Toxicities of Irgarol 1051 derivatives, M2 and M3, to two marine diatom species.

Irgarol 1051 is highly toxic to marine autotrophs and has been widely used as an antifouling booster biocide. This study tested the toxicities of two s-triazine derivatives of Irgarol, namely M2 (3-[4-tert-butylamino-6-methylthiol-s-triazin-2-ylamino]propionaldehyde) and M3 (2-methylthio-4,6-bis-tert-butylamino-s-triazine) to two marine diatom species, Skeletonema costatum and Thalassiosira pseudonana through standard acute (96h) and chronic (7d) growth inhibition tests. Results showed that both of the two chemicals significantly inhibited the growth of S. costatum (M2: 96h-EC50 = 6789.7 µg L-1, 7d-EC50 = 3503.7 µg L-1; M3: 96h-EC50 = 45193.9 µg L-1, 7d-EC50 = 5330.0 µg L-1) and T. pseudonana (M2: 96h-EC50 = 366.2 µg L-1, 7d-EC50 = 312.5 µg L-1; M3: 96h-EC50 = 2633.4 µg L-1, 7d-EC50 = 710.5 µg L-1), while their toxicity effects were much milder than Irgarol and its major degradation product M1. By comparing with previous findings, the susceptibilities of these s-triazine compounds to two tested species were ranked as: Irgarol > M1 ≫ M2 > M3. This study promotes future research efforts on better understanding of the ecotoxicities of M2 and M3, and incorporating such information to improve the current monitoring, risk assessment and regulation of the use of Irgarol.

Dual-Gated Transistor Platform for On-Site Detection of Lead Ions at Trace Levels.

On-site monitoring of heavy metals in drinking water has become crucial because of several high profile instances of contamination. Presently, reliable techniques for trace level heavy metal detection are mostly laboratory based, while the detection limits of contemporary field-based methods are barely meeting the exposure limits set by regulatory bodies such as the World Health Organization (WHO). Here, we show an on-site deployable, Pb2+ sensor on a dual-gated transistor platform whose lower detection limit is 2 orders of magnitude better than the traditional sensor and 1 order of magnitude lower than the exposure limit set by WHO. The enhanced sensitivity of our design is verified by numerically solving PNP (Planck-Nernst-Poisson) model. We demonstrate that the enhanced sensitivity is due to the suppression of ionic flux. The simplicity and the robustness of the design make it applicable for on-site screening, thereby facilitating rapid response to contamination events.

Glucuronide and Sulfate Conjugates of Bisphenol A: Chemical Synthesis and Correlation Between Their Urinary Levels and Plasma Bisphenol A Content in Voluntary Human Donors.

Bisphenol A (BPA) glucuronide and sulfate conjugates are major products of Phase II metabolism of BPA in humans. In the past, their determination in body fluids usually involves tedious enzymatic hydrolysis and multiresidual analysis. The recent availability of authentic standards of these conjugates enables our better understand of the human metabolism of BPA and the distribution of their metabolites in body fluids. In this work, we report the chemical synthesis and purification of BPA mono- and di-glucuronide and BPA mono- and di-sulfate. Their levels, as well as that of BPA, in 140 paired human plasma and urine samples collected randomly from voluntary donors in Hong Kong SAR, China, were determined by solid-phase extraction and liquid chromatography-tandem mass spectrometry (LC-MS/MS). BPA was found in more than 135 human plasma and urine samples. Its Phase II metabolites, ranging from N.D. to 36.7 µg g-1-creatinine, also were detected in 139 of the 140 urine samples. Good correlation (r = 0.911) between molar concentration of BPA in the plasma and that of "total urinary BPA" (i.e., ln [(BPA + ∑ BPA phase II conjugate)molar concentration]) was observed. Direct quantification of Phase II metabolites of BPA in human urine can be a useful assessment tool for population exposure to this potent endocrine disrupting chemical.

A Photo-Triggered Traceless Staudinger-Bertozzi Ligation Reaction.

