Instrumental neutron activation analysis of extractable organohalogens in marine mammal,harbour porpoise (<Emphasis Type="Italic">Phocoena phocoena</Emphasis>) and its feed,Atlantic herring (<Emphasis Type="Italic">Clupea harengus</Emphasis>), from the Baltic Sea

Instrumental neutron activation analysis (INAA) was conducted for the analysis of extractable organohalogens (EOX) in the blubber samples of harbour porpoise (Phocoena phocoena) and whole body samples of Atlantic herring (Clupea harengus) from the Baltic Sea. The concentration order of EOX was: extractable organochlorine (EOCl) > extractable organobromine (EOBr) > extractable organoiodine (EOI). As the results of investigation into the biomagnification properties of EOX, EOBr in low molecular weight fraction was the highest among the organic halogens investigated, suggesting the presence of high persistent organic bromine compounds in the marine environment, and accumulation through food chains.     

Neutron activation analysis of organohalogens in Chinese human hair

To effectively extract organohalogens from human hair, two factors, the extracting time and hair length on the extraction efficiency of organohalogens were studied by neutron activation analysis (NAA) and gas chromatograph-electron capture detector (GC-ECD), respectively. Furthermore, the concentrations of extractable organohalogens (EOX) and extractable persistent organohalogens (EPOX) in hair samples from angioma and control babies were also measured by the established method. The results indicated that the optimal Soxhlet-extraction time for EOX and EPOX in hair was from 8 to 11 hours, and the extraction efficiencies for organochlorine pesticides in hair were in the order of powder >2 mm>5 mm. Also, the mean levels of EOC1 and EPOC1 in hair of the angioma babies were significantly higher than those in the control babies (P _EOC1<0.01; P _EPOC1<0.05), which implied the possible relationship between the environmental pollution and angioma.     

Neutron activation analysis of extractable organohalogens in milk from China

Instrumental neutron activation analysis (INAA) has been used for the determination of extractable organohalogens (EOX) in milk. The detection limits are 50 ng, 8 ng and 3.5 ng for Cl, Br and I, respectively. The EOX concentrations in milk samples from various regions of China were determined. Meanwhile, organochlorine pesticides residues were detected by gas chromatography. The concentrations of the EOX in the milk samples are decreasing in the order of EOCl >> EOBr > EOI, and EOCl accounts for 95% of the total EOX. The average concentration of EOCl in milk is 4.44 ·g/g expressed as fat weight basis, with the highest value of 17.6 ·g/g from South China. The mean concentrations of total HCH and DDT are 0.038 ·g/g and 0.046 ·g/g, respectively. Organochlorine pesticides account only for 1.6% of the EOCl, indicating the very high proportion of the unknown EOCl in the milk sample. This revised version was published online in August 2006 with corrections to the Cover Date.     

Determination of extractable organohalogens in the atmosphere by instrumental neutron activation analysis

Summary Air samples were collected at a downtown site in Beijing from January to July 2004 and analyzed by instrumental neutron activation analysis (INAA) combined with organic solvent extraction method for the concentrations and distributions of extractable organohalogens (EOX), including extractable organochlorinated (EOCl), organobrominated (EOBr) and organoiodinated compounds (EOI). The concentrations of EOX were increasing in the order of EOCl >> EOBr ~ EOI in both gaseous and particulate phase. EOCl accounted for 75.8-100% and 83.7-100% of EOX in particulate and gaseous phase, respectively, suggesting that EOCl was the major component of the organohalogens in the atmosphere. In the plots of the logarithm of the EOX concentrations versus the reciprocal temperature, their linear relations were observed for EOCl (R = -0.9), for EOBr (R = -0.6) and EOI (R = -0.7) in gaseous phase, which indicated that the concentrations of EOCl, EOBr and EOI in gaseous phase exhibited a strong temperature dependence, i.e., their concentrations increased with increasing of temperature.     

Instrumental Neutron Activation Analysis of Extractable

Instrumental neutron activation analysis was performed to measure the levels of extractable organohalogens (EOX) in the organisms from the Antarctic marine ecosystem. The results show that EOX (EOCl, EOBr and EOI) were found in all the samples analyzed. The highest concentration was determined in the ascidian sample. The concentration order of EOX was mainly EOCl>EOBr>EOI with the exception of nemertine, ascidian, fish and adelie penguin samples. The concentrations of man-made organochlorines (DDTs and CHLs) were analyzed by GC-MS, and the results were compared with the concentrations of EOX determined in the same samples. The results show that the contribution of known man-made organochlorines in EOCl was less than 3%. This means that a large amount of unknown organochlorine compounds is present in Antarctic marine organisms.     

