Abstract  A bioassay-guided column chromatographic strategy was adopted in the present study to fractionate the culture extract of Photorhabdus temperata M1021 to identify potential insecticidal and antimicrobial compounds. An ethyl acetate (EtOAc) culture extract of P. temperata was assayed against Galleria mellonella larvae through intra-hemocoel injection and exhibited 100% insect mortality within 60 h. The EtOAc fraction and an isolated compound exhibited phenoloxidase (PO) inhibition of up to 60% and 63%, respectively. The compound was identified as 1,2-benzenedicarboxylic acid (phthalic acid, PA) by gas chromatography-mass spectrometry and nuclear magnetic resonance. PA exhibited insecticidal activity against G. mellonella in a dose-dependent manner, and 100% insect mortality was observed at 108 h after injection of 1 M PA. In a PO inhibition assay, 0.5 and 1 M concentrations of PA were found to inhibit PO activity by 74% and 82%, respectively; and in a melanotic nodule formation assay, nodule formation was significantly inhibited (27 and 10 nodules) by PA (0.5 and 1 M, respectively). PA was furthermore found to have substantial antioxidant activity and maximum antioxidant activity was 64.7% for 0.5 M PA as compare to control. Antibacterial activity was assessed by The MIC values ranged from 0.1 M to 0.5 M of PA. This study reports a multifunctional PA, a potential insecticidal agent, could a factor of insect mortality along with other toxins produced by P. temperata M1021.

Abstract  Industrial poly(vinyl chloride) (PVC) plastisols are often formulated using phthalate plasticizers due to their costeffectiveness and high compatibility with PVC. However, there is a current need to replace these additives by plasticizers that (i) present reduced migration/leaching and volatilization profiles, (ii) can optimize production processes while maintaining the performance of the final plasticized materials, and (iii) reduce toxicological risks to consumers and to the environment. The main objective of this work was to evaluate the effects of the partial replacement (15 and 30% (w/w)) of two conventional plasticizers (diisononyl phthalate (DINP) and acetyltri-2-ethylhexyl citrate (CITROFOL AHII)) by two low-volatility ionic liquids of the phosphonium-type (trihexyl(tetradecyl) phosphonium dicyanamide and trihexyl(tetradecyl) phosphonium bis- trifluoromethylsulfonyl)imide) on the rheological and thermomechanical properties of an emulsion-grade PVC which is usually employed in the production of automotive industry upholsteries. Rheological profiles and plastisols’ particle size distributions were monitored over time (up to 14 days) to study the effects of plastisols aging on the thermal stability and thermomechanical properties of PVC films obtained after gelation of the plastisols. Obtained results showed that the incorporation of these two phosphonium-type ionic liquids into DINP- and CITROFOL-based PVC plastisols significantly reduced their viscosities and changed their rheological profiles (from pseudoplastic to near-Newtonian behavior). Plastisols aging had a noticeable impact on the final thermomechanical properties of PVC films plasticized with DINP while no significant effects were observed for films plasticized with CITROFOL. These results are in good agreement with the correspondent time dependent rheological profiles

Abstract  Four coordination polymers, [Cu(4-dpyh)(0.5)(1,2-BDC)(H2O)(3)]H2O (1), [Cu(4-dpyh)(1,3-BDC)(H2O)] (2), [Cd(3-dpyh)(0.5)(1,3-BDC)(H2O)(2)]H2O (3), and [Zn(3-dpyh)(1,3-BDC)]3H(2)O (4) [4-dpyh=N,N-bis(4-pyridinecarboxamide)-1,6-hexane, 3-dpyh=N,N-bis(3-pyridinecarboxamide)-1,6-hexane, 1,2-H2BDC=1,2-benzenedicarboxylic acid and 1,3-H2BDC=1,3-benzenedicarboxylic acid], have been hydrothermally synthesized. X-ray diffraction analyses reveal that 1 is a discrete [Cu-2(4-dpyh)(1,2-BDC)(2)] dinuclear structure. Compound 2 exhibits a 2-D grid layer constructed from 1-D linear [Cu(1,3-BDC)](n) chains and [Cu(4-dpyh)](n) chains. Compound 3 features a 1-D ladder-like chain formed by the 1-D linear [Cd(1,3-BDC)](n) chains and 3-dpyh bridging ligands. Compound 4 displays a 2-D undulated layer containing meso-helical [Zn(3-dpyh)](n) chains and linear [Zn(1,3-BDC)](n) chains. The neighboring dinuclear complexes for 1, adjacent chains for 3, and adjacent layers for 2 and 4 are further linked by hydrogen bonding interactions to form 2-D (for 1) or 3-D supramolecular networks (for 2-4). The influences of the different dicarboxylates and metal on the structures of 1-4 have been discussed. The electrochemical behaviors of 1 and 2, the thermal stabilities and fluorescent properties of 1-4, and the fluorescent selectivities of 3 and 4 have been investigated.

