全文获取类型
收费全文 | 948篇 |
免费 | 36篇 |
国内免费 | 3篇 |
专业分类
化学 | 755篇 |
晶体学 | 8篇 |
力学 | 13篇 |
数学 | 53篇 |
物理学 | 158篇 |
出版年
2022年 | 4篇 |
2021年 | 17篇 |
2020年 | 17篇 |
2019年 | 21篇 |
2018年 | 18篇 |
2017年 | 11篇 |
2016年 | 24篇 |
2015年 | 21篇 |
2014年 | 22篇 |
2013年 | 42篇 |
2012年 | 59篇 |
2011年 | 70篇 |
2010年 | 30篇 |
2009年 | 17篇 |
2008年 | 58篇 |
2007年 | 59篇 |
2006年 | 64篇 |
2005年 | 57篇 |
2004年 | 57篇 |
2003年 | 59篇 |
2002年 | 45篇 |
2001年 | 20篇 |
2000年 | 22篇 |
1999年 | 14篇 |
1998年 | 5篇 |
1997年 | 6篇 |
1996年 | 6篇 |
1995年 | 3篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1991年 | 4篇 |
1990年 | 6篇 |
1989年 | 7篇 |
1988年 | 7篇 |
1987年 | 8篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 9篇 |
1983年 | 3篇 |
1982年 | 8篇 |
1981年 | 10篇 |
1980年 | 4篇 |
1979年 | 9篇 |
1978年 | 6篇 |
1977年 | 4篇 |
1976年 | 6篇 |
1975年 | 4篇 |
1974年 | 6篇 |
1973年 | 4篇 |
1936年 | 3篇 |
排序方式: 共有987条查询结果,搜索用时 31 毫秒
921.
The ruthenium-catalyzed alkenylation of C-H bonds with alkenylboronates has been explored for a series of aromatic ketones. The coupling reaction of pivalophenone (1) with 2-isopropenyl-5,5-dimethyl[1,3,2]dioxaborinane (2) gave the corresponding isopropenylation product in 73% yield. In the case of the reaction of a sterically congested alkenylboronate, such as 2-methylpropenylboronate (8), the yield was decreased slightly. When beta-styrylboronates were used, the corresponding coupling products were obtained in good yields. The reaction of acetophenone with alpha-styrylboronate afforded the corresponding 1:1 coupling product, exclusively. 相似文献
922.
Mitsunori Oda Kazutaka Ogura Sayaka Kishi Kunihide Fujimori Noritaka Abe 《Tetrahedron letters》2007,48(26):4471-4475
The title azaazulene 3 was synthesized either by reaction of tropone with N-{(2-pyridyl)acetyl}pyridinium iodide in the presence of ammonium acetate or by palladium-catalyzed cross-coupling between 2-halo-1-azaazulene and 2-substituted pyridine. The compound shows relatively stronger basicity compared with 2,2′-bipyridyl. While 3 showed no emission from the S1 state but from the S2 state like azulene does, the protonated species of 3 exhibited emission from the S1 state. Cationic metal-dependent absorption and emission relating to complexation were also studied. 相似文献
923.
Nakano M Nakagawa N Kishi R Ohta S Nate M Takahashi H Kubo T Kamada K Ohta K Champagne B Botek E Morita Y Nakasuji K Yamaguchi K 《The journal of physical chemistry. A》2007,111(37):9102-9110
Adopting density functional theory and a hybrid exchange-correlation functional, the relationship between the second hyperpolarizability (gamma) and the diradical character has been investigated for diphenalenyl-based compounds containing different heterocyclic five-membered central rings (C(4)H(4)X, where X = NH, PH, O, S, CH(2), SiH(2), BH, GaH, C=O, C=S, and C=Se) or substituted by donor (NH(2))/acceptor(NO(2)) groups. It turns out that these structural modifications can tune the diradical character from 0.0 to 0.968 and lead to variations of gamma over more than 1 order of magnitude, demonstrating the controllability of gamma in this family of compounds. In particular, when the central ring is strongly aromatic, the diradical character is larger than 0.7, which is associated with pretty large gamma values except for almost the pure diradical case (y approximately 1). On the other hand, when the aromaticity decreases--or the antiaromaticity increases--the diradical character and the second hyperpolarizability get smaller. These relationships are correlated to structural (bond length alternation) and charge distribution (charge transfer between the phenalenyl rings and the central ring) properties, which account for the relative importance of the resonance diradical, zwitterionic, and quinoid forms. Therefore, the diradical character and the second hyperpolarizability can be controlled by the aromaticity of the ring while the paradigm of the enhancement of gamma for intermediate diradical character is globally verified. Then, upon introducing donor groups, the zwitterionic character increases, leading to closed-shell species and small second hyperpolarizabilities. In the case of substitution by acceptor groups, the charge transfer is reduced but the diradical character and the second hyperpolarizability hardly changes. 相似文献
924.
