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.

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.

Cr(VI) removal by Penicillium oxalicum SL2: Reduction with acidic metabolites and form transformation in the mycelium.

Bioremediation of Cr(VI) contamination using microorganisms is a promising method for reducing its environmental risks. The objective of this study was to clarify Cr(VI) removal by Penicillium oxalicum SL2 in terms of indirect Cr(VI) reduction by metabolites, interaction sites, and form transformation of chromium. Strain SL2 could sequentially remove Cr(VI) in the bioreactor. Oxalic acid produced by the fungus contributed to Cr(VI) reduction. Scanning transmissiony X-ray microscop (STXM) analysis suggested strain SL2 could partly reduce Cr(VI) to Cr(III) in the cell. Amine, carboxyl, and phosphate groups were related to Cr(VI) removal. Chromium K-edge X-ray absorption near edge structure (XANES) analysis implied Cr(III)-Cys potentially acted as an intermediate for the formation of chromium oxalate complexes during the process of treatment. This study would support the application of strain SL2 in Cr(VI) bioremediation and expand knowledge on the interaction of chromium with fungus.

Comprehensive Clinicopathologic Analyses of Acquired Cystic Disease-associated Renal Cell Carcinoma With Focus on Adverse Prognostic Factors and Metastatic Lesions.

Acquired cystic disease of kidney-associated renal cell carcinoma (ACD-RCC) is a distinct subtype of renal cell carcinoma with unique morphologic and clinicopathologic features. Generally, ACD-RCC is regarded as an indolent tumor; however, prognostic and outcomes data have been conflicted by the limited and relatively low number of cases with patient follow-up or adverse events. In this study, we focused on the histology of metastatic lesions and identifying prognostic factors associated with metastatic progression. From 32 cases in the cohort, 9 patients had metastasis [ACD-RCC (M+)] and 23 patients were without metastasis [ACD-RCC (M-)]. The median age of patients was 52 years; right side, n=10; left side, n=18; bilateral, n=4; median tumor size=2.6 cm; median hemodialysis duration=17 y; and the median duration of follow-up was 50 mo. Immunohistochemistry showed ACD-RCC to be racemase positive and CK7 negative to focally positive within tumor cells, with consistent positivity for renal histogenesis-associated markers (PAX8 and RCC antigen); S100A1 was a less reliable marker at metastatic sites. All metastatic ACD-RCC except 2 cases involved lymph nodes (para-aortic, renal hilar, subclavicular). Overall, 6/9 (67%) had visceral metastasis to sites including lung (n=3), liver (n=3), bone (n=5), stomach (n=1), and brain (n=1). In total, 5/9 (56%) metastatic tumors had distinctive cystic growth pattern at the metastatic site; intriguingly metastatic tumors had intrametastatic oxalate crystal deposition, a pathognomonic feature associated with primary tumors. Four of nine (44%) patients with ACD-RCC (M+) had fatal outcomes due to metastatic disease. Clinically significant adverse prognostic features associated with metastasis [median follow-up 47 mo, ACD-RCC (M+) vs. ACD-RCC (M-), 50 mo] included: duration of hemodialysis (≥20 vs. <20 y, P=0.0085) and tumor necrosis (P=0.049). Because of sufficient overlap between these parameters, the study was not able to identify parameters that would be reliable in further management strategies, in clinical settings. Our data indicate that ACD-RCC is a tumor which has distinct metastatic potential with nodal and visceral tropism and proclivity for cystic morphology at metastatic sites; this is the first report of the presence of oxalate crystals in metastatic tumors. Our data suggest that ACD-RCC patients with prolonged hemodialysis and tumoral coagulative necrosis require additional surveillance in view of the association of these parameters with metastatic progression.

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.

Root-induced changes in aggregation characteristics and potentially toxic elements (PTEs) speciation in a revegetated artificial zinc smelting waste slag site.

