首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 46 毫秒
1.
Value for the activation energy, U act, and the entropy change, S, for the reaction 2Li + S2O 4 2– Li2S2O4+2e in acetonitrile have been found to be 72 kJ mol–11 and — 0.3 kJ mol–1 K–1, respectively, by a combination of impedance techniques and the use of a temperature-controlled environment on commercially manufactured cells which acted as constant volume containers.  相似文献   

2.
The electrochemical oxidation of dimethyl disulfide was investigated in acetonitrile and dichloromethane. The nature of the oxidation strongly depends on the nucleophilicity of the solvent. In acetonitrile a one-electron oxidation is observed and the consecutive species did not exhibit any reactivity towards aromatic compounds subject to electrophile substitution. On the contrary, the oxidation of dimethyl disulfide in methylene chloride afforded a two-electron process with the formation of a species consistent with CH3S+. Its reactivity towards phenols and aromatic ethers was confirmed and showed a selective monomethylsulfanylation in most of the cases.  相似文献   

3.
The increasing sulphur (S) deficiency in soils of several parts of world has led to the use of fertilizer S, an important factor in enhancing the production and quality of crops. Very limited information is available on the use of elemental sulphur (S0) as a fertilizer, its oxidation into SO42- and transformation into organic S in semiarid subtropical soils. We studied the impact of three temperature regimes on the mineralization of soil organic S, and the oxidation and immobilization of S0 in acidic (pH 4.9), neutral (pH 7.1) and alkaline (pH 10.2) subtropical soils of north-western India. Repacked soil cores were incubated under aerobic conditions (60% water-filled pore space) for 0, 14, 28 and 42 d with and without incorporated S0 (500 g g-1 soil). Temperature had profound effects on all three soils processes, the rates of mineralization of native soil organic S, oxidation of applied S0 and transformation of S0 into soil organic S being greatest at 36 °C, irrespective of soil pH. Mineralization of native soil organic S (without added S0) resulted in the accumulation of 39, 66 and 47 g SO42-–S g-1 soil in acidic, neutral and alkaline soil in 42 d period at 36 °C. Of the total mineralization, the majority (62 – 74%) occurred during the first 14 d period. Oxidation rate of added S0 during initial 14 d period at 36 °C was highest in alkaline soil (292 g S cm-2 d-1), followed by neutral soil ((180 g S cm-2 d-1) and lowest in acidic soil (125 g S cm-2 d-1). Of the applied 500 g S0 g-1 soil, 3.2 – 10.0%, 6.8 – 15.4% and 10.0 – 23.0% oxidized to SO42-, and 13.4 – 28.6%, 16.0 – 29.0% and 14.6 – 29.0% were transformed into organic S in 42 d period in acidic, neutral and alkaline soil, respectively. The results of our study suggest that in order to synchronize the availability of S with plant need, elemental S may be applied well before the seeding of crops, especially in acidic soil and in regions where temperature remains low. Substantial mineralization of native soil organic S in the absence of applied S0 and immobilization of applied S0 into organic S suggest that the role of soil biomass as source and sink could be exploited in long term S management.  相似文献   

4.
The thermogalvanic e.m.f. of O2– conducting solid oxide cells can be used to detect small electronic contributions to the oxide conductivity, as a function of the ambient O2 partial pressure. When this contribution is negligible, the thermocell can serve as an oxygen gauge. Gas-tightness of the oxide specimen is not required, in contrast to more conventional (concentration cell) techniques.List of symbols E potential (V) - p partial pressure (atm) - S entropy (J K–1 mole–1) - S 0 standard entropy (at 1 atm) - S transported entropy - ¯S partial (ionic) entropy - Q * ionic heat of transport (J mole–1) - Seebeck coefficient or thermo (galvanic) power (V K–1) - R,T,F usual significance  相似文献   

