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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2024 · IF 7.7

Multiple enzyme-mimic polypeptide based carbon nanoparticles by ROP and Fe coordination for ROS regulation and photo-thermal therapy against bacterial infection

Ya-li Xiang,Ling-ling Yan,Luo-lin Deng,De-yu Tang,Xin-yang Liu,Juan Lin,Qing-han Zhou

Novel strategy is urgently needed to overcome the bacterial infection all over the world due to unreasonable use of biotics. In recent years, nanozymes have attracted great interests of researchers for their high catalytic efficiency and biocompatibility. In this study, a novel multiple enzyme-mimic polypeptide-based carbon nanoparticle was synthesized by N-carboxyanhydride mediated ring opening polymerization (ROP) and Fe coordination for actualizing ROS regulation and photo-thermal therapy. The multiple enzyme-mimic activities of the nanozyme, such as peroxidase, oxidase, catalase, and glutathione peroxidase, were detailly explored in ROS regulation for potential utilization in bacterial inhibition. The photo-thermal effect of the nanozyme was investigated under 808 nm NIR irradiation. Enhanced inhibition rate of the as prepared nanozyme was observed against Gram-negative Escherichia coli (99.03 %) and Gram positive Staphylococcus aureus (99.78 %) planktonic bacteria. Methicillin-resistant Staphylococcus aureus ( MRSA ) was chosen as the drug resistant bacteria model to evaluate the efficiency in bacterial biofilm disruption. Improved healing efficacy of 99.05 % against MRSA wound infection and excellent biosafety were observed in mice model experiments for the as prepared nanozyme. In conclusion, the as synthesized nanozyme with ROS regulation, enhanced bacteria inhibition, and excellent biocompatibility could be potentially applied in clinic against bacterial infection.

CAS / MDL: 766-39-2
研究领域: 纳米技术 · 生物医学工程 · 材料科学 · 微生物学 · 治疗学
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COMPOSITE STRUCTURES · 2021 · IF 5.407

Modified MXene-doped conductive organosilicon elastomer with high-stretchable, toughness, and self-healable for strain sensors

Zhe Wang,Kaiming Zhang,Yuetao Liu,Haoyu Zhao,Chuanhui Gao,Yumin Wu

Polymers/nanomaterials conductive elastomers based on reversible interactions are of great significance in the application of resistive sensors because they repair themselves after mechanical injury, just like living things. The electronic devices developed with such materials will be more stable and reliable. Herein, we innovatively used ring opening polymerization (ROP) of sulfur-containing five membered rings to endow organosilicon supermolecule and MXene with hyperbranched structure which had terminal carboxyl groups. Subsequently, organosilicon conductive elastomer (PDMS@MXene) crosslinked by hydrogen bonds and metal–ligand bonds was prepared. The fully disconnected PDMS@MXene could recover 91.7% of its original mechanical properties after spontaneous repair. The well-organized composite had high stretchability and excellent tensile strength , which enhanced its application prospects in soft robots , motion monitoring and other fields. This novel design idea and simple preparation process will provide a reference for the development of self-healable conductive elastomer in the future.

CAS / MDL: 1122-58-3 25952-53-8
研究领域: 材料科学 · 纳米技术 · 高分子科学 · 传感技术 · 机器人技术
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POLYMER · 2010 · IF 3.573

Synthesis of biodegradable pentaarmed star-block copolymers via an asymmetric BIS-TRIS core by combination of ROP and RAFT: From star architectures to double responsive micelles

Jianbo Li,Jie Ren,Yang Cao,Weizhong Yuan

Biodegradable star-shaped poly( ɛ -caprolactone) and poly( ɛ -caprolactone- b - l -lactide) (5sPCL- b -PLLA) with five arms were synthesized by ring-opening polymerization (ROP) from an asymmetric BIS-TRIS core via “core-first” strategy. Subsequently, a series of amphiphilic and double responsive star-block copolymers were synthesized by Z -RAFT star polymerization of N , N -dimethylamino-2-ethyl methacrylate (DMAEMA) from the star-shaped macro-RAFT agent, which was prepared by attaching 3-benzylsulfanylthiocarbonylthiocarbonylsufanylpropionic acid (BSPA) to 5sPCL- b -PLLA using a simple two-step reaction sequence. GPC and 1 H NMR data demonstrated the polymerization courses are under control. The molecular weight of 5sPCL- b -PLLA- b -DMAEMA increased with the monomer conversion, and the molecular weight distribution was in the range of 1.19–1.37. The spherical micelles with degradable core and pH/thermo-double sensitive shell had been prepared from the aqueous medium of the amphiphilic star-shaped copolymers by dialysis method. Both pH and thermal-responsive behaviours of copolymer micelles obtained in this study were investigated. The micelle size and morphology were measured by DLS, AFM and TEM .

