A method for the simultaneous analysis of eight kinds of preservatives and sodium saccharin (SacNa) in food products using ion-pair high performance liquid chromatography (HPLC) was developed. The preservatives of interest were dehydroacetic acid (DHA), sorbic acid (SoA), benzoic acid (BA), ethyl p-hydroxybenzoate (Et-PHBA), propyl p-hydroxybenzoate (n-Pro-PHBA), isopropyl p-hydroxybenzoate (iso-Pr-PHBA), butyl p-hydroxybenzoate (n-Bu-PHBA) and isobutyl p-hydroxybenzoate (iso-Bu-PHBA). These food additives were separated on an inertsil ODS-2 column (150 x 4.6 mm I.D.) using 50 mM monosodium dihydrogenphosphate-acetonitrile solution (66:34) containing 2 mM cetyltrimethylammonium bromide as the mobile phase and detected with a photodiode array detector at 305 nm for DHA, 254 nm for SoA, Et-PHBA, n-Pr PHBA, iso-Pr-PHBA, n-Bu-PHBA and iso-Bu-PHBA, and 230 nm for BA and SacNa. Comparison of the measured spectra with reference spectra allowed qualitative analysis (Fig. 1 and 2). The combination of dialysis extraction and liquid extraction with organic solvent is often used for pretreatment. However, purification with large amounts of organic solvents after dialysis extraction is a serious concern in terms of inductrial hygiene. In addition, the use of many types of analytical instruments causes operational complexity. For these reasons, a new method for concentrating and purifying dialysis extracts was developed. A comparison of four types of mini-columns revealed the Sep-Pak PS-2 column to have the best retainability (Fig. 3). Ten ml of methanol was used as the eluent from this column (Fig. 4). When 3, 0.5 and 0.01 g/kg of standard substances were added to the samples, excellent average recoveries of 99.1% were achieved (Table 1). The results obtained from 21 samples, preservatives or SacNa being detected were in excellent agreement with the values of dialysis-gas chromatography (Table 2 and Fig. 5). Thus, combination of dialysis extraction and solid phase extraction facilitates handling of many samples of various types, reducing the work load and the amounts of organic solvents required.

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1) 1976～1981年 (昭和51～56年) の6年間, 札幌, 仙台, 東京, 山梨, 長野, 大阪・ 神戸, 和歌山, 島根, 北九州において, 安息香酸3, 319検体, デヒドロ酢酸1, 468検体, プロピオン酸1, 160検体, 類2, 424検体について分析を行なった。 各試料よりの検出率は, 安息香酸24.1%, デヒドロ酢酸6.5%, プロピオン酸20.1%, 類28.9%であった。
2) 国民栄養調査成績を用いた含量実態調査方式による1日総摂取量およびモデル献立から求めた推定値は, それぞれ安息香酸が10.9mg, 0.400mg, デヒドロ酢酸0.595mg, 0mg, プロピオン酸17.5mg, 0.177mg, 類1.011mg, 0.141mgであった。
3) FAO/WHOの評価によるADIの50kg体重値, すなわち安息香酸250mg, プロピオン酸1,000mg, 類500mgに対する本報告の摂取量はそれぞれ0.2～4.4%, 0.02～1.8%, 0.03～0.2%であった。

