全文获取类型
收费全文 | 1080篇 |
免费 | 19篇 |
国内免费 | 4篇 |
专业分类
化学 | 736篇 |
晶体学 | 14篇 |
力学 | 5篇 |
数学 | 37篇 |
物理学 | 311篇 |
出版年
2023年 | 6篇 |
2021年 | 9篇 |
2020年 | 7篇 |
2019年 | 19篇 |
2018年 | 14篇 |
2017年 | 8篇 |
2016年 | 12篇 |
2015年 | 14篇 |
2014年 | 22篇 |
2013年 | 46篇 |
2012年 | 52篇 |
2011年 | 57篇 |
2010年 | 30篇 |
2009年 | 22篇 |
2008年 | 70篇 |
2007年 | 48篇 |
2006年 | 59篇 |
2005年 | 54篇 |
2004年 | 52篇 |
2003年 | 38篇 |
2002年 | 40篇 |
2001年 | 22篇 |
2000年 | 27篇 |
1999年 | 6篇 |
1998年 | 13篇 |
1997年 | 7篇 |
1996年 | 14篇 |
1995年 | 15篇 |
1994年 | 19篇 |
1993年 | 23篇 |
1992年 | 22篇 |
1991年 | 22篇 |
1990年 | 24篇 |
1989年 | 21篇 |
1988年 | 11篇 |
1987年 | 12篇 |
1986年 | 14篇 |
1985年 | 19篇 |
1984年 | 13篇 |
1983年 | 10篇 |
1982年 | 10篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1978年 | 10篇 |
1977年 | 15篇 |
1976年 | 8篇 |
1975年 | 13篇 |
1974年 | 14篇 |
1968年 | 5篇 |
排序方式: 共有1103条查询结果,搜索用时 15 毫秒
61.
Takuma Shinya Nakashima Noriyuki Tantirungkij Manee Kinoshita Shinichi Okada Hirosuke Sew TatsÜji Yoshida Toshiomi 《Applied biochemistry and biotechnology》1991,28(1):327-340
Applied Biochemistry and Biotechnology - A NADPH/NADH-dependent xylose reductase gene was isolated from the xylose-assimilating yeast,Pichia stipitis. DNA sequence analysis showed that the gene... 相似文献
62.
Suzuka Kinoshita Ryota Yamano Dr. Yu Shibata Yusuke Tanaka Kyoichi Hanada Dr. Takashi Matsumoto Prof. Dr. Kazunori Miyamoto Dr. Atsuya Muranaka Prof. Dr. Masanobu Uchiyama Prof. Dr. Ken Tanaka 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(27):11113-11120
An S-shaped double helicene-like molecule (>99 % ee), possessing stable helical chirality, has been synthesized by the rhodium(I)/difluorphos complex-catalyzed highly diastereo- and enantioselective intramolecular double [2+2+2] cycloaddition of a 2-naphthol- and benzene-linked hexayne. The collision between two terminal naphthalene rings destabilizes the helical chirality of the S-shaped double helicene-like molecule, but the introduction of two additional fused benzene rings significantly increases the configurational stability. Thus, no epimerization and racemization were observed even at 100 °C. The enantiopure S-shaped double helicene-like molecule forms a trimer through the multiple C−H⋅⋅⋅π and C−H⋅⋅⋅O interactions in the solid-state. The trimers stack to form columnar packing structures, in which neighboring stacks have opposite dipole directions. The accumulation of helical structures in the same direction in the S-shaped double helicene-like molecule enhanced the chiroptical properties. 相似文献
63.
A solid material consisting of dimethyl glyoxime (DMG), acenaphthenequinone dioxime (ANDO) or DMG-ANDO on naphthalene provides a very convenient, rapid and economical method for the preconcentration of palladium in synthetic samples. Pd-DMG, Pd-ANDO and Pd-DMG-ANDO are quantitatively retained on naphthalene in the column in the pH ranges 2.2–4.4, 1.8–5.6 and 1.7–6.8, respectively. The solid mixture consisting of the metal complex together with naphthalene is stripped from the column with 5 ml of dimethylformamide (DMF)-n-butylamine and the absorbance is measured at 247.6 nm with an atomic absorption spectrometer. Calibration graphs are linear over the palladium concentration range 5–25 μg per 5 ml of the final solution for all the three complexes. Ten replicate determinations of a sample solution containing 10 μg of palladium gave mean absorbances of 0.180, 0.225 and 0.230 with relative standard deviations of 1.8, 1.7 and 1.6% using the reagents DMg, ANDO and DMG-ANDO, respectively. The sensitivity of the method is better than the direct atomic absorption spectrometric determination of palladium. It is highest in case of the mixed ligands, i.e., DMG-ANDO (0.038 μg ml?1 for 1% absorption). The method can be applied to the trace determination of palladium in complex materials. 相似文献
64.
65.
