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1.
Since γ-glutamyltranspeptidase (GGT) especially catalyses the transfer of the γ-glutamyl moiety to a variety of amino acids and short peptides, GGT has important practical value for enzymatic synthesis of γ-glutamyl compounds. In this paper, the GGT produced from Bacillus subtilis NX-2 was purified by a combination of ammonium sulfate fractionation and ion exchange chromatography, and the properties of purified GGT were investigated. At the conditions of pH 10.0, D-glutamine (D-Gln)/L-tryptophan (L-Trp) with a molar ratio of 5: 7, a temperature 40°C and a reaction time of 4 h, a higher conversion rate of 42% was obtained. According to the time course, the catalytic mechanism of enzymatic synthesis of γ-D-glutamyl-L-tryptophan (γ-D-Gln-L-Trp) was discussed. It was demonstrated that the GGT can catalyze not only the reaction of transpeptidation, but also the irreversible hydrolysis of the products which results in the decrease of the yield of the products. The affinity parameter of GGT to D-Gln (Km) was 5.08 mmol·L−1 and the maximum reaction rate of transpeptidation (r max) was determined as 0.034 mmol·min−1·L−1, while the affinity parameter of GGT to γ-D-Gln-L-Trp (Km) was 2.267 mmol·L−1, and the maximum reaction rate of hydrolysis (rmax) was 0.012 mmol·min−1·L−1. __________ Translated from Journal of Chemical Engineering of Chinese Universities, 2008, 22(2): 288–293 [译自: 高校化学工程学报]  相似文献   

2.
The kinetic model of asymmetric reduction of 3-oxo-3-phenylpropionic acid ethyl ester using Saccharomyces cerevisiae CGMCC No.2266 with 10% glucose as co-substrate to realize the regeneration of NADPH was established. The effect factors on reduction, the type and the content of co-substrate and coenzyme, and the changes of the substrate and product content vs. time during the reaction process were investigated. The results indicate that 10% glucose can increase the reaction conversion from 23.0% to 98.4% and NADPH is reducer. The reduction process conforms with sequence mechanisms. The model parameters are as follows: v m =5.0×10−4 mol·L−1·h−1, k1=1.5×10−6 mol·L−1·h−1, k2=3.0×10−3 mol·L−1·h−1. The kinetic model is in good agreement with the experimental data.  相似文献   

3.
The results of the hydrogenation of coal from the Zashulanskoe deposit in the Chita oblast under conditions of a short reaction time (no longer than 10 min) are given. It was found that, to reach a 78–80% degree of coal conversion under the conditions of high-speed heating (∼200 K/min), the reaction time can be no longer than 10 min (the coal: paste-forming agent ratio = 50: 50), which corresponds to a feed space velocity of 2.5–3.0 kg l−1·h−1. This value, which determines the process productivity of coal hydrogenation, is higher by a factor of 3–3.5 than that under analogous conditions used in second generation processes, which were developed in the 1990s.  相似文献   

4.
Information on the phosphorus (P) forms of pasture soils is central to agricultural and environmental sustainability. We used a combination of 31P nuclear magnetic resonance (NMR) spectroscopy of NaOH–EDTA extracts and sequential fractionation to investigate P forms, with an emphasis on organic P in relation to environmental and biophysical variables, in 24 diverse pasture soils taken from around New Zealand (organic C 19–102 g kg−1, total P 116–2746 mg kg−1, pH 5.2–7.0). Soils were separated by cluster analysis of soil physicochemical properties and sequentially extracted P pools into those either derived from volcanic-ash materials or not. This separation was also evident for organic P species in NaOH–EDTA extracts, which removed about 75% of total soil organic P. The major organic P compound class was monoesters (24–60% of extracted P), made up of 14 to 91% myo-inositol hexakisphosphate. The next largest organic P class was diesters (0–4% of P extracted), which were enriched in volcanic-ash soils (monoester to diester ratio = 14) compared to non volcanic-ash soils (ratio = 30). Correlation analysis indicated that mean annual temperature had a significant negative and positive effect on monoester and diester concentrations, respectively. This was attributed to better physical protection of monoesters (especially inositol phosphates) from mineralization, and increased diesters from microbial activity and biological turnover. The anomalous behaviour of volcanic-ash soils was attributed to slow mineralization and the sampling of soils at different times of year without full knowledge of the large and highly dynamic microbial biomass P pool which is predominantly diesters.  相似文献   

