全文获取类型
收费全文 | 6261篇 |
免费 | 612篇 |
国内免费 | 927篇 |
专业分类
化学 | 7010篇 |
晶体学 | 14篇 |
力学 | 4篇 |
综合类 | 26篇 |
数学 | 259篇 |
物理学 | 487篇 |
出版年
2024年 | 1篇 |
2023年 | 58篇 |
2022年 | 81篇 |
2021年 | 139篇 |
2020年 | 281篇 |
2019年 | 232篇 |
2018年 | 175篇 |
2017年 | 176篇 |
2016年 | 283篇 |
2015年 | 252篇 |
2014年 | 259篇 |
2013年 | 600篇 |
2012年 | 367篇 |
2011年 | 383篇 |
2010年 | 357篇 |
2009年 | 375篇 |
2008年 | 480篇 |
2007年 | 465篇 |
2006年 | 448篇 |
2005年 | 419篇 |
2004年 | 413篇 |
2003年 | 307篇 |
2002年 | 232篇 |
2001年 | 167篇 |
2000年 | 100篇 |
1999年 | 99篇 |
1998年 | 85篇 |
1997年 | 70篇 |
1996年 | 66篇 |
1995年 | 74篇 |
1994年 | 78篇 |
1993年 | 80篇 |
1992年 | 58篇 |
1991年 | 38篇 |
1990年 | 30篇 |
1989年 | 18篇 |
1988年 | 14篇 |
1987年 | 6篇 |
1986年 | 10篇 |
1985年 | 4篇 |
1984年 | 6篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有7800条查询结果,搜索用时 15 毫秒
61.
Haicun Yang Shuipi Cai Yu Jiang Zheng Cao Wenzhong Ma Fanghong Gong Guoliang Tao Chunlin Liu 《Journal of polymer science. Part A, Polymer chemistry》2022,60(10):1571-1587
The commonly used multi-center initiation methods always lead to the formation of quantities of homopolymer in the surface tailoring based on reverse atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization. In this study, a monocenter redox pair constructed of silica bearing tert-butyl hydroperoxide groups and ascorbic acid (SiO2-TBHP/AsAc) was applied to substitute the commonly used initiation method of R-supported RAFT grafting polymerization. All the propagating radicals were restricted on the surface of solid particles during the whole procedure theoretically, resulting in a higher grafting efficiency of 95.1% combined with the “controllable” feature at 10 h. This redox pair was also used to initiate the reverse ATRP in miniemulsion successfully with a grafting efficiency of 86.3% at 10 h. The grafting efficiency obtained under this monocenter initiation method was significantly higher than that of the frequently reported surface modification by reverse ATRP and RAFT polymerization. In addition, the high-efficient surface tailoring was traced and confirmed by nuclear magnetic resonance, Fourier transform infrared, X-ray photoelectron spectroscopy, thermogravimetric analysis, transmission electron microscopy, and other analysis tests. The advantage of this monocenter redox pair will open a new avenue for the potential “high-efficient” surface tailoring of various materials. 相似文献
62.
Miguel Reina Eduardo Gabriel Guzmán-López Annia Galano 《International journal of quantum chemistry》2023,123(2):e27011
A set of new rasagiline derivatives is presented. They were designed to be antioxidant compounds with the potential to be used for treating neurodegenerative disorders. They are expected to be multifunctional molecules that can help reduce oxidative stress, which is thought to contribute to neurodegenerative disorders. The CADMA-Chem computational protocol was used to produce rasagiline derivatives and to evaluate their likeliness as oral drugs and antioxidants. Three of them were identified as the most promising ones. They are proposed to be better free radical scavengers than rasagiline. In addition, they are expected to keep the parent's molecule neuroprotective capability. Hopefully, the results presented here would promote further experimental and theoretical investigations on these compounds. 相似文献
63.
