Method for trace determination of N-nitrosamines impurities in metronidazole benzoate using high-performance liquid chromatography coupled with atmospheric-pressure chemical ionization tandem mass spectrometry.

Genotoxic impurity control has been a great concern in the pharmaceutical industry since the recall of the large round of sartans worldwide in 2018. In these sartans, N-nitrosamines were the main contaminants in active pharmaceutical ingredients and formulations. Numerous analytical methods have been developed to detect N-nitrosamines in food, drugs, and environmental samples. In this study, a sensitive method is developed for the trace determination of N-nitrosamine impurities in metronidazole benzoate pharmaceuticals using high-performance liquid chromatography/atmospheric-pressure chemical ionization tandem mass spectrometry in the multiple reaction monitoring mode. The method was validated regarding system suitability, selectivity, linearity, accuracy, precision, sensitivity, solution stability, and robustness. The method showed good linearity with R2 ≥ 0.999 and FMandel  < Ftab(95%) ranging from 0.33 to 8.00 ng/ml. The low limits of detection of N-nitrosamines were in the range of 0.22-0.80 ng/ml (0.0014-0.0050 ppm). The low limits of quantification were in the range of 0.33-1.20 ng/ml (0.0021-0.0075 ppm), which were lower than the acceptable limits in metronidazole benzoate pharmaceuticals and indicated the high sensitivity of the method. The recoveries of N-nitrosamines ranged from 84% to 97%. Thus, this method exhibits good selectivity, sensitivity, and accuracy. Moreover, it is a simple, convenient, and scientific strategy for detecting N-nitrosamine impurities in pharmaceuticals to support the development of the pharmaceutical industry.

Screening of in Vitro Inhibition of Lactoperoxidase Enzyme by Methyl Benzoate Derivatives with Molecular Docking Studies.

Lactoperoxidase enzyme (LPO) is secreted from salivary, mammary, and other mucosal glands including the bronchi, lungs, and nose, which had functions as a natural and the first line of defense towards viruses and bacteria. In this study, methyl benzoates were examined in LPO enzyme activity. Methyl benzoates are used as precursors in the synthesis of aminobenzohydrazides used as LPO inhibitors. For this purpose, LPO was purified in a single step using sepharose-4B-l-tyrosine-sulfanilamide affinity gel chromatography with a yield of 9.91 % from cow milk. Also, some inhibition parameters including the half maximal inhibitory concentration (IC50 ) value and an inhibition constant (Ki ) values of methyl benzoates were determined. These compounds inhibited LPO with Ki values ranging from 0.033±0.004 to 1540.011±460.020 µM. Compound 1 a (methyl 2-amino-3-bromobenzoate) showed the best inhibition (Ki =0.033±0.004 µM). The most potent inhibitor (1 a) showed with a docking score of -3.36 kcal/mol and an MM-GBSA value of -25.05 kcal/mol, of these methyl benzoate derivatives (1 a-16 a) series are established H-bond within the binding cavity with residues Asp108 (distance of 1.79 Å), Ala114 (distance of 2.64 Å), and His351 (distance of 2.12 Å).

Quantitative vapor delivery for improved canine threshold testing.

The canine olfactory system is a highly efficient and intricate tool often exploited by humans for detection for its many attributes, including impressive sensitivity to trace analyte vapors. Canine detectors are often touted as having lower limits of detection, or olfactory detection threshold (ODT), than other field-relevant detection technologies; however, previous attempts to quantify canine ODTs have resulted in reported estimates spanning multiple orders of magnitude, even for the same analyte. A major contributor to these discrepancies is the vapor delivery method used for testing, where losses due to adsorption and dilution are often unaccounted for, and the presence of unattended compounds in the vapor stream due to carryover may go unnoticed. In this research, a trace vapor generator (TV-Gen) was used to deliver quantitatively accurate amounts of vapor reproducibly over time for canine testing. Analyte losses due to adsorption to surfaces in the flow path, dilution in the sniff port at the outlet, and analyte carryover were considered. Computational fluid dynamic (CFD) modeling was used to visualize analyte vapor spread throughout the port. CFD simulations revealed the need for a diffuser to encourage the diffusion of the analyte throughout the port. As a result, the modified vapor generator provides analyte air as a diffuse flow that is evenly distributed through the custom sampling orifice, as opposed to a narrow stream of air at the chosen concentration which exits directly into the environment. Laboratory validations were carried out for three analytes, amyl acetate, 2,4-dinitrotoluene (DNT), and methyl benzoate. A linear response across more than two orders of magnitude vapor concentration range was achieved for all analytes. These efforts will be applied in further research utilizing this TV-Gen vapor delivery system for canine ODT testing, eliminating many quantitative changes seen previously. Graphical abstract.

