Optimization of Physical Refining Process of Camellia Oil for Reduction of 3-Monochloropropane-1,2-Diol (3-MCPD) Ester Formation Using Response Surface Methodology on a Laboratory Scale.

Refined and deodorized camellia oil has been reported to contain a high amount of 3-monochloropropane-1,2-diol esters (3-MCPDE) due to the high-temperature deodorization step. To reduce 3-MCPDE in camellia oil, the physical refining process of camellia oil was simulated on a laboratory scale. Response surface methodology (RSM) was designed to modify and optimize the refining process with five processing parameters (water degumming dosage, degumming temperature, activated clay dosage, deodorization temperature and deodorization time). The optimized new refining approach achieved a 76.9% reduction in 3-MCPDE contents, in which the degumming moisture was 2.97%, the degumming temperature was 50.5 °C, the activated clay dosage was 2.69%, the deodorizing temperature was 230 °C, and the deodorizing time was 90 min. A significance test and analysis of variance results demonstrated that the deodorization temperature and deodorization time contributed significantly to the reduction of 3-MCPD ester. The joint interaction effects of activated clay dosage and deodorization temperature were significant for 3-MCPD ester formation.

[Chloropropanol and glycidyl esters content in edible vegetable oils in China in 2015-2017].

OBJECTIVE: To investigate the occurrence data for fatty acid esters of chloropropanol and glycidyl in edible vegetable oils purchased in China. METHODS: The 1309 samples of edible vegetable oil were collected and the data of chloropropanol and glycidyl were detected by the gas chromatography-mass spectrometry from 2015 to 2017. RESULTS: The detection rate of 3-monochloropropanediol esters in vegetable oils was 81. 83% with the mean level of 1. 21 mg/kg. The mean content of tea-seed oil was significantly higher than that of other varieties, followed by peanut oil(1. 36 mg/kg), rapeseed oil(1. 12 mg/kg). The sunflower seed oil has the lowest mean content(0. 54 mg/kg). The detection rate of 2-monochloropropanediol esters in vegetable oils was 82. 84% with the mean level of 0. 39 mg/kg. The content of peanut oil was significantly higher than that of other varieties, followed by blended oil(0. 30 mg/kg) and soybean oil(0. 25 mg/kg). There was no significant difference with rapeseed oil(0. 66 mg/kg). The exceeding rate of glycidyl ester was 19. 90% with the mean level of 0. 68 mg/kg. The average content of glycidyl ester in blended oil(0. 78 mg/kg) was significantly higher than that in peanut oil(0. 54 mg/kg). There was no significant difference among other varieties. CONCLUSION: The pollution of chloropropanol esters is common in edible vegetable oils in China. The contamination is different in kinds of edible oils.

Dietary exposure of general Chinese population to fatty acid esters of 3-monochloropropane-1, 2-diol (3-MCPD) from edible oils and oil-containing foods.

Edible oils and oil-containing foods have been regarded as the main source of 3-monochloropropane-1, 2-diol (3-MCPD) esters. A total of 3,847 individual food samples were collected in China to carry out 3-MCPD fatty acid esters analysis. The samples comprising edible oils, fried foods and bakery foods from 31 Chinese provinces, municipalities and autonomous regions were obtained from the national food contaminant information system during 2015-2017. The dietary exposure and potential risks associated with the consumption of 3-MPCD esters from edible oils and oil-containing foods were estimated using a semi-probabilistic assessment model. Concentrations of 3-MCPD fatty acid esters in food samples were detected by gas chromatography-mass spectrometry (GC-MS). The mean levels of 3-MCPD fatty acid esters in edible oils, fried foods and bakery foods were 0.862, 0.249 and 0.145 mg/kg, respectively. The range of mean dietary intakes of 3-MCPD esters in different subpopulation groups (classified by gender and age) was from 0.586 to 1.539 µg/kg bw/day, which were all lower than 2 µg/kg bw/day - the tolerable daily intake (TDI) established by the European Food Safety Authority (EFSA). The range of dietary intake of 3-MCPD esters in high consumers (95th percentile) in each group was from 1.511 to 4.027 µg/kg bw/day, which accounted for 75.6% to 201.4% of the TDI. The 3-MCPD esters exposure level of 3.5% of the total Chinese population exceeded the TDI. The findings indicate that the potential health risks caused by dietary 3-MCPD esters from edible oils and oil-containing foods were of low concern for most of the Chinese population. However, the exposure risk of the consumers with excessive edible oil consumption calls for attention.

Estimated assessment of cumulative dietary exposure to organophosphorus residues from tea infusion in China.