Munakata R Katakai H Ueki T Kurosaka J Takao K Tadano K 《Journal of the American Chemical Society》2003,125(48):14722-14723
The first total synthesis of (+)-macquarimicin A (1), a novel inhibitor of neutral sphingomyelinase (N-SMase) with antiinflammatory activity, has been accomplished. The present work determined the absolute configuration of (+)-1 and revised the C(2)-C(3) geometry to be Z. The synthesis features a transannular Diels-Alder reaction, which constructed the tetracyclic framework stereoselectively, and a convergent and efficient synthetic pathway, which afforded (+)-macquarimicin A (1) in 27 steps (longest linear sequence) with 9.9% overall yield. 相似文献
66.
Non-extractable photoinitiators based on thiol-functionalized benzophenones and thioxanthones 总被引:1,自引:0,他引:1
Hironori Matsushima Qin Li Masamitsu Shirai Charles E. Hoyle 《European Polymer Journal》2010,46(6):1278-1287
Non-extractable photoinitiators could be advantageous for use in biological, electronic, and food packaging applications. Therefore, thioxanthone and benzophenone derivatives were synthesized from 1,6-hexane dithiol and chlorinated benzophenone or thioxanthone. The efficiency of thiol-functionalized photoinitiators in combination with amine co-initiators was compared to benzophenone and isopropylthioxanthone with amine co-initiators, and the cleavage of photoinitiator 2,2-dimethoxy-1,2-diphenylethan-1-one in acrylic resins. The reaction kinetics were analyzed using photo-differential scanning calorimetry and real-time FTIR. Coating physical properties were evaluated by pendulum and pencil hardness, steel-wool scratch and mandrel bend tests. The non-extractable photoinitiators had higher absorbance than their benzophenone or isopropylthioxanthone counterparts due to the sulfide substitution on the phenyl ring, and the free thiol groups reacted with the acrylate by either an amine catalyzed Michael addition or a free-radical chain process. The combination of thiol-functionalized photoinitiators with secondary amines provides an efficient photoinitiator system that is locked into the photopolymerized network and cannot be extracted with typical solvents. 相似文献
67.
Shinji Suzuki Furitsu Suzuki Yasumasa Kanie Koji Tsujitani Asako Hirai Hironori Kaji Fumitaka Horii 《Cellulose (London, England)》2012,19(3):713-727
The structure and crystallization of carefully isolated sub-elementary fibrils (SEFs) of bacterial cellulose have been investigated
using TEM, WAXD, and high-resolution solid-state 13C NMR. The addition of a suitable amount of fluorescent brightener (FB) to the incubation medium of Acetobacter xylinum effectively suppressed the aggregation of the SEFs into the microfibrils, as previously reported. However, this study confirmed
for the first time that serious structural change in the SEFs occurs during the removal of excess FB by washing with buffer
solutions having pH values higher than 6 or with the alkaline aqueous solution that was frequently used in previous studies.
In contrast, the isolation of unmodified SEFs was successfully performed by utilizing a washing protocol employing pH 7 citrate–phosphate
buffer solution containing 1% sodium dodecyl sulfate. High-resolution solid-state 13C NMR and WAXD measurements revealed that the SEFs thus isolated are in the noncrystalline state in which the pyranose rings
of the almost parallel cellulose chains appear to be stacked on each other. The respective CH2OH groups of the SEFs adopt the gt conformation instead of the tg conformation found in cellulose I
α
and I
β
crystals, and undergo significantly enhanced molecular motion in the absence of intermolecular hydrogen bonding associated
with these groups. The main chains are also subject to rapid motional fluctuations while maintaining the parallel orientation
of the respective chains, indicating that the SEFs have a liquid crystal-like structure with high molecular mobility. Moreover,
the SEFs crystallize into cellulose I
β
when the FB molecules that may adhere to the surface of the SEFs are removed by extraction with boiling 70 v/v% ethanol and
0.1N NaOH aqueous solution. On the basis of these results, the crystallization of the SEFs into the I
α
and I
β
forms is discussed, including the possible formation of the crystalline-noncrystalline periodic structure in native cellulose. 相似文献
68.
Hironori Tohmyoh Shoho Ishikawa Mikio Muraoka 《Surface and interface analysis : SIA》2012,44(9):1294-1298
An eddy current microscopy technique to evaluate the electrical conductivity of thin metallic films in a non‐contact manner is reported. A narrow track formed in an approximately 100 nm thick Au film was prepared, and a Co–Cr coated magnetic tip was driven to oscillate above the track both with and without current passing through the track. Despite the absence of current, the electromagnetic interaction between the tip and the stray magnetic field from the track gave rise to a phase delay in the probe. This was due to an eddy current being induced within part of the track. Moreover, measurements of the phase change in the probe oscillation for different metallic films with thicknesses of about 100 nm found this to be proportional to the electrical conductivity of the film. Finally, the electrical conductivity of an Al film was evaluated using the eddy current microscopy technique. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
69.
70.