Different chromatographic methods for determination of alogliptin benzoate, metformin hydrochloride, and metformin impurity in bulk and pharmaceutical dosage form.

Two simple, sensitive, and reproducible methods were developed for the determination of alogliptin and metformin hydrochloride in presence of metformin impurity "melamin" in pure form and in pharmaceutical formulation. Method (A) was a thin layer chromatographic method in which separation was achieved using ethyl acetate-methanol-formic acid (6:3.8:0.2, by volume) as a developing system followed by densitometric scanning at 230 nm. Method (B) was a high-performance liquid chromatography method; separation was achieved on C18 column, the mobile phase consisted of a mixture of sodium lauryl sulfate buffer 0.1% w/v, pH 3: methanol in the ratio 70:30, v/v and measurement was done at 220 nm. System suitability testing parameters were calculated to ascertain the quality performance of the developed chromatographic methods. The proposed methods have been validated regarding accuracy, precision, and selectivity, moreover they have been successfully applied to Westirizide tablets containing both alogliptin and metformin hydrochloride, results indicate that there was no interference from additives. No significance difference was found when these methods were compared to the reported one.

In-vitro evaluation of rice straw biochars' effect on bispyribac-sodium dissipation and microbial activity in soil.

Dissipation of bispyribac-sodium was estimated in an unamended sandy loam soil and soil amended with rice straw and its biochars in pot culture experiment. Effect of herbicide and amendments on abundance and activity of soil microbial parameters was also assessed by determining soil biological parameters. Amendment type, application rate and soil moisture had differential influence on bispyribac-sodium dissipation and soil's microbial parameters. Amendment of soil with rice straw and its biochars enhanced the dissipation of bispyribac-sodium (DT50 = 7.55-18.44 days) as compared to unamended soil (DT50 = 23.13-28.60 days) and dissipation decreased in this order: rice straw >350BC > 550BC > CBC amended soil > unamended soil. Dissipation of bispyribac-sodium decreased with increase in amendment level of rice straw and its biochars in soil. Irrespective of amendment type and application rate, bispyribac sodium was more persistent under submerged conditions than at field capacity and its DT50 was 10.13 to 28.60 and 7.55-27.14 days, respectively. Dehydrogenase, alkaline phosphatase activity and bacterial population indicated that application of the organic amendment decreased negative effects of the herbicide on soil enzymatic activities. These findings prove that biostimulation using rice straw and its biochars has the potential to decrease the persistence of bispyribac-sodium and minimize its environmental hazards.

Ultimate fate of herbicide tembotrione and its metabolite TCMBA in soil.

Tembotrione is a triketone group herbicide having worldwide applications for weed management in maize. It is considered to be less stable in the environment and its degradation products may have toxicological consequences due to longer persistence and off-site movements. We studied the persistence behavior and leaching potential of tembotrione and its major metabolite TCMBA in clay loam and sandy loam soils having different physico-chemical properties. The rapid transformation of parent tembotrione to degradation products and their high interactions with soil provided challenging task of residues separation from complex soil matrix. Therefore, a novel sample preparation method (modified QuEChERS) was optimized for trace estimation of tembotrione and TCMBA which offered 86.6-95.6% recoveries with limit of detection (LOD) and quantification (LOQ) as 0.001 and 0.003 µg/g, respectively in both soils without any matrix interference. A first order dissipation kinetics was followed by tembotrione and TCMBA residues with half-life ranged from 7.2 to 13.4 days in both soils. Residues reached below detectable limit on 45-60 days after treatments in two application doses. Leaching experiment revealed maximum retention of tembotrione residues from 15 to 25 cm depth in both soils whereas TCMBA show appreciable leaching potential. It was concluded that tembotrione can be phytotoxic to the succeeding crops if applied at late post-emergence stage. TCMBA can contaminate surface and ground water due to continuous and prolonged use of tembotrione particularly in light textured soils.

