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AUSTRALIAN JOURNAL OF CHEMISTRY · 2015 ·Vol. 69 ·期 1 ·112-118 · IF 1.558

Water-Soluble Copolypeptides with Oligo-Ethylene-Glycol and Benzyl Pendants: Synthesis, Characterization, and Thermoresponsive Properties

Yu Yang,Yan Wu,Ruirui Li,Ying Ling,Haoyu Tang

A series of random copolypeptides, i.e. poly(γ-propyl-l-glutamate)-graft-(oligo-ethylene-glycol)-random-poly(γ-benzyl-l-glutamate)s (PPLG-g-OEG3-ran-PBLG) with similar main chain lengths and various compositions of OEG and benzyl pendants were synthesized in three steps, including ring-opening polymerization of γ-chloropropyl-l-glutamic acid-based N-carboxyanhydride (CPLG-NCA) and γ-benzyl-l-glutamic acid-based N-carboxyanhydride (BLG-NCA), nucleophilic substitution in the presence of NaN3, and copper-mediated alkyne–azide 1,3-dipolar cycloaddition. 1H NMR, Fourier transform infrared spectroscopy, and gel permeation chromatography results confirmed the molecular structures of the resulting copolypeptides and characterized their molar masses, molar mass distributions, and the OEG/benzyl compositions. Fourier transform infrared spectroscopy and circular dichroism analysis revealed that PPLG-g-OEG3-ran-PBLG samples adopted α-helical conformations both in aqueous solution and solid state. Variable-temperature UV-visible spectroscopy revealed that PPLG-g-OEG3-ran-PBLG samples with high OEG molar content (x ≥ 0.57) possessed lower critical solution temperature-type phase transitions in water. The cloud point temperature, in the range of 22–53°C, can be readily obtained by controlling the OEG/benzyl composition.

研究领域: 高分子化学 · 材料科学
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COLLOIDS AND SURFACES B-BIOINTERFACES · 2012 · IF 3.456

Amphiphilic cylindrical copolypeptide brushes as potential nanocarriers for the simultaneous encapsulation of hydrophobic and cationic drugs

Xiang Zeng,Jinhu Li,Jinhong Zheng,Ying Pan,Jinzhi Wang,Lumian Zhang,Xiaoying He,Daojun Liu

Cylindrical copolypeptide brushes PLLF- g -(PLF- b -PLG) with poly( l -lysine- co - l -phenylalanine) (PLLF) as the backbone and poly( l -phenylalanine)- b -poly( l -glutamic acid) (PLF- b -PLG) as the side chains have been synthesized and evaluated as drug delivery carriers. The synthesized copolypeptide brushes were characterized by 1 H NMR, gel permeation chromatography (GPC), and transmission electron microscopy (TEM). In aqueous solution, the copolypeptide brushes adopt cylindrical morphologies and resemble unimolecular polymeric micelles with a hydrophobic poly( l -phenylalanine) core and a hydrophilic poly( l -glutamate) shell. An encapsulation study demonstrated that these water soluble, biodegradable copolypeptide brushes encapsulate hydrophobic compounds and cationic hydrophilic guest molecules simultaneously. Furthermore, the encapsulated cationic model compounds exhibit a pH-responsive releasing property.

研究领域: 生物材料 · 药剂学 · 高分子化学
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MACROMOLECULES · 2016 · IF 5.554

SO2-Induced Solution Phase Transition of Water-Soluble and α-Helical Polypeptides

Mengxiang Zhu,Yan Wu,Chenglong Ge,Ying Ling,Haoyu Tang

Water-soluble random copolypeptides bearing pyridinium tetrafluoroborate (PyBF4) and oligo-ethylene glycol (OEG) pendants (PPLG-PyBF4-r-OEG) showed SO2-induced solution phase transition. They were prepared by sequential postpolymerizations including nucleophilic substitution of poly(γ-3-chloropropyl-l-glutamate) with sodium azide to partially convert chloro groups into azido groups, copper-mediated [2 + 3] alkyne–azide 1,3-dipolar cycloaddition to conjugate OEG pendants, another nucleophilic substitution to conjugate pyridinium chloride, and ion-exchange reaction. FTIR and CD analysis revealed that PPLG-PyBF4-r-OEG samples with suitable molar content of PyBF4 (x ≤ 0.4) were water-soluble and adopted α-helical conformation in both the solid-state and aqueous solution. UV–vis spectroscopy and dynamic light scattering (DLS) results revealed that PPLG-PyBF4-r-OEG aqueous solution underwent a reversible solution phase transition by sequentially bubbling SO2 and N2. 1H NMR analysis suggested that SO2 interacted with triazole groups and induced the solution phase transition.

研究领域: 生物化学 · 高分子化学
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EUROPEAN POLYMER JOURNAL · 2018 · IF 3.741

Synthesis of triblock amphiphilic copolypeptides with excellent antibacterial activity

Xinyu Zhou,Xiaokai Su,Zhengzhong Tan,Chuncai Zhou

Antibacterial peptides as a novel antimicrobial agent have overwhelmingly caught researchers’ attention with unique superiority. Here, we report a series of triblock copolypeptides K 10 -b- F n -b- K 10 synthesized by sequential NCA ring-opening polymerization. The obtained triblock copolypeptides have good antibacterial efficacy against both S. aureus and E. coli . The hemolysis test has been conducted and it suggests that the triblock copolypeptides have low cytotoxicity and good biocompatibility. Furthermore, we present a systematic study on their self-assembly behavior and confirm that they can self-assemble into vesicles. Hence, such triblock copolypeptides have potential applications in antibacterial therapy and biomedical application field.

