Search results for "Organometallic Compounds"
showing 10 items of 240 documents
Exceptional affinity of nanostructured organic-inorganic hybrid materials towards dioxygen: confinement effect of copper complexes
2007
We report the exceptional reactivity towards dioxygen of a nanostructured organic-inorganic hybrid material due to the confinement of copper cyclam within a silica matrix. The key step is the metalation reaction of the ligand, which can occur before or after xerogel formation through the sol-gel process. The incorporation of a Cu(II) center into the material after xerogel formation leads to a bridged Cu(I)/Cu(II) mixed-valence dinuclear species. This complex exhibits a very high affinity towards dioxygen, attributable to auto-organization of the active species in the solid. The remarkable properties of these copper complexes in the silica matrix demonstrate a high cooperative effect for O(2…
Enzyme-Controlled Nanodevice for Acetylcholine-Triggered Cargo Delivery Based on Janus Au–Mesoporous Silica Nanoparticles
2017
[EN] This work reports a new gated nanodevice for acetylcholine-triggered cargo delivery. We prepared and characterized Janus Au-mesoporous silica nanoparticles functionalized with acetylcholinesterase on the Au face and with supramolecular b-cyclodextrin: benzimidazole inclusion complexes as caps on the mesoporous silica face. The nanodevice is able to selectively deliver the cargo in the presence of acetylcholine via enzyme-mediated acetylcholine hydrolysis, locally lowering the pH and opening the supramolecular gate. Given the key role played by ACh and its relation with Parkinson's disease and other nervous system diseases, we believe that these findings could help design new therapeuti…
Simulations of a Graphene Nanoflake as a Nanovector To Improve ZnPc Phototherapy Toxicity: From Vacuum to Cell Membrane
2017
International audience; We propose a new approach to improving photodynamic therapy (PDT) by transporting zinc phthalocyanine (ZnPc) in biological systems via a graphene nanoflake, to increase its targeting. Indeed, by means of time-dependent density functional theory simulations, we show that the ZnPc molecule in interaction with a graphene nanoflake preserves its optical properties not only in a vacuum but also in water. Moreover, molecular dynamic simulations demonstrate that the graphene nanoflake/ZnPc association, as a carrier, permits one to stabilize the ZnPc/graphene nanoflake system on the cellular membrane, which was not possible when using ZnPc alone. We finally conclude that the…
A Rational Design for Imidazolate-Bridged Linear Trinuclear Compounds from Mononuclear Copper(II) Complexes with 2-[((Imidazol-2-ylmethylidene)amino)…
2001
Two mononuclear copper(II) complexes with the unsymmetrical tridentate ligand 2-[((imidazol-2-ylmethylidene)amino)ethyl]pyridine (HL), [Cu(HL)(H2O)](ClO4)2.2H2O (1) and [Cu(HL)Cl2] (2), have been prepared and characterized. The X-ray analysis of 2 revealed that the copper(II) ion assumes a pentacoordinated square pyramidal geometry with an N3Cl2 donor set. When 1 and 2 are treated with an equimolecular amount of potassium hydroxide, the deprotonation of the imidazole moiety promotes a self-assembled process, by coordination of the imidazolate nitrogen atom to a Cu(II) center of an adjacent unit, leading to the polynuclear complexes [[Cu(L)(H2O)](ClO4)]n (3) and [[Cu(L)Cl].2H2O]n (4). Variab…
Stereoselective syntheses of piperidinones and their modification by organometallic coupling reactions
2007
Dehydropiperidinones stereoselectively obtained from N-arabinosyl imines were iodinated at the enaminone structure. Knochel iodine-magnesium exchange afforded Grignard compounds of these piperidinone derivatives which reacted, either directly or after transmetalation to zinc or copper intermediates, with alkyl-, aryl- or acylhalides to give correspondingly substituted piperidinones. Stereoselective conjugate allyl cuprate addition to a thus obtained 5-allyl dehydropiperidinone and ring-closing metathesis of the product gave a hydroquinolinone containing three stereogenic centers.