Non-target effect of bispyribac sodium on soil microbial community in paddy soil.

Bispyribac sodium is frequently used herbicide in the rice field. Though, it has been targeted to kill rice weeds, but its non-target effect on soil microbes in paddy soil was largely unknown. Therefore, in the present study, an attempt was made to assess the non-target effect of bispyribac sodium on alteration of functional variation of soil microbial community and their correlation with microbial biomass carbon (MBC) and soil enzymes. A microcosm experiment set up was made comprising three treatments viz., control (CON) (without application of bispyribac sodium), recommended dose of bispyribac sodium (35 g ha-1) (BS), and double the dose of BS (70 g ha-1) (DBS). Results indicated that the MBC and soil enzyme activities (dehydrogenase, alkaline phosphatase and urease) in BS and DBS-treated soil were significantly (p < 0.05) declined from 1st to 30th day after application as compared to CON. Counts of heterotrophic bacteria, actinomycetes and fungal population were also decreased in BS and DBS-treated soil. The average well color development (AWCD) values derived from Biolog®ecoplates followed the order of DBS ˂ BS ˂ CON. Shannon index value was high (p ≤ 0.05) in CON compared to soil-treated with BS and DBS. Principal component analysis (PCA) showed a clear distinction of the cluster of treatments between CON, BS and DBS. Biplot analysis and heatmap suggested that carboxylic compounds and amino acids showed positive response towards BS-treated soil, whereas phenolic compounds had positive correlation with DBS-treated soil. PCA analysis indicated that oligotrophs was rich in BS-treated paddy soil, whereas copiotrophs and asymbiotic nitrogen fixers were richer in DBS treatment. Overall, the present study revealed that application of recommended dose of BS and its double dose alter the soil microbial population, enzyme activities and functional microbial diversity in paddy soil.

Preparation of a polyhedral oligomeric silsesquioxanes hybrid monolith via a single-step ring-opening polymerization for pressurized capillary electrochromatography.

An organic-silica hybrid monolith was prepared by a single-step ring-opening polymerization of octaglycidyldimethylsilyl polyhedral oligomeric silsesquioxane (POSS-epoxy), polyethylenimine (PEI), and ß-cyclodextrin (ß-CD) in a ternary porogenic solvent consisting of polyethylene glycol, 1,4-butanediol, and 1-propanol. The framework of POSS-PEI hybrid monolith could offer well-defined 3D skeleton, while ß-CD with the ability of forming a host-guest inclusion complexes with a variety of compounds could show an ability of specific selection. The obtained hybrid monoliths were successfully applied for separation of phenols, benzoic acids, and nucleobases. Especially due to the introduction of ß-CD, positional isomers including hydroquinone and resorcinol, o-nitrophenol and p-nitrophenol, as well as p-chlorophenol and o-chlorophenol were baseline separated and the column efficiency reached 82 300 plates/m for hydroquinone.

A permethrin metabolite is associated with adaptive immune responses in Gulf War Illness.

Gulf War Illness (GWI), affecting 30% of veterans from the 1991 Gulf War (GW), is a multi-symptom illness with features similar to those of patients with autoimmune diseases. The objective of the current work is to determine if exposure to GW-related pesticides, such as permethrin (PER), activates peripheral and central nervous system (CNS) adaptive immune responses. In the current study, we focused on a PER metabolite, 3-phenoxybenzoic acid (3-PBA), as this is a common metabolite previously shown to form adducts with endogenous proteins. We observed the presence of 3-PBA and 3-PBA modified lysine of protein peptides in the brain, blood and liver of pyridostigmine bromide (PB) and  PER (PB+PER) exposed mice at acute and chronic post-exposure timepoints. We tested whether 3-PBA-haptenated albumin (3-PBA-albumin) can activate immune cells since it is known that chemically haptenated proteins can stimulate immune responses. We detected autoantibodies against 3-PBA-albumin in plasma from PB + PER exposed mice and veterans with GWI at chronic post-exposure timepoints. We also observed that in vitro treatment of blood with 3-PBA-albumin resulted in the activation of B- and T-helper lymphocytes and that these immune cells were also increased in blood of PB + PER exposed mice and veterans with GWI. These immune changes corresponded with elevated levels of infiltrating monocytes in the brain and blood of PB + PER exposed mice which coincided with alterations in the markers of blood-brain barrier disruption, brain macrophages and neuroinflammation. These studies suggest that pesticide exposure associated with GWI may have resulted in the activation of the peripheral and CNS adaptive immune responses, possibly contributing to an autoimmune-type phenotype in veterans with GWI.

