全文获取类型
收费全文 | 1882篇 |
免费 | 71篇 |
国内免费 | 14篇 |
专业分类
化学 | 1481篇 |
晶体学 | 10篇 |
力学 | 12篇 |
数学 | 105篇 |
物理学 | 359篇 |
出版年
2023年 | 9篇 |
2022年 | 16篇 |
2021年 | 20篇 |
2020年 | 14篇 |
2019年 | 39篇 |
2018年 | 27篇 |
2017年 | 11篇 |
2016年 | 24篇 |
2015年 | 52篇 |
2014年 | 40篇 |
2013年 | 112篇 |
2012年 | 112篇 |
2011年 | 116篇 |
2010年 | 68篇 |
2009年 | 65篇 |
2008年 | 119篇 |
2007年 | 125篇 |
2006年 | 135篇 |
2005年 | 121篇 |
2004年 | 109篇 |
2003年 | 74篇 |
2002年 | 88篇 |
2001年 | 42篇 |
2000年 | 39篇 |
1999年 | 21篇 |
1998年 | 11篇 |
1997年 | 15篇 |
1996年 | 23篇 |
1995年 | 7篇 |
1994年 | 9篇 |
1993年 | 19篇 |
1992年 | 14篇 |
1991年 | 14篇 |
1990年 | 17篇 |
1989年 | 11篇 |
1988年 | 12篇 |
1987年 | 8篇 |
1986年 | 12篇 |
1985年 | 42篇 |
1984年 | 20篇 |
1983年 | 11篇 |
1982年 | 20篇 |
1981年 | 16篇 |
1980年 | 12篇 |
1979年 | 13篇 |
1978年 | 8篇 |
1977年 | 12篇 |
1976年 | 7篇 |
1975年 | 8篇 |
1973年 | 15篇 |
排序方式: 共有1967条查询结果,搜索用时 15 毫秒
21.
Five new natural labdane-type diterpenoids (5-9), designated leoheteronins A-E, together with four known diterpenoids (1-4), two phytosterols as a mixture of beta-sitosterol and stigmasterol, and the flavone genkwanin (10) were isolated from the aerial parts of Leonurus heterophyllus SW. (Lamiaceae) collected in northern Vietnam. Compound 1 was isolated for the first time from a Leonurus species, and 10 is considered to be a chemotaxonomic marker of the Leonurus genus. Their structures were determined using spectroscopic analyses. 相似文献
22.
Kazuhiro Kobayashi Atsushi Takanohashi Kenichi Hashimoto Osamu Morikawa Hisatoshi Konishi 《Tetrahedron》2006,62(44):10379-10382
A facile synthetic method for 4,5-diaminopyrrolo[1,2-a]quinoline derivatives has been developed. Treatment of 2-(pyrrol-1-yl)benzaldehydes with secondary amine hydrochloride/NaI/TMSCl/Et3N in the presence of an isocyano compound leads to the formation of 4-alkyl(or aryl)amino-5-dialkylaminopyrrolo[1,2-a]quinolines. 相似文献
23.
Tsuyoshi Otsuka 《Tetrahedron letters》2004,45(12):2643-2647
A novel and efficient oxidative dimerization of 1-naphthols 1 with dioxygen in the presence of several semiconductors including SnO2, ZrO2, and activated charcoal as catalytic mediators took place selectively to give the corresponding 2,2′-binaphthols 2 or 2,2′-binaphthyl-1,1′-quinones 3 in excellent yields without light irradiation. Among these semiconductors, the catalytic activity of SnO2 could be fully restored by appropriate reactivation treatment after oxidation. The products 2 and 3 should be useful as synthetic intermediates for natural binaphthyls. 相似文献
24.
Kazuhiro Endo Hideo Ihara Kazuhiro Watanabe Shun-Ichi Gonda 《Journal of solid state chemistry》1982,44(2):268-272
X-Ray photoelectron spectra of TiS3 with a one-dimensional structure were measured. TiS3 may be regarded as Ti4+(S2)2?S2? with pairs of S atoms (S2) and isolated S atoms. The spectra of the sulfur core-levels are assigned by comparison with those of TiS2, where all S atoms are largely separated. The binding energy of the S2 pairs is found to be 1.4 eV higher than that of the isolated S atoms, which is consistent with the larger negative charge of the isolated atoms. The structures of the valence band of TiS3 are discussed in terms of a molecular orbital scheme for the S2 pairs. 相似文献
25.
