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Heydenrych, Greta. "New amino- and titanoxycarbene complexes of group 6 metals." Thesis, Stellenbosch : Stellenbosch University, 2001. http://hdl.handle.net/10019.1/52355.
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O'Sullivan, Michael B. "Homochiral group transfer via diazocarbonyl intermediates derived from natural amino acids." Thesis, Queen's University Belfast, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.388067.
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Booysen, Irvin Noel. "Rhenium(V)-Imido complexes with potentially multidentate ligands containing the amino group." Thesis, Nelson Mandela Metropolitan University, 2007. http://hdl.handle.net/10948/479.
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The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab=1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. The complex trans-[Re(ada)Cl3(PPh3)2] (H2ada=2-aminodiphenylamine) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2ada in acetonitrile. The ligand ada is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. Surprisingly, the Re-Cl bond length trans to the Re=N bond is shorter than the two equatorial Re-Cl bond lengths. The reaction of equimolar quantities of cis-[ReO2I(PPh3)2] with 5,6-diamino-1,3- dimethyluracil (H2ddd) in acetonitrile led to the formation of [Re(ddd)(Hddd)I(PPh3)2](ReO4). The X-ray crystal structure shows that the ligand ddd is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hddd is coordinated bidentately via the neutral amino nitrogen, which is coordinated trans to the imido nitrogen, and the singly deprotonated amido nitrogen, trans to the iodide. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux conditions led to the isolation of [C12H12N6O4] as only product. The [ReO4]- ion is therefore instrumental in the formation of [C12H12N6O4], and since the product contains no rhenium in any oxidation state, the conclusion is that [ReO4]- catalyses the oxidative deamination of H2ddd. The X-ray crystal structure consists of two centrosymmetric, tricyclic rings, comprising a central pyrazine ring and two terminal pyrimidine rings. The reaction of a twofold molar excess of H2apb (H2apb=2-(2-aminophenyl)-1Hbenzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of the formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonal-bipyramidal environment. The two imidazole N(2) atoms lie in the apical positions trans to each other, with the oxo-oxygen and two amido N(1) atoms in the trigonal plane. The complex has C2-symmetry. The two amino groups are singly deprotonated and provide a negative charge each, so that they are coordinated as amides. The oxo group provides two negative charges. In order to obtain electroneutrality for the rhenium(V) complex, the two coordinated imidazole nitrogens provide one negative charge. The complex salt trans-[Re(mps)Cl(PPh3)2](ReO4) (H3mps=N-(2-amino-3- methylphenyl)salicylideneimine) was prepared by the reaction of trans- [ReOCl3(PPh3)2] with a twofold molar excess of H3mps. The X-ray crystal structure shows that the trianionic ligand mps acts as a tridentate chelate via the doubly deprotonated amino nitrogen (which is present in trans- [Re(mps)Cl(PPh3)2](ReO4) as an imide), the neutral imino nitrogen and the deprotonated phenolic oxygen. The [ReO4]- anion has approximately regular tetrahedral geometry. Two significant hydrogen bonds are formed between two of the perrhenyl oxygens and the water of crystallization. The six-coordinated complex cis-[Re(mps)Cl2(PPh3)2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps in benzene. The Xray crystal structure shows that the mps ligand coordinates as a tridentate chelate via the doubly deprotonated 2-amino nitrogen, the neutral imino nitrogen and the phenolate oxygen. The imide and phenolate oxygen coordinate trans to each other in a distorted octahedral geometry around the rhenium(V) centre, with the two chlorides in cis positions.
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Zhou, Guannan. "Polycondensation of Bridged Amino-Functionalized Trialkoxysilanes." Digital Commons @ East Tennessee State University, 2011. https://dc.etsu.edu/etd/1292.
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The reduction of CO2 emission has been a worldwide mission to resolve global warming predicament. Mesoporous silsesquioxanes, which stabilized by organobridges and has high content aminon absorption site, can serve as a potential CO2 adsorbent. Synthesis of such material is done by hydrolysis and polycondensation of trialkoxysilane. The fastest gelation was observed at reaction in the absence of acids or bases. However, addition of surfactant to the reaction mixture catalyzed formation of silsesquioxanes in acidic media. Obtained materials are strongly hydrophilic and possess a high thermostability. Study of particle size distributions showed that in all cases it was bimodal. The largest particles formed in basic media. Mesoporous silsesquioxanes were obtained from bridged alkyltrimethoxysilanes in the presence of surfactants.
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Booysen, Irvin Noel. "Rhenium (I) and (V) complexes with potentially mulidentate ligands containing the Amino group." Thesis, Nelson Mandela Metropolitan University, 2009. http://hdl.handle.net/10948/1270.
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The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab = 1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only in a distorted octahedral coordination geometry around the metal ion. The complex trans- [Re(ada)Cl3(PPh3)2] (H2ada = 2-aminodiphenylamine) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2ada in acetonitrile. The ligand ada is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. The ‘2 + 1’ complex fac- [Re(CO)3(Hamp)(amp)] (Hamp = 2-aminophenol) was isolated from the reaction of a two molar ratio of Hamp with [Re(CO)5Br] in toluene. The reaction of a 1:1 molar ratio of [Re(CO)5Br] and H2ada led to the isolation of the Re(I) complex, fac- [Re(CO)3Br(H2ada)]. The reaction of equimolar quantities of cis-[ReO2I(PPh3)2] with 5,6-diamino-1,3- dimethyluracil (H2ddd) in acetonitrile led to the formation of [Re(ddd)(Hddd)I(PPh3)2](ReO4). The X-ray crystal structure shows that the ligand ddd is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hddd is coordinated bidentately via the neutral amino nitrogen, which is coordinated trans to the imido nitrogen, and the singly deprotonated amido nitrogen, trans to the iodide. The reaction of trans-[ReOCl3(PPh3)2] with N-(2-aminobenzylidene)-5-amino-1,3-dimethyl uracil (H3dua) in ethanol gave a mixed crystal which contains both the neutral oxorhenium(V) complex [ReOCl(Hdua)] and the imido rhenium(V) [Re(dua)Cl2(PPh3)] in an equimolar ratio in the asymmetric unit. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux led to the isolation of [C12H12N6O4] as only product. The [ReO4]- anion is therefore instrumental in the formation of [C12H12N6O4], and since the product contains no rhenium in any oxidation state, the conclusion is that [ReO4]- catalyses the oxidative deamination Abstract I.N. Booysen Nelson Mandela Metropolitan University vii of H2ddd. The X-ray crystal structure consists of two centrosymmetric, tricyclic rings, comprising a central pyrazine ring and two terminal pyrimidine rings. The reaction of 2-(2-aminophenyl)benzothiazole (Habt) with [Re(CO)5Br] led to the isolation of the rhenium(I) complex fac-[Re(Habt)(CO)3Br]. With trans-[ReOCl3(PPh3)2], the ligand Habt decomposed to form the oxofree rhenium(V) complex [Re(itp)2Cl(PPh3)] (itp = 2-amidophenylthiolate). From the reaction of trans-[ReOBr3(PPh3)2] with 2-(2- hydroxyphenyl)benzothiazole (Hhpd) the complex [ReVOBr2(hpd)(PPh3)] was obtained. The reaction of a twofold molar excess of H2apb (2-(2-aminophenyl)-1-benzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonalbipyramidal environment. The two imidazole N(2) atoms lie in the apical positions trans to each other, with the oxo-oxygen and two amido N(1) atoms in the trigonal plane. A new nitrosylrhenium(II) complex salt, [Re(NO)BrL2(PPh3)2](ReO4) (H2L2 = 2-amino-5- (triphenylphosphino)phenol), is the first example of a complex containing the triphenylphosphonium-amidophenolate ligand L2, formed by the nucleophilic attack of a PPh3 on a coordinated amidophenolate ring. The complex salt trans-[Re(mps)Cl(PPh3)2](ReO4) (H3mps = N-(2-amino-3- methylphenyl)salicylideneimine) was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps. The X-ray crystal structure shows that the trianionic ligand mps acts as a tridentate chelate via the doubly deprotonated amino nitrogen (an imide), the neutral imino nitrogen and the deprotonated phenolic oxygen. The six-coordinated complex cis-[Re(mps)Cl2(PPh3)2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps in benzene. The X-ray crystal structure show that the mps ligand coordinates as a tridentate chelate via the doubly deprotonated 2-amino nitrogen, the neutral imino nitrogen and the phenolate oxygen. The imide and phenolate oxygen coordinate trans to each other in a distorted octahedral geometry, around the rhenium(V) centre, with the two chlorides in cis positions. A new oxofree rhenium(V) complex salt, [Re(bbd)2](ReO4) ( H2bbd = N-(2- Abstract I.N. Booysen Nelson Mandela Metropolitan University viii aminobenzylidene)benzene-1,2-diamine), has been synthesized and the chelates bbd are coordinated as dianionic tridentate N,N,N-donor diamidoimines. The rhenium(V) ion is centered in a distorted trigonal prism. The rhenium(I) compound fac-[Re(CO)3(daa)].Hpab.H2O (Hpab = N1,N2-(1,2- phenylene)bis(2-aminobenzamide); Hdaa = 2-amino-N-(2-aminophenyl)benzamide) was synthesized from the reaction of [Re(CO)5Br] with a two equivalents of Hpab in toluene. The monoanionic tridentate ligand daa was formed by the rhenium-mediated cleavage of an amido N-C bond of the potentially tetradentate ligand Hpab. Daa is coordinated as a diaminoamide via three nitrogen-donor atoms. The reaction of a twofold molar excess of H2amben (H2amben = N1,N2-bis(2-aminobenzylidene)ethane-1,2-diamine) with trans- [ReOBr3(PPh3)2] gave the oxorhenium(V) cationic complex [ReO(amben)]X (X = Br-, PF6 -). The Re(V) oxo-bridged compound, {μ-O}[ReO(omben)]2.H2O (H2omben = N1,N2- bis(2-hydroxybenzylidene)ethane-1,2-diamine) was isolated from the reaction of a 2:1 molar ratio of H2omben and trans-[ReO2(py)4]Cl in methanol. The seven-coordinate rhenium(III) complex cation [ReIII(dhp)(PPh3)2]+ was isolated as the [ReO4]- salt from the reaction of cis-[ReVO2I(PPh3)2] with 2,6-bis(2- hydroxyphenyliminomethyl)pyridine (H2dhp) in ethanol. In the complex fac- [Re(CO)3(H2dhp)Br], prepared from [Re(CO)5Br] and H2dhp in toluene, the H2dhp ligand acts as a neutral bidentate N,N-donor chelate. An equimolar ratio reaction of 2-aminobenzaldehyde and 2-(2-aminophenyl)-1- benzimidazole in methanol led to 2-(5,6-dihydrobenzimidazolo[1,2-c]-quinazolin-6- yl)aniline. In an attempt to explore the template formation of this class of ligand with rhenium, the reaction of salicylaldehyde and 2-(2-aminophenyl)-1-benzimidazole in ethanol which was followed by the addition of trans-[ReOBr3(PPh3)2] led to the formation of the salt, 6-(2-hydroxyphenyl)-5,6-dihydrobenzimidazolo[1,2-c]quinazolin- 12-ium bromide. The compound 6-(2-methylthiophenyl)-5,6-dihydrobenzimidazolo[1,2- c]quinazolin-12-ium was synthesized via the reaction of 2-aminobenzaldehyde and 2- methylthiobenzaldehyde in methanol.
