全文获取类型
收费全文 | 251篇 |
免费 | 0篇 |
专业分类
化学 | 181篇 |
晶体学 | 9篇 |
力学 | 1篇 |
数学 | 9篇 |
物理学 | 51篇 |
出版年
2021年 | 4篇 |
2020年 | 4篇 |
2019年 | 3篇 |
2014年 | 3篇 |
2013年 | 7篇 |
2012年 | 10篇 |
2011年 | 8篇 |
2010年 | 11篇 |
2009年 | 5篇 |
2008年 | 11篇 |
2007年 | 8篇 |
2006年 | 13篇 |
2005年 | 15篇 |
2004年 | 6篇 |
2003年 | 16篇 |
2002年 | 3篇 |
2001年 | 6篇 |
2000年 | 10篇 |
1999年 | 3篇 |
1998年 | 3篇 |
1997年 | 4篇 |
1996年 | 4篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 8篇 |
1992年 | 4篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1986年 | 2篇 |
1985年 | 6篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1973年 | 3篇 |
1972年 | 3篇 |
1971年 | 2篇 |
1970年 | 4篇 |
1969年 | 3篇 |
1968年 | 4篇 |
1967年 | 4篇 |
1966年 | 6篇 |
排序方式: 共有251条查询结果,搜索用时 15 毫秒
51.
Ueki S Kobayashi Y Ishida T Nogami T 《Chemical communications (Cambridge, England)》2005,(41):5223-5225
One-dimensional polymeric complexes consisting of alternating dicopper(II) and digadolinium(III) units exhibited ferrimagnetic behavior which was ascribable to antiferromagnetic coupling across the oximate N-O bridges between the high-spin homodinuclear units. 相似文献
52.
Sol-gel method was applied to prepare CdS
x
Se1–x
microcrystals doped glasses. Gels were synthesized through the hydrolysis of Si(OC2H5)4, CdSeO4, and NH4SCN, and then heated in H2-N2 gas atmosphere to precipitate CdS
x
Se1–x
microcrystals in the glasses. The composition of crystals was preliminarily determined during the synthesis of the gels. The optical band gap energies were blue shifted compared with those of the bulk crystals due to the quantum-sized confinement effect. 相似文献
53.
Yasuyoshi Miki Noriko Nakamura Hiroko Hachiken Shoji Takemura 《Journal of heterocyclic chemistry》1989,26(6):1739-1745
Treatment of 3-(hydroxymethyl)pyrazolo[1,5-a]pyridines with trifluoroacetic acid in refluxing dichloro-methane led to the formation of bis(pyrazolo[1,5-a]pyrid-3-yl)methanes or bis[(pyrazolo[1,5-a]pyrid-3-yl)]-methyl ethers depending upon the concentration of trifluoroacetic acid. In contrast, similar treatment of 3-(1-hydroxyethyl)pyrazolo[1,5-a]pyridines gave a mixture of 3-vinylpyrazolo[1,5-a]pyridines and 1,3-bis(pyrazolo-[1,5-a]pyrid-3-yl)-1-butenes. 相似文献
54.
M Kubo T Nakagami N Yamasaki M Ito M Nogami S Taji 《Chemical & pharmaceutical bulletin》1989,37(12):3409-3411
Anti-allergic activities of animal biles and commercially available bile acids were evaluated in experimental allergic disease models. Pig bile exhibited marked preventive effects on the models of delayed-type hypersensitivity (type IV allergy), picryl chloride-induced contact dermatitis (PC-CD) and sheep red blood cells (SRBC)-induced footpad swelling in mice. Fel ursi (dried bear gallbladder) also had an inhibitory effect on PC-CD, whereas ox bile, chicken bile and bile acids had no effect on ether of the models. 相似文献
55.
Complexation of 4,6-bis{3-(2-pyridyl)-1H-pyrazol-1-yl}pyrimidine (bppp) and copper(II) tetrafluoroborate in methanol gave a self-assembled [Cu2(CH3O)2(bppp)2]2+ ion having a betweenanene-type structure. Each bppp spans across the common Cu2O2 plane in a trans fashion to ligate each copper center. The antiferromagnetic interaction observed in the Cu2O2 core is ascribable to the superexchange along the Cu-O-Cu linkage and found to be one of the largest among the analogous compounds, owing to the large Cu-O-Cu angle perturbed with the two bppp molecular tweezers. 相似文献
56.
