全文获取类型
收费全文 | 756篇 |
免费 | 27篇 |
国内免费 | 2篇 |
专业分类
化学 | 588篇 |
晶体学 | 6篇 |
力学 | 9篇 |
数学 | 16篇 |
物理学 | 166篇 |
出版年
2022年 | 4篇 |
2021年 | 11篇 |
2020年 | 16篇 |
2019年 | 20篇 |
2018年 | 7篇 |
2017年 | 6篇 |
2016年 | 21篇 |
2015年 | 15篇 |
2014年 | 19篇 |
2013年 | 47篇 |
2012年 | 40篇 |
2011年 | 45篇 |
2010年 | 26篇 |
2009年 | 32篇 |
2008年 | 35篇 |
2007年 | 30篇 |
2006年 | 33篇 |
2005年 | 28篇 |
2004年 | 29篇 |
2003年 | 27篇 |
2002年 | 30篇 |
2001年 | 23篇 |
2000年 | 11篇 |
1999年 | 16篇 |
1998年 | 9篇 |
1997年 | 9篇 |
1996年 | 12篇 |
1995年 | 4篇 |
1994年 | 8篇 |
1993年 | 8篇 |
1992年 | 13篇 |
1991年 | 9篇 |
1990年 | 12篇 |
1989年 | 18篇 |
1987年 | 8篇 |
1985年 | 8篇 |
1984年 | 10篇 |
1982年 | 5篇 |
1981年 | 7篇 |
1980年 | 4篇 |
1979年 | 8篇 |
1978年 | 4篇 |
1975年 | 5篇 |
1974年 | 4篇 |
1972年 | 3篇 |
1971年 | 3篇 |
1970年 | 4篇 |
1969年 | 3篇 |
1967年 | 3篇 |
1930年 | 4篇 |
排序方式: 共有785条查询结果,搜索用时 31 毫秒
141.
Kishi Y Nagura H Inagi S Fuchigami T 《Chemical communications (Cambridge, England)》2008,(33):3876-3878
Prins cyclization of homoallylic alcohols, thiols, and amines with various aldehydes in an ionic liquid HF salt (Et(4)NF.5HF) afforded the corresponding 4-fluorinated heterocycles in excellent yields. 相似文献
142.
143.
Sakai K Umezawa S Tamura M Takamatsu Y Tsuchiya K Torigoe K Ohkubo T Yoshimura T Esumi K Sakai H Abe M 《Journal of colloid and interface science》2008,318(2):440-448
The adsorption and micellization behavior of novel sugar-based gemini surfactants (N,N(')-dialkyl-N,N(')-digluconamide ethylenediamine, Glu(n)-2-Glu(n), where n is the hydrocarbon chain length of 8, 10 and 12) has been studied on the basis of static/dynamic surface tension, fluorescence, dynamic light scattering (DLS) and cryogenic transmission electron microscope (cryo-TEM) data. The static surface tension of the aqueous Glu(n)-2-Glu(n) solutions measured at the critical micelle concentration (cmc) is observed to be significantly lower than that of the corresponding monomeric surfactants. This suggests that the gemini surfactants, newly synthesized in the current study, are able to form a closely packed monolayer film at the air/aqueous solution interface. The greater ability in the molecular association is supported by the remarkably (approximately 100-200 times) lower cmc of the gemini surfactants compared with the corresponding monomeric ones. With a combination of the fluorescence and DLS data, a structural transformation of the Glu(n)-2-Glu(n) micelles is suggested to occur with an increase in the concentration. The cryo-TEM measurements clearly confirm the formation of worm-like micelles of Glu(12)-2-Glu(12) at the concentration well above the cmc. 相似文献
144.
Hori T Peng X Aratani N Takagi A Matsumoto T Kawai T Yoon ZS Yoon MC Yang J Kim D Osuka A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(2):582-595
Starting from 1,3-phenylene linked diporphyrin zinc(II) complex 2ZA, repeated stepwise Ag I-promoted coupling reactions provided linear oligomers from 2nZA up to 128ZA. Of these zigzag shaped porphyrin arrays, the Ag I-promoted intramolecular cyclization reaction of 2 nZA (n=5, 6, 8, 9, 12, and 16) under dilute conditions gave the corresponding cyclic porphyrin wheels C2nZA (n=5, 6, 8, 9, 12, and 16), whereas large arrays 2nZA (n=24, 32, and 48) did not provide cyclic porphyrin products. These large discrete porphyrin arrays and wheels were fully characterized by means of 1H NMR spectroscopy, MALDI-TOF mass spectrometry, UV/Vis absorption spectroscopy, GPC-HPLC analysis, and the scanning tunneling microscopy (STM) technique. The STM images of C12ZA and C18ZA reveal their large circular structures. In the cyclic structures of C2nZA in solution, however, the gradual decrease in fluorescence quantum yields and fluorescence lifetimes are observed, reflecting some conformational heterogeneities. Collectively, the present work provides an important contribution to the construction of fully covalently linked large cyclic arranged porphyrin arrays with ample electronic interactions as a model of light-harvesting antenna. 相似文献
145.
Himeda Y Onozawa-Komatsuzaki N Miyazawa S Sugihara H Hirose T Kasuga K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(35):11076-11081
Transfer hydrogenation catalyzed by an iridium catalyst with 4,4'-dihydroxy-2,2'-bipyridine (DHBP) in an aqueous formate solution exhibits highly pH-dependent catalytic activity and chemoselectivity. The substantial change in the activity is due to the electronic effect based on the acid-base equilibrium of the phenolic hydroxyl group of DHBP. Under basic conditions, high turnover frequency values of the DHBP complex, which can be more than 1000 times the value of the unsubstituted analogue, are obtained (up to 81 000 h(-1) at 80 degrees C). In addition, the DHBP catalyst exhibits pH-dependent chemoselectivity for alpha,beta-unsaturated carbonyl compounds. Selective reduction of the C=C bond of enone with high activity are observed under basic conditions. The ketone moieties can be reduced with satisfactory activity under acidic conditions. In particular, pH-selective chemoselectivity of the C=O versus C=C bond reduction was observed in the transfer hydrogenation of cinnamaldehyde. 相似文献
146.
