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      Ultrafast intersystem crossing in nickel porphyrins

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          Abstract

          We study the relaxation dynamics and intersystem-crossing to the metastable state in laser-pumped tetra and hexa-coordinated nickel porphyrins. We use a ligand-field model which takes into account the crystal field created by the porphyrin ring and axial ligands. By accounting for the energy redistribution of the lattice vibrations of the metal-ligand stretch mode we get an irreversible decay within the order of the hundreds of femtoseconds timescale. We show how non-equilibrium time-dependent x-ray absorption atthe Ni K-edge measurements can elucidate the nature of the intermediate states involved in the decay. Understanding radiationless transitions in this system is of interest for their relevance in photocatalytic systems and photothermal sensitizers for cancer treatment.

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          Photothermal sensitisation as a novel therapeutic approach for tumours: studies at the cellular and animal level.

          Irradiation of B78H1 murine amelanotic melanoma cells with 850 nm light emitted from a Ti:sapphire laser, operated in a pulsed mode at high fluence rates and in the presence of Ni(II)-octabutoxy-naphthalocyanine (NiNc), promoted a photothermally sensitised process leading to fast and irreversible cell death. This resulted in the ejection of a consistent mass of cytoplasmic material from the irradiated cells that was detected by scanning electron microscopy. The extensive chemical and mechanical damage was probably caused by the photoinduced generation of an acoustic shock wave. The efficiency of the photoprocess was modulated by intracellular concentration of NiNc and maximally by the formation of aggregated naphthalocyanine clusters in specific subcellular areas. Very similar results were obtained upon irradiation of NiNc-loaded C32 human amelanotic melanoma cells and transformed murine HT-1080 and HaCaT fibroblasts. From these results, photothermal sensitisation appears to be a general phenomenon and preliminary studies with mice bearing subcutaneously transplanted amelanotic melanomas, irradiated with 850 nm light 24 h after intravenous injection of NiNc, suggest that this approach has potential for the therapy of some types of skin tumours.
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            Ultrafast X-ray spectroscopy as a probe of nonequilibrium dynamics in ruthenium complexes

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              Determination of the energy of the (d,d) electronic state involved in the radiationless deactivation of photoexcited nickel tetraphenylporphine

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                Author and article information

                Journal
                2015-10-29
                Article
                1510.08668
                2643a917-3e97-4285-bc1b-9758aaad465e

                http://arxiv.org/licenses/nonexclusive-distrib/1.0/

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                Custom metadata
                cond-mat.str-el cond-mat.mtrl-sci

                Condensed matter
                Condensed matter

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