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901.
1,2,3-三氮唑化合物是一类具有重要生理活性的含氮杂环化合物, 其在医药、农药、材料科学等领域都具有广泛的应用. 不断开发基于三氮唑骨架的新型结构, 寻找新型高效的合成三氮唑衍生物的方法具有重要的意义和应用价值. 过渡金属催化的C—H键活化策略具有操作简便、效率高、三废少等优点, 是现代有机合成中高效构筑C—C键和C—X键的强大工具. 近年来, 过渡金属催化的三氮唑导向的C—H官能团化反应受到科学工作者的广泛关注, 该方法以不同结构的1,2,3-三氮唑作为导向基团, 在不同反应条件下通过直接活化C—H键来构建新的C—C键和C—X键, 高效合成复杂的三氮唑衍生物. 综述了近年来1,2,3-三氮唑导向下过渡金属催化的C—H键官能团化反应研究进展, 按照成键类型(碳-碳键、碳-杂键以及环化反应)对这些反应进行了梳理和总结, 并对今后该领域的发展进行了展望. 相似文献
902.
M. R. Ajayakumar Marco Di Giovannantonio Carlo A. Pignedoli Lin Yang Pascal Ruffieux Ji Ma Roman Fasel Xinliang Feng 《Journal of polymer science. Part A, Polymer chemistry》2022,60(12):1912-1917
The precise introduction of nonplanar pores in the backbone of graphene nanoribbon represents a great challenge. Here, we explore a synthetic strategy toward the preparation of nonplanar porous graphene nanoribbon from a predesigned dibromohexabenzotetracene monomer bearing four cove-edges. Successive thermal annealing steps of the monomers indicate that the dehalogenative aryl-aryl homocoupling yields a twisted polymer precursor on a gold surface and the subsequent cyclodehydrogenation leads to a defective porous graphene nanoribbon containing nonplanar [14]annulene pores and five-membered rings as characterized by scanning tunneling microscopy and noncontact atomic force microscopy. Although the C–C bonds producing [14]annulene pores are not achieved with high yield, our results provide new synthetic perspectives for the on-surface growth of nonplanar porous graphene nanoribbons. 相似文献
903.
Dr. Josep Mas-Roselló Prof. Dr. Nicolai Cramer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(10):e202103683
Catalytic reduction of oximes represents a direct efficient approach to synthesize valuable hydroxylamine derivatives. However this transformation presents significant challenges: oximes are hard to reduce and, if reactive, reductive cleavage of the weak N−O bond often leads to primary amine side products. The first suitable systems involved the use of platinum-based heterogeneous catalysts with hydrogen as reductant and stoichiometric amounts of a strong Brønsted acid. More recently metal-free and transition-metal-based homogeneous catalysts have been developed, which display the highest turnovers (up to 4000). In the asymmetric variants, the E/Z-geometry of the oxime double bond affects significantly the stereoselectivity, sometimes requiring extra synthetic efforts in substrate preparation. This minireview provides an overview of the advances and limitations in catalytic oxime to hydroxylamine reduction. Emphasis is put on highlighting and comparing the practical aspects of the existing methods, such as their reaction conditions and substrate scope. Additionally, future directions for improving this young research area are suggested. 相似文献
904.
Dr. Paolo Zardi Prof. Tommaso Carofiglio Prof. Michele Maggini 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(9):e202103132
Oxide nanoparticles (oxide NPs) are advanced materials with a wide variety of applications in different fields. The use of continuous flow methods is particularly appealing for their synthesis due to the high control achieved over the reaction conditions and the easy process scalability. The present review focuses on the preparation of oxide NPs using microfluidic setups at low temperature (≤80 °C), since the employment of mild reaction conditions is crucial for developing sustainable and cost-effective processes. A particular emphasis will be put on the improvement over the final product features (e. g., size, shape, and size distribution) given by flow methods with respect to conventional batch procedures. The main issues that arise by treating NPs suspensions in microfluidic systems are product deposition or channel clogging; mitigation strategies to overcome these drawbacks will also be presented and discussed. 相似文献
905.
