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   766篇
  免费   59篇
  国内免费   42篇
化学   434篇
晶体学   26篇
力学   27篇
综合类   2篇
数学   184篇
物理学   194篇
  2024年   3篇
  2023年   5篇
  2022年   15篇
  2021年   13篇
  2020年   24篇
  2019年   24篇
  2018年   33篇
  2017年   33篇
  2016年   33篇
  2015年   28篇
  2014年   53篇
  2013年   154篇
  2012年   56篇
  2011年   51篇
  2010年   46篇
  2009年   35篇
  2008年   39篇
  2007年   32篇
  2006年   34篇
  2005年   9篇
  2004年   16篇
  2003年   5篇
  2002年   12篇
  2001年   15篇
  2000年   6篇
  1999年   13篇
  1998年   8篇
  1997年   4篇
  1996年   6篇
  1995年   5篇
  1994年   4篇
  1993年   3篇
  1992年   3篇
  1989年   6篇
  1985年   5篇
  1984年   3篇
  1983年   2篇
  1980年   3篇
  1979年   5篇
  1977年   2篇
  1976年   1篇
  1975年   1篇
  1974年   2篇
  1973年   1篇
  1972年   4篇
  1971年   1篇
  1965年   1篇
  1961年   1篇
  1956年   1篇
  1937年   1篇
排序方式: 共有867条查询结果,搜索用时 0 毫秒
21.
22.
Çapan  Hüsamettin  Başar  Feyzi 《Positivity》2019,23(2):493-506

In this paper, we study the difference spaces \({\mathcal {F}}(\varDelta )\), \({\mathcal {F}}_0(\varDelta )\), \({\mathcal {[F]}}(\varDelta )\) and \({\mathcal {[F]}}_0(\varDelta )\) of double sequences obtained as the domain of four-dimensional backward difference matrix \(\varDelta \) in the spaces \({\mathcal {F}}\), \({\mathcal {F}}_{0}\), \({\mathcal {[F]}}\) and \({\mathcal {[F]}}_{0}\) of almost convergent, almost null, strongly almost convergent and strongly almost null double sequences; respectively. We examine general topological properties of those spaces and give some inclusion theorems. Furthermore, we deal with their dual spaces.

  相似文献   
23.
Horseradish peroxidase (HRP) was immobilized into an electrochemically prepared copolymer of pyrrole–PAMAM (PAMAM; polyamidoamine) dendrimers for the construction of amperometric hydrogen peroxide biosensor. First, second, and third generation amidoamine–pyrrole dendrons having branched amine periphery and focal pyrrole functionality were synthesized via divergent pathway. Pyrrole dendrimers were covalently attached onto the electrode surface and polymerized by electrochemical copolymerization with pyrrole monomer. The synthesized dendrimers and copolymers have been characterized by FTIR-ATR and NMR. These copolymers have been utilized as conducting films for amperometric hydrogen peroxide sensing. The HRP retains its bioactivity after immobilization into the dendronized pyrrole-copolymers. Amperometric response was measured as a function of concentration of hydrogen peroxide, at fixed potential of +0.35 V vs. Ag/AgCl in a phosphate buffered saline (pH 7.5). The effect of pH and temperature of the medium, storage, and reusability properties were investigated. The results indicate an efficient immobilization of enzyme onto the PAMAM type dendrimer modified surface containing pyrrole monomer, which leads to high enzyme loading, and increased lifetime stability of the electrode.  相似文献   
24.
The interaction of components in the TlSe-Pr2Se3 system was studied by differential thermal, X-ray powder diffraction, and microstructural analyses and also by microhardness and density measurements. The state diagram of this system was constructed. It was found that the section TlSe-Pr2Se3 is a quasi-binary section of the Tl-Pr-Se ternary system. In the TlSe-Pr2Se3 system at the component ratio 1: 1, a new chemical compound, TlPr2Se4, forms, which melts congruently at 1295°C. In the system based on TlSe, solid solutions form until 3.5 mol % Pr2Se3, and in the system based on Pr2Se3, solid solutions occur until 2.5 mol % TlSe.  相似文献   
25.
Trinitrotoluene, known as TNT, is a widely used powerful explosive. It is a poisonous material, which injures almost all cells, especially those of liver, bone marrow, and kidney. Estrone is a sex hormone having an electron rich aromatic (phenolic) ring that is capable of forming a π complex with molecules containing an electron deficient π system. This study has focused on investigating the tendency of the complex formation of TNT with estrone. It has been thought that the formation of estrone‐TNT π complex might take place in a human body exposed to acute or prolong period of this hazardous chemical and consequently estrone activities might be impaired. The complex formation reaction was investigated mainly using DFT method with B3LYP/6‐31G(d, p) basis set in gas phase. The existence of π interaction between estrone and TNT was demonstrated by computational spectroscopic analyses (UV/Vis, IR, and 1H NMR techniques). The frontier molecular orbital (HOMO and LUMO) analyses have shown that the considered π complex is very resistant to oxidation with respect to its components, estrone and TNT.  相似文献   
26.
The syntheses of four aza-15-crown-5 ethers bearing phenyl and phenoxymethyl moieties attached to a stereogenic centre on the crown ring were achieved. Macrocycles have exhibited strong binding ability (Ka = 5364–12,969 M? 1) and modest enantiomeric discrimination towards the enantiomers of amino acid methyl ester salts by UV titration method in CHCl3 at 25°C. Computer modelling results supported experimental data providing a detailed understanding of the molecular recognition mode between hosts and guests and the likely binding sites involved. Macrocycles were used for chiral discrimination of amino acids in their zwitterionic forms or as potassium and sodium salts in transport experiments across a bulk chloroform membrane with satisfactory selectivity.  相似文献   
27.
A series of piperidoimidazolinium salts which differ in the chain lengths (butyl, octyl, dodecyl, octadecyl) and their Pd–N‐heterocyclic carbene complexes with pyridine were synthesized and characterized using elemental analysis and spectroscopic methods. The effects of these ligands on catalyst activation and the performance of the complexes were studied in Suzuki–Miyaura reactions of arylboronic acid with aryl chlorides. The complex with the ligand having the longest chain length was found to be most active. The results demonstrated that the length of the alkyl chain of the piperidoimidazolin‐2‐ylidene controlled the dispersion and composition of the nanoparticles and it affected the catalytic activity. The impact of alkyl chain length of piperidoimidazolin‐2‐ylidene on the Suzuki–Miyaura reactions of arylboronic acid with aryl halides was systematically investigated.  相似文献   
28.
29.
Abstract

