全文获取类型
收费全文 | 551篇 |
免费 | 45篇 |
国内免费 | 3篇 |
专业分类
化学 | 484篇 |
晶体学 | 5篇 |
力学 | 3篇 |
数学 | 17篇 |
物理学 | 90篇 |
出版年
2023年 | 6篇 |
2022年 | 8篇 |
2021年 | 9篇 |
2020年 | 14篇 |
2019年 | 14篇 |
2018年 | 17篇 |
2017年 | 4篇 |
2016年 | 19篇 |
2015年 | 26篇 |
2014年 | 22篇 |
2013年 | 38篇 |
2012年 | 43篇 |
2011年 | 63篇 |
2010年 | 23篇 |
2009年 | 33篇 |
2008年 | 28篇 |
2007年 | 25篇 |
2006年 | 29篇 |
2005年 | 22篇 |
2004年 | 22篇 |
2003年 | 25篇 |
2002年 | 10篇 |
2001年 | 4篇 |
2000年 | 2篇 |
1999年 | 2篇 |
1998年 | 4篇 |
1997年 | 6篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 4篇 |
1990年 | 3篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 2篇 |
1984年 | 7篇 |
1983年 | 2篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1977年 | 7篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1973年 | 3篇 |
1970年 | 2篇 |
1969年 | 2篇 |
1968年 | 3篇 |
1967年 | 3篇 |
排序方式: 共有599条查询结果,搜索用时 343 毫秒
91.
Mizukoshi Y Tsuru Y Tominaga A Seino S Masahashi N Tanabe S Yamamoto TA 《Ultrasonics sonochemistry》2008,15(5):875-880
Aqueous sample solutions containing noble metal ions (HAuCl4, Na2PdCl4, H2PtCl6), polyethyleneglycol monostearate, and magnetic maghemite nanoparticles were irradiated with high power ultrasound. Analyses of the products showed that noble metal ions were reduced by the effects of ultrasound, and the formed noble metal nanoparticles were uniformly immobilized on the surface of the maghemite. The present “one pot process” significantly simplifies the immobilization of noble metal nanoparticles on the surface of supports, compared with the conventional impregnation method. The average diameter of immobilized Au was 7–13 nm, and the diameters of Pd and Pt were several nm. The diameters depended upon the concentration of polyethyleneglycol monostearate and the concentration of noble metal ions, but not upon the maghemite concentration, indicating the possibility of the morphological controls of the products by adjusting these preparation conditions. The measurements of the average diameters and the numbers of immobilized Au nanoparticles obtained under various conditions suggest that the nucleation of Au does not occur on the surface of maghemite, but it might occur in the homogeneous bulk solution. 相似文献
92.
Pandur Venkatesan Balaji Lennart Brewitz Naoya Kumagai Masakatsu Shibasaki 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(9):2670-2674
Thioureas have emerged as effective hydrogen‐bonding catalysts over the last two decades, and they are broadly utilized in asymmetric catalysis. We report that achiral trisubstituted thioureas function as beneficial secondary ligands to CuI catalysts, thereby enabling highly diastereo‐ and enantioselective addition of α‐fluoronitriles to imines. The structure of the thiourea significantly affects the reaction outcome, and kinetic experiments indicate that the thioureas enhance the stereocontrol by binding to the CuI complex. The reaction products can be readily transformed into valuable β‐amino acid derivatives bearing a fluorinated tetrasubstituted stereogenic center. 相似文献
93.
Tatsuya Sakakura Assoc. Prof. Naoya Murakami Dr. Yoshiyuki Takatsuji Masayuki Morimoto Prof. Tetsuya Haruyama 《Chemphyschem》2019,20(11):1467-1474
Electric-discharge nitrogen comprises three main types of excited nitrogen species-atomic nitrogen (Natom), excited nitrogen molecules (N2*), and nitrogen ions (N2+) – which have different lifetimes and reactivities. In particular, the interfacial reaction locus between the discharged nitrogen and the water phase produces nitrogen compounds such as ammonia and nitrate ions (denoted as N-compounds generically); this is referred to as the plasma/liquid interfacial (P/L) reaction. The Natom amount was analyzed quantitatively to clarify the contribution of Natom to the P/L reaction. We focused on the quantitative relationship between Natom and the produced N-compounds, and found that both N2* and N2+, which are active species other than Natom, contributed to P/L reaction. The production of N-compounds from N2* and N2+ was enhanced upon UV irradiation of the water phase, but the production of N-compounds from Natom did not increase by UV irradiation. These results revealed that the P/L reactions starting from Natom and those starting from N2* and N2+ follow different mechanisms. 相似文献
94.
A novel implementation of quantum-noise optical cryptography is proposed, which is based on a simplified architecture that allows long-haul, high-speed transmission in a fiber optical network. By using a single multiport encoder/decoder and 16 phase shifters, this new approach can provide the same confidentiality as other implementations of Yuen's encryption protocol, which use a larger number of phase or polarization coherent states. Data confidentiality and error probability for authorized and unauthorized receivers are carefully analyzed. 相似文献
95.
