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Sample records for amine catalyzed silica

  1. Understanding amine catalyzed silica polymerization : diatoms as bioarchitects.

    SciTech Connect

    Spoerke, Erik David; Aubry, Sylvie; Lane, Pamela; Robinson, David B; Bauer, Christina A.; Zendejas, Frank; Tran, Huu; Lane, Todd W.; Simmons, Blake Alexander

    2007-10-01

    Current state-of-the-art biomimetic methodologies employed worldwide for the realization of self-assembled nanomaterials are adequate for certain unique applications, but a major breakthrough is needed if these nanomaterials are to obtain their true promise and potential. These routes typically utilize a 'top-down' approach in terms of controlling the nucleation, growth, and deposition of structured nanomaterials. Most of these techniques are inherently limited to primarily 2D and simple 3D structures, and are therefore limited in their ultimate functionality and field of use. Zeolites, one of the best-known and understood synthetic silica structures, typically possess highly ordered silica domains over very small length scales. The development of truly organized and hierarchical zeolites over several length scales remains an intense area of research world wide. Zeolites typically require high-temperature and complex synthesis routes that negatively impact certain economic parameters and, therefore, the ultimate utility of these materials. Nonetheless, zeolite usage is in the tons per year worldwide and is quickly becoming ubiquitous in its applications. In addition to these more mature aspects of current practices in materials science, one of the most promising fields of nanotechnology lies in the advent and control of biologically self-assembled materials, especially those involved with silica and other ceramics such as hydroxyapatite. Nature has derived, through billions of years of evolutionary steps, numerous methods by which fault-tolerant and mechanically robust structures can be created with exquisite control and precision at relatively low temperature ranges and pressures. Diatoms are one of the best known examples that exhibit this degree of structure and control known that is involved with the biomineralization of silica. Diatoms are eukaryotic algae that are ubiquitous in marine and freshwater environments. They are a dominant form of phytoplankton

  2. Knoevenagel reaction in water catalyzed by amine supported on silica gel.

    PubMed

    Isobe, Kohei; Hoshi, Takashi; Suzuki, Toshio; Hagiwara, Hisahiro

    2005-01-01

    An environmentally benign and sustainable Knoevenagel reaction of aldehyde with ethyl cyanoacetate has been achieved at ambient temperature in water employing 3-aminopropylated silica gel (NAP) as a catalyst. Wide applicability of the reaction is illustrated by the results that not only arylaldehydes of both electronic characters but also aliphatic aldehydes afforded the products. The reaction condition was so mild that aldehydes having acid- or base-sensitive substituents provided substituted alpha-cyano-alpha, beta-unsaturated esters. The catalyst has been efficiently recycled more than five times without any pre-treatment. Catalyst loading was successfully reduced to 0.0029 mmol% (TON = up to 9,226). This protocol was also applicable to the Knoevenagel reaction of malononitrile in good yields in water.

  3. Amine catalyzed condensation of tetraethylorthosilicate

    NASA Technical Reports Server (NTRS)

    Jones, S.

    2001-01-01

    The catalysis of the condensation of hydrolyzed metal alkoxides by amines has been mentioned in the literature, but there has been no systematic study of their influence on the rate of the condensation reaction of the alkoxide and the microstructure of the resultant gel.

  4. Aminated hollow silica spheres for electrochemical DNA biosensor

    NASA Astrophysics Data System (ADS)

    Ariffin, Eda Yuhana; Heng, Lee Yook; Futra, Dedi; Ling, Tan Ling

    2015-09-01

    An electrochemical DNA biosensor for e.coli determination based on aminated hollow silica was successfully developed. Aminated hollow silica spheres were prepared through the reaction of Tween 20 template and silica precursor. The template was removed by the thermal decomposition at 620°C. Hollow silica spheres were modified with (3-Aminopropyl) triethoxysilane (APTS) to form aminated hollow silica spheres.Aminated DNA probe were covalently immobilized on to the amine functionalized hollow silica spheres through glutaradehyde linkers. The formation hollow silica was characterized using FTIR and FESEM. A range of 50-300nm particle size obtained from FESEM micrograph. Meanwhile for the electrochemical study, a quasi-reversible system has been obtain via cyclic voltammetry (CV).

  5. Bulk Gold-Catalyzed Reactions of Isocyanides, Amines, and Amine N-Oxides

    SciTech Connect

    Klobukowski, Erik; Angelici, Robert; Woo, Keith L.

    2012-01-26

    Bulk gold powder (5–50 μm particles) catalyzes the reactions of isocyanides with amines and amine N-oxides to produce ureas. The reaction of n-butyl isocyanide (nBu–N≡C) with di-n-propylamine and N-methylmorpholine N-oxide in acetonitrile, which was studied in the greatest detail, produced 3-butyl-1,1-dipropylurea (O═C(NHnBu)(NnPr2)) in 99% yield at 60 °C within 2 h. Sterically and electronically different isocyanides, amines, and amine N-oxides react successfully under these conditions. Detailed studies support a two-step mechanism that involves a gold-catalyzed reaction of adsorbed isocyanide with the amine N-oxide to form an isocyanate (RN═C═O), which rapidly reacts with the amine to give the urea product. These investigations show that bulk gold, despite its reputation for poor catalytic activity, is capable of catalyzing these reactions.

  6. Acid-catalyzed dehydrogenation of amine-boranes

    DOEpatents

    Stephens, Frances Helen; Baker, Ralph Thomas

    2010-01-12

    A method of dehydrogenating an amine-borane using an acid-catalyzed reaction. The method generates hydrogen and produces a solid polymeric [R.sup.1R.sup.2B--NR.sup.3R.sup.4].sub.n product. The method of dehydrogenating amine-boranes may be used to generate H.sub.2 for portable power sources.

  7. Ruthenium-catalyzed tertiary amine formation from nitroarenes and alcohols.

    PubMed

    Feng, Chao; Liu, Yong; Peng, Shengming; Shuai, Qi; Deng, Guojun; Li, Chao-Jun

    2010-11-05

    A highly selective ruthenium-catalyzed C-N bond formation was developed by using the hydrogen-borrowing strategy. Various tertiary amines were obtained efficiently from nitroarenes and primary alcohols. The reaction tolerates a wide range of functionalities. A tentative mechanism was proposed for this direct amination reaction of alcohols with nitroarenes.

  8. Palladium-catalyzed amination of allyl alcohols.

    PubMed

    Ghosh, Raju; Sarkar, Amitabha

    2011-10-21

    An efficient catalytic amination of aryl-substituted allylic alcohols has been developed. The complex [(η(3)-allyl)PdCl](2) modified by a bis phosphine ligand, L, has been used as catalyst in the reaction that afforded a wide range of allyl amines in good to excellent yield under mild conditions.

  9. Palladium-catalyzed amination of dichloroquinolines with adamantane-containing amines.

    PubMed

    Abel, Anton S; Averin, Alexei D; Maloshitskaya, Olga A; Savelyev, Evgenii N; Orlinson, Boris S; Novakov, Ivan A; Beletskaya, Irina P

    2013-02-06

    Pd-catalyzed amination of isomeric 2,6-, 2,8-, 4,8- and 4,7-dichloroquinolines was studied using adamantane-containing amines in which substituents at the nitrogen atom differ in bulkiness. The selectivity of the amination of 2,6-dichloroquinoline was very low, substantially better results were obtained with 2,8-dichloroquinoline, and 4,8- and 4,7-dichloroquinolines provided the best yields of the amination products. Diamination of 4,8- and 4,7-dichloroquinolines was carried out with two amines which differ strongly in the bulkiness of the alkyl group. In the majority of cases BINAP ligand was successfully applied, however, it had to be replaced with DavePhos in certain reactions when using the most sterically hindered amine as well as for the diamination reactions.

  10. Microwave assisted N-alkylation of amine functionalized crystal-like mesoporous phenylene-silica.

    PubMed

    Lourenço, Mirtha A O; Siegel, Renée; Mafra, Luís; Ferreira, Paula

    2013-04-28

    N-alkylation reaction of amine functionalized phenylene moieties in crystal-like mesoporous silica is successfully achieved with about 87% of conversion in two reaction cycles. A potassium iodide catalyzed method commonly used for the selective N-monoalkylation of aniline is adapted and optimized to the N-monoalkylation reactions of the amine functionalized periodic mesoporous phenylene-silica (NH2-PMO) under microwave irradiation with preservation of the ordered mesostructure and of the crystal-like molecular scale periodicity of the material. This functionalization opens an avenue for the preparation of new materials with different amino-alkyl groups specially designed for a desired application, namely on the adsorption or catalytic fields.

  11. Biaryl Phosphine Ligands in Palladium-Catalyzed Amination

    PubMed Central

    Surry, David S.

    2012-01-01

    Palladium-catalyzed amination of aryl halides has undergone rapid development in the last 12 years. This has been largely driven by implementation of new classes of ligands. Biaryl phosphines have proven to provide especially active catalysts in this context. This review discusses the applications that these catalysts have found in C-N cross-coupling in heterocycle synthesis, pharmaceuticals, materials science and natural product synthesis. PMID:18663711

  12. Lactoperoxidase-catalyzed activation of carcinogenic aromatic and heterocyclic amines.

    PubMed

    Gorlewska-Roberts, Katarzyna M; Teitel, Candee H; Lay, Jackson O; Roberts, Dean W; Kadlubar, Fred F

    2004-12-01

    Lactoperoxidase, an enzyme secreted from the human mammary gland, plays a host defensive role through antimicrobial activity. It has been implicated in mutagenic and carcinogenic activation in the human mammary gland. The potential role of heterocyclic and aromatic amines in the etiology of breast cancer led us to examination of the lactoperoxidase-catalyzed activation of the most commonly studied arylamine carcinogens: 2-amino-1-methyl-6-phenylimidazo[4,5-b]-pyridine (PhIP), benzidine, 4-aminobiphenyl (ABP), 2-amino-3-methylimidazo[4,5-f]quinoline (IQ), and 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx). In vitro activation was performed with lactoperoxidase (partially purified from bovine milk or human milk) in the presence of hydrogen peroxide and calf thymus DNA. Products formed during enzymatic activation were monitored by HPLC with ultraviolet and radiometric detection. Two of these products were characterized as hydrazo and azo derivatives by means of mass spectrometry. The DNA binding level of 3H- and 14C-radiolabeled amines after peroxidase-catalyzed activation was dependent on the hydrogen peroxide concentration, and the highest levels of carcinogen binding to DNA were observed at 100 microM H2O2. Carcinogen activation and the level of binding to DNA were in the order of benzidine > ABP > IQ > MeIQx > PhIP. One of the ABP adducts was identified, and the level at which it is formed was estimated to be six adducts/10(5) nucleotides. The susceptibility of aromatic and heterocyclic amines for lactoperoxidase-catalyzed activation and the binding levels of activated products to DNA suggest a potential role of lactoperoxidase-catalyzed activation of carcinogens in the etiology of breast cancer.

  13. Dirhodium Catalyzed C-H Arene Amination using Hydroxylamines

    PubMed Central

    Paudyal, Mahesh P.; Adebesin, Adeniyi Michael; Burt, Scott R.; Ess, Daniel H.; Ma, Zhiwei; Kürti, László; Falck, John R.

    2016-01-01

    Primary and N-alkyl arylamine motifs are key functional groups in pharmaceuticals, agrochemicals and functional materials as well as in bioactive natural products. However, there is a dearth of generally applicable methods for the direct replacement of aryl hydrogens with –NH2/-NH-alkyl moieties. Here, we present a mild dirhodium-catalyzed C-H amination for conversion of structurally diverse monocyclic and fused aromatics to the corresponding primary and N-alkyl arylamines using either NH2/NHalkyl-O-(sulfonyl)hydroxylamines as aminating agents; the relatively weak RSO2O-N bond functions as an internal oxidant. The methodology is operationally simple, scalable, and fast at or below ambient temperature, furnishing arylamines in moderate-to-good yields and with good regioselectivity. It can be readily extended to the synthesis of fused N-heterocycles. PMID:27609890

  14. Palladium-catalyzed vinylation of aminals with simple alkenes: a new strategy to construct allylamines.

    PubMed

    Xie, Yinjun; Hu, Jianhua; Wang, Yanyu; Xia, Chungu; Huang, Hanmin

    2012-12-26

    A novel, highly selective palladium-catalyzed vinylation reaction for the direct synthesis of allylic amines from styrenes and aminals has been established. The utility of this method was also demonstrated by the rapid synthesis of cinnarizine from aldehydes, amines, and simple alkenes in one-pot manner. Mechanistic studies suggested that the reaction proceeds through a valuable cyclometalated Pd(II) complex generated by the oxidative addition of aminal to a Pd(0) species.

  15. Palladium-catalyzed hydroaminocarbonylation of alkenes with amines: a strategy to overcome the basicity barrier imparted by aliphatic amines.

    PubMed

    Zhang, Guoying; Gao, Bao; Huang, Hanmin

    2015-06-22

    A novel and efficient palladium-catalyzed hydroaminocarbonylation of alkenes with aminals has been developed under mild reaction conditions, and allows the synthesis of a wide range of N-alkyl linear amides in good yields with high regioselectivity. On the basis of this method, a cooperative catalytic system operating by the synergistic combination of palladium, paraformaldehyde, and acid was established for promoting the hydroaminocarbonylation of alkenes with both aromatic and aliphatic amines, which do not react well under conventional palladium-catalyzed hydroaminocarbonylation.

  16. Boron-Catalyzed N-Alkylation of Amines using Carboxylic Acids.

    PubMed

    Fu, Ming-Chen; Shang, Rui; Cheng, Wan-Min; Fu, Yao

    2015-07-27

    A boron-based catalyst was found to catalyze the straightforward alkylation of amines with readily available carboxylic acids in the presence of silane as the reducing agent. Various types of primary and secondary amines can be smoothly alkylated with good selectivity and good functional-group compatibility. This metal-free amine alkylation was successfully applied to the synthesis of three commercial medicinal compounds, Butenafine, Cinacalcet. and Piribedil, in a one-pot manner without using any metal catalysts.

  17. Highly efficient heterogeneous gold-catalyzed direct synthesis of tertiary and secondary amines from alcohols and urea.

    PubMed

    He, Lin; Qian, Yue; Ding, Ran-Sheng; Liu, Yong-Mei; He, He-Yong; Fan, Kang-Nian; Cao, Yong

    2012-04-01

    Urea, the white gold: The efficient synthesis of tertiary and secondary amines is achieved by heterogeneous gold-catalyzed direct amination of stoichiometric alcohols with urea in good to excellent yields. Via a hydrogen autotransfer pathway, the reactions of primary alcohols with urea give tertiary amines exclusively, while secondary alcohols selectively afford secondary amines.

  18. Silanol-assisted carbinolamine formation in an amine-functionalized mesoporous silica surface: Theoretical investigation by fragmentation methods

    DOE PAGES

    de Lima Batista, Ana P.; Zahariev, Federico; Slowing, Igor I.; ...

    2015-12-15

    The aldol reaction catalyzed by an amine-substituted mesoporous silica nanoparticle (amine-MSN) surface was investigated using a large molecular cluster model (Si392O958C6NH361) combined with the surface integrated molecular orbital/molecular mechanics (SIMOMM) and fragment molecular orbital (FMO) methods. Three distinct pathways for the carbinolamine formation, the first step of the amine-catalyzed aldol reaction, are proposed and investigated in order to elucidate the role of the silanol environment on the catalytic capability of the amine-MSN material. Here the computational study reveals that the most likely mechanism involves the silanol groups actively participating in the reaction, forming and breaking covalent bonds in the carbinolaminemore » step. Furthermore, the active participation of MSN silanol groups in the reaction mechanism leads to a significant reduction in the overall energy barrier for the carbinolamine formation. In addition, a comparison between the findings using a minimal cluster model and the Si392O958C6NH361 cluster suggests that the use of larger models is important when heterogeneous catalysis problems are the target.« less

  19. Silanol-assisted carbinolamine formation in an amine-functionalized mesoporous silica surface: Theoretical investigation by fragmentation methods

    SciTech Connect

    de Lima Batista, Ana P.; Zahariev, Federico; Slowing, Igor I.; Braga, Ataualpa A. C.; Ornellas, Fernando R.; Gordon, Mark S.

    2015-12-15

    The aldol reaction catalyzed by an amine-substituted mesoporous silica nanoparticle (amine-MSN) surface was investigated using a large molecular cluster model (Si392O958C6NH361) combined with the surface integrated molecular orbital/molecular mechanics (SIMOMM) and fragment molecular orbital (FMO) methods. Three distinct pathways for the carbinolamine formation, the first step of the amine-catalyzed aldol reaction, are proposed and investigated in order to elucidate the role of the silanol environment on the catalytic capability of the amine-MSN material. Here the computational study reveals that the most likely mechanism involves the silanol groups actively participating in the reaction, forming and breaking covalent bonds in the carbinolamine step. Furthermore, the active participation of MSN silanol groups in the reaction mechanism leads to a significant reduction in the overall energy barrier for the carbinolamine formation. In addition, a comparison between the findings using a minimal cluster model and the Si392O958C6NH361 cluster suggests that the use of larger models is important when heterogeneous catalysis problems are the target.

  20. Iron-Catalyzed Oxyfunctionalization of Aliphatic Amines at Remote Benzylic C-H Sites.

    PubMed

    Mbofana, Curren T; Chong, Eugene; Lawniczak, James; Sanford, Melanie S

    2016-09-02

    We report the development of an iron-catalyzed method for the selective oxyfunctionalization of benzylic C(sp(3))-H bonds in aliphatic amine substrates. This transformation is selective for benzylic C-H bonds that are remote (i.e., at least three carbons) from the amine functional group. High site selectivity is achieved by in situ protonation of the amine with trifluoroacetic acid, which deactivates more traditionally reactive C-H sites that are α to nitrogen. The scope and synthetic utility of this method are demonstrated via the synthesis and derivatization of a variety of amine-containing, biologically active molecules.

  1. Enantioselective Synthesis of β-Arylamines via Chiral Phosphoric Acid-Catalyzed Asymmetric Reductive Amination.

    PubMed

    Kim, Kyung-Hee; Lee, Chun-Young; Cheon, Cheol-Hong

    2015-06-19

    A new method for the synthesis of chiral β-aryl amines via chiral phosphoric acid-catalyzed enantioselective reductive amination of benzyl methyl ketone derivatives with Hantzsch ester was developed. Various chiral β-aryl amines were obtained in high yields and with good to high enantioselectivities. This transformation is applicable to gram-scale reactions, and the catalyst loading can be reduced to 1 mol % without sacrificing any catalytic efficacy. Furthermore, the resulting β-aryl amine was successfully converted into a tetrahydroisoquinoline compound without any loss of enantioselectivity.

  2. Pd-catalyzed asymmetric allylic amination using easily accessible metallocenyl P,N-ligands.

    PubMed

    Wu, Hongwei; Xie, Fang; Wang, Yanlan; Zhao, Xiaohu; Liu, Delong; Zhang, Wanbin

    2015-04-14

    Compared to their C1-symmetric counterparts, planar chiral C2-symmetric metallocenyl P,N-ligands are efficient chiral ligands for Pd-catalyzed asymmetric allylic aminations, providing a number of amination products with high enantioselectivities. A non-C2-symmetric ferrocenyl P,N-ligand (a by-product obtained during the synthesis of the above C2-symmetric species) was also found to be an efficient ligand for asymmetric allylic aminations. A mixed ligand system consisting of both C2- and non-C2-symmetric ferrocene complexes was examined and showed high catalytic activity with the amination products being obtained with excellent enantioselectivities.

  3. Palladium-catalyzed/norbornene-mediated ortho-amination/N-tosylhydrazone insertion reaction: an approach to the synthesis of ortho-aminated vinylarenes.

    PubMed

    Zhou, Ping-Xin; Ye, Yu-Ying; Ma, Jun-Wei; Zheng, Lan; Tang, Qian; Qiu, Yi-Feng; Song, Bo; Qiu, Zi-Hang; Xu, Peng-Fei; Liang, Yong-Min

    2014-07-18

    ortho-Aminated vinylarene derivatives were obtained via a reaction of aryl iodides, N-benzoyloxyamines, and N-tosylhydrazones. This approach involves a palladium-catalyzed, norbornene-mediated ortho-amination/N-tosylhydrazone insertion reaction. In this transformation, one C-N bond and one C-C bond are formed and an amine group is introduced at the ortho position successfully.

  4. Iron-Catalyzed Allylic Amination Directly from Allylic Alcohols.

    PubMed

    Emayavaramban, Balakumar; Roy, Moumita; Sundararaju, Basker

    2016-03-14

    Allylic amination, directly from alcohols, has been demonstrated without any Lewis acid activators using an efficient and regiospecific molecular iron catalyst. Various amines and alcohols were employed and the reaction proceeded through the oxidation/reduction (redox) pathway. A direct one-step synthesis of common drugs, such as cinnarizine and nafetifine, was exhibited from cinnamyl alcohol that produced water as side product.

  5. Silver-catalyzed synthesis of amides from amines and aldehydes

    DOEpatents

    Madix, Robert J; Zhou, Ling; Xu, Bingjun; Friend, Cynthia M; Freyschlag, Cassandra G

    2014-11-18

    The invention provides a method for producing amides via the reaction of aldehydes and amines with oxygen adsorbed on a metallic silver or silver alloy catalyst. An exemplary reaction is shown in Scheme 1: (I), (II), (III). ##STR00001##

  6. Magnetic Silica Supported Copper: A Modular Approach to Aqueous Ullmann-type Amination of Aryl Halides

    EPA Science Inventory

    One-pot synthesis of magnetic silica supported copper catalyst has been described via in situ generated magnetic silica (Fe3O4@SiO2); the catalyst can be used for the efficacious amination of aryl halides in aqueous medium under microwave irradiation.

  7. Gold(I)-catalyzed intramolecular amination of allylic alcohols with alkylamines.

    PubMed

    Mukherjee, Paramita; Widenhoefer, Ross A

    2011-03-18

    A 1:1 mixture of (1)AuCl [1 = P(t-Bu)(2)o-biphenyl] and AgSbF(6) catalyzes the intramolecular amination of allylic alcohols with alkylamines to form substituted pyrrolidine and piperidine derivatives. Gold(I)-catalyzed cyclization of (R,Z)-8-(N-benzylamino)-3-octen-2-ol (96% ee, 95% de) led to isolation of (R,E)-1-benzyl-2-(1-propenyl)piperidine in 99% yield with 96% ee, consistent with the net syn addition of the amine relative to the departing hydroxyl group.

  8. Versatile synthesis of thiol- and amine-bifunctionalized silica nanoparticles based on the ouzo effect.

    PubMed

    Chiu, Shih-Jiuan; Wang, Su-Yuan; Chou, Hung-Chang; Liu, Ying-Ling; Hu, Teh-Min

    2014-07-08

    In this article, we report a novel, nanoprecipitation-based method for preparing silica nanoparticles with thiol and amine cofunctionalization. (3-Mercaptopropyl)trimethoxysilane (MPTMS) and 3-aminopropyltrimethoxysilane (APTMS) were used as the organosilane precursors, which were subjected to acid-catalyzed polycondensation in an organic phase containing a water-miscible solvent (e.g., dimethyl sulfoxide). A pale colloidal solution could be immediately formed when the preincubated organic phase was directly injected into water. The initial composition ratio between MPTMS and APTMS is an important factor governing the formation of nanoparticles. Specifically, large, unstable micrometer-sized particles were formed for preparation using MPTMS as the sole silane source. In contrast, when APTMS was used alone, no particles could be formed. By reducing the fraction of APTMS (or increasing that of MPTMS) in the initial mixture of organosilanes, the formation of nanometer-sized particles occurred at a critical fraction of APTMS (i.e., 25%). Remarkably, a tiny fraction (e.g., 1%) of APTMS was sufficient to produce stable nanoparticles with a hydrodynamic diameter of about 200 nm. Other factors that would also affect particle formation were determined. Moreover, an interesting temperature effect on particle formation was observed. The TEM micrographs show spherical nanospheres with mean sizes of 130-150 nm in diameter. The solid-state (29)Si NMR spectra demonstrate that the hybrid silica materials contain fully and partially condensed silicon structures. The bifunctionalized silica nanoparticles have positive zeta potentials whose magnitudes are positively correlated with the amount of APTMS. The total thiol content, however, is negatively correlated with the amount of APTMS. The cationic nanoparticles can bind an antisense oligonucleotide in a composition-dependent manner.

  9. Amine functionalized cubic mesoporous silica nanoparticles as an oral delivery system for curcumin bioavailability enhancement

    NASA Astrophysics Data System (ADS)

    Budi Hartono, Sandy; Hadisoewignyo, Lannie; Yang, Yanan; Meka, Anand Kumar; Antaresti; Yu, Chengzhong

    2016-12-01

    In the present work, a simple method was used to develop composite curcumin-amine functionalized mesoporous silica nanoparticles (MSN). The nanoparticles were used to improve the bioavailability of curcumin in mice through oral administration. We investigated the effect of particle size on the release profile, solubility and oral bioavailability of curcumin in mice, including amine functionalized mesoporous silica micron-sized-particles (MSM) and MSN (100-200 nm). Curcumin loaded within amine functionalized MSN (MSN-A-Cur) had a better release profile and a higher solubility compared to amine MSM (MSM-A-Cur). The bioavailability of MSN-A-Cur and MSM-A-Cur was considerably higher than that of ‘free curcumin’. These results indicate promising features of amine functionalized MSN as a carrier to deliver low solubility drugs with improved bioavailability via the oral route.

  10. Trimodal nanoporous silica as a support for amine-based CO2 adsorbents: Improvement in adsorption capacity and kinetics

    NASA Astrophysics Data System (ADS)

    Chen, Chao; Bhattacharjee, Samiran

    2017-02-01

    A trimodal nanoporous silica (TS) having unique trimodal pore structure viz., internal mesopores, textural mesopores and interconnected macropores, has been functionalized with amine using two different methods covalent grafting and wet impregnation. Both were studied as nanocomposite sorbents for CO2 capture. The effects of the amine loading, immobilization processes and the type of support were investigated. Commercially available silica gel (SG) with a purely mesoporous structure was studied as the support for the amine in order to compare differences in pore structure and amine loading with differences in CO2 adsorption capacity and kinetics. Amine-grafted TS exhibited much faster CO2 adsorption kinetics at 35 °C than amine-grafted SG. At the same amine loading, amine-impregnated TS showed higher CO2 adsorption capacity and faster CO2 adsorption kinetics than amine-impregnated SG. The CO2 adsorption capacity of amine-impregnated TS increased as the amine loading increased until 70%, with the highest value of 172 mg/g, while the amine-impregnated SG reached the highest CO2 adsorption capacity of only 78 mg/g at 40% amine loading. More importantly, amine-impregnated as-prepared TS exhibited even higher CO2 capture capacity than amine-impregnated TS when the amine loading was below 60%. Results suggest that amine-modified trimodal nanoporous silica sorbents meet the challenges of current CO2 capture technology.

  11. Palladium-Catalyzed Enantioselective C-H Activation of Aliphatic Amines Using Chiral Anionic BINOL-Phosphoric Acid Ligands.

    PubMed

    Smalley, Adam P; Cuthbertson, James D; Gaunt, Matthew J

    2017-02-01

    The design of an enantioselective Pd(II)-catalyzed C-H amination reaction is described. The use of a chiral BINOL phosphoric acid ligand enables the conversion of readily available amines into synthetically valuable aziridines in high enantiomeric ratios. The aziridines can be derivatized to afford a range of chiral amine building blocks incorporating motifs readily encountered in pharmaceutically relevant molecules.

  12. Synthesis of chiral sultams via palladium-catalyzed intramolecular asymmetric reductive amination.

    PubMed

    Song, Bo; Yu, Chang-Bin; Ji, Yue; Chen, Mu-Wang; Zhou, Yong-Gui

    2017-02-04

    A novel palladium-catalyzed intramolecular reductive amination of ketones with weakly nucleophilic sulfonamides has been developed in the presence of a Brønsted acid, giving a wide range of chiral γ-, δ-, and ε-sultams in high yields and up to 99% of enantioselectivity.

  13. Enantioselective synthesis of β-substituted chiral allylic amines via Rh-catalyzed asymmetric hydrogenation.

    PubMed

    Wang, Qingli; Gao, Wenchao; Lv, Hui; Zhang, Xumu

    2016-09-27

    An asymmetric mono-hydrogenation of 2-acetamido-1,3-dienes catalyzed by a Rh-DuanPhos complex has been developed. This approach provides easy access to chiral allylic amines with excellent enantioselectivities and high regioselectivities. The products are valuable chiral building blocks for pharmaceuticals.

  14. Dialkylbiaryl Phosphines in Pd-Catalyzed Amination: A User’s Guide

    PubMed Central

    Surry, David S.

    2012-01-01

    Dialkylbiaryl phosphines are a valuable class of ligand for Pd-catalyzed amination reactions and have been applied in a range of contexts. This review attempts to aid the reader in the selection of the best choice of reaction conditions and ligand of this class for the most commonly encountered and practically important substrate combinations. PMID:22432049

  15. Gold(I)-catalyzed amination of allylic alcohols with cyclic ureas and related nucleophiles.

    PubMed

    Mukherjee, Paramita; Widenhoefer, Ross A

    2010-03-19

    A 1:1 mixture of [P(t-Bu)(2)-o-biphenyl]AuCl and AgSbF(6) catalyzes the intermolecular amination of allylic alcohols with 1-methylimidazolidin-2-one and related nucleophiles that, in the case of gamma-unsubstituted or gamma-methyl-substituted allylic alcohols, occurs with high gamma-regioselectivity and syn-stereoselectivity.

  16. Amine modification of nonporous silica nanoparticles reduces inflammatory response following intratracheal instillation in murine lungs.

    PubMed

    Morris, Angie S; Adamcakova-Dodd, Andrea; Lehman, Sean E; Wongrakpanich, Amaraporn; Thorne, Peter S; Larsen, Sarah C; Salem, Aliasger K

    2016-01-22

    Amorphous silica nanoparticles (NPs) possess unique material properties that make them ideal for many different applications. However, the impact of these materials on human and environmental health needs to be established. We investigated nonporous silica NPs both bare and modified with amine functional groups (3-aminopropyltriethoxysilane (APTES)) in order to evaluate the effect of surface chemistry on biocompatibility. In vitro data showed there to be little to no cytotoxicity in a human lung cancer epithelial cell line (A549) for bare silica NPs and amine-functionalized NPs using doses based on both mass concentration (below 200μg/mL) and exposed total surface area (below 14m(2)/L). To assess lung inflammation, C57BL/6 mice were administered bare or amine-functionalized silica NPs via intra-tracheal instillation. Two doses (0.1 and 0.5mg NPs/mouse) were tested using the in vivo model. At the higher dose used, bare silica NPs elicited a significantly higher inflammatory response, as evidence by increased neutrophils and total protein in bronchoalveolar lavage (BAL) fluid compared to amine-functionalized NPs. From this study, we conclude that functionalization of nonporous silica NPs with APTES molecules reduces murine lung inflammation and improves the overall biocompatibility of the nanomaterial.

  17. Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration

    DOE PAGES

    Eedugurala, Naresh; Wang, Zhuoran; Chaudhary, Umesh; ...

    2015-11-04

    The hydroboration of aldehydes and ketones using a silica-supported zirconium catalyst is reported. Reaction of Zr(NMe2)4 and mesoporous silica nanoparticles (MSN) provides the catalytic material Zr(NMe2)n@MSN. Exhaustive characterization of Zr(NMe2)n@MSN with solid-state (SS)NMR and infrared spectroscopy, as well as through reactivity studies, suggests its surface structure is primarily ≡SiOZr(NMe2)3. The presence of these nitrogen-containing zirconium sites is supported by 15N NMR spectroscopy, including natural abundance 15N NMR measurements using dynamic nuclear polarization (DNP) SSNMR. The Zr(NMe2)n@MSN material reacts with pinacolborane (HBpin) to provide Me2NBpin and the material ZrH/Bpin@MSN that is composed of interacting surface-bonded zirconium hydride and surface-bonded borane ≡SiOBpinmore » moieties in an approximately 1:1 ratio, as well as zirconium sites coordinated by dimethylamine. The ZrH/Bpin@MSN is characterized by 1H/2H and 11B SSNMR and infrared spectroscopy and through its reactivity with D2. The zirconium hydride material or the zirconium amide precursor Zr(NMe2)n@MSN catalyzes the selective hydroboration of aldehydes and ketones with HBpin in the presence of functional groups that are often reduced under hydroboration conditions or are sensitive to metal hydrides, including olefins, alkynes, nitro groups, halides, and ethers. Remarkably, this catalytic material may be recycled without loss of activity at least eight times, and air-exposed materials are catalytically active. These supported zirconium centers are robust catalytic sites for carbonyl reduction and that surface-supported, catalytically reactive zirconium hydride may be generated from zirconium-amide or zirconium alkoxide sites.« less

  18. Adsorption of formaldehyde vapor by amine-functionalized mesoporous silica materials.

    PubMed

    Srisuda, Saeung; Virote, Boonamnuayvitaya

    2008-01-01

    The amine-functionalized mesoporous silica materials were prepared via the co-condensation reaction of tetraethoxysilane and three types of organoalkoxysilanes: 3-aminopropyl-trimethoxysilane, n-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and 3-(2-(2-aminoehtylamino)ethylamino) propyl-trimethoxysilane. Cetyltrimethylammonium bromide was used as a template for forming pores. Specific surface area and pore volume of the amine-functionalized mesoporous silica materials were determined using surface area and pore size analyzer. Fourier transform infrared (FTIR) spectroscope was employed for identifying the functional groups on pore surface. In addition, the amine-functionalized mesoporous silica materials were applied as adsorbents for adsorbing formaldehyde vapor. FTIR spectra showed the evidence of the reaction between formaldehyde molecules and amine groups on pore surface of adsorbents. The equilibrium data of formaldehyde adsorbed on the adsorbents were analyzed using the Langmuir, Freundlich and Temkin isotherm. The sample functionalized from n-(2-aminoethyl)-3-aminopropyltrimethoxysilane showed the highest adsorption capacity owing to its amine groups and the large pore diameter.

  19. Cobalt-catalyzed intramolecular C-H amination with arylsulfonyl azides.

    PubMed

    Ruppel, Joshua V; Kamble, Rajesh M; Zhang, X Peter

    2007-11-08

    Cobalt complexes of porphyrins are effective catalysts for intramolecular C-H amination with arylsulfonyl azides. The cobalt-catalyzed process can proceed efficiently under mild and neutral conditions in low catalyst loading without the need of other reagents or additives, generating nitrogen gas as the only byproduct. The catalytic system can be applied to primary, secondary, and tertiary C-H bonds and is suitable for a broad range of arylsulfonyl azides, leading to high-yielding syntheses of various benzosultams.

  20. Enantioselective Aminomethylamination of Conjugated Dienes with Aminals Enabled by Chiral Palladium Complex-Catalyzed C-N Bond Activation.

    PubMed

    Liu, Yang; Xie, Yinjun; Wang, Hongli; Huang, Hanmin

    2016-04-06

    A novel highly enantioselective aminomethylamination of conjugated dienes with aminals catalyzed by a chiral palladium complex ligated with BINOL-derived chiral diphosphinite has been successfully developed. This reaction proceeds via a Pd-catalyzed cascade C-N bond activation, aminomethylation, and asymmetric allylic amination reaction under mild reaction conditions, providing a unique and efficient strategy for the synthesis of enantiomerically pure allylic 1,3-diamines.

  1. In(III)-catalyzed tandem reaction of chromone-derived Morita-Baylis-Hillman alcohols with amines.

    PubMed

    Wu, Chen; Liu, Yuliang; Zeng, Hao; Liu, Li; Wang, Dong; Chen, Yongjun

    2011-01-07

    The reaction of chromone-derived cyclic Morita-Baylis-Hillman alcohols with amines catalyzed by In(OTf)(3) in a one pot process was developed for the convenient and efficient synthesis of 2-substituted-3-aminomethylenechromans. The tandem allylic amination/chromen ring-opening/Michael cyclization reactions were involved in this protocol.

  2. Amine-functionalized magnetic mesoporous silica nanoparticles for DNA separation

    NASA Astrophysics Data System (ADS)

    Sheng, Wei; Wei, Wei; Li, Junjian; Qi, Xiaoliang; Zuo, Gancheng; Chen, Qi; Pan, Xihao; Dong, Wei

    2016-11-01

    We report a modified approach for the functionalized magnetic mesoporous silica nanoparticles (MMSN) using polymer microspheres incorporated with magnetic nanoparticles in the presence of cetyltrimethylammonium bromide (CTAB) and the core-shell magnetic silica nanoparticles (MSN). These particles were functionalized with amino groups via the addition of aminosilane directly to the particle sol. We then evaluate their DNA separation abilities and find the capacity of DNA binding significantly increased (210.22 μg/mg) compared with normal magnetic silica spheres (138.44 μg/mg) by using an ultraviolet and visible spectrophotometer (UV). The morphologies, magnetic properties, particle size, pore size, core-shell structure and Zeta potential are characterized by Fourier transform infrared spectroscopy (FT-IR), vibrating sample magnetometer (VSM), Transmission electron microscopy (TEM), Powder X-ray diffraction (XRD), and dynamic light scattering (DLS). This work demonstrates that our MMSN own an excellent potential application in bioseparation and drug delivery.

  3. Design of Modified Amine Transfer Reagents Allows the Synthesis of α-Chiral Secondary Amines via CuH-Catalyzed Hydroamination.

    PubMed

    Niu, Dawen; Buchwald, Stephen L

    2015-08-05

    The CuH-catalyzed hydroamination of alkenes and alkynes using a silane and an amine transfer reagent represents a simple strategy to access chiral amine products. We have recently reported methods to prepare chiral amines with high efficiency and stereoselectivity using this approach. However, the current technology is limited to the synthesis of trialkylamines from dialkylamine transfer reagents (R2NOBz). When monoalkylamine transfer reagents [RN(H)OBz] were used for the synthesis of chiral secondary amines, competitive, nonproductive consumption of these reagents by the CuH species resulted in poor yields. In this paper, we report the design of a modified type of amine transfer reagent that addresses this limitation. This effort has enabled us to develop a CuH-catalyzed synthesis of chiral secondary amines using a variety of amine coupling partners, including those derived from amino acid esters, carbohydrates, and steroids. Mechanistic investigations indicated that the modified amine transfer reagents are less susceptible to direct reaction with CuH.

  4. Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration

    SciTech Connect

    Eedugurala, Naresh; Wang, Zhuoran; Chaudhary, Umesh; Nelson, Nicholas; Kandel, Kapil; Kobayashi, Takeshi; Slowing, Igor I.; Pruski, Marek; Sadow, Aaron D.

    2015-11-04

    The hydroboration of aldehydes and ketones using a silica-supported zirconium catalyst is reported. Reaction of Zr(NMe2)4 and mesoporous silica nanoparticles (MSN) provides the catalytic material Zr(NMe2)n@MSN. Exhaustive characterization of Zr(NMe2)n@MSN with solid-state (SS)NMR and infrared spectroscopy, as well as through reactivity studies, suggests its surface structure is primarily ≡SiOZr(NMe2)3. The presence of these nitrogen-containing zirconium sites is supported by 15N NMR spectroscopy, including natural abundance 15N NMR measurements using dynamic nuclear polarization (DNP) SSNMR. The Zr(NMe2)n@MSN material reacts with pinacolborane (HBpin) to provide Me2NBpin and the material ZrH/Bpin@MSN that is composed of interacting surface-bonded zirconium hydride and surface-bonded borane ≡SiOBpin moieties in an approximately 1:1 ratio, as well as zirconium sites coordinated by dimethylamine. The ZrH/Bpin@MSN is characterized by 1H/2H and 11B SSNMR and infrared spectroscopy and through its reactivity with D2. The zirconium hydride material or the zirconium amide precursor Zr(NMe2)n@MSN catalyzes the selective hydroboration of aldehydes and ketones with HBpin in the presence of functional groups that are often reduced under hydroboration conditions or are sensitive to metal hydrides, including olefins, alkynes, nitro groups, halides, and ethers. Remarkably, this catalytic material may be recycled without loss of activity at least eight times, and air-exposed materials are catalytically active. These supported zirconium centers are robust catalytic sites for carbonyl reduction and that surface-supported, catalytically reactive zirconium hydride may be generated from zirconium-amide or zirconium alkoxide sites.

  5. Amines immobilized double-walled silica nanotubes for CO2 capture.

    PubMed

    Ko, Young Gun; Lee, Hyun Jeong; Oh, Hyun Chul; Choi, Ung Su

    2013-04-15

    Novel silica support has been required for high amine loading and good CO2 molecule diffusion into its pores to increase the performance of CO2 adsorbents. Herein, amine groups supported on double-walled silica nanotubes (DWSNTs) have been prepared via the immobilization of various aminosilanes (primary, secondary, tertiary, di-, and tri-aminosilanes) on DWSNT, and found to be a very effective adsorbent for CO2 capture. Amine groups immobilized DWSNTs captured CO2 reversibly in a temperature swing process at various adsorption temperatures (25°C, 50°C, 75°C, and 100°C). The amines on modified DWSNTs showed high CO2 capture capacity in the order of tri-, di-, primary, secondary, and tertiary amines. The CO2 capture capacity of all aminosilanes immobilized DWSNTs decreased linearly with the increase of the adsorption temperature. We expect that DWSNT would be able to inspire researchers to use it not only as a support for CO2 capture but also as a promising candidate for various applications.

  6. Aerobic oxidation of cyclic amines to lactams catalyzed by ceria-supported nanogold

    DOE PAGES

    Dairo, Taiwo O.; Nelson, Nicholas C.; Slowing, Igor I.; ...

    2016-09-23

    Here, the oxidative transformation of cyclic amines to lactams, which are important chemical feedstocks, is efficiently catalyzed by CeO2-supported gold nanoparticles (Au/CeO2) and Aerosil 200 in the presence of an atmosphere of O2. The complete conversion of pyrrolidine was achieved in 6.5 h at 160 °C, affording a 97 % yield of the lactam product 2-pyrrolidone (γ-butyrolactam), while 2-piperidone (δ-valerolactam) was synthesized from piperidine (83 % yield) in 2.5 h. Caprolactam, the precursor to the commercially important nylon-6, was obtained from hexamethyleneimine in 37 % yield in 3 h. During the oxidation of pyrrolidine, two transient species, 5-(pyrrolidin-1-yl)-3,4-dihydro-2H-pyrrole (amidine-5) andmore » 4-amino-1-(pyrrolidin-1-yl)butan-1-one, were observed. Both of these compounds were oxidized to 2-pyrrolidone under catalytic conditions, indicating their role as intermediates in the reaction pathway. In addition to the reactions of cyclic secondary amines, Au/CeO2 also efficiently catalyzes the oxidation of N-methyl cyclic tertiary amines to the corresponding lactams at 80 and 100 °C.« less

  7. Aerobic oxidation of cyclic amines to lactams catalyzed by ceria-supported nanogold

    SciTech Connect

    Dairo, Taiwo O.; Nelson, Nicholas C.; Slowing, Igor I.; Angelici, Robert J.; Woo, L. Keith

    2016-09-23

    Here, the oxidative transformation of cyclic amines to lactams, which are important chemical feedstocks, is efficiently catalyzed by CeO2-supported gold nanoparticles (Au/CeO2) and Aerosil 200 in the presence of an atmosphere of O2. The complete conversion of pyrrolidine was achieved in 6.5 h at 160 °C, affording a 97 % yield of the lactam product 2-pyrrolidone (γ-butyrolactam), while 2-piperidone (δ-valerolactam) was synthesized from piperidine (83 % yield) in 2.5 h. Caprolactam, the precursor to the commercially important nylon-6, was obtained from hexamethyleneimine in 37 % yield in 3 h. During the oxidation of pyrrolidine, two transient species, 5-(pyrrolidin-1-yl)-3,4-dihydro-2H-pyrrole (amidine-5) and 4-amino-1-(pyrrolidin-1-yl)butan-1-one, were observed. Both of these compounds were oxidized to 2-pyrrolidone under catalytic conditions, indicating their role as intermediates in the reaction pathway. In addition to the reactions of cyclic secondary amines, Au/CeO2 also efficiently catalyzes the oxidation of N-methyl cyclic tertiary amines to the corresponding lactams at 80 and 100 °C.

  8. Enantioselective amine α-functionalization via palladium catalyzed C–H arylation of thioamides

    PubMed Central

    Jain, Pankaj; Verma, Pritha; Xia, Guoqin; Yu, Jin-Quan

    2016-01-01

    Saturated aza-heterocycles are highly privileged building blocks that are commonly encountered in bioactive compounds and approved therapeutic agents. These N-heterocycles are also incorporated as chiral auxiliaries and ligands in asymmetric synthesis. As such, development of methods to functionalize the α-methylene C–H bonds of these systems enantioselectively is of great importance, especially in drug discovery. Currently, enantioselective lithiation with (–)-sparteine followed by Pd(0) catalyzed cross coupling to prepare α-arylated amines is largely limited to pyrrolidines. Here we report a Pd(II)-catalyzed enantioselective α-C–H coupling of a wide range of amines, including ethyl amines, azetidines, pyrrolidines, piperidines, azepanes, indolines, and tetrahydroisoquinolines. Chiral phosphoric acids are demonstrated as effective anionic ligands for the enantioselective coupling of methylene C–H bonds with aryl boronic acids. This catalytic reaction not only affords high enantioselectivities, but also provides exclusive regioselectivity in the presence of two methylene groups in different steric environments. PMID:28282045

  9. Palladium-Catalyzed Transannular C–H Functionalization of Alicyclic Amines

    PubMed Central

    Saper, Noam I.; Sanford, Melanie S.

    2016-01-01

    The discovery of pharmaceutical candidates is a resource-intensive enterprise that frequently requires the parallel synthesis of hundreds or even thousands of molecules. Carbon-hydrogen bonds are present in almost all pharmaceutical agents. As such, the development of selective, rapid, and efficient methods for converting carbon-hydrogen bonds into new chemical entities has the potential to dramatically streamline pharmaceutical development1,2,3,4. Saturated nitrogen-containing heterocycles (alicyclic amines) feature prominently in pharmaceuticals, including treatments for depression (paroxetine, amitifadine), diabetes (gliclazide), leukemia (alvocidib), schizophrenia (risperidone, belaperidone), and nicotine addiction (cytisine and varenicline)5. However, existing methods for the C–H functionalization of saturated nitrogen heterocycles, particularly at sites remote to nitrogen, remain extremely limited 6,7. Here we report a new approach to selectively manipulate the carbon–hydrogen bonds of alicyclic amines at sites remote to nitrogen. Our reaction leverages the boat conformation of the substrates to achieve the palladium-catalyzed amine-directed conversion of C–H bonds to C–C bonds on various alicyclic amine scaffolds. This approach is applied to the synthesis of novel derivatives of several bioactive molecules, including the top-selling smoking cessation drug varenicline (Chantix®). We anticipate that this method should prove broadly useful in medicinal chemistry. PMID:26886789

  10. Entrapment of Enzymes and Carbon Nanotubes in Biologically Synthesized Silica: Glucose Oxidase-catalyzed Direct Electron Transfer, Preprint

    DTIC Science & Technology

    2007-08-01

    orthosilicate (TMOS), 99%, lysozyme from chicken egg white (EC3.2.1.17) and carboxylated single-walled carbon nanotubes were obtained from Sigma...provides significant mechanical stability to the resulting silica matrix. Lysozyme , for example, catalyzes the formation of silica particles when...demonstrated by entrapping GOx in a silica/CNT composite obtained through lysozyme -catalyzed synthesis of silica. 2. Results and discussion

  11. Analyzing site selectivity in Rh2(esp)2-catalyzed intermolecular C-H amination reactions.

    PubMed

    Bess, Elizabeth N; DeLuca, Ryan J; Tindall, Daniel J; Oderinde, Martins S; Roizen, Jennifer L; Du Bois, J; Sigman, Matthew S

    2014-04-16

    Predicting site selectivity in C-H bond oxidation reactions involving heteroatom transfer is challenged by the small energetic differences between disparate bond types and the subtle interplay of steric and electronic effects that influence reactivity. Herein, the factors governing selective Rh2(esp)2-catalyzed C-H amination of isoamylbenzene derivatives are investigated, where modification to both the nitrogen source, a sulfamate ester, and substrate are shown to impact isomeric product ratios. Linear regression mathematical modeling is used to define a relationship that equates both IR stretching parameters and Hammett σ(+) values to the differential free energy of benzylic versus tertiary C-H amination. This model has informed the development of a novel sulfamate ester, which affords the highest benzylic-to-tertiary site selectivity (9.5:1) observed for this system.

  12. Palladium-catalyzed amination of meso-(bromophenyl)porphyrins with diamines and azamacrocycles.

    PubMed

    Mikhalitsyna, E A; Tyurin, V S; Khrustalev, V N; Lonin, I S; Beletskaya, I P

    2014-03-07

    Novel diamino and azamacrocycle functionalized porphyrins were efficiently synthesized by palladium-catalyzed amination of mono- and bis(meso-(bromophenyl))porphyrins. The optimization of reaction conditions allowed us to achieve high yields of products with substrates of different types. Supramolecular utility of the thus obtained aminoporphyrins was shown by investigations of processes of coordination self-assembly in solution by NMR and UV-Vis spectroscopy. The crystalline 1D-coordination polymer formed via self-assembly of N,N-dimethylethylenediamine substituted zinc porphyrin was characterized by X-ray diffraction.

  13. Alcohol amination with ammonia catalyzed by an acridine-based ruthenium pincer complex: a mechanistic study.

    PubMed

    Ye, Xuan; Plessow, Philipp N; Brinks, Marion K; Schelwies, Mathias; Schaub, Thomas; Rominger, Frank; Paciello, Rocco; Limbach, Michael; Hofmann, Peter

    2014-04-23

    The mechanistic course of the amination of alcohols with ammonia catalyzed by a structurally modified congener of Milstein's well-defined acridine-based PNP-pincer Ru complex has been investigated both experimentally and by DFT calculations. Several key Ru intermediates have been isolated and characterized. The detailed analysis of a series of possible catalytic pathways (e.g., with and without metal-ligand cooperation, inner- and outer-sphere mechanisms) leads us to conclude that the most favorable pathway for this catalyst does not require metal-ligand cooperation.

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

    EPA Science Inventory

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

  15. Amine-modified ordered mesoporous silica: The effect of pore size on CO2 capture performance

    NASA Astrophysics Data System (ADS)

    Wang, Lin; Yao, Manli; Hu, Xin; Hu, Gengshen; Lu, Jiqing; Luo, Mengfei; Fan, Maohong

    2015-01-01

    The objective of current research is to investigate the effect of pore size of mesoporous silica supports on the CO2 capture performance of solid amine sorbents. Two ordered mesoporous silicas (OMS) with different pore sizes (5.6 nm and 7.6 nm) were synthesized as tetraethylenepentamine (TEPA) supports. A serious of techniques, such as physical adsorption, infrared spectroscopy and thermal gravimetric analysis were used to characterize the solid amine sorbents. The CO2 capture performances of the sorbents were evaluated using breakthrough method with a fixed-bed reactor equipped with an online mass spectrometer. The experimental results indicate that the pore size has significant influence on CO2 capture performance. Larger pore size could decrease the mass transfer resistance and increase the interaction between CO2 and TEPA. Therefore, OMS-7.6 is better than OMS-5.6 as amine support. The highest CO2 sorption capacities achieved with OMS-7.6 with 50 wt% TEPA loading (OMS-7.6-50) in the absence and presence of moisture are 3.45 mmol/g and 4.28 mmol/g, respectively, under the conditions of 10.0% CO2/N2 mixture at 75 °C. Cyclic CO2 adsorption-desorption experiments indicate that the solid amine sorbents are fairly stable and regenerable.

  16. Rh(III)-Catalyzed C-H Bond Addition/Amine-Mediated Cyclization of Bis-Michael Acceptors.

    PubMed

    Potter, Tyler J; Ellman, Jonathan A

    2016-08-05

    A Rh(III)-catalyzed C-H bond addition/primary amine-promoted cyclization of bis-Michael acceptors is reported. The C-H bond addition step occurs with high chemoselectivity, and the subsequent intramolecular Michael addition, mediated by a primary amine catalyst, sets three contiguous stereocenters with high diastereoselectivity. A broad range of directing groups and both aromatic and alkenyl C-H bonds were shown to be effective in this transformation, affording functionalized piperidines, tetrahydropyrans, and cyclohexanes.

  17. Novel multiparametric approach to elucidate the surface amine-silanization reaction profile on fluorescent silica nanoparticles.

    PubMed

    Roy, Shibsekhar; Dixit, Chandra K; Woolley, Robert; MacCraith, Brian D; O'Kennedy, Richard; McDonagh, Colette

    2010-12-07

    This Article addresses the important issue of the characterization of surface functional groups for optical bioassay applications. We use a model system consisting of spherical dye-doped silica nanoparticles (NPs) that have been functionalized with amine groups whereby the encapsulated cyanine-based near-infrared dye fluorescence acts as a probe of the NP surface environment. This facilitates the identification of the optimum deposition parameters for the formation of a stable ordered amine monolayer and also elucidates the functionalization profile of the amine-silanization process. Specifically, we use a novel approach where the techniques of fluorescence correlation spectroscopy (FCS) and fluorescence lifetime measurement (FL) are used in conjunction with the more conventional analytical techniques of zeta potential measurement and Fourier transfer infrared spectroscopy (FTIR). The dynamics of the ordering of the amine layer in different stages of the reaction have been characterized by FTIR, FL, and FCS. The results indicate an optimum reaction time for the formation of a stable amine layer, which is optimized for further biomolecular conjugation, whereas extended reaction times lead to a disordered cross-linked layer. The results have been validated using an immunoglobulin (IgG) plate-based direct binding assay where the maximum number of IgG-conjugated aminated NPs were captured by immobilized anti-IgG antibodies for the NP sample corresponding to the optimized amine-silanization condition. Importantly, these results point to the potential of FCS and FL as useful analytical tools in diverse fields such as characterization of surface functionalization.

  18. Liquid chromatography of hydrocarbonaeous quaternary amines on cyclodextrin bonded silica

    USGS Publications Warehouse

    Abidi, S.L.

    1986-01-01

    Mixtures of n-alkylbenzyldimethylammonium chloride (ABDAC) were resolved into homologous components by high-performance liquid chromatography (HPLC) with a cyclodextrin-bonded silica stationary phase. With a few exceptions, results from this study are similar to those obtained from traditional reversed-phase HPLC. It was found that the presence of electrolytes in aqueous mobile phases is not a critical factor in determining the success of HPLC separation. Under normal HPLC conditions, a mobile phase consisting of either methanol–water (50:50) or acetonitrile–water (30:70) was employed for obtaining adequate resolution of the quaternary ammonium mixtures. Although the percent organic modifier–water profiles were similar to those in previous studies with these compounds, resolution (R) and selectivity (α) parameters were found to be quite susceptible to changes in the mobile phase solvent composition. The retention behavior of the cationic analytes in the homologous series is consistent with the hydrophobic-interaction concept proposed for the retention mechanism via dominant inclusion complex formation. Several electrolytes were chosen for a study of the counter ion effect on the chromatographic characteristics of ABDAC components. Among the electrolytes examined, the perchlorate ion was found most likely to act as an ion-pairing counter ion for ammonium cations in the HPLC system studied. A correlation study established linear relationships between the chain length of ABDAC and the logarithmic capacity factor (k2). The analytical utility of the HPLC method was demonstrated by the analysis of various unknown mixtures.

  19. Rh-Catalyzed, Regioselective, C-H Bond Functionalization: Access to Quinoline-Branched Amines and Dimers.

    PubMed

    Reddy, M Damoder; Fronczek, Frank R; Watkins, E Blake

    2016-11-04

    Rh-catalyzed, chelation-induced, C-5 regioselective C-H functionalization of 8-amidoquinolines with a range of N-Boc aminals is reported for the first time. The addition of in situ generated imines to C(sp(2))-H bonds afforded branched amines in good to excellent yields. Moreover, this transformation features good functional group compatibility, broad substrate scope, and mild reaction conditions and is suitable for gram-scale synthesis. In addition, an unprecedented, chelation-induced, site-selective, remote dimerization of quinolines led to the formation of dimer frameworks in moderate yields under Rh-catalyzed conditions.

  20. Organic/inorganic hybrid amine and sulfonic acid tethered silica materials: Synthesis, characterization and application

    NASA Astrophysics Data System (ADS)

    Hicks, Jason Christopher

    The major goals of this thesis were to: (1) create a site-isolated aminosilica material with higher amine loadings than previously reported isolation methods, (2) use spectroscopic, reactivity, and catalytic (olefin polymerization precatalysts) probes to determine isolation of amine groups on these organic/inorganic hybrid materials, (3) synthesize an organic/inorganic hybrid material capable of activating Group 4 olefin polymerization precatalysts, and (4) synthesize a high amine loaded organic/inorganic hybrid material capable of reversibly capturing CO2 in a simulated flue gas stream. The underlying motivation of this research involved the synthesis and design of novel amine and sulfonic acid materials. Traditional routes to synthesize aminosilicas have led to the formation of a high loading of multiple types of amine sites on the silica surface. Part of this research involved the creation of a new aminosilica material via a protection/deprotection method designed to prevent multiple sites, while maintaining a relatively high loading. As a characterization technique, fluorescence spectroscopy of pyrene-based fluorophores loaded on traditional aminosilicas and site-isolated aminosilicas was used to probe the degree of site-isolation obtained with these methods. Also, this protection/deprotection method was compared to other reported isolation techniques with heterogeneous Group 4 constrained-geometry inspired catalysts (CGCs). It was determined that the degree of separation of the amine sites could be controlled with protection/deprotection methods. Furthermore, an increase in the reactivity of the amines and the catalytic activity of CGCs built off of the amines was determined for aminosilicas synthesized by a protection/deprotection method. The second part of this work involved developing organic/inorganic hybrid materials as heterogeneous Bronsted acidic cocatalysts for activation of olefin polymerization precatalysts. This was the first reported organic

  1. Spacing and Site Isolation of Amine Groups in 3-Aminopropyl-Grafted Silica Materials - The Role of Protecting Groups

    SciTech Connect

    Hicks, Jason C; Dabestani, Reza T; Buchanan III, A C; Jones, Christopher W

    2006-01-01

    The relative spacing of amines in 3-aminopropylsilyl-grafted silica is studied by solid-state fluorescence spectroscopy of 1-pyrenecarboxylic acid (PCA) and 1-pyrenebutyric acid (PBA) bound to traditionally prepared, deprotected benzyl- or deprotected trityl-spaced aminosilicas. Thermogravimetric analysis and FT-Raman spectroscopy results show evidence that the protected imine can be cleaved to yield the corresponding amine in essentially quantitative yield. The steady-state fluorescence spectroscopic data of either PCA or PBA indicate that the number of amine pairs on the surface separated by a distance of 1 nm or less decreases as the total amine loading decreases. Both the intensity ratio of the excimer band to the monomer band (I{sub 470}/I{sub 384} or I{sub exc}/I{sub mon}) and lifetime decay studies of the fluorophore are useful probes of the amine spacing. Separation of amines on the surface can be achieved by either use of a protected synthesis route or through reduction of the concentration of the unprotected 3-aminopropyltrimethoxysilane used in the grafting solution. However, the two routes lead to materials with significantly different average amine spacings. Due to clustering of unprotected amines in solution before grafting or on the surface during the grafting process, amine-amine distances on the surface of materials prepared by an unprotected synthesis are on average smaller than when a protected synthesis is used. With the protected synthesis, evidence suggests that the amines are more isolated, with larger average amine-amine distances when compared to corresponding materials with a similar amine loading prepared via an unprotected synthesis. This is attributed to both the steric influence of the protecting groups and a reduction in silane clustering in solution due to protection of the amines before grafting. Thus, the mechanism of surface amine spacing when using the protection-deprotection strategy appears to involve both of these factors

  2. Palladium(0)-catalyzed amination, Stille coupling, and Suzuki coupling of electron-deficient aryl fluorides.

    PubMed

    Kim, Young Mi; Yu, Shu

    2003-02-19

    The amination of 2-fluoronitrobenzene was Pd(0) catalyzed at 65 degrees C in DMF, and the effectiveness of the catalysis was ligand-dependent. Among the five catalyst systems investigated, Pd(PPh3)4 was the most effective catalyst. The control experiments revealed that Pd(OAc)2 or PPh3 was not responsible for the catalysis. 4-Fluoro-3-nitro-benzonitrile and 4-fluoro-3-nitro-benzaldehyde also underwent Stille coupling and Suzuki coupling in the presence of Pd(PPh3)4, and the reactions afforded the coupling products in 28-86% yields. The control experiments showed no sign of reaction in the absence of palladium. These results were in agreement with the oxidative addition/reductive elimination pathway, where the oxidative addition could conceivably proceed via the SNAr mechanism.

