高效液相色谱法测定土壤中6种邻苯二甲酸酯的含量及其生物有效性的评价

取土壤样品10.000g两份,其中一份用10mL甲醇超声提取30min使其所含6种邻苯二甲酸酯(PAEs)[包括邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁基苄酯(BBP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二(2-乙基)己酯(DEHP)及邻苯二甲酸二辛酯(DNOP)]溶于甲醇中。于提取液中加入硫酸镁和氯化钠,离心3 min。取上清液,定容至10.0mL。经0.45μm滤膜过滤,取滤液按色谱条件进行测定。以Zorbax Eclipse C18色谱柱为固定相,以不同比例的乙腈(A)和水(B)的混合液为流动相进行梯度洗脱,并用紫外检测器于245nm处测定。上述6种PAEs的质量浓度均在0.10~10.0mg·L^-1内与其对应的色谱峰面积呈线性关系,检出限在0.01~0.04mg·L^-1之间。另一份样品先用10mL胃液在37℃振荡提取1h,用碳酸氢钠调节消化液pH至7.0,加入55.0mg胆汁盐和15mg胰液素,在37℃振荡提取2h,完成体外胃肠模拟处理。经离心3min,取上清液,按上述方法加入甲醇提取,并用高效液相色谱法进行测定。所得结果表明:PAEs的脂溶性越高,其生物有效性越低。此外,土壤的理化参数对PAEs的生物有效性也有影响。     

Medicinal Values and Potential Risks Evaluation of Ginkgo biloba Leaf Extract (GBE) Drinks Made from the Leaves in Autumn as Dietary Supplements

Ginkgo tea and ginkgo wine are two familiar Ginkgo biloba leaf extract (GBE) drinks in the form of dietary supplements (DS) used for healthcare in east Asia. Nevertheless, a comprehensive evaluation of their safety and efficacy is still lacking. In this study, GBE drinks were prepared from naturally newly senescent yellow leaves (YL) and green leaves (GL) in autumn. Their total flavonoids, antioxidant capacity and prescribed ingredients were investigated. In brief, the proportions of total flavonoids, total flavonol glycosides (TFs), total terpene trilactones (TTLs) and ginkgolic acids in the GBE drinks all did not meet the standards of worldwide pharmacopoeias. Specifically, the levels of TFs in the ginkgo tea prepared from YL were significantly higher than that prepared from GL. Further analyses revealed a substandard ratio of isorhamnetin/quercetin and an accumulation of leaf-age-related compounds, which were both unqualified. The proportions of specific TTLs varied between the ginkgo tea and ginkgo wine, although no significant differences were detected in terms of the total levels of TTLs. Noticeably, numerous biflavones and thousands of times over the limiting concentration of ginkgolic acids, including newly identified types, were only detected in ginkgo wine. Finally, the use of the GBE drinks as DSs was comprehensively evaluated according to the acceptable daily intake. This study showed the limited healthcare effects of GBE drinks despite their powerful antioxidant capacity.     

膳食纤维降血脂作用及其机制的研究进展

综述了近年膳食纤维降脂作用及其机制的研究进展.膳食纤维能使血清中胆固醇、甘油三酯、低密度脂蛋白水平降低,高密度脂蛋白水平升高.其主要机制为通过减少膳食中胆固醇的吸收、影响机体中胆固醇的代谢、促进胆固醇的排泄等降低血浆中胆固醇水平;通过增加食物在肠道内的过渡时间、延缓胃排空、减缓或降低脂肪的吸收等机制降低血浆中甘油三酯水...     

Fast Detection of Cadmium in Chocolate by Solid Sampling Electrothermal Vaporization Atomic Absorption Spectrometry and Its Application on Dietary Exposure Risk Assessment

