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1.
The kinetics of the hydrolysis of methyl cellulose (MC, DS 1.27 and 1.95) was studied by a two-step procedure, comprising partial hydrolysis in 1 M TFA in water and water/acetone at 120 °C for various time periods, labeling of generated reducing ends by reductive amination, complete depolymerization by methanolysis followed by trimethylsilylation, and gas chromatographic analysis of the two sets of partially O-methylated glucose derivatives. Rate constants of MCs were all in the order of 10?4 s?1. In aqueous TFA, overall rate of hydrolysis of the MC with lower DS was faster than of the MC with higher DS. When substituting half of the water by acetone, reaction was slowed down while selectivity regarding different O-methyl glucosyl residues increased. Compared to the parent glucosyl unit methylation at O-2 and at O-6 decreased rate of hydrolysis, while 3-O-methyl favored it especially in the early stage of the conversion of the macromolecules. Beside slight differences between the two MCs and reaction conditions, rate constants k i (i = position of methyl) followed the order k 36 ≈ k 3 > k 0 ≈ k 23 > k 6 > k 2 ≥ k 236 > k 26. For the higher substituted MC2 an initial slow phase with more pronounced differences of k i, followed by a faster less selective period was observed. Regioselectivity of hydrolysis with respect to methyl positions was expressed as standard deviation of k i and was between 16 and 46% depending on MC and conditions. Findings are discussed with respect to electronic effects, solvent-effect, H-bonding pattern and solution state.  相似文献   

2.
A simple, semi-empirical, generalized expression was developed for the LDF mass transfer coefficient k as a function of the half cycle time θ c that encompasses and transitions between the well-known regions governed by the long cycle time constant Glueckauf k and the short cycle time dependent k. This new expression can be used to estimate k = f(θ c ) for any system, irrespective of the loading and irrespective of θ c , no matter if k is in the cycle time dependent region or not. A three times wider transition region between the Glueckauf k and the cycle time dependent k was also established, with the Glueckauf LDF limit now valid for θ c  > 0.3 and the short cycle time limit now valid for θ c  < 0.01. When evaluating this region for several adsorbate-adsorbent systems, the minimum Glueckauf θ c spanned three orders of magnitude from thousands of seconds to just a few seconds, indicating a cycle time dependent k is not necessarily limited to what is normally considered a short cycle time. For virtually any θ c less than this minimum Glueckauf θ c , this new first-of-its-kind expression can be used to readily provide an accurate value of k = f(θ c ). Since the widely accepted half cycle time concept does not apply to the actual simulation of a multi-step, unequal step time, pressure swing adsorption process, the value of k = f(θ c ) from this new expression can be based on either the shortest cycle step in the cycle or a different value of k = f(θ c ) for each cycle step time in the cycle, with validity confirmed either by experiment or by process simulation using the exact solution to the pore diffusion equation.  相似文献   

3.
The optimal conditions for acetone–butanol–ethanol (ABE) production were evaluated using waste seaweed from Gwangalli Beach, Busan, Korea. The waste seaweed had a fiber and carbohydrate, content of 48.34%; these are the main resources for ABE production. The optimal conditions for obtaining monosaccharides based on hyper thermal (HT) acid hydrolysis of waste seaweed were slurry contents of 8%, sulfuric acid concentration of 138 mM, and treatment time of 10 min. Enzymatic saccharification was performed using 16 unit/mL Viscozyme L, which showed the highest affinity (Km?=?1.81 g/L). After pretreatment, 34.0 g/L monosaccharides were obtained. ABE fermentation was performed with single and sequential fermentation of Clostridium acetobutylicum and Clostridium tyrobutyricum; this was controlled for pH. A maximum ABE concentration of 12.5 g/L with YABE 0.37 was achieved using sequential fermentation with C. tyrobutyricum and C. acetobutylicum. Efficient ABE production from waste seaweed performed using pH-controlled culture broth and sequential cell culture.  相似文献   

