Kinetics and mechanism of proton transfer between disubstituted benzoic acids and carbinol base of crystal violet in chlorobenzene

An investigation on the detailed kinetics of proton transfer between a set of di- and monofluoro- and chloro- (2,3-, 2,5-, 2,6-, 3,5-, 2-, and 3-) benzoic acids (HA) and Crystal Violet carbinol base in chlorobenzene favors a mechanism in terms of fast equilibrium between HA and D to form a H-bonded complex, D...HA, followed by rate-limiting proton transfer along the H-bond to form the colored ion pair DH+A- under the combined influence of monomer HA catalyst, nonreactive cyclic dimer (HA)2 inhibitor, and hyperacidic homoconjugated complex H(HA2) catalyst through a transition state with nearly 60% charge separation.     

A study of field induced transitions (FiT) in the nematic phase of an inter hydrogen bonded ferroelectric liquid crystal

A novel series of hydrogen bonded ferroelectric liquid crystals (HBFLC) have been isolated. Hydrogen bond is formed between non mesogen chiral ingredient (S)-1, 2–cholo-3-(4-hydroxy) phenyl propionic acid and mesogenic p-n alkoxy benzoic acids. Phase diagram is constructed from the transition temperatures obtained by differential scanning calorimetry (DSC) and polarizing optical microscopic (POM) studies. Thermal and electrical properties exhibited by a hydrogen bonded complex namely (S)-1,2–cholo-3-(4-hydroxy)phenyl propionic acid with octyloxy benzoic acid (CTy + 8BA) are discussed. Observation of dielectric hysteresis in CTy + 8BA makes it more suitable for device applications. Salient feature of the present work is observation of a field induced transitions in nematic phases pertaining to the above complex designated as FiT. This phenomenon has been confirmed by optical textures of POM, helicoidal measurements, optical intensity and dielectric studies. Four threshold electrical field values are noticed which in turn contributed to four new phases (E₁, E_2, E₃ and E₄) induced by electric field and helical pitch measurements supports the above observation. FiT is reversible in the sense that when applied field is removed the original texture is restored.     

Exploratory analysis in thermodynamics of equilibria. Classification and prediction of benzoic acid strength in aqueous-organic solvents

Decisive rule for classification and prediction of benzoic acid strength from dielectric constant and Kamlet–Taft parameter of the mixed solvents (water–methanol, water–ethanol, and water–2-propanol) has been elaborated basing on the results of multivariate exploratory analysis. The rule has been verified using the independent experimental data on dissociation constant of benzoic acid in water–dioxane and water–dimethylsulfoxide mixtures. Two-parameter linear regression model of the Gibbs energy of benzoic acid dissociation as a function of the properties of aqueous-alcoholic solvents has been built, and the contributions of dielectric and cohesion medium properties to the decrease in the acid strength have been shown.     

Ultrafast Internal Conversion in a Model Anthocyanin–Polyphenol Complex: Implications for the Biological Role of Anthocyanins in Vegetative Tissues of Plants

The red flavylium cations of anthocyanins form ground‐state charge‐transfer complexes with several naturally occurring electron‐donor copigments, such as hydroxylated flavones and hydroxycinnamic or benzoic acids. Excitation of the 7‐methoxy‐4‐methyl‐flavylium–protocatechuic acid complex results in ultrafast (240 fs) internal conversion to the ground state of the complex by way of a low‐lying charge‐transfer state. Thus, both uncomplexed anthocyanins, whose excited state decays by fast (5–20 ps) excited‐state proton transfer, and anthocyanin–copigment complexes have highly efficient mechanisms of deactivation that are consistent with the proposed protective role of anthocyanins against excess solar radiation in the vegetative tissues of plants.     

