全文获取类型
收费全文 | 18685篇 |
免费 | 2035篇 |
国内免费 | 1761篇 |
专业分类
化学 | 12976篇 |
晶体学 | 388篇 |
力学 | 725篇 |
综合类 | 115篇 |
数学 | 2630篇 |
物理学 | 5647篇 |
出版年
2023年 | 220篇 |
2022年 | 352篇 |
2021年 | 430篇 |
2020年 | 542篇 |
2019年 | 562篇 |
2018年 | 498篇 |
2017年 | 552篇 |
2016年 | 906篇 |
2015年 | 776篇 |
2014年 | 963篇 |
2013年 | 1549篇 |
2012年 | 1400篇 |
2011年 | 1442篇 |
2010年 | 1063篇 |
2009年 | 989篇 |
2008年 | 1306篇 |
2007年 | 1212篇 |
2006年 | 1025篇 |
2005年 | 881篇 |
2004年 | 664篇 |
2003年 | 474篇 |
2002年 | 475篇 |
2001年 | 394篇 |
2000年 | 392篇 |
1999年 | 295篇 |
1998年 | 267篇 |
1997年 | 184篇 |
1996年 | 202篇 |
1995年 | 214篇 |
1994年 | 187篇 |
1993年 | 158篇 |
1992年 | 144篇 |
1991年 | 142篇 |
1990年 | 122篇 |
1989年 | 107篇 |
1988年 | 107篇 |
1987年 | 99篇 |
1986年 | 91篇 |
1985年 | 140篇 |
1984年 | 131篇 |
1983年 | 85篇 |
1982年 | 87篇 |
1981年 | 89篇 |
1980年 | 74篇 |
1979年 | 68篇 |
1978年 | 56篇 |
1977年 | 43篇 |
1976年 | 49篇 |
1975年 | 43篇 |
1974年 | 37篇 |
排序方式: 共有10000条查询结果,搜索用时 750 毫秒
21.
Solid‐state 31P NMR investigation on the status of guanine nucleotides in paclitaxel‐stabilized microtubules
下载免费PDF全文
![点击此处可从《Magnetic resonance in chemistry : MRC》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Ga Hyang Lee Su Young Oh Kwon Joo Yeo Taslima Ferdous Meeyeon Cho Younkee Paik 《Magnetic resonance in chemistry : MRC》2015,53(5):330-336
Microtubule dynamics is a target for many chemotherapeutic drugs. In order to understand the biochemical effects of paclitaxel on the GTPase activity of tubulin, the status of guanine nucleotides in microtubules was investigated by 31P cross‐polarization magic angle spinning (CPMAS) NMR. Microtubules were freshly prepared in vitro in the presence of paclitaxel and then lyophilized in sucrose buffer for solid‐state NMR experiments. A 31P CPMAS NMR spectrum with the SNR of 25 was successfully acquired from the lyophilized microtubule sample. The broadness of the 31P spectral lines in the spectrum indicates that the molecular environments around the guanine nucleotides inside tubulin may not be as crystalline as reported by many diffraction studies. Deconvolution of the spectrum into four spectral components was carried out in comparison with the 31P NMR spectra obtained from five control samples. The spectral analysis suggested that about 13% of the nucleotides were present as GTP and 37% as GDP in the β‐tubulin (E‐site) of the microtubules. It was found that most of the GDPs were present as GDP‐Pi complex in the microtubules, which seems to be one of the effects of paclitaxel binding. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
22.
Prof. Piotr Bałczewski Dr. Emilia Kowalska Dr. Ewa Różycka-Sokołowska Dr. Joanna Skalik Dr. Krzysztof Owsianik Dr. Marek Koprowski Dr. Bernard Marciniak Dr. Dariusz Guziejewski Prof. Witold Ciesielski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(62):14148-14161
The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (Tdecomp.=331–354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60–70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel–Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S1 state by molecular oxygen. 相似文献
23.
