全文获取类型
收费全文 | 1829篇 |
免费 | 48篇 |
国内免费 | 7篇 |
专业分类
化学 | 1423篇 |
晶体学 | 27篇 |
力学 | 22篇 |
数学 | 87篇 |
物理学 | 325篇 |
出版年
2023年 | 7篇 |
2022年 | 9篇 |
2021年 | 13篇 |
2020年 | 14篇 |
2019年 | 25篇 |
2018年 | 18篇 |
2017年 | 15篇 |
2016年 | 29篇 |
2015年 | 31篇 |
2014年 | 50篇 |
2013年 | 56篇 |
2012年 | 89篇 |
2011年 | 115篇 |
2010年 | 59篇 |
2009年 | 56篇 |
2008年 | 119篇 |
2007年 | 111篇 |
2006年 | 102篇 |
2005年 | 98篇 |
2004年 | 107篇 |
2003年 | 81篇 |
2002年 | 100篇 |
2001年 | 40篇 |
2000年 | 36篇 |
1999年 | 18篇 |
1998年 | 19篇 |
1997年 | 20篇 |
1996年 | 27篇 |
1995年 | 26篇 |
1994年 | 25篇 |
1993年 | 16篇 |
1992年 | 29篇 |
1991年 | 18篇 |
1990年 | 24篇 |
1989年 | 17篇 |
1988年 | 19篇 |
1987年 | 17篇 |
1986年 | 20篇 |
1985年 | 21篇 |
1984年 | 21篇 |
1983年 | 23篇 |
1982年 | 23篇 |
1981年 | 18篇 |
1980年 | 17篇 |
1979年 | 11篇 |
1978年 | 12篇 |
1977年 | 8篇 |
1976年 | 12篇 |
1975年 | 11篇 |
1974年 | 6篇 |
排序方式: 共有1884条查询结果,搜索用时 0 毫秒
81.
Emission Mössbauer spectra of mixedvalence trinuclear complexes,57Co-labelled [CoFe2O(CH3CO2)6(H2O)3] and [CoFe2O(CH3CO2)6 (py)3]py were compared with that of [CoCr2O(CH3CO2)6 (py)3]py. It was found that the57Fe atoms produced in57Co-labelled [CoFe2O(CH3CO2)6(H2O)3] and [CoFe2O(CH3CO2)6 (py)3]py showed a temperature-dependent mixed-valence state as observed in the absorption Mössbauer spectra of [Fe3O(CH3CO2)6 (H2O)3] and [Fe3O(CH3CO2)6 (py)3]py, respectively, while57Co-labelled [CoCr2O(CH3CO2)6 (py)3]py showed a temperature-independent divalent iron/II/ state. The results indicate that the decayed atoms keep their position at the sites of original57Co atoms and that the valence electrons are transferred through the intramolcular bondings. 相似文献
82.
Kazumi Ohya Hiroaki Kitaoka Yasuhiko Yotsui Mitsuji Sano 《Journal of mass spectrometry : JMS》1983,18(4):139-146
The mechanism of the pyrolysis reaction of carpronium chloride [(CH3)3N+? (CH2)3? COOCH3CI?] leading to γ-butyrolactone and tetramethylammonium chloride was investigated by means of thermal analysis, pyrolysis gas chromatography mass spectrometry and field desorption mass spectrometry, using deuterium labelling. The results indicated that carpronium chloride pyrolysed to yield equimolar amounts of γ-butyrolactone and tetramethylammonium chloride, methyl transfer occurred between N and O during the pyrolysis process. The mechanism is discussed on the basis of the experimental results, and with the aid of the theoretical results calculated by the CNDO/2 method. The mechanism presented is as follows. γ-Butyrolactone is formed by the intramolecular migration of the π-orbital of C?O to the carbon adjacent to [(CH3)3N]+ via a 5-membered ring transition state, accompanied by a bimolecular reaction between [(CH3)3N]+ and the CH3 of O? CH3, resulting in the formation of tetramethylammonium chloride in an amount equimolar with γ-butyrolactone. 相似文献
83.
