全文获取类型
收费全文 | 1215篇 |
免费 | 129篇 |
国内免费 | 356篇 |
专业分类
化学 | 1506篇 |
晶体学 | 15篇 |
综合类 | 17篇 |
数学 | 1篇 |
物理学 | 161篇 |
出版年
2024年 | 1篇 |
2023年 | 15篇 |
2022年 | 37篇 |
2021年 | 44篇 |
2020年 | 78篇 |
2019年 | 52篇 |
2018年 | 29篇 |
2017年 | 47篇 |
2016年 | 60篇 |
2015年 | 56篇 |
2014年 | 49篇 |
2013年 | 120篇 |
2012年 | 83篇 |
2011年 | 76篇 |
2010年 | 45篇 |
2009年 | 59篇 |
2008年 | 82篇 |
2007年 | 69篇 |
2006年 | 65篇 |
2005年 | 68篇 |
2004年 | 59篇 |
2003年 | 69篇 |
2002年 | 51篇 |
2001年 | 46篇 |
2000年 | 38篇 |
1999年 | 54篇 |
1998年 | 31篇 |
1997年 | 33篇 |
1996年 | 32篇 |
1995年 | 24篇 |
1994年 | 24篇 |
1993年 | 25篇 |
1992年 | 22篇 |
1991年 | 14篇 |
1990年 | 10篇 |
1989年 | 9篇 |
1988年 | 3篇 |
1987年 | 1篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1984年 | 5篇 |
1983年 | 2篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1978年 | 1篇 |
1972年 | 1篇 |
1969年 | 1篇 |
排序方式: 共有1700条查询结果,搜索用时 8 毫秒
31.
5,10,15,20—四(对—乙酯苯基)卟啉LB膜的结构 总被引:1,自引:0,他引:1
对卟啉类化合物LB膜的结构、电性质和气敏性的研究已见报道。本文利用膜天平和UV-Vis分光光度计研究了标题化合物在气-液界面上的成膜特性、分子间相互作用和LB膜的结构。5,10,15,20-四(对-乙酯苯基)卟啉(TPEPP)由5,10,15,20-四(对-氰苯基)卟啉和乙醇酯化得到。元素分析测定值与计算值相符。λ(CHCl_3,nm):421,515,550,590,645;ν(KBr压 相似文献
32.
Ivan J. B. Lin 《中国化学会会志》1983,30(1):17-20
Some halo or mercaptide bridged palladium (II) dimers, [Pd(S2CNR2)X]3 (R=ibutyl, X=Cl, Br, I, S-ethyl and S-t-butyl) were studied by variable temperature 1H nmr spectroscopy. Line shape changes of the chloro and bromo bridged dimers were interpretated by the solvolytic breaking of the Pd-X bond, while mercaptide bridged complexes were explained in terms of slow N-C single bond rotation. The results consist with the strengthness of the class b metal ion with various soft donor ligands. 相似文献
33.
A unique approach to non-covalent electron and energy transfer is described that is based on the formation of salt bridges between oppositely charged porphyrin units. A new class of electrostatically linked dimeric and pentameric porphyrins was synthesized by interaction of novel anionic boron containing porphyrins such as 5-(benzamidodecahydro-closo-dodecaborate)-10,15,20-triphenylporphyrin (N1) and meso-tetrakis-benzamidodecahydro-closo-dodecaborate)porphyrin (N2) and a variety of cationic meso-tetraarylporphyrin units. A bipyridine linked dimer (N1 · bpy · N1) was also prepared by employing N,N′-dimethyl-4,4′-bipyridinium (bpy) as a spacer between two mono-anionic species. A quinone-porphyrin dyad was also prepared for electron or energy transfer demonstration. All the synthesized assemblies were characterized by NMR, IR, UV-Vis, and mass spectroscopy. Significant spectral changes occurred in the absorption spectra of these non-covalent porphyrin assemblies compared to those of the reference monomers, indicating the presence of electronic interaction between the adjacent porphyrin units. Resonance light scattering was also used to study the formation of these assemblies in solution. 相似文献
34.
35.
