全文获取类型
收费全文 | 2101篇 |
免费 | 33篇 |
国内免费 | 3篇 |
专业分类
化学 | 1688篇 |
晶体学 | 25篇 |
力学 | 12篇 |
数学 | 136篇 |
物理学 | 276篇 |
出版年
2021年 | 15篇 |
2020年 | 17篇 |
2019年 | 25篇 |
2018年 | 18篇 |
2017年 | 12篇 |
2016年 | 22篇 |
2015年 | 31篇 |
2014年 | 29篇 |
2013年 | 92篇 |
2012年 | 55篇 |
2011年 | 93篇 |
2010年 | 51篇 |
2009年 | 58篇 |
2008年 | 91篇 |
2007年 | 116篇 |
2006年 | 108篇 |
2005年 | 104篇 |
2004年 | 102篇 |
2003年 | 102篇 |
2002年 | 100篇 |
2001年 | 65篇 |
2000年 | 40篇 |
1999年 | 25篇 |
1998年 | 26篇 |
1997年 | 29篇 |
1996年 | 28篇 |
1995年 | 18篇 |
1994年 | 20篇 |
1993年 | 17篇 |
1992年 | 29篇 |
1991年 | 31篇 |
1990年 | 24篇 |
1989年 | 20篇 |
1988年 | 28篇 |
1987年 | 20篇 |
1986年 | 28篇 |
1985年 | 29篇 |
1984年 | 45篇 |
1983年 | 17篇 |
1982年 | 27篇 |
1981年 | 33篇 |
1980年 | 43篇 |
1979年 | 40篇 |
1978年 | 31篇 |
1977年 | 24篇 |
1976年 | 26篇 |
1975年 | 28篇 |
1974年 | 23篇 |
1973年 | 16篇 |
1972年 | 13篇 |
排序方式: 共有2137条查询结果,搜索用时 15 毫秒
1.
Dr. Manussada Ratanasak Takumi Murata Taishin Adachi Prof. Jun-ya Hasegawa Prof. Tadashi Ema 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(58):e202202210
BPh3 catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO2 and PhSiH3; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C6F5)3 shows little or no activity. 11B NMR spectra suggested the generation of [HBPh3]−. The detailed mechanism of the BPh3-catalyzed N-methylation of N-methylaniline ( 1 ) with CO2 and PhSiH3 was studied by using DFT calculations. BPh3 promotes the conversion of two substrates (N-methylaniline and CO2) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N+CO2−⋅⋅⋅BPh3]. The carbamate and BPh3 act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH3 to generate [HBPh3]−, which is used to produce key CO2-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh3]− species. 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.
Yoshiaki Murata Cheng-Huang Lin Totaro Imasaka 《Fresenius' Journal of Analytical Chemistry》1993,346(6-9):543-544
Summary A supersonic jet spectrum of 9,10-dichloroanthracene is measured by stimulated-emission-pumping fluorescence dip spectrometry and conventional fluorescence spectrometry. The performance obtained is compared for these spectrometric methods, providing same information concerned with the energy level of the ground state. The former is more preferential for measurement of a high-resolution spectrum, since the spectral resolution is determined by the linewidth of the dumping laser. On the other hand, the latter is more preferential for measurement with better sensitivity at the expense of the spectral resolution, since the fluorescence throughput can be improved by increasing the slit width of the monochromator.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday 相似文献
4.
The chemiluminescence (CL) intensities of various indole derivatives substituted with a glyoxylyl group at the 3-position and a hydroxyl group at the 5-position of the indole ring were compared upon the addition of H2O2 in alkaline media. The CL intensities of 3-indoleglyoxylyl chloride, 3-indoleglyoxylic acid, 5-hydroxyindole and 5-benzyloxyindole in CH3CN were 5.9-, 48-, 5.9- and 3.3-fold stronger than that of 3-methylindole. A lasting CL of 3-indoleglyoxylyl chloride was found. Under appropriate conditions, the CL emission reached a maximum within 10 min after the addition of H2O2 in the presence of NaOH, and the intensity was retained for 25 min. One of the final products via the CL reaction of 3-indoleglyoxylyl chloride was indole-3-carboxylic acid. 3-Indoleglyoxylyl chloride emitted light by decompositions via both dioxetane and dioxetanedione. An enhancement effect of beta-cyclodextrin and bovine serum albumin on the CL of 3-indoleglyoxylyl chloride was also found. 相似文献
5.
Aging of concrete buildings and determining the pH value on the surface of concrete by using a handy semi-conductive pH meter. 总被引:1,自引:0,他引:1
A new method was devised for measuring the pH of a concrete surface by pHBOY-P2 with a piece of filter paper by extracting the pH value from concrete. This is a simple and inexpensive method that does not damage the concrete building, and is easy to apply on concrete samples for monitoring. By using the method mentioned above, a drastic decrease of the pH value of concrete bridges and buildings has investigated. The method is environmentally friendly to detect the pH value change of concrete as an environmental sample investigation. 相似文献
6.
Kiyoshi Mochizuki 《Journal of Mathematical Analysis and Applications》2007,326(1):582-588
We show that the energy of solutions to the initial boundary value problem for the wave equation in exterior domains with a dissipation which is localized only near infinity tends to zero as the time goes to infinity. We do not make any geometrical condition like star-shapedness on the boundary. 相似文献
7.
Asymmetric Horner-Wadsworth-Emmons reactions of selected meso-α-dicarbonyl compounds with chiral phosphonate reagents, which possessed axially dissymmetric 1,1′-bi-2- or 8-naphthol at the carboxylate moiety as a chiral auxiliary, were examined. The reactions proceeded smoothly with good chemical yields as well as with high diastereoselectivities. Z-olefins were preferentially formed, and it was found that the free hydroxy group at the 2′- or 8′-position on the naphthalene ring plays a crucial role in the high diastereoselectivity, probably due to a complex-induced proximity effect. Mechanistic considerations are also described. 相似文献
8.
The self-restoration properties in VWP networks are investigated with optimization about spare wavelength by simulations. Rapid restoration can be achieved by selection of rerouting path with long delay and no delay-limitation for new routes. 相似文献
9.
Infrared and nuclear magnetic resonance (NMR) spectroscopies have been applied for quantitative comparison on unsaturated bonds in tetrafluoroethylene (TFE)-propylene (P)-vinylidene fluoride (VdF) terpolymers. These spectroscopies have led to consistent results while they are based on completely different principles. It is shown that the absolute concentration can be evaluated from NMR measurements. The behavior of unsaturation has been discussed in terms of after-treatment such as wet and dry treatments. The result obtained here can give the important information to improve the performance of fluoroelastomer based on TFE-P-VdF terpolymers. 相似文献
10.
In this paper, we investigate the exact distribution of the waiting time for ther-th ℓ-overlapping occurrence of success-runs of a specified length in a sequence of two state Markov dependent trials. The
probability generating functions are derived explicitly, and as asymptotic results, relationships of a negative binomial distribution
of orderk and an extended Poisson distribution of orderk are discussed. We provide further insights into the run-related problems from the viewpoint of the ℓ-overlapping enumeration
scheme. We also study the exact distribution of the number of ℓ-overlapping occurrences of success-runs in a fixed number
of trials and derive the probability generating functions. The present work extends several properties of distributions of
orderk and leads us a new type of geneses of the discrete distributions. 相似文献