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RSC Advances · 2018 ·Vol. 8 ·期 28 ·15604-15612 · IF 2.936

Thermosensitive star polymer pompons with a core–arm structure as thermo-responsive controlled release drug carriers

Na Xu,Xiaobei Huang,Guangfu Yin,Meijiao Bu,Ximing Pu,Xianchun Chen,Xiaoming Liao,Zhongbing Huang

In contrast with traditional chemotherapy, controlled drug delivery systems provide many advantages. Herein, a thermosensitive star polymer pompon with a core–arm structure was synthesized using a grafting-on method as a thermo-responsive controlled release drug carrier. Single-chain cyclized/knotted poly tetra(ethylene glycol) diacrylate (polyTEGDA) was used as the hydrophobic core, and thermosensitive linear poly(N-isopropylacrylamide-co-N-methylolacrylamide) (poly(NIPAM-co-NMA)) was selected as the hydrophilic arm. Below or above its lower critical solution temperature (LCST), the linear poly(NIPAM-co-NMA) grafted onto the polyTEGDA core adopted a stretched or curled status, respectively, then the drug could be loaded in or extruded out. The LCST of star polyTEGDA-b-poly(NIPAM-co-NMA) was adjusted to slightly above body temperature (37 °C). The antitumor drug doxorubicin (DOX) was successfully loaded into the pompons with a high loading capacity of 19.45%. The cumulative release of DOX from loaded pompons in vitro for 72 hours was 71% and 20.7% at 42 °C and 37 °C, respectively, indicating that the excellent temperature-controlled release characteristics result from the unique thermo-responsive extrusion effect. Moreover, DOX loaded polyTEGDA-b-poly(NIPAM-co-NMA) pompons achieved better antitumor ability against ovarian carcinoma SKOV3 cells at 42 °C compared with that at 37 °C. These results suggest that star polyTEGDA-b-poly(NIPAM-co-NMA) pompons have considerable promise as thermo-responsive controlled drug delivery carriers.

研究领域: 生物材料学 · 药物递送系统 · 肿瘤治疗
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MACROMOLECULAR CHEMISTRY AND PHYSICS · 2017 ·Vol. 218 ·期 19 ·1700148 · IF 2.5

Spherical Compound Micelles with Lamellar Stripes Self-Assembled from Star Liquid Crystalline Diblock Copolymers in Solution

Pingping Wang,Shubo Cao,Yongbin Zhao,Tomokazu Iyoda,Aihua Chen

Detailed investigations on the self-assembly of amphiphilic star block copolymers composed of three-arm poly(ethylene oxide) (PEO) and poly(methacrylate) (PMAAz) with an azobenzene side chain (denoted as 3PEO- b -PMAAz) into stable spherical aggregates with clear lamellar stripes in solution are demonstrated. Four block copolymers, 3PEO 12 - b -PMA(Az) 33 , 3PEO 22 - b -PMA(Az) 31 , 3PEO 22 - b -PMA(Az) 62 , and linear PEO 68 - b -PMA(Az) 31 , are synthesized. The liquid crystalline properties of the block copolymers are studied by differential scanning calorimetry, polarized optical microscopy techniques, and wide-angle X-ray diffraction. The morphologies of the compound micelles self-assembled in tetrahydrofuran (THF)/water mixtures are observed by means of transmission electron microscopy and scanning electron microscopy. The size of the spherical micelles is influenced by the self-assembly conditions and the lengths of two blocks. The well-defined three-arm architecture of the hydrophilic blocks is a key structural element to the formation of stable spherical compound micelles. The micelle surface integrity is affected by the lengths of PEO blocks. The lamellar stripes are clearly observed on these micelles. This work provides a promising strategy to prepare functional stable spherical compound micelles self-assembled by amphiphilic block copolymers in solution.

