全文获取类型
收费全文 | 18981篇 |
免费 | 859篇 |
国内免费 | 99篇 |
专业分类
化学 | 13081篇 |
晶体学 | 120篇 |
力学 | 420篇 |
数学 | 2895篇 |
物理学 | 3423篇 |
出版年
2023年 | 122篇 |
2022年 | 172篇 |
2021年 | 268篇 |
2020年 | 377篇 |
2019年 | 397篇 |
2018年 | 234篇 |
2017年 | 236篇 |
2016年 | 600篇 |
2015年 | 556篇 |
2014年 | 644篇 |
2013年 | 1025篇 |
2012年 | 1115篇 |
2011年 | 1248篇 |
2010年 | 744篇 |
2009年 | 661篇 |
2008年 | 1036篇 |
2007年 | 1020篇 |
2006年 | 949篇 |
2005年 | 880篇 |
2004年 | 772篇 |
2003年 | 637篇 |
2002年 | 605篇 |
2001年 | 308篇 |
2000年 | 300篇 |
1999年 | 274篇 |
1998年 | 241篇 |
1997年 | 231篇 |
1996年 | 264篇 |
1995年 | 249篇 |
1994年 | 218篇 |
1993年 | 212篇 |
1992年 | 203篇 |
1991年 | 176篇 |
1990年 | 174篇 |
1989年 | 174篇 |
1988年 | 150篇 |
1987年 | 125篇 |
1986年 | 115篇 |
1985年 | 166篇 |
1984年 | 161篇 |
1983年 | 126篇 |
1982年 | 153篇 |
1981年 | 157篇 |
1980年 | 133篇 |
1979年 | 140篇 |
1978年 | 158篇 |
1977年 | 115篇 |
1976年 | 100篇 |
1975年 | 117篇 |
1974年 | 90篇 |
排序方式: 共有10000条查询结果,搜索用时 13 毫秒
991.
Hideyuki Tatsuno Kasper S. Kjr Kristjan Kunnus Tobias C. B. Harlang Cornelia Timm Meiyuan Guo Pavel Chbera Lisa A. Fredin Robert W. Hartsock Marco E. Reinhard Sergey Koroidov Lin Li Amy A. Cordones Olga Gordivska Om Prakash Yizhu Liu Mads G. Laursen Elisa Biasin Frederik B. Hansen Peter Vester Morten Christensen Kristoffer Haldrup Zoltn Nmeth Dorottya Srosin Szemes va Bajnczi Gyrgy Vank Tim B. Van Driel Roberto Alonso‐Mori James M. Glownia Silke Nelson Marcin Sikorski Henrik T. Lemke Dimosthenis Sokaras Sophie E. Canton Asmus O. Dohn Klaus B. Mller Martin M. Nielsen Kelly J. Gaffney Kenneth Wrnmark Villy Sundstrm Petter Persson Jens Uhlig 《Angewandte Chemie (International ed. in English)》2020,59(1):364-372
Iron N‐heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub‐ps X‐ray spectroscopy study of an FeIINHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot 3MLCT state, from the initially excited 1MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the 3MC state, in competition with vibrational relaxation and cooling to the relaxed 3MLCT state. The relaxed 3MLCT state then decays much more slowly (7.6 ps) to the 3MC state. The 3MC state is rapidly (2.2 ps) deactivated to the ground state. The 5MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the 3MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition‐metal complexes for similar ultrafast decays to optimize photochemical performance. 相似文献
992.
Jonas Scharfbier Benjamin M. Gross Martin Oestreich 《Angewandte Chemie (International ed. in English)》2020,59(4):1577-1580
A method for the synthesis of benzylsilanes starting from the corresponding ammonium triflates is reported. Silyl boronic esters are employed as silicon pronucleophiles, and the reaction is catalyzed by copper(I) salts. Enantioenriched benzylic ammonium salts react stereospecifically through an SN2‐type displacement of the ammonium group to afford α‐chiral silanes with inversion of the configuration. A cyclopropyl‐substituted substrate does not undergo ring opening, thus suggesting an ionic reaction mechanism with no benzyl radical intermediate. 相似文献
993.
Erik Barwa Tobias F. Pascher Milan On
k Christian van der Linde Martin K. Beyer 《Angewandte Chemie (International ed. in English)》2020,59(19):7467-7471
We investigate activation of carbon dioxide by singly charged hydrated magnesium cations Mg .+(H2O)n, through infrared multiple photon dissociation (IRMPD) spectroscopy combined with quantum chemical calculations. The spectra of [MgCO2(H2O)n].+ in the 1250–4000 cm?1 region show a sharp transition from n=2 to n=3 for the position of the CO2 antisymmetric stretching mode. This is evidence for the activation of CO2 via charge transfer from Mg .+ to CO2 for n≥3, while smaller clusters feature linear CO2 coordinated end‐on to the metal center. Starting with n=5, we see a further conformational change, with CO2.? coordination to Mg2+ gradually shifting from bidentate to monodentate, consistent with preferential hexa‐coordination of Mg2+. Our results reveal in detail how hydration promotes CO2 activation by charge transfer at metal centers. 相似文献
994.
