全文获取类型
收费全文 | 586篇 |
免费 | 73篇 |
国内免费 | 120篇 |
专业分类
化学 | 673篇 |
晶体学 | 8篇 |
力学 | 14篇 |
综合类 | 4篇 |
物理学 | 80篇 |
出版年
2024年 | 2篇 |
2023年 | 14篇 |
2022年 | 29篇 |
2021年 | 37篇 |
2020年 | 46篇 |
2019年 | 45篇 |
2018年 | 29篇 |
2017年 | 46篇 |
2016年 | 39篇 |
2015年 | 27篇 |
2014年 | 41篇 |
2013年 | 61篇 |
2012年 | 32篇 |
2011年 | 25篇 |
2010年 | 18篇 |
2009年 | 30篇 |
2008年 | 25篇 |
2007年 | 20篇 |
2006年 | 28篇 |
2005年 | 25篇 |
2004年 | 28篇 |
2003年 | 24篇 |
2002年 | 9篇 |
2001年 | 9篇 |
2000年 | 11篇 |
1999年 | 12篇 |
1998年 | 11篇 |
1997年 | 8篇 |
1996年 | 2篇 |
1995年 | 7篇 |
1994年 | 11篇 |
1993年 | 8篇 |
1992年 | 8篇 |
1991年 | 6篇 |
1990年 | 1篇 |
1989年 | 3篇 |
1987年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有779条查询结果,搜索用时 11 毫秒
1.
《Magnetic resonance in chemistry : MRC》2003,41(1):37-41
The oxidation of symmetrical disulfides [D ,L ‐cystine ( 1 ) and 3,3′‐dithiobis(propionic acid) ( 2 )] with hydrogen peroxide in D2O–NaOH solution (pH 10–11) was studied by NMR spectroscopy. Assignments of the proton and carbon NMR signals of starting materials ( 1 and 2 ) and products of oxidation are based on conventional 1D NMR methods (DEPT, selective spin decoupling). Formation of C—S bond cleavage products or, in case of 2 , partially oxidized intermediates was not detected. The accelerating effect of Cu2+ cations, but not Fe3+ cations, on the oxidation rate of 1 in basic medium was demonstrated. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
2.
《Magnetic resonance in chemistry : MRC》2003,41(8):585-588
A novel, radical responsive MRI contrast agent based on a gadolinium chelate conjugated to a liposome through a disulfide linker was synthesized, with the aim of pursuing the in vivo mapping of radicals. The liposome was prepared by incorporating a thiol‐activated phospholipid, which was subsequently reacted with a gadolinium chelate containing a free thiol group. The long reorientational motion of the supramolecular adduct endows the paramagnetic agent with a relaxivity significantly higher than that of the free complex. The disulfide bond represents a radical‐sensitive moiety and a large decrease in contrast efficacy (T1 relaxivity) is shown upon its cleavage. A preliminary assessment of the system was made by means of in vitro gamma‐irradiation and thiol–disulfide bond exchange with dithiothreitol. Both methods showed a clear dose‐dependent decrease in T1‐relaxivity. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
3.
Improved reaction conditions for the preparation of poly(p‐phenylene sulfide) (PPS) directly from bis(4‐bromophenyl) disulfide (BBD) have been established. Heating BBD with magnesium metal afforded only a low molecular weight polymer. PPS with a melting temperature around 280 °C was obtained from BBD in the presence of sodium carbonate or zinc metal. The best results were obtained with the addition of a catalytic amount of KI to the zinc–BBD mixture. Polymers prepared by the above methods are semicrystalline and dissolve in 1‐chloronaphthalene and have properties comparable to commercial PPS. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 900–904, 2006 相似文献
4.
Carbamazepine (CBZ), as a typical pharmaceutical and personal care product (PPCP), cannot be efficiently removed by the conventional drinking water and wastewater treatment process. In this work, the CoS2/Fe2+/PMS process was applied for efficient elimination of CBZ. The CBZ removal efficiency of CoS2/Fe2+/PMS was 2.5 times and 23 times higher than that of CoS2/PMS and Fe2+/PMS, respectively. The intensity of DMPO-HO• and DMPO- followed the order of Fe2+/PMS < CoS2/PMS < CoS2/Fe2+/PMS, also suggesting the CoS2/Fe2+/PMS process has the highest oxidation activity. The effects of reaction conditions (e.g., CoS2 dosage, Fe2+ concentration, PMS concentration, initial CBZ concentration, pH, temperature) and water quality parameters (e.g., , , , , , humic acid) on the degradation of CBZ were also studied. Response surface methodology analysis was carried out to obtain the best conditions for the removal of CBZ, which are: Fe2+ = 70 µmol/L, PMS = 240 µmol/L, CoS2 = 0.59 g/L. The sustainability test demonstrated that the repeated use of CoS2 for 8 successive cycles resulted in little function decrease (<10%). These findings suggest that CoS2/Fe2+/PMS may be a promising method for advanced treatment of tailwater from sewage treatment plant. 相似文献
5.
