Urinary Metabolomic Differentiation of Infants Fed on Human Breastmilk and Formulated Milk.

Human breastmilk is an invaluable nutritional and pharmacological resource with a highly diverse metabolite profile, which can directly affect the metabolism of infants. Application of metabolomics can discriminate the complex relationship between such nutrients and infant health. As the most common biological fluid in metabolomic study, infant urinary metabolomics may provide the physiological impacts of different nutritional resources, namely human breastmilk and formulated milk. In this study, we aimed to identify possible differences in the urine metabolome of 30 infants (1-14 days after birth) fed with breast milk (n = 15) or formulated milk (n = 15). From metabolomic analysis with gas chromatography-mass spectrometry, 163 metabolites from single mass spectrometry (GC-MS), and 383 metabolites from tandem mass spectrometry (GC-MS/MS) were confirmed in urinary samples. Various multivariate statistical analysis were performed to discriminate the differences originating from physiological/nutritional variables, including human breastmilk/formulate milk feeding, sex, and duration of feeding. Both unsupervised and supervised discriminant analyses indicated that feeding resources (human breastmilk/formulated milk) gave marginal but significant differences in urinary metabolomes, while other factors (sex, duration of feeding) did not show notable discrimination between groups. According to the biomarker analyses, several organic acid and amino acids showed statistically significant differences between different feeding resources, such as 2-hydroxyhippurate.

Quantitative Profiling of Carotenoids, Tocopherols, Phytosterols, and Fatty Acids in the Flower Petals of Ten Marigold (Tagetes spp. L.) Cultivars.

Marigold (Tagetes spp.) flower petals are the most vital sources of carotenoids, especially lutein esters, for the production of natural lutein to use for food, feed, and pharmaceutical industries. Several marigold cultivars are cultivated globally; however, their lutein ester composition and contents have not been widely investigated. Considering this, this study aimed to identify and quantify prominent carotenoid esters from the flower petals of ten marigold cultivars by liquid chromatography (LC)-diode-array detection (DAD)-mass spectrometry (MS). In addition, tocopherols, phytosterols, and fatty acids were analyzed by gas chromatography (GC)-flame ionization detection (FID) and GC-MS. Furthermore, the 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid (ABTS•+) and 2,2-diphenyl-1-picrylhydrazyl (DPPH•) radical scavenging abilities of lipophilic extracts were determined. The total carotenoid contents varied significantly (p < 0. 05, Tukey HSD) among cultivars, ranging from 25.62 (cv. Alaska)-2723.11 µg/g fresh weight (cv. Superboy Orange). Among the five major lutein-diesters, (all-E)-lutein-3-O-myristate-3'-O-palmitate and lutein dipalmitate were predominant. Among the studied cultivars, α-tocopherol was recorded, ranging from 167.91 (cv. Superboy Yellow) to 338.50 µg/g FW (cv. Taishan Orange). Among phytosterols, ß-sitosterol was the most prevalent phytosterol, ranging between 127.08 (cv. Superboy Yellow) and 191.99 µg/g FW (cv. Taishan Yellow). Palmitic acid (C16:0; 33.36-47.43%) was the most dominant among the fatty acids. In this study, the highest contents of lutein were recorded from cv. Superboy Orange; however, due to the substantially higher flower petal yield, the cv. Durango Red can produce the highest lutein yield of 94.45 kg/ha. These observations suggest that cv. Durango Red and cv. Superboy Orange are the ideal candidates for lutein fortification in foods and also for commercial lutein extraction.

Dissipation Kinetics and Risk Assessment of Diniconazole, Dinotefuran, Metconazole, and Tebuconazole in Raphanus sativus L.