Polyaniline doped by a new class of dopants,benzoic acid and substituted benzoic acid: synthesis and characterization

This work reports on a new class of dopants, benzoic acid and substituted benzoic acids such as 2‐hydroxybenzoic acid, 2‐chlorobenzoic acid, 4‐nitrobenzoic acid, 2‐methoxybenzoic acid, 3‐methylbenzoic acid, 4‐methylbenzoic acid, 3‐aminobenzoic acid and 4‐aminobenzoic acid, for polyaniline. Benzoic acids can be used to dope polyaniline by mixing benzoic acid (or a substituted benzoic acid) with polyaniline in the common solvent 1‐methyl‐2‐pyrrolidone. Properties of benzoic acid doped polyaniline salts are studied using Fourier transform infra‐red, X‐ray diffraction spectroscopy, scanning electron microscopy, thermogravimetric analysis and conductivity measurements. The conductivity of polyaniline‐benzoic acid salt was found to be high (10⁻² S/cm) when compared to polyaniline‐substituted benzoic acid salts (10⁻³–10⁻⁵ S/cm). Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis of 1,2- and 1,3-dicarboxylic acids via Pd(II)-catalyzed carboxylation of aryl and vinyl C-H bonds

A Pd(II)-catalyzed reaction protocol for the direct carboxylation of benzoic and phenylacetic acid derivatives to form dicarboxylic acids has been developed. The reaction conditions are also applicable for the carboxylation of vinyl C-H bonds. The first C-H insertion Pd-aryl complex from carboxylic acids has been characterized by X-ray crystallography.     

Dosage simultane par chromatographie liquide a haute performance de l'acide benzoique et de l'acide sorbique: High-performance liquid chromatographic determination of benzoic and sorbic acids

High-performance liquid chromatographic determination of benzoic and sorbic acids. Quantitative h.p.l.c. for benzoic and sorbic acids in foodstuffs, especially soft drinks, is described. Recoveries were 101.49% ± 1.39 for sorbic acid and 99.52% ± 1.05 for benzoic acid in the concentration ranges normally used (50–100 mgl^-1).     

Infrared and ab initio studies of hydrogen bonding and proton transfer in the complexes formed by pyrazoles

The results of experimental studies and quantum mechanical calculations of vibrational spectra and structure of hydrogen bonded complexes formed by pyrazole (P) and 3,5-dimethylpyrazole (DMP) are presented. IR spectra of pyrazoles in solutions, gas phase, and solid state have been investigated in wide range of concentrations and temperatures. It has been found that in the gas phase both P and DMP reveal the equilibrium between monomers, dimers, and trimers. In solutions the equilibrium between monomers and trimers dominates, no bands, which can be attributed to dimers were detected. DMP retains the trimer structure in solid state, while in the case of pyrazole P, formation of the crystal provides another type of association. Geometrical and spectral characteristics of dimers and trimers, obtained by ab initio calculations, are presented and compared with experimental data.

IR spectra of solutions containing P and DMP with a number of acids (acetic and trifluoroacetic acids, pentachlorophenol, HBr) have been studied in parallel with ab initio calculations. It has been found that pentachlorophenol forms with pyrazoles complexes with one strong hydrogen bond O–HN, while NH pyrazole group remains unbonded. With carboxylic acids DMP forms 1:1 cyclic complexes with two hydrogen bonds. In the case of acetic acid, the complex in CH₂Cl₂ solution reveals molecular structure with OHN and C=OHN bonds, in accordance with results of the calculations. For trifluoroacetic acid, the calculations predict the molecular structure to be energetically more stable in the case of the isolated binary complex (in gas phase), while the experimental spectrum of CH₂Cl₂ solution gives an evidence of the proton transfer with formation of the cyclic ionic pair with two NH⁺O⁻ bonds. The agreement with experimental results can be improved by taking into account the influence of environment in the framework of Onsager or Tomasi models. The shape of proton potential function of the complexes and medium effect on its parameters, resulted from experimental data and calculations, are discussed. It has been found that the number of potential minima and their relative depth depend strongly on the method of calculations and the basic set. Under excess of trifluoroacetic acid, the formation of 2:1 acid–DMP complex has been detected. Spectral characteristics and results of calculations point to the cyclic structure of this complex, which includes homoconjugated bis-trifluoroacetate anion and DMPH⁺ cation. With HBr both studied pyrazoles were found to form ionic complexes including one or two pyrazole molecules per one acid molecule and correspondingly monocation or homoconjugated cation BHB⁺.     

