Abstract  A method based on liquid-liquid extraction (LLE) and automated large volume injection (LVI)GC-MS analysis was developed for the trace determination of phthalate di-esters in water samples at sub-mu g L-1 (ppb) levels. Strategies applied to reduce contamination include (i) careful selection of tools, glassware and solvents, (ii) systematic blank checks of the chromatographic system, glassware and solvents and (iii) frequent verifications of blanks during sequences. Background levels could be reduced to those present in the extraction solvent. For phthalates not present in the extraction solvent the limits of quantitation (LOQ) are 6 ng L-1 for di-methyl phthalate (DMP), 3 ng L-1 for benzylbutyl phthalate (BzBP) and 45 ng L-1 for the isomeric phthalate mixtures di-isononyl phthalate (DiNP) and di-isodecyl phthalate (DOP). For the other phthalates, the LOQ was set at twice the blank (extraction solvent) level and are 20 ng L-1 for di-ethyl phthalate (DEP), 60 ng L-1 for di-isobutyl phthalate (DiBP), 80 ng L-1 for di-n-butyl phthalate (DBP) and 30 ng L-1 for bis-(2-ethylhexyl) phthalate (DEHP).

Abstract  Diethyl phthalate (1,2-benzenedicarboxylic acid diethyl ester, DEP) is one of a group of widely used plasticizers, which can lead to serious environmental problems. Because of manufacturing and application, DEP can be released into the atmosphere where it can undergo transport and chemical transformation. To assess the atmospheric behavior of pollutants, it is critical to know their atmospheric reactions. In this paper, the reaction mechanism and possible oxidation products for the OH-initiated atmospheric reaction of DEP were theoretically investigated by using the density functional theory (DFT) method. The geometries and frequencies of the reactants, intermediates, transition states, and products were calculated at the MPWB1K/6-31+G(d,p) level, and the energetic parameters were further refined by the MPWB1K/6-311+G(3df,2p) method. The present study shows that H abstractions from the CH(3) and CH(2) groups, as well as OH addition to the benzene ring, are energetically favorable reaction pathways for the reaction of DEP with OH radicals. Detailed degradation products are provided.

Abstract  A novel coordination polymer based on a nanosized flexible aromatic carboxylic acid ligand has been successfully synthesized by solvothermal reaction, [Cd(obda)(0.5)(bpy)(H2O)]center dot 2H(2)O (1) (H(4)obda = 1,4-bis(4-oxy-1,2-benzenedicarboxylic acid)benzene, bpy = 4,4'- bipyridine), exhibiting a (4,4)-connected self-penetrating pillared-layered metal-organic framework. In addition, photoluminescence was also performed on 1.

Abstract  Hydrothermal reactions of lanthanide(ill) oxide and copper halide with isonicotinic acid (Hina) and pyridine-2,3-dicarboxylic acid (H(2)pdc) or 1,2- benzenedicarboxylic acid (H(2)bdc) lead to three novel lanthanide(III)-copper(I) heterometallic compounds, namely, [Ce-2(ina)(5)(na)(2)(H2O)(2)][Cu5Br4] (1, na = nicotinic acid), [Er-4(ina)(8) (bdc)(2)(OH)(H2O)(5)][CU(8)l(7)] (2), and [Ce-3(ina)(8)(bdc)(H2O)(4)][CU7Br6] (3). Compound 1 is constructed from two distinct units of the Ln-organic double chains and inorganic [CU5Br4](n)(n+) chains. Compound 2 consists of 2D Ln-organic layers and 1D [CU(8)l(7)](n)(n+) cluster chains. Compound 3 can be viewed as a 1D [CU6Br6](n) chainlike motif inserted into the channels of a 3D Ln-Cu-organic motif. Compounds 1-3 exhibit three different 1D inorganic copper(I)-halide chains interconnected with metal-organic 1D chains, 2D layers, and 3D nets resulting in three mixed- motif non-interpenetrating heterometallic Cu-halide-lanthanide (Ln)-organic frameworks, which represent good examples and a facile method to construct such mixed-motif heterometallic compounds. Furthermore, the IR, TGA, and UV-vis spectra of 1-3 were also studied.

