Magnitude and direction of the spontaneous polarization of ferroelectric liquid crystals with several bond moments

The magnitude and direction of the spontaneous polarization in most ferroelectric liquid crystals have been confirmed to be determined by the location and magnitude of the bond moment around the chiral carbon and the core. In compounds with several bond moments their relative orientation is very important for obtaining a large spontaneous polarization. Compounds with benzene rings in the core substituted with OH also have a large spontaneous polarization, perhaps due to the formation of hydrogen bonds. Reversal of the direction of the spontaneous polarization with temperature has been found for EFPPOPB. This anomalous behaviour has been explained tentatively in terms of a conformation change due to the existence of a flexible -CH₂- unit between the chiral carbon and the dipole moment.     

Quantitative Structure-Activity Studies of Octopaminergic Agonists and Antagonists Against Locusta migratoria Using Similarity Indexes

Abstract

The quantitative structure-activity relationship of 39 octopamine (OA) agonists and 12 antagonists against the thoracic nerve cord of the migratory locust, Locusta migratoria L. was analyzed using atom based rigid fit method or flexible fitting offered by PowerFit 1.0 from MicroSimulation. For OA agonists, the more similar to reference compound NC (24) the structure of test compound, the higher the activity, whereas for OA antagonists it was not the case. Antagonists may not interact with the same part of the membrane with which the agonists interact. Taken the part of the membrane with which the agonist interacts as the true receptor, the antagonist may well interact with an area surrounding the receptor including the ionophore.     

Magnetic transition in dimerized radical cation salt of (BPDT-TTF)2ICl2 studied by heat capacity measurements

Thermodynamic investigation using the relaxation calorimetry technique and the microchip calorimetry technique is performed to clarify low-temperature behaviors of a radical cation salt consisting of a donor molecule of bispropylenedithiotetrathiafulvalene (BPDT-TTF) and a linear anion of ${{\text{ICl}}_{2}^{-}}$ ICl 2 ? . This compound has a layered structure similar to numerous BEDT-TTF compounds. The donor molecules form a dimerized arrangement in the layer. Temperature dependence of heat capacity obtained by the relaxation technique shows a broad hump structure around 20–25 K corresponding to the temperature where the magnetic susceptibility shows a drastic decrease due to the formation of the singlet spin state. The microchip calorimetry technique detected a step-like anomaly around 23 K in the temperature dependence of C _p T ^?1 of which entropy is evaluated as only few % of Rln2 corresponding to the full entropy of localized π-electrons located on each dimer unit. The negligibly small T-linear term in the low-temperature heat capacity and absence of magnetic fields dependence below 3.2 K predict opening of rigid gap structure in the spin excitations, which is consistent with a spin-singlet formation due to the formation of spin-Peierls type ordering or charge ordering state.     

Separation and Identification of Glycosaminoglycans

The term “mucopolysaccharides” was originally introduced by Meyer to describe “hexosamine-containing heteropolysaccharides of animal origin occurring in a pure state or as protein salts”. Many of the names originally assigned to the mucopolysaccharides have since been revised in an effort to systematize the nomenclature (Table 1). Jeanloz² in 1960 proposed the term “glycosaminoglycuronoglycans” in place of mucopolysaccharides as in most cases they are composed of amino sugars (glycosamino-) and uronic acids (glycurono-) joined in long chains(-glycans). For the sake of simplicity, the term “glycosaminoglycans” is getting acceptance in place of the rather lengthy term “glycosaminoglycuronoglycans” as well as the old and perhaps more familiar term “mucopolysaccharides”. As a matter of convenience, the term “polysaccharides” will be frequently used here, instead of glycosaminoglycans.     

Ferroelectricity in hBN intercalated double-layer graphene

Van der Waals (vdW) assembly of two-dimensional materials has long been recognized as a powerful tool for creating unique systems with properties that cannot be found in natural compounds [Nature 499, 419 (2013)]. However, among the variety of vdW heterostructures and their various properties, only a few have revealed metallic and ferroelectric behaviour signatures [Sci. Adv. 5, eaax5080 (2019); Nature560, 336 (2018)]. Here we show ferroelectric semimetal made of double-gated double-layer graphene separated by an atomically thin crystal of hexagonal boron nitride. The structure demonstrates high room temperature mobility of the order of 10 m²·V⁻¹·s⁻¹ and exhibits ambipolar switching in response to the external electric field. The observed hysteresis is reversible and persists above room temperature. Our fabrication method expands the family of ferroelectric vdW compounds and offers a promising route for developing novel phase-changing devices. A possible microscopic model of ferroelectricity is discussed.     

