Motoh Mutsuga

Migration of lactic acid, lactide and oligomers from polylactide food-contact materials

Polylactide (PLA) is used for manufacturing lunch boxes and for packaging fresh food in Japan. PLA can be hydrolysed relatively easily to produce lactic acid, lactide and oligomers. Different types of PLA sheet were subjected to migration tests under various conditions and the lactic acid, lactide and oligomers contents of the migration solutions were determined using liquid chromatography/mass spectrometry (LC/MS). Furthermore, the change in molecular weight was determined by a migration test. PLA was stable at 40°C for 180 days; the total of lactic acid, lactide and oligomers migration levels were 0.28–15.00 µg cm−2. PLA decomposed clearly at 60°C for only 10 days, the total migration levels were increased to 0.73–2840 µg cm−2. PLA sheets with a high D-lactic acid content decomposed particularly rapidly. The amounts of alkali decomposition products, based on the conversion of lactide and oligomers to lactic acid by alkali hydrolysis, corresponded with the total migration levels.

Estrogenic activities of chemicals related to food contact plastics and rubbers tested by the yeast two-hybrid assay.

Food contact plastics and rubbers possibly contain many kinds of chemicals such as monomers, oligomers, additives, degradation products of polymers and additives, and impurities. Among them, bisphenol A, nonylphenol, benzylbutyl phthalate, styrene oligomers and hydroxylated benzophenones have been reported to possess estrogenic activities. In this study, other chemicals related to food contact plastics and rubbers, and their metabolites induced by the S9-mixture were tested for their estrogenic activities using the yeast two-hybrid assay. Among the 150 chemicals, 10 chemicals such as bis(4-hydroxyphenyl) methane, 4-cyclohexylphenol, 4-phenylphenol, 4,4′-isopropylidenediphenol alkylphosphite, two type of styrenated phenol (including mono type), tris(nonylphenyl) phosphite, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone and 2,4-diphenyl-4-methyl-1-pentene, their metabolites and the metabolites of 6 other chemicals, such as 2-(phenylmethyl) phenol, styrenated phenol (di and tri type), 1-(N-phenylamino)naphthalene, 4-tert-butylphenylsalicylate, nonylphenol ethoxylates and 2-methyl-6-tert-butylphenol, displayed estrogenic activities. All of them contained a phenol group in their chemical structures or formed one easily by hydrolysis or metabolism. However, most of the chemicals related to food contact plastics and rubbers, and their metabolites did not show any estrogenicity.

Survey of formaldehyde, acetaldehyde and oligomers in polyethylene terephthalate food-packaging materials.

Polyethylene terephthalate (PET) is frequently used as a packaging material for beverage bottles, fruit and vegetable trays, and egg crates in Japan. Levels of formaldehyde (FA), acetaldehyde (AA) and PET oligomers in various PET food packaging were determined. PET samples were initially dissolved in trifluoroacetic acid with 2,4-dinitrophenylhydrazine to derivatize formaldehyde and acetaldehyde to their dinitrophenylhydrazones. The stable derivatives along with the oligomers were analysed using HPLC with ultraviolet light detection at 360 and 254 nm, respectively. The PET pellets contained 3.5–12.4 µg g−1 AA and 4.0–7.2 mg g−1 oligomers, while FA was below the determination limit. FA, AA and oligomer levels in Japanese bottles were 0.6–3.0 µg g−1, 8.4–25.7 µg g−1 and 5.0–8.7 mg g−1, ND–1.6 µg g−1, 5.0–13.1 µg g−1 and 4.9–8.2 mg g−1 in French and Italian bottles, and ND–1.2 µg g−1, 9.1–18.7 µg g−1 and 5.6–8.0 mg g−1 in US and Canadian bottles, respectively. Compared with European bottles, Japanese bottles contain higher FA and AA levels. In sheet-moulding products, their contents were determined as ND–1.1 µg g−1, 11.5–43.1 µg g−1 and 4.6–9.2 mg g−1, respectively. The results show that sheet-moulding products contain lower FA and higher AA in comparison with bottles. FA and AA are considered to be generated from PET during the heating process for moulding the pellets to bottles or sheet-moulding articles and de-aeration during the sheet-moulding process is effective in removing FA. In contrast, the level of the oligomers remains unchanged during the moulding process from pellets to bottles or sheet products.

