PEG基功能化离子液体的脱硫性能

合成一系列含有长醚链的PEG基咪唑对甲苯磺酸盐(PEG基功能化离子液体), 检测其脱硫与再生性能, 并测定其脱硫过程中物性(密度、黏度和表面张力)变化。结果表明, PEG基功能化离子液体具有良好的脱硫与再生性能, 而且该离子液体的脱硫性能随醚链增长而增强, 20℃时SO₂与离子液体摩尔比达到5.51以上, 吸收的SO₂在80℃条件下可彻底解吸。由¹H NMR图谱和Raman光谱分析结果表明, PEG基咪唑功能化离子液体对SO₂的吸收为物理吸收。脱硫后的PEG基功能化离子液体密度增大, 表面张力减小, 黏度较脱硫之前显著降低。     

Poly(dopamine)-assisted preparation of star poly(ethylene glycol)-based coatings: A detailed study of their protein resistance and application in CE

In this study, a set of well-defined multiarm star copolymers, hyperbranched poly(ethylenimine)-graft-poly(ethylene glycol) (bPEI-g-PEG) with different PEG grafting ratios were synthesized. The star PEG-based coatings were then prepared by immobilizing the corresponding copolymers onto poly(dopamine) (PDA)-coated substrates. The chemical composition, hydrophilicity, surface topography, and thickness of the coatings were studied by X-ray photoelectron spectroscopy (XPS), water contact angle (WCA), atomic force microscopy (AFM), and variable angle spectroscopic ellipsometry (VASE), respectively. Furthermore, the surface PEG chain density of star PEG-based coating was evaluated quantitatively and compared with that of linear PEG-based coating. Our results showed that the amount of proteins (albumin from bovine serum, fibrinogen, and lysozyme) adsorbed on the star PEG-based coating as measured by surface plasmon resonance (SPR) was found to be dependent on the surface PEG chain density, which was controlled by the polymer incubation concentrations and PEG grafting ratios. Generally, the star-shaped PEG gave the surface with higher PEG chain density than linear ones and the amount of adsorbed proteins decreased with increasing surface PEG chain density. At last, the star PEG-based coating was successfully applied into the capillary inner surface for protein separation by capillary electrophoresis (CE).     

Solid–solid phase-change materials cross-linked by carbon quantum dots: Address leakage and high super-cooling degree simultaneously

Leakage and super-cooling are two main disadvantages of polyethylene glycol (PEG) when used as phase-change materials (PCMs) for thermal energy storage, which seriously restrict the practical applications of the materials. In this study, we employ carbon quantum dots (CQDs) as cross-linkers to fabricate PEG-based solid–solid PCMs, which not only address the leakage issue of PEG during melting process, but also have much lower super-cooling degree compared with PEG, exhibiting extraordinary thermal energy storage performance. CQDs serve as a heterogeneous nucleating agent in the crystal domains of these PEG-based PCMs according to the characterizations. Additionally, CQDs are also beneficial to the thermal stability of the PCMs. And these PEG-based PCMs have high phase-change enthalpies (94.4 J/g) and applicable phase-change temperatures (25–37°C), showing potential for thermal energy storage.     

Synthesis of sharply thermo and PH responsive PMA-b-PNIPAM-b-PEG-b-PNIPAM-b-PMA by RAFT radical polymerization and its schizophrenic micellization in aqueous solutions

Sharply thermo- and pH-responsive pentablock terpolymer with a core-shell-corona structure was prepared by RAFT polymerization of N-isopropylacrylamide and methacrylic acid monomers using PEG-based benzoate-type of RAFT agent. The PEG-based RAFT agent could be easily synthesized by dihydroxyl-capped PEG with 4-cyano-4-(thiobenzoyl) sulfanylpentanoic acids, using esterification reaction. This pentablock terpolymer was characterized by ¹H NMR, FT-IR, and GPC. The PDI was obtained by GPC, indicating that the molecular weight distribution was narrow and the polymerization was well controlled. The thermo- and pH-responsive micellization of the pentablock terpolymer in aqueous solution was investigated using ?uorescence spectroscopy technique, UV–vis transmittance, and TEM. The LCST of pentablock terpolymer increased (over 50 °C) compared to the NIPAM homopolymer (~32 °C), due to the incorporation of the hydrophilic PEG and PMA blocks in pentablock terpolymer (PNIPAM block as the core, PEG the block and the hydrophilic PMA block as the shell and the corona). Also, pH-dependent phase transition behavior shows at a pH value of about ~5.8, according to pKa of MAA. Thus, in acidic solution at room temperature, the pentablock terpolymer self-assembled to form core–shell–corona micelles, with the hydrophobic PMA block as the core, the PNIPAM block and the hydrophilic PEG block as the shell and the corona, respectively.     