5.
The experimental data concerning kinetics of a continuous mass crystallization in L-sorbose - water system are presented and discussed. Influences of L-sorbose concentration in a feeding solution and mean residence time of suspension in a working volume of laboratory DT MSMPR crystallizer on the resulting crystal size distributions, thus on the nucleation and growth kinetics, were determined. The kinetic parameter values were evaluated on the basis of size-independent growth (SIG) kinetic model (McCabe’s ΔL law). It was observed that within the investigated range of crystallizer productivity (220–2,200 kg of L-sorbose crystals m−3 h−1), a crystal product of mean size Lm from 0.22 to 0.28 mm and CV from 68.8 to 44.0% was withdrawn. The values of linear growth rate show increasing trend (from 6.6·10−8 to 7.6·10−8 m s−1) with the productivity enlargement (assuming constant residence time τ=900 s). Occurrence of secondary nucleation phenomena within the circulated suspension, resulting from the crystals attrition and breakage was observed. The parameter values in a design equation, matching linear growth rate and suspension density with nucleation rate were determined.  相似文献   

6.
Saccharide–fatty acid esters, important biobased and biodegradable emulsifiers in foods, cosmetics, and pharmaceuticals, were produced with high yields and productivity via immobilized Rhizomucor miehei lipase-catalyzed esterification in solvent-free systems at 65 °C. Preliminary experiments demonstrated high rates of reaction occurred in the presence of acetone near or above its boiling point, due to the formation of 10–200 μm suspensions of saccharide particles. Subsequently, a two-step process was developed to produce a solvent-free supersaturated solution of 1.5–2.0 wt% saccharide that remained stable for ≥10–12 h. The solvent-free suspensions were used in a bioreactor system at 65 °C, consisting of a reservoir open to the atmosphere that contained molecular sieves, a peristaltic pump, and a packed bed bioreactor, operated under continuous recirculation. At 10 h intervals, suspensions were re-formed by treating the substrate/product mixture with additional acyl acceptor and applying strong agitation. Using this system and approach, a product mixture containing 88% fructose oleate was formed, of which 92% was monoester, within 6 days. This equates to a productivity of 0.2 mmol h−1 g−1, which is similar to values reported for synthesis in the presence of solvent.  相似文献   

7.
Interest in the polyunsaturated fatty acid eicosapentaenoic acid (EPA) as a therapeutic agent is steadily increasing. The microalgaMonodus subterraneus produces EPA, which is concentrated mainly in the galactolipid fraction, as its major fatty acid. Nitrogen starvation increased the fatty acid content but reduced the proportion and content of EPA to 19.5% (of fatty acids) and 1.8% (of dry weight), respectively. Cultivation under low light intensity or high biomass concentration enhanced the proportion of EPA up to 36.7% of fatty acids and the content to 4.4% of dry weight. Maximal EPA productivity of 25.7 mg·L−1·d−1 was obtained at the biomass concentration that resulted in the highest biomass productivity.M. subterraneus is thus one of the most promising candidates for phototrophic production of EPA.  相似文献   

8.
The novel thermal stable composite nanofiltration membranes were prepared through the interfacial polymerization of piperazine and trimesoyl chloride on the poly (phthalazinone ether) ultrafiltration substrate. The effects of polymerization and testing conditions on membrane performance were studied. The surface morphologies of the substrate and the composite membranes were observed by means of scanning electron microscopy (SEM) and atomic force microscopy (AFM). The separation properties of membranes for dyes and salts were tested. The composite membranes show good thermal stability. The rejection for Na2SO4 was kept over 96%, while the flux reached 400 L·m−2·h−1 when it was tested at 1.0 MPa and 80°C. When tested at 1.0 MPa and 60°C, the rejection of the composite membrane for dyes was kept at high level, and the flux reached 180–210 L·m−2·h−1, while the rejection for NaCl was lower than 20%. __________ Translated from the Journal of Functional Materials, 2007, 38(12): 2025–2027, 2031 [译自: 功能材料]  相似文献   

9.
Co–BaCO3 catalysts exhibited high catalytic performance for oxidative dehydrogenation of ethane (ODE) using CO2 as oxidant. The maximal formation rate of C2H4 was 0.264 mmol · min−1 · (g · cat.)−1 (48.0% C2H6 conversion, 92.2% C2H4 selectivity, 44.3% C2H4 yield) on 7 wt% Co–BaCO3 catalyst at 650 °C and 6000 ml. (g · cat.)−1. h−1. Co–BaCO3 catalysts were comparatively characterized by XRF, N2 isotherm adsorption-desorption, XRD, H2-TPR and LRs. It was found that Co4+–O species were active sites on these catalysts in ODE with CO2. The redox cycle of Co–O species played an important role on the catalytic performance of Co–BaCO3 catalysts. On the other hand, the co-operation of BaCO3 and BaCoO3 was considered to be one of possible reasons for the high catalytic activity of these catalysts.  相似文献   