The use of light to control the course of a chemical/biochemical reaction is an attractive idea because of its ease of administration with high precision and fine spatial resolution. Staudinger ligation is one of the commonly adopted conjugation processes that involve a spontaneous reaction between azides and arylphosphines to form iminophosphoranes, which further hydrolyze to give stable amides. We designed an anthracenylmethyl diphenylphosphinothioester (1) that showed promising Staudinger ligation reactivity upon photo-excitation. Broadband photolysis at 360-400 nm in aqueous organic solvents induced heterolytic cleavage of its anthracenylmethyl-phosphorus bond, releasing a diphenylphosphinothioester (2) as an efficient traceless Staudinger-Bertozzi ligation reagent. The quantum yield of such a photo-induced heterolytic bond-cleavage at the optimal wavelength of photolysis (376 nm) at room temperature is ≥0.07. This work demonstrated the feasibility of photocaging arylphosphines to realize the photo-triggering of the Staudinger ligation reaction.

Mechanisms of toxicity of hydroxylated polybrominated diphenyl ethers (HO-PBDEs) determined by toxicogenomic analysis with a live cell array coupled with mutagenesis in Escherichia coli.

Results of previous studies have indicated that 6-HO-BDE-47, the addition of the hydroxyl (HO) group to the backbone of BDE-47, significantly increased the toxicity of the chemical compared to its postulated precursor analogues, BDE-47 and 6-MeO-BDE-47. However, whether such a result is conserved across polybrominated diphenyl ether (PBDE) congeners was unknown. Here, cytotoxicity of 32 PBDE analogues (17 HO-PBDEs and 15 MeO-PBDEs) was further tested and the underlying molecular mechanism was investigated. A total of 14 of the 17 HO-PBDEs inhibited growth of Escherichia coli during 4 or 24 h durations of exposure, but none of the MeO-PBDEs was cytotoxic at the concentrations tested. 6-HO-BDE-47 and 2-HO-BDE-28 were most potent with 4 h median effect concentrations (EC50) of 12.13 and 6.25 mg/L, respectively, which trended to be lesser with a longer exposure time (24 h). Expression of 30 modulated and validated genes by 6-HO-BDE-47 in a previous study was also observed after exposure to other HO-PBDE analogues. For instance, uhpT was upregulated by 13 HO-PBDEs, and three rRNA operons (rrnA, rrnB, and rrnC) were downregulated by 8 HO-PBDEs. These unanimous responses suggested a potential common molecular signaling modulated by HO-PBDEs. To explore new information on mechanisms of action, this work was extended by testing the increased susceptibility of 182 mutations of transcriptional factors (TFs) and 22 mutations as genes modulated by 6-HO-BDE-47 after exposure to 6-HO-BDE-47 at the 4 h IC50 concentration. Although a unanimous upregulation of uhpT was observed after exposure to HO-PBDEs, no significant shift in sensitivity was observed in uhpT-defective mutants. The 54 genes, selected by cut-offs of 0.35 and 0.65, were determined to be responsible for "organic acid/oxoacid/carboxylic acid metabolic process" pathways, which supported a previous finding.

Design and synthesis of heterobimetallic Ru(II)-Ln(III) complexes as chemodosimetric ensembles for the detection of biogenic amine odorants.

The detection of neutral biogenic amines plays a crucial role in food safety. Three new heterobimetallic Ru(II)-Ln(III) donor-acceptor complexes, KPrRu, KNdRu, and KSmRu, K{[Ru((II))((t)Bubpy)(CN)4]2-Ln((III))(H2O)4} (where (t)Bubpy = 4,4'-di-tert-butyl-2,2'-bipyridine), have been synthesized and characterized. Their photophysical and X-ray crystallographic data were reported in this study. These complexes were found to be selective for biogenic amine vapors, such as histamine, putrescine, and spermidine, with a detection limit down to the ppb level. The sensitivities of these complexes to the amines were recorded as ~log K = 3.6-5.0. Submicron rods of the complexes, with a nanoscale diameter and microscale length, were obtained through a simple precipitation process. Free-standing polymeric films with different degrees of porosity were fabricated by blending the submicron rods with polystyrene polymer. The polymer with the highest level of porosity exhibited the strongest luminescence enhancement after amine exposure. Real time monitoring of gaseous biogenic amines was applied to real fish samples (Atlantic mackerel) by studying the spectrofluorimetric responses of the Ru(II)-Ln(III) blended polymer film.

A Dual-Enzyme Amplification Loop for the Sensitive Biosensing of Endopeptidases.

