[Rapid determination of 22 functional components in cosmetics using ultra-high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry].

Plant components from extracts of Sophora flavescens, rhodiola, ginseng, Centella asiatica, and tea play important roles in skin whitening, moisturizing, anti-aging, sun protection, anti-inflammation, antiseptic, bacteriostatic, and other effects of cosmetics. At present, no relevant standard methods have been established to detect the addition amounts of plant extracts in cosmetics. In addition, plant extracts listed in product labels may be undetectable due to their addition in trace quantities and the lack of technical support. Therefore, a quantitative method for the simultaneous determination of 22 functional components in cosmetics was established by ultra-high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry (UHPLC-LTQ/Orbitrap MS). Target compounds were extracted with methanol from samples using ultrasonic extraction, and then separated on a C18 column (100 mm × 2.1 mm, 1.8 µm) with gradient elution of 0.1% (v/v) formic acid aqueous solution (A) and acetonitrile (B). The gradient elution program were as follows: 0-5 min, 5%B-8%B; 5-25 min, 8%B-60%B; 25-35 min, 60%B-80%B; 35-36 min, 80%B-5%B; 36-45 min, 5%B. The flow rate was 0.3 mL/min and the injection volume was 5 µL. Accurate masses of precursor ions were used to detect cosmetic functional components in positive ionization mode. The fragment ions obtained by higher energy collisional dissociation were used for confirmation of the functional components. Each compound showed good linearity. The limits of detection (LODs) were in the range of 0.003-2.01 mg/kg, and the limits of quantification (LOQs) were in the range of 0.02-4.36 mg/kg. Recoveries at three levels were 63.2%-125.1%, and relative standard deviations (RSDs) were 0.18%-10.9%. Fifty-four batches of samples labeled with four monomer functional components and nine plant extracts were tested. In the 17 batches of samples labeled with nicotinamide, 4 batches labeled with caffeine, and 6 batches labeled with Sophora flavescens root extract, the labeled functional components were detected. One out of 11 batches of samples labeled with D-panthenol was not detected. Three of the seven batches of samples labeled with ascorbyl glucoside were not detected. In the 21 batches of samples labeled with licorice extracts, the corresponding functional components were not detected in 9 batches. In the 21 batches of samples labeled with Centella asiatica extract, the corresponding functional components were not detected in 11 batches. In the 13 batches of samples labeled with tea extract, the corresponding functional components were not detected in 8 batches. In 11 of the 12 batches containing ginseng root extract, the corresponding functional components were not detected. In five of the six batches of astragalus membranaceus root extract samples, the corresponding functional components were not detected. In samples labeled with Polygonum cuspidatum root extract, Rehmannia glutinosa root extract, and Ophiopogon japonicus root extract, the corresponding functional components were detected. The method is simple, rapid, reliable, accurate, and suitable for the determination of the 22 functional components in cosmetics.

Dissipation, Processing, Leaching, and Safety Evaluation of Flonicamid and Its Metabolites in Tea.

BACKGROUND: Tea is a popular traditional non-alcoholic beverage worldwide. Flonicamid is a selective systemic pyridine carboxamide insecticide that is widely used for controlling tea leafhopper in tea. OBJECTIVE: The leaching rates, dissipation dynamics, and residue levels of flonicamid and its metabolites in tea leaves during processing and transferring were investigated to validate the safe risk in tea and transfer behavior using high performance liquid chromatography-tandem mass spectrometry with a convenient pretreatment method. METHOD: The extracting method and immersion rate experiments were optimized by single factor analysis and orthogonal tests. The acetonitrile extracting solvent with 0.5% formic acid was used and optimal leaching conditions were obtained with a regime of 15 min immersion time, 100°C temperature, three immersions and a tea-to-water ratio of 1:50. RESULTS: Average recoveries in processed green tea and infusions were 80.85-98.75% with relative standard deviations <5.87%. LODs and LOQs of flonicamid, 4-trifluoromethylnicotinic acid (TFNA), N-(4-trifluoromethylnicotinoyl) glycine (TFNG), and 4-trifluoromethylnicotinamide (TFNA-AM) were 0.0013-0.350 and 0.004-1 µg/g, respectively. The processing factor of flonicamid was 0.36-5.52 during green tea manufacture. The leaching rates were 22.9-97.4% from processed tea to infusion. CONCLUSIONS: The risk of long-term and short-term dietary intake of flonicamid was safe in tea infusions with the risk quotient (RQ) values <1 for the Chinese consumer. This work may provide guidance for safe and reasonable consumption of flonicamid in tea in China. HIGHLIGHTS: The suitable leaching factors of flonicamid and its metabolites in tea infusions were optimized by orthogonal experimentation for the first time.