Abstract  By using isomeric N,N'-di(2-pyridyl)-adipoamide (L-1), N,N'-di(3-pyridyl)adipoamide (L-2) and N,N'-di(4-pyridyl)adipoamide (L-3) and isomeric 1,2- benzenedicarboxylic acid (1,2-H2BDC), 1,3-benzenedicarboxylic acid (1,3-H2BDC) and 1,4- benzenedicarboxylic acid (1,4-H2BDC), eight Zn(II) and Cd(II) coordination polymers [Zn(1,2-BDC) (L-2)(infinity), 1; [Zn-2(1,3-BDC)(2)(L-2)(H2O)(2)](infinity), 2; [Zn-2(1,4-BDC)(2) (L-1)(H2O) (2)](infinity), 3; {[Zn-2 (1,2-BDC)(2)(L-3)(H2O)(2)]center dot 2H(2)O}(infinity), 4; {[Cd(1,2- BDC)(L-2)(H2O)]center dot H2O}(infinity), 5; [Cd-2(1,3-BDC)(2)(L-2)(H2O)(4)](infinity), 6; {[Cd- 2(1,4-BDC)(2)(L-2)(2)]center dot(H2O)(3)}(infinity), 7; [Cd-2(1,4-BDC)(2)(L-1)(H2O)(2)] (infinity), 8, have been synthesized under hydrothermal conditions. Complexes 1, 4, and 5 form 11) double-looped chain, 11) chain with loops and 2D layer with loops, respectively, and complex 6 exhibits a 1D ladder chain. Complex 2 shows rare 3-fold interpenetrated hcb layers, in which each layer interdigitates with other four parallel layers by directing the 1,3-BDC ligands into the windows of the adjacent nets, whereas complexes 3 and 8 forms planar and undulated hcb layers, respectively. Complex 7 shows a 3D self-penetrating net of {4(24).5.6(3)}-ilc topology with a unique arrangement for the L-2 spacer ligands. The L-1 ligands in complexes 3 and 8 adopt the new tetradentate bonding mode involving chelation and bridge through two pyridyl nitrogen atoms and two amide oxygen atoms, whereas the L-2 and L-3 ligands in other complexes show the bidentate bonding mode through the two pyridyl nitrogen atoms. The various bonding modes and the ligand-isomerism of the spacer ligands BDC2- and L-1-L-3 as well as the identity of the metal center play important roles in determining the structural diversity.

Abstract  Fourteen samples of fresh curry leaves (Murraya Koenigii) were collected from 13 states of India and analyzed for 6 minor (Ca, Cl, K, Mg, Na and P) and 14 trace (Br, Ce, Co, Cr, Cs, Fe, Hg, Mn, Rb, Sb, Sc, Se Th and Zn) elements by 2-minute irradiation in a reactor followed by high resolution gamma-ray spectrometry. Peach Leaves (SRM-1547) and Mixed Polish Herbs (MPH-2) were used as comparator standards. Phosphorus was determined by counting the P-activity from P-32 using an end-window GM counter. Most elements were found to vary in a wide range depending on their origin of location, e.g., Na (104-455 mu g/g), K (10.3- 30.3 mg/g), Ca (9.44-28.3 mg/g), Mg (1.14-7.19 mg/g), P (0.43-1.69 mg/g), Mn (24.8-63.0 mu g/g), Fe (72.5-195 mu g/g), Se (40.1-131 ng/g) and Zn (7.90-70.5 mu g/g). Variation in the elemental concentrations of the same species of different origin may be attributed to ecological and geographical variations. Further, column and thin layer chromatography were used for separating three organic constituents from the ethanolic extract; 3-methylthiopropanenitrile; 1,2- benzenedicarboxylic acid, mono (2-ethylhexyl ester) and 1-penten-3-ol and characterized by IR and GC-MS. Inorganic elements may be present as complexes with the organic compounds.

