Acidity of Several Anilinium Derivatives in Pure Tetrahydrofuran

The acidity constant (pK _a) of eleven substituted anilinium ions and the dissociation constants of their perchlorate salts (pK _salt) were determined in pure tetrahydrofuran by potentiometry and conductometry. The pK _a values of the studied aniliniums extend downward the range of previously determined pK _a values. The resolution of acid strength for cationic acids in tetrahydrofuran was compared with those obtained in other amphiprotic and aprotic solvents. It is shown that the resolution in tetrahydrofuran is higher than the ones in water and methanol, similar to those in acetone, dimethyl sulfoxide and isobutylmethylketone, but lower than those in acetonitrile and nitromethane.     

Ion transport and states of water in charged poly(allylamine) membranes

Cationically charged poly(allylamine) (PAA) membranes having various water contents [0.49 < H < 0.63 (g H₂O/g wet membrane)] were prepared. Sorption and permeation of simple salts (sodium chloride and sodium tetraphenylborate) were investigated, taking into account the state of the water in these membranes. The weight ratios of freezable water and free water to total water (W_fz/W_t, and W_f/W_t) in the membranes were estimated by means of DSC and pulsed ¹H-NMR measurements, respectively. Partition coefficients K for total water were converted into those in freezable and free water, K_fz and K_f, using W_fz/W_t and W_f/W_t. The permeability of both salts in the membranes could be interpreted satisfactorily by an equation derived from the Teorell-Meyer-Sievers theory using values of K_f. The free water is mainly involved in the permeation of simple salts through PAA membranes while bound water hardly takes part.     

Energy dispersive polarized X-ray Fluorescence spectra of alkali and alkali earth metal chloride salts with amino acids at 25°C

Electron impulse in counts per second (CPS) of innermost electrons of solid salts, with water (aq) and aqueous glycine and DL-α-alanine with 0.5 M alkali salts solutions, at 35 kV and 1.5 mA were studied with Energy Dispersive Polarized X-ray Fluorescence (EDPXRF or XRF) around 0 to 12.5 keV energies. The CPS values derived from XRF spectra were regressed against concentrations for limiting CPS⁰ values. Different CPS values for each composition of salts and amino acids were noted due to hydration and salt-amino acid interaction. The XRF values illustrate ion-water-amino acid interactions. The CPS⁰ values are higher for solid salts(s) than those of aqueous and amino acids enhanced the CPS⁰ values of aq salts with stronger hydration energies (ΔG _HE) due to perturbation of ion-dipole and ion-dipole-amino acid interactions. A quantum treatment for a response of innermost electron of salts is used to explain an ionic hydration. The CPS values of solid salts vary at a rate of 11944 as compared to aqueous solutions. The article is published in the original.     

Clouding behavior of nonionic–cationic and nonionic–anionic mixed surfactant systems in presence of carboxylic acids and their sodium salts

The study is focused on evaluation of clouding phenomena of the aqueous single nonionic surfactant system Triton X-100 (TX-100) and its mixed systems with anionic aerosol-OT (AOT) and cationic dodecylpyridinium chloride (DPC) in presence of hydrophobic ions furnished by sodium salts of carboxylic acids, viz., sodium ethanoate, sodium propanoate, sodium butanoate, and sodium hexanoate and the respective carboxylic acids [ethanoic acid, propanoic acid, butanoic acid, and hexanoic acid]. The influence of salts on the cloud point (CP) has been explained on the basis of salt effect as well as the solubilization of higher alkyl chain hydrophobic ions furnished by these salts. Moreover, the co- and counterion effect has been taken into account to explain the variation of the CP in the mixed systems. However, the effect of acids on CP has been explained in the light of their aqueous solubility and their partitioning ability between octanol and water as reflected by their K _OW values.     

