The Interactions of Aqueous Solutions of Chlorine with Citric Acid. A Source of Mutagens. (A Preliminary Report)

Abstract

Citric acid, an additive to an important acrylamide based polymeric flocculant, was found to react with an aqueous solution of chlorine to give several chlorinated propanones, di- and trichloroacetic acid, chloroform, and a number of as yet unidentified chlorine containing compounds. Formation of these alledged carcinogens and mutagens also takes place by treating diluted aqueous solutions of frozen orange juice concentrate with such chlorine solutions. The formation and ratios of the detected chlorinated compounds is pH-dependent. A tentative scheme which could account for these findings is presented.     

Physicochemical Properties,Fatty Acid Composition,Volatile Compounds of Blueberries,Cranberries, Raspberries,and Cuckooflower Seeds Obtained Using Sonication Method

Every year, thousands of tons of fruit seeds are discarded as agro-industrial by-products around the world. Fruit seeds are an excellent source of oils, monounsaturated fatty acids, and n-6 and n-3 polyunsaturated essential fatty acids. This study aimed to develop a novel technology for extracting active substances from selected seeds that were obtained after pressing fruit juices. The proposed technology involved sonification with the use of ethyl alcohol at a low extraction temperature. Seeds of four species—blueberry (Vaccinium myrtillus L.), raspberry (Rubus idaeus), cranberry (Vaccinium macrocarpon), and cuckooflower (Cardamine pratensis)—were used for extraction. Following alcohol evaporation under nitrogen, the antioxidant activity, chemical composition, and volatile compounds of the obtained extracts were analyzed using chromatographic methods, including gas chromatography (GC)–mass spectrometry (MS) (GC–MS/MS), and high-performance liquid chromatography–MS. We analyzed physicochemical properties, fatty acid, and volatile compounds composition, sterol and tocochromanol content of blueberry, cranberry, raspberry, and cuckooflower seed oils obtained by sonication. This method is safe and effective, and allows for obtaining valuable oils from the seeds.     

Gas chromatographic-mass spectrometric fragmentation study of flavonoids as their trimethylsilyl derivatives: analysis of flavonoids, sugars, carboxylic and amino acids in model systems and in citrus fruits

The fragmentation patterns and quantitation possibilities of three anthocyanidins (pelargonidin, cyanidin, malvidin), one flavonol (quercetin), two flavones (apigenin, luteolin) and two flavanones (naringenin, hesperetin) have been investigated as trimethylsilyl and as trimethylsilyl (oxime) derivatives by gas chromatography-mass spectrometry. Results proved that anthocyanidins and flavanones form trimethylsilyl (oximes), while flavonol and flavones provide simple trimethylsilyl derivatives. In all cases, characteristic fragments of high masses are formed proper for quantitation purposes. Hydrolysis conditions for naringin, hesperidin and rutin have been optimized, resulting in the quantitative release of naringenin, hesperetin and quercetin together with their corresponding saccharides. These basic studies made possible the identification and quantification of the flavonoid, carboxylic-/amino acid and sugar constituents of citrus fruit juices and albedos, without any extraction/enrichment procedure. In total 33 compounds have been determined in hydrolyzed samples, such as 2 flavonoids (naringenin and hesperetin), 6 phenolic acids (trimethoxybenzoic, 4-hydroxybenzoic, vanillic, quinic, chlorogenic and rosmarinic acids), 3 aliphatic carboxylic acids (levulinic, malic, citric acids), phosphoric acid, 4 amino acids (aspartic, glutamic acids, alanine, proline), 9 monosaccharides (xylose, arabinose, rhamnose, fucose, fructose, galactose, glucose, galacturonic acid, sedoheptulose), inositol, sugarphosphate, 5 disaccharides and tocopherol. Measurements were carried out as the trimethylsilyl (oxime) ether/ester derivatives of constituents, in the concentration range of 2 x 10(-3) to 49.9%. Identification level of samples varied between 26.4 and 77.5%, expressed in dry matter content of juices and albedos.     

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...     

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.     

