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991.
Pd/C as a Catalyst for Completely Regioselective CH Functionalization of Thiophenes under Mild Conditions 下载免费PDF全文
Dan‐Tam D. Tang Dr. Karl D. Collins Johannes B. Ernst Prof. Dr. Frank Glorius 《Angewandte Chemie (International ed. in English)》2014,53(7):1809-1813
The completely C3‐selective arylation of thiophenes and benzo[b]thiophenes was achieved by using Pd/C as a heterogeneous catalyst without ligands or additives under mild reaction conditions. The practicability of this transformation is demonstrated by notable functional group tolerance and the insensitivity of the reaction to H2O and air. This method is also applicable to nitrogen‐ and oxygen‐containing heterocycles, yielding the corresponding C2‐arylated products. Three‐phase tests along with Hg‐poisoning and hot‐filtration tests suggest that the catalytically active species is heterogeneous in nature. 相似文献
992.
Azobenzene‐Functionalized Metal–Organic Polyhedra for the Optically Responsive Capture and Release of Guest Molecules 下载免费PDF全文
Dr. Jinhee Park Dr. Lin‐Bing Sun Ying‐Pin Chen Zachary Perry Prof. Dr. Hong‐Cai Zhou 《Angewandte Chemie (International ed. in English)》2014,53(23):5842-5846
Stimuli‐responsive metal–organic polyhedra (srMOPs) functionalized with azobenzene showed UV‐irradiation‐induced isomerization from the insoluble trans‐srMOP to the soluble cis‐srMOP, whereas irradiation with blue light reversed this process. Guest molecules were trapped and released upon cis‐to‐trans and trans‐to‐cis isomerization of the srMOPs, respectively. This study provides a new direction in the ever‐diversifying field of MOPs, while laying the groundwork for a new class of optically responsive materials. 相似文献
993.
Transition from π Radicals to σ Radicals: Substituent‐Tuned Cyclization of Hydrazonyl Radicals 下载免费PDF全文
Xiu‐Long Yang Prof. Dr. Wei Yu Prof. Dr. Bing Han 《Angewandte Chemie (International ed. in English)》2014,53(12):3158-3162
Hydrazonyl radicals are known for their π‐electronic structures; however, their σ‐electronic structures have not been reported as yet. Herein, we show that readily accessible β,γ‐ and γ,δ‐unsaturated N‐trichloroacetyl and N‐trifluoroacetyl hydrazones can be conveniently converted into hydrazonyl σ radicals, which subsequently undergo 5‐exo‐trig radical cyclization at the N1 or N2 atom to form pyrazolines and azomethine imines, respectively. 相似文献
994.
Mechanistic Insights into the Interface‐Directed Transformation of Thiols into Disulfides and Molecular Hydrogen by Visible‐Light Irradiation of Quantum Dots 下载免费PDF全文
Xu‐Bing Li Zhi‐Jun Li Yu‐Ji Gao Qing‐Yuan Meng Shan Yu Prof. Dr. Richard G. Weiss Prof. Dr. Chen‐Ho Tung Prof. Dr. Li‐Zhu Wu 《Angewandte Chemie (International ed. in English)》2014,53(8):2085-2089
Quantum dots (QDs) offer new and versatile ways to harvest light energy. However, there are few examples involving the utilization of QDs in organic synthesis. Visible‐light irradiation of CdSe QDs was found to result in virtually quantitative coupling of a variety of thiols to give disulfides and H2 without the need for sacrificial reagents or external oxidants. The addition of small amounts of nickel(II) salts dramatically improved the efficiency and conversion through facilitating the formation of hydrogen atoms, thereby leading to faster regeneration of the ground‐state QDs. Mechanistic studies reveal that the coupling reaction occurs on the QD surfaces rather than in solution and offer a blueprint for how these QDs may be used in other photocatalytic applications. Because no sacrificial agent or oxidant is necessary and the catalyst is reusable, this method may be useful for the formation of disulfide bonds in proteins as well as in other systems sensitive to the presence of oxidants. 相似文献
995.
Zhi Zeng Ke Tang Qianmin Ma Qianming Wang 《Journal of Sol-Gel Science and Technology》2014,69(1):231-236
Magnolol and honokiol as pharmaceutical ligands have been introduced into terbium complex systems for the first time and two hybrid organic–inorganic materials were successfully prepared. Both of them can sensitize terbium characteristic green emission effectively based on intra-molecular energy transfer channel. Moreover, they selectively recognized Cu2+ and Fe3+ through luminescence quenching effects. The photophysical properties and morphological structures were extensively investigated. 相似文献
996.