4.
A novel 1-benzhydryl piperazine derivative 1-benzhydryl-4-(2-nitro-benzenesulfonyl)-piperazine was synthesized by the nucleophilic substitution of 1-benzhydryl piperazine with 2-nitro-benzenesulfonyl chloride. The product obtained was characterized spectroscopically and finally confirmed by X-ray diffraction study. The title compound, C23H23N3O4S crystallizes in the monoclinic space group C2/c with cell parameters a = 13.1120(9) Å, b = 21.4990(9) Å, c = 16.655(1) Å, β = 111.352(2)°, Z = 8, and V = 4372.7(4) Å. The structure reveals that the piperazine ring is in a chair conformation. The geometry around the S atom is distorted tetrahedral. There is a large discrepancy in the bond angles around the piperazine N atoms. The structure is stablized by C–H···O type intermolecular hydrogen bonding interactions.  相似文献   

5.
In a majority of environments, microbes live as interacting communities. Microbial communities are composed of a mix of microbes with often unknown functions. Polymicrobial diseases represent the clinical and pathological manifestations induced by the presence of multiple infectious agents. These diseases are difficult to diagnose and treat and usually are more severe than monomicrobial infections. The interaction relationship between Enterococcus faecalis and Escherichia coli was researched using a Calvet calorimeter. Three mixtures of both bacteria were prepared in the following proportions: 20 + 80 % (0.2 mL E. faecalis + 0.8 mL E. coli), 50 + 50 % (0.5 mL E. faecalis + 0.5 mL E. coli) and 80 + 20 % (0.8 mL E. faecalis + 0.2 mL E. coli). Experiments were carried out at concentration of 106 CFU mL?1 and a constant temperature of 309.65 K. The differences in shape of graph of E. faecalis, E. coli and their mixtures were compared. Also, the thermokinetic parameters such as detection time (t d), growth constant (k), generation time (G) and the amount of heat released (Q) were calculated.  相似文献   

6.
Two cis-dioxomolybdenum(VI) complexes [MoO2L] (L: L 1, 2 and L: L 2, 3) in a phenol-based sterically encumbered N2O2 ligand environment have been synthesized, and their crystallographic characterizations are reported. The orange crystals of 2 are monoclinic, space group P21/a with unit cell dimensions as a=16.2407(17) Å, b=7.2857(8) Å, c=18.400(2) Å, β=98.002(9)°, Z=4, and d cal=1.486 g cm?3. The light orange crystals of 3, however, are orthorhombic, space group, Pbcn, with unit cell dimensions a=8.3110(12) Å, b=12.637(3) Å, c=34.673(5) Å, Z=4, and d cal=1.187 g cm?3. The structures were refined by a full-matrix least-squares procedure on F 2 to a final R=0.046 (0.055 for 3) using 4944 (3677) all independent data. In both the cases, the Mo atom exists in a distorted octahedral geometry defined by a N2O4 donor set, which features a cis-Mo(–O)2 and a trans-Mo(OPh)2 arrangement. Compound 2 undergoes a quasireversible one-electron reduction at ?1.3 V vs Ag/AgCl reference due to MoVIO2/MoVO2 electron transfer and thus providing a rare example of steric solution to the comproportionation–dimerization problem encountered frequently in the development of valid biomimetic models for the active sites of oxomolybdenum enzymes.  相似文献   

