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291.
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293.
Optimized precursor ion selection for labile ions in a linear ion trap mass spectrometer and its impact on quantification using selected reaction monitoring
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Hyun‐Seok Lee Kyong‐Oh Shin Sung‐Chan Jo Yong‐Moon Lee Yong‐Hyeon Yim 《Journal of mass spectrometry : JMS》2014,49(12):1234-1238
The fragmentation of fragile ions during the application of an isolation waveform for precursor ion selection and the resulting loss of isolated ion intensity is well‐known in ion trap mass spectrometry (ITMS). To obtain adequate ion intensity in the selected reaction monitoring (SRM) of fragile precursor ions, a wider ion isolation width is required. However, the increased isolation width significantly diminishes the selectivity of the channels chosen for SRM, which is a serious problem for samples with complex matrices. The sensitive and selective quantification of many lipid molecules, including ceramides from real biological samples, using a linear ion trap mass spectrometer is also hindered by the same problem because of the ease of water loss from protonated ceramide ions. In this study, a method for the reliable quantification of ceramides using SRM with near unity precursor ion isolation has been developed for ITMS by utilizing alternative precursor ions generated by in‐source dissociation. The selected precursor ions allow the isolation of ions with unit mass width and the selective analysis of ceramides using SRM with negligible loss of sensitivity. The quantification of C18:0‐, C24:0‐ and C24:1‐ceramides using the present method shows excellent linearity over the concentration ranges from 6 to 100, 25 to 1000 and 25 to 1000 nM, respectively. The limits of detection of C18:0‐, C24:0‐ and C24:1‐ceramides were 0.25, 0.25 and 5 fmol, respectively. The developed method was successfully applied to quantify ceramides in fetal bovine serum. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
294.
Won Chan Hwang Mi Kyoung Kim Ju Hyun Song Kang-Yell Choi Do Sik Min 《Experimental & molecular medicine》2014,46(12):e124
Autophagy is a conserved lysosomal self-digestion process used for the breakdown of long-lived proteins and damaged organelles, and it is associated with a number of pathological processes, including cancer. Phospholipase D (PLD) isozymes are dysregulated in various cancers. Recently, we reported that PLD1 is a new regulator of autophagy and is a potential target for cancer therapy. Here, we investigated whether PLD2 is involved in the regulation of autophagy. A PLD2-specific inhibitor and siRNA directed against PLD2 were used to treat HT29 and HCT116 colorectal cancer cells, and both inhibition and genetic knockdown of PLD2 in these cells significantly induced autophagy, as demonstrated by the visualization of light chain 3 (LC3) puncta and autophagic vacuoles as well as by determining the LC3-II protein level. Furthermore, PLD2 inhibition promoted autophagic flux via the canonical Atg5-, Atg7- and AMPK-Ulk1-mediated pathways. Taken together, these results suggest that PLD2 might have a role in autophagy and that its inhibition might provide a new therapeutic basis for targeting autophagy. 相似文献
295.
Xuan Thang Cao Ali Md Showkat Chan Park Yeong Soon Gal 《Molecular Crystals and Liquid Crystals》2015,618(1):103-110
Poly(?-caprolactone) grafted poly(2-hydroxyethyl methacrylate) functionalized hydroxyapatite (HAP@PHEMA-g-PCL) nanocomposites were synthesized by the combination of reversible addition fragmentation chain transfer (RAFT) polymerization and ring-opening polymerization (ROP). The RAFT agent was anchored on the surface of hydroxyapatite nanocrystals (HAPs) through the silane condensation process of 3-chloropropyltrimethoxysilane followed by reaction with potassium xanthogenate. Poly(2-hydroxyethyl methacrylate) (PHEMA) was covalently functionalized on the surface of HAPs by RAFT polymerization. Then, poly(?-caprolactone) (PCL) was grafted on HAPs by ROP based on the hydroxyl groups of PHEMA to afford HAP@PHEMA-g-PCL. The structure and composition of HAP@PHEMA-g-PCL nanocomposites were characterized by FT-IR, XRD, and TGA analyses. The morphology and formation of the polymer encapsulating HAPs were demonstrated from SEM and TEM images, while the 1H MNR analysis of the cleaved PHEMA-g-PCL confirmed the grafting. 相似文献
296.
