全文获取类型
收费全文 | 73427篇 |
免费 | 12852篇 |
国内免费 | 7286篇 |
专业分类
化学 | 50825篇 |
晶体学 | 659篇 |
力学 | 4746篇 |
综合类 | 311篇 |
数学 | 8196篇 |
物理学 | 28828篇 |
出版年
2024年 | 279篇 |
2023年 | 1601篇 |
2022年 | 2718篇 |
2021年 | 2788篇 |
2020年 | 3106篇 |
2019年 | 2908篇 |
2018年 | 2562篇 |
2017年 | 2336篇 |
2016年 | 3570篇 |
2015年 | 3474篇 |
2014年 | 4136篇 |
2013年 | 5309篇 |
2012年 | 6730篇 |
2011年 | 6725篇 |
2010年 | 4469篇 |
2009年 | 4252篇 |
2008年 | 4595篇 |
2007年 | 4110篇 |
2006年 | 3760篇 |
2005年 | 3132篇 |
2004年 | 2429篇 |
2003年 | 1921篇 |
2002年 | 1751篇 |
2001年 | 1471篇 |
2000年 | 1356篇 |
1999年 | 1533篇 |
1998年 | 1304篇 |
1997年 | 1291篇 |
1996年 | 1289篇 |
1995年 | 1050篇 |
1994年 | 922篇 |
1993年 | 763篇 |
1992年 | 674篇 |
1991年 | 580篇 |
1990年 | 501篇 |
1989年 | 385篇 |
1988年 | 335篇 |
1987年 | 274篇 |
1986年 | 249篇 |
1985年 | 204篇 |
1984年 | 143篇 |
1983年 | 102篇 |
1982年 | 80篇 |
1981年 | 67篇 |
1980年 | 65篇 |
1979年 | 33篇 |
1978年 | 30篇 |
1977年 | 40篇 |
1976年 | 30篇 |
1973年 | 28篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
921.
Yu Liu Yong Chen Shi-Zhao Kang Li Li Chun-Hua Diao Heng-Yi Zhang 《Journal of inclusion phenomena and macrocyclic chemistry》2003,47(1-2):91-95
Two novel benzo-15-crown-5 tethered β-cyclodextrins 1 and 2have been synthesized by coupling substituted benzo-15-crown-5 with correspondingβ-cyclodextrin derivatives. Their inclusion complexation behavior withrepresentative guests, such as cyclohexanol, cyclohexane carboxylic acid, cyclohexaneacetic acid, sodium cyclohexane carboxylate, and potassium cyclohexane carboxylate,was investigated in aqueous solution by means of fluorescence spectrometry. As compared with parent β-cyclodextrin, benzo-15-crown-5 tethered β-cyclodextrins 1–2 display significantly enhanced molecular binding abilities and selectivities towards model substrates, especially towards substrates containing alkali-metal cations. These results indicate that, bearing two recognition sites in a single molecule, these supramolecular architectures can strongly enhance the molecular binding ability of parent β-cyclodextrin by the cooperative binding of the β-cyclodextrin cavity and the crown ether moiety. Possessing a shorter linker, crown ether-β-cyclodextrin 2 shows much higher binding affinity with guest molecules than crown ether-β-cyclodextrin 1, which may be attributed to the binding size and molecular multiple recognition behavior between host and guest. 相似文献
922.
用火焰原子吸收法测定了2000例甲亢病人的血清镁含量及1200例天津市正常人群血清镁含量,结果显示,甲亢病人血清镁含量显著低于正常人群,有显著统计意义(P〈0.01)。提示:甲亢病人血清镁含量对甲亢病诊断及治疗过程的镁的摄入补充有重要的意义。 相似文献
923.
叙述了同步辐射白光全反射X射线荧光分析的实验装置,给出了几种标准物质TXRF实验的检出限,并对实验结果进行了讨论。 相似文献
924.
Both absolute molecular weight and molecular sizes (radius of gyration and hydrodynamic radius) of a vinyl-type polynorbornene eluting from size-exclusion chromatography columns were determined by combined with a static and dynamic laser light scattering detector. The hydrodynamic radius of polymer fraction eluting from size-exclusion chromatography columns was obtained from dynamic laser light scattering measurements at only a single angle of 90° by introducing a correction factor. According to the scaling relationship between molecular sizes and molecular weight and the ratio between radius of gyration and hydrodynamic radius, the vinyl-type polynorbornene took a random coil conformation in 1,2,4-trichlorobenzene at 150 °C. 相似文献
925.
