全文获取类型
收费全文 | 5639篇 |
免费 | 130篇 |
国内免费 | 20篇 |
专业分类
化学 | 3952篇 |
晶体学 | 69篇 |
力学 | 74篇 |
数学 | 247篇 |
物理学 | 1447篇 |
出版年
2022年 | 29篇 |
2021年 | 32篇 |
2020年 | 58篇 |
2019年 | 69篇 |
2018年 | 52篇 |
2017年 | 36篇 |
2016年 | 87篇 |
2015年 | 91篇 |
2014年 | 129篇 |
2013年 | 275篇 |
2012年 | 262篇 |
2011年 | 285篇 |
2010年 | 159篇 |
2009年 | 165篇 |
2008年 | 298篇 |
2007年 | 254篇 |
2006年 | 283篇 |
2005年 | 274篇 |
2004年 | 256篇 |
2003年 | 204篇 |
2002年 | 210篇 |
2001年 | 153篇 |
2000年 | 163篇 |
1999年 | 89篇 |
1998年 | 61篇 |
1997年 | 63篇 |
1996年 | 66篇 |
1995年 | 45篇 |
1994年 | 69篇 |
1993年 | 92篇 |
1992年 | 95篇 |
1991年 | 75篇 |
1990年 | 64篇 |
1989年 | 56篇 |
1988年 | 72篇 |
1987年 | 73篇 |
1986年 | 75篇 |
1985年 | 106篇 |
1984年 | 98篇 |
1983年 | 40篇 |
1982年 | 69篇 |
1981年 | 79篇 |
1980年 | 70篇 |
1979年 | 60篇 |
1978年 | 54篇 |
1977年 | 64篇 |
1976年 | 52篇 |
1975年 | 39篇 |
1974年 | 49篇 |
1973年 | 30篇 |
排序方式: 共有5789条查询结果,搜索用时 15 毫秒
71.
Tokuyama R Takahashi Y Tomita Y Suzuki T Yoshida T Iwasaki N Kado N Okezaki E Nagata O 《Chemical & pharmaceutical bulletin》2001,49(4):347-352
A structure-activity relationship (SAR) study on 5-substituted oxazolidinones as an antibacterial agent is described. The oxazolidinones, of which 5-acetylaminomethyl moiety was converted into other functions, were prepared and evaluated for antibacterial activity. Elongation of the methylene chain (8) and conversion of the acetamido moiety into guanidino moiety (12) decreased the antibacterial activity. The replacement of carbonyl oxygen (=O) by thiocarbonyl sulfur (=S) enhanced in vitro antibacterial activity. Especially, compound 16, which had the 5-thiourea group, showed 4-8 stronger in vitro activity than linezolid. Our SAR study revealed that the antibacterial activity was greatly affected by the conversion of 5-substituent. 相似文献
72.
A simple and effective method of preparing fast-response gels is developed. The freeze-drying and subsequent rehydration of thermosensitive gels alters the microstructural properties of the gels in a way that leads to rapid shrinking rates. Microporous hydroxypropyl cellulose (HPC) gels were created by this method to investigate the influence of the process on the swelling and shrinking kinetics of the gels in response to temperature changes. Micropores of different size ranges were produced by freezing gels with different amounts of water at −20 °C. Water content was the key factor to control the microporosity and the shrinking rates of gels. After the freezing treatment, an effective diffusion coefficient for shrinking could be determined by fitting Fick's law to the data (5.2 × 10−4 cm2/s). This was an increase of two orders of magnitude over that of the untreated, non-porous gel (6.0 × 10−6 cm2/s). The magnitude of the shrinking coefficient indicates that the shrinking rate of the microporous gel is probably limited by the convective flow, as unsteady flow through porous media follows the same differential equation as Fick's law, but with much greater transport coefficients, as observed here. Physically, the shrinking rate may be determined by the level of interconnected-cells in a microporous structure present at the beginning of shrinking process because the convection through the interconnected-cells is estimated to be much slower than the polymer network diffusion rate of the struts of micropores (0.1–3.0 μm) as well as heat transfer. 相似文献
73.
Shuzi Hayase Yasunobu Onishi Shuichi Suzuki Moriyasu Wada Atushi Kurita 《Journal of polymer science. Part A, Polymer chemistry》1987,25(3):753-763
o-Nitrobenzyl triphenylsilyl ehther/aluminum compound has been previously shown by the authors to act as catalyst in the photopolymerization of epoxides. The dependence of the structure of the silyl ether on the catalyst activity was examined. There were two steps in the photopolymerization. The first step (“Step 1”) is photodecomposition of the silyl ether to silanol. The second step (“Step 2”) is the initiation of polymerization by silanol and the aluminum compound. The introduction of an electron withdrawing group, Cl, CF3, on the benzene ring bonded to Si made the quantum yield of Step 1 low, however, the rate of Step 2 was increased. The low quantum yield of Step 1 was explained in terms of the rate of electron transfer that is controlled by the relative electron density between the CH2 and NO2 in the o-nitrobenzyl group. The acceleration of Step 2 was explained in terms of an increase in silanol acidity that was promoted by the introduction of an electron withdrawing group. The overall rate of the photopolymerizatiol depends to a greater degree on the rate of Step 2 than on that of Step 1. 相似文献
74.
