全文获取类型
收费全文 | 1347篇 |
免费 | 154篇 |
国内免费 | 317篇 |
专业分类
化学 | 1668篇 |
晶体学 | 5篇 |
力学 | 6篇 |
综合类 | 4篇 |
数学 | 2篇 |
物理学 | 133篇 |
出版年
2024年 | 1篇 |
2023年 | 16篇 |
2022年 | 36篇 |
2021年 | 57篇 |
2020年 | 75篇 |
2019年 | 51篇 |
2018年 | 51篇 |
2017年 | 44篇 |
2016年 | 83篇 |
2015年 | 72篇 |
2014年 | 67篇 |
2013年 | 89篇 |
2012年 | 92篇 |
2011年 | 81篇 |
2010年 | 74篇 |
2009年 | 83篇 |
2008年 | 82篇 |
2007年 | 85篇 |
2006年 | 62篇 |
2005年 | 90篇 |
2004年 | 59篇 |
2003年 | 55篇 |
2002年 | 48篇 |
2001年 | 42篇 |
2000年 | 33篇 |
1999年 | 38篇 |
1998年 | 40篇 |
1997年 | 23篇 |
1996年 | 23篇 |
1995年 | 22篇 |
1994年 | 22篇 |
1993年 | 20篇 |
1992年 | 16篇 |
1991年 | 17篇 |
1990年 | 10篇 |
1989年 | 10篇 |
1988年 | 12篇 |
1987年 | 10篇 |
1986年 | 7篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 4篇 |
1977年 | 1篇 |
排序方式: 共有1818条查询结果,搜索用时 14 毫秒
1.
Dr. Zuzanna Wojdyla Prof. Tomasz Borowski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(18):e202104106
Fe(II)/2-oxoglutarate dependent dioxygenases (ODDs) share a double stranded beta helix (DSBH) fold and utilise a common reactive intermediate, ferryl species, to catalyse oxidative transformations of substrates. Despite the structural similarities, ODDs accept a variety of substrates and facilitate a wide range of reactions, that is hydroxylations, desaturations, (oxa)cyclisations and ring rearrangements. In this review we present and discuss the factors contributing to the observed (regio)selectivities of ODDs. They span from inherent properties of the reactants, that is, substrate molecule and iron cofactor, to the interactions between the substrate and the enzyme's binding cavity; the latter can counterbalance the effect of the former. Based on results of both experimental and computational studies dedicated to ODDs, we also line out the properties of the reactants which promote reaction outcomes other than the “default” hydroxylation. It turns out that the reaction selectivity depends on a delicate balance of interactions between the components of the investigated system. 相似文献
2.
3.
A photoinduced decarboxylative three-component coupling reaction involving amine, maleic anhydride, and fluorinated alkyl iodides has been developed, leading to synthetically valuable fluoroalkyl-containing acrylamides with a high E selectivity. A broad array of substrates including monoprotected amino acid are capable coupling partners. Preliminary mechanistic studies suggest a stepwise process. This reaction represents the first example of photoinduced decarboxylative difunctionalization of maleic anhydride. 相似文献
4.
Dr. Ting Ouyang Sheng Huang Xiao-Tong Wang Prof. Zhao-Qing Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(62):14024-14035
One of the most effective ways to cope with the problems of global warming and the energy shortage crisis is to develop renewable and clean energy sources. To achieve a carbon-neutral energy cycle, advanced carbon sequestration technologies are urgently needed, but because CO2 is a thermodynamically stable molecule with the highest carbon valence state of +4, this process faces many challenges. In recent years, electrochemical CO2 reduction has become a promising approach to fix and convert CO2 into high-value-added fuels and chemical feedstock. However, the large-scale commercial use of electrochemical CO2 reduction systems is hindered by poor electrocatalyst activity, large overpotential, low energy conversion efficiency, and product selectivity in reducing CO2. Therefore, there is an urgent need to rationally design highly efficient, stable, and scalable electrocatalysts to alleviate these problems. This minireview also aims to classify heterogeneous nanostructured electrocatalysts for the CO2 reduction reaction (CDRR). 相似文献
5.
Dr. Carlos Lázaro-Milla Jon Macicior Dr. Hikaru Yanai Prof. Dr. Pedro Almendros 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(41):8983-8989
Herein, we report investigations embodying the first example of reversal of the native regioselectivity in the reaction of allenols with electrophiles. The effortlessness of C−C bond formation, mild reaction conditions, neither catalysts nor light irradiation, and exquisite selectivity, both in terms of functional-group tolerance and chemo-, site-, and stereo-selectivity, converts this trifluorosulfonylation-rearrangement sequence into an appealing protocol for the preparation of novel functionalized enones. The synthetic utility of this method has been validated by the conversion of the initially prepared bis(triflyl)enones into a variety of bis(triflyl)-functionalized molecules such as 1,3-dienes, allylic alcohols, pyrroles, pyrazoles, and chromenes. Besides, DFT calculations have provided a reliable understanding of observed selectivity. 相似文献
6.