Griffiths WJ Alvelius G Liu S Sjövall J 《European journal of mass spectrometry (Chichester, England)》2004,10(1):63-88
Neutral oxosteroids have been derivatised with Girard T and P hydrazine reagents to give the corresponding Girard hydrazone quaternary ammonium salts. Both Girard T (GT) and Girard P (GP) hydrazones of oxosteroids give very intense [M](+) ion signals in electrospray (ES) mass spectra and fragment within the ES interface and collision cell to give characteristic fragment ions. GT and GP derivatives give informative high-energy collision-induced dissociation spectra, from which the structure of the precursor oxosteroid can be determined. Both charge-remote and charge-mediated mechanisms are responsible for the formation of the fragment ions at high collision-energy. 相似文献
926.
927.
In the 21st century, hydrogen energy is a novel energy source. Its use is expected to mitigate the problems of environmental pollution and global warming caused by the excessive use of conventional fossil fuels. The hydrogen evolution reaction (HER) for water splitting has attracted considerable attention because of its environmental friendliness. To improve electrocatalyst performance and reduce operation cost, carbon-based metal hybrid materials exhibiting high efficiency and catalytic activity have been developed. Among them, carbon dots (CDs) have garnered significant research attention and have been widely applied in biosensing, bioimaging, and energy conversion/storage because of their facile synthesis, biocompatibility, tunable photoluminescence, excellent stability, and good electronic properties. CDs are widely used as carriers in the construction of electrocatalysts prepared from carbon-based metal hybrid materials. At present, it is believed that CDs exhibit excellent confinement effects, which can effectively inhibit the growth and agglomeration of metal nanoparticles, thereby preparing well-distributed carbon-based metal hybrid materials with a uniform and controllable size. However, the formation process of the small-molecule raw materials of CDs has not been elucidated. In this study, CDs and small-molecule raw materials from synthetic CDs were used as precursors to prepare nitrogen-doped CD-supported ruthenium nanoparticle (Ru@CDs) and small-molecule-supported ruthenium nanoparticle (Ru@Molecule) hybrid materials, respectively. The interaction between the small molecules and Ru in the process of CD formation and the effect on HER performance were explored. Moreover, we prepared different carriers such as metal organic frameworks(MOF), carbon nanotubes (CNTs), and graphene (GO)-supported ruthenium nanoparticle hybrid materials. Among them, Ru@CDs exhibited controllable size and excellent dispersibility and exhibited outstanding HER activity and good stability. Ru@CDs were found to require a low overpotential of 22 mV to reach a current density of 10 mA·cm−2. Moreover, we observed the presence of an intermediate state between the molecules and CDs and demonstrated that the intermediate state exhibits no confinement effect. Furthermore, we found that with increasing calcination temperature, the intermediate state gradually changes to CDs. The unique spatial confinement between CDs and metal ions is key to the formation of monodisperse Ru nanoparticles. Our results confirmed that Ru@CDs serve as excellent HER catalyst supports. This work not only reveals the effect of the unique spatial confinement of CDs on the supported metals and their promoting effect on electrocatalytic activity but also provides guides the future development of CD-based metal hybrid electrocatalysts. 相似文献
928.
自1971年Peacock等首次合成出以杂多阴离子为配位体的镧系元素的一些杂多配合物[Ln(XW_(11)O_(39))_2]~(n-)(X=P,Si)以来,Zuhairi等又合成出镧的一些其它杂多钨酸盐[La(XW_(11)O_(39))_2]~(n-)(X=B,Si,Ge,P,As)。 为开发新型的镧系元素催化剂,我们系统地研究了镧系元素的杂多钨酸盐和杂多钼酸盐。本文报道有关K_(11)[Ln(PW_9Mo_2O_(39))_2]·nH_2O(Ln=La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Er,Yb)的合成及性质的研究结果。 相似文献
929.
To obtain new materials with synergetic or complementary behaviors, polyaniline composite filled with ZnO rods in ramification-like
structure was prepared by a hydrothermal approach. Comparative experiments of ZnO preparation in the presence of some metal
ions were also carried out. The results indicated that the morphology of ZnO was strongly affected by the preparation condition.
The method to grow ZnO rods in the presence of polyaniline offers a simple approach to obtain polyaniline composite filled
with linear ZnO structure. The results of X-ray photoelectron spectroscopy show that the strong interaction between ZnO and
polyaniline possibly exists to cause the charge transfer. 相似文献
930.