10.
Two sodium nonylphenol ethoxylate(10) sulfoitaconate ester surfactants, namely disodium nonylphenol ethoxylate(10) sulfoitaconate monoester (DNE(10)SIM) and sodium nonylphenol ethoxylate(10) sulfoitaconate diester (SNE(10)SID), were synthesized through the esterification and sulfonation reactions with nonylphenol ethoxylate(10) ester, itaconic acid and sodium sulfite as the raw materials. The chemical structures of the prepared surfactants were confirmed by FTIR and 1H NMR. The surface tension of the synthesized surfactants was measured at 25 °C and the surface active properties were characterized. The DNE(10)SIM had better surface activity. The CMC was 1.77 × 10−6 mol L−1 and γCMC was 35.45 mN m−1. The CMC and γCMC for the SNE(10)SID were 5.42 × 10−5 mol L−1 and 37.67 mN m−1, respectively. Moreover, the emulsification power of SNE(10)SID was better.  相似文献   

11.
A conversion of 80–93% was achieved for esterification of oleic acid and fructose (or sucrose) catalyzed by immobilized Rhizomucor miehei lipase (Lipozyme IM; Novozymes, Franklinton, NC) at 65°C using near-stoichiometric amounts of substrates. The product consisted of mono- and diester at a ratio of 9∶1 gg−1. The main obstacle for achieving a high rate of reaction, the poor miscibility of the substrates, was overcome by taking advantage of the greatly increased solubility of fructose as the proportion of ester increased. A phase diagram demonstrated that the solubility of fructose increased linearly from 0.002 to 0.07 to 0.13 gg−1 as the ester mass fraction increased from 0.00 to 0.47 to 0.80, respectively. Solvent (tert-butanol) was present only during the first phase of the time course of the reaction to enhance fructose solubility and was allowed to evaporate away completely on reaching 25% conversion. A conversion higher than 80–93% could not be achieved by reducing the bioreactor's water content through use of vacuum pressure or water activity control. Water adsorption isotherms demonstrate the significant increase of equilibrium liquid phase water content as the reaction progressed, which was due to higher water adsorption by the monoester relative to oleic acid. Increased removal of liquid phase water may result in the loss of water from the lipase, resulting in a reduction of its biocatalytic activity. Initial rate experiments were used to derive a Ping-Pong Bi Bi kinetic model that strongly agreed with measured data for the time course of the reaction. Lipozyme IM did not lose activity when employed for three successive fructose-oleate esterification batch reactions or, equivalently, for a 24-d reaction period.  相似文献   

12.
The effects of temperature and temperature shift on the fatty acid composition and docosahexaenoic acid (DHA, C22∶6n−3) content and productivity of the marine microalga Crypthecodinium cohnii ATCC 30556 were investigated. The microalga grew well over the entire range of temperatures (15–30°C) studied. High temperature favored the growth of the microalga with the highest specific growth rate of 0.092 h−1 at 30°C. In contrast, low temperature favored the formation of polyunsaturated fatty acids. The highest DNA content was obtained at 15°C in the early stationary phase (i.e., 72h). In order to achieve high DHA productivity, a shift from high temperature to low temperature at a later stage of cultivation (i.e., 48h) was also attempted. A temperature shift from 25°C (for 48 h) to 15°C (for 24 h) resulted in an increase in cellular DHA content by 19.9% and productivity by 6.5% as compared to that maintained at 25°C (for 72 h).  相似文献   

13.
Nutritional requirements for maximal production of biosurfactant by an oil field bacterium Pseudomonas putida were determined. The optimal concentrations of nitrogen, phosphate, sulfur, magnesium, iron, potassium, sodium, calcium, and trace elements for maximal production of biosurfactants were ascertained, and a new “Pruthi and Cameotra” salt medium was formulated. Data show that maximal biomass (2.4 g L−1) and biosurfactant production (6.28 g L−1) takes place after 72 h of growth on 2% hexadecane. The biosurfactant was produced optimally over pH and temperature ranges of 6.4–7.2 and 30–40°C, respectively. That the highest biosurfactant yield was obtained during late log phase of growth indicates that the biosurfactant is a secondary metabolite.  相似文献   

