In-silico green toxicology approach toward discovering safer ligands for development of safe-by-design metal-organic frameworks.

A vast variety of chemical compounds have been fabricated and commercialized, they not only result in industrial exposure during manufacturing and usage, but also have environmental impacts throughout their whole life cycle. Consequently, attempts to assess the risk of chemicals in terms of toxicology have never ceased. In-silico toxicology, also known as predictive toxicology, has advanced significantly over the last decade as a result of the drawbacks of experimental investigations. In this study, ProTox-III was applied to predict the toxicity of the ligands used for metal-organic framework (MOF) design and synthesis. Initially, 35 ligands, that have been frequently utilized for MOF synthesis and fabrication, were selected. Subsequently, canonical simplified molecular-input line-entry system (SMILES) of ligands were extracted from the PUBCHEM database and inserted into the ProTox-III online server. Ultimately, webserver outputs including LD50 and the probability of toxicological endpoints (cytotoxicity, carcinogenicity, mutagenicity, immunotoxicity, and ecotoxicity) were obtained and organized. According to retrieved LD50 data, the safest ligand was 5-hydroxyisophthalic. In contrast, the most hazardous ligand was 5-chlorobenzimidazole, with an LD50 of 8 mg/kg. Among evaluated endpoints, ecotoxicity was the most active and was detected in several imidazolate ligands. This data can open new horizons in design and development of green MOFs.

Health risk assessment of occupational exposure to heavy metals among green space workers in Iran.

Exposure to heavy metals can result in various adverse health effects. Tehran is rated as one of the world's most polluted cities. Green space workers are continuously exposed to such pollutants in this city. Thus, this study aimed to estimate the health risks caused by exposure to heavy metals among green space workers. Eighty-eight workers and office personnel in two regions with different air quality levels were chosen for sampling. Air samples were collected using the NIOSH-7300 method and analyzed using an Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) instrument. The hazard quotient (HQ) and the lifetime cancer risk (LTCR) were calculated to assess carcinogenic and non-carcinogenic risk levels. The results revealed that the rank order of heavy metals was determined as Zn, Pb, Mn, Ni, Co, and Cd. Workers were subjected to higher concentrations of Ni, Pb, Zn, and Co than office personnel. Furthermore, the Cd, Co, and Zn exposure levels stood significantly higher in region 6 than in region 14. Non-carcinogenic risk levels for all participants fell within the acceptable range. Moreover, no employee had a carcinogenic risk level within the acceptable range when exposed to Cd. Also, 2.3% of individuals demonstrated Ni's acceptable carcinogenic risk level. Owing unacceptable risk levels, proper interventions are required to minimize occupational exposure to heavy metals. These interventions include optimizing shift schedules, using personal protective equipment, and conducting regular health assessments.

Development of a Green Single Drop Microextraction Based on Deep Eutectic Solvent and HPLC-UV for Trace Residue Analysis of Three Frequent-Used Pesticides.

Background: A green sample preparation method named deep eutectic solvent-based single drop microextraction (DES-SDME) was developed and optimized for determining trace metribuzin, dichlorvos, and fenthion. Methods: Two hundred seventy experimental runs were performed, and the optimal values of the five influential factors in the DES-SDME method were determined. The design of the study was based on one factor at a time and the peak area of high-performance liquid chromatography was used as a benchmark for comparing analysis results. Results: After optimizing the effective factors, the linearity range, detection limit and quantification limit of the method were determined by drawing calibration curves for the studied analytes. Conclusion: The results indicated the success of the developed method in obtaining acceptable figures of merit as a green preparation method with accuracy and precision.

Reconstruction of exposure to methylene diphenyl-4,4'-diisocyanate (MDI) aerosol using computational fluid dynamics, physiologically based toxicokinetics and statistical modeling.