This study investigated the degradation characteristics and conducted a risk assessment of four pesticides (Diniconazole, Dinotefuran, Metconazole, and Tebuconazole) in the leaves and roots of radish. Radish was cultivated in two greenhouse fields, and samples were collected at 0, 1, 2, 3, 5, 7, and 10 days after pesticide application. Sample analysis was performed using LC-MS/MS, and the recovery rates ranged from 70.1% to 118.6%. The biological half-life of Diniconazole was found to be 6.2 days (leaf and root), Dinotefuran was 5.3 days (leaf) and 4.6 days (root), Metconazole was 9.3 days (leaf) and 3.2 days (root), and Tebuconazole was 8.0 days (leaf) and 5.1 days (root). After comparing the maximum residue limits (MRL) of each pesticide in Korea with the residues during the pre-harvest interval (PHI), Diniconazole showed a Hazard quotient (HQ) exceeding 1, indicating potential risks for true consumers. Furthermore, Tebuconazole showed an HQ of 0.3 or higher, indicating a significant level of risk.

Dynamic modeling of pesticide residue in proso millet under multiple application situations.

Proso millet (Panicum miliaceum L.) is a cereal crop with potential resistance to drought and heat stress, making it a promising alternative crop for regions with hot and dry climates. Because of its importance, it is crucial to investigate pesticide residues in proso millet and assess their potential risks to the environment and human health to protect it from insects or pathogens. This study aimed to develop a model for predicting pesticide residues in proso millet using dynamiCROP. The field trials consisted of four plots, with each plot containing three replicates of 10 m2. The applications of pesticides were conducted two or three times for each pesticide. The residual concentrations of the pesticides in the millet grains were quantitatively analyzed using gas and liquid chromatography-tandem mass spectrometry. The dynamiCROP simulation model, which calculates the residual kinetics of pesticides in plant-environment systems, was employed for predicting pesticide residues in proso millet. Crop-specific, environment-specific, and pesticide-specific parameters were utilized to optimize the model. Half-lives of pesticides in grain of proso millet, which were needed to input for dynamiCROP, were estimated using a modified first-order equation. Proso millet-specific parameters were obtained from previous studies. The accuracy of the dynamiCROP model was assessed using statistical criteria, including the coefficient of correlation (R), coefficient of determination (R2), mean absolute error (MAE), relative root mean square error (RRMSE), and root mean square logarithmic error (RMSLE). The model was then validated using additional field trial data, which showed that it could accurately predict pesticide residues in proso millet grain under different environmental conditions. The results demonstrated the accuracy of the model in predicting pesticide residues in proso millet after multiple applications.

Metabolomic Responses of Lettuce (Lactuca sativa) to Allelopathic Benzoquinones from Iris sanguinea Seeds.

Weed management is important in modern crop protection. Chemical weed control using synthetic herbicides, however, suffers from resistance and ecotoxicity. Metabolomic investigation of allelopathy (or allelochemicals) may provide novel alternatives to synthetic herbicides. This study aimed to investigate the detailed metabolomic responses of plants to allelochemicals in Iris seed extracts. The seed extracts of Iris sanguinea showed the strongest growth inhibitory activity against alfalfa, barnyard grass, lettuce, and mustard. 3-Hydroxyirisquinone (3-[10(Z)-heptadecenyl]-2-hydroxy-5-methoxy-1,4-benzoquinone) was isolated as a major allelochemical from I. sanguinea seeds through bioassay-guided fractionation. The compound inhibited the growth of shoots and roots by browning root tips. Discriminant analysis identified 33 differentially regulated lettuce metabolites after treatment with 3-hydroxyirisquinone (3HIQ). Metabolic pathway analysis revealed that several metabolic pathways, including aromatic amino acid biosynthesis and respiratory pathways, were affected by the compounds. Differential responses of membrane lipids (accumulation of unsaturated fatty acids) and extensive formation of reactive oxygen species were observed in root tissues following treatment with 3HIQ. Overall, alkylbenzoquinone from I. sanguinea induced extensive metabolic modulation, oxidative stress, and growth inhibition. The metabolomic responses to allelochemicals may provide fundamental information for the development of allelochemical-based herbicides.

Metabolomic approach of azole fungicides in radish (Raphanus sativus): Perspective of functional metabolites.

