全文获取类型
收费全文 | 24174篇 |
免费 | 3886篇 |
国内免费 | 2629篇 |
专业分类
化学 | 16906篇 |
晶体学 | 296篇 |
力学 | 1440篇 |
综合类 | 239篇 |
数学 | 2659篇 |
物理学 | 9149篇 |
出版年
2024年 | 78篇 |
2023年 | 505篇 |
2022年 | 819篇 |
2021年 | 849篇 |
2020年 | 985篇 |
2019年 | 904篇 |
2018年 | 752篇 |
2017年 | 726篇 |
2016年 | 1101篇 |
2015年 | 1036篇 |
2014年 | 1292篇 |
2013年 | 1672篇 |
2012年 | 2076篇 |
2011年 | 2077篇 |
2010年 | 1424篇 |
2009年 | 1366篇 |
2008年 | 1529篇 |
2007年 | 1404篇 |
2006年 | 1343篇 |
2005年 | 1085篇 |
2004年 | 870篇 |
2003年 | 720篇 |
2002年 | 623篇 |
2001年 | 519篇 |
2000年 | 512篇 |
1999年 | 591篇 |
1998年 | 487篇 |
1997年 | 429篇 |
1996年 | 436篇 |
1995年 | 387篇 |
1994年 | 357篇 |
1993年 | 325篇 |
1992年 | 269篇 |
1991年 | 229篇 |
1990年 | 235篇 |
1989年 | 159篇 |
1988年 | 119篇 |
1987年 | 84篇 |
1986年 | 97篇 |
1985年 | 65篇 |
1984年 | 37篇 |
1983年 | 39篇 |
1982年 | 37篇 |
1981年 | 21篇 |
1980年 | 8篇 |
1979年 | 6篇 |
1976年 | 1篇 |
1957年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
151.
In the presence of n-Bu4NBr acting as phase-transfer reagent, n-Bu4N+ salts of organophosphoryl polyoxotungstate derivatives [RP(O)]2X
n+W11O39
(8–n)– [R = PhCH2CH2P(O), X = P, Si; R = C6H11P(O); X = Ge, Ga] have been prepared and characterized by elemental analysis, i.r., 31P- and 183W-n.m.r. spectroscopy. According to the elemental analysis and spectroscopic data, the hybrid anions consist of an -[XW11O39] framework on which are grafted two equivalent organophosphoryl groups through P—O—W bridges; these new species still retain the Keggin structure. The six-line 183W spectrum indicates that hybrid anions possess C
s symmetry in MeCN. 相似文献
152.
A facile one-step method has been developed for the synthesis of N-protected α-amino aldehyde acetals in moderate to good yields by three-component reaction of fluoroalkanesulfonyl azides, vinyl ethers and alcohol at 0 °C within 10 min. This practical synthetic method provides a convenient and expeditious access to N-per(poly)fluoroalkanesulfonyl α-amino aldehyde acetals. 相似文献
153.
Ch. V. Subba Reddy Y. Y. Qi W. Jin Q. Y. Zhu Z. R. Deng W. Chen Sun-il Mho 《Journal of Solid State Electrochemistry》2007,11(9):1239-1243
Molybdenum trioxide (MoO3) xerogel films modified with poly(vinyl alcohol)+poly(vinyl pyrrolidone) (PVP+PVA) polyblends were obtained by ion-exchange
method with sol-gel technique. Investigations were conducted using X-ray “diffractometry”, Fourier transform infrared spectroscopy,
and cyclic voltammetry. The results show that the H atoms in polyblend are H-bonded with the O atoms in the Mo=O bonds of
MoO3 xerogel, which effectively shield the electrostatic interaction between MoO3 interlayer and Li+ ions when MoO3 xerogel is modified by the intercalation of (PVP+PVA). The reversibility of the insertion/extraction of Li+ ions is greatly improved by the modification with polyblend of MoO3 nanocomposite films. MoO3 and (PVP+PVA)
x
MoO3 (x = 0, 0.5) nanobelts were obtained by a simple hydrothermal process from MoO3 sol. The electrochemical cells with configuration Li/(LiPF6+EC+DMC)/MoO3 modified by (PVP+PVA) were fabricated and their discharge profiles studied. 相似文献
154.
Investigation of Tomato Plant Defence Response to Tobacco Mosaic Virus by Determination of Methyl Salicylate with SPME-Capillary GC-MS 总被引:2,自引:0,他引:2
Headspace SPME was applied to investigation of tomato plant defence response to tobacco mosaic virus (TMV) by determination of compounds emitted from tomato plants at the extraction conditions of 25 °C and 15 min. It was found that TMV-inoculated tomato plant released large amount of methyl salicylate (MeSA) as response to TMV and MeSA concentration changed dramatically with time after inoculation. Gaseous MeSA as a signaling compound could induce in surrounding tomato plants to produce salicylic acid (SA) and synthesize and release MeSA. These results show that MeSA might be an airborne plant-signalling molecule in tomato plant response to TMV. The present method provided low detection limit of 2.0 ng L–1 and needed little sample preparation time (15 min), so the method makes it easy to find the critical times of tomato plant response to TMV by fast determination of MeSA released from tomato plant. 相似文献
155.
β-Trifluoroacetyl vinyl ethers ROCHCHCOCF3 react smoothly as dienophiles with α,β-unsaturated carbonyl compounds to give the unexpected 2-alkoxyl-5-trifluoroacetyl-3,4-dihydro-2H pyrans. These products are formed by elimination and addition of the alcohol to the products of the normal hetero Diels-Alder reaction (2-alkoxyl-3-trifluoroacetyl-2,3-dihydro-2H pyrans). In contrast, 1,3-dipolar cycloaddition of ROCHCHCOCF3 with ArCHN(O)Me proceeds via a Z-endo transition state to give regio- and stereospecific 4-trifluoroacetyl substituted isoxazolidines and their derivatives. 相似文献
156.
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
157.
H2CCF自由基与HNCO反应机理的理论研究 总被引:4,自引:0,他引:4
采用密度泛函理论的B3LYP方法, 在6-311++G(d,p)基组水平上研究了H2CCF自由基与HNCO的微观反应机理, 优化了反应过程中的反应物、中间体、过渡态和产物, 为了获得更精确的能量信息, 还在QCISD(T)/6-311++G(d,p)基组水平上计算了各物质的能量.振动分析结果和IRC分析结果证实了中间体和过渡态的真实性, 计算所得的成键临界点电荷密度的变化也确认了反应过程.对于H2CCF自由基与HNCO反应, 我们找到了六条可行的反应通道, 结果分析表明通道H2CCF+HNCO→IM3→TS5→H2CCFH+NCO控制步骤活化能最低, 是该反应的主要通道, 在此反应过程中有稳定的氢键复合物IM3生成, 还表现出氢原子迁移的反应特征. 相似文献
158.
159.
MingZhuLIU ShengYiZHANG YuHuaSHEN MingLiangZHANG 《中国化学快报》2004,15(10):1249-1252
Selenium nanoparticles were prepared by a reverse microemulsion system. Sodium selenosulfate was used as selenium source. The results showed that hydrochloric acid concentration and reaction temperature had great influence on the morphology of products. The crystalline selenium nanowires and amorphous selenium nanorods were obtained in given condition. 相似文献
160.