A rapid and sensitive approach for the detection of endopeptidases via a new analyte-triggered mutual emancipation of linker-immobilized enzymes (AMELIE) mechanism has been developed and demonstrated using a matrix metallopeptidase, a collagenase, as the model endopeptidase analyte. AMELIE involves an autocatalytic loop created by a pair of selected enzymes immobilized on solid substrates via linkers with specific sites that can be proteolyzed by one another. These bound enzymes are spatially separated so that they cannot act upon their corresponding substrates until the introduction of the target endopeptidase analyte that can also cleave one of the linkers. This triggers the self-sustained loop of enzymatic activities to emancipate all the immobilized enzymes. In this proof of concept, signal transduction was achieved by a colorimetric horseradish peroxidase-tetramethylbenzidine (HRP-TMB-H2O2) reaction with HRP that are also being immobilized by one of the linkers. The pair of immobilized enzymes were collagenase and alginate lyase, and they were immobilized by an alginate linker and a short peptide chain containing the amino acid sequence of Leu-Gly-Pro-Ala for collagenase. A detection limit of 2.5 pg collagenase mL-1 with a wide linear range up to 4 orders of magnitude was achieved. The AMELIE biosensor can detect extracellular collagenase in the supernatant of various bacteria cultures, with a sensitivity as low as 103 cfu mL-1 of E. coli. AMELIE can readily be adapted to provide the sensitive detection of other endopeptidases.

Synthesis and characterization of bromophenol glucuronide and sulfate conjugates for their direct LC-MS/MS quantification in human urine as potential exposure markers for polybrominated diphenyl ethers.

Bromophenol glucuronide and sulfate conjugates have been reported to be products of mammalian metabolism of polybrominated diphenyl ethers (PBDEs), a group of additive flame-retardants found ubiquitously in the environment. In order to explore their occurrence in human urine, four water-soluble bromophenol conjugates, namely, 2,4-dibromophenyl glucuronide, 2,4,6-tribromophenyl glucuronide, 2,4-dibromophenyl sulfate, and 2,4,6-tribromophenyl sulfate, were synthesized, purified, and characterized. An analytical protocol using solid-phase extraction and ion-paired liquid chromatography-electrospray tandem mass spectrometry (LC-ESI-MS/MS) quantification has been developed for the direct and simultaneous determination of these glucuronide and sulfate conjugates in human urine samples. The limit of detections for all analytes were below 13 pg mL(-1), with 73-101% analyte recovery and 7.2-8.6% repeatability. The method was applied to analyze 20 human urine samples collected randomly from voluntary donors in Hong Kong SAR, China. All the samples were found to contain one or more of the bromophenol conjugates, with concentration ranging from 0.13-2.45 µg g(-1) creatinine. To the best of our knowledge, this is the first analytical protocol for the direct and simultaneous monitoring of these potential phase II metabolites of PBDEs in human urine. Our results have also suggested the potential of these bromophenol conjugates in human urine to be convenient molecular markers for the quantification of population exposure to PBDEs.

Accumulation and biotransformation of BDE-47 by zebrafish larvae and teratogenicity and expression of genes along the hypothalamus-pituitary-thyroid axis.

Accumulation and effects of BDE-47 and two analogues, 6-OH-BDE-47 and 6-MeO-BDE-47, on ontogeny and profiles of transcription of genes along the hypothalamus-pituitary-thyroid (HPT) axis of zebrafish (Danio rerio) embryos exposed from 4 h post fertilization (hpf) to 120 hpf were investigated. The 96 h-LC(50) of the most toxic compound, based on teratogenicity, was 330 µg of 6-OH-BDE-47/L. 6-OH-BDE-47 significantly down-regulated expression of mRNA of thyroid stimulating hormone receptor (TSHR), thyroid hormone receptors (TRs, including TRα and TRß), sodium/iodide symporter (NIS), and transthyretin (TTR) while up-regulating expression of thyroglobulin (TG) and thyrotropin-releasing hormone (TRH). Spontaneous movement was affected by 1 mg of 6-OH-BDE-47/L or 5 mg of 6-MeO-BDE-47/L. BDE-47 did not alter activity of larvae at any concentration tested. 6-MeO-BDE-47 significantly up-regulated expression of mRNA of TRH, TRα, TRß and NIS. Both 6-OH-BDE-47 and 6-MeO-BDE-47 affected the thyroid hormone pathway. BDE-47 and 6-MeO-BDE-47 were accumulated more than 6-OH-BDE-47. 6-MeO-BDE-47 was transformed into 6-OH-BDE-47, but BDE-47 was not transformed into it. In summary, the synthetic brominated flame retardant, BDE-47, did not elicit the adverse effects caused by the other two analogues and appeared to have less toxicological relevance than the two natural product analogues 6-OH- and 6-MeO-BDE-47.