5.
Summary Four soluble styrenic polymers containing 3-substituted pendant pyrrole rings with ester or amide arm spacer were synthesized. Their electroactive characteristics were investigated by cyclic voltammetry. The chemical oxidation was accomplished by adding FeCl3 into a solution of styrenic polymers dissolved in 1:1 mixture of dimethylformamide (DMF) and acetonitrile (ACN). The electrical conductivities of the chemically oxidized black powder of the styrenic polymers were in the range of 10-1010-9 S/cm.  相似文献   

6.
Highly regio‐ and enantioselective alcohol dehydrogenases BDHA (2,3‐butanediol dehydrogenase from Bacillus subtilis BGSC1A1), CDDHPm (cyclic diol dehydrogenase from Pseudomonas medocina TA5), and CDDHRh (cyclic diol dehydrogenase from Rhodococcus sp. Moj‐3449) were discovered for the oxidation of racemic trans‐cyclic vicinal diols. Recombinant Escherichia coli expressing BDHA was engineered as an efficient whole‐cell biocatalyst for the oxidation of (±)‐1,2‐cyclopentanediol, 1,2‐cyclohexanediol, 1,2‐cycloheptane‐diol, and 1,2‐cyclooctanediol, respectively, to give the corresponding (R)‐α‐hydroxy ketones in >99% ee and (S,S)‐cyclic diols in >99% ee at 50% conversion in one pot. Escherichia coli (BDHA‐LDH) co‐expressing lactate dehydrogenase (LDH) for intracellular regeneration of NAD+ catalyzed the regio‐ and enantioselective oxidation of (±)‐1,2‐dihydroxy‐1,2,3,4‐tetrahydronaphthalene to produce the corresponding (R)‐α‐hydroxy ketone in >99% ee and (S,S)‐cyclic diol in 96% ee at 49% conversion. Preparative biotransformations were also demonstrated. Thus, a novel and useful method for the one‐pot synthesis of both vicinal diols and α‐hydroxy ketones in high ee was developed via highly regio‐ and enantioselective oxidations of the racemic vicinal diols.

  相似文献   


7.
Mass transfer coefficients were measured for the deposition of a copper from acidified copper sulphate solution at a vertical cylinder cathode stirred by oxygen evolved at a coaxial vertical cylinder lead anode placed upstream from the cathode and flush with it. The cathodic mass transfer coefficient was increased by a factor of 2.75–6.7 over the natural convection value depending on the rate of oxygen discharge at the lead anode and height of the cathode. The data were correlated by the equation:J=0.66(FrRe)–0.21 An electrochemical reactor built of a series of vertical coaxial annular cells stirred by the counter electrode gases is proposed as offering an efficient way of stirring with no external stirring power consumption.Nomenclature a, b, c constants - C concentration of copper sulphate, mol cm–3 - d cylinder diameter, cm - D diffusivity, cm2 s–1 - F Faraday's constant - g acceleration due to gravity, cm2 s–1 - h electrode height, cm - i current density at the oxygen generating anode, A cm–2 - I L limiting current density, A cm–2 - K mass transfer coefficient, cm s–1 - P gas pressure, atm - R gas constant, atm cm3 mol–1 K–1 - T temperature, K - u solution viscosity, poise - V oxygen discharge rate as defined by Equation 9, cm3 cm–2 s–1 or cm s–1 - Z number of electrons involved in the reaction - J mass transferJ factor (S tSc 0.66) - S t Stanton number (K/V) - S c Schmidt number (v/D) - S h Sherwood number (Kh/D) - R e Reynold's number (/Vh/u) - F r Froude number (V 2 /hg) - Gr Grashof number [gh 3/v2 (1–)] - density of the solution, g cm–3 - kinematic viscosity, cm2 s–1 - void fraction of the gas in the liquid-gas dispersion  相似文献   

