首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   499篇
  免费   37篇
  国内免费   12篇
化学   389篇
晶体学   2篇
力学   18篇
数学   40篇
物理学   99篇
  2024年   1篇
  2023年   2篇
  2022年   11篇
  2021年   16篇
  2020年   24篇
  2019年   26篇
  2018年   25篇
  2017年   20篇
  2016年   39篇
  2015年   25篇
  2014年   43篇
  2013年   66篇
  2012年   39篇
  2011年   38篇
  2010年   42篇
  2009年   16篇
  2008年   25篇
  2007年   17篇
  2006年   18篇
  2005年   11篇
  2004年   12篇
  2003年   8篇
  2002年   11篇
  2001年   2篇
  2000年   2篇
  1998年   1篇
  1993年   3篇
  1992年   2篇
  1990年   1篇
  1986年   1篇
  1981年   1篇
排序方式: 共有548条查询结果,搜索用时 515 毫秒
21.
Alkyl halides are efficiently converted to their corresponding S-alkyl thioacetates under mild and nonaqueous conditions, using polymer-supported sodium thioacetate as a new polymeric reagent at room temperature in high yields and purity. The spent polymeric reagent can be removed quantitatively by filtration and pure products can be obtained by evaporation of the solvent. The spent polymeric reagent can be regenerated and reused several times without its activity changing appreciably.  相似文献   
22.
The emergence of multi‐drug resistant (MDR) bacteria and dynamic pattern of infectious diseases demand to develop alternative and more effective therapeutic strategies. Silver nanoparticles (AgNPs) are among the most widely commercialized engineered nanomaterials, because of their unique properties and increasing use for various applications in nanomedicine. This study for the first time aimed to evaluate the antibacterial and antibiofilm activities of newly synthesized nanochelating based AgNPs against several Gram‐positive and ‐negative nosocomial pathogens. Nanochelating technology was used to design and synthesize the AgNPs. The cytotoxicity was tested in human cell line using the MTT assay. AgNPs minimal inhibitory concentration (MIC) was determined by standard broth microdilution. Antibiofilm activity was assayed by a microtiter‐plate screening method. The two synthesized AgNPs including AgNPs (A) with the size of about 20‐25 nm, and AgNPs (B) with 30‐35 nm were tested against Staphylococcus aureus, Staphylococcus epidermidis, Acinetobacter baumannii, and Pseudomonas aeruginosa. AgNPs exhibited higher antibacterial activity against Gram‐positive strains. AgNPs were found to significantly inhibit the biofilm formation of tested strains in concentration 0.01 to 10 mg/mL. AgNPs (A) showed significant effective antibiofilm activity compared to AgNPs (B). In summary, our results showed the promising antibacterial and antibiofilm activity of our new nanochelating based synthesized AgNPs against several nosocomial pathogens.  相似文献   
23.
We report a new simple technique for the simultaneous measurements of absorption-, emission cross-sections, background loss coefficient, and dopant density of doped optical fibers with low dopant concentration. Using our proposed technique, the experimental characterization of a sample Ge–Er-doped optical fiber is presented, and the results are analyzed and compared with other reports. This technique is suitable for production line of doped optical fibers.  相似文献   
24.
In this work a cloud-point extraction has been used for the preconcentration of the trace amounts of titanium after complex formation with morin (2′,3,4′,5,7-pentahydroxyflavone) using Triton X-114 as surfactant. The chemical variables affecting the phase separation and the viscosity affecting the detection by flame atomic absorption spectrometry (FAAS) were optimized. At pH 4.5, preconcentration of 50 mL of sample in the presence of 0.08% Triton X-114 and 1.0 × 10?4 M morin enabled the detection limit (c L = 3S b/m) of 2.9 ng/mL titanium and linear range 0.02–2.0 μg/mL to be achived. The preconcentration factor was 61, and the relative standard deviation was 3.8% for 0.1 μg/mL solution of Ti(IV) by repeated assays (n = 9). The proposed method has been applied to the determination of titanium in well water, spiked water and plant (Haloxylon).  相似文献   
25.