Dioxin-like potency of HO- and MeO- analogues of PBDEs' the potential risk through consumption of fish from eastern China.

Polybrominated diphenyl ethers (PBDEs) and their analogues, such as hydroxylated PBDE (HO-PBDEs) and methoxylated PBDE (MeO-PBDEs) are of interest due to their wide distribution, bioaccumulation and potential toxicity to humans and wildlife. While information on the toxicity/biological potencies of PBDEs was available, information on analogues of PBDEs was limited. Dioxin-like toxicity of 34 PBDEs analogues was evaluated by use of the H4IIE-luc, rat hepatoma transactivation bioassay in 384-well plate format at concentrations ranging from 0 to 10 000 ng/mL. Among the 34 target analogues of PBDEs studied here, 19 activated the aryl hydrocarbon receptor (AhR) and induced significant dioxin-like responses in H4IIE-luc cells. Efficacies of the analogues of PBDEs ranged from 5.0% to 101.8% of the maximum response caused by 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD-max) and their respective 2,3,7,8-TCDD potency factors (ReP(H4IIE-luc)) ranged from 7.35 × 10(-12) to 4.00 × 10(-4), some of which were equal to or more potent than some mono-ortho-substituted PCBs (TEF-(WHO) = 3 × 10(-5)). HO-PBDEs exhibited greater dioxin-like activity than did the corresponding MeO-PBDEs. Analogues of PBDEs were detected mostly in marine organisms. Of these 11 detected analogues of PBDEs, 6 were found to have measurable dioxin-like potency. Though some analogues of PBDEs exhibited significant dioxin-like potency as measured by responses of the H4IIE-luc transactivation assay, concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents ((PBDEs analogues)TEQ(H4IIE-luc)), calculated as the sum of the product of concentrations of individual PBDE and their ReP(H4IIE-luc), were less than the tolerance limit proposed by European Union and the oral reference dose (RfD) derived by U.S. Environmental Protection Agency, respectively. (Hazard Quotients (HQ) < 0.005) Additional investigations should be conducted to evaluate the toxic potencies of these chemicals, especially for 2'-MeO-BDE-28, 4-HO-BDE-90, 6-HO-BDE-47, and 6-MeO-BDE-47, which had been detected in other environmental media, including human blood.

Polybrominated diphenyl ethers (PBDEs) alter larval settlement of marine intertidal organisms across three phyla via reducing bacterial abundance on the biofilms.

Polybrominated diphenyl ethers (PBDEs) have been widely used as flame retardants over the last three decades, and are now ubiquitous in the marine environment. While the harmful effects of PBDEs on the abnormal development and reproductive impairment in mammals and fish are well documented, the effects on marine invertebrates remain virtually unknown. Using three model intertidal species accross three phyla, including the polychaete Hydroides elegans (Phylum Annelida), the gastropod Crepidula onyx (Phylum Mollusca), and the barnacle Balanus amphitrite (Phylum Arthopoda), this study demonstrated that (a) chronic exposure to BDE-47 (at spiking concentrations up to 1000 ng L(-1)) throughout the entire larval stage did not affect settlement, development or growth of all three species per se, despite bioaccumulation was clearly evident (measured body burden ranging from approximately 7000 to 13 000 ng BDE-47 g(-1) lipid), and (b) BDE-47, at measured concentrations of 15 and 113 ng g(-1) lipid, reduced the bacterial abundance in biofilms and resulted in a concomitant change in larval settlement pattern of all the model intertidal species across three phyla.

Toxicogenomic mechanisms of 6-HO-BDE-47, 6-MeO-BDE-47, and BDE-47 in E. coli.