BACKGROUND: China has the world's largest tea plantation area in the world. To sustain high yields of the tea, multiple pesticides are used on tea crops to control pests. Organophosphorus (OP) pesticides are among the most widely used types of agricultural pesticides in China. As tea is a significant potential source of exposure to pesticide residues, the public concern has increased in relation to pesticide residues found in tea in China. The aim of the study was to estimate cumulative dietary exposure to OP residues from tea infusion for Chinese tea consumers to determine whether exposure to OP residues from tea infusion is a cause of health concern for tea consumers in China. METHODS: OP residue data were obtained from the China National Monitoring Program on Food Safety (2013-2014), encompassing 1687 tea samples from 12 provinces. Tea consumption data were obtained from the China National Nutrient and Health Survey (2002), comprising 506 tea consumers aged 15-82 years. The transfer rates of residues from tea leaves into tea infusions were obtained from the literature. The relative potency factor (RPF) approach was used to estimate acute cumulative exposure to 20 OP residues from tea infusion using methamidophos as the index compound. Dietary exposure was calculated in a probabilistic way. RESULTS: For tea consumers, the mean and the 99.9th percentile (P99.9) of cumulative dietary exposure to OP residues from tea infusion equalled 0.08 and 1.08 µg/kg bw/d. When compared with the acute reference dose (ARfD), 10 µg/kg bw/d for methamidophos, this accounts for 0.8 and 10.8% of the ARfD. CONCLUSIONS: Even when considering OP residues from vegetables, fruits and other foods, there are no health concerns based on acute dietary exposure to OP residues from tea infusion. However, it is necessary to strengthen the management of the OP pesticides used on tea in China to reduce the risk of chronic dietary exposure to OPs from tea infusion.

Isotope dilution gas chromatography with mass spectrometry for the analysis of 4-octyl phenol, 4-nonylphenol, and bisphenol A in vegetable oils.

By the combination of solid-phase extraction as well as isotope dilution gas chromatography with mass spectrometry, a sensitive and reliable method for the determination of endocrine-disrupting chemicals including bisphenol A, 4-octylphenol, and 4-nonylphenol in vegetable oils was established. The application of a silica/N-(n-propyl)ethylenediamine mixed solid-phase extraction cartridge achieved relatively low matrix effects for bisphenol A, 4-octylphenol, and 4-nonylphenol in vegetable oils. Experiments were designed to evaluate the effects of derivatization, and the extraction parameters were optimized. The estimated limits of detection and quantification for bisphenol A, 4-octylphenol, and 4-nonylphenol were 0.83 and 2.5 µg/kg, respectively. In a spiked experiment in vegetable oils, the recovery of the added bisphenol A was 97.5-110.3%, recovery of the added 4-octylphenol was 64.4-87.4%, and that of 4-nonylphenol was 68.2-89.3%. This sensitive method was then applied to real vegetable oil samples from Zhejiang Province of China, and none of the target compounds were detected.

Simultaneous determination of 17 phthalate esters in edible vegetable oils by GC-MS with silica/PSA-mixed solid-phase extraction.

A quantified method for the determination of 17 phthalate esters (PAEs) in edible vegetable oil by GC-MS with the pretreatment of acetonitrile extraction and silica/N-(n-Propyl)ethylenediamine-mixed SPE column was established. By the quantification of internal standard of D(4)-di(2-ethylhexyl) phthalate, a good linearity range of related 17 PAEs was observed. The correlation coefficient was ranged at 0.994~1.000, and the standard lowest quantified level was 0.05~0.15 mg/L. The spiking recoveries of 17 PAEs were 78.3~108.9% with the relative standard deviations of 4.3~12.1% (n = 6). The method detection limits were 0.1~0.2 mg/kg. Meanwhile, PAEs were determined in 30 plastic buckets of edible vegetable oil from supermarkets in Hangzhou city of China. The survey of 30 oil samples showed di(2-ethylhexyl) phthalate (DEHP) had the 100% (30/30) detection rate. The levels of diisobutyl phthalate with 86.7% (26:30), di-n-butyl phthalate (DBP) with 70% (21:30) and diethyl phthalate with 10% (3:30) were detected. It was worth note that DBP with 16.7% (5:30) samples and DEHP with 10% (3:30) samples were beyond the regular migrating limit, which indicated that more attention should be paid to the PAEs in oil with plastic package.

[The determination of phthalic acid esters in edible vegetable oils by gas chromatography-mass spectrometry].