A new solid phase extraction (SPE) method has been developed for the speciation of Cr(III) and Cr(VI). This method is based on the adsorption of Cr(VI) on modified alumina‐coated magnetite nanoparticles (ACMNPs). Total chromium in different samples was determined as Cr(VI) after oxidation of Cr(III) to Cr(VI) using H2O2. The chromium concentration has been determined by flame atomic absorption spectrometric (FAAS) technique and amount of Cr(III) was calculated by substracting the concentration of Cr(VI) from total chromium concentration. The effect of parameters such as pH, amount of adsorbent, contact time, sample volume, eluent type, H2O2 concentration and cetyltrimethylammonium bromide (CTAB) concentration as modifier on the quantitative recovery of Cr(VI) were investigated. Under the optimal experimental conditions, the preconcentration factor, detection limit, linear range and relative standard deviation (RSD) of Cr(VI) were 140 (for 350 mL of sample solution), 0.083 ng mL?1, 0.1‐10.0 ng mL?1 and 4.6% (for 5.0 ng mL?1, n = 7), respectively. This method avoided the time‐consuming column‐passing process of loading large volume samples in traditional SPE through the rapid isolation of CTAB@ACMNPs with an adscititious magnet. The proposed method was successfully applied to the determination and speciation of chromium in different water and wastewater samples and suitable recoveries were obtained.  相似文献   
26.
The reduction of a variety of carbonyl compounds was efficiently carried out with NaBH4/DOWEX(R)50WX4 system. The reactions were performed to give the corresponding alcohols derivatives in perfect yields in THF at room temperature. Reduction of acyloins and a‐diketones by this reducing system produced efficiently the corresponding vicinal diols. Also, the reduction of aldehydes over ketones has been accomplished successfully by this system. Regioselectivity of this system was also investigated with exclusive 1,2‐reduction of conjugated carbonyl compounds to their corresponding allylic alcohols in high to excellent yields.  相似文献   
27.
A novel chiral ionic liquid (CIL) based on nicotinium salt has been synthesized and used as an efficient asymmetric chiral catalyst for reduction of acetophenone derivatives with NaBH4 in methanol at room temperature. The optically active alcohols were obtained in low to moderate enantiomeric excess in a short reaction time.  相似文献   
28.
Various types of trimethylsilyl and tert-butyldimethylsilyl ethers of primary and secondary benzylic alcohols could be selectively converted to their corresponding carbonyl compounds with MnO2 in the presence of AlCl3 in good to excellent yields.  相似文献   
29.
Lipases are one of the highest value commercial enzymes as they have broad applications in detergent, food, pharmaceutical, and dairy industries. To provide chimeric Bacillus thermocatenulatus lipase (BTL2), the completely conserved pentapeptide (112Ala-His-Ser-Gln-Gly116) was replaced with similar sequences (207Gly-Glu-Ser-Ala-Gly211) of Candida rugosa lipase (CLR) at the nucleophilic elbow region. For this purpose, three mutations including A112G, H113E, and Q115A were inserted in the conserved pentapeptide sequence of btl2 gene. Based on the crystal structures of 2W22, the best structure of opened form of the chimeric lipases were garnered using the MODELLER v9.10 software. The native and chimeric lipases were docked to a set of ligands, and a trial version of Molegro Virtual Docker (MVD) software was used to obtain the energy values. Docking results confirmed chimeric lipase to be better than the native lipase. Following the in silico study, cloning experiments were conducted and expression of native and chimeric btl2 gene in Pichia pastoris was performed. The native and chimeric lipases were purified, and the effect of these mutations on characteristics of chimeric lipase studied and then compared with those of native lipase. Chimeric lipase exhibited 1.6-fold higher activity than the native lipase at 55 °C. The highest percentage of both lipases activity was observed at 60 °C and pH of 8.0. The ion Ca2+ slightly inhibited the activity of both lipases, whereas the organic solvent enhanced the lipase stability of chimeric lipase as compared with the native lipase. According to the results, the presence of two glycine residues at the conserved pentapeptide region of this chimeric lipase (112 Gly-Glu-Ser-Ala-Gly 116) may increase the flexibility of the nucleophilic elbow region and affect the enzyme activity level.  相似文献   
30.
In this study, the effect of phosphorous compound concentration on the production of glucosamine by Mucor indicus was investigated. Changes in the yield of ethanol, the major metabolite of the fungus, were also followed besides. The alkali insoluble material of the biomass of the fungus mainly contained phosphates and polymers of glucosamine and N-acetyl glucosamine, i.e., chitin and chitosan. Yields of glucosamine (78–113 g/kg dry fungal biomass) and ethanol (200–370 g/kg glucose) were significantly affected by the phosphorous concentration. The results showed that lower concentrations of phosphorous favored the production of glucosamine while higher ethanol as well as biomass yields was obtained at higher concentrations. The best concentration was 0.5 g/l where glucosamine yield was 0.37 g/l (11 % of the biomass). At this phosphate concentration, ethanol and biomass yields were 360 and 76 g/kg glucose, respectively. On average, proteins comprised 51.5 % of the biomass. Glycerol was the second important metabolite during the fermentation by the fungus which appeared at lower yields (20–34 g/kg glucose).  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