GC-MS quantitation of isocitric acid in the presence of a large excess of citric acid

A GC-MS method has been developed for the analysis of the sugar and carboxylic acid content of citrus fruits, including the quantitation of isocitric acid in the presence of a large excess of citric acid. Optimum conditions have been determined for the analysis (from one solution, by one injection, on a 30 m DB-5 column) of the TMS oxime and/or TMS derivatives of sugars and acids obtained from various lemon, grapefruit, and orange samples. Quantitation was based on the monitoring of the total ion current and of selective fragments. The utility of the method has been demonstrated by the determination of isocitric acid in the presence of 10- to 200-fold excess of citric acid.     

近红外光谱法快速检测烟草中部分香气物的应用研究

应用傅立叶变换近红外漫反射光谱仪,从500个样品中按高、中、低含量挑选出具代表性的150～172个烟草样品建立了近红外光谱与烟草中的苹果酸、柠檬酸和石油醚提取物成分含量间的数学模型,用建立的模型对36个样品进行预测,结果表明,各成分近红外预测值与实测值之间的平均偏差:苹果酸为0.090,柠檬酸为0.040,石油醚提取物为0.124;且近红外预测值与化学法不存在显著性差异,近红外光谱分析技术可初步用于烟草部分香气成分的快速定量分析.     

Dissolution of kaolinite induced by citric, oxalic, and malic acids

Kaolinite is a dominant clay mineral in the soils in tropical and subtropical regions, and its dissolution has an influence on a variety of soil properties. In this work, kaolinite dissolution induced by three kinds of low-molecular-weight organic acid, i.e., citric, oxalic, and malic acids, was evaluated under far-from-equilibrium conditions. The rates of kaolinite dissolution depended on the kind and concentration of organic acids, with the sequence R(oxalate)>R(citrate)>R(malate). Chemical calculation showed the change in concentration of organic ligand relative to change in concentration of organic acid in suspensions of kaolinite and organic acid. The effect of organic acid on kaolinite dissolution was modeled by species of organic anionic ligand. For oxalic acid, L(2-)(oxalic) and HL(-)(oxalic) jointly enhanced the dissolution of kaolinite, but for malic and citric acids, HL(-)(malic) and H2L-(citric) made a higher contribution to the total dissolution rate of kaolinite than L(2-)(malic) and L(3-)(citric), respectively. For oxalic acid, the proposed model was R(Si)=1.89x10(-12)x[(25x)/(1+25x)]+1.93x10(-12)x[(1990x1)/(1+1990x1)] (R2=0.9763), where x and x1 denote the concentrations of HL(oxalic) and L(oxalic), respectively, and x1=10(-3.81)xx/[H+]. For malic acid, the model was R(Si)=4.79x10(-12)x[(328x)/(1+328x)]+1.67x10(-13)x[(1149x1)/(1+1149x1)] (R2=0.9452), where x and x1 denote the concentrations of HL(malic) and L(malic), respectively, and x1=10(-5.11)xx/[H+], and for citric acid, the model was R(Si)=4.73x10(-12)x[(845x)/(1+845x)]+4.68x10(-12)x[(2855x1)/(1+2855x1)] (R2=0.9682), where x and x1 denote the concentrations of H2L(citric) and L(citric), respectively, and [Formula: see text] .     

Quantitative analysis of malic and citric acids in fruit juices using proton nuclear magnetic resonance spectroscopy

¹H NMR spectroscopy was applied to the quantitative determination of malic and citric acids in apple, apricot, pear, kiwi, orange, strawberry and pineapple juices. Aspartic acid was studied as a potential interference. The effect of the sample pH on the chemical shifts of signals from malic, citric and aspartic acids was examined and a value of 1.0 was selected to carry out the determination. Integration of NMR signals at 2.89-2.95 and 3.00-3.04 ppm were used for calculating the concentration of malic and citric acids, respectively. At this pH the integrated signals were not overlapped. Sodium 3-(trimethylsilyl)tetradeuteropropionate (TSP) was used as an internal reference. The obtained results applying NMR procedures to analyze the juices from different fruits were compared to those obtained using enzymatic methods and both were in close agreement. The intra- and inter-day repeatability was tested for apple juice (7.86 g l⁻¹ malic acid, 0.32 g l⁻¹ citric acid) and apricot juice (5.06 g l⁻¹ malic acid, 4.79 g l⁻¹ citric acid) obtaining coefficients of variation lower than 3.4% for intra-day measures (n = 10) and lower than 3.8% for inter-day measures (n = 20).     