Preparation of dummy molecularly imprinted polymers based on dextran-modified magnetic nanoparticles Fe3O4 for the selective detection of acrylamide in potato chips.

Novel dummy magnetic molecularly imprinted polymers (dex-MMIPs) were prepared for highly selective recognition and fast enrichment of acrylamide (AA) in potato chips. Propionamide (PA) was used as dummy template molecule and the Fe3O4 nanoparticles modified with carboxymethyl dextran were developed as supports. Methacrylic acid (MAA) and ethyleneglycoldimethacrylate (EGDMA) were chosen as the functional monomer and cross-linker, respectively. Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) were used to characterize the synthesized dex-MMIPs. The adsorption of dex-MMIPs reached equilibrium within 20 min, and the maximum adsorption quantity (Qm) was 19.28 mg/g with the dissociation constant (Kd) of 35.7 mg/L. Moreover excellent recognition toward acrylamide was achieved compared to analogs, such as N, N'-methylenebisacrylamide (MBA) and nicotinamide (VPP). The satisfactory recoveries of 83.9-96.8% were achieved for selective separation and enrichment of AA in spiked potato chips by dex-MMIPs.

Determination of pesticide residual levels in strawberry (Fragaria) by near-infrared spectroscopy.

BACKGROUND: In this study, an infrared-based prediction method was developed for easy, fast and non-destructive detection of pesticide residue levels measured by reference analysis in strawberry (Fragaria × ananassa Duch, cv. Albion) samples using near-infrared spectroscopy and demonstrating its potential alternative or complementary use instead of traditional pesticide determination methods. Strawberries of Albion variety, which were supplied directly from greenhouses, were used as the study material. A total of 60 batch sample groups, each consisting of eight strawberries, was formed, and each group was treated with a commercial pesticide at different concentrations (26.7% boscalid + 6.7% pyraclostrobin) and varying residual levels were obtained in strawberry batches. The strawberry samples with pesticide residuals were used both to collect near-infrared spectra and to determine reference pesticide levels, applying QuEChERS (quick, easy, cheap, rugged, safe) extraction, followed by liquid chromatographic-mass spectrometric analysis. RESULTS AND CONCLUSION: Partial least squares regression (PLSR) models were developed for boscalid and pyraclostrobin active substances. During model development, the samples were randomly divided into two groups as calibration (n = 48) and validation (n = 12) sets. A calibration model was developed for each active substance, and then the models were validated using cross-validation and external sets. Performance evaluation of the PLSR models was evaluated based on the residual predictive deviation (RPD) of each model. An RPD of 2.28 was obtained for boscalid, while it was 2.31 for pyraclostrobin. These results indicate that the developed models have reasonable predictive power. © 2019 Society of Chemical Industry.

Effect of supplementation of nicotinamide and sodium butyrate on the growth performance, liver mitochondrial function and gut microbiota of broilers at high stocking density.

This study was conducted to investigate the effects of stocking density and dietary nicotinamide (NAM) and butyrate sodium (BA) supplementation on the growth performance, liver mitochondrial function and gut microbiota of broilers at high stocking density. A total of 342, 26-d-old Cobb500 broilers were divided into 5 groups with 6 replicates. Treatments were as follows: (a) Low stocking density (L, 9 birds per cage); (b) High stocking density (H, 12 birds per cage); (c) H + 50 ppm NAM; (d) H + 500 ppm BA; (e) H + 50 ppm NAM + 500 ppm BA (COMB). The results showed that high stocking density significantly reduced the feed intake and body weight gain of broilers, while COMB improved the growth performance at high stocking density. High stocking density significantly reduced the liver metallothionein content, liver mitochondrial membrane potential and the activities of Na+K+-ATPase and Ca2+Mg2+-ATPase. In contrast, the liver metallothionein contents in the NAM, BA and COMB fed group were higher than those in the H group. COMB increased the activity of ATPase as well, but it failed to enhance the mitochondrial membrane potential. Stocking density also affected gut microbiota of broilers. The high-density group increased the relative abundance of Blautia. Supplementation of BA and NAM increased the abundance of Lactobacillus and Bifidobacteria, respectively. In conclusion, a combination of NAM and BA can improve the performance, antioxidant capacity, mitochondrial function and intestinal microbiota of broilers at high stocking density.

