Degradation of furfural (2- furaldehyde) to methane and carbon dioxide by an anaerobic consortium

Furfural, a byproduct formed during the thermal/chemical pre-treatment of hemicellulosic biomass, was degraded to methane and carbon dioxide under anaerobic conditions. The consortium of anaerobic microbes responsible for the degradation was enriched using small continuously stirred tank reactor (CSTR) systems with daily batch feeding of biomass pretreatment liquor and continuous addition of furfural. Although the continuous infusion of furfural was initially inhibitory to the anaerobic CSTR system, adaptation of the consortium occurred rapidly with high rates of furfural addition. Addition rates of 7.35 mg furfural/700-mL reactor/d resulted in biogas productions of 375%, of that produced in control CSTR systems, fed the biomass pretreatment liquor only. The anaerobic CSTR system fed high levels of furfural was stable, with a sludge pH of 7.1 and methane gas composition of 69%, compared to the control CSTR, which had a pH of 7.2 and 77% methane. CSTR systems in which furfural was continuously added resulted in 80% of the theoretically expected biogas. Intermediates in the anaerobic biodegradation of furfural were determined by spike additions in serum-bottle assays using the enriched consortium from the CSTR systems. Furfural was converted to several intermediates, including furfuryl alcohol, furoic acid, and acetic acid, before final conversion to methane and carbon dioxide.     

Reductive dechlorination of tetrachloroethylene (PCE) catalyzed by cyanocobalamin

A biomimetic system has been developed for the reductive dechlorination of tetrachloroethylene (PCE). PCE was dechlorinated to trichloroethylene (TCE) and 1,2-dichloroethylene (DCE) in the presence of dithiothreitol or Ti (III) citrate and catalytic amounts of cyanocobalamin in both homogeneous reaction mixtures and packed bed reactor systems. In packed bed reactors with Ti (III) citrate as the reductant, PCE (0.18 mM) conversion averaged 55% at residence times of 1.75 and 3.5 h. The product distribution was 94% TCE and 6% DCE at the lower residence time. DCE formation increased to 45% at the higher residence time. No reduction of PCE was observed in the absence of cyanocobalamin. This system may be useful as a means of pretreatment of halogenated aliphatic hydrocarbons in advance of biological treatment.     

Kinetics and mechanism of methylthiomethyl acetate conversion into bis(methylthio)methane

Methylthiomethyl acetate can be rapidly and quantitatively converted into bis(methylthio)methane via an acid-catalyzed reaction under mild conditions. This conversion in the system benzene-aqueous sulfuric acid is interpreted in terms of a complex scheme of consecutive and parallel steps. It begins with the hydrolysis of the ester by the mechanisms A _AC2 and A _AL1 (in Ingold’s terminology), and the subsequent interactions involve intermediate products. The kinetics of the process is analyzed. A procedure for the synthesis of bis(methylthio)methane from dimethyl sulfoxide is suggested.     

Effect of diluents on poly(vinyl acetate) dynamics

The effect of diluents and temperature on segmental motion in poly(vinyl acetate) was investigated by both NMR and ESR spectroscopy. Three classes of diluents were studied: chloroform, a thermodynamically good solvent; water, a poor solvent which slightly swells the polymer and lowers its glass transition temperature; and decane, a nonsolvent so poor it does not appear to swell the polymer nor lower the calorimetric glass transition temperature. At all temperatures investigated each type of diluent increased the segmental motion of the polymer over that of the bulk sample. Under the conditions studied, ¹³C and ²H NMR and nitroxide spin-label ESR data gave similar views of segmental motion of the polymer, indicating that in this amorphous polymer the segmental motion of the polymer may be safely inferred from spin-label data.     

Effect of myricetin on deoxycorticosterone acetate (DOCA)-salt-hypertensive rats

Chronic administration of myricetin (100 and 300?mg?kg?1, p.o., for 4 weeks) isolated from Vitis vinifera (Vitaceae) ameliorated hypertension and oxidative stress induced by deoxycorticosterone acetate (DOCA)-salt in rats. Myricetin treatment reduced systolic blood pressure, vascular reactivity changes and reversed the DOCA-induced increase in heart rate. Urinary sodium excretion was significantly decreased in animals treated with myricetin compared to the DOCA group when measured by flame photometer. The cumulative concentration response curve of serotonin (5-HT) and angiotensin II (Ang II) were shifted towards the right in rats treated with myricetin using the isolated rat fundus strip and ascending colon, respectively. Increased levels of thiobarbituric acid reactive substances and decreased levels of superoxide dismutase, catalase and reduced glutathione in the heart tissue were observed in animals treated with DOCA, which were reversed by myricetin. Thus, myricetin shows antihypertensive and antioxidant properties in the DOCA model of hypertension.     

