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Pharmaceutics · 2018 ·Vol. 10 ·期 4 ·230 · IF 3.746

Polypeptides Micelles Composed of Methoxy-Poly(Ethylene Glycol)-Poly(l-Glutamic Acid)-Poly(l-Phenylalanine) Triblock Polymer for Sustained Drug Delivery

Xingzheng Liu,Rongrong Fan,Boting Lu,Yuan Le

Methoxy-poly(ethylene glycol)-poly(l-glutamic acid)-poly(l-phenylalanine) triblock polymers with different architecture were synthesized as drug carrier to obtain sustained and controlled release by tuning the composition. These triblock polymers were prepared by ring opening polymerization and poly(ethylene glycol) was used as an initiator. Polymerization was confirmed by1H NMR, FT-IR and gel penetration chromatography. The polymers can self-assemble to form micelles in aqueous medium and their critical micelle concentrations values were examined. The micelles were spherical shape with size of 50–100 nm and especially can arranged in a regular manner. Sorafenib was selected as the model drug and the drug loading performance was dependent on the composition of the block copolymer. In vitro drug release indicated that the polymers can realize controlled and sustained drug release. Furthermore, in vitro cytotoxicity assay showed that the polymers were biocompatible and the drug-loaded micelles can increase toxicity towards tumor cells. Confocal fluorescence microscopy assays illustrated that the micelles can be uptaken quickly and release drug persistently to inhibit tumor cell growth.Keywords:methoxy-poly(ethylene glycol);polypeptide;methoxy-poly(ethylene glycol)-poly(l-glutamic acid)-poly(l-phenylalanine);micelles;drug delivery

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Journal of Cleaner Production · 2018 · IF 5.651

Dopamine functionalization for improving crystallization behaviour of polyethylene glycol in shape-stable phase change material with silica fume as the matrix

Yan Chen,Han Ding,Beifu Wang,Qian Shi,Junkai Gao,Zhixing Cui,Yechao Wan

A new shape-stable phase change material (PEG/Dop-SF) was developed by using biomimetic modification of silica fume (SF) with dopamine (Dop) as the supporting matrix (Dop-SF). Biomimetic modification with dopamine has many advantages, such as a lack of toxicity and pollution, mild conditions and easy operation, and could improve the crystallization behaviours of PEG molecules in the PEG/Dop-SF. Moreover, the DSC results shows that the phase change enthalpy of PEG/Dop-SF is higher than that of PEG/SF. When the poly-dopamine adhered to the SF , the o-dihydroxybenzene of the dopamine linked with the hydroxyl of the SF by hydrogen bonding, leading to the freeing of the imino groups of poly-dopamine; therefore, in the process of fixing PEG in Dop-SF, the free imino groups of the poly-dopamine combined with the hydroxyl of the PEG by hydrogen bonding. This mechanism is inferred to characterize the interaction between PEG and Dop-SF. According to the results of the DSC and TGA measurements, the PEG/Dop-SF exhibited favourable heat storage capacity and thermal stability properties.

CAS / MDL: 25322-68-3
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CHINESE JOURNAL OF POLYMER SCIENCE · 2015 ·Vol. 33 ·期 9 ·1283-1293 · IF 1.835

Synthesis of poly(butylene terephthalate)-poly(tetramethylene glycol) copolymers using terephthalic acid as starting material: A comparation between two synthetic strategies

Zhang Jun-wu,Liu Fei,Wang Jing-gang,Na Hai-ning,Zhu Jin

Poly(butylene terephthalate)-poly(tetramethylene glycol) (PBT-PTMG) copolymer is prepared with terephthalic acid (PTA) rather than its dimethyl ester (DMT) as starting material by a two-step melt polycondensation. This process includes the synthesis of PBT prepolymer from PTA with 1,4-butanediol (BDO) in the first step, followed by the synthesis of PBT-PTMG copolymer from PBT prepolymer with PTMG in the second step. The molecular weight, composition as well as thermal and mechanical properties of the products from the two-step melt polycondensation are compared with the properties of the PBT-PTMG from the traditional one-step melt polycondensation. When the PTMG content is low, there is only slight difference in molecular weight, composition, thermal and mechanical properties among PBT-PTMG copolymers obtained from these two methods. However, when the PTMG content is high, only the two-step strategy is able to give high molecular weight products, and the products have comparable thermal and mechanical properties with those from traditional one-step strategy using DMT as starting material.