OBJECTIVES: This study employed computational fluid dynamics (CFD), physiologically based toxicokinetics (PBTK), and statistical modeling to reconstruct exposure to methylene diphenyl-4,4'-diisocyanate (MDI) aerosol. By utilizing a validated CFD model, human respiratory deposition of MDI aerosol in different workload conditions was investigated, while a PBTK model was calibrated using experimental rat data. Biomonitoring data and Markov Chain Monte Carlo (MCMC) simulation were utilized for exposure assessment. RESULTS: Deposition fraction of MDI in the respiratory tract at the light, moderate, and heavy activity were 0.038, 0.079, and 0.153, respectively. Converged MCMC results as the posterior means and prior values were obtained for several PBTK model parameters. In our study, we calibrated a rat model to investigate the transport, absorption, and elimination of 4,4'-MDI via inhalation exposure. The calibration process successfully captured experimental data in the lungs, liver, blood, and kidneys, allowing for a reasonable representation of MDI distribution within the rat model. Our calibrated model also represents MDI dynamics in the bloodstream, facilitating the assessment of bioavailability. For human exposure, we validated the model for recent and long-term MDI exposure using data from relevant studies. CONCLUSION: Our computational models provide reasonable insights into MDI exposure, contributing to informed risk assessment and the development of effective exposure reduction strategies.

Investigation of asbestos concentration in ambient and lavage fluids of patients referred for bronchoscopy, Ahvaz.

Introduction: The amount of fibers in the lungs is considered to reflect the cumulative intensity of past asbestos exposure, and bronchoalveolar lavage (BAL) has been proposed to be a good indicator of the presence and quantity of asbestos particles in the lungs. This study evaluated the asbestos concentration in BAL fluids of asbestos-exposed and unexposed pulmonary patients and the environment of Ahvaz city. Methods: This prospective study was conducted on 80 patients underwent diagnostic fiberoptic bronchoscopy referred to Imam Khomeini Hospital in Ahvaz, Iran, in 2019. Patients with Lung diseases were divided into three groups based on CT scan results: normal (n = 32), lung cancer (n = 40) and Interstitial lung disease (n = 8). The analysis of asbestos fiber concentration in BAL fluid was carried out by Scanning Electron Microscope (SEM). Results: The positive asbestos test was detected in 69% of all subjects, including 64% of whom had asbestos-related jobs and 74.5% of those with non-related jobs (p = 0.240). The concentrations of asbestos fiber in the BAL in normal patients, lung cancer and interstitial fibrosis (ILD) were 8.13 ± 5.38, 9.66 ± 7.30 and 6.31 ± 1.98 f/ml, respectively (P = 0.492). There was no significant difference between the asbestos levels and exposure history (P = 0.877). The mean concentration of asbestos in the ambient air during the current year was 2.69 ± 0.57 f/ml (2.26-3.70), and the correlation between asbestos levels in BAL and the air was not significant (r = 0.147; P = 0.243). Conclusions: The exposure of different occupational and non-occupational groups to this carcinogenic substance indicates the need for environmental and individual control measures to reduce and prevent asbestos exposure.

Downregulation of GJB2 and SLC26A4 genes induced by noise exposure is associated with cochlear damage.

BACKGROUND: Noise-induced hearing loss (NIHL) is one the major causes of acquired hearing loss in developed countries. Noise can change the pattern of gene expression, inducing sensorineural hearing impairment. There is no investigation on the effects of noise frequency on the expression of GJB2 and SLC26A4 genes involved in congenital hearing impairment in cochlear tissue. Here we investigated the impacts of white and purple noise on gene expression and pathologic changes of cochlear tissue. METHODS: In this study, 32 adult male Westar rats were randomly divided into experimental groups: WN, animals exposed to white noise with a frequency range of 100-20000 Hz; PN, animals exposed to purple noise with a frequency range of 4-20 kHz, and control group, without noise. The experimental groups were exposed to a 118-120 dB sound pressure level for 8 h per 3 days and 6 days. 1 h and 1 week after termination of noise exposure, cochlear tissue was prepared for pathology and gene expression analysis. RESULTS: Both white and purple noises caused permanent damage to the cortical, estrosilica systems of hair cells and ganglion of the hearing nerve. GJB2 and SLC26A4 were downregulated in both groups exposed with white and purple noise by increasing the time of noise exposure. However, differences are notably more significant in purple noise, which is more intensified. Also, 1 weak post noise exposure, the downregulation is remarkably higher than 1 h. CONCLUSIONS: Our findings suggest that downregulation of GJB2 and SLC26A4 genes are associated with pathological injury in response to noise exposure in cochlear tissue. It would be suggested the demand for assessment of RNA and protein expression of genes involved in noise-induced hearing loss and subsequently the practice of hearing protection programs.

Ultrasound-assisted dispersive micro-solid-phase extraction based on N-doped mesoporous carbon and high-performance liquid chromatographic determination of 1-hydroxypyrene in urine samples.