引发剂对聚醋酸乙烯酯微乳液聚合的影响

考察了3种引发体系[过硫酸铵一碳酸氢钠(Ⅰ1),偶氮二异丁腈(Ⅰ2),过氧化氢-抗坏血酸(Ⅰ3)]对聚醋酸乙烯酯微乳液聚合的影响.结果表明:Ⅰ2使微乳液聚合体系反应剧烈;Ⅰ3反应较为平稳;Ⅰ1的表现中等.Ⅰ1～Ⅰ3所制得的乳液分子量出现典型的双峰分布.在高分子量部分,Ⅰ3对应的聚合物分子量较高;在低分子量部分,Ⅰ1～ⅠI3差别不大;Ⅰ2对应的乳胶粒径较小,分布也较窄;Ⅰ3次之;Ⅰ1对应的乳胶粒径较大,分布也较宽.     

Extraction of uranium(VI) by bis(hexylsulfinyl)methane

The extraction of uranium(VI) with bis(hexylsulfinyl)methane (BHxSM) from nitric acid aqueous solution has been investigated. It was found that the extraction increased with increasing nitric acid concentration up 8.5 mol/l and then decreased. Extraction distribution ratio also increased with the bis(hexylsulfinyl)methane concentration. The extraction species appear to be UO₂(NO₃)₂ ^.2BHxSM. The influences of temperature, salting-out concentration and oxalate concentration on the extraction equilibrium were also investigated, and the enthalpy of the extraction reaction was obtained. The result shows that the reaction of uranium(VI) extraction with BHxSM is an exothermic one.     

Amelioration of methane yield in cheese whey fermentation by controlling the pH of the methanogenic stage

A two-stage, no-mix anaerobic digester of 145 L capacity was used to investigate the effect of controlling the pH of the methanogenic stage on the biogas production and the pollution potential reduction of acid cheese whey. The digester was operated at a 15-d hydraulic retention time, and a temperature of 35°C. Controlling the pH of the methanogenic stage increased the biogas production rate and methane yield by 77.77 and 289.00%, respectively. Reductions of up to 32.19, 44.44, and 35.86% in the COD, solids and nitrogen were achieved.     

Effect of organic load on the performance and methane production of an AnSBBR treating effluent from biodiesel production

Currently, there is an increasing demand for the production of biodiesel and, consequently, there will be an increasing need to treat wastewaters resulting from the production process of this biofuel. The main objective of this work was, therefore, to investigate the effect of applied volumetric organic load (AVOL) on the efficiency, stability, and methane production of an anaerobic sequencing batch biofilm reactor applied to the treatment of effluent from biodiesel production. As inert support, polyurethane foam cubes were used in the reactor and mixing was accomplished by recirculating the liquid phase. Increase in AVOL resulted in a drop in organic matter removal efficiency and increase in total volatile acids in the effluent. AVOLs of 1.5, 3.0, 4.5 and 6.0 g COD L⁻¹ day⁻¹ resulted in removal efficiencies of 92%, 81%, 67%, and 50%, for effluent filtered samples, and 91%, 80%, 63%, and 47%, for non-filtered samples, respectively, whereas total volatile acids concentrations in the effluent amounted to 42, 145, 386 and 729 mg HAc L⁻¹, respectively. Moreover, on increasing AVOL from 1.5 to 4.5 g COD L⁻¹ day⁻¹ methane production increased from 29.5 to 55.5 N mL CH₄ g COD⁻¹. However, this production dropped to 36.0 N mL CH₄ g COD⁻¹ when AVOL was increased to 6.0 g COD L⁻¹ day⁻¹, likely due to the higher concentration of volatile acids in the reactor. Despite the higher concentration of volatile acids at the highest AVOL, alkalinity supplementation to the influent, in the form of sodium bicarbonate, at a ratio of 0.5–1.3 g NaHCO₃ g COD_fed⁻¹, was sufficient to maintain the pH near neutral and guarantee process stability during reactor operation.     

Effect of pressure on the production of hydrogen and nanofilamentous carbon by the catalytic pyrolysis of methane on Ni-containing catalysts

An experimental study of the production of hydrogen and nanofilamentous carbon (NFC) by methane pyrolysis on Ni- and Ni + Cu-containing catalysts at 675°C and pressures of up to 5 atm is reported. As the pressure and the copper content of the catalyst are increased, the stable service life of the catalyst and the hydrogen and NFC yield per unit weight of the catalyst, as well as the specific surface area and micropore volume of the resulting NFC, increase markedly.     

