Search results for "Titration"
showing 10 items of 312 documents
Very strong −N–X+⋯−O–N+ halogen bonds
2016
A new (-)N-X(+)(-)O-N(+) paradigm for halogen bonding is established by using an oxygen atom as an unusual halogen bond acceptor. The strategy yielded extremely strong halogen bonded complexes with very high association constants characterized in either CDCl3 or acetone-d6 solution by (1)H NMR titrations and in the solid-state by single crystal X-ray analysis. The obtained halogen bond interactions, RXB, in the solid-state are found to be in the order of strong hydrogen bonds, viz. RXB ≈ RHB.
On the physicochemical properties of pyridohelicenes.
2014
A comprehensive study on the physicochemical properties of a series of mono- and diaza[5]helicenes as well as mono- and diaza[6]helicenes is reported. Through the use of both computational and experimental methods, these helically chiral pyridohelicenes with the nitrogen atom(s) in various positions are characterised according to their inversion barriers, protonation constants and redox potentials. By using DFT calculations, kinetic measurements, UV/Vis titrations, cyclic voltammetry and EPR spectroscopy, a self-contained picture of their behaviour under conventional treatment by heat, acids and oxidising/reducing agents is provided.
Mechanism of sulfur transfer across protein-protein interfaces: The cysteine desulfurase model system
2016
CsdA cysteine desulfurase (the sulfur donor) and the CsdE sulfur acceptor are involved in biological sulfur trafficking and in iron-sulfur cluster assembly in the model bacterium Escherichia coli. CsdA and CsdE form a stable complex through a polar interface that includes CsdA Cys328 and CsdE Cys61, the two residues known to be involved in the sulfur transfer reaction. Although mechanisms for the transfer of a sulfur moiety across protein-protein interfaces have been proposed based on the IscS-IscU and IscS-TusA structures, the flexibility of the catalytic cysteine loops involved has precluded a high resolution view of the active-site geometry and chemical environment for sulfur transfer. H…
On the Complexation of Cu(II) and Cd(II) With Polycarboxyl Ligands. Potentiometric Studies With ISE-H+, ISE-Cu2+, and ISE-Cd2+
2009
The interaction of Cu2+ and Cd2+ ions with polyacrylates (PAA, 2 kDa and 100 kDa), polymetacrylate(PMA, 5.4 kDa), and alginate (AA, 70 kDa to 100 kDa) was studied by potentiometry, using ISE-Cu2+, ISE-Cd2+, and ISE-H+ electrodes. The investigations were performed in NaNO3 aqueous solutions, in the ionic strength range 0.10 e I (mol ·L-1) e 0.75, at T ) 298.15 K. The “diprotic-like model” was used to explain the acid-base behavior of the polycarboxylates under investigation (for this model, the monomeric unit of the polyelectrolyte is considered as a dicarboxylate). The results give evidence for the formation of the ML species in all the systems investigated. In addition, the MLH species was…
A step forward in the development of superoxide dismutase mimetic nanozymes: the effect of the charge of the surface on antioxidant activity
2019
Two binucleating hezaaza macrocycles containing a pyridinol spacer have been prepared and characterised. Protonation studies indicate the deprotonation of the phenol group at relatively low pH values with the concomitant occurrence of a keto-enolic equilibrium. These ligands readily form binuclear Cu2+ and Zn2+ complexes as denoted by potentiometric and spectroscopic studies. The binding of the metals yields to the ready deprotonation of the phenol with the stabilisation of the keto form that results in complexes of greater stabilities than the analogous ones containing pyridine as spacer instead of pyridine. Mixed Cu2+–Zn2+-complexes were also detected in aqueous solutions containing equim…
An Off-On-Off Fluorescent Sensor for pH Windows Based on the 13aneN4-Zn 2+ System
2016
International audience; The new ligand L was prepared and features a 13-membered tetraaza macrocyclic ring with a 1,8-naphthalimide fluorophore appended to a C atom of its backbone. The protonation constants of L as well as its complexation constants with Zn2+ ions were determined in 1:1 water/methanol solutions by potentiometric titrations. Fluorimetric pH titrations were performed with L alone and L in the presence of Zn2+ ions (1:1), and the species distributions (%) versus pH were compared. A window-shaped fluorescence trend was observed with pH for the L/Zn2+ system, which behaves as an off-on-off pH sensor. The on window is centred in the 6.5-7.5 pH range, in correspondence with the f…
Synthesis, Characterization, and Cu(2+) Coordination Studies of a 3-Hydroxy-4-pyridinone Aza Scorpiand Derivative.
2016
The synthesis, acid-base behavior, and Cu(2+) coordination chemistry of a new ligand (L1) consisting of an azamacrocyclic core appended with a lateral chain containing a 3-hydroxy-2-methyl-4(1H)-pyridinone group have been studied by potentiometry, cyclic voltammetry, and NMR and UV-vis spectroscopy. UV-vis and NMR studies showed that phenolate group was protonated at the highest pH values [log K = 9.72(1)]. Potentiometric studies point out the formation of Cu(2+) complexes of 1:2, 2:2, 4:3, 1:1, and 2:1 Cu(2+)/L1 stoichiometries. UV-vis analysis and electrochemical studies evidence the implication of the pyridinone moieties in the metal coordination of the 1:2 Cu(2+)/L1 complexes. L1 shows …
Mössbauer spectroscopy on the reaction center of Rhodopseudomonas viridis
1992
Proteins called “reaction centers” (RC) can be isolated from many photosynthetic bacteria. They have one non-heme iron in a quinone acceptor region. The RC of Rhodopseudomonas viridis contains an additional tightly bound tetra-heme cytochrome c subunit. The electronic configuration of both cytochrome and the non-heme iron has been studied in the crystallized protein by Mossbauer spectroscopy at different redox potentials, pH-values, and with an addition of o-phenanthroline. At high potentials (Eh=+500mV) all heme irons are in the low spin Fe3+-state, and at low potential (Eh=−150mV) they are low spin Fe2+ with the same Mossbauer parameters for all hemes independent of pH. Redox titrations c…
Impact of α,β-dehydroamino acid residues on the binding abilities of di-, tri- and tetra-peptides
2000
Insertion of a dehydroamino acid residue into a sequence of di-, tri- or tetra-peptide changed considerably the binding abilities of peptide ligands towards copper(II) ions. Potentiometric and spectroscopic (EPR, UV-VIS and CD) data have shown that the amide nitrogen of the dehydroamino acid residue is more effective in co-ordination than its parent analogue. In the case of the bulky ΔPhe residue also the (Z–E) isomerisation has a critical impact on the co-ordination equilibria in the system studied.
Hydrothermally Synthesized Strontium Peroxyapatite
2015
The current research focuses on peroxide ion incorporation in the structure of strontium hydroxyapatite (SrHAp) by exposure to H2O2 ina closed hydrothermal vessel under mild conditions at 130 to 170 °C. Peroxide enriched strontium apatite (SrPerAp) was characterized for structure by X-Ray diffraction, for peroxide content- by permanganometric titration and then viewed by SEM. This study continued from previous work that used 30%H2O2 and showed a higher included peroxide content after processing with 50% H2O2 at 130 °C 70% of the theoretical peroxide content in apatitic channels of strontium apatite. This is the highest peroxide content incorporated to date and employs a lower temperature th…