In this work, a rapid detection method using solid sampling electrothermal vaporization atomic absorption spectrometry (SS-ETV-AAS) was established for cadmium in chocolate. The instrumental system includes a solid sampling ETV unit, a catalytic pyrolysis furnace, an AAS detector, and a gas supply system with only an air pump and a hydrogen generator. Herein, MgO material with 1.0–1.5 mm particle size was first employed to replace the kaolin filler previously used to further shorten the peak width and to thereby improve the sensitivity. With 350 mL/min of air, a chocolate sample was heated for 25 s from 435 to 464 °C to remove water and organic matrices; then, after supplying 240 mL/min hydrogen and turning down air to 120 mL/min, a N₂/H₂ mixture gas was formed to accelerate Cd vaporization from chocolate residue under 465 to 765 °C. Under the optimized conditions, the detection limit (LOD) was obviously lowered to 70 pg/g (vs. previous 150 pg/g) with R² > 0.999; the relative standard deviations (RSD) of repeated measurements for real chocolate samples ranged from 1.5% to 6.4%, indicating a favorable precision; and the Cd recoveries were in the range of 93–107%, proving a satisfied accuracy. Thus, the total analysis time is less than 3 min without the sample digestion process. Thereafter, 78 chocolate samples with different brands from 9 producing countries in China market were collected and measured by this proposed method. Based on the measured Cd concentrations, a dietary exposure assessment was performed for Chinese residents, and the target hazard quotient (THQ) values are all less than 1, proving no significant health risk from intaking chocolate cadmium for Chinese residents.     

Multicriteria Decision Analysis and Grouping of Analytical Procedures for Phthalates Determination in Disposable Baby Diapers

This study presents the application of one of the tools from the multicriteria decision analysis set (MCDA), the Technique for Order Preference by Similarity to Ideal Solution (TOPSIS). Selected green analytical chemistry metrics were used to rank analytical procedures for the phthalate determination in disposable baby diapers. Nine analytical procedures were assessed in order to find one that has the lowest environmental impact and the best analytical figures of merit. Nine different criteria, where weighting was based on the experts’ evaluation, were used in the procedures’ assessment. With the use of TOPSIS, an easy and straightforward technique, selection of the most appropriate procedure was made.     

太阳神健康饮品对学龄前儿童血红蛋白及血微量元素的影响

选择5～6岁儿童72名,随机分为两组,分别服用太阳神健康饮品和一般乳酸奶,每天服用100mL,连服9周,经检测,服用太阳冲健康饮品组,血红蛋白和微量元素Zn、Fe、Mn含量均升高,而服一般乳酸奶组,除Zn升高外,其它无变化。     

Investigation and Analysis of Pesticide Residues in Four Common Vegetables and Risk Assessment of Dietary Exposure in Ceramic Capital,China

In order to understand the basic situation of pesticide residues in vegetables in China’s porcelain capital, four kinds of common vegetables on the market were selected in this study for detection and analysis of pesticide residues. The pesticide residues in vegetables were analyzed through sample selection, optimization of instrument and equipment conditions, and comparison of detection pass rates. The sampling locations were common vegetables purchasing places such as large and medium-sized supermarkets. QuEChERS method was used as the sample pretreatment, and gas chromatography (GC-MS/MS) was used for quantitative analysis. Finally, the exposure risk of pesticides was assessed according to the test results. The results showed that all the pesticides were detected in four kinds of vegetables, but the detected pesticides did not exceed the national standard (GB 2763-2014, China). Moreover, the target risk coefficient (THQ) and risk index (HI) values of four vegetables were less than one, indicating that the combined and toxic effect of pesticide residual mixed contamination was smaller in four vegetables. Therefore, there was no significant harm from people using these vegetables.     

重庆某地区居民膳食及发铁、血红蛋白含量分析

通过对重庆市某地区居民膳食结构和营养状况的调查,了解居民营养状况,特别是铁的营养状况。采用五日回顾法进行了膳食调查,氰化高铁血红蛋白法测定血红蛋白值及示波极谱法测定了发铁含量。结果表明,居民膳食蛋白质、多种维生素、矿物质摄入不足;贫血率为67.81%,发铁含量低于正常值的仅为6.70%。提示两地居民膳食属发展中国家模式,应调整膳食结构,增加豆类及动物性食物的摄入量,并增加含铁食物的摄入量,提高机体对铁的吸收和利用。     

广东省某民办中学膳食中微量元素调查及其评价

为调查和评价民办中学膳食中微量元素营养情况,探讨最佳膳食模式,全面改善学生的营养,采用称质量法调查三天膳食。结果表明,每人每天微量元素摄入量(RDA)为:Ca523.00mg、Fe10.72mg、Zn10.91mg、Se58.07μg;用RDA标准评价,Ca、Fe、Zn、Se达标率(%)分别为:初中男生45.58、76.00、68.07、100.00;女生33.59、39.50、50.00、100;高中男生52.80、70.87、77.00、100.00;女生47.50、46.70、76.33、100.00。结论是该中学学生Se达标;Ca、Fe、Zn均未达标,有待研究最佳膳食模式,全面改善学生营养。     

A Nationwide Study of Residual Fate of Fluxapyroxad and Its Metabolites in Peanut Crops Across China: Assessment of Human Exposure Potential