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Miller, Suzanne M. "Examination of specific amino acid residues of desulfovibrio desulfuricans cytochrome C₃ in electron transfer." Diss., Columbia, Mo. : University of Missouri-Columbia, 2005. http://hdl.handle.net/10355/4252.
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Thesis (M.S.)--University of Missouri-Columbia, 2005."December 2005" The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Vita. Includes bibliographical references.
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Lundberg, Helena. "Group (IV) Metal-Catalyzed Direct Amidation : Synthesis and Mechanistic Considerations." Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2015. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-116955.
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The amide unit constitutes the backbone of proteins, and it is present in a large number of pharmaceutically active molecules, polymeric materials such as nylon and Kevlar, as well as in food additives like aspartame. Amides are produced in enormous amounts every year, thus, environmentally friendly and selective methods for their formation are of great importance. This thesis deals with the direct formation of amides from non-activated carboxylic acids and amines with the aid of group (IV) metal complexes. Water is the only by-product of this environmentally benign process. This fact stands in contrast to the most common methods for amide formation to date, which involve the use of waste-intensive, expensive and often toxic coupling reagents. The catalytic protocols presented herein use titanium, zirconium and hafnium complexes under mild reaction conditions to produce amides in good to excellent yields. Furthermore, carbamates are demonstrated to be suitable sources of gaseous amines for the formation of primary and tertiary amides under catalytic conditions. In addition, preliminary results from on-going mechanistic investigations of the zirconium- and hafnium-catalyzed processes are presented.Amidbindningen är en kemisk enhet som utgör ryggraden i proteiner, och som även återfinns i en stor mängd läkemedelsmolekyler, polymera material som nylon och Kevlar, samt i tillsatser i livsmedelsindustrin, exempelvis aspartam. Amider produceras i enorma mängder varje år, och det är av stor vikt att utveckla miljövänliga och selektiva metoder för deras framställning. Denna avhandling behandlar direkt amidering av icke-aktiverade karboxylsyror och aminer med hjälp av katalytiska mängder metallkomplex, baserade på titan, zirkonium och hafnium. Den enda biprodukten från denna amideringsreaktion är vatten. Jämfört med de metoder som generellt används idag för amidsyntes, så är de presenterade metoderna avsevärt mer miljövänliga med avseende på toxicitet hos reagensen såväl som på mängden avfall som genereras. Dessutom redovisas här en katalytisk metod för syntes av primära och tertiära amider genom att använda olika karbamat som källa till gasformiga aminer, vilka annars kan vara praktiskt svåra att arbeta med. Preliminära resultat från en pågående mekanistisk studie av de zirkonium- och hafnium-katalyserade processerna är också inkluderade.
At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 2: Accepted.
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Göring, M., A. Seifert, K. Schreiter, P. Müller, and S. Spange. "A non-aqueous procedure to synthesize amino group bearing nanostructured organic–inorganic hybrid materials." Universitätsbibliothek Chemnitz, 2014. http://nbn-resolving.de/urn:nbn:de:bsz:ch1-qucosa-152006.
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Amino-functionalized organic–inorganic hybrid materials with a narrow distributed nanostructure of 2–4 nm in size were obtained by means of a template-free and non-aqueous procedure. Simultaneous twin polymerization of novel amino group containing twin monomers with 2,2′-spirobi[4H-1,3,2-benzodioxasiline] has been applied for this purpose. The amino groups of the organic–inorganic hybrid material are useful for post derivatizationDieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich
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Inokuma, Tsubasa. "Development of Novel Hydrogen-Bond Donor Catalysts Bearing Amino or Hydroxy Group for Asymmetric Synthesis." 京都大学 (Kyoto University), 2011. http://hdl.handle.net/2433/152053.
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Zhu, Li. "Studies of soy protein adhesive performance on the effects of ph, amino acid group, and temperature /." Search for this dissertation online, 2006. http://wwwlib.umi.com/cr/ksu/main.
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Wallén, Helena. "Olfactory sensitivity in CD-1 mice for six L- and D amino acids." Thesis, Linköping University, Department of Physics, Chemistry and Biology, 2010. http://urn.kb.se/resolve?urn=urn:nbn:se:liu:diva-56783.
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Virstedt, Signe Johanna. "Effect of the purine 2-amino group on the structure and nucleosome binding of some high affinity DNA sequences." Thesis, University of Cambridge, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.620352.
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Han, Richard I.-Ming. "Early calcification patterns of bioprosthetic aortic tissue : a comparison of amino versus carboxyl group and combination cross-linked tissue." Master's thesis, University of Cape Town, 2003. http://hdl.handle.net/11427/2780.
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El, Berjawi Rayane. "Construction and characterizations of new perylenediimide based molecular assemblies derived from nitro or amino bay-substituted derivatives." Thesis, Angers, 2019. http://www.theses.fr/2019ANGE0062.
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Les dérivés de pérylènediimide (PDI) font partie des accepteurs d’électrons les plus performants. Leur squelette rigide liéà un système π aromatique étendu, des propriétés optiques et électroniques remarquables et une bonne stabilité chimique et thermique en font de bons candidats comme matériaux de type-n avec de nombreuses applications, en particulier dans le domaine du photovoltaïque organique. Ce travail étudie la réactivité de dérivés pérylènediimides en position «bay» pour la synthèse et la caractérisation de nouveaux systèmes accepteurs originaux dont certains seront utilisés comme matériaux dans des cellules solaires organiques.Dans la première partie de cette thèse, une procédure alternative à la réaction de couplage type Suzuki-Miyaura a été développée pour la synthèse de dérivés PDI à partir du composépossédant un groupement nitro en position «bay». Une dyade associant le PDI au fullerène C60a ensuite été étudiée. Dans une seconde partie, l’étude s’est portée sur la synthèse et la caractérisation de nouveaux dimères de PDI et leurs utilisations comme matériaux dans des cellules solaires organiques. Dans le dernier chapitre, des recherches ont été menées sur la réactivité d’un PDI possédant un groupement amino en position «bay», d’abord via la chimie des sels de diazonium, puis dans la synthèse d’azacoronènes pour former de nouvelles dyades à base de PDI. Ces nouveaux composés ont fait l’objet d’études préliminaires comme nouveaux matériaux accepteurs pour des applications en photovoltaïqueAmong the powerful organic electron acceptors are those based on perylenediimide derivatives. Their rigid planar backbone and extended π-conjugation with outstanding optical and electronic properties, chemical and thermal stabilities allowed them to be potentially useful as n-type materials in applications such as organic photovoltaic cells (OPVs).This dissertation describes the study of perylenediimide reactivity at the bay region for the synthesis and characterizations of new original acceptor systems. Some of them were applied in organic solar cells. In the first part of this thesis, an alternative procedure to conventional Suzuki-Miyaura coupling method was developed for the synthesis of PDI derivatives starting from mono-nitro PDI. From this was targeted the construction of PDI-C60dyad.In the second part, synthesis and characterizations of PDI dimer and its application in organic solar cells are discussed. In the last part, investigations on the reactivity of mono-amino PDI are described via the chemistry of the diazonium salt or through the synthesis of PDI-based azacoronene dyads. Preliminary studies of some of these acceptors in organic solar cells are also presented
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Shao, Pengcheng Patrick. "Synthesis, characterization and reactivity studies of group 2, 3 and 4 metal complexes bearing chelating amino siloxide and alkoxide ligands." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1997. http://www.collectionscanada.ca/obj/s4/f2/dsk2/tape16/PQDD_0005/NQ32722.pdf.
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Běťák, Lukáš. "Příprava materiálů na bázi reaktivně modifikovaných polyolefinů." Master's thesis, Vysoké učení technické v Brně. Fakulta chemická, 2010. http://www.nusl.cz/ntk/nusl-216618.
