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   1363篇
  免费   44篇
  国内免费   13篇
化学   1036篇
晶体学   24篇
力学   40篇
数学   107篇
物理学   213篇
  2024年   3篇
  2023年   11篇
  2022年   83篇
  2021年   99篇
  2020年   51篇
  2019年   60篇
  2018年   48篇
  2017年   24篇
  2016年   70篇
  2015年   43篇
  2014年   71篇
  2013年   113篇
  2012年   112篇
  2011年   108篇
  2010年   68篇
  2009年   58篇
  2008年   77篇
  2007年   49篇
  2006年   40篇
  2005年   34篇
  2004年   33篇
  2003年   21篇
  2002年   19篇
  2001年   5篇
  2000年   15篇
  1999年   8篇
  1998年   10篇
  1997年   2篇
  1996年   6篇
  1995年   4篇
  1994年   6篇
  1993年   5篇
  1992年   6篇
  1991年   7篇
  1990年   6篇
  1989年   8篇
  1988年   4篇
  1987年   6篇
  1985年   2篇
  1984年   3篇
  1983年   2篇
  1982年   1篇
  1981年   4篇
  1980年   5篇
  1979年   4篇
  1977年   2篇
  1975年   1篇
  1973年   2篇
  1970年   1篇
排序方式: 共有1420条查询结果,搜索用时 0 毫秒
291.
Blood samples were acquired from 60 women aged 20–44 years having decreased fertility, infertile or with uterine tumors in the Iraqi Kurdistan region. The concentrations of α emitters in fresh blood ranged from 0.0029 to 0.0088 ppm, whereas those in powdered blood ranged from 0.0036 ppm in Eiskan to 0.0096 ppm in Halabjay–Kon in Sulaymania. The α emitter concentrations in fresh blood ranged from 0.0029 to 0.0139 ppm, whereas those in powdered blood ranged from 0.0031 ppm in Shorsh to 0.0146 ppm in Sedakan in the Erbil Governorate. However, the concentrations of α emitters in the blood of women with decreased fertility were higher in the North than women from South Iraq. The difference significantly p < 0.001 revealed higher means of track density of fresh and powder blood in Erbil compared to Sulaymania. α are more damaging to the living tissue and exposure of the gonads leads to decreased fertility in women, most of data have been significant therefore, the result shown the radiation effect on women fertility.  相似文献   
292.
A series of N‐heterocyclic carbene (NHC) precursors, 1‐methoxylethyl‐3‐allylimidazolium hexafluorophosphate ( 1 ), 1‐ethyl‐3‐allylimidazolium hexafluorophosphate ( 2 ), and 1‐pentyl‐3‐allylimidazolium hexafluorophosphate ( 3 ) were synthesized. These salts were treated with Ag2O to afford their corresponding mononuclear Ag(I)‐NHC complexes, namely 1‐methoxylethyl‐3‐allylimidazolium silver(I) hexafluorophosphate ( 4 ), 1‐ethyl‐3‐allylimidazolium silver(I) hexafluorophosphate ( 5 ), and 1‐pentyl‐3‐allylimidazolium silver(I) hexafluorophosphate ( 6 ), respectively. These compounds were characterized by physicochemical and spectroscopy techniques. Compounds 4 and 5 were structurally characterized by single crystal X‐ray diffraction, and their stability in solution was investigated and found to be acceptable for the antibacterial studies. These new NHC precursors and their respective Ag–NHC complexes were screened for their antibacterial activities against Staphylococcus aureus (ATCC 12600) and Escherichia coli (ATCC 25922). Compounds 1–3 showed no inhibition, whereas 4–6 inhibited the growth of these bacteria. The nuclease activities of the reported compounds against plasmid DNA and RNA were assessed by gel electrophoresis, and the results indicate that complexes 5 and 6 can degrade both DNA and RNA in the absence of an oxidant.  相似文献   
293.
Spectroscopic methods and theoretical calculations were used to study the photophysical properties of colchicine (1). The characteristic bands of colchicine (1) transitions occurring at ∼245 nm and 350 nm arise from n–π * and ππ * transitions, and were found to be blue shifted with increasing polarity index of the solvent and red shifted (bathocrhomic) with increasing acidity of the media. Solvent type and polarity were found to affect both the rate constant and photo conversion yield. Excitation of colchicine (1) at 366 nm populates the S1 orbital, from which the photoreaction of colchicine (1) initially produces lumicolchicine directly in its ground state by a concerted disrotatory electrocyclization (i.e., 4π electrocyclization involving the tropolone ring). The acidity of the media affects both rate constants and conversion yield; both of these were inversely proportional to the acid concentration. The presence of acid decreases the photo conversion yield of colchicine (1) from 90% to 40%. The ionic strength affects both the rate constants and the photo conversion yield; rate constants are inversely related to the ionic strength. The photochemistry of colchicine (1) is explained on the basis of the initial formation of a solvation complex in the ground state.  相似文献   
294.
A method for the extraction and gas chromatographic determination of methylmercury in biological matrices is presented. By combining the advantages of two extraction techniques-microwave-assisted extraction (MAE) and solid-phase microextraction (SPME)--the separation of methylmercury from biological samples is possible. Specifically, the procedure involves microwave extraction with 3 M hydrochloric acid, followed by aqueous-phase derivatization with sodium tetraphenylborate and headspace SPME with a silica fibre coated with polydimethylsiloxane (PDMS). For optimization of the derivatization-SPME procedure, a central composite experimental design with alpha = 1.682 and two central points was used to model gas-chromatographic peak areas as functions of pH, extraction temperature and sorption time. A desirability function was then used for the simultaneous optimization for methylmercury and Hg(II). The optimal derivatization-SPME conditions identified were close to pH 5, temperature 100 degrees C, and sorption time 15 min. The identification and quantification of the extracted methylmercury is carried out by gas chromatography with microwave-induced plasma atomic emission spectrometry detection. The validity of the new procedure is shown by the results of analyses of certified reference materials.  相似文献   
295.