7.
Two series of water-soluble metalloporphyrin-cored amphiphilic star block copolymers were synthesized by controlled radical polymerizations such as atom transfer radical polymerization (ATRP) and reversible addition fragmentation chain transfer (RAFT), which gave eight amphiphilic block copolymer arm chains consisting of poly(n-butyl acrylate-b-poly(ethylene glycol) methyl ether methacylate) (PnBA-b-PEGMEMA, Mn,GPC = 78,000, Mw/Mn = 1.2, 70 wt% of PPEGMEMA) and poly(styrene-b-2-dimethylamino ethyl acrylate) (PS-b-PDMAEA, Mn,GPC = 83,000, Mw/Mn = 1.2, 67 wt% of PDMAEA), yielding porphyrin(Pd)-(PnBA-b-PPEGMEMA)8 and porphyrin(Pd)-(PS-b-PDMAEA)8, respectively. Obtained metalloporphyrin polymer photocatalysts were homogeneously solubilized in water to apply to the removal of chlorophenols in water, and was distinguished from conventional water-insoluble small molecular metalloporphyrin photocatalysts. Notably, we found that the water-soluble star block copolymers with hydrophobic–hydrophilic core–shell structures more effectively decomposed the chlorophenol, 2,4,6-trichlorophenol (2,4,6-TCP), in water under visible light irradiation (k = 1.39 h?1, t1/2 = 0.5 h) in comparison to the corresponding water-soluble star homopolymer, because the hydrophobic core near the metalloporphyrin effectively captured and decomposed the hydrophobic chlorophenols in water.  相似文献   

8.
We have refined single crystals of Na2Ti6O13 through the X-ray Rietveld method. The synthesis of the Na2Ti6O13 was carried out by sol–gel method at 70 °C, and the obtained gel was heat treated at different temperatures. Through different analytical techniques such as X-ray Diffraction (XRD), Scanning Electronic Microscopy (SEM), Infrared Spectroscopy (FTIR), and Thermal Analysis (DTA/TGA), it was determined that Na2Ti6O13 can be prepared at low temperature (750 °C) by sol–gel method. The product crystallizes in rectangular shape micro-fibers, free of impurities. Rietveld refinement was performed using X-ray diffraction technique taking as basis a monoclinic cell with space group C2/m. The following refined parameters were obtained: a = 15.095(7) Å, b = 3.745(3) Å, c = 9.174(1) Å, β = 99.01. Additionally, Na2Ti6O13 was tested as photocatalysts on the degradation of methylene blue (MB) under UV light. The degradation reaction follows a first order reaction model with kinetic parameters k = 0.0089 min?1, and t 1/2 = 78 min.  相似文献   

9.
In higher plants, multiple copies of the cysteine synthase gene are present for cysteine biosynthesis. Some of these genes also have the potential to produce various kinds of β-substitute alanine. In the present study, we cloned a 1275-bp cDNA for cytosolic O-acetylserine(thiol)lyase (cysteine synthase) (Cy-OASTL) from Leucaena leucocephala. The purified protein product showed a dual function of cysteine and mimosine synthesis. Kinetics studies showed pH optima of 7.5 and 8.0, while temperature optima of 40 and 35 °C, respectively, for cysteine and mimosine synthesis. The kinetic parameters such as apparent Km, kcat were determined for both cysteine and mimosine synthesis with substrates O-acetylserine (OAS) and Na2S or 3-hydroxy-4-pyridone (3H4P). From the in vitro results with the common substrate OAS, the apparent kcat for Cys production is over sixfold higher than mimosine synthesis and the apparent Km is 3.7 times lower, suggesting Cys synthesis is the favored pathway.  相似文献   

10.
The dissolution of silver nanoparticles in their reaction with aqueous HNO3 solubilized to an reverse micelle solution of sodium bis(2-ethylhexyl)sulfosuccinate in decane is studied spectrophotometrically. A physicochemical model is advanced for quantifying the process kinetics on th basis of the following autocatalytic scheme: Ag0 + H+ + NO 3 ? → Ag+ + products (k 1), and Ag0 + Ag+ + NO 3 ? → 2Ag+ + products (k 2). The effective rate constant k 2 decreases with decreasing solubilization capacity V S/V O (where V S is the volume of the solubilized dispersed aqueous phase and V O is the volume of the micelle solution); the solubilization capacity determines the size of the micelle cavities in which the reaction between Ag0 and HNO3 occurs: k 2 = 74 (V S/V O) · 100% ≈ 3.8%), 41 (2.9), and 35 (2.0) L/(mol s). The effective constant k 1 is determined with a high uncertainty; the effect of V S/V O on k 1 has the opposite tendency.  相似文献   

