A Convenient Synthesis of ω-[(Arylphosphonomethyl)Amino] Alkylphosphonic and Carboxylic Acids via in Situ–Generated Arylideneaminoalkyl- Phosphonic or Carboxylic Acids

ω-[(Arylphosphonomethyl)amino]alkylphosphonic and carboxylic acids are prepared in an easy work-up procedure, by addition of diethyl phosphite to in situ–generated arylideneaminoalkylphosphonic or carboxylic acids followed by hydrolysis with hydrochloric acid     

Ion-exclusion chromatography of carboxylic acids on silica gel modified with aluminium

The modification of silica gel with aluminium by a coating method was effective for the preparation of a silica-based stationary phase, which acted as a cation exchanger under strongly acidic conditions. In order to expand the utility of the laboratory-made aluminium-adsorbing silica gel it was applied as a stationary phase to the ion-exclusion chromatography of various carboxylic acids. Good separations for both aliphatic carboxylic acids and benzenecarboxylic acids with a hydrophobic nature under acidic eluent conditions were achieved in 25 min.     

Preconcentration and separation of haloacetic acids by ion chromatography

A comparative study was made of the chromatographic behaviour of five haloacetic acids (mono-, dibromoacetic and mono-, di-, trichloroacetic acids). The techniques investigated included reversed-phase ion interaction chromatography with UV detection, suppressed and non-suppressed anion-exchange chromatography. The systems are discussed studying the retention as a function of the mobile phase parameters and the stationary phases used (LiChrospher 100 RP-18, IonPac AS9, AS10 and AS11). A preconcentration step, performed on different substrates, namely LiChrolut-EN and activated vegetal carbon, has been optimized in order to reduce the method detection limits. Results obtained for drinking water samples are shown.     

Capillary electrophoretic separation of dicarboxylic acids in atmospheric aerosol particles

2,3-Pyrazinedicarboxylic acid (PZDA), 2,6-pyridinedicarboxylic acid (PDA) and 2,3-pyridinedicarboxylic acid (QUIN) solutions were studied as background electrolytes (BGEs) in the capillary electrophoretic analysis of dicarboxylic acids in aerosol particles with indirect UV detection. The BGEs were selected on the basis of similarity in structure with the analytes so that mobilities would be compatible. Optimised pH values for PZDA, PDA and QUIN solutions were 10.6, 11.0 and 10.2, respectively. Myristyltrimethylammonium hydroxide and myristyltrimethylammonium bromide were added to reverse the electroosmotic flow in the solutions in the direction of anode to enable fast anion detection. Separation was obtained for nine dicarboxylic acids (C₂–C₁₀) differing in the number of CH₂ groups in their skeleton. The electrophoretic mobilities were determined to lie in the range 3.0×10⁻⁴–7.0×10⁻⁴ cm² V⁻¹ s⁻¹. The relative standard deviations (RSDs) for the absolute migration times of the analytes were mostly less than 0.5% (n=6) in PZDA solution. In PDA solution the within-day and day-to-day RSD values for migration were less than 1% and between 2 and 4%, respectively. Peak heights and areas mostly deviated between 1 and 15% in both PZDA and PDA solutions. Detection limits ranged between 1 and 5 mg/l. Methods were applied to the analysis of dicarboxylic acids isolated from aerosol particles.     

A simple one-pot synthesis of 3-alkoxy-3-cyanocarboxylic acids: a rapid entry to new GABA derivatives

A simple one-pot procedure to obtain a series of new 3-alkoxy-3-cyanocarboxylic acids from the reaction of 4-alkoxy-1,1,1-trichloro-but-3-en-2-ones with sodium cyanide is described.     

Chemistry and Biochemistry of Unsaturated Fatty Acids

Although unsaturated fatty acids have long been known to accompany saturated fatty acids in most lipids, qualitative and quantitative determination of fatty acid patterns only became possible with the advent of modern analytical methods. Present day knowledge of the chemical structure, physical properties, and metabolism of unsaturated fatty acids provides the basis for the development of new concepts of their function. Thus unsaturated fatty acids crucially determine the properties of biological membranes. Moreover, essential fatty acids are precursors of prostaglandins.     

