Lipase-catalyzed Synthesis of Feruloylated Lysophospholipid in Toluene-Ionic Liquids and Its Antioxidant Activity.

In this study, Novozym 435-catalyzed interesterification of ethyl ferulate (EF) with phosphatidylcholine (PC) in a two-phase system consisting of an ionic liquid (IL) and toluene was optimized to prepare feruloylated lysophospholipids (FLPs). Optimum conditions for the interesterification process were found to be [Bmim][Tf2N]/toluene ratio of 1:1 (v/v), solvent volume of 4 mL, molecular sieves (4 Å) concentration of 80 mg/mL, reaction temperature of 55°C, substrate molar ratio of 5:1 (PC/EF), Novozym 435 concentration of 50 mg/mL. Under these conditions, two FLPs products (1-FLP and 2-FLP) with total conversion rate of 50.79% were obtained. Because the formation of 1-FLP was significantly higher than 2-FLP, 1-FLP was purified and characterized by LC-MS and NMR. In addition, 1-FLP showed DPPH scavenging activity comparable with those of EF and BHT. Therefore, this study provides a good method for transformation of ferulic acid to improve its solubility and promote its application as functional ingredient in the food and pharmaceutical industries.

Flow Cytometry Assessment of Procoagulant Platelets Using a Dithiol-Reactive Probe.

Flow cytometry assessment of platelets using the combination of GSAO [4-(N-(S-glutathionylacetyl)amino)phenylarsonous acid], a dithiol-reactive probe, and P-selectin, a platelet activation marker, is a novel and powerful assay in the identification and quantification of the procoagulant subpopulation of platelets that has the capacity to support thrombin generation. In this chapter, we provide the flow cytometry protocols aimed at the study of procoagulant platelets under resting and agonist-stimulated conditions in whole blood and washed platelets of both human and murine (mouse) samples.

The Concentration of BTEX in the Air of Tehran: A Systematic Review-Meta Analysis and Risk Assessment.

In the current study, the concentration of some pollutants which are categorized as volatile organic compounds (VOCs), including benzene (B), toluene (T), ethylbenzene (E), and o-xylenes (o-X), in the air of Tehran was evaluated by the aid of a systematic review and meta-analysis approach. Also, the health risk for the exposed population was estimated using the recommended methods by the Environmental Protection Agency (EPA). The rank order based on their concentration in BTEX was benzene (149.18 µg/m³: 31%) > o-xylene (127.16 µg/m³: 27%) > ethylbenzene (110.15 µg/m³: 23%) > toluene (87.97 µg/m³: 19%). The ratio B/T in this study was calculated as 1.69, repressing that both stationary and mobile sources of emission can be considered as the main sources for benzene and toluene. Moreover, strong photochemical activity in Tehran was demonstrated by the high ratio of E/o-X. Meta-regression indicates that the concentration of BTEX has insignificantly (p-value > 0.05) increased over time. The BTEX compounds based on the target hazard quotient (THQ) were ordered as benzene > o-xylene > ethylbenzene > toluene. Percentile 95% of THQ due to benzene (4.973) and o-xylene (1.272) was higher than a value of 1. Percentile 95% excessive cancer risk (ECR) for benzene (1.25 × 106) and ethylbenzene (1.11 × 106) was higher than a value of 1.00 × 106. The health risk assessment indicated that the population of Tehran are at considerable non-carcinogenic and carcinogenic risks.

Assessment of the inhalation risks associated with working in printing rooms: a study on the staff of eight printing rooms in Beijing, China.

The concentration of pollution directly determines the occupational health risk, and the exposure time is an important influencing factor. We evaluated the inhalation risks of working in a printing room. Eight units with centralized printing rooms were randomly selected. Formaldehyde, ozone, benzene, toluene, xylene, and fine particulate matter were detected by spectrophotometry, gas chromatography, and direct reading instruments, respectively. The U.S. EPA inhalation risk assessment model was used to assess cancer and non-cancer risks. The formaldehyde inhalation cancer risk value was 1.35-3.45 × 10-6, which is greater than the limit of 1 × 10-6, suggesting a risk of squamous cell carcinoma. The benzene inhalation cancer risk in five of the rooms was 1.09-4.65 × 10-6, which is greater than the limit of 1 × 10-6, suggesting a risk of leukemia. In terms of non-cancer risk, in five of the rooms, the hazard quotient (HQ) was > 1 (range 1.99-4.69) due to benzene pollution, suggesting a risk of reduced lymphocyte count. In one room, due to benzene and xylene pollution, the HQ was > 1, suggesting a risk of lymphocyte count drop and motor coordination impairment. Collectively, the study concludes that staff members of printing rooms are exposed to both cancer and non-cancer occupational health risks.

