Comparative antioxidant and metabolomic analysis for the identification of differential response of mussel (Mytilus coruscus) to four succinate dehydrogenase inhibitor fungicides.

Succinate dehydrogenase inhibitor fungicides (SDHIs) are frequently detected in the marine environment. However, studies on the toxicity of SDHIs to marine organisms, Mytilus coruscus (M. coruscus), are poorly reported. Therefore, the antioxidant activities and metabolomic response of four SDHIs, namely, boscalid (BC), thifluzamide (TF), fluopyram (FO), and bixafen (BIX), to (M. coruscus), were comprehensively investigated. The antioxidant activity of BC and TF was significantly increased (p<0.05), whereas those of FO and BIX were significantly decreased. Furthermore, metabolite discriminations among M. coruscus to four SDHIs were illustrated by an untargeted metabolomics approach. A total of 52, 50, 93, and 129 differential metabolites were obtained for BC, TF, FO, and BIX. KEGG of the different metabolites show that the four SDHIs had differential effects on the metabolic pathways of M. coruscus. The current study demonstrated four SDHIs triggered glucose metabolism, lipid metabolism, tricarboxylic acid cycle, and oxidative phosphorylation processes and caused the disruption of nutrient and energy conversion processes in mussels. Finally, five biomarkers were screened by analyzing common differential metabolites that emerged from the four SDHI exposures, which could be used for risk assessment of marine ecosystem exposure to SDHIs. Our results demonstrated the use of metabolomics to understand the potential mechanisms of toxicity of four SDHIs to mussels and to identify potential targets for future targeted risk assessment.

The combination of uridine and nitrogen-deprivation promotes the efficient formation of astaxanthin-rich motile cells in Haematococcus pluvialis.

Astaxanthin accumulation in Haematococcus pluvialis typically occurs alongside the formation of secondary cell wall (SCW), hindering astaxanthin extraction and bio-accessibility. A potential solution lies in cultivating astaxanthin-rich motile cells lacking SCW. This study explored the influence and underlying mechanism of nitrogen-deprivation (ND) on SCW formation and established a connection between pyrimidine metabolism and SCW development. Then, various pyrimidine and ND combinations were examined to cultivate astaxanthin-rich motile cells. The results indicated that, compared to the nitrogen-replete group, the combination of uridine and ND increased the proportion of motile cells by 25-33 times, achieving 95 %, and enhanced astaxanthin yield by 26.52 %. Moreover, the efficiency of astaxanthin extraction from intact, wet motile cells was 91 % - 95 %, which was 5.6-9.0 times that from non-motile cells. This study not only presents a promising method for producing astaxanthin-rich motile cells in H. pluvialis but also provides insights into the relationship between pyrimidine metabolism and SCW development.

Enhancement of astaxanthin production, recovery, and bio-accessibility in Haematococcus pluvialis through taurine-mediated inhibition of secondary cell wall formation under high light conditions.

This study explored the use of taurine in enhancing the production and bio-accessibility of astaxanthin in Haematococcus pluvialis, which typically forms a secondary cell wall hindering astaxanthin extraction. The biomass of taurine-treated group significantly increased by 18%, and astaxanthin yield surged by 34% in comparison to the control group. Without cell disruption, astaxanthin recovery from thin-walled cells in the taurine-treated group, using dimethyl sulfoxide and ethanol as extraction reagents, was 97% and 75%, respectively, which were 30-fold higher than those of thick-walled cells in the control group. Additionally, the cell fragmentation rate increased by 86% in taurine-treated group relative to the control group. Comparative transcriptome analysis identified taurine-induced upregulation of genes involved in the astaxanthin biosynthesis pathway and downregulation of those associated with secondary cell wall synthesis. This study thus offers an innovative taurine-based strategy to enhance astaxanthin production and bio-accessibility while shedding light on the mechanisms driving this process.

Simultaneous determination and dietary intake risk assessment of 60 herbicide residues in aquatic products.

