5-Methyl-2,4-bis(methylsulfanyl)tricyclo[6.2.1.0(2,7)]undeca-4,9-diene-3,6-dione

The structure analysis of the title compound, C(14)H(16)O(2)S(2), shows the SMe and H atoms of the bond linking the six-membered rings to be syn and also to be syn to the bridgehead -CH(2)- group. Each of the five-membered rings adopts an envelope conformation at the bridgehead -CH(2)- group. The dione-substituted ring adopts a folded conformation about the 1,4-C center dot center dot center dot C vector, with the ketone groups lying to one side. The cyclohexene ring adopts a boat conformation.

Intermolecular vibrations and fast relaxations in supercooled ionic liquids

Short-time dynamics of ionic liquids has been investigated by low-frequency Raman spectroscopy (4 < omega < 100 cm(-1)) within the supercooled liquid range. Raman spectra are reported for ionic liquids with the same anion, bis(trifluoromethylsulfonyl)imide, and different cations: 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-butyl-1-methylpiperidinium, trimethylbutylammonium, and tributylmethylammonium. It is shown that low-frequency Raman spectroscopy provides similar results as optical Kerr effect (OKE) spectroscopy, which has been used to study intermolecular vibrations in ionic liquids. The comparison of ionic liquids containing aromatic and non-aromatic cations identifies the characteristic feature in Raman spectra usually assigned to librational motion of the imidazolium ring. The strength of the fast relaxations (quasi-elastic scattering, QES) and the intermolecular vibrational contribution (boson peak) of ionic liquids with non-aromatic cations are significantly lower than imidazolium ionic liquids. A correlation length assigned to the boson peak vibrations was estimated from the frequency of the maximum of the boson peak and experimental data of sound velocity. The correlation length related to the boson peak (similar to 19 angstrom) does not change with the length of the alkyl chain in imidazolium cations, in contrast to the position of the first-sharp diffraction peak observed in neutron and X-ray scattering measurements of ionic liquids. The rate of change of the QES intensity in the supercooled liquid range is compared with data of excess entropy, free volume, and mean-squared displacement recently reported for ionic liquids. The temperature dependence of the QES intensity in ionic liquids illustrates relationships between short-time dynamics and long-time structural relaxation that have been proposed for glass-forming liquids. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3604533]

2-(4-Methylphenyl)-1H-anthraceno-[1,2-d]imidazole-6,11-dione: a fluorescent chemosensor

In the title compound, C(22)H(14)N(2)O(2), the five rings of the molecule are not coplanar. There is a significant twist between the four fused rings, which have a slightly arched conformation, and the pendant aromatic ring, as seen in the dihedral angle of 13.16 (8)degrees between the anthraquinonic ring system and the pendant aromatic ring plane.

Nickel sorption capacity of ground xylem of Quercus ilex trees and effects of selected ligands present in the xylem sap

In this work the influence of four different ligands present in the xylem sap of Quercus ilex (histidine, citric, oxalic and aspartic acids) on Ni(II) adsorption by xylem was investigated. Grinded xylem was trapped in acrylic columns and solutions of Ni(II), in the absence and presence of the four ligands prepared in KNO(3) 0-1 mol L(-1) at pH 5.5, were percolated through the column. Aliquots of solutions were recovered in the column end for Ni determination by graphite furnace atomic absorption spectrometry (GFAAS). The experimental. data to describe Ni sorption by xylem in both the presence and absence of ligands was better explained by the Freundlich isotherm model. The decreasing affinity order of ligands for Ni was: oxalic acid > citric acid > histidine > aspartic acid. On the other hand, the Ni(II) adsorption by xylem increased following the inverse sequence of ligands. Potentiometric titrations of acidic groups were carried out to elucidate the sorption site groups available in Q. ilex xylem. The potentiometric titration has shown three sorption sites: pK(a) 2.6 (57.7% of the sorption sites), related to monobasic aliphatic carboxylic acids or nitrogen aromatic bases, pK(a) 8.1 (9.6%) and pK(a) 9.9 (32.7%), related to phenolic groups. (C) 2008 Elsevier GmbH. All rights reserved.

