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41.
A Peroxygenase from Chaetomium globosum Catalyzes the Selective Oxygenation of Testosterone 下载免费PDF全文
Jan Kiebist Dr. Kai‐Uwe Schmidtke Jörg Zimmermann Dr. Harald Kellner Dr. Nico Jehmlich Dr. René Ullrich Daniel Zänder Prof. Dr. Martin Hofrichter Prof. Dr. Katrin Scheibner 《Chembiochem : a European journal of chemical biology》2017,18(6):563-569
Unspecific peroxygenases (UPO, EC 1.11.2.1) secreted by fungi open an efficient way to selectively oxyfunctionalize diverse organic substrates, including less‐activated hydrocarbons, by transferring peroxide‐borne oxygen. We investigated a cell‐free approach to incorporate epoxy and hydroxyl functionalities directly into the bulky molecule testosterone by a novel unspecific peroxygenase (UPO) that is produced by the ascomycetous fungus Chaetomium globosum in a complex medium rich in carbon and nitrogen. Purification by fast protein liquid chromatography revealed two enzyme fractions with the same molecular mass (36 kDa) and with specific activity of 4.4 to 12 U mg?1. Although the well‐known UPOs of Agrocybe aegerita (AaeUPO) and Marasmius rotula (MroUPO) failed to convert testosterone in a comparative study, the UPO of C. globosum (CglUPO) accepted testosterone as substrate and converted it with total turnover number (TTN) of up to 7000 into two oxygenated products: the 4,5‐epoxide of testosterone in β‐configuration and 16α‐hydroxytestosterone. The reaction performed on a 100 mg scale resulted in the formation of about 90 % of the epoxide and 10 % of the hydroxylation product, both of which could be isolated with purities above 96 %. Thus, CglUPO is a promising biocatalyst for the oxyfunctionalization of bulky steroids and it will be a useful tool for the synthesis of pharmaceutically relevant steroidal molecules. 相似文献
42.
Pipecolic Acid Hydroxylases: A Monophyletic Clade among cis‐Selective Bacterial Proline Hydroxylases that Discriminates l‐Proline 下载免费PDF全文
Johanna Mattay Dr. Wolfgang Hüttel 《Chembiochem : a European journal of chemical biology》2017,18(15):1523-1528
Proline hydroxylases are iron(II)/2‐oxoglutarate‐dependent enzymes that hydroxylate l ‐proline and derivatives, such as l pipecolic acid, which is the six‐membered‐ring homologue of l ‐proline. It has been established that there is a distinct group of conserved bacterial enzymes that hydroxylate l ‐pipecolic acid and trans‐3‐ and trans‐4‐methyl‐l ‐proline, but virtually no l ‐proline. This allows the organism to produce hydroxyproline congeners without hydroxylation of the physiologically omnipresent l ‐proline. In vitro conversions showed that the substrate spectrum of the pipecolic acid hydroxylases GetF (from a Streptomyces sp.; producer of the tetrapeptide antibiotic GE81112) and PiFa (from Frankia alni) overlaps that of proline hydroxylases, except for the nonacceptance of l ‐proline and smaller homologues. Distinct and conserved residues were determined for both types of enzymes. However, site‐directed mutagenesis in GetF did not yield variants that accepted l ‐proline; this suggested a complex interaction of several residues around the active site, which resulted in delicate changes in substrate specificity. This is supported by substrate docking in a homology model of GetF, which revealed an altered orientation for l ‐proline relative to that of preferred substrates. 相似文献
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Mantri M Loik ND Hamed RB Claridge TD McCullagh JS Schofield CJ 《Chembiochem : a European journal of chemical biology》2011,12(4):531-534
Amino acid analyses reveal that JMJD6-catalysed hydroxylation of RNA-splicing regulatory protein fragments occurs to give hydroxylysine products with 5S stereochemistry. This contrasts with collagen lysyl hydroxylases, which give 5R-hydroxylated products. The work suggests that more than one subfamily of lysyl hydroxylases has evolved and illustrates the importance of stereochemical assignments in proteomic analyses. 相似文献
45.
