Search results for "Protonation"
showing 10 items of 583 documents
Chemical and photochemical properties of chloroharmine derivatives in aqueous solutions
2015
Thermal and photochemical stability (ΦR), room temperature UV-vis absorption and fluorescence spectra, fluorescence quantum yields (ΦF) and lifetimes (τF), quantum yields of hydrogen peroxide (ΦH2O2) and singlet oxygen (ΦΔ) production, and triplet lifetimes (τT) have been obtained for the neutral and protonated forms of 6-chloroharmine, 8-chloroharmine and 6,8-dichloroharmine, in aqueous media. When it was possible, the effect of pH and oxygen concentration was evaluated. The nature of electronic transitions of protonated and neutral species of the three investigated chloroharmines was established using Time-Dependent Density Functional Theory (TD-DFT) calculations. The impact of all the fo…
Tetradihydrobenzoquinonate and Tetrachloranilate Zr(IV) Complexes: Single-Crystal-to-Single-Crystal Phase Transition and Open-Framework Behavior for …
2013
The molecular complexes K4[Zr(DBQ)4] and K 4[Zr(CA)4], where DBQ2- and CA2- stand respectively for deprotonated dihydroxybenzoquinone and chloranilic acid, are reported. The anionic metal complexes consist of Zr(IV) surrounded by four O,O-chelating ligands. Besides the preparation and crystal structures for the two complexes, we show that in the solid state the DBQ complex forms a 3-D open framework (with 22% accessible volume) that undergoes a crystal-to-crystal phase transition to a compact structure upon guest molecule release. This process is reversible. In the presence of H2O, CO2, and other small molecules, the framework opens and accommodates guest molecules. CO2 adsorption isotherms…
Horseradish peroxidase-catalyzed oxidation of chlorophyll a with hydrogen peroxide
2010
Horseradish peroxidase was verified to catalyze, without any phenol, the hydrogen peroxide oxidation of chlorophyll a (Chl a), solubilized with Triton X-100. The 13(2)(S) and 13(2)(R) diastereomers of 13(2)-hydroxyChl a were characterized as major oxidation products (ca. 60%) by TLC on sucrose, UV-vis, (1)H, and (13)C NMR spectra, as well as fast-atom bombardment MS. A minor amount of the 15(2)-methyl, 17(3)-phytyl ester of Mg-unstable chlorin was identified on the basis of its UV-vis spectrum and reactivity with diazomethane, which converted it to the 13(1),15(2)-dimethyl, 17(3)-phytyl ester of Mg-purpurin 7. The side products (ca. 10%) were suggested to include the 17(3)-phytyl ester of M…
Solvent extraction studies of uranium(VI) from phosphoric acid: Role of synergistic reagents in mixture with bis(2-ethylhexyl) phosphoric acid
2014
Abstract The extraction of uranium(VI) from 5.3 mol·L − 1 H 3 PO 4 (a typical concentration of wet phosphoric acid) with a series of neutral organosphosphorus synergistic reagents (0.125–0.250 mol·L − 1 ) used in mixture with 0.5 mol·L − 1 bis(2-ethylhexyl) phosphoric acid (D2EHPA) in Isane IP 185 (a 100% isoparaffinic aliphatic diluent) has been investigated. The series of synergistic reagents includes tri- n -butyl phosphate (TBP), di- n -butyl n -butyl phosphonate (DBBP), n -butyl di- n -butyl phosphinate (BDBP), tri- n -butyl phosphine oxide (TBPO), tri- n -hexyl phosphine oxide (THPO), tri- n -octyl phosphine oxide (TOPO), tri- n -decyl phosphine oxide (TDPO), di- n -hexyl n -decyl pho…
pH-responsive physically and chemically cross-linked glutamic-acid-based hydrogels and nanogels
2018
Abstract Given the great demand for polymers prepared from renewable materials, the synthesis of a glutamic-acid-based hydrogel by solution and inverse miniemulsion polymerization is herein presented. Free radical initiated homopolymerizations of N-acryloyl- l -glutamic acid (l- AGA) resulted in either a readily water-soluble polymer or a physically cross-linked hydrogel, being the formation of physical cross-linking junctions closely related to monomer concentration and mixture viscosity. Chemically cross-linked poly( l -AGA-co-BIS) hydrogels were also synthesized by copolymerization of l -AGA and N,N′-methylenebis(acrylamide) (BIS). Both poly (l- AGA) and poly( l -AGA-co-BIS) swelling beh…
