全文获取类型
收费全文 | 24197篇 |
免费 | 2363篇 |
国内免费 | 6446篇 |
专业分类
化学 | 29949篇 |
晶体学 | 373篇 |
力学 | 150篇 |
综合类 | 182篇 |
数学 | 379篇 |
物理学 | 1973篇 |
出版年
2024年 | 10篇 |
2023年 | 229篇 |
2022年 | 333篇 |
2021年 | 606篇 |
2020年 | 895篇 |
2019年 | 734篇 |
2018年 | 766篇 |
2017年 | 826篇 |
2016年 | 1173篇 |
2015年 | 1156篇 |
2014年 | 1475篇 |
2013年 | 2508篇 |
2012年 | 1703篇 |
2011年 | 1765篇 |
2010年 | 1480篇 |
2009年 | 1690篇 |
2008年 | 1759篇 |
2007年 | 1819篇 |
2006年 | 1821篇 |
2005年 | 1735篇 |
2004年 | 1661篇 |
2003年 | 1432篇 |
2002年 | 843篇 |
2001年 | 592篇 |
2000年 | 496篇 |
1999年 | 435篇 |
1998年 | 395篇 |
1997年 | 442篇 |
1996年 | 353篇 |
1995年 | 349篇 |
1994年 | 311篇 |
1993年 | 293篇 |
1992年 | 269篇 |
1991年 | 146篇 |
1990年 | 97篇 |
1989年 | 96篇 |
1988年 | 86篇 |
1987年 | 46篇 |
1986年 | 31篇 |
1985年 | 41篇 |
1984年 | 32篇 |
1983年 | 11篇 |
1982年 | 13篇 |
1981年 | 11篇 |
1980年 | 13篇 |
1979年 | 5篇 |
1978年 | 4篇 |
1976年 | 4篇 |
1975年 | 4篇 |
1973年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 156 毫秒
71.
Wenxiang Liu Lele Lu Qiang Li Boyuan Wu Ruizhe Zhang Wei Shi Peng Cheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(53):12206-12211
Photocatalytic hydrogen evolution by water splitting is highly important for the application of hydrogen energy and the replacement of fossil fuel by solar energy, which needs the development of efficient catalysts with long-term catalytic stability under light irradiation in aqueous solution. Herein, Zn0.5Cd0.5S solid solution was synthesized by a metal–organic framework-templated strategy and then loaded with MoS2 by a hydrothermal method to fabricate a MoS2/Zn0.5Cd0.5S heterojunction for photocatalytic hydrogen evolution. The composition of MoS2/Zn0.5Cd0.5S was fine-tuned to obtain the optimized 5 wt % MoS2/Zn0.5Cd0.5S heterojunction, which showed a superior hydrogen evolution rate of 23.80 mmol h−1 g−1 and steady photocatalytic stability over 25 h. The photocatalytic performance is due to the appropriate composition and the formation of an intimate interface between MoS2 and Zn0.5Cd0.5S, which endows the photocatalyst with high light-harvesting ability and effective separation of photogenerated carriers. 相似文献
72.
Prof. Yongjun Li Jingyi He Han Shen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(54):12310-12321
Graphdiyne (GDY) exhibits unique characteristics of a highly conjugated π system, evenly distributed nanopores, and a direct band gap. This has encouraged multidisciplinary research groups to investigate its application in energy conversion and storage, catalysts, electronic devices, sensing, and separation. Herein, the achievements of synthetic strategies for preparing small-molecule diyne structures (GDY substructure), 1D nanoribbons, and 2D GDY are presented. These studies may help future investigations into the basic structure-related properties of GDY and synthetic methodology for the future developments of GDY-related 2D carbon materials. 相似文献
73.
