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1.
BACKGROUND: Microbial transformation of steroids has attracted widespread attention, especially the transformation of those steroids synthesized with difficulty by chemical methods. In this study, microbial transformation of androst‐4‐ene‐3, 17‐dione (AD) by Bordetella sp. B4 was investigated, and the effect of temperature on transformation was studied. RESULTS: Three metabolites were purified by preparative TLC and HPLC, and identified as androsta‐1,4‐diene‐3,17‐dione (ADD), 9α‐hydroxyandrost‐4‐ene‐3, 17‐dione (9α‐OH‐AD), and 3‐hydroxy‐9, 10‐secoandrost‐1, 3, 5‐triene‐9, 17‐dione (3‐OH‐SATD) by nuclear magnetic resonance imaging (NMR), Fourier transform infrared spectroscopy (FTIR) and mass spectroscopy (MS). It was first reported that the genus of Bordetella has the capability of AD degradation. Microbial transformation of AD was performed at 30 °C, 37 °C, 40 °C and 45 °C. The 9α‐OH‐AD yield reached a maximum within 16 h when the strain was cultivated in media with AD as sole carbon at 37 °C. Surprisingly, ADD was produced by the strain cultivated at 40 °C but not at 37 °C, which was different from previous reports. It was deduced that the alcohol dehydrogenase that catalyzed the transformation of AD to ADD may be temperature sensitive. CONCLUSION: Androst‐4‐ene‐3,17‐dione was converted into 9α‐hydroxyandrost‐4‐ene‐3, 17‐dione and other metabolites rapidly by Bordetella sp. B4. It is anticipated that the strain Bordetella sp. B4 CGMCC 2229 can be used in the steroids industry. Copyright © 2009 Society of Chemical Industry  相似文献   

2.
BACKGROUND: A large number of bacterial, fungal and microalgal species are able to bio‐transform steroid compounds. Among them, fungi from the Mucor genus have been shown to mediate hydroxylation, oxidation, and desaturation by the double bond formation and epoxidation of various steroid substances. Mucor racemocus has not been studied for its ability to modify androst‐1,4‐dien‐3,17‐dione, a pharmaceutically important steroid precursor. RESULTS: The filamentous fungus M. racemosus was applied for bioconversion of androst‐1,4‐dien‐3,17‐dione (ADD, I ) in a 5‐day fermentation. Microbial metabolites were purified chromatographically and identified on the basis of their spectral data as 17β‐hydroxyandrost‐1,4‐dien‐3‐one ( II ), 14α‐hydroxyandrost‐1,4‐dien‐3,17‐dione ( III ), 15α‐hydroxyandrost‐1,4‐dien‐3,17‐dione ( IV ), 15α,17β‐dihydroxyandrost‐1,4‐dien‐3‐one ( V ), 14α,17β‐dihydroxyandrost‐1,4‐dien‐3‐one ( VI ), and 6β,17β‐dihydroxyandrost‐1,4‐dien‐3‐one ( VII ). CONCLUSION: Observed modifications included hydroxylation at C‐6β, C‐14α, C‐15α positions and 17‐carbonyl reduction. The best fermentation conditions for production of hydroxysteroid‐1,4‐dien‐3‐one derivatives were found to be 25 °C at 150 rpm for 5 days with a substrate concentration of 0.5 g L?1. Copyright © 2009 Society of Chemical Industry  相似文献   