研究领域: 高分子化学 · 材料科学 · 纳米医学
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Polymer Chemistry · 2018 ·Vol. 9 ·期 29 ·3974-3986 · IF 4.927

Hyperbranched polypeptides synthesized from phototriggered ROP of a photocaged Nε-[1-(2-nitrophenyl)ethoxycarbonyl]-L-lysine-N-carboxyanhydride: microstructures and effects of irradiation intensity and nitrogen flow rate

Pan Li,Yingying Song,Chang-Ming Dong

Controlled polymerization to synthesize hyperbranched polypeptides (HBPPs) with tunable degree of branching (DB) and molecular weight (MW) is still challenging in synthetic polypeptides and their biomaterials fields. A new photocaged amino acid monomer Nε-(1-(2-nitrophenyl)ethoxycarbonyl)-L-lysine-N-carboxyanhydride (NPE-Lys NCA) was designed. Without the addition of any catalyst/initiator and/or scavenger, lysine-based HBPPs were directly synthesized from the UV phototriggered ring-opening polymerization (ROP) of NPE-Lys NCA by a one-pot method and at room temperature. Their branched structures were fully characterized by means of 1H NMR, 1H,1H-COSY, 1H,13C-HSQC, and quantitative 13C NMR techniques. The effects of irradiation intensity and N2 flow rate on the phototriggered ROP and MWs, DBs, and conformations of the resulting polypeptides were investigated. At a lower irradiation intensity of 0.3 mW cm−2, the actual MWs (Mw,LLS) of P1 to P3 increased from 34.9 kDa to 62.8 kDa when N2 flow rate shifted to 300 mL min−1; DB reduced from 0.43 to 0.21; and the α-helix content rose from 35% to 63%, while the random coil decreased from 50% to 26%. By tuning the UV irradiation intensity and/or the N2 flow rate, this methodology can efficiently produce lysine-based HBPPs with tunable DBs of 0.21–0.54 and higher actual MWs of 13.7–62.8 kDa.

CAS / MDL: 32315-10-9
研究领域: 高分子化学 · 生物材料科学
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JOURNAL OF MEMBRANE SCIENCE · 2024 · IF 8.4

A novel amphiphilic polypeptoid based ultrafiltration membrane with excellent biocompatible property

Ronglu Cui,Kai Hao,Yunyun Xue,Chuyao Wang,Shuyang Shen,Zihao Zhao,Yu Zhao,Jun Ling,Baoku Zhu,Lifeng Fang

Polysarcosine (PSar), a polypeptoid with a chemical structure resembling natural amino acids, stands out as a prominent non-ionic polypeptoid due to its outstanding water solubility and biocompatibility. These extraordinary properties make PSar a highly appealing material for a wide range of biomedical applications, especially in biocompatible membranes. However, due to its high-water solubility, PSar is inherently not stable enough for membranes. It is an effective way to apply PSar in membrane field by improving its stability while ensuring the hydrophilicity. Here, a novel copolymer, consisting of PSar and polysulfone (PSF) blocks (PSF- b -PSar, denoted as PSbS), is presented and synthesized by ring-opening polymerization (ROP) of N -phenyloxycarbonyl-sarcosine (Sar-NPC), which is used as a functional skin layer on PSF substrates. The results demonstrated that the PSbS performed a highly hydrated layer on the membrane surface, thus mitigating interactions between biomolecules and biological entities. Notably, the PSbS/PSF membrane showed improved antifouling, biocompatibility, hemocompatibility and stability. Moreover, the hemolysis rate of the composite membrane was reduced to 0.56%, and the activated partial thromboplastin time (APTT) was effectively prolonged. In summary, this work proposed a strategy for solidifying PSar on the membrane surface as the non-water-soluble amphiphilic polymer, which is promising in the biomedical applications, especially in biocompatible membranes.