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Methods for the determination of six preservatives used in solid, semi-solid, and liquid foods were examined. Extraction procedures were divided into four steps : Step 1 : Extraction of preservatives from food with organic solvent. Step 2 : Separation of the preservatives from fatty substances by transfer of the former into an alkaline solution. Step 3 : Acidification of the alkaline layer with an acid followed by re-extraction of the acidic layer with an organic solvent. Step 4 : Concentration of organic solvent in vacuo and injection of an aliquot of the concentrate into an FID gas chromatograph. In Step 1, the homogenization and organic solvent extraction were carried out simultaneously in a Waring blender, since it had been confirmed that removal of protein and fat by use of suitable precipitant did affect the recovery of the preservatives. Ether was found to be suitable for the organic solvent of extraction. In Step 2, it became clear that the normality of the alkaline solution used must not be lower than 0.2. In order to avoid hydrolysis of p-hydroxybenzoates, 0.4 N potassium hydroxide solution in 50% methanol was finally chosen. In Step 3, the final pH of the solution must be brought to lower than 2 so that the preservatives may be successfully re-extracted with ether. In Step 4, the conditions for gas chromatography were as follows : Glass tube, 2 m in length, packed with 5% DEGS+1% H₃PO₄/Chromosorb W 60-80 mesh, column temp., 144° ; injection temp., 190° for sorbic acid, dehydroacetic acid, benzoic acid and salicylic acid ; glass tube, 1.5 m in length, packed with 3% SE-30/Chromosorb W 60-80 mesh, column temp., 180° ; injection temp. 230°for ethyl p-hydroxybenzoate and buthyl p-hydroxybenzoate. Recoveries were measured on Samsoe cheese, cream cheese, blue cheese, butter, wines, pickles, Korean ginseng extract, and honey, spiked at either 200 or 20 ppm of each preservative excluding SA. The recoveries at 200 ppm level ranged from 86.4 to 99.4%, while at 20 ppm level the recoveries were 84.0-95.1%. The minimum detection level of the 5 preservatives was 2 ppm.

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安息香酸および類とヘプタキス-(2,6-ジ-O-メチル)-β-シクロデキストリンの物理的混合物の熱的挙動を示差走査熱量測定(DSC)により検討した。DSC曲線上には2種類の吸熱ピークが認められた。IRスペクトル測定ならびに粉末X線回折測定からこれらの吸熱ピークはそれぞれ,包接化合物の形成,また包接化合物からのゲスト分子の放出に対応するものであることが確認された。

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食品防腐剤であるパラオキシ安息香酸のアルキルエステルが, J1ファージ感染L. casei菌細胞の早期溶菌を誘起することを見い出した.この早期溶菌は,感染初期に添加されたときでも生起した,早期溶菌誘起作用力は, iso-ブチル>n-ブチル>n-プロビル>iso-プロビル>エチルの順であった.エステル化されていない遊離のパラオキシ安息香酸は,この作絹を有しなかった.
早期溶菌は,ファージ感染による菌細胞膜の透過性の変化に起因するものであって,感染後に合成されるファージェンドリジンは,関与していないことが示された.
早期溶菌が起こる条件下で,遊離ファージは不活性化されなかった.種々検討して,細胞内ファージ定量のための条件を設定した.
の菌生育,菌生体高分子生合成,遊離ファージ,ファージ吸着およびファージ増殖に対する影響について検した結果も合わせ記述した.

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Alkyl p-hydroxybenzoates such as isobutyl p-hydroxybenzoate (PHBA-iBu), butyl p-hydroxybenzoate (PHBA-nBu), isopropyl p-hydroxybenzoate (PHBA-iPr), propyl p-hydroxybenzoate (PHBA-nPr), ethyl p-hydroxybenzoate (PHBA-Et), and methyl p-hydroxybenzoate (PHBA-Me) are widely used as preservatives, stabilizers and antiseptics for medical supplies, cosmetics, foodstuffs etc. We determined the binding affinity of alkyl p-hydroxybenzoates to human estrogen receptor α (ERα) and β (ERβ) by non-RI receptor binding assays. PHBA-iBu had a high binding affinity for ERα (IC₅₀ : 6.0×10^-6M, the relative binding affinity (RBA) : 0.267) and ERβ (IC₅₀ : 5.0×10^-6M, RBA : 0.340). These IC₅₀ values and RBA were almost the same as those of bisphenol A. The ranking of the estrogenic potency of alkyl p-hydroxybenzoates for both ERs is different; that is, PHBA-iBu>PHBA-nBu≒PHBA-iPr≒PHBA-nPr>PHBA-Et»PHBA-Me. Alkyl p-hydroxybenzoates bound with equal relative affinity to both ERα and β proteins. Alkyl p-hydroxybenzoate having a long alkyl side-chain showed a high affinity for ERα and β. These findings suggest that p-hydroxybenzoates may be endocrine disruptors.