  3. Palladium-catalyzed asymmetric allylic amination of racemic butadiene monoxide with isatin derivatives.

    PubMed

    Li, Gen; Feng, Xiangqing; Du, Haifeng

    2015-05-28

    Isatins and their derivatives are important functional moities and building blocks in pharmaceutical and synthetic chemistry. Numerous enantioselective transformations at the C-3 carbonyl group have been well developed. However, the asymmetric substitution reaction with isatins and their derivatives as nucleophiles based on the free N-H groups has been less studied due to the relatively weaker nucleophilicity resulting from the two electron-withdrawing carbonyl groups. In this paper, a palladium-catalyzed asymmetric allylic amination of racemic butadiene monoxide with isatin derivatives using a chiral phosphoramidite olefin hybrid ligand has been successfully developed under mild conditions. A variety of chiral amino alcohols were afforded in 55-87% yields with 10/1->20/1 regioselectivity ratios and 80-97% ees.

  4. [Novel access to indazoles based on palladium-catalyzed amination chemistry].

    PubMed

    Inamoto, Kiyofumi

    2008-07-01

    Two efficient methods to construct the indazole nucleus have been developed, both of which utilize palladium-catalyzed intramolecular carbon-nitrogen bond formation. One is based on intramolecular Buchwald-Hartwig amination reaction of 2-halobenzophenone tosylhydrazones. The catalyst system we developed for this reaction allows the cyclization to proceed under very mild conditions and thus could be applied to a wide range of substrates with acid- or base-sensitive functional groups. Furthermore, this methodology could be applied for the construction of benzoisoxazole ring system. In addition, catalytic C-H activation with palladium followed by intramolecular amination of benzophenone tosylhydrazones was also accomplished with the aid of the catalyst system such as Pd(OAc)(2)/Cu(OAc)(2)/AgOCOCF(3), which gave another route to indazoles. Using this combination, indazoles with various functional groups could be obtained in good to high yields, especially in the case of substrates having electron donating group such as methoxy group on benzene ring. Interesting chemo- and regioselectivity were also observed in this reaction.

  5. Spectroscopic investigation into oxidative degradation of silica-supported amine sorbents for CO(2) capture.

    PubMed

    Srikanth, Chakravartula S; Chuang, Steven S C

    2012-08-01

    Oxidative degradation characteristics of silica-supported amine sorbents with varying amounts of tetraethylenepentamine (TEPA) and polyethylene glycol (PEG; P(200) or P(600) represents PEG with molecular weights of 200 or 600) have been studied by IR and NMR spectroscopy. Thermal treatment of the sorbents and liquid TEPA at 100 °C for 12 h changed their color from white to yellow. The CO(2) capture capacity of the TEPA/SiO(2) sorbents (i.e., SiO(2)-supported TEPA with a TEPA/SiO(2) ratio of 25:75) decreased by more than 60 %. IR and NMR spectroscopy studies showed that the yellow color of the degraded sorbents resulted from the formation of imide species. The imide species, consisting of NH associated with two C=O functional groups, were produced from the oxidation of methylene groups in TEPA. Imide species on the degraded sorbent are not capable of binding CO(2) due to its weak basicity. The addition of P(200) and P(600) to the supported amine sorbents improved both their CO(2) capture capacities and oxidative degradation resistance. IR spectroscopy results also showed that TEPA was immobilized on the SiO(2) surface through hydrogen bonding between amine groups and the silanol groups of SiO(2). The OH groups of PEG interact with NH(2) /NH of TEPA through hydrogen bonding. Hydrogen bonds disperse TEPA on SiO(2) and block O(2) from accessing TEPA for oxidation. Oxidative degradation resistance and CO(2) capture capacity of the supported amine sorbents can be optimized through adjusting the ratio of hydroxyl to amine groups in the TEPA/PEG mixture.

  6. Spectroscopic Investigation into Oxidative Degradation of Silica-Supported Amine Sorbents for CO2 Capture

    PubMed Central

    Srikanth, Chakravartula S; Chuang, Steven S C

    2012-01-01

    Oxidative degradation characteristics of silica-supported amine sorbents with varying amounts of tetraethylenepentamine (TEPA) and polyethylene glycol (PEG; P200 or P600 represents PEG with molecular weights of 200 or 600) have been studied by IR and NMR spectroscopy. Thermal treatment of the sorbents and liquid TEPA at 100 °C for 12 h changed their color from white to yellow. The CO2 capture capacity of the TEPA/SiO2 sorbents (i.e., SiO2-supported TEPA with a TEPA/SiO2 ratio of 25:75) decreased by more than 60 %. IR and NMR spectroscopy studies showed that the yellow color of the degraded sorbents resulted from the formation of imide species. The imide species, consisting of NH associated with two C—O functional groups, were produced from the oxidation of methylene groups in TEPA. Imide species on the degraded sorbent are not capable of binding CO2 due to its weak basicity. The addition of P200 and P600 to the supported amine sorbents improved both their CO2 capture capacities and oxidative degradation resistance. IR spectroscopy results also showed that TEPA was immobilized on the SiO2 surface through hydrogen bonding between amine groups and the silanol groups of SiO2. The OH groups of PEG interact with NH2/NH of TEPA through hydrogen bonding. Hydrogen bonds disperse TEPA on SiO2 and block O2 from accessing TEPA for oxidation. Oxidative degradation resistance and CO2 capture capacity of the supported amine sorbents can be optimized through adjusting the ratio of hydroxyl to amine groups in the TEPA/PEG mixture. PMID:22744858

  7. Pentacoordinated carboxylate π-allyl nickel complexes as key intermediates for the Ni-catalyzed direct amination of allylic alcohols.

    PubMed

    Kita, Yusuke; Sakaguchi, Hironobu; Hoshimoto, Yoichi; Nakauchi, Daisuke; Nakahara, Yasuhito; Carpentier, Jean-François; Ogoshi, Sensuke; Mashima, Kazushi

    2015-10-05

    Direct amination of allylic alcohols with primary and secondary amines catalyzed by a system made of [Ni(1,5-cyclooctadiene)2 ] and 1,1'-bis(diphenylphosphino)ferrocene was effectively enhanced by adding nBu4 NOAc and molecular sieves, affording the corresponding allyl amines in high yield with high monoallylation selectivity for primary amines and high regioselectivity for monosubstituted allylic alcohols. Such remarkable additive effects of nBu4 NOAc were elucidated by isolating and characterizing some nickel complexes, manifesting the key role of a charge neutral pentacoordinated η(3) -allyl acetate complex in the present system, in contrast to usual cationic tetracoordinated complexes earlier reported in allylic substitution reactions.

  8. Copper-catalyzed direct amination of ortho-functionalized haloarenes with sodium azide as the amino source.

    PubMed

    Zhao, Haibo; Fu, Hua; Qiao, Renzhong

    2010-05-21

    A simple copper-catalyzed direct amination of ortho-functionalized haloarenes (2-halobenzoic acid, 2-halobenzamide, and N-(2-bromophenyl)acetamide derivatives) has been developed with use of NaN(3) as the amino source in ethanol, and the corresponding ortho-functionalized aromatic amines were synthesized in good to excellent yields. The protocol undergoes one-pot Ullmann-type coupling of ortho-functionalized haloarenes with NaN(3) to lead to ortho-functionalized azidoarenes, followed by reduction with ethanol.

  9. Sodium hydroxide catalyzed monodispersed high surface area silica nanoparticles

    PubMed Central

    Bhakta, Snehasis; Dixit, Chandra K; Bist, Itti; Jalil, Karim Abdel; Suib, Steven L; Rusling, James F

    2016-01-01

    Understanding of the synthesis kinetics and our ability to modulate medium conditions allowed us to generate nanoparticles via an ultra-fast process. The synthesis medium is kept quite simple with tetraethyl orthosilicate (TEOS) as precursor and 50% ethanol and sodium hydroxide catalyst. Synthesis is performed under gentle conditions at 20 °C for 20 min Long synthesis time and catalyst-associated drawbacks are most crucial in silica nanoparticle synthesis. We have addressed both these bottlenecks by replacing the conventional Stober catalyst, ammonium hydroxide, with sodium hydroxide. We have reduced the overall synthesis time from 20 to 1/3 h, ~60-fold decrease, and obtained highly monodispersed nanoparticles with 5-fold higher surface area than Stober particles. We have demonstrated that the developed NPs with ~3-fold higher silane can be used as efficient probes for biosensor applications. PMID:27606068

  10. Sodium hydroxide catalyzed monodispersed high surface area silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Bhakta, Snehasis; Dixit, Chandra K.; Bist, Itti; Abdel Jalil, Karim; Suib, Steven L.; Rusling, James F.

    2016-07-01

    Understanding of the synthesis kinetics and our ability to modulate medium conditions allowed us to generate nanoparticles via an ultra-fast process. The synthesis medium is kept quite simple with tetraethyl orthosilicate (TEOS) as precursor and 50% ethanol and sodium hydroxide catalyst. Synthesis is performed under gentle conditions at 20 °C for 20 min Long synthesis time and catalyst-associated drawbacks are most crucial in silica nanoparticle synthesis. We have addressed both these bottlenecks by replacing the conventional Stober catalyst, ammonium hydroxide, with sodium hydroxide. We have reduced the overall synthesis time from 20 to 1/3 h, ∼60-fold decrease, and obtained highly monodispersed nanoparticles with 5-fold higher surface area than Stober particles. We have demonstrated that the developed NPs with ∼3-fold higher silane can be used as efficient probes for biosensor applications.

  11. Chemical, Physical, and Mechanical Characterization of Isocyanate Cross-linked Amine-Modified Silica Aerogels

    NASA Technical Reports Server (NTRS)

    Katti, Atul; Shimpi, Nilesh; Roy, Samit; Lu, Hongbing; Fabrizio, Eve F.; Dass, Amala; Capadona, Lynn A.; Leventis, Nicholas

    2006-01-01

    We describe a new mechanically strong lightweight porous composite material obtained by encapsulating the skeletal framework of amine-modified silica aerogels with polyurea. The conformal polymer coating preserves the mesoporous structure of the underlying silica framework and the thermal conductivity remains low at 0.041 plus or minus 0.001 W m(sup -1 K(sup -1). The potential of the new cross-linked silica aerogels for load-carrying applications was determined through characterization of their mechanical behavior under compression, three-point bending, and dynamic mechanical analysis (DMA). A primary glass transition temperature of 130 C was identified through DMA. At room temperature, results indicate a hyperfoam behavior where in compression cross-linked aerogels are linearly elastic under small strains (less than 4%) and then exhibit yield behavior (until 40% strain), followed by densification and inelastic hardening. At room temperature the compressive Young's modulus and the Poisson's ratio were determined to be 129 plus or minus 8 MPa and 0.18, respectively, while the strain at ultimate failure is 77% and the average specific compressive stress at ultimate failure is 3.89 x 10(exp 5) N m kg(sup -1). The specific flexural strength is 2.16 x 10(exp 4) N m kg(sup -1). Effects on the compressive behavior of strain rate and low temperature were also evaluated.

  12. Preferential oxidation of carbon monoxide catalyzed by platinum nanoparticles in mesoporous silica.

    PubMed

    Fukuoka, Atsushi; Kimura, Jun-ichi; Oshio, Tadashi; Sakamoto, Yuzuru; Ichikawa, Masaru

    2007-08-22

    Preferential oxidation (PROX) of CO is an important practical process to purify H2 for use in polymer electrolyte fuel cells. Although many supported noble metal catalysts have been reported so far, their catalytic performances remain insufficient for operation at low temperature. We found that Pt nanoparticles in mesoporous silica give unprecedented activity, selectivity, and durability in the PROX reaction below 353 K. We also studied the promotional effect of mesoporous silica in the Pt-catalyzed PROX reaction by infrared spectroscopy using the isotopic tracer technique. Gas-phase O2 is not directly used for CO oxidation, but the oxygen of mesoporous silica is incorporated into CO2. These results suggest that CO oxidation is promoted by the attack of the surface OH groups to CO on Pt without forming water.

  13. Important roles of enthalpic and entropic contributions to CO2 capture from simulated flue gas and ambient air using mesoporous silica grafted amines.

    PubMed

    Alkhabbaz, Mustafa A; Bollini, Praveen; Foo, Guo Shiou; Sievers, Carsten; Jones, Christopher W

    2014-09-24

    The measurement of isosteric heats of adsorption of silica supported amine materials in the low pressure range (0-0.1 bar) is critical for understanding the interactions between CO2 and amine sites at low coverage and hence to the development of efficient amine adsorbents for CO2 capture from flue gas and ambient air. Heats of adsorption for an array of silica-supported amine materials are experimentally measured at low coverage using a Calvet calorimeter equipped with a customized dosing manifold. In a series of 3-aminopropyl-functionalized silica materials, higher amine densities resulted in higher isosteric heats of adsorption, clearly showing that the density/proximity of amine sites can influence the amine efficiency of adsorbents. In a series of materials with fixed amine loading but different amine types, strongly basic primary and secondary amine materials are shown to have essentially identical heats of adsorption near 90 kJ/mol. However, the adsorption uptakes vary substantially as a function of CO2 partial pressure for different primary and secondary amines, demonstrating that entropic contributions to adsorption may play a key role in adsorption at secondary amine sites, making adsorption at these sites less efficient at the low coverages that are important to the direct capture of CO2 from ambient air. Thus, while primary amines are confirmed to be the most effective amine types for CO2 capture from ambient air, this is not due to enhanced enthalpic contributions associated with primary amines over secondary amines, but may be due to unfavorable entropic factors associated with organization of the second alkyl chain on the secondary amine during CO2 adsorption. Given this hypothesis, favorable entropic factors may be the main reason primary amine based adsorbents are more effective under air capture conditions.

  14. Tuning cooperativity by controlling the linker length of silica-supported amines in catalysis and CO2 capture.

    PubMed

    Brunelli, Nicholas A; Didas, Stephanie A; Venkatasubbaiah, Krishnan; Jones, Christopher W

    2012-08-29

    Cooperative interactions between aminoalkylsilanes and silanols on a silica surface can be controlled by varying the length of the alkyl linker attaching the amine to the silica surface from C1 (methyl) to C5 (pentyl). The linker length strongly affects the catalytic cooperativity of amines and silanols in aldol condensations as well as the adsorptive cooperativity for CO(2) capture. The catalytic cooperativity increases with the linker length up to propyl (C3), with longer, more flexible linkers (up to C5) providing no additional benefit or hindrance. Short linkers (C1 and C2) limit the beneficial amine-silanol cooperativity in aldol condensations, resulting in lower catalytic rates than with the C3+ linkers. For the same materials, the adsorptive cooperativity exhibits similar trends for CO(2) capture efficiency.

  15. Stereocontrol in proline-catalyzed asymmetric amination: a comparative assessment of the role of enamine carboxylic acid and enamine carboxylate.

    PubMed

    Sharma, Akhilesh K; Sunoj, Raghavan B

    2011-05-28

    The transition state models in two mechanistically distinct pathways, involving (i) an enamine carboxylic acid (path-A, 4) and (ii) an enamine carboxylate (path-B, 8), in the proline-catalyzed asymmetric α-amination have been examined using DFT methods. The path-A predicts the correct product stereochemistry under base-free conditions while path-B accounts for reversal of configuration in the presence of a base.

  16. Highly regio- and enantioselective synthesis of N-substituted 2-pyridones: iridium-catalyzed intermolecular asymmetric allylic amination.

    PubMed

    Zhang, Xiao; Yang, Ze-Peng; Huang, Lin; You, Shu-Li

    2015-02-02

    The first iridium-catalyzed intermolecular asymmetric allylic amination reaction with 2-hydroxypyridines has been developed, thus providing a highly efficient synthesis of enantioenriched N-substituted 2-pyridone derivatives from readily available starting materials. This protocol features a good tolerance of functional groups in both the allylic carbonates and 2-hydroxypyridines, thereby delivering multifunctionalized heterocyclic products with up to 98% yield and 99% ee.

  17. Carboxylate-Assisted Iridium-Catalyzed C-H Amination of Arenes with Biologically Relevant Alkyl Azides.

    PubMed

    Zhang, Tao; Hu, Xuejiao; Wang, Zhen; Yang, Tiantian; Sun, Hao; Li, Guigen; Lu, Hongjian

    2016-02-24

    An iridium-catalyzed C-H amination of arenes with a wide substrate scope is reported. Benzamides with electron-donating and -withdrawing groups and linear, branched, and cyclic alkyl azides are all applicable. Cesium carboxylate is crucial for both reactivity and regioselectivity of the reactions. Many biologically relevant molecules, such as amino acid, peptide, steroid, sugar, and thymidine derivatives can be introduced to arenes with high yields and 100 % chiral retention.

  18. Chiral Phosphoric Acid-Catalyzed Enantioselective Reductive Amination of 2-Pyridyl Ketones: Construction of Structurally Chiral Pyridine-Based Ligands.

    PubMed

    Abudu Rexit, Abulikemu; Luo, Shiwei; Mailikezati, Maihemuti

    2016-11-18

    A chiral phosphoric acid-catalyzed one-pot enantioselective reductive amination of 2-pyridyl ketones was realized to provide chiral pyridine-based ligands in excellent yields with high enantioselectivities (up to 98% yield, 94% ee). Computational studies on the key intermediate imine and transition state of the hydride transfer process revealed that the nitrogen atom of the pyridyl ring might be an important factor to significantly promote both the reaction activity and enantioselectivity.

  19. Ruthenium-catalyzed N-alkylation of amines with alcohols under mild conditions using the borrowing hydrogen methodology.

    PubMed

    Enyong, Arrey B; Moasser, Bahram

    2014-08-15

    Using a simple amino amide ligand, ruthenium-catalyzed one-pot alkylation of primary and secondary amines with simple alcohols was carried out under a wide range of conditions. Using the alcohol as solvent, alkylation was achieved under mild conditions, even as low as room temperature. Reactions occurred with high conversion and selectivity in many cases. Reactions can also be carried out at high temperatures in organic solvent with high selectivity using stoichiometric amounts of the alcohol.

  20. A novel synthesis of 2-aryl-2H-indazoles via a palladium-catalyzed intramolecular amination reaction.

    PubMed

    Song, J J; Yee, N K

    2000-02-24

    [reaction: see text] A variety of 2-aryl-2H-indazoles were synthesized by the palladium-catalyzed intramolecular amination of the corresponding N-aryl-N(o-bromobenzyl)hydrazines. Of several sets of reaction conditions surveyed, the combination of Pd(OAc)2/dppf/tBuONa gave the best results. This method applies to a wide scope of substrates containing electron-donating and electron-withdrawing substituents.

  1. Divergent Coupling of Alcohols and Amines Catalyzed by Isoelectronic Hydride Mn(I) and Fe(II) PNP Pincer Complexes.

    PubMed

    Mastalir, Matthias; Glatz, Mathias; Gorgas, Nikolaus; Stöger, Berthold; Pittenauer, Ernst; Allmaier, Günter; Veiros, Luis F; Kirchner, Karl

    2016-08-22

    Herein, we describe an efficient coupling of alcohols and amines catalyzed by well-defined isoelectronic hydride Mn(I) and Fe(II) complexes, which are stabilized by a PNP ligand based on the 2,6-diaminopyridine scaffold. This reaction is an environmentally benign process implementing inexpensive, earth-abundant non-precious metal catalysts, and is based on the acceptorless alcohol dehydrogenation concept. A range of alcohols and amines including both aromatic and aliphatic substrates were efficiently converted in good to excellent isolated yields. Although in the case of Mn selectively imines were obtained, with Fe-exclusively monoalkylated amines were formed. These reactions proceed under base-free conditions and required the addition of molecular sieves.

  2. Interactions of amines with silicon species in undersaturated solutions leads to dissolution and/or precipitation of silica.

    PubMed

    Patwardhan, Siddharth V; Tilburey, Graham E; Perry, Carole C

    2011-12-20

    The biogeochemical silicon cycle is the focus for many researchers studying the dissolution of silicon species from quartz, amorphous, and biogenic silica. Furthermore, the precipitation of biogenic silica by diatoms, radiolarian, sponges, and plants is also a popular focus for research. The ornate silica structures created by these species has attracted interest from biomaterial scientists and biochemists who have studied mineral formation in an attempt to understand how biogenic silica is formed, often in the presence of proteins and long chain polyamines. This article is at the interface of these seemingly distinct research areas. Here we investigate the effect of a range of amines in globally undersaturated silicon environments. Results are presented on the effect of amine-containing molecules on the formation of silica from undersaturated solutions of orthosilicic acid and globally undersaturated silicon environments. We sought to address two questions: can silica be precipitated/harvested from undersaturated solutions, and can we identify the silicon species that are most active in silica formation? We demonstrate that none of the bioinspired additives investigated here (e.g., poly(allylamine hydrochloride), pentaethylenehexamine, and propylamines) have any influence on orthosilicic acid at undersaturated concentrations. However, under globally undersaturated silicon concentrations, small molecules and polymers containing amine groups were able to interact with oligomers of silicic acid to either generate aggregated materials that can be isolated from solution or increase rates of oligomer dissolution back to orthosilicic acid. Additional outcomes of this study include an extended understanding of how polyelectrolytes and small molecules can promote and/or inhibit silica dissolution and a new method to explore how (bio)organic molecules interact with a forming mineral phase.

  3. Quaternary ammonium-functionalized silica sorbents for the solid-phase extraction of aromatic amines under normal phase conditions.

    PubMed

    Vidal, Lorena; Robin, Orlane; Parshintsev, Jevgeni; Mikkola, Jyri-Pekka; Riekkola, Marja-Liisa

    2013-04-12

    Quaternary ammonium-functionalized silica materials were synthesized and applied for solid-phase extraction (SPE) of aromatic amines, which are classified as priority pollutants by US Environmental Protection Agency. Hexamethylenetetramine used for silica surface modification for the first time was employed as SPE sorbent under normal phase conditions. Hexaminium-functionalized silica demonstrated excellent extraction efficiencies for o-toluidine, 4-ethylaniline and quinoline (recoveries 101-107%), while for N,N-dimethylaniline and N-isopropylaniline recoveries were from low to moderate (14-46%). In addition, the suitability of 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica as SPE sorbent was tested under normal phase conditions. The recoveries achieved for the five aromatic amines ranged from 89 to 99%. The stability of the sorbent was evaluated during and after 150 extractions. Coefficients of variation between 4.5 and 10.2% proved a high stability of the synthesized sorbent. Elution was carried out using acetonitrile in the case of hexaminium-functionalized silica and water for 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica sorbent. After the extraction the analytes were separated and detected by liquid chromatography ultraviolet detection (LC-UV). The retention mechanism of the materials was primarily based on polar hydrogen bonding and π-π interactions. Comparison made with activated silica proved the quaternary ammonium-functionalized materials to offer different selectivity and better extraction efficiencies for aromatic amines. Finally, 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica sorbent was successfully tested for the extraction of wastewater and soil samples.

  4. Crosslinking Amine-Modified Silica Aerogels with Epoxies: Mechanically Strong Lightweight Porous Materials

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Fabrizio, Eve F.; Ilhan, Faysal; Dass, Amala; Zhang, Guo-Hui; Vassilaras, Plousia; Johnston, J. Chris; Leventis, Nicholas

    2005-01-01

    The mesoporous surfaces of TMOS-derived silica aerogels have been modified with amines by co-polymerization of TMOS with APTES. The amine sites have become anchors for crosslinking the nanoparticles of the skeletal backbone of the aerogel by attachment of di-, tri and tetra-functional epoxies. The resulting conformal coatings increase the density of the native aerogels by a factor of 2-3 but the strength of the resulting materials may increase by more than two orders of magnitude. Processing variables such as amount of APTES used to make the gels, the epoxy type and concentration used for crosslinking, as well as the crosslinking temperature and time were varied according to a multivariable design-of-experiments (DOE) model. It was found that while elastic modulus follows a similar trend with density, maximum strength is attained neither at the maximum density nor at the highest concentration of -NH2 groups, suggesting surface saturation effects. Aerogels crosslinked with the tri-functional epoxide always show improved strength compared with aerogels crosslinked with the other two epoxides under identical conditions. Solid C-13 NMR studies show residual unreacted epoxides, which condense with ne another by heating crosslinked aerogels at 150 C.

  5. Acid-base bifunctional catalysis of silica-alumina-supported organic amines for carbon-carbon bond-forming reactions.

    PubMed

    Motokura, Ken; Tomita, Mitsuru; Tada, Mizuki; Iwasawa, Yasuhiro

    2008-01-01

    Acid-base bifunctional heterogeneous catalysts were prepared by the reaction of an acidic silica-alumina (SA) surface with silane-coupling reagents possessing amino functional groups. The obtained SA-supported amines (SA-NR2) were characterized by solid-state 13C and 29Si NMR spectroscopy, FT-IR spectroscopy, and elemental analysis. The solid-state NMR spectra revealed that the amines were immobilized by acid-base interactions at the SA surface. The interactions between the surface acidic sites and the immobilized basic amines were weaker than the interactions between the SA and free amines. The catalytic performances of the SA-NR2 catalysts for various carbon-carbon bond-forming reactions, such as cyano-ethoxycarbonylation, the Michael reaction, and the nitro-aldol reaction, were investigated and compared with those of homogeneous and other heterogeneous catalysts. The SA-NR2 catalysts showed much higher catalytic activities for the carbon-carbon bond-forming reactions than heterogeneous amine catalysts using other supports, such as SiO2 and Al2O3. On the other hand, homogeneous amines hardly promoted these reactions under similar reaction conditions, and the catalytic behavior of SA-NR2 was also different from that of MgO, which was employed as a typical heterogeneous base. An acid-base dual-activation mechanism for the carbon-carbon bond-forming reactions is proposed.

  6. Biomimetic metal-radical reactivity: aerial oxidation of alcohols, amines, aminophenols and catechols catalyzed by transition metal complexes.

    PubMed

    Chaudhuri, Phalguni; Wieghardt, Karl; Weyhermüller, Thomas; Paine, Tapan K; Mukherjee, Soumen; Mukherjee, Chandan

    2005-10-01

    The contributions of the authors to the research program 'Radicals in Enzymatic Catalysis' over the last ca. 5 years are summarized. Significant efforts were directed towards the design and testing of phenol-containing ligands for synthesizing radical-containing transition metal complexes as potential candidates for catalysis of organic substrates like alcohols, amines, aminophenols and catechols. Functional models for different copper oxidases, such as galactose oxidase, amine oxidases, phenoxazinone synthase and catechol oxidase, are reported. The copper complexes synthesized can mimic the function of the metalloenzymes galactose oxidase and amine oxidases by catalyzing the aerial oxidation of alcohols and amines. Even methanol could be oxidized, albeit with a low conversion, by a biradical-copper(II) compound. The presence of a primary kinetic isotope effect, similar to that for galactose oxidase, provides compelling evidence that H-atom abstraction from the alpha-C-atom of the substrates is the rate-limiting step. Although catechol oxidase and phenoxazinone synthase contain copper, manganese(IV) complexes containing radicals have been found to be useful to study synthetic systems and to understand the naturally occurring processes. An 'on-off' mechanism of the radicals without redox participation from the metal centers seems to be operative in the catalysis involving such metal-radical complexes.

  7. Functionalized Polysilsesquioxane-Based Hybrid Silica Solid Amine Sorbents for the Regenerative Removal of CO2 from Air.

    PubMed

    Abhilash, Kochukunju Adisser Saraladevi; Deepthi, Thomas; Sadhana, Retnakumari Amma; Benny, K George

    2015-08-19

    Functionalized polysilsesquioxane-based hybrid silica materials are presented as solid amine sorbents for direct CO2 capture from air. The sorbent was synthesized from amine and vinyl functionalized alkoxysilanes by a simple, energy efficient, and cost-effective co-condensation method. The material, containing bound amine functionalities, was found to have a selective CO2 capturing capacity of 1.68 mmol/g from atmospheric air with an adsorption half time of 50 min. This material also showed a maximum adsorption capacity of 2.28 mmol/g in pure CO2 and 1.92 mmol/g in 10% CO2. Desorption started at a temperature as low as 60 °C, and complete desorption occurred at 80 °C. The sorbent exhibited high recycling ability, and 100 cycles of adsorption/desorption were demonstrated in pure CO2 and 50 cycles in ambient air without any loss in efficiency.

  8. Efficient and reversible CO2 capture by amine functionalized-silica gel confined task-specific ionic liquid system.

    PubMed

    Aboudi, Javad; Vafaeezadeh, Majid

    2015-07-01

    Simple, efficient and practical CO2 capture method is reported using task-specific ionic liquid (IL) supported onto the amine-functionalized silica gel. The results have been shown that both the capacity and rate of the CO2 absorption notably increase in the supported IL/molecular sieve 4 Å system in comparison of homogeneous IL. Additionally, it has shown that the prepared material is capable for reversible carbon dioxide absorption for at least 10 cycles without significant loss of efficiency. The presence of the amine-based IL and the surface bonded amine groups increase the capacity of CO2 absorption even in a CO2/CH4 gas mixture through the formation of ammonium carbamate onto the surface of mesoporous material.

  9. Efficient and reversible CO2 capture by amine functionalized-silica gel confined task-specific ionic liquid system

    PubMed Central

    Aboudi, Javad; Vafaeezadeh, Majid

    2014-01-01

    Simple, efficient and practical CO2 capture method is reported using task-specific ionic liquid (IL) supported onto the amine-functionalized silica gel. The results have been shown that both the capacity and rate of the CO2 absorption notably increase in the supported IL/molecular sieve 4 Å system in comparison of homogeneous IL. Additionally, it has shown that the prepared material is capable for reversible carbon dioxide absorption for at least 10 cycles without significant loss of efficiency. The presence of the amine-based IL and the surface bonded amine groups increase the capacity of CO2 absorption even in a CO2/CH4 gas mixture through the formation of ammonium carbamate onto the surface of mesoporous material. PMID:26199747

  10. Redox-Neutral Copper (II) Carboxylate Catalyzed α-Alkynylation of Amines**

    PubMed Central

    Das, Deepankar; Sun, Aaron X.

    2013-01-01

    A new strategy for iminium ion isomerization was applied to the direct, redox-neutral α-alkynylation of amines. Cu(II) 2-ethylhexanoate was identified as the optimal catalyst for this three-component coupling reaction of secondary amines, aldehydes and alkynes. PMID:23440869

  11. Synthesis of anthranilic acid derivatives through iron-catalyzed ortho amination of aromatic carboxamides with N-chloroamines.

    PubMed

    Matsubara, Tatsuaki; Asako, Sobi; Ilies, Laurean; Nakamura, Eiichi

    2014-01-15

    Arenes possessing an 8-quinolinylamide group as a directing group are ortho aminated with N-chloroamines and N-benzoyloxyamines in the presence of an iron/diphosphine catalyst and an organometallic base to produce anthranilic acid derivatives in high yield. The reaction proceeds via iron-catalyzed C-H activation, followed by the reaction of the resulting iron intermediate with N-chloroamine. The choice of the directing group and diphosphine ligand is crucial for obtaining the anthranilic acid derivative with high yield and product selectivity.

  12. The synthesis of chiral β-aryl-α,β-unsaturated amino alcohols via a Pd-catalyzed asymmetric allylic amination.

    PubMed

    Quan, Mao; Butt, Nicholas; Shen, Jiefeng; Shen, Kaiji; Liu, Delong; Zhang, Wanbin

    2013-11-14

    Chiral β-aryl-α,β-unsaturated amino alcohols were synthesized via a Pd-catalyzed asymmetric allylic amination of 4-aryl-1,3-dioxolan-2-one using planar chiral 1,2-disubstituted ferrocene-based phosphinooxazolines as ligands. Under the optimized reaction conditions, a series of substrates were examined and the products were obtained in good to excellent yields (up to 92%) and enantioselectivities (up to 98% ee) under mild reaction conditions. The desired products were determined to be of (R)-configuration and could subsequently be transformed into compounds with interesting biological activity using simple transformations.

  13. Remarkable Differences in Reactivity between Benzothiazoline and Hantzsch Ester as a Hydrogen Donor in Chiral Phosphoric Acid Catalyzed Asymmetric Reductive Amination of Ketones.

    PubMed

    Kim, Kyung-Hee; Akiyama, Takahiko; Cheon, Cheol-Hong

    2016-01-01

    Described herein are differences in behavior between a Hantzsch ester and a benzothiazoline as hydrogen donors in the chiral phosphoric acid catalyzed asymmetric reductive amination of ketones with p-anisidine. The asymmetric reductive amination of ketones with a Hantzsch ester as a hydrogen donor provided the corresponding chiral amines exclusively, regardless of the structures of the ketones, whereas a similar transformation with a benzothiazoline provided chiral amines and p-methoxyphenyl-protected primary amines in variable yields, depending on the structures of both the ketones and benzothiazolines. Because a benzothiazoline has an N,S-acetal moiety that is vulnerable to p-anisidine, the primary amine can be formed through transimination of the benzothiazoline with p-anisidine followed by reduction of the resulting aldimine with remaining benzothiazoline.

  14. A Highly Effective Ruthenium System for the Catalyzed Dehydrogenative Cyclization of Amine-Boranes to Cyclic Boranes under Mild Conditions.

    PubMed

    Wallis, Christopher J; Alcaraz, Gilles; Petit, Alban S; Poblador-Bahamonde, Amalia I; Clot, Eric; Bijani, Christian; Vendier, Laure; Sabo-Etienne, Sylviane

    2015-09-07

    We recently disclosed a new ruthenium-catalyzed dehydrogenative cyclization process (CDC) of diamine-monoboranes leading to cyclic diaminoboranes. In the present study, the CDC reaction has been successfully extended to a larger number of diamine-monoboranes (4-7) and to one amine-borane alcohol precursor (8). The corresponding NB(H)N- and NB(H)O-containing cyclic diaminoboranes (12-15) and oxazaborolidine (16) were obtained in good to high yields. Multiple substitution patterns on the starting amine-borane substrates were evaluated and the reaction was also performed with chiral substrates. Efforts have been spent to understand the mechanism of the ruthenium CDC process. In addition to a computational approach, a strategy enabling the kinetic discrimination on successive events of the catalytic process leading to the formation of the NB(H)N linkage was performed on the six-carbon chain diamine-monoborane 21 and completed with a (15) N NMR study. The long-life bis-σ-borane ruthenium intermediate 23 possessing a reactive NHMe ending was characterized in situ and proved to catalyze the dehydrogenative cyclization of 1, ascertaining that bis σ-borane ruthenium complexes are key intermediates in the CDC process.

  15. Transition metal-catalyzed process for addition of amines to carbon-carbon double bonds

    DOEpatents

    Hartwig, John F.; Kawatsura, Motoi; Loeber, Oliver

    2002-01-01

    The present invention is directed to a process for addition of amines to carbon-carbon double bonds in a substrate, comprising: reacting an amine with a compound containing at least one carbon-carbon double bond in the presence a transition metal catalyst under reaction conditions effective to form a product having a covalent bond between the amine and a carbon atom of the former carbon-carbon double bond. The transition metal catalyst comprises a Group 8 metal and a ligand containing one or more 2-electron donor atoms. The present invention is also directed to enantioselective reactions of amine compounds with compounds containing carbon-carbon double bonds, and a calorimetric assay to evaluate potential catalysts in these reactions.

  16. Synthesis of chiral cyclic amines via Ir-catalyzed enantioselective hydrogenation of cyclic imines.

    PubMed

    Zhang, Ying; Kong, Duanyang; Wang, Rui; Hou, Guohua

    2017-04-05

    A highly enantioselective hydrogenation of cyclic imines for synthesis of chiral cyclic amines has been realized. With the complex of iridium and (R,R)-f-spiroPhos as the catalyst, a range of cyclic 2-aryl imines were smoothly hydrogenated under mild conditions without any additive to provide the corresponding chiral cyclic amines with excellent enantioselectivities of up to 98% ee. Moreover, this method could be successfully applied to the synthesis of (+)-(6S,10bR)-McN-4612-Z.

  17. Using aqueous ammonia in hydroaminomethylation reactions: ruthenium-catalyzed synthesis of tertiary amines.

    PubMed

    Wu, Lipeng; Fleischer, Ivana; Zhang, Min; Liu, Qiang; Franke, Robert; Jackstell, Ralf; Beller, Matthias

    2014-12-01

    The direct synthesis of tertiary amines from ammonia and olefins is presented. Using a combination of Ru3 (CO)12 and 2-phosphino-substituted imidazole ligand as catalyst system allows for hydroaminomethylation reactions of bulk aliphatic and functionalized olefins. Tertiary amines are obtained in an atom-efficient domino process in moderate to good isolated yields (45-76%) with excellent regioselectivities (n/iso up to 99:1).

  18. Direct use of allylic alcohols for platinum-catalyzed monoallylation of amines.

    PubMed

    Utsunomiya, Masaru; Miyamoto, Yoshiki; Ipposhi, Junji; Ohshima, Takashi; Mashima, Kazushi

    2007-08-16

    A new direct catalytic amination of allylic alcohols promoted by the combination of platinum and a large bite-angle ligand DPEphos was developed in which the allylic alcohol was effectively converted to a pi-allylplatinum intermediate without the use of an activating reagent. The use of the DPEphos ligand was essential for obtaining high catalyst activity and high monoallylation selectivity of primary amines, allowing the formation of a variety of monoallylation products in good to excellent yield.

  19. Site-specific indolation of proline-based peptides via copper(II)-catalyzed oxidative coupling of tertiary amine N-oxides.

    PubMed

    Wu, Xiaowei; Zhang, Dengyou; Zhou, Shengbin; Gao, Feng; Liu, Hong

    2015-08-14

    The first site-specific and purely chemical method for modifying proline-based peptides was developed via a convenient, copper-catalyzed oxidative coupling of tertiary amine N-oxides with indoles. This novel approach features high regioselectivity and diastereoselectivity, mild conditions, and compatibility with various functional groups. In addition, a simplified process was realized in one pot and two steps via in situ oxidative coupling of tertiary amine and indoles.

  20. Synthesis of quinazolines and tetrahydroquinazolines: copper-catalyzed tandem reactions of 2-bromobenzyl bromides with aldehydes and aqueous ammonia or amines.

    PubMed

    Fan, Xuesen; Li, Bin; Guo, Shenghai; Wang, Yuanyuan; Zhang, Xinying

    2014-03-01

    An efficient synthesis of diversely substituted quinazolines and 1,2,3,4-tetrahydroquinazolines through copper-catalyzed tandem reactions of the readily available 2-bromobenzyl bromides, aldehydes, and aqueous ammonia or amines has been developed. By using ammonia and simple aliphatic amines as the nitrogen source, the present method provides a versatile and practical protocol for the synthesis of quinazolines and 1,2,3,4-tetrahydroquinazolines.

  1. Effect of polyvinylpyrrolidone on mesoporous silica morphology and esterification of lauric acid with 1-butanol catalyzed by immobilized enzyme

    SciTech Connect

    Zhang, Jinyu; Zhou, Guowei Jiang, Bin; Zhao, Minnan; Zhang, Yan

    2014-05-01

    Mesoporous silica materials with a range of morphology evolution, i.e., from curved rod-shaped mesoporous silica to straight rod-shaped mesoporous silica, were successfully prepared using polyvinylpyrrolidone (PVP) and triblock copolymer as dual template. The effects of PVP molecular weight and concentration on mesoporous silica structure parameters were studied. Results showed that surface area and pore volume continuously decreased with increased PVP molecular weight. Mesoporous silica prepared with PVP K30 also possessed larger pore diameter, interplanar spacing (d{sub 100}), and cell parameter (a{sub 0}) than that prepared with PVP K15 and PVP K90. In addition, with increased PVP concentration, d{sub 100} and a{sub 0} continuously decreased. The mechanism of morphology evolution caused by the change in PVP concentration was investigated. The conversion rate of lauric acid with 1-butanol catalyzed by immobilized Porcine pancreatic lipase (PPL) was also evaluated. Results showed that PPL immobilized on amino-functionalized straight rod-shaped mesoporous silica maintained 50% of its esterification conversion rate even after five cycles of use with a maximum conversion rate was about 90.15%. - Graphical abstract: Curved rod-shaped mesoporous silica can be obtained at low and the highest PVP concentration, while straight rod-shaped mesoporous silica can be obtained at higher PVP concentration. - Highlights: • Mesoporous silica with morphology evolution from CRMS to SRMS were prepared. • Effects of PVP molecular weight and concentration on silica morphology were studied. • A possible mechanism for the formation of morphology evolution SiO{sub 2} was proposed. • Esterification of lauric acid with 1-butanol catalyzed by immobilized PPL.

  2. P450-catalyzed intramolecular sp(3) C-H amination with arylsulfonyl azide substrates.

    PubMed

    Singh, Ritesh; Bordeaux, Melanie; Fasan, Rudi

    2014-01-06

    The direct amination of aliphatic C-H bonds represents a most valuable transformation in organic chemistry. While a number of transition metal-based catalysts have been developed and investigated for this purpose, the possibility to execute this transformation with biological catalysts has remained largely unexplored. Here, we report that cytochrome P450 enzymes can serve as efficient catalysts for mediating intramolecular benzylic C-H amination reactions in a variety of arylsulfonyl azide compouds. Under optimized conditions, the P450 catalysts were found to support up to 390 total turnovers leading to the formation of the desired sultam products with excellent regioselectivity. In addition, the chiral environment provided by the enzyme active site allowed for the reaction to proceed in a stereo- and enantioselective manner. The C-H amination activity, substrate profile, and enantio/stereoselectivity of these catalysts could be modulated by utilizing enzyme variants with engineered active sites.

  3. Fast solid-phase extraction of N-linked glycopeptides by amine-functionalized mesoporous silica nanoparticles.

    PubMed

    Miao, Weili; Zhang, Cheng; Cai, Yan; Zhang, Ying; Lu, Haojie

    2016-04-21

    Selective enrichment is a crucial step before the mass spectrometric analysis of glycoproteins. A new approach using 3-aminopropyltriethoxysilane (APTES)-functionalized mesoporous silica materials (SBA-15) was reported to enrich the glycoproteins. Selective extraction of glycopeptides was achieved through coupling the oxidized glycan chains on the glycopeptides with the amine groups on SBA-15 through a reductive amination reaction, then the captured glycopeptides were detached from the SBA-15 for the following MS analysis using the enzyme PNGase F. Because the mesoporous material has a confinement effect, the efficiency of enrichment and enzymatic deglycosylation was improved dramatically. The coupling time was shortened from 4 hours to 1 hour, and the deglycosylation time was greatly shortened from 6 hours to 3 hours. This approach was successfully applied to profile the N-glycoproteome of human colorectal cancer serum. 84 N-linked glycosylation sites from 56 N-linked glycoproteins were identified from as little as 5 μL serum.

  4. Chiral primary amine catalyzed asymmetric Michael addition of malononitrile to α-substituted vinyl ketone.

    PubMed

    Fu, Niankai; Zhang, Long; Luo, Sanzhong

    2015-01-16

    The first efficient and highly enantioselective Michael addition-protonation reaction of malononitriles to α-substituted vinyl ketones has been developed by using a chiral primary amine as the organocatalyst. With a Hantzsch ester as the hydride source, an enantioselective tandem reduction, Michael addition-protonation reaction of benzylidenemalononitrile has also been achieved with good yields and high enantioselectivities.

  5. Squaramide-tertiary amine catalyzed asymmetric cascade sulfa-Michael/Michael addition via dynamic kinetic resolution: access to highly functionalized chromans with three contiguous stereocenters.

    PubMed

    Yang, Wen; Yang, Yi; Du, Da-Ming

    2013-03-15

    An efficient asymmetric cascade sulfa-Michael/Michael addition reaction catalyzed by a chiral bifunctional squaramide-tertiary amine catalyst has been developed. This organocatalytic cascade reaction provides easy access to highly functionalized chromans with three contiguous stereocenters, including one quaternary center. In addition, a novel cascade sulfa Michael/retro-sulfa-Michael/sulfa-Michael/Michael reaction process, involving dynamic kinetic resolution, is described.

  6. Distinct reactivity of Morita-Baylis-Hillman acetates as a novel C(2) component in amine-catalyzed [2 + 2 + 2] and [2 + 4] annulations.

    PubMed

    Chen, Rongshun; Xu, Silong; Wang, Liyi; Tang, Yuhai; He, Zhengjie

    2013-05-04

    Amine-catalyzed [2 + 2 + 2] and [2 + 4] annulations of Morita-Baylis-Hillman (MBH) acetates with cyano activated alkenes and 1,3-azadienes have been developed to provide cyclohexanes and tetrahydropyridines. In the annulations, MBH acetates serve as a novel C(2) component with an inactive homoallylic methyl involved in the bond formation.

  7. Energy-efficient green catalysis: supported gold nanoparticle-catalyzed aminolysis of esters with inert tertiary amines by C-O and C-N bond activations.

    PubMed

    Bao, Yong-Sheng; Baiyin, Menghe; Agula, Bao; Jia, Meilin; Zhaorigetu, Bao

    2014-07-18

    Catalyzed by supported gold nanoparticles, an aminolysis reaction between various aryl esters and inert tertiary amines by C-O and C-N bond activations has been developed for the selective synthesis of tertiary amides. Comparison studies indicated that the gold nanoparticles could perform energy-efficient green catalysis at room temperature, whereas Pd(OAc)2 could not.

  8. nBu4NI-catalyzed oxidative cross-coupling of carbon dioxide, amines, and aryl ketones: access to O-β-oxoalkyl carbamates.

    PubMed

    Peng, Youbin; Liu, Juan; Qi, Chaorong; Yuan, Gaoqing; Li, Jiawei; Jiang, Huanfeng

    2017-02-28

    The first nBu4NI-catalyzed oxidative cross-coupling reaction of carbon dioxide, amines and arylketones has been successfully developed by using TBHP as the oxidant, providing an efficient, atom-economical and metal-free strategy for the synthesis of a range of O-β-oxoalkyl carbamates.

  9. Sulfonic acid functionalized silica: an efficient heterogeneous catalyst for a three-component synthesis of 1,4-dihydropyridines under solvent-free conditions.

    PubMed

    Das, Biswanath; Suneel, Kanaparthy; Venkateswarlu, Katta; Ravikanth, Bommena

    2008-03-01

    Sulfonic acid functionalized silica catalyzed the three-component reaction of aromatic amines, alpha,beta-unsaturated aldehydes and beta-keto esters forming the corresponding 1,4-dihydropyridines in short reaction times and in high yields.

  10. Ionic liquid-functionalized silica for selective solid-phase extraction of organic acids, amines and aldehydes.

    PubMed

    Vidal, Lorena; Parshintsev, Jevgeni; Hartonen, Kari; Canals, Antonio; Riekkola, Marja-Liisa

    2012-02-24

    Three ionic liquid (IL)-functionalized silica materials, imidazolium, N-methylimidazolium and 1-alkyl-3-(propyl-3-sulfonate) imidazolium, were synthesised and applied in solid-phase extraction (SPE) of organic acids, amines and aldehydes, which are important compound families in atmospheric aerosol particles. 1-Alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica was tested as sorbent for SPE for the first time. The analytes were separated and detected by liquid chromatography-mass spectrometry (LC-MS). To confirm the results achieved by LC-MS, the acids were additionally determined by gas chromatography-mass spectrometry (GC-MS). The stability of the IL-functionalized silica materials was tested at low and high pH. The effect of the pH on the extraction was also informative of the retention mechanism of the materials. The results showed anion exchange to be the main interaction, but hydrophobic and π interactions and hydrogen bonding also played a role in the extraction. Extraction efficiencies for organic acids ranged from 87 to 110%, except for cis-pinonic acid (19-29%). Lower extraction efficiencies for amines and aldehydes confirmed that anionic exchange was the predominant interaction. Comparisons made with two commercial SPE materials--silica-based strong anion exchange (SAX) and polymer-based mixed-mode anion exchange and reverse-phase (MAX)--showed the IL-functionalized materials to offer different selectivity and better extraction efficiency than SAX for aromatic compounds. Finally, the new materials were successfully tested in the extraction of an atmospheric aerosol sample.

  11. Platinum-catalyzed direct amination of allylic alcohols under mild conditions: ligand and microwave effects, substrate scope, and mechanistic study.

    PubMed

    Ohshima, Takashi; Miyamoto, Yoshiki; Ipposhi, Junji; Nakahara, Yasuhito; Utsunomiya, Masaru; Mashima, Kazushi

    2009-10-14

    Transition metal-catalyzed amination of allylic compounds via a pi-allylmetal intermediate is a powerful and useful method for synthesizing allylamines. Direct catalytic substitution of allylic alcohols, which forms water as the sole coproduct, has recently attracted attention for its environmental and economical advantages. Here, we describe the development of a versatile direct catalytic amination of both aryl- and alkyl-substituted allylic alcohols with various amines using Pt-Xantphos and Pt-DPEphos catalyst systems, which allows for the selective synthesis of various monoallylamines, such as the biologically active compounds Naftifine and Flunarizine, in good to high yield without need for an activator. The choice of the ligand was crucial toward achieving high catalytic activity, and we demonstrated that not only the large bite-angle but also the linker oxygen atom of the Xantphos and DPEphos ligands was highly important. In addition, microwave heating dramatically affected the catalyst activity and considerably decreased the reaction time compared with conventional heating. Furthermore, several mechanistic investigations, including (1)H and (31)P{(1)H} NMR studies; isolation and characterization of several catalytic intermediates, Pt(xantphos)Cl(2), Pt(eta(2)-C(3)H(5)OH)(xantphos), etc; confirmation of the structure of [Pt(eta(3)-allyl)(xantphos)]OTf by X-ray crystallographic analysis; and crossover experiments, suggested that formation of the pi-allylplatinum complex through the elimination of water is an irreversible rate-determining step and that the other processes in the catalytic cycle are reversible, even at room temperature.

  12. Mechanism of arylboronic acid-catalyzed amidation reaction between carboxylic acids and amines.

    PubMed

    Wang, Chen; Yu, Hai-Zhu; Fu, Yao; Guo, Qing-Xiang

    2013-04-07

    Arylboronic acids were found to be efficient catalysts for the amidation reactions between carboxylic acids and amines. Theoretical calculations have been carried out to investigate the mechanism of this catalytic process. It is found that the formation of the acyloxyboronic acid intermediates from the carboxylic acid and the arylboronic acid is kinetically facile but thermodynamically unfavorable. Removal of water (as experimentally accomplished by using molecular sieves) is therefore essential for overall transformation. Subsequently C-N bond formation between the acyloxyboronic acid intermediates and the amine occurs readily to generate the desired amide product. The cleavage of the C-O bond of the tetracoordinate acyl boronate intermediates is the rate-determining step in this process. Our analysis indicates that the mono(acyloxy)boronic acid is the key intermediate. The high catalytic activity of ortho-iodophenylboronic acid is attributed to the steric effect as well as the orbital interaction between the iodine atom and the boron atom.

  13. An Inner-Sphere Mechanism for Molecular Oxygen Reduction Catalyzed by Copper Amine Oxidases

    PubMed Central

    Mukherjee, Arnab; Smirnov, Valeriy V.; Lanci, Michael P.; Brown, Doreen E.; Shepard, Eric M.; Dooley, David M.; Roth, Justine P.

    2008-01-01

    Copper and topaquinone (TPQ) containing amine oxidases utilize O2 for the metabolism of biogenic amines while concomitantly generating H2O2 for use by the cell. The mechanism of O2 reduction has been the subject of long-standing debate due to the obscuring influence of a proton-coupled electron transfer between the tyrosine-derived TPQ and copper, a rapidly established equilibrium precluding assignment of the enzyme in its reactive form. Here we show that substrate-reduced pea seedling amine oxidase (PSAO) exists predominantly in the CuI, TPQ semiquinone state. A new mechanistic proposal for O2 reduction is advanced on the basis of thermodynamic considerations together with kinetic studies (at varying pH, temperature and viscosity), the identification of steady-state intermediates and the analysis of competitive oxygen kinetic isotope effects: 18O KIEs, [kcat/KM(16,16O2)]/[kcat/KM(16,18O2)]. The 18O KIE = 1.0136 ± 0.0013 at pH 7.2 is independent of temperature from 5 to 47°C and insignificantly changed to 1.0122 ± 0.0020 upon raising the pH to 9, thus indicating the absence of kinetic complexity. Using density functional methods, the effect is found to be precisely in the range expected for reversible O2 binding to CuI to afford a superoxide, [CuII(η1-O2)−I]+, intermediate. Electron transfer from the TPQ semiquinone follows in the first irreversible step to form a peroxide, CuII(η1-O2)−II, intermediate driving the reduction of O2. The similar 18O KIEs reported for copper amine oxidases from other sources raise the possibility that all enzymes react by related inner-sphere mechanisms although additional experiments are needed to test this proposal. PMID:18582059

  14. Origin of fast catalysis in allylic amination reactions catalyzed by Pd-Ti heterobimetallic complexes.

    PubMed

    Walker, Whitney K; Kay, Benjamin M; Michaelis, Scott A; Anderson, Diana L; Smith, Stacey J; Ess, Daniel H; Michaelis, David J

    2015-06-17

    Experiments and density functional calculations were used to quantify the impact of the Pd-Ti interaction in the cationic heterobimetallic Cl2Ti(N(t)BuPPh2)2Pd(η(3)-methallyl) catalyst 1 used for allylic aminations. The catalytic significance of the Pd-Ti interaction was evaluated computationally by examining the catalytic cycle for catalyst 1 with a conformation where the Pd-Ti interaction is intact versus one where the Pd-Ti interaction is severed. Studies were also performed on the relative reactivity of the cationic monometallic (CH2)2(N(t)BuPPh2)2Pd(η(3)-methallyl) catalyst 2 where the Ti from catalyst 1 was replaced by an ethylene group. These computational and experimental studies revealed that the Pd-Ti interaction lowers the activation barrier for turnover-limiting amine reductive addition and accelerates catalysis up to 10(5). The Pd-Ti distance in 1 is the result of the N(t)Bu groups enforcing a boat conformation that brings the two metals into close proximity, especially in the transition state. The turnover frequency of classic Pd π allyl complexes was compared to that of 1 to determine the impact of P-Pd-P coordination angle and ligand electronic properties on catalysis. These experiments identified that cationic (PPh3)2Pd(η(3)-CH2C(CH3)CH2) catalyst 3 performs similarly to 1 for allylic aminations with diethylamine. However, computations and experiment reveal that the apparent similarity in reactivity is due to very fast reaction kinetics. The higher reactivity of 1 versus 3 was confirmed in the reaction of methallyl chloride and 2,2,6,6-tetramethylpiperidine (TMP). Overall, experiments and calculations demonstrate that the Pd-Ti interaction induces and is responsible for significantly lower barriers and faster catalysis for allylic aminations.

  15. Copper(II)/amine synergistically catalyzed enantioselective alkylation of cyclic N-acyl hemiaminals with aldehydes.

    PubMed

    Sun, Shutao; Mao, Ying; Lou, Hongxiang; Liu, Lei

    2015-07-07

    The first catalytic asymmetric alkylation of N-acyl quinoliniums with aldehydes has been described. A copper/amine synergistic catalytic system has been developed, allowing the addition of functionalized aldehydes to a wide range of electronically varied N-acyl quinoliniums in good yields with excellent enantiocontrol. The synergistic catalytic system was also effective for N-acyl dihydroisoquinoliniums and β-caboliniums, demonstrating the general applicability of the protocol in the enantioselective alkylation of diverse cyclic N-acyl hemiaminals.

  16. Rhodium(III)-catalyzed allylic C-H bond amination. Synthesis of cyclic amines from ω-unsaturated N-sulfonylamines.

    PubMed

    Cochet, Thomas; Bellosta, Véronique; Roche, Didier; Ortholand, Jean-Yves; Greiner, Alfred; Cossy, Janine

    2012-11-11

    For the first time, intramolecular allylic amination was conducted using rhodium(III) according to an "inner-sphere" type mechanism with amines activated by only one electron-withdrawing group. The activation of C(sp(3))-H bonds was chemoselective and allows the access to a variety of substituted cyclic amines such as pyrrolidines and piperidines.

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

    PubMed

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

    2014-06-20

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

  18. Effect of polyvinylpyrrolidone on mesoporous silica morphology and esterification of lauric acid with 1-butanol catalyzed by immobilized enzyme

    NASA Astrophysics Data System (ADS)

    Zhang, Jinyu; Zhou, Guowei; Jiang, Bin; Zhao, Minnan; Zhang, Yan

    2014-05-01

    Mesoporous silica materials with a range of morphology evolution, i.e., from curved rod-shaped mesoporous silica to straight rod-shaped mesoporous silica, were successfully prepared using polyvinylpyrrolidone (PVP) and triblock copolymer as dual template. The effects of PVP molecular weight and concentration on mesoporous silica structure parameters were studied. Results showed that surface area and pore volume continuously decreased with increased PVP molecular weight. Mesoporous silica prepared with PVP K30 also possessed larger pore diameter, interplanar spacing (d100), and cell parameter (a0) than that prepared with PVP K15 and PVP K90. In addition, with increased PVP concentration, d100 and a0 continuously decreased. The mechanism of morphology evolution caused by the change in PVP concentration was investigated. The conversion rate of lauric acid with 1-butanol catalyzed by immobilized Porcine pancreatic lipase (PPL) was also evaluated. Results showed that PPL immobilized on amino-functionalized straight rod-shaped mesoporous silica maintained 50% of its esterification conversion rate even after five cycles of use with a maximum conversion rate was about 90.15%.

  19. Ligand-Free Pd-Catalyzed Double Carbonylation of Aryl Iodides with Amines to α-Ketoamides under Atmospheric Pressure of Carbon Monoxide and at Room Temperature.

    PubMed

    Du, Hongyan; Ruan, Qing; Qi, Minghao; Han, Wei

    2015-08-07

    A general Pd-catalyzed double carbonylation of aryl iodides with secondary or primary amines to produce α-ketoamides at atmospheric CO pressure has been developed. This transformation proceeds successfully even at room temperature and in the absence of any ligand and additive. A wide range of aryl iodides and amines can be coupled to the desired α-ketoamides in high yields with excellent chemoselectivities. Importantly, the current methodology has been demonstrated to be applied in the synthesis of bioactive molecules and chiral α-ketoamides.

  20. Improved Synthesis of 5-Substituted 1H-Tetrazoles via the [3+2] Cycloaddition of Nitriles and Sodium Azide Catalyzed by Silica Sulfuric Acid

    PubMed Central

    Du, Zhenting; Si, Changmei; Li, Youqiang; Wang, Yin; Lu, Jing

    2012-01-01

    A silica supported sulfuric acid catalyzed [3+2] cycloaddition of nitriles and sodium azide to form 5-substituted 1H-tetrazoles is described. The protocol can provide a series of 5-substituted 1H-tetrazoles using silica sulfuric acid from nitriles and sodium azide in DMF in 72%–95% yield. PMID:22606004

  1. Improved synthesis of 5-substituted 1H-tetrazoles via the [3+2] cycloaddition of nitriles and sodium azide catalyzed by silica sulfuric acid.

    PubMed

    Du, Zhenting; Si, Changmei; Li, Youqiang; Wang, Yin; Lu, Jing

    2012-01-01

    A silica supported sulfuric acid catalyzed [3+2] cycloaddition of nitriles and sodium azide to form 5-substituted 1H-tetrazoles is described. The protocol can provide a series of 5-substituted 1H-tetrazoles using silica sulfuric acid from nitriles and sodium azide in DMF in 72%-95% yield.

  2. Comparative analyses of laccase-catalyzed amination reactions for production of novel β-lactam antibiotics.

    PubMed

    Mikolasch, Annett; Manda, Katrin; Schlüter, Rabea; Lalk, Michael; Witt, Sabine; Seefeldt, Simone; Hammer, Elke; Schauer, Frieder; Jülich, Wolf-Dieter; Lindequist, Ulrike

    2012-01-01

    Seven novel β-lactam antibiotics with activities against Gram-positive bacterial strains, among them methicillin-resistant Staphylococcus aureus and vancomycin-resistant enterococci, were synthesized by amination of 2,5-dihydroxyphenylacetic acid in usable yields (30-60%). These products protected mice against an infection with S. aureus lethal to the control animals. The results show the usefulness of laccase for the synthesis of potential new antibiotics, in addition to the interdependence of the laccase substrates, the amino coupling partners, and the product formation, yield, and activity. The syntheses of β-lactam antibiotics with 2,5-dihydroxyaromatic acid substructures (para-substituted) are then compared with those of 3,4-dihydroxyaromatic acid substructures (ortho-substituted). Para-substituted laccase substrates were better reaction partners in these syntheses than ortho-substituted compounds.

  3. Asymmetric Michael addition/intramolecular cyclization catalyzed by bifunctional tertiary amine-squaramides: construction of chiral 2-amino-4H-chromene-3-carbonitrile derivatives.