Comparison of GC-MS and MEKC methods for caffeine determination in preworkout supplements.

In this study, GC-MS- and MEKC-based methods for determination of caffeine (CAF) in preworkout supplements were developed and validated. The proposed protocols utilized minimal sample preparation (simple dilution and syringe filtration). The developed methods achieved satisfactory validation parameters, i.e. good linearity (R2 > 0.9988 and R2 > 0.9985 for GC-MS- and MEKC-based method, respectively), satisfactory intra- and interaccuracy (within 92.6-100.7% for method utilizing GC-MS and 92.1-110.3% for protocol based on MEKC) and precision (CV < 15.9% and CV < 6.3% for GC-MS- and MEKC-based method, respectively) and recovery (within 100.1-100.8% for method utilizing GC-MS and 101.5-106.2% for protocol based on MEKC). The LOD was 0.03 and 3 µg/mL for method utilizing GC-MS and MEKC, respectively. The CAF concentrations determined by GC-MS- and MEKC-based methods were found to be in the range of 8.53-11.23 and 8.20-11.61 µg/mL, respectively. Taking into consideration information on the labels, the investigated supplements were found to contain from 110.0 to 167.3% of the declared CAF content, which confirmed the literature reports on incompatibility of the declared product compositions with real ones. Nevertheless, the consumption of examined supplements as recommended by producers did not lead to exceeding the CAF safe limit of 400 mg per day. Additionally, the MEKC-based method allowed for detection and identification of vitamin B3 and B6 in all of the investigated supplement samples, which demonstrated that MEKC-based protocols may be an appropriate assays for simultaneous determination of CAF and vitamins.

NMR-Based Metabolomics Approach To Study the Influence of Different Conditions of Water Irrigation and Greenhouse Ventilation on Zucchini Crops.

This study describes the approach of 1H NMR metabolomic profiling for the differentiation of zucchini produced under different conditions of water irrigation (desalinated seawater -0.397 dS/m, 0.52 €/m3 vs groundwater -2.36 dS/m, 0.29 €/m3) and ventilation (surface area of the vent openings/greenhouse area was 15.0% for one sector and 9.8% for the other). Overall, 72 extracts of zucchini ( Cucubirta pepo L. cv Victoria) under four different conditions were regularly analyzed during the spring-summer cycle from April to July 2017. We have found that zucchini plants irrigated with desalinated seawater increased the zucchini production yield, presented fruits with higher concentration of glucose, fructose, and vitamin B3, and displayed an increased antioxidant activity. On the contrary, plant groundwater irrigation produced the increment of sucrose level that could rise the sweetness perception of the fruits. Finally, the ventilation variable produced a higher concentration of trigonelline, histidine, and phenylalanine but only on those zucchinis irrigated with groundwater.

Positive effects of an oil adjuvant on efficacy, dissipation and safety of pyrimethanil and boscalid on greenhouse strawberry.

