全文获取类型
收费全文 | 97篇 |
免费 | 9篇 |
国内免费 | 15篇 |
专业分类
化学 | 112篇 |
晶体学 | 4篇 |
物理学 | 5篇 |
出版年
2021年 | 3篇 |
2019年 | 3篇 |
2017年 | 2篇 |
2016年 | 3篇 |
2015年 | 1篇 |
2014年 | 9篇 |
2013年 | 13篇 |
2012年 | 5篇 |
2011年 | 6篇 |
2010年 | 4篇 |
2009年 | 2篇 |
2008年 | 6篇 |
2007年 | 10篇 |
2006年 | 6篇 |
2005年 | 5篇 |
2004年 | 8篇 |
2003年 | 5篇 |
2002年 | 7篇 |
2001年 | 3篇 |
2000年 | 3篇 |
1999年 | 5篇 |
1998年 | 2篇 |
1997年 | 1篇 |
1996年 | 1篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 1篇 |
1991年 | 1篇 |
排序方式: 共有121条查询结果,搜索用时 250 毫秒
51.
Adsorption of methanol and methoxy at four selected sites(top,bridge,hcp,fcc)on Cu(111)surface has beeninvestigated by density functional theory method at the generalized gradient approximation(GGA)level.The cal-culation on adsorption energies,geometry and electronic structures,Mulliken charges,and vibrational frequenciesof CH_3OH and CH_3O on clean Cu(111)surface was performed with full-geometry optimization,and compared withthe experimental data.The obtained results are in agreement with available experimental data.The most favoriteadsorption site for methanol on Cu(111)surface is the top site,where C-O axis is tilted to the surface.Moreover,the preferred adsorption site for methoxy on Cu(111)surface is the fcc site,and it adsorbs in an upright geometrywith pseudo-C_(3v) local symmetry.Possible decomposition pathways also have been investigated by transition-statesearching methods.Methoxy radical,CH_3O,was found to be the decomposition intermediate.Methanol can be ad-sorbed on the surface with its oxygen atom directly on a Cu atom,and weakly chemisorbed on Cu(111)surface.Incontrast to methanol,methoxy is strongly chemisorbed to the surface. 相似文献
52.
Yuanyuan Zhang Wei Zhang Xinrong Chen Zhenping Cheng Jianhong Wu Jian Zhu Xiulin Zhu 《Journal of polymer science. Part A, Polymer chemistry》2008,46(3):777-789
A three‐arm star azo side‐chain liquid crystalline (LC) homopolymer, poly[6‐(4‐methoxy‐4‐oxy‐azobenzene) hexyl methacrylate] (PMMAZO), was synthesized by atom transfer radical polymerization (ATRP) method. The polymerization of 6‐(4‐methoxy‐4‐oxy‐azobenzene) hexyl methacrylate proceeded in a controlled/“living” way. A series of three‐arm star LC block copolymers (PMMAZO‐b‐PMMA) were also synthesized. The polymers were characterized by 1H NMR, gel permeation chromatograph, and UV–vis spectra, respectively. The both polymers of PMMAZO and copolymers of PMMAZO‐b‐PMMA exhibited a smetic phase and a nematic phase. As concern to the PMMAZO, the glass‐transition temperature (Tg) and phase‐transition temperature from the smetic to nematic phase and from the nematic to isotropic phase increased with the increase of molecular weight (Mn(GPC)) of PMMAZO. The phase transition temperature of the block copolymers, PMMAZO‐b‐PMMA, with the same PMMA block was similar to that of PMMAZO. However, the Tg of the PMMAZO‐b‐PMMA decreased at low azo content and then increased with the increasing Mn(GPC) when azo content was above 61.3%. With illumination of linearly polarized Kr+ laser beam at modest intensities (35 mW/cm2), significant surface relief gratings formed on PMMAZO films with different molecular weights were observed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 777–789, 2008 相似文献
53.
