全文获取类型
收费全文 | 3031篇 |
免费 | 83篇 |
国内免费 | 10篇 |
专业分类
化学 | 2240篇 |
晶体学 | 33篇 |
力学 | 34篇 |
数学 | 159篇 |
物理学 | 658篇 |
出版年
2023年 | 12篇 |
2021年 | 17篇 |
2020年 | 38篇 |
2019年 | 51篇 |
2018年 | 40篇 |
2017年 | 20篇 |
2016年 | 59篇 |
2015年 | 48篇 |
2014年 | 71篇 |
2013年 | 155篇 |
2012年 | 150篇 |
2011年 | 176篇 |
2010年 | 106篇 |
2009年 | 93篇 |
2008年 | 157篇 |
2007年 | 154篇 |
2006年 | 147篇 |
2005年 | 148篇 |
2004年 | 124篇 |
2003年 | 136篇 |
2002年 | 101篇 |
2001年 | 70篇 |
2000年 | 70篇 |
1999年 | 38篇 |
1998年 | 23篇 |
1997年 | 30篇 |
1996年 | 29篇 |
1995年 | 24篇 |
1994年 | 32篇 |
1993年 | 40篇 |
1992年 | 37篇 |
1991年 | 49篇 |
1990年 | 46篇 |
1989年 | 32篇 |
1988年 | 43篇 |
1987年 | 44篇 |
1986年 | 36篇 |
1985年 | 63篇 |
1984年 | 43篇 |
1983年 | 21篇 |
1982年 | 34篇 |
1981年 | 35篇 |
1980年 | 24篇 |
1979年 | 36篇 |
1978年 | 33篇 |
1977年 | 42篇 |
1976年 | 31篇 |
1975年 | 23篇 |
1974年 | 18篇 |
1973年 | 22篇 |
排序方式: 共有3124条查询结果,搜索用时 15 毫秒
101.
Molydbenum and tungsten-catalyzed oxidations of alcohols with dilute hydrogen peroxide under phase-transfer conditions have been focused in recent years 1–3. In a previous paper, we have reported that tricetylpyridinium-12-molybdophosphate(CMP), [π - C5H5N+(CH2 15CH3]3 (PMO12O40)3-, prepared from 12-molybdophosphoric acid (MPA) and cetylpyridinium chloride (CPC), catalyzed the oxidation of secondary alcohols to carbonyl compounds with tert-butylhydroperoxide(t-BuOOH)4. When hydrogen peroxide in place of t-BuOOH was employed as the oxidant for the above oxidation, however, alcohols were oxidized with difficulty to give carbonyl compounds in poor yields. In continuation of this study, we wish to report here the selective oxidation of secondary hydroxy group of alcohols and diols and diols with H2O2 under the influence to tricetylpyridinium-12 tungstophosphate (CWP), [π-C5H5N+ (CH2) 15 CH3]3(PW12O40)3-, derived from 12-tungstophosporic acid (WPA) and CPC. 相似文献
102.
A mechanistic study was carried out for the asymmetric Michael addition reaction of malonates to enones catalyzed by a primary amino acid lithium salt to elucidate the origin of the asymmetric induction. A primary β-amino acid salt catalyst, O-TBDPS β-homoserine lithium salt, exhibited much higher enantioselectivity than that achieved with the corresponding catalysts derived from α- and γ-amino acids for this reaction. Detailed studies of the transition states with DFT calculations revealed that the lithium cation and carboxylate group of the β-amino acid salt catalyst have important roles in achieving high enantioselectivity in the Michael addition reaction of malonates to enones. 相似文献
103.
Abstract The epoxidation of allylic alcohols with H2O2 catalyzed by a new Mo-species, [PMo12O40]3?[C5H5N+(CH2)15CH3]3 (MPCP), prepared from 12-molybdatophosphoric acid (H3PMo12O40) and cetylpyridinium chloride [C5H5N+(CH2)15CH3 · Cl?], has recently rep0rted.) The high regioselectivity for the epoxidation by this MPCP-H2O2 system was comparable to that of Sharpless method using t-BuOOH as oxidant. 相似文献
104.
Unsaturated nitriles have been synthesized from trisubstituted olefins via ene-type chlorination and regioselective substitution with cyanide ion followed by double bond migration. 相似文献
105.
Yuki Goto Masahiro Shiosaki Takeshi Hanamoto Masato Yoshida Hideo Sawada 《Colloid and polymer science》2013,291(5):1211-1217
Fluoro(silyl)acetylenes, which were prepared by reaction of 1,1-difluoroethylene with silyl chlorides, reacted with triethylamine to give dark-brown colored polyfluoro(silyl)acetylene powders in excellent to moderate isolated yields. In contrast, the corresponding nonfluorinated acetylene was unable to react with triethylamine at all to afford poly(silyl)acetylene under similar conditions. Polyfluoro(silyl)acetylenes thus obtained were nanometer size-controlled cubic fine particles with a good dispersibility and stability in a variety of solvents. These polyfluoro(silyl)acetylene nanoparticles exhibited clear absorption and emission spectra related to the conjugated units in polymer main chain. Furthermore, these polyfluoro(silyl)acetylene nanoparticles were applied to the surface modification of poly(methyl methacrylate) [PMMA] film to exhibit a higher oleophobicity imparted by fluorine on their surface, compared to that on the reverse side. Figure
New polyfluoro(silyl)acetylenes were prepared by reaction of the creesponding fluoro(silyl)acetylenes with triethylamine in excellent to moderate isolated yields. In contrast, the corresponding nonfluorinated silylacetylene was unable to give poly(silyl)acetylene under similar conditions. These polyfluoro(silyl)acetylenes thus obtained can form the nanometer size-controlled cubic fine particles (within 100 nm) in a variety of solvents. 相似文献
106.