Thermal Studies on Some Substituted Aminobenzoic Acids

The thermal behaviour of various substituted aminobenzoic acids(3-aminobenzoic acid (3-ABA), 4-aminobenzoic acid (4-ABA), 3-aminosalicylic acid(3-ASA), 4-aminosalicylic acid (4-ASA), and 5-aminosalicylic acid (5-ASA), as well as the‘parent’ benzoic acid (BA) and salicylic acid (SA) as reference substances, and possible decomposition products: 2-aminophenol (2-AP), 3-aminophenol (3-AP) and 4-aminophenol(4-AP) in the solid state has been examined. The various sets of isomers studied showed considerable and interesting differences. Most sublimed well before melting, generally with an increasing rate of mass loss beyond their very different melting points. The differences in behaviour of 4-ASA and 5-ASA were the most remarkable, with 5-ASA being far more stable and apparently not decarboxylating readily, while 4-ASA sublimed at temperatures below the melting point, becoming less stable and decarboxylating in the liquid form. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation of Some Substituted Terephthalic Acids

We report in detail the preparation of two substituted terephthalic acids: 2‐sulfomethylterephthalic acid (1) and 2‐phosphonoterephthalic acid (2). Efficient, short syntheses have been developed for both compounds. They are potentially useful monomers for construction of acid‐pendant polymer chains.     

Surface Tension of Liquid Organic Acids: An Artificial Neural Network Model

An artificial neural network model is proposed for the surface tension of liquid organic fatty acids covering a wide temperature range. A set of 2051 data collected for 98 acids (including carboxylic, aliphatic, and polyfunctional) was considered for the training, testing, and prediction of the resulting network model. Different architectures were explored, with the final choice giving the best results, in which the input layer has the reduced temperature (temperature divided by the critical point temperature), boiling temperature, and acentric factor as an independent variable, a 41-neuron hidden layer, and an output layer consisting of one neuron. The overall absolute percentage deviation is 1.33%, and the maximum percentage deviation is 14.53%. These results constitute a major improvement over the accuracy obtained using corresponding-states correlations from the literature.     

Separation of perfluoroalkylsulfinic acids and perfluoroalkylsulfonic acids by ion-exclusion chromatography

Ion-exclusion chromatography has been successfully applied to the separation of a number of perfluoroalkylsulfinic acids and perfluoroalkylsulfonic acids. The separation of various perfluoroalkylsulfinic and perfluoroalkylsulfonic acids, with different alkyl groups, was investigated on a polymethacrylate-based, weakly acidic, cation-exchange resin (TSK gel OApak-A) in the H⁺-form and using conductimetric detection. When water was used as the eluent, these perfluoroalkylsulfinic and perfluoroalkylsulfonic acids could not be resolved. When an aqueous solution of benzoic acid and o-phthalic acid was used, the separation of each of these acids occurred. In order to improve their separation, the effect of the addition of methanol and 2,2,2-trifluoroethanol, as organic modifiers, was also investigated.     

A Convenient Laboratory Preparation of N,N-Dimethyl-dichloro-methylene-iminium Chloride (Phosgene-iminium chloride)

A method of preparation of the title compound 1a avoiding the use of gaseous chlorine is described. Tetramethylthiuram disulfide 4 is oxidized with sulfuryl chloride to dime thyl thiocarbamoyl chloride 5, which is converted to 1a by means of phosphorus pentachloride.     

Highly efficient fluorescent sensing for α-hydroxy acids with C3-symmetric boronic acid-based receptors

Two boronic acid-based fluorescent chemosensors in C₃ symmetry have been prepared with a facial method. These compounds show remarkable ability to recognize α-hydroxycarboxy acids and sugar acids over most saccharides. The fluorescence intensity of the receptors decreased obviously upon adding the α-hydroxy acids in a pH 8.71 buffer of methanol-water, which can be explained with the internal charge-transfer (ICT) mechanism.     

