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DRUG DELIVERY · 2021 · IF 6.419

Star polyester-based folate acid-targeting nanoparticles for doxorubicin and curcumin co-delivery to combat multidrug-resistant breast cancer

Fangyuan Guo,Nan Yu,Yunlong Jiao,Weiyong Hong,Kang Zhou,Xugang Ji,Huixing Yuan,Haiying Wang,Aiqin Li,Guoping Wang,Gensheng Yang

Chemotherapeutic treatments are indispensable in the treatment of breast cancer. However, the emergence of multidrug-resistance, strong cell toxicity, and poor targeting selection has inhibited their clinical application. In this study, two synergistic drugs, doxorubicin (DOX) and curcumin (CUR), were co-administered to overcome multidrug resistance (MDR). Based on the characteristics of the tumor microenvironment, we developed folic acid-modified nanoparticles ((DOX + CUR)-FA-NPs) based on a star-shaped polyester (FA-TRI-CL) to enhance the tumor targeting selectivity and drug loading (DL) capacity. The (DOX + CUR)-FA-NPs displayed a characteristic spheroid morphology with an ideal diameter (186.52 nm), polydispersity index (0.024), zeta potential (–18.87 mV), and good entrapment efficiency (97.64%/78.13%, DOX/CUR) and DL (20.27%/11.29%, DOX/CUR) values. In vitro pharmacokinetic and pharmacodynamic experiments demonstrated that the (DOX + CUR)-FA-NPs were gradually released, and they displayed the highest cell apoptosis and cellular uptake in MCF-7/ADR cells. Additionally, in vivo results illustrated that (DOX + CUR)-FA-NPs not only displayed significant tumor targeting and anticancer efficacy, but also induced less pathological damage to the normal tissue. In summary, co-administered DOX and CUR appeared to reverse MDR, and this targeted combinational nanoscale delivery system could thus be a promising carrier for tumor therapies in the future.

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SEPARATION AND PURIFICATION TECHNOLOGY · 2018 · IF 3.927

Synthesis of a novel tunable lignin-based star copolymer and its flocculation performance in the treatment of kaolin suspension

Zuguang Liu,Xiang Lu,Junkang Xie,Bo Feng,Qiaoning Han

In current work, lignin-based multi-arm star copolymer phenolated kraft lignin-graft-poly (2-methacryloyloxyethyl) trimethyl ammonium chloride (PKL-g-PDMC) was designed and synthesized as a new kind of cationic flocculant via Steglich esterification of PKL and subsequent RAFT polymerization with DMC, and its flocculation performance in the removal of kaolin particles from simulated wastewater was evaluated. The star PKL-g-PDMCs with varying graft density and arm length of PDMCs chains were characterized by 1 H NMR, 31 P NMR, GPC and TGA. The effects of graft density and arm length, PKL-g-PDMC dosage, suspension pH and settling time on flocculating performance were investigated by measuring residual turbidity of the settled suspension. The treatment was effective, as demonstrated by 96.4% efficiency of turbidity removal. Above all, the chemical structure of the copolymers, including graft density and the arm length, can be designable and tunable by simply changing feeding ratios of Steglich esterification and subsequent RAFT polymerization, and thus the best flocculation performance can be obtained. This work provides a blueprint for the design, synthesis and use of novel lignin-based multi-arm star copolymers for wastewater treatment with tunable properties.

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NEW JOURNAL OF CHEMISTRY · 2019 ·Vol. 43 ·期 22 ·8517-8526 · IF 3.069

Preparation of functionalized star polymer nanoparticles by RAFT polymerization and their application in positionally assembled enzymes for cascade reactions