In this research, a new ultrasound-assisted dispersive micro-solid-phase extraction method based on N-doped mesoporous carbon sorbent followed by high-performance liquid chromatography equipped with diode array detector for trace measurement of 1-hydroxypyrene as a metabolite of exposure to polycyclic aromatic hydrocarbons was optimized. Herein, the hard template method was used for the preparation of N-doped mesoporous carbon sorbent. The prepared sorbent was characterized using the Brunauer-Emmett-Teller method, transmission electron microscopy, and elemental analysis. Parameters affecting the extraction of the target metabolite were investigated using the Box-Behnken design method. Considering optimum parameters, the plotted calibration curve for 1-hydroxypyrene was linearly correlated with the concentration span of 0.1-50 µg/L for urine media. The accuracy of the optimized procedure was examined through the relative recovery tests on the fortified urine specimens. The relative recoveries fell between 95 and 101%. The method detection limit of the proposed procedure was also calculated to be 0.03 µg/L.

Development of Dispersive Liquid-Liquid Microextraction Procedure for Trace Determination of Malathion Pesticide in Urine Samples.

BACKGROUND: Measurement of pesticides in biological matrices is become a serious challenge for researches because of their very low concentration in different matrices. The aim of this study was to develop a new sample preparation method with high accuracy and validity, simplicity and short retention time for determination of malathion. METHODS: Dispersive liquid-liquid micro-extraction (DLLME) technique coupled with high-performance liquid chromatography equipped with ultraviolet detector (HPLC-UV) developed for trace extraction and determination of malathion pesticide in human urine samples. This study was done in 2017 at Tehran University of Medical Sciences, Tehran, Iran. One variable at a time (OVAT) method was used to optimize parameters affecting the malathion extraction. Different parameters such as extraction solvent, disperser solvent, and volume of the extraction solvent, volume of the disperser solvent, centrifugation time and speed, salt addition, and sample pH were studied and optimized. RESULTS: Under the optimized conditions, the limit of detection and enrichment factor of the method were 0.5 µg L-1 and 200, respectively. The calibration curve was linear in the concentration range of 2-250 µg L-1. The relative standard deviation for six replicate experiments at 200 µg L-1 concentration was less than 3%. The relative recoveries of spiked urine samples were 96.3%, 101.7% and 97.3% at three different concentration levels of 50, 200 and 1000 µg L-1, respectively. CONCLUSION: DLLME procedure was successfully developed for the extraction of malathion from human urine samples. Compared to other extraction techniques, the proposed procedure had some advantages such as shorter extraction time, better reproducibility, and higher enrichment factor.

Optimization of dispersive liquid-liquid microextraction procedure for detecting chlorpyrifos in human urine samples.

Background: Selecting an effective sample preparation method to measure target pesticides in biological matrices is a serious challenge for researchers. This study aimed to optimize the dispersive liquid-liquid microextraction (DLLME) technique to obtain a simple, valid, and fast method with high efficiency to detect chlorpyrifos in urine samples. Methods: DLLME, coupled with high performance liquid chromatography equipped with ultra violet detector, was used to extract chlorpyrifos pesticide in human urine samples. Different affecting parameters on the efficiency of the method were optimized using one factor at a time method. Results: The limit of detection and enrichment factor of the method was 0.5 and 230 µg L-1, respectively. Linear calibration curve with 1-500 µg L-1 concentration range was used. The relative standard deviation (RSD) for 6 replicate experiments at the concentration of 200 µg L-1 was less than 5%. The relative recoveries of spiked urine samples were 96.3%, 102.3%, and 98.7% at 3 different concentration levels of 50, 200, and 1000 µg L-1, respectively. Conclusion: Compared to other extraction techniques, the optimized DLLME resulted in some advantages such as shorter extraction time, high extraction efficiency, and good enrichment factor for the extraction of chlorpyrifos from human urine samples.

Synthesis of molecularly imprinted nanoparticles for selective exposure assessment of permethrin: optimization by response surface methodology.

