全文获取类型
收费全文 | 630篇 |
免费 | 69篇 |
国内免费 | 91篇 |
专业分类
化学 | 509篇 |
晶体学 | 18篇 |
力学 | 18篇 |
综合类 | 6篇 |
数学 | 122篇 |
物理学 | 117篇 |
出版年
2024年 | 3篇 |
2023年 | 12篇 |
2022年 | 5篇 |
2021年 | 8篇 |
2020年 | 30篇 |
2019年 | 13篇 |
2018年 | 10篇 |
2017年 | 17篇 |
2016年 | 20篇 |
2015年 | 24篇 |
2014年 | 44篇 |
2013年 | 40篇 |
2012年 | 33篇 |
2011年 | 32篇 |
2010年 | 27篇 |
2009年 | 24篇 |
2008年 | 39篇 |
2007年 | 43篇 |
2006年 | 36篇 |
2005年 | 36篇 |
2004年 | 47篇 |
2003年 | 37篇 |
2002年 | 46篇 |
2001年 | 47篇 |
2000年 | 20篇 |
1999年 | 17篇 |
1998年 | 6篇 |
1997年 | 5篇 |
1996年 | 3篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 3篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1976年 | 5篇 |
1975年 | 3篇 |
1965年 | 2篇 |
1939年 | 2篇 |
1936年 | 2篇 |
1933年 | 1篇 |
排序方式: 共有790条查询结果,搜索用时 203 毫秒
111.
112.
With water-soluble anionic tetra (p-carboxyphenyl) porphyrin (TCPP) to solubilize multi-walled carbon nanotubes (MCNTs), we obtained a suspension that could be stable more than 1 week. With this TCPP/MCNTs suspension, we propose a spectrofluorometric method of DNA hybridization in this contribution. Our basic finding for this work is that the fluorescence from a dye-tagged single stranded DNA (ssDNA), which was directly added to the TCPP/MCNTs suspension, gets quenched, and the fluorescence could be remained if the dye-tagged single stranded DNA is first to be hybridized with its complementary target DNA to form a double stranded DNA (dsDNA) hybrid and added into the TCPP/MCNTs suspension. Mechanism investigations showed that the reason for the former is due to the adsorption of ssDNA on the surfaces of MCNTs, and that for the latter is due to the strong electrostatic repulsion force between the negative charge TCPP/MCNTs complexes and dsDNA. Thus, target DNA in a DNA sample and single-base mismatch in DNA sequences could be easily detected. 相似文献
113.
Kim DE Kim IS Ratovelomanana-Vidal V Genêt JP Jeong N 《The Journal of organic chemistry》2008,73(20):7985-7989
An efficient asymmetric PKR mediated by Rh(I) catalyst at ambient temperature was developed. The reaction utilizing a Rh(I) catalyst bearing a (R)-3,5-diMeC4H4-BINAP ligand at 18-20 degrees C under a reduced partial pressure of CO (0.1 atm) provided PKR products in high chemical yield as well as high enantioselectivity. 相似文献
114.
With the gradual depletion of traditional zinc resources, the full use of various non-traditional zinc-containing resources has received intensive attention. However, the efficient recovery of zinc ions with low concentrations remains challenging. Here efficient and continuous recovery of zinc ions in ammoniacal chloride media by a flat supported liquid membrane system is achieved, using Cyanex923 and TBP mixed extractant as the membrane phase. This article discusses the synergistic effect between Aliquat336, Cyanex923 and TBP, the effects of feed pH, total ammonia concentration, Cl− concentration and temperature on Zn(II) transport. 相似文献
115.
差示扫描量热法测定马来酸酐纯度 总被引:1,自引:0,他引:1
用差示扫描量热法(DSC)测定马来酸酐的纯度,测定条件为升温速率0.8℃/min,样品量2.6~2.8mg,氮气流速为40mL/min。纯度测定结果的相对标准偏差(RSD)为0.02%(n=5)。将DSC法、液相色谱法、药典法、滴定分析法对不同物质纯度的测定结果进行了比对,4种方法的测定结果基本一致。DSC法简便、快速、准确、重现性好,适合马来酸酐纯度的测定。 相似文献
116.
Yunpeng Zhong Xuesong Xie Prof. Zhiyuan Zeng Prof. Bingan Lu Prof. Gen Chen Prof. Jiang Zhou 《Angewandte Chemie (International ed. in English)》2023,62(40):e202310577
Aqueous rechargeable zinc-ion batteries (ARZBs) are impeded by the mutual problems of unstable cathode, electrolyte parasitic reactions, and dendritic growth of zinc (Zn) anode. Herein, a triple-functional strategy by introducing the tetramethylene sulfone (TMS) to form a hydrated eutectic electrolyte is reported to ameliorate these issues. The activity of H2O is inhibited by reconstructing hydrogen bonds due to the strong interaction between TMS and H2O. Meanwhile, the preferentially adsorbed TMS on the Zn surface increases the thickness of double electric layer (EDL) structure, which provides a shielding buffer layer to suppress dendrite growth. Interestingly, TMS modulates the primary solvation shell of Zn2+ ultimately to achieve a novel solvent co-intercalation ((Zn-TMS)2+) mechanism, and the intercalated TMS works as a “pillar” that provides more zincophilic sites and stabilizes the structure of cathode (NH4V4O10, (NVO)). Consequently, the Zn||NVO battery exhibits a remarkably high specific capacity of 515.6 mAh g−1 at a low current density of 0.2 A g−1 for over 40 days. This multi-functional electrolytes and solvent co-intercalation mechanism will significantly propel the practical development of aqueous batteries. 相似文献
117.
