ANIONIC SYNTHESIS OF A “CLICKABLE” MIDDLE-CHAIN AZIDE-FUNCTIONALIZED POLYSTYRENE AND ITS APPLICATION IN SHAPE AMPHIPHILES

"Click chemistry" is, by definition, a general functionalization methodology (GFM) and its marriage with living anionic polymerization is particularly powerful in precise macromolecular synthesis. This paper reports the synthesis of a "clickable" middle-chain azide-functionalized polystyrene (mPS-N3 ) by anionic polymerization and its application in the preparation of novel shape amphiphiles based on polyhedral oligomeric silsesquioxane (POSS). The mPS-N3 was synthesized by coupling living poly(styryl)lithium chains (PSLi) with 3-chloropropylmethyldichlorosilane and subsequent nucleophilic substitution of the chloro group in the presence of sodium azide. Excess PSLi was end-capped with ethylene oxide to facilitate its removal by flash chromatography. The mPS-N3 was then derived into a giant lipid-like shape amphiphile in two steps following a sequential "click" strategy. The copper(I)-catalyzed azide-alkyne cycloaddition between mPS-N3 and alkyne-functionalized vinyl-substituted POSS derivative (VPOSS-alkyne) ensured quantitative ligation to give polystyrene with VPOSS tethered at the middle of the chain (mPS-VPOSS). The thiol-ene reaction with 1-thioglycerol transforms the vinyl groups on the POSS periphery to hydroxyls, resulting in an amphiphilic shape amphiphile, mPS-DPOSS. This synthetic approach is highly efficient and modular. It demonstrates the "click" philosophy of facile complex molecule construction from a library of simple building blocks and also suggests that mPS-N3 can be used as a versatile "clickable" motif in polymer science for the precise synthesis of complex macromolecules.     

Synthesis and characterization of poly(ɛ-caprolactone-co-ethylene glycol) star-type amphiphilic copolymers by “click” chemistry and ring-opening polymerization

Abstract

The synthesis of poly(?-caprolactone-co-ethylene glycol) AAB star-type amphiphilic copolymers were carried out by use of a “click” chemistry reaction to block propargyl polyethylene glycol (propargyl-PEG) to terminally azide poly(?-caprolactone) (PCL-N₃). For this purpose, propargyl-PEG was synthesized by the reaction of PEGs (3000?Da, 2000?Da, 1500?Da, and 1000?Da) and propargyl chloride. Terminally chloride poly(?-caprolactone) (PCL-Cl) was carried out by means of ring-opening polymerization (ROP) of ?-caprolactone (CL) and 3-chloro-1,2-propanediol. Synthesis of PCL-N₃ was obtained by the chemical interaction of PCL-Cl and sodium azide. By reacting propargyl-PEG and PCL-N₃, the star-type amphiphilic copolymers were obtained. The characterization of products was accomplished by using multiple instruments including ¹H-NMR, FT-IR, GPC, TGA, contact angles, and elemental analysis techniques.     

Asymmetric “Janus” Biogel for Human-Machine Interfaces

Human-machine interfaces (HMIs) are essential for effective communication between machines and tissues. However, mechanical and biological mismatches, along with weak adhesion between rigid electronic devices and soft tissue, often cause unreliable responses and affect the signal recording of HMIs. In this study, an asymmetrical “Janus” biogel patch with one side firmly adhering to tissues, and the other surface having little adhesion and minimal interactions with surrounding environments has been developed. A series of analytical, mechanical, and electrical tests are performed to investigate the “Janus” biogel patch as a functional and biocompatible HMI. It is found that the gallic acid-modified gelatin adhesive surface on one side exhibits body temperature-dependent tissue adhesion, enabling low modulus and seamless skin contact. The other side is a tough gelatin/glycerol gel layer, which is thermally welded into the adhesive layer and functions as an encapsulant to prevent external interference due to adhesion. The encapsulation layer also exhibits a low friction coefficient when wet and proves to be a reliable alternative barrier to conventional encapsulation materials. The scientific insights and engineering principles revealed in this type of “Janus” biogel will be applicable to a broad range of biomedical applications, such as epidermal adhesive electrodes or skin-adhesive wearable devices.     

“Duet-Insurance” Eutectic Electrolytes for Zinc-Ion Capacitor Pouch Cells

Eutectic electrolytes are emerging to be explored to meet the high demand for aqueous zinc-ion capacitors (AZICs) due to their high electrochemical stability and environmental-friendly feature. Notably, a large-scale requirement for a practical AZIC has been addressed to balance decent performance and increase package size. Thus, a “duet-insurance” eutectic electrolyte (DIEE) is proposed by introducing successively heavy water (D₂O) and dimethyl sulfoxide in an aqueous chaotropic Zn salt solution, which hindered the severe irreversibility of Zn anodes compared to that lacking this dual-solvent protection. For example, the optimal DIEE delivered a high capacitance of 352.9 F g⁻¹ at 0.5 A g⁻¹ and excellent capacitance retention of ≈100% over 30,000 cycles at 2 A g⁻¹ implementing in pouch cells and showing the ability to operate at a low temperature. Besides, experimental (e.g., nuclear magnetic resonance spectroscopy, Raman spectroscopy, electric double-layer capacitance, etc.) and theoretical techniques (e.g., molecular dynamics simulation, density functional theory) illustrate the vital presence of contact ion pairs and aggregates ion species. Ultimately, this efficient DIEE system employing “duet-insurance” protections provides a promising direction for designing novel eutectic electrolytes for AZICs chemistries.     

Highly conductive oriented PEO-based polymer electrolytes

This contribution presents an overview of the study of the effect of stretching on semicrystalline and amorphous complexes of poly(ethylene oxide) (PEO) with different salts, such as lithium iodide, lithium trifluoromethane-sulfonate, lithium hexafluoroarsenate, lithium bis(oxalato)borate and lithium trifluoromethanesulfonimide. In spite of the conventional belief that ion transport in polymer electrolytes (PE) is mediated primarily by polymer segmental motion, we suggest that ion transport occurs preferentially along the PEO helical axis, at least in the crystalline phase. It was found that the more amorphous the PE, the less its lengthwise conductivity is influenced by stretching. It is suggested that the rate-determining step of ion conduction in semicrystalline LiX:P(EO)₂₀, polymer electrolytes below the melting point (T_m) is “interchain” hopping.     

国际象棋"马"数控车加工工艺实践

国际象棋棋子在数控车车削加工中,较为复杂的棋子造型是“马”。属于典型的异形类零件。本文在数控车加工中对其加工工艺、工装思路进行分析,重点对特殊外形零件的加工辅助夹具设计作实践探讨。     

Electrostimulated shift of the precipitation temperature of aqueous polyzwitterionic solutions

The precipitation temperature (T_pr) value of aqueous poly(dimethylamino-ethoxyacryloyl-propylsulphonate) (PDMAPS) solutions decreases with the rise of electric field intensity both in the absence and in the presence of a low molecular salt. This electrostimulated T_pr shift is explained qualitatively by means of the model taking into account both the dominating intermacromolecular dipole-dipole interaction and the dipole cluster formation.