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JOURNAL OF MOLECULAR LIQUIDS · 2022 · IF 6.633

Formation of ultrathin scarf-like micelles, ultrathin disk-like micelles and spherical micelles by self-assembly of polyurethane diblock copolymers

Rui Qi,Baohua Liu,Hongmei Li,Jian Wang,Xiaohong Li,Yong Jin,Songzhi Xie

Controlling the shape and size of the nanomicelles attracts great interest and is still challenging. Herein, we synthesized a kind of diblock copolymers with the hydrophilic block (poly (ethylene glycol) methyl ether, PEG) and the core-forming block composed alternately by hydrophobic segments, hydrogen-bonding carbamates and pH-responsive groups. The synergy effect of the pH variation and the core-forming block length on the morphologies of the assemblies was well studied. Ultrathin scarf-like micelles, ultrathin disk-like micelles and spherical micelles were obtained by tailoring the pH values and the lengths of the core-forming blocks. The ultrathin scarf-like micelles and ultrathin disk-like micelles were proved to be composed of   a lamellar   bimolecular layer   of the block copolymers. This study will supply an effective method to fabricate well-defined nanostructures.

研究领域: 高分子化学 · 纳米材料科学
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CARBOHYDRATE POLYMERS · 2021 · IF 9.381

Self-assembly behavior and conformation of amphiphilic hemicellulose-graft-fatty acid micelles

Feng Shen,Hao Ling,Wenjiao Ge,Yang Yang,Xiaoying Wang,Junli Ren,Xiaohui Wang

In this work, a series of amphiphilic hemicellulose-based grafting polymers are synthesized by homogeneous esterification with various hydrophobic chain fatty acids. With the flexible chain conformation of hemicelluloses, the hemicellulose-graft-fatty acid is self-assembled into hard sphere micelles in aqueous solution through hydrophobic interactions. The resultant micelles show apparent hydrodynamic radius (R h ) varying in the range of 34–57 nm and radius of gyration (R g) varying from 30 to 44 nm. Moreover, the R h , R g , zeta potential and critical micelle concentration (CMC) of the micelles gradually decreases with the increasing hydrophobic chain length. The aggregation number of micelles can be tuned by varying alkyl chain lengths. Taking curcumin (Cur) as a model drug, the hemicellulose micelles were investigated as drug carriers, which exhibit a chain length-controlled drug release behavior. Taken together, structure and property tunable hemicellulose-based micelles were obtained, and showed potential of application in pharmaceutical, food, and cosmetics fields.

研究领域: 材料科学 · 药学 · 生物化学
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Colloid and Interface Science Communications · 2021 · IF 4.914

The effect of topology of PEG chain on the stability of micelles in brine and serum

Bin Wu,Wei-Qiang Huang,Xuan Nie,Ze Zhang,Guang Chen,Hai-Li Wang,Fei Wang,Shen-Gang Ding,Zong-Yao Hao,Ye-Zi You

Polymeric micelles are promising vehicles for drug delivery these years. The stability of micelles in blood system is very important for the encapsulated therapeutic agents reaching the targeting area. However, generally, micelles are not stable in the presence of proteins and ions after being injected intravenously. The topology of polymer chain on the surface of micelles plays a key role on the stability of micelles. Here we have prepared flower micelles and the traditional micelles via self-assembly of triblock and diblock copolymer of polyethylene glycol (PEG) and poly(ε-caprolactone) (PCL) in water. The special PEG shell of flower micelles prevents micelles from ions and proteins, which endows the micelles with the ability to resist aggregation. The experiment results show that flower micelles are much more stable in the presence of serum and salt than traditional micelles, which indicates these micelles would be promising in drug delivery in the future.

研究领域: 药剂学 · 生物医学工程
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CHEMICAL ENGINEERING JOURNAL · 2012 · IF 3.461

Synthesis, micellization and caffeine drug release kinetics of novel PBMA-b-PNIPAAm block polymer brushes