Methylated vegetable oil adjuvants can enhance initial deposition and decrease the required dosages of pesticides sprayed on plants, so an oil adjuvant mixed with fungicides were used to prevent and control gray mold in greenhouse strawberry. As the persistence and dietary exposure risks from fungicides on strawberries after using adjuvants have not been assessed, the efficacy, dissipation and safety of pyrimethanil and boscalid in the presence and absence of a methylated vegetable oil adjuvant were evaluated. To better describe the actual use of fungicides in greenhouse strawberry, twice repeated application of fungicides were conducted follower by an optimized QuEChERS pre-treatment method. When applied at 60% of their recommended dosages with the adjuvant, the efficacy of pyrimethanil and boscalid for gray mold was similar to that shown by the treatment of 100% fungicides in absence of the adjuvant based on Duncan's Multiple-Range test, and their average residues increased to 89.0% and 89.3%, respectively. The adjuvant enhanced the accumulation effect of pyrimethanil residue by 31.7% after repeated applications, and the half-lives were similar (5.2 and 4.2 d). The adjuvant had comparable accumulation effects (1.75 and 1.83) and similar half-lives (5.4 and 5.5 d) for boscalid. In absence of adjuvant, the risk quotients (RQs) of pyrimethanil (0.41 and 0.33) and boscalid (0.49 and 0.63) after twice applications at pre-harvest interval were lower than 1. Adding the methylated vegetable oil adjuvant to fungicides would result in unprolonging half-life and acceptably low dietary exposure risk on strawberries, but lower dosage of fungicides were used.

Dietary Exposure Risk Assessment of Flonicamid and Its Effect on Constituents after Application in Lonicerae Japonicae Flos.

To investigate the dietary exposure risk of flonicamid application on Lonicerae Japonicae Flos and the effect of flonicamid on constituents of Lonicerae Japonicae Flos, field experiments were conducted in Fengqiu, Henan province, and flonicamid residue in samples collected was detected by gas chromatography equipped with electron capture detector (GC-ECD). And chlorogenic acid and luteoloside were determined by HPLC. Dietary exposure risk assessment was conducted through comparing the estimated daily intake (EDI) which was calculated by using the consumed residual level along with the acceptable daily intake (ADI). The effect of flonicamid on chlorogenic acid and luteoloside were obtained by ANOVA statistical analysis and least significant difference (LSD)-t test. The results showed that the terminal-residue contents of flonicamid were under 1.6 mg kg-1. And risk quotient ranged from 0.0011 to 0.0028, indicating the long-term exposure to flonicamid residual through consumption of Lonicerae Japonicae Flos in consumers was relatively low. Flonicamid could suppress the generation of luteoloside, so it was not advised to be used in L. japonica flowering phase. The study aims at providing the useful suggestion on the reasonable flonicamid usage and the reference for the establishment of maximum residue limits (MRLs) of flonicamid in Lonicerae Japonicae Flos.

Dissipation behaviour and dietary risk assessment of boscalid, triflumizole and its metabolite (FM-6-1) in open-field cucumber based on QuEChERS using HPLC-MS/MS technique.

BACKGROUND: To resist plant diseases, boscalid and triflumizole have been applied to cucumbers frequently. However, the residue and dietary risk assessment of these fungicides in cucumber should be given attention for food safety. RESULTS: An effective and highly sensitive method based on the liquid chromatography-tandem mass spectrometry technique for simultaneous multidetermination of boscalid, triflumizole and its metabolite (FM-6-1) in a cucumber ecosystem was established and validated. Field experiments were conducted in three different locations, where boscalid and triflumizole (35% suspension concentration) were applied at 253 g of active ingredient (a.i.) per hectare (the recommended high dosage) and 379.5 g a.i. ha-1 (1.5 times the recommended high dosage) in each location. The limits of quantification and the limits of detection of the proposed method ranged from 0.01 to 0.05 mg kg-1 and 3.9 × 10-5 to 7.5 × 10-4 mg L-1 respectively. The mean recoveries and relative standard deviations of these compounds were 80-105% and 1.0-6.1% respectively. The dissipation dynamics of compounds followed pseudo-first-order kinetic models remarkably, with a half-value period of 2.3-40.8 days. The residues of boscalid and triflumizole in cucumber at harvest were below 0.66 mg kg-1 and 0.07 mg kg-1 respectively. The results of the dietary risk assessments have shown a low dietary risk of compounds in cucumber with hazard ratios <1 and hazard index <1. CONCLUSION: These results from the experiments are the most important for putting a guide on reasonable usage of these fungicides under the open-field conditions in China. © 2018 Society of Chemical Industry.

Gluten-Free Flours from Different Raw Materials as the Source of Vitamin B1, B2, B3 and B6.