3.
4‐(4′‐Aminophenyl)‐1,2,4‐triazolidine‐3,5‐dione ( 1 ) was reacted with 1,8‐naphthalic anhydride ( 2 ) in a mixture of acetic acid and pyridine (3 : 2) under refluxing temperature and gave 4‐(4′‐N‐1,8‐naphthalimidophenyl)‐1,2,4‐triazolidine‐3,5‐dione ( NIPTD ) ( 3 ) in high yield and purity. The compound NIPTD was reacted with excess n‐propylisocyanate in N,N‐dimethylacetamide solution and gave 1‐(n‐propylamidocarbonyl)‐4‐[4′‐(1,8‐naphthalimidophenyl)]‐1,2,4‐triazolidine‐3,5‐dione ( 4 ) and 1,2‐bis(n‐propylamidocarbonyl)‐4‐[4′‐(1,8‐naphthalimidophenyl)]‐1,2,4‐ triazolidine‐3,5‐dione ( 5 ) as model compounds. Solution polycondensation reactions of monomer 3 with hexamethylene diisocyanate ( HMDI ), isophorone diisocyanate ( IPDI ), and tolylene‐2,4‐diisocyanate ( TDI ) were performed under microwave irradiation and conventional solution polymerization techniques in different solvents and in the presence of different catalysts, which led to the formation of novel aliphatic‐aromatic polyureas. The polycondensation proceeded rapidly, compared with conventional solution polycondensation, and was almost completed within 8 min. These novel polyureas have inherent viscosities in a range of 0.06–0.20 dL g?1 in conc. H2SO4 or DMF at 25°C. Some structural characterization and physical properties of these novel polymers are reported. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2861–2869, 2003  相似文献   

4.
Low density (≤13.9 mg cm?3), compressible poly(bis(benzimidazo)benzophenanthroline‐dione) (BBB) sponges with high temperature resistance are reported. The processing of BBB is limited due to its insolubility in organic solvents and infusibility. Therefore, the sponges are made in two steps: first, the BBB fibers are prepared by electrospinning the starting monomers with a template polymer followed by polycondensation of monomers on solid fibers at high temperature. In the second step, the BBB fibers are mechanically cut and self‐assembled from a dispersion during freeze‐drying. The use of poly(vinyl alcohol) is critical in getting self‐assembled hierarchically double‐pore‐structured, mechanically stable sponges. The sponges show very high pyrolytic stability, high compressibility (more than 92% recovery after 50% compression), very low thermal conductivity (0.028–0.038 W mK?1), and high oil absorption capacity.  相似文献   

5.
4‐(4′‐Aminophenyl)‐1,2,4‐triazolidine‐3,5‐dione was reacted with 1 mol of acetyl chloride in dry N,N‐dimethylacetamide (DMAc) at ?15°C and 4‐(4′‐acetamidophenyl)‐1,2,4‐triazolidine‐3,5‐dione [4‐(4′‐acetanilido)‐1,2,4‐triazolidine‐3,5‐dione] (APTD) was obtained in high yield. The reaction of the APTD monomer with excess n‐isopropylisocyanate was performed at room temperature in DMAc solution. The resulting bis‐urea derivative was obtained in high yield and was finally used as a model for the polymerization reaction. The step‐growth polymerization reactions of monomer APTD with hexamethylene diisocyanate, isophorone diisocyanate, and tolylene‐2,4‐diisocyanate were performed under microwave irradiation and solution polymerization in the presence of pyridine, triethylamine, or dibutyltin dilaurate as a catalyst. Polycondensation proceeded rapidly, compared with conventional solution polycondensation; it was almost completed within 8 min. The resulting novel polyureas had an inherent viscosity in the range of 0.07–0.17 dL/g in dimethylformamide or sulfuric acid at 25°C. These polyureas were characterized by IR, 1H‐NMR, elemental analysis, and thermogravimetric analysis. The physical properties and structural characterization of these novel polyureas are reported. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2103–2113, 2004  相似文献   

6.
An expression system based on Escherichia coli and the T5 promoter allowed the overproduction of a his‐tagged rhamnulose‐1‐phosphate aldolase (RhuA; EC 4.1.2.19), an enzyme with applications in the production of deoxyazasugars and deoxysugars compounds. Shake flask and bioreactor cultivation with E coli M15 (pQErham) were performed under different media and inducing conditions for RhuA expression. A Defined Medium (DM) with glucose as carbon source gave a high volumetric and enzyme productivity (3460 AU dm?3 and 288 AU dm?3 h?1 respectively) compared with Luria–Bertoni (LB) medium (2292 AU dm? 3 and 255 AU dm?3 h?1). The minimum quantity of (isopropyl‐β‐D ‐thiogalactoside) IPTG for optimal induction was estimated in 18–20 µmol IPTG gDCW?1. The highest volumetric production of RhuA (8333 AU dm?3) was obtained when IPTG was added in the late log‐phase. No significant differences were found in specific RhuA activity for induction temperatures of 30 and 37 °C. An effective two‐step purification process comprising affinity chromatography and gel permeation has been developed (overall recovery 66.5%). These studies provide the basis for the further development of an integrated process for recombinant RhuA production suitable for biotransformation applications. Copyright © 2003 Society of Chemical Industry  相似文献   

