全文获取类型
收费全文 | 19955篇 |
免费 | 3453篇 |
国内免费 | 4375篇 |
专业分类
化学 | 14598篇 |
晶体学 | 569篇 |
力学 | 1242篇 |
综合类 | 388篇 |
数学 | 2864篇 |
物理学 | 8122篇 |
出版年
2024年 | 31篇 |
2023年 | 202篇 |
2022年 | 506篇 |
2021年 | 589篇 |
2020年 | 614篇 |
2019年 | 693篇 |
2018年 | 616篇 |
2017年 | 718篇 |
2016年 | 840篇 |
2015年 | 987篇 |
2014年 | 1246篇 |
2013年 | 1558篇 |
2012年 | 1643篇 |
2011年 | 1804篇 |
2010年 | 1552篇 |
2009年 | 1606篇 |
2008年 | 1803篇 |
2007年 | 1586篇 |
2006年 | 1560篇 |
2005年 | 1344篇 |
2004年 | 1046篇 |
2003年 | 842篇 |
2002年 | 915篇 |
2001年 | 777篇 |
2000年 | 670篇 |
1999年 | 417篇 |
1998年 | 264篇 |
1997年 | 207篇 |
1996年 | 183篇 |
1995年 | 142篇 |
1994年 | 145篇 |
1993年 | 91篇 |
1992年 | 95篇 |
1991年 | 77篇 |
1990年 | 64篇 |
1989年 | 78篇 |
1988年 | 58篇 |
1987年 | 36篇 |
1986年 | 33篇 |
1985年 | 28篇 |
1984年 | 21篇 |
1983年 | 14篇 |
1982年 | 7篇 |
1981年 | 8篇 |
1980年 | 11篇 |
1979年 | 11篇 |
1978年 | 16篇 |
1977年 | 3篇 |
1976年 | 4篇 |
1974年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
971.
A Mechanistic Switch in C-H Bond Activation by Elusive Fe\begin{document}$^\text{V}$\end{document} (O)(TAML) Reaction Intermediate: A Theoretical Study
下载免费PDF全文
![点击此处可从《化学物理学报(中文版)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
The divergent behavior of C-H bond oxidations of aliphatic substrates compared to those of aromatic substrates shown in Gupta's experiment was mechanistically studied herein by means of density functional theory calculations. Our calculations reveal that such difference is caused by different reaction mechanisms between two kinds of substrates (the aliphatic cyclohexane, 2, 3-dimethylbutane and the aromatic toluene, ethylbenzene and cumene). For the aliphatic substrates, C-H oxidation by the oxidant Fe\begin{document}$^{\rm{V}}$\end{document} (O)(TAML) is a hydrogen atom transfer process; whereas for the aromatic substrates, C-H oxidation is a proton-coupled electron transfer (PCET) process with a proton transfer character on the transition state, that is, a proton-coupled electron transfer process holding a proton transfer-like transition state (PCET(PT)). This difference is caused by the strong \begin{document}$\pi$\end{document} -\begin{document}$\pi$\end{document} interactions between the tetra-anionic TAML ring and the phenyl ring of the aromatic substrates, which has a "pull" effect to make the electron transfer from substrates to the Fe=O moiety inefficient. 相似文献
972.
本研究探讨一站式CT检查系统在急性胸痛患者管理中干预方案的应用。将符合急性胸痛患者49例纳入研究,采用自动触发方式采集患者上胸部volume数据集和心胸部volume数据集,经过处理后获得胸主动脉、冠状动脉、肺动脉及全胸部图像。本研究中,测量结果发现平均CT值主动脉弓是(332±51)Hu,升主动脉是(435±53)Hu,肺动脉干是(491±93)Hu,降主动脉是(454±70)Hu,而左冠状动脉和右冠状动脉分别是(425±60)Hu、(415±62)Hu。病变鉴定发现,急性肺栓塞12例,主动脉弓动脉粥样硬化斑块破裂8例,肺组织实变4例,慢性肺栓塞伴右心衰竭2例,胸腔积液2例,左冠状动脉非关键性狭窄11例,右冠状动脉非关键性狭窄7例,心包积液2例,复合解剖畸形1例。总之,本研究通过一站式CT检查系统对急性胸痛患者干预方案的制定提供了重要指导。 相似文献
973.
