Application of validated migration models for the risk assessment of styrene and acrylonitrile in ABS plastic toys.

With styrene and acrylonitrile in ABS plastic toys as examples, this paper introduces to the development of a systematic strategy for studying the chemical migration risk in toys. The approach, included the detection method, establishment of migration model, model verification, and the practical application of the model in risk assessment. First, simple and sensitive methods for detecting analyte residues and migration were developed by headspace GC-MS. Then, the migration models were established based on the migration data from 5 min to 168 h and verified using 11 ABS samples. The results showed that the predicted values of the models and the experimental values had a good fit (RMSE=0.10-8.72 %). Subsequently, the migration of analytes in 94 ABS toys was predicted with these models at specific migration times. The daily average exposure level to styrene and acrylonitrile were estimated for children (3 months to 3 years). At last, the migration models reasonably predicted that the cancer risk of styrene and acrylonitrile in ABS toys were 1.6 × 10-8-1.4 × 10-6 and 3.1 × 10-8-1.6 × 10-6, respectively. This research contributes to promote toy safety and child health by enriching migration models and risk assessments.

A comprehensive assessment of a new series of 5',6'-difluorobenzotriazole-acrylonitrile derivatives as microtubule targeting agents (MTAs).

Microtubules (MTs) are the principal target for drugs acting against mitosis. These compounds, called microtubule targeting agents (MTAs), cause a mitotic arrest during G2/M phase, subsequently inducing cell apoptosis. MTAs could be classified in two groups: microtubule stabilising agents (MSAs) and microtubule destabilising agents (MDAs). In this paper we present a new series of (E) (Z)-2-(5,6-difluoro-(1H)2H-benzo[d] [1,2,3]triazol-1(2)-yl)-3-(R)acrylonitrile (9a-j, 10e, 11a,b) and (E)-2-(1H-benzo[d] [1,2,3]triazol-1-yl)-3-(R)acrylonitrile derivatives (13d,j), which were recognised to act as MTAs agents. They were rationally designed, synthesised, characterised and subjected to different biological assessments. Computational docking was carried out in order to investigate the potential binding to the colchicine-binding site on tubulin. From this first prediction, the di-fluoro substitution seemed to be beneficial for the binding affinity with tubulin. The new fluorine derivatives, here presented, showed an improved antiproliferative activity when compared to the previously reported compounds. The biological evaluation included a preliminary antiproliferative screening on NCI60 cancer cells panel (1-10 µM). Compound 9a was selected as lead compound of the new series of derivatives. The in vitro XTT assay, flow cytometry analysis and immunostaining performed on HeLa cells treated with 9a showed a considerable antiproliferative effect, (IC50 = 3.2 µM), an increased number of cells in G2/M-phase, followed by an enhancement in cell division defects. Moreover, ß-tubulin staining confirmed 9a as a MDA triggering tubulin disassembly, whereas colchicine-9a competition assay suggested that compound 9a compete with colchicine for the binding site on tubulin. Then, the co-administration of compound 9a and an extrusion pump inhibitor (EPI) was investigated: the association resulted beneficial for the antiproliferative activity and compound 9a showed to be client of extrusion pumps. Finally, structural superimposition of different colchicine binding site inhibitors (CBIs) in clinical trial and our MDA, provided an additional confirmation of the targeting to the predicted binding site. Physicochemical, pharmacokinetic and druglikeness predictions were also conducted and all the newly synthesised derivatives showed to be drug-like molecules.

The dissipation behavior, household processing factor and risk assessment for cyenopyrafen residues in strawberry and mandarin fruits.

A modified QuEChERS method for determining cyenopyrafen in strawberries, mandarins and their processed products was established with a good linearity (R2 > 0.9981), accuracy (recoveries of 83% to 111%) and precision (relative standard deviations of 0.9% to 14%). The limit of quantification (LOQ) was 0.01 mg/kg. Field results showed that the half-lives of cyenopyrafen were 6.8 and 11.8 d in strawberry and mandarin respectively, and that the final residues were within established maximum residue limits (MRLs). The household processing factors (PFs) for cyenopyrafen residues in strawberry and mandarin fruits were also studied: residues increased in strawberry jam (PF 1.51) and mandarin juice (1.31) but decreased in strawberries (0.58) and mandarin pulp (<0.17) after washing and peeling, respectively. A risk assessment showed that the risk from long-term dietary exposures to cyenopyrafen was 73.73%, indicating that consuming these products was unlikely to present a public health concern.

