The different decomposition properties of diazolidinyl urea in cosmetics and patch test materials.

BACKGROUND: Diazolidinyl urea is a formaldehyde-releasing compound that releases formaldehyde through its decomposition. However, there have been few reports about the decomposition properties of diazolidinyl urea in cosmetics and patch test materials. OBJECTIVES: The aim of this study was to show how diazolidinyl urea decomposes in cosmetics and patch test vehicles, and to determine which cosmetic compounds should be evaluated in patch test studies of diazolidinyl urea. METHOD: We fractionated diazolidinyl urea-dissolving buffers or diazolidinyl urea-containing cosmetics with high-performance liquid chromatography-photodiode array detector (HPLC-PDA), and characterized them in liquid chromatography-mass spectrometry (LC-MS) and (1) H-nuclear magnetic resonance studies. Diazolidinyl urea-containing cosmetics and diazolidinyl urea patch test materials were also analysed with HPLC-PDA and LC-MS. RESULTS: Diazolidinyl urea was decomposed to (4-hydroxymethyl-2,5-dioxo-imidazolidine-4-yl)-urea (HU) and (3,4-bis-hydroxymethyl-2,5-dioxo-imidazolidine-4-yl)-urea (3,4-BHU) in most of the cosmetic samples tested. The peak patterns of the patch test materials analysed with the HPLC-PDA were different from those of the cosmetic samples. CONCLUSIONS. The diazolidinyl urea-derived decomposition products differed between the cosmetics and patch test preparations. To test the contact sensitivity of the diazolidinyl urea present in cosmetics, patch tests with HU and 3,4-BHU in petrolatum should be performed.

Rapid determination of atropine and scopolamine content in scopolia extract powder by HPLC.

A rapid method that does not require a complicated preparation was developed for determining by HPLC the content of atropine (At) and scopolamine (Sc) in a sample of scopolia extract powder. The sample solution for HPLC was extracted using 0.1 mol/L HCl/methanol (8:2). At and Sc were separated using a pentafluorophenylpropyl column and detected at a wavelength of 210 nm. Acetonitrile-10 mmol/L ammonium acetate adjusted to pH 5.0 (8:2, v/v) was used as the mobile phase. The linearity was good in the 5.0-500 µg/mL range for At and 0.5-500 µg/mL range for Sc. The specificity for both At and Sc was satisfactory. The quantitation limits were 5.0 µg/mL for At and 0.5 µg/mL for Sc. The quantitative values of total alkaloid calculated using this method were higher (1.3-3.7%) than those obtained using the Japanese Pharmacopoeia Fifteenth Edition (JP15) method. The precision of this method, measured as the standard deviation, was found to be satisfactory and comparable to that of the JP15 method, determined by an analysis of 3 commercial scopolia extract powder samples.

Simultaneous measurement of diazolidinyl urea, urea, and allantoin in cosmetic samples by hydrophilic interaction chromatography.

A new HPLC method for simultaneous measurement of diazolidinyl urea (DU), urea, and allantoin by hydrophilic interaction chromatography using a column packed with triazol-bonded silica particles is described. The calibration curves of DU, urea, and allantoin were linear over the ranges 2.5-125.0, 30-1250, and 0.25-18.75mg/L, respectively. The recoveries of DU, urea, and allantoin from homemade cosmetic samples ranged from 92.84% to 101.69%, 98.19% to 103.22%, and 95.75% to 102.09%, respectively. The peak relative standard deviation (RSD) values for the recovery tests of 3 concentrations/5 replicates were 3.03% for all compounds. In day-to-day measurement of recovery tests from homemade lotions over 3 consecutive days, the RSDs were less than 2.5% in all cases. This method was well validated and would be helpful for quickly analyzing these compounds in cosmetic samples.

Determination of pyrethroid pesticides in cinnamomi cortex.

In Japan, maximum residue levels (MRL) have been set for eight pesticides (alpha-BHC, beta-BHC, gamma-BHC, delta-BHC (BHCs), p,p'-DDE, o,p'-DDT, p,p'-DDD, p,p'-DDT (DDTs)) in 14 crude drugs (below 0.2 ppm as total of BHCs, below 0.2 ppm as total of DDTs). There are fears that pesticides present in crude drugs for which MRL are set will be changed from BHCs and DDTs to other pesticides with MRL setting as the turning point. There are few surveys of pyrethroid pesticide in crude drugs distributed in Japan. The actual situation of pyrethroid pesticides in crude drugs distributed in Japan after setting MRL is not unclear and should be clarified. Although a method to analyze permethrin, cypermethrin and fenvalerate in 11 crude drugs was reported, it is not adequate because the recovery rates of permethrin, cypermethrin and fenvalerate from Cinnamomi cortex were very low and the method, including liquid-liquid partition is difficult. In this study, we developed a method using solid-phase extraction to analyze permethrin, cypermethrin and fenvalerate in Cinnamomi cortex with acceptable recovery rates. The sample solution was determined by gas chromatography/mass spectrometry with negative chemical ionization. The recovery rates of permethrin, cypermethrin and fenvalerate from Cinnamomi cortex were between 87.9 and 90.7%. Five samples of Cinnamomi cortex were analyzed according to the proposed method. No samples contained permethrin, cypermethrin and fenvalerate over detection limits. The proposed method could analyze permethrin, cypermethrin and fenvalerate in all crude drugs for which MRL are set.

