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Keywords = dietary amines

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17 pages, 1009 KiB  
Article
Analysis of Five Biogenic Amines in Foods on the Chinese Market and Estimation of Acute Histamine Exposure from Fermented Foods in the Chinese Population
by Pei Cao, Mengmeng Gao, Dongmei Huang, Xiaomin Xu, Zhujun Liu, Qing Liu, Yang Lu, Feng Pan, Zhaoxin Li, Jinfang Sun, Lei Zhang and Pingping Zhou
Foods 2025, 14(14), 2550; https://doi.org/10.3390/foods14142550 - 21 Jul 2025
Viewed by 309
Abstract
Biogenic amines (BAs) are frequently detected in seafood products, wines, and fermented foods, and they pose potential risks to human health. The current study analyzed the concentrations of five common BAs in seafood, fermented food, and complementary food for infants and children (fish [...] Read more.
Biogenic amines (BAs) are frequently detected in seafood products, wines, and fermented foods, and they pose potential risks to human health. The current study analyzed the concentrations of five common BAs in seafood, fermented food, and complementary food for infants and children (fish sausage, canned complementary food for infants containing fish and shrimp ingredients, and fish floss) in China and estimated the acute health risks of histamine (HIS) from fermented foods in Chinese consumers. Among all the samples analyzed, HIS exhibited the highest detection rate (51.9%), followed by PUT (50.1%), and the detection rate of TRY (12.5%) was the lowest. The total average concentration of the five BAs across major food categories revealed that fermented bean curd had the highest total concentration of BAs (816.8 mg/kg), followed by shrimp (383.2 mg/kg) and cheese (328.0 mg/kg). In contrast, samples of complementary food for infants and children contained the lowest concentrations of BAs; the total average concentration of the five BAs was 12.0 mg/kg. The point assessment results showed that acute dietary exposure to HIS was highest from cheese (76.2 mg/d), followed by fermented bean products (74.5 mg/d). Furthermore, the probability assessment indicated that the probability of acute health risks from exposure to HIS was 0.44% for fermented bean product consumers and 0.014% for cheese consumers, respectively. Thus, for the general consumer, the probability of acute health risks caused by HIS in seafood and fermented foods is low. However, individuals with high consumption of cheese and fermented bean products may need to be concerned. Full article
(This article belongs to the Section Food Quality and Safety)
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14 pages, 1769 KiB  
Article
Analysis of the Digestion Dynamics and Dietary Risk Assessment of Fluridone in Cotton Fields via QuEChERS Coupled with HPLC
by Sen Wang, Ruitong Yang, Yuxuan Li, Zhiqiang Jin, Yutian Xia, Yipin Zhao, Xiaoqiang Han, Guoqiang Zhang, Chunjuan Wang, Ting Ma, Cailan Wu and Desong Yang
Toxics 2025, 13(7), 526; https://doi.org/10.3390/toxics13070526 - 23 Jun 2025
Viewed by 244
Abstract
Fluridone is a pyrrolidone soil-sealing herbicide that has been widely used in cotton fields in Xinjiang in recent years. The purpose of this study was to establish a method for determining fluridone residues in cotton fields and to perform residue digestion tests, final [...] Read more.
Fluridone is a pyrrolidone soil-sealing herbicide that has been widely used in cotton fields in Xinjiang in recent years. The purpose of this study was to establish a method for determining fluridone residues in cotton fields and to perform residue digestion tests, final residue analysis, and dietary risk assessment. Samples were extracted with acetonitrile, purified with primary secondary amine (PSA) and multi-walled carbon nanotubes (MWCNTs), and analyzed by high-performance liquid chromatography (HPLC). The results showed that in a certain concentration range, the concentration and peak area of fluridone showed a good linear relationship (R2 > 0.99), with limit of detection (LOD) and limit of quantification (LOQ) values of 0.00090–0.00108 mg·kg−1 and 0.0030–0.0033 mg·kg−1, respectively. The relative standard deviation (RSD) values of fluridone were 0.46% to 4.57% at the spiked level of 0.1, 0.5, and 1.0 mg·kg−1, respectively. The average daily recovery rate of fluridone was 85.08% to 95.07%. The residual levels of fluridone in cottonseed oil were below the safety threshold, indicating no significant dietary risk to consumers. Full article
(This article belongs to the Section Agrochemicals and Food Toxicology)
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31 pages, 1792 KiB  
Review
Fermentation of Fruits and Vegetables: Bridging Traditional Wisdom and Modern Science for Food Preservation and Nutritional Value Improvements
by Prasad S. Gangakhedkar, Hemant W. Deshpande, Gréta Törős, Hassan El-Ramady, Tamer Elsakhawy, Neama Abdalla, Ayaz Shaikh, Béla Kovács, Rushikesh Mane and József Prokisch
Foods 2025, 14(13), 2155; https://doi.org/10.3390/foods14132155 - 20 Jun 2025
Viewed by 1049
Abstract
Fermented fruits and vegetables are gaining increased attention due to their enhanced nutritional properties, extended shelf life, and potential health benefits. Driven by consumer demand for natural, plant-based, and functional foods, fermentation is emerging as a sustainable alternative to conventional preservation methods. This [...] Read more.
