On water" contdiions) is described. This rapid method produced the products in short reaction times (10-15 min) and excellent yields (87-95%). The antibacterial activity of the synthesized products was examined. Some products showed promising activities.

  2. Surfactant-free green synthesis of Fe3O4 nanoparticles capped with 3,4-dihydroxyphenethylcarbamodithioate: stable recyclable magnetic nanoparticles for the rapid and efficient removal of Hg(ii) ions from water.

    PubMed

    Venkateswarlu, Sada; Yoon, Minyoung

    2015-11-14

    Mercury is considered one of the most notorious global pollutants due to its high toxicity and widespread use in industry. Although many materials have been developed for the removal of mercury for water purification, most of these materials are difficult to reuse, which may lead to an increase in the mercury handling expense. Therefore, new sustainable materials that can be easily recycled and are highly efficient for the removal of mercury are required. Herein, we report the surfactant-free green synthesis of Fe3O4 magnetic nanoparticles (MNPs) using a watermelon (Citrullus lanatus) rind extract. The Fe3O4 MNPs were further functionalized with 3,4-dihydroxyphenethylcarbamodithioate (DHPCT) and applied to the removal of Hg(ii). Evaluation of the mercury removal efficiency and the amount adsorbed by DHPCT@Fe3O4 MNPs demonstrated a high Hg(ii) removal efficiency (98%) with a maximum Hg(ii) adsorption capacity of 52.1 mg g(-1). Systematic studies of the adsorption mechanism and selectivity suggest that the soft ligand (DHPCT) can preferentially coordinate with the soft metal ion (Hg(ii)) resulting in selective mercury removal. The developed DHPCT@Fe3O4 MNPs were readily recycled several times using an external magnet by exploiting their ferromagnetic character, without a significant decline in the Hg(ii) removal efficiency. This study provides a new insight into the preparation of a highly efficient adsorbent for Hg(ii) removal by an eco-friendly method. PMID:26436867

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

    PubMed

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

    2015-11-19

    An azobenzene-containing zirconium metal-organic framework was demonstrated to be an effective heterogeneous catalyst for the direct amidation of benzoic acids in tetrahydrofuran at 70 °C. This finding was applied to the synthesis of several important, representative bioactive compounds. PMID:26455380

  4. Flexible synthesis of polyfunctionalised 3-fluoropyrroles.

    PubMed

    Cogswell, Thomas J; Donald, Craig S; Marquez, Rodolfo

    2015-12-15

    An efficient and selective approach for the synthesis of polyfunctionalised 3-fluoropyrroles has been developed starting from commercial aldehydes. The methodology is concise, efficient and allows for the modular and systematic assembly of polysubstituted 3-fluoropyrroles. This synthesis provides an alternative and highly convergent strategy for the generation of these chemically and biologically important units. PMID:26555030

  5. Oxenoids in organic synthesis.

    PubMed

    Minko, Yury; Marek, Ilan

    2014-03-14

    Experimental and theoretical studies of metalated peroxides confirmed their unique properties as oxenoids (electrophilic oxidants) allowing for a highly selective and efficient oxidation processes of nucleophilic organometallic species. In this short review we present the most prominent examples of the application of this class of reagents towards organic synthesis. PMID:24477293

  6. An efficient one-pot two catalyst system in the construction of 2-substituted benzimidazoles: synthesis of benzimidazo[1,2-c]quinazolines.

    PubMed

    Cimarelli, Cristina; Di Nicola, Matteo; Diomedi, Simone; Giovannini, Riccardo; Hamprecht, Dieter; Properzi, Roberta; Sorana, Federico; Marcantoni, Enrico

    2015-12-28

    The benzimidazole core is a common moiety in a large number of natural products and pharmacologically active small molecules. The synthesis of novel benzimidazole derivatives remains a main focus in medicinal research. In continuation of the efforts towards Ce(iii) catalysts for organic transformations, we observed for the first time the activity of the iodide ion and copper cation in activating CeCl3·7H2O in the selective formation of prototypical 2-substituted benzimidazoles. The one-pot CeCl3·7H2O-CuI catalytic system procedure includes the cyclo-dehydrogenation of aniline Schiff's bases, generated in situ from the condensation of 1,2-phenylenediamine and aldehydes, followed by the oxidation with iodine, which works as a hydrogen sponge. Mild reaction conditions, good to excellent yields, and clean reactions make the procedure a useful contribution to the synthesis of biologically active fused heterocycles containing benzimidazoquinazolines. PMID:26477673

  7. Palladium-catalyzed intramolecular asymmetric C-H functionalization/cyclization reaction of metallocenes: an efficient approach toward the synthesis of planar chiral metallocene compounds.

    PubMed

    Deng, Ruixian; Huang, Yunze; Ma, Xinna; Li, Gencheng; Zhu, Rui; Wang, Bin; Kang, Yan-Biao; Gu, Zhenhua

    2014-03-26

    A palladium-catalyzed asymmetric synthesis of planar chiral metallocene compounds is reported. The reaction stereoselectively functionalized one of the ortho C-H bonds of Cp rings by intramolecular cyclization to form indenone derivatives in high yields with excellent enantioselectivity. The mild set of reaction conditions allowed a wide variety of chiral metallocene compounds to be synthesized with broad functional group tolerance. The influences of preinstalled chiralities on the other Cp-ring were also investigated. PMID:24617772

  8. Concise total synthesis of (+)-bionectins A and C

    E-print Network

    Coste, Alexis

    The concise and efficient total synthesis of (+)-bionectins A and C is described. Our approach to these natural products features a new and scalable method for erythro-?-hydroxytryptophan amino acid synthesis, an intramolecular ...

  9. Simple, Chemoselective, Catalytic Olefin Isomerization

    PubMed Central

    2015-01-01

    Catalytic amounts of Co(SaltBu,tBu)Cl and organosilane irreversibly isomerize terminal alkenes by one position. The same catalysts effect cycloisomerization of dienes and retrocycloisomerization of strained rings. Strong Lewis bases like amines and imidazoles, and labile functionalities like epoxides, are tolerated. PMID:25398144

  10. Synthesis of Structurally Diverse 2,3-Fused Indoles via Microwave-Assisted AgSbF6-Catalysed Intramolecular Difunctionalization of o-Alkynylanilines

    PubMed Central

    Huang, Yuanqiong; Yang, Yan; Song, Hongjian; Liu, Yuxiu; Wang, Qingmin

    2015-01-01

    2,3-Fused indoles are found in numerous natural products and drug molecules. Although several elegant methods for the synthesis of this structural motif have been reported, long reaction times and harsh conditions are sometimes required, and the yields tend to be low. Herein, we report a microwave method for straightforward access to various types of 2,3-fused indoles via AgSbF6-catalysed intramolecular difunctionalization of o-alkynylanilines. AgSbF6 played a role in both the hydroamination step and the imine-formation step. This method, which exhibited excellent chemoselectivity (no ring-fused 1,2-dihydroquinolines were formed), was used for formal syntheses of the natural products conolidine and ervaticine and the antihistamine drug latrepirdine. PMID:26310858

  11. General and efficient one-pot synthesis of novel sugar/heterocyclic(aryl) 1,2-diketones from sugar terminal alkynes by Sonogashira/tetra-n- butylammonium permanganate oxidation.

    PubMed

    Zhang, Fuyi; Wu, Xiaopei; Wang, Liming; Liu, Hong; Zhao, Yufen

    2015-11-19

    A new approach for one-pot synthesis of novel sugar/heterocyclic(aryl) 1,2-diketones has been achieved by the reaction of various sugar terminal alkynes with heterocyclic(aryl) iodides at room temperature. This one-pot protocol includes Sonogashira coupling and mild n-Bu4NMnO4 oxidation reaction. This method is mild, general and efficient. Fifty-six examples have been given and the sugar/heterocyclic(aryl) 1,2-diketones were obtained in 71-94% yields. The sugar terminal alkynes include 9 structurally different sugars in pyranose, furanose, and acyclic form which have various protecting groups, sensitive groups, and sterically bulky substituents. The heterocyclic(aryl) iodides include sterically bulky heterocyclic compounds and iodobenzenes with electron-donating, electron-neutral, and electron-withdrawing substituents. PMID:26406454

  12. An efficient catalytic system based on 7,8-dihydroxy-4-methylcoumarin and copper(II) for the click synthesis of diverse 1,4-disubstituted-1,2,3-triazoles under green conditions.

    PubMed

    Sharghi, Hashem; Shiri, Pezhman; Aberi, Mahdi

    2014-08-01

    In this work, the combination of 7,8-dihydroxy-4-methyl coumarin (DHMC) as a novel bidentate O,O-chelating agent and copper(II) acetate monohydrate (2:1 molar ratio) has been found to form an efficient catalytic system. This catalyst provided good to excellent yields in the multi-component click synthesis of 1,4-disubstituted-1,2,3-triazoles by using various structurally diverse organic halides, different non-activated terminal alkynes, and sodium azide. This catalytic system eliminates the need for the isolation of the hazardous azide intermediates which are generated in situ. The reaction is carried out in aqueous phase at room temperature and it can be accelerated by sonication or by increasing the reaction temperature. Moreover, the reaction can be performed in large scale. It is noteworthy that DHMC is commercially available and that it can be easily synthesized with low cost materials. PMID:24866914

  13. Three Component Reaction: An Efficient Synthesis and Reactions of 3,4-Dihydropyrimidin-2(1H)-Ones and Thiones Using New Natural Catalyst

    PubMed Central

    Elmaghraby, A. M.; Mousa, I. A.; Harb, A. A.; Mahgoub, M. Y.

    2013-01-01

    Synthesis of 3,4-dihydropyrimidin-2(1H)-one and 3,4-dihydropyrimidin-2(1H)-thione derivatives from aldehydes, 1,3-dicarbonyl derivatives and urea or thiourea using granite and quartz as new, natural and reusable catalysts. Some of the 3,4-dihydropyrimidin-2(1H)-thione derivatives were used to prepare new heterocyclic compounds. The antimicrobial activity of selected examples of the synthesized compounds was tested and showed moderate activity. PMID:24052868

  14. Smart core-shell microgel support for acetyl coenzyme A synthetase: a step toward efficient synthesis of polyketide-based drugs.

    PubMed

    Dubey, Nidhi C; Tripathi, Bijay P; Stamm, Manfred; Ionov, Leonid

    2014-07-14

    The flexibility in tuning the structure and charge properties of PNIPAm microgels during their synthesis makes them a suitable choice for various biological applications. Two-step free radical polymerization, a common method employed for synthesis of core-shell microgel has been well adopted to obtain cationic poly(N-isopropylacrylamide-aminoethyl methacrylate) (PNIPAm-AEMA) shell and PNIPAm core. Scanning electron microscopy (SEM), dynamic light scattering (DLS), zeta potential, and ninhydrin assay suggests nearly monodispersed particles of cationic nature. Amino groups on the microgel provides suitable attachment point for covalent immobilization of acetyl coenzyme A synthetase (Acs) via 1-ethyl-3-(3-N,N- dimethylaminopropyl) carbodiimide (EDC) chemistry. On immobilization, 61.55% of initial activity of Acs has been retained, while Michaelis-Menten kinetics of the immobilized Acs indicates identical K(m) (Michaelis constant) but decrease in the V(max) (maximum substrate conversion rate) compared to free enzyme. Immobilized Acs shows an improvement in activity at wide temperature and pH range and also demonstrates good thermal, storage, and operational stability. The Acs-microgel bioconjugate has been successfully reused for four consecutive operation cycles with more than 50% initial activity. PMID:24938082

  15. Nitrogen-atom endohedral fullerene synthesis with high efficiency by controlling plasma-ion irradiation energy and C{sub 60} internal energy

    SciTech Connect

    Cho, Soon Cheon; Kaneko, Toshiro Ishida, Hiroyasu; Hatakeyama, Rikizo

    2015-03-28

    The nitrogen-atom endohedral fullerene (N@C{sub 60}) has been synthesized by controlling the plasma ion irradiation energy (E{sub i}) and fullerene (C{sub 60}) behavior in the sublimation phase. We examined the relationship between the synthesis purity of N@C{sub 60} [molar concentration ratio of N@C{sub 60} to pristine fullerene (C{sub 60})] and E{sub i}, which was controlled by changing the substrate bias voltages (V{sub sub}) and gas pressure (P{sub N2}) during the plasma irradiation process. High-density nitrogen-molecular ions (N{sub 2}{sup +}) with a suitable E{sub i} near 80 eV are confirmed to be the optimum condition of the nitrogen plasma for the synthesis of high-purity N@C{sub 60}. In addition, high sublimation of C{sub 60} contributes to a higher yield due to the high internal energy of C{sub 60} and the related cage defects that are present under these conditions. As a result, a purity of 0.83% is realized for the first time, which is almost two orders of magnitude higher than that using other methods.

  16. Green chemistry for nanoparticle synthesis.

    PubMed

    Duan, Haohong; Wang, Dingsheng; Li, Yadong

    2015-08-21

    The application of the twelve principles of green chemistry in nanoparticle synthesis is a relatively new emerging issue concerning the sustainability. This field has received great attention in recent years due to its capability to design alternative, safer, energy efficient, and less toxic routes towards synthesis. These routes have been associated with the rational utilization of various substances in the nanoparticle preparations and synthetic methods, which have been broadly discussed in this tutorial review. This article is not meant to provide an exhaustive overview of green synthesis of nanoparticles, but to present several pivotal aspects of synthesis with environmental concerns, involving the selection and evaluation of nontoxic capping and reducing agents, the choice of innocuous solvents and the development of energy-efficient synthetic methods. PMID:25615873

  17. An efficient solid-state synthesis of fluorescent surface carboxylated carbon dots derived from C60 as a label-free probe for iron ions in living cells.

    PubMed

    Lan, Jing; Liu, Chunfang; Gao, Mingxuan; Huang, Chengzhi

    2015-11-01

    In order to achieve the simple, easily repeated, and large scale preparation of fluorescent CDs, a new solid-state synthesis (SSS) approach was developed by calcining the mixture of fullerenes (C60) and solid sodium hydroxide. The cage of fullerenes could be opened and the hydroxyl and carboxyl were successfully introduced in the presence of sodium hydroxide under high temperature. The as-prepared surface carboxylated CDs possess many good properties, such as high water solubility, good photostability, salt tolerance, and nontoxicity. Especially, the fluorescence of CDs could be highly quenched by Fe(3+) because of the strong interaction of hydroxyl or carboxyl on the as-obtained CDs with Fe(3+), which realized a sensitive detection of Fe(3+) in the linear range of 0.02-0.6?mol/L. What is more, we further applied the obtained CDs into the intracellular imaging of Fe(3+). PMID:26452796

  18. Gas-assisted growth of boron-doped nickel nanotube arrays: rapid synthesis, growth mechanisms, tunable magnetic properties, and super-efficient reduction of 4-nitrophenol

    NASA Astrophysics Data System (ADS)

    Li, Xiang-Zi; Wu, Kong-Lin; Ye, Yin; Wei, Xian-Wen

    2013-04-01

    Highly ordered noncrystalline boron-doped nickel nanotube arrays are rapidly synthesized within 150 s by template-based electroless deposition. The as-prepared nanotubes have tunable magnetic properties and exhibit super efficient catalytic activity (~70 s) for the reduction of 4-nitrophenol.Highly ordered noncrystalline boron-doped nickel nanotube arrays are rapidly synthesized within 150 s by template-based electroless deposition. The as-prepared nanotubes have tunable magnetic properties and exhibit super efficient catalytic activity (~70 s) for the reduction of 4-nitrophenol. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00411b

  19. Gas-assisted growth of boron-doped nickel nanotube arrays: rapid synthesis, growth mechanisms, tunable magnetic properties, and super-efficient reduction of 4-nitrophenol.

    PubMed

    Li, Xiang-Zi; Wu, Kong-Lin; Ye, Yin; Wei, Xian-Wen

    2013-05-01

    Highly ordered noncrystalline boron-doped nickel nanotube arrays are rapidly synthesized within 150 s by template-based electroless deposition. The as-prepared nanotubes have tunable magnetic properties and exhibit super efficient catalytic activity (?70 s) for the reduction of 4-nitrophenol. PMID:23546439

  20. Solution-phase synthesis of single-crystal Cu3Si nanowire arrays on diverse substrates with dual functions as high-performance field emitters and efficient anti-reflective layers

    NASA Astrophysics Data System (ADS)

    Yuan, Fang-Wei; Wang, Chiu-Yen; Li, Guo-An; Chang, Shu-Hao; Chu, Li-Wei; Chen, Lih-Juann; Tuan, Hsing-Yu

    2013-09-01

    There is strong and growing interest in applying metal silicide nanowires as building blocks for a new class of silicide-based applications, including spintronics, nano-scale interconnects, thermoelectronics, and anti-reflective coating materials. Solution-phase environments provide versatile materials chemistry as well as significantly lower production costs compared to gas-phase synthesis. However, solution-phase synthesis of silicide nanowires remains challenging due to the lack of fundamental understanding of silicidation reactions. In this study, single-crystalline Cu3Si nanowire arrays were synthesized in an organic solvent. Self-catalyzed, dense single-crystalline Cu3Si nanowire arrays were synthesized by thermal decomposition of monophenylsilane in the presence of copper films or copper substrates at 420 to 475 °C and 10.3 MPa in supercritical benzene. The solution-grown Cu3Si nanowire arrays serve dual functions as field emitters and anti-reflective layers, which are reported on copper silicide materials for the first time. Cu3Si nanowires exhibit superior field-emission properties, with a turn-on-voltage as low as 1.16 V ?m-1, an emission current density of 8 mA cm-2 at 4.9 V ?m-1, and a field enhancement factor (?) of 1500. Cu3Si nanowire arrays appear black with optical absorption less than 5% between 400 and 800 nm with minimal reflectance, serving as highly efficient anti-reflective layers. Moreover, the Cu3Si nanowires could be grown on either rigid or flexible substrates (PI). This study shows that solution-phase silicide reactions are adaptable for high-quality silicide nanowire growth and demonstrates their promise towards fabrication of metal silicide-based devices.There is strong and growing interest in applying metal silicide nanowires as building blocks for a new class of silicide-based applications, including spintronics, nano-scale interconnects, thermoelectronics, and anti-reflective coating materials. Solution-phase environments provide versatile materials chemistry as well as significantly lower production costs compared to gas-phase synthesis. However, solution-phase synthesis of silicide nanowires remains challenging due to the lack of fundamental understanding of silicidation reactions. In this study, single-crystalline Cu3Si nanowire arrays were synthesized in an organic solvent. Self-catalyzed, dense single-crystalline Cu3Si nanowire arrays were synthesized by thermal decomposition of monophenylsilane in the presence of copper films or copper substrates at 420 to 475 °C and 10.3 MPa in supercritical benzene. The solution-grown Cu3Si nanowire arrays serve dual functions as field emitters and anti-reflective layers, which are reported on copper silicide materials for the first time. Cu3Si nanowires exhibit superior field-emission properties, with a turn-on-voltage as low as 1.16 V ?m-1, an emission current density of 8 mA cm-2 at 4.9 V ?m-1, and a field enhancement factor (?) of 1500. Cu3Si nanowire arrays appear black with optical absorption less than 5% between 400 and 800 nm with minimal reflectance, serving as highly efficient anti-reflective layers. Moreover, the Cu3Si nanowires could be grown on either rigid or flexible substrates (PI). This study shows that solution-phase silicide reactions are adaptable for high-quality silicide nanowire growth and demonstrates their promise towards fabrication of metal silicide-based devices. Electronic supplementary information (ESI) available: Additional SEM, TEM images, and FTIR spectrum of Cu3Si nanowires. See DOI: 10.1039/c3nr03045h

  1. Rapid synthesis of new block copolyurethanes derived from L-leucine cyclodipeptide in reusable molten ammonium salts: novel and efficient green media for the synthesis of new hydrolysable and biodegradable copolyurethanes.