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RSC Advances · 2015 ·Vol. 5 ·期 48 ·38382-38390 · IF 3.84

Smart cleaning cotton fabrics cross-linked with thermo-responsive and flexible poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-ethylene glycol methacrylate)

Q. Zhong,Y. Y. Chen,S. L. Guan,Q. S. Fang,T. Chen,P. Müller-Buschbaum,J. P. Wang

The smart cleaning ability of cotton fabrics is realized by cross-linking thermo-responsive random copolymer to the cotton. Poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-ethylene glycol methacrylate), denoted as P(MEO2MA-co-EGMA), is synthesized from 2-(2-methoxyethoxy)ethoxyethyl methacrylate (MEO2MA) and ethylene glycol methacrylate (EGMA) with a molar ratio of 17 : 3. Its dilute aqueous solution (1 mg mL−1) presents a lower critical solution temperature (LCST) of 38 °C. Furthering increase the solution concentration, the LCST shifts towards lower temperature. By applying citric acid as a cross-linker, P(MEO2MA-co-EGMA) is successfully immobilized onto cotton fabrics. The obtained cotton fabrics also possess thermo-responsive property with a LCST at 37 °C. The smart cleaning ability is confirmed by single fiber cleaning experiments using a confocal microscope. It is observed that the cleaning ability of the cotton with cross-linked P(MEO2MA-co-EGMA) can be prominently enhanced at low temperature (below LCST). In addition, due to the low glass transition temperature of P(MEO2MA-co-EGMA) (−26 °C), the polymer is in a gel state at room temperature and will not negatively impact fabric softness. P(MEO2MA-co-EGMA) is a promising candidate for preparing textiles with smart cleaning ability and great fabric hand.

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POLYMER INTERNATIONAL · 2014 ·Vol. 64 ·期 4 ·477-485 · IF 2.247

Development of shape memory polyurethane based on polyethylene glycol and liquefied 4,4′-diphenylmethane diisocyanate using a bulk method for biomedical applications

Funian Mo,Faxing Zhou,Shaojun Chen,Haipeng Yang,Zaochuan Ge,Shiguo Chen

In this study, a series of shape memory polyurethanes (SMPUs) were synthesized successfully by the bulk polymerization method from liquefied 4,4′-diphenylmethane diisocyanate (L-MDI), 1,4-butanediol (BDO) and polyethylene glycol (PEG). The influence of the hard segment content (HSC) on the structure, morphology, properties and biocompatibility of PEG based SMPUs (PEGSMPUs) was carefully investigated. The results show that a microphase separation structure composed of a semicrystalline soft phase and an amorphous hard phase is formed in the PEG6000/L-MDI/BDO system. Crystallization of the PEG soft segment is influenced by the hard segments. The PEG semicrystalline soft phase serves as a reversible phase while the L-MDI−BDO hard segment acts as physical netpoints. Finally, a cyclic tensile test shows that all PEGSMPUs have good shape recovery (e.g. above 80%), whereas good shape fixity can only be achieved when the HSC is less than 35 wt%. The Cell Counting Kit 8 assay also demonstrates that only PEGSMPUs containing less than 40 wt% HSC have low cytotoxicity. It is thus concluded that PEGSMPUs bearing both good shape memory effects and good biocompatibility can be used as shape memory materials for biomedical applications when the HSC is less than 35 wt%. © 2014 Society of Chemical Industry

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Biomed Research International · 2013 · IF 0

Novel 4-Arm Poly(Ethylene Glycol)-Block-Poly(Anhydride-Esters) Amphiphilic Copolymer Micelles Loading Curcumin: Preparation, Characterization, and In Vitro Evaluation

