全文获取类型
收费全文 | 6092篇 |
免费 | 164篇 |
国内免费 | 24篇 |
专业分类
化学 | 4338篇 |
晶体学 | 76篇 |
力学 | 87篇 |
数学 | 263篇 |
物理学 | 1516篇 |
出版年
2022年 | 35篇 |
2021年 | 38篇 |
2020年 | 64篇 |
2019年 | 68篇 |
2018年 | 57篇 |
2017年 | 37篇 |
2016年 | 101篇 |
2015年 | 101篇 |
2014年 | 128篇 |
2013年 | 289篇 |
2012年 | 273篇 |
2011年 | 307篇 |
2010年 | 181篇 |
2009年 | 178篇 |
2008年 | 334篇 |
2007年 | 305篇 |
2006年 | 307篇 |
2005年 | 323篇 |
2004年 | 293篇 |
2003年 | 239篇 |
2002年 | 237篇 |
2001年 | 158篇 |
2000年 | 174篇 |
1999年 | 98篇 |
1998年 | 66篇 |
1997年 | 74篇 |
1996年 | 69篇 |
1995年 | 46篇 |
1994年 | 77篇 |
1993年 | 92篇 |
1992年 | 99篇 |
1991年 | 79篇 |
1990年 | 65篇 |
1989年 | 56篇 |
1988年 | 74篇 |
1987年 | 74篇 |
1986年 | 76篇 |
1985年 | 117篇 |
1984年 | 102篇 |
1983年 | 42篇 |
1982年 | 76篇 |
1981年 | 78篇 |
1980年 | 71篇 |
1979年 | 63篇 |
1978年 | 55篇 |
1977年 | 67篇 |
1976年 | 57篇 |
1975年 | 39篇 |
1974年 | 49篇 |
1973年 | 32篇 |
排序方式: 共有6280条查询结果,搜索用时 12 毫秒
1.
Yuki Shintani Taku Ohtomi Dr. Aya Shibata Dr. Yoshiaki Kitamura Koichiro M. Hirosawa Prof. Kenichi G. N. Suzuki Prof. Masato Ikeda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(8):e202104421
Aqueous self-assembly of short peptides has attracted growing attention for the construction of supramolecular materials for various bioapplications. Herein, we describe how the thermolysin-assisted biocatalytic construction of a dipeptide hydrazide from an N-protected amino acid and an amino acid hydrazide leads to the formation of thermally stable supramolecular hydrogels. In addition, we demonstrate the post-assembly modification of the supramolecular architectures constructed in situ tethering hydrazide groups as a chemical handle by means of fluorescence imaging. 相似文献
2.
Takumi Watanabe Yuichiro Nishizawa Haruka Minato Dr. Chihong Song Prof. Dr. Kazuyoshi Murata Prof. Dr. Daisuke Suzuki 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):8934-8938
The three-dimensional structure of nanocomposite microgels was precisely determined by cryo-electron micrography. Several nanocomposite microgels that differ with respect to their nanocomposite structure, which were obtained from seeded emulsion polymerization in the presence of microgels, were used as model nanocomposite materials for cryo-electron micrography. The obtained three-dimensional segmentation images of these nanocomposite microgels provide important insights into the interactions between the hydrophobic monomers and the microgels, that is, hydrophobic styrene monomers recognize molecular-scale differences in polarity within the microgels during the emulsion polymerization. This result led to the formation of unprecedented multi-layered nanocomposite microgels, which promise substantial potential in colloidal applications. 相似文献
3.
The effect of Re addition on the microstructure and hardening behaviour of the dual two-phase Ni3Al (L12) and Ni3V (D022) intermetallic alloy was investigated by scanning electron microscopy, transmission electron microscopy and Vickers hardness test. The two-phase eutectoid microstructure accompanying the Re-rich precipitates were observed in the channel region of the alloys in which Re substituted for Ni but not in those in which Re substituted for Al and V. The concomitant addition of Nb (or Ta) with Re more stabilized the two-phase eutectoid microstructure and consequently more induced the fine precipitates in the channel region. The annealing at temperatures below the eutectoid temperature was necessary to induce the fine precipitates in the channel region and thereby result in the precipitation hardening. The fine precipitation in the channel region and related hardening was attributed to the alloying feature so that Re is soluble in the A1 (fcc) phase at high temperatures and becomes less soluble in the two intermetallic phases decomposed from the A1 phase at low temperatures. 相似文献
4.
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
5.
