Selectively Identifying Exposed-over-Unexposed C-C+ Pairs in Human Telomeric i-Motif Structures with Length-Dependent Polymorphism.

The i-motif structure (iM) has attracted much attention, because of its in vivo bioactivity and wide in vitro applications such as DNA-based switches. Herein, the length-dependent folding of cytosine-rich repeats of the human telomeric 5'-(CCCTAA)n-1CCC-3' (iM-n, where n = 2-8) was fully explored. We found that iM-4, iM-5, and iM-8 mainly form the intramolecular monomer iM structures, while a tetramolecular structure populates only for iM-3. However, iM-6 and iM-7 have the potential to fold as well into the dimeric iM structures besides the monomer ones. The natural hypericin (Hyp) was used as the polymorphism-selective probe to recognize the iM structures. Interestingly, only iM-3, iM-6, and iM-7 can efficiently switch on the Hyp fluorescence by specifically binding with the outmost C-C+ base pairs that are exposed directly to solution. However, other iM structures that fold in a way with a coverage of the outmost C-C+ pairs by loop sequences are totally unavailable for the Hyp binding. Theoretical modeling indicates that adaptive π-π and cation-π interactions contribute to the Hyp recognition toward the exposed C-C+ pairs. This specific iM recognition can be boosted by a photocatalytic DNAzyme construct. Our work provides a reliable fluorescence method to selectively explore the polymorphism of iM structures.

A theoretical insight into excited-state decay and proton transfer of p-nitrophenylphenol in the gas phase and methanol solution.

The excited-state decay (ESD) and proton transfer (EPT) of p-nitrophenylphenol (NO2-Bp-OH), especially in the triplet states, were not characterized with high-level theoretical methods to date. Herein, the MS-CASPT2//CASSCF and QM(MS-CASPT2//CASSCF)/MM methods were employed to gain an atomic-level understanding of the ESD and EPT of NO2-Bp-OH in the gas phase and its hydrogen-bonded complex in methanol. Our calculation results revealed that the S1 and S2 states of NO2-Bp-OH are of 1ππ* and 1nπ* characters at the Franck-Condon (FC) point, which correspond to the ICT-EPT and intramolecular charge-transfer (ICT) states in spectroscopic experiments. The former state has a charge-transfer property that could facilitate the EPT reaction, while the latter one might be unfavorable for EPT. The vertical excitation energies of these states are almost degenerate at the FC region and the electronic configurations of 1ππ* and 1nπ* will exchange from the S1 FC region to the S1 minimum, which means that the 1nπ* state will participate in ESD once NO2-Bp-OH departs from the S1 FC region. Besides, we found that three triplets lie below the first bright state and will play very important roles in intersystem crossing processes. In terms of several pivotal surface crossings and relevant linearly interpolated internal coordinate (LIIC) paths, three feasible but competing ESD channels that could effectively lead the system to the ground state or the lowest triplet state were put forward. Once arrived at the T1 state, the system has enough time and internal energy to undergo the EPT reaction. The methanol solvent has a certain effect on the relative energies and spin-orbit couplings, but does not qualitatively change the ESD processes of NO2-Bp-OH. By contrast, the solvent effects will remarkably stabilize the proton-transferred product by the hydrogen bond networks and assist to form the triplet anion. Our present work would pave the road to properly understand the mechanistic photochemistry of similar hydroxyaromatic compounds.

Generalized Ab Initio Nonadiabatic Dynamics Simulation Methods from Molecular to Extended Systems.

Nonadiabatic dynamics simulation has become a powerful tool to describe nonadiabatic effects involved in photophysical processes and photochemical reactions. In the past decade, our group has developed generalized trajectory-based ab initio surface-hopping (GTSH) dynamics simulation methods, which can be used to describe a series of nonadiabatic processes, such as internal conversion, intersystem crossing, excitation energy transfer and charge transfer of molecular systems, and photoinduced nonadiabatic carrier dynamics of extended systems with and without spin-orbit couplings. In this contribution, we will first give a brief introduction to our recently developed methods and related numerical implementations at different computational levels. Later, we will present some of our latest applications in realistic systems, which cover organic molecules, biological proteins, organometallic compounds, periodic organic and inorganic materials, etc. Final discussion is given to challenges and outlooks of ab initio nonadiabatic dynamics simulations.