Abstract  The International Union against Tuberculosis and Lung Disease (IUATLD) Bronchial Symptoms Questionnaire (1984) was developed for use in studies of asthma and its reliability measured in an earlier survey in England. The association of the symptoms elicited by this questionnaire to bronchial response to histamine has also been described. This paper presents the results of studies of the questionnaire in four clinical centres in Europe. The reliability of the questionnaire and its ability to predict the bronchial response to histamine were compared for English, Finnish, French and German translations of the questionnaire in samples of diagnosed asthmatics and controls in Nottingham, Berlin, Helsinki and Paris. The answers to questions showed good repeatability, especially in Finland and Germany, particularly those questions on asthma and wheeze. The most sensitive symptom for predicting hyperresponsiveness was the question on wheeze, the most specific questions were those on waking at night with shortness of breath (Paris and Nottingham) and morning tightness (Helsinki and Berlin). This study shows that the IUATLD (1984) questionnaire may provide useful, valid and comparable data even in translation but these studies will need to be repeated in representative samples before such a possibility is accepted as fully demonstrated.

Abstract  Although an association between exposure to phthalates in house dust and childhood asthma or allergies has been reported in recent years, there have been no reports of these associations focusing on both adults and children. We aimed to investigate the relationships between phthalate levels in Japanese dwellings and the prevalence of asthma and allergies in both children and adult inhabitants in a cross-sectional study. The levels of seven phthalates in floor dust and multi-surface dust in 156 single-family homes were measured. According to a self-reported questionnaire, the prevalence of bronchial asthma, allergic rhinitis, allergic conjunctivitis, and atopic dermatitis in the 2 years preceding the study was 4.7%, 18.6%, 7.6%, and 10.3%, respectively. After evaluating the interaction effects of age and exposure categories with generalized liner mixed models, interaction effects were obtained for DiNP and bronchial asthma in adults (Pinteraction=0.028) and for DMP and allergic rhinitis in children (Pinteraction=0.015). Although not statistically significant, children had higher ORs of allergic rhinitis for DiNP, allergic conjunctivitis for DEHP, and atopic dermatitis for DiBP and BBzP than adults, and liner associations were observed (Ptrend<0.05). On the other hand, adults had a higher OR for atopic dermatitis and DEHP compared to children. No significant associations were found in phthalates levels collected from multi-surfaces. This study suggests that the levels of DMP, DEHP, DiBP, and BBzP in floor dust were associated with the prevalence of allergic rhinitis, conjunctivitis, and atopic dermatitis in children, and children are more vulnerable to phthalate exposure via household floor dust than are adults. The results from this study were shown by cross-sectional nature of the analyses and elaborate assessments for metabolism of phthalates were not considered. Further studies are needed to advance our understanding of phthalate toxicity.

Abstract  Many toxic substances in the workplace can modify human health and quality of life and there is still insufficient data on respiratory outcomes in adults exposed to phthalates. The aim of this work was to assess in waste management workers from the Nitra region of Slovakia (n = 30) the extent of exposure to phthalates and health-related outcomes. Four urinary phthalate metabolites mono(2-ethylhexyl) phthalate (MEHP), monobutyl phthalate (MnBP), monoethyl phthalate (MEP) and monoisononyl phthalate (MiNP) were determined by high-performance liquid chromatography with mass spectrometry (HPLC-MS/MS). Urinary concentration of MEHP was positively associated with ratio of forced expiratory volume in 1 s to forced vital capacity % (FEV1/FVC) (r = 0.431; p = 0.018) and MiNP with fat free mass index (FFMI) (r = 0.439; p = 0.015). The strongest predictor of pulmonary function was the pack/year index as smoking history that predicted a decrease of pulmonary parameters, the FEV1/FVC, % of predicted values of peak expiratory flow (PEF % of PV) and FEV1 % of PV. Unexpectedly, urinary MEHP and MINP were positively associated with pulmonary function expressed as PEF % of PV and FEV1/FVC. We hypothesize that occupational exposure to phthalates estimated from urinary metabolites (MEHP, MiNP) can modify pulmonary function on top of lifestyle factors.