Technological advances and mechanistic basis for fungal biopulping

Biopulping fundamentals, technology and mechanisms are reviewed in this article. Mill evaluation of Eucalyptus grandis wood chips biotreated by Ceriporiopsis subvermispora on a 50-tonne pilot-plant demonstrated that equivalent energy savings can be obtained in lab- and mill-scale biopulping. Some drawbacks concerning limited improvements in pulp strength and contamination of the chip pile with opportunist fungi have been observed. The use of pre-cultured wood chips as inoculum seed for the biotreatment process minimized contamination problems related to the use of blended mycelium and corn-steep liquor in the inoculation step. Alkaline wash restored part of the brightness in biopulps and marketable brightness values were obtained by one-stage bleaching with 5% H2O2 when bio-TMP pulps were under evaluation. Considering the current scenario, the understanding of biopulping mechanisms has gained renewed attention because more resistant and competitive fungal species could be selected with basis on a function-directed screening project. A series of studies aimed to elucidate structural changes in lignin during wood biodegradation by C. subvermispora had indicated that lignin depolymerization occurs during initial stages of wood biotreatment. Aromatic hydroxyls did not increase with the split of aryl-ether linkages, suggesting that the ether-cleavage-products remain as quitione-type structures. On the other hand, cellulose is more resistant to the attack by C subvermispora. MnP-initiated lipid peroxidation reactions have been proposed to explain degradation of non-phenolic lignin substructures by C subvermispora, while the lack of cellobiohydrolases and the occurrence of systems able to suppress Fenton`s reaction in the cultures have explained non-efficient cellulose degradation by this biopulping fungus. (C) 2007 Elsevier Inc. All rights reserved.

Treatment of wastewater from a cotton dyeing process with UV/H(2)O(2) using a photoreactor covered with reflective material

Wastewater containing several dyes, including sulfur black from the dyeing process in a textile mill, was treated using a UV/H(2)O(2) process. The wastewater was characterized by a low BOD/ COD ratio, intense color and high acute toxicity to the algae species Pseudokirchneriella subcaptata. The influence of the pH and H(2)O(2) concentration on the treatment process was evaluated by a full factorial design 2(2) with three replicates of the central experiment. The removal of aromatic compounds and color was improved by an increase in the H(2)O(2) concentration and a decrease in pH. The best results were obtained at pH 5.0 and 6 g L(-1). With these conditions and 120 min of UV irradiation, the removal of the color, aromatic compounds and COD were 74.1, 55.1 and 44.8%, respectively. Under the same conditions, but using a photoreactor covered with aluminum foil, the removal of the color, aromatic compounds and COD were 92.0, 77.6 and 59.4%, respectively. Moreover, the use of aluminum foil reduced the cost of the treatment by 40.8%. These results suggest the potential application of reflective materials as a photoreactor accessory to reduce electric energy consumption during the UV/H(2)O(2) process.

Use of activated charcoal and ion-exchange resin to cleaN up and concentrate enzymes in extracts from biodegraded wood.

Use of activated charcoal and ion-exchange resin to cleaN up and concentrate enzymes in extracts from biodegraded wood. Ceriporiopsis subvermispora was used for the biodegradation of Eucalyptus grandis chips in the presence or absence of co-substrates (glucose and corn steep liquor) during 7, 14 and 28 days. Afterwards, the biodegraded chips were extracted with 50 mM sodium acetate buffer (pH 5.5) supplemented with 0.01% Tween 60. High activities of manganese peroxidases (MnPs) were observed in all the extracts, both in the absence (430, 765 and 896 UI kg(-1) respectively) and in the presence of co-substrates (1,013; 2,066 and 2,323 UI kg(-1) respectively). The extracts presented a high ratio between absorbances at 280 and 405 nm, indicating a strong abundance of aromatic compounds derived from lignin over heme-peroxidases. Adsorption into activated charcoal showed to be an adequate strategy to reduce the absorbance at 280 urn in all the extracts. Moreover, it allowed to maximize the capacity of an anion exchange resin bed (DEAE-Sepharose) used to concentrate the MnPs present in the extracts. It was concluded that the use of activated charcoal followed by adsorption into DEAE Sepharose is a strategy that can be used to concentrate MnPs in extracts obtained during the biodegradation of E. grandis by C. subvermispora.

