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1. 北京大学化学学院高分子科学与工程系
2. 清华大学化学系
纸质出版日期:2011-2-1,
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李武松, 滕明俊, 贾欣茹, 危岩. 萘和丹酰基修饰的扇形树枝状分子聚集体的能量转移行为[J]. 高分子学报, 2011,(2):210-216.
ENERGY TRANSFER PROPERTY OF THE AGGREGATES FROM NAPHTHYL AND DANSYL MODIFIED POLY (AMIDOAMINE) DENDRONS[J]. Acta Polymerica Sinica, 2011,(2):210-216.
李武松, 滕明俊, 贾欣茹, 危岩. 萘和丹酰基修饰的扇形树枝状分子聚集体的能量转移行为[J]. 高分子学报, 2011,(2):210-216. DOI: 10.3724/SP.J.1105.2011.10033.
ENERGY TRANSFER PROPERTY OF THE AGGREGATES FROM NAPHTHYL AND DANSYL MODIFIED POLY (AMIDOAMINE) DENDRONS[J]. Acta Polymerica Sinica, 2011,(2):210-216. DOI: 10.3724/SP.J.1105.2011.10033.
分别对1-3代聚 (酰胺-胺) (PAMAM) 结构的dendron分子的外端基和focal point进行了修饰
得到了外端基为萘 (给体) 色团、焦点 (focal point) 为丹酰 (受体) 色团的树枝状化合物Dan-ABn-Nap (n=2
4
8) .利用荧光光谱测定了不同浓度下所得一系列树枝状分子在水中的荧光强度
并计算了它们的临界聚集浓度 (CAC) 值.发现Dan-ABn-Nap (n=2
4
8) 的CAC值随代数的增加而减小
这是由于随着代数增加
分子的聚集能力增强所造成的.TEM观察可见
Dan-ABn-Nap在水中形成不规则的球形聚集体
尺寸约在150 nm至650 nm之间.测试了Dan-ABn-Nap所形成聚集体的荧光性质.结果表明
当用萘的最大吸收波长激发聚集体Dan-ABn-Nap时
萘的荧光被大大猝灭
而发射出丹酰的荧光 (400~650 nm) .这说明在聚集体中发生了从萘到丹酰色团的能量转移.研究发现
在CAC浓度以下时
只发生低效率的能量转移
例如Dan-AB8-Nap的能量转移效率只有5.7%.而当浓度增至CAC以上时
由于形成聚集体
其对应的能量转移效率大大提高
达到77.1%.这是由于聚集体的形成
使树枝状分子的排列更加有序
色团间距离更加靠近
同时既可发生分子内的能量转移
又可发生分子间的能量转移
因此能量转移效率提高.
The aggregation behavior of the amphiphilic poly (amidoamine) (PAMAM) dendrons (ABn-Nap
Dan-ABn and Dan-ABn-Nap
n denotes the generation of the dendrons
Dan = Dansyl
Nap = Naphthyl) in water was explored and their energy transfer property was studied by using UV-Vis
fluorescence spectroscopy and transmission electron microscopy (TEM) .It was found that the modified dendritic molecules aggregated to irregular sphere-like assemblies with the size range of 150 ~ 650 nm.The critical aggregation concentration (CAC) values of ABn-Nap and Dan-ABn-Nap decreased with the generation of dendron increasing
which indicated the enhanced aggregation ability of them.Specially
Dan-AB4 displayed the lowest CAC value
indicating the dendron possessed an appropriate hydrophilic-hydrophobic balance that was a key factor for the aggregation.Notably
the efficient energy transfer occurred from the peripheral naphthyl groups to the focal dansyl unit in the aggregates.While Dan-ABn-Nap aggregates were excited at 282 nm
the fluorescence of naphthyl groups was quenched greatly
instead
strong fluorescence (400 ~ 650 nm) of dansyl groups appeared.The energy transfer efficiencies of different generation dendrons at different concentrations in water were calculated by using Frster theory.Energy transfer occurred with low efficiency when the concentration of dendrons was lower than CAC
for example
the energy transfer efficiency of Dan-AB8-Nap was only 5.7% at the concentration of 1.0 × 10-7 mol/L.However
when the concentration was above CAC (1.0 × 10-4 mol/ L)
the energy transfer efficiency improved greatly (77.1%) .Interestingly
the energy transfer efficiency of the aggregates in water was higher than that in organic solution at the same concentration.These results can be attributed to the more ordered stacking of the chromophores
closer distance between chromophores and both intermolecular and intramolecular energy transfer in the aggregates.
树枝状分子聚集体能量转移萘丹酰
Poly (amidoamine) dendonsSpherical aggregatesEnergy transferNaphthylDansyl
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