Anling Li Qianrui Kang Shuaiyang Ren Yong Zhang Fengwei Zhang Qiang He 《Arabian Journal of Chemistry》2021,14(8):103247
To study the influence of different concentrations of zinc oxide (ZnO)/silicon dioxide (SiO2) composite coating on hydrophobic property and mechanical stability of paper mulch film, three kinds of ZnO/SiO2 composite coating paper mulch films (2%, 4%, 6%) with different coating substance contents were prepared by brush coating method. Through particle size analysis, contact angle, rolling angle and mechanical stability test, combined with scanning electron microscope, three-dimensional morphology and roughness measuring instrument, the optimal concentration of ZnO/SiO2 composite coated paper mulch film was screened out. Through acid-base salt corrosion test, silver mirror reaction and surface self-cleaning, the optimal concentration of composite coated paper mulch film was compared with the original paper mulch film to prove its excellent chemical stability and hydrophobicity. The results show that the paper mulch film with 4% coating material has excellent hydrophobicity and mechanical stability, can effectively reduce the surface roughness of paper mulch film, and has remarkable effects in resisting acid, alkali and salt and self-cleaning. 相似文献
974.
Enhanced Static Modulated Fourier Transform Spectrometer for Fast Approximation in Field Application
We discuss the data sampling frequency, the spectral resolution, and the limit for non-aliasing in the static modulated Fourier transform spectrometer based on a modified Sagnac interferometer. The measurement was performed in a very short 4 ms, which is applicable for real time field operation. The improved spectrometer characteristics were used to investigate the spectral properties of an InGaAs light emitting diode. In addition, The measured spectral peak was shifted from 6420 cm−1 to 6365 cm−1, as the temperature increased from 25 °C to 40 °C, when the operating current is fixed to be 0.55 A. As the applied current increased from 0.30 A to 0.55 A at room temperature, the spectral width was broadened from 316 cm−1 to 384 cm−1. Compared to the conventional Fourier transform spectrometer, the measured spectral width by the static modulated Fourier transform spectrometer showed a deviation less than 10%, and the spectral peak shift according to the temperature rise showed a difference within 2%. 相似文献
975.
Eui-Baek Byun Ha-Yeon Song Woo Sik Kim Jeong Moo Han Ho Seong Seo Woo Yong Park Kwangwook Kim Eui-Hong Byun 《Molecules (Basel, Switzerland)》2021,26(6)
Although our previous study revealed that gamma-irradiated chrysin enhanced anti-inflammatory activity compared to intact chrysin, it remains unclear whether the chrysin derivative, CM1, produced by gamma irradiation, negatively regulates toll-like receptor (TLR) signaling. In this study, we investigated the molecular basis for the downregulation of TLR4 signal transduction by CM1 in macrophages. We initially determined the appropriate concentration of CM1 and found no cellular toxicity below 2 μg/mL. Upon stimulation with lipopolysaccharide (LPS), CM1 modulated LPS-stimulated inflammatory action by suppressing the release of proinflammatory mediators (cytokines TNF-α and IL-6) and nitric oxide (NO) and downregulated the mitogen-activated protein kinase (MAPK) and nuclear factor-κB (NF-κB) signaling pathways. Furthermore, CM1 markedly elevated the expression of the TLR negative regulator toll-interacting protein (Tollip) in dose- and time-dependent manners. LPS-induced expression of cell surface molecules (CD80, CD86, and MHC class I/II), proinflammatory cytokines (TNF-α and IL-6), COX-2, and iNOS-mediated NO were inhibited by CM1; these effects were prevented by the knockdown of Tollip expression. Additionally, CM1 did not affect the downregulation of LPS-induced expression of MAPKs and NF-κB signaling in Tollip-downregulated cells. These findings provide insight into effective therapeutic intervention of inflammatory disease by increasing the understanding of the negative regulation of TLR signaling induced by CM1. 相似文献
976.