A sensitive and rugged analytical method was first established to simultaneously determine 60 herbicides in aquatic products with gas chromatography-tandem mass spectroscopy (GC-MS/MS). After extraction with acetonitrile (MeCN), NaCl and anhydrous Na2SO4 were added, concentrated supernatants were directly passed through the Carb/NH2 solid phase extraction column. Then, the cartridge was rinsed with elution solution (MeCN/toluene, 3:1, v/v), followed by GC-MS/MS analysis with multiple reaction monitoring. An excellent linearity (1.0-100.0 µg/L) with R2 value of ≥0.9991 was obtained, and the limits of quantification were 0.018-3.852 µg/kg. Satisfactory recoveries (70.8 %-117.6 %) with RSDs below 11.0 % of herbicide residues were obtained at spiked levels of 0.010-0.050 mg/kg. Furthermore, herbicide residues in actual aquatic products were analyzed, and the acute/chronic risk assessment of dietary exposure was carried out. The wide use of herbicides for controlling weed and removing moss and harmful algae may obviously increase the risk of contamination of the aquaculture environment and fishery products. Therefore, considerable attention and more research are necessary to monitor residue levels for herbicides in aquatic products and ensure the quality of marine products and consumer safety.

Prediction models for monitoring selenium and its associated heavy-metal accumulation in four kinds of agro-foods in seleniferous area.

Se-rich agro-foods are effective Se supplements for Se-deficient people, but the associated metals have potential risks to human health. Factors affecting the accumulation of Se and its associated metals in Se-rich agro-foods were obscure, and the prediction models for the accumulation of Se and its associated metals have not been established. In this study, 661 samples of Se-rich rice, garlic, black fungus, and eggs, four typical Se-rich agro-foods in China, and soil, matrix, feed, irrigation, and feeding water were collected and analyzed. The major associated metal for Se-rich rice and garlic was Cd, and that for Se-rich black fungus and egg was Cr. Se and its associated metal contents in Se-rich agro-foods were positively correlated with Se and metal contents in soil, matrix, feed, and matrix organic contents. The Se and Cd contents in Se-rich rice grain and garlic were positively and negatively correlated with soil pH, respectively. Eight models for predicting the content of Se and its main associated metals in Se-rich rice, garlic, black fungus, and eggs were established by multiple linear regression. The accuracy of the constructed models was further validated with blind samples. In summary, this study revealed the main associated metals, factors, and prediction models for Se and metal accumulation in four kinds of Se-rich agro-foods, thus helpful in producing high-quality and healthy Se-rich.

Transcriptome analysis provides new insight into the distribution and transport of selenium and its associated metals in selenium-rich rice.

Selenium is an essential trace element for humans and obtained from diary diets. The consumption of selenium-rich agricultural food is an efficient way to obtain selenium, but the quality and safety of selenium-rich agro-food are always affected by their associated heavy metals, even poses a potential threaten to human health. In this research, a sampling survey of heavy metals contents in selenium-rich rice was conducted, 182 sets of selenium-rich rice samples were collected from five selenium-rich rice-producing areas of China, and the accumulation of selenium and cadmium were found to be associated in rice and soil. Subsequently, a pot experiment was performed in the greenhouse via treating the soil samples with 12 different concentrations of selenium and heavy metals, and the contents of selenium and cadmium in rice grain were confirmed to be significantly associated. Moreover, transcriptome analysis revealed that the up-regulation of transporter-coding may promote the absorption of selenium and cadmium. The expression of antioxidant-coding genes and cadmium chelator transporter coding-genes was up-regulated to reduce the toxicity of cadmium. Meanwhile, the up-regulation of key genes of the ascorbic acid-glutathione metabolic pathway were responsible for the association between selenium and cadmium in Se-rich rice. Our work suggested the correlation between selenium and cadmium accumulation in selenium-rich rice, clarified their accumulation mechanism, provides a direction for the scientific production of selenium-rich agro-foods.

Resonance-Mediated Dynamic Modulation of Perovskite Crystallization for Efficient and Stable Solar Cells.