Two alkaloids from Zephyranthes carinata

Abstract Two new Amaryllidaceae alkaloids, 1- O -(3-hydroxybutyryl) pancratistanin and 1-O-(3-O-β- d -glucopyranosylbutyryl) pancratistatin, were isolated from the bulbs of Zephyranthes carinata . The structures of the two alkaloids were established by comprehensive spectral analysis. The cytotoxicity of these two alkaloids and pancratistatin is appraised.

Isolation and identification of some unknown substances in disposable nitrile-butadiene rubber gloves used for food handling

In Japan, disposable gloves made from nitrile-butadiene rubber (NBR) are frequently used in contact with foods. In a previous paper, we investigated substances migrating from various gloves made of polyvinyl chloride, polyethylene, natural rubber and NBR. Zinc di-n-butyldithiocarbamate (ZDBC), diethyldithiocarbamate (ZDEC) used as vulcanization accelerators, di(2-ethylhexyl)phthalate (DEHP) used as a plasticizer and many unknown compounds that migrated from NBR gloves into n-heptane were detected by GC/MS. In this paper, six unknown compounds were obtained from one kind of NBR glove by n-hexane extraction and each was isolated by silica gel chromatography. From the results of NMR and mass spectral analysis of the six unknown compounds, their structures are proposed as 1,4-dione-2,5-bis(1,1-dimethylpropyl)cyclohexadiene (1), 2-(1,1-dimethylethyl)-4-(1,1,3,3-tetra methylbutyl)phenol (2), 2,6-bis(1,1-dimethylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol (3), 2,4-bis(1,1,3,3-tetramethylbutyl)phenol (4), 2-(1,1-dimethylethyl)4,6-bis(1,1,3,3-tetramethylbutyl)phenol (5) and 2,4,6-tris(1,1,3,3-tetramethylbutyl)phenol (6). Compound 1 was observed in five of the seven kinds of NBR gloves, and compounds 2-4 and 6, which are not listed in Chemical Abstract (CA), were present in four kinds of gloves.

Bisphenol A in domestic and imported canned foods in Japan.

Bisphenol A (BPA) concentrations were surveyed in 100 domestic and 60 imported canned foods purchased from the Japanese market in 2011–12. BPA was extracted from the canned foods, derivatised by ethylation and analysed using GC-MS. In the domestic canned foods, the maximum and average BPA concentrations were 30 and 3.4 ng g−1, respectively, while in the imported canned foods they were 390 and 57 ng g−1, respectively. The BPA level in the domestic canned foods was significantly lower than that in the imported canned foods. Based on these results, the intakes of BPA from the domestic and imported canned foods in Japan were estimated as 644 ng person−1 day−1. The Japanese BPA intake was the second lowest following New Zealand, although imported canned foods increased. It was sufficiently lower than the tolerable daily intake of EFSA and the USEPA. The drastic reduction of BPA in the domestic canned foods should be due to the ‘BPA reduced cans’ that Japanese can manufacturers had developed in the late 1990s and became widely used in Japan.

Analytical methods for SiO2 and other inorganic oxides in titanium dioxide or certain silicates for food additive specifications

An analytical method has been developed for the detection of SiO2 and other oxides in titanium dioxide and certain silicates used in food additives using inductively coupled plasma (ICP) atomic emission spectrometry without hydrofluoric acid. SiO2 and other oxides in titanium dioxide or certain silicates were resolved by alkali fusion with KOH and boric acid and then dissolved in dilute hydrochloric acid as a test solution for ICP. The recovery of SiO2 and Al2O3 added at 0.1 and 1.0%, respectively, in TiO2 was 88–104%; coefficient of variation was <4%. The limit of determination of SiO2 and Al2O3 was about 0.08%, and the accuracy of the ICP method was better than that of the Joint FAO/WHO Expert Committee on Food Additives (JECFA) test method. The recovery of SiO2 and other oxides in silicates was 95–107% with a coefficient of variation of <4%. Using energy dispersive X-ray fluorescence spectrometry (EDX) with fundamental parameter determination, the content of SiO2 and other oxide in titanium dioxide and silicate showed good agreement with the ICP results. ICP with alkali fusion proved suitable as a test method for SiO2, Al2O3 and other oxides in titanium dioxide and certain silicates, and EDX proves useful for screening such impurities in titanium dioxide and componential analysis of certain silicates.