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This thesis deals with a preparation of modified polypropylene. Modified polypropylene was prepared by reaction itaconic anhydride and compounds contain primary and secondary amino group (diaminododecane, aminoethylethanolamine and aminoethylpiperazine). Knowledge of radical and condensation modification of polypropylene were summarized in the theoretical part. New application of modified polypropylene ware summarized at the theoretical part as well. In the experimental part polypropylene was functionalized by grafting with itaconic anhydride during reactive extrusion. Extrusion was carried on the co-rotating twin-screw extruder (Brabender 25 DSE L/D = 34) at 230 °C and 30 RPM. Residence time of reactive blend was 3 minutes. The modified polypropylene PP-g-IAH) contained 0.5 wt% of itaconic anhydride. 2,5 dimethyl 2,5bis(tert buthyl-peroxy)hexane (Luperox 101) was used as a radical initiator. A ratio initiator/monomer was 1:0.6 (mol/mol). PP-g-IAH was used for condensation reaction with amino compounds in molar ratios IAH/amine from 1:0,3 to 1:1. This reaction carried out in single screw extruder (Betol 1825 L/D = 39) at 210 °C and 30 RPM. Residence time of reactive blend was 3 minutes. Fourier transform infrared spectroscopy was used for a calculation of reaction conversion and for description of new functional groups in the materials. This analysis confirmed the presence of amide and imide groups in the samples. Influence of amino compounds to polymer crystallinity was studied by differential scanning calorimetry. Termogravimetric analysis focused on thermal stability of prepared samples and changes of thermal stability was observed in dependence of additives amount. The rheological behaviors of modified PP were analyzed by measuring the complex viscosity.
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Fazal, Abidali. "Assessment of the modulation of excitatory amino acid release by group I metabotropic glutamate receptors : in vitro and in vivo studies using D-[{195]H] aspartic acid as a surrogate marker." Thesis, Imperial College London, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.413640.
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Cherif, Mohamed Amine. "Sur l'approximation rationnelle pour le semi-groupe de transport." Poitiers, 2010. http://theses.edel.univ-poitiers.fr/2010/Cherif-Mohamed-Amine/2010-Cherif-Mohamed-Amine-These.pdf.
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La notion de l'approximation rationnelle est normalement conçue pour la discrétisation en temps. Dans cette thèse nous mélangeons cette notion avec la notion de la convergence au sens de Kato qui découle d'une discrétisation en espace pour l'équation de transport neutronique. Nous appliquons cette procedure aux schémas d'Euler explicite et implicite, Crank-Nicolson et Prédicateur-Correcteur qui ont le degré de convergence 1,2 et 3 au sens de l'approximation rationnelle. Pour démontrer la convergence nous utiliserons le théorème de Cherno et nous donnons aussi des illustrations numérique pour justifier ces degrés de convergence. Dans le dernier chapitre nous donnons quelques nouvelles généralisations des théorèmes de point fixe de type Schauder et de type Krasnoselskii qui se basent sur la notion de la compacité faible sur des espaces Fréchet ayant la propriété de Dunford- Pettis et sur la notion de la U-équicontractionIn this thesis we mix the rational approximation procedure, which is a time approximation with approximation in the sense of Kato, which is a space approximation for neutron transport equation. We apply this procedure for explicit and implicit Euler, Crank-Nicolson and Predictor-Corrector schemes which have the rate 1,2 and 3 in the sense of rational approximation. By using Cherno's Theorem, we prove the convergence and we construct also the numerical illustration for justifying the above rate of convergence. In the last chapter, we give some generalization of Schauder and Krasnoselskii fixed point theorems in Dunford-Pettis Frechet spaces and which based on the notion of weakly compactness and U-equicontraction
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Henklein, Petra. "N alpha -Arensulfonyl-Aminosäurechloride." Doctoral thesis, Humboldt-Universität zu Berlin, Mathematisch-Naturwissenschaftliche Fakultät I, 2000. http://dx.doi.org/10.18452/14600.
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Obwohl die methodische Entwicklung der Peptidsynthese gewöhnlich eine automatisierte Herstellung erlaubt, sind für die Herstellung einer Reihe von Peptiden auch gegenwärtig Grenzen gesetzt. Einerseits kann eine im Verlauf der Kettenverlängerung auftretende Bildung intra- und /oder intermolekularer Wasserstoffbrücken zu einer begrenzten Solvatation und damit Zugänglichkeit der zu acylierenden Aminokomponente am Syntheseharz führen, andererseits kommt es beim Einbau sterisch anspruchsvoller Aminosäuren zu ungenügenden Acylierungsausbeuten. Urethangeschützte Aminosäurefluoride haben sich für den Einbau von alpha, alpha-Dialkylaminosäuren als geeignet erwiesen. Die reaktiveren urethangeschützten Aminosäurechloride sind zwar herstellbar, besitzen aber in Gegenwart einer Hilfsbase, die zum Abfangen der während ihrer Reaktion gebildeten HCl notwendig ist, eine zu geringe Stabilität (Oxazolonbildung, Abspaltung der Schutzgruppen). Erst die Verwendung von N(alpha)-Schutzgruppen, die keinen reaktionsfähigen Carbonylkohlenstoff enthalten, wie Arensulfonyl- Schutzgruppen, ermöglichen die volle Ausschöpfung der hohen Reaktivität der Aminosäurechloride. Mit Hilfe dieser Schutzgruppen gelang ein erster Vergleich der Reaktivität der Aminosäurechloride und -fluoride. Bei den durchgeführten Reaktionen wurde keine Stereomutation beobachtet. Unter Verwendung von Arensulfonylschutzgruppen war es erstmals möglich, zwei aufeinanderfolgende N-Alkyl-alpha, alpha-dialkylaminosäuren in Peptide einzubauen. Weiterhin konnten wir zeigen, daß derart geschützte Aminosäuren sich für in situ Aktivierungen mit Thionylchlorid eignen. Als Fänger für überschüssiges Aktivierungsreagenz wurden tertiäre Alkohole bzw. Amine eingesetzt. Arensulfonyl-geschützte Aminosäurechloride haben wir darüber hinaus erfolgreich in der Festphasenpeptidsynthese verwendet. In Kombination von Arensylfonyl-Schutz mit der Standard-Fmoc-Strategie gelang die Synthese eines biologisch aktiven Analogen des CRF, eines 41-mer Peptides mit einer eingefügten Tetrapeptidsequenz -Ala-MeAib-MeAib-Aib-.Despite its wide field of application automatic peptide synthesis is still limited in certain cases. One of the limiting factors is the possibility of intra- or intermolecular hydrogen bond formation during the elongation of the peptide chain. This causes decreased solvation and thus reduced accessibility to the resin-bound amino component. Another limitation is the incorporation of sterically hindered amino acids that usually give rise to insufficient yields of acylation. Urethane protected amino acid fluorides have been shown suitable for the incorporation of alpha,alpha-dialkyl amino acids. Though the more reactive urethane protected amino acid chlorides can be readily synthesized, they do not possess the necessary stability in the presence of an auxiliary base that must be used for trapping of the hydrochloric acid formed during the reaction. Formation of oxazolons and deprotection of formerly protected functional groups would occur. Only the advent of protecting groups for the amino acid N-alpha that do not have a reactive carbonyl function - like arene sulfonyl groups - allowed to take full advantage of the high reactivity of the amino acid chlorides. These protecting groups enabled us to compare the reactivities of amino acid chlorides and fluorides for the first time. We didn't observe any stereo mutation in our experiments. The use of arene sulfonyl protecting groups permitted the consecutive incorporation of two N-alkyl-alpha,alpha-dialkyl amino acids into a peptide for the first time. Furthermore we could show, that amino acids protected in this way, are suitable for in situ activation with thionyl chloride. Tertiary alcohols and amines were used as scavenger for excessive activating reagent. Arene sulfonyl protected amino acids were also successfully used in solid phase peptide synthesis. By combining this protecting concept with the standard Fmoc approach we were able to synthesize a biologically active analogue of CRF, a peptide containing 41 residues into which we inserted the tetrapeptide Ala-MeAib-MeAib-Aib.
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Yung, M. W. "Aminoglycoside ototoxicity : role of amino groups." Thesis, University of Liverpool, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.293012.
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Pudelko, Maciej. "Antigens derived from the mucin MUC1 : Solution and solid-phase synthesis of saccharides, peptides and glycopeptides." Doctoral thesis, Umeå : Department of Chemistry, Umeå Univ, 2008. http://urn.kb.se/resolve?urn=urn:nbn:se:umu:diva-1630.
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Chapman, Rebecca. "Development and Application of Chlorine Solid-State Nuclear Magnetic Resonance and Quantum Chemical Calculations to the Study of Organic and Inorganic Systems." Thèse, Université d'Ottawa / University of Ottawa, 2012. http://hdl.handle.net/10393/20555.
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Chlorine solid-state nuclear magnetic resonance (SSNMR) is an ideal site specific probe of chloride-containing solids as SSNMR tensor properties are sensitive to the local chlorine environment. In this thesis, the development and use of chlorine SSNMR as a method to characterize a wide variety of chemical environments was explored. Ultrahigh field, and multi-field studies were essential to overcome the difficulties associated with the collection of chlorine SSNMR spectra.
Benchmark chemical shift (CS) and electric field gradient (EFG) tensor data were collected for organic chloride systems, including several amino acid hydrochlorides. These experiments demonstrated the sensitivity of chlorine SSNMR to slight changes in chemical environment. Quantum chemical calculations were used to complement experimental data, with the gauge-including projector augmented wave DFT (GIPAW-DFT) method shown to yield better agreement than B3LYP or RHF methods. The GIPAW-DFT method was found to slightly, but systematically, overestimate the chlorine quadrupolar coupling constant and the CS tensor span. Other organic chlorides examined by chlorine SSMR included a known ion receptor, meso-octamethylcalix[4]pyrrole. This compound was found to have a very small quadrupole interaction (QI), but significant chemical shift anisotropy (CSA). GIPAW-DFT calculations were also utilized and, in combination with the experimental results, used to identify the solvate structure of the material analyzed by NMR.