Abstract  Thermally assisted hydrolysis and methylation (THM) in the presence of tetramethylammonium hydroxide (TMAH) was applied to the analysis of red dyes based on the 9,10-anthracenedione skeleton (anthraquinone), namely alizarin, quinizarin, purpurin, carminic acid, and the blue pigment indigo. Alizarin and purpurin are the principal coloured compounds of madder, and carninic acid of cochineal red. Synthetic dyes were dissolved in aqueous TMAH, pyrolysed at 700 degrees C for 10 s and the evolved thermochemolytic products were analysed by gas chromatography/mass spectrometry (GC/MS). The resulting chromatograms of all the madder dyes were characterised by the presence of the methyl esters of 1,2-benzenedicarboxylic acid (dimethyl-o-phthalate) and benzoic acid. In addition, thermochemolysis of alizarin and quinizarin afforded 1,2-dimethoxyanthraquinone and 1,4-dimethoxyanthraquinone, respectively. Carminic acid produced a series of methylated fragments deriving from both the substituted anthraquinoid moiety and the glycosidically-Clinked glucose. Finally, the principal thermochemolysis products of indigo were the N-methylated derivatives of 2-amino benzoic acid methyl ester followed by methylated aniline and indoles. The potential of THM as a rapid technique for the identification of dyes in real samples was illustrated by the analysis of madder lake, cochineal lake, and natural indigo dispersed in a binder. (C) 2000 Elsevier Science B.V. All rights reserved.

Abstract  Industrial dyeing wastewater was oxidized in supercritical water in a transpiring-wall reactor, using hydrogen peroxide as an oxidant. Experiments were performed at 595 to 704 K and 18 to 30 MPa, with an oxidant dosage ratio ranging from 0.6 to 2.0. A chemical oxygen demand (COD) removal of more than 98.4% was achieved at 704 K and 28 MPa, with a retention time less than 35 seconds, which increased with the temperature, pressure, and oxidant. A modified first-order rate expression was regressed from experimental data, taking into account the influence of induction time. The resulting pre-exponential factor, A, and activation energy, Ea, were 1.07 seconds(-1) and 12.12 kJ x mol(-1), respectively, while the reaction order for feed wastewater (based on COD) and oxidant were assumed to be 1 and 0, respectively. Gas chromatography/mass spectrometry analysis for effluents indicated that carbon dioxide, carbon monoxide, and nitrogen were the main reaction products, and phenol; benzenecarboxylic acid; 1, 2-benzenedicarboxylic acid; and isoquinoline were detected as intermediates.

Abstract  By control of mixed ligands with particular coordination sites, three novel three-dimensional (3D) 4d-4f heterometallic coordination polymers, [Ln(4) (H2O)(2)Ag(1,3-bdc)(4)(inic)(5)] center dot nH(2)O (Ln) Nd ( 1), n = 0.25; Eu ( 2), n = 0; 1,3- H(2)bdc = 1,3-benzenedicarboxylic acid and Hinic) isonicotinic acid) and [Nd(H2O) Ag(1,2-bdc) (inic)(2)] ( 3) (1,2-H(2)bdc) 1,2-benzenedicarboxylic acid), have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, thermogravimetric (TG) analysis, and single-crystal X-ray diffraction. Compounds 1-3 crystallize in the monoclinic system, space group C2/c. Compounds 1 and 2 are isostructural and exhibit novel 3D coordination frameworks constructed from two-dimensional (2D) wavelike lanthanide carboxylate layers and Ag( inic) 4 complexes. To the best of our knowledge, they represent the first examples of 3D 4d-4f heterometallic coordination frameworks, in which the transition metal complexes bond to a 3D lanthanide carboxylate supramolecular framework with nanometer-sized channels built up from 2D wavelike layers. Compound 3 possesses an unusual 3D framework based on linkage of neodymium- carboxylate chains and silver( I) centers by inic ligands. The difference between both kinds of frameworks can be ascribed to the geometry effect of benzenedicarboxylate. Furthermore, the luminescent properties of 2 were studied.

Abstract  One low-cost improved oil recovery (IOR) technology making significant advances is reservoir flooding with thermophilic microbes. The gram-negative cells of the Thermus SP3 strain were grown at high temperatures up to 85degrees C in the neutral to alkaline pH range. Depending on the culture conditions, the organism occurred as single rods, or as filamentous aggregates. Thermus SP3 was grown chemoorganotrophically and produced volatile fatty acids, 4-hydroxy-4-methyl-2-pentanone, xylene, undecane, 1,2-benzenedicarboxylic acid, bis (2-methylprophl) ester, dibutyl phthalate, di-n-octyl phthalate and surfactants, which had various effects on crude oil. Thermus SP3 could decrease the viscosity and paraffin content of crude oil, degrade heavy fractions, increase the content of light compositions of crude oil, improving the physical and chemical properties, and improve oil recovery (12.59%). Thermophilic Thermus SP3 strain was screened to begin optimizing the process and core-flood was performed to quantify oil recovery. A laboratory core-flood experiment using microbial flooding methodology showed that oil recovery was better than with chemical flooding oil recovery.

