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. Formal chemoselective synthesis of leucascandrolide A.

    PubMed

    Ferrié, Laurent; Reymond, Sébastien; Capdevielle, Patrice; Cossy, Janine

    2007-06-21

    A chemoselective synthesis of the macrocyclic core of leucascandrolide A has been achieved, utilizing highly enantioselective allylmetalations, an enantioselective Noyori reduction of a propargylic ketone and olefin metatheses as the key steps. PMID:17536809

  3. Chemoselective synthesis of oligosaccharides of 2-deoxy-2-aminosugars

    PubMed Central

    Bongat, Aileen F. G.; Kamat, Medha N.; Demchenko, Alexei V.

    2008-01-01

    Along with the application of the S-benzoxazolyl glycosides to the high-yielding synthesis of disaccharides of the 2-amino-2-deoxy series, chemoselective assembly of oligosaccharides containing multiple residues of 2-amino-2-deoxyglycoses is reported. This modified armed-disarmed approach is relying on the observation that 2-N-trichloroethoxycarbonyl derivatives of S-benzoxazolyl glycosides are significantly more reactive than their 2-N-phthaloyl counterparts in MeOTf-promoted glycosylations. This allowed efficient chemoselective synthesis of 1,2-trans-linked oligosaccharides, the disarmed reducing end of which can be activated for immediate second step glycosidation in the presence of a more powerful activator AgOTf. As a result of this two-step activation, trans-trans-patterned trisaccharides could be assembled in a highly efficient manner. This result differs from the classic armed-disarmed technique, according to which usually cis-trans-patterned oligosaccharides are generated. PMID:17253751

  4. Total Synthesis of Bryostatin 16 via Atom Economical and Chemoselective Approaches

    PubMed Central

    Trost, Barry M.; Dong, Guangbin

    2009-01-01

    Atom economy1 and chemoselectivity2 constitute two of the major challenges for enhancement of synthetic efficiency. The syntheses of complex natural products constitute the most demanding arena for exploration of such principles. The combination of extraordinary promising biological activity and the structural complexity of the bryostatins with the benchmark provided by earlier syntheses of some members make them an excellent target for such studies. Herein, we report a concise total synthesis of bryostatin 16 (1). Bryostatin 16 was chosen as the specific synthetic target, most critically because bryostatin 16 could potentially act as a pivotal parent structure to allow access to almost all other bryostatins. Moreover, its synthesis could provide an essential chemical probe by enabling facile analogue syntheses with variations in most parts of the structure, to allow fine-tuning of the biological functions. Application of atom economical and chemoselective reactions under development in these laboratories provides ready access to polyhydropyrans, common structural features of numerous polyacetate-polypropionate derived natural products. Most notably, our strategy of employing the combination of two transition metal catalysts (palladium and gold) demonstrates a new chemoselective and atom-economical macrocyclization reaction between two different alkynes and subsequent formation of the C-ring dihydropyran in the context of a complex natural product synthesis. PMID:19037312

  5. Total synthesis of bryostatin 16 using atom-economical and chemoselective approaches.

    PubMed

    Trost, Barry M; Dong, Guangbin

    2008-11-27

    Of the concepts used to improve the efficiency of organic syntheses, two have been especially effective: atom economy (the use of routes in which most of the atoms present in the reactants also end up in the product) and chemoselectivity (the use of reactions that take place only at desired positions in a molecule). Synthesis of complex natural products is the most demanding arena in which to explore such principles. The bryostatin family of compounds are especially interesting targets, because they combine structural complexity with promising biological activity. Furthermore, synthetic routes to some bryostatins have already been reported, providing a benchmark against which new syntheses can be measured. Here we report a concise total synthesis of bryostatin 16 (1), a parent structure from which almost all other bryostatins could in principle be accessed. Application of atom-economical and chemoselective reactions currently under development provides ready access to polyhydropyran motifs in the molecule, which are common structural features of many other natural products. The most notable transformations are two transition-metal-catalysed reactions. The first is a palladium-catalysed reaction of two different alkynes to form a large ring. The product of this step is then converted into a dihydropyran (the 'C ring' of bryostatins) in the second key reaction, which is catalysed by a gold compound. Analogues of bryostatin that do not exist in nature could be readily made by following this route, which might allow the biological activity of bryostatins to be fine-tuned. PMID:19037312

  6. 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

  7. Highly efficient and chemoselective ?-iodination of acrylate esters through Morita-Baylis-Hillman-type chemistry.

    PubMed

    Pace, Vittorio; Vilkauskait?, Gyt?; Ša?kus, Algirdas; Holzer, Wolfgang

    2013-02-21

    The chemoselective ?-iodination of various simple and multi-functionalised acrylic esters is efficiently accomplished by a Morita-Baylis-Hillman protocol involving the use of N-iodophthalimide, 3-quinuclidinol and KF-Celite in acetonitrile. No degradation of the obtained compounds was observed under the optimized conditions thus, furnishing ?-iodoacrylates suitable for organometallic reactions (i.e. Nozaki-Kishi-Hiyama type coupling). PMID:23303274

  8. Transfer hydrogenation using recyclable polyurea-encapsulated palladium: efficient and chemoselective reduction of aryl ketones.

    PubMed

    Yu, Jin-Quan; Wu, Hai-Chen; Ramarao, Chandrashekar; Spencer, Jonathan B; Ley, Steven V

    2003-03-21

    A robust and recyclable palladium catalyst [Pd0EnCat] has been prepared by ligand exchange of polyurea-encapsulated palladium(II) acetate with formic acid, resulting in deposition of Pd(0) in the support material; Pd0EnCat is shown to be a highly efficient transfer hydrogenation catalyst for chemoselective reduction of a wide range of aryl ketones to benzyl alcohols. PMID:12703769

  9. 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).

  10. 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).

  11. 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).

  12. 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).

  13. 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).

  14. 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).

  15. 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).

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

    PubMed

    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

    2012-01-01

    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 hematopoietic stem cells. 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 myelosuppressive 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 extrahematopoietic tissues in HPRT wild-type mice, while hematopoietic stem cells deficient in HPRT activity were highly resistant to its cytotoxic effects. Combined 6TG conditioning and post-transplantation 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 for both myelosuppressive 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

  17. 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

  18. 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

  19. Chemoselective approaches to glycoprotein assembly

    SciTech Connect

    Hang, Howard C.; Bertozzi, Carolyn R.

    2001-02-23

    Oligosaccharides on proteins and lipids play central roles in human health and disease. The molecular analysis of glycoconjugate function has benefited tremendously from new methods for their chemical synthesis, which provides homogeneous material not attainable from biosynthetic systems. Still, glycoconjugate synthesis requires the manipulation of multiple stereocenters and protecting groups and remains the domain of a few expert laboratories around the world. This account summarizes chemoselective approaches for assembling homogeneous glycoconjugates that attempt to reduce the barriers to their synthesis. The objective of these methods is to make glycoconjugate synthesis accessible to a broader community, thereby accelerating progress in glycobiology.

  20. Palladium-catalyzed chemoselective synthesis of indane-1,3-dione derivatives via tert-butyl isocyanide insertion.

    PubMed

    Duan, Huaqing; Chen, Zhong; Han, Li; Feng, Yulin; Zhu, Yongming; Yang, Shilin

    2015-06-10

    A simple and efficient strategy for the synthesis of indane-1,3-dione derivatives through a palladium(0)-catalyzed reaction incorporating tert-butyl isocyanide has been developed. In addition, by applying this protocol as the key step, indenopyrazole derivatives can be easily synthesized in high yields in a one-pot procedure. This methodology is tolerant of a wide range of substrates and applicable to library synthesis. PMID:26007325

  1. Synthesis of tetraarylpyridines by chemo-selective Suzuki-Miyaura reactions of 3,5-dibromo-2,6-dichloropyridine.

    PubMed

    Reimann, Sebastian; Parpart, Silvio; Ehlers, Peter; Sharif, Muhammad; Spannenberg, Anke; Langer, Peter

    2015-06-10

    Chemoselective Suzuki-Miyaura reactions on 3,5-dibromo-2,6-dichloropyridine were studied. The optimized reaction conditions allow for the facile access of 3-aryl- and 3,5-diarylpyridines in good yields. Suzuki-Miyaura reactions of the selectively synthesized 2,6-dichloro-3,5-diarylpyridines gave the corresponding 2,3,5,6-tetraarylpyridines, containing two different aryl moieties. PMID:26014108

  2. Chemoselective hydrosilylation of hydroxyketones.

    PubMed

    Lage, Marta L; Bader, Scott J; Sa-Ei, Kanicha; Montgomery, John

    2013-07-01

    A chemoselective method for the hydrosilylation of ketones has been developed, using the combination of triphenylsilane and a catalyst prepared from Ni(COD)2 and the simple N-heterocyclic carbene IMes. The most notable feature of this method is that free hydroxyls are largely unaffected, thus providing a simple one-step procedure for the conversion of hydroxyketones to mono-protected diols, wherein the protecting group is exclusively installed on the ketone-derived hydroxyl. The process is typically high yielding with both simple ketones and more complex hydroxyketone substrates. PMID:23997314

  3. Remodelling glycoforms on proteins and cells by chemoselective ligation

    SciTech Connect

    Bertozzi, C.R. [Univ. of California, Berkeley, CA (United States); [Lawrence Berkeley National Lab., CA (United States)

    1997-12-31

    The chemoselective ligation strategy has found tremendous success in the synthesis of macromolecular protein conjugates. At the heart of this approach is the introduction of mutually and uniquely reactive functional groups onto unprotected fragments and the coupling of these fragments in an aqueous environment. We have extended the principle of chemoselective ligation to the generation of glycoproteins and cells with tailor-made glycoforms. New enzymatic and biosynthetic methods for introducing uniquely reactive functional groups onto protein-bound oligosaccharides will be presented, along with applications to glycoform engineering.

  4. Chemoselective CaO-mediated acylation of alcohols and amines in 2-methyltetrahydrofuran.

    PubMed

    Pace, Vittorio; Hoyos, Pilar; Alcántara, Andrés R; Holzer, Wolfgang

    2013-05-01

    Calcium oxide is proposed as an innocuous acid scavenger for the chemoselective synthesis of amide- and ester-type compounds. Although these molecules have wide spread applications in organic and pharmaceutical chemistry, and a large number of routes have been designed for their synthesis, the development of more efficient and environmentally friendly acylation strategies remains an ongoing challenge. The use of CaO allows for the stoichiometric acylation of primary alcohols in the presence of phenols or tertiary alcohols; amines can also be subjected to acylation reactions in the presence of hydroxyl groups. Chirality is obtained through acylation if the starting material is an optically pure alcohol or if a chiral acylating agent is used. Furthermore, the use of 2-methyltetrahydrofuran (2-MeTHF), a more ecofriendly solvent, leads to maximized yields. This protocol is successfully applied to the synthesis of an interesting N-aryloxazolidin-2-one intermediate for the preparation of linezolid-type compounds. PMID:23532956

  5. Chemoselective hydrolysis of tert-butyl esters in acetonitrile using molecular iodine as a mild and efficient catalyst

    Microsoft Academic Search

    J. S. Yadav; E. Balanarsaiah; S. Raghavendra; M. Satyanarayana

    2006-01-01

    A simple, mild and efficient method for the hydrolysis of tert-butyl esters using molecular iodine as a catalyst is described. Acid labile protecting groups, such as N-Boc, OBn, OAc and double bonds, are compatible under the reaction conditions.

  6. Copper nitrate\\/acetic acid as an efficient synergistic catalytic system for the chemoselective tetrahydropyranylation of alcohols and phenols

    Microsoft Academic Search

    Min Wang; Zhi-Guo Song; Hong Gong; Heng Jiang

    2009-01-01

    \\u000a Abstract  Tetrahydropyranylation of alcohols and phenols was accomplished successfully using copper nitrate and acetic acid as a synergistic\\u000a catalyst at room temperature under solvent-free condition. Compared with other synergistic catalytic systems, copper nitrate\\/acetic\\u000a acid proved to be the most efficient. Both alcohols (primary, secondary, tertiary, benzylic, cyclic, allyl, cinnamyl, and\\u000a furyl) and phenols reacted smoothly in high yields.\\u000a \\u000a \\u000a \\u000a Graphical abstract  

  7. Micelles catalyzed chemoselective synthesis 'in water' and biological evaluation of oxygen containing hetero-1,4-naphthoquinones as potential antifungal agents.

    PubMed

    Tandon, Vishnu K; Maurya, Hardesh K; Mishra, Nripendra N; Shukla, Praveen K

    2011-11-01

    Various oxygen containing 1,4-naphthoquinone derivatives have been synthesized chemoselectively by an economical, viable green methodology approach using water as solvent with or without surfactants such as Triton X-100, SDS, LD (laundry detergent), and TBAB, a phase transfer catalyst and evaluated for their in vitro antifungal and antibacterial activity. The antifungal profile of 3, 4a, 4b, and 6 indicated that compounds 3a, 3b, 4b, 6a, and 6c have potent antifungal activity compared to clinically prevalent antifungal drugs Fluconazole and Amphotericin-B against Sporothrix schenckii, Trichophyton mentagraphytes, and Candida parapsilosis and compound 3b has been found to be a lead antifungal agent for further study. PMID:21930375

  8. Development of highly chemoselective bulky zincate complex, tBu4ZnLi2: design, structure, and practical applications in small-/macromolecular synthesis.

    PubMed

    Furuyama, Taniyuki; Yonehara, Mitsuhiro; Arimoto, Sho; Kobayashi, Minoru; Matsumoto, Yotaro; Uchiyama, Masanobu

    2008-01-01

    We present full details of the unique reactivities of the newly developed dianion-type bulky zincate, dilithium tetra-tert-butylzincate (tBu(4)ZnLi(2)). With this reagent, halogen-zinc exchange reaction of variously functionalized haloaromatics and anionic polymerization of N-isopropylacrylamide (NIPAm)/styrene with excellent chemoselectivity were realized. Halogen-zinc exchange reaction followed by electrophilic trapping with propargyl bromide provided a convenient route to functionalized phenylallenes, particularly those with electrophilic functional groups (such as cyano, amide and halogens). Spectral and computational studies of the structure in the gas and liquid phases indicated extraordinary stabilization of this dianion-type zincate by its bulky ligands. PMID:18816554

  9. Critical evaluation and rate constants of chemoselective ligation reactions for stoichiometric conjugations in water.

    PubMed

    Saito, Fumito; Noda, Hidetoshi; Bode, Jeffrey W

    2015-04-17

    Chemoselective ligation reactions have contributed immensely to the development of organic synthesis and chemical biology. However, the ligation of stoichiometric amounts of large molecules for applications such as protein-protein conjugates is still challenging. Conjugation reactions need to be fast enough to proceed under dilute conditions and chemoselective in the presence of unprotected functional groups; the starting materials and products must be stable under the reaction conditions. To compare known ligation reactions for their suitability under these conditions, we determined the second-order rate constants of ligation reactions using peptide substrates with unprotected functional groups. The reaction conditions, the chemoselectivity of the reactions, and the stability of the starting materials and products were carefully evaluated. In some cases, the stability could be improved by modifying the substrate structure. These data obtained under the ligation conditions provide a useful guide to choose an appropriate ligation reaction for synthesis of large molecules by covalent ligation reactions of unprotected substrates in water. PMID:25572124

  10. Direct C-2 arylation of 7-azaindoles: chemoselective access to multiarylated derivatives.

    PubMed

    Kannaboina, Prakash; Anilkumar, K; Aravinda, S; Vishwakarma, Ram A; Das, Parthasarathi

    2013-11-15

    Pd-catalyzed direct C-H arylation of N-methyl-7-azaindole at the C-2 position by diverse arylboronic acids was achieved at room temperature. The method is general and was applied in chemoselective synthesis of multiarylated 7-azaindole derivatives bearing three different aryl groups at the 2, 3, and 5 positions. PMID:24171392

  11. A mild and highly convenient chemoselective alkylation of thiols using Cs 2CO 3–TBAI

    Microsoft Academic Search

    Ralph Nicholas Salvatore; Robert A. Smith; Adam K. Nischwitz; Terrence Gavin

    2005-01-01

    A mild and improved method for the synthesis of thioethers has been developed. In the presence of cesium carbonate, tetrabutylammonium iodide, and DMF, various alkyl and aryl thiols underwent S-alkylation to afford structurally diverse sulfides in high yield. Unprotected mercaptoalcohols and thioamines reacted chemoselectively at the sulfur moiety exclusively. An example of a one-pot, solid-phase synthesis of a thioether is

  12. Chemoselective reduction of aldehydes by ruthenium trichloride and resin-bound formates

    PubMed Central

    Mandal, Bablee; Das, Sajal; Das, Pralay; Nanda, Ashis K

    2008-01-01

    Summary A simple, chemoselective transfer hydrogenation of aryl aldehydes with the aid of Amberlite® resin formate (ARF), a stable H-donor, in the presence of catalytic ruthenium trichloride is described. Aromatic aldehydes and 1,2-diketones are reduced efficiently and selectively, while aryl ketones remain unchanged. Several other potentially reducible groups attached to the aromatic moiety are unaffected. PMID:19190744

  13. Palladium-catalyzed chemoselective decarboxylative ortho acylation of benzoic acids with ?-oxocarboxylic acids.

    PubMed

    Miao, Jinmin; Ge, Haibo

    2013-06-21

    Palladium-catalyzed chemoselective decarboxylative cross coupling of benzoic acids with ?-oxocarboxylic acids was realized via an arene sp(2) C-H functionalization process. This work represents the first example of transition-metal-catalyzed cross-coupling reactions with two acids acting in different roles. The synthetic utility of this method was confirmed by the synthesis of pitofenone, an antispasmodic used in the combined drug Spasmalgon. PMID:23721458

  14. Efficient Synthesis of Feature Models Nele Andersen

    E-print Network

    Czarnecki, Krzysztof

    - clude an e-commerce platform or not. The solution space model explains how the problem space decisions affect the realization--for example, how the e-commerce platform is woven into the implementationEfficient Synthesis of Feature Models Nele Andersen Krzysztof Czarnecki Steven She Andrzej W

  15. Chemoselective addition of isocyanides to N-tert-butanesulfinimines.

    PubMed

    Janssen, Guido V; Janssen, Elwin; Vande Velde, Christophe M L; Ehlers, Andreas W; Slootweg, J Chris; Ruijter, Eelco; Lammertsma, Koop; Orru, Romano V A

    2014-10-01

    The reaction of isocyanides with N-tert-butanesulfinimines shows remarkable chemoselectivity. ?-Sulfinylamino isocyanides are formed exclusively with aromatic sulfinimines, while ?-sulfeneimino acetamides result when using aliphatic derivatives. A mechanism is suggested for the latter transformation, together with an explanation for the observed selectivity. Finally, a scope study is presented for this remarkably chemoselective reaction. PMID:25229182

  16. 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

  17. 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

  18. Efficient Synthesis and Properties of Novel Near-Infrared Electrochromic

    E-print Network

    Wan, Xin-hua

    Efficient Synthesis and Properties of Novel Near-Infrared Electrochromic Anthraquinone Imides@pku.edu.cn Received December 13, 2007 ABSTRACT An efficient synthesis of novel near-infrared electrochromic 6 are electrochromic and absorb intensely in the near-infrared range of 700-1600 nm upon electrochemical reduction

  19. Efficient BDD Algorithms for FSM Synthesis and Verification

    Microsoft Academic Search

    Rajeev K. Ranjan; Adnan Aziz; Robert K. Brayton; Bernard Plessier; Carl Pixley

    1995-01-01

    We describe a set of BDD based algorithms for efficient FSM synthesis and verification. We establish that the core compu- tation in both synthesis and verification is forming the image and pre-image of sets of states under the transition relatio n characterizing the design. To make these steps as efficient as possible, we address BDD variable ordering, use of parti-

  20. 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.

  1. One-Pot Synthesis and Applications of N-Heteroaryl Iodonium Salts

    PubMed Central

    Bielawski, Marcin; Malmgren, Joel; Pardo, Leticia M; Wikmark, Ylva; Olofsson, Berit

    2014-01-01

    An efficient one-pot synthesis of N-heteroaryl iodonium triflates from the corresponding N-heteroaryl iodide and arene has been developed. The reaction conditions resemble our previous one-pot syntheses, with suitable modifications to allow N-heteroaryl groups. The reaction time is only 30?min, and no anion exchange is required. The obtained iodonium salts were isolated in a protonated form, these salts can either be employed directly in applications or be deprotonated prior to use. The aryl groups were chosen to induce chemoselective transfer of the heteroaryl moiety to various nucleophiles. The reactivity and chemoselectivity of these iodonium salts were demonstrated by selectively introducing a pyridyl moiety onto both oxygen and carbon nucleophiles in good yields. PMID:24688890

  2. Chemoselective silicification of synthetic peptides and polyamines

    PubMed Central

    Abacilar, Maryna; Daus, Fabian

    2015-01-01

    Summary 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 1H 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. Overturning Established Chemoselectivities: Selective Reduction of Arenes over Malonates and Cyanoacetates by Photoactivated Organic Electron Donors

    PubMed Central

    2013-01-01

    The prevalence of metal-based reducing reagents, including metals, metal complexes, and metal salts, has produced an empirical order of reactivity that governs our approach to chemical synthesis. However, this reactivity may be influenced by stabilization of transition states, intermediates, and products through substrate–metal bonding. This article reports that in the absence of such stabilizing interactions, established chemoselectivities can be overthrown. Thus, photoactivation of the recently developed neutral organic superelectron donor 5 selectively reduces alkyl-substituted benzene rings in the presence of activated esters and nitriles, in direct contrast to metal-based reductions, opening a new perspective on reactivity. The altered outcomes arising from the organic electron donors are attributed to selective interactions between the neutral organic donors and the arene rings of the substrates. PMID:23859883

  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 ...

  5. Efficient synthesis of 2-(thiocyanomethylthio)benzothiazole

    Microsoft Academic Search

    Lakshmi Muthusubramanian; V. S. Sundara Rao; Rajat B Mitra

    2001-01-01

    In the leather industry phenolic-based fungicides have been in use until recently. As a result of legislation limiting the content of pentachlorophenol (PCP) in leather, non-chlorophenolics based on 2-(thiocyanomethylthio)benzothiazole (TCMTB) have become more widely used in the leather industry for controlling the growth of fungi and sulphate-reducing bacteria. This paper reports a clean and simple method of synthesis of TCMTB,

  6. Dynamic 3D cell culture via a chemoselective photoactuated ligand.

    PubMed

    Westcott, Nathan P; Luo, Wei; Goldstein, Jeffrey; Yousaf, Muhammad N

    2014-09-01

    A new strategy to create a dynamic scaffold for three-dimensional (3D) cell experiments based on a photo-activated cell adhesive peptide ligand is described. After polymerization, the inert matrix becomes cell adhesive by chemoselective modification through the conjugation of oxyamine-terminated ligands. Furthermore, spatial and temporal control of cell culture within the 3D matrix was achieved by the use of a biospecific photoprotected peptide and visualized by confocal microscopy. PMID:25280846

  7. Chemoselective Polymerization Control: From Mixed-Monomer Feedstock to Copolymers**

    PubMed Central

    Romain, Charles; Williams, Charlotte K

    2014-01-01

    A novel chemoselective polymerization control yields predictable (co)polymer compositions from a mixture of monomers. Using a dizinc catalyst and a mixture of caprolactone, cyclohexene oxide, and carbon dioxide enables the selective preparation of either polyesters or polycarbonates or copoly(ester-carbonates). The selectivity depends on the nature of the zinc–oxygen functionality at the growing polymer chain end, and can be controlled by the addition of exogeneous switch reagents. PMID:24453135

  8. Efficient Scheduling of Conditional Behaviors for High-Level Synthesis

    E-print Network

    Paris-Sud XI, Université de

    and time-to-market constraints get tighter there is strong motivation for high-level synthesis (HLS). HLS of a mixed nature. In the past efficient tools for the former type have been developed but so far HLS the development of the CODESIS HLS tool for further experimentation. Categories and Subject Descriptors: J.6

  9. Efficient Synthesis of Trisimidazole and Glutaric Acid Bearing Porphyrins

    E-print Network

    Dinolfo, Peter H.

    Efficient Synthesis of Trisimidazole and Glutaric Acid Bearing Porphyrins: Ligands for Active and 1H NMR chemical shifts under the ring current effect of the porphyrin. Biological denitrification a porphyrin covalently linked to a tetradentate chelate (TMPA, tris(2-pyridylmethyl)amine).5 In these models

  10. Efficient Synthesis of 1-Sulfonyl-1,2,3-triazoles

    PubMed Central

    Raushel, Jessica; Fokin, Valery V.

    2010-01-01

    An efficient room temperature method for the synthesis of 1-sulfonyl-1,2,3-triazoles from in situ generated copper(I) acetylides and sulfonyl azides is described. Copper(I) thiophene-2-carboxylate (CuTC) catalyst produces the title compounds under both non-basic anhydrous and aqueous conditions in good yields. PMID:20931987

  11. An efficient synthesis of valienamine via ring-closing metathesis.

    PubMed

    Chang, Young-Kil; Lee, Bo-Young; Kim, Dong Jun; Lee, Gwan Sun; Jeon, Heung Bae; Kim, Kwan Soo

    2005-04-15

    An efficient synthesis of valienamine is described. Valienamine was synthesized starting from commercially available 2,3,4,6-tetra-O-benzyl-D-glucose in nine steps, using ring-closing metathesis of (4S,5S,6S)-4,5,6-tribenzyloxy-7-(benzyloxymethyl)octa-1,7-dien-3-ol as a key step. PMID:15823000

  12. Desilylative activation of TMSCN in chemoselective Strecker-Ugi type reaction: functional fused imidazoles as building blocks as an entry route to annulated purines.

    PubMed

    Guchhait, Sankar K; Chaudhary, Vikas

    2014-09-14

    A pathway of desilylative activation of TMSCN as a functional isonitrile equivalent, and DABCO-THF as an appropriate system for activation in a chemoselective Strecker-Ugi type reaction, has rendered ethyl glyoxalate and various heterocyclic-2-amidines as feasible substrates, and afforded the successful synthesis of 3-amino-2-carboxyethyl substituted fused imidazoles as useful building blocks. This class of functional scaffold has provided, via construction of the fused pyrimidinone motif, the synthesis of biologically important C8-N9 annulated purines, adenines and their oxo/thio analogs. This new approach is convenient and flexible for the preparation of versatile purine-condensed heterocycles. PMID:25032666

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

    PubMed

    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

  14. Chemoselective Oxidation of Benzyl, Amino, and Propargyl Alcohols to Aldehydes and Ketones under Mild Reaction Conditions.

    PubMed

    Reddy, C B Rajashekar; Reddy, Sabbasani Rajasekhara; Naidu, Shivaji

    2015-04-01

    Catalytic oxidation reactions often suffer from drawbacks such as low yields and poor selectivity. Particularly, selective oxidation of alcohols becomes more difficult when a compound contains more than one oxidizable functional group. In order to deliver a methodology that addresses these issues, herein we report an efficient, aerobic, chemoselective and simplified approach to oxidize a broad range of benzyl and propargyl alcohols containing diverse functional groups to their corresponding aldehydes and ketones in excellent yields under mild reaction conditions. Optimal yields were obtained at room temperature using 1?mmol substrate, 10?mol?% copper(I) iodide, 10?mol?% 4-dimethylaminopyridine (DMAP), and 1?mol?% 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) in acetonitrile, under an oxygen balloon. The catalytic system can be applied even when sensitive and oxidizable groups such as alkynes, amines, and phenols are present; starting materials and products containing such groups were found to be stable under the developed conditions. PMID:25969806

  15. 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

  16. Carboxy-directed asymmetric hydrogenation of ?-alkyl-?-aryl terminal olefins: highly enantioselective and chemoselective access to a chiral benzylmethyl center.

    PubMed

    Yang, Shuang; Zhu, Shou-Fei; Guo, Na; Song, Song; Zhou, Qi-Lin

    2014-04-01

    A carboxy-directed asymmetric hydrogenation of ?-alkyl-?-aryl terminal olefins was developed by using a chiral spiro iridium catalyst, providing a highly efficient approach to the compounds with a chiral benzylmethyl center. The carboxy-directed hydrogenation prohibited the isomerization of the terminal olefins, and realized the chemoselective hydrogenation of various dienes. The concise enantioselective syntheses of (S)-curcudiol and (S)-curcumene were achieved by using this catalytic asymmetric hydrogenation as a key step. PMID:24569889

  17. Efficient synthesis of Au??(SR)?? nanoclusters.

    PubMed

    Liu, Chao; Lin, Jizhi; Shi, Yangwei; Li, Gao

    2015-04-14

    We report a new synthetic protocol of Au99(SPh)42 nanoclusters with moderate efficiency (?15% yield based on HAuCl4), via a combination of the ligand-exchange and "size-focusing" processes. The purity of the as-prepared gold nanoclusters is characterized by matrix-assisted laser desorption ionization mass spectrometry and size exclusion chromatography. PMID:25772552

  18. A Synthesis of Alsmaphorazine B Demonstrates the Chemical Feasibility of a New Biogenetic Hypothesis.

    PubMed

    Hong, Allen Y; Vanderwal, Christopher D

    2015-06-17

    An N-oxide fragmentation/hydroxylamine oxidation/intramolecular 1,3-dipolar cycloaddition cascade efficiently converted an oxidized congener of akuammicine into the complex, hexacyclic architecture of the alsmaphorazine alkaloids. This dramatic structural change shows the chemical feasibility of our novel proposal for alsmaphorazine biogenesis. Critical to these endeavors was a marked improvement in our previously reported Zincke aldehyde cycloaddition approach to indole alkaloids, which permitted the gram-scale synthesis of akuammicine. The chemoselective oxidations of akuammicine leading up to the key rearrangement also generated several biogenetically related alkaloids of the alstolucine and alpneumine families. PMID:26034815

  19. 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 dissociation. These results demonstrate the efficient conversion of methane to synthesis gas, CO+2H2 fuel production Fischer-Tropsch or methanol synthesis . Moreover, under the reaction conditions

  20. Diazo Groups Endure Metabolism and Enable Chemoselectivity in Cellulo

    PubMed Central

    2015-01-01

    We introduce a stabilized diazo group as a reporter for chemical biology. ManDiaz, which is a diazo derivative of N-acetylmannosamine, is found to endure cellular metabolism and label the surface of a mammalian cell. There its diazo group can undergo a 1,3-dipolar cycloaddition with a strained alkyne, providing a signal comparable to that from the azido congener, ManNAz. The chemoselectivity of diazo and alkynyl groups enables dual labeling of cells that is not possible with azido and alkynyl groups. Thus, the diazo group, which is approximately half the size of an azido group, provides unique opportunities for orthogonal labeling of cellular components. PMID:25658416

  1. Chemoselective surface immobilization of proteins through a cleavable peptide.

    PubMed

    Dettin, Monica; Muncan, Natali; Bugatti, Antonella; Grezzo, Francesca; Danesin, Roberta; Rusnati, Marco

    2011-09-21

    Surface immobilization of biomolecules is a fundamental step in several experimental techniques such as surface plasmon resonance analysis and microarrays. Oxime ligation allows reaching chemoselective protein immobilization with the retention of native-like conformation by proteins. Beside the need for chemoselective ligation of molecules to surface/particle, equally important is the controlled release of the immobilized molecules, even after a specific binding event. For this purpose, we have designed and assessed in an SPR experiment a peptide linker able to (i) anchor a given protein (enzymes, receptors, or antibodies) to a surface in a precise orientation and (ii) release the immobilized protein after selective enzymatic cleavage. These results open up the possibility to anchor to a surface a protein probe leaving bioactive sites free for interaction with substrates, ligands, antigens, or drugs and successively remove the probe-ligand complex by enzymatic cleavage. This peptide linker can be considered both an improvement of SPR analysis for macromolecular interaction and a novel strategy for drug delivery and biomaterial developments. PMID:21819154

  2. Energy efficiency in nanoscale synthesis using nanosecond plasmas

    PubMed Central

    Pai, David Z.; (Ken) Ostrikov, Kostya; Kumar, Shailesh; Lacoste, Deanna A.; Levchenko, Igor; Laux, Christophe O.

    2013-01-01

    We report a nanoscale synthesis technique using nanosecond-duration plasma discharges. Voltage pulses 12.5?kV in amplitude and 40?ns in duration were applied repetitively at 30?kHz across molybdenum electrodes in open ambient air, generating a nanosecond spark discharge that synthesized well-defined MoO3 nanoscale architectures (i.e. flakes, dots, walls, porous networks) upon polyamide and copper substrates. No nitrides were formed. The energy cost was as low as 75?eV per atom incorporated into a nanostructure, suggesting a dramatic reduction compared to other techniques using atmospheric pressure plasmas. These findings show that highly efficient synthesis at atmospheric pressure without catalysts or external substrate heating can be achieved in a simple fashion using nanosecond discharges. PMID:23386976

  3. Enantioselective synthesis of a dual orexin receptor antagonist.

    PubMed

    Mangion, Ian K; Sherry, Benjamin D; Yin, Jingjun; Fleitz, Fred J

    2012-07-01

    A concise, enantioselective synthesis of the potent dual orexin inhibitor suvorexant (1) is reported. Key features of the synthesis include a mild copper-catalyzed amination, a highly chemoselective conjugate addition, and a tandem enantioselective transamination/seven-membered ring annulation. The synthesis requires inexpensive starting materials and only four linear steps for completion. PMID:22725839

  4. Introducing deep eutectic solvents to polar organometallic chemistry: chemoselective addition of organolithium and Grignard reagents to ketones in air.

    PubMed

    Vidal, Cristian; García-Álvarez, Joaquín; Hernán-Gómez, Alberto; Kennedy, Alan R; Hevia, Eva

    2014-06-01

    Despite their enormous synthetic relevance, the use of polar organolithium and Grignard reagents is greatly limited by their requirements of low temperatures in order to control their reactivity as well as the need of dry organic solvents and inert atmosphere protocols to avoid their fast decomposition. Breaking new ground on the applications of these commodity organometallics in synthesis under more environmentally friendly conditions, this work introduces deep eutetic solvents (DESs) as a green alternative media to carry out chemoselective additions of ketones in air at room temperature. Comparing their reactivities in DES with those observed in pure water suggest that a kinetic activation of the alkylating reagents is taking place, favoring nucleophilic addition over the competitive hydrolysis, which can be rationalized through formation of halide-rich magnesiate or lithiate species. PMID:24771680

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

    PubMed

    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

  6. Chemoselective Esterification of Phenolic Acids in the Presence of Sodium Bicarbonate in Ionic Liquids

    Microsoft Academic Search

    Ambika; Pradeep Pratap Singh; S. M. S. Chauhan

    2008-01-01

    Chemoselective esterification of phenolic acids with dialkyl sulphates or alkyl halides in the presence of sodium bicarbonate in 1,3?dialkylimidazolium ionic liquids is reported in excellent yields and less reaction time as compared to organic solvents.

  7. Transforming nonselective into chemoselective metal catalysts for the hydrogenation of substituted nitroaromatics.

    PubMed

    Corma, Avelino; Serna, Pedro; Concepción, Patricia; Calvino, José Juan

    2008-07-01

    It is generally accepted that good hydrogenation noble and nonnoble metal catalysts such as Pt, Ru, or Ni are not chemoselective for hydrogenation of nitro groups in substituted aromatic molecules. We have found that it is possible to transform nonchemoselective into highly chemoselective metal catalysts by controlling the coordination of metal surface atoms while introducing a cooperative effect between the metal and a properly selected support. Thus, highly chemoselective and general hydrogenation Pt, Ru, and Ni catalysts can be prepared by generating nanosized crystals of the metals on the surface of a TiO 2 support and decorating the exposed (111) and (100) crystal faces by means of a simple catalyst activation procedure. By doing this, it has been possible to change the relative rate for hydrogenating competitive groups present in the molecule by almost 2 orders of magnitude, increasing the chemoselectivity from less than 1% to more than 95%. PMID:18597431

  8. Kinetic study of chemoselective acylation of amino-alditol by immobilized lipase in organic solvent: effect of substrate ionization.

    PubMed

    Maugard, T; Remaud-Simeon, M; Monsan, P

    1998-09-01

    The kinetics of the lipase-catalyzed synthesis of oleoyl-N-methylglucamide and 6-O-oleoyl-N-methylglucamine in organic systems were investigated. We have shown that in apolar media, the ionic state of substrates and the ionic state of enzyme microenvironment play an important role in immobilized Candida antarctica lipase activity and chemoselectivity of the reaction. In order to define the optimal conditions of the reaction, to obtain the highest initial rate for amide formation, the influence of acid/N-methylglucamine molar ratio is studied. This ratio determines the protonation states of substrates and of ionizable groups of catalytic site, on which the enzyme activity is dependent. To confirm our hypothesis, we have added to the medium a non-reactive base which is not a substrate of the enzyme. We observed that when the acid/base ratio is higher than 1, the initial rate of ester synthesis increases whereas that of amide synthesis decreases. On the opposite, when the acid/base ratio is lower than 1, the initial rate of amide synthesis becomes preponderant. PMID:9748563

  9. Efficient Solid-Phase Synthesis of Peptide-Substituted Alkanethiols for the

    E-print Network

    Mrksich, Milan

    Efficient Solid-Phase Synthesis of Peptide-Substituted Alkanethiols for the Preparation describe a rapid and efficient method, based on solid-phase peptide synthesis, for preparing alkanethiols short peptide ligands are an important class of model substrates for studies of the interactions

  10. Exploiting Orthogonally Reactive Functionality: Synthesis and Stereochemical Assignment of (?)-Ushikulide A

    PubMed Central

    Trost, Barry M.; O’Boyle, Brendan M.

    2009-01-01

    In spite of the tremendous advances in modern spectroscopic methods, organic synthesis continues to play a pivotal role in elucidating the full structures of complex natural products. This method has the advantage that even in the absence of a firm structural assignment, a combination of logic and spectroscopic comparison can arrive at the correct structure. Herein, we report execution of this strategy with respect to ushikulide A, a newly isolated and previously stereochemically-undefined member of the oligomycin-rutamycin family. To maximize synthetic efficiency, we envisioned chemoselective manipulation of orthogonally reactive functional groups, notably alkenes and alkynes as surrogates for certain carbonyl and hydroxyl functionalities. This approach has the dual effect of minimizing the number of steps and protecting groups required for our synthetic route. This strategy culminated in the efficient synthesis and stereochemical assignment of ushikulide A. PMID:18989964

  11. Engineering the elongation factor Tu for efficient selenoprotein synthesis

    PubMed Central

    Haruna, Ken-ichi; Alkazemi, Muhammad H.; Liu, Yuchen; Söll, Dieter; Englert, Markus

    2014-01-01

    Selenocysteine (Sec) is naturally co-translationally incorporated into proteins by recoding the UGA opal codon with a specialized elongation factor (SelB in bacteria) and an RNA structural signal (SECIS element). We have recently developed a SECIS-free selenoprotein synthesis system that site-specifically—using the UAG amber codon—inserts Sec depending on the elongation factor Tu (EF-Tu). Here, we describe the engineering of EF-Tu for improved selenoprotein synthesis. A Sec-specific selection system was established by expression of human protein O6-alkylguanine-DNA alkyltransferase (hAGT), in which the active site cysteine codon has been replaced by the UAG amber codon. The formed hAGT selenoprotein repairs the DNA damage caused by the methylating agent N-methyl-N?-nitro-N-nitrosoguanidine, and thereby enables Escherichia coli to grow in the presence of this mutagen. An EF-Tu library was created in which codons specifying the amino acid binding pocket were randomized. Selection was carried out for enhanced Sec incorporation into hAGT; the resulting EF-Tu variants contained highly conserved amino acid changes within members of the library. The improved UTu-system with EF-Sel1 raises the efficiency of UAG-specific Sec incorporation to >90%, and also doubles the yield of selenoprotein production. PMID:25064855

  12. Sulfated zirconia as an efficient catalyst for organic synthesis and transformation reactions

    Microsoft Academic Search

    Benjaram M. Reddy; Pavani M. Sreekanth; Pandian Lakshmanan

    2005-01-01

    The efficacy of sulfated zirconia catalyst was investigated towards various acid-catalyzed organic syntheses and transformation reactions in the liquid phase. The SO42?\\/ZrO2 efficiently catalyzes synthesis of 1,5-benzodiazepine derivatives, electrophilic substitution of indoles with aldehydes to afford the corresponding bis(indolyl)methanes, synthesis of 3,4-dihydropyrimidinones, synthesis of diaryl sulfoxides, and tetrahydropyranylation of alcohols and phenols. Various advantages associated with these protocols include, simple

  13. A concise enantioselective synthesis of (+)-febrifugine

    Microsoft Academic Search

    Lourdusamy Emmanuvel; Dayanand A. Kamble; Arumugam Sudalai

    2009-01-01

    A short enantioselective synthesis of (+)-febrifugine, a potent antimalarial alkaloid, has been described based on the regioselective asymmetric dihydroxylation of a 1,4-dienic ester as the key step. The strategy also involves chemoselective [3,3]-sigmatropic rearrangement of 1,5-hexadiene-3-ol and intramolecular lactamization of azidolactone for the construction of piperidine core.

  14. Synthesis of Application-Specific Highly Efficient Multi-Mode Cores for

    E-print Network

    Bhunia, Swarup

    with efficient scheduling and allocation is used to automatically synthesize a Multi-Mode system from its synthesis, synthesis, reconfigurable system 1. INTRODUCTION State-of-the-art multimedia, communications parameters such as power consumption, area, processing speed, and reconfigurability of the system

  15. Chemoselective per-O-trimethylsilylation and homogeneous N-functionalisation of amino sugars.

    PubMed

    Joseph, A Abragam; Dhurandhare, Vijay M; Chang, Chun-Wei; Verma, Ved Prakash; Mishra, Girija Prasad; Ku, Chiao-Chu; Lin, Chun-Cheng; Wang, Cheng-Chung

    2015-01-01

    A highly efficient CH3CN-promoted hexamethyldisilazane per-O-trimethylsilylation of amino sugars was developed. Its applications in homogenous N-functionalisation and a concise synthesis of glucosamine 6-phosphate are described. PMID:25384128

  16. [Development of efficient methods for synthesis of nitrogen-containing compounds using carbamates, acylhydrazines, and ammonia].