Manipulating perovskite crystallization to prepare high-quality perovskite films is the key to achieving highly efficient and stable perovskite solar cells (PSCs). Here, a dynamic strategy is proposed to modulate perovskite crystallization using a resonance hole-transporting material (HTM) capable of fast self-adaptive tautomerization between multiple electronic states with neutral and charged resonance forms for mediating perovskite crystal growth and defect passivation in situ. This approach, based on resonance variation with self-adaptive molecular interactions between the HTM and the perovskite, produces high-quality perovskite films with smooth surface, oriented crystallization, and low charge recombination, leading to high-performance inverted PSCs with power conversion efficiencies approaching 22% for small-area devices (0.09 cm2 ) and up to 19.5% for large-area devices (1.02 cm2 ). Also, remarkably high stability of the PSCs is observed, retaining over 90%, 88%, or 83% of the initial efficiencies in air with relative humidity of 40-50%, under continuous one-sun illumination, or at 75 °C annealing for 1000 h without encapsulation.

Effects of preheating and drying methods on pyridoxine, phenolic compounds, ginkgolic acids, and antioxidant capacity of Ginkgo biloba nuts.

Although ginkgo nuts are very nutritious and loaded with numerous bioactive compounds, the nuts contain significant levels of unwanted compounds (ginkolic acids) which are toxic to consumption. To reduce or eliminate these toxic compounds without impacting the nutritional value and the bioactivity of the final product, an appropriate processing technology is needed. Thus, the effect of preheating (90 and 120°C) prior to drying (freeze drying: FD, hot air drying: HAD, and HAD in tandem with FD: HAD-FD) was evaluated on ginkgolic acids, pyridoxine analogues, phenolic compounds, and antioxidant properties of ginkgo nuts. Our results pointed out a significant decrease (below 50%) of ginkgolic acids in ginkgo nuts samples processed at 90°C compared to the control. The major compounds found after treatments were respectively, kaempferol (36.66-354.38 µg/g), quercetin (9.04-183.71 µg/g), and caffeic acid (19.66-106.88 µg/g). Principal component analysis (PCA) revealed that preheating at 90°C prior to HAD-FD would be a proper and reasonable approach for preserving the bioactive compounds and antioxidant capacity of ginkgo nuts (EC50 ranged from 2.25 to 4.60 mg/mL) while significantly reducing their content in toxic compounds.

Benefit-risk assessment of dietary selenium and its associated metals intake in China (2017-2019): Is current selenium-rich agro-food safe enough?

Dietary consumption of selenium-rich agro-food is an effective way to avoid selenium deficiency diseases, however, over consumption of selenium-rich agro-food will result in potential risk of selenosis and problems with associated metals. In this study, we measured the concentrations of selenium and its associated metals in 2756 common and 4894 selenium-rich agro-food samples in 10 regions of China. We found that selenium-rich rice, flour, edible fungi and algae, meat, and tea contain higher levels of associated metals than other selenium-rich agro-food samples. Increasing the consumption of selenium-rich agro-food could make the actual intakes (AIs) of selenium for all population to meet respective recommended daily intakes (RDIs). Benefit-risk assessment results indicated that increasing the consumption of selenium-rich agro-food make AIs of selenium for all populations meet RDIs, chromium intakes for people under 18 years old exceed provisional tolerated daily intake (PTDIs), while arsenic and cadmium intakes are close to PTDIs. The main dietary contributors of selenium, chromium, arsenic and cadmium were meat, edible fungi and algae, rice, and rice, respectively. The study supported the consumption of selenium-rich agro-food for effective selenium supplement, but also emphasized potential risk from associated metals in selenium-rich agro-food, especially chromium.

Determination of Selenium in Common and Selenium-Rich Rice from Different Areas in China and Assessment of Their Dietary Intake.

In this study, 41 common rice varieties and 211 selenium-rich rice varieties from ten representative areas in China were collected in 2017-2019. The selenium contents of rice were analyzed with optimized inductively coupled plasma mass spectrometry (ICP-MS). Selenium concentrations of common rice and selenium-rich rice ranges were 0.81-7.26 and 0.76-180.73 µg/100 g, respectively. The selenium contents in selenium-rich rice from different areas were significantly different (p < 0.001) while those in common rice from different areas were not. The selenium-rich rice in Harbin and Keshan showed the lowest selenium level and those from selenium-rich areas (Enshi and Ankang) were highest. Based on the estimation of the risk assessment software @risk7.0 (Palisade Corporation, New York, NY, USA), the consumption of selenium-rich rice can effectively increase dietary selenium intake for the population. However, the risk index of P95 (Percentile 95) selenium exposure at the tolerable upper intake level for children at 2-14 years old exceeded 100%, with potential risk currently. Therefore, the consumption of selenium-rich rice should be properly monitored for young children and adolescents.

