Separation, synthesis and estrogenic activity of 4-nonylphenols: two sets of new diastereomeric isomers in a commercial mixture

Two sets of new diastereomeric 4-nonylphenol (NP) isomers [4-(3,4-dimethylheptan-4-yl)phenol (344NP, NP-J, L) and 4-(3,4-dimethylheptan-3-yl)phenol (343NP, NP-K, P)] were separated from a commercial NP mixture. The mixture of these diastereomers was synthesized at the same time by a single Friedel-Crafts reaction of 3,4-dimethyl-4-heptanol and phenol, and the mixture was separated into individual NPs by HPLC equipped with Hypercarb column. For the first time, in this study the stereostructure-estrogenic activity relationship of NP diastereomers was investigated. The NP isomers (NP-L and NP-P) having the beta-methyl group over the benzene ring were found to be 2-4 times more estrogenic than their diastereomers (NP-J and NP-K). In the case of the other set of diastereomer [4-(3,5-dimethylheptan-3-yl)phenol, (353NP, NP-E, G)] containing gamma-methyl group in the molecule, the gamma-methyl proton signal (delta 0.49) in the more estrogenic isomer (NP-G) also appeared in a higher field than the corresponding methyl signal (delta 0.76) of the less estrogenic isomer (NP-E).     

Estrogen equivalent concentration of 13 branched para-nonylphenols in three technical mixtures by isomer-specific determination using their synthetic standards in SIM mode with GC-MS and two new diasteromeric isomers

Thirteen isomers of branched para-nonylphenols (para-NP) in three technical mixtures were isomer-specifically determined using their synthesized standards by SIM of structurally specific ions, m/z 135, 149 or 163 with GC–MS. Of the 13 isomers, four isomers, 4-(2,4-dimethylheptan-4-yl)phenol, 4-(4-methyloctan-4-yl)phenol, 4-(3-ethyl-2-methylhexan-2-yl)phenol (3E22NP) and 4-(2,3-dimethylheptan-2-yl)phenol synthesized for their determinations were first used as standard substances. The 13 isomers in the technical mixtures individually occurred at mass percent portion of more than 2%. The total mass percent portions in the mixtures from Tokyo Chemical Industry (TCI), Aldrich, and Fluka covered with 89 ± 2%, 75 ± 4% and 77 ± 2%, respectively. The abundance of 4-(3,6-dimethylheptan-3-yl)phenol in the three mixtures was the largest with 11.1 ± 2% to 9.9 ± 0.3%, while that of 4-(2-methyloctan-2-yl)phenol was the smallest with 2.9 ± 0.3% to 3.0 ± 0.2%. Additionally, structures of four new isomers of more than 1% portion present in a technical mixture were elucidated as two pairs of diastereomeric isomers: two types of 4-(3,4-dimethylheptan-4-yl)phenol (344NP) and those of 4-(3,4-dimethylheptan-3-yl)phenol (343NP). By estrogenic assay of 13 isomers with yeast estrogen screen system, the activity of 3E22NP was the highest, while that of 4-(3-methyloctan-3-yl)phenol was the least. Their relative activities to that of 3E22NP were individually calculated. Estrogenic equivalent concentrations of the three technical mixtures were predictively evaluated. The ratio of the EEC to the conventional concentration, total mass percent portions of the 13 isomers in technical mixtures were 0.208 for TCI, 0.206 for Aldrich and 0.205 for Fluka. The predicted estrogenic activity of measured concentration of para-NP in technical mixtures was approximately 5-fold greater than the measured estrogen agonist activity.     

Study on 14C-BHA absorption and distribution in rat

BHA was administered to rats at doses of 5 or 500 mg/kg for seven days. ¹⁴C-BHA absorption was investigated on the eighth day and compared with animals receiving a single dose of 5 or 500 mg/kg BHA. Absorption of ¹⁴C-BHA was proportionately greater at the high dose rats. ¹⁴C distribution was 3–6 times higher in the forestomach than in the pyloric region of the stomach. The urinary excretion of BHA conjugates was not dependent on pretreatment with BHA or on the dose.     

Polychlorinated dibenzo-p-dioxins and related compounds: correlations of levels in human tissues and in blood

We investigated PCDDs and related compounds levels in human tissue and blood obtained from the general population, and the correlation factor was calculated from the findings. None of the congeners in brain, muscle and lung were correlated except for 2,3,7,8-tetrachlorodibenzo-p-dioxin and octachlorodibenzo-p-dioxin in the brain (p < 0.05). In other tissues, all congeners had relatively good correlations to those in blood (r > 0.707). These congeners detected in blood were at high concentrations in the environment and human body. Therefore, we concluded that these congener levels in the blood might be useful for estimating these congener levels in human tissue.     

