Development of a polyurethane-coated thin film solid phase microextraction device for multi-residue monitoring of pesticides in fruit and tea beverages.

A novel solid-phase microextraction device coated with an efficient and cheap thin film of polyurethane was developed for trace determination of 13 widely used pesticides in fruit and tea beverages. A round-shaped polyurethane film covering the bottom of a glass vial was fabricated as the sorbent to exhibit a superior capacity for preconcentrating target compounds and reducing matrix interferences. After optimization of the key parameters including the film type, extraction time, solution pH, ionic strength, desorption solvent, and conditions, this device allowed an efficient adsorption-desorption cycle for the pesticides accomplished in one vial. Coupled with gas chromatography-electron capture detection, the polyurethane-coated thin film microextraction method was successfully established and applied for the analysis of real fruit and tea drinks, showing low limits of detection (0.001-0.015 µg/L), wide linear ranges (1.0-500.0 µg/L, r2  > 0.9931), good relative recoveries (77.2%-106.3%) and negligible matrix effects (86.1%-107.5%) for the target pesticides. The proposed approach revealed strong potential of extending its application by flexibly modifying the type or size of the coating film. This study provides insights into the enrichment of contaminants from complex samples using inexpensive and reusable microextraction devices that can limit the environmental and health impact of the sample preparation protocol.

Emission of methylene diphenyl diisocyanate and methylene dianiline during use of cure-in-place methylene diphenyl diisocyanate-based consumer products.

The aim of this study was to provide realistic isocyanate and amine emission data when using different methylene diphenyl diisocyanate (MDI)-based polyurethane consumer products. Emission testing (air sampling) of diisocyanates and corresponding diamines was performed in a full-scale controlled-environment chamber during different work operations, such as gluing, mixing and foaming. The polyurethane products used were construction glue, one-component foam and two different two-component adhesives used in parquet flooring. Air sampling for isocyanates and amines was performed in the breathing zone of the worker and at different positions inside the controlled-environment chamber while the work operations were performed. Air sampling was also performed after the application, at different positions inside the chamber, to cover the post curing phase. Low air concentrations (0.1-0.7 µg MDI/m3, 0.03-0.2 µg isocyanate group (NCO)/m3) were found in the breathing zone and close to the work operation for some of the gluing applications. No methylene diphenyl diamine (MDA) concentrations above the limit of quantification were found for any of the applications in the breathing zone air. These results indicated that inhalation exposure to MDA or MDI would be expected to be minimal during application of do-it-yourself consumer products containing MDI.

Assessment of personal inhalation and skin exposures to polymeric methylene diphenyl diisocyanate during polyurethane fabric coating.

Methylene diphenyl diisocyanate (MDI) monomers and polymeric MDI (pMDI) are aromatic isocyanates widely used in the production of polyurethanes. These isocyanates can cause occupational asthma, hypersensitivity pneumonitis, as well as contact dermatitis. Skin exposure likely contributes toward initial sensitization but is challenging to monitor and quantitate. In this work, we characterized workers' personal inhalation and skin exposures to pMDI in a polyurethane fabric coating factory for subsequent health effect studies. Full-shift personal and area air samples were collected from eleven workers in representative job areas daily for 1-2 weeks. Skin exposure to hands was evaluated concomitantly with a newly developed reagent-impregnated cotton glove dosimeter. Samples were analyzed for pMDI by liquid chromatography-tandem mass spectrometry. In personal airborne samples, the concentration of 4,4'-MDI isomer, expressed as total NCO, had a geometric mean (GM) and geometric standard deviation (GSD) of 5.1 and 3.3 ng NCO/m3, respectively (range: 0.5-1862 ng NCO/m3). Other MDI isomers were found at much lower concentrations. Analysis of 4,4'-MDI in the glove dosimeters exhibited much greater exposures (GM: 10 ng/cm2) and substantial variability (GSD: 20 ng NCO/cm2; range: 0-295 ng NCO/cm2). MDI inhalation exposure was well below occupational limits for MDI for all the job areas. However, MDI skin exposure to hands was substantial. These findings demonstrated the potential for substantial isocyanate skin exposure in work settings with very low airborne levels. This exposure characterization should inform future studies that aim to assess the health effects of work exposures to MDI and the effectiveness of protective measures.