PEG-based Polyplex Design for Gene and Nucleotide Delivery

Gene delivery is a multiple-step process which depends on the ability of a gene carrier to overcome several biological barriers and safely deliver a transgene to its target cells. Polymeric gene delivery systems, e. g., polyplexes, have emerged as a safe alternative to viral vectors. Poly(ethylene glycol) (PEG) conjugation is a common modification approach to provide polyplexes with prolonged circulation time and reduced toxicity, and to allow their accumulation in tumor tissue through the enhanced permeability and retention (EPR) effect. This review describes physicochemical properties related to the biological activity of PEG-based polyplexes, and approaches undertaken to promote a rational design for their in vivo applications.     

Separation selectivity of aqueous polyethylene glycol-based separation systems: DSC, LC and aqueous two-phase extraction studies

The distribution behavior of n-alcohols, ketones and nitroalkanes in aqueous liquid chromatography with a column packed with polyethylene glycol (PEG) gel, TSKgel Ether-250, was compared with that in aqueous two-phase systems (ATPSs) formed from PEG and Na₂SO₄ or (NH₄)₂SO₄. The plots of the distribution data obtained for the PEG gel system against those for the ATPS reveal that the separation selectivities exerted by the PEG gel system and the PEG-based ATPS are approximately the same. Differential scanning calorimetry studies on aqueous PEG solutions suggest that PEG polymer forms a hydration structure of which the composition is 50% (w/w) PEG or the hydration number per ethylene oxide is 2.4 and the separation selectivity of the PEG-water systems can be attributed to partition of solute compounds into the hydrated PEG polymer structure.     

A PEG-based biocompatible block catiomer with high buffering capacity for the construction of polyplex micelles showing efficient gene transfer toward primary cells

Nonviral gene vectors from synthetic catiomers (polyplexes) are a promising alternative to viral vectors. In particular, many recent efforts have been devoted to the construction of biocompatible polyplexes for in vivo nonviral gene therapy. A promising approach in this regard is the use of poly(ethylene glycol) (PEG)-based block catiomers, which form a nanoscaled core-shell polyplex with biocompatible PEG palisades. In this study, a series of PEG-based block catiomers with different amine functionalities were newly prepared by a simple and affordable synthetic procedure based on an aminolysis reaction, and their utility as gene carriers was investigated. This study revealed that the block catiomers carrying the ethylenediamine unit at the side chain are capable of efficient and less toxic transfection even toward primary cells, highlighting critical structural factors of the cationic units in the construction of polyplex-type gene vectors. Moreover, the availability of the polyplex micelle for transfection with primary osteoblasts will facilitate its use for bone regeneration in vivo mediated by nonviral gene transfection.     

Rationally designed curcumin laden glycopolymeric nanoparticles: Implications on cellular uptake and anticancer efficacy