    PubMed

    Sugiura, Masaharu

    2006-12-01

    For the efficient synthesis of divergent nitrogen-containing compounds of pharmaceutical and agricultural importance, the development of efficient, complementary, and new synthetic methodologies is essential. One of the key subjects is how to introduce nitrogen atoms in to organic molecules. This review summaries our recent efforts on this issue, focusing on the use of carbamates, acylhydrazines, and ammonia as nitrogen sources. PMID:17139157

  17. 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

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

    PubMed

    Kristensen, Tor E

    2015-01-01

    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

  19. 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

  20. 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

  1. High efficiency synthesis of a bioconjugatable near-infrared fluorochrome.

    PubMed

    Pham, Wellington; Lai, Wen-Fu; Weissleder, Ralph; Tung, Ching-Hsuan

    2003-01-01

    Near-infrared (NIR) fluorochromes have become important reporter molecules for many biomedical applications, including FACS sorting, confocal microscopy, and more recently in vivo imaging. While the structures of several stable 800 nm fluorochromes have been published, their synthesis is often complex and there are difficulties in rapidly purifying these compounds in large quantities. Here we report on the synthesis of NIR820, ex/em = 790/820, with excellent physicochemical properties. Importantly, NIR820 is conveniently synthesized in a three-step reaction and can be purified by flash column chromatography rather than by HPLC. NIR820 is chemically stable and can be directly coupled to peptides during the solid-phase synthesis. In addition, NIR820 is also suitable for conjugation to proteins and other affinity molecules in aqueous buffer. PMID:13129411

  2. A Subsystem Synthesis Method for Efficient Vehicle Multibody Dynamics

    Microsoft Academic Search

    Sung-Soo Kim

    2002-01-01

    A subsystem synthesis method has been proposed for dynamicanalysis of a vehicle multibody system that consists of severalsubsystems. In this method, each subsystem can be independently analyzedwith a virtual reference body. For overall vehicle system analysis,subsystems can be synthesized to the chassis with effective inertiamatrix and force vector from the virtual reference body of eachsubsystem. Using this matrix and vector,

  3. Regiocontrol in an intramolecular Schmidt reaction: total synthesis of (+)-aspidospermidine.

    PubMed

    Iyengar, R; Schildknegt, K; Aubé, J

    2000-06-01

    [reaction--see text] A total synthesis of (+)-aspidospermidine (1) is described, featuring an intramolecular Schmidt reaction as the key step. The effects of stereochemistry and protecting group status on the regio- and chemoselectivity of this reaction were examined. PMID:10841495

  4. Efficient synthesis of deuterium labeled hydroxyzine and aripiprazole.

    PubMed

    Vohra, Mohit; Sandbhor, Mahendra; Wozniak, Andrew

    2015-06-15

    Hydroxyzine and aripiprazole are active pharmaceutical ingredients that have been largely acknowledged for their antipsychotic properties. Deuterium labeled isotopes of hydroxyzine and aripiprazole are internal standards that can aid in the further research of non-isotopic forms via quantification analysis using HPLC-MS/MS. The synthesis of hydroxyzine-d8 was accomplished by coupling piperazine-d8 with 4-chlorobenzhydryl chloride followed by the reaction of the first intermediate with 2-(2-chloroethoxy) ethanol to afford 11.7% of hydroxyzine-d8 with 99.5% purity. The synthesis of aripiprazole-d8 was also achieved in two steps. 1,4-Dibromobutane-d8 reacted with 7-hydroxy-3,4-dihydro-2(1H)-quinolinone. The first intermediate was then coupled with 1-(2, 3-dichlorophenyl)piperazine hydrochloride to produce 33.4% of aripiprazole-d8 with 99.93% purity. PMID:26011470

  5. 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

  6. Solvent-controlled chemoselective palladium-catalyzed oligomerization of tert-butyl acetylene

    Microsoft Academic Search

    Jin-Sheng Cheng; Guo-Feng Wei; Shi-Wen Huang; Jin-Zhao; Huan-Feng Jiang

    2007-01-01

    A solvent-controlled chemoselective palladium-catalyzed oligomerization of tert-butyl acetylene was reported in this paper. The reaction was carried out smoothly in benzene\\/n-BuOH binary solvents system. When benzene, unpolar aprotic solvent, became preponderating in the binary solvents system, a cyclotrimerization process occurred to produce 1,3,5-tri-tert-butylbenzene via a mechanism of three acetylene molecular to insert step by step forming ?-butadienyl-Pd and ?-hexatrienyl-Pd intermediates,

  7. Superior copper promoted bimetallic catalysts for chemoselective hydrogenation of ortho-chloro-nitrobenzene

    Microsoft Academic Search

    Komateedi N. Rao; Benjaram M. Reddy; Sang-Eon Park

    2009-01-01

    In the present study, highly dispersed copper promoted bimetallic nanocomposite oxides with superior catalytic performance for vapor phase chemoselective hydrogenation of ortho-chloro-nitrobenzene were successfully prepared by deposition–precipitation and impregnation methods and characterized using different techniques. XRD and TPR results revealed the presence of small and extremely well dispersed metal oxide particles over the high surface area ceria–silica support. TEM analysis

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

    PubMed Central

    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.

    2014-01-01

    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

  9. Efficient and practical synthesis of both enantiomers of 3-phenylcyclopentanol derivatives

    Microsoft Academic Search

    Yoshiyuki Okumura; Akemi Ando; Rodney William Stevens; Makoto Shimizu

    2002-01-01

    An efficient, multigram scale synthesis of the respective optical isomers of 3-(substituted-phenyl) cyclopentanols was achieved by a lipase-catalyzed transesterification (kinetic resolution) in organic medium. This enzymatic reaction proceeded with great efficiency as measured by chemical yield and enantioselectivity. The racemic cis-alcohol 3 was successfully resolved to yield (1R,3S)-acetate 7 and the corresponding (1S,3R)-alcohol 3. The utility of this procedure was

  10. Partial Update of Active Textures for Efficient Expression Synthesis in Model-Based Coding

    Microsoft Academic Search

    Lijun Yin; Anup Basu

    2000-01-01

    An image-based facial expression synthesis method is presented in this paper for a realistic face animation in model based coding. Differing from the conventional whole texture update method, we propose a partial texture update scheme in active texture areas to reduce the bitrate efficiently. Facial expressions are synthesized using temporal blending and spatial filtering so that a smooth texture fusion

  11. 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.

  12. The effect of substrate structure on the chemoselectivity of Candida1 antarctica lipase B-catalyzed acylation of amino-alcohols2

    E-print Network

    Boyer, Edmond

    1 The effect of substrate structure on the chemoselectivity of Candida1 antarctica lipase B challenge. The current work describes the different15 behavior shown by Candida antarctica lipase B (Novozym antarctica lipase B; Organic solvent;32 Chemoselectivity33 34 hal-00789681,version1-18Feb2013 #12;3 1

  13. Efficient discovery of bioactive scaffolds by activity-directed synthesis.

    PubMed

    Karageorgis, George; Warriner, Stuart; Nelson, Adam

    2014-10-01

    The structures and biological activities of natural products have often provided inspiration in drug discovery. The functional benefits of natural products to the host organism steers the evolution of their biosynthetic pathways. Here, we describe a discovery approach--which we term activity-directed synthesis--in which reactions with alternative outcomes are steered towards functional products. Arrays of catalysed reactions of ?-diazo amides, whose outcome was critically dependent on the specific conditions used, were performed. The products were assayed at increasingly low concentration, with the results informing the design of a subsequent reaction array. Finally, promising reactions were scaled up and, after purification, submicromolar ligands based on two scaffolds with no previous annotated activity against the androgen receptor were discovered. The approach enables the discovery, in tandem, of both bioactive small molecules and associated synthetic routes, analogous to the evolution of biosynthetic pathways to yield natural products. PMID:25242481

  14. 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

  15. Efficient synthesis of dichlorodenafil, an unapproved sildenafil analogue appearing in non-prescription supplements.

    PubMed

    Kim, Jong Yup; Hwang, In Gyun; Oh, Jae Ho; Kang, Il Hyun; Kwon, Sung Won; Kim, Deukjoon

    2013-01-01

    We have developed an efficient synthesis of dichlorodenafil (4), an unapproved sildenafil analogue isolated from dietary supplements. Our sequence employs POCl(3)-mediated chlorination of readily available chloroacetyl compound 7 followed by selective hydrolysis of the chloro-heterocycle function. Our synthesis confirms the structure of the illegal additive, and will provide regulatory agencies with ready access to authentic standard samples of dichlorodenafil (4) to aid in their mission to protect the public from unapproved and potentially harmful erectile dysfunction (ED) drug analogues that are added to herbal and dietary supplements without providing users with appropriate toxicological or pharmacological information. PMID:23649199

  16. Aerobic Dehydrogenation of Cyclohexanone to Cyclohexenone Catalyzed by Pd(DMSO)2(TFA)2: Evidence for Ligand-Controlled Chemoselectivity

    PubMed Central

    Diao, Tianning; Pun, Doris; Stahl, Shannon S.

    2013-01-01

    The dehydrogenation of cyclohexanones affords cyclohexenones or phenols via removal of one or two equivalents of H2, respectively. We recently reported several PdII catalyst systems that effect aerobic dehydrogenation of cyclohexanones with different product selectivities. Pd(DMSO)2(TFA)2 is unique in its high chemoselectivity for the conversion of cyclohexanones to cyclohexenones, without promoting subsequent dehydrogenation of cyclohexenones to phenols. Kinetic and mechanistic studies of these reactions reveal the key role of the dimethylsulfoxide (DMSO) ligand in controlling this chemoselectivity. DMSO has minimal kinetic influence on the rate of Pd(TFA)2-catalyzed dehydrogenation of cyclohexanone to cyclohexenone, while it strongly inhibits the second dehydrogenation step, conversion of cyclohexenone to phenol. These contrasting kinetic effects of DMSO provide the basis for chemoselective formation cyclohexenones. PMID:23662700

  17. 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.

  18. 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.

  19. 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

  20. Highly Efficient Synthesis of Clean Biofuels from Biomass Using FeCuZnAlK Catalyst

    NASA Astrophysics Data System (ADS)

    Qiu, Song-bai; Xu, Yong; Ye, Tong-qi; Gong, Fei-yan; Yang, Zhi; Yamamoto, Mitsuo; Liu, Yong; Li, Quan-xin

    2011-12-01

    Highly efficient synthesis of clean biofuels using the bio-syngas obtained from biomass gasification was performed over Fe1.5Cu1Zn1Al1K0.117 catalyst. The maximum biofuel yield from the bio-syngas reaches about 1.59 kg biofuels/(kgcatal·h) with a contribution of 0.57 kg alcohols/(kgcatal·h) and 1.02 kg liquid hydrocarbons/(kgcatal·h). The alcohol products in the resulting biofuels were dominated by the C2+ alcohols (mainly C2—C6 alcohols) with a content of 73.55%-89.98%. The selectivity of the liquid hydrocarbons (C5+) in the hydrocarbon products ranges from 60.37% to 70.94%. The synthesis biofuels also possess a higher heat value of 40.53-41.49 MJ/kg. The effects of the synthesis conditions, including temperature, pressure, and gas hourly space velocity, on the biofuel synthesis were investigated in detail. The catalyst features were characterized by inductively coupled plasma and atomic emission spectroscopy, X-ray diffraction, temperature programmed reduction, and the N2 adsorption-desorption isotherms measurements. The present biofuel synthesis with a higher biofuel yield and a higher selectivity of liquid hydrocarbons and C2+ alcohols may be a potentially useful route to produce clean biofuels and chemicals from biomass.

  1. Efficient enzymatic synthesis of ampicillin by mutant Alcaligenes faecalis penicillin G acylase.

    PubMed

    Deng, Senwen; Su, Erzheng; Ma, Xiaoqiang; Yang, Shengli; Wei, Dongzhi

    2015-04-10

    Semi-synthetic ?-lactam antibiotics (SSBAs) are one of the most important antibiotic families in the world market. Their enzymatic synthesis can be catalyzed by penicillin G acylases (PGAs). In this study, to improve enzymatic synthesis of ampicillin, site-saturating mutagenesis was performed on three conserved amino acid residues: ?F24, ?R146, and ?F147 of thermo-stable penicillin G acylase from Alcaligenes faecalis (Af PGA). Four mutants ?F24G, ?F24A, ?F24S, and ?F24P were recovered by screening the mutant bank. Kinetic analysis of them showed up to 800-fold increased kcat/Km value for activated acyl donor D-phenylglycine methyl ester (D-PGME). When ?F24G was used for ampicillin synthesis under kinetic control at industrially relevant conditions, 95% of nucleophile 6-aminopenicillanic acid (6-APA) was converted to ampicillin in aqueous medium at room temperature while 12% process time is needed to reach maximum product accumulation at 25% enzyme concentration compared with the wild-type Af PGA. Consequently, process productivity of enzymatic synthesis of ampicillin catalyzed by Af PGA was improved by more than 130 times, which indicated an enzyme viable for efficient SSBAs synthesis. PMID:25681630

  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(C6 F5 )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. Novel solvent-controlled chemoselective palladium\\/copper(II) halide catalyzed oligomerization of tert -butyl acetylene

    Microsoft Academic Search

    Jin-Sheng Cheng; Guo-Feng Wei; Zu-Liang Huang

    2007-01-01

    Solvent-controlled chemoselective palladium-catalyzed oligomerization of tert-butyl acetylene is reported in this paper. The reaction was carried out smoothly in benzene\\/n-BuOH binary solvent system. When unpolar aprotic benzene was the preponderating component in the binary system, a cyclotrimerization\\u000a process occurred to produce 1,3,5-tri-tert-butylbenzene via a mechanism of three acetylene molecules, inserted step by step, forming ?-butadienyl-Pd and ?-hexatrienyl-Pd intermediates. While when

  4. A protecting group-free synthesis of the Colorado potato beetle pheromone.

    PubMed

    Wu, Zhongtao; Jäger, Manuel; Buter, Jeffrey; Minnaard, Adriaan J

    2013-01-01

    A novel synthesis of the aggregation pheromone of the Colorado potato beetle, Leptinotarsa decemlineata, has been developed based on a Sharpless asymmetric epoxidation in combination with a chemoselective alcohol oxidation using catalytic [(neocuproine)PdOAc]2OTf2. Employing this approach, the pheromone was synthesized in 3 steps, 80% yield and 86% ee from geraniol. PMID:24367402

  5. Combinatorial design and synthesis of peptidomimics and small molecules for protein-protein interactions

    E-print Network

    Park, Chihyo

    2007-04-25

    dimerization with 1,5-hexadiyne gave a homodimer as a byproduct. Solidphase synthesis of bivalent turn mimics with fluorescent tags has been demonstrated. The key feature of this synthetic route is that homo- and hetero-dimers can be formed chemoselectively...

  6. Alum: An efficient catalyst for one-pot synthesis of ?-aminophosphonates

    Microsoft Academic Search

    Swapnil S. Sonar; Kiran F. Shelke; Gopal K. Kakade; Bapurao B. Shingate; Murlidhar S. Shingare

    2009-01-01

    Alum (KAl(SO4)2·12H2O) is an inexpensive, efficient, non-toxic and mild catalyst for the one-pot synthesis of ?-aminophosphonates. A three component reaction of an aldehyde\\/ketone, an amine and triethyl phosphite was carried out under solvent-free conditions to afford the corresponding ?-aminophosphonates in short reaction times and high yields with the green aspects by avoiding toxic catalysts and solvents.

  7. Alum catalyzed simple and efficient synthesis of 5-arylidene-2,4-thiazolidinedione in aqueous media

    Microsoft Academic Search

    Kiran F. Shelke; Suryakant B. Sapkal; Gopal K. Kakade; Sandip A. Sadaphal; Bapurao B. Shingate; Murlidhar S. Shingare

    2010-01-01

    Alum (KAl(SO4)2·12H2O) is an inexpensive, efficient, and non-toxic catalyst used for the synthesis of 5-arylidine-2,4-thiazolidinediones by the Knoevenagel condensation of aromatic aldehydes with 2,4-thiazolidinedione in aqueous media at 90°C. This method affords the 5-arylidine-2,4-thiazolidinediones in short reaction times, high yields, and green aspects by avoiding toxic catalysts and hazardous solvents.

  8. Combining module selection and resource sharing for efficient FPGA pipeline synthesis

    Microsoft Academic Search

    Welson Sun; Michael J. Wirthlin; Stephen Neuendorffer

    2006-01-01

    In FPGA designs significant area savings can be achieved by using slower, more area-efficient circuit modules or by time-multiplexing faster circuit modules. Unfortunately, the ability of designers to manually make such trade-offs is limited by the large number of different architectural possibilities. In order to automatically perform these trade-offs, we have developed a synthesis methodology that generates pipelined data-path circuits

  9. 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

  10. 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

  11. Chemoselective catalytic hydrogenation of acrolein on Ag(111): effect of molecular orientation on reaction selectivity.

    PubMed

    Brandt, Katrin; Chiu, May E; Watson, David J; Tikhov, Mintcho S; Lambert, Richard M

    2009-12-01

    The adsorption and hydrogenation of acrolein on the Ag(111) surface has been investigated by high resolution synchrotron XPS, NEXAFS, and temperature programmed reaction. The molecule adsorbs intact at all coverages and its adsorption geometry is critically important in determining chemoselectivity toward the formation of allyl alcohol, the desired but thermodynamically disfavored product. In the absence of hydrogen adatoms (H(a)), acrolein lies almost parallel to the metal surface; high coverages force the C=C bond to tilt markedly, likely rendering it less vulnerable toward reaction with hydrogen adatoms. Reaction with coadsorbed H(a) yields allyl alcohol, propionaldehyde, and propanol, consistent with the behavior of practical dispersed Ag catalysts operated at atmospheric pressure: formation of all three hydrogenation products is surface reaction rate limited. Overall chemoselectivity is strongly influenced by secondary reactions of allyl alcohol. At low H(a) coverages, the C=C bond in the newly formed allyl alcohol molecule is strongly tilted with respect to the surface, rendering it immune to attack by H(a) and leading to desorption of the unsaturated alcohol. In contrast with this, at high H(a) coverages, the C=C bond in allyl alcohol lies almost parallel to the surface, undergoes hydrogenation by H(a), and the saturated alcohol (propanol) desorbs. PMID:19888721

  12. 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

  13. N-triazinylammonium tetrafluoroborates. A new generation of efficient coupling reagents useful for peptide synthesis.

    PubMed

    Kami?ski, Zbigniew J; Kolesi?ska, Beata; Kolesi?ska, Justyna; Sabatino, Giuseppina; Chelli, Mario; Rovero, Paolo; B?aszczyk, Micha?; G?ówka, Marek L; Papini, Anna Maria

    2005-12-01

    A new generation of triazine-based coupling reagents (TBCRs), designed according to the concept of "superactive esters", was obtained by treatment of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium (DMTMM) chloride with lithium or silver tetrafluoroborate. The structure of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium tetrafluoroborate was confirmed by X-ray diffraction. Activation of carboxylic acids by using this reagent proceeds via triazine "superactive ester". The coupling reagent was successfully used for the synthesis of Z-, Boc-, and Fmoc-protected dipeptides derived from natural and unnatural sterically hindered amino acids and for fragment condensation, in 80-100% yield and with high enantiomeric purity. The manual SPPS of the ACP(65-74) peptide fragment (H-Val-Gln-Ala-Ala-Ile-Asp-Tyr-Ile-Asn-Gly-OH) proceeded significantly faster than with TBTU or HATU, as well as the automated SPPS of the same fragment gave a purer product than by using TBTU or PyBOP. The reagent was also demonstrated to be efficient in on-resin head-to-tail cyclization of constrained cyclopeptides, in SPPS synthesis of Aib peptides, and in the synthesis of esters from appropriate acids, alcohols, and phenols. The high efficiency and versatility of this new generation of TBCRs confirm, for the first time, the usefulness of the concept of "superactive esters" in rational design of the structure of coupling reagents. PMID:16316237

  14. 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

  15. Efficient Retrograde Transport of Pseudorabies Virus within Neurons Requires Local Protein Synthesis In Axons

    PubMed Central

    Koyuncu, Orkide O.; Perlman, David H.; Enquist, Lynn W.

    2012-01-01

    Summary After replicating in epithelial cells, alphaherpesviruses such as Pseudorabies Virus (PRV) invade axons of peripheral nervous system neurons and undergo retrograde transport toward the distant cell bodies. Although several viral proteins engage molecular motors to facilitate transport, the initial steps and neuronal responses to infection are poorly understood. Using compartmented neuron cultures to physically separate axon infection from cell bodies, we found that PRV infection induces local protein synthesis in axons, including proteins involved in cytoskeletal remodeling, intracellular trafficking, signaling, and metabolism. This rapid translation of axonal mRNAs is required for efficient PRV retrograde transport and infection of cell bodies. Furthermore, induction of axonal damage, which also induces local protein synthesis, prior to infection reduces virion trafficking, suggesting that host damage signals and virus particles compete for retrograde transport. Thus, similar to axonal damage, virus infection induces local protein translation in axons and viruses likely exploit this response for invasion. PMID:23332155

  16. In situ tracing of cell surface sialic acid by chemoselective recognition to unload gold nanocluster probe from density tunable dendrimeric array.

    PubMed

    Chen, Yunlong; Ding, Lin; Ju, Huangxian

    2013-01-30

    A density tunable dendrimeric array was designed for assembly of a gold nanocluster probe, which was unloaded by its chemoselective recognition to cell surface sialic acid for in situ tracing of sialic acid density. PMID:23223313

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

    E-print Network

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

    2015-04-14

    - native to devices employing organic dyes. The manufacture of Sb2S3 absorber layers is however slow and cumbersome. Here, we report the modi- fied aqueous chemical bath synthesis of Sb2S3 ab- sorber layers for sensitized solar cells. Our method is based... . Steiner and S. K. Pathak, Chem. Commun., 2015, DOI: 10.1039/C5CC01966D. Efficient room temperature aqueous Sb2S3 synthesis for inorganic-organic sensitized solar cells with 5.1% efficiencies† Karl C. Go¨del,a Yong Chan Choi,b Bart Roose,ac Aditya Sadhanala...

  18. Efficient synthesis of quantum gates on a three-spin system with triangle topology

    SciTech Connect

    Yuan, Haidong; Khaneja, Navin [School of Engineering and Applied Science, Harvard University, 33 Oxford Street, Cambridge, Massachusetts 02138 (United States)

    2011-12-15

    Experiments in coherent nuclear and electron magnetic resonance and optical spectroscopy correspond to control of quantum-mechanical ensembles, guiding them from initial states to target states by unitary transformations. The control inputs (pulse sequences) that accomplish these unitary transformations should take as little time as possible so as to minimize the effects of relaxation and decoherence, and to optimize the sensitivity of the experiments. Here, we give an efficient synthesis of a class of unitary transformations on a three coupled spin-(1/2) system with equal Ising coupling strengths. We show a significant time saving compared with conventional methods.

  19. Solvent-controlled halo-selective selenylation of aryl halides catalyzed by Cu(II) supported on Al2O3. A general protocol for the synthesis of unsymmetrical organo mono- and bis-selenides.

    PubMed

    Chatterjee, Tanmay; Ranu, Brindaban C

    2013-07-19

    Alumina-supported Cu(II) efficiently catalyzes selenylation of aryl iodides and aryl bromides by diaryl, dialkyl, and diheteroaryl diselenides in water and PEG-600, respectively, leading to a general route toward synthesis of unsymmetrical diaryl, aryl-alkyl, aryl-heteroaryl, and diheteroaryl selenides. A sequential reaction of bromoiodobenzene with one diaryl/diheteroaryl/dialkyl diselenide in water and another diaryl/diheteroaryl/dialkyl diselenide in PEG-600 in the second step produces unsymmetrical diaryl, diheteroaryl, or aryl-alkyl bis-selanyl benzene. A library of functionalized organo mono- and bis-selenides, including a potent biologically active molecule and a couple of analogues of bioactive selenides, were obtained in high yields by this protocol. The reactions are chemoselective and high yielding. The Cu-Al2O3 catalyst is recycled for seven runs without any appreciable loss of activity. PMID:23786642

  20. Breaking the dichotomy of reactivity vs. chemoselectivity in catalytic S(N)1 reactions of alcohols.

    PubMed

    Hellal, Malik; Falk, Florian C; Wolf, Eléna; Dryzhakov, Marian; Moran, Joseph

    2014-08-21

    The inability to decouple Lewis acid catalysis from undesirable Brønsted acid catalysed side reactions when water or other protic functional groups are necessarily present has forced chemists to choose between powerful but harsh catalysts or poor but mild ones, a dichotomy that restricts the substrate scope of dehydrative transformations such as the direct SN1 reaction of alcohols. A systematic survey of Lewis and Brønsted acids reveals that the strong non-hydrolyzable Lewis acid B(C6F5)3 leads to highly chemoselective alcohol substitution in the presence of acid-sensitive alkenes, protecting groups and other functional groups without the typical compromise in reaction rates, substrate scope and catalyst loading. PMID:24987941

  1. Chemoselective immobilization of proteins by microcontact printing and bio-orthogonal click reactions.

    PubMed

    Tolstyka, Zachary P; Richardson, Wade; Bat, Erhan; Stevens, Caitlin J; Parra, Dayanara P; Dozier, Jonathan K; Distefano, Mark D; Dunn, Bruce; Maynard, Heather D

    2013-12-16

    Herein, a combination of microcontact printing of functionalized alkanethiols and site-specific modification of proteins is utilized to chemoselectively immobilize proteins onto gold surfaces, either by oxime- or copper-catalyzed alkyne-azide click chemistry. Two molecules capable of click reactions were synthesized, an aminooxy-functionalized alkanethiol and an azide-functionalized alkanethiol, and self-assembled monolayer (SAM) formation on gold was confirmed by IR spectroscopy. The alkanethiols were then individually patterned onto gold surfaces by microcontact printing. Site-specifically modified proteins-horse heart myoglobin (HHMb) containing an N-terminal ?-oxoamide and a red fluorescent protein (mCherry-CVIA) with a C-terminal alkyne-were immobilized by incubation onto respective stamped functionalized alkanethiol patterns. Pattern formation was confirmed by fluorescence microscopy. PMID:24166802

  2. Chemoselective reduction of the carbonyl functionality through hydrosilylation: integrating click catalysis with hydrosilylation in one pot.

    PubMed

    Roy, Sudipta Raha; Sau, Samaresh Chandra; Mandal, Swadhin K

    2014-10-01

    Herein we report the chemoselective reduction of the carbonyl functionality via hydrosilylation using a copper(I) catalyst bearing the abnormal N-heterocyclic carbene 1 with low (0.25 mol %) catalyst loading at ambient temperature in excellent yield within a very short reaction time. The hydrosilylation reaction of ?,?-unsaturated carbonyl compounds takes place selectively toward 1,2-addition (C?O) to yield the corresponding allyl alcohols in good yields. Moreover, when two reducible functional groups such as imine and ketone groups are present in the same molecule, this catalyst selectively reduces the ketone functionality. Further, 1 was used in a consecutive fashion by combining the Huisgen cycloaddition and hydrosilylation reactions in one pot, yielding a range of functionalized triazole substituted alcohols in excellent yields. PMID:25188382

  3. 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

  4. Suppression of HLA Expression by Lentivirus-mediated Gene Transfer of siRNA Cassettes and In Vivo Chemoselection to Enhance Hematopoietic Stem Cell Transplantation

    PubMed Central

    Hacke, Katrin; Falahati, Rustom; Flebbe-Rehwaldt, Linda; Kasahara, Noriyuki; Gaensler, Karin M. L.

    2010-01-01

    Current approaches for hematopoietic stem cell (HSC) and organ transplantation are limited by donor and host-mediated immune responses to allo-antigens. Application of these therapies is limited by the toxicity of preparative and post-transplant immunosuppressive regimens and a shortage of appropriate HLA-matched donors. We have been exploring two complementary approaches for genetically modifying donor cells that achieve long-term suppression of cellular proteins that elicit host immune responses to mismatched donor antigens, and provide a selective advantage to genetically engineered donor cells after transplantation. The first approach is based on recent advances that make feasible targeted down-regulation of HLA expression. Suppression of HLA expression could help to overcome limitations imposed by extensive HLA polymorphisms that restrict the availability of suitable donors. Accordingly, we have recently investigated whether knockdown of HLA by RNA interference (RNAi) enables allogeneic cells to evade immune recognition. For efficient and stable delivery of short hairpin-type RNAi constructs (shRNA), we employed lentivirus-based gene transfer vectors that integrate into genomic DNA, thereby permanently modifying transduced donor cells. Lentivirus-mediated delivery of shRNA targeting pan-Class I and allele-specific HLA achieved efficient and dose-dependent reduction in surface expression of HLA in human cells, and enhanced resistance to allo-reactive T lymphocyte-mediated cytotoxicity, while avoiding non-MHC restricted killing. Complementary strategies for genetic engineering of HSC that would provide a selective advantage for transplanted donor cells and enable successful engraftment with less toxic preparative and immunosuppressive regimens would increase the numbers of individuals to whom HLA suppression therapy could be offered. Our second strategy is to provide a mechanism for in vivo selection of genetically modified HSC and other donor cells. We have uniquely combined transplantation during the neonatal period, when tolerance may be more readily achieved, with a positive selection strategy for in vivo amplification of drug-resistant donor HSC. This model system enables the evaluation of mechanisms of tolerance induction to neo-antigens, and allogeneic stem cells during immune ontogeny. HSC are transduced ex vivo by lentivirus-mediated gene transfer of P140K-O6-methylguanine-methyltransferase (MGMTP140K). The MGMTP140K DNA repair enzyme confers resistance to benzylguanine, an inhibitor of endogenous MGMT, and to chloroethylating agents such as BCNU. In vivo chemoselection enables enrichment of donor cells at the stem cell level. Using complementary approaches of in vivo chemoselection and RNAi-induced silencing of HLA expression may enable the generation of histocompatibility-enhanced, and eventually, perhaps “universally” compatible cellular grafts. PMID:19048410

  5. Efficient Synthesis of Eriodictyol from l-Tyrosine in Escherichia coli

    PubMed Central

    Zhu, Saijie; Wu, Junjun; Du, Guocheng

    2014-01-01

    The health benefits of flavonoids for humans are increasingly attracting attention. Because the extraction of high-purity flavonoids from plants presents a major obstacle, interest has emerged in biosynthesizing them using microbial hosts. Eriodictyol is a flavonoid with anti-inflammatory and antioxidant activities. Its efficient synthesis has been hampered by two factors: the poor expression of cytochrome P450 and the low intracellular malonyl coenzyme A (malonyl-CoA) concentration in Escherichia coli. To address these issues, a truncated plant P450 flavonoid, flavonoid 3?-hydroxylase (tF3?H), was functionally expressed as a fusion protein with a truncated P450 reductase (tCPR) in E. coli. This allowed the engineered E. coli to produce eriodictyol from l-tyrosine by simultaneously coexpressing the fusion protein with tyrosine ammonia lyase (TAL), 4-coumarate-CoA ligase (4CL), chalcone synthase (CHS), and chalcone isomerase (CHI). In addition, metabolic engineering was employed to enhance the availability of malonyl-CoA so as to achieve a new metabolic balance and rebalance the relative expression of genes to enhance eriodictyol accumulation. This approach made the production of eriodictyol 203% higher than that in the control strain. By using these strategies, the production of eriodictyol from l-tyrosine reached 107 mg/liter. The present work offers an approach to the efficient synthesis of other hydroxylated flavonoids from l-tyrosine or even glucose in E. coli. PMID:24610848

  6. Efficient synthesis of eriodictyol from L-tyrosine in Escherichia coli.

    PubMed

    Zhu, Saijie; Wu, Junjun; Du, Guocheng; Zhou, Jingwen; Chen, Jian

    2014-05-01

    The health benefits of flavonoids for humans are increasingly attracting attention. Because the extraction of high-purity flavonoids from plants presents a major obstacle, interest has emerged in biosynthesizing them using microbial hosts. Eriodictyol is a flavonoid with anti-inflammatory and antioxidant activities. Its efficient synthesis has been hampered by two factors: the poor expression of cytochrome P450 and the low intracellular malonyl coenzyme A (malonyl-CoA) concentration in Escherichia coli. To address these issues, a truncated plant P450 flavonoid, flavonoid 3'-hydroxylase (tF3'H), was functionally expressed as a fusion protein with a truncated P450 reductase (tCPR) in E. coli. This allowed the engineered E. coli to produce eriodictyol from l-tyrosine by simultaneously coexpressing the fusion protein with tyrosine ammonia lyase (TAL), 4-coumarate-CoA ligase (4CL), chalcone synthase (CHS), and chalcone isomerase (CHI). In addition, metabolic engineering was employed to enhance the availability of malonyl-CoA so as to achieve a new metabolic balance and rebalance the relative expression of genes to enhance eriodictyol accumulation. This approach made the production of eriodictyol 203% higher than that in the control strain. By using these strategies, the production of eriodictyol from l-tyrosine reached 107 mg/liter. The present work offers an approach to the efficient synthesis of other hydroxylated flavonoids from l-tyrosine or even glucose in E. coli. PMID:24610848

  7. Efficient Total Synthesis of Bongkrekic Acid and Apoptosis Inhibitory Activity of Its Analogues.

    PubMed

    Matsumoto, Kenji; Suyama, Masaki; Fujita, Satoshi; Moriwaki, Takuya; Sato, Yukiko; Aso, Yoshifumi; Muroshita, Satoshi; Matsuo, Hiroshi; Monda, Keishi; Okuda, Katsuhiro; Abe, Masato; Fukunaga, Hiroyuki; Kano, Arihiro; Shindo, Mitsuru

    2015-08-01

    Bongkrekic acid (BKA), isolated from the bacterium Burkholderia cocovenenans, is an inhibitor of adenine nucleotide translocator, which inhibits apoptosis, and is thus an important tool for the mechanistic investigation of apoptosis. An efficient total synthesis of BKA has been achieved by employing a three-component convergent strategy based on Kocienski-Julia olefination and Suzuki-Miyaura coupling. It is noteworthy that segment?B has been prepared as a new doubly functionalized coupling partner, which contributes to shortening of the number of steps. Torquoselective olefination with an ynolate has also been applied for the efficient construction of an unsaturated ester. Furthermore, it is revealed that 1-methyl-2-azaadamantane N-oxyl is an excellent reagent for final oxidation to afford BKA in high yield. Based on the total synthesis, several BKA analogues were prepared for structure-activity relationship studies, which indicated that the carboxylic acid moieties were essential for the apoptosis inhibitory activity of BKA. More easily available BKA analogues with potent apoptosis inhibitory activity were also developed. PMID:26126659

  8. The total synthesis of (-)-nitidasin.

    PubMed

    Hog, Daniel T; Huber, Florian M E; Mayer, Peter; Trauner, Dirk

    2014-08-01

    Nitidasin is a pentacyclic sesterterpenoid with a rare 5-8-6-5 carbon skeleton that was isolated from the Peruvian folk medicine "Hercampuri". It belongs to a small class of sesterterpenoids that feature an isopropyl trans-hydrindane moiety fused to a variety of other ring systems. As a first installment of our general approach toward these natural products, we report the total synthesis of the title compound. Our stereoselective, convergent route involves the addition of a complex alkenyl lithium compound to a trans-hydrindanone, followed by chemoselective epoxidation, ring-closing olefin metathesis, and redox adjustment. PMID:24962933

  9. Efficient Hybrid Grid Synthesis Method Based on Genetic Algorithm for Power/Ground Network Optimization with Dynamic Signal Consideration

    NASA Astrophysics Data System (ADS)

    Yang, Yun; Kimura, Shinji

    This paper proposes an efficient design algorithm for power/ground (P/G) network synthesis with dynamic signal consideration, which is mainly caused by Ldi/dt noise and Cdv/dt decoupling capacitance (DECAP) current in the distribution network. To deal with the nonlinear global optimization under synthesis constraints directly, the genetic algorithm (GA) is introduced. The proposed GA-based synthesis method can avoid the linear transformation loss and the restraint condition complexity in current SLP, SQP, ICG, and random-walk methods. In the proposed Hybrid Grid Synthesis algorithm, the dynamic signal is simulated in the gene disturbance process, and Trapezoidal Modified Euler (TME) method is introduced to realize the precise dynamic time step process. We also use a hybrid-SLP method to reduce the genetic execute time and increase the network synthesis efficiency. Experimental results on given power distribution network show the reduction on layout area and execution time compared with current P/G network synthesis methods.

  10. Tandem reactions for streamlining synthesis: enantio- and diastereoselective one-pot generation of functionalized epoxy alcohols.

    PubMed

    Hussain, Mahmud M; Walsh, Patrick J

    2008-08-01

    [Reaction: see text] 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 co-workers 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

  11. Highly efficient solid phase synthesis of large polypeptides by iterative ligations of

    E-print Network

    Paris-Sud XI, Université de

    to the synthesis of a 60 amino acid-long latent peptide thioester or to the assembly of five peptide segments by the combination of several essential chemical tools. Solid phase peptide synthesis (SPPS)1 enables the synthesis for protein total synthesis.9 The ligation of two peptide segments potentially gives access to polypeptides

  12. Use of Bacillus brevis for efficient synthesis and secretion of human epidermal growth factor.

    PubMed Central

    Yamagata, H; Nakahama, K; Suzuki, Y; Kakinuma, A; Tsukagoshi, N; Udaka, S

    1989-01-01

    Using previously isolated Bacillus brevis strains that secrete large amounts of proteins but little protease into the medium, we have developed a host-vector system for very efficient synthesis and secretion of heterologous proteins. The multiple promoters and the signal-peptide-coding region of the MWP gene, a structural gene for one of the major cell wall proteins of B. brevis strain 47, were used to construct expression-secretion vectors. With this system, a synthetic gene for human epidermal growth factor (hEGF) was expressed efficiently and a large amount (0.24 g per liter of culture) of mature hEGF was secreted into the medium. hEGF purified from the culture supernatant had the same NH2-terminal amino acid sequence, COOH-terminal amino acid, and amino acid composition as natural hEGF, and it was fully active in biological assays. These results, in combination with previous results, showed that mammalian proteins can be produced in active form 10-100 times more efficiently in B. brevis than has been reported in other systems. Images PMID:2786200

  13. 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.

  14. Efficient Synthesis of Simvastatin by Use of Whole-Cell Biocatalysis?

    PubMed Central

    Xie, Xinkai; Tang, Yi

    2007-01-01

    Simvastatin is a semisynthetic derivative of the fungal polyketide lovastatin and is an important drug for lowering cholesterol levels in adults. We have developed a one-step, whole-cell biocatalytic process for the synthesis of simvastatin from monacolin J. By using an Escherichia coli strain overexpressing the previously discovered acyltransferase LovD (X. Xie, K. Watanabe, W. A. Wojcicki, C. C. Wang, and Y. Tang, Chem. Biol. 13:1161-1169, 2006), we were able to achieve >99% conversion of monacolin J to simvastatin without the use of any chemical protection steps. The key finding was a membrane-permeable substrate, ?-dimethylbutyryl-S-methyl-mercaptopropionate, that was efficiently utilized by LovD as the acyl donor. The process was scaled up for gram-scale synthesis of simvastatin. We also demonstrated that simvastatin synthesized via this method can be readily purified from the fermentation broth with >90% recovery and >98% purity as determined by high-performance liquid chromatography. Bioconversion using high-cell-density, fed-batch fermentation was also examined. The whole-cell biocatalysis can therefore be an attractive alternative to currently used multistep semisynthetic transformations. PMID:17277201

  15. Amino acid assisted templating synthesis of hierarchical zeolitic imidazolate framework-8 for efficient arsenate removal.

    PubMed

    Wu, Yi-nan; Zhou, Meimei; Zhang, Bingru; Wu, Baozhen; Li, Jie; Qiao, Junlian; Guan, Xiaohong; Li, Fengting

    2014-01-21

    We report the strategy of using the cationic surfactant cetyltrimethylammonium bromide (CTAB) and amino acid L-histidine (His) as co-templates to produce hierarchical ZIF-8 in an aqueous system at room temperature. The hierarchical ZIF-8 had both meso- and microporous structure, resulting in a high mesopore volume as well as specific surface area which can be controlled by the synthesis conditions. We put forward the hypothesis for the formation of a mesoporous structure and the enhancement of the porosity of ZIF-8 that the histidine plays a key role on the stabilization of CTAB micelles and avoiding the production of unexpected by-products therefore promotes the fabrication of pure phase ZIF-8 containing the mesopores interconnected with micropores. The prepared hierarchical ZIF-8 exhibited an excellent performance as a new kind of porous absorbent for efficient removal of the toxic arsenate. PMID:24296611

  16. 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.

  17. 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

  18. A Novel and Efficient One-Step Parallel Synthesis of Dibenzopyranones via Suzuki-Miyaura Cross Coupling

    PubMed Central

    Vishnumurthy, Kodumuru; Makriyannis, Alexandros

    2010-01-01

    Microwave promoted novel and efficient one-step parallel synthesis of dibenzopyranones and heterocyclic analogues from bromo arylcarboxylates and o-hydroxyarylboronic acids via Suzuki-Miyaura cross coupling reaction is described. Spontaneous lactonization gave dibenzopyranones and heterocyclic analogues bearing electron donating and withdrawing groups on both aromatic rings in good to excellent yields. PMID:20831265

  19. Tetramethylguanidine-[ bmim ][BF 4 ]. An Efficient and Recyclable Catalytic System for One-Pot Synthesis of 4 H -Pyrans

    Microsoft Academic Search

    Yanqing Peng; Gonghua Song; Feifei Huang

    2005-01-01

    Summary. A clean and efficient method for the synthesis of 4H-pyran derivatives through the one-pot condensation of aromatic aldehydes, malononitriles, and ß-dicarbonyl compounds, using guanidine base tetramethylguanidine in [bmim][BF4] ionic liquid as a recyclable catalytic system, was described.

  20. Fast and Efficient Synthesis of Sulfinamides by the Oxidation of Sulfenamides Using Potassium Fluoride and m-Chloroperoxybenzoic Acid

    Microsoft Academic Search

    Mrityunjoy Datta; Alan J. Buglass

    2012-01-01

    A procedure for the synthesis of N-alkyl-, N-cycloalkyl-, N,N-dialkyl-, and N-arylarenesulfinamides from the corresponding sulfenamides using KF\\/m-CPBA in CH3CN-H2O is described. High efficiency (fast reactions, ease of manipulation and high yields) and absence of over-oxidation are the major advantageous features of this protocol.

  1. Toward a protecting-group-free halogen-metal exchange reaction: practical, chemoselective metalation of functionalized aromatic halides using dianion-type zincate, tBu4ZnLi2.

    PubMed

    Uchiyama, Masanobu; Furuyama, Taniyuki; Kobayashi, Minoru; Matsumoto, Yotaro; Tanaka, Kentaro

    2006-07-01

    A versatile preparation method for aromatic zincate compounds through a halogen-zinc exchange reaction using dilithium tetra-tert-butylzincate (tBu4ZnLi2) has been developed. This reagent permits efficient preparation of highly functionalized aromatic zincates, particularly, those with electrophilic functional groups, such as ester, amide, alcohol, and phenol. Halogen-zinc exchange reactions followed by electrophilic trapping (with allyl bromide or benzaldehyde) proved to be a powerful tool for C-C bond formation on functionalized aromatic rings. The functionalized aromatic zincate intermediate was also found to undergo copper- and palladium-catalyzed C-C bond-forming reactions with good yields and high chemoselectivity. PMID:16802798

  2. Effects of nitric oxide and its synthesis inhibitor on neuron efficiency detected by a fiber-optic-based multisensor

    NASA Astrophysics Data System (ADS)

    Shen, Zheng; Hua, Jun; Lin, Shuzhi; Liu, Xiangfeng

    1998-01-01

    Sodium nitroprusside (SNP) as an exogenous nitric oxide (NO) donor and N(omega) -nitro-L-arginine methyl ester(L-NAME) as NO synthesis inhibitor was driven into monkey cortex by iontophoresis, their effects on face recognition of monkey were observed, and neuron firing as well as neuron efficiency were monitored by fiberoptic-based multisensor during face recognition. The results show that L-NAME and low dose of SNP(5 nM) did not have any significant effect on face recognition and neuron efficiency, however high dose of SNP(50 nM) increased simultaneously both correct rate of face recognition and neuron efficiency, but not neuron firing. The results were discussed according to NO and its synthesis mechanism.

  3. 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

  4. 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

  5. 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

  6. 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

  7. A Highly Practical Copper(I)/TEMPO Catalyst System for Chemoselective Aerobic Oxidation of Primary Alcohols

    PubMed Central

    Hoover, Jessica M.; Stahl, Shannon S.

