Dissipation and dietary risk assessment of tristyrylphenol ethoxylate homologues in cucumber after field application.

The potential for tristyrylphenol ethoxylates (TSPEOs) residues to contaminate crops or be released into the environment is of increasing concern, as they are toxic to living organisms. This study determined the dissipation of TSPEO homologues in cucumber under field conditions. TSPEOn (n = 6-29) dissipated more rapidly in cucumber than in soil samples, with half-lives of 1.80-4.30 d and 3.73-6.52 d, respectively. Short-chain TSPEOn (n = 6-11) persisted for longer than other oligomers in soil. Concentrations of the final residues (∑TSPEOs) in cucumber and soil were 24.3-1349 µg/kg and 47.3-1337 µg/kg, respectively. TSP15EO or TSP16EO was the dominant oligomer, with concentrations of 2.30-150 µg/kg. The risk assessment showed that the acute and chronic dietary exposure risks of ∑TSPEOs in cucumber were 0.03-0.57% and 0.05-0.39%, respectively, suggesting little or no health risk to Chinese consumers.

Biocompatible and Rapid Cyclization of Peptides with 2,4-Difluoro-6-hydroxy-1,3,5-benzenetricarbonitrile for the Development of Cyclic Peptide Libraries.

We report a biocompatible and rapid reaction between cysteine thiols and 2,4-difluoro-6-hydroxy-1,3,5-benzenetricarbonitrile (DFB), which enables the efficient cyclization of peptides in neutral aqueous solutions. The reaction was further applied to cyclize peptides displayed on the phage surface without reducing phage infectivity, thus affording high-quality cyclic peptide libraries useful for screening of cyclic peptide ligands. Using the DFB-cyclic peptide library, we identified ligands that can distinguish the pro-survival protein Bcl-xl from its close relative Bcl-2. Therefore, this study on one hand reports a useful reaction for the construction of cyclic peptide libraries, and on the other hand presents valuable hits for further design of selective Bcl-xl ligands.

Safety Assessment of Benzyne Generation from a Silyl Triflate Precursor.

Silyl triflate precursors to benzyne and related intermediates have emerged as valuable synthetic building blocks. However, data addressing the safety of employing these silyl triflate precursors are lacking. We report the calorimetric analysis of a typical Kobayashi procedure for forming and trapping benzyne using a silyl triflate precursor. Our findings suggest that, unlike benzenediazonium carboxylate precursors to benzyne, silyl triflates may be employed under mild conditions without severe concern for runaway reaction.

New anthranilic acid-incorporating N-benzenesulfonamidophthalimides as potent inhibitors of carbonic anhydrases I, II, IX, and XII: Synthesis, in vitro testing, and in silico assessment.

The carbonic anhydrase (CA) inhibitory activity of newly synthesized compounds 4-21 against the human CA (hCA) isoforms I, II, IX, and XII was measured and compared to that of standard sulfonamide inhibitors, acetazolamide (AAZ) and SLC-0111. Among this series; benzensulfonamides 6-11 gave the best potent hCA inhibitors with inhibition constants (KIs) ranging from 81.9 to 456.6 nM (AAZ and SLC-0111: KIs, 250.0 and 5080 nM, respectively). Compounds 6-11 proved to be effective hCA II inhibitors (KIs, 8.9-51.5 nM); they were almost equally potent to AAZ (KI, 12.0 nM) and had superior potency to SLC-0111 (KI, 960.0 nM). For hCA IX inhibition, compounds 6-11 proved to be potent inhibitors, with KI values of 3.9-36.0 nM, which were greater than or equal to that of AAZ and greater than that of SLC-0111 (KIs, 25.0 and 45.0 nM, respectively). For hCA XII inhibitory activity, compounds 6-11 displayed effective inhibition with KI values ranging from 4.6 to 86.3 nM and were therefore comparable to AAZ and SLC-0111 (KIs, 5.7 and 4.5 nM, respectively). Molecular docking studies of compounds 6, 7, 10, and 11 were conducted using the crystal structures of hCA isozymes I, II, IX, and XII to study their binding interactions for further lead optimization.

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 Ab Initio and Density Functional Theory Methods for the Excitations of Donor-Acceptor Complexes: The Case of the Benzene-Tetracyanoethylene Model.

