The dangers of lead exposure have been recognized for millennia. In the first century a.d., Dioscorides observed in his De Materia Medica that “lead makes the mind give way.” The first industrial hygiene act passed in the colonies, in 1723, prohibited the use of lead in the apparatus used to distill rum, because “the strong liquors and spirits that are distilld through leaden heads or pipes are judged on good grounds to be unwholsom and hurtful.” More recently, large amounts of lead were used to boost the octane rating of gasoline and improve the performance of paint. One would be . . .
Benzene, a hazardous component of gasoline, is a genotoxic class I human carcinogen. This study evaluated the genotoxic effects of occupational exposure to benzene in gasoline stations. Genotoxicity of exposure to benzene was assessed in peripheral blood leucocytes of 62 gasoline station workers and compared with an equal numbers of matched controls using total genomic DNA fragmentation, micronucleus test and cell viability test. An ambient air samples were collected and analyzed for Monitoring of benzene, toluene, ethyl benzene and xylene (BTEX) in work environment and control areas. DNA fragmentation, micronucleus and dead cells percent were significantly higher in exposed workers than controls. Level of benzene, Toluene, Ethyl benzene and xylene in the work environment were higher than the control areas and the permissible limits. Gasoline station workers occupationally exposed to benzene are susceptible to genotoxic effects indicated by increased DNA fragmentation, higher frequency of micronucleus and decreased leukocytes viability.
Trinitrobenzene (TNB) and trinitrotoluene (TNT) react in N,N-dimethylformamide (DMF) to form multiple species in solution. Despite structural similarities, electronic spectra show that the reactivity is different for TNB and TNT. In addition to reaction with the DMF solvent, residual water in nominally dry DMF generates sufficient hydroxide for reaction with TNB and TNT. Multiple sigma adducts are formed and observed to be fluorescent, which has not been previously reported. Both TNB and TNT show the capacity to form sigma adducts with hydroxide and DMF, while methyl hydrogens of TNT can be deprotonated by hydroxide.
Various technologies have been used for the treatment and remediation of areas contaminated by BTEX (benzene, toluene, ethylbenzene and xylenes), which are organic compounds that are of particular concern due to their toxicity. Potential applications of synthetic zeolites for environmental fieldwork have also been reported worldwide. In this work, a hexadecyltrimethyl ammonium (HDTMA) surfactant-modified synthetic zeolite was investigated for its efficiency in removing BTEX from aqueous solutions. Three surfactant-modified zeolites were synthesized, with amounts of surfactant corresponding to 50%, 100%, and 200% of the total cation-exchange capacity (CEC) of the synthetic zeolite Y. The results of the BTEX adsorption experiments onto both synthetic zeolite and surfactant-modified zeolites (SMZ) showed that the SMZ-100 (zeolite modified with surfactant levels at 100% of CEC) was the most efficient modified zeolite for BTEX removal. Kinetics studies indicated that the multicomponent adsorption equilibrium was reached within 6 h and followed pseudo-second-order kinetics. The Langmuir, Freundlich, Redlich-Peterson and Temkin models were used to evaluate the BTEX adsorption capacity by SMZ-100. The Temkin model was found to be suitable for all BTEX compounds in a multicomponent system. Regeneration cycles of the modified zeolite were also performed, and the results showed that the adsorbent could be used efficiently in as many as four adsorption cycles, except for benzene.
In this study, flotation-assisted homogeneous liquid-liquid microextraction (FA-HLLME) was developed as a fast, simple, and efficient method for extraction of four polycyclic aromatic hydrocarbons (PAHs) in soil samples followed by gas chromatography-flame ionization detector (GC-FID) analysis. A special home-made extraction cell was designed to facilitate collection of the low-density extraction solvent without a need for centrifugation. In this method, PAHs were extracted from soil samples into methanol and water (1:1, v/v) using ultrasound in two steps followed by filtration as a clean-up step. The filtrate was added into the home-made extraction cell contained mixture of 1.0mL methanol (homogenous solvent) and 150.0μL toluene (extraction solvent). Using N(2) flotation, the dispersed extraction solvent was transferred to the surface of the mixture and was collected by means of a micro-syringe. Then, 2μL of the collected organic solvent was injected into the GC-FID for subsequent analysis. Under optimal conditions, linearity of the method was in the range of 40-1000μgkg(-1) soil (dry weight). The relative standard deviations in real samples varied from 5.9 to 15.2% (n=4). The proposed method was successfully applied to analyze the target PAHs in soil samples, and satisfactory results were obtained.
Lost and found: In situ exohedral trifluoromethylation of endohedral fullerenes using an arc-discharge method gives access to a wide variety of missing unconventional metallofullerenes. Such otherwise insoluble and unstable metallofullerenes become soluble and stable in organic solvents after an exterior functionalization.