Toluene diisocyanate occupational exposure data in the polyurethane industry (2005-2020): A descriptive summary from an industrial hygiene perspective.

This article provides an overview of toluene diisocyanate (TDI) workplace air concentration data. Data were collected between 2005-2020 in workplaces across the United States, Canada, and the European Union by a number of different organizations, primarily using the sampling procedures published in OSHA Methods 42 and 5002. The data were then collated and organized by the International Isocyanate Institute. Air samples were collected from several market segments, with a large portion of the data (87%) from the flexible foam industry. The air samples (2534 in total) were categorized into "area" or "personal," and the personal samples were subcategorized into "task," "short term," and "long term." Most of the air sample concentrations (87%) were less than 5 ppb. However, the presence of airborne TDI greater than 5 ppb indicated the importance of respiratory protection in some situations; therefore, respirator use patterns were studied and summarized. Additionally, this article provides a summary of air sample concentrations at different flexible foam manufacturing job roles. The information on air sampling concentrations and respiratory protection during TDI applications collected in this paper could be useful for product stewardship and industrial hygiene purposes in the industries studied.

Guidance on the Application of Polyurethane Foam Disk Passive Air Samplers for Measuring Nonane and Short-Chain Chlorinated Paraffins in Air: Results from a Screening Study in Urban Air.

This study provides guidance on using polyurethane foam-based passive air samplers (PUF-PASs) for atmospheric nonane chlorinated paraffins (C9-CPs) and short-chain CPs (SCCPs) and reports SCCP concentrations in air in the Greater Toronto Area (GTA), Canada. We estimated the partition coefficients between PUF and air (KPUF-A) and between octanol and air (KOA) for C9-CP and SCCP congeners using the COSMO-RS method, so that PUF disk uptake profiles for each formula group could be calculated. We then measured SCCP concentrations in PUF disk samples collected from distinct source sectors in urban air across the GTA. Concentrations in samplers were used to calculate C9-CP and SCCP concentrations in air and the PUF disk uptake profiles revealed that time-weighted linear phase sampling was possible for congeners having log KOA values greater than 8.5. The highest SCCP concentrations, with an annual average concentration of 35.3 ng/m3, were measured at the industrial site, whereas lower but comparable SCCP concentrations were found in residential and background sites, with annual averages of 7.73 and 10.5 ng/m3, respectively. No consistent seasonal variation in SCCP concentrations was found in the six distinct source sectors. Direct measurements of KPUF-A and KOA values as a function of temperature could be used to increase accuracy in future studies.

A novel identification method for CPPU-treated kiwifruits based on images.

BACKGROUND: The application of exogenous plant growth regulator, for example forchlorfenuron (CPPU), on kiwifruits has become an important factor that influences kiwifruit economic efficiency and the health development of the kiwifruit industry. Owing to the slight difference in calyx shape between the kiwifruits treated with CPPU (CPPU-treated kiwifruits) and the kiwifruits without CPPU treatment (CPPU-untreated kiwifruits), this study aims to provide a cheap, quick, convenient, and non-destructive method for identifying CPPU-treated kiwifruits based on the images of kiwifruits captured at visible lights. RESULTS: The identification method includes three steps. Firstly, the kiwifruit was extracted from the background by using Otsu algorithm, hole filling operation and 'bwareaopen' function. Secondly, the calyx was extracted by using corrosion, image enhancement, hole filling and closing operations. Finally, the length/width ratio of the minimum enclosing rectangle of calyx region was calculated. The kiwifruit was regarded as a CPPU-treated kiwifruit if the length/width ratio of the rectangle was higher than 1.6. Otherwise, the kiwifruit was regarded as a CPPU-untreated one. The method had the total identification accuracy rate of 90.0% when the kiwifruit images were captured either by utilizing a smartphone at normal lighting condition or by using an image acquisition system. CONCLUSION: The programs run on computer and smartphone were developed, and they could realize kiwifruit identification in 0.6 s and 2 s, respectively. The study makes identifying CPPU-treated kiwifruits in online processing be realizable, and offers a convenient method for kiwifruit consumers. © 2019 Society of Chemical Industry.

