全文获取类型
收费全文 | 579篇 |
免费 | 10篇 |
国内免费 | 3篇 |
专业分类
化学 | 490篇 |
晶体学 | 15篇 |
力学 | 3篇 |
数学 | 10篇 |
物理学 | 74篇 |
出版年
2022年 | 7篇 |
2021年 | 8篇 |
2020年 | 10篇 |
2019年 | 12篇 |
2018年 | 3篇 |
2017年 | 5篇 |
2016年 | 17篇 |
2015年 | 10篇 |
2014年 | 12篇 |
2013年 | 31篇 |
2012年 | 33篇 |
2011年 | 34篇 |
2010年 | 28篇 |
2009年 | 14篇 |
2008年 | 42篇 |
2007年 | 39篇 |
2006年 | 35篇 |
2005年 | 35篇 |
2004年 | 30篇 |
2003年 | 25篇 |
2002年 | 25篇 |
2001年 | 8篇 |
2000年 | 12篇 |
1999年 | 5篇 |
1998年 | 7篇 |
1997年 | 7篇 |
1996年 | 6篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 7篇 |
1992年 | 7篇 |
1990年 | 4篇 |
1989年 | 4篇 |
1988年 | 5篇 |
1987年 | 2篇 |
1986年 | 5篇 |
1985年 | 6篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1981年 | 7篇 |
1980年 | 8篇 |
1979年 | 6篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1973年 | 1篇 |
1970年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有592条查询结果,搜索用时 15 毫秒
21.
Two trans stereoisomers of 3‐methylcyclopentadecanol (=muscol), (1R,3R)‐ 2 and (1S,3S)‐ 2 , were efficiently synthesized from (3RS)‐3‐methylcyclopentadecanone (=muscone; (3RS)‐ 1 ) by a highly stereoselective reduction (Scheme). L‐Selectride® (=lithium tri(sec‐butyl)borohydride) was used, followed by the enantiomer resolution by lipase QLG (Alcaligenes sp.). The cis stereoisomers of muscol, (1S,3R)‐ 2 and (1R,3S)‐ 2 , were obtained by the Mitsunobu inversion of (1R,3R)‐ 2 and (1S,3S)‐ 2 , respectively (Scheme). The absolute configuration of (1R,3R)‐ 2 was determined by X‐ray crystal‐structure analysis of its 3‐nitrophthalic acid monoester, 2‐[(1R,3R)‐3‐methylcyclopentadecyl hydrogen benzene‐1,2‐dicarboxylate ((1R,3R)‐ 3b ), and by oxidation of (1R,3R)‐ 2 to (3R)‐muscone. 相似文献
22.
Two oxinylporphyrins, 5-(8-hydroxy-5-quinolinyl)-10,15,20-( p -tolyl)- porphyrin ( 1 ) and 5,15-bis(8-hydroxy-5-quinolinyl)-10,20-bis( n -heptyl)-porphyrin ( 2 ), were prepared and coordinated with Ga(III) to afford tris(oxinato) complex 3 and poly(oxinato) complex 4 , respectively. The structure of 3 was analyzed by variable temperature NMR study with referring to tris(8-hydroxy-5-quinolinyl)Ga(III) complex 5 to be in a meridional form. Oxinato ligands of 3 and 5 were exchanged with one another, with keeping the meridional structure. UV-Vis and fluorescence spectra of tris(oxinato)complex 3 and poly(oxinato)complex 4 were compared with each monomeric compound 1 and 2 . The absorption spectra showed only a slight broadening of the Soret band, suggesting trivial electronic and excitonic interactions. The fluorescence intensity was increased significantly compared with each monomeric compound 1 and 2 . At the same time, efficient excitation energy transfer among three porphyrins has been observed. 相似文献
23.
Shigekazu Usuda Kenichiro Yasuda Yoko Saito-Kokubu Fumitaka Esaka Chi-Gyu Lee Masaaki Magara 《International journal of environmental analytical chemistry》2013,93(9):663-675
From a viewpoint of physical and chemical form estimation, ultra-trace analytical techniques of nuclear materials in environmental samples for safeguards have been investigated at Japan Atomic Energy Research Institute. This article deals with (1) an outline of the developed techniques for bulk and particle analyses of uranium and plutonium in the safeguards environmental samples; (2) current R&D on techniques relating to estimation of the physical and chemical form, such as SEM images and EDX spectra for fine particles of nuclear materials and fission track observation applicable to fissile materials; and (3) possible analytical methodologies, as future works, applicable to ultra-trace amounts of nuclear materials in environmental samples. 相似文献
24.
Excited state intramolecular hydrogen atom transfer of phenylethynyl-substituted 2′-hydroxychalcones
Satomi Tasaki Atsuya Momotake Yoko Kanna Tatsuo Arai 《Research on Chemical Intermediates》2013,39(1):61-72
(E)-1-[2-Hydroxy-4-(phenylethynyl)phenyl]-3-[4-(phenylethynyl)phenyl]prop-2-en-1-one (1), (E)-1-[2-hydroxy-4-(phenylethynyl)phenyl]-3-phenylprop-2-en-1-one (2), and (E)-1-(2-hydroxyphenyl)-3-[4-(phenylethynyl)phenyl]prop-2-en-1-one (3), which belong to a new class of 2′-hydroxychalcones with phenylethynyl group(s) at the para position of the phenyl ring, were synthesized, and their photochemical properties were investigated. The lowest energy absorption band of 1 peaks at a longer wavelength (383 nm) with a much larger molar extinction coefficient (5.0 × 104 M ?1 cm?1) than that of the parent 2′-hydroxychalcone (2′HC) (2.0 × 104 M ?1 cm?1 at 318 nm). Upon photoexcitation, all three compounds underwent excited-state intramolecular hydrogen atom transfer (ESIHT) to produce an excited tautomer that emitted fluorescence with a large Stokes shift in the longer wavelength region at 600–700 nm. The quantum yield of the tautomer fluorescence of 1 was not high at 298 K (Φ f = 9.1 × 10?5), but was highest among 2′HC and its analogues. The Φ f values of 1–3 increased 10–30 fold upon reducing the temperature from 298 to 77 K. 相似文献
25.
