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261.
Biosynthesis of Streptolidine Involved Two Unexpected Intermediates Produced by a Dihydroxylase and a Cyclase through Unusual Mechanisms 下载免费PDF全文
Dr. Chin‐Yuan Chang Syue‐Yi Lyu Dr. Yu‐Chen Liu Ning‐Shian Hsu Dr. Chih‐Chung Wu Dr. Cheng‐Fong Tang Kuan‐Hung Lin Dr. Jin‐Yuan Ho Dr. Chang‐Jer Wu Dr. Ming‐Daw Tsai Dr. Tsung‐Lin Li 《Angewandte Chemie (International ed. in English)》2014,53(7):1943-1948
Streptothricin‐F (STT‐F), one of the early‐discovered antibiotics, consists of three components, a β‐lysine homopolymer, an aminosugar D ‐gulosamine, and an unusual bicyclic streptolidine. The biosynthesis of streptolidine is a long‐lasting but unresolved puzzle. Herein, a combination of genetic/biochemical/structural approaches was used to unravel this problem. The STT gene cluster was first sequenced from a Streptomyces variant BCRC 12163, wherein two gene products OrfP and OrfR were characterized in vitro to be a dihydroxylase and a cyclase, respectively. Thirteen high‐resolution crystal structures for both enzymes in different reaction intermediate states were snapshotted to help elucidate their catalytic mechanisms. OrfP catalyzes an FeII‐dependent double hydroxylation reaction converting L ‐Arg into (3R,4R)‐(OH)2‐L ‐Arg via (3S)‐OH‐L ‐Arg, while OrfR catalyzes an unusual PLP‐dependent elimination/addition reaction cyclizing (3R,4R)‐(OH)2‐L ‐Arg to the six‐membered (4R)‐OH‐capreomycidine. The biosynthetic mystery finally comes to light as the latter product was incorporation into STT‐F by a feeding experiment. 相似文献
262.
Back Cover: Synthesis,Characterization, Self‐Assembly,Gelation, Morphology and Computational Studies of Alkynylgold(III) Complexes of 2,6‐Bis(benzimidazol‐2′‐yl)pyridine Derivatives (Chem. Eur. J. 32/2014) 下载免费PDF全文
263.
Hye Mi Oh Ji Eun Park Jisu Kim Ju Hyun Kim Prof. Youn K. Kang Prof. Young Keun Chung 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(29):9024-9036
A method for the synthesis of bicyclo[4.1.0]heptenes from 1,6‐enynes through Pd‐catalyzed cycloisomerization has been developed. N‐ and O‐tethered 1,6‐enynes were successfully transformed to their corresponding 3‐aza‐ and 3‐oxabicyclo[4.1.0]heptenes in reasonable‐to‐high yields using the catalysts [PdCl2(CH3CN)2]/P(OPh)3 or [Pd(maleimidate)2(PPh3)2] in toluene. The computational calculations using density functional theory indicate that [PdCl2{P(OPh)3}] in the oxidation state PdII acts as the active catalyst species for the formation of 3‐azabicyclo[4.1.0]heptenes through 6‐endo‐dig cyclization. 相似文献
264.
Hexanuclear Gold(I) Phosphide Complexes as Platforms for Multiple Redox‐Active Ferrocenyl Units 下载免费PDF全文
Dr. Terence Kwok‐Ming Lee Dr. Eddie Chung‐Chin Cheng Dr. Nianyong Zhu Prof. Dr. Vivian Wing‐Wah Yam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(1):304-310
The synthesis, X‐ray crystal structures, electrochemical, and spectroscopic studies of a series of hexanuclear gold(I) μ3‐ferrocenylmethylphosphido complexes stabilized by bridging phosphine ligands, [Au6(P?P)n(Fc‐CH2‐P)2][PF6]2 (n=3, P?P=dppm (bis(diphenylphosphino)methane) ( 1 ), dppe (1,2‐bis(diphenylphosphino)ethane) ( 2 ), dppp (1,3‐bis(diphenylphosphino)propane) ( 3 ), Ph2PN(C3H7)‐PPh2 ( 4 ), Ph2PN(Ph‐CH3‐p)PPh2 ( 5 ), dppf (1,1′‐bis(diphenylphosphino)ferrocene) ( 6 ); n=2, P?P=dpepp (bis(2‐diphenylphosphinoethyl)phenylphosphine) ( 7 )), as platforms for multiple redox‐active ferrocenyl units, are reported. The investigation of the structural changes of the clusters has been probed by introducing different bridging phosphine ligands. This class of gold(I) μ3‐ferrocenylmethylphosphido complexes has been found to exhibit one reversible oxidation couple, suggestive of the absence of electronic communication between the ferrocene units through the Au6P2 cluster core, providing an understanding of the electronic properties of the hexanuclear AuI cluster linkage. The present complexes also serve as an ideal system for the design of multi‐electron reservoir and molecular battery systems. 相似文献
265.
