High and low oxalate content in spinach: an investigation of accumulation patterns.

BACKGROUND: Oxalic acid is a common antinutrient in the human diet, found in large quantities in spinach. However, spinach is highly regarded by vegetable producers because of its nutritional content and economic value. One of the primary purposes of spinach-breeding programs is to improve the nutritional value of spinach by adjusting oxalate accumulation. Knowledge of the biosynthetic patterns of oxalic acid, and its different forms, is important for a better understanding of this process. RESULTS: We found three biosynthetic patterns of accumulation and concentration of oxalates. Two of them are related to the maximum type and one is related to the minimum type. We also developed a general model of variations in these compounds in the genotypes that were studied. CONCLUSION: This study introduced a unique type of spinach with high oxalate accumulation, which could be particularly suitable for consumption. This had the highest ratio of insoluble oxalate to soluble oxalate. It also accumulated more ascorbic acid (AA) than other types. Our findings in this study also indicate a small role for AA as a precursor to oxalate production in spinach, possibly confirming the significant role of glyoxylate as the most critical precursor in this plant. © 2021 Society of Chemical Industry.

Simple and ultrasensitive electrochemical sensor for oxalic acid detection in real samples by one step co-electrodeposition strategy.

Oxalic acid (OA), naturally available in vegetables and foodstuffs derived from them, easily combines with calcium and iron to form insoluble oxalates. Their chelation will result in various renal diseases; thus, the accurate determination of OA is quite significant in the evaluation of food quality and healthcare settings. Here, we developed an electrochemically induced alcohol-free sol-gel method to obtain platinum nanoparticles (PtNPs) adhered with porous silica on glassy carbon electrode (PSiO2-PtNPs/GCE) by a one-step process, which can be potentially used as an excellent catalyst towards electrochemical oxidation of OA for the first time. Without any redox mediator, PSiO2-PtNPs/GCE exhibited a low oxidation overpotential and a significantly high current signal, achieving a wide linear range of concentration from 0 to 45 µM and a detection limit as low as to 25 nM for OA detection. Moreover, this present alcohol-free sol-gel approach towards OA determination was verified in real samples, which is promising for foodstuff analysis and clinical diagnosis. Graphical abstract.

Chemical Speciation of Aluminum in Wine by LC-ICP-MS.

Aluminum is very common in the natural environment and in everyday human life. We are living in the "aluminum age." Its average daily intake should not exceed a few mg/day. Unfortunately, despite the growing number of alarming data about the toxicity of this element, human exposure to aluminum is constantly increasing. The toxicity and bioavailability of aluminum depends mainly on the form in which it occurs. The main variables conditioning the form are the concentration, the type, the molar ratio of aluminum to ligand, the pH value, and the temperature. This research presents a new method for speciation analysis of both inorganic and organic aluminum complexes in model solutions by LC-ICP-MS. Different solutions with variable pH values and different Al/ligand molar ratios (fluorides and several organic ligands, e.g., citrates and oxalates ions) were used. The chromatographic separation process was carried out based on isocratic and gradient elution, using a cation exchange analytical column. All determinations have been confirmed based on chemical equilibrium modeling programs. The new developed method was successfully applied for the first time in speciation analysis of real samples: white and red wine.

Effects of different cooking methods on the antioxidant capacity and flavonoid, organic acid and mineral contents of Galega Kale (Brassica oleracea var. acephala cv. Galega).

Brassica spp. are good sources of bioactive substances, which are known to have beneficial health effects. The objective of this work was to evaluate the effect of different cooking methods (boiling, steaming, microwaving, pressure cooking and vacuum cooking) on the antioxidant capacity and on the flavonoid, organic acid and mineral contents of Galega kale. Results indicate that this vegetable has a high antioxidant capacity and high contents of total flavonoids, organic acids, and minerals such as potassium and calcium. All of the cooking methods yielded losses of antioxidant capacity and of total flavonoids, organic acids and minerals, relative to the contents in fresh kale. Steaming proved to be the best method of preserving the antioxidant capacity and bioactive compounds. Although cooking did not cause large losses of oxalic acid, the resulting oxalate:calcium ratio was rather low (<2). The present data demonstrate that the different cooking methods have different effects on the bioactive compounds in kale, and that it is important the optimisation of such methods in order to minimise losses of the nutritional properties.