Overexpression of glucose transport proteins (GLUTs) plays a pivotal role in the survival of cancer cells. Hence, targeting GLUTs receptors using glucose-based polymers can fill up the lacuna of cancer treatment by confining the dissemination and accumulation of chemotherapeutic drugs on cancer cells. The present study addressed the preparation of glycohomopolymer (PMG), PEG-based di- (PEG-b-PMG) and tri-block (PMG-b-PEG-b-PMG) polymers using atom transfer radical polymerization and their potential in the development of novel nanoparticulate drug delivery system. Curcumin-loaded glycopolymer nanoparticles were fabricated by nanoprecipitation method and investigated for various physicochemical parameters such as particle size, zeta potential, polydispersity index, drug loading, morphology, and dissolution profile. Homoglycopolymer nanoparticles exhibited lower average particle size (240.16 ± 21.41 nm), higher zeta potential (−28.72 ± 4.25 mV), and entrapment efficiency (74.61 ± 5.03%) compared to their block copolymer counterparts. Optimized formulation exhibited diffusion and dissolution-controlled drug release behavior. In vitro cell line studies demonstrated significantly superior cytotoxicity, clonogenic inhibitory and cellular uptake potential in MCF-7 cells besides receptor recognizing property of optimized curcumin nanoparticulate formulation compared to free curcumin. These findings elucidate that curcumin homoglucopyranoside nanocarriers can be a promising drug delivery option for effective management of breast cancer. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48954.     

Alternating Magnetic Field Controlled, Multifunctional Nano-Reservoirs: Intracellular Uptake and Improved Biocompatibility

Biocompatible magnetic nanoparticles hold great therapeutic potential, but conventional particles can be toxic. Here, we report the synthesis and alternating magnetic field dependent actuation of a remotely controllable, multifunctional nano-scale system and its marked biocompatibility with mammalian cells. Monodisperse, magnetic nanospheres based on thermo-sensitive polymer network poly(ethylene glycol) ethyl ether methacrylate-co-poly(ethylene glycol) methyl ether methacrylate were synthesized using free radical polymerization. Synthesized nanospheres have oscillating magnetic field induced thermo-reversible behavior; exhibiting desirable characteristics comparable to the widely used poly-N-isopropylacrylamide-based systems in shrinkage plus a broader volumetric transition range. Remote heating and model drug release were characterized for different field strengths. Nanospheres containing nanoparticles up to an iron concentration of 6 mM were readily taken up by neuron-like PC12 pheochromocytoma cells and had reduced toxicity compared to other surface modified magnetic nanocarriers. Furthermore, nanosphere exposure did not inhibit the extension of cellular processes (neurite outgrowth) even at high iron concentrations (6 mM), indicating minimal negative effects in cellular systems. Excellent intracellular uptake and enhanced biocompatibility coupled with the lack of deleterious effects on neurite outgrowth and prior Food and Drug Administration (FDA) approval of PEG-based carriers suggest increased therapeutic potential of this system for manipulating axon regeneration following nervous system injury.     

PTPFCBBMA-b-PEG-b-PTPFCBBMA amphiphilic triblock copolymer: Synthesis and self-assembly behavior

We present the synthesis and self-assembly behavior of a new semi-fluorinated amphiphilic triblock copolymer. A series of perfluorocyclobutyl aryl ether-based amphiphilic ABA triblock copolymer containing hydrophilic poly(ethylene glycol) segment as the middle block were synthesized by atom transfer radical polymerization (ATRP). ATRP of 4-(4′-p-tolyloxyperfluorocyclobutoxy)benzyl methacrylate was initiated by PEG-based bifunctional macroinitiators with different molecular weights to obtain the desired copolymers with narrow molecular weight distributions (M_w/M_n ≤ 1.30) and the number of perfluorocyclobutyl linkage can be tuned by the feed ratio and the conversion of the fluorine-containing methacrylic monomer. The critical micelle concentrations of these amphiphilic ABA triblock copolymers in aqueous media were determined by fluorescence probe technique. They could aggregate to form spherical and cylindrical micelles visualized by TEM with varying the content of hydrophobic segment.     

一种纤维用新型聚乙二醇固-固相变储能材料

根据固-固相变材料的性质与结构特点,通过分子设计合成出了一种新型的芳香族四羟基化合物——4,4'-二苯基甲烷二异氰酸甘油酯(MTE),同时以4,4'-二苯基甲烷二异氰酸酯(MDI)-MTE为硬段,以聚乙二醇为相变单元和软段,通过原位聚合法制备出了一种聚乙二醇固-固相变储能材料(P-PCM)。利用红外光谱、核磁共振光谱、差示扫描量热法、动态热机械分析法研究了P-PCM的结构、相变行为及热稳定性,表明了P-PCM是一种新型的性能优异的相变材料。由于材料的刚性、可熔融和可溶解性,适合于纤维与织物的加工使用。     

