全文获取类型
收费全文 | 13846篇 |
免费 | 3083篇 |
国内免费 | 1805篇 |
专业分类
化学 | 9883篇 |
晶体学 | 298篇 |
力学 | 62篇 |
综合类 | 51篇 |
数学 | 68篇 |
物理学 | 3215篇 |
无线电 | 5157篇 |
出版年
2024年 | 76篇 |
2023年 | 369篇 |
2022年 | 537篇 |
2021年 | 837篇 |
2020年 | 1084篇 |
2019年 | 804篇 |
2018年 | 639篇 |
2017年 | 635篇 |
2016年 | 895篇 |
2015年 | 872篇 |
2014年 | 981篇 |
2013年 | 1095篇 |
2012年 | 956篇 |
2011年 | 914篇 |
2010年 | 723篇 |
2009年 | 670篇 |
2008年 | 690篇 |
2007年 | 709篇 |
2006年 | 653篇 |
2005年 | 543篇 |
2004年 | 501篇 |
2003年 | 474篇 |
2002年 | 960篇 |
2001年 | 348篇 |
2000年 | 310篇 |
1999年 | 230篇 |
1998年 | 207篇 |
1997年 | 157篇 |
1996年 | 147篇 |
1995年 | 117篇 |
1994年 | 117篇 |
1993年 | 70篇 |
1992年 | 99篇 |
1991年 | 60篇 |
1990年 | 59篇 |
1989年 | 47篇 |
1988年 | 22篇 |
1987年 | 13篇 |
1986年 | 18篇 |
1985年 | 14篇 |
1984年 | 15篇 |
1983年 | 10篇 |
1982年 | 10篇 |
1981年 | 13篇 |
1980年 | 5篇 |
1979年 | 7篇 |
1978年 | 4篇 |
1977年 | 6篇 |
1975年 | 7篇 |
1973年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 375 毫秒
31.
Chunhong Wang Qi Cui Zhixin Zhang Prof. Zhu-Jun Yao Dr. Shaozhong Wang Prof. Zhi-Xiang Yu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(42):9821-9826
1,3-Azaprotio transfer of propargylic α-ketocarboxylate oximes, a new type of alkynyl oximes featuring an ester tether, has been explored by taking advantage of gold catalysis. The incorporation of an oxygen atom to the chain of alkynyl oximes led to the formation of two different oxa-cyclic nitrones. It was found that internal alkynyl oximes with an E-configuration deliver five-membered nitrones, whereas terminal alkynyl oximes with an E-configuration afford six-membered nitrones. DFT calculations on four possible pathways supported a stepwise formation of C−N and C−H bonds, in which a 1,3-acyloxy-migration competes with the 1,3-azaprotio-transfer, especially in the case of internal alkynyl oximes. The relative nucleophilic properties of oxygen in the carbonyl group and the nitrogen in the oxime, the electronic effects of alkynes, and the influence of the ring system have been investigated computationally. 相似文献
32.
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
33.
34.
James E. Tyrrell Martyn G. Boutelle Alasdair J. Campbell 《Advanced functional materials》2021,31(1):2007086
Biological environments use ions in charge transport for information transmission. The properties of mixed electronic and ionic conductivity in organic materials make them ideal candidates to transduce physiological information into electronically processable signals. A device proven to be highly successful in measuring such information is the organic electrochemical transistor (OECT). Previous electrophysiological measurements performed using OECTs show superior signal-to-noise ratios than electrodes at low frequencies. Subsequent development has significantly improved critical performance parameters such as transconductance and response time. Here, interdigitated-electrode OECTs are fabricated on flexible substrates, with one such state-of-the-art device achieving a peak transconductance of 139 mS with a 138 µs response time. The devices are implemented into an array with interconnects suitable for micro-electrocorticographic application and eight architecture variations are compared. The two best-performing arrays are subject to the full electrophysiological spectrum using prerecorded signals. With frequency filtering, kHz-scale frequencies with 10 µV-scale voltages are resolved. This is supported by a novel quantification of the noise, which compares the gate voltage input and drain current output. These results demonstrate that high-performance OECTs can resolve the full electrophysiological spectrum and suggest that superior signal-to-noise ratios could be achieved in high frequency measurements of multiunit activity. 相似文献
35.