Azole fungicides is one of the major fungicides in agricultural field. In this study, toxic effects of diniconazole (DIN), metconazole (MET), and tebuconazole (TEB) to radish leaves and roots were investigated using targeted metabolomics with gas chromatography-mass spectrometry (GC-MS/MS). Especially, the changes of functional chemicals, including phytosterols and glucosinolates evaluated. Radish leaves and roots were harvested after 7 days and 14 days from last exposure. In multivariate analysis, the experimental groups showed clear separation in PCA and PLS-DA score plots. Phytosterols and glucosinolates were significantly changed by azole fungicide. Six metabolic pathways which are affected by fungicides were selected and showed similar patterns regardless of the type of azole fungicide used. As a result, azole fungicide induces the defense mechanisms of plants and affects both primary and secondary metabolism.

Profiling of Nutritionally Vital Bioactive Compounds in Emerging Green Leafy Vegetables: A Comparative Study.

Green leafy vegetables (GLVs), especially lettuce and spinach, are the key source of bioactive antioxidants in a diet. This research compared the contents and composition of lettuce and spinach bioactive compounds with emerging GLVs, moringa and fenugreek. Liquid chromatography (LC)-mass spectrometry (MS) with single ion monitoring (SIM) was used to examine carotenoids and tocols, while phytosterols were examined using gas chromatography (GC)-MS. Among the studied GLVs, the (all-E)-lutein was the most dominating carotenoid ranging between 31.3 (green/red lettuce)−45.3 % (fenugreek) of total carotenoids, followed by (all-E)-violaxanthin and (all-E)-ß-carotene. Surprisingly, (all-E)-ß-carotene, a provitamin A carotenoid, was the second most dominating carotenoid in moringa, accounting for 109.2 µg/g fresh weight (FW). Moreover, the significantly highest (p < 0.05; Tukey HSD) contents of total carotenoids (473.3 µg/g FW), α-tocopherol (83.7 µg/g FW), and total phytosterols (206.4 µg/g FW) were recorded in moringa. Therefore, moringa foliage may serve as an affordable source of nutritionally vital constituents in a diet.

Profiling of Redox-Active Lipophilic Constituents in Leaf Mustard (Brassica juncea (L.) Czern.) Cultivars Using LC-MS and GC-MS.

Leaf mustard is an important commercial and culinary vegetable. However, only limited information is available on the content and composition of the nutritionally important lipophilic constituents in these leaves. This research presents information on the contents and composition of carotenoids, tocols, phytosterols, and fatty acids in four cultivars of leaf mustard. The carotenoids and tocols were analyzed utilizing liquid chromatography (LC)-mass spectrometry (MS) with single ion monitoring (SIM), while phytosterols and fatty acids were analyzed using gas chromatography (GC)-MS and GC-flame ionization detection (FID), respectively. The LC-MS results revealed the dominance of (all-E)-lutein, within the range of 37.12 (cv. Asia Curled)-43.54% (cv. Jeok) of the total carotenoids. The highest amount of all of the individual carotenoids and total carotenoids (143.85 µg/g fresh weight; FW) were recorded in cv. Cheong. Among the studied leaf samples, 67.16 (cv. Asia Curled)-83.42 µg/g FW (cv. Cheong) of α-tocopherol was recorded. Among the phytosterols, ß-sitosterol was the most dominant one among the studied mustard leaves, accounting for 80.42 (cv. Jeok)-83.14% (cv. Red frill) of the total phytosterols. The fatty acid analysis revealed the presence of a significant amount of rare hexadecatrienoic acid (C16:3n3) in the studied mustard leaves, which accounted for 27.17 (cv. Asia Curled)-32.59% (cv. Red frill) of the total fatty acids. Overall, the cv. Cheong represented the highest contents of carotenoids, tocols, and phytosterols. Moreover, cv. Red frill contains the highest amount of n-3 PUFAs and antioxidant compounds. Thus, these cultivars can be promoted in cuisines which can be eaten to obtain the highest health benefits.

Anticancer Potential of Lipophilic Constituents of Eleven Shellfish Species Commonly Consumed in Korea.

