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A series of novel synthetic monohydroxy polychlorinated biphenyls (OH-PCBs) (5 trichloro-, 5 tetrachloro- and 5 pentachloro-compounds) have been characterized (1H and 13C NMR and high resolution MS) and their estrogenic and thyroid hormone activities assessed using a yeast two-hybrid assay, both with and without possible metabolic activation by rat liver S9 preparation. Moderate estrogenic activity was found for 2,3,4(')-trichlorobiphenyl-4-ol (compound 5) but this was eliminated when exposed to the S9 mix. 2,2('),3('),4,6-Pentachlorobiphenyl-3-ol (13) and 2('),3,3('),6-tetrachlorobiphenyl-4-ol (10) both showed weak estrogenicity in the absence of the S9 mix. The estrogenicity of compound (10) was enhanced 10-fold by exposure to S9 metabolic activation but that of compound (13) remained unchanged. 2('),4,5('),6-Tetrachlorobiphenyl-2-ol (6) showed strong thyroid hormonal activity (5% of that of T4) whereas 3('),4,6-trichlorobiphenyl-3-ol (4), compound (10) and 2,3('),4,5('),6-pentachlorobiphenyl-3-ol (14) showed moderate activity, and 2('),3,3('),5-tetrachlorobiphenyl-2-ol (8) and 3,3('),5,5('),6-pentachlorobiphenyl-2-ol (11) showed weak activity. The activity of (4) was eliminated by S9 metabolic activation whereas those of (6) and (14) were weakened and that of (10) remained unchanged.

Kidneys of clams of the genus Tridacna accumulate metabolic products from symbiotic unicellular algae that grow in the mantles of the clams. These metabolites include organoarsenic compounds that are biosynthesised by algae from arsenate in seawater. The arsenic compounds in aqueous extracts of the kidney of the giant clam T. derasa were investigated by liquid chromatography/electrospray ionisation mass spectrometry. About 50% of the water-soluble arsenic was present as dimethylarsinoylribosides and dimethylarsinate which are common algal metabolites. The major compound in the kidney (50% of water-soluble arsenic) was identified as a 5-dimethylarsinoyl-2,3,4-trihydroxycarboxylic acid, a new natural product., (Copyright 2001 John Wiley & Sons, Ltd.)

Background: Chemical speciation analysis is essential for the biological monitoring of inorganic arsenic exposure using urine as indicator medium. There is increasing demand for a certified reference material (CRM) of urine matrix for arsenic speciation., Methods: Urine (10 L) was collected from non-occupationally exposed Japanese males. We prepared 954 bottles of urine, each containing approximately 10 mL, after filtering and blending the urine stock. The urine in each bottle was freeze-dried. Between-bottle homogeneity was confirmed by measuring the concentrations of selected minor and trace elements in the material and subsequent statistical analysis. Certification was based on a collaborative analysis involving 15 laboratories., Results: Certified values were determined for arsenobetaine (0.069+/-0.012 mg As/L), dimethylarsinic acid (0.036+/-0.009 mg As/L), and total arsenic (0.134+/-0.011 mg/L) as well as for total selenium (0.059+/-0.005 mg/L) and zinc (0.62+/-0.05 mg/L), based on the analytical values from the collaborating laboratories. Reference values are given for copper (0.010 mg/L) and lead (0.0011 mg/L), based on definitive analysis at the National Institute for Environmental Studies (NIES)., Conclusions: The present CRM, NIES CRM No. 18 Human Urine, is the first human urine CRM for arsenic speciation and will be of value for analytical quality assurance of the biological monitoring of arsenic exposure.

Separation and 1H NMR spectra of a pair of arsenic-containing diastereoisomers (1a and 1b) isolated from a brown alga has provided support for their structures (proposed on the basis of NMR spectra of the unseparated mixture). The diastereoisomerism and analogies with nitrogen-containing algal lipids indicated that they were derived from an analogue of methionine in which the dimethylarsinoyl- group had replaced amino. Although S-adenosylmethionine is probably the source of methyl and 5'-deoxyribose-5'-yl groups in arsenic-containing natural products, the arsenic-carbon bonds in some compounds might be formed by a process in which arsenic replaces nitrogen in amino-acid synthesis.

