Synthesis of a Pillar[5]arene with Both Hydroxyl and Methoxycarbonyl‐Methoxy Groups and Its Host‐Guest Complexation with a Bis(imidazolium) Salt

By the introduction of methoxycarbonyl‐methoxy groups and hydroxyl groups into a pillar structure, a pillararene entirely with two types of functional groups was successfully prepared, which can form a stable 1:1 complex with a bis(imidazolium) salt in CHCl₃/acetone solution (V:V=1:1).     

Modification of hydrophilic channels in Nafion membranes by DMBA: Mechanism and effects on proton conductivity

Modification of proton conductive channels (PCCs) in Nafion has been achieved with the assistance of 3, 4‐dimethylbenzaldehyde (DMBA). During annealing, ionic clusters develop from small isolated spheres (1.72 nm) to wide continuous channels (5.15 nm), and the crystallinity of Nafion/DMBA membranes is also improved from 17% to 32% as shown by X‐ray diffraction. Molecular dynamic simulation reveals that hydrogen bonding and hydrophobic interaction between DMBA and Nafion work synergistically to achieve better phase separation. The morphology–property relationship shows that, versus various PCCs width, the corresponding proton conductivities vary greatly from 0.079 to 0.139 S/cm at 80 °C. By carefully tuning the width of PCCs, the proton conductivity shows an improvement of 22–34% as compared with pristine Nafion. A significant enhancement on the maximum power density is achieved for the membrane electrode assembly on Nafion/DMBA‐8h (as high as 1018 mW/cm^?2), yielding an enhancement of 39% on pristine Nafion‐8h (730 mW/cm^?2). © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 52, 1107–1117     

Solvent‐Controlled Assembly of Aromatic Glutamic Dendrimers for Efficient Luminescent Color Conversion

A binary supramolecular system where self‐sorting and coassembly behavior can be switched by changing the solvent polarity is hereby reported. Glutamic dendron is separately conjugated with pyrene and naphthalimide luminophores through an alkyl spacer. The resulting structurally similar building units can self‐assemble into one‐dimensional micro/nanostructures with hexagonal and lamellar packing, respectively. Varying solvents from polar aqueous solution to nonpolar decane is evidenced to profoundly inverse the superchirality and switch self‐sorted assembly to coassembly of the two building blocks. The moisture sensitivity of the naphthalimide moiety is considered the primary driving force for the self‐sorting phenomenon in aqueous solution, resulting in inevitable hydration to repel its stacking with hydrophobic pyrene moiety. On the other hand, the naphthalimide unit can integrate segmentally with the pyrene unit in decane, greatly facilitating the nanofiber growth and supramolecular gel formation along with improved energy transfer efficiency between luminophores. As a result, the coassembly‐based thin films show efficient luminescent color conversion upon the UV light irradiation. This research presents a useful route for the fabrication of controllable solution‐processed light emitting devices from self‐assembled multicomponent systems.     

On the Lipschitz equivalence of self‐affine sets

Recently Lipschitz equivalence of self‐similar sets on has been studied extensively in the literature. However for self‐affine sets the problem is more awkward and there are very few results. In this paper, we introduce a w‐Lipschitz equivalence by repacing the Euclidean norm with a pseudo‐norm w. Under the open set condition, we prove that any two totally disconnected integral self‐affine sets with a common matrix are w‐Lipschitz equivalent if and only if their digit sets have equal cardinality. The main methods used are the technique of pseudo‐norm and Gromov hyperbolic graph theory on iterated function systems.     

Self‐emulsion polymerization of amphiphilic monomers—a green route to synthesis of polymeric nanoscaffolds

Self‐emulsion polymerization (SEP), a green route developed by us for the polymerization of amphiphilic monomers, does not require any emulsifier or an organic solvent except that the water‐soluble initiators such as 2,2′‐azobis[2‐(2‐imidazolin‐2‐yl)propane]dihydrochloride (VA‐044) and potassium persulfate (KPS) are only used. We report here the polymer nanoscaffolds from a number of amphiphilic monomers, which can be used for in situ encapsulation of a variety of nanoparticles. As a demonstration of the efficacy of these nanoscaffolds, the synthesis of a biocompatible hybrid nanoparticle (nanohybrid), prepared by encapsulating Fe₃O₄ magnetic nanoparticle (Fe₃O₄ MNPs) in poly(2‐hydroxyethyl methacrylate) in water, for MRI application is presented. The nanohybrid prepared following the SEP in the form of an emulsion does not involve the use of any stabilizing agent, crosslinker, polymeric emulsifier, or surfactant. This water‐soluble, spherical, and stable nanohybrid containing Fe₃O₄ MNPs of average size 10 ± 2 nm has a zeta potential value of ?41.89 mV under physiological conditions. Magnetic measurement confirmed that the nanohybrid shows typical magnetic behavior having a saturation magnetization (Ms) value of 32.3 emu/g and a transverse relaxivity (r2) value of 29.97 mM^?1 s^?1, which signifies that it can be used as a T2 contrast agent in MRI. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019     