[Determination of the content of organic acids in the saliva of patients with breast cancer by capillary electrophoresis.]

A technique for quantitative determination of low molecular weight organic acids in saliva by the method of capillary electrophoresis has been developed. The method was tested on volunteers, divided into 3 groups: the main one (breast cancer, n=21), the comparison group (fibroadenomas, n=29) and the control group (conditionally healthy, n=26). It is shown that the concentration of lactic, acetic and propionic acids increases uniformly when passing from the control group to the comparison group, and then to the main group. Against the background of breast cancer, the concentration of oxalic and formic acids decreases in comparison with the control, whereas in fibroadenomas the concentration of oxalic acid decreases, and the formic acid grows. In general, the proposed method can be a valuable tool in the study of metabolic changes associated with cancer.

Potential use of cuminic acid as a botanical fungicide against Valsa mali.

Valsa canker caused by Valsa mali is commonly present in eastern Asia and cause large economic losses. Because of limited agricultural measures and chemical residues of commonly used fungicides there is an urgent need of alternative plant protecting agents. On this background the activity of cuminic acid, a plant extract from the seed of Cuminum cyminum L, was assessed. The median effective concentration (EC50) values for inhibition of mycelial growth of seven V. mali strains ranged from 3.046 to 8.342 µg/mL, with an average EC50 value of 4.956 ± 0.281 µg/mL. The antifungal activity was the direct activity of cuminic acid instead of the influence on the pH of media by cuminic acid. After treated with cuminic acid, mycelia dissolved with decreased branches and swelling; cell membrane permeability increased while pectinases activity decreased significantly. Moreover, peroxidase (POD) activity of the apple leaves increased after treated with cuminic acid. Importantly, on detached branches of apple tree, cuminic acid exhibited both protective and curative activity. These results indicated that cuminic acid not only showed the antifungal activity, but also could improve the defense capacity of the plants. Taken together, cuminic acid showed the potential as a natural alternative to commercial fungicides or a lead compound to develop new fungicides for the control of Valsa canker.

Characteristics of organic acid profiles in 16 species of wild growing edible mushrooms.

The aim of study was to determine 9 organic acids in nine aboveground and seven wood-growing wild edible mushroom species originated from an area under the direct influence of a busy trunk road in Poland. The organic acids in the extracts of samples were identified by reversed-phase column liquid chromatography (RPLC). The presented results show that all the mushroom species were characterized by high variation in the profile and content of the analyzed acids. Each of mushroom species contained oxalic acid, the profiles of the other acids strictly depended on mushroom species. Among aboveground species, the highest total content of organic acids was found in Lepista gilva (267.5 ± 26.6 mg g-1 dry weight (DW)), while Laccaria amethystina was characterized by the lowest content (37.7 ± 6.5 mg g-1 DW). Within wood-growing species, the highest content of organic acids was determined in Flammulina velutipes (171.9 ± 26.7 mg g-1 DW), whereas the lowest content (34.2 ± 2.9 mg g-1 DW) of the studied acids was observed in Grifola frondosa.

Chemical Composition and Yield of Six Genotypes of Common Purslane (Portulaca oleracea L.): An Alternative Source of Omega-3 Fatty Acids.