14.
Using chemical reduction-deposition method, a type of metallic cobalt-decorated multi-walled carbon nanotubes, noted as y%(mass percentage)Co/MWCNTs, was prepared. TEM, SEM and XRD measurements demonstrated that the metallic cobalt was evenly coated on the MWCNT substrate, with granule-diameter of the Co x 0 -crystallites of 5–8 nm. Using the y%Co/MWCNTs as support, a type of supported Co–Mo–K sulfide catalysts, noted as x%(Co i Mo j K k )/(y%Co/MWCNTs), for higher alcohol synthesis (HAS) was developed. It was experimentally shown that using the Co-modified MWCNTs in place of simple MWCNTs or activated carbon (AC) as the catalyst support led to a significant increase in activity of CO hydrogenation conversion and improvement in the selective formation of C2+-alcohols. Under the reaction condition of 5.0 MPa, 613 K, CO/H2/N2 = 45/45/10 (v/v) and GHSV = 3600 mlSTPh−1 g −cat. −1 , the observed STY of C1–4-alcohols reached 154.1 mgh−1g −cat. −1 at 12.6% conversion of CO over the 11.6%(Co1Mo1K0.6)/(6.4%Co/MWCNTs) catalyst, which was 1.76 and 2.33 times as high as that (87.7 and 66.1 mgh−1g −cat. −1 ) of the reference systems supported by simple MWCNTs and AC respectively. Ethanol became the predominant product of the CO hydrogenation, with carbon-based selectivity ratio of C2–4-alcohols to CH3OH reaching 3.6 in the products. It was experimentally found that using the Co-modified MWCNTs in place of simple MWCNTs or AC as the catalyst support caused little change in the apparent activation energy for the conversion of CO, but led to a slight increase in the molar percentage of catalytically active Mo-species (Mo4+) in the total Mo-amount at the surface of the functioning catalyst. Based upon the results of TPD investigation, it could be inferred that, under the reaction condition of HAS, there existed a considerably larger amount of adsorbed H-species and CO-species on the functioning catalyst, thus in favour of increasing the rate of a series of surface hydrogenation reactions in HAS.  相似文献   

15.
The electrochemical oxidation of olive mill wastewater (OMW) over a Ti/RuO2 anode was studied by means of cyclic voltammetry and bulk electrolysis and compared with previous results over a Ti/IrO2 anode. Experiments were conducted at 300–1,220 mg L−1 initial chemical oxygen demand (COD) concentrations, 0.05–1.35 V versus SHE and 1.39–1.48 V versus SHE potential windows, 15–50 mA cm−2 current densities, 0–20 mM NaCl, Na2SO4, or FeCl3 concentrations, 80 °C temperature, and acidic conditions. Partial and total oxidation reactions occur with the overall rate being near first-order kinetics with respect to COD. Oxidation at 28 Ah L−1 and 50 mA cm−2 leads to quite high color and phenols removal (86 and 84%, respectively), elimination of ecotoxicity, and a satisfactory COD and total organic carbon reduction (52 and 38%, respectively). Similar performance can be achieved at the same charge (28 Ah L−1) using lower current densities (15 mA cm−2) but in the presence of various salts. For example, COD removal is less than 7% at 28 Ah L−1 in a salt-free sample, while addition of 20 mM NaCl results in 54% COD reduction. Decolorization of OMW using Ti/RuO2 anode seems to be independent of the presence of salts in contrast with Ti/IrO2 where addition of NaCl has a beneficial effect on decolorization.  相似文献   

16.
To assess the validity of two techniques used to measure human cholesterol synthesis, the rate of uptake of deuterium (D) into plasma free cholesterol (FC), and plasma cholesterol precursor (squalene, lanosterol, desmosterol and lathosterol) levels were compared in 14 women [65–71 yr with low density lipoprotein-cholesterol (LDL-C)≥3.36 mmol·l −1]. Subjects consumed each of six diets for 5-wk periods according to a randomized crossover design. The experimental diets included a baseline diet (39% energy as fat, 164 mg chol·4.2 MJ−1) and five reduced-fat diets (30% of energy as fat), where two-thirds of the fat was either soybean oil; squeeze, tub or stick margarines; or butter. Fractional and absolute synthesis rates (FSR and ASR) of FC were determined using the deuterium incorporation (DI) method, while cholesterol precursor levels were measured using gas-liquid chromatography. Data were pooled across diets for each variable and correlation coefficients were calculated to determine if associations were present. There was good agreement among levels of the various cholesterol precursors. In addition, FSR in pools/d (p·d−1) and ASR in grams/d (g·d−1) were strongly associated with lathosterol (r=0.72 and 0.71, P=0.0001), desmosterol (r=0.75 and 0.75, P=0.0001), lanosterol (r=0.67 and 0.67), and squalene (r=0.69 and 0.68) when levels of the precursors were expressed as μmol·mmol−1C. Significant but lower correlations were observed between the D uptake and plasma cholesterol precursor levels when the latter were expressed in absolute amounts (μmol·L−1). The wide range of fatty acid profiles of the experimental diets did not influence the degree of association between methods. In conclusion, the DI method and levels of some cholesterol precursors correspond as methods for shortterm measurement of cholesterol synthesis.  相似文献   

