Oxygen-Binding Profile of the Iron Porphyrin Complex Embedded in Polymerized Liposome: Effect of the Polymerized Liposome on the Stability and the Oxygen-Binding Ability of the Iron Porphyrin Complex

5,10,15,20-Tetra(α,α,α,α, -o-(2′, 2′-dimethyl-20′-(2′ α-trimethylammonioethyl)phosphonatoxyeicosanamido)phenyl)porphinatoiron(II) (lipidheme) complex embedded in polymerized liposome was prepared by polymerizing l-(9-(p-vinylbenzoyl)nonanoyl)-2-O-octadecyl-rac-glycero-3-phosphocholine in the presence of lipid-heme under ultraviolet irradiation. The polymerization proceeded rapidly, and the reduction of the hemin to the heme occurred spontaneously during the polymerization. The lipid-heme complex embedded in the polymerized liposome bound molecular oxygen reversibly under physiological conditions (pH 7, 37°C) and was chemically, physically, and mechanically stable during storage for a long period and even in a high-speed flow system. The oxygen-binding affinity was not affected by the type of medium due to the effect of the rigid polymerized liposome.     

Ion Tunneling in Polymeric Solid Electrolytes for Batery and Electrochromic Display in the Dry State

Polymeric solid electrolytes which show bi-or single-ionic tunneling were prepared, and their unique ion conduction was applied for the design of some devices. Poly [(oligooxyethylene) methacrylatel] /MX hybrids and poly [(oligooxyethylene) methacrylate-co-methacrylic acid alkali metal salts] were prepared as typical models of those tunneling systems. These showed ionic conductivities above 10^?5 and 10^?7 S/cm at room temperature, respectively. An all-solid-state electrochromic display and a dry battery were prepared with these polymeric solid electrolytes. The all-solid-state electrochromic display showed excellent coloring and bleaching response by 1–3 V. The all-solid-state battery showed V _oc = 3.1 V stability for over 2 weeks. Their characteristics as well as their mechanism are also reported.     

Synthesis of green organogelators with a sulfide linkage via solvent-free Michael addition: soft templates for the preparation of size-controlled gold nanoparticles

Green organogelators with a sulfide linkage and free amino groups were synthesized via phase transfer catalysis using a N-benzylcinchonidinium bromide catalyst. Their self-assemblies in various common solvents were examined. These compounds exhibit high gelation ability especially in aromatic and highly polar solvents with a low critical gelation of 0.1 wt %. The organogels were analyzed by ¹H nuclear magnetic resonance (¹H NMR) and Fourier transfer-infrared spectroscopies (FT-IR), and their phase transition temperatures were determined by differential scanning calorimetry. The homogeneity of the gel networks was examined by field emission scanning electron microscopy and transmission electron microscopy (TEM). A lamellar structure was also confirmed by X-ray diffraction analysis. The organogels were employed as soft-templates for the in situ generation of stable gold nanoparticles dispersed in the gel matrix, and the resulting GNP dispersions were studied by ¹H NMR and UV–vis absorption. Transmission electron microscopy showed that GNPs assemble into a thin membrane-like structure.     

Room-Temperature Phosphorescence from a Series of 3-Pyridylcarbazole Derivatives

Exploration of pure metal-free organic molecules that exhibit strong room-temperature phosphorescence (RTP) is an emerging research topic. In this regard, unveiling the design principles for an efficient RTP molecule is an essential, but challenging, task. A small molecule is an ideal platform to precisely understand the fundamental role of each functional component because the parent molecule can be easily derivatized. Here, the RTP behaviors of a series of 3-pyridylcarbazole derivatives are presented. Experimental studies in combination with theoretical calculations reveal the crucial role of the n orbital on the central pyridine ring in the dramatic enhancement of the intersystem crossing between the charge-transfer-excited singlet state and the locally excited triplet states. Single-crystal X-ray crystallographic studies apparently indicate that both the pyridine ring and fluorine atom contribute to the enhancement of the RTP because of the restricted motion owing to weak C−H⋅⋅⋅N and H⋅⋅⋅F hydrogen-bonding interactions. The single crystal of the fluorine-substituted derivative shows an ultra-long phosphorescent lifetime (τ_P) of 1.1 s and a phosphorescence quantum yield (Φ_P) of 1.2 %, whereas the bromine-substituted derivative exhibits τ_P of 0.15 s with a Φ_P of 7.9 %. We believe that this work provides a fundamental and universal guideline for the generation of pure organic molecules exhibiting strong RTP.     