NAA for study of organohalogen levels in placenta, umbilical cord and hair of mothers with disabled newborns

The concentrations of extractable organohalogens (EOX) and extractable persistent organohalogens (EPOX) in placenta, umbilical cord and hair of mothers delivering disabled or normal newborns as well as the compositions of EPOCl in three analyzed matrices were determined by a combination of NAA, gas chromatography and chemical separation. The results indicated that both EOX and EPOX decreased in the order: hair > umbilical cord > placenta. Organochlorines were the major fraction of organohalogens. More than 77% of EPOCl were unidentified. High organohalogens exposure may induce adverse health effects, and hair, as a biomonitor for organohalogens assessment, is more recommendable.     

Study of organohalogen contaminants in yogurt by NAA and GC-ECD

The concentrations and distributions of total halogen (TX), extractable organohalogen (EOX) and extractable persistent organohalogen (EPOX) were determined in 20 kinds of yogurt specimens collected from Chinese supermarkets using neutron activation analysis (NAA) and gas chromatography equipped with a ⁶³Ni electron capture detector (GC-ECD). The results indicated that the halogens in yogurt mainly existed as non-extractable organohalogen compounds. About 25–30% of EOX was EPOX. EOCl and EPOCl were the main organohalogen species in yogurt. The average concentration of the identified organochlorine, such as organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs), was below 4% of EPOCl.     

INAA for the determination of extractable organohalogens in precipitation in Shanghai, China

The paper presents the results of determination of extractable organohalogens (EOX) by instrumental neutron activation analysis (INAA), and polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) by gas chromatography (GC), in atmospheric precipitation in Shanghai, China, from January to August 2005. The results showed that EOCI was the major component of organohalogens in precipitation. A significant correlation between the concentrations of EOBr and EOI was observed (r ² = 0.75), which suggested that EOBr and EOI in precipitation might mainly come from the same sources. There were no clear seasonal trends for the concentrations of EOX. The concentrations of ΣPCBs ranged from 0.2–2.8 ng/l, with the dominant PCBs containing 3 to 5 chlorine atoms. HCH was the predominant pesticide in precipitation, accounting for over 80% of total OCPs, in which β-HCH took 28%–72% of total HCH. Also, there may be an evidence for significantly historical usage of DDT.     

Recent trends of plutonium fallout observed in Japan: Comparison with natural lithogenic radionuclides, thorium isotopes

PM_2.5 and PM₁₀ samples were simultaneously collected monthly at a downtown site in Beijing from May 2002 to April 2003 and analyzed by instrumental neutron activation analysis (INAA) combined with organic solvent extraction method for the concentrations and distributions of extractable organohalogens (EOX), including extractable organochlorinated (EOCl), organobrominated (EOBr) and organoiodinated compounds (EOI). The concentrations of EOCl, EOBr and EOI were 10.5–79.2 ng/m³, ND-8.2 ng/m³ and 1.6–8.2 ng/m³ in PM_2.5, respectively, and 37.0–73.3 ng/m³, 1.6–12.8 ng/m³ and 1.6–8.5 ng/m³ in PM₁₀, respectively, which were increasing in the order of EOCl≫EOBr∼EOI. EOCl accounted for 73–88% and 69–91% of EOX in PM_2.5 and PM₁₀, respectively, which showed that EOCl was the major component of the organohalogens. There was a significant difference of EOCl concentrations in PM_2.5 and PM₁₀ in different seasons, which suggested that the concentrations of EOCl in the atmosphere were significantly affected by the meteorologic conditions and anthropogenic activities.     

Synthesis of multihydroxyl branched polyethers by cationic copolymerization of 3,3‐bis(hydroxymethyl)oxetane and 3‐ethyl‐3‐(hydroxymethyl)oxetane