Root-induced changes play a crucial role in influencing the fate and speciation of potentially toxic elements (PTEs) in contaminated soils, but their role in the phytostabilization of waste slag sites remain unclear. The aim of this study was to determine the effect of four phytostabilization plants, Broussonetia papyrifera, Arundo donax, Robinia pseudoacacia, and Cryptomeria fortunei, planted in a zinc smelting waste slag site for 5 years on PTEs speciation and the mineral and aggregation characteristics at the interface of the waste slag-plant system. The results showed that the presence of a higher content of oxalic acid in the rhizosphere slags of the four plant species than in the bare slag. Revegetation of the waste slag with the four plant species significantly changed the mineral composition and morphology of the waste slag. The mass percentage of large particles (1-5 mm) and small particles (0.5-1 mm, 0.25-0.5 mm, and <0.25 mm) in the rhizosphere slags decreased and increased, respectively. The PTEs (Cu, Pb, Zn, and Cd) in most of the rhizosphere slags were mainly distributed within the small particles, and the enrichment coefficients of PTEs in the large particles and small particles were less than and greater than 1, respectively. The bioavailability of the PTEs in the waste slag increased with decreasing particle size. Root-induced the transformation of acid-soluble PTEs into their reducible, oxidizable, and residual forms in the different waste slag particles weathered in the rhizosphere. These results suggested that there are root-induced changes in the aggregation characteristics and geochemical behaviours of PTEs in waste slag fractions during the phytoremediation of waste slag sites.

Decomposition of spruce wood and release of volatile organic compounds depend on decay type, fungal interactions and enzyme production patterns.

Effect of three wood-decaying fungi on decomposition of spruce wood was studied in solid-state cultivation conditions for a period of three months. Two white rot species (Trichaptum abietinum and Phlebia radiata) were challenged by a brown rot species (Fomitopsis pinicola) in varying combinations. Wood decomposition patterns as determined by mass loss, carbon to nitrogen ratio, accumulation of dissolved sugars and release of volatile organic compounds (VOCs) were observed to depend on both fungal combinations and growth time. Similar dependence of fungal species combination, either white or brown rot dominated, was observed for secreted enzyme activities on spruce wood. Fenton chemistry suggesting reduction of Fe3+ to Fe2+ was detected in the presence of F. pinicola, even in co-cultures, together with substantial degradation of wood carbohydrates and accumulation of oxalic acid. Significant correlation was perceived with two enzyme activity patterns (oxidoreductases produced by white rot fungi; hydrolytic enzymes produced by the brown rot fungus) and wood degradation efficiency. Moreover, emission of four signature VOCs clearly grouped the fungal combinations. Our results indicate that fungal decay type, either brown or white rot, determines the loss of wood mass and decomposition of polysaccharides as well as the pattern of VOCs released upon fungal growth on spruce wood.

Electrochemical degradation of oxalic acid over highly reactive nano-textured γ- and α-MnO2/carbon electrode fabricated by KMnO4 reduction on loofah sponge-derived active carbon.

Manganese dioxide incorporated activated carbon (MnO2/AC) was synthesized and used to electrochemically degrade oxalic acid in aqueous solutions. The highly porous carbon provided reactive sites for the electro-sorption of oxalic acid and MnO2, with a specific polymorphism efficiently mediating the electron transfer between the electrode and organic pollutants. The activated carbon, made from the pyrolysis of dry loofah sponge using ZnCl2 as activating agent, exhibited a high double-layer capacitance dependent upon the heating temperature (100 F/g at 800 °C). The γ-MnO2 was in-situ deposited over the microporous structure of activated carbon through the redox reaction between KMnO4 and carbon. Simple further calcination converted γ-MnO2 to α-MnO2 nano-whisker at temperatures above 500 °C. Cyclic voltammetry showed that oxalic acid significantly improved the anodic current of the Mn(III)/Mn(IV) redox couple on the MnO2/AC electrode at an electrode potential around + 0.6 V (vs. Ag/AgCl). About 95% of oxalic acid degradation was achieved at pH < 4; meanwhile, 80% of the mineralization (total organic carbon removal) was attained independent of pH. Calcination converted γ-MnO2 to α-MnO2 which had higher electrochemical stability and inhibited the dissolution of Mn(II) from the electrode.

Degradation kinetics of cold plasma-treated antibiotics and their antimicrobial activity.