Elucidation of non-intentionally added substances migrating from polyester-polyurethane lacquers using automated LC-HRMS data processing.

An untargeted strategy aiming at identifying non-intentionally added substances (NIAS) migrating from coatings was developed. This innovative approach was applied to two polyester-polyurethane lacquers, for which suppliers previously provided the identity of the monomers involved. Lacquers were extracted with acetonitrile and analyzed by liquid chromatography-high resolution mass spectrometry (LC-HRMS). Data, acquired in the full scan mode, were processed using an open-source R-environment (xcms and CAMERA packages) to list the detected features and deconvolute them in groups related to individual compounds. The most intense groups, accounting for more than 85% of cumulated feature intensities, were then investigated. A homemade database, populated with predicted polyester oligomer combinations from a relevant selection of diols and diacids, enabled highlighting the presence of 14 and 17 cyclic predicted polyester oligomers in the two lacquers, including three mutual combinations explained by common known monomers. Combination hypotheses were strengthened by chromatographic considerations and by the investigation of fragmentation patterns. Regarding unpredicted migrating substances, four monomers were hypothesised to explain several polyester or caprolactam oligomer series. Finally, considering both predicted and tentatively elucidated unpredicted oligomers, it was possible to assign hypotheses to features representing up to 82% and 90% of the cumulated intensities in the two lacquers, plus 9% and 3% (respectively) originating from the procedural blank. Graphical abstract Elucidation of non-intentionally added substances.

Nontarget Analysis via LC-QTOF-MS to Assess the Release of Organic Substances from Polyurethane Coating.

A novel approach was investigated for the assessment of leaching from a one-component polyurethane (1C-PU) coating used for hydraulic structures using nontarget analysis via LC-QTOF-MS. Leaching behavior of the 1C-PU coating was studied using experiments in which the coating was exposed to water for defined periods (6 h, 24 h, 3 d, 14 d). Three hardening durations for the 1C-PU coating were tested (0 h, 24 h, 14 d) as well as two water matrices (ultrapure water and river water), including a successive water renewal. Dissolved organic carbon, total nitrogen bound and nontarget measurements via LC-QTOF-MS showed that under all tested conditions organic substances were leached out of the 1C-PU coating. The shorter the hardening duration and the longer the leaching duration, the higher were the number and quantities of the eluted substances, while the influence of the water matrix was minor with respect to substance elution. Based on the MS2 spectra from the LC-QTOF-MS measurements, 30 substances released from the 1C-PU coating were tentatively identified. These substances belong to five chemical groups: derivatives of (i) N-(tosyl)carbamate, (ii) p-toluenesulfonamide (PTSA), (iii) 4,4'-methylenediphenyl diisocyanate (4,4'-MDI), (iv) toluenediisocyanate (TDI), and (v) oligo(ethylene) ([C2H4O]n) as well as p-toluenesulfonic acid. The identity of seven substances was confirmed by authentic reference standards, all of which exhibited an elevated bacterial toxicity to Aliivibrio fischeri. p-Toluenesulfonic acid was present in a German canal (Teltowkanal) with concentrations of up to 11 µg L-1.

[OCCUPATIONAL RISK ASSESSMENT IN MODERN CONDITIONS OF EXPLOITATION OF POLYURETHANEFOAM INDUSTRIES].

