全文获取类型
收费全文 | 339篇 |
免费 | 30篇 |
专业分类
化学 | 308篇 |
晶体学 | 2篇 |
力学 | 5篇 |
数学 | 9篇 |
物理学 | 45篇 |
出版年
2024年 | 1篇 |
2023年 | 9篇 |
2022年 | 13篇 |
2021年 | 14篇 |
2020年 | 16篇 |
2019年 | 11篇 |
2018年 | 11篇 |
2017年 | 12篇 |
2016年 | 18篇 |
2015年 | 13篇 |
2014年 | 14篇 |
2013年 | 35篇 |
2012年 | 29篇 |
2011年 | 28篇 |
2010年 | 21篇 |
2009年 | 12篇 |
2008年 | 20篇 |
2007年 | 17篇 |
2006年 | 16篇 |
2005年 | 14篇 |
2004年 | 10篇 |
2003年 | 4篇 |
2002年 | 6篇 |
2000年 | 1篇 |
1990年 | 1篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1987年 | 1篇 |
1985年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 3篇 |
1972年 | 1篇 |
1968年 | 2篇 |
1967年 | 1篇 |
1966年 | 2篇 |
排序方式: 共有369条查询结果,搜索用时 15 毫秒
101.
Kaho Tanaka Naohiko Akasaka Tomoyuki Kosai Shunya Honda Yuya Ushijima Shintaro Ishida Takeaki Iwamoto 《Molecules (Basel, Switzerland)》2021,26(6)
π-Electron systems of silicon have attracted attention because of their narrow HOMO-LUMO gap and high reactivity, but the structural diversity remains limited. Herein, new dialkylboryl-substituted disilenes were synthesized by the selective desilylation-borylation of the corresponding trimethylsilyl-substituted disilenes. The dialkylboryl-substituted disilenes were fully characterized by a combination of NMR spectroscopy, MS spectrometry, single-crystal X-ray diffraction analysis, and theoretical calculations. The longest-wavelength absorption bands of boryldisilenes were bathochromically shifted compared to the corresponding silyl-substituted disilenes, indicating a substantial conjugation between π(Si=Si) and vacant 2p(B) orbitals. In the presence of 4-(dimethylamino)pyridine (DMAP), the dialkylboryl groups in the boryl-substituted disilenes were easily converted to trimethylsilyl groups, suggesting the dialkylboryl-substituted disilenes in the presence of a base serve as the surrogates of disilenyl anions (disilenides). 相似文献
102.
Wataru Uchida Maiki Yoshikawa Tomohiro Seki Ryotaro Miki Toshinobu Seki Takashi Fujihara Yoshihiro Ishimaru Yuya Egawa 《Journal of inclusion phenomena and macrocyclic chemistry》2017,89(3-4):281-288
A boronic acid-appended γ-cyclodextrin (BA-CyD) was synthesized as a hybrid cross-linker of polyvinyl alcohol (PVA) to form a new type of hydrogel. The CyD moiety of BA-CyD forms an inclusion complex with the PVA chain to produce a mechanically interlocking structure. At the same time, the BA moiety of BA-CyD forms covalent bonds with the 1,3-diol moieties of PVA. On the basis of these two modes of interaction, the hybrid cross-linker connects two PVA chains, thus resulting in the formation of a hydrogel. To investigate the possibility of this hydrogel becoming the basis for an intelligent material for drug delivery, sugar-responsive drug release from the hydrogel was demonstrated. 相似文献
103.
Tomonori Ichibakase Tetsuya Kaneko Yuya Orito Shunsuke Kotani Makoto Nakajima 《Tetrahedron》2012,68(22):4210-4224
The aldol reactions of trimethoxysilyl enol ethers catalyzed by lithium binaphtholate were found to be powerful tools for the construction of quaternary asymmetric carbon centers. The stereoselectivities were greatly affected by the presence of water. Trimethoxysilyl enol ether derived from a cyclic ketone, such as cyclohexanone, was used as a substrate to obtain the anti-adduct preferentially under anhydrous conditions; by contrast, the syn-adduct was preferentially obtained under aqueous conditions with high stereoselectivity. The aldol-Tishchenko reaction of a trimethoxysilyl enol ether derived from acyclic ketones proceeded to give monoacyl 1,3-diol derivatives in high enantioselectivities. 相似文献
104.
