The ultrafast primary charge separation in Photosystem I (PS I) excited by femtosecond pulses centered at 720 and 760nm was studied by pump-to-probe laser spectroscopy. The absorbance in the red edge of PS I absorption spectrum has an unusual exponential dependence on wavelength. The cutoff of short wavelength components of 760nm pulse allows direct excitation of reaction center chlorophyll molecules without involvement of light-harvesting antenna. The transient spectrum manifests the features of the primary ion-radical pair PA at time delay <180fs, followed by formation of the secondary pair PA with a characteristic time of 26ps. The obtained data are rationalized in the framework of adiabatic three-state model that includes the chlorophyll dimer P and two symmetrically arranged nearest chlorophyll molecules of A. The arrangement of chlorophylls results in strong electronic coupling between P and A. Excitation in the maximum of P absorption generates electronic states with the highest contribution from P*, whereas excitation in the far-red edge predominantly generates charge transfer state PA in both branches of redox-cofactors. The three-level model accounts for a flat-bottomed potential surface of the excited state and adiabatic character of electron transfer between P and A, providing a microscopic explanation of the ultrafast formation of PA and exponential decline of PS I absorption.

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In the present work, we provide evidence for visible light irradiation of the Au/TiO2 nanoparticles’ surface plasmon resonance band (SPR) leading to electron injection from the Au nanoparticles to the conduction band of TiO2. The Au/TiO2 SPR band is shown to greatly enhance the light absorption of TiO2 in the visible region. Evidence is presented for the light absorption by the Au/TiO2 plasmon bands leading to the dissolution of Au nanoparticles. This dissolution occurs concomitantly with the injection of the hot electrons generated by the Au plasmon into the conduction band of TiO2. The electron injection from the Au nanoparticles into TiO2 was followed by femtosecond spectroscopy. The formation of Au ions was further confirmed by the spectral shift of the transient absorption spectra of Au/TiO2. The spectral changes of the SPR band of Au/TiO2 nanoparticles induced by visible light were detected by spectrophotometer, and the morphological transformation of Au/TiO2 was revealed by electron microscopy techniques as well. Subsequently, the fate of the Au ions was sorted out during the growth and biofilm formation for some selected Gram-negative bacteria. This study compares the bactericidal mechanism of Au ions and Ag ions, which were found to be substantially different depending on the selected cell used as a probe.

Age-related macular degeneration (AMD) is the primary cause of central blindness among the elderly. AMD is associated with progressive accumulation of lipofuscin granules in retinal pigment epithelium (RPE) cells. Lipofuscin contains bisretinoid fluorophores, which are photosensitizers and are phototoxic to RPE and neuroretinal cells. In the presence of oxygen, bisretinoids are also oxidized, forming various products, consisting primarily of aldehydes and ketones, which are also potentially cytotoxic. In a prior study, we identified that in AMD, bisretinoid oxidation products are increased in RPE lipofuscin granules. The purpose of the present study was to determine if these products were toxic to cellular structures. The physicochemical characteristics of bisretinoid oxidation products in lipofuscin, which were obtained from healthy donor eyes, were studied. Raman spectroscopy and time-of-flight secondary ion mass spectrometry (ToF–SIMS) analysis identified the presence of free-state aldehydes and ketones within the lipofuscin granules. Together, fluorescence spectroscopy, high-performance liquid chromatography, and mass spectrometry revealed that bisretinoid oxidation products have both hydrophilic and amphiphilic properties, allowing their diffusion through lipofuscin granule membrane into the RPE cell cytoplasm. These products contain cytotoxic carbonyls, which can modify cellular proteins and lipids. Therefore, bisretinoid oxidation products are a likely aggravating factor in the pathogenesis of AMD.