11.
A new high-nitrogen complex [Cu(Hbta)2]·4H2O (H2bta = N,N-bis-(1(2)H-tetrazol-5-yl) amine) was synthesized and characterized by elemental analysis, single crystal X-ray diffraction and thermogravimetric analyses. X-ray structural analyses revealed that the crystal was monoclinic, space group P2(1)/c with lattice parameters a = 14.695(3) Å, b = 6.975(2) Å, c = 18.807(3) Å, β = 126.603(1)°, Z = 4, D c = 1.888 g cm?3, and F(000) = 892. The complex exhibits a 3D supermolecular structure which is built up from 1D zigzag chains. The enthalpy change of the reaction of formation for the complex was determined by an RD496–III microcalorimeter at 25 °C with the value of ?47.905 ± 0.021 kJ mol?1. In addition, the thermodynamics of the reaction of formation of the complex was investigated and the fundamental parameters k, E, n, \( \Updelta S_{ \ne }^{{{\uptheta}}} \), \( \Updelta H_{ \ne }^{{{\uptheta}}} \), and \( \Updelta G_{ \ne }^{{{\uptheta}}} \) were obtained. The effects of the complex on the thermal decomposition behaviors of the main component of solid propellant (HMX and RDX) indicated that the complex possessed good performance for HMX and RDX.  相似文献   

12.
The expansion of an oxygen low-pressure microwave plasma was investigated in order to determine the optimal plasma parameters for the growth of functional oxide semiconductors. Langmuir probe measurements show that the electron density (n e ) increases with the injected power up to a saturation value of 3.0 × 109 cm?3 determined at 10 mTorr while electron temperature (T e ) remains constant at a value of 1.5 eV. When pressure is varied, n e shows a maximum value at a range from 12 to 20 mTorr while T e decreases monotonously with increasing pressure. In addition, both n e and T e decrease with the axial distance from the plasma source. These effects were discussed through the loss mechanisms in the remote plasma. For a pressure of 13 mTorr and at a substrate temperature of 500 °C, plasma enhanced oxidation of pure metallic Ti thin films lead to the formation of a pure TiO2 anatase phase compared to a mixed phase of TiO2 and TiO in the absence of plasma activation. For Mn thin films, the exposure to oxygen remote plasma led to the formation of MnO2 as opposed to obtaining Mn3O4 when oxidation is performed in the oxygen gas ambient. Remote plasma processing was thus found to provide selective pathways to control oxidation states, stoichiometry and phase composition of technologically attractive oxide thin films.  相似文献   

13.
The oxygen-deficient Sr0.75Y0.25Co0.9Ru0.1O3?δ (SYCR) cathode is systematically evaluated for the application of solid oxide fuel cells. X-ray diffraction analysis indicates that SYCR presents a tetragonal structure with space group of I4/mmm (139). In the measured high oxygen partial pressure (pO2) region (0.01–0.21 atm), the conductivity increases with increasing pO2 because of the oxygen vacancy annihilation and hole creation, relating to a general p-type semiconducting mechanism. To get an insight into the rate-limiting step of SYCR cathode, behaviors of individual polarization resistance (R 1 and R 2) are investigated in different pO2. The obtained fitting results reveal that R 1 is nearly independent on the pO2, while R 2 presents a (pO2)?0.5 dependence. At 800 °C, SYCR cathode exhibits an R p value of 0.14 Ω cm2, moreover, when using the wet hydrogen (~ 3% H2O) as fuel and ambient air as oxidant, the maximum power density of single cell Ni-YSZ (yttria-stabilized zirconia)|YSZ|SYCR reaches 452.9 W cm?2.  相似文献   