The cationic ring‐opening polymerization of 3,3‐bis(hydroxymethyl)oxetane (BHMO) and the copolymerization of BHMO with 3‐ethyl‐3‐(hydroxymethyl)oxetane (EOX) were studied. Medium molecular weight polymers (number‐average molecular weight ≈ 2 × 10³) were obtained in bulk polymerization. Poly[3,3‐bis(hydroxymethyl)oxetane], as highly insoluble, was only characterized by gel permeation chromatography and NMR methods in the esterified form. Copolymers of BHMO and EOX that were slightly soluble in organic solvents were characterized in more detail. In a copolymerization from a 1:1 mixture, the comonomers were consumed at equal rates. Matrix‐assisted laser desorption/ionization time‐of‐flight analysis confirmed that a random 1:1 copolymer was formed. ¹³C NMR analysis indicated that in contrast to previously described homopolymers of EOX in which the degree of branching was limited, the homopolymers of BHMO were highly branched. This pattern was preserved in the copolymers; EOX units were predominantly linear, whereas BHMO units were predominantly branched. The copolymerization of BHMO with EOX provides, therefore, a route to multihydroxyl branched‐polyethers with various degrees of branching containing ? OH groups exclusively as ≡C? CH₂? OH units. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1991–2002, 2002     

Investigation of heavy-metal uptake by vegetables growing in contaminated soils using the modified BCR sequential extraction method

The heavy metal (Cu, Fe, Co, Ni, Cd, Cr, Pb, Zn, and Mn) concentrations in soils and in vegetable samples, i.e. lettuce (Lactuca sativa L.), parsley (Petroselinum crispum), dill (Anethum graveolens), and onion (Allium cepa L.), taken from three urban vegetable gardens in Kayseri, Turkey, were determined by FAAS. The modified three-step sequential extraction procedure proposed by the European Bureau of References (BCR), now the Standards, Measurements and Testing Programme, was used in order to evaluate trace elements mobility in soil samples, and heavy-metal uptake by vegetables. Three operationally defined fractions were isolated using the BCR procedure: acid extractable (i.e. bound to carbonates), reducible (bound to Fe/Mn oxides), and oxidizable (bound to organic matter and sulphides). The vegetable samples were prepared to analysis using the wet-ashing procedure. To estimate the accuracy of the method used in analysis of the vegetable samples, the standard reference material (NIST SRM 1573a, Tomato leaves) was used. The results of recovery for all the elements were relatively satisfactory (87.7–108%). For the soil samples, the recovery values were calculated by proportioning the sum of the steps of the BCR procedure to those of the pseudototal digestion (i.e. aqua regia). In soils, the mobility of heavy metals followed the order Mn>Cd>Cu>Pb>Zn>Cr>Ni>Co>Fe. The relationship between the vegetable–metal and soil–extractable metal concentrations was examined in order to evaluate the bioavailability of metals, and the positive correlation, especially for the first (i.e. water, acid-soluble and exchangeable fraction) and for the third (i.e. oxidizable fraction) extraction steps, was obtained.     

Syntheses,antitumor activities,and antiangiogenesis of exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalimidoethanoyl‐ 5‐fluorouracil and its polymers

A new monomer, exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalimidoethanoyl‐5‐fluorouracil (ETFU), was synthesized by the reaction of exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalimidoethanoyl chloride (ETPC) and 5‐fluorouracil (5‐FU). The homopolymer of ETFU and its copolymers with acrylic acid (AA) and vinyl acetate (VAc) were prepared via photopolymerizations with 2,2‐dimethoxy‐2‐phenylacetophenone at 25 °C for 48 h. The structures of the synthesized monomer and polymers were identified by Fourier transform infrared, ¹H NMR, and ¹³C NMR spectroscopy and elemental analysis. The ETFU contents in poly(ETFU‐co‐AA) and poly(ETFU‐co‐VAc) were 26 mol % and 26 mol %, respectively. The number‐average molecular weights of the polymers, as determined by gel permeation chromatography, ranged from 5600 to 17,000. The in vitro cytotoxicities of 5‐FU and the synthesized samples against mouse mammary carcinoma and human histiocytic lymphoma cancer cell lines increased in the following order: ETFU > 5‐FU > poly(ETFU‐co‐AA) > poly(ETFU) > poly(ETFU‐co‐VAc). The in vivo antitumor activities of the polymers against Balb/C mice bearing the sarcoma 180 tumor cells were greater than those of 5‐FU at all doses tested. The inhibitions of the samples for SV40 DNA replication and antiangiogenesis were much greater than the inhibition of the control. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4272–4281, 2000     

Chain‐growth limiting reactions in the cationic polymerization of 3‐ethyl‐3‐hydroxymethyloxetane