Habit modification of calcium carbonate in the presence of malic acid

The ability of malic acid to control calcium carbonate morphology has been investigated by aging calcium chloride solution in the presence of urea in a 90 °C bath. Malic acid favors the formation of calcite. A transition from single block to aggregate with special morphology occurs upon increasing malic acid concentration. The morphological development of CaCO₃ crystal obviously depends on the starting pH. CaCO₃ crystal grows from spindle seed to dumbbell in the pH regime from 7 to 11; while it evolves from spindle seed, through peanut, to sphere at pH=11.5. Both dumbbell and sphere consist of rods that are elongated along c-axis and capped with three smooth, well-defined rhombic {1 0 4} faces. A tentative growth mechanism is proposed based on the fractal model suggested by R. Kniep and S. Busch [Angew. Chem. Int. Ed. Engl. 35 (1996) 2624].     

Enantioseparation of DL-isocitric acid by a chiral ligand exchange CE with Ni(II)-D-quinic acid system

The ratio of citric acid to D ‐isocitric acid can be used to distinguish authentic and adulterated fruit juices. To separate DL ‐isocitric acid enantiomers, we used ligand exchange CE. D ‐Quinic acid was used as a chiral selector ligand and Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) ions were used as the central ions of the chiral selector in the BGE. DL ‐Isocitric acid was found to be enantioseparated with the above metal ions except for Mn(II) ion. The optimum running conditions for the analysis of D ‐ and L ‐isocitric acids along with citric acid, an isomer of isocitric acid, were found to be a BGE (pH 5.0) containing 30% ACN, 20 mM acetic acid, 20 mM NiSO₄, and 80 mM D ‐quinic acid. Under these conditions, DL ‐isocitric and citric acids in fruit juices were analyzed successfully.     

Flow injection determinations of citric acid: a review

A review of the flow injection (FI) analytical methods used to determine citric acid (CA) is presented. These flow determinations are described and compared according to the detection technique used. In addition to the advantages involving the use of the continuous flow systems, the analytical figures of merit and interferences are also discussed.     

Trace determination of cobalt ion by using malic acid-malonic acid double substrate oscillating chemical system

A novel kinetic method for determination of trace amounts of cobalt ion was proposed and validated. The method is based on adding malic acid into classical Belousov-Zhabotinskii （B-Z） oscillating chemical system to form a double substrate one. The results showed that when the concentration of cobalt ion was in the range of 5.27× 10^-8 to 5.37 × 10^-12 mol L^-1, the change of the oscillating period was directly proportional to the negative logarithm of cobalt ion concentration. The sensitivity and precision of the developed method were quite satisfactory. The limit of detection was down to 5.20 × 10^-13 mol L^-1 which was a highest sensitivity found for determination of metal ions using oscillating chemical reaction so far. Some factors influencing the determination were also examined. The method has been successfully used to determine cobalt ion in vitamin B12 injection.     

Ultrasound-assisted extraction and determination of tartaric and malic acids from grapes and winemaking by-products

The optimization of an ultrasound-assisted extraction (UAE) method for tartaric and malic acids from grape derived samples is shown. A fractional factorial experimental design allowed for the determination of the effects of seven extraction variables. Relationships between all the variables were examined. By applying graphical analysis, the best extractions conditions were obtained. The most important variables were the extracting liquid and the extraction temperature. Later, a central composite design was applied for optimizing the temperature and the composition of the extracting liquid. The optimized method was applied to grapes and to winemaking by-products. The repeatability of the method was studied and the recovery of tartaric and malic acids was established. Organic acids quantification was done by liquid chromatography (LC) using a post-column buffer and a conductivity detector.     

柠檬酸试剂中痕量无机阴阳离子的离子色谱法测定

选用柱容量较高、亲水性较强的阴离子分析柱IonPac AS18,以30mmol／L KOH为淋洗液,等度淋洗分析了高浓度柠檬酸中的痕量无机阴离子。选用柱容量较高的阳离子分析柱IonPac CS12A,以H2SO4作淋洗液分析了柠檬酸试剂中的痕量阳离子。在所选色谱条件下,无需样品前处理,直接进样,电导检测,高浓度柠檬酸不影响痕量阴离子或阳离子的测定。方法具有良好的线性(r=0．9941～1．000),样品中所测离子峰面积的相对标准偏差(RSD)均在9．0％以下(n=7),回收率在82．7％～110％之间,检出限低于3．7μg/L。     

Peroxidase based biosensors for the selective determination of D,L-lactic acid and L-malic acid in wines