    2011-01-01

    Aerobic oxidation reactions have been the focus of considerable attention, but their use in mainstream organic chemistry has been constrained by limitations in their synthetic scope and by practical factors, such as the use of pure O2 as the oxidant or complex catalyst synthesis. Here, we report a new (bpy)CuI/TEMPO catalyst system that enables efficient and selective aerobic oxidation of a broad range of primary alcohols, including allylic, benzylic and aliphatic derivatives, to the corresponding aldehydes using readily available reagents, at room temperature with ambient air as the oxidant. The catalyst system is compatible with a wide range of functional groups and the high selectivity for 1° alcohols enables selective oxidation of diols that lack protecting groups. PMID:21861488

  8. Chemoselective quantum control of carbonyl bonds in Grignard reactions using shaped laser pulses.

    PubMed

    Gollub, Caroline; Kowalewski, Markus; Thallmair, Sebastian; de Vivie-Riedle, Regina

    2010-12-28

    Grignard reactants like methylmagnesium chloride are not selective with respect to different carbonyl bonds. We present a theoretical study where shaped laser pulses are utilized to prefer specific bonds in a mixture of more than one carbonyl reactant. A mixture of cyclohexanone and cyclopentanone has been chosen as a representative example. The light pulse is supposed to provide the activation energy and to adopt the function of a protecting group. The control aim is to stretch exclusively the C-O bond of one compound to the length required in the Grignard transition state. To guarantee an experimentally realizable bandwidth for the unshaped pulse, we use our recently developed optimal control theory algorithm, which allows the simultaneous optimization of the light field in the time and frequency domain. Highly selective picosecond control pulses could be optimized in the infrared regime suggesting that laser assisted chemoselectivity is possible to a large extent. To obtain control not only on the final product but also on the excitation mechanism, various initial conditions and frequency restrictions were investigated. PMID:21082089

  9. Scalable Synthesis of Cortistatin A and Related Structures

    PubMed Central

    Shi, Jun; Manolikakes, Georg; Yeh, Chien-Hung; Guerrero, Carlos A.; Shenvi, Ryan A.; Shigehisa, Hiroki

    2011-01-01

    Full details are provided for an improved synthesis of cortistatin A and related structures as well as the underlying logic and evolution of strategy. The highly functionalized cortistatin A-ring embedded with a key heteroadamantane was synthesized by a simple and scalable 5-step sequence. A chemoselective, tandem geminal dihalogenation of an unactivated methyl group, a reductive fragmentation/trapping/elimination of a bromocyclopropane, and a facile chemoselective etherification reaction afforded the cortistatin A core, dubbed “cortistatinone”. A selective ?16-alkene reduction with Raney Ni provided cortistatin A. With this scalable and practical route, copious quantities of cortistatinone, ?16-cortistatin A-the equipotent direct precursor to cortistatin A, and its related analogs were prepared for further biological studies. PMID:21539314

  10. A regioselective facile synthesis of furo[3,4-b]carbazolones: application to the total synthesis of mafaicheenamine E and claulansine D.

    PubMed

    Mal, Dipakranjan; Roy, Joyeeta

    2015-05-27

    1-Hydroxycarbazole-2,3-dicarboxylates have been shown to undergo chemoselective reductive cyclization to furo[3,4-b]carbazolones on reaction with LiAlH4. One of the furocarbazolones is utilized to accomplish the first total synthesis of claulansine D and mafaicheenamine E in 9 and 6 steps respectively. The other key steps of the syntheses are addition of an allylic indium reagent and CC double bond isomerization. PMID:25970723

  11. Effect of total mixed ration composition on fermentation and efficiency of ruminal microbial crude protein synthesis in vitro.

    PubMed

    Boguhn, J; Kluth, H; Rodehutscord, M

    2006-05-01

    The goal of this study was to identify dietary factors that affect fermentation and efficiency of microbial crude protein (CP(M)) synthesis in the rumen in vitro. We used 16 total mixed, dairy cow rations with known digestibilities that varied in ingredient composition and nutrient content. Each ration was incubated in a Rusitec (n = 3) for 15 d, and fermentation of different fractions was assessed. Observed extents of fermentation in 24 h were 35 to 47% for organic matter, 25 to 60% for crude protein, 3 to 28% for neutral detergent fiber, and 31 to 45% for gross energy. Organic matter fermentation depended on the content of crude protein and neutral detergent fiber in the ration. We studied net synthesis of CP(M) using an 15N dilution technique and found that 7 d of continuous 15N application are needed to achieve an 15N enrichment plateau in the N of isolated microbes in this type of study. The efficiency of CP(M) synthesis was 141 to 286 g/kg of fermented organic matter or 4.9 to 11.1 g/MJ of metabolizable energy, and these ranges agree with those found in the literature. Multiple regressions to predict the efficiency of CP(M) synthesis by diet data showed that crude protein was the only dietary chemical fraction that had a significant effect. Fat content and the inclusion rate of corn silage in the ration also tended to improve efficiency. We suggest that microbial need for preformed amino acids may explain the crude protein effect. A large part of the variation in efficiency of microbial activity still remains unexplained. PMID:16606728

  12. 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

  13. 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

  14. Rapid and highly efficient trimethylsilylation of alcohols and phenols with hexamethyldisilazane (HMDS) catalyzed by reusable zirconyl triflate, [ZrO(OTf) 2

    Microsoft Academic Search

    Majid Moghadam; Shahram Tangestaninejad; Valiollah Mirkhani; Iraj Mohammadpoor-Baltork; Shahin Chahardahcheric; Ziba Tavakoli

    2008-01-01

    In this paper, rapid and efficient trimethylsilylation of alcohols and phenols with hexamethyldisilazane in the presence of catalytic amounts of ZrO(OTf)2 is reported. Primary, secondary and tertiary alcohols as well as phenols were efficiently converted to their corresponding TMS ethers in short reaction times at room temperature. It is noteworthy that this method can be used for chemoselective silylation of

  15. Efficient Synthesis of Fmoc-Protected Phosphinic Pseudodipeptides: Building Blocks for the Synthesis of Matrix Metalloproteinase Inhibitors

    E-print Network

    Lepore, Salvatore D.

    for the Synthesis of Matrix Metalloproteinase Inhibitors Manishabrata Bhowmick,1 Ravinder R. Sappidi,1 Gregg B) inhibitors as activa- tion of these enzymes have been associated with primary and metastatic tumor growth to the design of an inhibitor of metallo-proteases involves replacing a trigonal planar amide or ester bond

  16. 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

  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. 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, 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

  19. 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

  20. A new and efficient synthesis of 6-o-methylscutellarein, the major metabolite of the natural medicine scutellarin.

    PubMed

    Zhang, Wei; Dong, Ze-Xi; Gu, Ting; Li, Nian-Guang; Zhang, Peng-Xuan; Wu, Wen-Yu; Yu, Shao-Peng; Tang, Yu-Ping; Yang, Jian-Ping; Shi, Zhi-Hao

    2015-01-01

    In this paper, a new and efficient synthesis of 6-O-methylscutellarein (3), the major metabolite of the natural medicine scutellarin, is reported. Two hydroxyl groups at C-4' and C-7 in 2 were selectively protected by chloromethyl methyl ether after the reaction conditions were optimized, then 6-O-methyl-scutellarein (3) was produced in high yield after methylation of the hydroxyl group at C-6 and subsequent deprotection of the two methyl ether groups. PMID:26042857

  1. One-pot hydrazide-based native chemical ligation for efficient chemical synthesis and structure determination of toxin Mambalgin-1.

    PubMed

    Pan, Man; He, Yao; Wen, Ming; Wu, Fangming; Sun, Demeng; Li, Sijian; Zhang, Longhua; Li, Yiming; Tian, Changlin

    2014-06-01

    An efficient one-pot chemical synthesis of snake venom toxin Mambalgin-1 was achieved using an azide-switch strategy combined with hydrazide-based native chemical ligation. Synthetic Mambalgin-1 exhibited a well-defined structure after sequential folding in vitro. NMR spectroscopy revealed a three-finger toxin family structure, and the synthetic toxin inhibited human acid-sensing ion channel 1a. PMID:24619065

  2. A simple and efficient synthesis of substituted 2,2'-bithiophene and 2,2':5',2?-terthiophene.

    PubMed

    Kostyuchenko, Anastasia S; Averkov, Alexey M; Fisyuk, Alexander S

    2014-04-01

    A simple and efficient approach is developed for the synthesis of substituted 2,2'-bithiophene- and 2,2':5',2?-terthiophene-5-carboxylic acids and esters which is based on thiophene ring closure in the Fiesselmann reaction. Using this method, derivatives containing a long alkyl chain with or without an end functional group or an aryl substituent can be conveniently prepared. PMID:24624889

  3. Efficient sonochemical synthesis of alkyl 4-aryl-6-chloro-5-formyl-2-methyl-1,4-dihydropyridine-3-carboxylate derivatives.

    PubMed

    Ruiz, Enrique; Rodríguez, Hortensia; Coro, Julieta; Niebla, Vladimir; Rodríguez, Alfredo; Martínez-Alvarez, Roberto; de Armas, Hector Novoa; Suárez, Margarita; Martín, Nazario

    2012-03-01

    A facile, efficient and environment-friendly protocol for the synthesis of 6-chloro-5-formyl-1,4-dihydropyridine derivatives has been developed by the convenient ultrasound-mediated reaction of 2(1H)pyridone derivatives with the Vilsmeier-Haack reagent. This method provides several advantages over current reaction methodologies including a simpler work-up procedure, shorter reaction times and higher yields. PMID:21840238

  4. Correction: Facile synthesis of mesoporous spinel NiCo2O4 nanostructures as highly efficient electrocatalysts for urea electro-oxidation.

    PubMed

    Ding, Rui; Qi, Li; Jia, Mingjun; Wang, Hongyu

    2015-06-01

    Correction for 'Facile synthesis of mesoporous spinel NiCo2O4 nanostructures as highly efficient electrocatalysts for urea electro-oxidation' by Rui Ding et al., Nanoscale, 2014, 6, 1369-1376. PMID:25955973

  5. 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

  6. Palladium-catalyzed allylic C-OH functionalization for efficient synthesis of functionalized allylsilanes.

    PubMed

    Selander, Nicklas; Paasch, Jennifer R; Szabó, Kálmán J

    2011-01-26

    A new method is described for palladium-catalyzed allylic silylation using allylic alcohols and disilanes as precursors. The reactions proceed smoothly under mild and neutral conditions, and this method is suitable for synthesis of regio- and stereodefined allylsilanes. The presented silylation reaction can be easily extended to include synthesis of allylboronates by change of the dimetallic reagent. The presented synthetic procedure offers a broad platform for the selective synthesis of functionalized allyl metal reagents, which are useful precursors in advanced organic chemistry and natural product synthesis. PMID:21162529

  7. Sequence and structure-specific elements of HERG mRNA determine channel synthesis and trafficking efficiency

    PubMed Central

    Sroubek, Jakub; Krishnan, Yamini; McDonald, Thomas V.

    2013-01-01

    Human ether-á-gogo-related gene (HERG) encodes a potassium channel that is highly susceptible to deleterious mutations resulting in susceptibility to fatal cardiac arrhythmias. Most mutations adversely affect HERG channel assembly and trafficking. Why the channel is so vulnerable to missense mutations is not well understood. Since nothing is known of how mRNA structural elements factor in channel processing, we synthesized a codon-modified HERG cDNA (HERG-CM) where the codons were synonymously changed to reduce GC content, secondary structure, and rare codon usage. HERG-CM produced typical IKr-like currents; however, channel synthesis and processing were markedly different. Translation efficiency was reduced for HERG-CM, as determined by heterologous expression, in vitro translation, and polysomal profiling. Trafficking efficiency to the cell surface was greatly enhanced, as assayed by immunofluorescence, subcellular fractionation, and surface labeling. Chimeras of HERG-NT/CM indicated that trafficking efficiency was largely dependent on 5? sequences, while translation efficiency involved multiple areas. These results suggest that HERG translation and trafficking rates are independently governed by noncoding information in various regions of the mRNA molecule. Noncoding information embedded within the mRNA may play a role in the pathogenesis of hereditary arrhythmia syndromes and could provide an avenue for targeted therapeutics.—Sroubek, J., Krishnan, Y., McDonald, T V. Sequence- and structure-specific elements of HERG mRNA determine channel synthesis and trafficking efficiency. PMID:23608144

  8. Convenient and efficient synthesis of functionalized oligopyridine ligands bearing accessory pyrromethene-BF2 fluorophores.

    PubMed

    Ulrich, Gilles; Ziessel, Raymond

    2004-03-19

    The synthesis of stable and highly luminescent pyridine-, bipyridine-, phenanthroline-, bipyrimidine-, and terpyridine-based ligands bearing one or two 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (bodipy) modules has demonstrated the advantages of three different protocols which have been adapted in light of the chemical stability of the alkyne-grafted starting building blocks and the chemical reactivity of the bromo-substituted starting materials. A classical method of condensation of aldehydes or acid chlorides with Kryptopyrrole has been used for direct linkage of a bodipy to the oligopyridinic platform. For the phenylethynyl-linked molecules, direct coupling between the bodipy-phenyliodo and the stable 4'-ethynyl-2,2':6',2' '-terpyridine, 6,6' '-diethynyl-2,2':6',2' '-terpyridine, 5-ethynyl-2,2'-bipyridine, 5,5'-diethynyl-2,2'-bipyridine, 6,6'-diethynyl-2,2'-bipyridine, and 5,5'-diethynyl-2,2'-bipyrimidine substrates is feasible and is promoted by Pd catalysts and sonication. This procedure provides the advantages of efficiency, versatility, and rapidity. A second set of experimental conditions is required to produce the 4-substituted pyridine, 3,8-disubstituted-1,10-phenanthroline, and 5,5' '-disubstituted-2,2':6',2' '-terpyridine derivatives. Cross coupling of a bodipy-phenylethynyl molecule with the bromo-substituted partners takes place smoothly with the pyridine but with low yields in the other cases due to the efficient formation of the homocoupled diphenylbutadiyne bodipy compounds. A third convenient protocol enabled the preparation of these target molecules in a one-pot reaction where the deprotection of the alkyne was conducted in situ by a phase-transfer process with aqueous NaOH and with Et(3)BnN(+)Cl(-) as mediator and the cross-coupling reaction realized in the benzene phase with [Pd(PPh(3))(4)] as catalyst and CuI as co-reagent. The nascent acid was quenched in the aqueous phase. This method is much more efficient when a trimethylsilyl protecting group is used instead of a propargylic alcohol. The pyridino-bodipy bases were alkylated smoothly in good yields in the presence of methyl iodide. The photophysical and electrochemical properties for these new molecules have been investigated and are discussed in terms of substitution patterns of the bipyridine and terpyridine platforms. In the pyridinium salt 18, the fluorescence from the first singlet excited state at lambda(em) = 547 nm is totally quenched at the expense of a low-lying charge-transfer emitting state located at lambda(em) = 660 nm. PMID:15058955

  9. 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

  10. 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.

  11. A Unique Chemoenzymatic Synthesis of r-Galactosyl Epitope Derivatives Containing Free Amino Groups: Efficient Separation

    E-print Network

    Chen, Xi

    , facilitates the lengthy and high-cost process of carbohydrate synthesis. The prepared oligosaccharides rangeG. This method provides a practical approach for the preparation and purification of oligosaccharides containing of the cell surface antigenic determinants (epitopes).2 The chemical synthesis of oligosaccharides containing

  12. 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

  13. Chemoselectivity in Chemical Biology: Acyl Transfer Reactions with Sulfur and Selenium

    PubMed Central

    2012-01-01

    A critical source of insight into biological function is derived from the chemist’s ability to create new covalent bonds between molecules, whether they are endogenous or exogenous to a biological system. A daunting impediment to selective bond formation, however, is the myriad of reactive functionalities present in biological milieu. The high reactivity of the most abundant molecule in biology, water, makes the challenges all the more difficult. We have met these challenges by exploiting the reactivity of sulfur and selenium in acyl transfer reactions. The reactivity of both sulfur and selenium is high compared with that of their chalcogen congener, oxygen. In this Account, we highlight recent developments in this arena, emphasizing contributions from our laboratory. One focus of our research is furthering the chemistry of native chemical ligation (NCL) and expressed protein ligation (EPL), two related processes that enable the synthesis and semisynthesis of proteins. These techniques exploit the lower pKa of thiols and selenols relative to alcohols. Although a deprotonated hydroxyl group in the side chain of a serine residue is exceedingly rare in a biological context, the pKa values of the thiol in cysteine (8.5) and of the selenol in selenocysteine (5.7) often render these side chains anionic under physiological conditions. NCL and EPL take advantage of the high nucleophilicity of the thiolate as well as its utility as a leaving group, and we have expanded the scope of these methods to include selenocysteine. Although the genetic code limits the components of natural proteins to 20 or so ?-amino acids, NCL and EPL enable the semisynthetic incorporation of a limitless variety of nonnatural modules into proteins. These modules are enabling chemical biologists to interrogate protein structure and function with unprecedented precision. We are also pursuing the further development of the traceless Staudinger ligation, through which a phosphinothioester and azide form an amide. We first reported this chemical ligation method, which leaves no residual atoms in the product, in 2000. Our progress in effecting the reaction in water, without an organic cosolvent, was an important step in the expansion of its utility. Moreover, we have developed the traceless Staudinger reaction as a means for immobilizing proteins on a solid support, providing a general method of fabricating microarrays that display proteins in a uniform orientation. Along with NCL and EPL, the traceless Staudinger ligation has made proteins more readily accessible targets for chemical synthesis and semisynthesis. The underlying acyl transfer reactions with sulfur and selenium provide an efficient means to synthesize, remodel, and immobilize proteins, and they have enabled us to interrogate biological systems. PMID:21639109

  14. Highly efficient synthesis of DNA-binding polyamides using a convergent fragment-based approach.

    PubMed

    Fallows, Andrew J; Singh, Ishwar; Dondi, Ruggero; Cullis, Paul M; Burley, Glenn A

    2014-09-01

    Two advances in the synthesis of hairpin pyrrole-imidazole polyamides (PAs) are described. First, the application of a convergent synthetic strategy is shown, involving the Boc-based solid phase synthesis of a C-terminal fragment and the solution phase synthesis of the N-terminal fragment. Second a new hybrid resin is developed that allows for the preparation of hairpin PAs lacking a C-terminal ?-alanine tail. Both methods are compatible with a range of coupling reagents and provide a facile, modular route to prepare PA libraries in high yield and crude purity. PMID:25162625

  15. 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

  16. One-Step Synthesis of Self-Supported Nickel Phosphide Nanosheet Array Cathodes for Efficient Electrocatalytic Hydrogen Generation.

    PubMed

    Wang, Xiaoguang; Kolen'ko, Yury V; Bao, Xiao-Qing; Kovnir, Kirill; Liu, Lifeng

    2015-07-01

    Nickel phosphide is an emerging low-cost, earth-abundant catalyst that can efficiently reduce water to generate hydrogen. However, the synthesis of nickel phosphide catalysts usually involves multiple steps and is laborious. Herein, a convenient and straightforward approach to the synthesis of a three-dimensional (3D) self-supported biphasic Ni5 P4 -Ni2 P nanosheet (NS) array cathode is presented, which is obtained by direct phosphorization of commercially available nickel foam using phosphorus vapor. The synthesized 3D Ni5 P4 -Ni2 P-NS array cathode exhibits outstanding electrocatalytic activity and long-term durability toward the hydrogen evolution reaction (HER) in acidic medium. The fabrication procedure reported here is scalable, showing substantial promise for use in water electrolysis. More importantly, the approach can be readily extended to synthesize other self-supported transition metal phosphide HER cathodes. PMID:26032688

  17. Tailor Made Synthesis of T-Shaped and ?-STACKED Dimers in the Gas Phase: Concept for Efficient Drug Design and Material Synthesis

    NASA Astrophysics Data System (ADS)

    Kumar, Sumit; Das, Aloke

    2013-06-01

    Non-covalent interactions play a key role in governing the specific functional structures of biomolecules as well as materials. Thus molecular level understanding of these intermolecular interactions can help in efficient drug design and material synthesis. It has been found from X-ray crystallography that pure hydrocarbon solids (i.e. benzene, hexaflurobenzene) have mostly slanted T-shaped (herringbone) packing arrangement whereas mixed solid hydrocarbon crystals (i.e. solid formed from mixtures of benzene and hexafluorobenzene) exhibit preferentially parallel displaced (PD) ?-stacked arrangement. Gas phase spectroscopy of the dimeric complexes of the building blocks of solid pure benzene and mixed benzene-hexafluorobenzene adducts exhibit similar structural motifs observed in the corresponding crystal strcutures. In this talk, I will discuss about the jet-cooled dimeric complexes of indole with hexafluorobenzene and p-xylene in the gas phase using Resonant two photon ionzation and IR-UV double resonance spectroscopy combined with quantum chemistry calculations. In stead of studying benzene...p-xylene and benzene...hexafluorobenzene dimers, we have studied corresponding indole complexes because N-H group is much more sensitive IR probe compared to C-H group. We have observed that indole...hexafluorobenzene dimer has parallel displaced (PD) ?-stacked structure whereas indole...p-xylene has slanted T-shaped structure. We have shown here selective switching of dimeric structure from T-shaped to ?-stacked by changing the substituent from electron donating (-CH3) to electron withdrawing group (fluorine) in one of the complexing partners. Thus, our results demonstrate that efficient engineering of the non-covalent interactions can lead to efficient drug design and material synthesis.

  18. A simple and efficient procedure for the synthesis of 5'-aminoalkyl oligodeoxynucleotides.

    PubMed Central

    Wachter, L; Jablonski, J A; Ramachandran, K L

    1986-01-01

    Synthetic deoxyoligonucleotides have been 5'-aminoalkylated at the end of step-wise synthesis on the polymer support. This was achieved through the activation of the 5'-hydroxyl group as its 5'-imidazolyl derivative using carbonyldiimidazole, which was subsequently displaced with hexamethylene diamine to yield the title compound. The alkyl carbamate linkage thus generated withstands the deprotection conditions used in oligonucleotide synthesis. Purification by gel electrophoresis and further derivatization at the 5'-amino group with N-hydroxysuccinimidobiotin is described. Images PMID:3774550

  19. Deep eutectic solvents and glycerol: a simple, environmentally benign and efficient catalyst\\/reaction media for synthesis of N-aryl phthalimide derivatives

    Microsoft Academic Search

    Hyacintha Rennet Lobo; Balvant Shyam Singh; Ganapati Subray Shankarling

    2012-01-01

    Deep eutectic solvents (DES) and glycerol have been successfully employed as efficient catalysts\\/reaction media in the synthesis of N-aryl phthalimide derivatives from phthalic anhydride and primary aromatic amines. The DES prepared from choline chloride and malonic acid proved to be an efficient catalyst whereas glycerol and the DES of choline chloride and urea played a dual role of catalyst and

  20. Synthesis of macrocyclic organo-peptide hybrids from ribosomal polypeptide precursors via CuAAC-/hydrazide-mediated cyclization.

    PubMed

    Smith, Jessica M; Fasan, Rudi

    2015-01-01

    Macrocyclic peptides have attracted increasing attention as a potential new source of chemical probes and therapeutics. In particular, their conformationally restricted structure combined with a high degree of functional and stereochemical complexity makes them promising scaffolds for targeting biomolecules with high affinity and selectivity. The exploration of this structural class relies on the availability of efficient and versatile methods for the generation of large and diversified libraries of macrocyclic peptide-based molecules. To this end, we have developed a methodology for the synthesis of hybrid organo-peptide macrocycles via the cyclization of ribosomally derived polypeptide sequences with non-peptidic organic linkers. This strategy relies on the chemoselective and bioorthogonal ligation of azide/hydrazide-based "synthetic precursors" with intein-fused polypeptides harboring a side-chain alkyne functionality. This macrocyclization approach was found to proceed with high efficiency across a range of different target peptide sequences spanning 4-12 residues as well as across multiple mono- and diaryl-based synthetic precursors. This versatility combined with the possibility to integrate non-proteinogenic scaffolds into genetically encoded peptide sequences makes this methodology of particularly high value toward the creation and screening of highly diverse libraries of peptide-based macrocycles. PMID:25616323

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

    PubMed

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

    2013-04-01

    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

  2. CuFe2O4 magnetic heterogeneous nanocatalyst: Low power sonochemical-coprecipitation preparation and applications in synthesis of 4H-chromene-3-carbonitrile scaffolds.

    PubMed

    Rajput, Jaspreet Kaur; Arora, Priya; Kaur, Gagandeep; Kaur, Manpreet

    2015-09-01

    The paper presents the synthesis and catalytic activity of CuFe2O4 nanoparticles. The CuFe2O4 nanoparticles have been prepared by sonochemical route under low power ultrasonic irradiation (UI) and using silent stirring at room temperature only (ST) along with co-precipitation method, without using any additive/capping agent. The synthesized magnetic nanoparticles were successfully used and compared for the synthesis of 4H-chromene-3-carbonitrile derivatives. The CuFe2O4 nanoparticles obtained by sonochemical route exhibit higher catalytic activity because of small size (0.5-5nm), high surface area (214.55m(2)/g), high thermal stability up to 700°C, recyclability and reusability due to its magnetic characteristics than CuFe2O4 nanoparticles obtained by room temperature silent stirring. The synthesized CuFe2O4 nanoparticles were characterized by FT-IR, SEM-EDX, HR-TEM, XRD, TGA/DTA/DTG, BET, VSM techniques. The present method is of great interest due to its salient features such as environmentally compatible, efficient, short reaction time, chemoselectivity, high yield, cheap, moisture insensitive, green and recyclable catalyst which make it sustainable protocol. PMID:25649833

  3. [Development of a novel type of Pd/C-catalyzed chemoselective hydrogenation using a nitrogen catalyst poison].

    PubMed

    Sajiki, H

    2000-11-01

    The development of modified Pd catalysts for chemoselective hydrogenation has been a long-standing goal in synthetic chemistry. Several applications of catalyst poisons for this purpose have been studied. But these methods usually lack rules of generality except for a few examples such as Lindlar catalyst and Rosenmund's reaction. Recently, we found that the addition of a nitrogen containing base such as ammonia, triethylamine, pyridine, ammonium acetate, to a Pd/C-catalyzed reduction system selectively inhibited the hydrogenolysis of an aliphatic benzyl ether with smooth hydrogenation of other reducible functions such as olefin, N-Cbz, benzyl ester and azido. However, the selective suppression of hydrogenolysis was not applicable to the benzyl protective group with phenolic hydroxyl functions. The problem has been temporarily, solved by the employment of a 4-methoxybenzyl (MPM) protective group instead of the more reducible benzyl group with phenolic hydroxyl functions. During the course of our further study on the Pd/C-catalyzed chemoselective hydrogenolysis, we further found large differences in the suppressive effect on the hydrogenolysis of O-benzyl protective groups depending upon the nitrogen-containing bases employed as additives. By the use of Pd/C-2,2'-dipyridyl combination as a catalyst for the hydrogenation, aliphatic and phenolic O-benzyl protective groups can be retained without any hydrogenolysis. Further-more, we found that the Pd/C catalyst formed an isolable complex with ethylenediamine employed as a catalytic poison, selectively catalyzing the hydrogenation of various functional groups without hydrogenolysis of O-benzyl protective groups even in phenolic benzyl ethers. PMID:11190196

  4. Prins-Type Macrocyclizations as an Efficient Ring-Closing Strategy in Natural Product Synthesis

    PubMed Central

    Crane, Erika A.; Scheidt, Karl A.

    2011-01-01

    Prins-type macrocyclizations have recently emerged as a successful strategy in the synthesis of polyketide-derived natural products. This reaction provides a concise and selective means to form tetrahydropyran-containing macrocyclic rings of varying size. A high degree of functionality within the macrocycle is tolerated and the yields for these transformations are typically good to excellent. Since the initial report of a Prins macrocyclization reaction in 1979, examples of this approach did not re-emerge until 2008. However, the use of this method in natural product synthesis has rapidly gained momentum in the synthetic community, with multiple examples of this macrocyclization tactic reported in the recent literature. PMID:20931580

  5. Unusual pyrimidine participation: efficient stereoselective synthesis of potent dual orexin receptor antagonist MK-6096.

    PubMed

    Chung, John Y L; Zhong, Yong-Li; Maloney, Kevin M; Reamer, Robert A; Moore, Jeffrey C; Strotman, Hallena; Kalinin, Alexei; Feng, Ronnie; Strotman, Neil A; Xiang, Bangping; Yasuda, Nobuyoshi

    2014-11-21

    An asymmetric synthesis of dual orexin receptor antagonist MK-6096 (1) is described. Key steps for the trans-2,5-disubstituted piperidinyl ether fragment include a biocatalytic transamination, a trans-selective Mukaiyama aldol, and a regioselective pyridyl SNAr process. The pyrimidyl benzoic acid was synthesized via a Negishi coupling and a nitrile hydrolysis. Coupling of the two fragments via a catalytic T3P-mediated amidation completed the synthesis. Unusual behaviors in the hydrolysis of pyrimidyl benzonitrile and the amide coupling of the pyrimidyl benzoic acid are also described. PMID:25365229

  6. Short and Efficient Synthesis of Alkyl- and Aryl-Ortho-Hydroxy-Anilides and their Antibiotic Activity

    PubMed Central

    Krauß, Jürgen; Plesch, Eva; Clausen, Sabine; Bracher, Franz

    2014-01-01

    Abstract Ortho-hydroxy-anilides are part of natural products like the new antibiotics platencin (A) and platensimycin (B). An important step in the total synthesis of these antibiotics or their derivatives is the preparation of the o-hydroxy-anilide partial structure. The presented method allows the preparation of o-hydroxy-anilides and o-dihydroxy-anilides from 2-nitrophenol esters in a one-step synthesis without protecting the hydroxy group. Aryl- and alkyl-anilides were prepared following this method as simple analogues of platensimycin (A). The resulting compounds were tested in an agar diffusion assay for their antibiotic potency. PMID:25853064

  7. Facile solvothermal synthesis of cube-like Ag@AgCl: a highly efficient visible light photocatalyst

    NASA Astrophysics Data System (ADS)

    Han, Lei; Wang, Ping; Zhu, Chengzhou; Zhai, Yueming; Dong, Shaojun

    2011-07-01

    In this paper, a stable and highly efficient plasmonic photocatalyst, Ag@AgCl, with cube-like morphology, has been successfully prepared via a simple hydrothermal method. Using methylene dichloride as chlorine source in the synthesis can efficiently control the morphology of Ag@AgCl, due to the low release rate of chloride ions. Scanning electron microscopy (SEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV-vis diffuse reflectance spectra were used to characterize the obtained product. The photocatalytic activity of the obtained product was evaluated by the photodegradation of methyl orange (MO) under visible light irradiation, and it was found, interestingly, that Ag@AgCl exhibits high visible light photocatalytic activity and good stability.In this paper, a stable and highly efficient plasmonic photocatalyst, Ag@AgCl, with cube-like morphology, has been successfully prepared via a simple hydrothermal method. Using methylene dichloride as chlorine source in the synthesis can efficiently control the morphology of Ag@AgCl, due to the low release rate of chloride ions. Scanning electron microscopy (SEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV-vis diffuse reflectance spectra were used to characterize the obtained product. The photocatalytic activity of the obtained product was evaluated by the photodegradation of methyl orange (MO) under visible light irradiation, and it was found, interestingly, that Ag@AgCl exhibits high visible light photocatalytic activity and good stability. Electronic supplementary information (ESI) available: SEM images of the AgCl samples synthesized by changing the addition amount of PVP and AgNO3. See DOI: 10.1039/c1nr10247h

  8. Rapid microwave synthesis of indium filled skutterudites: An energy efficient route to high performance thermoelectric materials

    SciTech Connect

    Biswas, Krishnendu, E-mail: krishnendu.biswas@oregonstate.edu [Department of Chemistry, Oregon State University, Corvallis, OR 97331 (United States)] [Department of Chemistry, Oregon State University, Corvallis, OR 97331 (United States); Muir, Sean, E-mail: muirs@onid.orst.edu [Department of Chemistry, Oregon State University, Corvallis, OR 97331 (United States)] [Department of Chemistry, Oregon State University, Corvallis, OR 97331 (United States); Subramanian, M.A., E-mail: mas.subramanian@oregonstate.edu [Department of Chemistry, Oregon State University, Corvallis, OR 97331 (United States)

    2011-12-15

    Graphical abstract: Filled skutterudites are promising thermoelectric materials. We report the microwave assisted synthesis of CoSb{sub 3} and In{sub 0.2}Co{sub 4}Sb{sub 12}. This method reduces the calcination time for skutterudite phase formation from 2 days to 2 min, thereby significantly reducing the time and energy needed to produce materials suitable for property and device testing. Highlights: Black-Right-Pointing-Pointer The microwave assisted solid state synthesis of CoSb{sub 3} and In{sub 0.2}Co{sub 4}Sb{sub 12} is reported. Black-Right-Pointing-Pointer This method allows the calcination time to be reduced from 2 days to 2 min. Black-Right-Pointing-Pointer Physical properties of microwave samples match those prepared conventionally. -- Abstract: Filled skutterudites are promising thermoelectric materials due to reduced thermal conductivity upon inserting a guest atom or 'rattler' into the CoSb{sub 3} structure. By using an indium rattler dimensionless Figure of Merit (ZT) values >1 at 650 K have been reported. The conventional synthesis of these compounds typically takes several days ({approx}3 days) to obtain the final well-sintered material for property measurements. We report here a microwave-assisted synthesis method that reduces the initial calcination time from 2 days to 2 min. This route significantly reduces the time needed to produce materials suitable for property and device testing.

  9. Efficient propylene carbonate synthesis from propylene glycol and carbon dioxide via organic bases

    Microsoft Academic Search

    Shiyong Huang; Jun Ma; Junping Li; Ning Zhao; Wei Wei; Yuhan Sun

    2008-01-01

    Organic bases were first used as effective catalysts for the synthesis of propylene carbonate from propylene glycol and carbon dioxide in the presence of acetonitrile. Acetonitrile in the reaction acted as not only the solvent but also the dehydrating reagent to remove the water produced from the reaction. It was interesting that upon ammonium carbonate being introduced into the reaction

  10. Size-Controlled Synthesis of Gold Clusters as Efficient Catalysts for Aerobic Oxidation

    Microsoft Academic Search

    Hironori Tsunoyama; Yongmei Liu; Tomoki Akita; Nobuyuki Ichikuni; Hidehiro Sakurai; Songhai Xie; Tatsuya Tsukuda

    This article summarizes our recent research on the size-controlled synthesis of Au clusters stabilized by a polymer or supported\\u000a by a solid, and related work reported by others. Small Au clusters have excellent, size-specific catalytic activity in the\\u000a aerobic oxidation of alcohols and alkanes.

  11. Chemoselectivity in the microwave-assisted solvent-free solid–liquid phase benzylation of phenols: O- versus C-alkylation

    Microsoft Academic Search

    György Keglevich; Erika Bálint; Éva Karsai; Alajos Grün; Mária Bálint; István Greiner

    2008-01-01

    The outcome of the solvent-free benzylation of phenol and 4-substituted phenols (such as 4-cresol and 4-chlorophenol) under MW irradiation was found to depend on the absence or presence of the base (K2CO3) and catalyst (triethylbenzylammonium chloride (TEBAC)). Reaction of benzyl halides at 80–120°C in the presence of K2CO3 and TEBAC resulted in O-alkylation in high (89–96%) chemoselectivities. In the absence

  12. Selective synthesis of ?,?-dideuterio alcohols by the reduction of carboxylic acids using SmI2 and D2O as deuterium source under SET conditions.

    PubMed

    Szostak, Michal; Spain, Malcolm; Procter, David J

    2014-10-01

    The first general method for the chemoselective synthesis of ?,?-dideuterio alcohols directly from feedstock carboxylic acids under single electron transfer conditions using SmI2 is reported. This reaction proceeds after the activation of Sm(II) with a Lewis base, results in excellent levels of deuterium incorporation across a wide range of substrates, and represents an attractive alternative to processes mediated by pyrophoric alkali metal deuterides. PMID:25247236

  13. Efficient utilization of greenhouse gases in a gas-to-liquids process combined with CO2/steam-mixed reforming and Fe-based Fischer-Tropsch synthesis.

    PubMed

    Zhang, Chundong; Jun, Ki-Won; Ha, Kyoung-Su; Lee, Yun-Jo; Kang, Seok Chang

    2014-07-15

    Two process models for carbon dioxide utilized gas-to-liquids (GTL) process (CUGP) mainly producing light olefins and Fischer-Tropsch (F-T) synthetic oils were developed by Aspen Plus software. Both models are mainly composed of a reforming unit, an F-T synthesis unit and a recycle unit, while the main difference is the feeding point of fresh CO2. In the reforming unit, CO2 reforming and steam reforming of methane are combined together to produce syngas in flexible composition. Meanwhile, CO2 hydrogenation is conducted via reverse water gas shift on the Fe-based catalysts in the F-T synthesis unit to produce hydrocarbons. After F-T synthesis, the unreacted syngas is recycled to F-T synthesis and reforming units to enhance process efficiency. From the simulation results, it was found that the carbon efficiencies of both CUGP options were successfully improved, and total CO2 emissions were significantly reduced, compared with the conventional GTL processes. The process efficiency was sensitive to recycle ratio and more recycle seemed to be beneficial for improving process efficiency and reducing CO2 emission. However, the process efficiency was rather insensitive to split ratio (recycle to reforming unit/total recycle), and the optimum split ratio was determined to be zero. PMID:24933030

  14. An efficient one-pot synthesis of anthraquinone derivatives catalyzed by alum in aqueous media

    Microsoft Academic Search

    Balaji R. Madje; Kiran F. Shelke; Suryakant B. Sapkal; Gopal K. Kakade; Murlidhar S. Shingare

    2010-01-01

    Alum (KAl(SO4)2·12H2O) performs as a novel catalyst for the synthesis of anthraquinone derivatives from phthalic anhydride and substituted benzenes in good to excellent yields (70–96%) using water as a solvent at ambient temperature. Several solvents were examined for this reaction; however, in terms of reaction yield and time, water was found to be the optimum solvent. The remarkable advantages offered

  15. Chitosan-DNA nanoparticles as gene carriers: synthesis, characterization and transfection efficiency

    Microsoft Academic Search

    Hai-Quan Mao; Krishnendu Roy; Vu L. Troung-Le; Kevin A. Janes; Kevin Y. Lin; Yan Wang; J. Thomas August; Kam W. Leong

    2001-01-01

    Chitosan-DNA nanoparticles were prepared using a complex coacervation process. The important parameters for the nanoparticle synthesis were investigated, including the concentrations of DNA, chitosan and sodium sulfate, temperature of the solutions, pH of the buffer, and molecular weights of chitosan and DNA. At an amino group to phosphate group ratio (N\\/P ratio) between 3 and 8 and a chitosan concentration

  16. Synthesis of the Apelsvoll Cropping System Experiment in Norway – Nutrient Balances, Use Efficiencies and Leaching

    Microsoft Academic Search

    Audun Korsaeth; Ragnar Eltun

    In this overview, a synthesis of the first 10 years of the Apelsvoll cropping system experiment, located in southeast Norway,\\u000a is given. All major flows of N, P and K in six different cropping systems, each covering 0.18 ha of separately tile-drained\\u000a plots, were either measured or estimated. The effects of the cropping system on the soil nutrient pools (total-N,

  17. Facile synthesis of silver nano particles with highly efficient anti-microbial property

    Microsoft Academic Search

    Sougata Sarkar; Atish Dipankar Jana; Samir Kumar Samanta; Golam Mostafa

    2007-01-01

    A simple surfactant assisted aqueous solution approach, based on the conventional Tollen’s reaction has been applied for the facile syntheses of silver nano-assembly. Nano particle morphologies strongly depend on the temperature adopted during the synthesis. Two-dimensional (2 D) nano-disks and three-dimensional (3D) nano-globules with “Cauliflower” like morphology were observed. The unique and distinctive feature of the synthesized silver nano particle

  18. An efficient, mild and solvent-free synthesis of benzene ring acylated harmalines.

    PubMed

    Begum, Sabira; Zubair, Farhat; Nawazish, Ali Syed; Siddiqui, Bina Shaheen

    2010-01-01

    A facile synthesis of a series of benzene ring acylated analogues of harmaline has been achieved by Friedel-Crafts acylation under solvent-free conditions at room temperature using acyl halides/acid anhydrides and AlCl3. The reaction afforded 10- and 12-acyl analogues of harmaline in good yield, along with minor quantities of N-acyl-tryptamines and 8-acyl analogues of N-acyltryptamines. PMID:20110872

  19. Relation of Macromolecular Synthesis in Streptococci to Efficiency of Transformation by Markers of Homospecific and Heterospecific Origin

    PubMed Central

    Deddish, Peter A.; Ravin, Arnold W.

    1974-01-01

    In previous studies with Streptococcus sanguis and S. pneumoniae as recipients and donors of transforming deoxyribonucleic acid (DNA), it was found that heating recipients just prior to exposure to DNA caused an increase in the number of transformants induced by heterospecific DNA relative to that induced by homospecific DNA. In the present studies, S. sanguis recipients were found to recover from this effect of heat (48 C, 15 min) when incubated at 37 C before exposure to DNA. Inhibitors of nucleic acid synthesis, such as rifampin, 5-fluorodeoxyuridine, actinomycin, and p-hydroxyphenylazo-uracil, but not inhibitors of protein synthesis, such as chloramphenicol and erythromycin, prevented recovery from the effect of heat. Inhibitors of nucleic acid synthesis caused changes in unheated cells similar to those observed with heat treatment; these changes included increased transformability by genetically hybrid DNA and by low-efficiency markers in homospecific DNA. The effect of a combination of heat and inhibitors on transformation by heterospecific DNA was greater than when single treatments were used. The most effective inhibitor used alone was rifampin: in treated recipient cells, the yield of transformants produced by a given amount of irreversibly bound heterospecific DNA was increased without a significant change in the yield of transformants produced by bound homospecific DNA. A cell being doubly transformed by homospecific and heterospecific DNA was enhanced specifically in its transformability with the latter as a consequence of rifampin treatment. Treatment with rifampin also increased co-transformation by linked heterospecific markers. The period during which recipient cells were sensitive to the effects induced by rifampin and fluorodeoxyuridine lasted from 10 to 20 min after DNA uptake. PMID:4130687

  20. Efficient synthesis of secondary alkyl fluorides via Suzuki cross-coupling reaction of 1-halo-1-fluoroalkanes.

    PubMed

    Jiang, Xiaojian; Sakthivel, Sekarpandi; Kulbitski, Kseniya; Nisnevich, Gennady; Gandelman, Mark

    2014-07-01

    Organofluorine compounds have found extensive applications in various areas of science. Consequently, the development of new efficient and selective methods for their synthesis is an important goal in organic chemistry. Here, we present the first Suzuki cross-coupling reaction which utilizes dihalo compounds for the preparation of secondary alkyl fluorides. Namely, an unprecedented use of simple 1-halo-1-fluoroalkanes as electrophiles in C(sp(3))-C(sp(3)) and C(sp(3))-C(sp(2)) cross-couplings allows for the formal site-selective incorporation of F-group in the alkyl chain with no adjacent activating functional groups. Highly effective approach to the electrophilic substrates, 1-halo-1-fluoroalkanes, via iododecarboxylation of the corresponding ?-fluorocarboxylic acids is also presented. The conceptually new route to organofluorides was used for the facile preparation of biomedically valuable compounds. In addition, we demonstrated that an asymmetric version of the developed reaction for the stereoconvergent synthesis of chiral secondary alkyl fluorides is feasible. PMID:24958322

  1. Nano-sized copper as an efficient catalyst for one pot three component synthesis of thiazolidine-2,4-dione derivatives

    Microsoft Academic Search

    Ajeet Kumar; Prashant Singh; Amit Saxena; Arnab De; Ramesh Chandra; Subho Mozumdar

    2008-01-01

    A simple, efficient, stereoselective, one pot three component condensation reaction between thiazolidine-2,4-dione, aldehyde and amine derivatives using monodispersed, recyclable and inexpensive Cu-nanoparticles for the synthesis of thiazolidine-2,4-dione derivatives in excellent yields and high purity has been described here for the first time.

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

    PubMed

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

    2014-10-31

    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. PMID:25300279

  3. Gold-catalyzed efficient tandem assembly of terminal alkynes and arynes: synthesis of alkynylated biphenyl derivatives.