Determination of ink photoinitiators in packaged beverages by gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry

A new analytical method, using gas chromatography-mass spectrometry (GC/MS) and liquid chromatography-mass spectrometry (LC/MS) techniques, was developed for the determination in packaged food beverages of five ink photoinitiator residues: 2-isopropylthioxanthone (ITX), benzophenone, 2-ethylhexyl-4-dimethylaminobenzoate (EHDAB), 1-hydroxycyclohexyl-1-phenyl ketone (IRGACURE 184) and ethyl-4-dimethylaminobenzoate (EDAB). Samples were extracted from selected beverages (milk, fruit juices and wine) and relative packagings, using n-hexane and dichloromethane, respectively, purified on solid-phase extraction (SPE) silica gel cartridges, and then analyzed in GC/MS and LC/MS. The recovery percentages, obtained spiking the beverage samples at concentrations of 4 and 10 microgl(-1) with a standard mixture of photoinitiators, were in the range 42-108% (milk), 50-84% (wine), and 48-109% (fruit juices). The repeatability of the method was assessed in all cases by the % of correlation value, that was lower than 19%. The lowest limits of detection (LODs) and limits of quantification (LOQs), obtained using GC/MS, were in the range 0.2-1 and 1-5 microgl(-1), respectively. The method was applied to the analysis of forty packaged food beverages (milk, fruit juices and wine samples). The most significant contamination was that of benzophenone, found in all samples in a concentration range of 5-217mugl(-1). Its presence was confirmed by an LC/Atmospheric-Pressure PhotoIonization (APPI)/MS/MS analysis. The photoinitiator (EHDAB) was found in eleven out of forty beverages in a concentration range of 0.13-0.8 microgl(-1). Less important was the ITX contamination, found in three out of forty samples in a range 0.2-0.24 microgl(-1). The work proposes a new method to analyze ink photoinitiator residues in polycoupled carton packaging and in contained food beverages.     

Determination of α‐hydroxy acids and their enantiomers in fruit juices by ligand exchange CE with a dual central metal ion system

The content of α‐hydroxy acids and their enantiomers can be used to distinguish authentic and adulterated fruit juices. Here, we investigated the use of ligand exchange CE with two kinds of central metal ion in a BGE for the simultaneous determination of enantiomers of dl ‐malic, dl ‐tartaric and dl ‐isocitric acids, and citric acid. Ligand exchange CE with 100 mM d ‐quinic acid as a chiral selector ligand and 10 mM Cu(II) ion as a central metal ion could enantioseparate dl ‐tartaric acid but not dl ‐malic acid or dl ‐isocitric acid. Addition of 1.8 mM Sc(III) ion to the BGE with 10 mM Cu(II) ion to create a dual central metal ion system permitted the simultaneous determination of these α‐hydroxy acid enantiomers and citric acid. The proposed ligand exchange CE was thus well suited for detecting adulteration of fruit juices.     

两种煤的次氯酸钠水溶液降解产物的分离与分析

两种煤于温和条件下在次氯酸钠水溶液中进行降解,所得水溶液经酸化后,水溶物依次用乙醚、CS2、石油醚、乙酸乙酯和苯进行分级萃取,萃取物经重氮甲烷酯化后用GC/MS分析。结果发现氯代物、脂肪酸和芳酸是煤的NaOCl水溶液降解的典型化合物,不同极性溶剂分级萃取可以实现产物的初步族组分分离。通过该研究建立煤的次氯酸钠氧化反应混合物有效分离和分析的方法,为煤的高附加值利用提供有效的途径。     

Photodegradation and by-products identification of commercial extractant Cyanex 302

The photodegradation of the organothiophosphorous extractant Cyanex 302 and purified bis(2,4,4-trimethylpentyl)monothiophosphinic acid dissolved in toluene was carried out in photoreactor using UV–Vis light irradiation. Possible degradation products were identified with the assistance of FT-IR, LC/MS/MS and GC/MS. The catalytic influence of zinc(II), copper(II) and cobalt(II) ions and the presence of trace values of water and aqueous solutions of sulphuric acids on the photodecomposition of Cyanex 302 were studied. The results demonstrated that the presence of trace amounts of water causes mainly the degradation of bis(2,4,4-trimethylpentyl)monothiophosphinic acid with the simultaneously fourfold increase in bis(2,4,4-trimethylpentyl)phosphinic acid concentration. The shaking with aqueous solution of sulphuric acids results in the decrease in the photodegradation probably by blocking of OH radical. Metal ions also affect the degradation causing the increase in bis(2,4,4-trimethylpentyl)phosphinic acid concentration. The photodegradation was also carried out in open atmosphere under sunlight and the obtained results were compared with those obtained in a Heraeus photoreactor.     