Yoshihide Usami Yumika Kubo Toshiki Takagaki Nao Kuroiwa Jun Ono Kohei Nishikawa Ayaka Nakamizu Yuya Tatsui Shinya Harusawa Noboru Hayama Hiroki Yoneyama 《Molecules (Basel, Switzerland)》2021,26(11)
The direct 4-alkoxylation of 4-iodo-1H-pyrazoles with alcohols was achieved by a CuI-catalyzed coupling protocol. The optimal reaction conditions employed excess alcohol and potassium t-butoxide (2 equiv) in the presence of CuI (20 mol%) and 3,4,7,8-tetramethyl-1,10-phenanthroline (20 mol%) at 130 °C for 1 h under microwave irradiation. The present method was efficiently applied to the synthesis of withasomnine and its six- and seven-membered cyclic homologs. 相似文献
105.
Yuya Shinohara Naoko Yamamoto Hiroyuki Kishimoto Yoshiyuki Amemiya 《Journal of synchrotron radiation》2015,22(1):119-123
X‐ray photon correlation spectroscopy (XPCS) of swollen rubber containing spherical silica nanoparticles is reported. It is shown that irradiation by intense X‐rays leads to the breakdown of cross‐links, thereby inducing the local rearrangement of silica nanoparticles. This rearrangement process depends on the cross‐link density and is characterized by a compressed exponential relaxation with aging behaviour, which resembles a common feature of complex fluids observed with XPCS. 相似文献
106.
Liquid‐Crystalline Biomacromolecular Templates for the Formation of Oriented Thin‐Film Hybrids Composed of Ordered Chitin and Alkaline‐Earth Carbonate 下载免费PDF全文
Dr. Tatsuya Nishimura Ken Toyoda Takahiro Ito Dr. Yuya Oaki Yukiko Namatame Prof. Takashi Kato 《化学:亚洲杂志》2015,10(11):2356-2360
Macroscopically ordered inorganic thin films have been formed on unidirectionally oriented, liquid‐crystalline chitin matrices. In the presence of poly(acrylic acid) (PAA), unidirectionally oriented chitin films act as templates for the formation of oriented thin‐film crystals of alkaline‐earth carbonates such as SrCO3 and BaCO3. The morphology and orientation of crystals are dependent on the metal ion concentration. For SrCO3 crystallization, unidirectional thin films and hexagonal‐shaped thin films have been deposited from 200 and 25 mm concentration strontium solutions, respectively. 相似文献
107.
Dr. Aiichiro Nagaki Heejin Kim Yuya Moriwaki Chika Matsuo Prof. Jun‐ichi Yoshida 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(36):11167-11177
A flow microreactor system consisting of micromixers and microtube reactors provides an effective tool for the generation and reactions of aryllithiums bearing an alkoxycarbonyl group at para‐, meta‐, and ortho‐positions. Alkyl p‐ and m‐lithiobenzoates were generated by the I/Li exchange reaction with PhLi. The Br/Li exchange reactions with sBuLi were unsuccessful. Subsequent reactions of the resulting aryllithiums with electrophiles gave the desired products in good yields. On the other hand, alkyl o‐lithiobenzoates were successfully generated by the Br/Li exchange reaction with sBuLi. Subsequent reactions with electrophiles gave the desired products in good yields. 相似文献
108.
109.
A pseudorotaxane consisting of a 24-membered crown ether and secondary ammonium salt with the hydroxy group at the terminus was quantitatively acylated by bulky acid anhydride in the presence of tributylphosphane as catalyst to afford the corresponding rotaxane in high yield. Large-scale synthesis without chromatographic separation was easily achieved. The ammonium group in the resulting rotaxane was quantitatively acylated with excess electrophile in the presence of excess trialkylamine. Various N-functionalized rotaxanes were prepared by this sequential double-acylation protocol. 1H NMR spectra and X-ray crystallographic analyses of the rotaxanes showed that the crown ether component was captured on the ammonium group in ammonium-type rotaxane by strong hydrogen-bonding intercomponent interaction. The conformation around the ammonium group was fixed by the hydrogen-bonding interaction. Meanwhile, the conformation of the amide-type rotaxane was determined by the weak CH/pi interaction between the methylene group in crown ether and the benzene ring of the axle component. The N-acylation of ammonium-type rotaxane is useful for the preparation of both functionalized rotaxanes and weak intercomponent interaction-based rotaxanes. 相似文献
110.