全文获取类型
收费全文 | 24118篇 |
免费 | 2184篇 |
国内免费 | 6474篇 |
专业分类
化学 | 29836篇 |
晶体学 | 372篇 |
力学 | 162篇 |
综合类 | 183篇 |
数学 | 229篇 |
物理学 | 1994篇 |
出版年
2024年 | 10篇 |
2023年 | 348篇 |
2022年 | 323篇 |
2021年 | 609篇 |
2020年 | 866篇 |
2019年 | 748篇 |
2018年 | 790篇 |
2017年 | 817篇 |
2016年 | 1129篇 |
2015年 | 1100篇 |
2014年 | 1469篇 |
2013年 | 2385篇 |
2012年 | 1657篇 |
2011年 | 1789篇 |
2010年 | 1465篇 |
2009年 | 1700篇 |
2008年 | 1755篇 |
2007年 | 1850篇 |
2006年 | 1866篇 |
2005年 | 1763篇 |
2004年 | 1738篇 |
2003年 | 1359篇 |
2002年 | 823篇 |
2001年 | 585篇 |
2000年 | 481篇 |
1999年 | 438篇 |
1998年 | 384篇 |
1997年 | 430篇 |
1996年 | 324篇 |
1995年 | 336篇 |
1994年 | 296篇 |
1993年 | 281篇 |
1992年 | 267篇 |
1991年 | 142篇 |
1990年 | 94篇 |
1989年 | 90篇 |
1988年 | 74篇 |
1987年 | 42篇 |
1986年 | 30篇 |
1985年 | 36篇 |
1984年 | 30篇 |
1983年 | 11篇 |
1982年 | 9篇 |
1981年 | 9篇 |
1980年 | 7篇 |
1976年 | 3篇 |
1975年 | 5篇 |
1974年 | 2篇 |
1971年 | 2篇 |
1968年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
31.
Imine Macrocycle with a Deep Cavity: Guest‐Selected Formation of syn/anti Configuration and Guest‐Controlled Reconfiguration 下载免费PDF全文
Dr. Zhenfeng He Gang Ye Dr. Wei Jiang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(7):3005-3012
A dynamic covalent bond is one of the ideal linkages for the construction of large and robust organic architectures. In the present article, we show how organic templates can efficiently transform a complex dynamic imine library into a dynamic imine macrocycle. Not only is the constitution well controlled, but also the syn/anti host configuration is efficiently selected and even the orientation of the guest in the asymmetric cavity of the host can be well aligned. This is attributed to the delicate balance and the cooperation of multiple noncovalent interactions between the hosts and the guests. Through sequential additions of three guests in appropriate amounts, controlled structural reconfiguration of dynamic covalent architectures has been achieved for the first time. 相似文献
32.
Palladium‐catalyzed decarboxylative coupling of α,β‐unsaturated carboxylic acids with aryl tosylates
We report a general method for selective cross‐coupling of α,β‐unsaturated carboxylic acids with aryl tosylates enabled by versatile Pd(II) complexes. This method features the general cross‐coupling of ubiquitous α,β‐unsaturated carboxylic acids by decarboxylation. The transformation is characterized by its operational simplicity, the use of inexpensive, air‐stable Pd(II) catalysts, scalability and wide substrate scope. The reaction proceeds with high trans selectivity to furnish valuable (E)‐1,2‐diarylethenes. 相似文献
33.
Chunhong Wang Qi Cui Zhixin Zhang Prof. Zhu-Jun Yao Dr. Shaozhong Wang Prof. Zhi-Xiang Yu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(42):9821-9826
1,3-Azaprotio transfer of propargylic α-ketocarboxylate oximes, a new type of alkynyl oximes featuring an ester tether, has been explored by taking advantage of gold catalysis. The incorporation of an oxygen atom to the chain of alkynyl oximes led to the formation of two different oxa-cyclic nitrones. It was found that internal alkynyl oximes with an E-configuration deliver five-membered nitrones, whereas terminal alkynyl oximes with an E-configuration afford six-membered nitrones. DFT calculations on four possible pathways supported a stepwise formation of C−N and C−H bonds, in which a 1,3-acyloxy-migration competes with the 1,3-azaprotio-transfer, especially in the case of internal alkynyl oximes. The relative nucleophilic properties of oxygen in the carbonyl group and the nitrogen in the oxime, the electronic effects of alkynes, and the influence of the ring system have been investigated computationally. 相似文献
34.