Phenolic acid profiles of common food and estimated natural intake with different structures and forms in five regions of China.

Phenolic acids have been reported to have many biological activities, but daily intake information is scarce. In this study, the phenolic acid contents of 116 commonly consumed food in five regions of China (Beijing, Hangzhou, Wuhan, Chongqing and Guangzhou) were analyzed by high performance liquid chromatography-mass spectrometry (HPLC-MS) and dietary intakes estimated. Tea had the highest total phenolic acids (TPA) content in all regions investigated. Phenolic acids were in esterified and bound forms, and hydroxycinnamic acids accounted for more than half of TPA content, except in tea and legumes. Average TPA intake was 193.50 mg/ day at the national level but ranged from 157.09 to 263.01 mg/ day among the regions. Rice, tea, and fruits were the main contributors to dietary intakes of TPA. Also, TPA intake in the period 2009-2013 increased 31.65 mg/ day compared with 2002, largely due to increased intakes of fruits, vegetables, and legumes.

Determination of phenolic acid profiles by HPLC-MS in vegetables commonly consumed in China.

This study aimed to establish a precise HPLC-MS approach to determine the concentrations and distribution of major phenolic acids in six categories of vegetables that are commonly consumed in China. We detected 17 phenolic acids within 15 min under optimized conditions. The method showed detection limits varying from 0.008 mg/L to 0.042 mg/L, average recoveries ranging from 71.0% to 110.7%, and a RSD of ≤9.98%. The average concentrations of total phenolic acids followed the order of flower > root > leafy > stem > bean > fruit vegetables. The phenolic acids were more abundant in the leafy, root, and stem vegetables than in the other vegetable samples. Furthermore, the levels of isoferulic acid, p-coumaric acid, and ferulic acid were greater than those of other phenolic acids in the vegetables. Free soluble phenolic acids were the dominant species in all vegetables (P < 0.001), except in the stem vegetables (P < 0.027).

Organic-inorganic hybrid perovskite quantum dot light-emitting diodes using a graphene electrode and modified PEDOT:PSS.

Perovskite quantum dot (PQD) light-emitting diodes (LEDs) have rapidly developed in the past several years due to the excellent optoelectronic properties of lead halide perovskites. However, PQD LEDs using graphene electrodes have not been reported despite their huge potential for applications in flexible displays and lighting sources. Herein, graphene was first used as the electrode of PQD LEDs. To overcome graphene's limitations such as hydrophobicity and graphene-induced film nonuniformity, the modification of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) with Triton X-100 and dimethyl sulfoxide (DMSO) codoping was reported, which not only improved the wettability of the graphene surface and the sequent film quality, but also reduced the dissolution of the PQD solvent to the bottom poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine] and PEDOT:PSS. More importantly, the synergistic effect of Triton X-100 and DMSO altered the PEDOT:PSS morphology from a coiled structure to a nanofibril conductive network, sufficiently enhancing the electrical conductivity of PEDOT:PSS. With this modification strategy, green PQD LEDs with CH3NH3PbBr3 emission layers were successfully fabricated on graphene anodes, with 3.7- and 4.4-fold enhancements in luminance and current efficiency, respectively, compared to those of their counterparts without PEDOT:PSS modification. The film modification strategy and graphene-based PQD LEDs in this work are expected to shed light on the further design and manufacture of flexible highly efficient PQD display and lighting devices.

Phytosterol Profiles of Common Foods and Estimated Natural Intake of Different Structures and Forms in China.