Mussels (Mytilus edulis) were exposed to trimethyl(carboxymethyl)arsonium bromide (arsenobetaine, C-1 betaine), trimethyl(2-carboxyethyl)arsonium bromide (C-2 betaine), or trimethyl(3-carboxypropyl)arsonium bromide (C-3 betaine). Arsenic was accumulated by the mussels in all cases but the efficiency of uptake decreased with the number of methylene units in the carboxyalkyl group. Arsenobetaine (C-1 betaine) was the most readily accumulated, followed by the C-2 betaine (70% as efficient as arsenobetaine) and the C-3 betaine (approximately 7%). Chromatographic analysis (HPLC-ICPMS) of extracts of the mussels demonstrated that the arsenic compounds were accumulated unchanged. A 46-day depuration period which followed exposure did not significantly reduce the arsenic concentration in any of the three groups. Comparison with previous data on accumulation of arsenic compounds by M. edulis indicates that uptake may be influenced by the presence of a quaternary arsonium group and the zwitterionic nature of the arsenic-betaines.

The digestive gland of the western rock lobster, Panulirus cygnus, was shown to contain phosphatidylarsenocholine and a phosphatidyldimethylarsinylriboside by HPLC ICP-MS examination of lipid materials rendered water-soluble by hydrolysis. Water-soluble arsenic material in the digestive gland was chiefly arsenobetaine but the deacylated analogue of the phosphatidyldimethylarsinylriboside and an unidentified compound were also present.

It is ten years since arsenobetaine was first isolated from the western rock lobster Palinurus cygnus. Subsequently this naturally-occurring arsenical has been found in many species of marine animals contributing to the human diet. The identification of arsenic-containing ribofuranosides in algae and the production of dimethylarsinoylethanol from their anaerobic decomposition has allowed speculation on arsenic metabolism in marine organisms and has suggested a possible route to arsenobetaine from oceanic arsenate.

A new angiotensin converting enzyme inhibitor, enalaprilic acid (MK-422), was given in a bolus of 0.5 mg/kg i.v., followed by an infusion of 0.25 mg/kg/hr to determine its effects in hemorrhagic shock. MK-422 produced no significant hemodynamic effects in sham shock controls, yet it effectively blocked the pressor effect of exogenously administered angiotensin I throughout the 260-min experimental period and reduced angiotensin converting enzyme activity by 90% as determined by radiochemical assay. In vitro studies on cat papillary muscles and pancreatic homogenates revealed no direct inotropic or antiproteolytic effect of enalaprilic acid. Nevertheless, converting enzyme inhibitor treatment maintained postreinfusion mean arterial blood pressure at a significantly higher value (P less than .01) than that of untreated hemorrhaged animals (66 +/- 5 vs. 27 +/- 10 mm Hg, respectively). Superior mesenteric artery flow for hemorrhaged cats was significantly higher (P less than .05) in the treated group both during the end of the oligemic period (6.1 +/- 0.4 vs. 3.8 +/- 0.8 ml/kg/min) and during the postreinfusion period (6.5 +/- 0.7 vs. 1.9 +/- 1.0 ml/kg/min). Moreover, enalaprilic acid blunted the marked rise in plasma cathepsin D (P less than .01) and myocardial depressant factor activities (P less than .01), and plasma amino-nitrogen concentrations (P less than .05) observed in the untreated hemorrhaged cats. These results indicate that enalaprilic acid improved the hemodynamic and metabolic status of cats in hemorrhagic shock.

1. Samples of tail muscle of the western king prawn, Penaeus latisulcatus collected from two locations were examined separately for the presence of arsenobetaine and other arsenic compounds. 2. For both samples the aqueous extract accounted for greater than 97% of the total arsenic. 3. The water-soluble arsenic was present as one compound only which was isolated and identified as arsenobetaine.

Oral administration of sodium arsenate to estuary catfish (Cnidoglanis macrocephalus) and school whiting (Sillago bassensis) resulted in an accumulation of trimethylarsine oxide in their tissues. The levels of arsenobetaine, which occurs naturally in these fish, did not appear to be affected by the oral dosing with sodium arsenate. Trimethylarsine oxide also occurred as a natural component of estuary catfish and its presence may be related to the mode of feeding of this fish.

Groups of yelloweye mullet (Aldrichetta forsteri) were maintained for several weeks on diets containing one of a range of organoarsenic compounds (arsenobetaine, arsenocholine, 2-dimethylarsinylethanol, 2-dimethylarsinylacetic acid, 2-dimethylarsinothioylethanol) or arsenate. Fish fed 2-dimethylarsinylethanol, 2-dimethylarsinylacetic acid or 2-dimethylarsinothioylethanol showed no increase in arsenic concentrations in their muscle tissue, while fish fed arsenate showed small increases. The two groups of fish which received either arsenobetaine or arsenocholine had greatly elevated arsenic concentrations in their muscle tissue resulting from an estimated approximately 40% retention of ingested arsenic. Examination of the form of arsenic accumulated by fish fed arsenocholine showed that most of the arsenic (89%) was accumulated as arsenobetaine.