Vinyl acetate formation by the reaction of ethylene with acetate species on oxygen-covered Pd(111)

The reaction pathway of vinyl acetate synthesis is scrutinized by reacting gas-phase ethylene (at an effective pressure of 1 x 10-4 Torr) with eta2-acetate species (with a coverage of 0.31 +/- 0.02 monolayer) on a Pd(111)-O(2x2) model catalyst surface in ultrahigh vacuum. It is found that the 1414 cm-1 infrared feature due to the symmetric OCO stretching mode of the acetate species decreases in intensity due to reaction with gas-phase ethylene, while temperature-programmed desorption experiments demonstrate that vinyl acetate is formed. The formation of ethylidyne species is detected when almost all of the acetate species have been removed. The experimental removal kinetics are reproduced by a model in which adsorbed acetates react with an ethylene-derived (possibly ethylene or vinyl) species, where ethylene adsorption is blocked by the acetate present on the surface.     

Kinetics of uranium(VI) extraction by bis(octylsulfinyl)methane

The kinetics and mechanism of uranium(VI) extraction from nitric acid solution by bis(octylsulfinyl)methane (BOSM) are studied with the method of stationary interface cell. The effects of temperature, extractant and nitric acid concentrations are discussed. The results showed that the extraction process is controlled by the following reaction: UO₂(NO₃)₂ + BOSM_(i)⇄_k1 ^k-1UO₂(NO₃)₂BOSM_(i). The variation of enthalpy associated with the extraction is -22.1±2.1 kJ/mol. This revised version was published online in July 2006 with corrections to the Cover Date.     

Metallation of tris(1-pyrazolyl)methane by dimethylplatinum(II)

Tris(1-pyrazolyl)methane (HCpz₃) reacts with Pt(CH₃)₂(COD) to form Pt(CH₃)₂(HCpz₃), and when this complex is heated in pyridine metallation of the pyrazole ring at C(5) occurs to form Pt(CH₃)(HCpz₂(pzH_₁))(py). A triphenylphosphine derivative, Pt(CH₃)(HCpz₂(pzH_₁))(PPh₃)₂, when slowly heated to 185°C forms Pt(HCpz₂(pzH_₁))(C₆H₄PPh₂); this complex has both the nitrogen and phosphorus donor ligands metallated to form six and four-membered rings, respectively.     

Synthesis of Poly(vinyl acetate)-block-poly(dimethylsiloxane)-block-poly(vinyl acetate) Copolymers by Iodine Transfer Photopolymerization in Miniemulsion

Summary: Iodine transfer polymerization of vinyl acetate in aqueous miniemulsion, initiated by UV radiation in the presence of an α,ω-diiodo-poly(dimethylsiloxane) macrophotoiniferter has been performed. The formation of a triblock copolymer latex PVAc-b-PDMS-b-PVAc has been evidenced by ¹H-NMR and size exclusion chromatography. The size of the PDMS and PVAc blocks were modulated thus opening the way to a wide range of copolymers with different properties. A detailed study of the reaction mechanism showed the importance of the aqueous dispersed medium to achieve a controlled polymerization.     

Effect of polyethyleneglycol (PEG) on gas permeabilities and permselectivities in its cellulose acetate (CA) blend membranes

The effect of polyethyleneglycol (PEG) on gas permeabilities and selectivities was investigated in a series of miscible cellulose acetate (CA) blend membranes. The permeabilities of CO₂, H₂, O₂, CH₄, N₂ were measured at temperatures from 30 to 80°C and pressures from 20 to 76 cmHg using a manometric permeation apparatus. It was determined that the blend membrane having 10 wt% PEG20000 exhibited higher permeability for CO₂ and higher permselectivity for CO₂ over N₂ and CH₄ than those of the membranes which contained 10% PEG of the molecular weight in the range 200–6000. The CA blend containing 60 wt% PEG20000 showed that its permeability coefficients of CO₂ and ideal separation factors for CO₂ over N₂ reached above 2 × 10⁻⁸ [cm³ (STP) cm/cm² s cmHg] and 22, respectively, at 70°C and 20 cmHg. Based on the data of gas permeability coefficients, time lags and characterization of the membranes, it is proposed that the apparent solubility coefficients of all CA and PEG blend membranes for CO₂ were lower than those of the CA membrane. However, almost all the blend membranes containing PEG20000 showed higher apparent diffusivity coefficients for CO₂, resulting in higher permeability coefficients of CO₂ with relation to those of the CA membrane. It is attributed to the high diffusivity selectivities of CA and PEG20000 blend membranes that their ideal separation factors for CO₂ over N₂ were higher than those of the CA membrane in the range 50–80°C, even though the ideal separation factors of almost all PEG blend membranes for CO₂ over CH₄ became lower than those of the CA membrane over nearly the full range from 30° to 80°C.     