    PubMed

    Gao, Yu; Du, Da-Ming

    2014-10-01

    The efficient asymmetric Michael addition/intramolecular cyclization of malononitrile with dienones catalyzed by a chiral bifunctional tertiary amine-squaramide catalyst for the synthesis of chiral 2-amino-4H-chromene-3-carbonitrile derivatives was developed. The corresponding products were obtained in good to excellent yields (up to 99%) with excellent enantioselectivities (up to 98% ee) for most of the bisarylidenecyclopentanones.

  4. Application of ruthenium catalyzed oxidation of [tris(2-aminoethyl)amine] in trace determination of ruthenium in environmental water samples

    NASA Astrophysics Data System (ADS)

    Prasad, Surendra; Naik, Radhey M.; Srivastava, Abhishek

    2008-10-01

    The ruthenium catalyzed oxidation of tris(2-aminoethyl)amine (TREN) by hexacyanoferrate(III) has been utilized for the development of a new and sensitive catalytic kinetic method (CKM) for the determination of ruthenium(III). The reaction was followed spectrophotometrically by the decrease in absorbance at 420 nm ( λmax of [Fe(CN) 6] 3-). The CKM developed utilizes fixed time procedure under optimum reaction conditions where the change in absorbance (Δ At) versus ruthenium(III) concentrations is plotted. The calibration curve recommended for the method is linear in the concentration range 10.11-252.67 ng ml -1 with very good accuracy and reproducibility and a maximum error 2.20%. The detection limits of the method for ruthenium(III) corresponding to 10, 15 and 20 min are 8.02, 5.03 and 3.15 ng ml -1, respectively. The ruthenium(III) has also been determined in the presence of several other interfering and non-interfering cations and anions and no foreign ions interfered in the determination of ruthenium(III) up to five-fold higher concentration of the foreign ions tested. The method is highly sensitive, selective and stable. It has successfully been applied for the determination of trace ruthenium(III) in some synthetic and environmental water samples. A review of most of the published catalytic kinetic and some other important methods for the determination of ruthenium has also been presented.

  5. Gold-catalyzed intramolecular allylic amination of 2-tosylaminophenylprop-1-en-3-ols. A concise synthesis of (+/-)-angustureine.

    PubMed

    Kothandaraman, Prasath; Foo, Shi Jia; Chan, Philip Wai Hong

    2009-08-21

    An efficient synthetic route to 1,2-dihydroquinolines that relies on AuCl(3)/AgSbF(6)-catalyzed intramolecular allylic amination of 2-tosylaminophenylprop-1-en-3-ols is described herein. Uniquely, the reactions were found to only proceed rapidly at room temperature in the presence of the gold and silver catalyst combination and produce the 1,2-dihydroquinoline products in yields of 40-91%. The method was shown to be applicable to a broad range of 2-tosylaminophenylprop-1-en-3-ols containing electron-withdrawing, electron-donating, and sterically demanding substrate combinations. The mechanism is suggested to involve activation of the alcohol substrate by the AuCl(3)/AgSbF(6) catalyst. This is followed by ionization of the starting material, which causes intramolecular nucleophilic addition of the sulfonamide unit to the allylic cation moiety and construction of the 1,2-dihydroquinoline. The utility of this N-heterocyclic ring forming strategy as a synthetic tool that makes use of alcohols as pro-electrophiles was exemplified by its application to the synthesis of the bioactive tetrahydroquinoline alkaloid (+/-)-angustureine.

  6. Amino acid-catalyzed seed regrowth synthesis of photostable high fluorescent silica nanoparticles with tunable sizes for intracellular studies

    NASA Astrophysics Data System (ADS)

    Shahabi, Shakiba; Treccani, Laura; Rezwan, Kurosch

    2015-06-01

    Size-controlled fluorescence silica nanoparticles (NPs) are widely used for nanotoxicological studies, and diagnostic and targeted therapies. Such particles can be easily visualized and localized within cell environments and their interactions with cellular components can be monitored. We developed an amino acid-catalyzed seed regrowth technique (ACSRT) to synthesize spherical rhodamine-doped silica NPs with tunable sizes, low polydispersity index as well as high labeling efficiency and enhanced fluorescence photostability. Via ACSRT, fluorescent silica NPs can be obtained by introducing the fluorophore in seed formation step, while a precise control over particle size can be achieved by simply adjusting the concentration of reactants in the regrowth step. Unlike the conventional methods, the proposed ACSRT permits the synthesis of fluorescent silica NPs in a water-based system, without the use of any surfactants and co-surfactants. By this approach, additional linkers for covalent coupling of the fluorophore to silica matrix can be omitted, while a remarkable doping efficiency is achieved. The suitability of these particles for biomedical application is demonstrated by in vitro tests with normal and malignant bone cells. We show that the particles can be easily and unambiguously visualized by a conventional fluorescence microscope, localized, and distinguished within intracellular components. In addition, it is presented that the cellular uptake and cytotoxic profile of silica NPs are strongly correlated to the particle size, concentration, and cell line. The results of in vitro experiments demonstrate that tunable fluorescent silica NPs synthesized with ACSRT can be potentially used for toxicological assessments and nanomedical studies.

  7. Enhancement of formaldehyde degradation by amine functionalized silica/titania films.

    PubMed

    Photong, Somjate; Boonamnuayvitaya, Virote

    2009-01-01

    Doping amine functional groups into SiO2/TiO2 films for enhancing the decomposition of formaldehyde has been investigated using the modified sol-gel method to prepare organic-inorganic hybrid photocatalysts via the co-condensation reaction of methyltrimethoxysilane (MTMOS) and amine functional groups. n-(2-Aminoethyl)-3-aminopropyl-trimethoxysilane (AEAPTMS) and 3-aminopropyl-trimethoxysilane (APTMS) were selected to study the effect of amine functional groups on the enhancement of formaldehyde adsorption and degradation under a UV irradiation process. Physicochemical properties of prepared photocatalysts were characterized with nitrogen adsorption-desorption isotherms measurement, X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy. The results indicated that the APTMS/SiO2/TiO2 film demonstrated a degradation efficiency of 79% superior to those of SiO2/TiO2 and AEAPTMS/SiO2/TiO2 films due to the synergetic effect of adsorption and photocatalytic properties. The APTMS/SiO2/TiO2 film can be recycled with about 7% decreasing of degradation efficiency after seven cycles.

  8. Bulk gold catalyzed oxidation reactions of amines and isocyanides and iron porphyrin catalyzed N-H and O-H bond insertion/cyclization reactions of diamines and aminoalcohols

    SciTech Connect

    Klobukowski, Erik

    2011-01-01

    This work involves two projects. The first project entails the study of bulk gold as a catalyst in oxidation reactions of isocyanides and amines. The main goal of this project was to study the activation and reactions of molecules at metal surfaces in order to assess how organometallic principles for homogeneous processes apply to heterogeneous catalysis. Since previous work had used oxygen as an oxidant in bulk gold catalyzed reactions, the generality of gold catalysis with other oxidants was examined. Amine N-oxides were chosen for study, due to their properties and use in the oxidation of carbonyl ligands in organometallic complexes. When amine N-oxides were used as an oxidant in the reaction of isocyanides with amines, the system was able to produce ureas from a variety of isocyanides, amines, and amine N-oxides. In addition, the rate was found to generally increase as the amine N-oxide concentration increased, and decrease with increased concentrations of the amine. Mechanistic studies revealed that the reaction likely involves transfer of an oxygen atom from the amine N-oxide to the adsorbed isocyanide to generate an isocyanate intermediate. Subsequent nucleophilic attack by the amine yields the urea. This is in contrast to the bulk gold-catalyzed reaction mechanism of isocyanides with amines and oxygen. Formation of urea in this case was proposed to proceed through a diaminocarbene intermediate. Moreover, formation of the proposed isocyanate intermediate is consistent with the reactions of metal carbonyl ligands, which are isoelectronic to isocyanides. Nucleophilic attack at coordinated CO by amine N-oxides produces CO{sub 2} and is analogous to the production of an isocyanate in this gold system. When the bulk gold-catalyzed oxidative dehydrogenation of amines was examined with amine N-oxides, the same products were afforded as when O{sub 2} was used as the oxidant. When the two types of oxidants were directly compared using the same reaction system and

  9. Mechanistic studies of hydrogen evolution in aqueous solution catalyzed by a tertpyridine-amine cobalt complex

    SciTech Connect

    Lewandowska-Andralojc, Anna; Baine, Teera; Zhao, Xuan; Muckerman, James T.; Fujita, Etsuko; Poyansky, Dmitry E.

    2015-04-22

    The ability of cobalt-based transition metal complexes to catalyze electrochemical proton reduction to produce molecular hydrogen has resulted in a large number of mechanistic studies involving various cobalt complexes. In addition, while the basic mechanism of proton reduction promoted by cobalt species is well understood, the reactivity of certain reaction intermediates, such as CoI and CoIII–H, is still relatively unknown owing to their transient nature, especially in aqueous media. In this work we investigate the properties of intermediates produced during catalytic proton reduction in aqueous solutions promoted by the [(DPA-Bpy)Co(OH₂)]n+ (DPA-Bpy = N,N-bis(2-pyridinylmethyl)-2,20-bipyridine-6-methanamine) complex ([Co(L)(OH₂)]n+ where L is the pentadentate DPA-Bpy ligand or [Co(OH₂)]n+ as a shorthand). Experimental results based on transient pulse radiolysis and laser flash photolysis methods, together with electrochemical studies and supported by DFT calculations indicate that, while the water ligand is strongly coordinated to the metal center in the oxidation state 3+, one-electron reduction of the complex to form a CoII species results in weakening the Co–O bond. The further reduction to a CoI species leads to the loss of the aqua ligand and the formation of [CoI–VS)]⁺ (VS = vacant site). Interestingly, DFT calculations also predict the existence of a [CoI(κ⁴-L)(OH₂)]⁺ species at least transiently, and its formation is consistent with the experimental Pourbaix diagram. Both electrochemical and kinetics results indicate that the CoI species must undergo some structural change prior to accepting the proton, and this transformation represents the rate-determining step (RDS) in the overall formation of [CoIII–H]⁺. We propose that this RDS may originate from the slow removal of a solvent ligand in the

  10. Mechanistic studies of hydrogen evolution in aqueous solution catalyzed by a tertpyridine-amine cobalt complex

    DOE PAGES

    Lewandowska-Andralojc, Anna; Baine, Teera; Zhao, Xuan; ...

    2015-04-22

    The ability of cobalt-based transition metal complexes to catalyze electrochemical proton reduction to produce molecular hydrogen has resulted in a large number of mechanistic studies involving various cobalt complexes. In addition, while the basic mechanism of proton reduction promoted by cobalt species is well understood, the reactivity of certain reaction intermediates, such as CoI and CoIII–H, is still relatively unknown owing to their transient nature, especially in aqueous media. In this work we investigate the properties of intermediates produced during catalytic proton reduction in aqueous solutions promoted by the [(DPA-Bpy)Co(OH₂)]n+ (DPA-Bpy = N,N-bis(2-pyridinylmethyl)-2,20-bipyridine-6-methanamine) complex ([Co(L)(OH₂)]n+ where L is the pentadentatemore » DPA-Bpy ligand or [Co(OH₂)]n+ as a shorthand). Experimental results based on transient pulse radiolysis and laser flash photolysis methods, together with electrochemical studies and supported by DFT calculations indicate that, while the water ligand is strongly coordinated to the metal center in the oxidation state 3+, one-electron reduction of the complex to form a CoII species results in weakening the Co–O bond. The further reduction to a CoI species leads to the loss of the aqua ligand and the formation of [CoI–VS)]⁺ (VS = vacant site). Interestingly, DFT calculations also predict the existence of a [CoI(κ⁴-L)(OH₂)]⁺ species at least transiently, and its formation is consistent with the experimental Pourbaix diagram. Both electrochemical and kinetics results indicate that the CoI species must undergo some structural change prior to accepting the proton, and this transformation represents the rate-determining step (RDS) in the overall formation of [CoIII–H]⁺. We propose that this RDS may originate from the slow removal of a solvent ligand in the intermediate [CoI(κ⁴-L)(OH₂)]⁺ in addition to the significant structural reorganization of the metal complex and

  11. Controlling First-Row Catalysts: Amination of Aryl and Heteroaryl Chlorides and Bromides with Primary Aliphatic Amines Catalyzed by a BINAP-Ligated Single-Component Ni(0) Complex

    PubMed Central

    2015-01-01

    First-row metal complexes often undergo undesirable one-electron redox processes during two-electron steps of catalytic cycles. We report the amination of aryl chlorides and bromides with primary aliphatic amines catalyzed by a well-defined, single-component nickel precursor (BINAP)Ni(η2-NC-Ph) (BINAP = 2,2′-bis(biphenylphosphino)-1,1′-binaphthalene) that minimizes the formation of Ni(I) species and (BINAP)2Ni. The scope of the reaction encompasses electronically varied aryl chlorides and nitrogen-containing heteroaryl chlorides, including pyridine, quinoline, and isoquinoline derivatives. Mechanistic studies support the catalytic cycle involving a Ni(0)/Ni(II) couple for this nickel-catalyzed amination and are inconsistent with a Ni(I) halide intermediate. Monitoring the reaction mixture by 31P NMR spectroscopy identified (BINAP)Ni(η2-NC-Ph) as the resting state of the catalyst in the amination of both aryl chlorides and bromides. Kinetic studies showed that the amination of aryl chlorides and bromides is first order in both catalyst and aryl halide and zero order in base and amine. The reaction of a representative aryl chloride is inverse first order in PhCN, but the reaction of a representative aryl bromide is zero order in PhCN. This difference in the order of the reaction in PhCN indicates that the aryl chloride reacts with (BINAP)Ni(0), formed by dissociation PhCN from (BINAP)Ni(η2-NC-Ph), but the aryl bromide directly reacts with (BINAP)Ni(η2-NC-Ph). The overall kinetic behavior is consistent with turnover-limiting oxidative addition of the aryl halide to Ni(0). Several pathways for catalyst decomposition were identified, such as the formation of the catalytically inactive bis(amine)-ligated arylnickel(II) chloride, (BINAP)2Ni(0), and the Ni(I) species [(BINAP)Ni(μ-Cl)]2. By using a well-defined nickel complex as catalyst, the formation of (BINAP)2Ni(0) is avoided and the formation of the Ni(I) species [(BINAP)Ni(μ-Cl)]2 is minimized. PMID:24397570

  12. Equilibrium and kinetics analysis of carbon dioxide capture using immobilized amine on a mesoporous silica

    SciTech Connect

    Monazam, E., Shadle, L., Pennline, H., Miller, D., Fauth, D., Hoffman, J., Gray, M.

    2012-01-01

    The equilibrium and conversion-time data on the absorption of carbon dioxide (CO{sub 2}) with amine-based solid sorbent were analyzed over the range of 303–373 K. Data on CO{sub 2} loading on amine based solid sorbent at these temperatures and CO{sub 2} partial pressure between 10 and 760 mm Hg obtained from volumetric adsorption apparatus were fitted to a simple equilibrium model to generate the different parameters (including equilibrium constant) in the model. Using these constants, a correlation was obtained to define equilibrium constant and maximum CO{sub 2} loading as a function of temperature. In this study, a shrinking core model (SCM) was applied to elucidate the relative importance of pore diffusion and surface chemical reaction in controlling the rate of reaction. Application of SCM to the data suggested a surface reaction-controlled mechanism for the temperature of up to 40°C and pore-diffusion mechanism at higher temperature.

  13. Robust and Porous β-Diketiminate-Functionalized Metal–Organic Frameworks for Earth-Abundant-Metal-Catalyzed C–H Amination and Hydrogenation

    SciTech Connect

    Thacker, Nathan C.; Lin, Zekai; Zhang, Teng; Gilhula, James C.; Abney, Carter W.; Lin, Wenbin

    2016-05-27

    We have designed a strategy for postsynthesis installation of the β-diketiminate (NacNac) functionality in a metal–organic framework (MOF) of UiO-topology. Metalation of the NacNac-MOF (I) with earth-abundant metal salts afforded the desired MOF-supported NacNac-M complexes (M = Fe, Cu, and Co) with coordination environments established by detailed EXAFS studies. The NacNac-Fe-MOF catalyst, I•Fe(Me), efficiently catalyzed the challenging intramolecular sp3 C–H amination of a series of alkyl azides to afford α-substituted pyrrolidines. The NacNac-Cu-MOF catalyst, I•Cu(THF), was effective in promoting the intermolecular sp3 C–H amination of cyclohexene using unprotected anilines to provide access to secondary amines in excellent selectivity. Finally, the NacNac-Co-MOF catalyst, I•Co(H), was used to catalyze alkene hydrogenation with turnover numbers (TONs) as high as 700 000. All of the NacNac-M-MOF catalysts were more effective than their analogous homogeneous catalysts and could be recycled and reused without a noticeable decrease in yield. The NacNac-MOFs thus provide a novel platform for engineering recyclable earth-abundant-element-based single-site solid catalysts for many important organic transformations.

  14. The interaction of diamines and polyamines with the peroxidase-catalyzed metabolism of aromatic amines: a potential mechanism for the modulation of aniline toxicity.

    PubMed

    Michail, Karim; Aljuhani, Naif; Siraki, Arno G

    2013-03-01

    Synthetic and biological amines such as ethylenediamine (EDA), spermine, and spermidine have not been previously investigated in free-radical biochemical systems involving aniline-based drugs or xenobiotics. We aimed to study the influence of polyamines in the modulation of aromatic amine radical metabolites in peroxidase-mediated free radical reactions. The aniline compounds tested caused a relatively low oxidation rate of glutathione in the presence of horseradish peroxidase (HRP), and H2O2; however, they demonstrated marked oxygen consumption when a polyamine molecule was present. Next, we characterized the free-radical products generated by these reactions using spin-trapping and electron paramagnetic resonance (EPR) spectrometry. Primary and secondary but not tertiary polyamines dose-dependently enhanced the N-centered radicals of different aniline compounds catalyzed by either HRP or myeloperoxidase, which we believe occurred via charge transfer intermediates and subsequent stabilization of aniline-derived radical species as suggested by isotopically labeled aniline. Aniline/peroxidase reaction product(s) were monitored at 435 nm by kinetic spectrophotometry in the presence and absence of a polyamine additive. Using gas chromatography-mass spectrometry, the dimerziation product of aniline, azobenzene, was significantly amplified when EDA was present. In conclusion, di- and poly-amines are capable of enhancing the formation of aromatic-amine-derived free radicals, a fact that is expected to have toxicological consequences.

  15. Regioselective Copper-Catalyzed Amination of Chlorobenzoic Acids: Synthesis and Solid-State Structures of N-Aryl Anthranilic Acid Derivatives

    PubMed Central

    Mei, Xuefeng; August, Adam T.; Wolf, Christian

    2008-01-01

    A chemo- and regioselective copper-catalyzed cross-coupling reaction for effective amination of 2-chlorobenzoic acids with aniline derivatives has been developed. The method eliminates the need for acid protection and produces a wide range of N-aryl anthranilic acid derivatives in up to 99%. The amination was found to proceed with both electron-rich and electron-deficient aryl chlorides and anilines and also utilizes sterically hindered anilines such as 2,6-dimethylaniline and 2-tert-butylaniline. The conformational isomerism of appropriately substituted N-aryl anthranilic acids has been investigated in the solid state. Crystallographic analysis of seven anthranilic acid derivatives showed formation of two distinct supramolecular architectures exhibiting trans-anti- and unprecedented trans-syn-dimeric structures. PMID:16388629

  16. Regioselective Synthesis of Quinazolinone-/Phenanthridine-Fused Heteropolycycles by Pd-Catalyzed Direct Intramolecular Aerobic Oxidative C-H Amination from Aromatic Strained Amides.

    PubMed

    Banerji, Biswadip; Bera, Suvankar; Chatterjee, Satadru; Killi, Sunil Kumar; Adhikary, Saswati

    2016-03-01

    A new route for the expedient synthesis of specific regioisomer of quinazolinone- and phenanthridine-fused heterocycles through a palladium-catalyzed regioselective intramolecular oxidative C-H amination from cyclic strained amides of aromatic amido-amidine systems (quinazolinones) has been developed. The amine functionalization of an aromatic C-H bond from a strained amide nitrogen involved in aromaticity has been a challenging work so far. The fusion of two heterocyclic cores, quinazolinone and phenanthridine, can occur in two different ways (linear and angular), but under the conditions reported here, only linear type isomer is exclusively produced. This approach provides a variety of substituted quinazolinone- and phenanthridine-fused derivatives in moderate to excellent yields. Moreover, such fused molecules show excellent fluorescent properties and have great potential to be a new type of fluorophores for the use in medicinal and material science.

  17. Copper-catalyzed amination of (bromophenyl)ethanolamine for a concise synthesis of aniline-containing analogues of NMDA NR2B antagonist ifenprodil.

    PubMed

    Bouteiller, Cédric; Becerril-Ortega, Javier; Marchand, Patrice; Nicole, Olivier; Barré, Louisa; Buisson, Alain; Perrio, Cécile

    2010-03-07

    An operationally simple and concise synthesis of anilinoethanolamines, as NMDA NR2B receptor antagonist ifenprodil analogues, was developed via a copper-catalyzed amination of the corresponding bromoarene. Coupling was achieved with linear primary alkylamines, alpha,omega-diamines, hexanolamine and benzophenone imine, as well as with aqueous ammonia, in good yields using CuI and N,N-diethylsalicylamide, 2,4-pentadione or 2-acetylcyclohexanone as catalytic systems. Amination with ethylene diamine was efficient even in the absence of an additive ligand, whereas no reaction occurred with ethanolamine whatever the conditions used. The anilinoethanolamines were evaluated as NR2B receptor antagonists in a functional inhibition assay. Aminoethylanilines displayed inhibition effects close to that of ifenprodil.

  18. Ir-catalyzed allylic amination/ring-closing metathesis: a new route to enantioselective synthesis of cyclic beta-amino alcohol derivatives.

    PubMed

    Lee, Jun Hee; Shin, Seunghoon; Kang, Jahyo; Lee, Sang-gi

    2007-09-14

    Ir-catalyzed allylic aminations of (E)-4-benzyloxy-2-butenyl methyl carbonate with benzylamine using Feringa's (Sa,Sc,Sc)-phosphoramidite as a chiral ligand afforded linear-aminated achiral product N,O-dibenzyl-4-amino-2-buten-1-ol regioselectively (linear/branched = >99/1), whereas the (E)-5-benzyloxy-2-pentenyl methyl carbonate showed completely opposite regioselectivity (linear/branched = >1/99) and afforded the optically active (3R)-N,O-dibenzylated 3-amino-1-penten-5-ol with very high enantioselectivity (96% ee), which was used as a key intermediate for the effective synthesis of various cyclic beta-amino alcohol derivatives through ring-closing metathesis in high yields.

  19. Amine-functionalized monodispersed porous silica microspheres with enhanced CO2 adsorption performance and good cyclic stability.

    PubMed

    Le, Yao; Guo, Daipeng; Cheng, Bei; Yu, Jiaguo

    2013-10-15

    Carbon dioxide capture using solid adsorbent has caused more and more attention in the world. Herein, amine-functionalized monodispersed porous silica microspheres (MPSM) were prepared by the hydrolysis and condensation of tetraethoxysilane (TEOS) in a water-ethanol-dodecylamine mixed solution, then calcined at 600°C, and finally functionalized with tetraethylenepentamine (TEA). The CO2 adsorption performance of the prepared samples was measured using a Chemisorb 2720 pulse chemisorption system (Micromeritics, USA). The results showed that the specific surface area and pore volume of the 600°C-calcined SiO2 microspheres reached 921m(2)/g and 0.48cm(3)/g, respectively. All the TEA-functionalized samples exhibited good CO2 adsorption performance, which were related to the amount of loaded TEA, adsorption temperatures, and the specific surface areas of the prepared samples. An optimal TEA loading amount (34wt%) and adsorption temperature (75°C) were determined. The maximum CO2 adsorption amount (4.27mmolg(-1) adsorbent) was achieved on the 600°C-calcined SiO2 microsphere sample with TEA loading of 34wt%. Repeated adsorption/desorption cycle experiments revealed that the TEA-functionalized SiO2 microspheres were good CO2 adsorbents exhibiting excellent cyclic stability.

  20. Synthesis of silica chemically bonded with poly(ethylene oxide) 4-arm, amine-terminated for copper cation removal.

    PubMed

    Kurczewska, Joanna; Schroeder, Grzegorz

    2010-12-01

    Chemically modified silica containing a poly(ethylene oxide) 4-arm, amine-terminated unit has been obtained in the multi-step synthesis. The synthesized material was characterized by elemental, thermogravimetric analysis and infrared spectroscopy. The surface morphology was analyzed by scanning electron microscopy. The support studied was applied for selective extraction of copper(II) [Cu(II)] from water solutions. The influence of different parameters (pH, amount of the support studied, and contact time) on the copper extraction was investigated. At the optimum conditions, the copper extraction was approximately 90%, significantly greater than that of the other coexisting ions--nickel(II) [Ni(II)], cobalt(II) [Co(II)], and manganese(II) [Mn(II)]. The exception was calcium(II) [Ca(II)], which reached 30% of the extraction percentage. The solid support retained its properties after treatment with different organic and inorganic solvents. The recovery of adsorbed Cu(II) ions was approximately 97%. The sorbent studied can be applied effectively for the pre-concentration of a low level of Cu(II) in the different water samples.

  1. In situ infrared study of the role of PEG in stabilizing silica-supported amines for CO(2) capture.

    PubMed

    Tanthana, Jak; Chuang, Steven S C

    2010-08-23

    The CO(2) capture capacity, adsorption mechanism, and degradation characteristics of two sorbents, silica-supported tetraethylenepentamine (TEPA/SiO(2)) and polyethylene-glycol-modified TEPA/SiO(2) (PEG/TEPA/SiO(2)), are studied by diffuse reflectance infrared Fourier transform spectroscopy and mass spectrometry. The CO(2) capture capacities of TEPA/SiO(2) and PEG/TEPA/SiO(2) are determined to be 2087 and 1110 micromol CO(2) g(-1) sorbent, respectively. Both sorbents adsorb CO(2) as hydrogen-bonding species, NH(2)--O, and carbamate/carboxylate species. The CO(2) adsorption half-time increases with the number of CO(2) capture cycles. Infrared results suggest that the increased adsorption half-time is a result of diffusion limitation, caused by accumulation of TEPA and PEG species on the surface of the sorbent particles. The degradation of TEPA/SiO(2) is found to correlate with the accumulation of carboxylate/carbamic species. The addition of PEG decreases the degradation rate of the sorbent and slows down the formation of carboxylate species. These carboxylate species can block CO(2) capture on amine (NH(2)/NH) sites. The stabilizing role of PEG on TEPA/SiO(2) can be attributed to hydrogen-bonding between TEPA (NH(2)/NH)and PEG (OH).

  2. Platinum-Catalyzed Friedel-Crafts-Type C-H Coupling-Allylic Amination Cascade to Synthesize 3,4-Fused Tricyclic Indoles.

    PubMed

    Suzuki, Yuta; Tanaka, Yuito; Nakano, Shun-ichi; Dodo, Kosuke; Yoda, Natsumi; Shinohara, Ken-Ichi; Kita, Kazuko; Kaneda, Atsushi; Sodeoka, Mikiko; Hamada, Yasumasa; Nemoto, Tetsuhiro

    2016-03-18

    A novel platinum-catalyzed cascade cyclization reaction was developed by intramolecular Friedel-Crafts-type C-H coupling of aniline derivatives with a propargyl carbonate unit-allylic amination sequence. Treatment of various propargyl carbonates tethered to meta-aniline derivatives with a Pt(dba)3/DPEphos catalyst system afforded the corresponding 3,4-fused tricyclic 3-alkylidene indolines in 42-99% yield, which were transformed into 3,4-fused indole derivatives by reaction with trifluoroacetic acid. The reaction products exhibited antiproliferative activities against cancer cells, but not normal cells, revealing the potential usefulness of this reaction for medicinal chemistry.

  3. Acid synthesis of luminescent amine-functionalized or erbium-doped silica spheres for biological applications.

    PubMed

    Enrichi, Francesco; Trave, Enrico; Bersani, Marco

    2008-03-01

    In this work we discuss and investigate the morphological and optical properties of luminescent silica spheres which can have interesting applications in bioimaging and biosensing. The spheres are synthesized following an acid route by the hydrolysis and condensation of tetraethylortosilicate (TEOS) and can be functionalized by incorporation of aminopropyl-triethoxysilane (APTES) during the synthesis, inducing a significant luminescence that can be attributed to a recombination mechanism from localized organic defects related to -NH(2) groups. It is shown that the acid synthesis route produces very regular spherical particles, but their diameter vary in the range of 200-4,000 nm. The luminescence properties have been investigated and optimized by variation of the annealing temperature for the functionalized spheres, obtaining the most efficient PL emission after a thermal treatment of 1 h at 600 degrees C in air. Moreover, the possibility to introduce rare earths like erbium in the spheres was also studied and the corresponding Er(3) luminescence emission at 1.53 microm is reported in terms of intensity and lifetime, pointing out that erbium can be easily and efficiently incorporated during the acid synthesis giving high PL intensity with a good lifetime of 3.9 ms.

  4. Amine-Impregnated Mesoporous Silica Nanotube as an Emerging Nanocomposite for CO2 Capture.

    PubMed

    Niu, Mengya; Yang, Huaming; Zhang, Xiangchao; Wang, Yutang; Tang, Aidong

    2016-07-13

    Pristine halloysite nanotubes (HNTs) were pretreated to produce mesoporous silica nanotubes (MSiNTs), which was further impregnated with polyethenimine (PEI) to prepare an emerging nanocomposite MSiNTs/PEI (MP) for CO2 capture. Thermogravimetric analysis (TGA) was employed to analyze the influences of PEI loading amount and adsorption temperature on CO2 adsorption capacity of the nanocomposite. The Brunauer-Emmett-Teller (BET) surface area (SBET) of MSiNTs was six times higher than that of HNTs, and the corresponding pore volume was more than two times higher than that of HNTs. The well dispersion of PEI within the nanotubes of MSiNTs benefits more CO2 gas adsorption, and the adsorption capacity of the nanocomposite could reach 2.75 mmol/g at 85 °C for 2 h. The CO2 adsorption on the nanocomposite was demonstrated to occur via a two-stage process: initially, a sharp linear weight increase at the beginning, and then a relatively slow adsorption step. The adsorption capacity could reach as high as 70% within 2 min. Also, the nanocomposite exhibited good stability on CO2 adsorption/desorption performance, indicating that the as-prepared emerging nanocomposite show an interesting application potential in the field of CO2 capture.

  5. The role of hydroxyl group acidity on the activity of silica-supported secondary amines for the self-condensation of n-butanal.

    PubMed

    Shylesh, Sankaranarayanapillai; Hanna, David; Gomes, Joseph; Canlas, Christian G; Head-Gordon, Martin; Bell, Alexis T

    2015-02-01

    The catalytic activity of secondary amines supported on mesoporous silica for the self-condensation of n-butanal to 2-ethylhexenal can be altered significantly by controlling the Brønsted acidity of M--OH species present on the surface of the support. In this study, M--OH (M=Sn, Zr, Ti, and Al) groups were doped onto the surface of SBA-15, a mesoporous silica, prior to grafting secondary propyl amine groups on to the support surface. The catalytic activity was found to depend critically on the synthesis procedure, the nature and amount of metal species introduced and the spatial separation between the acidic sites and amine groups. DFT analysis of the reaction pathway indicates that, for weak Brønsted acid groups, such as Si--OH, the rate-limiting step is C--C bond formation, whereas for stronger Brønsted acid groups, such as Ti and Al, hydrolysis of iminium species produced upon C--C bond formation is the rate-limiting step. Theoretical analysis shows further that the apparent activation energy decreases with increasing Brønsted acidity of the M--OH groups, consistent with experimental observation.

  6. Enhanced CO2 adsorption over polymeric amines supported on heteroatom-incorporated SBA-15 silica: impact of heteroatom type and loading on sorbent structure and adsorption performance.

    PubMed

    Kuwahara, Yasutaka; Kang, Dun-Yen; Copeland, John R; Bollini, Praveen; Sievers, Carsten; Kamegawa, Takashi; Yamashita, Hiromi; Jones, Christopher W

    2012-12-21

    Silica supported amine materials are promising compositions that can be used to effectively remove CO(2) from large stationary sources, such as flue gas generated from coal-fired power plants (ca. 10 % CO(2)) and potentially from ambient air (ca. 400 ppm CO(2)). The CO(2) adsorption characteristics of prototypical poly(ethyleneimine)-silica composite adsorbents can be significantly enhanced by altering the acid/base properties of the silica support by heteroatom incorporation into the silica matrix. In this study, an array of poly(ethyleneimine)-impregnated mesoporous silica SBA-15 materials containing heteroatoms (Al, Ti, Zr, and Ce) in their silica matrices are prepared and examined in adsorption experiments under conditions simulating flue gas (10 % CO(2) in Ar) and ambient air (400 ppm CO(2) in Ar) to assess the effects of heteroatom incorporation on the CO(2) adsorption properties. The structure of the composite adsorbents, including local information concerning the state of the incorporated heteroatoms and the overall surface properties of the silicate supports, are investigated in detail to draw a relationship between the adsorbent structure and CO(2) adsorption/desorption performance. The CO(2) adsorption/desorption kinetics are assessed by thermogravimetric analysis and in situ FT-IR measurements. These combined results, coupled with data on adsorbent regenerability, demonstrate a stabilizing effect of the heteroatoms on the poly(ethyleneimine), enhancing adsorbent capacity, adsorption kinetics, regenerability, and stability of the supported aminopolymers over continued cycling. It is suggested that the CO(2) adsorption performance of silica-aminopolymer composites may be further enhanced in the future by more precisely tuning the acid/base properties of the support.

  7. Esterification of fatty acid catalyzed by hydrothermally stable propylsulfonic acid-functionalized mesoporous silica SBA-15.

    PubMed

    Mar, Win Win; Somsook, Ekasith

    2013-01-01

    Propylsulfonic acid-functionalized mesoporous silica SBA-15 has been synthesized via one-step strategy at 130°C based on the co-condensation of TEOS and MPTMS in the presence of Pluronic 123 polymer and H₂O₂ in HCl aqueous solution. The synthesized solid exhibited hydrothermal stability in boiling water without significant change in textural properties. The catalytic performance of the synthesized solid was studied in the esterification of oleic acid with methanol. The experimental results revealed that the large mesopore structures of SBA-15-PrSO₃H solid synthesized at 130°C could favor a facile access of oleic acid to the acid sites, making the comparable activity to that of phenyl ethyl sulfonic acid functionalized silica and higher than that of dry amberlyst-15.

  8. Extrusion polymerization: catalyzed synthesis of crystalline linear polyethylene nanofibers within a mesoporous silica

    PubMed

    Kageyama; Tamazawa; Aida

    1999-09-24

    Crystalline nanofibers of linear polyethylene with an ultrahigh molecular weight (6,200,000) and a diameter of 30 to 50 nanometers were formed by the polymerization of ethylene with mesoporous silica fiber-supported titanocene, with methylalumoxane as a cocatalyst. Small-angle x-ray scattering analysis indicated that the polyethylene fibers consist predominantly of extended-chain crystals. This observation indicates a potential utility of the honeycomb-like porous framework as an extruder for nanofabrication of polymeric materials.

  9. Amine-tethered adsorbents based on three-dimensional macroporous silica for CO(2) capture from simulated flue gas and air.

    PubMed

    Liu, Fa-Qian; Wang, Lei; Huang, Zhao-Ge; Li, Chao-Qin; Li, Wei; Li, Rong-Xun; Li, Wei-Hua

    2014-03-26

    New covalently tethered CO2 adsorbents are synthesized through the in situ polymerization of N-carboxyanhydride (NCA) of l-alanine from amine-functionalized three-dimensional (3D) interconnected macroporous silica (MPS). The interconnected macropores provide low-resistant pathways for the diffusion of CO2 molecules, while the abundant mesopores ensure the high pore volume. The adsorbents exhibit high molecular weight (of up to 13058 Da), high amine loading (more than 10.98 mmol N g(-1)), fast CO2 capture kinetics (t1/2 < 1 min), high adsorption capacity (of up to 3.86 mmol CO2 g(-1) in simulated flue gas and 2.65 mmol CO2 g(-1) in simulated ambient air under 1 atm of dry CO2), as well as good stability over 120 adsorption-desorption cycles, which allows the overall CO2 capture process to be promising and sustainable.

  10. Aniline-catalyzed reductive amination as a powerful method for the preparation of reducing end-"clickable" chitooligosaccharides.

    PubMed

    Guerry, Alexandre; Bernard, Julien; Samain, Eric; Fleury, Etienne; Cottaz, Sylvain; Halila, Sami

    2013-04-17

    Functionalized oligosaccharides are useful intermediates to prepare products for biological research or for the development of advanced functional materials. Here, we report the unprecedented use of aniline as an efficient organocatalyst reaction with "clickable" (azide or alkyne) amine for the transimination-mediated reductive amination of a chitooligosaccharide. Moreover, we demonstrate that alkyne-bearing aniline constitutes an excellent tool for the easy derivatization of chitosan oligosaccharides. Evidence for such improvement has been illustrated by the straightforward design of a FRET substrate to probe chitinase activity and of amphiphilic polycaprolactone-grafted-chitosan. This efficient methodology paves the way to the preparation of novel chitosan oligosaccharide-based advanced materials.

  11. Functional-Group-Tolerant, Silver-Catalyzed N-N Bond Formation by Nitrene Transfer to Amines.

    PubMed

    Maestre, Lourdes; Dorel, Ruth; Pablo, Óscar; Escofet, Imma; Sameera, W M C; Álvarez, Eleuterio; Maseras, Feliu; Díaz-Requejo, M Mar; Echavarren, Antonio M; Pérez, Pedro J

    2017-02-15

    Silver(I) promotes the highly chemoselective N-amidation of tertiary amines under catalytic conditions to form aminimides by nitrene transfer from PhI═NTs. Remarkably, this transformation proceeds in a selective manner in the presence of olefins and other functional groups without formation of the commonly observed aziridines or C-H insertion products. The methodology can be applied not only to rather simple tertiary amines but also to complex natural molecules such as brucine or quinine, where the products derived from N-N bond formation were exclusively formed. Theoretical mechanistic studies have shown that this selective N-amidation reaction proceeds through triplet silver nitrenes.

  12. Soluble B-N polymers: poly(alpha-olefin) analogs via metal complex-catalyzed amine borane dehydrogenation

    SciTech Connect

    Pons, Vincent; Baker, R Tom

    2008-01-01

    Over the last few decades, catalytic dehydrocoupling has evolved from a mechanistically interesting chemical transformation to a practical route to inorganic polymers that have shown utility as new materials and processable ceramic precursors. In attempting to make new B-P and B-N inorganic polymers, Manners et al studied the heteronuclear dehydrocoupling of phosphine boranes and amine boranes. While the former gave high polymers such as (PhHP-BH2), evaluation of a variety of catalysts with primary and secondary amine boranes or even ammonia borane lead only to B-N cyclic oligomers. However, using an iridium phosphinito pincer complex originally employed by Goldberg and Heinekey6 for dehydrogenation of ammonia borane (AB, H3N-BH3), M3.nners now reports formation of soluble aminoborane polymers and copolymers derived from primary amine boranes (Scheme 1) With this report, an analogy is made between primary amine boranes and {alpha}-olefins. The prospects of tuning metal complex catalysts for control of B-N polymer microstructure are exciting for synthesis of new B-N materials. In addition, variation of the N substituent offers promise for processable precllISors to carbon-free B-N ceramics.

  13. Asymmetric Synthesis of α-Branched Amines via Rh(III)-Catalyzed C–H Bond Functionalization

    PubMed Central

    2015-01-01

    The first asymmetric intermolecular addition of non-acidic C–H bonds to imines is reported. The use of the activating N-perfluorobutanesulfinyl imine substituent is essential for achieving sufficient reactivity and provides outstanding diastereoselectivity (>98:2 dr). Straightforward removal of the sulfinyl group with HCl yields the highly enantiomerically enriched amine hydrochlorides. PMID:24901217

  14. Chiral Cu(salen)-Based Metal-Organic Framework for Heterogeneously Catalyzed Aziridination and Amination of Olefins.

    PubMed

    Liu, Yan; Li, Zijian; Yuan, Guozan; Xia, Qingchun; Yuan, Chen; Cui, Yong

    2016-12-19

    A homochiral 3D porous metal-organic framework was assembled from a chiral dicarboxylic acid-functionalized Cu(salen)-based catalyst and could serve as an efficient heterogeneous catalyst for aziridination and allylic amination of olefins. Besides easy separation and reuse of the catalyst, the chiral framework confinement could impart substrate size selectivity, enhance catalyst activity, and induce product enantioselectivity.

  15. MICROWAVE-ASSISTED CU (I) CATALYZED SOLVENT-FREE THREE COMPONENT COUPLING OF ALDEHYDE, ALKYNE AND AMINE

    EPA Science Inventory

    Direct Grignard type addition of terminal alkynes to in situ generated imines, from aldehydes and amines, occurs under microwave irradiation using CuBr alone in a one-pot operation. This solventless approach provides ready access to propargylamines and is applicable both...

  16. Visible-Light-Catalyzed Direct Benzylic C(sp(3))-H Amination Reaction by Cross-Dehydrogenative Coupling.

    PubMed

    Pandey, Ganesh; Laha, Ramkrishna

    2015-12-01

    A conceptually new and synthetically valuable cross-dehydrogenative benzylic C(sp(3))-H amination reaction is reported by visible-light photoredox catalysis. This protocol employs DCA (9,10-dicyanoanthracene) as a visible-light-absorbing photoredox catalyst and an amide as the nitrogen source without the need of either a transition metal or an external oxidant.

  17. Organoselenium-catalyzed, hydroxy-controlled regio- and stereoselective amination of terminal alkenes: efficient synthesis of 3-amino allylic alcohols.

    PubMed

    Deng, Zhimin; Wei, Jialiang; Liao, Lihao; Huang, Haiyan; Zhao, Xiaodan

    2015-04-17

    An efficient route to prepare 3-amino allylic alcohols in excellent regio- and stereoselectivity in the presence of bases by orangoselenium catalysis has been developed. In the absence of bases α,β-unsaturated aldehydes were formed in up to 97% yield. Control experiments reveal that the hydroxy group is crucial for the direct amination.

  18. Bifunctional heterogeneous catalysis of silica-alumina-supported tertiary amines with controlled acid-base interactions for efficient 1,4-addition reactions.

    PubMed

    Motokura, Ken; Tanaka, Satoka; Tada, Mizuki; Iwasawa, Yasuhiro

    2009-10-19

    We report the first tunable bifunctional surface of silica-alumina-supported tertiary amines (SA-NEt(2)) active for catalytic 1,4-addition reactions of nitroalkanes and thiols to electron-deficient alkenes. The 1,4-addition reaction of nitroalkanes to electron-deficient alkenes is one of the most useful carbon-carbon bond-forming reactions and applicable toward a wide range of organic syntheses. The reaction between nitroethane and methyl vinyl ketone scarcely proceeded with either SA or homogeneous amines, and a mixture of SA and amines showed very low catalytic activity. In addition, undesirable side reactions occurred in the case of a strong base like sodium ethoxide employed as a catalytic reagent. Only the present SA-supported amine (SA-NEt(2)) catalyst enabled selective formation of a double-alkylated product without promotions of side reactions such as an intramolecular cyclization reaction. The heterogeneous SA-NEt(2) catalyst was easily recovered from the reaction mixture by simple filtration and reusable with retention of its catalytic activity and selectivity. Furthermore, the SA-NEt(2) catalyst system was applicable to the addition reaction of other nitroalkanes and thiols to various electron-deficient alkenes. The solid-state magic-angle spinning (MAS) NMR spectroscopic analyses, including variable-contact-time (13)C cross-polarization (CP)/MAS NMR spectroscopy, revealed that acid-base interactions between surface acid sites and immobilized amines can be controlled by pretreatment of SA at different temperatures. The catalytic activities for these addition reactions were strongly affected by the surface acid-base interactions.

  19. Self-encapsulation of homogeneous catalyst species into polymer gel leading to a facile and efficient separation system of amine products in the Ru-catalyzed reduction of carboxamides with polymethylhydrosiloxane (PMHS).

    PubMed

    Motoyama, Yukihiro; Mitsui, Kaoru; Ishida, Toshiki; Nagashima, Hideo

    2005-09-28

    A practical procedure for production of amines is offered by the ruthenium-catalyzed reduction of carboxamides with polymethylhydrosiloxane, in which encapsulation of the catalyst species into the formed insoluble siloxane resins contributes to the separation of both metallic and siloxane residues from the product.

  20. Amine-free reversible hydrogen storage in formate salts catalyzed by ruthenium pincer complex without pH control or solvent change.

    PubMed

    Kothandaraman, Jotheeswari; Czaun, Miklos; Goeppert, Alain; Haiges, Ralf; Jones, John-Paul; May, Robert B; Prakash, G K Surya; Olah, George A

    2015-04-24

    Due to the intermittent nature of most renewable energy sources, such as solar and wind, energy storage is increasingly required. Since electricity is difficult to store, hydrogen obtained by electrochemical water splitting has been proposed as an energy carrier. However, the handling and transportation of hydrogen in large quantities is in itself a challenge. We therefore present here a method for hydrogen storage based on a CO2 (HCO3 (-) )/H2 and formate equilibrium. This amine-free and efficient reversible system (>90 % yield in both directions) is catalyzed by well-defined and commercially available Ru pincer complexes. The formate dehydrogenation was triggered by simple pressure swing without requiring external pH control or the change of either the solvent or the catalyst. Up to six hydrogenation-dehydrogenation cycles were performed and the catalyst performance remained steady with high selectivity (CO free H2 /CO2 mixture was produced).

  1. Reaction of CO2 with propylene oxide and styrene oxide catalyzed by a chromium(III) amine-bis(phenolate) complex.

    PubMed

    Dean, Rebecca K; Devaine-Pressing, Katalin; Dawe, Louise N; Kozak, Christopher M

    2013-07-07

    A diamine-bis(phenolate) chromium(III) complex, {CrCl[O2NN'](BuBu)}2 catalyzes the copolymerization of propylene oxide with carbon dioxide. The synthesis of this metal complex is straightforward and it can be obtained in high yields. This catalyst incorporates a tripodal amine-bis(phenolate) ligand, which differs from the salen or salan ligands typically used with Cr and Co complexes that have been employed as catalysts for the synthesis of such polycarbonates. The catalyst reported herein yields low molecular weight polymers with narrow polydispersities when the reaction is performed at room temperature. Performing the reaction at elevated temperatures causes the selective synthesis of propylene carbonate. The copolymerization activity for propylene oxide and carbon dioxide, as well as the coupling of carbon dioxide and styrene oxide to give styrene carbonate are presented.

  2. Selective iridium-catalyzed alkylation of (hetero)aromatic amines and diamines with alcohols under mild reaction conditions.

    PubMed

    Blank, Benoît; Michlik, Stefan; Kempe, Rhett

    2009-01-01

    A P,N-ligand-coordinated iridium complex has been employed as an efficient catalyst for the selective monoalkylation of (hetero)aromatic amines with alcohols. A significant improvement of this alkylation method has been achieved, such that it can be performed at a temperature of 70 degrees C and with catalyst loadings as low as 0.1 mol % Ir, while still affording excellent yields of secondary amines. Furthermore, the high selectivity of this catalyst for the monoalkylation of aromatic amino functions has been successfully exploited for the alkylation of diamines in both symmetric and nonsymmetric fashions, providing a novel and very efficient synthetic tool for the preparation of N,N'-dialkylated aromatic diamines.

  3. Highly enantioselective direct Michael addition of nitroalkanes to nitroalkenes catalyzed by amine-thiourea bearing multiple hydrogen-bonding donors.

    PubMed

    Dong, Xiu-Qin; Teng, Huai-Long; Wang, Chun-Jiang

    2009-03-19

    A highly diastereoselective and enantioselective Michael addition of nitroalkanes to nitroalkenes has been achieved by chiral bifunctional amine-thiourea catalyst bearing multiple hydrogen-bonding donors. This catalytic system performs well over a broad scope of substrates, furnishing various 1,3-dinitro compounds in high diastereoselectivity (up to 98:2) and excellent enantioselectivity (up to 99% ee) under mild conditions. Multiple hydrogen bonding donors play a significant role in accelerating reactions, improving diastereoselectivities and enantioselectivities.

  4. Chemoenzymatic dynamic kinetic resolution of primary amines catalyzed by CAL-B at 38-40 °C.

    PubMed

    Poulhès, Florent; Vanthuyne, Nicolas; Bertrand, Michèle P; Gastaldi, Stéphane; Gil, Gérard

    2011-09-02

    The (R)-selective chemoenzymatic dynamic kinetic resolution of primary amines was performed at 38-40 °C in MTBE, in good to high yields and with high enantiomeric excesses. These reactions associating CAL-B to octanethiol as radical racemizing agent were carried out in the presence of methyl β-methoxy propanoate as acyl donor, under photochemical irradiation at 350 nm in glassware.

  5. Dipeptide-Based Chiral Tertiary Amine-Catalyzed Asymmetric Conjugate Addition Reactions of 5H-Thiazol/Oxazol-4-Ones.

    PubMed

    Li, Jiangtao; Qiu, Shuai; Ye, Xinyi; Zhu, Bo; Liu, Hongjun; Jiang, Zhiyong

    2016-12-02

    Highly enantio- and chemo-selective 1,4-conjugate addition process of 5H-thiazol-4-ones with maleimides or 1,4-naphthoquinones, and 5H-oxazol-4-ones with maleimides were performed under a dipeptide-based tertiary amine (DP-UAA) catalyst. A series of valuable N,S- and N,O-containing heterocyclic compounds with excellent enantio- and disastereo-selectivities (up to >99% ee, > 20:1 dr) were attained.

  6. Palladium-catalyzed C-H activation/intramolecular amination reaction: a new route to 3-aryl/alkylindazoles.

    PubMed

    Inamoto, Kiyofumi; Saito, Tadataka; Katsuno, Mika; Sakamoto, Takao; Hiroya, Kou

    2007-07-19

    A method for the catalytic C-H activation of hydrazone compounds followed by intramolecular amination is described. It requires the use of a catalytic amount of Pd(OAc)2 in the presence of Cu(OAc)2 and AgOCOCF3, which efficiently effects the cyclization to afford variously substituted indazoles. The reactions proceed under relatively mild conditions and thus tolerate a variety of functional groups, including alkoxycarbonyl and cyano groups and halogen atoms.

  7. Palladium-catalyzed one-pot three- or four-component coupling of aryl iodides, alkynes, and amines through C-N bond cleavage: efficient synthesis of indole derivatives.

    PubMed

    Hao, Wei; Geng, Weizhi; Zhang, Wen-Xiong; Xi, Zhenfeng

    2014-02-24

    An efficient synthesis of N-substituted indole derivatives was realized by combining the Pd-catalyzed one-pot multicomponent coupling approach with cleavage of the C(sp(3))-N bonds. Three or four components of aryl iodides, alkynes, and amines were involved in this coupling process. The cyclopentadiene-phosphine ligand showed high efficiency. A variety of aryl iodides, including cyclic and acyclic tertiary amino aryl iodides, and substituted 1-bromo-2-iodobenzene derivatives could be used. Both symmetric and unsymmetric alkynes substituted with alkyl, aryl, or trimethylsilyl groups could be applied. Cyclic secondary amines such as piperidine, morpholine, 4-methylpiperidine, 1-methylpiperazine, 2-methylpiperidine, and acyclic amines including secondary and primary amines all showed good reactivity. Further application of the resulting indole derivatives was demonstrated by the synthesis of benzosilolo[2,3-b]indole.

  8. Generation of reactive species and fate of thiols during peroxidase-catalyzed metabolic activation of aromatic amines and phenols

    SciTech Connect

    Ross, D.; Moldeus, P.

    1985-12-01

    The horseradish peroxidase (HRP)-catalyzed oxidation of p-phenetidine and acetaminophen was investigated. Studies using the spin probe 2-ethyl-1-hydroxy-2,5,5-trimethyl-3-oxazolidine (OXANOH) suggested these oxidations involve the generation of substrate-derived free radicals. This was confirmed by using glutathione (GSH) in these incubations in the presence of the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), DMPO-glutathionyl radical adducts were observed using EPR spectroscopy during HRP-catalyzed oxidation of both p-phenetidine and acetaminophen. Investigations of oxygen uptake and oxidized glutathione (GSSG) formation during HRP-catalyzed oxidations of p-phenetidine and acetaminophen suggested that further reactions of the glutathionyl radical involve glutathione peroxysulfenyl radical and glutathione sulfenyl hydroperoxide production. Quinonoid products of the peroxidatic oxidations of p-phenetidine and acetaminophen, and their interaction with GSH via both conjugation and redox mechanisms are described. The relevance of these reactions of GSH with reactive species as detoxification mechanisms is discussed. 29 references.

  9. CYP-450 isoenzymes catalyze the generation of hazardous aromatic amines after reaction with the azo dye Sudan III.

    PubMed

    Zanoni, Thalita Boldrin; Lizier, Thiago M; Assis, Marilda das Dores; Zanoni, Maria Valnice B; de Oliveira, Danielle Palma

    2013-07-01

    This work describes the mutagenic response of Sudan III, an adulterant food dye, using Salmonella typhimurium assay and the generation of hazardous aromatic amines after different oxidation methods of this azo dye. For that, we used metabolic activation by S9, catalytic oxidation by ironporphyrin and electrochemistry oxidation in order to simulate endogenous oxidation conditions. The oxidation reactions promoted discoloration from 65% to 95% of Sudan III at 1 × 10(-4)molL(-1) and generation of 7.6 × 10(-7)molL(-1) to 0.31 × 10(-4)molL(-1) of aniline, o-anisidine, 2-methoxi-5-methylaniline, 4-aminobiphenyl, 4,4'-oxydianiline; 4,4'-diaminodiphenylmethane and 2,6-dimethylaniline. The results were confirmed by LC-MS-MS experiments. We also correlate the mutagenic effects of Sudan III using S. typhimurium with the strain TA1535 in the presence of exogenous metabolic activation (S9) with the metabolization products of this compound. Our findings clearly indicate that aromatic amines are formed due to oxidative reactions that can be promoted by hepatic cells, after the ingestion of Sudan III. Considering that, the use of azo compounds as food dyestuffs should be carefully controlled.

  10. Cloning and characterization of a new laccase from Lactobacillus plantarum J16 CECT 8944 catalyzing biogenic amines degradation.

    PubMed

    Callejón, S; Sendra, R; Ferrer, S; Pardo, I

    2016-04-01

    In our search for degrading activities of biogenic amines (BAs) in lactic acid bacteria, a protein annotated as laccase enzyme was identified in Lactobacillus plantarum J16 (CECT 8944). In this study, the gene of this new laccase was cloned and heterologously overexpressed in Escherichia coli. The recombinant laccase protein was purified and characterized biochemically. The purified laccase showed characteristic spectroscopic properties of blue multicopper oxidases. The enzyme has a molecular weight of ∼ 62.5 kDa and activity toward typical laccase substrates 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and 2,6-dimethoxyphenol (2,6-DMP). The pH optima on ABTS and 2,6-DMP were 3.5 and 7.0, respectively. Kinetic constants Km and Vmax were of 0.21 mM and 0.54 U/mg for ABTS and 1.67 mM and 0.095 U/mg for 2,6-DMP, respectively. The highest oxidizing activity toward 2,6-DMP was obtained at 60 °C. However, after a preincubation step at 85 °C for 10 min, no residual activity was detected. It has been demonstrated that recombinant L. plantarum laccase oxidizes biogenic amines, mainly tyramine, and thus presents new biotechnological potential for the enzyme in eliminating toxic compounds present in fermented food and beverages.

  11. Pd-catalyzed amination in the synthesis of a new family of macropolycyclic compounds comprising diazacrown ether moieties.

    PubMed

    Yakushev, Alexei A; Chernichenko, Nataliya M; Anokhin, Maxim V; Averin, Alexei D; Buryak, Alexei K; Denat, Franck; Beletskaya, Irina P

    2014-01-15

    N,N'-bis(bromobenzyl) and N,N'-bis(halopyridinyl) derivatives of diaza-12-crown-4, diaza-15-crown-5 and diaza-18-crown-6 ethers were synthesized in high yields. The Pd-catalyzed macrocyclization reactions of these compounds were carried out using a variety of polyamines and oxadiamines were carried out to give novel macrobicyclic and macrotricyclic compounds of the cryptand type. The dependence of the yields of macropolycycles on the nature of the starting diazacrown derivatives and polyamines was established. Generally N,N'-bis(3-bromobenzyl)-substituted diazacrown ethers and oxadiamines provided better yields of the target products. The highest yield of the macrobicyclic products reached 57%.

  12. Complementation of biotransformations with chemical C-H oxidation: copper-catalyzed oxidation of tertiary amines in complex pharmaceuticals.

    PubMed

    Genovino, Julien; Lütz, Stephan; Sames, Dalibor; Touré, B Barry

    2013-08-21

    The isolation, quantitation, and characterization of drug metabolites in biological fluids remain challenging. Rapid access to oxidized drugs could facilitate metabolite identification and enable early pharmacology and toxicity studies. Herein, we compared biotransformations to classical and new chemical C-H oxidation methods using oxcarbazepine, naproxen, and an early compound hit (phthalazine 1). These studies illustrated the low preparative efficacy of biotransformations and the inability of chemical methods to oxidize complex pharmaceuticals. We also disclose an aerobic catalytic protocole (CuI/air) to oxidize tertiary amines and benzylic CH's in drugs. The reaction tolerates a broad range of functionalities and displays a high level of chemoselectivity, which is not generally explained by the strength of the C-H bonds but by the individual structural chemotype. This study represents a first step toward establishing a chemical toolkit (chemotransformations) that can selectively oxidize C-H bonds in complex pharmaceuticals and rapidly deliver drug metabolites.

  13. Electrochemical Oxidation of H₂ Catalyzed by Ruthenium Hydride Complexes Bearing P₂N₂ Ligands With Pendant Amines as Proton Relays

    SciTech Connect

    Liu, Tianbiao L.; Rakowski DuBois, Mary; DuBois, Daniel L.; Bullock, R. Morris

    2014-01-01

    Two Ru hydride complexes (Cp*Ru(PPh₂NBn₂)H, (1-H) and Cp*Ru(PtBu₂NBn₂)H, (2-H) supported by cyclic PR₂NR'₂ ligands (Cp* = n⁵-C₅Me₅; 1,5-diaza-3,7-diphosphacyclooctane, where R = Ph or tBu and R' = Bn) have been synthesized and fully characterized. Both complexes are demonstrated to be electrocatalysts for oxidation of H₂ (1 atm, 22 °C) in the presence of external base, DBU (1,8-diazabicyclo[5.4.0]undec-7-ene). The turnover frequency of 2-H is 1.2 s-1, with an overpotential at Ecat/2 of 0.45 V, while catalysis by 1-H has a turnover frequency of 0.6 s-1 and an overpotential of 0.6 V at Ecat/2. Addition of H₂O facilitates oxidation of H₂ by 2-H and increases its turnover frequency to 1.9 s-1 while , H₂O slows down the catalysis by 1-H. The different effects of H₂O for 1-H and 2-H are ascribed to different binding affinities of H₂O to the Ru center of the corresponding unsaturated species, [Cp*Ru(PPh₂NBn₂)]+ and [Cp*Ru(PPh₂NBn₂)]+. In addition, studies of Cp*Ru(dmpm)H (where dmpm = bis(dimethylphosphino)methane), a control complex lacking pendent amines in its diphosphine ligand, confirms the critical roles of the pendent amines of P₂N₂ ligands for oxidation of H₂. We thank the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences, for supporting initial parts of the work. Current work is supported by the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  14. Enantioselective synthesis of syn/anti-1,3-amino alcohols via proline-catalyzed sequential alpha-aminoxylation/alpha-amination and Horner-Wadsworth-Emmons olefination of aldehydes.

    PubMed

    Jha, Vishwajeet; Kondekar, Nagendra B; Kumar, Pradeep

    2010-06-18

    A novel and general method for asymmetric synthesis of both syn/anti-1,3-amino alcohols is described. The method uses proline-catalyzed sequential alpha-aminoxylation/ alpha-amination and Horner-Wadsworth-Emmons (HWE) olefination of aldehydes as the key step. By using this method, a short synthesis of a bioactive molecule, (R)-1-((S)-1-methylpyrrolidin-2-yl)-5-phenylpentan-2-ol, is also accomplished.