Cytotoxicity of 6-HO-BDE-47 and its two analogues, BDE-47 and 6-MeO-BDE-47, and the associated molecular mechanisms were assessed by use of a live cell reporter assay system which contains a library of 1820 modified green fluorescent protein (GFP) expressing promoter reporter vectors constructed from E. coli K12 strains. 6-HO-BDE-47 inhibited growth of E. coli with a 4 h median effect concentration (EC50) of 22.52 ± 2.20 mg/L, but neither BDE-47 nor 6-MeO-BDE-47 were cytotoxic. Thus, 6-HO-BDE-47 might serve as an antibiotic in some living organisms. Exposure to 6-HO-BDE-47 resulted in 65 (fold change >2) or 129 (fold change >1.5) genes being differentially expressed. The no observed transcriptional effect concentration (NOTEC) and median transcriptional effect concentration (TEC50) based on transcriptional end points, of 6-HO-BDE-47 were 0.0438 and 0.580 mg/L, respectively. The transcriptional responses were 514- and 39-fold more sensitive than the acute EC50 to inhibit cell growth. Most of the genes that were differentially expressed in response to 6-HO-BDE-47 were not modulated by BDE-47 or 6-MeO-BDE-47. These results suggest that cytotoxicity of 6-HO-BDE-47 to E. coli was via a mechanism that was different from that of either BDE-47 or 6-MeO-BDE-47. Gene expression associated with metabolic pathways was more responsive to 6-HO-BDE-47, which suggests that this pathway might be the primary target of this compound.

Identification of nitrate sources in Taihu Lake and its major inflow rivers in China, using δ(15)N-NO(3)(-) and δ(18)O-NO(3)(-) values.

In the present study, δ(15)N and δ(18)O-NO(3)(-) values, as well as concentrations of some major ion tracers were determined in seasonal water samples from Taihu Lake and major watersheds to investigate the temporal and spatial variations of nitrate sources and assess the underlying nitrogen (N) biogeochemistry process. The results lead to the conclusion that the nitrate concentrations in Taihu Lake are lower in summer than that in winter due to the dilution effect of wet deposition. In winter, sewage and manure were the primary nitrate sources in major inflow rivers and North Taihu Lake (NTL), while nitrate sources in East Taihu Lake (ETL) probably derived from soil organic N. In summer, atmospheric deposition and sewage/manure inputs appear to play an important role in controlling the distribution of nitrates in the whole lake. The δ(18)O-NO(3)(-) values suggest that the nitrate produced from microbial nitrification is another major nitrate source during both winter and summer months. The variations in isotopic values in nitrate suggest denitrification enriched the heavier isotopes of nitrate in NTL in winter and in ETL in summer.

Heterobimetallic Ru(II)-Eu(III) complex as chemodosimeter for selective biogenic amine odorants detection in fish sample.

Gaseous biogenic amines such as putrescine, spermidine, aniline, and trimethylamine are important biomolecules that play many crucial roles in metabolism and medical diagnostics. A chemodosimetric detection assay has been developed for those gaseous amines by Ru(II)-Eu(III) heterobimetallic complexes, K{[Ru(II)((t)Bubpy)(CN)(4)](2)Eu(III)(H(2)O)(4)} (where (t)Bubpy = 4,4'-di-tert-butyl-2,2'-bipyridine). Synthesis, X-ray crystal characterization, and spectroscopic properties of this Ru(II)-Eu(III) heterobimetallic complex were reported. Binding properties of the Ru(II)-Eu(III) complex with common gases revealed that this complex is very selective to gaseous amine molecules. Sensitivity of this complex toward the amines was found as ∼log k() = 4.5-4.8. Real time monitoring of gaseous biogenic amines was applied to real fish samples (Atlantic mackerel) by studying the spectrofluorimetric responses of the Ru(II)-Eu(III) complex toward different biogenic amine concentration. GC/MS studies were also used as a reference for the studies. A linear spectrofluorimetric response was found toward biogenic amine concentration in real fish samples. This complex was found to respond specifically to those biogenic amines down to 10 ppb.

Photoassisted Fenton degradation of polystyrene.