Electrosynthesis of 4-chloropyrazolecarboxylic acids

4-Chlorosubstituted pyrazolecarboxylic acids were synthesized via chlorination of the corresponding acids at the Pt anode in NaCl aqueous solutions under conditions of divided galvanostatic electrolysis. The efficiency of the process depends on the structures of the initial pyrazolecarboxylic acids, particularly, on the donor-acceptor properties of the substituents and on their position in the pyrazole ring. The yields of the 4-chlorosubstituted products of chlorination of pyrazole-3(5)-carboxylic acid, 1-methylpyrazole-5-carboxylic acid, 1-methyl-pyrazole-3-carboxylic acid, 1-ethylpyrazole-3-carboxylic acid, and 1-methyl-3-nitropyrazole- 5-carboxylic acid are 92, 93, 69, 80, and 4%, respectively.     

Novel tandem reaction of benzyne with cyclic ethers and active methines: synthesis of ω-trichloroalkyl phenyl ethers

The reaction of benzenediazonium carboxylate with chloroform in refluxing tetrahydrofuran afforded 5,5,5-trichloropentyl phenyl ether in 61% yield along with benzoic acid (7%). When dichloroacetonitrile was used as a reactant, 5,5-dichloro-5-cyanopentyl phenyl ether was obtained in 65% yield. Reactive benzyne derived from diazonium carboxylate initially reacted with THF to give a dipole intermediate, which further reacted with chloroform or dichloroacetonitrile to give ring opened products.     

Analytical Characterization of Fatty Acids Composition of Bioactive Stem Oil of Maytenus royleanus by Gas Chromatography Mass Spectrometry

The significant inhibition and selectivity for human solid tumor cell by oily fraction of Maytenus royleanus, was subjected to GC‐MS analysis for determination of its chemical constituents. GC‐MS profile of methyl ester derivatives of fatty acids, showed that Palmitic acid (35.41%), Oleic acid (10.91%), Stearic acid (5.31%), Margaric acid (5.13%), Behenic acid (5.18%) and Hexanoic acid (4.97%) were the major components in the isolated oily fraction, while rest of the other fatty acids were present in minor concentration. The literature revealed that no such work has been done for the determination of fatty acids in M. royleanus stem oil.     

特丁二甲硅烷基衍生化气相色谱-质谱法检测尿中4种苯氧羧酸类除草剂

建立了尿中2,4-滴(2,4-D)、2,4-滴丙酸(2,4-DP)2、甲4氯(MCPA)和2甲4氯丙酸(MCPP)4种苯氧羧酸类除草剂的气相色谱-质谱(GC-MS)分析方法。尿样加氯化钠饱和,酸化后用乙醚萃取,萃取物进行特丁二甲硅烷基(TBDMS)衍生化后分析。尿中4种除草剂的浓度在3~3 000 ng/mL范围内工作曲线的线性关系良好,检出限在1 ng/mL以下,3、100和1 000 ng/mL水平加标回收率在97.0%~102.2%之间,精密度在6.2%~14.2%之间。该法灵敏,可用于中毒者和职业接触者尿中苯氧羧酸类除草剂的分析。     

秸秆稀酸水解液的气相色谱／质谱法研究

在秸秆两步稀酸水解工艺中,用气相色谱/质谱(GC/MS)法对其水解液中的单糖成分进行测定,采用2%硼氢化钠的氨溶液将稀酸水解液中的单糖还原成糖醇,然后在甲基咪唑催化剂的作用下和乙酸酐在水相中直接反应生成乙酰化的糖醇,用二氯甲烷萃取后进行GC/MS测定.研究结果表明:秸秆稀酸水解液中有五种单糖,主要是木糖和葡萄糖,其次是阿拉伯糖、半乳糖和少量的甘露糖;利用此方法测定了一批秸秆稀酸水解液,得到了该秸秆稀酸水解过程的最佳的反应时间.该方法可快速、准确测定秸秆稀酸水解液中单糖的浓度,为水解工艺的研究提供一种有效的分析方法.     

Lipophilic constituents from two processed products and three different parts of Changium smyrnioides Wolff.

