全文获取类型
收费全文 | 42240篇 |
免费 | 10541篇 |
国内免费 | 2591篇 |
专业分类
化学 | 45732篇 |
晶体学 | 391篇 |
力学 | 806篇 |
综合类 | 86篇 |
数学 | 3700篇 |
物理学 | 4657篇 |
出版年
2024年 | 6篇 |
2023年 | 163篇 |
2022年 | 180篇 |
2021年 | 488篇 |
2020年 | 1617篇 |
2019年 | 2901篇 |
2018年 | 1312篇 |
2017年 | 940篇 |
2016年 | 3831篇 |
2015年 | 3935篇 |
2014年 | 3926篇 |
2013年 | 4780篇 |
2012年 | 3932篇 |
2011年 | 3213篇 |
2010年 | 3544篇 |
2009年 | 3413篇 |
2008年 | 3136篇 |
2007年 | 2511篇 |
2006年 | 2127篇 |
2005年 | 2161篇 |
2004年 | 1913篇 |
2003年 | 1423篇 |
2002年 | 1018篇 |
2001年 | 852篇 |
2000年 | 578篇 |
1999年 | 232篇 |
1998年 | 160篇 |
1997年 | 137篇 |
1996年 | 145篇 |
1995年 | 116篇 |
1994年 | 73篇 |
1993年 | 79篇 |
1992年 | 61篇 |
1991年 | 59篇 |
1990年 | 64篇 |
1989年 | 43篇 |
1988年 | 34篇 |
1987年 | 39篇 |
1986年 | 29篇 |
1985年 | 39篇 |
1984年 | 26篇 |
1983年 | 18篇 |
1982年 | 10篇 |
1981年 | 8篇 |
1980年 | 15篇 |
1979年 | 10篇 |
1978年 | 7篇 |
1975年 | 6篇 |
1974年 | 6篇 |
1970年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
31.
Robin F. Weitkamp Beate Neumann Hans‐Georg Stammler Berthold Hoge 《Angewandte Chemie (International ed. in English)》2020,59(14):5494-5499
We report on the first examples of isolated silanol–silanolate anions, obtained by utilizing weakly coordinating phosphazenium counterions. The silanolate anions were synthesized from the recently published phosphazenium hydroxide hydrate salt with siloxanes. The silanol–silanolate anions are postulated intermediates in the hydroxide‐mediated polymerization of aryl and alkyl siloxanes. The silanolate anions are strong nucleophiles because of the weakly coordinating character of the phosphazenium cation, which is perceptible in their activity in polysiloxane depolymerization. 相似文献
32.
Yuan‐Yuan Che Yanni Yue Ling‐Zhi Lin Bingbing Pei Xuezu Deng Chao Feng 《Angewandte Chemie (International ed. in English)》2020,59(38):16414-16419
Herein, we report a highly efficient and practical method for pyridine‐derived heterobiaryl synthesis through palladium‐catalyzed electrophilic functionalization of easily available pyridine‐derived quaternary phosphonium salts. The nice generality of this reaction was goes beyond arylation, enabling facile incorporation of diverse carbon‐based fragments, including alkenyl, alkynyl, and also allyl fragments, onto the pyridine core. Notably, the silver salt additive is revealed to be of vital importance for the success of this transformation and its pivotal role as transmetallation mediator, which guarantees a smooth transfer of pyridyl group to palladium intermediate, is also described. 相似文献
33.
34.
35.
Dr. Chih‐Min Wang Li‐Wei Lee Tsung‐Yuan Chang Yen‐Chieh Chen Prof. Hsiu‐Mei Lin Prof. Kuang‐Lieh Lu Prof. Kwang‐Hwa Lii 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(5):1878-1881
An organic–inorganic hybrid zinc phosphate with 28‐ring channels was synthesized by use of an organic ligand instead of organic amine template under a hydro(solvo)thermal condition. This crystalline zinc phosphate contains large channels constructed from 28 zinc and phosphate tetrahedral units. The walls of the channels consist of two types of zincophosphate chains, in which the Zn atoms are coordinated by 2,4,5‐tri(4‐pyridyl)‐imidazole ligands as pendent groups. This compound exhibits yellow emission and interesting properties of removing cobalt, cadmium, and mercury cations from aqueous solution. A new two‐dimensional organic–inorganic hybrid zincophosphate was also obtained by changing the solvent mixture ratios in the synthesis. 相似文献
36.
Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons 下载免费PDF全文
Dr. François Riobé Rózsa Szűcs Dr. Pierre‐Antoine Bouit Dr. Denis Tondelier Bernard Geffroy Fátima Aparicio Julia Buendía Prof. Luis Sánchez Prof. Régis Réau Prof. László Nyulászi Prof. Muriel Hissler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(17):6547-6556
We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs). 相似文献
37.