CAS / MDL: 3326-32-7
研究领域: 材料科学 · 生物医学工程 · 聚合物化学 · 膜技术
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JOURNAL OF CONTROLLED RELEASE · 2022 · IF 11.467

Immunomodulation of MiRNA-223-based nanoplatform for targeted therapy in retinopathy of prematurity

Keke Huang,Zhiqing Lin,Yuanyuan Ge,Xuhao Chen,Yining Pan,Ziru Lv,Xiaoting Sun,Hao Yu,Jiangfan Chen,Qingqing Yao

Retinopathy of prematurity (ROP) is characterized by pathological angiogenesis and associated inflammation in the retina and is the leading cause of childhood blindness. MiRNA-223 (miR-223) drives microglial polarization toward the anti-inflammatory phenotype and offers a therapeutic approach to suppress inflammation and consequently pathological neovascularization . However, miRNA-based therapy is hindered by the low stability and non-specific cell-targeting ability of delivery systems. In the present study, we developed folic acid–chitosan (FA–CS)-modified mesoporous silica nanoparticles (PMSN) loaded with miR-223 to regulate retinal microglial polarization. The FA–CS/PMSN/miR-223 nanoparticles exhibited high stability and loading efficiency, achieved targeted delivery, and successfully escaped from lysosomes. In cultured microglial cells, treatment with FA–CS/PMSN/miR-223 nanoparticles upregulated the anti-inflammatory gene YM1/2 and IL-4RA, and downregulated the proinflammatory genes iNOS , IL-1β , and IL-6 . Notably, in a mouse oxygen-induced retinopathy model of ROP, intravitreally injected FA–CS/PMSN/miR-223 nanoparticles (1 μg) decreased the retinal neovascular area by 52.6%. This protective effect was associated with the reduced and increased levels of pro-inflammatory (M1) and anti-inflammatory (M2) cytokines, respectively. Collectively, these findings demonstrate that FA–CS/PMSN/miR-223 nanoparticles provide an effective therapeutic strategy for the treatment of ROP by modulating the miR-223-mediated microglial polarization to the M2 phenotype.

研究领域: 眼科学 · 纳米技术 · 分子生物学 · 炎症 · 治疗学
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Biomaterials Science · 2021 ·Vol. 10 ·期 3 ·834-845 · IF 6.843

Preparation of antibacterial polypeptides with different topologies and their antibacterial properties

Xiaodan Wang,Fangping Yang,Huawei Yang,Xu Zhang,Haoyu Tang,Shifang Luan

Antimicrobial peptides (AMPs) are attractive antimicrobial agents used to combat bacterial infections, and have been advanced to be one of the most promising alternatives to conventional antibiotics. They stand out for their attractive broad-spectrum activity, unmatched antibacterial mechanism that is not prone to develop drug resistance and diversified topologies, which can be fabricated with manifold amino acid blocks. In this study, using n-hexylamine and amine-terminated polyamidoamine dendrimers (Gx-PAMAM, x = 1–2) as initiators, a series of AMPs with linear and star-shaped topological structures were constructed via the controllable ring-opening polymerization (ROP) of N-carboxyanhydrides (NCAs). The antibacterial performances of the tailored linear and star-shaped AMPs were comprehensively evaluated in both solution states and surface-bonded states. The results indicated that the star-shaped AMPs exhibited enhanced bactericidal activity against Gram-negative E. coli and similar bactericidal activity against Gram-positive S. aureus when compared with the linear AMPs. It is worth mentioning that star-shaped AMPs demonstrated a significantly faster bactericidal efficiency (completely killed bacteria within 5 min at a concentration of 2 × MIC for S. aureus) than their linear analogues (took 15 min to achieve the same effect). However, when the AMPs were immobilized to the surface, they similarly exhibited superior antibacterial activity and fast bactericidal efficiency towards S. aureus and E. coli in the case of the same surface grafting amount. In addition, both the surfaces grafted with AMPs of different topologies demonstrated favorable biocompatibility in vitro.

