Article
Chemistry, Multidisciplinary
J. Patrick Zobel, Anna M. Wernbacher, Leticia Gonzalez
Summary: The mechanism of reverse intersystem crossing (rISC) in metal-based TADF emitters is still not clear, as the small singlet/triplet energy gaps necessary for thermal rISC in donor-acceptor systems with charge-transfer excited states have spin-orbit couplings that are too small for effective rISC. In this study, the first nonadiabatic dynamics simulation of rISC process in a carbene-copper(I)-carbazolyl TADF emitter is reported. Efficient rISC on a picosecond time scale is demonstrated, involving an intermediate higher-lying triplet state of metal-to-ligand charge transfer character ((MLCT)-M-3) that enables large spin-orbit couplings with the lowest singlet charge transfer state. The mechanism is completed in the S-1 state where the complex can return to a co-planar coordination geometry with high fluorescence efficiency.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Spectroscopy
Anna Szemik-Hojniak, Irena Deperasinska, Yuval Erez, Monika Gawlowska, L. Jerzykiewicz
Summary: In this study, the 2E6M molecule belonging to the Proton Coupled Electron Transfer (PCET) compounds was investigated. It was found that this compound undergoes both charge transfer and proton transfer processes in excited states. The study revealed the nature of these processes in different solvents and observed changes in the dipole moment and fluorescence characteristics of the molecule.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2023)
Article
Chemistry, Physical
Xue-Ping Chang, Feng-Ran Fan, Teng-Shuo Zhang, Bin-Bin Xie
Summary: The excited state properties and deactivation pathways of two DNA methylation inhibitors in aqueous solution are comprehensively explored using the QM(CASPT2//CASSCF)/MM protocol. The study provides insights into the photophysics and photochemistry of these compounds.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Zichun Zhou, Xue Tang, Yanhong Cui, Shuai Xue, Zihua Yu, Yujin Li
Summary: The research introduced a series of pyridinyl coumarincarboxymides derivatives that exhibited high fluorescence quantum yield and intense blue fluorescence. Through spectral measurement and analysis, it was identified that these compounds displayed their fluorescence properties in nonpolar solvents.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Biochemistry & Molecular Biology
Ziwei Chen, Xueli Wang, Menghui Jia, Xiaoxiao He, Haifeng Pan, Jinquan Chen
Summary: In this study, the excited-state dynamics of 5-azacytidine and 2'-deoxy-5-azacytidine were investigated using femtosecond transient absorption and quantum-chemical calculations, while also revisiting the properties of 5-AC. It was found that glycosyl substitution led to ultrafast excited-state relaxation in both nucleosides, which was different from the longer lifetime observed in 5-AC.
PHOTOCHEMISTRY AND PHOTOBIOLOGY
(2022)
Review
Chemistry, Multidisciplinary
Meng-Chi Chen, Deng-Gao Chen, Pi-Tai Chou
Summary: The nitro group has unique characteristics in photochemical research, such as strong electron-withdrawing ability and facile conversion to reduced substituents, making it a popular feature in various molecules. Recent studies have shown fluorescent chromophores containing the nitro group, with 3-nitrophenothiazine having a 100% emission quantum yield in nonpolar solvents. The advancement of fluorescent nitro chromophores in intramolecular charge transfer, fluorescent probes, and nonlinear properties has been systematically reviewed, with a focus on the rationalization of emission spectroscopy for insights into the structure-photophysics relationship.
Article
Biochemistry & Molecular Biology
Rem Jalab, Mohammed A. Saad, Mostafa H. Sliem, Aboubakr M. Abdullah, Ibnelwaleed A. Hussein
Summary: This study investigates the corrosion inhibition performance of an environment-friendly surfactant Quaternium-22 (Q-22) on C-steel in a 5M HCl medium. The results reveal that adding Q-22 significantly decreases the corrosion rate of C-steel, with physisorption onto the surface.
Article
Optics
Zhedong Zhang, Tao Peng, Xiaoyu Nie, Girish S. Agarwal, Marlan O. Scully
Summary: This study investigates the new capabilities provided by entangled photons in coherent Raman spectroscopy and develops an ultrafast frequency-resolved Raman spectroscopy using entangled photons. By utilizing quantum correlation between photons, this technique exhibits both temporal and spectral resolutions. The study also reveals a microscopic theory for electronic coherence dynamics.