    PubMed

    Rafiemanzelat, Fatemeh; Abdollahi, Elahe

    2012-06-01

    This study concerns the synthesis of novel multi block polyurethane (PU) copolymers containing cyclodipeptide, taking the advantage of ionic liquids (ILs) under microwave irradiation. For this, L-leucine anhydride cyclodipeptide (LACP) was prepared and then a new class of poly(ether-urethane-urea)s (PEUUs) was synthesized in molten ammonium type ILs. ILs were used as reaction media and PUs were prepared via two-step polymerization method. In the first step, 4,4'-methylene-bis-(4-phenylisocyanate) (MDI) was reacted with LACP to produce isocyanate-terminated oligo(imide-urea) as hard segment (NCO-OIU). Chain extension of the aforementioned pre-polymer with polyethyleneglycol (PEG) of molecular weights of 1000 (PEG-1000) was the second step to furnish a series of new PEUUs. These multiblock copolymers are thermally stable, soluble in amide-type solvents, hydrolysable and biodegradable. PEUUs prepared in ILs under microwave irradiation showed more phase separation and crystallinity than PEUUs prepared under conventional method. The protocol presented here has the merits of environmentally benign, simple operation, convenient work-up, short reaction time and good yields without using volatile organic solvents, and catalysts. Ammonium type reaction media were air and water stable, and relatively cheap, which makes them suitable for application. The results demonstrate that they can be easily separated into water and reused without losing activity. Reusability of tetrabutylammonium bromide as reaction media makes the method a cost effective and environmentally benign method under microwave irradiation. Thus, we could prepare environmentally friendly polymers via environmentally benign method. PMID:21706232

  2. (5RS)-6H-Spiro[pyrazolo[1,5-c]quinazoline-5,4'-thiochroman]: efficient synthesis under mild conditions, molecular structure and supramolecular assembly.

    PubMed

    Quiroga, Jairo; Gálvez, Jaime; Cobo, Justo; Glidewell, Christopher

    2015-11-01

    Pyrazolo[1,5-c]quinazolines are fused-quinazoline derivatives which have been reported as potential agents against neurological disorders. The normal synthesis routes to these compounds require harsh reaction conditions, long reaction times or multistep sequences. The title compound, C18H15N3S, has been prepared under very mild conditions by condensation of thiochroman-4-one with 5-(2-aminophenyl)-1H-pyrazole, which had itself been prepared by the reaction of hydrazine hydrate with 4-hydroxyquinoline mediated by a brief period of microwave heating. Within the molecule in the crystal structure, the reduced pyrimidine ring adopts an envelope conformation, whereas the thiane ring adopts a half-chair conformation. Molecules are linked into sheets by a combination of one N-H...S hydrogen bond and two independent C-H...?(arene) hydrogen bonds, which utilize the same aryl ring as the acceptor, with one C-H bond donating to each face of the ring. Comparisons are made with some related compounds. PMID:26524179

  3. Eco-friendly methodology for efficient synthesis and scale-up of 2-ethylhexyl-p-methoxycinnamate using Rhizopus oryzae lipase and its biological evaluation.

    PubMed

    Kumar, Vinod; Jahan, Firdaus; Kameswaran, Karthikeya; Mahajan, Richi V; Saxena, Rajendra Kumar

    2014-06-01

    Lipase-mediated synthesis of phenolic acid esters is a green and economical alternative to current chemical methods. Octyl methoxycinnamate, an important UVB-absorbing compound, was synthesized by the esterification of p-methoxycinnamic acid with 2-ethyl hexanol using Rhizopus oryzae lipase. A molar ratio of 1:2 of p-methoxycinnamic acid and 2-ethyl hexanol was found to give an optimum yield using cyclo-octane (50 ml) as reaction solvent, at a temperature of 45 °C, and 750 U of lipase, resulting in a yield of 91.3 % in 96 h. This reaction was successfully scaled up to 400-ml reaction size where 88.6 %bioconversion was achieved. The synthesized compound was found to have superior antioxidant activity as compared to ascorbic acid. The synthesized compound also exhibited good antimicrobial activity against Escherichia coli, Klebsiella pneumonia, Salmonella typhi, Staphylococcus aures, Candida albicans (yeast), Aspergillus niger, Alternaria solani, and Fussarium oxysporum by well diffusion method in terms of zone of inhibitions (in mm). PMID:24668019

  4. An asymmetric [3+2] cycloaddition of alkynes with oxiranes by selective C-C bond cleavage of epoxides: highly efficient synthesis of chiral furan derivatives.

    PubMed

    Chen, Weiliang; Fu, Xuan; Lin, Lili; Yuan, Xiao; Luo, Weiwei; Feng, Juhua; Liu, Xiaohua; Feng, Xiaoming

    2014-10-01

    An efficient enantioselective [3+2] cycloaddition of alkynes with oxiranes via selective C-C bond cleavage of epoxides was developed. A number of optically active 2,5-dihydrofurans were obtained in excellent yields (up to 99%) and enantioselectivities (up to 95% ee) under mild reaction conditions. Moreover, chiral tetrahydrofuran could also be obtained by cycloaddition of alkene and oxirane or hydrogenation of chiral 2,5-dihydrofuran. PMID:25133274

  5. A new hypercrosslinked supermicroporous polymer, with scope for sulfonation, and its catalytic potential for the efficient synthesis of biodiesel at room temperature.

    PubMed

    Bhunia, Subhajit; Banerjee, Biplab; Bhaumik, Asim

    2015-03-25

    We have designed a new hypercrosslinked supermicroporous polymer (HMP-1) with a BET surface area of 913 m(2) g(-1) by FeCl3 via a catalyzed Friedel-Crafts alkylation reaction between carbazole and ?,?'-dibromo-p-xylene. Upon sulfonation HMP-1 yielded a very efficient solid acid catalyst for the production of biodiesels via esterification/transesterification of free fatty acids (FFA)/esters at room temperature. PMID:25702885

  6. Synthesis and investigation of singlet oxygen production efficiency of photosensitizers based on meso-phenyl-2,5-thienylene linked porphyrin oligomers and polymers.

    PubMed

    Khan, Rehan; Idris, Muazzam; Tuncel, Dönüs

    2015-11-14

    Three new Zn(ii)-, oligo- and poly(2,5-thienylene)-linked porphyrins, bearing multiple triethylene glycol (TEG) groups, on all meso aryl positions were synthesized via Stille and Suzuki coupling reactions and their photophysical properties as well as singlet oxygen generation efficiencies have been investigated to elucidate the possibility of their use as a photosensitizer for photodynamic therapy (PDT) and photodynamic inactivation of bacteria. PMID:26332671

  7. Synthesis, optical and electrochemical properties of the A-?-D-?-A porphyrin and its application as an electron donor in efficient solution processed bulk heterojunction solar cells

    NASA Astrophysics Data System (ADS)

    Vijay Kumar, Challuri; Cabau, Lydia; Koukaras, Emmanuel N.; Sharma, Ganesh D.; Palomares, Emilio

    2014-11-01

    A conjugated acceptor-donor-acceptor (A-?-D-?-A) with the Zn-porphyrin core and the di-cyanovinyl substituted thiophene (A) connected at meso positions denoted as VC62 was designed and synthesized. The optical and electrochemical properties of VC62 were investigated. This new porphyrin exhibits a broad and intense absorption in the visible and near infrared regions. Bulk-heterojunction (BHJ) solution processed organic solar cells based on this porphyrin, as electron donor material, and PC71BM ([6,6]-phenyl C71 butyric acid methyl ester), as electron acceptor material, were fabricated using THF and a pyridine-THF solvent exhibiting a power conversion efficiency of 3.65% and 5.24%, respectively. The difference in efficiencies is due to the enhancement of the short circuit current Jsc and FF of the solar cell, which is ascribed to a stronger and broader incident photon to current efficiency (IPCE) response and a better balanced charge transport in the device processed with the pyridine-THF solvent.

  8. The reaction of primary aromatic amines with alkylene carbonates for the selective synthesis of bis-N-(2-hydroxy)alkylanilines: the catalytic effect of phosphonium-based ionic liquids.

    PubMed

    Selva, Maurizio; Fabris, Massimo; Lucchini, Vittorio; Perosa, Alvise; Noè, Marco

    2010-11-21

    At T? 140 °C, different primary aromatic amines (pX-C(6)H(4)NH(2); X = H, OCH(3), CH(3), Cl) react with both ethylene- and propylene-carbonates to yield a chemoselective N-alkylation process: bis-N-(2-hydroxyalkyl)anilines [pX-C(6)H(4)N(CH(2)CH(R)OH)(2); R = H, CH(3)] are the major products and the competitive formation of carbamates is substantially ruled out. At 140 °C, under solventless conditions, the model reaction of aniline with ethylene carbonate goes to completion by simply mixing stoichiometric amounts of the reagents. However, a class of phosphonium ionic liquids (PILs) such as tetraalkylphosphonium halides and tosylates turn out to be active organocatalysts for both aniline and other primary aromatic amines. A kinetic analysis monitored by (13)C NMR spectroscopy, shows that bromide exchanged PILs are the most efficient systems, able to impart a more than 8-fold acceleration to the reaction. The reactions of propylene carbonate take place at a higher temperature than those of ethylene carbonate, and only in the presence of PIL catalysts. A mechanism based on the Lewis acidity of tetraalkylphosphonium cations and the nucleophilicity of halide anions has been proposed to account for both the reaction chemoselectivity and the function of the catalysts. PMID:20844790

  9. Microwave-assisted solvothermal synthesis of flower-like Ag/AgBr/BiOBr microspheres and their high efficient photocatalytic degradation for p-nitrophenol

    SciTech Connect

    Li, Tingting; Luo, Shenglian; Yang, Lixia

    2013-10-15

    Flower-like Ag/AgBr/BiOBr microspheres were successfully fabricated by the approach of microwave-assisted solvothermal and in situ photo-assisted reduction. A reactive ionic liquid 1-hexadecyl-3-methylimidazolium bromide ([C{sub 16}mim]Br) was employed as Br source in the presence of surfactant polyvinylpyrrolidone (PVP). The photocatalytic activity of Ag/AgBr/BiOBr towards the decomposition of p-nitrophenol under visible light irradiation was evaluated. The results indicated that Ag/AgBr/BiOBr showed enhanced photocatalytic activity towards p-nitrophenol, comparing with P25, BiOBr and Ag/AgBr. More than 96% of p-nitrophenol was decomposed in 3.5 h under visible-light irradation. The excellent photocatalytic activity of flower-like Ag/AgBr/BiOBr microspheres can be attributed to the large specific surface area, strong visible-light absorption, suitable energy band structure and surface plasmon resonance effect of Ag nanoparticles. The possible photocatalytic mechanism was proposed based on the active species test and band gap structure analysis. - Graphical abstract: The photocatalytic reaction mechanisms of the as-prepared Ag/AgBr/BiOBr. Display Omitted - Highlights: • Successful synthesis of flower-like Ag/AgBr/BiOBr microspheres. • The Ag/AgBr/BiOBr showed much higher photocatalytic activity towards p-nitrophenol as compared to BiOBr and Ag/AgBr. • The reasons for the excellent photocatalytic activity are the large specific surface area, strong visible-light absorption and surface plasmon resonance effect of Ag nanoparticles. • The O{sub 2}·{sup ?}, Br{sup 0} and photogenerated h{sup +} play key roles in the photocatalytic degradation process.

  10. Magnetic Cross-Linked Enzyme Aggregates (mCLEAs) of Candida antarctica Lipase: An Efficient and Stable Biocatalyst for Biodiesel Synthesis

    PubMed Central

    Cruz-Izquierdo, Álvaro; Picó, Enrique A.; López, Carmen; Serra, Juan L.; Llama, María J.

    2014-01-01

    Enzyme-catalyzed production of biodiesel is the object of extensive research due to the global shortage of fossil fuels and increased environmental concerns. Herein we report the preparation and main characteristics of a novel biocatalyst consisting of Cross-Linked Enzyme Aggregates (CLEAs) of Candida antarctica lipase B (CALB) which are covalently bound to magnetic nanoparticles, and tackle its use for the synthesis of biodiesel from non-edible vegetable and waste frying oils. For this purpose, insolubilized CALB was covalently cross-linked to magnetic nanoparticles of magnetite which the surface was functionalized with –NH2 groups. The resulting biocatalyst combines the relevant catalytic properties of CLEAs (as great stability and feasibility for their reutilization) and the magnetic character, and thus the final product (mCLEAs) are superparamagnetic particles of a robust catalyst which is more stable than the free enzyme, easily recoverable from the reaction medium and reusable for new catalytic cycles. We have studied the main properties of this biocatalyst and we have assessed its utility to catalyze transesterification reactions to obtain biodiesel from non-edible vegetable oils including unrefined soybean, jatropha and cameline, as well as waste frying oil. Using 1% mCLEAs (w/w of oil) conversions near 80% were routinely obtained at 30°C after 24 h of reaction, this value rising to 92% after 72 h. Moreover, the magnetic biocatalyst can be easily recovered from the reaction mixture and reused for at least ten consecutive cycles of 24 h without apparent loss of activity. The obtained results suggest that mCLEAs prepared from CALB can become a powerful biocatalyst for application at industrial scale with better performance than those currently available. PMID:25551445

  11. Synthesis of SnO2 pillared carbon using long chain alkylamine grafted graphene oxide: an efficient anode material for lithium ion batteries.

    PubMed

    Reddy, M Jeevan Kumar; Ryu, Sung Hun; Shanmugharaj, A M

    2015-12-17

    With the objective of developing new advanced composite materials that can be used as anodes for lithium ion batteries (LIBs), herein we describe the synthesis of SnO2 pillared carbon using various alkylamine (hexylamine; dodecylamine and octadecylamine) grafted graphene oxides and butyl trichlorotin precursors followed by its calcination at 500 °C for 2 h. While the grafted alkylamine induces crystalline growth of SnO2 pillars, thermal annealing of alkylamine grafted graphene oxide results in the formation of amorphous carbon coated graphene. Field emission scanning electron microscopy (FE-SEM) results reveal the successful formation of SnO2 pillared carbon on the graphene surface. X-ray diffraction (XRD), transmission electron microscopy (TEM) and Raman spectroscopy characterization corroborates the formation of rutile SnO2 crystals on the graphene surface. A significant rise in the BET surface area is observed for SnO2 pillared carbon, when compared to pristine GO. Electrochemical characterization studies of SnO2 pillared carbon based anode materials showed an enhanced lithium storage capacity and fine cyclic performance in comparison with pristine GO. The initial specific capacities of SnO2 pillared carbon are observed to be 1379 mA h g(-1), 1255 mA h g(-1) and 1360 mA h g(-1) that decrease to 750 mA h g(-1), 643 mA h g(-1) and 560 mA h g(-1) depending upon the chain length of grafted alkylamine on the graphene surface respectively. Electrochemical impedance spectral analysis reveals that the exchange current density of SnO2 pillared carbon based electrodes is higher, corroborating its enhanced electrochemical activity in comparison with GO based electrodes. PMID:26628211

  12. One-pot synthesis of C??-functionalized core-shell magnetic mesoporous silica composite as efficient sorbent for organic dye.

    PubMed

    Zhang, Xiaole; Zeng, Tao; Wang, Saihua; Niu, Hongyun; Wang, Xiaoke; Cai, Yaqi

    2015-06-15

    In this work, a facile one-pot strategy was proposed for the synthesis of C18-functionalized core-shell magnetic mesoporous silica composite (Fe3O4/mSiO2-C18). The Fe3O4/mSiO2-C18 composite, with an average size of 80 nm and a functionalized mesoporous silica shell of about 30 nm in thickness, has excellent adsorption ability toward methylene blue dye (MB) due to the large surface area (303 m(2) g(-1)) and the abundant hydrophobic C18 groups. The adsorption equilibrium was achieved within 20 min and the adsorption behavior of MB on Fe3O4/mSiO2-C18 composite fitted the pseudo-second-order kinetic model well (k2=1.29×10(-2) g mg(-1) min(-1), q(e)=144.72 mg g(-1), h(o)=270.27 mg g(-1) min(-1) under 25 °C and an initial MB concentration of 10 mg L(-1)). Langmuir and Freundlich isothermal adsorption models can both be used to describe the adsorption process and the maximum Langmuir adsorption capacity of MB on Fe3O4/mSiO2-C18 at 25 °C and pH 7.5 is 363.64 mg g(-1). Thermodynamic parameters show that the adsorption reaction is exothermic and spontaneous (?H(0)=-63.49 kJ mol(-1), ?G(0)=-7.80 kJ mol(-1)). Ionic strength and pH affected the adsorption slightly. In addition, the MB adsorbed sorbent can be readily separated from water solution by an external magnet because of the high magnetic saturation value (22.62 emu g(-1)). After being regenerated by treatment with acidic methanol, the sorbent could be reused for at least 5 cycles with a little decrease in adsorption capacity. PMID:25734221

  13. Microwave Induced Combustion Synthesis of Ceramic and Ceramic-Metal Composites

    NASA Technical Reports Server (NTRS)

    Yiin, T.; Barmatz, M.; Feng, H.; Moore, J.

    1995-01-01

    In recent years, there has been a renewed interest in combustion synthesis reactions, commonly called self-propagating high-temperature synthesis. These reactions are an attractive, energy efficient approach to the synthesis of high temperature composite materials and metastable phases. Microwaves are used to induce self-propagating high temperature synthesis of ceramic and ceramic-metal composites.

  14. Synthesis of Mn-intercalated layered titanate by exfoliation-flocculation approach and its efficient photocatalytic activity under visible-light

    SciTech Connect

    Fu, Jie; Tian, Yanlong; Chang, Binbin; Li, Gengnan; Xi, Fengna; Dong, Xiaoping

    2012-12-15

    A novel Mn-intercalated layered titanate as highly active photocatalyst in visible-light region has been synthesized via a convenient and efficient exfoliation-flocculation approach with divalent Mn ions and monolayer titanate nanosheets. The 0.91 nm interlayer spacing of obtained photocatalyst is in accordance with the sum of the thickness of titanate nanosheet and the diameter of Mn ions. The yellow photocatalyst shows a spectral response in visible-light region and the calculated band gap is 2.59 eV. The photocatalytic performance of this material was evaluated by degradation and mineralization of an aqueous dye methylene blue under visible-light irradiation, and an enhanced photocatalytic activity in comparison with protonated titanate as well as the P25 TiO{sub 2} and N-doped TiO{sub 2} was obtained. Additionally, the layered structure is retained, no dye ions intercalating occurs during the photocatalysis process, and a {approx}90% photocatalytic activity can be remained after reusing 3 cycles. - Graphical abstract: Mn-intercalated layered titanate as a novel and efficient visible-light harvesting photocatalyst was synthesized via a convenient and efficient exfoliation-flocculation approach in a mild condition. Highlights: Black-Right-Pointing-Pointer Mn-intercalated titanate has been prepared by exfoliation-flocculation approach. Black-Right-Pointing-Pointer The as-prepared catalyst shows spectral response in the visible-light region. Black-Right-Pointing-Pointer Heat treatment at certain temperature enables formation of Mn-doped TiO{sub 2}. Black-Right-Pointing-Pointer Dye can be degradated effectively by the catalyst under visible light irradiation.

  15. Lipophilic M(?,?'-OC5H11)8phthalocyanines (M = H2 and Ni(ii)): synthesis, electronic structure, and their utility for highly efficient carbonyl reductions.

