全文获取类型
收费全文 | 956篇 |
免费 | 9篇 |
国内免费 | 6篇 |
专业分类
化学 | 641篇 |
晶体学 | 14篇 |
力学 | 13篇 |
数学 | 52篇 |
物理学 | 251篇 |
出版年
2022年 | 4篇 |
2020年 | 5篇 |
2019年 | 12篇 |
2018年 | 15篇 |
2017年 | 7篇 |
2016年 | 7篇 |
2015年 | 10篇 |
2014年 | 20篇 |
2013年 | 41篇 |
2012年 | 33篇 |
2011年 | 71篇 |
2010年 | 30篇 |
2009年 | 22篇 |
2008年 | 61篇 |
2007年 | 46篇 |
2006年 | 61篇 |
2005年 | 48篇 |
2004年 | 42篇 |
2003年 | 36篇 |
2002年 | 39篇 |
2001年 | 30篇 |
2000年 | 17篇 |
1999年 | 10篇 |
1998年 | 7篇 |
1997年 | 7篇 |
1996年 | 7篇 |
1995年 | 11篇 |
1994年 | 19篇 |
1993年 | 14篇 |
1992年 | 15篇 |
1991年 | 15篇 |
1990年 | 13篇 |
1989年 | 11篇 |
1988年 | 7篇 |
1987年 | 9篇 |
1986年 | 19篇 |
1985年 | 17篇 |
1984年 | 15篇 |
1983年 | 10篇 |
1982年 | 13篇 |
1981年 | 12篇 |
1980年 | 11篇 |
1979年 | 6篇 |
1978年 | 7篇 |
1977年 | 12篇 |
1976年 | 8篇 |
1975年 | 4篇 |
1974年 | 6篇 |
1973年 | 8篇 |
1972年 | 4篇 |
排序方式: 共有971条查询结果,搜索用时 15 毫秒
21.
Kaname Takagi Tomoji Aotsuka And Hikari Morita Yoshihisa Okamoto 《Journal of heterocyclic chemistry》1986,23(5):1443-1449
Reactions of 4-ethoxycarbonylamino-1H-1,5-benzodiazepine-3-carbonitrile (2) with aliphatic primary amines gave 1-substituted 4-(2-aminoanilino)pyrimidin-2(1H)-one-5-carbonitriles 3. Analogous reactions of 2 with aromatic primary amines afforded 2-(2′-anilino-1′-cyanovinyl)benzimidazoles 5 and 6. Upon treatment with triethylamine, 3 underwent intramolecular cyclization to give 3-substituted 5-aminopyrimidino[4,5-b]-[1,5]benzodiazepin-2(3H,11H)-ones 8 . Heating of 3 with p-toluenesulfonic acid in ethanol gave 2-substituted pyrimidino[1,6-a]benzimidazol-1(2H)one-4-carbonitriles 9 . Reactions of 2 with hydrazines were also described. Mechanistic pathways are proposed to account for the products. 相似文献
22.
Tadahiro Kato Motoyuki Tanaka Shin‐suke Takagi Keita Nakanishi Masahiro Hoshikawa 《Helvetica chimica acta》2004,87(1):197-214
The synthesis of kempa‐6,8‐dien‐3β‐ol ( 4a ), as a synthetic leading model of the natural product 4b , was carried out starting from intermediate 12 , the synthetic route of which has been developed previously (Scheme 1). The conversion of 12 to the model compound 4a involved the elaboration of three structure modifications by three processes, Tasks A, B, and C (see Scheme 2). Task A was achieved by epoxy‐ring opening of 41 with Me3SiCl (Scheme 9), and Task B being performed by oxidation at the 13‐position, followed by hydrogenation, and then epimerization (Schemes 4 and 5). The removal of the 2‐OH group from 12 (Task C) was achieved via 30b according to Scheme 6, whereby 30b was formed exclusively from 30a / 31a 1 : 1 (Scheme 7). In addition, some useful reactions from the synthetic viewpoint were developed during the course of the present experiments. 相似文献
23.
Photoelectron angular distributions in the laboratory frame (LF-PADs) from the A((2)sigma(+)) state of NO molecule were measured by femtosecond time-resolved photoelectron imaging with (1 + 1(')) resonance enhanced multiphoton ionization via the A state. High-precision measurements of the anisotropy parameters of LF-PADs were performed for the photoelectron kinetic energy from 0.03 to 1.05 eV as a function of the pump-probe delay time. The revival feature of the rotational wave packet on the A state was clearly observed in the time dependence of the photoelectron anisotropy parameters. By approximating the phase shifts of the photoelectron partial waves by the quantum defects in the high-lying Rydberg states using the multichannel quantum defect theory, the energy-dependent photoionization transition dipole moments were determined, for the first time, from time-dependent LF-PADs measured by time-resolved photoelectron spectroscopy. 相似文献
24.