电化学合成氨近年来受到较多关注, 直接的电化学固氮法(NRR)存在产氨来源不明的问题, 而间接的锂式合成氨(LiNR)被认为是一种可行的固氮方案. LiNR的研究多为电沉积锂, 本工作以Li-N2电池体系为基础, 利用电池的放电反应固定N2, 质子源H2O同时参与反应, 理论上提高了Li-N2电池的放电电压. 结合充电反应锂盐分解, 构成了清晰的锂循环方案. 研究发现, 当N2和H2O共同通入电池, 可以实现连续式的NH3生产, 且放电电位与理论值接近. 充放电循环显示, 每个循环均可以产生NH3, 产氨量随循环次数而增加. 该方案可循环利用锂, 对于开发新型的固氮方式有较大的研究与利用价值. 相似文献
906.
Dr. Frederik Schleife Dr. Clément Bonnot Dr. Jean-Claude Chambron Dr. Martin Börner Prof. Dr. Berthold Kersting 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(21):e202104255
The syntheses and properties of expanded 4-tert-butyl-mercaptocalix[4]arenes, in which the methylene linkers are replaced by −CH2NRCH2− or −CH2NRCH2− and −CH2NRCH2CH2CH2NRCH2− units, are described. The new macrocycles were obtained in a step-wise manner, utilizing fully protected, i. e. S-alkylated, derivatives of the oxidation-sensitive thiophenols in the cyclisation steps. Reductive cleavage of the macrobicyclic or macrotricyclic intermediates ( 6 , 7 , 11 ) afforded the free thiophenols (H4 8 , H4 9 , and H4 12 ) in preparative yields as their hydrochloride salts. The protected proligands can exist in two conformations, resembling the “cone” and “1,3-alternate” conformations found for the parent calix[4]arenes. The free macrocycles do not show conformational isomerism, but are readily oxidized forming intramolecular disulfide linkages. Preliminary complexation experiments show that these expanded mercaptocalixarenes can serve as supporting ligands for tetranuclear thiolato clusters. 相似文献
907.
Abdurrahman Turksoy Samir Bouayad-Gervais Prof. Franziska Schoenebeck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(46):e202201435
While the N-trifluoromethylation of cyclic ureas is of interest for the potential to fundamentally change the properties of these biologically relevant moieties, the single synthetic procedure known to date describing their access only gives 4,4-disubstituted or fused aromatic cyclic N-CF3 urea derivatives. We herein report an alternative approach to unleash access to the 4-monosubstituted imidazolidinone motif. The strategy relies on straightforward cyclization of readily accessible acyclic ureas, enabled by Ag-catalysis or light-assisted proton coupled electron transfer. The cyclic core is shown to be highly robust and amenable to various derivatizations, such as tandem Ni-catalysis, C−B, C−N, C−C cross couplings or C−H functionalizations, tolerating basic, nucleophilic and/or oxidizing conditions. 相似文献
908.
909.
910.
《Arabian Journal of Chemistry》2022,15(2):103586
A series of metal ion complexes was prepared in solid state from Cu(II), Hg(II) and UO2(II) ions with 3-oxo-3-(2-(2-oxoindolin-3-ylidene)hydrazineyl)-N-phenylpropanamide (H3L) ligand through solvent free synthesis methodology. The chemical formulae of the new compounds were estimated according to variable spectral and analytical investigations. The ligand exhibited a neutral or mononegative tetradentate mode of coordination towards the central ions inside the octahedral arrangement that proposed for the three complexes. The DFT/B3LYP method was applied under different basis sets (6-31G*or SDD) to optimize the structures of new compounds except the UO2(II) complex. The computational data were investigated to verify the binding mode that suggested spectrally. Moreover, studies in solution regarding Cu(II) ion via cyclic voltammetry were performed in absence or presence of H3L, to realize the significant effect of complex formation on the electrochemical manners of copper. The shifts in the potential peaks accompanied by the changes in the values of parameters correspond to kinetic and thermodynamic. Also, the solvation and kinetic characteristics for the cathodic and anodic potential of Cu(II) ion in absence or presence of H3L at different scan rates, were estimated. Finally, the ligand and copper ion exhibited high affinity towards complexation in solution. Furthermore, the activity of the new compounds towards inhibiting microbes was studied against Staphylococcus aureus (G+) and Escherichia coli (G-) bacteria as well as Candida albicans (fungus) by determining the inhibition zone diameter. Also, both the antioxidant and cytotoxic activity of the isolated compounds were evaluated. Commonly, a remarkable antimicrobial and anticancer activity was appeared with UO2(II) complex and the ligand. While, the antioxidant activity of all compounds appeared lower. 相似文献