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101.
Guang‐Tao Xu Liang‐Liang Wu Xiao‐Yong Chang Tim Wai Hung Ang Wai‐Yeung Wong Jie‐Sheng Huang Chi‐Ming Che 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(45):16443-16452
Supramolecular ensembles adopting ring‐in‐ring structures are less developed compared with catenanes featuring interlocked rings. While catenanes with inter‐ring closed‐shell metallophilic interactions, such as d10–d10 AuI–AuI interactions, have been well‐documented, the ring‐in‐ring complexes featuring such metallophilic interactions remain underdeveloped. Herein is described an unprecedented ring‐in‐ring structure of a AuI‐thiolate Au12 cluster formed by recrystallization of a AuI‐thiolate Au10 [2]catenane from alkane solvents such as hexane, with use of a bulky dibutylfluorene‐2‐thiolate ligand. The ring‐in‐ring AuI‐thiolate Au12 cluster features inter‐ring AuI–AuI interactions and underwent cluster core change to form the thermodynamically more stable Au10 [2]catenane structure upon dissolving in, or recrystallization from, other solvents such as CH2Cl2, CHCl3, and CH2Cl2/MeCN. The cluster‐to‐cluster transformation process was monitored by 1H NMR and ESI‐MS measurements. Density functional theory (DFT) calculations were performed to provide insight into the mechanism of the “ring‐in‐ring? [2]catenane” interconversions. 相似文献
102.
Inspired by the recent interest of halogen bonding (XB) in the solid state, we detail a comprehensive benchmark study of planewave DFT geometry and interaction energy of lone-pair (LP) type and aromatic (AR) type halogen bonded complexes, using PAW and USPP pseudopotentials. For LP-type XB dimers, PBE-PAW generally agrees with PBE/aug-cc-pVQZ(−pp) geometries but significantly overbinds compared to CCSD(T)/aug-cc-pVQZ(-pp). Grimme's D3 dispersion corrections to PBE-PAW gives better agreement to the MP2/cc-pVTZ(-pp) results for AR-type dimers. For interaction energies, PBE-PAW may overbind or underbind for weaker XBs but clearly overbinds for stronger XBs. D3 dispersion corrections exacerbate the overbinding problem for LP-type complexes but significantly improves agreement for AR-type complexes compared to CCSD(T)/CBS. Finally, for periodic XB crystals, planewave PBE methods slightly underestimate the XB lengths by 0.03 to 0.05 Å. © 2019 Wiley Periodicals, Inc. 相似文献
103.
104.
105.
Lin Yingzi Zhu Yang Li Ang Wu Tianmo Song Yingji 《Research on Chemical Intermediates》2020,46(2):1405-1424
Research on Chemical Intermediates - In this study, biomorphic WO3-Cx nanomaterial was successfully prepared with rice hull as biological templates. The structure and morphology of the nanomaterial... 相似文献
106.
Shuangshuang Ji Xiuzhu Yang Xiaolong Chen Ang Li Doudou Yan Haiyan Xu Hao Fei 《Chemical science》2020,11(34):9126
The development of chemotherapy, an important cancer treatment modality, is hindered by the frequently found drug-resistance phenomenon. Meanwhile, researchers have been enthused lately by the synergistic use of chemotherapy with emerging immunotherapeutic treatments. In an effort to address both of the two unmet needs, reported herein is a study on a series of membrane active iridium(iii) complexed oligoarginine peptides with a new cell death mechanism capable of overcoming drug resistance as well as stimulating immunological responses. A systematic structure–activity relationship study elucidated the interdependent effects of three structural factors, i.e., hydrophobicity, topology and cationicity, on the regulation of the cytotoxicity of the Ir(iii)-oligoarginine peptides. With the most prominent toxicities, Ir-complexed octaarginines (R8) were found to display a progressive oncotic cell death featuring cell membrane-penetration and eruptive cytoplasmic content release. Consequently, this membrane-centric death mechanism showed promising potential in overcoming multiple chemical drug-resistance of cancer cells. More interestingly, the eruptive mode of cell death proved to be immunogenic by stimulating the dendritic cell maturation and inflammatory factor accumulation in mice tumours. Taking these mechanisms together, this work demonstrates that membrane active compounds may become the next generation chemotherapeutics because of their combined advantages.Structure optimized Ir-complexed cyclic octa-arginine shows a potential of “one-drug two-effects” for cancer treatment. 相似文献
107.
Zhaohong Lu Ming Yang Pengxi Chen Xiaochun Xiong Prof. Dr. Ang Li 《Angewandte Chemie (International ed. in English)》2014,53(50):13840-13844
A unified and bioinspired oxidative cyclization strategy was used in the first total syntheses of naturally occurring 12‐epi‐hapalindole Q isonitrile, hapalonamide H, deschloro 12‐epi‐fischerindole I nitrile, and deschloro 12‐epi‐fischerindole W nitrile, as well as the structural revision of the latter. Hapalindoles H and Q were also synthesized. 相似文献
108.
109.
Xuan Liu Dr. Chengxi Huang Dr. Bo Ouyang Dr. Yongping Du Boyu Fu Zhengwei Du Qiang Ju Dr. Jingjing Ma Prof. Dr. Ang Li Prof. Dr. Erjun Kan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(43):e202201034
The CO2 reduction reaction (CRR) represents a promising route for the clean utilization of renewable resources. But mass-transfer limitations seriously hinder the forward step. Enhancing the surface hydrophobicity by using polymers has been proved to be one of the most efficient strategies. However, as macromolecular organics, polymers on the surface hinder the transfer of charge carriers from catalysts to reactants. Herein, we describe an in-situ surface fluorination strategy to enhance the surface hydrophobicity of TiO2 without a barrier layer of organics, thus facilitating the mass transfer of CO2 to catalysts and charge transfer. With less obstruction to charge transfer, a higher CO2, and lower H+ surface concentration, the photocatalytic CRR generation rate of methanol (CH3OH) is greatly enhanced to up to 247.15 μmol g−1 h−1. Furthermore, we investigated the overall defects; enhancing the surface hydrophobicity of catalysts provides a general and reliable method to improve the competitiveness of CRR. 相似文献
110.
Angélica Garzon-Fontecha Harvi Castillo Daniel Escobar-Rincón Elisabeth Restrepo-Parra Wencel De La Cruz 《Surface and interface analysis : SIA》2019,51(9):906-913
Cr, Nb, Cr/Nb, CrNx, NbNx, CrNbN, and (CrN/NbN)n structures were produced on Si and glass substrates, using the d.c. magnetron sputtering technique. Compositional analysis, based on binding energies of Cr, Nb, and N, was carried out by means of X-ray photoelectron spectroscopy (XPS). Through Auger electron spectroscopy (AES), depth profiles were obtained, allowing to demonstrate the multilayers production. Surface morphological characteristics, as roughness and grain size, were evaluated by atomic force microscopy (AFM), revealing very smooth surfaces, that is a consequence of the deposition parameters used in the synthetization experiments. Finally, for different configurations, conductivity measurements were carried out, revealing the influence of nitrogen content and temperature on electron transport. It was found that substoichiometric nitrides (CrN0.35 and NbN0.12) exhibited the highest conductivity, because the nitrogen atoms act as donor of electrons. 相似文献