Investigation and radiometric determination of saturated and unsaturated aliphatic monocarboxylic acids and aromatic dicarboxylic acids

Investigations have been carried out on the precipitation of calcium salts of saturated and unsaturated aliphatic monocarboxylic acids and of aromatic dicarboxylic acids. The optimum ethanol/water solvent ratio has been studied at which the sodium, ammonium or triethylammonium salts of the acids have a good solubility, whereas the calcium salts are poorly soluble and can be precipitated. Based on these investigations the radiometric determination of formic acid, palmitic acid, stearic acid, methacrylic acid, oleic acid, and o-, m- and p-phthalic acids has become possible. A linear correlation has been found between the solubilities of the calcium salts of o-, m- and p-phthalic acids and the dielectric constant of the solvent mixture. CaCl₂ solution labelled with⁴⁵CaCl₂ was used for the titrations, with a solvent composition identical to that of the solution to be titrated. Radiometric titrations were carried out in 0.05M solutions for dicarboxylic acids, and in 0.1M solutions for monocarboxylic acids. For palmitic and stearic acids titrations were also carried out in the 0.01M concentration range. The equipment used for titrations was capable of detecting isotopes of soft β-radiation.     

Thermodynamic Properties of Peptide Solutions. Part 18. Partial Molar Isentropic Compressibilities of Gly-X-Gly Tripeptides (X = Tyr,Pro, Gln,Asp and Glu), and the Peptide Salts K[GlyAspGly], Na[GlyGluGly] and GlyLysGly Acetate in Aqueous Solution at 25 <Superscript>∘</Superscript>C

The partial molar isentropic compressibilities at infinite dilution, K∘_S,2, have been determined for several tripeptides of the sequence glycyl-X-glycine, where X is one of the amino acids tyrosine, proline, glutamine, aspartic acid, glutamic acid and lysine in aqueous solution at 25 ^∘C. These results, along with those for triglycine, were used to estimate the contributions of the amino acid side-chains to the partial molar isentropic compressibilities of polypeptides. Values for K∘_S,2 have also been determined for aqueous solutions of the two peptide salts K[glyaspgly] and Na[glyglugly]. The K∘_S,2 results for the peptides and their salts have been combined with literature data for electrolytes to calculate the changes in isentropic compressibility upon ionization of the acidic side-chains. The results are compared with those for other carboxylic acid systems.     

Extraction of mono- and dicarboxylic acids from a curative water

A method for the analysis of mono- and dicarboxylic acids from water is presented. For this purpose two techniques, a C₁₈ solid phase extraction (SPE) and a combination method of liquid-liquid extraction (LLE) and aminopropyl SPE, were tested. With the combination method all analytes, short-chain mono- and long-chain dicarboxylic acids, could be analysed in one approach. The C₁₈ SPE was not suitable for short-chain mono- but for dicarboxylic acids. Concentrations in the investigated water ranged from 315 mg/l (butanoic acid) to 2.9 mg/l (octanoic acid). Dicarboxylic acids were found from 5 mg/l (octanedioic acid) to 0.5 mg/l (dodecanedioic acid).     

A direct link between the Passerini reaction and α-lactams

α-Lactams (aziridinones) can function to replace two of the three reactants, the oxo-compound and the isonitrile, in the Passerini reaction. Four α-lactams (5a-d) were reacted with mono- and dicarboxylic acids of positive pK_a values to give 2-acyloxycarboxamides (4) and bis-2-acyloxycarboxamide products 12 and 13, respectively. The same compounds were also prepared via the Passerini reaction. Acids with a negative pK_a decarbonylate α-lactams to give immonium salts. The main path of the reaction depends on the pK_a of the acid component, the reactivity of the α-lactam, and the reaction conditions.     

The Oxidation of Metals with Liebig Acids

In Liebig's definition, an acid is a compound which contains one or more hydrogen atoms which may be substituted by metal atoms. Hence, reactions of Liebig acids in substance, excluding water or any other solvent, with non‐noble metals yield salts and release hydrogen. In this sense, not only the classical mineral acids such as sulfuric or nitric acid, respectively, are Liebig acids. Rather, there is a large variety of organic compounds with, for example, HO‐ or HN‐functions with acid constants that allow for substitution of the hydrogen atoms by a metal atom. Simple covalent hydrides like water and ammonia or even methane may also act as Liebig acids with conditions properly chosen. The ammonium ion, (NH₄)⁺, represents a special case as it is available in a large variety of salts and may react as an acid/oxidant or as a (base)/reductant and is also a pseudo alkali‐metal cation. The versatility of the ammonium ion is reviewed with special emphasis to its ability to function as a Liebig acid, i.e., reactions of, especially, ammonium halides with non‐noble metals.     