Tachi Y Aita K Teramae S Tani F Naruta Y Fukuzumi S Itoh S 《Inorganic chemistry》2004,43(15):4558-4560
A dicopper(I) complex supported by a novel asymmetric pentapyridine dinucleating ligand, consisting of tetradentate and tridentate metal-binding sites, has been synthesized and characterized. The dicopper(I) complex reacted with molecular oxygen at a low temperature to give an unprecedented mu-peroxo dicopper(II) complex presumably having a mu-eta1:eta2 binding mode, the spectroscopic features and the reactivity of which have been explored in detail. 相似文献
84.
H. Sano 《Journal of Radioanalytical and Nuclear Chemistry》1977,36(1):105-111
Absorption Mössbauer spectra of high-spin57Fe(acac)3 incorporated in diamagnetic Co(acac)3 and in paramagnetic Mn(acac)3 and of the γ-ray irradiated (57Fe, Co) (acac)3 and (57Fe, Mn) (acac)3 were compared with emission spectra of57Co-labelled Co(acac)3. Magnetic hfs is found in the spectra of (57Fe, Co) (acac)3 at 78 to 195 K, whereas such hfs is observed neither for the spectrum of57Co-labelled Co(acac)3 nor for that of γ-ray irradiated (57Fe, Co) (acac)3). The absence of magnetic hfs in the spectrum of diamagnetic57Co-labelled cobalt(III) compounds was ascribed to the spin-spin interaction due to the radicals produced in the vicinity of the decayed atom. 相似文献
85.
86.
87.
88.
Tatsuhiko Nagao Daichi Yukihira Yoshinori Fujimura Kazunori Saito Katsutoshi Takahashi Daisuke Miura Hiroyuki Wariishi 《Analytica chimica acta》2014
In mass spectrometry (MS)-based metabolomics studies, reference-free identification of metabolites is still a challenging issue. Previously, we demonstrated that the elemental composition (EC) of metabolites could be unambiguously determined using isotopic fine structure, observed by ultrahigh resolution MS, which provided the relative isotopic abundance (RIA) of 13C, 15N, 18O, and 34S. Herein, we evaluated the efficacy of the RIA for determining ECs based on the MS peaks of 20,258 known metabolites. The metabolites were simulated with a ≤25% error in the isotopic peak area to investigate how the error size effect affected the rate of unambiguous determination of the ECs. The simulation indicated that, in combination with reported constraint rules, the RIA led to unambiguous determination of the ECs for more than 90% of the tested metabolites. It was noteworthy that, in positive ion mode, the process could distinguish alkali metal-adduct ions ([M + Na]+ and [M + K]+). However, a significant degradation of the EC determination performance was observed when the method was applied to real metabolomic data (mouse liver extracts analyzed by infusion ESI), because of the influence of noise and bias on the RIA. To achieve ideal performance, as indicated in the simulation, we developed an additional method to compensate for bias on the measured ion intensities. The method improved the performance of the calculation, permitting determination of ECs for 72% of the observed peaks. The proposed method is considered a useful starting point for high-throughput identification of metabolites in metabolomic research. 相似文献
89.
Yoshiki Horikawa Naoya Konakahara Tomoya Imai Abe Kentaro Yoshinori Kobayashi Junji Sugiyama 《Polymer Degradation and Stability》2013
The enzymatic hydrolysis of cellulose I achieves almost complete digestion when sufficient enzyme loading as much as 20 mg/g-substrate is applied. However, the yield of digestion reaches the limit when the enzyme dosage is decreased to 2 mg/g-substrate. Therefore, we have performed three pretreatments such as mercerization, dissolution into phosphoric acid and EDA treatment. Transformation into cellulose II hydrate by mercerization and dissolution into phosphoric acid were not sufficient because substrate changed to highly crystalline structure during saccharification. On the other hand, in the case of crystalline conversion of cellulose I to IIII by EDA, almost perfect digestion was achieved even in enzyme loading as small as 0.5 mg/g-substrate, furthermore, hydrolyzed residue was typical cellulose I. The structural analysis of substrate after saccharification provides an insight into relationships between cellulose crystalline property and cellulase toward better enzymatic digestion. 相似文献
90.