聚乙二醇定形相变材料的热稳定性

利用热重分析仪对不同分子量、不同支撑材料、不同配方的聚乙二醇(PEG)定形相变材料的热稳定性进行了分析。结果表明,机械加工方法有可能会对PEG分子链有破坏作用,PEG定形相变材料具有良好的热稳定性。随着PEG分子量的增加,PEG定形相变材料的热分解温度越来越高,热稳定性更好。活性炭颗粒(ACG)和膨胀石墨(EG)都会使PEG相变材料的热分解温度降低,热稳定性有所降低。随着PEG定形相变材料中支撑材料含量的增加,定形相变材料的热稳定性降低。     

Synthesis and aqueous solution properties of aliphatic double chain end-capped poly(ethylene glycol)

Summary A PEG-based amphiphilic polymer bearing two aliphatic double chain moieties was prepared. Its diluted aqueous solution properties were studied by viscometry, dye solubilization and rheology. At concentrations lower than (6–8)×10⁻³ g/mL ring-shaped macromolecules were formed due to intrachain hydrophobic interactions. At concentrations about (6–8)×10⁻³ g/mL a formation of "flower" type aggregates took place. 1,6-Diphenyl-1,3,5-hexatriene solubilization was used to prove the existence of hydrophobic domains and a critical aggregation concentration of 7×10⁻³ g/mL was determined. The peculiar viscosity profile and the rheopectic behavior of the amphiphilic polymer were attributed to the existence of aggregates and to a temporary network formation during deformation, respectively. Received: 13 February 2001/Revised version: 15 June 2001/Accepted: 15 June 2001     

Development of CO2-Philic Blended Membranes Using PIM–PI and PIM–PEG/PPG

Blending is a simple method through which one can effectively tailor new polymers exhibiting the properties of their parent ones. Because the original properties of polymers are maintained after blending, various studies have used these films as gas separation membranes. In this study, a new CO₂ separation membrane is developed by physically mixing a polymer of intrinsic microporosity (PIM) with high gas permeability, polyimide (PIM-PI), as the hard segment and CO₂-philic PIM-poly(ethylene glycol)/poly(propylene glycol), or PIM-PEG/PPG, as the soft segment. Prepared by adding 5 mol.% of PIM-PEG/PPG to PIM-PI, the blended membrane PPB-5, with a tensile strength of 54 MPa and 35.5% elongation at break, shows better mechanical properties than commercial high-performance polymer membranes developed for gas separation, PEG-based blended membranes, and corresponding copolymer membranes with similar compositions developed in a previous study. In addition, it shows high CO₂ permeability (1552.6 Barrer) and CO₂/N₂ selectivity (29.3) due to the well-developed microphase separation characteristics originating from the optimal two-component composition, and the gas separation performance is close to the Robeson (2008) upper bound.     

Injectable polyethylene glycol-laponite composite hydrogels as articular cartilage scaffolds with superior mechanical and rheological properties

In this study, injectable PEG-based hydrogels containing Laponite particles with mechanical and structural properties close to the natural articular cartilage are introduced. The nanocomposites are fabricated by imide ring opening reactions utilizing synthesized copolymers containing PEG blocks and nanoclay through a two-step thermal poly-(amic acid) process. Butane diamine is used as nucleophilic reagent and hydrogels with interconnected pores with sizes in the range of 100–250?µm are prepared. Improved viscoelastic properties compared with the conventional PEG hydrogels are shown. Evaluation of cell viability utilizing human mesenchymal stem cells determines cytocompatibility of the nanocomposite hydrogels.     

