Search results for "Constants"
showing 10 items of 150 documents
Oxoanion binding to a cyclic pseudopeptide containing 1,4-disubstituted 1,2,3-triazole moieties
2016
A macrocyclic pseudopeptide 3 is described featuring three amide groups and three 1,4-disubstituted 1,2,3-triazole units along the ring. This pseudopeptide was designed such that the amide NH groups and the triazole CH groups converge toward the cavity, thus creating an environment well suited for anion recognition. Conformational studies in solution combined with X-ray crystallography confirmed this preorganisation. Solubility of 3 restricted binding studies to organic media such as 5 vol% DMSO/acetone or DMSO/water mixtures with a water content up to 5 vol%. These binding studies demonstrated that 3 binds to a variety of inorganic anions in DMSO/acetone including chloride, nitrate, sulfat…
Aza-macrocyclic triphenylamine ligands for G-quadruplex recognition
2018
A new series of triphenylamine-based ligands with one (TPA1PY), two (TPA2PY) or three pendant aza-macrocycle(s) (TPA3PY) has been synthesised and studied by means of pH-metric titrations, UV/Vis spectroscopy and fluorescence experiments. The affinity of these ligands for G-quadruplex (G4) DNA and the selectivity they show for G4s over duplex DNA were investigated by Forster resonance energy transfer (FRET) melting assays, fluorimetric titrations and circular dichroism spectroscopy. Interestingly, the interactions of the bi- and especially the tri-branched ligands with G4s lead to a very intense redshifted fluorescence emission band that may be associated with intermolecular aggregation betw…
A theoretical study of the 1B2u and 1B1u vibronic bands in benzene
2000
The two lowest bands, 1B2u and 1B1u, of the electronic spectrum of the benzene molecule have been studied theoretically using a new method to compute vibronic excitation energies and intensities. The complete active space (CAS) self-contained field (SCF) method (with six active π-orbitals) was used to compute harmonic force field for the ground state and the 1B2u and 1B1u electronic states. A linear approximation has been used for the transition dipole as a function of the nuclear displacement coordinates. Derivatives of the transition dipole were computed using a variant of the CASSCF state interaction method. Multiconfigurational second-order perturbation theory (CASPT2) was used to obtai…
Quantum-chemical determination of Born–Oppenheimer breakdown parameters for rotational constants: the open-shell species CN, CO+ and BO
2013
The quantum-chemical protocol for computing Born-Oppenheimer breakdown corrections to rotational constants in the case of diatomic molecules is extended to open-shell species. The deviation from the Born-Oppenheimer equilibrium rotational constant is obtained by considering three contributions: the adiabatic correction to the equilibrium bond distance, the electronic contribution to the moment of inertia requiring the computation of the rotational g-tensor, and the so-called Dunham correction. Values for the Born-Oppenheimer breakdown parameters of CN, CO+, and BO in their (2)sigma(+) electronic ground states are reported based on coupled-cluster calculations of the involved quantities and …
Solubility and acid-base properties and activity coefficients of chitosan in different ionic media and at different ionic strengths, at T=25°C
2009
Studies on the acid-base properties and solubility of a polyammonium polyelectrolyte (chitosan) with different molecular weights (MW 310 and 50 kDa), were performed at T=25 °C, in the pH range 2.5–7. The protonation of chitosan was investigated by potentiometry ([H+]-glass electrode) in NaCl, NaNO3 and mixed NaNO3+Na2SO4 ionic media, at different ionic strengths. Protonation constants were calculated as a function of dissociation degree α by means of two different models, namely, a simple linear model and the modified Henderson–Hasselbalch equation. Experimental data were also fitted using a model independent of α (Diprotic-like model), according to which the acid-base properties can be sim…
Polyfunctional recognition of pyridinedicarboxylate anions with macrocyclic polyamine receptors containing heteroaromatic groups.
2008
The interaction of the biologically relevant anions deriving from the six pyridinedicarboxylic acids (H2PDC) with two macrocyclic receptors containing a pentamine chain and a bipyridine (1) or a phenanthroline (2) moiety, as well as with the aliphatic analogue [21]aneN7 (3), was studied by means of spectroscopic methods (UV-vis, NMR) and potentiometric titrations affording the stability constants of the adducts formed. All three receptors form stable complexes with the substrates thanks to the formation of several salt bridges and hydrogen bond contacts, as observed in the crystal structure of the H8[3(2,6-PDC)4] x H2O x 0.5 EtOH solid compound. Additional pi-stacking interactions between t…
The interaction of amino acids with the major constituents of natural waters at different ionic strengths
2000
Abstract The interaction of amino acids with the major constituents of natural waters has been studied potentiometrically by determining protonation constants at different ionic strengths (e.g., I ≤5.6 mol (kg H 2 O) −1 (NaCl)) and in artificial seawater (containing Na + , K + , Ca 2+ , Mg 2+ , Cl − and SO 4 2− ) at different salinities. For glycine determinations in mixed NaCl–MgCl 2 , electrolyte solutions were also performed. The data included in this work, together with some already published, make it possible to calculate parameters for dependence on ionic strength using different models, i.e. an extended Debye–Huckel type equation and Pitzer equations. The results can be interpreted b…
Complexation of the potassium ion by diaza crown compounds in aqueous solutions
1988
The conductance behavior of potassium nitrate in water with and without 1,7,10,16-tetraoxa-4,13-diazacyclooctandecane[2.2] and 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo-8.8.8-exacosane[2.2.2] macrocyclic ligands have been studied in order to analyze the complexation behavior of potassium cations in water. The absence of the complexation found in the [2.2] system is discussed in terms of the ligand structural features (presence of hydrogen bond donor and acceptor sites). The ion pair association constant of potassium cryptate as obtained from conductance measurements is also reported and discussed.
Violurato complexes of nickel(II). Formation equilibria. Deprotonation equilibria of the coordinated ligands and related stereochemical changes
1986
The formation equilibria of nickel(II) violurato-complexes in water and dimethylsulphoxide-water (80∶20) as well as deprotonation of the coordinated ligands and related stereochemical changes are reported. The stability constants of the Ni2+-H2V− complexes logβ1=5.06, Iogβ2=9.38, logβ3=12.98 as well as the acidity constants of the [Ni(H2V)3]− complex, logβj1= 8.37, logβj2=15.76, logβj3=22.37 are determined at 25 °C and 0.1M NaClO4. A new violurato-complex of Ni2+, Na4[Ni(HV)3]5H2O, is isolated and characterized.
Sequestration of organometallic compounds by natural organic matter. binding of trimethyltin(IV) by fulvic and alginic acids
2006
The binding capacity of fulvic and alginic acids towards trimethyl tin(IV) cation was quantitatively determined in order to evaluate the sequestering ability of toxic organometallic compounds by natural organic matter. Investigations were performed in the pH range of natural waters (5–8.5) where the carboxylate groups, largely present in both sequestering agents, are the main binding sites. A chemical interaction model, according to which both the protonation of polyelectrolyte ligands and the hydrolysis of the organotin cation in NaCl aqueous solution were considered, was used to define the speciation of the systems under investigation. Measurements performed at different ionic strength va…