Dr. Cheng‐Chung Lee Dr. Manuel Maestre‐Reyna Dr. Kai‐Cheng Hsu Prof. Dr. Hao‐Ching Wang Prof. Dr. Chia‐I Liu Prof. Dr. Wen‐Yih Jeng Li‐Ling Lin Richard Wood Dr. Chia‐Cheng Chou Prof. Dr. Jinn‐Moon Yang Prof. Dr. Andrew H.‐J. Wang 《Angewandte Chemie (International ed. in English)》2014,53(48):13054-13058
Crown ethers are small, cyclic polyethers that have found wide‐spread use in phase‐transfer catalysis and, to a certain degree, in protein chemistry. Crown ethers readily bind metallic and organic cations, including positively charged amino acid side chains. We elucidated the crystal structures of several protein‐crown ether co‐crystals grown in the presence of 18‐crown‐6. We then employed biophysical methods and molecular dynamics simulations to compare these complexes with the corresponding apoproteins and with similar complexes with ring‐shaped low‐molecular‐weight polyethylene glycols. Our studies show that crown ethers can modify protein surface behavior dramatically by stabilizing either intra‐ or intermolecular interactions. Consequently, we propose that crown ethers can be used to modulate a wide variety of protein surface behaviors, such as oligomerization, domain–domain interactions, stabilization in organic solvents, and crystallization. 相似文献
266.
Hyun-Shik Yun Hongkyun Lee Young-Tae Park Min-Kyu Ji Akhil N. Kabra Chung Jeon Byong-Hun Jeon Jaeyoung Choi 《Applied biochemistry and biotechnology》2014,173(8):2054-2064
Microalgae were selected and isolated from acid mine drainage in order to find microalgae species which could be cultivated in low pH condition. In the present investigation, 30 microalgae were isolated from ten locations of acid mine drainage in South Korea. Four microalgae were selected based on their growth rate, morphology, and identified as strains of KGE1, KGE3, KGE4, and KGE7. The dry biomass of microalgae species ranged between 1 and 2 g L?1 after 21 days of cultivation. The growth kinetics of microalgae was well described by logistic growth model. Among these, KGE7 has the highest biomass production (2.05?±?0.35 g L?1), lipid productivity (0.82?±?0.14 g L?1), and C16–C18 fatty acid contents (97.6 %). These results suggest that Scenedesmus sp. KGE 7 can be utilized for biodiesel production based on its high biomass and lipid productivity. 相似文献
267.
Young-Hun Cho Jae-Gyoung Seong Jae-Hyun Noh Da-Young Kim Yong-Sik Chung Tae Hoon Ko Byoung-Suhk Kim 《Molecules (Basel, Switzerland)》2020,25(24)
In this work, we report the carbon fiber-based wire-type asymmetric supercapacitors (ASCs). The highly conductive carbon fibers were prepared by the carbonized and graphitized process using the polyimide (PI) as a carbon fiber precursor. To assemble the ASC device, the CoMnO2-coated and Fe2O3-coated carbon fibers were used as the cathode and the anode materials, respectively. Herein, the nanostructured CoMnO2 were directly deposited onto carbon fibers by a chemical oxidation route without high temperature treatment in presence of ammonium persulfate (APS) as an oxidizing agent. FE-SEM analysis confirmed that the CoMnO2-coated carbon fiber electrode exhibited the porous hierarchical interconnected nanosheet structures, depending on the added amount of APS, and Fe2O3-coated carbon fiber electrode showed a uniform distribution of porous Fe2O3 nanorods over the surface of carbon fibers. The electrochemical properties of the CoMnO2-coated carbon fiber with the concentration of 6 mmol APS presented the enhanced electrochemical activity, probably due to its porous morphologies and good conductivity. Further, to reduce the interfacial contact resistance as well as improve the adhesion between transition metal nanostructures and carbon fibers, the carbon fibers were pre-coated with the Ni layer as a seed layer using an electrochemical deposition method. The fabricated ASC device delivered a specific capacitance of 221 F g−1 at 0.7 A g−1 and good rate capability of 34.8% at 4.9 A g−1. Moreover, the wire-type device displayed the superior energy density of 60.2 Wh kg−1 at a power density of 490 W kg−1 and excellent capacitance retention of 95% up to 3000 charge/discharge cycles. 相似文献
268.
