全文获取类型
收费全文 | 1871篇 |
免费 | 351篇 |
国内免费 | 250篇 |
专业分类
化学 | 1346篇 |
晶体学 | 57篇 |
力学 | 103篇 |
综合类 | 29篇 |
数学 | 211篇 |
物理学 | 726篇 |
出版年
2024年 | 7篇 |
2023年 | 54篇 |
2022年 | 132篇 |
2021年 | 100篇 |
2020年 | 146篇 |
2019年 | 118篇 |
2018年 | 110篇 |
2017年 | 91篇 |
2016年 | 110篇 |
2015年 | 118篇 |
2014年 | 126篇 |
2013年 | 117篇 |
2012年 | 147篇 |
2011年 | 125篇 |
2010年 | 119篇 |
2009年 | 109篇 |
2008年 | 115篇 |
2007年 | 91篇 |
2006年 | 91篇 |
2005年 | 68篇 |
2004年 | 55篇 |
2003年 | 45篇 |
2002年 | 42篇 |
2001年 | 29篇 |
2000年 | 25篇 |
1999年 | 15篇 |
1998年 | 21篇 |
1997年 | 20篇 |
1996年 | 30篇 |
1995年 | 16篇 |
1994年 | 4篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1991年 | 9篇 |
1990年 | 4篇 |
1989年 | 4篇 |
1988年 | 4篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1983年 | 4篇 |
1982年 | 6篇 |
1981年 | 4篇 |
1980年 | 5篇 |
1979年 | 5篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1974年 | 1篇 |
1935年 | 1篇 |
排序方式: 共有2472条查询结果,搜索用时 15 毫秒
1.
Hao Lu Xiaodong Wang Hang Wang Andong Zhang Xinming Zheng Na Yu Zheng Tang Xinjun Xu Yahui Liu Ya-Nan Chen Zhishan Bo 《中国科学:化学(英文版)》2022,65(3):594-601
Three nonfused ring electron acceptors (NFREAs) TTC6,TT-C8T and TT-TC8 were purposefully designed and synthesized.The molecular geometry can be adjusted by the steric hindrance of lateral substituents.According to the DFT calculations,from TTC6 to TT-C8T and TT-TC8,planarity of the molecular backbone is gradually improved,accompanying with the enhancing of intramolecular charge transfer effect.As for TT-TC8,the two phenyl substituents are almost perpendicular to the molecular backbone,which endues the acceptor with good solubility and suppresses it to form over-aggregation.Multidirectional regular molecular orientation and closer molecular stacking are formed in TT-TC8 film.As a result,TT-TC8 based devices afford the highest PCE of 13.13%,which is much higher than that of TTC6 (4.41%) and TT-C8T (10.42%) and among the highest PCE values based on NFREAs. 相似文献
2.
Simultaneous determination of cinnamaldehyde and its metabolite in rat tissues by gas chromatography–mass spectrometry
下载免费PDF全文
![点击此处可从《Biomedical chromatography : BMC》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Hang Zhao Qian Yang Yanhua Xie Jiyuan Sun Honghai Tu Wei Cao Siwang Wang 《Biomedical chromatography : BMC》2015,29(2):182-187
Cinnamaldehyde (CA), an active ingredient isolated from the traditional Chinese medicine Cortex Cinnamomi, has a wide range of bioactivities. To clarify the distribution characteristics of CA, a selective and sensitive method utilizing gas chromatography–mass spetrometry was initially developed for simultaneously determining the concentration of CA and its metabolite cinnamyl alcohol in rat tissues. Selected ion masses of m/z 131, 105 and 92 were chosen, and separation of the analytes was performed on a DB‐5 ms (30 m × 0.25 mm, 0.25 µm, thickness) capillary column by gas chromatography–mass spectrometry. The calibration curves demonstrated good linearity and reproducibility over the range of 20–2000 and 20–4000 ng/mL for various tissue samples. Recoveries ranged from 86.8 to 107.5%, while intra‐ and interday relative standard deviations were all <11.3%. The analysis method was successfully applied in tissue distribution studies for CA and cinnamyl alcohol. As CA and cinnamyl alcohol may inter‐convert to one another, simultaneous determination of both analytes provides a comparative and accurate data for tissue study. The concentrations of CA and cinnamyl alcohol remaining in spleen were the highest among the main organs, including heart, liver, spleen, lung, kidney and brain. In addition, there was no long‐term accumulation of CA in rat tissues. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
3.
Hang Sun 《Tetrahedron letters》2004,45(3):615-617
A versatile and efficient sequence was developed for the synthesis of 1-desoxy-Δ8-THC analogues and is demonstrated by the synthesis of sulfonamide analogues with an acetylene group at the C-2′ position in the side chain. In this procedure the 1-desoxy-Δ8- THC ring structure is built first and the synthesis of the side chain is then developed. 相似文献
4.
