全文获取类型
收费全文 | 880篇 |
免费 | 19篇 |
国内免费 | 2篇 |
专业分类
化学 | 667篇 |
晶体学 | 11篇 |
力学 | 14篇 |
综合类 | 1篇 |
数学 | 30篇 |
物理学 | 178篇 |
出版年
2022年 | 6篇 |
2021年 | 13篇 |
2020年 | 9篇 |
2019年 | 18篇 |
2018年 | 7篇 |
2017年 | 5篇 |
2016年 | 18篇 |
2015年 | 18篇 |
2014年 | 13篇 |
2013年 | 24篇 |
2012年 | 42篇 |
2011年 | 57篇 |
2010年 | 24篇 |
2009年 | 24篇 |
2008年 | 51篇 |
2007年 | 57篇 |
2006年 | 50篇 |
2005年 | 48篇 |
2004年 | 49篇 |
2003年 | 40篇 |
2002年 | 37篇 |
2001年 | 14篇 |
2000年 | 21篇 |
1999年 | 7篇 |
1998年 | 7篇 |
1997年 | 5篇 |
1996年 | 10篇 |
1995年 | 7篇 |
1994年 | 9篇 |
1993年 | 9篇 |
1992年 | 12篇 |
1991年 | 8篇 |
1990年 | 13篇 |
1988年 | 6篇 |
1987年 | 11篇 |
1986年 | 8篇 |
1985年 | 16篇 |
1984年 | 15篇 |
1983年 | 10篇 |
1982年 | 7篇 |
1981年 | 7篇 |
1980年 | 11篇 |
1979年 | 7篇 |
1978年 | 7篇 |
1977年 | 8篇 |
1976年 | 10篇 |
1975年 | 5篇 |
1974年 | 16篇 |
1973年 | 6篇 |
1964年 | 3篇 |
排序方式: 共有901条查询结果,搜索用时 15 毫秒
11.
Shigeru Shimada Osamu Yamazaki Yohichi Suzuki 《Journal of organometallic chemistry》2004,689(19):3012-3023
Hypervalent organobismuth compounds, 6-tert-butyl-5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocines, with 13 different substituents on the bismuth atom including halogens, alkyl, alkenyl, alkynyl, aryl, or phenylthio groups have been synthesized. A key compound, 12-chloro-6-tert-butyl-5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocine, which is a precursor for other azabismocines, has been synthesized by two different procedures; one is based on Akiba’s method using 2-bromobenzylbromide as one of the starting materials and the other is a newly developed one using a cheaper starting material, 2-chlorobenzyl chloride. The structures of 12 new bismuth compounds were determined by X-ray diffraction. The eight-membered tetrahydroazabismocine ring has proved to be highly flexible and the hypervalent Bi-N bond distances vary ranging from 2.568(3) to 2.896(5) Å, depending on the electronic nature of the substituents on the bismuth atom. The Bi-N bond distances have good linear relationship against Hammett’s σm constants. 相似文献
12.
13.
Annaraj J Suh Y Seo MS Kim SO Nam W 《Chemical communications (Cambridge, England)》2005,(36):4529-4531
A mononuclear nonheme ferric-peroxo complex bearing a macrocyclic tetradentate N4 ligand, [(TMC)Fe(III)-O2]+, was prepared and used in mechanistic studies of aldehyde deformylation; a catalytic aldehyde deformylation by a nonheme iron(II) complex, [Fe(II)(TMC)]2+, and molecular oxygen is reported as well. 相似文献
14.
Shigeo Tazuke Kiyoo Shimada Seizo Okamura 《Journal of polymer science. Part A, Polymer chemistry》1969,7(3):879-888
The radical polymerizability of vinylpyridines in the presence of cobaltous chloride was studied in DMF solution, and the results were correlated with the spectroscopic data obtained for methanol solution. In general, the behavior of vinylpyridine complexed with cobaltous chloride is qualitatively the same as that of zinc complexes reported previously. The rates of polymerization were enhanced by the addition of cobaltous chloride when 4-vinylpyridine(4-VP) or 2-methyl-5-vinylpyridine(MVP) was the monomer, whereas the polymerization of 2-vinylpyridine(2-VP) was retarded by cobaltous chloride. The monomer reactivity of all the vinylpyridines was also enhanced by complex formation as studied by copolymerization with styrene. The enhancement of reactivity of 4-VP complexed with cobaltous chloride is somewhat smaller than that of the corresponding zinc complex. 相似文献
15.
The effect of propranolol (PPL), phenoxybenzamine (PBZ) or bicuculline (BCL) on the diazepam (DZP)-induced changes of pineal melatonin synthesis in male rats was examined in vivo and in vitro. Administration of PBZ did not affect the inhibitory action of DZP on pineal melatonin synthesis in vivo. A single injection of PPL inhibited the pineal melatonin synthesis similarly to the administration of DZP alone, but the two drugs together did not exhibit additive or synergistic effects on the melatonin synthesis. Significant decreases in the N-acetyltransferase (NAT) activity and the N-acetylserotonin (NAS) and melatonin contents were observed in the BCL-injected group, being greater than those in the DZP-treated group. Unexpectedly, however, the combination treatment of DZP and BCL causes an increase in the NAT activity and melatonin content compared with the BCL-alone group. Incubation with DZP at higher concentrations resulted in an increase of pineal NAT activity in vitro, but this increase was inhibited by preincubation with PPL, PBZ or BCL. DZP treatment thus appeared to have different effects on pineal NAT activity in vivo and in vitro. These results suggest that both a GABAergic mechanism and peripheral benzodiazepine (BZP) receptors in rat pineal gland may be involved in the modulation of melatonin synthesis by DZP. 相似文献
16.