Yan-Ling Luo,Li-Li Zhang,Feng Xu

Brush-like block copolymers with poly( t -butyl methacrylate) (PBMA) and poly(N-ispropylacrylamide) (PNIPAAm) as side arms, PBMA-b-PNIPAAm, were designed and synthesized via a simple free radical polymerization route. The chemical structure and molecular weight of these polymer brushes were characterized and determined by nuclear magnetic resonance ( 1 H NMR), Fourier transform infrared spectrometry (FT-IR) and gel permeation chromatography (GPC). The polymer brushes can spontaneously assembled into regularly spherical core–shell nanostructured micelles with well-dispersed individual nanoparticles in aqueous solutions, and physiochemical properties of the micelles formed were detected by a surface tension technique, nanoparticle analyzer, transmission electron microscope (TEM), dynamic light scattering (DLS) and UV–vis transmittance measurements. Low critical micelle concentration (CMC) and high zeta potentials revealed the micellar stability and the micellar particle size was in the range from 36 to 93   nm by TEM and less than 200   nm by DLS. The resulting block polymer brushes were temperature-sensitive with low critical solution temperature (LCST) about 28.80–29.40   °C. These characteristic parameters were affected by their compositional ratios and the length of hydrophilic or hydrophobic chains. The evaluation for caffeine drug release and release kinetics demonstrated that the drug release and bioavailability may be mediated or improved by the temperature-induced structural changes of the micelles and different diffusion mechanism.

研究领域: 高分子化学 · 药剂学 · 纳米技术
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CHEMISTRY-A EUROPEAN JOURNAL · 2019 ·Vol. 25 ·期 24 ·6203-6211 · IF 5.16

Polyoxometalate-Based Photochromic Supramolecular Hydrogels with Highly Ordered Spherical and Cylindrical Micellar Nanostructures

Na Sun,Aoli Wu,Yang Yu,Xinpei Gao,Liqiang Zheng

Graphical Gelling behavior : Polyoxometalate-based supramolecular hydrogels with highly ordered spherical and cylindrical micellar nanostructures exhibit excellent photochromic ability (see figure). By adjusting the molar ratio of the zwitterionic amphiphile component to the polyoxometalate, ordered spherical micelle-based hydrogels and aligned wormlike micelle-based hydrogels can be obtained. Polyoxometalates (POMs) have attracted much attention in the field of photochromic materials. However, POM-based photochromic supramolecular hydrogels with high transparency and good photochromic properties are seldom reported. In this work, a homogenous, optically transparent, injectable, and photochromic supramolecular hydrogel was fabricated through the coassembly of ammonium heptamolybdate (Mo 7 ) and an imidazolium-based zwitterionic amphiphile (3-(1-hexadecyl-3-imidazolio)propanesulfonate (C 16 IPS)). The balance between electrostatic attraction and repulsion of Mo 7 clusters and zwitterionic amphiphiles enables them to coassemble into a homogenous and transparent supramolecular hydrogel. By adjusting the molar ratio of C 16 IPS/Mo 7 , ordered spherical micelle-based hydrogels and aligned wormlike micelle-based hydrogels can be obtained. The incorporation of Mo 7 into hydrogels endows these hydrogels with excellent photochromic properties. Specifically, after coassembly with C 16 IPS, the photochromic ability of hydrogels is significantly enhanced compared with that of a pure aqueous solution of Mo 7 . These hydrogels exhibit great potential applications as photochromic materials for the recording of rewritable information.

研究领域: 材料科学 · 化学
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INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES · 2022 ·Vol. 23 ·期 17 ·9698 · IF 6.208

Intelligent Drug Delivery by Peptide-Based Dual-Function Micelles

Dong Wan,Yujun Liu,Xinhao Guo,Jianxin Zhang,Jie Pan

To endow the polymeric prodrug with smart properties through a safe and simple method, matrix metalloproteinase (MMPs) responsive peptide GPLGVRGDG was introduced into the block copolymer to prepare TPGS3350-GPLGVRGDG-DOX&DOX micelles, where TPGS3350is D-α-tocopheryl polyethylene glycol 3350 succinate. During the doxorubicin delivery, the cleavage of the peptide chain triggers de-PEGylation, and the remaining VRGDG sequence was retained on the surface of the micelles, which can act as a ligand to facilitate cell uptake. Moreover, the cytotoxicity of TPGS3350-GPLGVRGDG-DOX&DOX micelles against 4T1 cells was significantly improved, compared with TPGS3350-GPLGVRG-DOX&DOX micelles and TPGS3350-DOX&DOX micelles. During in vivo studies, TPGS3350-GPLGVRGDG-DOX&DOX micelles exhibited good anticancer efficacy with long circulation in the body and more efficient accumulation at the tumor site. Therefore, TPGS3350-GPLGVRGDG-DOX&DOX micelles have improved antitumor activity and reduced toxic side effects. This work opens new potential for exploring the strategy of drug delivery in clinical applications.Keywords:drug delivery;peptide;micelles