    PubMed

    Xie, Chunsong; Zhang, Yuhong; Yang, Yuzhu

    2008-10-21

    Gold catalysts have been found to catalyze the tandem assembly of arynes and terminal alkynes efficiently in the presence of CuI under mild reaction conditions to provide useful alkynylated biphenyl derivatives. PMID:18830501

  4. A primase subunit essential for efficient primer synthesis by an archaeal eukaryotic-type primase.

    PubMed

    Liu, Bing; Ouyang, Songying; Makarova, Kira S; Xia, Qiu; Zhu, Yanping; Li, Zhimeng; Guo, Li; Koonin, Eugene V; Liu, Zhi-Jie; Huang, Li

    2015-01-01

    Archaea encode a eukaryotic-type primase comprising a catalytic subunit (PriS) and a noncatalytic subunit (PriL). Here we report the identification of a primase noncatalytic subunit, denoted PriX, from the hyperthermophilic archaeon Sulfolobus solfataricus. Like PriL, PriX is essential for the survival of the organism. The crystallographic analysis complemented by sensitive sequence comparisons shows that PriX is a diverged homologue of the C-terminal domain of PriL but lacks the iron-sulfur cluster. Phylogenomic analysis provides clues on the origin and evolution of PriX. PriX, PriL and PriS form a stable heterotrimer (PriSLX). Both PriSX and PriSLX show far greater affinity for nucleotide substrates and are substantially more active in primer synthesis than the PriSL heterodimer. In addition, PriL, but not PriX, facilitates primer extension by PriS. We propose that the catalytic activity of PriS is modulated through concerted interactions with the two noncatalytic subunits in primer synthesis. PMID:26095544

  5. Design and Synthesis of Efficient Fluorescent Dyes for Incorporation into DNA Backbone and Biomolecule Detection

    PubMed Central

    Wang, Wei; Li, Alexander D. Q.

    2008-01-01

    We report here the design and synthesis of a series of ?-conjugated fluorescent dyes with D-A-D (D: donor; A: Acceptor), D-?-D, A-?-A, and D-?-A for applications as the signaling motif in biological-synthetic hybrid foldamers for DNA detection. Horner-Wadsworth-Emmons (HWE) reaction and Knoevenagel condensation were demonstrated as the optimum ways for construction of long ?-conjugated systems. Such rod-like chromophores have distinct advantages, as their fluorescence properties are not quenched by the presence of DNA. To be incorporated into the backbone of DNA, the chromophores need to be reasonably soluble in organic solvent for solid-phase synthesis, and therefore a strategy of using flexible tetra(ethylene glycol) (TEG) linkers at either end of these rod-like dyes were developed. The presence of TEG facilitates the protection of the chain-growing hydroxyl group with DMTrCl (dimethoxy trityl chloride) as well as the activation of the coupling step with phosphoramidite chemistry on an automated DNA synthesizer. To form fluorescence resonance energy transfer (FRET) pairs, six synthetic chromophores with blue to red fluorescence have been developed and those with orthogonal fluorescent emission were chosen for incorporation into DNA-chromophore hybrid foldamers. PMID:17508711

  6. Efficient synthesis of methyl lycotetraoside, the tetrasaccharide constituent of the tomato defence glycoalkaloid alpha-tomatine.

    PubMed

    Jones, Nigel A; Nepogodiev, Sergey A; Field, Robert A

    2005-09-01

    Branched oligosaccharide lycotetraose, beta-D-glucopyranosyl-(1-->2)-[beta-D-xylopyranosyl-(1-->3)]-beta-D-glucopyranosyl-(1-->4)-beta-D-galactopyranose, is a key constituent of many steroidal saponins, including glycoalkaloid alpha-tomatine, which is involved in protection of plants from invading pathogens. A new synthesis of the methyl beta-lycotetraoside () is described. Key steps of the synthesis include two successive glycosylation reactions of disaccharide acceptor methyl (4,6-O-benzylidene-3-O-p-methoxybenzyl-beta-D-glucopyranosyl)-(1-->4)-2,3,6-tri-O-benzyl-beta-D-galactopyranoside with readily available benzoylated trichloroacetimidates of alpha-D-glucopyranose and alpha,beta-D-xylopyranose. This scheme allows sequential glycosylation in one-pot on account of the convenient in situ removal of a p-methoxybenzyl protecting group under the acid conditions of the first glycosylation step. Following deprotection, tetrasaccharide was obtained in 19% yield over eight steps. PMID:16106302

  7. One-pot RAFT/"click" chemistry via isocyanates: efficient synthesis of ?-end-functionalized polymers.

    PubMed

    Gody, Guillaume; Rossner, Christian; Moraes, John; Vana, Philipp; Maschmeyer, Thomas; Perrier, Sébastien

    2012-08-01

    A new methodology has been developed for preparing ?-functional polymers in a one-pot simultaneous polymerization/isocyanate "click" reaction. Our original synthetic strategy is based on the preparation of a carbonyl-azide chain transfer agent (CTA) precursor that undergoes the Curtius rearrangement in situ during reversible addition-fragmentation chain transfer (RAFT) polymerization yielding well-controlled ?-isocyanate modified polymers. This strategy overcomes numerous difficulties associated with the synthesis of a polymerization mediator bearing an isocyanate at the R group and with the handling of such a reactive functionality. This new carbonyl-azide CTA can control the polymerization of a wide range of monomers, including (meth)acrylates, acrylamides, and styrenes (M(n) = 2-30 kDa; ? = 1.16-1.38). We also show that this carbonyl-azide CTA can be used as a universal platform for the synthesis of ?-end-functionalized polymers in a one-pot RAFT polymerization/isocyanate "click" procedure. PMID:22731785

  8. Automated synthesis of reliable and efficient systems through game theory: a case study

    E-print Network

    Randour, Mickael

    2012-01-01

    Reactive computer systems bear inherent complexity due to continuous interactions with their environment. While this environment often proves to be uncontrollable, we still want to ensure that critical computer systems will not fail, no matter what they face. Examples are legion: railway traffic, power plants, plane navigation systems, etc. Formal verification of a system may ensure that it satisfies a given specification, but only applies to an already existing model of a system. In this work, we address the problem of synthesis: starting from a specification of the desired behavior, we show how to build a suitable system controller that will enforce this specification. In particular, we discuss recent developments of that approach for systems that must ensure Boolean behaviors (e.g., reachability, liveness) along with quantitative requirements over their execution (e.g., never drop out of fuel, ensure a suitable mean response time). We notably illustrate a powerful, practically useable algorithm for the aut...

  9. Origin of chemoselective behavior of S-covered Cu(1 1 1) towards catalytic hydrogenation of unsaturated aldehydes

    NASA Astrophysics Data System (ADS)

    Boronat, Mercé; May, Marcos; Illas, Francesc

    2008-11-01

    The molecular structure of acrolein and crotonaldehyde adsorbed on clean and S-covered Cu(1 1 1) surfaces has been theoretically investigated in order to explain the mechanism of selective activation of the carbonyl group induced by the presence of small amounts of S on the metal surface. While on clean Cu(1 1 1) there is an equilibrium between a physisorbed and chemisorbed species, it is found that addition of small amounts of S enhances and modifies the metal-molecule interaction, in agreement with experimental evidence. On the S-covered Cu(1 1 1) the aldehyde is bonded to the surface through the O of the carbonyl group which is slightly stretched whereas the C dbnd C bond remains undistorted and far away from the surface. This geometrical conformation induced by the presence of coadsorbed S activates the C dbnd O group and renders the C dbnd C bond inaccessible to hydrogen adatoms. We argue that this is the origin of the chemoselectivity enhancement towards the crotyl alcohol experimentally observed.

  10. Synthesis of Bismuth-Nanoparticle-Enriched Nanoporous Carbon on Graphene for Efficient Electrochemical Analysis of Heavy-Metal Ions.

    PubMed

    Cui, Lin; Wu, Jie; Ju, Huangxian

    2015-08-01

    A BiNPs@NPCGS nanocomposite was designed for highly efficient detection of multiple heavy-metal ions by in situ synthesis of bismuth-nanoparticle (BiNP)-enriched nanoporous carbon (NPS) on graphene sheet (GS). The NPCGS was prepared by pyrolysis of zeolitic imidazolate framework-8 (ZIF-8) nanocrystals deposited on graphene oxide and displayed a high surface area of 1251?m(2) ?g(-1) and a pore size of 3.4?nm. BiNPs were deposited on NPCGS in situ by chemical reduction of Bi(3+) with NaBH4 . Due to the restrictive effect of the pore/surface structure of NPCGS, the BiNPs were uniform and well dispersed on the NPCGS. The BiNPs@NPCGS showed good conductivity and high effective area, and the presence of BiNPs allowed it to act as an efficient material for anodic-stripping voltammetric detection of heavy-metal ions. Under optimized conditions, the BiNPs@NPCGS-based sensor could simultaneously determine Pb(2+) and Cd(2+) with detection limits of 3.2 and 4.1?nM, respectively. Moreover, the proposed sensor could also differentiate Tl(+) from Pb(2+) and Cd(2+) . Owing to its advantages of simple preparation, environmental friendliness, high surface area, and fast electron-transfer ability, BiNPs@NPCGS showed promise for practical application in sensing heavy-metal ions. PMID:26130217

  11. 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: yangyunxia@ecust.edu.cn, E-mail: grchen@ecust.edu.cn; Chen, Guorong, E-mail: yangyunxia@ecust.edu.cn, E-mail: grchen@ecust.edu.cn [Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China); Zhang, Bo [Department of Physics, East China University of Science and Technology, Shanghai 200237 (China)

    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%.

  12. Study on systematizing the synthesis of the a-series ganglioside glycans GT1a, GD1a, and GM1 using the newly developed N-Troc-protected GM3 and GalN intermediates

    Microsoft Academic Search

    Tatsuya Komori; Akihiro Imamura; Hiromune Ando; Hideharu Ishida; Makoto Kiso

    2009-01-01

    A first systematic synthesis of the glycan parts of the a-series gangliosides (GT1a, GD1a, and GM1) utilizing the newly developed N-Troc-protected GM3 and galactosaminyl building blocks is described. The key processes, including the assembly of the GM2 sequence and its conversion into the 3-hydroxy acceptor, were facilitated mainly by the high degree of participation and chemoselective cleavability of the Troc

  13. An efficient synthesis of isoquinolines via rhodium-catalyzed direct C-H functionalization of arylhydrazines.

    PubMed

    Zhang, Sai; Huang, Daorui; Xu, Guangyang; Cao, Shengyu; Wang, Rong; Peng, Shiyong; Sun, Jiangtao

    2015-08-01

    A highly efficient rhodium-catalyzed C-H activation of arylhydrazines and coupling with internal alkynes has been realized under mild conditions. The isoquinolines have been prepared in moderate to excellent yields in high efficiency. This methodology features the use of readily available starting materials, and a simple hydrazine moiety as a directing group, in the absence of an external metal co-oxidant under an air atmosphere. The C-H bond activation and the N-N bond cleavage have been successively realized under mild conditions. PMID:26138437

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

    E-print Network

    Cao, Guozhong

    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. Li-ion batteries, functioning as a key component of energy-storage, have been heralded

  15. Efficient Methodology for the Synthesis of 3-Amino-1,2,4-triazoles

    PubMed Central

    Noël, Romain; Song, Xinyi; Jiang, Rong; Chalmers, Michael J.; Griffin, Patrick R.; Kamenecka, Theodore M.

    2010-01-01

    A general and efficient method for the preparation of 3-amino-1,2,4-triazoles has been developed. The desired 3-amino-1,2,4-triazoles (1) were prepared in good overall yield via two convergent routes. The key intermediate within both routes is substituted hydrazinecarboximida-mide derivative 2. PMID:19731897

  16. Synthesis and Preliminary Demulsification Efficiency Evaluation of New Demulsifiers Based on Fatty Oils

    Microsoft Academic Search

    Rasha A. El-Ghazawy; Ahmed M. Al-Sabagh; Nadia G. Kandile; Mahmoud R. Noor El-Din

    2010-01-01

    Three raw fatty oils were used as precursors for demulsifiers. The hydrolyzed form of each oil was adducted with maleic anhydride then modified by esterification with polyethylene glycols or ethyleneoxide-propyleneoxide block copolymers. The demulsfication efficiency, coalescence rate, some surface active, thermodynamic properties, and partition coefficient of a selected demulsifier were investigated. The best demulsifier shows 100% demulsification after 19 minutes

  17. An Efficient Synthesis of the Fully Elaborated Isoindolinone Unit of Muironolide A

    PubMed Central

    Xiao, Qing; Young, Kyle

    2013-01-01

    An efficient stereocontrolled construction of the fully substituted isoindolone subunit of muironolide A is described. The approach is centered on the intramolecular Diels-Alder reaction between the enol form of the ?-keto amide and an ? ? ? ?-unsaturated ester, followed by the installation of the cyclohexene double bond. PMID:23826676

  18. Efficient production of isotopically labeled proteins by cell-free synthesis: A practical protocol

    Microsoft Academic Search

    Takuya Torizawa; Masato Shimizu; Masato Taoka; Hiroshi Miyano; Masatsune Kainosho

    2004-01-01

    We provide detailed descriptions of our refined protocols for the cell-free production of labeled protein samples for NMR spectroscopy. These methods are efficient and overcome two critical problems associated with the use of conventional Escherichia coli extract systems. Endogenous amino acids normally present in E. coli S30 extracts dilute the added labeled amino acids and degrade the quality of NMR

  19. A Methodology for Synthesis of Efficient Intrusion Detection Systems on FPGAs

    Microsoft Academic Search

    Zachary K. Baker; Viktor K. Prasanna

    2004-01-01

    Intrusion detection for network security is a computa- tion intensive application demanding high system perfor- mance. System level design, a relatively unexplored field in this area, allows more efficient communication and ex- tensive reuse of hardware components for dramatic in- creases in area-time performance. By applying optimiza- tion strategies to the entire database, we reduce hardware requirements compared to architectures

  20. Peptide arrays on cellulose support: SPOT synthesis, a time and cost efficient method for synthesis of large numbers of peptides in a parallel and addressable fashion

    Microsoft Academic Search

    Dirk FH Winkler; Robert EW Hancock; Kai Hilpert

    2007-01-01

    Peptide synthesis on cellulose using SPOT technology allows the parallel synthesis of large numbers of addressable peptides in small amounts. In addition, the cost per peptide is less than 1% of peptides synthesized conventionally on resin. The SPOT method follows standard fluorenyl-methoxy-carbonyl chemistry on conventional cellulose sheets, and can utilize more than 600 different building blocks. The procedure involves three

  1. A facile low temperature synthesis of TiO2 nanorods for high efficiency dye sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Shalan, A. E.; Rashad, M. M.; Yu, Youhai; Lira-Cantú, Mónica; Abdel-Mottaleb, M. S. A.

    2013-01-01

    Titania (TiO2) nanorods have been synthesized with controlled size for dye-sensitized solar cells (DSSCs) via hydrothermal route at low hydrothermal temperature of 100 °C for 24 h. The titania nanorods were characterized using XRD, SEM, TEM/HRTEM, UV-vis Spectroscopy, FTIR and BET specific surface area ( S BET), as well as pore-size distribution by BJH. The results indicated that the bulk traps and the surface states within the TiO2 nanorods films have enhanced the efficiency of DSSCs. The size of the titania nanorods was 6.7 nm in width and 22 nm in length. The high surface area can provide more sites for dye adsorption, while the fast photoelectron-transfer channel can enhance the photogenerated electron transfer to complete the circuit. The specific surface area S BET was 77.14 m2 g-1 at the synthesis conditions. However, the band gap energy of the obtained titania nanorods was 3.2 eV. The oriented nanorods with appropriate lengths are beneficial in improving the electron transport property and thus leading to the increase of photocurrent, together enhancing the power conversion efficiency. A nearly quantitative absorbed photon-to-electrical current conversion achieved upon excitation at wave length of 550 nm and the power efficiency was enhanced from 5.6 % for commercial TiO2 nanoparticles Degussa (P25) cells to 7.2 % for TiO2 nanorods cells under AM 1.5 illumination (100 mW cm-2). The TiO2 cells performance was improved due to their high surface area, hierarchically mesoporous structures and fast electron-transfer rate compared with the Degussa (P25).

  2. Efficient synthesis and cell-transfection properties of a new multivalent cationic lipid for nonviral gene delivery.

    PubMed

    Ewert, Kai; Ahmad, Ayesha; Evans, Heather M; Schmidt, Hans-Werner; Safinya, Cyrus R

    2002-11-01

    Lipid-mediated delivery of DNA into cells holds great promise both for gene therapy and basic research applications. This paper describes the efficient and facile synthesis and the characterization of a new multivalent cationic lipid with a double-branched headgroup structure for gene delivery applications. The synthetic scheme can be extended to give cationic lipids of different charge, spacer, or lipid chain length. The chemical and physical properties of self-assembled complexes of the cationic liposomes (CLs) with DNA give indications of why multivalent cationic lipids possess superior transfection properties. The lipid bears a headgroup with five charges in the fully protonated state, which is attached to an unsaturated double-chain hydrophobic moiety based on 3,4-dihydroxybenzoic acid. Liposomes consisting of the new multivalent lipid and the neutral lipid 1,2-dioleoyl-sn-glycerophosphatidylcholine (DOPC) were used to prepare complexes with DNA. Investigations of the structures of these complexes by optical microscopy and small-angle X-ray scattering reveal a lamellar L(alpha)(C) phase of CL-DNA complexes with the DNA molecules sandwiched between bilayers of the lipids. Experiments using plasmid DNA containing the firefly luciferase reporter gene show that these complexes efficiently transfect mammalian cells. When compared to the monovalent cationic lipid 2,3-dioleyloxypropyltrimethylammonium chloride (DOTAP), the higher charge density of the membranes of CL-DNA complexes achievable with the new multivalent lipid greatly increases transfection efficiency in the regime of small molar ratios of cationic to neutral lipid. This is desired to minimize the known toxicity effects of cationic lipids. PMID:12408712

  3. 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.

  4. The Efficient Synthesis and Biological Evaluation of Novel Bi-Functionalized Sarcophagine for 64Cu Radiopharmaceuticals

    PubMed Central

    Liu, Shuanglong; Li, Dan; Huang, Chiun-Wei; Yap, Li-Peng; Park, Ryan; Shan, Hong; Li, Zibo; Conti, Peter S.

    2012-01-01

    Purpose We and others have reported that Sarcophagine-based bifunctional chelators could be effectively used in the syntheses of 64Cu radiopharmaceuticals. The resulted 64Cu-Sarcophagine complexes demonstrated great in vivo stability. The goal of this study was to further derivatize Sarcophagine cage with amino and maleimide functional groups for conjugation with bioligands. Methods Starting from DiAmSar, three novel chelators (AnAnSar, BaMalSar, and Mal2Sar) with two functional groups have been synthesized. Among those, BaMalSar and Mal2Sar have been conjugated with cyclic peptide c(RGDyC) (denoted as RGD) and the resulted conjugates, BaMalSar-RGD and Mal2Sar-RGD2 have been labeled with 64Cu. The tumor targeting efficacy of 64Cu-labeled RGD peptides were evaluated in a subcutaneous U87MG glioblastoma xenograft model. Results The conjugates, BaMalSar-RGD and Mal2Sar-RGD2 could be labeled with 64CuCl2 in 10 min with high purity (>98%) and high radiochemical yield (>90%). Both 64Cu-BaMalSar-RGD and 64Cu-Mal2Sar-RGD2 exhibited high tumor uptake and tumor-to-normal tissue ratios. Conclusion Three novel chelators with two functional groups have been developed based on Sarcophagine cage. The platform developed in this study could have broad applications in the design and synthesis of 64Cu-radiopharmaceuticals. PMID:22737194

  5. A new and efficient method for the synthesis of Ulipristal acetate.

    PubMed

    Cheng, Xu; Li, Xiaocen; Duan, Yanjun; Yu, Yongguo; Hai, Li; Wu, Yong

    2014-06-01

    In this study, we describe another new and efficient route for preparing Ulipristal acetate. The 1,4-addition compound 5 was greatly improved after the starting material ketone 1 was underwent epoxidation, cyanation, hydroxyl group protection and Grignard addition. The synthetic procedure is only 6 steps and the total yield is about 27.4%, which is much suitable for industrial process. PMID:24686204

  6. Efficient and facile synthesis of acrylamide libraries for protein-guided tethering.

    PubMed

    Allen, Charlotte E; Curran, Peter R; Brearley, Andrew S; Boissel, Valerie; Sviridenko, Lilya; Press, Neil J; Stonehouse, Jeffrey P; Armstrong, Alan

    2015-02-01

    A kinetic template-guided tethering (KTGT) strategy has been developed for the site-directed discovery of fragments that bind to defined protein surfaces, where acrylamide-modified fragments can be irreversibly captured in a protein-templated conjugate addition reaction. Herein, an efficient and facile method is reported for the preparation of acrylamide libraries from a diverse range of amine fragments using a solid-supported quaternary amine base. PMID:25582165

  7. Efficient Synthesis of Octahydrophenanthrene Derivatives with Mild Cascade Reactions of Isochromenylium Tetrafluoroborates and Bifunctional Styrenes.

    PubMed

    Mo, Lei; Wu, Lin-Lin; Wang, Shaozhong; Yao, Zhu-Jun

    2015-07-01

    A highly efficient catalyst-free cascade reaction of air-stable isochromenylium tetrafluoroborates and bifunctional styrenes containing a 1,3-diketone moiety has been developed, affording the corresponding single diastereomeric ocatahydrophenanthrene derivatives (21 examples, up to 86% yield). A cascade process of [4 + 2]-cyclization and subsequent intramolecular nucleophilic addition is proposed to generate the three new C-C bonds diastereoselectively in the reactions. PMID:26098712

  8. Energy-Efficient Synthesis of Periodic Task Systems upon Identical Multiprocessor Platforms

    Microsoft Academic Search

    James H. Anderson; Sanjoy K. Baruah

    2004-01-01

    Multiprocessor implementations of real-time systems tend to be more energy-efficient than uniprocessor implementations. However several factors, including the nonexistence of optimal multiprocessor scheduling algorithms, combine to prevent all the computing capacity of a multiprocessor platform from being guaranteed available for executing the real-time workload. In this paper, this tradeoff - that while increasing the number of processors results in lower

  9. Efficient synthesis of carbazolespirooxindole skeletons via asymmetric Diels-Alder reaction of 3-vinylindoles and methyleneindolinones.

    PubMed

    Zheng, Haifeng; He, Peng; Liu, Yangbin; Zhang, Yulong; Liu, Xiaohua; Lin, Lili; Feng, Xiaoming

    2014-08-14

    A highly efficient catalytic asymmetric Diels-Alder reaction between 3-vinylindoles and methyleneindolinones has been achieved using chiral N,N'-dioxide-Ni(II) complexes as the catalysts. A wide variety of substrates were readily tolerated, generating exclusively the corresponding exo-carbazolespirooxindole derivatives in excellent yields with high enantiomeric excesses (up to 98% yield, >99?:?1 d.r., and 98% ee) under mild reaction conditions. PMID:24967917

  10. 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

  11. 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

  12. Polyvinyl alcohol: an efficient fuel for synthesis of superparamagnetic LSMO nanoparticles for biomedical application.

    PubMed

    Thorat, N D; Shinde, K P; Pawar, S H; Barick, K C; Betty, C A; Ningthoujam, R S

    2012-03-14

    La(0.7)Sr(0.3)MnO(3) (LSMO) nanoparticles have been prepared using glycine and polyvinyl alcohol (PVA) as fuels. Their crystal structure, particle morphology and compositions are characterized using X-ray diffraction, transmission electron microscopy, field-emission electron microscopy and energy dispersive analysis of X-ray. They show a pseudo-cubic perovskite structure. The spherical particle sizes of 30 and 20 nm have been obtained from samples prepared by glycine and PVA respectively. The field cooled (FC) and zero field cooled (ZFC) magnetizations have been recorded from 5 to 375 K at 500 Oe and superparamagnetic blocking temperatures (T(B)) of 75 and 30 K are obtained from samples prepared by glycine and PVA respectively. Particle size distribution is observed from dynamic light scattering measurements. Dispersion stability of the particles in water is studied by measuring the Zeta potential with varying the pH of the medium from 1 to 12. Under induction heating experiments, a hyperthermia temperature (42-43 °C) is achieved by both the samples (3-6 mg mL(-1)) at magnetic fields of 167-335 Oe and at a frequency of 267 kHz. The bio-compatibility of the LSMO nanoparticles is studied on the L929 and HeLa cell lines by MTT assay for up to 48 h. The present work reveals the importance of synthesis technique and fuel choice on structural, morphological, magnetic, hyperthermia and biocompatible properties of LSMO and predicts the suitability for biomedical applications. PMID:22277953

  13. Efficient chemoenzymatic synthesis of novel galacto-N-biose derivatives and their sialylated forms.

    PubMed

    Li, Lei; Liu, Yonghui; Li, Tiehai; Wang, Wenjun; Yu, Zaikuan; Ma, Cheng; Qu, Jingyao; Zhao, Wei; Chen, Xi; Wang, Peng G

    2015-06-11

    Galacto-N-biose (GNB) derivatives were efficiently synthesized from galactose derivatives via a one-pot two-enzyme system containing two promiscuous enzymes from Bifidobacterium infantis: a galactokinase (BiGalK) and a d-galactosyl-?1-3-N-acetyl-d-hexosamine phosphorylase (BiGalHexNAcP). Mono-sialyl and di-sialyl galacto-N-biose derivatives were then prepared using a one-pot two-enzyme system containing a CMP-sialic acid synthetase and an ?2-3-sialyltransferase or an ?2-6-sialyltransferase. PMID:26023910

  14. Autographa californica multiple nucleopolyhedrovirus ac66 is required for the efficient egress of nucleocapsids from the nucleus, general synthesis of preoccluded virions and occlusion body formation

    SciTech Connect

    Ke Jianhao [State Key Laboratory of Biocontrol, School of Life Sciences, Sun Yat-sen University, 510275 Guangzhou (China)], E-mail: kejhkejh@yahoo.cn; Wang Jinwen; Deng Riqiang [State Key Laboratory of Biocontrol, School of Life Sciences, Sun Yat-sen University, 510275 Guangzhou (China); Wang Xunzhang [State Key Laboratory of Biocontrol, School of Life Sciences, Sun Yat-sen University, 510275 Guangzhou (China)], E-mail: wxz@mail.sysu.edu.cn

    2008-05-10

    Although orf66 (ac66) of Autographa californica multiple nucleopolyhedrovirus (AcMNPV) is conserved in all sequenced lepidopteran baculovirus genomes, its function is not known. This paper describes generation of an ac66 knockout AcMNPV bacmid mutant and analyses of the influence of ac66 deletion on the virus replication in Sf-9 cells so as to determine the role of ac66 in the viral life cycle. Results indicated that budded virus (BV) yields were reduced over 99% in ac66-null mutant infected cells in comparison to that in wild-type virus infected cells. Optical microscopy revealed that occlusion body synthesis was significantly reduced in the ac66 knockout bacmid-transfected cells. In addition, ac66 deletion interrupted preoccluded virion synthesis. The mutant phenotype was rescued by an ac66 repair bacmid. On the other hand, real-time PCR analysis indicated that ac66 deletion did not affect the levels of viral DNA replication. Electron microscopy revealed that ac66 is not essential for nucleocapsid assembly, but for the efficient transport of nucleocapsids from the nucleus to the cytoplasm. These results suggested that ac66 plays an important role for the efficient exit of nucleocapsids from the nucleus to the cytoplasm for BV synthesis as well as for preoccluded virion and occlusion synthesis.

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

    SciTech Connect

    Xu, Fang [Engineering Technology Research Center of Motive Power and Key Materials of Henan Province, Xinxiang 453007 (China); School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007 (China); Yuan, Yafei [School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007 (China); Wu, Dapeng [Engineering Technology Research Center of Motive Power and Key Materials of Henan Province, Xinxiang 453007 (China); School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007 (China); Zhao, Mei [QUE MING HU Scientific and Technological Industry Park, Yingkou 115010 (China); Gao, Zhiyong [Engineering Technology Research Center of Motive Power and Key Materials of Henan Province, Xinxiang 453007 (China); School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007 (China); Jiang, Kai, E-mail: jiangkai6898@126.com [Engineering Technology Research Center of Motive Power and Key Materials of Henan Province, Xinxiang 453007 (China); School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007 (China)

    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.

  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. 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

  18. Synthesis efficiency of heavy carbon clusters from ETFE ablated by different numbers of laser pulse in vacuum

    NASA Astrophysics Data System (ADS)

    Shibagaki, K.; Takada, N.; Sasaki, K.; Kadota, K.

    2002-09-01

    We have carried out mass spectral analysis of positive ions produced by laser ablation of a copolymer of ethylene and tetrafluoroethylene (ETFE: [?CH 2?CH 2?CF 2?CF 2?] n) in vacuum using time-of-flight mass spectrometry (TOF-MS). The surfaces of the ETFE targets irradiated by different numbers of laser pulse were analyzed by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Heavy carbon cluster ions C n+ with n?30 were observed in the mass spectra. The fractional abundance of heavy clusters in the mass spectrum decreased with the number of laser pulse. On the other hand, carbon became rich in the atomic composition of the laser-irradiated surface, and the eroded area on the surface increased with the number of laser pulse. From these results, it is suggested that the carbon-rich material surface results in the less efficient production of heavy carbon clusters. In addition, it is also suggested that clustering reactions in eroded craters do not contribute to the synthesis of heavy clusters.

  19. 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

  20. Efficient Synthesis and Anti-Tubercular Activity of a Series of Spirocycles: An Exercise in Open Science

    PubMed Central

    Badiola, Katrina A.; Quan, Diana H.; Triccas, James A.; Todd, Matthew H.

    2014-01-01

    Tuberculosis afflicts an estimated 2 billion people worldwide and causes 1.3 million deaths annually. Chemotherapeutic solutions rely on drugs developed many years ago, with only one new therapeutic having been approved in the last 40 years. Given the rise of drug-resistant strains, there is an urgent need for the development of a more robust drug development pipeline. GlaxoSmithKline recently placed the structures and activities of 177 novel anti-tubercular leads in the public domain, as well as the results of ongoing optimisation of some of the series. Since many of the compounds arose from screening campaigns, their provenance was unclear and synthetic routes were in many cases not reported. Here we present the efficient synthesis of several novel analogues of one family of the GSK compounds—termed “Spiros”—using an oxa-Pictet–Spengler reaction. The new compounds are attractive from a medicinal chemistry standpoint and some were potent against the virulent strain, suggesting this class is worthy of further study. The research was carried out using open source methodology, providing the community with full access to all raw experimental data in real time. PMID:25493550

  1. Highly efficient synthesis of (R)-3-quinuclidinol in a space-time yield of 916 g L(-1) d(-1) using a new bacterial reductase ArQR.

    PubMed

    Zhang, Wen-Xia; Xu, Guo-Chao; Huang, Lei; Pan, Jiang; Yu, Hui-Lei; Xu, Jian-He

    2013-10-01

    A new keto reductase (ArQR), identified from Agrobacterium radiobacter ECU2556, can efficiently reduce 3-quinuclidinone in excellent enantioselectivity and high space-time yield for the synthesis of (R)-3-quinuclidinol, a chiral building block of many antimuscarinic agents. This is the first time that a high yield of (R)-3-quinuclidinol up to 916 g L(-1) d(-1) using a bioreduction approach is reported. PMID:24050153

  2. Dual-activation protocol for tandem cross-aldol condensation: An easy and highly efficient synthesis of ?,??-bis(aryl\\/alkylmethylidene)ketones

    Microsoft Academic Search

    Srikant Bhagat; Ratnesh Sharma; Asit K. Chakraborti

    2006-01-01

    Commercially available lithium hydroxide monohydrate (LiOH·H2O) was found to be a novel ‘dual activation’ catalyst for tandem cross-aldol condensation between cyclic\\/acyclic ketones and aromatic\\/heteroaromatic\\/styryl\\/alkyl aldehydes leading to an efficient and easy synthesis of ?,??-bis(aryl\\/alkylmethylidene)ketones at r.t. in short times. The reaction of aryl, heteroaryl, styryl and alkyl aldehydes with acyclic and five\\/six-membered cyclic ketones afforded excellent yields after 2min to

  3. A novel and efficient one step synthesis of 2-amino-5-cyano-6-hydroxy-4-aryl pyrimidines and their anti-bacterial activity

    Microsoft Academic Search

    M. B. Deshmukh; S. M. Salunkhe; D. R. Patil; P. V. Anbhule

    2009-01-01

    The first simple and efficient approach towards one step synthesis of 2-amino-5-cyano-6-hydroxy-4-aryl pyrimidines has been developed by three component condensation of aromatic aldehydes, ethyl cyanoacetate and guanidine hydrochloride in alkaline ethanol. The synthesized compounds evaluated for their anti-bacterial activity against Gram-positive and Gram-negative bacteria. The some of the compounds showed excellent zone of inhibition against tested bacteria.

  4. An efficient one-pot organocatalyzed synthesis of spiro[chroman-3,6'- furo[2,3-d]pyrimidine]-tetraones.

    PubMed

    Ahadi, Somayeh; Mirzaei, Peiman; Bazgir, Ayoob

    2013-07-01

    An efficient synthesis of new spiro[chroman-3,6'-furo[2,3-d]pyrimidine]- tetraones by an organocatalyzed three-component condensation reaction of aldehydes, barbituric acids and 3-bromo-4-hydroxy-2H-chromen-2-one in refluxing acetic acid in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is reported. We are hopeful that the products will lead to a wider range pharmacological and physiological activity. PMID:23363063

  5. ONE-POT SYNTHESIS OF 2,4,5TRISUBSTITUTED IMIDAZOLES USING [BPy]H2PO4, AN EFFICIENT AND RECYCLABLE CATALYST

    Microsoft Academic Search

    Yuliang Zhang; Zhongqiang Zhou

    2012-01-01

    [BPy]H2PO4 was easily prepared and used as efficient and recyclable catalyst for the one-pot synthesis of 2,4,5-trisubstituted imidazoles under solvent-free conditions in good to excellent yields. Solvent-free conditions, simple experimental and work-up procedures, along with the use of non-toxic, recyclable catalyst of an environmentally benign nature are remarkable features of the procedure.

  6. Efficient Conversion of N-Terminal of L-Tyrosine, DL-Phenyl Alanine, and Glycine to Substituted 2-Thioxo-thiazolidine-4-ones: A Stereospecific Synthesis

    Microsoft Academic Search

    B. R. Prashantha Kumar; Prabudha Basu; L. Adhikary; M. J. Nanjan

    2012-01-01

    We report facile and efficient conversion of the amino functional group of amino acids such a s L-tyrosine, DL-phenylalanine, and glycine to the corresponding (±)-2-thioxo-thiazolidine-4-ones (rhodanines). Stereospecific synthesis of amino acid–incorporated rhodanine is achieved in the case of L-tyrosine. Knoevenagel condensation over the active methylene group at the fifth position of the corresponding rhodanines is also described. The substituted rhodanine

  7. Efficient, Conversion of N-terminal of L-tyrosine, DL-phenyl Alanine and Glycine to Substituted 2-thioxo-thiazolidine-4-ones: A Stereospecific Synthesis

    Microsoft Academic Search

    B. R. Prashantha Kumar; Prabudha Basu; L. Adhikary; M. J. Nanjan

    2012-01-01

    We report facile and efficient conversion of the amino functional group of amino acids such a s L-tyrosine, DL-phenylalanine and glycine to the corresponding (±)-2-thioxo-thiazolidine-4-ones (rhodanines). Stereospecific synthesis of amino acid incorporated rhodanine is achieved in the case of L-tyrosine. Knoevenagel condensation over the active methylene group at the fifth position of the corresponding rhodanines is also described. The substituted

  8. Efficient synthesis and characterization of new photoactive dextran esters showing nanosphere formation.

    PubMed

    Wondraczek, Holger; Heinze, Thomas

    2008-07-01

    Different types of photoactive dextran derivatives with high degree of substitution were prepared by an efficient and mild esterification of the biopolymer with 2-methoxycinnamic acid, [(4-methyl-2-oxo-2H-chromen-7-yl)oxy]acetic acid, and azobenzene-4-carboxylic acid via in situ activation of the carboxylic acid groups with N,N'-carbonyldiimidazole. The structures of the novel dextran esters were evaluated by means of NMR spectroscopy applying the perpropionylated samples. Perpropionylation yields samples soluble in chloroform and acetonitrile that are very useful solvents not only for NMR but also for UV-vis spectroscopic studies. The photochemistry was studied by NMR and UV-vis spectroscopy in the dissolved state and the changes observed may be used to control the properties. The photoactive dextran esters form spherical nanoparticles of a size below 200 nm that are of interest in the design of smart materials. PMID:18551455

  9. 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

  10. One-pot synthesis of aryl sulfones from organometallic reagents and iodonium salts.

    PubMed

    Margraf, Natalie; Manolikakes, Georg

    2015-03-01

    A transition-metal-free arylation of lithium, magnesium, and zinc sulfinates with diaryliodonium salts is described. The sulfinic acid salts were prepared from the reaction of the corresponding organometallic reagents and sulfur dioxide. Combination of the three single steps (preparation of the organometallic compound, sulfinate formation, and arylation) leads to a one-pot sequence for the synthesis of aryl sulfones from simple starting materials. The chemoselectivity of unsymmetrical diaryliodonium salts has been investigated. Potential and limitations of this method will be discussed. PMID:25650485

  11. 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

  12. 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

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

    PubMed

    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?m(2) g(-1)), excellent magnetic response (14.89?emu g(-1)), and large mesopore volume (0.09?cm(3) 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

  14. Synthesis of carbon black/carbon nitride intercalation compound composite for efficient hydrogen production.

    PubMed

    Wu, Zhaochun; Gao, Honglin; Yan, Shicheng; Zou, Zhigang

    2014-08-21

    The photoactivity of g-C3N4 is greatly limited by its high recombination rate of photogenerated carriers. Coupling g-C3N4 with other materials has been demonstrated to be an effective way to facilitate the separation and transport of charge carriers. Herein we report a composite of conductive carbon black and carbon nitride intercalation compound synthesized through facile one-step molten salt method. The as-prepared carbon black/carbon nitride intercalation compound composite was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), UV-vis absorption spectrum and photoluminescence spectroscopy (PL). The carbon black nanoparticles, homogeneously dispersed on the surface of carbon nitride intercalation compound, efficiently enhanced separation and transport of photogenerated carriers, thus improving the visible-light photocatalytic activity. The composite of 0.5 wt% carbon black and carbon nitride intercalation compound exhibited a H2 production rate of 68.9 ?mol h(-1), which is about 3.2 times higher than hydrogen production on pristine carbon nitride intercalation compound. PMID:24975427

  15. Versatile Synthesis of Stable, Functional Polypeptides via Reaction with Epoxides.

    PubMed

    Gharakhanian, Eric G; Deming, Timothy J

    2015-06-01

    Methodology was developed for efficient alkylation of methionine residues using epoxides as a general strategy to introduce a wide range of functional groups onto polypeptides. Use of a spacer between epoxide and functional groups further allowed addition of sterically demanding functionalities. Contrary to other methods to alkylate methionine residues, epoxide alkylations allow the reactions to be conducted in wet protic media and give sulfonium products that are stable against dealkylation. These functionalizations are notable since they are chemoselective, utilize stable and readily available epoxides, and allow facile incorporation of an unprecedented range of functional groups onto simple polypeptides using stable linkages. PMID:25974116

  16. Chemoselective C-4 aerobic oxidation of catechin derivatives catalyzed by the Trametes villosa laccase/1-hydroxybenzotriazole system: synthetic and mechanistic aspects.

    PubMed

    Bernini, Roberta; Crisante, Fernanda; Gentili, Patrizia; Morana, Fabio; Pierini, Marco; Piras, Monica

    2011-02-01

    Catechin derivatives were oxidized in air in the presence of the Trametes villosa laccase/1-hydroxybenzotriazole (HBT) system in buffered water/1,4-dioxane as reaction medium. The oxidation products, flavan-3,4-diols and the corresponding C-4 ketones, are bioactive compounds and useful intermediates for the hemisynthesis of proanthocyanidins, plant polyphenols which provide beneficial health properties for humans. Determinations of oxidation potentials excluded that catechin derivatives could be directly oxidized by laccase Cu(II), while it resulted in the H-abstraction from benzylic positions being promptly promoted by the enzyme in the presence of the mediator HBT, the parent species producing in situ the reactive intermediate benzotriazole-N-oxyl (BTNO) radical. A remarkable and unexpected result for the laccase/HBT oxidative system has been the chemoselective insertion of the oxygen atom into the C-4-H bond of catechin derivatives. Mechanistic aspects of the oxidation reaction have been investigated in detail for the first time in order to corroborate these results. Since the collected experimental findings could not alone provide information useful to clarify the origin of the observed chemoselectivity, these data were expressly supplemented with information derived by suitable molecular modeling investigations. The integrated evaluation of the dissociation energies of the C-H bonds calculated both by semiempirical and DFT methods and the differential activation energies of the process estimated by a molecular modeling approach suggested that the observed selective oxidation at the C-4 carbon has a kinetic origin. PMID:21204551

  17. Human DNA Polymerase ? Catalyzes Correct and Incorrect DNA Synthesis with High Catalytic Efficiency.

    PubMed

    Gowda, A S Prakasha; Moldovan, George-Lucian; Spratt, Thomas E

    2015-06-26

    DNA polymerase ? (pol ?) is a low fidelity A-family polymerase with a putative role in interstrand cross-link repair and homologous recombination. We carried out pre-steady-state kinetic analysis to elucidate the kinetic mechanism of this enzyme. We found that the mechanism consists of seven steps, similar that of other A-family polymerases. pol ? binds to DNA with a Kd for DNA of 9.2 nm, with an off-rate constant of 0.013 s(-1)and an on-rate constant of 14 ?m(-1) s(-1). dNTP binding is rapid with Kd values of 20 and 476 ?m for the correct and incorrect dNTP, respectively. Pyrophosphorylation occurs with a Kd value for PPi of 3.7 mm and a maximal rate constant of 11 s(-1). Pre-steady-state kinetics, examination of the elemental effect using dNTP?S, and pulse-chase experiments indicate that a rapid phosphodiester bond formation step is flanked by slow conformational changes for both correct and incorrect base pair formation. These experiments in combination with computer simulations indicate that the first conformational change occurs with rate constants of 75 and 20 s(-1); rapid phosphodiester bond formation occurs with a Keq of 2.2 and 1.7, and the second conformational change occurs with rate constants of 2.1 and 0.5 s(-1), for correct and incorrect base pair formation, respectively. The presence of a mispair does not induce the polymerase to adopt a low catalytic conformation. pol ? catalyzes both correct and mispair formation with high catalytic efficiency. PMID:25963146

  18. Graphene oxide based Pt-TiO2 photocatalyst: ultrasound assisted synthesis, characterization and catalytic efficiency.