Dissipation of bispyribac sodium in aridisols: Impact of soil type, moisture and temperature.

The study was conducted to evaluate the influence of physicochemical properties of soil, moisture and temperature on the dissipation behaviour of bispyribac sodium under laboratory conditions. Bispyribac sodium residues were extracted using matrix solid phase dispersion and were quantified using liquid chromatography tandem-mass spectrometry. The mean percent recovery of bispyribac sodium from studied soils ranged from 82.7 ±â€¯8.3-105.1±â€¯2.6%. The limit of quantification and limit of detection was 0.006 and 0.002 µg g-1, respectively. Dissipation of bispyribac sodium followed first order kinetics and soil type greatly influenced the dissipation behaviour of bispyribac sodium. Dissipation was faster in loam soil (DT50 = 12.79-14.52days) followed by clay loam (DT50 = 22.01-23.15days), sandy loam (DT50 = 23.34-25.17 days) and loamy sand soil (DT50 = 25.39-27.32days). The amendment of soil with FYM enhanced the dissipation of bispyribac sodium by 1.86-5.96-fold. It dissipated slowly under submerged (DT50 = 21.41-40.96days) conditions as compared to field capacity (DT50 = 12.79-27.32days) in studied soils. The degradation rate increased with the increase in temperature in studied soils and DT50 ranged from 12.79 to 40.96, 7.36-36.96 and 4.09-31.61days at 30, 40 and 50 °C, respectively.

Evaluation of the behaviour of propoxycarbazone herbicide in soils and water under different conditions. Post-targeted study.

The aim of this study is to understand the levels and behaviour of the herbicide propoxycarbazone in environmental compartments, which are poorly characterized considering degradation products that might reach either surface water as groundwater or soil samples. To this end, an analytical method, based on ultra-high performance liquid chromatography (UHPLC) coupled with Orbitrap mass spectrometry (MS), has been developed to determine the parent compound and its transformation products in soils and water. In addition, a set of laboratory trials has been designed to address the dissipation process of propoxycarbazone formulation in both environmental substrates. The study revealed that the dissipation in water followed a first order kinetics and a non-linear "First Order Multi Compartment" model (FOMC) to soil. Relevant advances have been also achieved in terms of the analytical methodology, as far as the UHPLC-Orbitrap-MS technique allows the development of a retrospective screening of pesticide transformation products in water and soils. For this purpose, an accurate-mass database has been built and used for the post-run screening analysis with 9 transformation products. Photodegradation presumably plays an important role in the dissipation of propoxycarbazone. The results of UHPLC-Orbitrap-MS revealed that four transformation products were formed during the degradation process of the herbicide.

Diethyl-Ether Flower Washings of Dianthus cruentus Griseb. (Caryophyllaceae): Derivatization Reactions Leading to the Identification of New Wax Constituents.

Some carnation species (Dianthus spp., Caryophyllaceae) exhibit a strong resistance to drought stress that is connected with the increased surface wax formation. Wax composition is unknown for the majority of Dianthus spp. Herein, mass spectral and gas chromatographic data, in combination with synthesis and chemical transformations (transesterification and synthesis of dimethyl disulfide adducts), enabled the identification of 151 constituents of diethyl-ether washings of fresh flowers of Dianthus cruentus Griseb. from Serbia. The flower wax contained, along with the dominant ubiquitous long-chain n-alkanes, homologous series of n- and branched (iso- and anteiso-) long-chain hexyl alkanoates/alkenoates and alkyl/alkenyl benzoates. The branching position in the mentioned hexyl esters was probed by synthesis of esters of three isomeric hexanols that were spectrally characterized (1 H- and 13 C-NMR, IR, MS). The washings also contained long-chain (Z)- and (E)-alkenes (C23 -C35 ) with several different double bond regiochemistries. Fifty-five of these constituents (eight hexyl esters, two benzoates, and forty-five alkenes) were detected for the first time in Plantae, while ten of these represent completely new compounds. The rare occurrence of these wax constituents makes them possible chemotaxonomic markers of this particular Dianthus sp.