In the article there are presented data on the evaluation of occupational risk on two types of modern production of polyurethane foam (PUF), one of which is a large-tonnage fast-growth production, the 2nd type is semidomestic industry being different in small volume of output products. An analysis and evaluation of occupational exposure to large-scale production was performed patient-specifically with the use of elaborated individual cards, where there was introduced information about occupational route, the level of harmful factors of the working environment in all the years of work, the duration of exposure. The research results allowed to establish that the occupational risk in representatives of the main professions in the large-scale production (operators and handlers) is referred to a class of working conditions 3.2, which corresponds to the risk categories--moderate (Important), and demonstrates the need for further improvement of the system of preventive measures. At the small production working conditions were characterized by the presence of a large number of manual operations and comply with Class 3.3--category of professional risk-high (Unbearable). To reduce the risk to the health of workers of this type of production it is necessary to develop documents, that will increase the responsibility of employers to ensure safe working conditions.

CIP10 optimization for 4,4-methylene diphenyl diisocyanate aerosol sampling and field comparison with impinger method.

4,4-methylene diphenyl diisocyanate (MDI) aerosol exposure evaluation in spray foam insulation application is known as being a challenge because the spray foam application actually involves a fast-curing process. Available techniques are either not user-friendly or are inaccurate or not validated for this application. To address these issues, a new approach using a CIP10M was developed to appropriately collect MDI aerosol in spray foam insulation while being suitable for personal sampling. The CIP10M is a commercially available personal aerosol sampler that has been validated for the collection of microbial spores into a liquid medium. Tributylphosphate with 1-(2-methoxyphenyl)piperazine (MOPIP) was introduced into the CIP10M to collect and stabilize the MDI aerosols. The limit of detection and limit of quantification of the method were 0.007 and 0.024 µg ml(-1), respectively. The dynamic range was from 0.024 to 0.787 µg ml(-1) (with R (2) ≥ 0.990), which corresponds to concentrations in the air from 0.04 to 1.3 µg m(-3), assuming 60 min of sampling at 10 l min(-1). The intraday and interday analytical precisions were <2% for all of the concentration levels tested, and the accuracy was within an appropriate range of 98 ± 1%. No matrix effect was observed, and a total recovery of 99% was obtained. Parallel sampling was performed in a real MDI foam spraying environment with a CIP10M and impingers containing toluene/MOPIP (reference method). The results obtained show that the CIP10M provides levels of MDI monomer in the same range as the impingers, and higher levels of MDI oligomers. The negative bias observed for MDI monomer was between 2 and 26%, whereas the positive bias observed for MDI oligomers was between 76 and 113%, with both biases calculated with a confidence level of 95%. The CIP10M seems to be a promising approach for MDI aerosol exposure evaluation in spray foam applications.

Flexural strengths of conventional and nanofilled fiber-reinforced composites: a three-point bending test.

OBJECTIVES: The purpose of this study was to evaluate the effect of the introduction of nanofillers on the mechanical properties of fiber-reinforced composites (FRCs) for stabilization and conservative treatment of multiple traumatized anterior teeth. In particular, the aim of the research was to point out the force levels of two sizes (diameters 0.6 and 0.9 mm) of both conventional and nanofilled FRCs. METHODS: Eighty FRCs samples were divided into eight groups, each consisting of 10 specimens. Conventional (groups 1, 2, 3, and 4) and nanofilled (groups 5, 6, 7, and 8) FRC samples were evaluated. Each FRC was tested in two diameters (0.6 and 0.9 mm) and under two deflections (1 and 2 mm). Each sample was polymerized with the same halogen curing unit and then evaluated with a 3-point bending test on a universal testing machine after 48 h of dry storage. RESULTS: Nanofilled FRCs showed significantly higher load values than conventional FRCs. Moreover, 0.9-mm-diameter FRCs showed significantly higher load value than 0.6-mm-diameter FRCs. Specimens tested at 2-mm deflection showed significantly higher load values than those tested at 1-mm deflection. CONCLUSIONS: Nanofilled FRCs showed significantly higher load values than conventional FRCs. Higher flexural strength values were recorded with 1-mm deflection for both FRC tested.