BACKGROUND: Extensive use of high-efficiency pyrethroid pesticides as pest-control agents lead to remarkable adsorption and release of these materials in soil and aquatic environment which could have serious adverse effects on water and food chain quality as well as human health. In this study, a molecularly imprinted polymer was synthesized and used as a selective sorbent in the sample preparation procedure in order to facilitate sensitive and quantitative exposure assessment of insecticide permethrin. METHODS: Molecular imprinted nanoparticles were prepared by precipitation polymerization technique using 1:4:20 mmol ratio of the template, functional monomer, and cross-linker, respectively, as well as 80 mL of chloroform as progen solvent. The obtained nanoparticles were characterized by field emission scanning electron microscopy (FESEM) and Fourier transform infrared spectrometry (FT-IR). The optimization of critical variables in the MISPE process was done using the central composite design (CCD) of the response surface methodology. RESULTS: Quadratic regressional models were developed to correlate the response and independent variables and the analysis of variance (ANOVA) verified the excellent fitting of proposed models for experimental data. Optimum conditions for the highest MISPE yield were selected as follow: sorbent mass of 7.71 mg, sample pH 5.58 and 5.68 for cis and trans-permethrin, respectively, sample flow rate of 0.6 mL/min, as well as 5 and 3.94 mL of methanol/acetic acid at the flow rate of 2 mL/min as elution solvents for cis and trans-permethrin, respectively. Under optimized conditions, the linear range was obtained 20-120 µg/L (R2 = 0.99) and the detection limits were 5.51 and 5.72 µg/L for cis and trans-permethrin, respectively. Analysis of real samples demonstrated the high extraction efficiency of designed protocol ranging from 93.01 to 97.14 with the relative standard deviation (RSD) less than 4.51%. CONCLUSIONS: The satisfactory results confirmed the reliability and efficiency of the proposed method for trace analysis of permethrin isomers in biological and environmental samples.

Assessment of contrast perception of obstacles in a tunnel entrance.

Background: The purpose of this study was to assess the contrast perception of obstacles in a tunnel entrance which was placed in Ilam Province, Iran. Methods: An obstacle with the reflection coefficient of 20% was mounted at the entrance of thetunnel and then, the car was placed near the tunnel entrance and the intrinsic luminance of the road (Lr,intrinsic) and obstacle (Lo,intrinsic) were measured inside the car using the luminance meter. Results: Intrinsic luminance of obstacle and road at the entrance of the tunnel were measured as 41 and 17 cd/m2, respectively. The contrast perception of obstacle in deriver's eyes and in the safe stopping distance (SSD) from the tunnel entrance was determined as 2.79 cd/m2. At the entrance of the studied tunnel, the contrast perception of obstacles with the reflection coefficient of 20% was lower than the minimum contrast perception (28%) recommended by International Commission on Illumination. Conclusion: The main conclusion that can be drawn from it, is that this obstacle in the SSD from the tunnel entrance cannot be conceived by the drivers, which may lead to higher rate of road traffic crashes.

Heavy metals determination in honey samples using inductively coupled plasma-optical emission spectrometry.

BACKGROUND: Honey contains a complex mixture of carbohydrates and other minor substances. Elements are minor constituents of honey that may threaten the human health in excess concentrations. So, determining the metals in honey helps its quality control as a food product. The aim of this study was to determine the concentrations of some metals in Iranian honey. METHODS: This study was performed in four regions of Ardabil, a province of Iran. Honey samples (n = 25) were digested in microwave oven by nitric acid and hydrogen peroxide, then analyzed using inductively coupled plasma- optic emission spectrophotometry (ICP-OES). RESULTS: No significant differences were observed in cadmium, zinc, nickel, and chromium levels between regions (P > 0.05). Zinc was the most abundant metal in honey samples (1481.64 µg/kg). Some metals had higher concentrations in the East region because of existence more industries there. The highest mean of lead level was 935.48 µg/kg in the East and the lowest was 205.4 µg/kg in the South region. The concentrations of metals were compared with recommended limits for foods. Some of them were higher than standard levels (lead) and some were lower than those (cadmium). CONCLUSIONS: Metals are released into the environment through their use in industrial processes and enter the food chain from uptake by plants from contaminated soil or water. Metals concentration in various places depends on many variables, leading to their different concentrations in honey. Some control measures like the quality control of food products, monitoring the soil in agricultural regions and limiting the use of fertilizers are recommended.

Pulmonary functions of welders in gas transmission pipelines in Iran.

