An Endoplasmic Reticulum Targeting Type I Photosensitizer for Effective Photodynamic Therapy against Hypoxic Tumor Cells

Organelle-targeted type I photodynamic therapy (PDT) shows great potential to overcome the hypoxic microenvironment in solid tumors. The endoplasmic reticulum (ER) is an indispensable organelle in cells with important biological functions. When the ER is damaged due to the production of reactive oxygen species (ROS), the accumulation of misfolded proteins will interfere with ER homeostasis, resulting in ER stress. Here, an ER-targeted benzophenothiazine-based photosensitizer NBS-ER was presented. ER targeting modification significantly reduced the dark toxicity and improved phototoxicity index (PI). NBS-ER could effectively produce O₂⁻⋅ with near-infrared irradiation, making its phototoxicity under hypoxia close to that under normoxia. Meanwhile, the photoinduced ROS triggered ER stress and induced apoptosis. In addition, NBS-ER possessed excellent photodynamic therapeutic effect in 4T1-tumor-bearing mice.     

Highly alkaline stable anion exchange membranes from nonplanar polybenzimidazole with steric hindrance backbone

The anion exchange membranes (AEMs) with both high ionic conductivity and alkali stability are always the research focus of the AEM fuel cells. Here, a novel nonplanar polymer for AEMs manufacture, mPBI‐TP‐x‐R, with excellent hydroxide stability and satisfactory processability is reported for the first time. The serial mPBI‐TP‐x resins with steric hindrance were prepared by copolymerization among 3,3′,4,4′‐tetraaminobiphenyl, isophthalic acid and tetraphenyl‐terephthalic acid (TP) in different ratios under microwave condensation. The copolymers mPBI‐TP‐x were quaternized at N1/N3‐sites of benzimidazole unit in backbone with alkyl groups (R?CH₃, C₂H₅, n‐C₃H₇, or n‐C₄H₉) to prepare soluble ionomers, and the corresponding membranes in hydroxyl ion form were prepared by a solution casting method and subsequent ion‐exchange process. The chemical structure of all membranes was characterized using FTIR and ¹H NMR spectroscopy. The properties of ion exchange capacity, water uptake, swelling ratio, tensile strength, ionic conductivity, and alkaline stability were measured. Among the prepared membranes, the mPBI‐TP‐15%‐(n‐Bu) exhibited the excellent alkaline stability (only degradation ca. 5% under 1M NaOH aqueous solution at 60 °C for 800 h) and satisfactory OH^? conductivity (46.66 mS/cm at 80 °C). The current research provides a useful exploration to commercial application of alkaline fuel cell. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1087–1096     

ThH5: An Actinide-Containing Superhalogen Molecule

Thorium and its compounds have been widely investigated as important nuclear materials. Previous research focused on the potential use of thorium hydrides, such as ThH₂, ThH₄, and Th₄H₁₅, as nuclear fuels. Here, we report studies of the anion, ThH₅⁻, by anion photoelectron spectroscopy and computations. The resulting experimental and theoretical vertical detachment energies (VDE) for ThH₅⁻ are 4.09 eV and 4.11 eV, respectively. These values and the agreement between theory and experiment facilitated the characterization of the structure of the ThH₅⁻ anion and showed its neutral counterpart, ThH₅ to be a superhalogen. ThH₅⁻, which exhibits a C_4v structure with five Th−H single bonds, possesses the largest known H/M ratio among the actinide elements, M. The adaptive natural density partitioning (AdNDP) method was used to further analyze the chemical bonding of ThH₅⁻ and to confirm the existence of five Th−H single bonds in the ThH₅⁻ molecular anion.     

Template‐free anion‐controlled synthesis of Pd (II) nano‐aggregates for the antifouling polymerization of CO and ethylene

The reaction of [(domppp) Pd (OAc)₂] [domppp = 1,3‐bis (di‐o‐methoxyphenylphosphino)propane] and imidazolium‐functionalized carboxylic acids containing various anions (Br^?, PF₆^?, SbF₆^? and BF₄^?) resulted in the formation of nano‐sized Pd (II) aggregates under template‐free conditions. The rate of formation of aggregates can be modulated by changing the anion, affecting the rate of polymerization of CO and olefins without fouling. Herein, we describe the analysis of Pd (II) catalysts by dynamic light scattering, atomic force microscopy, X‐ray photoelectron spectroscopy and X‐ray crystallography, and co‐ and terpolymerization results including the catalytic activity, and bulk density and molecular weight of polymers.     

