全文获取类型
收费全文 | 2152篇 |
免费 | 545篇 |
国内免费 | 190篇 |
专业分类
化学 | 2358篇 |
晶体学 | 42篇 |
力学 | 37篇 |
综合类 | 17篇 |
数学 | 27篇 |
物理学 | 406篇 |
出版年
2024年 | 7篇 |
2023年 | 33篇 |
2022年 | 68篇 |
2021年 | 90篇 |
2020年 | 130篇 |
2019年 | 107篇 |
2018年 | 90篇 |
2017年 | 84篇 |
2016年 | 191篇 |
2015年 | 154篇 |
2014年 | 131篇 |
2013年 | 246篇 |
2012年 | 173篇 |
2011年 | 106篇 |
2010年 | 122篇 |
2009年 | 115篇 |
2008年 | 106篇 |
2007年 | 112篇 |
2006年 | 103篇 |
2005年 | 114篇 |
2004年 | 74篇 |
2003年 | 98篇 |
2002年 | 86篇 |
2001年 | 36篇 |
2000年 | 23篇 |
1999年 | 31篇 |
1998年 | 17篇 |
1997年 | 41篇 |
1996年 | 28篇 |
1995年 | 40篇 |
1994年 | 10篇 |
1993年 | 17篇 |
1992年 | 25篇 |
1991年 | 12篇 |
1990年 | 12篇 |
1989年 | 13篇 |
1988年 | 8篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 9篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1978年 | 2篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1973年 | 3篇 |
1970年 | 1篇 |
排序方式: 共有2887条查询结果,搜索用时 31 毫秒
111.
Philipp Bissinger Prof. Dr. Holger Braunschweig Dr. Alexander Damme Dr. Rian D. Dewhurst Dr. Katharina Kraft Thomas Kramer Dr. Krzysztof Radacki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(40):13402-13407
The synthesis of base‐stabilized boryl and borylene complexes is reported. An N‐heterocyclic carbene (NHC)‐stabilized iron–dihydroboryl complex was prepared by two different routes including methane liberation and salt elimination. A range of base‐stabilized iron–dichloroboryl complexes was prepared by addition of Lewis bases to boryl complexes. Base‐stabilized, cationic monochloroborylene complexes were synthesized from these boryl complexes by halide abstraction by using weakly coordinating anions. 相似文献
112.
113.
Yanhong Chao Wenshuai Zhu Jiaxin Chen Peiwen Wu Huaming Li 《Green Chemistry Letters and Reviews》2014,7(4):330-336
Graphene-like layered hexagonal boron nitride (g-BN) was prepared and characterized. The performance of using g-BN as an adsorbent for removal of fluoroquinolone antibiotic gatifloxacin (GTF) from aqueous solution was evaluated. g-BN showed an excellent adsorption capability with notable GTF adsorption ratio of more than 90%. Data of equilibrium adsorption of GTF onto g-BN at different temperatures were represented by Langmuir, Freundlich and Tempkin isotherm models, and Langmuir exhibited the best fitting with the maximum adsorption capacity of 88.5 mg·g?1 at 288 K. GTF adsorption was insignificantly affected by solution pH. Competitive role of Na+ and Ca2+ in the solution inhibited the adsorption of GTF and decreased the adsorption capacity a bit. The adsorption process was spontaneous and exothermic. The adsorption was probably governed by π–π interaction between GTF and g-BN, and electrostatic interaction may also exist in the adsorption process. 相似文献
114.
115.
Constanze Keck Dr. Jennifer Hahn Divanshu Gupta Prof. Dr. Holger F. Bettinger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(5):e202103614
The boron-nitrogen analogue of ortho-benzyne, 1,2-azaborinine, is a reactive intermediate that features a formal boron-nitrogen triple bond. We here show by combining experimental and computational techniques that the Lewis acidity of the boron center of dibenzo[c,e][1,2]azaborinine allows interaction with the silicon containing single bonds Si−E through the silicon bonding partner E (E=F, Cl, OR, H). The binding to boron activates the Si−E bonds for subsequent insertion reaction. This shows that the BN-aryne is a ferocious species that even can activate and insert into the very strong Si−F bond. 相似文献
116.