Dr. Lei He Prof. Wen-Cui Li Shuang Xu Prof. An-Hui Lu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(13):3209-3218
Microporous carbons afford high surface areas, large pore volumes, and good conductivity, and are fascinating over a wide range of applications. Traditionally synthesized microporous carbon materials usually suffer from some limitations, such as poor accessibility and slow mass transport of molecules due to the micrometer-scale diffusion pathways and space confinement imposed by small pore sizes. Two-dimensional microporous carbon materials, denoted as microporous carbon nanosheets (MCNs), possess nanoscale thickness, which allows fast mass and heat transport along the z axis; thus overcoming the drawbacks of their bulk counterparts. Herein, recent breakthroughs in the synthetic strategies for MCNs are summarized. Three typical methods are discussed in detail with several examples: pyrolysis of organic precursors with 2D units, a templating method that uses wet chemistry, and the molten salt method. Among them, molecular-based assembly of MCNs in the liquid phase shows more controllable morphology, thickness, and pore size distribution. Finally, challenges in this research area are discussed to inspire future explorations. 相似文献
35.
Dr. Masaru Kondo Dr. Shinobu Takizawa Yuzhao Jiang Prof. Dr. Hiroaki Sasai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(42):9866-9869
The Mills reaction and cyclization of readily available 2-aminobenzyl alcohols and nitrosobenzenes using thionyl bromide provided 2H-indazoles in up to 88 % yields. In the metal-free process, acetic acid played a crucial role for the both Mills reaction and cyclization. A brominated 2H-indazole could also be obtained through the one-pot sequence. 相似文献
36.
Minoru Koyama Dr. Takafumi Kawakami Dr. Takashi Okazoe Prof. Dr. Kyoko Nozaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(46):10913-10917
Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF3CH2, and n-C6F13CH2CH2 esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C6F13CH2CH2 esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d6 and MeOH-d4, with DBU in acetonitrile afforded deuterated MMA (MMA-d8) in 70 % yield. 相似文献
37.
Ultrasound-assisted approach was successfully applied for the synthesis of mayenite from calcium and aluminum hydroxides and then subsequently impregnated with Ni by the wet impregnation method. The synthesis was performed with a 13 mm probe-type ultrasound, operating under an acoustic power of 30.5 W and a frequency of 20 kHz. Ultrasound application was studied in detail from a 3k experimental design, where the variables studied were ultrasound time (10–50 min) and calcination temperature (900–1200 °C). Ultrasound promoted an effective dispersion of the precursors in a short time of 10 min leading to a high conversion to mayenite after calcination at 1200 °C. Ultrasound treatment also had a positive effect on Ni impregnation, increasing the dispersion of the metal in the support and leading to a stronger interaction of nickel-containing species with mayenite support. The use of ultrasound application has proved to be attractive both for catalyst properties and for facilitating catalyst synthesis. 相似文献
38.
《Current Applied Physics》2020,20(3):456-461
Carbon-based electrocatalysts for oxygen reduction reaction (ORR), especially in anion exchange membrane fuel cells (AEMFCs), have received a lot of attention because they exhibit excellent stability and are comparable to commercial Pt/C catalysts. Currently, to maximize the catalytic activity of carbon-based electrocatalysts, there are two major strategies: heteroatom doping or exposing active edge sites. However, the approach of increasing heteroatomic dopants of active edge sites has been rarely addressed. In this study, we present a simple strategy to prepare edge-enriched graphene catalysts with an increased ratio of heteroatomic dopants suitable for ORR of AEMFCs. The catalysts were prepared under harsh oxidation conditions, followed by a simple co-doping process with boron and nitrogen. The ORR activity of the catalysts was observed to be related to an increase of edge sites with heteroatomic dopants. We believe that the edge-enriched structure leads to accelerated electron transfer with enhanced oxygen adsorption. 相似文献
39.
《Discrete Mathematics》2020,343(12):112118
40.
Dr. Antonio M. Rodríguez Dr. Pilar Prieto Prof. Antonio de la Hoz Prof. Ángel Díaz-Ortiz D. Raúl Martín Prof. José I. García 《ChemistryOpen》2015,4(3):308-317
The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol−1 and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation. 相似文献