7.
4‐[4′‐(2‐Hydroxy‐1‐naphthylazo)phenyl]‐1,2,4‐triazolidine‐3,5‐dione ( HNAPTD ) ( 1 ) has been reacted with excess amount of n‐propylisocyanate in DMF (N,N‐dimethylformamide) solution at room temperature. The reaction proceeded with high yield, and involved reaction of both N? H of the urazole group. The resulting bis‐urea derivative 2 was characterized by IR, 1H‐NMR, elemental analysis, UV‐Vis spectra, and it was finally used as a model compound for the polymerization reaction. Solution polycondensation reactions of monomer 1 with Hexamethylene diisocyanate ( HMDI ) and isophorone diisocyanate ( IPDI ) were performed in DMF in the presence of pyridine as a catalyst and lead to the formation of novel aliphatic azo‐containing polyurea dyes, which are soluble in polar solvents. The polymerization reaction with tolylene‐2,4‐diisocyanate ( TDI ) gave novel aromatic polyurea dye, which is insoluble in most organic solvents. These novel polyureas have inherent viscosities in a range of 0.15–0.22 g dL?1 in DMF at 25°C. Some structural characterization and physical properties of these novel polymers are reported. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3177–3183, 2001  相似文献   

8.
Soybean extract residue (scum), a waste of soybean oil production, was examined as a raw material for C17‐ketosteroid production. As a model process, its bioconversion to 9α‐hydroxyandrost‐4‐ene‐3,17‐dione (9‐OH‐AD) by Mycobacterium sp VKM Ac‐1817D was studied. The content of transformable sterols (sitosterol, stigmasterol and campesterol) in scum was estimated at ~14%. The bioconversion of scum to 9‐OH‐AD was characterized by a long lag‐period (300–350 h) followed by 9‐OH‐AD accumulation. The microbial or chemical elimination of fatty non‐identified components resulted in sterol‐enriched scum preparations. Effective conversion of these preparations by Mycobacterium sp was demonstrated: 9‐OH‐AD molar yield ~65% was reached at 60 h from the scum preparation containing 10 g dm?3 transformable sterols. The process productivity was comparable with that for high quality‐sitosterol of wood origin (tall‐oil sitosterol). Copyright © 2004 Society of Chemical Industry  相似文献   

9.
In this article, graft copolymerization of N‐vinyl‐2‐pyrrolidone onto xanthan gum initiated by potassium peroxydiphosphate/Ag+ system in an aqueous medium has been studied under oxygen free nitrogen atmosphere. Grafting ratio, grafting efficiency, and add on increase on increasing the concentration of potassium peroxydiphosphate (2.0 × 10?3 to 12 × 10?3 mol dm?3), Ag+(0.4 × 10?3 to 2.8 × 10?3 mol dm?3), and hydrogen ion concentration from 2 × 10?3 to 14.0 × 10?3 mol dm?3. Maximum grafting has been obtained when xanthan gum and monomer concentration were 0.4 g dm?3 and 16 × 10?2 mol dm?3, respectively, at 35°C and 120 min. Water swelling capacity, swelling ratio, metal ion uptake, and metal retention capacity have also been studied, and it has been found that graft copolymer shows enhancement in these properties than pure xanthan gum. The graft copolymer has been characterized by FTIR and thermal analysis. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