8.
In order to develop an optimal subunit as a T‐recognition element in hairpin polyamides, 15 novel chirality‐modified polyamides containing (R)‐α,β‐diaminopropionic acid (Rβ), (S)‐α,β‐diaminopropionic acid (Sβ), (1R,3S)‐3‐aminocyclopentanecarboxylic acid (RSCp), (1S,3R)‐3‐amino‐cyclopentanecarboxylic acid (RSCp), (1R,3R)‐3‐aminocyclopentanecarboxylic acid (RRCp) and (1S,3S)‐3‐amino‐cyclopentanecarboxylic acid (SSCp) residues were synthesized. Their binding characteristics to DNA sequences 5′‐TGC N CAT‐3′/3′‐ACG N′ GTA‐5′ ( N?N′ =A ? T, T ? A, G ? C and C ? G) were systemically studied by surface plasmon resonance (SPR) and molecular simulation (MSim) techniques. SPR showed that polyamide 4 , AcIm‐Sβ‐ImPy‐γ‐ImPy‐β‐Py‐βDp (β/Sβ pair), bound to a DNA sequence containing a core binding site of 5′‐TGC A CAT‐3′ with a dissociation equilibrium constant (KD) of 4.5×10?8 m. This was a tenfold improvement in specificity over 5′‐TGCTCAT‐3′ (KD=4.5×10?7 M ). MSim studies supported the SPR results. More importantly, for the first time, we found that chiral 3‐aminocyclopentanecarboxylic acids in polyamides can be employed as base readers with only a small decrease in binding affinity to DNA. In particular, SPR showed that polyamide 9 (RRCp/β pair) had a 15‐fold binding preference for 5′‐TGCTCAT‐3′ over 5′‐TGCACAT‐3′. A large difference in standard free energy change for A ? T over T ? A was determined (ΔΔGo=5.9 kJ mol?1), as was a twofold decrease in interaction energy by MSim. Moreover, a 1:1 stoichiometry ( 9 to 5′‐TGC T CAT‐3′/3′‐ACG A GTA‐5′) was shown by MSim to be optimal for the chiral five‐membered cycle to fit the minor groove. Collectively, the study suggests that the (S)‐α‐amino‐β‐aminopropionic acid and (1R,3R)‐3‐aminocyclopentanecarboxylic acid can serve as a T‐recognition element, and the stereochemistry and the nature of these subunits significantly influence binding properties in these recognition events. Subunit (1R,3R)‐3‐aminocyclopentanecarboxylic acid broadens our scope to design novel polyamides.  相似文献   

9.
Stegobinone, (2S, 3R, 1R)-2,3,-dihy dro-2,3,5-trimethyl-6-(1-methyl-2-oxobutyl)-4H-pyran-4-one, the sex pheromone of drugstore beetles (Stegobium paniceum L.), elicited the pheromonal response from the males of the species in our bioassay system; however, the synthesized diastereomeric mixture of this compound was actually inactive to the males. Although the stegobinone isolated from the beetles of this species had significant activity, its enantiomeric [(±)-2S,3R,1S-] and diatereomeric [(±)-2S,3S,1RS-] isomers were inactive. Adding the (±)-2S,3R,1S isomer to stegobinone significantly reduced the male response. Furthermore, the activity of Stegobinone vanished on keeping it at room temperature for two weeks. In such a stored stegobinone sample, the presence of 2S,3R,1S isomer, the inhibitory component, was confirmed. This isomer might be produced by C-1 epimerization during storage.  相似文献   

10.
Cyclic voltammetry at a glassy carbon electrode of 2,4,6-triphenylnitrobenzene (1) in DMF shows two reversible one-electron reductions. Preparative reduction of 1 yields 2,4,6-triphenylaniline under both acidic and alkaline conditions and in DMF in the presence of acetic anhydride. On reduction in dry DMF is formed a stable, violet radical anion with a broad maximum at 682 nm; in acetonitrile 1 is reported to yield an unstable bluish radical which is transformed to a yellow-purple radical with a maximum at 520 nm. Solid-state 13C NMR confirmed the existence of two stereoisomers in the crystals found by X-ray structure determination, whereas 13C NMR in chloroform at ambient temperature indicated one isomer in solution. 2,4,6-Triphenylaniline shows in CV in acetonitrile a reversible oxidation; in acetonitrile containing pyridine it is oxidized to azo(2,4,6-triphenylbenzene). This compound is in acidic aqueous DMF reduced to 2,4,6-triphenylaniline. The three phenyl groups act as electron donating groups during reductions akin to p-hydroxy or p-amino groups.  相似文献   