Zhiwu Chen,Hui Cao,Tianwei Tan

A well-defined functional star polymer nanoparticle was prepared using an “arm first” approach via RAFT polymerization. In this work, N-adamantylacrylamide and N-succinimidyl acrylate were copolymerized with N-isopropylacrylamide sucessfully. The obtained diblock copolymer regarded as an “arm” endowed the star polymer with multiple conjugate functions. By adjusting the amount of crosslinking agent, the size and polydispersity of the star polymer were controlled. With the star polymer as the scaffold, a sequential multi-enzyme system was constructed, where HRP was placed in the inner layer through covalent conjugation, and β-cyclodextrin-modified GOx was assembled in the outer layer through host–guest recognition. More interestingly, the activity of the enzyme modified by β-cyclodextrin was improved. In addition to the enhanced thermal stability, this multienzyme system also exhibited a reduced Km value (from 2.18 mM to 0.39 mM) and an excellent substrate affinity. The specificity constant (Kcat/Km) for GOx in the star polymer@HRP@GOx system was 1.7-fold higher than that of the free HRP with free GOx system. This strategy will promote the development of biocatalysis reactions and biosensors as a promising method.

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Journal of Materials Chemistry B · 2015 ·Vol. 3 ·期 27 ·5615-5628 · IF 4.726

Star-shaped poly(2-methyl-2-oxazoline)-based films: rapid preparation and effects of polymer architecture on antifouling properties

Chong Zhang,Songtao Liu,Lin Tan,Haikun Zhu,Yanmei Wang

Development of surfaces with antifouling properties is of great interest in biomedical applications. In this paper, the research was aimed at rapid preparation of poly(2-methyl-2-oxazoline)-based antifouling coating. We designed and synthesized a set of well-defined multiarm star copolymers hyperbranched poly(ethylenimine)-graft-poly(2-methyl-2-oxazoline) (PEI-g-PMOXA) with different PMOXA grafting ratios and chain lengths. The cytotoxicity of the polymer was tested and the PMOXA-based films were successfully deposited rapidly onto substrates via a simple one-step dopamine-assisted codeposition method. The effect of polymer architecture (linear PMOXA with different molecular weights, star PMOXA with different PMOXA grafting ratios and arm lengths) on deposited films with respect to their deposition kinetics, surface composition, wettability, morphology, cytotoxicity, and antifouling properties was investigated systematically. The antifouling properties of PMOXA-based films were found to be dependent on the surface PMOXA chain densities, which were controlled by the PMOXA grafting ratios and chain lengths. Moreover, the star PMOXA structures gave the surfaces with higher PMOXA chain densities and enhanced antifouling properties compared to the linear ones. Among the star copolymers, PEI-g(70)-PMOXA(5K)/polydopamine and PEI-g(70)-PMOXA(7K)/polydopamine deposited films showed the highest resistance to protein adsorption (96–99% relative to the bare gold surface) and cell attachment (97–99% relative to the bare glass surface), as well as complete inhibition against platelet adhesion. At last, the stability test results showed that the PMOXA-based film exhibited superior stability in long-term applications than the poly(ethylene glycol)-based film.

CAS / MDL: 822-06-0
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Polymer Chemistry · 2015 ·Vol. 6 ·期 12 ·2192-2203 · IF 5.52

Tuning multiple arms for camptothecin and folate conjugations on star-shaped copolymers to enhance glutathione-mediated intracellular drug delivery

Yun Zhang,Maohua Chen,Xiaoming Luo,Hong Zhang,Chaoyu Liu,Huiyan Li,Xiaohong Li

Micelle behaviors have been studied intensively for linear block copolymers, and amphiphilic polymers with a non-linear architecture, including star polymers, dendrimers, and hyperbranched polymers are showing advantages in the loading of anticancer drugs. In the current study, multiarmed amphiphilic copolymers with drug conjugates were developed for the construction of micelles to alleviate premature drug release during circulation and to achieve glutathione (GSH)-mediated intracellular drug delivery. Folic acid (FA) was grafted on some of the arms of 4-armed poly(ethylene glycol) (4-arm-PEG) as the targeting groups of micelles, and ε-caprolactone (ε-CL) was copolymerized with PEG from the rest of the arms, followed by camptothecin (CPT) conjugation through dithiodipropionic acid. The effect of the number of arms used for FA conjugation and the length of PCL blocks on micelle properties, reductive sensitivity, cellular uptake, and antitumor activities were evaluated. The amphiphilic copolymers with star-shaped miktoarms were self-assembled into micelles with an average size of around 100 nm and critical micelle concentrations (CMCs) as low as 0.8 μg mL−1. The distribution of hydrophobic PCL segments in more arms resulted in micelles with lower CMCs, higher structural stability, and greater sensitivity of CPT release in the presence of GSH. But, the conjugation of FA on fewer arms led to lower FA densities and less efficient cellular uptake of the micelles. In view of the performance of cellular uptake, CPT loading, and reduction-sensitive release, micelles from 4-armed copolymers with FA conjugation on two arms and PCL copolymerization on another two arms resulted in the most significant antitumor activities. It is suggested that the composition and arm structure of amphiphilic copolymers with star-shaped miktoarms show significant effects on micelle behavior, and optimal antitumor activities can be achieved through judicious selection of multiple arms for conjugating targeting groups and chemotherapeutic drugs.