Health risk assessment of VOC emissions in laboratory rooms via a modeling approach.

One of the important agents menacing buildings' employees and residents' health is the emission of volatile organic compounds (VOCs) into the indoor environment. The present research studied the VOC emission to evaluate indoor air quality (IAQ) through studying in-laboratory processes and tasks. On account of that, three different pollutants (acetone, benzene, and toluene) were chosen as candidate VOCs, and Environmental Engineering Research Center at Sahand University of Technology was selected as a sample laboratory for each VOC. Using CFD model, concentrations of pollutants under unsteady state in a three-dimensional geometry at various temperatures were provided. To validate the considered model, the modeling results were compared to experimental data. Health risk was evaluated through the building using the OEL-C, OEL-STEL, and OEL-TWA parameters for the three pollutants. According to the mentioned parameters and the modeling results, 1 h following the emission, in order to reduce the health risk associated with short-term exposure to the emission, the staff should observe a minimum distance of 3, 2, and 1.8 m to the sources of acetone, benzene, and toluene, respectively. This is while, since average concentration of emission within the laboratory in an 8-h period is several times as large as OEL-TWA, then the laboratory staffs are strictly recommended not to work in the laboratory for long hours. Furthermore, using the results of this research, the staff can detect safe locations within the laboratory without any need to use emission monitoring equipment.

Binding Modes of Ligands Using Enhanced Sampling (BLUES): Rapid Decorrelation of Ligand Binding Modes via Nonequilibrium Candidate Monte Carlo.

Accurately predicting protein-ligand binding affinities and binding modes is a major goal in computational chemistry, but even the prediction of ligand binding modes in proteins poses major challenges. Here, we focus on solving the binding mode prediction problem for rigid fragments. That is, we focus on computing the dominant placement, conformation, and orientations of a relatively rigid, fragment-like ligand in a receptor, and the populations of the multiple binding modes which may be relevant. This problem is important in its own right, but is even more timely given the recent success of alchemical free energy calculations. Alchemical calculations are increasingly used to predict binding free energies of ligands to receptors. However, the accuracy of these calculations is dependent on proper sampling of the relevant ligand binding modes. Unfortunately, ligand binding modes may often be uncertain, hard to predict, and/or slow to interconvert on simulation time scales, so proper sampling with current techniques can require prohibitively long simulations. We need new methods which dramatically improve sampling of ligand binding modes. Here, we develop and apply a nonequilibrium candidate Monte Carlo (NCMC) method to improve sampling of ligand binding modes. In this technique, the ligand is rotated and subsequently allowed to relax in its new position through alchemical perturbation before accepting or rejecting the rotation and relaxation as a nonequilibrium Monte Carlo move. When applied to a T4 lysozyme model binding system, this NCMC method shows over 2 orders of magnitude improvement in binding mode sampling efficiency compared to a brute force molecular dynamics simulation. This is a first step toward applying this methodology to pharmaceutically relevant binding of fragments and, eventually, drug-like molecules. We are making this approach available via our new Binding modes of ligands using enhanced sampling (BLUES) package which is freely available on GitHub.

Bioelectrochemical BTEX removal at different voltages: assessment of the degradation and characterization of the microbial communities.

