The effect of mixed cyclodextrin-surfactant systems on the ground and excited state proton transfer reactions of 4-methyl-2,6-diformylphenol (MFOH) in aqueous solution has been investigated by steady state and time-resolved fluorescence spectroscopy. It has been found that micellar media perturbs the solvation of MFOH and facilitates nanocaging. In the presence of micelle, MFOH preferentially resides in the interfacial region. Depending on the local pH due to compartmentalization of reaction media, normal or anionic form of MFOH dominates. Encapsulation of the probe within the cyclodextrin nanocavity enhances the shorter lifetime component of MFOH unexpectedly, which has been explained on the basis of reduced solvation and reduced dipolar effect due to confinement.
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http://dx.doi.org/10.1021/jp806211v | DOI Listing |
Photosynth Res
January 2025
Belozersky Institute of Physico-Chemical Biology, Lomonosov Moscow State University, Leninskie Gory, Moscow, Russia, 119991.
The femtosecond dynamics of energy transfer from light-excited spirilloxanthin (Spx) to bacteriochlorophyll (BChl) a in the reaction centers (RCs) of purple photosynthetic bacteria Rhodospirillum rubrum was studied. According to crio-electron microscopy data, Spx is located near accessory BChl a in the B-branch of cofactors. Spx was excited by 25 fs laser pulses at 490 nm, and difference absorption spectra were recorded in the range 500-700 nm.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
TU Dortmund: Technische Universitat Dortmund, Fakultät für Chemie und Chemische Biologie, Otto-Hahn Str.6, 44227, Dortmund, GERMANY.
This study introduces a novel class of carbon-centered diradicals: a monosubstituted C-atom stabilized by a phosphine. The diradical Ph3P→C was photochemically generated from a diazophosphorus ylide precursor (Ph3PCN2) and characterized by EPR and isotope-sensitive ENDOR spectroscopy at low temperatures. Ph3P→C features an axial zero-field splitting parameter D = 0.
View Article and Find Full Text PDFMaterials (Basel)
January 2025
Department of Civil Engineering, University of Texas Rio Grande Valley, Edinburg, TX 78539, USA.
This paper focuses on the theoretical and analytical modeling of a novel seismic isolator termed the Passive Friction Mechanical Metamaterial Seismic Isolator (PFSMBI) system, which is designed for seismic hazard mitigation in multi-story buildings. The PFSMBI system consists of a lattice structure composed of a series of identical small cells interconnected by layers made of viscoelastic materials. The main function of the lattice is to shift the fundamental natural frequency of the building away from the dominant frequency of earthquake excitations by creating low-frequency bandgaps (FBGs) below 20 Hz.
View Article and Find Full Text PDFNeuropharmacology
January 2025
Division of Molecular Psychiatry, Center of Mental Health, University Hospital Würzburg, Würzburg, Germany; Department of Psychiatry, Psychosomatics and Psychotherapy, Center of Mental Health, University Hospital Würzburg, Würzburg, Germany.
While healthy brain function relies on a dynamic but tightly regulated interaction between excitation (E) and inhibition (I), a spectrum of social cognition disorders, including antisocial behavior and antisocial personality disorder (ASPD), frequently ensuing from irregular neurodevelopment, may be associated with E/I imbalance and concomitant alterations in neural connectivity. Technological advances in the evaluation of structural and functional E/I balance proxies in clinical settings and in human cell culture models provide a general basis for identification of biomarkers providing a powerful concept for prevention and intervention across different dimensions of mental health and disease. In this perspective we outline a framework for research to characterize neurodevelopmental pathways to antisocial behavior and ASPD driven by (epi)genetic factors across life, and to identify molecular targets for preventing the detrimental effects of cognitive dysfunction and maladaptive social behavior, considering psychosocial experience; to validate signatures of E/I imbalance and altered myelination proxies as biomarkers of pathogenic neural circuitry mechanisms to determine etiological processes in the transition from mental health to antisocial behavior and ASPD and in the switch from prevention to treatment; to develop a neurobiologically-grounded integrative model of antisocial behavior and ASPD resultant of disrupted E/I balance, allowing to establish objective diagnoses and monitoring tools, to personalize prevention and therapeutic decisions, to predict treatment response, and thus counteract relapse; and finally, to promote transformation of dimensional disorder taxonomy and to enhance societal awareness and reception of the neurobiological basis of antisocial behavior and ASPD.
View Article and Find Full Text PDFJ Comput Chem
January 2025
Department of Chemistry, Gottwald Center for the Sciences, University of Richmond, Richmond, Virginia, USA.
The energies and geometries of the lowest lying singlet and triplet states of the four diradicals formed by removing two H atoms from thiophene have been characterized. We utilized the highly correlated, multireference methods configuration interaction with single and double excitations with and without the Pople correction for size-extensivity (MR-CISD+Q and MR-CISD) and averaged quadratic coupled cluster theory (MR-AQCC). CAS (8,7) and CAS (10,8) active spaces involving σ, σ*, π, and π* orbitals were employed along with the cc-pVDZ and cc-pVTZ basis sets.
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