Abstract  An Actinomycete isolate found to be prominent in the laterite soils of Acharya Nagarjuna University (ANU) Campus, Guntur was identified as Nocardia levis MK-VL_113 by 16S rRNA analysis. Cultural, morphological and physiological characteristics of the strain were recorded. Screening of secondary metabolites obtained from 4-day old culture broth of the strain led to the isolation of two fractions active against a wide variety of Gram-positive, Gram-negative bacteria and fungi. The structure of the first active fraction was elucidated using FT-IR, EI-MS, (1)H NMR and (13)C NMR spectra and identified as 1-phenylbut-3-ene-2-ol which is first time reported as a natural product. The compound exhibited good antimicrobial potential against the opportunistic and pathogenic bacteria and fungi. The antifungal activity of the strain and its metabolite were further confirmed with in vitro and in vivo studies. Evidence for the antagonism of the strain against Fusarium oxysporum, causing wilt disease in sorghum was demonstrated by the formation of inhibition zone in in vitro plate assay and reduction in the incidence of wilt of sorghum plants by using a green house trial. Analysis of the rhizosphere soil extracts by high performance liquid chromatography also demonstrated the production of the compound by the strain under in vivo conditions. As compared to the commercial fungicide mancozeb, the bioactive compound, 1-phenylbut-3-ene-2-ol was highly effective in controlling wilt of sorghum. Besides, the partially purified second fraction (PPF) subjected to gas chromatography-mass spectrometry revealed the presence of phenylethyl alcohol, dibutyl phthalate and 1,2-benzenedicarboxylic acid, 3-nitro.

Abstract  The photocatalytic degradation of dye Rhodamine B (RhB) in the presence of TiO2 nanostripe or P25 under visible light irradiation was investigated. The degradation intermediates were identified using Infrared spectra (IR spectra), H-1 nuclear magnetic resonance ((HNMR)-H-1) spectra, and gas chromatography-mass spectroscopy (GC-MS). The IR and the 1HNMR results showed that the large conjugated chromophore structure of RhB was efficiently destroyed under visible light irradiation in both the photocatalytic systems (TiO2 nanostripe or P25 and Rhodamine B systems). GC-MS results showed that the main identified intermediates were ethanediotic acid, 1,2-benzenedicarboxylic acid, 4-hydroxy benzoic acid and benzoic acid, which were almost the same in the TiO2 nanostripes and P25 systems. This work provides a good insight into the reaction pathway(s) for the TiO2-assisted photocatalytic degradation of dye pollutants under visible light irradiation.

Abstract  To explore the influence of isomeric benzenedicarboxylates on the self-assembly of coordination frameworks, six mixed-ligands Zn(II)/Co(II) coordination complexes, [Zn(pbmb)(1,4-bdc)](n) (1), {[Co(pbmb)(1,4-bdc)] center dot 1.5H2O}(n) (2), [M(pbmb) (1,3-bdc)](n) [M = Zn (3) or Co (4)], and [M(pbmb)(1,2-bdc)](n) [M = Zn (5) or Co (6)] (pbmb = 1,10-(1,3-propane) bis-(2-methylbenzimidazole), 1,2-bdc = 1,2-benzenedicarboxylic acid, 1,3-bdc = 1,3-benzenedicarboxylic acid, and 1,4-bdc = 1,4-benzenedicarboxylic acid), have been obtained and structurally characterized. Structural analyses reveal that complexes 1 and 2 display2D(4, 4) networks, of which complex 1 contains left-and right-handed helical chains arranged alternately and 2 owns a well-known paddle-wheel binuclear clusters. Complexes 3 and 4 feature 2D networks with 6(3) topologies, and complexes 5 and 6 exhibit 1D double-chain structures. Additionally, complexes 1-6 present high thermal stabilities, as well as 1, 3, and 5 show different photoluminescence behaviors in the solid state. (C) 2012 Elsevier B.V. All rights reserved.