OBJECTIVE: We aimed to establish a quantified method for the 17 phthalate acid esters (PAE) in edible vegetable oil by gas chromatography-mass spectrometry (GC-MS) with the pretreatment of acetonitrile extraction and silica/N-(n-propyl)ethylenediamine (silica/PSA) mixed solid phase extraction column and evaluated the PAE of 25 edible oil samples from supermarkets in Hangzhou city. METHODS: The internal standard solution (D4-DEHP) was added in edible vegetable oil sample. The analytes were extracted by acetonitrile with 1 min vortex, and centrifuged at 3050×g for 5 min. The supernatant was then cleaned with silica/PSA column, and eluted with acetonitrile. The elution was dried with N2 flow at 50°C and diluted to 1.0 ml with hexane. Then, 17 PAE were tested by GC-MS and quantified with internal standards. The repeatability and sensitivity of the assay were evaluated. PAE were then determined in 25 plastic buckets of edible vegetable oil from supermarkets in Hangzhou city. RESULTS: By the quantification of internal standard of D4-DEHP, a good linearity range of related 17 PAE was observed. The correlation coefficient was 0.994-1.000 and the standard lowest quantified level was 0.05-0.15 µg/ml. The spiking recoveries of 17 PAE were 78.3%-108.9% with the RSD of 4.3%-12.1% (n=6). The method detection limits were 0.1-0.2 mg/kg. In 25 plastic buckets of edible vegetable oil from Hangzhou, DMP, DEP, DIBP, DBP and DEHP were detected at the range of <0.1-1.8 mg/kg and the detection rates were 12% (3/25), 24% (6/25), 100% (25/25), 96% (24/25) and 100% (25/25), respectively. Other 12 PAE was not detected. For DBP with the level of <0.1 to 1.3 mg/kg, the results of 16% (4/25) samples exceeded the regular migrating limit of 0.3 mg/kg. For DEHP of <0.2-1.8 mg/kg, the data of 12% (3/25) samples were beyond the regular migrating limit of 1.5 mg/kg. CONCLUSION: The pretreatment by silica/PSA mixed solid phase extraction column can satisfy the PAE determination requirements in edible vegetable oils. The DMP, DIBP, DEP, DBP and DEHP were detected from the survey of 25 edible oil samples in Hangzhou city.

[Stability of disintegration in health food].

OBJECTIVE: To study the change of disintegration of different formulation samples which stored in the artificial climate box or room temperature and provide the technical support for health food monitoring. METHODS: According to the method of Chinese Pharmacopoeia and British Pharmacopoeia. Appendix XII A. Disintegration 2010. Disintegration of the non-accelerate, accelerated after 1, 2 and 3 months samples were determined by the disintegrator, respectively. RESULTS: Sample properties, the ingredients of the samples, the proportions of the capsule and treatment methods have some effect on the stability of the disintegration. CONCLUSION: The disintegration time of health food will be changed particularly after they were accelerated under the condition of (38 +/- 1) degrees C/75% RH. Especially the disintegration time of soft capsules were significantly prolonged. The composition and properties of samples were the main factors that affected the disintegration.

[Determination of sennoside A and sennoside B simultaneously in health food by HPLC].

OBJECTIVE: To develop an analytical method for determination of sennoside A and sennoside B simultaneously in health food by high performance liquid chromatography (HPLC). METHODS: Samples were extracted by ultrasound extraction and determined by HPLC with a UV detector. Using a Synergi Hydro-RP (250 mm x 4.6 mm, 4 microm) column and a mixture of CH3CN: 1.0% CH3COOH (17:83) as mobile phase for separation. The detection wavelength was at 270 nm. The contents were calculated with an external standard. RESULTS: The linearity was good in the ranges of 1.40 - 28.0 microg/ml for sennoside A and 1.45 - 29.0 microg/ml for sennoside B. The average recovery rates of sennoside A and sennoside B were 85.2% -97.2% and 86.1% -96.2%. The RSD was 7.5% and 6.8%, the limit of detection was 0.8 mg/kg and 0. 6 mg/kg, and the limit df quantification was 2.1 mg/kg and 2.0 mg/kg for sennoside A and sennoside B respectively. CONCLUSION: The method is simple, accurate and suitable for the determination of sennoside A and sennoside B in health food.

[Study on the determination method of the astragaloside IV in health food].

