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Journal of Chromatography. A Sep 2023It is well-known that an ideal extraction method enabling quantitative analysis should give complete extraction of the target analytes as well as minimal co-extraction...
It is well-known that an ideal extraction method enabling quantitative analysis should give complete extraction of the target analytes as well as minimal co-extraction of unwanted matrix substances. If the extraction method is part of a nontarget screening protocol, the desired analytes can differ widely in terms of chemical properties. In chromatography, terminologies such as recovery, selectivity, and comprehensiveness are well-established and can easily be determined. However, in extraction, these concepts are much less developed. Hence, the aim of our research is to develop and scrutinize theory in extraction with respect to numerical descriptors for extractability, selectivity, and comprehensiveness. Our approach is based on experiments determining the extractability of target analytes and selected interferences. As a case study, we use a pooled sample of three species of seaweed (Alaria esculenta, Laminaria digitata and Ascophyllum nodosum). Target analytes are β-carotene, fucoxanthin, δ-tocopherol, and phloroglucinol; and selected interferences are carbohydrates, proteins, ash, arsenic, and chlorophyll a. As a "green and clean" extraction technique, supercritical fluid extraction (SFE) using mixtures of CO, ethanol and water were explored using a design of experiment. The temperature was varied between 40-80°C, and the pressure was held constant at 300 bar. Obtained results clearly demonstrate that highest relative selectivity was achieved with CO containing only 5 vol% of ethanol and no water, which primarily enabled high extractability of β-carotene, and yielding an extract free of carbohydrates, proteins, and toxic metals such as arsenic. Best methods for highest extractability of the other target analytes varied quite widely. Analytes requiring the highest water content (fucoxanthin and phloroglucinol), also resulted in the lowest relative selectivity. Maximum relative comprehensiveness was achieved using CO/ethanol/water (40/55/5, v/v/v) at 70°C and 300 bar. Our study demonstrates the feasibility of using relative quantitative descriptors for extractability, selectivity, and comprehensiveness, in optimization strategies for analytical extractions.
Topics: Ethanol; Chromatography, Supercritical Fluid; Carbon Dioxide; beta Carotene; Seaweed; Arsenic; Chlorophyll A; Carbohydrates
PubMed: 37572535
DOI: 10.1016/j.chroma.2023.464267 -
Environmental cadmium exposure alters the internal microbiota and metabolome of Sprague-Dawley rats.Frontiers in Veterinary Science 2023Cadmium (Cd) is a toxic element that can negatively affect both humans and animals. It enters the human and animal bodies through the respiratory and digestive tracts,...
Cadmium (Cd) is a toxic element that can negatively affect both humans and animals. It enters the human and animal bodies through the respiratory and digestive tracts, following which it tends to accumulate in different organs, thereby seriously affecting human and animal health, as well as hampering social and economic development. Cd exposure can alter the composition of intestinal microbiota. In addition, it can damage the peripheral organs by causing the translocation of intestinal microbiota. However, the relationship between translocation-induced changes in the composition of microbiome in the blood and metabolic changes remains unclear. In the present study, we investigated the effects of Cd exposure on microbiota and serum metabolism in rats by omics analysis. The results demonstrated that Cd exposure disrupted the balance between the blood and intestinal flora in Sprague-Dawley (SD) rats, with a significant increase in gut microbiota (, ) and blood microbiome (, ). However, Cd exposure caused the translocation of and from the gut into the blood. In addition, Cd exposure was associated with the up-regulation of serum indoxyl sulfate, phenyl sulfate, and p-cresol sulfate; down-regulation of δ-tocopherol and L-glutamine; and changes in blood microbiome and metabolites. In conclusion, we identified novel metabolic biomarkers for Cd toxicity, which will also expand our understanding of the role of blood microbiome in Cd-induced injury.
PubMed: 37565077
DOI: 10.3389/fvets.2023.1219729 -
Molecules (Basel, Switzerland) Jun 2023Despite the high proportion of maize grain in animal diets, the contribution made by maize phytochemicals is neglected. Tocols and their contribution to the vitamin E...