Common purslane (Portulaca oleracea L.) is an annual weed rich in omega-3 fatty acids which is consumed for its edible leaves and stems. In the present study six different genotypes of common purslane (A-F) were evaluated for their nutritional value and chemical composition. Nutritional value and chemical composition depended on genotype. Oxalic acid content was the lowest for genotype D, whereas genotypes E and F are more promising for commercial cultivation, since they have low oxalic acid content. Genotype E had a very good antioxidant profile and a balanced composition of omega-3 and omega-6 fatty acids. Regarding yield, genotype A had the highest yield comparing to the other genotypes, whereas commercial varieties (E and F) did not differ from genotypes B and C. This study provides new information regarding common purslane bioactive compounds as affected by genotype and could be further implemented in food industry for products of high quality and increased added value.

Tungsten carbide nanotubes supported platinum nanoparticles as a potential sensing platform for oxalic acid.

Supported tungsten carbide is an efficient and vital nanomaterial for the development of high-performance, sensitive, and selective electrochemical sensors. In this work, tungsten carbide with tube-like nanostructures (WC NTs) supported platinum nanoparticles (PtNPs) are synthesized and explored as an efficient catalyst toward electrochemical oxidation of oxalic acid for the first the time. The WC NTs supported PtNPs modified glassy carbon (GC) electrode is highly sensitive toward the electrochemical oxidation of oxalic acid. A large decrease in the oxidation overpotential (220 mV) and significant enhancement in the peak current compared to unmodified and Pt/C modified GC electrodes have been observed without using any redox mediator. Moreover, WC NTs supported PtNPs modified electrode possessed wide linear concentration ranges from 0 to 125 nM and a higher sensitivity toward the oxidation of oxalic acid (80 nA/nM) achieved by the amperometry method. The present modified electrode showed an experimentally determined lowest detection limit (LOD) of 12 nM (S/N = 3). Further, WC NTs supported PtNPs electrode can be demonstrated to have an excellent selectivity toward the detection of oxalic acid in the presence of a 200-fold excess of major important interferents. The practical application of WC NTs supported PtNPs has also been demonstrated in the detection of oxalic acid in tomato fruit sample, by differential pulse voltammetry under optimized conditions.

Effect of ensiling treatment on secondary compounds and amino acid profile of tropical forage legumes, and implications for their pig feeding potential.

BACKGROUND: Smallholders in the tropics depend on local protein supplements to balance pig diets. Thus, various tropical forage legumes are a potential feeding option. Ensiling allows converting forages into a ready-to-feed-out choice, but the lactic acid fermentation may influence various (anti)nutritional components. The purpose of this study was to evaluate the effects of sucrose (SU) and a tropical Lactobacillus plantarum strain (LAB) as ensiling treatments (control, SU, LAB, LAB + SU) on the potential nutrient availability of 10 forage legume species. RESULTS: Ensiling commonly reduced antinutritional compounds such as tannins (by 49-84%) and trypsin inhibitory activity (by 74-78%), as well as oxalic acid (by 51-100%). An improved potential absorbability of protein and minerals for pigs is thus inferred. There was no major loss in total amino acids. In general, the species effect was stronger than the treatment effect. A clear effect of the treatments SU, LAB and LAB + SU over all 10 forage species was only observed for oxalic acid, single amino acids and trypsin inhibitory activity. CONCLUSION: Ensiling is a viable option to enhance nutrient utilization of tropical forages for pigs. Species-specific treatment of forage legumes is recommended.

Oxidative degradation of sulfathiazole by Fenton and photo-Fenton reactions.

This article presents experimental results on 47 µmol L(-1) sulfathiazole (STZ) degradation by Fenton and photo-Fenton reactions using multivariate analysis. The optimal experimental conditions for reactions were obtained by Response Surface Methodology (RSM). In the case of the Fenton reactions there were 192 µmol L(-1) ferrous ions (Fe(II)) and 1856 µmol L(-1) hydrogen peroxide (H2O2), as compared with 157 µmol L(-1) (Fe(II)) and 1219 µmol L(-1) (H2O2) for photo-Fenton reactions. Under these conditions, around 90% of STZ degradation were achieved after 8 minutes treatment by Fenton and photo-Fenton reactions, respectively. Moreover, a marked difference was observed in the total organic carbon (TOC) removal after 60-min treatment, achieving 30% and 75% for the Fenton and photo-Fenton reactions, respectively. Acetic, maleic, succinic and oxamic acids could be identified as main Fenton oxidation intermediates. A similar pattern was found in the case of photo-Fenton reaction, including the presence of oxalic acid and ammonia at short periods of irradiation with UV-A. The calculated values of Average Oxidation State (AOS) corroborate the formation of oxidized products from the initial steps of the reaction.