LIGHT-SCIENCE & APPLICATIONS
(2022)
Article
Chemistry, Analytical
Nyssa T. Emerson, Haw Yang
Summary: The study investigates the impact of plasmonic nanoparticles on nearby optical probes and presents methods for detecting and quantifying this effect. By optimizing sample concentration, light paths, and excitation-detection volume, fluorescence intensity can be maximized, while tools of DNA nanotechnology are utilized for quantitative measurements of enhancement.
ANALYTICAL CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Mahbobeh Morshedi, Oliver Nolden, Philipp Janke, Wiebke Haselbach, Michael Schmitt, Peter Gilch
Summary: The photophysics of 2-cyanoindole in different solvents was investigated using fluorescence and absorption spectroscopy. The fluorescence quantum yield of 2-cyanoindole is strongly influenced by the solvent, and the fluorescence decay behavior varies in different solvents.
PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES
(2023)
Article
Nanoscience & Nanotechnology
Toyoko Imae, Astrid Rahmawati, Andergachew Mekonnen Berhe, Mekuriaw Assefa Kebede
Summary: Gold quantum clusters and plasmonic quantum nanoparticles were synthesized using femtosecond laser irradiation. The method produced gold clusters and nanoparticles with quantum and plasmonic properties, different from the chemical reduction method. The incorporation of a metal-organic framework as a holder resulted in gold-encapsulated ZIF-8 material with enhanced fluorescence and catalytic performance.
ACS APPLIED NANO MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Hao-Jung Chang, Mykhailo Bondar, Natalia Munera, Sylvain David, Olivier Maury, Gerard Berginc, Boris Le Guennic, Denis Jacquemin, Chantal Andraud, David J. Hagan, Eric W. Van Stryland
Summary: This study investigated the fast relaxation processes in the excited electronic states of functionalized aza-boron-dipyrromethene (aza-BODIPY) derivatives, including their linear photophysical, photochemical, and nonlinear optical properties. It was found that nonfluorescent derivatives exhibited optical gain in the near infrared range under femtosecond excitation. The study also discussed the role of bromine substituents in the molecular structures of these derivatives, and the excited states involved in electronic transitions were investigated using quantum-chemical TD-DFT calculations. The high two-photon absorption and excited-state absorption cross-sections, along with the measured photostability, suggest potential applications in photonics and optical limiting.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Dong Li, Xiaoxiao He, Litao Zhao, Haoyang Li, Xiaolei Zhang, Jinquan Chen, Qingyuan Jin, Jianhua Xu
Summary: Graphene and its derivatives can be assembled with organic dyes to create composite materials for photovoltaic and photocatalytic assemblies. The quenching mechanisms of fluorescence in RdB-GO and RdB-RGO were investigated, revealing that the electron transfer process was more effective in RdB-RGO due to a change in energy levels caused by GO reduction. This suggests that RdB-RGO composite materials may have higher application values for dye-sensitized solar cells.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Materials Science, Multidisciplinary
David Hall, Pachaiyappan Rajamalli, Eimantas Duda, Subeesh Madayanad Suresh, Francesco Rodella, Sergey Bagnich, Cameron L. Carpenter-Warren, David B. Cordes, Alexandra M. Z. Slawin, Peter Strohriegl, David Beljonne, Anna Koehler, Yoann Olivier, Eli Zysman-Colman
Summary: In this study, a new acceptor for TADF emitters, pyridylbenzimidazole, is introduced, which, when combined with phenoxazine, facilitates efficient TADF. N-functionalization of benzimidazole allows for color tuning and suppression of ACQ, with minimal impact on TADF efficiency. The modified derivatives exhibit higher photoluminescence quantum yields at higher doping levels, compared to the parent compound undergoing ACQ at higher doping concentrations.
ADVANCED OPTICAL MATERIALS
(2021)
Article
Environmental Sciences
Jia Gu, Wei Zhang, Jun Ma, Zongli Huo, Yang Song
Summary: In this study, the UV-induced transformation of monochloro-p-benzoquinone (MCBQ) in aqueous solution was systematically investigated through quantum chemical calculations. It was found that the nucleophilic attack of OH- on carbon atoms was the central reaction, and the addition to olefinic carbon atoms was more feasible. Moreover, OH- preferred to add to the ortho-position of C-Cl bond.
