全文获取类型
收费全文 | 91302篇 |
免费 | 19639篇 |
国内免费 | 9708篇 |
专业分类
化学 | 79740篇 |
晶体学 | 1081篇 |
力学 | 4206篇 |
综合类 | 557篇 |
数学 | 9298篇 |
物理学 | 25767篇 |
出版年
2024年 | 154篇 |
2023年 | 1184篇 |
2022年 | 2145篇 |
2021年 | 2282篇 |
2020年 | 3479篇 |
2019年 | 4660篇 |
2018年 | 3007篇 |
2017年 | 2703篇 |
2016年 | 5970篇 |
2015年 | 6123篇 |
2014年 | 6680篇 |
2013年 | 8358篇 |
2012年 | 8202篇 |
2011年 | 7633篇 |
2010年 | 6702篇 |
2009年 | 6635篇 |
2008年 | 6505篇 |
2007年 | 5330篇 |
2006年 | 4749篇 |
2005年 | 4312篇 |
2004年 | 3497篇 |
2003年 | 3012篇 |
2002年 | 3724篇 |
2001年 | 2797篇 |
2000年 | 2515篇 |
1999年 | 1552篇 |
1998年 | 943篇 |
1997年 | 861篇 |
1996年 | 831篇 |
1995年 | 700篇 |
1994年 | 620篇 |
1993年 | 453篇 |
1992年 | 430篇 |
1991年 | 352篇 |
1990年 | 325篇 |
1989年 | 229篇 |
1988年 | 157篇 |
1987年 | 144篇 |
1986年 | 172篇 |
1985年 | 128篇 |
1984年 | 68篇 |
1983年 | 71篇 |
1982年 | 36篇 |
1981年 | 29篇 |
1980年 | 19篇 |
1979年 | 22篇 |
1977年 | 12篇 |
1975年 | 8篇 |
1957年 | 13篇 |
1925年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
31.
32.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
33.
34.
35.
Synthesis of Small‐Sized,Porous, and Low‐Toxic Magnetite Nanoparticles by Thin POSS Silica Coating
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Swee Kuan Yen D. Prathyusha Varma Wei Mei Guo Dr. Vincent H. B. Ho Dr. Vimalan Vijayaragavan Dr. Parasuraman Padmanabhan Prof. Kishore Bhakoo Prof. Subramanian Tamil Selvan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(10):3914-3918
In this communication, we report the synthesis of small‐sized (<10 nm), water‐soluble, magnetic nanoparticles (MNPs) coated with polyhedral oligomeric silsesquioxanes (POSS), which contain either polyethylene glycol (PEG) or octa(tetramethylammonium) (OctaTMA) as functional groups. The POSS‐coated MNPs exhibit superparamagnetic behavior with saturation magnetic moments (51–53 emu g?1) comparable to silica‐coated MNPs. They also provide good colloidal stability at different pH and salt concentrations, and low cytotoxicity to MCF‐7 human breast epithelial cells. The relaxivity data and magnetic resonance (MR) phantom images demonstrate the potential application of these MNPs in bioimaging. 相似文献
36.
A (di)graph is supereulerian if it contains a spanning eulerian sub(di)graph. This property is a relaxation of hamiltonicity. Inspired by this analogy with hamiltonian cycles and by similar results in supereulerian graph theory, we analyze a number of sufficient Ore type conditions for a digraph to be supereulerian. Furthermore, we study the following conjecture due to Thomassé and the first author: if the arc‐connectivity of a digraph is not smaller than its independence number, then the digraph is supereulerian. As a support for this conjecture we prove it for digraphs that are semicomplete multipartite or quasitransitive and verify the analogous statement for undirected graphs. 相似文献
37.
Unexpected benzimidazole ring formation from a quinoneimide species in the presence of ammonium acetate as supporting electrolyte used in the coupling of electrochemistry with mass spectrometry
下载免费PDF全文
![点击此处可从《Rapid communications in mass spectrometry : RCM》网站下载免费的PDF全文](/ch/ext_images/free.gif)
38.
Tianyu Gong Longhai Guo Jun Ye Lifan He Teng Qiu Xiaoyu Li 《Journal of polymer science. Part A, Polymer chemistry》2021,59(16):1807-1820
The implementation of covalent adaptable networks (CANs) in general resin system is becoming attractive. In this work, we propose a simple post-curing strategy based on the core-shell structured acrylate latex for the achievement on both the improved general performance and the CANs characteristics in latex films. The building to the CANs was relied on the introduction of 4,4′-diaminophenyl disulfide as the curing agent, which cured the acetoacetoxy decorated shell polymer through the ketoamine reaction. The metathesis reaction of aromatic disulfides in the crosslinking segments enabled the thermally induced dynamic behavior of the network as revealed in the stress relaxation tests by comparison with other diamine crosslinking agents without the incorporation of disulfide. The synergism of the dynamic crosslinking of the shell polymer and static crosslinking in the core polymer contributed to the improved mechanical strength (15 MPa, strain% = 250%) and the suppressed water adsorption (~1% in 24 h of soaking) of the latex film, which exhibited above 90% of recovery in both strength and strain from a cut-off film damage within 1 h at 80°C. Moreover, the cured latex film could be recycled, and 75% of the mechanical performance was regained after three fragmentation-hot-pressing cycles. These, in addition with the feasible and environmental friendly characteristics, suggest a sustainable paradigm toward the smart thermosetting latex polymers. 相似文献
39.
Natural products with a variety of pharmacological effects are important sources for commercial drugs, and it is very crucial to develop effective techniques to selectively extract and isolate bioactive natural components from the plants against the background of sustainable development. Ionic liquids (ILs) are a kind of designable material with unique physicochemical properties, including good thermal stability, negligible vapor pressure, good solvation ability, etc. ILs have already been used in pharmaceuticals for extraction, purification, drug delivery, etc. It has been reported that multi-interactions, like hydrogen bonding, hydrophobic interactions, play important roles in the extraction of bioactive components from the plants. In this review, recent progress in the understanding of scientific essence of hydrogen bonding, the special interaction, in ILs was summarized. The extraction of various natural products, one important area in pharmaceutical, by conventional and functional ILs as well as the specific roles of multi-interactions in this process were also reviewed. Moreover, problems existing in bioactive compound extraction by ILs and the future developing trends of this area are given, which might be helpful for scientists, especially beginners, in this field. 相似文献
40.
在中国科学技术大学夏季学期的研究型实验课程"化学科研基础训练"中开设"壳聚糖的制备与表征"综合实验,以龙虾壳为原料,通过除蛋白、脱盐、脱色、脱乙酰等一系列反应,制备得到目标产物壳聚糖。运用红外光谱、核磁共振仪、黏度法、滴定等对产品的结构及性能进行表征。 相似文献