Gluten-free (GF) products are those with a natural absence or acceptable level (<20 mg/kg) of gluten. They should be a part of a diet for people with gluten-related disorders, like celiac disease. Recently the popularity of a gluten-free diet (GFD) has risen extremely, because a lot of healthy individuals exclude gluten from their menus. According to the literature data on nutritional deficiencies in the GFD, this trend seems to be risky. This paper describes the nutritional value of 14 flours from different GF raw materials from the aspect of B-group vitamin content (B1, B2, B3, B6). Vitamins were determined using high performance liquid chromatography after enzymatic and acid hydrolysis of the samples. The vitamin contents significantly differed in the analysed flours. The content (in 100 g of the product) of vitamin B1 ranged from 0.01 mg (amaranth flour) to 0.60 mg (teff flour), vitamin B2 from 0.03 mg (GF flour with oats) to 0.22 mg (buckwheat flour), vitamin B3 from below 0.01 mg (amaranth flour) to 6.02 mg (millet flour), and vitamin B6 from 0.03 mg (acorn flour) to 0.69 mg (amaranth flour). The content of vitamins in the analysed GF flours was also compared to gluten-containing flours. Obtained results indicate that flours from teff, millet, chestnut, buckwheat, and amaranth are better sources of certain B-group vitamins than flours from corn, rice, and some flours with gluten.

Dissipation of Flonicamid in Honeysuckle and Its Transfer during Brewing Process.

The dissipation of flonicamid in Honeysuckle and transfer pattern from Honeysuckle to its tea infusion were investigated. Flonicamid was applied on Honeysuckle crop at two dosages, 60 g of active gradient per hectare (g a.i. hm-2) and 180 g a.i. hm-2 (recommended and triple the recommended) in Fenqiu, Henan Province in 2015 and 2016. Gas Chromatography-Electron Capture Detector (GC-ECD) detection methods were developed for the analysis of flonicamid residues in honeysuckles and its infusion. The recoveries in both honeysuckles and its infusion ranged from 81.5 to 101.7% with relative standard deviations (RSDs) of 3.2-9.1%. The dissipations of flonicamid in Honeysuckle were found to follow the first order kinetics with half-life ranging between 2.8 and 3.2 d. After recommended dose pesticide application, contents of flonicamid residues were lower than theoretical maximum residue limit (tMRL). Flonicamid residues can easily transfer from Honeysuckle to its tea infusion and transfer rates of flonicamid decrease with the brewing temperature reduction or the brewing times increase. These results are helpful to establish maximum residue limit and develop guidance on the appropriate and secure use of flonicamid in Honeysuckle.

Simultaneous quantitation of nicotinamide riboside, nicotinamide mononucleotide and nicotinamide adenine dinucleotide in milk by a novel enzyme-coupled assay.

Nicotinamide riboside, the most recently discovered form of vitamin B3, and its phosphorylated form nicotinamide mononucleotide, have been shown to be potent supplements boosting intracellular nicotinamide adenine dinucleotide (NAD) levels, thus preventing or ameliorating metabolic and mitochondrial diseases in mouse models. Here we report for the first time on the simultaneous quantitation of nicotinamide riboside, nicotinamide mononucleotide and NAD in milk by means of a fluorometric, enzyme-coupled assay. Application of this assay to milk from different species revealed that the three vitamers were present in human and donkey milk, while being selectively distributed in the other milks. Human milk was the richest source of nicotinamide mononucleotide. Overall, the three vitamers accounted for a significant fraction of total vitamin B3 content. Pasteurization did not affect the bovine milk content of nicotinamide riboside, whereas UHT processing fully destroyed the vitamin. In human milk, NAD levels were significantly affected by the lactation time.

Detection and quantification of boscalid and its metabolites in honeybees.

