Antiaggregation drugs play an important role in therapeutic approaches for Alzheimer's disease. Although a large number of small molecules that inhibit the aggregation of the tau protein have been identified, little is known about their mode of action. Here, we reveal the mechanism and the nature of tau species that are generated by interaction of tau with the organic compound pthalocyanine tetrasulfonate (PcTS). We demonstrate that PcTS interferes with tau filament formation by targeting the protein into soluble oligomers. A combination of NMR spectroscopy, electron paramagnetic resonance, and small-angle X-ray scattering reveals that the soluble tau oligomers contain a dynamic, noncooperatively stabilized core with a diameter of 30−40 nm that is distinct from the core of tau filaments. Our results suggest that specific modulation of the conformation of tau is a viable strategy for reduction of pathogenic tau deposits.
We demonstrate the use of electron spin resonance (ESR) to determine long-range distances and flexibility in water-soluble bis-peptide molecular rods. Bis-peptide oligomers with 4-8 monomer units were synthesized. ESR determined that the end-to-end length of the peptides is linearly proportional to the number of monomers. The linear shape is, therefore, easily interpreted from the data. In addition, the flexibility of the rods was quantified directly from the ESR-determined distance distribution functions. Quantitative information on chain length and flexibility is important to develop the use of these oligomers as rodlike structural elements for applications such as bivalent display of ligands and as elements of future nanoscale devices.
including oxygen vacancies ( V O ), [ 6 ] and zinc vacancies ( V Zn ), [ 7 ] interstitials (Zn i , O i ), [ 8 ] and antisite defects (Zn O , O Zn ) [ 9 ] as well as chemical impurities such as Cu. [ 10 ] The need to characterize point defects in ZnO is further amplifi ed with the recent applications of ZnO nanoparticles as hosts of single emitters for quantum information processing [11][12][13] and their use in random lasing [ 14 ] and other advanced sensing technologies. [ 15 ] These applications require precise control over the defect engineering in ZnO nanoparticles. Consequently, correlative characterization of point defects will be valuable to explore the luminescence properties and affi liate them with their chemical and paramagnetic spin features.In this work we perform comprehensive studies on the formation and photophysical properties of point defects in ZnO nanoparticles. In particular, we employ correlative characterization techniques to assign the optical emission peaks and electron paramagnetic resonance (EPR) lines to specifi c defects in ZnO nanoparticles. Our results provide new insight into optical luminescence properties of ZnO nanoparticles and promote them as potential candidate for nanophotonic technologies. [ 16 ] Results and DiscussionAfter being annealed in an Ar or Zn vapor environment at 700-900 °C the as-received ZnO nanoparticles (diameter ≈ 20 nm) coalescence [ 17,18 ] and display faceted morphologies ( Figure 1 ). The nanoparticles increase in average size up to about 120 nm after annealing in inert gas (Ar) or oxygen, and up to 150 nm for annealing in Zn vapor at 900 °C [see Figures S1 and S2, Supporting Information for nanoparticle sizes obtained from scanning electron microscopy (SEM) image and X-ray diffraction (XRD) analysis]. Since the Bohr radius of ZnO is 2.34 nm, [ 19 ] the nanoparticles are large enough to avoid quantum size effects but still possess a suffi ciently large surface area to allow defect engineering.To investigate the occurrence of defects in ZnO nanoparticles, EPR spectroscopy was performed. Figure 2 a shows EPR spectra of the as-received, O 2 annealed, Zn vapor annealed ZnO nanoparticles and a bare Si(100) substrate for comparison. The as-received ZnO nanoparticles exhibit a strong signal at g = 1.96, which has been previously assigned to zinc vacancies (V Zn − ), [ 20 ] oxygen interstitials (O i − ), [ 20 ] zinc interstitials (Zn i + ) [ 21 ] and to electrons in weakly bound or conduction band (CB) Zinc oxide (ZnO) nanoparticles have recently been identifi ed as a promising candidate for advanced nanophotonics applications and quantum technologies. This work reports the formation of luminescent point defects and describes their photophysical properties. In particular, it is shown using correlative photoluminescence, cathodoluminescence, electron paramagnetic resonance (EPR), and X-ray absorption near-edge spectroscopy that green luminescence at 2.48 eV and an EPR line at g = 2.00 belong to a surface oxygen vacancy (V o,s + ) center, while a second green emi...
Pulsed electron-electron double resonance (PELDOR, also known as DEER) has become a method of choice to measure distances in biomolecules. In this work we show how the performance of the method can be improved at high EPR frequencies (94 GHz) using variable dual frequency irradiation in a dual mode cavity in order to obtain enhanced resolution toward orientation selection. Dipolar evolution traces of a representative RNA duplex and an α-helical peptide were analysed in terms of possible bi-radical structures by considering the inherent ambiguity of symmetry-related solutions.
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