Dr. Chunfeng Chen Dr. Jorge S. Valera Prof. Takuji B. M. Adachi Prof. Thomas M. Hermans 《Chemistry (Weinheim an der Bergstrasse, Germany)》2023,29(1):e202202849
Photoreduction of perylenediimide (PDI) derivatives has been widely studied for use in photocatalysis, hydrogen evolution, photo-responsive gels, and organic semiconductors. Upon light irradiation, the radical anion (PDI⋅−) can readily be obtained, whereas further reduction to the dianion (PDI2−) is rare. Here we show that full 2-electron photoreduction can be achieved using UVC light: 1) in anaerobic conditions by ‘direct photoreduction’ of PDI aggregates, or 2) by ‘indirect photoreduction’ in aerobic conditions due to acetone ketyl radicals. The latter strategy is also efficient for other dyes, such as naphthalenediimide (NDI) and methylviologen (MV2+). Efficient photoreduction on the minute time-scale using simple LED light in aerobic conditions is attractive for use in dissipative light-driven systems and materials. 相似文献
64.
利用化学沉淀法和溶胶凝胶法,通过两步法成功制备出含有尖晶石钴铁氧体和氧化铜的复合催化剂CoFe2O4/CuO,通过扫描电子显微镜(SEM)、X射线光电子能谱(XPS)和X射线衍射(XRD)对制备出的CoFe2O4/CuO进行表征,探究不同高级氧化体系对磺胺甲恶唑(SMX)去除能力,考察过氧乙酸(PAA)浓度、催化剂投加量、水体中常见干扰物质(Cl-,HCO-3,SO42-,HA)和不同自由基捕获剂对SMX去除的影响。分析结果表明CoFe2O4/CuO同时具有CoFe2O4与CuO的特征,对比单独CoFe2O4与CuO,CoFe2O4/CuO对PAA展现出极高的活化性能,在最佳反应条件下(催化剂投加量=20mg·L-1,c(PAA)=200μ... 相似文献
65.
Luminescent open-shell organic radicals have recently been regarded as one of the most potential materials in organic light-emitting diodes(OLEDs). Herein, we have synthesized two new organic radicals, namely tris{4-[4-(tert-butyl)phenoxy]-2,6- dichlorophenyl}methane radical(TTM-O) and tris(4-{[4-(tert-butyl)- phenyl]thio}-2,6-dichlorophenyl)methane radical(TTM-S), by the substitution of chalcogen atom elements at the para position of conventional tris(2,4,6-trichlorophenyl)methyl(TTM) radical moiety. Interestingly, both TTM-O and TTM-S exhibited significantly enhanced photostability compared with the unsubstituted TTM radical parent. Moreover, the chalcogen atom also had a crucial impact on the photoluminescence quantum yield(PLQY) of the radicals, i.e., the PLQY of TTM-S was greatly enhanced compared to TTM radical while TTM-O was nearly non-emissive. Particularly, TTM-S showed intense PLQY of 37.54% and 185-fold longer photostability than that in cyclohexane solution of TTM. 相似文献
66.
Ahmad Bachir Fabiana Ciocchetti Daniel P. Couto Dr. Simone Di Noja Dr. Cristian Pezzato Dr. Giulio Ragazzon 《European journal of organic chemistry》2023,26(29):e202300498
Cyclobis(paraquat-p-phenylene), also known as “blue box”, is a highly electron-deficient macrocycle, widely used as a molecular receptor for small electron-rich molecules. Inserting a reactive functional group onto the molecular structure of this cyclophane is paramount for its inclusion into complex architectures. To this aim, including an alkyne moiety would be ideal, because it can participate in click reactions. However, the synthesis of such alkyne-functionalized cyclophane suffers from several drawbacks: the use of toxic and expensive CCl4, the need for high-pressure reactors, and overall low yield. We have revised the existing synthesis of this cyclophane derivative bearing an alkyne moiety, to overcome all these limitations. In particular, photochemical radical bromination is adopted to obtain a sensitive intermediate. We demonstrated that the synthesized host molecule can be functionalized via click reactions and take part in radical-radical interactions. Our work makes a key functionalized paraquat macrocycle more accessible, facilitating the development of novel redox-responsive systems. 相似文献
67.