Daisuke Uraguchi Fumito Ueoka Naoya Tanaka Tomohito Kizu Wakana Takahashi Takashi Ooi 《Angewandte Chemie (International ed. in English)》2020,59(28):11456-11461
Catalysis by chiral weakly‐coordinating anions (WCAs) remains underdeveloped due to the lack of a molecular design strategy for exploiting their characteristics, such as the non‐nucleophilic nature. Here, we report the development of a chiral borate ion comprising an O,N,N,O‐tetradentate backbone, which ensures hitherto unattainable structural robustness. Upon pairing with a proton, the hydrogen borate acts as an effective catalyst for the asymmetric Prins‐type cyclization of vinyl ethers, providing access to structurally and stereochemically defined dihydropyrans. The key to selectivity control is the distinct ability of the borate ion to discriminate the prochiral faces of the acyclic oxonium ion intermediate and dictate the regiochemical outcome. We anticipate that this study paves the way for exploring the untapped potential of WCA catalysis for selective chemical synthesis. 相似文献
96.
97.
98.
Dr. Hironobu Hayashi Yuki Kato Dr. Akinobu Matsumoto So Shikita Dr. Naoya Aizawa Prof. Dr. Mitsuharu Suzuki Prof. Dr. Naoki Aratani Prof. Dr. Takuma Yasuda Prof. Dr. Hiroko Yamada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(68):15565-15571
Substituted acene derivatives are regarded as promising materials for organic electronic devices such as organic light-emitting diodes (OLEDs). In particular, anthracene derivatives are known to exhibit good fluorescence property, with the air stability and solubility in common organic solvents expected to give advantages for solution-processed device fabrication. In this study, a series of bistriisopropylsilyl(TIPS)ethynyl anthracene derivatives with azaacene-containing iptycene wings have been synthesized by using condensation reactions. Effects of size of azaacenes on optical properties and packing structures were investigated. UV/Vis absorption and fluorescence spectra indicate that the π-elongation of iptycene units has small effects on the overall π-system, which is also supported by electrochemical measurements. Secondly, single-crystal X-ray analysis implies that the molecules likely have interactions with the iptycene units of adjacent molecules, while the iptycene wings and TIPSethynyl groups can prevent the central anthracene unit from undesirable non-radiative energy loss. Finally, the most emissive derivative was used as a dopant for solution-processed OLEDs, showing obvious electroluminescence with a luminance of over 920 cd m−2. 相似文献
99.
Nucleophilic and Electrophilic Activation of Non‐Heteroaromatic Amides in Atom‐Economical Asymmetric Catalysis 下载免费PDF全文
Dr. Naoya Kumagai Prof. Dr. Masakatsu Shibasaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(43):15192-15200
Recent advances in catalytic asymmetric carbon–carbon bond‐forming reactions of non‐heteroaromatic amide substrates are highlighted. Among carbonyl compounds, amides have received limited attention in catalytic asymmetric transformations mainly owing to their lower reactivity. Amides are reluctant to form enolates for nucleophilic addition, and α,β‐unsaturated amides exhibit diminished electrophilicity at the β‐carbon. Recent advances in asymmetric catalysis rendered these amides amenable to enantioselective reactions with perfect atom economy, producing synthetically useful chiral building blocks. This Minireview summarizes recent developments in the field. 相似文献
100.
Redox‐Driven Symmetry Change for Terbium(III) Bis(porphyrinato) Double‐Decker Complexes by the Azimuthal Rotation of the Porphyrin Macrocycles 下载免费PDF全文
Dr. Ken‐ichi Yamashita Takayo Yamanaka Naoya Sakata Prof. Dr. Takuji Ogawa 《化学:亚洲杂志》2018,13(13):1692-1698
Molecular structures for three oxidation forms (anion, radical, and cation) of terbium(III) bis(porphyrinato) double‐decker complexes have been systematically studied. We found that the redox state controls the azimuthal rotation angle (φ) between the two porphyrin macrocycles. For [TbIII(tpp)2]n (tpp: tetraphenylporphyrinato, n=?1, 0, and +1), φ decreases at each stage of the oxidation process. The decrease in φ is due to the higher steric repulsion between the phenyl rings on the porphyrin macrocycle and the β hydrogen atoms on the other porphyrin macrocycle, which results from the shorter interfacial distance between the two porphyrin macrocycles. Conversely, φ=45° for both [TbIII(oep)2]?1 and [TbIII(oep)2]0 (oep: octaethylporphyrinato), but φ=36° for [TbIII(oep)2]+1. Theoretical calculations suggest that the smaller azimuthal rotation angle of the cation form is due to the electronic interaction in the doubly oxidized ligand system. 相似文献