Abstract  The infrared spectra of a series of aqueous solutions containing phthalic acid (1,2-benzenedicarboxylic acid) and varying pH were examined using attenuated total reflection Fourier transform infrared spectroscopy and potentiometry. The basis spectra of phthalic acid, the hydrogen phthalate ion, and the phthalate ion were isolated using a factor analysis in which the absorbance of these species varies with pH and total phthalate concentration according to equilibrium and mass balance relations. Assignments of these basis spectra were made by comparison with spectra calculated ab initio. The conditional formation constants of phthalic acid and the hydrogen phthalate ion were determined at 25.0 +/- 0.1 degreesC in 0.6 M NaCl ionic media using infrared spectroscopy and in 1.5 M NaCl ionic media using both infrared spectroscopy and potentiometry. (C) 2001 Elsevier Science B.V. All rights reserved.

Abstract  The effect of propolis water solution (PWS) on the respiration of rat heart mitochondria with NAD-linked (pyruvate + malate), FAD-linked (succinate) substrates and fatty acids (palmitoyl-(L)-carnitine) was investigated in this study. PWS at the lowest concentration of 4 mu g mL(-1) of phenolic compounds (PC) had no effect on mitochondrial respiration with all investigated substrates. PWS at concentrations of 63 and 125 mu g mL(-1) of PC caused a significant decrease of basal (24 and 54 %) and maximal (58 and 70 %) respiration rates with succinate as substrate. At these PWS concentrations the oxidation of pyruvate+malate and palmitoyl-(L)-carnitine was diminished to a lower degree: the basal respiration rate decreased by 13-18 % and the maximal respiration rate by 15-28 %. Succinate oxidation was affected, probably because of the inhibition of succinate dehydrogenase by the 1,2- benzenedicarboxylic acid esters found in PWS. The PWS-caused decrease in the mitochondrial respiration rate with pyruvate+malate and fatty acids could be due to diminished activities of respiratory chain complexes and/or ADP/ATP translocator.

Abstract  The chain length dependence of bimolecular termination in the solution polymerization of styrene was examined at 25 degreesC with the solvents (50% per volume) toluene, cyclohexane, bis(3,5,5-trimethylhexyl)phthalate, and ethyl acetate. Irrespective of which method was applied, the ""good"" solvent systems with toluene and ethyl acetate exhibited a chain length dependence comparable to or even greater than that observed for the bulk polymerization of styrene, while a markedly weaker chain length dependence was observed with the ""bad"" solvents cyclohexane and bis( 3,5, 5-trimethylhexyl)phthalate. This is documented by the exponent b in the power law (k) over bar (t) = A . nu'(-b) connecting the average termination coefficient (k) over bar (t) and the chain length nu' of the radical chains at the moment of undergoing bimolecular termination: b approximate to 0.2 for styrene tin bulk) and in toluene solution, b approximate to 0.3 in ethyl acetate solution and 0.10 to 0.14 in cyclohexane and bis (3,5,5-trimethylhexyl)phthalate solution, respectively. Only in the case of the bad solvents the bulk viscosity and BL or the prefactor A are inversely correlated. In the case of the good solvents, the bulk viscosities were too close to detect such a relationship. The observed values of the parameter b (with the exception of the ethyl acetate system) are consistent with the idea of a chain length dependent shielding exercised by the rest of the chains on the two radical chain ends (some sort of ""kinetic"" excluded volume effect) which is much weaker in bad solvents.

Abstract  A bioactivity-guided isolation method was developed with the objective of isolating the allelochemicals in rice (Oryza sativa L.), Roots of the allelopathic rice cultivar Taichung Native 1, grown hydroponically, were extracted and fractionated, with the activity of the fractions followed using a 24-well culture plate microbioassay, Some of the fractions obtained consisted of pure compounds, but none inhibited the growth of barnyardgrass [Echinochloa crusgalli (L.) Beauv,] at the lower concentration at which they were tested, Identified compounds were azelaic acid; p-coumaric acid; 1H-indole-3-carboxaldehyde; 1H-indole-3-carboxylic acid; 1H-indole-5-carboxylic acid; and 1,2-benzenedicarboxylic acid bis(2-ethylhexyl)ester. rho -Coumaric acid, a known allelochemical, inhibited the germination of lettuce (Lactuca sativa L.) seedlings at 1 mM, However, rho -coumaric acid was active against barnyardgrass only at concentrations higher than 3 mM, The two most active fractions obtained from the bioassay-guided isolation were still a mixture of compounds as analyzed by gas chromatography-mass spectrometry (GC-MS), Further fractionation is being done to isolate and identify the allelochemical(s) in these active fractions. This work has demonstrated the use of bioassay-guided isolation in identifying allelochemicals in rice and has correlated observed field activity with laboratory experiments.

