全文获取类型
收费全文 | 1328篇 |
免费 | 50篇 |
国内免费 | 5篇 |
专业分类
化学 | 1120篇 |
晶体学 | 13篇 |
力学 | 20篇 |
数学 | 42篇 |
物理学 | 188篇 |
出版年
2021年 | 11篇 |
2020年 | 16篇 |
2019年 | 20篇 |
2018年 | 7篇 |
2017年 | 8篇 |
2016年 | 21篇 |
2015年 | 26篇 |
2014年 | 25篇 |
2013年 | 61篇 |
2012年 | 61篇 |
2011年 | 85篇 |
2010年 | 40篇 |
2009年 | 38篇 |
2008年 | 76篇 |
2007年 | 70篇 |
2006年 | 90篇 |
2005年 | 57篇 |
2004年 | 39篇 |
2003年 | 38篇 |
2002年 | 32篇 |
2001年 | 21篇 |
2000年 | 48篇 |
1999年 | 18篇 |
1998年 | 15篇 |
1997年 | 15篇 |
1996年 | 16篇 |
1995年 | 14篇 |
1994年 | 15篇 |
1993年 | 13篇 |
1992年 | 29篇 |
1991年 | 19篇 |
1990年 | 16篇 |
1989年 | 20篇 |
1988年 | 19篇 |
1987年 | 25篇 |
1986年 | 17篇 |
1985年 | 34篇 |
1984年 | 17篇 |
1983年 | 14篇 |
1982年 | 12篇 |
1981年 | 14篇 |
1980年 | 18篇 |
1979年 | 9篇 |
1978年 | 8篇 |
1977年 | 12篇 |
1976年 | 13篇 |
1975年 | 14篇 |
1974年 | 15篇 |
1973年 | 14篇 |
1966年 | 9篇 |
排序方式: 共有1383条查询结果,搜索用时 15 毫秒
1.
Dr. Nozomi Mihara Dr. Yasuyuki Yamada Dr. Hikaru Takaya Prof. Yasutaka Kitagawa Dr. Kazunobu Igawa Prof. Katsuhiko Tomooka Prof. Hiroshi Fujii Prof. Kentaro Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(13):3369-3375
Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 5+, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 5+ catalyzed ethane oxidation in the presence of H2O2 at a relatively low temperature. The site-selective complexation of 3 5+ with an additional anionic porphyrin (TPPS4−) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 5+ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS4− to 3 5+ enhanced the catalytic activity. 相似文献
2.
The mode of action of the anti-complementary acidic heteroglycans, AAF-IIb-2 and IIb-3 which consisted of rhamnogalacturonan core and arabinogalactan moieties, purified from the leaves of Artemisia princeps PAMP (Japanese name = Gaiyo) were investigated. The anti-complementary activities of AAF-IIb-2 and IIb-3 were reduced partially in the absence of Ca2+ ions. A marked consumption of C4 was observed to have occurred when serum was incubated with both polysaccharides in the presence of Ca2+ ions. AAF-IIb-2 showed more potent C4 consumption than IIb-3. After the incubation of the serum with AAF-IIb-2 in the absence of Ca2+ ions, a cleavage of C3 in the serum was detected by immunoelectrophoresis. AAF-IIb-2 showed more significant consumption of the complement than IIb-3 when rabbit erythrocytes were used in the assay system in the absence of Ca2+ ions. These results indicate that AAF-IIb-2 activates the complement via both the alternative and classical pathways, whereas IIb-3 mainly activates the complement via the classical pathway. The absorption of serum with Protein A-Sepharose results in a decrease of the activity of AAF-IIb-2 and IIb-3. However, the decrease of the activity was restored by the replacement of the immunoglobulin G (IgG) fraction after its recovery from the Protein A-Sepharose. These results suggest that IgG dependent mechanisms are both involved in the anti-complementary activity of AAF-IIb-2 and IIb-3. 相似文献
3.
J Szeman H Ueda J Szejtli E Fenyvesi Y Machida T Nagai 《Chemical & pharmaceutical bulletin》1987,35(1):282-288
4.
N Murakami T Morimoto H Imamura T Ueda S Nagai J Sakakibara N Yamada 《Chemical & pharmaceutical bulletin》1991,39(9):2277-2281
Seven new monogalactosyl diacylglycerols (1-7) and six new digalactosyl diacylglycerols (11-16) were isolated from an axenically cultured cyanobacterium, P. tenue. Their structures were elucidated on the basis of physicochemical evidence and the results of enzymatic hydrolysis using a lipase (from Rhizopus arrhizus). Comparison of antialgal activity for P. tenue between monogalactosyl diacylglycerols (1-8) and digalactosyl diacylglycerols (11-19) revealed that the former showed more potent activity than the latter. 相似文献
5.
6.
Toshiro Watanabe Tapan Kumar Mazumder Shiro Nagai Keisuke Tsuji Shigeru Terabe 《Analytical sciences》2003,19(1):159-161
A micellar electrokinetic chromatography (MEKC) method was developed for estimating the angiotensin-I converting enzyme (ACE) inhibitory activity by separating the hippuric acid liberated in the ACE reaction mixture in the presence of an inhibitor, captopril. The hippuric acid was successfully separated and detected by MEKC with a 25 mM sodium dodecyl sulfate solution in a 25 mM phosphate-50 mM borate buffer at pH 7.0; the total analysis took about 5 min. A good linear relationship was observed between the inhibitor and the peak area of hippuric acid release. No significant difference in the ACE inhibitory activity (IC50) of captopril (an antihypertensive medicine) or autolyzed-mushrooms (functional foods) was observed between the conventional method and the MEKC method. The MEKC method was found to be a useful technique for a rapid assay of the ACE inhibitory activity. 相似文献
7.