研究领域: 材料科学 · 高分子化学
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POLYMER BULLETIN · 2014 ·Vol. 71 ·期 6 ·1331-1347 · IF 1.491

Synthesis and characterization of star polylactide by ring-opening polymerization of l-lactic acid O-carboxyanhydride

Yuan Mingwei,He Zhengguo,Li Hongli,Jiang Lin,Yuan Minglong

Ring-opening polymerization of l -lactic acid O -carboxyanhydride was catalyzed by 4-dimethylaminopyridine in the presence of polyols pentaerythritol (PER) or dipentaerythritol (DPE). A high yield and relatively high molecular weight of 4- or 6-arm star PLA were obtained. The reaction was observed to be conducted easily and controllably. NMR analysis revealed that the end of the star PLA chain is a hydroxyl group and the central core is a PER or DPE group. The crystallinity of star PLA is lower than that of linear PLA. The crystallinity of 4-arm star PLA is lower than that of 6-arm PLA. Compared with that of 4-arm star PLA, the molecular arrangement of 6-arm star PLA may be relatively more regular.

CAS / MDL: 1122-58-3 127-18-4
研究领域: 材料科学 · 高分子化学
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JOURNAL OF APPLIED POLYMER SCIENCE · 2014 ·Vol. 131 ·期 16 · IF 1.64

Star-shaped POSS–methacrylate copolymers with phenyl–triazole as terminal groups, synthesis, and the pyrolysis analysis

Xiu Qiang,Fang Chen,Xiao-Yan Ma,Xian-Bing Hou

Star-shaped polyhedral oligomeric silsesquioxane (POSS)–methacrylate hybrid copolymers with phenyl–triazole as terminal groups had been designed and synthesized via sequential atom transfer radical polymerization (ATRP), azidation, and phenylacetylene-terminated procedures, and the hybrid copolymers here could be denoted as POSS–(PXMA-Pytl) 8 , where X can be M, B, L, and S, represented four different methacrylate monomers, such as methacrylate (MMA), butyl methacrylate (BMA), lauryl methacrylate (LMA), and stearyl methacrylate (SMA), respectively. Thermal gravimetric analysis (TGA) and in situ Fourier transform infrared spectroscopy (FTIR) were applied for studying the thermal stability and degradation mechanism, and it was found that all of the POSS–(PXMA-Cl) 8 and POSS–(PXMA-Pytl) 8 copolymers exhibited excellent thermal stabilities, which had great potential in heat-resistant material application. Different tendencies of decomposition temperatures at 5% and 10% weight loss ( T 5 and T 10 ) dependent on the side-chain length and terminal group species were investigated respectively. The longer alkyl side chains of the monomers, the lower thermal stabilities, and enhanced T 5 and T 10 were also shown with the introduction of phenyl–triazole groups instead of chlorine groups. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131 , 40652.

研究领域: 聚合物化学 · 材料科学 · 热分析
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CHINESE JOURNAL OF POLYMER SCIENCE · 2016 ·Vol. 35 ·期 1 ·54-65 · IF 1.811

Synthesis of star polymeric ionic liquids and use as the stabilizers for high internal phase emulsions

Chen Qi-jing,An Ze-sheng

A series of well-defined core cross-linked star (CCS) polymeric ionic liquids (PILs) were synthesized via a three-step approach. First, the styrenic imidazole-based CCS polymer (S-PVBnIm) was prepared by the RAFT-mediated heterogeneous polymerization in a water/ethanol solution, followed by the quaternization of S-PVBnIm with bromoalkanes and anion exchange. The CCS polymers were characterized by gel permeation chromatography (GPC), nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). The obtained CCS polymers were used as the effective emulsifiers for oil-in-water high internal phase emulsions (HIPEs). Multiple oils with different polarity including n -dodecane, undecanol, toluene and octanol were emulsified using 0.5 wt% S-PVBnIm aqueous solution under the acidic condition to form HIPEs with long-term stabilities. The excellent emulsification properties of CCS PILs were demonstrated by HIPE formation for a variety of oils. The properties of HIPEs in terms of emulsion type and oil droplet size were characterized by the confocal laser scanning microscopy (CLSM). The intriguing capability of CCS PILs to stabilize HIPEs of various oils holds great potentials for the practical applications.

