全文获取类型
收费全文 | 32608篇 |
免费 | 4113篇 |
国内免费 | 4608篇 |
专业分类
化学 | 13602篇 |
晶体学 | 306篇 |
力学 | 906篇 |
综合类 | 344篇 |
数学 | 2042篇 |
物理学 | 6852篇 |
综合类 | 17277篇 |
出版年
2024年 | 135篇 |
2023年 | 458篇 |
2022年 | 888篇 |
2021年 | 929篇 |
2020年 | 986篇 |
2019年 | 917篇 |
2018年 | 848篇 |
2017年 | 932篇 |
2016年 | 1137篇 |
2015年 | 1485篇 |
2014年 | 1832篇 |
2013年 | 2194篇 |
2012年 | 2464篇 |
2011年 | 2591篇 |
2010年 | 2235篇 |
2009年 | 2342篇 |
2008年 | 2491篇 |
2007年 | 2299篇 |
2006年 | 2117篇 |
2005年 | 1848篇 |
2004年 | 1492篇 |
2003年 | 1285篇 |
2002年 | 1487篇 |
2001年 | 1247篇 |
2000年 | 1101篇 |
1999年 | 758篇 |
1998年 | 428篇 |
1997年 | 390篇 |
1996年 | 349篇 |
1995年 | 290篇 |
1994年 | 256篇 |
1993年 | 227篇 |
1992年 | 184篇 |
1991年 | 144篇 |
1990年 | 121篇 |
1989年 | 107篇 |
1988年 | 85篇 |
1987年 | 66篇 |
1986年 | 49篇 |
1985年 | 29篇 |
1984年 | 18篇 |
1983年 | 16篇 |
1982年 | 12篇 |
1981年 | 11篇 |
1980年 | 10篇 |
1979年 | 5篇 |
1975年 | 5篇 |
1973年 | 4篇 |
1957年 | 5篇 |
1936年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 29 毫秒
991.
The [3 + 2] cycloaddition reaction between sodium azide and various organic nitriles proceeds smoothly in the presence of amine salts as catalyst in dimethylformamide. The corresponding 5-substituted 1-H tetrazoles were obtained under mild condition in good to excellent yields. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file. 相似文献
992.
Photoisomerization Mechanism of Ruthenium Sulfoxide Complexes: Role of the Metal‐Centered Excited State in the Bond Rupture and Bond Construction Processes 下载免费PDF全文
Dr. Huifang Li Lisheng Zhang lvyin Zheng Dr. Xun Li Dr. Xiaolin Fan Dr. Yi Zhao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(40):14285-14292
Phototriggered intramolecular isomerization in a series of ruthenium sulfoxide complexes, [Ru(L)(tpy)(DMSO)]n+ (where tpy=2,2’:6’,2’’‐terpyridine; DMSO=dimethyl sulfoxide; L=2,2’‐bipyridine (bpy), n=2; N,N,N’,N’‐tetramethylethylenediamine (tmen) n=2; picolinate (pic), n=1; acetylacetonate (acac), n=1; oxalate (ox), n=0; malonate (mal), n=0), was investigated theoretically. It is observed that the metal‐centered ligand field (3MC) state plays an important role in the excited state S→O isomerization of the coordinated DMSO ligand. If the population of 3MCS state is thermally accessible and no 3MCO can be populated from this state, photoisomerization will be turned off because the 3MCS excited state is expected to lead to fast radiationless decay back to the original 1GSS ground state or photodecomposition along the Ru2+?S stretching coordinate. On the contrary, if the population of 3MCS (or 3MCO) state is inaccessible, photoinduced S→O isomerization can proceed adiabatically on the potential energy surface of the metal‐to‐ligand charge transfer excited states (3MLCTS→3MLCTO). It is hoped that these results can provide valuable information for the excited state isomerization in photochromic d6 transition‐metal complexes, which is both experimentally and intellectually challenging as a field of study. 相似文献
993.