Chlorine SSNMR was further used to study different solvate structures and polymorphism. The technique was an effective means to distinguish different room temperature polymorphs of benzidine hydrochloride, despite the similarities of the chloride environments. In the case of magnesium chloride, chlorine SSNMR was sensitive to the level of hydration and through the use of GIPAW-DFT calculations, the identity of an unknown hydrate was determined.
An analysis of several group thirteen chlorides demonstrated that chlorine SSNMR was also capable of characterizing the chlorine environment in cases where the QI is large, despite the resulting broad line widths. In these systems GIPAW-DFT calculations also yielded excellent agreement with experimental values.
Throughout this research, chlorine SSNMR has been shown to be a useful and effective means to study both organic and inorganic chlorides, with computational methods proving to be an important complement to experimental data.
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McKnight, Michael Vincent. "Heterocycles as amine protecting groups." Thesis, University of Liverpool, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.328176.
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Esam, Odette Amana. "CO2 Capture on Porous Adsorbents Containing Surface Amino Groups." Digital Commons @ East Tennessee State University, 2013. https://dc.etsu.edu/etd/2304.
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The potential impact of carbon dioxide as a major source of global warming has led to extensive research in order to mitigate the greenhouse effect. In this work, four adsorbents were synthesized and studied. The adsorbents were obtained by grafting and sol-gel of amino-containing molecules such as bis[3-(trimethoxysilyl)propyl]amine as monoamine and [3-(2-aminoethylamino)propyl]- trimethoxysilane as diamine on the surface of silica gel. CO2 passed through adsorbents at room temperature for its capture, then desorbed at moderate heating, and stored in the form of insoluble BaCO3. The adsorbent synthesized by sol-gel synthesis was found to be more efficient due to its high content of amino groups. A demonstration experiment on reversible adsorption of CO2 on mesoporous modified silica gel was developed. This experiment visualizes a technology of post-combustion CO2 sequestration from industrial emission gases and its storage.
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Toda, Mitsuaki. "Complement activation on surfaces carrying hydroxyl or amino groups." 京都大学 (Kyoto University), 2010. http://hdl.handle.net/2433/120910.
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Davies, Aaron James. "Aspects of main group metal amido and carbene chemistry." Thesis, Cardiff University, 2004. http://orca.cf.ac.uk/55408/.
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Marsh, Sarah Margaret Beatrice. "New amine-substituted cyclopentadienyl and indenyl ligands." Thesis, Durham University, 1997. http://etheses.dur.ac.uk/5012/.
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This thesis concerns the new amine-substituted cyclopentadiene and indene ligands C(_5)H(_5)(CH(_2))(_3)N((^t)Bu)H and C(_9)H(_7)(CH(_2))(_3)N((^t)Bu)H which can co-ordinate to a metal through all five carbon atoms of the five-membered ring (η(^5)) and/ or through the nitrogen (σ). Chapter 1 reviews the recent literature concerning Lewis-base functionalised cyclopentadienyl and indenyl ligands and their compounds with s-, p-, d- and f-block metals. Chapter 2 contains a brief review of possible synthetic routes to amine-substituted cyclopentadienyl and indenyl ligands with some examples from the recent literature, and a detailed account of the synthesis of C(_5)H(_5)(CH(_2))(_3)N((^t)Bu)H and C(_9)H(_7)(CH(_2))(_3)N((^t)Bu)H. The amino alcohol (^t)BuNH(CH(_2))(_3) OH was synthesised by the conjugate addition of (^t)BuNH(_2) to ethyl acrylate and reduction of the product ester (^t)BuNH(CH(_2))(_2)C0(_2)Et using LiAIH(_4). (^t)BuNH(CH(_2))(_3)OH was converted into (^t)BuNH(CH(_2))(_3)Br.HBr and (^t)BuNH(CH(_2)(_3)Cl.HCl by reaction with HBr or SOCI(_2). Reaction between (^t)BuNH(CH(_2))(_3)C1.HC1 and two equivalents of Na(C(_5)H(_5)) gave C(_5)H(_5)(CH(_2))(_3)N((^t)Bu)H in good yield. Treatment of (^1)BuNH(CH(_2))(_3)C1.HC1 with excess NaOH followed by reaction with Li(C(_9)H(_7)) gave C(_9)H(_7)(CH(_2))(_3)N((^t)Bu)H, also in good yield. Chapter 3 describes the synthesis of various main group and iron compounds of C(_5)H(_5)(CH(_2))(_3)N((^t)Bu)H and C(_9)H(_7)(CH(_2))(_3)N((^t)Bu)H. Lithium salts Li[C(_5)H(_4)(CH(_2))(_3)N((^t)Bu)H], Li[C(_5)H(_4)(CH(_2))(_3)N((^t)Bu)]Li, Li[C(_9)H(_6)(CH(_2))(_3)N((^t)Bu)H] and Li[C(_9)H(_6)(CH(_2))(_3)N((^t)Bu)]Li were prepared for use as reactive intermediates and Li[C(_5)H(_4)(CH(_2))(_3)N((^t)Bu)H] was characterised as its THF-adduct by (^t)H NMR spectroscopy. The silyl derivatives (Me(_3)Si)C(_5)H(_4)(CH(_2))(_3)NH(^t)Bu and (Me(_3)Si)C(_5)H(_4)(CH(_2))(_3)N((^t)Bu)SiMe(_3) were synthesised and characterised by NMR spectroscopy, and (Me(_3)Si)C(_9)H(_6)(CH(_6))(_3)N((^t)Bu)H and (Me(_3)Si)C(_9)H(_6)(CH(_2))(_3)N((^t)Bu)(SiMe(_3)) were also synthesised. The anune-substituted ferrocene Fe{η(^5)-C(_5)H(_4)(CH(_2))(_3)N((^t)Bu)H}(_2) was synthesised and oxidised to the corresponding ferricenium ion which was isolated as its PF(_6)(^-) salt. Exploratory work was carried out into the preparation of heterobimetallic species by reaction between Fe{η(^5)-C(_5)H(_4)(CH(_2))(_3)N((^t)Bu)H}(_2) and MX(_2) (M = Co, Ni, X = CI, M = Mn, X = Br). The substituted bis(indenyl) iron(II) complex Fe{η(^5)-C(_9)H(_6)(CH(_2))(_3)N((^t)Bu)H}(_2) was also synthesised. Chapter 4 is an account of the chemistry of {η(^5) :σ-C(_5)H(_4) (CH(_2))(_3)N(^t)Bu}Ti(NMe(-2))(_2) which was synthesised by an aminolysis reaction between C(_5)H(_5)(CH(_2))(_3)NH(^t)Bu and Ti(NMe(_2))(_4) Reaction between this compound and various weak acids gave a range of new compounds including{η(^5):σ-C(_5)H(_4)(CH(_2))(-3)N(^t)Bu} Ti(O(^t)Pr)(_2), {η(^5):σ-C(_5)H(_4)(CH(_2))(_3)N(^t)Bu)(_2), {η(^5):σC, {η(^5):σ-C(_5)H(_4)(CH(_2))(_3)N(^t)Bu}Ti(C(_5)H(_5))(NMe(_2)) , {η(^5):σ-C(_5)H(_4)(CH(_2))(_3)N(^t)Bu}Ti(SnBu(_3))(_z) and the imido-bridged dimer [{η(^5):σ-C(_5)H(_4)(CH(_2))(_3)N(^t)Bu}Ti(NHPh)](_2)(µ-NPh)2, the X-ray structure of which is reported. Chapter 5 describes the experimental procedures used, and chapter 6 gives lists of characterising data for each compound. Appendix A gives details of the methods used for magnetic susceptibility determinations; appendix B lists X-ray crystallographic data for [ {η(^5):σ-C(_5)H(_4)(CH(_2))(_3)N(^t)Bu}Ti(NHPh)](_2)(µ-NPh)(_2) and appendix C lists departmental colloquia attended.
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Monera, Oscar D. "Chemical modification of amino groups in proteins : part I. Deamination of lysine residues in RNAse A part II. N-cyanomethylation of amino groups in RNAse A /." The Ohio State University, 1988. http://rave.ohiolink.edu/etdc/view?acc_num=osu14875968078243.
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Taylor, Morgan James. "Chemistry of β-diketiminate Group 14 and Group 2 complexes and macrocyclic amines and amine ethers." Thesis, University of Sussex, 2012. http://sro.sussex.ac.uk/id/eprint/39640/.
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Group 14 metal(II) alkyl complexes are very rare, with few examples being studied in great detail. To this end, a series of β-diketiminate lead(II) alkyl and aryl complexes, [{(2,6-iPr2C6H3)NC(CH3)}2CH]PbR (R = Me, iPr, sBu, Np, Bn, tBu and Ph) were synthesised and a number of computational studies were performed on them to increase the understanding of the nature of these compounds. Reactivity studies on both the lead, and the analogous tin systems, showed that they could be used as precursors to generate examples of very rare two-coordinate group 14 metal cation complexes, including the first example of a β-diketiminate two-coordinate lead(II) cation, and an analogous example of a rare low-coordinate tin(II) system. These were studied in detail by computational methods, including the stabilising effects of a coordinated solvent molecule on the metal centre. β-Diketiminate magnesium alkyl complexes were generated to investigate the +2 oxidation state metal environment without the presence of a stereochemically active lone pair, as present in the group 14 metal(II) complexes. A carbodiimide was successfully inserted into the magnesium-carbon bond, and novel magnesium phosphides were generated from the alkyl complexes. Solvent stabilisation effects on these phosphides were also studied by computational methods. A series of macrocyclic amines and amine ethers were synthesised to investigate the hydrolysis of a phosphate diester model RNA system by lead(II) salts, monitored by UV-visible kinetics. The reaction kinetics gave no reproducible results, but the syntheses of the macrocycles are presented in detail for further citation.