Mingming Huang Dr. Jiefeng Hu Shasha Shi Dr. Alexandra Friedrich Johannes Krebs Prof. Dr. Stephen A. Westcott Prof. Dr. Udo Radius Prof. Dr. Todd B. Marder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(24):e202200480
Defunctionalization of readily available feedstocks to provide alkenes for the synthesis of multifunctional molecules represents an extremely useful process in organic synthesis. Herein, we describe a transition metal-free, simple and efficient strategy to access alkyl 1,2-bis(boronate esters) via regio- and diastereoselective diboration of secondary and tertiary alkyl halides (Br, Cl, I), tosylates, and alcohols. Control experiments demonstrated that the key to this high reactivity and selectivity is the addition of a combination of potassium iodide and N,N-dimethylacetamide (DMA). The practicality and industrial potential of this transformation are demonstrated by its operational simplicity, wide functional group tolerance, and the late-stage modification of complex molecules. From a drug discovery perspective, this synthetic method offers control of the position of diversification and diastereoselectivity in complex ring scaffolds, which would be especially useful in a lead optimization program. 相似文献
117.
Daniel Vogler Maximilian Schöner Dr. Elisabeth Kaifer Prof. Dr. Dr. Hans-Jörg Himmel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(49):e202201389
In this work we report the first cycloaddition reactions between a diazido diborane(4) and terminal alkynes, providing unique access to bis-1,2,3-triazoles connected by a B−B bridge. The catalyst-free reactions are highly selective, yielding exclusively the thermodynamically disfavored bis-1,4-triazoles. The reactions are enabled by the high thermal stability of the diazido-diborane [B(hpp)(N3)]2 (hpp=1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-α]pyrimidinate). Due to the tetra-coordinate boron atoms in this reagent, the reactions are tolerant with respect to the introduction of Lewis-basic groups at the alkyne. The scope and limitations of the new reactions are discussed. 相似文献
118.
Dr. Masayuki Gon Junko Wakabayashi Masashi Nakamura Prof. Dr. Kazuo Tanaka Prof. Dr. Yoshiki Chujo 《化学:亚洲杂志》2021,16(6):696-703
We demonstrate that multi-fluorinated boron-fused azobenzene (BAz) complexes can work as a strong electron acceptor in electron donor-acceptor (D-A) type π-conjugated polymers. Position-dependent substitution effects were revealed, and the energy level of the lowest unoccupied molecular orbital (LUMO) was critically decreased by fluorination. As a result, the obtained polymers showed near-infrared (NIR) emission (λPL=758–847 nm) with high absolute photoluminescence quantum yield (ΦPL=7–23%) originating from low-lying LUMO energy levels of the BAz moieties (−3.94 to −4.25 eV). Owing to inherent solid-state emissive properties of the BAz units, deeper NIR emission (λPL=852980 nm) was detected in film state. Clear solvent effects prove that the NIR emission is from a charge transfer state originating from a strong D-A interaction. The effects of fluorination on the frontier orbitals are well understandable and predictable by theoretical calculation with density functional theory. This study demonstrates the effectiveness of fluorination to the BAz units for producing a strong electron-accepting unit through fine-tuning of energy gaps, which can be the promising strategy for designing NIR absorptive and emissive materials. 相似文献
119.
Mihaela Tertis Oana Hosu Bogdan Feier Andreea Cernat Anca Florea Cecilia Cristea 《Molecules (Basel, Switzerland)》2021,26(11)
Food safety and quality control pose serious issues to food industry and public health domains, in general, with direct effects on consumers. Any physical, chemical, or biological unexpected or unidentified food constituent may exhibit harmful effects on people and animals from mild to severe reactions. According to the World Health Organization (WHO), unsafe foodstuffs are especially dangerous for infants, young children, elderly, and chronic patients. It is imperative to continuously develop new technologies to detect foodborne pathogens and contaminants in order to aid the strengthening of healthcare and economic systems. In recent years, peptide-based sensors gained much attention in the field of food research as an alternative to immuno-, apta-, or DNA-based sensors. This review presents an overview of the electrochemical biosensors using peptides as molecular bio-recognition elements published mainly in the last decade, highlighting their possible application for rapid, non-destructive, and in situ analysis of food samples. Comparison with peptide-based optical and piezoelectrical sensors in terms of analytical performance is presented. Methods of foodstuffs pretreatment are also discussed. 相似文献
120.
Peng Liu Hui Ruan Tiantian Li Jiaqi Chen Fuqiu Ma Duoqiang Pan Wangsuo Wu 《Molecules (Basel, Switzerland)》2021,26(4)
The low cost β-zeolite and ethylenediamine modified β-zeolite (EDA@β-zeolite) were prepared by self-assembly method and used for Cu(II) removal from contaminated aqueous solution. Removal ability of β-zeolite toward Cu(II) was greatly improved after ethylenediamine (EDA) modification, the removal performance was greatly affected by environmental conditions. XPS results illustrated that the amide group played important role in the removal process by forming complexes with Cu(II). The EDA@β-zeolite showed desirable recycling ability. The finding herein suggested that the proposed composite is a promising and suitable candidate for the removal of Cu(II) from contaminated natural wastewater and aquifer. 相似文献