Search results for "Protonation"
showing 10 items of 583 documents
Binding properties of heptakis-(2,6-di-O-methyl)-β-cyclodextrin and mono-(3,6-anhydro)-β-cyclodextrin: a polarimetric study
2011
The binding constants for the inclusion complexes formed between heptakis-(2,6-di-O-methyl)-β-cyclodextrin (MβCD) and mono-(3,6-anhydro)-β-cyclodextrin (AβCD) with a set of suitably selected organic guests, were measured by means of polarimetry. Measurements were carried out at various pH values in order to ensure the correct protonation state for ionizable guests. Experimental data suggest that the binding properties of MβCD may be rationalized considering the less polar and more hydrophobic character of the cavity, although similar variations in conformational/dynamic behaviour occur as for native βCD. On the other hand, AβCD shows some similarities with αCD, due to the significant distor…
Cation and Anion Coordination Chemistry of Palladium(II) with Polyazacycloalkanes. Thermodynamic and Structural Studies
1992
The interaction of PdCI2 4 - with the macrocyclic ligands of the series [3k]aneNk has been studied both in solution and in the solid state. [18]aneN6 and [21]aneN7 form both mono- and binuclear Pd2+ complexes, whose stability constants have been determined in 0.5 mol dm-3 NaCI at 298.15 K. [21]aneN7 also forms, in solution, a trinuclear species in which an amino group deprotonates to bridge two Pd2+ ions, as observed in the solid state. The crystal structure of the complexes [Pd2([18]aneN6)Cl2][CIO4]2 and [Pd3[21]aneN7)CI3][CIO4]2 ⋅ H2O have been solved by single crystal X-ray analysis. C12H30N6CI4O8Pd2: monoclinic, space group C2/m, a = 10.876(2), b = 18.117(2), c = 7.043(2) A, s = 113.78(…
1H NMR studies of paramagnetic ferricytochrome c-551 from Pseudomonas aeruginosa at high pH: The role of histidine 16 in the spin transition
2005
Abstract Cytochrome c-551 from the mesophile Pseudomonas aeruginosa is an electronic transfer protein that contains 82 amino-acid residues and a c-type heme as the prosthetic group with low spin Fe(II) in the reduced form and low spin Fe(III) in the oxidized form of cytochrome c-551. We have studied the electronic properties of ferricytochrome c-551 from P. aeruginosa at high pH (9–11.4) by means of paramagnetic 1H NMR spectra and the T1 and T2 values of isotropically shifted proton resonances. We have also analyzed the temperature dependence of the hyperfine-shifts. Resonance assignment of some signals was based on 2D saturation transfer experiments, EXSY. These results indicate the existe…
CuIIand ZnIICoordination Chemistry of Pyrazole‐Containing Polyamine Receptors − Influence of the Hydrocarbon Side Chain Length on the Metal Coordinat…
2004
The synthesis of a new macrocyclic receptor (L 4 ) containing two 3,5-dimethylpyrazole units connected by dipropylenetriamine bridges is reported for the first time; pH-metric titrations indicate that L 4 shows six protonation steps in the pH range 2-11. In the absence of metal ions, the pyrazole moieties are not involved in acid-base processes in this pH range. Addition of Cu I I and Zn I I results in deprotonation of the pyrazole moieties which act as bis(monodentate) η 1 :η 1 ligands. This induced deprotonation occurs at higher pH values than in the complexes of the analogous ligand containing diethylenetriamine bridges (L 1 ). The crystal structures of [Cu 2 (H - 2 L 4 )](ClO 4 ) 2 and …
Solvation chemistry of water-soluble thiol-protected gold nanocluster Au102 from DOSY NMR spectroscopy and DFT calculations
2014
The hydrodynamic diameter of Aum(pMBA)n [(m, n) = (102, 44) and (144, 60)] clusters in aqueous media was determined via DOSY NMR spectroscopy. The apparent size of the same (n, m) cluster depends on the counter ion of the deprotonated pMBA− ligand as explained by the competing ion-pair strength and hydrogen bonding interactions studied in DFT calculations. The choice of the counter ion affects the surface chemistry and molecular structure at the organic/water interface, which is relevant for biological applications.