A series of thiosemicarbazides were synthesized and structurally characterized by spectroscopic techniques (NMR, FT-IR) besides elemental analysis. These compounds were evaluated for their cytotoxicity against human breast cancer cell line MCF7 and prostate cancer cell line PC3 and nonmalignant fibroblast L929 cell line by MTT assay. Among the compounds, N-[2-(4-chlorophenyl)ethyl]-2-[(4-methylphenyl)sulfonyl]hydrazinecarbothioamide (3d) and 2-[(4-methylphenyl)sulfonyl]-N-[4-(trifluoromethoxy)phenyl]hydrazinecarbothioamide (3f) were found to display significant cytotoxicity with IC50 of 13.87?μM (against PC3 cell line) and 1.47?μM (against MCF7 cell line), respectively. These compounds were non-cytotoxic to normal cell line with IC50>100?μM. Western blotting studies demonstrated that compound 3f induced apoptosis and caused cell death in the MCF7 and PC3 cell lines via an increase in Bax protein expression and a slight decrease in Bcl-2 protein expression. The gene expression ratio Bax/Bcl-2 showed the induction of mitochondrial apoptosis in cancer cell lines. All of synthesized compounds have also been tested for antioxidant activity and all compounds achieved strong inhibition of the DPPH radical. These findings showed that compound 3f, displays potential to be further explored in the development of new anticancer agents.  相似文献   
30.
Abstract

The 4-H, 4-methyl and 4-phenyl derivatives of benzo-α-pyrone of 12-crown-4 and 15-crown-5 were synthesised starting from 4-substituted-6,7-dihydroxy- and 7,8-dihydroxybenzo-α-pyrones which reacted with dichloropolyethylene glycols in DMF/water/alkali carbonate. The coumarin-macrocycles were identified by elemental analysis, IR, EI-GC-MS as well as 1H, 13C NMR spectroscopy. The full experimental and spectral data is reported along with ion binding data studied in acetonitrile using fluorescence spectroscopy. The binding of the fluorogenic coumarin-crowns with Li+, Na+ and K+ were recognized as specific alterations on their fluorescence spectra that strongly originated from the structures. The observed CEQFS depending on the bound cation radii and macrocycle size evidenced the rules of cationic recognition of macrocycles. Some 15-crown-5 derivatives exhibited interesting Li+ and Na+ binding selectivities.  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