Duan Bortk Daniel Pecher Daniel Vgh Martin Breza Peter Miku Viktor Milata 《Journal of mass spectrometry : JMS》2020,55(10)
Twenty‐one pentafluorphenylhydrazones have been analyzed by means of tandem mass spectrometry (ESI MS/MS) conditions to compare their fragmentations with those ones obtained from quantum‐chemical calculations of the hydrazone moiety depending on the substitution from the aldehyde site. The hydrazone N–N bond is disrupted under such conditions, and these results are in accordance with the facts that an electron‐rich particle, such as an anion and or radical in a solution, can cause this disruption and simultaneous defluorination in para‐position of the hydrazone part of the molecule. 相似文献
995.
Al-Shantir Omar Csáki Štefan Ondro Tomáš Keppert Martin Minárik Peter Vrabec Marek Trník Anton 《Journal of Thermal Analysis and Calorimetry》2020,142(5):1759-1766
Journal of Thermal Analysis and Calorimetry - This paper presents mechanical-acoustic study of samples made from electroporcelain mixture (type C 130) under five different compression... 相似文献
996.
Van T. Tran Zi‐Qi Li Omar Apolinar Joseph Derosa Matthew V. Joannou Steven R. Wisniewski Martin D. Eastgate Keary M. Engle 《Angewandte Chemie (International ed. in English)》2020,59(19):7409-7413
We report that Ni(COD)(DQ) (COD=1,5‐cyclooctadiene, DQ=duroquinone), an air‐stable 18‐electron complex originally described by Schrauzer in 1962, is a competent precatalyst for a variety of nickel‐catalyzed synthetic methods from the literature. Due to its apparent stability, use of Ni(COD)(DQ) as a precatalyst allows reactions to be conveniently performed without use of an inert‐atmosphere glovebox, as demonstrated across several case studies. 相似文献
997.
Karen J. Ardila‐Fierro Stipe Lukin Martin Etter Krunoslav Uarevi Ivan Halasz Carsten Bolm Jos G. Hernndez 《Angewandte Chemie (International ed. in English)》2020,59(32):13458-13462
Recent progress in the field of mechanochemistry has expanded the discovery of mechanically induced chemical transformations to several areas of science. However, a general fundamental understanding of how mechanochemical reactions by ball milling occur has remained unreached. For this, we have now implemented in situ monitoring of a mechanochemically induced molecular rearrangement by synchrotron X‐ray powder diffraction, Raman spectroscopy, and real‐time temperature sensing. The results of this study demonstrate that molecular rearrangements can be accomplished in the solid state by ball milling and how in situ monitoring techniques enable the visualization of changes occurring at the exact instant of a molecular migration. The mechanochemical benzil–benzilic acid rearrangement is the focal point of the study. 相似文献
998.
Eder Toms‐Mendivil Marc Devillard Vianney Regnier Jacques Pecaut David Martin 《Angewandte Chemie (International ed. in English)》2020,59(28):11516-11520
Oxyallyl derivatives are typically elusive compounds. Even recently reported “stabilized” 1,3‐diaminooxyallyl species are still highly reactive and have short lifetimes at room temperature. Herein, we report the synthesis and preliminary study of mesoionic pyrimidine derivatives that feature 1,3‐bis(dimethylamino)oxyallyl patterns with an unprecedented level of stabilization. The latter are not only insensitive towards air and moisture, but they are also compatible with the formation of an ancillary stable N‐heterocyclic carbene moiety. As the oxyallyl pattern is proton‐responsive, it allows the reversible switching of the electronic properties of the carbene, as a ligand. 相似文献
999.
Alshymaa Abdel-Rahman Gomaa Usama Ramadan Abdelmohsen Markus Krischke Martin J. Mueller Amira Samir Wanas 《Natural product research》2020,34(18):2612-2615
AbstractThe present study evaluates the chemical composition of Zinnia elegans and Gazania rigens based on their metabolomic profiles using liquid chromatography coupled with high-resolution mass spectrometry (LC‐HR-MS), alongside with the anti-infective activities of their ethanol extracts, as well as, different fractions. A significant difference was observed between the LC-MS profiles of the two plants such as, coumarins, sesquiterpene lactones and phenylethanoids which were characteristic for Z. elegans, while amides and phenolic acid derivatives were characteristic for G. rigens. These results highlight the chemical potential of Z. elegans and G. rigens. Furthermore, the ethyl acetate fraction of Z. elegans showed a significant antimalarial activity with IC50 values of 21.03 and 13.72?µg/mL against Plasmodium falciparum D6 and P. falciparum W2, respectively. 相似文献
1000.
BoRa Lee Anthony C. Willis Jas S. Ward Warren T. Smith Ping Lan Martin G. Banwell 《化学:亚洲杂志》2020,15(19):3059-3081
Syntheses of a range of chemically well‐defined oligopyrrole/benzenoid hybrids are described using tandem Suzuki‐Miyaura cross‐coupling/bromo‐desilyation reaction sequences for linking borylated pyrroles, halogenated pyrroles and/or dibromobenzenes to one another. By such means, including iterative variants, a range of all α‐linked, all β‐linked oligopyrroles as well as certain combinations thereof have been assembled, some of them for the first time. The conductivities of iodine‐treated thin films formed from certain such systems have been determined. 相似文献