MACROMOLECULAR CHEMISTRY AND PHYSICS
·
2019
·Vol. 220
·期 12
·1900061
·
IF 2.622
Liang Zhao,Lin Zhang,Zelai Zheng,Ying Ling,Haoyu Tang
Homopolypeptide bearing azobenzene and triethylene glycol spacers, and 1-butylimidazolium pendants, namely P(Azo-OEG 3 -ImX) (X = Cl, I, BF 4 ) are prepared by 1,3-dipolar cycloaddition and subsequent ion-exchange reaction. Both 1 H NMR and FTIR confirm the polymer structures and reveal a high grafting efficiency (97%). P(Azo-OEG 3 -ImI) shows reversible upper critical solution temperature (UCST)-type thermoresponsive property in ethanol while P(Azo-OEG 3 -ImI/BF 4 ) shows a UCST in ethanol/water solvent mixtures. P(Azo-OEG 3 -ImI) shows UCST-type phase transitions in ethanol or ethanol/water solvent mixtures. After UV irradiation, the UCST-type cloud point temperature ( T cp ) remains constant in ethanol. However, it decreases after UV irradiation and increases after visible light irradiation in ethanol/water solvent mixtures due to the trans – cis isomerization of azobenzene moieties. P(Azo-OEG 3 -ImCl/I) shows NaI-induced UCST in water. The T cp of the P(Azo-OEG 3 -ImCl/I) aqueous solution is highly related to the polymer/salt concentration and nature of counteranions. P(Azo-OEG 3 -ImCl) also shows reversible light-responsive properties in NaI aqueous solutions. Higher NaI concentration is needed to induce a UCST for P(Azo-OEG 3 -ImCl) after UV irradiation. Moreover, ciprofloxacin-loaded hydrogel containing P(Azo-OEG 3 -ImCl) shows more efficient drug release while the UV irradiation leads to slightly low drug release.
研究领域:
高分子化学
·
材料科学
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DOI
高影响因子
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
·
2018
·Vol. 56
·期 10
·1067-1077
·
IF 2.588
Yuanfeng Gao,Chang-Ming Dong
Stimuli-responsive polypeptides are receiving much attention for drug delivery systems and tissue engineering scaffolds; however, it is challenging to construct multiple-responsive polypeptides and one-component polymeric hydrogels. Herein, a novel type of triple redox/temperature-responsive diselenide-containing poly(methoxydiethylene glycol- l -glutamate) homopolypeptide was facilely synthesized by selenocystamine-initiated ring-opening polymerization in DMF at 30 °C, and their chemical structures and physical properties were fully characterized by means of 1 H NMR, GPC, FT-IR, WAXD, and CD. They self-assembled into spherical micelles in aqueous solution, which possess a lower critical solution temperature, redox-responsiveness inherited from diselenide bond, and the triple stimuli-sensitive self-assembly behaviors, as characterized by means of turbidity, DLS, TEM, and zeta potential measurements. The diselenide-containing homopolypeptides formed supramolecular hydrogels at room temperature, exhibiting a thermal gel–sol transition. The rheological tests evidence that the mechanical modulus of the hydrogel is independent of angular frequency within 100 rad/s and at 25 °C, in which the storage modulus of G′ is order of magnitude greater than the loss modulus of G″, displaying a solid-like elastic behavior. Moreover, the mechanical modulus of the hydrogel can be tuned by changing the chain length of the homopolypeptide, the 10-mM 1,4-dithiothreitol (DTT) reduction, and 1 mM H 2 O 2 oxidation, respectively. Consequently, this work provides a simple strategy to fabricate triple-stimuli responsive polypeptide micelles and one-component hydrogels. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56 , 1067–1077
研究领域:
材料科学
·
生物医学工程
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产品关联
DOI
高影响因子
Biomaterials Science
·
2020
·Vol. 8
·期 24
·6969-6977
·
IF 6.183
Bo Zhang,Min Li,Min Lin,Xuan Yang,Jing Sun
Bioinspired polypeptoids show great potential in many applications. Here, we report a convenient approach to synthesize a novel type of polypeptoid containing both sulfonium and oligo(ethylene glycol) (OEG) moieties by ring-opening polymerization (ROP) and a post-modification strategy. Three types of epoxides with (OEG)n (n = 1–3) groups are involved to offer various functionalities. The obtained polypeptoid sulfonium salts show positive ζ potential, irrespective of the solution pH and the degree of polymerization (DP). We demonstrate that the polypeptoids exhibit excellent antibacterial activity against Staphylococcus aureus (S. aureus) with MIC (minimal inhibitory concentration) in the range of 3.9–7.8 μg mL−1. In addition, the polypeptoids have a low hemolysis property and good in vitro biocompatibility. Remarkably, the as-prepared polypeptoids show rapid and potent antibacterial activity within 5 min. These features suggest that the obtained polypeptoids offer great potential for antimicrobial agents.