    PubMed

    Jiang, Yu; Li, Minzhi; Liang, Xu; Mack, John; Wildervanck, Martijn; Nyokong, Tebello; Qin, Mingfeng; Zhu, Weihua

    2015-11-01

    A lipophilic and electron-rich phthalocyanine (?,?'-n-OC5H11)8-H2Pc and its nickel(ii) complex (?,?'-n-OC5H11)8-Ni(ii)Pc have been synthesized and characterized. Detailed analyses of the electronic structure were carried out by spectroscopy, electrochemistry, spectroelectrochemistry, and TD-DFT calculations. A series of experiments demonstrate that the (?,?'-n-OC5H11)8-Ni(ii)Pc complex can be used as a catalyst for highly efficient carbonyl reductions. PMID:26425817

  16. Concise synthesis of the core structures of saundersiosides.

    PubMed

    Cheng, Shou-Ling; Jiang, Xiao-Ling; Shi, Yong; Tian, Wei-Sheng

    2015-05-15

    A divergent synthesis of three core pentacyclic lactones of nine rearranged cholestane sapogenins, saundersiosides A-H (1-8) and candicanoside A (9), is reported. Key features include a one-flask CBS reduction/Brown hydroboration-oxidation, a SmI2-mediated intramolecular Reformatskii reaction, and an intramolecular transesterification. This synthesis provides a general strategy and key precursors for the collective synthesis of natural and designed saundersiosides. An efficient formal synthesis of candicanoside A is also achieved. PMID:25937005

  17. Synthesis of iron oxide/partly graphitized carbon composites as a high-efficiency and low-cost cathode catalyst for microbial fuel cells.

    PubMed

    Ma, Ming; Dai, Ying; Zou, Jin-long; Wang, Lei; Pan, Kai; Fu, Hong-gang

    2014-08-27

    Waste cornstalks and pomelo skins are used as carbon resources for preparing nanocomposites of iron oxide and partly graphitized carbon (Fe3O4/PGC-CS and Fe3O4/PGC-PS). The results showed that Fe3O4 with a face-centered cubic structure is uniformly dispersed on the skeleton of Fe3O4/GC, and the highest SBET values of Fe3O4/PGC-CS (476.5 m(2) g(-1)) and Fe3O4/PGC-PS (547.7 m(2) g(-1)) are obtained at 1000 °C. The electrical conductivity and density of catalytic active sites are correspondingly improved by the introduction of Fe species. Microbial fuel cells (MFCs) with a mixed composite (Fe3O4/PGC-CS:Fe3O4/PGC-PS = 1:1) cathode (three-dimensional structures) generate the highest power density of 1502 ± 30 mW m(-2), which is 26.01% higher than that of Pt/C (1192 ± 33 mW m(-2)) and only declines by 7.12% after 18 cycles. The Fe3O4/PGC-CS cathode has the highest Coulombic efficiency (24.3 ± 0.7%). The Fe3O4/PGC composites exhibit high oxygen reduction reactivity, low charge transfer resistances, and long-term stability and can be used as a low-cost and high-efficiency catalyst for MFCs. PMID:25084054

  18. Hierarchical structured carbon derived from bagasse wastes: A simple and efficient synthesis route and its improved electrochemical properties for high-performance supercapacitors

    NASA Astrophysics Data System (ADS)

    Feng, Haobin; Hu, Hang; Dong, Hanwu; Xiao, Yong; Cai, Yijin; Lei, Bingfu; Liu, Yingliang; Zheng, Mingtao

    2016-01-01

    Bagasse-derived hierarchical structured carbon (BDHSC) with tunable porosity and improved electrochemical performance is prepared via simple and efficient hydrothermal carbonization combined with KOH activation. Experimental results show that sewage sludge acts as a cheap and efficient structure-directing agent to regulate the morphology, adjust the porosity, and thus improve the supercapacitive performance of BDHSC. The as-resulted BDHSC exhibits an interconnected framework with high specific surface area (2296 m2 g-1), high pore volume (1.34 cm3 g-1), and hierarchical porosity, which offer a more favorable pathway for electrolyte penetration and transportation. Compared to the product obtained from bagasse without sewage sludge, the unique interconnected BDHSC exhibits enhanced supercapacitive performances such as higher specific capacitance (320 F g-1), and better rate capability (capacitance retention over 70.8% at a high current density of 50 A g-1). Moreover, the BDHSC-based symmetric supercapacitor delivers a maximum energy density of over 20 Wh kg-1 at 182 W kg-1 and presents an excellent long-term cycling stability. The developed approach in the present work can be useful not only in production of a variety of novel hierarchical structured carbon with promising applications in high-performance energy storage devices, but also in high-value utilization of biomass wastes and high-ash-content sewage sludge.

  19. Synthesis of high efficient Ca{sub 2}SiO{sub 4}:Eu{sup 2+} green emitting phosphor by a liquid phase precursor method

    SciTech Connect

    Luo, Y.Y.; Jo, D.S.; Senthil, K.; Tezuka, S.; Kakihana, M.; Toda, K.; Masaki, T.; Yoon, D.H.

    2012-05-15

    Green emitting Eu{sup 2+}-doped Ca{sub 2}SiO{sub 4} phosphors were synthesized by three different methods (a conventional solid state reaction (SSR) method, a novel liquid phase precursor approach using SiO{sub 2} sol (LPP-SiO{sub 2}(sol)) and water-soluble silicon compound (LPP-WSS)). The obtained phosphors exhibited a broad excitation spectrum ranging from 225 to 450 nm and a strong green emission peak at 502 nm due to the 4f{sup 6}5d{sup 1}{yields}4f{sup 7}({sup 8}S{sub 7/2}) transition of Eu{sup 2+}. The highest luminescent intensity was obtained for the samples fired at 1100 Degree-Sign C. The dependence of luminescence properties on Eu{sup 2+} concentration for the phosphors synthesized using LPP-WSS method was also examined from 0.1 to 5.0 mol% and the maximum emission intensity was observed at 3.0 mol% Eu{sup 2+}. A detailed analysis using various characterizations revealed that phosphors produced by the LPP-WSS process exhibited more homogenous phase distribution and higher luminescence intensity than those from the other two processes, which suggested the potential application of Ca{sub 2}SiO{sub 4}:Eu{sup 2+} in white light-emitting diodes and fluorescence lamps. - Graphical abstract: The synthesis of Eu{sup 2+} doped Ca{sub 2}SiO{sub 4} green emitting phosphors were carried out using LPP-SiO{sub 2}(sol), LPP-WSS and SSR methods. The adequate reaction of starting materials base on solution mixing and cellulose impregnating during LPP-WSS procedure resulted in single crystalline structure as well as fine morphology, and finally determined a superior luminescent intensity. Highlights: Black-Right-Pointing-Pointer Ca{sub 2}SiO{sub 4}:Eu{sup 2+} phosphor was synthesized by three methods (SSR, LPP-SiO{sub 2} and LPP-WSS). Black-Right-Pointing-Pointer Effect of different processes on the property of phosphor was studied. Black-Right-Pointing-Pointer Phosphor produced by LPP-WSS showed better homogenous phase and fluorescent property. Black-Right-Pointing-Pointer LPP-WSS approach was identified as the best method among these three approaches.

  20. One-pot synthesis of nitrogen and sulfur co-doped onion-like mesoporous carbon vesicle as an efficient metal-free catalyst for oxygen reduction reaction in alkaline solution

    NASA Astrophysics Data System (ADS)

    Han, Ce; Bo, Xiangjie; Zhang, Yufan; Li, Mian; Guo, Liping

    2014-12-01

    Nitrogen and sulfur co-doped onion-like mesoporous carbon vesicle (NS-MCV) with multilayer lamellar structure is synthesized as a metal-free catalyst through a convenient and economical procedure. The synthesized materials are systematically characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectra, nitrogen adsorption-desorption, and X-ray photoelectron spectroscopy (XPS). The characterization results demonstrate that N and S atoms can be successfully doped into the framework of MCV with little impact on the morphology and structure. The NS-MCV manifests a remarkably high electrocatalytic activity as a metal-free electrocatalyst for the oxygen reduction reaction (ORR) with mainly a four-electron transfer pathway. Moreover, in contrast to the commercially available Pt/C catalyst, the NS-MCV shows much better long-term stability and tolerance toward methanol crossover in an alkaline medium. Such excellent performances can be mainly attributed to the synergistic effect arising from the addition of N and S heteroatom, optimized S content and high surface area. The NS-MCV with a simple synthesis method may further exploited as potentially efficient and inexpensive metal-free ORR catalyst materials.

  1. Ligand-assisted soft-chemical synthesis of self-assembled different shaped mesoporous Co3O4: efficient visible light photocatalysts.

    PubMed

    Roy, Mouni; Ghosh, Sourav; Naskar, Milan Kanti

    2015-04-21

    Mesoporous self-assembled cobalt oxide (Co3O4) of different shapes was synthesized by a facile soft-chemical process using cobalt nitrate, oxalic acid and phosphoric acid in the presence of cationic templates, cetyltrimethylammonium bromide, 1-butyl-3-methylimidazolium bromide, and pyridinium bromide at 75 °C/2 h followed by calcination at 300 °C. The effect of cationic templates of the samples on the physico-chemical properties, and the photocatalytic efficiency for the degradation of Chicago Sky Blue 6B was studied. Pyridinium bromide and 1-butyl-3-methylimidazolium bromide facilitated formation of particles with different shaped morphology compared to cetyltrimethylammonium bromide. The rod-like particles having higher surface area exhibited higher photocatalytic performance. PMID:25792483

  2. Shape-controlled synthesis of Pd polyhedron supported on polyethyleneimine-reduced graphene oxide for enhancing the efficiency of hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Li, Jing; Zhou, Panpan; Li, Feng; Ma, Jianxin; Liu, Yang; Zhang, Xueyao; Huo, Hongfei; Jin, Jun; Ma, Jiantai

    2016-01-01

    The catalytic activity of noble-metal nanoparticles (NPs) often has closely connection with their sizes and geometric shape. In the work, polyhedral NPs of palladium (Pd) with controlled sizes, shapes, and different proportions of {100} to {111} facets on the surface were prepared by a seed-mediated approach. Electrochemical experiment demonstrates that the catalytic performance of the Pd nanocubes (NCs) enclosed by {100} facets is more active than Pd octahedrons enclosed by {111} facets for the hydrogen evolution reaction (HER), which is consistent with density functional theory (DFT) calculation results. Meanwhile, with the assistance of a polyethyleneimine-reduced graphene oxide (PEI-rGO) support, the examined Pd cube/PEI-rGO50:1 (10 wt. %) electrocatalyst presents outstanding HER activity comparable with that of commercial Pt/C catalyst. This correlation between the HER catalytic activity and surface structure will contribute to the reasonable design of Pd catalysts for HER with high efficiency and low metal loading.

  3. Single-crystalline Bi2Te3 nanosheets with uniform morphology via a simple, efficient, and high-yield microwave-assisted synthesis

    NASA Astrophysics Data System (ADS)

    Li, Zhiliang; Teng, Renyuan; Zheng, Shuqi; Zhang, Yuzhuo; Huang, Ting; Lu, Guiwu

    2014-11-01

    A simple but efficient microwave-assisted method with high-yield products was applied to synthesize regular hexagon Bi2Te3 nanosheets. Rhombohedral Bi2Te3 with pure single crystalline phase was demonstrated by XRD patterns, HRTEM images, and SAED figures. The SEM and TEM images showed that the Bi2Te3 nanosheets were uniform, and that the average lengths of the hexagon sides were approximately 320 nm. The growth mechanisms and morphological transformations were systematically studied by controlling the reaction time, KOH concentration, and polyvinylpyrrolidone (PVP) dosage. This work has indicated that abundant KOH benefited the formation of uniform Bi2Te3 nanosheets without Te nanorods. Meanwhile, long reaction time and abundant PVP favored the formation of regular hexagon nanosheets with smooth surfaces.

  4. Efficient synthesis of optically pure alcohols by asymmetric hydrogen-transfer biocatalysis: application of engineered enzymes in a 2-propanol-water medium.

    PubMed

    Itoh, Nobuya; Isotani, Kentaro; Nakamura, Masatoshi; Inoue, Kousuke; Isogai, Yasuhiro; Makino, Yoshihide

    2012-02-01

    We describe an efficient method for producing both enantiomers of chiral alcohols by asymmetric hydrogen-transfer bioreduction of ketones in a 2-propanol (IPA)-water medium with E. coli biocatalysts expressing phenylacetaldehyde reductase (PAR: wild-type and mutant enzymes) from Rhodococcus sp. ST-10 and alcohol dehydrogenase from Leifsonia sp. S749 (LSADH). We also describe the detailed properties of mutant PARs, Sar268, and HAR1, which were engineered to have high activity and productivity in media composed of polar organic solvent and water, and the construction of three-dimensional structure of PAR by homology modeling. The K(m) and V(max) values for some substrates and the substrate specificity of mutant PARs were quite different from those of wild-type PAR. The results well explained the increased productivity of engineered PARs in IPA-water medium. PMID:21739266

  5. One-pot synthesis of NiFe layered double hydroxide/reduced graphene oxide composite as an efficient electrocatalyst for electrochemical and photoelectrochemical water oxidation

    NASA Astrophysics Data System (ADS)

    Youn, Duck Hyun; Park, Yoon Bin; Kim, Jae Young; Magesh, Ganesan; Jang, Youn Jeong; Lee, Jae Sung

    2015-10-01

    As an efficient non-precious metal catalyst for oxygen evolution reaction (OER) in electrochemical and photoelectrochemical water splitting, NiFe layered double hydroxide (LDH)/reduced graphene oxide (NiFe/RGO) composite is synthesized by a simple solvothermal method in one-pot. NiFe LDHs are uniformly deposited on RGO layers of high electrical conductivity and large surface area. In electrochemical water splitting, NiFe/RGO shows superior OER performance compared to bare NiFe and reference IrO2 with a lower benchmark ?10 value (required overpotential to drive 10 mA cm-2) of 0.245 V. Furthermore, NiFe/RGO substantially increases the performance of a hematite photoanode in photoelectrochemical water oxidation, demonstrating its potential as an OER co-catalyst for photoelectrodes.

  6. 3,4,5-Trisubstituted Furan-2(5H)-one Derivatives: Efficient one-pot Synthesis and Evaluation of Cytotoxic Activity.

    PubMed

    Basyouni, W M; El-Bayouki, Kh A M; El-Sayed, A S; Tohamy, W M; Farag, M M S; Abd-El-Baseer, M A

    2015-09-01

    A series of 3,4,5-trisubstituted 2(5H)-furanone derivatives was synthesized through one-pot reaction of amines, aldehydes and diethyl acetylenedicarboxylate. Silica sulfuric acid efficiently catalyzes the 3-component reaction to afford the corresponding 2(5H)-furanones in high yields. The synthesized compounds were tested against HEPG2, MCF7 and CACO tumor cell lines. The cytotoxic activity for the tested compounds showed that: ethyl 2-(4-fluorophenyl)-5-oxo-4-(phenylamino)-2,5-dihydrofuran-3-carboxylate exhibited significant antitumor activity against HEPG2 and MCF7 cell lines (IC50 values 0.002 and 0.002 µM, respectively) more than reference drug (IC50 0.007, 0.005 µM). PMID:25207706

  7. Design and synthesis of a chiral uranium-based microporous metal organic framework with high SHG efficiency and sequestration potential for low-valent actinides.

    PubMed

    Wang, Yanlong; Li, Yuxiang; Bai, Zhuanling; Xiao, Chengliang; Liu, Zhiyong; Liu, Wei; Chen, Lanhua; He, Weiwei; Diwu, Juan; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

    2015-10-27

    The solvothermal reaction of [tris-(4-carboxylphenyl)phosphineoxide] (H3TPO) with UO2(NO3)2·6H2O in DMF affords a uranium-based chiral, microporous, metal-organic framework compound [(CH3)2NH2][UO2(TPO)]·4DMF·12.5H2O () that exhibits the highest void volume (68.8%) and second-harmonic generation (SHG) efficiency (1.54 KDP) for an actinide compound reported to date. The combination of large channels and the coordination capabilities of P[double bond, length as m-dash]O moieties in the structure enables to capture large amounts of Th(iv) from aqueous solutions, providing a new strategy for preparing heterobimetallic 5f/5f compounds, and may lead to applications in nuclear waste management. PMID:26459775

  8. A versatile cyclic 2,2'-azobenzenophane with a functional handle and its polymers: efficient synthesis and effect of topological structure on chiroptical properties.

    PubMed

    Lu, Jinjie; Xia, Aiyou; Zhou, Nianchen; Zhang, Wei; Zhang, Zhengbiao; Pan, Xiangqiang; Yang, Yonggang; Wang, Yong; Zhu, Xiulin

    2015-02-01

    Two novel cyclic azobenzenophanes (SC, RC) with functional handles have been synthesized efficiently by a Glaser coupling reaction. Through a Suzuki coupling reaction, alternating ring/linear polymers with rigid (conjugated)/flexible (unconjugated) bridges were obtained from the resultant cyclic azobenzenophanes. The optical activities of linear, cyclic, and macromolecular binaphethyl-azobenzene derivatives were investigated by UV/Vis and circular dichroism (CD) spectra and the time-dependent (TD)-DFT method. Experimental results and theoretical analyses indicated that the cyclic configurations exhibited better chiroptical features than the others, and the reverse conformation and difference of dextro-/levo-rotation of azobenzenophanes were detected by comparing linear and cyclic structures, which provides an opportunity for the optical-rotation-controlled "smart" materials systems in future. PMID:25510346

  9. The Environment of “Mycobacterium avium subsp. hominissuis” Microaggregates Induces Synthesis of Small Proteins Associated with Efficient Infection of Respiratory Epithelial Cells

    PubMed Central

    Babrak, Lmar; Danelishvili, Lia; Rose, Sasha J.; Kornberg, Tiffany

    2014-01-01

    “Mycobacterium avium subsp. hominissuis” is an opportunistic environmental pathogen that causes respiratory illness in immunocompromised patients, such as those with cystic fibrosis as well as other chronic respiratory diseases. Currently, there is no efficient approach to prevent or treat M. avium subsp. hominissuis infection in the lungs. During initial colonization of the airways, M. avium subsp. hominissuis forms microaggregates composed of 3 to 20 bacteria on human respiratory epithelial cells, which provides an environment for phenotypic changes leading to efficient mucosal invasion in vitro and in vivo. DNA microarray analysis was employed to identify genes associated with the microaggregate phenotype. The gene encoding microaggregate-binding protein 1 (MBP-1) (MAV_3013) is highly expressed during microaggregate formation. When expressed in noninvasive Mycobacterium smegmatis, MBP-1 increased the ability of the bacteria to bind to HEp-2 epithelial cells. Using anti-MBP-1 immune serum, microaggregate binding to HEp-2 cells was significantly reduced. By far-Western blotting, and verified by coimmunoprecipitation, we observed that MBP-1 interacts with the host cytoskeletal protein vimentin. As visualized by confocal microscopy, microaggregates, as well as MBP-1, induced vimentin polymerization at the site of bacterium-host cell contact. Binding of microaggregates to HEp-2 cells was inhibited by treatment with an antivimentin antibody, suggesting that MBP-1 expression is important for M. avium subsp. hominissuis adherence to the host cell. MBP-1 immune serum significantly inhibited M. avium subsp. hominissuis infection throughout the respiratory tracts of mice. This study characterizes a pathogenic mechanism utilized by M. avium subsp. hominissuis to bind and invade the host respiratory epithelium, suggesting new potential targets for the development of antivirulence therapy. PMID:25422262

  10. Single-Step Synthesis of SnS? Nanosheet-Decorated TiO? Anatase Nanofibers as Efficient Photocatalysts for the Degradation of Gas-Phase Diethylsulfide.

