全文获取类型
收费全文 | 586篇 |
免费 | 24篇 |
国内免费 | 20篇 |
专业分类
化学 | 372篇 |
晶体学 | 9篇 |
力学 | 7篇 |
综合类 | 1篇 |
数学 | 129篇 |
物理学 | 112篇 |
出版年
2023年 | 6篇 |
2022年 | 5篇 |
2021年 | 19篇 |
2020年 | 15篇 |
2019年 | 12篇 |
2018年 | 9篇 |
2017年 | 10篇 |
2016年 | 16篇 |
2015年 | 25篇 |
2014年 | 21篇 |
2013年 | 44篇 |
2012年 | 21篇 |
2011年 | 50篇 |
2010年 | 31篇 |
2009年 | 25篇 |
2008年 | 31篇 |
2007年 | 49篇 |
2006年 | 27篇 |
2005年 | 20篇 |
2004年 | 25篇 |
2003年 | 27篇 |
2002年 | 31篇 |
2001年 | 17篇 |
2000年 | 17篇 |
1999年 | 10篇 |
1998年 | 6篇 |
1997年 | 8篇 |
1996年 | 3篇 |
1994年 | 2篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 6篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1978年 | 1篇 |
1977年 | 4篇 |
1975年 | 1篇 |
1972年 | 1篇 |
1971年 | 1篇 |
1959年 | 1篇 |
1958年 | 1篇 |
1935年 | 1篇 |
排序方式: 共有630条查询结果,搜索用时 359 毫秒
81.
Choe YK Tsuchida E Ikeshoji T Yamakawa S Hyodo SA 《The journal of physical chemistry. B》2008,112(37):11586-11594
The effects of water content on water transport and electro-osmosis in a representative polymer electrolyte membrane, Nafion, are investigated in detail by means of first-principles molecular dynamics (MD) simulations in the presence of a homogeneous electric field. We have directly evaluated electro-osmotic drag coefficients (the number of water molecules cotransported with proton conduction) from the trajectories of the first-principles MD simulations and also explicitly evaluated factors that contribute to the electro-osmotic drag coefficients. In agreement with previously reported experiments, our calculations show virtually constant values ( approximately 1) of the electro-osmotic drag coefficients for both low and high water content states. Detailed comparisons of each factor contributing to the drag coefficient reveal that an increase in water content increases the occurrence of the Grotthuss-like effective proton transport process, whose contribution results in a decrease in the electro-osmotic drag coefficient. At the same time, an environment that is favorable for the Grotthuss-like effective proton transport process is also favorable for the transport of water arising from water transport occurring beyond the hydration shell around the protons, whose contribution results in an increase in the electro-osmotic drag coefficient. Conversely, an environment that is not favorable for proton conduction is also not favorable for water transport. As a result, the electro-osmotic drag coefficient shows virtually identical values with respect to change in the water content. 相似文献
82.
Seonghwa Jeong Eunji Park Jiyeon Kim Seok Bae Park Dr. Sung Hoon Kim Prof. Wonyoung Choe Prof. Joonghan Kim Prof. Young S. Park 《Angewandte Chemie (International ed. in English)》2023,62(50):e202314148
Increasing the chemical diversity of organic semiconductors is essential to develop efficient electronic devices. In particular, the replacement of carbon-carbon (C−C) bonds with isoelectronic boron-nitrogen (B−N) bonds allows precise modulation of the electronic properties of semiconductors without significant structural changes. Although some researchers have reported the preparation of B2N2 anthracene derivatives with two B−N bonds, no compounds with continuous multiple BN units have been prepared yet. Herein, we report the synthesis and characterization of a B2N2 anthracene derivative with a BNBN unit formed by converting the BOBN unit at the zigzag edge. Compared to the all-carbon analogue 2-phenylanthracene, BNBN anthracene exhibits significant variations in the C−C bond length and a larger highest occupied molecular orbital–lowest unoccupied molecular orbital energy gap. The experimentally determined bond lengths and electronic properties of BNBN anthracene are confirmed through theoretical calculations. The BOBN anthracene organic light-emitting diode, used as a blue host, exhibits a low driving voltage. The findings of this study may facilitate the development of larger acenes with multiple BN units and potential applications in organic electronics. 相似文献
83.
A sulfur compound, bis(4-hydroxybenzyl)sulfide (1) was isolated from the root extract of Pleuropterus ciliinervis. Its structure was elucidated using NMR spectroscopic techniques and mass spectrometric analysis. Compound 1 showed potent inhibitory activity in a histone deacetylase (HDAC) enzyme assay. It also exhibited growth inhibitory activity on five human tumor cell lines and more sensitive inhibitory activity on the MDA-MB-231 breast tumor cell line. 相似文献
84.
Neuroprotective activity of triterpenoid saponins from Platycodi radix against glutamate-induced toxicity in primary cultured rat cortical cells 总被引:1,自引:0,他引:1
During our investigation of the neuroprotective activity of Platycodi radix we found that an aqueous extract of this folk medicine exhibited significant protection against glutamate-induced toxicity in primary cultured rat cortical cells. In order to clarify the neuroprotective mechanism(s) of this observed effect, activity-guided isolation was performed to seek and identify active fractions and components. By such fractionation, four known triterpene saponin compounds--platycodins A, C and D and deapioplatycodin D--were isolated from the n-butanol fraction. Among these four compounds, platycodin A exhibited significant neuroprotective activities against glutamate-induced toxicity, exhibiting cell viability of about 50%, at concentrations ranging from 0.1 microM to 10 microM. Therefore, the neuroprotective effect of Platycodi radix might be due to the inhibition of glutamate-induced toxicity by the saponin compounds it contains. 相似文献
85.
86.