This study evaluated the influence of welding on pulmonary functions in welders. Spirometry tests were performed before and after work shift in 91 welders and 25 clerks (control group). We examined forced vital capacity (FVC), forced expiratory volume in 1 s (FEV1), FEV1/FVC ratio and forced expiratory flow 25%-75% (FEF 25-75). Significant differences were found for FVC and FEV1/FVC between welders and the control group in pre- and post-shift measurements (p < .001). In welders, smoking and nonsmoking habit had no significant effects on any pulmonary indices before or after shift. Work experience and fume concentrations also had no significant effects on the majority of spirometric indices (p > .05). Most welders had at least 1 of the respiratory symptoms. Significant differences were found between pre- and post-shift indices (as percentage of predicted values calculated with spirometer) and between the welders engaged in some welding tasks and the control group before work shift. This study documented work-related changes in pulmonary functions in the welders and marked drops in these functions without symptoms in some welders.

Descriptive Study of Occupational Accidents and their Causes among Electricity Distribution Company Workers at an Eight-year Period in Iran.

BACKGROUND: Occupational accidents are unplanned events that cause damage. The socio-economic impacts and human costs of accidents are tremendous around the world. Many fatalities happen every year in workplaces such as electricity distribution companies. Some electrical injuries are electrocution, electric shock, and burns. This study was conducted in an electricity distribution company (with rotational 12-hour shift work) in Iran during an 8-year period to survey descriptive factors of injuries. METHODS: Variables collected included accident time, age of injured worker, employment type, work experience, injury cause, educational background, and other information about accidents. RESULTS: Results indicated that most of the accidents occurred in summer, and 51.3% were during shift work. Worker negligence (malpractice) was the cause of 75% of deaths. Type of employment had a significant relationship with type of injuries (p < 0.05). Most injuries were electrical burns. CONCLUSION: High rate of accidents in summer may be due to the warm weather or insufficient professional skills in seasonal workers. Shift workers are at risk of sleep complaints leading to a high rate of work injuries. Acquiring knowledge about safety was related to job experiences. Temporary workers have no chance to work all year like permanent workers, therefore impressive experiences may be less in them. Because the lack of protective equipment and negligence are main causes of accidents, periodical inspections in workshops are necessary.

Evaluation of Occupational Exposure of Glazers of a Ceramic Industry to Cobalt Blue Dye.

BACKGROUND: Cobalt is one of the most important constituent present in ceramic industries. Glazers are the relevant workers when they are producing blue colored ceramic, causing occupational exposure to such metal. Through this study, urinary cobalt was determined in glazers in a ceramic industry when they were producing blue-colored ceramic glazes. METHODS: In this case-control study, spot urine samples were collected from 49 glazers at the start and end of work shifts (totally 98 samples) in 2011. Control group were well matched for age, height, and weight. A solid phase extraction system was used for separation and preconcentration of samples followed by analysis by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). All participants filled out a self administered questionnaire comprises questions about duration of exposure, work shift, use of mask, skin dermatitis, kind of job, ventilation system, overtime work, age, weight, and height. The lung function tests were performed on each control and cobalt exposed subjects. Analysis of covariance (ANCOVA) was used to evaluate the obtained results. RESULTS: Urinary levels of cobalt were significantly higher in the glazers compared to the control group. There were significant differences at urinary concentration of cobalt at the start and end of the work shift in glazers. Spirometric parameters were significantly lower in the glazers compared to the control group. Among the variables used in questionnaire the significant variables were dermatitis skin, mask, ventilation, and overtime work. CONCLUSION: This study verified existence of cobalt in the urine glazers, showing lower amount than the ACGIH standard.

Solid phase extraction for evaluation of occupational exposure to Pb (II) using XAD-4 sorbent prior to atomic absorption spectroscopy.

Lead is an important constituent widely used in different industrial processes. For evaluation of workers' exposure to trace toxic metal of Pb (II), solid-phase extraction (SPE) was optimized. SPE using mini columns filled with XAD-4 resin was developed with regard to sample pH, ligand concentration, loading flow rate, elution solvent, sample volume, elution volume, the amount of resins, and sample matrix interferences. Lead ions were retained on a solid sorbent and then eluted, followed by a simple determination of analytes with flame atomic absorption spectrometery. The obtained recoveries of metal ions were greater than 92%. This method was validated with 3 different pools of spiked urine samples; it showed a good reproducibility over 6 consecutive days as well as 6 within-day experiments. This optimized method can be considered successful in simplifying sample preparation for a trace residue analysis of lead in different matrices when evaluating occupational and environmental exposures is required.