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Kucheryna, Andriy. "Syntheses and properties of compounds containing the bis(trifluoromethyl)amido group." [S.l.] : [s.n.], 2006. http://deposit.ddb.de/cgi-bin/dokserv?idn=983674019.
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Whannel, Robert Alexander. "Synthesis and reactivity studies of novel group 4 diamido amine complexes." Thesis, University of Oxford, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.442983.
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Xie, Jenny X. "Regulation of BACH1/FANCJ Function in DNA Damage Repair: A Dissertation." eScholarship@UMMS, 2009. https://escholarship.umassmed.edu/gsbs_diss/435.
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The DNA damage response (DDR) pathway is a complicated network of interacting proteins that function to sense and remove DNA damage. Upon exposure to DNA damage, a signaling cascade is generated. The damage is either removed, restoring the original genetic sequence, or apoptosis is activated. In the absence of DDR, cells are unable to effectively process DNA damage. Unprocessed DNA damage can lead to chromosomal changes, gene mutations, and malignant transformation. Thus, the proteins involved in DDR are critical for maintaining genomic stability.
One essential DDR protein is the BRCA1 Associated C-terminal Helicase, BACH1. BACH1 was initially identified through its direct association with the BRCT domain of the Breast Cancer Associated Gene, BRCA1. Similar to BRCA1, germline mutations in BACH1were identified in patients with early onset breast cancer. Interestingly, the disease-associated mutations in BACH1 were shown to have altered helicase activity in vitro, providing a direct link between BACH1 helicase activity and disease development. The correlation between BACH1 and cancer predisposition was further confirmed by the identification of BACH1 as the cancer syndrome Fanconi anemia (FA) gene product, FANCJ. Similar to other FA proteins, suppression of FANCJ leads to decreased homologous recombination, enhanced sensitivity to DNA interstrand crosslinking (ICL) agents, and chromosomal instability.
In an effort to further understand the function of FANCJ in DDR, FANCJ was shown to directly associate with the mismatch repair (MMR) protein MLH1. This interaction is facilitated by lysines 141 and 142 within the helicase domain of FANCJ. Importantly, the FANCJ/MLH1 interaction is critical for ICL repair. Furthermore, in an attempt to dissect the binding site of FANCJ on MLH1, we discovered an HNPCC associated MLH1 mutation (L607H) that has intact mismatch repair, but lacks FANCJ interaction. In contrast to the MLH1 interaction, the FANCJ/BRCA1 interaction was not required for correcting the cellular defects in FANCJ null cells. Thus, in an effort to understand the functional significance of the FANCJ/BRCA1 interaction, we discovered that FANCJ promotes Pol η dependent translesion synthesis (TLS) bypass when uncoupled from BRCA1. In this thesis, we provide evidence suggesting that FANCJ and MLH1 are functionally linked and that the interaction of these proteins is critical for repair choice.
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Meyer-Plath, Asmus Andres. "Grafting of amino and nitrogen groups on polymers by means of plasma functionalisation." [S.l.] : [s.n.], 2002. http://deposit.ddb.de/cgi-bin/dokserv?idn=972339787.
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Melichar, Heather J. "SOX13, A γδ T Cell-Specific Gene, Is a WNT-Signaling Antagonist Regulating T Cell Development: A Dissertation." eScholarship@UMMS, 2006. https://escholarship.umassmed.edu/gsbs_diss/251.
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Mature αβ and γδ T cells arise from a common precursor population in the thymus. Much debate has focused on the mechanism of T cell lineage choice made by these multi-potential precursor cells. It is widely believed that the decision of these precursor cells to commit to the γδ or αβ T cell lineages is regulated primarily by a specific instructive signal relayed through the appropriate T cell receptor. Contrary to this model, we present evidence for a TCR-independent lineage commitment process. Comparison of global gene expression profiles from immature αβ and γδ lineage thymocytes identified Sox13, an HMG-box transcription factor, as a γδ T cell-specific gene. Unlike other HMG-box transcription factors such as TCF1, LEF1 and SOX4, that are critical for proper αβ T cell development, Sox13 expression is restricted to early precursor subsets and γδ lineage cells. Importantly, SOX13 appears to influence the developmental fate of T cell precursors prior to T cell receptor expression on the cell surface. Transgenic over-expression of Sox13 in early T cell precursors strongly inhibits αβ lineage development, in part, by inhibiting precursor cell proliferation and concomitantly, leading to increased cell death among αβ lineage subsets. Steady-state γδ T cell numbers, however, appear unaffected. Strikingly, the DP αβ lineage cells that do develop in Sox13 transgenic mice are imprinted with a γδ- or precursor-like molecular profile, suggesting that SOX13 plays an active role in the lineage fate decision process or maintenance. Sox13-deficient mice, on the other hand, have selectively reduced numbers of γδ thymocytes, indicating that SOX13 is essential for proper development of γδ T cells. We present additional data demonstrating that SOX13 is a canonical WNT signaling antagonist modulating TCF1 activity, raising a strong possibility that WNT signals, and their modulators, are at the nexus of γδ versus αβ T cell lineage commitment.
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Bonnin, Quentin. "New cationic group 4 metallocenes as potential organometallic frustrated Lewis pairs : synthesis, reactivity and catalysis." Thesis, Bourgogne Franche-Comté, 2017. http://www.theses.fr/2017UBFCK031.
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Le concept de “paires frustrées de Lewis” (plus communément désignés par l’acronyme anglais FLPs) a suscité un vif intérêt depuis sa formulation en 2006. Initialement décrit à partir d’une phosphine encombrée comme base de Lewis et d’un borane comme acide de Lewis pour l’activation coopérative d’hydrogène sans métal, ce concept a été ensuite très largement développé en utilisant divers éléments du groupe principal (N/B, P/Al, N/Al …). Le concept a ensuite été étendu aux métaux de transitions pour pallier cette faiblesse: sont ainsi apparues les premières paires frustrées de Lewis organométalliques (OmFLPs). Dans le but de développer de telles OmFLPs, nous nous sommes intéressés à la synthèse de complexes cationiques titanocèniques et zirconocèniques en présence d’une amine. La première partie de cette thèse présente les travaux précédemment décrits sur les ligands azotés, en vue de synthétiser des complexes du groupe 4 N-fonctionnalisés. Une description plus détaillée du concept de FLP est ensuite réalisée, et un parallèle est fait avec des concepts connexes (coopérativité métal-ligand, systèmes ambiphiles). La seconde partie de ce manuscrit développe la synthèse de nouveaux ligands (aminomethyl)cyclopentadiènylure de potassium ainsi qu’une étude de leur coordination aux métaux du groupe 4. Cette étude a permis d’accéder à toute une série de nouveaux complexes dichlorotitanocènes et zirconocènes porteurs d’une fonction amine tertiaire encombrée (diisopropylaminyl et 2,2,6,6-tétraméthylpipéridine) à proximité du centre métallique. Ces travaux ont montré que l’amine ne se coordine pas audit centre métallique. Les métallocènes ainsi formés ont ensuite été transformés en cation afin de renforcer le caractère acidité de Lewis du centre métallique. Ces espèces ont montré une réactivité inattendue donnant lieu à des réarrangements par activation CH au voisinage de l’atome d’azote. Ces réarrangements ainsi que des études mécanistiques font l’objet du troisième chapitre. La quatrième partie de ce mémoire porte sur la synthèse de complexes phosphido- et amidotitanocènes cationiques. Ces complexes montrent une très bonne activité en catalyse d’hydrogénation de petites molécules dans des conditions relativement douces, vraisemblablement pour des raisons d’effets coopératifs entre le métal et le ligand. Dans une dernière partie, la synthèse de complexes titanocéniques cationiques portant une fonction iminophosphorane est développée, suivie d’une étude de réactivité de ces complexes en tant que paires frustrées de Lewis organométalliquesIn 2006, the concept of “frustrated Lewis pairs” (called FLPs) was introduced. The main characteristic of these compounds is their ability to activate cooperatively small molecules without the use of a metal (H2, CO2, alkene alkyne…). Initially based on P/B combination, the concept has been extended to several other main group elements (N/B, P/Al, N/Al …). Recently, FLPs have been extended to the transition metal realm. These organometallic FLPs (OmFLPs) are obviously non-metal free systems but they extend significantly the scope of FLP applications. Seeking to develop such systems, a research toward new omFLP combinations (N/Ti+, N/Zr+) has been initiated in our group, based on the synthesis of N-based titanocene and zirconocene complexes. The first part of this manuscript deals with a survey of the literature of such compounds, and a more detailed presentation of FLPs and related concepts (metal-ligand cooperativity, ambiphilic ligands) are also developed. In a second chapter, the synthesis of new N-based cyclopentadienyl ligands and their coordination to group 4 metals is presented. The formation of a cationic complex is then developed in a third part on selected titanocenes. In these complexes, the amine function undergoes CH activation by the cationic metal centre, leading to unexpected rearrangements. Investigations on their plausible mechanism are also presented. In a fourth part, the synthesis of new cationic phosphido- and amidotitanocenes, discovered in the course of our study on OmFLPs, is developed. The cationic amidotitanocenes are shown to be catalytically active towards hydrogenation of small molecules. Lastly, the potential of cationic titanocenyl iminophosphoranes as OmFLPs, was developed
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Tinkler, Suzanne. "Synthesis and properties of group 4 amido complexes and related lithium amide intermediates." Thesis, University of Warwick, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.302651.
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Kister, Olesya Evgen'evna [Verfasser], and Frank [Akademischer Betreuer] Rößner. "Interaction of amino acids with different ionogenic groups / Olesya Evgen'evna Kister. Betreuer: Frank Rößner." Oldenburg : IBIT - Universitätsbibliothek, 2012. http://d-nb.info/1019362669/34.
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Mukiza, Janvier. "Rhenium complexes with pontentially multidentate ligands containing the amino, imino, hydroxy and thiol groups." Thesis, Nelson Mandela Metropolitan University, 2016. http://hdl.handle.net/10948/12308.
