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991.
Adam Jaffe Stephanie A. Mack Yu Lin Wendy L. Mao Jeffrey B. Neaton Hemamala I. Karunadasa 《Angewandte Chemie (International ed. in English)》2020,59(10):4017-4022
We show that the onset pressure for appreciable conductivity in layered copper‐halide perovskites can decrease by ca. 50 GPa upon replacement of Cl with Br. Layered Cu–Cl perovskites require pressures >50 GPa to show a conductivity of 10?4 S cm?1, whereas here a Cu–Br congener, (EA)2CuBr4 (EA=ethylammonium), exhibits conductivity as high as 2×10?3 S cm?1 at only 2.6 GPa, and 0.17 S cm?1 at 59 GPa. Substitution of higher‐energy Br 4p for Cl 3p orbitals lowers the charge‐transfer band gap of the perovskite by 0.9 eV. This 1.7 eV band gap decreases to 0.3 eV at 65 GPa. High‐pressure X‐ray diffraction, optical absorption, and transport measurements, and density functional theory calculations allow us to track compression‐induced structural and electronic changes. The notable enhancement of the Br perovskite's electronic response to pressure may be attributed to more diffuse Br valence orbitals relative to Cl orbitals. This work brings the compression‐induced conductivity of Cu‐halide perovskites to more technologically accessible pressures. 相似文献
992.
Wenjun Yang Bo Ling Bowen Hu Haolin Yin Jianyou Mao Patrick J. Walsh 《Angewandte Chemie (International ed. in English)》2020,59(1):161-166
An umpolung 1,4‐addition of aryl iodides to enals promoted by cooperative (terpy)Pd/NHC catalysis was developed that generates various bioactive β,β‐diaryl propanoate derivatives. This system is not only the first reported palladium‐catalyzed arylation of NHC‐bound homoenolates but also expands the scope of NHC‐induced umpolung transformations. A diverse array of functional groups such as esters, nitriles, alcohols, and heterocycles are tolerated under the mild conditions. This method also circumvents the use of moisture‐sensitive organometallic reagents. 相似文献
993.
Vladislav V. Klepov Anna A. Berseneva Kristen A. Pace Vancho Kocevski Mengqi Sun Peng Qiu Hui Wang Fanglin Chen Theodore M. Besmann Hans‐Conrad zur Loye 《Angewandte Chemie (International ed. in English)》2020,59(27):10836-10841
Most ternary sulfides belonging to the MGaS2 structure‐type have been known for many years and are well‐characterized. Surprisingly, there have been no reports of the NaGaS2 composition, which contains Na, a monovalent cation slightly larger in size than Li, found in LiGaS2, a compound known for its non‐linear optical properties. Now it is demonstrated for the first time that the unique reversible water absorption in NaGaS2 has resulted in its absence from previous reports owing to difficulties encountered when characterizing this compound by SC XRD. The layered structure of this compound coupled with uniquely easy migration of water molecules between the layers allows for ion exchange with 3d and 5f metal cations. Some cations, for example, Ni2+, facilitate exfoliation of the layers, providing a facile synthetic route to a new class of 2D chalcogenide materials and furthermore demonstrating that NaGaS2 can readily uptake uranyl species from aqueous solutions. 相似文献
994.
Hui Shao Xiaonan Gao Zhong‐Tian Wang Ziwei Gao Yu‐Ming Zhao 《Angewandte Chemie (International ed. in English)》2020,59(19):7419-7424
A divergent synthetic approach to six Ganoderma meroterpenoids, namely ganocins A–C, ganocochlearins C and D, and cochlearol T, has been developed for the first time. This synthetic route features a two‐phase strategy which includes early‐stage rapid construction of a common planar tricyclic intermediate followed by highly selective late‐stage transformations into various Ganoderma meroterpenoids. Key to the strategy are a bioinspired intramolecular hetero‐Diels–Alder reaction and Stahl‐type oxidative aromatization, allowing efficient formation of the common tricyclic phenol intermediate. A nucleophilic dearomatization of the phenol unit, combined with a regioselective 1,4‐reduction of the resulting dienone, enabled rapid access to ganocins B and C. Additionally, site‐selective Mukaiyama hydration, followed by an intramolecular oxa‐Michael addition/triflation cascade, served as a key strategic element in the chemical synthesis of ganocin A. 相似文献
995.
