全文获取类型
收费全文 | 24894篇 |
免费 | 3324篇 |
国内免费 | 2363篇 |
专业分类
化学 | 12463篇 |
晶体学 | 178篇 |
力学 | 1200篇 |
综合类 | 67篇 |
数学 | 1790篇 |
物理学 | 6813篇 |
综合类 | 8070篇 |
出版年
2024年 | 133篇 |
2023年 | 505篇 |
2022年 | 800篇 |
2021年 | 859篇 |
2020年 | 807篇 |
2019年 | 717篇 |
2018年 | 691篇 |
2017年 | 637篇 |
2016年 | 1019篇 |
2015年 | 997篇 |
2014年 | 1306篇 |
2013年 | 1487篇 |
2012年 | 1868篇 |
2011年 | 1836篇 |
2010年 | 1326篇 |
2009年 | 1282篇 |
2008年 | 1476篇 |
2007年 | 1322篇 |
2006年 | 1161篇 |
2005年 | 1042篇 |
2004年 | 778篇 |
2003年 | 635篇 |
2002年 | 622篇 |
2001年 | 592篇 |
2000年 | 552篇 |
1999年 | 720篇 |
1998年 | 673篇 |
1997年 | 645篇 |
1996年 | 639篇 |
1995年 | 590篇 |
1994年 | 490篇 |
1993年 | 416篇 |
1992年 | 391篇 |
1991年 | 334篇 |
1990年 | 311篇 |
1989年 | 269篇 |
1988年 | 203篇 |
1987年 | 156篇 |
1986年 | 102篇 |
1985年 | 64篇 |
1984年 | 39篇 |
1983年 | 26篇 |
1982年 | 15篇 |
1981年 | 16篇 |
1980年 | 12篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1957年 | 6篇 |
1955年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 4 毫秒
971.
Mechanistic Insights into the Interface‐Directed Transformation of Thiols into Disulfides and Molecular Hydrogen by Visible‐Light Irradiation of Quantum Dots 下载免费PDF全文
Xu‐Bing Li Zhi‐Jun Li Yu‐Ji Gao Qing‐Yuan Meng Shan Yu Prof. Dr. Richard G. Weiss Prof. Dr. Chen‐Ho Tung Prof. Dr. Li‐Zhu Wu 《Angewandte Chemie (International ed. in English)》2014,53(8):2085-2089
Quantum dots (QDs) offer new and versatile ways to harvest light energy. However, there are few examples involving the utilization of QDs in organic synthesis. Visible‐light irradiation of CdSe QDs was found to result in virtually quantitative coupling of a variety of thiols to give disulfides and H2 without the need for sacrificial reagents or external oxidants. The addition of small amounts of nickel(II) salts dramatically improved the efficiency and conversion through facilitating the formation of hydrogen atoms, thereby leading to faster regeneration of the ground‐state QDs. Mechanistic studies reveal that the coupling reaction occurs on the QD surfaces rather than in solution and offer a blueprint for how these QDs may be used in other photocatalytic applications. Because no sacrificial agent or oxidant is necessary and the catalyst is reusable, this method may be useful for the formation of disulfide bonds in proteins as well as in other systems sensitive to the presence of oxidants. 相似文献
972.
Clickable Periodic Mesoporous Organosilicas: Synthesis,Click Reactions,and Adsorption of Antibiotics 下载免费PDF全文
Dr. Jinsuo Gao Xueying Zhang Dr. Shutao Xu Prof. Feng Tan Prof. Xinyong Li Prof. Yaobin Zhang Prof. Zhenping Qu Prof. Xie Quan Dr. Jian Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(7):1957-1963
Pharmaceutical antibiotics are not easily removed from water by conventional water‐treatment technologies and have been recognized as new emerging pollutants. Herein, we report the synthesis of clickable azido periodic mesoporous organosilicas (PMOs) and their use as adsorbents for the adsorption of antibiotics. Ethane‐bridged PMOs, functionalized with azido groups at different densities, were synthesized by the co‐condensation of 1,2‐bis(trimethoxysilyl)ethane (BTME) and 3‐azidopropyltrimethoxysilane (AzPTMS), in the presence of nonionic‐surfactant triblock‐copolymer P123, in an acidic medium. Four different alkynes were conjugated to azide‐terminated PMOs by means of an efficient click reaction. The clicked PMOs showed improved adsorption capacity (241 μg g?1) for antibiotics (ciprofloxacin hydrochloride) compared with azido‐functionalized PMOs because of the enhanced π–π stacking interactions. These results indicate that click reactions can introduce multifunctional groups onto PMOs, thus demonstrating the great potential of PMOs for environmental applications. 相似文献
973.