Haidong Li Qichao Yao Feng Xu Yueqing Li Dayeh Kim Jeewon Chung Gain Baek Xiaofeng Wu Prima Fitria Hillman Eun Young Lee Haoying Ge Jiangli Fan Jingyun Wang Sang‐Jip Nam Xiaojun Peng Juyoung Yoon 《Angewandte Chemie (International ed. in English)》2020,59(25):10186-10195
Monitoring fluctuations in enzyme overexpression facilitates early tumor detection and excision. An AIEgen probe (DQM‐ALP) for the imaging of alkaline phosphatase (ALP) activity was synthesized. The probe consists of a quinoline‐malononitrile (QM) core decorated with hydrophilic phosphate groups as ALP‐recognition units. The rapid liberation of DQM‐OH aggregates in the presence of ALP resulted in aggregation‐induced fluorescence. The up‐regulation of ALP expression in tumor cells was imaged using DQM‐ALP. The probe permeated into 3D cervical and liver tumor spheroids for imaging spatially heterogeneous ALP activity with high spatial resolution on a two‐photon microscopy platform, providing the fluorescence‐guided recognition of sub‐millimeter tumorigenesis. DQM‐ALP enabled differentiation between tumor and normal tissue ex vivo and in vivo, suggesting that the probe may serve as a powerful tool to assist surgeons during tumor resection. 相似文献
269.
Saeromi Chung Mahmood H. Akhtar A. Benboudiaf Deog‐Su Park Yoon‐Bo Shim 《Electroanalysis》2020,32(3):520-527
An electrochemical sensor based on the conducting polymer composite with a palladium complex (Pd(C2H4N2S2)2) was developed for the detection of serotonin and dopamine simultaneously in the breast cancer cell and human plasma samples. The proposed sensor was fabricated using the Pd(C2H4N2S2)2 complex‐anchored poly2,2 : 5,2‐terthiophene‐3‐(p‐benzoic acid) (pTBA) layer on the AuNPs decorated reduced graphene oxide (AuNPs@rGO) substrate, which revealed the enhanced anodic current of the target species. The sensor probe was characterized by electrochemical and surface analysis methods. The experimental parameters affecting the sensor performance were optimized, in terms of AuNPs@rGO concentration, the number of electropolymerization cycle for pTBA, immobilization time of Pd(C2H4N2S2)2, and pH. The dynamic ranges for serotonin and dopamine were obtained from 0.02 to 200 μM, and from 0.1 to 200 μM with the detection limit of 2.5, and 24.0 nM, respectively. The reliability of proposed sensor was evaluated using cancer cell lines for the clinical applications. 相似文献
270.
Wai Chung Fu Timothy F. Jamison 《Angewandte Chemie (International ed. in English)》2020,59(33):13885-13890
The deuteriodifluoromethyl group (CF2D) represents a challenging functional group due to difficult deuterium incorporation and unavailability of precursor reagents. Herein, we report the use of chlorodifluoromethane (ClCF2H) gas in the continuous flow deuteriodifluoromethylation and gem‐difluoroalkenylation of aldehydes. Mechanistic studies revealed that the difluorinated oxaphosphetane (OPA) intermediate can proceed via alkaline hydrolysis in the presence of D2O to provide α‐deuteriodifluoromethylated benzyl alcohols or undergo a retro [2+2] cycloaddition under thermal conditions to provide the gem‐difluoroalkenylated product. 相似文献