Pharmacy services after a tank car derailment and toxic chemical release in Blount County, Tennessee.

OBJECTIVES: To assess the impact of an accidental release of volatilized acrylonitrile on pharmacy services in Blount County, Tennessee. METHODS: A paper questionnaire was mailed to all pharmacies located in Blount County, Tennessee. The questionnaire assessed 5 domains relevant to pharmacy services after the derailment disaster: (1) disaster preparedness, (2) disaster response, (3) disaster information source awareness, (4) Pharmacy Practice Act amendment preference, and (5) pharmacy impact. Continuous (ratio-level), binary, and free-text data were collected and evaluated with the use of multiple correspondence analysis, tetrachoric correlations, and multiple regression modeling. RESULTS: The data suggested that geographic proximity to and duration of the disaster and the number of patients presenting for 72-hour emergency prescription refills significantly influenced the overall impact on pharmacy service delivery. The increase in 72-hour prescription refill requests was strongly correlated with blood pressure and diabetes medications, with all respondents in favor of amending state law to allow pharmacists to dispense 30-day prescription refills in times of disaster. Pharmacy respondents are also largely unaware of online disaster-related information sources. CONCLUSION: Disasters have the potential to affect all pharmacies in a locality but appear to have a significant impact on those located close to the scene. The number of patients presenting to pharmacies and the total duration of the disaster also appear to influence the overall impact of disasters on pharmacies. Pharmacists would be benefited by an awareness of current disaster information sources and legal supports pertinent to pharmacy practice in times of disaster.

Manufacture of patient-specific vascular replicas for endovascular simulation using fast, low-cost method.

Patient-specific vascular replicas are essential to the simulation of endovascular treatment or for vascular research. The inside of silicone replica is required to be smooth for manipulating interventional devices without resistance. In this report, we demonstrate the fabrication of patient-specific silicone vessels with a low-cost desktop 3D printer. We show that the surface of an acrylonitrile butadiene styrene (ABS) model printed by the 3D printer can be smoothed by a single dipping in ABS solvent in a time-dependent manner, where a short dip has less effect on the shape of the model. The vascular mold is coated with transparent silicone and then the ABS mold is dissolved after the silicone is cured. Interventional devices can pass through the inside of the smoothed silicone vessel with lower pushing force compared to the vessel without smoothing. The material cost and time required to fabricate the silicone vessel is about USD $2 and 24 h, which is much lower than the current fabrication methods. This fast and low-cost method offers the possibility of testing strategies before attempting particularly difficult cases, while improving the training of endovascular therapy, enabling the trialing of new devices, and broadening the scope of vascular research.

San copolymer membranes with ion exchangers for Cu(II) removal from synthetic wastewater by electrodialysis.

Heterogeneous membranes were obtained by using styrene-acrylonitrile copolymer (SAN) blends with low content of ion-exchanger particles (5wt.%). The membranes obtained by phase inversion were used for the removal of copper ions from synthetic wastewater solutions by electrodialytic separation. The electrodialysis was conducted in a three cell unit, without electrolyte recirculation. The process, under potentiostatic or galvanostatic control, was followed by pH and conductivity measurements in the solution. The electrodialytic performance, evaluated in terms of extraction removal degree (rd) of copper ions, was better under potentiostatic control then by the galvanostatic one and the highest (over 70%) was attained at 8V. The membrane efficiency at small ion-exchanger load was explained by the migration of resin particles toward the pores surface during the phase inversion. The prepared membranes were characterized by various techniques i.e. optical microscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis and differential thermal analysis and contact angle measurements.

Acrylonitrile Butadiene Styrene (ABS) plastic based low cost tissue equivalent phantom for verification dosimetry in IMRT.

A novel IMRT phantom was designed and fabricated using Acrylonitrile Butadiene Styrene (ABS) plastic. Physical properties of ABS plastic related to radiation interaction and dosimetry were compared with commonly available phantom materials for dose measurements in radiotherapy. The ABS IMRT phantom has provisions to hold various types of detectors such as ion chambers, radiographic/radiochromic films, TLDs, MOSFETs, and gel dosimeters. The measurements related to pre-treatment dose verification in IMRT of carcinoma prostate were carried out using ABS and Scanditronics-Wellhoffer RW3 IMRT phantoms for five different cases. Point dose data were acquired using ionization chamber and TLD discs while Gafchromic EBT and radiographic EDR2 films were used for generating 2-D dose distributions. Treatment planning system (TPS) calculated and measured doses in ABS plastic and RW3 IMRT phantom were in agreement within +/-2%. The dose values at a point in a given patient acquired using ABS and RW3 phantoms were found comparable within 1%. Fluence maps and dose distributions of these patients generated by TPS and measured in ABS IMRT phantom were also found comparable both numerically and spatially. This study indicates that ABS plastic IMRT phantom is a tissue equivalent phantom and dosimetrically it is similar to solid/plastic water IMRT phantoms. Though this material is demonstrated for IMRT dose verification but it can be used as a tissue equivalent phantom material for other dosimetry purposes in radiotherapy.