The present study was aimed to investigate the composition and contents and the major lipophilic compounds, including the sterols, fatty acids, and tocols of shellfish species. Moreover, to explore the antitumor activity of these lipophilic constituents, their cytotoxicity potentials were determined against five different human cancer cells, including colon carcinoma (HCT116), epithelial melanoma (A2058), glioblastoma multiforme (T98G), lung carcinoma (A549), and adenocarcinoma (HeLa). The results show a significant variation in the contents and composition of lipophilic constituents among the studied species. The highest omega-3 (n-3) polyunsaturated fatty acids (PUFAs) were recorded from arrow squid and pacific oysters, accounting for 53.2% and 53.0% of their total fatty acids, respectively. However, the highest cholesterol content was also recorded in arrow squid (154.4 mg/100 g; 92.6% of total sterols). In contrast, in the Japanese littleneck, Yesso scallop, and common orient clam, cholesterol was just 17.1%, 18.3%, and 18.9% of total sterols, respectively, making them the richest source of non-cholesterol sterols (NCS). Lipids extracted from shellfish species showed ABTS+•- and DPPH•-scavenging activities. In the cytotoxicity analysis, lipids extracted from the Argentine red shrimp showed the highest cytotoxicity against glioblastoma multiforme T98G cells, with an IC50 value of 12.3 µg/mL. The composition and cytotoxicity data reported herein may help explore the nutritional and anticancer potentials of shellfish species.

Phytosterol Profiling of Apiaceae Family Seeds Spices Using GC-MS.

Phytosterols are nutritionally vital phytoconstituent owing to their cholesterol (low-density plasma lipoprotein-cholesterol, LDL-C)-lowering, anti-inflammatory, and antioxidant properties. Among the widely used spices and herbs, the seeds spices of the Apiaceae family represented the healthiest fatty acid profile. Thus, to explore the other health-beneficial lipids, the present study was aimed to analyze the phytosterol profile of eight seed spices of the Apiaceae family, utilizing gas chromatography (GC)-mass spectrometry (MS). The sterols contents calculated on an oil (mg/100 g of oil) and spice weight (mg/100 g spices; dry weight) basis varied significantly among the seed spices (p < 0.05; Turkey HSD). The ß-sitosterol and stigmasterol were the most dominating sterols among the studied spices, together accounted for 40.3 (Ajwain) to 69.8% (celery) of total sterols in the seed oil. Among the studied spices, the oil extracted from caraway seeds showed the highest total sterols (602.2 mg/100 g of oil). Interestingly, based on spice weight, fennel seeds also showed the similar highest number of total sterols (134.2 mg/100 g in fennel and 133.3 mg/100 g in caraway), owing to the high contents of oil (25.9%) in fennel seeds. Overall, celery, caraway, fennel, and anise seeds oil are rich sources of health-beneficial phytosterols.

Rapid Capillary-Assisted Solution Printing of Perovskite Nanowire Arrays Enables Scalable Production of Photodetectors.

Despite recent progress in producing perovskite nanowires (NWs) for optoelectronics, it remains challenging to solution-print an array of NWs with precisely controlled position and orientation. Herein, we report a robust capillary-assisted solution printing (CASP) strategy to rapidly access aligned and highly crystalline perovskite NW arrays. The key to the CASP approach lies in the integration of capillary-directed assembly through periodic nanochannels and solution printing through the programmably moving substrate to rapidly guide the deposition of perovskite NWs. The growth kinetics of perovskite NWs was closely examined by in situ optical microscopy. Intriguingly, the as-printed perovskite NWs array exhibit excellent optical and optoelectronic properties and can be conveniently implemented for the scalable fabrication of photodetectors.

5-(3',4'-Dihydroxyphenyl)-γ-valerolactone, a metabolite of procyanidins in cacao, suppresses MDI-induced adipogenesis by regulating cell cycle progression through direct inhibition of CDK2/cyclin O.

