Is 1-methylcytosine a faithful model compound for ultrafast deactivation dynamics of cytosine nucleosides in solution?

1-Methylcytosine (1mCyt) is the base for nucleoside N1-methylpseudodeoxycytidine of Hachimoji nucleic acids and a frequently used model compound for theoretical studies on excited states of cytosine nucleosides. However, there is little experimental characterization of spectra and photo-dynamic properties of 1mCyt. Herein, we report a comprehensive investigation into excited state dynamics and effects of solvents on fluorescence dynamics of 1mCyt in both water and acetonitrile. The study employed femtosecond broadband time-resolved fluorescence, transient absorption, and steady-state spectroscopy, along with density functional theory and time-dependent density functional theory calculations. The results obtained provide the first experimental evidence for identifying a dark-natured ∼5.7 ps lifetime nπ* state in the ultrafast non-radiative deactivation with 1mCyt in aqueous solution. This study also demonstrates a significant effect of the solvent on 1mCyt's fluorescence emission, which highlights the crucial role of solute-solvent hydrogen bonding in altering structures and reshaping the radiative as well as nonradiative dynamics of the 1mCyt's ππ* state in the aprotic solvent compared to the protic solvent. The solvent effect exhibited by 1mCyt is distinctive from that known for deoxycytidine, indicating the need for caution in using 1mCyt for modelling the ultrafast dynamics of Cyt nucleosides in solvents with varying properties. Overall, our study unveils a deactivation mechanism that confers a high degree of photo-stability for 1mCyt in solution, shedding light on the molecular basis for solvent-induced effects on the excited state dynamics of nucleobases and derivatives.

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. The results of our study provide the first direct evidence for a highly efficient nonradiative mechanism achieved through internal conversion from the ππ* state of the isocytosine keto-N(3)H form occurring within subpicoseconds and picoseconds following photo-excitation. Our study also unveils a crucial role of solvent, particularly solute-solvent hydrogen bonding, in determining the tautomeric composition and regulating the pathways and dynamics of the deactivation processes. The deactivation processes of isocytosine in the solvents examined are found to be distinct from those of cytosine and the case known for isocytosine in the gas phase mainly due to different tautomeric forms involved. Overall, our findings demonstrate the high photo-stability of isocytosine in the solution and showcase the remarkable effect of covalent modification in altering the spectral character and excited state dynamics of nucleobases.

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. The result revealed a multichannel decay containing an unusual high-energy excimer featuring charge transfer deactivated by rapid proton transfer in the tetrad core region. It also identified an unprecedented exciplex displaying massively red-shifted fluorescence produced from charge transfer in the loop region. The findings underscore the role of structural conformation and base content in determining the energy, electronic attribution, and decay dynamics of GQ excited states.

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. The result obtained from comparison of conformers with protonation at different sites revealed that the syn-conformer with protonation occurring at the N3 position (syn-N3) is the predominant form of AdoH+ in the ground state, similar to that of Ado. In contrast, the fluorescence of AdoH+ with maximum intensity at 385 nm, significantly red-shifted from that of Ado, displaying decay dynamics composed of an ultrafast component with the lifetime of ∼0.5 ps and a slower one of ∼2.9 ns. The former is because of the decay of the syn-N3 conformer, similar to that reported for AdoH+ under the gas phase condition. The latter is due to the syn-N1 conformer formed via ultrafast proton transfer of the syn-N3. The excited state of syn-N1 has a peculiar nonplanar conformation over the purine molecule, which is responsible for the substantial Stokes shift showed in the fluorescence spectrum and correlates with a large energy barrier for nonradiative decay likely involving a reversed proton transfer. This study demonstrates the importance of protonation and solvent environment in altering dramatically the excited states of Ado, providing insight for better understanding nonradiative dynamics of both the monomeric bases and the oligomeric or polymeric DNAs.

Breaking the 1,2-HOPO barrier with a cyclen backbone for more efficient sensitization of Eu(iii) luminescence and unprecedented two-photon excitation properties.

A cyclen backbone was utilized to study the effect of backbone rigidity on Eu(iii) luminescence sensitization using a 1,2-HOPO derivative and 2-thenoyltrifluoroacetonate (TTA) as chromophores. The restriction of molecular movement of Eu-Cy-HOPO brought about by the increased rigidity provided a tightly packed coordination environment for the octadentate Eu(iii) center which resulted in the highest overall quantum yield (30.2%) and sensitization efficiency (64.6%) among 1,2-HOPO sensitized Eu(iii) complexes. Eu-Cy-HOPO is also the first 1,2-HOPO-based lanthanide complex to emit Eu(iii) luminescence under two-photon excitation.

Zero-Dimensional Carbon Allotropes-Carbon Nanoparticles Versus Fullerenes in Functionalization by Electronic Polymers for Different Optical and Redox Properties.

Fullerene cages are known as being able to participate in radical initiated copolymerization reactions with vinyl monomers for polymer-functionalized fullerenes. In this work, poly(N-vinylcarbazole) (PVK) was selected as a representative of electronic polymers in the functionalization of fullerene C60 by the same copolymerization reaction to yield the PVK-C60. Similarly found was that small carbon nanoparticles could also participate in the same copolymerization reaction for the nanoparticles to be surface-functionalized and -passivated by the attached PVK polymers, which are structurally adhering to the general definition on carbon dots (CDots), thus PVK-CDots. In the comparison between PVK-CDots and PVK-C60, the former was found to be more absorptive and therefore more effective in photon harvesting across the visible spectral region and also brightly fluorescent, orders of magnitude more so than the latter. Similar to the PVK-C60 and C60 cages in general, the PVK-CDots exhibited significant photoinduced electron accepting characteristics and, at the same time, also extraordinary electron donating abilities that are not available to fullerenes. Because fullerene-based composites with electronic polymers including PVK have found significant applications in optoelectronic devices and systems, the prospect of CDots represented by the PVK-CDots for similar purposes is discussed.

Photoexcited State Properties of Carbon Dots from Thermally Induced Functionalization of Carbon Nanoparticles.

Carbon dots are small carbon nanoparticles with various surface passivation schemes, in which more effective has been the deliberate chemical functionalization of the nanoparticles for brighter fluorescence emissions, though the synthesis method is more tedious and subject to some limitations in the selection of functionalization molecules. Another more popular synthesis method has been the carbonization of organic species, with the method being more efficient and versatile, but less controllable in the synthesis and for the desired dot structure and performance. In this work, a hybrid approach combining the advantageous characteristics of the two synthesis methods was applied to the preparation of carbon dots with polyethyleneimine (PEI) for surface passivation, where pre-processed and selected small carbon nanoparticles were functionalized with PEI in microwave-induced thermal reactions. The optical absorption and fluorescence emission properties were evaluated, and the results suggested that the carbon dots thus prepared shared the same photoexcited state characteristics with those from the deliberate chemical functionalization, including comparable fluorescence colors and other properties. A further demonstration on the similarity in photoexcited state properties was based on the same visible light-activated bactericidal functions of the PEI-carbon dots as those found in carbon dots from the deliberate chemical functionalization. The advantages and potential limitations of the hybrid approach for more controllable yet versatile and efficient syntheses of carbon dots are highlighted and discussed.