Optimization of process parameters for acrylonitrile removal by a low-cost adsorbent using Box-Behnken design.

In the present work, acrylonitrile removal from wastewater was investigated using an agri-based adsorbent-sugarcane bagasse fly ash (BFA). The effect of such parameters as adsorbent dose (w), temperature (T) and time of contact (t) on the sorption of acrylonitrile by BFA was investigated using response surface methodology (RSM) based on Box-Behnken surface statistical design at an initial acrylonitrile concentration, C(0)=100mg/l as a fixed input parameter. The results of RSM indicate that the proposed models predict the responses adequately within the limits of input parameters being used. The isotherm shows a two-step adsorption, well represented by a two-step Langmuir isotherm equation. Thermodynamic parameters indicate the sorption process to be spontaneous and exothermic.

Substrate selectivity and conformational space available to bromoxynil and acrylonitrile in iron nitrile hydratase.

Nitrile hydratase (NHase) is used in the commercial conversion of acrylonitrile to acrylamide. There are two main types of NHase: the iron containing and the cobalt containing NHase. They catalyze the conversion of a wide variety of nitriles to their corresponding amides. The Co-NHases are more robust and have wider substrate specificity than the Fe-NHase. We have used dihedral and positional variational Monte Carlo conformational searches to determine the conformational space available to acrylonitrile and bromoxynil bound to the iron in the active site of NHase. Dioxane is an Fe-NHase inhibitor, but has no effect on Co-NHase activity. Our conformational searches showed that although the dioxane restricts the conformational freedom of the iron coordinated acrylonitrile, there is enough room in the active site for both the acrylonitrile and dioxane. A conformational search of dioxane in the active site of Fe-NHase, in the absence of a substrate, revealed that the acrylonitrile and dioxane do not share the same space. We have also shown that if the function of the metal ions in NHases is to activate the nitrile by binding to it and acting as a Lewis acid, then the entrance and channel residues are most likely responsible for Fe-NHase's inability to hydrolize bromoxynil.

Kinetics of 131I-beta2 microglobulin in hemodialysis patients: assessment using total body counting.

The kinetics of 131I-beta2-microglobulin (beta2-M) were studied using external total body gamma counting in a low noise chamber after administration of trace doses of radioactivity (4 microCi) in 14 uremic patients treated by either hemodialysis or hemofiltration. Data were collected over a 1 week period that included 3 dialysis sessions. The following artificial membranes were used: Cuprophan, polyacrylonitrile AN69, polysulfone, polymethylmethacrylate (PMMA), and polyamide. Radiolabeled beta2-M excretion by an extrarenal route was nearly nonexistent. The 131I-beta2-M half-life was between 2.4 and 8 days, shorter in patients with residual diuresis. A mean removal of 153+/-33 mg/L of beta2-M was obtained per dialysis session with a highly permeable membrane. A hemofiltration session (25 L exchange per session) was slightly more efficient in removing beta2-M than a 4 h hemodialysis session with the same AN69 highly permeable membrane. The amounts of 131I-beta2-M binding on the membranes, expressed as beta2-M equivalents, were 0, 16, 54, 58, and 59 mg/m2 for Cuprophan, polysulfone, polyacrylonitrile AN69, polyamide, and PMMA, respectively. In conclusion, the decrease of total body gamma counting directly reflected the beta2-M breakdown and removal in hemodialysis patients. Intact beta2-M was removed by convection with synthetic, highly permeable membranes. In addition, membrane adsorption accounted for 15% (polysulfone) to near 100% (PMMA) of the beta2-M removal per session. Adsorption was of the same magnitude regardless of the dialysis technique in use, indicating a membrane saturability process. None of the currently available dialysis procedures based on a 3 sessions per week schedule can balance beta2-M generation.