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Query: UMLS:C0847097 (acidity)
 15,165 document(s) hit in 31,850,051 MEDLINE articles (0.00 seconds)

The scope and limitations of the ruthenium-catalyzed propargylic substitution reaction of propargylic alcohols with heteroatom-centered nucleophiles are presented. Oxygen-, nitrogen-, and phosphorus-centered nucleophiles such as alcohols, amines, amides, and phosphine oxide are available for this catalytic reaction. Only the thiolate-bridged diruthenium complexes can work as catalysts for this reaction. Results of some stoichiometric and catalytic reactions indicate that the catalytic propargylic substitution reaction proceeds via an allenylidene complex formed in situ, whereby the attack of nucleophiles to the allenylidene C(gamma) atom is a key step. Investigation of the relative rate constants for the reaction of propargylic alcohols with several para-substituted anilines reveals that the attack of anilines on the allenylidene C(gamma) atom is not involved in the rate-determining step and rather the acidity of conjugated anilines of an alkynyl complex, which is formed after the attack of aniline on the C(gamma) atom, is considered to be the most important factor to determine the rate of this catalytic reaction. The key point to promote this catalytic reaction by using the thiolate-bridged diruthenium complexes is considered to be the ease of the ligand exchange step between a vinylidene ligand on the diruthenium complexes and another propargylic alcohol in the catalytic cycle. The reason why only the thiolate-bridged diruthenium complexes promote the ligand exchange step more easily with respect to other monoruthenium complexes in this catalytic reaction should be that one Ru moiety, which is not involved in the allenylidene formation, works as an electron pool or a mobile ligand to another Ru site. The catalytic procedure presented here provides a versatile, direct, and one-step method for propargylic substitution of propargylic alcohols in contrast to the so far well-known stoichiometric and stepwise Nicholas reaction.
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PMID:Ruthenium-catalyzed propargylic substitution reactions of propargylic alcohols with oxygen-, nitrogen-, and phosphorus-centered nucleophiles. 1565 Oct 18

An enzymatic method of producing a conducting polyelectrolyte complex of polyaniline (PANI) and poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) was developed. Acidic stable peroxidase isolated from royal palm tree (Roystonea regia L.) leaves was used as a catalyst in the oxidative polymerization of aniline at pH 2.8. The synthesis procedure was optimized. Spectroscopic and electrochemical characteristics of nanoparticles of obtained PANI/PAMPS complexes at different pH were studied. It was shown that the acidity of the medium affects their properties.
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PMID:[Enzymatic synthesis of a conducting complex of polyaniline and poly(2-arcylamido-2-methyl-1-propanesulfonic ACID) using palm tree peroxidase and its properties]. 1597 87

Kinetic degradation process of PAn films during aniline polymerization was in situ monitored by UV-Visible absorption spectrum. The effects of anodic potential, acidity and monomer concentration on the degradation process were also investigated. The experiment results displayed that the more positive the anodic potential, the higher the acidity of the solution, the higher the concentration of aniline, the faster the PAn films degradation speed. Which was similar to the results obtained when the kinetic degradation process of PAn films was studied in blank solutions by cyclic voltammetry.
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PMID:[In situ UV-visible absorption spectrum monitoring the electrochemical degradation of PAn films]. 1612 80

The course of aniline oxidation with ammonium peroxydisulfate in aqueous solutions has been investigated. The reaction was terminated at various times and the intermediates collected. Besides the precipitates, the films deposited in situ on silicon windows have also been studied. The kinetic course of polymerization is controlled by the acidity level, which changes during the polymerization from pH 8 to a final value close to pH 1. It has two distinct exothermic phases. Gel-permeation chromatography indicates that aniline oligomers are produced at first at high pH, while polyaniline follows after the pH becomes sufficiently low. The growth of polyaniline nanotubes was observed by optical microscopy and confirmed by electron microscopy. The molecular structure of the reaction intermediates was studied in detail by FTIR spectroscopy. Oxidation products are markedly sulfonated, and they contain phenazine units. Aniline oligomers are more soluble in chloroform than the polymer fraction, which contains nanotubes.
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PMID:Evolution of polyaniline nanotubes: the oxidation of aniline in water. 1668 91

