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TADPOLE
Polymer Chemistry · 2018 ·Vol. 9 ·期 33 ·4343-4353 · IF 4.927

A twin-tailed tadpole-shaped amphiphilic copolymer of poly(ethylene glycol) and cyclic poly(ε-caprolactone): synthesis, self-assembly and biomedical applications

Yanyan Zhou,Lei Li,Wei Chen,Dian Li,Nianchen Zhou,Jinlin He,Peihong Ni,Zhengbiao Zhang,Xiulin Zhu

A tadpole-shaped amphiphilic copolymer containing cyclic hydrophobic poly(ε-caprolactone) (PCL) and two hydrophilic poly(ethylene glycol) (PEG) tails, PEG-b-(c-PCL)-b-PEG, was rationally designed and prepared by a combination of ring-opening polymerization (ROP), chain end modification and intermolecular Cu-catalyzed azide–alkyne cycloaddition (CuAAC) “click” reaction. Firstly, cyclic PCL with two pendent alkynyl groups (c-PCL-2alkynyl) was prepared via successive ROP, a bimolecular CuAAC “click” reaction and transformation of pendent hydroxyl groups to alkynyl groups. Subsequently, a tadpole-shaped amphiphilic copolymer PEG-b-(c-PCL)-b-PEG was fabricated by the CuAAC “click” reaction between c-PCL-2alkynyl and azido-terminated PEG (PEG-N3). For the comparison purpose, a linear triblock copolymer [PEG-b-(l-PCL)-b-PEG] and a 4-arm star copolymer (2PEG-b-2PCL) with comparable molecular weights and compositions were also synthesized. All these polymers were fully characterized by size exclusion chromatography (SEC), nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry. In addition, the self-assembly behavior, drug loading capacity and in vitro cytotoxicity of the tadpole-shaped amphiphilic copolymer and its linear and 4-arm star analogues were preliminarily investigated. It was found that the assemblies of PEG-b-(c-PCL)-b-PEG showed a similar spherical morphology but a smaller size compared with those of PEG-b-(l-PCL)-b-PEG and 2PEG-b-2PCL. The in vitro cytotoxicities against L929 fibroblast cells and HeLa cells evaluated by MTT assays revealed that the copolymers, especially PEG-b-(c-PCL)-b-PEG and 2PEG-b-2PCL, exhibited favorable biocompatibility, which might be potentially used as nanoscale drug delivery systems.

研究领域: 材料科学 · 生物医学工程 · 药剂学
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POLYMER · 2017 · IF 3.684

Synthesis and self-assembly of amphiphilic tadpole-shaped block copolymer with disulfides at the junction points between cyclic PEG and linear PS

Yuanyuan Tao,Hanying Zhao

Shell-sheddable polymeric assemblies are a type of self-assembled structures formed by amphiphilic block copolymers with cleavable linkages at the junction points. The shell-sheddable self-assemblies have been used as nanocarriers for drugs and inorganic nanoparticles . In this research, synthesis and self-assembly of amphiphilic tadpole-shaped block copolymer with disulfide bonds at the junction points were investigated. Dialkyne-terminated polystyrene (Da-PS) was synthesized by reversible addition-fragmentation chain transfer polymerization and thiol-disulfide exchange reaction. The tadpole-shaped block copolymer was synthesized by bimolecular coupling between azido-terminated PEG and Da-PS. Size exclusion chromatograph , FTIR, 1 H NMR and matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass analysis results all indicated successful synthesis of the polymer. The tadpole-shaped block copolymer self-assembles into vesicles in aqueous solution. The disulfide bonds at the junction points can be cleaved by a reducing agent, resulting in aggregation of the assemblies.

研究领域: 材料科学 · 药物递送系统 · 高分子化学
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Laser & Photonics Reviews · 2024 · IF 9.8

Light-Guided Genetic Scissors Based on Phosphorene Quantum Dot

Zhi Chen,Hao Huang,Jiefeng Deng,Changle Meng,Yule Zhang,Taojian Fan,Lude Wang,Shuo Sun,Yi Liu,Huiling Lin,Shuang Li,Yunpeng Bai,Lingfeng Gao,Junle Qu,Dianyuan Fan,Xueji Zhang,Han Zhang

Genetic engineering faces persistent challenges in achieving precise Deoxyribonucleic acid (DNA) cleavage, especially with the limitations associated with current enzyme-based methods, exemplified by issues in CRISPR technologies. This study introduces a groundbreaking approach: utilizing reactive oxygen species (ROS) generated by Multiphoton Absorption (MPA)-excited Black Phosphorus Quantum Dots (BPQDs) under femto-second laser irradiation. This innovative method not only allows excitation with lower energy but also enhances overall efficiency. The integration of complementary RNA sequences facilitates high-efficiency, site-selective DNA cleavage in the system, named “TADPOLE” (Targeted DNA Precision Oriented Laser Excision). Beyond its precision in targeting arbitrary DNA sequences using quantum dots, TADPOLE harnesses the unique multiphoton absorption property of BPQDs, enabling excitation with lower-energy light sources suitable for in vivo applications in the future. Moreover, the approach integrates guiding RNA and ultrafast laser technology to provide precise control over local ROS generation and minimal heat production. This guarantees site-specific DNA cleavage while mitigating the risk of damage to non-targeted sequences. In summary, this study catalyzes advancements in enzyme-free DNA cleavage technologies, with transformative implications for genetic engineering, biotechnology, and medicine. The holistic precision, versatility, and endurance presented by TADPOLE open new avenues for targeted gene therapies and transformative applications in related fields.

CAS / MDL: 16940-66-2 7761-88-8
研究领域: 遗传学 · 生物技术 · 医学
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Small · 2024 · IF 13

Tadpole-Like Carbon Nanotube with Fe Nanoparticle Encapsulated at the Head and Zn Single-Atom Anchored on the Body: One-Pot Carbonization for Tetramodal Synergistic Cancer Therapy

Mengmeng Zhang,Mingzhu Lu,Yimin Gong,Yannan Yang,Junfei Song,Jianing Li,Zhenxia Chen,Yun Ling,Yaming Zhou

Precise integration of diverse therapeutic approaches into nanomaterials is the key to the development of multimodal synergistic cancer therapy. In this work, tadpole-like carbon nanotubes with Fe nanoparticle encapsulated at the head and Zn single-atom anchored on the body (Fe@CNT-Zn) is precisely designed and facilely prepared via one-pot carbonization. In vitro studies revealed the integration of chemotherapy (CT), chemodynamic therapy (CDT), photothermal therapy (PTT), and photodynamic therapy (PDT) in Fe@CNT-Zn as well as the near-infrared light (NIR)-responsive cascade therapeutic efficacy. Furthermore, in vivo studies demonstrated the NIR-triggered cascade-amplifying synergistic cancer therapy in a B16 tumor-bearing mouse model. The results not only showcased the Fe@CNT-Zn as a potential tetramodal therapeutic platform, but also demonstrated a proof-of-concept on metal–organic framework-based “one stone for multiple birds” strategy for in situ functionalization of carbon materials.

研究领域: 生物医学工程 · 纳米医学 · 肿瘤治疗
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