3‐Ethyl‐3‐hydroxymethyloxetane (EOX) polymerizes readily to branched multihydroxyl polyethers. Molecular weights of the polymers are, however, limited, and macromolecules are predominantly cyclic. This indicates that intramolecular chain transfer to polymer (back‐biting) proceeds in the system. Repeating units in poly‐EOX contain two nucleophilic sites that may participate in back‐biting, namely ether groups and hydroxyl groups. Analysis of matrix‐assisted laser desorption/ionization time‐of‐flight (MALDI‐TOF) mass spectra of poly‐EOX prepared in the presence of analogous polyether that does not contain HO? groups (poly(3,3‐dimethyloxetane)‐poly‐DMOX) shows that the ether group in the repeating unit of poly‐DMOX does not participate in chain transfer to the polymer. However, when DMOX was polymerized in the presence of poly‐EOX, clear evidence of participation of HO? groups in intramolecular chain transfer was obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 245–252, 2004     

Determination of d‐limonene in mice plasma and tissues by a new GC–MS/MS method: Comparison of the pharmacokinetics and tissue distribution by oral and inhalation administration in mice

The aim of the present study was to develop a method based on gas chromatography–tandem mass spectrometry (GC–MS/MS) to determine and quantify the d ‐limonene in mouse plasma and tissue samples. This new method was validated for the quantification of d ‐limonene with the linearity ranges 1.0–1000.0 ng/mL (r² > 0.9952) for plasma samples and 5.0–5000.0 ng/g (r² > 0.9940) for tissue samples. The intra‐ and inter‐day assay of precisions in plasma and tissues were <13.4% and the accuracies were within 91.1–105.8%. In the oral/inhalation administration pharmacokinetics and tissue distribution studies, the main pharmacokinetic parameters were the peak concentration = (97.150 ± 34.450)/(4336.415 ± 1142.418) ng/mL, the area under the curve = (162.828± 27.447)/(2085.721 ± 547.787) h ng/mL and the half‐life = (3.196 ± 0.825)/(0.989 ± 0.095) h. The tissue distribution of d ‐limonene in mice after oral/inhalation administration demonstrated a decreasing tendency in different tissues (liver > kidney > heart > lung > spleen).     

Advanced sample pretreatment for the monitoring of polycyclic aromatic hydrocarbons and extractable organic halogens in waste water. Flow based procedures with chromatomembrane cells

Polycyclic aromatic hydrocarbons (PAH) and extractable organic halogens (EOX) pollute industrial waste waters and need to be controlled continuously by automated procedures. Their sample pretreatment requires extraction first from complex matrices containing surfactants, humic acids, urine and electrolytes besides. When using chromatomembrane cells (CMC) for the extraction with pentane or hexane a flow based system can be established which preconcentrates the pollutants up to ratios of 100:1 at the same time. The extracted compounds become supplied to a gas chromatograph (PAH) using the split/splitless injection or to a combustion furnace (EOX), respectively. An aqueous solution later extracts the hydrogen halides from the exhaust gas for their simultaneous detection with an ion-chromatograph. The limits of lowest detection are attainable in the lower μg l⁻¹ range by matrix adjusted calibration. The CMC is a novel device containing a bloc of biporous PTFE which enables the contact of two immiscible phases. Polar liquids fill the macropores whereas the micropores remain available for non-polar liquids or gases.     

Molecular orientation and optical anisotropy in drawn films of cellulose diacetate-<Emphasis Type="Italic">graft</Emphasis>-PLLA: comparative investigation with poly(vinyl acetate-<Emphasis Type="Italic">co</Emphasis>-vinyl alcohol)-<Emphasis Type="Italic">graft</Emphasis>-PLLA

Cellulose diacetate-graft-poly(L-lactide) (CDA-g-PLLA) and poly(vinyl acetate-co-vinyl alcohol)-graft-PLLA (P(VAc-co-VOH)-g-PLLA) were synthesized over a range of compositions, by ring-opening copolymerization of L-lactide at the original hydroxyl positions of the respective trunk polymers, CDA (acetyl DS = 2.15) and P(VAc-co-VOH)-g-PLLA (VAc = 64.2 mol%). All the products of both graft copolymer series were non-crystallizable and their solution-cast films showed no domain segregation of the two components that constituted the trunk and side-chains. A comparative study on the molecular orientation and optical anisotropy induced by uniaxial stretching of film samples was undertaken for the two copolymer series with various side-chain lengths. Overall behaviour of the orientation was estimated from the statistical second (<cos² ω>) and fourth (<cos⁴ ω>) moments obtained by a fluorescence polarization method using a rod-like probe of ~2.5 nm. Upon stretching, any film of both series imparted a positive orientation function, i.e., f = (3 <cos² ω> − 1)/2 > 0, which increased with the extent of deformation. The degree of molecular orientation was higher in the CDA-graft series with a semi-rigid trunk, and, in both series, it declined monotonically with increasing content of the PLLA side-chain. With regard to the optical anisotropy, CDA-g-PLLA films always exhibited a positive birefringence (Δn > 0) upon stretching, while drawn films of P(VAc-co-VOH)-g-PLLA displayed a negative one. This contrast in polarity reflects a difference in the intrinsic birefringence between the two trunk polymers. Of interest was the finding of a discontinuous change in Δn value with copolymer composition (PLLA content) for the respective graft series, when compared at a given stage of elongation of the films. Discussion took into consideration the locally different orientation manners of the attached PLLA chain segments.     