BTEX compounds (Benzene, Toluene, Ethylbenzene and Xylenes) are toxic hydrocarbons that can be found in groundwater due to accidental spills. Bioelectrochemical systems (BES) are an innovative technology to stimulate the anaerobic degradation of hydrocarbons. In this work, single chamber BESs were used to assess the degradation of a BTEX mixture at different applied voltages (0.8V, 1.0V, 1.2V) between the electrodes. Hydrocarbon degradation was linked to current production and to sulfate reduction, at all the tested potentials. The highest current densities (about 200mA/m2 with a maximum peak at 480mA/m2) were observed when 0.8V were applied. The application of an external voltage increased the removal of toluene, m-xylene and p-xylene. The highest removal rate constants at 0.8V were: 0.4±0.1days-1, 0.34±0.09days-1 and 0.16±0.02days-1, respectively. At the end of the experiment, the microbial communities were characterized by high throughput sequencing of the 16S rRNA gene. Microorganisms belonging to the families Desulfobulbaceae, Desulfuromonadaceae and Geobacteraceae were enriched on the anodes suggesting that both direct electron transfer and sulfur cycling occurred. The cathodic communities were dominated by the family Desulfomicrobiaceae that may be involved in hydrogen production.

Assessment of the effectiveness of onsite exsitu remediation by enhanced natural attenuation in the Niger Delta region, Nigeria.

This study was conducted to quantify and rank the effectiveness of onsite exsitu remediation by enhanced natural attenuation using soil quality index. The investigation was conducted at three oil spill sites in the Niger Delta (5.317°N, 6.467°E), Nigeria with a predominance of Oxisols. Baseline assessment and a two-step post-remediation monitoring of the sites were conducted. Target contaminants including total petroleum hydrocarbon (TPH) and BTEX (benzene, toluene, ethylbenzene, and xylene) were analyzed by gas chromatography-mass spectrometry. Results of the baseline assessment showed that TPH concentrations across the study sites averaged between 5113 and 7640 mg/kg at 0- to 1-m depth, which was higher than the local regulatory value of 5000 mg/kg. The soil quality index across the sites ranged between 68 and 45, suggesting medium to high potential ecological health risks with medium to high priority for remediation. BTEX concentrations followed a similar trend. However, after remediation TPH degraded rapidly initially and then slowly but asymptotically during the post-remediation monitoring period. Then, soil quality index across the study sites ranged between 100 and 58, indicating very low to medium potential ecological health risks. This demonstrates the effectiveness of onsite exsitu remediation by enhanced natural attenuation as a remediation strategy for petroleum-contaminated soils, which holds great promise for the Niger Delta province.

Assessment of spatial variation of ambient volatile organic compound levels at a power station in Kuwait.

Twenty-four-hour integrated ambient air samples were collected in canisters at 10 locations within Kuwait's major power station: Doha West Power Station to assess the spatial distribution of volatile organic compounds (VOCs) within the perimeter of the station. A total of 30 samples, i.e., three samples per location, were collected during February and March. The samples were analyzed using a gas chromatography with flame ionization detection (GC-FID) system and following the U.S. EPA Method TO-14A with modification. The results reflected the emission activities on the site and the meteorological conditions during sampling. Generally speaking, there was a negative correlation between the ambient temperature and the VOC concentrations, which indicates the sources were local. The halogenated compounds formed the highest proportion (i.e. 50-75 %) of the total VOC concentrations at the ten locations. 1,2,4-Trichlorobenzene and Vinyl Chloride concentrations were the highest amongst the other halogenated compounds. The aromatic compounds formed the least proportion (i.e. 1-4%) of the total VOC levels at all locations with Toluene having the highest concentrations amongst the aromatic compounds at seven locations. Propene, which is a major constituent of the fuel used, was the highest amongst the aliphatic compounds. The findings of this study and other relevant work suggests the measured VOC levels were the highest over the year, nevertheless, further work is required to assess the precisely temporal variation of VOC due to change in meteorological conditions and the emission rates. IMPLICATIONS: Assessment of VOC concentrations around a power plant in Kuwait during the peak season showed halogenated compounds to be the dominant group. The calculated indoor concentrations were lower than those reported in a residential area about 12 km away.

Dynamics and the Regiochemistry of Nitration of Toluene.