研究领域: 聚合物化学 · 材料科学 · 胶体与表面化学
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International Journal of Nanomedicine · 2015 · IF 4.383

Doxorubicin-loaded aromatic imine-contained amphiphilic branched star polymer micelles: synthesis, self-assembly, and drug delivery

Liang Qiu,Chun-Yan Hong,Cai-Yuan Pan

Redox-and pH-sensitive branched star polymers (BSPs), BP(DMAEMA-co-MAEBA-co-DTDMA)(PMAIGP)ns, have been successively prepared by two steps of reversible addition–fragmentation chain transfer (RAFT) polymerization. The first step is RAFT polymerization of 2-(N,N-dimethylaminoethyl)methacrylate (DMAEMA) and p-(methacryloxyethoxy) benzaldehyde (MAEBA) in the presence of divinyl monomer, 2,2′-dithiodiethoxyl dimethacrylate (DTDMA). The resultant branched polymers were used as a macro-RAFT agent in the subsequent RAFT polymerization. After hydrolysis of the BSPs to form BP(DMAEMA-co-MAEBA-co-DTDMA)(PMAGP)ns (BSP-H), the anticancer drug doxorubicin (DOX) was covalently linked to branched polymer chains by reaction of primary amine of DOX and aldehyde groups in the polymer chains. Their compositions, structures, molecular weights, and molecular weight distributions were respectively characterized by nuclear magnetic resonance spectra and gel permeation chromatography measurements. The DOX-loaded micelles were fabricated by self-assembly of DOX-containing BSPs in water, which were characterized by transmission electron microscopy and dynamic light scattering. Aromatic imine linkage is stable in neutral water, but is acid-labile; controlled release of DOX from the BSP-H-DOX micelles was realized at pH values of 5 and 6, and at higher acidic solution, fast release of DOX was observed. In vitro cytotoxicity experiment results revealed low cytotoxicity of the BSPs and release of DOX from micelles in HepG2 and HeLa cells. Confocal laser fluorescence microscopy observations showed that DOX-loaded micelles have specific interaction with HepG2 cells. Thus, this type of BSP micelle is an efficient drug delivery system.

CAS / MDL: 25316-40-9
研究领域: 材料科学 · 药学 · 生物医学工程
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Journal of Materials Chemistry B · 2015 ·Vol. 4 ·期 1 ·141-151 · IF 4.726

Unimolecular micelles of camptothecin-bonded hyperbranched star copolymers via β-thiopropionate linkage: synthesis and drug delivery

Liang Qiu,Qing Liu,Chun-Yan Hong,Cai-Yuan Pan

In order to develop pH- and redox-responsive unimolecular micelles composed of camptothecin (CPT)-conjugated hyperbranched star copolymers via acid-labile β-thiopropionate linkage, a new monomer, methacryloyloxy-3-thiohexanoyl–CPT, is synthesized through conjugation of CPT with methacrylate via β-thiopropionate linkage, and then used in synthesis of the CPT-conjugated hyperbranched star copolymers by two steps of atom transfer radical polymerization (ATRP): self-condensation vinyl polymerization of the CPT-based monomer, 2-hydroxypropyl methacrylate and inimer, and subsequent ATRP of oligo(ethylene glycol) methacrylate using the obtained hyperbranched polymers as the macroinitiator. The obtained polymers dissolve in water to form unimolecular micelles, and their release of CPT in water at various pHs and their anticancer efficacy are studied. The CPT-loaded unimolecular micelles with diameters of 3.56–6.08 nm are quite stable under neutral environment, and are easily triggered by mild acidic pH, such as 6.0 and 5.0. They can be easily internalized by the tumor cells, releasing the CPT. The CPT-conjugated unimolecular micelles via acid-labile β-thiopropionate linkage have potential for application as tumor-targeted drug release systems.