17.
The influence of sorbitol or glycerol on the electrodeposition of ZnNi alloys and on the morphology, composition and structure of the ZnNi deposits was investigated. The highest current efficiency (CE), around 90%, was obtained in the presence of glycerol in the potential range from approximately −1.30 V to −1.40 V, while in the presence of sorbitol or absence of either polyalcohol the CE was 82–85%, for the same potential range. Scanning electron microscopy (SEM) analysis showed that ZnNi deposition at −1.26 V or −1.40 V from a bath with sorbitol led to the formation of more compact deposits than with glycerol. Energy dispersive X-ray spectroscopy (EDS) analysis showed that the Ni content in the deposit obtained in the presence of sorbitol remained in the range of 7–9.5 wt% Ni, over a large range of deposition conditions. On the other hand, ZnNi deposits with variable Ni content (5.5–19.5 wt% Ni) were obtained from baths with glycerol or without either polyalcohol, by shifting the deposition potential. All ZnNi deposits showed uniform distribution of the elements Zn and Ni. X-ray analysis of ZnNi deposits obtained from plating baths with and without polyalcohol’s at −1.26 and −1.40 V presented the γ, γ1 and Pt3–Zn phases.  相似文献   

18.
Under the conditions of phase transfer catalysis and nitrobenzene as the solvent, the halogen-exchange fluorination of 2,6-dichlorobenzaldehyde using KF as fluorinating agent was studied. The kinetics was investigated and the reaction rate constants were obtained under the optimum conditions of n(KF):n(2,6-dichlorobenzaldehyde): n(Ph4PBr):n(acetone-furan crown ether) = 4:1:0.1:0.05 and temperatures of 433 K, 443 K, 453 K and 463 K. The results illustrated the activation energy of the first and the second step is 4.57 × 104 J·mol−1 and 3.53 × 104 J·mol−1, respectively. The pre-exponential factor is 4.50 × 105 h−1 and 1.08 × 104 h−1, respectively. Thus a reliable kinetics data could be obtained for further research. __________ Translated from Chemical Engineering (China), 2007, 35(8): 33–36 [译自: 化学工程]  相似文献   

19.
A novel technique is utilized to detect trace amounts of phloroglucinol. In pH 5.0, 0.1 mol L−1 HAc–NaAc buffer solution, phloroglucinol exhibited a stable and sensitive oxidation signal at a glassy carbon electrode modified with multi-wall carbon nanotube. By using the surfactant cetyl pyridinium chloride, the electrochemical response was greatly enhanced. The mechanism was systematically explored. In the range 9.0 × 10−7–3.0 × 10−4 mol L−1, the oxidation peak currents of phloroglucinol have a linear relationship with concentration: the limit of detection was estimated to be 2.5 × 10−7 mol L−1 (S/N = 3). The method was adopted to detect the content of phloroglucinol injection, and the recovery was from 97.5% to 103.0%.  相似文献   

20.
“Conjunct oligomerization” of propylene or the isopentane–propylene alkylation catalyzed by an excess of 95% sulfuric acid was performed in two consecutive steps. First di-isopropylsulfate was prepared by interaction of sulfuric acid with propylene. The ester was then either decomposed at room temperature in the presence of the 5–10 molar excess of 95% acid or was used in the acid-catalyzed alkylation of isopentane. In situ 1H and 13C NMR study of the reaction mixture of “conjunct oligomerization” indicated that the diester participates in two equilibria with sulfuric acid. The first one transforms the diester into a monoester. The second equilibrium corresponds to protonation of the monoester with an excess of sulfuric acid. This converts a minor fraction of the mono-alkylsulfate into isopropyl carbenium ions that are only weakly solvated with sulfuric acid: C3H7HSO4 + H2SO4 ⇄ C3H7 + H2SO4 + HSO4 . The subsequent reactions of alkyl carbenium ions with the non-protonated alkylsulfate result in final products of “conjunct oligomerization” while in the presence in the reaction mixture of isopentane, alkylation with the predominant formation of C8 branched paraffins takes place. A very low yield of propane indicates a minor role of hydride transfer in alkylation. Another unexpected result is the absence in both reaction mixtures of propylene. These findings are in contradiction with the classical mechanism of isoparaffin–olefin alkylation by Schmerling. Therefore, an alternative mechanism of this reaction is suggested via a direct alkylation of isopentane with the mono-alkylsulfate. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

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