4-硫代胸腺嘧啶S_2(ππ~*)激发态的衰变动力学
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摘要
研究硫代核酸碱基衰变动力学对揭开其产生高产率的T1态理论机制有重大意义。运用共振拉曼技术和多态完全活化空间自洽场(MS-CASSCF//CASPT2)理论方法研究4-硫代胸腺嘧啶的激发态动力学。分析了4-硫代胸腺嘧啶的紫外光谱、振动光谱和共振拉曼光谱,获取了各激发态及势能面交叉点的最低能量结构和激发能,探讨了共振拉曼光谱的强度模式,探讨了S2态初始结构动力学与各弛豫路径的关系,通过与2-硫代尿嘧啶比较得出了硫取代位置对三条系间窜越通道的影响。结果表明:4-硫代胸腺嘧啶有3条非辐射和1条辐射弛豫路径,其中非辐射路径Ⅰ为主要衰减通道。乙腈中,4TT的3条非辐射路径的效率低于2TU,而其辐射路径的效率明显高于2TU。
Studying decay dynamics of thio-substituted nucleobases(thiobases)is of great significance for revealing the theoretical mechanism of its high yield of T1 state.The resonance Raman spectroscopy and the multi-state complete-active space self-consistent field(MS-CASSCF)calculations were adopted to investigate the excited state dynamics of 4-thiothymine(4 TT).Ultraviolet spectra,vibrational spectra and resonance Raman spectra were identified.The minimum energy structures and excitation energy of interaction between each excited state and potential energy surface were obtained.The intensity mode of the resonance Raman spectrum was analyzed.The relationship between the initial structure dynamics of the S2 state and the relaxation paths was discussed.By comparing with the 2-thiouracil,the effect of the sulfur substitution position on the three different ISC channels was finally obtained.The results show that there are three nonradiative and one radiative relaxation paths for 4 TT,and nonradiative path I is the main decay channel.In acetonitrile,the efficiency of the three nonradiative paths of 4 TT is lower than that of2 TU,while the efficiency of its radiation path is much higher than that of 2 TU.
Studying decay dynamics of thio-substituted nucleobases(thiobases)is of great significance for revealing the theoretical mechanism of its high yield of T1 state.The resonance Raman spectroscopy and the multi-state complete-active space self-consistent field(MS-CASSCF)calculations were adopted to investigate the excited state dynamics of 4-thiothymine(4 TT).Ultraviolet spectra,vibrational spectra and resonance Raman spectra were identified.The minimum energy structures and excitation energy of interaction between each excited state and potential energy surface were obtained.The intensity mode of the resonance Raman spectrum was analyzed.The relationship between the initial structure dynamics of the S2 state and the relaxation paths was discussed.By comparing with the 2-thiouracil,the effect of the sulfur substitution position on the three different ISC channels was finally obtained.The results show that there are three nonradiative and one radiative relaxation paths for 4 TT,and nonradiative path I is the main decay channel.In acetonitrile,the efficiency of the three nonradiative paths of 4 TT is lower than that of2 TU,while the efficiency of its radiation path is much higher than that of 2 TU.
引文
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[2]Crespo-Hernández C E,Cohen B,Kohler B.Base stacking controls excited-state dynamics in A.T DNA[J].Nature,2005,436(7054):1141-1144.
[3]Middleton C T,Harpe K D L,Su C,et al.DNA excited-state dynamics:From single bases to the double helix[J].Annual Review of Physical Chemistry,2009,60(1):217-239.
[4]Buchvarov I,Wang Q,Raytchev M,et al.Electronic energy delocalization and dissipation in single-and double-stranded DNA[J].Proceedings of the National Academy of Sciences of the United States of America,2007,104(12):4794-4797.
[5]Markovitsi D,Onidas D,Gustavsson T,et al.Collective behavior of franck-condon excited states and energy transfer in DNA double helices[J].Journal of the American Chemical Society,2005,127(49):17130-17131.
[6]Kuramochi H,Kobayashi T,Suzuki T,et al.Excitedstate dynamics of 6-aza-2-thiothymine and 2-thiothymine:Highly efficient intersystem crossing and singlet oxygen photosensitization[J].Journal of Physical Chemistry B,2010,114(26):8782-8989.
[7]Pollum M,Jockusch S,Crespohernández C E.Increase in the photoreactivity of uracil derivatives by doubling thionation[J].Physical Chemistry Chemical Physics Pccp,2015,17(41):27851-27861.