Wei-Chen Zhu Yi-Fan Jiang Xin-Yu Liu Shi-Yin Tian Prof. Weidong Rao Prof. Shu-Su Shen Assoc. Prof. Ping Song Dr. Daopeng Sheng Prof. Shun-Yi Wang 《European journal of organic chemistry》2023,26(25):e202300379
A photoinduced synthesis of β-keto thiosulfone/β-keto selenosulfone by the reaction of α-bromoacetophenone with thiosulfonate/selenosulfonate under metal-free and visible light irradiation conditions is developed. Two C−S bonds or one C−S bond and one C−Se bond were constructed simultaneously. 相似文献
68.
Ilya A. P. Jourjine Prof. Dr. Franz Bracher 《European journal of organic chemistry》2023,26(28):e202300399
4-Azafluorenones are typically obtained by acid-mediated cyclization of 2-arylnicotinates. However, this approach fails to give 5-oxygenated 4-azafluorenones due to lactonization of 2-(2-alkoxy)phenylnicotinate intermediates. Herein, we report two modifications of established approaches to 4-azafluorenone synthesis that, either in combination or by themselves, enable the flexible preparation of 4-azafluorenones with diverse oxygenation patterns in the benzenoid ring. Undesired lactonization was circumvented via tert-butyl hydroperoxide (TBHP)-mediated radical cyclization of 2-aryl-3-(hydroxymethyl)pyridines. In the absence of suitable protecting groups for phenolic intermediates, bromide substituents were regioselectively introduced as latent hydroxy groups and later converted under palladium catalysis. We present the first total syntheses of five 4-azafluorenone alkaloids muniranine, darienine, 5,8-dimethoxy-7-hydroxyonychine, 5,6,7,8-tetramethoxyonychine, and 6,8-dihydroxy-7-methoxyonychine in addition to new total syntheses of six 4-azafluorenone alkaloids and one related pyridocoumarin alkaloid. 相似文献
69.
Jie Sun Prof. Dr. Zhenjiang Liu Prof. Dr. Jian Jin 《European journal of organic chemistry》2023,26(13):e202300081
A modular protocol for the triarylamine synthesis has been developed using diarylamines and electron-rich arenes, such as phenols, as the building blocks. The KI/KIO4 system proves to be highly efficient for the cross-dehydrogenative coupling of phenothiazines/phenoxazines with phenols/anilines. A wide range of functional groups attached to both coupling partners were well tolerated. Through the manipulation of reaction temperatures, the sequential assembly of bis-triarylamines could be achieved to provide the unsymmetrically bis-aminated phenols efficiently. Furthermore, the multiple aminated polyphenols were rapidly constructed in good to high yields by a single operation. 相似文献
70.
Yilin Zhao Tingting Hou Liming Zhang Xue Wang Jingli Hou Yangping Liu Guifang Han Yuguang Song 《European journal of organic chemistry》2023,26(18):e202300253
An iron-catalyzed trifluoromethylation of indole-tethered alkene with Togni's reagent to construct CF3-containing spiro[indole-3,3′-pyrrolidine] and tetrahydrocarbazole derivatives under mild and convenient conditions has been disclosed. Mechanistic studies indicate that the reaction proceed through a CF3 radical addition to the alkene, followed by sequential dearomatizing spiocyclization of the indole and oxidation to afford the spiro[indole-3,3′-pyrrolidine] derivatives. Meanwhile, when the substituent at the C2 position of the indole is hydrogen, the CF3-containing tetrahydrocarbazole is obtained through trifluoromethylation of alkene and cyclization of indole. 相似文献