Despite the high proportion of maize grain in animal diets, the contribution made by maize phytochemicals is neglected. Tocols and their contribution to the vitamin E content of animal diets are one example, exacerbated by sparse information on the tocol bioaccessibility of commercial hybrids. In this study, the contents of individual and total tocols and their bioaccessibility were determined in the grain samples of 103 commercial hybrids using a standardized INFOGEST digestion procedure. In the studied hybrids, total tocol content ranged from 19.24 to 54.44 µg/g of dry matter. The contents of micellar α-, γ-, δ-tocopherols, γ-tocotrienol, and total tocols correlated positively with the corresponding contents in the grain samples of the studied hybrids. In contrast, a negative correlation was observed between the bioaccessibility of γ- tocopherol, α- and γ-tocotrienol, and total tocols, along with the corresponding contents in the grain of studied hybrids. The highest bioaccessibility was exhibited by γ-tocotrienol (532.77 g/kg), followed by δ-tocopherol (529.88 g/kg), γ-tocopherol (461.76 g/kg), α-tocopherol (406.49 g/kg), and α-tocotrienol (359.07 g/kg). Overall, there are significant differences in the content and bioaccessibility of total and individual tocols among commercial maize hybrids, allowing the selection of hybrids for animal production based not only on crude chemical composition but also on the content of phytochemicals.
Topics: Animals; Zea mays; Poultry; Tocopherols; Tocotrienols; Edible Grain; gamma-Tocopherol; Digestion
PubMed: 37446677
DOI: 10.3390/molecules28135015 -
Nutrients Jun 2023This study aimed to assess associations between forms of vitamin A and E (both individually and collectively) and the risk of prostate cancer, as well as identify...
PURPOSE
This study aimed to assess associations between forms of vitamin A and E (both individually and collectively) and the risk of prostate cancer, as well as identify potential effect modifiers.
METHODS
Utilizing data from the Singapore Prostate Cancer Study, a hospital-based case-control study, we measured the serum concentrations of 15 different forms of vitamins A and E in 156 prostate cancer patients and 118 control subjects, using a high-performance liquid chromatography technique. These forms included retinol, lutein, zeaxanthin, α-cryptoxanthin, β-cryptoxanthin, α-carotene, β-carotene, lycopene, ubiquinone, δ-tocopherol, γ-tocopherol, α-tocopherol, δ-tocotrienol, γ-tocotrienol, and α-tocotrienol. The odds ratio and 95% confidence interval for associations between vitamin A and E and prostate cancer risk were estimated using logistic regression models after adjustment for potential confounders. The analyses were further stratified by smoking and alcohol consumption status. The mixture effect of micronutrient groups was evaluated using weighted quantile sum regression.
RESULTS
Higher concentrations of retinol, lutein, α-carotene, β-carotene, ubiquinone, α-tocopherol, δ-tocotrienol, γ-tocotrienol, and α-tocotrienol were significantly and positively associated with overall prostate cancer risk. Among ever-smokers, associations were stronger for lutein, β-cryptoxanthin and β-carotene compared with never-smokers. Among regular alcohol drinkers, associations were stronger for lutein, β-cryptoxanthin, ubiquinone, γ-tocotrienol and α-tocotrienol compared with non-regular alcohol drinkers. Retinol and α-tocotrienol contributed most to the group indices 'vitamin A and provitamin A carotenoids' and 'vitamin E', respectively.
CONCLUSIONS
Several serum vitamin A and E forms were associated with prostate cancer risk, with significant effect modification by smoking and alcohol consumption status. Our findings shed light on prostate cancer etiology.
Topics: Male; Humans; Vitamin A; beta Carotene; Tocotrienols; Lutein; alpha-Tocopherol; Beta-Cryptoxanthin; Ubiquinone; Case-Control Studies; Singapore; Prostatic Neoplasms
PubMed: 37375581
DOI: 10.3390/nu15122677 -
Antioxidants (Basel, Switzerland) May 2023Charged interfaces may play an important role in the fate of chemical reactions. Alterations in, for instance, the interfacial acidity of emulsions induced by the charge...