  15. Structural changes of silica mesocellular foam supported amine-functionalized CO2 adsorbents upon exposure to steam.

    PubMed

    Li, Wen; Bollini, Praveen; Didas, Stephanie A; Choi, Sunho; Drese, Jeffrey H; Jones, Christopher W

    2010-11-01

    Three classes of amine-functionalized mesocellular foam (MCF) materials are prepared and evaluated as CO(2) adsorbents. The stability of the adsorbents under steam/air and steam/nitrogen conditions is investigated using a Parr autoclave reactor to simulate, in an accelerated manner, the exposure that such adsorbents will see under steam stripping regeneration conditions at various temperatures. The CO(2) capacity and organic content of all adsorbents decrease after steam treatment under both steam/air and steam/nitrogen conditions, primarily due to structural collapse of the MCF framework, but with additional contributions likely associated with amine degradation during treatment under harsh conditions. Treatment with steam/air is found to have stronger effect on the CO(2) capacity of the adsorbents compared to steam/nitrogen.

  16. Efficient alkene epoxidation catalyzed by molybdenyl acetylacetonate supported on aminated UiO-66 metal−organic framework

    SciTech Connect

    Kardanpour, Reihaneh; Tangestaninejad, Shahram; Mirkhani, Valiollah; Moghadam, Majid; Mohammadpoor-Baltork, Iraj; Zadehahmadi, Farnaz

    2015-03-15

    Metal–organic frameworks (MOFs) containing Mo Schiff base complexes were prepared by post-synthesis method and applied as efficient catalysts in the epoxidation of alkenes with tert-BuOOH. In this manner, UiO-66-NH{sub 2} (UiO=University of Oslo) MOF was reacted with salicylaldehyde and thiophene-2-carbaldehyde to produce bidentate Schiff bases. Then, the Schiff base ligands were used for immobilization of molybdenyl acetylacetonate. These new catalysts were characterized by FT-IR, UV–vis spectroscopic techniques, X-ray diffraction (XRD), BET, inductively coupled plasma atomic emission spectroscopy (ICP-AES) and field emission scanning electron microscopy (FE-SEM). These catalytic systems showed excellent activity in the epoxidation of alkenes such as cyclic and linear ones with tert-butyl hydroperoxide (TBHP) in 1,2-dichloroethane, and reused several times without any appreciable loss of their activity. - Graphical abstract: Efficient alkene epoxidation with TBHP catalyzed by heterogeneous and reusable molybdenum base catalysts is reported. - Highlights: • UiO-66-NH{sub 2} was modified with salicylaldehyde and thiophene-2-carbaldehyde. • The Schiff base groups were used for immobilization of MoO{sub 2}(acac){sub 2}. • The heterogeneous catalysts were prepared. • The prepared catalysts were used for epoxidation of alkenes. • Compared to other catalyst, our catalysts were more efficient and forceful.

  17. Effect of addition of silica- and amine functionalized silica-nanoparticles on the microstructure of calcium silicate hydrate (C-S-H) gel.

    PubMed

    Monasterio, Manuel; Gaitero, Juan J; Erkizia, Edurne; Guerrero Bustos, Ana M; Miccio, Luis A; Dolado, Jorge S; Cerveny, Silvina

    2015-07-15

    In this work we study the influence of adding nano-silica (SiO2, Nyasil™) and aminopropyl (-(CH2)3-NH2,) functionalized silica nanoparticles (Stoga) during the synthesis of calcium-silicate-hydrate (C-S-H gel). Characterization by solid state (29)Si NMR and ATR-FTIR spectroscopy showed that the addition of both particle types increases the average length of the silicate chains in C-S-H gel being this effect slightly more important in the case of Stoga particles. In addition, (13)C NMR and XPS confirmed that the aminopropyl chain remains in the final product cleaved to silicon atoms at the end of the silicate chain of C-S-H gel whereas XRD measurements showed that this result in an increment in the basal distance compared with ordinary CSH. In addition, the dynamics of water within the pores of C-S-H gel was analyzed by broadband dielectric spectroscopy. We observed that water confined in C-S-H formed with the addition of nanoparticles is faster than that in plain C-S-H which can be related to a different porous structure in these materials.

  18. Multifunctional mesoporous silica catalyst

    DOEpatents

    Lin, Victor Shang-Yi; Tsai, Chih-Hsiang; Chen, Hung-Ting; Pruski, Marek; Kobayashi, Takeshi

    2015-03-31

    The present invention provides bifunctional silica mesoporous materials, including mesoporous silica nanoparticles ("MSN"), having pores modified with diarylammonium triflate and perfluoroaryl moieties, that are useful for the acid-catalyzed esterification of organic acids with organic alcohols.

  19. Amine-bearing mesoporous silica for CO(2) and H(2)S removal from natural gas and biogas.

    PubMed

    Belmabkhout, Youssef; De Weireld, Guy; Sayari, Abdelhamid

    2009-12-01

    Triamine-grafted pore-expanded mesoporous silica (TRI-PE-MCM-41) exhibited high CO(2) and H(2)S adsorption capacity as well as high selectivity toward acid gases versus CH(4). Unlike physical adsorbents such as zeolites and activated carbons, the presence of moisture in the feed enhanced the CO(2) removal capability of TRI-PE-MCM-41 without altering its H(2)S adsorption capacity. Thus, depending on the feed composition, CO(2) and H(2)S may be removed over TRI-PE-MCM-41 simultaneously or sequentially. These findings are suitable for acid gas separation from CH(4)-containing mixtures such as natural gas and biogas.

  20. Silver nanoparticles deposited on amine-functionalized silica spheres and their amalgamation-based spectral and colorimetric detection of Hg(II) ions

    NASA Astrophysics Data System (ADS)

    Rameshkumar, Perumal; Manivannan, Shanmugam; Ramaraj, Ramasamy

    2013-05-01

    A facile synthetic method to decorate amine-functionalized silica spheres (SiO2) by silver nanoparticles (Ag NPs) is reported. The transmission electron microscopic (TEM) images showed that spherical Ag NPs with an average particle size of 14 nm were deposited on 250 nm-sized SiO2 spheres (SiO2/Ag NPs). The spectral and colorimetric detection of Hg(II) ions were carried out using the synthesized SiO2/Ag NPs with an experimental detection limit of 5 μM. It was found that the addition of Hg(II) ions (150 μM) into the solution of SiO2/Ag NPs completely quenched the SPR band of the Ag NPs due to the formation of anisotropic Ag amalgam crystals (AgHg). The selective detection of Hg(II) ions by SiO2/Ag NPs in the presence of other environmentally relevant metal ions was also demonstrated using spectral and colorimetric methods.

  1. Fluorescence and Textural Characterization of Ortho-Amine Tetraphenylporphyrin Covalently Bonded to Organo-Modified Silica Xerogels.

    PubMed

    García-Sánchez, M A; Serratos, I N; Sosa, R; Rojas-González, F; Tello-Solís, S R; Tapia-Esquivel, T; González-García, F; Esparza-Schulz, J M; Huerta-Figueroa, D E

    2016-09-01

    Most of the studies performed with porphyrins involve these species functionalized with peripheral substituents lying on the same macrocyclic molecular plane. The main objective of this work deals with the successful preservation and optimization of the fluorescence of a uncommonly used porphyrin species, i.e. tetrakis-(ortho-amino-phenyl)-porphyrin; a molecule with substituents localized not only at one but at both sides of its molecular plane. In cases like this, it must be stressed that fluorescence can only be partially preserved; nevertheless, intense fluorescence can still be reached by following a twofold functionalization strategy involving: (i) the bonding of substituted macrocycles to the pore walls of (ii) organo-modified silica monoliths synthesized by the sol-gel method. The analysis of both absorption and emission UV spectra evidenced a radiation energy transfer taking place between the porphyrin and the host silica matrix. Our results showed that the adequate displaying of the optical properties of macrocyclic species trapped in SiO2 xerogels depend on the polarity existing inside the pores, a property which can be tuned up through the adequate selection of organic groups used to modify the surface of the pore cavities. Additionally, the pore widths attained in the final xerogels can vary depending on the identity of the organic groups attached to the network. All these facts finally demonstrated that, even if using inefficient surface functionalization species, such as ortho-substituted tetraphenylporphyrins, it is still possible to modulate the pore shape, pore size, and physicochemical environment created around the trapped macrocycles. The most important aspect related to this research deals with the fact that the developed methodology offers a real possibility of controlling both the textural and morphological characteristics of a new kind of hybrid porous materials and to optimize the physicochemical properties of diverse active molecules

  2. Highly enantioselective reductive amination of simple aryl ketones catalyzed by Ir-f-Binaphane in the presence of titanium(IV) isopropoxide and iodine.

    PubMed

    Chi, Yongxiang; Zhou, Yong-Gui; Zhang, Xumu

    2003-05-16

    Using an Ir-f-Binaphane complex as the catalyst, complete conversions and high enantioselectivies (up to 96% ee) were achieved in the asymmetric reductive amination of aryl ketones in the presence of Ti(O(i)()Pr)(4) and I(2). A simple and efficient method of synthesizing chiral primary amines has been realized.

  3. Highly Reactive, General and Long-Lived Catalysts for Palladium-Catalyzed Amination of Heteroaryl and Aryl Chlorides, Bromides and Iodides: Scope and Structure-Activity Relationships

    PubMed Central

    Shen, Qilong; Ogata, Tokutaro; Hartwig, John F.

    2010-01-01

    We describe a systematic study of the scope and relationship between ligand structure and activity for a highly efficient and selective class of catalysts for the amination of heteroaryl and aryl chlorides, bromides and iodides containing sterically hindered chelating alkylphosphines. In the presence of this catalyst, aryl and heteroaryl chlorides, bromides and iodides react with many primary amines in high yields with part-per-million quantities of palladium precursor and ligand. Many reactions of primary amines with both heteroaryl and aryl chlorides, bromides and iodides occur to completion with 0.0005-0.05 mol % catalysts. A comparison of the reactivity of this catalyst for coupling of primary amines at these loadings is made with catalysts generated from hindered monophosphines and carbenes, and these data illustrate the benefits of chelation. Thus, these complexes constitute a fourth-generation catalyst for the amination of aryl halides, whose activity complements catalysts based on monophosphines and carbenes. PMID:18444639

  4. Oxidation of a mustard gas analogue using an aldehyde/O2 system catalyzed by V-doped mesoporous silica.

    PubMed

    Livingston, Stephanie R; Landry, Christopher C

    2008-10-08

    Vanadium-doped mesoporous silica was shown to be an effective heterogeneous catalyst for the oxidation of a mustard gas analogue, 2-chloroethyl ethyl sulfide (CEES), in the presence of an aldehyde and molecular oxygen. The oxidation was shown to involve a radical mechanism, which was indicated by the appearance of an induction period when the reaction occurred in the presence of a free radical scavenger. The reaction was initially selective for the oxidation of CEES to the sulfoxide, CEESO, although oxidation of the sulfoxide to the sulfone occurred once all the CEES had been oxidized. Chemical analysis indicated that V species did not leach from the silica support when the reaction was performed in the fluorinated solvent HFE-7100.

  5. Selective N-alkylation of amines using nitriles under hydrogenation conditions: facile synthesis of secondary and tertiary amines.

    PubMed

    Ikawa, Takashi; Fujita, Yuki; Mizusaki, Tomoteru; Betsuin, Sae; Takamatsu, Haruki; Maegawa, Tomohiro; Monguchi, Yasunari; Sajiki, Hironao

    2012-01-14

    Nitriles were found to be highly effective alkylating reagents for the selective N-alkylation of amines under catalytic hydrogenation conditions. For the aromatic primary amines, the corresponding secondary amines were selectively obtained under Pd/C-catalyzed hydrogenation conditions. Although the use of electron poor aromatic amines or bulky nitriles showed a lower reactivity toward the reductive alkylation, the addition of NH(4)OAc enhanced the reactivity to give secondary aromatic amines in good to excellent yields. Under the same reaction conditions, aromatic nitro compounds instead of the aromatic primary amines could be directly transformed into secondary amines via a domino reaction involving the one-pot hydrogenation of the nitro group and the reductive alkylation of the amines. While aliphatic amines were effectively converted to the corresponding tertiary amines under Pd/C-catalyzed conditions, Rh/C was a highly effective catalyst for the N-monoalkylation of aliphatic primary amines without over-alkylation to the tertiary amines. Furthermore, the combination of the Rh/C-catalyzed N-monoalkylation of the aliphatic primary amines and additional Pd/C-catalyzed alkylation of the resulting secondary aliphatic amines could selectively prepare aliphatic tertiary amines possessing three different alkyl groups. According to the mechanistic studies, it seems reasonable to conclude that nitriles were reduced to aldimines before the nucleophilic attack of the amine during the first step of the reaction.

  6. Synthesis of nearly enantiopure allylic amines by aza-Claisen rearrangement of Z-configured allylic trifluoroacetimidates catalyzed by highly active ferrocenylbispalladacycles.

    PubMed

    Jautze, Sascha; Seiler, Paul; Peters, René

    2008-01-01

    The development of the first highly active enantioselective catalyst for the aza-Claisen rearrangement of Z-configured allylic trifluoroacetimidates generating valuable almost enantiopure protected allylic amines is described. Usually Z-configured allylic imidates react significantly slower than their E-configured counterparts, but in the present study the opposite effect was observed. Z-Configured olefins have the principal practical advantage that a geometrically pure C=C double bond can be readily obtained, for example, by semihydrogenations of alkynes. Our catalyst, a C(2)-symmetric planar chiral bispalladacycle complex, is rapidly prepared from ferrocene in four simple steps. Key step of this protocol is an unprecedented highly diastereoselective biscyclopalladation providing dimeric macrocyclic complexes of fascinating structure. In the present study as little as 0.1 mol % of catalyst precursor were sufficient for most of the alkyl substituted substrates to give in general almost quantitative yields. NMR investigations revealed a monomeric structure for the active catalyst species. The bispalladacycle can also be used for the formation of almost enantiomerically pure allylic amines (ee > or =96 %) substituted with important functional groups such as ester, ketone, ether, silyl ether, acetal or protected amino moieties providing high-added-value allylic amine building blocks in excellent yield (> or =94 %). The preparative advantages should render this methodology highly appealing as a practical and valuable tool for the formation of allylic amines in target oriented synthesis.

  7. Immobilized Candida antarctica lipase B on ZnO nanowires/macroporous silica composites for catalyzing chiral resolution of (R,S)-2-octanol.

    PubMed

    Shang, Chuan-Yang; Li, Wei-Xun; Zhang, Rui-Feng

    2014-01-01

    ZnO nanowires were successfully introduced into a macroporous SiO2 by in situ hydrothermal growth in 3D pores. The obtained composites were characterized by SEM and XRD, and used as supports to immobilize Candida antarctica lipase B (CALB) through adsorption. The high specific surface area (233 m(2)/g) and strong electrostatic interaction resulted that the average loading amount of the composite supports (196.8 mg/g) was 3-4 times of that of macroporous SiO2 and approximate to that of a silica-based mesoporous material. Both adsorption capacity and the activity of the CALB immobilized on the composite supports almost kept unchanged as the samples were soaked in buffer solution for 48 h. The chiral resolution of 2-octanol was catalyzed by immobilized CALB. A maximum molar conversion of 49.1% was achieved with 99% enantiomeric excess of (R)-2-octanol acetate under the optimal condition: a reaction using 1.0 mol/L (R,S)-2-octanol, 2.0 mol/L vinyl acetate and 4.0 wt.% water content at 60°C for 8h. After fifteen recycles the immobilized lipase could retain 96.9% of relative activity and 93.8% of relative enantioselectivity.

  8. Towards the design of organocatalysts for nerve agents remediation: The case of the active hydrolysis of DCNP (a Tabun mimic) catalyzed by simple amine-containing derivatives.

    PubMed

    Barba-Bon, Andrea; Martínez-Máñez, Ramón; Sancenón, Félix; Costero, Ana M; Gil, Salvador; Pérez-Pla, Francisco; Llopis, Elisa

    2015-11-15

    We report herein a study of the hydrolysis of Tabun mimic DCNP in the presence of different amines, aminoalcohols and glycols as potential suitable organocatalysts for DCNP degradation. Experiments were performed in CD3CN in the presence of 5% D2O, which is a suitable solvent mixture to follow the DCNP hydrolysis. These studies allowed the definition of different DCNP depletion paths, resulting in the formation of diethylphosphoric acid, tetraethylpyrophosphate and phosphoramide species as final products. Without organocatalysts, DCNP hydrolysis occurred mainly via an autocatalysis path. Addition of tertiary amines in sub-stoichiometric amounts largely enhanced DCNP depletion whereas non-tertiary polyamines reacted even faster. Glycols induced very slight increment in the DCNP hydrolysis, whereas DCNP hydrolysis increased sharply in the presence of certain aminoalcohols especially, 2-(2-aminoethylamino)ethanol. For the latter compound, DCNP depletion occurred ca. 80-fold faster than in the absence of organocatalysts. The kinetic studies revealed that DCNP hydrolysis in the presence of 2-(2-aminoethylamino)ethanol occurred via a catalytic process, in which the aminoalcohol was involved. DCNP hydrolysis generally depended strongly on the structure of the amine, and it was found that the presence of the OHCH2CH2N moiety in the organocatalyst structure seems important to induce a fast degradation of DCNP.

  9. Insights into dehydrogenative coupling of alcohols and amines catalyzed by a (PNN)-Ru(II) hydride complex: unusual metal-ligand cooperation.

    PubMed

    Zeng, Guixiang; Li, Shuhua

    2011-11-07

    Density functional theory calculations were performed to elucidate the mechanism of dehydrogenative coupling of primary alcohols and amines mediated by a PNN-Ru(II) hydride complex (PNN = (2-(di-tert-butylphosphinomethyl)-6-(diethylaminomethyl)pyridine)). A plausible reaction pathway was proposed which contains three stages: (1) The alcohol dehydrogenation reaction to generate the aldehyde and H(2); (2) The aldehyde-amine condensation reaction to form the hemiaminal intermediate; (3) The dehydrogenation process of the hemiaminal intermediate to yield the final amide product with the liberation of H(2). The first and third stages occur via a similar pathway: (a) Proton transfer from the substrate to the PNN ligand; (b) Intramolecular rearrangement of the deprotonated substrate to form an anagostic complex; (c) Hydride transfer from the deprotonated substrate to the Ru center to yield the trans-dihydride intermediate and the aldehyde (or amide); (d) Benzylic proton migration from the PNN ligand to the metal center forming a dihydrogen complex and subsequent H(2) liberation to regenerate the catalyst. In all these steps, the metal-ligand cooperation plays an essential role. In proton transfer steps (a) and (d), the metal-ligand cooperation is achieved through the aromatization/dearomatization processes of the PNN ligand. While in steps (b) and (c), their collaboration are demonstrated by the formation of an anagostic interaction between Ru and the C-H bond and two ionic hydrogen bonds supported by the PNN ligand.

  10. Sunlight-induced effective heterogeneous photocatalytic decomposition of aqueous organic pollutants to CO2 assisted by a CO2 sorbent, amine-containing mesoporous silica.

    PubMed

    Ide, Yusuke; Kagawa, Noriko; Sadakane, Masahiro; Sano, Tsuneji

    2012-06-04

    Photocatalytic mineralization of aqueous formic acid and phenol on pure TiO(2) under sunlight irradiation was substantially accelerated to give a reliable photocatalytic efficiency by conducting the reactions in the presence of a CO(2) sorbent, amine-containing SBA-15, placed in the gas phase of the reactor.

  11. Ruthenium-catalyzed alkylation of indoles with tertiary amines by oxidation of a sp3 C-H bond and Lewis acid catalysis.

    PubMed

    Wang, Ming-Zhong; Zhou, Cong-Ying; Wong, Man-Kin; Che, Chi-Ming

    2010-05-17

    Ruthenium porphyrins (particularly [Ru(2,6-Cl(2)tpp)CO]; tpp=tetraphenylporphinato) and RuCl(3) can act as oxidation and/or Lewis acid catalysts for direct C-3 alkylation of indoles, giving the desired products in high yields (up to 82% based on 60-95% substrate conversions). These ruthenium compounds catalyze oxidative coupling reactions of a wide variety of anilines and indoles bearing electron-withdrawing or electron-donating substituents with high regioselectivity when using tBuOOH as an oxidant, resulting in the alkylation of N-arylindoles to 3-{[(N-aryl-N-alkyl)amino]methyl}indoles (yield: up to 82%, conversion: up to 95%) and the alkylation of N-alkyl or N-H indoles to 3-[p-(dialkylamino)benzyl]indoles (yield: up to 73%, conversion: up to 92%). A tentative reaction mechanism involving two pathways is proposed: an iminium ion intermediate may be generated by oxidation of an sp(3) C-H bond of the alkylated aniline by an oxoruthenium species; this iminium ion could then either be trapped by an N-arylindole (pathway A) or converted to formaldehyde, allowing a subsequent three-component coupling reaction of the in situ generated formaldehyde with an N-alkylindole and an aniline in the presence of a Lewis acid catalyst (pathway B). The results of deuterium-labeling experiments are consistent with the alkylation of N-alkylindoles via pathway B. The relative reaction rates of [Ru(2,6-Cl(2)tpp)CO]-catalyzed oxidative coupling reactions of 4-X-substituted N,N-dimethylanilines with N-phenylindole (using tBuOOH as oxidant), determined through competition experiments, correlate linearly with the substituent constants sigma (R(2)=0.989), giving a rho value of -1.09. This rho value and the magnitudes of the intra- and intermolecular deuterium isotope effects (k(H)/k(D)) suggest that electron transfer most likely occurs during the initial stage of the oxidation of 4-X-substituted N,N-dimethylanilines. Ruthenium-catalyzed three-component reaction of N-alkyl/N-H indoles

  12. Chemoselective Reductive Amination of Carbonyl Compounds for the Synthesis of Tertiary Amines Using SnCl2·2H2O/PMHS/MeOH.

    PubMed

    Nayal, Onkar S; Bhatt, Vinod; Sharma, Sushila; Kumar, Neeraj

    2015-06-05

    Stannous chloride catalyzed chemoselective reductive amination of a variety of carbonyl compounds with aromatic amines has been developed for the synthesis of a diverse range of tertiary amines using inexpensive polymethylhydrosiloxane as reducing agent in methanol. The present method is also applicable for the synthesis of secondary amines including heterocyclic ones.

  13. Synthesis of antireflective silica coatings through the synergy of polypeptide layer-by-layer assemblies and biomineralization

    NASA Astrophysics Data System (ADS)

    Lee, Yung-Lun; Lin, Ting-Xuan; Hsu, Feng-Ming; Jan, Jeng-Shiung

    2016-01-01

    We report a versatile approach to synthesize silica coatings with antireflective (AR) characteristics through the combination of a layer-by-layer (LbL) assembly technique and biomineralization. LbL assembled decanoyl-modified poly(l-lysine)/poly(l-glutamic acid) (PLL-g-Dec/PLGA) multilayer films were used as templates for silica mineralization, followed by calcination. The specific deposition of silica onto the LbL polypeptide assemblies through amine-catalyzed polycondensation resulted in silica coatings that exhibited the transcription of the nano-/microstructured polypeptide films and their film thickness and porosity can be tuned by varying the number of bilayers, degree of substitution, and PLL molecular weight. AR silica coatings exhibiting more than 6% increase in transmittance in the near UV/visible spectral range can be obtained at an optimized refractive index, thickness, and surface roughness. The abrasion test showed that the silica coatings exhibited sufficient structural durability due to continuous silica nanostructures and low surface roughness. This study demonstrated that nanostructured thin films can be synthesized for AR coatings using the synergy between the LbL assembly technique and biomineralization.We report a versatile approach to synthesize silica coatings with antireflective (AR) characteristics through the combination of a layer-by-layer (LbL) assembly technique and biomineralization. LbL assembled decanoyl-modified poly(l-lysine)/poly(l-glutamic acid) (PLL-g-Dec/PLGA) multilayer films were used as templates for silica mineralization, followed by calcination. The specific deposition of silica onto the LbL polypeptide assemblies through amine-catalyzed polycondensation resulted in silica coatings that exhibited the transcription of the nano-/microstructured polypeptide films and their film thickness and porosity can be tuned by varying the number of bilayers, degree of substitution, and PLL molecular weight. AR silica coatings exhibiting

  14. Bioinspired thermo- and pH-responsive polymeric amines: multimolecular aggregates in aqueous media and matrices for silica/polymer nanocomposites.

    PubMed

    Danilovtseva, Elena N; Aseyev, Vladimir; Belozerova, Olga Yu; Zelinskiy, Stanislav N; Annenkov, Vadim V

    2015-05-15

    Polymeric amines have been intensively studied for application in smart systems and as matrices for the design of composite materials, including bioinspired substances. A new thermo- and pH-responsive polymer was obtained by radical polymerization of N-(3-(diethylamino)propyl)-N-methylacrylamide. Upon heating, the polymer precipitated from aqueous solutions above pH 9; the observed cloud point was dependent on the polymer concentration and decreased from 95°C at pH 9 to 40°C at pH 11. The basicity of the polymer decreased at elevated temperatures owing to an increase in the hydrophobicity-driven compaction of the macromolecules. Dynamic light scattering analysis demonstrated that the formation of large multimolecular associates with radius 1000-2000 nm was initiated from 1 to 2°C below the cloud point. The new polymer is demonstrated to be an effective matrix for various siliceous composite structures, including 200-300 nm solid spherical raspberry-like particles and hollow hemispherical particles of more than 1000 nm diameter. Condensation of silicic acid in the presence of polymeric amines is a model reaction in biosilicification studies, and the obtained data are also discussed from the perspective of the matrix hypothesis for biosilica formation.

  15. Heterogeneous asymmetric Henry-Michael one-pot reaction synergically catalyzed by grafted chiral bases and inherent achiral hydroxyls on mesoporous silica surface.

    PubMed

    Yang, Shanshan; He, Jing

    2012-10-25

    Highly efficient and enantioselective asymmetric Henry-Michael one-pot reaction has been achieved on bifunctional heterogeneous catalysts with inherent achiral hydroxyls as acidic sites and immobilized chiral amines as basic sites. Final products were afforded in yields of up to 85% and ee of 99%.

  16. Amine-Promoted Organosilicate Hydrolysis Mechanism at Near-Neutral pH

    NASA Astrophysics Data System (ADS)

    Delak, K. M.; Sahai, N.

    2006-12-01

    Proteins bearing polylysine moeities and histidine and serine amino-aicd residues, isolated from diatoms and sponges, are known to promote biological nanoporous silica formation [1, 2]. Using 29Si NMR, we have shown quantitatively that monoamines and small polyamines can chemically accelerate the hydrolysis and condensation rates of organosilicate starting materials, in biomimetic silica synthesis pathways, at circum- neutral pHs and room temperature [3, 4]. The present study is focused on understanding the mechanistic role of these amines in catalyzing the hydrolysis step that precedes condensation [5]. We conducted 29Si NMR experimental studies over a range of temperature and pHs for the hydrolysis rates of trimethylethoxysilane (TMES), a model compound with only one hydrolyzable bond. Experimental results were combined with quantum mechanical hybrid Density Functional Theory calculations of putative intermediate and transition state structures for TMES and tetramethylorthosilicate (TMOS) which has four hydrolyzable bonds. Comparison of calculated energies with experimentally-determined activation energies indicated that amines promote TMES hydrolysis mainly due to the amine's acidity at neutral pH. The proton released by the amine is transferred to the organosilicate, producing a protonated, ethoxy leaving group that can be displaced by water in an SN2 reaction. For TMOS, the activation energy of proton-transfer coupled with SN2 substitution is comparable to that for Corriu's nucleophile-activated nucleophilic displacement mechanism [6], such that the mechanism of amine-catalyzed hydrolysis is mostly dependent on the ambient pH conditions as well as the type of amine. The molecular mechanisms of hydrolysis and aggregation are reflected, ultimately, on the larger scale in the silica morphology where amines promoting faster hydrolysis result in glassy products compared to slower hydrolyzing amines forming particulate silica [7, 8]. REFERENCES [1] Kroger N

  17. Solid-phase extraction of copper(II) in water and food samples using silica gel modified with bis(3-aminopropyl)amine and determination by flame atomic absorption spectrometry.

    PubMed

    Cagirdi, Duygu; Altundag, Hüseyin; Imamoglu, Mustafa; Tuzen, Mustafa

    2014-01-01

    A simple and selective separation and preconcentration method was developed for the determination of Cu(ll) ions. This method is based on adsorption of Cu(ll) ions from aqueous solution on a bis(3-aminopropyl)amine modified silica gel column and flame atomic absorption spectrometric determination after desorption. Various analytical parameters such as pH, type of eluent solution and its volume, flow rate of sample and eluent, and sample volume were optimized. Effects of some cation, anion, and transition metal ions on the recoveries of Cu(ll) ions were also investigated. Cu(ll) ions were quantitatively recovered at pH 6; 5.0 mL of 2 M HCI was used as the eluent. The preconcentration factor was found to be 150. The LOD was 0.12 microg/L for Cu(ll). The accuracy of the method was confirmed by analysis of Tea Leaves (INCT-TL-1) and Fish Protein (DORM-3) certified reference materials. The optimized method was applied to various water and food samples for the determination of Cu(ll).

  18. [Stardust Amines

    NASA Technical Reports Server (NTRS)

    Dworkin, Jason P.

    2008-01-01

    We investigated the abundances of amino acids and amines, as well as their enantiomeric composition in water extracts of comet Wild 2 exposed aerogel and aluminum foils returned by Stardust using liquid chromatography with UV fluorescence detection and time of flight-mass spectrometry (LC-FD/ToF-MS). A suite of amino acids and amines including glycine, L-alanine, methylamine (MA), and ethylamine (EA) were identified in the Stardust bulk aerogel. With the exception of MA and EA, all other primary amines detected in comet-exposed aerogels were also present in the aerogel witness tile that was not exposed to Wild 2, suggesting that most amines are terrestrial in origin. The enhanced abundances of MA, EA, and possibly glycine in comet-exposed aerogel compared to controls, coupled with MA to EA ratios (approx.1 to 2) that are distinct from preflight aerogels (approx.7 to lo), suggest that these amines were captured from Wild 2. The presence of cometary amines in Stardust material supports the hypothesis that comets were an important source of prebiotic organics on the early Earth. To better understand their origin, a systematic study of all these species with C, N, and H compound specific isotopic analysis (CSIA) via gas chromatography quadrupole mass spectrometry in with parallel with combustion isotope ratio mass spectrometry (GC-QMS/IRMS) is being conducted. We will discuss our latest C-CSIA measurements and what they indicate about the origin of the amino acids extracted from Stardust samples.

  19. Hydrothermal Reactivity of Amines

    NASA Astrophysics Data System (ADS)

    Robinson, K.; Shock, E.; Hartnett, H. E.; Williams, L. B.; Gould, I.

    2013-12-01

    The reactivity of aqueous amines depends on temperature, pH, and redox state [1], all of which are highly variable in hydrothermal systems. Temperature and pH affect the ratio of protonated to unprotonated amines (R-NH2 + H+ = R-NH3+), which act as nucleophiles and electrophiles, respectively. We hypothesize that this dual nature can explain the pH dependence of reaction rates, and predict that rates will approach a maximum at pH = pKa where the ratio of protonated and unprotonated amines approaches one and the two compounds are poised to react with one another. Higher temperatures in hydrothermal systems allow for more rapid reaction rates, readily reversible reactions, and unique carbon-nitrogen chemistry in which water acts as a reagent in addition to being the solvent. In this study, aqueous benzylamine was used as a model compound to explore the reaction mechanisms, kinetics, and equilibria of amines under hydrothermal conditions. Experiments were carried out in anoxic silica glass tubes at 250°C (Psat) using phosphate-buffered solutions to observe changes in reaction rates and product distributions as a function of pH. The rate of decomposition of benzylamine was much faster at pH 4 than at pH 9, consistent with the prediction that benzylamine acts as both nucleophile and an electrophile, and our estimate that the pKa of benzylamine is ~5 at 250°C and Psat. Accordingly, dibenzylamine is the primary product of the reaction of two benzylamine molecules, and this reaction is readily reversible under hydrothermal conditions. Extremely acidic or basic pH can be used to suppress dibenzylamine production, which also suppresses the formation of all other major products, including toluene, benzyl alcohol, dibenzylimine, and tribenzylamine. This suggests that dibenzylamine is the lone primary product that then itself reacts as a precursor to produce the above compounds. Analog experiments performed with ring-substituted benzylamine derivatives and chiral

  20. Quinoline-2-carboimine copper complex immobilized on amine functionalized silica coated magnetite nanoparticles: a novel and magnetically retrievable catalyst for the synthesis of carbamates via C-H activation of formamides.

    PubMed

    Sharma, R K; Dutta, Sriparna; Sharma, Shivani

    2015-01-21

    In the present study, we report the synthesis of a highly efficient and magnetically retrievable catalytic system (Cu-2QC@Am-SiO2@Fe3O4) through the covalent immobilization of quinoline-2-carboxaldehyde (2QC) on an amine functionalized silica coated ferrite nanosupport followed by metallation with copper acetate. The structure of the organic-inorganic hybrid nanomaterial has been confirmed using various physicochemical techniques such as Powder X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Energy Dispersive X-Ray Spectroscopy (EDS), Energy Dispersive X-Ray Fluorescence Spectroscopy (ED-XRF), Atomic Absorption Spectroscopy (AAS), Inductively Coupled Plasma Spectroscopy (ICP) and Vibrating Sample Magnetometry (VSM). The resulting nanocatalyst exhibits a remarkable catalytic efficacy in the synthesis of industrially and pharmaceutically significant carbamates via the C-H activation of formamides under solvent free conditions. The most important attribute of the present methodology is that the catalyst can be recovered simply through an external magnetic force and reused several times without any significant deterioration in its activity. Furthermore, the heterogeneity test has been carried out in order to ensure the intrinsic stability of the nanostructured catalyst. The activity of the Cu-2QC@Am-SiO2@Fe3O4 nanocatalyst has been found to be far more superior in comparison with the literature precedents in terms of the product yield, cost and reusability of the catalyst. Besides, ambient reaction conditions, simple workup procedure, wide substrate scope and cost effectiveness are some of the other outstanding features of this protocol that make it economical and sustainable.

  1. Tandem one-pot synthesis of flavans by recyclable silica-HClO4 catalyzed Knoevenagel condensation and [4 + 2]-Diels-Alder cycloaddition.

    PubMed

    Bharate, Sandip B; Mudududdla, Ramesh; Bharate, Jaideep B; Battini, Narsaiah; Battula, Satyanarayana; Yadav, Rammohan R; Singh, Baldev; Vishwakarma, Ram A

    2012-07-14

    An efficient one-pot multi-component synthesis of flavans using perchloric acid supported on silica as a recyclable heterogeneous catalyst has been described. This is the first report of direct one-step construction of a flavan skeleton from a phenolic precursor. The method involves a Knoevenagel-type condensation leading to in situ formation of transient O-quinone methide which further undergoes [4 + 2]-Diels-Alder cycloaddition with styrene to yield a flavan skeleton. The method provides easy access to a wide range of bio-active natural products viz. flavonoids, anthocyanins and catechins.

  2. Thermal behavior of poly(2-hydroxyethyl methacrylate-bis-[trimethoxysilylpropyl]amine) networks

    NASA Astrophysics Data System (ADS)

    Bustos Figueroa, L. A.; Salgado Delgado, R.; García Hernandez, E.; Vargas Galarza, Z.; Rubio Rosas, E.; Salgado Rodriguez, R.

    2013-06-01

    Poly(HEMA-BisSi) networks were prepared by using acid-catalyzed sol-gel of bis-[trimethoxysilylpropyl]amine (BisSi) and free radical polymerization of 2-hydroxyethyl methacrylate (HEMA). The thermal properties of the poly(HEMA-BisSi) networks were investigated with differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The thermal behavior of these networks was also compared with homopolymers (The networks formed in both PHEMA and PBisSi gels were identified). The glass transition temperature (Tg) of PHEMA homopolymer was found as 103.74 °C. The thermal degradation of the poly(HEMA-BisSi) networks with different silica contents (e.g. 10, 15 and 25 wt%) were evaluated with use of DTG. It was observed that the thermal degradation temperature of poly(HEMA-BisSi) networks changed much with the BisSi content.

  3. The sugar model: catalysis by amines and amino acid products

    NASA Technical Reports Server (NTRS)

    Weber, A. L.

    2001-01-01

    Ammonia and amines (including amino acids) were shown to catalyze the formation of sugars from formaldehyde and glycolaldehyde, and the subsequent conversion of sugars to carbonylcontaining products under the conditions studied (pH 5.5 and 50 degrees C). Sterically unhindered primary amines were better catalysts than ammonia, secondary amines, and sterically hindered primary amines (i.e. alpha-aminoisobutyric acid). Reactions catalyzed by primary amines initially consumed formaldehyde and glycolaldehyde about 15-20 times faster than an uncatalyzed control reaction. The amine-catalyzed reactions yielded aldotriose (glyceraldehyde), ketotriose (dihydroxyacetone), aldotetroses (erythrose and threose), ketotetrose (erythrulose), pyruvaldehyde, acetaldehyde, glyoxal, pyruvate, glyoxylate, and several unindentified carbonyl products. The concentrations of the carbonyl products, except pyruvate and ketotetrose, initially increased and then declined during the reaction, indicating their ultimate conversion to other products (like larger sugars or pyruvate). The uncatalyzed control reaction yielded no pyruvate or glyoxylate, and only trace amounts of pyruvaldehyde, acetaldehyde and glyoxal. In the presence of 15 mM catalytic primary amine, such as alanine, the rates of triose and pyruvaldehyde of synthesis were about 15-times and 1200-times faster, respectively, than the uncatalyzed reaction. Since previous studies established that alanine is synthesized from glycolaldehyde and formaldehyde via pyruvaldehyde as its direct precursor, the demonstration that the alanine catalyzes the conversion of glycolaldehyde and formaldehyde to pyruvaldehyde indicates that this synthetic pathway is capable of autocatalysis. The relevance of this synthetic process, named the Sugar Model, to the origin of life is discussed.

  4. Phenylethynyl amine

    NASA Technical Reports Server (NTRS)

    Hergenrother, Paul M. (Inventor); Bryant, Robert G. (Inventor); Jensen, Brian J. (Inventor); Havens, Stephen J. (Inventor)

    1997-01-01

    Four phenylethynyl amine compounds--3 and 4-aminophenoxy-4'-phenylethynylbenzophenone, and 3 and 4-amino-4'-phenylethynylbenzophenone--were readily prepared and were used to endcap imide oligomers. Phenylethynyl-terminated amide acid oligomers and phenylethynyl-terminated imide oligomers with various molecular weights and compositions were prepared and characterized. These oligomers were cured at 300.degree. C. to 400.degree. C. to provide crosslinked polyimides with excellent solvent resistance, high strength and modulus and good high temperature properties. Adhesive panels, composites, films and moldings from these phenylethynyl terminated imide oligomers gave excellent mechanical performance.

  5. High surface area Au-SBA-15 and Au-MCM-41 materials synthesis: tryptophan amino acid mediated confinement of gold nanostructures within the mesoporous silica pore walls.

    PubMed

    Selvakannan, Pr; Mantri, Kshudiram; Tardio, James; Bhargava, Suresh K

    2013-03-15

    Advantages of confining the gold nanostructures formation within the mesoporous silica pore walls during its silica condensation and consequent improvement in the textural properties such as specific surface area, pore volume, pore diameter have been demonstrated, while retaining gold nanostructures within the silica walls. This has been achieved by tryptophan mediated confinement of gold nanoparticles formation within the condensing silica framework, to obtain Au-SBA-15 (SSA 1247 m(2)/g, V(t)~1.37 cm(3)/g) and Au-MCM-41 (SSA 1287 m(2)/g, V(t)~1.1 cm(3)/g), mesoporous silica materials having the combination of very high surface area from the porous support as well as gold nanoparticles infiltrated silica walls. Choice of tryptophan for this purpose is that it has an indole group, which was known to reduce gold ions to form gold nanoparticles and its amine and carboxylic acid groups, catalyze the hydrolysis of silica precursors in a wide range of pH. These properties have been utilized in restricting the gold nanostructures formation inside the condensing silica phase without affecting the self assembly between the silica precursors and the triblock copolymer (for SBA-15) or cetyltrimethylammonium bromide template (for MCM-41). The polytryptophan and the gold nanostructures, which were encapsulated within the silica framework and upon removal of the template by calcination resulting in the formation mesoporous materials wherein the silica walls become microporous due to the removal of occluded polytryptophan and the resulting microchannels contain very small gold nanostructures. Hence, the resulting materials have very high surface area, high pore volume and narrow pore size distribution as compared to their parent SBA-15, MCM-41 and SBA-15, MCM-41 post functionalized with gold nanoparticles inside the pores.

  6. Parallel synthesis of ureas and carbamates from amines and CO2 under mild conditions.

    PubMed

    Peterson, Scott L; Stucka, Sabrina M; Dinsmore, Christopher J

    2010-03-19

    A mild and efficient library synthesis technique has been developed for the synthesis of ureas and carbamates from carbamic acids derived from the DBU-catalyzed reaction of amines and gaseous carbon dioxide. Carbamic acids derived from primary amines reacted with Mitsunobu reagents to generate isocyanates in situ which were condensed with primary and secondary amines to afford the desired ureas. Similarly, carbamic acids from secondary amines reacted with alcohols activated with Mitsunobu reagents to form carbamates.

  7. Enantioselective, iridium-catalyzed monoallylation of ammonia.

    PubMed

    Pouy, Mark J; Stanley, Levi M; Hartwig, John F

    2009-08-19

    Highly enantioselective, iridium-catalyzed monoallylations of ammonia are reported. These reactions occur with electron-neutral, -rich, and -poor cinnamyl carbonates, alkyl and trityloxy-substituted allylic carbonates, and dienyl carbonates in moderate to good yields and excellent enantioselectivities. This process is enabled by the use of an iridium catalyst that does not require a Lewis acid for activation and that is stable toward a large excess of ammonia. This selective formation of primary allylic amines allows for one-pot syntheses of heterodiallylamines and allylic amides that are not otherwise accessible via iridium-catalyzed allylic amination without the use of blocking groups and protective group manipulations.

  8. Enantioselective, Iridium-Catalyzed Monoallylation of Ammonia

    PubMed Central

    Pouy, Mark J.; Stanley, Levi M.; Hartwig, John F.

    2009-01-01

    Highly enantioselective, iridium-catalyzed monoallylations of ammonia are reported. These reactions occur with electron-neutral, -rich, and -poor cinnamyl carbonates, alkyl and trityloxy-substituted allylic carbonates, and dienyl carbonates in moderate to good yields and excellent enantioselectivities. This process is enabled by the use of an iridium catalyst that does not require a Lewis acid for activation and that is stable toward a large excess of ammonia. This selective formation of primary allylic amines allows for one-pot syntheses of heterodiallylamines and allylic amides that are not otherwise accessible via iridium-catalyzed allylic amination without the use of blocking groups and protective group manipulations. PMID:19722644

  9. Synthesis of 2,3-dihydroquinazolin-4(1H)-ones by three-component coupling of isatoic anhydride, amines, and aldehydes catalyzed by magnetic Fe(3)O(4) nanoparticles in water.

    PubMed

    Zhang, Zhan-Hui; Lü, Hong-Yan; Yang, Shu-Hong; Gao, Jian-Wu

    2010-09-13

    A simple and efficient protocol for one-pot three-component coupling of isatoic anhydride, amines, and aldehydes in water using magnetically recoverable Fe(3)O(4) nanoparticles is reported. This methodology results in the synthesis of a variety of 2,3-dihydroquinazolin-4(1H)-ones in high yields. The catalyst can be recovered and recycled without a significant loss in the catalytic activity.

  10. Non-directed aromatic C–H amination: catalytic and mechanistic studies enabled by Pd catalyst and reagent design†

    PubMed Central

    Bandara, H. M. D.; Jin, D.; Mantell, M. A.; Field, K. D.; Wang, A.; Narayanan, R. P.; Deskins, N. A.; Emmert, M. H.

    2016-01-01

    This manuscript describes the systematic development of pyridine-type ligands, which promote the Pd catalyzed, non-directed amination of benzene in combination with novel, hydroxylamine-based electrophilic amination reagents. DFT calculations and mechanistic experiments provide insights into the factors influencing the arene C–H amination protocol. PMID:28066540

  11. Polymer-silica hybrids for separation of CO2 and catalysis of organic reactions

    NASA Astrophysics Data System (ADS)

    Silva Mojica, Ernesto

    Porous materials comprising polymeric and inorganic segments have attracted interest from the scientific community due to their unique properties and functionalities. The physical and chemical characteristics of these materials can be effectively exploited for adsorption applications. This dissertation covers the experimental techniques for fabrication of poly(vinyl alcohol) (PVA) and silica (SiO2) porous supports, and their functionalization with polyamines for developing adsorbents with potential applications in separation of CO2 and catalysis of organic reactions. The supports were synthesized by processes involving (i) covalent cross-linking of PVA, (ii) hydrolysis and poly-condensation of silica precursors (i,e,. sol-gel synthesis), and formation of porous structures via (iii) direct templating and (iv) phase inversion techniques. Their physical structure was controlled by the proper combination of the preparation procedures, which resulted in micro-structured porous materials in the form of micro-particles, membranes, and pellets. Their adsorption characteristics were tailored by functionalization with polyethyleneimine (PEI), and their physicochemical properties were characterized by vibrational spectroscopy (FTIR, UV-vis), microscopy (SEM), calorimetry (TGA, DSC), and adsorption techniques (BET, step-switch adsorption). Spectroscopic investigations of the interfacial cross-linking reactions of PEI and PVA with glutaraldehyde (GA) revealed that PEI catalyzes the cross-linking reactions of PVA in absence of external acid catalysts. In-situ IR spectroscopy coupled with a focal plane array (FPA) image detector allowed the characterization of a gradient interface on a PEI/PVA composite membrane and the investigation of the cross-linking reactions as a function of time and position. The results served as a basis to postulate possible intermediates, and propose the reaction mechanisms. The formulation of amine-functionalized CO2 capture sorbents was based on the

  12. Tandem bis-aza-Michael addition reaction of amines in aqueous medium promoted by polystyrenesulfonic Acid

    EPA Science Inventory

    An efficient and environmentally benign tandem bis-aza-Michael addition of amines catalyzed by polystyrene sulfonic acid (PSSA) is described. This operationally simple high yielding microwave assisted synthetic protocol proceeded in water in the absence of any organic solvent.

  13. Catalytic Asymmetric Hydroamination of Unactivated Internal Olefins to Aliphatic Amines

    PubMed Central

    Yang, Yang; Shi, Shi-Liang; Niu, Dawen; Liu, Peng; Buchwald, Stephen L.

    2015-01-01

    Catalytic assembly of enantiopure aliphatic amines from abundant and readily available precursors has long been recognized as a paramount challenge in synthetic chemistry. Herein, we describe a mild and general copper-catalyzed hydroamination that effectively converts unactivated internal olefins, an important yet unexploited class of abundant feedstock chemicals, into highly enantioenriched α-branched amines (≥ 96% enantiomeric excess) featuring two minimally differentiated aliphatic substituents. This method provides a powerful means to access a broad range of advanced, highly functionalized enantioenriched amines of interest in pharmaceutical research and other areas. PMID:26138973

  14. Selective Hydrogenation of Nitriles to Primary Amines by using a Cobalt Phosphine Catalyst.

    PubMed

    Adam, Rosa; Bheeter, Charles Beromeo; Cabrero-Antonino, Jose R; Junge, Kathrin; Jackstell, Ralf; Beller, Matthias

    2017-01-09

    A general procedure for the catalytic hydrogenation of nitriles to primary amines by using a non-noble metal-based system is presented. Co(acac)3 in combination with tris[2-(dicyclohexylphosphino)ethyl]phosphine efficiently catalyzes the selective hydrogenation of a wide range of (hetero)aromatic and aliphatic nitriles to give the corresponding amines.

  15. Emerging Developments Using Nitrogen-Heteroatom Bonds as Amination Reagents in the Synthesis of Aminoarenes.

    PubMed

    Hendrick, Charles E; Wang, Qiu

    2017-01-20

    Aminoarenes constitute valuable building blocks in organic synthesis and an essential skeleton ubiquitously found in ligands, agrochemicals, and pharmaceuticals. This Synopsis presents recent amination methods using nitrogen-heteroatom bonds as a powerful and versatile platform to rapidly synthesize diverse aminoarenes, with a focus on aryne amino functionalization and transition-metal-catalyzed arene C-H amination.

  16. A Catalytic, Brønsted Base Strategy for Intermolecular Allylic C—H Amination

    PubMed Central

    Reed, Sean A.; Mazzotti, Anthony R.; White, M. Christina

    2009-01-01

    A Brønsted base activation mode for oxidative, Pd(II)/sulfoxide catalyzed, intermolecular C—H allylic amination is reported. N,N-diisopropylethylamine was found to promote amination of unactivated terminal olefins, forming the corresponding linear allylic amine products with high levels of stereo-, regio-, and chemoselectivity. The predictable and high selectivity of this C—H oxidation method enables late-stage incorporation of nitrogen into advanced synthetic intermediates and natural products. PMID:19645492

  17. Synthesis of unsymmetric tertiary amines via alcohol amination.

    PubMed

    Pang, Shaofeng; Deng, Youquan; Shi, Feng

    2015-06-11

    The first one-pot selective synthesis of unsymmetric tertiary amines is reported by the amination of two types of alcohols with primary amines via the development of a simple CuAlOx-HT catalyst and enables the synthesis of unsymmetric amines in a wide variety of primary amines and alcohols.

  18. Nitrosamine formation in amine scrubbing at desorber temperatures.

    PubMed

    Fine, Nathan A; Goldman, Mark J; Rochelle, Gary T

    2014-01-01

    Amine scrubbing is a thermodynamically efficient and industrially proven method for carbon capture, but amine solvents can nitrosate in the desorber, forming potentially carcinogenic nitrosamines. The kinetics of reactions involving nitrite and monoethanolamine (MEA), diethanolamine (DEA), methylethanolamine (MMEA), and methyldiethanolamine (MDEA) were determined under desorber conditions. The nitrosations of MEA, DEA, and MMEA are first order in nitrite, carbamate species, and hydronium ion. Nitrosation of MDEA, a tertiary amine, is not catalyzed by the addition of CO2 since it cannot form a stable carbamate. Concentrated and CO2 loaded MEA was blended with low concentrations of N-(2-hydroxyethyl) glycine (HeGly), hydroxyethyl-ethylenediamine (HEEDA), and DEA, secondary amines common in MEA degradation. Nitrosamine yield was proportional to the concentration of secondary amine and was a function of CO2 loading and temperature. Blends of tertiary amines with piperazine (PZ) showed n-nitrosopiperazine (MNPZ) yields close to unity, validating the slow nitrosation rates hypothesized for tertiary amines. These results provide a useful tool for estimating nitrosamine accumulation over a range of amine solvents.

  19. Synthetic Study of Dragmacidin E: Construction of the Core Structure Using Pd-Catalyzed Cascade Cyclization and Rh-Catalyzed Aminoacetoxylation.

    PubMed

    Inoue, Naoya; Nakano, Shun-Ichi; Harada, Shingo; Hamada, Yasumasa; Nemoto, Tetsuhiro

    2017-03-03

    We developed a novel synthetic method of the core structure of dragmacidin E bearing a 7-membered ring-fused bis(indolyl)pyrazinone skeleton. Formation of the 7-membered ring-fused tricyclic indole skeleton was accomplished using a palladium-catalyzed Heck insertion-allylic amination cascade. Vicinal difunctionalization of the 7-membered ring was realized via a rhodium-catalyzed aminoacetoxylation.

  20. Iron(II) triflate as a catalyst for the synthesis of indoles by intramolecular C-H amination.

    PubMed

    Bonnamour, Julien; Bolm, Carsten

    2011-04-15

    A practical iron-catalyzed intramolecular C-H amination reaction and its application in the synthesis of indole derivatives are presented. As a catalyst, commercially available iron(II) triflate is used.

  1. Silica-Immobilized Enzyme Reactors

    DTIC Science & Technology

    2007-08-01

    relief from the symptoms of inflammation and pain Silica-IMERs 10 and is the mode of action of drugs such as aspirin and ibuprofen .[61] Serotonin...supports and using the enantiomeric selectivity of the enzyme to resolve racemic mixtures.[100] Immobilization onto supports with various pore sizes and...activity (~37%) and used as a packed- bed IMER to catalyze the racemic resolution of (S)-ketoprofen from its constituent enantiomers . The optically pure (S

  2. Silica gel-catalyzed one-pot syntheses in water and fluorescence properties studies of 5-amino-2-aryl-3H-chromeno[4,3,2-de][1,6]naphthyridine-4-carbonitriles and 5-amino-2-aryl-3H-quinolino[4,3,2-de][1,6]naphthyridine-4-carbonitriles.

    PubMed

    Wu, Hui; Lin, Wei; Wan, Yu; Xin, Hai-qiang; Shi, Da-qing; Shi, Yan-hui; Yuan, Rui; Bo, Rong-cheng; Yin, Wei

    2010-01-01

    The silica gel-catalyzed synthesis of 5-amino-2-aryl-3H-chromeno[4,3,2-de][1,6]naphthyridine-4-carbonitriles and 5-amino-2-aryl-3H-quinolino[4,3,2-de][1,6]naphthyridine-4-carbonitriles were simply achieved upon the one-pot cascade reaction of malononitrile with substituted 2-hydroxyacetophenone (or 2-aminoacetophenone) and aromatic aldehyde in aqueous media. The mechanistic investigation results based on electrospray ionization mass spectrometry (ESI-MS) indicated that malononitrile displayed a dual role during this transformation. Thirteen bonds were cleaved and 12 new bonds were constructed in the formation of 5-amino-2-aryl-3H-chromeno[4,3,2-de][1,6]naphthyridine-4-carbonitriles, while only 2 H(2)O molecules were removed. The fluorescence properties screening showed five new compounds have high fluorescence quantum yields.

  3. Effect of Amine Surface Coverage on the Co-Adsorption of CO2 and Water: Spectral Deconvolution of Adsorbed Species.

    PubMed

    Didas, Stephanie A; Sakwa-Novak, Miles A; Foo, Guo Shiou; Sievers, Carsten; Jones, Christopher W

    2014-12-04

    Three primary amine materials functionalized onto mesoporous silica with low, medium, and high surface amine coverages are prepared and evaluated for binary CO2/H2O adsorption under dilute conditions. Enhancement of amine efficiency due to humid adsorption is most pronounced for low surface amine coverage materials. In situ FT-IR spectra of adsorbed CO2 on these materials suggest this enhancement may be associated with the formation of bicarbonate species during adsorption on materials with low surface amine coverage, though such species are not observed on high surface coverage materials. On the materials with the lowest amine loading, bicarbonate is observed on longer time scales of adsorption, but only after spectral contributions from rapidly forming alkylammonium carbamate species are removed. This is the first time that direct evidence for bicarbonate formation, which is known to occur in liquid aqueous amine solutions, has been presented for CO2 adsorption on solid amine adsorbents.

  4. One-pot and efficient synthesis of triazolo[1,2-a]indazole-triones via reaction of arylaldehydes with urazole and dimedone catalyzed by silica nanoparticles prepared from rice husk.

    PubMed

    Hamidian, Hooshang; Fozooni, Samieh; Hassankhani, Asadollah; Mohammadi, Sayed Zia

    2011-10-26

    A novel synthesis of triazolo[1,2-a]indazole-1,3,8-trione derivatives by reaction of urazole, dimedone and aromatic aldehydes under conventional heating and microwave irradiation and solvent-free conditions using silica nanoparticles prepared from rice husk ash as catalyst is described. The new method features high yields, multicomponent reactions and environmental friendliness.

  5. Utilization of rice husk ash as silica source for the synthesis of mesoporous silicas and their application to CO2 adsorption through TREN/TEPA grafting.

    PubMed

    Bhagiyalakshmi, Margandan; Yun, Lee Ji; Anuradha, Ramani; Jang, Hyun Tae

    2010-03-15

    Mesoporous MCM-41, MCM-48 and SBA-15 were synthesized using Rice husk ash (RHA) as the silica source and their defective Si-OH sites were functionalized by 3-chloropropyltrimethoxysilane (CPTMS) which was subsequently grafted with amine compounds, Tris(2-aminoethyl)amine (TREN) and Tetraethylenepentamine (TEPA). X-ray powder diffraction (XRD) and BET results of the parent mesoporous silica suggested their closeness of structural properties to those obtained from conventional silica sources. CO(2) adsorption of branched amine TREN and straight chain amine TEPA at 25, 50 and 75 degrees C was obtained by Thermogravimetric Analyser (TGA) at atmospheric pressure. TREN grafted mesoporous silica showed 7% of CO(2) adsorption while TEPA grafted mesoporous silicas showed less CO(2) adsorption, which is due to the presence of isolated amine groups in TREN. TREN grafted mesoporous silicas were also observed to be selective towards CO(2), thermally stable and recyclable. The order of CO(2) adsorption with respect to amount of amine grafting was observed to be MCM-48/TREN>MCM-41/TREN>SBA-15/TREN.

  6. Continuous Reductive Amination of Biomass-Derived Molecules over Carbonized Filter Paper-Supported FeNi Alloy.

    PubMed

    Chieffi, Gianpaolo; Braun, Max; Esposito, Davide

    2015-11-01

    This paper reports the continuous reductive amination of different molecules, including biomass-related compounds, over carbon-supported FeNi nanoparticles obtained on the basis of inexpensive and abundant metal precursors and cellulose. A biorefinery case study for the preparation of pyrrolidones via acid-catalyzed hydrolysis of glucose followed by reductive amination of the obtained levulinic acid is described.

  7. Surface treatment of silica nanoparticles for stable and charge-controlled colloidal silica

    PubMed Central

    Kim, Kyoung-Min; Kim, Hye Min; Lee, Won-Jae; Lee, Chang-Woo; Kim, Tae-il; Lee, Jong-Kwon; Jeong, Jayoung; Paek, Seung-Min; Oh, Jae-Min

    2014-01-01

    An attempt was made to control the surface charge of colloidal silica nanoparticles with 20 nm and 100 nm diameters. Untreated silica nanoparticles were determined to be highly negatively charged and have stable hydrodynamic sizes in a wide pH range. To change the surface to a positively charged form, various coating agents, such as amine containing molecules, multivalent metal cation, or amino acids, were used to treat the colloidal silica nanoparticles. Molecules with chelating amine sites were determined to have high affinity with the silica surface to make agglomerations or gel-like networks. Amino acid coatings resulted in relatively stable silica colloids with a modified surface charge. Three amino acid moiety coatings (L-serine, L-histidine, and L-arginine) exhibited surface charge modifying efficacy of L-histidine > L-arginine > L-serine and hydrodynamic size preservation efficacy of L-serine > L-arginine > L-histidine. The time dependent change in L-arginine coated colloidal silica was investigated by measuring the pattern of the backscattered light in a Turbiscan™. The results indicated that both the 20 nm and 100 nm L-arginine coated silica samples were fairly stable in terms of colloidal homogeneity, showing only slight coalescence and sedimentation. PMID:25565824

  8. Amine salts of nitroazoles

    DOEpatents

    Kienyin Lee; Stinecipher, M.M.

    1993-10-26

    Compositions of matter, a method of providing chemical energy by burning said compositions, and methods of making said compositions are described. These compositions are amine salts of nitroazoles. 1 figure.

  9. Method for inhibiting silica precipitation and scaling in geothermal flow systems

    DOEpatents

    Harrar, Jackson E.; Lorensen, Lyman E.; Locke, Frank E.

    1982-01-01

    A method for inhibiting silica scaling and precipitation in geothermal flow systems by on-line injection of low concentrations of cationic nitrogen-containing compounds, particularly polymeric imines, polymeric amines, and quaternary ammonium compounds.

  10. Method for inhibiting silica precipitation and scaling in geothermal flow systems

    DOEpatents

    Harrar, J.E.; Lorensen, L.E.; Locke, F.E.

    1980-06-13

    A method for inhibiting silica scaling and precipitation in geothermal flow systems by on-line injection of low concentrations of cationic nitrogen-containing compounds, particularly polymeric imines, polymeric amines, and quaternary ammonium compounds is described.

  11. Transport in Thermally Grown Silica on Silicon.

    DTIC Science & Technology

    1980-01-01

    catalyze the crvstallization of amorphous silica to cristobalite . 4 "" rhc activation ener- 4ies for oxidation when cristobalite forms increase but...categories. These are 65 kcal (due to formation of cristobalite ); " 40 kcal (in dry oxygen); and 30 kcal or less (in moist oxygen). S TU’ARY Based on

  12. Synthesis of benzimidazoles via iridium-catalyzed acceptorless dehydrogenative coupling.

    PubMed

    Sun, Xiang; Lv, Xiao-Hui; Ye, Lin-Miao; Hu, Yu; Chen, Yan-Yan; Zhang, Xue-Jing; Yan, Ming

    2015-07-21

    Iridium-catalyzed acceptorless dehydrogenative coupling of tertiary amines and arylamines has been developed. A number of benzimidazoles were prepared in good yields. An iridium-mediated C-H activation mechanism is suggested. This finding represents a novel strategy for the synthesis of benzimidazoles.

