Potentiometric detection of organic acids in liquid chromatography using polymeric liquid membrane electrodes incorporating macrocyclic hexaamines

Potentiometric detection employing coated-wire electrodes was applied to the determination of organic acids in liquid chromatography (LC). Poly(vinyl chloride)-based liquid membranes, incorporating lipophilic macrocyclic hexaamines as neutral ionophores were used as electrode coatings. The selectivity and sensitivity of the macrocycle-based electrodes were found to be superior to an electrode based on a lipophilic anion exchanger (a quaternary ammonium salt). Sensitive detection was obtained for the di- and tricarboxylic acids tartaric, malonic, malic, citric, fumaric, succinic, pyruvic, 2-oxoglutaric and maleic acids after separation in reversed-phase LC. Detection limits (signal/4sigmanoise=3) of 6 pmol for malonic acid and 2 pmol for maleic acid were attained. The detection was explained using a molecular recognition model. The hexaamine-based potentiometric electrodes had a 1-s response time at 1 ml min(-1) flow-rates. They were stable for at least 4 months, with an intra-electrode variation of 3.2% (n=5).     

Analysis of low-molecular-mass organic acids using capillary zone electrophoresis-electrospray ionization mass spectrometry

A capillary zone electrophoresis-electrospray ionization-mass spectrometry (CZE-ESI-MS) method was developed to facilitate identification and determination of eleven low-molecular-mass (LMW) organic acids (i.e. oxalic, lactic, malonic, maleic, citric, tartaric, adipic, glutaric, gluconic, isosaccharinic and succinic acid) in different sample matrices. This CZE method was adapted to suit MS conditions. Sheath liquid, sheath flow and MS parameters were optimized to achieve high mass spectrometric sensitivity. The CZE-ESI-MS procedure showed good sensitivity (limit of detection of < 0.05-0.7 mg/l for all acids), linearity (r2 = 0.9925-0.9998) and reproducibility (2.09-5.34% RSD). The applicability of the CZE-ESI-MS was demonstrated on LMW organic acids in an ale sample. In addition the (here presented) method also provided quantification of fumaric, galacturonic and 2-ketoglutaric acid with high sensitivity.     

Potentiometric determination of the total acidity and concentration of citric acid in wines

The method of potentiometric titration with a copper electrode is used for the determination of the total acidity and concentration of citric acid (CA) in identifying the adulteration of wines. The procedure is suitable for the determination of citric acid in wines in the range from 0.1 to 3.5 g/L in the presence of 30-fold amounts of tartaric, acetic, malic, succinic acids and a 10-fold amount of oxalic acid after the separation of organic carboxylic acids on an AV-17-8 anion exchanger. The procedure was developed and certified for the potentiometric determination of the mass fraction of citric acid in table wines and wine materials with an error not exceeding 20%. The criteria (mass fraction of citric acid, the percentage of citric acid in the total acidity, and the shape of the curves of potentiometric titration) were proposed for revealing the adulteration of the acid composition of wines.     

Simultaneous determination of organic acids and nitrate in xylem saps of the hyperaccumulator Alyssum murale by RP-HPLC after solid-phase extraction with nanosized hydroxyapatite

An analytical approach based on solid-phase extraction (SPE) with nanosized hydroxyapatite and reversed-phase high performance liquid chromatography (RP-HPLC) for the simultaneous determination of organic acids (oxalic, malic, malonic, citric, and fumaric) and nitrate in xylem saps of the hyperaccumulator Alyssum murale is presented in this study. The optimum experimental conditions for the separation and determination of organic acids and nitrate are studied. The interference from nitrate on oxalic acid in RP-HPLC is eliminated by SPE with nanosized hydroxyapatite, and the simultaneous determination of organic acids and nitrate is achieved by RP-HPLC at the optimum chromatographic conditions. The accuracy of the method is confirmed with an average recovery ranging between 95.2% and 99.8%, the relative standard deviations (RSD) are less than 2.0%. This method is successfully applied to determine the organic acids and nitrate in xylem saps of the hyperaccumulator Alyssum murale.     