Complexation and transport of amino acid esters and their salts with synthesised chiral novel aza crown ether derivatives

The syntheses of four aza-15-crown-5 ethers bearing phenyl and phenoxymethyl moieties attached to a stereogenic centre on the crown ring were achieved. Macrocycles have exhibited strong binding ability (K_a = 5364–12,969 M^? 1) and modest enantiomeric discrimination towards the enantiomers of amino acid methyl ester salts by UV titration method in CHCl₃ at 25°C. Computer modelling results supported experimental data providing a detailed understanding of the molecular recognition mode between hosts and guests and the likely binding sites involved. Macrocycles were used for chiral discrimination of amino acids in their zwitterionic forms or as potassium and sodium salts in transport experiments across a bulk chloroform membrane with satisfactory selectivity.     

pH-Driven adsorption and desorption of fatty acid at the liquid crystal–water interface

The pH-driven adsorption and desorption of fatty acid monolayers at the liquid crystal (LC)–water interface were studied. We doped fatty acids (stearic acid, palmitic acid, myristic acid, dodecanoic acid, and decanoic acid) into 4-cyano-4′-pentylbiphenyl (5CB), and employed sessile LC droplets as our experimental platform. Under a crossed polariser, the LC droplets displayed a bright flower bud-shaped texture at low pH, whereas at high pH, they exhibited a bright four-brush appearance due to desorption of the adsorbed fatty acids at the LC–water interface. Furthermore, we identified the critical transition pH of various concentrations of stearic acid and other fatty acids featuring distinct tail lengths. Based on the interfacial behaviour, we propose a new method to estimate the pK_a of fatty acids, which opens up new possibilities for simple, precise, and reliable measurement of the pK_a of other carboxylic acids. The findings presented herein will greatly facilitate the understanding of the interfacial behaviour of amphiphiles at the oil–water interface.     

Density functional theoretical study of pKa of RCOOH (RH,CH3, and C2H5) using the combination of the extended clusters‐continuum model

The accurate pK_a determinations for three carboxylic acids have been investigated using the combination of the extended clusters‐continuum model at B3LYP/6‐31+g(d,p) and B3LYP/6‐311++g(d,p) levels. To take into account of the effect of the water combined with carboxylic acids in different positions, eleven molecular clusters were considered. Among these clusters, the one involving the carboxylic acid wrapped up with water molecules and saturated with hydrogen bonds (four hydrogen bonds around ? COOH) leads to the best B3LYP pK_a results compared to the experimental data. For those clusters saturated with hydrogen bonds, when n = 3 (the number of water molecules), the average absolute errors between the calculated pK_a results and experimental data of these three carboxylic acids were 0.19 (0.23) and 0.12 (0.22) pK_a at B3LYP/6‐31+g(d,p)//PCM (IEFPCM) and B3LYP/6‐311++g(d,p)//PCM (IEFPCM) levels, respectively; when n = 4, they are 0.53 (1.23) and 1.09 (1.03) pK_a, respectively. On the basis of the above results, the molecular cluster saturated with four hydrogen bonds formed by three waters and one carboxylic acid molecule was the chief existence in the carboxylic acid solution. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