The regiochemistry of the nitration of toluene by NO2+BF4- in dichloromethane is accurately predicted from trajectories in explicit solvent. Simpler models and approaches based on transition state theory fail to account for the selectivity. Potential of mean force calculations find no free-energy barrier for reaction of the toluene/NO2+BF4- encounter complex, yet the trajectories require an extraordinary 3 ps to descend an exergonic slope. The selectivity is decided late in long trajectories because their completion requires solvent and counterion reorganization. The normal descriptive understanding of the regiochemistry based on transition-state energies is unsupported.

Quantification and human health risk assessment of by-products of photo catalytic oxidation of ethylbenzene, xylene and toluene in indoor air of analytical laboratories.

The by-products of TiO2-based photocatalytic oxidation (PCO) of ethylbenze, p,m-xylene, o-xylene and toluene (EXT) in vapour phase and those adsorbed on the catalyst surface (solid phase) were identified and quantified on GC/GC-MS. A factor was developed in terms of µg of by-product produced per mg of EXT removed per sq-meter surface area of catalyst for estimating the mass of by-products produced. The by-products quantified were: acetone, hexane, cyclohexane, benzene, crotonaldehyde, toulene, 1,4-benzoquinone, benzaldehyde, phenol, benzylalcohol, cresol, hydroquinone and benzoic acid. The by-products accounted for 2.3-4.2% of the total mass of EXT treated. For treating concentrations of 220µg/m(3) (ethylbenzene), 260µg/m(3) (p,m-xylene), 260µg/m(3) (o-xylene) and 320µg/m(3) (toluene), at a flow rate of 7L/min for 12h in a laboratory of volume 195m(3), the estimated cancer risks of by-products to the occupants were 1.51×10(-6), 1.06×10(-6), 4.69×10(-7), and 1.58×10(-9) respectively. The overall hazard index (HI) of the by-products for EXT was of the order 10(-4); which is much less than desired level of 1.0. The estimated risks were within the acceptable level. This study has also suggested the photocatalytic degradation pathways for EX which are through formation of toluene.

Assessment of lifetime resolution limits in time-resolved photoacoustic calorimetry vs. transducer frequencies: setting the stage for picosecond resolution.

Time-resolved photoacoustic calorimetry (PAC) gives access to lifetimes and energy fractions of reaction intermediates by deconvolution of the photoacoustic wave of a sample (E-wave) with that of the instrumental response (T-wave). The ability to discriminate between short lifetimes increases with transducer frequencies employed to detect the PAC waves. We investigate the lifetime resolution limits of PAC as a function of the transducer frequencies using the instrumental response obtained with the photoacoustic reference 2-hydroxybenzophenone in toluene or acetonitrile. The instrumental response was obtained for a set of transducers with central frequencies ranging from 0.5 MHz up to 225 MHz. The simulated dependence of the lifetime resolution with the transducer frequencies was anchored on experimental data obtained for the singlet state of naphthalene with a 2.25 MHz transducer. The shortest lifetime resolved with the 2.25 MHz transducer was 19 ns and our modelling of the transducer responses indicates that sub-nanosecond lifetimes of photoacoustic transients can be resolved with transducers of central frequencies above 100 MHz.

Comparative assessment of compost and zeolite utilisation for the simultaneous removal of BTEX, Cd and Zn from the aqueous phase: Batch and continuous flow study.

The present study focuses on the comparison of two materials, compost from municipal solid waste and natural zeolite for the simultaneous removal of petroleum hydrocarbons (benzene, toluene, ethylbenzene, xylenes - BTEX) and toxic metals from groundwater. First, batch experiments were conducted to identify the optimal removal conditions. All of the kinetic experiments were fitted to the pseudo-second-order kinetic model; equilibrium was reached within approximately 8 h for the zeolite and 12 h for the compost. An increase in the adsorbent dose and the pH value as well as a decrease in the initial concentration enhanced the pollutants' removal. The removal selectivity of both materials with slight differences follows the order Cd > Zn & toluene > ethylbenzene > m- & p-xylene > o-xylene > benzene. According, to the results derived from the continuous flow experiments the maximum adsorption capacity of the compost (90%) referred to Cd (0.88 mmol/g) whereas the minimum refers to benzene (65%) with a capacity up to 0.065 mmol/g. Zeolite had lower efficiencies for the studied pollutants with a higher performance corresponding to Cd (0.26 mmol/g), whereas the minimum zeolite capacity (63%) corresponds to toluene (0.045 mmol/g). Thus, this paper provides evidence that compost, a low cost material produced from waste, is capable for the simultaneous removal of both organic and inorganic pollutants from wastewater, and its performance is superior to zeolite.