Synthesis of Site‐Specifically Phosphate‐Caged siRNAs and Evaluation of Their RNAi Activity and Stability 下载免费PDF全文
Dr. Li Wu Fen Pei Jinhao Zhang Junzhou Wu Mengke Feng Yuan Wang Dr. Hongwei Jin Prof. Liangren Zhang Prof. Xinjing Tang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(38):12114-12122
A complete set of new photolabile nucleoside phosphoramidites were synthesized, then site‐specifically incorporated into sense or antisense strands of siRNA for phosphate caging. Single caging modification was made along siRNA strands and their photomodulation of gene silencing were examined by using the firefly luciferase reporter gene. Several key phosphate positions were then identified. Furthermore, multiple caging modifications at these key positions led to significantly enhanced photomodulation of gene silencing activity, suggesting a synergistic effect. The caging group on both the terminally phosphate‐caged siRNA and the single‐stranded caged RNA has comparatively high stability, whereas hydrolysis of the caged group from the internally caged siRNA was observed, irrespective of the presence of Mg2+. Molecular dynamic simulations demonstrated that enhanced hydrolysis of the caging group on internally phosphate‐caged siRNAs was due to easy fragmentation of the caging group upon formation of the pentavalent intermediate of the phosphotriester with attack by water. The caging group in the terminally phosphate‐caged siRNA or single‐stranded caged RNA prefers to form π–π stacks with nearby nucleobases. In addition to providing explanations for previous observations, this study sheds further light on the design of caged oligonucleotides and indicates the direction of future development of nucleic acid drugs with phosphate modifications. 相似文献
997.
Synthesis of Single‐Crystalline Spinel LiMn2O4 Nanorods for Lithium‐Ion Batteries with High Rate Capability and Long Cycle Life 下载免费PDF全文
Xiuqiang Xie Dr. Dawei Su Dr. Bing Sun Jinqiang Zhang Prof. Dr. Chengyin Wang Prof. Dr. Guoxiu Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):17125-17131
The long‐standing challenge associated with capacity fading of spinel LiMn2O4 cathode material for lithium‐ion batteries is investigated. Single‐crystalline spinel LiMn2O4 nanorods were successfully synthesized by a template‐engaged method. Porous Mn3O4 nanorods were used as self‐sacrificial templates, into which LiOH was infiltrated by a vacuum‐assisted impregnation route. When used as cathode materials for lithium‐ion batteries, the spinel LiMn2O4 nanorods exhibited superior long cycle life owing to the one‐dimensional nanorod structure, single‐crystallinity, and Li‐rich effect. LiMn2O4 nanorods retained 95.6 % of the initial capacity after 1000 cycles at 3C rate. In particular, the nanorod morphology of the spinel LiMn2O4 was well‐preserved after a long‐term cycling, suggesting the ultrahigh structural stability of the single crystalline spinel LiMn2O4 nanorods. This result shows the promising applications of single‐crystalline spinel LiMn2O4 nanorods as cathode materials for lithium‐ion batteries with high rate capability and long cycle life. 相似文献
998.
MnO2‐Modified Persistent Luminescence Nanoparticles for Detection and Imaging of Glutathione in Living Cells and In Vivo 下载免费PDF全文
Dr. Na Li Wei Diao Yaoyao Han Dr. Wei Pan Tingting Zhang Prof. Bo Tang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(50):16488-16491
Persistent luminescence nanoparticles (PLNPs) hold great promise for the detection and imaging of biomolecules. Herein, we have demonstrated a novel nanoprobe, based on the manganese dioxide (MnO2)‐modified PLNPs, that can detect and image glutathione in living cells and in vivo. The persistent luminescence of the PLNPs can be efficiently quenched by the MnO2 nanosheets. In the presence of glutathione (GSH), MnO2 was reduced to Mn2+ and the luminescence of PLNPs can be restored. The persistent luminescence property can allow detection and imaging without external excitation and avoid the background noise originating from the in situ excitation. This strategy can offer a promising platform for detection and imaging of reactive species in living cells or in vivo. 相似文献
999.
Qing He Dr. Yuchun Han Prof. Yilin Wang Prof. Zhi‐Tang Huang Prof. De‐Xian Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(24):7486-7491
Taking tetraoxacalix[2]arene[2]triazine as a functionalization platform, a series of new amphiphilic molecules were synthesized in 18 to 53 % yields by using a fragment coupling protocol. These amphiphilic molecules self‐assembled into stable vesicles in a mixture of THF and water, with the surface of the vesicles engineered by electron‐deficient cavities. Various anions are able to selectively influence the size of self‐assembled vesicles, following the order of F?<ClO4?<SCN?<BF4?<Br?<Cl?<NO3?, as revealed by DLS measurements. Such a sequence was independent with the hydration cost and in agreement with the binding strength of anions with tetraoxacalix[2]arene[2]triazine host molecule, indicating that the anion–π interaction most probably competed over other possible weak interactions and accounted for this interesting selectivity. In addition, the chloride permeation process across the membrane of the vesicles was also preliminarily studied by means of fluorescent experiments. This study, in addition to providing the potentiality of heteracalixaromatics as new models to construct functional vesicles, opens a new avenue to study the anion–π interactions in aqueous and also potentially in living systems. 相似文献
1000.
Highly Enantioselective Catalytic System for Asymmetric Copolymerization of Carbon Dioxide and Cyclohexene Oxide 下载免费PDF全文
Yuan‐Zhao Hua Liu‐Jie Lu Pei‐Jin Huang Dong‐Hui Wei Prof. Ming‐Sheng Tang Prof. Dr. Min‐Can Wang Prof. Dr. Jun‐Biao Chang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(39):12394-12398
A new ligand can be easily prepared, and its intramolecular dinuclear zinc complexes act as a high performance catalyst for the asymmetric alternating copolymerization of cyclohexene oxide and CO2 under very mild conditions (1 atm CO2, room temperature), affording completely alternating polycarbonates with up to 93.8 % enantiomeric excess (ee) and 98 % yield. A high Mn value of 28 600 and a relatively narrow polydispersity (Mw/Mn ratio) of 1.43 were also achieved. 相似文献