Abstract  The aroma compounds of melon fruits play a crucial role in commercial value. Aroma characterization of the 'Flavor No. 3' melon was detected using headspace-solid phase microextraction (HS-SPME) combined with gas chromatography-mass spectrometry (GC-MS). The results suggested that esters and ketones were the main aroma compositions, as more than 70% of the total volatile compounds yield, and the remains were alcohols, aldehydes, and others. 4-Hydroxy-1,2-benzenedicarboxylic acid (23.25%), pentadecanoic acid methyl ester (8.17%), and 1,2-benzenedicarboxylic acid butyl 2-methylpropyl ester (6.26%) presented as major compounds in the 'Flavor No. 3' fruit pulp.

Abstract  Seven new coordination polymers, [Co(3-bpcd)(1,3-BDC)(H2O) (3)]center dot H2O (1), [Co(3-bpcd)(1,2-BDC)-(H2O)]center dot H2O (2), [Co-3(3-bpcd)(1,2,4-BTC) (2)(H2O)(4)]center dot 4H(2)O (3), [Co(3-bpcd)(NPH)]center dot 2H(2)O (4), [Cu-(3-bpcd)(1,3-BDC)] (5), [Cu(3-bpcd)(1,2-BDC)] (6), [Cu(3-bpcd)(1,3,5-HBTC)(H2O)](2)center dot 2H(2)O (7) (3-bpcd = N,N'-bis(pyridin-3-yl) cyclohexane-1,4-dicarboxamide, 1,3-H2BDC = 1,3-benzenedicarboxylic acid, 1,2-H2BDC = 1,2-benzenedicarboxylic acid, 1,2,4-H3BTC = 1,2,4-benzenetricarboxylic acid, H2NPH = 3-nitrophthalic acid and 1,3,5-H3BTC = 1,3,5-benzenetricarboxylic acid) have been hydrothermally synthesized by assembling transition-metal cobalt-copper salts with semi-rigid bis-pyridyl-bis- amide ligand 3-bpcd and different aromatic polycarboxylic acids. Complex 1 exhibits a one- dimensional (1D) sinusoidal-like chain, which is further assembled into a three-dimensional (3D) supramolecular framework through hydrogen-bonding interactions. Complex 2 possesses a 3D framework with 4-connected 6(6) topology, which contains a two-dimensional (2D) distorted asymmetric hexagonal grid. When 1,2,4-BTC is used in complex 3, a 3D framework with (6(3)center dot 8(2)center dot 10)(2)(6(5)center dot 8)(2)(8) topology is constructed. Complex 4 possesses a 3D framework with 4-connected 6(6) topology, which is similar to that of 2 except for containing a 2D symmetric hexagonal grid. When Co-II ion is replaced by Cu-II ion, the 3D framework of complex 5 with (4 center dot 6(2))(4 center dot 6(6)center dot 8(3)) topology based on 3-bpcd and 1,3-BDC ligands is obtained. Complex 6 shows a 2D cross network consisting of a superposed Cu-3- bpcd 1D chain and 1,2-BDC, which is further expanded into a 3D supramolecular framework by hydrogen-bonding interactions. In complex 7, 1,3,5-HBTC is employed as the auxiliary ligand, and a 3D supramolecular framework based on the undulated 2D layers is formed through pi-pi stacking and hydrogen-bonding interactions. Both the metal ions and polycarboxylates play important roles in the construction of the title complexes. In addition, the electrochemical behaviors and the fluorescence properties of the seven complexes have been investigated.

Abstract  The volatile oils from Marchantia convoluta were obtained by microwave extraction (ME) and phytosol extraction (PE) methods. The attained extracts were analyzed by gas chromatography with mass spectrometric detector (GC-MS). The compounds were identified according to their retention indices and mass spectra (EI, 70 eV). A total of fourteen compounds were identified in ME extract accounting for 80.72% of total peak area. Isolongifolene (24.588%), 1, 2-benzenedicarboxylic acid, butyl cyclohexyl ester (10.768%), pyrene (9.328%) and hexadecanoic acid, ethyl ester (8.570%) were the major compounds identified from ME extract. The analytical results of ME extract were compared with PE method. The ME extract was found to be markedly different from that of PE extract. A total of seven compounds in PE extract were identified accounting for 74.275% total peak area. 1-Phenanthrenecarboxylic acid, 1,2,3,4,4a,9,10, 10a-octahydro-1, 4a-dimethyl-7-(1-methylethyl) methyl ester were the major compounds.