Li Lv,Yuanyuan Shen,Min Li,Xiaofen Xu,Mingna Li,Shengrong Guo,Shengtang Huang

A novel 4-arm poly(ethylene glycol)-block-poly(anhydride-esters) amphiphilic copolymer (4-arm PEG-b-PAE) was synthesized by esterization of 4-arm poly(ethylene glycol) and poly(anhydride-esters) which was obtained by melt polycondensation of α-, ω-acetic anhydride terminated poly(L-lactic acid). The obtained 4-arm PEG-b-PAE was characterized by 1H-NMR and gel permeation chromatography. The critical micelle concentration of 4-arm PEG-b-PAE was 2.38 μg/mL. The curcumin-loaded 4-arm PEG-b-PAE micelles were prepared by a solid dispersion method and the drug loading content and encapsulation efficiency of the micelles were 7.0% and 85.2%, respectively. The curcumin-loaded micelles were spherical with a hydrodynamic diameter of 151.9 nm. Curcumin was encapsulated within 4-arm PEG-b-PAE micelles amorphously and released from the micelles, faster in pH 5.0 than pH 7.4, presenting one biphasic drug release pattern with rapid release at the initial stage and slow release later. The hemolysis rate of the curcumin-loaded 4-arm PEG-b-PAE micelles was 3.18%, which was below 5%. The IC50 value of the curcumin-loaded micelles against Hela cells was 10.21 μg/mL, lower than the one of free curcumin (25.90 μg/mL). The cellular uptake of the curcumin-loaded micelles in Hela cell increased in a time-dependent manner. The curcumin-loaded micelles could induce G2/M phase cell cycle arrest and apoptosis of Hela cells.

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CHINESE JOURNAL OF CHEMICAL ENGINEERING · 2016 · IF 1.207

Preparation and shaping of solid acid SO42 −/TiO2 and its application for esterification of propylene glycol monomethyl ether and acetic acid

Zhixian Huang,Yixiong Lin,Ling Li,Changshen Ye,Ting Qiu

The solid acid SO 4 2   − /TiO 2 was prepared by immersion method and applied for synthesis of propylene glycol methyl ether acetate (PMA) through esterification reaction of propylene glycol monomethyl ether (PM) and acetic acid (HAc). The optimal catalyst preparation condition was determined by orthogonal analysis of parameters in a five-factor and four-level test. The obtained solid acid catalysts were characterized in detail by means of X-ray powder diffraction, thermogravimetry, pyridine adsorbed IR analysis, scanning electron microscopy, and BET surface area method. Synthesis of PMA was studied in this paper through experimental investigation of reaction conditions such as temperature, molar ratio of reactants, catalyst dosage and agitation speed. Based on its possible reaction mechanism, a pseudo-homogeneous kinetic model was established and its activation energies E a + and E a − , 65.68   ×   10 3   J·mol −   1 and 57.78   ×   10 3   J·mol −   1 , were estimated. To prepare shaped solid acid catalyst SO 4 2   − /TiO 2 , the shaping method of impregnation–shaping–impregnation was applied. The optimal molding formulation of solid acid catalyst, obtained from the orthogonal test, was found to be binder 7   wt.%, reinforcing agent 20   wt.%, pore forming material 2.5   wt.%, and lubricant 4   wt.%. The results of performance test of catalyst demonstrated that the shaped solid acid catalyst exhibited high activity and stability.

CAS / MDL: 64-19-7 13463-67-7
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POLYMER · 2016 · IF 3.586

Poly(lactic acid)/poly(ethylene glycol) supramolecular diblock copolymers based on three-fold complementary hydrogen bonds: Synthesis, micellization, and stimuli responsivity