Infrared photodissociation (IRPD) spectra of mass-selected clusters composed of protonated aniline (C6H8N+ = AnH+) and a variable number of neutral ligands (L = Ar, N2) are obtained in the N-H stretch range. The AnH+ -Ln complexes (n < or = 3) are produced by chemical ionization in a supersonic expansion of An, H2, and L. The IRPD spectra of AnH+-Ln feature the unambiguous fingerprints of at least two different AnH+ nucleation centers, namely, the ammonium isomer (5) and the carbenium ions (1 and/or 3) corresponding to protonation at the N atom and at the C atoms in the para and/or ortho positions, respectively. Protonation at the meta and ipso positions is not observed. Both classes of observed AnH+-Ln isomers exhibit very different photofragmentation behavior upon vibrational excitation arising from the different interaction strengths of the AnH+ cores with the surrounding neutral ligands. Analysis of the incremental N-H stretch frequency shifts as a function of cluster size shows that microsolvation of both 5 and 1/3 in Ar and N2 starts with the formation of intermolecular H bonds of the ligands to the acidic NH protons and proceeds by intermolecular pi bonding to the aromatic ring. The analysis of both the photofragmentation branching ratios and the N-H stretch frequencies demonstrates that the N-H bonds in 5 are weaker and more acidic than those in 1/3, leading to stronger intermolecular H bonds with L. The interpretation of the spectroscopic data is supported by density functional calculations conducted at the B3LYP level using the 6-31G* and 6-311G(2df,2pd) basis sets. Comparison with clusters of neutral aniline and the aniline radical cation demonstrates the drastic effect of protonation and ionization on the acidity of the N-H bonds and the topology of the intermolecular potential, in particular on the preferred aromatic substrate-nonpolar ligand recognition motif.
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PMID:Spectroscopic identification of carbenium and ammonium isomers of protonated aniline (AnH+): IR spectra of weakly bound AnH+ -Ln clusters (L = Ar, N2). 1712 93

The effect of a co-eluting halogenated phenol, spiked at 1% of the main analyte level, has been examined for a series of halogenated phenols using LC-MS techniques. Similarly, the effect of co-eluting anilines has been investigated. The purpose of the work presented here was to evaluate the degree of signal suppression for structurally similar halogenated phenols and for similar anilines utilizing atmospheric pressure chemical ionization (APCI) in the negative mode and electrospray (ESI) in positive mode, respectively. A correlation between the effects of analyte ionization efficiency resulting from co-eluting compounds (signal suppression) and pK(a) has been made for these compounds. It was found that minimal signal suppression occurs when the spiked impurity has a similar (Delta pK(a)<1.5) acidity when compared to the main peak it is co-eluting with. The degree of signal suppression sharply increases when the difference in pK(a)'s between the main peak and the spiked impurity was greater than 1.5 units. Thus, when the main peak is much less acidic (more than 1.5 pK(a) difference) than the co-eluting impurity, signal suppression of the latter would not occur in negative mode APCI. Similarly, when the main peak is much less basic than the co-eluting peak, signal suppression of the impurity will also not be found for aniline compounds in positive mode ESI. Furthermore, the degree of signal suppression decreases as a function of sample load such that injections of 3 microg or less show no discernible impact on the spiked impurity peak. Ultimately, these results indicate that the use of mass spectrometry (MS) in peak purity determinations requires numerous considerations prior to assessing main peak purity. The optimization of sample load during an impurities assay will maximize co-eluting impurity signal as purity determinations by mass spectrometry made at sample loads above the 3 microg (sample load) threshold increase the risk for false negative assessment of impurities.
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PMID:The effect of analyte acidity on signal suppression and the implications to peak purity determinations using atmospheric pressure ionization mass spectrometry. 1737 66

Most of the fluorescent pH probes work near neutral or acidic regions of the pH scale. In this work, two different fluorescent Schiff bases, chloro phenyl imino propenyl aniline (CPIPA) and nitro phenyl imino propenyl aniline (NPIPA), have been investigated for pH sensing in the alkaline region. Absorption and emission based spectral data, quantum yield, fluorescence lifetime, photostability and acidity constant (pK(a)) of the Schiff bases were determined in conventional solvents and in PVC. The long wavelength excitable immobilized Schiff bases CPIPA (lambda(ex)=556 nm) and NPIPA (lambda(ex)=570 nm) exhibited absorption and emission based optical response to proton in the pH range of 8.0-12.0 and 7.0-12.0, respectively. Response of the CPIPA was fully reversible within the dynamic working range. The response times were between 3-13 min. A relative signal change of 95% and 96% have been achieved for sensor dyes of CPIPA and NPIPA, respectively. The CPIPA displayed better fluorescence quantum yield (varphi(F)=3.7 x 10(-1)) and higher matrix compatibility compared to NPIPA (varphi(F)=1.6 x 10(-1)) in immobilized PVC. The CPIPA and NPIPA exhibited a slight cross sensitivity to the ions of Hg(+) and Fe(3+), respectively.
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PMID:Fiber optic pH sensing with long wavelength excitable Schiff bases in the pH range of 7.0-12.0. 1738 92