研究领域:
生物材料学
·
抗菌剂开发
·
高分子化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHINESE JOURNAL OF POLYMER SCIENCE
·
2015
·Vol. 33
·期 8
·1150-1161
·
IF 1.835
Yuan Qiu-lin,Liu Wen-jun,Deng Yong,Ling Ying,Tang Hao-yu
A series of polypeptides bearing biphenyl mesogenic side-chains and oligo-ethylene-glycol (OEG) tails (PPLG
n
- g -BPOEG
m
, n = 26 and 63, m = 2, 3, and 7) has been synthesized via a 1,3-dipolar cycloaddition with quantitative grafting density. FTIR results revealed that the polypeptides adopted highly stable α -helix in the temperature range of 25–200 °C. DSC, POM and WAXS analysis revealed that PPLG
n
- g -BPOEG
m
( m ≤ 3) samples with short OEG tail length showed two main phase transitions including crystal to liquid crystalline (smectic C, SmC) phase transition and the melting transition of crystalline E-phase, while PPLG
n
- g -BPOEG 7 with longer OEG tail length ( m = 7) exhibited the melting transitions without the formation of liquid crystalline phase.
研究领域:
材料科学
·
生物化学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF POLYMER SCIENCE
·
2022
·Vol. 40
·期 11
·1360-1368
·
IF 3.815
Lu Yan-Zhi,Gu An-Qi,Shen Tian-Lun,Sun Ji-Hong,Ling Jun
Modifications at polypeptide side chains have been found to affect conformational and properties, which is a vital strategy to prepare functional polypeptides. This contribution describes the synthesis of homo and co-polypeptides containing unsaturated bonds and thioether moieties, poly( S -allylcysteine) (PAC). The pendant vinyl groups provide an active binding site which are able to be further modified with cysteine by thiol-ene click reaction. The sulfoxide from thioether oxidation bestows the polypeptide water solubility and enzymatic catalytic sites. The self-assembly micelles of PEG- b -PAC are ruptured along with oxidation to release the Nile red payloads. Moreover, poly( S -allyl-cysteine sulfoxide), aka. polyalliin, is the oxidation product of PAC which undergoes side chain cleavage catalyzed by alliinase enzyme. The polypeptides are biocompatible as confirmed by cell viability assays and may find applications in drug delivery, biosensing and nanoreactor.