Xiaohua Chang,Chenlei Ma,Guorong Shan,Yongzhong Bao,Pengju Pan

Thymine-terminated poly(lactic acid) (PLA-THY) and diaminotriazine-terminated poly(ethylene glycol) (PEG-DAT) are synthesized and they can form the supramolecular amphiphilic diblock copolymers in solution through the thymine/diaminotriazine complementary hydrogen bonding interactions. Such supramolecular copolymers self-assemble into the stimuli-responsive micelles in aqueous solution. Micelle size, crystalline state, stimuli responsibility, drug loading and release behavior of the supramolecular micelles can be readily tuned from the block length, stereostructure, homo and stereocomplex crystallizations of hydrophobic PLA blocks. The enantiomerically-mixed supramolecular copolymers with both poly( l -lactic acid) (PLLA) and poly( d -lactic acid) (PDLA) blocks assemble into the stereocomplexed micelles, while those having the isotactic PLLA (or PDLA) and atactic poly( d , l -lactic acid) (PDLLA) blocks form the homocrystalline and amorphous micelles, respectively. The stereocomplexed and amorphous micelles exhibit smaller size than their homocrystalline analogs, all of which are much larger than the micelles formed from the conventional covalently-bonded diblock copolymers. The supramolecular micelles are sensitive to the external stimuli such as pH and ion. The homocrystalline and stereocomplexed micelles undergo fast aggregation in the acidic and salted solutions due to the disassociation of complementary hydrogen bonds. The stereocomplexed micelles exhibit larger drug loading content and slower drug release rate than the amorphous and homocrystalline ones, because of the larger polymer/drug interactions and tighter chain packing inside the micelle cores.

CAS / MDL: 538-75-0
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RSC Advances · 2016 ·Vol. 6 ·期 74 ·70243-70250 · IF 3.289

Biodegradable thermal- and redox-responsive poly(L-glutamate) with Y-shaped oligo(ethylene glycol) side-chain and tunable phase transition temperature

Xiaohui Fu,Yinan Ma,Jing Sun,Zhibo Li

A series of poly(L-glutamate) bearing Y-shaped oligo(ethylene glycol)x (OEGx) side-chains (PPLG-g-EGx, x = 2, 3 and 4) were synthesized via a combination of ring opening polymerization (ROP) of γ-propargyl-L-glutamate N-carboxyanhydride (PLG-NCA) with thiol–yne photoaddition. The solubility of the polypeptides in water was firstly investigated. PPLG-g-EG3 and PPLG-g-EG4 were soluble in water and displayed fully reversible thermal-responsive behaviors. Additionally, the polypeptides showed redox-responsive properties along with the conformation associated water solubility due to the presence of thioether groups in the side-chains. In particular, the clouding points (CPs) of the polypeptides are highly tunable depending on the degree of polymerization (DP), the side-chain length, the polymer/salt concentration, and the degree of oxidation/reduction. The key feature of our design is the simultaneous incorporation of thermal-responsive OEG units and redox-responsive thioether linkages by one-step thiol–yne photoaddition, which allows for precisely tuning the phase transition temperature by both stimuli. This synthetic approach offers a facile and efficient way to prepare polypeptide-based biomaterials with highly tunable properties.

CAS / MDL: 24650-42-8 107-06-2
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JOURNAL OF NANOPARTICLE RESEARCH · 2017 ·Vol. 19 ·期 6 ·1-13 · IF 2.02

Co-delivery of doxorubicin and AS1411 aptamer by poly(ethylene glycol)-poly(β-amino esters) polymeric micelles for targeted cancer therapy

Zhang Ran,Wang Shi-Bin,Wu Wen-Guo,Kankala Ranjith Kumar,Chen Ai-Zheng,Liu Yuan-Gang,Fan Jing-Qian

Recently, targeted drug delivery systems (TDDS) have offered a great potential and benefits towards the anti-tumor drug delivery. In this work, we designed the TDDS using a biocompatible poly(ethylene glycol)-poly( β -amino esters) amphiphilic block copolymer (PEG-PAEs) synthesized by Michael addition polymerization for combinatorial therapy. Further, the chemotherapeutic agents’ doxorubicin (DOX) and AS1411 DNA aptamer (Apt) are encapsulated in the PEG-PAEs NPs (PDANs) for co-delivery therapeutics. PDANs have shown the monodisperse spherical shape, smooth surface with a net positive charge (average diameter—183.1 ± 27.2 nm, zeta potential—31.2 ± 6.3 mV), and good colloidal stability (critical micelle concentration of PEG-PAEs is about 6.3 μg/mL). The pH-sensitive PAEs endowed PDANs both pH-triggered drug release characteristics and enhanced endo/lysosomal escape ability, thus improving the localization and cytotoxicity of DOX. AS1411 Apt conjugated PDANs precisely targeted nucleolin and their uptake correlates to a significant activity enhancement only in tumor cells (MCF-7) but not in normal cells (MCF-10A). Thus, PDANs can be a very promising targeted drug delivery platform for effective breast cancer therapy. Scheme 1 Schematic illustration of the preparation and cellular uptake of targeted co-delivery system