Abstract  Phthalates are used in industry products, household items, and medical tools as plasticizers. Human exposure to phthalates has raised concern about its toxicity. In the present study, optimization was conducted for the simultaneous analysis of eight kinds of phthalate metabolites using gas chromatography-mass spectrometry (GC-MS): MEP, MiBP, MnBP, MBzP, MiNP, MEHP, MEOHP, and MEHHP. In order to minimize the matrix effect and to do quantitative analysis, isotope dilution and LLE-GC-MS methods were performed. Urine samples were enzymatically hydrolyzed, extracted with a mixture of n-hexane and ethyl ether (8:2; v:v), and subsequently derivatized with trimethylsilylation. All eight kinds of analytes showed clear resolution and high reproducibility in GC-MS results. The method detection limit ranged from 0.05ng/mL to 0.2ng/mL. Calibration curves were found to be linear from 0.2 to 100ng/mL with -(2)>0.992. The relative standard deviation of the intraday precision using water and urine ranged from 2.1% to 16.3%. The analysis was performed with urine samples that were collected from adults residing in the Republic of Korea. The analyzed concentration results were compared according to gender and region. As a result, DEHP metabolites showed the highest detected concentration (75.92μg/g creatinine, 100%), and MiNP, a metabolite of DiNP, showed the lowest detected concentration (0.42μg/g creatinine, 22.5%). On average, female urine (200.76μg/g creatinine) had a higher detected concentration of ∑8 phthalate metabolites than male urine. Samples from rural regions (211.96μg/g creatinine) had higher levels than samples from urban regions.

Abstract  BACKGROUND: Environmental exposures to phthalates, particularly high molecular weight (HMW) phthalates, are suspected to contribute to allergy.

OBJECTIVE: To assess whether phthalate metabolites are associated with allergic symptoms and sensitization in a large nationally representative sample.

METHODS: We used data on urinary phthalate metabolites and allergic symptoms (hay fever, rhinitis, allergy, wheeze, asthma) and sensitization from participants 6 years and older in the National Health and Nutrition Examination Survey (NHANES) 2005-2006. Allergen sensitization was defined as positive to at least one of 19 specific IgE antigens (>0.35 kU/L). Odds ratios (ORs) per one log10 unit change in phthalate concentration were estimated using logistic regression adjusting for age, race, body mass index, gender, creatinine, and cotinine. Separate analyses were conducted for children (age 6-17 years) and adults.

RESULTS: The HMW phthalate metabolite mono-benzyl phthalate (MBzP) was the only metabolite positively associated with current allergic symptoms in adults (wheeze, asthma, hay fever, and rhinitis). Mono-(3-carboxypropyl) phthalate and the sum of diethylhexyl phthalate metabolites (both representing HMW phthalate exposures) were positively associated with allergic sensitization in adults. Conversely, in children, HMW phthalate metabolites were inversely associated with asthma and hay fever. Of the low molecular weight phthalate metabolites, mono-ethyl phthalate was inversely associated with allergic sensitization in adults (OR=0.79; 95% CI: 0.70, 0.90).

CONCLUSION: In this cross-sectional analysis of a nationally representative sample, HMW phthalate metabolites, particularly MBzP, were positively associated with allergic symptoms and sensitization in adults, but there was no strong evidence for associations between phthalates and allergy in children aged 6-17 years.

