全文获取类型
收费全文 | 5112篇 |
免费 | 113篇 |
国内免费 | 29篇 |
专业分类
化学 | 3635篇 |
晶体学 | 63篇 |
力学 | 63篇 |
综合类 | 1篇 |
数学 | 273篇 |
物理学 | 1219篇 |
出版年
2022年 | 17篇 |
2021年 | 40篇 |
2020年 | 47篇 |
2019年 | 70篇 |
2018年 | 48篇 |
2017年 | 33篇 |
2016年 | 63篇 |
2015年 | 83篇 |
2014年 | 87篇 |
2013年 | 265篇 |
2012年 | 202篇 |
2011年 | 284篇 |
2010年 | 134篇 |
2009年 | 182篇 |
2008年 | 267篇 |
2007年 | 276篇 |
2006年 | 273篇 |
2005年 | 238篇 |
2004年 | 237篇 |
2003年 | 211篇 |
2002年 | 218篇 |
2001年 | 151篇 |
2000年 | 120篇 |
1999年 | 79篇 |
1998年 | 74篇 |
1997年 | 72篇 |
1996年 | 65篇 |
1995年 | 59篇 |
1994年 | 65篇 |
1993年 | 70篇 |
1992年 | 82篇 |
1991年 | 70篇 |
1990年 | 63篇 |
1989年 | 67篇 |
1988年 | 60篇 |
1987年 | 66篇 |
1986年 | 53篇 |
1985年 | 76篇 |
1984年 | 79篇 |
1983年 | 52篇 |
1982年 | 48篇 |
1981年 | 57篇 |
1980年 | 42篇 |
1979年 | 63篇 |
1978年 | 56篇 |
1977年 | 37篇 |
1976年 | 40篇 |
1975年 | 28篇 |
1974年 | 33篇 |
1973年 | 23篇 |
排序方式: 共有5254条查询结果,搜索用时 31 毫秒
1.
Minoru Koyama Dr. Takafumi Kawakami Dr. Takashi Okazoe Prof. Dr. Kyoko Nozaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(46):10913-10917
Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF3CH2, and n-C6F13CH2CH2 esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C6F13CH2CH2 esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d6 and MeOH-d4, with DBU in acetonitrile afforded deuterated MMA (MMA-d8) in 70 % yield. 相似文献
2.
Hiroyuki Saimoto Tomoyuki Onitsuka Satoko Okabe Minoru Morimoto 《Tetrahedron letters》2004,45(48):8777-8780
Treatment of 1,3-dihydroxyacetone and acrolein with aqueous KOH gave a tetrahydrofuran derivative, 1,4-dihydroxy-3,7-dioxabicyclo[3.3.0]octane, in 80% yield. Similarly, 6-alkyl substituted 1,4-dihydroxy-3,7-dioxabicyclo[3.3.0]octanes were obtained by reaction of 1,3-dihydroxyacetone with various α,β-unsaturated aldehydes. In the cases of long chain alkenals, the reaction was effectively accelerated in the presence of organic co-solvent. On the other hand, the corresponding tricyclic products were synthesized by reaction of 1,3-dihydroxyacetone with cyclic enones, such as 2-cyclopentenone and 2-cyclohexenone. This method was successfully applied to the reaction of a tetrulose in the absence of any protecting groups. 相似文献
3.
It is theoretically predicted that the Nernst coefficient is strongly suppressed and the thermal conductance is quantized in the quantum Hall regime of the two-dimensional electron gas. The Nernst effect is the induction of a thermomagnetic electromotive force in the y-direction under a temperature bias in the x-direction and a magnetic field in the z-direction. The quantum nature of the Nernst effect is analyzed with the use of a circulating edge current and is demonstrated numerically. The present system is a physical realization of the non-equilibrium steady state. 相似文献
4.
Yoshiko Oi Nakamura 《Surface science》1987,180(2-3):518-549
By using a quantized theory of non-radiative surface plasmon in a semi-infinite electron gas, where retardation is taken into account, the differential surface loss intensity of electrons in a metal foil is calculated for the case of non-normal incidence of electron to the metal surface. The result shows that the differential surface loss intensity neither has a zero at θ = 0 for the case of normal incidence nor has a zero at a forward direction (θ ≠ 0, φ = 0) for the case of non-normal incidence, whose existences were predicted by electrostatic theories, but diverges as 1/θ at θ = 0 for both cases. It is also shown that, when the angle of incidence is greater than a certain critical value, there is a region of direction to which incident electrons can be scattered by exciting any one of surface plasmons with three different wave vectors. 相似文献
5.