Antibiotics, such as ofloxacin (OFX) and ciprofloxacin (CFX), are often detected in considerable concentrations in both wastewater effluents and surface water. This poses a risk to non-target organisms and to human health. The aim of this work was to study atmospheric cold plasma (ACP) degradation of antibiotics in water and meat effluent and to explore any residual antimicrobial activity of samples submitted to the plasma process. The results revealed that ACP successfully degraded the studied antibiotics and that the reaction mechanism is principally related to attack by hydroxyl radicals and ozone. According to the disk diffusion assay, the activity of both antibiotics was considerably reduced by the plasma treatment. However, a microdilution method demonstrated that CFX exhibited higher antimicrobial activity after ACP treatment than the corresponding control revealing a potentially new platform for future research to improve the efficiency of conventional antibiotic treatments. Importantly, short-term exposures to sub-lethal concentrations of the antibiotic equally reduced bacterial susceptibility to both ACP treated and untreated CFX. As a remediation process, ACP removal of antibiotics in complex wastewater effluents is possible. However, it is recommended that plasma encompass degradant structure activity relationships to ensure that biological activity is eliminated against non-target organisms and that life cycle safety of antibiotic compounds is achieved.

Bioactive compounds content and antimicrobial activities of wild edible Asteraceae species of the Mediterranean flora under commercial cultivation conditions.

Nine wild edible species belonging to Astreaceae family, native to the Mediterranean basin were tested for their chemical composition (phenolic compounds, tocopherols, and organic acids) and antimicrobial activities over two growing periods, apart from Scolymus hispanicus and Hedypnois cretica which were tested for only one growing period. Flavonoids were the most abundant phenolic compounds in all the species, except for the case of Taraxacum species where significant amounts of chicoric acid were detected, while phenolic compounds content increased in the 2nd growing period by 4.6-397.4% for the tested species. α- and ß-tocopherols were the main tocopherols, apart from Taraxacum sp. where significant amounts of γ-and δ-tocopherols (18.32 and 16.31 µg/100 g fresh weight) were detected, while total tocopherols content either increased (Reicardia picroides, Picris echioides, Urospermum picroides, and Taraxacum officinale) or decreased (Hymenonema graecum, Sonchus oleraceus, Taraxacum sp.) in the 2nd growing period. Oxalic acid was the most abundant organic acid, with the highest content (972 mg/100 g fresh weight) being observed in H. graecum (L.) DC. in the 1st growing period. Moreover, with the exception of H. graecum and S. olearaceus, total organic acids content increased in the 2nd growing period. Significant antimicrobial activities were observed against Bacillus cereus, Salmonella typhimurium and Penicillium ochrochloron for all the studied species. In conclusion, the studied species showed great potential for commercial cultivation, while plant extracts could find use in the food industry as alternative food preservatives.

Fermentation of yam (Dioscorea spp. L.) by indigenous phytase-producing lactic acid bacteria strains.

The use of lactic bacteria in the development of functional foods has increased in recent years. In addition to their probiotic characteristics, they can ferment a variety of substrates, such as cereals, roots, and tubers. Phytase producer lactic acid bacteria strains and their behavior during the fermentation process of yam-based food were studied. Leuconostoc lactis CCMA 0415, Lactobacillus plantarum CCMA 0744, and Lactobacillus fermentum CCMA 0745 were selected due to phytase production, pH reduction, and growth during 24 h of fermentation. Oxalate activity was not detected in all assays, suggesting its concentration was reduced due to the bleaching process. Among the selected strains, L. lactis CCMA 0415 appeared to be a promising strain in yam-based fermentations because it maintained a cell viability above 8 log CFU/mL and did not reduce diosgenin concentrations (around 8.0 µg/mL) after fermentation for 24 h, thereby, generating a potentially functional yam food. Furthermore, this strain promoted the decrease of pH value from 6.1 to 3.8 and produced 8.1 g/L lactic acid, at 6 h of fermentation. The L. lactis CCMA 0415 was reported as a starter culture in fermented products based on cereals, roots, and tubers.

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.