Dr. Jagadeesh Yerri Dr. José Dias Dr. Mallikajurna Reddy Nimmakayala Franck Razafindrainibe Charlotte Courageux Anne-Julie Gastellier Johanne Jegoux Dr. Caroline Coisne Dr. Christophe Landry Dr. Fabien Gosselet Johan Hachani Dr. Jean-François Goossens Prof. Marie-Pierre Dehouck Dr. Florian Nachon Dr. Rachid Baati 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(65):15035-15044
Novel 6-alkyl- and 6-alkenyl-3-fluoro-2-pyridinaldoximes have been synthesised by using a mild and efficient chemoselective hydrogenation of 6-alkynyl-3-fluoro-2-pyridinaldoxime scaffolds, without altering the reducible, unprotected, sensitive oxime functionality and the C−F bond. These novel 6-alkyl-3-fluoro-2-pyridinaldoximes may find medicinal application as antidotes to organophosphate poisoning. Indeed, one low-molecular-weight compound exhibited increased affinity for sarin-inhibited acetylcholinesterase (hAChE) and greater reactivation efficiency or resurrection for sarin-inhibited hAChE, compared with those of 2-pyridinaldoxime (2-PAM) and 1-({[4-(aminocarbonyl)pyridinio]methoxy}methyl)-2-[(hydroxyimino)methyl]pyridinium chloride (HI-6), two pyridinium salts currently used as antidote by several countries. In addition, the uncharged 3-fluorinated bifunctional hybrid showed increased in vitro blood–brain barrier permeability compared with those of 2-PAM, HI-6 and obidoxime. These promising features of novel low-molecular-weight alkylfluoropyridinaldoxime open up a new era for the design, synthesis and discovery of central non-quaternary broad spectrum reactivators for organophosphate-inhibited cholinesterases. 相似文献
74.
Dr. Kwan Yin Cheung Prof. Yasutomo Segawa Prof. Kenichiro Itami 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(65):14791-14801
The development of carbon nanobelts and related belt-shaped polycyclic aromatic hydrocarbons has gained momentum in recent years. This Minireview focuses on the synthetic strategies used in constructing these aesthetically appealing molecular nanocarbons. Examples of carbon nanobelts and related belt-shaped polycyclic aromatic hydrocarbons reported in recent years as well as some representative synthetic attempts in earlier times are discussed. 相似文献
75.
Kenna L. Salvatore Diana M. Lutz Dr. Haoyue Guo Dr. Shiyu Yue Joceline Gan Dr. Xiao Tong Dr. Ping Liu Dr. Esther S. Takeuchi Dr. Kenneth J. Takeuchi Dr. Amy C. Marschilok Dr. Stanislaus S. Wong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(42):9389-9402
Solution-based, anionic doping represents a convenient strategy with which to improve upon the conductivity of candidate anode materials such as Li4Ti5O12 (LTO). As such, novel synthetic hydrothermally-inspired protocols have primarily been devised herein, aimed at the large-scale production of unique halogen-doped, micron-scale, three-dimensional, hierarchical LTO flower-like motifs. Although fluorine (F) doping has been explored, the use of chlorine (Cl) dopants is the primary focus here. Several experimental variables, such as dopant amount, lithium hydroxide concentration, and titanium butoxide purity, were probed and perfected. Furthermore, the Cl doping process did not damage the intrinsic LTO morphology. The analysis, based on interpreting a compilation of SEM, XRD, XPS, and TEM-EDS results, was used to determine an optimized dopant concentration of Cl. Electrochemical tests demonstrated an increased capacity via cycling of 12 % for a Cl-doped sample as compared with pristine LTO. Moreover, the Cl-doped LTO sample described in this study exhibited the highest discharge capacity yet reported at an observed rate of 2C for this material at 143mAh g−1. Overall, these data suggest that the Cl dopant likely enhances not only the ion transport capabilities, but also the overall electrical conductivity of our as-prepared structures. To help explain these favorable findings, theoretical DFT calculations were used to postulate that the electronic conductivity and Li diffusion were likely improved by the presence of increased Ti3+ ion concentration coupled with widening of the Li migration channel. 相似文献
76.
Dr. Atash V. Gurbanov Dr. Maxim L. Kuznetsov Dr. Kamran T. Mahmudov Prof. Armando J. L. Pombeiro Prof. Giuseppe Resnati 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(65):14833-14837
Intramolecular chalcogen bonding in arylhydrazones of sulfamethizole is strengthened by conjugation in the π-system of a noncovalent five-membered ring. The S⋅⋅⋅O distance in the sulfamethizole moiety of these compounds ranges from 2.698(3) to 2.806(15) Å, which indicates its strong dependence on the attached arylhydrazone fragments. Information on the nature of the intramolecular chalcogen bond was afforded by DFT calculations. 相似文献
77.
