Concise synthesis of arnottin I and (-)-arnottin II

Application of the Buchwald protocol to the coupling of o-bromobenzoates and 1-tetralones directly affords benzodihydronaphthopyrones with a fused tetracyclic system. Aromatization of the 7,8-dimethoxy-2,3-methylenedioxy derivative yielded arnottin I, whereas oxidation with dioxirane afforded dihydroarnottin II composed of a spiro phthalide-tetralone system. Sharpless asymmetric dihydroxylation using AD-mix yielded optically active dihydroarnottin II with good enantioselectivity. The absolute stereochemistry of the stereogenic center in the (+)-spiro product was determined to be R by X-ray crystallographic analysis of the dibromo derivative. (+)-Dihydroarnottin II was subjected to successive bromination and dehydrobromination to prepare (-)-arnottin II. The R-configuration of natural (-)-arnottin II, previously assigned by application of the exciton chirality method to the Cotton effects observed in the CD spectrum, was confirmed by asymmetric synthesis.     

Limiting Current in a Flowing‐Electrolyte‐Type Droplet Cell

To the limit : Electrolyte flow accelerates the mass‐transfer process in a droplet cell (see picture). The limiting current in the cell is expressed as a sum of hydrodynamic and stagnant terms. The current derived from the latter term indicates that convective mass transfer in the cell would be changed dramatically at a significantly small volumetric flow rate.

     

The Structural Rule Distinguishing a Superfold: A Case Study of Ferredoxin Fold and the Reverse Ferredoxin Fold

Superfolds are folds commonly observed among evolutionarily unrelated multiple superfamilies of proteins. Since discovering superfolds almost two decades ago, structural rules distinguishing superfolds from the other ordinary folds have been explored but remained elusive. Here, we analyzed a typical superfold, the ferredoxin fold, and the fold which reverses the N to C terminus direction from the ferredoxin fold as a case study to find the rule to distinguish superfolds from the other folds. Though all the known structural characteristics for superfolds apply to both the ferredoxin fold and the reverse ferredoxin fold, the reverse fold has been found only in a single superfamily. The database analyses in the present study revealed the structural preferences of αβ- and βα-units; the preferences separate two α-helices in the ferredoxin fold, preventing their collision and stabilizing the fold. In contrast, in the reverse ferredoxin fold, the preferences bring two helices near each other, inducing structural conflict. The Rosetta folding simulations suggested that the ferredoxin fold is physically much more realizable than the reverse ferredoxin fold. Therefore, we propose that minimal structural conflict or minimal frustration among secondary structures is the rule to distinguish a superfold from ordinary folds. Intriguingly, the database analyses revealed that a most stringent structural rule in proteins, the right-handedness of the βαβ-unit, is broken in a set of structures to prevent the frustration, suggesting the proposed rule of minimum frustration among secondary structural units is comparably strong as the right-handedness rule of the βαβ-unit.     

Compressed sensing by two-directional line sensing

Optical Review - We propose an imaging method using commercially available profile sensor. Specifically, we use a multipixel CMOS area sensor capable of acquiring projection profiles and perform...     

Structural-transformation-induced Drastic Luminescence Changes in an Organic-Inorganic Hybrid [ReN(CN)4]2− Salt Triggered by Chemical Stimuli

We synthesized a (1-propylpyridinium)₂[ReN(CN)₄]-type organic–inorganic hybrid exhibiting water-vapor-induced drastic structural changes of the [ReN(CN)₄]²⁻ assemblies. Specifically, upon exposure to water vapor, dehydrated nitrido-bridged chains were converted to hydrated cyanido-bridged tetranuclear clusters via rearrangements of large molecular building units in the crystals. These switchable assembly forms display substantially different photo-physical properties, although in both cases the emission is caused by a metal-centered d–d transition. The nitrido-bridged chain exhibited a near-infrared (749 nm) emission, which blue-shifted as the temperature increased, while a visible (561 nm) emission and its red shift was demonstrated by the cyanido-bridged cluster.     

Measurement of image sensor tilt based on amplitude and phase of image

Optical Review - In this study, we present a new method for measuring the tilt of an image sensor to the lens. The assembly accuracy of the lens and image sensor units has a significant influence...     

Cover Picture: Electrochemical Method for G-quartet RNA Detection of COVID-19 Based on Cyclic Ferrocenylnaphthalene Diimide (Electroanalysis 4/2023)

To develop an electrochemical detection method for COVID-19, we have investigated the interaction between RG-1, a characteristic parallel four-strand RNA component of the COVID-19 genome, and cyclic ferrocenylnaphthalene diimides carrying different linker lengths 1 and 2 , which bind to RG-1 more strongly than cyclic naphthalene diimide 3 that lacks a ferrocene moiety. In particular, the binding affinity of 1 having short one showed the highest binding affinity to RG-1, and the redox current of 1 increased in the presence of RG-1 using a glassy carbon electrode. This increasing current of 1 in the presence of c-myc as a parallel G4 DNA or single-stranded RNA was lower than that in the presence of RG-1. Several RG-1 was electrochemically detected at the nanomolar level by 1 .     

A facile method for generation of carbon oxide sulfide

Carbon oxide sulfide was easily generated upon heating of amine salts of carbamothioic acids at 85°C which were produced in situ from amines, carbon monoxide, and elemental sulfur in the presence of a catalytic amount of selenium under mild conditions.