A new neolignan, 3,4-dimethoxy-3',4'-methylenedioxy-2,9-epoxy-6,7-cyclo-1,8-neolign-11-en-5(5H)-one, which has been named (+)-kunstlerone (1), together with six known alkaloids: (+)-norboldine (2), (+)-N-methylisococlaurine (3), (+)-cassythicine (4), (+)-laurotetanine (5), (+)-boldine (6) and (-)-pallidine (7), were isolated from the leaves of Beilschmiedia kunstleri. The structures were established through various spectroscopic methods notably 1D- and 2D-NMR, UV, IR and LCMS-IT-TOF. (+)- Kunstlerone (1) showed a strong antioxidant activity, with an SC(50) of 20.0 μg/mL.  相似文献   
296.
Ferritin was immobilized on a glassy carbon electrode with electrodeposited cobalt oxide nanoparticles, and its direct electron transfer behavior was studied. It exhibits a pair of redox peaks due to direct electron transfer between ferritin and the nanoparticles. Electrochemical parameters including the formal potential (E0??), the charge transfer coefficient (??), and the apparent heterogeneous electron transfer rate constant (ks) were determined. The sensor displays excellent biocatalytic activity in terms of reduction of hydrogen peroxide, and this was applied to electrochemical sensing of hydrogen peroxide.
Figure
In this work, cobalt oxide nanoparticles were electrodeposited on the surface of an electrode for immobilization of ferritin molecules to prepare hydrogen peroxide biosensor. The immobilized protein molecules still preserve their biological activities and have great capability in catalyzing the reduction of hydrogen peroxide.  相似文献   
297.
Five new limonoids, ceramicines E-I (1-5), have been isolated from the bark of Chisocheton ceramicus. The structures and relative stereochemistry of them were fully elucidated based on 1D- and 2D-NMR data. Ceramicines E-I (1-5) exhibited moderate cell growth inhibitory activities on a range of cell lines (HL-60, A549, MCF7, and HCT116). The absolute structure of previously isolated ceramicine B (6) was also elucidated by circular dichroism (CD) and X-ray analysis.  相似文献   
298.
Methanol–chloroform based protein precipitation is an essential step in many liquid chromatography–tandem mass spectrometry‐based cellular proteomics applications. However, re‐solubilization of the total protein precipitate is difficult using regular in‐solution digestion protocol. Sodium deoxycholate is reported as an efficient surfactant for re‐solubilization of membrane fractions. In this study, we demonstrated an application combining methanol–chloroform based protein precipitations and deoxycholic acid assisted re‐solubilization of pellets to evaluate the improvement of protein identifications in mass spectrometry‐based bottom‐up proteomics. We evaluated the modified method using an equal amount of Raw 264.7 mouse macrophage cell lysate. Detailed in‐solution trypsin digestion studies were presented on methanol–chloroform precipitated samples with or without deoxycholic acid treatments and compared with popular sample digestion methods. A mass spectrometric analysis confirmed an 82% increase in protein identification in deoxycholic acid‐treated samples compared to other established methods. Furthermore, liquid chromatography–tandem mass spectrometry analysis of an equal amount of proteins from methanol–chloroform precipitated, and methanol–chloroform/deoxycholic acid‐treated macrophage cell lysate showed a 14% increase and 27% unique protein identifications. We believe this improved digestion method could be a complementary or alternative method for mammalian cell sample preparations where sodium dodecyl sulfate based lysis buffer is frequently used.  相似文献   
299.
A new concept for the preparation of thin-film-composite (TFC) reverse osmosis (RO) membrane by interfacial polymerization on porous polysulfone (PS) support using novel additives is reported. Hydrophilic surface modifying macromolecules (LSMM) were synthesized both ex situ by conventional method (cLSMM), and in situ within the organic solvent of the TFC system (iLSMM). The effects of these LSMMs on the fouling of the TFC RO membranes used in the desalination processes were studied. FTIR results indicated that both cLSMM and iLSMM were present in the active layer of the TFC membranes. SEM micrographs depicted that heterogeneity of the surface increases for TFC membranes compared to the control PS membrane, and that higher concentrations of LSMM provided smoother surface. AFM characteristic data presented that the surface roughness of the skin surface increases for TFC membranes compared to the control. The RO performance results showed that the addition of the cLSMM significantly decreased the salt rejection of the membrane and slightly reduced the flux, while in the case of the iLSMM, salt rejection was improved but the flux declined at different rates for different iLSMM concentrations. The membrane prepared by the iLSMM exhibited less flux decay over an extended operational period.  相似文献   
300.
The kinetics and mechanism of the reaction of hydrogen peroxide with some Fe(II) Schiff base complexes were investigated spectrophotometrically in aqueous solution at pH 8 and 35 degrees C under pseudo-first-order conditions. The used ligands were derived from salicylaldehyde or o-hydroxynaphthaldehyde and some amino acids (l-leucine, l-iso-leucine, l-serine, l-methionine and dl-tryptophan). It was found that the formation of the purple interaperoxo complex appears only above pH 7.5. The reaction consists of two steps. The first step involves reversible formation of the intraperoxo intermediate which renders irreversible at pH 8. The second step consists of inner-sphere electron transfer. The suggested scheme illustrated first-order kinetics at low [H(2)O(2)] and zero-order at high [H(2)O(2)]. Moreover, the activation parameters of the reaction were evaluated.  相似文献   
[首页] « 上一页 [25] [26] [27] [28] [29] 30 [31] [32] [33] [34] [35] 下一页 » 末  页»
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