Dr. Kenichi Kato Dr. Hidetaka Kasai Dr. Akihiro Hori Prof. Dr. Masaki Takata Prof. Dr. Hiroshi Tanaka Prof. Dr. Susumu Kitagawa Akira Kobayashi Dr. Nobuki Ozawa Prof. Dr. Momoji Kubo Dr. Hidekazu Arikawa Prof. Dr. Tatsuya Takeguchi Dr. Masaaki Sadakiyo Prof. Dr. Miho Yamauchi 《化学:亚洲杂志》2016,11(10):1537-1541
The layered P2‐NaxMO2 (M: transition metal) system has been widely recognized as electronic or mixed conductor. Here, we demonstrate that Co vacancies in P2‐NaxCoO2 created by hydrogen reductive elimination lead to an ionic conductivity of 0.045 S cm?1 at 25 °C. Using in situ synchrotron X‐ray powder diffraction and Raman spectroscopy, the composition of the superionic conduction phase is evaluated to be Na0.61(H3O)0.18Co0.93O2. Electromotive force measurements as well as molecular dynamics simulations indicate that the ion conducting species is proton rather than hydroxide ion. The fact that the Co‐stoichiometric compound Nax(H3O)yCoO2 does not exhibit any significant ionic conductivity proves that Co vacancies are essential for the occurrence of superionic conductivity. 相似文献
147.
Inside Cover: Superionic Conduction in Co‐Vacant P2‐NaxCoO2 Created by Hydrogen Reductive Elimination (Chem. Asian J. 10/2016) 下载免费PDF全文
Dr. Kenichi Kato Dr. Hidetaka Kasai Dr. Akihiro Hori Prof. Dr. Masaki Takata Prof. Dr. Hiroshi Tanaka Prof. Dr. Susumu Kitagawa Akira Kobayashi Dr. Nobuki Ozawa Prof. Dr. Momoji Kubo Dr. Hidekazu Arikawa Prof. Dr. Tatsuya Takeguchi Dr. Masaaki Sadakiyo Prof. Dr. Miho Yamauchi 《化学:亚洲杂志》2016,11(10):1465-1465
148.
149.
Yoon MC Yoon ZS Cho S Kim D Takagi A Matsumoto T Kawai T Hori T Peng X Aratani N Osuka A 《The journal of physical chemistry. A》2007,111(38):9233-9239
A belt-shaped hexagonal cyclic porphyrin array 2 that comprises of six meso-meso, beta-beta, beta-beta triply linked diporphyrins 3 bridged by 1,3-phenylene spacers is prepared by oxidation from cyclic dodecameric array 1 consisting of six meso-meso directly linked diporphyrins 4 with DDQ and Sc(OTf)3. The absorption spectrum of 2 is similar to that of the constituent subunit 3 but shows a slight red-shift for the Q-bands in near-infrared (NIR) region, indicating the exciton coupling between the neighboring diporphyrin chromophores. Observed total exciton coupling energies in the absorption spectra were largely matched with the calculated values based on point-dipole exciton coupling approximation. It was found that the experimental exciton coupling strength (292 cm(-1)) of the Q-band in 2 is slightly larger than the calculated one (99 cm(-1)), indicating that the electronic communications are enhanced through 1,3-phenylene linkers in hexameric macromolecule. A rate of the excitation energy hopping (EEH) that occurs in 2 at the lowest excited singlet state in the near-infrared region has been determined to be (1.8 ps)(-1) on the basis of the pump-power dependent femtosecond transient absorption (TA) and the transient absorption anisotropy (TAA) decay measurements. The 2 times faster EEH rate of 2 than that of 1 (4.0 ps)(-1) mainly comes from involving through-bond energy transfer among diporphyrin subunits via 1,3-phenylene bridges as well as F?rster-type through-space EEH processes. STM measurement of 2 in the Cu(100) surface revealed that it takes several discrete conformations with respect to the relative orientation of neighboring diporphyrins. Collectively, an effective EEH in the NIR region is realized in 2 due largely to the intensified oscillator strength in the S(1) state (Q-band) and the close proximity held by 1,3-phenylene spacers. 相似文献
150.
The miscibility of polyvinylphenol (PVPh) or terpenephenol (TPh) with polyoxymethylene (POM) was examined by high-resolution solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. It was found that the driving force for the mixing of POM and PVPh is the hydrogen-bonding interaction between the phenolic OH group of PVPh and the ether oxygen of POM, and that the mixing is preferentially induced in the noncrystalline phase. 1H relaxation time experiments indicated that POM/PVPh blends were homogeneous on a scale of 20–30 nm but heterogeneous on a scale of 2–3 nm. On the other hand, Fourier transform infrared and cross-polarization/magic-angle-spinning 13C-NMR (nuclear magnetic resonance) spectra revealed that POM and TPh are also mixed in the noncrystalline phase through the intermolecular hydrogen-bonding interaction, while some fraction of POM is still crystallizable. Moreover, the domain size of the micro-phase separation was estimated to be about 1 nm by the direct 1H spin-diffusion measurements, suggesting almost homogeneous mixing on a molecular level in the noncrystalline phase. © 1997 John Wiley & Sons, Ltd. 相似文献