Fermented fruits and vegetables are gaining increased attention due to their enhanced nutritional properties, extended shelf life, and potential health benefits. Driven by consumer demand for natural, plant-based, and functional foods, fermentation is emerging as a sustainable alternative to conventional preservation methods. This review highlights the role of lactic acid bacteria and other microorganisms in transforming fruit and vegetable substrates into probiotic-rich, bioactive foods. It explores traditional and emerging fermentation techniques, the influence of microbial consortia on product quality, and the impact of fermentation on antioxidant activity, gut health, immune modulation, and chronic disease prevention. Furthermore, the review addresses food safety concerns related to biogenic amines, nitrite accumulation, and microbial contamination, describing current solutions involving both conventional and non-thermal processing technologies. By synthesizing recent advances in microbial fermentation science and biotechnological innovations, this paper underscores the potential of fermented fruits and vegetables to contribute to functional food development, dietary diversity, and sustainable food systems. Full article
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19 pages, 1349 KiB  
Review
N-Nitrosamines in Meat Products: Formation, Detection and Regulatory Challenges
by Tomislav Rot, Dragan Kovačević, Kristina Habschied and Krešimir Mastanjević
Processes 2025, 13(5), 1555; https://doi.org/10.3390/pr13051555 - 17 May 2025
Cited by 1 | Viewed by 1703
Abstract
Nitrosamines (NAs) are a class of chemical compounds predominantly formed during the processing, curing, and storage of meat products through the reaction of nitrites with amines. Decades of toxicological and epidemiological evidence have unequivocally established several NAs as potent human carcinogens, with strong [...] Read more.
Nitrosamines (NAs) are a class of chemical compounds predominantly formed during the processing, curing, and storage of meat products through the reaction of nitrites with amines. Decades of toxicological and epidemiological evidence have unequivocally established several NAs as potent human carcinogens, with strong associations with gastrointestinal, pancreatic, and liver cancers. This review critically examines the pathways of NA formation in meat, the influence of processing conditions, and the factors contributing to their variability in food products. It also outlines state-of-the-art analytical techniques for their detection and summarizes recent scientific efforts to reduce their formation. Despite scientific consensus on the health hazards posed by dietary exposure to NAs, regulatory control remains fragmented and insufficient. Therefore, this review highlights the pressing need for coordinated international action and the development of a harmonized regulatory framework to mitigate public health risks. Full article
(This article belongs to the Special Issue Food Biochemistry and Health: Recent Developments and Perspectives)
16 pages, 2145 KiB  
Article
Impact of Combined Macronutrient Diet on Amino Acids and Amines Plasma Levels
by Celia Chicharro, Patricia Romero-Marco, Luz M. González, Laura González-Rodríguez, Laura Mateo-Vivaracho, Eva Guillamón, Francisco Miguel-Tobal, Fernando Bandrés, Guillermo Gervasini, Ana Fernández-Araque and Zoraida Verde
Nutrients 2025, 17(10), 1694; https://doi.org/10.3390/nu17101694 - 16 May 2025
Viewed by 565
Abstract
Background: Nutritional biomarkers are essential for assessing the impact of dietary interventions on health. Amino Acids (AA) serve as potential biomarkers due to their role in metabolic pathways, although the influence of combining macronutrients on AA metabolism remains unclear. Objective: This study aims [...] Read more.