Zn-Enhanced Asp-Rich Antimicrobial Peptides N-Terminal Coordination by Zn(II) and Cu(II), Which Distinguishes Cu(II) Binding to Different Peptides
2021
The antimicrobial activity of surfactant-associated anionic peptides (SAAPs), which are isolated from the ovine pulmonary surfactant and are selective against the ovine pathogen Mannheimia haemolytica, is strongly enhanced in the presence of Zn(II) ions. Both calorimetry and ITC measurements show that the unique Asp-only peptide SAAP3 (DDDDDDD) and its analogs SAAP2 (GDDDDDD) and SAAP6 (GADDDDD) have a similar micromolar affinity for Zn(II), which binds to the N-terminal amine and Asp carboxylates in a net entropically-driven process. All three peptides also bind Cu(II) with a net entropically-driven process but with higher affinity than they bind Zn(II) and coordination that involves the N…
ChemInform Abstract: Synthesis of 1,2-Disubstituted Indoles from α-Aminonitriles and 2-Halobenzyl Halides.
2016
The α-alkylation of deprotonated Strecker products derived from primary amines and aromatic aldehydes with 2-halobenzyl halides furnishes intermediates that can be cyclized to 1,2-disubstituted indoles in moderate to high yields (up to 94% over two steps) by microwave-assisted copper- or palladium-catalyzed intramolecular cross-coupling.
Thermodynamics of Proton Binding of Halloysite Nanotubes
2016
In this paper, new information on physical and chemical properties of the widely used nanostructured Halloysite mineral are reported. Given that the Halloysite has a tubular structure formed by a variable number of wrapped layers containing Si-OH and Al-OH groups, their proton binding affinity was measured at different ionic strengths and ionic media by means of potentiometric measurements in heterogeneous phase. One protonation constant for the Si-OH groups and two for the Al-OH groups were determined. The protonation constant values increase with increasing of the ionic strength in all the ionic media. This suggests that the presence of a background electrolyte stabilizes the protonated s…
Synthesis, characterization and X-ray crystal structures of cyclam derivatives. Part VI. Proton binding studies of a pyridine-strapped 5,12-dioxocycl…
2005
The 14-membered cyclic diamide 1,4,8,11-tetraazacyclotetradecane-5,12-dione (5,12-dioxocyclam) can be considered as a trans-autodiprotected tetraazamacrocycle and provides a convenient starting material for the preparation of macrobicyclic receptors. As an example, the secondary amine nitrogen atoms located at the 1 and 8 positions were cross-bridged with a 1,3-pyridyl strap, affording the constrained ansa-dioxocyclam ligand 1,9,12,18,22-pentaazatricyclo[7.6.6.13,7]docosa-3,5,7(22)-triene-13,19-dione (L1). The proton binding properties of this cage-type compound, which possesses a hemispherical cavity, were fully investigated by spectroscopic (IR, NMR, UV, MALDI-TOF MS), quantum chemical, a…
(o-Hydroxyphenyl)methylphosphonic Acids: Spectrophotometric determination of their pKavalues and of the deprotonation sequence
1993
UV/VIS Absorption spectra of nitrosubsituted (o-hydroxyphenyl)methylphosphonic acids (o-(phosphonomethyl)phenols) were measured as a function of pH at 25° in 0.1M NaClo4 solutions. Computational treatment of the whole set of optical density data between 200 and 500 nm resulted in the determination of the dissociation constants of these polyacids and also of the individual electronic spectra of all the species involved in the deprotonation sequence. The spectral behavior gives information on the structure of the anions formed and consequently the order of the subsequent deprotonation steps could be deduced. For the (2-hydroxy-3-nitro(or 5-nitro)phenyl)methylphosphonic acid and the 2-hydroxy-…