Sulfonated poly(ether ether ketone) composite membranes based on amino-modified halloysite nanotubes that effectively immobilize phosphotungstic acid

In this work, we prepared amino-modified halloysite nanotubes (PEI-DHNTs) via the co-deposition of self-polymerized dopamine and polyethylenimine (PEI) on the surface of nanotubes, which was confirmed by X-ray photoelectron spectroscopy (XPS) and Thermogravimetric analysis (TGA). A series of composite proton exchange membranes (PEMs) were prepared by incorporating PEI-DHNTs and phosphotungstic acid (HPW) into sulfonated poly(ether ether ketone) (SPEEK). It was found that both PEI-DHNTs and HPW were well dispersed in the polymer matrix, exhibiting excellent filler-matrix compatibility. The composite membranes demonstrated enhanced proton conductivity, reaching as high as 0.078 S cm⁻¹ with 33.3 wt.% HPW loading, which was ~90% higher than that of SPEEK control membrane. Such improvement was mainly attributed to the strong acid–base pairs formed by PEI-DHNT with both SPEEK and HPW, which shortened proton hopping distance and created more continuous proton conduction pathways. Furthermore, the membrane conductivity remained almost constant after 1 year's immersion in liquid water, indicating the successful immobilization of HPW in the composite membranes.     

Architectural control of polystyrene physical properties using branched anionic polymerization initiated at ambient temperature

Ambient temperature-initiated anionic polymerization has generated branched polystyrenes of varying molecular weights and architectures by inclusion of a distyryl branching comonomer into a conventional sec-Butylithium-initiated polymerization of styrene. Primary chain length control within the branched polymers, and restriction of the branching points to varying segments of the primary chains, led to variations of glass transition temperature with no direct correlation to the branched polymer molecular weight but a strong relationship to the length of individual chains comprising the branched macromolecules.     

Stereodivergent Desymmetrization of Simple Dicarboxylates via Branch-Selective Pd/Cu Catalyzed Allylic Substitution

Asymmetric desymmetrization has been demonstrated to be a powerful strategy for building stereocenters in asymmetric synthesis. Herein, a Pd/Cu catalyzed asymmetric desymmetrization reaction with a simple geminal dicarboxylate is reported. A wide scope of imino esters bearing an aryl or heteroaromatic group were compatible with this bimetallic catalytic system. The reactions proceeded smoothly, giving the desired products in good yields with high to excellent regio-, diastereo-, and enantioselectivity (up to 20 : 1 branched:linear, >20 : 1 dr, >99 % ee). Notably, the reaction favored branched selectivity, which is unusual for the Pd-catalyzed allylic alkylation reaction. In addition, the standard product could be easily transformed to other valuable molecules such as chiral allylic alcohols, carbamates, and organic boron compounds. Furthermore, DFT calculations were conducted to explain the origin of the branched selectivity.     

Polyethylenimine‐Based Nanogels for Biomedical Applications

Nanogels (NGs) are 3‐dimensional (3D) networks composed of hydrophilic or amphiphilic polymer chains, allowing for effective and homogeneous encapsulation of drugs, genes, or imaging agents for biomedical applications. Polyethylenimine (PEI), possessing abundant positively charged amine groups, is an ideal platform for the development of NGs. A variety of effective PEI‐based NGs have been designed and much effort has been devoted to study the relationship between the structure and function of the NGs. In particular, PEI‐based NGs can be prepared either using PEI as the major NG component or using PEI as a crosslinker. This review reports the recent progresses in the design of PEI‐based NGs for gene and drug delivery and for bioimaging applications with a target focus to tackle the diagnosis and therapy of cancer.     