Synthesis of γ-Amino Acid Esters by 1,4-Addition of Deprotonated α-Aminonitriles and α-(Alkylideneamino)nitriles to α,β-Unsaturated Esters.
2007
α-Aminonitriles and α-(alkylideneamino)nitriles can serve as readily available α-aminocarbanion equivalents. Their conjugate addition to α,β-unsaturated esters followed by reduction furnishes polysubstituted γ-amino acid esters in moderate to high yield.
Formation rates and protonation constants of azo dyes in a sodium dodecylsulphate micellar solution.
1991
The effects of a sodium dodecylsulphate micellar solution on the coupling rates of several diazotizated arylamines with N-(1-naphthyl)-ethylenediamine and the shifts in the protonation constants of the corresponding azo dyes are quantitatively studied. Aniline, o-, m- and p-aminobenzoic acids, ethyl p-aminobenzoate and several sulphadrugs are used, and the relationships among the intensity of the effects and the molecular structure of the diazonium ions and the dyes are discussed. A single simplified procedure for the determination of all the substances at pH = 1.3 +/- 0.3, where coupling is quickly completed to directly produce the protonated form of the dyes, is established and applied to…
Spectroscopic behavior of metal–drug complexes. Infrared spectra of Cu(II) dimer complexes with acetazolamide (H2acm) and an analogue sulfonamide (B-…
1999
Abstract The infrared spectra of the drugs H2acm and B-H2ats, and their copper(II) dimer complexes with stoichiometries [Cu(acm)(NH3)2(OH2)]2·H2O and [Cu(B-ats)(NH3)2]2 are reported and discussed. The Raman spectra of H2acm and B-H2ats are also reported. An assignment of H2acm and B-H2ats modes in the complexes is proposed in comparison with the modes of the free ligands. The spectral modifications due to the deprotonation and coordination effects are analyzed. The ν(N–H) modes of the sulfonamido, carbonamido and Nring–H of the imine tautomer have been accurately assigned. Important information about the S–O and S–N vibrations has been obtained.
Complexes of tryptophan dipeptides with the R2Sn(IV)2+ ion (R=Me, Ph): Spectroscopic studies, solution properties and structural implications
1995
Tryptophan dipeptides such as L-tryptophyl-L-alanine (H 2 TrpAla), L-tryptophyl-L-tyrosine (H 2 TrpTyr), L-tryptophyl-L-tryptophan (H 2 TrpTrp), along with L-histidyl-L-tyrosine (H 2 HisTyr), were reacted with R 2 SnO (R=Me, Ph) yielding the corresponding complexes. The complexes have been characterized by IR and 119 Sn Mossbauer spectroscopy in the solid state and by 1 H and 13 C NMR in CD 3 OD solutions. Monomeric species were detected, with the tin atom arranged in a pentacoordinated trigonal-bipyramidal structure. The dipeptides are coordinated via the terminal amino group, deprotonated peptide nitrogen and terminal carboxylate group. No side-chain appears to be involved in bonding. Det…
CO2 as a C1-organic building block: Electrocarboxylation of aromatic ketones. A quantitative study of the effect of the concentration of substrate an…
2006
The purpose of this work is to establish and discuss quantitative relationships between the selectivity in preparative scale electrolysis and intrinsic and operational parameters for the electrocarboxylation of aromatic ketones. For the investigated ketones, under appopriate experimental conditions the selectivity of the process is mainly determined by the competition between carboxylation and protonation, de-halogenation reactions (when an halogenated ketone is involved), and possibly dimerizations involving the electrogenerated radical anion. A simple model was proposed to account for these unwanted side paths which allows to predict the dependence of the selectivity as a function of the …