    PubMed

    Neppolian, Bernaurdshaw; Bruno, Andrea; Bianchi, Claudia L; Ashokkumar, Muthupandian

    2012-01-01

    An ultrasound-assisted method was used for synthesizing nanosized Pt-graphene oxide (GO)-TiO2 photocatalyst. The Pt-GO-TiO2 nanoparticles were characterized by diffused reflectance spectroscopy, X-ray diffraction, N2 BET adsorption-desorption measurements, atomic force microscopy and transmission electron microscopy. The photocatalytic and sonophotocatalytic degradation of a commonly used anionic surfactant, dodecylbenzenesulfonate (DBS), in aqueous solution was carried out using Pt-GO-TiO2 nanoparticles in order to evaluate the photocatalytic efficiency. For comparison purpose, sonolytic degradation of DBS was carried out. The Pt-GO-TiO2 catalyst degraded DBS at a higher rate than P-25 (TiO2), prepared TiO2 or GO-TiO2 photocatalysts. The mineralization of DBS was enhanced by a factor of 3 using Pt-GO-TiO2 compared to the P-25 (TiO2). In the presence of GO, an enhanced rate of DBS oxidation was observed and, when doped with platinum, mineralization of DBS was further enhanced. The Pt-GO-TiO2 catalyst also showed a considerable amount of degradation of DBS under visible light irradiation. The initial solution pH had an effect on the rate of photocatalytic oxidation of DBS, whereas no such effect of initial pH was observed in the sonochemical or sonophotocatalytic oxidation of DBS. The intermediate products formed during the degradation of DBS were monitored using electrospray mass spectrometry. The ability of GO to serve as a solid support to anchor platinum particles on GO-TiO2 is useful in developing new photocatalysts. PMID:21684791

  19. 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…

  20. Total synthesis of neodolastane diterpenes trichoaurantianolides C and d.

    PubMed

    Williams, David R; Gladen, Paul T; Pinchman, Joseph R

    2015-06-01

    The first total synthesis of trichoaurantianolides C and D is described. An enantiocontrolled pathway leads to rapid construction of the tricyclic carbon skeleton and establishes the trans-dimethyl geometry of the quaternary bridgehead carbons via a reductive cyclization. Application of the ?-allyl Stille cross-coupling leads to a nonracemic allylic alcohol as a prerequisite for the introduction of asymmetry in the cycloheptane system. Two strategies have been examined for elaboration of the unsaturated tetrahydrofuranyl ring from a common tricyclic intermediate. These efforts reveal a number of unanticipated issues of reactivity and significant stereochemical requirements for a novel acyloin rearrangement as well as the elimination and cyclodehydration of chiral ?-hydroxy ketones. Key reactions leading to completion of the synthesis include the stereoselective addition of isopropenyllithium TMEDA complex and a facile chemoselective oxidation with selenium dioxide. PMID:25974179

  1. Novel and efficient synthesis of 22-alkynyl-13,24(23)-cyclo-18,21-dinorchol-22-en-20(23)-one analogues.

    PubMed

    Wang, Cunde; Liu, Lanhai; Xu, Hangxian; Zhang, Zonglei; Wang, Xingbin; Liu, Hui

    2011-04-01

    The efficient synthesis of some 22-alkynyl-13,24(23)-cyclo-18,21-dinorchol-22-en-20(23)-ones was investigated. 22-Iodocyclo-18,21-dinorcholenones were prepared from cyclo-18,21-dinorcholenones using I(2)/DMAP/pyridine system firstly. The cross coupling reaction of 22-iodocyclo-18,21-dinorcholenones and 1-alkynes was carried out efficiently catalyzed by tetrakis(triphenylphosphine) palladium/cuprous iodide in the presence of base diisopropylethylamine. This strategy offered a very straightforward and efficient method for access to conjugated alkynyl cyclo-18,21-dinorcholenones from the cyclo-18,21-dinorcholenones and 1-alkynes in excellent overall yields. Evaluation of the synthesized compounds for cytotoxicity against KB, HeLa, MKN-28 and MCF-7 cell lines showed that the 22-alkynylcyclodinorchoenones possessing hydroxylethyl and hydroxylmethyl mono-substituted side chain at the end of alkynyl group have significantly inhibition activity. PMID:21262249

  2. ZnO Nanoparticles as an Efficient, Heterogeneous, Reusable, and Ecofriendly Catalyst for Four-Component One-Pot Green Synthesis of Pyranopyrazole Derivatives in Water

    PubMed Central

    Sachdeva, Harshita; Saroj, Rekha

    2013-01-01

    An extremely efficient catalytic protocol for the synthesis of a series of pyranopyrazole derivatives developed in a one-pot four-component approach in the presence of ZnO nanoparticles as heterogeneous catalyst using water as a green solvent is reported. Greenness of the process is well instituted as water is exploited both as reaction media and medium for synthesis of catalyst. The ZnO nanoparticles exhibited excellent catalytic activity, and the proposed methodology is capable of providing the desired products in good yield (85–90%) and short reaction time. After reaction course, ZnO nanoparticles can be recycled and reused without any apparent loss of activity which makes this process cost effective and hence ecofriendly. All the synthesized compounds have been characterized on the basis of elemental analysis, IR, 1H NMR, and 13C NMR spectral studies. PMID:24282386

  3. ZnO nanoparticles as an efficient, heterogeneous, reusable, and ecofriendly catalyst for four-component one-pot green synthesis of pyranopyrazole derivatives in water.

    PubMed

    Sachdeva, Harshita; Saroj, Rekha

    2013-01-01

    An extremely efficient catalytic protocol for the synthesis of a series of pyranopyrazole derivatives developed in a one-pot four-component approach in the presence of ZnO nanoparticles as heterogeneous catalyst using water as a green solvent is reported. Greenness of the process is well instituted as water is exploited both as reaction media and medium for synthesis of catalyst. The ZnO nanoparticles exhibited excellent catalytic activity, and the proposed methodology is capable of providing the desired products in good yield (85-90%) and short reaction time. After reaction course, ZnO nanoparticles can be recycled and reused without any apparent loss of activity which makes this process cost effective and hence ecofriendly. All the synthesized compounds have been characterized on the basis of elemental analysis, IR, ¹H NMR, and ¹³C NMR spectral studies. PMID:24282386

  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. Ultrasonic activated efficient synthesis of chromenes using amino-silane modified Fe3O4 nanoparticles: A versatile integration of high catalytic activity and facile recovery

    NASA Astrophysics Data System (ADS)

    Safari, Javad; Zarnegar, Zohre

    2014-08-01

    An efficient synthesis of 2-amino-4H-chromenes is achieved by one pot three component coupling reaction of aldehyde, malononitrile, and resorcinol using amino-silane modified Fe3O4 nanoparticles (MNPs-NH2) heterogeneous nanocatalyst under sonic condition. The attractive advantages of the present process are mild reaction conditions, short reaction times, easy isolation of products, good yields and simple operational procedures. Combination of the advantages of ultrasonic irradiation and magnetic nanoparticles provides important methodology to carry out catalytic transformations.

  6. An efficient and convenient protocol for the synthesis of novel 1? H -spiro[isoindoline-1,2?-quinazoline]-3,4?(3? H )-dione derivatives

    Microsoft Academic Search

    M. Dabiri; Ali A. Mohammadi; Hassan Qaraat

    2009-01-01

    \\u000a Abstract  An efficient and direct procedure for the synthesis of novel spiro[isoindoline-1,2?-quinazoline]-3,4?(3?H)-dione derivatives is described. The process employs a condensation reaction of 2-aminobenzamides and isatins in the presence\\u000a of a catalytic amount of KAl(SO4)2.12H2O (alum) in ethanol under reflux.\\u000a \\u000a \\u000a \\u000a Graphical Abstract  

  7. An efficient solvent-free synthesis of 2-hydroxy-2-(trifluoromethyl)-2H-chromenes using silica-immobilized L-proline.

    PubMed

    Xu, Cuilian; Yang, Guoyu; Wang, Caixia; Fan, Sufang; Xie, Lixia; Gao, Ya

    2013-01-01

    An efficient synthesis of 2-hydroxy-2-(trifluoromethyl)-2H-chromene-3-carboxylates was carried out under solvent-free conditions in an oven or microwave oven via the Knoevenagel condensation of salicylaldehydes with ethyl trifluoroacetoacetate followed by intramolecular cyclization in the presence of silica-immobilized L-proline. The structures of the title compounds were characterized by IR, ¹H-NMR, ¹³C-NMR, HRMS and X-ray single crystal diffraction. The improved method described herein is economical, easily-operated and environmentally friendly. Furthermore, the catalyst can be recovered conveniently and reused without obvious loss of activity. PMID:24077175

  8. A metalloenzyme-like catalytic system for the chemoselective oxidative cross-coupling of primary amines to imines under ambient conditions.

    PubMed

    Largeron, Martine; Fleury, Maurice-Bernard

    2015-02-23

    The direct oxidative cross-coupling of primary amines is a challenging transformation as homocoupling is usually preferred. We report herein the chemoselective preparation of cross-coupled imines through the synergistic combination of low loadings of Cu(II) metal-catalyst and o-iminoquinone organocatalyst under ambient conditions. This homogeneous cooperative catalytic system has been inspired by the reaction of copper amine oxidases, a family of metalloenzymes with quinone organic cofactors that mediate the selective oxidation of primary amines to aldehydes. After optimization, the desired cross-coupled imines are obtained in high yields with broad substrate scope through a transamination process that leads to the homocoupled imine intermediate, followed by dynamic transimination. The ability to carry out the reactions at room temperature and with ambient air, rather than molecular oxygen as the oxidant, and equimolar amounts of each coupling partner is particularly attractive from an environmentally viewpoint. PMID:25643811

  9. 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. [Departamento de Quimica Inorganica, Facultad de Ciencias Quimicas, Universidad Complutense de Madrid, 28040 Madrid (Spain)] [Departamento de Quimica Inorganica, Facultad de Ciencias Quimicas, Universidad Complutense de Madrid, 28040 Madrid (Spain); Moran, E., E-mail: emoran@quim.ucm.es [Departamento de Quimica Inorganica, Facultad de Ciencias Quimicas, Universidad Complutense de Madrid, 28040 Madrid (Spain)

    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.

  10. An efficient and versatile synthesis of GlcNAcstatins—potent and selective O-GlcNAcase inhibitors built on the tetrahydroimidazo[1,2-a]pyridine scaffold

    PubMed Central

    Borodkin, Vladimir S.; van Aalten, Daan M.F.

    2010-01-01

    We report a novel approach to the synthesis of GlcNAcstatins—members of an emerging family of potent and selective inhibitors of peptidyl O-GlcNAc hydrolase build upon tetrahydroimidazo[1,2-a]pyridine scaffold. Making use of a streamlined synthetic sequence featuring de novo synthesis of imidazoles from glyoxal, ammonia and aldehydes, a properly functionalised linear GlcNAcstatin precursor has been efficiently prepared starting from methyl 3,4-O-(2?,3?-dimethoxybutane-2?,3?-diyl)-?-d-mannopyranoside. Subsequent ring closure of the linear precursor in an intramolecular SN2 process furnished the key fused d-mannose-imidazole GlcNAcstatin precursor in excellent yield. Finally, a sequence of transformations of this key intermediate granted expeditious access to a variety of the target compounds bearing a C(2)-phenethyl group and a range of N(8) acyl substituents. The versatility of the new approach stems from an appropriate choice of a set of acid labile permanent protecting groups on the monosaccharide starting material. Application was demonstrated by the synthesis of GlcNAcstatins containing polyunsaturated and thiol-containing amido substituents. PMID:20976183

  11. Comparing substrate specificity of two UDP-sugar pyrophosphorylases and efficient one-pot enzymatic synthesis of UDP-GlcA and UDP-GalA.

    PubMed

    Guo, Yuxi; Fang, Junqiang; Li, Tiehai; Li, Xu; Ma, Cheng; Wang, Xuan; Wang, Peng G; Li, Lei

    2015-06-26

    Uridine 5'-diphosphate-glucuronic acid (UDP-GlcA) and UDP-galacturonic acid (UDP-GalA), the unique carboxylic acid-formed sugar nucleotides, are key precursors involved in the biosynthesis of numerous cell components. Limited availability of those components has been hindering the development of efficient ways towards facile synthesis of bioactive glycans such as glycosaminoglycans. In current study, we biochemically characterized two UDP-sugar pyrophosphorylases from Arabidopsis thaliana (AtUSP) and Bifidobacterium infantis ATCC15697 (BiUSP), and compared their activities towards a panel of sugar-1-phosphates and derivatives. Both enzymes showed significant pyrophosphorylation activities towards GlcA-1-phosphate, and AtUSP also exhibited comparable activity towards GalA-1-phosphate. By combining with monosaccharide-1-phosphate kinases, we have developed an efficient and facile one-pot three-enzyme approach to quickly obtain hundreds milligrams of UDP-GlcA and UDP-GalA. PMID:25942062

  12. 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

  13. 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

  14. Efficient routes toward the synthesis of the D-rhamno-trisaccharide related to the A-band polysaccharide of Pseudomonas aeruginosa

    PubMed Central

    Chaudhury, Aritra; Maity, Sajal K

    2014-01-01

    Summary The present work describes efficient avenues for the synthesis of the trisaccharide repeating unit [?-D-Rhap-(1?3)-?-D-Rhap-(1?3)-?-D-Rhap] associated with the A-band polysaccharide of Pseudomonas aeruginosa. One of the key steps involved 6-O-deoxygenation of either partially or fully acylated 4,6-O-benzylidene-1-thiomannopyranoside by radical-mediated redox rearrangement in high yields and regioselectivity. The D-rhamno-thioglycosides so obtained allowed efficient access to the trisaccharide target via stepwise glycosylation as well as a one-pot glycosylation protocol. In a different approach, a 4,6-O-benzylidene D-manno-trisaccharide derivative was synthesized, which upon global 6-O-deoxygenation followed by deprotection generated the target D-rhamno-trisaccharide. The application of the reported regioselective radical-mediated deoxygenation on 4,6-O-benzylidene D-manno thioglycoside (hitherto unexplored) has potential for ramification in the field of synthesis of oligosaccharides based on 6-deoxy hexoses. PMID:25161705

  15. Total Synthesis of Bryostatin 7 via C-C Bond Forming Hydrogenation: Merged Redox-Construction Events for Synthetic Efficiency

    PubMed Central

    Lu, Yu; Woo, Sang Kook; Krische, Michael J.

    2011-01-01

    The marine macrolide bryostatin 7 is prepared in 20 steps (longest linear sequence) and 36 total steps. A total of 5 C-C bonds are formed using hydrogenative methods. The present approach represents the most concise synthesis of any bryostatin reported, to date, setting the stage for practical syntheses of simplified functional analogues. PMID:21780806

  16. Variants of mouse DNA polymerase ? reveal a mechanism of efficient and accurate translesion synthesis past a benzo[a]pyrene dG adduct

    PubMed Central

    Liu, Yang; Yang, Yeran; Tang, Tie-Shan; Zhang, Hui; Wang, Zhifeng; Friedberg, Errol; Yang, Wei; Guo, Caixia

    2014-01-01

    DNA polymerase ? (Pol?) is the only known Y-family DNA polymerase that bypasses the 10S (+)-trans-anti-benzo[a]pyrene diol epoxide (BPDE)-N2-deoxyguanine adducts efficiently and accurately. The unique features of Pol?, a large structure gap between the catalytic core and little finger domain and a 90-residue addition at the N terminus known as the N-clasp, may give rise to its special translesion capability. We designed and constructed two mouse Pol? variants, which have reduced gap size on both sides [Pol? Gap Mutant (PGM) 1] or one side flanking the template base (PGM2). These Pol? variants are nearly as efficient as WT in normal DNA synthesis, albeit with reduced accuracy. However, PGM1 is strongly blocked by the 10S (+)-trans-anti-BPDE-N2-dG lesion. Steady-state kinetic measurements reveal a significant reduction in efficiency of dCTP incorporation opposite the lesion by PGM1 and a moderate reduction by PGM2. Consistently, Pol?-deficient cells stably complemented with PGM1 GFP-Pol? remained hypersensitive to BPDE treatment, and complementation with WT or PGM2 GFP-Pol? restored BPDE resistance. Furthermore, deletion of the first 51 residues of the N-clasp in mouse Pol? (mPol?52–516) leads to reduced polymerization activity, and the mutant PGM252–516 but not PGM152–516 can partially compensate the N-terminal deletion and restore the catalytic activity on normal DNA. However, neither WT nor PGM2 mPol?52–516 retains BPDE bypass activity. We conclude that the structural gap physically accommodates the bulky aromatic adduct and the N-clasp is essential for the structural integrity and flexibility of Pol? during translesion synthesis. PMID:24449898

  17. Novel Protocol for the Chemical Synthesis of Crustacean Hyperglycemic Hormone Analogues — An Efficient Experimental Tool for Studying Their Functions

    PubMed Central

    Mosco, Alessandro; Zlatev, Vientsislav; Guarnaccia, Corrado; Pongor, Sándor; Campanella, Antonella; Zahariev, Sotir; Giulianini, Piero G.

    2012-01-01

    The crustacean Hyperglycemic Hormone (cHH) is present in many decapods in different isoforms, whose specific biological functions are still poorly understood. Here we report on the first chemical synthesis of three distinct isoforms of the cHH of Astacus leptodactylus carried out by solid phase peptide synthesis coupled to native chemical ligation. The synthetic 72 amino acid long peptide amides, containing L- or D-Phe3 and (Glp1, D-Phe3) were tested for their biological activity by means of homologous in vivo bioassays. The hyperglycemic activity of the D-isoforms was significantly higher than that of the L-isoform, while the presence of the N-terminal Glp residue had no influence on the peptide activity. The results show that the presence of D-Phe3 modifies the cHH functionality, contributing to the diversification of the hormone pool. PMID:22253873

  18. Novel protocol for the chemical synthesis of crustacean hyperglycemic hormone analogues--an efficient experimental tool for studying their functions.

    PubMed

    Mosco, Alessandro; Zlatev, Vientsislav; Guarnaccia, Corrado; Pongor, Sándor; Campanella, Antonella; Zahariev, Sotir; Giulianini, Piero G

    2012-01-01

    The crustacean Hyperglycemic Hormone (cHH) is present in many decapods in different isoforms, whose specific biological functions are still poorly understood. Here we report on the first chemical synthesis of three distinct isoforms of the cHH of Astacus leptodactylus carried out by solid phase peptide synthesis coupled to native chemical ligation. The synthetic 72 amino acid long peptide amides, containing L- or D-Phe³ and (Glp¹, D-Phe³) were tested for their biological activity by means of homologous in vivo bioassays. The hyperglycemic activity of the D-isoforms was significantly higher than that of the L-isoform, while the presence of the N-terminal Glp residue had no influence on the peptide activity. The results show that the presence of D-Phe³ modifies the cHH functionality, contributing to the diversification of the hormone pool. PMID:22253873

  19. Rapid Synthesis of Phenyl-Functionalized Mesoporous Silica Using as a Highly Efficient Fiber Coating of SolidPhase Microextraction

    Microsoft Academic Search

    Honghong Rao; Xinzhen Du; Xuemei Wang; Chunlan Li; Xu Cao

    2010-01-01

    A rapid synthesis of highly ordered phenyl-functionalized MCM-41 (Phen-MCM-41-R) mesoporous silica was performed by using cetyltrimethylammonium bromide as the template and tetraethyl orthosilicate as the silica source under alkaline conditions within 3 h. The samples were characterized by fourier transform infrared (FTIR) spectra, small-angle X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption-desorption, and thermogravimetric analysis (TGA).

  20. Stereoselective synthesis of highly functionalized indanes and dibenzocycloheptadienes through complex radical cascade reactions.

    PubMed

    Kong, Wangqing; Fuentes, Noelia; García-Domínguez, Andres; Merino, Estíbaliz; Nevado, Cristina

    2015-02-16

    Two highly stereoselective radical-mediated syntheses of densely functionalized indanes and dibenzocycloheptadienes from ortho-vinyl- and ortho-vinylaryl-substituted N-(arylsulfonyl)-acrylamides, respectively, are presented here. The chemoselective addition of in?situ generated radicals (X(·)) onto the styrene moieties triggers an unprecedented reaction cascade, resulting in the formation of one new C-X bond and two new C-C bonds, a formal 1,4-aryl migration, and the extrusion of SO2 to generate an amidyl radical intermediate. This intermediate, upon H?abstraction, leads to the observed 5- and 7-membered ring carbocyclic products, respectively, in a highly efficient manner. PMID:25597296

  1. The role of ?6-desaturase acyl-carrier specificity in the efficient synthesis of long-chain polyunsaturated fatty acids in transgenic plants.

    PubMed

    Sayanova, Olga; Ruiz-Lopez, Noemi; Haslam, Richard P; Napier, Johnathan A

    2012-02-01

    The role of acyl-CoA-dependent ?6-desaturation in the heterologous synthesis of omega-3 long-chain polyunsaturated fatty acids was systematically evaluated in transgenic yeast and Arabidopsis thaliana. The acyl-CoA ?6-desaturase from the picoalga Ostreococcus tauri and orthologous activities from mouse (Mus musculus) and salmon (Salmo salar) were shown to generate substantial levels of ?6-desaturated acyl-CoAs, in contrast to the phospholipid-dependent ?6-desaturases from higher plants that failed to modify this metabolic pool. Transgenic plants expressing the acyl-CoA ?6-desaturases from either O. tauri or salmon, in conjunction with the two additional activities required for the synthesis of C20 polyunsaturated fatty acids, contained higher levels of eicosapentaenoic acid compared with plants expressing the borage phospholipid-dependent ?6-desaturase. The use of acyl-CoA-dependent ?6-desaturases almost completely abolished the accumulation of unwanted biosynthetic intermediates such as ?-linolenic acid in total seed lipids. Expression of acyl-CoA ?6-desaturases resulted in increased distribution of long-chain polyunsaturated fatty acids in the polar lipids of transgenic plants, reflecting the larger substrate pool available for acylation by enzymes of the Kennedy pathway. Expression of the O. tauri?6-desaturase in transgenic Camelina sativa plants also resulted in the accumulation of high levels of ?6-desaturated fatty acids. This study provides evidence for the efficacy of using acyl-CoA-dependent ?6-desaturases in the efficient metabolic engineering of transgenic plants with high value traits such as the synthesis of omega-3 LC-PUFAs. PMID:21902798

  2. Uninterrupted galvanic reaction for scalable and rapid synthesis of metallic and bimetallic sponges/dendrites as efficient catalysts for 4-nitrophenol reduction.

    PubMed

    Barman, Barun Kumar; Nanda, Karuna Kar

    2015-03-01

    Here, we demonstrate an uninterrupted galvanic replacement reaction (GRR) for the synthesis of metallic (Ag, Cu and Sn) and bimetallic (Cu-M, M=Ag, Au, Pt and Pd) sponges/dendrites by sacrificing the low reduction potential metals (Mg in our case) in acidic medium. The acidic medium prevents the oxide formation on Mg surface and facilitates the uninterrupted reaction. The morphology of dendritic/spongy structures is controlled by the volume of acid used for this reaction. The growth mechanism of the spongy/dendritic microstructures is explained by diffusion-limited aggregate model (DLA), which is also largely affected by the volume of acid. The significance of this method is that the yield can be easily predicted, which is a major challenge for the commercialization of the products. Furthermore, the synthesis is complete in 1-2 minutes at room temperature. We show that the sponges/dendrites efficiently act as catalysts to reduce 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) using NaBH4-a widely studied conversion process. PMID:25628256

  3. Contribution of RpoS to metabolic efficiency and ectoines synthesis during the osmo- and heat-stress response in the halophilic bacterium Chromohalobacter salexigens.

    PubMed

    Salvador, Manuel; Argandoña, Montserrat; Pastor, Jose M; Bernal, Vicente; Cánovas, Manuel; Csonka, Laszlo N; Nieto, Joaquín J; Vargas, Carmen

    2015-04-01

    Chromohalobacter salexigens is a halophilic ?-proteobacterium that responds to osmotic and heat stresses by accumulating ectoine and hydroxyectoine respectively. Evolution has optimized its metabolism to support high production of ectoines. We analysed the effect of an rpoS mutation in C.?salexigens metabolism and ectoines synthesis. In long-term adapted cells, the rpoS strain was osmosensitive but not thermosensitive and showed unaltered ectoines content, suggesting that RpoS regulates ectoine(s)-independent osmoadaptive mechanisms. RpoS is involved in the regulation of C.?salexigens metabolic adaptation to stress, as early steps of glucose oxidation through the Entner-Doudoroff pathway were deregulated in the rpoS mutant, leading to improved metabolic efficiency at low salinity. Moreover, a reduced pyruvate (but not acetate) overflow was displayed by the rpoS strain at low salt, probably linked to a slowdown in gluconate production and/or subsequent metabolism. Interestingly, RpoS does not seem to be the main regulator triggering the immediate transcriptional response of ectoine synthesis to osmotic or thermal upshifts. However, it contributed to the expression of the ect genes in cells previously adapted to low or high salinity. PMID:25417903

  4. 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

  5. Solid-Phase Synthesis and Kinetic Characterization of Fluorogenic Enzyme-Degradable Hydrogel Crosslinkers

    PubMed Central

    Moss, Jason A.; Stokols, Shula; Hixon, Mark; Ashley, Fawn; Chang, Jason Y.; Janda, Kim D.

    2008-01-01

    Of critical importance in drug delivery and tissue engineering applications is the degradabilty of implanted polymeric materials. The use of peptide-derived crosslinkers in hydrogel design is a valuable approach by which polymeric carriers can be endowed with enzymatic degradability in a predictable, ‘programmable’ fashion. The solid-phase synthesis strategy described herein allows for an expeditious, flexible synthesis of bis-acrylamide-derivatized peptides with complex modifications, as exemplified by the incorporation of fluorophore and quencher moieties into a matrix metalloprotease (MMP)-degradable crosslinker. The crude synthetic product was obtained in high yield and purity, and purified by standard methods; it was then used directly for polymerization without the need for tedious and often non-chemoselective solution-phase modifications. Functional appendages incorporated for detection provided a direct, quantitative link between enzymatic activity and hydrogel degradation using routine methods for identification of optimal enzyme-specific degradability. PMID:16602715

  6. Biomolecule-assisted synthesis of carbon nitride and sulfur-doped carbon nitride heterojunction nanosheets: An efficient heterojunction photocatalyst for photoelectrochemical applications

    PubMed Central

    Tao, Hua Bing; Chen, Jiazang; Miao, Jianwei

    2014-01-01

    Summary A biomolecule-assisted pyrolysis method has been developed to synthesize sulfur-doped graphitic carbon nitride (CNS) nanosheets. During the synthesis, sulfur could be introduced as a dopant into the lattice of carbon nitride (CN). Sulfur doping changed the texture as well as relative band positions of CN. By growing CN on preformed sulfur-doped CN nanosheets, composite CN/CNS heterojunction nanosheets were constructed, which significantly enhanced the photoelectrochemical performance as compared with various control counterparts including CN, CNS and physically mixed CN and CNS (CN+CNS). The enhanced photoelectrochemical performance of CN/CNS heterojunction nanosheets could be ascribed to the efficient separation of photoexcited charge carriers across the heterojunction interface. The strategy of designing and preparing CN/CNS heterojunction photocatalysts in this work can open up new directions for the construction of all CN-based heterojunction photocatalysts. PMID:24991514

  7. Efficient Synthesis of Amides and Esters from Alcohols under Aerobic Ambient Conditions Catalyzed by a Au/Mesoporous Al2 O3 Nanocatalyst.

    PubMed

    Chng, Leng Leng; Yang, Jinhua; Ying, Jackie Y

    2015-06-01

    An efficient heterogeneous Au/mesoporous alumina nanocatalyst has been successfully developed for the synthesis of amides and esters from simple building blocks of readily available alcohols and amines. The processes were simple and were performed at room temperature and atmospheric pressure of O2 to form the desired products with up to 97?% isolated yield. The ability of Au/mesoporous alumina to catalyze these reactions under ambient conditions further enhances the sustainability of these chemical processes. Furthermore, the nanocatalyst was stable to air and water and could be recovered and reused easily. The enhanced catalytic activity of Au/mesoporous alumina might be attributed to the presence of negatively charged Au nanoparticles that could promote oxidation processes as well as the stability of the mesoporous alumina support calcined at a high temperature of 800?°C. PMID:25925279

  8. [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.

  9. 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

  10. 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

  11. Synthesis of an Amphiphilic Brush Copolymer by a Highly Efficient "Grafting onto" Approach via CO2 Chemistry.

    PubMed

    Zhang, Ying-Ying; Li, Yang; Zhou, Xian-Jing; Zhang, Xing-Hong; Du, Bin-Yang; Fan, Zhi-Qiang

    2015-05-01

    A novel and robust route for the synthesis of a new amphiphilic brush copolymer, poly(glycidyl methacrylate)-graft-polyethylene glycol (PGMA-g-PEG), with high grafting densities of 97%-98% through a "grafting onto" method via carbon dioxide chemistry is reported. PGMA-g-PEG can self-assemble and form stable spherical core-shell micelles in aqueous solution. Besides, the obtained PGMA-g-PEG polymer contains hydroxyurethane structures as the junction sites between the PGMA backbone and PEG side chain, which can be used for further modification. PMID:25823716

  12. An Efficient One-Pot, Four-Component Synthesis of 1,2,3-triazole Linked Tetrahydrobenzo[B]pyrans

    Microsoft Academic Search

    David I. MaGee; Peyman Salehi; Minoo Dabiri; Mahboobeh Bahramnejad

    2012-01-01

    A one-pot procedure has been developed for the synthesis of (1,2,3-triazolyl) methoxyphenyl tetrahydro-5-oxo-4H-chromene derivatives by concurrent reaction of aryl oxypropargylated aldehydes, various azides, active methylene compounds, and 1,3-cyclohexanediones using catalytic amounts of Cu(OAc)2\\/ sodium ascorbate and diammonium hydrogen phosphate in aqueous ethanol media. Excellent conversion of starting materials was achieved to the desired (1,2,3-triazolyl) methoxyphenyl tetrahydro-5-oxo-4H-chromene products.

  13. 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

  14. Efficient and Scalable Synthesis of 4-Carboxy-Pennsylvania Green Methyl Ester: A Hydrophobic Building Block for Fluorescent Molecular Probes.

    PubMed

    Woydziak, Zachary R; Fu, Liqiang; Peterson, Blake R

    2014-01-01

    Fluorinated fluorophores are valuable tools for studies of biological systems. However, amine-reactive single-isomer derivatives of these compounds are often very expensive. To provide an inexpensive alternative, we report a practical synthesis of 4-carboxy-Pennsylvania Green methyl ester. Derivatives of this hydrophobic fluorinated fluorophore, a hybrid of the dyes Oregon Green and Tokyo Green, are often cell permeable, enabling labeling of intracellular targets and components. Moreover, the low pKa of Pennsylvania Green (4.8) confers bright fluorescence in acidic cellular compartments such as endosomes, enhancing its utility for chemical biology investigations. To improve access to the key intermediate 2,7-difluoro-3,6-dihydroxyxanthen-9-one, we subjected bis-(2,4,5-trifluorophenyl)methanone to iterative nucleophilic aromatic substitution by hydroxide on scales of > 40 g. This intermediate was used to prepare over 15 grams of pure 4-carboxy-Pennsylvania Green methyl ester in 28% overall yield without requiring chromatography. This compound can be converted into the amine reactive N-hydroxysuccinimidyl ester in essentially quantitative yield for the synthesis of a wide variety of fluorescent molecular probes. PMID:24914246

  15. Efficient and Scalable Synthesis of 4-Carboxy-Pennsylvania Green Methyl Ester: A Hydrophobic Building Block for Fluorescent Molecular Probes

    PubMed Central

    Woydziak, Zachary R.; Fu, Liqiang

    2013-01-01

    Fluorinated fluorophores are valuable tools for studies of biological systems. However, amine-reactive single-isomer derivatives of these compounds are often very expensive. To provide an inexpensive alternative, we report a practical synthesis of 4-carboxy-Pennsylvania Green methyl ester. Derivatives of this hydrophobic fluorinated fluorophore, a hybrid of the dyes Oregon Green and Tokyo Green, are often cell permeable, enabling labeling of intracellular targets and components. Moreover, the low pKa of Pennsylvania Green (4.8) confers bright fluorescence in acidic cellular compartments such as endosomes, enhancing its utility for chemical biology investigations. To improve access to the key intermediate 2,7-difluoro-3,6-dihydroxyxanthen-9-one, we subjected bis-(2,4,5-trifluorophenyl)methanone to iterative nucleophilic aromatic substitution by hydroxide on scales of > 40 g. This intermediate was used to prepare over 15 grams of pure 4-carboxy-Pennsylvania Green methyl ester in 28% overall yield without requiring chromatography. This compound can be converted into the amine reactive N-hydroxysuccinimidyl ester in essentially quantitative yield for the synthesis of a wide variety of fluorescent molecular probes. PMID:24914246

  16. A rapid and efficient Sonogashira protocol and improved synthesis of free fatty acid 1 (FFA1) receptor agonists.

    PubMed

    Christiansen, Elisabeth; Due-Hansen, Maria E; Ulven, Trond

    2010-02-19

    A protocol for rapid and efficient Pd/Cu-catalyzed coupling of aryl bromides and iodides to terminal alkynes has been developed with use of 2-(di-tert-butylphosphino)-N-phenylindole (cataCXium PIntB) as ligand in TMEDA and water. The new protocol successfully couples substrates which failed with standard Sonogashira conditions, and enables an efficient general synthetic route to free fatty acid 1 (FFA1) receptor ligands from 3-(4-bromophenyl)propionic acid. PMID:20099863

  17. Synthesis of carbon embedded MFe2O4 (M = Ni, Zn and Co) nanoparticles as efficient hydrogenation catalysts.

    PubMed

    Nandan, Devaki; Sreenivasulu, Peta; Viswanadham, Nagabhatla; Chiang, Ken; Newnham, Jarrod

    2014-08-21

    Successful synthesis of stable MFe2O4 nanoparticles@C has been realized by applying the novel concept of using levulinic acid possessing carboxyl and carbonyl groups to facilitate the interaction with metal ions (M(2+) and Fe(3+)) and the carbon source (phloroglucinol) in the sol-gel polymerization method. All the samples have been characterized by XRD, SEM, FT-IR, TEM, HRTEM, ICP-AES, CHNS, and N2 adsorption-desorption, and were studied for their performance towards hydrogenation reaction of styrene. Out of three samples NiFe2O4 gave excellent selective hydrogenation activity of styrene to ethyl benzene (100% conversion and 100% selectivity). Optimal production of ethyl benzene over NiFe2O4 nanoparticles@C has been established at 80 °C reaction temperature after 24 h reaction time under 40 bar hydrogen pressure. PMID:24983775

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

    PubMed

    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

  19. 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

  20. 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).

  1. Facial synthesis of SnO2 nanoparticle film for efficient fiber-shaped dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Peng, Ming; Cai, Xin; Fu, Yongping; Yu, Xiao; Liu, Suqi; Deng, Bing; Hany, Kafafy; Zou, Dechun

    2014-02-01

    SnO2 nanoparticle film is directly prepared by in situ thermal calcining isopropanol solution of tin tetraisopropoxide, and is used to construct the SnO2-TiO2 junction on titanium wire substrate. The titanium wire supported SnO2-TiO2 junction is further applied to fiber-shaped dye-sensitized solar cells (FDSCs). High efficiency of 5.8% (Normal Model) and 12.4% (Diffuse Model) are achieved. Our results indicate that Jsc enhancement derived by SnO2-TiO2 junction and the recombination shielding effect of the compact TiO2 film could synergistically contribute to high efficiencies. This study offers a novel and alternative strategy for achieving efficient SnO2-TiO2 junction based solar cells in a facile, scalable and cost-effective way.

  2. 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

  3. A novel acylase from Streptomyces mobaraensis that efficiently catalyzes hydrolysis/synthesis of capsaicins as well as N-acyl-L-amino acids and N-acyl-peptides.

    PubMed

    Koreishi, Mayuko; Zhang, Demin; Imanaka, Hiroyuki; Imamura, Koreyoshi; Adachi, Shuji; Matsuno, Ryuichi; Nakanishi, Kazuhiro

    2006-01-11

    A novel enzyme that catalyzes efficient hydrolysis of capsaicin (8-methyl-N-vanillyl-6-nonenamide) was isolated from the culture broth of Streptomyces mobaraensis. The enzyme consisted of two dissimilar subunits with molecular masses of 61 and 19 kDa. The enzyme was activated and stabilized in the presence of Co2+. It showed a pH optimum of about 8 and was stable at temperatures of up to 55 degrees C for 1 h at pH 7.8. The specific activity of the enzyme for the hydrolysis of capsaicin was 10(2)-10(4) times higher than those for the enzymes reported to date. In an aqueous/n-hexane biphasic system, capsaicin analogues such as octanoyl, decanoyl, and lauroyl vanillylamides were synthesized from the corresponding fatty acids and vanillylamine at yields of 50% or greater. In addition, the enzyme catalyzed the deacylation of N-lauroyl-L-amino acids and N-lauroyl-L-dipeptides and the efficient synthesis of Nalpha-lauroyl-L-lysine, Nepsilon-lauroyl-L-lysine, and various N-lauroyl-peptides in aqueous solution in both the absence and the presence of glycerol. PMID:16390180

  4. One-Pot Synthesis of Mesoporous TiO2 Micropheres and Its Application for High-Efficiency Dye-Sensitized Solar Cells.

    PubMed

    Li, Zhao-Qian; Que, Ya-Ping; Mo, Li-E; Chen, Wang-Chao; Ding, Yong; Ma, Yan-Mei; Jiang, Ling; Hu, Lin-Hua; Dai, Song-Yuan

    2015-05-27

    TiO2 microspheres are of great interest for a great deal of applications, especially in the solar cell field. Because of their unique microstructure and light-scattering effect, TiO2 microsphere-based solar cells often exhibit superior photovoltaic performance. Hence, exploring new suitable TiO2 microspheres for high-efficiency solar cells is essential. In this work, we demonstrate a facile one-pot solvothermal approach for synthesis of TiO2 microspheres using acetone as solvent. The as-prepared TiO2 microspheres are composed of densely interconnected nanocrystals and possess a high specific surface area up to 138.47 m(2) g(-1). As the photoanode, the TiO2 microsphere-based DSSC gives higher dye loading and light adsorption ability as well as longer electron lifetime, resulting in higher short-circuit current value and superior power conversion efficiency (PCE) compared with Dyesol 18 nm TiO2 nanoparticle paste. Finally, the TiO2 microsphere-based DSSC were optimized by adding a TiO2 nanocrystal underlayer and TiCl4 post-treatment, giving a high PCE of 10.32%. PMID:25945694

  5. Ionic liquid mediated Cu-catalyzed cascade oxa-Michael-oxidation: efficient synthesis of flavones under mild reaction conditions.

    PubMed

    Du, Zhiyun; Ng, Huifen; Zhang, Kun; Zeng, Huaqiang; Wang, Jian

    2011-10-21

    Flavonoids are a class of natural products, found in a wide range of vascular plants and dietary components. Their low toxicity and extensive biological activities, including anti-cancer and anti-bacterial, have made them attractive candidates to serve as therapeutic agents for many diseases. Herein, we disclose a highly efficient synthetic method of CuI-catalyzed cascade oxa-Michael-oxidation, using chalcones as substrates, mediated by the ionic liquid [bmim][NTf2] at a low temperature. This efficient synthetic method has demonstrated high synthetic utility and can afford flavones in good to high yields (up to 98%). PMID:21897932

  6. Alum (KAl(SO 4 ) 2 · 12H 2 O): An Efficient and Inexpensive Catalyst for the One-pot Synthesis of 1,3,4-Oxadiazoles under Solvent-Free Conditions

    Microsoft Academic Search

    Minoo Dabiri; Peyman Salehi; Mostafa Baghbanzadeh; Mahboobeh Bahramnejad

    2007-01-01

    Summary.  Alum (KAl(SO4)2 · 12H2O) catalyzed the efficient synthesis of mono- and disubstituted 1,3,4-oxadiazoles by the condensation of acyl hydrazides with\\u000a orthoesters under solvent-free conditions at 100°C. This methodology offers significant improvements for the synthesis of\\u000a oxadiazoles with regard to the yield of products, simplicity in operation, inexpensive reagents, and green aspects by avoiding\\u000a toxic catalysts and solvents.

  7. Efficient Asymmetric Synthesis of 1-Cyano-tetrahydroisoquinolines from Lipase Dual Activity and Opposite Enantioselectivities in ?-Aminonitrile Resolution

    PubMed Central

    Sakulsombat, Morakot; Vongvilai, Pornrapee; Ramström, Olof

    2014-01-01

    Dual promiscuous racemization/amidation activities of lipases leading to efficient dynamic kinetic resolution protocols of racemic ?-aminonitrile compounds are described. ?-Amidonitrile products of high enantiomeric purity could be formed in high yields. Several lipases from different sources were shown to exhibit the dual catalytic activities, where opposite enantioselectivities could be recorded for certain substrates. PMID:25055970

  8. 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 ...

  9. 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

  10. Fully automated synthesis of (phospho)peptide arrays in microtiter plate wells provides efficient access to protein tyrosine kinase characterization

    PubMed Central

    Saxinger, Carl; Conrads, Thomas P; Goldstein, David J; Veenstra, Timothy D

    2005-01-01

    Background Synthetic peptides have played a useful role in studies of protein kinase substrates and interaction domains. Synthetic peptide arrays and libraries, in particular, have accelerated the process. Several factors have hindered or limited the applicability of various techniques, such as the need for deconvolution of combinatorial libraries, the inability or impracticality of achieving full automation using two-dimensional or pin solid phases, the lack of convenient interfacing with standard analytical platforms, or the difficulty of compartmentalization of a planar surface when contact between assay components needs to be avoided. This paper describes a process for synthesis of peptides and phosphopeptides on microtiter plate wells that overcomes previous limitations and demonstrates utility in determination of the epitope of an autophosphorylation site phospho-motif antibody and utility in substrate utilization assays of the protein tyrosine kinase, p60c-src. Results The overall reproducibility of phospho-peptide synthesis and multiplexed EGF receptor (EGFR) autophosphorylation site (pY1173) antibody ELISA (9H2) was within 5.5 to 8.0%. Mass spectrometric analyses of the released (phospho)peptides showed homogeneous peaks of the expected molecular weights. An overlapping peptide array of the complete EGFR cytoplasmic sequence revealed a high redundancy of 9H2 reactive sites. The eight reactive phospopeptides were structurally related and interestingly, the most conserved antibody reactive peptide motif coincided with a subset of other known EGFR autophosphorylation and SH2 binding motifs and an EGFR optimal substrate motif. Finally, peptides based on known substrate specificities of c-src and related enzymes were synthesized in microtiter plate array format and were phosphorylated by c-Src with the predicted specificities. The level of phosphorylation was proportional to c-Src concentration with sensitivities below 0.1 Units of enzyme. Conclusions The ability of this method to interface with various robotics and instrumentation is highly flexible since the microtiter plate is an industry standard. It is highly scalable by increasing the surface area within the well or the number of wells and does not require specialized robotics. The microtiter plate array system is well suited to the study of protein kinase substrates, antigens, binding molecules, and inhibitors since these all can be quantitatively studied at a single uniform, reproducible interface. PMID:15647109

  11. An efficient rhythmic component expression and weighting synthesis strategy for classifying motor imagery EEG in a brain computer interface

    NASA Astrophysics Data System (ADS)

    Wang, Tao; He, Bin

    2004-03-01

    The recognition of mental states during motor imagery tasks is crucial for EEG-based brain computer interface research. We have developed a new algorithm by means of frequency decomposition and weighting synthesis strategy for recognizing imagined right- and left-hand movements. A frequency range from 5 to 25 Hz was divided into 20 band bins for each trial, and the corresponding envelopes of filtered EEG signals for each trial were extracted as a measure of instantaneous power at each frequency band. The dimensionality of the feature space was reduced from 200 (corresponding to 2 s) to 3 by down-sampling of envelopes of the feature signals, and subsequently applying principal component analysis. The linear discriminate analysis algorithm was then used to classify the features, due to its generalization capability. Each frequency band bin was weighted by a function determined according to the classification accuracy during the training process. The present classification algorithm was applied to a dataset of nine human subjects, and achieved a success rate of classification of 90% in training and 77% in testing. The present promising results suggest that the present classification algorithm can be used in initiating a general-purpose mental state recognition based on motor imagery tasks.