免疫亲和质谱法研究/β2-微球蛋白抗原表位 总被引:1,自引:0,他引:1
采用免疫亲和分离与质谱分析相结合的方法,对β2-微球蛋白抗原表位进行了系统研究.完整的抗原分子和已固定在载体(CNBr-activated Sepharose beads)上的单克隆抗体发生免疫亲和反应后,用Endoproteinase Glu-C,Trypsin,AminopeptidaseM和carboxypeptidase Y四种不同的蛋白酶依次酶解抗原分了,并采用基质辅助激光解析电离飞行时间质谱(MALDI-TOF-MS)技术对与抗体连接受保护而未发生水解的肽段进行了研究.结果表明:β2-微球蛋白抗原表位位于整个蛋白分了氨基酸序列的61~67位,即为SFYLLYY.通过合成肽段的分析,证明了SFYLLYY即为抗原表位,与亲和质谱方法分析结果一致. 相似文献
118.
Lv G He F Wang X Gao F Zhang G Wang T Jiang H Wu C Guo D Li X Chen B Gu Z 《Langmuir : the ACS journal of surfaces and colloids》2008,24(5):2151-2156
Novel nanocomposites of polylactide (PLA) nanofibers and tetraheptylammonium-capped Fe3O4 magnetic nanoparticles have been prepared and utilized to realize the efficient accumulation of anticancer drug daunorubicin in target cancer cells. The observations of optical microscopy and confocal fluorescence microscopy indicate that the PLA nanofibers and Fe3O4 nanoparticles may contribute to their beneficial effects on intracellular drug uptake of leukemia K562 cell lines in which the efficiently enhanced accumulation of anticancer drug daunorubicin on the membrane of cancer cells could be observed. Meanwhile, the electrochemical detection and the microculture tetrazolium studies were also explored to probe the effect of the relevant nanomaterials on the drug uptake of cancer cells. The results illustrate that the nanocomposites could effectively facilitate the interaction of daunorubicin with leukemia cells and remarkably enhance the permeation and drug uptake of anticancer agents in the cancer cells, which could readily lead to the induction of the cell death of leukemia cells. This observation suggests a new perspective for the targeted therapeutic approaches of cancers. 相似文献
119.
Neaţu F Li Z Richards R Toullec PY Genêt JP Dumbuya K Gottfried JM Steinrück HP Pârvulescu VI Michelet V 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(30):9412-9418
A novel class of heterogeneous gold catalysts supported on zeolite beta-NH4+ was prepared by the deposition-precipitation method. This new class of catalyst showed interesting catalytic activities for the intramolecular cycloisomerization of gamma-acetylenic carboxylic acids leading to functionalized gamma-alkylidene gamma-butyrolactones. Analysis of the supported gold species with in situ X-ray photoelectron spectroscopy (in situ XPS) suggests that cationic Au (possibly AuIII) can play an important role in such reactions. The high discrepancy in catalyst stability in favor of the Au supported on the zeolite system over bulk Au2O3 is explained by 1) the size of the particles and 2) the reversibility of the redox deactivating process (AuIII-->AuI) in the presence of oxygen for the supported system. The efficiency of this system allowed reaction under mild heterogeneous conditions. The potential for catalyst recycling was also highlighted. 相似文献
120.
Qiang‐Gen Li Chao Deng Yi Ren Ning‐Bew Wong San‐Yan Chu Xin Wang 《International journal of quantum chemistry》2008,108(1):142-150
Computational investigations by an ab initio molecular orbital method (HF and MP2) with the 6‐311+G(d,p) and 6‐311++G(2df, 2pd) basis sets on the tautomerism of three monochalcogenosilanoic acids CH3Si(?O)XH (X = S, Se, and Te) in the gas phase and a polar and aprotic solution tetrahydrofuran (THF) was undertaken. Calculated results show that the silanol forms CH3Si(?X)OH are much more stable than the silanone forms CH3Si(?O)XH in the gas‐phase, which is different from the monochalcogenocarboxylic acids, where the keto forms CH3C(?O)XH are dominant. This situation may be attributed to the fact that the Si? O and O? H single bonds in the silanol forms are stronger than the Si? X and X? H single bonds in the silanone forms, respectively, even though the Si?X (X = S, Se, and Te) double bonds are much weaker than the Si?O double bond. These results indicate that the stability of the monochalcogenosilanoic acid tautomers is not determined by the double bond energies, contrary to the earlier explanation based on the incorrect assumption that the Si?S double bond is stronger than the S?O double bond for the tautomeric equilibrium of RSi(?O)SH (R?H, F, Cl, CH3, OH, NH2) to shift towards the thione forms [RSi(?S)OH]. The binding with CH3OCH3 enhances the preference of the silanol form in the tautomeric equilibrium, and meanwhile significantly lowers the tautomeric barriers by more than 34 kJ/mol in THF solution. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 相似文献