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APPLIED SURFACE SCIENCE · 2017 · IF 3.387

Improved surface hydrophilicity and antifouling property of polysulfone ultrafiltration membrane with poly(ethylene glycol) methyl ether methacrylate grafted graphene oxide nanofillers

Haidong Wang,Xiaofei Lu,Xinglin Lu,Zhenghui Wang,Jun Ma,Panpan Wang

In this study, the GO-g-P(PEGMA) nanoplates were first synthesized by grafting hydrophilic poly (poly (ethylene glycol) methyl ether methacrylate) via surface-initiated atom transfer radical polymerization (SI-ATRP) method. A novel polysulfone (PSF) nanocomposite membrane using GO-g-P(PEGMA) nanoplates as nanofillers was fabricated. FTIR, TGA, 1 H NMR, GPC and TEM were applied to verify the successful synthesis of the prepared nanoplates, while SEM, AFM, XPS, contact angle goniometry and filtration experiments were used to characterize the fabricated nanocomposite membranes. It was found that the new prepared nanofillers were well dispersed in organic PSF matrix, and the PSF/GO-g-P(PEGMA) nanocomposite membrane showed significant improvements in water flux and flux recovery rate. Based on the results of resistance-in-series model, the nanocomposite membrane exhibited superior resistance to the irreversible fouling. The excellent filtration and antifouling performance are attributed to the segregation of GO-g-P(PEMGA) nanofillers toward the membrane surface and the pore walls. Notably, the blended nanofillers appeared a stable retention in/on nanocomposite membrane after 30   days of washing time. The demonstrated method of synthesis GO-g-P(PEGMA) in this study can also be extended to preparation of other nanocomposite membrane in future.

CAS / MDL: 919-30-2
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JOURNAL OF MEMBRANE SCIENCE · 2016 · IF 5.557

Structures and antifouling properties of polyvinyl chloride/poly(methyl methacrylate)-graft-poly(ethylene glycol) blend membranes formed in different coagulation media

Li-Feng Fang,Bao-Ku Zhu,Li-Ping Zhu,Hideto Matsuyama,Shuaifei Zhao

Two new amphiphilic copolymers poly(methyl methacrylate- graft -poly(ethylene glycol) methacrylate) (PMMA -g- PEG) are synthesized and blended into polyvinyl chloride (PVC) to prepare membranes in different coagulation media (water and ethanol) via the non-solvent induced phase separation method. The prepared membranes are characterized by X-ray photoelectron spectroscopy, proton nuclear magnetic resonance , scanning electron microscopy, atomic force microscopy and water contact angle measurement. Their separation performance and fouling resistance (by protein adsorption and foulant filtration) are also compared. It is found that the membrane hydrophilicity is significantly increased by blending amphiphilic copolymer due to the introduction of hydrophilic poly(ethylene glycol) (PEG) segments of the copolymer. The membranes formed in water have more desirable structures (i.e., smoother surfaces and higher porosity) and better performance (i.e., higher permeability and rejection to bovine serum albumin) compared with those formed in ethanol. The amphiphilic copolymer blended membranes formed in the water coagulation bath exhibit excellent antifouling properties, in particular, showing ~100% fouling reversibility. Therefore, blending amphiphilic copolymers and selecting water as the coagulation media can be effective strategies to develop high performance antifouling membranes.

CAS / MDL: 3326-32-7 25736-86-1
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