Comparison of solvent/derivatization agent systems for determination of extractable toluene diisocyanate from flexible polyurethane foam.

Flexible polyurethane foam (FPF) is produced from the reaction of toluene diisocyanate (TDI) and polyols. Limited and conflicting results exist in the literature concerning the presence of unreacted TDI remaining in FPF as determined by various solvent extraction and analysis techniques. This study reports investigations into the effect of several solvent/derivatization agent combinations on extractable TDI results and suggests a preferred method. The suggested preferred method employs a syringe-based multiple extraction of foam samples with a toluene solution of 1-(2-methoxyphenyl)-piperazine. Extracts are analyzed by liquid chromatography using an ion trap mass spectrometry detection technique. Detection limits of the method are ~10ng TDI g(-1) foam (10 ppb, w/w) for each TDI isomer (i.e. 2,4-TDI and 2,6-TDI). The method was evaluated by a three-laboratory interlaboratory comparison using two representative foam samples. The total extractable TDI results found by the three labs for the two foams were in good agreement (relative standard deviation of the mean of 30-40%). The method has utility as a basis for comparing FPFs, but the interpretation of extractable TDI results using any solvent as the true value for 'free' or 'unreacted' TDI in the foam is problematic, as demonstrated by the difference in the extracted TDI results from the different extraction systems studied. Further, a consideration of polyurethane foam chemistry raises the possibility that extractable TDI may result from decomposition of parts of the foam structure (e.g. dimers, biurets, and allophanates) by the extraction system.

Polyaromatic hydrocarbon thin film layers on glass, dust, and polyurethane foam surfaces.

An investigation was conducted into the dynamic behavior of two polyaromatic hydrocarbon (PAH) semi-volatile organic compound (SVOC) naphthalene (NAP) and benzo [ghi]perylene (BghiP) in air and on various surfaces including glass, dust, and polyurethane foam (PUF) to understand their interaction with different media. A confocal fluorescence microscope and an infrared microscope were employed to detect and monitor the concentration-, time-, and temperature-dependent changes of the aromatic NAP and BghiP species on the surfaces. Infrared two-dimensional mapping of the vibrational characteristic peaks was used to track the two PAHs on the surfaces. Gas chromatography-mass spectrometry (GC-MS) was employed to measure the gaseous concentrations. The sorption of NAP and BghiP on the surfaces was estimated using Arizona desert sand fine (ISO 12103-1 A2) dust and organic contaminant household (SRM 2585) dust. The surface-to-air partition coefficients of NAP and BghiP were estimated on the different surfaces of glass, dust, and PUF. Molecular dynamic simulations were performed on dust surfaces based on the Hatcher model to understand the behavior of NAP and BghiP on dust surfaces. The Weschler-Nazaroff model was introduced to predictPAH film accumulation on the surfaces, providing a better understanding of PAH interaction with different environmental media. These findings could contribute to developing effective strategies to mitigate the adverse impact of PAHs on the environment and human health.

The use of polymer compounds in the deposits from the combustion of briquettes in domestic heating as an identifier of fuel quality.

The utilisation of waste wood from furniture production brings new problems connected with an incomplete thermochemical decomposition of additives (chemicals for improving properties of plastics) in small heating with the addition of sources. Unique organic compounds produced by the combustion of waste wood allow the identification of the type of fuel. The organic compounds contained in the char deposits were analysed by pyrolysis gas chromatography with mass spectrometry. The deposits from the combustion of briquettes from furniture production contain organic compounds originating by decomposition of phenolic resins, aminoplasts (urea-formaldehyde, resorcinol-formaldehyde and melamine), polyurethanes and wood glue. Additives contained in the deposits include plasticisers such as phthalates (DEHP, dibutyl phthalate and diisobutyl phthalate), flame retardants (2-propanol, 1-chlorophosphate (3:1) and p-terphenyl). Deposits from the combustion of briquettes from virgin wood do not contain these compounds. The total amount of compounds identified in the deposits from the boiler, which do not come from virgin wood combustion, varies in the range between 4.25 and 6.25 g/kg. Phthalates (55.5%) and PVAc adhesives (18.6%) are the main anthropogenic compounds in the deposits from domestic boilers.

