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261.
Maurizio Chiminelli Dr. Andrea Serafino Davide Ruggeri Prof. Luciano Marchiò Prof. Franca Bigi Prof. Raimondo Maggi Prof. Max Malacria Prof. Giovanni Maestri 《Angewandte Chemie (International ed. in English)》2023,62(12):e202216817
Dearomative cycloadditions are a powerful tool to access a large chemical space exploiting simple and ubiquitous building blocks. The energetic burden due to the loss of aromaticity has however greatly limited their synthetic potential. We devised a general intramolecular method that overcomes these limitations thanks to the photosensitization of allenamides. The visible-light-promoted process gives complex [2.2.2]-(hetero)-bicyclooctadienes at room temperature, likely through the stabilization of transient (bi)radicals by naphthalene. The reaction tolerates several valuable functionalities, offering a convenient handle for a myriad of applications, including original isoindoles and metal complexes. 相似文献
262.
Wang Jiang Dr. Xiuxiu Yang Lin Lin Prof. Dr. Chaoguo Yan Dr. Yue Zhao Prof. Dr. Minyan Wang Prof. Dr. Zhuangzhi Shi 《Angewandte Chemie (International ed. in English)》2023,62(47):e202309709
Metal-catalyzed C−H activation strategies provide an efficient approach for synthesis by minimizing atom, step, and redox economy. Developing milder, greener, and more effective protocols for these strategies is always highly desirable to the scientific community. In this study, the utilization of a single rhodium complex enabled the visible-light-induced late-stage C−H activation of biaryl-type phosphines with alkynyl bromides, employing inherent phosphorus atoms as directing groups. This chemistry combines P(III)-directed C−H activation with visible light photocatalysis, under exogenous photosensitizer-free conditions, offering a unique platform for ligand design and preparation. Furthermore, this study also explores the asymmetric catalysis and coordination chemistry of the resulting P-alkyne hybrid ligands with specific transition metals. Experimental results and density functional theory calculations demonstrate the mechanistic intricacies of this transformation. 相似文献
263.
Benedikt Wolff Dr. Zheng-Wang Qu Prof. Dr. Stefan Grimme Prof. Dr. Martin Oestreich 《Angewandte Chemie (International ed. in English)》2023,62(29):e202305295
An enantioselective reduction of simple carbenium ions with cyclohexadienes containing a hydridic C−H bond at an asymmetrically substituted carbon atom is disclosed. The net reaction is a transfer hydrogenation of alkenes (styrenes) only employing chiral cyclohexadienes as dihydrogen surrogates. The trityl cation is used to initiate a Brønsted acid-promoted process, in which a delicate intermolecular capture of a carbenium-ion intermediate by the aforementioned chiral hydride source is enantioselectivity determining. Exclusively non-covalent interactions are rendering one of the transition states energetically more favored, giving the reduction products in good enantiomeric ratios. The computed reaction mechanism supports the present findings as well as previous results obtained from studies on other transfer-hydrogenation methods involving the cyclohexadiene platform. 相似文献
264.
Dr. Yahui Chen Dr. Sheng Lu Syed Ali Abbas Abedi Minseok Jeong Dr. Haidong Li Prof. Myung Hwa Kim Prof. Sungnam Park Prof. Xiaogang Liu Prof. Juyoung Yoon Prof. Xiaoqiang Chen 《Angewandte Chemie (International ed. in English)》2023,62(40):e202311543
Excited-state intramolecular proton transfer (ESIPT)-based solid luminescent materials with multiple hydrogen bond acceptors (HBAs) remain unexplored. Herein, we introduced a family of Janus-type ESIPT chromophores featuring distinctive hydrogen bond (H-bond) selectivity between competitive HBAs in a single molecule. Our investigations showed that the central hydroxyl group preferentially forms intramolecular H-bonds with imines in imine-modified 2-hydroxyphenyl benzothiazole (HBT) chromophores but tethers the benzothiazole moiety in hydrazone-modified HBT chromophores. Imine-derived HBTs generally exhibit higher fluorescence efficiency, while hydrazone-derived HBTs show a reduced overlap between the absorption and fluorescence bands. Quantum chemical calculations unveiled the molecular origins of the biased intramolecular H-bonds and their impact on the ESIPT process. This Janus-type ESIPT chromophore skeleton provides new opportunities for the design of solid luminescent materials. 相似文献
265.