Elaborating on the residual fate of fluxapyroxad and its metabolites based on their nationwide application was vital to protect the human population from their hazardous effects. In this study, a rapid and sensitive analytical method was developed to trace fluxapyroxad and two of its metabolites in peanut matrices using an ultrahigh chromatography method coupled with mass spectrometry (UHPLC–MS/MS) within 3.5 min. The occurrence, pharmacokinetic degradation and terminal magnitudes of fluxapyroxad were reflected in the original deposition of 8.41–38.15 mg/kg, half–lives of 2.5–8.6 d and final concentrations of 0.004–37.38 mg/kg in peanut straw. The total concentrations of fluxapyroxad in peanut straw (0.04–39.28 mg/kg) were significantly higher than those in peanut kernels (<0.001–0.005 mg/kg) and an obvious concentration effect was observed in fresh (0.01–11.56 mg/kg) compared dried peanut straw (0.04–38.97 mg/kg). Fluxapyroxad was demethylated to 3–(difluoromethyl)–N–(3′,4′,5′–trifluoro[1,1′–biphenyl]–2–yl)–1H–pyrazole–4–carboxamide (M700F008, 0.02–5.69 mg/kg) and further N–glycosylated to 3–(difluoromethyl)–1–(ß–D–glucopyranosyl)–N–(3′,4′,5′–triflurobipheny–2–yl)–1H–pyrzaole–4–carboxamide (M700F048, 0.04–39.28 mg/kg).The risk quotients of the total fluxapyroxad for the urban groups were significantly higher than those for the rural groups, and were both negatively correlated with the age of the groups, although both acute (ARfD%, 0.006–0.012%) and chronic (ADI%, 0.415–1.289%) risks are acceptable for the human population. The high-potential health risks of fluxapyroxad should be continuously emphasized for susceptible toddlers (1–3 years), especially those residing in urban areas.     

Pitfalls and Solutions for the Trace Determination of Phthalates in Water Samples

A method based on liquid-liquid extraction (LLE) and automated large volume injection (LVI)-GC-MS analysis was developed for the trace determination of phthalate di-esters in water samples at sub-g L^–1 (ppb) levels. Strategies applied to reduce contamination include (i) careful selection of tools, glassware and solvents, (ii) systematic blank checks of the chromatographic system, glassware and solvents and (iii) frequent verifications of blanks during sequences. Background levels could be reduced to those present in the extraction solvent. For phthalates not present in the extraction solvent the limits of quantitation (LOQ) are 6 ng L^–1 for di-methyl phthalate (DMP), 3 ng L^–1 for benzylbutyl phthalate (BzBP) and 45 ng L^–1 for the isomeric phthalate mixtures di-isononyl phthalate (DiNP) and di-isodecyl phthalate (DiDP). For the other phthalates, the LOQ was set at twice the blank (extraction solvent) level and are 20 ng L^–1 for di-ethyl phthalate (DEP), 60 ng L^–1 for di-isobutyl phthalate (DiBP), 80 ng L^–1 for di-n-butyl phthalate (DBP) and 30 ng L^–1 for bis-(2-ethylhexyl) phthalate (DEHP).Dedicated to Professor K. Jinno on the occasion of his 60^th birthday     

东莞市城区儿童血锌、铁、钙元素与饮食习惯、生长发育关系的研究

探讨了莞城地区幼儿园3～7岁儿童血锌、铁、钙值与饮食习惯、身高、体重、易感染情况的关系，以便进一步指导喂养。采用群体自愿参加者取静脉血，检测了血清锌、铁、钙。检测前向家长发问卷调查饮食习惯、易感染情况。抽血后测量身高、体重。结果表明，在城区7所幼儿园1125例受检儿童中，检出血锌、铁、钙异常者831例(73．9％)，其中低于正常值者525例(63．2％)。有不良饮食习惯儿童342例(30．4％)。有轻度营养不良189例(16．8％)。身高不达标342例(30．4％)。复感儿508例(54．8％)。结论为：(1)本组儿童低血锌情况严重，而血锌值与饮食习惯、易感染情况、身高有密切关系。(2)未发现一例低血清铁者。(3)儿童低血钙者较少，低血钙与不良饮食习惯有关。     

Amaranth Seeds and Sprouts as Functional Ingredients for the Development of Dietary Fiber,Betalains, and Polyphenol-Enriched Minced Tilapia Meat Gels