The effect of solvent participation on the ligand-to-metal charge transfer (LMCT, L-->Co(III)) reduction of the of Co(III)(en)(2)Br(RC(6)H(4)NH(2))(2+) where R=m-OCH(3), p-F, H, m-CH(3), p-CH(3,)p-OC(2)H(5) and p-OCH(3) were examined in aqueous 2-methyl-2-propanol (Bu(t)OH) solutions. The change in the reduction behavior of Co(III) centre was also examined through cyclic voltammetric studies. The observed reduction in quantum yield due to LMCT excitation can mainly be accounted using linear solvation energy relationship (LSER) comprising model correlation equations. These consist of empirical parameters such as Grunwald-Winstein's solvent ionizing power, Y, Dimroth-Richardt's solvent micro-polarity parameter, E(T)(N), Gutmann's donor number, DN(N), along with Kamlet-Taft's solvatochromic parameters (hydrogen bond acceptor acidity/basicity alpha/beta and solvent dipolarity/polarizability, pi*). The origin of solvent effect is found to be due to microscopic interaction between the solvent donor and the nitrogen-bound hydrogen of the ligand. Cyclic voltammograms show an irreversible reduction of Co(III) in DMF using Glassy Carbon Electrode, GCE, the redox peaks for the aniline complexes appear at -0.20 and 0.525V. Irradiation of the complexes with UV light (lambda=254nm) in binary mixtures produce Co(II)(aq) and the concentration of this species are highly dependent on x(alc) (x(alc)=mole fraction of alcohol). The observed quantum yield (logPhi(Co(II))) is found to be linearly related to mole fraction of organic co-solvent added in the mixture, therefore, logPhi(Co(II))=26.41 x 10(-2) when x(2)=0.0094 and 43.75 x 10(-2) when x(2)=0.076 for a typical complex Co(III)(en)(2)Br(p-OCH(3)C(6)H(4)NH(2))(2+) in aqueous 2-methyl-2-propanol at 300K. Cyclic voltammetry and LSER analyses illustrate the variation of reduction property of Co(III) by the aryl ligand and homogeneous solvation of the excited state of the complex Co(III)(en)(2)Br(RC(6)H(4)NH(2))(2+) in H(2)O/Bu(t)OH mixtures.
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PMID:Homogeneous solvation controlled photoreduction of cobalt(III) complexes in aqueous 2-methyl-2-propanol solutions linear solvation energy relationship and cyclic voltammetric analyses. 1769 8

The progress of the oxidative polymerization of aniline with ammonium peroxydisulfate in an aqueous medium has been monitored in situ by attenuated total reflection Fourier transform infrared spectroscopy. The growth of polyaniline film at the crystal surface, as well as the changes proceeding in the surrounding aqueous medium, are reflected in the spectra. The evolution of the spectra during aniline polymerization in the presence of acetic or sulfuric acid was studied with the aim of understanding the influence of acidity on the observed morphology of the final polyaniline films, granular or nanotubes. The changes occurring during polymerization are discussed with the help of differential spectra. Several processes connected with the various stages of aniline oxidation, the evolution of film morphology, or protonation, were distinguished by using factor analysis applied to a large number of spectra obtained in the course of aniline polymerizations on the crystal.
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PMID:Polymerization of aniline in the solutions of strong and weak acids: the evolution of infrared spectra and their interpretation using factor analysis. 1802 93

The effect of cyano substituents on the photoacidity of mono- and dicyanoanilines has been investigated. It was demonstrated that the cyano substitution increases significantly the acidity of aniline derivatives in the excited state in comparison to the ground state. 3,5-Dicyanoaniline is the strongest acid in the lowest excited singlet state, while 4-cyanoaniline is the weakest one. The derivatives of aniline with two cyano groups in o,o'-position show different properties from those characteristic for aniline and other investigated cyanoanilines. In the methanol solution with sodium methanolate the anions of 2,6-dicyano-3,5-dimethylaniline and 2,6-dicyano-3,5-diphenylaniline appear already in the ground state. The electronic ground and excited state charge distributions and dipole moments of all investigated cyanoanilines have been evaluated by ab initio calculations using the GAMESS program.
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PMID:Protolytic dissociation of cyanoanilines in the ground and excited state in water and methanol solutions. 1837 86


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