全文获取类型
收费全文 | 15339篇 |
免费 | 2900篇 |
国内免费 | 4204篇 |
专业分类
化学 | 12054篇 |
晶体学 | 384篇 |
力学 | 768篇 |
综合类 | 457篇 |
数学 | 2143篇 |
物理学 | 6637篇 |
出版年
2024年 | 31篇 |
2023年 | 138篇 |
2022年 | 404篇 |
2021年 | 431篇 |
2020年 | 454篇 |
2019年 | 528篇 |
2018年 | 429篇 |
2017年 | 552篇 |
2016年 | 596篇 |
2015年 | 770篇 |
2014年 | 914篇 |
2013年 | 1208篇 |
2012年 | 1331篇 |
2011年 | 1413篇 |
2010年 | 1311篇 |
2009年 | 1305篇 |
2008年 | 1480篇 |
2007年 | 1367篇 |
2006年 | 1308篇 |
2005年 | 1062篇 |
2004年 | 876篇 |
2003年 | 742篇 |
2002年 | 706篇 |
2001年 | 594篇 |
2000年 | 499篇 |
1999年 | 367篇 |
1998年 | 249篇 |
1997年 | 174篇 |
1996年 | 160篇 |
1995年 | 143篇 |
1994年 | 130篇 |
1993年 | 124篇 |
1992年 | 102篇 |
1991年 | 86篇 |
1990年 | 75篇 |
1989年 | 58篇 |
1988年 | 64篇 |
1987年 | 56篇 |
1986年 | 44篇 |
1985年 | 46篇 |
1984年 | 20篇 |
1983年 | 28篇 |
1982年 | 12篇 |
1981年 | 9篇 |
1980年 | 8篇 |
1977年 | 5篇 |
1976年 | 4篇 |
1973年 | 5篇 |
1970年 | 3篇 |
1959年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
1.
Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by 18O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts. 相似文献
2.
This minireview describes the strategies for synthesis of fiuorinated surfactants potentially nonbioaccumulable.Various strategies have been focused on(Ⅰ) reducing the length of the perfluorocarbon chain,(Ⅱ) introducing hetero atoms into the fluorocarbon chain,(Ⅲ) introducing branch(herein and after branch means the fluoro-carbon chain section is not straight).In most cases,the surface tensions versus the surfactant concentrations have been assessed.These above strategies led to various highly fiuorinated(perfluorinated or not perfluorinated) surfactants whose chemical changes enabled to obtain novel alternatives to perfluorooctanoic acid(PFOA) and perfluorooctane sulphonate(PFOS). 相似文献
3.
4.
5.
Jia Tian-Cong Guo Jin-Tao Wang Zhen Zhu Xiao-Shan Zhang Qian-Xin Chen Ping Yao Kun Lv Wen-Ying Liu Guo-Guang 《Journal of Radioanalytical and Nuclear Chemistry》2019,321(3):823-829
Journal of Radioanalytical and Nuclear Chemistry - In the present work the final products of coumarin radiation chemical transformation are investigated by chromatography. During radiolysis of... 相似文献
6.
Metabolic profiles of dioscin in rats revealed by ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry 下载免费PDF全文
He Zhu Jin‐Di Xu Qian Mao Hong Shen Ming Kong Jian‐Ping Chen Song‐Lin Li 《Biomedical chromatography : BMC》2015,29(9):1415-1421
Dioscin (DIS), one of the most abundant bioactive steroidal saponins in Dioscorea sp., is used as a complementary medicine to treat coronary disease and angina pectoris in China. Although the pharmacological activities and pharmacokinetics of DIS have been well demonstrated, information regarding the final metabolic fates is very limited. This study investigated the in vivo metabolic profiles of DIS after oral administration by ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry method. The structures of the metabolites were identified and tentatively characterized by means of comparing the molecular mass, retention time and fragmentation pattern of the analytes with those of the parent compound. A total of eight metabolites, including seven phase I and one phase II metabolites, were detected and tentatively identified for the first time. Oxidation, deglycosylation and glucuronidation were found to be the major metabolic processes of the compound in rats. In addition, a possible metabolic pathway on the biotransformation of DIS in vivo was proposed. This study provides valuable and new information on the metabolism of DIS, which will be helpful for further understanding its mechanism of action. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
7.
对石英音叉增强型光声光谱(QEPAS)系统中常用的石英音叉进行了有限元模态计算,获得石英音叉前6阶振型与模态频率,认知了第4阶对称摆动振型为有效振动,利用单因素法分析了石英音叉的音臂长度l1、音臂宽度w1、音臂厚度t、音臂切角θ、音臂圆孔直径d及音臂圆孔高度h对低阶有效共振频率(Fre)的影响,敏感度依次为: l1> w1>d>θ>t>h,考虑实际设计情形,筛选出了l1,w1,d与h四个石英音叉设计变量,采用Box-Behnken实验设计方案与RSM(response surface methodology)方法,以Fre为函数目标,建立l1,w1,d与h的二次回归响应面模型,得到了参数之间的交互作用,利用Design-Expert软件对响应面模型进行设计参数反求,结果表明,在15 000 Hz≤Fre≤25 000 Hz计算区域内误差较小,基本满足QEPAS系统的计算需求,所提出的研究与设计方法具有一定通用性,可为QEPAS系统中石英音叉结构参数设计提供参考。 相似文献
8.
Dong Liangwei Qi Wei Peng Ping Wang Linxue Zhou Hui Huang Changming 《Nonlinear dynamics》2020,102(1):303-310
Nonlinear Dynamics - We address the nonlinear dynamics of binary Bose-Einstein condensates with mutually symmetric spinor components trapped in an optical lattice. The interaction between the... 相似文献
9.
Ping Chen Yanhong Hao Xinxin Wang Prof. Dr. Dan Yuan Prof. Dr. Yingming Yao Prof. Dr. Lutz Ackermann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(30):7292-7297
Highly position selective alkylations of N-alkylindoles at C7-positions have been enabled by cationic zirconium complexes. The strategy provides a straightforward access to install alkyl groups at C7-positions of indoles without a complex directing group. Mechanistic studies provided support for the importance of Brønsted acids in the catalytic manifold. 相似文献
10.
A new dinuclear iron(Ⅲ) complex has been synthesized and structurally characterized by X-ray crystallography: [FeⅢ2(L)(C6H5COO)(SO4)(CH3OH)2]·CH3CN·CH3OH(1, H3 L = N,N'-bis(salicylidene)-1,3-diamino-2-propanol). Complex 1 belongs to orthorhombic space group Pna21 with a = 11.4400(8), b = 22.9705(2), c = 12.5712(9) , V = 3303.5(4) 3, Z = 4, F(000) = 1576, Dc = 1.531 g·cm–3, Mr = 761.36, μ = 1.007 mm–1, S = 1.014, the final R = 0.0505 and wR = 0.1018. The crystal packing is stabilized by intermolecular O–H···O hydrogen bonds, forming an extended one-dimensional chain structure. The temperature dependence of magnetic susceptibility measurement shows that antiferromagnetic interaction is propagated between the metal centers. Fit as dinuclear arrangement gave parameters of J = 19.7 cm-1, g = 1.89 and R2 = 0.9999. 相似文献