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排序方式: 共有1480条查询结果,搜索用时 15 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.
Georges Belfort 《Angewandte Chemie (International ed. in English)》2019,58(7):1892-1902
After 70 years, modern pressure‐driven polymer membrane processes with liquids are mature and accepted in many industries due to their good performance, ease of scale‐up, low energy consumption, modular compact construction, and low operating costs compared with thermal systems. Successful isothermal operation of synthetic membranes with liquids requires consideration of three critical aspects or “legs” in order of relevance: selectivity, capacity (i.e. permeation flow rate per unit area) and transport of mass and momentum comprising concentration polarization (CP) and fouling (F). Major challenges remain with respect to increasing selectivity and controlling mass transport in, to and away from membranes. Thus, prediction and control of membrane morphology and a deep understanding of the mechanism of dissolved and suspended solute transport near and in the membrane (i.e. diffusional and convective mass transport) is essential. Here, we focus on materials development to address the relatively poor selectivity of liquid membrane filtration with polymers and discuss the critical aspects of transport limitations. Machine learning could help optimize membrane structure design and transport conditions for improved membrane filtration performance. 相似文献
3.
4.
Beatrice Adelizzi Andreas T. Rsch Daan J. vanRijen R. Simone Martire Serkan Esiner Martin Lutz Anja R. A. Palmans E. W. Meijer 《Helvetica chimica acta》2019,102(5)
Recent studies on water‐splitting photoelectrochemical cells (PECs) have demonstrated the intriguing possibility of controlling the spin state in this chemical reaction to form H2 and O2 by exploiting the chirality of organic π‐conjugated supramolecular polymers. Although this fascinating phenomenon has been disclosed, the chiral supramolecular materials reported thus far are not optimized for acting as efficient photosensitizer for dye‐sensitized PECs. In this work we report on the design, synthesis, and characterization of chiral supramolecular aggregates based on C3‐symmetric triphenylamine‐based dyes that are able to both absorb visible light and control the spin state of the process. Variable temperature‐dependent spectroscopic measurements reveal the assembly process of the dyes and confirm the formation of chiral aggregates, both in solution as well as on solid supports. Photoelectrochemical measurements on TiO2‐based anodes validate the advantage of using chiral supramolecular aggregates as photosensitizer displaying higher photocurrent compared to achiral analogues. Moreover, fluorimetric tests for the quantification of the hydrogen peroxide produced, confirm the possibility of controlling the spin of the reaction exerting spin‐selection with chiral supramolecular polymers. These results represent a further step towards the next‐generation of organic‐based water‐splitting solar cells. 相似文献
5.
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
6.
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
7.
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
8.
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
9.
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
10.
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