    PubMed

    Christoforidis, Konstantinos C; Sengele, Armelle; Keller, Valérie; Keller, Nicolas

    2015-09-01

    We report on a facile one-step soft hydrothermal process for synthesizing 1D anatase TiO2 nanofibers decorated with ultrathin SnS2 nanosheets. H-titanate nanofibers were used as preshaped Ti precursor. Under controlled conditions, the H-titanate structure was transformed into anatase maintaining the fibril morphology, while at the same time SnS2 nanosheets were grown in situ on the surface of the nanofibers. The successful formation of SnS2 nanosheets on the TiO2 nanofibers was confirmed by high-resolution TEM, and together with XPS spectroscopy, the tight interface formed between the SnS2 and the anatase TiO2 nanofibers was verified. The 1D SnS2/TiO2 hierarchical nanostructures with semiconductor heterojunction were proven to be very efficient under artificial solar irradiation in the photocatalytic degradation of gaseous diethylsulfide as simulant for live yperite chemical warfare agent as well as model substrate for malodorous organosulfide volatile organic compounds. SnS2 did not operate as a visible light sensitizer for TiO2 but rather as an oxidizing agent and charge-carrier separator. The semiconductor ratio in the heterostructure controlled the photoactivity. Samples with no or high content of SnS2 were less active than those with moderate SnS2 content. Enhanced reactivity was ascribed to an efficient separation of the photogenerated charge carriers driven by the differences in band edge positions and favored by the tight interface within the coupled heterostructure. PMID:26262595

  11. The use of N-urethane-protected N-carboxyanhydrides (UNCAs) in amino acid and peptide synthesis.

    PubMed

    Fehrentz, J A; Genu-Dellac, C; Amblard, M; Winternitz, F; Loffet, A; Martinez, J

    1995-01-01

    N-Urethane-protected N-carboxyanhydrides (UNCAs) are very reactive amino acid derivatives. They have been successfully used in peptide synthesis, in both solution and solid phase. We have demonstrated that UNCAs are interesting starting materials for the synthesis of various amino acid derivatives. Chemoselective reduction of UNCAs with sodium borohydride led the corresponding N-protected beta amino alcohols. Reaction of UNCAs with Meldrum's acid, followed by cyclisation, yielded enantiomerically pure tetramic acid derivatives. Diastereoselective reduction of tetramic acid derivatives produced [4S,5S)-N-alkoxycarbonyl-4-hydroxy-5-alkylpyrrolidin-2-ones derived from amino acids, which after hydrolysis yielded statine and statine analogues. Tetramic acid derivatives could also be obtained by reaction of UNCAs with benzyl ethyl malonate in the presence of sodium hydride to yield gamma-N-benzyloxycarbonylamino-beta-oxodicarboxyl esters followed by hydrogenolytic deprotection and decarboxylation. UNCAs also reacted with phosphoranes to produce the ketophosphorane in excellent yields. Subsequent oxidation with oxone or with [bis(acetoxy)-iodo]-benzene produced vicinal tricarbonyl derivatives. These reactions usually proceeded smoothly and with high yields. PMID:9222989

  12. Rational design of hyperbranched 3D heteroarrays of SrS/CdS: synthesis, characterization and evaluation of photocatalytic properties for efficient hydrogen generation and organic dye degradation

    NASA Astrophysics Data System (ADS)

    Khan, Ziyauddin; Chetia, Tridip Ranjan; Qureshi, Mohammad

    2012-05-01

    Hyperbranched 3D SrS/CdS nanostructures were synthesized using a one pot hydrothermal method. Transmission Electron Microscopy (TEM) and Field Emission-Scanning Electron Microscopy (FE-SEM) analysis showed the formation of flower-like structure and the crystalline phase was confirmed by powder X-ray diffraction. The prepared 3D SrS/CdS exhibited improved photocatalytic activity for water splitting leading to H2 generation (AQY 10%) and nearly complete degradation of methyl orange (MO) dye. The dye degradation followed first order kinetics and the apparent reaction rate constant (kapp) was 0.136 min-1. The present 3D SrS/CdS structure promise to be efficient photocatalysts due to (i) the facile intersystem charge transfer resulting from their band alignment (ii) enhanced specific surface area and (iii) crystallinity.Hyperbranched 3D SrS/CdS nanostructures were synthesized using a one pot hydrothermal method. Transmission Electron Microscopy (TEM) and Field Emission-Scanning Electron Microscopy (FE-SEM) analysis showed the formation of flower-like structure and the crystalline phase was confirmed by powder X-ray diffraction. The prepared 3D SrS/CdS exhibited improved photocatalytic activity for water splitting leading to H2 generation (AQY 10%) and nearly complete degradation of methyl orange (MO) dye. The dye degradation followed first order kinetics and the apparent reaction rate constant (kapp) was 0.136 min-1. The present 3D SrS/CdS structure promise to be efficient photocatalysts due to (i) the facile intersystem charge transfer resulting from their band alignment (ii) enhanced specific surface area and (iii) crystallinity. Electronic supplementary information (ESI) available: Schematic experimental setup for photocatalytic hydrogen generation, TEM of CdS NWs and SrS NPs, FESEM images of 3D SrS/CdS, Low resolution TEM images for 3D SrS/CdS, EDX and SAED, SEM of SrS/CdS at different ratios, progress of hydrogen production at different time interval, different UV-Vis absorption spectra of MO. See DOI: 10.1039/c2nr30666b

  13. Synthesis of Polysubstituted ?-Butenolides via a Radical Pathway: Cyclization of ?-Bromo Aluminium Acetals and Comparison with the Cyclization of ?-Bromoesters at High Temperature.

    PubMed

    Bénéteau, Romain; Despiau, Carole F; Rouaud, Jean-Christophe; Boussonnière, Anne; Silvestre, Virginie; Lebreton, Jacques; Dénès, Fabrice

    2015-08-01

    Polysubstituted butenolides were obtained in good to high yields from ?-bromoesters derived from propargyl alcohols by a one-pot reaction involving the radical cyclization of ?-bromo aluminium acetals, followed by the oxidation of the resulting cyclic aluminium acetals in an Oppenauer-type process and migration of the exocyclic C=C bond into the ?,?-position. Comparison with the direct cyclization of ?-bromoesters at high temperature and under high dilution conditions is described. Deuterium-labelling experiments allowed us to uncover "invisible" 1,5-hydrogen atom transfers (1,5-HATs) that occur during these cyclization processes, together with the consequences of the latter in the epimerization of stereogenic centres. Compared to the classical approach, the cyclization of aluminium acetals proved to be highly chemoselective and its efficiency was illustrated by the short total syntheses of optically enriched ?-butenolides isolated from Plagiomnium undulatum and from Kyrtuhrix maculans. PMID:26119100

  14. Direct synthesis of novel vanadium oxide embedded porous carbon nanofiber decorated with iron nanoparticles as a low-cost and highly efficient visible-light-driven photocatalyst.

    PubMed

    Taha, Ahmed Aboueloyoun; Hriez, Amir A; Wu, Yi-nan; Wang, Hongtao; Li, Fengting

    2014-03-01

    Template-free porous carbon nanofibers embedded by vanadium oxide and decorated with iron nanoparticles (Fe@V-CNF) were prepared in a time and cost-saving manner by combining electrospinning and heat treatment processes. Cost-saving ammonium metavanadate was used as a semiconductor precursor of vanadium oxide (VOx) as well as porogen. The generated pores in the carbon nanofiber (CNFs) matrix formed pathways between the embedded VOx and the surface of CNFs and Fe NPs, thus, facilitate photo-generated electron transfer. The characterization results revealed that Fe@V-CNF comprised graphitic fibers with well-dispersed distribution of nanosized Fe NPs (~7 nm) along the surface of CNF. Thereby, it enhanced the visible-light harvesting. The prepared Fe@V-CNF had remarkable light absorption in the visible region. It demonstrated much higher photocatalytic efficiency of photodegradation of organic dyes compared with the pure CNF and vanadium oxide embedded CNF (V-CNF). Notably, Fe@V-CNF achieved 99.9% dye degradation within 15-20 min. And, it could be conveniently recycled due to its one-dimensional nanostructural property. PMID:24407677

  15. Synthesis of an efficient white-light photocatalyst composite of graphene and ZnO nanoparticles: Application to methylene blue dye decomposition

    NASA Astrophysics Data System (ADS)

    Hossain, Muhammad Mohsin; Ku, Bon-Cheol; Hahn, Jae Ryang

    2015-11-01

    A graphene-ZnO nanoparticle composite was fabricated by an in situ solvothermal process at low temperatures without catalytic assistance. The as-prepared composite absorbs light at an extended range of wavelengths from the visible to the near IR (400-1665 nm), efficiently absorbs high-intensity light in the near IR region, and exhibits high electrical conductivity. The highly porous structure of aggregated ZnO nanoparticles on the graphene surface enables these particles to absorb dye and degrade it. X-ray photoelectron spectroscopy analysis suggests that a number of oxygen vacancy defects are created in the ZnO matrix and that Zn atoms are chemically bonded to Cdbnd O groups at the relatively amorphous sites of the graphene surface. Raman spectroscopy analysis indicates a strong interaction between the graphene surface and ZnO nanoparticles. Further analyses using scanning electron microscopy, transmission electron microscopy, UV-visible-near-IR absorption, band gap calculations, electrical conductivity measurements, and photocatalysis show that the incorporation of graphene with ZnO nanoparticles narrows the band gap of ZnO, facilitates an extended range of light absorption, improves the electrical conductivity of ZnO, creates oxygen vacancy defects in the ZnO crystal, and enhances stability against photocorrosion.

  16. Synthesis of Pt-Loaded Self-Interspersed Anatase TiO2 with a Large Fraction of (001) Facets for Efficient Photocatalytic Nitrobenzene Degradation.

    PubMed

    Wang, Wei-Kang; Chen, Jie-Jie; Li, Wen-Wei; Pei, Dan-Ni; Zhang, Xing; Yu, Han-Qing

    2015-09-16

    TiO2 is capable of directly utilizing solar energy for sustainable energy harvest and water purification. Facet-dependent performance of TiO2 has attracted enormous interests due to its tunable photocatalytic activity toward photoredox transformations, but information about the noble-metal-loaded TiO2 for its facet-dependent photocatalytic performance, especially in pollutant degradation systems, is limited. In this work, inspired by our previous theoretical calculations about the roles of the crystal surface in Pt-loaded TiO2 in its enhanced photocatalytic capacity, TiO2 nanocrystals with interspersed polyhedron nanostructures and coexposed (001) and (101) surfaces as a support of Pt nanoparticles are prepared in a simple and relatively green route. Also, their performance for photocatalytic degradation of nitrobenzene (NB), a model organic pollutant, is explored. The experimental results demonstrate that the NB photodegradation and photoconversion efficiencies are significantly enhanced by uniformly loading Pt nanoparticles on the crystal surfaces, but the Pt nanoparticles deposited on only the (101) surface have no contribution to the improved NB photodegradation. Furthermore, the liquid chromatography mass spectrometry results also show that NB photodegradation tends to proceed on the (001) surface of Pt/TiO2 for the generation of nitrophenol intermediates through the photooxidation pathway. This work provides a new route to design and construct advanced photocatalysts toward pollutant photoredox conversions and deepens our fundamental understanding about crystal surface engineering. PMID:26308282

  17. One-pot synthesis of CdS nanocrystals hybridized with single-layer transition-metal dichalcogenide nanosheets for efficient photocatalytic hydrogen evolution.

    PubMed

    Chen, Junze; Wu, Xue-Jun; Yin, Lisha; Li, Bing; Hong, Xun; Fan, Zhanxi; Chen, Bo; Xue, Can; Zhang, Hua

    2015-01-19

    Exploration of low-cost and earth-abundant photocatalysts for highly efficient solar photocatalytic water splitting is of great importance. Although transition-metal dichalcogenides (TMDs) showed outstanding performance as co-catalysts for the hydrogen evolution reaction (HER), designing TMD-hybridized photocatalysts with abundant active sites for the HER still remains challenge. Here, a facile one-pot wet-chemical method is developed to prepare MS2-CdS (M=W or Mo) nanohybrids. Surprisedly, in the obtained nanohybrids, single-layer MS2 nanosheets with lateral size of 4-10?nm selectively grow on the Cd-rich (0001) surface of wurtzite CdS nanocrystals. These MS2-CdS nanohybrids possess a large number of edge sites in the MS2 layers, which are active sites for the HER. The photocatalytic performances of WS2-CdS and MoS2-CdS nanohybrids towards the HER under visible light irradiation (>420?nm) are about 16 and 12?times that of pure CdS, respectively. Importantly, the MS2-CdS nanohybrids showed enhanced stability after a long-time test (16?h), and 70% of catalytic activity still remained. PMID:25470356

  18. Facile method for synthesis of TiO{sub 2} film and its application in high efficiency dye sensitized-solar cell (DSSC)

    SciTech Connect

    Widiyandari, Hendri Gunawan, S. K.V.; Suseno, Jatmiko Endro; Purwanto, Agus; Diharjo, Kuncoro

    2014-02-24

    Dye-sensitized solar cells (DSSC) is a device which converts a solar energy to electrical energy. Different with semiconductor thin film based solar cell, DSSC utilize the sensitized-dye to absorb the photon and semiconductor such as titanium dioxide (TiO{sub 2}) and zinc oxide (ZnO) as a working electrode photoanode. In this report, the preparation of TiO{sub 2} film using a facile method of spray deposition and its application in DSSC have been presented. TiO{sub 2} photoanode was synthesized by growing the droplet of titanium tetraisopropoxide diluted in acid solution on the substrate of conductive glass flourine-doped tin oxide (FTO) with variation of precursor volume. DSSC was assemblied by sandwiching both of photoanode electrode and platinum counter electrode subsequently filling the area between these electrodes with triodine/iodine electrolite solution as redox pairs. The characterization of the as prepared DSSC using solar simulator (AM 1.5G, 100 mW/cm{sup 2}) and I-V source meter Keithley 2400 showed that the performance of DSSC was affected by the precursor volume.. The overall conversion efficiency of DSSC using the optimum TiO{sub 2} film was about 1.97% with the open circuit voltage (V{sub oc}) of 0.73 V, short circuit current density (J{sub sc}) of 4.61 mA and fill factor (FF) of 0.58.

  19. Hydrothermal Synthesis of FeS2 as a High-Efficiency Fenton Reagent to Degrade Alachlor via Superoxide-Mediated Fe(II)/Fe(III) Cycle.

    PubMed

    Liu, Wei; Wang, Yueyao; Ai, Zhihui; Zhang, Lizhi

    2015-12-30

    In this study, we demonstrate that hydrothermally synthesized FeS2 (syn-FeS2) is highly efficient at catalyzing the H2O2 decomposition for alachlor degradation at a wide range of initial pH (3.2-9.2). The alachlor degradation rate of syn-FeS2 heterogeneous Fenton system was almost 55 times that of its commercial pyrite (com-FeS2) counterpart at an initial pH of 6.2. Experimental results revealed that the alachlor oxidation enhancement in the syn-FeS2 Fenton system was attributed to the molecular oxygen activation induced by more surface-bound ferrous ions on syn-FeS2. The molecular oxygen activation process could generate superoxide anions to accelerate the Fe(II)/Fe(III) cycle on the syn-FeS2 surface, which favored the H2O2 decomposition to generate more hydroxyl radicals for the alachlor oxidation. It was found that the hydroxyl radicals generation rate constant of syn-FeS2 Fenton system was 71 times that of its com-FeS2 counterpart, and even 1-3 orders of magnitude larger than those of commonly used Fe-bearing heterogeneous catalysts. We detected the alachlor degradation intermediates with gas chromatography-mass spectrometry to propose tentatively a possible alachlor degradation pathway. These interesting findings could provide some new insights on the molecular oxygen activation induced by FeS2 minerals and the subsequent heterogeneous Fenton degradation of organic pollutants in the environment. PMID:26646468

  20. A total-synthesis framework for the construction of high-order colloidal hybrid nanoparticles

    NASA Astrophysics Data System (ADS)

    Buck, Matthew R.; Bondi, James F.; Schaak, Raymond E.

    2012-01-01

    Colloidal hybrid nanoparticles contain multiple nanoscale domains fused together by solid-state interfaces. They represent an emerging class of multifunctional lab-on-a-particle architectures that underpin future advances in solar energy conversion, fuel-cell catalysis, medical imaging and therapy, and electronics. The complexity of these ‘artificial molecules’ is limited ultimately by the lack of a mechanism-driven design framework. Here, we show that known chemical reactions can be applied in a predictable and stepwise manner to build complex hybrid nanoparticle architectures that include M-Pt-Fe3O4 (M = Au, Ag, Ni, Pd) heterotrimers, MxS-Au-Pt-Fe3O4 (M = Pb, Cu) heterotetramers and higher-order oligomers based on the heterotrimeric Au-Pt-Fe3O4 building block. This synthetic framework conceptually mimics the total-synthesis approach used by chemists to construct complex organic molecules. The reaction toolkit applies solid-state nanoparticle analogues of chemoselective reactions, regiospecificity, coupling reactions and molecular substituent effects to the construction of exceptionally complex hybrid nanoparticle oligomers.

  1. Cyclobutane Synthesis and Fragmentation. A Cascade Route to the Lycopodium Alkaloid (-)-Huperzine A.

    PubMed

    White, James D; Li, Yang; Kim, Jungchul; Terinek, Miroslav

    2015-12-01

    An asymmetric total synthesis of the nootropic alkaloid (-)-huperzine A was completed using a cascade sequence initiated by an intramolecular aza-Prins reaction and terminated by a stereoelectronically guided fragmentation of a cyclobutylcarbinyl cation as the key step in assembling the bicyclo[3.3.1]nonene core of the natural product. Intramolecular [2 + 2]-photocycloaddition of the crotyl ether of (S)-4-hydroxycyclohex-2-enone afforded a bicyclo[4.2.0]octanone containing an embedded tetrahydrofuran in which the cyclohexanone moiety was converted to a triisopropylsilyl enol ether and functionalized as an allylic azide. The derived primary amine was acylated with ?-phenylselenylacrylic acid, and the resulting amide was reacted with trimethylaluminum to give a [2 + 2]-cycloadduct, which underwent retroaldol fission to produce a fused ?-phenylselenyl ?-lactam. Periodate oxidation of this lactam led directly to an ?-pyridone, which was converted to a fused 2-methoxypyridine. Reductive cleavage of the activated "pyridylic" C-O bond in this tetracycle and elaboration of the resultant hydroxy ketone to a diketone was followed by chemoselective conversion of the methyl ketone in this structure to an endo isopropenyl group. Condensation of the remaining ketone with methyl carbamate in the presence of acid initiated the programmed cascade sequence and furnished a known synthetic precursor to huperzine A. Subsequent demethylation of the carbamate and the methoxypyridine, accompanied by in situ decarboxylation of the intermediate carbamic acid, gave (-)-huperzine A. PMID:26355759

  2. Donor-substituted 1,1,4,4-tetracyanobutadienes (TCBDS): new chromophores with efficient intramolecular charge-transfer interactions by atom-economic synthesis.

    PubMed

    Michinobu, Tsuyoshi; Boudon, Corinne; Gisselbrecht, Jean-Paul; Seiler, Paul; Frank, Brian; Moonen, Nicolle N P; Gross, Maurice; Diederich, François

    2006-02-20

    A wide variety of monomeric and oligomeric, donor-substituted 1,1,4,4-tetracyanobutadienes (TCBDs) have been synthesized by [2+2] cycloaddition between tetracyanoethylene (TNCE) and donor-substituted alkynes, followed by electrocyclic ring opening of the initially formed cyclobutenes. Reaction yields are often nearly quantitative but can be affected by the electron-donating power and steric demands of the alkyne substituents. The intramolecular charge-transfer (CT) interactions between the donor and TCBD acceptor moieties were comprehensively investigated by X-ray crystallography, electrochemistry, UV-visible spectroscopy, and theoretical calculations. Despite the nonplanarity of the new chromophores, which have a substantial twist between the two dicyanovinyl planes, efficient intramolecular CT interactions are observed, and the crystal structures demonstrate a high quinoid character in strong donor substituents, such as N,N-dimethylanilino (DMA) rings. The maxima of the CT bands shift bathochromically upon reduction of the amount of conjugative coupling between strong donor and acceptor moieties. Each TCBD moiety undergoes two reversible, one-electron reduction steps. Thus, a tri-TCBD derivative with a 1,3,5-trisubstituted benzene core shows six reversible reduction steps within an exceptionally narrow potential range of 1.0 V. The first reduction potential E(red,1) is strongly influenced by the donor substitution: introduction of more donor moieties causes an increasingly twisted TCBD structure, a fact that results in the elevation of the LUMO level and, consequently, a more difficult first reduction. The potentials are also strongly influenced by the nature of the donor residues and the extent of donor-acceptor coupling. A careful comparison of electrochemical data and the correlation with UV-visible spectra made it possible to estimate unknown physical parameters such as the E(red,1) of unsubstituted TCBD (-0.31 V vs Fc+/Fc) as well as the maxima of highly broadened CT bands. Donor-substituted TCBDs are stable molecules and can be sublimed without decomposition. With their high third-order optical nonlinearities, as revealed in preliminary measurements, they should become interesting chromophores for ultra-thin film formation by vapor deposition techniques and have applications in opto-electronic devices. PMID:16389622

  3. Efficient and versatile catalysis of N-alkylation of heterocyclic amines with alcohols and one-pot synthesis of 2-aryl substituted benzazoles with newly designed ruthenium(II) complexes of PNS thiosemicarbazones.

