Sequential spectrofluorimetric determination of free and total glycerol in biodiesel in a multicommuted flow system

A new procedure for spectrofluorimetric determination of free and total glycerol in biodiesel samples is presented. It is based on the oxidation of glycerol by periodate, forming formaldehyde, which reacts with acetylacetone, producing the luminescent 3,5-diacetyl-1,4-dihydrolutidine. A flow system with solenoid micro-pumps is proposed for solution handling. Free glycerol was extracted off-line from biodiesel samples with water, and total glycerol was converted to free glycerol by saponification with sodium ethylate under sonication. For free glycerol, a linear response was observed from 5 to 70 mg L⁻¹ with a detection limit of 0.5 mg L⁻¹, which corresponds to 2 mg kg⁻¹ in biodiesel. The coefficient of variation was 0.9% (20 mg L⁻¹, n = 10). For total glycerol, samples were diluted on-line, and the linear response range was 25 to 300 mg L⁻¹. The detection limit was 1.4 mg L⁻¹ (2.8 mg kg⁻¹ in biodiesel) with a coefficient of variation of 1.4% (200 mg L⁻¹, n = 10). The sampling rate was ca. 35 samples h⁻¹ and the procedure was applied to determination of free and total glycerol in biodiesel samples from soybean, cottonseed, and castor beans.     

Evaluation of gamma irradiation effect on physico-chemical properties of a mixed beverage based in soy milk and grape juice

The effects of the main operation variables on the electrochemical oxidation of simulated tributyl phosphate (TBP) waste by a boron-doped diamond anode are individually studied. The optimum operating conditions are obtained as follows: 4 g L^?1 initial TBP concentration, 180 min degradation time, 40 mA cm^?2 current density, 0.5 mol L^?1 Na₂SO₄ as the supporting electrolyte, and unadjusted pH of the aqueous phase. Under such conditions, a chemical oxygen demand (COD) removal ratio of 82.3% is achieved, and the energy consumption is 26.16 kWh m^?3. A degradation mechanism of TBP is tentatively proposed.     

Applicability of Microaerobic Technology to Enhance BTEX Removal from Contaminated Waters

As the addition of low concentrations of oxygen can favor the initial degradation of benzene, toluene, ethylbenzene, and xylenes (BTEX) compounds, this work verified the applicability of the microaerobic technology to enhance BTEX removal in an anaerobic bioreactor supplemented with high and low co-substrate (ethanol) concentrations. Additionally, structural alterations on the bioreactor microbiota were assessed throughout the experiment. The bioreactor was fed with a synthetic BTEX-contaminated water (~ 3 mg L^?1 of each compound) and operated at a hydraulic retention time of 48 h. The addition of low concentrations of oxygen (1.0 mL min^?1 of atmospheric air at 27 °C and 1 atm) assured high removal efficiencies (> 80%) for all compounds under microaerobic conditions. In fact, the applicability of this technology showed to be viable to enhance BTEX removal from contaminated waters, especially concerning benzene (with a 30% removal increase), which is a very recalcitrant compound under anaerobic conditions. However, high concentrations of ethanol adversely affected BTEX removal, especially benzene, under anaerobic and microaerobic conditions. Finally, although bacterial community richness decreased at low concentrations of ethanol, in general, the bioreactor microbiota could deal with the different operational conditions and preserved its functionality during the whole experiment.     

Olefin Cyclopropanation by Radical Carbene Transfer Reactions Promoted by Cobalt(II)/Porphyrinates: Active‐Metal‐Template Synthesis of [2]Rotaxanes

A Co^II/porphyrinate‐based macrocycle in the presence of a 3,5‐diphenylpyridine axial ligand functions as an endotopic ligand to direct the assembly of [2]rotaxanes from diazo and styrene half‐threads, by radical‐carbene‐transfer reactions, in excellent 95 % yield. The method reported herein applies the active‐metal‐template strategy to include radical‐type activation of ligands by the metal‐template ion during the organometallic process which ultimately yields the mechanical bond. A careful quantitative analysis of the product distribution afforded from the rotaxane self‐assembly reaction shows that the Co^II/porphyrinate subunit is still active after formation of the mechanical bond and, upon coordination of an additional diazo half‐thread derivative, promotes a novel intercomponent C?H insertion reaction to yield a new rotaxane‐like species. This unexpected intercomponent C?H insertion illustrates the distinct reactivity brought to the Co^II/porphyrinate catalyst by the mechanical bond.     

(MeLi)4(dem)1.5]infinity] and [(thf)3Li3M3[(NtBu)3S--how to reduce aggregation of parent methyllithium

Organolithium compounds play the leading role among the organometallic reagents in synthesis and in industrial processes. Up to date industrial application of methyllithium is limited because it is only soluble in diethyl ether, which amplifies various hazards in large-scale processes. However, most reactions require polar solvents like diethyl ether or THF to disassemble parent organolithium oligomers. If classical bidentate donor solvents like TMEDA (TMEDA= N,N,N',N'tetramethyl-1,2-ethanediamine) or DME (DME=1,2-dimethoxyethane) are added to methyllithium, tetrameric units are linked to form polymeric arrays that suffer from reduced reactivity and/or solubility. In this paper we present two different approaches to tune methyllithium aggregation. In [[(MeLi)4(dem)1,5)infinity] (1; DEM = EtOCH2OEt, diethoxymethane) a polymeric architecture is maintained that forms microporous soluble aggregates as a result of the rigid bite of the methylene-bridged bidentate donor base DEM. Wide channels of 720 pm in diameter in the structure maintain full solubility as they are coated with lipophilic ethyl groups and filled with solvent. In compound 1 the long-range Li3CH3...Li interactions found in solid [[(MeLi)4]infinity] are maintained. A different approach was successful in the disassembly of the tetrameric architecture of [((MeLi)4]infinity]. In the reaction of dilithium triazasulfite both the parent [(MeLi)4] tetramer and the [[Li2[(NtBu)3S]]2] dimer disintegrate and recombine to give an MeLi monomer stabilized in the adduct complex [(thf)3Li3Me-[(NtBu)3S]] (2). One side of the Li3 triangle, often found in organolithium chemistry, is shielded by the tripodal triazasulfite, while the other face is mu3-capped by the methanide anion. This Li3 structural motif is also present in organolithium tetramers and hexamers. All single-crystal structures have been confirmed through solid-state NMR experiments to be the same as in the bulk powder material.