研究领域: 药物化学 · 高分子化学 · 肿瘤治疗学
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JOURNAL OF APPLIED POLYMER SCIENCE · 2016 ·Vol. 133 ·期 18 · IF 1.866

Synthesis, characterization, and cytotoxicity of star-shaped polyester-based elastomers as controlled release systems for proteins

Fangyuan Guo,Wei Zhang,Xiaohong Pei,Xia Shen,Qinying Yan,Weiyong Hong,Gensheng Yang

With the growing number of therapeutic proteins on the market, effective delivery systems are receiving particular attention. In this study, biodegradable elastomers, intended for protein drug delivery and based on methacrylic tripoly(ε-caprolactone- co - d , l -lactide) cyclic ester with different ratios of ɛ-caprolactone to d , l -lactide and methacrylic bipoly[ɛ-caprolactone- b -poly(ethylene glycol)- b -ɛ-caprolactone], were synthesized and characterized. The degradation behavior, bovine serum albumin (BSA)-releasing kinetics, and cytotoxicity of the elastomers in vitro were investigated. The elastomers were degraded by the hydrolysis of the ester bond; this resulted in pH changes, which further affected the degradation rate. The BSA-releasing behavior was strongly dependent on the diffusion mechanism. In the diffusion-controlled period, nearly sustained and stable BSA release was achieved. Furthermore, the elastomers displayed good biocompatibility, as demonstrated by a 3-(4,5-dimethyl thiazol-2-yl)−2,5-diphenyl tetrazolium bromide assay and inflammation–induction experiments, and are considered promising candidates for the controllable delivery of protein drugs. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133 , 43393.

研究领域: 生物材料 · 药剂学 · 生物医学工程
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JOURNAL OF FOOD COMPOSITION AND ANALYSIS · 2021 · IF 4.556

Molecular mechanisms of the irradiation-induced accumulation of polyphenols in star anise (Illicium verum Hook. f.)

Wei Jia,Yinghuan Yang,Shuxing Liu,Lin Shi

Irradiation technology has been shown to be a possible preservation technology used to prolong the shelf life and provide microbial decontamination of spices. In this study, the molecular mechanisms of the irradiation-induced accumulation of polyphenols in star anise were explored using metabolomics combined with ultra-high-performance liquid chromatography quadrupole-Orbitrap (UHPLC-Q-Orbitrap) high-resolution mass spectrometry. Fifty-six star anise samples from different areas processed with 2–10 kGy doses of irradiation were compared. The effect of post irradiation storage times ranging from 0 to 70 days was also evaluated. A total of 161 metabolites with variable importance on projection greater than 1 were characterized, and significant differences in flavonoid content in star anise were observed after irradiation. Absolute quantification was used for the quantification of distinctive compounds, and the limit of quantitation of the components was 1.90–6.53 μg/kg. The flavonoid content was stable on the 28th day of storage. The average content of flavonoids increased by 2–9 times due to the breaking of glycoside bonds in star anise by irradiation. C 15 H 11 O 7 + m/z 303.13045 and C 3 H 3 O 2 + m/z 71.01276 were defined as the characteristic fragments of flavonoids according to the mechanism of fragmentation. Checking the extraction ion chromatogram (EIC) characteristic fragments allows straightforward screening of untargeted flavonoids.

研究领域: 植物学 · 食品科学 · 分子生物学
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JOURNAL OF APPLIED POLYMER SCIENCE · 2019 ·Vol. 136 ·期 18 ·47458 · IF 2.188

Materials containing benzocyclobutene units with low dielectric constant and good thermostability prepared from star-shaped molecules