    PubMed

    Ramachandran, Rangasamy; Prakash, Govindan; Selvamurugan, Sellappan; Viswanathamurthi, Periasamy; Malecki, Jan Grzegorz; Ramkumar, Venkatachalam

    2014-06-01

    Ruthenium(II) carbonyl complexes with phosphine-functionalized PNS type thiosemicarbazone ligands [RuCl(CO)(EPh3)(L)] (1-6) (E = P or As, L = 2-(2-(diphenylphosphino)benzylidene) thiosemicarbazone (PNS-H), 2-(2-(diphenylphosphino)benzylidene)-N-methylthiosemicarbazone (PNS-Me), 2-(2-(diphenylphosphino)benzylidene)-N-phenylthiosemicarbazone (PNS-Ph)) have been synthesized and characterized by elemental analysis and spectroscopy (IR, UV-Vis, (1)H, (13)C, (31)P-NMR) as well as ESI mass spectrometry. The molecular structures of complexes 1, 2 and 6 were identified by means of single-crystal X-ray diffraction analysis. The analysis revealed that all the complexes possess a distorted octahedral geometry with the ligand coordinating in a uni-negative tridentate PNS fashion. All the ruthenium complexes (1-6) were tested as catalyst for N-alkylation of heteroaromatic amines with alcohols. Notably, complex 2 was found to be a very efficient and versatile catalyst towards N-alkylation of a wide range of heterocyclic amines with alcohols. Complex 2 can also catalyze the direct amination of 2-nitropyridine with benzyl alcohol to the corresponding secondary amine. Furthermore, a preliminary examination of performance for N,N-dialkylation of diamine showed promising results, giving good conversion and high selectivity. In addition, N-alkylation of ortho-substituted anilines (-NH2, -OH and -SH) led to the one-pot synthesis of 2-aryl substituted benzimidazoles, benzoxazoles and benzothiazoles, also revealing the catalytic activity of complex 2. PMID:24705796

  4. The development of new synthetic strategies and methodologies for complex alkaloid total synthesis : a concise synthesis of (+)-chimonanthine, (+)-WIN 64821, (-)-ditryptophenaline and related alkaloids

    E-print Network

    Schmidt, Michael Anthony, 1980-

    2008-01-01

    I. The Development of a General Strategy Towards Dimeric Hexahydropyrroloindole Alkaloids. A Concise Total Synthesis of (+)-Chimonanthine, (+)-Folicanthine and (-)Calycanthine. An efficient and convergent strategy for the ...

  5. A sustainable catalytic pyrrole synthesis

    NASA Astrophysics Data System (ADS)

    Michlik, Stefan; Kempe, Rhett

    2013-02-01

    The pyrrole heterocycle is a prominent chemical motif and is found widely in natural products, drugs, catalysts and advanced materials. Here we introduce a sustainable iridium-catalysed pyrrole synthesis in which secondary alcohols and amino alcohols are deoxygenated and linked selectively via the formation of C-N and C-C bonds. Two equivalents of hydrogen gas are eliminated in the course of the reaction, and alcohols based entirely on renewable resources can be used as starting materials. The catalytic synthesis protocol tolerates a large variety of functional groups, which includes olefins, chlorides, bromides, organometallic moieties, amines and hydroxyl groups. We have developed a catalyst that operates efficiently under mild conditions.

  6. Synthesis and Characterization of Oligodeoxyribonucleotides Modified with 2?-Amino-?-L-LNA Adenine Monomers: High-affinity Targeting of Single-Stranded DNA

    PubMed Central

    Andersen, Nicolai K.; Anderson, Brooke A.; Wengel, Jesper

    2014-01-01

    Development of conformationally restricted nucleotide building blocks continues to attract considerable interest due to their successful use within antisense, antigene and other gene-targeting strategies. Locked nucleic acid (LNA) and its diastereomer ?-L-LNA are two interesting examples hereof. Oligonucleotides modified with these units display greatly increased affinity toward nucleic acid targets, improved binding specificity and enhanced enzymatic stability relative to unmodified strands. Here, we present the synthesis and biophysical characterization of oligodeoxyribonucleotides (ONs) modified with 2?-amino-?-L-LNA adenine monomers W–Z. The synthesis of target phosphoramidites 1–4 initiates from pentafuranose 5, which upon Vorbrüggen glycosylation, O2?-deacylation, O2?-activation and C2?-azide introduction yields nucleoside 8. A one-pot tandem Staudinger/intramolecular nucleophilic substitution converts 8 into 2?-amino-?-L-LNA adenine intermediate 9, which after a series of non-trivial protecting group manipulations affords key intermediate 15. Subsequent chemoselective N2?-functionalization and O3?-phosphitylation gives targets 1–4 in ~1–3% overall yield over eleven steps from 5. ONs modified with pyrene-functionalized 2?-amino-?-L-LNA adenine monomers X-Z display greatly increased affinity toward DNA targets (?Tm/modification up to +14 °C). Results from absorption and fluorescence spectroscopy suggest that the duplex stabilization is a result of pyrene intercalation. These characteristics render N2?-pyrene-functionalized 2?-amino-?-L-LNA of considerable interest for DNA-targeting applications. PMID:24304240

  7. Efficient green methanol synthesis from glycerol.

    PubMed

    Haider, Muhammad H; Dummer, Nicholas F; Knight, David W; Jenkins, Robert L; Howard, Mark; Moulijn, Jacob; Taylor, Stuart H; Hutchings, Graham J

    2015-12-01

    The production of biodiesel from the transesterification of plant-derived triglycerides with methanol has been commercialized extensively. Impure glycerol is obtained as a by-product at roughly one-tenth the mass of the biodiesel. Utilization of this crude glycerol is important in improving the viability of the overall process. Here we show that crude glycerol can be reacted with water over very simple basic or redox oxide catalysts to produce methanol in high yields, together with other useful chemicals, in a one-step low-pressure process. Our discovery opens up the possibility of recycling the crude glycerol produced during biodiesel manufacture. Furthermore, we show that molecules containing at least two hydroxyl groups can be converted into methanol, which demonstrates some aspects of the generality of this new chemistry. PMID:26587720

  8. HIGH EFFICIENCY DESULFURIZATION OF SYNTHESIS GAS

    SciTech Connect

    Kwang-Bok Yi; Anirban Mukherjee; Elizabeth J. Podlaha; Douglas P. Harrison

    2004-03-01

    Mixed metal oxides containing ceria and zirconia have been studied as high temperature desulfurization sorbents with the objective of achieving the DOE Vision 21 target of 1 ppmv or less H{sub 2}S in the product gas. The research was justified by recent results in this laboratory that showed that reduced CeO{sub 2}, designated CeOn (1.5 < n < 2.0), is capable of achieving the 1 ppmv target in highly reducing gas atmospheres. The addition of ZrO{sub 2} has improved the performance of oxidation catalysts and three-way automotive catalysts containing CeO{sub 2}, and was postulated to have similar beneficial effects on CeO{sub 2} desulfurization sorbents. An electrochemical method for synthesizing CeO{sub 2}-ZrO{sub 2} mixtures was developed and the products were characterized by XRD and TEM during year 01. Nanocrystalline particles having a diameter of about 5 nm and containing from approximately 10 mol% to 80 mol% ZrO{sub 2} were prepared. XRD analysis showed the product to be a solid solution at low ZrO{sub 2} contents with a separate ZrO{sub 2} phase emerging at higher ZrO{sub 2} levels. Unfortunately, the quantity of CeO{sub 2}-ZrO{sub 2} that could be prepared electrochemically was too small to permit desulfurization testing. Also during year 01 a laboratory-scale fixed-bed reactor was constructed for desulfurization testing. All components of the reactor and analytical systems that were exposed to low concentrations of H{sub 2}S were constructed of quartz, Teflon, or silcosteel. Reactor product gas composition as a function of time was determined using a Varian 3800 gas chromatograph equipped with a pulsed flame photometric detector (PFPD) for measuring low H{sub 2}S concentrations from approximately 0.1 to 10 ppmv, and a thermal conductivity detector (TCD) for higher concentrations of H{sub 2}S. Larger quantities of CeO{sub 2}-ZrO{sub 2} mixtures from other sources, including mixtures prepared in this laboratory using a coprecipitation procedure, were obtained. Much of the work during year 02 consisted of characterization and desulfurization testing of materials obtained from commercial sources. Most of the commercial CeO{sub 2} and CeO{sub 2}-ZrO{sub 2} materials were capable of reducing H{sub 2}S concentration from 5000 ppmv in highly reducing feed gas to less than 1 ppmv in the product gas. However, to properly evaluate the effect of ZrO{sub 2} addition on desulfurization capability, the physical properties of the sorbent must be similar. That is, a CeO{sub 2}-ZrO{sub 2} mixture from source A would not necessarily be superior to pure CeO{sub 2} from source B if the properties of the pure CeO{sub 2} were superior. Therefore, research during year 03 concentrated on CeO{sub 2} and CeO{sub 2}-ZrO{sub 2} mixtures prepared in this laboratory using a coprecipitation procedure. The structural properties of these sorbents were similar and the effect of ZrO{sub 2} addition could better be separated from the structural effects. X-ray diffraction tests of the sorbents prepared in house confirmed the formation of a solid solution of ZrO{sub 2} in CeO{sub 2}. Crystallite sizes ranged from 12.7 to 18.8 nm and surface areas from 75 to 85 m{sup 2}/g. Reduction tests using an electrobalance reactor confirmed that CeO{sub 2}-ZrO{sub 2} mixtures were more easily reduced than pure CeO{sub 2}. Reduction of CeO{sub 2}-ZrO{sub 2} began at a lower temperature and the final value of n in CeO{sub n} (1.5 < n < 2.0) was smaller in CeO{sub 2}-ZrO{sub 2} than in pure CeO{sub 2}. Sorbent performance during desulfurization testing was judged both by the minimum H{sub 2}S concentration achieved during the so-called prebreakthrough period and by the duration of the prebreakthrough period. The end of the prebreakthrough period was defined as the time when the H{sub 2}S concentration in the product gas exceeded 1 ppmv. Both CeO{sub 2} and CeO{sub 2}-ZrO{sub 2} sorbents produced in house were capable of reaching the target sub-ppmv H{sub 2}S level in highly reducing gases for extended time periods. H{sub 2}S concentrations were reduced to

  9. HIGH EFFICIENCY DESULFURIZATION OF SYNTHESIS GAS

    SciTech Connect

    Kwang-Bok Yi; Elizabeth J. Podlaha; Douglas P. Harrison

    2003-11-01

    Mixed metal oxides containing CeO{sub 2} and ZrO{sub 2} are being studied as high temperature desulfurization sorbents capable of achieving the DOE Vision 21 target of 1 ppmv or less H{sub 2}S. The research is justified by recent results in this laboratory that showed that reduced CeO{sub 2}, designated CeOn (1.5 < n < 2.0), is capable of achieving the 1 ppmv target in highly reducing gas atmospheres. The addition of ZrO{sub 2} has improved the performance of oxidation catalysts and three-way automotive catalysts containing CeO{sub 2}, and should have similar beneficial effects on CeO{sub 2} desulfurization sorbents. An electrochemical method for synthesizing CeO{sub 2}-ZrO{sub 2} was developed and the products were characterized by XRD and TEM during year 01. Nanocrystalline particles having a diameter of about 5 nm and containing from approximately 10 mol% to 80 mol% ZrO{sub 2} were prepared. XRD analysis showed the product to be a solid solution at low ZrO{sub 2} contents with a separate ZrO{sub 2} phase emerging at higher ZrO{sub 2} levels. Unfortunately, the quantity of CeO{sub 2}-ZrO{sub 2} that could be prepared electrochemically was too small to permit full desulfurization testing. Also during year 01 a laboratory-scale fixed-bed reactor was constructed for desulfurization testing. All components of the reactor and analytical systems that may be exposed to low concentrations of H{sub 2}S are constructed of quartz, Teflon, or silcosteel. Reactor product gas composition as a function of time is determined using a Varian 3800 gas chromatograph equipped with a pulsed flame photometric detector (PFPD) for measuring low H{sub 2}S concentrations (<{approx}10 ppmv) and a thermal conductivity detector (TCD) for higher concentrations of H{sub 2}S. Larger quantities of CeO{sub 2}-ZrO{sub 2} mixtures from other sources, including mixtures prepared in this laboratory using a coprecipitation procedure, have been obtained. Much of the work during year 02 consisted of characterization and desulfurization testing of materials obtained from commercial sources. To properly evaluate the effect of ZrO{sub 2} addition on desulfurization capability, the physical properties of the sorbent must be similar. That is, a CeO{sub 2}-ZrO{sub 2} mixture from source A would not necessarily be superior to pure CeO{sub 2} from source B if the properties were dissimilar. Therefore, research during year 03 concentrated CeO{sub 2} and CeO{sub 2}-ZrO{sub 2} mixtures prepared in this laboratory using the coprecipitation procedure. The structure of these sorbents is similar and the effect of ZrO{sub 2} addition can better be separated from other effects. X-ray diffraction tests of the sorbents prepared in house have confirmed the existence of a solid solution of ZrO{sub 2} in CeO{sub 2}. Reduction tests using an electrobalance reactor have confirmed that CeO{sub 2}-ZrO{sub 2} mixtures are more easily reduced than pure CeO{sub 2}. Reduction of CeO{sub 2}-ZrO{sub 2} begins at a lower temperature and the final value of n in CeO{sub n} (1.5 < n < 2.0) is smaller in CeO{sub 2}-ZrO{sub 2} than in pure CeO{sub 2}. Desulfurization tests have shown that both CeO{sub 2} and CeO{sub 2}-ZrO{sub 2} sorbents are capable of reaching the target sub-ppmv H{sub 2}S level in highly reducing gases. Both CeO{sub 2} and CeO{sub 2}-ZrO{sub 2} sorbents have successfully removed H{sub 2}S to the minimum detectable limit of the PFPD detector, approximately 100 ppbv.

  10. HIGH EFFICIENCY DESULFURIZATION OF SYNTHESIS GAS

    SciTech Connect

    Anirban Mukherjee; Kwang-Bok Yi; Elizabeth J. Podlaha; Douglas P. Harrison

    2001-11-01

    Mixed metal oxides containing CeO{sub 2} and ZrO{sub 2} are being studied as high temperature desulfurization sorbents capable of achieving the DOE Vision 21 target of 1 ppmv of less H{sub 2}S. The research is justified by recent results in this laboratory that showed that reduced CeO{sub 2}, designated CeO{sub n} (1.5 < n < 2.0), is capable of achieving the 1 ppmv target in highly reducing gas atmospheres. The addition of ZrO{sub 2} has improved the performance of oxidation catalysts and three-way automotive catalysts containing CeO{sub 2}, and should have similar beneficial effects on CeO{sub 2} desulfurization sorbents. An electrochemical method for synthesizing CeO{sub 2}-ZrO{sub 2} has been developed and the products have been characterized by XRD and TEM during year 01. Nanocrystalline particles having a diameter of about 5 nm and containing from approximately 10 mol% to 80 mol% ZrO{sub 2} have been prepared. XRD showed the product to be a solid solution at low ZrO{sub 2} contents with a separate ZrO{sub 2} phase emerging at higher ZrO{sub 2} levels. Phase separation did not occur when the solid solutions were heat treated at 700 C. A flow reactor system constructed of quartz and teflon has been constructed, and a gas chromatograph equipped with a pulsed flame photometric detector (PFPD) suitable for measuring sub-ppmv levels of H{sub 2}S has been purchased with LSU matching funds. Preliminary desulfurization tests using commercial CeO{sub 2} and CeO{sub 2}-ZrO{sub 2} in highly reducing gas compositions has confirmed that CeO{sub 2}-ZrO{sub 2} is more effective than CeO{sub 2} in removing H{sub 2}S. At 700 C the product H{sub 2}S concentration using CeO{sub 2}-ZrO{sub 2} sorbent was near the 0.1 ppmv PFPD detection limit during the prebreakthrough period.

  11. HIGH EFFICIENCY DESULFURIZATION OF SYNTHESIS GAS

    SciTech Connect

    Kwang-Bok Yi; Elizabeth J. Podlaha; Douglas P. Harrison

    2002-11-01

    Mixed metal oxides containing CeO{sub 2} and ZrO{sub 2} are being studied as high temperature desulfurization sorbents capable of achieving the DOE Vision 21 target of 1 ppmv or less H{sub 2}S. The research is justified by recent results in this laboratory that showed that reduced CeO{sub 2}, designated CeO{sub n} (1.5 < n < 2.0), is capable of achieving the 1 ppmv target in highly reducing gas atmospheres. The addition of ZrO{sub 2} has improved the performance of oxidation catalysts and three-way automotive catalysts containing CeO{sub 2}, and should have similar beneficial effects on CeO{sub 2} desulfurization sorbents. An electrochemical method for synthesizing CeO{sub 2}-ZrO{sub 2} was developed and the products were characterized by XRD and TEM during year 01. Nanocrystalline particles having a diameter of about 5 nm and containing from approximately 10 mol% to 80 mol% ZrO{sub 2} were prepared. XRD showed the product to be a solid solution at low ZrO{sub 2} contents with a separate ZrO{sub 2} phase emerging at higher ZrO{sub 2} levels. Unfortunately, the quantity of CeO{sub 2}-ZrO{sub 2} that could be prepared electrochemically was too small to permit full testing in our desulfurization reactor. Also during year 01 a laboratory-scale fixed-bed reactor was constructed for desulfurization testing. All components of the reactor and analytical systems that may be exposed to low concentrations of H{sub 2}S are constructed of quartz, Teflon, or silcosteel. Reactor product gas composition as a function of time is determined using a Varian 3800 gas chromatograph equipped with a pulsed flame photometric detector (PFPD) for measuring low H{sub 2}S concentrations ({approx}< 10 ppmv) and a thermal conductivity detector (TCD) for higher concentrations of H{sub 2}S. Larger quantities of CeO{sub 2}-ZrO{sub 2} mixtures from other sources, including mixtures prepared in this laboratory using a coprecipitation procedure, have been obtained. Characterization and desulfurization testing of these sorbents began in year 02 and is continuing. To properly evaluate the effect of ZrO{sub 2} addition on desulfurization capability, the physical properties of the sorbent mixtures must be similar. That is, a CeO{sub 2}-ZrO{sub 2} mixture from source A would not necessarily be superior to pure CeO{sub 2} from source B if the properties were dissimilar. Therefore, current research is concentrating on CeO{sub 2} and CeO{sub 2}-ZrO{sub 2} mixtures prepared in this laboratory using the coprecipitation procedure. The structure of these sorbents is similar and the effect of ZrO{sub 2} addition can be separated from other effects. X-ray diffraction tests of the sorbents prepared in house have confirmed the existence of a solid solution of ZrO{sub 2} in CeO{sub 2}. Reduction tests using an electrobalance reactor have confirmed that CeO{sub 2}-ZrO{sub 2} mixtures are more easily reduced than pure CeO{sub 2}. Reduction of CeO{sub 2}-ZrO{sub 2} begins at a lower temperature and the final value of n in CeO{sub n} (1.5

  12. Total synthesis of leucosceptroids A and B.

    PubMed

    Guo, Sheng; Liu, Jie; Ma, Dawei

    2015-01-19

    Leucosceptroids?A and B are sesterterpenoids with potent antifeedant and antifungal activities. A more efficient gram-scale total synthesis of leucosceptroid?B and the first total synthesis of leucosceptroid?A are presented. The key transformations include an aldol reaction between a substituted dihydrofuranone and an (S)-citronellal-derived aldehyde, a SmI2-mediated intramolecular ketyl-olefin radical cyclization, and final-stage alcohol oxidation. PMID:25470240

  13. GLUTATHIONE SYNTHESIS

    PubMed Central

    Lu, Shelly C.