Attenuation of the Aggregation and Neurotoxicity of Amyloid‐β Peptides by Catalytic Photooxygenation

Alzheimer’s disease (AD), a progressive severe neurodegenerative disorder, is currently incurable, despite intensive efforts worldwide. Herein, we demonstrate that catalytic oxygenation of amyloid‐β peptides (Aβ) might be an effective approach to treat AD. Aβ1–42 was oxygenated under physiologically‐relevant conditions (pH 7.4, 37 °C) using a riboflavin catalyst and visible light irradiation, with modifications at the Tyr¹⁰, His¹³, His¹⁴, and Met³⁵ residues. The oxygenated Aβ1–42 exhibited considerably lower aggregation potency and neurotoxicity compared with native Aβ. Photooxygenation of Aβ can be performed even in the presence of cells, by using a selective flavin catalyst attached to an Aβ‐binding peptide; the Aβ cytotoxicity was attenuated in this case as well. Furthermore, oxygenated Aβ1–42 inhibited the aggregation and cytotoxicity of native Aβ.     

Ultrafast fluorescence dynamics of FMN-binding protein from Desulfovibrio vulgaris (Miyazaki F) and its site-directed mutated proteins

Ultrafast fluorescence dynamics of FMN in FMN-binding protein (FMN-bp), and its mutated proteins, W32Y and W32A, were investigated by the fluorescence up-conversion method. Fluorescence lifetimes were 167 fs (96%) and 1.5 ps (4%) in wild-type FMN-bp (WT), and 3.4 ps (23%), 18.2 ps (74%), and 96 ps (3%) at 530 nm in W32Y, and 30.1 ps in W32A. The fluorescence lifetime of W32A, in which Trp-32 was absent, was about 140 times longer than that of WT. Tyr-32 in W32Y was not so effective quencher as Trp-32 in WT. This was explained in terms of different ionization potentials of quenchers and average donor–acceptor distances in the protein.     

Linker-oriented design of binaphthol derivatives for optical resolution using lipase-catalyzed reaction

Candida antarctica lipase B (CAL-B) is one the most frequently used enzymes in organic synthesis for the preparation of optically active alcohols. However, it has not been used for the optical resolution of (+/-)-2,2'-binaphthol. We established an efficient linker-oriented design of 2,2'-binaphthol derivatives that is appropriate for optical resolution using CAL-B-catalyzed hydrolysis reaction. Methyl 4-(1-(6-bromo-2-methoxymethoxynaphthalen-1-yl)-6-bromonaphthalen-2-yloxy)butanoate was hydrolyzed by CAL-B to afford a corresponding acid with excellent enantioselectivity ( E > 200). Two types of optically active binaphthol derivatives, 1-(2-hydroxy-6-(naphthalen-1-yl)naphthalen-1-yl)-6-(naphthalen-1-yl)naphthalen-2-ol and 6-butyl-1-(6-butyl-2-hydroxynaphthalen-1-yl)naphthalen-2-ol, were prepared by this chemo-enzymatic reaction protocol and were used as chiral templates for symmetric reactions.     

Total synthesis of (±)-stemonamide, (±)-isostemonamide, (±)-stemonamine, and (±)-isostemonamine using a radical cascade

A total synthesis of (±)-stemonamide and (±)-isostemonamide has been achieved by using a radical cascade that involves two endo-selective cyclizations. (±)-Stemonamine and (±)-isostemonamine are synthesized by chemoselective reduction of (±)-stemonamide and (±)-isostemonamide, respectively.     

Facile fabrication of a novel high performance CO2 separation membrane: Immobilization of poly(amidoamine) dendrimers in poly(ethylene glycol) networks

Poly(amidoamine) (PAMAM) dendrimers showed high CO₂ separation properties and were successfully immobilized in a poly(ethylene glycol) (PEG) network upon photopolymerization of PEG dimethacrylate. The PAMAM dendrimer incorporation ratio was readily controlled, and a stable self-standing membrane containing up to 75 wt.% PAMAM dendrimer was obtained. The CO₂ separation properties over smaller H₂ were investigated by changing the PAMAM dendrimer content or generation and CO₂ partial pressure (ΔPCO₂$\mathrm{\Delta }{P}_{\text{C}{\text{O}}_2}$) under atmospheric conditions. Especially, a polymeric membrane containing 50 wt.% PAMAM dendrimer (0th generation) exhibited an excellent CO₂/H₂ selectivity of 500 with CO₂ permeability of 2.74 × 10⁻¹⁴ m³(STP)m/(m² s Pa) or 3.65 × 10³ barrer (1 barrer = 7.5 × 10⁻¹⁸ m³(STP)m/(m² s Pa)) when a mixture gas (CO₂/H₂: 5/95 by vol.) was fed at 25 °C and 100 kPa with 80% relative humidity. This polymeric materials are promising for a novel CO₂ separation membrane.