全文获取类型
收费全文 | 1171篇 |
免费 | 43篇 |
国内免费 | 6篇 |
专业分类
化学 | 980篇 |
晶体学 | 4篇 |
力学 | 7篇 |
数学 | 50篇 |
物理学 | 179篇 |
出版年
2023年 | 11篇 |
2022年 | 4篇 |
2021年 | 10篇 |
2020年 | 25篇 |
2019年 | 19篇 |
2018年 | 6篇 |
2017年 | 5篇 |
2016年 | 19篇 |
2015年 | 21篇 |
2014年 | 18篇 |
2013年 | 57篇 |
2012年 | 69篇 |
2011年 | 85篇 |
2010年 | 34篇 |
2009年 | 37篇 |
2008年 | 82篇 |
2007年 | 48篇 |
2006年 | 81篇 |
2005年 | 69篇 |
2004年 | 77篇 |
2003年 | 60篇 |
2002年 | 63篇 |
2001年 | 18篇 |
2000年 | 9篇 |
1999年 | 12篇 |
1998年 | 16篇 |
1997年 | 8篇 |
1996年 | 16篇 |
1995年 | 10篇 |
1994年 | 9篇 |
1993年 | 8篇 |
1992年 | 9篇 |
1991年 | 11篇 |
1990年 | 9篇 |
1989年 | 8篇 |
1988年 | 6篇 |
1987年 | 4篇 |
1986年 | 7篇 |
1985年 | 20篇 |
1984年 | 17篇 |
1983年 | 9篇 |
1982年 | 16篇 |
1981年 | 13篇 |
1980年 | 9篇 |
1979年 | 16篇 |
1978年 | 6篇 |
1977年 | 5篇 |
1976年 | 5篇 |
1975年 | 12篇 |
1974年 | 11篇 |
排序方式: 共有1220条查询结果,搜索用时 31 毫秒
71.
72.
Czesław Rudowicz Ireneusz Stefaniuk Roman Dziembaj Hitoshi Ohta Marcin Molenda Susumu Okubo Makoto Yoshida 《Research on Chemical Intermediates》2007,33(8):853-862
This paper deals with the analysis of the temperature dependence of high-frequency EMR (HF-EMR) spectra due to Mn3+ and Mn4+ ions in the lithium manganese spinel LiMn2O4. A range of powder samples obtained by the sol-gel method with calcinations in several temperature ranges were prepared for
this study. Based on the initial characterization carried out by a number of techniques, the physicochemical and structural
properties of the samples were earlier determined. Independently, temperature magnetization and HF-EMR measurements were carried
out. The EMR spectra vary strongly between samples, indicating possible structural or chemical changes. Quantitative analysis
of the temperature dependence of the HF-EMR spectra due to Mn3+ and Mn4+ ions in LiMn2O4 is presented in this paper. The spectral analysis concerns the line shape, linewidth, intensity and g-factors. Fittings using the Lorentzian spectral shape and, to a certain extent, the Gaussian spectral shape have been carried
out in order to parameterize the temperature dependence of the HF-EMR spectra. This parameterization of the HF-EMR experimental
data enables a deeper characterization of the samples. Subsequently, a better insight into the role of the Mn3+ and Mn4+ ions in accounting for the characteristics most suitable for application of LiMn2O4 as a cathode material may be gained. 相似文献
73.
Functional porous coordination polymers 总被引:18,自引:0,他引:18
The chemistry of the coordination polymers has in recent years advanced extensively, affording various architectures, which are constructed from a variety of molecular building blocks with different interactions between them. The next challenge is the chemical and physical functionalization of these architectures, through the porous properties of the frameworks. This review concentrates on three aspects of coordination polymers: 1). the use of crystal engineering to construct porous frameworks from connectors and linkers ("nanospace engineering"), 2). characterizing and cataloging the porous properties by functions for storage, exchange, separation, etc., and 3). the next generation of porous functions based on dynamic crystal transformations caused by guest molecules or physical stimuli. Our aim is to present the state of the art chemistry and physics of and in the micropores of porous coordination polymers. 相似文献
74.
Kawahara M Kabir MK Yamada K Adachi K Kumagai H Narumi Y Kindo K Kitagawa S Kawata S 《Inorganic chemistry》2004,43(1):92-100
Two new copper(II) compounds of chloranilate and 2,2':6',2' '-terpyridine have been synthesized, and the structures have been solved by the single-crystal X-ray diffraction method. The crystal structure of [[Cu(2)(CA)(terpy)(2)][Cu(CA)(2)]](n)(1), where H(2)CA = chloranilic acid and terpy = 2,2':6',2' '-terpyridine, consists of two modules, the dimer unit [Cu(2)(CA)(terpy)(2)](2+) and the anionic mononuclear unit [Cu(CA)(2)](2)(-), forming an alternated chain. The chain is stabilized by semicoordinating and additional but efficient secondary bonding interactions. The crystal structure of [[Cu(2)(CA)(terpy)(2)(dmso)(2)][Cu(CA)(2)(dmso)(2)](EtOH)](n)(2), where dmso = dimethyl sulfoxide, consists of solvent molecules and two discrete modules, the dimer unit [Cu(2)(CA)(terpy)(2)(dmso)(2)](2+) and the anionic mononuclear unit [Cu(CA)(2)(dmso)(2)](2)(-). The dimer units form a layer by secondary bonding interactions, and the monomer units and ethanol molecules are introduced between the layers. The magnetic properties of 1 and 2 have been investigated in the temperature range 2.0-300 K. A weak ferromagnetic interaction was observed in 1, J(a) = 2.36 cm(-)(1) and zJ(b) = -0.68 cm(-)(1) while no exchange coupling was observed in 2. 相似文献
75.