    2012-01-01

    BACKGROUND Glutathione (GSH) is present in all mammalian tissues as the most abundant non-protein thiol that defends against oxidative stress. GSH is also a key determinant of redox signaling, vital in detoxification of xenobiotics, regulates cell proliferation, apoptosis, immune function, and fibrogenesis. Biosynthesis of GSH occurs in the cytosol in a tightly regulated manner. Key determinants of GSH synthesis are the availability of the sulfur amino acid precursor, cysteine, and the activity of the rate-limiting enzyme, glutamate cysteine ligase (GCL), which is composed of a catalytic (GCLC) and a modifier (GCLM) subunit. The second enzyme of GSH synthesis is GSH synthetase (GS). SCOPE OF REVIEW This review summarizes key functions of GSH and focuses on factors that regulate the biosynthesis of GSH, including pathological conditions where GSH synthesis is dysregulated. MAJOR CONCLUSIONS GCL subunits and GS are regulated at multiple levels and often in a coordinated manner. Key transcription factors that regulate the expression of these genes include NF-E2 related factor 2 (Nrf2) via the antioxidant response element (ARE), AP-1, and nuclear factor kappa B (NF?B). There is increasing evidence that dysregulation of GSH synthesis contributes to the pathogenesis of many pathological conditions. These include diabetes mellitus, pulmonary and liver fibrosis, alcoholic liver disease, cholestatic liver injury, endotoxemia and drug-resistant tumor cells. GENERAL SIGNIFICANCE GSH is a key antioxidant that also modulates diverse cellular processes. A better understanding of how its synthesis is regulated and dysregulated in disease states may lead to improvement in the treatment of these disorders. PMID:22995213

  14. Bioinspired iterative synthesis of polyketides

    PubMed Central

    Zheng, Kuan; Xie, Changmin; Hong, Ran

    2015-01-01

    Diverse array of biopolymers and second metabolites (particularly polyketide natural products) has been manufactured in nature through an enzymatic iterative assembly of simple building blocks. Inspired by this strategy, molecules with inherent modularity can be efficiently synthesized by repeated succession of similar reaction sequences. This privileged strategy has been widely adopted in synthetic supramolecular chemistry. Its value also has been reorganized in natural product synthesis. A brief overview of this approach is given with a particular emphasis on the total synthesis of polyol-embedded polyketides, a class of vastly diverse structures and biologically significant natural products. This viewpoint also illustrates the limits of known individual modules in terms of diastereoselectivity and enantioselectivity. More efficient and practical iterative strategies are anticipated to emerge in the future development. PMID:26052510

  15. Bioinspired Iterative Synthesis of Polyketides

    NASA Astrophysics Data System (ADS)

    Hong, Ran; Zheng, Kuan; Xie, Changmin

    2015-05-01

    Diverse array of biopolymers and second metabolites (particularly polyketide natural products) has been manufactured in nature through an enzymatic iterative assembly of simple building blocks. Inspired by this strategy, molecules with inherent modularity can be efficiently synthesized by repeated succession of similar reaction sequences. This privileged strategy has been widely adopted in synthetic supramolecular chemistry. Its value also has been reorganized in natural product synthesis. A brief overview of this approach is given with a particular emphasis on the total synthesis of polyol-embedded polyketides, a class of vastly diverse structures and biologically significant natural products. This viewpoint also illustrates the limits of known individual modules in terms of diastereoselectivity and enantioselectivity. More efficient and practical iterative strategies are anticipated to emerge in the future development.

  16. Thesis proposal CSF Brazil 2014 ADVANCED CATALYSTS FOR THE SYNTHESIS OF FINE CHEMICALS FROM NATURAL

    E-print Network

    Bordenave, Charles

    model reactions, the most efficient catalytic systems will be applied to the synthesis of targetThesis proposal CSF Brazil 2014 Title: ADVANCED CATALYSTS FOR THE SYNTHESIS OF FINE CHEMICALS FROM for a more effective and cleaner synthesis of elaborate products. For that purpose, the design catalyst

  17. Highly Efficient GF (28 ) Inversion Circuit

    E-print Network

    International Association for Cryptologic Research (IACR)

    Highly Efficient GF (28 ) Inversion Circuit Based on Redundant GF Arithmetic and Its Application a compact and efficient GF(28 ) inver- sion circuit design based on a combination of non-redundant and redun of the proposed circuit by means of gate counts and logic synthesis with a 65 nm CMOS standard cell library

  18. Synthesis of pharmaceutically relevant 17-?-amino steroids using an ?-transaminase.

    PubMed

    Richter, Nina; Simon, Robert C; Kroutil, Wolfgang; Ward, John M; Hailes, Helen C

    2014-06-11

    An efficient and sustainable biocatalytic route for the synthesis of important 17-?-amino steroids has been developed using an ?-transaminase variant from Arthrobacter sp. Optimisation of the reaction conditions facilitated the synthesis of these valuable synthons on a preparative scale, affording excellent isolated yields and stereocontrol. PMID:24576951

  19. DNA Synthesis, Assembly and Applications in Synthetic Biology

    PubMed Central

    Ma, Siying; Tang, Nicholas; Tian, Jingdong

    2012-01-01

    The past couple of years saw exciting new developments in microchip-based gene synthesis technologies. Such technologies hold the potential for significantly increasing the throughput and decreasing the cost of gene synthesis. Together with more efficient enzymatic error correction and genome assembly methods, these new technologies are pushing the field of synthetic biology to a higher level. PMID:22633067

  20. Total synthesis of the Isodon diterpene sculponeatin?N.

    PubMed

    Moritz, Benjamin J; Mack, Daniel J; Tong, Liuchuan; Thomson, Regan J

    2014-03-10

    The total synthesis of sculponeatin?N, a bioactive polycyclic diterpene isolated from Isodon sculponeatus, is reported. Key features of the synthesis include diastereoselective Nazarov and ring-closing metathesis reactions, and a highly efficient formation of the bicyclo[3.2.1]octane ring system by a reductive radical cyclization. PMID:24519748

  1. Optimal synthesis of multivalued quantum circuit

    E-print Network

    Yao-Min Di; Hai-Rui Wei

    2015-06-14

    Although many of works have been done in multivalued quantum logic synthesis, the question whether multivalued quantum circuits are more efficient than the conventional binary quantum circuits is still open. In this article we devote to the optimization of generic multivalued quantum circuits. The multivalued quantum Shannon decompositions (QSD) are improved so that the circuits obtained are asymptotically optimal for all dimensionality d. The syntheses of uniformly multifold controlled $R_y$ rotations are also optimized to make the circuits further simplified. Moreover, the theoretical lower bound of complexity for multivalued quantum circuits is investigated, and a quantity known as efficiency index is proposed to evaluate the efficiency of synthesis of various quantum circuits. The algorithm for qudit circuits given here is an efficient synthesis routine which produces best known results for all dimensionality d, and for both cases the number of qudit n is small and that is asymptotic. The multivalued quantum circuits are indeed more efficient than the binary quantum circuits. The facts, the leading factor of the lower bound of complexity for qudit circuits is small by a factor of d-1 in comparison to that for qubit circuits and the asymptotic efficiency index is increased with the increase of dimensionality d, reveal the potential advantage of qudit circuits over generic qubit circuits. The generic n-qudit circuits with $d\\geq5$ and generic two-ququart circuits synthesized by the algorithm given here are practical circuits which are more efficient than the most efficient qubit circuits.

  2. Development of transitional metal-catalyzed reactions for organic synthesis

    E-print Network

    Rainka, Matthew P. (Matthew Paul)

    2005-01-01

    Chapter 1. A general catalyst system for the synthesis of tetra-ortho-substituted biaryls via the Suzuki-Miyaura cross-coupling reaction is described. It was found that the most efficient catalyst system is based on a ...

  3. Synthesis of a Precursor to Sacubitril Using Enabling Technologies

    E-print Network

    Lau, Shing-Hing; Bourne, Samuel L.; Martin, Benjamin; Schenkel, Berthold; Penn, Gerhard; Ley, Steven V.

    2015-10-28

    An efficient preparation of a precursor to the neprilysin inhibitor sacubitril is described. The convergent synthesis features a diastereoselective Reformatsky-type carbethoxyallylation and a rhodium-catalysed stereoselective hydrogenation...

  4. Palladium-Catalyzed Synthesis of N-Aryl Carbamates

    E-print Network

    Fors, Brett P.

    An efficient synthesis of aryl carbamates was achieved by introducing alcohols into the reaction of palladium-catalyzed cross-coupling of ArX (X = Cl, OTf) with sodium cyanate. The use of aryl triflates as electrophilic ...

  5. Concise Palladium-Catalyzed Synthesis of Dibenzodiazepines and Structural Analogs

    E-print Network

    Tsvelikhovsky, Dmitry

    A general and highly efficient protocol for the synthesis of dibenzodiazepines and their structural analogues is reported. In the presence of catalytic quantities of palladium, readily accessible precursors are cross-coupled ...

  6. Automatic Program Repair with Condition Synthesis and Compound Mutations

    E-print Network

    Long, Fan

    2015-02-12

    We present PCR, a new automatic patch generation system. PCR uses a new condition synthesis technique to efficiently discover logical expressions that generate desired control- flow transfer patterns. Presented with a set ...

  7. Mo-catalyzed asymmetric olefin metathesis in target-oriented synthesis: Enantioselective synthesis of (+)-africanol

    PubMed Central

    Weatherhead, Gabriel S.; Cortez, G. A.; Schrock, Richard R.; Hoveyda, Amir H.

    2004-01-01

    Catalytic asymmetric ring-opening metathesis (AROM) provides an efficient method for the synthesis of a variety of optically enriched small organic molecules that cannot be easily prepared by alternative methods. The development of Mo-catalyzed AROM transformations that occur in tandem with ring-closing metathesis are described. The utility of the Mo-catalyzed AROM/ring-closing metathesis is demonstrated through an enantioselective approach to the synthesis of (+)-africanol. PMID:15056762

  8. Reactor design issues for synthesis-gas fermentations

    SciTech Connect

    Bredwell, M.D.; Srivastava, P.; Worden, R.M.

    1999-10-01

    Synthesis gas is readily obtained by gasifying coal, oil, biomass, or waste organics and represents an abundant, potentially inexpensive, feedstock for bioprocessing. The primary components of synthesis gas, carbon monoxide and hydrogen, can be converted into methane, organic acids, and alcohols via anaerobic fermentations. Bioconversion of synthesis gas is an attractive alternative to catalytic processing because the biological catalysts are highly specific and often more tolerant of sulfur contaminants than inorganic catalysts. However, because the aqueous solubilities of carbon monoxide and hydrogen are low, synthesis-gas fermentations are typically limited by the rate of gas-to-liquid mass transfer. Consequently, a major engineering challenge in commercial development of synthesis-gas fermentations is to provide sufficient gas mass transfer in an energy-efficient manner. This paper reviews recent progress in the development of synthesis-gas fermentations, with emphasis on efforts to increase the efficiency of gas mass transfer. Metabolic properties of several microbes able to ferment synthesis gas are described. Results of synthesis-gas fermentations conducted in various bioreactor configurations are summarized. Recent results showing enhancement of synthesis-gas fermentations using microbubble dispersions are presented, and studies of the mass-transfer and coalescence properties of microbubbles are described.

  9. Simple, Chemoselective Hydrogenation with Thermodynamic Stereocontrol

    PubMed Central

    2015-01-01

    Few methods permit the hydrogenation of alkenes to a thermodynamically favored configuration when steric effects dictate the alternative trajectory of hydrogen delivery. Dissolving metal reduction achieves this control, but with extremely low functional group tolerance. Here we demonstrate a catalytic hydrogenation of alkenes that affords the thermodynamic alkane products with remarkably broad functional group compatibility and rapid reaction rates at standard temperature and pressure. PMID:24428640

  10. Chemoselective probes for metabolite enrichment and profiling

    E-print Network

    Cai, Long

    of human cancer cells treated with the antioxidant N-acetyl-L-cysteine. Understanding the metabolic that support cancer10. Still, general methods to enrich other classes of small-molecules (for example, polar

  11. Facile synthesis of efficient visible active C-doped TiO{sub 2} nanomaterials with high surface area for the simultaneous removal of phenol and Cr(VI)

    SciTech Connect

    Mani, A.Daya; Reddy, P.Manoj Kumar; Srinivaas, M.; Ghosal, P.; Xanthopoulos, N.; Subrahmanyam, Ch.

    2015-01-15

    Highlights: • Facile synthesis of C-doped TiO{sub 2} nanomaterials with high surface area. • Utilization of citric acid and ascorbic acid as fuels based on evolution of gases. • Enhanced visible activity for the oxidation of phenol and reduction of Cr(VI). • Study of simultaneous oxidation of phenol and reduction of Cr(VI) for the first time. • Proposed plausible mechanism for the simultaneous removal of phenol and Cr(VI). - Abstract: A single step synthesis of carbon doped TiO{sub 2} (anatase) nanomaterials have been reported by using combustion synthesis using ascorbic acid and citric acid fuels. X-ray diffraction studies indicated the formation of nanosized anatase titania, whereas, transmission electron microscopy confirmed the formation of nanosized TiO{sub 2} anatase. The carbon doping into TiO{sub 2} matrix was identified by X-ray photoelectron spectroscopy, whereas, thermogravimetric study quantified the carbon doping. Diffuse reflectance UV–vis spectra indicated the band gap of less than 3 eV, a prerequisite for the photocatalytic activity under visible light irradiation. The N{sub 2} adsorption studies revealed the high surface area (upto 290 m{sup 2}/g) of the synthesized photocatalysts. Typical photocatalytic activity data indicated that the simultaneous removal of Cr(VI) and phenol is advantageous than degradation of the individual pollutants.

  12. MICROWAVE PHOTOREACTOR FOR PHOTOCHEMICAL SYNTHESIS Milan Hajeka

    E-print Network

    Cirkva, Vladimir

    MICROWAVE PHOTOREACTOR FOR PHOTOCHEMICAL SYNTHESIS Milan Hajeka , Vladimir Cirkvaa and Petr Klanb University, Kotlarska 2, 611 37 Brno, Czech Republic Introduction Microwave chemistry is a very young scientific discipline and microwave (MW) irradiation represents a new way to increase the efficiency of many

  13. Synthesis of Polycyclic Natural Products

    SciTech Connect

    Tuan Hoang Nguyen

    2003-05-31

    With the continuous advancements in molecular biology and modern medicine, organic synthesis has become vital to the support and extension of those discoveries. The isolations of new natural products allow for the understanding of their biological activities and therapeutic value. Organic synthesis is employed to aid in the determination of the relationship between structure and function of these natural products. The development of synthetic methodologies in the course of total syntheses is imperative for the expansion of this highly interdisciplinary field of science. In addition to the practical applications of total syntheses, the structural complexity of natural products represents a worthwhile challenge in itself. The pursuit of concise and efficient syntheses of complex molecules is both gratifying and enjoyable.

  14. Total Synthesis of Atisane-Type Diterpenoids: Application of Diels-Alder Cycloadditions of Podocarpane-Type Unmasked ortho-Benzoquinones.

    PubMed

    Song, Liqiang; Zhu, Guili; Liu, Yongjiang; Liu, Bo; Qin, Song

    2015-10-28

    Few examples of [4 + 2] cycloaddition with unmasked ortho-benzoquinones (UMOBs) as carbodiene have been reported in complex molecule synthesis. Herein we report that this cycloaddition with podocarpane-type UMOB was developed and applied to construct fully functionalized bicyclo[2.2.2]octanes. Based on this methodology, divergent total syntheses of atisane-type diterpenoids, including (±)-crotobarin, crotogoudin, atisane-3?,16?-diol, and 16S,17-dihydroxy-atisan-3-one, were accomplished in 14, 14, 12, and 16 steps, respectively. Key elements in these total syntheses include: (1) FeCl3-catalyzed cationic cascade cyclization to construct podocarpane-type skeleton; (2) Mn(III)/Co(II)-catalyzed radical hydroxylation of alkene with high regio-, diastereo-, and chemoselectivities; (3) and a ketal-deprotection/lactone-opening/deprotonation/lactonization cascade. Additionally, the synthetic utility of the fully functionalized bicyclo[2.2.2]octane framework was further elucidated by applying ring distortion strategy to afford different skeleton-rearranged natural product-like compounds. PMID:26434364

  15. An Efficient Protocol for the Green and Solvent-Free Synthesis of Azine Derivatives at Room Temperature Using BiCl3-Loaded Montmorillonite K10 as a New Recyclable Heterogeneous Catalyst

    PubMed Central

    Ravi, K.; Krishnakumar, B.; Swaminathan, M.

    2012-01-01

    A new BiCl3-loaded montmorillonite K10 catalyst has been prepared by solid dispersion method and was characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and cyclic voltammetry (CV) measurements. BiCl3 loaded K10 (BiCl3-K10) has been used as solid acid catalyst for the synthesis of azine derivatives from benzophenone hydrazone and ketones/aldehydes by simple physical grinding. This BiCl3-K10 gives an excellent yield with short reaction time and is an inexpensive, easily recyclable catalyst for this reaction. PMID:24052847

  16. Total Synthesis of (?)-Himandrine

    E-print Network

    Movassaghi, Mohammad

    We describe the first total synthesis of (?)-himandrine, a member of the class II galbulimima alkaloids. Noteworthy features of this chemistry include a diastereoselective Diels?Alder reaction in the rapid synthesis of the ...

  17. A Sustainable Multicomponent Pyrimidine Synthesis.

    PubMed

    Deibl, Nicklas; Ament, Kevin; Kempe, Rhett

    2015-10-14

    Since alcohols are accessible from indigestible biomass (lignocellulose), the development of novel preferentially catalytic reactions in which alcohols are converted into important classes of fine chemicals is a central topic of sustainable synthesis. Multicomponent reactions are especially attractive in organic chemistry as they allow the synthesis of large libraries of diversely functionalized products in a short time when run in a combinatorial fashion. Herein, we report a novel, regioselective, iridium-catalyzed multicomponent synthesis of pyrimidines from amidines and up to three (different) alcohols. This reaction proceeds via a sequence of condensation and dehydrogenation steps which give rise to selective C-C and C-N bond formations. While the condensation steps deoxygenate the alcohol components, the dehydrogenations lead to aromatization. Two equiv of hydrogen and water are liberated in the course of the reactions. PN5P-Ir-pincer complexes, recently developed in our laboratory, catalyze this sustainable multicomponent process most efficiently. A total of 38 different pyrimidines were synthesized in isolated yields of up to 93%. Strong points of the new protocol are its regioselectivity and thus the immediate access to pyrimidines that are highly and unsymmetrically decorated with alkyl or aryl substituents. The combination of this novel protocol with established methods for converting alcohols to nitriles now allows to selectively assemble pyrimidines from four alcohol building blocks and 2 equiv of ammonia. PMID:26414993

  18. Reversible derivatization to enhance enzymatic synthesis: Chemoenzymatic synthesis of Doxorubicin-14-O-Esters

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An efficient three-step, chemoenzymatic synthesis of unprotected doxorubicin-14-O-esters from doxorubicin hydrochloride salt is described. The key step is a lipase-catalyzed regioselective transesterification/esterification using commercially-available acyl donors and doxorubicin reversibly derivat...

