全文获取类型
收费全文 | 1199篇 |
免费 | 40篇 |
国内免费 | 3篇 |
专业分类
化学 | 919篇 |
晶体学 | 16篇 |
力学 | 30篇 |
数学 | 63篇 |
物理学 | 214篇 |
出版年
2023年 | 5篇 |
2022年 | 6篇 |
2021年 | 10篇 |
2020年 | 10篇 |
2019年 | 21篇 |
2018年 | 9篇 |
2017年 | 14篇 |
2016年 | 16篇 |
2015年 | 21篇 |
2014年 | 36篇 |
2013年 | 44篇 |
2012年 | 28篇 |
2011年 | 60篇 |
2010年 | 34篇 |
2009年 | 30篇 |
2008年 | 63篇 |
2007年 | 65篇 |
2006年 | 61篇 |
2005年 | 60篇 |
2004年 | 74篇 |
2003年 | 49篇 |
2002年 | 66篇 |
2001年 | 40篇 |
2000年 | 32篇 |
1999年 | 23篇 |
1998年 | 10篇 |
1997年 | 16篇 |
1996年 | 19篇 |
1995年 | 16篇 |
1994年 | 11篇 |
1993年 | 14篇 |
1992年 | 24篇 |
1991年 | 16篇 |
1990年 | 12篇 |
1989年 | 7篇 |
1988年 | 13篇 |
1987年 | 13篇 |
1986年 | 7篇 |
1985年 | 24篇 |
1984年 | 30篇 |
1983年 | 17篇 |
1982年 | 16篇 |
1981年 | 15篇 |
1980年 | 14篇 |
1979年 | 8篇 |
1978年 | 10篇 |
1977年 | 10篇 |
1976年 | 5篇 |
1975年 | 10篇 |
1973年 | 11篇 |
排序方式: 共有1242条查询结果,搜索用时 203 毫秒
71.
Dr. Yohei Hattori Tatsuya Maejima Yumi Sawae Jun-ichiro Kitai Prof. Masakazu Morimoto Dr. Ryojun Toyoda Prof. Hiroshi Nishihara Prof. Satoshi Yokojima Dr. Shinichiro Nakamura Prof. Kingo Uchida 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(50):11441-11450
The cyclization reaction of diarylethenes having an azulene ring occurs only via higher excited states. Novel diarylethenes having an azulene ring with a strong donor or acceptor were synthesized and examined in these reactions. A derivative having an electron-donating 1,3-benzodithiol-2-ylidenemethyl group at the 1-position of the azulene ring showed photochromism, whereas neither a derivative having a π-conjugated electron-donating group at the 3-position of the azulene ring nor derivatives having a π-conjugated electron-withdrawing group at the 1- or 3-position of the azulene ring showed any photochromism. The photoreactivities of these compounds were explained by calculating forces and bond orders on the excited states using density functional theory (DFT) and time-dependent (TD)-DFT. 相似文献
72.
Nobuyuki Otozawa Rio Hamajima Masataka Yoshioka Raito Kato Arisa Tanaka Hiroto Fukuma Toshiki Terao Kei Manabe Syuji Fujii Yoshinobu Nakamura Atsushi Takahara Tomoyasu Hirai 《Journal of polymer science. Part A, Polymer chemistry》2020,58(14):1960-1964
This study investigates the effect of ionic liquids (ILs) on the anionic polymerization of methyl methacrylate (MMA). Polymethyl methacrylate (PMMA), an isotactic polymer, is prepared by anionic polymerization at a high reaction temperature with an IL that acts as both solvent and additive. The most plausible reaction mechanism is determined using 1H NMR and Fourier-transform infrared spectroscopy. The electrostatic interaction between MMA and the IL increases the apparent steric hindrance in MMA, resulting in the isotactic PMMA. 相似文献
73.
The secondary radiation after resonant excitation of F center and its linear polarization P correlated to the polarization of resonant light have been measured for five alkali halides at low temperatures. In KC1, the spectrum of P over the whole Stokes region is divided into three successive regions, the depolarization range at the one-phonon Raman scattering, the near plateau range, and the depolarization range down to vanishing. The former two have common relevance to resonant energy and symmetries of coupled phonons. These relevances are interpreted adopting a configuration coordinate model for 2s- and 2p-like excited states. 相似文献
74.