Novel eco-friendly methodology to determine polycyclic aromatic hydrocarbons in polyurethane foam for air monitoring: Application to spatial and temporal distribution survey.

This study aimed at developing a new method for the extraction of polycyclic aromatic hydrocarbons (PAHs) in polyurethane foam (PUF). In the field of PAH monitoring, passive samplers using PUF disks are widely used. However, current extraction methods are time and solvent consuming. This new method employs 3 times a sixteenth of the PUF disk, with method detection limits (MDL) values below 5 and 13 ng/sampler for 3- and 4-rings PAHs, respectively. The use of only parts of the disk allows extraction by ultrasounds using exclusively 120 mL of ethanol, making it environmentally friendly. Ethanolic extracts are then purified and concentrated using microextraction by packed sorbent (MEPS) before GC-MS analyses. This method was applied for an environmental survey in a French urban area with an oceanic climate. Variations in PAH concentrations were observed depending on the site studied (urban, traffic, periurban and rural), as well as temporal variations.

Highly Stretchable and Robust Electrochemical Sensor Based on 3D Graphene Oxide-CNT Composite for Detecting Ammonium in Sweat.

Wearable electrochemical sensors have attracted tremendous attention and have been experiencing rapid growth in recent years. Sweat, one of the most suitable biological fluids for non-invasive monitoring, contains various chemical elements relating abundant information about human health conditions. In this work, a new type of non-invasive and highly stretchable potentiometric sweat sensor was developed based on all-solid-state ion-selective electrode (ISE) coupled with poly(dimethylsiloxane; PDMS) and polyurethane (PU). This highly stretchable composite of PDMS-PU allows the sensor to be robust, with the PDMS providing a flexible backbone and the PU enhancing the adhesion between the electrodes and the substrate. In addition, graphene-carbon nanotube (CNT) network 3D nanomaterials were introduced to modify the ion selective membrane (ISM) in order to increase the charge transfer activity of the ISEs, which also could minimize the formation of water layers on the electrode surface, as such nanomaterials are highly hydrophobic. As a result, the sensor demonstrated a wide detection range of NH4+ from 10-6 M to 10-1 M with high stability and sensitivity-showing a high sensitivity of 59.6 ± 1.5 mV/log [NH4+] and an LOD lower than 10-6 M. Under a strain of 40%, the sensor still showed a sensitivity of 42.7 ± 3.1 mV/log [NH4+]. The proposed highly stretchable and robust electrochemical sweat sensor provides a new choice for wearable-device-based personal daily healthcare management beyond hospital-centric healthcare monitoring.

Novel and high volume use flame retardants in US couches reflective of the 2005 PentaBDE phase out.

California's furniture flammability standard Technical Bulletin 117 (TB 117) is believed to be a major driver of chemical flame retardant (FR) use in residential furniture in the United States. With the phase-out of the polybrominated diphenyl ether (PBDE) FR mixture PentaBDE in 2005, alternative FRs are increasingly being used to meet TB 117; however, it was unclear which chemicals were being used and how frequently. To address this data gap, we collected and analyzed 102 samples of polyurethane foam from residential couches purchased in the United States from 1985 to 2010. Overall, we detected chemical flame retardants in 85% of the couches. In samples purchased prior to 2005 (n = 41) PBDEs associated with the PentaBDE mixture including BDEs 47, 99, and 100 (PentaBDE) were the most common FR detected (39%), followed by tris(1,3-dichloroisopropyl) phosphate (TDCPP; 24%), which is a suspected human carcinogen. In samples purchased in 2005 or later (n = 61) the most common FRs detected were TDCPP (52%) and components associated with the Firemaster550 (FM 550) mixture (18%). Since the 2005 phase-out of PentaBDE, the use of TDCPP increased significantly. In addition, a mixture of nonhalogenated organophosphate FRs that included triphenyl phosphate (TPP), tris(4-butylphenyl) phosphate (TBPP), and a mix of butylphenyl phosphate isomers were observed in 13% of the couch samples purchased in 2005 or later. Overall the prevalence of flame retardants (and PentaBDE) was higher in couches bought in California compared to elsewhere, although the difference was not quite significant (p = 0.054 for PentaBDE). The difference was greater before 2005 than after, suggesting that TB 117 is becoming a de facto standard across the U.S. We determined that the presence of a TB 117 label did predict the presence of a FR; however, lack of a label did not predict the absence of a flame retardant. Following the PentaBDE phase out, we also found an increased number of flame retardants on the market. Given these results, and the potential for human exposure to FRs, health studies should be conducted on the types of FRs identified here.

