全文获取类型
收费全文 | 521篇 |
免费 | 13篇 |
国内免费 | 1篇 |
专业分类
化学 | 417篇 |
晶体学 | 2篇 |
力学 | 5篇 |
数学 | 10篇 |
物理学 | 101篇 |
出版年
2023年 | 3篇 |
2021年 | 6篇 |
2020年 | 9篇 |
2019年 | 11篇 |
2017年 | 3篇 |
2016年 | 7篇 |
2015年 | 8篇 |
2014年 | 9篇 |
2013年 | 22篇 |
2012年 | 19篇 |
2011年 | 34篇 |
2010年 | 18篇 |
2009年 | 17篇 |
2008年 | 34篇 |
2007年 | 19篇 |
2006年 | 22篇 |
2005年 | 24篇 |
2004年 | 35篇 |
2003年 | 22篇 |
2002年 | 20篇 |
2001年 | 18篇 |
2000年 | 8篇 |
1999年 | 17篇 |
1997年 | 3篇 |
1996年 | 10篇 |
1993年 | 4篇 |
1992年 | 7篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 7篇 |
1987年 | 7篇 |
1985年 | 15篇 |
1984年 | 12篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 8篇 |
1980年 | 4篇 |
1979年 | 9篇 |
1978年 | 5篇 |
1977年 | 5篇 |
1976年 | 3篇 |
1975年 | 6篇 |
1974年 | 5篇 |
1973年 | 3篇 |
1972年 | 2篇 |
1971年 | 2篇 |
1970年 | 4篇 |
1968年 | 2篇 |
1967年 | 2篇 |
排序方式: 共有535条查询结果,搜索用时 15 毫秒
21.
Ion-pair formation constants (KMLA mol−1 dm3) of Na+– and K+–18-crown-6 ether (18C6) complexes with MnO4− in water (w) were determined potentiometrically at 25 °C. Simultaneously, extraction constants (Kex mol−2 dm6) of the permanganates with 18C6 from w into 1,2-dichloroethane at 25 °C were obtained from the spectrophotometric determination of distribution ratios of the permanganates. These Kex values were divided into KMLA and other three component equilibrium constants and thereby extraction-selectivity and -ability were discussed in comparison with corresponding metal picrate–18C6 extraction systems reported before. 相似文献
22.
Gamma-rays of nuclides of uranium and thorium series in silicone resin and ceramics were measured with a Ge(Li) detector. The state of radioactive equilibrium was determined by comparing the concentrations of uranium and thorium with the radioactive concentrations of214Pb and212Pb. The radioactive equilibrium was attained in silicone resin but not in ceramics. The -flux was calculated from the concentrations of uranium and thorium and their daughter nuclides. The calculated values of -flux agreed with that of -flux measured. 相似文献
23.
Sakamoto S Ito A Kudo K Yoshikawa S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(15):3717-3726
The introduction of a flavin chromophore on the myoglobin (Mb) surface and an effective electron-transfer (ET) reaction through the flavin were successfully achieved by utilizing the self-assembly of heterostranded coiled-coil peptides. We have prepared a semiartificial Mb, named Mb-1alphaK, in which an amphiphilic and cationic alpha-helix peptide is conjugated at the heme propionate (Heme-1alphaK). Heme-1alphaK has a covalently bound iron-protoporphyrin IX (heme) at the N terminus of a 1alphaK peptide sequence. This sequence was designed to form a heterostranded coiled-coil in the presence of a counterpart amphiphilic and anionic 1alphaE peptide sequence in a parallel orientation. Two peptides, Fla(1)-1alphaE and Fla(31)-1alphaE, both incorporating a 10-methylisoalloxazine moiety as an artificial flavin molecule, were also prepared (Fla=2-[7-(10-methyl)isoalloxazinyl]-2-oxoethyl). Heme-1alphaK was successfully inserted into apomyoglobin to give Mb-1alphaK. Mb-1alphaK recognized the flavin-modified peptides and a two-alpha-helix structure was formed. In addition, an efficient ET from reduced nicotinamide adenine dinucleotide to the heme center through the flavin unit was observed. The ET rate was faster in the presence of Fla(1)-1alphaE than in the presence of Fla(31)-1alphaE or the equivalent molecule that has no peptide chain. These results demonstrate that the introduction of a functional chromophore on the Mb surface can be achieved by using specific peptide-peptide interactions. Moreover, the dependence of the ET rate on the position of the flavin indicated that the distance between the heme active site and the flavin chromophore was regulated by the three-dimensional structure of the designed polypeptide. 相似文献
24.
The substoichiometric precipitation of fluoride with lanthanum was studied by using18F and140La tracers and it was found that fluoride could be precipitated substoichiometrically with lanthanum and the reaction ratio
between fluoride and lanthanum was 3∶1. The pH range at which fluoride can be separated substoichiometrically with lanthanum
is between 2 and 8. Barium and indium interfere in the precipitation of fluoride, sodium, copper and manganese, however, not.
Fluorosilicate can also be precipitated substoichiometrically by using lanthanum as a precipitant and the reaction ratio between
fluorosilicate and lanthanum was 1∶2. This separation was applied for the determination of oxygen in silicon crystals. The
concentration of oxygen measured in some silicon crystals was between 5 and 27 ppm and in good agreement with those by non-destructive
method and infrared spectrophotometry. 相似文献
25.