[Spectroscopic methods applied to component determination and species identification for coffee].

Spectroscopic analysis was applied to the determination of the nutrient quality of ground, instant and chicory coffees. By using inductively coupled plasma atomic emission spectrometry (ICP-ES), nine mineral elements were determined in solid coffee samples. Caffeine was determined by ultraviolet (UV) spectrometry and organic matter was investigated by Fourier transform infrared (FTIR) spectroscopy. Oxidation-reduction titration was utilized for measuring the oxalate. The differences between ground coffee and instant coffee was identified on the basis of the contents of caffeine, oxalate and mineral elements. Experimental evidence showed that, caffeine in instant coffee was 2-3 times higher than in ground coffee. Oxalate in instant coffee was significantly higher in ground coffee. Mineral elements of Mg, P and Zn in ground coffee is lower than in instant coffee, while Cu is several times higher. The mineral content in chicory coffee is overall lower than the instant coffee. In addition, we determined the content of Ti for different types of coffees, and simultaneously detected the elements of Cu, Ti and Zn in chicory coffee. As a fast detection technique, FTIR spectroscopy has the potential of detecting the differences between ground coffee and instant coffee, and is able to verify the presence of caffeine and oxalate.

Aerobic to anaerobic transition in Biomphalaria glabrata (Say, 1818) infected with different miracidial doses of Echinostoma paraensei (Lie and Basch, 1967) by high-performance liquid chromatography.

The glucose content in the hemolymph and glycogen content in the digestive gland-gonad complex (DGG) and cephalopedal mass of Biomphalaria glabrata exposed to different parasite doses (5 and 50 miracidia) of Echinostoma paraensei as well as the activity of lactate dehydrogenase were evaluated. HPLC (high-performance liquid chromatography) analyses were also performed to determine the concentrations of four organic acids (oxalic, succinic, pyruvic and lactic) present in the hemolymph of infected and uninfected snails, to better understand the effect of infection on the host's energetic/oxidative metabolism. The snails were dissected 1-4 weeks after infection to collect the hemolymph and separate the tissues. There was alteration in the glycemia of the snails at both parasite doses, with a significant increase of glycemia from of the third week after infection in comparison to the control group. Changes were also observed in the lactate dehydrogenase activity, with increased activity as the infection progressed. In parallel, there was a decrease in the glycogen content in the storage tissues, with a markedly greater reduction in the digestive gland-gonad complex (larval development site) in comparison with the cephalopedal mass. Additionally, the infection by both miracidial doses resulted in an increase of oxalic and lactic acid levels, as well as in a decline of piruvic and succinic acid levels in B. glabrata, thus explaining the reduction of the oxidative decarboxylation rate in the tricarboxylic acid cycle and acceleration of the anaerobic degradation of carbohydrates in the snails, through lactic fermentation, which is essential to ensure energy supply and success of the infection.

Effect of processing on proximate composition, anti-nutrient status and amino acid content in three accessions of African locust bean (Parkia biglobosa (jacq.) benth.

Proximate composition, amino acid levels and anti-nutrient factors (polyphenols, phytic acid and oxalate) in the seeds of Parkia biglobosa were determined at three stages: raw, boiled and fermented. The highest anti-nutrient factor present in the raw state was oxalate, while phytic acid was the least. The amino acid of the raw seeds matched favourably to the World Health Organization reference standard. After processing, boiling increased fat, crude fibre and protein, while it reduced moisture, ash and the anti-nutrient content in 64% of the cases examined. Fermentation reduced ash, crude fibre and carbohydrate in all the accessions. It increased the moisture, fat and protein, while reducing the anti-nutrient factors in 78% of the cases. The high levels of protein, fat and amino acids coupled with the low levels of the anti-nutrients in the boiled and fermented seeds make Parkia a good source of nutrients for humans and livestock.