Shin Y Yoon SH Choe EY Cho SH Woo CH Rho JY Kim JH 《Experimental & molecular medicine》2007,39(1):97-105
Expression of matrix metalloproteinase-9 (MMP-9) is associated with airway remodeling and tissue injury in asthma. However, little is known about how MMP-9 is up-regulated in airway epithelial cells. In this study, we show that phorbol myristate acetate (PMA) induces MMP-9 expression via a protein kinase Calpha (PKCalpha)-dependent signaling cascade in BEAS-2B human lung epithelial cells. Pretreatment with either GF109203X, a general PKC inhibitor, or Go6976, a PKCalpha/beta isozyme inhibitor, inhibited PMA-induced activation of the MMP-9 promoter, as did transient transfection with PKCalpha antisense oligonuclotides. PMA activated NF-kappaB by phosphorylating IkappaB in these cells and this was also inhibited by GF109203X and Go6976, suggesting that PKCa acts as an upstream regulator of NF-kappaB in PMA-induced MMP-9 induction. Our results indicate that a "PKCalpha-NF- kappaB"-dependent cascade is involved in the signaling leading to PMA-induced MMP-9 expression in the lung epithelium. 相似文献
87.
Ferrer M Gutiérrez A Mounir M Rossell O Ruiz E Rang A Engeser M 《Inorganic chemistry》2007,46(8):3395-3406
The self-assembly reactions between the fluorinated ditopic ligand 1,4-bis(4-pyridyl)tetrafluorobenzene (A) and different nitrogen-protected palladium(II) and platinum(II) complexes have been investigated. While dynamic equilibria between molecular triangles and squares were observed when the diimine compounds 4,4'-R2bipy (bipy = 2,2'-bipyridine; R = H, Me, t-Bu) were employed as ancillary ligands, only square species were obtained from ethylenediamine (en) derivatives. Characterization of the obtained metallomacrocycles was accomplished by 1H and 19F NMR spectroscopy in combination with electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR). Molecular dynamics simulations (UFF) have been performed to interpret the influence of the fluorinated ring on the square/triangle relative stability. Density functional calculations using the GIAO method have been employed for the interpretation of the chemical shift assignments. The study of the ability of these compounds to act as hosts of electron-rich aromatic guests has shown that the palladium ethylenediamine square is capable of establishing this type of intermolecular interaction exclusively in aqueous media. The host-guest stoichiometry and association constants have been determinated by 1H NMR spectroscopy. 相似文献
88.
The cross-type (C-VUM) and linear-type (L-VUM) bifunctional vinyl urethane macromonomers and polystyrene (PS) using these macromonomers were synthesized in the dispersion polymerization in ethanol, and the reaction and stabilizing mechanism of the macromonomers was proposed. The structural verification of the macromonomers and PS was studied using (1)H NMR. The weight-average particle size of C-PS (PS prepared with C-VUM) and L-PS (PS prepared with L-VUM) decreased from 4.41 to 1.36 microm and from 3.56 to 1.52 microm, whereas the average-molecular weight of those increased from 34,100 to 100,500 g/mol and from 32,200 to 71,800 g/mol, respectively. The XPS result showed that the C-PS was anchored with a larger amount of PEG than that of the L-PS on the particle surface. Thus, the reaction and stabilizing mechanism of the macromonomers for the formation of PS particles is proposed as the following. The particle surface of the C-PS is surrounded by a large amount of tail shaped macromonomers leading to higher molecular weights and smaller particle sizes. On the other hand, the particle surface of the L-PS is comprised of relatively small amounts of loop shaped macromonomers inducing lower molecular weights and larger particles of L-PS than C-PS. 相似文献
89.
Separation of negatively charged molecules, such as plasmid DNA (pDNA), RNA and endotoxin forms a bottleneck for the development of pDNA vaccine production process. The use of affinity interactions of transition metal ions with these molecules may provide an ideal separation methodology. In this study, the binding behaviour of pDNA, RNA and endotoxin to transition metal ions, either in immobilised or free form, was investigated. Transition metal ions: Cu2+, Ni2+, Zn2+, Co2+ and Fe3+, typically employed in the immobilised metal affinity chromatography (IMAC), showed very different binding behaviour depending on the type of metal ions and their existing state, i.e. immobilised or free. In the alkaline cell lysate, pDNA showed no binding to any of the IMAC chemistries tested whereas RNA interacted significantly with Cu2+-iminodiacetic acid (IDA) and Ni2+-IDA but showed no substantial binding to the rest of the IMAC chemistries. pDNA and RNA, however, interacted to varying degrees with free metal ions in the solution. The greatest selectivity in terms of pDNA and RNA separation was achieved with Zn2+ which enabled almost full precipitation of RNA while keeping pDNA soluble. For both immobilised and free metal ions, ionic strength of solution affected the metal ion-nucleic acid interaction significantly. Endotoxin, being more flexible, was able to interact better with the immobilised metal ions than the nucleic acids and showed binding to all the IMAC chemistries. The specific interactions of immobilised and/or free metal ions with pDNA, RNA and endotoxin showed a good potential, by selectively removing RNA and endotoxin at high efficiency, to develop a simplified pDNA purification process with improved process economics. 相似文献
90.
Guang Lin RANG Zhi Yuan HUANG 《数学学报(英文版)》2007,23(5):895-904
In this paper a complete proof for the existence of generalized operators satisfying abstract 02 dynamical equations of quantum motions δ^2/δt^2Ф(t, x) + ( △- m^2)Ф(t, x) = -λ :Ф^3(t, x), subject to a suitable initial condition, is given under the framework of white noise analysis. Also some important commutation relations related to Ф44 quantum fields are discussed and proved in detail. 相似文献