Bioorthogonal Peptide Enrichment from Complex Samples Using a Rink-Amide-Based Catch-and-Release Strategy

Uptake and processing of antigens by antigen presenting cells (APCs) is a key step in the initiation of the adaptive immune response. Studying these processes is complex as the identification of low abundant exogenous antigens from complex cell extracts is difficult. Mass-spectrometry based proteomics – the ideal analysis tool in this case – requires methods to retrieve such molecules with high efficiency and low background. Here, we present a method for the selective and sensitive enrichment of antigenic peptides from APCs using click-antigens; antigenic proteins expressed with azidohomoalanine (Aha) in place of methionine residues. We here describe the capture of such antigens using a new covalent method namely, alkynyl functionalized PEG-based Rink amide resin, that enables capture of click-antigens via copper-catalyzed azide-alkyne [2 + 3] cycloaddition (CuAAC). The covalent nature of the thus formed linkage allows stringent washing to remove a-specific background material, prior to retrieval peptides by acid-mediated release. We successfully identified peptides from a tryptic digest of the full APC proteome containing femtomole amounts of Aha-labelled antigen, making this a promising approach for clean and selective enrichment of rare bioorthogonally modified peptides from complex mixtures.     

Long-term stability of PEG-based antifouling surfaces in seawater

Poly(ethylene glycol) (PEG) is a hydrophilic polymer that has been extensively used in the biomedical and marine environment due to its antifouling properties. In the biomedical field, PEG has been successfully used to functionalize surfaces due to its resistance to cell and nonspecific protein adsorption. However, the long-term stability of PEG has limited its use in some areas. In the shipping industry, there is a great need for long-term solutions to keep the hulls of the ships fouling-free. The long-term stability of PEG in polydimethylsiloxane (PDMS) fouling-release coatings is studied here, in both accelerated laboratory tests and real seawater conditions. This article shows how PEG-based copolymers, which have been exposed in fouling-release coatings to real-life seawater conditions, are isolated and compared to those exposed to accelerated laboratory testing with successful results. The influence of the chemistry of the PEG compounds, the chosen laboratory degrading agents, and the possible degradation pathways and products are discussed.     

Interpenetrating hydrogel networks based on gelatin and polyacrylamide: Synthesis,swelling, and drug release analysis

Interpenetrating hydrogel network has been synthesized from gelatin and polyacrylamide by cross-linking with their respective cross-linking agents. The swelling behavior of this Interpenetrating polymer network (IPN) system was analyzed in water and in citric acid-phosphate buffer solution at various pH. The effect of temperature on swelling behavior of these gels has been analyzed by variation from 25 to 60°C at physiological pH. The drug release behavior of these gels was also analyzed with temperature variation at physiological pH. © 1994 John Wiley & Sons, Inc.     

Bending behavior of hydrogels composed of poly(methacrylic acid) and alginate by electrical stimulus

Interpenetrating polymer networks (IPNs) prepared from poly(methacrylic acid) (PMAAc) and sodium alginate (SA) exhibited electrical sensitive behavior. The swelling behavior of the PMAAc/SA IPN hydrogel was studied by immersion of the gel into aqueous HCl solutions at various concentrations and into various pH buffer solutions, and their responses to electric fields were also investigated. When swollen IPN hydrogel was placed between a pair of electrodes it exhibited bending behavior on application of an electric field, and showed stepwise bending behavior depending on the magnitude of the electrical stimulus. Copyright © 2004 Society of Chemical Industry     

Crosslinking of poly(ethylene glycol) with divalent metal salts of mono(hydroxyethyl) phthalate,anhydride, and bisepoxide

Poly(ethylene glycol)s (PEG) were crosslinked with divalent metal salts of mono(hydroxyethyl) phthalate, anhydride, and bisepoxide to give metal-containing cured rubbers. As the anhydride, hexahydrophthalic anhydride was used, and bisphenol A diglycidyl ether was the bisepoxide used. As for the physical properties of the cured rubbers obtained, the rubbers containing Mg showed much better physical properties than those containing Ca. In addition, the rubbers with high hard block contents and high overall crosslinking densities exhibited high tensile strength and Shore A hardness, and so did the rubbers having a high degree of crystallinity of the PEG soft block. The occurrence of crystallization became easy as the soft block length became longer and the soft block content became higher, or as the crosslinking density of the hard block became lower. The PEG-based rubbers showed much higher water absorption than the previously reported poly(propylene glycol)-based rubbers, due to the much higher hydrophilicity of the PEG block. Resistance to chemical attack and stress–relaxation are also discussed.