Thomas Wittmann Dr. Renée Siegel Nele Reimer Dr. Wolfgang Milius Prof. Dr. Norbert Stock Prof. Dr. Jürgen Senker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):314-323
The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH2 by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N2 and H2O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m2 g?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with 1H‐27Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking. 相似文献
36.
Ping Chen Yanhong Hao Xinxin Wang Prof. Dr. Dan Yuan Prof. Dr. Yingming Yao Prof. Dr. Lutz Ackermann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(30):7292-7297
Highly position selective alkylations of N-alkylindoles at C7-positions have been enabled by cationic zirconium complexes. The strategy provides a straightforward access to install alkyl groups at C7-positions of indoles without a complex directing group. Mechanistic studies provided support for the importance of Brønsted acids in the catalytic manifold. 相似文献
37.
Hideaki Murasugi Dr. Shohei Kumagai Dr. Hiroaki Iguchi Prof. Dr. Masahiro Yamashita Dr. Shinya Takaishi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(42):9885-9891
Crystal structures of a series of organic–inorganic hybrid gold iodide perovskites, formulated as A2[AuII2][AuIIII4] [A=methylammonium (MA) ( 1 ) and formamidinium (FA) ( 2 )], A′2[I3]1−x[AuII2]x[AuIIII4] [A′=imidazolium (IMD) ( 3 ), guanidinium (GUA) ( 4 ), dimethylammonium (DMA) ( 5 ), pyridinium (PY) ( 6 ), and piperizinium (PIP) ( 7 )], systematically changed depending on the cation size. In addition, triiodide (I3−) ions were partly incorporated into the AuI2− sites of 3 – 7 , whereas they were not incorporated into those of 1 and 2 . Such a difference comes from the size of the organic cation. Optical absorption spectra showed characteristic intervalence charge-transfer bands from AuI to AuIII species, and the optical band gap increased as the size of the cation became larger. 相似文献
38.
The strong tendency of organic nanoparticles to rapidly self‐assemble into highly aligned superlattices at room temperature when solution‐cast from dispersions or spray‐coated directly onto various substrates is described. The nanoparticle dispersions are stable for years. The novel precipitation process used is believed to result in molecular distances and alignments in the nanoparticles that are not normally possible. Functional organic light‐emitting diodes (OLEDs)—which have the same host–dopant emissive‐material composition—with process‐tunable electroluminescence have been built with these nanoparticles, indicating the presence of novel nanostructures. For example, only changing the conditions of the precipitation process changes the OLED emission from green light to yellow. 相似文献
39.
在陷阱电荷限制电流传导理论的基础上,提出了双层有机电致发光器件的数值模型,研究了结构为"阳极/空穴输运层(HTL)/发光层(EML)/阴极"的器件中电流密度和量子效率随有机层的特征陷阱能量、陷阱密度和载流子迁移率的依赖关系. 研究发现,对于给定的HTL和EML的特征陷阱能量、陷阱密度和载流子迁移率,存在一个最优的HTL和EML之间的厚度比率,在此最优厚度比下,器件的电流密度和量子效率达到最大.通过有机层厚度的优化,器件的电流密度和量子效率可提高多达两个数量级.另外,还研究了最优厚度比随有机层特征陷阱能量、总陷阱密度和载流子迁移率之间的定量关系. 相似文献
40.
半导体芯片的检测是芯片生产企业生产过程中的重要环节,芯片在检测过程中,由于圆形硅片的结构特点而造成的漏测又是困扰芯片生产企业不可小视的实际问题。本文介绍了利用双探边器解决由于硅圆片结构所造成的漏测的有效办法及具体操作方法。 相似文献