10.
The direct treatment of whey wastewater at various sludge ages (10–75 days) and high biomass concentration (above 50 g mixed liquor suspended solid (MLSS) dm?3) in a submerged membrane bioreactor (sMBR) is described. The chemical oxygen demand (COD) of raw whey varied in the range of 60 and 90 g dm?3. After feeding the sMBR with raw whey, effluent COD reduced to about 20 g dm?3. The effluent was free of suspended solids and total coliform bacteria. Total phosphorus (TP) and orthophosphate (Ortho‐P) in the influent varied between 204 and 880 mg dm?3 and between 180 and 620 mg dm?3, and effluent TP and Ortho‐P reduced to 113 and 109 mg dm?3, respectively. The ammonium and nitrate concentrations in the influent were in the ranges of 3.4 and 120 mg dm?3 and 10 and 503 mg dm?3, respectively. The effluent ammonium concentration varied between 17.6 and 198 mg dm?3 and nitrate concentrations varied between 0.9 and 69 mg dm?3. Effluent turbidity varied between 23 and 111 FAU (Formazin Attenuation Unit). The results show that sMBR is an effective pre‐treatment system for high‐strength agro‐wastewaters because of its ability to reduce the pollution load. Copyright © 2004 Society of Chemical Industry  相似文献   

11.
β‐fructofuranosidase (EC 3.2.1.26) from Aspergillus sp 27H isolated from soil was investigated for production of fructooligosaccharides (FOS) using whole cells. It possesses hydrolytic and transfructosylating activities that can be altered by modifying the reaction conditions. The optimal conditions for the transfructosylating activity occur in the pH range 5.5–6.0 and at 60 °C, while hydrolytic activity was highest at pH 4.0 and 55 °C. At low sucrose concentration (10 g dm?3) there was rapid conversion of sucrose to glucose and fructose and very low concentrations of FOS were obtained. However, at sucrose concentrations higher than 216 g dm?3 the concentrations of hydrolysis products were reduced. Under the following conditions: pH 5.5, temperature 40 °C, sucrose concentration 615 g dm?3 and enzyme concentration 20β‐fructofuranosidase units g?1 of sucrose, the FOS concentration reached a maximum value of 376 g dm?3 (234 g dm?3 1‐kestose and 142 g dm?3 nystose) and the proportion of FOS in the solids in the reaction mixture was 600–620 g kg?1 at 6 h. These results suggest that β‐fructofuranosidase from Aspergillus sp 27H could be an appropriate enzyme for the commercial production of FOS. Copyright © 2004 Society of Chemical Industry  相似文献   

12.
The effect of the reaction conditions on the grafting parameters during grafting of 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid onto sodium carboxymethylcellulose using H2O2/Fe+2 redox pair are studied at 30°C. The grafting ratio, add on, and conversion initially increase with the H2O2 concentration in the range of (10.0–15.0) × 10?2 mol dm?3. Thereafter, these parameters decrease with the H2O2 concentration. The grafting ratio, add on, and conversion increase when increasing the ferrous ion concentration from (0.5 to 4.0) × 10?2 mol dm?3 and decrease with a further increase in the concentration. It is observed that the grafting ratio and add on increase with the monomer concentration, whereas the conversion decrease. The hydrogen ions seem to be facilitating the grafting reaction up to a certain concentration and after this concentration seem to be retarding the process. The grafting ratio, add on, and conversion decrease with the sodium carboxymethylcellulose concentration. When increasing the time period from 60 to 90 min, the grafting parameters increase but decrease thereafter. Similarly, when increasing the temperature from 25 to 30°C, the grafting parameters increase and decrease thereafter. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4819–4825, 2006  相似文献   