Dehydropeptides containing dehydroamino acid (ΔAA) are frequently found in natural resources with important biological activity. Herein, we report the selective synthesis of Z- and E-ΔAbu from l- and l-allo-threonine as starting materials through selenation and oxidative elimination. The detailed reaction mechanism of phosphine-assisted selenoether formation is also discussed. 相似文献
6.
Takayuki Yaegashi Shinya Yodoya Masahiko Nakamura Hiroki Takeshita Katsuhiko Takenaka Tomoo Shiomi 《Journal of polymer science. Part A, Polymer chemistry》2004,42(4):999-1007
Free‐radical homo‐ and copolymerization behavior of N,N‐diethyl‐2‐methylene‐3‐butenamide (DEA) was investigated. When the monomer was heated in bulk at 60 °C for 25 h without initiator, rubbery, solid gel was formed by the thermal polymerization. No such reaction was observed when the polymerization was carried out in 2 mol/L of benzene solution with with 1 mol % of azobisisobutyronitrile (AIBN) as an initiator. The polymerization rate (Rp) equation was Rp ∝ [DEA]1.1[AIBN]0.51, and the overall activation energy of polymerization was calculated 84.1 kJ/mol. The microstructure of the resulting polymer was exclusively a 1,4‐structure where both 1,4‐E and 1,4‐Z structures were included. From the product analysis of the telomerization with tert‐butylmercaptan as a telogen, the modes of monomer addition were estimated to be both 1,4‐ and 4,1‐addition. The copolymerizations of this monomer with styrene and/or chloroprene as comonomers were also carried out in benzene solution at 60 °C. In the copolymerization with styrene, the monomer reactivity ratios obtained were r1 = 5.83 and r2 = 0.05, and the Q and e values were Q = 8.4 and e = 0.33, respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 999–1007, 2004 相似文献
7.
Yasushi Seike Ryoko Fukumori Yukiko Senga Hiroki Oka Kaoru Fujinaga Minoru Okumura 《Analytical sciences》2004,20(1):139-142
A new and simple method for the determination of hydroxylamine in environmental water, such as fresh rivers and lakes using hypochlorite, followed by its gas choromatographic detection, has been developed. A glass vial filled with sample water was sealed by a butyl-rubber stopper and aluminum cap without head-space, and then sodium hypochlorite solution was injected into the vial through a syringe to convert hydroxylamine to nitrous oxide. The head-space in the glass vial was prepared with 99.9% grade N2 using a gas-tight syringe. After the glass vial was shaken for a few minutes, nitrous oxide in the gas-phase was measured by a gas chromatograph with an electron-capture detector. The dissolved nitrous oxide in the liquid-phase was calculated according to the solubility formula. The proposed method was applied to the analysis of fresh-water samples taken from Iu river and Hii river, flowing into brackish Lakes Nakaumi and Shinji, respectively. 相似文献
8.
Minoru Itoh 《Mathematische Zeitschrift》2004,246(1-2):125-154
9.
H. Yonemura S. Moribe K. Hayashi M. Noda H. Tokudome S. Yamada H. Nakamura 《Applied magnetic resonance》2003,23(3-4):289-307
Photoinduced intramolecular electron-transfer reactions in carbazole (Cz)-fullerene (C60) (Cz(8)C60) and phenothiazine (Ph)-C60 (Ph(n)C60 (n=8, 10, 12)) linked compounds have been investigated in benzene and benzonitrile by fluorescence, transient absorption, and time-resolved electron paramagnetic resonance measurements, and by magnetic field effects on the decay rate constants of the photogenerated biradicals. In benzonitrile, photoinduced intramolecular electron transfer from Cz to the singlet excited state of C60 (1C60 *) occurred in Cz(8)C60, but not to the triplet excited state (3C60 *), while the intramolecular electron-transfer to both1C60 * and3C60 * occurred in Ph(n)C60 (n=8, 10, 12). In benzene, on the other hand, no electron transfer to both1C60 * and3C60 * took place in all linked compounds. These results were interpreted in terms of the different Gibbs free energy changes in the two solvents. 相似文献
10.
T Akamatsu D Wang K Nakamura K Wang 《The Journal of the Acoustical Society of America》1998,104(4):2511-2516
The interclick intervals of captive dolphins are known to be longer than the two-way transit time between the dolphin and a target. In the present study, the interclick intervals of free-ranging baiji, finless porpoises, and bottlenose dolphins in the wild and in captivity were compared. The click intervals in open waters ranged up to 100-200 ms, whereas the click intervals in captivity were in the order of 4-28 ms. Echolocation of free-ranging dolphins appears to adapt to various distance in navigation or ranging, sometimes up to 140 m. Additionally, the difference of waveform characteristics of clicks between species was recognized in the frequency of maximum energy and the click duration. 相似文献