Takashi Kitayama Maki Nakahira Kae Yamasaki Hiromi Inoue Chika Imada Yuji Yonekura Masataka Awata Hikaru Takaya Yasushi Kawai Kohta Ohnishi Akira Murakami 《Tetrahedron》2013
Zerumbone 1, having powerful latent reactivity and containing two conjugated double bonds and a double conjugated carbonyl group is the major component of the essential oil of wild ginger, Zingiber zerumbet Smith. The conjugation system plays an important role in the expression of biological activity. N-Bromosuccinimide (NBS) reaction of 1 gave high reactive intermediate 2 with an exo-methylene group, which was obtained from 1 quantitatively. Treatment of 2 with nucleophiles gave various zerumbone-pendant derivatives, including C–H, C–O, C–N, and C–C bond formation, maintaining the conjugation system through SN2′-type reaction. Almost all zerumbone-pendant derivatives showed a good value of IC50 against the suppressive effect of NO generation. Among them, amine derivative 5, binding with 2 mol of zerumbone, showed the strongest activity (IC50: 0.24 μM). 相似文献
75.
Photochromic acrylates containing both biphenylene and spiro-oxazine moieties with a chiral substituent and the related polymers were prepared and yielded photochromic chiral liquid crystalline systems. The photochromic acrylates containing both an undecamethylene group and a (2S, 3S)-2-chloro-3-methylpentanoyloxy group (A11SOP) or a (-)-menthoxyacetoxy group (A11SOM) gave a supercooled mesophase; the latter reflected right-handed visible light (blue colour) at room temperature. On the other hand, the photochromic acrylate containing both the (R)-(-)-2-methylpropylene and (2S, 3S)-2-chloro-3-methylpentanoyloxy groups (A3SOP) showed no mesophase. The related homopolymers, PA11SOP and PA11SOM, did not exhibit mesophases because of steric hindrance between the side groups of the polymers. However, only PA11SOM exhibited shear-induced birefringence under 100-104°C. Several copolymers consisting of the nematogenic monomer, 4-[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzonitrile (A6CN), and A11SOP or A11SOM possessed a smectic phase due to reduction of the steric hindrance between the potentially smectogenic A11SOP or A11SOM moieties. 相似文献
76.
Kazuhiko Semba Masataka Shinomiya Prof. Dr. Tetsuaki Fujihara Prof. Dr. Jun Terao Prof. Dr. Yasushi Tsuji 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(22):7125-7132
The highly selective copper‐catalyzed hydroboration of allenes has been developed. Allylboranes and alkenylboranes were selectively prepared by the judicious choice of catalytic species (copper hydride and boryl copper). Furthermore, two types of alkenylboranes could be selectively synthesized by the choice of an appropriate ligand. Mechanistic studies confirmed that the protonation of a (Z)‐σ‐allyl copper species, which was isolated and structurally characterized by single‐crystal X‐ray diffraction, was a key step in these reactions. Besides allenes, this method is also applicable to the selective hydroboration of 1,3‐diene derivatives to afford allylboranes and homoallylboranes. 相似文献
77.
I. Sugai M. Oyaizu Y. Takeda H. Kawakami K. Kawasaki T. Hattori T. Kadono 《Journal of Radioanalytical and Nuclear Chemistry》2014,299(2):1023-1028
Nitrided carbon stripper (NCS) foils with high nitrogen content were produced by ion beam sputtering of reactive nitrogen gas. Such foils seem to be very useful as strippers in high-intensity heavy ion accelerators. We have conducted comprehensive research, development, and production of such foils with high reproducibility. Krypton, a heavy noble gas, was mixed with the reaction nitrogen gas (IBSRN) in the ion beam sputtering process to produce stripper foils with short sputtering deposition time and long lifetimes in the high intensity ion beam irradiation. With the (N2 + Kr) mixed gas ions we investigated the influence of different sputtering angles (α) on the lifetime of the NCS-foils in case of poly-graphite material. The lifetime measurement of these foils of 20 ± 5 μg/cm2 was performed with a 3.2 MeV Ne+ ion beam as usual. The foils made at a sputtering angle of 15° showed a maximum of 11.0 and 7.5 C/cm2 average charge density, respectively, which corresponded to about 275 and 187 times the lifetime of the best commercially available foils. 相似文献
78.