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JOURNAL OF APPLIED POLYMER SCIENCE · 2015 ·Vol. 132 ·期 27 · IF 1.768

Synthesis and characterization of star-shaped PLLA with sorbitol as core and its microspheres application in controlled drug release

Lijing Teng,Wangyan Nie,Yifeng Zhou,Linyong Song,Pengpeng Chen

The purpose of this study was to investigate the suitability of a six-arm star-shaped poly( l -lactide)s (s-PLLA) as controlled drug carriers for hydrophobic drug molecules. First, s-PLLA was synthesized by ring-opening polymerization of l -lactide using sorbitol as initiator and stannous octoate as catalyst. The structure and molecular weight ( M w ) of s-PLLA was characterized with 1 H NMR, 13 C NMR, and GPC. Second, rifampicin (RIF) used as a model drug was encapsulated within the microspheres of s-PLLA via oil-in-water emulsion/solvent evaporation technique. The morphology, drug encapsulation efficiency (EE), and in vitro release behavior of the prepared microspheres were studied in details. Results indicated that the average diameters of s-PLLA microspheres can be controlled between 8 and 20 µm by varying the copolymer's concentration or M w . The EE of RIF was mainly determined by the concentration of s-PLLA. The in vitro study showed that the burst release behavior can be depressed by increasing the M w of the s-PLLA. Present work suggests that the synthesized s-PLLA could be used as a new material for drug delivery. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132 , 42213.

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ELECTROCHIMICA ACTA · 2014 · IF 4.086

Preparations and characterizations of tunable and multicolored electrochromic copolymers derived from a novel star-shaped monomer and BEDOT-V

Kai Wang,Wenge Yang,Yonghong Hu,Yumei Kai,Ying Shi

A novel star-shaped monomer 1,3,5-Tri[2-(3,4-ethylenedioxythien-2-yl)vin-1-yl]benzene (TEDOT-V-B) was synthesized by Wittig coupling reaction. The copolymers with BEDOT-V at different feed ratios were prepared onto the ITO-coated glass by cyclic voltammetry (CV) method and the electrochromic properties were reported. The influences of different feed ratios on the spectroelectrochemical and kinetic properties were investigated. Spectroelectrochemical studies indicated that the maximum absorption wavelengths of the copolymer films bathochromically shifted with feed ratios. In addition, the copolymers had tunable and low band gaps. When the feed ratio of BEDOT-V-B/BEDOT-V was 1:3, the copolymer film showed the fastest oxidation switching time of 0.9s (567   nm) and 0.9s (967   nm) and the fastest reduction switching time of 0.8s (567   nm) and 0.9s (967   nm). Compared with PBEDOT-V, the copolymers showed tunable and multicolored electrochromism through feed ratios and the RGB colors were achieved. Additionally, the surface morphology of the copolymer film was investigated by scanning electron microscope (SEM).