13.
BACKGROUND: Arthrobacter simplex cells immobilised in sodium cellulose sulfate/poly‐dimethyl‐diallyl‐ammonium chloride microcapsules were used for the microbial dehydrogenation of 11α‐hydroxy‐16α,17‐epoxyprogesterone to 11α‐hydroxy‐16α,17α‐epoxypregn‐1,4‐diene‐3,20‐dione in an aqueous/organic solvent two‐liquid‐phase system, which is a key reaction in the production of glucocorticoid pharmaceuticals. The aim of the study was to establish a suitable aqueous/organic solvent two‐liquid‐phase system for performing semi‐continuous production in an airlift loop reactor by encapsulated A. simplex cells with the addition of suitable surfactants to achieve a higher yield of the product. RESULTS: n‐Hexane was selected as the most suitable organic solvent. In optimised Tween‐80 emulsion feed mode the conversion in the airlift loop reactor was as high as 97.54% when the time of reaction was 2 h, and the reaction time was greatly shortened. In semi‐continuous production the cultivation with immobilised cells was carried out for five batches in total. The conversion in each batch was above 95% and the enzymatic activity still remained quite high after five batches of biotransformation. CONCLUSION: The results showed that performing the conversion by this method shortened the reaction time and increased the productivity, thus demonstrating the great potential of the method for the dehydrogenation of 11α‐hydroxy‐16α,17‐epoxyprogesterone. Copyright © 2008 Society of Chemical Industry  相似文献   

14.
A new series of conjugated copolymers (PBDT‐TPD , PBDT ‐Th‐TPD , PBDT‐TT‐TPD ) containing donor–acceptor (D ? A) structure electron‐rich benzo[1,2‐b :4,5‐b ′]dithiophene (BDT ) units with branched alkyl thiophene side chains and electron‐deficient 5‐(2‐octyl)‐4H ‐thieno[3,4‐c ]pyrrole‐4,6(5H )‐dione (TPD) units was designed and synthesized. To tune the optical and electrochemical properties of the copolymers, the conjugation length of the copolymers was extended by introducing π‐conjugated spacers such as thiophene and thieno[3,2‐b ]thiophene units. It was observed that PBDT‐TPD showed broader absorption spectra in the longer wavelength region and the absorption maximum was red‐shifted compared to that of PBDT‐Th‐TPD, PBDT‐TT‐TPD. Stokes shifts were calculated to be 52 nm for PBDT‐TPD, 153 nm for PBDT‐Th‐TPD and 146 nm for PBDT‐TT‐TPD. Further, PBDT‐TPD exhibited a deeper highest occupied molecular orbital energy level of ?5.53 eV as calculated by cyclic voltammetry. Bulk heterojunction solar cells fabricated using PBDT‐TPD as donor material exhibited a power conversion efficiency of 1.92%. © 2017 Society of Chemical Industry  相似文献   

15.
Tetralin‐1,4‐dione, the stable tautomer of dihydroxynaphthalene, was reduced with catecholborane in the presence of 3,3‐diphenyl‐1‐butyltetrahydro‐3H‐pyrrolo[1,2‐c][1,3,2]oxazaborole as catalyst to give enantiomerically highly enriched 4‐hydroxy‐1‐tetralone (99% ee) in an efficient one‐pot procedure. The R‐enantiomer provided a rapid access to sertraline while the S‐enantiomer was converted into 2‐epicatalponol and catalponol. A more selective enantioselective route to the antithermitic catalponol made use of the planar chiral tricarbonylchromium complex of hydroxytetralone. Its precursor chromium(tricarbonyl)[η6‐(1‐4,4a,8a)‐tetralin‐5,8‐dione] was obtained via direct complexation of 1,4‐dihydroxynaphthalene using chromium(tricarbonyl)‐ tris(ammonia) and boron trifluoride etherate as source of the chromium(tricarbonyl) fragment. Enolate prenylation was best carried out in the presence of a tetraamine ligand. Complete inversion of the stereogenic center bearing the prenyl group of the initially obtained tetralone complex was achieved via enolate formation followed by protonation.  相似文献   

16.
Graft copolymerization of 4‐vinylpyridine (4‐VP) onto guar gum (GOH) using potassium monopersulfate (PMS)/thioacetamide (TAA) as a redox pair was studied in an aqueous medium under inert atmosphere. The concentration of potassium monopersulfate and thioacetamide should be 1.0 × 10?2 and 5.0 × 10?3 mol dm?3, respectively, for highest grafting ratio and efficiency. Efficient grafting was observed at 19.25 × 10?2 and 4.87 × 10?2 mol dm?3 concentration of 4‐vinylpyridine and sulfuric acid, respectively. The optimum temperature for grafting is 30°C. As the time period of reaction is increased, the grafting ratio increases, whereas efficiency decreases. The plausible mechanism of grafting has been suggested. A sample of guar gum and guar‐ g‐4‐vinylpyridine were subjected to thermogravimetric analysis with the objective of studying the effect of grafting 4‐vinylpyridine on the thermal stability of guar gum. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2380–2385, 2002  相似文献   