Two water‐soluble 6‐(pyrazin‐2‐yl)‐1,3,5‐triazine‐2,4‐diamino (pzta)‐based Cu(II) complexes, namely [Cu(l ‐Val)(pzta)(H2O)]ClO4 ( 1 ) and [Cu(l ‐Thr)(pzta)(H2O)]ClO4 ( 2 ) (l ‐Val: l ‐valinate; l ‐Thr: l ‐threoninate), were synthesized and characterized using elemental analyses, molar conductance measurements, spectroscopic methods and single‐crystal X‐ray diffraction. The results indicated that the molecular structures of the complexes are five‐coordinated and show a distorted square‐pyramidal geometry, in which the central copper ions are coordinated to N,N atoms of pzta and N,O atoms of amino acids. The interactions of the complexes with DNA were investigated using electronic absorption, competitive fluorescence titration, circular dichroism and viscosity measurements. These studies confirmed that the complexes bind to DNA through a groove binding mode with certain affinities (Kb = 4.71 × 103 and 1.98 × 103 M?1 for 1 and 2 , respectively). The human serum albumin (HSA) binding properties of the complexes were also evaluated using fluorescence and synchronous fluorescence spectroscopies, indicating that the complexes could quench the intrinsic fluorescence of HSA in a static quenching process. The relevant thermodynamic parameters revealed the involvement of van der Waals forces and hydrogen bonds in the formation of complex–HSA systems. Finally, molecular docking technology was also used to further verify the interactions of the complexes with DNA/HSA. 相似文献
994.
995.
996.
997.
覃彬芯 《黔西南民族师范高等专科学校学报》2014,(2):1-4
利率反映资金的价格,市场化可以提升市场资金配置的效率。国际实践表明,在经济发展的过程中,如何让资金资源得到最优化的配置,让利率成为资金供给市场的风向标,是利率市场化的重点,也是我国金融改革的重点所在,我国商业银行也会因此受到重大影响。 相似文献
998.
Yi Yuan Zong-Lin Jiang Jia-Ming Yan Ge Gao Albert S. C. Chan Ru-Gang Xie 《合成通讯》2013,43(24):4555-4561
Two new macrobicyclic imidazolium and benzimidazolium phanes were synthesized by direct quaternization of the corresponding tripodal azacycles with tribromide under high dilution condition in excellent yields. The cyclophanes were identified by 1H-NMR, 13C-NMR, FAB-MS, IR, elemental analysis and X-ray diffraction analysis. 相似文献
999.
We develop the wave-optics approach for calculating the diffraction distribution of gradient refractiveindex lenses and observing the diffraction pattern of gradient refractive-index lenses in the experiments. The results of our calculation are in good agreement with the experimental results obtained. We show that the diffraction can be regarded as a method to check the quality of the refractive-index distributions of gradient refractive-index lenses. 相似文献
1000.
Quantitative study of cellular heterogeneity in doxorubicin uptake and its pharmacological effect on cancer cells 下载免费PDF全文
Bin Deng Zhi‐Ming Wang Zi‐Hao Zhou Yi‐Meng Liu Xi‐Liang Yang Jian Song Yu‐Xiu Xiao 《Biomedical chromatography : BMC》2014,28(10):1393-1401
Cellular heterogeneity in doxorubicin (DOX) uptake and its relationship with pharmacological effect on cancer cells were quantitatively investigated for the first time. An in vitro experimental model was established by treating human leukemia K562 and breast cancer MCF‐7 cells with different schedules of DOX with or without surface P‐glycoprotein (P‐gp) inhibitor verapamil (VER). The cellular heterogeneity in DOX uptake was quantitatively examined by single‐cell analysis using capillary electrophoresis coupled with laser‐induced fluorescence detection. The corresponding cytotoxic effect was tested by cellular morphology, 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl‐tetrazolium and flow cytometry assays. The expression of cellular membrane surface P‐gp was determined by flow cytometry. Results showed that the cellular heterogeneity exists in DOX uptake. The single‐high DOX schedule leads to lower uptake heterogeneity and higher mean drug uptake. The cellular heterogeneity in DOX uptake was found to be negatively correlated with drug cytotoxicity and surface P‐gp expression, with r = ?0.7680 to ~ ?0.9587. VER reduces the cellular variation in DOX uptake, suggesting that surface P‐gp may be one of the causes of the cellular heterogeneity in DOX uptake. This research demonstrates the importance of quantitative study of cellular heterogeneity in drug uptake and its potential application in drug schedule design, response prediction and therapy modulation. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献