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求高手翻译Figure 1 shows the normalized absorption spectra of

707943 2010-06-10
Figure 1 shows the normalized absorption spectra of [Ru(bpy)3-n(dpb)n]2þ (n=1-3) and [Ru(bpy)3]2þ. Comparison of these spectra can lead to the assignments of a πfπ* transition to the bpy ligand centered at 286 nm, a πfπ* ... Figure 1 shows the normalized absorption spectra of [Ru(bpy)3-n(dpb)n]2þ (n=1-3) and [Ru(bpy)3]2þ. Comparison of these spectra can lead to the assignments of a πfπ* transition to the bpy ligand centered at 286 nm, a πfπ* transition to the dpb ligand centered at both 315 and 400 nm, and a 1MLCT transition over the visible region, in good agreement with the previous results.8 The dpb ligand renders the 1MLCT of [Ru(bpy)3-n(dpb)n]2þ 100 nm red-shifted compared to that of [Ru(bpy)3]2þ. In aqueous solutions, [Ru(bpy)3-n(dpb)n]2þ undergoes a further bathochromic shift (Supporting Information), favorable for PDT application. The 3MLCT emissions of [Ru(bpy)3-n(dpb)n]2þ fall in the region of NIR (Table 1 and Supporting Information), recorded on a Confocal Laser Micro-Raman Spectroscope (532 nm excitation). On the same instrument, an emission centered at 619nmwas observed for [Ru(bpy)3]2þ, in linewith the result obtained on a conventional fluorescence spectrophotometer. The electrochemical properties of these complexes were examined using cyclic voltammetry (Table 1 and Supporting Information). [Ru(bpy)2(dpb)]2þ displays a reversible Ru- (III/II) based oxidation wave at þ1.43 V versus SCE. The 0.14 V of anodic shift compared to that of [Ru(bpy)3]2þ (þ1.29 V) may be attributed to the more electronegative character or stronger π-accepting feature of dpb than bpy. This is supported by the less negative reduction potential of -0.60 V for dpb compared to -1.33 V for bpy (Table 1). For [Ru(bpy)(dpb)2]2þ and [Ru(dpb)3]2þ, the dpb ligand-based first reduction potentials appear at -0.50 V and -0.47 V, respectively, in accordance with the previous results.8 The oxidation processes of [Ru(bpy)(dpb)2]2þ and [Ru(dpb)3]2þ are no longer reversible with the peak potentials at 1.65 and 1.64 V, respectively. Carlson and RorerMurphy ascribed the irreversible oxidation wave of [Ru(dpb)3]2þ to the oxidation of the dpb ligand.8 The DNA titration approach was used to examine the binding abilities of these complexes toward calf thymusDNA (CT-DNA). The absorption spectrum of [Ru(bpy)2(dpb)]2þ shows negligible changes upon the addition of DNA, indicative of a weak interaction. For [Ru(bpy)(dpb)2]2þ and [Ru(dpb)3]2þ, the MLCT absorbance increased at first and then decreased continuously with the addition of CT-DNA. Such behavior was also observed for other Ru(II) complexes, probably due to the DNA-induced complex aggregation. 3g,5,13 Thus, an EB displacement assay was carried out to compare the DNA binding affinities of these complexes (Table 1 and Supporting Information). The binding constants of [Ru(bpy)(dpb)2]2þ and [Ru(dpb)3]2þ are much higher than that of [Ru(bpy)2(dpb)]2þ, presumably due to themore hydrophobic property of dpb than bpy (Supporting Information)
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丰山桂
图1示出了[Ru(bpy)3-n(dpb)n]2+(n=1-3)和[Ru(bpy)3]2+的归一化吸收谱。比较这些谱可以得出以下现象的陈述,即ZX在286nm处的bpy配体的π→π*跃迁,ZX在315和400nm处的dpb配体的π→π*跃迁,以及在可见光区的1MLCT跃迁,这和以前的结果很符合8。相比于[Ru(bpy)3]2+的吸收谱,dpb配体授予[Ru(bpy)3-n(dpb)n]2+的1MLCT以100nm的红移。在含水溶液中,[Ru(bpy)3-n(dpb)n]2+经历进一步的红移(支持信息),这有利于PDT的应用。[Ru(bpy)3-n(dpb)n]2+的3MLCT发射落在近红外区(表1和支持信息),在共焦激光显微拉曼光谱仪(532nm激发)上记录下来。在相同的仪器上,观察到了[Ru(bpy)3]2+的ZX位于619nm的发射,与在常规荧光分光光度计上得到的结果一致。
这些络合物的电化学性质用循环伏安法进行了研究(表1和支持信息)。[Ru(bpy)2(dpb)]2+在+1.43V相对于SCE下显示了可逆的基于Ru(III/II)的氧化波。相比于[Ru(bpy)3]2+(+1.29V)的0.14V的阳极偏移可以归因于dpb比bpy更大的负电特性或更强的π接受特征。这受到了dpb相比于bpy-1.33V较低的(-0.60V)负还原电位的支持(表1)。对于[Ru(bpy)(dpb)2]2+和[Ru(dpb)3]2+来说,基于dpb配体的diyi个还原电位分别出现在-0.50V和-0.47V。Carlson和Rorer Murphy把[Ru(dpb)3]2+的不可逆氧化波归因于dpb配体的氧化8。
采用了DNA滴定法来研究这些络合物对小牛胸腺DNA(CT-DNA)的结合亲和力。[Ru(bpy)2(dpb)]2+的吸收谱在添加DNA时显示出可忽略不计的变化,表明了弱的互作用。对于[Ru(bpy)(dpb)2]2+和[Ru(dpb)3]2+来说,MLCT吸光率先是增加,然后随着CT-DNA的添加而不断下降。这样的性状对于其他Ru(II)络合物也观察到了,这或许是由于DNA诱导的络合物聚集3g,5,13。因此,为了对比这些络合物的结合亲和力,进行了EB(溴化乙锭)置换测定(表1和支持信息)。[Ru(bpy)(dpb)2]2+和[Ru(dpb)3]2+的结合常数明显要高于[Ru(bpy)2(dpb)]2+的,这大概是由于dpb比bpy有更强的疏水性(支持信息)
14 0 2010-06-12 0条评论 回复
叔说你狠傻
昏倒,翻译些什么啊。上这儿回答的都是用翻译器的,又乱,错误率又高。还是自己想吧,悬赏分再高,也不会有人愿意认认真真帮你的忙。抱歉,你只能想别的办法解决了。
13 0 2010-06-11 0条评论 回复
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