Dosage de sept agents conservateurs dans les denrées alimentaires par chromatographie liquide a haute performance

(Determination of seven food preservatives by high-performance liquid chromatography.) Solvent-programmed h.p.l.c. is applied for the determination of sorbic, benzoic and salicylic acids and p-hydroxybenzoic acid as well as three of its esters, singly or in mixture; quantitative separation takes less than 20 min. Recoveries varied from 90.9 to 99.4% for the concentration range 200–1000 ppm when the method was applied to mayonnaise.     

Effect of ligand structure on synergism in Tb3+-aromatic acid complexes: fluorescence lifetime studies

The fluorescence of Tb3+ sensitized by aromatic carboxylic acid ligands (benzoic, monomethylphthalic, monomethylterephthalic, trimesic, terephthalic, isophthalic, phthalic and mellitic acids) and the synergism displayed by these complexes when treated with TOPO/Triton X-100 have been studied by measuring lifetimes of Tb3+ emission. The lifetime of Tb3+ fluorescence was not significantly altered following complex formation with aromatic carboxylic acids, even though a significant enhancement in the Tb3+ fluorescence intensity was observed in every single case. However, when these Tb3+-aromatic acid complexes were treated with TOPO/Triton X-100, the lifetimes of the Tb3+ fluorescence increased markedly, but only with certain acids. Interestingly, even amongst the acids that showed an increase in lifetime with TOPO/Triton X-100, the lifetimes as a function of the pH of the solution was strongly dependent on the structure of the ligand. These differences and the reasons for such behavior are discussed, which shed light on the role of the structure of the ligand on the synergism process.     

Theoretical studies of inclusion complexes of β-cyclodextrin with methylated benzoic acids

AM1 semiempirical molecular orbital calculations have been performed on the inclusion complexes of β-cyclodextrin (β-CD) with methylated benzoic acids in two orientations, the “head-first” and “tail-first” positions. In the former, the CO₂H group points toward the primary hydroxyls of the CD. In the latter, it points away from them. Out of 30 possible inclusion complexes, AM1 results predict only three clearly stable inclusion complexes. These are β-CD with 4-methyl benzoic acid in the head-first position, β-CD with 2,4-dimethyl benzoic acid in the head-first position, and β-CD with 3,5-dimethyl benzoic acid in the tail-first position. The orientations of the stable inclusion complexes correlate with the total number of intramolecular hydrogen bonds and intermolecular hydrogen bonds. The stability of a complex also correlates with the closeness of the host and guest geometries in the complex to their isolated molecule geometries. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 64 : 711–719, 1997     

Simultaneous determination of sorbic and benzoic acids in food dressing by headspace solid-phase microextraction and gas chromatography

A facile headspace solid-phase microextraction (HS-SPME) procedure using 85 microm polyacrylate (PA) fiber is presented for the simultaneous determination of preservatives (sorbic and benzoic acids) in food dressing, including Thousand Island Dressing, HellMANN'S Salad Dressing and Tomato Ketchup, by gas chromatography (GC) with flame ionization detector (FID). The method presented preserves the advantages typical of HS-SPME such as simplicity, low intensity of labor, low cost and solvent free. The main factors affecting the HS-SPME process, such as extraction temperature and time, desorption temperature and time, the acidity and salt concentration of the solution, were optimized. Limits of detection (LODs) of the method were 2.00 microg/L for sorbic acid and 1.22 microg/L for benzoic acid. Relative standard deviations (RSDs) for quintuplicate analyses at three concentration levels of 0.10, 2.0 and 20 mg/L ranged between 3.86 and 14.8%. The method also showed good linearity n a range from 0.02 to 40 mg/L with correlation coefficients (R2) of 0.9986 for sorbic acid and 0.9994 for benzoic acid. Recoveries for the two analytes in all the samples tested ranged from 83.44 to 113.2%. Practical applicability was demonstrated through the simultaneous determination of sorbic and benzoic acids in the three complex samples.     

