Visible‐Light‐Induced Trifluoromethylation of Isonitrile‐Substituted Methylenecyclopropanes: Facile Access to 6‐(Trifluoromethyl)‐7,8‐Dihydrobenzo[k]phenanthridine Derivatives

A new visible‐light‐induced trifluoromethylation of isonitrile‐substituted methylenecyclopropanes is developed. A range of substituted 6‐(trifluoromethyl)‐7,8‐dihydrobenzo[k]phenanthridine derivatives are readily furnished by this newly developed tandem reaction with moderate to good yields. This reaction allows the direct formation of two six‐membered rings and three new C?C bonds, including the C?CF₃ bond, under visible light irradiation.     

Thermal Decomposition Kinetics of Ginkgo biloba Leaves Polyprenol in Nitrogen Atmosphere

The nonisothermal decomposition kinetics of Ginkgo biloba leaves polyprenol (GBP) and cleaved situation of its chemical bond during thermal decomposition process were first investigated using thermogravimetric (TG) and TG‐FTIR technology. The results of thermal decomposition kinetics revealed that the nonisothermal decomposition mechanism of GBP corresponds to first‐order chemical reaction with n = 1, integral form g(a) = –ln(1 – a) and differential form f(a) = 1 – a. TG‐FTIR results demonstrated that absorbance of –CH₃, unsaturated C–H bond, =CH₂, accumulated C=C, –OH, and so on constantly increased with thermal decomposition reaction went on. In addition, storage life of GBP was also evaluated. These data could provide theoretical guidance for purification under high temperature and other thermal application of GBP.     

Extraordinary transport behavior of gases in isothermally annealed poly(4‐methyl‐1‐pentene) membranes

Poly(4‐methyl‐1‐pentene) (PMP) membranes were modified through isothermal annealing to investigate the change of their crystalline structure and rigid and mobile amorphous fractions (RAF and MAF), assuming a three‐phase model, affected the gas transport behavior. The crystalline structure was characterized by wide‐angle X‐ray diffraction (WAXD) and small‐angle X‐ray scattering (SAXS) techniques, and the free volume properties were analyzed by positron annihilation lifetime spectroscopy. Compared with the pristine membrane, the annealed membranes show higher crystallinity; the crystals undergo partial structural change from form III to form I. The lamellar crystal thickness, rigid amorphous fraction thickness, and long period in the lamellar stacks increase with crystallinity. The annealed PMP membranes exhibit higher permeability due to the increase in larger size free volumes in MAF and higher selectivity due to the increase in smaller size free volumes in RAF, respectively. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2368–2376     

Temperature‐dependent phase‐segregation behavior and antifouling performance of UV‐curable methacrylated PDMS/PEG coatings

Controllable phase segregation adjustment for immiscible polymer blends has always been tough, which hinders the development of amphiphilic antifouling coatings from more accessible blends. Herein, methacrylated poly(dimethylsiloxane) (PDMS‐MA) was synthesized and mixed with poly(ethylene glycol)methylether methacrylate (PEG‐MA). It was interestingly discovered that these PDMS‐MA/PEG‐MA blends displayed upper critical solution temperatures (UCST) due to thermo‐induced conformational change of PEG‐MA and the UCST changed with PDMS‐MA/PEG‐MA mass ratios. Micro‐/nano‐phase segregation, nanophase segregation, or homogenous morphology were therefore achieved. These PDMS‐MA/PEG‐MA blends with different mass ratios were UV‐cured under varying temperatures to fabricate coatings. Their surface morphology and wettability are readily adjusted by phase segregation. For the first time, highly hydrophilic surface was achieved for coatings with microphase segregation because of the exposure of PEG‐rich domains, which exhibited an enhanced protein resistance against bovine serum albumin (BSA). Anti‐bacterial performance (Shewanella loihica) was also observed for these PDMS/PEG coatings. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1612–1623     

NMR‐based analysis of the chemical composition of Japanese persimmon aqueous extracts

Japanese persimmon (Diospyros kaki L.) is recognized as an outstanding source of biologically active compounds relating to many health benefits. In the present study, NMR spectroscopy provided a comprehensive metabolic overview of Japanese persimmon juice. Detailed signal assignments of Japanese persimmon juice were carried out using various 2D NMR techniques incorporated with broadband water suppression enhanced through T₁ effects (BB‐WET) or WET sequences, and 26 components, including minor components, were identified. In addition, most components were quantitatively evaluated by the integration of signals using conventional ¹H NMR and BB‐WET NMR. This is the first detailed analysis combined with quantitative characterization of chemical components using NMR for Japanese persimmon. Copyright © 2015 John Wiley & Sons, Ltd.     

An Unprecedented Two‐Fold Nested Super‐Polyrotaxane: Sulfate‐Directed Hierarchical Polythreading Assembly of Uranyl Polyrotaxane Moieties

The hierarchical assembly of well‐organized submoieties could lead to more complicated superstructures with intriguing properties. We describe herein an unprecedented polyrotaxane polythreading framework containing a two‐fold nested super‐polyrotaxane substructure, which was synthesized through a uranyl‐directed hierarchical polythreading assembly of one‐dimensional polyrotaxane chains and two‐dimensional polyrotaxane networks. This special assembly mode actually affords a new way of supramolecular chemistry instead of covalently linked bulky stoppers to construct stable interlocked rotaxane moieties. An investigation of the synthesis condition shows that sulfate can assume a vital role in mediating the formation of different uranyl species, especially the unique trinuclear uranyl moiety [(UO₂)₃O(OH)₂]²⁺, involving a notable bent [O=U=O] bond with a bond angle of 172.0(9)°. Detailed analysis of the coordination features, the thermal stability as well as a fluorescence, and electrochemical characterization demonstrate that the uniqueness of this super‐polyrotaxane structure is mainly closely related to the trinuclear uranyl moiety, which is confirmed by quantum chemical calculations.