Base Equilibria of Substituted Pyridines in Nitromethane

In the framework of our studies on acid=nbase equilibria in systems comprisingsubstituted pyridines and nonaqueous solvents, acid dissociation constants havebeen determined potentiometrically for a variety of cationic acids conjugatedwith pyridine and its derivatives in the polar protophobic aprotic solvent nitromethane. The potentiometric method enabled a check as to whether and to whatextent cationic homoconjugation equilibria of the BH⁺/B type, as well as cationicheteroconjugation equilibria in BH⁺/B₁ systems without proton transfer, are setup in nitromethane. The equilibrium constants were compared with thosedetermined in water and two other polar protophobic aprotic solvents, propylenecarbonate and acetonitrile. The pK _a values of acids conjugate to the N-bases innitromethane fall in the pK _a range of 5.84 to 17.67, i.e., 6 to 7 pK _a units, onaverage, higher than in water, 1 to 2 units higher than in propylene carbonate,and less than 1 unit lower than in acetonitrile. This means that the basicity ofthe pyridine derivatives increases on going from propylene carbonate throughnitromethane to acetonitrile. Further, it was found that the sequence of the pK _achanges of the protonated amines was consistent in all three media, thus providingthe basis for establishing linear correlations among these values. In the majorityof the BH⁺/B systems in nitromethane, cationic homoconjugation equilibria havebeen established. The cationic homoconjugation constants, log K _BHB+, arerelatively low, falling in the range 1.60–2.89. A comparison of the homoconjugationconstants in nitromethane with those in propylene carbonate and acetonitrile showsthat nitromethane is a more favorable solvent for the cationic homoconjugationequilibria than the other two solvents. Moreover, results of the potentiometricmeasurements revealed that cationic heteroconjugation equilibria were not presentin the majority of the BH⁺/B₁ systems in nitromethane. The heteroconjugationconstant could be determined in one system only, with logdiK _BHB1 + = 2.56.     

Effect of counterion condensation on the acid-base equilibrium of a pH-sensitive merocyanine dye covalently attached to polyelectrolytes

Effects of monovalent and divalent counterions on the acid-base equilibrium of a pH-sensitive merocyanine dye covalently attached to copolymers of acrylic acid and acrylamide with varying charge densities (0.28 < ξ < 2.8) were investigated. Added chloride salts of Li⁺, Na⁺, K⁺, and NH⁺₄ (< 0.2 mM) had essentially no effect on pK observed (pK^obs) for the equilibrium. By contrast, the salts of Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺ caused a significant decrease in pK^obs for the copolymers with larger ξ. With smaller ξ, most likely when ξ < 0.5, no decrease in pK^obs was observed upon addition of the salts of divalent cations. A competitive effect of Ca²⁺ and Na²⁺ ions on pK^obs in the presence of an excess of Na⁺ ions implied that Ca²⁺ ions at very low concentrations were preferentially, and therefore exhaustively, condensed on the polyanions with sufficiently large ξ probably until effective charge density was lowered to 0.5. The observed difference in the influence of the monovalent and divalent cations on pK^obs was discussed in terms of the difference in the microscopic behavior of the condensed monovalent and divalent cations. © 1993 John Wiley & Sons, Inc.     

Electronic absorption of carboxylic acids and their anions

Electronic spectra of formic, acetic, mono-, di-, trichloro- and trifluoroacetic, glycolic, cyanoacetic, pivalic, α-methoxyacetic, lactic, oxalic, tartaric and citric acids and betaine and of corresponding anions were recorded. The acid forms of all the carboxylic acids studied show a medium-strong π → π^* and a weak n → π^* absorption band, the latter in the 220–250-nm region. The corresponding anions (or the completely dissociated forms of polybasic acids) show the π → π^* absorption bands, but no indication of a shoulder corresponding to a n → π^* transition. Changes in the absorbance in the wavelength region corresponding to the n → π^* transition with addition of alkali metal hydroxides can be used for end-point detection in titrations. Changes of these absorbances in solutions of buffers or strong acids can be used for pK determinations. A pK value of 0.89 (at μ = 0.5) was found for dichloroacetic acid; approximate pK values were established by means of the H_o acidity scale for trichloroacetic acid (—0.80) and trifluoroacetic acid (—0.92). Finally, absorbances in the 220–250-nm region can be used for determination of carboxylic acids in solutions of strong acids, and some buffers, like phosphate or borate.     