  13. Palladium catalyzed alkoxy- and aminocarbonylation of vinyl tosylates.

    PubMed

    Reeves, Diana C; Rodriguez, Sonia; Lee, Heewon; Haddad, Nizar; Krishnamurthy, Dhileepkumar; Senanayake, Chris H

    2011-05-06

    The palladium catalyzed alkoxycarbonylation and aminocarbonylation of vinyl tosylates are described. A variety of ketone and aldehyde derived vinyl tosylates may be carbonylated in the presence of primary, secondary, and tertiary alcohols, or primary and secondary amines, to provide the corresponding esters and amides in good yields. The alkoxycarbonylation was applied to a short synthesis of isoguvacine.

  14. Production of Primary Amines by Reductive Amination of Biomass-Derived Aldehydes/Ketones.

    PubMed

    Liang, Guanfeng; Wang, Aiqin; Li, Lin; Xu, Gang; Yan, Ning; Zhang, Tao

    2017-03-06

    Transformation of biomass into valuable nitrogen-containing compounds is highly desired, yet limited success has been achieved. Here we report an efficient catalyst system, partially reduced Ru/ZrO2 , which could catalyze the reductive amination of a variety of biomass-derived aldehydes/ketones in aqueous ammonia. With this approach, a spectrum of renewable primary amines was produced in good to excellent yields. Moreover, we have demonstrated a two-step approach for production of ethanolamine, a large-market nitrogen-containing chemical, from lignocellulose in an overall yield of 10 %. Extensive characterizations showed that Ru/ZrO2 -containing multivalence Ru association species worked as a bifunctional catalyst, with RuO2 as acidic promoter to facilitate the activation of carbonyl groups and Ru as active sites for the subsequent imine hydrogenation.

  15. Amine-Catalyzed Isomerization of Diethylmaleate to Diethylfumarate.

    ERIC Educational Resources Information Center

    Glover, Irving T.; And Others

    1978-01-01

    This reaction is used in an introductory organic chemistry course to illustrate principles of gas-liquid chromatography, geometrical isomerism, homogeneous catalysis, and activation energy determinations. (BB)

  16. Selective palladium(ii)-mediated oxidation of homoallylic N-tert-butanesulfinyl amine derivatives.

    PubMed

    Sirvent, Ana; Soler, Tatiana; Foubelo, Francisco; Yus, Miguel

    2017-02-28

    The palladium(ii)-catalyzed oxidation of homoallylic amine derivatives resulting from the allylation of N-tert-butanesulfinyl imines with allyl bromide led to the formation of the corresponding terminal allylic acetates in a regioselective fashion in moderate yields. In the case of the homoallylic amine derivatives obtained using cyclohexenyl bromide as the allylating reagent, the allylic oxidation took place with high regio- and diastereoselectivity and yields ranging from 40 to 85%.

  17. OleD Loki as a Catalyst for Tertiary Amine and Hydroxamate Glycosylation.

    PubMed

    Hughes, Ryan R; Shaaban, Khaled A; Zhang, Jianjun; Cao, Hongnan; Phillips, George N; Thorson, Jon S

    2017-02-16

    We describe the ability of an engineered glycosyltransferase (OleD Loki) to catalyze the N-glycosylation of tertiary-amine-containing drugs and trichostatin hydroxamate glycosyl ester formation. As such, this study highlights the first bacterial model catalyst for tertiary-amine N-glycosylation and further expands the substrate scope and synthetic potential of engineered OleDs. In addition, this work could open the door to the discovery of similar capabilities among other permissive bacterial glycosyltransferases.

  18. A Simple Secondary Amine Synthesis: Reductive Amination Using Sodium Triacetoxyborohydride

    NASA Astrophysics Data System (ADS)

    Carlson, Merle W.; Ciszewski, James T.; Bhatti, Micah M.; Swanson, Wesley F.; Wilson, Anne M.

    2000-02-01

    We present a reductive amination experiment for a second-semester organic chemistry class. It utilizes an imine intermediate and sodium triacetoxyborohydride, a mild reducing agent. The progress of the reaction is followed by TLC as the starting materials (the aldehyde and primary amine), the imine intermediate, and the secondary amine product are visible under ultraviolet light. This experiment provides an introduction to the observation of intermediates, the synthesis of amines, and the concept of mild reducing agents.

  19. Enzymatic network for production of ether amines from alcohols.

    PubMed

    Palacio, Cyntia M; Crismaru, Ciprian G; Bartsch, Sebastian; Navickas, Vaidotas; Ditrich, Klaus; Breuer, Michael; Abu, Rohana; Woodley, John M; Baldenius, Kai; Wu, Bian; Janssen, Dick B

    2016-09-01

    We constructed an enzymatic network composed of three different enzymes for the synthesis of valuable ether amines. The enzymatic reactions are interconnected to catalyze the oxidation and subsequent transamination of the substrate and to provide cofactor recycling. This allows production of the desired ether amines from the corresponding ether alcohols with inorganic ammonium as the only additional substrate. To examine conversion, individual and overall reaction equilibria were established. Using these data, it was found that the experimentally observed conversions of up to 60% observed for reactions containing 10 mM alcohol and up to 280 mM ammonia corresponded well to predicted conversions. The results indicate that efficient amination can be driven by high concentrations of ammonia and may require improving enzyme robustness for scale-up. Biotechnol. Bioeng. 2016;113: 1853-1861. © 2016 Wiley Periodicals, Inc.

  20. High capacity immobilized amine sorbents

    DOEpatents

    Gray, McMahan L.; Champagne, Kenneth J.; Soong, Yee; Filburn, Thomas

    2007-10-30

    A method is provided for making low-cost CO.sub.2 sorbents that can be used in large-scale gas-solid processes. The improved method entails treating an amine to increase the number of secondary amine groups and impregnating the amine in a porous solid support. The method increases the CO.sub.2 capture capacity and decreases the cost of utilizing an amine-enriched solid sorbent in CO.sub.2 capture systems.

  1. Degradation and transformation of atrazine under catalyzed ozonation process with TiO2 as catalyst.

    PubMed

    Yang, Yixin; Cao, Hongbin; Peng, Pai; Bo, Hongmiao

    2014-08-30

    Degradation of atrazine by heterogeneously catalyzed ozonation was carried out with TiO2 in the form of rutile as the catalyst. Some experimental factors such as catalyst dose, ozone dose and initial concentration of atrazine were investigated for their influence on catalyzed ozonation process. Although atrazine was effectively removed from aqueous solution by catalyzed ozonation process, the mineralization degree only reached 56% at the experimental conditions. Five transformation products were identified by GC/MS analysis. The degradation of atrazine involved de-alkylation, de-chlorination and de-amination. Diaminotriazine and 5-azauracil were the de-chlorinated and de-aminated products, respectively. The evolution of concentration of transformation products during catalyzed ozonation process was compared with uncatalyzed ozonation to show the degradation pathway. Toxicity tests based on the inhibition of the luminescence emitted by Vibrio fisheri indicated the detoxification of atrazine by catalyzed ozonation.

  2. Enzymatic treatment of sulfonated aromatic amines generated from reductive degradation of reactive azo dyes.

    PubMed

    Biswas, Mousumi Mani; Taylor, Keith E; Bewtra, Jatinder K; Biswas, Nihar

    2007-04-01

    Anaerobic degradation, an effective treatment process of textile industry effluent, generates sulfonated aromatic amines, which are carcinogenic, mutagenic, and resistant to microbial degradation. These aromatic amines can be effectively removed by oxidative polymerization catalyzed by peroxidase enzyme. The amines, generated in this study from the anaerobic reduction by zero-valent iron of two reactive azo dyes (Reactive Red 2 [RR2] and Reactive Black 5 [RB5]), were successfully removed (90%) by Arthromyces ramosus peroxidase (ARP). For better understanding of the process, enzymatic treatment of two model compounds, diphenylamine (DPA) and 2-amino-8-naphthol-3,6-disulfonic acid (ANDSA), were also studied. Diphenylamine has a similar diarylamine bond as RR2. The ANDSA has a similar structure as the dye reduction products. The secondary amine bond in DPA and RR2 were oxidized by ARP. Enzymatic reaction of sulfonated aromatic amines generated soluble colored compounds, which were removed by coagulant. Optimum reaction parameters were also determined.

  3. Mechanistic Elucidation of Zirconium-Catalyzed Direct Amidation.

    PubMed

    Lundberg, Helena; Tinnis, Fredrik; Zhang, Jiji; Algarra, Andrés G; Himo, Fahmi; Adolfsson, Hans

    2017-02-15

    The mechanism of the zirconium-catalyzed condensation of carboxylic acids and amines for direct formation of amides was studied using kinetics, NMR spectroscopy, and DFT calculations. The reaction is found to be first order with respect to the catalyst and has a positive rate dependence on amine concentration. A negative rate dependence on carboxylic acid concentration is observed along with S-shaped kinetic profiles under certain conditions, which is consistent with the formation of reversible off-cycle species. Kinetic experiments using reaction progress kinetic analysis protocols demonstrate that inhibition of the catalyst by the amide product can be avoided using a high amine concentration. These insights led to the design of a reaction protocol with improved yields and a decrease in catalyst loading. NMR spectroscopy provides important details of the nature of the zirconium catalyst and serves as the starting point for a theoretical study of the catalytic cycle using DFT calculations. These studies indicate that a dinuclear zirconium species can catalyze the reaction with feasible energy barriers. The amine is proposed to perform a nucleophilic attack at a terminal η(2)-carboxylate ligand of the zirconium catalyst, followed by a C-O bond cleavage step, with an intermediate proton transfer from nitrogen to oxygen facilitated by an additional equivalent of amine. In addition, the DFT calculations reproduce experimentally observed effects on reaction rate, induced by electronically different substituents on the carboxylic acid.

  4. Enantioselective synthesis of planar chiral ferrocenes via Pd(0)-catalyzed intramolecular direct C-H bond arylation.

    PubMed

    Gao, De-Wei; Yin, Qin; Gu, Qing; You, Shu-Li

    2014-04-02

    A highly efficient synthesis of planar chiral ferrocenes by enantioselective Pd(0)-catalyzed direct C-H arylation from readily available starting materials under mild reaction conditions was developed (up to 99% yield, 99% ee). The products can be easily transformed to the highly efficient planar ferrocene ligands, which have demonstrated high efficiency in Pd-catalyzed asymmetric allylic alkylation and amination reactions.

  5. Amination of surfaces via self-assembly of dopamine.

    PubMed

    Liu, Ying; Yu, Bo; Hao, Jingcheng; Zhou, Feng

    2011-10-01

    Catechols can strongly bind to a variety of substrates so as to functionalize the target surfaces by forming self-assembled monolayer. However, catecholic amine might self-oxidize and polymerize at high pH since the amine is susceptible to nucleophilic addition reaction that results in polymerized oligomers on surfaces. Therefore, the availability of amines for further derivation reaction would be restricted to a large extent. Herein, by controlling pH values to avoid self-oxidative polymerization, dopamine (DA) forms thin and surface-adherent monolayers onto a wide range of inorganic and organic materials, including mica, silica, and Au surface, allowing amination of the surfaces that resemble commercially used aminosilanization. The self-assembly process was traced by surface topography and elemental composition analysis using atomic force microscope (AFM), X-ray photoelectron spectroscopy (XPS), and electrochemical characterization (electrochemical impedance spectroscopy and cyclic voltammetry measurements). Then, the aminated surfaces were used for secondary derivation reactions to create a variety of ad-layers, including patterned streptavidin through specific binding interaction with biotin and ferrocene surface via amidation reaction. The surface and interface properties of the obtained surfaces were tested by electrochemical measurements.

  6. From racemic alcohols to enantiopure amines: Ru-catalyzed diastereoselective amination.

    PubMed

    Oldenhuis, Nathan J; Dong, Vy M; Guan, Zhibin

    2014-09-10

    A commercially available ruthenium(II) PNP-type pincer catalyst (Ru-Macho) promotes the formation of α-chiral tert-butanesulfinylamines from racemic secondary alcohols and Ellman's chiral tert-butanesulfinamide via a hydrogen borrowing strategy. The formation of α-chiral tert-butanesulfinylamines occurs in yields ranging from 31% to 89% with most examples giving >95:5 dr.

  7. Metal-silica sol-gel materials

    NASA Technical Reports Server (NTRS)

    Stiegman, Albert E. (Inventor)

    2002-01-01

    The present invention relates to a single phase metal-silica sol-gel glass formed by the co-condensation of a transition metal with silicon atoms where the metal atoms are uniformly distributed within the sol-gel glass as individual metal centers. Any transition metal may be used in the sol-gel glasses. The present invention also relates to sensor materials where the sensor material is formed using the single phase metal-silica sol-gel glasses. The sensor materials may be in the form of a thin film or may be attached to an optical fiber. The present invention also relates to a method of sensing chemicals using the chemical sensors by monitoring the chromatic change of the metal-silica sol-gel glass when the chemical binds to the sensor. The present invention also relates to oxidation catalysts where a metal-silica sol-gel glass catalyzes the reaction. The present invention also relates to a method of performing oxidation reactions using the metal-silica sol-gel glasses. The present invention also relates to organopolymer metal-silica sol-gel composites where the pores of the metal-silica sol-gel glasses are filled with an organic polymer polymerized by the sol-gel glass.

  8. The interaction of encapsulated pharmaceutical drugs with a silica matrix.

    PubMed

    Morais, Everton C; Correa, Gabriel G; Brambilla, Rodrigo; Radtke, Claudio; Baibich, Ione Maluf; dos Santos, João Henrique Z

    2013-03-01

    A series of seven drugs, namely, fluoxetine, gentamicin, lidocaine, morphine, nifedipine, paracetamol and tetracycline, were encapsulated. The encapsulated systems were characterized using a series of complementary techniques: Fourier-transform infrared spectroscopy (FT-IR), diffusive reflectance spectroscopy in the UV-vis region (DRS) and X-ray photoelectron spectroscopy (XPS). According to the DRS spectra, most of the encapsulated systems showed a band shift of the maximum absorption when compared with the corresponding bare pharmaceutical. Additionally, after encapsulation, the drugs exhibited infrared band shifts toward higher wavenumbers, which in turn provided insight into potential sites for interaction with the silica framework. The amine group showed a band shift in the spectra of almost all the drugs (except nifedipine and tetracycline). This finding indicates the possibility of a hydrogen bonding interaction between the drug and the silica via electron donation from the amine group to the silica framework. XPS confirmed this interaction between the pharmaceuticals and the silica through the amine group. A correlation was observed between the textural characteristics of the solids and the spectroscopic data, suggesting that the amine groups from the pharmaceuticals were more perturbed upon encapsulation.

  9. Amine terminated bisaspartimide polymer

    NASA Technical Reports Server (NTRS)

    Kumar, D. (Inventor); Fohlen, G. M. (Inventor); Parker, J. A. (Inventor)

    1986-01-01

    Novel amine terminated bisaspartimides are prepared by a Michael-type reaction of an aromatic bismalteimide and an aromatic diamine in an aprotic solvent. These bisaspartimides are thermally polymerized to yield tough, resinous polymers cross-lined through -NH- groups. Such polymers are useful in applications requiring materials with resistance to change at elevated temperatures, e.g., as lightweight laminates with graphite cloth, molding material prepregs, adhesives and insulating material.

  10. New porous polycaprolactone-silica composites for bone regeneration.

    PubMed

    Plazas Bonilla, Clara E; Trujillo, Sara; Demirdögen, Bermali; Perilla, Jairo E; Murat Elcin, Y; Gómez Ribelles, José L

    2014-07-01

    Polycaprolactone porous membranes were obtained by freeze extraction of dioxane from polycaprolactone-dioxane solid solutions. Porosities as high as 90% with interconnected structures were obtained by this technique. A silica phase was synthesized inside the pores of the polymer membrane by sol-gel reaction using tetraethylorthosilicate (TEOS) as a silica precursor and catalyzed in acidic and basic conditions. Two different morphologies of the inorganic phase were obtained depending on the type of catalyst. In acid catalyzed sol-gel reaction, a homogeneous layer of silica was deposited on the pores, and discrete microspheres were synthesized on the pore walls when a basic catalyst was used. The morphology of the inorganic phase influenced the mechanical and thermal behavior, as well as the hydrophilic character of the composites. Bioactivity of the porous materials was tested in vitro by measuring the deposition of hydroxyapatite on the surfaces of the porous composite membranes. Polycaprolactone/silica composites revealed a superior bioactivity performance compared with that of the pure polymer; evidenced by the characteristic cauliflower structures on the material surface, increase in weight and Ca/P ratio of the hydroxyapatite layer. Also, the acid catalyzed composites presented better bioactivity than the base catalyzed composites, evidencing the importance in the morphology of the silica phase.

  11. Catalytic enantioselective [2,3]-rearrangements of amine N-oxides.

    PubMed

    Bao, Hongli; Qi, Xiangbing; Tambar, Uttam K

    2011-02-09

    The first Pd-catalyzed enantioselective [2,3]-rearrangement of allylic amine N-oxides is described, which formally represents an asymmetric Meisenheimer rearrangement. The mild reaction conditions enable the synthesis of chiral nonracemic aliphatic allylic alcohol derivatives with reactive functional groups. On the basis of preliminary studies, a cyclization-mediated mechanism is proposed.

  12. Organocatalytic asymmetric allylic amination of Morita–Baylis–Hillman carbonates of isatins

    PubMed Central

    Zhang, Hang; Zhang, Shan-Jun; Zhou, Qing-Qing; Dong, Lin

    2012-01-01

    Summary The investigation of a Lewis base catalyzed asymmetric allylic amination of Morita–Baylis–Hillman carbonates derived from isatins afforded an electrophilic pathway to access multifunctional oxindoles bearing a C3-quaternary stereocenter, provided with good to excellent enantioselectivity (up to 94% ee) and in high yields (up to 97%). PMID:23019454

  13. Aminosilane-grafted polymer/silica hollow fiber adsorbents for CO₂ capture from flue gas.

    PubMed

    Rezaei, Fateme; Lively, Ryan P; Labreche, Ying; Chen, Grace; Fan, Yanfang; Koros, William J; Jones, Christopher W

    2013-05-01

    Amine/silica/polymer composite hollow fiber adsorbents are produced using a novel reactive post-spinning infusion technique, and the obtained fibers are shown to capture CO2 from simulated flue gas. The post-spinning infusion technique allows for functionalization of polymer/silica hollow fibers with different types of amines during the solvent exchange step after fiber spinning. The post-spinning infusion of 3-aminopropyltrimethoxysilane (APS) into mesoporous silica/cellulose acetate hollow fibers is demonstrated here, and the materials are compared with hollow fibers infused with poly(ethyleneimine) (PEI). This approach results in silica/polymer composite fibers with good amine distribution and accessibility, as well as adequate porosity retained within the fibers to facilitate rapid mass transfer and adsorption kinetics. The CO2 adsorption capacities for the APS-infused hollow fibers are shown to be comparable to those of amine powders with similar amine loadings. In contrast, fibers that are spun with presynthesized, amine-loaded mesoporous silica powders show negligible CO2 uptake and low amine loadings because of loss of amines from the silica materials during the fiber spinning process. Aminosilica powders are shown to be more hydrophilic than the corresponding amine containing composite hollow fibers, the bare polymer as well as silica support. Both the PEI-infused and APS-infused fibers demonstrate reduced CO2 adsorption upon elevating the temperature from 35 to 80 °C, in accordance with thermodynamics, whereas PEI-infused powders show increased CO2 uptake over that temperature range because of competing diffusional and thermodynamic effects. The CO2 adsorption kinetics as probed via TGA show that the APS-infused hollow fiber adsorbents have more rapid uptake kinetics than their aminosilica powder analogues. The adsorption performance of the functionalized hollow fibers is also assessed in CO2 breakthrough experiments. The breakthrough results show a

  14. Molecular-level insights into the oxidative degradation of grafted amines.

    PubMed

    Ahmadalinezhad, Asieh; Tailor, Ritesh; Sayari, Abdelhamid

    2013-08-05

    The oxidative degradation of CO2 adsorbents consisting of amine-grafted pore-expanded mesoporous MCM-41 silica was investigated. The adsorbents were treated under flowing air at various temperatures, and the degree of deactivation was evaluated through the measurement of their CO2 adsorption capacity prior and subsequent to exposure to air. To decipher the chemical structure of surface species upon air-deactivation of grafted amines, a solvent extraction procedure was developed using a deuterated basic solution. The obtained solutions were analyzed by a variety of 1D and 2D NMR spectroscopy techniques, such as (29)Si, (13)C, (1)H, [(1)H,(15)N] HMBC, [(1)H,(13)C] HMQC, COSY and DOSY. The surface species generated by oxidative degradation of amine-grafted silica were found to contain functional groups such as imine, amide and carboxylic groups. Several structural units were conclusively demonstrated.

  15. Unexpected role of activated carbon in promoting transformation of secondary amines to N-nitrosamines.

    PubMed

    Padhye, Lokesh; Wang, Pei; Karanfil, Tanju; Huang, Ching-Hua

    2010-06-01

    Activated carbon (AC) is the most common solid phase extraction material used for analysis of nitrosamines in water. It is also widely used for the removal of organics in water treatment and as a catalyst or catalyst support in some industrial applications. In this study, it was discovered that AC materials can catalyze transformation of secondary amines to yield trace levels of N-nitrosamines under ambient aerobic conditions. All 11 commercial ACs tested in the study formed nitrosamines from secondary amines. Among the different ACs, the N-nitrosodimethylamine (NDMA) yield at pH 7.5 ranged from 0.001% to 0.01% of initial amount of aqueous dimethylamine (DMA) concentration, but at 0.05-0.29% of the amount of adsorbed DMA by AC. Nitrosamine yield increased with higher pH and for higher molecular weight secondary amines, probably because of increased adsorption of amines. Presence of oxygen was a critical factor in the transformation of secondary amines, since ACs with adsorbed secondary amines dried under air for longer period of time exhibited significantly higher nitrosamine yields. The AC-catalyzed nitrosamine formation was also observed in surface water and wastewater effluent samples. Properties of AC play an important role in the nitrosamine yields. Preliminary evaluation indicated that nitrosamine formation was higher on reduced than oxidized AC surfaces. Overall, the study results show that selecting ACs and reaction conditions are important to minimize analytical errors and undesirable formation associated with nitrosamines in water samples.

  16. Solid amine development program

    NASA Technical Reports Server (NTRS)

    Lovell, J. S.

    1973-01-01

    A regenerable solid amine material to perform the functions of humidity control and CO2 removal for space shuttle type vehicle is reported. Both small scale and large scale testing have shown this material to be competitive, especially for the longer shuttle missions. However, it had been observed that the material off-gasses ammonia under certain conditions. This presents two concerns. The first, that the ammonia would contaminate the cabin atmosphere, and second, that the material is degrading with time. An extensive test program has shown HS-C to produce only trace quantities of atmospheric contaminants, and under normal extremes, to have no practical life limitation.

  17. Enantio- and Regioselective CuH-Catalyzed Hydroamination of Alkenes

    PubMed Central

    Zhu, Shaolin; Niljianskul, Nootaree; Buchwald, Stephen L.

    2013-01-01

    A highly enantio- and regioselective copper-catalyzed hydroamination reaction of alkenes has been developed using diethoxy(methyl)silane (DEMS) and esters of hydroxylamines. The process tolerates a wide variety of substituted styrenes, including trans-, cis-, and β,β-disubstituted styrenes to yield α–branched amines. In addition, aliphatic alkenes coupled to generate exclusively the anti-Markovnikov hydroamination products. PMID:24106781

  18. Gold(I)-Catalyzed Enantioselective Ring Expansion of Allenylcyclopropanols

    PubMed Central

    Kleinbeck, Florian; Toste, F. Dean

    2009-01-01

    The asymmetric gold(I)-catalyzed ring expansion of 1-allenylcyclopropanols is described. The method provides synthetically valuable cyclobutanones with a vinyl-substituted quaternary stereogenic center in high enantioselectivities and yields. The method shows a broad substrate scope, tolerating protected alcohols and amines, alkenes, unsaturated esters and acetals. The reaction is easily adjustable to large scale synthesis, leading to product formation without significant loss of selectivity or yield with only 0.5 mol% catalyst loading. PMID:19530649

  19. Asymmetric Arylation of Imines Catalyzed by Heterogeneous Chiral Rhodium Nanoparticles.

    PubMed

    Yasukawa, Tomohiro; Kuremoto, Tatsuya; Miyamura, Hiroyuki; Kobayashi, Shu̅

    2016-06-03

    Asymmetric arylation of aldimines catalyzed by heterogeneous chiral rhodium nanoparticles has been developed. The reaction proceeded in aqueous media without significant decomposition of the imines by hydrolysis to afford chiral (diarylmethyl)amines in high yields with outstanding enantioselectivities. This catalyst system exhibited the highest turnover number (700) in heterogeneous catalysts reported to date for these reactions. The reusability of the catalyst was also demonstrated.

  20. Development of an amine dehydrogenase for synthesis of chiral amines.

    PubMed

    Abrahamson, Michael J; Vázquez-Figueroa, Eduardo; Woodall, Nicholas B; Moore, Jeffrey C; Bommarius, Andreas S

    2012-04-16

    A leucine dehydrogenase has been successfully altered through several rounds of protein engineering to an enantioselective amine dehydrogenase. Instead of the wild-type α-keto acid, the new amine dehydrogenase now accepts the analogous ketone, methyl isobutyl ketone (MIBK), which corresponds to exchange of the carboxy group by a methyl group to produce chiral (R)-1,3-dimethylbutylamine.

  1. High resolution patterning of silica aerogels

    SciTech Connect

    Bertino, M.F.; Hund, J.F.; Sosa, J.; Zhang, G.; Sotiriou-Leventis, C.; Leventis, N.; Tokuhiro, A.T.; Terry, J.

    2008-10-30

    Three-dimensional metallic structures are fabricated with high spatial resolution in silica aerogels. In our method, silica hydrogels are prepared with a standard base-catalyzed route, and exchanged with an aqueous solution typically containing Ag{sup +} ions (1 M) and 2-propanol (0.2 M). The metal ions are reduced photolytically with a table-top ultraviolet lamp, or radiolytically, with a focused X-ray beam. We fabricated dots and lines as small as 30 x 70 {micro}m, protruding for several mm into the bulk of the materials. The hydrogels are eventually supercritically dried to yield aerogels, without any measurable change in the shape and spatial resolution of the lithographed structures. Transmission electron microscopy shows that illuminated regions are composed by Ag clusters with a size of several {micro}m, separated by thin layers of silica.

  2. Enzymatic Ugi Reaction with Amines and Cyclic Imines.

    PubMed

    Żądło-Dobrowolska, Anna; Kłossowski, Szymon; Koszelewski, Dominik; Paprocki, Daniel; Ostaszewski, Ryszard

    2016-11-07

    The application of the Ugi reaction to the construction of new peptide scaffolds is an important goal of organic chemistry. To date, there are no examples of the Ugi reaction being performed with a cyclic imine and amine simultaneously. The application of 2-substituted cyclic imines in an enzymatic three-component Ugi-type reaction provides an elegant and attractive synthesis of substituted pyrrolidine and piperidine derivatives in up to 60 % yield. Results on studies of the selection of an enzyme, amount of water, and solvent used in a novel three-component Ugi reaction and the limitations thereof are reported herein. The presented methodology exploiting enzyme promiscuity in the multicomponent reaction fulfills the requirements associated with green chemistry. Several methods, such as isotope labeling and enzyme inhibition, were used to probe the possible mechanism of this complex synthesis. This research is the first example of an enzyme-catalyzed Ugi-type reaction with an imine, amine, and isocyanide.

  3. Uptake of N-(4'-pyridoxyl)amines and release of amines by renal cells: a model for transporter-enhanced delivery of bioactive compounds.

    PubMed Central

    Zhang, Z M; McCormick, D B

    1991-01-01

    The importing of vitamin B6 by renal proximal tubular cells from the rat is facilitated and Na(+)-dependent and reflects specificity for the meta-phenolate pyridinium structure with a 5-hydroxymethyl function. This transporter can, however, accept competitively each of the natural nonphosphorylated vitamers (pyridoxine, pyridoxamine, and pyridoxal) and other B6 analogues differing only in the groups at position 4. A series of N-(4'-pyridoxyl)amines was synthesized by sodium borohydride or boro[3H]hydride reduction of aldimines formed by condensing the amines with pyridoxal. The unlabeled B6-secondary amine compounds were found to competitively inhibit the uptake of [4'-3H]pyridoxine by the renal cells. Moreover, the 3H-labeled N-(4'-pyridoxyl)amines were shown to enter the cells by the process facilitated by the B6 transporter. Upon entry the labeled compounds were converted to N-(5'-phospho-4'-pyridoxyl)amines in a reaction catalyzed by pyridoxal kinase, an enzyme that tolerates considerable functional variation in position 4 of the B6 structure. The 5'-phosphates were subsequently converted within the cell to pyridoxal 5'-phosphate with liberation of the original amine in a reaction catalyzed by pyridoxamine (pyridoxine) 5'-phosphate oxidase, an enzyme with broad specificity for 4'-substituted amines on the 5'-phospho-B6 structure. This system illustrates how knowledge of transporter specificity can permit design of a compound with potential biologic activity. A drug or other intracellular effector may be piggybacked onto a transported solute (e.g., vitamin or other nutrient) that gains facilitated entry to a cell and is, thereafter, metabolized to release the active compound. PMID:1961706

  4. Silica and titanium dioxide nanoparticles cause pregnancy complications in mice

    NASA Astrophysics Data System (ADS)

    Yamashita, Kohei; Yoshioka, Yasuo; Higashisaka, Kazuma; Mimura, Kazuya; Morishita, Yuki; Nozaki, Masatoshi; Yoshida, Tokuyuki; Ogura, Toshinobu; Nabeshi, Hiromi; Nagano, Kazuya; Abe, Yasuhiro; Kamada, Haruhiko; Monobe, Youko; Imazawa, Takayoshi; Aoshima, Hisae; Shishido, Kiyoshi; Kawai, Yuichi; Mayumi, Tadanori; Tsunoda, Shin-Ichi; Itoh, Norio; Yoshikawa, Tomoaki; Yanagihara, Itaru; Saito, Shigeru; Tsutsumi, Yasuo

    2011-05-01

    The increasing use of nanomaterials has raised concerns about their potential risks to human health. Recent studies have shown that nanoparticles can cross the placenta barrier in pregnant mice and cause neurotoxicity in their offspring, but a more detailed understanding of the effects of nanoparticles on pregnant animals remains elusive. Here, we show that silica and titanium dioxide nanoparticles with diameters of 70 nm and 35 nm, respectively, can cause pregnancy complications when injected intravenously into pregnant mice. The silica and titanium dioxide nanoparticles were found in the placenta, fetal liver and fetal brain. Mice treated with these nanoparticles had smaller uteri and smaller fetuses than untreated controls. Fullerene molecules and larger (300 and 1,000 nm) silica particles did not induce these complications. These detrimental effects are linked to structural and functional abnormalities in the placenta on the maternal side, and are abolished when the surfaces of the silica nanoparticles are modified with carboxyl and amine groups.

  5. Optimization of silica silanization by 3-aminopropyltriethoxysilane.

    PubMed

    Howarter, John A; Youngblood, Jeffrey P

    2006-12-19

    Thin films of 3-aminopropyltriethoxysilane (APTES) are commonly used to promote adhesion between silica substrates and organic or metallic materials with applications ranging from advanced composites to biomolecular lab-on-a-chip. Unfortunately, there is confusion as to which reaction conditions will result in consistently aminated surfaces. A wide range of conflicting experimental methods are used with researchers often assuming the creation of smooth self-assembled monolayers. A range of film morphologies based on the film deposition conditions are presented here to establish an optimized method of APTES film formation. The effect of reaction temperature, solution concentration, and reaction time on the structure and morphology was studied for the system of APTES on silica. Three basic morphologies were observed: smooth thin film, smooth thick film, and roughened thick film.

  6. Gold(III)-catalyzed three-component coupling reaction (TCC) selective toward furans.

    PubMed

    Li, Jian; Liu, Li; Ding, Dong; Sun, Jiangtao; Ji, Yangxuan; Dong, Jialing

    2013-06-07

    An efficient three-component coupling reaction toward a variety of furan derivatives has been developed. This cascade transformation proceeds via the gold-catalyzed coupling reaction of phenylglyoxal derivatives, secondary amines, and terminal alkynes, under the reaction conditions, that undergoes cyclization into the furan core.

  7. Osmium-catalyzed vicinal oxyamination of alkenes by N-(4-toluenesulfonyloxy)carbamates.

    PubMed

    Masruri; Willis, Anthony C; McLeod, Malcolm D

    2012-10-05

    N-(4-toluenesulfonyloxy)carbamates based on a range of common amine protecting groups serve as preformed nitrogen sources in the intermolecular osmium-catalyzed oxyamination reaction of a variety of mono-, di-, and trisubstituted alkenes. The reactions occur with low catalyst loadings and good yields and afford high regioselectivity for unsymmetrically substituted alkenes.

  8. Copper-catalyzed aminooxygenation of styrenes with N-fluorobenzenesulfonimide and N-hydroxyphthalimide derivatives

    PubMed Central

    Li, Yan; Zhou, Xue; Zheng, Guangfan

    2015-01-01

    Summary A copper-catalyzed aminooxygenation reaction of styrenes with N-fluorobenzenesulfonimide and N-hydroxyphthalimide derivatives has been developed. The aminooxygenation product could be converted into the corresponding alcohol or free amine through the cleavage of the N–O or C–N bond of the N-hydroxyphthalimide moiety. PMID:26877794

  9. Copper(I) catalyzed regioselective asymmetric alkoxyamination of aryl enamide derivatives.

    PubMed

    Nakanishi, Masafumi; Minard, Corinne; Retailleau, Pascal; Cariou, Kevin; Dodd, Robert H

    2011-11-04

    The copper(I) catalyzed reaction of an enamide with an iminoiodane, in the presence of an alcohol, triggers the direct alkoxyamination of the double bond. This transformation represents a straightforward access to α-amino aminals in a completely regio- and diastereoselective manner. Use of a chiral Box ligand allows this reaction to be carried out in an enantioselective fashion.

  10. Muon Catalyzed Fusion

    NASA Technical Reports Server (NTRS)

    Armour, Edward A.G.

    2007-01-01

    Muon catalyzed fusion is a process in which a negatively charged muon combines with two nuclei of isotopes of hydrogen, e.g, a proton and a deuteron or a deuteron and a triton, to form a muonic molecular ion in which the binding is so tight that nuclear fusion occurs. The muon is normally released after fusion has taken place and so can catalyze further fusions. As the muon has a mean lifetime of 2.2 microseconds, this is the maximum period over which a muon can participate in this process. This article gives an outline of the history of muon catalyzed fusion from 1947, when it was first realised that such a process might occur, to the present day. It includes a description of the contribution that Drachrnan has made to the theory of muon catalyzed fusion and the influence this has had on the author's research.

  11. Catalyzing RE Project Development

    SciTech Connect

    Anderson, Kate; Elgqvist, Emma; Walker, Andy; Cutler, Dylan; Olis, Dan; DiOrio, Nick; Simpkins, Travis

    2016-09-01

    This poster details how screenings done with REopt - NREL's software modeling platform for energy systems integration and optimization - are helping to catalyze the development of hundreds of megawatts of renewable energy.

  12. Mechanisms and Kinetics for Sorption of CO2 on Bicontinuous Mesoporous Silica Modified with n-Propylamine

    PubMed Central

    2011-01-01

    We studied equilibrium adsorption and uptake kinetics and identified molecular species that formed during sorption of carbon dioxide on amine-modified silica. Bicontinuous silicas (AMS-6 and MCM-48) were postsynthetically modified with (3-aminopropyl)triethoxysilane or (3-aminopropyl)methyldiethoxysilane, and amine-modified AMS-6 adsorbed more CO2 than did amine-modified MCM-48. By in situ FTIR spectroscopy, we showed that the amine groups reacted with CO2 and formed ammonium carbamate ion pairs as well as carbamic acids under both dry and moist conditions. The carbamic acid was stabilized by hydrogen bonds, and ammonium carbamate ion pairs formed preferably on sorbents with high densities of amine groups. Under dry conditions, silylpropylcarbamate formed, slowly, by condensing carbamic acid and silanol groups. The ratio of ammonium carbamate ion pairs to silylpropylcarbamate was higher for samples with high amine contents than samples with low amine contents. Bicarbonates or carbonates did not form under dry or moist conditions. The uptake of CO2 was enhanced in the presence of water, which was rationalized by the observed release of additional amine groups under these conditions and related formation of ammonium carbamate ion pairs. Distinct evidence for a fourth and irreversibly formed moiety was observed under sorption of CO2 under dry conditions. Significant amounts of physisorbed, linear CO2 were detected at relatively high partial pressures of CO2, such that they could adsorb only after the reactive amine groups were consumed. PMID:21774480

  13. Allylic C-H amination for the preparation of syn-1,3-amino alcohol motifs.

    PubMed

    Rice, Grant T; White, M Christina

    2009-08-26

    A highly selective and general Pd/sulfoxide-catalyzed allylic C-H amination reaction en route to syn-1,3-amino alcohol motifs is reported. Key to achieving this reactivity under mild conditions is the use of electron-deficient N-nosyl carbamate nucleophiles that are thought to promote functionalization by furnishing higher concentrations of anionic species in situ. The reaction is shown to be orthogonal to classical C-C bond-forming/-reduction sequences as well as nitrene-based C-H amination methods.

  14. Homopiperazine grafted mesoporous silicas from rice husk ash for CO2 adsorption.

    PubMed

    Vinodh, Rajangam; Bhagiyalakshmi, Margandan; Hemalatha, Pushparaj; Ganesh, Mani; Peng, Mei Mei; Palanichamy, Muthiahpillai; Cha, Wang Seog; Jang, Hyun Tae

    2014-06-01

    Chloro-functionalized mesoporous MCM-41, SBA-15, MCM-48 and KIT-6 were synthesized by co-condensation of 3-chloropropyl-trimethoxy-silane (CPTMS) and rice husk ash sodium silicate solution, which is subsequently grafted with a heterocyclic amine, homopiperazine (HPZ). X-ray powder diffraction and BET analysis of the chloro-functionalized mesoporous silicas confirmed the similarity between their structural properties and those obtained from conventional silica sources. CO2 adsorption studies of all HPZ-grafted mesoporous silicas exhibited 8-10 wt% of adsorption capacity and are found to be selective, recyclable and thermally stable. Here, the CO2 adsorption reaction is via the traditional carbamate mechanism. The presence of both secondary and tertiary amine in HPZ influences the high CO2 adsorption capacity. Hence, these HPZ-grafted mesoporous silicas could contribute to CO2 capture as a green, tunable, selective and efficient sorbent.

  15. Immobilization of bacteriophages on modified silica particles.

    PubMed

    Cademartiri, Rebecca; Anany, Hany; Gross, Isabelle; Bhayani, Rahul; Griffiths, Mansel; Brook, Michael A

    2010-03-01

    Bacteriophages are selective anti-bacterial agents, which are receiving increasing acceptance by regulatory agencies for use both in the food industry and in clinical settings for biocontrol. While immobilized phage could be particularly useful to create antimicrobial surfaces, current immobilization strategies require chemical bioconjugation to surfaces or more difficult processes involving modification of their head proteins to express specific binding moieties, for example, biotin or cellulose binding domains; procedures that are both time and money intensive. We report that morphologically different bacteriophages, active against a variety of food-borne bacteria: Escherichia coli; Salmonella enterica; Listeria monocytogenes; and Shigella boydii, will effectively physisorb to silica particles, prepared by silica surface modification with poly(ethylene glycol), carboxylic acid groups, or amines. The phages remain infective to their host bacteria while adsorbed on the surface of the silica particles. The number of infective phage bound to the silica is enhanced by the presence of ionic surfaces, with greater surface charge - to a maximum - correlating with greater concentration of adsorbed phage. Above the maximum charge concentration, the number of active phage drops.

  16. Enantioselective Generation of Adjacent Stereocenters in a Copper‐Catalyzed Three‐Component Coupling of Imines, Allenes, and Diboranes

    PubMed Central

    Yeung, Kay; Ruscoe, Rebecca E.; Rae, James; Pulis, Alexander P.

    2016-01-01

    Abstract A highly enantio‐ and diastereoselective copper‐catalyzed three‐component coupling affords the first general synthesis of homoallylic amines bearing adjacent stereocenters from achiral starting materials. The method utilizes a commercially available NHC ligand and copper source, operates at ambient temperature, couples readily available simple imines, allenes, and diboranes, and yields high‐value homoallylic amines that exhibit versatile amino, alkenyl, and boryl units. PMID:27539673

  17. Cu-catalyzed aerobic oxidative three-component coupling route to N-sulfonyl amidines via an ynamine intermediate.

    PubMed

    Kim, Jinho; Stahl, Shannon S

    2015-02-20

    Cu-catalyzed aerobic oxidative three-component coupling of a terminal alkyne, secondary amine, and sulfonamide enables efficient synthesis of amidines. The use of Cu(OTf)2 (5 mol %) produces amidines selectively without Glaser-Hay alkyne homocoupling products. Preliminary studies suggest that the reaction pathway involves initial oxidative coupling of the terminal alkyne with the secondary amine, followed by hydroamidation of the ynamine intermediate with the sulfonamide.

  18. Silica extraction from geothermal water

    DOEpatents

    Bourcier, William L; Bruton, Carol J

    2014-09-23

    A method of producing silica from geothermal fluid containing low concentration of the silica of less than 275 ppm includes the steps of treating the geothermal fluid containing the silica by reverse osmosis treatment thereby producing a concentrated fluid containing the silica, seasoning the concentrated fluid thereby producing a slurry having precipitated colloids containing the silica, and separating the silica from the slurry.

  19. Formation of hollow silica nanospheres by reverse microemulsion.

    PubMed

    Lin, Cheng-Han; Chang, Jen-Hsuan; Yeh, Yi-Qi; Wu, Si-Han; Liu, Yi-Hsin; Mou, Chung-Yuan

    2015-06-07

    Uniform hollow silica nanospheres (HSNs) synthesized with reverse microemulsion have great application potential as nanoreactors because enzymes or nanocatalysts can be easily encapsulated de novo in synthesis. Water-in-oil (w/o) reverse microemulsions comprising the polymeric surfactant polyoxyethylene (5) isooctylphenyl ether (Igepal CA-520), ammonia and water in a continuous oil phase (alkanes) coalesce into size-tunable silica nanoparticles via diffusion aggregation after the introduction of silica precursors. Here, we elucidate in detail the growth mechanism for silica nanoparticles via nucleation of ammonium-catalyzed silica oligomers from tetraethylorthosilicate (TEOS) and nanoporous aminopropyltrimethoxy silane (APTS) in the reverse microemulsion system. The formation pathway was studied in situ with small-angle X-ray scattering (SAXS). We find a four-stage process showing a sigmoidal growth behavior in time with a crossover from the induction period, early nucleation stage, coalescence growth and a final slowing down of growth. Various characterizations (TEM, N2 isotherm, dynamic light scattering, zeta potential, NMR, elemental analysis) reveal the diameters, scattering length density (SLD), mesoporosity, surface potentials and chemical compositions of the HSNs. Oil phases of alkanes with different alkyl chains are systematically employed to tune the sizes of HSNs by varying oil molar volumes, co-solvent amounts or surfactant mixture ratios. Silica condensation is incomplete in the core region, with the silica source of TEOS and APTS leading to the hollow silica nanosphere after etching with warm water.

  20. In vitro studies of interaction of modified silica nanoparticles with different types of immunocompetent cells.

    PubMed

    Kulikova, Galina A; Parfenyuk, Elena V; Ryabinina, Irina V; Antsiferova, Yuliya S; Sotnikova, Nataliya Yu; Posiseeva, Lubov V; Eliseeva, Mariya A

    2010-11-01

    Interactions between different types of immune cells and organically-modified silica nanoparticles were studied. The silica particles functionalized with amine groups were prepared by sol-gel technique. Sheep immunoglobulin labeled with fluoresceine isothiocyanate was immobilized by adsorption onto the nanoparticles. The presence of the functional groups was confirmed by infrared absorption measurements. The level of immunocompetent cells interacting with the silica nanoparticles was estimated as the amount of fluorescence-bright cells by flow cytometry method. A low level of interaction of the peripheral blood lymphocytes with the silica nanoparticles was found. On the contrary, the macrophages are actively involved in interaction with the silica nanoparticles. The influence of different size of the silica nanoparticles and incubation time on viability and functional activity of peripheral blood lymphocytes and peritoneal macrophages were investigated.

  1. Palladium-Catalyzed Aminocarbonylation of Allylic Alcohols.

    PubMed

    Li, Haoquan; Neumann, Helfried; Beller, Matthias

    2016-07-11

    A benign and efficient palladium-catalyzed aminocarbonylation reaction of allylic alcohols is presented. The generality of this novel process is demonstrated by the synthesis of β,γ-unsaturated amides including aliphatic, cinnamyl, and terpene derivatives. The choice of ligand is crucial for optimal carbonylation processes: Whereas in most cases the combination of PdCl2 with Xantphos (L6) gave best results, sterically hindered substrates performed better in the presence of simple triphenylphosphine (L10), and primary anilines gave the best results using cataCXium® PCy (L8). The reactivity of the respective catalyst system is significantly enhanced by addition of small amounts of water. Mechanistic studies and control experiments revealed a tandem allylic alcohol amination/C-N bond carbonylation reaction sequence.

  2. Deciphering the origin of cooperative catalysis by dirhodium acetate and chiral spiro phosphoric acid in an asymmetric amination reaction.

    PubMed

    Kisan, Hemanta K; Sunoj, Raghavan B

    2014-12-04

    The mechanism of asymmetric amination of diazo-acetate by tert-butyl carbamate catalyzed by dirhodium tetra(trifluoro)acetate and chiral SPINOL-phosphoric acid is examined using DFT (M06 and B3LYP) computations. A cooperative participation of both catalysts is noticed in the stereo-controlling transition state of the reaction.

  3. Development and validation of a hydrophilic interaction liquid chromatographic method for determination of aromatic amines in environmental water

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A simple, precise, and accurate hydrophilic interaction liquid chromatographic (HILIC) method has been developed for the determination of 5 aromatic amines in environmental water samples. Chromatography was carried out on a bare silica column, using a mixture of acetonitrile: phosphate buffer (10 mM...

  4. Amine-Amine Exchange in Aminium-Methanesulfonate Aerosols

    SciTech Connect

    Dawson, Matthew L.; Varner, Mychel E.; Perraud, Veronique M.; Ezell, Michael J.; Wilson, Jacqueline M.; Zelenyuk, Alla; Gerber, Robert B.; Finlayson-Pitts, Barbara J.

    2014-12-18

    Aerosol particles are ubiquitous in the atmosphere and have been shown to impact the Earth’s climate, reduce visibility, and adversely affect human health. Modeling the evolution of aerosol systems requires an understanding of the species and mechanisms involved in particle growth, including the complex interactions between particle- and gas-phase species. Here we report studies of displacement of amines (methylamine, dimethylamine or trimethylamine) in methanesulfonate salt particles by exposure to a different gas-phase amine, using a single particle mass spectrometer, SPLAT II. The variation of the displacement with the nature of the amine suggests that behavior is dependent on water in or on the particles. Small clusters of methanesulfonic acid with amines are used as a model in quantum chemical calculations to identify key structural elements that are expected to influence water uptake, and hence the efficiency of displacement by gas-phase molecules in the aminium salts. Such molecular-level understanding of the processes affecting the ability of gas-phase amines to displace particle-phase aminium species is important for modeling the growth of particles and their impacts in the atmosphere.

  5. Bacterial degradation of monocyclic aromatic amines.

    PubMed

    Arora, Pankaj K

    2015-01-01

    Aromatic amines are an important group of industrial chemicals, which are widely used for manufacturing of dyes, pesticides, drugs, pigments, and other industrial products. These compounds have been considered highly toxic to human beings due to their carcinogenic nature. Three groups of aromatic amines have been recognized: monocyclic, polycyclic, and heterocyclic aromatic amines. Bacterial degradation of several monocyclic aromatic amines has been studied in a variety of bacteria, which utilizes monocyclic aromatic amines as their sole source of carbon and energy. Several degradation pathways have been proposed and the related enzymes and genes have also been characterized. Many reviews have been reviewed toxicity of monocyclic aromatic amines; however, there is lack of review on biodegradation of monocyclic aromatic amines. The aim of this review is to summarize bacterial degradation of monocyclic aromatic amines. This review will increase our current understanding of biochemical and molecular basis of bacterial degradation of monocyclic aromatic amines.

  6. Synthesis and adsorption of silica gel modified 3-aminopropyltriethoxysilane (APTS) from corn cobs against Cu(II) in water

    NASA Astrophysics Data System (ADS)

    Purwanto, Agung; Yusmaniar, Ferdiani, Fatmawati; Damayanti, Rachma

    2017-03-01

    Silica gel modified APTS was synthesized from silica gel which was obtained from corn cobs via sol-gel process. Silica gel was synthesized from corn cobs and then chemically modified with silane coupling agent which has an amine group (NH2). This process resulting modified silica gel 3-aminopropyltriethoxysilane (APTS). Characterization of silica gel modified APTS by SEM-EDX showed that the size of the particles of silica gel modified APTS was 20µm with mass percentage of individual elements were nitrogen (N) 15.56%, silicon (Si) 50.69% and oxygen (O) 33.75%. In addition, silica gel modified APTS also showed absorption bands of functional groups silanol (Si-OH), siloxane (Si-O-Si), and an aliphatic chain (-CH2-), as well as amine (NH2) from FTIR spectra. Based on the characterization of XRD, silica gel 2θ of 21.094° and 21.32° respectively. It indicated that both material were amorphous. Determination of optimum pH and contact time on adsorption of silica gel 3-aminopropyltriethoxysilane (APTS) against Cu(II). The optimum pH and contact time was measured by using AAS. Optimum pH of adsorption silica gel modified APTS against metal Cu(II) could be obtained at pH 6 while optimum contact time was at 30 minutes, with the process of adsorption metal Cu(II) occured based on the model Freundlich isotherm.

  7. Highly efficient palladium-catalyzed hydrostannation of ethyl ethynyl ether.

    PubMed

    Andrews, Ian P; Kwon, Ohyun

    2008-12-08

    The palladium-catalyzed hydrostannation of acetylenes is widely exploited in organic synthesis as a means of forming vinyl stannanes for use in palladium-catalyzed cross-coupling reactions. Application of this methodology to ethyl ethynyl ether results in an enol ether that is challenging to isolate from the crude reaction mixture because of incompatibility with typical silica gel chromatography. Reported here is a highly efficient procedure for the palladium-catalyzed hydrostannation of ethyl ethynyl ether using 0.1% palladium(0) catalyst and 1.0 equiv of tributyltin hydride. The product obtained is a mixture of regioisomers that can be carried forward with exclusive reaction of the beta-isomer. This method is highly reproducible; relative to previously reported procedures, it is more economical and involves a more facile purification procedure.

  8. Aryl Amination using Ligand-Free Ni(II) Salts and Photoredox Catalysis

    PubMed Central

    Corcoran, Emily B.; Pirnot, Michael T.; Lin, Shishi; Dreher, Spencer D.; DiRocco, Daniel A.; Davies, Ian W.; Buchwald, Stephen L.; MacMillan, David W. C.

    2016-01-01

    Over the past two decades, there have been major developments in transition metal-catalyzed aminations of aryl halides to form anilines, a common structure found in drug agents, natural product isolates, and fine chemicals. Many of these approaches have enabled highly efficient and selective coupling through the design of specialized ligands, which facilitate reductive elimination from a destabilized metal center. We postulated that a general and complementary method for C–N bond formation could be developed through the destabilization of a metal amido complex via photoredox catalysis, thus providing an alternative approach to the use of structurally complex ligand systems. Herein, we report the development of a distinct mechanistic paradigm for aryl amination using ligand-free nickel(II) salts, in which facile reductive elimination from the nickel metal center is induced via a photoredox-catalyzed electron-transfer event. PMID:27338703

  9. Amine Swingbed Payload Project Management

    NASA Technical Reports Server (NTRS)

    Hayley, Elizabeth; Curley, Su; Walsh, Mary

    2011-01-01

    The International Space Station (ISS) has been designed as a laboratory for demonstrating technologies in a microgravity environment, benefitting exploration programs by reducing the overall risk of implementing such technologies in new spacecraft. At the beginning of fiscal year 2010, the ISS program manager requested that the amine-based, pressure-swing carbon dioxide and humidity absorption technology (designed by Hamilton Sundstrand, baselined for the ORION Multi-Purpose Crew Vehicle, and tested at the Johnson Space Center in relevant environments, including with humans, since 2005) be developed into a payload for ISS Utilization. In addition to evaluating the amine technology in a flight environment before the first launch of the ORION vehicle, the ISS program wanted to determine the capability of the amine technology to remove carbon dioxide from the ISS cabin environment at the metabolic rate of the full 6-person crew. Because the amine technology vents the absorbed carbon dioxide and water vapor to space vacuum (open loop), additional hardware needed to be developed to minimize the amount of air and water resources lost overboard. Additionally, the payload system would be launched on two separate Space Shuttle flights, with the heart of the payload the swingbed unit itself launching a full year before the remainder of the payload. This paper discusses the project management and challenges of developing the amine swingbed payload in order to accomplish the technology objectives of both the open-loop ORION application as well as the closed-loop ISS application.

  10. Amine Swingbed Payload Project Management

    NASA Technical Reports Server (NTRS)

    Walsch, Mary; Curley, Su

    2013-01-01

    The International Space Station (ISS) has been designed as a laboratory for demonstrating technologies in a microgravity environment, benefitting exploration programs by reducing the overall risk of implementing such technologies in new spacecraft. At the beginning of fiscal year 2010, the ISS program manager requested that the amine-based, pressure-swing carbon dioxide and humidity absorption technology (designed by Hamilton Sundstrand, baselined for the Orion Multi-Purpose Crew Vehicle, and tested at the Johnson Space Center in relevant environments, including with humans, since 2005) be developed into a payload for ISS Utilization. In addition to evaluating the amine technology in a flight environment before the first launch of the Orion vehicle, the ISS program wanted to determine the capability of the amine technology to remove carbon dioxide from the ISS cabin environment at the metabolic rate of the full 6 ]person crew. Because the amine technology vents the absorbed carbon dioxide and water vapor to space vacuum (open loop), additional hardware needed to be developed to minimize the amount of air and water resources lost overboard. Additionally, the payload system would be launched on two separate Space Shuttle flights, with the heart of the payload-the swingbed unit itself-launching a full year before the remainder of the payload. This paper discusses the project management and challenges of developing the amine swingbed payload in order to accomplish the technology objectives of both the open -loop Orion application as well as the closed-loop ISS application.

  11. Electrochemically assisted fabrication of size-exclusion films of organically modified silica and application to the voltammetry of phospholipids

    PubMed Central

    Mehdi, B. Layla; Rutkowska, Iwona A.; Kulesza, Pawel J.

    2013-01-01

    Modification of electrodes with nm-scale organically modified silica films with pores diameters controlled at 10- and 50-nm is described. An oxidation catalyst, mixed-valence ruthenium oxide with cyano crosslinks or gold nanoparticles protected by dirhodium-substituted phosophomolybdate (AuNP-Rh2PMo11), was immobilized in the pores. These systems comprise size-exclusion films at which the biological compounds, phosphatidylcholine and cardiolipin, were electrocatalytically oxidized without interference from surface-active concomitants such as bovine serum albumin. 10-nm pores were obtained by adding generation-4 poly(amidoamine) dendrimer, G4-PAMAM, to a (CH3)3SiOCH3 sol. 50-nm pores were obtained by modifying a glassy carbon electrode (GC) with a sub-monolayer film of aminopropyltriethoxylsilane, attaching 50-nm diameter poly(styrene sulfonate), PSS, spheres to the protonated amine, transferring this electrode to a (CH3)3SiOCH3 sol, and electrochemically generating hydronium at uncoated GC sites, which catalyzed ormosil growth around the PSS. Voltammetry of Fe(CN)63− and Ru(NH3)63+ demonstrated the absence of residual charge after removal of the templating agents. With the 50-nm system, the pore structure was sufficiently defined to use layer-by-layer electrostatic assembly of AuNP-Rh2PMo11 therein. Flow injection amperometry of phosphatidylcholine and cardiolipin demonstrated analytical utility of these electrodes. PMID:23935394

  12. Catalytic dehydrogenative N-((triisopropylsilyl)oxy)carbonyl (Tsoc) protection of amines using iPr3SiH and CO2.

    PubMed

    Tanaka, S; Yamamura, T; Nakane, S; Kitamura, M

    2015-08-25

    A versatile method has been found to catalyze the dehydrogenative N-((triisopropylsilyl)oxy)carbonyl (Tsoc) protection of amines using Pd/C, volatile iPr3SiH and CO2 gas without the liberation of any salts. A simple filtration/evaporation process facilitates the easy isolation of the product, thereby enhancing the utility of Tsoc as an amine-protecting group in organic synthesis.

  13. Silica Synthesis by Sponges: Unanticipated Molecular Mechanism

    NASA Astrophysics Data System (ADS)

    Morse, D. E.; Weaver, J. C.

    2001-12-01

    Oceanic diatoms, sponges and other organisms synthesize gigatons per year of silica from silicic acid, ultimately obtained from the weathering of rock. This biogenic silica exhibits a remarkable diversity of structures, many of which reveal a precision of nanoarchitectural control that exceeds the capabilities of human engineering. In contrast to the conditions of anthropogenic and industrial manufacture, the biological synthesis of silica occurs under mild physiological conditions of low temperatures and pressures and near-neutral pH. In addition to the differentiation between biological and abiotic processes governing silica formation, the biomolecular mechanisms controlling synthesis of these materials may offer insights for the development of new, environmentally benign routes for synthesis of nanostructurally controlled silicas and high-performance polysiloxane composites. We found that the needle-like silica spicules made by the marine sponge, Tethya aurantia, each contain an occluded axial filament of protein composed predominantly of repeating assemblies of three similar subunits we named "silicateins." To our surprise, analysis of the purified protein subunits and the cloned silicatein DNAs revealed that the silicateins are highly homologous to a family of hydrolytic enzymes. As predicted from this finding, we discovered that the silicatein filaments are more than simple, passive templates; they actively catalyze and spatially direct polycondensation to form silica, (as well as the phenyl- and methyl-silsesquioxane) from the corresponding silicon alkoxides at neutral pH and low temperature. Catalytic activity also is exhibited by the silicatein subunits obtained by disaggregation of the protein filaments and those produced from recombinant DNA templates cloned in bacteria. This catalytic activity accelerates the rate-limiting hydrolysis of the silicon alkoxide precursors. Genetic engineering, used to produce variants of the silicatein molecule with

  14. Enantioselective Terminal Addition to Allenes by Dual Chiral Primary Amine/Palladium Catalysis.

    PubMed

    Zhou, Han; Wang, Yaning; Zhang, Long; Cai, Mao; Luo, Sanzhong

    2017-03-15

    We herein describe a synergistic chiral primary amine/achiral palladium catalyzed enantioselective terminal addition to allenes with α-branched β-ketocarbonyls and aldehydes. The reactions afford allylic adducts bearing acyclic all-carbon quaternary centers with high regio- and enantioselectivity. A wide range of allenes including those aliphatic or 1,1'-disubstituted could be employed, thus expanding the scope of typical asymmetric allylic alkylation reactions.

  15. Amine Swingbed Payload Technology Demonstration

    NASA Technical Reports Server (NTRS)

    Sweterlitsch, Jeffrey

    2014-01-01

    The Amine Swingbed is an amine-based, vacuum-regenerated adsorption technology for removing carbon dioxide and humidity from a habitable spacecraft environment, and is the baseline technology for the Orion Program’s Multi-Purpose Crew Vehicle (MPCV). It uses a pair of interleaved-layer beds filled with SA9T, the amine sorbent, and a linear multiball valve rotates 270° back and forth to control the flow of air and vacuum to adsorbing and desorbing beds. One bed adsorbs CO2 and H2O from cabin air while the other bed is exposed to vacuum for regeneration by venting the CO2 and H2O. The two beds are thermally linked, so no additional heating or cooling is required. The technology can be applied to habitable environments where recycling CO2 and H2O is not required such as short duration missions.