6.
Direct visualization of the structural defects in two-dimensional (2D) semiconductors at a large scale plays a significant role in understanding their electrical/optical/magnetic properties, but is challenging. Although traditional atomic resolution imaging techniques, such as transmission electron microscopy and scanning tunneling microscopy, can directly image the structural defects, they provide only local-scale information and require complex setups. Here, we develop a simple, non-invasive wet etching method to directly visualize the structural defects in 2D semiconductors at a large scale, including both point defects and grain boundaries. Utilizing this method, we extract successfully the defects density in several different types of monolayer molybdenum disulfide samples, providing key insights into the device functions. Furthermore, the etching method we developed is anisotropic and tunable, opening up opportunities to obtain exotic edge states on demand. 相似文献
7.
Consistency-dependent optical properties of lubricating grease studied by terahertz spectroscopy 下载免费PDF全文
The optical properties of four kinds of lubricating greases (urea, lithium, extreme pressure lithium, molybdenum disulfide lithium greases) with different NLGL (National Lubricant Grease Institute of America) numbers were investigated using terahertz time-domain spectroscopy. Greases with different NLGL grades have unique spectral features in the terahertz range. Comparison of the experimental data with predictions based on Lorentz--Lorenz theory exhibited that the refractive indices of each kind of lubricating grease were dependent on the their consistency. In addition, molybdenum disulfide (MoS2) as a libricant additive shows strong absorption from 0.2 to 1.4 THz, leading to higher absorption of MoS2-lithium grease than that of lithium grease. 相似文献
8.
Jaegeun Noh Soonmin Jang Donghyung Lee Seokmin Shin Young Joon Ko Eisuke Ito Sang-Woo Joo 《Current Applied Physics》2007,7(6):605-610
Adsorption of dimethyl disulfide (DMDS) on gold colloidal nanoparticle surfaces has been examined to check its binding mechanism. Differently from previous results, DMDS molecules adsorbed on the gold surface at high concentration showed the S–S stretching band at 500 cm−1 in surface-enhanced Raman scattering (SERS) spectra, which indicates the presence of intact adsorption of DMDS molecules. However, it was found that the S–S bond of disulfides was easily cleaved on the gold surface at low concentration. These behaviors were not observed for diethyl disulfide (DEDS) or diphenyl disulfide (DPDS). Our results indicate that DMDS molecules with the shortest alkyl chains on the gold surface can be inserted into self-assembled monolayers (SAMs) without the S–S bond cleavage during self-assembly due to insufficient lateral van der Waals interaction and the low adsorption activity of disulfides, whereas DEDS with longer alkyl chains or DPDS with the weak disulfide bond dissociation energy would not. These unusual DMDS adsorption behaviors were examined by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). We also compared the bonding dissociation energy of the S–S bonds of various disulfides by means of a density functional theory (DFT) calculation. 相似文献
9.
Xun Fu Danmei Wu Xiaodong Zhou Huaqiang Shi Zhengshui Hu 《Journal of nanoparticle research》2007,9(4):675-681
Hollow spherical molybdenum disulfide has been successfully synthesized via a solvothermal method using Cyanex 301 as sulfur
source and modification agent. The hollow spheres are characterized by transmission electron microscopy, scanning electron
microscopy, X-ray diffraction and Energy-Dispersive X-ray analysis. The influences of reaction conditions are also discussed
while a mechanism is proposed to explain the formation of the peculiar morphology. 相似文献
10.
将单层二硫化钼用石墨烯进行封装,构造了石墨烯和二硫化钼的范德瓦耳斯异质结构,并且分别在氩气(Ar)和氢气(H2)氛围下,详细研究了被封装的二硫化钼的热稳定性.结果表明:在氩气氛围中,石墨烯封装的二硫化钼在400–1000℃下一直保持稳定,而石墨烯和氧化硅上裸露的二硫化钼在1000℃时几乎全部分解;在氢气氛围中,石墨烯封装的二硫化钼在400–1000℃下一直稳定存在,而石墨烯和氧化硅上裸露的二硫化钼在800℃下已经完全分解.综上可得,在氩气和氢气的氛围下,被石墨烯封装的二硫化钼的热稳定性得到了显著的提高.该研究通过用石墨烯将单层的二硫化钼进行封装以提高其热稳定性,在未来以单层二硫化钼作为基础材料的电子器件中,可以保证其在高温下能够正常工作.该研究也为提高其他二维材料的热稳定性提供了一种可行的方法和思路. 相似文献