14.
A series of Ni–La/γ-Al2O3 catalysts were prepared by adopting the methods of isometric impregnation and microwave impregnation. The catalysts were characterized with XRD, BET, and SEM, respectively. Inspecting the effects of adding La and the methods of impregnation on the hydrogenation activity of catalysts. The results show that adding a moderate amount of La promotes the dispersing of Ni on the carrier, the methods of microwave impregnation weaks the interaction between Ni and the carrier further, inhibits the formation of NiAl2O4, and the activity of catalyst prepared by the methods of microwave impregnation was significantly higher than that prepared by the methods of isometric impregnation. The hydrogenation activity of the Ni–La/γ-Al2O3 (WB) dipped with n(Ni): n(La) = 4: 1, microwave irradiation time 30 min with power 600W as well as calcined at 400°C exhibited the best performance. The conversion rate is 91.21% with reaction conditions: T = 160°C, p = 0.8 MPa, air speed 5 h–1, n(H2): n(benzene) = 2: 1.  相似文献   

15.
Densities for aqueous solutions of magnesium tetraborate MgB4O7(aq) at the molalities of (0.00556–0.03341) mol·kg?1 were measured with an Anton Paar Digital vibrating-tube densimeter at temperature intervals of 5 K from 283.15 to 363.15 K and 0.1 MPa. Apparent molar volumes were obtained based on the experimental density data, and the 3D diagrams of the apparent molar volume (V ? ) of MgB4O7(aq) against temperature (T) and molality (m) were plotted. On the basis of the Vogel–Tamman–Fulcher equation, the coefficients of the correlation equation for densities of MgB4O7(aq) against temperature and molality were parameterized. According to the Pitzer ion-interaction model of the apparent molar volume, the temperature correlation equations of Pitzer single-salt parameters F(i,p,T)?=?a0?+?a1?×?T?+?a2?×?T 2?+?a3/T?+?a4?×?ln(T)?+?a5?×?T 3 (where T is temperature in Kelvin, a i are model parameters) for MgB4O7 were obtained for the first time.  相似文献   

16.
A new three-dimensional platinum(II)–thallium(I) coordination polymer [{Pt(pda)(NHCOtBu)2}4Tl4][Pt(CN)4]2·2H 2 O (pda = 1,2-propyldiamine) has been prepared from the direct reaction of [Tl2Pt(CN)4] and [Pt(pda)(NHCOtBu)2] in water, and its structure was characterized by X-ray diffraction analysis. The compound crystallizes in monoclinic, space group Pn, a = 11.567(2) Å, b = 11.570(2) Å, c = 37.677(8)Å, β = 94.64(3)°, V = 5025.8(17) Å3, Z = 2, R1 = 0.0679 and wR2 = 0.1574 [I >  2σ (I)], Goodness-of-fit on F 2 = 1.055. The compound exhibits a novel 3D network structure consisting of [Pt(CN)4]2? connected 1D infinite Pt–Tl–Pt–Tl chains via strong Pt–Tl bonds.  相似文献   

17.
Polycrystalline samples in the lutetium-doped zinc tungstate system Zn1?x Lu x WO4 with 0 ≤ x ≤ 0.08 were synthesized using the coprecipitation method followed by thermal treatment at 1000 °C during 4 h. The polycrystalline samples were characterized by X-ray diffraction analysis, scanning electron microscopy (SEM), infrared spectroscopy, and luminescence analysis under X-ray excitation. Rietveld analyses were performed. The variation of the wolframite structure cell parameters in the range 0 ≤ x ≤ 0.05 were congruent with substitution of Zn2+ by Lu3+. SEM micrographs of the obtained samples presented improved crystallization with morphology depending on the lutetium fraction. The luminescence spectra obtained under X-ray excitation (E < 40 keV) were in the blue–green region, and their intensity increased with x up to x = 0.05. The differences in the intensities of the X-ray luminescence spectra could be related to additional cation vacancies resulting from substitution of Zn2+ by Lu3+.  相似文献   

