全文获取类型
收费全文 | 28214篇 |
免费 | 1485篇 |
国内免费 | 5167篇 |
专业分类
化学 | 32322篇 |
晶体学 | 319篇 |
力学 | 54篇 |
综合类 | 245篇 |
数学 | 19篇 |
物理学 | 1907篇 |
出版年
2024年 | 26篇 |
2023年 | 262篇 |
2022年 | 448篇 |
2021年 | 801篇 |
2020年 | 828篇 |
2019年 | 852篇 |
2018年 | 742篇 |
2017年 | 881篇 |
2016年 | 1070篇 |
2015年 | 1001篇 |
2014年 | 1195篇 |
2013年 | 2556篇 |
2012年 | 1961篇 |
2011年 | 1549篇 |
2010年 | 1357篇 |
2009年 | 1583篇 |
2008年 | 1710篇 |
2007年 | 1860篇 |
2006年 | 1748篇 |
2005年 | 1658篇 |
2004年 | 1531篇 |
2003年 | 1252篇 |
2002年 | 1689篇 |
2001年 | 810篇 |
2000年 | 748篇 |
1999年 | 613篇 |
1998年 | 488篇 |
1997年 | 515篇 |
1996年 | 471篇 |
1995年 | 443篇 |
1994年 | 375篇 |
1993年 | 318篇 |
1992年 | 307篇 |
1991年 | 220篇 |
1990年 | 168篇 |
1989年 | 186篇 |
1988年 | 135篇 |
1987年 | 87篇 |
1986年 | 64篇 |
1985年 | 62篇 |
1984年 | 67篇 |
1983年 | 33篇 |
1982年 | 47篇 |
1981年 | 36篇 |
1980年 | 26篇 |
1979年 | 22篇 |
1978年 | 24篇 |
1977年 | 7篇 |
1976年 | 8篇 |
1973年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
41.
A highly efficient substitution of the vinyl fluoride of perfluoroketene dithioacetals was achieved using trimethylsilylacetate to give 2-perfluoroalkyl succinic acid derivatives and 2-trifluoromethyl succinimides. This chain process was initiated by a catalytic amount of fluoride salt, whereas reaction failed with the corresponding lithium enolate. 相似文献
42.
Jing Lin 《Tetrahedron letters》2004,45(1):103-106
Bisbinaphthyl-based macrocycles are found to carry out enantioselective fluorescent recognition of α-amino acid derivatives. It is observed that one enantiomer of a N-protected phenyl glycine can increase the fluorescence intensity of the binaphthyl fluorophores by over 4-fold but the other enantiomer does not cause much fluorescence enhancement. This highly enantioselective fluorescent response makes the binaphthyl macrocycles practically useful for the enantioselective fluorescent recognition of the amino acid substrate. 相似文献
43.
Reaction of acetylene dicarboxaldehyde monoacetal with substituted Meldrum’s acid leads good yields in 2-pyranones-4-carboxaldehydes substituted in position 3. 相似文献
44.
A simple, efficient and highly chemoselective method for tetrahydropyranylation of alcohols and phenols has been developed by their reaction with 3,4-dihydro-2H-pyran at room temperature in the presence of a catalytic amount of polystyrene supported AlCl3. The method is also highly selective for monoprotection of symmetrical diols. 相似文献
45.
Grindstone Chemistry--a greatly evolved version of Toda’s method of grinding solids together for solvent-free chemical reactions--has been described and its usefulness illustrated by the successful application of this technique to a simplified process for conducting the multi-component Biginelli reaction for the synthesis of physiologically active tetrahydropyrimidinones. 相似文献
46.
Chin‐Ping Yang Ruei‐Shin Chen Kuei‐Hung Chen 《Journal of polymer science. Part A, Polymer chemistry》2003,41(7):922-938
To investigate the position and amount of the CF3 group affecting the coloration of polyimides (PIs), we prepared 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]hexafluoropropane ( 2 ) with four CF3 groups with 2‐chloro‐5‐nitrobenzotrifluoride and 2,2‐bis(4‐hydroxyphenol)hexafluoropropane. A series of soluble and light‐colored fluorinated PIs ( 5 ) were synthesized from 2 and various aromatic dianhydrides ( 3a – 3f ). 5a – 5f had inherent viscosities ranging from 0.80 to 1.19 dL/g and were soluble in amide polar solvents and even in less polar solvents. The glass‐transition temperatures of 5 were 221–265 °C, and the 10% weight‐loss temperatures were above 493 °C. Their films had cutoff wavelengths between 343 and 390 nm, b* values (a yellowness index) ranging from 5 to 41, dielectric constants of 2.68–3.01 (1 MHz), and moisture absorptions of 0.03–0.29 wt %. In a comparison of the PI series 6 – 8 based on 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane, 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]propane, and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane, we found that the CF3 group close to the imide group was more effective in lowering the color; this means that CF3 of 5 , 7 , and 8f was more effective than that of 6c . The color intensity of the four PI series was lowered in the following order: 5 > 7 > 6 > 8 . The PI 5f , synthesized from diamine 2 and 4,4′‐hexafluoroisopropylidenediphthalic anhydride, had six CF3 groups in a repeated segment, so it exhibited the lightest color among the four series. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 922–938, 2003 相似文献
47.
48.
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
49.
[3,3]-Sigmatropic rearrangements of allyl tetronates and allyl tetramates to give 3-allyltetronic or -tetramic acids, respectively, proceed within 20-60 min under microwave irradiation (300 W, 130-190 °C). Consecutive (homo)sigmatropic [1,5] H-shifts such as oxa-ene reactions are promoted less effectively, which allows the isolation of Claisen intermediates of sigmatropic domino sequences, in contrast to conventional heating. 相似文献
50.
Katsunari Inoue Kazuaki Kato Norimitsu Tohnai Mikiji Miyata 《Journal of polymer science. Part A, Polymer chemistry》2004,42(18):4648-4655
We studied simulations by computer graphics to estimate the steric mechanism of the asymmetric polymerization of prochiral diene monomers in channels of inclusion compounds of steroidal bile acids, such as deoxycholic acid (DCA) and cholic acid. We applied a hierarchization method to interpret the crystal structures of bile acids, clarifying that the chiral host molecules associated to form characteristic 21-helical assemblies with uneven surfaces. A detailed analysis of the uneven channels in a close-packing state indicated that there were many possible arrangements of the monomers in the channels. The plausible arrangements in the channel could explain a previous study, which showed that the polymerization in the DCA channel yielded chiral polymers with a predominant configuration from prochiral diene monomers, such as 2-methyl-trans-1,3-pentadiene. On the basis of such simulation studies of the arrangements of guest monomers in the channel, we examined a plausible steric mechanism for asymmetric inclusion polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4648–4655, 2004 相似文献