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The chemistry of rhenium has received considerable interest due to its versatility in various catalytic applications, fixation and especially the potential use of 186Re and 188Re radionuclides in nuclear medicine. This study investigates the synthesis and characterisation of rhenium complexes with potentially multidentate ligands containing the amino, imino, hydroxyl and thiol groups. It reports new rhenium complexes in the +1, +3, +4 and +5 oxidation states, which display structural diversity, from monomers to ligand-bridged dimers as well as metal-metal multiply bonded dimers. The reaction of orotic acid (H2oa) and 2-mercapto-orotic acid (H2moa) with trans- [ReOX3(PPh3)2] (X = Cl, Br) were studied and led to the formation of ligand-bridged dimers with metal-metal multiple bonds i.e. (μ-Br)(μ-O)(μ-oa)[Re2 IVBr(OEt)2(PPh3)2], (μ-X)(μ-O)(μ-oa)[Re2 IVX2(OiPr)(PPh3)2] and (μ-Cl)(μ-O)(μ-moa)2[Re(PPh3)]2. The reaction of H2oa with [ReO2(py)4]Cl, [Re(dab)Br3(PPh3)2] (H2dab = 1,2- diaminobenzene) and [Re(CO)5Cl] were also studied and monomeric complexes [ReO(py)2(OEt)(oa)], [Re(dab)Br(oa)(PPh3)2] and (Ph4P)[Re(CO)3(H2O)(oa)] were isolated. The treatment of 5-amino-orotic acid (H2aoa) with [ReOBr3(PPh3)2] led to dimers with metal-metal triple bonds ReIV≡ReIV i.e. (μ-Br)(μ-O)(μ-oa)[Re2 IVBr(OEt)2(PPh3)2], (μ-Br)(μ-O)(μ-oa)[Re2 IVBr2(OiPr)(PPh3)2], as well as the monomer [ReV(apd)Br(aoa)(PPh3)2] (apd2− = 5-imidopyrimidine-2,4-dione). The chelating ligand 5-aminopyrimidine-2,4-dione (H2apd) was formed by oxorhenium(V)-catalysed decarboxylation of 5-amino-orotic acid (H2aoa) (see Scheme 1). The reaction of the Schiff base derivative of 5-amino-ortic acid, salicylimine-orotic acid (H2soa), with trans-[ReOI2(OEt)(PPh3)2] in ethanol was also investigated and led to the formation of the rhenium(III) complex salt [Re(coa)I(PPh3)2]I [Hcoa = 5-(2- hydroxybenzylideneamino)pyrimidine-2,4(1H,3H)-dione]. The chelating Hcoa is also formed from the oxorhenium(V)-catalysed decarboxylation of H2soa and coordinates to the rhenium(III) ion as a monoanionic tridentate N,O,O-donor chelate via the phenolate and ketonic oxygens, and the imino nitrogen atom. However, decarboxylation of H2soa was not observed in its reaction with [ReOCl3(PPh3)2], which led to the isolation of [ReOCl(soa)(PPh3)]. The reaction of the carboxamide derivative of 5-aminoorotic acid, 5-(5-aminopyrimidine-2,4(1H,3H)- dioxamido)-1,2,3,6-tetrahedro-2,6-dioxopyrimidine-4-carboxylic acid (H2ampa) with [Re(CO)5Cl] in ethanol led to the formation of a zwitterionic rhenium(I) complex [Re(CO)3(H2O)(amef)] [amef = {5-(5-ammoniumpyrimidine-2,4(1H,3H)-dioxamido)- 1,2,3,6-tetrahedro-2,6-dioxopyrimidine-4-ethylformate}]. The chelating ion amef was formed from the combined tricarbonylrhenium(I)-catalysed esterification and aminoprotonation of H2ampa (see Scheme 1) and coordinates to the fac-[Re(CO)3]+ core as a dianionic bidentate N,N-donor chelate via the amido nitrgens.
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Voelk, Eric K. "Synthesis of 3,8-dicarbethoxyamino-2,4,7,9-tetrafluorophenanthridine and 3,8-dicarbethoxyamino-2,4,7,9-tetrafluorobenzo(c)cinnoline /." Connect to this title online, 1987. http://rave.ohiolink.edu/etdc/view?acc%5Fnum=osu1106769279.
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Silva, José Gláucio da. "Propriedades Vibracionais do Dipeptídeo L-Alanil-Alanina submetido a deformações homogêneas." reponame:Repositório Institucional da UFC, 2015. http://www.repositorio.ufc.br/handle/riufc/15578.
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SILVA, José Gláucio da. Propriedades Vibracionais do Dipeptídeo L-Alanil-Alanina submetido a deformações homogêneas. 2015. 131 f. Tese (Doutorado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2015.Submitted by Edvander Pires (edvanderpires@gmail.com) on 2016-03-18T16:45:00Z No. of bitstreams: 1 2015_tese_jgsilva.pdf: 4602304 bytes, checksum: c589f914ff64a0ac8fd63892133504ba (MD5)
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The dipeptide L-Alanyl – L-Alanine crystal was studied through polarized Raman scattering submitted to homogeneous deformations. The crystals were grown by slow evaporation technique from an aqueous supersaturated solution of the crystal powder. Rays-x diffractions measurements were realized to confirm a crystalline structure of the crystal. Polarized Raman scattering measurements were performed at room temperature, as well as the analysis of the group theory to the C4 factor group and a tentative assignment of the vibrational modes of crystal. Raman scattering measurements in the crystals as a function of temperature were realized between two intervals of temperature: first, at low temperature between 300 K and 11 K e 11 K and 300 K, and second, at high temperature between 300 K e 520 K and 520 K e 300 K, in the spectral range of 50 cm-1 to 3400 cm-1. From the results of low temperature measurements, it was possible to conclude that the crystal undergoes a second-order phase transition between 80 K and 60 K, from a tetragonal structure with C4 factor group to a monoclinic structure with C2 factor group, maintaining the same number of the molecules per primitive cell. The suggested mechanism to explain the phase transition is the occupation of non-equivalent sites by CH3 molecular groups present at Ala-Ala molecule. On the other hand, the crystal remained stable in the high temperature range studied, and the changes observed in the Raman spectra showed no evidence that the Ala-Ala crystal undergone phase transition or changes in molecule conformation. In those experiments were observed only quantitative changes in frequency and widths of the Raman modes, which are normal for any material subjected to variations in temperatures around 220 K. Raman scattering measurements in the crystals as a function of pressure in the pressure range between 0,1 GPa and 6,3 GPa, in compression and of 6,3 GPa and 0,1 GPa, in decompression, in the spectral region between 100 cm-1 and 3400 cm-1 showed two ranges where several qualitative changes occurred; the first, in low pressure interval between 1.7 GPa and 2.3 GPa and the second, at high pressure interval, between 4.5 GPa and 4.9 GPa. Between 1.7 GPa and 2.3 GPa, it was observed qualitative changes as well as the disappearance of an external mode around of 130 cm-1 and the anomalous behavior of other external mode around of 110 cm-1 for pressures of the order of 1,7 GPa. These qualitative changes suggest that the crystal exhibits a second order structural phase transition. Qualitative changes also were observed in others regions of the Raman spectrum through of special reorientation of the molecular groups CO2, CH3 and NH3. These qualitative changes characterize a structural second order phase transition. The mains qualitative changes observed between 4,5 GPa and 5,2 GPa were the disappearance of the external modes and the an large increasing of the width of the Raman modes, suggesting that the crystal exhibits a structural disorder in the crystalline structure when undergoes a phase transition for high pressures, possibly a amorphization. When performing decompression of the sample, the Raman spectrum returns to its initial form relative to pressure of 0,1 GPa indicating reversibility of phase transitions.
O cristal dipeptídeo L-Alanil-L-alanina (Ala-Ala) foi estudado através da técnica de espalhamento Raman polarizado submetido a deformações homogêneas. Os cristais foram crescidos pela técnica de evaporação lenta a partir de uma solução aquosa supersaturada do pó do cristal. Medidas de raios-x foram realizadas para confirmar a estrutura cristalina do cristal. Foram realizadas medidas de espalhamento Raman polarizado a temperatura ambiente, bem como análise da teoria de grupos para o grupo fator C4 juntamente com uma classificação exploratória dos modos normais de vibração do cristal. As medidas de espalhamento Raman foram realizadas em baixas temperaturas, entre 300 K e 11 K e 11 K e 300 K, e altas temperaturas, entre 300 K e 520 K e 520 K e 300 K, na região espectral de 50 a 3300 cm-1. Da análise dos resultados das medidas de baixas temperaturas foi possível concluir que o cristal exibe uma transição de fase de segunda ordem, entre 80 e 60 K, passando continuamente da estrutura tetragonal com grupo fator C4 para uma estrutura monoclínica com grupo fator C2 mantendo o mesmo número de moléculas na célula primitiva. O mecanismo proposto para explicar a transição de fase é a ocupação de sítios de simetria C1 não equivalentes pelos íons moleculares CH3 numa estrutura monoclínica pertencente ao grupo fator C2. O cristal manteve-se estável em todo o intervalo de alta temperatura estudado. Nestas experiências foram observadas apenas mudanças quantitativas nas frequências e larguras de linha dos modos Raman estudados, que é normal para qualquer material submetido a variações de temperaturas da ordem de 220 K. Medidas de espalhamento polarizado no cristal de Ala – Ala no intervalo de pressão entre 0,1 GPa e 6,3 GPa, na compressão, e de 6,3 GPa e 0,1 GPa, na descompressão, na região espectral de 100 cm-1 a 3400 cm-1 mostraram dois intervalos de pressão em que ocorrem diversas mudanças qualitativas; o primeiro entre 1,7 GPa e 2,3 GPa e o segundo entre 4,5 GPa e 4,9 GPa. Entre 1,7 GPa e 2,3 GPa foram observadas mudanças qualitativas significantes na região dos modos externos, tais como, o desaparecimento de um modo da rede em torno de 130 cm-1 e o comportamento anômalo de outro modo da rede em torno de 110 cm-1 para pressão de 1,7 GPa. Estas mudanças qualitativas sugerem que o cristal exibe uma transição de fase estrutural de segunda ordem. As outras regiões do espectro Raman do cristal apresentaram diversas mudanças qualitativas continuas no comportamento dos modos Raman das unidades que participam diretamente das pontes de hidrogênio, indicando que o cristal apresenta reorientações espaciais dos grupos moleculares CO2, CH3 e NH3. Estas mudanças qualitativas caracterizam uma transição de fase estrutural de segunda ordem. As principais mudanças qualitativas observadas entre 4,5 GPa e 5,2 GPa são o desaparecimento dos modos externos e, quantitativamente, um grande aumento na largura de linha dos modos Raman indicando que o cristal exibe uma desordem na estrutura cristalina durante a transição de fase de altas pressões, possivelmente uma amorfização. Na descompressão da amostra os espectros Raman são quase que totalmente recuperados na sua forma inicial indicando que o cristal apresenta transições de fase reversíveis.