研究领域: 生物材料 · 生物技术 · 微生物学 · 高分子化学
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APPLIED SURFACE SCIENCE · 2023 · IF 6.7

Fabrication of ionic liquid-functionalized aliphatic polycarbonate brushes for self-polishing antibacterial application

Yijia Yu,Shengjie Liu,Wenjuan Xia,Zhichen Zhu,Wenjin Wang,Chuanjiang Zhou,Zhaoqiang Wu,Hong Chen

To meet the development of multifunctional surfaces with long-term antibacterial activity for biomaterials and implantable devices, herein, a novel self-polishing antibacterial surface was developed. The functionalized surface was prepared by first surface-initiated ring-opening grafting polymerization (SI-ROP) of a cyclic carbonate monomer 4′-(fluorosulfonyl)benzyl-5-methyl-2-oxo-1,3-dioxane-5-carboxylate (FMC) containing a sulfonyl fluoride group in the side chain onto the material surface and then by a “sulfur(IV)-fluorine” exchange (SuFEx) postclick modification reaction to link the imidazolium salt ionic liquid to the polyFMC (PFMC) brush. In vitro experimental results showed that the functionalized surface has good biocompatibility, enzymatic biodegradable properties and excellent bactericidal properties, which can effectively kill E. coli (∼94%) and S. aureus (∼93%). In addition, the functionalized surface can release the killed bacteria (∼90%) several times efficiently under the action of lipase enzymatic degradation, restoring the original bactericidal function of the surface, thus forming a dynamic self-polishing and self-renewing antibacterial surface. Therefore, this method for the fabrication of self-polishing antibacterial surfaces may offer innovative insights into applications of biomedical implant materials.

研究领域: 材料科学 · 生物医学工程 · 表面化学 · 抗菌技术
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Polymers · 2020 ·Vol. 12 ·期 11 ·2482 · IF 3.426

Novel Temperature/Reduction Dual-Stimulus Responsive Triblock Copolymer [P(MEO2MA-co- OEGMA)-b-PLLA-SS-PLLA-b-P(MEO2MA-co-OEGMA)] via a Combination of ROP and ATRP: Synthesis, Characterization and Application of Self-Assembled Micelles

Fei Song,Zhidan Wang,Wenli Gao,Yu Fu,Qingrong Wu,Shouxin Liu

Novel temperature/reduction dual stimulus-responsive triblock copolymers, poly [2-(2-methoxyethoxy) ethyl methacrylate-co-oligo (ethylene glycol) methacrylate]-b-(L-polylactic acid)-SS-b-(L-polylactic acid)-b-poly[2-(2-methoxyethoxy) ethyl methacrylate-co-oligo(ethylene glycol)methacrylate] [P(MEO2MA-co-OEGMA)-b-PLLA-SS-PLLA-b-P(MEO2MA-co-OEGMA)] (SPMO), were synthesized by ring opening polymerization (ROP) of L-lactide and 2,2’-dithio diethanol (SS-DOH), and random copolymerization of MEO2MA and OEGMA monomers via atom transfer radical polymerization (ATRP) technology. The chemical structures and compositions of the novel copolymers were demonstrated by proton nuclear magnetic resonance (1H NMR) and Fourier transform infrared spectroscopy (FTIR). The molecular weights of the novel copolymers were measured by size exclusive chromatography (SEC) and proved to have a relatively narrow molecular weight distribution coefficient (ÐM ≤ 1.50). The water solubility and transmittance of the novel copolymers were tested via visual observation and UV–Vis spectroscopy, which proved the SPMO had a good hydrophilicity and suitable low critical solution temperature (LCST). The critical micelle concentration (CMC) of the novel polymeric micelles were determined using surface tension method and fluorescent probe technology. The particle size and morphology of the novel polymeric micelles were characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The sol–gel transition behavior of the novel copolymers was studied via vial flip experiments. Finally, the hydrophobic anticancer drug doxorubicin (DOX) was used to study the in vitro release behavior of the novel drug-loaded micelles. The results show that the novel polymeric micelles are expected to become a favorable drug carrier. In addition, they exhibit reductive responsiveness to the small molecule reducing agent dithiothreitol (DTT) and temperature responsiveness with temperature changes.Keywords:temperature/reductive dual-stimulus responsiveness;block copolymers;amphiphilic;ring-opening polymerization;atom transfer radical polymerization

CAS / MDL: 26915-72-0 4511-42-6
研究领域: 高分子化学 · 药物递送系统 · 材料科学
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COLLOIDS AND SURFACES B-BIOINTERFACES · 2024 · IF 5.4

PEG-functionalized aliphatic polycarbonate brushes with self-polishing dynamic antifouling properties