Abstract  A GC/MS method was developed for the identification and quantification of 14 phthalates: 8 phthalates classified H360 (DBP, DEHP, BBP, DMEP, DnPP, DiPP, DPP and DiBP), 3 phthalates proposed to be forbidden in medical devices (DnOP, DiNP and DiDP) and 3 other phthalates none regulated (DMP, DCHP and DEP) which may interfere with hormone function. In order to identify and quantify other plasticizers that are commonly used in PVC medical devices such as DEHP substitute, 5 non-phthalate plasticizers (ATBC, DEHA, DEHT, TOTM, and DINCH) were included in this study. Analyses are carried out on a GC/MS system with electron impact ionization mode (EI). The separation of plasticizers is obtained on a cross-linked 5%-phenyl/95%-dimethylpolysiloxane capillary column 30m×0.25mm (i.d.)×0.25μm film thickness using a gradient temperature. Compounds quantification is performed by external calibration using an internal standard. Validation elements on standard solutions were determined using the ISO 12787 standard approach. Plasticizers are extracted from PVC medical devices using THF for dissolving the PVC part of the sample followed by precipitation of the PVC by addition of ethanol. The supernatant is injected into a GC/MS system after dilution in ethanol. Different validation elements, including extraction recoveries for all compounds or for DEHP a cross-validation of the extraction process using the European pharmacopoeia monograph 3.1.14 as reference method, are discussed. Results obtained on 61 medical devices in PVC and 12 raw materials used as plasticizers are given.

Abstract  in their 10th or 11th years, while others who are equally healthy may not experience menarche until they 'are 14, 15, or even older. Menarche is, however, only a single event in the combination of physical changes which constitute puberty. The adolescent growth spurt, the development of the breasts, and the growth of the pubic hair occur more or less concurrently, and take, on the average, about 3 years from beginning to completion, with menarche occurring usually in the latter half of this period (Tanner, 1962). At present we lack detailed information about the rate at which girls progress through the stages of puberty and about the relation of one event to another. Only longitudinal studies (i.e. studies in which the same individuals are examined repeatedly over a period of time) can provide this information, which would be helpful both to the clinician in distinguishing the normal from the abnormal, and to the neuro-endocrinologist in constructing hypotheses about the mechanisms by which puberty is controlled. Present knowledge is based on studies carried out on small numbers of children in the United States a generation ago, together with some German studies of a similar period (for literature see Tanner, 1962).

Abstract  The Fourth National Report on Human Exposure to Environmental Chemicals, Updated Tables, September 2013 provides nationally representative biomonitoring data that has become available since the publication of the Fourth National Report on Human Exposure to Environmental Chemicals, 2009. The Updated Tables, September 2013 includes all the updates previously provided in Updated Tables, July 2010 through Updated Tables, March 2013. The Updated Tables, September 2013 present data for 91 chemicals measured in serum pooled samples that have not been reported in any previous Updated Tables. Since publication of the Fourth Report, 2009, 201 chemicals have updated tables and 49 chemicals have been added, for a total of 250 chemicals presented in these Updated Tables.

Abstract  BACKGROUND: Phthalate contamination exists in the North Coast karst aquifer system in Puerto Rico. In light of potential health impacts associated with phthalate exposure, targeted action for elimination of exposure sources may be warranted, especially for sensitive populations such as pregnant women. However, information on exposure to phthalates from a variety of sources in Puerto Rico is lacking. The objective of this study was to determine concentrations and predictors of urinary phthalate biomarkers measured at multiple times during pregnancy among women living in the Northern karst area of Puerto Rico.

METHODS: We recruited 139 pregnant women in Northern Puerto Rico and collected urine samples and questionnaire data at three separate visits (18±2weeks, 22±2weeks, and 26±2weeks of gestation). Urine samples were analyzed for eleven phthalate metabolites: mono-2-ethylhexyl phthalate (MEHP), mono-2-ethyl-5-hydroxyhexyl phthalate, mono-2-ethyl-5-oxohexyl phthalate, mono-2-ethyl-5-carboxypentyl phthalate, mono-ethyl phthalate (MEP), mono-n-butyl phthalate, mono-benzyl phthalate, mono-isobutyl phthalate, mono-3-carboxypropyl phthalate (MCPP), mono carboxyisononyl phthalate (MCNP), and mono carboxyisooctyl phthalate (MCOP).