Fenton and photoassisted Fenton degradation of ordinary hydrophobic cross-linked polystyrene microspheres and sulfonated polystyrene beads (DOWEX 50WX8) have been attempted. While the Fenton process was not able to degrade these polystyrene materials, photoassisted Fenton reaction (mediated by broad-band UV irradiation from a 250 W Hg(Xe) light source) was found to be efficient in mineralizing cross-linked sulfonated polystyrene materials. The optimal loadings of the Fe(III) catalyst and the H(2)O(2) oxidant for such a photoassisted Fenton degradation were found to be 42 µmol-Fe(III) and 14.1 mmol-H(2)O(2) per gram of the sulfonated polystyrene material. The initial pH for the degradation was set at pH 2.0. This photoassisted Fenton degradation process was also able to mineralize commonly encountered polystyrene wastes. After a simple sulfonation pretreatment, a mineralization efficiency of >99% (by net polymer weight) was achieved within 250 min. The mechanism of this advanced oxidative degradation process was investigated. Sulfonate groups introduced to the surface of the treated polystyrene polymer chains were capable of rapidly binding the cationic Fe(III) catalyst, probably via a cation-exchange mechanism. Such a sorption of the photoassisted Fenton catalyst was crucial to the heterogeneous degradation process.

Endocrine disruption effects of 2,2',4,4',6-pentabromodiphenylether (BDE100) in reporter gene assays.

Polybrominated diphenyl ethers (PBDEs) constitute an important group of flame retardants. 2,2',4,4',6-Pentabromodiphenylether (BDE100) is a prominent PBDE congener in some human populations. The potential of BDE100 to modulate responses mediated by the estrogen (ER), thyroid hormone (ThR) or androgen receptors (AR) were investigated by use of transactivation reporter gene assays. The African green monkey kidney CV-1 cell transiently transfected with the constructed reporter gene plasmid ERE-TATA-Luc and pUAS-tk-Luc with luciferase (Luc) under control of the estrogen response (ERE), or thyroid hormone response (ThRE) elements were used to evaluate (anti)estrogen and thyroid effects of BDE100. The (anti)androgenic potency of BDE100 was also evaluated by use of MDA-kb2 cells, which were stably transfected with MMTV-luciferase. The assays displayed appropriate responses to known natural estrogen 17ß-estradiol (E2), ThR ligand triiodothyronine (T3), and the AR agonist 5α-dihydrotestosterone (DHT). 10 or 50 µM BDE100 significantly up-regulated expression of Luc under control of the ER. Antiestrogenic potency was observed for BDE100 (IC50 = 6.21 µM). Co-exposure to 50 µM BDE100 significantly enhanced expression of Luc caused by 5 nM T3. BDE100 was antiandrogenic at 10 and 50 µM with an IC50 of 28.60 µM BDE100. These results suggest that BDE100 can modulate the endocrine system in multiple ways by interfering with several hormonal signaling pathways simultaneously.

Portable molecularly imprinted polymer-based platform for detection of histamine in aqueous solutions.

Histamine, which is a naturally occurring chemical in seafood, is known to cause undesirable inflammatory response when consumed in large amounts. Histamine is produced in unsafe amounts in colored seafood when improperly stored for just a few hours. Food and health regulatory bodies across the world have guidelines limiting the amount of histamine in fresh as well as processed seafood. Conventional histamine detection is performed in testing labs, which is a slow process and results in bottlenecks in the seafood supply-chain system. A system to rapidly detect the seafood histamine levels on site is very desirable for seafood suppliers. Herein, we describe an impedance-based histamine detection sensor built on a flexible substrate that can detect histamine in the range of 100-500 ppm. Moreover, our sensor discriminates histamine in the presence of DL-histidine and other biogenic amines, with the selectivity provided by molecular imprinting technology. As a proof of concept, a smartphone controlled, portable semi-quantitative histamine sensing device was fabricated that gave out reliable testing results for histamine in different test solutions as well as for real seafood. We believe this technology can be extended towards determination of other food contaminants in aqueous solutions.

A triphenylphosphonium-functionalised cyclometalated platinum(II) complex as a nucleolus-specific two-photon molecular dye.

