The Total Squared Curvature of Curves and Approximation by Piecewise Circular Curves

For a smooth curve in the Euclidean spaces, the total squared curvature is defined as the integral of the square of the curvature. If one takes three points on the curve which are close to one another, the reciprocal of the radius of the circle passing through those points approximates the curvature. We use this to approximate the total squared curvature and study its convergence rate.     

Structural phase transitions in KMnF3

The structural transitions of the perovskite KMnF₃ are studied with an energy-dispersive X-ray diffractometer. It is found that the 83 K transition is of first order, though the transition related to the condensation of a M₃-soft phonon mode is considerably affected by crystallographic domain-walls occurring below the 186 K transition. The latter transition is observed at 88.0 K (first-order), and 92.0 K (second-order) in different single crystals, respectively. The difference of the transition temperature and the transition order is interpreted in terms of inner strains appeared in the domain walls.     

Incommensurate cooperative tilting modes of MnF6 octahedra relatedto the structural phasetransitions in BaMnF4

The structural phase transitions of the layer compound BaMnF₄ were studied by high-resolution X-ray diffraction using synchrotron radiation. The intensities and profiles of two kinds of superlattice reflections having incommensurate reduced wave vectors q ₁= (～ ± 1/5,0,0) _p and q ₂ =(～ ± 2/5,1/2,1/2)_p, respectively, were measured as a function of temperature from 25 K to 280 K. These temperature dependencies show that incommensurate structural phase transitions of second order occur at 234 K and 244 K. These structural phase transitions are interpreted as successive condensations of a folding-screen-like incommensurate plane-distortion mode and a commensurate anti-ferro-distortive tilting mode of the MnF₆ octahedra around the primitive a₀ - and b₀ -axes, when cooled down. It is also found that there is another structural phase transition at about 45 K related to a precursor structural distortion for the antiferromagnetic transition occurring at about 26 K.     

Synthesis of C12-Keto Saxitoxin Derivatives with Unusual Inhibitory Activity Against Voltage-Gated Sodium Channels

A novel series of C12-keto-type saxitoxin (STX) derivatives bearing an unusual nonhydrated form of the ketone at C12 has been synthesized, and their Na_V-inhibitory activity has been evaluated in a cell-based assay as well as whole-cell patch-clamp recording. Among these compounds, 11-benzylidene STX ( 3 a ) showed potent inhibitory activity against neuroblastoma Neuro 2A in both cell-based and electrophysiological analyses, with EC₅₀ and IC₅₀ values of 8.5 and 30.7 nm , respectively. Interestingly, the compound showed potent inhibitory activity against tetrodotoxin-resistant subtype of Na_V1.5, with an IC₅₀ value of 94.1 nm . Derivatives 3 a – d and 3 f showed low recovery rates from Na_V1.2 subtype (ca 45–79 %) compared to natural dcSTX ( 2 ), strongly suggesting an irreversible mode of interaction. We propose an interaction model for the C12-keto derivatives with Na_V in which the enone moiety in the STX derivatives 3 works as Michael acceptor for the carboxylate of Asp¹⁷¹⁷.     

DNA Origami Scaffolds as Templates for Functional Tetrameric Kir3 K+ Channels

In native systems, scaffolding proteins play important roles in assembling proteins into complexes to transduce signals. This concept is yet to be applied to the assembly of functional transmembrane protein complexes in artificial systems. To address this issue, DNA origami has the potential to serve as scaffolds that arrange proteins at specific positions in complexes. Herein, we report that Kir3 K⁺ channel proteins are assembled through zinc‐finger protein (ZFP)‐adaptors at specific locations on DNA origami scaffolds. Specific binding of the ZFP‐fused Kir3 channels and ZFP‐based adaptors on DNA origami were confirmed by atomic force microscopy and gel electrophoresis. Furthermore, the DNA origami with ZFP binding sites nearly tripled the K⁺ channel current activity elicited by heterotetrameric Kir3 channels in HEK293T cells. Thus, our method provides a useful template to control the oligomerization states of membrane protein complexes in vitro and in living cells.     

Characterization of atenolol transformation products on light-activated TiO2 surface by high-performance liquid chromatography/high-resolution mass spectrometry

We have studied the photocatalytic transformation of atenolol, 4-[2-hydroxy-3-[(1-methyl)amino]propoxyl]benzeneacetamide, a cardioselective beta-blocking agent used to treat cardiac arrhythmias and hypertension, under simulated solar irradiation using titanium dioxide as photocatalyst. The investigation involved monitoring drug decomposition, identifying intermediate compounds, assessing mineralization, and evaluating toxicity. High-performance liquid chromatography (HPLC) coupled to high-resolution mass spectrometry (HRMS) via an electrospray ionization (ESI) interface was a powerful tool for the identification and measurement of the degradation products; 23 main species were identified. Intermediates were characterized through their chromatographic behavior and evolution kinetics, coupled with accurate mass information. Through the full analysis of MS and MS(n) spectra and a comparison with parent drug fragmentation pathways, the diverse isomers were characterized. Neither atenolol nor the intermediates formed exhibit acute toxicity. All intermediates are easily degraded and no compound identified could withstand 2 h irradiation. Photomineralization of the substrate in terms of carbon mineralization and nitrogen release was rapid and, within 4 h of irradiation, organic nitrogen and carbon were completely mineralized.     

Metal‐Free Enantioselective Oxidative Arylation of Alkenes: Hypervalent‐Iodine‐Promoted Oxidative C−C Bond Formation

The enantioselective oxyarylation of (E)‐6‐aryl‐1‐silyloxylhex‐3‐ene was achieved using a lactate‐based chiral hypervalent iodine(III) reagent in the presence of boron trifluoride diethyl etherate. The silyl ether promotes the oxidative cyclization, and enhances the enantioselectivity. In addition, the corresponding aminoarylation was achieved.