Ohta S Nakano M Kubo T Kamada K Ohta K Kishi R Nakagawa N Champagne B Botek E Takebe A Umezaki SY Nate M Takahashi H Furukawa S Morita Y Nakasuji K Yamaguchi K 《The journal of physical chemistry. A》2007,111(18):3633-3641
We have investigated the static second hyperpolarizabilities (gamma) of the singlet diradical systems with intermediate diradical character involving phenalenyl radicals connected by acetylene and vinylene pi-conjugated linkers, 1 and 2, using the hybrid density functional theory. For comparison, we have also examined the gamma values of the closed-shell and pure diradical systems with almost the same molecular size as 1 and 2. In agreement with our previous prediction of the diradical character dependence of gamma, it turns out that the gamma values of 1 and 2 are significantly enhanced compared to those of the closed-shell and pure diradical systems. In the present case, distinct differences in gamma values are not observed between the two pi-conjugated linkers, though the diradical character is found to depend on the kind of linker. Furthermore, we have investigated the spin multiplicity effect on gamma. Changing from the singlet to the triplet state, the gamma values of the systems with intermediate diradical character in the singlet state are quite reduced, though those of the pure diradical systems are hardly changed. Such spin multiplicity dependence of gamma is understood by considering the difference of diradical character between their singlet states together with the Pauli principle. The present results provide a possibility of a novel control scheme of gamma for phenalenyl radical systems involving pi-conjugated linkers by adjusting the diradical character through the change of the linked position of pi-conjugated linkers and the spin multiplicity. 相似文献
925.
Photografting and patterning of oligonucleotides on benzophenone-modified boron-doped diamond 总被引:1,自引:0,他引:1
Szunerits S Shirahata N Actis P Nakanishi J Boukherroub R 《Chemical communications (Cambridge, England)》2007,(27):2793-2795
Irradiation of a patterned benzophenone-terminated boron-doped diamond (BDD) surface with UV light (lambda = 350 nm) in the presence of a 15(mer) oligonucleotide resulted in the covalent linking of the DNA strand to the BDD interface. 相似文献
926.
927.
Harada Y Nakanishi J Fujihara H Tobisu M Fukumoto Y Chatani N 《Journal of the American Chemical Society》2007,129(17):5766-5771
The Rh-catalyzed reaction of alkynes with 2-bromophenylboronic acids involves carbonylative cyclization to give indenones. The key steps in the reaction involve the addition of an arylrhodium(I) species to an alkyne and the oxidative addition of C-Br bonds on the adjacent phenyl ring to give vinylrhodium(I) species II. The regioselectivity depends on both the electronic and the steric nature of the substituents on the alkynes. A bulky group and an electron-withdrawing group favor the -position of indenones. In the case of silyl- or ester-substituted alkynes, the regioselectivity is extremely high. The selectivity increases in the order SiMe3 > COOR > aryl > alkyl. The reaction of norbornene with 2-bromophenylboronic acids under 1 atm of CO gives the corresponding indanone derivative. The reaction of alkynes with 2-bromophenylboronic acids under nitrogen gives naphthalene derivatives, in which two molecules of alkynes are incorporated. A vinylrhodium complex similar to II can also be generated by a different route by employing 2-bromophenyl(trimethylsilyl)acetylene and arylboronic acids in the presence of Rh(I) complex as the catalyst, resulting in the formation of indenones. The reaction of 1-(2-bromophenyl)-hept-2-yn-1-one with PhB(OH)2 in the presence of Rh(I) complex also resulted in carbonylative cyclization to give an indan-1,3-dione derivative. 相似文献
928.