RESULTS: Detectable concentrations of phthalate metabolites among pregnant women living in Puerto Rico was prevalent, and metabolite concentrations tended to be higher than or similar to those measured in women of reproductive age from the general US population. Intraclass correlation coefficients ranged from very weak (MCNP; 0.05) to moderate (MEP; 0.44) reproducibility among all phthalate metabolites. We observed significant or suggestive positive associations between urinary phthalate metabolite concentrations and water usage/storage habits (MEP, MCNP, MCOP), use of personal care products (MEP), and consumption of certain food items (MCPP, MCNP, and MCOP).

CONCLUSIONS: To our knowledge this is the first study to report concentrations, temporal variability, and predictors of phthalate biomarkers among pregnant women in Puerto Rico. Preliminary results suggest several potentially important exposure sources to phthalates in this population and future analysis from this ongoing prospective cohort will help to inform targeted approaches to reduce exposure.

Abstract  OBJECTIVES: Potential environmental risks caused by chemicals that could be released from a recycled plastic product were assessed using a screening risk assessment procedure for chemicals in recycled products.

METHODS: Plastic slope protection blocks manufactured from recycled plastics were chosen as model recycled products. Ecological risks caused by four model chemicals -di-(2-ethylhexyl) phthalate (DEHP), diisononyl phthalate (DINP), cadmium (Cd), and lead (Pb)- were assessed. Two exposure models were built for soil below the block and a hypothetic stream receiving runoff water. Based on the predicted no-effect concentrations for the selected chemicals and exposure scenarios, the allowable leaching rates from and the allowable contents in the recycled plastic blocks were also derived.

RESULTS: Environmental risks posed by slope protection blocks were much higher in the soil compartment than in the hypothetic stream. The allowable concentrations in leachate were 1.0×10(-4), 1.2×10(-5), 9.5×10(-3), and 5.3×10(-3) mg/L for DEHP, DINP, Cd, and Pb, respectively. The allowable contents in the recycled products were 5.2×10(-3), 6.0×10(-4), 5.0×10(-1), and 2.7×10(-1) mg/kg for DEHP, DINP, Cd, and Pb, respectively.

CONCLUSIONS: A systematic ecological risk assessment approach for slope protection blocks would be useful for regulatory decisions for setting the allowable emission rates of chemical contaminants, although the method needs refinement.

Abstract  Consumer products and building materials emit a number of semivolatile organic compounds (SVOCs) in the indoor environment. Because indoor SVOCs accumulate in dust, we explore the use of dust to determine source strength and report here on analysis of dust samples collected in 30 U.S. homes for six phthalates, four personal care product ingredients, and five flame retardants. We then use a fugacity-based indoor mass-balance model to estimate the whole house emission rates of SVOCs that would account for the measured dust concentrations. Di-2-ethylhexyl phthalate (DEHP) and di-iso-nonyl phthalate (DiNP) were the most abundant compounds in these dust samples. On the other hand, the estimated emission rate of diethyl phthalate (DEP) is the largest among phthalates, although its dust concentration is over two orders of magnitude smaller than DEHP and DiNP. The magnitude of the estimated emission rate that corresponds to the measured dust concentration is found to be inversely correlated with the vapor pressure of the compound, indicating that dust concentrations alone cannot be used to determine which compounds have the greatest emission rates. The combined dust-assay modeling approach shows promise for estimating indoor emission rates for SVOCs.

Abstract  Ten normal young males were investigated in order to examine diurnal and short-term variations in serum TSH and serum thyroid hormones. In five subjects blood samples were obtained every 30 min during a 24 h period of daily life. A synchronous diurnal rhythm was found for free T3 and serum TSH with low levels in the day-time and higher levels at night. The mean increase from day to night was 15 and 140 per cent, respectively. There was a tendency to a similar rhythm in free T4, but the increase of 7 per cent fell short of statistical significance. In the other five men blood samples were obtained every 5 min in a 6 to 7 h period starting within the interval from 19.15 to 22.00 h. A significant regular variation with a cycle-length of half an hour was found in TSH, free T3 and free T4. This rhythm accounted for a significant part of the total variation in the levels of TSH, free T3 and free T4. The mean amplitude of the short-term variation is 13, 15 and 11 per cent of the mean level of the respective hormones. The data suggest a pulsatile release of hormones from the thyroid gland governed by a pulsatile TSH secretion.