  12. Facile additive-free synthesis of iron oxide nanoparticles for efficient adsorptive removal of Congo red and Cr(VI)

    NASA Astrophysics Data System (ADS)

    Hao, Tao; Yang, Chao; Rao, Xuehui; Wang, Jide; Niu, Chunge; Su, Xintai

    2014-02-01

    The iron oxide nanoparticles had been successfully synthesized via an additive-free hydrolysis process at 75 °C for 12 h. The product was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and N2 adsorption-desorption. The results of XRD and N2 adsorption-desorption demonstrated that the as-prepared product was mainly ?-Fe2O3 with a large surface area of 164.1 m2 g-1. The TEM images illustrated that the as-prepared product was found to consist of a mixture of irregular spherical nanoparticles (a diameter of ?50 nm) and nanowhiskers (a diameter of ?50 nm and uneven length). The as-prepared product was used to investigate its promising applications in water treatment. Due to its small size and large surface area, the maximum adsorption capacities of Congo red and Cr(VI) have been determined using the Langmuir equation and found to reach up to 253.8 and 17.0 mg g-1, respectively. The facile synthesis method and the superior adsorption performance derived from the iron oxide nanoparticles display the potential applications for the removal of Congo red and Cr(VI) from aqueous solution.

  13. Scalable and scalably-verifiable sequential synthesis

    Microsoft Academic Search

    Alan Mishchenko; Michael Case; Robert Brayton; Stephen Jang

    2008-01-01

    This paper describes an efficient implementation of sequential synthesis that uses induction to detect and merge sequentially-equivalent nodes. State-encoding, scan chains, and test vectors are essentially preserved. Moreover, the sequential synthesis results are sequentially verifiable using an independent inductive prover similar to that used for synthesis, with guaranteed completeness. Experiments with this sequential synthesis show effectiveness. When applied to a

  14. Solvothermal synthesis of InP quantum dots and their enhanced luminescent efficiency by post-synthetic treatments.

    PubMed

    Byun, Ho-June; Lee, Ju Chul; Yang, Heesun

    2011-03-01

    InP quantum dots (QDs) were solvothermally synthesized by using a greener phosphorus source of P(N(CH(3))(2))(3) instead of highly toxic P(TMS)(3) widely used, and subsequently subjected to a size-sorting processing. While as-grown QDs showed an undetectably low emission intensity, post-synthetic treatments such as photo-etching, photo-radiation, and photo-assisted ZnS shell coating gave rise to a substantial increase in emission efficiency due to the effective removal and passivation of surface states. The emission efficiency of the photo-etched QDs was further enhanced by a consecutive UV photo-radiation, attributable to the photo-oxidation at QD surface. Furthermore, a relatively thick ZnS shell on the surface of InP QDs that were surface-modified with hydrophilic ligands beforehand was photochemically generated in an aqueous solution at room temperature. The resulting InP/ZnS core/shell QDs, emitting from blue to red wavelengths, were more efficient than the above photo-treated InP QDs, and their luminescent properties (emission bandwidth and quantum yield) were comparable to those of InP QDs synthesized with P(TMS)(3). Structural, size, and compositional analyses on InP/ZnS QDs were also conducted to elucidate their core/shell structure. PMID:21194707

  15. 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

  16. Brønsted Acid-Mediated Annulation of ?-Oxo Ketene Dithioacetals with Pyrroles: Efficient Synthesis of Structurally Diverse Cyclopenta[b]pyrroles.

    PubMed

    Yang, Xiaoge; Wu, Kaikai; Wu, Ping; Chen, Jiping; Sun, Chenglin; Yu, Zhengkun

    2015-06-22

    Brønsted acid-mediated annulation of internal olefins ?-oxo ketene dithioacetals to pyrroles was efficiently achieved to afford cyclopenta[b]pyrroles. A pair of Brønsted acids with acid strengths, that is, trifluoroacetic acid, and para-toluenesulfonic acid hydrate, were applied to promote the annulation reactions. The resultant products were readily oxidized to sulfones by meta-chloroperoxybenzoic acid. Subsequent treatment with 1,8-diazabicyclo[5.4.0]undec-7-ene gave desulfurized terminal olefins or [2+2] cycloaddition products from the desulfurized olefin intermediates. The present protocol provides facile access to structurally diverse cyclopenta[b]pyrrole derivatives under mild conditions. PMID:26010358

  17. One-step synthesis of xanthones catalyzed by a highly efficient copper-based magnetically recoverable nanocatalyst.

    PubMed

    Menéndez, Cintia A; Nador, Fabiana; Radivoy, Gabriel; Gerbino, Darío C

    2014-06-01

    A versatile and highly efficient strategy to construct a xanthone skeleton via a ligand-free intermolecular catalytic coupling of 2-substituted benzaldehydes and a wide range of phenols has been developed. For this purpose, a novel and magnetically recoverable catalyst consisting of copper nanoparticles on nanosized silica coated maghemite is presented. The reaction proceeds smoothly with easy recovery and reuse of the catalyst. The methodology is compatible with various functional groups and provides an attractive protocol for the generation of a small library of xanthones in very good yield. PMID:24869459

  18. 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.

  19. Effect of post-synthesis acid activation of TiO2 nanofilms on the photocatalytic efficiency under visible light

    NASA Astrophysics Data System (ADS)

    Stambolova, I.; Blaskov, V.; Shipochka, M.; Eliyas, A.; Vassilev, S.

    2014-12-01

    Nanosized TiO2 films were deposited by spray pyrolysis and thermally treated at 400oC. Then the films were dipped in 1M aqueous solution of HCl. The activated samples were divided into two parts - one part was dried (A) and another was annealed (AT) in air. The photocatalytic degradation of Reactive Black (RB5) textile dye under visible light was tested. The following instrumental methods: X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were applied for the phase and surface characterization of obtained samples. According to Raman and XRD analyses all films are anatase. The XRD showed that activated films are better crystallized than non activated TiO2 film. The presence of chlorine at 200.3 eV was registered for acid activated samples by X-Ray photoelectron spectroscopy. The acidic activated films exhibited higher rate of dye photodegradation than that of the reference TiO2 sample. The photocatalytic efficiency decreases in the order A > AT> non activated TiO2 films. The degradation rate constant for acid activated films is two times higher than those of the reference film. The hydroxyl content in TiO2 acidic activated films is greater than that of the non- activated films, which results in significant increase in the photocatalytic activity. In addition, the presence of chlorine may also lead to enhancement in efficiency.

  20. 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

  1. 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

  2. Highly efficient synthesis of ethyl (S)-4-chloro-3-hydroxybutanoate and its derivatives by a robust NADH-dependent reductase from E. coli CCZU-K14.

    PubMed

    He, Yu-Cai; Tao, Zhi-Cheng; Zhang, Xian; Yang, Zhen-Xing; Xu, Jian-He

    2014-06-01

    An NADH-dependent reductase (CmCR) from Candida magnoliae was discovered by genome mining for carbonyl reductases. After CmCR was overexpressed in Escherichia coli BL21, a robust reductase-producing strain, recombinant E. coli CCZU-K14, was employed for the efficient synthesis of ethyl (S)-4-chloro-3-hydroxybutanoate ((S)-CHBE) from the reduction of ethyl 4-chloro-3-oxobutanoate (COBE). After the optimization, the optimum reaction conditions were obtained. Notably, E. coli CCZU-K14 had broad substrate specificity in reducing both aliphatic and aromatic substrates, and excellent enantioselectivity of CCZU-K14 was observed for most of the tested substrates, resulting in chiral alcohols of over 99.9% ee. Moreover, COBE at a high concentration of (3000mM) could be asymmetrically reduced to (S)-CHBE in the high yield (>99.0%) and high enantiometric excess value (>99.9% ee) after 14h. Significantly, E. coli CCZU-K14 shows high potential in the industrial production of (S)-CHBE and its derivatives (>99.9% ee). PMID:24745897

  3. 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.

  4. Supported Pd and PdAu Nanoparticles on Ti-MCM-41 Prepared by a Photo-assisted Deposition Method as Efficient Catalysts for Direct Synthesis of H 2 O 2 from H 2 and O 2

    Microsoft Academic Search

    Kohsuke Mori; Takashi Araki; Sayoko Shironita; Joji Sonoda; Hiromi Yamashita

    2009-01-01

    An efficient methodology to synthesize highly active Pd nanoparticles using a single-site photocatalyst under UV-light irradiation\\u000a has been developed for the synthesis of hydrogen peroxide (H2O2) from H2 and O2. By the photo-assisted deposition (PAD) method, Pd precursor can be deposited directly on the photo-excited tetrahedrally\\u000a coordinated metal-oxide moiety within the silica frameworks, and subsequently transformed into Pd nanoparticles by

  5. An efficient cascade synthesis of various 2H-1,4-benzoxazin-3-(4H)-ones from o-halophenols and 2-halo-amides catalyzed by CuI.

    PubMed

    Chen, Dingben; Shen, Guodong; Bao, Weiliang

    2009-10-01

    A novel and efficient one-pot cascade synthesis of 2H-1,4-benzoxazin-3-(4H)-ones has been developed through copper-catalyzed coupling of o-halophenols and 2-halo-amides. Various 2H-1,4-benzoxazin-3-(4H)-ones with diversity at three substituents on their scaffold have been synthesized conveniently in good to excellent yields. PMID:19763313

  6. 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.

  7. Efficient 11C-carbonylation of isolated aryl palladium complexes for PET: application to challenging radiopharmaceutical synthesis.

    PubMed

    Andersen, Thomas L; Friis, Stig D; Audrain, Hélène; Nordeman, Patrik; Antoni, Gunnar; Skrydstrup, Troels

    2015-02-01

    We describe the successful implementation of palladium-aryl oxidative addition complexes as stoichiometric reagents in carbonylation reactions with (11)CO to produce structurally challenging, pharmaceutically relevant compounds. This method enables the first (11)C-carbonyl labeling of an approved PET tracer, [(11)C]raclopride, for the dopamine D2/D3 receptor by carbonylation with excellent radiochemical purity and yield. Two other molecules, [(11)C]olaparib and [(11)C]JNJ 31020028, were efficiently labeled in this manner. The technique distinguishes itself from existing methods by the markedly improved purity profiles of the tracer molecules produced and provides access to complex structures in synthetically useful yields, hereby offering a viable alternative to other (11)C-labeling strategies. PMID:25569730

  8. 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

  9. Synthesis of Fondaparinux: modular synthesis investigation for heparin synthesis.

    PubMed

    Lin, Feng; Lian, Gaoyan; Zhou, Ying

    2013-04-19

    The anti-thromboembolic pentasaccharide Fondaparinux was synthesized in 36 steps for the longest linear route, with 0.017% overall yield from D-glucose. Only three kinds of protecting groups were used for hydroxyl protection, Bn, Ac, and Bz, to accomplish this complex synthesis without decreasing the synthetic efficiency. Three L-idopyranosyl donors were investigated. Thioethyl glycoside is an efficient donor for L-idopyranosyl glycosylation with full ?-selectivity, while L-idopyranosyl trichloroacetimidate resulted in poor ?/? selectivity. A practical synthesis of key intermediate 1,6-anhydro-L-idopyranose 17 by H(+)/?-CD catalyst was developed. PMID:23474455

  10. Efficient Electrochemical Synthesis, Antimicrobial and Antiinflammatory Activity of 2–amino-5-substituted- 1,3,4-oxadiazole Derivatives

    PubMed Central

    Kumar, S.; Srivastava, D. P.

    2010-01-01

    An efficient electrochemical method for the preparation of 2-amino-5-substituted-1,3,4-oxadiazoles (4a-k) at platinum anode through the electrooxidation of semicarbazone (3a-k) at controlled potential electrolysis has been reported in the present study. The electrolysis was carried out in the acetic acid solvent and lithium perchlorate was used as supporting electrolyte. The products were characterized by IR,1H-NMR,13C-NMR, mass spectra and elemental analysis. The synthesized compounds were screened for their in vitro growth inhibiting activity against different strains of bacteria viz., Klebsilla penumoniae, Escherichia coli, Bassilus subtilis and Streptococcus aureus and antifungal activity against Aspergillus niger and Crysosporium pannical and results have been compared with the standard antibacterial streptomycin and antifungal griseofulvin. Compounds exhibits significant antibacterial activity and antifungal activity. Compounds 4a and g exhibited equal while 4c, d, i and j slightly less antibacterial activity than standard streptomycin. Compounds 4a and g exhibited equal while 4b, c, d, f and i displayed slightly less antifungal activity than standard griseofulvins. PMID:21218056

  11. High-yield synthesis of sub-10 nm Pt nanotetrahedra with bare ?111? facets for efficient electrocatalytic applications.

    PubMed

    Rana, Moumita; Chhetri, Manjeet; Loukya, B; Patil, Pramod K; Datta, Ranjan; Gautam, Ujjal K

    2015-03-01

    Unlike other shapes, the design of tetrahedral Pt nanocrystals (Pt-NTd), which have the largest number of Pt(111) surface atoms and highest catalytic activities toward the electron transfer reactions, has widely been considered a synthetic challenge due to their thermodynamic instability. Here, we show that, by inducing their nucleation on functionalized carbon, Pt NTds can be obtained with tunable sizes and high yields. The carbon support anchors the nanocrystals early and prevents their oriented attachment leading to nanowire formation. Therein, an in situ generated amine is crucial for stabilization of Pt-NTds, which can later be removed to expose the Pt(111) facets for higher catalytic efficiency. The bare nanocrystals exhibit much improved stability and electrocatalytic activity characteristic of Pt(111) toward oxygen reduction reaction (ORR) and methanol and formic acid oxidation reactions. For example, ?90% of their activity was retained after 5000 potential cycles, while the ORR onset potential was recorded to be very high, 1.01 V vs reversible hydrogen electrode (RHE). PMID:25660263

  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. 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

  14. Total synthesis of marinomycin A using salicylate as a molecular switch to mediate dimerization.

    PubMed

    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. PMID:22824902

  15. Synthesis of zwitterionic polymer brushes hybrid silica nanoparticles via controlled polymerization for highly efficient enrichment of glycopeptides.

    PubMed

    Huang, Guang; Xiong, Zhichao; Qin, Hongqiang; Zhu, Jun; Sun, Zhen; Zhang, Yi; Peng, Xiaojun; ou, Junjie; Zou, Hanfa

    2014-01-27

    Zwitterionic hydrophilic interaction chromatography (ZIC-HILIC) materials have been increasingly attractive in glycopeptide enrichment. However, the traditional ZIC-HILIC materials are modified with monolayer zwitterionic molecules on the surface, therefore, the hydrophilicity, detection sensitivity and loading capacity are limited. In this work, we synthesized novel silica nanoparticles with uniform poly(2-(methacryloyloxy)ethyl)dimethyl-(3-sul-fopropyl)ammonium hydroxide (PMSA) brushes grafted onto the surface via reversible addition-fragmentation chain transfer (RAFT) polymerization (denoted as SiO2-RAFT@PMSA). The resulting SiO2-RAFT@PMSA nanoparticles demonstrated low detection limit (10 fmol) and high recovery yield (over 88%) for glycopeptide enrichment from tryptic digest of human IgG. The SiO2-RAFT@PMSA nanoparticles were further applied for the analysis of mouse liver glycoproteome, a total number of 303 unique N-glycosylation sites corresponding to 185 glycoproteins was reliably profiled in three replicate nano-LC-MS/MS runs. Significantly, more glycopeptides were identified than those of nanoparticles, monolayer MSA molecules modified SiO2@single-MSA and nonuniform multi-layer PMSA brushes coated SiO2@PMSA, as well as commercial ZIC@HILIC beads and Click Maltose beads. The excellent performance of SiO2-RAFT@PMSA nanoparticles results from the non-fouling property, a large quantity of functional molecules and suitable link arms provided by uniform PMSA brushes, as well as efficient interaction between glycopeptides and uniform PMSA brushes. It is concluded that the synthesized SiO2-RAFT@PMSA nanoparticles exhibit great potential in glycoproteome analysis. Moreover, this strategy to modify nanopaticles with uniform polymer brushes via RAFT polymerization can also be explored to design other types of materials for bioseparation application. PMID:24418134

  16. 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. (UNC); (Connecticut)

    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.

  17. 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.

  18. Optimization of a two-step process comprising lipase catalysis and thermal cyclization improves the efficiency of synthesis of six-membered cyclic carbonate from trimethylolpropane and dimethylcarbonate.

    PubMed

    Bornadel, Amin; Hatti-Kaul, Rajni; Sörensen, Kent; Lundmark, Stefan; Pyo, Sang-Hyun

    2013-01-01

    Six-membered cyclic carbonates are potential monomers for phosgene and/or isocyanate free polycarbonates and polyurethanes via ring-opening polymerization. A two-step process for their synthesis comprising lipase-catalyzed transesterification of a polyol, trimethylolpropane (TMP) with dimethylcarbonate (DMC) in a solvent-free system followed by thermal cyclization was optimized to improve process efficiency and selectivity. Using full factorial designed experiments and partial least squares (PLS) modeling for the reaction catalyzed by Novozym®435 (N435; immobilized Candida antarctica lipase B), the optimum conditions for obtaining either high proportion of monocarbonated TMP and TMP-cyclic-carbonate (3 and 4), or dicarbonated TMP and monocarbonated TMP-cyclic-carbonate (5 and 6) were found. The PLS model predicted that the reactions using 15%-20% (w/w) N435 at DMC:TMP molar ratio of 10-30 can reach about 65% total yield of 3 and 4 within 10 h, and 65%-70% total yield of 5 and 6 within 32-37 h, respectively. High consistency between the predicted results and empirical data was shown with 66.1% yield of 3 and 4 at 7 h and 67.4% yield of 5 and 6 at 35 h, using 18% (w/w) biocatalyst and DMC:TMP molar ratio of 20. Thermal cyclization of the product from 7 h reaction, at 110°C in the presence of acetonitrile increased the overall yield of cyclic carbonate 4 from about 2% to more than 75% within 24 h. N435 was reused for five consecutive batches, 10 h each, to give 3+4 with a yield of about 65% in each run. PMID:23125051

  19. Monosaccharides as Scaffolds for the Synthesis of Novel Compounds

    NASA Astrophysics Data System (ADS)

    Murphy, Paul V.; Velasco-Torrijos, Trinidad

    This chapter focuses on monosaccharides and scaffolds their derivatives as scaffolds for the synthesis of primarily bioactive compounds. Such carbohydrate derivatives have been designed to modulate mainly protein-protein and peptide-protein interactions although modulators of carbohydrate-protein and carbohydrate-nucleic acid interactions have also been of interest. The multiple hydroxyl groups that are present on saccharides have made pyranose, furanose and iminosugars ideal templates or scaffolds to which recognition or pharmacophoric groups can be grafted to generate novel compounds for medicinal chemistry. The synthesis of compounds for evaluations require strategies for regioselective reactions of saccharide hydroxyl groups and use of orthogonally stable protecting groups. Syntheses have been carried out on the solid phase and in solution. Also the use of uronic acids, amino sugars and sugar amino acids has facilitated the synthesis of peptidomimetics and prospecting libraries as they enable, through presence of amino or carboxylic acid groups, chemoselective approaches to be employed in solution and on solid phase. Sugar amino acids are readily incorporated, as peptide isosteres, to generate sugar-peptide hybrids or for the synthesis of novel carbopeptoids . The synthesis of new cyclic compounds, derived in part from saccharides, and their application as scaffolds is an emerging area and recent examples include spirocyclic compounds, benzodiazepine-saccharide hybrids and macrolide-saccharide hybrids. Potent bioactive saccharide derivatives have been identified that include enzyme inhibitors , somatostatin receptor ligands, integrin ligands, anti-viral compounds, shiga toxin inhibitors and cell growth inhibitors. Some saccharide derivatives have demonstrated improved cellular permeability when compared with peptides and are in clinical trials.

  20. Efficient synthesis of functionalized dihydroquinolines, quinolines and dihydrobenzo[b]azepine via an iron(III) chloride-catalyzed intramolecular alkyne-carbonyl metathesis of alkyne tethered 2-amino benzaldehyde/acetophenone derivatives.

    PubMed

    Jalal, Swapnadeep; Bera, Krishnendu; Sarkar, Soumen; Paul, Kartick; Jana, Umasish

    2014-03-21

    In this study we have developed an efficient synthesis of 1,2-dihydroquinoline and dihydrobenzo[b]azepine derivatives involving the iron(III) chloride intramolecular alkyne-carbonyl metathesis reaction for the first time. Various functionalized 1,2-dihydroquinolines and dihydrobenzo[b]azepines were prepared from easily accessible substrates in the presence of environmentally friendly and inexpensive iron(III) chloride (10 mol%) under mild conditions. The method is applicable to a wide range of substrates containing different functional groups and furnishing products in good to excellent yields. This methodology was further extended to the one-pot synthesis of 3-acyl quinolines via alkyne-carbonyl metathesis/detosylation/aromatization of N-propargyl-2-aminobenzaldehyde/acetophenone derivatives by the addition of NaOH/EtOH. While many Lewis acid and Brønsted acid catalysts were investigated, anhydrous iron(III) chloride turned out to be the best catalyst for this transformation. PMID:24500306

  1. Alum Catalyzed Simple, Efficient, and Green Synthesis of 2-[3-Amino-5-methyl-5-(pyridin-3-yl)-1,5-dihydro-4H-1,2,4-triazol-4-yl]propanoic Acid Derivatives in Aqueous Media

    PubMed Central

    Sachdeva, Harshita; Dwivedi, Diksha; Saroj, Rekha

    2013-01-01

    Alum (KAl(SO4)2·12H2O) is an inexpensive, efficient, and nontoxic catalyst used for the synthesis of 2-[3-amino-5-methyl-5-(pyridin-3-yl)-1,5-dihydro-4H-1,2,4-triazol-4-yl]propanoic acid derivatives in aqueous media by the reaction of 3-acetyl pyridine (1), amino acids (2)/(6), and thiosemicarbazide (4) at 80°C. This methodology offers significant improvements for the synthesis of products with regards to the yield of products, simplicity in operation, and green aspects by avoiding toxic catalysts which uphold the motto of green chemistry. Synthesized compounds have been characterized by FT-IR, 13C NMR, and 1HNMR spectroscopy. PMID:24288503

  2. An eco-friendly procedure for the efficient synthesis of arylidinemalononitriles and 4,4?-(arylmethylene)bis(3-methyl-1-phenyl-1H-pyrazol-5-ols) in aqueous media

    Microsoft Academic Search

    Moustafa A. Gouda; Ameen A. Abu-Hashem

    2012-01-01

    Commercially available lithium hydroxide monohydrate (LiOH·H2O) was found to be a novel “dual activation” catalyst for Knoevenagel condensation between malononitrile (1) or 3-methyl 1-phenyl-1H-pyrazol-5-(4H)-one (6) with aromatic aldehydes 2a–e leading to an efficient and easy synthesis of arylidenemalononitriles 3a–d and 4,4?-(arylmethylene)bis(3-methyl-1-phenyl-1H-pyrazol-5-ols) 7a–c in short times. The reaction of aryl aldehydes with malononitrile afforded excellent yields after 1–6 min in aqueous

  3. An efficient and facile one-pot synthesis of structurally unique 2,4,6-tris(arylchalcogeno)-1,3,5-triazine and 1,3,5-tris(arylchalcogeno)-2,4,6-trimethylbenzene

    Microsoft Academic Search

    Marilyn Daisy Milton; Naveen Kumar; Sarbjot Singh Sokhi; Sarika Singh; Jai Deo Singh

    2004-01-01

    An efficient one-pot synthesis of a novel class of 2,4,6-tris(arylchalcogeno)-1,3,5-triazine (sulfur, selenium and tellurium) and 1,3,5-tris(arylchalcogeno)-2,4,6-trimethylbenzene (sulfur and selenium)-containing ligands has been developed based on the reaction of 2,4,6-trichloro-1,3,5-triazine and 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene with the corresponding arylchalcogenide anions generated in aqueous tetrahydrofuran.

  4. Scalable and scalably-verifiable sequential synthesis

    Microsoft Academic Search

    Alan Mishchenko; Michael L. Case; Robert K. Brayton; Stephen Jang

    2008-01-01

    This paper describes an efficient implementation of an effective sequential synthesis operation that uses induction to detect and merge sequentially-equivalent nodes. State-encoding, scan chains, and test vectors are essentially preserved. Moreover, the sequential synthesis results are guaranteed to be sequentially verifiable against the original circuits. Verification can use an independent inductive prover similar to that used for synthesis, with guaranteed

  5. Enantioselective total synthesis of (-)-laurenditerpenol.

    PubMed

    Pitsinos, Emmanuel N; Athinaios, Nikolaos; Vidali, Veroniki P

    2012-09-01

    A highly convergent total synthesis of (-)-laurenditerpenol has been accomplished through an organolithium to aldehyde nucleophilic addition. Preparation of the prerequisite key intermediates in optically pure form was based on an improved, short, and efficient synthesis of "wine lactone" from (S)-limonene and Corey's catalytic enantioselective Diels-Alder reaction of 2,5-dimethyl furan with diethyl fumarate. PMID:22905649

  6. Vanillin Synthesis from 4-Hydroxybenzaldehyde

    ERIC Educational Resources Information Center

    Taber, Douglass F.; Patel, Shweta; Hambleton, Travis M.; Winkel, Emma E.

    2007-01-01

    A regioselective, safe and efficient method for the synthesis of vanillin from 4-hydroxybenzaldehyde is being described. The vanillin derived from the process is cheap and can be used as a flavor or in the paper industry.

  7. Efficient and Convenient Synthesis of 1,8-Dioxodecahydroacridine Derivatives Using Cu-Doped ZnO Nanocrystalline Powder as a Catalyst under Solvent-Free Conditions

    PubMed Central

    Alinezhad, Heshmatollah; Mohseni Tavakkoli, Sahar

    2013-01-01

    A simple and convenient one-step method for synthesis of acridines and their derivatives from condensation of aromatic aldehydes, cyclic diketones, and aryl amines using Cu-doped ZnO nanocrystalline powder as a catalyst is reported. The present protocol provides several advantages such as good yields, short reaction time, easy workup, and simplicity in operation. PMID:24294130

  8. Synthesis of (-)-9,10-epi-stemoamide.

    PubMed

    Khim, Seock-Kyu; Schultz, Arthur G

    2004-10-29

    An efficient synthesis of (-)-9,10-epi-stemoamide has been accomplished in nine steps and 13% overall yield. The synthesis features a lithium hydroxide-promoted fragmentation and an intramolecular 7-exo-trig radical cyclization. PMID:15498004

  9. Concise total synthesis of (+)-gliocladins B and C

    E-print Network

    Movassaghi, Mohammad

    The first total synthesis of (+)-gliocladin B is described. Our concise and enantioselective synthesis takes advantage of a new regioselective Friedel–Crafts-based strategy to provide an efficient multigram-scale access ...

  10. A rapid and efficient method for the synthesis of selectively S-Trt or S-Mmt protected Cys-containing peptides.

    PubMed

    Stathopoulos, Panagiotis; Papas, Serafim; Sakka, Marianna; Tzakos, Andreas G; Tsikaris, Vassilios

    2014-05-01

    Selective removal of protecting groups under different cleavage mechanisms could be an asset in peptide synthesis, since it provides the feasibility to incorporate different functional groups in similar reactive centres. However, selective protection/deprotection of orthogonal protecting groups in peptides is still challenging, especially for Cys-containing peptides, where protection of the cysteine side-chain is mandatory since the nucleophilic thiol can be otherwise alkylated, acylated or oxidized. Herein, we established a protocol for the synthesis of Cys-selective S-Trt or S-Mmt protected Cys-containing peptides, in a rapid way. This was achieved by, simply fine-tuning the carbocation scavenger in the final acidolytic release of the peptide from the solid support in the classic SPPS. PMID:24609270

  11. Introduction of poly(4-vinylpyridinium) perchlorate as a new, efficient, and versatile solid acid catalyst for one-pot synthesis of substituted coumarins under ultrasonic irradiation.

    PubMed

    Khaligh, Nader Ghaffari; Shirini, Farhad

    2013-01-01

    Poly(4-vinylpyridinium) perchlorate, is a supported, recyclable, eco-benign catalyst for synthesis of substituted coumarins via Pechmann reaction using ultrasound irradiation at room temperature and neat condition in high yields with short reaction times. The catalyst was studied by FT-IR, X-ray diffraction, scanning electron microscope, thermo-gravimetric and energy dispersion X-ray analyses. All the products were extensively characterized by (1)H NMR, FT-IR, MS and melting point analyses. This methodology offers momentous improvements over various options for the synthesis of coumarins with regard to yield of products, simplicity in operation and green aspects by avoiding toxic catalysts and solvents. Further, the catalyst can be reused and recovered for several times without loss of activity. PMID:22922036

  12. An efficient biomaterial supported bifunctional organocatalyst (ES-SO3- C5H5NH+) for the synthesis of ?-amino carbonyls.

    PubMed

    Verma, Sanny; Jain, Suman L; Sain, Bir

    2011-04-01

    A biomaterial supported organocatalyst, readily synthesized by the reaction of chemically modified sulfonic group containing expanded corn starch with pyridine exhibited excellent catalytic activity for the synthesis of ?-amino carbonyls in excellent yields via aza-Michael addition of amines to electron deficient alkenes. A remarkable enhancement in the reaction rates was observed with the prepared bifunctional organocatalyst in comparison to the either starch grafted sulfonic acid or the corresponding homogeneous pyridinium p-toluenesulfonate. PMID:21321768

  13. At the same hepatic amino acid load, portal infusion of amino acids is more efficient than peripheral infusion in stimulating liver protein synthesis in the dog

    PubMed Central

    Dardevet, Dominique; Kimball, Scot R; Jefferson, Leonard S; Cherrington, Alan D; Rémond, Didier; DiCostanzo, Catherine A; Moore, Mary Courtney

    2009-01-01

    Background Hepatic glucose uptake is enhanced by portal delivery of glucose which creates a negative arterio-portal substrate gradient. Hepatic amino acid (AA) utilization may be regulated by the same phenomenon, but this has not been proven. Objective We aimed to assess hepatic AA balance and protein synthesis with or without a negative arterio-portal AA gradient. Design Somatostatin was infused IV, and insulin and glucagon were replaced intraportally at 4- and 3-fold basal rates, respectively, in 3 groups (n=9 each) of conscious dogs with catheters for hepatic balance measurement. Arterial glucose concentrations were clamped at 9 mM. An AA mixture was infused IV to maintain basal concentrations (EuAA), intraportally to mimic the post-meal AA increase (PoAA), or IV (PeAA) to match the hepatic AA load in PoAA. Protein synthesis was assessed with a primed, continuous [14C]leucine infusion. Results Net hepatic glucose uptake in PoAA was ?50% of that in EuAA and PeAA (P<0.05). The hepatic intracellular leucine concentration was 2- to 2.5-fold greater in PoAA and PeAA than EuAA (P<0.05); net hepatic leucine uptake and 14C leucine utilization were ?2-fold greater (P<0.05) and albumin synthesis was 30% greater (P<0.05) in PoAA than EuAA and PeAA, Phosphorylation of ribosomal protein S6 (downstream of the mammalian target of Rapamycin complex 1 [mTORC1]) was significantly increased in PoAA, but not PeAA, vs EuAA. Conclusions Portal, but not peripheral, AA delivery significantly enhanced hepatic protein synthesis under conditions where AA, glucose, insulin and glucagon did not differ at the liver, an effect apparently mediated by mTORC1 signalling. PMID:18842785

  14. The formulation of a quantitative series of simulation-based tools for the expeditious and effective synthesis of comprehensive energy efficient building structures

    Microsoft Academic Search

    Casimir P. Kotarba

    2006-01-01

    The construction of a detailed equivalent circuit model has been developed as a valid approach to accurately gauge the magnitude of energy performance of a given building and to conceptualize the inherent efficiency of a series of contributing design features. It has been demonstrated that a reliance on fuel cell technology adds substantial support to a state of energy efficiency

  15. Large-scale synthesis of TiO2 microspheres with hierarchical nanostructure for highly efficient photodriven reduction of CO2 to CH4.

    PubMed

    Fang, Baizeng; Bonakdarpour, Arman; Reilly, Kevin; Xing, Yalan; Taghipour, Fariborz; Wilkinson, David P

    2014-09-10

    In this study, a simple and reproducible synthesis strategy was employed to fabricate TiO2 microspheres with hierarchical nanostructure. The microspheres are macroscopic in the bulk particle size (several hundreds to more than 1000 ?m), but they are actually composed of P25 nanoparticles as the building units. Although it is simple in the assembly of P25 nanoparticles, the structure of the as-prepared TiO2 microspheres becomes unique because a hierarchical porosity composed of macropores, larger mesopores (ca. 12.4 nm), and smaller mesopores (ca. 2.3 nm) has been developed. The interconnected macropores and larger mesopores can be utilized as fast paths for mass transport. In addition, this hierarchical nanostructure may also contribute to some extent to the enhanced photocatalytic activity due to increased multilight reflection/scattering. Compared with the state-of-the-art photocatalyst, commercial Degussa P25 TiO2, the as-prepared TiO2 microsphere catalyst has demonstrated significant enhancement in photodriven conversion of CO2 into the end product CH4. Further enhancement in photodriven conversion of CO2 into CH4 can be easily achieved by the incorporation of metals such as Pt. The preliminary experiments with Pt loading reveal that there is still much potential for considerable improvement in TiO2 microsphere based photocatalysts. Most interestingly and significantly, the synthesis strategy is simple and large quantity of TiO2 microspheres (i.e., several hundred grams) can be easily prepared at one time in the lab, which makes large-scale industrial synthesis of TiO2 microspheres feasible and less expensive. PMID:25140917

  16. An efficient and expeditious synthesis of di- and trisubstituted amino-phenyl and -benzyl derivatives of tetrazole and [1,3,4]oxadiazol-2-one.

    PubMed

    Desforges, Gwenaelle; Bombrun, Agnes; Quattropani, Anna

    2008-01-01

    A practical protocol for the parallel synthesis and purification of amino tetrazole and [1,3,4]oxadiazol-2-one derivatives as carboxylic acid bioisosteres is described. Phenyl- and benzyl-amines, substituted with tetrazole or [1,3,4]oxadiazol-2-one, were transformed into functionally diverse and novel compounds, with p K a values ranging from 4.9 to 8.4, by two sequential reductive alkylation reactions. These series of di- and trisubstituted amino-phenyl and -benzyl derivatives were produced in solution using solid-supported reagents and were purified by solid-phase extraction (SPE) techniques. PMID:18707176

  17. 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

  18. An efficient approach to Aspidosperma alkaloids via [4 + 2] cycloadditions of aminosiloxydienes: stereocontrolled total synthesis of (+/-)-tabersonine. Gram-scale catalytic asymmetric syntheses of (+)-tabersonine and (+)-16-methoxytabersonine. Asymmetric syntheses of (+)-aspidospermidine and (-)-quebrachamine.

    PubMed

    Kozmin, Sergey A; Iwama, Tetsuo; Huang, Yong; Rawal, Viresh H

    2002-05-01

    Described is a concise, highly stereocontrolled strategy to the Aspidosperma family of indole alkaloids, one that is readily adapted to the asymmetric synthesis of these compounds. The strategy is demonstrated by the total synthesis of (+/-)-tabersonine (rac-1), proceeding through a 12-step sequence. The basis for this approach was provided by a highly regio- and stereoselective [4 + 2] cycloaddition of 2-ethylacrolein with 1-amino-3-siloxydiene developed in our laboratory. Subsequent elaboration of the initial adduct into the hexahydroquinoline DE ring system was accomplished efficiently by a ring-closing olefin metathesis reaction. A novel ortho nitrophenylation of an enol silyl ether with (o-nitrophenyl)phenyliodonium fluoride was developed to achieve an efficient, regioselective introduction of the requisite indole moiety. The final high-yielding conversion of the ABDE tetracycle into pentacyclic target rac-1 relied on intramolecular indole alkylation and regioselective C-carbomethoxylation. Our approach differs strategically from previous routes and contains built-in flexibility necessary to access many other members of the Aspidosperma family of indole alkaloids. The versatility of the synthetic strategy was illustrated through the asymmetric syntheses of the following Aspidosperma alkaloids: (+)-aspidospermidine, (-)-quebrachamine, (-)-dehydroquebrachamine, (+)-tabersonine, and (+)-16-methoxytabersonine. Of these, (+)-tabersonine and (+)-16-methoxytabersonine were synthesized in greater than 1-g quantities and in enantiomerically enriched form ( approximately 95% ee). The pivotal asymmetry-introducing step was a catalyzed enantioselective Diels-Alder reaction, which proceeded to afford the cycloadducts in up to 95% ee. Significantly, the synthetic sequence was easy to execute and required only four purifications over the 12-step synthetic route. PMID:11971711

  19. Synthesis and characterization of NaYF4: Yb, Er nanoparticles with efficient up-conversion fluorescence based on new type solar cells

    Microsoft Academic Search

    X. D. Zhang; X. Jin; Z. F. Lei; N. Cai; S. Z. Xiong; Y. Zhao

    2008-01-01

    An up-converting material, which can be efficiently excited by near infrared light and emit strong visible light through a process termed dasiaup-conversion fluorescencepsila, has shown great potential for use in silicon thin films solar cells. This kind of material when placed on the rear side of p-i-n type silicon thin films solar cells will increase the overall efficiency of the

  20. Total Synthesis of (+)-Irciniastatin A (a.k.a. Psymberin) and (?)-Irciniastatin B

    PubMed Central

    An, Chihui; Jurica, Jon A.; Walsh, Shawn P.; Hoye, Adam T.; Smith, Amos B.

    2013-01-01

    A unified synthetic strategy to access (+)-irciniastatin A (a.k.a. psymberin) and (?)- irciniastatin B, two cytotoxic secondary metabolites, has been achieved. Highlights of the convergent strategy comprise a boron-mediated aldol union to set the C(15)–C(17) syn-syn triad, reagent control to set the four stereocenters of the tetrahydropyran core, and a late-stage Curtius rearrangement to install the acid-sensitive stereogenic N,O-aminal. Having achieved the total synthesis of (+)-irciniastatin A, we devised an improved synthetic route to the tetrahydropyran core (13 steps) compared to the first-generation synthesis (22 steps). Construction of the structurally similar (?)-irciniastatin B was then achieved via modification of a late-stage (?)-irciniastatin A intermediate to implement a chemoselective deprotection/oxidation sequence to access the requisite oxidation state at C(11) of the tetrahydropyran core. Of particular significance, the unified strategy will permit late-stage diversification for analogue development, designed to explore the biological role of substitution at the C(11) position of these highly potent tumor cell growth inhibitory molecules. PMID:23510264

  1. An efficient solid-phase strategy for total synthesis of naturally occurring amphiphilic marine siderophores: amphibactin-T and moanachelin ala-B.

    PubMed

    Cherkupally, Prabhakar; Ramesh, Suhas; Govender, Thavendran; Kruger, Hendrik G; de la Torre, Beatriz G; Albericio, Fernando

    2015-04-28

    Microorganisms such as bacteria, fungi and some plants secrete an abundance of suites of low molecular weight, high-affinity iron(iii)-chelating acylated siderophores. The peptide composition of a suite of amphiphilic siderophores generated by a Vibrio species, isolated from oligotrophic open ocean water, contained the same iron(iii)-scavenging polar head group and is attached to a fatty acid. In the present study, we report the first total synthesis of the naturally obtainable marine siderophores amphibactin-T and moanachelin ala-B on solid-phase using standard Fmoc-chemistry. Furthermore, we discuss the preparation of orthogonal protected Orn amino acid 'N(?)-Fmoc-N(?)-(acetyl)-N(?)-(benzoyloxy)-ornithine' [Fmoc-Orn(Ac,OBz)-OH], which is the most important constructive building block for amphibactin and moanachelin siderophores syntheses. The applications of this Orn unit on solid-phase have also been discussed. PMID:25806414

  2. Synthesis, Spectroscopic and Thermal Characterization of Copper(II) and Iron(III) Complexes of Folic Acid and Their Absorption Efficiency in the Blood

    PubMed Central

    Hamed, E.; Attia, M. S.; Bassiouny, K.

    2009-01-01

    The absorption efficiency of any drug in blood is of prime importance. Compounds having the general formula: Kn[M(FO)2(H2O)2] · xH2O, where (M = Cu(II) or Fe(III), n = 2 or 1, FO = folate anion, x = 2 or 3 with respect), were prepared, and their absorption efficiency in rodent's blood was determined. The obtained compounds were characterized by elemental analysis, infrared as well as thermogravimetric analysis and polarization of light. The results suggest that the two folate complexes were formed in 1 : 2 molar ratio (metal : folic acid) which acted as a bidentate ligand through both carboxylic groups. Polarization of light proved that the folate complexes have symmetric geometry. Biological application proved that Cu(II) and Fe(III) complexes were absorbed more efficiently in rodent blood than folic acid itself. PMID:19746175

  3. Efficient construction of pyrano[3,2-a]carbazoles: application to a biomimetic total synthesis of cyclized monoterpenoid pyrano[3,2-a]carbazole alkaloids.

    PubMed

    Hesse, Ronny; Gruner, Konstanze K; Kataeva, Olga; Schmidt, Arndt W; Knölker, Hans-Joachim

    2013-10-11

    We have developed a highly efficient route to 2-hydroxy-3-methylcarbazole (1) via a palladium-catalyzed construction of the carbazole skeleton. Using 1 as relay compound, different methods for annulations of pyran rings by reaction with terpenoid building blocks have been tested. The Lewis acid promoted reaction of 1 with prenal (21) opened up an efficient route to girinimbine (3) and the corresponding reaction with citral (25) afforded mahanimbine (5). Oxidation of compounds 3 and 5 provided murrayacine (4) and murrayacinine (6). Following the biogenetic proposal, mahanimbine (5) has been exploited for efficient biomimetic syntheses of the cyclized monoterpenoid pyrano[3,2-a]carbazole alkaloids cyclomahanimbine (7), mahanimbidine (8) and bicyclomahanimbine (9). The interconversions of 5, 7, 8 and 9 are described and mechanistic implications are discussed. Structural assignments are unambiguously verified by X-ray crystal structure determinations. Moreover, cyclomahanimbine (7) was transformed into murrayazolinine (10) and exozoline (11). PMID:24030919

  4. Eco-friendly and Efficient Synthesis of Pyrano[2,3-d] pyrimidinone and Tetrahydrobenzo[b]pyran Derivatives in Water

    Microsoft Academic Search

    Akbar Mobinikhaledi; Naser Foroughifar; Mohammad Ali Bodaghi Fard

    2010-01-01

    Tetrahydrobenzo[b]pyran and pyrano[2,3-d]pyrimidinone derivatives were synthesized efficiently in the presence of KAl(SO4)2.12H2O (alum) in water. Green media, lack of toxicity, short reaction times, easy work-up and high yields are some advantages of this method.

  5. KAl(SO 4) 2·12H 2O catalyzed efficient synthesis of 3,4,6-trisubstituted 2-pyridone in water

    Microsoft Academic Search

    Majid M. Heravi; Hossein A. Oskooie; Narges Karimi; Hoda Hamidi

    2011-01-01

    An efficient green protocol for the preparation 3,4,6-trisubstituted 2-pyridone of employing a condensation reaction of cyanoacetamide and acetylacetone in the presence of KAl(SO4)2·12H2O in water has been described. The present procedure offers advantage such as shorter reaction time, simple workup, and excellent yields.

  6. Combustion synthesis

    Microsoft Academic Search

    Kashinath C Patil; Singanahally T Aruna; Sambandan Ekambaram

    1997-01-01

    Many innovative self-propagating high-temperature synthesis (SHS) techniques such as filtration, combustion, the centrifugal thermite process, field activated combustion, solid-state metathesis, flame synthesis and simultaneous SHS and densification have been developed for the synthesis of ‘advanced materials’. A novel gas producing self-propagating process initiated at low temperature using redox compounds and mixtures has been used for the preparation of fine particle

  7. 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

  8. Schema Induction for Logic Program Synthesis

    Microsoft Academic Search

    Nancy Lynn Tinkham

    1998-01-01

    Prolog program synthesis can be made more efficient by using schemata which capture similarities in previously-seen programs. Such schemata narrow the search involved in the synthesis of a new program. We define a generalization operator for forming schemata from programs and a downward refinement operator for constructing programs from schemata. These operators define schema-hierarchy graphs which can be used to

  9. Template-free synthesis of cube-like Ag/AgCl nanostructures via a direct-precipitation protocol: highly efficient sunlight-driven plasmonic photocatalysts.