Yijia Yu,Wenjuan Xia,Wenjin Wang,Zhaoqiang Wu,Hong Chen

Hydrophilic antifouling polymers provide excellent antifouling effects under usual short-term use conditions, but the long-term accumulation of contaminants causes them to lose their antifouling properties. To overcome this drawback, surface-initiated ring-opening graft polymerization (SI-ROP) was performed on the surface of the material by applying the cyclic carbide monomer 4′-(fluorosulfonyl)benzyl-5-methyl-2-oxo-1,3-dioxane-5-carboxylate (FMC), which contains a sulfonylfluoride group on the side chain, followed by a “sulfur(IV)-fluorine exchange” (SuFEx) post click modification reaction to link the hydrophilic polyethylene glycol (PEG) to the polyFMC (PFMC) brush, and a novel antifouling strategy for self-polishing dynamic antifouling surfaces was developed. The experimental results showed that the antifouling surface could effectively prevent the adsorption of proteins such as bovine serum albumin (BSA, ∼96.4%), fibrinogen (Fg, ∼87.8%) and lysozyme (Lyz ∼69.4%) as well as the adhesion of microorganisms such as the bacteria Staphylococcus aureus ( S. aureus ) (∼87.5%) and HeLa cells (∼67.2%). Moreover, the enzymatically self-polished surface still has excellent antifouling properties. Therefore, this modification method has potential applications in the field of biosensors and novel antifouling materials.

研究领域: 材料科学 · 表面化学 · 生物医学工程 · 高分子科学 · 生物材料
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EUROPEAN POLYMER JOURNAL · 2021 · IF 4.598

Reinvestigation of the ring-opening polymerization of ε-caprolactone with 1,8-diazacyclo[5.4.0]undec-7-ene organocatalyst in bulk

Yang Chen,Jie Zhang,Wenhao Xiao,Anfu Chen,Zhixian Dong,Jinbao Xu,Wenhua Xu,Caihong Lei

1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) was used as organocatalyst to reinvestigate the ring-opening polymerization (ROP) of ε -caprolactone (CL) with benzyl alcohol (BnOH) initiator in bulk at 90 °C considering the unsuccessful ROP of CL at RT in previously reported publications. Kinetic study indicates that the PCLs could be well-designed with a controlled/living character of polymerization. The use of functional initiators, such as 2-hydroxyethyl methacrylate (HEMA), propargyl alcohol (PGA), 6-azido-1-hexanol (AHA) and methoxy poly(ethylene glycol) (mPEG) leads to end-functionalized PCLs. Accordingly, the block copolymerization of CL with δ-valerolactone (VL), trimethylene carbonate (TMC) and lactide (LA) successfully proceeded to give PCL- b -PVL, PCL- b -PTMC and PCL- b -PLA copolymers. Finally, the reaction mechanism was studied with DFT calculations and NMR measurements.

研究领域: 高分子化学 · 材料科学 · 有机化学
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Polymer Chemistry · 2024 · IF 4.1

Facile synthesis of asymmetric molecular brushes with triple side chains using a multivalent monomer strategy

Shiya Cao,Wenyi Liu,Bicai Yang,Yuan Zheng,Shaoliang Lin,Binbin Xu

Heterografted molecular brushes (HMBs) bearing two or more types of side chains have attracted tremendous attention because of their asymmetric structures and multiple functionalities. However, the controlled synthesis of HMBs with three types of side chains remains a challenge. The structure–property–application correlations of HMBs with three types of side chains are still not clear. Herein, based on the multivalent monomer strategy, we report the synthesis of well-defined asymmetric HMBs comprising three different side chains by sequential reversible addition–fragmentation chain transfer (RAFT) polymerization, atom transfer radical polymerization (ATRP), thiol–epoxy coupling reaction, and ring-opening polymerization (ROP). PA-g-PAzo/PEG/PLA with a polyacrylate (PA) backbone, hydrophobic poly(azobenzene-methacrylate) (PAzo) brush, hydrophilic polyethylene glycol (PEG) brush, and hydrophobic polylactide (PLA) brush was synthesized and characterized. The self-assembly behavior of PA-g-PAzo/PEG/PLA with a short backbone and relatively strong intermolecular association in solutions was investigated. Well-defined platelets with tunable morphologies were constructed. Subsequently, PA-g-PFA/PEG/PLA with a fluorophilic poly(pentafluoropropyl acrylate) (PFA) brush, hydrophilic PEG brush, and lipophilic PLA brush was synthesized and further used as an efficient surfactant for the stabilization of different emulsions. Our study offers a platform for exploring the unique properties of asymmetric HMBs.

研究领域: 高分子化学 · 材料科学 · 纳米技术 · 胶体科学
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