Dr. Victor Malgras Dr. Priyanka Jood Dr. Ziqi Sun Prof. Shi Xue Dou Prof. Yusuke Yamauchi Prof. Jung Ho Kim 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10451-10455
Porous titanium dioxide synthesized with a bicontinuous surfactant template is a promising method that leads to a high active surface area electrode. The template used is based on a water/isooctane/dioctyl sodium sulfosuccinate salt together with lecithin. Several parameters were varied during the synthesis to understand and optimize channel formation mechanisms. The material is patterned in stacked conical channels, widening towards the centre of the grains. The active surface area increased by 116 % when the concentration of alkoxide precursors was decreased and increased by 241 % when the template formation temperature was decreased to 10 °C. Increasing the oil phase viscosity tends to widen the pore aperture, thus decreasing the overall active surface area. Changing the phase proportions alters the microemulsion integrity and disrupts channel formation. 相似文献
974.
Shujun Cai Zheming Xiao Yingbo Shi Prof. Dr. Shuanhu Gao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(28):8677-8681
The reaction conditions and scope of the photo‐Nazarov reaction of aryl vinyl ketones were investigated. In contrast to the conventional acid‐catalyzed methods, this photolytic electrocyclization proceeds in the neutral or basic conditions. Irradiating substrates bearing various aromatic rings, acid‐sensitive groups, cyclohexenyl, cycloheptenyl, and unsaturated pyran with UV‐light (254 nm) smoothly yielded hexahydrofluorenones and related structures. This photo‐Nazarov reaction could also be applicable to the substrates carrying β‐alkyl groups on the enone, which gave corresponding polycyclic rings containing quaternary centers. These photo‐electrocyclized products may prove useful for synthesizing a variety of natural products and their derivatives. Further application of this mild photo‐Nazarov reaction in the synthesis of taiwaniaquinol B was achieved. 相似文献
975.
Back Cover: Two‐Dimensional Tetrathiafulvalene Covalent Organic Frameworks: Towards Latticed Conductive Organic Salts (Chem. Eur. J. 45/2014) 下载免费PDF全文
976.
Cong‐Li Gao Xiang Li Dr. Yuan‐Zhi Tan Xin‐Zhou Wu Dr. Qianyan Zhang Prof.Dr. Su‐Yuan Xie Prof. Rong‐Bin Huang 《Angewandte Chemie (International ed. in English)》2014,53(30):7853-7855
Previously reported fused‐pentagon fullerenes stabilized by exohedral derivatization do not share the same cage with those stabilized by endohedral encapsulation. Herein we report the crystallographic identification of #4348C66Cl10, which has the same cage as that of previously reported Sc2@C66. According to the geometrical data of #4348C66Cl10, both strain relief (at the fused pentagons) and local aromaticity (on the remaining sp2‐hybrided carbon framework) contribute to the exohedral stabilization of this long‐sought 66 carbon atom cage. 相似文献
977.
A Protic Ionic Liquid Catalyzes CO2 Conversion at Atmospheric Pressure and Room Temperature: Synthesis of Quinazoline‐2,4(1H,3H)‐diones 下载免费PDF全文
Dr. Yanfei Zhao Bo Yu Dr. Zhenzhen Yang Dr. Hongye Zhang Leiduan Hao Xiang Gao Prof. Zhimin Liu 《Angewandte Chemie (International ed. in English)》2014,53(23):5922-5925
The chemical fixation of CO2 under mild reaction conditions is of significance from a sustainable chemistry viewpoint. Herein a CO2‐reactive protic ionic liquid (PIL), [HDBU+][TFE?], was designed by neutralization of the superbase 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) with a weak proton donor trifluoroethanol (TFE). As a bifunctional catalyst for simultaneously activating CO2 and the substrate, this PIL displayed excellent performance in catalyzing the reactions of CO2 with 2‐aminobenzonitriles at atmospheric pressure and room temperature, thus producing a series of quinazoline‐2,4(1H,3H)‐diones in excellent yields. 相似文献
978.
Yingbo Shi Baochao Yang Shujun Cai Prof. Dr. Shuanhu Gao 《Angewandte Chemie (International ed. in English)》2014,53(36):9539-9543
The total synthesis of gracilamine, a pentacyclic Amaryllidaceae alkaloid, was achieved from simple building blocks. The synthesis features a mild photo‐Nazarov reaction, intramolecular 1,4‐addition, and an intramolecular Mannich reaction. This approach not only confirms the C6 stereochemistry of natural gracilamine, and also provides a novel solution to prepare its derivatives and structurally related natural products. 相似文献
979.
We present the design and synthesis of polyoxazole‐based macrocycles containing a phosphonate group. A reliable route was established that allows for convenient and versatile incorporation of various phosphonate functionalities such as phosphonate ester, acid, and salt at the macrocyclic ring periphery. Such unprecedented macrocyclic compounds are anticipated to be appealing candidates as telomerase inhibitors. 相似文献
980.
We utilized the glycosyl acceptor tagging method with ionic liquid support for synthesis of the core segment of Clostridium botulinum C2 toxin ligand through a divergent synthetic strategy without chromatographic purification.The total yield was 57.1% and the reaction was completed in 10 h.The efficient ionic liquid supported glycosylation and purification procedure was applied for the synthesis of branched glucosamine-containing oligosaccharides for the first time,which expanded the scope of ionic liquid supported synthesis of biologically important oligosaccharides. 相似文献