Enantioselective Copper‐Catalyzed Azide–Alkyne Click Cycloaddition to Desymmetrization of Maleimide‐Based Bis(alkynes) 下载免费PDF全文
Tao Song Dr. Li Li Dr. Wei Zhou Dr. Zhan‐Jiang Zheng Dr. Yuan Deng Dr. Zheng Xu Prof. Dr. Li‐Wen Xu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(2):554-558
A copper catalyst system derived from TaoPhos and CuF2 was used successfully for catalytic asymmetric Huisgen [3+2] cycloaddition of azides and alkynes to give optically pure products containing succinimide‐ and triazole‐substituted quaternary carbon stereogenic centers. The desired products were obtained in good yields (60–80 %) and 85:15 to >99:1 enantiomeric ratio (e.r.) in this click cycloaddition reaction. 相似文献
38.
Deep oxidative desulfurization of benzothiophene and dibenzothiophene with a peroxophosphotungstate–ionic liquid brush assembly 下载免费PDF全文
A novel, efficient and reusable heterogeneous catalytic assembly of peroxophosphotungstate held in an ionic liquid brush was synthesized and an extraction and catalytic oxidative desulfurization (ECODS) procedure was developed for a model oil of benzothiophene (BT) and dibenzothiophene (DBT) using 30 wt% hydrogen peroxide as terminal oxidant and methanol as solvent under mild conditions. Several factors that affect sulfur removal were investigated in detail. The highest sulfur removal can reach 100% for BT in 7 h at 70 °C when the molar ratio of H2O2, S and catalyst is 10:1:0.025. The sulfur removal for DBT can also reach 100% in 4 h at 50 °C with the same molar ratio of H2O2, S and catalyst. The experimental results demonstrate that this ECODS process has no apparent scale‐up effect. The catalyst can be easily recovered (via simple filtration) and recycled five times without a significant decrease in activity. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
39.
Selective extraction of catecholamines by packed fiber solid‐phase using composite nanofibers composing of polymeric crown ether with polystyrene 下载免费PDF全文
Li‐Qin Chen Yu Wang Jian‐Song Qu Jian‐Jun Deng Xue‐Jun Kang 《Biomedical chromatography : BMC》2015,29(1):103-109
For the first time, electrospun composite nanofibers comprising polymeric crown ether with polystyrene (PCE‐PS) have been used for the selective extraction of catecholamines – dopamine (DA), norepinephrine (NE) and epinephrine (E) – prior to their analysis by high‐performance liquid chromatography–electrochemical detection. Using a minicartridge packed with PCE‐PS composite nanofibers, the target compounds were extracted effectively from urine samples to which diphenylborinic acid 2‐aminoethyl ester was added as a complexing reagent. The extracted catecholamines could be liberated from the fiber by the addition of acetic acid. A good linearity was observed for catecholamines in the range of 2.0–200 ng mL?1 (NE, E and DA). The detection limits of catecholamines (signal‐to‐noise ratio = 3) were 0.5 ng mL?1 (NE), 0.2 ng mL?1 (E) and 0.2 ng mL?1 (DA), respectively. Under the optimized conditions, the absolute recoveries of the above three catecholamines were 90.6% (NE), 88.5% (E) and 94.5% (DA). The repeatability of extraction performance was from 5.4 to 9.2% (expressed as relative standard deviation). Our results indicate that the proposed method could be used for the determination of NE, E and DA in urine. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
40.
Thermodynamic study of transthyretin association (wild‐type and senile forms) with heparan sulfate proteoglycan: pH effect and implication of the reactive histidine residue 下载免费PDF全文
Ambre Geneste Claire André Nadine Magy‐Bertrand Lydie Lethier Gharbi Tijani Yves Claude Guillaume 《Biomedical chromatography : BMC》2015,29(4):514-522
The tetramer destabilization of transthyretin into monomers and its fibrillation are phenomena leading to amyloid deposition. Heparan sulfate proteoglycan (HSPG) has been found in all amyloid deposits. A chromatographic approach was developed to compare binding parameters between wild‐type transthyretin (wtTTR) and an amyloidogenic transthyretin (sTTR). Results showed a greater affinity of sTTR for HSPG at pH 7.4 compared with wtTTR owing to the monomeric form of sTTR. Analysis of the thermodynamic parameters showed that van der Waals interactions were involved at the complex interface for both transthyretin forms. For sTTR, results from the plot representing the number of protons exchanged vs pH showed that the binding mechanism was pH‐dependent with a critical value at a pH 6.5. This observation was due to the protonation of a histidine residue as an imidazolium cation, which was not accessible when TTR was in its tetrameric structure. At pH >6.5, dehydration at the binding interface and several contacts between nonpolar groups of sTTR and HSPG were also coupled to binding for an optimal hydrogen‐bond network. At pH <6.5, the protonation of the His residue from sTTR monomer when pH decreased broke the hydrogen‐bond network, leading to its destabilization and thus producing slight conformational changes in the sTTR monomer structure. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献