CAS / MDL: 7791-03-9 7646-69-7
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Soft Matter · 2016 ·Vol. 12 ·期 8 ·2473-2480 · IF 3.798

Understanding the thermosensitivity of POEGA-based star polymers: LCST-type transition in water vs. UCST-type transition in ethanol

Lei Hou,Qijing Chen,Zesheng An,Peiyi Wu

The lower critical solution temperature (LCST) transition in water and the upper critical solution temperature (UCST) transition in ethanol of poly(oligo(ethylene glycol) acrylate) (POEGA)-based core cross-linked star (CCS) polymers have been investigated and compared by employing turbidity, dynamic light scattering (DLS), 1H NMR and FTIR measurements. Macroscopic phase transitions in water and in ethanol were observed to occur when passing through the transition temperature, as revealed by DLS and turbidity measurements. Analysis by IR indicated that the interactions between the polymer chains and solvent molecules in water are stronger than those in ethanol such that the CCS polymer arm chains in water adopt more extended conformations. Moreover, hydrophobic interaction among the aliphatic groups plays a predominant role in the LCST-type transition in water whereas weak solvation of the polymer chains results in the UCST-type transition in ethanol. Additionally, the LCST-type transition in water was observed to be much more abrupt and complete than the UCST-type transition in ethanol, as suggested by 1H NMR and IR at the molecular level. Finally, an abnormal “forced hydration” phenomenon was observed during the LCST transition upon heating. This study provides a detailed understanding of the subtle distinctions between the thermal transitions of CCS polymers in two commonly used solvents, which may be useful to guide future materials design for a wide range of applications.

CAS / MDL: 7789-20-0 1514-82-5
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APPLIED SURFACE SCIENCE · 2016 · IF 3.15

Amino-functionalized alkaline clay with cationic star-shaped polymer as adsorbents for removal of Cr(VI) in aqueous solution

Yuanfeng Pan,Pingxiong Cai,Madjid Farmahini-Farahani,Yiduo Li,Xiaobang Hou,Huining Xiao

Pentaerythritol (PER) was esterified with 2-bromoisobutyryl bromide to synthesize a four-arm initiator 4Br-PER for atom transfer radical polymerization (ATRP). Star-shaped copolymers (P(AM- co -DMAEMA) 4 , CSP) were prepared via ATRP using dimethyl aminoethyl methacrylate (DMAEMA) and acrylamide (AM) as comonomers, while Br-PER and CuBr/2,2′-bipyridine (BPY) as the initiator and the catalyst, respectively. The resulting four-arm initiator and star-shaped polymer (CSP) were characterized with FT-IR, 1 H NMR and Ubbelohde viscometry. Alkaline clay (AC) was immobilized with CSPs to yield amino groups, and the cationic star polymer-immobilized alkaline clay (CSP-AC) was applied to remove Cr(VI) from the aqueous solution in batch experiments. Various influencing factors, including pH, contact time and immobilization amount of CSP on adsorption capacity of CSP-AC for Cr(VI) were also investigated. The results demonstrated that Cr(VI) adsorption was highly pH dependent. The optimized pH value was 4.0. The adsorption isotherms of the adsorbent fit the Langmuir model well, with the maximum adsorption capacity of 137.9   mg/g at 30   °C. The material should be a promising adsorbent for Cr(VI) removal, with the advantages of high adsorption capacity.

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ELECTROCHIMICA ACTA · 2017 · IF 4.798

Ordered mesogenic units-containing hyperbranched star liquid crystal all-solid-state polymer electrolyte for high-safety lithium-ion batteries

Shi Wang,Ailian Wang,Xu Liu,Hao Xu,Jie Chen,Liaoyun Zhang

Functional liquid crystal polymers have attracted much attention as new all-solid-state polymer electrolytes due to their ability of orientation. In this paper, a hyperbranched star liquid crystal polymer (HSLCP) electrolyte for lithium-ion batteries (LIBs) is developed for the first time. This type of HSLCP bears a hyperbranched poly(glycidol) (HPG) as core, poly-ε-caprolactone (PCL) and poly (4-cyano-biphenyl methylmethacrylate) ((LC) x ) compose the block arms of the HSLCP. (LC) x segments, one part of the arms, are assisted to promote transmission of Li-ion via orientation and PCL segments are used to dissociate lithium salt and efficiently migrate charge carriers. The good self-standing all-solid-state polymer electrolyte film composed of HSLCP and lithium bis(trifluoromethanesulfonimide (LiTFSI) can be formed by solution casting method. It is demonstrated that such a HSLCP exhibits good thermal stability (368°C), the HSLCP-based electrolyte shows high ionic conductivity (5.98 × 10 −5  S cm −1 at 30°C), outstanding ion transference number (0.63), and wide electrochemical window (5.12 V). In addition, LiFePO 4 /Li batteries employing the electrolyte deliver good cycling performance and rate capability. Simultaneously, the corresponding half-cell can still power a LED lamp at room temperature . Thus, this is a great progress for liquid crystal-based polymer electrolytes to be applied to high energy LIBs.

