全文获取类型
收费全文 | 17418篇 |
免费 | 2656篇 |
国内免费 | 1914篇 |
专业分类
化学 | 12533篇 |
晶体学 | 186篇 |
力学 | 1192篇 |
综合类 | 135篇 |
数学 | 2019篇 |
物理学 | 5923篇 |
出版年
2024年 | 55篇 |
2023年 | 331篇 |
2022年 | 537篇 |
2021年 | 604篇 |
2020年 | 626篇 |
2019年 | 661篇 |
2018年 | 529篇 |
2017年 | 537篇 |
2016年 | 760篇 |
2015年 | 760篇 |
2014年 | 950篇 |
2013年 | 1166篇 |
2012年 | 1526篇 |
2011年 | 1538篇 |
2010年 | 1051篇 |
2009年 | 930篇 |
2008年 | 1081篇 |
2007年 | 975篇 |
2006年 | 973篇 |
2005年 | 789篇 |
2004年 | 599篇 |
2003年 | 543篇 |
2002年 | 543篇 |
2001年 | 458篇 |
2000年 | 343篇 |
1999年 | 360篇 |
1998年 | 288篇 |
1997年 | 269篇 |
1996年 | 297篇 |
1995年 | 234篇 |
1994年 | 203篇 |
1993年 | 159篇 |
1992年 | 169篇 |
1991年 | 173篇 |
1990年 | 128篇 |
1989年 | 123篇 |
1988年 | 81篇 |
1987年 | 70篇 |
1986年 | 80篇 |
1985年 | 60篇 |
1984年 | 54篇 |
1983年 | 44篇 |
1982年 | 32篇 |
1981年 | 31篇 |
1980年 | 29篇 |
1978年 | 24篇 |
1977年 | 25篇 |
1976年 | 23篇 |
1974年 | 20篇 |
1973年 | 26篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
81.
The preparation of functionalized 4,5,6,7-tetrahydroisoindole via a traceless solid-phase sulfone linker strategy is described. Thermolytic extrusion of SO(2) from polymer-bound 3-(phenylsulfonyl)-3-sulfolene (7) generated polymer-bound 2-(phenylsulfonyl)-1,3-butadiene (9) in situ which underwent Diels--Alder cycloaddition with various dienophiles to furnish vinyl sulfone resins 10-14. To complete a traceless linker cleavage strategy, (p-tolysulfonyl)methyl isocyanide or ethyl isocyanoacetate was employed to react with the vinyl sulfone moiety to liberate functionalized 4,5,6,7-tetrahydroisoindole products from the resin. Using this chemistry, nine tetrahydroisoindole derivatives (6, 15-22) were prepared in 32-41% overall yields from polystyrene/divinylbenzene sulfinate 1. 相似文献
82.
[reaction: see text] A facile synthesis of highly functionalized 3-aminofuran derivatives by the multicomponent reactions of thiazolium salts, aldehydes, and DMAD is described. 相似文献
83.
Rong Chen Yu-Hui Cheng Lei Liu Xiao-Song Li Qing-Xiang Guo 《Research on Chemical Intermediates》2002,28(1):41-48
MP2/6-31+G* calculations were performed on the cation- complexes of ethylene, cyclobutadiene and benzene with a number of atomic cations. It was found that except B+ all the atomic cations form -type cation- complexes with ethylene. On the other hand, with cyclobutadiene Li+, N+, Na+, P+ and K+ form -type complexes, whereas H+, F+, and Cl+ form covalent -type complexes. With benzene Li+, B+, Na+, Al+, and K+ form -type complexes whereas H+, F+, and Cl+ form -type complexes. It was concluded that the driving force to form the -type complex is chemical bonding, and that for metal cations to form -type complexes is non-covalent interaction. 相似文献
84.
85.
Krasnovsky AA Cheng P Blankenship RE Moore TA Gust D 《Photochemistry and photobiology》1993,57(2):324-330
Measurements of pigment triplet-triplet absorption, pigment phosphorescence and photosensitized singlet oxygen luminescence were carried out on solutions containing monomeric bacteriochlorophylls (Bchl) c and d, isolated from green photosynthetic bacteria, and their magnesium-free and farnesyl-free analogs. The energies of the pigment triplet states fell in the range 1.29-1.34 eV. The triplet lifetimes in aerobic solutions were 200-250 ns; they increased to 280 +/- 70 microseconds after nitrogen purging in liquid solutions and to 0.7-2.1 ms in a solid matrix at ambient or liquid nitrogen temperatures. Rate constants for quenching of the pigment triplet state by oxygen were (2.0-2.5) x 10(9) M-1 s-1, which is close to 1/9 of the rate constant for diffusion-controlled reactions. This quenching was accompanied by singlet oxygen formation. The quantum yields for the triplet state formation and singlet oxygen production were 55-75% in air-saturated solutions. Singlet oxygen quenching by ground-state pigment molecules was observed. Quenching was the most efficient for magnesium-containing pigments, kq = (0.31-1.2) x 10(9) M-1 s-1. It is caused mainly by a physical process of singlet oxygen (1O2) deactivation. Thus, Bchl c and d and their derivatives, as well as chlorophyll and Bchl a, combine a high efficiency of singlet oxygen production with the ability to protect photochemical and photobiological systems against damage by singlet oxygen. 相似文献
86.