Xuelian Wei,Huan Hu,Xian Li,Qiang Yin,Li Fan,Yawen Huang,Junxiao Yang

With the development of ultralarge-scale integrated circuits, polymers with low dielectric constant and high thermal stability have aroused great interest. We prepared two novel bridged siloxane-based benzocyclobutene (BCB) star-shaped monomers, tetrakis[dimethyl siloxy-4-(1′,1′-dimethyl-1′-ethyl silicon)-benzocyclobutene] (TDSDES-BCB) and tetrakis(hexamethyl siloxane vinyl-benzocyclobutene) (THSV-BCB), and the corresponding resins were obtained by curing. The structures of TDSDES-BCB and THSV-BCB were confirmed by 1 H-NMR, 13 C-NMR, and 29 Si-NMR spectra and time-of-flight mass spectrometry analysis. The curing behavior of these monomers was investigated by Fourier transform infrared spectroscopy and differential scanning calorimetry. The dielectric constant of cured TDSDES-BCB is only 2.43 at 10 MHz (that of THSV-BCB is 2.46). In addition, these resins display high thermal stability: the 5 wt % weight loss temperature of cured TDSDES-BCB is about 467 °C (454 °C for THSV-BCB resin). The excellent low dielectric property is attributable to the free volume created by the star-shaped structure and crosslinked network structure of BCB after curing. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136 , 47458.

CAS / MDL: 18497-13-7
研究领域: 材料科学 · 高分子化学
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Materials Today Communications · 2023 · IF 3.8

Structure-property study of novel star-shaped block polycarboxylate superplasticizers prepared via ATRP in Portland cement

Jialin Li,Shanshan Zhou,Hao Pang,Yuewen Huang,Bin Wang

Star-shaped superplasticizers exhibited excellent dispersion performance on cement paste , but the molecular structure remained poorly controlled. This study develops three star-shaped block superplasticizers via atom transfer radical polymerization to investigate their effects on fluidity and early hydration in the Portland cement system. The three star-shaped block superplasticizers with acid to ether monomer ratio of 28, 36 and 100, are marked as SPCE-1, SPCE-2 and SPCE-3 respectively. Fluidity test shows that SPCE-1 and SPCE-3 with higher hydrodynamic radius exhibit better initial fluidizing effect than SPCE-2. Besides, there is competitive adsorption of SPCEs between the clinker phase and nano-ettringite in pore solution. SPCE-1 behaves best in fluidity retention due to the increase of adsorption amount over hydration time. A dispersion mechanism based on the extended-DLVO theory was proposed that SPCEs reduce hydrophobic interaction between cement grains and prevent agglomeration between cement grains and air bubbles.

研究领域: 材料科学 · 化学工程
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Processes · 2023 ·Vol. 11 ·期 12 ·3429 · IF 3.5

Functionalization of Violet Phosphorus Quantum Dots with Azo-Containing Star-Shape Polymer for Optically Controllable Memory

Fan Shu,Weilin Chen,Gang Liu

Quantum dots (QDs) are emerging as promising candidates for innovative memristive materials, owing to their distinct surface, quantum size, and edge effects. Recent research has focused on tailoring QDs with specific organic molecules to fine-tune charge transfer states between the host and grafted species, as well as enhancing their dispersibility and processability. Violet phosphorus (VP), a newly discovered two-dimensional phosphorus allotrope, offers excellent carrier dynamics, predictable modifiability, and superior oxidation resistance, making it a promising contender in this domain. In this study, we synthesized a rich azobenzene-containing star-shaped polymer diazonium salt (AzoSPD) to functionalize violet phosphorus quantum dots (VPQDs), with the dual objectives of enhancing organic dispersibility and introducing photo-switching capabilities. The synthesized AzoSPD–VPQDs exhibit intramolecular charge transfer characteristics under electrical stimuli of ambient conditions, displaying significant non-volatile rewriteable memory properties and a substantial switching ratio exceeding 2 × 103. Furthermore, the high resistance state (HRS) current can be enhanced by nearly 40 times under 465 nm illumination, enabling optoelectronic information sensing and storage within a single device. This work not only provides insights into enhancing the optoelectronic properties of QDs through functional organic molecular modification but also represents a pioneering exploration of the potential applications of VPQDs in novel memristors.Keywords:violet phosphorus quantum dots;star-shape polymer diazonium salt;memristor;charge transfer mechanism;photoelectric regulation

研究领域: 材料科学 · 纳米技术 · 光电材料
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