Single‐Crystal‐like Nanoporous Spinel Oxides: A Strategy for Synthesis of Nanoporous Metal Oxides Utilizing Metal‐Cyanide Hybrid Coordination Polymers
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Masataka Imura Rahul R. Salunkhe Naoto Umezawa Hicham Hamoudi Alexei A. Belik Yusuke Yamauchi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(52):17375-17384
Development of a new method to synthesize nanoporous metal oxides with highly crystallized frameworks is of great interest because of their wide use in practical applications. Here we demonstrate a thermal decomposition of metal‐cyanide hybrid coordination polymers (CPs) to prepare nanoporous metal oxides. During the thermal treatment, the organic units (carbon and nitrogen) are completely removed, and only metal contents are retained to prepare nanoporous metal oxides. The original nanocube shapes are well‐retained even after the thermal treatment. When both Fe and Co atoms are contained in the precursors, nanoporous Fe?Co oxide with a highly oriented crystalline framework is obtained. On the other hand, when nanoporous Co oxide and Fe oxide are obtained from Co‐ and Fe‐contacting precursors, their frameworks are amorphous and/or poorly crystallized. Single‐crystal‐like nanoporous Fe?Co oxide shows a stable magnetic property at room temperature compared to poly‐crystalline metal oxides. We further extend this concept to prepare nanoporous metal oxides with hollow interiors. Core‐shell heterostructures consisting of different metal‐cyanide hybrid CPs are prepared first. Then the cores are dissolved by chemical etching using a hydrochloric acid solution (i.e., the cores are used as sacrificial templates), leading to the formation of hollow interiors in the nanocubes. These hollow nanocubes are also successfully converted to nanoporous metal oxides with hollow interiors by thermal treatment. The present approach is entirely different from the surfactant‐templating approaches that traditionally have been utilized for the preparation of mesoporous metal oxides. We believe the present work proves a new way to synthesize nanoporous metal oxides with controlled crystalline frameworks and architectures. 相似文献
79.
New analytical method for the study of the metabolism of gentiopicroside in rats after oral administration by LC–TOF‐MS following picolinoyl derivatization
下载免费PDF全文
![点击此处可从《Journal of separation science》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Zhigang Wang Shanshan Wang Yujia Sun Huiyu Wang Guang Chen Xijun Wang Masao Hattori Hailong Zhang 《Journal of separation science》2014,37(3):237-243
The metabolism of gentiopicroside (GPS) in vivo was studied for the first time by LC–MS following picolinoyl derivatization. Incubation of erythrocentaurin, one of the main in vitro metabolites of GPS by intestinal bacteria, with liver microsome indicated that GPS might be metabolized to a final metabolite 3,4‐dihydro‐5‐(hydroxymethyl)isochroman‐1‐one (HMIO) in vivo. After hydrolysis with sulfatase, HMIO was successfully detected in rat plasma after oral administration of GPS by LC–MS following picolinoyl derivatization. 4‐Methoxyphenyl methanol was used as an internal standard to quantify HMIO in rat plasma. A metabolic pathway of GPS in rats is proposed. The monoterpene compound GPS was found to be metabolized to dihydroisocoumarin, which may be responsible for the pharmacological effect of GPS. 相似文献
80.
Muhammet Uyanik Naoto Sahara Mayuko Tsukahara Yuhei Hattori Kazuaki Ishihara 《Angewandte Chemie (International ed. in English)》2020,59(39):17110-17117
We report high‐performance I+/H2O2 catalysis for the oxidative or decarboxylative oxidative α‐azidation of carbonyl compounds by using sodium azide under biphasic neutral phase‐transfer conditions. To induce higher reactivity especially for the α‐azidation of 1,3‐dicarbonyl compounds, we designed a structurally compact isoindoline‐derived quaternary ammonium iodide catalyst bearing electron‐withdrawing groups. The nonproductive decomposition pathways of I+/H2O2 catalysis could be suppressed by the use of a catalytic amount of a radical‐trapping agent. This oxidative coupling tolerates a variety of functional groups and could be readily applied to the late‐stage α‐azidation of structurally diverse complex molecules. Moreover, we achieved the enantioselective α‐azidation of 1,3‐dicarbonyl compounds as the first successful example of enantioselective intermolecular oxidative coupling with a chiral hypoiodite catalyst. 相似文献