This article reports the lipophilic chemical composition of different processed products (Changii Radix, Changii Radix Alba) and parts (root bark, leaf and fruit) of Changium smyrnioides Wolff.. The lipophilic constituents were extracted with petroleum ether in Soxhlet apparatus, subsequently identified and determined by gas chromatography–mass spectroscopy (GC–MS). Yield of lipophilic constituents from Changii Radix (3.65%) was about three times more than Changii Radix Alba's (1.07%), which indicated processing by boiling in water had an impact on the content of lipophilic constituents. Moreover, the major compounds in different processed products and parts were found to be fatty acids and sesquiterpenes. The results are a contribution for the lipophilic chemical composition and can serve as a reference for product development of Changium smyrnioides Wolff..     

Evaluation of pesticide residue in grape juices and the effect of natural antioxidants on their degradation rate

Various studies have been drawn toward the beneficial properties of fruit juices because they have several components, such as phenols, vitamins, and flavonoids, with antioxidant effects. However, fruit juices can also contain residues of pesticides used as standard pest control methods in crops. Many of these pesticides are degraded through oxidative mechanisms, and their persistence in juices can be enhanced by antioxidants. This study covers the degradation of four pesticides, aldicarb, demeton-S-methyl, fenamiphos, and methiocarb, to their respective sulfoxide and sulfone in grape juices, water (pH 3.5) and water (pH 3.5) with quercetin (one of the most important flavonoids of grape) added in an attempt to establish whether the presence of antioxidants can affect the degradation rate of pesticides. For this purpose, a multiresidue method based on solid-phase extraction (SPE) was developed for the simultaneous determination of these pesticides and their metabolites in commercial juices. The extraction procedure was carried out in C₁₈ columns. The subsequent elution of pesticides was performed with dichloromethane prior to the determination by liquid chromatography-tandem mass spectrometry (LC-MS/MS), using two precursor-product ion transitions. Average recoveries for all the pesticides studied were higher than 80%, with relative standard deviations lower than 15% in the concentration range 0.005–0.05 μg/mL, and the quantification limits achieved ranged from 0.1 to 4.6 μg/L. The results demonstrated that degradation was slower in fruit juices and aqueous solutions with quercetin than in water. Several commercial grape juices were also analyzed to establish the levels of these pesticides. Methiocarb, fenamiphos, and demeton-S-methyl were found at low levels in some samples.     

高效液相色谱法测定果酸

本文研究了反相高效液相色谱法同时分离和测定6种果酸的色谱条件,提出了有效提取果酸的方法,并对苹果梨、香水梨等样品进行了实际分析。结果表明,该法简更快速,具有较高的准确度和精密度。     

Oxidation of Linoleic Acid in Low-Density Lipoprotein: An Important Event in Atherogenesis

Contrary to earlier views the main oxidation products of low-density lipoprotein (LDL) are derived from linoleic acid and not arachidonic acid, as determined by GC/MS investigations of the in vitro oxidation of LDL samples. A similar product spectrum, in which epoxyhydroxyoctadecenoic acids such as 1 and 2 have been identified for the first time, is obtained from minimally oxidized (that is, aged) LDL. Since this is still recognized by the LDL receptor, it is concluded that toxic oxidation products are introduced in endothelial cells in vivo and cause damage there.     

Determination of alpha hydroxy acids in fruits by capillary electrophoresis.

Alpha hydroxy acids, malic acid, citric acid, tartaric acid, glycolic acid and lactic acid, were analyzed simultaneously using capillary electrophoresis with direct UV detection at 200 nm. The separation was carried out with uncoated fused-silica (50 cm x 50 microns i.d.), pressure injection at 15 psi s and operated at -15 kV potential. The separation buffers were prepared with 180 mM Na2HPO4, 1 mM cetyltrimethylammonium bromide and 15% (v/v) methanol and adjusted to pH 7.2 by phosphoric acid. Validation was performed for citric acid and malic acid. The obtained parameters were adequate and the limits of detection were 2.5 and 5 micrograms ml-1 for citric acid and malic acid, respectively. AHAs from natural fruit juices (orange and grape) were determined and measured with this method.     

Chromatographic separation and determination of fruit acids

A method is described for the determination of malic, tartaric and citric acids and sugar in fruit juices. It consists of the separation of these constituents by ion-exchange chromatography through a column of Dowex I-X8 with an acetate buffer as eluent, treatment of aliquots of the separated constituents with dichromate and sulfuric acid and measurement of the absorbance of the resultant green chromium(lll).