Search results for "Proton"
showing 10 items of 5886 documents
Recognition of Li+ by a Salophen−UO2 Homodimeric Complex
2009
Self-assembly via mutual U-coordination of the salophen-UO(2) complex 1 creates a dimeric species which is shown to be useful for metal binding. Indeed, the 1 dimer has affinity for alkali metal cations and, interestingly, a marked selectivity for Li(+), determined by electrospray ionization mass spectrometry and (1)H NMR techniques. X-ray diffraction helped in the elucidation of the dimeric complex structure, which presents a crown-ether-type coordination site, in analogy to the more familiar 12-crown-4, responsible for the metal interaction. Comparison with isomer 2, and the salen derivative 3, increases the understanding of the behavior of such systems in solution and in the solid state.
Electrochemical and DFT studies of the oxidative decomposition of the trihydride complexes Cp*M(dppe)H3 (M = Mo, W) in acetonitrile
2006
International audience; A detailed electrochemical study of the oxidative decomposition of the trihydride complexes Cp*M(dppe)H3 (M = Mo, W) in acetonitrile is presented. For the Mo complex, the decomposition occurs by four different pathways involving classical and non-classical tautomers, whereas only the classical form is accessible for the W derivative. Each of the decomposition pathways has been quantitatively assessed by analyses of the linear sweep voltammograms. In addition to the previously established (B. Pleune, D. Morales, R. Meunier-Prest, P. Richard, E. Collange, J. C. Fettinger and R. Poli, J. Am. Chem. Soc., 1999, 121, 2209–2225) deprotonation, disproportionation, and H2 red…
13C NMR spectra of eudesmane derivatives
1992
The 13C NMR spectral data of 18 eudesmane derivatives, mainly acids and esters of natural and synthetic origin, are reported, and the γ-effect of the epoxide ring in two diastereoisomeric epoxy esters is discussed.
Mixed micelles composed of Peptides and Gadolinium complexes as tumor-specific contrast agents in MRI: a SANS study
2004
A detailed structural investigation on mixed micelle aggregates as target-specific contrast agents for magnetic resonance imaging technique has been carried out by way of small angle neutron scattering measurements. These mixed micelles are formed by two new amphiphilic molecules formed by a bioactive peptide and a claw moiety. The first molecule, C18H37CONH(AdOO)(x)-G-CCK8 (C18LxCCK8, x = 2, 5), contains an 18-carbon-atom alkylic chain bound to the C-terminal of the cholecystokinin octapeptide amide (CCK 26-33 or CCK8) and is able to bind to the overexpressed CCK receptor of some tumor cells. The second molecule, C(18)H(37)CONHLys(DTPAGlu)CONH25- (C18DTPAGlu) or its gadolinium complex [C(1…
Protonation constants and association of polycarboxylic ligands with the major components of seawater
2000
Apparent protonation constants, log βjH*, of 11 carboxylic acids were determined potentiometrically ([H+]-glass electrode) in artificial seawater containing six of the major components (Na+, K+, Mg2+, Ca2+, Cl-, and SO42-) at different salinities: S (‰) = 5, 15, 25, 35, 45. Values of log βjH* were fitted by the simple polynomial equation log βjH* = log TβjH + a1S1/2 + a2S + a3S3/2 (log TβjH = protonation constants at infinite dilution; a1, a2, a3 = empirical parameters), for mono-, di-, and tricarboxylates. For carboxylic anions with charge < −3, a better fit was obtained using the equation log βjH* = log TβjH + b1I + b0z* log(1 + b2I) (b0, b1, b2 = empirical parameters, z* = square sum of…
Molecular recognition of naphthalene diimide ligands by telomeric quadruplex-DNA: the importance of the protonation state and mediated hydrogen bonds.
2016
In depth Monte Carlo conformational scans in combination with molecular dynamics (MD) simulations and electronic structure calculations were applied in order to study the molecular recognition process between tetrasubstituted naphthalene diimide (ND) guests and G-quadruplex (G4) DNA receptors. ND guests are a promising class of telomere stabilizers due to which they are used in novel anticancer therapeutics. Though several ND guests have been studied experimentally in the past, the protonation state under physiological conditions is still unclear. Based on chemical intuition, in the case of N-methyl-piperazine substitution, different protonation states are possible and might play a crucial …
Determination of the electron-detachment energies of 2'-deoxyguanosine 5'-monophosphate anion: influence of the conformation.
2009
The vertical electron-detachment energies (VDEs) of the singly charged 2'-deoxyguanosine 5'-monophosphate anion (dGMP - ) are determined by using the multiconfigurational second-order perturbation CASPT2 method at the MP2 ground-state equilibrium geometry of relevant conformers. The origin of the unique low-energy band in the gas phase photoelectron spectrum of dGMP - , with maximum at around 5.05 eV, is unambiguously assigned to electron detachment from the highest occupied molecular orbital of π-character belonging to guanine fragment of a syn conformation. The presence of a short H-bond linking the 2-amino and phosphate groups, the guanine moiety acting as proton donor, is precisely resp…
Long-range substituent and temperature effect on prototropic tautomerism in 2-(acylmethyl)quinolines
2001
Tautomeric equilibria between 2-(cinnamoylmethyl)quinoline, (Z)-1,2-dihydro-2-(cinnamoylmethylene)quinoline and (Z)-4-phenyl-1-(2-quinolyl)-1,3-butadien-2-ol were studied by 1H, 13C and 15N NMR methods. The —CHCH— fragment conjugated with phenyl and a strong electron donor p-(1-pyrrolidine) substituent were found to favour the enolimine tautomer. This undergoes fast exchange (on the NMR time-scale) with the enaminone form. The amount of the latter tautomer was found to increase at low temperatures. Copyright © 2001 John Wiley & Sons, Ltd.
Synthesis, characterization, X-ray crystallography, and antimicrobial activities of Ni(II) and Cu(II) complexes with a salicylaldehyde-based thiosemi…
2014
A new salicylaldehyde-based ‘ONS’ tridentate salicylaldehyde-N(4)-diethylthiosemicarbazone (H2SANEt2) has been synthesized and characterized by elemental analyses, mass, IR, and 1H NMR spectral parameters. The coordination mode of the synthesized ligand is reported by solid state isolation and physico-chemical identification of Ni(II) and Cu(II) complexes, [Ni(SANEt2)]2 (1) and [Cu(SANEt2)]2 (2). Both complexes are neutral and oxygen-bridged dinuclear species. The ligand is bideprotonated ‘ONS’ tridentate in both complexes. IR spectral data indicate that coordination of each metal of the two complexes occurs through phenolic oxygen, azomethine nitrogen, and thiolato sulfur. X-ray crystallog…
Conformations and coordination schemes of carboxylate and carbamoyl derivatives of the tetraazamacrocycles cyclen and cyclam, and the relation to the…
1998
Abstract This paper discusses and rationalizes the metal coordination pattern of 12- and 14-membered tetraazamacrocyclic carboxylate and carbamoyl ligands based on the cyclen and cyclam framework in light of their acido–basic properties. Structural and protonation data are reviewed in order to illustrate the influence of the free ligand's protonation state and of the pH conditions during the complexation reaction on the final coordination mode of the metallic cations.