Photoelectrochemical determination of the activity of histone acetyltransferase and inhibitor screening by using MoS2 nanosheets.

The enzyme histone acetyltransferase (HAT) catalyzes the acetylation of a substrate peptide, and acetyl coenzyme A is converted to coenzyme A (CoA). A photoelectrochemical method is described for the determination of the HAT activity by using exfoliated MoS2 nanosheets, phos-tag-biotin, and ß-galactosidase (ß-Gal) based signal amplification. The MoS2 nanosheets are employed as the photoactive material, graphene nanosheets as electron transfer promoter, gold nanoparticles as recognition and capture reagent for CoA, and phos-tag-biotin as the reagent to link CoA and ß-Gal. The enzyme ß-Gal catalyzes the hydrolysis of substrate O-galactosyl-4-aminophenol to generate free 4-aminophenol which is a photoelectrochemical electron donor. The photocurrent increases with the activity of HAT. Under optimal conditions, the response is linear in the 0.3 to 100 nM activity range, and the detection limit is 0.14 nM (at S/N = 3). The assay was applied to HAT inhibitor screening, specifically for the inhibitors C646 and anacardic acid. The IC50 values are 0.28 and 39 µM, respectively. The method is deemed to be a promising tool for epigenetic research and HAT-targeted cancer drug discovery. Graphical abstract Histone acetyltransferase was detected using a sensitive photoelectrochemical method using MoS2 nanosheets as photoactive material.

Liquid chromatography/isotope ratio mass spectrometry analysis of halogenated benzoates for characterization of the underlying degradation reaction in Thauera chlorobenzoica CB-1T.

RATIONALE: Halogenated benzoic acids occur in the environment due to their widespread agricultural and pharmaceutical use. Compound-specific stable isotope analysis (CSIA) has developed over the last decades for investigation of in situ transformation and reaction mechanisms of environmental pollutants amenable by gas chromatography (GC). As polar compounds are unsuitable for GC analysis we developed a method to perform liquid chromatography (LC)/CSIA for halogenated benzoates. METHODS: LC/isotope ratio mass spectrometry (IRMS) utilizing a LC-Surveyor pump coupled to a MAT 253 isotope ratio mass spectrometer via a LC-Isolink interface was applied. For chromatographic separation a YMC-Triart C18 column and a potassium hydrogen phosphate buffer (150 mM, pH 7.0, 40°C, 200 µL mL-1 ) were used, followed by wet oxidation deploying 1.5 mol L-1 ortho-phosphoric acid and 200 g L-1 sodium peroxodisulfate at 75 µL mL-1 . RESULTS: Separation of benzoate and halogenated benzoates could be achieved in less than 40 min over a concentration range of 2 orders of magnitude. Under these conditions the dehalogenation reaction of Thauera chlorobenzoica 3CB-1T using 3-chloro-, 3-bromo- and 4-chlorobenzoic acid was investigated resulting in inverse carbon isotope fractionation for meta-substituted benzoic acids and minor normal fractionation for para-substituted benzoic acids. Together with the respective growth rates this led to the assumption that dehalogenation of para-halobenzoic acids follows a different mechanism from that of meta-halobenzoic acids. CONCLUSIONS: A new LC/IRMS method for the quantitative determination of halogenated benzoates was developed and used to investigate the in vivo transformation pathways of these compounds, providing some insights into degradation and removal of these widespread compounds by T. chlorobenzoica 3CB-1T .

Chemical application strategies to protect water quality.