An organometallic cyclometalated platinum(II) complex, [Pt(L(3))Cl][PF(6)], has been synthesised from a specially designed cyclometalating ligand, HL(3) (triphenyl{5-[3-(6-phenylpyridin-2-yl)-1H-pyrazol-1-yl]pentyl}phosphonium chloride), that contains a pendant carbon chain carrying a terminal cationic triphenylphosphonium moiety. Aside from its room temperature single-photon luminescent properties in solution, [Pt(L(3))Cl](+) can also produce two-photon-induced luminescence at room temperature upon excitation at 700 nm from a mode-locked Ti:sapphire laser. Its two-photon absorption cross-section in DMF at room temperature was measured to be 28.0x10(-50) cm(4) s photon(-1). [Pt(L(3))Cl](+) is able to selectively stain the cell nucleolus. This has been demonstrated by two-photon confocal imaging of live and methanol-fixed HeLa (human cervical carcinoma) and 3T3 (mouse skin fibroblasts) cells. This organelle specificity is likely to be related to its special affinity for proteins within cell nucleoli. As a result of such protein affinity, [Pt(L(3))Cl](+) is an efficient RNA transcription inhibitor and shows rather profound cytotoxicity. On the other hand, the organelle-specific labelling and two-photon-induced luminescent properties of [Pt(L(3))Cl](+) renders it a useful nuclear dye for the 3-dimensional reconstruction of optical sections of thick tissues, for example, mouse ileum tissues, by multiphoton confocal microscopy.

Tissue concentrations of polybrominated compounds in Chinese sturgeon (Acipenser sinensis): origin, hepatic sequestration, and maternal transfer.

Information on concentrations of polybrominated compounds in various tissues of wild fish is limited. Concentrations of polybrominated diphenyl ethers (PBDEs), methoxylated PBDEs (MeO-PBDEs), and hydroxylated PBDEs (OH-PBDEs) were measured in 12 organs and eggs of 17 female Chinese sturgeon (Acipenser sinensis). The highest concentrations of PBDEs (42.8+/-39.4 ng/g ww), and MeO-PBDEs (135+/-63.6 pg/g ww) occurred in adipose followed by liver (PBDEs: 25.0+/-27.0 ng/g ww, MeO-PBDEs: 32.3+/-29.1 pg/g ww) and eggs (PBDEs: 21.2+/-19.4 ng/g ww, MeO-PBDEs: 120+/-119 pg/g ww), and the highest concentration of OH-PBDEs was observed in liver (185+/-174 pg/g ww) and eggs (178+/-294 pg/g ww). The lack of in vitro transformation of 6-MeO-BDE47 or BDE47 by microsomes prepared from Chinese sturgeon liver suggests that most 6-OH-BDE47 was directly accumulated as a natural product. Lipid-normalization revealed preferential accumulation of PBDEs in liver, and ratios of concentrations between eggs and liver were 0.10+/-0.11 to 0.22+/-0.26, which was lower than that for MeO-PBDEs (6-MeO-BDE47: 0.57+/-0.60, 2'-MeO-BDE68: 0.65+/-0.85) and 6-OH-BDE47 (0.59+/-0.51). Concentrations of PBDEs were negatively correlated with age, but no significant relationships between concentrations of OH-PBDEs or MeO-PBDEs and age were observed.

Contribution of synthetic and naturally occurring organobromine compounds to bromine mass in marine organisms.

An extraction, separation, and purification method was developed for the identification and quantification of total bromine (TBr), extractable organobromine (EOBr), and five classes of identified EOBrs. Instrumental neutron activation analysis (INAA) was utilized to quantify EOBr and TBr. The method was then applied to liver samples of tuna, albatross, and polar bear collected from remote marine locations. Polybrominated biphenyls (PBBs), polybrominated diphenyl ethers (PBDEs), bromophenols (BRPs), hydroxylated (OH-) and methoxylated (MeO-) PBDEs were analyzed as identified EOBr. The majority of the bromine in these marine organisms was nonextractable or inorganic, with EOBr accounting for 10-28% of the TBr. Of the identified EOBr, in tuna and albatross, naturally occurring compounds, including MeO-PBDEs, OH-PBDEs, and BPRs, were prevalent. However, the identifiable EOBr in polar bears consisted primarily of synthetic compounds, including PBDEs and PBBs. Overall, 0.08-0.11% and 0.008-0.012% of EOBr and TBr, respectively, were identified. The proportion of EOBr that was identified in marine organisms was relatively small compared to the proportions for organofluorine and organochlorine compounds. This could be related to the great diversity of naturally occurring organobromine compounds in the environment. Naturally occurring brominated fatty acids were estimated to be the predominant compounds in the EOBr fraction.