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食品中の保存料の前処理法及び分析法についての検討を行った. 硫酸アンモニウム飽和溶液をリン酸でpH 2に調整することで, すべての保存料を同時に水蒸気蒸留することができた. 安息香酸, ソルビン酸, デヒドロ酢酸, 類は高速液体クロマトグラフィーで, プロピオン酸はガスクロマトグラフィーで分析した. 回収率は, 安息香酸89.3～101.4%, ソルビン酸96.3～100.8%, デヒドロ酢酸82.3～95.4%, 類84.7～103.5%, プロピオン酸96.7～100.8%であった.

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食品添加物の保存料として許可されている類 (エチル, n-プロピル, イソプロピル, n-ブチル, イソブチル) をトリフルオロアセチル化することによって, ガスクロマトグラフィーにより一斉に分離, 定量する方法を確立した.
また, トリフルオロアセチル誘導体は著しく揮発性であるため, 検出感度も良く, 低温度で分析可能であった.
これを用いて市販のしょう油10検体について定量分析を行ったところ, 簡易迅速定量法として十分適用できることを認めた.

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1) 1982年11月上旬～中旬に, 厚生省の食品添加物1日摂取量調査方式 (マーケットバスケット方式) に従い, 各種食品を, 東京で大手スーパーより, 東京, 大阪で中堅スーパーより, 仙台, 和歌山, 北九州で中小スーパーより, 札幌, 山梨, 長野, 島根で地元小売店より購入し, 1人1日喫食量に相当する試料量を採取し, 8食品群ごとに集め, 各種食品添加物含量を分析し, 1日摂取量を求めた。
2) 48品目の各種食品添加物の10機関の平均1日総摂取量は119.8mgであり, 個々の食品添加物の平均1日摂取量は, プロピレングリコール43mg, ソルビン酸36.3mg, 硝酸35.5mg, 安息香酸1.44mg, グリチルリチン酸1.39mg, サッカリンナトリウム0.91mg, プロピオン酸0.60mg, 類0.23mg, デヒドロ酢酸0.19mg, 合成着色料0.096mg, 亜硫酸0.073mg, BHT0.023mg, 亜硝酸0.018mg, BHA0.001mgであった。
3) 各種食品添加物の1日摂取量のADIに対する割合は, 天然由来も含む硝酸以外0～3%の範囲内にあり, 購入先の規模別では, 地元小売店の食品で保存料, 甘味料が多く, 中堅スーパーでは添加物含量が若干低い傾向が見られた。

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Sorbic acid (SOA), dehydroacetic acid (DA), benzoic acid (BA), and five esters of phydroxybenzoic acid (PHBA) in imported fruit vinegars were first passed through a Sep-Pak C₁8 cartridge and then analyzed simultaneously by gas-liquid chromatography. In brief, the vinegar samples were further acidified with hydrochloric acid, the test solution was saturated with sodium chloride and stirred vigorously, and the solution was put on the cartridge. Acetone as the solvent gave satisfactory results. A wide-bore capillary column was used for the gas chromatography. An FFAP column was most suitable for analysis of SOA, DA, and BA, and an MS column was most suitable for analysis of the five esters of PHBA in terms of stability, separability and sensitivity. Five fruit vinegars, fortified with 20μg/ml of eight food presertives, gave recovery of 91.6-100.5%, and the coefficient variation was 0.16% to 2.23%. The detection limit was 2μg/ml for each vinegar. This method could be used for various vinegars and was superior to conventional systematic methods for the assay of food preservatives. By this method, analytical results for 20 samples of imported fruit vinegars showed that SOA was present at the concertration of l.0-6.5μg/ml in two red wine vinegars, two sherry vinegars, and a balsamic vinegar. BA was detected at the concentration of 2.8μg/ml in a cider vinegar.

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