Direct evidence for the enhanced acquisition of phosphorus in the rhizosphere of aquatic plants: A case study on Vallisneria natans.

There are few studies about the processes and mechanisms for aquatic plants to take up phosphorus (P) in wetland soils and sediments. Direct observation of P mobilization in rhizosphere is lacking. In this study, high-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) techniques were used to capture the small-scale changes of soluble reactive P (SRP) and soluble Fe, and labile P in the rhizosphere of Vallisneria natans (V. natans), respectively. The results showed 5.92- and 3.12-fold enrichments of P and Fe in the Fe plaques formed on the root surfaces, respectively, in comparison with the P and Fe concentrations in the non-rhizosphere sediments. Moreover, simultaneous releases of P and Fe appeared in rhizosphere and the SRP concentration showed up to 114-fold increases compared to the non-rhizosphere sediments. Five kinds of low-molecular weight organic acids (LMWOAs) were detected in the root exudates; oxalic acid accounted for 87.5% of the total. Extraction of Fe and P in the Fe plaques was greatly enhanced by root exudates compared to deionized water, and oxalic acid contributed to 67% and 75% of the total extracted Fe and P, respectively. The coupling processes of Fe plaque enrichment of P and oxalic acid complexation of Fe(III) led to significantly enhanced P acquisition in the rhizosphere of V. natans.

[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.

Oxalic acid quantification in mouse urine and primary mouse hepatocyte cell culture samples by ion exclusion chromatography-mass spectrometry.

Due to medical relevance and a direct correlation with some diseases, accurate quantification of oxalic acid in different complex matrices is required. Effective chromatographic separation of this strong carboxylic acid was achieved by ion exclusion chromatography (IELC). Sensitive and selective detection was carried out by means of electrospray ionization-tandem mass spectrometry. Furthermore, it was shown that the isobaric interference of lactic acid is chromatographically resolved. Structurally similar compounds like glyoxylic acid and glycolic acid were baseline separated as well. The application of stable isotope dilution analysis with 13C2 oxalic acid facilitated precise quantification. The developed method was validated with a reference oxalate sample of human urine diluted to a range of 10-500µM. Finally, the applicability of this method was demonstrated on complex matrices, like mouse urine and supernatants of primary mouse hepatocyte cell cultures.

Removal of NO with the hexamminecobalt solution catalyzed by the carbon treated with oxalic acid.

NO can be removed at the same time with SO2 by aqueous Co(NH3)62+ solution. The reduction of Co(NH3)63+ to Co(NH3)62+ is catalyzed by activated carbon to regain the NO absorption ability of the scrubbing solution. Oxalic acid solution is explored to change the carbon surface to ameliorate its catalytic capability. The experimental results suggest that the best catalyst is prepared by impregnating the carbon sample in 0.7 mol l-1 oxalic acid solution for 24 h followed by being activated at 600 °C for 5 h under nitrogen atmosphere. After being treated with oxalic acid solution, the surface area and the acidity on the carbon surface increase. The experiments show that the carbon modified with oxalic acid can get a much higher NO removal efficiency than the original carbon.

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.

Metabolic profiling of root exudates from two ecotypes of Sedum alfredii treated with Pb based on GC-MS.

Phytoremediation is an effective method to remediate Pb-contaminated soils and root exudates play an important role in this process. Based on gas chromatography-mass spectrometry (GC-MS) and metabolomics method, this study focuses on the comparative metabolic profiling analysis of root exudates from the Pb-accumulating and non-accumulating ecotypes of Sedum alfredii treated with 0 and 50 µmol/L Pb. The results obtained show that plant type and Pb stress can significantly change the concentrations and species of root exudates, and fifteen compounds were identified and assumed to be potential biomarkers. Leaching experiments showed that l-alanine, l-proline and oxalic acid have a good effect to activate Pb in soil, glyceric acid and 2-hydroxyacetic acid have a general effect to activate Pb in soil. 4-Methylphenol and 2-methoxyphenol might be able to activate Pb in soil, glycerol and diethyleneglycol might be able to stabilize Pb in soil, but these activation effect and stabilization effect were all not obvious.

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.