Quinone-Bodipy H-bonding interaction over π-stacking in toluene.

Quinone type compounds (o-chloranil, p-chloranil and DDQ) demonstrate excellent H-bonding interactions with a meso-phenol Bodipy dye (1) in both ground and excited state in a non-polar toluene medium. The spectroscopic detection of isosbestic absorption occurs with both quinones and fullerenes, but only quinones form isoemissive complexes with dye 1. (1)H NMR study and Monte Carlo global minima searching justified the above mentioned results with efficiency.

A highly efficient three-phase single drop microextraction technique for sample preconcentration.

A highly efficient three-phase single drop microextraction (SDME) method is presented by using an organic-aqueous compound droplet. A coupling microdevice is designed to produce compound droplets in different sizes conveniently. In this way, the volume ratio of organic phase to aqueous phase in a compound droplet can be significantly reduced. Good operability and droplet stability were observed during extraction under vigorous stirring conditions. Five statins were used as model compounds and spiked in river water and human serum samples to evaluate the analytical performance of the proposed method. By using a 1.2 µL toluene-aqueous compound droplet (volume ratio 0.2 : 1), a 350 to 1712 fold enrichment of statins was obtained within 4 minutes. The results indicate that the proposed method is a very rapid and efficient sample pretreatment method, and is promising for automated and high-throughput applications.

Modeling the selectivity of indoor pollution gases over N2 on covalent organic frameworks.

The selectivity of indoor pollution gases (including formaldehyde, benzene, and toluene) over N2 on a set of 37 covalent organic frameworks (COFs) was modeled by combining classical grand canonical Monte Carlo (GCMC) methods and periodic density functional theory with dispersion correction (DFT-D2). The pore volume, pore size, and the isosteric heat (Q st) of gases on COFs were investigated to explore the origin of the high selectivity of pollution gases over N2. We found that the size match between the pore of the COFs and the corresponding pollution gases is the key factor for high selectivity. Additionally, the Q st for the investigated four gases follows the order of toluene > benzene > formaldehyde > N2, which is consistent with the order of selectivity. Furthermore, the favorite sites and interaction energies of pollution gases on COFs were calculated by the periodic DFT-D2 method. Our simulation procedure offers an alternative approach with which to evaluate or design the best candidate porous materials in capture pollution gases.

Exploring the C-X π halogen bonding motif: an infrared and Raman study of the complexes of CF3X (X = Cl, Br and I) with the aromatic model compounds benzene and toluene.

The formation of halogen bonded complexes formed between the trifluorohalomethanes CF3Cl, CF3Br and CF3I and the Lewis bases benzene and toluene at temperatures below 150K was investigated using FTIR and Raman spectroscopy. Experiments using liquid krypton as solvent show that for both CF3Br and CF3I substantial fractions of the monomers can be involved in 1:1 complexes. In addition, weak absorptions illustrating the formation of 2:1 complexes between CF3I and benzene are observed. Using spectra recorded at temperatures between 120 and 140 K, observed information on the relative stability was obtained for all complexes by determining the complexation enthalpies in solution. The resulting values for CF3Br.benzene, CF3I.benzene and (CF3I)2.benzene are -6.5(3), -7.6(2) and -14.5(9) kJ mol⁻¹. The values for CF3Br.toluene and CF3I.toluene are -6.2(5) and -7.4(5) kJ mol⁻¹. The experimental complexation enthalpies are compared with theoretical data obtained by combining results from MP2/aug-cc-pVDZ(-PP) and MP2/aug-cc-pVTZ(-PP) ab initio calculations, from statistical thermodynamical calculations and from Monte Carlo Free Energy Perturbation simulations. The data are also compared with results derived for other C-X···π halogen bonded complexes involving unsaturated Lewis bases such as ethene and ethyne.