Supramolecular liquid crystals formed by hydrogen bonding between a benzocrown-bearing stilbazole and carboxylic acids

The mesomorphism of hydrogen bonded complexes formed between 4'-carboxybenzo-15-crown-5 stilbazolyl ester (CBCSE) as proton acceptor and carboxylic acids as proton donors is discussed. CBCSE is a monotropic mesogen, forming a nematic phase upon quench cooling. A total of 32 hydrogen bonded complexes has been studied. Hydrogen bonding with carboxylic acids stabilizes the nematic phase, and/or induces a smectic A (SmA) phase. CBCSE forms 1:1 complexes (molar ratio) with alkanoic acids (fatty acids) and 2:1 complexes with alkanedioic acids. None of these proton donors is a mesogen itself, but the hydrogen bonded complexes are. The influence of the chain or spacer length on the transition temperatures is discussed. Besides the homologous series of the alkanoic and alkanedioic acids, the following carboxylic acids were used in this study: diglycolic acid, pyridine-2,6-dicarboxylic acid, 4-dodecyloxybenzoic acid, 3,4-bis(dodecyloxy)benzoic acid, 2,3,4-tris(dodecyloxy)benzoic acid and 3,4,5-tris(dodecyloxy)benzoic acid, phthalic acid, isophthalic acid and terephthalic acid.     

Chemical ionization (NO) spectra of n-alkenoic acids and their esters

It is shown that the position of one double bond in long-chain unsaturated fatty acids and their esters can be determined by chemical ionization (NO) mass spectra. Homoconjugated dienoic acids (as linoleic acid) do not give a characteristic framentation pattern, in contrast to those which contain three or more homoconjugated double bonds.     

Supramolecular liquid crystals formed by hydrogen bonding between a benzocrown-bearing stilbazole and carboxylic acids

The mesomorphism of hydrogen bonded complexes formed between 4'-carboxybenzo-15-crown-5 stilbazolyl ester (CBCSE) as proton acceptor and carboxylic acids as proton donors is discussed. CBCSE is a monotropic mesogen, forming a nematic phase upon quench cooling. A total of 32 hydrogen bonded complexes has been studied. Hydrogen bonding with carboxylic acids stabilizes the nematic phase, and/or induces a smectic A (SmA) phase. CBCSE forms 1:1 complexes (molar ratio) with alkanoic acids (fatty acids) and 2:1 complexes with alkanedioic acids. None of these proton donors is a mesogen itself, but the hydrogen bonded complexes are. The influence of the chain or spacer length on the transition temperatures is discussed. Besides the homologous series of the alkanoic and alkanedioic acids, the following carboxylic acids were used in this study: diglycolic acid, pyridine-2,6-dicarboxylic acid, 4-dodecyloxybenzoic acid, 3,4-bis(dodecyloxy)benzoic acid, 2,3,4-tris(dodecyloxy)benzoic acid and 3,4,5-tris(dodecyloxy)benzoic acid, phthalic acid, isophthalic acid and terephthalic acid.     