The understanding of the excited-state properties of electron donors, acceptors and their interfaces in organic optoelectronic devices is a fundamental issue for their performance optimization. In order to obtain a balanced description of the different excitation types for electron-donor-acceptor systems, including the singlet charge transfer (CT), local excitations, and triplet excited states, several ab initio and density functional theory (DFT) methods for excited-state calculations were evaluated based upon the selected model system of benzene-tetracyanoethylene (B-TCNE) complexes. On the basis of benchmark calculations of the equation-of-motion coupled-cluster with single and double excitations method, the arithmetic mean of the absolute errors and standard errors of the electronic excitation energies for the different computational methods suggest that the M11 functional in DFT is superior to the other tested DFT functionals, and time-dependent DFT (TDDFT) with the Tamm-Dancoff approximation improves the accuracy of the calculated excitation energies relative to that of the full TDDFT. The performance of the M11 functional underlines the importance of kinetic energy density, spin-density gradient, and range separation in the development of novel DFT functionals. According to the TDDFT results, the performances of the different TDDFT methods on the CT properties of the B-TCNE complexes were also analyzed.

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.

Pd-Metalated Conjugated Nanoporous Polycarbazoles for Additive-Free Cyanation of Aryl Halides: Boosting Catalytic Efficiency through Spatial Modulation.

Transition-metal-catalyzed cyanation of aryl halides is a common route to benzonitriles, which are integral to many industrial procedures. However, traditional homogeneous catalysts for such processes are expensive and suffer poor recyclability, so a heterogeneous analogue is highly desired. A novel spatial modulation approach has been developed to fabricate a heterogeneous Pd-metalated nanoporous polymer, which catalyzes the cyanation of aryl halides without need for ligands. The catalyst displays high activity in the synthesis of benzonitriles, including high product yields, excellent stability and recycling, and broad functional-group tolerance.

Prediction of Aquatic Toxicity of Benzene Derivatives to Tetrahymena pyriformis According to OECD Principles.

BACKGROUND: Many QSAR studies have been developed to predict acute toxicity over several biomarkers like Pimephales promelas, Daphnia magna and Tetrahymena pyriformis. Regardless of the progress made in this field there are still some gaps to be resolved such as the prediction of aquatic toxicity over the protozoan T. pyriformis still lack a QSAR study focused in accomplish the OECD principles. METHODS: Atom-based quadratic indices are used to obtain quantitative structure-activity relationship (QSAR) models for the prediction of aquatic toxicity. Our models agree with the principles required by the OECD for QSAR models to regulatory purposes. The database employed consists of 392 substituted benzenes with toxicity values measured in T. pyriformis (defined endpoint), was divided using cluster analysis in two series (training and test sets). RESULTS: We obtain (with an unambiguous algorithm) two good multiple linear regression models for non-stochastic (R2=0.807 and s=0.334) and stochastic (R2=0.817 and s=0.321), quadratic indices. The models were internally validated using leave-one-out, bootstrapping as well as Y-scrambling experiments. We also perform an external validation using the test set, achieving values of R2 pred values of 0.754 and 0.760, showing that our models have appropriate measures of goodness- of-fit, robustness and predictivity. Moreover, we define a domain of applicability for our best models. CONCLUSION: The achieved results demonstrated that, the atom-based quadratic indices could provide an attractive alternative to the experiments currently used for determining toxicity, which are costly and time-consuming.

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.

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.

A selective, expeditious and sustainable entry en route to benzopyrazines and bis-benzopyrazines.

A convenient green synthesis of benzopyrazines and bis-benzopyrazines has been performed by the condensation of diversely substituted diamines and dicarbonyl compounds in water using indium powder as catalyst under controlled microwave exposure. The effects of microwave power, and temperature on this reaction are investigated in detail to identify the best condition. A wide range of diversely substituted diamines and dicarbonyl compounds produce excellent yield of the corresponding benzopyrazines and bis-benzopyrazines. A comparative study has also been made between microwave-induced procedure and conventional method. The present method is atom-economical, environmentally friendly, and affords synthetically useful and challenging products very rapidly.

Determination of partial molar volumes from free energy perturbation theory.

Partial molar volume is an important thermodynamic property that gives insights into molecular size and intermolecular interactions in solution. Theoretical frameworks for determining the partial molar volume (V°) of a solvated molecule generally apply Scaled Particle Theory or Kirkwood-Buff theory. With the current abilities to perform long molecular dynamics and Monte Carlo simulations, more direct methods are gaining popularity, such as computing V° directly as the difference in computed volume from two simulations, one with a solute present and another without. Thermodynamically, V° can also be determined as the pressure derivative of the free energy of solvation in the limit of infinite dilution. Both approaches are considered herein with the use of free energy perturbation (FEP) calculations to compute the necessary free energies of solvation at elevated pressures. Absolute and relative partial molar volumes are computed for benzene and benzene derivatives using the OPLS-AA force field. The mean unsigned error for all molecules is 2.8 cm(3) mol(-1). The present methodology should find use in many contexts such as the development and testing of force fields for use in computer simulations of organic and biomolecular systems, as a complement to related experimental studies, and to develop a deeper understanding of solute-solvent interactions.