Willi Keller Joachim Ballmann Menyhárt B. Sárosi Jindřich Fanfrlík Drahomír Hnyk 《Angewandte Chemie (International ed. in English)》2023,62(24):e202219018
Six-vertex closo-TeB5Cl5 ( 1 ) and twelve-vertex closo-TeB11Cl11 ( 2 ) telluraboranes have been prepared via co-pyrolysis of B2Cl4 with TeCl4 in vacuo at temperatures between 360 °C and 400 °C. Both compounds are sublimable, off-white solids, and they have been characterized by one- and two-dimensional 11B NMR and high-resolution mass spectroscopy. Both ab initio/GIAO/NMR and DFT/ZORA/NMR computations support octahedral and icosahedral geometries for 1 and 2 , respectively, as expected due to their closo-electron counts. The octahedral structure of 1 has been confirmed by single-crystal X-ray diffraction on an incommensurately modulated crystal. The corresponding bonding properties have been analyzed in terms of the intrinsic bond orbital (IBO) approach. 1 is the first example of a polyhedral telluraborane with a cluster size smaller than 10 vertices. 相似文献
266.
Maike Lettow Kim Greis Eike Mucha Tyler R. Lambeth Murat Yaman Vasilis Kontodimas Christian Manz Waldemar Hoffmann Gerard Meijer Ryan R. Julian Gert von Helden Mateusz Marianski Kevin Pagel 《Angewandte Chemie (International ed. in English)》2023,62(24):e202302883
Fucose is a signaling carbohydrate that is attached at the end of glycan processing. It is involved in a range of processes, such as the selectin-dependent leukocyte adhesion or pathogen-receptor interactions. Mass-spectrometric techniques, which are commonly used to determine the structure of glycans, frequently show fucose-containing chimeric fragments that obfuscate the analysis. The rearrangement leading to these fragments—often referred to as fucose migration—has been known for more than 25 years, but the chemical identity of the rearrangement product remains unclear. In this work, we combine ion-mobility spectrometry, radical-directed dissociation mass spectrometry, cryogenic IR spectroscopy of ions, and density-functional theory calculations to deduce the product of the rearrangement in the model trisaccharides Lewis x and blood group H2. The structural search yields the fucose moiety attached to the galactose with an α(1→6) glycosidic bond as the most likely product. 相似文献
267.
Nanxi Miao Prof. Yutong Gong Huaiyu Zhang Qing Shen Rui Yang Prof. Jianping Zhou Prof. Hideo Hosono Prof. Junjie Wang 《Angewandte Chemie (International ed. in English)》2023,62(36):e202308436
The practical applications of two-dimensional (2D) transition-metal borides (MBenes) have been severely hindered by the lack of accessible MBenes because of the difficulties in the selective etching of traditional ternary MAB phases with orthorhombic symmetry (ort-MAB). Here, we discover a family of ternary hexagonal MAB (h-MAB) phases and 2D hexagonal MBenes (h-MBenes) by ab initio predictions and experiments. Calculations suggest that the ternary h-MAB phases are more suitable precursors for MBenes than the ort-MAB phases. Based on the prediction, we report the experimental synthesis of h-MBene HfBO by selective removal of In from h-MAB Hf2InB2. The synthesized 2D HfBO delivered a specific capacity of 420 mAh g−1 as an anode material in lithium-ion batteries, demonstrating the potential for energy-storage applications. The discovery of this h-MBene HfBO added a new member to the growing family of 2D materials and provided opportunities for a wide range of novel applications. 相似文献