There is an increasing interest in the development of meat processed products enriched with antioxidant dietary fiber to augment the consumption of these health beneficial compounds. This study aimed to evaluate the nutritional, nutraceutical, and antioxidant potential, as well as the physicochemical properties of minced tilapia fillets (meat) gels with added amaranth seed or sprout flours (0%, 2%, 4%, 8%, and 10% w/w). Dietary fiber content was significantly increased with the addition of amaranth seed (1.25–1.75-fold) and sprout flours (1.99–3.21-fold). Tilapia gels with added 10% amaranth seed flour showed a high content of extractable dihydroxybenzoic acid and cinnamic acid, whereas the addition of 10% amaranth sprout flour provided a high and wide variety of bioactive compounds, mainly amaranthine and bound ferulic acid. The addition of amaranth seed and sprout flours increased hardness (1.01–1.73-fold) without affecting springiness, decreased luminosity (1.05–1.15-fold), and increased redness and yellowness. Therefore, amaranth seed and sprout flours could be used as functional ingredients for the development of fish products rich in bioactive compounds.     

响应面法优化萃取条件用于高效液相色谱分析饮用水中痕量邻苯二甲酸二(2-乙基己基)酯及其迁移规律

应用响应面法辅助分析塑料瓶装饮用水中邻苯二甲酸二（2-乙基己基）酯（DEHP）的迁移,建立了一种快速、简便、环保的痕量塑化剂类污染物检测方法。在盐析作用下,使用正己烷涡旋萃取,经氮气浓缩后进行高效液相色谱-紫外检测。响应面最优分析法考察了盐量、涡旋时间和萃取液体积3个因素作为萃取条件对DEHP回收率的影响,得到最佳萃取条件：盐量为16 g/L、涡旋时间为90 s、萃取液体积为5.28 mL。在此实验条件下,DEHP的最大理论回收率为92.91%,实验验证值为92.97%,与理论值相差0.06%。本方法检出限为0.006 mg/L,满足中国国家标准规定的生活饮用水安全标准要求（0.008 mg/L）,在0.01~15 mg/L范围内线性关系良好（相关系数R=0.9996）。选取常见市售饮用水样品进行分析,研究了塑料包装饮用水中痕量DEHP迁移的规律。与传统的优化方法相比,响应面模型分析法综合考虑了各因素的影响,而且更加简便、低成本、对环境友好,是实现样品中微痕量污染物精准检测的重要辅助手段。     

A method for determination of acetaldehyde in bottled waters and the effect of time and temperature on concentrations

ABSTRACT

Solid phase extraction (SPE) technique followed by gas chromatography (GC) coupled with flame ionisation detector was evaluated for the analysis of acetaldehyde concentration in water contained in polyethylene terephthalate (PET) bottles. Fifteen fresh samples of 1.5 L of different brands were collected from the local market and stored in the laboratory under controlled temperatures at 20°C, 30°C and 40°C. The samples were analysed at regular intervals of time. The acetaldehyde determined in these samples was found in the range of 9.88–139.44 µg/L. Moreover, the level of acetaldehyde was found to increase with increase in temperature and storage time. Furthermore, the results indicate that the proposed method is very simple, low cost and efficient for the determination and recovery of trace amount of acetaldehyde in bottled water.     

Anti-Colon Cancer Activity of Dietary Phytochemical Soyasaponin I and the Induction of Metabolic Shifts in HCT116

Dietary phytochemicals play an important role in the prevention and treatment of colon cancer. It is reported that group B of soyasaponin, derived from dietary pulses, has anti-colonic effects on some colon cancer cell lines. However, it is uncertain which specific soybean saponins play a role. In our study, as one of the group B soyasaponin, the anti-colon cancer activity of soyasaponins I (SsI) was screened, and we found that it had the inhibitory effect of proliferation on colon cancer cell lines HCT116 (IC₅₀ = 161.4 μM) and LoVo (IC₅₀ = 180.5 μM), but no effect on HT29 between 0–200 μM. Then, nine potential targets of SsI on colon cancer were obtained by network pharmacology analysis. A total of 45 differential metabolites were identified by metabolomics analysis, and the KEGG pathway was mainly enriched in the pathways related to the absorption and metabolism of amino acids. Finally, molecular docking analysis predicted that SsI might dock with the protein of DNMT1, ERK1. The results indicated that the effect of SsI on HCT116 might be exerted by influencing amino acid metabolism and the estrogen signaling pathway. This study may provide the possibility for the application of SsI against colon cancer.     