Shoichi Katsuta Hirokazu Wakabayashi Mariko Tamaru Yoshihiro Kudo Yasuyuki Takeda 《Journal of solution chemistry》2007,36(4):531-547
Equilibria concerning picrates of tetraalkylammonium ions (Me4N+, Et4N+, Pr4N+, Bu4N+, Bu3MeN+) in a dichloromethane−water system have been investigated at 25 ∘C. The 1:1 ion-pair formation constants (K
IP,o
o) in dichloromethane at infinite dilution were conductometrically determined. The distribution constants (K
D
o) of the ion pairs and the free cations between the solvents were determined by a batch-extraction method. The K
IP,o
o value varies in the cation sequence, Bu4N+ ≈ Pr4N+ ≈ Et4N+ < Bu3MeN+ < < Me4N+; this trend is explained by the electrostatic cation−anion interaction taking into account the structures of the ion pairs
determined by density functional theory calculations. For the ion pairs of the symmetric R4N+ cations, there is a linear positive relationship between log10
K
D
o and the number of methylene groups in the cation (N
CH
2). The ion pair of asymmetric Bu3MeN+ has a higher distribution constant than that expected from the above log10
K
D
o
versus
N
CH
2 relationship. These cation dependencies of log10
K
D
o for the ion pairs are explained theoretically by using the Hildebrand-Scatchard equation. For all the cations, the log10
K
D
o value of the free cation increases linearly with N
CH
2; the variation of log10
K
D
o is discussed by decomposing the distribution constant into the Born-type electrostatic contribution and the non-Born one,
and attributed to the latter that is governed by the differences in the molar volumes of the cations. The cation dependencies
of the ion-pair extractability and ion pairing in water are also discussed.
An erratum to this article can be found at 相似文献
26.
[reaction: see text] This paper describes a novel method to synthesize a quinoline backbone by incorporating allenyl cations into a catalytic intramolecular Friedel-Crafts reaction. The initial products were isomerized and aromatized upon treatment with acid and base, respectively, to give quinolines. The basic concept also proved to be promising for 1-benzazepine, 1-benzazocine, or isoquinoline synthesis. 相似文献
27.
Tadao Ishii Takeshi Tsuchida Ryusaburo Furuichi Hiroshi Haga Kazuhiko Kudo 《Thermochimica Acta》1982,53(1):89-103
The chlorination processes of fly ash and bauxite in the presence of carbon were studied by means of a gas-flow type DTA, X-ray analysis and SEM observation, and the reactivity of Al-compounds as their constituents was compared. In the case of fly ash, the exothermic peak due to the formation of AlCl3 (mainly) and FeCl3 appeared at about 790–920°C. The reactivity of Al estimated from the DTA peak temperature depended on the particle size, carbon content and preparation temperature of fly ash, and was much lower than that of bauxite. Fractional conversion of Al was about 60–70%, when fly ash (?300 mesh) was heated up to 900°C in Cl2 at 5°C min?1 of heating rate. In the case of bauxite, two exothermic peaks due to the chlorination of Fe and Al appeared at about 270 and 490°C, respectively. The chlorination of Al was completed at 550°C under the above conditions. 相似文献
28.
Shoichi Katsuta Tokutaro Kimura Yoshihiro Kudo Ryozo Nakagawa Yasuyuki Takeda Mikio Ouchi 《Journal of inclusion phenomena and macrocyclic chemistry》1998,31(2):89-98
The overall extraction constants (Kex) of uni- andbivalent metal picrates with 15-(2,5-dioxahexyl)-15-methyl-16-crown-5(L16C5) were determined between benzene and water at 25°C. TheKex values were analyzed into the constituent equilibriumconstants, i.e., the extraction constant of picric acid, the distributionconstant of the crown ether, the stability constant of the metalion–crown ether complex in water, and the ion-pair extraction constantof the complex cation with the picrate anion. The Kex valuedecreases in the orders Ag+ > Na+ >Tl+ > K+ > Li+ andPb2+ > Ba2+ > Sr2+ for theuni- and bivalent metals, respectively, which are the same as those observedfor 16C5. The extraction selectivity was found to be governed by theselectivity of the ion-pair extraction of the L16C5–metal picratecomplex rather than by that of the complex formation in water. Theextraction ability of L16C5 is smaller for all the metals than that of 16C5,which is mostly attributed to the higher lipophilicity of L16C5. Differencesin the extraction selectivity between L16C5 and 16C5 were observed for thebivalent metals but little for the univalent metals. The side-arm effect onthe extraction selectivity was interpreted on the basis of the negativecorrelation between the effect on the complex stability constant in waterand that on the ion-pair extraction constant. 相似文献
29.
Ikuya Tagawa Yosuke UrakamiMaki Maeda Youji MaruyamaKazue Kudo Hiromi ShiinaMasafumi Mochizuki 《Journal of magnetism and magnetic materials》2012,324(3):327-329
To make the write-field much stronger with sharper cross-track field gradient in Shingled perpendicular Magnetic Recording (SMR), we have successfully developed asymmetric SMR heads with one-side shield design. Using these heads, higher track density capability on the shielded-side was demonstrated, which came from narrower erase-band width at shielded side. 相似文献
30.
Dr. Yuki Ohishi Kentaro Masuda Kazuki Kudo Prof. Dr. Hajime Abe Prof. Dr. Masahiko Inouye 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(2):785-793
Generally, cage-shaped hosts for saccharides can bind strongly to guest molecules because of the three-dimensional preorganized hydrogen-bonding sites. However, the preparation of cage molecules is often difficult because of the low yield of the macrocyclization step. Here, we report a three-arm-shaped molecule possessing pyridine-acetylene-phenol units as a new kind of host having a preorganized three-dimensional hydrogen-bonding site. This three-arm-shaped host was readily prepared compared to a cage-shaped analogue. This host associated with lipophilic glycosides to form chiral complexes, and the association constants were sufficiently high as to be comparable to those of the cage-shaped analogue. Furthermore, this host extracted native monosaccharides into a lipophilic solvent. 相似文献