市场需求信息不对称下的保兑仓融资风险控制策略

信息不对称风险广泛存在于保兑仓融资过程当中,本文运用Stackelberg博弈模型刻画融资系统成员关系,运用动态规划优化分析方法求解对应博弈均衡策略。总结出需求信息不对称的三种表现形式:信息造假,信息优势及信息隐匿,分析各类信息不对称情形对融资系统所造成影响,并相应提出实现信息显示功能的契约甄别机制。研究表明:零售商可从信息不对称中获取巨大信息优势,但对其他成员造成损害,其中信息隐匿对生产商损害程度更高;二部定价机制可实现信息甄别,但生产商须为之付出信息租金,造成效率损失;而合理参数设定下的二部定价加回购机制有助于进一步改进融资系统及各成员收益,甚至达到次协调状态,最终实现融资成员收益的帕累托改进。本研究对于控制供应链融资中的信息风险、改善融资效率提供了理论依据及决策参考。     

Sub‐5 nm Dendrimer Directed Self‐Assembly with Large‐Area Uniform Alignment by Graphoepitaxy

Directed self‐assembly (DSA) using soft materials is an important method for producing periodic nanostructures because it is a simple, cost‐effective process for fabricating high‐resolution patterns. Most of the previously reported DSA methods exploit the self‐assembly of block copolymers, which generates a wide range of nanostructures. In this study, cylinders obtained from supramolecular dendrimer films with a high resolution (<5 nm) exhibit planar ordering over a macroscopic area via guiding topographical templates with a high aspect ratio (>10) and high spatial resolution (≈20 nm) of guiding line patterns. Theoretical and experimental studies reveal that this property is related to geometrical anchoring on the meniscus region and physical surface anchoring on the sidewall. Furthermore, this DSA of dendrimer cylinders is demonstrated by the non‐regular geometry of the patterned template. The macroscopic planar alignment of the dendrimer nanostructure reveals an extremely small feature size (≈4.7 nm) on the wafer scale (>16 cm²). This study is expected to open avenues for the production of a large family of supramolecular dendrimers with different phases and feature dimensions oriented by the DSA approach.     

Effects of graft length and density of well‐defined graft polymers on the thermoresponsive behavior and self‐assembly morphology

A series of well‐defined thermoresponsive graft polymers with different lengths and graft densities, poly(glycidyl methacrylate)‐graft‐poly(N‐isopropylacrylate) (PGMA‐g‐PNIPAM), were successfully prepared by combination of controlled/living free radical polymerization and click chemistry. Effects of grafting length and density on the thermoresponsive behavior, aggregating mean diameter, and self‐assembly morphology are systematically investigated. The thermosensitive characteristics of graft polymers in aqueous solution prove that the length and graft density had positive co‐relationship with the lower critical solution temperature value and mean diameter of micelles as well as the size distribution, while the effect of graft length of polymers is more significant than that of density. Transmission electron microscopy analysis shows that the conformations of PGMA₄₅‐g‐PNIPAM₂₀ and PGMA₄₅‐g‐PNIPAM₄₆ with longer length and bigger grafting density in aqueous solutions are spherical nanoparticles with the increasing trend of the diameters, while that of PGMA₄₅‐g‐PNIPAM_{(73, 50%)} shows a spherical‐like morphology, which indicates that the graft length and density have a significant effect on the mean diameter of micelle but not on the self‐assembly morphology. These results reveal that to obtain desired thermoresponsive behavior and self‐assembly morphology of functional polymers, it is essential to design and fabricate the structure of graft polymers with proper length and graft density. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2442–2453     

Acrylate nanolatex via self‐initiated photopolymerization

The use of UV light to initiate emulsion polymerization processes is generally overlooked, whilst extensive literature exists on photocuring of monomer films. In this study, the unique potential of UV light to produce at ambient temperature polyacrylate latexes without initiator was exploited. Although radical initiators are utilized at low concentration, their cost, toxicity, and odor provide incentives for finding alternatives. Starting with concentrated (30 wt %) and low scattering acrylate miniemulsions (droplet diameter <100 nm), it was demonstrated that acrylate self‐initiation can promote an efficient and fast photopolymerization in micrometer‐scale reactor (spectrophotometric cell) and lab‐scale photoreactor. Herein, all kinetic, colloidal, and mechanistic aspects involved in the self‐initiation of acrylate miniemulsion were extensively examined to provide a complete picture. In particular, the effects of droplet size, initiating wavelength, optical path, and irradiance on the course of the polymerization were thoroughly discussed. A diradical self‐initiation pathway is the most likely mechanism. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1843–1853