  19. Zeolite catalyzed solvent-free one-pot synthesis of dihydropyrimidin-2(1H)-ones – A practical synthesis of monastrol

    PubMed Central

    Chavhan, Sanjay W; Shinde, Mahadev P; Gaikwad, Dnyaneshwar D; Borhade, Ajit S; Dhondge, Attrimuni P; Shaikh, Yunnus B; Ningdale, Vijay B; Desai, Mayur P; Birhade, Deekshaputra R

    2009-01-01

    Summary A zeolite-catalyzed, simple, one-pot, solvent-free, cost effective, and environmentally benign process for the synthesis of dihydropyrimidones is described. This reaction is scaleable to multigram scale and the catalyst is recyclable. This methodology has resulted in an efficient synthesis of monastrol, a potent inhibitor of kinesin Eg5. PMID:19259340

  20. Two Palladium-Catalyzed Domino Reactions from One Set of Substrates/Reagents: Efficient Synthesis of Substituted Indenes and cis-Stilbenoid Hydrocarbons from the Same Internal Alkynes and Hindered Grignard Reagents

    PubMed Central

    Dong, Cheng-Guo; Yeung, Pik; Hu, Qiao-Sheng

    2008-01-01

    Two types of domino reactions from the same internal alkynes and hindered Grignard reagents based on carbopalladation, Pd-catalyzed cross-coupling reaction and C-H activation strategy are described. The realization of these domino reactions relied on the control of the use of the ligand and the reaction temperature. Our study provides an efficient access to useful polysubstituted indenes and cis-substituted stilbenes, and may offer new means to the development of tandem/domino reactions in a more efficient way. PMID:17217305

  1. Facile Synthesis of Spirocyclic Lactams from ?-Keto Carboxylic Acids.

    PubMed

    Yang, Wei; Sun, Xianyu; Yu, Wenbo; Rai, Rachita; Deschamps, Jeffrey R; Mitchell, Lauren A; Jiang, Chao; MacKerell, Alexander D; Xue, Fengtian

    2015-06-19

    A facile synthesis of spirocyclic lactams starting from ?-keto carboxylic acids via a one-pot cascade reaction involving a Curtius rearrangement and an intramolecular nucleophilic addition of the enol carbon to the isocyanate intermediate is reported. The same conditions have also been used for the generation of fused cyclic lactams with similar good yields. The synthetic value of this method has been demonstrated by efficient synthesis of tetracyclic spirolactam 8 and pentacyclic spirolactam 9. PMID:26043081

  2. The origin of polynucleotide-directed protein synthesis

    NASA Technical Reports Server (NTRS)

    Orgel, Leslie E.

    1989-01-01

    If protein synthesis evolved in an RNA world it was probably preceded by simpler processes by means of which interaction with amino acids conferred selective advantage on replicating RNA molecules. It is suggested that at first the simple attachment of amino acids to the 2'(3') termini of RNA templates favored initiation of replication at the end of the template rather than at internal positions. The second stage in the evolution of protein synthesis would probably have been the association of pairs of charged RNA adaptors in such a way as to favor noncoded formation of peptides. Only after this process had become efficient could coded synthesis have begun.

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

    PubMed

    de Léséleuc, Mylène; Collins, Shawn K

    2015-07-01

    Efficient direct synthesis of macrodiolides via catalysis using Hf(OTf)4 is possible in high yields, forming water as the sole by-product. The first protocol for the direct synthesis of macrodiolides from equimolar mixtures of diols and dicarboxylic acids was developed (58-96%). In addition, modification of the reaction concentration allows for the synthesis of head-to-tail macrodiolides from the corresponding seco acids. The catalytic preparation of the macrodiolides using a commercially available catalyst without the need for slow addition or azeotropic condition provides an operationally simple alternative to protocols which employ toxic tin catalysts or stoichiometric activation strategies. PMID:26028490

  4. Homogeneously catalyzed synthesis gas transformations to oxygenate fuels

    SciTech Connect

    Mahajan, D.; Mattas, L.; Sanchez, J.

    1992-04-01

    At Brookhaven National Laboratory (BNL), the ongoing oxygenates synthesis program is addressing the catalytic synthesis gas conversion to liquid fuels and fuel additives. The major thrust of this effort is to enhance carbon conversion, reaction rates, product selectivity and overall process efficiency. To this effect, a series of liquid phase homogeneous catalysts have been developed and successfully utilized in the synthesis of methanol and other oxygenates. This paper identifies advantages and uncertainties associated with these newly developed catalysts. The effect of system parameters on the overall process scheme is discussed.

  5. Homogeneously catalyzed synthesis gas transformations to oxygenate fuels

    SciTech Connect

    Mahajan, D.; Mattas, L.; Sanchez, J.

    1992-01-01

    At Brookhaven National Laboratory (BNL), the ongoing oxygenates synthesis program is addressing the catalytic synthesis gas conversion to liquid fuels and fuel additives. The major thrust of this effort is to enhance carbon conversion, reaction rates, product selectivity and overall process efficiency. To this effect, a series of liquid phase homogeneous catalysts have been developed and successfully utilized in the synthesis of methanol and other oxygenates. This paper identifies advantages and uncertainties associated with these newly developed catalysts. The effect of system parameters on the overall process scheme is discussed.

  6. Tremorgenic indole alkaloids. The total synthesis of (-)-penitrem D.

    PubMed

    Smith, Amos B; Kanoh, Naoki; Ishiyama, Haruaki; Minakawa, Noriaki; Rainier, Jon D; Hartz, Richard A; Cho, Young Shin; Cui, Haifeng; Moser, William H

    2003-07-01

    A convergent, stereocontrolled total synthesis of the architecturally complex tremorgenic indole alkaloid (-)-penitrem D (4) has been achieved. Highlights of the synthesis include an efficient, asymmetric synthesis of the western hemisphere; the stereocontrolled assembly of the I-ring; discovery of a novel autoxidation to introduce the C(22) tertiary hydroxyl group, required for tremorgenic activity; union of fully elaborated eastern and western hemispheres, exploiting an indole synthetic protocol developed expressly for this purpose; and a late-stage, stereoselective construction of the A and F rings exploiting a Sc(OTf)(3-)promoted reaction cascade. The longest linear sequence leading to (-)-penitrem D (4) was 43 steps. PMID:12837093

  7. Hydrogenation processes in the synthesis of perfumery ingredients.

    PubMed

    Saudan, Lionel A

    2007-12-01

    Homogeneous catalytic hydrogenation has played an important role in the development of modern organic synthesis. Indeed, the discovery of highly regio- and stereoselective catalysts for C=C and C=O bonds reductions has allowed the efficient synthesis of optically active compounds. As the fragrance industry has turned to synthetic ingredients to fulfill the need for novel, cost-effective, and environment-friendly products, the use of catalytic processes are more and more in demand. In this Account, we thus highlight the application of catalytic hydrogenation in the synthesis of fragrance ingredients. PMID:17960898

  8. Microwaves and nanoparticles: from synthesis to imaging

    NASA Astrophysics Data System (ADS)

    Meissner, Kenith E.; Majithiaa, Ravish; Brown, R. A.; Wang, Lihong V.; Maffeis, T. G. G.

    2011-03-01

    We investigate the use of energy delivery using microwave radiation for both synthesis of nanoparticles as well as a hybrid imaging technique known as thermoacoustic tomography (TAT). In each instance, the absorption of microwave radiation is converted into heat. In the case of nanoparticle synthesis, water is used as the solvent and heated to induce synthesis of the nanostructures. For this aqueous synthesis technique, we demonstrate the use of both pulsed and continuous wave (CW) microwave systems operating at 2.45 GHz. In this report, we concentrate on ZnO nanostructures including nanorods, nanowire arrays and nanobelts. These are compared with nanowire arrays and nanobelts grown by vapor transport through both electron microscopy and photo-excited luminescence. We also review the use of iron oxide (Fe3O4) nanoparticles as contrast agents in TAT as previously reported. Here, we measured the properties of the colloidal nanoparticles in the microwave regime and compared the absorption with the TAT signal produced by our thermoacoustic imaging system at 3 GHz. The nanoparticles directly absorb the microwave radiation and produce a thermo-acoustic signal. The results from nanoparticles are compared to the signal produced by deionized water. The results demonstrate that microwaves represent an efficient method for the delivery of energy for both synthesis and biomedical imaging.

  9. Towards High-Assurance High-Performance Program Synthesis

    NASA Technical Reports Server (NTRS)

    Lowry, Michael; Roach, Steven; vanBaalen, Jeffrey

    1997-01-01

    Domain-specific automatic program synthesis tools, also called application generators, are playing an ever-increasing role in software development. However, high-performance application generators require difficult manual construction, and are very difficult to verify correct. This paper describes research and an implemented system that transforms program synthesis tools based on deductive synthesis into high-performance application generators. Deductive synthesis uses theorem-proving to construct solutions when given problem specifications. The verification condition for a deductive synthesis tool is essentially the soundness of the implemented inference rules. Theory Operationalization for Program Synthesis (TOPS) synergistically combines reformulation, automated mathematical classification, and compilation through partial deduction to decision procedures. It transforms general-purpose deductive synthesis, with exponential performance, into efficient special-purpose deductive synthesis, with near-linear performance. This paper describes our experience with and empirical results of PD(TH) theory-based partial deduction - in which partial deduction of a set of first-order formulae is performed within the context of a background theory. The implemented TOPS system currently performs a special variant of PD(TH) in which the compilation process results in the transformation of a set of first order formulae into the theory of an instantiated library decision procedure augmented by a compiled unit theory.

  10. AutoBayes Program Synthesis System System Internals

    NASA Technical Reports Server (NTRS)

    Schumann, Johann Martin

    2011-01-01

    This lecture combines the theoretical background of schema based program synthesis with the hands-on study of a powerful, open-source program synthesis system (Auto-Bayes). Schema-based program synthesis is a popular approach toward program synthesis. The lecture will provide an introduction into this topic and discuss how this technology can be used to generate customized algorithms. The synthesis of advanced numerical algorithms requires the availability of a powerful symbolic (algebra) system. Its task is to symbolically solve equations, simplify expressions, or to symbolically calculate derivatives (among others) such that the synthesized algorithms become as efficient as possible. We will discuss the use and importance of the symbolic system for synthesis. Any synthesis system is a large and complex piece of code. In this lecture, we will study Autobayes in detail. AutoBayes has been developed at NASA Ames and has been made open source. It takes a compact statistical specification and generates a customized data analysis algorithm (in C/C++) from it. AutoBayes is written in SWI Prolog and many concepts from rewriting, logic, functional, and symbolic programming. We will discuss the system architecture, the schema libary and the extensive support infra-structure. Practical hands-on experiments and exercises will enable the student to get insight into a realistic program synthesis system and provides knowledge to use, modify, and extend Autobayes.

  11. Functionality, antibacterial efficiency and biocompatibility of nanosilver/chitosan/silk/phosphate scaffolds 1. Synthesis and optimization of nanosilver/chitosan matrices through gamma rays irradiation and their antibacterial activity

    NASA Astrophysics Data System (ADS)

    Abdel-Fattah, Wafa I.; Sallam, Abdel Sattar M.; Atwa, Nagwa A.; Salama, E.; Maghraby, Ahmed M.; Ali, Ghareib W.

    2014-09-01

    Silver nanoparticles (SN) were synthesized via the green approach of gamma radiation. Chitosan was used as both reducing and stabilizing agent. Studies involved the influence of various parameters of four irradiation doses and three silver precursor concentrations on the produced silver nanoparticles. The UV-vis spectra proved characteristic surface plasmon resonance (SPR) of SN whose intensities and positions were dependant on silver concentrations. X-ray diffraction analyses and transmission electron microscopy (TEM) observations proved the fabrication of spherical crystalline face centered cubic SN with a mean diameter of 7-22 nm. Further characterization of the fabricated silver nanoparticles/chitosan composite (SNCC) was conducted using Fourier transform infrared spectroscopy and zeta potential measurements. Finally, the bactericidal effect of the SNCC with glutaraldehyde was tested against three different medically relevant strains of gram negative and gram positive bacteria. Excellent selective inhibiting function of the films was proved by the gram positive strain compared to the other gram negative ones. The synthesis and successful size selection of SN obtained through gamma irradiation reduction of silver nitrate using chitosan as a protective agent was achieved presenting high bactericidal functions, especially for the gram positive strain.

  12. Efficient delivery to human lung fibroblasts (WI-38) of pirfenidone incorporated into liposomes modified with truncated basic fibroblast growth factor and its inhibitory effect on collagen synthesis in idiopathic pulmonary fibrosis.

    PubMed

    Togami, Kohei; Miyao, Aki; Miyakoshi, Kei; Kanehira, Yukimune; Tada, Hitoshi; Chono, Sumio

    2015-01-01

    In the present in vitro study, we assessed the delivery of pirfenidone incorporated into liposomes modified with truncated basic fibroblast growth factor (tbFGF) to lung fibroblasts and investigated the anti-fibrotic effect of the drug. The tbFGF peptide, KRTGQYKLC, was used to modify the surface of liposomes (tbFGF-liposomes). We used the thin-layer evaporation method, followed by sonication, to prepare tbFGF-liposomes containing pirfenidone. The cellular accumulation of tbFGF-liposomes was 1.7-fold greater than that of non-modified liposomes in WI-38 cells used as a model of lung fibroblasts. Confocal laser scanning microscopy showed that tbFGF-liposomes were widely localized in WI-38 cells. The inhibitory effects of pirfenidone incorporated into tbFGF-liposomes on transforming growth factor-?1 (TGF-?1)-induced collagen synthesis in WI-38 cells were evaluated by measuring the level of intracellular hydroxyproline, a major component of the protein collagen. Pirfenidone incorporated into tbFGF-liposomes at concentrations of 10, 30, and 100 µM significantly decreased the TGF-?1-induced hydroxyproline content in WI-38 cells. The anti-fibrotic effect of pirfenidone incorporated into tbFGF-liposomes was enhanced compared with that of pirfenidone solution. These results indicate that tbFGF-liposomes are a useful drug delivery system of anti-fibrotic drugs to lung fibroblasts for the treatment of idiopathic pulmonary fibrosis. PMID:25747986

  13. DNA-Encoded Solid-Phase Synthesis: Encoding Language Design and Complex Oligomer Library Synthesis.

    PubMed

    MacConnell, Andrew B; McEnaney, Patrick J; Cavett, Valerie J; Paegel, Brian M

    2015-09-14

    The promise of exploiting combinatorial synthesis for small molecule discovery remains unfulfilled due primarily to the "structure elucidation problem": the back-end mass spectrometric analysis that significantly restricts one-bead-one-compound (OBOC) library complexity. The very molecular features that confer binding potency and specificity, such as stereochemistry, regiochemistry, and scaffold rigidity, are conspicuously absent from most libraries because isomerism introduces mass redundancy and diverse scaffolds yield uninterpretable MS fragmentation. Here we present DNA-encoded solid-phase synthesis (DESPS), comprising parallel compound synthesis in organic solvent and aqueous enzymatic ligation of unprotected encoding dsDNA oligonucleotides. Computational encoding language design yielded 148 thermodynamically optimized sequences with Hamming string distance ? 3 and total read length <100 bases for facile sequencing. Ligation is efficient (70% yield), specific, and directional over 6 encoding positions. A series of isomers served as a testbed for DESPS's utility in split-and-pool diversification. Single-bead quantitative PCR detected 9 × 10(4) molecules/bead and sequencing allowed for elucidation of each compound's synthetic history. We applied DESPS to the combinatorial synthesis of a 75,645-member OBOC library containing scaffold, stereochemical and regiochemical diversity using mixed-scale resin (160-?m quality control beads and 10-?m screening beads). Tandem DNA sequencing/MALDI-TOF MS analysis of 19 quality control beads showed excellent agreement (<1 ppt) between DNA sequence-predicted mass and the observed mass. DESPS synergistically unites the advantages of solid-phase synthesis and DNA encoding, enabling single-bead structural elucidation of complex compounds and synthesis using reactions normally considered incompatible with unprotected DNA. The widespread availability of inexpensive oligonucleotide synthesis, enzymes, DNA sequencing, and PCR make implementation of DESPS straightforward, and may prompt the chemistry community to revisit the synthesis of more complex and diverse libraries. PMID:26290177

  14. DNA-Encoded Solid-Phase Synthesis: Encoding Language Design and Complex Oligomer Library Synthesis

    PubMed Central

    2015-01-01

    The promise of exploiting combinatorial synthesis for small molecule discovery remains unfulfilled due primarily to the “structure elucidation problem”: the back-end mass spectrometric analysis that significantly restricts one-bead-one-compound (OBOC) library complexity. The very molecular features that confer binding potency and specificity, such as stereochemistry, regiochemistry, and scaffold rigidity, are conspicuously absent from most libraries because isomerism introduces mass redundancy and diverse scaffolds yield uninterpretable MS fragmentation. Here we present DNA-encoded solid-phase synthesis (DESPS), comprising parallel compound synthesis in organic solvent and aqueous enzymatic ligation of unprotected encoding dsDNA oligonucleotides. Computational encoding language design yielded 148 thermodynamically optimized sequences with Hamming string distance ? 3 and total read length <100 bases for facile sequencing. Ligation is efficient (70% yield), specific, and directional over 6 encoding positions. A series of isomers served as a testbed for DESPS’s utility in split-and-pool diversification. Single-bead quantitative PCR detected 9 × 104 molecules/bead and sequencing allowed for elucidation of each compound’s synthetic history. We applied DESPS to the combinatorial synthesis of a 75?645-member OBOC library containing scaffold, stereochemical and regiochemical diversity using mixed-scale resin (160-?m quality control beads and 10-?m screening beads). Tandem DNA sequencing/MALDI-TOF MS analysis of 19 quality control beads showed excellent agreement (<1 ppt) between DNA sequence-predicted mass and the observed mass. DESPS synergistically unites the advantages of solid-phase synthesis and DNA encoding, enabling single-bead structural elucidation of complex compounds and synthesis using reactions normally considered incompatible with unprotected DNA. The widespread availability of inexpensive oligonucleotide synthesis, enzymes, DNA sequencing, and PCR make implementation of DESPS straightforward, and may prompt the chemistry community to revisit the synthesis of more complex and diverse libraries. PMID:26290177

  15. Total Synthesis and Study of Myrmicarin Alkaloids

    PubMed Central

    Ondrus, Alison E.

    2010-01-01

    The myrmicarins are a family of air and temperature sensitive alkaloids that possess unique structural features. Our concise enantioselective synthesis of the tricyclic myrmicarins enabled evaluation of a potentially biomimetic assembly of the complex members via direct dimerization of simpler structures. These studies revealed that myrmicarin 215B undergoes efficient and highly diastereoselective Brønsted acid-induced dimerization to generate a new heptacyclic structure, isomyrmicarin 430A. Mechanistic analysis demonstrated that heterodimerization between myrmicarin 215B and a conformationally restricted azafulvenium ion precursor afforded a functionalized isomyrmicarin 430A structure in a manner that was consistent with a highly efficient, non-concerted ionic process. Recent advancement in heterodimerization between tricyclic derivatives has enabled the preparation of strategically functionalized hexacyclic structures. The design and synthesis of structurally versatile dimeric compounds has greatly facilitated manipulation of these structures en route to more complex myrmicarin derivatives. PMID:19585010

  16. A Convenient Synthesis of Hydroxytyrosol Monosulfate Metabolites.

    PubMed

    Gomes, Vânia Patrícia Martins; Torres, Carmen; Rodríguez-Borges, José Enrique; Paiva-Martins, Fátima

    2015-11-01

    The growing interest in the bioactivity of natural polyphenols and of their metabolites requires metabolites to be used in bioassays and as standards in research protocols. We report here on the synthesis of several hydroxytyrosol metabolite monosulfates achieved using a simplified protocol with improved yields. A synthetic solution based on avoidance of high temperature conditions during the synthesis and of low pressure conditions during purification has been established. Monosulfates of several phenolic compounds, namely, hydroxytyrosol, hydroxytyrosol acetate, homovanillyl alcohol, homovanillyl alcohol acetate, homovanillic acid, ferulic acid, and 3,4-dihydroxyphenylethanoic acid, were efficiently synthesized in 1-2 steps in good yield and isolated using simple procedures. The proposed protocol was shown to be relatively rapid, efficient, cheap, and widely applicable to a number of catechol scaffolds. PMID:26492463

  17. An efficient synthesis of 3,4-Dihydropyrimidin-2(1H)-ones and thiones catalyzed by a novel Brønsted acidic ionic liquid under solvent-free conditions.

