全文获取类型
收费全文 | 22781篇 |
免费 | 2016篇 |
国内免费 | 4944篇 |
专业分类
化学 | 26231篇 |
晶体学 | 137篇 |
力学 | 276篇 |
综合类 | 119篇 |
数学 | 426篇 |
物理学 | 2552篇 |
出版年
2024年 | 64篇 |
2023年 | 359篇 |
2022年 | 689篇 |
2021年 | 802篇 |
2020年 | 1188篇 |
2019年 | 993篇 |
2018年 | 1028篇 |
2017年 | 932篇 |
2016年 | 1015篇 |
2015年 | 953篇 |
2014年 | 1433篇 |
2013年 | 2244篇 |
2012年 | 1244篇 |
2011年 | 1550篇 |
2010年 | 1177篇 |
2009年 | 1286篇 |
2008年 | 1371篇 |
2007年 | 1501篇 |
2006年 | 1393篇 |
2005年 | 1312篇 |
2004年 | 1284篇 |
2003年 | 979篇 |
2002年 | 592篇 |
2001年 | 481篇 |
2000年 | 500篇 |
1999年 | 419篇 |
1998年 | 375篇 |
1997年 | 334篇 |
1996年 | 305篇 |
1995年 | 303篇 |
1994年 | 256篇 |
1993年 | 196篇 |
1992年 | 193篇 |
1991年 | 143篇 |
1990年 | 112篇 |
1989年 | 104篇 |
1988年 | 85篇 |
1987年 | 54篇 |
1986年 | 50篇 |
1985年 | 53篇 |
1984年 | 48篇 |
1983年 | 26篇 |
1982年 | 36篇 |
1981年 | 35篇 |
1980年 | 26篇 |
1979年 | 24篇 |
1978年 | 27篇 |
1977年 | 29篇 |
1976年 | 36篇 |
1974年 | 38篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
211.
Theoretical studies of cobalt(I)‐catalyzed hydroacylation of vinylsilanes and alkyl aldehydes 下载免费PDF全文
Density functional theory (DFT) was used to investigate computationally cobalt(I)‐catalyzed hydroacylation of vinylsilanes and alkyl aldehydes to give ketones. Calculation indicated that cobalt(I)‐catalyzed hydroacylation had eight possible reaction pathways. In the cobalt‐hydride complexes IM2a and IM2b, the hydrogen migration occurred prior to the carbon–carbon bond‐forming reaction. In the complexes IM3a1 and IM3b1, the carbonyl elimination reaction occurred prior to the direct reductive elimination reaction. In the cobalt–carbonyl complexes IM4a and IM4b, the carbonyl insertion reaction was much easier to achieve than the decarbonylation reaction. The dominant reaction pathway was the reaction channel IM1a → TS1a → IM2a → TS2a1 → IM3a1 → TS4a → IM4a → TS5a → IM5a → TS6a → IM6a, and the reductive elimination reaction was the rate‐determining step for this channel, so the dominant product predicted theoretically was the linear ketone. Furthermore, the solvation effect was remarkable, and it decreased generally the free energies of the species. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
212.
Significant progress has been made in the last few years toward synthesizing highly dispersible inorganic catalysts for application in the electrodes of direct methanol fuel cells. In addition, research toward achieving an efficient catalyst supporting matrix has also attracted much attention in recent years. Carbon black- (Vulcan XC-72) supported Platinum and Platinum-Ruthenium catalysts have for long served as the conventional choice as the cathode and the anode catalyst materials, respectively. Oxygen reduction reaction at the cathode and methanol oxidation reaction at the anode occur simultaneously during the operation of a direct methanol fuel cell. However, inefficiencies in these reactions result in a generation of mixed potential. This, in turn, gives rise to reduced cell voltage, increased oxygen stoichiometric ratio, and generation of additional water that is responsible for water flooding in the cathode chamber. In addition, the lack of long-term stability of Pt-Ru anode catalyst, coupled with the tendency of Ru to cross through the polymer electrolyte membrane and eventually get deposited on the cathode, is also a serious drawback. Another source of potential concern is the fact that the natural resource of Pt and the rare earth metal Ru is very limited, and has been predicted to become exhausted very soon. To overcome these problems, new catalyst systems with high methanol tolerance and higher catalytic activity than Pt need to be developed. In addition, the catalyst-supporting matrix is also witnessing a change from traditionally used carbon powder to transition metal carbides and other high-performance materials. This article surveys the recent literature based on the advancements made in the field of highly dispersible inorganic catalysts for application in direct methanol fuel cells, as well as the progress made in the area of catalyst-supporting matrices. 相似文献
213.