Rhodium‐Catalyzed Ketone Methylation Using Methanol Under Mild Conditions: Formation of α‐Branched Products
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Dr. Louis K. M. Chan Darren L. Poole Di Shen Dr. Mark P. Healy Prof. Timothy J. Donohoe 《Angewandte Chemie (International ed. in English)》2014,53(3):761-765
The rhodium‐catalyzed methylation of ketones has been accomplished using methanol as the methylating agent and the hydrogen‐borrowing method. The sequence is notable for the relatively low temperatures that are required and for the ability of the reaction system to form α‐branched products with ease. Doubly alkylated ketones can be prepared from methyl ketones and two different alcohols by using a sequential one‐pot iridium‐ and rhodium‐catalyzed process. 相似文献
297.
Elevated Catalytic Activity of Ruthenium(II)–Porphyrin‐Catalyzed Carbene/Nitrene Transfer and Insertion Reactions with N‐Heterocyclic Carbene Ligands
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Ka‐Ho Chan Dr. Xiangguo Guan Dr. Vanessa Kar‐Yan Lo Prof. Dr. Chi‐Ming Che 《Angewandte Chemie (International ed. in English)》2014,53(11):2982-2987
Bis(NHC)ruthenium(II)–porphyrin complexes were designed, synthesized, and characterized. Owing to the strong donor strength of axial NHC ligands in stabilizing the trans M?CRR′/M?NR moiety, these complexes showed unprecedently high catalytic activity towards alkene cyclopropanation, carbene C? H, N? H, S? H, and O? H insertion, alkene aziridination, and nitrene C? H insertion with turnover frequencies up to 1950 min?1. The use of chiral [Ru(D4‐Por)(BIMe)2] ( 1 g ) as a catalyst led to highly enantioselective carbene/nitrene transfer and insertion reactions with up to 98 % ee. Carbene modification of the N terminus of peptides at 37 °C was possible. DFT calculations revealed that the trans axial NHC ligand facilitates the decomposition of diazo compounds by stabilizing the metal–carbene reaction intermediate. 相似文献
298.
Gold‐Catalyzed Cycloisomerization of 1,6,8‐Dienyne Carbonates and Esters to cis‐Cyclohepta‐4,8‐diene‐Fused Pyrrolidines
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Dr. Weidong Rao Sally Stuart Neil Berry Prof. Dr. Philip Wai Hong Chan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13174-13180
A synthetic approach that provides access to cis‐cyclohepta‐4,8‐diene‐fused pyrrolidines efficiently through AuI‐catalyzed cycloisomerization of 1,6,8‐dienyne carbonates and esters at a low catalyst loading of 2 mol % is reported. Starting carbonates and esters with a pendant alkyl group on the terminal alkenyl carbon center were found to favor tandem 1,2‐acyloxy migration/cyclopropanation followed by Cope rearrangement of the resulting cis‐3‐azabicyclo[3.1.0]hexane intermediate. On the other hand, substrates containing a terminal diene or starting materials in which the distal alkene moiety bears a phenyl substituent were observed to undergo competitive but reversible 1,3‐acyloxy migration prior to the nitrogen‐containing bicyclic ring formation. The delineated reaction mechanism also provides experimental evidence for the reversible interconversion between the oft‐proposed organogold intermediates obtained in this step of the tandem process. 相似文献
299.
300.
Using Simple Spray Pyrolysis to Prepare Yolk–Shell‐Structured ZnO–Mn3O4 Systems with the Optimum Composition for Superior Electrochemical Properties
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Seung Ho Choi Prof. Yun Chan Kang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(11):3014-3018
A spray‐pyrolysis process is introduced as an effective tool for the preparation of yolk–shell‐structured materials with electrochemical properties suitable for anode materials in Li‐ion batteries (LIBs). Yolk–shell‐structured ZnO–Mn3O4 systems with various molar ratios of the Zn and Mn components are prepared. The yolk–shell‐structured ZnO–Mn3O4 powders with a molar ratio of 1:1 of the Zn and Mn components are shown to have high capacities and good cycling performances. 相似文献