    PubMed

    Zhu, Mingshan; Chen, Penglei; Ma, Wanhong; Lei, Bin; Liu, Minghua

    2012-11-01

    In this paper, we report that cube-like Ag/AgCl nanostructures could be facilely fabricated in a one-pot manner through a direct-precipitation protocol under ambient conditions, wherein no additional issues such as external energy (e.g., high temperature or high pressure), surfactants, or reducing agents are required. In terms of using sodium chloride (NaCl) as chlorine source and silver acetate (CH?COOAg) as silver source, it is disclosed that simply by adding an aqueous solution of NaCl into an aqueous solution of CH?COOAg, Ag/AgCl nanostructures with a cube-like geometry, could be successfully formulated. We show that thus-formulated cube-like Ag/AgCl nanospecies could be used as high-performance yet durable visible-light-driven or sunlight-driven plasmonic photocatalysts for the photodegradation of methyl orange (MO) and 4-chlorophenol (4-CP) pollutants. Compared with the commercially available P25-TiO?, and the Ag/AgCl nanospheres previously fabricated via a surfactant-assisted method, our current cube-like Ag/AgCl nanostructures could exhibit much higher photocatalytic performance. Our template free protocol might open up new and varied opportunities for an easy synthesis of cube-like Ag/AgCl-based high-performance sunlight-driven plasmonic photocatalysts for organic pollutant elimination. PMID:23138343

  10. Eco-friendly and efficient one-pot synthesis of alkyl- or aryl-14 H-dibenzo[ a, j]xanthenes in water

    Microsoft Academic Search

    Minoo Dabiri; Mostafa Baghbanzadeh; Maryam Shakouri Nikcheh; Elham Arzroomchilar

    2008-01-01

    Alkyl- or aryl-14H-dibenzo[a,j]xanthene derivatives are synthesized efficiently by the reaction of ?-naphthol and aliphatic and aromatic aldehydes in the presence of KAl(SO4)2·12H2O (alum) under aqueous condition at 100°C. Different types of aromatic and aliphatic aldehydes are used in the reaction and in all cases the products synthesized successfully. Several solvents were examined for this reaction; however, in terms of reaction

  11. Graphite-supported perchloric acid (HClO4-C): an efficient and recyclable heterogeneous catalyst for the one-pot synthesis of amidoalkyl naphthols.

    PubMed

    Lei, Zhen-Kai; Xiao, Li; Lu, Xiao-Quan; Huang, He; Liu, Chen-Jiang

    2013-01-01

    An efficient and direct protocol for the preparation of amidoalkylnaphthols employing a multi-component, one-pot condensation reaction of 2-naphthol, aromatic aldehydes and acetamide or benzamide in the presence of graphite supported perchloric acid under solvent-free conditions is described. The thermal solvent-free procedure offers advantages such as simple work-up, shorter reaction times and higher product yields, and the catalyst exhibited remarkable reactivity and can be recycled. PMID:23358323

  12. Copper(ii)-catalyzed oxidative [3+2] cycloaddition reactions of secondary amines with ?-diazo compounds: a facile and efficient synthesis of 1,2,3-triazoles.

    PubMed

    Li, Yi-Jin; Li, Xue; Zhang, Shao-Xiao; Zhao, Yu-Long; Liu, Qun

    2015-07-25

    A novel copper-catalyzed [3+2] cycloaddition reaction of secondary amines with ?-diazo compounds has been developed via a cross-dehydrogenative coupling process. The reaction involves a sequential aerobic oxidation/[3+2] cycloaddition/oxidative aromatization procedure and provides an efficient method for the construction of 1,2,3-triazoles in a single step in an atom-economic manner from readily available starting materials under very mild conditions. PMID:26076660

  13. Asymmetric Catalysis Special Feature Part II: Development of an efficient, scalable, aldolase-catalyzed process for enantioselective synthesis of statin intermediates

    Microsoft Academic Search

    William A. Greenberg; Alexander Varvak; Sarah R. Hanson; Kelvin Wong; Hongjun Huang; Pei Chen; Mark J. Burk

    2004-01-01

    A process is reported for efficient, enantioselective production of key intermediates for the common chiral side chain of statin-type cholesterol-lowering drugs such as Lipitor (atorvastatin) and Crestor (rosuvastatin). The process features a one-pot tandem aldol reaction catalyzed by a deoxyribose-5-phosphate aldolase (DERA) to form a 6-carbon intermediate with installation of two stereogenic centers from 2-carbon starting materials. An improvement of

  14. Synthesis of FeCo nanocrystals encapsulated in nitrogen-doped graphene layers for use as highly efficient catalysts for reduction reactions.

    PubMed

    Hu, Lin; Zhang, Ruirui; Wei, Lingzhi; Zhang, Fapei; Chen, Qianwang

    2015-01-14

    A facile strategy to fabricate FeCo nanocrystals with nitrogen-doped graphene shells has been designed, which involves one-step thermal decomposition of Prussian blue analogue (PBA) Fe3[Co(CN)6]2 spheres. The as-prepared product can be used as a non-precious-metal catalyst with a highly efficient catalytic activity and a magnetically separable capability in the reduction of 4-nitrophenol. PMID:25429694

  15. One-step synthesis of highly efficient three-dimensional Cd1-xZnxS photocatalysts for visible light photocatalytic water splitting

    PubMed Central

    2013-01-01

    Visible light accounts for about 43% of the solar spectrum, and developing highly efficient visible-light-driven photocatalyst is of special significance. In this work, highly efficient three-dimensional (3D) Cd1?xZnxS photocatalysts for hydrogen generation under the irradiation of visible light were synthesized via one-step solvothermal pathway. Scanning electron microscope, X-ray diffractometer, Raman spectrometer, and X-ray photoelectron spectrometer were utilized to characterize the morphology, crystal structure, vibrational states, and surface composition of the obtained 3D Cd1?xZnxS. UV-Vis spectra indicated that the as-synthesized Cd1?xZnxS had appropriate bandgap and position of the conduction band that is beneficial for visible light absorption and photo-generated electron-hole pair separation. Moreover, the 3D structure offers a larger surface area thus supplying more surface reaction sites and better charge transport environment, and therefore, the efficiency of water splitting was improved further. PMID:23883429

  16. Magnetic Cross-Linked Enzyme Aggregates (mCLEAs) of Candida antarctica lipase: an efficient and stable biocatalyst for biodiesel synthesis.

    PubMed

    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

  17. Microwave-assisted solvothermal synthesis of flower-like Ag/AgBr/BiOBr microspheres and their high efficient photocatalytic degradation for p-nitrophenol

    SciTech Connect

    Li, Tingting, E-mail: tingtingli1983@hotmail.com [Department of Chemistry and Chemical Engineering, Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Changsha 410082 (China); State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University, Changsha 410082 (China); Department of Environment and Chemical Engineering, Key Laboratory of Jiangxi Province for Ecological Diagnosis, Remediation and Pollution Control, Nanchang Hangkong University, Nanchang 330063 (China); Luo, Shenglian, E-mail: sllou@hnu.edu.cn [Department of Chemistry and Chemical Engineering, Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Changsha 410082 (China); State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University, Changsha 410082 (China); Department of Environment and Chemical Engineering, Key Laboratory of Jiangxi Province for Ecological Diagnosis, Remediation and Pollution Control, Nanchang Hangkong University, Nanchang 330063 (China); Yang, Lixia [Department of Environment and Chemical Engineering, Key Laboratory of Jiangxi Province for Ecological Diagnosis, Remediation and Pollution Control, Nanchang Hangkong University, Nanchang 330063 (China)

    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.

  18. 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 [Department of Chemistry, School of Sciences, Zhejiang Sci-Tech University, 5 Second Avenue, Xiasha Higher Education Zone, Hangzhou 310018 (China)] [Department of Chemistry, School of Sciences, Zhejiang Sci-Tech University, 5 Second Avenue, Xiasha Higher Education Zone, Hangzhou 310018 (China); Dong, Xiaoping, E-mail: xpdong@zstu.edu.cn [Department of Chemistry, School of Sciences, Zhejiang Sci-Tech University, 5 Second Avenue, Xiasha Higher Education Zone, Hangzhou 310018 (China)] [Department of Chemistry, School of Sciences, Zhejiang Sci-Tech University, 5 Second Avenue, Xiasha Higher Education Zone, Hangzhou 310018 (China)

    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.

  19. Efficient synthesis, structural characterization and anti-microbial activity of chiral aryl boronate esters of 1,2-O-isopropylidene-?-D-xylofuranose.

    PubMed

    Trivedi, Rajiv; Rami Reddy, E; Kiran Kumar, Ch; Sridhar, B; Pranay Kumar, K; Srinivasa Rao, M

    2011-07-01

    A simple and efficient synthetic approach toward a series of chiral aryl boronate esters, starting from D-xylose, as anti-microbial agents, is described herein. Minimum inhibitory concentration and zone of inhibition revealed that these derivatives exhibit potent anti-bacterial and anti-fungal properties. Herein, we report the first anti-microbial activity of this class of compounds. All products have been characterized by NMR ((1)H, (13)C and (11)B), IR, elemental and mass spectral study. PMID:21641208

  20. Sulfonic acid functionalized poly (ethylene glycol dimethacrylate-1-vinyl-1,2,4-triazole) as an efficient catalyst for the synthesis of methyl propionate

    Microsoft Academic Search

    Beyhan Erdem; Ali Kara

    2011-01-01

    Sulfonic acid functionalized poly (ethylene glycol dimethacrylate-1-vinyl-1,2,4-triazole), poly (EGDMA–VTAZ–SO3H) (average diameter 1.0–1.5mm), was found to be efficient solid acid catalyst for the esterification of methanol and propionic acid under heterogeneous reaction conditions. The pristine polymer, poly (EGDMA–VTAZ), was produced by suspension polymerization and then proton-conducting polymer was obtained by blending of poly (EGDMA–VTAZ) with different percentage of H2SO4 solutions. The

  1. 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

  2. Folate-PEG modified poly(2-(2-aminoethoxy)ethoxy)phosphazene/DNA nanoparticles for gene delivery: synthesis, preparation and in vitro transfection efficiency.

    PubMed

    Zhang, Pengcheng; Zhang, Zhiwen; Yang, Yongxin; Li, Yaping

    2010-06-15

    Target-specific technique can significantly enhance the efficacy of gene delivery system which was limited by many cellular barriers. In this work, a new folate-PEG modified poly(2-(2-aminoethoxy)ethoxy)phosphazene (PAEP), namely, folate-PEG-PAEP was synthesized as a folate receptor (FR) targeted carrier, and the cytotoxicity, transfection efficiency, cellular uptake and intracellular trafficking of folate-PEG-PAEP/DNA nanoparticles (FPPN) were investigated. Compared with the PAEP/DNA nanoparticles (PN), the cytotoxicity of FPPN decreased significantly at high dose. FPPN showed much higher transfection efficiency (15.85+/-1.23%) compared with PN (6.71+/-0.42%) in FR overexpressing Hela cells, but no significant difference was observed in CHO-k1 cells lacking FR. The transfection activity of FPPN could be reversed in the presence of 1.0mM free folic acid in Hela cells. The cellular uptake of FPPN was 37.38% higher than that of PN in Hela cells. These results indicated that FPPN could be a potential targeted gene delivery system. PMID:20298769

  3. Synthesis of TiO2 nanorod-decorated graphene sheets and their highly efficient photocatalytic activities under visible-light irradiation.

    PubMed

    Lee, Eunwoo; Hong, Jin-Yong; Kang, Haeyoung; Jang, Jyongsik

    2012-06-15

    The titanium dioxide (TiO(2)) nanorod-decorated graphene sheets photocatalysts with different TiO(2) nanorods population have been synthesized by a simple non-hydrolytic sol-gel approach. Electron microscopy and X-ray diffraction analysis indicated that the TiO(2) nanorods are well-dispersed and successfully anchored on the graphene sheet surface through the formation of covalent bonds between Ti and C atoms. The photocatalytic activities are evaluated in terms of the efficiencies of photodecomposition and adsorption of methylene blue (MB) in aqueous solution under visible-light irradiation. The as-synthesized TiO(2) nanorod-decorated graphene sheets showed unprecedented photodecomposition efficiency compared to the pristine TiO(2) nanorods and the commercial TiO(2) (P-25, Degussa) under visible-light. It is believed that this predominant photocatalytic activity is due to the synergistic contribution of both a retarded charge recombination rate caused by a high electronic mobility of graphene and an increased surface area originated from nanometer-sized TiO(2) nanorods. Furthermore, photoelectrochemical study is performed to give deep insights into the primary roles of graphene that determines the photocatalytic activity. PMID:22497717

  4. 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.

  5. Enol Ethers as Substrates for Efficient Z- and Enantioselective Ring-Opening/Cross-Metathesis Reactions Promoted by Stereogenic-at-Mo Complexes. Utility in Chemical Synthesis and Mechanistic Attributes

    PubMed Central

    Yu, Miao; Ibrahem, Ismail; Hasegawa, Masayuki; Schrock, Richard R.; Hoveyda, Amir H.

    2012-01-01

    The first examples of catalytic enantioselective ring-opening/cross-metathesis (EROCM) reactions that involve enol ethers are reported. Specifically, we demonstrate that catalytic EROCM of several oxa- and azabicycles, cyclobutenes and a cyclopropene with an alkyl- or aryl-substituted enol ether proceed readily in the presence of a stereogenic-at-Mo monopyrrolide-monoaryloxide. In some instances, as little as 0.15 mol % of the catalytically active alkylidene is sufficient to promote complete conversion within 10 minutes. The desired products are formed in up to 90% yield and >99:1 enantiomeric ratio (er) with the disubstituted enol ether generated in >90% Z selectivity. The enol ether of the enantiomerically enriched products can be easily differentiated from the terminal alkene through a number of functionalization procedures that lead to the formation of useful intermediates for chemical synthesis (e.g., efficient acid hydrolysis to afford the enantiomerically enriched carboxaldehyde). In certain cases, enantioselectivity is strongly dependent on enol ether concentration: larger equivalents of the cross partner leads to the formation of products of high enantiomeric purity (versus near racemic products with one equivalent). The length of reaction time can be critical to product enantiomeric purity; high enantioselectivity in reactions that proceed to >98% conversion in as brief a reaction time as 30 seconds can be nearly entirely eroded within 30 minutes. Mechanistic rationale that accounts for the above characteristics of the catalytic process is provided. PMID:22272931

  6. 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. [School of Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Tezuka, S.; Kakihana, M. [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1, Katahira, Aoba-ku, Sendai, 980-8577 (Japan); Toda, K. [Department of Chemistry and Chemical Engineering, Faculty of Engineering, Niigata University, Ikarashi 2 nocho 8050, Niigata 950-2181 (Japan); Masaki, T. [School of Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Yoon, D.H., E-mail: dhyoon@skku.edu [School of Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); SKKU Advanced Institute of Nanotechnology (SAINT), Sungkyunkwan University, Suwon 440-746 (Korea, Republic of)

    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.

  7. Fast texture synthesis using tree-structured vector quantization

    Microsoft Academic Search

    Li-Yi Wei; Marc Levoy

    2000-01-01

    Texture synthesis is important for many applications in computer graphics, vision, and image processing. However, it remains difficult to design an algorithm that is both efficient and capable of generating high quality results. In this paper, we present an efficient algorithm for realistic texture synthesis. The algorithm is easy to use and requires only a sample texture as input. It

  8. Synthesis of honeycomb-like mesoporous pyrite FeS2 microspheres as efficient counter electrode in quantum dots sensitized solar cells.

    PubMed

    Xu, Jun; Xue, Hongtao; Yang, Xia; Wei, Huaixin; Li, Wenyue; Li, Zhangpeng; Zhang, Wenjun; Lee, Chun-Sing

    2014-11-01

    Honeycomb-like mesoporous pyrite FeS2 microspheres, with diameters of 500-800 nm and pore sizes of 25-30 nm, are synthesized by a simple solvothermal approach. The mesoporous FeS2 microspheres are demonstrated to be an outstanding counter electrode (CE) material in quantum dot sensitized solar cells (QDSSCs) for electrocatalyzing polysulfide electrolyte regeneration. The cell using mesoporous FeS2 microspheres as CE shows 86.6% enhancement in power conversion efficiency (PCE) than the cell using traditional noble Pt CE. Furthermore, it also shows 11.4% enhancement in PCE than the cell using solid FeS2 microspheres as CE, due to the mesoporous structure facilitating better contact with polysulfide electrolyte and fast diffusion of redox couple species in electrolyte. PMID:24986216

  9. A facile and green method for synthesis of reduced graphene oxide/Ag hybrids as efficient surface enhanced Raman scattering platforms.

    PubMed

    Huang, Qingli; Wang, Jiaming; Wei, Wenxian; Yan, Qiuxiang; Wu, Changle; Zhu, Xiashi

    2015-02-11

    Reduced graphene oxide/Ag nanoparticles hybrids (rGO/AgNPs) were fabricated via a green and facile hydrothermal method. The as-synthesized materials were characterized in detail using various spectroscopic and microscopic techniques. Under a suitable dosage of silver ions, well-dispersed AgNPs on the reduced graphene oxide sheets were obtained. The surface plasmon resonance properties of AgNPs on graphene show that there is an interaction between AgNPs and graphene. Trace detection of organic dyes is studied based on rGO/AgNPs hybrids as efficient surface enhanced Raman scattering platforms. It has been found that the suitable experiment parameter is crucial to trace detection of organic dyes molecules. This work is of importance in the practical application in device-design based on the SERS effect of noble metal/reduced oxide graphene (or oxide graphene) hybrids. PMID:25262484

  10. Highly efficient Yb3+/Tm3+ co-doped NaYF4 nanotubes: Synthesis and intense ultraviolet to infrared up-conversion luminescence

    NASA Astrophysics Data System (ADS)

    Zhang, Y. Y.; Wang, Y.; Deng, J. Q.; Wang, J.; Ni, S. C.

    2014-02-01

    Nanocrystals of up-conversion (UC) phosphor Yb3+/Tm3+ co-doped NaYF4 are prepared by a facile hydrothermal method using oleic acid as a stabilizing agent. The as-prepared nanocrystals are of hexagonal phase, and have tube-like morphology and strong ultraviolet (UV) and blue UC fluorescence intensity, which have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and luminescence spectroscopy. The effect of Yb3+ concentration on the UC emission properties is also analyzed. Our results reveal that the intensity of emission peaks can be controlled by varying the Yb3+ concentration and these NaYF4 nanotubes are highly efficient host material. The as-prepared NaYF4 nanotubes show potential applications in UV compact solid state lasers and multi-channel fluorescent label.

  11. Synthesis, characterization and application of a nano-manganese-catalyst as an efficient solid catalyst for solvent free selective oxidation of ethylbenzene, cyclohexene, and benzylalcohol

    NASA Astrophysics Data System (ADS)

    Habibi, Davood; Faraji, Ali Reza

    2013-07-01

    The object of this study is to synthesize the heterogeneous Mn-nano-catalyst (MNC) which has been covalently anchored on a modified nanoscaleSiO2/Al2O3, and characterized by FT-IR, UV-Vis, CHN elemental analysis, EDS, TEM, and EDX. The method is efficient for the highly selective oxidation of ethylbenzene, cyclohexene, and benzylalcohol without the need to any solvents, using tert-butyl hydroperoxide (TBHP) as an oxidant. Oxidation of ethylbenzene, cyclohexene, and benzylalcohol gave acetophenone, 2-cyclohexene-1-one and benzaldehyde, respectively, as major products. Reaction conditions have been optimized by considering the effect of various factors such as reaction time, amounts of substrates and oxidant, Mn-nano-catalyst and application of various solvents.

  12. 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.

  13. Facile synthesis of V(4+) self-doped, [010] oriented BiVO4 nanorods with highly efficient visible light-induced photocatalytic activity.

    PubMed

    Zhang, Yangyang; Guo, Yiping; Duan, Huanan; Li, Hua; Sun, Chongyang; Liu, Hezhou

    2014-11-28

    Monodispersed monoclinic BiVO4 nanorods grown along the [010] direction were prepared using a one-step low temperature hydrothermal method in the presence of the low-cost, nontoxic sodium oleate serving as a chelating agent. The BiVO4 nanorods with diameters of 15-20 nm possess a huge specific surface area as large as 28.2 m(2) g(-1), which can endow them with high photocatalytic activity and strong adsorption of reactants. Meanwhile, the specific [010] growth direction is capable of facilitating efficient electron-hole separation by accumulating electrons on {010} facets. Thus, the highly efficient photocatalytic activity of the as-prepared BiVO4 nanorods under visible light, which far surpasses that of commercial P25, is demonstrated by the degradation of rhodamine B and phenol. Plentiful V(4+) species, which can create oxygen vacancies, is detected implying that the as-obtained nanorods are self-doped BiVO4. Significantly, 61% of rhodamine B is adsorbed by the BiVO4 nanorods before irradiation owing to the appearance of plentiful O(2-) and OH(-) species on the surface adsorbed by oxygen vacancies. More excitingly, the excellent visible-light-driven photocatalytic activity of the as-obtained BiVO4 nanorods can be further elevated to an unprecedented level, roughly doubled, after applying a low temperature heat treatment process at 230 °C for 2 h and this improvement could primarily be ascribed to their optimized charge-carrier transport characteristics resulting from elevated crystallinity and decreased V(4+) species. PMID:25308747

  14. 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

  15. Strategies and limitations in dendrimeric immunogen synthesis. The influenza virus M2e epitope as a case study.

    PubMed

    Kowalczyk, Wioleta; de la Torre, Beatriz G; Andreu, David

    2010-01-01

    Dendrimeric platforms such as multiple antigen peptides (MAPs) are regarded as one of the most efficacious approaches for antigenic presentation. Originally described as available by stepwise solid-phase peptide synthesis (SPPS), MAPs have also been prepared by chemical (thioether, oxime, hydrazone) ligation of appropriately functionalized tetra- or octavalent polylysine scaffolds with the peptide antigen to be multiply displayed. In this work, the advantages and limitations of two of the most frequent methods of MAP preparation, namely, chemoselective thioether ligation in solution, and all-solid-phase synthesis, have been tested in the case of a particularly troublesome epitope model, the ectodomain of protein M2 from influenza virus (M2e). The strong tendency of M2e to self-associate is a serious inconvenient for conjugation in solution, which as a result fails to produce the target MAPs with the specified number of M2e copies. In contrast, the fully stepwise SPPS approach is shown to be quite practical, especially when 6-aminohexanoic acid spacer units providing increased internal flexibility are inserted at each branching point. PMID:20025260

  16. Toward More “Ideal” Polyketide Natural Product Synthesis: A Step-Economical Synthesis of Zincophorin Methyl Ester

    PubMed Central

    Harrison, Tyler; Ho, Stephen; Leighton, James L.

    2011-01-01

    A highly efficient and step-economical synthesis of zincophorin methyl ester has been achieved. The unprecedented step-economy of this zincophorin synthesis is principally due to an application of the tandem silylformylation-crotylsilylation/Tamao oxidation-diastereoselective tautomerization reaction that achieves in a single step what would typically require a significant multi-step sequence. PMID:21524078

  17. Incremental Synthesis for Engineering Changes

    Microsoft Academic Search

    Yosinori Watanabe; Robert K. Brayton

    1991-01-01

    The problem of rectifying design incorrectness due to specification changes as well as design errors of VLSI circuits is formulated and a basic approach using logic synthesis techniques is presented. An efficient approach is presented for rectifying the functional incorrectness by attaching circuitry exterior to the original design. A necessary and sufficient condition for full rectification of the design is

  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, E-mail: h.widiyandari@undip.ac.id; Gunawan, S. K.V.; Suseno, Jatmiko Endro [Department of Physics, Diponegoro University, Jl. Prof. H. Soedarto SH, Semarang, Central Java 50275 (Indonesia); Purwanto, Agus [Department of Chemical Engineering, Sebelas Maret University, Jl. Ir. Sutami No. 36 A, Surakarta (Indonesia); Diharjo, Kuncoro [Department of Mechanical Engineering, Sebelas Maret University, Jl. Ir. Sutami No. 36 A, Surakarta (Indonesia)

    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. Design and Synthesis of High Affinity Inhibitors of Plasmodium falciparum and Plasmodium vivax N-Myristoyltransferases Directed by Ligand Efficiency Dependent Lipophilicity (LELP)

    PubMed Central

    2014-01-01

    N-Myristoyltransferase (NMT) is an essential eukaryotic enzyme and an attractive drug target in parasitic infections such as malaria. We have previously reported that 2-(3-(piperidin-4-yloxy)benzo[b]thiophen-2-yl)-5-((1,3,5-trimethyl-1H-pyrazol-4-yl)methyl)-1,3,4-oxadiazole (34c) is a high affinity inhibitor of both Plasmodium falciparum and P. vivax NMT and displays activity in vivo against a rodent malaria model. Here we describe the discovery of 34c through optimization of a previously described series. Development, guided by targeting a ligand efficiency dependent lipophilicity (LELP) score of less than 10, yielded a 100-fold increase in enzyme affinity and a 100-fold drop in lipophilicity with the addition of only two heavy atoms. 34c was found to be equipotent on chloroquine-sensitive and -resistant cell lines and on both blood and liver stage forms of the parasite. These data further validate NMT as an exciting drug target in malaria and support 34c as an attractive tool for further optimization. PMID:24641010

  20. 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

  1. One-pot synthesis of water-swellable Mg-Al layered double hydroxides and graphene oxide nanocomposites for efficient removal of As(V) from aqueous solutions.

    PubMed

    Wen, Tao; Wu, Xilin; Tan, Xiaoli; Wang, Xiangke; Xu, Anwu

    2013-04-24

    In this Article, we report a remarkably simple and efficient method for the preparation of layered double hydroxides and graphene oxide (LDHs/GO) nanocomposites with varying GO amounts via a hydrothermal process. The graphene nature in the resulting LDHs/GO nanocomposites was confirmed by X-ray diffraction (XRD), Fourier transformed infrared (FTIR) spectroscopy, field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), N2 adsorption-desorption, and X-ray photoelectron spectroscopy (XPS). The LDHs/GO nanocomposites exhibited swelling behavior in water and forming a gel. The adsorption performance of the LDHs/GO nanocomposites was evaluated for the removal of arsenate (As(V)) from aqueous solutions, and the results showed that the ratio of GO to LDHs in the nanocomposites significantly affected the adsorption capacity. Higher and lower amounts of GO in LDHs/GO nanocomposites showed lower adsorption capacity of As(V). A maximum adsorption capacity of 183.11 mg/g (2.44 mmol/g) was achieved on the LDHs/GO containing 6.0% GO due to the higher Brunauer-Emmett-Teller (BET) surface area than other samples. Owing to their high uptake capability of As(V), water-swellable LDHs/GO nanocomposites are expected to have potential applications as adsorbents for As(V) polluted water cleanup. PMID:23528072

  2. Efficient synthesis of piperidine derivatives. Development of metal triflate-catalyzed diastereoselective nucleophilic substitution reactions of 2-methoxy- and 2-acyloxypiperidines.

    PubMed

    Okitsu, O; Suzuki, R; Kobayashi, S

    2001-02-01

    Nucleophilic substitution reactions of 2-methoxy- and 2-acyloxypiperidines were investigated. First, new and efficient methods for the preparation of the starting piperidine derivatives were developed. N-Benzyloxycarbonyl-2-methoxypiperidine (3) and 3-substituted-2-acyloxy-N-benzyloxycarbonylpiperidines (4a-d), which are recognized as the simplest imino-sugars, were prepared and were examined as substrates for nucleophilic substitution reactions with silyl enolates under the influence of catalytic amounts of metal triflates (Sc(OTf)3, Sn(OTf)2, Cu(OTf)2, Hf(OTf)4, etc). Among the triflates tested, Sc(OTf)3 gave the best results. It was found that 2-acetoxy-3-benzyloxy-N-benzyloxycarbonylpiperidine (4a) reacted with silyl enolates to afford the 2-alkylated adducts in high cis-selectivity, while 2,3-diacyloxy-N-benzyloxycarbonylpiperidines (4b-d) showed transselectivity. The stereochemical assignments were carefully performed using NMR analysis, X-ray crystallography, and synthetic transformations. Febrifugine (1), a potent antimalarial alkaloid, was successfully synthesized from 2,3-diacetoxy-N-benzyloxycarbonylpiperidine (4b) on the basis of these diastereoselective nucleophilic substitution reactions. PMID:11430100

  3. Microemulsion-assisted synthesis of hierarchical porous Ni(OH)2/SiO2 composites toward efficient removal of formaldehyde in air.

    PubMed

    Xu, Zhihua; Yu, Jiaguo; Liu, Gang; Cheng, Bei; Zhou, Peng; Li, Xinyang

    2013-07-28

    Ni(OH)2/SiO2 composites with hierarchical flake-like nanostructures were synthesized using water-in-oil microemulsion and characterized by X-ray diffraction, thermogravimetry, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption, and X-ray photoelectron spectroscopy. The as-prepared hierarchical porous Ni(OH)2/SiO2 composites show an excellent performance for formaldehyde (HCHO) removal in air at an ambient temperature. It was found that the aging time had a significant impact on the pore structure, surface area and HCHO adsorption. The Ni(OH)2/SiO2 composite aged for 4 h in the presence of tetraethyl orthosilicate (TEOS) exhibited a relatively high HCHO adsorption capacity as well as good recyclability compared with Ni(OH)2, attributed to a relatively large BET surface area, an optimal pore size, a suitable proportion between Ni(OH)2 and SiO2, and a synergistic effect between Ni(OH)2 and SiO2. The results from this work not only demonstrate that hierarchical porous Ni(OH)2/SiO2 composites can act as an efficient adsorbent toward HCHO in air, but suggest a new route for the rational design of cost-effective, high-performance and environmentally benign adsorbents for indoor air cleanup. PMID:23727657

  4. Synthesis of Z-scheme g-C3N4-Ti(3+)/TiO2 material: an efficient visible light photoelectrocatalyst for degradation of phenol.

    PubMed

    Liao, Wenjuan; Murugananthan, Muthu; Zhang, Yanrong

    2015-04-14

    In this study, a photocatalytic material g-C3N4-Ti(3+)/TiO2 nanotube arrays was prepared by a facile and viable approach involving a heat treatment followed by an electrochemical reduction step, and it was characterized using instrumental techniques such as X-ray diffraction pattern, Fourier transform-infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy and UV-vis diffuse reflectance spectra. The photocatalytic efficiency of the as-prepared samples towards treating aqueous solution contaminated with phenol was systematically evaluated by a photoelectrocatalytic method and found to be highly dependent on the content of the g-C3N4. At the optimal content of g-C3N4, the apparent photocurrent density of g-C3N4-Ti(3+)/TiO2 was four times higher than that of the pristine TiO2 under visible-light illumination. The enhanced photoelectrocatalytic behavior observed for g-C3N4-Ti(3+)/TiO2 was ascribed to a cumulative impact of both g-C3N4 and Ti(3+), which enhances the photoresponsive behavior of the material into the visible region and facilitates the effective charge separation of photoinduced charge carriers. PMID:25744448

  5. Rapid Facile Microwave-assisted Solvothermal Synthesis of Rod-like CuO/TiO2 for High Efficiency photocatalytic Hydrogen Evolution

    NASA Astrophysics Data System (ADS)

    Yu, Yi-Hsien; Chen, Ying-Pin; Cheng, Zhengdong

    2015-03-01

    Rod-like CuO/TiO2 was prepared by a rapid facile microwave-assisted solvothermal method for high efficiency photocatalytic hydrogen evolution. The structure of obtained CuO/TiO2 samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy (HR-TEM), and the amount of produced hydrogen was analyzed by gas chromatography (GC). CuO decorated TiO2 rods exhibited greatly improvement of photocatalytic hydrogen evolution. Utilizing 30 mg of CuO/TiO2 rods sample showed highest hydrogen evolution rate over utilizing 50 mg and 100 mg. Comparing to hydrogen evolution rate of 45.4 ?mol h-1 g1 by using bare Rod-like TiO2, 1 wt% CuO loaded TiO2 rods presented the highest hydrogen evolution rate of 3508.7 ?mol h-1 g-1 while hydrogen evolution rate of 0.5 wt%, 5 wt%, and 10 wt% CuO loaded TiO2 rods were 157.1, 2817, and 2595 ?mol h-1 g-1, respectively. Such enhancement of photocatalytic activity could be ascribed to that CuO improves not only light harvesting but also enhanced separation of electron-hole charge carriers

  6. Synthesis of Highly Efficient CaO-Based, Self-Stabilizing CO2 Sorbents via Structure-Reforming of Steel Slag.

    PubMed

    Tian, Sicong; Jiang, Jianguo; Yan, Feng; Li, Kaimin; Chen, Xuejing

    2015-06-16

    Capturing anthropogenic CO2 in a cost-effective and highly efficient manner is one of the most challenging issues faced by scientists today. Herein, we report a novel structure-reforming approach to convert steel slag, a cheap, abundant, and nontoxic calcium-rich industrial waste, as the only feedstock into superior CaO-based, self-stabilizing CO2 sorbents. The CO2 capture capacity of all the steel slag-derived sorbents was improved more than 10-fold compared to the raw slag, with the maximum uptake of CO2 achieving at 0.50 gCO2 gsorbent(-1). Additionally, the initial steel slag-derived sorbent could retain 0.25 gCO2 gsorbent(-1), that is, a decay rate of only 12% over 30 carbonation-calcination cycles, the excellent self-stabilizing property allowed it to significantly outperform conventional CaO, and match with most of the existing synthetic CaO-based sorbents. A synergistic effect that facilitated CO2 capture by CaO-based sorbents was clearly recognized when Mg and Al, the most common elements in steel slag, coexisted with CaO in the forms of MgO and Al2O3, respectively. During the calcium looping process, MgO served as a well spacer to increase the porosity of sorbents together with Al2O3 serving as a durable stabilizer to coresist the sintering of CaCO3 grains at high temperatures. PMID:25961319

  7. Connection of metallamacrocycles via dynamic covalent chemistry: a versatile method for the synthesis of molecular cages.

    PubMed

    Granzhan, Anton; Schouwey, Clément; Riis-Johannessen, Thomas; Scopelliti, Rosario; Severin, Kay

    2011-05-11

    A modular approach for the synthesis of cage structures is described. Reactions of [(arene)RuCl(2)](2) [arene = p-cymene, 1,3,5-C(6)H(3)Me(3), 1,3,5-C(6)H(3)(i-Pr)(3)] with formyl-substituted 3-hydroxy-2-pyridone ligands provide trinuclear metallamacrocycles with pendant aldehyde groups. Subsequent condensation reactions with di- and triamines give molecular cages with 3, 6, or 12 Ru centers in a diastereoselective and chemoselective (self-sorting) fashion. Some of the cages can also be prepared in one-pot reactions by mixing [(arene)RuCl(2)](2) with the pyridone ligand and the amine in the presence of base. The cages were comprehensively analyzed by X-ray crystallography. The diameter of the largest dodecanuclear complex is ?3 nm; the cavity sizes range from 290 to 740 Å(3). An amine exchange process with ethylenediamine allows the clean conversion of a dodecanuclear cage into a hexanuclear cage without disruption of the metallamacrocyclic structures. PMID:21495636

  8. Heck-Mizoroki coupling of vinyliodide and applications in the synthesis of dienes and trienes.

    PubMed

    Madden, Katrina S; David, Sylvain; Knowles, Jonathan P; Whiting, Andrew

    2015-07-01

    Vinyliodide reacts chemoselectively under Heck-Mizoroki conditions with terminal alkenes, including vinylboronate esters, to give dienes. The resulting dienylboronates undergo Suzuki-Miyaura couplings with aryl, heteroaryl and alkenyl halides to access dienes and trienes. PMID:26086853

  9. A highly efficient and eco-friendly method for the synthesis of 1,3-indandione ring-fused 3-oxindoles bearing two contiguous quaternary stereocenters via an aldol reaction in aqueous media.

    PubMed

    Liu, Xiong-Li; Pan, Bo-Wen; Zhang, Wen-Hui; Yang, Chao; Yang, Jun; Shi, Yang; Feng, Ting-Ting; Zhou, Ying; Yuan, Wei-Cheng

    2015-01-14

    A highly efficient and environmentally benign method for the synthesis of oxindoles featuring two contiguous quaternary carbon centers via an aldol reaction starting from various 3-substituted oxindoles has been established. A wide variety of such featured multi-substituted 1,3-indandione ring-fused 3-oxindole scaffolds were obtained smoothly in good yields (up to 98%) employing the most green of solvents, namely water, as reaction medium. Furthermore, their biological activity has been preliminarily demonstrated by in vitro evaluation against human prostate cancer cells PC-3, human lung cancer cells A549 and human leukemia cells K562 by MTT-based assays, using the commercially available standard drug, cisplatin, as a positive control. Gratifyingly, compounds 3s, 3u, 3y and 3c' exhibited the best levels of in vitro inhibitory activity against human leukemia cells K562, which were almost 2.0, 2.8, 2.5 and 2.2 times, respectively, the activity of the positive control, cisplatin. Compound 3y had 2.7 times the activity of the positive control, cisplatin, against PC-3 cancer cells, and 3s, 3u and 3c' showed levels of in vitro inhibitory activity against PC-3 cancer cells that were comparable to that of cisplatin. Compounds 3s, 3u and 3y had good inhibitory ability against human lung cancer cells A549. The results indicated that 1,3-indandione ring-fused 3-oxindole analogs may be useful leads for further biological screenings. PMID:25382357

  10. 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 ...

  11. A total synthesis of spirastrellolide A methyl ester.

    PubMed

    Arlt, Alexander; Benson, Stefan; Schulthoff, Saskia; Gabor, Barbara; Fürstner, Alois

    2013-03-11

    A concise total synthesis of spirastrellolide?A methyl ester (1?a, R(1) =Me) as the parent compound of a series of highly cytotoxic marine macrolides is disclosed, which exploits and expands the flexibility of a synthesis plan previously developed by our group en route to the sister compound spirastrellolide?F methyl ester (6?a, R(1) =Me). Key to success was the masking of the signature ?(15,16) -bond of 1?a as a C16-carbonyl group until after the stereogenic center at C24 had been properly set by a highly selective hydrogenation of the C24 exo-methylene precursor 66. Conformational control over the macrocyclic frame allowed the proper stereochemical course to be dialed into this reduction process. The elaboration of the C16 ketone to the C15-C16 double bond was accomplished by a chemoselective alkenyl triflate formation followed by a palladium-catalyzed hydride delivery. The role of the ketone at C16 as a strategic design element is also evident up-stream of the key intermediate 66, the assembly of which hinged upon the addition of the polyfunctionalized dithiane 37 to the similarly elaborate aldehyde fragment 46. Other crucial steps of the total synthesis were an alkyl-Suzuki coupling and a Yamaguchi lactonization that allowed the Northern and the Southern sector of the target to be stitched together and the macrocyclic perimeter to be forged. The lateral chain comprising the remote C46 stereocenter was finally attached to the core region by a modified Julia-Kocienski olefination. The preparation of the individual building blocks led to some methodological spin-offs, amongst which the improved procedure for the N-O-bond cleavage of isoxazolines by zero-valent molybdenum and the ozonolysis of a double bond in the presence of other oxidation-prone functionality are most noteworthy. Preliminary biological data suggest that the entire carbon framework, that is the macrocyclic core plus the lateral chain, might be necessary for high cytotoxicity. PMID:23420709

  12. Synthesis of benzobicycloheptanones via the trap of photogenerated ketene methide intermediate with olefins.

    PubMed

    Liu, Qiang; Meng, Jiang; Liu, Yang; Yang, Chao; Xia, Wujiong

    2014-09-01

    Irradiation of ortho-formyl dienes with UV light led to benzobicycloheptanones in high yields and chemoselectivities via a photogenerated ketene methide/Diels-Alder cascade reaction. The reaction mechanism was proposed to be a [1,5]-H shift process rather than a radical pathway based on control experiments. DFT calculations indicate that the energy of transition states is responsible for the high chemoselectivity observed in this protocol. PMID:25133849

  13. 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.

  14. Aldehyde capture ligation for synthesis of native Peptide bonds.

    PubMed

    Raj, Monika; Wu, Huabin; Blosser, Sarah L; Vittoria, Marc A; Arora, Paramjit S

    2015-06-01

    Chemoselective reactions for amide bond formation have transformed the ability to access synthetic proteins and other bioconjugates through ligation of fragments. In these ligations, amide bond formation is accelerated by transient enforcement of an intramolecular reaction between the carboxyl and the amine termini of two fragments. Building on this principle, we introduce an aldehyde capture ligation that parlays the high chemoselective reactivity of aldehydes and amines to enforce amide bond formation between amino acid residues and peptides that are difficult to ligate by existing technologies. PMID:25966041

  15. Enantioselective cascade formal reductive insertion of allylic alcohols into the C(O)-C bond of 1,3-diketones: ready access to synthetically valuable 3-alkylpentanol units.

    PubMed

    Roudier, Mylène; Constantieux, Thierry; Quintard, Adrien; Rodriguez, Jean

    2014-06-01

    An unprecedented cascade reaction combining dual iron-amine-catalyzed enantioselective functionalization of allylic alcohols and chemoselective acyl transfer is presented. It allows, from diketones and allylic alcohols, preparation of efficiently functionalized ?-chiral alcohols in up to 96% yield and 96:4 er. The interest of this redox-, atom-, and step-economomical approach was further demonstrated in the short synthesis of several key fragments of biologically active natural products or odorant molecules. PMID:24849709

  16. The HIV-1 reverse transcriptase mutants G190S and G190A, which confer resistance to non-nucleoside reverse transcriptase inhibitors, demonstrate reductions in RNase H activity and DNA synthesis from tRNALys,3 that correlate with reductions in replication efficiency

    PubMed Central

    Wang, J.; Dykes, C.; Domaoal, R.A.; Koval, C.E.; Bambara, R.A.; Demeter, L.M.

    2015-01-01

    We evaluated the replication efficiency of the HIV reverse transcriptase (RT) mutants K103N, G190A, and G190S, which confer resistance to the non-nucleoside RT inhibitor efavirenz, using growth competition assays in cell culture. In the absence of efavirenz, the fitness hierarchy was G190S < G190A < K103N < wild-type. The fitness reduction of G190S relative to K103N was less evident at high efavirenz concentrations, although K103N still replicated more efficiently. Efficiency of RNase H cleavage and RNA-dependent DNA synthesis from tRNALys,3 correlated with relative fitness, in biochemical studies of mutant RTs. Presteady state and steady state polymerization assays using DNA primers detected no abnormalities. This work is consistent with previous studies demonstrating that initiation of viral DNA synthesis is reduced in mutants with slowed RNase H cleavage, and suggests that both abnormalities contribute to the replication defect of these mutants. It also suggests that high concentrations of efavirenz are unlikely to favor the selection of G190S clinically. PMID:16504235

  17. 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

  18. 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.

  19. 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.