11.
The effect of sodium lauryl sulphate surfactant on the mass transfer coefficient of the cathodic reduction of ferricyanide ion and the anode oxidation of ferrocyanide ion at hydrogen- and oxygen-evolving electrodes, respectively, was studied. Also, the effect of sodium lauryl sulphate on the gas hold-up and cell voltage was studied. The presence of surfactant in the electrolyte was found to decrease the mass transfer coefficient by an amount ranging from 7.6 to 81% depending on the operating conditions. Gas hold-up and cell voltage were found to increase in the presence of surfactant.Nomenclature C concentration - F Faraday constant (96 487 C mol–1) - I I limiting current under natural convection - I current consumed in ferricyanide reduction or ferrocyanide oxidation during electrolysis with gas evolution - K mass transfer coefficient - V gas discharge rate - Z number of electrons involved in the reaction - gas hold-up  相似文献   

12.
The present work deals with the photooxidative degradation of tylosin antibiotic (TYL) in the presence of potassium peroxydisulfate (K2S2O8) irradiated by UV-C in the presence of immobilized nano silver. Effects of pH, temperature, peroxydisulfate concentration and immobilized nano silver dosage on the degradation efficiency of TYL were examined. Degradation efficiency was small when the oxidation was carried out in the absence of UV irradiation. Results showed that degradation of TYL increases with temperature, nano Ag and peroxydisulfate initial concentration and decreases with pH. Due to UV/nano Ag/S2O 8 2? processes, more than 90% of TYL can be degraded at room temperature in 35 min at an initial concentration of 50 mgl?. Degradation reaction order of TYL by UV/nano Ag/S2O 8 2? process is 1.89. Meanwhile, the initial rates of degradation in UV/nano Ag/S2O 8 2? processes can be described well by the Langmuir-Hinshelwood kinetic model.  相似文献   

13.
Temperature-programmed desorption (TPD) and oxidation (TPO) were used to investigate the decomposition and oxidation of ethanol on Al2O3, Pd/Al2O3, and PdO/Al2O3. Ethyl--13C alcohol (CH3 13CH2OH) was adsorbed on the catalysts so that reaction pathways of the two carbons could be distinguished. Alumina was mainly a dehydration catalyst, but dehydrogenation was also observed and some carbon remained on the surface. In the presence of O2, A12O3 oxidized the decomposition products and the-carbon was oxidized faster. Ethanol, which was adsorbed on A12O3, decomposed much faster on Pd/A12O3 by diffusing to Pd and undergoing CO elimination to form CH4,13CO, H2, and surface carbon. On PdO/A12O3, the decomposition was slower than on Pd/A12O3 until lattice oxygen was extracted above 450 K; the decomposition products were oxidized by lattice oxygen. In the presence of gas phase O2, Pd/Al2O3 was an active oxidation catalyst at low temperature, but lattice oxygen had to be extracted from PdO/A12O3 before it had significant oxidation activity.  相似文献   

