Thesis (doctoral)--Christian-Albrechts-Universität zu Kiel, 1994.

Amidines [RNC(R')NR, I] and their complexes of the nickel group metals have been studied. Accurate mass spectrometry applied to (R'=H, R=Ph; R'=CH(_3), R=Ph; R'=Ph=R) have given detailed fragmentation patterns which form the basis for the interpretation of related amidines. Differences in skeletal fragmentation patterns were noted between formamidines and acetamidines/benzamidines, (^1)H, (^13)C and (^19)F n.m.r. and mass spectroscopy of lithioamidines indicate a bidentate symmetrically bonded amidine. The reactions of amidines [RN(X)C(R^)NR] X=H, Li) with compounds of the nickel group metals, results in a wide variety of complexes; their nature depending on the amidine substituents, the metal and the synthetic route used. Complexes with N,N'chelate, or't/20-metallated, and bridging groups were prepared and characterised together with complexes containing new N,N'chelate and bridging groups, resulting from nucleophilic attack of an amidine at a coordinated nitrile. The reactions of M(PhCN)(_2)C1(_2) (M=Pd, Pt) and anhydrous NiC1(_2) with lithioamidines result in yellow Pt(Am)(_2), where Am = RNC(R')NR, red Pd(_2)(Am)(_4) and dark green Ni(_2)(Am)(_4) complexes. The platinum complexes are monomeric for the acetamidine (R'=CH(_3)), and benzamidine (R(_6)H(_5)) ligands, though for palladium the benzamidine complexes are dimeric. The nickel complexes are dimeric for the acetamidine,and benzamidine ligands. Spectroscopic studies indicate that the amidino-groups adopt a carboxylate type mode of bonding through the two nitrogen atoms, and the structure of one of the complexes, bis, N,N'diphenylbenzamicline-platinum(II) has been characterised by X-ray crystallography. The structure showed a monomeric PtN(_4) square planar unit. N.m.r. ((^19)F and (^13)C) studies have indicated fluxionality when M=Pd, R'=C(_6)H(_5), R=C(_6)H(_4)-F-p. With K(_2)MCl(_4)(M=Pd, Pt) and NiC1(_2), N,N'diarylamidines form polymeric ortho-metallated complexes, N,N' diarylformamidines and acetamidines form six-membered rings, benzamidines five-membered. Treatment of Pt(PhCN)(_2)C1(_2) with HN(Li)(C(_6)H(_5))NH results in nucleophilic attack at the nitrile and formation of Pt[HNC(C(_6)H(_5))NC(C(_6)H(_5))NH](_2). A similar reaction occurred with Pd(PhCN)(_2)C1(_2) and HNLiC(C(_4)(_9))NH.

Thesis (doctoral)--Freien Universität Berlin, 1980.

Universiẗat, Diss., 2003--Jena.

Universiẗat-Gesamthochsch., Diss.--Paderborn, 1995.

Les lipides cationiques sont des molécules amphiphiles chargées positivement et couramment utilisées comme vecteur de transfection tant in vitro qu'in vivo avec une bonne efficacité. Cependant, la transfection in vivo par voie intraveineuse à l'aide de complexes lipides cationiques/ADN (lipoplexes) induit une réponse inflammatoire, attribuée à la présence de séquences CpG dans les plasmides transportés, et qui limite l'efficacité de transfection des complexes. Il a été montré dans notre laboratoire que la pré-injection de liposomes de diC14-amidine, un lipide cationique mis au point dans notre laboratoire, avant l'injection des lipoplexes diC14-amidine/ADN permettait d'augmenter l'efficacité de transfection tout en diminuant la production de TNF-¦Á dans le sérum [Elouahabi et al., 2003b]. Ce résultat suggérait une nouvelle propriété anti-inflammatoire de la diC14-amidine dans le cas d'une inflammation causée par les lipoplexes de diC14-amidine/ADN. Dans le présent travail, nous d¨¦montrons que les macrophages de la rate sont les principales cellules productrices de TNF-¦Á suite à l'injection intraveineuse des lipoplexes à des souris. Ces mêmes cellules sont également la principale cible des liposomes de diC14-amidine après injection intraveineuse. Nous avons dès lors centré notre étude sur ce type cellulaire, en utilisant une lignée établie de macrophages murins. Nos résultats ont permis de confirmer la capacité des liposomes de diC14-amidine à inhiber la sécrétion des cytokines pro-inflammatoires induites par des séquences CpG, des lipopolysaccharides ou des poly(I :C). Fait intéressant, la présence de sérum est indispensable à la propriété anti-inflammatoire des liposomes de diC14-amidine. Par fractionnement successifs des composants du sérum, nous avons pu montrer que seuls les phospholipides des lipoprotéines pouvaient conférer cette propriété aux liposomes de diC14-amidine.

Thesis (doctoral)--Christian-Albrechts-Universität zu Kiel, 1998.

This thesis is an investigation into the development of amidine and guanidine based compounds to be employed as switchable surfactants. The surface activity of these molecules can be triggered by reaction with a benign gas, CO2. The ultimate application of these surfactants was to be used as emulsifying and demulsifying agents of crude oil and water emulsions. Synthesis and characterization of the following desired bases: N’-octyl-N,N-dimethylacetamidine (1), 2-octyl-2-imidazoline (2), 1-methyl-2-octyl-2-imidiazoline (3), N’-(4-heptylphenyl)-N,N-dimethylacetamidine (4), N’-(4-(octyloxy)phenyl)-N,N-dimethylacetamidine (5), N’-(4-(methyloxy)phenyl)-N,N-dimethylacetamidine (6), and N-octyl-N',N',N",N"-tetramethylguanidine (7) was carried out. Their solubility in water was quantified with NMR spectroscopy. All bases were reacted with CO2 and H2O to form bicarbonate salts, of which in situ characterization was achieved by IR and NMR spectroscopy. Percent conversion to the protonated forms at elevated temperatures was determined using NMR spectroscopy. A direct correlation between switchability and basicity was observed, as the strongest bases possessed the largest conversions to the protonated species, even at higher temperatures. The enthalpy of protonation was determined for each base through calorimetry experiments. These compounds were tested as demulsifying surfactants of crude oil and water emulsions. Demulsifying ability was determined to differ greatly with the head group structure of the various surfactants. / Thesis (Master, Chemistry) -- Queen's University, 2009-10-27 16:56:13.631

Universiẗat, Diss., 2002--Jena.

Universiẗat, Diss., 2004--Jena.