All solid-state battery with sulfur electrode and thio-LISICON electrolyte

A high-capacity type of all solid-state battery was developed using sulfur electrode and the thio-LISICON electrolyte. New nano-composite of sulfur and acetylene black (AB) with an average particle size of 1–10 nm was fabricated by gas-phase mixing and showed a reversible capacity of 900 mAh g⁻¹ at a current density of 0.013 mA cm⁻².     

Novel anion exchange membranes having fluorocarbon backbone: Preparation and stability

Anion exchange membranes with excellent durability were prepared by chemical modification of Nafion. The modification was achieved by transformation of the sulfonic acid group into quaternary ammonium group. Namely, Nafion membrane was first converted into an amide-type membrane. Reduction of the carbonxyl group to methylene followed by quaternarization with alkyl iodide resulted in the formation of an anion exchange membrane. The electric resistance of the resulting membranes depends on the equivalent weight of the starting membranes (4.4–6.0 Ω cm² in 0.5N NaCl). The characteristics of the membranes are the excellent stability toward chemical substances such as organic solvents, oxidizing agents, acids, etc. For example, the membranes are stable in aqueous saturated chlorine solution at 60°C for 1000 hr.     

[FeII(MeCN)4]2+(ClO4−)2 and [FeIIICl33] as Mimics for the Catalytic Centers of Peroxidase,Catalase and Cvtochrome P-450

Addition of [Fe^II(MeCN)²₄⁺(ClO⁻₄)₂ to solutions of hydrogen peroxide in dry acetonitrile (MeCN) catalyzes a rapid disproportionation of H₂O₂ via the initial formation of an adduct, [Fe^II(HOOH)↔Fe(O)(OH₂)]²⁺, which oxidizes a second H₂O₂ to dioxygen. This intermediate also cleanly oxidizes substituted hydrazines, alcohols, aldehydes, and thioethers by a two-electron process. The products for these H₂O₂ oxidations are consistent with those that result from catalase- and some peroxidase-catalyzed processes. In the same aprotic medium (MeCN) anhydrous Fe^IIICl₃ catalyzes the demethylation of N,N-dimethylaniline, the epoxidation of olefins, and the oxidative cleavage of 1-phenyl-1,2-ethanediol (and other 1,2-diols) by hydrogen peroxide. A mechanism is proposed in which an initial Lewis acid-base interaction of Fe^IIICl₃ with H₂O₂ generates a highly electrophilic Fe^III-oxene species as the reactive intermediate. For each class of substrate the products closely parallel those that result from their enzymatic oxidation by cytochrome P-450. Because of (a) the close congruence of products, (b) the catalytic nature of the Fe^IIICl₃/H₂O₂ reaction mimic, and (c) the similarity of the dipolar aprotic solvent (acetonitrile) to the proteinaceous lipid matrix of the biomembrane, the form of the reactive intermediate may be the same in each case. This is in contrast to the prevailing view that cytochrome P-450 acts as a redox catalyst to generate an Fe(V)-oxo species or an Fe(IV)-oxo cation radical as the reactive intermediate.     

Enzymatic Synthesis of 1‐Alkyl‐2‐hydroxy‐sn‐glycero‐2,3‐cyclic‐phosphate Using a Novel Lysoplasmalogen‐Specific Phopholipase D

Many phospholipase Ds (PLDs) are known to catalyze transphosphatidylation as well as hydrolysis of phospholipids. Transphosphatidylation of lysoplasmalogen (LyPls)‐specific phospholipase D (LyPls‐PLD), which catalyzes hydrolysis of ether lysophospholipids such as LyPls and 1‐hexadecyl‐2‐hydroxy‐sn‐glycero‐3‐phosphocholine (Lyso‐PAF), still remains unclear. This study aims to reveal the transphosphatidylation activity of LyPls‐PLD, that is, the production of cyclic ether lysophospholipid. The enzymatic reaction is conducted in a buffer system, and the reaction products of a novel LyPls‐PLD from Thermocrispum sp. are investigated using mass spectrometry (MS). MS analyses demonstrate the reaction products to consist of 100% 1‐hexadecyl‐2‐hydroxy‐sn‐glycero‐2,3‐cyclic‐phosphate (cLyPA) and choline from Lyso‐PAF; however, 1‐alkenyl‐2‐hydroxy‐sn‐glycero‐2,3‐cyclic‐phosphate from 1‐O‐1′‐(Z)‐octadecenyl‐2‐hydroxy‐sn‐glycero‐3‐phosphocholine and 1‐O‐1′‐(Z)‐octadecenyl‐2‐hydroxy‐sn‐glycero‐3‐phosphoethanolamine is not produced. These results are expected to help in elucidating the catalytic mechanism of LyPls‐PLD, that is, the rate‐limiting step, and indicate LyPls‐PLD to be useful for the one‐pot synthesis of cLyPA. Practical Applications: A novel phospholipase D, LyPls‐PLD, can exclusively synthesize cLyPA from Lyso‐PAF using a one‐step enzymatic reaction without an organic solvent. cLyPA could be expected to show bioactivities similar to those of cyclic phosphatidic acid, which promotes normal cell differentiation, hyaluronic acid synthesis, antiproliferative activity in fibroblasts, and inhibitory activity toward cancer cell invasion and metastasis.     