A series of Zn (II), Pd (II) and Cd (II) complexes, [(L) n MX 2 ] m (L = L‐a–L‐c; M = Zn, Pd; X = Cl; M = Cd; X = Br; n, m = 1 or 2), containing 4‐methoxy‐N‐(pyridin‐2‐ylmethylene) aniline ( L‐a ), 4‐methoxy‐N‐(pyridin‐2‐ylmethyl) aniline ( L‐b ) and 4‐methoxy‐N‐methyl‐N‐(pyridin‐2‐ylmethyl) aniline ( L‐c ) have been synthesized and characterized. The X‐ray crystal structures of Pd (II) complexes [L 1 PdCl 2 ] (L = L‐b and L‐c) revealed distorted square planar geometries obtained via coordinative interaction of the nitrogen atoms of pyridine and amine moieties and two chloro ligands. The geometry around Zn (II) center in [(L‐a)ZnCl 2 ] and [(L‐c)ZnCl 2 ] can be best described as distorted tetrahedral, whereas [(L‐b) 2 ZnCl 2 ] and [(L‐b) 2 CdBr 2 ] achieved 6‐coordinated octahedral geometries around Zn and Cd centers through 2‐equivalent ligands, respectively. In addition, a dimeric [(L‐c)Cd(μ ‐ Br)Br] 2 complex exhibited typical 5‐coordinated trigonal bipyramidal geometry around Cd center. The polymerization of methyl methacrylate in the presence of modified methylaluminoxane was evaluated by all the synthesized complexes at 60°C. Among these complexes, [(L‐b)PdCl 2 ] showed the highest catalytic activity [3.80 × 104 g poly (methyl methacrylate) (PMMA)/mol Pd hr?1], yielding high molecular weight (9.12 × 105 g mol?1) PMMA. Syndio‐enriched PMMA (characterized using 1H‐NMR spectroscopy) of about 0.68 was obtained with Tg in the range 120–128°C. Unlike imine and amine moieties, the introduction of N‐methyl moiety has an adverse effect on the catalytic activity, but the syndiotacticity remained unaffected. 相似文献
54.
Kodakandla Venkata Syamasundar Guvvala Vinodh Kalavagunta Venkata Naga Satya Srinivas Bogineni Srinivasulu 《Helvetica chimica acta》2012,95(4):643-646
Chemical examination of the MeOH extract of Plectranthus bishopianus Benth ., a rare and endangered plant, resulted in isolation of a new abietane diterpene, 6β‐hydroxy‐7α‐methoxyroyleanone ( 1 ), along with two more diterpenoids, 6,7‐dehydroroyleanone, and 6β,7α‐dihydroxyroyleanone, a triterpene oleanolic acid, and two sterols, β‐sistosterol and stigmasterol. The structures of the isolated compounds were elucidated on the basis of spectroscopic data and also by comparison with authentic samples. 相似文献
55.
Jieming Gao Yingzhi Guo Zhongwei Gu Xingdong Zhang 《Frontiers of Chemistry in China》2009,4(1):104-109
Amphiphilic block copolymers composed of D,L-lactide, trimethylene carbonate and the methoxy poly (ethylene glycol) (PETLA)
were synthesized with ringopening copolymerization. Studies on the micellization and drug-controlled release behavior of PETLA
were performed. Both of the copolymers and the micelles were characterized with the methods of 1H nuclear magnetic resonance (1H-NMR), fluorescence spectroscopy, gel permeation chromatographic (GPC), dynamic light scattering (DLS), transmission electron
microscopy (TEM) and ultraviolet-visible spectroscopy (UV). As a result, the critical micelle concentration of the copolymer
was decreased with the increase of the hydrophobic chain length. DLS results indicated the diameters of the micelle were increased
with increasing hydrophobic length. TEM photographs illustrated that micelles MT1 were regularly spherical with the diameter
from 30 nm to 40 nm. Taking 9-nitro-20(S)-camptothecin (9-NC) for the model drug, the release profiles in vitro show that the release behavior from micelles was controllable and nearly in zero order after the initial burst release.
