全文获取类型
收费全文 | 1565篇 |
免费 | 73篇 |
国内免费 | 8篇 |
专业分类
化学 | 1304篇 |
晶体学 | 9篇 |
力学 | 15篇 |
数学 | 82篇 |
物理学 | 236篇 |
出版年
2024年 | 3篇 |
2023年 | 21篇 |
2022年 | 19篇 |
2021年 | 20篇 |
2020年 | 36篇 |
2019年 | 46篇 |
2018年 | 40篇 |
2017年 | 16篇 |
2016年 | 34篇 |
2015年 | 56篇 |
2014年 | 58篇 |
2013年 | 92篇 |
2012年 | 110篇 |
2011年 | 101篇 |
2010年 | 78篇 |
2009年 | 63篇 |
2008年 | 114篇 |
2007年 | 86篇 |
2006年 | 112篇 |
2005年 | 109篇 |
2004年 | 92篇 |
2003年 | 67篇 |
2002年 | 55篇 |
2001年 | 19篇 |
2000年 | 16篇 |
1999年 | 11篇 |
1998年 | 10篇 |
1997年 | 11篇 |
1996年 | 13篇 |
1995年 | 8篇 |
1994年 | 9篇 |
1993年 | 7篇 |
1992年 | 8篇 |
1991年 | 5篇 |
1990年 | 5篇 |
1988年 | 5篇 |
1987年 | 6篇 |
1986年 | 7篇 |
1985年 | 9篇 |
1982年 | 6篇 |
1981年 | 10篇 |
1980年 | 7篇 |
1979年 | 3篇 |
1978年 | 6篇 |
1977年 | 7篇 |
1975年 | 6篇 |
1973年 | 3篇 |
1972年 | 5篇 |
1969年 | 4篇 |
1965年 | 2篇 |
排序方式: 共有1646条查询结果,搜索用时 15 毫秒
41.
Ionic liquids (ILs) are salts with an extremely low melting point. Substantial efforts have been made to address their low melting point from the enthalpic standpoint (i.e. interionic interactions). However, this question is still open. In this study, we report our findings that entropic (large fusion entropy), rather than enthalpic, contributions are primarily responsible for lowering the melting point in many cases, based on a large thermodynamic dataset. We have established a computational protocol using molecular dynamics simulations to decompose fusion entropy into kinetic (translational, rotational, and intramolecular vibrational) and structural (conformational and configurational) terms and successfully applied this approach for two representatives of ILs and NaCl. It is revealed that large structural contribution, particularly configurational entropy in the liquid state, plays a deterministic role in the large fusion entropy and consequently the low melting point of the ILs.Large structural entropy makes salts liquid at room temperature. 相似文献
42.
Antonio M. Scarfone Hiroki Suyari Tatsuaki Wada 《Central European Journal of Physics》2009,7(3):414-420
We reformulate the Gauss’ law of error in presence of correlations which are taken into account by means of a deformed product
arising in the framework of the Sharma-Taneja-Mittal measure. Having reviewed the main proprieties of the generalized product
and its related algebra, we derive, according to the Maximum Likelihood Principle, a family of error distributions with an
asymptotic power-law behavior.
相似文献
43.
Hiroki Matsunaga Hiroto Habu Atsumi Miyake 《Journal of Thermal Analysis and Calorimetry》2013,113(3):1387-1394
Ammonium dinitramide (ADN) is one of the several promising new solid propellant oxidizers. ADN is of interest because its oxygen balance and energy content are high, and it also halogen-free. One of the most important characteristics of a propellant oxidizer, however, is stability and ADN is known to degrade to ammonium nitrate (AN) during storage, which will affect its performance. This study focused on the effects of aging on the thermal decomposition mechanism of ADN. The thermal behaviors of ADN and ADN/AN mixtures were studied, as were the gases evolved during their decomposition, using differential scanning calorimetry (DSC), thermogravimetry–differential thermal analysis-infrared spectrometry (TG–DTA-IR), and thermogravimetry–differential thermal analysis-mass spectrometry (TG–DTA-MS). The results of these analyses demonstrated that the decomposition of ADN occurs via a series of distinct stages in the condensed phase. The gases evolved from ADN decomposition were N2O, NO2, N2, and H2O. In contrast, ADN mixed with AN (to simulate aging) did not exhibit the same initial reaction. We conclude that aging inhibits early stage, low temperature decomposition reactions of ADN. Two possible reasons were proposed, these being either a decrease in the acidity of the material due to the presence of AN, or inhibition of the acidic dissociation of dinitramic acid by NO 3 ? . 相似文献
44.