Abstract  Poplar engineering biocomposites is a new engineering materials. In order to evaluate its potential environmental risk to human, the volatile organic compounds of poplar engineering biocomposites were adsorbed and determined by TD-GC-MS. The result were: (1) The main constituents of volatiles at 40 degrees C: were bicyclo[2.2.1]heptan-2 -one, 1.7,7- trimethyl-, (1r)-(31.55%), 1,2-benzenedicarboxylic acid. mono(2-ethylhexyl) ester (14.94%). 2,6,10,14,18,22-tetracosahexaene, 2,6,10,15,19,23-hexamethyl-(7.34%), [1,1':3',1 ''-terphenyl]-2'-ol(5.97%). cedrol (5.29%), caryophyllenc(5.26%), 3-[(1z)-1,3-butaclienyl]-4- vinylcyc lopentene(3.92%), etc. (2) The main constituents of volatiles at 60 C were 1,2- benzenedicarboxylic acid, mono(2-ethylhexyl) ester(17.13%). [1,1':3',1 ''-terphenyl]-2'-ol (9.11%), camphor(8.6%), 4-imidazolidinone. 5-(phenylmethyl)-2-thioxo- (7.6%), cedrol(7.26%), 2,5 -cyclohexadiene-1,4-dione, 2,5-diphenyl-(4.58%), 1h-indole, 5-methyl- 2-phenyl-(3.94%), 2,6.10.14.18.22-tetracosahexaene. 2.6.10.15.19,23-hexamethyl- (3.63%), phenol,2,4-bis(1,1- dimethylethyl) (3.56%), etc. So the poplar engineering biocomposites was safe under 40-60 degrees C.

Abstract  The effects of the peroxisome proliferators di-isononyl phthalate (DINP) and di-2-ethylhexyl phthalate (DEHP) were evaluated in young adult male cynomolgus monkeys after 14 days of treatment, with emphasis on detecting hepatic and other effects seen in rats and mice after treatment with high doses of phthalates. Groups of 4 monkeys received DINP (500 mg/kg/day), DEHP (500 mg/kg/day), or vehicle (0.5% methyl cellulose, 10 ml/kg) by intragastric intubation for 14 consecutive days. Clofibrate (250 mg/kg/day), a hypolipidemic drug used for cholesterol reduction in human patients was used as a reference substance. None of the test substances had any effect on body weight or liver weights. Histopathological examination of tissues from these animals revealed no distinctive treatment-related effects in the liver, kidney, or testes. There were also no changes in any of the hepatic markers for peroxisomal proliferation, including peroxisomal beta-oxidation (PBOX) or replicative DNA synthesis. Additionally, in situ dye transfer studies using fresh liver slices revealed that DINP, DEHP, and clofibrate had no effect on gap junctional intercellular communication (GJIC). None of the test substances produced any toxicologically important changes in urinalysis, hematology, or clinical chemistry; however, clofibrate produced some emesis, small increases in serum triglyceride, decreased calcium, and decreased weights of testes/epididymides and thyroid/parathyroid. The toxicological significance of these small changes is questionable. The absence of observable hepatic effects in monkeys at doses that produce hepatic effects in rodents suggests that DINP, DEHP, and clofibrate would also not elicit in primates other effects such as liver cancer. These data, along with results from in vitro hepatocyte studies, indicate that rodents are not good animal models for predicting the hepatic effects of phthalates in primates, including humans.