[Determination of sulfonamides in livestock products and seafoods by liquid chromatography/tandem mass spectrometry using glass bead homogenization].

A simple and rapid method using liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS) was developed for the determination of 25 kinds of sulfonamides in livestock products and seafoods. The sulfonamides were extracted with acetonitrile by glass bead homogenization and cleaned up with a tandem-connected ODS and basic alumina column. The quantification limits of 25 kinds of sulfonamides were 0.0025-0.005 microg/g. When two sulfonamides of specific samples were excluded, the recoveries and relative standard deviations were 70 to 120% and less than 15%. These results show that the developed method, which minimizes the matrix effect, offers high precision and should be useful for the determination of sulfonamides in livestock products and seafoods.

[Inhibitory effect of zinc on beta-hexosaminidase release from RBL-2H3 cells by synthetic chemicals].

The effects of foods and chemicals related to food hygiene on degranulation were evaluated using a method for assaying the enzyme activity of beta-hexosaminidase as an index of chemical mediator release from RBL-2H3 cells in vitro. Using a previously developed assay system, we had found a large number of inhibitors and promoters of degranulation of RBL-2H3 cells. In the present study, we examined the inhibitory effect of zinc chloride on the degranulation (beta-hexosaminidase release) from RBL-2H3 cells with or without antigen in the presence of the degranulation-promotive chemicals, namely, 4 food additives, 7 pesticides and 2 veterinary drugs. These promotive chemicals were classified into two types on the basis of inhibitory profile by zinc chloride: 1) those which showed marked degranulation-inhibitory action when the cells were stimulated with antigen, such as butylhydroxyanisole, dibutylhydroxytoluene, EPN, cis- and trans-permethrin, prothiofos, pyridaben, terbufos, 2) those which showed marked degranulation-inhibitory action whether the cells were stimulated with antigen or not, such as butyl p-hydroxybenzoate, o-phenylphenol, bitertanol, salinomycin. In conclusion, zinc had a dramatic inhibitory effect on enhanced degranulation induced by synthetic chemicals in vitro.

[Occurrence of an organochlorine synergist S-421 in fish and shellfish].

S-421 is a synergist for pyrethroid and organophosphorus pesticides, and is widely used in termiticides or commercial household insecticides. S-421 is mutagenic, stable and ubiquitous in the environment, and has been detected in household dust, surface water, sediments and rain-water. Here we describe the concentration of S-421 residues in domestic and imported fish collected in Osaka. S-421 was extracted with acetone/hexane, purified through silica gel 40 and quantified by ECD-GC. S-421 was detected in 36 out of 44 samples of domestic fish and shellfish analyzed, at a level of < 0.2 to 2.3 ng/g (mean: 0.6 ng/g), and in 27 out of 43 imported samples at a level of < 0.2 to 1.0 ng/g (mean: 0.2 ng/g). The levels of S-421 detected in fish were lower than those of DDTs and almost the same as those of HCHs. More attention should be paid to the behavior in the environment of S-421, as well as other persistent organochlorine pollutants, such as HCHs, DDTs and chlordane.

[Rapid analysis of aflatoxins in raw peanuts, corn, buckwheat and red pepper by a new mini-column cleanup and HPLC using post-column photochemical derivatization system].

A rapid and clean method for the analysis of aflatoxins (AFs) was developed by using a new column and post-column photochemical derivatization HPLC with fluorescence detection. The new cleanup column consisted of magnesia and basic alumina poured on the top of a commercial multi-functional mini-column. It was extremely effective for the cleanup of AFs from raw peanut, corn, buckwheat and red pepper. Fluorescent substances, which interfered with the analysis of AFs from corn, were completely absorbed at the top of the magnesia layer. Recoveries of AFs (B1, B2, G1, G2) added to raw peanuts, corn, buckwheat and red pepper were over 80% at two levels of fortification (higher level: 10, 3, 10, 3 ng/g, respectively, lower level: 1.0, 0.3, 1.0, 0.3 ng/g, respectively). Coefficients of variation were smaller than 12%, except the lower fortified level for red pepper. Limits of detection for AFs in raw peanuts, corn and buckwheat were 0.3 ng/g for B1 and G1, and 0.1 ng/g for B2 and G2. Those in red pepper were 0.5 ng/g for B1, B2, G1 and G2.

[Effects of veterinary drugs on beta-hexosaminidase release from rat basophilic leukemia cells (RBL-2H3)].

Little is known about the effects of residual veterinary drugs on the allergic reaction, except for the antigenicity of antibiotics and synthetic antimicrobials. Therefore, 59 kinds of veterinary drugs were investigated for their effects on the IgE receptor-mediated beta-hexosaminidase release from RBL-2H3 cells as an index of immediate allergic reaction. We found that the antibiotics chlorotetracycline, doxycycline, monensin, the synthetic antimicrobial pyrimethamine and the steroid hormone testosterone inhibited beta-hexosaminidase release. Most of the veterinary drugs showed no action, though the ionophores lasalocid, salinomycin and the steroid hormone hexestrol promoted beta-hexosaminidase release from injured cells. Based on the residual levels of these drugs and the frequencies of detection in actual food samples, it seems unlikely that these drugs have any immediate allergic effect in practice.