Ultrafast excited state dynamics of isocytosine unveiled by femtosecond broadband time-resolved spectroscopy combined with density functional theoretical study.

Isocytosine, having important applications in antivirus and drug development, is among the building blocks of Hachimoji nucleic acids. In this report, we present an investigation of the excited state dynamics of isocytosine in both protic and aprotic solvents, which was conducted by a combination of methods including steady-state spectroscopy, femtosecond broadband time-resolved fluorescence, and transient absorption. These methods were coupled with density functional and time-dependent density functional theory calculations.

Excited-State Charge Transfer, Proton Transfer, and Exciplex Formation Revealed by Ultrafast Time-Resolved Spectroscopy in Human Telomeric Ribonucleic Acid Quadruplex.

Guanine quadruplexes (GQs), important for genome stability and biotechnology application, can form from both DNA and RNA. However, unlike the study of DNA GQs, little research has been conducted on excited states of GQs from RNA, which due to the ribose 2'-hydroxy group have structures distinct from their DNA counterparts. Combining ultrafast broadband time-resolved fluorescence and transient absorption measurements, we report the first direct probe of excitation dynamics for a bimolecular GQ from human telomeric repeat-containing RNA taking the typical highly compacted parallel folding with a propeller-like loop structure.

Dual Time-Scale Proton Transfer and High-Energy, Long-Lived Excitons Unveiled by Broadband Ultrafast Time-Resolved Fluorescence in Adenine-Uracil RNA Duplexes.

In contrast to the immense amount of research on electronically excited DNA, surprisingly little has been done about the excited states of RNA. Herein, we demonstrate an ultrafast broadband time-resolved fluorescence and fluorescence anisotropy study to probe directly the intrinsic fluorescence and overall dynamics of the fluorescence from a homopolymeric adenine·uracil RNA duplex adopting the A-form structure. The results unveiled complex deactivation through distinctive multichannels mediated by states of varied energy, a character of charge transfer, and a lifetime from sub-picosecond to nanoseconds.

Long living excited state of protonated adenosine unveiled by ultrafast fluorescence spectroscopy and density functional theoretical study.

Adenosine (Ado) possesses ultrafast nonradiative dynamics accounting for its remarkably high photostability. The deactivation dynamics of Ado after protonation in an aqueous solution remains an elusive issue. Herein we report an investigation of the excited state dynamics of protonated Ado (AdoH) performed using ultrafast time-resolved fluorescence spectroscopy combined with density functional theoretical calculation.

A long lasting sunscreen controversy of 4-aminobenzoic acid and 4-dimethylaminobenzaldehyde derivatives resolved by ultrafast spectroscopy combined with density functional theoretical study.

4-Aminobenzoic acid (PABA) is one of the earliest patented and most commonly used sunscreen components. There is however a long-lasting controversy on its photo-protective efficacy owing to the lack of information on its protolytic equilibrium and photo-dynamics after absorption of ultraviolet radiation in physiologically relevant aqueous solution. The excitation dynamics in water also remains largely unknown for analogs of PABA such as 4-dimethylaminoacetophenone (DMAAP) and 4-dimethylaminobenzaldehyde (DMABA) which are recognized as prototypes for photo-induced twisted intramolecular charge transfer (TICT).

Fluorescence and Ultrafast Fluorescence Unveil the Formation, Folding Molecularity, and Excitation Dynamics of Homo-Oligomeric and Human Telomeric i-Motifs at Acidic and Neutral pH.

i-Motifs are tetraplex DNAs known to be stable at acidic pH. The structure of i-motifs is important in DNA nanotechnology; i-motif-forming sequences with consecutive cytosine (C) molecules are abundant throughout the human genome. There is, however, little information on the structure of C-rich DNAs under physiologically relevant neutral conditions.

Photoprotection or photodamage: a direct observation of nonradiative dynamics from 2-ethylhexyl 4-dimethylaminobenzoate sunscreen agent.

Apart from being an analogue of the prototype for photoinduced intramolecular charge transfer (ICT), 2-ethylhexyl 4-dimethylaminobenzoate (EHDMABA) is also one of the earliest patented and most commonly used sunscreen components. There is, however, little documented information about the photophysics and factors affecting the photophysics of this molecule. Such information is of importance for both the understanding of the ICT reaction and assessing the underlying process of photoprotection, especially in view of the "sunscreen controversy" that has arisen from the contrasting in vivo vs.

Nonradiative dynamics determined by charge transfer induced hydrogen bonding: a combined femtosecond time-resolved fluorescence and density functional theoretical study of methyl dimethylaminobenzoate in water.

As a case study of the interplay and the consequence of the interplay between intramolecular charge transfer (ICT) and intermolecular hydrogen (H)-bonding, a combined femtosecond time-resolved fluorescence (fs-TRF) and density functional theoretical (DFT) and time-dependent DFT (TDDFT) study has been conducted on methyl dimethylaminobenzoate (MDMABA) largely in a water solvent. Direct observation of the broadband spectra, anisotropy, and kinetic decays of fs-TRF from photo-excited MDMABA revealed a rapid ICT reaction occurring with a time constant of ∼0.7 ps from an initial locally excited (LE) state identified to have the Lππ* character; this produced a weakly emissive ICT state featuring radiative rate constant decreased by more than two orders of magnitude.