Radical polymerization in the presence of peroxide and reducing agent monomer for branched polymers

In this article, we report the radical polymerization in the presence of peroxide and commercially available or designed reducing agent monomer (RAM) for the preparation of branched poly(methyl methacrylate)s (PMMAs). The reaction behavior of the RAM was studied by NMR. Triple‐detection SEC (TD‐SEC) analysis was used to confirm the branching structure of the prepared PMMAs and to investigate the influence of peroxide concentration and RAM concentration on molecular weight and branched structure. The obtained branched PMMAs exhibited high molecular weights and relatively narrow polydispersities at high conversion of MMA. Interestingly, a significant increase in molecular weight and degree of branching of the obtained polymers are observed in higher BPO concentration, these results are quite different from that reported in the literature. The unique radical polymerization mechanism in the RAM/BPO redox‐initiated radical polymerization system resulted in branched PMMAs with high molecular weights at relatively high RAM and BPO concentrations. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 833–840     

Optimal control problem in a domain with branched structure and homogenization

We consider a linear parabolic problem in a thick junction domain which is the union of a fixed domain and a collection of periodic branched trees of height of order 1 and small width connected on a part of the boundary. We consider a three‐branched structure, but the analysis can be extended to n‐branched structures. We use unfolding operator to study the asymptotic behavior of the solution of the problem. In the limit problem, we get a multi‐sheeted function in which each sheet is the limit of restriction of the solution to various branches of the domain. Homogenization of an optimal control problem posed on the above setting is also investigated. One of the novelty of the paper is the characterization of the optimal control via the appropriately defined unfolding operators. Finally, we obtain the limit of the optimal control problem. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis and Application of Low Molecular Weight PEI-Based Copolymers for siRNA Delivery with Smart Polymer Blends

Polyethylenimine (PEI) is a commonly used cationic polymer for small-interfering RNA (siRNA) delivery due to its high transfection efficiency at low commercial cost. However, high molecular weight PEI is cytotoxic and thus, its practical application is limited. In this study, different formulations of low molecular weight PEI (LMW-PEI) based copolymers polyethylenimine-g-polycaprolactone (PEI–PCL) (800 Da–40 kDa) and PEI–PCL–PEI (5–5–5 kDa) blended with or without polyethylene glycol-b-polycaprolactone (PEG–PCL) (5 kDa-4 kDa) are investigated to prepare nanoparticles via nanoprecipitation using a solvent displacement method with sizes ≈100 nm. PEG–PCL can stabilize the nanoparticles, improve their biocompatibility, and extend their circulation time in vivo. The nanoparticles composed of PEI–PCL–PEI and PEG–PCL show higher siRNA encapsulation efficiency than PEI–PCL/PEG–PCL based nanoparticles at low N/P ratios, higher cellular uptake, and a gene silencing efficiency of ≈40% as a result of the higher molecular weight PEI blocks. These results suggest that the PEI–PCL–PEI/PEG–PCL nanoparticle system could be a promising vehicle for siRNA delivery at minimal synthetic effort.     

长链支化聚丙烯的非线性流变行为

通过大幅振荡剪切试验方法, 研究了长链支化聚丙烯的非线性流变学行为, 揭示了长链支化结构与非线性黏弹响应的关系. 利用傅里叶变换流变学方法得到试样的三次倍频相对振幅I_3/1与应变的标度关系, 用于界定线性聚丙烯和长链支化聚丙烯非线性流变行为的差异, 并定义了非线性系数来量度长链支化程度. 在高应变下, I_3/1与应变的变化关系可以进一步描述长链支化在非线性流场下的特性, 并得到了长链支化程度与其非线性响应之间的变化关系. 通过应力波的Lissajous曲线分解, 发现了环内和环间黏弹性的差异, 长链支化结构在大应变流场下的非线性黏弹性响应弱于线性结构, 支化程度越高非线性响应越弱.     

Biodegradable and Biocompatible Silatrane Polymers

In this study, new biodegradable and biocompatible amphiphilic polymers were obtained by modifying the peripheral hydroxyl groups of branched polyethers and polyesters with organosilicon substituents. The structures of the synthesized polymers were confirmed by NMR and GPC. Organosilicon moieties of the polymers were formed by silatranes and trimethylsilyl blocks and displayed hydrophilic and hydrophobic properties, respectively. The effect of the ratio of hydrophilic to hydrophobic organosilicon structures on the surface activity and biological activity of macromolecules was studied, together with the effect on these activities of the macromolecules’ molecular weight and chemical structure. In particular, the critical micelle concentrations were determined, the effect of the structure of the polymers on their wetting with aqueous solutions on glass and parafilm was described, and the aggregation stability of emulsions was studied. Finally, the effect of the polymer structures on their antifungal activity and seed germination stimulation was examined.