Ling-Yang Hsu Qiumin Liang Zhiheng Wang Hsin-Hung Kuo Wun-Shan Tai Shi-Jian Su Xiuwen Zhou Yi Yuan Yun Chi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(67):15375-15386
Iridium complexes bearing chelating cyclometalates are popular choices as dopant emitters in the fabrication of organic light-emitting diodes (OLEDs). In this contribution, we report a series of blue-emitting, bis-tridentate IrIII complexes bearing chelates with two fused five-six-membered metallacycles, which are in sharp contrast to the traditional designs of tridentate chelates that form the alternative, fused five-five metallacycles. Five IrIII complexes, Px-21 – 23 , Cz-4 , and Cz-5 , have been synthesized that contain a coordinated dicarbene pincer chelate incorporating a methylene spacer and a dianionic chromophoric chelate possessing either a phenoxy or carbazolyl appendage to tune the coordination arrangement. All these tridentate chelates afford peripheral ligand–metal–ligand bite angles of 166–170°, which are larger than the typical bite angle of 153–155° observed for their five-five-coordinated tridentate counterparts, thereby leading to reduced geometrical distortion in the octahedral frameworks. Photophysical measurements and TD-DFT studies verified the inherent transition characteristics that give rise to high emission efficiency, and photodegradation experiments confirmed the improved stability in comparison with the benchmark fac-[Ir(ppy)3] in degassed toluene at room temperature. Phosphorescent OLED devices were also fabricated, among which the carbazolyl-functionalized emitter Cz-5 exhibited the best performance among all the studied bis-tridentate phosphors, showing a maximum external quantum efficiency (EQEmax) of 18.7 % and CIEx,y coordinates of (0.145, 0.218), with a slightly reduced EQE of 13.7 % at 100 cd m−2 due to efficiency roll-off. 相似文献
24.
Gas-phase 21Ne nuclear magnetic resonance spectra were measured at the natural abundance of 21Ne isotope for samples consisting of pressurized neon up to 60 bar at room temperature and applying the magnetic field of the strength B0 = 11.7574 T. It showed that the nuclear magnetic resonance frequency is linearly dependent on the density of gaseous neon. The resonance frequency was extrapolated to the zero-density point, and it permitted the determination of the 21Ne nuclear magnetic moment, μ(21Ne) = 0.6617774(10) μN. The present value of μ(21Ne) is not influenced by the bulk magnetic susceptibility of neon and interactions between neon atoms; therefore, it is more precise and reliable than the previous result obtained for μ(21Ne). 相似文献
25.
26.
ZHAO Shan-Rong CHEN Kai-Xian JIANG Hua-Liang WANG Qin-Mi JI Ru-YunShanghai Institute of Materia Medica Chinese Academy of Sciences Shanghai China 《中国化学》1997,15(1):84-89
We have used quantum mechanical method to study the transition states(TSs) of uridine phosphorolysis reaction. Comparing the four different reaction pathways and the five transition states obtained, we conclude that enzymatic uridine phosphorolysis takes place mainly according to acid-catalyzed SN2 mechanism. The proposed reaction pathway is consistent with many experimental results. 相似文献
27.
28.
瞄准线高精度稳定是机载光电稳瞄系统的主要指标和关键技术。根据四框架稳瞄系统的工作原理,以手动跟踪模式为主要研究对象,建立了稳瞄伺服控制系统模型。考虑到直升机扰动特点,对线扰动、角速率扰动、摩擦力矩、弹性力矩等各种扰动因素也建立相应的数学模型,同时在各种扰动因素作用下利用Matlab对机载高精度稳瞄系统的手动跟踪控制模式进行了仿真设计分析和理论研究,设计出适合的控制器。此模型在实际系统中获得验证,对稳瞄伺服控制系统的设计具有参考意义。 相似文献
29.
30.
M. A. Augustyniak-Jabłokow K. Łukaszewicz A. Pietraszko V. E. Petrashen Yu. V. Yablokov 《Physics of the Solid State》2002,44(8):1480-1483
The EPR spectra evolution of Cs2Zn1?x Cux(ZrF6)2 · 6H2O (x=0.01, 0.6, 0.8, and 1.0) in the temperature range 4.2–330 K and the x-ray structure analysis of the compound with x=1.0 in the range 150–327 K show that the Jahn-Teller (JT) complex Cu(H2O)6 coordination sphere undergoes a plastic deformation. The observed effect is due to the combined influence of small lattice strains existing in the paraphase and a new one appearing as a result of a ferroelastic phase transition and increasing with decreasing temperature below T c . It is proved that both cooperative interactions between JT complexes and ferroelastic strain stabilize a certain JT configuration. The problem of instability of a JT configuration compressed at T ~ 265 K is discussed. 相似文献