T. Suzuki M. Aida Y. Ban Y. Fujii M. Hara T. Mitsugashira 《Journal of Radioanalytical and Nuclear Chemistry》2003,255(3):581-583
The separation of trivalent actinides and lanthanides was studied by using newly developed tertiary pyridine-type anion-exchange resin embedded in silica beads. Chromatographic elution experiments were carried out by using a packed column of the new resin and methanol-hydrochloric acid solution as an effluent. We confirmed that the actinides were eluted well from the elution bands of lanthanides. Actinides and lanthanides were eluted according to the reverse order of their atomic number. 相似文献
75.
Ultrasonic slurry sampling electrothermal atomic absorption spectrometry with a metal tube atomizer has been applied to the determination of lead in Bangladeshi fish samples. The slurry sampling conditions, such as slurry stabilizing agent, slurry concentration, pyrolysis temperature for the slurried fish samples, particle size and ultrasonic agitation time, were optimized for electrothermal atomic absorption spectrometry with the Mo tube atomizer. Thiourea was used as the chemical modifier for the interference of matrix elements. The detection limit was 53 fg (3S/N). The determined amount of lead in Bangladeshi fish samples was consistent with those measured in the dissolved acid-digested samples. The advantages of the proposed methods are easy calibration, simplicity, low cost and rapid analysis. 相似文献
76.
To make clear the reason of unsuitability of poly(vinyl alcohol) (PVA) protective colloid for the emulsion polymerization
of conjugated monomers, a model experiment of emulsion polymerization of methyl methacrylate (MMA) was carried out with ammonium
persulfate (APS) or azobis(isobutyronitrile) (AIBN) initiators, where a small amount of MMA (1/100th of the concentration
compared with ordinary emulsion polymerization) was employed. This corresponds to the initial stage of the emulsion polymerization.
Grafting of MMA onto PVA took place remarkably irrespective of the kind of the initiators. Formation of homo-poly(MMA) was
observed to a small extent. The formation of new emulsion particles smaller than 100 nm continued to increase to almost the
end of the polymerization. PVA molecules in the grafted polymer are supposed to act as stabilizers of newly formed particles.
From kinetic treatment using the experimental data, the important issues were derived as follows. Firstly, the sulfate anion
radical from APS is much more reactive than the isobutyronitrile radical from AIBN in terms of hydrogen abstraction from PVA.
Secondly, high grafting ability of the latter initiator system, notwithstanding the much lower reactivity in the hydrogen
abstraction compared with the APS system, is attributed to the relative reactivity of the primary radicals, i.e., hydrogen
abstraction reaction from PVA to initiation reaction with MMA. The much slower rate of addition of the isobutyronitrile radical
to the monomer compared with that of hydrogen abstraction from PVA facilitates the grafting, although the rate constant of
hydrogen abstraction is far smaller than that with the sulfate anion radical by 10−4 times.
Received: 26 April 2001 Accepted: 6 September 2001 相似文献
77.
Motohiko Hikuma Haruo Obana Takeo Yasuda Isao Karube Shuichi Suzuki 《Analytica chimica acta》1980,116(1):61-67
The sensor consists of immobilized E. coli (which contains glutamate decarboxylase) and a carbon dioxide gas-sensor. Continuous introduction of sample solution into a flow system incorporating the sensor gives a potential which increases until a steady state is reached after 5 min. Measurements can also be made with only a 1- or 3-min introduction period with little loss of sensitivity. Calibration plots of mV measurements vs. logarithmic glutamic acid concentration are linear in the range 100–800 mg l-1. The sensor is highly selective, stable and reproducible. It has been applied to the determination of glutamic acid in fermentation broths. 相似文献
78.
Kawai H Katoono R Fujiwara K Tsuji T Suzuki T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(3):815-824
The molecular recognition of catecholamines by hydrindacene-based receptors 1 and 2, as well as the durene-based receptor 3, and the guest-induced conformational changes are reported. These receptors selectively bind adrenaline and dopamine salts through the guests' ammonium group and 3-hydroxyl group on the aromatic ring. In the case of adrenaline, an additional hydrogen bond with a benzylic hydroxyl group is formed. In 2 % CD3CN/CDCl3, the association constants are of the order of 10(4) M(-1), which is much larger than with guests without the 3-hydroxyl groups (10(3) M(-1)). The two amide groups of receptor 1 can rotate freely around the C(aromatic)--C(amide) bond, whereas the tert-amide in 2 changes between two stable conformations at a slow enough rate to allow detection by (1)H NMR spectroscopy. In the absence of a guest molecule, the syn-conformer is less stable than the anti-conformer. On complex formation with adrenaline, the syn-conformer becomes dominant due to an intramolecular dipole-reversal effect in addition to multipoint hydrogen bonding. 相似文献
79.
A sensitive and rapid method is presented for the determination of vanadium at ng to sub-ng ml(-1) levels in natural waters, in which in-line preconcentration/separation is directly coupled with catalytic detection of vanadium in a flow-injection system. Vanadium was adsorbed on a small column packed with Sephadex G-25 gel and desorbed with a small volume of 0.010 M HCl. The catalytic action of vanadium on the oxidation of chromotropic acid (1,8-dihydroxy-3,6-naphthalenedisulphonic acid) by bromate in pH 3.8 buffered media was used in the sensitive determination of vanadium. Effective preconcentration/separation of trace vanadium can be achieved from Fe(III), Cu(II) and a large excess of sodium chloride in seawater sample. A linear calibration using a 5 m sample loop was obtained for vanadium in the range 0-2.5 ng ml(-1). The limit of detection was 0.02 ng ml(-1) and the relative standard deviation was 1.2% for 1.0 ng ml(-1) vanadium (n=5). The present FIA system is rapid and sensitive and can be readily applied to river water and coastal seawater samples. 相似文献
80.