Management of turfgrass on golf courses and athletic fields often involves application of plant protection products to maintain or enhance turfgrass health and performance. However, the transport of fertilizer and pesticides with runoff to adjacent surface waters can enhance algal blooms, promote eutrophication and may have negative impacts on sensitive aquatic organisms and ecosystems. Thus, we evaluated the effectiveness of chemical application setbacks to reduce the off-site transport of chemicals with storm runoff. Experiments with water soluble tracer compounds confirmed an increase in application setback distance resulted in a significant increase in the volume of runoff measured before first off-site chemical detection, as well as a significant reduction in the total percentage of applied chemical transported with the storm runoff. For example, implementation of a 6.1 m application setback reduced the total percentage of an applied water soluble tracer by 43%, from 18.5% of applied to 10.5% of applied. Evaluation of chemographs revealed the efficacy of application setbacks could be observed with storms resulting in lesser (e.g. 100 L) and greater (e.g. > 300 L) quantities of runoff. Application setbacks offer turfgrass managers a mitigation approach that requires no additional resources or time inputs and may serve as an alternative practice when buffers are less appropriate for land management objectives or site conditions. Characterizing potential contamination of surface waters and developing strategies to safeguard water quality will help protect the environment and improve water resource security. This information is useful to grounds superintendents for designing chemical application strategies to maximize environmental stewardship. The data will also be useful to scientists and regulators working with chemical transport and risk models.

Responses of macroinvertebrate communities to pesticide application in irrigated rice fields.

The ability to recover to original states after disturbances makes macroinvertebrates useful tools for assessing the impacts of pesticides. Many studies showed that direct exposure to pesticides decreases macroinvertebrate richness and alters their composition. The main objective of this study was to assess recovery patterns in macroinvertebrate communities after pesticide application in irrigated rice fields. We analyzed short-term temporal dynamics of macroinvertebrate communities after application of the herbicides bispyribac-sodium and clomazone and the insecticide chlorantraniliprole, over the rice-growing season in southern Brazil. We selected three conventional rice fields and the recovery of macroinvertebrate communities was also compared with three adjacent natural ponds. The study was developed from November 2011 to February 2012 (rice-growing season). Five macroinvertebrate collections were carried out 3, 7, 14, 38, and 60 days after pesticide application (November 25). Rice fields showed lower richness and abundance than ponds in the period immediately after pesticide application, and recovery rates in the richness of macroinvertebrate communities were more conspicuous as pesticide residuals dissipated from the fields. Macroinvertebrate community structure in rice fields also became more similar to natural ponds as pesticide traces were scarcer. However, macroinvertebrate abundance patterns were not related to pesticide concentrations in the fields. Our results supported the general hypothesis on the negative effects of pesticide application on macroinvertebrate community in irrigated rice fields, although other environmental features (e.g., length of the flooded period) also contributed to explain temporal dynamics in the macroinvertebrate communities from irrigated rice fields.

Effect of pH on the Transformation of a New Readymix Formulation of the Herbicides Bispyribac Sodium and Metamifop in Water.

A laboratory experiment was conducted to investigate the effect of pH on the persistence and the dissipation of the new readymix formulation of bispyribac sodium and metamifop. The experiment was conducted in water of three different pH viz. 4.0, 7.0 and 9.2. The spiking level of both the compounds in water was 1.0 and 2.0 µg/mL. The residues were extracted by a simple, quick and reliable method and quantified by liquid chromatography tandem mass spectrometry (LC-MS/MS). The method was justified based on the recovery study, which was > 85%. The dissipation of both compounds followed first order kinetics. The half-life values ranged between 19.86-36.29 and 9.92-19.69 days for bispyribac sodium and metamifop, respectively. The pH of water has a prominent effect on degradation of both the compounds. The rate of dissipation of both the compounds was highest in water of acidic pH followed by neutral and alkaline pH.

Synthetic Co-Attractants of the Aggregation Pheromone of the Date Palm Root Borer Oryctes agamemnon.

Laboratory and field investigations to identify and evaluate plant co-attractants of the aggregation pheromone of the date palm pest Oryctes agamemnon are reported. Volatiles emitted by freshly cut palm core and palm core with feeding males, were collected, analyzed by gas chromatography coupled to mass spectrometry and evaluated in olfactometers alone or combined with synthetic pheromone. A collection of palm odor without male effluvia was attractive alone and enhanced attraction to synthetic pheromone in an olfactometer similar to that to a collection of palm odor emitted with feeding males and containing natural pheromone. Behavioral responses to collections of palm volatiles were correlated to the amount of volatiles material in them. Enhancement of the attractiveness of the pheromone was not correlated to chemicals specific to beetle feeding. The chemicals common to the active collections extracts were benzoate esters, mostly ethyl benzoate, anisole derivatives and sesquiterpenes. Blends of the most abundant components of the extracts were evaluated for enhancement of the attractiveness of pheromone (1 µg) in olfactometers at 1 or 10 µg doses. The mixtures were further evaluated by field trapping in Tunisia at 3-10 mg/day using reference (6 mg/day) or experimental pheromone formulations. A mixture of ethyl benzoate, 4-methylanisole and farnesol (1:1:1 w/w at 6.5 mg/day) enhanced captures in pheromone baited traps in 2014 and 2015 and this mixture was as active as the natural palm bait. The practical prospect of the result for the management for O. agamemnon, and other palm beetles is discussed.