__________
Translated from Acta Polymerica Sinica, 2008, 2 (in Chinese) 相似文献
56.
57.
Adsorption of the methoxy radical on clean and on low oxygen precovered Ru(0 0 0 1) metallic surfaces has been studied by density-functional theory cluster calculations. Methoxy is predicted to be preferentially chemisorbed on both hollow sites (hcp and fcc) of such surfaces, and adopts an upright orientation (C3ν local symmetry). Such prediction is supported by the good agreement found between the calculated vibrational frequencies and the experimentally observed RAIRS spectra. Regarding the charge transfer process between the adsorbate and the surface, our results suggest that the bonding is dominantly polar covalent which arises from a charge donation from the ruthenium surface to the radical, and the co-adsorbed electronegative oxygens deplete slightly the surface electron density. However, the major difference is not induced through much O-Ru bonding, but indirectly, by lowering the valence d-band center of the system. This results in a lower adsorption energy for methoxy than on the clean Ru(0 0 0 1) surface, in accordance with experimental data. Further, accordingly to the present calculations, the radical is expected to dissociate or desorb more easily on the modified surface but with no participation from the co-adsorbed oxygen atoms. 相似文献
58.
A. Sabrina Restrepo Neissa M. Pinzn Lu‐Kwang Ju 《Journal of polymer science. Part A, Polymer chemistry》2004,42(12):2950-2959
For the development of pH‐sensitive surfactants to be used in water‐in‐oil fermentation, the free‐radical terpolymerization of methacrylic acid (MAA), methoxy poly(ethylene glycol) methacrylate (MPEGMA), and lauryl methacrylate (LMA), at a molar ratio of 1.0:0.04:0.76, was studied with two initiators, azobisisobutyronitrile (AIBN) and hydrogen peroxide, at different concentrations. The polymer synthesized with 0.45% AIBN as the initiator was the most promising, giving similar conversions of all three monomers throughout the 10‐h polymerization. The subsequent study on AIBN‐initiated systems indicated that MPEGMA caused an increase‐then‐decrease profile of the MAA conversion with a plateau around an ethylene glycol/MAA ratio of 1–2. This observation was fairly consistent with the well‐known type II template polymerization of poly(ethylene glycol) (PEG)–MAA systems. The reactivity ratios obtained in this study suggested that the polymer synthesized with AIBN as the initiator had a structure of alternating blocks of MAA and LMA, with isolated PEG grafts. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2950–2959, 2004 相似文献
59.
I2‐Catalyzed Divergent Regioselective Addition of Methoxybenzenes with Ethenylbenzenes under Microwave Irradiation 下载免费PDF全文
Nalajala Nageswara Rao Maddi Raghavender Reddy Konakalla Ramakrishna Harshadas Mitaram Meshram 《Helvetica chimica acta》2014,97(5):744-749
A highly efficient synthesis of 1,2,2‐triarylethanones has been developed from simple and commercially available electron‐rich arenes and styrenes (ethenylbenzenes). 相似文献
60.
M. N'dollo P.S. Moussounda T. Dintzer B. M'Passi‐Mabiala F. Garin 《Surface and interface analysis : SIA》2013,45(9):1410-1418
The adsorption of methanol on flat Au (100) surface with different coverages (θ = 1.0, 0.5 and 0.25 monolayer (ML)) is studied using density functional theory. Among the three sites (top, bridge and hollow) and coverages investigated in the present work, no adsorption is stable for θ = 1.0 ML. The most energetically preferred site of adsorption for CH3OH is found to be the hollow site for coverages of 0.25 ML and 0.50 ML. We also find that for all adsorption sites, an increase in CH3OH coverage triggers a decrease in the adsorption energy. The geometric parameters, local density of states and work function changes are analysed in detail. The coadsorption of methoxy and hydrogen has also investigated. In addition, the dissociation of methanol on Au(100) has been studied, and an activation energy was found to be 1.72 eV. This result compare with existing data in the literature for Au(111) surface. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献