Survey of volatile substances in kitchen utensils made from acrylonitrile–butadiene–styrene and acrylonitrile–styrene resin in Japan

Residual levels of 14 volatile substances, including 1,3-butadiene, acrylonitrile, benzene, ethylbenzene, and styrene, in 30 kitchen utensils made from acrylonitrile–butadiene–styrene resin (ABS) and acrylonitrile–styrene resin (AS) such as slicers, picks, cups, and lunch boxes in Japan were simultaneously determined using headspace gas chromatography/mass spectroscopy (HS-GC/MS). The maximum residual levels in the ABS and AS samples were found to be 2000 and 2800 μg/g of styrene, respectively. The residual levels of 1,3-butadiene ranged from 0.06 to 1.7 μg/g in ABS, and three of 15 ABS samples exceeded the regulatory limit for this compound as established by the European Union (EU). The residual levels of acrylonitrile ranged from 0.15 to 20 μg/g in ABS and from 19 to 180 μg/g in AS. The levels of this substance in seven ABS and six AS samples exceeded the limit set by the U.S. Food and Drug Administration (FDA). Furthermore, the levels of acrylonitrile in three AS samples exceeded the voluntary standard established by Japanese industries. These results clearly indicate that the residual levels of some volatile compounds are still high in ABS and AS kitchen utensils and further observations are needed.

Quantification of isocyanates and amines in polyurethane foams and coated products by liquid chromatography-tandem mass spectrometry.

An analytical method for the identification and quantification of 10 different isocyanates and 11 different amines in polyurethane (PUR) foam and PUR-coated products was developed and optimized. Isocyanates were extracted and derivatized with di-n-butylamine, while amines were extracted with methanol. Quantification was subsequently performed by liquid chromatography–tandem mass spectrometry. Using this methodology, residual levels of isocyanates and amines in commercial PUR products were quantified. Although the recoveries of certain isocyanates and amines were low, the main compounds used as monomers in the production of PUR products, and their decomposition species, were clearly identified at quantifiable levels. 2,4-and 2,6-toluenediisocyanate were detected in most PUR foam samples and a pastry bag in the range of 0.02–0.92 mg/kg, with their decomposition compounds, 2,4-and 2,6-toluenediamine, detected in all PUR foam samples in the range of 9.5–59 mg/kg. PUR-coated gloves are manufactured using 4,4′-methylenebisphenyl diisocyanate as the main raw material, and a large amount of this compound, in addition to 4,4′-methylenedianiline and dicyclohexylmethane-4,4′-diamine were found in these samples.

Isolation and Quantification of Polyamide Cyclic Oligomers in Kitchen Utensils and Their Migration into Various Food Simulants

Small amounts of cyclic monomers and oligomers are present in polyamide (PA)-based kitchen utensils. In this study, we isolated eight PA-based cyclic monomers and oligomers from kitchen utensils made from PA6 (a polymer of ε-caprolactam) and PA66 (a polymer of 1,6-diaminohexane and adipic acid). Their structures were identified using high-resolution mass spectrometry and 1H- and 13C-nuclear magnetic resonance spectroscopy, and their residual levels in PA-based kitchen utensils and degree of migration into food simulants were quantified by high-performance liquid chromatography/mass spectrometry using purchased PA6 monomer and isolated PA66 monomers, and isolated PA6 and PA66 oligomers as calibration standards. Their total residual levels among 23 PA-based kitchen utensils made from PA6, PA66, and copolymers of PA6 and PA66 (PA6/66) ranged from 7.8 to 20 mg/g. Using water, 20% ethanol, and olive oil as food simulants, the total migration levels of the PA monomers and oligomers ranged from 0.66 to 100 μg/cm2 under most examined conditions. However, the total migration levels of the PA66 monomer and oligomers from PA66 and PA6/66 kitchen utensils into 20% ethanol at 95°C were very high (1,700 and 2,200 μg/cm2, respectively) due to swelling by high-temperature ethanol.