A novel bioelectrochemical method for the direct determination of D(−) L(+) lactic acid and of L(−) malic acid in wines is presented. Multienzymatic biosensors were realized for the selective determination of the three analytes: D(−) and L(+) lactic acid were measured by a trienzymatic biosensor based on the catalytic activities of the enzymes L(+) lactate oxidase (LOD), D(−) lactate dehydrogenase (D-LDH) and horseradish peroxidase (HRP); L(−) malic acid was measured by a bienzymatic electrode, realized by coupling the enzymes L(−) malic dehydrogenase (L-MDH) and horseradish peroxidase (HRP). In both cases the enzymes were immobilized on an oxygen selective Clark electrode.The simultaneous determination of the two organic acids can be accomplished either in batch or in a flow injection analysis apparatus using the same biosensors as detectors. The analytical performance of the method, tested in standard aqueous solutions and on real samples of wines, showing high repeatability, short response times and reduced cost of analysis, suggest that the experimental approach here described could be followed to monitor the progress of malolactic fermentation.     

Extraction of aqueous of malic acid by trioctylamine extractant in various diluents

In this study malic acid were extracted from aqueous solution by different solvents with and without trioctylamine (TOA). The TOA was dissolved in five different esters (dimethyl phthalate, dimethyl adipate, dimethyl succinate, dimethyl glutarate, and diethyl carbonate), five different alcohols (isoamyl alcohol, hexan-1-ol, octan-1-ol, nonan-1-ol, and decan-1-ol) and two different ketones (diisobutyl ketone (DIBK) and methyl isobutyl ketone (MIBK)). The results are reported as distribution coefficients (K_D), loading factors (T_T), stoichiometric loading factor (T_S), separation factor (S_f) and extraction efficiency (E). The most effective solvent was determined as isoamyl alcohol with a distribution value coefficient of 17.811. The maximum values of equilibrium complexation constants in isoamyl alcohol for (acid:amine) (1:1) K₁₁ and (2:1) K₂₁ were 9.9 and 225.6, respectively. A linear solvation energy relationship (LSER) was accurately regressed to the experimental distribution coefficients.     

Ultrasound assisted pseudo-digestion for determination of iron and manganese in citric acid fermentation mediums by electrothermal atomic absorption spectroscopy

A sensitive, simple and rapid method for ultra-trace determination of iron and manganese based on ultrasound assisted pseudodigestion in citric acid fermentation medium samples (beet and cane molasses and raw sugar based mediums) is described. Parameters influencing pseudo-digestion, such as sonication time, sample mass and solvent system were fully optimized. Final solutions obtained upon sonication were analyzed by electrothermal atomic absorption spectrometry (ETAAS). The best conditions for metal pseudo-digestion were as follows: a 25, 30 and 20 min sonication time for beet molasses, cane molasses and raw sugar based medium samples, respectively, 0.7 g sample mass of raw sugar based samples, 0.5 g sample mass of molasses based samples and an extraction mixture of concentrated HNO₃-H₂O₂, in 25 mL of solvent. Analytical results obtained for the two metals by ultrasound assisted pseudo-digestion and conventional wet digestion methods showed a good agreement. This method reduces the time required for all treatments (heating to dryness, cooling and separation) in comparison with conventional wet digestion method. The accuracy of the method was tested by comparing the obtained results with that of conventional wet digestion method.      

阻抑动力学荧光法测定柠檬酸

基于在高氯酸介质中柠檬酸能抑制铁(Ⅲ)催化H2O2氧化吡咯红Y的反应，建立了一种测定柠檬酸的动力学荧光分析法。方法的线性范围为0．12-2．4μg/mL，检出限为0．05μg/mL。将方法用于汽水中柠檬酸的测定，回收率为97％-106％。     

离子色谱法测定威力酸中的有机酸

采用离子排斥分离,电导检测模式,对威力酸中的4种有机酸成份进行分离测定。将威力酸样品通过萃取、洗涤、过滤之后进样,可以测定其柠檬酸、乳酸、苹果酸、富马酸4种有机酸,在一定的色谱条件下,4种阴离子都具有很好的线性和较低的检出限。威力酸中的柠檬酸,乳酸,苹果酸,富马酸的检出限分别是0.10、0.14、0.30和0.12μg/L,线性相关系数r2在0.9997~0.9999范围内,样品中待测离子峰面积的RSD在4.3%以下(n=10),回收率在94%~105%之间。采用抑制电导的离子色谱法是分析威力酸中的有机酸成份的高效与准确的方法。     