Toxicity and recalcitrant compound removal from bleaching pulp plant effluents by an integrated system: anaerobic packed-bed bioreactor and ozone

Effluents originated in cellulose pulp manufacturing processes are usually toxic and recalcitrant, specially the bleaching effluents, which exhibit high contents of aromatic compounds (e.g. residual lignin derivates). Although biological processes are normally used, their efficiency for the removal of toxic lignin derivates is low. The toxicity and recalcitrance of a bleached Kraft pulp mill were assessed through bioassays and ultraviolet absorption measurements, i.e. acid soluble lignin (ASL), UV(280), and specific ultraviolet absorption (SUVA), before and after treatment by an integrated system comprised of an anaerobic packed-bed bioreactor and oxidation step with ozone. Furthermore, adsorbable organic halides (AOX) were measured. The results demonstrated not only that the toxic recalcitrant compounds can be removed successfully using integrated system, but also the ultraviolet absorption measurements can be an interesting control-parameter in a wastewater treatment.

Bioremediation of gasoline-contaminated groundwater in a pilot-scale packed-bed anaerobic reactor

This work reports on the anaerobic treatment of gasoline-contaminated groundwater in a pilot-scale horizontal-flow anaerobic immobilized biomass reactor inoculated with a methanogenic consortium. BTEX removal rates varied from 59 to 80%, with a COD removal efficiency of 95% during the 70 days of in situ trial. BTEX removal was presumably carried out by microbial syntrophic interactions, and at the observed concentrations, the interactions among the aromatic compounds may have enhanced overall biodegradation rates by allowing microbial growth instead of co-inhibiting biodegradation. There is enough evidence to support the conclusion that the pilot-scale reactor responded similarly to the lab-scale experiments previously reported for this design. (C) 2009 Elsevier Ltd. All rights reserved.

Analysis of the emissions of volatile organic compounds from the compression ignition engine fueled by diesel-biodiesel blend and diesel oil using gas chromatography

This paper describes the procedures of the analysis Of Pollutant gases, as volatile organic compounds (benzene, toluene, ethylbenzene, o-xylene, m-xylene and p-xylene) emitted by engines, using high-resolution gas chromatography (HRGC). In a broad sense, CI engine burning diesel was compared with B10 and a drastic reduction was observed in the emissions of the aromatic compounds by using B10. Especially for benzene, the reduction of concentrations occurs on the level of about 19.5%. Although a concentration value below 1 mu g ml(-1) has been obtained, this reduction is extremely significant since benzene is a carcinogenic compound. (c) 2008 Elsevier Ltd. All rights reserved.

Changes in optical properties caused by UV-irradiation of aquatic humic substances from the amazon river basin: Seasonal variability evaluation

Aquatic humic substances (AHS) isolated from two characteristic seasons of the Negro river, winter and summer corresponding to floody and dry periods, were structurally characterized by (13)C nuclear magnetic ressonance. Subsequently, AHS aqueous solutions were irradiated with a polychromatic lamp (290-475 nm) and monitored by its total organic carbon (TOC) content, ultraviolet-visible (UV-vis) absorbance, fluorescence and Fourier transformed infrared spectroscopy (FTIR). As a result, a photobleaching upto 80% after irradiation of 48 h was observed. Conformational rearrangements and formation of low molecular complexity structures were formed during the irradiation, as deduced from the pH decrement and the fluorescence shifting to lower wavelengths. Additionally a significant mineralization with the formation Of CO(2), CO, and inorganic carbon compounds was registered, as assumed by TOC losses of up to 70%. The differences in photodegradation between samples expressed by photobleaching efficiency were enhanced in the summer sample and related to its elevated aromatic content. Aromatic structures are assumed to have high autosensitization capacity effects mediated by the free radical generation from quinone and phenolic moieties.