Analytical tools for identification of non-intentionally added substances (NIAS) coming from polyurethane adhesives in multilayer packaging materials and their migration into food simulants.

Adhesives used in food packaging to glue different materials can provide several substances as potential migrants, and the identification of potential migrants and migration tests are required to assess safety in the use of adhesives. Solid-phase microextraction in headspace mode and gas chromatography coupled to mass spectrometry (HS-SPME-GC-MS) and ChemSpider and SciFinder databases were used as powerful tools to identify the potential migrants in the polyurethane (PU) adhesives and also in the individual plastic films (polyethylene terephthalate, polyamide, polypropylene, polyethylene, and polyethylene/ethyl vinyl alcohol). Migration tests were carried out by using Tenax(®) and isooctane as food simulants, and the migrants were analyzed by gas chromatography coupled to mass spectrometry. More than 63 volatile and semivolatile compounds considered as potential migrants were detected either in the adhesives or in the films. Migration tests showed two non-intentionally added substances (NIAS) coming from PU adhesives that migrated through the laminates into Tenax(®) and into isooctane. Identification of these NIAS was achieved through their mass spectra, and 1,6-dioxacyclododecane-7,12-dione and 1,4,7-trioxacyclotridecane-8,13-dione were confirmed. Caprolactam migrated into isooctane, and its origin was the external plastic film in the multilayer, demonstrating real diffusion through the multilayer structure. Comparison of the migration values between the simulants and conditions will be shown and discussed.

Detection and quantification of monomers in unstimulated whole saliva after treatment with resin-based composite fillings in vivo.

Resin-based dental restorative materials contain allergenic methacrylate monomers, which may be released into saliva after restorative treatment. Monomers from resin-based composite materials have been demonstrated in saliva in vitro; however, studies analyzing saliva after restorative therapy are scarce. The aim of this study was to quantify methacrylate monomers in saliva after treatment with a resin-based composite filling material. Saliva was collected from 10 patients at four start points--before treatment, and 10 min, 24 h, and 7 d after treatment--and analysed by combined chromatography/mass spectrometry. The monomers bisphenol-A diglycidyl methacrylate (Bis-GMA), 2-hydroxyethyl methacrylate (HEMA), and urethane dimethacrylate (UDMA) were detected and quantified in the samples collected shortly (10 min) after treatment. The amounts detected ranged from 0.028 to 9.65 µg ml(-1) for Bis-GMA, from 0.015 to 0.19 µg ml(-1) for HEMA, and from 0.004 to 1.2 µg ml(-1) for UDMA. Triethyleneglycol dimethacrylate (TEGDMA) was detected in four of the samples. Ethoxylated bisphenol-A dimethacrylate (Bis-EMA) was not detected. Monomers were not detected in saliva samples collected before treatment, or 24 h or 7 d after treatment, with the exception of one sample, 24 h after treatment, in which HEMA was detected. In conclusion, monomers from the investigated resin-based composite and adhesive system were present in saliva shortly after treatment. One week after treatment, no monomers could be detected in patients' saliva samples.