Cacao (Theobroma cacao) has a significant polyphenol content and has been reported to elicit anti-obesity effects. Previous studies have focused on the properties of cacao extract and procyanidins, while the potential mechanisms have not been fully elucidated. Here, we investigated the inhibitory effects of procyanidin metabolites on adipogenic cocktail-induced adipogenesis and lipogenesis in 3T3-L1 preadipocytes. It was observed that 5-(3',4'-dihydroxyphenyl)-γ-valerolactone (DHPV), a major procyanidin metabolite, exhibited the greatest inhibitory effects on adipogenesis and lipogenesis. DHPV dose-dependently reduced the expression levels of proteins involved in adipogenesis including peroxisome proliferator-activated receptor γ (PPAR γ) and CCAT/enhancer-binding protein α (C/EBP α), as well as lipogenesis-related factors such as fatty acid synthase and acetyl-CoA carboxylase. These inhibitory effects were primarily due to G1 phase arrest and the suppression of cell proliferation during mitotic clonal expansion, the early stage of adipogenesis. In an extensive kinase array, DHPV directly suppressed activation of the CDK2/cyclin O complex, and inhibited the phosphorylation of C/EBP ß, which is responsible for the induction of PPAR γ and C/EBP α. Taken together, these findings suggest that DHPV is a highly biologically active compound with potential anti-obesity effects and works by inhibiting the intracellular lipid content and cell differentiation.

Convenient and Robust Route to Photoswitchable Hierarchical Liquid Crystal Polymer Stripes via Flow-Enabled Self-Assembly.

Hierarchically arranged stripes of photoswitchable liquid crystal polymers (LCPs) containing azobenzene moieties were conveniently crafted via a flow-enabled self-assembly (FESA). Interestingly, by subjecting a drop of LCP solution to dry in a restricted geometry comprising two nearly parallel plates with a stationary upper plate and a movable lower plate that programmably traveled in a "stop-and-move" manner during the FESA process, photoswitchable LCP stripes were yielded, displaying two modes of deposition, namely, periodic primary stripes of large dimensions and regularly spaced secondary stripes of small dimensions situated between adjacent primary stripes (i.e., forming hierarchical LCP stripes). Notably, these hierarchical azobenzene moieties-containing stripes demonstrated sequential photoinduced reversible phase transition (i.e., photoswitching) due to the thickness difference between primary and secondary stripes. A UV light-induced expansion effect was observed on the LCP stripes. Clearly, such rapid creation of hierarchical stripes by FESA represents a robust means of organizing polymers, nanoparticles, colloids, DNA, etc. into complex yet ordered patterns over a large area in a simple and controllable manner for potential use in surface relief grating, photoactuators, photoswitchable devices, antifake labels, etc.

Light-Driven Shape-Memory Porous Films with Precisely Controlled Dimensions.

Shape-memory polymers (SMPs) are an intriguing class of smart materials possessing reversible shape change and recovery capabilities. Effective routes to shape-memory porous films (SMPFs) are few and limited in scope owing to the difficulty in manipulating the shape change of pores by conventional methods. Herein we report an unconventional strategy for crafting light-driven SMPFs by judiciously constructing highly ordered porous films via a facile "breath figure" approach, followed by sequential vapor crosslinking and nondestructive directional light manipulation. Micropores can thus be transformed into other shapes including rectangle, rhombus and size-reduced micropores at room temperature. The transformed micropores can be reverted to their original shapes by either thermal annealing or UV irradiation. As such, this strategy expands the rich diversity of SMPs accessible.

Flexible Electronics: An Epidermal Stimulation and Sensing Platform for Sensorimotor Prosthetic Control, Management of Lower Back Exertion, and Electrical Muscle Activation (Adv. Mater. 22/2016).

The design of an ultrathin, conformal electronic device that integrates electrotactile stimulation with electromyography, temperature, and strain sensing in a single, simple platform is reported by J. A. Rogers and co-workers on page 4462. Demonstrated application possibilities include prosthetic control with sensory feedback, monitors, and stimulation signals related to lower back exertion, and electrical muscle stimulation with feedback control.

An Epidermal Stimulation and Sensing Platform for Sensorimotor Prosthetic Control, Management of Lower Back Exertion, and Electrical Muscle Activation.

The design of an ultrathin, conformal electronic device that integrates electrotactile stimulation with electromyography, temperature, and strain sensing in a single, simple platform is reported. Experiments demonstrate simultaneous use of multiple modes of operation of this type of device in the sensorimotor control of robotic systems, in the monitoring of lower back exertion and in muscle stimulation.