《Current Applied Physics》2015,15(12):1580-1586
The characteristics of gasification reactions for carbon–carbonate mixtures were experimentally investigated at high temperatures up to 900 °C, considering the application of the mixtures to the external anode media of a direct carbon fuel cell. A thermo-gravimetric analysis (TGA) was conducted in either a nitrogen or carbon dioxide ambient environment for Li2CO3, K2CO3 and a mixture of these two substances with carbon black. Changes in the exit gas composition were also monitored during the heating process. It was shown that gasification in the mixture media occurs much more rapidly than carbonate decomposition at elevated temperatures, even for low concentrations of CO2. It was also shown that the loading of carbonates to carbon significantly affects the global gasification reaction; it increased the reaction rate by an order of magnitude and decreased its activation energy. Based on the experimental observations, a simplified reaction model of gasification was suggested for the anode media of a DCFC, regarding carbonate-catalysed and metal-catalysed pathways of Boudouard reactions. 相似文献
214.
Quinones as Dienophiles in the Diels–Alder Reaction: History and Applications in Total Synthesis 下载免费PDF全文
Dr. Christopher C. Nawrat Prof. Dr. Christopher J. Moody 《Angewandte Chemie (International ed. in English)》2014,53(8):2056-2077
In the canon of reactions available to the organic chemist engaged in total synthesis, the Diels–Alder reaction is among the most powerful and well understood. Its ability to rapidly generate molecular complexity through the simultaneous formation of two carbon? carbon bonds is almost unrivalled, and this is reflected in the great number of reported applications of this reaction. Historically, the use of quinones as dienophiles is highly significant, being the very first example investigated by Diels and Alder. Herein, we review the application of the Diels–Alder reaction of quinones in the total synthesis of natural products. The highlighted examples span some 60 years from the landmark syntheses of morphine (1952) and reserpine (1956) by Gates and Woodward, respectively, through to the present day examples, such as the tetracyclines. 相似文献
215.
Dr. Dominikus Heift Dr. Zoltán Benkő Prof. Dr. Hansjörg Grützmacher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(36):11326-11330
Unsaturated phosphorus compounds, such as phosphaalkenes and phosphaalkynes, show a versatile reactivity in cycloadditions. Although phosphaketenes (R?P?C?O) have been known for three decades, their chemistry has remained limited. Herein, we show that heteroatom‐substituted phosphaketenes, R3E?P?C?O (E=Si, Sn), are building blocks for silyl‐ and stannyl‐substituted five‐membered heterocycles containing three phosphorous atoms. The structure of the heterocyclic anion depends on the nature of the tetrel atom involved. Although the silyl analogue [P3C2(OSiR3)2]? is an aromatic 1,2,4‐triphospholide, the stannyl compound [P(CO)2(PSnR3)2]? is a 1,2,4‐triphosphacyclopenta‐3,5‐dionate with a delocalized OCPCO fragment. Because of their anionic character, these compounds can easily be used as building blocks, for example, in the preparation of a silyl‐functionalized hexaphosphaferrocene or the parent 1,2,4‐triphosphacyclopenta‐3,5‐dionate [P(CO)2(PH)2]?. NMR spectroscopic investigations and computations have shown that the heterocycle‐formation reactions presented herein are remarkably complex. 相似文献
216.
Combining Experimental and Computational Studies to Understand and Predict Reactivities of Relevance to Homogeneous Catalysis 下载免费PDF全文
Dr. Althea S.‐K. Tsang Italo A. Sanhueza Prof. Dr. Franziska Schoenebeck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(50):16432-16441
This article showcases three major uses of computational chemistry in reactivity studies: the application after, in combination with, and before experiment. Following a brief introduction of suitable computational tools, challenges and opportunities in the implementation of computational chemistry in reactivity studies are discussed, exemplified with selected case studies from our and other laboratories. 相似文献
217.
