Relaxation times of the principal (Debye-type) relaxation terms in the dielectric spectra of water and normal alcohols have been evaluated in order to eliminate the effect of multi-molecular cross-correlations and to thus yield reorientation times of the molecular electric dipole moments. The reorientation times have been compared to relaxation times from ultraviolet and X-ray Brillouin spectra as well as from broadband ultrasonic spectra, which are considered as the structure relaxation times characterizing the density fluctuations of the liquid hydrogen bond networks. With some alcohols, shear impedance spectra indicate the network fluctuations to be tightly associated with shear viscosity relaxation. Within the limits of uncertainty, the molecular dipole moment reorientation times and the structure relaxation times feature close correlations. This finding suggests a coupling between translational and orientational molecular motions, and it is discussed in the light of the wait-and-switch model of dielectric relaxation.
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http://dx.doi.org/10.1063/1.4991850 | DOI Listing |
Chem Biomed Imaging
January 2025
Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 3, CH-8093 Zürich, Switzerland.
Three water-soluble Mn(III)-porphyrin complexes with cationic pyridyl side groups bearing COOH- or OH-terminated carbon chains in the meta or para positions have been synthesized as probes for both magnetic resonance imaging (MRI) and photodynamic therapy (PDT). The complexes , , and are highly water-soluble, and their relaxivities range between 10 and 15 mM s, at 20-80 MHz and 298 K, 2-3 times higher than that of commercial Gd(III)-based agents. The complexes containing carboxylate () or alcoholic () side chains in the para position are endowed with higher relaxivities and have also shown efficient photoinduced DNA cleavage and singlet oxygen (O) generation.
View Article and Find Full Text PDFAppl Magn Reson
October 2024
Laboratory of Chemical Physics, National Institute of Diabetes and Digestive and Kidney Diseases, National Institutes of Health, Bethesda, MD 20892-0520 USA.
Unlabelled: Temperature-dependent DEER effects are observed as a function of methyl rotation by either leucine- or nitroxide-specific protonated methyl groups in an otherwise deuterated background. Both species induce a site-specific enhancement in the apparent relaxation of the paramagnetic nitroxide label. The presence of a single protonated methyl group in close proximity (4-10 Å) to only one of the two nitroxide rotamer ensembles in AviTagged immunoglobulin-binding B domain of protein A results in a selective and substantial decrease in , manifested by differential decay of the peak intensities in the bimodal distance distribution as a function of the total dipolar evolution time, temperature, or both.
View Article and Find Full Text PDFACS Appl Bio Mater
January 2025
Department of Materials Science and Engineering, and Centre for Functional Photonics (CFP), City University of Hong Kong, Hong Kong SAR 999077, P. R. China.
Bioimaging probes based on carbon dots (CDs) can become a useful replacement for existing commercial probes, benefiting clinical diagnostics. While the development of dual-mode CD-based probes for magnetic resonance imaging (MRI), which provides the ability for photoluminescence (PL) detection at the same time, is ongoing, several challenges have to be addressed. First, most of the CD-based probes still emit at shorter wavelengths (blue/green spectral range), which is harmful to biological objects or have very low PL intensity in the biological window of tissue transparency (red/near-infrared spectral range).
View Article and Find Full Text PDFSci Rep
January 2025
Department of Pharmacology and Experimental Therapeutics; MS 1015, College of Pharmacy and Pharmaceutical Sciences, The University of Toledo, Health Education Building; Room 282E, 3000 Arlington Ave, Toledo, OH, 43614, USA.
We previously demonstrated that the inability of primary endothelial cilia to sense fluid shear stress can lead to nitric oxide (NO) deficiency and cause hypertension (HTN). Decreased biosynthesis of NO contributes to cerebral amyloid angiopathy in Alzheimer's disease (AD) patients through increased deposition of amyloid beta (Aβ). However, the molecular mechanisms underlying the pathogenesis of HTN and AD are incompletely understood.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
College of Physics Science and Technology, Yangzhou University, Yangzhou 225009, China.
Developing high-performance solar cells is a practical way to improve clean energy conversion efficiency. However, the performance of solar cells faces challenges such as fast carrier combination, poor stability, and limited solar light harvesting. Herein, we propose a strategy by decorating periodic holes in two-dimensional (2D) porous carbon-nitrogen (CN) materials with a zero-dimensional (0D) semiconducting (ZnO) cluster.
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