Background: Nutritional biomarkers are essential for assessing the impact of dietary interventions on health. Amino Acids (AA) serve as potential biomarkers due to their role in metabolic pathways, although the influence of combining macronutrients on AA metabolism remains unclear. Objective: This study aims to evaluate the effects of combining macronutrients (fat, protein, and fiber) on AA metabolism. Methods: A dietary intervention was conducted with 41 participants who were assigned to two groups: the Protein Fat (PF) group and the Protein Fat and Fiber (PFF) group. AA concentration was measured using LC-MS/MS. Results: Our findings indicated that combining macronutrients reduced plasma levels of AA with statistically significant differences between the two diets (p < 0.05 for EAA and BCAA; p < 0,01 for NEAA and AAA). Metabolic profile analysis showed differences between the groups, especially at 55 days (55 D) (R2X: 0.749; R2Y: 0.589; Q2: 0.582, p < 0.001) and 98 days (98 D) (R2X: 0.886; R2Y: 0.7; Q2: 0.605, p < 0.001). Five metabolites (leucine, asparagine, alanine, cysteine, and creatine) were the most influential factors in group differentiation (VIP score), with values ranging between 1.04 and 1.75. Conclusions: The combination of macronutrients led to a significant reduction in plasma amino acids and amines in the PFF group, with recovery post-intervention. These findings highlight the possibility that these metabolites are related to different health statuses. Full article
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12 pages, 1539 KiB  
Article
Evaluation of Chronic Dietary Risk of Trifloxystrobin and Bupirimate in Cucumber Based on Supervised Residue Test
by Yanli Qi, Weirong Wang, Pengcheng Ren, Shu Qin, Jindong Li and Junli Cao
Foods 2025, 14(10), 1745; https://doi.org/10.3390/foods14101745 - 14 May 2025
Viewed by 436
Abstract
Trifloxystrobin and bupirimate are widely used as fungicides for controlling powdery mildew in cucumber cultivation. Supervised field trials were conducted in 12 representative regions across China, following Good Agricultural Practices (GAP) guidelines, to investigate their residue patterns and potential dietary exposure risks. Cucumber [...] Read more.
Trifloxystrobin and bupirimate are widely used as fungicides for controlling powdery mildew in cucumber cultivation. Supervised field trials were conducted in 12 representative regions across China, following Good Agricultural Practices (GAP) guidelines, to investigate their residue patterns and potential dietary exposure risks. Cucumber samples were analyzed using a validated method involving extraction with acidified acetonitrile (2% acetic acid, v/v), cleanup with primary secondary amine (PSA) and graphitised carbon black (GCB), and quantification by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The method demonstrated excellent recovery rates (85–103%) throughout four spiking levels (0.01, 0.1, 0.3, and 1 mg/kg), with relative standard deviations (RSD) ≤ 4.8%. At 3 days after treatment, the residues of trifloxystrobin (including trifloxystrobin acid), bupirimate, and ethirimol in cucumbers were found to range from <0.01 to 0.013 mg/kg, <0.01 to 0.076 mg/kg, and <0.01 to 0.04 mg/kg, respectively. A chronic dietary risk assessment was conducted using a probabilistic model. The results showed an acceptable chronic risk (RQc ≤ 2.476%) for trifloxystrobin, bupirimate, and ethirimol across different sexes and ages, supporting the conclusion that the use of these fungicides in cucumber cultivation under the tested conditions was safe for Chinese consumers. More research was needed on children because they are at higher risk than other groups. Full article
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15 pages, 1669 KiB  
Systematic Review
Prevalence of Intolerance to Amines and Salicylates in Individuals with Atopic Dermatitis: A Systematic Review and Meta-Analysis
by Karen Fischer, Mark Jones and Hayley M. O’Neill
Nutrients 2025, 17(10), 1628; https://doi.org/10.3390/nu17101628 - 9 May 2025
Viewed by 2014
Abstract
Background/Objectives: Elimination diets targeting amines and salicylates have been used since the 1980s to diagnose pharmacological food intolerance in individuals with atopic dermatitis (eczema), yet supporting evidence regarding relevance is limited. To our knowledge, this systematic review with meta-analysis is the first to [...] Read more.