Chromatographic Determination of the Mycotoxin Patulin in 219 Chinese Tea Samples and Implications for Human Health

Patulin (PAT) is a mycotoxin, with several acute, chronic, and cellular level toxic effects, produced by various fungi. A limit for PAT in food of has been set by authorities to guarantee food safety. Research on PAT in tea has been very limited although tea is the second largest beverage in the world. In this paper, HPLC−DAD and GC−MS methods for analysis of PAT in different tea products, such as non-fermented (green tea), partially fermented (oolong tea, white tea, yellow tea), completely fermented (black tea), and post-fermented (dark tea and Pu-erh tea) teas were developed. The methods showed good selectivity with regard to tea pigments and 5-hydroxymethylfurfural (5-HMF) and a recovery of 90–102% for PAT at a 10–100 ppb spiking level. Limit of detection (LOD) and limit of quantification (LOQ) in tea were 1.5 ng/g and 5.0 ng/g for HPLC−UV, and 0.25 ng/g and 0.83 ng/g for GC−MS. HPLC was simpler and more robust, while GC−MS showed higher sensitivity and selectivity. GC−MS was used to validate the HPLC−UV method and prove its accuracy. The PAT content of 219 Chinese tea samples was investigated. Most tea samples contained less than 10 ng/g, ten more than 10 ng/g and two more than 50 ng/g. The results imply that tea products in China are safe with regard to their PAT content. Even an extreme daily consumption of 25 g of the tea with the highest PAT content (124 ng/g), translates to an intake of only 3 μg/person/day, which is still an order of magnitude below the maximum allowed daily intake of 30 µg for an adult.     

Automatic in-tube SPME and fast liquid chromatography: a cost-effective method for the estimation of dibuthyl and di-2-ethylhexyl phthalates in environmental water samples

A 80-cm length commercially available capillary coated with 95% polydimethylsiloxane and 5% polydiphenylsiloxane (TBR-5) was employed to carry out on-line extraction and preconcentration of dibuthyl phthalate (DBP) and di-2-ethylhexyl phthalate (DEHP) in the chromatographic system. The coated capillary was placed between the sample injection loop and the injection needle of an autosampler. Variables affecting the automatic in-tube solid-phase microextraction (SPME) were optimized. A Genesis C₁₈ (5 cm × 4.6 mm i.d., 4 μm particle size) was employed as analytical column. The achieved limits of detection by use of diode array detection were 1 and 2.5 μg L⁻¹, respectively. The proposed conditions have been applied to determine those compounds at low ppb levels (≤250 μg L⁻¹) in aqueous samples. No matrix effect was found, and recoveries between 85 and 115% were obtained. The precision of the method was good, and the achieved intra- and inter-day variation coefficients were between 5 and 20%. The analysis time per sample was 20 min and any off-line pre-treatment of the samples was needed. The taken sample volume was 100 μL. Data on the application of the described method to the analysis of different water samples are presented.     

Occurrence of Disinfection By-Products in Swimming Pools in the Area of Thessaloniki,Northern Greece. Assessment of Multi-Pathway Exposure and Risk

This study investigated the occurrence of disinfection by-products (DBPs) (trihalomethanes (THMs), haloacetic acids (HAAs), halonitriles (HANs), halonitromethane (TCNM) and haloketones (HKs)) in different type of swimming pools in the area of Thessaloniki, northern Greece by employing the EPA methods 551.1 and 552.3. Moreover, general water quality parameters (pH, residual chlorine, dissolved organic carbon, UV₂₅₄ absorption, total nitrogen, alkalinity and conductivity) were also measured. The concentrations of DBPs showed great variability among swimming pools as well as within the same pool between sampling campaigns. HAAs exhibited the highest concentrations followed by THMs, HANs, TCNM and HKs. Exposure doses for four age groups (3–<6 y, 6–<11 y, 11–<16 y and adults) were calculated. Route-specific exposures varied among DBPs groups. Inhalation was the dominant exposure route to THMs and TCNM (up to 92–95%). Ingestion and dermal absorption were the main exposure routes to HAAs (40–82% and 18–59%, respectively), depending on the age of swimmers. HANs contributed up to 75% to the calculated cytotoxicity of pool water. Hazard indices for different exposure routes were <1, suggesting non-carcinogenic risk. Inhalation posed the higher carcinogenic risk for THMs, whereas risk via oral and dermal routes was low. Ingestion and dermal contact posed the higher risk for HAAs. Risk management strategies that minimise DBPs exposure without compromising disinfection efficiency in swimming pools are necessary.