The singlet molecular oxygen-oxidation of tryptophan generates diastereoisomeric dioxindolylalanine (diOia) along with hydroperoxides, alcohols and carbonyl compounds. Mechanistic investigations based on isotopic labeling and MS/MS analyses support diOia formation through a dioxetane intermediate.
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http://dx.doi.org/10.1039/c1pp05181d | DOI Listing |
ACS Cent Sci
January 2025
Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, California 92093, United States.
In quantum information science and sensing, electron spins are often purified into a specific polarization through an optical-spin interface, a process known as optically detected magnetic resonance (ODMR). Diamond-NV centers and transition metals are both excellent platforms for these so-called color centers, while metal-free molecular analogues are also gaining popularity for their extended polarization lifetimes, milder environmental impacts, and reduced costs. In our earlier attempt at designing such organic high-spin π-diradicals, we proposed to spin-polarize by shelving triplet = ±1 populations as singlets.
View Article and Find Full Text PDFPhotodiagnosis Photodyn Ther
January 2025
Maebashi-Institute of Technology, Systems Life Engineering, Gunma, 371-0816 Japan. Electronic address:
Introduction: The successful diagnosis and treatment of early-stage breast cancer enhances the quality of life of patients. As a promising alternative to recently developed magnetic resonance imaging-guided radiotherapy, we proposed fluorescence molecular imaging-guided photodynamic therapy (FMI-guided PDT), which requires no expensive equipment. In the FMI simulations, ICG-C11 which has emission peaks at near-infrared wavelengths was used as the FMI agent.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Department of Chemistry and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455-0431, United States.
The energy gaps, spin-orbit coupling (SOC), and admixture coefficients over a series of the configurations are evaluated by the SA-CASSCF/6-31G, SA-CASSCF/6-31G*, SA-CASSCF/ANO-RCC-VDZP, and MS-CASPT2/ANO-RCC-VDZP to reveal the extent of the inaccuracy of the SA-CASSCF. By comparing the mean absolute errors for the energy gaps and the admixture coefficient magnitudes (ACMs) measured between the SA-CASSCF/6-31G, SA-CASSCF/6-31G*, or SA-CASSCF/ANO-RCC-VDZP and the MS-CASPT2/ANO-RCC-VDZP, the SA-CASSCF/6-31G is selected as the electronic structure method in the nonadiabatic molecular dynamics simulation. The major components of the ACMs of the SA-CASSCF/6-31G and MS-CASPT2/ANO-RCC-VDZP are identified and compared; we find that the ACMs are underestimated by the SA-CASSCF/6-31G, which is verified by the reasonable triplet quantum yield simulated by the trajectory surface hopping and the calibrated SA-CASSCF/6-31G.
View Article and Find Full Text PDFMolecules
January 2025
Istituto di Biostrutture e Bioimmagini-CNR (IBB-CNR), Via De Amicis 95, I-80145 Napoli, Italy.
We perform DFT calculations with different hybrid (ωB97X-D and M05-2X) and double hybrid (B2PLYP-D3 and ωB2PLYP) functionals to characterize the lowest energy triplet excited states of naphthalene monomer and dimers in different stacking arrangements and to simulate their absorption spectra. We show that both excimer and localized triplet minima exist. In the former, the spin density is delocalized over the two monomers, adopting a face-to-face arrangement with a short inter-molecular distance.
View Article and Find Full Text PDFMolecules
January 2025
Enikolopov Institute of Synthetic Polymeric Materials, Russian Academy of Science, Profsoyuznaya 70, Moscow 117393, Russia.
Multiresonant fluorophores are a novel class of organic luminophores with a narrow emission spectrum. They can yield organic light-emitting devices, e.g.
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