Background/Objectives: Elimination diets targeting amines and salicylates have been used since the 1980s to diagnose pharmacological food intolerance in individuals with atopic dermatitis (eczema), yet supporting evidence regarding relevance is limited. To our knowledge, this systematic review with meta-analysis is the first to examine the prevalence and association between atopic dermatitis flares and amine intolerance (including histamine intolerance) and salicylate intolerance in individuals with atopic dermatitis. Methods: Following the PRISMA guidelines, searches of PubMed, Embase, CINAHL, and Cochrane were conducted. Included studies involved children and adults with atopic dermatitis who underwent dietary elimination and double-blind placebo-controlled challenges involving histamine, other amines, or salicylates. Risk of bias was assessed using the Joanna Briggs Institute Checklist for Prevalence Studies. Meta-analysis of the prevalence of atopic dermatitis flare by food chemical type was performed using a random effects model in Stata/MP, version 16.1 for Windows. Heterogeneity was assessed using the I2 statistic and Cochrane’s Q test. Results: A total of 2323 titles and abstracts were screened, with 46 full-text articles evaluated independently by two reviewers, resulting in the inclusion of four prevalence studies involving 188 participants. Meta-analysis of two trials showed histamine intolerance prevalence at 31% [95% CI, 20–41%] with no heterogeneity (I2 = 0.01%). Two trials showed amine intolerance prevalence at 32% [95% CI, 16–48%] with moderate heterogeneity (I2 = 34.91%). Two trials showed salicylate intolerance prevalence at 53% [95% CI, 44–62%] with no heterogeneity (I2 = 0.00%). Conclusions: This review suggests there may be low-certainty evidence linking intolerance to histamine, amines, and salicylates to atopic dermatitis flare in a substantial proportion of individuals with atopic dermatitis. Further, well-designed studies are needed to confirm these findings and clarify the role of pharmacological food intolerance in atopic dermatitis. Full article
(This article belongs to the Section Nutritional Immunology)
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15 pages, 250 KiB  
Article
Impact of the Dietary Fat Concentration and Source on the Fecal Microbiota of Healthy Adult Cats
by Nadine Paßlack, Kathrin Büttner, Wilfried Vahjen and Jürgen Zentek
Metabolites 2025, 15(4), 215; https://doi.org/10.3390/metabo15040215 - 22 Mar 2025
Viewed by 513
Abstract
Background/Objectives: The dietary fat supply might interact with the intestinal microbiota via different mechanisms. Research on this topic, however, remains scarce in cats. For this reason, the present study was conducted to evaluate the impact of the fat concentration and fatty acid profile [...] Read more.
Background/Objectives: The dietary fat supply might interact with the intestinal microbiota via different mechanisms. Research on this topic, however, remains scarce in cats. For this reason, the present study was conducted to evaluate the impact of the fat concentration and fatty acid profile in the diet on the fecal microbiota of healthy cats. Methods: A low-fat basal diet was fed to ten healthy adult cats. The diet was offered without or with the daily addition of 0.5 g or 1 g of sunflower oil, fish oil or lard per kg body weight of the cats, using a randomized cross-over design. Each feeding period lasted for 21 days, and the fecal samples were collected on the last days of each period. The fecal microbiota was analyzed by 16S rDNA sequencing. Additionally, microbial metabolites (short-chain fatty acids, lactate, ammonium, biogenic amines) were measured in the fecal samples. Results: The dietary treatment had no impact on the alpha-diversity of the fecal microbiota or on the relative abundance of bacterial phyla in the samples. Only a few changes were observed in the relative abundance of bacterial genera and the concentrations of microbial metabolites in the feces, probably being of minor physiological relevance. Conclusions: The balanced intestinal microbiota of cats seems to be relatively resistant to moderate variations in the dietary fat supply over a short feeding period. Longer-term treatments and higher dietary fat levels should be evaluated in future studies to further clarify the relevance of fat intake for the feline gut microbiome. Full article
(This article belongs to the Special Issue Metabolic Research in Animal Nutrition and Production)
18 pages, 2314 KiB  
Article
Photochemical Redox Cycling of Naphthoquinones Mediated by Methylene Blue and Pheophorbide A
by Lisa M. Landino and Joseph A. Reed
Molecules 2025, 30(6), 1351; https://doi.org/10.3390/molecules30061351 - 18 Mar 2025
Cited by 1 | Viewed by 925
Abstract
The photoreduction of plastoquinone, a para-benzoquinone, by chlorophyll initiates photosynthesis in chloroplasts. The direct photoreduction of biologically relevant quinones by dietary chlorophyll metabolites has been reported and may influence health outcomes. We examined red light-mediated photoreduction of ortho- and para-naphthoquinones including vitamin K [...] Read more.