LC Determination of Trace Short-Chain Organic Acids in Wheat Root Exudates Under Aluminum Stress

A novel and reliable high-performance liquid chromatographic method for trace short-chain organic acids measurement in wheat root exudates under aluminum stress has been optimized and validated. The chromatographic separation of the short-chain organic acids (citric, oxalic, malonic, succinic, tartaric, malic, and acetic acids) was achieved with Bio-rad Aminex HPX-87H cation exchange resin column. These seven organic acids were identified and quantified in 25 min. Well-shaped peaks were obtained for trace organic acids using dilute sulfuric acid as mobile phase. Under optimum conditions, Bio-rad Aminex HPX-87H column showed distinct advantages of the ability to well separate different short-chain organic acids (especially for tartaric and malic acids, as well as malonic and acetic acids) in wheat root exudates under aluminum stress, and offered accurate and precise results for the analysis of these organic acids. This HPLC method can efficiently eliminate the aluminum’s interference and is quite suitable to the trace detection of trace organic acids in wheat root exudates under aluminum stress.

     

LC Determination of Trace Short-Chain Organic Acids in Wheat Root Exudates Under Aluminum Stress

A novel and reliable high-performance liquid chromatographic method for trace short-chain organic acids measurement in wheat root exudates under aluminum stress has been optimized and validated. The chromatographic separation of the short-chain organic acids (citric, oxalic, malonic, succinic, tartaric, malic, and acetic acids) was achieved with Bio-rad Aminex HPX-87H cation exchange resin column. These seven organic acids were identified and quantified in 25 min. Well-shaped peaks were obtained for trace organic acids using dilute sulfuric acid as mobile phase. Under optimum conditions, Bio-rad Aminex HPX-87H column showed distinct advantages of the ability to well separate different short-chain organic acids (especially for tartaric and malic acids, as well as malonic and acetic acids) in wheat root exudates under aluminum stress, and offered accurate and precise results for the analysis of these organic acids. This HPLC method can efficiently eliminate the aluminum’s interference and is quite suitable to the trace detection of trace organic acids in wheat root exudates under aluminum stress.     

Naturally occurring organic acids for organocatalytic synthesis of pyrroles via Paal–Knorr reaction

Research on Chemical Intermediates - In this study, common naturally occurring organic acids, namely oxalic, malonic, succinic, tartaric and citric acid (as safe, inexpensive, and biodegradable...     

离子交换色谱法对8种有机酸含量的同时测定

建立了淋洗液自动发生梯度淋洗的离子交换色谱法同时测定果汁中乳酸、乙酸、苹果酸、丙二酸、马来酸、草酸、柠檬酸、异柠檬酸8种有机酸的分析方法.样品经处理后用lonPac AS11-HC分离柱和lonPac AG11-HC型保护柱分离,以EG40自动淋洗液发生器生成的0.8～30 mmol/L KOH为淋洗液梯度洗脱,抑制型...     

Adsorption of dicarboxylic acids on lithiated nickel oxide electrode

Adsorption of dicarboxylic acids on NiO electrodes was studied by means of the galvanostatic transient method, mainly for oxalic acid. The oxalate or hydrogen oxalate anion or both were concluded to adsorb on the electrode. The adsorption was maximal at a potential less positive than the flat-band potential of the electrode, owing to preferential adsorption of hydroxyl anion in the region above the maximum adsorption potential. The quantity of adsorption was dependent on carrier concentration of the electrode, and high for the electrode of high carrier concentration. This phenomenon is connected to the charged condition of the electrode that when the maximum adsorption takes place, positively charged sites remain on the surface of the electrode which is charged negatively as a whole and the amount of the sites is much more different between the electrodes of different N than their bulk carrier concentrations. Adsorptions of malonic and succinic acid were distinctly low compared with that of oxalic acid. The adsorbability was in the order; oxalic acid>malonic acid>succinic acid. This order was in accord with the stability constants of nickel dicarboxylic acid chelates.     

PREBIOTIC FORMATION OF HIGHER MOLECULAR WEIGHT COMPOUNDS FROM THE PHOTOLYSIS OF AQUEOUS ACETIC ACID

In the study of chemical evolution, experiments simulating primitive earth conditions have shown that many compounds of biological significance can be produced from simple precursors. In an attempt to search for the origin of polycarboxylic acids, the UV irradiation of aqueous acetic acid was performed. Among the products detected were succinic, citric and malonic acids which are key compounds in metabolic pathways, suggesting that these compounds might have been formed on the primitive Earth prior to life itself.     