Charged interfaces may play an important role in the fate of chemical reactions. Alterations in, for instance, the interfacial acidity of emulsions induced by the charge of the surfactant head group and associated counterions may change the ionization status of antioxidants, modifying their effective concentrations. The chemical reactivity between interfacial reactants and charged species of opposite charge (protons, metallic ions, etc.) is usually interpreted in terms of pseudophase ion-exchange models, treating the distribution of charged species in terms of partitioning and ion exchange. Here, we focus on analyzing the effects of charged interfaces on the oxidative stability of soybean oil-in-water (o/w) emulsions prepared with anionic (sodium dodecyl sulfate, SDS), cationic (cetyltrimethylammonium bromide, CTAB) and neutral (Tween 20) surfactants, and some of their mixtures, in the presence and absence of δ-tocopherol (δ-TOC). We have also determined the effective concentrations of δ-TOC in the oil, interfacial and aqueous regions of the intact emulsions. In the absence of δ-TOC, the relative oxidative stability order was CTAB < TW20 ~ TW20/CTAB < SDS. Surprisingly, upon the addition of δ-TOC, the relative order was SDS ≈ TW20 << TW20/CTAB < CTAB. These apparently surprising results can be rationalized in terms of the nice correlation that exists between the relative oxidative stability and the effective interfacial concentrations of δ-TOC in the various emulsions. The results emphasize the importance of considering the effective interfacial concentrations of antioxidants in interpreting their relative efficiency in emulsions.
PubMed: 37371888
DOI: 10.3390/antiox12061158 -
Plants (Basel, Switzerland) Mar 2023The seeds of 111 sp. different fruit use (dessert and cider apples) cultivars/genotypes developed in 18 countries were analysed to evaluate composition of tocopherol...
The seeds of 111 sp. different fruit use (dessert and cider apples) cultivars/genotypes developed in 18 countries were analysed to evaluate composition of tocopherol homologues and identify crop-specific profile, including diploid, triploid, and tetraploid apple cultivars with and without scab-resistance to ensure high genetic diversity. The percentage of individual tocopherols was as follows: alpha-tocopherol (alpha-T) (38.36%), beta-tocopherol (beta-T) (40.74%), gamma-tocopherol (gamma-T) (10.93%), and delta-tocopherol (delta-T) (9.97%), represented by average measurements of 17.48, 18.56, 4.98, and 4.54 mg/100 g dry weight, respectively. The values of the variation coefficient showed high variability for delta (0.695) and gamma (0.662) homologue content, whereas measurements of alpha-T and beta-T were less variable (coefficient of variation 0.203 and 0.256, respectively). The unweighted pair group method with arithmetic mean (UPGMA) revealed three main cultivar groups characterised by almost equal content of all four tocopherol homologues (Group I), high concentrations of alpha-T and beta-T, but very low content of gamma-T and delta-T (Group II), and relatively high average content of alpha-T and beta-T, but higher gamma-T and delta-T content (Group III). Specific tocopherol homologues showed association with certain valuable traits, such as harvesting time (total content of tocopherols) and resistance to apple scab (alpha-T and total content of tocopherols). This study represents the first large-scale tocopherol homologue (alpha, beta, gamma, and delta) screening in apple seeds. The dominant tocopherol homologues in cultivated apple cultivars are alpha-T and beta-T, with the prevalence of alpha-T or beta-T depending on genotype. It is a unique finding due to the rare occurrence of beta-T in the plant world and is considered a unique feature of the species.
PubMed: 36904029
DOI: 10.3390/plants12051169 -
Food Research International (Ottawa,... Mar 2023Chemical constituents and bioactive properties of rambutan (Nephelium lappaceum L.) peel were characterized and heat-/ultrasound-assisted extractions (HAE/UAE) of...
Chemical constituents and bioactive properties of rambutan (Nephelium lappaceum L.) peel were characterized and heat-/ultrasound-assisted extractions (HAE/UAE) of anthocyanins were optimized by response surface methodology. Five organic acids, the α-, γ-, and δ-tocopherol isoforms, and twenty-five fatty acids (36.8 % oleic acid) were identified, as well as a phenolic profile composed of ellagitannin derivatives, geraniin isomers, ellagic acid, and delphinidin-O derivatives. The extract showed antioxidant activity via lipid peroxidation (IC = 2.79 ± 0.03 µg/mL) and oxidative hemolysis (IC = 72 ± 2 µg/mL) inhibition, and displayed antibacterial and antifungal properties (MIC ≤ 1 mg/mL). On the other hand, no cytotoxicity was observed in tumor and non-tumor cell lines up to 400 µg/mL. The recovery of anthocyanins was more effective using HAE than UAE, allowing greater yields (16.2 mg/g extract) in just 3 min and using lower ethanol proportions. Overall, rambutan peel could be upcycled into bioactive ingredients and natural colorants for industrial applications.