Phytosterols are well-known for their cholesterol-lowering effects, and the structures and forms of phytosterols affect their bioactivity. We aimed to illustrate the phytosterol profiles in common foods and estimate their natural intake in five geographical regions and among different age groups in China. In total, 12 phytosterols in free and esterified forms of 119 foods from five regions across China were examined using gas chromatography-mass spectrometry. Then, the dietary intake of phytosterols was calculated combined with the dietary foods intake data of Chinese people. The total phytosterol content was highest in vegetable oils (150.4-1230.9 mg/100 g), followed by legumes (129.6-275.6 mg/100 g), nuts (18.9-255.2 mg/100 g), and cereals (11.9-93.8 mg/100 g). Vegetables and fruits contained lower contents of total phytosterols. Phytosterols were mainly esterified in most common foods except in nuts. The predominant phytosterols were ß-sitosterol, campesterol, and stigmasterol, all of which belonged to plant sterols and 4-desmethylsterols. Total phytosterol intake varied across different regions, ranging between 257.7 and 473.7 mg/standard-person (sp)/day, with the highest intake in Beijing, followed by Hangzhou, Wuhan, Chongqing, and Guangzhou. However, phytosterol proportion was similar across regions, with ß-sitosterol accounting for 46.5-50.3% of the natural intake. Phytosterol intake was mainly constituted by plant sterols and 4-desmethylsterols in esterified form (61.9-74.6%). At the age of 2-70 years, phytosterol intake ranged from 154.3 mg/day to 348.0 mg/day in the national scale.

Degradation of phenylethanoid glycosides in Osmanthus fragrans Lour. flowers and its effect on anti-hypoxia activity.

This study was aimed at investigating the chemical stability (the thermal, light and pH stability) of phenylethanoid glycosides (PhGs) in Osmanthus fragrans Lour. flowers, identifying the degradation products of acteoside and salidroside (major PhGs in O. fragrans flowers) by UPLC-QTOF-MS and studying the anti-hypoxia activity of PhGs after degradation. The degradation of PhGs followed first-order reaction kinetics, and the rate constant of acteoside (4.3 to 203.4 × 10-3 day-1) was higher than that of salidroside (3.9 to 33.3 × 10-3 day-1) in O. fragrans flowers. Salidroside was mainly hydrolyzed to tyrosol during storage, and the degradation products of acteoside were verbasoside, caffeic acid, isoacteoside, etc. In a model of cobalt chloride (CoCl2)-induced hypoxia in PC12 cells, the anti-hypoxia ability of PhGs decreased after degradation, which resulted from the reduction of PhGs contents. Particularly, caffeic acid exhibited stronger anti-hypoxia ability than acteoside and could slightly increase the anti-hypoxia ability of degraded acteoside. The results revealed that high temperature, high pH and light exposure caused PhGs degradation, and thus the anti-hypoxia ability of PhGs reduced.

Metal ions accelerated phytosterol thermal degradation on Ring A & Ring B of steroid nucleus in oils.

This study aimed to investigate the effect of metal ions on the degradation of phytosterols in oils. The oil was heated at 180°C for 1h with/without addition of Fe3+, Fe2+, Cu2+, Mn2+, Zn2+, Na+, Al3+ and Mg2+. Variations of ß-sitosterol, stigmasterol, campesterol, brassicasterol and their degradation products were confirmed by the GC-MS analysis. In general, the increase of the metal ion concentration resulted in more phytosterol degradation, and the ability of metal ions following decreasing order: Fe3+>Fe2+>Mn2+≥Cu2+≥Zn2+>Na+≥Mg2+>Al3+. Metal ions significantly induced phytosterol autoxidation on C5, C6 and C7 on Ring B of steroid nucleus at even a low concentration, and induced dehydration on the C3 hydroxyl to form dienes and trienes at high concentration. The metal ions in oils are accounted for increasing phytosterol degradation, which decreases food nutritional quality and gives rise to the formation of undesirable compounds.

Phenolic compounds, antioxidant potential and antiproliferative potential of 10 common edible flowers from China assessed using a simulated in vitro digestion-dialysis process combined with cellular assays.