Local Epidermal Endocrine Estrogen Protects Human Melanocytes against Oxidative Stress,a Novel Insight into Vitiligo Pathology

As the outermost barrier of the body, skin is a major target of oxidative stress. In the brain, estrogen has been reported synthesized locally and protects neurons from oxidative stress. Here, we explored whether estrogen is also locally synthesized in the skin to protect from oxidative stress and whether aberrant local estrogen synthesis is involved in skin disorders. Enzymes and estrogen receptor expression in skin cells were examined first by quantitative real-time PCR and Western blot analyses. Interestingly, the estrogen synthesis enzyme was mainly localized in epidermal keratinocytes and estrogen receptors were mainly expressed in melanocytes among 13 kinds of cultured human skin cells. The most abundant estrogen synthesis enzyme expressed in the epidermis was 17β-hydroxysteroid dehydrogenase 1 (HSD17β1) localized in keratinocytes, and the most dominant estrogen receptor expressed in the epidermis was G protein-coupled estrogen receptor 1 (GPER1) in melanocytes. To investigate whether keratinocyte-derived estradiol could protect melanocytes from oxidative stress, cultured human primary epidermal melanocytes (HEMn-MPs) were treated with H₂O₂ in the presence or absence of 17β estradiol or co-cultured with HSD17β1 siRNA-transfected keratinocytes. Keratinocyte-derived estradiol exhibited protective effects against H₂O₂-induced cell death. Further, reduced expression of HSD17β1 in the epidermis of skin from vitiligo patients was observed compared to the skin from healthy donors or in the normal portions of the skin in vitiligo patients. Our results suggest a possible new target for interventions that may be used in combination with current therapies for patients with vitiligo.     

Reduced Claudin-12 Expression Predicts Poor Prognosis in Cervical Cancer

Background: Within the claudin (CLDN) family, CLDN12 mRNA expression is altered in various types of cancer, but its clinicopathological relevance has yet to be established due to the absence of specific antibodies (Abs) with broad applications. Methods: We generated a monoclonal Ab (mAb) against human/mouse CLDN12 and verified its specificity. By performing immunohistochemical staining and semiquantification, we evaluated the relationship between CLDN12 expression and clinicopathological parameters in tissues from 138 cases of cervical cancer. Results: Western blot and immunohistochemical analyses revealed that the established mAb selectively recognized the CLDN12 protein. Twenty six of the 138 cases (18.8%) showed low CLDN12 expression, and the disease-specific survival (DSS) and recurrence-free survival rates were significantly decreased compared with those in the high CLDN12 expression group. We also demonstrated, via univariable and multivariable analyses, that the low CLDN12 expression represents a significant prognostic factor for the DSS of cervical cancer patients (HR 3.412, p = 0.002 and HR 2.615, p = 0.029, respectively). Conclusions: It can be concluded that a reduced CLDN12 expression predicts a poor outcome for cervical cancer. The novel anti-CLDN12 mAb could be a valuable tool to evaluate the biological relevance of the CLDN12 expression in diverse cancer types and other diseases.     

Preparation of All Polyester‐Based Semi‐IPN Elastomers Containing Self‐Associative or Non‐Associative Guest Chains via Post‐Blending Cross‐Linking

Mechanical properties of semi‐interpenetrating polymer network (semi‐IPN) elastomers consisting of chemical networks and self‐associative/non‐associative guest chains are demonstrated. Amorphous low T_g polyesters with thiol side groups (PE‐SH) are first synthesized by melt polycondensation. PE‐SH are then converted to polyesters containing COOH side groups (PE‐COOH) and amide side groups (PE‐amide) through Michael addition reaction of thiol groups with acrylic acid and acrylamide, respectively. Homogeneous semi‐IPN elastomers are obtained by thermal cross‐linking for bulk mixtures of PE‐COOH and PE‐amide in the presence of diepoxy cross‐linkers, where COOH and epoxy groups are reacted to form chemical cross‐links while the amide units form self‐complementary hydrogen bonds. Another sample containing non‐associative chains is also prepared by using polyester with N,N‐dimethylamide units, instead of PE‐amide. Dynamic mechanical analysis reveals that guest chain incorporation systematically brings plateau modulus reduction and a unique relaxation with higher tan δ value depending on the fraction and nature of guest chains. Tensile properties are also affected by the fraction and nature of guest chains; the incorporation of hydrogen bonded chains are beneficial to enhance breaking elongation and toughness without the sacrifice of maximum stress. The knowledge found in this work will be thus beneficial for creating tough soft materials with damping applications.     

Quantitation of vitamin K in human milk

A quantitative method was developed for the assay of vitamin K in human colostrum and milk. The procedure combines preparative and analytical chromatography on silica gel in a nitrogen atmosphere followed by reversed phase high performance liquid chromatography (HPLC). Two HPLC steps were used: gradient separation with ultraviolet (UV) detection followed by isocratic separation detected electrochemically. Due to co-migrating impurities, UV detection alone is insufficient for identification of vitamin K. Exogenous vitamin K was shown to equilibrate with endogenous vitamin K in the samples. A statistical method was incorporated to control for experimental variability. Vitamin K₁ was analyzed in 16 pooled milk samples from 7 donors and in individual samples from 15 donors at 1 month post-partrum. Vitamin K₁ was present at 2.94±1.94 and 3.15±2.87 ng/mL in pools and in individuals, respectively. Menaquinones, the bacterial form of the vitamin, were not detected. The significance of experimental variation to studies of vitamin K in individuals is discussed.