We have exploited potential utility of 4,4,5,5-tetramethylimidazolin-1-oxyl (hin) and 4,4,5,5-tetramethylimidazolin-1-oxyl 3-oxide (hnn) as mu-1,4 and mu-1,5 bridging ligands, respectively, carrying an unpaired electron in development of metal-radical hybrid magnets. X-ray diffraction measurements of [Cu(hfac)(2)hin] (1), [Mn(hfac)(2)hin] (2), and [Mn(hfac)(2)hnn] (3) revealed one-dimensional metal-radical alternating chain structures, where hfac denotes 1,1,1,5,5,5-hexafluoropentane-2,4-dionate. Magnetic measurements of 1 indicate the presence of intrachain ferromagnetic coupling between copper and radical spins. The magnetic exchange parameter was estimated as 2J/k = 56.8 K based on an S = 1/2 equally spaced ferromagnetic chain model (H = -2J summation operator S(i).S(i+1)). This ferromagnetic interaction can be explained in terms of the axial coordination of the hin nitrogen or oxygen to Cu(II). The chi(m)T value of 2 and 3 increased on cooling, and the magnetic data could be analyzed by Seiden's ferrimagnetic chain model, giving 2J/k = -325 and -740 K, respectively. The antiferromagnetic interaction of 2 and 3 can be attributed to orbital overlap between the manganese and the oxygen or nitrogen magnetic orbitals. The exchange interactions between Cu-hin and Mn-hnn are larger than those of typical Cu- and Mn-nitronyl nitroxide complexes, indicating that the choice of small ligands is a promising strategy to bestow strong exchange interaction. Compound 3 became a ferrimagnet below 4.4 K, owing to ferromagnetic coupling among the ferrimagnetic chains. 相似文献
57.
58.
Assimilation, dissimilation, and detoxification of formaldehyde, a central metabolic intermediate of methylotrophic metabolism 总被引:9,自引:0,他引:9
Methanol is a valuable raw material used in the manufacture of useful chemicals as well as a potential source of energy to replace coal and petroleum. Biotechnological interest in the microbial utilization of methanol has increased because it is an ideal carbon source and can be produced from renewable biomass. Formaldehyde, a cytotoxic compound, is a central metabolic intermediate in methanol metabolism. Therefore, microorganisms utilizing methanol have adopted several metabolic strategies to cope with the toxicity of formaldehyde. Formaldehyde is initially detoxified through trapping by some cofactors, such as glutathione, mycothiol, tetrahydrofolate, and tetrahydromethanopterin, before being oxidized to CO2. Alternatively, free formaldehyde can be trapped by sugar phosphates as the first reaction in the C1 assimilation pathways: the xylulose monophosphate pathway for yeasts and the ribulose monophosphate (RuMP) pathway for bacteria. In yeasts, although formaldehyde generation and consumption takes place in the peroxisome, the cytosolic formaldehyde oxidation pathway also plays a role in formaldehyde detoxification as well as energy formation. The key enzymes of the RuMP pathway are found in a variety of microorganisms including bacteria and archaea. Regulation of the genes encoding these enzymes and their catalytic mechanisms depend on the physiological traits of these organisms during evolution. 相似文献
59.
Matsuzaki Y Nogami A Iwaki Y Ohta N Yoshida N Aratani N Osuka A Tanaka K 《The journal of physical chemistry. A》2005,109(4):703-713
The electroabsorption (EA) spectra of directly meso-meso-linked porphyrin arrays (Zn, n = 1-3) have been investigated by means of the sum-over-states (SOS) approach at the INDO/S-SCI level theory. The experimental EA spectra of Zn (n > or = 2) exhibit an unusual second-derivative line shape at the exciton split low-energy B(x) band in contrast to the first-derivative spectrum of Z1, which is readily ascribed to a quadratic Stark shift of the B (Soret) band. Although the second-derivative line shape is usually attributed to a difference in the permanent dipole moment (Deltamu) between the ground and excited states, it should be vanishing for Zn due to their essentially D(2)(d) or D(2)(h) symmetry. As pointed out in our previous studies, the interporphyrinic charge-transfer (CT) excited states are accidentally overlapping with the excitonic B bands and the present calculations reveal that the B(x) state is strongly coupled via a transition dipole moment with two such CT states. These situations give rise to a quadratic Stark effect on the B(x) band that is intermediate between Stark shift (first derivative) and Stark broadening (second derivative), and play a central role in establishing the anomalous second derivative nature of the EA spectrum. Moreover, based on the comparison between the theoretical and experimental spectra, there must be an additional factor that further enhances the second derivative nature of the EA spectrum of porphyrin arrays. Discussions on this issue including the preliminary investigations on the role of solvent (PMMA)-induced asymmetry are also presented. 相似文献
60.
Ge nanocrystal-embedded SiO2 glasses were prepared by a sol-gel process. The glasses synthesized through the hydrolysis of Si(OC2H5)4 and GeCl4 were heated in H2 gas atmosphere at 500 to 800°C, in which Ge4+ ions were reduced to precipitate nanosized Ge crystals with the size smaller than 10 nm diameter. Glasses doped with Ge nanocrystals
of diameter of ≈5 nm showed the optical absorption edge at ≈2.8 eV and a broad photoluminescence exhibiting the peak at around
2.2 eV. Large Ge crystals precipitated by heating above 800°C showed no photoluminescence. 相似文献