The effects of dopant acids on structure and properties of poly(o‐methoxyaniline)

Poly(o‐methoxyaniline) (POMA) was chemically synthesized using ammonium persulfate (APS) as oxidant. Methane sulfonic acid (MSA), hydrochloric acid (HCl), and p‐toluene sulfonic acid (pTSA) were used as dopants, under the same reaction conditions. For comparison, undoped POMA was also synthesized. The polymer samples were characterized by Fourier transform infrared spectroscopy (FTIR), four‐probe conductivity measurement, scanning electron microscopy (SEM), electron spin resonance (ESR), gel permeation chromatography (GPC), and determination of specific surface area. The antioxidant activities of POMA were assessed via reaction with 1,1‐diphenyl‐2‐picrylhydrazyl (DPPH) free radical, and the anti‐microbial activities were determined as minimum bactericidal concentrations against E. coli 25422 and S. aureus 6838. When doped with relatively strong acids, high yield (above 84%) was achieved, compared to the relatively low yield (45%) when no dopant was present. The conductivity decreased in the order POMA‐pTSA > POMA‐HCl > POMA‐MSA > undoped POMA. A polaron conduction mechanism was supported by FTIR and ESR spectra. The morphology of the polymers was found to be effectively controlled by dopants. All POMA polymers showed strong free radical scavenging ability, which was highly correlated with the specific surface areas of the polymer particles. All the tested samples showed activity against S. aureus 6838, but not at the concentrations tested against E. coli 25422. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Syntheses and biological activities of α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil and its polymers

The new monomer, α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil (MMTFU), was synthesized from 5-fluorouracil (5-FU) and α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl chloride (MMTC). Poly(α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil) [poly(MMTFU)], poly(α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil-co-acrylicco-AA), and poly(α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil-co-vinyl acetate) [poly(MMTFU-co-VAc)] were synthesized by photopolymerizations using 2,2-dimethoxy-2-phenylacetophenone (DMP) as the photoinitiator. The synthesized MMTFU and the polymers were identified by FT-IR, ¹H-NMR, and ¹³C-NMR spectroscopies. The contents of MMTFU in poly(MMTFU-co-AA) and poly(MMTFU-co-VAc) determined by elemental analysis were 63 and 57 mol %, respectively. The number average molecular weights and polydispersity indices of synthesized polymers determined with GPC were in range of 7,700–19,100 and 1.6–2.7. The in vitro cytotoxicities of samples were evaluated with mouse mammary carcinoma (FM3A), mouse leukemia (P388), and human histiocytic lymphoma (U937) as cancer cell lines and mouse liver cells (AC2F) as a normal cell line. The cytotoxicities of 5-FU and synthesized samples against cancer cell lines increased in following orders: 5-FU > MMTFU > poly(MMTFU) > poly(MMTFU-co-AA) > poly(MMTFU-co-VAc). The in vivo antitumor activities of the synthesized samples against mice bearing the sarcoma 180 tumor cell line were evaluated. The in vivo antitumor activities of the polymers were greater than that of 5-FU at a dose of 80 mg/kg. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1625–1632, 1998     

Seasonal changes in arsenic speciation in Fucus species

Arsenic speciation in a brown alga, Fucus gardneri, collected in Vancouver, B.C., Canada, was carried out by using high-performance liquid chromatography–inductively coupled plasma–mass spectrometry (HPLC–ICP–MS). Hydride generation–atomic absorption spectrometry (HG–AAS) was used for total arsenic determination. The relative amounts of some arsenosugars 1 in growing tips are found to be different in comparison with the remainder of the plant. Fucus samples collected in summer contain 9 ppm of total arsenic. Most of the arsenic species are extractable. Fucus samples collected in winter contain relatively higher amounts of arsenic, 16–22 ppm, but only low amounts of this are extractable. © 1998 John Wiley & Sons, Ltd.