Comparison of chorionic villus sampling and amniocentesis: Current status of prenatal diagnosis in Japan

Data were tabulated and compared for cases involving prenatal diagnostic procedures performed in the 8 years between January 1985 and December 1992. Of a total of 2781 pregnancies, 2546 cases (91·5 per cent) were diagnosed by amniocentesis, and 235 (8·5 per cent) by chorionic villus sampling (CVS). These findings reflect the fact that amniocentesis has taken deep root as the prenatal diagnostic procedure widely acknowledged by society, whereas even the existence of CVS has yet to be generally recognized. Analysis of our clinical and laboratory results and complication rates, however, suggests that CVS is a safe and accurate alternative to amniocentesis which should and can be positively presented to all patients who are candidates for prenatal diagnosis.     

Effects of a composition change of ordinary Portland cement on waste utilization and CO2 emissions in Japan

Journal of Material Cycles and Waste Management - This paper estimates the effects of a composition change of ordinary Portland cement on waste utilization and CO2 emissions in the Japanese cement...     

In vitro evaluation of atmospheric particulate matter and sedimentation particles using yeast bioassay system.

Little information on the evaluation of airborne particulate matter (APM) and sedimentation particles from subway stations is available. The thermal metamorphism of train wheels generating toxic particles in subway stations is a possibility. In this study, the toxicity and physiological effects of particles from subway stations were evaluated using a yeast bioassay system. Estrogenic and antiestrogenic activities of APM in APM extracts from subway stations were determined. No estrogenic activity was found in the APM fractions and their S9-activated APM samples. Sedimentation dust samples also showed no estrogen activity. In contrast, extracts from sedimentation dust samples showed antiestrogen activity. Marked yeast toxicity was observed in the samples extracted from sedimentation dust. Potent yeast toxicity was also found in the S9-activated extracts from sedimentation dust. The results suggest that sedimentation dust from a semiclosed area of a subway system has antiestrogen activity, although both the origin and generation system of this activity are uncertain. These pollutants in sedimentation dust may change to a more toxic form in vivo by S9 activation.     

A case study of radon-222 transport from continental North-East Asia to the Japanese islands in winter by numerical analysis

A case study of the regional transport ( approximately 3000 km) of radon-222 ((222)Rn) from continental North-East Asia to the Japanese islands was performed by numerical analysis using five separate source areas (South, Middle and North China, Russia and Korea), while a seasonal northwest wind blew over the Japan Sea. The results for three periods (Term I: 16-18, Term II: 22-25 and Term III: 27-28 in December 1990) were compared with concentrations measured at the Kanazawa site (near the coast of the Japan Sea facing the seasonal wind) and the Nagoya site (overland and downwind on the shores of the Pacific Ocean). Most of the (222)Rn at the Kanazawa site was calculated to come from North China and Korea in Term I, Middle China, North China, and Korea in Term II, and Russia and Korea in Term III. The considerable differences in the origins of (222)Rn emanated from the continent were estimated between Terms I, II and III, even though the similar northwest wind was dominant over the Japan Sea. A contour line analysis indicated movement of (222)Rn emanated from Middle China in a northerly direction first and then a southeasterly direction, resulting from low pressure. The results suggest that the low-pressure systems play an important role in the transport of (222)Rn in North-East Asia.     

Evaluation of 14C abundance in soil respiration using acclerator mass spectrometry

To clarify the behavior of 14C in terrestrial ecosystems, 14C abundance in soil respiration was evaluated in an urban forest with a new method involving a closed chamber technique and 14C measurement by accelerator mass spectrometry (AMS). Soil respiration had a higher Delta14C than the contemporary atmosphere. This indicates that a significant portion of soil respiration is derived from the decomposition of soil organic matter enriched in 14C by atmospheric nuclear weapons tests, with a notable time lag between atmospheric 14C addition and re-emission from soil. On the other hand, delta14C in soil respiration demonstrated that 14C abundance ratio itself in soil-respired CO2 is not always high compared with that in atmospheric CO2 because of the isotope fractionation during plant photosynthesis and microbial decomposition of soil organic matter. The Delta14C in soil respiration was slightly lower in August than in March, suggesting a relatively high contribution of plant root respiration and decomposition of newly accumulated and/or 14C-depleted soil organic matter to the total soil respiration in August.     

Air pollution by concrete dust from the Great Hanshin Earthquake

Air pollution in the areas affected by the Great Hanshin Earthquake (Hyogo, Japan) of 17 Jan. 1995 was quite serious. We performed three investigations of dust. In the first investigation, we measured the total suspended particulate (TSP) concentration in the greatly damaged areas, located around the Sannomiya Station where a few hundred thousand people walked by during the daytime of 3 February. The maximum concentration at five points reached 150 microg/m3. In the second investigation, eight samples, which were classified into three groups (concrete, mortar, and soil dusts) as sources, were analyzed elementally by X-ray fluorescence. The elements found in concrete dust (Ca and S) were similar to those found in mortar dust. These differed from those found in soil dust (Ti, Fe, and Zr). The elements found in soil dust were important from the viewpoint of heavy metal contamination. In the third investigation, the alkalinity of concrete dust was observed by dissolution. This solution was equivalent to pH 11 to 12 and electrical conductivity 20 to 30 microS/m. We suspect that the alkaline component in the dust from debris in all the devastated areas was approximately comparable with the alkaline solution by which the acid rain falling over the Hanshin district of Osaka Megalopolis in one year could be neutralized into water of pH 7.0.