Topics: Anthocyanins; Anti-Bacterial Agents; Antifungal Agents; Ellagic Acid; Ethanol
PubMed: 36869553
DOI: 10.1016/j.foodres.2023.112574 -
Foods (Basel, Switzerland) Jan 2023The extraction of total lipids and tocopherol compounds from Patagonian squid () by-products (viscera, heads, skin, etc.), resulting from squid mantel commercialisation,...
The extraction of total lipids and tocopherol compounds from Patagonian squid () by-products (viscera, heads, skin, etc.), resulting from squid mantel commercialisation, was studied. An optimisation simplex-lattice design by employing low-toxicity solvents (ethanol, acetone, and ethyl acetate) was carried out taking into account their relative concentrations. The variance analysis of data showed that the quadratic model was statistically significant ( < 0.05); empirical coded equations were obtained as a function of the low-toxicity solvent ratios. The optimised lipid extraction was obtained by employing the 0.642/0.318/0.040 (ethanol/acetone/ethyl acetate) solvent ratio, respectively, leading to an 84% recovery of the total lipids extracted by the traditional procedure. In all extracting systems tested, the presence of α-, γ-, and δ-tocopherol compounds was detected, α-tocopherol being the most abundant. For α-, γ-, and δ-tocopherol compounds, the optimisation process showed that acetone extraction led to the highest concentrations in the lipid extract obtained (2736.5, 36.8, and 2.8 mg·kg lipids, respectively). Taking into account the recovery yield on a by-product basis, the values obtained for the three tocopherols were included in the 88.0-97.7%, 80.0-95.0%, and 25-75% ranges, respectively, when compared to the traditional extraction. This study provides a novel and valuable possibility for α-tocopherol extraction from marine by-products.
PubMed: 36766033
DOI: 10.3390/foods12030504 -
International Journal of Molecular... Jan 2023Tocopherols are natural bioactive compounds with several health benefits. This study evaluated the effect of different ratios of α- and δ- tocopherol homologs to...
Evaluation of the Efficacy and Synergistic Effect of α- and δ-Tocopherol as Natural Antioxidants in the Stabilization of Sunflower Oil and Olive Pomace Oil during Storage Conditions.
Tocopherols are natural bioactive compounds with several health benefits. This study evaluated the effect of different ratios of α- and δ- tocopherol homologs to protect sunflower oil (SO) and olive pomace oil (OPO) against oxidation. A synergistic effect was recorded when the two tocopherols were combined at a ratio of 7:1 (α-T/δ-T). The oil samples were exposed to accelerated oxidation conditions using a Rancimat (90 °C and airflow of 15 L/h for 24 h) and protection from tocopherols was compared with that from butylated hydroxytoluene (BHT). Assessment of oil stability was examined using well-known parameters such as peroxide value (PV), thiobarbituric acid reactive substances (TBARS), p-anisidine value (p-AV), conjugated dienes (CD) and trienes (CT), and total oxidation (Totox) value, which were all significantly reduced when tocopherols were added at a ratio of 7:1 α-T/δ-T. Primary oxidative compounds measured according to PV were only reduced in SO samples (6.11%). Off-flavor compounds measured via TBARS assay in SO samples were reduced by above 20%, while p-AV was also reduced. CDvalue was correlated with PV in SO samples, while the 7:1 mixture was more effective than BHT for CTvalue. Total oxidation values in SO samples and OPO samples were reduced by 6.02% and 12.62%, respectively. These values in SO samples also provided a remarkable correlation (R2 > 0.95) with incubation time. Moreover, the synergistic effect was not only effective in reducing the oxidation values of oil samples, but also in lowering the degradation rate of tocopherols. Protective effects from tocopherols were mainly observed in SO samples, as OPO samples were more resistant to oxidation processes. This effect was even observed in fatty acid analysis, where the 7:1 mixture provided better results than BHT-spiked samples. Thus, it is suggested that tocopherol mixtures might be used as a natural preservative in the food industry to restrain lipid oxidation processes.
Topics: Antioxidants; Sunflower Oil; Olive Oil; Thiobarbituric Acid Reactive Substances; Tocopherols; Oxidation-Reduction; Plant Oils
PubMed: 36674630
DOI: 10.3390/ijms24021113