  16. Amine promiscuity and toxicology analysis.

    PubMed

    Lee, Esther C Y; Steeno, Gregory; Wassermann, Anne Mai; Zhang, Liying; Shah, Falgun; Price, David A

    2017-02-01

    Drug discovery programs often face challenges to obtain sufficient duration of action of the drug (i.e. seek longer half-lives). If the pharmacodynamic response is driven by free plasma concentration of the drug then extending the plasma drug concentration is a valid approach. Half-life is dependent on the volume of distribution, which in turn can be dependent upon the ionization state of the molecule. Basic compounds tend to have a higher volume of distribution leading to longer half-lives. However, it has been shown that bases may also have higher promiscuity. In this work, we describe an analysis of in vitro pharmacological profiling and toxicology data investigating the role of primary, secondary, and tertiary amines in imparting promiscuity and thus off-target toxicity. Primary amines are found to be less promiscuous in in vitro assays and have improved profiles in in vivo toxicology studies compared to secondary and tertiary amines.

  17. Enzyme-controlled nitrogen-atom transfer enables regiodivergent C-H amination.

    PubMed

    Hyster, Todd K; Farwell, Christopher C; Buller, Andrew R; McIntosh, John A; Arnold, Frances H

    2014-11-05

    We recently demonstrated that variants of cytochrome P450BM3 (CYP102A1) catalyze the insertion of nitrogen species into benzylic C-H bonds to form new C-N bonds. An outstanding challenge in the field of C-H amination is catalyst-controlled regioselectivity. Here, we report two engineered variants of P450BM3 that provide divergent regioselectivity for C-H amination-one favoring amination of benzylic C-H bonds and the other favoring homo-benzylic C-H bonds. The two variants provide nearly identical kinetic isotope effect values (2.8-3.0), suggesting that C-H abstraction is rate-limiting. The 2.66-Å crystal structure of the most active enzyme suggests that the engineered active site can preorganize the substrate for reactivity. We hypothesize that the enzyme controls regioselectivity through localization of a single C-H bond close to the iron nitrenoid.

  18. Complex amine-based reagents

    NASA Astrophysics Data System (ADS)

    Suslov, S. Yu.; Kirilina, A. V.; Sergeev, I. A.; Zezyulya, T. V.; Sokolova, E. A.; Eremina, E. V.; Timofeev, N. V.

    2017-03-01

    Amines for a long time have been applied to maintaining water chemistry conditions (WCC) at power plants. However, making use of complex reagents that are the mixture of neutralizing and the filmforming amines, which may also contain other organic components, causes many disputes. This is mainly due to lack of reliable information about these components. The protective properties of any amine with regard to metal surfaces depend on several factors, which are considered in this article. The results of applying complex reagents to the protection of heating surfaces in industrial conditions and estimated behavior forecasts for various reagents under maintaining WCC on heat-recovery boilers with different thermal circuits are presented. The case of a two-drum heat-recovery boiler with in-line drums was used as an example, for which we present the calculated pH values for various brands of reagents under the same conditions. Work with different reagent brands and its analysis enabled us to derive a composition best suitable for the conditions of their practical applications in heat-recovery boilers at different pressures. Testing the new amine reagent performed at a CCPP power unit shows that this reagent is an adequate base for further development of reagents based on amine compounds. An example of testing a complex reagent is shown created with the participation of the authors within the framework the program of import substitution and its possible use is demonstrated for maintaining WCC of power-generating units of combined-cycle power plants (CCPP) and TPP. The compliance of the employed reagents with the standards of water chemistry conditions and protection of heating surfaces were assessed. The application of amine-containing reagents at power-generating units of TPP makes it possible to solve complex problems aimed at ensuring the sparing cleaning of heating surfaces from deposits and the implementation of conservation and management of water chemistry condition

  19. Quinone-Catalyzed Selective Oxidation of Organic Molecules

    PubMed Central

    Wendlandt, Alison E.

    2016-01-01

    Lead In Quinones are common stoichiometric reagents in organic chemistry. High potential para-quinones, such as DDQ and chloranil, are widely used and typically promote hydride abstraction. In recent years, many catalytic applications of these methods have been achieved by using transition metals, electrochemistry or O2 to regenerate the oxidized quinone in situ. Complementary studies have led to the development of a different class of quinones that resemble the ortho-quinone cofactors in Copper Amine Oxidases and mediate efficient and selective aerobic and/or electrochemical dehydrogenation of amines. The latter reactions typically proceed via electrophilic transamination and/or addition-elimination reaction mechanisms, rather than hydride abstraction pathways. The collective observations show that the quinone structure has a significant influence on the reaction mechanism and have important implications for the development of new quinone reagents and quinone-catalyzed transformations. PMID:26530485

  20. Polymorphisms for aromatic amine metabolism in humans: relevance for human carcinogenesis.

    PubMed Central

    Kadlubar, F F; Butler, M A; Kaderlik, K R; Chou, H C; Lang, N P

    1992-01-01

    The metabolic pathways associated with carcinogenic aromatic amines in humans provide an excellent example of polymorphisms that appear to be relevant to human carcinogenesis. In this regard, the N-acetylation of arylamines and the O-acetylation of their N-hydroxy metabolites are catalyzed preferentially by a genetically polymorphic acetyltransferase, high activity of which has been correlated with decreased risk for urinary bladder cancer and increased susceptibility to colorectal cancer. Cytochrome P450IA2, the principal liver enzyme involved in aromatic amine N-oxidation, exhibits a wide interindividual variation that appears trimodal in several populations and is clearly inducible by cigarette smoking and probably other host factors as well. UDP-Glucuronosyltransferases, which catalyze the N-glucuronidation of N-hydroxyarylamines and are likely to be responsible for their transport to the colon, show widely varied but unimodal distributions in humans. In contrast, human liver sulfotransferase activity for N-hydroxyarylamines, which would be expected to decrease their transport through the circulation, is catalyzed by a polymorphic enzyme(s) that is expressed at higher levels in blacks, as compared to whites, and could contribute to their relatively lower incidence of urinary bladder cancer. Peroxidative activation of aromatic amines can also occur, especially from prostaglandin H synthase in the urinary bladder and myeloperoxidase in the lungs of cigarette smokers, and both show considerable individual variability, apparently due to the extent of tissue inflammation.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:1486865

  1. Fluorescent quantification of amino groups on silica nanoparticle surfaces.

    PubMed

    Chen, Yang; Zhang, Yanqin

    2011-03-01

    Functionalization of the surfaces of silica particles is often the first step in their various applications. An improved heterogeneous Fmoc-Cl fluorescent assay using an aqueous solution was developed to detect the number of amino groups on solid-phase supports. The fluorescent Fmoc-Cl method is 50-fold more sensitive than the current UV assay using an organic solvent. This method, together with the homogeneous fluorescamine and OPA assays, is used to detect amino groups on the silica particle surface. The accuracy and effect factors of these methods were examined and the assays were optimized. The results showed that the amine groups on silica particles can produce stronger fluorescence than small amine molecules in solution, because the porous structure of the particle surface is a more hydrophobic environment. The number of active amino groups that can be conjugated with biomolecules is much less than the total number of amino groups on the silica particle. Compared with physical methods, chemical assays involving direct reaction with amino groups would furnish the closest result to the number of active amino groups on the particle surface.

  2. Glycosylation of aromatic amines II: Kinetics and mechanisms of the hydrolytic reaction between kynurenine and glucose.

    PubMed

    Gokhale, Madhushree Y; Kirsch, Lee E

    2009-12-01

    The kinetics of the weakly basic aromatic amine, kynurenine, with glucose were studied as model reactants aimed at mechanistic understanding of pharmaceutically relevant amine-aldehyde reactions. The reaction kinetics of the forward and reverse processes (glycosylamine formation and hydrolysis) were studied under first-order conditions in aqueous solutions at 40 degrees C in the pH range 1-6.5 in the presence of various buffers. The alpha-and beta-glycosylamines were reversibly formed via an acyclic imine that was not present in detectable quantities. Rate-limiting formation of the imine was complex and involved the addition of the amine and aldehyde to form the carbinolamine followed by the acid-catalyzed dehydration to the imine. The pH-rate profile was characterized by three kinetically distinguishable processes. At lower pH values, the profile was consistent with specific acid-catalyzed rate-determining addition of amine and aldehyde. In the pH range of 4-6 a downward bend was attributable to the change in rate determining step from addition to dehydration. In the pH region of 2-3 the rate law was described by specific acid catalysis and solvolysis of the zwitterionic form of kynurenine. Nonlinear buffer effects and Brönsted plots were shown to be consistent with this interpretation of the pH-rate profile.

  3. Catalyzed sodium chlorate candles

    NASA Technical Reports Server (NTRS)

    Malich, C. W.; Wydeven, T.

    1972-01-01

    The catalytic effect of cobalt powder on chlorate decomposition has been confirmed. Catalysis is enhanced by oxidation of the metal during burning. Catalysts other than cobalt compounds should also be effective; the complete elimination of fuel has shown that the oxidation of cobalt during decomposition is not a vital factor in the improved performance of catalyzed candles.

  4. Silica-Ceria Hybrid Nanostructures

    SciTech Connect

    Munusamy, Prabhakaran; Sanghavi, Shail P.; Nachimuthu, Ponnusamy; Baer, Donald R.; Thevuthasan, Suntharampillai

    2012-04-25

    A new hybrid material system that consists of ceria attached silica nanoparticles has been developed. Because of the versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and antioxidant properties of ceria nanoparticles, this material system is ideally suited for biomedical applications. The silica particles of size ~50nm were synthesized by the Stöber synthesis method and ceria nanoparticles of size ~2-3nm was attached to the silica surface using a hetrocoagulation method. The presence of silanol groups on the surface of silica particles mediated homogenous nucleation of ceria which were attached to silica surface by Si-O-Ce bonding. The formations of silica-ceria hybrid nanostructures were characterized by X-photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (HRTEM). The HRTEM image confirms the formation of individual crystallites of ceria nanoparticles attached to the silica surface. The XPS analysis indicates that ceria nanoparticles are chemically bonded to surface of silica and possess mixture of +3 and +4 chemical states.

  5. Mesoporous silicas with tunable morphology for the immobilization of laccase.

    PubMed

    Gascón, Victoria; Díaz, Isabel; Márquez-Álvarez, Carlos; Blanco, Rosa M

    2014-05-30

    Siliceous ordered mesoporous materials (OMM) are gaining interest as supports for enzyme immobilization due to their uniform pore size, large surface area, tunable pore network and the introduction of organic components to mesoporous structure. We used SBA-15 type silica materials, which exhibit a regular 2D hexagonal packing of cylindrical mesopores of uniform size, for non-covalent immobilization of laccase. Synthesis conditions were adjusted in order to obtain supports with different particle shape, where those with shorter channels had higher loading capacity. Despite the similar isoelectric points of silica and laccase and the close match between the size of laccase and the pore dimensions of these SBA-15 materials, immobilization was achieved with very low leaching. Surface modification of macro-/mesoporous amorphous silica by grafting of amine moieties was proved to significantly increase the isoelectric point of this support and improve the immobilization yield.

  6. Lipase-catalyzed aza-Michael reaction on acrylate derivatives.

    PubMed

    Steunenberg, Peter; Sijm, Maarten; Zuilhof, Han; Sanders, Johan P M; Scott, Elinor L; Franssen, Maurice C R

    2013-04-19

    A methodology has been developed for an efficient and selective lipase-catalyzed aza-Michael reaction of various amines (primary and secondary) with a series of acrylates and alkylacrylates. Reaction parameters were tuned, and under the optimal conditions it was found that Pseudomonas stutzeri lipase and Chromobacterium viscosum lipase showed the highest selectivity for the aza-Michael addition to substituted alkyl acrylates. For the first time also, some CLEAs were examined that showed a comparable or higher selectivity and yield than the free enzymes and other formulations.

  7. New modes for the osmium-catalyzed oxidative cyclization.

    PubMed

    Donohoe, Timothy J; Lindsay-Scott, Peter J; Parker, Jeremy S; Callens, Cedric K A

    2010-03-05

    The osmium-catalyzed oxidative cyclization of amino alcohol initiators formally derived from 1,4-dienes is an effective method for the construction of pyrrolidines, utilizing a novel reoxidant (4-nitropyridine N-oxide = NPNO). The cyclization of enantiopure syn- and anti-amino alcohols gives rise to enantiopure cis- and trans-2,5-disubstituted pyrrolidines, respectively. Moreover, the cyclization of bis-homoallylic amines bearing an exocyclic chelating group is shown to be a complementary method for trans-pyrrolidine formation.

  8. Synthesis of Dihydrobenzofurans via Palladium-Catalyzed Heteroannulations

    SciTech Connect

    Rozhkov, Roman Vladimirovich

    2004-01-01

    Palladium-catalyzed heteroannulation of 1,3-dienes with 3-iodo-2-alkenols, and 2-iodo-2-alkenols, as well as their amino analogs, affords the corresponding cyclic ethers and amines respectively. The presence of a β-hydrogen in the vinylic halide results in β-hydride elimination giving the corresponding alkyne. The presence of a bulky group in the α-position of the vinylic halide results in failure or reduced amounts of annulation products. A chloride source, pyridine base and electron-rich phosphine are essential for this reaction.

  9. Silica Nanoconstruct Cellular Toleration Threshold In Vitro

    PubMed Central

    Herd, Heather L.; Malugin, Alexander; Ghandehari, Hamidreza

    2011-01-01

    The influence of geometry of silica nanomaterials on cellular uptake and toxicity on epithelial and phagocytic cells was studied. Three types of amine-terminated silica nanomaterials were prepared and characterized via the modified Stober method, namely spheres (178±27 nm), worms (232±22 nm × 1348±314 nm) and cylinders (214±29 nm × 428±66 nm). The findings of the study suggest that in this size range and for the cell types studied, geometry does not play a dominant role in the modes of toxicity and uptake of these particles. Rather, a concentration threshold and cell type dependent toxicity of all particle types was observed. This correlated with confocal microscopy observations, as all nanomaterials were observed to be taken up in both cell types, with a greater extent in phagocytic cells. It must be noted that there appears to be a concentration threshold at ~100 µg/mL, below which there is limited to no impact of the nanoparticles on membrane integrity, mitochondrial function, phagocytosis or cell death. Analysis of cell morphology by transmission electron microscopy, colocalization experiments with intracellular markers and Western Blot results provide evidence of potential involvement of lysosomal escape, autophagic like activity, compartmental fusion and recycling in response to intracellular nanoparticle accumulation. These processes could be involved in cellular coping or defense mechanisms. The manipulation of physicochemical properties to enhance or reduce toxicity paves the way for the safe design of silica-based nanoparticles for use in nanomedicine. PMID:21342660

  10. Silazine to silica

    NASA Technical Reports Server (NTRS)

    Harvey, Gale A.

    1993-01-01

    Thin film silica and/or methyl silicone were detected on most external surfaces of the retrieved LDEF. Both solar ultraviolet radiation and atomic oxygen can convert silicones to silica. Known sources of silicone in or on the LDEF appear inadequate to explain the ubiquitous presence of the silica and silicone films. Hexamethyldisilazane (HMDS) was used as the Challenger tile waterproofing compound for the Challenger/LDEF deployment mission. HMDS is both volatile and chemically reactive at STP. In addition, HMDS releases NH3 which depolymerizes silicone RTV's. Polyurethanes are also depolymerized. Experiments are reported that indicate much of the silicone and silica contamination of LDEF resulted directly or indirectly from HMDS.

  11. FeCl3-catalyzed self-cleaving deprotection of methoxyphenylmethyl-protected alcohols.

    PubMed

    Sawama, Yoshinari; Masuda, Masahiro; Asai, Shota; Goto, Ryota; Nagata, Saori; Nishimura, Shumma; Monguchi, Yasunari; Sajiki, Hironao

    2015-02-06

    4-Methoxyphenylmethyl ethers are widely utilized as alcohol protecting groups. FeCl3 effectively catalyzes the deprotection of methoxyphenylmethyl-type ethers in a self-cleaving manner to produce oligomeric derivatives and alcohols. Remarkably, the highly pure mother alcohols can be obtained without silica gel column chromatography by using the 2,4-dimethoxyphenylmethyl group as a protective group.

  12. Erythrocyte enzymes catalyze 1-nitropyrene and 3-nitrofluoranthene nitroreduction.

    PubMed

    Belisario, M A; Pecce, R; Garofalo, A; Sannolo, N; Malorni, A

    1996-04-15

    Nitroarenes are environmental contaminants produced during incomplete combustion processes. Nitroreduction, the most important pathway of nitroarene toxification, occurs mainly in the liver and intestine. In the present study, we show that human red cells may also possess the metabolic competence to reduce 1-nitropyrene (NP) and 3-nitrofluoranthene (NF), the nitroarenes chosen as model compounds, to their corresponding amino derivatives, 1-aminopyrene (AP) and 3-aminofluoranthene (AF). The requirement of the cofactor couple NADH/FMN suggests that erythrocyte nitroreductase activity occurs via one electron transfer. The presence of oxygen strongly inhibited the haemolysate-catalyzed nitroarene reduction, whether measured as amine formation or nitroarene disappearance. Intermediate reactive species, that bind covalently to haemoglobin and/or other erythrocyte proteins, are formed during nitroreduction catalyzed by human haemolysate. In fact, the reduced metabolites AP and AF were released after mild acid hydrolysis of red cell proteins exposed to NP and NF, thus suggesting that sulphinamide adducts have been formed.

  13. Click on silica: systematic immobilization of Co(II) Schiff bases to the mesoporous silica via click reaction and their catalytic activity for aerobic oxidation of alcohols.

    PubMed

    Rana, Bharat S; Jain, Suman L; Singh, Bhawan; Bhaumik, Asim; Sain, Bir; Sinha, Anil K

    2010-09-07

    The systematic immobilization of cobalt(II) Schiff base complexes on SBA-15 mesoporous silica via copper catalyzed [3 + 2] azide-alkyne cycloaddition (CuAAC) "click reaction" involving either step-wise synthesis of silica-bound Schiff base ligand followed by its subsequent complexation with cobalt ions, or by the direct immobilization of preformed Co(II) Schiff base complex to the silica support is described. The catalytic activity of the prepared complexes was studied for the oxidation of alcohols to carbonyl compounds using molecular oxygen as oxidant. The immobilized complexes were recycled for several runs without loss in catalytic activity and no leaching was observed during this course.

  14. Highly selective room-temperature copper-catalyzed C-N coupling reactions.

    PubMed

    Shafir, Alexandr; Buchwald, Stephen L

    2006-07-12

    Through the use of cyclic beta-diketones as supporting ligands, the copper-catalyzed coupling of aryl iodides with aliphatic amines occurs at room temperature in as little as 1 h. These high reaction rates allow for the coupling of a wide range of aryl and heteroaryl iodides at room temperature. This method is highly tolerant of a number of reactive functional groups, including -Br and aromatic -NH2 as well as phenolic and aliphatic -OH. The high selectivity of the CuI-beta-diketone catalyst for aliphatic amines represents a useful complement to the palladium-based methods.

  15. Homologation of α-aryl amino acids through quinone-catalyzed decarboxylation/Mukaiyama-Mannich addition.

    PubMed

    Haugeberg, Benjamin J; Phan, Johnny H; Liu, Xinyun; O'Connor, Thomas J; Clift, Michael D

    2017-03-09

    A new method for amino acid homologation by way of formal C-C bond functionalization is reported. This method utilizes a 2-step/1-pot protocol to convert α-amino acids to their corresponding N-protected β-amino esters through quinone-catalyzed oxidative decarboxylation/in situ Mukaiyama-Mannich addition. The scope and limitations of this chemistry are presented. This methodology provides an alternative to the classical Arndt-Eistert homologation for accessing β-amino acid derivatives. The resulting N-protected amine products can be easily deprotected to afford the corresponding free amines.

  16. Facile Access to Ring-Fused Aminals via Direct α-Amination of Secondary Amines with ortho-Aminobenzaldehydes. Synthesis of Vasicine, Deoxyvasicine, Deoxyvasicinone, Mackinazolinone and Ruteacarpine

    PubMed Central

    Richers, Matthew T.; Deb, Indubhusan; Platonova, Alena Yu.; Zhang, Chen

    2013-01-01

    Secondary amines undergo redox-neutral reactions with aminobenzaldehydes under conventional and microwave heating to furnish polycyclic aminals via amine α-amination/N-alkylation. This unique α-functionalization reaction proceeds without the involvement of transition metals or other additives. The resulting aminal products are precursors for various quinazolinone alkaloids and their analogues. PMID:24052668

  17. Aliphatic amines in the Murchison meteorite

    NASA Technical Reports Server (NTRS)

    Jungclaus, G.; Cronin, J. R.; Moore, C. B.; Yuen, G. U.

    1976-01-01

    The paper reports on the determination of aliphatic amines in water extracts of the Murchison meteorite. The amines were analyzed by gas chromatography both as the free amines and as 2,4-dinitrophenyl (DNP) derivatives. The results give evidence for the presence of all of the possible primary aliphatic monoamines (eight) with fewer than five carbon atoms. Two of the seven possible secondary or tertiary aliphatic monoamines were identified. The identified primary amines total 80 nmol per g meteorite, and seem to be chemically or physically trapped in the meteorite. Similarities between the water-extractable amines and amino acids suggest that (1) a simple carbon compound, methane, for example, is the precursor of meteorite amines and amino acids, and (2) both amines and amino acids are extracted from the meteorite both as such and in the form of acid-hydrolyzable derivative or precursor species.

  18. CO2-induced degradation of amine-containing adsorbents: reaction products and pathways.

    PubMed

    Sayari, Abdelhamid; Heydari-Gorji, Aliakbar; Yang, Yong

    2012-08-22

    A comprehensive study was conducted to investigate the stability of a wide variety of mesoporous silica-supported amine-containing adsorbents in the presence of carbon dioxide under dry conditions. CO(2)-induced degradation of grafted primary and secondary monoamines (pMono, sMono), diamines with one primary and one secondary amines (Diamine) and triamine with one primary and two secondary amines (TRI) as well as different impregnated polyamines such as branched and linear polyethylenimine (BPEI and LPEI) and polyallylamine (PALL) was investigated using extensive CO(2) adsorption-desorption cycling as well as diffuse reflectance infrared Fourier transform (DRIFT) and (13)C CP MAS NMR measurements. Except for sMono, all other supported amines underwent significant deactivation in the presence of dry CO(2) under mild conditions. In all cases, the decrease in CO(2) uptake was associated with the formation of urea linkages at the expense of amine groups. The urea-containing species were identified, and the deactivation pathways were delineated.

  19. Haemoglobin adducts of aromatic amines: diamines and polyaromatic amines.

    PubMed

    Sabbioni, G; Beyerbach, A

    2000-07-21

    Aromatic amines and nitroarenes are important antioxidants and intermediates in the synthesis of dyes, pesticides and plastics. In the present paper we introduce methods for the synthesis of deuterated standards: 3-[2H8]aminofluoranthene, 3,3'-dimethyl-[2H4]benzidine, [2H4]benzidine, N'-acetyl-[2H4]benzidine, 2,4-[2H6]toluenediamine, 2,6-[2H6]toluenediamine. These standards have been used for the quantification of haemoglobin adducts of diamines and polyaromatic amines. Haemoglobin was hydrolysed in 0.1 M sodium hydroxide and the hydrolysate extracted with dichloromethane. The extracts were derivatised with heptafluorobutyric anhydride and analysed by GC-MS with negative chemical ionisation. In one run up to 15 aromatic amines can be determined: 6-aminochrysene, 3-aminofluoranthene, 2-aminofluorene, 1-aminopyrene, benzidine, 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, 3,3'-dimethylbenzidine, 3,3'-methylenedianiline, 4,4'-methylenedianiline, N'-acetyl-benzidine, N'-acetyl-4,4'-methylenedianiline, 4,4'-methylene bis(2-chloroaniline), 2,4-toluenediamine and 2,6-toluenediamine.

  20. On the role of the colloidal stability of mesoporous silica nanoparticles as gene delivery vectors

    NASA Astrophysics Data System (ADS)

    Cebrián, Virginia; Yagüe, Clara; Arruebo, Manuel; Martín-Saavedra, Francisco M.; Santamaría, Jesus; Vilaboa, Nuria

    2011-09-01

    Mesoporous silica nanoparticles have been synthesized and functionalized with four different types of molecules containing amino groups, i.e., with primary amines only, with quaternary amines, with quaternized cyclic amines, or with polyethylenimine (PEI), which is formed by primary, secondary, and tertiary amines. These nanoparticles were then incubated with reporter plasmids and the ability of the resulting complexes to transfect human cells was studied. Only nanoparticles functionalized with PEI were efficient for transfection. The agglomeration behavior and the electrokinetic potential of the nanoparticle-plasmid complexes have been studied, as well as their cell internalization behavior using a fluorescent-labeled plasmid that allows its monitorization by confocal microscopy. The results indicate that the efficiency of PEI-functionalized nanoparticles for transfection resides to some extent in the different characteristics imparted to the nanoparticles regarding agglomeration and surface charge behavior.

  1. Direct formation of S-nitroso silica nanoparticles from a single silica source.

    PubMed

    Chou, Hung-Chang; Chiu, Shih-Jiuan; Liu, Ying-Ling; Hu, Teh-Min

    2014-01-28

    Nitric oxide (NO) is a ubiquitous molecule in the body. Because of its multiple pathophysiologic roles, the potential for treating various diseases by the exogenous administration of NO has been under intensive investigation. However, the unstable, radical nature of NO poses a major challenge to the effective delivery of NO. Previously, silica nanoparticles synthesized by the traditional method have been developed into NO-carrying systems. In the present study, for the first time NO-carrying silica nanoparticles were prepared from a single silica precursor using a simple nanoprecipitation method. (3-Mercaptopropyl)-trimethoxysilane (MPTMS) was used as the sole silane source, which was subjected to acid-catalyzed S-nitrosation and condensation reactions in a one-pot organic phase. S-Nitroso silica nanoparticles (SNO-SiNPs) were then produced by injecting a smaller quantity of the organic phase into a larger amount of water without surfactants. Various preparation parameters were tested to obtain optimized conditions. Moreover, a phase diagram demonstrating the ouzo effect was constructed. The prepared SNO-SiNPs were spherical particles with a tunable size in the range of 100-400 nm. The nanoparticles in aqueous dispersions exhibited high colloid stability, possibly resulting from highly negatively charged surfaces. The result of solid-state (29)Si NMR shows the predominance of T(2) and T(3) silicon structures, suggesting that nanoparticles were formed from polycondensed silica species. In conclusion, NO-loaded silica nanoparticles have been directly prepared from a single silane precursor using a surfactant-free, low-energy, one-step nanoprecipitation approach. The method precludes the need for the initial formation of bare particles and subsequent functionalization steps.

  2. Silica, Silicosis, and Autoimmunity

    PubMed Central

    Pollard, Kenneth Michael

    2016-01-01

    Inhalation of dust containing crystalline silica is associated with a number of acute and chronic diseases including systemic autoimmune diseases. Evidence for the link with autoimmune disease comes from epidemiological studies linking occupational exposure to crystalline silica dust with the systemic autoimmune diseases systemic lupus erythematosus, systemic sclerosis, and rheumatoid arthritis. Although little is known regarding the mechanism by which silica exposure leads to systemic autoimmune disease, there is a voluminous literature on silica exposure and silicosis that may help identify immune processes that precede development of autoimmunity. The pathophysiology of silicosis consists of deposition of silica particles in the alveoli of the lung. Ingestion of these particles by macrophages initiates an inflammatory response, which stimulates fibroblasts to proliferate and produce collagen. Silica particles are encased by collagen leading to fibrosis and the nodular lesions characteristic of the disease. The steps in the development of silicosis, including acute and chronic inflammation and fibrosis, have different molecular and cellular requirements, suggesting that silica-induced inflammation and fibrosis may be mechanistically separate. Significantly, it is unclear whether silica-induced inflammation and fibrosis contribute similarly to the development of autoimmunity. Nonetheless, the findings from human and animal model studies are consistent with an autoimmune pathogenesis that begins with activation of the innate immune system leading to proinflammatory cytokine production, pulmonary inflammation leading to activation of adaptive immunity, breaking of tolerance, and autoantibodies and tissue damage. The variable frequency of these immunological features following silica exposure suggests substantial genetic involvement and gene/environment interaction in silica-induced autoimmunity. However, numerous questions remain unanswered. PMID:27014276

  3. Origins of Stereoselectivity of Chiral Vicinal Diamine-Catalyzed Aldol Reactions.

    PubMed

    Simon, Adam; Yeh, Alexander J; Lam, Yu-Hong; Houk, K N

    2016-12-16

    The sources of asymmetric induction in aldol reactions catalyzed by cinchona alkaloid-derived amines, and chiral vicinal diamines in general, have been determined by density functional theory calculations. Four vicinal diamine-catalyzed aldol reactions were examined. The cyclic transition states of these reactions involve nine-membered hydrogen-bonded rings in distinct conformations. Using nomenclature from eight-membered cycloalkanes, the heavy atoms of the low-energy transition states are in crown (chair-chair) and chair-boat conformations. The factors that control which of these are favored have been identified.

  4. Ammonia hardening of porous silica antireflective coatings

    NASA Astrophysics Data System (ADS)

    Belleville, Philippe F.; Floch, Herve G.

    1994-10-01

    The adhesion of sol-gel antireflective porous silica coatings on vitreous optical substrates has been dramatically improved by exposure to ammonia vapors or a dip in basic solutions. The approximately 70 to 270-nm thick coatings consisted of monolayers of spherical, 20-nm diameter amorphous silica particles deposited from ethanolic colloidal suspensions by conventional liquid coating techniques. Although, the as-deposited coatings had only low adhesion and were easily damaged when cleaned by standard drag-wiping procedures, coatings exposed over 5 hours to ammonia vapors passed both adhesive-tape and moderate abrasive- resistance tests. The increase in strength was accompanied by a roughly 20% shrinkage of the original coating thickness but the antireflective properties were retained. Our explanation of this chemical effect is a base-catalyzed phenomenon leading to surface silanol condensation and hydrogen-bonding of neighbor silica particles. In addition, since this basic treatment enhanced the laser damage resistance, such strengthened antireflective coatings have been successfully evaluated on flashlamps used on Phebus, Europe's most powerful laser. This allows an increase of the laser-disk pumping efficiency.

  5. Application of silica nanoparticles for increased silica availability in maize

    NASA Astrophysics Data System (ADS)

    Suriyaprabha, R.; Karunakaran, G.; Yuvakkumar, R.; Prabu, P.; Rajendran, V.; Kannan, N.

    2013-02-01

    Silica nanoparticles were extracted from rice husk and characterised comprehensively. The synthesised silica powders were amorphous in size with 99.7% purity (20-40 nm). Nanosilica was amended with red soil at 15 kg ha-1 along with micron silica. The influence of nanoscale on silica uptake, accumulation and nutritional variations in maize roots were evaluated through the studies such as root sectioning, elemental analysis and physiological parameters (root length and silica content) and compared with micron silica and control. Nanosilica treated soil reveals enhanced silica uptake and elongated roots which make the plant to resist in stress conditions like drought.

  6. Mesoporous silica and organosilica films templated by nanocrystalline chitin.

    PubMed

    Nguyen, Thanh-Dinh; Shopsowitz, Kevin E; MacLachlan, Mark J

    2013-11-04

    Liquid crystalline phases can be used to impart order into inorganic solids, creating materials that mimic natural architectures. Herein, mesoporous silica and organosilica films with layered structures and high surface areas have been templated by nanocrystalline chitin. Aqueous suspensions of spindle-shaped chitin nanocrystals were prepared by sequential deacetylation and hydrolysis of chitin fibrils isolated from king crab shells. The nanocrystalline chitin self-assembles into a nematic liquid-crystalline phase that has been used to template silica and organosilica composites. Removal of the chitin template by either calcination or sulfuric-acid-catalyzed hydrolysis gave mesoporous silica and ethylene-bridged organosilica films. The large, crack-free mesoporous films have layered structures with features that originate from the nematic organization of the nanocrystalline chitin.

  7. High Resolution, Single-Step Patterning of Silica Aerogels

    NASA Technical Reports Server (NTRS)

    Bertino, M. F.; Hund, J. F.; Sosa, J.; Zhang, G.; Sotiriou-Leventis, C.; Leventis, N.; Tokuhiro, A. T.; Terry, J.

    2003-01-01

    Three-dimensional metallic structures are fabricated with high spatial resolution in silica aerogels. In our method, silica hydrogels are prepared with a standard base-catalyzed route, and exchanged with an aqueous solution typically containing Ag' ions (1 M) and 2-propanol (0.2 M). The metal ions are reduced photolytically with a table-top ultraviolet lamp, or radiolytically, with a focused X-ray beam. We fabricated dots and lines as small as 30 x 70 km, protruding for several mm into the bulk of the materials. The hydrogels are eventually supercritically dried to yield aerogels, without any measurable change in the shape and spatial resolution of the lithographed structures. Transmission electron microscopy shows that illuminated regions are composed of Ag clusters with a size of several pm, separated by thin layers of silica.

  8. Catalyzed Ceramic Burner Material

    SciTech Connect

    Barnes, Amy S., Dr.

    2012-06-29

    Catalyzed combustion offers the advantages of increased fuel efficiency, decreased emissions (both NOx and CO), and an expanded operating range. These performance improvements are related to the ability of the catalyst to stabilize a flame at or within the burner media and to combust fuel at much lower temperatures. This technology has a diverse set of applications in industrial and commercial heating, including boilers for the paper, food and chemical industries. However, wide spread adoption of catalyzed combustion has been limited by the high cost of precious metals needed for the catalyst materials. The primary objective of this project was the development of an innovative catalyzed burner media for commercial and small industrial boiler applications that drastically reduce the unit cost of the catalyzed media without sacrificing the benefits associated with catalyzed combustion. The scope of this program was to identify both the optimum substrate material as well as the best performing catalyst construction to meet or exceed industry standards for durability, cost, energy efficiency, and emissions. It was anticipated that commercial implementation of this technology would result in significant energy savings and reduced emissions. Based on demonstrated achievements, there is a potential to reduce NOx emissions by 40,000 TPY and natural gas consumption by 8.9 TBtu in industries that heavily utilize natural gas for process heating. These industries include food manufacturing, polymer processing, and pulp and paper manufacturing. Initial evaluation of commercial solutions and upcoming EPA regulations suggests that small to midsized boilers in industrial and commercial markets could possibly see the greatest benefit from this technology. While out of scope for the current program, an extension of this technology could also be applied to catalytic oxidation for volatile organic compounds (VOCs). Considerable progress has been made over the course of the grant

  9. Purification and characterization of amine oxidase from pea seedlings.

    PubMed

    Vianello, F; Malek-Mirzayans, A; Di Paolo, M L; Stevanato, R; Rigo, A

    1999-03-01

    A novel, simple, and rapid procedure for the purification of pea seedling amine oxidase is reported. The crude enzyme, obtained by ammonium sulfate fractionation, was purified in two steps: the first one by anion-exchange chromatography and the second one by affinity chromatography. The first chromatography step was carried out on a diethylaminoethyl-cellulose column. By lowering the amount of protein loaded on the column and the buffer concentration it was possible to obtain an enzyme pure at 95% (sp act 1.2 microkat/mg). To achieve a higher degree of purification various affinity resins were prepared and tested. The resins were obtained by covalent immobilization of polyamines on Sepharose according to three different procedures. The best results were obtained with 6-aminohexyl-Sepharose 2B, prepared using CNBr as coupling agent, and eluting the enzyme by a solution containing 1, 4-diaminocyclohexane. This last compound was found to be a relatively strong competitive inhibitor of the oxidative deamination of cadaverine catalyzed by pea seedling amine oxidase (Ki = 32 microM). According to this procedure an electrophoretically homogeneous enzyme, characterized by a specific activity of 1.63 microkat/mg, was obtained.

  10. Formation of hollow silica nanospheres by reverse microemulsion

    NASA Astrophysics Data System (ADS)

    Lin, Cheng-Han; Chang, Jen-Hsuan; Yeh, Yi-Qi; Wu, Si-Han; Liu, Yi-Hsin; Mou, Chung-Yuan

    2015-05-01

    Uniform hollow silica nanospheres (HSNs) synthesized with reverse microemulsion have great application potential as nanoreactors because enzymes or nanocatalysts can be easily encapsulated de novo in synthesis. Water-in-oil (w/o) reverse microemulsions comprising the polymeric surfactant polyoxyethylene (5) isooctylphenyl ether (Igepal CA-520), ammonia and water in a continuous oil phase (alkanes) coalesce into size-tunable silica nanoparticles via diffusion aggregation after the introduction of silica precursors. Here, we elucidate in detail the growth mechanism for silica nanoparticles via nucleation of ammonium-catalyzed silica oligomers from tetraethylorthosilicate (TEOS) and nanoporous aminopropyltrimethoxy silane (APTS) in the reverse microemulsion system. The formation pathway was studied in situ with small-angle X-ray scattering (SAXS). We find a four-stage process showing a sigmoidal growth behavior in time with a crossover from the induction period, early nucleation stage, coalescence growth and a final slowing down of growth. Various characterizations (TEM, N2 isotherm, dynamic light scattering, zeta potential, NMR, elemental analysis) reveal the diameters, scattering length density (SLD), mesoporosity, surface potentials and chemical compositions of the HSNs. Oil phases of alkanes with different alkyl chains are systematically employed to tune the sizes of HSNs by varying oil molar volumes, co-solvent amounts or surfactant mixture ratios. Silica condensation is incomplete in the core region, with the silica source of TEOS and APTS leading to the hollow silica nanosphere after etching with warm water.Uniform hollow silica nanospheres (HSNs) synthesized with reverse microemulsion have great application potential as nanoreactors because enzymes or nanocatalysts can be easily encapsulated de novo in synthesis. Water-in-oil (w/o) reverse microemulsions comprising the polymeric surfactant polyoxyethylene (5) isooctylphenyl ether (Igepal CA-520), ammonia and

  11. Enantioselective synthesis of tunable chiral Clickphine P,N-ligands and their application in Ir-catalyzed asymmetric hydrogenation.

    PubMed

    Wassenaar, Jeroen; Detz, Remko J; de Boer, Sandra Y; Lutz, Martin; van Maarseveen, Jan H; Hiemstra, Henk; Reek, Joost N H

    2015-04-03

    A small library of highly tunable chiral Clickphine P,N-ligands has been prepared in an enantioselective fashion by Cu(I)-catalyzed asymmetric propargylic amination using a single chiral complex and a subsequent in situ cycloaddition click reaction. The scope of the propargylic amination to yield optically active triazolyl amines is described. The amines are transformed in a one-pot procedure to the corresponding Ir-Clickphine complexes, which serve as catalysts for the asymmetric hydrogenation of di-, tri-, and tetrasubstituted unfunctionalized alkenes. Enantioselectivities of up to 90% ee were obtained in these hydrogenations, which are among the best reported in the case of the tetrasubstituted substrate 2-(4'-methoxyphenyl)-3-methylbut-2-ene (9) (87% ee). This is a demonstration of the effective use of the chiral pool, as from one chiral catalyst a library of chiral Ir complexes has been synthesized that can hydrogenate various alkenes with high selectivity.

  12. Asymmetric Petasis Borono-Mannich Allylation Reactions Catalyzed by Chiral Biphenols.

    PubMed

    Jiang, Yao; Schaus, Scott E

    2017-02-01

    Chiral biphenols catalyze the asymmetric Petasis borono-Mannich allylation of aldehydes and amines through the use of a bench-stable allyldioxaborolane. The reaction proceeds via a two-step, one-pot process and requires 2-8 mole % of 3,3'-Ph2 -BINOL as the optimal catalyst. Under microwave heating the reaction affords chiral homoallylic amines in excellent yields (up to 99 %) and high enantioselectivies (er up to 99:1). The catalytic reaction is a true multicomponent condensation reaction whereas both the aldehyde and the amine can possess a wide range of structural and electronic properties. Use of crotyldioxaborolane in the reaction results in stereodivergent products with anti- and syn-diastereomers both in good diastereoselectivities and enantioselectivities from the corresponding E- and Z-borolane stereoisomers.

  13. Iodine-catalyzed aminosulfonation of hydrocarbons by imidoiodinanes. A synthetic and mechanistic investigation.

    PubMed

    Lamar, Angus A; Nicholas, Kenneth M

    2010-11-19

    The amino-functionalization of a range of benzylic and some aliphatic saturated and unsaturated hydrocarbons by reaction with imido-iodinanes (PhI═NSO2Ar) is catalyzed by I2 under operationally simple and mild conditions. The first examples of 1,2-functionalization of unactivated C-H bonds using imido-iodinanes as aminating agents are reported. Mechanistic investigations, including Hammett analysis, kinetic isotope effects, a cyclopropane clock experiment, and stereoselectivity tests, are indicative of a stepwise pathway in C-N bond formation. Investigation into the nature of the active aminating species has led to the isolation of a novel aminating agent formulated as (ArSO2N)(x)I(y) (x = 1, y = 2; or x = 3, y = 4).

  14. N-Dealkylation of aliphatic amines and selective synthesis of monoalkylated aryl amines.

    PubMed

    Hollmann, Dirk; Bähn, Sebastian; Tillack, Annegret; Beller, Matthias

    2008-07-21

    Highly selective alkyl transfer processes of mono-, di- and trialkyl amines in the presence of the Shvo catalyst have been realized; in addition, a general method for N-alkylation of aniline with di- and trialkyl amines is presented.

  15. Regioselective synthesis of 1-alkyl- or 1-aryl-1H-indazoles via copper-catalyzed cyclizations of 2-haloarylcarbonylic compounds.

    PubMed

    Viña, Dolores; del Olmo, Esther; López-Pérez, José L; San Feliciano, Arturo

    2007-02-01

    [reaction: see text] A general method for the one-step regioselective synthesis of 1-alkyl- or 1-aryl-1H-indazoles from ortho-halogenated alkanoylphenones, benzophenones, and arylcarboxylic acids, via copper-catalyzed amination, was developed by using 0.2% mol of CuO in the presence of K(2)CO(3). The reaction involves amination followed by intramolecular dehydration. Different functionalized alkyl aryl ketones, diaryl ketones, and benzoic acid derivatives were efficiently coupled with several hydrazines. Ligands commonly employed as catalysts for intermolecular amination were shown to be ineffective for this cyclization.

  16. Highly Chemoselective Iridium Photoredox and Nickel Catalysis for the Cross-Coupling of Primary Aryl Amines with Aryl Halides.

    PubMed

    Oderinde, Martins S; Jones, Natalie H; Juneau, Antoine; Frenette, Mathieu; Aquila, Brian; Tentarelli, Sharon; Robbins, Daniel W; Johannes, Jeffrey W

    2016-10-10

    A visible-light-promoted iridium photoredox and nickel dual-catalyzed cross-coupling procedure for the formation C-N bonds has been developed. With this method, various aryl amines were chemoselectively cross-coupled with electronically and sterically diverse aryl iodides and bromides to forge the corresponding C-N bonds, which are of high interest to the pharmaceutical industries. Aryl iodides were found to be a more efficient electrophilic coupling partner. The coupling reactions were carried out at room temperature without the rigorous exclusion of molecular oxygen, thus making this newly developed Ir-photoredox/Ni dual-catalyzed procedure very mild and operationally simple.

  17. Immobilization and stabilization of cephalosporin C acylase on aminated support by crosslinking with glutaraldehyde and further modifying with aminated macromolecules.

    PubMed

    He, Hua; Wei, Yanmei; Luo, Hui; Li, Xi; Wang, Xiaona; Liang, Chen; Chang, Yanhong; Yu, Huimin; Shen, Zhongyao

    2015-01-01

    In this work, cephalosporin C acylase (CA), a heterodimeric enzyme of industrial potential in direct hydrolysis of cephalosporin C (CPC) to 7-aminocephalosporanic acid (7-ACA), was covalently immobilized on the aminated support LX1000-HA (HA) with two different protocols. The stability of CA adsorbed onto the HA support followed by crosslinking with glutaraldehyde (HA-CA-glut) was better than that of the CA covalently immobilized on the glutaraldehyde preactivated HA support (HA-glut-CA). The thermostabilization factors (compared with the free enzyme) of these two immobilized enzymes were 11.2-fold and 2.2-fold, respectively. In order to improve the stability of HA-CA-glut, a novel strategy based on postimmobilization modifying with aminated molecules was developed to take advantage of the glutaraldehyde moieties left on the enzyme and support. The macromolecules, such as polyethyleneimine (PEI) and chitosan, had larger effects than small molecules on the thermal stability of the immobilized enzyme perhaps due to crosslinking of the enzymes and support with each other. The quaternary structure of the CA could be much stabilized by this novel approach including physical adsorption on aminated support, glutaraldehyde treatment, and macromolecule modification. The HA-CA-glut-PEI20000 (the HA-CA-glut postmodified with PEI Mw = 20,000) had a thermostabilization factor of 20-fold, and its substrate affinity (Km = 14.3 mM) was better than that of HA-CA-glut (Km = 33.4 mM). The half-life of the immobilized enzymes HA-CA-glut-PEI20000 under the CPC-catalyzing conditions could reach 28 cycles, a higher value than that of HA-CA-glut (21 cycles).

  18. Antiproton catalyzed fusion

    SciTech Connect

    Morgan, D.L. Jr.; Perkins, L.J.; Haney, S.W.

    1995-05-15

    Because of the potential application to power production, it is important to investigate a wide range of possible means to achieve nuclear fusion, even those that may appear initially to be infeasible. In antiproton catalyzed fusion, the negative antiproton shields the repulsion between the positively charged nuclei of hydrogen isotopes, thus allowing a much higher level of penetration through the repulsive Coulomb barrier, and thereby greatly enhancing the fusion cross section. Because of their more compact wave function, the more massive antiprotons offer considerably more shielding than do negative muons. The effects of the shielding on fusion cross sections are most predominate, at low energies. If the antiproton could exist in the ground state with a nucleus for a sufficient time without annihilating, the fusion cross sections are so enhanced that at room temperature energies, values up to about 1,000 barns (that for d+t) would be possible. Unfortunately, the cross section for antiproton annihilation with the incoming nucleus is even higher. A model that provides an upper bound for the fusion to annihilation cross section for all relevant energies indicates that each antiproton will catalyze no more than about one fusion. Because the energy required to make one antiproton greatly exceeds the fusion energy that is released, this level of catalysis is far from adequate for power production.

  19. Electrochemical Sensors: Functionalized Silica

    SciTech Connect

    Fryxell, Glen E.; Lin, Yuehe; Yantasee, Wassana

    2009-03-24

    This chapter summarizes recent devellopment of electrochemical sensors based on functionlized mesoporous silica materials. The nanomatrials based sensors have been developed for sensitive and selective enrironmental detection of toxic heavy metal and uranium ions.

  20. Cellulose-silica aerogels.

    PubMed

    Demilecamps, Arnaud; Beauger, Christian; Hildenbrand, Claudia; Rigacci, Arnaud; Budtova, Tatiana

    2015-05-20

    Aerogels based on interpenetrated cellulose-silica networks were prepared and characterised. Wet coagulated cellulose was impregnated with silica phase, polyethoxydisiloxane, using two methods: (i) molecular diffusion and (ii) forced flow induced by pressure difference. The latter allowed an enormous decrease in the impregnation times, by almost three orders of magnitude, for a sample with the same geometry. In both cases, nanostructured silica gel was in situ formed inside cellulose matrix. Nitrogen adsorption analysis revealed an almost threefold increase in pores specific surface area, from cellulose aerogel alone to organic-inorganic composite. Morphology, thermal conductivity and mechanical properties under uniaxial compression were investigated. Thermal conductivity of composite aerogels was lower than that of cellulose aerogel due to the formation of superinsulating mesoporous silica inside cellulose pores. Furthermore, composite aerogels were stiffer than each of reference aerogels.

  1. Pushing the limits of catalytic C-H amination in polyoxygenated cyclobutanes.

    PubMed

    Nocquet, Pierre-Antoine; Hensienne, Raphaël; Wencel-Delord, Joanna; Laigre, Eugénie; Sidelarbi, Khadidja; Becq, Frédéric; Norez, Caroline; Hazelard, Damien; Compain, Philippe

    2016-03-07

    A synthetic route to a new class of conformationally constrained iminosugars based on a 5-azaspiro[3.4]octane skeleton has been developed by way of Rh(ii)-catalyzed C(sp(3))-H amination. The pivotal stereocontrolled formation of the quaternary C-N bond by insertion into the C-H bonds of the cyclobutane ring was explored with a series of polyoxygenated substrates. In addition to anticipated regioselective issues induced by the high density of activated α-ethereal C-H bonds, this systematic study showed that cyclobutane C-H bonds were, in general, poorly reactive towards catalytic C-H amination. This was demonstrated inter alia by the unexpected formation of a oxathiazonane derivative, which constitutes a very rare example of the formation of a 9-membered ring by way of catalyzed C(sp(3))-H amination. A complete stereocontrol could be however achieved by activating the key insertion position as an allylic C-H bond in combination with reducing the electron density at the undesired C-H insertion sites by using electron-withdrawing protecting groups. Preliminary biological evaluations of the synthesized spiro-iminosugars were performed, which led to the identification of a new class of correctors of the defective F508del-CFTR gating involved in cystic fibrosis.

  2. Development and validation of a hydrophilic interaction liquid chromatographic method for determination of aromatic amines in environmental water.

    PubMed

    Li, Ruiping; Zhang, Yi; Lee, Charles C; Lu, Rongrong; Huang, Yingping

    2010-03-12

    A simple, precise, and accurate hydrophilic interaction liquid chromatographic (HILIC) method has been developed for the determination of five aromatic amines in environmental water samples. Chromatography was carried out on a bare silica column, using a mixture of acetonitrile and a buffer of NaH(2)PO(4)-H(3)PO(4) (pH 1.5, containing 10mM NaH(2)PO(4)) (85:15, v/v) as a mobile phase at a flow rate of 1 mL min(-1). Aromatic amines were detected by UV absorbance at 254 nm. The linear range of amines was good (r(2)>0.998) and limit of detection (LOD) within 0.02-0.2 mg L(-1) (S/N=3). The retention mechanism for the analytes under the optimum conditions was determined to be a combination of adsorption, partition and ionic interactions. The proposed method was applied to the environmental water samples. Aromatic amines were isolated from aqueous samples using solid-phase extraction (SPE) with Oasis HLB cartridges. Recoveries of greater than 75% with precision (RSD) less than 12% were obtained at amine concentrations of 5-50 microg L(-1) from 100mL river water and influents from a wastewater treatment plant (WWTP). The present HILIC technique proved to be a viable method for the analysis of aromatic amines in the environmental water samples.

  3. Surface arming magnetic nanoparticles with amine N-halamines as recyclable antibacterial agents: Construction and evaluation.

    PubMed

    Yao, Quanfu; Gao, Yangyang; Gao, Tianyi; Zhang, Yanling; Harnoode, Chokto; Dong, Alideertu; Liu, Ying; Xiao, Linghan

    2016-08-01

    Magnetic recyclable antibacterial nanomaterials, i.e., magnetic amine N-halamine nanoparticles (Fe3O4@SiO2/CTMP NPs), were constructed by arming magnetic silica nanoparticles (Fe3O4@SiO2 NPs) with amine N-halamine (CTMP). Magnetic iron oxide nanoparticles were encapsulated into silica layers followed by anchoring antibacterial amine N-halamines to give magnetic/antibacterial bi-functional agents with core-shell structure. Since the presence of Fe3O4 NPs in core, the products offer super-paramagnetic behavior, which made them separable magnetically after the antibacterial behavior. Their sterilizing effect on bacterial strain was evaluated using Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) as model bacteria via the plate counting technique, zone of inhibition study, and time kill assay. Antibacterial mechanism study illustrated that the products integrate both the contact mechanism and the release mechanism for attacking bacteria. The significant effect of oxidative chlorine content and concentration of the products on antibiotic action were confirmed. Thanks to the magnetic property, the potential recyclability of the products was achieved. Most significantly, the products retain effective antibacterial action even after five cycles. These findings revealed that the products Fe3O4@SiO2/CTMP NPs have promising applications in the antibacterial fields.

  4. Crystalline Silica Primer

    USGS Publications Warehouse

    ,

    1992-01-01

    substance and will present a nontechnical overview of the techniques used to measure crystalline silica. Because this primer is meant to be a starting point for anyone interested in learning more about crystalline silica, a list of selected readings and other resources is included. The detailed glossary, which defines many terms that are beyond the scope of this publication, is designed to help the reader move from this presentation to a more technical one, the inevitable next step.

  5. Silica, hybrid silica, hydride silica and non-silica stationary phases for liquid chromatography.

    PubMed

    Borges, Endler M

    2015-04-01

    Free silanols on the surface of silica are the "villains", which are responsible for detrimental interactions of those compounds and the stationary phase (i.e., bad peak shape, low efficiency) as well as low thermal and chemical stability. For these reasons, we began this review describing new silica and hybrid silica stationary phases, which have reduced and/or shielded silanols. At present, in liquid chromatography for the majority of analyses, reversed-phase liquid chromatography is the separation mode of choice. However, the needs for increased selectivity and increased retention of hydrophilic bases have substantially increased the interest in hydrophilic interaction chromatography (HILIC). Therefore, stationary phases and this mode of separation are discussed. Then, non-silica stationary phases (i.e., zirconium oxide, titanium oxide, alumina and porous graphitized carbon), which afford increased thermal and chemical stability and also selectivity different from those obtained with silica and hybrid silica, are discussed. In addition, the use of these materials in HILIC is also reviewed.

  6. Nitric oxide-releasing fumed silica particles: synthesis, characterization, and biomedical application.

    PubMed

    Zhang, Huiping; Annich, Gail M; Miskulin, Judiann; Stankiewicz, Kelly; Osterholzer, Kathryn; Merz, Scott I; Bartlett, Robert H; Meyerhoff, Mark E

    2003-04-30

    The preparation, characterization, and preliminary biomedical application of various nitric oxide (NO)-releasing fumed silica particles (0.2-0.3 microm) are reported. The tiny NO-releasing particles are synthesized by first tethering alkylamines onto the surface of the silica using amine-containing silylation reagents. These amine groups are then converted to corresponding N-diazeniumdiolate groups via reaction with NO(g) at high pressure in the presence of methoxide bases (e.g., NaOMe). N-Diazeniumdiolate groups were found to form more readily with secondary amino nitrogens than primary amino nitrogens tethered to the silica. Different alkali metal cations of the methoxide bases, however, have little effect on the degree of N-diazeniumdiolate formation. The N-diazeniumdiolate moieties attached on the silica surface undergo a primarily proton-driven dissociation to NO under physiological conditions, with an "apparent" reaction order somewhat greater than 1 owing to local increases in pH at the surface of the particles as free amine groups are generated. The rates of N-diazeniumdiolate dissociation are further related to the parent amine structures and the pH of the soaking buffer. The N-diazeniumdiolate groups also undergo slow thermal dissociation to NO, with zero-order dissociation observed at both -15 and 23 degrees C. It is further shown that the resulting NO-releasing fumed silica particles can be embedded into polymer films to create coatings that are thromboresistant, via the release of NO at fluxes that mimic healthy endothelial cells (EC). For example a polyurethane coating containing 20 wt % of NO-releasing particles prepared with pendant hexane diamine structure (i.e., Sil-2N[6]-N(2)O(2)Na) is shown to exhibit improved surface thromboresistivity (compared to controls) when used to coat the inner walls of extracorporeal circuits (ECC) employed in a rabbit model for extracorporeal blood circulation.

  7. New Stable Cu(I) Catalyst Supported on Weakly Acidic Polyacrylate Resin for Green C-N Coupling: Synthesis of N-(Pyridin-4-yl)benzene Amines and N,N-Bis(pyridine-4-yl)benzene Amines.

    PubMed

    Kore, Nitin; Pazdera, Pavel

    2016-12-22

    A method for preparation of a new stable Cu(I) catalyst supported on weakly acidic polyacrylate resin without additional stabilizing ligands is described. A simple and efficient methodology for Ullmann Cu(I) catalyzed C-N cross coupling reactions using this original catalyst is reported. Coupling reactions of 4-chloropyridinium chloride with anilines containing electron donating (EDG) or electron withdrawing (EWG) groups, naphthalen-2-amine and piperazine, respectively, are successfully demonstrated.

  8. Probing Intramolecular versus Intermolecular CO2 Adsorption on Amine-Grafted SBA-15.

    PubMed

    Yoo, Chun-Jae; Lee, Li-Chen; Jones, Christopher W

    2015-12-15

    A mesoporous silica SBA-15 is modified with an array of amine-containing organosilanes including (i) propylamine, SiCH2CH2CH2NH2 (MONO), (ii) propylethylenediamine, SiCH2CH2CH2NHCH2CH2NH2 (DI), (iii) propyldiethylenetriamine, SiCH2CH2CH2NHCH2CH2NHCH2CH2NH2 (TRI), and (iv) propyltriethylenetetramine, SiCH2CH2CH2NHCH2CH2N(CH2CH2NH2)2 (TREN) and the low loading silane adsorbents (∼0.45 mmol silane/g) are evaluated for their CO2 adsorption properties, with a focus on gaining insight into the propensity for intramolecular vs intermolecular CO2 adsorption. Adsorption isotherms at low CO2 coverages are measured while simultaneously recording the heat evolved via a Tian-Calvet calorimeter. The results are compared on a silane molecule efficiency basis (mol CO2 adsorbed/mol silane) to assess the potential for intramolecular CO2 adsorption, employing two amine groups in a single silane molecule. As the number of amines in the silane molecule increases (MONO < DI < TREN ∼ TRI), the silane molecule efficiency is enhanced owing to the ability to intramolecularly capture CO2. Analysis of the CO2 uptake for samples with the surface silanols removed by capping demonstrates that cooperative uptake due to amine-CO2-silanol interactions is also possible over these adsorbents and is the primary mode of sorption for the MONO material at the studied low silane loading. As the propensity for intramolecular CO2 capture increases due to the presence of multiple amines in a single silane molecule (MONO < DI < TREN ∼ TRI), the measured heat of adsorption also increases. This study of various amine-containing silanes at low coverage is the first to provide significant, direct evidence for intramolecular CO2 capture in a single silane molecule. Furthermore, it provides evidence for the relative heats of adsorption for physisorption on a silanol laden surface (ca. 37 kJ/mol), a silanol-capped surface (ca. 25 kJ/mol), via amine-CO2-silanol interactions (ca. 46 kJ/mol), and via amine-CO2

  9. Synthesis of 1,3-Amino Alcohols, 1,3-Diols, Amines, and Carboxylic Acids from Terminal Alkynes.

    PubMed

    Zeng, Mingshuo; Herzon, Seth B

    2015-09-04

    The half-sandwich ruthenium complexes 1-3 activate terminal alkynes toward anti-Markovnikov hydration and reductive hydration under mild conditions. These reactions are believed to proceed via addition of water to metal vinylidene intermediates (4). The functionalization of propargylic alcohols by metal vinylidene pathways is challenging owing to decomposition of the starting material and catalytic intermediates. Here we show that catalyst 2 can be employed to convert propargylic alcohols to 1,3-diols in high yield and with retention of stereochemistry at the propargylic position. The method is also amenable to propargylic amine derivatives, thereby establishing a route to enantioenriched 1,3-amino alcohol products. We also report the development of formal anti-Markovnikov reductive amination and oxidative hydration reactions to access linear amines and carboxylic acids, respectively, from terminal alkynes. This chemistry expands the scope of products that can be prepared from terminal alkynes by practical and high-yielding metal-catalyzed methods.

  10. Hydroxide-catalyzed bonding

    NASA Technical Reports Server (NTRS)

    Gwo, Dz-Hung (Inventor)

    2003-01-01

    A method of bonding substrates by hydroxide-catalyzed hydration/dehydration involves applying a bonding material to at least one surface to be bonded, and placing the at least one surface sufficiently close to another surface such that a bonding interface is formed between them. A bonding material of the invention comprises a source of hydroxide ions, and may optionally include a silicate component, a particulate filling material, and a property-modifying component. Bonding methods of the invention reliably and reproducibly provide bonds which are strong and precise, and which may be tailored according to a wide range of possible applications. Possible applications for bonding materials of the invention include: forming composite materials, coating substrates, forming laminate structures, assembly of precision optical components, and preparing objects of defined geometry and composition. Bonding materials and methods of preparing the same are also disclosed.

  11. Speaking Personally--with Amin Qazi

    ERIC Educational Resources Information Center

    Ragan, Lawrence

    2016-01-01

    This article provides an interview with Amin Quazi, the founding chief executive officer of Unizin, a university-owned consortium focused on the emerging digital teaching and learning ecosystem. Amin has a bachelor's degree in chemical engineering from The University of Iowa and a master's degree in business administration from the Carlson School…

  12. Determination of equivalent weight of amines

    SciTech Connect

    Selig, W.S.

    1987-01-08

    A procedure for the determination of equivalent weight of amines is described. This procedure is based on an acid-base reaction performed in glacial acetic acid. The sum of primary, secondary, and tertiary amines are determined by titration with standard perchloric acid in glacial acetic acid. 1 ref.