17.
A pilot‐scale anaerobic/aerobic ultrafiltration system was tested to treat high‐strength tomato‐processing wastewater, to achieve stringent dry‐ditch discharge criteria of soluble biochemical oxygen demand (SBOD) <10 mg dm?3, total suspended solids <10 mg dm?3, ammonia nitrogen <3 mg dm?3 and soluble phosphorus <0.5 mg dm?3. The anaerobic/aerobic system achieved 99.4% SBOD removal, 91.9% NH3 N removal and 100% phosphorus removal at an overall hydraulic retention time of 1.5 days and solids retention time of 5 days during the tomato canning season. Respirometric studies confirmed that the pretreatment of tomato‐processing wastewater in the anaerobic reactor increased the readily biodegradable fraction, improved kinetics, and eliminated nutrient deficiency problem. Copyright © 2006 Society of Chemical Industry  相似文献   

18.
The removal of phenol by peroxidase‐catalysed polymerization was examined using Coprinus cinereus peroxidase in the presence of surfactants. The non‐ionic surfactants with poly(oxyethene) residues, Triton X‐100, Triton X‐405 and Tween 20, enhanced the phenol removal efficiency at a level similar to high relative molecular mass poly(ethylene glycol) (relative molecular mass 3000). Although the improvement in the removal efficiency was less than that of Triton X‐100, Span 20, sodium lauryl sulfate (SDS) and lauryl trimethylammonium bromide (DTAB) also enhanced the removal efficiency. The requirement of the enzyme for almost 100% removal of 100 mg dm?3 phenol decreased to one‐fourth by the addition of 30 mg dm?3 Triton X‐100. Triton X‐100, Triton X‐405, Tween 20 and DTAB could reactivate the enzyme precipitated with the phenol polymer, leading to the restarting of the phenol removal reaction. Copyright © 2003 Society of Chemical Industry  相似文献   

19.
Unreported graft copolymer of 2‐acrylamido‐2‐methyl‐1‐propanesulphonic acid (AMPS) with sodium carboxymethylcellulose (Na‐CMC) was synthesized and reaction conditions were optimized using a bromate/thiourea redox pair under an inert atmosphere at 40°C. Grafting ratio, add on, and conversion increase as the concentration of thiourea and [H+] increases up to 3.6 × 10?3 and 0.6 × 10?2 mol dm?3, respectively, while on increasing the concentration of bromate ion and Na‐CMC, grafting ratio, add on, and conversion decrease. The samples of Na‐CMC and grafted Na‐CMC with AMPS were subjected to thermogravimetric analysis, with the objective of studying the effect of grafting of AMPS on the thermal stability of graft copolymer. The graft copolymer was found to be more thermally stable than pure Na‐CMC. Comparing the IR spectra of pure with grafted Na‐CMC confirm the evidence of grafting. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 100: 26–34, 2006  相似文献   

20.
The poly‐o‐toluidine (POT) was prepared under different magnetization in solution containing 0.5 mol dm?3o‐toluidine, 1.0 mol dm?3 HCl with and without 0.5 mol dm?3 DyCl3, respectively. Their conductivity, UV–vis, FTIR spectra, X‐ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscope (SEM) were investigated. The results of conductivity showed that magnetic field and the cooperative effect of Dy3+ and magnetic field do obvious effect to conductivity of POT. Meantime, they also can make the energy for the π–π* transitions and quinoid ring transition in UV–vis spectra smaller. At high magnetization the peaks of POT due to Q? NH+? B or B? NH+? B and C? H out of plane on 1,4‐ring or 1,2,4‐ring disappeared in FTIR spectra. Magnetic field and Dy3+ can make three dimensions morphologies of the POT clear, but they scarcely affect the crystallinity of POT. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2174–2179, 2007  相似文献   

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