The photoreduction of plastoquinone, a para-benzoquinone, by chlorophyll initiates photosynthesis in chloroplasts. The direct photoreduction of biologically relevant quinones by dietary chlorophyll metabolites has been reported and may influence health outcomes. We examined red light-mediated photoreduction of ortho- and para-naphthoquinones including vitamin K3 using the photosensitizers methylene blue and pheophorbide A, a chlorophyll metabolite. Naphthoquinone reduction was monitored by UV/Visible spectroscopy and required a photosensitizer, red light and a tertiary amine electron donor. Combinations of methylene blue and ethylenediaminetetraacetic acid or pheophorbide A and triethanolamine in 20% dimethylformamide were employed for all photoreduction experiments. Hydrogen peroxide was generated during the photochemical reactions by singlet oxygen-dependent oxidation of the reduced naphthoquinones. Hydrogen peroxide was quantified with horseradish peroxidase following irradiation; the reduced naphthoquinones acted as peroxidase co-substrates. Histidine, a singlet oxygen scavenger, enhanced the rate of photoreduction by limiting the re-oxidation process. Catalase slowed the rate of photoreduction by regenerating molecular oxygen from hydrogen peroxide so that it could be photoexcited to singlet oxygen. The rates and extent of naphthoquinone photoreduction were dependent on molecular oxygen exposure in different reaction formats including in a cuvette and a plate well. Reduction of the tetrazolium salt MTT to the formazan via electron transfer from the photoreduced quinones was also used to quantitate the extent of photoreduction. Full article
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24 pages, 1625 KiB  
Review
Nitric Oxide in Parkinson’s Disease: The Potential Role of Dietary Nitrate in Enhancing Cognitive and Motor Health via the Nitrate–Nitrite–Nitric Oxide Pathway
by Gianluca Tripodi, Mauro Lombardo, Sercan Kerav, Gilda Aiello and Sara Baldelli
Nutrients 2025, 17(3), 393; https://doi.org/10.3390/nu17030393 - 22 Jan 2025
Cited by 4 | Viewed by 3426
Abstract
Background/Objectives: Parkinson’s disease (PD) is a progressive neurodegenerative disorder characterized by the loss of dopaminergic neurons in the substantia nigra pars compacta, leading to motor symptoms such as tremor, rigidity, and bradykinesia. The pathological hallmarks of PD include Lewy bodies and mechanisms [...] Read more.
Background/Objectives: Parkinson’s disease (PD) is a progressive neurodegenerative disorder characterized by the loss of dopaminergic neurons in the substantia nigra pars compacta, leading to motor symptoms such as tremor, rigidity, and bradykinesia. The pathological hallmarks of PD include Lewy bodies and mechanisms like oxidative/nitrosative stress, chronic inflammation, and mitochondrial dysfunction. Nitric oxide (NO), produced by nitric oxide synthase (NOS) isoforms, plays a dual role in neuroprotection and neurodegeneration. Excessive NO production exacerbates neuroinflammation and oxidative/nitrosative damage, contributing to dopaminergic cell death. This review explores NO’s role in PD pathogenesis and investigates dietary nitrate as a therapeutic strategy to regulate NO levels. Methods: A literature review of studies addressing the role of NO in PD was conducted using major scientific databases, including PubMed, Scopus, and Web of Science, using keywords such as “nitric oxide”, “NOSs”, “Parkinson’s disease”, and “nitrate neuroprotection in PD”. Studies on nitrate metabolism via the nitrate–nitrite–NO pathway and its effects on PD hallmarks were analyzed. Studies regarding the role of nitrosamine formation in PD, which are mainly formed during the nitrification process of amines (nitrogen-containing compounds), often due to chemical reactions in the presence of nitrite or nitrate, were also examined. In particular, nitrate has been shown to induce oxidative stress, affect the mitochondrial function, and contribute to inflammatory phenomena in the brain, another factor closely related to the pathogenesis of PD. Results: Excessive NO production, particularly from iNOS and nNOS, was strongly associated with neuroinflammation and oxidative/nitrosative stress, amplifying neuronal damage in PD. Dietary nitrate was shown to enhance NO bioavailability through the nitrate–nitrite–NO pathway, mitigating inflammation and oxidative/nitrosative damage. Conclusions: Dysregulated NO production contributes significantly to PD progression via inflammatory and oxidative/nitrosative pathways. Dietary nitrate, by modulating NO levels, offers a promising therapeutic strategy to counteract these pathological mechanisms. Further clinical trials are warranted to establish its efficacy and optimize its use in PD management. Full article
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12 pages, 472 KiB  
Article
Polyamine Content of Enteral Nutrition Formulas: Effect of Daily Intake on the Feeding Tolerance of Patients During the First Week in the Intensive Care Unit
by Manuel Sánchez, Eva Rodríguez-Hernández, Lorena Suárez, Begoña Cantabrana and María González-García
Appl. Sci. 2025, 15(2), 659; https://doi.org/10.3390/app15020659 - 11 Jan 2025
Cited by 1 | Viewed by 1106
Abstract
Enteral nutrition (EN) formulas are necessary for critically ill patients to meet their metabolic requirements. Polyamines (putrescine, spermidine, and spermine) are crucial dietary components, with spermidine being particularly interesting due to its multiple proposed benefits. The requirements for and intake of polyamines have [...] Read more.
