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The i-motif is a DNA structure formed by cytosine-rich sequences, very relevant from a biochemical point of view and potentially useful in nanotechnology as pH-sensitive nanodevices or nanomotors. To provide a different view on the structural changes and dynamics of direct excitation processes involving i-motif structures, the use of rapid-scan FTIR spectroscopy is proposed. Hybrid hard- and soft-modelling based on the Multivariate Curve Resolution by Alternating Least Squares (MCR-ALS) algorithm has been used for the resolution of rapid-scan FTIR spectra and the interpretation of the photochemically induced time-dependent conformational changes of i-motif structures. The hybrid hard- and soft-modelling version of MCR-ALS (HS-MCR), which allows the introduction of kinetic models to describe process behavior, provides also rate constants associated with the transitions modeled. The results show that UV irradiation does not produce degradation of the studied sequences but induces the formation of photodimers. The presence of these affect much more the stability of i-motif structures formed by short sequences than that of those formed by longer sequences containing additional structural stabilizing elements, such as hairpins.
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http://dx.doi.org/10.1039/c8cp00850g | DOI Listing |
Appl Spectrosc
May 2025
Department of Materials Science and Engineering, University of Delaware, Newark, DE, USA.
Time-resolved, rapid-scan Fourier transform infrared (FT-IR) difference spectra have been recorded upon illumination on photosynthetic reaction centers (RCs) from under fixed hydration conditions (relative humidity = 76%). Two different illumination schemes were adopted. Whereas the use of a laser flash (duration: 7 ns) made it possible to follow the kinetics of recombination of the light-induced state PQ to the neutral state PQ, the use of a 20.
View Article and Find Full Text PDFBiochemistry
November 2024
Department of Physics, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.
The secondary plastoquinone (PQ) electron acceptor Q in photosystem II (PSII) undergoes a two-step photoreaction through electron transfer from the primary PQ electron acceptor Q, converting into plastoquinol (PQH). However, the detailed mechanism of the Q reactions remains elusive. Here, we investigated the reaction mechanism of Q in cyanobacterial PSII core complexes using two time-revolved infrared (TRIR) methods: dispersive-type TRIR spectroscopy and rapid-scan Fourier transform infrared spectroscopy.
View Article and Find Full Text PDFPlant Physiol Biochem
November 2024
Department of Microbiology & Immunology, University of British Columbia, Vancouver, Canada. Electronic address:
ACS Catal
September 2024
Department of Chemical Engineering, MESA+ Institute for Nanotechnology, University of Twente Faculty of Science and Technology, Drienerlolaan 5, Enschede 7522 NB, The Netherlands.
J Phys Chem B
August 2024
Department of Physics, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.
The early stages of the photoassembly of the water-oxidizing MnCaO cluster in spinach photosystem II (PSII) were monitored using rapid-scan time-resolved Fourier transform infrared (FTIR) spectroscopy. Carboxylate stretching and the amide I bands, which appeared upon the flash-induced oxidation of a Mn ion, changed their features during the subsequent dark rearrangement process, indicating the relocation of the Mn ion concomitant with protein conformational changes. Monitoring the isotope-edited FTIR signals of a Mes buffer estimated that nearly two protons are released upon the Mn oxidation.
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