Boscalid is a new-generation fungicide that has been detected in several bee matrices. The objective of this work was to characterize boscalid metabolites in honeybees based on in vivo experimentation, and next to verify the presence of theses metabolites into honeybees from colonies presenting troubles. A methodology based on complementary mass spectrometric tools, namely ultra-high performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-QToF) or triple quadrupole mass spectrometry (UHPLC-QqQ) was implemented. Honeybees were sprayed with boscalid, at field rate (to induce the metabolization process) and the parent compound with its generated metabolites were then extracted using modified EU-QuEChERS method. The mass characteristics including exact mass, isotopic profile and mass fragments allowed assuming the structure of several metabolites. Some of them were unambiguously identified by comparison with synthesized analytical standards. The metabolites were resulted from hydroxylation and dechlorination of the parent compound as well as the substitution of a chlorine atom with an hydroxyl group. The metabolites were then quantified in bee samples collected from various beehives located in France. Boscalid and three of its metabolites were present in some samples at a level ranged between 0.2 and 36.3 ng/g.

A dark brown roast coffee blend is less effective at stimulating gastric acid secretion in healthy volunteers compared to a medium roast market blend.

Coffee consumption sometimes is associated with symptoms of stomach discomfort. This work aimed to elucidate whether two coffee beverages, containing similar amounts of caffeine, but differing in their concentrations of (ß) N-alkanoyl-5-hydroxytryptamides (C5HTs), chlorogenic acids (CGAs), trigonelline, and N-methylpyridinium (N-MP) have different effects on gastric acid secretion in healthy volunteers. The intragastric pH after administration of bicarbonate with/without 200 mL of a coffee beverage prepared from a market blend or dark roast blend was analyzed in nine healthy volunteers. Coffee beverages were analyzed for their contents of C5HT, N-MP, trigonelline, CGAs, and caffeine using HPLC-DAD and HPLC-MS/MS. Chemical analysis revealed higher concentrations of N-MP for the dark brown blend (87 mg/L) compared to the market blend coffee (29 mg/L), whereas concentrations of C5HT (0.012 versus 0.343 mg/L), CGAs (323 versus 1126 mg/L), and trigonelline (119 versus 343 mg/L) were lower, and caffeine concentrations were similar (607 versus 674 mg/mL). Gastric acid secretion was less effectively stimulated after administration of the dark roast blend coffee compared to the market blend. Future studies are warranted to verify whether a high ratio of N-MP to C5HT and CGAs is beneficial for reducing coffee-associated gastric acid secretion.

Flour fortification in South Africa: post-implementation survey of micronutrient levels at point of retail.

BACKGROUND: Fortification of staple foods is an effective strategy to deliver and increase the intake of micronutrients in the diet and can reduce micronutrient deficiencies. It is important to ensure that the food vehicle consistently contains adequate amounts of nutrients at the point of consumption for effective impact. OBJECTIVE: This survey aimed to gauge the level of fortification of maize and wheat flour at the retail level compared with staple food fortification regulations in South Africa to better understand the current obstacles to effective delivery of micronutrients through flour fortification and consider approaches to strengthening the program. METHODS: White bread flour and maize meal samples were collected from retail points across all provinces and analyzed for vitamin A, iron, and nicotinamide, and a database capturing the origins of the sample was populated. Nicotinamide and vitamin A results were compared against each other and evaluated against food regulations. RESULTS: The level of compliance with statutory fortification requirements was low, both for bread flour and for maize meal. There is evidence of insufficient addition of premix as opposed to losses due to vitamin A stability as seen from the strong correlation between vitamin A and nicotinamide in maize meal. CONCLUSIONS: The current levels of micronutrients added to maize meal and bread flour are unsatisfactory. This is likely to be because of insufficient addition of premix at the mills. This affects the availability and intake by consumers of fortified product and potentially prevents the desired reduction in vitamin and mineral deficiencies expected from the flour fortification program.

Minor crops for export: a case study of boscalid, pyraclostrobin, lufenuron and lambda-cyhalothrin residue levels on green beans and spring onions in Egypt.

