Nuclear magnetic resonance (NMR) is a very powerful tool in physics, chemistry, and life sciences, although limited by low sensitivity. This problem can be overcome by hyperpolarization techniques dramatically enhancing the NMR signal. However, this approach is restricted to relatively short time scales depending on the nuclear spin-lattice relaxation time T(1) in the range of seconds. This makes long-lived singlet states very useful as a way to extend the hyperpolarization lifetimes. Para-hydrogen induced polarization (PHIP) is particularly suitable, because para-H(2) possesses singlet symmetry. Most PHIP experiments, however, are performed on asymmetric molecules, and the initial singlet state is directly converted to a NMR observable triplet state decaying with T(1), in the order of seconds. We demonstrate that in symmetric molecules, a long-lived singlet state created by PHIP can be stored for several minutes on protons in high magnetic fields. Subsequently, it is converted into observable high nonthermal magnetization by controlled singlet-triplet conversion via level anticrossing.
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http://dx.doi.org/10.1021/ja304285s | DOI Listing |
Photochem Photobiol
December 2024
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata (UNLP), CCT La Plata-CONICET, La Plata, Argentina.
Phototoxicity of skin due to the application of skincare products or fragrances is increasing from day to day, since a lot of natural extracts, with low or no toxicity in the dark, are being used in the skin exposed to solar radiation. In particular, the use of 4-hydroxy-3-methoxy benzaldehyde, known as vanillin, in the pharmaceutical, food, and cosmetic industries has increased in the last years. This compound is generally considered as safe for humans, and it has been used in a wide range of applications.
View Article and Find Full Text PDFThe development of efficient and long-lived halogen-free organic phosphorescent molecules remains a challenge. For the single-heteroatomic 9,10-dihydroacridine (AcH), the evolution of singlet and triplet excited state absorption signals reveals an intersystem crossing (ISC) lifetime of 8.2 ns and a triplet state lifetime of 0.
View Article and Find Full Text PDFChem Asian J
December 2024
Indian Institute of Science Education and Research Bhopal, Department of Chemistry, Bhopal by-pass road, Bhauri, 462066, Bhopal, INDIA.
Organic thermally activated delayed fluorescence (TADF) materials, known for their long-lived emission properties, are highly sought after for background-free imaging of selective analytes in time-resolved modes. However, their practical application faces significant challenges, including the air sensitivity of triplet states, lack of organelle specificity, and the absence of precise analyte recognition centres. These limitations hinder their effectiveness in detecting key cancer biomarkers such as nitroreductase (NTR).
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Biology and Chemistry, Osnabrück University, Barbarastraße 7, Osnabrück 49076, Germany.
Light energy conversion often relies on photosensitizers with long-lived excited states, which are mostly made of precious metals such as ruthenium or iridium. Photoactive complexes based on highly abundant iron seem attractive for sustainable energy conversion, but this remains very challenging due to the short excited state lifetimes of the current iron complexes. This study shows that a luminescent Fe(III) complex sensitizes triplet-triplet annihilation upconversion with anthracene derivatives via underexplored doublet-triplet energy transfer, which is assisted by preassociation between the photosensitizer and the annihilator.
View Article and Find Full Text PDFJ Chem Phys
December 2024
Novosibirsk State University, Novosibirsk 630090, Russia.
Determining the stability constant of the complex formed by an organic ligand with a protein is the first stage in the screening of new drugs. Nuclear spin long-lived states, in particular the singlet state, can be used to study the reversible binding of ligands to proteins. In a complex with a protein, the spins of the ligand interact with the spins of the protein, the system of protein and ligand nuclei can relax by a dipole-dipole mechanism, and the lifetime of the singlet state is strongly reduced.
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