Acid/base and hydrogen bonding effects on the proton-coupled electron transfer of quinones and hydroquinones in acetonitrile: Mechanistic investigation by voltammetry, H NMR and computation

This report seeks to address the role of hydrogen bonding with Brønsted acids and bases in proton-coupled electron transfer (PCET) as it pertains to concerted or stepwise pathways of quinone (Q) and hydroquinone (QH₂) electrochemistry. This study was performed using a series of techniques that included cyclic voltammetry (CV), digital simulations, computational chemistry and ¹H NMR. Hydrogen bonding was inferred by a decrease in diffusion coefficient (D) values measured using a pulsed gradient echo- (PGE-) ¹H NMR technique. Changes of 40.8% and 37.9% in D values were only noted after the addition of two equivalents of acetate to 1,4-hydroquinone (1,4-QH₂) and catechol (1,2-QH₂), respectively. In contrast, the D values for the addition of selected amines (pyridine, N,N-diisopropylethylamine and triethylamine) changed only 3.2% on average. Quantum mechanical calculations were conducted to determine the pK_a of all quinoid species to serve as a starting point for the determination of equilibrium constants in voltammetric simulations. Simulations indicate that 1,4-benzoquinone undergoes stepwise electron-proton transfer upon addition of acetic acid, N-ethyldiisopropylammonium perchlorate and pyridinium nitrate and were simulated without the presence of hydrogen bonds. The QH₂ compounds show stepwise proton-electron transfers after addition of the both the conjugate amines and acetate.     

DIMENSIONLESS CORRELATION FOR THE HEAT TRANSFER COEFFICIENT IN A BATCH-INDIRECT ROTARY DRIER

A batch-indirect rotary drier heated with steam was experimentally operated to obtain data of moisture content and temperature versus time for soy meal and fish meal. Operation conditions were as follow: steam pressure (1 to 4 bar), rotation speed (3.7 to 11.6 r.p.m.) and rate of vapor extraction (0.059 to 0.256 m/s).

From experimental data the effective heat transfer coefficient between the hot surface and the bed of solids was determined. These data were correlated by means of dimensional analysis as a function of the drying process variables. The equation obtained for the effective Nusselt number predicts adequately the effective heat transfer coefficient, for both substrates, in the range of the operating variables studied.     

A two-channel microfluidic sensor that uses anodic electrogenerated chemiluminescence as a photonic reporter of cathodic redox reactions

This paper describes a new approach for sensing electrochemically active substrates in microfluidic systems. This two-electrode sensor relies on electrochemical detection at one electrode and electrogenerated chemiluminescent (ECL) reporting at the other. Each microfabricated indium tin oxide electrode is located in a separate microfluidic channel, but the channels are connected downstream of the electrodes to maintain a complete electrical circuit. Because of laminar flow, there is no bulk mixing of the fluids in the detecting and reporting channels. This approach allows the ECL reaction to be physically and chemically decoupled from the sensing channel of the device, which greatly expands the number of analytes that can be detected. However, because the cathode and anode are connected, electron-transfer processes occurring at the sensing electrode are electrically coupled to the ECL reaction. Charge balance permits the ECL light output to be quantitatively correlated to electrochemical reductions at the cathode. The system is used to detect Fe(CN)6(3-), Ru(NH3)6(3+), and benzyl viologen and report their presence via Ru(bpy)3(2+) (bpy = bipyridine) luminescence. Each different redox target initiates ECL at a unique potential bias related to its standard redox potential. The influence of the concentrations of Ru(bpy)3(2+) and the target analytes is discussed.     