逐级提取-高效液相色谱法快速测定植物组织中8种有机酸

针对植物组织中草酸存在的不同形态,建立了水和稀盐酸作为提取介质的逐级提取方法,获得了水溶态和酸溶态草酸及乙醇酸、乙醛酸、酒石酸、苹果酸、乙酸、柠檬酸、琥珀酸等有机酸。采用Hypersil ODS (200 mm×4.6 mm, 5 μm)色谱柱,以5 mmol/L磷酸二氢钾水溶液(pH 2.8)作为流动相,在进样量5 μL、检测波长210 nm、柱温30 ℃的条件下,通过分时段控制流速实现了8种有机酸的快速分离,同时去除了盐酸对酸溶态草酸测定的干扰。本方法精确灵敏、回收率高、重复性好,可应用于实际样品的测定分析。     

LC–MS analysis of low molecular weight organic acids derived from root exudation

A sensitive method for quantification of citric, fumaric, malic, malonic, oxalic, trans aconitic, and succinic acid in soil- and root-related samples is presented. The method is based on a novel, fast, and simple esterification procedure and subsequent analysis via liquid chromatography–mass spectrometry. Derivatization comprises in situ generation of HCl, which catalyzes the Fischer esterification with benzyl alcohol. As a key advance, the esterification with the aromate allows reversed-phase separation and improves electrospray ionization efficiency. The method provided procedural detection limits of 1 nM for citric, 47 nM for fumaric, 10 nM for malic, 10 nM for malonic, 16 nM for oxalic, 15 nM for succinic, and 2 nM for aconitic acid utilizing 500 μL of liquid sample. The working range was 3 nM to 10 μM for citric acid, 158 nM to 10 μM for fumaric acid, 34 nM to 10 μM for malic acid, 33 nM to 10 μM for malonic acid, 53 nM to 10 μM for oxalic acid, 48 nM to 10 μM for succinic acid, and 6 nM to 10 μM for aconitic acid. Quantification of the analytes in soil-related samples was performed via external calibration of the entire procedure utilizing ¹³C-labeled oxalic and citric acid as internal standards. The robustness of the method was tested with soil extracts and samples from hydroponic experiments. The latter concerned the regulation of phosphorus solubilization via plant root exudation of citric, malic, and oxalic acid.     

Development and optimization of a method for the analysis of low-molecular-mass organic acids in plants by capillary electrophoresis with indirect UV detection

Capillary zone electrophoresis was developed to analyze low-molecular-mass organic acids including oxalic, tartaric, formic, malic, citric, succinic, glutaric, acetic and lactic acid. The influences of some crucial parameters such as buffer concentration, pH value, surfactant concentration and separation temperature, on electrophoretic separation were investigated. Under the conditions of 15 mM phthalate containing 0.6 mM tetradecyltrimethylammonium bromide as the run buffer (pH 5.6); separation voltage -15 kV (-263.2 V/cm) and temperature 25 degrees C, a satisfactory separation of nine organic acids was accomplished within 7 min. The detection limits (S/N=3) ranged from 0.008 to 0.08 microg/ml and the quantification limits ranged from 0.01 to 0.1 microg/ml for electrokinetic injection. The method was successfully applied to analyze organic acids in different parts of Var splendens (an edible vegetable in China). The recoveries of organic acids in real samples ranged from 88 to 121%.     

Single-column method of chelation ion chromatography for the analysis of trace metals in complex samples

A single-column chelation ion chromatographic system for the preconcentration and separation of trace transition metals is described. The system includes standard chromatographic equipment with a post-column reagent system based on the reaction with 4-(2-pyridylazo)resorcinol followed by photometric detection at 495 nm. Iminodiacetic acid bonded to 5 μm silica (Diasorb IDA) was used as a chelating stationary phase. The strong complexing ability in combination with good kinetics of complexation and ion-exchange selectivity of iminodiacetic functional groups allow both preconcentration of Mn, Co, Cd, Zn, Ni and Cu from waters of high salinity and efficient separation with the same column. The retention characteristics of alkaline-earth and transition metal ions on Diasorb IDA silica (250×4 mm I.D.) column was investigated for a variety of eluents including nitric acid, maleic, malonic, citric, dipicolinic, picolinic, tartaric and oxalic acids. The influence of ionic strength on retention of metal ions involving high nitrate and chloride concentrations was also evaluated. The baseline separation of preconcentrated metals was achieved using a three-step gradient elution scheme which involved first, flushing of the column loaded with the sample with 0.5 M KCl−0.5mMHNO₃ for 10 min, followed by 80 mM tartaric acid for 20 min and finally 10 mM picolinic acid for 20 min.     

Triethanolammonium salts of biologically active carboxylic acids

Triethanolammonium salts (protatranes) of biologically active carboxylic acids (nicotinic, cinnamic, benzoic, salicylic, oxalic, malonic, succinic, malic, citric) were synthesized in yields exceeding 90%. The structure of the synthesized compounds was studied by IR spectroscopy and X-ray diffraction analysis.     