苯酚直接羟化制备苯二酚为液-固相的强放热快反应,催化剂的活性衰减很快,催化剂失活对催化过程的工艺流程、设备及操作条件的选择起着决定性的作用,本文利用催化剂的活性关联式计算了不同流程和操作条件下反应器中催化剂的平均活性,结果表明:宜采用三釜阶式串联反应流程,催化剂回用比例为0.8,过氧化氢加人总量应与平均活性相对应,调节回用比例可控制产物分布,延长催化剂开始失活时间有利于减少生产成本。 相似文献
46.
探索不同乳化剂sp60、sp80、tw60、tw80及其复合乳化剂对坎利酮羟基化的影响。结果表明乳化剂对坎利酮有增溶作用,且tw80、复合乳化剂tw80—sp60对坎利酮微生物转化有促进作用。其中单组分乳化剂tw80的最佳质量分数为0.18%,转化率为90.32%;复合乳化剂tw80-sp60,最佳质量分数为0.09%,转化率为92.22%。 相似文献
47.
Selective oxidation reactions like the oxyfunctionalization of alkanes, hydroxylation of aromatics and sulfoxidation of thioethers have been carried out with dilute hydrogen peroxide over titanium and vanadium metallosilicate molecular sieves with MEL topology, viz., TS-2 and VS-2. Though both the catalysts possess similar activities, substantial differences in the product distribution are observed. The oxyfunctionalization of the primary carbon atoms of the alkanes and the oxidation of the methyl substituents of the aromatic hydrocarbons distinguish VS-2 from TS-2. Both the catalysts are found to be equally active in the hydroxylation of phenol, though they possess different activities in different solvents. In general, the oxidations are deeper over VS-2 than on TS-2. 相似文献
48.
Guangde Jiang Yi Zhang Magan M. Powell Sarah M. Hylton Nicholas W. Hiller Prof. Rosemary Loria Prof. Yousong Ding 《Chembiochem : a European journal of chemical biology》2019,20(8):1068-1077
Cytochrome P450 enzymes generally functionalize inert C−H bonds, and thus, they are important biocatalysts for chemical synthesis. However, enzymes that catalyze both aliphatic and aromatic hydroxylation in the same biotransformation process have rarely been reported. A recent biochemical study demonstrated the P450 TxtC for the biosynthesis of herbicidal thaxtomins as the first example of this unique type of enzyme. Herein, the detailed characterization of substrate requirements and biocatalytic applications of TxtC are reported. The results reveal the importance of N-methylation of the thaxtomin diketopiperazine (DKP) core on enzyme reactions and demonstrate the tolerance of the enzyme to modifications on the indole and phenyl moieties of its substrates. Furthermore, hydroxylated, methylated, aromatic DKPs are synthesized through a biocatalytic route comprising TxtC and the promiscuous N-methyltransferase Amir_4628; thus providing a basis for the broad application of this unique P450. 相似文献
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石墨相氮化碳(g-C3N4)以其独特的电子结构和化学特性引起了广泛关注。以双氰胺和硝酸铁为原料,制备了Fe改性的石墨相氮化碳(Fe/ g-C3N4),采用红外光谱、XRD和N2吸附-脱附等分析手段对g-C3N4和 Fe/g-C3N4 进行了表征,并用以催化苯酚羟基化反应合成二酚,研究了Fe/ g-C3N4催化性能的影响因素。结果表明,Fe/ g-C3N4材料具有良好的介孔结构,Fe的引入改变了g-C3N4层状结构的层间距。当苯酚/H2O2摩尔比为2/1、铁负载量为0.7%(质量分数)、反应温度为50 ℃、反应时间为6 h时,苯酚的转化率达到39.7%,邻苯二酚和对苯二酚的总选择性为85.8%。重复实验结果证实该催化剂可以重复使用。 相似文献