Effect of decortication and protease treatment on the kinetics of liquefaction,saccharification, and ethanol production from sorghum

BACKGROUND: This study analyzes the effect of decortication and protease treatment on the kinetics of liquefaction, saccharification and ethanol production from sorghum kernels. In general, bioethanol yields from sorghum are lower than those from maize. This has been attributed to reduced access of starch‐degrading enzymes due to the crosslinked protein net in the sorghum kernels. RESULTS: Liquefaction is described as a zero order kinetics process, with reaction rates enhanced by protease treatment. The use of protease almost doubled the liquefaction rate in both whole and decorticated sorghum, compared with untreated kernels. During saccharification of decorticated sorghum, protease treatment significantly affected the glucose/starch yield and the glucose concentration profile over time. When compared with maize, protease treatment of decorticated sorghum resulted in superior ethanol production rates. Specific ethanol yields during fermentation were statistically comparable with those for maize. CONCLUSION: Protease treatment of decorticated sorghum kernels can impart substantial economic benefits in terms of improvement of bioethanol yield (13% over whole sorghum) and in reduced fermentation time (approximately 50% with respect to maize). Copyright © 2010 Society of Chemical Industry     

Perovskite-type oxides in methane dry reforming: Effect of their incorporation into a mesoporous SBA-15 silica-host

A series of Ni-based perovskite-type oxides LaNiO₃, La_0.8Ca_0.2NiO₃ and La_0.8Ca_0.2Ni_0.6Co_0.4O₃, were synthesized as catalyst precursors both bulk and built-in a highly ordered mesoporous SBA-15 silica-host with the aim of using them as heterogeneous catalysts in syngas production by the methane dry reforming with CO₂. The solids were characterized by means of FT-IR, XRD, BET surface area and TPR techniques. All synthesized oxides showed a perovskite-type structure. Incorporation of the oxides into the mesoporous silica-host generates a higher metal–support interaction increasing the Ni reduction temperature. A decrease in CH₄ and CO₂ conversion was observed when a second cation in A- and/or B-site was added to the bulk perovskite. The built-in of these solids in the SBA-15 mesoporous silica-host allows working at lower temperature with an increase in conversions and selectivity towards syngas which represent an attractive perspective for industrial application.     

Biguanide-, imine-, and guanidine-based networks as catalysts for transesterification of vegetable oil

Polycationic systems based on poly(hexamethylene biguanide) (PHMBG), branched polyethyleneimine (PEI) and poly(N-vinylguanidine) (PVG) have been evaluated as heterogeneous catalysts for the transesterification of sunflower oil by methanol. Insoluble networks are synthesized via cross-linking of PHMBG by either 4,4′-methylenebis(N,N-diglycidylaniline) or polyisocyanate prepolymer, PEI with sebacoyl chloride, and PVG with 1,4-butanediol diglycidyl ether. PHMBG and its cross-linked networks appeared to be remarkably efficient catalysts, enabling 80–100% triglyceride conversion within 0.5 h at 70 °C. PEI-based networks catalyzed triglyceride transesterification with rates 8- to 12-fold slower than their PHMBG-based counterparts. The PVG-based networks, which were devoid of hydrophobic moieties, appeared to be inefficient catalysts due to limited accessibility of the basic guanidine groups to reactants. The PHMBG networks were shown to be recyclable by a simple centrifugal filtration. After 15 cycles of recovery and reuse, only 10–15% decline in performance was observed.     

Enhancement of immune response in mice fed with Streptococcus thermophilus and Lactobacillus acidophilus

Swiss mice, fed for 8 consecutive d with 50 micrograms/d of viable cultures of Lactobacillus acidophilus and Streptococcus thermophilus, showed significant variation in their immune system. In order to study this phenomenon assays for macrophage and lymphocyte function were carried out. Both lactic acid bacteria enhanced significantly the enzymatic and phagocytic activity of peritoneal macrophages as checked against the controls and also accelerated the phagocytic function of the reticuloendothelial system as revealed by the carbon clearance test. On the 2nd d (100 micrograms), L. acidophilus reached a peak of K = .271, which remained high. Streptococcus thermophilus was effective only on the 2nd d and then decreased. The lymphocytic activity studied by immunoglobulin secreting cells was assayed by Jerne's method of plaque-forming cells (PFC). This activity also was increased by the two microorganisms. Streptococcus thermophilus proved more effective than L. acidophilus. Lactobacillus acidophilus and S. thermophilus activated macrophages and lymphocytes and produced the same increase in the immune response of mice whether administered orally or intraperitoneally.