  20. Total synthesis of bafilomycin A1.

    PubMed

    Kleinbeck, Florian; Fettes, Gabriela J; Fader, Lee D; Carreira, Erick M

    2012-03-19

    A convergent synthesis of bafilomycin A(1), a potent inhibitor of V-type ATPases, is presented. The synthesis relies on the zinc triflate mediated diastereoselective addition of a complex enyne to a sensitive aldehyde as the key fragment coupling. A ruthenium-catalyzed trans-reduction of the resulting propargylic enyne efficiently installs the required C10-C13 trans,trans-diene subunit, implementing an alternative strategy to traditional palladium-catalyzed cross-coupling strategies. A highly selective oxidation of a secondary hydroxyl group in a triol sets the stage for the completion of the synthesis. PMID:22344969

  1. 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

  2. Multistep Synthesis of a Radiolabeled Imaging Probe Using Integrated Microfluidics

    Microsoft Academic Search

    Chung-Cheng Lee; Guodong Sui; Arkadij Elizarov; Chengyi Jenny Shu; Young-Shik Shin; Alek N. Dooley; Jiang Huang; Antoine Daridon; Paul Wyatt; David Stout; Hartmuth C. Kolb; Owen N. Witte; Nagichettiar Satyamurthy; James R. Heath; Michael E. Phelps; Stephen R. Quake; Hsian-Rong Tseng

    2005-01-01

    Microreactor technology has shown potential for optimizing synthetic efficiency, particularly in preparing sensitive compounds. We achieved the synthesis of an [18F]fluoride-radiolabeled molecular imaging probe, 2-deoxy-2-[18F]fluoro-D-glucose ([18F]FDG), in an integrated microfluidic device. Five sequential processes-[18F]fluoride concentration, water evaporation, radiofluorination, solvent exchange, and hydrolytic deprotection-proceeded with high radiochemical yield and purity and with shorter synthesis time relative to conventional automated synthesis. Multiple

  3. 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

  4. Systematic investigation on the synthesis of androstane-based 3-, 11- and 17-carboxamides via palladium-catalyzed aminocarbonylation.

    PubMed

    Acs, Péter; Takács, Attila; Kiss, Mercédesz; Pálinkás, Noémi; Mahó, Sándor; Kollár, László

    2011-02-01

    3,17-Dicarboxamido-androst-3,5,16-triene, 3-carboxamido-androst-3,5-dien-17-one, 17-carboxamido-androst-4,16-dien-3-one and 11-carboxamido-androst-5,9(11)-dien-3,17-dione derivatives were synthesized in homogeneous carbonylation reactions from the corresponding 3,17-diiodo-androst-3,5,16-triene, 3-iodo-androst-3,5-diene-17-ethylene ketal, 17-iodo-androst-5,16-dien-3-ethylene ketal, 11-iodo-androst-5,9(11)-diene-3,17-bis(ethylene ketal) derivatives, respectively. A highly chemoselective palladium-catalyzed aminocarbonylation of the corresponding iodo-alkene, carried out under mild reaction conditions, can be considered as the key-step for the introduction of the carboxamide functionalities. The synthesis of the iodo-alkene substrate is based on the transformation of the corresponding keto derivative to hydrazone, which was treated with iodine in the presence of a base (1,1,3,3-tetramethyl guanidine). The aminocarbonylation reaction is highly tolerant towards the N-nucleophiles, i.e. various primary and secondary amines including amino acid methyl esters can also be used. PMID:21130794

  5. 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

  6. Oligonucleotide Synthesis Using Ionic Liquids as Soluble Supports

    Microsoft Academic Search

    Robert A. Donga; Matthew Hassler; Tak-Hang Chan; Masad J. Damha

    2007-01-01

    The continuing evolution of the methodology for the solution-phase synthesis of oligonucleotides using soluble ionic tags as handles for easy purification is described. This methodology may provide a more cost efficient route for the large scale synthesis of oligonucleotides.

  7. Application of global sensitivity equations in multidisciplinary aircraft synthesis

    Microsoft Academic Search

    P. Hajela; C. L. Bloebaum; Jaroslaw Sobieszczanski-Sobieski

    1990-01-01

    The present paper investigates the applicability of the Global Sensitivity Equation (GSE) method in the multidisciplinary synthesis of aeronautical vehicles. The GSE method provides an efficient approach for representing a large coupled system by smaller subsystems and accounts for the subsystem interactions by means of first-order behavior sensitivities. This approach was applied in an aircraft synthesis problem with performance constraints

  8. Galacto-oligosaccharide synthesis by immobilized Aspergillus oryzae ?-galactosidase

    Microsoft Academic Search

    Ruchi Gaur; Hema Pant; Ruchi Jain; S. K. Khare

    2006-01-01

    Aspergillus oryzae ?-galactosidase was immobilized by three different techniques, namely adsorption on celite, covalent coupling to chitosan and aggregation by cross-linking. These techniques were compared in terms of the yield of immobilized preparation, enzymatic characteristics, stability and efficiency in oligosaccharide synthesis. Immobilization led to increase in Km in each case. Immobilization on chitosan gave maximum enzyme yield and oligosaccharide synthesis.

  9. Synthesis and Rendering of Bidirectional Texture Functions on Arbitrary Surfaces

    E-print Network

    North Carolina at Chapel Hill, University of

    the effectiveness of our synthesis and rendering algorithms using both real and synthetic BTF samples. Index Terms--Bidirectional texture function, reflectance and shading models, texture synthesis, mesh parameterization, texture from real-world materials [2] or generated synthe- tically [5]. Synthetic BTFs provide an efficient way

  10. Gold nanorods: Synthesis, structural manipulation, and self-assembly

    Microsoft Academic Search

    Bishnu Prasad Khanal

    2009-01-01

    This work describes methods for the synthesis, structural manipulation, and self-assembly of one-dimensional gold nanostructures. The thesis begins with an efficient technique for the synthesis and separation of gold nanorods from a complex mixture, which has been a long standing challenge in the field of inorganic nanocrystals. The key aspect of our approach is the combination of partial oxidative dissolution

  11. 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

  12. The Synthesis of a ?-Keto-?-amino Acid, a Key Intermediate in the Synthesis of Monatin, a New Natural Sweetener

    Microsoft Academic Search

    Cedric W. Holzapfel; Johan Olivier

    1993-01-01

    An efficient method was developed for the synthesis of the ketoamino acid 2, a key intermediate in the synthesis of the novel sweet compound, monatin 1. Preparation of 2 entails coupling of a suitably protected indole acetate anion to an aspartic acid derivative.

  13. A Facile Stereoselective Total Synthesis of (R)-Rugulactone

    PubMed Central

    Reddy, B. Narasimha; Singh, R. P.

    2014-01-01

    An efficient and novel synthesis of (R)-rugulactone has been achieved employing Sharpless asymmetric epoxidation of allyl alcohols followed by selective hydride reduction of epoxy alcohols and olefin cross metathesis reactions. PMID:24971179

  14. A facile stereoselective total synthesis of (R)-rugulactone.

    PubMed

    Reddy, B Narasimha; Singh, R P

    2014-01-01

    An efficient and novel synthesis of (R)-rugulactone has been achieved employing Sharpless asymmetric epoxidation of allyl alcohols followed by selective hydride reduction of epoxy alcohols and olefin cross metathesis reactions. PMID:24971179

  15. New approaches to analysis and synthesis of reflector antennas

    NASA Technical Reports Server (NTRS)

    Galindo-Israel, V.; Mittra, R.

    1978-01-01

    Recently developed techniques are reviewed for analyzing and synthesizing single and dual antennas for high efficiency and wide angle scan. The problem of contour beam synthesis using superposition of pencil beams is also discussed.

  16. Oxacycle Synthesis via Intramolecular Reaction of Carbanions and Peroxides

    PubMed Central

    2015-01-01

    The intramolecular reaction of dialkyl peroxides with carbanions, generated via chemoselective metal-heteroatom exchange or deprotonation, provides a new approach to cyclic ethers. Applied in tandem with C–C bond formation, the strategy enables a one-step annelation to form oxaospirocycles. PMID:24702123

  17. Total synthesis of (+)-aspidospermidine: a new strategy for the enantiospecific synthesis of aspidosperma alkaloids.

    PubMed

    Marino, Joseph P; Rubio, Maria B; Cao, Ganfeng; de Dios, Alfonso

    2002-11-13

    A new strategy was developed for the enantiospecific synthesis of aspidosperma alkaloids. The key steps involve a novel ketene-lactonization reaction of a chiral vinyl sulfoxide to efficiently set up the quaternary carbon center, and a tandem Michael addition-alkylation reaction sequence to form the polycyclic core structure. This new strategy was employed in the total synthesis of natural product (+)-aspidospermidine. PMID:12418888

  18. Microwave-assisted synthesis of chromenes: biological and chemical importance.

    PubMed

    Patil, Shivaputra A; Patil, Siddappa A; Patil, Renukadevi

    2015-06-01

    Chromenes constitute chemically important class of heterocyclic compounds having diverse biological and chemical importance. Development of environmentally benign, efficient and economical methods for the synthesis of chromenes remains a significant challenge in synthetic chemistry. The synthesis of chromenes, therefore, has attracted enormous attention from medicinal and organic chemists. Researchers have embraced the concepts of microwave (high speed) synthesis to produce biologically and chemically important chromenes in a time sensitive manner. This review will summarize the recent biological applications such as anticancer, antimicrobial, neurodegenerative and insecticidal activity of new chromenes prepared via microwave irradiation. The development of new methodologies for the synthesis of chromenes including green chemistry processes has also been discussed. PMID:26061107

  19. Texture Synthesis Michael Kazhdan

    E-print Network

    Kazhdan, Michael

    Texture Synthesis Michael Kazhdan (600.357 / 600.457) An Image Synthesizer. Perlin, 1985 Texture Synthesis by Non-Parametric Sampling. Efros and Leung, 1999 Wang Tiles for Image and Texture Generation. Cohen et al., 2003 #12;Overview · Texture synthesis Introduction Procedural texture synthesis Image

  20. Highly diastereoselective synthesis of quaternary ?-trifluoromethyl ?-amino acids from chiral imines of trifluoropyruvate.

    PubMed

    Min, Qiao-Qiao; He, Chun-Yang; Zhou, Haibing; Zhang, Xingang

    2010-11-14

    An efficient method for highly diastereoselective synthesis of quaternary ?-trifluoromethyl ?-amino acids was developed via indium mediated allylation of (R)-phenylglycinol methyl ether based imines of trifluoropyruvate in good yields with high diastereoselectivities at room temperature; to illustrate the application of this method in organic synthesis, 2-allyl-2-(trifluoromethyl) aziridine was prepared in an efficient manner. PMID:20856962

  1. Total synthesis of zoanthamine alkaloids.

    PubMed

    Yoshimura, Fumihiko; Tanino, Keiji; Miyashita, Masaaki

    2012-05-15

    Zoanthamine alkaloids, isolated from organisms in the Zoanthus genus, constitute a distinctive family of marine metabolites. These molecules exhibit a broad spectrum of unique biological properties. For example, norzoanthamine inhibits interleukin-6, the key mediator of bone resorption in osteoporosis, providing a promising drug candidate for a disease that affects more than 10 million people over age 50 in the United States. In addition, these natural products are characterized by a densely functionalized heptacyclic framework, as exemplified by the structures of zoanthamine, norzoanthamine, and zoanthenol, which makes them extremely attractive targets for chemical synthesis. Prior to our first total synthesis of norzoanthamine in 2004, the densely functionalized and complex stereostructures of the zoanthamine alkaloids had impeded synthetic studies of these molecules. In this Account, we describe our synthetic approach toward the total synthesis of zoanthamine alkaloids, focusing on how we overcame various synthetic challenges. At the beginning of our synthetic studies, we aimed to develop an efficient route that was flexible enough to provide access to several members of the family while allowing the synthesis of various analogues for biological testing. Our first project was the total synthesis of norzoanthamine, and we established an efficient synthetic route based on a novel strategy involving the following key features. First, we used a sequential three-component coupling reactions and subsequent photosensitized oxidation of a furan moiety to synthesize the precursor for the key intramolecular Diels-Alder reaction. Second, the key intramolecular Diels-Alder reaction constructed the ABC-ring carbon framework bearing two adjacent quaternary asymmetric carbon atoms at the C12 and C22 positions in a single stereoselective step. Third, we installed the third quaternary asymmetric carbon center at the C9 position by an intramolecular acylation of a keto alcohol followed by successive O-methylation and C-methylation reactions with complete stereoselectivity. Through the exploitation of a deuterium kinetic isoptope effect, we then efficiently synthesized the alkyne segment. Next, a coupling reaction between the alkyne segment and the amino alcohol segment and several subsequent synthetic transformations afforded the bis-aminoacetalization precursor. Finally, bis-aminoacetalization reactions carried out in one-pot constructed the DEFG-ring system and culminated in the total synthesis of norzoanthamine. Our synthetic route to norzoanthamine also allowed access to other zoanthamine alkaloids from a common synthetic intermediate, by way of stereoselective introduction of the C19 methyl group for zoanthamine, and isoaromatization for construction of the aromatic A-ring in zoanthenol. The chemistry described here not only allowed us to overcome formidable synthetic challenges but also opened a completely chemical avenue to naturally occurring zoanthamine alkaloids and their synthetic derivatives. PMID:22340011

  2. Efficient Screening Methods for Glucosyltransferase Genes in Lactobacillus Strains

    Microsoft Academic Search

    S. KRALJa; G. H. van Geel-Schutten; M. J. E. C. VAN DER MAARELa; L. Dijkhuizen

    2003-01-01

    Limited information is available about homopolysaccharide synthesis in the genus Lactobacillus. Using efficient screening techniques, extracellular glucosyltransferase (GTF) enzyme activity, resulting in ?-glucan synthesis from sucrose, was detected in various lactobacilli. PCR with degenerate primers based on homologous boxes of known glucosyltransferase (gtf) genes of lactic acid bacteria strains allowed cloning of fragments of 10 putative gtf genes from eight

  3. VLSI array synthesis for polynomial GCD computation

    Microsoft Academic Search

    Yongjin Jeong; Wayne Burleson

    1993-01-01

    Polynomial GCD (greatest common divisor) finding is an important problem in algebraic computation, especially in decoding error correcting codes. The authors show a new systolic array structure for the polynomial GCD problem using a systematic array synthesis technique. The VLSI implementation of the array structure is area-efficient and achieves maximum throughput with pipelining. The dependency graph (DG) of the Euclid

  4. Fast Calibration of Haptic Texture Synthesis Algorithms

    Microsoft Academic Search

    Gianni Campion; Vincent Hayward

    2009-01-01

    Calibrating displays can be a time-consuming process. We describe a fast technique for adjusting the subjective experience of roughness produced by different haptic texture synthesis algorithms. Its efficiency is due to the exponential convergence of the ldquomodified binary search methodrdquo (mobs) applied to find points of subjective equivalence between virtual haptic textures synthesized by different algorithms. The method was applied

  5. Polymer synthesis: Chaining up carbon dioxide

    NASA Astrophysics Data System (ADS)

    Dove, Andrew P.

    2014-04-01

    The development of methods for efficiently using carbon dioxide in synthesis would enable chemists to tap into this abundant resource. Now, an indirect route to the copolymerization of alkenes with carbon dioxide shows how this greenhouse gas may prove useful in the search for new 'green' materials.

  6. Individually addressable parallel peptide synthesis on microchips

    Microsoft Academic Search

    Jean Philippe Pellois; Xiaochuan Zhou; Onnop Srivannavit; Tiecheng Zhou; Erdogan Gulari; Xiaolian Gao

    2002-01-01

    Miniaturized, spatially addressable microchips of peptides and peptidomimetics are powerful tools for high-throughput biomedical and pharmaceutical research and the advancement of proteomics. Here we report an efficient and flexible method for the parallel synthesis of peptides on individually addressable microchips, using digital photolithography and photogenerated acid in the deprotection step. We demonstrate that we are able to synthesize thousands of

  7. Software synthesis for DSP using ptolemy

    Microsoft Academic Search

    José Luis Pino; Soonhoi Ha; Edward A. Lee; Joseph T. Buck

    1995-01-01

    Ptolemy is an environment for simulation, prototyping, and software synthesis for heterogeneous systems. It uses modern object-oriented software technology (in C++) to model each subsystem in a natural and efficient manner, and to integrate these subsystems into a whole. The objectives of Ptolemy encompass practically all aspects of designing signal processing and communica- tions systems, ranging from algorithms and communica-

  8. Synthesis of [(18) O2 ]-curcumin.

    PubMed

    Shen, Xiurui; Yang, Xiaomei; Zhu, Ying; Liu, Xihuan; Wen, Hongliang

    2014-09-01

    Curcumin, a pigment isolated from rhizomes of Curcuma longa, is a potent cancer chemopreventive and chemotherapeutic agent and is now evaluated in phase III human clinical trials. This report describes an efficient synthesis of [(18) O2 ]-curcumin. [(18) O2 ]-Curcumin was prepared in three steps from 1-iodo-2-methoxy-4-methylbenzene in an overall yield of 53%. PMID:25267481

  9. Microwave-Assisted Synthesis of Functional Polysilanes

    Microsoft Academic Search

    Mihaela Simionescu; Liviu Sacarescu; Gabriela Sacarescu

    2012-01-01

    The presence of reactive Si–H groups in polyhydrosilanes allows to obtain different polysilane structures with various functionalities through catalytic addition of unsaturated organic compounds. An efficient synthesis method of such functional polysilanes has been achieved using a conventional method as well as microwave irradiation. The effect of microwave irradiation on chemical reactions is generally evaluated by comparing the time needed

  10. Formal total synthesis of aliskiren.

    PubMed

    Peters, Byron K; Liu, Jianguo; Margarita, Cristiana; Andersson, Pher G

    2015-05-01

    The efficient and selective formal total synthesis of aliskiren is described. Aliskiren, a renin inhibitor drug, has received considerable attention, primarily because it is the first of the renin inhibitor drugs to be approved by the FDA. Herein, the formal synthesis of aliskiren by iridium-catalyzed asymmetric hydrogenation of two allylic alcohol fragments is reported. Screening a number of N,P-ligated iridium catalysts yielded two catalysts that gave the highest enantioselectivity in the hydrogenation, which gave the saturated alcohols in 97 and 93?% ee. In only four steps after hydrogenation, the fragments were combined by using the Julia-Kocienski reaction to produce late-stage intermediate in an overall yield of 18?%. PMID:25783891

  11. Semi-synthesis of biologically active nisin hybrids composed of the native lanthionine ABC-fragment and a cross-stapled synthetic DE-fragment.

    PubMed

    Slootweg, Jack C; Peters, Nienke; Quarles van Ufford, H Linda C; Breukink, Eefjan; Liskamp, Rob M J; Rijkers, Dirk T S

    2014-10-01

    The antimicrobial peptide nisin is a promising template for designing novel peptide-based antibiotics to improve its drug-like properties. First steps in that direction represent the synthesis of hybrid nisin derivatives that contain a native nisin ABC-part and synthesized cross-stapled DE-ring fragments and are described here. The biological activity of the newly synthesized nisin derivatives was evaluated in order to compare the bioactivity of the synthetic DE-ring containing mimic and native lanthionine-bridged DE-ring containing nisin. The native nisin ABC-ring system was obtained via chymotrypsin digestion of full-length nisin, and was subsequently functionalized at the C-terminal carboxylate with two different amino alkyne moieties. Next, nisin hybrids were successfully prepared using Cu(I)-catalyzed azide alkyne cycloaddition 'click' chemistry by chemo-selective ligation of the ABC-alkyne with the N-terminal azido functionalized dicarba-DE ring mimic. The newly synthesized compounds were active as potent lipid II binders and retained antimicrobial activity in a growth inhibition assay. However, pore formation was not observed, possibly either due to the different character of the 'staples' as compared to the parent sulfides, or due to the triazole moiety as a sub-optimal amide bond isostere. PMID:25199583

  12. Combustion synthesis of metal-matrix composites: Part I, the Ti-TiC-Al 2O 3 system

    Microsoft Academic Search

    A. O. Kunrath; T. R. Strohaecker; J. J. Moore

    1996-01-01

    Combustion synthesis or Self-propagating High-temperature Synthesis (SHS) is a process that involves a reaction which is sufficiently exothermic to sustain itself, and, as such, provides considerable potential for the development of an affordable (low cost), energetically efficient means of producing advanced materials. In the combustion synthesis process, a mix of the reactant powders, pressed into a pellet, is heated to

  13. Iodine-mediated oxidative annulation for one-pot synthesis of pyrazines and quinoxalines using a multipathway coupled domino strategy.

    PubMed

    Viswanadham, K K Durga Rao; Prathap Reddy, Muktapuram; Sathyanarayana, Pochampalli; Ravi, Owk; Kant, Ruchir; Bathula, Surendar Reddy

    2014-11-14

    An efficient iodine-mediated oxidative annulation of aryl acetylenes-arylethenes-aromatic ketones with 1,2-diamines for the synthesis of pyrazines and regioselective synthesis of quinoxalines is presented. A multipathway coupled domino approach has been developed for the one-pot synthesis of 1,4-diazines with high functional group compatibility. PMID:25238170

  14. An efficient procedure for the preparation of (E)-alpha-alkylidenecycloalkanones mediated by a CeCl(3) x 7H(2)O-NaI system. Novel methodology for the synthesis of (S)-(-)-pulegone.

    PubMed

    Bartoli, Giuseppe; Bosco, Marcella; Dalpozzo, Renato; Giuliani, Arianna; Marcantoni, Enrico; Mecozzi, Tiziana; Sambri, Letizia; Torregiani, Elisabetta

    2002-12-13

    2-Alkylidenecycloalkanones are powerful synthons used as the key intermediates in many important syntheses. Because of their potential, a general method of preparation from readily available starting materials, under very mild conditions, was considered to be worthwhile. Cerium(III) chloride heptahydrate in combination with sodium iodide in refluxing acetonitrile promotes a regio- and stereoselective beta-elimination reaction to (E)-2-alkylidenecycloalkanones in 2-(1-hydroxyalkyl)cycloalkanones. The synthetic value of the present procedure is demonstrated by the synthesis of monoterpene (S)-(-)-pulegone (8) in its optically active form. PMID:12467442

  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. Enzymatic de Novo Pyrimidine Nucleotide Synthesis

    PubMed Central

    Schultheisz, Heather L.; Szymczyna, Blair R.; Scott, Lincoln G.

    2011-01-01

    The use of stable isotope labeling has revolutionized NMR studies of nucleic acids, and there is a need for methods of incorporation of specific isotope labels to facilitate specific NMR experiments and applications. Enzymatic synthesis offers an efficient and flexible means to synthesize nucleoside triphosphates from a variety of commercially available specifically labeled precursors, permitting isotope labeling of RNAs prepared by in vitro transcription. Here, we recapitulate de novo pyrimidine biosynthesis in vitro, using recombinantly expressed enzymes to perform efficient single-pot syntheses of UTP and CTP that bear a variety of stable isotope labeling patterns. Filtered NMR experiments on 13C, 15N, 2H-labeled HIV-2 TAR RNA demonstrate the utility and value of this approach. This flexible enzymatic synthesis will make implementing detailed and informative RNA stable isotope labeling schemes substantially more cost effective and efficient, providing advanced tools for the study of structure and dynamics of RNA molecules. PMID:21166398

  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. Cerium(III) Chloride Heptahydrate (CeCl 3 · 7H 2 O) as an Efficient Enamination Catalyst in Aqueous Media

    Microsoft Academic Search

    M. M. Khodaei; A. R. Khosropour; M. Kookhazadeh

    2005-01-01

    Cerium(III) chloride heptahydrate CeCl3 · H2O catalyzes enamination of ?-dicarbonyl compounds with primary amines in aqueous medium at room temperature to afford the corresponding ?-enamino ketones with high chemoselectivity.

  20. Efficient Windows

    NSDL National Science Digital Library

    The Efficient Windows Collaborative (EWC) operates this informative site about the benefits and energy saving characteristics of efficient windows. A good overview of the various types is given in the How Windows Work section. This explains many different glazings, frames, and operating designs of the windows. The three main technologies used to improve insulating performance are covered, and another section highlights some advantages of efficient windows. The Web site also offers fact sheets with statistics for various cities around the US. If users are interested in switching to efficient windows for their homes, there is plenty of information about how to make the best selection.

  1. Recent Progress towards Transition-Metal-Catalyzed Synthesis of Fluorenes.

    PubMed

    Zhou, Ai-Hua; Pan, Fei; Zhu, Chunyin; Ye, Long-Wu

    2015-07-13

    Fluorenes are a commonly encountered structural motif in materials science, pharmaceutical chemistry, and organic synthesis. Among various strategies towards the synthesis of this unique structure, transition metal-catalyzed functionalization has emerged as one of the most efficient methods. This Minireview presents an overview of the recent advances in this emerging area by highlighting the reactions' specificity and applicability and, where possible, provides a mechanistic rationale. PMID:25858775

  2. 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.

  3. 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.

  4. The Art of Total Synthesis Through Cascade Reactions

    PubMed Central

    Chen, Jason S.

    2009-01-01

    The growing importance of cascade reactions reflects and imparts advances in the state of the art of organic synthesis and underscores the desire of synthetic chemists to achieve higher levels of elegance and efficiency. Besides their aesthetic appeal, cascade processes offer economical and environmentally friendly means for generating molecular complexity. Because of their many advantages, these reactions have found numerous applications in the synthesis of complex molecules, both natural and designed. In this Tutorial Review, we highlight the design and execution of cascade reactions within the context of total synthesis as demonstrated with selected examples from these laboratories. PMID:19847336

  5. 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.

  6. Solution Combustion Synthesis Impregnated Layer Combustion Synthesis is a Novel

    E-print Network

    Mukasyan, Alexander

    Solution Combustion Synthesis Impregnated Layer Combustion Synthesis is a Novel Methodology Engineering University of Notre Dame University of Notre Dame #12;Outline: Overview of combustion synthesis Reaction system Combustion front analaysis Theoretical model results Conclusions Acknowledgements #12

  7. The Rate of Polymerase Release upon Filling the Gap between Okazaki Fragments is Inadequate to Support Cycling During Lagging Strand Synthesis

    PubMed Central

    Dohrmann, Paul R.; Manhart, Carol M.; Downey, Christopher D.; McHenry, Charles S.

    2011-01-01

    Upon completion of synthesis of an Okazaki fragment, the lagging strand replicase must recycle to the next primer at the replication fork in under 0.1 second to sustain the physiological rate of DNA synthesis. We tested the collision model that posits that cycling is triggered by the polymerase encountering the 5?-end of the preceding Okazaki fragment. Probing with surface plasmon resonance, DNA polymerase III holoenzyme initiation complexes were formed on an immobilized gapped template. Initiation complexes exhibit a half-life of dissociation of approximately 15 minutes. Reduction of gap size to one nucleotide increased the rate of dissociation 2.5-fold and complete filling of the gap increased the off rate an additional three-fold (t½ ? 2 min). An exogenous primed template and ATP accelerated dissociation an additional four-fold in a reaction that required complete filling of the gap. Neither a 5?-triphosphate nor 5?-RNA terminated oligonucleotide downstream of the polymerase accelerated dissociation further. Thus, the rate of polymerase release upon gap completion and collision with a downstream Okazaki fragment is 1000-fold too slow to support an adequate rate of cycling and likely provides a backup mechanism to enable polymerase release when the other cycling signals are absent. Kinetic measurements indicate that addition of the last nucleotide to fill the gap is not the rate-limiting step for polymerase release and cycling. Modest (approximately 7 nucleotide) strand displacement is observed after the gap between model Okazaki fragments is filled. To determine the identity of the protein that senses gap filling to modulate affinity of the replicase for the template, we performed photo-crosslinking experiments with highly reactive and non-chemoselective diazirines. Only the ? subunit cross-linked, indicating it serves as the sensor. PMID:21986197

  8. Synthesis and in vitro cytotoxicity of haloderivatives of noscapine

    Microsoft Academic Search

    Akhilesh Kumar Verma; Sandhya Bansal; Jaspal Singh; Rakesh Kumar Tiwari; V. Kasi Sankar; Vibha Tandon; Ramesh Chandra

    2006-01-01

    Three haloderivatives of noscapine 2–4 were synthesized chemoselectively and their in vitro cytotoxicity was assessed by MTT assay on U-87 human glioblastoma cell lines. At 50?M concentration after 72h, 9-chloronoscapine 2, 9-bromonoscapine 3 (EM011), and 9-iodonoscapine 4 killed 87.8%, 51.2%, and 56.8% cells, respectively, however noscapine kills only 40% of the cells; revealing 9-chloronoscapine as a potential cytotoxic agent than

  9. 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.

  10. Total synthesis of (+)-schweinfurthins B and E.

    PubMed

    Topczewski, Joseph J; Neighbors, Jeffrey D; Wiemer, David F

    2009-09-18

    The first total synthesis of (+)-schweinfurthin B, a potent and differentially active cytotoxic agent, has been accomplished. Completion of the synthesis required just 16 steps in the longest linear sequence from commercially available vanillin. Key synthetic transformations included a Shi epoxidation and an efficient cascade cyclization initiated by treatment of the resulting epoxide with BF(3).OEt(2). Furthermore, use of a methyl ether as a stable protecting group for benzylic alcohols dramatically increased the efficiency of the overall sequence. The benzylic ether can be removed from this electron-rich aromatic system through oxidation with DDQ that provided the desired aldehyde intermediate in quantitative yield and shortened the synthetic sequence. Introduction of the A-ring diol in the required cis stereochemistry then became viable through a short sequence highlighted by an aldol condensation with benzaldehyde to introduce an olefin as a latent carbonyl group at the C-3 position. This synthesis established for the first time the absolute stereochemistry of the natural product, and provides access to material on a scale that will advance biological studies. The total synthesis of the closely related compound (+)-schweinfurthin E also is reported. PMID:19697910

  11. A weighted overlap-add method of short-time Fourier analysis\\/Synthesis

    Microsoft Academic Search

    R. E. CROCHIERE

    1980-01-01

    In this correspondence we present a new structure and a simplified interpretation of short-time Fourier synthesis using synthesis windows. We show that this approach can be interpreted as a modification of the overlap-add method where we inverse the Fourier transform and window by the synthesis window prior to overlap-adding. This simplified interpretation results in a more efficient structure for short-time

  12. Expedient access to enantiopure cyclopentanic natural products: total synthesis of (-)-cyclonerodiol.

    PubMed

    Pérez Morales, Carmen; Mar Herrador, M; Quílez del Moral, José F; Barrero, Alejandro F

    2015-01-01

    Following the principles of collective total synthesis, a number of natural products sharing an optically pure, multifunctional, cyclopentanic core were synthesized from a common precursor: plinol A (1). This intermediate was efficiently obtained in only four steps from (-)-linalool (2) using as the key step a Ti(III)-mediated diastereoselective radical cyclization. The feasibility of this approach was confirmed with the expedient enantiospecific synthesis of cyclonerodiol (3), and the formal synthesis of chocol G (4) and piperitone (5). PMID:25920207

  13. Transition-Metal Catalyzed Synthesis of Aspergillide B: An Alkyne Addition Strategy

    PubMed Central

    Bartlett, Mark J.

    2012-01-01

    A catalytic enantioselective formal total synthesis of aspergillide B is reported. This linchpin synthesis was enabled by the development of new conditions for Zn-ProPhenol catalyzed asymmetric alkyne addition. This reaction was used in conjunction with ruthenium-catalyzed trans-hydrosilylation to affect the rapid construction of a late-stage synthetic intermediate of aspergillide B to complete a formal synthesis of aspergillide B in a highly efficient manner. PMID:22356535

  14. 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.

  15. Convenient synthesis of N-methylamino acids compatible with Fmoc solid-phase peptide synthesis.

    PubMed

    Biron, Eric; Kessler, Horst

    2005-06-24

    N(alpha)-Methylamino acid containing peptides exhibit interesting therapeutic profiles and are increasingly recognized as potentially useful therapeutics. Unfortunately, their synthesis is hampered by the high price and unavaibility of many N(alpha)-methylamino acids. An efficient and practical preparation of N(alpha)-methyl-N(alpha)-(o-nitrobenzenesulfonyl)-alpha-amino acids without extensive purification is described. The procedure is based on the well-known N-alkylation of N(alpha)-arylsulfonylamino esters which was improved by using dimethyl sulfate and DBU as base. Ester cleavage is efficiently achieved by using an S(N)2-type saponification with lithium iodide, avoiding racemization observed with lithium hydroxide hydrolysis. Compatibility of the synthesized N(alpha)-methylamino acids with Fmoc solid-phase peptide synthesis is demonstrated by using normal coupling conditions to efficiently prepare N-methyl dipeptides. The described procedure allows the preparation of N(alpha)-methylamino acids in a very short period of time and a rapid synthesis of N-methyl peptides using Fmoc solid-phase peptide synthesis. PMID:15960522

  16. 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.

  17. 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

  18. Catalytic chemical amide synthesis at room temperature: one more step toward Peptide synthesis.

    PubMed

    Mohy El Dine, Tharwat; Erb, William; Berhault, Yohann; Rouden, Jacques; Blanchet, Jérôme

    2015-05-01

    An efficient method has been developed for direct amide bond synthesis between carboxylic acids and amines via (2-(thiophen-2-ylmethyl)phenyl)boronic acid as a highly active bench-stable catalyst. This catalyst was found to be very effective at room temperature for a large range of substrates with slightly higher temperatures required for challenging ones. This methodology can be applied to aliphatic, ?-hydroxyl, aromatic, and heteroaromatic acids as well as primary, secondary, heterocyclic, and even functionalized amines. Notably, N-Boc-protected amino acids were successfully coupled in good yields with very little racemization. An example of catalytic dipeptide synthesis is reported. PMID:25849872

  19. Efficient synthesis of mono- and disubstituted 2,3-dihydroquinazolin-4(1 H)-ones using KAl(SO 4) 2·12H 2O as a reusable catalyst in water and ethanol

    Microsoft Academic Search

    Minoo Dabiri; Peyman Salehi; Somayeh Otokesh; Mostafa Baghbanzadeh; Gholamreza Kozehgary; Ali A. Mohammadi

    2005-01-01

    KAl(SO4)2·12H2O was found to catalyze efficiently a one-pot three-component cyclocondensation of isatoic anhydride and primary amines or ammonia sources such as (NH4)2CO3, NH4OAc and NH4Cl with aromatic aldehydes under mild conditions to afford the corresponding mono- and disubstituted 2,3-dihydroquinazolin-4(1H)-ones in good yields.

  20. AlCl3-Promoted Facile E-to-Z Isomerization Route to (Z)-2-Methyl-1-buten-1,4-ylidene Synthons for Highly Efficient and Selective (Z)-Isoprenoid Synthesis

    PubMed Central

    Wang, Guangwei; Negishi, Ei-ichi

    2013-01-01

    Zr-catalyzed methylalumination of 3-butyn-1-ols followed by AlCl3-promoted stereoisomerization at 50 °C for 6 h provides 4-iodo-3-methyl-3-buten-1-ols 2b and 6 of ?98 Z configuration in 87 and 67% yields, respectively. (Z)-1,4-Diiodo-2-methyl-1-butene (1b) obtainable by iodination of 2b is a valuable synthon for efficient and selective syntheses of (Z)-alkene containing isoprenoids. PMID:24307863

  1. Mild and Efficient One-Pot Synthesis of 2-(Perfluoroalkyl)indoles by Means of Sequential Michael-Type Addition and Pd(II)-Catalyzed Cross-Dehydrogenative Coupling (CDC) Reaction.

    PubMed

    Shen, Dandan; Han, Jing; Chen, Jie; Deng, Hongmei; Shao, Min; Zhang, Hui; Cao, Weiguo

    2015-07-01

    2-Perfluoroalkylated indoles were efficiently synthesized via a one-pot cascade Michael-type addition/palladium-catalyzed intramolecular cross-dehydrogenative coupling (CDC) process, using molecular oxygen as the sole oxidant at 100 °C in DMSO. This process allows atom economical assembly of indole rings from inexpensive and readily available anilines and methyl perfluoroalk-2-ynoates and tolerates a broad range of functional groups. PMID:26090551

  2. Synthesis of QS-21-Based Immunoadjuvants

    PubMed Central

    Dai, Qipu; Thogaripally, Punith; Zhang, Ping; Michalek, Suzanne M.

    2014-01-01

    Three structurally defined QS-21-based immune adjuvant candidates (2a-2c) have been synthesized. Application of the two-stage activation glycosylation approach utilizing allyl glycoside building blocks improved the synthetic accessibility of the new adjuvants. The efficient synthesis and establishment of the stand-alone adjuvanticity of the examined synthetic adjuvant (2b) open the door to the pursuit of a new series of structurally defined QS-saponin based synthetic adjuvants. PMID:24147602

  3. Minimum weight aerospace structural synthesis program 

    E-print Network

    Walker, John Michael

    1975-01-01

    Webs Weight Equations General 12 15 16 Multirib Weight Multispar Weight III. PROGRAM DEVELOPMENT 21 27 30 IV. Minimum Weight Analysis of Multirib and Multiweb Wing Box Structures Minimum Weight Aerospace Structural Synthesis Program... The Desk Top Calculator Plot Routines Increased Efficiency PLASTICITY CORRECTION FACTORS Upper Cover ? Multirib Upper Cover ? Multispar 30 35 35 36 37 53 CHAPTER VI. Shear Webs ? Multirib and Multispar Ribs ? Multirib EFFECTIVE DEPTH FACTOR...

  4. Total synthesis of enantiopure potassium aeshynomate.

    PubMed

    Rizos, Stergios R; Stefanakis, John G; Kotoulas, Stefanos S; Koumbis, Alexandros E

    2014-07-18

    Potassium aeshynomate (1) is the leaf-opening factor of the nyctinastic plant Aeshynomene indica L. In this article a convenient and efficient strategy for the total synthesis of enantiomerically pure 1 is described, starting from the l-arabinose derived chiron ent-6. The realized synthetic scheme involves a postcoupling oxidation approach and securely determines the absolute configuration of the targeted natural product, which remained unknown until now. PMID:24967505

  5. Carbon combustion synthesis of nanostructured perovskites

    Microsoft Academic Search

    K. S. Martirosyan; M. Iliev; D. Luss

    2007-01-01

    A novel, economical, and energy-efficient process to produce nanostructured particles of several perovskite oxides, such as\\u000a ferroelectrics BaTiO3, SrTiO3 and LiNbO3, is described. This process, referred to as carbon combustion synthesis of oxides (CCSO) is a modified SHS process that uses\\u000a carbon as a fuel instead of a pure metal. In CCSO of nanostructured materials, the exothermic oxidation of carbon

  6. Synthesis and Optimization of Pipelined Packet Processors

    Microsoft Academic Search

    Cristian Soviani; Ilija Hadzic; Stephen A. Edwards

    2009-01-01

    We consider pipelined architectures of packet proces- sors consisting of a sequence of simple packet-processing mod- ules interconnected by first-in first-out buffers. We propose a new model for describing their function, an automated synthesis technique that generates efficient hardware for them, and an algorithm for computing minimum buffer sizes that allow such pipelines to achieve their maximum throughput. Our functional

  7. Facile construction of the oxaphenalene skeleton by peri ring closure. Formal synthesis of mansonone F

    E-print Network

    Suh, Young-Ger

    . (94% in 3 steps); iv, PhB(OH)2, (CHO)n, propionic acid, PhH, reflux, 1 h, then H2O2, THF; v, 10% PFacile construction of the oxaphenalene skeleton by peri ring closure. Formal synthesis and divergent total synthesis of mansonone F has been accomplished via an efficient construction

  8. Synthesis of speed-independent circuits from STG-unfolding segment

    Microsoft Academic Search

    Alexei L. Semenov; Alexandre Yakovlev; Enric Pastor; Marco A. Peña; Jordi Cortadella

    1997-01-01

    This paper presents a novel technique for synthesis of speed-independentcircuits. It is based on partial order representation ofthe state graph called STG-unfolding segment. The new methoduses approximation technique to speed up the synthesis process.The method is illustrated on the basic implementation architecture.Experimental results demonstrating its efficiency are presented anddiscussed.

  9. Synthesis Of Speed-independent Circuits From STG-unfolding Segment

    Microsoft Academic Search

    A. Semenov; A. Yakovlev; E. Pastor; M. A. Pefia; J. Cortadella

    1997-01-01

    This gaper presents a novel technique for synthesis of speed-independent circuits. It is based on partial order representation of the state graph called STG-unfolding segment. The new method uses approximation technique to speed up the synthesis process. The method is illustrated on the basic implementation architecture. Experimental results demonstrating its efficiency are presented and discussed.

  10. Synthesis of antimicrobial natural products targeting FtsZ: (+)-totarol and related totarane diterpenes.

    PubMed

    Kim, Michelle B; Shaw, Jared T

    2010-08-01

    An efficient, convergent synthesis of totarol by a diastereoselective epoxide/alkene/arene bicyclization is described. The reported synthesis enables the preparation of related diterpenes totaradiol and totarolone as well as previously unavailable derivatives that exhibit comparable inhibition of the bacterial cell division protein FtsZ. PMID:20597470

  11. Synthesis of Antimicrobial Natural Products Targeting FtsZ: (+)-Totarol and Related Totarane Diterpenes

    PubMed Central

    Kim, Michelle B.; Shaw, Jared T.

    2010-01-01

    An efficient, convergent synthesis of totarol by a diastereoselective epoxide/alkene/arene bicyclization is described. The reported synthesis enables the preparation of related diterpenes totaradiol and totarolone as well as previously unavailable derivatives that exhibit comparable inhibition of the bacterial cell division protein FtsZ. PMID:20597470

  12. Microwave initiated synthesis and application of polyacrylic acid grafted carboxymethyl cellulose

    Microsoft Academic Search

    Sumit Mishra; G. Usha Rani; Gautam Sen

    An environmentally benign and efficient route of synthesis of polyacrylic acid grafted carboxymethyl cellulose (CMC-g-PAA) is developed using microwave radiation alone to initiate the grafting reaction. The synthesis is optimized in terms of percentage grafting and intrinsic viscosity, by varying the microwave irradiation time and monomer (acrylic acid) concentration. The grafted product has been characterized by various physicochemical characterization techniques

  13. Potential for Coal-to-Liquids Conversion in the United States--FischerTropsch Synthesis

    E-print Network

    Patzek, Tadeusz W.

    Potential for Coal-to-Liquids Conversion in the United States--Fischer­Tropsch Synthesis Tad W valuable use for the coal, nor will it ever be, as long as it is economical to use natural gas for electric power generation. This finding results from the low efficiency inherent in FT synthesis

  14. Cost optimization in ASIC implementation of periodic hard-real time systems using behavioral synthesis techniques

    Microsoft Academic Search

    Miodrag Potkonjak; Wayne Wolf

    1995-01-01

    Abstract: Modern applications are often defined as sets of several computational tasks. This paper presents a synthesis algorithm for ASIC implementations which realize multiple computational tasks under hard real-time deadlines. The algorithm analyzes constraints imposed by task sharing as well as the traditional datapath synthesis criteria. In particular we demonstrated an efficient technique to combine rate-monotonic scheduling, a widely used

  15. STARLIGHT: Spectral Synthesis Code

    NASA Astrophysics Data System (ADS)

    Cid Fernandes, R.; Mateus, A.; Sodré, L.; Stasinska, G.; Gomes, J. M.

    2011-08-01

    The study of stellar populations in galaxies is entering a new era with the availability of large and high quality databases of both observed galactic spectra and state-of-the-art evolutionary synthesis models. The power of spectral synthesis can be investigated as a mean to estimate physical properties of galaxies. Spectral synthesis is nothing more than the decomposition of an observed spectrum in terms of a superposition of a base of simple stellar populations of various ages and metallicities, producing astrophysically interesting output such as the star-formation and chemical enrichment histories of a galaxy, its extinction and velocity dispersion. This is what the STARLIGHT spectral synthesis code does.

  16. 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

  17. 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 a-tosyloxy ketones with variety of thioamides/amidines in water ...

  18. Scalable and Scalably-Verifiable Sequential Synthesis Alan Mishchenko Michael Case Robert Brayton Stephen Jang

    E-print Network

    Mishchenko, Alan

    Scalable and Scalably-Verifiable Sequential Synthesis Alan Mishchenko Michael Case Robert Brayton, brayton}@eecs.berkeley.edu sjang@xilinx.com Abstract This paper describes an efficient implementation

  19. 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.

  20. Synthesis of 2H-Indazoles by the [3+2] Cycloaddition of Arynes and Sydnones

    PubMed Central

    Wu, Chunrui; Fang, Yuesi; Larock, Richard C.; Shi, Feng

    2010-01-01

    A rapid and efficient synthesis of 2H-indazoles has been developed, which involves the [3+2] dipolar cycloaddition of arynes and sydnones. The process proceeds under mild reaction conditions in good to excellent yields. PMID:20394430