Chitosan (CS) with good hydrophilicity and charged property was used to modify graphene oxide (GO), the obtained GO‐CS was used as a novel modifier to fabricate thin film composite forward osmosis (FO) membranes. The results revealed that the amino groups on CS reacted with carboxyl groups on GO, and the lamellar structure of the GO nanosheets was peeled off by CS, resulting in the reducing of their thicknesses. The GO‐CS improved the hydrophilicity of polyethersulfone (PES) substrate, and their contact angles decreased to 64° with the addition of GO‐CS in the substrate. GO‐CS also increased the porosity of the substrate and surface roughness of FO membrane, thereby optimizing the water flux and reverse salt flux of FO membrane. The average water flux of the FO membrane reached the optimal flux of 21.34 L/(m2 h) when GO‐CS addition was 0.5 wt%, and further addition of GO‐CS to the substrate would decrease the water flux of FO membrane, and the reverse salt flux also decreased to the lowest value of 2.26 g/(m2 h). However, the salt rejection of the membrane increased from 91.4% to 95.1% when GO‐CS addition increased from 0.5 to 1.0 wt% under FO mode using 1 mol/L sodium chloride (NaCl) solution as draw solution (DS). In addition, high osmotic pressure favored water permeation, and at the same concentration of DS, magnesium chloride (MgCl2) exhibited better properties than NaCl. These results all suggested that GO‐CS was a good modifier to fabricate FO membrane, and MgCl2 was a good DS candidate. 相似文献
996.
997.
[Fe]‐hydrogenase is an efficient biological hydrogenation catalyst. Despite intense research, Fe complexes mimicking the active site of [Fe]‐hydrogenase have not achieved turnovers in hydrogenation reactions. Herein, we describe the design and development of a manganese(I) mimic of [Fe]‐hydrogenase. This complex exhibits the highest activity and broadest scope in catalytic hydrogenation among known mimics. Thanks to its biomimetic nature, the complex exhibits unique activity in the hydrogenation of compounds analogous to methenyl‐H4MPT+, the natural substrate of [Fe]‐hydrogenase. This activity enables asymmetric relay hydrogenation of benzoxazinones and benzoxazines, involving the hydrogenation of a chiral hydride transfer agent using our catalyst coupled to Lewis acid‐catalyzed hydride transfer from this agent to the substrates. 相似文献
998.
Lanfang Ren Jia Lv Hui Wang Yiyun Cheng 《Angewandte Chemie (International ed. in English)》2020,59(12):4711-4719
Cytosolic protein delivery is a prerequisite for the development of protein therapeutics that act on intracellular targets. Proteins are generally membrane‐impermeable and thus need a carrier such as a polymer to facilitate their internalization. However, the efficient binding of proteins with different isoelectric points to polymeric carriers is challenging. In this study, we designed a coordinative dendrimer to solve this problem. The dendrimers modified with dipicolylamine/zinc(II) complex were capable of binding proteins through a combination of ionic and coordination interactions. The best polymer efficiently delivered 30 cargo proteins and peptides into the cytosol, while maintaining their bioactivity after intracellular release. The removal or replacement of zinc ions in the polymer with other transition‐metal ions lead to significantly decreased efficiency in cytosolic protein delivery. This study provides a new strategy to develop robust and efficient polymers for cytosolic protein delivery. 相似文献
999.
Shen‐Yi Guo Qing‐Hui Guo Shuo Tong Mei‐Xiang Wang 《Angewandte Chemie (International ed. in English)》2020,59(21):8078-8083
Reported here are the syntheses, conformational structures, electrochemical properties, and noncovalent anion binding of corona[5]arenes. A (3+2) fragment coupling reaction proceeded efficiently under mild reaction conditions to produce a number of novel heteroatom‐ and methylene‐bridged corona[3]arene[2]tetrazine macrocycles. Selective oxidation of the sulfur atom between two phenylene rings afforded sulfoxide‐ and sulfone‐linked corona[5]arenes in good yields. All corona[5]arenes synthesized adopted similar 1,2,4‐alternate conformational structures, forming pentagonal cavities. The cavity sizes and the electronic properties such as redox potentials, were measured with CV and DPV, and were influenced by the different bridging units. As electron‐deficient macrocycles, the acquired corona[3]arene[2]tetrazines served as highly selective hosts, forming complexes with the hydrogen‐bonded dimer of dihydrogen phosphate through cooperative anion–π interactions. 相似文献
1000.
Mimi Wan Qi Wang Xiaoyun Li Bo Xu Dan Fang Ting Li Yueqi Yu Leyi Fang Yue Wang Meng Wang Fenghe Wang Chun Mao Jian Shen Jia Wei 《Angewandte Chemie (International ed. in English)》2020,59(34):14458-14465
Limited tumor permeability of therapeutic agents is a great challenge faced by current cancer therapy methods. Herein, a kind of near infrared light (NIR)‐driven nanomotor with autonomous movement, targeted ability, hierarchical porous structure, multi‐drugs for cancer chemo/photothermal therapy is designed, prepared and characterized. Further, we establish a method to study the interaction between nanomotors and cells, along with their tumor permeability mechanism, including 2D cellular models, 3D multicellular tumor spheroids and in vivo models. In vivo tumor elimination results verify that the movement behaviour of the nanomotors can greatly facilitate them to eliminate tumor through multiple therapeutic methods. This work tries to establish systematic research and evaluation models, providing strategies to understand the relationship between motion behaviour and tumor permeation efficiency of nanomotors in depth. 相似文献