Susumu Tajima Yukiyoshi Nagai Osamu Sekiguchi Masao Fujishige Nozomu Uchida 《Journal of the American Society for Mass Spectrometry》1995,6(3):202-206
The spontaneous unimolecular dissociation reaction of methyl lactate (1) ionized by electron impact was investigated by a combination of mass-analyzed ion kinetic energy spectrometry and deuterium labeling. The metastable ions 1+· decompose in a variety of ways: four fragment peaks are observed at m/z 89, 76, 61, and 45, which correspond to the losses of ?H3, CO, CH3?O, and ?OOCH3, respectively. Double hydrogen atom transfer occurs in the third reaction. The source-generated m/z 61 ions decompose into oxygen-protonated methanols at m/z 33 ([CH3OH 2 + ]) by the loss of CO with double hydrogen atom migration. Both hydroxyl and methyne hydrogen atoms in 1 +· are present in the resultant protonated methanols. 相似文献
76.
Sato S Komoto T Kanamaru Y Kawamoto N Okada T Kaiho T Mogi K Morimoto S Umehara N Koda T Miyashita A Sakamoto T Niino Y Oka T 《Chemical & pharmaceutical bulletin》2002,50(2):292-297
New muq-opioid receptor (MOR) agonists containing 4-hydroxypiperidine, piperidine and piperazine moieties were synthesized and evaluated to find a peripheral opioid analgesic. Among the synthesized compounds, 12-[1-[3-(N,N-dimethylcarbamoyl)-3,3-diphenylpropyl]-4-hydroxypiperidin-4-yl]phenoxy]acetic acid (8: SS620) having phenoxyacetic acid and 4-hydroxypiperidine moieties showed the highest agonist potency on the MOR in an isolated guinea-pig ileum preparation, and it also had selectivity to the human MOR expressed in Chinese hamster ovary (CHO)-K1 cells compared with the same types of delta- and kappa-opioid receptors (DOR and KOR). In addition, compound 8 showed a 10 times more potent MOR agonist activity than loperamide. Furthermore, compound 8 showed a peripheral analgesic activity in vivo screening on rat. 相似文献
77.
For the purpose of evaluating optimal fill level of starting materials in a high-shear mixer, discrete element method (DEM) simulation was conducted to visualize kinetic status between particles. The simulation results obtained by changing fill levels were used to determine solid fraction of particles, particle velocity, particle velocity vector, and kinetic energy and discuss the flow pattern. Optimal fill level was obtained from the information on these matters. It was pointed out that understanding the kinetic energy between particles in an agitating vessel was effective in determining the optimal fill level. Granulation experiment was conducted to validate the optimal fill level obtained by the simulation, confirming the good agreement between these two results. It was pointed out that determination of kinetic energy between particles through the simulation was effective in obtaining an index of the kinetic status of particles. Further, it was confirmed that the simulation could provide more information than conventional granulation experiments could provide and also helpful in optimizing the operating conditions. 相似文献
78.
Utilization of a metalloligand, ([Cu(2,4-pydca)2(H2O)].2Et3NH) (1) (2,4-pydca = pyridine-2,4-dicarboxylate), as a building unit provides a novel porous coordination polymer, ([ZnCu(2,4-pydca)2(H2O)3(DMF)].DMF)n (2), in which the Zn(II) ion at the node of the network acts as a linker and the Cu(II) ion in the channel wall is available for guest-coordination. 相似文献
79.
Noda Susumu Imada Masahiro Chutinan Alongkarn Yamamoto Noritsugu 《Optical and Quantum Electronics》2002,34(8):723-736
Three-dimensional (3D) and two-dimensional (2D) photonic crystals based on III–V semiconductors are described. On the 3D photonic crystals, the development of complete photonic crystals at optical wavelengths and their applications to ultrasmall optical integrated circuits including 3D sharp bend waveguide are described. On the 2D photonic crystals, two-unique device and/or phenomena are demonstrated. 相似文献
80.
The rhodium catalyzed isomerization of α-, β-, and γ-silylated allyl alcohols has been successfully applied to the selective synthesis of acylsilane, α-silyl ketones, and β-silyl ketones, respectively. 相似文献