Takayuki Yaegashi Shinya Yodoya Masahiko Nakamura Hiroki Takeshita Katsuhiko Takenaka Tomoo Shiomi 《Journal of polymer science. Part A, Polymer chemistry》2004,42(4):999-1007
Free‐radical homo‐ and copolymerization behavior of N,N‐diethyl‐2‐methylene‐3‐butenamide (DEA) was investigated. When the monomer was heated in bulk at 60 °C for 25 h without initiator, rubbery, solid gel was formed by the thermal polymerization. No such reaction was observed when the polymerization was carried out in 2 mol/L of benzene solution with with 1 mol % of azobisisobutyronitrile (AIBN) as an initiator. The polymerization rate (Rp) equation was Rp ∝ [DEA]1.1[AIBN]0.51, and the overall activation energy of polymerization was calculated 84.1 kJ/mol. The microstructure of the resulting polymer was exclusively a 1,4‐structure where both 1,4‐E and 1,4‐Z structures were included. From the product analysis of the telomerization with tert‐butylmercaptan as a telogen, the modes of monomer addition were estimated to be both 1,4‐ and 4,1‐addition. The copolymerizations of this monomer with styrene and/or chloroprene as comonomers were also carried out in benzene solution at 60 °C. In the copolymerization with styrene, the monomer reactivity ratios obtained were r1 = 5.83 and r2 = 0.05, and the Q and e values were Q = 8.4 and e = 0.33, respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 999–1007, 2004 相似文献
8.
Yukio Iida Masahiro Shibutani Katsuhiko Kobayashi Kazuhiko Ohnuma Yoichi Miyake Toru Noda 《Optical Review》2006,13(2):87-92
The double-pass method is thought to obtain the point spread function (PSF) in human eyes based on two techniques: the symmetric
double-pass method using the same pupil size and the asymmetric double-pass method using a different pupil size. The symmetric
double-pass method provides autocorrelation of the retinal PSF and, thus, the modulation transfer function. The asymmetric
double-pass method provides low-frequency partial-phase information and the partial phase-retrieval algorithm is applied to
obtain the complete-phase information, and to estimate the PSF. The partial phase-retrieval algorithm is based on the iteration
method proposed by Fineup and Kowalczyk and requires a lengthy computation. In this study, we propose a new high-speed phase-retrieval
algorithm based on the property that the real and imaginary parts of optical transfer functions (OTFs) continuously change
in value. 相似文献
9.
H. Okumura T. Takahagi N. Nagai S. Shingubara 《Journal of Polymer Science.Polymer Physics》2003,41(17):2071-2078
The structural change in the depth direction of a polyimide (UPILEX‐S) film treated in alkaline solution, which was a representative surface treatment used to form a seed layer for plating and to improve the adhesive strength, was analyzed by means of micro Fourier transform infrared attenuated total reflection (FTIR‐ATR) line analysis with gradient shaving preparation. The polyimide film was treated with KOH. The imide ring opened through the alkaline treatment, and the amide structure and carboxylic acid salt were formed. The attainment depth of this structural change was almost proportional to the treatment time, and it reached about 8 μm after a 30‐min treatment. The degree of structural change through the alkaline treatment was almost constant after it reached a considerably degraded stage, and the chemically changed region penetrated into the inner part of the film from the surface. An intermediate layer before the final degraded stage appeared in the treated layer, and its thickness increased with the treatment time. The region that was changed chemically by the alkaline treatment progressed to the inner part simultaneously and continuously as the treatment time increased. The combined use of gradient shaving preparation and micro FTIR‐ATR line analysis was found to be extremely effective for the depth profiling of organic materials. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2071–2078, 2003 相似文献
10.
Teruhisa Horita Katsuhiko Yamaji Natsuko Sakai Yueping Xiong Harumi Yokokawa Tatsuya Kawada 《Ionics》2002,8(1-2):108-117
The oxygen reduction active sites were visualized around the O2/SOFC cathode/electrolyte triple phase boundaries (TPB) by the16O/18O exchange techniques and secondary ion mass spectrometry (SIMS) analysis. The higher18O concentration is observed on the cathode top surfaces (La0.9Sr0.1MnO3-mesh, Au-mesh, and Ag-porous), which suggested the promotion of oxygen adsorption and oxygen surface exchange at the cathode.
The oxygen diffusion through the bulk of cathode occurred at the La0.9Sr0.1MnO3-mesh and the Ag-porous cathodes, not at the Au-mesh cathode. On the YSZ surfaces after removing the cathode, the active sites
for oxygen incorporation were analyzed by SIMS. The active sites for oxygen incorporation were at the La0.9Sr0.1MnO3/YSZ interface as well as the TPB. On the other hand, the active sites for oxygen incorporation are limited to the TPB in
the case of the Au-mesh removed YSZ surface. From the SIMS analysis, the expansion of the active sites for oxygen incorporation
is less than a few μm from the TPB lines.
Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001. 相似文献