全文获取类型
收费全文 | 2586篇 |
免费 | 87篇 |
国内免费 | 13篇 |
专业分类
化学 | 1962篇 |
晶体学 | 35篇 |
力学 | 33篇 |
数学 | 173篇 |
物理学 | 483篇 |
出版年
2021年 | 24篇 |
2020年 | 27篇 |
2019年 | 46篇 |
2018年 | 35篇 |
2017年 | 22篇 |
2016年 | 54篇 |
2015年 | 44篇 |
2014年 | 60篇 |
2013年 | 155篇 |
2012年 | 132篇 |
2011年 | 150篇 |
2010年 | 103篇 |
2009年 | 84篇 |
2008年 | 143篇 |
2007年 | 127篇 |
2006年 | 122篇 |
2005年 | 133篇 |
2004年 | 111篇 |
2003年 | 108篇 |
2002年 | 94篇 |
2001年 | 33篇 |
2000年 | 25篇 |
1999年 | 33篇 |
1998年 | 27篇 |
1997年 | 35篇 |
1996年 | 22篇 |
1995年 | 20篇 |
1994年 | 36篇 |
1993年 | 31篇 |
1992年 | 39篇 |
1991年 | 28篇 |
1990年 | 15篇 |
1989年 | 23篇 |
1988年 | 18篇 |
1987年 | 17篇 |
1986年 | 24篇 |
1985年 | 24篇 |
1984年 | 44篇 |
1983年 | 25篇 |
1982年 | 31篇 |
1981年 | 28篇 |
1980年 | 22篇 |
1979年 | 29篇 |
1977年 | 22篇 |
1976年 | 31篇 |
1975年 | 29篇 |
1974年 | 26篇 |
1973年 | 25篇 |
1972年 | 19篇 |
1969年 | 17篇 |
排序方式: 共有2686条查询结果,搜索用时 15 毫秒
41.
Kengo Shamoto Atsushi Miyazaki Mika Matsukura Yuki Kobayashi Takayuki Shioiri 《合成通讯》2013,43(10):1425-1431
A nonenzymatic kinetic resolution of (±)-trans-2-arylcyclohexanols was carried out by esterification using polymer-supported N,N′-dicyclohexylcarbodiimide (DCC), dimethylaminopyridine (DMAP), and 3β-acetoxyetienic acid. The efficiency of the kinetic resolution was comparable to the enzymatic method when arylcyclohexanols bearing a condensed-aromatic ring were used. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communication® to view the free supplemental file. 相似文献
42.
Yoshinori SaitoYuriko Takashima Aya KamadaYurika Suzuki Midori SuenagaYasuko Okamoto Yoichi MatsunagaRyo Hanai Takayuki KawaharaXun Gong Motoo Tori Chiaki Kuroda 《Tetrahedron》2012,68(48):10011-10029
Root chemicals and DNA sequences were analyzed for Ligularia virgaurea collected in the northern Sichuan Province and adjacent areas of China. Thirty-eight samples were found to contain five chemotypes, two known and three new ones. From samples of the new chemotypes, 13 new compounds were isolated, including 3 sesquiterpene dimers and some rearranged eremophilanes. The DNA sequences suggested that the chemotype differentiation had a genetic origin. 相似文献
43.
The title compounds, Ph2bNO and Ph3bNO, were designed as a biradical paramagnetic host, and their chelation ability was confirmed by inclusion of a size-matched alkaline-earth metal ion. The crystal structures of [Ca(hfac)2(Ph2bNO)] and [Ba(hfac)2(Ph3bNO)] were determined, where Hhfac stands for 1,1,1,5,5,5-hexafluoropentane-2,4-dione. The solution electron paramagnetic resonance spectra showed switching behavior. Five lines were found for Ph3bNO and charecterized as the hyperfine splitting due to the two nitrogen atoms. After addition of barium(II) ion, the spectrum turned to be three lines. Removal of the barium ion recovered the five line pattern. The present system can be regarded as a reversible magnetic-coupling switch by means of a supramolecular technique. 相似文献
44.
Front Cover: Construction of a Triangle‐Shaped Trimer and a Tetrahedron Using an α‐Helix‐Inserted Circular Permutant of Cytochrome c555 (Chem. Asian J. 10/2018) 下载免费PDF全文
45.
Shota Ooi Takayuki Tanaka Kyu Hyung Park Dongho Kim Atsuhiro Osuka 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2016,128(22):6645-6649
The oxidation of 10–10′ singly linked corrole dimers with DDQ at low concentration in CHCl3 afforded meso–meso, β–β, β–β triply linked 2H‐corrole dimers (with two inner NH groups in each corrole unit), which exhibited characteristic 1H NMR and absorption spectra attributable to their nonaromatic electronic networks. These 2H‐corrole dimers were reduced with NaBH4 to aromatic 3H‐corrole dimers, which were unstable and easily oxidized back to the 2H‐corrole dimers upon exposure to air. Bis(zinc(II)) complexes of the 2H‐corrole dimers were synthesized and characterized as rare examples of nonaromatic zinc(II) corrole complexes. 相似文献
46.