    PubMed

    Zhang, Yonghong; Wang, Bin; Zhang, Xiaomei; Huang, Jianbin; Liu, Chenjiang

    2015-01-01

    We report here an efficient and green method for Biginelli condensation reaction of aldehydes, ?-ketoesters and urea or thiourea catalyzed by Brønsted acidic ionic liquid [Btto][p-TSA] under solvent-free conditions. Compared to the classical Biginelli reaction conditions, the present method has the advantages of giving good yields, short reaction times, near room temperature conditions and the avoidance of the use of organic solvents and metal catalyst. PMID:25730389

  18. Scalable Synthesis of Human Ultralong Chain Ceramides.

    PubMed

    Opálka, Lukáš; Ková?ik, Andrej; Sochorová, Michaela; Roh, Jaroslav; Kuneš, Ji?í; Len?o, Juraj; Vávrová, Kate?ina

    2015-11-01

    Ceramides with ultralong chains (?30 carbons), also known as acylceramides, play a critical role in the survival of mammals on dry land. An efficient and scalable synthesis of four major classes of ultralong human skin ceramides is reported. The key approach involves the use of a succinimidyl ester that acts as a protective group, helps overcome the extremely low solubility, and simultaneously activates the fatty acid for its clean and high-yielding attachment to a sphingoid base. PMID:26479675

  19. Direct synthesis of methyl phosphoramidates in carbohydrates.

    PubMed

    Dhurandhare, Vijay M; Mishra, Girija Prasad; Lam, Sarah; Wang, Cheng-Chung

    2015-09-28

    A direct installation of a methyl phosphoramidate group by using methyl benzylphosphoramidochloridate into carbohydrates and amino acid is described. This one-step synthesis is efficient for both primary and secondary alcohols and exhibited excellent regioselectivity and functional group compatibility. Formation of a single diastereomer is observed in certain cases. The N-benzyl protecting group on methyl phosphoramidates is easily removed under mild conditions. PMID:26247390

  20. Crossed Intermolecular [2+2] Cycloaddition of Styrenes by Visible Light Photocatalysis

    PubMed Central

    Ischay, Michael A.; Ament, Michael S.; Yoon, Tehshik P.

    2012-01-01

    We report a method for the crossed [2+2] cycloaddition of styrenes using visible light photocatalysis. Few methods for the synthesis of unsymmetrically substituted cyclobutanes by photochemical [2+2] cycloaddition are known. We show that careful tuning of the electrochemical properties of a ruthenium photocatalyst enable the efficient crossed [2+2] cycloaddition of styrenes upon irradiation with visible light. We outline the logic that enables high crossed chemoselectivity, and we also demonstrate that this reaction is remarkably efficient; gram-scale reactions can be conducted with as little as 0.025 mol% of the photocatalyst. PMID:22984640

  1. A convergent synthesis of the fully elaborated macrocyclic core of TMC-95A.

    PubMed

    Coste, Alexis; Bayle, Alexandre; Marrot, Jérome; Evano, Gwilherm

    2014-03-01

    A concise and straightforward synthesis of the fully elaborated macrocyclic core of TMC-95A is reported. A highly efficient organocatalyzed aldolization between isatin and dihydroxyacetone derivatives and formation of the biaryl subunit with concomitant macrocyclization are the characteristic features of this synthesis. PMID:24559256

  2. Catalytic enantioselective synthesis of naturally occurring butenolides via hetero-allylic alkylation and ring closing metathesis.

    PubMed

    Mao, Bin; Geurts, Koen; Fañanás-Mastral, Martín; van Zijl, Anthoni W; Fletcher, Stephen P; Minnaard, Adriaan J; Feringa, Ben L

    2011-03-01

    An efficient catalytic asymmetric synthesis of chiral ?-butenolides was developed based on the hetero-allylic asymmetric alkylation (h-AAA) in combination with ring closing metathesis (RCM). The synthetic potential of the h-AAA-RCM protocol was illustrated with the facile synthesis of (-)-whiskey lactone, (-)-cognac lactone, (-)-nephrosteranic acid, and (-)-roccellaric acid. PMID:21268603

  3. NHC-Catalyzed Asymmetric Synthesis of Functionalized Succinimides from Enals and ?-Ketoamides

    PubMed Central

    Wang, Lei; Ni, Qijian; Blümel, Marcus; Shu, Tao; Raabe, Gerhard; Enders, Dieter

    2015-01-01

    The efficient asymmetric synthesis of highly substituted succinimides from ?,?-unsaturated aldehydes and ?-ketoamides via NHC-catalyzed [3+2] cycloaddition has been developed. The new scalable protocol significantly expands the utility of NHC catalysis for the synthesis of heterocycles and provides easy access to assemble a wide range of succinimides from simple starting materials. PMID:25877658

  4. Synthesis of the C4-epi-lomaiviticin B core reveals subtle stereoelectronic effects.

    PubMed

    Lee, Amy S; Shair, Matthew D

    2013-05-17

    An efficient synthesis of the C4-epi-lomaiviticin B core is reported. The synthesis features a diastereoselective anionic formal furan Diels-Alder reaction and a stereoselective oxidative enolate dimerization. During the investigation, subtle yet critical stereoelectronic effects imparted by the C4-stereocenter were observed. PMID:23659351

  5. Formal Synthesis of Anticoagulant Drug Fondaparinux Sodium.

    PubMed

    Dai, Xiang; Liu, Wentao; Zhou, Qilong; Cheng, Chunwei; Yang, Chao; Wang, Shuqing; Zhang, Min; Tang, Pei; Song, Hao; Zhang, Dan; Qin, Yong

    2016-01-01

    The practical formal synthesis of the anticoagulant drug fondaparinux sodium 1 was accomplished using an optimized modular synthetic strategy. The important pentasaccharide 2, a precursor for the synthesis of fondaparinux sodium, was synthesized on a 10 g scale in 14 collective steps with 3.5% overall yield from well-functionalized monosaccharide building blocks. The strategy involved a convergent [3 + 2] coupling approach, with excellent stereoselectivity in every step of glycosylation from the monosaccharide building blocks. Efficient routes to the syntheses of these fully functionalized building blocks were developed, minimizing oligosaccharide stage functional-group modifications. The syntheses of all building blocks avoided rigorous reaction conditions and the use of expensive reagents. In addition, common intermediates and a series of one-pot reactions were employed to enhance synthetic efficiency, improving the yield considerably. In the monosaccharide-to-oligosaccharide assembly reactions, cheaper activators (e.g., NIS/TfOH, TESOTf, and TfOH) were used to facilitate highly efficient glycosylations. Furthermore, crystallization of several monosaccharide and oligosaccharide intermediates significantly simplified purification procedures, which would be greatly beneficial to the scalable synthesis of fondaparinux sodium. PMID:26650028

  6. Phenylthiocarbamate or N-Carbothiophenyl Group Chemistry in Peptide Synthesis and Bioconjugation

    PubMed Central

    2015-01-01

    The design of novel chemoselective and site-specific ligation methods provides new tools for obtaining complex scaffolds, peptidomimetics, and peptide conjugates. The chemistry of the N-phenylthiocarbonyl group has led to several developments in peptide ligation chemistry and peptide bioconjugation during the last 10 years. The aim of this review is to provide an overview of this emerging field. PMID:24641212

  7. A Synthesis of the Chlorosulfolipid Mytilipin A via a Longest Linear Sequence of Seven Steps

    PubMed Central

    Chung, Won-jin; Carlson, Joseph S.; Bedke, D. Karl

    2013-01-01

    The chlorosulfolipid mytilipin A has been synthesized in racemic form in only seven steps and in enantioenriched form in eight steps. Key transformations include a highly diastereoselective bromoallylation of a sensitive ?,?-dichloroaldehyde, a kinetic resolution of a complex vinyl epoxide, a convergent and highly Z-selective alkene cross metathesis, and a chemoselective and diastereoselective dichlorination of a complex diene. PMID:23929596

  8. Facile Synthesis of Novel Redox-Mediator-free Direct Z-Scheme CaIn2S4 Marigold-Flower-like/TiO2 Photocatalysts with Superior Photocatalytic Efficiency.

    PubMed

    Jo, Wan-Kuen; Sivakumar Natarajan, Thillai

    2015-08-12

    Novel redox-mediator-free direct Z-scheme CaIn2S4 marigold-flower-like/TiO2 (CIS/TNP) photocatalysts with different CaIn2S4 weight percentages were synthesized using a facile wet-impregnation method. Uniform hierarchical marigold-flower-like CaIn2S4 (CIS) microspheres were synthesized using a hydrothermal method. Field-emission scanning electron microscopy and transmission electron microscopy analyses suggested that the formation and aggregation of nanoparticles, followed by the growth of petals or sheets and their subsequent self-assembly, led to the formation of the uniform hierarchical marigold-flower-like CIS structures. The photocatalytic degradation efficiency of the direct Z-scheme CIS/TNP photocatalysts was evaluated through the degradation of the pharmaceutical compounds isoniazid (ISN) and metronidazole (MTZ). The direct Z-scheme CaIn2S4 marigold-flower-like/TiO2 (1%-CIS/TNP) photocatalyst showed enhanced performance in the ISN (71.9%) and MTZ (86.5%) photocatalytic degradations as compared to composites with different CaIn2S4 contents or the individual TiO2 and CaIn2S4. A possible enhancement mechanism based on the Z-scheme formed between the CIS and TNP for the improved photocatalytic efficiency was also proposed. The recombination rate of the photoinduced charge carriers was significantly suppressed for the direct Z-scheme CIS/TNP photocatalyst, which was confirmed by photoluminescence analysis. Radical-trapping studies revealed that photogenerated holes (h+), •OH, and O2•- are the primary active species, and suggested that the enhanced photocatalytic efficiency of the 1%-CIS/TNP follows the Z-scheme mechanism for transferring the charge carriers. It was further confirmed by hydroxyl (•OH) radical determination via fluorescence techniques revealed that higher concentration of •OH radical were formed over 1%-CIS/TNP than over bare CIS and TNP. The separation of the charge carriers was further confirmed using photocurrent and electron spin resonance measurements. Kinetic and chemical oxygen demand analyses were performed to confirm the ISN and MTZ degradation. The results demonstrated that the direct Z-scheme CIS/TNP photocatalyst shows superior decomposition efficiency for the degradation of these pharmaceuticals under the given reaction conditions. PMID:26186618

  9. A facile and eco-friendly synthesis of diarylthiazoles and diarylimidazoles in water

    EPA Science Inventory

    A simple, efficient and high yielding greener protocol for the synthesis of substituted thiazoles and imidazoles is described that utilizes the reaction of readily available ?-tosyloxy ketones with variety of thioamides/amidines in water

  10. Synthesis of Benzyl Esters via Functionalization of Multiple C-H Bonds by Palladium Catalysis.

    PubMed

    Li, Danyang; Yu, Ming; Zhang, Jitan; Liu, Zhanxiang; Zhang, Yuhong

    2015-11-01

    A highly efficient, selective synthesis of benzyl esters by palladium catalysis is developed through the bidentate directing group assisted functionalization of multiple C(sp(3))-H bonds. PMID:26461958

  11. Synthesis of Densely Functionalized Cyclopropanes via Diastereoselective Nucleophilic Additions to in Situ Generated Cyclopropenes

    E-print Network

    Ryabchuk, Pavel

    2013-12-31

    three describes a highly efficient and diastereoselective synthesis of tetrasubstituted donor-acceptor cyclopropanes that can be obtained in a homochiral form from corresponding bromocyclopropyl carboxylic acids. A single chiral center...

  12. Tandem benzannulation-ring closing metathesis strategy for the synthesis of benzo-fused nitrogen heterocycles ;

    E-print Network

    Mak, Xiao Yin

    2008-01-01

    A tandem benzannulation-ring closing metathesis strategy for the efficient synthesis of benzo-fused nitrogen heterocycles such as dihydroquinolines, benzazepines, and benzazocines has been developed. This strategy is based ...

  13. Generation of octave-spanning multiple harmonics for ultrafast waveform synthesis

    E-print Network

    Hsu, Wei-Chun

    Up to seven laser harmonics covering more than two octaves in frequency have been generated efficiently in a single PPLT crystal, permitting the synthesis of 1.5 femtosecond pulses in a stable and compact setting.

  14. Dimethylamine as the key intermediate generated in situ from dimethylformamide (DMF) for the synthesis of thioamides

    PubMed Central

    Chen, Cui

    2015-01-01

    Summary An improved and efficient method for the synthesis of thioamides is presented. For this transformation, dimethylamine as the key intermediate is generated in situ from dimethylformamide (DMF). All the tested substrates produced the desired products with excellent isolated yields.

  15. The N-hydroxymethyl group for stereoselective conjugate addition: application to the synthesis of (-)-statine.

    PubMed

    Yoo, Dongwon; Oh, Joon Seok; Kim, Young Gyu

    2002-04-01

    [reaction: see text] Efficient synthesis of enantiomerically pure (-)-statine was achieved with the stereoselective intramolecular conjugate addition of the hydroxyl group tethered to the amino group of a configurationally stable N-Boc-L-leucinal derivative. PMID:11922821

  16. Batch efficiency

    NASA Astrophysics Data System (ADS)

    Schwickerath, Ulrich; Silva, Ricardo; Uria, Christian

    2010-04-01

    A frequent source of concern for resource providers is the efficient use of computing resources in their centers. This has a direct impact on requests for new resources. There are two different but strongly correlated aspects to be considered: while users are mostly interested in a good turn-around time for their jobs, resource providers are mostly interested in a high and efficient usage of their available resources. Both things, the box usage and the efficiency of individual user jobs, need to be closely monitored so that the sources of the inefficiencies can be identified. At CERN, the Lemon monitoring system is used for both purposes. Examples of such sources are poorly written user code, inefficient access to mass storage systems, and dedication of resources to specific user groups. As a first step for improvements CERN has launched a project to develop a scheduler add-on that allows careful overloading of worker nodes that run idle jobs.

  17. Designed synthesis of multifunctional Fe{sub 3}O{sub 4}@SiO{sub 2}–NH{sub 2}@CS–Co(II) towards efficient oxidation of ethylbenzene

    SciTech Connect

    Li, Shi; Zhai, Shang-Ru; An, Qing-Da; Li, Ming-Hui; Song, Yu; Song, Xiao-Wei

    2014-12-15

    Highlights: • Cooperative integration of magnetic cores and chitosan layers. • Efficient and durable catalyst for the oxidation of ethylbenzene to acetophenone. • Exceptional results of 82.5% EB conversion and 80.4% AP selectivity. • Magnetic recoverable catalyst with excellent reusability even after 10 times run. - Abstract: The preparation of Co(II) supported magnetic heterogeneous catalyst, i.e. Fe{sub 3}O{sub 4}@SiO{sub 2}–NH{sub 2}@CS–Co, and its efficient and selective catalytic properties toward the oxidation of ethylbenzene to acetophenone are presented. The materials were characterized by various physicochemical techniques such as scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, vibrating sample magnetometer, elemental analysis, inductively coupled plasma-atomic emission spectrometer and X-ray photoelectron spectroscopy, etc. The reaction conditions were thoroughly investigated and highly improved catalytic performance (82.5% conversion of ethylbenzene and 80.1% selectivity to acetophenone) was gained under more mild reaction conditions of lower temperature (70 °C), shorter reaction period (60 min) and cheaper and greener oxygen source (H{sub 2}O{sub 2}). More importantly, it could be reused successively at least 10 times when more than 80% of its catalytic activity maintained.

  18. Total synthesis of (+)-iresin.

    PubMed

    Wang, Bian-Lin; Gao, Hai-Tao; Li, Wei-Dong Z

    2015-05-15

    The first asymmetric total synthesis of (+)-iresin (4), an historically important ent-Drimane sesquiterpene lactone, was realized from aldehyde 3 via cyclic orthoester 6 in 5 steps. Notable transformations in this synthesis include a tandem trifluoroperacetic acid (TFPAA)-mediated Baeyer-Villiger oxidation-olefin epoxidation-epoxy ester cyclization, regioselective Burgess dehydration, and regioselective Fétizon oxidative lactonization. PMID:25906145

  19. Reaction synthesis of intermetallics

    SciTech Connect

    Deevi, S.C.; Sikka, V.K.

    1994-12-31

    Exothermicity associated with the synthesis of aluminides was utilized to obtain nickel, iron, and cobalt aluminides. Combustion synthesis, extrusion, and hot pressing were utilized to obtain intermetallics and their composites. Extrusion conditions, reduction ratios, and hot-pressing conditions of the intermetallics and their composites are discussed.

  20. Novel synthesis of manganese and vanadium mixed oxide (V{sub 2}O{sub 5}/OMS-2) as an efficient and selective catalyst for the oxidation of alcohols in liquid phase

    SciTech Connect

    Mahdavi, Vahid Soleimani, Shima

    2014-03-01

    Graphical abstract: Oxidation of various alcohols is studied in the liquid phase over new composite mixed oxide (V{sub 2}O{sub 5}/OMS-2) catalyst using tert-butyl hydroperoxide (TBHP). The activity of V{sub 2}O{sub 5}/OMS-2 samples was considerably increased with respect to OMS-2 catalyst and these samples are found to be suitable for the selective oxidation of alcohols. - Highlights: • V{sub 2}O{sub 5}/K-OMS-2 with different V/Mn molar ratios prepared by the impregnation method. • Oxidation of alcohols was studied in the liquid phase over V{sub 2}O{sub 5}/K-OMS-2 catalyst. • V{sub 2}O{sub 5}/K-OMS-2 catalyst had excellent activity for alcohol oxidation. • Benzyl alcohol oxidation using excess TBHP followed a pseudo-first order kinetic. • The selected catalyst was reused without significant loss of activity. - Abstract: This work reports the synthesis and characterization of mixed oxide vanadium–manganese V{sub 2}O{sub 5}/K-OMS-2 at various V/Mn molar ratios and prepared by the impregnation method. Characterization of these new composite materials was made by elemental analysis, BET, XRD, FT-IR, SEM and TEM techniques. Results of these analyses showed that vanadium impregnated samples contained mixed phases of cryptomelane and crystalline V{sub 2}O{sub 5} species. Oxidation of various alcohols was studied in the liquid phase over the V{sub 2}O{sub 5}/K-OMS-2 catalyst using tert-butyl hydroperoxide (TBHP) and H{sub 2}O{sub 2} as the oxidant. Activity of the V{sub 2}O{sub 5}/K-OMS-2 samples was increased considerably with respect to K-OMS-2 catalyst due to the interaction of manganese oxide and V{sub 2}O{sub 5}. The kinetic of benzyl alcohol oxidation using excess TBHP over V{sub 2}O{sub 5}/K-OMS-2 catalyst was investigated at different temperatures and a pseudo-first order reaction was determined with respect to benzyl alcohol. The effects of reaction time, oxidant/alcohol molar ratio, reaction temperature, solvents, catalyst recycling potential and leaching were investigated.