18.
S-allyl-β-N-[(2-hydroxyphenyl)methylene]hyrazinecarbodithioate) (1, H2L), the Schiff base of dithiocarbazate with unsaturated allyl substitution, can act as a new tridentate SNO ligand H2–L and react with cobalt(II) nitrate hexahydrate to form the novel linear trinuclear isovalence Co(II) complex, [Co3(H–L)2(L)2] 2C2H5OH (2). The compounds were characterized by elemental analysis, infrared, and ultraviolet spectroscopy. Compound 2 was also characterized by single-crystal X-ray analysis and crystallizes in the orthorhombic space group, Pbcn, with a = 30.643(1) Å, b = 9.118(4) Å, c = 19.017(7) Å, α = β γ = 90°, V = 5312.95 Å3, Z = 4, and R 1 = 0.0790, (wR 2) = 0.1223. The six-coordinate central Co(II) atom is bonded to two deprotonated metal-containing ligands. The terminal Co(II) atoms are in a square planar SNON four-coordinate environment and connected to the central Co(II) by N-atoms from the ligand backbone. For quantifying the intermolecular interactions in crystal lattice, the new d norm surface and the breakdown of fingerprint plots have been used for visualizing and exploring the compound 2.  相似文献   

19.
A new sandwich polyoxometalate Na4Zn2[Zn2(H2O)10(ZnCl)6(B-α- BiW9O33)2] · 40.5H2O (1) has been obtained in aqueous solution and characterized by IR, UV, element analysis, TG and single-crystal X-ray analysis. Polyoxoanion 1 is composed of a Zn 6 12+ hexagon sandwiched by two [BiW9O33]9? units, which is firstly observed in tungstobismutate. The crystal data for compound 1: Triclinic, space group P–1, a = 15.426(3) Å, b = 15.467(3) Å, c = 15.526(3) Å, α = 74.24(3)°, β = 64.37(3)°, γ = 60.73(3)°, V = 2905.3(1) Å3, Z = 1.  相似文献   

20.
A mixed oxide-covered mesh electrode composed of NiCo2O4 (MOME-NiCo2O4) was prepared on a stainless-steel substrate using thermal decomposition (slow-cooling rate method). Surface, bulk and electrochemical properties of MOME were studied using different techniques, namely scanning electron microscopy (SEM), X-ray diffraction (XRD), cyclic voltammetry (CV) with determination of the electrochemical porosity (?) and morphology factor (φ) parameters, quasi-stationary polarisation curves (PC) and electrochemical impedance spectroscopy (EIS). SEM images revealed a good coverage of the metallic wires by a compact oxide layer (absence of cracks). XRD analysis confirmed the formation of the spinel NiCo2O4 with the presence of NiO. The ‘in situ’ surface parameters denoted as ? and φ exhibited values of 0.39 and 0.33, respectively, revealing that the electrochemically active surface area is mainly confined to the ‘outer/external’ surface regions of the oxide layer. The PC was characterised by two Tafel slopes distributed in the low (b 1 = 46 mV dec?1) and high (b 2 = 59 mV dec?1) overpotential domains. The corresponding apparent exchange current densities were j 0(1) = (3.43 ± 0.11) × 10?6 A cm?2 and j 0(2) = (6.70 ± 0.08) × 10?6 A cm?2, respectively. The EIS study accomplished in the low-overpotential domain revealed a Tafel slope (b 1) of 51 mV dec?1. According to the spin-trapping reaction using N,N-dimethyl-p-nitrosoaniline (RNO), the MOME-NiCo2O4 electrode exhibited good performance for the generation of weakly adsorbed hydroxyl radicals (HO?) during the OER in electrolyte-free water.  相似文献   

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