Abstract  Di-isononyl phthalate esters (DINPs) are endocrine-disrupting chemicals and have replaced di(2-ethylhexyl) phthalate (DEHP) as the major plasticizer for polyvinylchloride products in recent years. Exposure marker discovery of DINPs is crucial because of their high potential for human exposure and toxicity. We propose here an alternative approach for tracing signals derived from stable isotope-labeled precursors with varied labeling ratios to efficiently filter probable metabolite signals. The statistical process, signal mining algorithm with isotope tracing (SMAIT), effectively filtered 13 probable DINP metabolite signals out of the 8,867 peaks in the LC-MS data obtained from incubated stable isotope-labeled precursors with liver enzymes. Seven of the 13 probable metabolite signals were confirmed as DINP structure-related metabolites by preliminary MS/MS analyses. These 7 structure-related metabolite signals were validated as effective DINP exposure markers using urine samples collected from DINP-administered rats without time-consuming comprehensive structure identification. We propose that the 7 identified possible DINP metabolite signals of m/z 279.1, 293.1, 305.1, 307.1, 321.1, 365.1, and 375.1 are potential markers for DINP exposure and should be further investigated. The integrated approach described here can efficiently and systematically filter probable metabolite signals from a complex LC-MS dataset for toxic exposure marker discovery. It is a relatively low cost/rapid workflow for exposure marker discovery.

Abstract  BACKGROUND: Anogenital distance (AGD), a sexually dimorphic measure of genital development, is a marker for endocrine disruption in animal studies and may be shorter in infant males with genital anomalies. Given the correlation between anogenital distance and genital development, we sought to determine if anogenital distance varied in fertile compared to infertile adult men.

METHODS: A cross sectional study of consecutive men being evaluated for infertility and men with proven fertility was recruited from an andrology clinic. Anogenital distance (the distance from the posterior aspect of the scrotum to the anal verge) and penile length (PL) were measured using digital calipers. ANOVA and linear regression were used to determine correlations between AGD, fatherhood status, and semen analysis parameters (sperm density, motility, and total motile sperm count).

FINDINGS: A total of 117 infertile men (mean age: 35.3±17.4) and 56 fertile men (mean age: 44.8±9.7) were recruited. The infertile men possessed significantly shorter mean AGD and PL compared to the fertile controls (AGD: 31.8 vs 44.6 mm, PL: 107.1 vs 119.5 mm, p<0.01). The difference in AGD persisted even after accounting for ethnic and anthropomorphic differences. In addition to fatherhood, on both unadjusted and adjusted linear regression, AGD was significantly correlated with sperm density and total motile sperm count. After adjusting for demographic and reproductive variables, for each 1 cm increase in a man's AGD, the sperm density increases by 4.3 million sperm per mL (95% CI 0.53, 8.09, p = 0.03) and the total motile sperm count increases by 6.0 million sperm (95% CI 1.34, 10.58, p = 0.01). On adjusted analyses, no correlation was seen between penile length and semen parameters.

CONCLUSION: A longer anogenital distance is associated with fatherhood and may predict normal male reproductive potential. Thus, AGD may provide a novel metric to assess reproductive potential in men.

Abstract  Phthalates are used as plasticizers and solvents in industrial, medical and consumer products; however, occupational exposure information is limited. We sought to obtain preliminary information on occupational exposures to diethyl phthalate (DEP), di-n-butyl phthalate (DBP) and di(2-ethylhexyl) phthalate (DEHP) by analyzing for their metabolites in urine samples collected from workers in a cross-section of industries. We also obtained data on metabolites of dimethyl phthalate (DMP), benzylbutyl phthalate (BzBP), di-isobutyl phthalate and di-isononyl phthalate. We recruited 156 workers in 2003-2005 from eight industry sectors. We assessed occupational contribution by comparing end-shift metabolite concentrations to the US general population. Evidence of occupational exposure to DEHP was strongest in polyvinyl chloride (PVC) film manufacturing, PVC compounding and rubber boot manufacturing where geometric mean (GM) end-shift concentrations of DEHP metabolites exceeded general population levels by 8-, 6- and 3-fold, respectively. Occupational exposure to DBP was most evident in rubber gasket, phthalate (raw material) and rubber hose manufacturing, with DBP metabolite concentrations exceeding general population levels by 26-, 25- and 10-fold, respectively, whereas DBP exposure in nail-only salons (manicurists) was only 2-fold higher than in the general population. Concentrations of DEP and DMP metabolites in phthalate manufacturing exceeded general population levels by 4- and >1000-fold, respectively. We also found instances where GM end-shift concentrations of some metabolites exceeded general population concentrations even when no workplace use was reported, e.g. BzBP in rubber hose and rubber boot manufacturing. In summary, using urinary metabolites, we successfully identified workplaces with likely occupational phthalate exposure. Additional work is needed to distinguish occupational from non-occupational sources in low-exposure workplaces.