Kenichiro Todoroki Hiroki Hashimoto Kazuyuki Machida Miki Itoyama Tadashi Hayama Hideyuki Yoshida Hitoshi Nohta Manabu Nakashima Masatoshi Yamaguchi 《Journal of separation science》2013,36(2):232-238
In this study, we combined a column‐switching system with a fluorous scavenging derivatization method to develop a fully automated reagent peak‐free LC fluorescence detection protocol for the analysis of highly polar carboxylic acids. In this method, highly polar carboxylic acids were derivatized with fluorescent 1‐pyrenemethylamine in the presence of 1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide and 1‐hydroxy‐1H‐benzotriazole. Residual excess of the unreacted reagent was tagged with 2‐(perfluorooctyl)ethyl isocyanate and then removed selectively using a fluorous column‐switching system placed in front of an analytical reversed‐phase column. The signal of the fluorous‐tagged unreacted reagent was completely absent in the resulting chromatograms; therefore, it did not interfere with the quantification of each acid especially those eluted before 20 min. The detection limits (S/N = 3) for the examined acids were in the range from 4.0 to 22 fmol per injection. We have applied this method to comparative analysis of highly polar carboxylic acids in urine samples obtained from diabetes mellitus type‐II model mice and their control. 相似文献
45.
Mitsuru Kitamura Kenji KuboShogo Yoshinaga Hiroki MatsuzakiKantaro Ezaki Taisuke MatsuuraDaigo Matsuura Noriyuki FukuzumiKeiichiro Araki Masafumi Narasaki 《Tetrahedron letters》2014
A synthetic study of kosinostatin aglycone is reported. Synthesis of key intermediate lactone 3, which corresponds to the BCDE ring fragment, was accomplished, and the precursor BCD ring fragment 5 was synthesized via two routes. First, 5 was synthesized from 2,5-dimethoxybenzaldehyde 16 by the combination of typical known transformations including efficient application of non-aqueous OsO4 oxidation in the presence of PhB(OH)2. However the synthesis required 15 long steps, and its main difficulty was ortho-alkoxycarbonylmethylation of 1-naphthol. Next we attempted to apply our recently developed alkoxycarbonylmethylation of diazonaphthoquinone for the synthesis of 5, and 5 was successfully synthesized in 9 steps from the same starting compound 16. Finally, 5 was stereoselectively converted to lactone 3 via trifluoroacetic acid-mediated cyclization of the 3,4-epoxycylohexanecarboxylic acid derivative. 相似文献
46.
In this study, 8 new spirobenzopyrans were synthesized. A novel, three-step, facile route for the synthesis of 3′-allylindoline spirobenzopyrans via 3-allyl-3H-indoles was developed. The newly synthesized spirobenzopyrans were evaluated for their photochromic properties. The presence of an allyl moiety at the 3′ position did not disturb the photochromic response. The steric effects of the diallyl groups at the 3′ position affected the interconversion between colored and colorless forms. Therefore, the allyl chain in 3′-allylindoline spirobenzopyrans can be utilized to attach these compounds to a molecular matrix. Consequently, this synthetic methodology could be readily applied to the creation of new photo-switchable materials. 相似文献
47.