研究领域:
生物材料
·
高分子化学
·
药物递送
✓ 已验证
产品关联
DOI
高影响因子
MACROMOLECULAR CHEMISTRY AND PHYSICS
·
2017
·Vol. 219
·期 2
·1700427
·
IF 2.5
Pan Yuan,Zheng Ruan,Le Liu,Tuanwei Li,Titao Jing,Lifeng Yan
Supramolecular self-assembly of polymeric molecules for sharp-pH-sensitive (SPS) nanoparticles is an especially important application in biology. Here, amphiphilic polypeptide copolymers are synthesized and spontaneously assembled to micelles in aqueous solution, and protonation of the tertiary amine groups in the side-chain of the copolymer under weak acid causes the micelle disassembly, which is sharp-pH-sensitive, and the responsive pHs can be adjusted by adding salts. Size and morphologic change of the polymeric micelles are characterized by means of dynamic lighting scattering, transmission electron microscope (TEM), and atomic force microscope (AFM) in sequential pH alterations. It is found that the Hofmeister ions play a key factor in controlling the subtle interaction of different noncovalent bonds among polypeptide molecules during their self-assembly or disassembly. The physical property exploration of the SPS micelles may provide a new chance for the development of dynamic, complex nanostructures in various pH-responsive applications.
研究领域:
生物材料学
·
高分子化学
·
纳米医学
✓ 已验证
DOI
高影响因子
LANGMUIR
·
2021
·
IF 3.882
Ashish Trital,Weili Xue,Longgang Wang,Shengfu Chen
Chemotherapeutic nanodrugs have to penetrate through many biological barriers before reaching the tumor cells. Thus, high stability of the nanocarrier before reaching tumor cells and fast release of the carried drugs in targeted tumor cells are required. In this work, inspired by the intrinsic zwitterionic surface property, mainly formed by glutamic acid and lysine residues, of the plasma protein surface, the zwitterionic poly(glutamyl lysine-co-aspartic acid-co-cysteine) peptide (P(EK-D-C)) was synthesized for conjugating n-mercaptoalkanoic acid (MA) with different chain lengths on cysteine residues through a disulfide linkage to load hydrophobic doxorubicin (DOX). The results showed that the slightly negative-biased zwitterionic nanodrugs were very stable in both resistance to nonspecific plasma protein adsorption and prevention of premature DOX release at physiological pH 7.4 due to the zwitterionic polypeptide shell and the sharp contrast in polarity between the shell and DOX-loaded core, while they can quickly release the loaded DOX through responding to both low pH values in the endosome/lysosome and high glutathione concentrations in the tumor cell cytoplasm. Furthermore, the enhanced internalization of these nanodrugs led to about 60% higher in vitro cytotoxicity against MCF-7 cells at pH 6.7 than at pH 7.4, whereas the in vitro cytotoxicity of DOX·HCl at pH 6.7 was only 75% of the value at pH 7.4. In vivo results revealed that the stable nanodrugs conjugated with the long hydrophobic 12-mercaptododecanoic acid had higher tumor inhibition rate and lower systematic toxicity on MCF-7 tumor-bearing mice than the less stable nanodrugs conjugated with the short 8-mercaptooctaoic acid and were significantly superior to DOX·HCl. These results indicate that the combination of high stability in circulation and fast release in tumor cells of nanodrugs can enhance high efficacy targeted chemotherapy. This pH/redox-sensitive zwitterionic polypeptide nanocarrier might provide an excellent vehicle for solid tumor treatment.
研究领域:
生物材料学
·
肿瘤学
·
药剂学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHINESE JOURNAL OF CHEMISTRY
·
2023
·Vol. 41
·期 18
·2305-2310
·
IF 5.4
Rongye Li,Yue Zhao,Min Lin,Jing Sun
Comprehensive Summary Great efforts have been lately devoted to fabricating well-defined nanostructures using crystallization-driven self-assembly (CDSA) strategy. The influence of self-assembly on crystallization is also of great interest. Here, a series of amphiphilic diblock copolypeptoids poly( N -allylglycine)- b -poly( N -octylglycine) modified with cysteamine hydrochloride ((PNAG- g -NH 2 )- b -PNOG) were synthesized by ring-opening polymerization (ROP) and post-polymerization functionalization. The diblock copolypeptoid is comprised of one hydrophobic crystalline PNOG block and one hydrophilic amorphous block, which can aggregate into nanostructured assemblies with soluble PNAG- g -NH 2 as the corona layer and PNOG as the inner core in aqueous solution. With a systematic study by differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS), we demonstrated that the self-assembly of the block copolymers strengthens the crystallization of the PNOG block.