Ionic strength dependence of formation constants-I Protonation constants of organic and inorganic acids

The protonation constants of formic, acetic, benzoic, oxalic, phthalic, maleic, malonic, succinic, dl-malic, dl-tartaric, aminoacetic, citric, nitrilotriacetic, ethylenediaminetetra-acetic, sulphuric and orthophosphoric acids have been determined from pH measurements, in tetraethylammonium iodide solution, at various ionic strengths in the range 0.01-1.0M (for phosphoric and sulphuric acids 0.01-0.5M). For each acid the dependence of the protonation constants on ionic strength was determined and an equation, valid for all the acids studied, to describe this was derived. The use of tetraethyl-ammonium salts as background to avoid ion-pair formation is discussed.     

离子排斥色谱法同时测定果汁中11种有机酸

 用离子排斥色谱法实现了对果汁中 11种有机酸 (草酸、柠檬酸、酒石酸、苹果酸、抗坏血酸、乳酸、琥珀酸、甲酸、乙酸、戊二酸、富马酸 )的分离测定。以 17mmol/L硫酸为淋洗液 ,样品在ICE ION 30 0离子排斥柱上分离后 ,用紫外检测器在 2 10nm处测定其中的有机酸。各组分质量浓度测定的相对标准偏差在 1.5 %～ 9.8% (n =10 )。     

Analysis of low molecular mass organic acids in natural waters by ion exclusion chromatography tandem mass spectrometry

A sensitive and selective method for the analysis of aliphatic low molecular mass organic acids (LMMOAs) in natural waters is presented. The method is based on separation with ion exclusion chromatography and detection with electrospray ionization tandem mass spectrometry (LC-MS/MS). The extra selectivity gained by applying MS/MS allows for a minimum of sample preparation and the use of a sub-optimal mobile phase regarding chromatographic resolution. Instead the mobile phase, comprising aqueous formic acid with methanol as organic modifier, was mainly optimized for maximum sensitivity and long term MS stability. Detection limits for malonic, fumaric, maleic, succinic, citraconic, glutaric, malic, alpha-ketoglutaric, tartaric, shikimic, trans-aconitic, cis-aconitic, isocitric and citric acid were in the range 1-50 nM, while the detection limits for pyruvic, oxalic and lactic acid were around 250 nM for an injection volume of 100 microL. Due to their metal-chelating properties, these LMMOAs are all considered to affect the bioavailability of metals and to be involved in soil forming processes. It is thus of interest to be able to monitor their presence in natural waters, and the method developed within this work was successfully applied for the analysis of LMMOAs in soil solution and stream water samples.     

Specific features of physical chemistry and electronic structure of lower dicarboxylic acids

The static and complex dielectric permittivities and dc electrical conductivities of solid oxalic, malonic, and succinic acids were measured. The relaxation times of single crystal blocks (3–5 days) and mean relaxation frequencies of molecules and low-molecular-weight associates of oxalic acid dihydrate (5 MHz) and malonic acid (160 kHz) at 19°C were estimated. Aqueous oxalic acid can absorb electromagnetic energy owing to the presence of solvated electrons and holes. The electrical conductivity of this acid is protonic, and that of the anhydrous acids, electronic; the electron-hole pairs are mainly generated in these acids by lattice vibrations. The applied alternating electric field caused desorption of active gases from the acids. In some experiments with malonic acid, fast isothermal rearrangements of hydrogen bond networks and avalanche ionization of molecules were observed at a slight increase in temperature. The diagrams of charge distribution in the free acid molecules were constructed on the basis of the previous dipole moment measurements and IR data.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 11, 2004, pp. 1828–1834.Original Russian Text Copyright © 2004 by Ponomarenko, Borovikov, Sivachek.This revised version was published online in April 2005 with a corrected cover date.     

Application of Capillary Zone Electrophoresis for the Analysis of Low Molecular Weight Organic Acids in Environmental Samples

Abstract

The applicability of a recently developed capillary zone electrophoretic (CZE) method for the determination of low molecular weight (LMW) organic acids in water was tested on five types of environmental samples (rainwater, water extract from peat, and soil water from two polluted sites). A full baseline resolved separation of fourteen commonly found LMW carboxylic acids in natural waters (malonic, oxalic, fumaric, maleic, formic, succinic, tartaric, glutaric, adipic, acetic, propionic, butyric, valeric and citric acids), was achieved within eight minutes. The limits of detection (2 X noise) were in the ranges 90–200 μg/l and 0.5 – 5 μg/l for hydrodynamic and electrokinetic injection, respectively. Two different CZE systems, a Waters Quanta 4000 and a Hewlett Packard HP ^3DCE system, were used and their performance compared.