Synthetic Studies on Spirolides A and B: Formation of the Upper Carbon Framework Based on a Lewis Acid Template-Catalyzed Diels–Alder Reaction

The upper fragment of spirolides A and B, which are marine phycotoxins that exhibit strong antagonistic activities on nicotinic acetylcholine receptors, was constructed. The functionalized cyclohexene in spirolides was stereoselectively synthesized from the bicyclic lactone, which could be readily accessed by the Lewis acid template-catalyzed asymmetric Diels–Alder reaction of the pentadienol and methyl acrylate.     

A Nonenzymatic Kinetic Resolution of (±)-trans-2-Arylcyclohexanols via Esterification Using Polymer-Supported DCC,DMAP, and 3β-Acetoxyetienic Acid

A nonenzymatic kinetic resolution of (±)-trans-2-arylcyclohexanols was carried out by esterification using polymer-supported N,N′-dicyclohexylcarbodiimide (DCC), dimethylaminopyridine (DMAP), and 3β-acetoxyetienic acid. The efficiency of the kinetic resolution was comparable to the enzymatic method when arylcyclohexanols bearing a condensed-aromatic ring were used.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communication® to view the free supplemental file.     

Synthesis of Bis(phosphanyl)alkane Monosulfides by the Addition of Diphosphane Monosulfides to Alkenes under Light

Bis-phosphanated compounds are regarded as the most ubiquitous privileged ligand structures in transition-metal catalysis. The development of highly atom economical reactions is of great importance for their syntheses because less atom economical methods often require complicated purification procedures under inert atmospheres to remove excess starting materials and byproducts. Herein, the photoinduced addition reactions of diphosphane monosulfides bearing P^V(S)−P^III single bonds to alkenes is disclosed. These reactions require only equimolar amounts of the diphosphane monosulfide relative to the alkene and facilitate highly selective introduction of two different types of phosphorus-containing groups, such as thiophosphoryl and phosphanyl groups, into a variety of alkenes without any catalyst, base, or additive.     

Synthesis and Systematic Structural Analysis of Cationic Half-Sandwich Ruthenium Chalcogenocarbonyl Complexes

Although the chemistry of transition-metal complexes with carbonyl (CO) and thiocarbonyl (CS) ligands has been well developed, their heavier analogues, namely selenocarbonyl (CSe) and tellurocarbonyl (CTe) complexes remain scarce. The limited availability of such CSe and CTe complexes has so far hampered our understanding of the differences between such chalcogenocarbonyl (CE: E=O, S, Se, Te) ligands. Herein, we report the synthesis and properties of a series of cationic half-sandwich ruthenium CE complexes of the type [CpRu(CE)(H₂IMes)(CNCH₂Ts)][BAr^F₄] (Cp=η⁵-C₅H₅⁻; H₂IMes=1,3-dimesitylimidazolin-2-ylidene; Ar^F=3,5-(CF₃)₂C₆H₃). A combination of X-ray diffraction analyses, NMR spectroscopic analyses, and DFT calculations revealed an increasing π-accepting ability of the CE ligands in the order O<S<Se<Te. A variable-temperature NMR analysis of the thus obtained chiral-at-metal CE complexes indicated high stereochemical stability.     

Effects of graded porous structure on local strain distribution under compression in silicone rubber

Silicone rubber samples with gradually changing pore sizes within the range of 70–610 μm are produced using an improved spacer method. The samples are scanned using an X‐ray computed tomography to evaluate their graded structure as compared to uniform rubber. A compressive test reveals that graded porous silicone rubber has characteristic stress–strain curves whose slope changes within a specific strain range depending on the porous structure. Analysis results of local strain based on a digital image correlation of the graded porous silicone rubber under compression demonstrate that the characteristic stress–strain properties are caused by shifts in the main deformation region in the graded structure. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1033–1042