Enteral nutrition (EN) formulas are necessary for critically ill patients to meet their metabolic requirements. Polyamines (putrescine, spermidine, and spermine) are crucial dietary components, with spermidine being particularly interesting due to its multiple proposed benefits. The requirements for and intake of polyamines have yet to be investigated in adult patients hospitalised in intensive care units (ICUs) who are exclusively fed via commercial EN formulas. The aim of this study was to determine the polyamine content and other biogenic amines of EN formulas and the total intake and gastric residual volume (GRV) in adult ICU patients during their first seven days of hospitalisation. The amines were analysed in 16 EN formulas using high-performance liquid chromatography (HPLC). The clinical data of eight patients of both sexes aged 47 to 77 admitted to the ICU were analysed. Differences existed among the analysed EN formulas. The N-acetyl putrescine content was higher than that of the remaining amines. The daily intake of polyamines in the ICU was less than 100 μmol (the dietary intake is above 400 μmol). An inverse correlation existed between total daily polyamine intake and daily GRV, without effects from other biogenic amines being analysed. Polyamine intake in critically ill patients receiving EN is low and could impact these patients’ feeding tolerance. These findings underscore the need for further research to explore the clinical implications of increasing the polyamine content of EN formulas. Full article
(This article belongs to the Special Issue Advances in Food Metabolomics)
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16 pages, 1606 KiB  
Article
Biomonitoring PhIP, a Potential Prostatic Carcinogen, in the Hair of Healthy Men of African and European Ancestry
by Robert J. Turesky, Clarence Jones, Jingshu Guo, Kari Cammerrer, Laura A. Maertens, Emmanuel S. Antonarakis, Zhanni Lu and Logan G. Spector
Toxics 2025, 13(1), 42; https://doi.org/10.3390/toxics13010042 - 8 Jan 2025
Viewed by 1373
Abstract
Heterocyclic aromatic amines (HAAs), formed during the cooking of meat, are potential human carcinogens, underscoring the need for long-lived biomarkers to assess exposure and cancer risk. Frequent consumption of well-done meats containing 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), a prevalent HAA that is a prostatic [...] Read more.
Heterocyclic aromatic amines (HAAs), formed during the cooking of meat, are potential human carcinogens, underscoring the need for long-lived biomarkers to assess exposure and cancer risk. Frequent consumption of well-done meats containing 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), a prevalent HAA that is a prostatic carcinogen in rodents and DNA-damaging agent in human prostate cells, has been linked to aggressive prostate cancer (PC) pathology. African American (AA) men face nearly twice the risk for developing and dying from PC compared to White men. We previously demonstrated that scalp hair is a reliable biospecimen for measuring PhIP intake using liquid chromatography-mass spectrometry. This study aimed to determine whether PhIP dietary intake is higher in AA men, potentially contributing to this health disparity. Healthy AA men were found to have a significantly higher mean hair PhIP level (2.12-fold) than White men on free-choice diets. However, this difference was not statistically significant after adjusting for melanin content. Further research is needed to understand how hair pigmentation, follicular density, and other morphological features of hair influence PhIP accumulation. These insights can improve the accuracy of using hair PhIP levels as a biomarker for exposure and its potential associations with cancer risk. Full article
(This article belongs to the Section Novel Methods in Toxicology Research)
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38 pages, 5445 KiB  
Article
Speciation of Potentially Carcinogenic Trace Nickel(II) Ion Levels in Human Saliva: A Sequential Metabolomics-Facilitated High-Field 1H NMR Investigation
by Kayleigh Hunwin, Georgina Page, Mark Edgar, Mohammed Bhogadia and Martin Grootveld
Metabolites 2025, 15(1), 4; https://doi.org/10.3390/metabo15010004 - 30 Dec 2024
Viewed by 937
Abstract
Introduction/Objectives: Since the biological activities and toxicities of ‘foreign’ and/or excess levels of metal ions are predominantly determined by their precise molecular nature, here we have employed high-resolution 1H NMR analysis to explore the ‘speciation’ of paramagnetic Ni(II) ions in human saliva, [...] Read more.