Article
Chemistry, Physical
Evangelos Balanikas, Thomas Gustavsson, Dimitra Markovitsi
Summary: This paper investigates the fluorescence characteristics of guanine quadruplexes (G4) formed by the association of two DNA strands in the presence of K+ cations. The maximum fluorescence spectrum is located at 334 nm with a quantum yield of 5.8 x 10-4. Ultrafast excitation transfer is found to be more efficient in this specific G4 structure due to the arrangement of peripheral thymines and their interaction with guanines. Additionally, a weak intensity excimer/exciplex emission band at 445 nm was observed, along with a long-lived fluorescence component at the blue side of the spectrum, which is uncommon for G4 structures.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Article
Electrochemistry
Mattia Belotti, Mohsen M. T. El-Tahawy, Nadim Darwish, Marco Garavelli, Simone Ciampi
Summary: This study explores the current response, light intensity, and spectral signatures of the cathodic electrochemiluminescence (ECL) in room temperature ionic liquids (RTILs). It demonstrates the viability of using electrode reactions to generate light emitters in RTILs and discovers that the ECL signal can persist for a certain duration after the removal of the external cathodic pulse due to the stabilization of superoxide.
Article
Chemistry, Medicinal
Haritha Asha, James A. Green, Luciana Esposito, Fabrizio Santoro, Roberto Improta
Summary: This study uses the FrDEx model to simulate the ECD spectra of guanine-rich DNA sequences in quadruple helices with different topologies. The parameters of the FrDEx Hamiltonian are obtained from TD-DFT calculations with the M052X functional. The FrDEx spectra are in good agreement with the TD-DFT ones and show improvement compared to a standard excitonic Hamiltonian. The inclusion of the inner K+ cation in the calculation affects the ECD spectra.
Article
Chemistry, Physical
Francesco Segatta, Daniel Aranda Ruiz, Flavia Aleotti, Martha Yaghoubi, Shaul Mukamel, Marco Garavelli, Fabrizio Santoro, Artur Nenov
Summary: This paper presents an accurate and efficient approach for calculating the linear and nonlinear optical spectroscopy of a closed quantum system. The method includes the effect of ultrafast nonadiabatic dynamics by numerically propagating the nuclear wave packet. The expressions for the evaluation of response functions are recast in a general form and validated using the multiconfiguration time-dependent Hartree method. The application to pyrene reveals the remarkable influence of ultrafast nonadiabatic dynamics on spectral line shapes.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Thomas Gustavsson, Dimitra Markovitsi
Summary: Several studies have found that a significant part of DNA duplexes' intrinsic fluorescence decays with surprisingly long lifetimes at shorter wavelengths. This high-energy nanosecond emission (HENE) is hardly detectable in the fluorescence spectra of most duplexes, but it contrasts with the expected low-energy excimers/exciplexes. The excited states responsible for HENE remain unknown, and this Perspective provides a critical summary of experimental observations and theoretical approaches to foster future studies.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Abed Mohamadzade, Artur Nenov, Marco Garavelli, Irene Conti, Susanne Ullrich
Summary: Sulfur-substituted nucleobases are efficient in photoinduced intersystem crossing (ISC), making them versatile for various applications. However, a comprehensive understanding of wavelength-dependent changes in IC and ISC events is still lacking.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Qiushuang Xu, Yanli Liu, Meishan Wang, Javier Cerezo, Roberto Improta, Fabrizio Santoro
Summary: In this study, the vibrational Resonance Raman (vRR) spectra of cytosine in water were computationally investigated using potential energy surfaces (PES) calculated by time-dependent density functional theory (TD-DFT) and CAM-B3LYP and PBE0 functionals. The close-lying and coupled electronic states of cytosine posed a challenge for the commonly used approach to compute vRR spectra. Two recently developed time-dependent approaches, based on either quantum dynamical numerical propagations or analytical correlation functions, were adopted to compute the vRR spectra. The inclusion of specific solute-solvent interactions remarkably improved the agreement with experiments by altering the composition of the normal modes.
