全文获取类型
收费全文 | 1197篇 |
免费 | 25篇 |
国内免费 | 8篇 |
专业分类
化学 | 908篇 |
晶体学 | 21篇 |
力学 | 16篇 |
综合类 | 1篇 |
数学 | 92篇 |
物理学 | 192篇 |
出版年
2021年 | 7篇 |
2019年 | 16篇 |
2018年 | 12篇 |
2017年 | 12篇 |
2016年 | 9篇 |
2015年 | 18篇 |
2014年 | 24篇 |
2013年 | 103篇 |
2012年 | 34篇 |
2011年 | 66篇 |
2010年 | 32篇 |
2009年 | 45篇 |
2008年 | 69篇 |
2007年 | 69篇 |
2006年 | 64篇 |
2005年 | 66篇 |
2004年 | 72篇 |
2003年 | 59篇 |
2002年 | 43篇 |
2001年 | 15篇 |
2000年 | 6篇 |
1998年 | 13篇 |
1997年 | 10篇 |
1996年 | 10篇 |
1995年 | 15篇 |
1994年 | 16篇 |
1993年 | 9篇 |
1992年 | 6篇 |
1991年 | 14篇 |
1990年 | 12篇 |
1989年 | 9篇 |
1988年 | 17篇 |
1987年 | 9篇 |
1986年 | 5篇 |
1985年 | 20篇 |
1984年 | 31篇 |
1983年 | 12篇 |
1982年 | 23篇 |
1981年 | 15篇 |
1980年 | 12篇 |
1979年 | 18篇 |
1978年 | 16篇 |
1977年 | 12篇 |
1976年 | 10篇 |
1975年 | 6篇 |
1974年 | 5篇 |
1972年 | 7篇 |
1967年 | 6篇 |
1959年 | 5篇 |
1956年 | 6篇 |
排序方式: 共有1230条查询结果,搜索用时 15 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.
Shofu Matsuda Yuuki Okuda Yoshiki Obu Norio Nagayama Minoru Umeda 《Electroanalysis》2019,31(12):2466-2471
With the objective of understanding the kinetic redox properties of triphenylamine derivatives in association with chemical reactions, for their future application in functional organic semiconductor devices, the electrochemical characteristics of 4‐(2,2‐diphenylethenyl)‐N,N‐bis(4‐methylphenyl)‐benzenamine (TPA) were evaluated. Based on cyclic voltammograms of TPA on Pt disk electrodes with diameters of 300 μm and 10 μm at slow and fast scan rates in an acetonitrile solution, the TPA.+ is stable, while the TPA2+ is unstable. Importantly, the unstable TPA2+ appears to break down by a subsequent chemical reaction. A Cottrell plot analysis from chronoamperometry of a solution containing TPA reveals that both the first and second oxidations are one‐electron reactions. Concerning the stabilization mechanism of the first oxidation state of TPA, the results of molecular orbital calculations indicate that the electrons of the HOMO level are distributed in the triphenylamine group, which induces a resonance‐stabilized TPA.+. Based on these results, TPA/TPA.+ is suggested to have a sufficient stability for further application in organic semiconductor devices. 相似文献
3.
We consider a Schrödinger operator on , where V is a real-valued measurable function, and give an explicit and simple characterization of intrinsic ultracontractivity (IU) of the Schrödinger semigroup generated by L for a wide class of potentials. By making use of it, we also give new examples of potentials for which the semigroups satisfy (IU) or non-(IU). 相似文献
4.
Proton Order–Disorder Phenomena in a Hydrogen‐Bonded Rhodium–η5‐Semiquinone Complex: A Possible Dielectric Response Mechanism 下载免费PDF全文
Dr. Minoru Mitsumi Kazunari Ezaki Yuuki Komatsu Prof. Dr. Koshiro Toriumi Dr. Tatsuya Miyatou Prof. Dr. Motohiro Mizuno Nobuaki Azuma Prof. Dr. Yuji Miyazaki Prof. Dr. Motohiro Nakano Prof. Dr. Yasutaka Kitagawa Dr. Takayasu Hanashima Dr. Ryoji Kiyanagi Dr. Takashi Ohhara Prof. Dr. Kazuhiro Nakasuji 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9682-9696
A newly synthesized one‐dimensional (1D) hydrogen‐bonded (H‐bonded) rhodium(II)–η5‐semiquinone complex, [Cp*Rh(η5‐p‐HSQ‐Me4)]PF6 ([ 1 ]PF6; Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl; HSQ=semiquinone) exhibits a paraelectric–antiferroelectric second‐order phase transition at 237.1 K. Neutron and X‐ray crystal structure analyses reveal that the H‐bonded proton is disordered over two sites in the room‐temperature (RT) phase. The phase transition would arise from this proton disorder together with rotation or libration of the Cp* ring and PF6? ion. The relative permittivity εb′ along the H‐bonded chains reaches relatively high values (ca., 130) in the RT phase. The temperature dependence of 13C CP/MAS NMR spectra demonstrates that the proton is dynamically disordered in the RT phase and that the proton exchange has already occurred in the low‐temperature (LT) phase. Rate constants for the proton exchange are estimated to be 10?4–10?6 s in the temperature range of 240–270 K. DFT calculations predict that the protonation/deprotonation of [ 1 ]+ leads to interesting hapticity changes of the semiquinone ligand accompanied by reduction/oxidation by the π‐bonded rhodium fragment, producing the stable η6‐hydroquinone complex, [Cp*Rh3+(η6‐p‐H2Q‐Me4)]2+ ([ 2 ]2+), and η4‐benzoquinone complex, [Cp*Rh+(η4‐p‐BQ‐Me4)] ([ 3 ]), respectively. Possible mechanisms leading to the dielectric response are discussed on the basis of the migration of the protonic solitons comprising of [ 2 ]2+ and [ 3 ], which would be generated in the H‐bonded chain. 相似文献
5.