Retention prediction and hydrophobicity estimation of weak acidic compounds by reversed-phase liquid chromatography using acetic and perchloric acids as ion suppressors

Simple acids are usually applied to suppress the ionization of weakly ionizable acidic analytes in reversed-phase liquid chromatography. The purpose of this study is to investigate the retention behavior of various weak acidic compounds (monoprotic, diprotic, triprotic, and tetraprotic acids) using acetic or perchloric acid as ion suppressor in a binary hydroorganic mobile phase. The apparent n-octanol–water partition coefficient (K _ow ″) was proposed to calibrate the n-octanol–water partition coefficient (K _ow) of weak acidic compound. LogK _ow ″ was found to have a better linear correlation with logk _w, the logarithm of the retention factor obtained by extrapolating to neat aqueous fraction of the mobile phase, for all weakly ionizable acidic compounds. This straightforward relationship offers a potential medium for direct measurement of K _ow data of weak acidic analytes and can be used to predict retention behavior of these compounds in the ion suppression reversed-phase liquid chromatographic mode.     

3-Fluoroalkyl (CF3, CHF2, CH2F) Cyclobutane-Derived Building Blocks for Medicinal Chemistry: Synthesis and Physicochemical Properties

Synthesis and physicochemical characterization of all possible cis- and trans-1,3-disubstituted cyclobutane-derived amines and carboxylic acids bearing mono-, di- and trifluoromethyl groups at the C-3 position is disclosed. Tetramethylammonium fluoride (TMAF)- or morpholinosulfur trifluoride (Morph-DAST)-mediated nucleophilic fluorination of appropriate cis- and trans-diastereomeric substrates was used as the key step for the preparation of CH₂F- and CHF₂-substituted derivatives. To obtain the corresponding cis- and trans-isomeric CF₃-substituted derivatives, resolution of known 3-(trifluoromethyl)cyclobutanecarboxylic acid (obtained as a mixture of diastereomers) was applied. The proposed procedures were suitable for the preparation of corresponding fluoroalkyl-substituted cyclobutane-derived amines and carboxylic acids on up to 50 g scale. All 12 building blocks obtained were characterized by measuring dissociation constants (pK_a) and lipophilicities (LogP, for model derivatives) to evaluate the effect of the fluoroalkyl substituents on their physicochemical properties relevant to further drug discovery applications.     

The extraction of actinides by diphenyl(dibutylcarbamoylmethyl)phosphine oxide in the absence of a solvent

The possibility of changing the aggregate state of several solid mono- and bidentate neutral organophosphorus compounds in contact with various mineral acids was demonstrated. The formation of the liquid phase immiscible with water was observed. The, phase exhibits a high extraction capability with respect to actinides in various oxidation states. The diphenyl(dibutylcarbamoylmethyl)phosphine oxide-NHO₃ extraction system was studied in detail. The composition of the liquid phase was shown to the Ph₂P(O)CH₂C(O)NBu₂·HNO₃·nH₂O (n=2 or 3). The kinetics of formation of this phase and extraction of Amⁱⁱⁱ from solutions of nitric acid and its salts was studied. The organic phase exhibits redox properties, due to which some actinides change the oxidation state during extraction. The “aryl strengthening effect” was suggested to exist for extraction of Am^III in the absence of a solvent. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1739–1745, September, 1998.     

Determination of bioconcentration factors of isomeric polycyclic aromatic hydrocarbons in polychaete worms by HRGC on selective liquid crystalline stationary phases

The bioconcentration factors (K_b) of parent and alkylated PAHs isolated from polychaete worms collected in coastal sediments were determined for the first time. Capillary gas chromatography using a polymeric liquid crystalline (MPMS) and SE-54 stationary phases coupled to FID, MS and concurrent elution with authentic standards permitted positive identifications of parent PAHs. The K_b values of 18 compounds were accurately determined on the liquid crystalline column and the those of mono- and dialkyl-phenathrene, -pyrene and -chrysene were determined by GC-MS on a SE-54 coated column. The experimental K_b values exhibited a moderate correlation (r=0.7–0.8) with the reported octanol-water partition coefficients (K_ow) for these compounds. Consequently, kinetic considerations, i.e. biouptake-release and enzymatic activity seem to be relevant, in addition of biota-media equilibrium. Therefore, integrated bioconcentration models are needed.