14.
The thermodynamics of aqueous sulphur-water systems are summarized in the form of potential-pH diagrams, calculated from recently reported critically assessed standard Gibbs energies of formation of the species considered. However, there is convincing evidence from the literature that a value of pK a(HS) = 17–19 is appropriate, whereas a value of 13 is widely accepted; hence, the higher value of 19, corresponding to G f 0 (S2–) = 120.5 kJ mol–1 , was used in these calculations, rather than G f 0 (S2-) = 86.31 kJ mol–1 quoted in the main data source.Under ambient conditions, only – 2 (sulphide), 0 (elemental sulphur) and + 6 (sulphate) oxidation states are thermodynamically stable in water, which is predicted to be oxidized by peroxodisulphate (H2 S2 O8/SO 8 2– and peroxomonosulphate (HSO 5 /SO 5 2– ). However, when sulphate is excluded from the calculations to allow for the large energy of activation/slow kinetics of its formation from sulphide, then other sulphoxy species appear on the diagram for what is then a metastable system. Similarly, if all sulphoxy species (i.e. any species with oxidation states > 0) are excluded, then polysulphide ions (S n 2– , 2 n 5) have areas of predominance at high pH, each with a narrow potential window of predominance. Hence, this information is complemented with S n 2– /HS activity-potential diagrams at pH 9 and 14.Some species have no area of stability even on the metastable diagrams. Hence, potential-pH diagrams are also presented for the sulphite-dithionite system (excluding elemental sulphur), and that involving peroxomonosulphate (HSO 5 /SO 5 2– ) in place of peroxodisulphate (H2S2O8/SO 8 ¨– ).  相似文献   

15.
Biosynthesis of the four monoterpene compounds that comprise the pheromone of the male boll weevil,Anthonomus grandis Boheman, [1, (+)-cis-2-isopropenyl-1-methylcyclobutaneethanol; II, (Z)-3,3-dimethyl-1,-cyclohexaneethanol; III, (Z)-3,3-dimethyl-1,-cyclohexaneacetaldehyde; and IV, (E)-3,3-dimethyl-1,-cyclohexane-acetaldehyde] was studied. More pheromone was biosynthesized in the summer months, somewhat less was produced by males in the presence of females than by isolated males, and the pheromone was concentrated in the gut and surrounding tissue of the abdomen of the males. Incubation of abdomens with the pheromone alcohols yielded related hydrocarbons, aldehydes, and alcohols, which suggested the presence of several enzyme systems. Boll weevils were able to allylically oxidize myrcene and limonene to alcohols, a capability that suggests pheromone precursors may be at least in part inhaled rather than ingested. The hemolymph may then transport the precursor to the gut or some alternative site where allylic oxidation to the pheromone occurs.Coleoptera: Curculionidae.In cooperation with the Mississippi Agricultural and Forestry Experiment Station, Mississippi State, Mississippi 39762. Received for publication.  相似文献   

16.
To understand the molecular architectures of styrene‐butadiene four‐arm star (SBS) copolymers, a size exclusion chromatography combined with laser light scattering (SEC‐LLS) has been used to determine their weight‐average molecular weight (Mw) and radius of gyration (〈S21/2), and a new method for the establishment of the Mark‐Houwink equation from one sample has been developed. Based on the Flory viscosity theory, we successfully have reduced the 〈S21/2 values of numberless fractions estimated from many experimental points in the SEC chromatogram to intrinsic viscosities ([η]). For the first time, the dependences of 〈S21/2 and [η] on Mw for the four‐arm star SBS in tetrahydrofuran at 25°C were found, respectively, to be 〈S21/2 = 2.62 × 10?2 M (nm) and [η] = 3.68 × 10?2 M (mL/g) in the Mw range from 1.4 × 105 to 3.0 × 105. From data of [η] and 〈S21/2 for linear and star SBS, we have obtained the information about the branching, namely, the ratios (g and g′) of 〈S2〉 and [η] for star SBS to that of the linear SBS of the same molecular weight, which agree with theoretical predictions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 961–965, 2005  相似文献   

17.
Tetraazamacrocyclic nickel(II) complexes linked by the system of conjugated double bonds with one or two benzo-15-crown-5 moieties (2Ni and 3Ni) were synthesized and characterized. The CV of these complexes in acetonitrile (ACN) solution exhibited reversible NiII/III redox process. At more positive potentials oxidation of the bezno-15-crown-5 ether (B15C5) moiety was found. In complexes 2Ni and 3Ni redox potential of NiII/III did not change after the interactions of alkali and alkaline earth metal cations with B15C5 unit. However, the presence of guest cations caused a significant change of B15C5 oxidation potential. Complexation of two Cl anions to the coordinated NiII in 2Ni and 3Ni resulted in an appreciable shift of both NiII/III and B15C5 redox processes after addition of metal cations. Behaviour of complexes 2Ni and 3Ni was compared with behaviour of similar CuII complexes.  相似文献   