Katsuya Maeyama Kenji Yamashita Shugo Maeda Noriyuki Yonezawa Shunichi Aikawa Yasuhiko Yoshida 《合成通讯》2013,43(23):4158-4170
Optically active aromatic ether ketone macrocycles containing 2,2′-dimethoxy-1,1′-binaphthyl-6,6′-diyl moieties were synthesized through electrophilic aromatic substitution reaction and stepwise nucleophilic aromatic substitution reactions. Structures of the resulting macrocycles were confirmed by NMR and matrix assisted laser desorption/ionization time of flight (MALDI-TOF) mass measurements. 相似文献
107.
Norimitsu Yoshida Sho Terazawa Kotaro Hayashi Tomonari Hamaguchi Hironori Natsuhara Shuichi Nonomura 《Journal of Non》2012,358(17):1987-1989
Effects of deposition conditions on the structure of microcrystalline silicon carbide (μc-SiC) films prepared by hot-wire chemical vapor deposition (hot-wire CVD) method have been investigated. It is found from X-ray diffraction patterns of the film that a diffraction peak from crystallites from hexagonal polytypes of SiC is observed in addition to those of 3 C-SiC crystallites. This result is obtained in the film under a narrow deposition conditions of SiH3CH3 gas pressure of 8 Pa, the H2 gas pressure of 80–300 Pa and the total gas pressure of 40–300 Pa under fixed substrate and filament temperatures employed in this study. Furthermore, the grain size of hexagonal crystallites (about 20 nm) on c-Si substrates becomes larger than that of 3 C-SiC crystallites (about 10 nm) for the films deposited under the total gas pressure of 36–88 Pa. The fact that microcrystalline hexagonal SiC can be deposited under limited deposition conditions could be interpreted in the context of a result for c-SiC polytypes prepared by thermal CVD method. 相似文献
108.
Akira Ishida Yuichi Sasaki Ginga Akimoto Taikan Suehara Toshio Namba Shoji Asai Tomio Kobayashi Haruo Saito Mitsuhiro Yoshida Kenichi Tanaka Akira Yamamoto 《Hyperfine Interactions》2012,212(1-3):133-140
Positronium is an ideal system for the research of the quantum electrodynamics (QED) in bound state. The hyperfine splitting (HFS) of positronium, ΔHFS, gives a good test of the bound state calculations and probes new physics beyond the Standard Model. A new method of QED calculations has revealed the discrepancy by 15 ppm (3.9σ) of ΔHFS between the QED prediction and the experimental average. There would be possibility of new physics or common systematic uncertainties in the previous all experiments. We describe a new experiment to reduce possible systematic uncertainties and will provide an independent check of the discrepancy. We are now taking data and the current result of ΔHFS?=?203.395 1 ±0.002 4 (stat., 12 ppm) ±0.001 9 (sys., 9.5 ppm) GHz has been obtained so far. A measurement with a precision of O(ppm) is expected within a year. 相似文献
109.
Yoshida K Yamaguchi T Kittaka S Bellissent-Funel MC Fouquet P 《J Phys Condens Matter》2012,24(6):064101
Neutron spin echo measurements of monolayer and capillary condensed heavy water (D(2)O) confined in MCM-41 C10 (pore diameter 2.10 nm) were performed in a temperature range of 190-298 K. The intermediate scattering functions were analyzed by the Kohlrausch-Williams-Watts stretched exponential function. The relaxation times of confined D(2)O in the capillary condensed state follow remarkably well the Vogel-Fulcher-Tammann equation between 298 and 220 K, whereas below 220 K they show an Arrhenius type behavior. That is, the fragile-to-strong (FTS) dynamic crossover occurs, which has never been seen in experiments on bulk water. On the other hand, for monolayer D(2)O, the FTS dynamic crossover was not observed in the temperature range measured. The FTS dynamic crossover observed in capillary condensed water would take place in the central region of the pore, not near the pore surface. Because the tetrahedral-like water structure in the central region of the pore is more preserved than that near the pore surface, the FTS dynamic crossover would be concerned with the tetrahedral-like water structure. 相似文献
110.
Despite the conceptional importance of realizing spin liquids in solid states only few compounds are known. On the other hand the effect of lattice distortions and anisotropies on the magnetic exchange topology and the fluctuation spectrum is an interesting problem. We compare the excitation spectra of the two s = 1/2 kagome lattice compounds, volborthite and vesignieite, using Raman scattering. We demonstrate that even small modifications of the crystal structure may have a huge effect on the phonon spectrum and low-temperature properties. 相似文献