Introduction/Objectives: Since the biological activities and toxicities of ‘foreign’ and/or excess levels of metal ions are predominantly determined by their precise molecular nature, here we have employed high-resolution 1H NMR analysis to explore the ‘speciation’ of paramagnetic Ni(II) ions in human saliva, a potentially rich source of biomolecular Ni(II)-complexants/chelators. These studies are of relevance to the in vivo corrosion of nickel-containing metal alloy dental prostheses (NiC-MADPs) in addition to the dietary or adverse toxicological intake of Ni(II) ions by humans. Methods: Unstimulated whole-mouth human saliva samples were obtained from n = 12 pre-fasted (≥8 h) healthy participants, and clear whole-mouth salivary supernatants (WMSSs) were obtained from these via centrifugation. Microlitre aliquots of stock aqueous Ni(II) solutions were sequentially titrated into WMSS samples via micropipette. Any possible added concentration-dependent Ni(II)-mediated pH changes therein were experimentally controlled. 1H NMR spectra were acquired on a JEOL JNM-ECZ600R/S1 spectrometer. Results: Univariate and multivariate (MV) metabolomics and MV clustering analyses were conducted in a sequential stepwise manner in order to follow the differential effects of increasing concentrations of added Ni(II). The results acquired showed that important Ni(II)-responsive biomolecules could be clustered into distinguishable patterns on the basis of added concentration-dependent responses of their resonance intensities and line widths. At low added concentrations (71 µmol/L), low-WMSS-level N-donor amino acids (especially histidine) and amines with relatively high stability constants for this paramagnetic metal ion were the most responsive (severe resonance broadenings were observed). However, at higher Ni(II) concentrations (140–670 µmol/L), weaker carboxylate O-donor ligands such as lactate, formate, succinate, and acetate were featured as major Ni(II) ligands, a consequence of their much higher WMSS concentrations, which were sufficient for them to compete for these higher Ni(II) availabilities. From these experiments, the metabolites most affected were found to be histidine ≈ methylamines > taurine ≈ lactate ≈ succinate > formate > acetate ≈ ethanol ≈ glycine ≈ N-acetylneuraminate, although they predominantly comprised carboxylato oxygen donor ligands/chelators at the higher added Ni(II) levels. Removal of the interfering effects arising from the differential biomolecular compositions of the WMSS samples collected from different participants and those from the effects exerted by a first-order interaction effect substantially enhanced the statistical significance of the differences observed between the added Ni(II) levels. The addition of EDTA to Ni(II)-treated WMSS samples successfully reversed these resonance modifications, an observation confirming the transfer of Ni(II) from the above endogenous complexants to this exogenous chelator to form the highly stable diamagnetic octahedral [Ni(II)-EDTA] complex (Kstab = 1.0 × 1019 M−1). Conclusions: The results acquired demonstrated the value of linking advanced experimental design and multivariate metabolomics/statistical analysis techniques to 1H NMR analysis for such speciation studies. These provided valuable molecular information regarding the identities of Ni(II) complexes in human saliva, which is relevant to trace metal ion speciation and toxicology, the in vivo corrosion of NiC-MADPs, and the molecular fate of ingested Ni(II) ions in this biofluid. The carcinogenic potential of these low-molecular-mass Ni(II) complexes is discussed. Full article
(This article belongs to the Section Endocrinology and Clinical Metabolic Research)
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11 pages, 982 KiB  
Article
Dissipation and Dietary Risk Assessment of the Fungicide Pyraclostrobin in Apples Using Ultra-High Performance Liquid Chromatography–Mass Spectrometry
by Bin Wang, Lei Shi, Pengcheng Ren, Shu Qin, Jindong Li and Junli Cao
Molecules 2024, 29(18), 4434; https://doi.org/10.3390/molecules29184434 - 18 Sep 2024
Viewed by 1365
Abstract
The fungicide pyraclostrobin is the main measure used to control apple alternaria blotch in production. To evaluate the potential dietary risks for consumers, the dissipation and terminal residues of pyraclostrobin were investigated using ultra-high performance liquid chromatography–mass spectrometry (UHPLC–MS/MS). Pyraclostrobin in apples was [...] Read more.
