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911.
自20世纪70年代起,人们利用原位光谱技术(拉曼、红外等)对电化学界面进行了系统的研究,进而发展出原位谱学电化学的研究方向,由于其具有良好的表面灵敏度和能量分辨率,可以提供更多的表面反应信息,进而从微观上揭示反应机理. 伴随着纳米技术的兴起,表面增强拉曼光谱技术取得了快速的发展. 近来,壳层隔绝纳米粒子增强拉曼光谱(shell-isolated nanoparticle-enhanced Raman spectroscopy,SHINERS)技术更是得到人们的广泛关注. SHINERS的出现为研究单晶模型电极上的催化反应提供了一种非常好的原位光谱技术. 本文主要对原位电化学SHINERS技术在单晶电极界面研究的具体应用及其发展前景进行相关论述. 相似文献
912.
Fang Hu Guobin Qi Kenry Duo Mao Shiwei Zhou Min Wu Wenbo Wu Bin Liu 《Angewandte Chemie (International ed. in English)》2020,59(24):9288-9292
Protected by the host cells, the hidden intracellular bacteria are typically difficult to kill by common antibiotics and cannot be visualized without complex cellular pretreatments. Herein, we successfully developed a bacteria‐metabolizable dual‐functional probe TPEPy‐d ‐Ala, which is based on d ‐alanine and a photosensitizer with aggregation‐induced emission for fluorescence turn‐on imaging of intracellular bacteria in living host cells and photodynamic ablation in situ. Once metabolically incorporated into bacterial peptidoglycan, the intramolecular motions of TPEPy‐d ‐Ala are inhibited, leading to an enhanced fluorescent signal, which allows the clear visualization of the intracellular bacteria. Moreover, TPEPy‐d ‐Ala can effectively ablate the labeled intracellular bacteria in situ owing to covalent ligation to peptidoglycan, yielding a low intracellular minimum inhibitory concentration (MIC) of 20±0.5 μg mL?1, much more efficient than that of a commonly used antibiotic, vancomycin. 相似文献
913.
Yang Li Yuan‐Yuan An Jian‐Zhong Fan Xiao‐Xu Liu Xin Li F. Ekkehardt Hahn Yao‐Yu Wang Ying‐Feng Han 《Angewandte Chemie (International ed. in English)》2020,59(25):10073-10080
A series of supramolecular assemblies of types [Ag8( L )4](PF6)8 and [Ag4( L )2](PF6)4, obtained from the tetraphenylethylene (TPE) bridged tetrakis(1,2,4‐triazolium) salts H4‐L(PF6)4 and AgI ions, is described. The assembly type obtained dependends on the N‐wingtip substituents of H4‐L(PF6)4. Changes in the lengths of the N4‐wingtip substituents enables controlled formation of assemblies with either [Ag4( L )2](PF6)4 or [Ag8( L )4](PF6)8 stoichiometry. The molecular structures of selected [Ag8( L )4](PF6)8 and [Ag4( L )2](PF6)4 assemblies were determined by X‐ray diffraction analyses. While H4‐ L (PF6)4 does not exhibit fluorescence in solution, their tetra‐NHC (NHC=N‐heterocyclic carbene) assemblies do upon NHC–metal coordination. Upon irradiation, all assemblies undergo a light‐induced, supramolecule‐to‐supramolecule structural transformation by an oxidative photocyclization involving phenyl groups of the TPE core, resulting in a significant change of the luminescence properties. 相似文献
914.
Jin‐Yue Zeng Xiao‐Shuang Wang Bo‐Ru Xie Min‐Jie Li Xian‐Zheng Zhang 《Angewandte Chemie (International ed. in English)》2020,59(25):10087-10094
Fluorescent materials exhibiting two‐photon induction (TPI) are used for nonlinear optics, bioimaging, and phototherapy. Polymerizations of molecular chromophores to form π‐conjugated structures were hindered by the lack of long‐range ordering in the structure and strong π–π stacking between the chromophores. Reported here is the rational design of a benzothiadiazole‐based covalent organic framework (COF) for promoting TPI and obtaining efficient two‐photon induced fluorescence emissions. Characterization and spectroscopic data revealed that the enhancement in TPI performance is attributed to the donor‐π‐acceptor‐π‐donor configuration and regular intervals of the chromophores, the large π‐conjugation domain, and the long‐range order of COF crystals. The crystalline structure of TPI‐COF attenuates the π–π stacking interactions between the layers, and overcomes aggregation‐caused emission quenching of the chromophores for improving near‐infrared two‐photon induced fluorescence imaging. 相似文献
915.