Article
Pharmacology & Pharmacy
Meryem El Ouardi, Lorena Tamarit, Ignacio Vaya, Miguel A. Miranda, Inmaculada Andreu
Summary: This study investigated the photosensitivity and mechanisms of gefitinib metabolites. It was found that only 4-Defluoro-4-hydroxy gefitinib (DF-GFT) did not display phototoxicity, while O-Demethyl gefitinib (DMT-GFT) and O-Demorpholinopropyl gefitinib (DMOR-GFT) showed varying degrees of photosensitivity. Additionally, DMOR-GFT induced lipid photoperoxidation, while DMT-GFT had minimal effects on protein oxidation. Interestingly, DMT-GFT caused the most severe damage to cellular DNA, which was insufficiently repaired after an 18-hour recovery period. These findings can guide oncologists in prescribing TKIs and establishing photoprotection guidelines for cancer patients.
FRONTIERS IN PHARMACOLOGY
(2023)
Article
Engineering, Environmental
Maria Cabrero-Antonino, Arianna Melillo, Eva Montero-Lanzuela, Mercedes Alvaro, Belen Ferrer, Ignacio Vaya, Herme G. Baldovi, Sergio Navalon
Summary: In this study, multi-metallic UiO-66(Zr/Ce/Ti) solids-supported RuOx nanoparticles were developed as photocatalysts for selective gas phase CO2 methanation. The trimetallic UiO-66(Zr/Ce/Ti) photocatalyst showed higher activity than mono- or bimetallic derivatives and previous reports on metal-organic frameworks (MOFs). Spectroscopic techniques were used to obtain experimental evidence and insights into the photocatalytic activity and mechanism. This research highlights the advantages of using multimetallic MOF-supported metal nanoparticles for solar-driven CO2 conversion.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Biochemistry & Molecular Biology
Roberto Improta
Summary: I-motifs are non-canonical DNA structures composed of intercalated hemiprotonated (CH.C)+ pairs. This study characterizes the photoactivated behavior of the (CH.C)+ core of I-motifs using time-dependent DFT calculations, providing a comprehensive understanding of their absorption, emission, and possible photochemical reactions. The results reproduced and assigned the spectral signatures of I-motifs, including infrared, absorption, fluorescence, and circular dichroism spectra, and proposed potential photoproducts through a photodimerization reaction with strong C?CH+ charge transfer character.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Physical
Juliana Cuellar-Zuquin, Ana Julieta Pepino, Ignacio Fdez Galvan, Ivan Rivalta, Francesco Aquilante, Marco Garavelli, Roland Lindh, Javier Segarra-Marti
Summary: We characterized the photochemically relevant conical intersections between different DNA/RNA nucleobases using CASSCF algorithms. Our results show that the size of the active space significantly affects the conical intersection topographies, while the basis set size seems to have a minor effect. We ruled out structural changes as a key factor and highlighted the importance of accurately describing the electronic states involved in these intersections.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Vasilis Petropoulos, Lorenzo Uboldi, Margherita Maiuri, Giulio Cerullo, Lara Martinez-Fernandez, Evangelos Balanikas, Dimitra Markovitsi
Summary: The polarity of DNA has been found to have an impact on the relaxation of DNA electronic excited states, with different nucleotide sequences leading to different optical properties.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Lorena Tamarit, Laura Garcia-Gabarda, M. Consuelo Jimenez, Miguel A. Miranda, Ignacio Vaya
Summary: The interaction dynamics between Flurbiprofen (FBP) and tryptophan (Trp) were studied using fluorescence and ultrafast transient absorption spectroscopy. It was found that covalently linked dyads and human serum albumin (HSA) can serve as excellent models to investigate photoinduced processes in proteins. The results obtained may provide insights into the mechanistic pathways involved in photobiological damage.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Henar Mateo-delaFuente, Davide Avagliano, Marco Garavelli, Juan J. Nogueira
Summary: The absorption and emission spectra of luciferine/luciferase were calculated using molecular dynamics simulations, hybrid quantum mechanics/molecular mechanics calculations, and transition density analysis. The presence of the enzyme hampers the torsional motion of the chromophore, reducing the intramolecular charge transfer nature of the absorbing and emitting state. However, a polar environment around the oxygen atom enhances the charge transfer character of the emitting state.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)