  13. Development of an efficient amine-functionalized glass platform by additional silanization treatment with alkylsilane.

    PubMed

    Kamisetty, Nagendra Kumar; Pack, Seung Pil; Nonogawa, Mitsuru; Devarayapalli, Kamakshaiah Charyulu; Kodaki, Tsutomu; Makino, Keisuke

    2006-11-01

    Aminosilane-treated molecular layers on glass surfaces are frequently used as functional platforms for biosensor preparation. All the amino groups present on the surface are not available in reactive forms, because surface amino groups interact with remaining unreacted surface silanol groups. Such nonspecific interactions might reduce the efficiency of chemical immobilization of biomolecules such as DNA, enzymes, antibodies, etc., in biosensor fabrication. To improve immobilization efficiency we have used additional surface silanization with alkylsilane (capping) to convert the remaining silanol groups into Si-O-Si linkages, thereby liberating the amino groups from nonspecific interaction with the silanol groups. We prepared different types of capped amine surface and evaluated the effect of capping on immobilization efficiency by investigating the fluorescence intensity of Cy3-NHS (N-hydroxysuccinimide) dye that reacted with amino groups. The results indicate that most of the capped amine surfaces resulted in enhanced efficiency of immobilization of Cy3-NHS compared with the untreated control amine surface. We found a trend that trialkoxysilanes had greater capping effects on immobilization efficiency than monoalkoxysilanes. It was also found that the aliphatic chain of alkylsilane, which does not participate in the capping of the silanol, had an important function in enhancing immobilization efficiency. These results would be useful for preparation of an amine-modified surface platform, with enhanced immobilization efficiency, which is essential for developing many kinds of biosensors on a silica matrix.

  14. 15N NMR investigation of the covalent binding of reduced TNT amines to soil humic acid, model compounds, and lignocellulose

    USGS Publications Warehouse

    Thorn, K.A.; Kennedy, K.R.

    2002-01-01

    The five major reductive degradation products of TNT-4ADNT (4-amino-2,6-dinitrotoluene), 2ADNT (2-amino-4,6-dinitrotoluene), 2,4DANT (2,4-diamino-6-nitrotoluene), 2,6DANT (2,6-diamino-4-nitrotoluene), and TAT (2,4,6-triaminotoluene)-labeled with 15N in the amine positions, were reacted with the IHSS soil humic acid and analyzed by 15N NMR spectrometry. In the absence of catalysts, all five amines underwent nucleophilic addition reactions with quinone and other carbonyl groups in the soil humic acid to form both heterocyclic and nonheterocyclic condensation products. Imine formation via 1,2-addition of the amines to quinone groups in the soil humic acid was significant with the diamines and TAT but not the monoamines. Horseradish peroxidase (HRP) catalyzed an increase in the incorporation of all five amines into the humic acid. In the case of the diamines and TAT, HRP also shifted the binding away from heterocyclic condensation product toward imine formation. A comparison of quantitative liquid phase with solid-state CP/MAS 15N NMR indicated that the CP experiment underestimated imine and heterocyclic nitrogens in humic acid, even with contact times optimal for observation of these nitrogens. Covalent binding of the mono- and diamines to 4-methylcatechol, the HRP catalyzed condensation of 4ADNT and 2,4DANT to coniferyl alcohol, and the binding of 2,4DANT to lignocellulose with and without birnessite were also examined.

  15. Amine Measurements in Boreal Forest Air

    NASA Astrophysics Data System (ADS)

    Hemmilä, Marja; Hellén, Heidi; Makkonen, Ulla; Hakola, Hannele

    2015-04-01

    Amines are reactive, volatile bases in the air with a general formula of RNH2, R2NH or R3N. Especially small amines can stabilize sulphuric acid clusters and hence affect nucleation. Amines react rapidly with hydroxyl radical (OH˙) thus affecting oxidative capacity of the atmosphere. The amine concentrations are higher in forest air than in urban air (Hellén et al., 2014), but the sources are not known. In order to get more information concerning amine sources, we conducted a measurement campaign in a boreal forest. At SMEAR II station at Hyytiälä, Southern Finland (61°510'N, 24°170'E, 180 m a.s.l.) The measurements cover seven months, from June to December 2014. For sampling and measuring we used MARGA (The instrument for Measuring AeRosols and Gases in Ambient air) which is an on-line ion chromatograph (IC) connected to a sampling system. The IC component of the MARGA system was coupled to an electrospray ionization quadrupole mass spectrometer (MS) to improve sensitivity of amine measurements. This new set-up enabled amine concentration measurements in ambient air both in aerosol and gas phases with a time resolution of only 1 hour. With MARGA-MS we analysed 7 different amines: monomethylamine (MMA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA), propylamine (PA) and butylamine (BA). In preliminary data-analysis we found out, that in June and July most of the measured amines were in gas phase, and particle phase amine concentrations were mostly under detection limits (<1.7 pptv). In June the gaseous amine concentrations were higher than in July. The measured concentrations of gaseous amines followed temperature variation, which could indicate that amines are produced and emitted from the environment or re-emitted from the surfaces as temperature rises after deposition during night-time. All measured amines had similar diurnal variation with maxima during afternoon and minima during night. Results from other months will also

  16. Thermal Decomposition Chemistry of Amine Borane (U)

    SciTech Connect

    Stowe, A. C.; Feigerle, J.; Smyrl, N. R.; Morrell, J. S.

    2010-01-29

    The conclusions of this presentation are: (1) Amine boranes potentially can be used as a vehicular hydrogen storage material. (2) Purity of the hydrogen stream is critical for use with a fuel cell. Pure H{sub 2} can be provided by carefully conditioning the fuel (encapsulation, drying, heating rate, impurities). (3) Thermodynamics and kinetics can be controlled by conditioning as well. (4) Regeneration of the spent amine borane fuel is still the greatest challenge to its potential use. (5) Addition of hydrocarbon-substituted amine boranes alter the chemistry dramatically. (6) Decomposition of the substituted amine borane mixed system favors reaction products that are more potentially easier to regenerate the hydrogenated fuel. (7) t-butylamine borane is not the best substituted amine borane to use since it releases isobutane; however, formation of CNBH{sub x} products does occur.

  17. Amine(imine)diphosphine iron catalysts for asymmetric transfer hydrogenation of ketones and imines.

    PubMed

    Zuo, Weiwei; Lough, Alan J; Li, Young Feng; Morris, Robert H

    2013-11-29

    A rational approach is needed to design hydrogenation catalysts that make use of Earth-abundant elements to replace the rare elements such as ruthenium, rhodium, and palladium that are traditionally used. Here, we validate a prior mechanistic hypothesis that partially saturated amine(imine)diphosphine ligands (P-NH-N-P) activate iron to catalyze the asymmetric reduction of the polar bonds of ketones and imines to valuable enantiopure alcohols and amines, with isopropanol as the hydrogen donor, at turnover frequencies as high as 200 per second at 28°C. We present a direct synthetic approach to enantiopure ligands of this type that takes advantage of the iron(lI) ion as a template. The catalytic mechanism is elucidated by the spectroscopic detection of iron hydride and amide intermediates.

  18. Biocatalytic asymmetric synthesis of chiral amines from ketones applied to sitagliptin manufacture.

    PubMed

    Savile, Christopher K; Janey, Jacob M; Mundorff, Emily C; Moore, Jeffrey C; Tam, Sarena; Jarvis, William R; Colbeck, Jeffrey C; Krebber, Anke; Fleitz, Fred J; Brands, Jos; Devine, Paul N; Huisman, Gjalt W; Hughes, Gregory J

    2010-07-16

    Pharmaceutical synthesis can benefit greatly from the selectivity gains associated with enzymatic catalysis. Here, we report an efficient biocatalytic process to replace a recently implemented rhodium-catalyzed asymmetric enamine hydrogenation for the large-scale manufacture of the antidiabetic compound sitagliptin. Starting from an enzyme that had the catalytic machinery to perform the desired chemistry but lacked any activity toward the prositagliptin ketone, we applied a substrate walking, modeling, and mutation approach to create a transaminase with marginal activity for the synthesis of the chiral amine; this variant was then further engineered via directed evolution for practical application in a manufacturing setting. The resultant biocatalysts showed broad applicability toward the synthesis of chiral amines that previously were accessible only via resolution. This work underscores the maturation of biocatalysis to enable efficient, economical, and environmentally benign processes for the manufacture of pharmaceuticals.

  19. Chemically Responsive Nanoporous Pigments: Colorimetric Sensor Arrays and the Identification of Aliphatic Amines

    PubMed Central

    Bang, Jin Ho; Lim, Sung H.; Park, Erwin; Suslick, Kenneth S.

    2008-01-01

    A general method has been developed for the preparation of microspheres of nanoporous pigments, their formulation into chemically responsive pigment inks, and the printing of these inks as calorimetric sensor arrays. Using an ultrasonic-spray aerosol–gel synthesis from chemically responsive dyes and common silica precursors, 16 different nanoporous pigment microspheres have been prepared and characterized. New calorimetric sensor arrays have been created by printing inks of these chemically responsive pigments as primary sensor elements; these arrays have been successfully tested for the detection, identification, and quantitation of toxic aliphatic amines. Among 11 structurally similar amines, complete identification of each analyte without confusion was achieved using hierarchical cluster analysis (HCA). Furthermore, visual identification of ammonia gas was easily made at the IDLH (immediately dangerous to life or health), PEL (permissible exposure limits), and 0.1 PEL concentrations with high reproducibility. PMID:18950204

  20. Kinetics of silica polymerization

    SciTech Connect

    Weres, O.; Yee, A.; Tsao, L.

    1980-05-01

    The polymerization of silicic acid in geothermal brine-like aqueous solutions to produce amorphous silica in colloidal form has been studied experimentally and theoretically. A large amount of high quality experimental data has been generated over the temperature rang 23 to 100{sup 0}C. Wide ranges of dissolved silica concentration, pH, and sodium chloride concentration were covered. The catalytic effects of fluoride and the reaction inhibiting effects of aluminum and boron were studied also. Two basic processes have been separately studied: the formation of new colloidal particles by the homogeneous nucleation process and the deposition of dissolved silica on pre-existing colloidal particles. A rigorous theory of the formation of colloidal particles of amorphous silica by homogeneous nucleation was developed. This theory employs the Lothe-Pound formalism, and is embodied in the computer code SILNUC which quantitatively models the homogeneous nucleation and growth of colloidal silica particles in more than enough detail for practical application. The theory and code were extensively used in planning the experimental work and analyzing the data produced. The code is now complete and running in its final form. It is capable of reproducing most of the experimental results to within experimental error. It is also capable of extrapolation to experimentally inaccessible conditions, i.e., high temperatures, rapidly varying temperature and pH, etc.

  1. Investigation into the role of silica in lithium polysulfide adsorption for lithium sulfur battery

    SciTech Connect

    Kim, Miso; Kang, Sung-Hwan; Manuel, James; Zhao, Xiaohui; Cho, Kwon Koo; Ahn, Jou Hyeon

    2015-09-15

    Highlights: • Amine functionalized silica nanoparticles (AFSN) were prepared. • Polysulfide adsorption studies were carried out with silica nanoparticles and AFSN. • Sulfur cathodes were prepared with SN and AFSN for Li–S batteries. • AFSN showed excellent polysulfide adsorption. - Abstract: A new type of sulfur electrodes with the ability for polysulfide adsorption was prepared by incorporating silica nanoparticles (SN) or amine functionalized silica nanoparticles (AFSN). AFSN was synthesized by a simple and cost-effective method. The functionalization and surface morphology of silica were confirmed with Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM), respectively. Polysulfide adsorption studies were carried out using UV–vis spectrometer, which confirmed the excellent adsorption of polysulfides by AFSN. Interaction of polysulfides with SN or AFSN was studied using FTIR and FT-Raman spectroscopy. The effective polysulfide adsorption by SN and AFSN leads to good and stable cycle performance of lithium sulfur cells. The results show that the incorporation of SN or AFSN with sulfur is a promising method to prepare cathode material for lithium sulfur batteries.

  2. Phase Transformation in Silica-Coated FePt Nanoparticles

    NASA Astrophysics Data System (ADS)

    Colak, Levent; Hadjipanayis, George

    2009-03-01

    The A1 to L10 phase transformation has been examined in silica-coated FePt particles. The nanoparticles were synthesized by reduction of platinum acetylacetonate (Pt (acac) 2) followed by thermal decomposition of iron pentacarbonyl (Fe(CO)5) in the presence of oleic acid (OA) and oleyl amine (OY) as surfactants at low temperature ^[1]. The monodispersed FePt nanoparticles, with a size of 5.8 nm were then coated with silica (SiO2) shells ^[2] . The thickness of the silica shell could be controlled between 7.5-25 nm. The coated particles were subjected to thermal processing at 800 C for various amounts of times. No significant sintering was observed up to 2 hours of annealing for the shell thickness of 15.0 nm. In some silica-coated samples an increase in the particle size was observed after annealing. Selected Area Diffraction analysis and magnetic measurements showed the development of ordered L10 structure. Coercivity values up to 15 kOe at 7K are obtained. The phase transformation is currently being examined in other samples annealed at different times and temperatures and the results will be reported.1.Levent Colak and George C. Hadjipanayis, Nanotechnology 19 (2008) 235703.2.M. Aslam, L. Fu, S. Li, Vinayak P. Dravid, Journal of Colloid and Interface Science 290 (2005) 444--449.

  3. Silica Precipitation and Lithium Sorption

    SciTech Connect

    Jay Renew

    2015-09-20

    This file contains silica precipitation and lithium sorption data from the project. The silica removal data is corrected from the previous submission. The previous submission did not take into account the limit of detection of the ICP-MS procedure.

  4. Efficient Cu(OTf)2-catalyzed synthesis of novel and diverse 2,3-dihydroquinazolin-4(1H)-ones.

    PubMed

    Zhu, Xiaoyan; Kang, So Rang; Xia, Likai; Lee, Jihye; Basavegowda, Nagaraj; Lee, Yong Rok

    2015-02-01

    An efficient one-pot synthesis of various 2,3-dihydroquinazolin-4(1H)-one derivatives was accomplished using Cu(OTf)2-catalyzed multi-component reactions between isatoic anhydride, ketones, and amines. The method has several significant advantages; mild reaction conditions, easy handling, and efficiency of catalyst.

  5. Copper-catalyzed aerobic C(sp2)-H functionalization for C-N bond formation: synthesis of pyrazoles and indazoles.

    PubMed

    Li, Xianwei; He, Li; Chen, Huoji; Wu, Wanqing; Jiang, Huanfeng

    2013-04-19

    A simple, practical, and highly efficient synthesis of pyrazoles and indazoles via copper-catalyzed direct aerobic oxidative C(sp(2))-H amination has been reported herein. This process tolerated a variety of functional groups under mild conditions. Further diversification of pyrazoles was also investigated, which provided its potential for drug discovery.

  6. Consecutive condensation, C-N and N-N bond formations: a copper- catalyzed one-pot three-component synthesis of 2H-indazole.

    PubMed

    Kumar, Manian Rajesh; Park, Ahbyeol; Park, Namjin; Lee, Sunwoo

    2011-07-01

    2H-Indazoles are synthesized using copper-catalyzed, one-pot, three-component reactions of 2-bromobenzaldehydes, primary amines, and sodium azide. A copper catalyst plays the key role in the formation of C-N and N-N bonds. This method has a broad substrate scope with a high tolerance for a variety of functional groups.

  7. A general and efficient approach to 2H-indazoles and 1H-pyrazoles through copper-catalyzed intramolecular N-N bond formation under mild conditions.

    PubMed

    Hu, Jiantao; Cheng, Yongfeng; Yang, Yiqing; Rao, Yu

    2011-09-28

    A new efficient copper-catalyzed intramolecular amination reaction has been developed to readily synthesise a wide variety of multi-substituted 2H-indazole and 1H-pyrazole derivatives from easily accessible starting materials under mild conditions. A highly selective ligand for estrogen receptor β was prepared in three steps by employing this method.

  8. Simultaneous structure-activity studies and arming of natural products by C–H amination reveal cellular targets of eupalmerin acetate

    PubMed Central

    Li, Jing; Cisar, Justin S.; Zhou, Congying; Vera, Brunilda; Williams, Howard; Rodríguez, Abimael D.; Cravatt, Benjamin F.; Romo, Daniel

    2014-01-01

    To fully exploit the inherent and enduring potential of natural products for fundamental cell biology and drug lead discovery, synthetic methods for functionalizing unique sites are highly desirable. Here we describe a strategy for the derivatization of natural products at ‘unfunctionalized’ positions via Rh(II)-catalyzed amination enabling simultaneous structure-activity relationship (SAR) studies and arming (alkynylation) of natural products. Employing Du Bois C–H amination, allylic and benzylic C–H bonds underwent amination and olefins underwent aziridination. With tertiary amine-containing natural products, amidines were produced via C–H amination/oxidation and unusual N-aminations provided hydrazine sulfamate inner salts. The alkynylated derivatives are readied for subsequent conjugation to access cellular probes for mechanism of action studies. Both chemo- and site-selectivity was studied by application to a diverse set of natural products including the marine-derived anticancer diterpene, eupalmerin acetate (EPA). Quantitative proteome profiling with an alkynyl EPA derivative obtained by site-selective, allylic C–H amination led to identification of several protein targets in HL-60 cells, including several known to be associated with cancer proliferation, suggestive of a polypharmacological mode of action for EPA. PMID:23695633

  9. Application of Silica-Supported Alkylating Reagents in a One-Pot, Sequential Protocol to Diverse Benzoxathiazepine 1,1-Dioxides.

    PubMed

    Faisal, Saqib; Maity, Pradip K; Zang, Qin; Samarakoon, Thiwanka B; Sourk, Robert L; Hanson, Paul R

    2016-07-11

    Applications of silica-ROMP reagents in a one-pot, sequential protocol have been developed for the synthesis of a variety of diverse benzoxathiazepine 1,1-dioxides. This protocol includes sulfonylation, intramolecular SNAr, alkylation with silica-supported oligomeric benzyl (Si-OBPn) and triazole (Si-OTPn) phosphates, and intermolecular SNAr addition with a number of secondary amines in one-pot to afford a variety of unique benzoxathiazepine 1,1-dioxides sultams in good to excellent yields.

  10. Synthetic Studies on Tricyclic Diterpenoids: Direct Allylic Amination Reaction of Isopimaric Acid Derivatives†

    PubMed Central

    Timoshenko, Mariya A.; Kharitonov, Yurii V.; Shakirov, Makhmut M.; Bagryanskaya, Irina Yu.

    2015-01-01

    Abstract A selective synthesis of 7‐ or 14‐nitrogen containing tricyclic diterpenoids was completed according to a strategy in which the key step was the catalyzed direct allylic amination of methyl 14α‐hydroxy‐15,16‐dihydroisopimarate with a wide variety of nitrogenated nucleophiles. It was revealed that the selectivity of the reaction depends on the nature of nucleophile. The catalyzed reaction of the mentioned diterpenoid allylic alcohol with 3‐nitroaniline, 3‐(trifluoromethyl)aniline, and 4‐(trifluoromethyl)aniline yield the subsequent 7α‐, 7β‐ and 14αnitrogen‐containing diterpenoids. The reaction with 2‐nitroaniline, 4‐nitro‐2‐chloroaniline, 4‐methoxy‐2‐nitroaniline, phenylsulfamide, or tert‐butyl carbamate proceeds with the formation of 7α‐nitrogen‐substituted diterpenoids as the main products. PMID:27308214

  11. Amine-Oxide Hybrid Materials for CO2 Capture from Ambient Air.

    PubMed

    Didas, Stephanie A; Choi, Sunho; Chaikittisilp, Watcharop; Jones, Christopher W

    2015-10-20

    Oxide supports functionalized with amine moieties have been used for decades as catalysts and chromatographic media. Owing to the recognized impact of atmospheric CO2 on global climate change, the study of the use of amine-oxide hybrid materials as CO2 sorbents has exploded in the past decade. While the majority of the work has concerned separation of CO2 from dilute mixtures such as flue gas from coal-fired power plants, it has been recognized by us and others that such supported amine materials are also perhaps uniquely suited to extract CO2 from ultradilute gas mixtures, such as ambient air. As unique, low temperature chemisorbents, they can operate under ambient conditions, spontaneously extracting CO2 from ambient air, while being regenerated under mild conditions using heat or the combination of heat and vacuum. This Account describes the evolution of our activities on the design of amine-functionalized silica materials for catalysis to the design, characterization, and utilization of these materials in CO2 separations. New materials developed in our laboratory, such as hyperbranched aminosilica materials, and previously known amine-oxide hybrid compositions, have been extensively studied for CO2 extraction from simulated ambient air (400 ppm of CO2). The role of amine type and structure (molecular, polymeric), support type and structure, the stability of the various compositions under simulated operating conditions, and the nature of the adsorbed CO2 have been investigated in detail. The requirements for an effective, practical air capture process have been outlined and the ability of amine-oxide hybrid materials to meet these needs has been discussed. Ultimately, the practicality of such a "direct air capture" process is predicated not only on the physicochemical properties of the sorbent, but also how the sorbent operates in a practical process that offers a scalable gas-solid contacting strategy. In this regard, the utility of low pressure drop monolith

  12. Epoxy Grout With Silica Thickener

    NASA Technical Reports Server (NTRS)

    Mcclung, C. E.

    1984-01-01

    Grout cures quickly, even in presence of hydraulic oil. Grout is mixture of aggregate particles, finely-divided silica, epoxy resin, and triethylenetetramine curing agent, with mixture containing about 85 percent silica and aggregate particle sand 15 percent resin and curing agent. Silica is thickening agent and keeps grout from sagging.

  13. Interaction energies of CO2·amine complexes: effects of amine substituents.

    PubMed

    Jorgensen, Kameron R; Cundari, Thomas R; Wilson, Angela K

    2012-10-25

    To focus on the identification of potential alternative amine carbon capture compounds, CO(2) with methyl, silyl, and trifluoromethyl monosubstituted and disubstituted amine compounds were studied. Interaction energies of these CO(2)·amine complexes were determined via two methods: (a) an ab initio composite method, the correlation consistent composite approach (ccCA), to determine interaction energies and (b) density functional theories, B3LYP/aug-cc-pVTZ and B97D/aug-cc-pVTZ. Substituent effects on the interaction energies were examined by interchanging electron donating and electron withdrawing substituents on the amine compounds. The calculations suggested two different binding modes, hydrogen bonding and acid-base interactions, which arise from the modification of the amine substituents, echoing previous work by our group on modeling protein·CO(2) interactions. Recommendations have been noted for the development of improved amine scrubber complexes.

  14. 78 FR 14540 - Cyromazine, Silica Silicates (Silica Dioxide and Silica Gel), Glufosinate Ammonium, Dioctyl...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-03-06

    ... AGENCY Cyromazine, Silica Silicates (Silica Dioxide and Silica Gel), Glufosinate Ammonium, Dioctyl Sodium... ammonium, dioctyl sodium sulfosuccinate (DSS) and undecylenic acid (UDA) and opens a public comment period...-HQ-OPP-2006-0108... Kelly Ballard, (703) 305-8126, Ballard.kelly@epa.gov . Dioctyl...

  15. Silica nanoparticles and biological dispersants: genotoxic effects on A549 lung epithelial cells

    NASA Astrophysics Data System (ADS)

    Brown, David M.; Varet, Julia; Johnston, Helinor; Chrystie, Alison; Stone, Vicki

    2015-10-01

    Silica nanoparticle exposure could be intentional (e.g. medical application or food) or accidental (e.g. occupational inhalation). On entering the body, particles become coated with specific proteins depending on the route of entry. The ability of silica particles of different size and charge (non-functionalized 50 and 200 nm and aminated 50 and 200 nm) to cause genotoxic effects in A549 lung epithelial cells was investigated. Using the modified comet assay and the micronucleus assay, we examined the effect of suspending the particles in different dispersion media [RPMI or Hanks' balanced salt solution (HBSS), supplemented with bovine serum albumin (BSA), lung lining fluid (LLF) or serum] to determine if this influenced the particle's activity. Particle characterisation suggested that the particles were reasonably well dispersed in the different media, with the exception of aminated 50 nm particles which showed evidence of agglomeration. Plain 50, 200 nm and aminated 50 nm particles caused significant genotoxic effects in the presence of formamidopyrimidine-DNA glycosylase when dispersed in HBSS or LLF. These effects were reduced when the particles were dispersed in BSA and serum. There was no significant micronucleus formation produced by any of the particles when suspended in any of the dispersants. The data suggest that silica particles can produce a significant genotoxic effect according to the comet assay in A549 cells, possibly driven by an oxidative stress-dependent mechanism which may be modified depending on the choice of dispersant employed.

  16. Transition Metals Catalyzed Element-Cyano Bonds Activations

    PubMed Central

    Wang, Rui; Falck, John R.

    2014-01-01

    Cyano group as a versatile functionalized intermediate has been explored for several decades, as it readily transfers to many useful functionalization groups such as amine, amide, acid, etc., which make it possess high popularization and use value in organic synthesis. Reactions involved with element-cyano bond cleavage can provide not only a new cyano group but also a freshly functionalized skeleton in one-pot, consequently making it of high importance. The highlights reviewed herein include H-CN, Si-CN, C-CN, B-CN, Sn-CN, Ge-CN, S-CN, Halo-CN, N-CN, and O-CN bonds cleavages and will summarize progress in such an important research area. This review article will focus on transition metal catalyzed reactions involving element-cyano bond activation. PMID:25558119

  17. Biomimetic mineral self-organization from silica-rich spring waters

    PubMed Central

    García-Ruiz, Juan Manuel; Nakouzi, Elias; Kotopoulou, Electra; Tamborrino, Leonardo; Steinbock, Oliver

    2017-01-01

    Purely inorganic reactions of silica, metal carbonates, and metal hydroxides can produce self-organized complex structures that mimic the texture of biominerals, the morphology of primitive organisms, and that catalyze prebiotic reactions. To date, these fascinating structures have only been synthesized using model solutions. We report that mineral self-assembly can be also obtained from natural alkaline silica-rich water deriving from serpentinization. Specifically, we demonstrate three main types of mineral self-assembly: (i) nanocrystalline biomorphs of barium carbonate and silica, (ii) mesocrystals and crystal aggregates of calcium carbonate with complex biomimetic textures, and (iii) osmosis-driven metal silicate hydrate membranes that form compartmentalized, hollow structures. Our results suggest that silica-induced mineral self-assembly could have been a common phenomenon in alkaline environments of early Earth and Earth-like planets. PMID:28345049

  18. Infrared and Raman spectroscopic characterization of some organic substituted hybrid silicas.

    PubMed

    Capeletti, Larissa B; Baibich, Ione M; Butler, Ian S; dos Santos, João H Z

    2014-12-10

    Nine hybrid silicas bearing the organic substituent groups methyl, octyl, octadecyl, vinyl, phenyl, mercaptopropyl, isocyanatopropyl, chloropropyl and glycidoxypropyl were synthesized by an acid-catalyzed, hydrolytic sol-gel process. The resulting solid materials were characterized by their absorbance and attenuated total reflection (ATR) IR and Raman spectra. The latter technique proved to be particularly useful in the identification of the organic moieties in the hybrid silicas. The effect of the presence of the organic groups on the silica networks was also investigated - there were increases observed in both the SiOSi bond angles and bond lengths. Moreover, deconvolution of the IR-active antisymmetric SiOSi stretching bands permitted detection of the four- and six-membered siloxane rings present in the silicas. There proved to be a greater number of four-membered rings on the surfaces of the particles. Both IR and Raman spectroscopy proved to be invaluable in the characterization of these hybrid materials.

  19. Controllable synthesis of hollow mesoporous silica spheres and application as support of nano-gold

    NASA Astrophysics Data System (ADS)

    Wang, Tao; Ma, Weihua; Shangguan, Junnan; Jiang, Wei; Zhong, Qin

    2014-07-01

    Hollow silica spheres with mesoporous structure were synthesized by sol-gel/emulsion method. In the process, the surfactant, cetyltrimethylammonium bromide (CTAB) was used to stabilize the oil droplet and also used as structure direct agent. The diameter of the hollow silica spheres, ranging from 895 nm to 157 nm, can be controlled by changing the ratio of ethanol to water and the concentration of the surfactant as well. The shell thickness of the spheres decreased when the ratio of ethanol to water decreased. The proposed mechanism of the formation of silica spheres could elucidate the experimental results well. Furthermore, the resultant hollow mesoporous silica spheres were then employed as support of nano-gold which was used to catalyze the isomerization reaction of propylene oxide to produce allyl alcohol.

  20. Amines as occupational hazards for visual disturbance

    PubMed Central

    JANG, Jae-Kil

    2015-01-01

    Various amines, such as triethylamine and N,N-dimethylethylamine, have been reported to cause glaucopsia in workers employed in epoxy, foundry, and polyurethane foam industries. This symptom has been related to corneal edema and vesicular collection of fluid within the corneal subepithelial cells. Exposure to amine vapors for 30 min to several hours leads to blurring of vision, a blue-grey appearance of objects, and halos around lights, that are probably reversible. Concentration-effect relationships have been established. The visual disturbance is considered a nuisance, as it could cause onsite accidents, impair work efficiency, and create difficulties in driving back home. Occupational exposure limits have been established for some amines, but there is shortage of criteria. Volatility factors, such as vapor pressure, should be considered in industrial settings to prevent human ocular risks, while trying to reduce levels of hazardous amines in the atmosphere. PMID:26538000

  1. Sediment-Associated Reactions of Aromatic Amines

    EPA Science Inventory

    Sorption of aromatic amines to sediments and soils can occur by both reversible physical processes and irreversible chemical processes. To elucidate the significance of these sorption pathways, the sorption kinetics of aniline and pyridine were studied in resaturated pond sedimen...

  2. Khalil Amine on Lithium-air Batteries

    SciTech Connect

    Khalil Amine

    2009-09-14

    Khalil Amine, materials scientist at Argonne National Laboratory, speaks on the new technology Lithium-air batteries, which could potentially increase energy density by 5-10 times over lithium-ion batteries.

  3. Khalil Amine on Lithium-air Batteries

    ScienceCinema

    Khalil Amine

    2016-07-12

    Khalil Amine, materials scientist at Argonne National Laboratory, speaks on the new technology Lithium-air batteries, which could potentially increase energy density by 5-10 times over lithium-ion batteries.

  4. Efficient addition of alcohols, amines and phenol to unactivated alkenes by Au(III) or Pd(II) stabilized by CuCl2.

    PubMed

    Zhang, Xin; Corma, Avelino

    2008-01-21

    The nucleophilic addition of alcohols, amines and phenol to unactivated alkenes catalyzed by cationic gold and palladium becomes limited due to the fast reduction into metallic gold under reaction conditions. The presence of CuCl2 retards the reduction of Au(III) and Pd", strongly increasing the turnover number of gold and palladium catalysts. It is shown that new Au(III)-CuCl2 and Pd(II)-CuCl2 catalysts are active and selective for the nucleophilic addition of alcohols, amines and phenol to unactivated alkenes.

  5. Role of planar chirality of S,N- and P,N-ferrocene ligands in palladium-catalyzed allylic substitutions.

    PubMed

    You, Shu-Li; Hou, Xue-Long; Dai, Li-Xin; Yu, Yi-Hua; Xia, Wei

    2002-07-12

    Palladium-catalyzed asymmetric allylic substitutions using thioether and phosphino derivatives of ferrocenyloxazoline as ligands have been investigated with a focus on studying the role of planar chirality. In allylic alkylation, up to 98% ee and 95% ee were achieved with S,N- and P,N-ligands, respectively. In allylic amination, 97% ee was realized with P,N-ligands in the presence of TBAF. Several palladium allylic complexes were characterized by X-ray diffraction and/or solution NMR. Thioether derivatives of ferrocenyloxazolines with only planar chirality showed lower enantioselectivity in the allylic alkylation except 5c because of the formation of a new chirality on sulfur atom during the coordination of sulfur with palladium. On the other hand, in the planar chiral P,N-ligands without central chirality, (Sp)-11a-c there was no such disturbance and comparatively higher enantioselectivity in both palladium-catalyzed allylic alkylation and amination was provided.

  6. Optical patterning of photosensitive thin film silica mesophases

    SciTech Connect

    DOSHI,DHAVAL A.; HUESING,NICOLA K.; LU,MENGCHENG; FAN,HONGYOU; HURD,ALAN J.; BRINKER,C. JEFFREY

    2000-02-09

    Photosensitive films incorporating molecular photoacid generators compartmentalized within a silica-surfactant mesophase were prepared by an evaporation-induced self-assembly process. UV-exposure promoted localized acid-catalyzed siloxane condensation, enabling selective etching of unexposed regions, thereby serving as a resistless technique to prepare patterned mesoporous silica. The authors also demonstrated an optically-defined mesophase transformation (hexagonal {r_arrow} tetragonal) and patterning of refractive index and wetting behavior. Spatial control of structure and function on the macro- and mesoscales is of interest for sensor arrays, nano-reactors, photonic and fluidic devices, and low dielectric constant films. More importantly, it extends the capabilities of conventional lithography from spatially defining the presence or absence of film to spatial control of film structure and function.

  7. Reactions and clustering of water with silica surface.

    PubMed

    Ma, Yuchen; Foster, A S; Nieminen, R M

    2005-04-08

    The interaction between silica surface and water is an important topic in geophysics and materials science, yet little is known about the reaction process. In this study we use first-principles molecular dynamics to simulate the hydrolysis process of silica surface using large cluster models. We find that a single water molecule is stable near the surface but can easily dissociate at three-coordinated silicon atom defect sites in the presence of other water molecules. These extra molecules provide a mechanism for hydrogen transfer from the original water molecule, hence catalyzing the reaction. The two-coordinated silicon atom is inert to the water molecule, and water clusters up to pentamer could be stably adsorbed at this site at room temperature.

  8. Analysis of amines in plant materials.

    PubMed

    Bouchereau, A; Guénot, P; Larher, F

    2000-09-29

    Biogenic amines are conveniently divided into aliphatic monoamines, aliphatic di- and polyamines and aromatic amines. These compounds are shown to fulfill an array of roles in cellular metabolism. Thus, amines are needed for growth and development and their metabolism appears to be coordinated with the cell cycle. Di- and polyamines, among which are putrescine, spermidine and spermine, are ubiquitous polycationic molecules that occur in all living cells. However, plants accumulate a number of specific related compounds under free or conjugated forms. In plant tissues, the molecular diversity combined with the fact that amine contents are highly responsive to developmental and environmental signals encouraged analysts to develop specific procedures for their isolation and characterization. The main goals were to develop high performance routine procedures in terms of selectivity, repeatability and detectability with minimum running costs. Domains of application concern not only fundamental aspects of amine biochemistry and physiology in plants but also increasing needs in the control of food and beverage quality from plant origin. The present review reports the most recent advances in extraction, identification and quantitation of amines in plant tissues with special interest in the analysis of original and uncommon metabolites. Emphasis is directed towards chromatographic and electrophoretic separation methodologies and new detection technologies of both derivatized and underivatized compounds including photometry, fluorometry, amperometry and mass spectrometry.

  9. Solubility of nitrous oxide in amine solutions

    SciTech Connect

    Bensetiti, Z.; Iliuta, I.; Larachi, F.; Grandjean, B.P.A.

    1999-01-01

    The solubility of nitrous oxide (N{sub 2}O) in 13 amine solvents and solutions was correlated to amine mole fractions and temperature using feedforward neural networks. This general correlation, using a massive database, predicted N{sub 2}O solubility at temperatures between 283 and 398 K in pure solvents [H{sub 2}O, monoethanolamine (MEA), diethanolamine (DEA), methyldiethanolamine (MDEA), and 2-amino-2-methyl-1-propanolamine (AMP)], in binary aqueous amine solutions [H{sub 2}O/MEA, H{sub 2}O/DEA, H{sub 2}O/MDEA, and H{sub 2}O/AMP], and in ternary aqueous amine blends [AMP/MDEA/H{sub 2}O, AMP/DEA/H{sub 2}O, DEA/MDEA/H{sub 2}O, MDEA/MEA/H{sub 2}O, and AMP/MEA/H{sub 2}O]. Combined with the N{sub 2}O analogy, this present improved correlation can be advantageously implemented in amine plant design software and procedures for the prediction of CO{sub 2} solubility in amine blend solutions over wide temperature and concentration ranges.

  10. Inhibition and oxygen activation in copper amine oxidases.

    PubMed

    Shepard, Eric M; Dooley, David M

    2015-05-19

    Copper-containing amine oxidases (CuAOs) use both copper and 2,4,5-trihydroxyphenylalanine quinone (TPQ) to catalyze the oxidative deamination of primary amines. The CuAO active site is highly conserved and comprised of TPQ and a mononuclear type II copper center that exhibits five-coordinate, distorted square pyramidal coordination geometry with histidine ligands and equatorially and axially bound water in the oxidized, resting state. The active site is buried within the protein, and CuAOs from various sources display remarkable diversity with respect to the composition of the active site channel and cofactor accessibility. Structural and mechanistic factors that influence substrate preference and inhibitor sensitivity and selectivity have been defined. This Account summarizes the strategies used to design selective CuAO inhibitors based on active site channel characteristics, leading to either enhanced steric fits or the trapping of reactive electrophilic products. These findings provide a framework to support the future development of candidate molecules aimed at minimizing the negative side effects associated with drugs containing amine functionalities. This is vital given the existence of human diamine oxidase and vascular adhesion protein-1, which have distinct amine substrate preferences and are associated with different metabolic processes. Inhibition of these enzymes by antifungal or antiprotozoal agents, as well as classic monoamine oxidase (MAO) inhibitors, may contribute to the adverse side effects associated with drug treatment. These observations provide a rationale for the limited clinical value associated with certain amine-containing pharmaceuticals and emphasize the need for more selective AO inhibitors. This Account also discusses the novel roles of copper and TPQ in the chemistry of O2 activation and substrate oxidation. Reduced CuAOs exist in a redox equilibrium between the Cu(II)-TPQAMQ (aminoquinol) and Cu(I)-TPQSQ (semiquinone). Elucidating

  11. Kinetics of phenolic polymerization catalyzed by peroxidase in organic media

    SciTech Connect

    Xu, Y.P.; Huang, G.L; Yu, Y.T.

    1995-07-05

    Phenolic polymerization was carried out by enzymatic catalysis in organic media, and its kinetics was studied by using high-pressure liquid chromatography (HPLC). Phenols and aromatic amines with electron-withdrawing groups could hardly be polymerized by HRP catalysis, but phenols and aromatic amines with electron-donating groups could easily by polymerized. The reaction rate of either the para-substituted substrate or meta-substituted substrate was higher than that of ortho-substituted substrate. When ortho-position of hydroxy group of phenols was occupied by an electron-donating group and if another electron-donating group occupied para-position of hydroxy group, the reaction rate increased. Horseradish peroxidase and lactoperoxidase could easily catalyze the polymerization, but chloroperoxidase and laccase failed to yield polymers. Metallic ions such as Mn{sup 2+}, Fe{sup 2+}, or Fe{sup 3+}, and Cu{sup 2+} could poison horseradish peroxidase to various extents, but ions such as Co{sup 2+}, Cd{sup 2+}, Zn{sup 2+}, and K{sup +} were not found to inhibit the reaction.

  12. Pyrrole-2-Carboxylic Acid as a Ligand for the Cu-Catalyzed Reactions of Primary Anilines with Aryl Halides

    PubMed Central

    Altman, Ryan A.; Anderson, Kevin W.; Buchwald, Stephen L.

    2008-01-01

    Pyrrole 2-carboxylic acid (L5) was found to be an effective ligand for the Cu-catalyzed mono-arylation of anilines with aryl iodides and bromides. Under the reported conditions (10% CuI/20% L5/DMSO/K3PO4/80–100 °C/20–24 h), a variety of useful functional groups were tolerated, and moderate to good yields of the diaryl amine products were obtained. PMID:18543973

  13. Wet Nano-Bonding of Silica-to-Si and Silica-to-Silica below 200^o C by H2O catalysis and a 2-D precursor phase: TMAFM, Hydroaffinity and Surface Free Energy Analysis

    NASA Astrophysics Data System (ADS)

    Bennett-Kennett, Ross; Whaley, Shawn; Herbots, Nicole; Watson, Clarizza; Culbertson, Robert; Rez, Peter; Murphy, Ashlee; Farmer, Sam; Sell, David; Hughes, Brett; Acharya, Ajju

    2012-10-01

    Hydroxylated silica about 2.1 ± 0.1 nm thick are nucleated on OH(1x1)Si(100) as precursor phase to cross-bond directly silica to Si, and silica to silica using planarization via extended atomic terraces, T<= 200^oC, an H2O/O2 ambient, and p >= 1 atm. This method,``Wet Nano-Bonding,#039;' relies on the Herbots-Atluri process [1] to nucleate precursor phases to bond via direct hydroxylated silica molecular cross-bridges two surfaces brought into contact at the nano-scale. Ordered Si2(OH)4 β-cristobalite precursor phases exhibit atomic terraces that extend to 20 nm, in contrast to the 2 nm width in ``as received'' Si(100) wafers. β-cristobalite nano-phases can desorb at low temperatures (T / ˜ 200^o C) [3]. These ordered oxides can promote the growth of flatter, smoother, better controlled oxides at low temperatures in ambient air. When put into close contact at T>= 200^o C with oxygen-deficient phases of SiOx used in microelectronics, they can consistently nucleate a cross-bridging between the two substrates, or ``nano-bonding'' inter-phase [4] between various combinations Si and silica provided an H2O/O2 ambient catalyzes low temperature oxidation and nano-contacting is achieved via pressurization in the nano-bonding chamber.

  14. Why platinum catalysts involving ligands with large bite angle are so efficient in the allylation of amines: design of a highly active catalyst and comprehensive experimental and DFT study.

    PubMed

    Mora, Guilhem; Piechaczyk, Olivier; Houdard, Romaric; Mézailles, Nicolas; Le Goff, Xavier-Frederic; le Floch, Pascal

    2008-01-01

    The platinum-catalyzed allylation of amines with allyl alcohols was studied experimentally and theoretically. The complexes [Pt(eta(3)-allyl)(dppe)]OTf (2) and [Pt(eta(3)-allyl)(DPP-Xantphos)]PF(6) (5) were synthesized and structurally characterized, and their reactivity toward amines was explored. The bicyclic aminopropyl complex [Pt(CH(2)CH(2)CH(2)NHBn-kappa-C,N)(dppe)]OTf (3) was obtained from the reaction of complex 2 with an excess of benzylamine, and this complex was shown to be a deactivated form of catalyst 2. On the other hand, reaction of complex 5 with benzylamine and allyl alcohol led to formation of the 16-VE platinum(0) complex [Pt(eta(2)-C(3)H(5)OH)(DPP-Xantphos)] (7), which was structurally characterized and appears to be a catalytic intermediate. A DFT study showed that the mechanism of the platinum-catalyzed allylation of amines with allyl alcohols differs from the palladium-catalyzed process, since it involves an associative ligand-exchange step involving formation of a tetracoordinate 18-VE complex. This DFT study also revealed that ligands with large bite angles disfavor the formation of platinum hydride complexes and therefore the formation of a bicyclic aminopropyl complex, which is a thermodynamic sink. Finally, a combination of 5 and a proton source was shown to efficiently catalyze the allylation of a broad variety of amines with allyl alcohols under mild conditions.

  15. N-nitrosamines formation from secondary amines by nitrogen fixation on the surface of activated carbon.

    PubMed

    Padhye, Lokesh P; Hertzberg, Benjamin; Yushin, Gleb; Huang, Ching-Hua

    2011-10-01

    Our previous study demonstrated that many commercial activated carbon (AC) particles may catalyze transformation of secondary amines to yield trace levels of N-nitrosamines under ambient aerobic conditions. Because of the widespread usage of AC materials in numerous analytical and environmental applications, it is imperative to understand the reaction mechanism responsible for formation of nitrosamine on the surface of ACs to minimize their occurrence in water treatment systems and during analytical methods employing ACs. The study results show that the AC-catalyzed nitrosamine formation requires both atmospheric oxygen and nitrogen. AC's surface reactive sites react with molecular oxygen to form reactive oxygen species (ROS), which facilitate fixation of molecular nitrogen on the carbon surfaces to generate reactive nitrogen species (RNS) likely nitrous oxide and hydroxylamine that can react with adsorbed amines to form nitrosamines. AC's properties play a crucial role as more nitrosamine formation is associated with carbon surfaces with higher surface area, more surface defects, reduced surface properties, higher O(2) uptake capacity, and higher carbonyl group content. This study is a first of its kind on the nitrosamine formation mechanism involving nitrogen fixation on AC surfaces, and the information will be useful for minimization of nitrosamines in AC-based processes.

  16. Adsorption at cell surface and cellular uptake of silica nanoparticles with different surface chemical functionalizations: impact on cytotoxicity

    NASA Astrophysics Data System (ADS)

    Kurtz-Chalot, A.; Klein, J. P.; Pourchez, J.; Boudard, D.; Bin, V.; Alcantara, G. B.; Martini, M.; Cottier, M.; Forest, V.

    2014-11-01

    Silica nanoparticles are particularly interesting for medical applications because of the high inertness and chemical stability of silica material. However, at the nanoscale their innocuousness must be carefully verified before clinical use. The aim of this study was to investigate the in vitro biological toxicity of silica nanoparticles depending on their surface chemical functionalization. To that purpose, three kinds of 50 nm fluorescent silica-based nanoparticles were synthesized: (1) sterically stabilized silica nanoparticles coated with neutral polyethylene glycol molecules, (2) positively charged silica nanoparticles coated with amine groups, and (3) negatively charged silica nanoparticles coated with carboxylic acid groups. RAW 264.7 murine macrophages were incubated for 20 h with each kind of nanoparticles. Their cellular uptake and adsorption at the cell membrane were assessed by a fluorimetric assay, and cellular responses were evaluated in terms of cytotoxicity, pro-inflammatory factor production, and oxidative stress. Results showed that the highly positively charged nanoparticle were the most adsorbed at cell surface and triggered more cytotoxicity than other nanoparticle types. To conclude, this study clearly demonstrated that silica nanoparticles surface functionalization represents a key parameter in their cellular uptake and biological toxicity.

  17. Simple Fabrication of Mesoporous Silica with Remarkable High Temperature Stability at Neutral pH and Ambient Conditions from TEOS

    NASA Astrophysics Data System (ADS)

    Hess, David; Vippagunta, Radha; Watkins, James

    2007-03-01

    Traditional silica synthesis processes can yield well ordered materials, but the synthesis conditions also lead to incomplete condensation of the silica network, which results in significant structural contraction upon calcination and limited thermal, hydrothermal and mechanical stability. Here we report the synthesis that, surprisingly, yields nearly complete condensation of the silica network (virtually all Q4 linkages) using cysteamine as the catalyst and polyoxyethylene surfactants as the structure directing agents in buffered solution at neutral pH and ambient temperature. Recently, small molecule bifunctional amines, including cysteamine, were evaluated by Morse and co-workers and found to produce silica from TEOS(JACS 2005, 127, 35). Our work combines the cysteamine catalyst system with structure-directing block copolymer surfactants at neutral pH and ambient temperature to produce mesoporous silica. The addition of tetraethyl orthosilicate (TEOS) to a solution of containing cysteamine, citrate buffer (pH 7.2) and 5wt Brij amphiphilic block copolymer (polyethylene oxide-polyethylene) yields mesoporous silica. The resulting mesoporous silica powder was analyzed using XRD, TGA, FTIR, TEM, and NMR. The materials were found to exhibit stability under extreme temperature calcinations (up to 800 C) in the presence of water. SAXS shows that 1.0 shrinkage upon calcination up to 800C. 29Si NMR analysis indicates a fully condensed silica network, Q4 linkages, in accordance with this observation.

  18. DNA-Catalyzed Amide Hydrolysis

    PubMed Central

    Zhou, Cong; Avins, Joshua L.; Klauser, Paul C.; Brandsen, Benjamin M.; Lee, Yujeong; Silverman, Scott K.

    2016-01-01

    DNA catalysts (deoxyribozymes) for a variety of reactions have been identified by in vitro selection. However, for certain reactions this identification has not been achieved. One important example is DNA-catalyzed amide hydrolysis, for which a previous selection experiment instead led to DNA-catalyzed DNA phosphodiester hydrolysis. Subsequent efforts in which the selection strategy deliberately avoided phosphodiester hydrolysis led to DNA-catalyzed ester and aromatic amide hydrolysis, but aliphatic amide hydrolysis has been elusive. In the present study, we show that including modified nucleotides that bear protein-like functional groups (any one of primary amino, carboxyl, or primary hydroxyl) enables identification of amide-hydrolyzing deoxyribozymes. In one case, the same deoxyribozyme sequence without the modifications still retains substantial catalytic activity. Overall, these findings establish the utility of introducing protein-like functional groups into deoxyribozymes for identifying new catalytic function. The results also suggest the longer-term feasibility of deoxyribozymes as artificial proteases. PMID:26854515

  19. Accurate determination of aldehydes in amine catalysts or amines by 2,4-dinitrophenylhydrazine derivatization.

    PubMed

    Barman, Bhajendra N

    2014-01-31

    Carbonyl compounds, specifically aldehydes, present in amine catalysts or amines are determined by reversed-phase liquid chromatography using ultraviolet detection of their corresponding 2,4-dinitrophenylhydrazones. The primary focus has been to establish optimum conditions for determining aldehydes accurately because these add exposure concerns when the amine catalysts are used to manufacture polyurethane products. Concentrations of aldehydes determined by this method are found to vary with the pH of the aqueous amine solution and the derivatization time, the latter being problematic when the derivatization reaction proceeds slowly and not to completion in neutral and basic media. Accurate determination of aldehydes in amines through derivatization can be carried out at an effective solution pH of about 2 and with derivatization time of 20min. Hydrochloric acid has been used for neutralization of an amine. For complete derivatization, it is essential to protonate all nitrogen atoms in the amine. An approach for the determination of an adequate amount of acid needed for complete derivatization has been described. Several 0.2M buffer solutions varying in pH from 4 to 8 have also been used to make amine solutions for carrying out derivatization of aldehydes. These solutions have effective pHs of 10 or higher and provide much lower aldehyde concentrations compared to their true values. Mechanisms for the formation of 2,4-dinitrophenylhydrazones in both acidic and basic media are discussed.

  20. Selective Radical Amination of Aldehydic C(sp2)–H Bonds with Fluoroaryl Azides via Co(II)-Based Metalloradical Catalysis: Synthesis of N-Fluoroaryl Amides from Aldehydes under Neutral and Nonoxidative Conditions

    PubMed Central

    Jin, Li-Mei; Lu, Hongjian; Cui, Yuan; Lizardi, Christopher L.; Arzua, Thiago N.; Wojtas, Lukasz; Cui, Xin

    2014-01-01

    The Co(II) complex of the D2h-symmetric amidoporphyrin 3,5-DitBu-IbuPhyrin, [Co(P1)], has proven to be an effective metalloradical catalyst for intermolecular amination of C(sp2)–H bonds of aldehydes with fluoroaryl azides. The [Co(P1)]-catalyzed process can employ aldehydes as the limiting reagents and operate under neutral and non-oxidative conditions, generating nitrogen gas as the only byproduct. The metalloradical aldehydic C–H amination is suitable for different combinations of aldehydes and fluoroaryl azides, producing the corresponding N-fluoroaryl amides in good to excellent yields. A series of mechanistic studies support a stepwise radical mechanism for the Co(II)-catalyzed intermolecular C–H amination. PMID:25071929

  1. Subtilisin-catalyzed resolution of N-acyl arylsulfinamides.

    PubMed

    Savile, Christopher K; Magloire, Vladimir P; Kazlauskas, Romas J

    2005-02-23

    We report the first biocatalytic route to sulfinamides (R-S(O)-NH2), whose sulfur stereocenter makes them important chiral auxiliaries for the asymmetric synthesis of amines. Subtilisin E did not catalyze hydrolysis of N-acetyl or N-butanoyl arylsulfinamides, but did catalyze a highly enantioselective (E > 150 favoring the (R)-enantiomer) hydrolysis of N-chloroacetyl and N-dihydrocinnamoyl arylsulfinamides. Gram-scale resolutions using subtilisin E overexpressed in Bacillus subtilis yielded, after recrystallization, three synthetically useful auxiliaries: (R)-p-toluenesulfinamide (42% yield, 95% ee), (R)-p-chlorobenzenesulfinamide (30% yield, 97% ee), and (R)-2,4,6-trimethylbenzenesulfinamide (30% yield, 99% ee). Molecular modeling suggests that the N-chloroacetyl and N-dihydrocinnamoyl groups mimic a phenylalanine moiety and thus bind the sulfinamide to the active site. Molecular modeling further suggests that enantioselectivity stems from a favorable hydrophobic interaction between the aryl group of the fast-reacting (R)-arylsulfinamide and the S1' leaving group pocket in subtilisin E.

  2. Curcumin loaded mesoporous silica: an effective drug delivery system for cancer treatment.

    PubMed

    Kotcherlakota, Rajesh; Barui, Ayan Kumar; Prashar, Sanjiv; Fajardo, Mariano; Briones, David; Rodríguez-Diéguez, Antonio; Patra, Chitta Ranjan; Gómez-Ruiz, Santiago

    2016-03-01

    In the present study, we report the delivery of anti-cancer drug curcumin to cancer cells using mesoporous silica materials. A series of mesoporous silica material based drug delivery systems (S2, S4 and S6) were first designed and developed through the amine functionalization of KIT-6, MSU-2 and MCM-41 followed by the loading of curcumin. The curcumin loaded materials were characterized with several physico-chemical techniques and thoroughly screened on cancer cells to evaluate their in vitro drug delivery efficacy. All the curcumin loaded silica materials exhibited higher cellular uptake and inhibition of cancer cell viability compared to pristine curcumin. The effective internalization of curcumin in cancer cells through the mesoporous silica materials initiated the generation of intracellular reactive oxygen species and the down regulation of poly ADP ribose polymerase (PARP) enzyme levels compared to free curcumin leading to the activation of apoptosis. This study shows that the anti-cancer activity of curcumin can be potentiated by loading onto mesoporous silica materials. Therefore, we strongly believe that mesoporous silica based curcumin loaded drug delivery systems may have future potential applications for the treatment of cancers.

  3. Di-Isocyanate Crosslinked Aerogels with 1, 6-Bis (Trimethoxysilyl) Hexane Incorporated in Silica Backbone

    NASA Technical Reports Server (NTRS)

    Vivod, Stephanie L.; Meador, Mary Ann B.; Nguyen, Baochau N.; Quade, Derek; Randall, Jason; Perry, Renee

    2008-01-01

    Silica aerogels are desirable materials for many applications that take advantage of their light weight and low thermal conductivity. Addition of a conformal polymer coating which bonds with the amine decorated surface of the silica network improves the strength of the aerogels by as much as 200 times. Even with vast improvement in strength they still tend to undergo brittle failure due to the rigid silica backbone. We hope to increase the flexibility and elastic recovery of the silica based aerogel by altering the silica back-bone by incorporation of more flexible hexane links. To this end, we investigated the use of 1,6-bis(trimethoxysilyl)hexane (BTMSH), a polysilsesquioxane precursor3, as an additional co-reactant to prepare silica gels which were subsequently cross-linked with di-isocyanate. Previously, this approach of adding flexibility by BTMSH incorporation was demonstrated with styrene cross-linked aerogels. In our study, we varied silane concentration, mol % of silicon from BTMSH and di-isocyanate concentration by weight percent to attempt to optimize both the flexibility and the strength of the aerogels.

  4. Primary, secondary, and tertiary amines for CO2 capture: designing for mesoporous CO2 adsorbents.

    PubMed

    Ko, Young Gun; Shin, Seung Su; Choi, Ung Su

    2011-09-15

    CO(2) emissions, from fossil-fuel-burning power plants, the breathing, etc., influence the global worming on large scale and the man's work efficiency on small scale. The reversible capture of CO(2) is a prominent feature of CO(2) organic-inorganic hybrid adsorbent to sequester CO(2). Herein, (3-aminopropyl) trimethoxysilane (APTMS), [3-(methylamino)propyl] trimethoxysilane (MAPTMS), and [3-(diethylamino) propyl] trimethoxysilane (DEAPTMS) are immobilized on highly ordered mesoporous silicas (SBA-15) to catch CO(2) as primary, secondary, and tertiary aminosilica adsorbents. X-ray photoelectron spectroscopy was used to analyze the immobilized APTMS, MAPTMS, and DEAPTMS on the SBA-15. We report an interesting discovery that the CO(2) adsorption and desorption on the adsorbent depend on the amine type of the aminosilica adsorbent. The adsorbed CO(2) was easily desorbed from the adsorbent with the low energy consumption in the order of tertiary, secondary, and primary amino-adsorbents while the adsorption amount and the bonding-affinity increased in the reverse order. The effectiveness of amino-functionalized (1(o), 2(o), and 3(o) amines) SBA-15s as a CO(2) capturing agent was investigated in terms of adsorption capacity, adsorption-desorption kinetics, and thermodynamics. This work demonstrates apt amine types to catch CO(2) and regenerate the adsorbent, which may open new avenues to designing "CO(2) basket".

  5. Novel palladium complex-catalyzed reaction of magnesium amides with allylic electrophiles

    SciTech Connect

    Dzhemilev, U.M.; Ibragimov, A.G.; Minsker, D.L.; Muslukhov, R.R.

    1987-08-20

    In order to develop an efficient method for the synthesis of higher order unsaturated tertiary amines, and also to explore a new method for the formation of C-N bonds, they have investigated the transition metal complex-catalyzed reaction of magnesium amides with electrophiles; the electrophiles selected for study included allyl ethers and esters, as well as sulfones, sulfides and quaternized allylamines. The effects of the nature and structure of the catalyst components, as well as of the reaction conditions, on product yield were examined in the case of the reaction of diethyl (bromomagnesium)amine with diallyl ether, and revealed that the highest yield of diethylallyl-amine (I) was achieved using Pd(acac)/sub 2/ (3-5 mole %) and Ph/sub 3/P (1:2) as catalyst in THF solution at 50/sup 0/C for 5 h. Other transition metal (Ni, Fe, Zr, Ti, Cu) compounds were also examined as catalysts, but the yield of (I) did not exceed 15% with these compounds. Bimetallic catalysts based on Zr (Cp/sub 2/ZrCl, Py/sub 2/ZrCl/sub 6/, (RO)/sub 4/Zr) and Ni (Ni(acac)/sub 2/ and NiCl/sub 2/) were successful in forming (I) from diethyl (bromomagnesium)amine and diallyl ether in 60% yield.

  6. Surface properties and water treatment capacity of surface engineered silica coated with 3-(2-aminoethyl) aminopropyltrimethoxysilane

    NASA Astrophysics Data System (ADS)

    Majewski, Peter; Keegan, Alexandra

    2012-01-01

    This study's focus was on the water-based, one-pot preparation and characterisation of silica particles coated with 3-(2-aminoethyl)aminopropyltrimethoxysilane (Diamo) and the efficiency of the material in removing the pathogens Escherichia coli, Pseudomonas aeruginosa, Mycobacterium immunogenum, Vibrio cholerae, poliovirus, and Cryptosporidium parvum. The water-based processing resulted in Diamo coated silica particles with significantly increased positive surface charge as determined by zeta potential measurements. In addition, X-ray photoelectron spectrometry of pure and Diamo coated silica confirmed the presence of Diamo on the surface of the particles. Thermogravimetric measurements and chemical analysis of the silica indicated a surface concentration of amine groups of about 1 mmol/gsilica. Water treatment tests with the pathogens showed that a dose of about 10 g appeared to be sufficient to remove pathogens from pure water samples which were spiked with pathogen concentrations between about 102 and 104 cfu/mL.

  7. Infrared method for in situ studies of polymer/surfactant adsorption on silica powders from aqueous solution.

    PubMed

    Jiang, Cuihong; Li, Haiyan; Tripp, Carl P

    2003-11-01

    This article presents a general infrared spectroscopic method that enables the monitoring of the adsorption of surfactants and polyelectrolytes on high surface area silica particles from aqueous solution. The method is based on the use of a ZnSe internal reflection element (IRE) coated with a layer of titania particles. The titania surface is the converted to silica using atomic layer deposition with sequential addition of an amine catalyst, gaseous SiCl4, and water vapor. A minimum of three cycles is needed to produce a surface that mimics silica, as evidenced by the reaction of hexamethyldisilazane and zeta potential measurements. It is shown that the silicacoated titania particles on the ZnSe crystals are stable to flowing aqueous solutions below pH = 8 and can be used to study the dynamics of polymer/surfactant adsorption on silica.