Exceedingly Fast Copper(II)‐Promoted ortho CH Trifluoromethylation of Arenes using TMSCF3 下载免费PDF全文
Ming Shang Shang‐Zheng Sun Dr. Hong‐Li Wang Dr. Brian N. Laforteza Prof. Dr. Hui‐Xiong Dai Prof. Dr. Jin‐Quan Yu 《Angewandte Chemie (International ed. in English)》2014,53(39):10439-10442
The direct ortho‐trifluoromethylation of arenes, including heteroarenes, with TMSCF3 has been accomplished by a copper(II)‐promoted C? H activation reaction which completes within 30 minutes. Mechanistic investigations are consistent with the involvement of C? H activation, rather than a simple electrophilic aromatic substitution (SEAr), as the key step. 相似文献
218.
A Protic Ionic Liquid Catalyzes CO2 Conversion at Atmospheric Pressure and Room Temperature: Synthesis of Quinazoline‐2,4(1H,3H)‐diones 下载免费PDF全文
Dr. Yanfei Zhao Bo Yu Dr. Zhenzhen Yang Dr. Hongye Zhang Leiduan Hao Xiang Gao Prof. Zhimin Liu 《Angewandte Chemie (International ed. in English)》2014,53(23):5922-5925
The chemical fixation of CO2 under mild reaction conditions is of significance from a sustainable chemistry viewpoint. Herein a CO2‐reactive protic ionic liquid (PIL), [HDBU+][TFE?], was designed by neutralization of the superbase 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) with a weak proton donor trifluoroethanol (TFE). As a bifunctional catalyst for simultaneously activating CO2 and the substrate, this PIL displayed excellent performance in catalyzing the reactions of CO2 with 2‐aminobenzonitriles at atmospheric pressure and room temperature, thus producing a series of quinazoline‐2,4(1H,3H)‐diones in excellent yields. 相似文献
219.
On‐Line Monitoring of Chemical Reactions by using Bench‐Top Nuclear Magnetic Resonance Spectroscopy 下载免费PDF全文
Dr. E. Danieli Dr. J. Perlo Dr. A. L. L. Duchateau G. K. M. Verzijl Dr. V. M. Litvinov Prof. Dr. B. Blümich Dr. F. Casanova 《Chemphyschem》2014,15(14):3060-3066
Real‐time nuclear magnetic resonance (NMR) spectroscopy measurements carried out with a bench‐top system installed next to the reactor inside the fume hood of the chemistry laboratory are presented. To test the system for on‐line monitoring, a transfer hydrogenation reaction was studied by continuously pumping the reaction mixture from the reactor to the magnet and back in a closed loop. In addition to improving the time resolution provided by standard sampling methods, the use of such a flow setup eliminates the need for sample preparation. Owing to the progress in terms of field homogeneity and sensitivity now available with compact NMR spectrometers, small molecules dissolved at concentrations on the order of 1 mmol L?1 can be characterized in single‐scan measurements with 1 Hz resolution. Owing to the reduced field strength of compact low‐field systems compared to that of conventional high‐field magnets, the overlap in the spectrum of different NMR signals is a typical situation. The data processing required to obtain concentrations in the presence of signal overlap are discussed in detail, methods such as plain integration and line‐fitting approaches are compared, and the accuracy of each method is determined. The kinetic rates measured for different catalytic concentrations show good agreement with those obtained with gas chromatography as a reference analytical method. Finally, as the measurements are performed under continuous flow conditions, the experimental setup and the flow parameters are optimized to maximize time resolution and signal‐to‐noise ratio. 相似文献
220.
In the presence of zinc chloride, the in situ generated β‐enamino ester from the reaction of morpholine, piperidine and pyrrolidine with methyl propiolate reacted, with aromatic aldehydes and thiourea in ethanol resulting in the functionalized tetrahydropyrimidin‐2‐thiones in satisfactory yields and with good diastereoselectivity. When aromatic aldehydes bearing electron‐withdrawing group were used in the reaction, the 4‐hydroxytetrahydropyrimidin‐2‐thione derivatives were obtained as the main product. 相似文献