Jun Soo Park Jeong Soo Kim Myoung Jin Ho Dong Woo Park Eun A. Kim Yong Seok Choi Sun Woo Jang Myung Joo Kang 《Molecules (Basel, Switzerland)》2021,26(6)
The incorporation of permeation enhancers in topical preparations has been recognized as a simple and valuable approach to improve the penetration of antifungal agents into toenails. In this study, to improve the toenail delivery of efinaconazole (EFN), a triazole derivative for onychomycosis treatment, topical solutions containing different penetration enhancers were designed, and the permeation profiles were evaluated using bovine hoof models. In an in vitro permeation study in a Franz diffusion cell, hydroalcoholic solutions (HSs) containing lipophilic enhancers, particularly prepared with propylene glycol dicaprylocaprate (Labrafac PG), had 41% higher penetration than the HS base. Moreover, the combination of hydroxypropyl-β-cyclodextrin with Labrafac PG further facilitated the penetration of EFN across the hoof membrane. In addition, this novel topical solution prepared with both lipophilic and hydrophilic enhancers was physicochemically stable, with no drug degradation under ambient conditions (25 °C, for 10 months). Therefore, this HS system can be a promising tool for enhancing the toenail permeability and therapeutic efficacy of EFN. 相似文献
977.
Su Ying Li Weili Liu Wenmao Li Yong Li Dong 《Journal of Thermal Analysis and Calorimetry》2021,146(5):2279-2289
Journal of Thermal Analysis and Calorimetry - The stator ventilation duct is the main path for fluid flowing to cool the stator bar and the core. Considering the complexity of the ventilation... 相似文献
978.
Winges FATIMA Muhammad TARIQUE LI Min CHEN Mingyi Muzamil KHATRI Muhammad Nauman SARWAR Icksoo KIM Farooq AHMED Zeeshan KHATRI CHEN Rouxi WEI Kai 《高等学校化学研究》2021,37(3):535-540
Based on the functional properties of electrospun cellulose nanofibers(CNF), scientists are showing substantial interest to enhance the aesthetic properties. However, the lower color yield has remained a big challenge due to the higher surface area of nanofibers. In this study, we attempted to improve the color yield properties of CNF by the pad-steam dyeing method. Neat CNF was obtained by deacetylation of electrospun cellulose acetate(CA) nanofibers. Three different kinds of reactive dyes were used and pad-steam dyeing parameters were optimized. SEM images revealed smooth morphology with an increase in the average diameter of nanofibers. FTIR results showed no change in the chemical structure after dyeing of CNF. Color fastness results demonstrated excellent ratings for reactive dyes, which indicate good dye fixation properties and no color loss during the washing process. The results confirm that the pad-steam dyeing method can be potentially considered to improve the aesthetic properties of CNF, which can be utilized for functional garments, such as breathable raincoats and disposable face masks. 相似文献
979.
Ping Zhang Wenju Chang Hongyun Jiao Yanshang Kang Wenxuan Zhao Peipei Cui Yong Liang Wei-Yin Sun Yi Lu 《中国化学快报》2021,32(5):1717-1720
An electron-deficient [CpERhCl2]2 catalyzed annulation of N-pentafluorophenylbenzamides with internal alkynes was successfully established under mild reaction conditions, with the assistance of Lewis acid silver salt. Particularly, electron-deficient benzamide substrates were smoothly transformed into the desired products in this catalytic system. The catalytic system showed a broad tolerance for different substituents on the aromatic rings or aryl, alkyl-substituted alkynes. 相似文献
980.