全文获取类型
收费全文 | 565篇 |
免费 | 19篇 |
国内免费 | 1篇 |
专业分类
化学 | 482篇 |
晶体学 | 6篇 |
力学 | 5篇 |
数学 | 10篇 |
物理学 | 82篇 |
出版年
2023年 | 1篇 |
2022年 | 7篇 |
2021年 | 3篇 |
2020年 | 5篇 |
2019年 | 8篇 |
2018年 | 3篇 |
2016年 | 17篇 |
2015年 | 10篇 |
2014年 | 11篇 |
2013年 | 34篇 |
2012年 | 35篇 |
2011年 | 33篇 |
2010年 | 20篇 |
2009年 | 15篇 |
2008年 | 22篇 |
2007年 | 34篇 |
2006年 | 41篇 |
2005年 | 43篇 |
2004年 | 40篇 |
2003年 | 23篇 |
2002年 | 28篇 |
2001年 | 13篇 |
2000年 | 12篇 |
1999年 | 9篇 |
1998年 | 3篇 |
1997年 | 6篇 |
1996年 | 11篇 |
1995年 | 9篇 |
1994年 | 2篇 |
1993年 | 9篇 |
1992年 | 2篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1987年 | 2篇 |
1986年 | 7篇 |
1985年 | 6篇 |
1984年 | 5篇 |
1982年 | 5篇 |
1981年 | 5篇 |
1980年 | 6篇 |
1979年 | 3篇 |
1978年 | 5篇 |
1977年 | 4篇 |
1976年 | 5篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1973年 | 4篇 |
1970年 | 2篇 |
1924年 | 1篇 |
排序方式: 共有585条查询结果,搜索用时 15 毫秒
21.
Hidemasa Azuma Yuzuru Katagiri Shinichi Yamabe 《Journal of polymer science. Part A, Polymer chemistry》1996,34(8):1407-1414
Transition states (TSs) of radical addition homopolymerization reactions of methyl acrylate, methyl methacrylate, dimethyl itaconate, and N-methyl itaconimide were examined with two-unit radical models using MOPAC (PM3 UHF) semiempirical method. Calculated activation energies (Eas) show good correlations with experimental values. Calculated activation entropies (−ΔS‡s) are found to be well proportional to Eas. The entropy terms play an important role as well as Ea in radical additions. Ea depends on the angle (θrs) between reaction points of radical and of monomer at TS. The bond length between reaction points at TS is constant regardless of monomers studied. The geometries and thermodynamical properties calculated here for TS indicate the importance of steric effects caused by substituted group(s) rather than electronic perturbation energies reported previously. © 1996 John Wiley & Sons, Inc. 相似文献
22.
Shinichi Kinugasa Hisae Nakahara Jun-Ichi Kawahara Yoshinori Koga Haruo Takaya 《Journal of Polymer Science.Polymer Physics》1996,34(3):583-586
Static light scattering measurements were performed on dilute solutions of monodisperse poly(ethylene oxide) (PEO) in methanol at 25°C. PEOs of five different molecular weights ranging from nominal Mw = 8.6 × 104 to 9.13 × 105 were used. Linear Zimm plots were obtained for all the PEO samples: no downturn was observed at small angles, indicating that no large aggregates of PEO molecules exist in the solution. From the plots, values of the weight-average molecular weight, Mw, the radius gyration, RG, and the second virial coefficient, A2, were successfully determined for respective PEOs. Observed relationship between RG and Mw indicates that methanol is certainly a good solvent for the polymer. © 1996 John Wiley & Sons, Inc. 相似文献
23.
24.
Surasak Seesukphronrarak Shinichi Kawasaki Shigeki Kuwata Toshikazu Takata 《Journal of polymer science. Part A, Polymer chemistry》2019,57(24):2602-2605
Two novel 9,9‐difunctionalized fluorene‐type monomers, 9,9‐bis(4‐hydroxyphenyl‐ and 4‐aminophenyl)‐2,3:6,7‐dibenzofluorenes, are synthesized by the reaction of dibenzenzofluorenone with phenol and aniline. These monomers are used for the preparation of polyester and polyimide as the typical polymers to evaluate the property change such as thermal stability caused by the benzene rings fused to the fluorene skeleton with keeping good solubility, in comparison with the polymers derived from simple fluorenone. In fact, these two new polymers have the fairly enhanced thermal stability and refractive index value along with satisfactory solubility in organic solvents, enough to emphasize the fusion effect. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2602–2605 相似文献
25.
Ayumi Suzuki Dr. Yuichiro Mutoh Dr. Noriko Tsuchida Chi-Wai Fung Dr. Shoko Kikkawa Prof. Isao Azumaya Prof. Shinichi Saito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(17):3795-3802
Although the chemistry of transition-metal complexes with carbonyl (CO) and thiocarbonyl (CS) ligands has been well developed, their heavier analogues, namely selenocarbonyl (CSe) and tellurocarbonyl (CTe) complexes remain scarce. The limited availability of such CSe and CTe complexes has so far hampered our understanding of the differences between such chalcogenocarbonyl (CE: E=O, S, Se, Te) ligands. Herein, we report the synthesis and properties of a series of cationic half-sandwich ruthenium CE complexes of the type [CpRu(CE)(H2IMes)(CNCH2Ts)][BArF4] (Cp=η5-C5H5−; H2IMes=1,3-dimesitylimidazolin-2-ylidene; ArF=3,5-(CF3)2C6H3). A combination of X-ray diffraction analyses, NMR spectroscopic analyses, and DFT calculations revealed an increasing π-accepting ability of the CE ligands in the order O<S<Se<Te. A variable-temperature NMR analysis of the thus obtained chiral-at-metal CE complexes indicated high stereochemical stability. 相似文献
26.