Shinsuke Takagi Miharu Eguchi Tetsuya Shimada Satoshi Hamatani Haruo Inoue 《Research on Chemical Intermediates》2007,33(1-2):177-189
Photochemical energy transfer of non-aggregated cationic porphyrins on an anionic-type clay (Smecton SA) surface was investigated. The efficiency of energy transfer and excited-state quenching in the absence of energy transfer were evaluated at various loading levels of porphyrin on the clay surface and were found to be significantly affected by the loading level. As the latter increased, both energy transfer efficiency and excited-state quenching increased. Judging from the dependency of energy-transfer efficiency on the porphyrin loading level, a partially clustered structure, but without aggregation, of porphyrins on the clay surface is proposed. 相似文献
25.
Crown ether dyes with pendent anionic side-arms were synthesized for extractionspectrophotometry of alkali and alkaline earth metal ions. Dramatic changes in metal selectivity were obtained simply by changing the nature of the anionic side-arm on the same crown ether skeleton. A structure/metal selectivity relationship is discussed in detail in terms of “chelate” and “intramolecular ion-pair” formation. Small metal cations (high charge density) are preferred in the extraction by a crown ether reagent with a charge-localized anionic side-arm through the formation of a “chelate”. Large metal cations (low charge density) are preferred in the extraction by reagents with a charge-delocalized anionic side-arm through the formation of an “intramolecular ion-pair”. Steric restrictions imposed by the side-arm on the metal ion approaching the crown ether are also important factor in controlling the selectivity of these reagents. 相似文献
26.
Ryohei Yamakado Shin-ichi Matsuoka Masato Suzuki Koji Takagi Kosuke Katagiri Isao Azumaya 《Tetrahedron》2013,69(5):1516-1520
m-Calix[3]amide bearing three pyrenes (1a) was prepared by the condensation reaction of 3-nonylaminobenzoic acid derivative using Ph3PCl2. Pyrenyl groups were found to be aligned in the screw-like fashion by m-calix[3]amide as confirmed by the X-ray crystallography. Aromatic proton signals observed at the up-field region in the 1H NMR spectrum at low temperature indicated that pyrenyl groups in 1a are aligned in close proximity in THF solution. UV–vis absorption and fluorescence emission spectra did not show marked peak shift nor concentration fluorescence quenching compared with reference compounds implying no significant electronic interaction between pyrenyl groups. These results can be explained by the steric effect of the m-calix[3]amide platform. On the other hand, an excimer emission was observed for m-calix[3]amide having a flexible spacer between pyrene and m-calix[3]amide (1b). 相似文献
27.
28.
29.
Ganesh Shenoy Jessica Ettedgui Chandrasekhar Mushti Jennifer Hong Kelly Lane Burchelle Blackman Hak-Sung Jung Yasuharu Takagi Yeonee Seol Martin Brechbiel Rolf E. Swenson Keir C. Neuman 《Molecules (Basel, Switzerland)》2022,27(3)
Carboxylic acid is a commonly utilized functional group for covalent surface conjugation of carbon nanoparticles that is typically generated by acid oxidation. However, acid oxidation generates additional oxygen containing groups, including epoxides, ketones, aldehydes, lactones, and alcohols. We present a method to specifically enrich the carboxylic acid content on fluorescent nanodiamond (FND) surfaces. Lithium aluminum hydride is used to reduce oxygen containing surface groups to alcohols. The alcohols are then converted to carboxylic acids through a rhodium (II) acetate catalyzed carbene insertion reaction with tert–butyl diazoacetate and subsequent ester cleavage with trifluoroacetic acid. This carboxylic acid enrichment process significantly enhanced nanodiamond homogeneity and improved the efficiency of functionalizing the FND surface. Biotin functionalized fluorescent nanodiamonds were demonstrated to be robust and stable single-molecule fluorescence and optical trapping probes. 相似文献
30.
Kakuyanagi K Saitoh M Kumagai K Takashima S Nohara M Takagi H Matsuda Y 《Physical review letters》2005,94(4):047602
We present a 115In NMR study of the quasi-two-dimensional heavy-fermion superconductor CeCoIn5 believed to host a Fulde-Ferrel-Larkin-Ovchinnikov (FFLO) state. In the vicinity of the upper critical field and with a magnetic field applied parallel to the ab plane, the NMR spectrum exhibits a dramatic change below T*(H) which well coincides with the position of reported anomalies in specific heat and ultrasound velocity. We argue that our results provide the first microscopic evidence for the occurrence of a spatially modulated superconducting order parameter expected in a FFLO state. The NMR spectrum also implies an anomalous electronic structure of vortex cores. 相似文献