研究领域:
材料科学
·
高分子化学
·
生物材料
✓ 已验证
产品关联
DOI
高影响因子
AUSTRALIAN JOURNAL OF CHEMISTRY
·
2015
·Vol. 69
·期 1
·112-118
·
IF 1.558
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
✓ 已验证
DOI
高影响因子
Nature Protocols
·
2024
·
IF 13.1
Wu Yueming,Chen Kang,Wang Jiangzhou,Dai Wenhui,Yu Haowen,Xie Xinyi,Chen Minzhang,Liu Runhui
Synthetic polypeptides, also known as poly(α-amino acids), have the same polyamide backbone structures as natural proteins and peptides. As an important class of biomaterials, polypeptides have been widely used because of their biocompatibility, bioactivity and biodegradability. Ring-opening polymerization of N -carboxyanhydride (NCA) is a classical and widely used method for the synthesis of polypeptides. The dominantly used primary amine–initiated NCA polymerization can yield well-defined polymers and complex macromolecular architectures, but the reaction is slow and sensitive to moisture, making it necessary to use anhydrous solvents and a glovebox. One solution is to use lithium hexamethyldisilazide (LiHMDS) as the initiator, as described in this protocol. LiHMDS-initiated NCA polymerization is less sensitive to moisture and can be carried out in an open vessel outside the glovebox. It is also very fast; the reaction can be complete within 5 min to produce 30-mer polypeptides. In this protocol, poly(γ-benzyl- l -glutamate) is prepared as an example, but the protocol can easily be adapted to the synthesis of other polypeptides by generating NCAs from different amino acids, making it particularly suitable for the efficient parallel synthesis of polypeptide libraries. We provide detailed procedures for NCA synthesis and purification, the method of polymer end-group modification and measurement of polymerization kinetics and reactivity ratio. The procedure for synthesis of monomers and polymerization to form polypeptides requires <1 d. The superfast and open-vessel NCA polymerization method described here will probably enable a wide range of applications in the synthesis and functional study of polypeptide biomaterials.
研究领域:
生物化学
·
高分子化学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
·
2020
·
IF 8.758
Weili Xue,Ashish Trital,Jian Shen,Longgang Wang,Shengfu Chen
To augment the antitumor efficacy and minimize the significant side effects of chemotherapeutic drugs on health organs, a novel albumin-mimicking nanodrug, which is based on zwitterionic poly(glutamatyl lysine-co-cysteine) peptides scaffold, is developed to enhance pH-triggered tumor targeting via prolonging circulation time and accelerating cellular internalization. Results showed that the internalization of the nanodrug by MCF-7 cells is much faster than that by Doxil and even comparable to that by free doxorubicin (Dox) at tumor microenvironmental pH 6.7, whereas the internalization of the nanodrug is only 27.4 ± 7.6% of the Doxil by RAW-264.7 cells. Moreover, the significantly prolonged circulation time of the “stealthy” nanodrug was also comparable to that of the long circulating Doxil. As a result, the accumulation of the nanodrug in the tumor is much higher than that in the liver and kidney before the circulation half-life, which is significantly different from most other nanodrugs accumulated in the liver and kidney in this time scale. The tumor inhibition rate of the nanodrug was much higher than that of Doxil (93.2 ± 3.0% vs 54.2 ± 6.5%) after 18 day treatment, while the average bodyweight of the mice treated by the nanodrug was 26.9 ± 6.7% higher than that by Doxil. This indicated that the synergetic effect of long circulation time and fast cellular internalization of the nanodrug can significantly augment tumor targeting. This method might rejuvenate the traditional chemotherapeutic treatment.
研究领域:
药学
·
肿瘤学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
COLLOIDS AND SURFACES B-BIOINTERFACES
·
2012
·
IF 3.456
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
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）