Tandem mass spectrometric studies show that SiH+5 is formed in bimolecular reactions of SiH4 and NH+2, C2H+3, C2H+6 and C3H+8 ions. The dependence of the reaction cross sections on ion energy indicates the formation of SiH+5 from NH+2, C2H+3, and C2H+6 to be exothermic reactions, while formation from C3H+8 is endothermic. Using known thermochemical data, these facts permit the assignment of 150 and 156 kcal/mole to the lower and upper limits of the proton affinity of monosilane. 相似文献
87.
Weakly bound linear and bent dimers, FH—X (where X = CO, OC, CNH, NCH, N2O and ON2), are investigated using the DFT B3LYP and ab initio MP2 methods with the same basis sets (6–311++G(3df,2pd)). The strengths of the H—C or H—N H‐bonds in dimers FH—CO, FH—CNH, and FH—N2O are compared with those of the H—O or H—N H‐bonds in dimers FH—OC, FH—NCH, and FH—ON2. The results obtained for the H‐bond distances, the elongation effect of the HF bond, the red shift of the HF stretching frequency, and the energy difference between the dimer and the charge transfer reveal that the H‐bonds of the first group of dimers are stronger than those of the second. The Gibbs energies calculated for the six dimer formations indicate that the weakly bound dimers are unstable at room temperature (T = 298 K) (FH—X's → FH + X's, ΔG < 0). 相似文献
88.
UB3LYP/6-31G(d) and ROMP2/6-311++G(d,2p) methods were used to calculate the Si-X bond dissociation energies (BDEs) of a number of para-substituted aromatic silanes (4-Y-C(6)H(4)-SiH(2)X, where X = H, F, Cl, or Li). It was found that the substituent effect on the Si-H BDE of 4-Y-C(6)H(4)-SiH(3) was small, as the slope (rho(+)()) of the BDE- regression was only 0.09 kJ/mol. In comparison, the substituent effect on the Si-F BDE of 4-Y-C(6)H(4)-SiH(2)F was much stronger, whose rho(+ )()value was -2.34 kJ/mol. The substituent effect on the Si-Cl BDE of 4-Y-C(6)H(4)-SiH(2)Cl was also found to be strong with a rho(+)() value of -1.70 kJ/mol. However, the substituent effect on the Si-Li BDE of 4-Y-C(6)H(4)-SiH(2)Li was found to have a large and positive slope (+9.12 kJ/mol) against. The origin of the above remarkably different substituent effects on the Si-X BDEs was found to be associated with the ability of the substituent to stabilize or destabilize the starting material (4-Y-C(6)H(4)-SiH(2)X) as well as the product (4-Y-C(6)H(4)-SiH(2)* radical) of the homolysis. Therefore, the direction and magnitude of the effects of Y-substituents on the Z-X BDEs in compounds such as 4-YC(6)H(4)Z-X should have some important dependence on the polarity of the Z-X bond undergoing homolysis. This conclusion was in agreement with that from earlier studies (for example, J. Am. Chem. Soc. 1991, 113, 9363). However, it indicated that the proposal from a recent work (J. Am. Chem. Soc. 2001, 123, 5518) was unfortunately not justified. 相似文献
89.
The photochemical reaction of Re2(CO)10 with thiophene in hexane solution was investigated under vacuum. Three rhenium clusters: H2Re3(CO)12, HRe3(CO)14 and Re3(CO)14(OH)4, were isolated. The structure of Fellmann-Kaesz cluster Complex HRe3(CO)14 was determined by use of the X-ray diffraction method. The three rhenium atoms form a plane of symmetry and L: Re1Re2Re3 is 107°. The ten carbonyl groups bonded to the two terminal rhenium atoms Re1 and Re3, are staggered with respect to the central rhenium atoms. The bond lengths are 3.10 Å for Re2-Re3 and 3.34 Å for Re1-Re2. The bridging hydride is between Re1 and Re2. 相似文献
90.
T. C. E. Cheng 《The Journal of the Operational Research Society》1991,42(2):177-181
This paper considers the problem of optimal assignment of total-work-content due-dates to n jobs and of sequencing them on a single machine to minimize an objective function depending on the assigned due-date multiple value and maximum tardiness penalty. It is shown that both the earliest due-date and shortest processing time orders yield an optimal sequence. A simple analytical solution method is presented to find the optimal due-dates. After the theoretical treatment an illustrative example is presented for discussion. 相似文献