Jie Yang Xiao‐Ming Zhang Fu‐Min Zhang Shao‐Hua Wang Yong‐Qiang Tu Zhen Li Xi‐Chao Wang Hong Wang 《Angewandte Chemie (International ed. in English)》2020,59(22):8471-8475
An enantioselective aldehyde α‐alkylation/semipinacol rearrangement was achieved through organo‐SOMO catalysis. The catalytically generated enamine radical cation serves as a carbon radical electrophile that can stereoselectively add to the alkene of an allylic alcohol and initiate ensuing ring‐expansion of cyclopropanol or cyclobutanol. This tandem reaction enables the production of a wide range of nonracemic functionalizable α‐quaternary‐δ‐carbonyl cycloketones in high yields and excellent enantioselectivity from simple aldehydes and allylic alcohols. As a key step, the intramolecular reaction was also successfully applied in the asymmetric total synthesis of (+)‐cerapicol. 相似文献
916.
Chao Wang Min Hu Yueying Chu Xue Zhou Qiang Wang Guodong Qi Shenhui Li Jun Xu Feng Deng 《Angewandte Chemie (International ed. in English)》2020,59(18):7198-7202
The understanding of catalyst deactivation represents one of the major challenges for the methanol‐to‐hydrocarbon (MTH) reaction over acidic zeolites. Here we report the critical role of intermolecular π‐interactions in catalyst deactivation in the MTH reaction on zeolites H‐SSZ‐13 and H‐ZSM‐5. π‐interaction‐induced spatial proximities between cyclopentenyl cations and aromatics in the confined channels and/or cages of zeolites are revealed by two‐dimensional solid‐state NMR spectroscopy. The formation of naphtalene as a precursor to coke species is favored due to the reaction of aromatics with the nearby cyclopentenyl cations and correlates with both acid density and zeolite topology. 相似文献
917.
Min Bai Feng Chen Xiaowen Cao Yue Zhao Jing Xue Xu Yu Chunhai Fan Yongxi Zhao 《Angewandte Chemie (International ed. in English)》2020,59(32):13267-13272
Tumor progressions such as metastasis are complicated events that involve abnormal expression of different miRNAs and enzymes. Monitoring these biomolecules in live cells with computational DNA nanotechnology may enable discrimination of tumor progression via digital outputs. Herein, we report intracellular entropy‐driven multivalent DNA circuits to implement multi‐bit computing for simultaneous analysis of intracellular telomerase and microRNAs including miR‐21 and miR‐31. These three biomolecules can trigger respective DNA strand displacement recycling reactions for signal amplification. They are visualized by fluorescence imaging, and their signal outputs are encoded as multi‐bit binary codes for different cell types. The results can discriminate non‐tumorigenic, malignant and metastatic breast cells as well as respective tumors. This DNA computing circuit is further performed in a microfluidic chip to differentiate rare co‐cultured cells, which holds a potential for the analysis of clinical samples. 相似文献
918.
Wooseup Hwang Jejoong Yoo In‐Chul Hwang Jiyeon Lee Young Ho Ko Hyun Woo Kim Younghoon Kim Yeonsang Lee Moon Young Hur Kyeng Min Park Jongcheol Seo Kangkyun Baek Kimoon Kim 《Angewandte Chemie (International ed. in English)》2020,59(9):3460-3464
Hierarchical self‐assembly of building blocks over multiple length scales is ubiquitous in living organisms. Microtubules are one of the principal cellular components formed by hierarchical self‐assembly of nanometer‐sized tubulin heterodimers into protofilaments, which then associate to form micron‐length‐scale, multi‐stranded tubes. This peculiar biological process is now mimicked with a fully synthetic molecule, which forms a 1:1 host‐guest complex with cucurbit[7]uril as a globular building block, and then polymerizes into linear poly‐pseudorotaxanes that associate laterally with each other in a self‐shape‐complementary manner to form a tubular structure with a length over tens of micrometers. Molecular dynamic simulations suggest that the tubular assembly consists of eight poly‐pseudorotaxanes that wind together to form a 4.5 nm wide multi‐stranded tubule. 相似文献
919.
Peng‐Ju Xia Dan Song Zhi‐Peng Ye Yuan‐Zhuo Hu Jun‐An Xiao Hao‐Yue Xiang Xiao‐Qing Chen Hua Yang 《Angewandte Chemie (International ed. in English)》2020,59(17):6706-6710
A photoinduced SET process enables the direct B?H bond activation of NHC–boranes. In contrast to common hydrogen atom transfer (HAT) strategies, this photoinduced reaction simply takes advantage of the beneficial redox potentials of NHC–boranes, thus obviating the need for extra radical initiators. The resulting NHC–boryl radical was used for the borylation of a wide range of α‐trifluoromethylalkenes and alkenes with diverse electronic and structural features, providing facile access to highly functionalized borylated molecules. Labeling and photoquenching experiments provide insight into the mechanism of this photoinduced SET pathway. 相似文献
920.
Al-Shantir Omar Csáki Štefan Ondro Tomáš Keppert Martin Minárik Peter Vrabec Marek Trník Anton 《Journal of Thermal Analysis and Calorimetry》2020,142(5):1759-1766
Journal of Thermal Analysis and Calorimetry - This paper presents mechanical-acoustic study of samples made from electroporcelain mixture (type C 130) under five different compression... 相似文献