全文获取类型
收费全文 | 3900篇 |
免费 | 102篇 |
国内免费 | 14篇 |
专业分类
化学 | 3137篇 |
晶体学 | 32篇 |
力学 | 33篇 |
数学 | 233篇 |
物理学 | 581篇 |
出版年
2023年 | 21篇 |
2022年 | 33篇 |
2021年 | 28篇 |
2020年 | 48篇 |
2019年 | 47篇 |
2018年 | 34篇 |
2017年 | 33篇 |
2016年 | 60篇 |
2015年 | 58篇 |
2014年 | 94篇 |
2013年 | 214篇 |
2012年 | 166篇 |
2011年 | 220篇 |
2010年 | 144篇 |
2009年 | 135篇 |
2008年 | 233篇 |
2007年 | 208篇 |
2006年 | 225篇 |
2005年 | 226篇 |
2004年 | 208篇 |
2003年 | 170篇 |
2002年 | 174篇 |
2001年 | 67篇 |
2000年 | 66篇 |
1999年 | 41篇 |
1998年 | 53篇 |
1997年 | 47篇 |
1996年 | 35篇 |
1995年 | 27篇 |
1994年 | 44篇 |
1993年 | 34篇 |
1992年 | 46篇 |
1991年 | 41篇 |
1990年 | 35篇 |
1989年 | 37篇 |
1988年 | 41篇 |
1987年 | 21篇 |
1986年 | 26篇 |
1985年 | 58篇 |
1984年 | 67篇 |
1983年 | 39篇 |
1982年 | 58篇 |
1981年 | 57篇 |
1980年 | 35篇 |
1979年 | 46篇 |
1978年 | 28篇 |
1977年 | 34篇 |
1976年 | 34篇 |
1975年 | 28篇 |
1974年 | 20篇 |
排序方式: 共有4016条查询结果,搜索用时 15 毫秒
1.
D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity 下载免费PDF全文
Yohei Ohkoda Akane Asaishi Tomoya Namiki Tomoaki Hashimoto Midori Yamada Koichiro Shirai Yuta Katagami Dr. Tomoaki Sugaya Prof. Makoto Tadokoro Prof. Akiharu Satake 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(33):11745-11756
The one‐step synthesis of D3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η3‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η3‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands. 相似文献
2.
A new family of positive photosensitive polyimide (PPI) systems composed of solvent soluble polyimides (Pls) with cyclobutane (CBDA) structures and diazonaphthoquinone compounds (DNQ) has been prepared. Heat and catalytic imidizations were carried out to obtain CBDA Pls; the former was better than the latter in controlling the molecular weight of the Pl. The ? OH groups in the Pls were easily acetylated during catalytic imidization, so ? COOH groups were selected as weak acidic groups in the Pls. The ? COOH groups were also effective in giving the Pls an alkaline solubility. Therefore, Pls having ? COOH groups were superior to those having ? OH groups for PPI systems. The photosensitive properties of various PPl systems containing ? COOH were found to vary with the fraction of ? COOH groups in the Pls, the content of DNQ in the systems, and the molecular weight of the Pls. 相似文献
3.
4.
A large-volume (100 microl) injection-ETAAS with W-treated PG furnace combined with a phosphate modifier was applied to the determination of unpolluted levels of Cd in tap, snow and river-water samples. The limit of detection of 1.1 ng l(-1) was observed for a 4 w/v% NH4H2PO4 modifer. Matrix interference studies were tested for major ion species well found in fresh water. The direct determination of Cd in certified river water (12 +/- 2 ng l(-1)) was carried out and the observed value was in agreement with the certified one. The good recoveries of Cd added to real environmental water samples were also observed. This method was applied to the determination of Cd in unpolluted environmental water samples. 相似文献
5.
Yoshiyuki Watabe Takuya Kondo Hiroe Imai Masatoshi Morita Nobuo Tanaka Jun Haginaka Ken Hosoya 《Analytical sciences》2004,20(1):133-137
A new high-performance liquid chromatography (HPLC) method has been developed to detect ultra-low concentrations of bisphenol-A (BPA) (below 1 ng/L (ppt)) using column switching electrochemical detection (ECD). The results were superior to those obtained from manual pretreatment procedure with membrane stationary phase. BPA is inherently ubiquitous in the environment, including tools and solvents used for its analysis; to obtain meaningful results, therefore, the concentration of the overall BPA contamination must be below the detection limit for BPA using the analytical system. Therefore, purified water for preparing the standard BPA solution must be filtered with a hydrophobic membrane to suppress BPA background levels of contamination. In addition, we investigated methods for effectively preserving environmental water containing BPA. The addition of a small amount of ethylenediaminetetraacetic acid (EDTA) provided good recovery even after overnight storage. By employing these precautionary measures and procedures to reduce BPA contamination from the analytical procedure, we could accurately determine l(-10) ppt of BPA in environmental water samples using a column switching HPLC system. 相似文献
6.
The potential of an N-Troc-protected sialic acid donor, equipped with phenylsulfenyl functionality as a leaving group, has been explored. As a result, the entitled donor was proven to be highly reactive and to have broad applicability toward the synthesis of variant sialo-glycans, which have N-glycolyl, de-N-acetyl, 1,5-lactam and 8-O-sulfo sialic acid analogs. 相似文献
7.
Makoto Sakata Takafumi Itsubo Yutakata Moritomo Yasuo Ohishi 《Journal of Physics and Chemistry of Solids》2004,65(12):1973-1976
The experimental and analytical method of the high-pressure powder experiment at BL10XU, SPring-8, is described. There is no doubt that BL10XU must be one of the most appropriate beam lines for high pressure X-ray diffraction experiment taking advantage of third generation synchrotron source. As an example of the advanced charge density study under high pressure, the structural change of Cs2Au2Br6 by applying pressure is studied by Rietveld/MEM analysis. It reveals that the structural change of Cs2Au2Br6 by applying pressure occurs basically at electron level, such as valence state change and chemical bonding, which may be called the electronic phase transition. 相似文献
8.
We propose an extrapolation algorithm for initial value problems in ordinary differential equations. In the algorithm, an appropriately chosen stepsizeH is divided into smaller stepsizes by a sequence and a new stopping rule is proposed. The sequences applied to the algorithm are Romberg {2,4,8,16,32,...}, Bulirsch {2,4,6,8,16...} and Harmonic {2,4,6,8,10,12,...} types. The proposed algorithm is compared numerically with the algorithm introduced by Stoer. In view of the accuracy of numerical solutions, the relatively small number of calculations, the stability and reliability of the algorithm, we found that the algorithm with the Romberg sequence is the best. 相似文献
9.