全文获取类型
收费全文 | 4184篇 |
免费 | 104篇 |
国内免费 | 21篇 |
专业分类
化学 | 2953篇 |
晶体学 | 43篇 |
力学 | 49篇 |
数学 | 192篇 |
物理学 | 1072篇 |
出版年
2023年 | 24篇 |
2022年 | 25篇 |
2021年 | 43篇 |
2020年 | 52篇 |
2019年 | 64篇 |
2018年 | 47篇 |
2017年 | 32篇 |
2016年 | 74篇 |
2015年 | 78篇 |
2014年 | 85篇 |
2013年 | 184篇 |
2012年 | 193篇 |
2011年 | 252篇 |
2010年 | 121篇 |
2009年 | 149篇 |
2008年 | 218篇 |
2007年 | 217篇 |
2006年 | 225篇 |
2005年 | 184篇 |
2004年 | 172篇 |
2003年 | 159篇 |
2002年 | 176篇 |
2001年 | 132篇 |
2000年 | 106篇 |
1999年 | 69篇 |
1998年 | 51篇 |
1997年 | 56篇 |
1996年 | 55篇 |
1995年 | 42篇 |
1994年 | 53篇 |
1993年 | 62篇 |
1992年 | 74篇 |
1991年 | 58篇 |
1990年 | 50篇 |
1989年 | 57篇 |
1988年 | 43篇 |
1987年 | 56篇 |
1986年 | 47篇 |
1985年 | 55篇 |
1984年 | 51篇 |
1983年 | 39篇 |
1982年 | 27篇 |
1981年 | 41篇 |
1980年 | 30篇 |
1979年 | 48篇 |
1978年 | 40篇 |
1977年 | 25篇 |
1976年 | 31篇 |
1975年 | 24篇 |
1974年 | 28篇 |
排序方式: 共有4309条查询结果,搜索用时 15 毫秒
161.
162.
163.
Matsuo Y Tahara K Sawamura M Nakamura E 《Journal of the American Chemical Society》2004,126(28):8725-8734
Selective penta-addition of a methylcopper reagent followed by addition of a phenylcopper reagent to a suitably modified synthetic intermediate results in creation of 40pi-electron systems-hoop- and bowl-shaped cyclic benzenoid compounds, [10]cyclophenacene, and dibenzo-fused corannulene derivatives. The 40pi-electron cyclophenacene derivatives have been found to be chemically stable, yellow-colored, luminescent (560 nm), and EPR-silent. X-ray crystallographic analysis provided precision structural data sets. The dibenzo-fused corannulene derivatives exhibit blue-green (460 nm) to red (649 nm) fluorescence. 相似文献
164.
Hiraoka K Asakawa Y Kawashima Y Okazaki S Nakamura M Yamamoto Y Takamizawa A 《Rapid communications in mass spectrometry : RCM》2004,18(20):2437-2442
The effect of the presence of foreign salts (NaCl, aerosol OT, tetra-n-hexylammonium bromide, and CH3COONH4) on the formation of gaseous ions for electrospray (ES) and laser spray (LS) was studied in the positive and negative modes of operations. The ion signals for amino acids show sudden decrease with the concentration of foreign salts greater than 10(-5) M for both ES and LS. When the surface-active counter ions were added, the signal intensities showed a marked decrease for both ES and LS. This may be due to the enrichment of the surface-active counter ions on the surface of the charged droplets. When CH3COONH4 was added to an aqueous solution of 10(-6) M lysozyme chloride, an increase of the signal intensities for (lysozyme+nH)n+ and a decrease in the values of n were observed. The decrease in n may be due to the salt formation of (lysozyme+nH)n+ with the negative acetate ion leading to the reduction of positive charges. 相似文献
165.
Kondo M Irie Y Shimizu Y Miyazawa M Kawaguchi H Nakamura A Naito T Maeda K Uchida F 《Inorganic chemistry》2004,43(20):6139-6141
Reversible construction of a nanoporous framework from a nonporous framework has been found in the zinc(II) coordination polymer with 4,4'-oxybis(benzoate) (oba). [Zn(2)(oba)(2)(dmf)(2)].2DMF (1), which has 1 nm scale channels, transforms to the nonporous coordination polymer [Zn(oba)(H(2)O)] (2) with the loss of the open framework. Compound 2 on treatment with DMF reversibly yields nanoporous compound 1. 相似文献
166.
Itaka K Kanayama N Nishiyama N Jang WD Yamasaki Y Nakamura K Kawaguchi H Kataoka K 《Journal of the American Chemical Society》2004,126(42):13612-13613
An siRNA nanocarrier formed through self-assembly of PEG-based block catiomer possessing two distinct amino groups with different pKa values in a side chain was developed. This design provided the carrier with a sufficient siRNA complexation and an assumed buffering capacity in the endosomes, allowing it to exhibit remarkable gene knockdown abilities as well as sufficient serum tolerability. 相似文献
167.
Knöevenagel-type reaction between diketene and aldehydes proceeded in the presence of Ti(O-i-Pr)4. This reaction proceeded via titanium enolate derived from Ti(O-i-Pr)4 and diketene. As for the stereoselectivity of the products, E-isomers were produced predominantly in the case of aromatic aldehydes. 相似文献
168.
169.
[reaction: see text] Substituted cyclopentadienone acetals (CPDAs) were synthesized by a thermal or palladium-catalyzed [3 + 2] cycloaddition reaction of a substituted cyclopropenone acetal to an electron-deficient acetylene. The synthesis afforded di-, tri-, and tetra-substituted CPDAs of considerable structural varieties that undergo Diels-Alder reaction to produce bicyclo[2.2.1]heptenes. 相似文献
170.
Hwang IW Kamada T Ahn TK Ko DM Nakamura T Tsuda A Osuka A Kim D 《Journal of the American Chemical Society》2004,126(49):16187-16198
meso-Pyridine-appended zinc(II) porphyrins Mn and their meso-meso-linked dimers Dn assemble spontaneously, in noncoordinating solvents such as CHCl3, into tetrameric porphyrin squares Sn and porphyrin boxes Bn, respectively. Interestingly, formation of Bn from Dn proceeds via homochiral self-sorting assembly, which has been verified by optical separations of B1 and B2. Optically pure enantiomers of B1 and B2 display strong Cotton effects in the CD spectra, which reflect the length of the pyridyl arm, thus providing evidence for the exciton coupling between the noncovalent neighboring porphyrin rings. Excitation energy migration processes within Bn have been investigated by steady-state and time-resolved spectroscopic methods in conjunction with polarization anisotropy measurements. Both the pump-power dependence on the femtosecond transient absorption and the transient absorption anisotropy decay profiles are directly associated with the excitation energy migration process within the Bn boxes, where the exciton-exciton annihilation time and the polarization anisotropy rise time are well described in terms of the F?rster-type incoherent energy hopping model by assuming a number of hopping sites of N = 4 and an exciton coherence length of L = 2. Consequently, the excitation energy hopping rates between the zinc(II) diporphyrin units have been estimated for B1 (48 ps)(-1), B2 (98 +/- 3 ps)(-1), and B3 (361 +/- 6 ps)(-1). Overall, the self-assembled porphyrin boxes Bn serve as a well-defined three-dimensional model for the light-harvesting complex. 相似文献