2种PRODAN衍生物分子激发态氢键的理论计算
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摘要
氢键是一种存在于溶质和溶剂之间非常重要的弱相互作用,对有机分子及生物体系的光化学性质有至关重要的影响。PRODAN(6-丙酰基-2-二甲基氨基萘)分子是一种微极性摩尔探针,主要用于研究膜和生物大分子的物理和化学性质,在有机溶剂中有较强的荧光响应。主要采用了密度泛函理论(DFT)方法和含时密度泛函理论(TDDFT)方法,研究了PRODAN衍生物1a和3a分子在气相中的单体以及其在甲醇溶液中所形成的氢键复合物在基态和激发态的氢键性质。通过对分子在不同状态下的几何结构、电子光谱和氢键结合能的计算结果对比分析,可以确定PRODAN衍生物1a和3a分子在甲醇溶液中的激发态氢键作用更强,同时PRODAN衍生物1a和3a分子在甲醇溶液中光谱信号的明显增加也是由于分子间氢键作用的影响。
Hydrogen bonding is a very important weak interaction between solute and solvent, which has a crucial influence on the photochemical properties of organic molecules and biological systems. PRODAN(6-propionyl-2-dimethylaminonaphthalene) is a micropolar molar probe, which is mainly used to study the physical and chemical properties of membranes and biological macromolecules, and has a strong fluorescence response in organic solvents. Density functional theory(DFT) and time-dependent density functional theory(TDDFT) methods were used to study the properties of the hydrogen bond of PRODAN derivative molecules(1a and 3a) in gas phase and methanol solution on ground state and excited state. By comparing the calculated results of the geometrical structure, electronic spectra and hydrogen bond energy of the molecule in different states, it is determined that the excited hydrogen bond of the PRODAN derivativemolecule(1a and 3a) in methanol solution is stronger. At the same time, the significant increase of the spectral signal of the two PRODAN derivatives(1a and 3a) in methanol solution and red shift of spectra are both due to the effect of strength of intermolecular hydrogen bond.
Hydrogen bonding is a very important weak interaction between solute and solvent, which has a crucial influence on the photochemical properties of organic molecules and biological systems. PRODAN(6-propionyl-2-dimethylaminonaphthalene) is a micropolar molar probe, which is mainly used to study the physical and chemical properties of membranes and biological macromolecules, and has a strong fluorescence response in organic solvents. Density functional theory(DFT) and time-dependent density functional theory(TDDFT) methods were used to study the properties of the hydrogen bond of PRODAN derivative molecules(1a and 3a) in gas phase and methanol solution on ground state and excited state. By comparing the calculated results of the geometrical structure, electronic spectra and hydrogen bond energy of the molecule in different states, it is determined that the excited hydrogen bond of the PRODAN derivativemolecule(1a and 3a) in methanol solution is stronger. At the same time, the significant increase of the spectral signal of the two PRODAN derivatives(1a and 3a) in methanol solution and red shift of spectra are both due to the effect of strength of intermolecular hydrogen bond.
引文
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[ 2 ]ZHAO G J,HAN K L.Hydrogen bonding in the electronic excited state[J].Accounts Chem Res,2012,45(3):404-413.
[ 3 ]ZHAO G J,HAN K L.Effects of hydrogen bonding on tuning photochemistry:concerted hydrogen-bond strengthening and weakening[J].Chem Phys Chem,2008,9:1842-1846.
[ 4 ]ZHAO G J,HAN K L.Ultrafast hydrogen bond strengthening of the photoexcited fluorenone in 37alcohols for facilitating the fluorescence quenching[J].J Phys Chem A,2007,111:9218-9223.
[ 5 ]SAHA S K,DOGRA S K.Solvatochromic effects in in the absorption and fluorescence spectra of indazole and its amino derivatives[J].Photochem Photobiol A:Chem,1997,110:257-266.
[ 6 ]WEBER G,FARRIS F J.Synthesis and spectral properties of a hydrophobic fluorescent probe:6-propionyl-2-(dimethylamino) naphthalene[J].Biochemistry,1979,18:3075-3078.
[ 7 ]HOROCHOWSKA M,CIESLIK-BOCZULA B K,ROSPENK M.Ethanol-and trifluoroethanol-induced changes in phase states of DPPC membranes.Prodan emission-excitation fluorescence spectroscopy supported by PARAFAC analysis[J].Spectrochim Acta A,2018,192:16-22.
[ 8 ]ZHARKOVA O M,RAKHIMOV S I,MOROZOVA Y P.Quantum-chemical investigation of the spectral properties of fluorescent probes based on naphthalene derivatives(prodan,promen)[J].Russ Phys J,2013,56(4):411-419.
[ 9 ]FUKUDA R,CHIDTHONG R,CAMMI R.Optical absorption and fluorescence of PRODAN in solution:quantum chemical study based on the symmetry-adapted cluster-configuration interaction method[J].Chem Phys Lett,2012,552:53-57.
[10]CWIKLIK L,AQUINO A J A,VAZDAR M.Absorption and fluorescence of PRODAN in phospholipid bilayers:a combined quantum mechanics and classical molecular dynamics study[J].J Phys Chem A,2011,115:11428-11437.
[11]ADHIKARY R,BARNESC A,PETRICH J W.Solvation dynamics of the fluorescent probe PRODAN in heterogeneous environments:contributions from the locally excited and charge-transferred states[J].J Phys Chem B,2009,113:11999-12004.
[12]ROWE B A,ROACH C A,LIN J.Spectral heterogeneity of PRODAN fluorescence in isotropic solvents revealed by multivariate photokinetic analysis[J].J Phys Chem A,2008,112:13402-13412.
[13]丁耀光.荧光探针在生物大分子中的应用[J].沈阳师范大学学报(自然科学版),2018,26(4):480-484.
[14]ALTY I G,CHEEK D W,CHEN T,et al.Intramolecular hydrogen-bonding effects on the fluorescence of PRODAN derivatives[J].J Phys Chem A,2016,120:3518-3544.
[15]FRISCH M J,TRUCKS G W,SCHLEGEL H B,et al.Gaussian 09[M].Gaussian Inc.Wallingford,CT,2009.
[16]BECKE A D.Density-functional exchange-energy approximation with correct asymptotic behavior[J].Phys Rev A,1988,38(6):3098-3100.