18.
Laboratory experiments were conducted to evaluate the variation ofpopulation size of methanotrophs (MOB) and CH4 oxidation pattern inflooded rice soils sampled at three spatial points (rhizosphere, bulk and baresoils). Rhizosphere soil had higher MOB population size (301.1 ×105 cells g–1 dry soil) than bulk(37.2× 105 cells g–1 dry soil) andbare soil (19.1 × 105 cells g–1dry soil). The population size of MOB followed a decreasing trend with respectto fertilizer (urea NH4NO3 NH4Cl control). The result indicated that rhizosphere soil presented thestrongestCH4 oxidation activities, as shown by the highest values of the twokinetic parameters (K m(app) andV max). K m andV max increased significantly from bare to bulkto rhizosphere soil in control and fertilized soil and ranged from 6.2 to 133.2g g–1 dry soil and from 0.03 to 0.41g h–1 g–1 dry soil,respectively. The differences in K m andV max among the three soils (rhizosphere, bulkand bare) in this study could be due to differential species composition ofmethanotrophic community and/or to conditioning of MOB under different soilmicroenvironments. The present study has demonstrated a competitive inhibition effectof NH4 +-N on CH4 oxidation.  相似文献   

19.
Mesoporous VO x /SBA-15 samples have been prepared by different impregnation methods, characterized by N2 adsorption and diffuse reflectance UV–visible spectroscopy, and their photocatalytic reactivity evaluated for the selective oxidation of methane with oxygen at 220 °C under UV irradiation. Vanadium in dehydrated VO x /SBA-15 samples was found to be predominantly as isolated four-coordinated V5+ species, especially at V loading below 2.5 wt%. VO x /SBA-15 catalysts prepared by impregnation with an aqueous solution of ammonium metavanadate (AMV) showed a maximum rate of formation of formaldehyde of 525 mol g-1 h-1 (selectivity of 93.8 mol%) at a vanadium content of 2.65 wt%. Both the rate of formation and selectivity of formaldehyde were improved when vanadium was impregnated on the SBA-15 support from a vanadyl sulfate methanolic solution (rate of formation of HCHO = 733 mol g-1 h-1, selectivity = 95.4 mol%). VO x /SBA-15 catalysts were seen to be more effective for the selective photo-assisted oxidation of methane than VO x /SiO2 catalysts.  相似文献   

20.
Summary A new method for the synthesis of conducting polypyrroles (PPy), based on chemical and combined electrochemical-chemical oxidation of pyrrole monomers in the presence of nitroxyl radical (TEMPOL-2,2,6,6-tetramethyl-4-hydroxy-1-oxy-piperidyl) as oxidation agent (in its oxidation state) and redox mediator respectively is described. The PPy films obtained are extremely porous and the electrical conductivity () of the resulting PPy samples ranges from 1 to 100 S cm–1. PPy prepared in aqueous solutions has a lower conductivity 1 S cm–1 as compared to the PPy prepared in acetonitrile solutions with conductivity of about 100 S cm–1. The PPy films are quite compact and thick films (1 mm) can be pealed off from the electrode surface and pressed as a disc for further studies. Only after partial reduction of polypyrrole film the spin-probed PPy was obtained. The concentration of nitroxyl radicals incorporated in the polymer matrix can be changed using various degrees of polymer reduction. The anisotropic broadening of the observed ESR lines indicates a low mobility of incorporated nitroxyl radicals in the PPy matrix. The electronic interaction between the nitroxyl groups and the paramagnetic centers of the polymer chains, polarons, causes an ESR line broadening of polaron signal both on air (1.1 mT) and in vacuum (0.7 mT) as compared to unmodified PPy (0.2 mT on air, 0.05 mT in vacuum).  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号