Thermally activated delayed fluorescence (TADF) is fluorescence arising from a reverse intersystem crossing (RISC) from the lowest triplet (T1) to the singlet excited state (S1), where these states are separated by a small energy gap (Est), followed by a radiative transition to the ground state (S0). Rate constants relating TADF processes in 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) were determined at four different solvent polarities (toluene, dichloromethane, ethanol and acetonitrile). We revealed that the rate constant of RISC, kRISC, which is the most important factor for TADF, was significantly enhanced by a reduced Est in more polar solvents. The smaller Est was mainly attributable to a stabilization of the S1 state. This stabilization also induced a Stokes shift in fluorescence through a relatively large change of the dipole moment between S1 and S0 states (17 D). Despite of this factor, we observed a negative correlation between Est and efficiency of the delayed fluorescence (d). This was ascribed to a lower intersystem crossing rate, kISC, and increased non-radiative decay from S1, k_nr^s, in polar solvents.
The reaction of Ru(5)(CO)(15)(μ(5)-C) with Ni(COD)(2) in acetonitrile at 80 °C affords the bimetallic octahedral ruthenium-nickel cluster complex Ru(5)Ni(NCMe)(CO)(15)(μ(6)-C), 3. The acetonitrile ligand in 3 can be replaced by CO and NH(3) to yield Ru(5)Ni(CO)(16)(μ(6)-C), 4, and Ru(5)Ni(NH(3))(CO)(15)(μ(6)-C), 5, respectively. Photolysis of compound 3 in benzene and toluene solvent yielded the η(6)-coordinated benzene and toluene Ru(5)Ni carbido cluster complexes Ru(5)Ni(CO)(13)(η(6)-C(6)H(6))(μ(6)-C), 6, and Ru(5)Ni(CO)(13)(η(6)-C(7)H(8))(μ(6)-C), 7, respectively. All five new compounds were structurally characterized by single-crystal X-ray diffraction analyses.
A poly(o-anisidine)/graphene oxide nanosheets (PoA/GONSs) coating is fabricated by a simple and efficient electrochemical deposition method on steel wire. The incorporation of PoA and GONSs allows preparing a nanocomposite that can successfully integrate the advantages of both. Then, the prepared fiber is applied to the headspace solid-phase microextraction (HS-SPME) and gas chromatographic analysis of benzene, toluene, ethylbenzene and xylenes. In order to obtain an adherent, stable and efficient fiber to extract target analytes, experimental parameters related to the coating process such as deposition potential, deposition time, concentration of the monomer and concentration of GONSs were studied. The prepared composite fiber were characterized by Fourier transform infrared spectroscopy, powder X-ray diffraction and scanning electron microscopy. The effect of various parameters on the efficiency of HS-SPME process consisting of desorption temperature and time, extraction temperature and time and ionic strength were also optimized. Under the optimal conditions, the method was linear for orders of magnitude with correlation coefficients varying from 0.9888 to 0.9993. Intra- and inter-day precisions of the method were determined from mixed aqueous solutions containing 5.0ngmL(-1) of each BTEX. The intra-day precisions varied from 3.1% for toluene to 5.7% for ethylbenzene, while the inter-day precisions varied from 4.9% for o-xylene to 7.3% for m,p-xylene. Limits of detection were in the range 0.01-0.06ngmL(-1). The proposed method was applied to monitor BTEX compounds in some water samples and the accuracies found through spiking river water samples showed high recoveries between 92.0 and 101.2%.
The potential energy surfaces in gas phase and in aqueous solution for the nitration of benzene, chlorobenzene, and phenol have been elucidated with density functional theory at the M06-2X/6-311G(d,p) level combined with the polarizable continuum solvent model (PCM). Three reaction intermediates have been identified along both surfaces: the unoriented π-complex (I), the oriented reaction complex (II), and the σ-complex (III). In order to obtain quantitatively reliable results for positional selectivity and for modeling the expulsion of the proton, it is crucial to take solvent effects into consideration. The results are in agreement with Olah’s conclusion from over 40 years ago that the transition state leading to (II) is the rate-determining step in activated cases, while it is the one leading to (III) for deactivated cases. The simplified reactivity approach of using the free energy for the formation of (III) as a model of the rate-determining transition state has previously been shown to be very successful for halogenations, but problematic for nitrations. These observations are rationalized with the geometric and energetic resemblance, and lack of resemblance respectively, between (III) and the corresponding rate determining transition state. At this level of theory, neither the σ-complex (III) nor the reaction complex (II) can be used to accurately model the rate-determining transition state for nitrations.