烷氧桥相连的四苯基双金属卟啉配合物的红外光谱研究 总被引:1,自引:1,他引:1
研究了烷氧桥相连的四苯基双卟啉及其Mn(Ⅱ),Fe(Ⅲ),Co(Ⅱ)配合物的红外光谱(3600~150cm^-1),对一些主要吸收谱带进行了经验归属,金属敏感谱带出现1558.2(以H2P-H2P为例)、1477.2,1401.9,1350.5,1001.7,965.9,877.3和798.8cm^-1附近,金属和烷氧桥都敏感的谱带出现在1595.1(以H2P为例)、1491.1,851.1和72 相似文献
36.
Toshikatsu Takanami 《Tetrahedron letters》2005,46(16):2893-2896
The catalytic Z-selective Claisen rearrangement of simple aliphatic allyl vinyl ethers can be achieved using a chromium(III) porphyrin complex, Cr(TPP)Cl, as a catalyst: Cr(TPP)Cl significantly enhances reversal of E-Z selectivity in the thermal Claisen rearrangement of allyl vinyl ethers, especially, 4,5- and 4,6-disubstituted derivatives, at low catalyst loading. 相似文献
37.
Rondeau D Martineau C Blanchard P Roncali J 《Journal of mass spectrometry : JMS》2002,37(10):1081-1085
Oligothienylenevinylenes/C(60) dyads n-C and triads n-C(2) are studied by electrospray mass spectrometry. A clear correlation is observed between the nature of the charged species detected by mass spectrometry, i.e. protonated molecule [M + H], (+) cation radical M(+.) and dication M(++), and the oxidation potentials of the molecules. Moreover, under defined solubility conditions, mass spectrometry provides conclusive evidences for the reversible dimerization of cation-radicals of n-C(2) compounds. 相似文献
38.
《Electroanalysis》2006,18(7):649-654
For the first time, the voltammetry of an ensemble of immobilized benzonitrile microdroplets containing 5,10,15,20‐tetraphenyl‐21H,23H‐porphine iron (III) chloride, TPPFeCl immobilized at platinum electrodes immersed in various aqueous electrolytes has been explored. The reduction of TPPFeCl was observed with the voltammetric response seen to be highly dependent on the nature of ions in the surrounding aqueous phase. Unlike voltammetry in purely homogeneous solution the nature of the aqueous electrolyte can influence the voltammetry in the droplet phase. The electrochemical reduction of TPPFeCl contained within tetrabutylammonium chloride (TBACl) supported benzonitrile (PhCN) microdroplets immersed into an aqueous solution of TBACl was first studied. During TPPFeCl reduction the resulting [TPPFeCl]? species is stabilized due to the excess of chloride anions inside the oil droplet. Voltammograms of homogeneous solutions of PhCN supported with TBACl show similar chemically reversible process which is also attributed to the stable [TPPFeCl]? species. This anion stabilization was not observed when the oil droplets were supported with tetrabutylammonium perchlorate (TBAP) or when the PhCN solution bathing the microdroplet ensemble was supported with TBAP resulting in a chemically irreversible process. The voltammetry of unsupported droplets immobilized on a platinum electrode immersed in different aqueous electrolytes was also explored and the fate of the [TPPFeCl]? species formed considered during the reduction sweep. Similarities and difference to voltammetry in purely homogeneous media are noted and the use of droplet voltammetry provides complimentary information. 相似文献
39.
Herein, we discuss the analyses and quantification of the different components in porphyrin mixtures, prepared from p-anisaldehyde, p-tolualdehyde, and 5-(4-bromophenyl)-dipyrromethane with acid catalysis, using NMR and HPLC. The advantages and disadvantages of these analytical methods are emphasized. Due to the similar size of a bromine atom and a methyl group it was possible to grow crystals suitable for X-ray crystallographic studies from a mixture of porphyrins, where the 4-position of the meso-phenyl rings was either substituted with methyl groups or bromine atoms. We also show that X-ray studies are inferior to NMR analysis for determining the components in a porphyrin mixture. 相似文献
40.
The coordination compounds of acctylacetonate-5,10,15,20-tctrasubstituted phcnyl-porphyrin with Yttrium, Y(o-Cl)Tppacac, Y(m- Cl)Tppacac, Y(p-Cl)Tppacac, Y(o-CH3O) Tppacac, and Y(p-CH3O)Tppacac (H2Tpp: tetraphcnylporphyrin, Hacac: acetylacctonc), were prepared and characterised on the basis of elemental analysis, infrared spectra, UV-visiblc spectra and thermal analysis. 相似文献