Yasuyuki Kawahigashi 《Communications in Mathematical Physics》2002,226(2):269-287
We study the recent construction of subfactors by Rehren which generalizes the Longo–Rehren subfactors. We prove that if
we apply this construction to a non-degenerately braided subfactor N⊂M and α±-induction, then the resulting subfactor is dual to the Longo–Rehren subfactor M⊗M
opp⊂R arising from the entire system of irreducible endomorphisms of M resulting from αplusmn;-induction. As a corollary, we solve a problem on existence of braiding raised by Rehren negatively. Furthermore, we generalize
our previous study with Longo and Müger on multi-interval subfactors arising from a completely rational conformal net of factors
on S
1 to a net of subfactors and show that the (generalized) Longo–Rehren subfactors and α-induction naturally appear in this context.
Received: 11 September 2001 / Accepted: 7 October 2001 相似文献
6.
Yasuyuki Agari Kiyofumi Sakai Yosikazu Kano Ryoki Nomura 《Journal of Polymer Science.Polymer Physics》2007,45(21):2972-2981
We prepared biodegradable poly(ethylene oxide) (PEO)/poly(L ‐lactic acid) (PLLA) graded blends by the dissolution–diffusion process, and discussed the biodegradability and tensile strength of the graded blends by comparing isotropic blend and PLLA only. All the graded blends were degraded more largely than the PLLA only and isotropic blend (PEO: 37.5 wt %), which had the same content as the total content of those graded blends. The graded blend having most excellent wide compositional gradient was degraded most largely with the enzyme. Thus, graded structure of the blends promoted their biodegradabilities large. It was considered that the dissolution of PEO with water increased the surface area attacked by the enzyme, while PEO caught PLLA oligomers to promote the biodegradation of PLLA. Then, the biodegradabilities of the graded blends were suppressed by the increasing crystallinity of PLLA. Furthermore, the strengths of all the graded blends were larger than those of the isotropic blend. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2972–2981, 2007 相似文献
7.
Akira Yanagisawa Prof. Dr. Takahiro Suzuki Takanori Koide Shogo Okitsu Takayoshi Arai Prof. Dr. 《化学:亚洲杂志》2008,3(10):1793-1800
A Barbier‐type regioselective propargylation of aldehydes and ketones with (3‐bromobut‐1‐ynyl)trimethylsilane has been achieved using reactive barium as a low‐valent metal in THF. Especially in the case of ketones, the corresponding homopropargylic alcohols form almost exclusively. In the reaction of α,β‐unsaturated carbonyl compounds, only 1,2‐adducts have been observed. This method is also applicable to propargylation of imines, and the corresponding homopropargylic amines are obtained regiospecifically in good yields with diastereomeric ratios of up to 87:13. 相似文献
8.
Ultrasonic longitudinal velocity and adsorption have been measured in ceramic superconductors YBa2Cu3Oy with various porosity and also in BiSrCaCu2Oy. A velocity drop of about 400 ppm was found at Tc only in the measurements on cooling. The magnitude of the velocity drop is anomalously large compared with the value expected from the thermodynamics. A hysteresis of velocity with respect to temperature was observed in all the samples studied. It is suggested that some structural change at pore size level is responsible for this phenomenon. 相似文献
9.
Yoshio Suzuki Noriyuki Tanji Chikako Ikeda Aki Honda Kenji Ookubo Daniel Citterio Suzuki Koji 《Analytical sciences》2004,20(3):475-482
Novel labeling reagents, called MS probes, which possess a positively charged quaternary amine moiety and can transform a neutral analyte into a charged compound by simply mixing with the analyte and allowing the mixture to stand from several minutes to 30 min at room temperature or while heating to 50 degrees C, were designed and synthesized for the highly sensitive detection of carbonyl, alcohol, carboxylic acid and primary amine samples by electrospray ionization mass spectrometry (ESI-MS). The positively charged products can be detected with high sensitivity in an ESI-MS system, which is the most popular liquid MS instrument. All of the labeled products showed a remarkably large increase in the molecular-ion peak abundance detection sensitivity of over 500-fold at picomolar concentration levels compared to that of unlabeled analytes in an ESI-MS system. These MS probes, used together with liquid MS detection, are widely applicable as a convenient method for the highly sensitive detection of less than picomolar levels of analytes, and therefore greatly enhance the power of ESI-MS analysis. 相似文献
10.
Spectral data during a chelatometric titration were utilized for determining an equivalence point of the titration. Three-dimensional titration data were analyzed by fitting to a theoretical equation that was derived from equilibrium equations among a metal ion, an indicator and EDTA. The equation with optimized parameters successfully explained the three-dimensional titration data. This method was applied to EDTA titration systems of zinc, cadmium and lead with xylenol orange (XO) as an indicator. These systems were analyzed while taking the formation of 1:1 and 2:1 metal-indicator complexes into account. By this method, an accurate equivalence point was determined as well as stability constants and molar absorption spectra of metal-indicator complexes in each titration system. Moreover, the comparability among the concentrations of the metal standard solutions prepared from pure metals (Zn, Pb, and Cd) was also confirmed by the proposed evaluation method. 相似文献