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Piet, Marvin. "Synthesis and characterization of new adsorbents for CO2 capturing." University of the Western Cape, 2014. http://hdl.handle.net/11394/4464.
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Philosophiae Doctor - PhDCarbon dioxide emissions have become a major concern as they are one of the contributing factors to the “green-house” effect. Recently, much effort has been put into separating carbon dioxide (CO2) from flue gases linked to the combustion processes at fixed point sources. The development of solid sorbents for adsorption based on CO2 capture has attracted much attention. Ordered Mesoporous Silica (OMS) materials have recently attracted much attention as solid adsorbents for capturing CO2. OMS have been investigated for this purpose owing to their high pore volume, large surface area and ease of functionalizationIn this work we report on the synthesis of OMS viz. MCM-41 and SBA-15 along with amorphous silica as adsorbents for CO2 capture. MCM-41 was prepared with surfactants having different alkyl chain lengths (C14TABr, C16TABr and C18TABr) where TABr is trimethylammonium bromide. SBA-15 was prepared using a Triblock copolymer as a structure directing agent for the organization of polymerizing silica species. Commercial amorphous silica gel was used for comparative purposes. Initial characterization OMS with powder X-Ray diffraction (XRD) and small angle diffraction (SAXS) yielded diffraction patterns which may be associated with well-ordered structures of hexagonal mesoporous material. Ease of preparation for MCM-41 materials allowed for convenient scale- up, obtaining highly ordered mesoporous silica MCM-41 at room temperature. SBA-15 was also found to be scaled up with considerable ease through increasing the volume of the autoclave during hydrothermal treatment. Structural, morphological and textural properties of the adsorbents were characterized by N2 physisorption measurements, Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM) and Thermogravimetric Analysis (TGA). TEM confirmed the hexagonal structure; SEM showed that C14MCM-41 had spheroidal particle morphology whereas SBA-15 displayed rod-like structures. High surface areas of up to 1302, 1186, 1211 and 1024 m2/g for C14MCM-41, C16MCM-41, C18MCM-41 and SBA-15, respectively were obtained. The pore size of MCM-41 materials was increased from 2.6 nm for C14MCM-41 to 4.4 nm in diameter for C18MCM-41 using surfactants with different alkyl chain lengths. CO2 adsorption characteristics of OMS were studied using CO2-temperature programmed desorption (TPD). The results showed that C14MCM-41, C16MCM- 41, C18MCM-41 and SBA-15 desorbed 0.19, 0.16, 0.11 and 0.26 mmol/g respectively. The synthesized OMS were then further modified by grafting various amine moieties on their surfaces in order to increase their CO2 adsorptive capabilities. 3-(Aminopropyl)triethoxysilane (APS), N-[3-(trimethoxysilyl)propyl]ethylene- diamine (TPED), 3-chloropropyl)-trimethoxysilane (CPS), ethyl 2-bromopropanoate, tris(2-aminoethyl)amine (TREN) and guanidine. Several characterization techniques such as XRD, SAXS, HRTEM, HRSEM, TGA, Fourier Transform Infra-Red (FT-IR) spectroscopy, CO2 isotherms and CO2-TPD were used to analyze amine grafted solid sorbents for CO2 capture. The results revealed that the structural integrity of the amine modified sorbents was not compromised during the grafting process. The structural properties of the supports, such as surface area and pore size, nature of amine and the number of amine groups, affected the loading and CO2 adsorption capacity of chemically grafted sorbents. APS grafted amorphous silica gel adsorbed 0.67 mmol/g CO2, which proved to be the highest compared to C18MCM-41 and SBA-15 grafted with APS and TPED. C18MCM-41, SBA-15 and amorphous silica gel were also grafted with TREN and adsorbed 0.42, 0.51 and 0.27 mmol/g of CO2, respectively. A systematic study of guanidine grafted on C14MCM-41, C16MCM-41 and C18MCM-41 was investigated, for the first time, to the best of our knowledge. Structural properties like variation in pore size, proved to enhance the adsorption capacity of the adsorbent, coupled with the guanidine molecules grafted on MCM-41 materials. C18MCM-41-guanidine showed the highest CO2 uptake of the guanidine grafted MCM-41 materials, adsorbing 0.30 mmol/g. A novel synthetic route to TPED-TREN grafted C18MCM-41 and SBA-15, using ethyl 2-bromopropanoate as a linker, was investigated as a potential adsorbent for CO2 capture, for the first time. C18MCM-41-TPED-TREN and SBA-15-TPED-TREN CO2 adsorption capacity were found to be 0.14 and 0.14 mmol/g, respectively.
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Hafeez, Muhammad [Verfasser]. "Novel Group 4 Metal Amido Complexes - syntheses, reactivity and olefin polymerization catalysis / Muhammad Hafeez." Bayreuth : Universität Bayreuth, 2012. http://d-nb.info/1059413191/34.
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Hua, Zeai. "Photoinduced birefringent properties of amorphous polymers containing amino-sulfonyl azobenzene groups in their side chains." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape7/PQDD_0003/MQ42632.pdf.
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Moyes, Christopher D. "Catabolism of osmotically-active amino acids in two groups of osmoconformers, bivalve molluscs and elasmobranchs." Thesis, University of Ottawa (Canada), 1986. http://hdl.handle.net/10393/5139.
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Caetano, Mariana. "Estudo das perdas de amido em confinamentos brasileiros e do uso do amido fecal como ferramenta de manejo de bovinos confinados." Universidade de São Paulo, 2008. http://www.teses.usp.br/teses/disponiveis/11/11139/tde-28072008-152702/.
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O número de animais terminados em sistema de confinamento cresce rapidamente no Brasil, concomitante com aumento no teor de amido das dietas utilizadas. A expansão da agricultura e custos mais baixos por unidade de energia digestível proveniente do grão em relação aos volumosos deve acelerar este processo. Os objetivos deste trabalho foram: a) avaliar as perdas de amido em confinamentos comerciais; b) calibrar a metodologia de NIRS para estimativa do teor de amido fecal; c) estudar as relações entre parâmetros fecais (% de amido, MS e pH) com desempenho e eficiência de bovinos Nelore e cruzados recebendo dietas de médio/alto concentrado; d) avaliar o efeito do horário de coleta e da raça dos animais no teor de amido fecal. Foram avaliados os teores de amido fecal de animais de experimentos controlados e de confinamentos comerciais. Resultados de 2.003 amostras para teor de amido fecal foram analisados. Foi observada diferença no teor de amido fecal em função do horário de coleta tanto em experimento quanto em confinamentos comerciais (P < 0,01). Os teores de amido fecal em animais 100% Nelores foram maiores em comparação com o de animais cruzados (P < 0,01). Há necessidade de padronização do horário da coleta e grupo genético para utilizar o teor de amido nas fezes como indicador do uso de amido. Para os dados de experimentos controlados houve efeito de experimento (P < 0,0001), sexo (P = 0,006) e grupo genético (P = 0,0466), sendo maior o teor de amido fecal para machos e animais Nelore, quando comparados com fêmeas e cruzados. A correlação com amido nas fezes foi baixa (r < 0,20) para as variáveis peso médio metabólico (kg0,75), consumo de matéria seca (kg/dia) e eficiência alimentar (kg/kg). Não houve correlação entre teor de amido fecal e consumo alimentar residual (CAR) para novilhas e touros Nelore, demonstrando que talvez o amido nas fezes não seja um boa ferramenta para selecionar os animais mais eficientes em dietas de baixo teor de amido. A correlação entre o teor de amido fecal com pH fecal para animais em confinamentos comerciais apresentou correlação negativa de r = -0,57 e -0,51 quando a fonte de amido foi milho e sorgo, respectivamente. Foi detectada diferença (P =0,0006) no teor de pH fecal em função da fonte de amido da dieta (milho ou sorgo), 6,55 para o milho e 6,04 para o sorgo, sugerindo um menor aproveitamento do amido para os grãos de sorgo, embora o teor de amido fecal para as diferentes fontes avaliadas não tenha sido diferente (P = 0,29). Já para a %MS fecal, houve efeito de fonte de amido (P = 0,06), sendo os teores para milho menores (20,5%) em relação ao sorgo (23,1%). As 1.985 análises de amido nas fezes tanto dos experimentos quanto dos confinamentos comerciais permitiram a obtenção e validação de uma equação de calibração do NIRS para teor de amido fecal. Uma parte dos dados coletados foram utilizados na calibração e outra parte na validação independente da equação. Foram feitas equações para três diferentes conjuntos de amostras: a) todas independente da fonte de amido; b) amostras contendo o milho como principal fonte de amido; c) amostras contendo o sorgo como principal fonte de amido. Todas as equações apresentaram boa habilidade preditiva (R2 > 0,92), alta acurácia (erros sistemático inferior a 2% do teor de amido fecal) sendo que uma única equação pode ser utilizada para estimar o teor de amido fecal independente da fonte de amido da dieta.The number of animals finished in the feedlot system is rapidly growing in Brazil. At the same time there is an increase in the starch content of the diets. The expansion of grain production and lower costs of digestible energy from grain compared to roughages should accelerate this process. The objectives of this work were: a) evaluate starch losses in commercial feedlots; b) develop the NIRS methodology for fecal starch content; c) study the relationships between fecal parameters (%starch, dry matter and pH) with performance efficiency of Nellore and crossbreed cattle receiving diets of medium/high concentrate; d) evaluate the effect of time at fecal sample collection and animal breed on fecal starch content. The fecal starch content was determined on 2,003 samples. Fecal starch content was affected by time of fecal sample collection both in the controlled experiment and in commercial feedlots (P < 0.01). There was higher fecal starch content in animals 100% zebu compared to B. taurus crossbreds (P < 0.01). There is a need to standardize the time of collection and genetic group to use fecal starch as a management tool. There was an effect of experiment (P < 0.0001), sex (P = 0.006) and genetic group (P = 0.0466), with higher fecal starch content found for males, Nellore, when compared to females and crossbreds. The correlations between fecal starch and metabolic mid weight (kg0.75), dry matter intake (kg/day) and feed efficiency (kg/kg) were low (r < 0.20). There was no correlation between fecal starch content and residual feed intake for Nellore heifers or bulls, suggesting starch content is not a good tool to determine efficient animals fed medium concentrate diets. The correlation between the level of fecal starch and fecal pH for animals in commercial feedlots showed a negative correlation of r = -0.57 and -0.51 when corn and sorghum were the sources of starch. Fecal pH was different (P = 0.0006) depending on the source of the dietary starch, 6.55 and 6.04 for corn and sorghum respectively, suggesting lower efficiency of starch use with sorghum. However there was no difference in fecal starch percentage for the two starch sources evaluated (P = 0.29). For the fecal DM, there was an effect of source of starch (P = 0.06), lower for corn (20.5%) when compared to sorghum (23.1%). The database obtained with the 1,985 lab analysis of fecal starch from both controlled experiments and commercial feedlots were used to develop a NIRS calibration equation for fecal starch content. Part of the analysis was used to independently validate the equations. Equations were developed from three different sets of samples: a) all samples regardless the starch source; b) samples where corn was the main source of starch c) samples were sorghum was the main source of starch. All equations had good predictive ability, with high regression coefficients (R2 > 0.92) and low bias (< 2%) indicating high accuracy with independent data. Results suggest a single equation can be used to estimate the fecal starch regardless the source of starch in the diet.