Preparation of Titania Monolith Column and Application in Determination of Benzoic Acid by HILIC

The titania monolith column has been synthesized through a template-free sol–gel route, and a simple and reliable method for the determination of benzoic acid by hydrophilic interaction liquid chromatography using the prepared titania monolith has been developed. The influences of acetonitrile, acetate buffer and buffer pH on the retention of benzoic acid were investigated. Benzoic acid in carbonated drinks and fruit beverages samples were determined within 5?min and quantitative analysis was carried out by external standard method with a correlation coefficient (R ²) of 0.9984. The relative standard deviation was 0.91?% and the recovery ranged from 92.5 to 101.3?%. The proposed method is suitable for the analysis of benzoic acid in beverage samples.     

Induction of mesomorphism in mixtures of poly[4-(3-methacryloylpropyl)pyridine] with partially fluorinated derivatives of benzoic acid

LC complexes of nonmesomorphic poly[4-(3-methacryloylpropyl)pyridine] with partially fluorinated derivatives of benzoic acid have been prepared via intermolecular hydrogen bonding between complex components. The induction of mesomorphic state has been observed for both mesomorphic and nonmesomorphic acids. It has been shown that the type of a mesophase manifested by the complexes varies from layered to columnar and cubic depending on the number of substituents in a low-molecular-mass component.     

Preparation of Titania Monolith Column and Application in Determination of Benzoic Acid by HILIC

The titania monolith column has been synthesized through a template-free sol–gel route, and a simple and reliable method for the determination of benzoic acid by hydrophilic interaction liquid chromatography using the prepared titania monolith has been developed. The influences of acetonitrile, acetate buffer and buffer pH on the retention of benzoic acid were investigated. Benzoic acid in carbonated drinks and fruit beverages samples were determined within 5 min and quantitative analysis was carried out by external standard method with a correlation coefficient (R ²) of 0.9984. The relative standard deviation was 0.91 % and the recovery ranged from 92.5 to 101.3 %. The proposed method is suitable for the analysis of benzoic acid in beverage samples.

     

Chemiluminescence Determination of Benzoic Acid Using A Solid-Phase Verdigris Reactor

Benzoicacidisacommonadditiveusedwidelyasfoodpreservativeandplasticizer.Itcouldpromoteseverereactiontoallergicpopulationevenatlowconcentrationlevel1.Routinemethodsfortheassayofbenzoicacidincludeschromatographic2-6,spectrophotometry7,8,capillaryelectrophoresis9-13andelectrochemicaltitration14.Stokes15etal.monitoredairbornebenzoicacidbasedonsurface-enhancedRamanscatteringtechniques.Thereisalsoreportonamicrobialsensorusingpseudomonasforbenzoicacidandtheirderivativesinaqua16.Interestofusinglumines…     

Structural characterization of fatty acids cationized with copper by electrospray ionization mass spectrometry under low-energy collision-induced dissociation

Fatty acids have for many years been characterized by mass spectrometry using electron ionization after chemical derivatization. When fatty acids are ionized using desorption/ionization methods such as electrospray ionization or fast atom bombardment, structural information is usually obtained through high-energy collision-induced dissociation (CID) using sector instruments. It has been shown that copper displays very interesting properties in the gas phase during CID. In this study, the reactivity of saturated and unsaturated fatty acid-copper [M-H+Cu(II)]+ complex and the role of the copper ion in promoting fragmentations were investigated under low-energy collisional activation conditions. The decomposition of these species in an ion trap instrument led to diagnostic ion series that reflect C--C bond cleavage, which involves Cu(II) reduction followed by the release of an alkyl radical. It was demonstrated that in this way the localization of one or two homoconjugated double bonds is possible using low-energy CID. Moreover, the distinction of cis and trans isomers is possible through characteristic product ions related to a specific loss of CO2. When these experiments are repeated using a triple-quadrupole instrument with argon as collision gas, a different behavior is observed as in this case, in addition to the product ion distributions observed in the ion trap, other distributions are observed that reflect the influence of the different kinetic shifts and the occurrence of consecutive decompositions. Different examples are presented with various saturated and unsaturated fatty acid chains. Mechanisms are proposed in order to rationalize the experimental observations.