Nakai I Kondoh H Amemiya K Nagasaka M Shimada T Yokota R Nambu A Ohta T 《The Journal of chemical physics》2005,122(13):134709
The mechanism of CO oxidation reaction on oxygen-precovered Pt(111) surfaces has been studied by using time-resolved near-edge x-ray absorption fine structure spectroscopy. The whole reaction process is composed of two distinct paths: (1) a reaction of isolated oxygen atoms with adsorbed CO, and (2) a reaction of island-periphery oxygen atoms after the CO saturation. CO coadsorption plays a role to induce the dynamic change in spatial distribution of O atoms, which switches over the two reaction paths. These mechanisms were confirmed by kinetic Monte Carlo simulations. The effect of coadsorbed water in the reaction mechanism was also examined. 相似文献
17.
Nakanishi I Miyazaki K Shimada T Iizuka Y Inami K Mochizuki M Urano S Okuda H Ozawa T Fukuzumi S Ikota N Fukuhara K 《Organic & biomolecular chemistry》2003,1(22):4085-4088
Electron-transfer reduction of molecular oxygen (O2) by the phenolate anion (1-) of a vitamin E model, 2,2,5,7,8-pentamethylchroman-6-ol (1H), occurred to produce superoxide anion, which could be directly detected by a low-temperature EPR measurement. The rate of electron transfer from 1- to O2 was relatively slow, since this process is energetically unfavourable. The one-electron oxidation potential of 1- determined by cyclic voltammetric measurements is sufficiently negative to reduce 2,2-bis(4-tert-octylphenyl)-1-picrylhydrazyl radical (DOPPH*) to the corresponding one-electron reduced anion, DOPPH-, suggesting that 1- can also act as an efficient radical scavenger. 相似文献
18.
Clot O Akahori Y Moorlag C Leznoff DB Wolf MO Batchelor RJ Patrick BO Ishii M 《Inorganic chemistry》2003,42(8):2704-2713
The preparations of two new phosphinothiophene ligands, 3,3'-bis(diphenylphosphino)-2,2'-bithiophene (dppbt; 1) and 3,3' "-dihexyl-3',3' '-bis(diphenylphosphino)-2,5':2',2' ':5' ',2' "-quaterthiophene (hdppqt; 2) are reported. Oxidation of 1 gives 3,3'-bis(diphenylphosphine oxide)-2,2'-bithiophene (3), and the crystal structure of this compound was determined. Pd(II) and Au(I) complexes of these ligands have been synthesized and characterized. Crystal structures of [(dppbt)PdCl(2)] (1-Pd), [(hdppqt)PdCl(2)] (2-Pd), [(dppbt)(AuCl)(2)] (1-Au), and [(hdppqt)(AuCl)(2)] (2-Au) were obtained. [(dppbt)(AuCl)(2)] crystallized in two solid-state forms; crystals grown from CH(2)Cl(2)/Et(2)O show a gold-gold interaction of 3.3221(4) A, but from CH(2)Cl(2)/toluene, the molecule crystallizes as a toluene adduct (1-Au-tol) and does not show any gold-gold interaction. All the complexes were characterized via UV-vis spectroscopy and cyclic voltammetry, and the effect of the metal on the energy of the pi-pi transition and oxidation potential was determined. These data are correlated to the interannular torsion angles in the oligothienyl groups from the crystal structure studies. 相似文献
19.
K. Ajiki D. Shimada T. Kido N. Miyakawa N. Tsuda 《Applied Physics A: Materials Science & Processing》1991,52(1):1-6
fine structure was observed in the conductance curve of a tunneling junction composed of a single crystalline Bi2212 and an evaporated SnO2 film. It is similar to those of Bi2212-GaAs mechanical junctions and there is a certain correspondence between the structure and the phonon density of states. Thus the previous conclusion that the structure is due to phonons has been complemented by this work. The energy gap 2 was 57 meV at 13 K and T
c was 78 K. 2(0)/k
B
T
c is then 8.3. (T) showed the BCS-like temperature dependence. 相似文献
20.
Shinsuke Takagi Miharu Eguchi Tetsuya Shimada Satoshi Hamatani Haruo Inoue 《Research on Chemical Intermediates》2007,33(1-2):177-189
Photochemical energy transfer of non-aggregated cationic porphyrins on an anionic-type clay (Smecton SA) surface was investigated. The efficiency of energy transfer and excited-state quenching in the absence of energy transfer were evaluated at various loading levels of porphyrin on the clay surface and were found to be significantly affected by the loading level. As the latter increased, both energy transfer efficiency and excited-state quenching increased. Judging from the dependency of energy-transfer efficiency on the porphyrin loading level, a partially clustered structure, but without aggregation, of porphyrins on the clay surface is proposed. 相似文献