Emissions from the premixed combustion of gasified polyethylene

An investigation was conducted on pollutants emitted from steady-state, steady-flow gasification and combustion of polyethylene (PE) in a two-stage furnace. The polymer, in pulverized form, was first pyrolyzed at 1000 degrees C, and subsequently, its gaseous pyrolyzates were burned, upon mixing with air at high temperatures (900-1100 degrees C). The motivation for this indirect type of burning PE was to attain nominally premixed combustion of the pyrolyzate gases with air, thereby achieving lower pollutant emissions than those emanating from the direct burning of the solid PE polymer. This work assessed the effluents of the two-stage furnace and examined the effects of the combustion temperature, as well as the polymer feed rate and the associated fuel/air equivalence ratio (0.3 < phi < 1.4). It was found that, whereas the yield of pyrolysis gas decreased with an increasing polymer feed rate, its composition was nearly independent of the feed rate. CO2 emissions peaked at an equivalence ratio near unity, while the CO emissions increased with an increasing equivalence ratio. The total light volatile hydrocarbon and semivolatile polycyclic aromatic hydrocarbon (PAH) emissions of combustion increased with an increasing equivalence ratio. The generated particulates were mostly submicrometer in size. Overall, PAH and soot emissions from this indirect burning of PE were an order of magnitude lower than corresponding emissions from the direct burning of the solid polymer, obtained previously in this laboratory using identical sampling and analytical techniques. Because pyrolysis of this polymer requires a nominal heat input that amounts to only a diminutive fraction of the heat released during its combustion, implementation of this technique is deemed advantageous.

Synthesis, characterization and evaluation of phosphorylated resins in the removal of Pb(2+) from aqueous solutions

Phosphinic-derivative poly(styrene-co-divinylbenzene)-based on PS-DVB copolymers with different porosity degrees have been prepared by aromatic electrophilic substitution reaction using PCl(3)/AlCl(3) followed by base-promoted hydrolysis. The phosphorylation reaction was analyzed by infra-red spectroscopy (FTIR), scanning electron microscopy (SEM), and thermogravimetry (TG/DTG). In addition, the phosphorous content of the phosphorylated copolymers was determined by spectrophotometry using the method based on sodium molybdate reactant so that the extension of that modification could be assessed. The performance of the phosphorylated resins in the extraction of Pb(2+) from aqueous solutions in a batch system was also evaluated. The Pb(2+) content was determined by atomic absorption spectrometry (AAS). These materials presented excellent extraction capacity under the contact time of 30 min and pH 6.

Application of Fluorescence to the Study of Crude Petroleum

Crude petroleum oils are complex mixtures of different compounds (mainly organic), which are obtained from an extensive range of different geological sources. The fluorescence of crude petroleum oils derives largely from the aromatic hydrocarbon fraction, and this fluorescence emission is strongly influenced by the chemical composition (e.g., fluorophore and quencher concentrations) and physical characteristics (e.g., viscosity and optical density) of the oil. The fluorescence spectroscopy (FS) is increasingly used in petroleum technology due the availability of better optical detection techniques, because FS offers high sensitivity, good diagnostic potential, and relatively simple instrumentation. In this work we analyzed crude petroleum at different dilution in Nujol, a transparent mineral oil. The main objective of this work was to verify the possibility to measure crude oil emission spectroscopic without use of volatile solvents. The mixtures of nujol with different -crude oil concentrations were measured with a 10 mm optical path cuvette thus simplifying the fluorescence spectroscopy signal detection. The emission spectra were obtained by exciting the samples with a 400 W Xenon lamp at 350 nm, 450 nm and 532 nm. The emissions of the samples were collected perpendicularly with the excitation axis.

Batch Liquid-Liquid Extraction of Phenol from Aqueous Solutions

The aim of this work is the study of batch liquid-liquid extraction of phenol from aqueous solutions in a bench-scale well-mixed reactor. The influence of the ratio of phase volumes, temperature, and rotational speed on phenol removal (0.72-1.1% w/w) was investigated using methyl isobutyl ketone as an extracting solvent. For this purpose, the ratio of phase volumes were set at 0.1 and 0.2, the temperature at 10, 20, and 30 degrees C, and the rotational speed at 300, 400, and 500 rpm. A physical model based on the material balance of the phases as well as the equation of mass flux between the phases allowed the estimation of the overall coefficient of mass transfer coupled with the superficial area. Moreover, it proved to fit, satisfactorily well, the experimental data of residual phenol concentration in the organic phase versus time under all the conditions investigated.