To determine the fluorescence properties of cyanobacterial Photosystem I (PS I) in relatively intact systems, fluorescence emission from 20 to 295 K and polarization at 77 K have been measured from phycobilisomes-less thylakoids of Synechocystis sp. PCC 6803 and a mutant strain lacking Photosystem II (PS II). At 295 K, the fluorescence maxima are 686 nm in the wild type from PS I and PS II and at 688 nm from PS I in the mutant. This emission is characteristic of bulk antenna chlorophylls (Chls). The 690-nm fluorescence component of PS I is temperature independent. For wild-type and mutant, 725-nm fluorescence increases by a factor of at least 40 from 295 to 20 K. We model this temperature dependence assuming a small number of Chls within PS I, emitting at 725 nm, with an energy level below that of the reaction center, P700. Their excitation transfer rate to P700 decreases with decreasing temperature increasing the yield of 725-nm fluorescence.Fluorescence excitation spectra of polarized emission from low-energy Chls were measured at 77 and 295 K on the mutant lacking PS II. At excitation wavelengths longer than 715 nm, 760-nm emission is highly polarized indicating either direct excitation of the emitting Chls with no participation in excitation transfer or total alignment of the chromophores. Fluorescence at 760 nm is unpolarized for excitation wavelengths shorter than 690 nm, inferring excitation transfer between Chls before 760-nm fluorescence occurs.Our measurements illustrate that: 1) a single group of low-energy Chls (F725) of the core-like PS I complex in cyanobacteria shows a strongly temperature-dependent fluorescence and, when directly excited, nearly complete fluorescence polarization, 2) these properties are not the result of detergent-induced artifacts as we are examining intact PS I within the thylakoid membrane of S. 6803, and 3) the activation energy for excitation transfer from F725 Chls to P700 is less than that of F735 Chls in green plants; F725 Chls may act as a sink to locate excitations near P700 in PS I.
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J Phys Chem A
January 2025
Laboratory of Advanced Computation and Theory for Materials and Chemistry, Department of Chemistry, National Institute of Technology Warangal (NITW), Warangal, Telangana 506004, India.
We report nonconjugated monocyclic dienes (nCMDs) as unique photoswitchable molecules that hold promise for harvesting substantial solar energy and storing it for extended durations. Herein, cyclohepta-1,4-diene and its N-heterocyclic analogue have been considered as prototypical models for investigating photoswitching behavior in nCMDs. Initially, the nonradiative deactivation pathway of nCMD from the low-lying excited state to the [2 + 2]-cycloadduct has been evaluated.
View Article and Find Full Text PDFAnal Chim Acta
March 2025
Zhejiang Key Laboratory of Advanced Optical Functional Materials and Devices, Ningbo University, Ningbo, 315211, China; Engineering Research Center for Advanced Infrared Photoelectric Materials and Devices of Zhejiang Province, Ningbo University, Ningbo, 315211, China. Electronic address:
Background: Permethrin is a pesticide used to kill insects, and once used in excess, it poses a great threat to the environment and human health, therefore, it is necessary to realize the rapid and accurate detection of permethrin. Fiber optic surface enhanced Raman scattering (SERS) probes have the advantages of small volume and can be used for remote monitoring, which have great potential for application in achieving in-situ detection of pesticide residues.
Results: Fiber taper waist (FTW) SERS probes modified by silver nanocubes-graphene oxide (Ag NCs-GO) composite structures were prepared for in situ detection of permethrin in lake water.
Phys Rev Lett
December 2024
Chalmers University of Technology, Department of Physics, 412 96 Göteborg, Sweden.
The phonon inverse Faraday effect describes the emergence of a dc magnetization due to circularly polarized phonons. In this work we present a microscopic formalism for the phonon inverse Faraday effect. The formalism is based on time-dependent second order perturbation theory and electron phonon coupling.
View Article and Find Full Text PDFJ Chem Phys
January 2025
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.
Time-resolved spectroscopy is an important tool for probing photochemically induced nonequilibrium dynamics and energy transfer. Herein, a method is developed for the ab initio simulation of vibronic spectra and dynamical processes. This framework utilizes the recently developed nuclear-electronic orbital time-dependent configuration interaction (NEO-TDCI) approach, which treats all electrons and specified nuclei quantum mechanically on the same footing.
View Article and Find Full Text PDFJ Phys Chem C Nanomater Interfaces
January 2025
Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, U.K.
Using many-body perturbation theory, we study the optical properties of phenylthiolate-capped cadmium sulfide nanoparticles to understand the origin of the experimentally observed blue shift in those properties with decreasing particle size. We show that the absorption spectra predicted by many-body perturbation theory agree well with the experimentally measured spectra. The results of our calculations demonstrate that all low-energy excited states correspond to a mixture of two fundamental types of excitations: intraligand and ligand-to-metal charge-transfer excitations.
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