Investigation of low-molecular weight organic acids and their spatiotemporal variation characteristics in Hongfeng Lake, China.

The identities and concentrations of low-molecular-weight organic acids (LMWOAs) were determined by ion chromatography throughout a 20-m water column in Hongfeng Lake, China. The spatiotemporal variations of LMWOAs and their contributions to dissolved organic matter (DOM) in a research period of 24 hr were also investigated. The results demonstrated that five LMWOAs (lactic, acetic, pyruvic, sorbic, oxalic acid) were detected, and their total concentration and proportion in DOC were 6.55 micromol/L and 7.47%. Their average levels were 2.50, 0.65, 2.35, 0.96 and 0.09 micromol/L, respectively. LMWOAs were higher during daytime (10:00-18:00 on Jun 13, 2008) than nighttime (21:00-6:00 the next morning), in particular 4.99 micromol/L high in the epilimnion (< or = 1 m water depth), reflecting the fact that direct import from terrigenous sources and photochemical production from humic materials were dominant during LMWOAs' origin and accumulation. The same factors caused LMWOAs to be 0.63 micromol/L in the epilimnion higher than in the hypolimnion. The rapid decrease of total organic acid (TOA) up until 18:00 mainly resulted from bio-uptake and mineralization in the hypolimnion (>1 m water depth). Pyruvic acid increased with time in the epilimnion and decreased in the hypolimnion, largely related to the two contrary processes of continuous degradation and synthesis of macromolecular organic matter during life materials' cycle mediated by organisms. Simultaneously, plankton behavior and thermal stratification played a pivotal role in LMWOAs' behavior in the water column, causing decreasing and increasing profiles. The distribution of LMWOAs represents an interesting resource for biogeochemical research of DOM in aquatic ecosystems.

Facile and rapid determination of oxalic acid by fading spectrophotometry based on Fe(III)-sulfosalicylate as colorimetric chemosensor.

Spectrophotometry is an economic and rapid method for detecting oxalic acid (OA), while the reported methods have some drawbacks, such as narrow linear range, long response time, delicate operation and required expensive reagents. Herein, we found that the as-synthesized Fe(III)-sulfosalicylate (FeSSA) could be used as an efficient colorimetric chemosensor to detect OA, and the established FeSSA-based fading spectrophotometry showed prominent advantages over the existing ones in detecting OA. The as-established method has wider linear range of 0.80-160 mg/L with regression coefficient ≥ 0.999, while the widest linear range is just 2.7-54 mg/L among the reported ones. Moreover, the method has low limit of detection (0.74 mg/L), extremely fast response (several seconds), satisfactory selectivity, high accuracy and precision. Most importantly, its reliability was further verified by employing it to determine OA concentration during the degradation process of organic pollutants. The measured OA concentration at any time interval was perfectly consistent with those determined by the well-recognized high performance liquid chromatography (HPLC). These confirmed that the FeSSA-based fading spectrophotometry is an efficient, simple, fast, accurate and economic method to determine OA in a wide concentration range.

Iron ore weathering potentials of ectomycorrhizal plants.