Fluorimetric kinetic method for the determination of total ascorbic acid with o-phenylenediamine

A fluorimetric reaction-rate method for the determination of L-ascorbic acid (AA) in aqueous solution is presented. The technique is based on the rapid oxidation of AA by mercury(II) chloride to dehydro-L-ascorbic acid, which then reacts with o-phenylenediamine to form a fluorescent quinoxaline. The formation of the product is monitored fluorimetrically with a data acquisition system based on a microcomputer, a voltage-to-frequency converter and a timer-counter board. The initial rate is estimated with a fixed-time computational method. With a 20-s measurement time (after a 5-s delay from initiation of the reaction), the detection limit for AA is 0.02 μg ml^?1 with a linear dynamic range extending to 10 μg ml^?. The procedure is applied to the determination of the AA in vitamin pills and juice. The relative standard deviation is 1.9% or better.     

Exploring the potential of biodiesel derived crude glycerol into high value malic acid: Biosynthesis,process optimization and kinetic assessment

In this study, Zygosaccharomyces rouxii, a sugar tolerant yeast culture was explored for the production of high value malic acid using crude glycerol from biodiesel plant. In addition, the effect of addition of glutamic acid (precursor) (0.25 to 1%), temperature (15 to 30 ​°C) and time (0 to 24 days) of the fermentation process was also investigated by both conventional as well as Response Surface Methodology (RSM). The highest malic acid of 72.1 ​± ​0.05 ​g/L was obtained and RSM predicts the accurate optimized conditions such as 30% crude glycerol concentration in the fermentative media with 0.75% addition of precursor with initial pH 5 ​at 20 ​°C for 20 days. This study reveals that the crude glycerol can be efficiently used and the production of malic acid was raised with 3 folds correspond to no precursor under optimal conditions. The growth and product kinetics were studied by Monod, Logistic, Leudeking Piret as well as Logistic incorporated Leudeking-Piret models with and without precursor and Logistic incorporated Leudeking-Piret model allowed the best fit for the malic acid production.     

Determination of citric acid in fermentation media by pyrolysis mass spectrometry

Rapid and sensitive determination of citric acid in fermentation media by pyrolysis mass spectrometry (Py–MS) is proposed. Owing to high specificity of this method, distinguishing the citric acid from the matrix and by-products formed in the Krebs cycle is possible. Selected ion monitoring (SIM) mode is used for quantitative measurements, in which mass to charge (m/z) values of 175 of citric acid and 138 of 3-nitroaniline as internal standard are chosen. Limit of detection (LOD) for this method has been found to be 1 ng ml⁻¹ and the linear working range was 10 ng ml⁻¹–100 mg ml⁻¹. Relative standard deviation (R.S.D.) of the method for five replicates was 0.84%. Results of Py–MS are compared with those obtained by UV–vis spectrophotometric method. Also, factor analysis is used for evaluating the influence of pH, molasses concentration, time and shaker intensity on the production of citric acid by Aspergillus niger.     

Separation of thorium by anion-exchange chromatography in malic acid media

Summary Systematic studies on the anion-exchange behaviour of thorium in malic acid solution on Amberlite IRA-401 have been carried out. Acids such as HNO₃, HCl, H₂SO₄, HClO₄ and salts such as NH₄Cl, (NH₄)₂SO₄, NaClO₄, NaCl and NaNO₃ have been tested as eluants for thorium, their efficiency being evaluated in terms of their distribution coefficients. HNO₃ is the best eluent for thorium. Methods have been developed for the separation of thorium from several elements in malic acid media using selective adsorption or selective elution. The proposed method is applied to the analysis of thorium in monazite where HClO₄ is a better eluant than HNO₃. The method is simple and the accuracy about ±3%.     

固相萃取-抑制电导离子色谱法测定水产品中有机酸

建立了梯度淋洗-抑制型电导离子色谱法检测水产品中有机酸的方法。在2～3个数量级范围内,该方法对目标化合物的检测线性良好。酒石酸的线性范围为15～500 ng/mL,检测限为0.05 mg/kg;柠檬酸线性范围为8～500 ng/mL,检测限为0.03 mg/kg。以大黄鱼、中华绒螯蟹、南美白对虾、文蛤为空白样品,加入酒石酸和柠檬酸质量分数分别为0.05,0.07和0.10 mg/kg,酒石酸的加标回收率介于84.4%～89.2%,RSD<6.5%,柠檬酸的加标回收率介于87.5%～93.8%,RSD<5.9%。