全文获取类型
收费全文 | 61962篇 |
免费 | 13722篇 |
国内免费 | 5085篇 |
专业分类
化学 | 58800篇 |
晶体学 | 659篇 |
力学 | 1968篇 |
综合类 | 319篇 |
数学 | 5668篇 |
物理学 | 13355篇 |
出版年
2023年 | 546篇 |
2022年 | 600篇 |
2021年 | 987篇 |
2020年 | 2194篇 |
2019年 | 3448篇 |
2018年 | 1887篇 |
2017年 | 1503篇 |
2016年 | 4507篇 |
2015年 | 4662篇 |
2014年 | 4784篇 |
2013年 | 5979篇 |
2012年 | 5403篇 |
2011年 | 4969篇 |
2010年 | 4696篇 |
2009年 | 4639篇 |
2008年 | 4384篇 |
2007年 | 3594篇 |
2006年 | 3143篇 |
2005年 | 3062篇 |
2004年 | 2561篇 |
2003年 | 2207篇 |
2002年 | 2015篇 |
2001年 | 1471篇 |
2000年 | 1091篇 |
1999年 | 688篇 |
1998年 | 621篇 |
1997年 | 550篇 |
1996年 | 541篇 |
1995年 | 473篇 |
1994年 | 440篇 |
1993年 | 425篇 |
1992年 | 366篇 |
1991年 | 348篇 |
1990年 | 278篇 |
1989年 | 226篇 |
1988年 | 185篇 |
1987年 | 144篇 |
1986年 | 162篇 |
1985年 | 171篇 |
1984年 | 115篇 |
1983年 | 74篇 |
1982年 | 78篇 |
1981年 | 56篇 |
1980年 | 52篇 |
1979年 | 59篇 |
1978年 | 40篇 |
1976年 | 39篇 |
1975年 | 32篇 |
1974年 | 42篇 |
1973年 | 49篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
81.
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
82.
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
83.
Norbornene derivatives from a metal‐free,strain‐promoted cycloaddition reaction: New building blocks for ring‐opening metathesis polymerization reactions 下载免费PDF全文
Christopher E. Hobbs Binhong Lin Thomas Malinski 《Journal of polymer science. Part A, Polymer chemistry》2015,53(20):2357-2362
The preparation of new ring opening metathesis polymerization (ROMP) monomers using a 1,3‐dipolar cycloaddition between aryl azides and norbornadiene is described. Various norbornenetriazolines, obtained through a solvent‐and catalyst‐free reaction, can subsequently be incorporated into polymer backbones through ROMP reactions. Furthermore, thermal decomposition of the triazoline moiety can allow for further polymer functionalization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2357–2362 相似文献
84.
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
85.
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
86.
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
87.
Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes 下载免费PDF全文
María González‐Esguevillas Ana Pascual‐Escudero Dr. Javier Adrio Prof. Dr. Juan C. Carretero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4561-4565
The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine. 相似文献
88.
Beyond Stereoselectivity,Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters 下载免费PDF全文
Dr. Sophie M. Guillaume Dr. Evgueni Kirillov Dr. Yann Sarazin Prof. Dr. Jean‐François Carpentier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):7988-8003
Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted. 相似文献
89.
Shang‐Xiong Huang‐Fu Jin‐Ni Shen Prof. Hua Lin Prof. Ling Chen Prof. Li‐Ming Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9809-9815
A novel type of supertetrahedral connectivity is exhibited by the 72‐atom discrete supercubooctahedron in (Cs6Cl)2Cs5[Ga15Ge9Se48] ( 1 ), which undergoes both cation and anion exchange, as revealed by unambiguous single‐crystal X‐ray diffraction data. Electronic‐structure studies helped to understand the Ge/Ga distribution. 相似文献
90.
Rational Design and Application of a Redox‐Active,Photoresponsive, Discrete Metallogelator 下载免费PDF全文
Dr. Rouzbeh Afrasiabi Prof. Dr. Heinz‐Bernhard Kraatz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(21):7695-7700
A photoresponsive discrete metallogelator was rationally designed by incorporating a photochromic azobenzene subunit in the structure of a redox‐active ferrocene–peptide conjugate. The target molecule was purposefully equipped with a dipeptide unit capable of self‐assembly in response to sonication. The designed molecule was shown to undergo supramolecular self‐assembly and achieve organogelation in response to ultrasound, light, heat, and redox signals. The sol–gel phase transition of the designed gelator was found to be sensitive to a plethora of input stimuli, allowing the application of the sol–gel transition behavior in basic logic gate operations. A gel‐based NOT logic gate operation was realized when the redox‐active property of the organogel was examined by using different oxidizing agents. The smart response of the gelator was further exploited in designing XOR operations under oxidizing or non‐oxidizing conditions. 相似文献