[8]Tarsa-Goslinska K,Burdzinski G,Wenska G.Relaxation of the T1,excited state of 2-thiothymine,its riboside and deoxyriboside-enhanced nonradiative decay rate induced by sugar substituent[J].Journal of Photochemistry and Sphotobiology A:Chemistry,2014,275(11):89-95.
[9]Pollum M,Jockusch S,Crespo-Hernández C E.2,4-Dithiothymine as a potent UVA chemotherapeutic agent[J].Journal of the American Chemical Society,2014,136(52):17930-17933.
[10]Harada Y,Suzuki T,Ichimura T,et al.Triplet formation of 4-thiothymidine and its photosensitization to oxygen studied by time-resolved thermal lensing technique[J].Journal of Physical Chemistry B,2007,111(19):5518-5524.
[11]Harada Y,Okabe C,Kobayashi T,et al.Ultrafast intersystem crossing of 4-thiothymidine in aqueous solution[J].Journal of Physical Chemistry Letters,2010,1(2):480-484.
[12]Reichardt C,Crespo-Hernández C E.Room-temperature phosphorescence of the DNA monomer analogue 4-thiothymidine in aqueous solutions after UVA excitation[J].Journal of Physical Chemistry Letters,2010,1(15):2239-2243.
[13]Reichardt C,Crespo-Hernández C E.Ultrafast spin crossover in 4-thiothymidine in an ionic liquid[J].Chemical Communications,2010,46(32):5963-5965.
[14]Zhang Y,Zhu X,Smith J,et al.Direct observation and quantitative characterization of singlet oxygen in aqueous solution upon UVA excitation of 6-thioguanines[J].Journal of Physical Chemistry B,2011,115(8):1889-1894.
[15]Reichardt C,Guo C,Crespo-Hernández C E.Excitedstate dynamics in 6-thioguanosine from the femtosecond to microsecond time scale[J].Journal of Physical Chemistry B,2011,115(12):3263-3270.
[16]Zou X,Dai X,Liu K,et al.Photophysical and photochemical properties of 4-thiouracil:Time-resolved IR spectroscopy and DFT studies[J].Journal of Physical Chemistry B,2014,118(22):5864-5872.
[17]Mai S,Philipp M,Leticia G.Intersystem crossing pathways in the noncanonical nucleobase 2-thiouracil:a time-dependent picture[J].Journal of Physical Chemistry Letters,2016,7(11):1978-1983.
[18]Mai S,Pollum M,Martínez-Fernández L,et al.The origin of efficient triplet state population in sulfursubstituted nucleobases[J].Nature Communications,2016,7(13077):1-8.
[19]Koyama D,Milner M J,Orr-Ewing A J.Evidence for a double well in the first triplet excited state of 2-thiouracil[J].Journal of Physical Chemistry B,2017,121(39):9274-9280.
[20]Cui G,Fang W H.State-specific heavy-atom effect on intersystem crossing processes in 2-thiothymine:A potential photodynamic therapy photosensitizer[J].Journal of Chemical Physics,2013,138(4):1977.
[21]Pollum M,Crespo-Hernández C E.Communication:The dark singlet state as a doorway state in the ultrafast and efficient intersystem crossing dynamics in2-thiothymine and 2-thiouracil[J].Journal of Chemical Physics,2014,140(7):071101-071106.
[22]Jiang J,Zhang T,Zheng X,et al.Short-time dynamics of 2-thiouracil in the light absorbing S2(ππ*)state[J].Journal of Chemical Physics,2015,143(17):175103-175108.
[23]Frisch M J,Trucks G W,Schlegel H B,et al.Gaussian 09[M],Wallingford,CT:Gaussian Inc,2009:67-69.
[24]Werner H J.Third-order multireference perturbation theory The CASPT3 method[J].Molecular Physics,1996,89(2):645-661.
[25]Celani P,Werner H J.Multireference perturbation theory for large restricted and selected active space reference wave functions[J].Journal of Chemical Physics,2000,112(13):5546-5557.
[26]Werner H J,Knowles P J,Knizia G,et al.Molpro:A general-purpose quantum chemistry program package[J].Wiley Interdisciplinary Reviews Computational Molecular Science,2012,2(2):242-253.
[27]Jamróz M H.Vibrational energy distribution analysis VEDA 4[M].Warsaw,2004:88-98.
[28]Martínez-Fernández L,Granucci P G,Crespo-Hernández C E,et al.Decoding the molecular basis for the population mechanism of the triplet phototoxic precursors in UVA light-activated pyrimidine anticancer drugs[J].Chemistry,2017,23(11):2619-2627.