OBJECTIVE: To built an analytical methods to test Astragaloside NV in health food. METHODS: The reaction conditions of ultrasonic extraction, liquid-liquid extraction, macroporousresin column chromatography, solid-phase extraction, derivatization and HPLC method were analyzed. RESULTS: The sample preparations were set up as followed: The samples were extracted with methanol. The extraction solutions were liquid-liquid extracted by ether, water-saturation n-butyl alcohol and 1% KOH. The extraction solutions were further purified by DM-301 macroporousresin column chromatography and Oasis HLB 3cc extraction catridge in turn. The purified solutions were derived with chloroform and benzoyl chloride. The linear ranges were 3.84 - 153.60 microg/ml. The detection limits were 2.13 microg/ml. The recoveries were 74.85% - 91.83%. CONCLUSION: The method was applied to detect the concentration of Astragaloside IV in health food. It was enough to wipe out impurity of samples. Detection limit and recycle ratio were satisfied.

[A new method for safety monitoring of natural dietary supplements--quality profile].

OBJECTIVE: A new method for safety monitoring of natural dietary supplements--quality profile was proposed. It would convert passive monitoring of synthetic drug to active, and guarantee the security of natural dietary supplements. Preliminary research on quality profile was completed by high performance liquid chromatography (HPLC) and mass spectrometry (MS). METHODS: HPLC was employed to analyze chemical constituent profiles of natural dietary supplements. The separation was completed on C18 column with acetonitrile and water (0.05% H3PO4) as mobile phase, the detection wavelength was 223 nm. Based on HPLC, stability of quality profile had been studied, and abnormal compounds in quality profile had been analyzed after addition of phenolphthalein, sibutramine, rosiglitazone, glibenclamide and gliclazide. And by MS, detector worked with ESI +, capillary voltage: 3.5 kV, cone voltage: 30 V, extractor voltage: 4 V, RF lens voltage: 0.5 V, source temperature: 105 degrees C, desolvation temperature: 300 degrees C, desolvation gas flow rate: 260 L/h, cone gas flow rate: 50 L/h, full scan mass spectra: m/z 100-600. Abnormal compound in quality profile had been analyzed after addition of N-mono-desmethyl sibutramine. RESULTS: Quality profile based on HPLC had good stability (Similarity > 0.877). Addition of phenolphthalein, sibutramine, rosiglitazone, glibenclamide and gliclazide in natural dietary supplements could be reflected by HPLC, and addition of N-mono-desmethyl sibutramine in natural dietary supplements could be reflected by MS. CONCLUSION: Quality profile might monitor adulteration of natural dietary supplements, and prevent addition of synthetic drug after "approval".

Simultaneous determination of sildenafil, vardenafil and tadalafil as forbidden components in natural dietary supplements for male sexual potency by high-performance liquid chromatography-electrospray ionization mass spectrometry.

A high-performance liquid chromatographic method coupled with ultraviolet detection and electrospray ionization mass spectrometry (HPLC-UV-ESI-MS) was developed for simultaneous determination of banned additives-sildenafil, vardenafil and tadalafil in dietary supplements for male sexual potency. The separation was achieved on a C18 column with acetonitrile and aqueous solution (20 mmol ammonium acetate, 0.2% formic acid) as mobile phase at a flow rate of I ml/min with a linear gradient program. UV detection was at 292 nm. Identification of drugs was accomplished using ESI-MS. Good linearity between response (peak area) and concentration was found over a concentration range of 0.8-80 microg/ml for sildenafil; 2.25-225 microg/ml for vardenafil; and 1.1-110 microg/ml for tadalafil, with regression coefficient is better than 0.999. The recovery of the method ranged from 93.3 to 106.1%, and the relative standard deviation varied from 2.0 to 5.6% (n = 6). The method has been successfully applied to the analysis of practical samples of natural dietary supplements.

Simultaneous analysis of theanine, chlorogenic acid, purine alkaloids and catechins in tea samples with the help of multi-dimension information of on-line high performance liquid chromatography/electrospray-mass spectrometry.

A reverse phase high performance liquid chromatography (RP-HPLC) separation coupled with photo diode array detection (DAD) and electrospray ionization mass spectrometry (ESI-MS) detection was established for the analyzing of multiple bioactive compounds in tea and tea extracts. Theanine, chlorogenic acid, purine alkaloids and catechins were identified with authentic standard compounds and with MS-spectra. The content of theanine and catechins was measured by employing DAD and caffeine, chlorogenic acid, theobromine and theopylline by protonated molecular ion on selective ion recording (SIR) mode. The unity of LC/ESI-MS provides more qualitative and quantitative information comparing with general HPLC in the analysis of multi-components in tea, and complex extraction or sample pretreatment is unnecessary. The chromatogram acquired by using this method can be used as a bioactive components fingerprint for the quality control of tea and its extracts. With the help of multi-dimension information of HPLC-DAD-ESIMS, the compounds owning different chemical structure such as amino acid, catechins, etc. in tea and its extracts could be identified and determined in one run successfully.