Kazuki Inaba Masato Endo Naoto Iibuchi Prof. Dr. Daisuke Takahashi Prof. Dr. Kazunobu Toshima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(45):10222-10225
The first total synthesis of terpioside B ( 1 ) has been accomplished. Key steps include the stereoselective installments of a set of challenging 1,2-cis-glycosidic linkages. Thus, α(1,4)-linked d -galactoside was effectively constructed from a 1,2-anhydrogalactose donor and an unprotected 1,6-anhydrogalactose acceptor by using a boron-mediated aglycon delivery (BMAD) method. In addition, α-l -fucofuranosides were stereoselectively and simultaneously constructed by remote group-assisted 1,2-cis-α-stereoselective glycosylations. 相似文献
78.
Pierre Thesmar Seemon Coomar Dr. Alessandro Prescimone Prof. Dr. Daniel Häussinger Prof. Dr. Dennis Gillingham Prof. Dr. Olivier Baudoin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(66):15298-15312
This article provides a detailed report of our efforts to synthesize the dithiodiketopiperazine (DTP) natural products (−)-epicoccin G and (−)-rostratin A using a double C(sp3)−H activation strategy. The strategy's viability was first established on a model system lacking the C8/C8’ alcohols. Then, an efficient stereoselective route including an organocatalytic epoxidation was secured to access a key bis-triflate substrate. This bis-triflate served as the functional handles for the key transformation of the synthesis: a double C(sp3)−H activation. The successful double activation opened access to a common intermediate for both natural products in high overall yield and on a multigram scale. After several unsuccessful attempts, this intermediate was efficiently converted to (−)-epicoccin G and to the more challenging (−)-rostratin A via suitable oxidation/reduction and protecting group sequences, and via a final sulfuration that occurred in good yield and high diastereoselectivity. These efforts culminated in the synthesis of (−)-epicoccin G and (−)-rostratin A in high overall yields (19.6 % over 14 steps and 12.7 % over 17 steps, respectively), with the latter being obtained on a 500 mg scale. Toxicity assessments of these natural products and several analogues (including the newly synthesized epicoccin K) in the leukemia cell line K562 confirmed the importance of the disulfide bridge for activity and identified dianhydrorostratin A as a 20x more potent analogue. 相似文献
79.
Tomasz Nienałtowski Paweł Szczepanik Paweł Małecki Dr. Dorota Czajkowska-Szczykowska Dr. Stefan Czarnocki Dr. Jolanta Pawłowska Dr. Anna Kajetanowicz Prof. Karol Grela 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(67):15708-15717
A large-scale synthesis of known Ru olefin metathesis catalyst VII featuring an unsymmetrical N-heterocyclic carbene (NHC) ligand with one 2,5-diisopropylphenyl (DIPP) and one thiophenylmethylene N-substituent is reported. The optimised procedure does not require column chromatography in any step and allows for preparation of up to 0.5 kg batches of the catalyst from simple precursors. The application profile of the obtained catalyst was studied in environmentally friendly dimethyl carbonate (DMC). Although VII exhibited low efficiency in cross-metathesis (CM) with electron-deficient partners, good to excellent results were noted for substrates featuring easy to isomerise C−C double bonds. This includes polyfunctional substrates of medicinal chemistry interest, such as analogues of psychoactive 5F-PB-22 and NM-2201 and two PDE5 inhibitors—Sildenafil and Vardenafil. Finally, a larger scale ring-closing metathesis (RCM) of a Vardenafil derivative was conducted in DMC, allowing for straightforward isolation of the expected product (23 g) in high yield and with low Ru contamination level (7.7 ppm). 相似文献
80.
Amit Vijay Sasane Dr. Antony Sekar Kulandai Raj Tzu-Hsuan Chao Dr. Mu-Jeng Chen Dr. Rai-Shung Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(70):16932-16938
Gold-catalyzed oxidations of propargyl alcohols with nitrones by using a P(tBu)2(o-biphenyl)Au+ catalyst, afforded bicyclic annulation products from the Mannich reactions of gold enolates. The same reactions of propargyl amines with nitrones by using the same gold catalyst gave distinct oxoarylation products. Our DFT calculations indicate that oxidation of propargyl alcohols with nitrones by using electron-rich gold catalysts lead only to gold carbenes, which can generate gold enolates or oxoarylation intermediates with enolate species having a barrier smaller than that of oxoarylation species. 相似文献