全文获取类型
收费全文 | 920篇 |
免费 | 44篇 |
国内免费 | 3篇 |
专业分类
化学 | 689篇 |
晶体学 | 9篇 |
力学 | 5篇 |
数学 | 59篇 |
物理学 | 205篇 |
出版年
2022年 | 5篇 |
2021年 | 11篇 |
2020年 | 13篇 |
2019年 | 10篇 |
2018年 | 7篇 |
2017年 | 4篇 |
2016年 | 20篇 |
2015年 | 19篇 |
2014年 | 21篇 |
2013年 | 30篇 |
2012年 | 42篇 |
2011年 | 61篇 |
2010年 | 33篇 |
2009年 | 41篇 |
2008年 | 59篇 |
2007年 | 50篇 |
2006年 | 45篇 |
2005年 | 46篇 |
2004年 | 43篇 |
2003年 | 63篇 |
2002年 | 31篇 |
2001年 | 12篇 |
2000年 | 15篇 |
1999年 | 6篇 |
1998年 | 6篇 |
1997年 | 8篇 |
1996年 | 19篇 |
1995年 | 7篇 |
1994年 | 11篇 |
1993年 | 9篇 |
1992年 | 8篇 |
1991年 | 12篇 |
1990年 | 9篇 |
1989年 | 7篇 |
1988年 | 6篇 |
1987年 | 7篇 |
1986年 | 14篇 |
1985年 | 20篇 |
1984年 | 11篇 |
1983年 | 9篇 |
1982年 | 10篇 |
1981年 | 17篇 |
1980年 | 18篇 |
1979年 | 11篇 |
1978年 | 9篇 |
1977年 | 8篇 |
1976年 | 7篇 |
1975年 | 5篇 |
1974年 | 9篇 |
1973年 | 8篇 |
排序方式: 共有967条查询结果,搜索用时 78 毫秒
71.
Lifang Chen Yulv Yu Masako Kuwa Tao Cheng Yan Liu Hiroshi Murakami Harada Masafumi Yuan Wang 《物理化学学报》2020,36(1):1907008-0
碱-乙二醇法制备的"非保护型"金属及合金纳米簇由表面吸附的溶剂分子和简单离子实现稳定化,它们被广泛用于制备高性能复相催化剂和研究复相催化剂中的尺寸、组成、载体表面基团以及修饰剂对催化性能的影响。关于此类非保护金属纳米簇的形成过程及机理的认识尚有待进一步深化。本文采用原位快速扫描X射线吸收精细结构谱(QXAFS)、原位紫外-可见(UV-Vis)吸收光谱、透射电子显微镜和动态光散射技术研究了碱-乙二醇法合成中非保护型金属胶体纳米簇的形成过程与机理。结果表明,在碱-乙二醇法合成非保护型Pt金属纳米簇的过程中,室温下即有部分Pt(IV)被还原至Pt(II)。随着反应温度的升高,OH-逐渐取代与Pt离子配位的Cl-,在Pt―Pt键形成之前,反应体系的UV-Vis吸收光谱中可观察到明显的纳米粒子的散射信号,原位QXAFS分析表明Pt纳米簇是由Pt氧化物纳米粒子还原所形成的;在Ru金属纳米簇的形成过程中,OH-首先取代了Ru Cl_3中的Cl~-,形成羟基配合物Ru(OH) _6~(3-),后者进一步缩合形成氧化钌纳米粒子,最终Ru金属纳米簇由乙二醇还原氧化钌纳米粒子形成。由于先形成了氧化物纳米粒子,后续的还原反应被限制在氧化物纳米粒子内,使最终得到的非保护型金属纳米簇具有尺寸小、分布窄的特点。本工作所获得的知识对发展高性能能源转化催化剂、精细化学合成催化剂、传感器等功能体系具有重要意义。 相似文献
72.
Satoshi Nagao Ayaka Suda Hisashi Kobayashi Naoki Shibata Yoshiki Higuchi Shun Hirota 《化学:亚洲杂志》2020,15(11):1743-1749
Domain swapping is an exception to Anfinsen's dogma, and more than one structure can be produced from the same amino acid sequence by domain swapping. We have previously shown that myoglobin (Mb) can form a domain‐swapped dimer in which the hinge region is converted to a helical structure. In this study, we showed that domain‐swapped dimerization of Mb was achieved by a single Ala mutation of Gly at position 80. Multiple Ala mutations at positions 81 and 82 in addition to position 80 facilitated dimerization of Mb by stabilization of the dimeric states. Domain swapping tendencies correlated well with the helical propensity of the mutated residue in a series of Mb mutants with amino acids introduced to the hinge region. These findings demonstrate that a single mutation in the hinge loop to modify helical propensity can control oligomer formation, providing new ideas to create high‐order protein oligomers using domain swapping. 相似文献
73.