Acetate anion-selective encapsulation in the ellipsoidal cavity of symmetrical α,α′,δ,δ′-tetramethyl-cucurbit[6]uril

Four symmetrical α,α′,δ,δ′-tetramethyl-cucurbit[6]uril-based compounds have been prepared and characterised by X-ray crystallography. Their crystal structures displayed the acetate anion-selective encapsulating capability of symmetrical α,α′,δ,δ′-tetramethyl-cucurbit[6]uril. The host–guest interaction between the symmetrical α,α′,δ,δ′-tetramethyl-cucurbit[6]uril and the acetate anion in aqueous solution has also been observed by variable temperature ¹H NMR spectroscopy.     

Comb‐shaped guanidinium functionalized poly(ether sulfone)s for anion exchange membranes: Effects of the spacer types and lengths

A series of poly(ether sulfone)‐based anion exchange membranes (AEMs), tethering with guanidinium side chains with different spacers, were synthesized via azide‐alkyne cycloaddition, deprotection, and the subsequent ion exchange reactions. The designed polymer structures were verified by the ¹H NMR spectra. Because of the appropriate water uptake and formation of interconnected ionic clusters, the GPES‐3C with propyl spacer showed higher conductivity than the GPES‐1C and GPES‐9C, with methylene and nonyl spacers, respectively. Comparatively, the GPES‐EO AEM with two ethylene oxide (EO) spacers exhibited even higher conductivity, these can be interpreted by interconnectivity of ionic channels and hydrophilicity nature of the EO spacer. Additionally, although the GPES membranes displayed sufficient thermal stability, the chemical stability of as‐prepared materials needs to be much improved for fuel cell applications. Overall, these results demonstrated that the properties of “pendent‐type” AEM can be tuned facilely by the spacer types and lengths. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1313–1321     

钼酸根阴离子印迹陶瓷膜的制备与吸附性能

以三氧化二铝陶瓷膜为载体,以钼酸根阴离子为模板离子,1-乙烯基咪唑为功能单体,1,6-二溴己烷为交联剂,采用表面印迹和接枝聚合方法制备了能选择性吸附Mo(Ⅵ)的新型印迹陶瓷膜(IIP-PVI/CM).采用红外光谱、X射线光电子能谱、热重分析及扫描电子显微镜等方法对陶瓷膜进行结构表征.研究了pH值对吸附性能的影响,当pH值范围为2~4时,IIP-PVI/CM具有良好吸附能力;动力学和热力学结果表明,IIP-PVI/CM对Mo(Ⅵ)的吸附符合准二级动力学模型和Langmuir吸附模型;当pH=4.0和温度为30℃时,IIP-PVI/CM对Mo(Ⅵ)具有良好选择性,Mo(Ⅵ)对W(Ⅵ)的选择性系数高达7.48;动态吸附结果表明,IIP-PVI/CM对W(Ⅵ)和Mo(Ⅵ)的吸附饱和时间分别为24和47 min,饱和吸附量分别为0.163和0.672 mmol/100 g,动态吸附时IIP-PVI/CM亦具有良好选择性;经9次吸附与解吸后,IIP-PVI/CM对Mo(Ⅵ)吸附容量仍可达到初始值的92%,再生和循环使用性能良好.     

Responsive Gels with the Polymer Containing Alternating Naphthalene Diimide and Fluorinated Alkyl Chains: Gel Formation and Responsiveness as Well as Electrical Conductivity of Polymer Thin Films

A new electroactive polymer 1 with alternating NDI (naphthalene diimide) moieties and fluorinated alkyl chains was prepared and characterized. Gels of polymer 1 were formed in several solvents. Interestingly, gels of polymer 1 exhibited responsiveness toward N₂H₄, F^? and CN^?. Absorption and ESR spectroscopic studies revealed that such responsiveness is owing to the reduction of NDI moieties into the respective NDI^.?. In addition, thin films of polymer 1 were easily prepared with spin‐coating technique and the electrical conductivity of thin films reached 52.4 S/m after exposure to N₂H₄ vapor.