Improvement in desulfurization of dibenzothiophene and dibenzothiophene sulfone by Paenibacillus strains using immobilization or nanoparticle coating.

AIMS: Biodesulfurization of fossil fuels is a promising technology for deep desulfurization. Previously, we have shown that Paenibacillus strains 32O-W and 32O-Y can desulfurize dibenzothiophene (DBT) and DBT sulfone (DBTS) effectively. In this work, improvements in DBT and DBTS desulfurization by these strains were investigated through immobilization and nanoparticle coating of cells. METHODS AND RESULTS: Paenibacillus strains 32O-W and 32O-Y immobilized in alginate gel beads or coated with Fe3 O4 magnetite nanoparticles were grown at various concentrations (0.1-2 mmol l-1 ) of DBT or DBTS for 96 h. The production of 2-hydroxybiphenyl (2-HBP) from the 4S pathway biotransformation of DBT or DBTS was measured. The highest amounts of 2-HBP production occurred at concentrations of 0.1 and 0.5 mmol l-1 . Compared to planktonic cultures maximum 2-HBP production increased by 54% for DBT and 90% for DBTS desulfurization with immobilized strains, and 44% for DBT and 66% for DBTS desulfurization by nanoparticle-coated strains. CONCLUSIONS: Nanoparticle-coated and immobilized cells may be of use in efforts to increase the efficiency of biodesulfurization. SIGNIFICANCE AND IMPACT OF THE STUDY: Alginate immobilization or nanoparticle coating of bacterial cells may be useful approaches for the enhancement of biodesulfurization for eventual use on an industrial scale.

Kinetics and thermodynamics of organo-sulfur-compound desorption from saturated neutral activated alumina.

Desulfurization of liquid fuels mitigates the amount of noxious sulfur oxides and particulates released during fuel combustion. Existing literature on oxidative-adsorptive desulfurization technologies focus on sulfur-in-fuel removal by various materials, but very little information is presented about their desorption kinetics and thermodynamics. Herein, we report for the first time, the mechanism of sulfur desorption from neutral activated alumina saturated with dibenzothiophene sulfone. Batch experiments were conducted to examine the effects of agitation rate, desorption temperature, sulfur content, and eluent type on sulfur desorption efficiencies. Results show enhanced desorption capacities at higher agitation rate, desorption temperature, and initial sulfur content. Desorption efficiency and capacity of acetone were found to be remarkably superior to ethanol, acetone:ethanol (1:1), and acetone:isopropanol (1:1). Desorption kinetics reveal excellent fit of the nonlinear pseudo-second-order equation on desorption data, indicating chemisorption as the rate-determining step. Results of the thermodynamics study show the spontaneous (ΔG° ≤ -2.08 kJ mol-1) and endothermic (ΔH° = 32.35 kJ mol-1) nature of sulfur desorption using acetone as eluent. Maximum regeneration efficiency was attained at 93% after washing the spent adsorbent with acetone followed by oven-drying. Scanning electron microscopy, Fourier transform infrared, and X-ray diffraction spectroscopy analyses reveal the intact and undamaged structure of neutral activated alumina even after adsorbent regeneration. Overall, the present work demonstrates the viability of neutral activated alumina as an efficient and reusable adsorbent for the removal of sulfur compounds from liquid fossil fuels.

Development of molecular driven screening for desulfurizing microorganisms targeting the dszB desulfinase gene.

COnsensus DEgenerate Hybrid Oligonucleotide Primers (CODEHOP) were developed for the detection of the dszB desulfinase gene (2'-hydroxybiphenyl-2-sulfinate desulfinase; EC 3.13.1.3) by polymerase chain reaction (PCR), which allow to reveal larger diversity than traditional primers. The new developed primers were used as molecular monitoring tool to drive a procedure for the isolation of desulfurizing microorganisms. The primers revealed a large dszB gene diversity in environmental samples, particularly in diesel-contaminated soil that served as inoculum for enrichment cultures. The isolation procedure using the dibenzothiophene sulfone (DBTO2) as sole sulfur source reduced drastically the dszB gene diversity. A dszB gene closely related to that carried by Gordonia species was selected. The desulfurization activity was confirmed by the production of desulfurized 2-hydroxybiphenyl (2-HBP). Metagenomic 16S rRNA gene sequencing showed that the Gordonia genus was represented at low abundance in the initial bacterial community. Such observation highlighted that the culture medium and conditions represent the bottleneck for isolating novel desulfurizing microorganisms. The new developed primers constitute useful tool for the development of appropriate cultural-dependent procedures, including medium and culture conditions, to access novel desulfurizing microorganisms useful for the petroleum industry.

Spectral-Luminescent and Electroluminescent Properties of Charge-transfer Systems Based On Electron-donating Diphenylamine Derivatives and Acceptors of Dibenzothiophene Sulfone and Phenanthridine.

Spectral characteristics and luminescence under the photo- and electro-excitation of substituted dibenzthiophene sulfone and phenanthridine were studied in this paper. Diphenylamines are substituents introduced in the 2nd and 7th positions (linear configuration) or the 3rd and 6th positions (angular configuration) of dibenzthiophene sulfone or phenanthridine. All molecules show delayed fluorescence, both in solutions and films produced by thermal vacuum deposition. The value of the energy gap between the S1 and T1 states has been estimated and is shown to depend not only on the spatial arrangement of the fragments among themselves (linear or angular), but also on the nature of the substituent in diphenylamine. The highest electroluminescence brightness was found for the molecules, in which triplet levels are involved, both through the process of triplet-triplet annihilation and through thermally activated delayed fluorescence.

Combining co-culturing of Paenibacillus strains and Vitreoscilla hemoglobin expression as a strategy to improve biodesulfurization.

Enhancement of the desulfurization activities of Paenibacillus strains 32O-W and 32O-Y were investigated using dibenzothiophene (DBT) and DBT sulfone (DBTS) as sources of sulphur in growth experiments. Strains 32O-W, 32O-Y and their co-culture (32O-W plus 32O-Y), and Vitreoscilla hemoglobin (VHb) expressing recombinant strain 32O-Yvgb and its co-culture with strain 32O-W were grown at varying concentrations (0·1-2 mmol l-1 ) of DBT or DBTS for 96 h, and desulfurization measured by production of 2-hydroxybiphenyl (2-HBP) and disappearance of DBT or DBTS. Of the four cultures grown with DBT as sulphur source, the best growth occurred for the 32O-Yvgb plus 32O-W co-culture at 0·1 and 0·5 mmol l-1 DBT. Although the presence of vgb provided no consistent advantage regarding growth on DBTS, strain 32O-W, as predicted by previous work, was shown to contain a partial 4S desulfurization pathway allowing it to metabolize this 4S pathway intermediate.

PET-modified red mud as catalysts for oxidative desulfurization reactions.

This work describes the synthesis of catalysts based on red mud/polyethylene terephthalate (PET) composites and their subsequent heat treatment under N2 atmosphere. The materials were characterized by scanning electron microscopy (SEM), temperature programmed reduction (TPR), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric (TG) analysis and N2 adsorption/desorption. The catalysts were evaluated in the oxidative desulfurization reaction of dibenzothiophene (DBT) in a biphasic system. The results indicated that the PET impregnation on red mud increased the affinity of the catalyst with the nonpolar phase (fuel), in which the contaminant was dissolved, allowing a higher conversion (up to 80%) and selectivity to the corresponding dibenzothiophene sulfone. The sulfone compound is more polar than DBT and diffused into the polar solvent as indicated by the data obtained via gas chromatography-mass spectrometry (GC-MS).