Trimethylstannyl (diphenylphosphino)acetate: a source of (diphenylphosphino)acetate ligand in the synthesis of coordination compounds

Trimethylstannyl (diphenylphosphino)acetate (1), which is readily accessible from potassium (diphenylphosphino)acetate and trimethylstannyl chloride, may serve as the source of (diphenylphosphino)acetate anion in the preparation of coordination compounds. Thus, the reactions between [M(cod)Cl₂] (M = Pd and Pt; cod = η²:η²-cycloocta-1,5-diene) and two equivalents of 1 give [M(Ph₂PCH₂CO₂-κ²O,P)₂] (2 and 3), while the reaction of [{Pd(μ-Cl)Cl(PFur₃)}₂] (4; Fur = 2-furyl) with one equivalent of 1 yields [SP-4-3]-[PdCl(Ph₂PCH₂CO₂-κ²O,P)(PFur₃)] (5). The reactions of 1 with the dimers [{Rh(η⁵-C₅Me₅)Cl(μ-Cl)}₂] and [{Ru(η⁶-1,4-MeC₆H₄(CHMe₂))Cl(μ-Cl)}₂] (at 1-to-metal ratio 1:1) produce O,P-chelated complexes as well, albeit as stable adducts with the liberated Me₃SnCl: [RhCl(η⁵-C₅Me₅)(Ph₂PCH₂CO₂-κ²O,P)] · Me₃SnCl (6) and[RuCl(η⁶-1,4-MeC₆H₄(CHMe₂))(Ph₂PCH₂CO₂-κ²O,P)] · Me₃SnCl (8). The related complexes with P-monodentate (diphenylphosphino)acetic acid, [RhCl₂(η⁵-C₅Me₅)(Ph₂PCH₂CO₂H-κ,P)] (7) and [RuCl₂(η⁶-1,4-MeC₆H₄(CHMe₂))(Ph₂PCH₂CO₂H-κP)] (9), were obtained by bridge splitting in the dimers with the phosphinocarboxylic ligand. All new compounds were characterized by spectral methods and combustion analyses, and the structures of 2 · 3CH₂Cl₂, 3, 4, 5, 6 and 8 were determined by X-ray crystallography.     

Synthesis and performance of a Mono (dodecafluoroheptyl) acetate surfactant

A novel fluorinated surfactant, sodium 1?H, 1?H, 7H-dodecafluoro-1-heptyloxy acetate (DFHAS), was synthesized via a facile two-step synthetic procedure. The structure of product on each step was characterized by ^1?H NMR, ^19?F NMR, ¹³C NMR, FT-IR, and mass spectrum (MS). Ultraviolet absorption (UV) and ring measurements were performed to obtain detailed information of its surface properties. The results demonstrated that the novel surfactant possessed very low critical micelle concentration (CMC, 7.94?mM) and surface tension (20.01?mN/m). Furthermore, the surfactant had preferable thermal stability compared with other perfluorocarboxylates characterized by thermal gravimetric analysis (TGA). The practical application performance of DFHAS was finally validated through the emulsion polymerization of vinylidene fluoride (VDF) by means of its excellent emulsifying activities. It is expected that this versatile synthetic strategy may help fabricate satisfying green surfactant systems for the application in fields of emulsion polymerization, drug delivery and greases.GRAPHICAL ABSTRACT     

Formation of C=C and Si-Cl adstructures by insertion reactions of cis-dichloroethylene and perchloroethylene on Si(100)2 x 1

The room-temperature adsorption and thermal evolution of cis-dichloroethylene (DCE) and perchloroethylene (PCE) on Si(100)2 x 1 have been studied by X-ray photoelectron spectroscopy and temperature programmed desorption (TPD) mass spectrometry. Unlike ethylene that is found to adsorb on Si(100)2 x 1 through a [2+2] cycloaddition reaction, cis-DCE and PCE appear to dechlorinate upon adsorption on the 2 x 1 surface through an insertion reaction preserving the C=C bond. Our C 1s XPS spectra are consistent with the existence of mono-sigma-bonded and di-sigma bonded dechlorinated adstructures for both cis-DCE and PCE. The presence of the XPS C 1s feature at 283.9 eV, characteristic of the (=C<(Si)(Si)) component, supports the formation of a unique tetra-sigma-bonded C(2) dimer (i.e., by full dechlorination) for PCE, which is found to be stable to 800 K. In marked contrast to PCE for which no organic desorption fragments are observed, m/z 26 TPD features at 590 and 750 K have been observed for cis-DCE. These features could be attributed to the formation of acetylene resulting from Cl beta-elimination of 2-chlorovinyl adspecies and to direct desorption of vinylene, respectively. Further annealing the cis-DCE and PCE samples to above 800 K produces SiC and/or carbon clusters. The TPD data also show HCl evolution over 810-850 K for both cis-DCE and PCE, the latter of which also exhibits an additional SiCl(2) evolution above 850 K. The present work illustrates that the insertion mechanism could be quite common in the surface chemistry of chlorinated ethylenes on the 2 x 1 surface.