Izuho Itoh Yoko Matsusaki Akitoshi Fujiya Norihiro Tada Tsuyoshi Miura Akichika Itoh 《Tetrahedron letters》2014
In this Letter, we report the aerobic photo-oxidative synthesis of diacylamines from benzylamides in the presence of molecular oxygen and catalytic amounts of 2-chloroanthraquinones under visible light irradiation from a fluorescent lamp. 相似文献
26.
27.
Yoko Hirohara Yoshitaka OKawa Toshifumi Mihashi Tatsuo Yamaguchi Naoki Nakazawa Yasuko Tsuruga Hiroyuki Aoki Naoyuki Maeda Ichiro Uchida Takashi Fujikado 《Optical Review》2007,14(3):151-158
The purpose of this paper was to investigate the feasibility of a newly developed hyperspectral fundus imaging camera with
a liquid crystal tunable filter. The intensities of different wavelengths of light transmitted through an artery, vein, and
the area surrounding these vessels and reflected out were measured, and the differential spectral absorptions were analyzed.
Measurements were made from 16 normal eyes and from two artificial capillaries. The ratios of absorption (ROA) of arteries
to veins from 500 to 580 nm (range 1) and from 600 to 720 nm (range 2) were calculated. For all eyes, the ROArange1 was larger than ROArange2. The ROA obtained from the artificial capillary filled with blood saturated with oxygen or nitrogen was similar to that of
simulated data of oxy- and deoxyhemoglobin extinction rate. Most ROAs of human eyes were lower than those of the simulated
data and the artificial capillaries. Oxygen saturation analysis by hyperspectral fundus imaging of retinal vessels were qualitatively
in agreement with thein vitro analysis or simulated values. However, further improvements are necessary to evaluate the oxygen saturation quantitatively
in the retinal blood vessels. 相似文献
28.
Hiroya Yamaguchi Yoshie Yotsukura Hirosaku Sata Yoko Watanabe Hajime Hirose Noriko Kobayashi Diane M. Bless 《Journal of voice》1993,7(3)
A voice therapy program using pushing exercises to correct glottal incompetence is described. The program utilizes various types of instrumentation to determine whether or not a given patient is likely to benefit from the treatment. The program also provides feedback of target voices. Three cases with incomplete glottal closure and subsequent vocal dysphonia characterized by an asthenic breathy quality are used to illustrate the program. Details of the program, termination criteria, and problems and precautions learned from treating 29 patients over a 3-year period are presented. 相似文献
29.
Extremely Photostable Electron-Deficient Phthalocyanines that Generate High Levels of Singlet Oxygen
Prof. Dr. Taniyuki Furuyama Yusuke Miyaji Kazuya Maeda Prof. Dr. Hajime Maeda Prof. Dr. Masahito Segi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(7):1678-1682
A robust lead-mediated synthetic procedure for the generation of phthalocyanines substituted with electron-withdrawing groups has been developed. The free-base phthalocyanine and various metal complexes were prepared without discernible degradation of the peripheral electron-withdrawing substituents. Upon irradiation with red light, some of the thus-obtained metal complexes generated high levels of singlet oxygen. In particular, a palladium complex exhibited attractive photostability upon exposure to singlet oxygen as a bleaching agent. The photostability of such complexes that may manifest concomitantly to the generation of high levels of singlet oxygen was attributed to the presence of the electron-withdrawing groups, which results in energetically low-lying highest occupied molecular orbitals. 相似文献
30.
Kenta Yamaguchi Dr. Toshinori Matsushima Dr. Atula S. D. Sandanayaka Yoko Homma Naoki Uchida Prof. Chihaya Adachi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(25):5598-5602
In organic light-emitting diodes (OLEDs) based on materials that show thermally activated delayed fluorescence (TADF), the internal quantum efficiency of 100 % can be obtained without using phosphorescence-based organometallics that contain rare metals. Therefore, with TADF-based emitters, it is possible to fabricate high-performing OLEDs at a lower cost. However, compared with fluorescence- and phosphorescence-based OLEDs, an understanding of degradation mechanisms in TADF-based OLEDs is still insufficient for future commercialization. In particular, it is widely recognized that the development of electron transport materials is crucial for improving OLED characteristics, especially driving voltages and operational durability. In this study, it was demonstrated that the operational durability of TADF-based OLEDs was greatly improved by introducing a triazine-based material of 2,4,6-tris(1,1′-biphenyl-4-yl)-[1,3,5]triazine (pT2T) as a hole-blocking layer (HBL) compared with a conventional HBL material of 2,4,6-tris(biphenyl-3-yl)-[1,3,5]triazine (T2T). Several experiments were carried out to make the reasons of the improved durability clearer, and attributed the improved durability to the shift of a carrier recombination zone from the emitting layer/HBL interface and the suppressed formation of excited-state quenchers in the pT2T HBL, because of the higher electron mobility of pT2T and the better stability of its radical anion state. 相似文献