Stereodivergent Synthesis and Stereochemical Reassignment of the C79–C104 Fragment of Symbiodinolide 下载免费PDF全文
Prof. Dr. Hiroyoshi Takamura Takayuki Fujiwara Yohei Kawakubo Prof. Dr. Isao Kadota Prof. Dr. Daisuke Uemura 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(6):1984-1996
We have synthesized eight possible diastereoisomers 3 a – h of the C79–C97 fragment of symbiodinolide ( 1 ) in a stereodivergent manner by utilizing a dithiane addition to the aldehyde as a key step. Comparison of the 13C NMR chemical shifts of the natural product 1 and the synthetic products 3 a – h indicated that the relative stereostructure of this fragment in symbiodinolide ( 1 ) is that represented in 3 a or f . We have stereodivergently synthesized eight possible diastereoisomers of the C94–C104 fragment 4 a – h , and we have compared their 13C NMR chemical shifts with those of the natural product, which established the relative stereochemistry of this fragment to be that described in diastereoisomers 4 a or e . By combining the stereostructural outcomes of the C79–C97 and C94–C104 fragments, we have proposed four candidate compounds of the C79–C104 fragment 2 a – d . We also synthesized diastereoisomers 2 a and b ( 2 a in the preceding article; Chem. Eur. J. 2015 , DOI: 10.1002/chem.201503880) by a Julia–Kocienski olefination and diastereoisomers 2 c and d by a Wittig reaction. By comparing the 13C NMR chemical shifts of natural symbiodinolide ( 1 ) with those of the synthetic products 2 a – d , we have reassigned the stereostructure of the C79–C104 fragment of natural product 1 to be that depicted in diastereoisomer 2 b . 相似文献
47.
48.
Takayuki MaruyamaYasuyuki Fujie Noriyuki OyaEisuke Hosaka Aki KanazawaDaisuke Tanaka Yoshiyuki HattoriJiro Motoyoshiya 《Tetrahedron》2011,67(36):6927-6933
The control of peroxyoxalate chemiluminescence (PO-CL) by the coordination of nitrogen-containing ligands and metal cations was investigated. Turning the CL off and on was done by PO-CL using 15-monoazacrown-5-tethered anthracene and alkali metal ions. CL quenching and regeneration was also observed in the separated molecular system of 15-monoazacrown-5 and the fluorophores. CL quenching by a number of ligands bearing dipicolylamino groups was evaluated by these PO-CL reactions and found to be closely related to their oxidation potentials, which is dependent on the Weller rate law for electron exchange and this provides strong support for the existence of the CIEEL PO-CL process. When Zn2+ or Cu2+ are added to the PO-CL system quenched by the ligand, N-[2-(2,2′-dipicolylamino)ethyl]aniline, CL was turned on because the electron donating ability of the ligands was modulated. This was controlled by the coordination of the studied metal ions and, therefore, this system results in CL because of host-guest interactions. 相似文献
49.
Iwao Okamoto Masayuki TerashimaHyuma Masu Mayumi NabetaKaori Ono Nobuyoshi MoritaKosuke Katagiri Isao AzumayaOsamu Tamura 《Tetrahedron》2011,67(44):8536-8543
A series of cis-preferential aromatic N-methyl amides was designed and synthesized, and acid-induced conformational alteration of these compounds was investigated by means of NMR measurements in solution and X-ray crystal structure analysis. Compounds with a terminal N-methyl-N-(2-pyridyl) amide unit showed acid-induced conformational change from cis to trans, while those with a terminal N-methyl-2-pyridinecarboxamide unit showed a change of the carbonyl orientation from anti to syn with retention of cis conformation. 相似文献
50.
Naokazu Kano Hideaki Miyake Keishi Sasaki Takayuki Kawashima 《Heteroatom Chemistry》2015,26(2):183-186
The Si Si bond of a pentacoordinated disilicate was readily cleaved by treatment with 2,3‐dichloro‐5,6‐dicyano‐p‐benzoquinone in the presence of sodium carbonate under mild conditions. The bond cleavage did not proceed under the same conditions after conversion of the disilicate into the corresponding monoanionic silylsilicate and neutral disilane by protonation. The difference in the charges of the Si Si bond compounds affects the reactivity toward an oxidant, resulting in the Si Si bond cleavage, considering that all of these compounds have a bond between pentacoordinated silicon atoms. 相似文献