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GaucheÌ, CeÌline. "Amine end groups in nylon fabrics and their effect on photostability." Thesis, University of Leeds, 2007. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.439573.
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Cline, Meredith R. "The reactions of acetylphenyl and tetrafluoro acetylphenylnitrene with functional groups present in amino and nucleic acids." Connect to resource, 2006. http://hdl.handle.net/1811/6522.
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Thesis (Honors)--Ohio State University, 2006.Title from first page of PDF file. Document formatted into pages: contains 133 p.; also includes graphics. Includes bibliographical references (p. 130-133). Available online via Ohio State University's Knowledge Bank.
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Litman, Rachel. "Characterization of the BACH1 Helicase in the DNA Damage Response Pathway: a Dissertation." eScholarship@UMMS, 2007. https://escholarship.umassmed.edu/gsbs_diss/329.
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DNA damage response pathways are a complicated network of proteins that function to remove and/or reverse DNA damage. Following genetic insult, a signal cascade is generated, which alerts the cell to the presence of damaged DNA. Once recognized, the damage is either removed or the damaged region is excised, and the original genetic sequence is restored. However, when these pathways are defective the cell is unable to effectively mediate the DNA damage response and the damage persists unrepaired. Thus, the proteins that maintain the DNA damage response pathway are critical in preserving genomic stability.
One essential DNA repair protein is the Breast Cancer Associated gene, BRCA1. BRCA1 is essential for mediating the DNA damage response, facilitating DNA damage repair, and activating key cell cycle checkpoints. Moreover, mutations in BRCA1 lead to a higher incidence of breast and ovarian cancer, highlighting the importance of BRCA1 as a tumor suppressor. In an effort to better understand how BRCA1 carried out these functions, researchers sought to identify additional BRCA1 interacting proteins. This led to the identification of several proteins including the BRCA1 Associated C-terminal Helicase, BACH1. Due to the direct interaction of BACH1 with a region of BRCA1 essential for DNA repair and tumor suppression, it was speculated that BACH1 may help support these BRCA1 function(s). In fact, initial genetic screenings confirmed that mutations in BACH1 correlated not only with hereditary breast cancer, but also with defects in DNA damage repair processes.
The initial correlation between BACH1 and cancer predisposition was further confirmed when mutations in BACH1 were identified in the cancer syndrome Fanconi anemia (FA) (complementation group FA-J), thus giving BACH1 its new name FANCJ. These findings supported a previously established link between the FA and BRCA pathways and between FA and DNA repair. In particular, we demonstrated that similar to other FA/BRCA proteins, suppression of FANCJ lead to a substantial decrease in homologous recombination and enhanced both the cellular sensitivity to DNA interstrand cross-linking agents and chromosomal instability. What remained unknown was specifically how FANCJ functioned and whether these functions were dependent on its interaction with BRCA1 or other associated partners. In fact, we identified that FANCJ interacted directly with the MMR protein MLH1. Moreover, we found that the FANCJ/BRCA1 interaction was not required to correct the cellular defects in FA-J cells, but rather that the FANCJ/MLH1 interaction was required. Although both the FA/BRCA and MMR pathways undoubtedly mediate the DNA damage response, there was no evidence to suggest that these pathways were linked, until recently. Our findings not only indicate a physical link between these pathways by protein-protein interaction, but also demonstrated a functional link.
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Guardado, Puentes Julian. "Trans diequatorially fused 3',3'-Diphenyl-2'-morpholinone derivatives of 2-Amino-2-deoxy-D-glucose." Scholarly Commons, 1985. https://scholarlycommons.pacific.edu/uop_etds/2113.
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The chemistry of amino sugar compounds has been studied in the last years in connection with the study of natural products, and many of them have been isolated. 57,17,18 Amino sugars play an important role in biochemistry, forming blocks of homo- and heteropolymers and complex molecules such as microbial polysaccharides, enzymes, gangliosides, glycoproteins, and antibiotics.
This research project had the purpose of preparing a derivative of 2-amino-2-deoxy-D-glucose, with a free hydroxyl group at the anomeric carbon, with the 4,6-positions blocked with the benzylidene cyclic acetal, and the 2,3-positions being blocked by a 3,3-diphenyl-2-morpholinone ring trans diequatorially fused to the amino sugar ring. The C-1 position was initially protected with a β-benzyl aglycon, which was expected to be removable selectively by catalytic hydrogenation. It was also hoped that we could optimize conditions for the synthesis of the morpholinone derivative. Selective cleavages of the blocking groups were to be investigated.
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Mouselmani, Rim. "Reduction of Organic Functional Groups Using Hypophosphites." Thesis, Lyon, 2018. http://www.theses.fr/2018LYSE1241/document.
Full textAbstract:
Récemment, les exigences en chimie ont évolué rapidement, car le développement durable a retenu plus d'attention. Les principes de la chimie verte ont encouragé les chimistes à développer des produits chimiques et des procédés qui réduisent ou éliminent les substances dangereuses. Les travaux de recherche décrits dans cette thèse portent sur le développement de nouveaux systèmes réducteurs en utilisant des hypophosphites comme substituts aux agents réducteurs toxiques traditionnels.Pour atteindre cet objectif, les nitriles aromatiques ont été réduits en aldéhydes correspondants par la formation du gaz de l’hydrogène et de nanoparticules de nickel en combinant un précurseur de nickel avec de l'hypophosphite de calcium en présence d'une base dans un milieu biphasique. De plus, les nitriles aromatiques ont été réduits en amines primaires en utilisant de l'hypophosphite de calcium et le catalyseur hétérogène palladium sur le carbone. La nature du catalyseur métallique, les additifs, les solvants, la température et les concentrations ont été étudiés en détail.D'autre part, l'amination réductrice directe des cétones aliphatiques et aromatiques a été réalisée pour la première fois en utilisant du palladium hétérogène sur du carbone et de l'hypophosphite d'ammonium qui agit comme une source d'ammoniac et un agent réducteur en même temps. Au cours de l'optimisation, des différents paramètres ont été étudiésRecently, requirements in chemistry are changing fast, since sustainable development has retained more attention. Green chemistry principles have promoted chemists to develop chemical products and processes that reduce or eliminate hazardous substances. The research work described in this thesis is focused on the development of new reducing systems using hypophosphites as substitutes for traditional toxic reducing agents.In order to achieve this goal, aromatic nitriles were reduced into the corresponding aldehydes by the formation of hydrogen gas and nickel nanoparticles upon combining a nickel precursor with calcium hypophosphite in the presence of base in a biphasic medium. Moreover, aromatic nitriles were reduced into primary amines using calcium hypophosphite and the heterogeneous catalyst palladium on carbon. The nature of the metal catalyst, additives, solvents, temperature, and concentrations were studied in details.On the other hand, the well-known direct reductive amination of aliphatic and aromatic ketones was done for the first time using heterogeneous palladium on carbon, and ammonium hypophosphite which acts as a source of ammonia and as a reducing agent at the same time. During optimization different parameters were studied