全文获取类型
收费全文 | 532篇 |
免费 | 36篇 |
国内免费 | 5篇 |
专业分类
化学 | 386篇 |
晶体学 | 1篇 |
力学 | 41篇 |
数学 | 41篇 |
物理学 | 104篇 |
出版年
2024年 | 2篇 |
2023年 | 1篇 |
2022年 | 11篇 |
2021年 | 20篇 |
2020年 | 28篇 |
2019年 | 29篇 |
2018年 | 26篇 |
2017年 | 25篇 |
2016年 | 49篇 |
2015年 | 25篇 |
2014年 | 26篇 |
2013年 | 69篇 |
2012年 | 46篇 |
2011年 | 47篇 |
2010年 | 29篇 |
2009年 | 28篇 |
2008年 | 22篇 |
2007年 | 20篇 |
2006年 | 9篇 |
2005年 | 8篇 |
2004年 | 5篇 |
2003年 | 8篇 |
2002年 | 8篇 |
2001年 | 1篇 |
2000年 | 1篇 |
1997年 | 3篇 |
1993年 | 2篇 |
1992年 | 5篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1975年 | 1篇 |
排序方式: 共有573条查询结果,搜索用时 15 毫秒
11.
12.
Synthesis of diaryl sulfides via nickel ferrite‐catalysed C─S bond formation in green media 下载免费PDF全文
NiFe2O4 magnetic nanoparticles (MNPs) were synthesized, characterized and applied as an air‐stable, inexpensive and magnetically separable nanocatalyst for the synthesis of structurally diverse sulfides. Efficient methodologies were developed for the synthesis of unsymmetric diaryl sulfides via odourless and one‐pot reactions of triphenyltin chloride/S8 or arylboronic acid/S8 as thiolating agents with aryl halides or nitroarenes as starting materials in the presence of base (K2CO3 or NaOH) and NiFe2O4 MNPs as a catalyst in water or poly (ethylene glycol) as solvent at 80–110 °C. Free from ligand and the unpleasant smell of thiols and with the use of magnetically reusable nanocatalyst, green solvents and commercially available and cheap sulfur source and starting materials, these methods are more eco‐friendly and practical than available protocols for the synthesis of sulfides. 相似文献
13.
14.
Dr. Renata Kaczmarek Samuel Ward Dipra Debnath Taisiya Jacobs Alexander D. Stark Dariusz Korczyński Prof. Dr. Anil Kumar Prof. Dr. Michael D. Sevilla Dr. Sergey A. Denisov Dr. Viacheslav Shcherbakov Dr. Pascal Pernot Prof. Dr. Mehran Mostafavi Prof. Dr. Roman Dembinski Prof. Dr. Amitava Adhikary 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(43):9495-9505
The directionality of the hole-transfer processes between DNA backbone and base was investigated by using phosphorodithioate [P(S−)=S] components. ESR spectroscopy in homogeneous frozen aqueous solutions and pulse radiolysis in aqueous solution at ambient temperature confirmed initial formation of G.+-P(S−)=S. The ionization potential of G-P(S−)=S was calculated to be slightly lower than that of guanine in 5′-dGMP. Subsequent thermally activated hole transfer from G.+ to P(S−)=S led to dithiyl radical (P-2S.) formation on the μs timescale. In parallel, ESR spectroscopy, pulse radiolysis, and density functional theory (DFT) calculations confirmed P-2S. formation in an abasic phosphorodithioate model compound. ESR investigations at low temperatures and higher G-P(S−)=S concentrations showed a bimolecular conversion of P-2S. to the σ2-σ*1-bonded dimer anion radical [-P-2S 2S-P-]− [ΔG (150 K, DFT)=−7.2 kcal mol−1]. However, [-P-2S 2S-P-]− formation was not observed by pulse radiolysis [ΔG° (298 K, DFT)=−1.4 kcal mol−1]. Neither P-2S. nor [-P-2S 2S-P-]− oxidized guanine base; only base-to-backbone hole transfer occurs in phosphorodithioate. 相似文献
15.
Mandana Amiri Zahra Tofighi Ali Khodayari Abolfazl Bezaatpour Shabnam Sohrabnezhad Vladyslav Mishyn Rabah Boukherroub Sabine Szunerits 《应用有机金属化学》2020,34(10):e5871
We report a Cu-based metal–organic framework (MOF) decorated by CuO nanostructures as an efficient catalyst for the oxygen evolution reaction (OER). MIL-53(Cu) was synthesized by a hydrothermal approach using 1,4-bezenedicarboxylic acid as organic precursor and further annealed at 300°C to form CuO nanostructures on its surface. The produced electrocatalyst, CuO@MIL-53(Cu), was characterized using various techniques. Under alkaline conditions, the developed electrocatalyst exhibited an overpotential of 801 and 336 mV versus RHE at 10 and 1 mA cm−2, respectively. The reproducibility of the catalytic performance was validated using several electrodes. It was confirmed that the CuO hair-like nanostructures grown on MIL-53(Cu) using thermal treatment exhibit high OER activity, good kinetics and durability. CuO@MIL-53(Cu) is an economic noble-metal-free OER electrocatalyst. It has potential for application as anode material for sustainable energy technologies like batteries, fuel cells and water electrolysis. 相似文献
16.
Nanostructured γ-Al2O3 with high surface area and mesoporous structure was synthesized by sol-gel method and employed as catalyst support for nickel catalysts in methane reforming with carbon dioxide. The prepared samples were characterized by XRD, N2adsorption-desorption,TPR, TPO, TPH, NH3-TPD and SEM techniques. The BET analysis showed a high surface area of 204 m2 g-1and a narrow pore-size distribution centered at a diameter of 5.5 nm for catalyst support. The BET results revealed that addition of lanthanum oxide to aluminum oxide decreased the specific surface area. In addition, TPR results showed that addition of lanthanum oxide increased the reducibility of nickel catalyst. The catalytic evaluation results showed an increase in methane conversion with increasing lanthanum oxide to 3 mol% and further increase in lanthanum content decreased the catalytic activity. TPO analysis revealed that the coke deposition decreased with increasing lanthanum oxide to 3 mol%. SEM and TPH analyses confirmed the formation of whisker type carbon over the spent catalysts. Addition of steam and O2 to dry reforming feed increased the methane conversion and led to carbon free operation in combined processes. 相似文献
17.
18.
Taghavizadeh Yazdi Mohammad Ehsan Modarres Masoomeh Amiri Mohammad Sadegh Darroudi Majid 《Research on Chemical Intermediates》2019,45(3):1105-1116
Research on Chemical Intermediates - We have synthesized silver nanoparticles (Ag-NPs) via a simple and eco-friendly method through the utilization of aqueous aerial parts of Salvia leriifolia... 相似文献
19.
20.