Application of zirconium-modified silica gel as a stationary phase in the ion-exclusion chromatography of carboxylic acids I. Separation of benzenecarboxylic acids with tartaric acid as eluent and with UV-photometric detection

The application of zirconium-modified silica gels (Zr–Silicas) as stationary phases for ion-exclusion chromatography with UV-photometric detection (IEC–PD) for mono-, di-, tri- and tetrabenzenecarboxylic acids (pyromellitic, trimellitic, hemimellitic, o-phthalic, salicylic and benzoic acids) and phenol was carried out using tartaric acid as the eluent. Zr–Silicas were prepared by the reaction of the silanol group on the surface of silica gel with zirconium tetrabutoxide [Zr(OCH₂CH₂CH₂CH₃)₄] in ethanol solution. The effect of the amount of zirconium adsorbed on silica gel on chromatographic behavior of these benzenecarboxylic acids and phenol was investigated. As a result, Zr–Silica adsorbed on 20 mg zirconium g⁻¹ silica gel was the most suitable stationary phase in the IEC–PD for the simultaneous separation of these benzenecarboxylic acids and phenol. Excellent simultaneous separation and highly sensitive UV detection at 254 nm for these benzenecarboxylic acids and phenol were achieved in 20 min by the IEC–PD using the Zr–Silica column (250×4.6 mm I.D.) and a 10 mM tartaric acid at pH 2.5 as eluent.     

β-Homoalanyl PNAs: Synthesis and Indication of Higher Ordered Structures

Self-pairing complexes with extraordinarily high stability are formed by β-PNAs with four to six units of the nucleo-β-amino acid 1 . The key step in the synthesis is a Mitsunobu reaction between a β-homoserine and a purine derivative.     

Synthesis of 4-monofluoromethylenyl- and cis-4-monofluoromethyl-l-pyroglutamic acids via a novel dehydrofluorination

Novel dehydrofluorination reactions accidentally found were used to synthesize terminal monofluoro olefin lactam analogues in good yield. The following hydrogenation of the resulting defluorinated product was systematically investigated. Two important fluorinated amino acids: 4-monofluoromethylenyl-l-pyroglutamic acid 16 and cis-4-monofluoromethyl-l-pyroglutamic acid 17 were synthesized using the methodology.     

吸附型“人工肝”辅助材料的合成及其性能研究Ⅰ大孔吸附树脂对芳香氨基酸的吸附性能

合成了苯乙烯型大孔吸附剂（MacroreticularAdsorbentMA）测定其孔结构参数，考察吸附剂对芳香氨基酸的吸附性能。实验结果表明，MA－2型吸附剂对芳香氨基酸具有特异性吸附，而对支链氨基酸吸附为非特异性吸附，其血液相容性良好。     

Benzylidene Acetal Protecting Group as Carboxylic Acid Surrogate: Synthesis of Functionalized Uronic Acids and Sugar Amino Acids

Direct oxidation of the 4,6‐O‐benzylidene acetal protecting group to C‐6 carboxylic acid has been developed that provides an easy access to a wide range of biologically important and synthetically challenging uronic acid and sugar amino acid derivatives in good yields. The RuCl₃–NaIO₄‐mediated oxidative cleavage method eliminates protection and deprotection steps and the reaction takes place under mild conditions. The dual role of the benzylidene acetal, as a protecting group and source of carboxylic acid, was exploited in the efficient synthesis of six‐carbon sialic acid analogues and disaccharides bearing uronic acids, including glycosaminoglycan analogues.     

High-performance liquid chromatographic analysis of free long chain fatty acids produced during lipolysis by anaerobic digestor sludge

The development of sample extraction techniques in conjunction with application of a modified version of an established HPLC technique allowed the rapid estimation of concentrations of long chain fatty acids (LCFA) produced by the lipolytic activity of bacteria in anaerobic digestor sludges or experiments using the sludges as inocula. It was established that free long chain fatty acids will preferentially partition into certain phases in the sludge or experimental cultures. These data, and application of the developed techniques for monitoring of LCFA, may lead to the avoidance of toxicity and failure of full-scale anaerobic digestors treating high lipid content waste in the future.     

Evaluation of methods for measuring amino acid hydrophobicities and interactions

The concept of hydrophobicity has been addressed by researchers in all aspects of science, particularly in the fields of biology and chemistry. Over the past several decades, the study of the hydrophobicity of biomolecules, particularly amino acids has resulted in the development of a variety of hydrophobicity scales. In this review, we discuss the various methods of measuring amino acid hydrophobicity and provide explanations for the wide range of rankings that exist among these published scales. A discussion of the literature on amino acid interactions is also presented. Only a surprisingly small number of papers exist in this rather important area of research; measuring pairwise amino acid interactions will aid in understanding structural aspects of proteins.