Effects of domestic chemical stressors on expression of allergen genes in the European house dust mite.

The expression of allergen genes in house dust mites is influenced by temperature and relative humidity, but little is known of the impacts of other environmental factors that may alter the repertoire of allergens released by mites in home microhabitats. Bioassays were conducted in concave microscope slides in combination with real-time quantitative polymerase chain reaction (RT-qPCR) to analyse gene expression of 17 allergens of Dermatophagoides pteronyssinus (Acariformes: Pyroglyphidae) exposed to three chemical stressors that can be present in domestic environments. Short-term exposure (5-12 days) to diesel exhaust particles (DEPs) (1 µg/cm2 ), bacterial lipopolysaccharide endotoxin (0.1 µg/cm2 ) and benzyl benzoate (3.2 µg/cm2 ), at concentrations exceeding those expected in homes, had no significant effect on allergen transcription. A significant increase in the transcription of allergens Der p 3, Der p 8 and Der p 21 was observed only after exposing mites to a higher concentration of DEPs (10 µg/cm2 ) over a whole generation. In combination, the present results suggest that the analysed factors have low impact on allergen production. The methodology described here offers a sound and rapid approach to the broad-spectrum study of factors affecting allergen-related mite physiology, and allows the simultaneous screening of different factors in a relatively short period with consideration of the full spectrum of allergen genes.

Exposure of hospitalised pregnant women to plasticizers contained in medical devices.

BACKGROUND: Medical devices (MDs) in polyvinyl chloride (PVC) are not a well-known source of exposure to plasticizers, in particular during pregnancy. Because of its toxicity, the di-(2-ethylhexyl) phthalate (DEHP) has been replaced by other plasticizers such as di (isononyl)-cyclohexane-1,2-dicarboxilic acid (DINCH), tri-octyltrimellitate (TOTM) and di-(isononyl) phthalate (DiNP). Our study aimed to quantify the plasticizers (DEHP and alternative plasticizers) contained in PVC medical devices used for hospitalised pregnant women and to describe which these MDs had been used (type, number, duration of exposure). METHODS: The plasticizers contained in the MDs used for daily care in the Obstetrics Department of a French University Hospital were extracted from PVC (after contact with a chloroform solution), identified and quantified by gas-chromatography-mass-spectrometry analysis. A total of 168 pregnant women hospitalised in the Obstetrics Department with at least one catheter were included in the observational study. The median number of MDs containing plasticizers used and the daily duration of exposure to the MDs were compared in three groups of pregnant women: "Pathology group" (women hospitalised for an obstetric disorder who did not give birth during this hospitalisation; n = 52), "Pathology and delivery group" (hospitalised for an obstetric disorder and who gave birth during this stay; n = 23) and "Delivery group" (admitted for planned or spontaneous delivery without obstetric disorder; n = 93). RESULTS: DiNP, TOTM and DINCH were the predominant plasticizers contained in the MDs at an amount of 29 to 36 g per 100 g of PVC. Women in the "Pathology group" (preterm labour or other pathology) were exposed to a median number of two MDs containing TOTM and one MD containing DiNP, fewer than those in the "Pathology and delivery group" (p < 0.05). Women in the "Pathology group" had a median exposure of 3.4 h/day to MDs containing DiNP and 8.2 h/day to MDs containing TOTM, longer than those in the "Delivery group" (p < 0.01). CONCLUSIONS: Our study shows that the medical management of pregnant women in a hospital setting entails exposure to MDs containing alternative plasticizers (DiNP, TOTM and DINCH).