用密度泛函B3LYP/ 6 3 1G(d)方法 ,对质子化丙酮分子团簇 (CH3COCH3) nH+ (n =1~ 7)弱相互作用体系进行了全自由度能量梯度优化 ,得到了该系列团簇的稳定结构及其对应的体系能量 .通过对构型的分析得出了质子化丙酮分子团簇 (CH3COCH3) nH+ (n =1~ 7)的生长规律 .计算了中性丙酮分子团簇体系的质子亲合能并总结出其变化趋势 .分析讨论了质子化团簇的红外振动光谱 ,发现质子化团簇的振动光谱普遍较中性环型团簇的振动光谱复杂 ,最强的振动峰来源于质子在溶剂壳中两个氧原子之间的振动 ,而且随着团簇尺寸的增加羰基的伸缩振动峰的数目也随之增多 相似文献
5.
In this paper, we discuss the controllability of a nonlinear degenerate parabolic system with bilinear control. Based on the shrinking property of the solutions, we prove that the system is not globally approximately controllable. Furthermore, we give an approximate null controllability result. We also prove that the system is not globally exactly null controllable by a comparison principle. 相似文献
6.
膨润土对结晶紫的吸附 总被引:5,自引:0,他引:5
用分光光度、显微电泳和x-射线衍射等方法研究了膨润土对结晶紫的吸附;实验表明,钙型膨润土在吸收结晶紫溶液时,加入钠盐可明显改善吸附效果。 相似文献
7.
稀土在鼠肝中的物种分布 总被引:23,自引:0,他引:23
采用 ICP-MS、微量蛋白层析分离技术 ,研究了长时间、低剂量混合稀土及短时间、高剂量硝酸镧分别对大鼠及小鼠作用后 ,稀土在鼠肝中的代谢累积及其物种分布 .结果表明 ,鼠肝中各稀土含量随给药剂量的增加而增大 ,其累积速度大小顺序为 La>Ce>Nd>Pr;经柱层析分离未得到与稀土特异结合的鼠肝蛋白 ;稀土可与多种鼠肝蛋白 (包括多种重要的酶 )结合 ,在一定条件下 ,稀土与其结合蛋白可发生解离 相似文献
8.
Yao Zhu Siyuan Fang Shaoqin Chen Youjie Tong Chunling Wang Yun Hang Hu 《Chemical science》2021,12(16):5825
Photocatalytic ethane conversion into value-added chemicals is a great challenge especially under visible light irradiation. The production of ethyl hydroperoxide (CH3CH2OOH), which is a promising radical reservoir for regulating the oxidative stress in cells, is even more challenging due to its facile decomposition. Here, we demonstrated a design of a highly efficient visible-light-responsive photocatalyst, Au/WO3, for ethane oxidation into CH3CH2OOH, achieving an impressive yield of 1887 μmol gcat−1 in two hours under visible light irradiation at room temperature for the first time. Furthermore, thermal energy was introduced into the photocatalytic system to increase the driving force for ethane oxidation, enhancing CH3CH2OOH production by six times to 11 233 μmol gcat−1 at 100 °C and achieving a significant apparent quantum efficiency of 17.9% at 450 nm. In addition, trapping active species and isotope-labeling reactants revealed the reaction pathway. These findings pave the way for scalable ethane conversion into CH3CH2OOH as a potential anticancer drug.Highly efficient visible-light driven photocatalytic oxidation of ethane into ethyl hydroperoxide was realized for the first time over Au/WO3. 相似文献
9.
合成了新型手性Salen配体(H3L)及新型手性Salen双核锌配合物(主体).通过研究主体对咪唑类客体及氨基酸酯类客体的分子识别行为,测定了这些配位反应的缔合常数.主体对咪唑类客体分子识别的缔合常数顺序为:K(Im) >K(2-MeIm) >K(2-Et-4-MeIm).主体对氨基酸酯类客体分子识别的缔合常数顺序为:K(LeuOCH3) >K(ValOCH3) >K(AlaOCH3) >K(SerOCH3),配位数均为2.主体与D、 L型氨基酸酯分子识别反应在不同温度下的缔合常数结果表明,随着温度的升高,对映选择性下降.实验发现反应体系中存在焓熵补偿关系. CD光谱的研究结果也反映了主体对不同客体识别能力的差异. 相似文献
10.
The glow discharge may be powered by direct current (dc), radio frequency (rf) and pulsed discharge sources. Each has specific advantages and special features that should be considered by analysts using the various forms of glow discharge spectroscopy. This paper reviews some of the factors that contribute to the selection of a power source for the glow discharge. 相似文献