BACKGROUND: Phenolic compounds could be sensitive to digestive conditions, thus a simulated in vitro digestion-dialysis process and cellular assays was used to determine phenolic compounds and antioxidant and antiproliferative potentials of 10 common edible flowers from China and their functional components. RESULTS: Gallic acid, ferulic acid, and rutin were widely present in these flowers, which demonstrated various antioxidant capacities (DPPH, ABTS, FRAP and CAA values) and antiproliferative potentials measured by the MTT method. Rosa rugosa, Paeonia suffruticosa and Osmanthus fragrans exhibited the best antioxidant and antiproliferative potentials against HepG2, A549 and SGC-7901 cell lines, except that Osmanthus fragrans was not the best against SGC-7901 cells. The in vitro digestion-dialysis process decreased the antioxidant potential by 33.95-90.72% and the antiproliferative potential by 13.22-87.15%. Following the in vitro digestion-dialysis process, phenolics were probably responsible for antioxidant (R2 = 0.794-0.924, P < 0.01) and antiproliferative (R2 = 0.408-0.623, P < 0.05) potential. Moreover, gallic acid may be responsible for the antioxidant potential of seven flowers rich in edible flowers. CONCLUSION: The antioxidant and antiproliferative potential of 10 edible flowers revealed a clear decrease after digestion and dialysis along with the reduction of phenolics. Nevertheless, they still had considerable antioxidant and antiproliferative potential, which merited further investigation in in vivo studies. © 2017 Society of Chemical Industry.

Production and Characterization of Monoclonal Antibody Broadly Recognizing Cry1 Toxins by Use of Designed Polypeptide as Hapten.

In this study, by use of synthesized polypeptides as haptens, a monoclonal antibody with broad recognition against seven major Cry1 toxins (Cry1Aa, Cry1Ab, Cry1Ac, Cry1B, Cry1C, Cry1E, and Cry1F) has been produced and characterized. First, by comparing the three-dimensional structures of seven Cry1 toxins, analyzing the conserved sequences, and considering the antigenicity and hydrophilicity, three polypeptides (T1, T2, and T3) have been chosen and coupled to keyhole limpet hemocyanin as immunogens for the generic monoclonal antibody (Mab) generation. Thereafter, a double antibody sandwich enzyme-linked immunosorbent assay method (DAS-ELISA) was developed for simultaneous determination of seven Cry1 toxins. The results revealed that the haptens T1, T2, and T3 had different effects in the production of antibodies. Among them, the obtained Mab (strain 2D3) generated by T2 can recognize seven Cry1 toxins simultaneously. Equilibrium dissociation constant (KD) values for seven Cry1 toxins with Mab 2D3 were 1.198 × 10(-8) M for Cry1Aa, 2.197 × 10(-8) M for Cry1Ab, 1.367 × 10(-8) M for Cry1Ac, 2.092 × 10(-8) M for Cry1B, 5.177 × 10(-8) M for Cry1C, 4.016 × 10(-8) M for Cry1E, and 3.497 × 10(-8) M for Cry1F. For 2D3-based DAS-ELISA, the limits of detection (LOD) and limits of quantification (LOQ) can reach 15 and 30 ng·mL(-1) for each Cry1 toxin, respectively. Our study is the first report of a broadly specific immunoassay for multidetermination of seven major Cry1 toxins, and it will provide a new idea and technical routes for development of multidetermination immunoassays.

[Synthesis and biological evaluation of novel diphenyl methane sulfinyl and diphenylthio-acetamide derivatives].

According to the structure-activity relationships (SARs) of modafinil, a therapeutic drug of hypnolepsy, we designed and synthesized two series of compounds 2-[(diphenylmethane)sulfinyl] acetamides and 2-[(diphenylmethyl)thio] acetamides, and measured their biological activities. The target compounds (6a-6o) were synthesized beginning with diphenyl carbinol by substitution, oxidation, acylation and so on. Their structures were confirmed by ESI-MS, 1H NMR and elemental analysis. The central stimulatory effects of the target compounds were determined by the independent activity assay on mice. Compounds 6c, 6f and 6n have considerable activities, while the central stimulative effect of 6h is slightly better than the positive control modafinil.