CAS / MDL: 4345-03-3
研究领域: 药学 · 肿瘤学
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JOURNAL OF POLYMER RESEARCH · 2024 ·Vol. 31 ·期 9 ·1-10 · IF 2.6

Hydroxyethyl methacrylate modified polylactic acids and their micelle properties

Luo Shi-He,Xiao Ying,Gao Juan-Juan,Cao Xi-Ying,Fang Yong-Gan,Lin Jian-Yun,Li Huan-Qing,Wang Zhao-Yang

Polylactic acid (PLA) is one of promising biocompatible and biodegradable polyester. Poly(2-hydroxyethyl methacrylate) (PHEMA) is a polymer with good hydrophilicity. The hydrophilic PHEMA may improve PLA’s amphiphilic properties. Hence, directly starting from hydroxyethyl methacrylate (HEMA), lactic acid (LA), maleic anhydride (MAH) and 2,2'-azobis(2-methyl-propionitrile) (AIBN), a series of new amphiphilic copolymers PLA 20 MH n were obtained through direct melt polycondensation (DMP) and subsequent free radical polymerization (FRP) in one pot. The results show that PLA 20 MH n can self-assemble in aqueous solution to form stable spherical micelles and dissolve hydrophobic pyrene molecules. What’s more, The CMC value can be adjusted by the polymerization ratio. Therefore, this method is expected to further realize the encapsulation and controlled release of hydrophobic drug molecules for systemic circulation in vivo.

CAS / MDL: 78-67-1
研究领域: 材料科学 · 生物医学工程
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Frontiers in Chemistry · 2022 · IF 5.545

A peptide-DNA hybrid bio-nanomicelle and its application for detection of caspase-3 activity

Fan Zhang,Changqing Mao,Siyu Cao,Runchi Zhang,Yi Guo,Guifang Chen,Chang Feng

Bio-nanomicelles based on biomaterials such as nucleic acids, peptides, glycans, and lipids have developed rapidly in the field of bioanalysis. Although DNA and peptides have unique advantages, unfortunately, there are few bio-nanomicelles integrating DNA with peptides. Here, we designed a peptide-DNA hybrid bio-nanomicelle for the activity detection of caspase-3. The detection mechanism is based on caspase-3 specific recognition and cleavage of peptide substrates, which owns high sensitivity and selectivity. Under optimal conditions, the detection of caspase-3 activity can be achieved using our designed bio-nanomicelles and the detection limit is 0.72 nM. Furthermore, the proposed method was also successfully applied for the detection of caspase-3 in cell lysate samples after apoptosis-inducing.

研究领域: 生物分析 · 纳米技术 · 生物医学工程
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Polymers · 2025 ·Vol. 17 ·期 3 ·349 · IF 4.9

Predicting the Key Properties of a Modified Product to Pre-Select a Pluronic F127 Modification Scheme for Preparing High-Quality Nano-Micelles

Jizheng Song,Yu Hu,Shiyu Yang,Dexue Liu,Yiider Tseng,Lingjun Li

Hydrophobic modification alters the properties of Pluronic F127 to form micelles more efficiently and enhances its drug-loading capacity. However, selecting the appropriate hydrophobic group for modification is laborious. In this paper, we propose an efficient approach for predicting key parameters to select hydrophobic groups for F127 modification prior to synthesis, in order to improve the formability and stability of the micelles. The results of nuclear magnetic resonance and isothermal titration calorimetry were utilized to establish a function for predicting the hydrophile–lipophile balance, critical micelle concentration, and Gibbs free energy of the products based on the structure of raw material. These predicted values can assist us in selecting suitable hydrophobic groups for F127 modification. Subsequently, we successfully tested our method and validated our work using pharmaceutical evaluation methods, such as appearance observation, particle size measurement, drug loading determination, equilibrium binding rate assessment, storage stability testing, and the plotting of accumulation release curves. Therefore, we suggest that our work could provide a model linking the molecular structure to properties, with the purpose of pre-selecting modification products that have advantages in micelle preparation. This can facilitate the application of F127 in preparing nano-micelles.