Effects of substrate and transfer on CVD-grown graphene over sapphire-induced Cu films 总被引:1,自引:0,他引:1
HU BaoShan WEI ZiDong AGO Hiroki JIN Yan XIA MeiRong LUO ZhengTang PAN QingJiang LIU YunLing 《中国科学:化学(英文版)》2014,57(6):895-901
We differentiated the effects of Cu films deposited on single crystalline a-,r-,and c-plane sapphire substrates upon graphene films synthesized with atmospheric pressure chemical vapor deposition(CVD).The data illustrate that the realization of high-crystalline Cu film is dependent not only on the crystallinity of underlying substrate,but also on the symmetric match of crystallographic geometry between metal film and substrate.We also systematically investigated the effects of PMMA removal on the Raman ID/IG and IG/I2D values of transferred graphene.The results reveal that different PMMA removal methods do not alter the ID/IG values;instead,the residue of PMMA increases the IG/I2D values and the thermal decomposition of PMMA leads to higher IG/I2D values than the removal of PMMA with acetone.The effects of PMMA removal on variations of the Raman spectra are also discussed. 相似文献
48.
Chaolumen Hiroki Enno Dr. Michihisa Murata Prof. Dr. Atsushi Wakamiya Prof. Dr. Yasujiro Murata 《化学:亚洲杂志》2014,9(11):3136-3140
Perylene bisimides (PBIs) are fascinating dyes with various potential applications. To study the effects of introducing a dibenzo‐fused structure to the perylene moiety, π‐extended PBI derivatives with a dibenzo‐fused structure at both of the a and f bonds were synthesized. The twisted structure was characterized by X‐ray crystal structure analysis. In the cyclic voltammograms, the dibenzo[a,f]‐fused PBI showed a reversible oxidation wave at much less positive potential, relative to a dibenzo[a,o]‐fused PBI derivative. These data indicated that two ring fusions at both sides of a naphthalene moiety, which construct a tetracene core, effectively raise the HOMO level compared to fusion of one ring at each naphthalene moiety (two anthracene cores). The dibenzo[a,f]‐fused PBI derivative showed an absorption band at 735 nm with a shoulder band reaching 900 nm. 相似文献
49.
Hiroki Yamamoto Takuya Fujiwara Takashi Funatsu Makoto Tsunoda 《Molecules (Basel, Switzerland)》2021,26(8)
Biothiols, such as cysteine and glutathione, play important roles in various intracellular reactions represented by the redox equilibrium against oxidative stress. In this study, a method for intracellular thiol quantification using HPLC-fluorescence detection was developed. Thiols were derivatized with a thiol-specific fluorescence derivatization reagent, viz. ammonium 7-fluoro-2,1,3-benzoxadiazole-4-sulfonate (SBD-F), followed by reversed-phase separation on an InertSustain AQ-C18 column. Six different SBD-thiols (homocysteine, cysteine, cysteinylglycine, γ-glutamylcysteine, glutathione, and N-acetylcysteine as an internal standard) were separated within 30 min using a citric buffer (pH 3.0)/MeOH mobile phase. The calibration curves of all the SBD-thiols had strong linearity (R2 > 0.999). Using this developed method, the thiol concentrations of human chronic myelogenous leukemia K562 cell samples were found to be 5.5–153 pmol/1 × 106 cells. The time-dependent effect of a thiol scavenger, viz. N-ethyl maleimide, on intracellular thiol concentrations was also quantified. This method is useful for elucidating the role of intracellular sulfur metabolism. 相似文献
50.
Dr. Koichi Mitsudo Ren Matsuo Toki Yonezawa Haruka Inoue Dr. Hiroki Mandai Prof. Dr. Seiji Suga 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(20):7877-7881
The first electrochemical dehydrogenative C−S bond formation leading to thienoacene derivatives is described. Several thienoacene derivatives were synthesized by dehydrogenative C−H/S−H coupling. The addition of nBu4NBr, which catalytically promoted the reaction as a halogen mediator, was essential. 相似文献