Takashi Kato Norifumi Hirota Akira Fujishima Jean M. J. Frchet 《Journal of polymer science. Part A, Polymer chemistry》1996,34(1):57-62
Supramolecular liquid–crystalline polymeric complexes based on a backbone that contains vinyl pyridine units and azobenzene or biphenyl derivatives that posses alkyl chains terminated by carboxylic acid have been obtained by the formation of intermolecular hydrogen bonds between the carboxylic acid and the pyridyl moieties. The polymeric complexes behave as side-chain liquid–crystalline polymers and exhibit smectic phases. A new type of H-bonded host-guest liquid–crystalline system is also reported. The liquid–crystalline host copolymers contain both mesogenic acrylate and 4-vinylpyridine units. The guest molecule is an azobenzene that has a carboxylic acid moiety at one of its extremities. The H-bonded polymeric host–guest complexes exhibit nematic phases. Sequential UV and visible light irradiation of the polymeric complex causes reversible photochemically induced phase transitions. The isothermal nematic–isotropic and isotropic–nematic transitions result from the trans-cis and cis-trans photoisomerization of the guest azobenzene in the host–guest system. © 1996 John Wiley & Sons, Inc. 相似文献
74.
75.
The dynamic changes in ferroelectric liquid crystal (FLC) molecular alignments under an applied electric field are examined
by observing the formation of conoscopic figures with a time resolution of 0.1 ms. Close agreements between observed and simulated
conoscopic figures under low voltage (30 V) were obtained. Under high voltage (120 V), however, the observed conoscopic figures
became blurred between 0.8 ms and 1.1 ms after reversal of the electric field. The light scattering producing the blurriness
occurred due to the development of fast transient molecular alignments during the switching transition above the applied voltage
70 V. 相似文献
76.
Front Cover: Construction of a Triangle‐Shaped Trimer and a Tetrahedron Using an α‐Helix‐Inserted Circular Permutant of Cytochrome c555 (Chem. Asian J. 10/2018)
下载免费PDF全文
![点击此处可从《化学:亚洲杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
77.
Yoshiyuki Kawashima Tsuyoshi Usami G. Yu. Golubiatnikov Eizi Hirota 《Journal of Molecular Spectroscopy》2010,263(1):11-20
Rotational spectra of both trans and cis forms of the N-methylformamide normal as well as deuterated (HCONDCH3, referred to as N-D) species were observed by Fourier transform microwave spectroscopy in the frequency region from 5 to 118 GHz. Samples were prepared in the form of a beam by a pulsed jet valve maintained at 50 °C and were introduced in a high-vacuum cavity cell, with either Ne or Ar as a carrier gas at a backing pressure of 100 kPa. The observed spectra were analyzed to yield molecular parameters including rotational constants and barrier, V3, to CH3 internal-rotation: 53.9 (6) and 301 (4) cm−1 for the trans and cis forms of the normal species, respectively, and 41.9 (6) and 309 (4) cm−1 for the trans and cis forms of the N-D species, respectively. Spectra of four trans isotopologues with 13C, 15N, or 18O singly-substituted in the internal-rotation A state were observed and analyzed to derive the rs structure of the trans form. For comparison with the experimental data, ab initio calculations were carried out at MP2/6-31G∗∗ level to derive molecular structure, potential barrier to CH3 internal rotation, and the energy difference between the cis and trans forms. An extensive coupling was found between the CH3 internal rotation and N-H out-of-plane bending, suggesting that the potential function for the CH3 internal-rotation deviates considerably from a simple cos(3α) form. The effects of the V6 term is briefly discussed. 相似文献
78.
Okuda K Abeta C Hirota T Mochizuki M Mashino T 《Chemical & pharmaceutical bulletin》2002,50(7):985-987
Water-soluble C60-porphyrin hybrid molecules were first synthesized toward their pharmaceutical applications. 相似文献
79.
80.