Dissipation rates of boscalid [2-chloro-N-(4' -chlorobiphenyl-2-yl)nicotinamide], pyraclostrobin [methyl 2-[1-(4-chlorophenyl) pyrazol-3-yloxymethyl]-N-methoxycarbanilate], lufenuron [(RS)-1-[2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-3-(2,6-difluorobenzoyl)urea] and lambda-cyhalothrin [(R)-cyano(3-phenoxyphenyl)methyl (1S,3S)-rel-3-[(1Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropanecarboxylate] in green beans and spring onions under Egyptian field conditions were studied. Field trials were carried out in 2008 in a Blue Nile farm, located at 70 kilometer (km) from Cairo (Egypt). The pesticides were sprayed at the recommended rate and samples were collected at pre-determined intervals. After treatment (T(0)) the pesticide residues in green beans were 7 times lower than in spring onions. This is due to a different structure of vegetable plant in the two crops. In spring onions, half-life (t(1/2)) of pyraclostrobin and lufenuron was 3.1 days and 9.8 days respectively. At day 14th (T(14)) after treatment boscalid residues were below the Maximum Residue Limit (MRL) (0.34 versus 0.5 mg/kg), pyraclostrobin and lambda -cyhalothrin residues were not detectable (ND), while lufenuron residues were above the MRL (0.06 versus 0.02 mg/kg). In green beans, at T(0), levels of boscalid, lufenuron and lambda -cyhalothrin were below the MRL (0.28 versus 2 mg/kg; ND versus 0.02 mg/kg; 0.06 versus 0.2 mg/kg, respectively) while, after 7 days treatment (T(7)) pyraclostrobin residues were above the MRL (0.03 versus 0.02 mg/kg). However, after 14 days the residue level could go below the MRL (0.02 mg/kg), as observed in spring onions.

Simultaneous determination of B-group vitamins in enriched Brazilian dairy products.

In addition to serving as good natural sources of vitamin B(2), milk and milk products are currently being enriched with the vitamins B(1), B(2), B(6), and nicotinamide in Brazil. The objective of this research was to evaluate the levels of enrichment of these products according to their availability in supermarkets in the Campinas (SP, Brazil) region. The separation of the vitamins was carried out on a C 18 column with gradient elution with acetonitrile and aqueous phase. Detection of vitamins was effected in the ultraviolet region and quantification by an external standard. The levels of vitamin B(2) determined in powdered whole milk, skimmed milk powder, and one brand of flavored lactic beverage, were practically double those stated on the packages. The same occurred with vitamins B(6) and PP (nicotinic acid + nicotinamide), when determined in the same lactic beverage and with vitamin B(6), determined in acidified milk. The high levels of vitamin B(2), naturally present in whole milk, and the predominance of the free form, allowed for the determination of this vitamin in non-enriched milk.

Desenvolvimento e validação de métodos cromatográficos e avaliação da estabilidade de vitaminas hidrossolúveis em alimentos / Development and validation of chromatographic methods and stability study of hidrossoluble vitamins in food

A adição de vitaminas aos produtos industrializados tornou-se prática comum para as indústrias de alimentos e os teores adicionados devem obedecer à legislação brasileira durante toda a vida de prateleira dos produtos. Sabendo da sensibilidade das vitaminas a fatores como oxigênio, luz e calor, é essencial conhecer o comportamento destes compostos no alimento frente aos fatores críticos. Informações confiáveis sobre teores de vitaminas somente podem ser obtidas com métodos analíticos validados. A perspectiva deste trabalho é desenvolver metodologias analíticas por cromatografia líquida de alta eficiência para determinação de vitaminas B1, B2, B6 e PP, validá-las e então analisar amostras submetidas a diferentes condições de estocagem durante 10 meses para verificação do comportamento destas vitaminas

Rapid determination of thiamine, riboflavin, pyridoxine, and niacinamide in infant formulas by liquid chromatography.

A simplified, simultaneous determination of vitamins B1, B2, B3, and B6 in supplemented infant formulas was developed from a single deproteinized sample extract, with analysis by reversed-phase, ion-pair chromatography with an acidified methanol-water mobile phase. The dioctylsulfosuccinate counter-ion facilitates unique retention of the pyridine-based vitamins (niacinamide and pyridoxine) and allows for concurrent measurement of both the pyridoxal and riboflavin 5'-phosphate endogenous components of milk. Other naturally occurring undetected vitamin congeners have minimal analytical significance. UV detection is used for niacinamide, and programmed fluorescence detection is used for riboflavin and the B6 vitamins. Thiamine is routinely determined sequentially under modified elution conditions.