Soto-Chinchilla JJ Gámiz-Gracia L García-Campaña AM Imai K García-Ayuso LE 《Journal of chromatography. A》2005,1095(1-2):60-67
The determination of seven sulfonamides by means of HPLC with chemiluminescence detection is proposed for the first time. The analytes are derivatized with fluorescamine, separated and subsequently they participate in the post-column chemiluminescence (CL) peroxyoxalate system using imidazole as a catalyst. Among the different peroxyoxalates tested, bis[4-nitro-2-(3,6,9-trioxadecyloxycarbonyl)phenyl] oxalate provides higher sensitivities and stabilities, avoiding precipitation problems. A rigorous optimization of the significant variables by means of experimental designs has been developed in order to reconcile the chromatographic conditions with the CL reaction. The method provides detection limits in the low microgl(-1) range and has been satisfactorily applied to the analysis of spiked raw milk samples. 相似文献
26.
Staphylionosides A-K: megastigmane glucosides from the leaves of Staphylea bumalda DC 总被引:1,自引:0,他引:1
Chemical investigation of leaves of Staphylea bumalda DC., collected in the suburbs of Hiroshima City, afforded 11 new megastigmane glucosides, named staphylionosides A-K (3-13), along with two known megastigmane glucosides (1, 2). The relative structures were elucidated from spectroscopic evidence, and the absolute structures of the aglycones were determined by means of the combination of beta-D-glucosylation-induced shift-trends and the modified Mosher's method. 相似文献
27.
Itoh T Nagata K Yokoya M Miyazaki M Kameoka K Nakamura S Ohsawa A 《Chemical & pharmaceutical bulletin》2003,51(8):951-955
Chiral 1-substituted isoquinoline derivatives, which were obtained by the reaction using alanine derivatives as chiral auxiliaries, were transformed to (S)-2,3,9,10,11-pentamethoxyhomoprotoberberine (7) and a synthetic intermediate for O-methylkreysigine (9) in good yields and high stereoselectivity. The corresponding chiral allyl derivative of isoquinoline was transformed to a pyrrolidinoisoquinoline (16) in a highly enantioselective manner. 相似文献
28.
From the leaves of Alangium paltanifolium var. platanifolium, collected in Fukuoka Prefecture, twelve further megastigmane glycosides were isolated. Seven of them, named platanionosides D-J (1-7), were found to be new compounds. Their structures were elucidated from spectroscopic evidence and their absolute structures were determined from beta-D-glucosylation-induced shift trends of 13C-NMR and by application of a modified Mosher's method. 相似文献
29.
Kawasaki H Sasaki A Kawashima T Sasaki S Kakehashi R Yamashita I Fukada K Kato T Maeda H 《Langmuir : the ACS journal of surfaces and colloids》2005,21(13):5731-5737
Lyotropic phase behavior of the nonionic and the half-ionized oleyldimethylamine oxide (OlDMAO)/water systems was investigated using polarized light microscopy, small-angle X-ray diffraction, and differential scanning calorimetry. Nonionic OlDMAO formed isotropic micellar solution, nematic, hexagonal, cubic, and lamellar liquid crystalline phases as the surfactant concentration increased. In contrast, half-ionized OlDMAO (i.e., 1:1 mixture of the nonionic and the protonated species) had a greater tendency to form bilayer structures, and the phase diagram became quite similar to those of double-chained ionic surfactants rather than single-chained ones, despite the introduction of positive charges to the nonionic one. The preference of the bilayer structures in the half-ionized OlDMAO was interpreted in terms of the dimers stabilized by the hydrogen bond between the nonionic and protonated species. For alkyldimethylamine oxides with a saturated hydrocarbon chain (CnDMAO, chain length: n = 14, 16, and 18), the phase sequence of lyotropic liquid crystals was hardly affected by the protonation, but an elongation of the cylinders of the hexagonal phase was observed for the half-ionized C14DMAO. Consequently, it can be considered that the dominant bilayer formation of the half-ionized OlDMAO is attributed to the combined effect of the hydrogen-bonded dimer formation and the cis-double-bond configuration of the alkyl chain. 相似文献
30.
Hamao Umezawa Tomohisa Takita Yukio Sugiura Masami Otsuka Susumu Kobayashi Masaji Ohno 《Tetrahedron》1984,40(3):501-509
Biosynthetic intermediates and synthetic analogues of bleomycin (BLM) have been investigated for their metal binding, dioxygen activation, and DNA cleavage. Molecular O2 was activated by the Fe(II) complex of a synthetic model ligand. Nucleotide sequence specificities in DNA cleavage by the BLM-Fe(II) and deglyco-BLM-Fe(II) complexes were almost identical. It has been shown that (1) the β-aminoalanine-pyrimidine-β-hydroxyhistidine portion of BLM is essential for the metal binding and dioxygen activation and (2) the bithiazole moiety contributes to the specific binding to guanine base of DNA. 相似文献