Zhongxian Song Yun Xing Tingji Zhang Jinggang Zhao Junkai Wang Yanli Mao Baolin Zhao Xuejun Zhang Min Zhao Ziang Ma 《应用有机金属化学》2020,34(3):e5446
A series of Ce-Fe-Ox catalysts prepared by the different calcination temperatures (marked as CF-X, where X represented calcination temperature) were used to the selectivity catalytic reduction of NOx by NH3. The results explained the relationship between calcination temperature and the sulfate species over Ce-Fe-Ox, and then investigated the surface acidity and catalytic performance. The large amounts of sulfate species were formed over CF-450 and CF-550 while it was decomposed with further the increasing of calcination temperature, which resulted in the loss of surface acidity, causing a decrease in the catalytic activity over Ce-Fe-Ox. Thereby, the CF-450 catalyst showed the best catalytic activity and over 90% NOx conversion was obtained at 244–450 °C. Besides, the favored pore structure, more Fe3+ active species, higher Ce3+ concentration and the abundance of chemical adsorbed oxygen species, as well as the surface acid sites, would together contribute to the excellent catalytic activity of CF-450 catalyst. 相似文献
7.
Guanlin Li Ling Zhao Yicong Luo Youbin Peng Kai Xu Dr. Xiaohong Huo Prof. Dr. Wanbin Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(24):e202200273
Asymmetric desymmetrization has been demonstrated to be a powerful strategy for building stereocenters in asymmetric synthesis. Herein, a Pd/Cu catalyzed asymmetric desymmetrization reaction with a simple geminal dicarboxylate is reported. A wide scope of imino esters bearing an aryl or heteroaromatic group were compatible with this bimetallic catalytic system. The reactions proceeded smoothly, giving the desired products in good yields with high to excellent regio-, diastereo-, and enantioselectivity (up to 20 : 1 branched:linear, >20 : 1 dr, >99 % ee). Notably, the reaction favored branched selectivity, which is unusual for the Pd-catalyzed allylic alkylation reaction. In addition, the standard product could be easily transformed to other valuable molecules such as chiral allylic alcohols, carbamates, and organic boron compounds. Furthermore, DFT calculations were conducted to explain the origin of the branched selectivity. 相似文献
8.
How Does Solvation Affect the Binding of Hydrophilic Amino Saccharides to Cucurbit[7]uril with Exceptional Anomeric Selectivity? 下载免费PDF全文
Jianping Wang Yoonjung Jang Jayshree K. Khedkar Jin Young Koo Yonghwi Kim Chang Jun Lee Young Min Rhee Kimoon Kim 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(44):15791-15799
Cucurbit[7]uril (CB[7]) is known to bind strongly to hydrophilic amino saccharide guests with exceptional α‐anomer selectivities under aqueous conditions. Single‐crystal X‐ray crystallography and computational methods were used to elucidate the reason behind this interesting phenomenon. The crystal structures of protonated galactosamine (GalN) and glucosamine (GluN) complexes confirm the inclusion of α anomers inside CB[7] and disclose the details of the host–guest binding. Whereas computed gas‐phase structures agree with these crystal structures, gas‐phase binding free energies show preferences for the β‐anomer complexes over their α counterparts, in striking contrast to the experimental results under aqueous conditions. However, when the solvation effect is considered, the binding structures drastically change and the preference for the α anomers is recovered. The α anomers also tend to bind more tightly and leave less space in the CB[7] cavity toward inclusion of only one water molecule, whereas loosely bound β anomers leave more space toward accommodating two water molecules, with markedly different hydrogen‐bonding natures. Surprisingly, entropy seems to contribute significantly to both anomeric discrimination and binding. This suggests that of all the driving factors for the strong complexation of the hydrophilic amino saccharide guests, water mediation plays a crucial role in the anomer discrimination. 相似文献
9.
A simple, highly efficient synthetic protocol is developed for the synthesis of unsymmetrical diaryl vinyl selenides from diaryldiselenide and β-bromo styrene under transition-metal free conditions in N,N′-dimethyl propylene urea and 130 °C to afford high yields and excellent selectivities. This method provides a new strategy to fabricate a wide variety of important substituted molecular skeletons and an alternative to conventionally used metal salts, additives, and ligands. 相似文献
10.
Dr. Yi Jiang Lei-Li Sun Guang-Zong Ren Xiang Niu Wen-zhou Hu Prof. Zhi-Qiang Hu 《ChemistryOpen》2015,4(3):378-382
The development of novel selective probes with high sensitivity for the detection of Al3+ is widely considered an important research goal due to the importance of such probes in medicine, living systems and the environment. Here, we describe a new fluorescent probe, N′-(4-diethylamino-2-hydroxybenzylidene)-2-hydroxybenzohydrazide (1), for Al3+. Probe 1 was evaluated in a solution of acetonitrile/water (1:1 v/v). Compared with previously reported probes for Al3+, probe 1 can be synthesized easily and in high yield. A Job plot confirmed that probe 1 is able to complex Al3+ in a 1:1 ratio, and the binding constant was determined to be 4.25×108 m−1. Moreover, the detection limit was as low as 6.7×10−9 m, suggesting that probe 1 has a high sensitivity. Common coexistent metal ions, such as K+, Co2+, Ca2+, Ba2+, Ni2+, Pb2+, Hg2+, Ce2+, Zn2+, Cd2+, Fe3+, showed little or no interference in the detection of Al3+ in solution, demonstrating the high selectivity of the probe. Finally, the ability of probe 1 to act as a fluorescent probe for Al3+ in living systems was evaluated in Gram-negative bacteria, Escherichia coli, and confocal laser scanning microscopy confirmed its utility. The results of this study suggest that 1 has appropriate properties to be developed for application as a fluorescent probe of Al3+ for use in biological studies. 相似文献