Spectroscopic Properties of Amine‐substituted Analogues of Firefly Luciferin and Oxyluciferin 下载免费PDF全文
Michio Kakiuchi Soichiro Ito Minoru Yamaji Vadim R. Viviani Shojiro Maki Takashi Hirano 《Photochemistry and photobiology》2017,93(2):486-494
Spectroscopic and photophysical properties of firefly luciferin and oxyluciferin analogues with an amine substituent (NH2, NHMe and NMe2) at the C6' position were studied based on absorption and fluorescence measurements. Their π‐electronic properties were investigated by DFT and TD‐DFT calculations. These compounds showed fluorescence solvatochromism with good quantum yields. An increase in the electron‐donating strength of the substituent led to the bathochromic shift of the fluorescence maximum. The fluorescence maxima of the luciferin analogues and the corresponding oxyluciferin analogues in a solvent were well correlated with each other. Based on the obtained data, the polarity of a luciferase active site was explained. As a result, the maximum wavelength of bioluminescence for a luciferin analogue was readily predicted by measuring the photoluminescence of the luciferin analogue in place of that of the corresponding oxyluciferin analogue. 相似文献
6.
Reaction of 2-propargylphenylcarbamates with diphenyliodonium salts via Meyer-Schuster rearrangement
Hideki Minami Noriko Okamoto Takuya Sueda Takatsugu Sakaguchi Minoru Ishikura Reiko Yanada 《Tetrahedron letters》2017,58(45):4277-4280
The syntheses of 2,3-dihydro-4-quinolones from 2-propargylphenylcarbamates by one-pot tandem process that involves Meyer-Schuster rearrangement or arylative Meyer-Schuster rearrangement/Michael addition of carbamate nitrogen to the resulting vinyl ketones have been developed. Phenylcarbamates tethering tertiary propargyl alcohols underwent arylative Meyer-Schuster rearrangement/Friedel-Crafts alkylation to produce 2,3-dihydroindenones. 相似文献
7.
We point out that it is immediate by our character formula that in the case of a boundary level the characters of admissible representations of affine Kac–Moody algebras and the corresponding W-algebras decompose in products in terms of the Jacobi form . 相似文献
8.
A new type of optically active N-(L-menthylcarboxylatomethyl)maleimide (MGMI) was synthesized from maleic anhydride, glycine, and L-menthol. Radical homopolymerization of MGMI was performed at 50°C for 24 h to give optically active polymer having [α]D = -57°. Radical copolymerizations of MGMI (M 1) were performed with styrene (ST, M 2), methyl methacrylate (MMA, M 2) in benzene at 50°C. From the results, the monomer reactivity ratios (r 1, r 2) and the Alfrey-Price Q, e values were determined as follows: r 1 = 0.16, r 2 = 0.006 for the MGMI-ST system; r 1 = 0.15, r 2 = 1.65 for the MGMI-MMA system, and Q 1 = 0.72, e 1 = 1.59 calculated from the MGMI-MMA system. Anionic homopolymerizations of MGMI were also carried out. Chiroptical properties of the polymers were investigated. 相似文献
9.
Abstract The binary system of tetramethyl tetrazene (TMT) and Co(II) chloride was used as initiator of acrylonitrile (AN) in dimethylformamide. The initial rate of polymerization (Rp) was found to be expressed by Rp = k[TMT]0.62[Co(II) chloride]0.57 [AN]2.00 The polymerization was confirmed to proceed via a radical mechanism. The over-all activation energy for the polymerization was estimated as 15.1 kcal/mole. On the basis of these results and the product analysis of the reaction between the catalyst components in the absence of monomer, the initiation mechanism of the polymerization is discussed. 相似文献
10.
Tatsuro Ouchi Kazuhiro Nomoto Yoshifumi Hosaka Minoru Imoto Tadao Nakaya Tsutomu Iwamoto 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(6-7):859-866
Abstract Three kinds of betaine-type polymers, which are macromolecular amphoteric electrolytes, were found to be able to polymerize vinyl monomers in aqueous solution through a radical mechanism without any further initiator. Betain-type polymers form hydrophobic areas (HA) in water. Vinyl polymerization commenced in the HA. The effect of the pH of the aqueous solution on polymerization was investigated. 相似文献