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POLYMER · 2024 · IF 4.1

Compatibilization of Poly(lactic acid)/Poly(propylene carbonate) blends by star-shaped multi-arm polymer with low molecular weight

Xuhui Zhang,Xing Li,Guangyao Ji,Jing Huang,Ting Li,Bihua Xia,Shibo Wang,Weifu Dong

Compatibilizing polymer blends via a facile and efficient manner is of great significance since polymer blends are practical in industrial applications but limit severely by poor compatibility. Herein, we propose a novel compatibilization strategy that star-shaped multi-arm polymer with low molecular weight can be an excellent compatibilizer for polymer blends. As an example of the concept, a modified tannic acid (mTA) with a star-shaped multi-arm structure is fabricated to compatibilize biodegradable poly(lactic acid)/poly(propylene carbonate) (PLA/PPC) blend. Compared to traditional compatibilization methods, mTA shows higher compatibilization efficiency and lower limitation in distribution as mTA can exert compatibilization at the interface and in PLA and PPC phases. Consequently, mTA compatibilizes the PLA/PPC blend efficiently, leading to strikingly reduced size of PPC dispersed phase and optimized interface. The mechanism is revealed to stem from the reduced interfacial tension and regulated viscosity ratio. With the improved compatibility, PLA70/PPC30/mTA4 shows an elongation at break of 307.5 ± 15.4 % and a toughness of 85.2 ± 4.5 MJ/m 3 , which is 680 % and 800 % of that of PLA70/PPC30 respectively. We envision that this work provides a novel and facile compatibilization strategy and will promote the fabrication of high-performance polymer blends.

CAS / MDL: 108-32-7 1401-55-4
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JOURNAL OF APPLIED POLYMER SCIENCE · 2025 · IF 2.8

Inhibition of Wax Crystallization and Asphaltene Deposition by Star Poly(Octadecyl Acrylate-Styrene) (POA-St) for African Crude Oil

Zuojia Xi,Xubiao Zhang,Chaohe Yang,Jun Xu

In the global energy landscape, the development of desert oil in Africa has increased the diversity of world oil supply and helped maintain the balance of the global energy market. However, wax precipitation and asphaltene deposition cause numerous challenges during the recovery and pipeline transportation of African crude oil. Traditional linear polymer additives often have limited wax-modifying and asphaltene-dispersing efficiency. In this work, linear poly(octadecyl acrylate-styrene) (POA-St) and a series of star POA-St copolymers with different arm numbers (3, 4, and 6) were synthesized through reversibly additive fragment chain transfer polymerization. The effects of the linear and star POA-St on the wax precipitating properties, pour point, rheology, and asphaltene stability of African waxy crude oil were studied in detail. The star POA-St copolymers show superior performance compared with linear polymers in inhibiting wax crystal formation, improving crude oil rheology, and stabilizing asphaltene. Increasing the arm number of star POA-St greatly improves its performance. Star POA-St-6 reduces the wax appearance temperature of the crude oil from 53.7°C to 51.1°C. At 20°C, the addition of the star POA-St-6 reduces the pour point of crude oil from 30°C to 21°C, and the viscosity and yield stress decrease by 74% and 55.2%, respectively. In addition, star POA-St-6 increases the initial precipitation points of asphaltene from 44.3% to 57.1%, showing a splendid asphaltene inhibiting efficiency. We speculate that the star POA-St stabilizes asphaltene aggregates among its arms and changes the wax crystal morphology through co-crystallization and nucleation effects, thereby exhibiting good performance. These findings provide prospective insights and avenues for the structural optimization and innovation of a new type of pour point depressant.

CAS / MDL: 100-42-5
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