Diaminodiacid Bridges to Improve Folding and Tune the Bioactivity of Disulfide‐Rich Peptides

Disulfide‐rich peptides containing three or more disulfide bonds are promising therapeutic and diagnostic agents, but their preparation is often limited by the tedious and low‐yielding folding process. We found that a single cystine‐to‐diaminodiacid replacement could significantly increase the folding efficiency of disulfide‐rich peptides and thus improve their production yields. The practicality of this strategy was demonstrated by the synthesis and folding of derivatives of the μ‐conotoxin SIIIA, the preclinical hormone hepcidin, and the trypsin inhibitor EETI‐II. NMR and X‐ray crystallography studies confirmed that these derivatives of disulfide‐rich peptide retained the correct three‐dimensional conformations. Moreover, the cystine‐to‐diaminodiacid replacement enabled structural tuning, thereby leading to an EETI‐II derivative with higher bioactivity than the native peptide.     

Magnetic,Mössbauer and optical spectroscopic properties of the AFe3O(PO4)3 (A = Ca,Sr, Pb) series of powder compounds

AFe₃O(PO₄)₃ (A = Ca, Sr and Pb) powder compounds were studied by means of X-ray diffraction (XRD), electron-probe microanalysis (EPMA) coupled with wavelength dispersion spectroscopy (WDS), Raman and diffuse reflectance spectroscopies, specific heat and magnetic properties measurements. Magnetization, magnetic susceptibility and specific heat measurements carried out on AFe₃O(PO₄)₃ (A = Sr, Ca and Pb) powders firmly establish a series of three ferromagnetic (FM)-like second order phase transitions spanned over the 32–8 K temperature range. Room temperature Mössbauer spectroscopy and associated DFT calculations confirm the existence of three crystallographically non equivalent Fe³⁺ sites in the three compounds. Mössbauer spectra recorded as a function of temperature in the PbFe₃O(PO₄)₃ compound also establishes the occurrence of two purely magnetic and reversible phase transitions at 32 and 10 K. Diffuse reflectance measurements reveal two broad absorption bands at 1047 and 837 nm, in both PbFe₃O(PO₄)₃ and SrFe₃O(PO₄)₃ powders, with peak cross sections ∼10⁻²⁰ cm² typical of spin-forbidden and forced electric dipole intraconfigurational transitions.     

Ultrathin Co3S4 Nanosheets that Synergistically Engineer Spin States and Exposed Polyhedra that Promote Water Oxidation under Neutral Conditions

Development of efficient and affordable electrocatalysts in neutral solutions is paramount importance for the renewable energy. Herein, we report that the oxygen evolution reaction (OER) performance of Co₃S₄ under neutral conditions can be enhanced by exposed octahedral planes and self‐adapted spin states in atomically thin nanosheets. A HAADF image clearly confirmed that the active octahedra with Jahn–Teller distortions were exposed exclusively. Most importantly, in the atomically thin nanosheets, the spin states of Co³⁺ in the octahedral self‐adapt from low‐spin to high‐spin states. As a result, the synergistic effect endow the Co₃S₄ nanosheets with superior OER performance, with exceptional low onset overpotentials of circa 0.31 V in neutral solutions, which is state‐of‐the‐art among inorganic non‐noble metal compounds.     

Approach of charge disproportionation in the perovskite oxide TlNiO3 from ab initio electronic structures

The experimentally observed phenomenon of charge disproportionation (CD) of nickel in the perovskite TlNiO₃ is addressed from band theoretical computations within the augmented spherical wave (ASW) method of the respective distorted orthorhombic and monoclinic structures. From a careful analysis of the chemical bonding as derived from the covalent bond energy ECOV approach an integration of the DOS within the valence band leads to an imbalance of charge of ∼±0.35 electrons pointing to a CD within range of experimentally obtained values through Mössbauer spectroscopy of ⁵⁷Fe probe and bond valence calculations.     

Electron paramagnetic resonance studies on manganite Pr0.5Sr0.5Mn1−x Ga x O3 (x=0 and 0.05)

In this paper, we present the investigations of electron paramagnetic resonance on perovskite manganite Pr_0.5Sr_0.5MnO₃ and Ga-doped Pr_0.5Sr_0.5Mn_0.95Ga_0.05O₃. The temperature dependent paramagnetic resonance spectra parameters (effective g-factor, peak-to-peak linewidth ΔH _pp and double integrated intensities) have been used to study the paramagnetic spin correlations and spin dynamics. The gradual increase of effective g-factor is attributed to the presence of orbital ordering above T _C. The model fittings of temperature dependent double integrated intensities reveal Arrhenius law is appropriate for describing Pr_0.5Sr_0.5Mn_0.95Ga_0.05O₃ instead of Pr_0.5Sr_0.5MnO₃ system. As for Pr_0.5Sr_0.5MnO₃, the broadening of linewidth with the temperature increase origins from the contribution of small polaron hopping in the PM regime. However, as for Pr_0.5Sr_0.5Mn_0.95Ga_0.05O₃, the broadening of EPR linewidth can be understood with the spin-lattice relaxation mechanism.     

Direct Observation of Transition Metal Dichalcogenides in Liquid with Scanning Tunneling Microscopy

We present atomic-resolution images of TiSe\begin{document}$_2$\end{document}, MoTe\begin{document}$_2$\end{document} and TaS\begin{document}$_2$\end{document} single crystals in liquid condition using our home-built scanning tunneling microscopy (STM). By facilely cleaving of single crystals in liquid, we were able to keep the fresh surface not oxidized within a few hours. Using the high-stable home-built STM, we have obtained atomic resolution images of TiSe\begin{document}$_2$\end{document} accompanied with the single atom defects as well as the triangle defects in solution for the first time. Besides, the superstructure of MoTe\begin{document}$_2$\end{document} and hexagonal charge-density wave domain structure in nearly commensurate phase of TaS\begin{document}$_2$\end{document} were also obtained at room temperature (295 K). Our results provide a more efficient method in investigating the lively surface of transition metal dichalcogenides. Besides, the high stable liquid-phase STM will support the further investigations in liquid-phase catalysis or electrochemistry.     

C 1s NEXAFS study of rare-earth’s (La,Eu)-graphite intercalation compounds

Electronic structure of unoccupied states of Eu- and thin surface layer of La-intercalation compounds was studied by light polarization dependent NEXAFS at the C 1s threshold in a bulk sensitive (E_kin=1–2 eV) and a more surface sensitive (E_kin=265 eV) partial electron yield mode. It was shown that the C 1s spectra in both cases are mainly characterized by the π*- and σ*-symmetry graphite-derived features. For both systems the π*-derived peak was found at similar energies of exciting photons as for pristine graphite. A decrease of relative intensity of the π*-originated structure in intercalation compounds can be understood by partial occupation of the π*-derived states upon intercalation due to a charge transfer from rare-earth (RE) atoms. NEXAFS features found on both sides of the π* response may be related to pd hybrids forming as a result of chemical interaction between RE atoms and graphite layers.