  8. CO2 capture from the atmosphere and simultaneous concentration using zeolites and amine-grafted SBA-15.

    PubMed

    Stuckert, Nicholas R; Yang, Ralph T

    2011-12-01

    CO(2) capture from the atmosphere and concentration by cyclic adsorption-desorption processes are studied for the first time. New high microporosity materials, zeolite types Li-LSX and K-LSX, are compared to zeolite NaX and amine-grafted SBA-15 with low amine content. Breakthrough performance showed low silica type X (LSX) to have the most promise for application in dry conditions and capable of high space velocities of at least 63,000 h(-1), with minimal spreading of the CO(2) breakthrough curve. Amine-grafted silica was the only adsorbent able to operate in wet conditions, but at a lower space velocity of 1500 h(-1), due to slower uptake rates. The results illustrate that the uptake rate is as important as the equilibrium adsorbed amount in determining the cyclic process performance. Li-LSX was found to have double the capacity of zeolite NaX at atmospheric conditions, also higher than all other reported zeolites. It is further demonstrated that by using a combined temperature and vacuum swing cycle, the CO(2) concentration in the desorption product is >90% for all adsorbents in pellet form. This is the first report of such high CO(2) product concentrations from a single cycle, using atmospheric air.

  9. Enhanced adsorption of quaternary amine using modified activated carbon.

    PubMed

    Prahas, Devarly; Wang, M J; Ismadji, Suryadi; Liu, J C

    2014-01-01

    This study examined different methodologies to modify activated carbon (AC) for the removal of quaternary amine, tetramethylammonium hydroxide (TMAH), from water. Commercial carbon (WAC) was treated by nitric acid oxidation (NA-WAC), silica impregnation (SM-WAC0.5), and oxygen plasma (P10-WAC), and their characteristics and adsorption capacity were compared. The Langmuir model fitted the equilibrium adsorption data well under different pH. The maximum adsorption capacity of WAC was 27.77 mg/g, while those of NA-WAC, SM-WAC 0.5, and P10-WAC were 37.46, 32.83 and 29.03 mg/g, respectively. Nitric acid oxidation was the most effective method for enhancing the adsorption capacity of TMAH. Higher pH was favorable for TMAH adsorption. Desorption study revealed that NA-WAC had no considerable reduction in performance even after five cycles of regeneration by 0.1 N hydrochloric acid. It was proposed that electrostatic interaction was the main mechanism of TMAH adsorption on activated carbon.

  10. Multistep divergent synthesis of benzimidazole linked benzoxazole/benzothiazole via copper catalyzed domino annulation.

    PubMed

    Liao, Jen-Yu; Selvaraju, Manikandan; Chen, Chih-Hau; Sun, Chung-Ming

    2013-04-21

    An efficient, facile synthesis of structurally diverse benzimidazole integrated benzoxazole and benzothiazoles has been developed. In a multi-step synthetic sequence, 4-fluoro-3-nitrobenzoic acid was converted into benzimidazole bis-heterocycles, via the intermediacy of benzimidazole linked ortho-chloro amines. The amphiphilic reactivity of this intermediate was designed to achieve the title compounds by the reaction of various acid chlorides and isothiocyanates in a single step through the in situ formation of ortho-chloro anilides and thioureas under microwave irradiation. A versatile one pot domino annulation reaction was developed to involve the reaction of benzimidazole linked ortho-chloro amines with acid chlorides and isothiocyanates. The initial acylation and urea formation followed by copper catalyzed intramolecular C-O and C-S cross coupling reactions furnished the angularly oriented bis-heterocycles which bear a close resemblance to the streptomyces antibiotic UK-1.

  11. CCN activity of aliphatic amine secondary aerosol

    NASA Astrophysics Data System (ADS)

    Tang, X.; Price, D.; Praske, E.; Vu, D.; Purvis-Roberts, K.; Silva, P. J.; Cocker, D. R., III; Asa-Awuku, A.

    2014-01-01

    Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g. hydroxyl radical and nitrate radical). The particle composition can contain both secondary organic aerosol (SOA) and inorganic salts. The fraction of organic to inorganic materials in the particulate phase influences aerosol hygroscopicity and cloud condensation nuclei (CCN) activity. SOA formed from trimethylamine (TMA) and butylamine (BA) reactions with hydroxyl radical (OH) is composed of organic material of low hygroscopicity (single hygroscopicity parameter, κ ≤ 0.25). Secondary aerosol formed from the tertiary aliphatic amine (TMA) with N2O5 (source of nitrate radical, NO3), contains less volatile compounds than the primary aliphatic amine (BA) aerosol. TMA + N2O5 form semi-volatile organics in low RH conditions that have κ ~ 0.20, indicative of slightly soluble organic material. As RH increases, several inorganic amine salts are formed as a result of acid-base reactions. The CCN activity of the humid TMA-N2O5 aerosol obeys Zdanovskii, Stokes, and Robinson (ZSR) ideal mixing rules. Higher CCN activity (κ > 0.3) was also observed for humid BA+N2O5 aerosols compared with dry aerosol (κ ~ 0.2), as a result of the formation of inorganic salts such as NH4NO3 and butylamine nitrate (C4H11N · HNO3). Compared with TMA, BA+N2O5 reactions produce more volatile aerosols. The BA+N2O5 aerosol products under humid experiments were found to be very sensitive to the temperature within the stream-wise continuous flow thermal gradient CCN counter. The CCN counter, when set above a 21 °C temperature difference, evaporates BA+N2O5 aerosol formed at RH ≥ 30%; κ ranges from 0.4 to 0.7 and is dependent on the instrument supersaturation (ss) settings. The aerosol behaves non-ideally, hence simple ZSR rules cannot be applied to the CCN results from the primary aliphatic amine system. Overall, aliphatic amine aerosol systems κ ranges from 0.2 < κ < 0.7. This work indicates that

  12. Kinetic study on Michael-type reactions of β-nitrostyrenes with cyclic secondary amines in acetonitrile: transition-state structures and reaction mechanism deduced from negative enthalpy of activation and analyses of LFERs.

    PubMed

    Um, Ik-Hwan; Kang, Ji-Sun; Park, Jong-Yoon

    2013-06-07

    A kinetic study is reported for the Michael-type reactions of X-substituted β-nitrostyrenes (1a-j) with a series of cyclic secondary amines in MeCN. The plots of pseudo-first-order rate constant k(obsd) vs [amine] curve upward, indicating that the reactions proceed through catalyzed and uncatalyzed routes. The dissection of k(obsd) into Kk2 and Kk3 (i.e., the rate constants for the uncatalyzed and catalyzed routes, respectively) revealed that Kk3 is much larger than Kk2, implying that the reactions proceed mainly through the catalyzed route when [amine] > 0.01 M. Strikingly, the reactivity of β-nitrostyrene (1g) toward piperidine decreases as the reaction temperature increases. Consequently, a negative enthalpy of activation is obtained, indicating that the reaction proceeds through a relatively stable intermediate. The Brønsted-type plots for the reactions of 1g are linear with β(nuc) = 0.51 and 0.61, and the Hammett plots for the reactions of 1a-j are also linear with ρX = 0.84 and 2.10 for the uncatalyzed and catalyzed routes, respectively. The reactions are concluded to proceed through six-membered cyclic transition states for both the catalyzed and uncatalyzed routes. The effects of the substituent X on reactivity and factors influencing β(nuc) and ρX obtained in this study are discussed.

  13. Structure and properties of polybenzimidazole/silica nanocomposite electrolyte membrane: influence of organic/inorganic interface.

    PubMed

    Singha, Shuvra; Jana, Tushar

    2014-12-10

    Although increased number of reports in recent years on proton exchange membrane (PEM) developed from nanocomposites of polybenzimidazole (PBI) with inorganic fillers brought hope to end the saga of contradiction between proton conductivity and variety of stabilities, such as mechanical, thermal,chemical, etc.; it still remains a prime challenge to develop a highly conducting PEM with superior aforementioned stabilities. In fact the very limited understanding of the interactions especially interfacial interaction between PBI and inorganic filler leads to confusion over the choice of inorganic filler type and their surface functionalities. Taking clue from our earlier study based on poly(4,4'-diphenylether-5,5'-bibenzimidazole) (OPBI)/silica nanocomposites, where silica nanoparticles modified with short chain amine showed interfacial interaction-dependent properties, in this work we explored the possibility of enhanced interfacial interaction and control over the interface by optimizing the chemistry of the silica surface. We functionalized the surface of silica nanoparticles with a longer aliphatic chain having multiple amine groups (named as long chain amine modified silica and abbreviated as LAMS). FTIR and (13)C solid-state NMR provided proof of hydrogen bonding interactions between the amine groups of modifier and those of OPBI. LAMS nanoparticles yielded a more distinguished self-assembly extending all over the OPBI matrix with increasing concentrations. The crystalline nature of these self-assembled clusters was probed by wide-angle X-ray diffraction (WAXD) studies and the morphological features were captured by transmission electron microscope (TEM). We demonstrated the changes in storage modulus and glass transition temperature (Tg) of the membranes, the fundamental parameters that are more sensitive to interfacial structure using temperature dependent dynamic mechanical analysis (DMA). All the nanocomposite membranes displayed enhanced mechanical, thermal

  14. The world ocean silica cycle.

    PubMed

    Tréguer, Paul J; De La Rocha, Christina L

    2013-01-01

    Over the past few decades, we have realized that the silica cycle is strongly intertwined with other major biogeochemical cycles, like those of carbon and nitrogen, and as such is intimately related to marine primary production, the efficiency of carbon export to the deep sea, and the inventory of carbon dioxide in the atmosphere. For nearly 20 years, the marine silica budget compiled by Tréguer et al. (1995) , with its exploration of reservoirs, processes, sources, and sinks in the silica cycle, has provided context and information fundamental to study of the silica cycle. Today, the budget needs revisiting to incorporate advances that have notably changed estimates of river and groundwater inputs to the ocean of dissolved silicon and easily dissolvable amorphous silica, inputs from the dissolution of terrestrial lithogenic silica in ocean margin sediments, reverse weathering removal fluxes, and outputs of biogenic silica (especially on ocean margins and in the form of nondiatomaceous biogenic silica). The resulting budget recognizes significantly higher input and output fluxes and notes that the recycling of silicon occurs mostly at the sediment-water interface and not during the sinking of silica particles through deep waters.

  15. Allyl-silica Hybrid Monoliths For Chromatographic Application

    NASA Astrophysics Data System (ADS)

    Guo, Wenjuan

    Column technology continues to be the most investigated topics in the separation world, since the column is the place where the chromatographic separation happens, making it the heart of the separation system. Allyl-silica hybrid monolithic material has been exploited as support material and potential stationary phases for liquid chromatography; the stationary phase anchored to the silica surface by Si-C bond, which is more pH stable than traditional stationary phase. First, nuclear magnetic resonance spectroscopy has been used to study the sol in the synthesis of allyl-silica hybrid monoliths. Allyl-trimethoxysilane (allyl-TrMOS), dimethyldimethoxysilane (DMDMOS) and tetramethoxysilane (TMOS) have been served as co-precursors in the sol-gel synthesis of organo-silica hybrid monolithic columns for liquid chromatography (LC). 29Si nuclear magnetic resonance (NMR) and 1H NMR spectroscopy were employed to monitor reaction profiles for the acid-catalyzed hydrolysis and initial condensation reactions of the individual precursor and the hybrid system. 29Si-NMR has also been used to identify different silane species formed during the reactions. The overall hydrolysis rate has been found to follow the trend DMDMOS > allyl-TrMOS > TMOS, if each precursor is reacted individually (homo-polymerization). Precursors show different hydrolysis rate when reacted together in the hybrid system than they are reacted individually. Cross-condensation products of TMOS and DMDMOS (QD) arise about 10 minutes of initiation of the reaction. The allyl-silica monolithic columns for capillary liquid chromatography can only be prepared in capillaries with 50 im internal diameter with acceptable performance. One of the most prominent problems related to the synthesis of silica monolithic structures is the volume shrinkage. The synthesis of allylfunctionalized silica hybrid monolithic structures has been studied in an attempt to reduce the volume shrinkage during aging, drying and heat treatment

  16. Iodine-Catalyzed Polysaccharide Esterification

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A review is provided of the recent reports to use iodine-catalyzed esterification reaction to produce esters from polysaccharides. The process entails reaction of the polysaccharide with an acid anhydride in the presence of a catalytic level of iodine, and in the absence of additional solvents. T...

  17. Performance of catalyzed hydrazine in field applications

    SciTech Connect

    Allgood, T.B.

    1987-01-01

    The performance of newly developed oxygen scavengers for boilers is often compared to sulfite and hydrazine. Catalyzed hydrazine out-performs hydrazine and might be preferred when catalyzed sulfite cannot be used. Data from a Midwest Utility confirms that, under field conditions, catalyzed hydrazine out-performance hydrazine and carbohydrazine when feedwater oxygen and iron levels were critical. Catalyzed hydrazine might be preferred when high performance and economics are the primary concerns.

  18. Correlation fluorescence method of amine detection

    NASA Astrophysics Data System (ADS)

    Myslitsky, Valentin F.; Tkachuk, Svetlana S.; Rudeichuk, Volodimir M.; Strinadko, Miroslav T.; Slyotov, Mikhail M.; Strinadko, Marina M.

    1997-12-01

    The amines fluorescence spectra stimulated by UV laser radiation are investigated in this paper. The fluorescence is stimulated by the coherent laser beam with the wavelength 0.337 micrometers . At the sufficient energy of laser stimulation the narrow peaks of the fluorescence spectra are detected besides the wide maximum. The relationship between the fluorescence intensity and the concentration of amines solutions are investigated. The fluorescence intensity temporal dependence on wavelength 0.363 micrometers of the norepinephrine solution preliminarily radiated by UV laser with wavelength 0.337 micrometers was found. The computer stimulated and experimental investigations of adrenaline and norepinephrine mixtures fluorescence spectra were done. The correlation fluorescent method of amines detection is proposed.

  19. Total synthesis of palau'amine

    PubMed Central

    Namba, Kosuke; Takeuchi, Kohei; Kaihara, Yukari; Oda, Masataka; Nakayama, Akira; Nakayama, Atsushi; Yoshida, Masahiro; Tanino, Keiji

    2015-01-01

    Palau'amine has received a great deal of attention in the past two decades as an attractive synthetic target by virtue of its intriguing molecular architecture and significant immunosuppressive activity. Here we report the total synthesis of palau'amine characterized by the construction of an ABDE tetracyclic ring core including a trans-bicylo[3.3.0]octane skeleton at a middle stage of total synthesis. The ABDE tetracyclic ring core is constructed by a cascade reaction of a cleavage of the N–N bond, including simultaneous formation of imine, the addition of amide anion to the resulting imine (D-ring formation) and the condensation of pyrrole with methyl ester (B-ring formation) in a single step. The synthetic palau'amine is confirmed to exhibit excellent immunosuppressive activity. The present synthetic route has the potential to help elucidate a pharmacophore as well as the mechanistic details of immunosuppressive activity. PMID:26530707

  20. Biogenic amines and microbial quality of sprouts.

    PubMed

    Simon-Sarkadi, L; Holzapfel, W H

    1995-04-01

    Changes in the biogenic amine content relative to microbial activities in mung bean, lentil and radish sprouts were investigated in prepacked and "home-grown" products. Biogenic amines were determined by ion-exchange chromatography. The major groups of micro-organisms were enumerated by aerobic plate count procedures, using universal and selective media. Putrescine, cadaverine, spermidine, agmatine and spermine were detected in different concentrations, depending on the type of sprouts. In prepacked retail products the total biogenic amine content was higher than in home-grown samples (mung bean 106 micrograms/g compared to 87 micrograms/g; lentil 316 micrograms/g compared to 181 micrograms/g; radish 1486 micrograms/g compared to 252 micrograms/g). It is concluded that sprouting time and storage conditions play a major part in the hygienic quality of legume sprouts.

  1. Synthesis of Chiral Aminocyclopropanes by Rare-Earth-Metal-Catalyzed Cyclopropene Hydroamination.

    PubMed

    Teng, Huai-Long; Luo, Yong; Wang, Baoli; Zhang, Liang; Nishiura, Masayoshi; Hou, Zhaomin

    2016-12-05

    The search for efficient and selective routes for the synthesis of chiral aminocyclopropane derivatives is of great interest and importance as these structures are important components of biologically active natural products and pharmaceuticals. We herein report the enantioselective intermolecular hydroamination of substituted cyclopropenes with various amines catalyzed by chiral half-sandwich rare-earth-metal complexes. This method constitutes a 100 % atom-efficient route for the synthesis of a variety of chiral α-aminocyclopropane derivatives in high yields (up to 96 %) and excellent stereoselectivity (up to >20:1 d.r. and 99 % ee) under mild reaction conditions (25 °C).

  2. L-proline-catalyzed synthesis of highly functionalized multisubstituted 1,4-dihydropyridines.

    PubMed

    Jiang, Huanfeng; Mai, Ronghuan; Cao, Hua; Zhu, Qiuhua; Liu, Xiaohang

    2009-12-07

    Highly functionalized multisubstituted 1,4-dihydropyridines 5 have been concisely synthesized in moderate to good yields via L-proline-catalyzed one-pot multicomponent reactions (MCRs) of alkynoates or alkynones 1, amines 2, beta-dicarbonyl compounds 3 and aldehydes 4 under mild conditions. The MCR process involves hydroamination/Knoevenagel condensation/Michael-type addition/intramolecular cyclization processes and leads to the formation of 1,4-dihydropyridines 5. The molecular structure of 5ckaa was confirmed by single-crystal X-ray diffraction. This method is energy saving and environmentally friendly, providing easy access to diverse multisubstituted polyfunctional 1,4-dihydropyridines.

  3. Isocyanate Cross-Linked Silica: Structurally Strong Aerogels

    NASA Technical Reports Server (NTRS)

    Leventis, Nicholas; Sotiriou-Leventis, Chariklia; Zhang, Guo-Hui; Rawashdeh, Abdel-Monem M.

    2002-01-01

    Molecular-level synergism between the silica nanoparticles of pre-formed monoliths and molecular cross-linkers inverts the relative host-guest roles in glass-polymer composites, leading to new strong low-density materials. Attempts to load gels with variable amounts of polyurethane precursors such as di-ISO and diol end-capped polybutylene adipate followed by heat treatment, washing, and supercritical drying led to opaque materials, somewhat stronger than silica but still quite brittle and much inferior to the materials described above. Direct mixing of a diisocyanate and an alcohol-free sol has been attempted recently by Yim et al. Reportedly, that procedure leads to week-long gelation times and requires an at least equally long aging period. In our attempt to add various amounts of di-ISO in a base-catalyzed sol in PC, we also noticed a week-long gelation time. The resulting aerogels were translucent but no less brittle than native silica. According to more recent studies, if propylene carbonate is replaced with acetone, it leads not only to shorter processing times, but also to much stronger gels that can tolerate loads in excess of 40 kg in the arrangement presented. We attribute that behavior to the lower viscosity of acetone, that allows faster diffusion of the di-ISO solution within the pores before di-ISO has time to react with the surface of silica. Further studies are underway to vary the chemical identity of the diisocyanate, as well as the composition and density of silica.

  4. Copper and silver complexes of tris(triazole)amine and tris(benzimidazole)amine ligands: evidence that catalysis of an azide-alkyne cycloaddition ("click") reaction by a silver tris(triazole)amine complex arises from copper impurities.

    PubMed

    Connell, Timothy U; Schieber, Christine; Silvestri, Ilaria Proietti; White, Jonathan M; Williams, Spencer J; Donnelly, Paul S

    2014-07-07

    The synthesis and characterization of a silver complex of the tripodal triazole ligand, tris(benzyltriazolylmethyl)amine (TBTA, L(1)), that is used as promoter to enhance Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reactions is reported. X-ray analysis of the silver(I) complex with L(1) reveals a dinuclear cation, [Ag2(L(1))2](2+), that is essentially isostructural to the copper(I) analogue. While the [Ag2(L(1))2](BF4)2 complex provides catalysis for the azide-alkyne cycloaddition process, evidence is presented that this arises from trace copper contamination. The synthesis of silver(I), copper(II), and copper(I) complexes of a second tripodal ligand, tris(2-benzimidazolymethyl)amine (L(2)), which is used to enhance the rate of CuAAC reactions, is also reported. X-ray crystallography of the Cu(I) complex [Cu(I)3(L(2))2(CH3CN)2](BF4)3 offers structural insight into previous mechanistic speculation about the role of this ligand in the CuAAC reaction.

  5. The Impact of Silica Nanoparticle Design on Cellular Toxicity and Hemolytic Activity

    PubMed Central

    Yu, Tian; Malugin, Alexander; Ghandehari, Hamidreza

    2011-01-01

    Understanding the toxicity of silica nanoparticles (SiO2) on the cellular level is crucial for rational design of these nanomaterials for biomedical applications. Herein, we explore the impacts of geometry, porosity and surface charge of SiO2 on cellular toxicity and hemolytic activity. Nonporous Stöber silica nanospheres (115 nm diameter), mesoporous silica nanospheres (120 nm diameter, aspect ratio 1), mesoporous silica nanorods with aspect ratio of 2, 4 and 8 (width by length 80 × 200 nm, 150 × 600 nm, 130 × 1000 nm) as well as their cationic counterparts were evaluated on macrophages, lung carcinoma cells, and human erythrocytes. It was shown that the toxicity of SiO2 is cell-type dependent and that surface charge and pore size govern cellular toxicity. Using inductively coupled plasma mass spectrometry, the cellular association of SiO2 was quantitated with the association amount increasing in the following order: mesoporous SiO2 (aspect ratio 1, 2, 4, 8) < amine-modified mesoporous SiO2 (aspect ratio 1, 2, 4, 8) < amine-modified nonporous Stöber SiO2 < nonporous Stöber SiO2. Geometry did not seem to influence the extent of SiO2 association at early or extended time points. The level of cellular association of the nanoparticles was directly linked to the extent of plasma membrane damage, suggesting a biological cause-and-effect relationship. Hemolysis assay showed that the hemolytic activity was porosity- and geometry- dependent for bare SiO2 and surface charge-dependent for amine-modified SiO2. A good correlation between hemolytic activity and cellular association was found on a similar dosage basis. These results can provide useful guidelines for the rational design of SiO2 in nanomedicine. PMID:21630682

  6. Autoinduced catalysis and inverse equilibrium isotope effect in the frustrated Lewis pair catalyzed hydrogenation of imines.

    PubMed

    Tussing, Sebastian; Greb, Lutz; Tamke, Sergej; Schirmer, Birgitta; Muhle-Goll, Claudia; Luy, Burkhard; Paradies, Jan

    2015-05-26

    The frustrated Lewis pair (FLP)-catalyzed hydrogenation and deuteration of N-benzylidene-tert-butylamine (2) was kinetically investigated by using the three boranes B(C6F5)3 (1), B(2,4,6-F3-C6H2)3 (4), and B(2,6-F2-C6H3)3 (5) and the free activation energies for the H2 activation by FLP were determined. Reactions catalyzed by the weaker Lewis acids 4 and 5 displayed autoinductive catalysis arising from a higher free activation energy (2 kcal mol(-1)) for the H2 activation by the imine compared to the amine. Surprisingly, the imine reduction using D2 proceeded with higher rates. This phenomenon is unprecedented for FLP and resulted from a primary inverse equilibrium isotope effect.

  7. Helical-Peptide-Catalyzed Enantioselective Michael Addition Reactions and Their Mechanistic Insights.

    PubMed

    Ueda, Atsushi; Umeno, Tomohiro; Doi, Mitsunobu; Akagawa, Kengo; Kudo, Kazuaki; Tanaka, Masakazu

    2016-08-05

    Helical peptide foldamer catalyzed Michael addition reactions of nitroalkane or dialkyl malonate to α,β-unsaturated ketones are reported along with the mechanistic considerations of the enantio-induction. A wide variety of α,β-unsaturated ketones, including β-aryl, β-alkyl enones, and cyclic enones, were found to be catalyzed by the helical peptide to give Michael adducts with high enantioselectivities (up to 99%). On the basis of X-ray crystallographic analysis and depsipeptide study, the amide protons, N(2)-H and N(3)-H, at the N terminus in the α-helical peptide catalyst were crucial for activating Michael donors, while the N-terminal primary amine activated Michael acceptors through the formation of iminium ion intermediates.

  8. Comparative Studies of Cathodically-Promoted and Base-Catalyzed Michael Addition Reactions of Levoglucosenone.

    PubMed

    Samet, Alexander V.; Niyazymbetov, Murat E.; Semenov, Victor V.; Laikhter, Andrei L.; Evans, Dennis H.

    1996-12-13

    Regioselective Michael addition of nitro and heterocyclic compounds to levoglucosenone, 1, is effectively catalyzed by amines and also by cathodic electrolysis. In comparison to the base-catalyzed reaction, it was found that under electrochemical conditions the reaction proceeds under milder conditions and with higher yields. Cathodically-initiated Michael addition of thiols to levoglucosenone using small currents produces the previously unknown threo addition product in several instances. The normal erythro isomer, identified as the kinetic product, tends to be formed when large currents are used. In contrast, slow, low current electrolyses promote equilibration of the two forms so that erythro can be converted to threo by the retro reaction and readdition. Addition of 2-naphthalenethiol to (R)-(+)-apoverbenone is also reported.

  9. Stereoselective synthesis of imidazolidin-2-ones via Pd-catalyzed alkene carboamination. Scope and limitations

    PubMed Central

    Fritz, Jonathan A.; Wolfe, John P.

    2008-01-01

    A method for the synthesis of imidazolidin-2-ones from N-allylureas and aryl or alkenyl bromides via Pd-catalyzed carboamination reactions is described. The N-allylurea precursors are prepared in one step from readily available allylic amines and isocyanates, and the Pd-catalyzed reactions effect the formation of a C–C bond, a C–N bond, and up to two stereocenters in a single step. Good diastereoselectivities are obtained for the conversion of substrates bearing allylic substituents to 4,5-disubstituted imidazolidin-2-ones, and excellent selectivity for the generation of products resulting from syn-addition across the alkene is observed when substrates derived from cyclic alkenes or E-1,2-disubstituted alkenes are employed. A brief discussion of reaction mechanism and product stereochemistry is presented. PMID:19122758

  10. Silica Fillers for elastomer Reinforement

    SciTech Connect

    Kohls, D.J.; Schaefer, D.W.

    2009-08-26

    This article summarizes recent work on the structure of precipitated silica used in the reinforcement of elastomers. Silica has a unique morphology, consisting of multiple structural levels that can be controlled through processing. The ability to control and characterize the multiple structures of precipitated silica is an example of morphological engineering for reinforcement applications. In this summary of some recent research efforts using precipitated silica, small-angle scattering techniques are described and their usefulness for determining the morphology of silica in terms of primary particles, aggregates, and agglomerates are discussed. The structure of several different precipitated silica powders is shown as well as the mechanical properties of elastomers reinforced with these silica particles. The study of the mechanical properties of filled elastomer systems is a challenging and exciting topic for both fundamental science and industrial application. It is known that the addition of hard particulates to a soft elastomer matrix results in properties that do not follow a straightforward rule of mixtures. Research efforts in this area have shown that the properties of filled elastomers are influenced by the nature of both the filler and the matrix, as well as the interactions between them. Several articles have reviewed the influence of fillers like silica and carbon black on the reinforcement of elastomers. In general, the structure-property relationships developed for filled elastomers have evolved into the following major areas: Filler structure, hydrodynamic reinforcement, and interactions between fillers and elastomers.

  11. Silica Fillers for elastomer Reinforement

    SciTech Connect

    Kohls, D.J.; Schaefer, D.W.

    2012-09-10

    This article summarizes recent work on the structure of precipitated silica used in the reinforcement of elastomers. Silica has a unique morphology, consisting of multiple structural levels that can be controlled through processing. The ability to control and characterize the multiple structures of precipitated silica is an example of morphological engineering for reinforcement applications. In this summary of some recent research efforts using precipitated silica, small-angle scattering techniques are described and their usefulness for determining the morphology of silica in terms of primary particles, aggregates, and agglomerates are discussed. The structure of several different precipitated silica powders is shown as well as the mechanical properties of elastomers reinforced with these silica particles. The study of the mechanical properties of filled elastomer systems is a challenging and exciting topic for both fundamental science and industrial application. It is known that the addition of hard particulates to a soft elastomer matrix results in properties that do not follow a straightforward rule of mixtures. Research efforts in this area have shown that the properties of filled elastomers are influenced by the nature of both the filler and the matrix, as well as the interactions between them. Several articles have reviewed the influence of fillers like silica and carbon black on the reinforcement of elastomers. In general, the structure-property relationships developed for filled elastomers have evolved into the following major areas: Filler structure, hydrodynamic reinforcement, and interactions between fillers and elastomers.

  12. High-pressure liquid chromatography of aromatic amines

    NASA Technical Reports Server (NTRS)

    Young, P. R.

    1979-01-01

    Analysis made on commercially available liquid chromatograph demonstrates high-pressure liquid chromatographic conditions for separation of approximately 50 aromatic amines ranging from simple aniline derivatives to complex multiring di- and tri-amines.

  13. DIRECT SYNTHESIS OF TERTIARY AMINES IN WATER USING MICROWAVES

    EPA Science Inventory

    A direct synthesis of tertiary amines is presented that proceeds expeditiously via N-alkylation of amines using alkyl halides in alkaline aqueous medium. This environmentally benign reaction is accelerated upon exposure to microwave irradiation resulting in shortened reaction tim...

  14. SEDIMENT-ASSOCIATED REACTIONS OF AROMATIC AMINES: QSAR DEVELOPMENT

    EPA Science Inventory

    Despite the common occurrence of the aromatic amine functional group in environmental contaminants, few quantitative structure-activity relationships (QSARs) have been developed to predict sorption kinetics for aromatic amines in natural soils and sediments. Towards the goal of d...

  15. SEDIMENT-ASSOCIATED REACTIONS OF AROMATIC AMINES. 2. QSAR DEVELOPMENT

    EPA Science Inventory

    The fate of aromatic amines in soils and sediments is dominated by irreversible binding through nucleophilic addition and oxidative radical coupling. Despite the common occurrence of the aromatic amine functional group in organic chemicals, the molecular properties useful for pr...

  16. Kinetics of silica particle formation in nonionic W/O microemulsions from TEOS

    SciTech Connect

    Chang, C.L.; Fogler, H.S.

    1996-11-01

    The kinetics of silica particle formation by the ammonia-catalyzed hydrolysis of tetraethyl orthosilicate (TEOS) in water-in-oil (W/O) microemulsions containing a nonionic surfactant was investigated using Fourier-transform infrared spectroscopy, transmission electron microscopy, and light-scattering techniques. The results show that TEOS hydrolysis and silica-particle growth occur at the same rate, indicating the growth of silica particles is rate-controlled by the hydrolysis of TEOS. The rate of TEOS hydrolysis in microemulsions is first order with respect to the concentration of aqueous ammonia (29 wt. % NH{sub 3}), but depends weakly on the concentration of water. Based on the fact that TEOS hydrolysis follows a nucleophilic substitution of the TEOS`s ethoxy group with hydroxyl ion, the kinetic data suggest that both water and ammonia remain predominantly in W/O microemulsion droplets. The rate of TEOS hydrolysis also depends on the surfactant concentration that controls the molecular contact between hydroxyl ions and TEOS in the solution. Due to the reaction-controlled growth mechanism, the silica-particle size distribution retains virtually the same shape over the growth period. The final average size of silica particles can be varied from 26 to 43 nm by adjusting concentrations of water and surfactant. Increasing the water concentration decreases the average size and uniformity of silica particles. For a given water concentration, the smallest and most uniform silica particles are produced at intermediate water-to-surfactant molar ratios (about 1.9). The results are discussed in terms of the effect of water concentration on the stability of the hydrolyzed silica reacting species during the nucleation of particles and of the water-to-surfactant molar ratio on the compartmentalization of silica species in microemulsions.

  17. CO2 adsorption on Santa Barbara Amorphous-15 (SBA-15) and amine-modified Santa Barbara Amorphous-15 (SBA-15) with and without controlled microporosity.

    PubMed

    Yan, Xinlong; Komarneni, Sridhar; Yan, Zifeng

    2013-01-15

    Mesoporous silica SBA-15 samples with and without controlled framework microporosity were prepared and used directly or impregnated with polymer amine as adsorbent for CO(2). These samples were evaluated for their ability to adsorb CO(2) by obtaining their equilibrium adsorption isotherms using volumetric adsorption at three different temperatures of 273 K, 278 K and 283 K. The data obtained were analyzed using Freundlich adsorption isotherm model while the isosteric heats of adsorption were estimated by the Clausius-Clapeyron equation. Under comparable conditions, the adsorption performance of silica SBA-15 was found to be strongly dependent upon the framework microporosity. However, the microporosity contribution to CO(2) adsorption in amine-modified SBA-15 was not obvious as amine blocked micropores and dominated CO(2) adsorption. The SBA-15 sample with higher microporosity displayed higher CO(2) uptake and the CO(2) uptake by amine-modified SBA-15 samples correlated with their total surface areas, as expected. These findings revealed the importance of surface area in designing an adsorbent for CO(2.).

  18. Preparation and characterization of monodisperse large-porous silica microspheres as the matrix for protein separation.

    PubMed

    Xia, Hongjun; Wan, Guangping; Zhao, Junlong; Liu, Jiawei; Bai, Quan

    2016-11-04

    High performance liquid chromatography (HPLC) is a kind of efficient separation technology and has been used widely in many fields. Micro-sized porous silica microspheres as the most popular matrix have been used for fast separation and analysis in HPLC. In this paper, the monodisperse large-porous silica microspheres with controllable size and structure were successfully synthesized with polymer microspheres as the templates and characterized. First, the poly(glycidyl methacrylate-co-ethyleneglycol dimethacrylate) microspheres (PGMA-EDMA) were functionalized with tetraethylenepentamine (TEPA) to generate amino groups which act as a catalyst in hydrolysis of tetraethyl orthosilicate (TEOS) to form Si-containing low molecular weight species. Then the low molecular weight species diffused into the functionalized PGMA-EDMA microspheres by induction force of the amino groups to form polymer/silica hybrid microspheres. Finally, the organic polymer templates were removed by calcination, and the large-porous silica microspheres were obtained. The compositions, morphology, size distribution, specific surface area and pore size distribution of the porous silica microspheres were characterized by infrared analyzer, scanning-electron microscopy, dynamic laser scattering, the mercury intrusion method and thermal gravimetric analysis, respectively. The results show that the agglomeration of the hybrid microspheres can be overcome when the templates were functionalized with TEPA as amination reagent, and the yield of 95.7% of the monodisperse large-porous silica microspheres can be achieved with high concentration of polymer templates. The resulting large-porous silica microspheres were modified with octadecyltrichlorosilane (ODS) and the chromatographic evaluation was performed by separating the proteins and the digest of BSA. The baseline separation of seven kinds of protein standards was achieved, and the column delivered a better performance when separating BSA digests

  19. Double emulsions and colloidosomes-in-colloidosomes using silica-based Pickering emulsifiers.

    PubMed

    Williams, Mark; Armes, Steven P; Verstraete, Pierre; Smets, Johan

    2014-03-18

    Poly(ethylene imine) (PEI) has been adsorbed onto the surface of fumed silica particles at pH 10 in order to produce an effective "hybrid" Pickering emulsifier. Systematically increasing the PEI/silica mass ratio at a fixed silica concentration of 1.0% w/w modifies the silica particle surface and hence allows the formation of oil-in-water (o/w) Pickering emulsions prepared via homogenization of an aldehyde-rich multi-component fragrance oil (at 12,000 rpm for 2 min at 20 °C). Further increasing the PEI/silica mass ratio leads to phase inversion, producing water-in-oil (w/o) Pickering emulsions. Thus this approach allows formation of stable water-in-oil-in-water (w/o/w) double emulsions using two batches of hydrophilic and hydrophobic PEI/silica hybrid particles that differ only in their PEI/silica mass ratios prior to homogenization. Stable w/o/w double emulsions can be prepared with oil volume fractions ranging from 5 to 42%. Moreover, controlling the volume fraction of the w/o Pickering emulsion homogenized in the presence of an aqueous dispersion of the hydrophilic PEI/silica particles allows the mean diameter of the resulting oil droplets to be conveniently controlled between 20 and 160 μm. Fluorescence microscopy studies confirm that controlling the mean diameter of these oil droplets allows encapsulation of either single or multiple droplets within them. Although these double emulsions do not require cross-linking at either interface to withstand an alcohol challenge, epoxy-amine cross-linking between the physically-adsorbed PEI chains and either an oil-soluble or a water-soluble bisepoxy-based polymeric cross-linker can be achieved to produce novel colloidosomes-in-colloidosomes, which may offer payload retention benefits over conventional colloidosomes.

  20. Peptide -- Silica Hybrid Networks

    NASA Astrophysics Data System (ADS)

    Altunbas, Aysegul; Sharma, Nikhil; Nagarkar, Radhika; Schneider, Joel; Pochan, Darrin

    2010-03-01

    In this study, a bio-inspired route was used to fabricate scaffolds that display hierarchical organization of an inorganic layer around an organic self-assembled peptide fibril template. The 20 amino acid peptide used in this study intramolecular folds into a beta-hairpin conformation on addition of a desired solution stimulus. This intramolecular folding is followed by intermolecular self-assembly of the peptides into a three dimensional network of entangled fibrils rich in beta-sheet with a high density of lysine groups exposed on the fibril-surfaces. The lysine-rich surface chemistry was utilized to create a silica shell around the fibrils. The mineralization process of the fibrils results in a rigid, porous silica network that retains the microscale and nanoscale structure of the peptide fibril network. Structural characterization via Transmission Electron Microscopy, cryogenic-Scanning Electron Microscopy, mechanical characterization via oscillatory rheology, Small Angle X-ray and Neutron Scattering of the silicified hydrogels will be presented.

  1. New insights into the molecular-level control of silica mineralization by diatoms

    NASA Astrophysics Data System (ADS)

    Wallace, A. F.; Dove, P. M.

    2007-12-01

    microscopy with elements of modern materials chemistry, to directly measure the rate of amorphous silica nucleation on COOH, NH3+, and COOH / NH3+-terminated surfaces under controlled solution conditions. Our results provide new insights into the molecular-level control of silica mineralization in diatoms. We show that differences between substrate-specific nucleation rates are controlled largely by kinetic factors rather than thermodynamic drivers, and that amine-terminated surfaces are not capable of triggering the onset of silica deposition without the synergistic activity of neighboring negatively charged species on the surface or in solution (e.g. carboxyl or phosphoryl groups). In light of this result we conclude that sites on the organic matrix that have phosphate and amine moieties in close proximity serve not only as contact points between the constituent macromolecules in the matrix, but also as initial sites of silica deposition.

  2. Metabolism of alkyl amines by the filamentous fungus Aspergillus versicolor.

    PubMed Central

    Lindley, N D

    1987-01-01

    A variety of monoalkyl-substituted amines were able to act as nitrogen sources for heterotrophically growing cultures of Aspergillus versicolor. Only amines whose alkyl chains were at least five carbon atoms long were capable of supporting significant growth in the absence of a separate carbon substrate. However, biomass yields were significantly higher during growth on glucose-amine than on glucose-ammonia, indicating that some energy-generating dissimilation of the amine to CO2 took place. PMID:3566265

  3. Hydroxyatrazine N-Ethylaminohydrolase (AtzB): an Amidohydrolase Superfamily Enzyme Catalyzing Deamination and Dechlorination▿

    PubMed Central

    Seffernick, Jennifer L.; Aleem, Asma; Osborne, Jeffrey P.; Johnson, Gilbert; Sadowsky, Michael J.; Wackett, Lawrence P.

    2007-01-01

    Hydroxyatrazine [2-(N-ethylamino)-4-hydroxy-6-(N-isopropylamino)-1,3,5-triazine] N-ethylaminohydrolase (AtzB) is the sole enzyme known to catalyze the hydrolytic conversion of hydroxyatrazine to N-isopropylammelide. AtzB, therefore, serves as the point of intersection of multiple s-triazine biodegradative pathways and is completely essential for microbial growth on s-triazine herbicides. Here, atzB was cloned from Pseudomonas sp. strain ADP and its product was purified to homogeneity and characterized. AtzB was found to be dimeric, with subunit and holoenzyme molecular masses of 52 kDa and 105 kDa, respectively. The kcat and Km of AtzB with hydroxyatrazine as a substrate were 3 s−1 and 20 μM, respectively. Purified AtzB had a 1:1 zinc-to-subunit stoichiometry. Sequence analysis revealed that AtzB contained the conserved mononuclear amidohydrolase superfamily active-site residues His74, His76, His245, Glu248, His280, and Asp331. An intensive in vitro investigation into the substrate specificity of AtzB revealed that 20 of the 51 compounds tested were substrates for AtzB; this allowed for the identification of specific substrate structural features required for catalysis. Substrates required a monohydroxylated s-triazine ring with a minimum of one primary or secondary amine substituent and either a chloride or amine leaving group. AtzB catalyzed both deamination and dechlorination reactions with rates within a range of one order of magnitude. This differs from AtzA and TrzN, which do not catalyze deamination reactions, and AtzC, which is not known to catalyze dechlorination reactions. PMID:17660279

  4. Silaffins in Silica Biomineralization and Biomimetic Silica Precipitation

    PubMed Central

    Lechner, Carolin C.; Becker, Christian F. W.

    2015-01-01

    Biomineralization processes leading to complex solid structures of inorganic material in biological systems are constantly gaining attention in biotechnology and biomedical research. An outstanding example for biomineral morphogenesis is the formation of highly elaborate, nano-patterned silica shells by diatoms. Among the organic macromolecules that have been closely linked to the tightly controlled precipitation of silica in diatoms, silaffins play an extraordinary role. These peptides typically occur as complex posttranslationally modified variants and are directly involved in the silica deposition process in diatoms. However, even in vitro silaffin-based peptides alone, with and without posttranslational modifications, can efficiently mediate biomimetic silica precipitation leading to silica material with different properties as well as with encapsulated cargo molecules of a large size range. In this review, the biomineralization process of silica in diatoms is summarized with a specific focus on silaffins and their in vitro silica precipitation properties. Applications in the area of bio- and nanotechnology as well as in diagnostics and therapy are discussed. PMID:26295401

  5. 40 CFR 721.6140 - Dialkyldithiophosphoric acid, aliphatic amine salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., aliphatic amine salt. 721.6140 Section 721.6140 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.6140 Dialkyldithiophosphoric acid, aliphatic amine salt. (a) Chemical... as a dialkyldithiophosphoric acid, aliphatic amine salt (P-90-1839) is subject to reporting...

  6. 40 CFR 721.638 - Silyl amine, potassium salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Silyl amine, potassium salt (generic... Substances § 721.638 Silyl amine, potassium salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as silyl amine, potassium...

  7. 40 CFR 721.638 - Silyl amine, potassium salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Silyl amine, potassium salt (generic... Substances § 721.638 Silyl amine, potassium salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as silyl amine, potassium...

  8. 40 CFR 721.9490 - Coco alklydimethyl amine salts (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Coco alklydimethyl amine salts... Specific Chemical Substances § 721.9490 Coco alklydimethyl amine salts (generic). (a) Chemical substances... coco alkyldimethyl amine salts (PMNs P-98-412/414/415/416/417) are subject to reporting under...

  9. 40 CFR 721.6140 - Dialkyldithiophosphoric acid, aliphatic amine salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., aliphatic amine salt. 721.6140 Section 721.6140 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.6140 Dialkyldithiophosphoric acid, aliphatic amine salt. (a) Chemical... as a dialkyldithiophosphoric acid, aliphatic amine salt (P-90-1839) is subject to reporting...

  10. Solid amine compounds as sorbents for carbon dioxide: A concept

    NASA Technical Reports Server (NTRS)

    Sutton, J. G.; Heimlich, P. F.; Tepper, E. H.

    1972-01-01

    Solid amine compounds were examined as possible absorbents for removal of carbon dioxide in life support systems of type which may be employed in high altitude aircraft, spacecraft, or submarines. Many solid amine compounds release absorbed carbon dioxide when heated in vacuum, therefore, when properly packaged spent amine compounds can be readily regenerated and put back into service.

  11. 40 CFR 721.7286 - Amines, N-tallowalkyltripropylenetetra-, citrates.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amines, N-tallowalkyltripropylenetetra... Specific Chemical Substances § 721.7286 Amines, N-tallowalkyltripropylenetetra-, citrates. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified as amines,...

  12. 40 CFR 721.7285 - Amines, N-cocoalkyltrimethylenedi-, citrates.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amines, N-cocoalkyltrimethylenedi... Specific Chemical Substances § 721.7285 Amines, N-cocoalkyltrimethylenedi-, citrates. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified as amines,...

  13. 40 CFR 721.7285 - Amines, N-cocoalkyltrimethylenedi-, citrates.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Amines, N-cocoalkyltrimethylenedi... Specific Chemical Substances § 721.7285 Amines, N-cocoalkyltrimethylenedi-, citrates. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified as amines,...

  14. 40 CFR 721.7286 - Amines, N-tallowalkyltripropylenetetra-, citrates.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Amines, N-tallowalkyltripropylenetetra... Specific Chemical Substances § 721.7286 Amines, N-tallowalkyltripropylenetetra-, citrates. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified as amines,...

  15. 40 CFR 721.7285 - Amines, N-cocoalkyltrimethylenedi-, citrates.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Amines, N-cocoalkyltrimethylenedi... Specific Chemical Substances § 721.7285 Amines, N-cocoalkyltrimethylenedi-, citrates. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified as amines,...

  16. 40 CFR 721.7285 - Amines, N-cocoalkyltrimethylenedi-, citrates.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Amines, N-cocoalkyltrimethylenedi... Specific Chemical Substances § 721.7285 Amines, N-cocoalkyltrimethylenedi-, citrates. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified as amines,...

  17. 40 CFR 721.7286 - Amines, N-tallowalkyltripropylenetetra-, citrates.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Amines, N-tallowalkyltripropylenetetra... Specific Chemical Substances § 721.7286 Amines, N-tallowalkyltripropylenetetra-, citrates. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified as amines,...

  18. 40 CFR 721.7286 - Amines, N-tallowalkyltripropylenetetra-, citrates.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Amines, N-tallowalkyltripropylenetetra... Specific Chemical Substances § 721.7286 Amines, N-tallowalkyltripropylenetetra-, citrates. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified as amines,...

  19. 40 CFR 721.10046 - Polyaromatic amine phosphate (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polyaromatic amine phosphate (generic... Specific Chemical Substances § 721.10046 Polyaromatic amine phosphate (generic). (a) Chemical substance and... amine phosphate (PMN P-02-747) is subject to reporting under this section for the significant new...

  20. 40 CFR 721.10046 - Polyaromatic amine phosphate (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Polyaromatic amine phosphate (generic... Specific Chemical Substances § 721.10046 Polyaromatic amine phosphate (generic). (a) Chemical substance and... amine phosphate (PMN P-02-747) is subject to reporting under this section for the significant new...

  1. 40 CFR 721.10046 - Polyaromatic amine phosphate (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Polyaromatic amine phosphate (generic... Specific Chemical Substances § 721.10046 Polyaromatic amine phosphate (generic). (a) Chemical substance and... amine phosphate (PMN P-02-747) is subject to reporting under this section for the significant new...

  2. 40 CFR 721.10046 - Polyaromatic amine phosphate (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Polyaromatic amine phosphate (generic... Specific Chemical Substances § 721.10046 Polyaromatic amine phosphate (generic). (a) Chemical substance and... amine phosphate (PMN P-02-747) is subject to reporting under this section for the significant new...

  3. 40 CFR 721.10046 - Polyaromatic amine phosphate (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Polyaromatic amine phosphate (generic... Specific Chemical Substances § 721.10046 Polyaromatic amine phosphate (generic). (a) Chemical substance and... amine phosphate (PMN P-02-747) is subject to reporting under this section for the significant new...

  4. Reductive amination with zinc powder in aqueous media.

    PubMed

    Giovenzana, Giovanni B; Imperio, Daniela; Penoni, Andrea; Palmisano, Giovanni

    2011-01-01

    Zinc powder in aqueous alkaline media was employed to perform reductive amination of aldehydes with primary amines. The corresponding secondary amines were obtained in good yields along with minor amounts of hydrodimerization byproducts. The protocol is a green alternative to the use of complex hydrides in chlorinated or highly flammable solvents.

  5. 40 CFR 721.639 - Amine aldehyde condensate.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Amine aldehyde condensate. 721.639... Substances § 721.639 Amine aldehyde condensate. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an amine aldehyde condensate (PMN...

  6. 40 CFR 721.639 - Amine aldehyde condensate.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Amine aldehyde condensate. 721.639... Substances § 721.639 Amine aldehyde condensate. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an amine aldehyde condensate (PMN...

  7. 40 CFR 721.639 - Amine aldehyde condensate.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amine aldehyde condensate. 721.639... Substances § 721.639 Amine aldehyde condensate. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an amine aldehyde condensate (PMN...

  8. 40 CFR 721.639 - Amine aldehyde condensate.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Amine aldehyde condensate. 721.639... Substances § 721.639 Amine aldehyde condensate. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an amine aldehyde condensate (PMN...

  9. 40 CFR 721.639 - Amine aldehyde condensate.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Amine aldehyde condensate. 721.639... Substances § 721.639 Amine aldehyde condensate. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an amine aldehyde condensate (PMN...

  10. Solvent-Free Reductive Amination: An Organic Chemistry Experiment

    ERIC Educational Resources Information Center

    Goldstein, Steven W.; Cross, Amely V.

    2015-01-01

    The reductive amination reaction between an amine and an aldehyde or ketone is an important method to add an additional alkyl group to an amine nitrogen. In this experiment, students react a selection of benzylamines with aldehydes to form the corresponding imines. These imines are reduced with a mixture of "p"-toluenesulfonic acid…

  11. Reductive amination with zinc powder in aqueous media

    PubMed Central

    Imperio, Daniela; Penoni, Andrea; Palmisano, Giovanni

    2011-01-01

    Summary Zinc powder in aqueous alkaline media was employed to perform reductive amination of aldehydes with primary amines. The corresponding secondary amines were obtained in good yields along with minor amounts of hydrodimerization byproducts. The protocol is a green alternative to the use of complex hydrides in chlorinated or highly flammable solvents. PMID:21915212

  12. 40 CFR 721.9490 - Coco alklydimethyl amine salts (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Coco alklydimethyl amine salts... Specific Chemical Substances § 721.9490 Coco alklydimethyl amine salts (generic). (a) Chemical substances... coco alkyldimethyl amine salts (PMNs P-98-412/414/415/416/417) are subject to reporting under...

  13. 40 CFR 721.638 - Silyl amine, potassium salt (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Silyl amine, potassium salt (generic... Substances § 721.638 Silyl amine, potassium salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as silyl amine, potassium...

  14. 40 CFR 721.6140 - Dialkyldithiophosphoric acid, aliphatic amine salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., aliphatic amine salt. 721.6140 Section 721.6140 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.6140 Dialkyldithiophosphoric acid, aliphatic amine salt. (a) Chemical... as a dialkyldithiophosphoric acid, aliphatic amine salt (P-90-1839) is subject to reporting...

  15. 40 CFR 721.10569 - Tricyclic quaternary amine salt (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Tricyclic quaternary amine salt... Specific Chemical Substances § 721.10569 Tricyclic quaternary amine salt (generic). (a) Chemical substance... tricyclic quaternary amine salt (PMN P-08-471) is subject to reporting under this section for...

  16. 40 CFR 721.9490 - Coco alklydimethyl amine salts (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Coco alklydimethyl amine salts... Specific Chemical Substances § 721.9490 Coco alklydimethyl amine salts (generic). (a) Chemical substances... coco alkyldimethyl amine salts (PMNs P-98-412/414/415/416/417) are subject to reporting under...

  17. 40 CFR 721.9490 - Coco alklydimethyl amine salts (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Coco alklydimethyl amine salts... Specific Chemical Substances § 721.9490 Coco alklydimethyl amine salts (generic). (a) Chemical substances... coco alkyldimethyl amine salts (PMNs P-98-412/414/415/416/417) are subject to reporting under...

  18. 40 CFR 721.6140 - Dialkyldithiophosphoric acid, aliphatic amine salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., aliphatic amine salt. 721.6140 Section 721.6140 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.6140 Dialkyldithiophosphoric acid, aliphatic amine salt. (a) Chemical... as a dialkyldithiophosphoric acid, aliphatic amine salt (P-90-1839) is subject to reporting...

  19. 40 CFR 721.10569 - Tricyclic quaternary amine salt (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Tricyclic quaternary amine salt... Specific Chemical Substances § 721.10569 Tricyclic quaternary amine salt (generic). (a) Chemical substance... tricyclic quaternary amine salt (PMN P-08-471) is subject to reporting under this section for...

  20. 40 CFR 721.6140 - Dialkyldithiophosphoric acid, aliphatic amine salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., aliphatic amine salt. 721.6140 Section 721.6140 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.6140 Dialkyldithiophosphoric acid, aliphatic amine salt. (a) Chemical... as a dialkyldithiophosphoric acid, aliphatic amine salt (P-90-1839) is subject to reporting...

  1. 40 CFR 721.638 - Silyl amine, potassium salt (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Silyl amine, potassium salt (generic... Substances § 721.638 Silyl amine, potassium salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as silyl amine, potassium...

  2. 40 CFR 721.638 - Silyl amine, potassium salt (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Silyl amine, potassium salt (generic... Substances § 721.638 Silyl amine, potassium salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as silyl amine, potassium...

  3. 40 CFR 721.750 - Aromatic amine compound.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Aromatic amine compound. 721.750... Substances § 721.750 Aromatic amine compound. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance aromatic amine compound (PMN P-86-334) is subject to reporting...

  4. 40 CFR 721.750 - Aromatic amine compound.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Aromatic amine compound. 721.750... Substances § 721.750 Aromatic amine compound. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance aromatic amine compound (PMN P-86-334) is subject to reporting...

  5. 40 CFR 721.750 - Aromatic amine compound.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Aromatic amine compound. 721.750... Substances § 721.750 Aromatic amine compound. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance aromatic amine compound (PMN P-86-334) is subject to reporting...

  6. 40 CFR 721.750 - Aromatic amine compound.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Aromatic amine compound. 721.750... Substances § 721.750 Aromatic amine compound. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance aromatic amine compound (PMN P-86-334) is subject to reporting...

  7. 40 CFR 721.7286 - Amines, N-tallowalkyltripropylenetetra-, citrates.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Amines, N-tallowalkyltripropylenetetra... Specific Chemical Substances § 721.7286 Amines, N-tallowalkyltripropylenetetra-, citrates. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified as amines,...

  8. 40 CFR 721.7285 - Amines, N-cocoalkyltrimethylenedi-, citrates.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Amines, N-cocoalkyltrimethylenedi... Specific Chemical Substances § 721.7285 Amines, N-cocoalkyltrimethylenedi-, citrates. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified as amines,...

  9. 40 CFR 721.10199 - Substituted aliphatic amine (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted aliphatic amine (generic... Specific Chemical Substances § 721.10199 Substituted aliphatic amine (generic). (a) Chemical substance and... aliphatic amine (PMN P-06-702) is subject to reporting under this section for the significant new...

  10. 40 CFR 721.640 - Amine substituted metal salts.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Amine substituted metal salts. 721.640... Substances § 721.640 Amine substituted metal salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as amine substituted metal...

  11. 40 CFR 721.640 - Amine substituted metal salts.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Amine substituted metal salts. 721.640... Substances § 721.640 Amine substituted metal salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as amine substituted metal...

  12. 40 CFR 721.640 - Amine substituted metal salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amine substituted metal salts. 721.640... Substances § 721.640 Amine substituted metal salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as amine substituted metal...

  13. 40 CFR 721.640 - Amine substituted metal salts.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Amine substituted metal salts. 721.640... Substances § 721.640 Amine substituted metal salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as amine substituted metal...

  14. 40 CFR 721.640 - Amine substituted metal salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Amine substituted metal salts. 721.640... Substances § 721.640 Amine substituted metal salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as amine substituted metal...

  15. Thiourea-Catalyzed Enantioselective Cyanosilylation of Ketones

    PubMed Central

    Fuerst, Douglas E.; Jacobsen, Eric N.

    2011-01-01

    The new chiral amino thiourea catalyst 3d promotes the highly enantioselective cyanosilylation of a wide variety of ketones. The hindered tertiary amine substituent plays a crucial role both with regard to stereoinduction and reactivity, suggesting a cooperative mechanism involving electrophile activation by thiourea and nucleophile activation by the amine. PMID:15969569

  16. Copper-catalyzed azide alkyne cycloaddition polymer networks

    NASA Astrophysics Data System (ADS)

    Alzahrani, Abeer Ahmed

    The click reaction concept, introduced in 2001, has since spurred the rapid development and reexamination of efficient, high yield reactions which proceed rapidly under mild conditions. Prior to the discovery of facile copper catalysis in 2002, the thermally activated azide-alkyne or Huisgen cycloaddition reaction was largely ignored following its discovery in large part due to its slow kinetics, requirement for elevated temperature and limited selectivity. Now, arguably, the most prolific and capable of the click reactions, the copper-catalyzed azide alkyne cycloaddition (CuAAC) reaction is extremely efficient and affords exquisite control of the reaction. The orthogonally and chemoselectivity of this reaction enable its wide utility across varied scientific fields. Despite numerous inherent advantages and widespread use for small molecule synthesis and solution-based polymer chemistry, it has only recently and rarely been utilized to form polymer networks. This work focuses on the synthesis, mechanisms, and unique attributes of the CuAAC reaction for the fabrication of functional polymer networks. The photo-reduction of a series of copper(II)/amine complexes via ligand metal charge transfer was examined to determine their relative efficiency and selectivity in catalyzing the CuAAC reaction. The aliphatic amine ligands were used as an electron transfer species to reduce Cu(II) upon irradiation with 365 nm light while also functioning as an accelerating agent and as protecting ligands for the Cu(I) that was formed. Among the aliphatic amines studied, tertiary amines such as triethylamine (TEA), tetramethyldiamine (TMDA), N,N,N',N",N"-pentamethyldiethylenetriamine (PMDTA), and hexamethylenetetramine (HMTETA) were found to be the most effective. The reaction kinetics were accelerated by increasing the PMDETA : Cu(II) ratio with a ratio of ligand to Cu(II) of 4:1 yielding the maximum conversion in the shortest time. The sequential and orthogonal nature of the photo

  17. Improvement of thermal stability of polypropylene using DOPO-immobilized silica nanoparticles

    PubMed Central

    Dong, Quanxiao; Ding, Yanfen; Wen, Bin; Wang, Feng; Dong, Huicong; Zhang, Shimin

    2014-01-01

    After the surface silylation with 3-methacryloxypropyltrimethoxysilane, silica nanoparticles were further modified by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). The immobilization of DOPO on silica nanoparticles was confirmed by Fourier transform infrared spectroscopy, UV–visible spectroscopy, magic angle spinning nuclear magnetic resonance, and thermogravimetric analysis. By incorporating the DOPO-immobilized silica nanoparticles (5 wt%) into polypropylene matrix, the thermal oxidative stability exhibited an improvement of 62 °C for the half weight loss temperature, while that was only 26 °C increment with incorporation of virgin silica nanoparticles (5 wt%). Apparent activation energies of the polymer nanocomposites were estimated via Flynn–Wall–Ozawa method. It was found that the incorporation of DOPO-immobilized silica nanoparticles improved activation energies of the degradation reaction. Based on the results, it was speculated that DOPO-immobilized silica nanoparticles could inhibit the degradation of polypropylene and catalyze the formation of carbonaceous char on the surface. Thus, thermal stability was significantly improved. PMID:24729654

  18. The Synthesis of Methyl Salicylate: Amine Diazotization.

    ERIC Educational Resources Information Center

    Zanger, Murray; McKee, James R.

    1988-01-01

    Notes that this experiment takes safety and noncarcinogenic reactants into account. Demonstrates the use of diazonium salts for the replacement of an aromatic amine group by a phenolic hydroxyl. Involves two pleasant-smelling organic compounds, methyl anthranilate (grape) and methyl salicylate (oil of wintergreen). (MVL)

  19. Atmospheric reactivity studies of aliphatic amines

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ambient studies of particulate matter have shown that alkyl amines are often present in particles in areas impacted by agricultural emissions. These locations include California’s Central Valley and Inland Empire and Utah’s Cache Valley. These compounds are not typically observed in airsheds that so...

  20. DETERMINATION OF AROMATIC AMINES IN SOILS

    EPA Science Inventory

    A rapid liquid chromatographic(LC)method with ultraviolet(UV)or fluorescence detection was developed for parts-per-billion levels of aromatic amines in soils. 2,4-Diaminotoluene, pyridine,aniline,2-picoline,2-toluidine,5-nitro-2-toluidine,2-methyl-6-ethylaniline,4-aminobiphenyl,4...