研究领域: 药学 · 化学工程 · 材料科学 · 纳米技术
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EUROPEAN POLYMER JOURNAL · 2019 · IF 3.621

Cationic micelles self-assembled from quaternized cellulose-g-oligo (ε-caprolactone) amphiphilic copolymers

Suzhen Liu,Li Zhang,Xiaohong Chen,Tingting Chu,Yanzhu Guo,Meihong Niu

A novel kind of cationic cellulose- g -oligo(ε-caprolactone) amphiphilic polymer (QC- g -OCL) was obtained by homogeneous ring-opening polymerization of ε-caprolactone (ε-CL) from quaternized cellulose (QC) in 1-butyl-3-methylimidazolium chloride (BmimCl) ionic liquids. Chemical structures and properties of the copolymers were characterized by FT-IR, 1 H NMR, 13 C NMR, XRD and TGA techniques. The grafting ratios of OCL chain onto QC- g -OCL were adjusted by changing the molar ratio of CL to QC. The micelles self-assembled from QC- g -OCL were prepared by ultrasonic-assisted dissolution method, and comprehensively analyzed by dynamic light scattering (DLS), TEM and fluorescence spectroscopy techniques. The micelles were in spherical shape with average hydrodynamic radiuses (R h ) in the range of 170–237 nm. Moreover, their critical micelle concentration (CMC) values were decreased from 0.302 mg/mL to 0.089 mg/mL with increasing the degree substitution values of OCL (DS OCL ) from 0.16 to 0.60. The ζ-potentials of micelles in water were ranged from 37.2 mV to 48.3 mV, indicating that the shells of micelles were constituted by ationic quaternary ammonium group. All of these findings established that the cationic cellulose-based micelles would be a promising aqueous carrier for hydrophobic drug.

研究领域: 材料科学 · 药物传递系统
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FOOD HYDROCOLLOIDS · 2020 · IF 7.053

Acetylated debranched starch micelles as a promising nanocarrier for curcumin

Qing Liu,Fang Li,Na Ji,Lei Dai,Liu Xiong,Qingjie Sun

Natural amphiphilic polymer micelles are of great interest as a carrier of hydrophobic functional ingredients due to their relatively easy synthesis, biocompatibility, and extensive sources. This study modified debranched starch (DBS) with acetic anhydride to introduce the hydrophobic acetyl group, and micelles were then obtained through the self-assembly of acetylated debranched starch (ADBS). The degree of substitution (DS) and the structural and thermal properties of ADBS were systematically investigated; the maximum DS value was 0.17. Proton nuclear magnetic resonance spectra of ADBS confirmed the presence of acetyl methyl protons, and Fourier transform infrared spectra exhibited a new absorption band of carbonyl C = O vibration at 1730 cm −1 due to the introduction of acetyl. The developed micelles were mostly spherical, and the particle size was about 50–100 nm. The critical micelle concentration was 0.45 mg/mL. Curcumin was incorporated into the micelles successfully, and the curcumin-loaded micelles exhibited sustained release properties in simulated gastric and intestinal fluids.

CAS / MDL: 458-37-7
研究领域: 食品科学与工程 · 生物材料学
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POLYMER · 2014 · IF 3.766

Synthesis and self-assembly of amphiphilic polyphosphazene with controllable composition via two step thiol-ene click reaction

Chen Chen,Xiao-Jun Huang,Yang Liu,Yue-Cheng Qian,Zhi-Kang Xu

Sequential thiol-ene click reaction is reported for amphiphilic glycosylated polyphosphazene. Poly[bis(allylamino)phosphazene] was used as precursor to go through UV irradiation with 2,3,4,6-tetra-O-acetyl-1-thiol- β -D-glucopyranose (SH-GlcAc 4 ) and 1-dodecanethiol in sequence. Variation of the reaction conditions, including click reaction time and the dose of photoinitiator , led to different hydrophilic/hydrophobic ratios. As a result, glycosylated polyphosphazenes were synthesized with 53.3%, 77.7% and 85.0% of glucose moieties. The different residual composition could give rise to different self-assembly behaviors. Micelles of amphiphilic polyphosphazenes were formed in aqueous solution and the CMC value (0.79 × 10 −3 –4.00 × 10 −3  mg/mL) as well as mean diameter (170–220 nm) varied along with the hydrophilic glucose moiety/hydrophobic dodecyl moiety ratio.

研究领域: 材料科学 · 化学工程 · 生物材料
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