The fungicide pyraclostrobin is the main measure used to control apple alternaria blotch in production. To evaluate the potential dietary risks for consumers, the dissipation and terminal residues of pyraclostrobin were investigated using ultra-high performance liquid chromatography–mass spectrometry (UHPLC–MS/MS). Pyraclostrobin in apples was extracted by acetonitrile with 2% ammonia and then purified using primary secondary amine (PSA) and graphitized carbon black (GCB). The method showed good linearity within the concentration range of 0.005–0.1 mg L−1, with a coefficient of determination (R2) ≥ 0.9958. The recoveries ranged from 96.0% to 103.8%, with relative standard deviations (RSDs) between 0.8% and 2.3%. The limit of quantification (LOQ) was 0.01 mg kg−1. Pyraclostrobin dispersible oil suspension was applied in 12 apple fields across China according to good agricultural practices (GAPs). In Beijing and Shandong, the dissipation of pyraclostrobin followed first-order kinetic equations, with a half-life of 11 days. The terminal residues ranged from <0.01 to 0.09 mg kg−1. The national estimated daily intake (NEDI) of pyraclostrobin was compared with the acceptable daily intake (ADI), resulting in risk quotient (RQc) of 80.8%. These results suggest that pyraclostrobin poses a low health risk to consumers under GAP conditions and according to recommended dosages. Full article
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15 pages, 2224 KiB  
Article
Concurrent Photooxidation and Photoreduction of Catechols and Para-Quinones by Chlorophyll Metabolites
by Katherine Phan, Emily E. Lessard, Joseph A. Reed, Meredith G. Warsen, Soren Zimmer and Lisa M. Landino
Photochem 2024, 4(3), 346-360; https://doi.org/10.3390/photochem4030021 - 15 Aug 2024
Cited by 3 | Viewed by 2437
Abstract
Photosynthesis is initiated when the sun’s light induces electron transfer from chlorophyll to plastoquinone, a para-quinone. While photosynthesis occurs in the intact chloroplasts of living plants, similar photochemical reactions between dietary chlorophyll metabolites and quinones are likely and may affect health outcomes. Herein, [...] Read more.
Photosynthesis is initiated when the sun’s light induces electron transfer from chlorophyll to plastoquinone, a para-quinone. While photosynthesis occurs in the intact chloroplasts of living plants, similar photochemical reactions between dietary chlorophyll metabolites and quinones are likely and may affect health outcomes. Herein, we continue our studies of the direct photoreduction of para-quinones and ortho-quinones that were generated by the photo-oxidation of catechols. Chlorophyll metabolites, including pheophorbide A, chlorin e6, and pyropheophorbide A, as well as methylene blue were employed as photosensitizers. We detected hydrogen peroxide using horseradish peroxidase following the photo-oxidation of the catechol dopamine, even in the presence of EDTA, a tertiary amine electron donor. Under ambient oxygen, hydrogen peroxide was also detected after the photoreduction of several para-quinones, including 2,3-dimethoxy-5-methyl-p-benzoquinone (CoQ0), methoxy-benzoquinone, and methyl-benzoquinone. The combinations of methylene blue and EDTA or pheophorbide A and triethanolamine as the electron donor in 20% dimethylformamide were optimized for photoreduction of the para-quinones. Chlorin e6 and pyropheophorbide A were less effective for the photoreduction of CoQ0 but were equivalent to pheophorbide A for generating hydrogen peroxide in photo-oxidation reactions with photosensitizers, oxygen, and triethanolamine. We employed dinitrophenylhydrazine to generate intensely colored adducts of methoxy-benzoquinone, methyl-benzoquinone, and 1,4-benzoquinone. Full article
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