研究领域: 生物材料学 · 微生物学 · 合成生物学
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Soft Matter · 2014 ·Vol. 11 ·期 3 ·545-550 · IF 4.151

Tuning the phase transition temperature of thermal-responsive OEGylated poly-L-glutamate via random copolymerization with L-alanine

Lei Yu,Wenxin Fu,Zhibo Li

Two series of copolymers were prepared by ring-opening polymerization (ROP) of γ-(2-methoxyethoxy)esteryl-L-glutamate (L-EG2Glu) N-carboxyanhydride (NCA) and L-alanine (L-Ala) using HMDS and PEG-NH2 as initiator, respectively. Poly-(L-EG2Glu-co-L-Ala) displayed lower critical solution temperature (LCST) behavior but had a lower phase transition temperature than poly-L-EG2Glu at similar molecular weight (MW). The clouding point (CP) of random copolypeptides can be tuned by altering the alanine content and overall MW. Circular dichroism (CD) and Fourier transform infrared spectroscopy (FTIR) indicated that the thermal-responsive properties depended on the content of ordered conformations. PEG-b-poly-(L-EG2Glu-co-L-Ala) can spontaneously form hydrogels in water at room temperature. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) revealed that these hydrogels were formed by nanoribbons. The intermolecular hydrogen bonding among copolypeptide blocks accounted for the nanoribbon assemblies and hydrogel network formation.

CAS / MDL: 111-77-3 32315-10-9
研究领域: 聚合物化学 · 材料科学 · 生物物理学
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LANGMUIR · 2021 · IF 3.882

Development of Nonfouling Zwitterionic Copolymerized Peptides Based on Glutamic Acid and Lysine Dimers for Adjustable Enzymatic Degradation

Yumeng Guo,Liangbo Xu,Weifeng Lin,Shengfu Chen

Nonspecific protein adsorption-resistant materials, the so-called nonfouling materials, are crucial biomaterials in biomedical applications. Up-to-date, little attention was paid to the biodegradability of these materials. In this work, nonfouling zwitterionic copolymerized peptides composed of the N-l-glumatyl-l-lysine dimer (EK) and δ-l-lysinyl-l-glutamic acid dimer (E-K, glutamic acid with the lysine side chain) at various ratios were synthesized to investigate the enzymatic degradation rate. Two types of proteases (trypsin and alkaline protease), which represent a site-specific and less site-specific cleavage protease, respectively, were used to demonstrate the adjustable degradability by tracking the molecular weight (Mw) at different digestion times. Results showed that higher compositions of the E-K dimer lead to slower degradation rates by both proteases and larger fragments after 120 min digestion. With the composition of the E-K dimer over 50%, the degradation of copolymerized peptides by both proteases becomes very slow. This indicated that the bulky lysinyl side chain on E-K can alter the enzymolysis process for adjusting the enzymatic degradability of the newly synthesized zwitterionic copolymerized peptides, which could be promising candidates for biomedical applications in vivo.

研究领域: 生物材料 · 生物医学工程 · 高分子化学 · 酶学
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JOURNAL OF MATERIALS CHEMISTRY · 2012 ·Vol. 22 ·期 41 ·22290-22300 · IF 5.968

Synthesis of polypeptide conjugated with near infrared fluorescence probe and doxorubicin for pH-responsive and image-guided drug delivery

Tao Xing,Xianzhu Yang,Feng Wang,Bin Lai,Lifeng Yan

A near infrared fluorescent polymeric drug delivery system (NIRF DDS) with pH-responsive drug release properties has been designed and developed. This material was prepared by chemical conjugation of the anticancer drug doxorubicin and hydrophobic aminocyanine dye to triblock copolypeptide via hydrazone and amide bonds, respectively. Conjugation with aminocyanine shows almost no toxicity of the material, while conjugation with doxorubicin induces pronounced toxicity on the original biocompatible material. The pH sensitive drug release nature of the near infrared fluorescent polymeric drug (NIRF prodrug) was confirmed by accelerated drug release at pH of 5.0 via an in vitro drug release experiment and gradual drug cleavage from the NIRF prodrug during a confocal laser scanning microscopic (CLSM) experiment. The CLSM experiment also reveals that the released drug subsequently migrated to the nucleus, while the polymeric residue still remained in cytoplasm, indicating that the as-prepared polymer can be a promising candidate for theranosis of cancer.

研究领域: 药学 · 癌症研究 · 聚合物化学 · 分子影像
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Polymers · 2024 ·Vol. 16 ·期 8 ·1082 · IF 4.7

Self-Assembly Study of Block Copolypeptoids in Response to pH and Temperature Stimulation

Di Liu,Kang Yang,Liugen Xu,Xiran Shen,Lei Feng,Yangang Jiang,Amjad Ali,Jianwei Lu,Li Guo

Polypeptoids with well-designed structures have the ability to self-assemble into nanomaterials, which have wide potential applications. In this study, a series of diblock copolypeptoids were synthesized via ring-opening polymerization followed by click chemistry and exhibited both temperature and pH stimulation responsiveness. Under specific temperature and pH conditions, the responsive blocks in the copolypeptoids became hydrophobic and aggregated to form micelles. The self-assembly process was monitored using the UV-Vis and DLS methods, which suggested the reversible transition of free molecules to micelles and bigger aggregates upon instituting temperature and pH changes. By altering the length and proportion of each block, the copolypeptoids displayed varying self-assembly characteristics, and the transition temperature could be tuned. With good biocompatibility, stability, and no cytotoxicity, the polypeptoids reported in this study are expected to be applied as bionanomaterials in fields including drug delivery, tissue engineering, and intelligent biosensing.

研究领域: 材料科学 · 纳米技术 · 生物医学工程 · 高分子化学
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