Plants in association with soil microorganisms play an important role in mineral weathering. Studies have shown that plants in symbiosis with ectomycorrhizal (ECM) fungi have the potential to increase the uptake of mineral-derived nutrients. However, it is usually difficult to study many of the different factors that influence ectomycorrhizal weathering in a single experiment. In the present study, we carried out a pot experiment where Pinus patula seedlings were grown with or without ECM fungi in the presence of iron ore minerals. The ECM fungi used included Pisolithus tinctorius, Paxillus involutus, Laccaria bicolor and Suillus tomentosus. After 24 weeks, harvesting of the plants was carried out. The concentration of organic acids released into the soil, as well as potassium and phosphorus released from the iron ore were measured. The results suggest that different roles of ectomycorrhizal fungi in mineral weathering such as nutrient absorption and transfer, improving the health of plants and ensuring nutrient circulation in the ecosystem, are species specific, and both mycorrhizal roots and non-mycorrhizal roots can participate in the weathering process of iron ore minerals.

[The evaluation of anti-nutritive components in beer on the example of oxalic acid]. / Ocena zawartosci skladników antyodzywczych w piwie na przykladzie kwasu szczawiowego.

BACKGROUND: Food in its composition contains anti-nutritional substances that reduces or prevents the use of valuable nutrients. The oxalic acid, as phytate and dietary fiber, occurs naturally in foods of plant origin, to which the beer is classified. The negative effect of oxalic acid is reducing the bioavailability of calcium and magnesium, and disorder of metabolism of the body's absorption of these elements from the diet. The excess of oxalic acid and its salt in the diet contributes to the formation of certain diseases, such as oxalate urolithiasis, osteoporosis, arthritis, etc. Due to the diuretic effect of beer, drinking moderate amounts of it is recommended as a preventive and support urinary tract disorders. OBJECTIVE: The aim of this study was to determine and comparison the oxalic acid content in selected beers available on the Polish market. MATERIAL AND METHOD: Fifty seven samples of beer were used for this study. These samples were divided into three groups depending on the alcohol concentration declared by the producers (1st group--below 5.5% vol., 2nd group--from 5.5 to 6.5% vol., 3rd group--above 6.5% vol.). The beer samples were incubated in the ultrasonic bath for 15 minutes following pH adjustments up to pH = 2 with the 1 mol/L hydrochloric acid to transform calcium oxalates into soluble form, then filtered. The oxalic acid concentration was measured by high performance liquid chromatography (HPLC) with conductivity detection. RESULTS: The concentration of oxalic acid in tested samples of beer ranged from 1.8 to 30.3 mg/L. No considerable differences between the concentration of oxalic acid in the three tested group of beer with the various content of the alcohol were found. Basing on the average concentrations of the oxalic acid in the different groups of the tested beers the positive trend in oxalic acid concentration related to the increase of alcohol could be observed. CONCLUSIONS: The very low concentration of oxalic acid allows to classify beer as food product safe for the human health in terms of low oxalates content.

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 (13)C-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.

Organic acid bioavailability from banana and sweet potato using an in vitro digestion and Caco-2 cell model.

INTRODUCTION: Organic acids from plant food have been shown to play an important role in the prevention of chronic diseases (osteoporosis, obesity), inherent to western diets, but little is known about their bioavailability in the small intestine, information that needs to be determined in order to quantify likely effects on human health. METHODS: An in vitro model of human digestion was carried out, comprising simulated oral, gastric and pancreatic digestion followed by an in vitro model of small intestine absorption using Caco-2 cell monolayers. As models for fruits and vegetables, freeze-dried or raw samples of banana and sweet potato were used. RESULTS: Organic acids have been found to be slowly released from the food matrix during simulated digestion of both banana and sweet potato, either raw or after freeze-drying. In the Caco-2 cell assay, malic and oxalic acids were absorbed more than citric acid. Oxalic and citric acids, but not malic acid, were transported across the cell monolayer. The release and uptake of major organic acids from model fruits and vegetables using established in vitro simulation processes was not quantitative and varied with acid type. CONCLUSION: Partial uptake is consistent with a dual nutritional role for organic acids as alkalinising agents (fraction which is taken up) and as modulators of large intestinal function (fraction which is not taken up in the small intestine). Studies of in vivo digestive release and uptake are needed in order to identify the contribution of organic acids to the nutritional value of fruits and vegetables.