Two-electron oxidation of [{Pc(OEt)8}2TbIII]- [Pc(OEt)8=dianion of 2,3,9,10,16,17,23,24-octaethoxyphthalocyanine], which leads to a longitudinal contraction of the coordination space of the single-4f-ionic single-molecule magnet (SMM), resulted in a significant increase of the magnetization-reversal barrier energy and a remarkable upward temperature shift of chi' peaks and chi'T drops. This is the first evidence that the dynamic magnetism of 4f SMMs can be controlled by a redox reaction on the ligand side without introducing any additional magnetic site or spin system. 相似文献
929.
Takahashi H Tanabe K Aketa M Kishi R Furukawa S Nakano M 《The Journal of chemical physics》2007,126(8):084508
The Beckmann rearrangement of acetone oxime promoted by proton transfers in the supercritical water has been investigated by means of the hybrid quantum mechanical/molecular mechanical approach combined with the theory of energy representation (QM/MM-ER) recently developed. The transition state (TS) structures have been explored by ab initio calculations for the reaction of hydrated acetone oxime on the assumption that the reaction is catalyzed by proton transfers along the hydrogen bonds connecting the solute and the solvent water molecules. Up to two water molecules have been considered as reactants that take part in the proton transfers. As a result of the density functional theory calculations with B3LYP functional and aug-cc-pVDZ basis set, it has been found that participation of two water molecules in the reaction reduces the activation free energy by -12.3 kcal/mol. Furthermore, the QM/MM-ER simulations have revealed that the TS is more stabilized than the reactant state in the supercritical water by 2.7 kcal/mol when two water molecules are involved in the reaction. Solvation free energies of the reactant and the TS have been decomposed into terms due to the electronic polarization of the solute, electron density fluctuation, and others to elucidate the origin of the stabilization of the TS as compared with the reactant. It has been revealed that the promotion of the chemical reaction due to the hydration mainly originates from the interaction between the nonpolarized solute and the solvent water molecules at the supercritical state. 相似文献
930.
The evolution of the electronic structure of molecular aggregates is investigated using anion photoelectron (PE) spectroscopy for anionic clusters of anthracene (Ac) and its alkyl derivatives: 1-methylanthracene (1MA), 2-methylanthracene (2MA), 9-methylanthracene (9MA), 9,10-dimethylanthracene (DMA), and 2-tert-butylanthracene (2TBA). For their monomer anions (n=1), electron affinities are confined to the range from 0.47 to 0.59 eV and are well reproduced by density functional theory calculations, showing the isoelectronic character of these molecules. For cluster anions (n=2-100) of Ac and 2MA, two types of isomers I and II coexist over a wide size range: isomers I and II-1 (4< or =n<30) or isomers I and II-2 (n> or = approximately 40 for Ac and n> or = approximately 55 for 2MA). However, for the other alkyl-substituted Ac cluster anions (i.e., 1MA, 9MA, DMA, and 2TBA), only isomer I is exclusively formed, and neither isomer II-1 nor II-2 is observed. The vertical detachment energies (VDEs) of isomer I in all the anionic clusters depend almost linearly on n(-1/3). In contrast, the VDEs of isomers II-1 (n> or =14) and II-2 (n=40-100), appeared only in Ac and 2MA cluster anions, remain constant with n and are approximately 0.5 eV lower than those of isomer I. The PE spectra revealed the characteristics of each isomer: isomer I possesses a monomeric anion core that is gradually embedded into the interior of the cluster with increasing n. On the other hand, isomers II-1 and II-2 possess a multimeric (perhaps tetrameric) anion core, but they differ in the number of layers from which they are made up; monolayer (isomer II-1) and multilayers (isomer II-2) of a two-dimensionally ordered, finite herringbone-type structure, in which electron attachment produces only little geometrical rearrangement. Moreover, the agreement of the constant VDEs of isomer II-2 with the bulk data demonstrates the largely localized nature of the electronic polarization around the excess charge in a crystal-like environment, where about 50 molecules provide a charge stabilization energy comparable to the bulk. 相似文献