Reduction of ferricytochrome c catalyzed by optically active chromium(III) complexes
2009
The reduction rates of horse heart ferricytochrome c by amalgamated zinc or by electrolysis at fixed potential on a mercury pool as the cathode have been measured in a buffered solution at pH 7.5 by absorption spectrophotometry. In both cases, the reaction was strongly accelerated by the presence of the optically active complexes Lambda-[Cr(III)((S,S)-promp)H(2)O](+) (H(2)promp = N,N'-[(pyridine-2,6-diyl)bis(methylene)]-bis[(S)-proline]), Delta-[Cr(III)((R,R)-alamp)H(2)O](+) (H(2)alamp = N,N'-[(pyridine-2,6-diyl)bis(methylene)]-bis[(R)-alanine]) and Lambda-[Cr(III)((S,S)-alamp)(H(2)O)(2)](+). These were shown to undergo reversible one-electron reduction to the corresponding labile chromium(…
Ferromagnetic coupling and magnetic anisotropy in oxalato-bridged trinuclear chromium(iii)-cobalt(ii) complexes with aromatic diimine ligands
2010
Two novel heterotrinuclear chromium(III)-cobalt(II) complexes of formula {[Cr(III)(bpy)(ox)(2)](2)Co(II)(Me(2)bpy)}.2H(2)O (1) and {[Cr(III)(phen)(ox)(2)](2)Co(II)(Me(2)bpy)}.1.5H(2)O (2) [ox = oxalato, bpy = 2,2'-bipyridine, Me(2)bpy = 6,6'-dimethyl-2,2'-bipyridine, and phen = 1,10-phenanthroline] have been synthesized using the "complex-as-ligand/complex-as-metal" strategy. The X-ray crystal structure of 2 consists of neutral oxalato-bridged Cr(III)(2)Co(II) bent entities formed by the coordination of two anionic [Cr(III)(phen)(ox)(2)](-) complexes through one of their oxalato groups toward a cationic cis-[Co(II)(Me(2)bpy)](2+) complex. The three tris(chelated), six-coordinated metal atom…
Spectroscopic study of the interaction of Ni(II)-5-triethyl ammonium methyl salicylidene ortho-phenylendiiminate with native DNA.
2009
The interaction of native calf thymus DNA with the cationic Ni(II) complex of 5-triethyl ammonium methyl salicylidene ortho-phenylendiimine (NiL(2+)), in 1mM Tris-HCl aqueous solutions at neutral pH, has been monitored as a function of the metal complex-DNA molar ratio by UV absorption spectrophotometry, circular dichroism (CD) and fluorescence spectroscopy. The dramatic modification of the DNA CD spectrum, the appearance of a broad induced CD band in the range 350-400nm, the strong increase of the DNA melting temperature (T(m)) and the fluorescence quenching of ethidium bromide-DNA solutions, in the presence of increasing amounts of the NiL(2+) metal complex, support the existence of a tig…
The interaction of native DNA with Zn(II) and Cu(II) complexes of 5-triethyl ammonium methyl salicylidene orto-phenylendiimine
2007
The interaction of native calf thymus DNA with the Zn(II) and Cu(II) complexes of 5-triethyl ammonium methyl salicylidene orto-phenylendiimine (ZnL(2+) and CuL(2+)), in 1 mM Tris-HCl aqueous solutions at neutral pH, has been monitored as a function of the metal complex-DNA molar ratio by UV absorption spectrophotometry, circular dichroism (CD) and fluorescence spectroscopy. The results support for an intercalative interaction of both ZnL(2+) and CuL(2+) with DNA, showing CuL(2+) an affinity of approximately 10 times higher than ZnL(2+). In particular, the values of the binding constant, determined by UV spectrophotometric titration, equal to 7.3x10(4) and 1.3x10(6)M(-1), for ZnL(2+) and CuL…
Confinement effects on the interactions of native DNA with Cu(II)-5-triethyl ammonium methyl salicylidene orto-phenylendiiminate in C12E4 liquid crys…
2008
Confinement effects of native calf thymus DNA interacting with the complex Cu(ii)-5-(triethylammoniummethyl)salicylidene ortho-phenylendiiminate (CuL(2+)) perchlorate in tetraethylene glycol monododecyl ether (C(12)E(4)) liquid crystals have been investigated by UV absorption spectrophotometry, circular dichroism (CD) and small angle X-ray scattering (SAXS). The results indicate the occurrence of dramatic structural changes of both the DNA and the CuL(2+)-DNA system, when going from aqueous solution to C(12)E(4) liquid crystals, due to confinement constrains imposed by the closed structure of C(12)E(4) reverse micelles. Further marked departures from the behaviour observed in aqueous soluti…