In developing a new method to measure the phase distribution of a light wave utilizing the adaptive control of the pupil function with a liquid crystal panel, the optimization procedure for the adaptive control is shown to improve when a local algorithm is adopted. The feasibility of the proposed system is confirmed by computer simulation as well as by some basic experiments. 相似文献
27.
28.
Shingo Kato Kakuya Kitagawa Yeonyee E. Yoon Hiroshi Nakajima Motonori Nagata Shinichi Takase Shiro Nakamori Masaaki Ito Hajime Sakuma 《Magnetic resonance imaging》2014
Purpose
The purposes of this study were to evaluate the reproducibility for measuring the cold pressor test (CPT)-induced myocardial blood flow (MBF) alteration using phase-contrast (PC) cine MRI, and to determine if this approach could detect altered MBF response to CPT in smokers.Materials and methods
After obtaining informed consent, ten healthy male non-smokers (mean age: 28 ± 5 years) and ten age-matched male smokers (smoking duration ≥ 5 years, mean age: 28 ± 3 years) were examined in this institutional review board approved study. Breath-hold PC cine MR images of the coronary sinus were obtained with a 3 T MR imager with 32 channel coils at rest and during a CPT performed after immersing one foot in ice water. MBF was calculated as coronary sinus flow divided by the left ventricular (LV) mass which was given as a total LV myocardial volume measured on cine MRI multiplied by the specific gravity (1.05 g/mL).Results
In non-smokers, MBF was 0.86 ± 0.25 mL/min/g at rest, with a significant increase to 1.20 ± 0.36 mL/min/g seen during CPT (percentage change of MBF (?MBF (%)); 39.2% ± 14.4%, p < 0.001). Inter-study reproducibility for ?MBF (%) measurements by different MR technologist was good, as indicated by the intraclass correlation coefficient of 0.93 and reproducibility coefficient of 10.5%. There was no significant difference between smokers and non-smokers for resting MBF (0.85 ± 0.32 mL/min/g, p = 0.91). However, ?MBF (%) in smokers was significantly reduced (-4.0 ± 32.2% vs. 39.2 ± 14.4%, p = 0.011).Conclusion
PC cine MRI can be used to reproducibly quantify MBF response to CPT and to detect impaired flow response in smokers. This MR approach may be useful for monitoring the sequential change of coronary blood flow in various potentially pathologic conditions and for investigating its relationship with cardiovascular risk. 相似文献29.
Kaoru Nakajima Shinichi Oshima Motofumi Suzuki Kenji Kimura 《Surface science》2012,606(21-22):1693-1699
Surface structures of equimolar mixtures of imidazolium-based ionic liquids (ILs) having a common cation (1-butyl-3-methylimidazolium ([C4MIM]) or 1-hexyl-3-methylimidazolium ([C6MIM])) and different anions (bis(trifluoromethanesulfonyl)imide ([TFSI]), hexafluorophosphate ([PF6]) or chlorine) are studied using high-resolution Rutherford backscattering spectroscopy (HRBS). Both cations and anions have the same preferential orientations at the surface as in the pure ILs. In the mixture, the larger anion is located shallower than the smaller anion. The [TFSI] anion is slightly enriched at the surface relative to [PF6] with coverage of ~ 60% for the equimolar mixtures of [C4(6)MIM] [TFSI] and [C4(6)MIM] [PF6]. No surface segregation is observed for [C6MIM] [TFSI]0.5[Cl]0.5 and [C6MIM] [PF6]0.5[Cl]0.5. These results are different from the recent TOF-SIMS measurement where very strong surface segregation of [TFSI] was concluded for the mixture of [C4MIM] [TFSI] and [C4MIM] [PF6]. 相似文献
30.
Mass spectrometric monitoring of oxidation of aliphatic C6–C8 hydrocarbons and ethanol in low pressure oxygen and air plasmas 下载免费PDF全文
Dilshadbek T. Usmanov Lee Chuin Chen Kenzo Hiraoka Hiroshi Wada Hiroshi Nonami Shinichi Yamabe 《Journal of mass spectrometry : JMS》2016,51(12):1187-1195
Experimental and theoretical studies on the oxidation of saturated hydrocarbons (n‐hexane, cyclohexane, n‐heptane, n‐octane and isooctane) and ethanol in 28 Torr O2 or air plasma generated by a hollow cathode discharge ion source were made. Ions corresponding to [M + 15]+ and [M + 13]+ in addition to [M ? H]+ and [M ? 3H]+ were detected as major ions where M is the sample molecule. The ions [M + 15]+ and [M + 13]+ were assigned as oxidation products, [M ? H + O]+ and [M ? 3H + O]+, respectively. By the tandem mass spectrometry analysis of [M ? H + O]+ and [M ? 3H + O]+, H2O, olefins (and/or cycloalkanes) and oxygen‐containing compounds were eliminated from these ions. Ozone as one of the terminal products in the O2 plasma was postulated as the oxidizing reagent. As an example, the reactions of C6H14+? with O2 and of C6H13+ (CH3CH2CH+CH2CH2CH3) with ozone were examined by density functional theory calculations. Nucleophilic interaction of ozone with C6H13+ leads to the formation of protonated ketone, CH3CH2C(=OH+)CH2CH2CH3. In air plasma, [M ? H + O]+ became predominant over carbocations, [M ? H]+ and [M ? 3H]+. For ethanol, the protonated acetic acid CH3C(OH)2+ (m/z 61.03) was formed as the oxidation product. The peaks at m/z 75.04 and 75.08 are assigned as protonated ethyl formate and protonated diethyl ether, respectively, and that at m/z 89.06 as protonated ethyl acetate. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献