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Polymer Chemistry · 2015 ·Vol. 6 ·期 48 ·8343-8353 · IF 5.52

Synthesis, characterization, micellization and application of novel multiblock copolymers with the same compositions but different linkages

Lingdi Chen,Jiaxing Zhang,Yujie Liu,Hongdong Zhang,Guowei Wang

Several novel multiblock copolymers, (PEO-b-PS-b-PEO-Diyne)s, [PEO-b-PS-b-PEO-(OH)4]s and (PEO-b-PS-b-PEO-Acetal)s, with the same compositions but different linkages were constructed, and their micellization and application were studied. First, the precursor HO-PEO-b-PS-b-PEO-OH was prepared by sequential LAP and ROP mechanisms, and the precursor Propargyl-PEO-b-PS-b-PEO-Propargyl was achieved by a subsequent modification procedure. Subsequently, using the efficient Glaser coupling reaction, the multiblock copolymer (PEO-b-PS-b-PEO-Diyne)s was synthesized and the dyine groups embedded in the main chain were modified by a thiol–yne reaction to give multiblock copolymer [PEO-b-PS-b-PEO-(OH)4]s. Also, using the efficient Williamson reaction, the multiblock copolymer (PEO-b-PS-b-PEO-Acetal)s was obtained. Finally, the micellar morphologies formed from the synthesized copolymers were investigated and compared by DLS and TEM measurements, and the in vivo distribution of the micelles was also studied by loading them with a fluorescent probe. The results revealed that, under the same conditions, the multiblock copolymers can form micelles of different sizes. Due to the hydrophobicity of the introduced dyine groups and PS segments, smaller sized micelles can be formed, which traverse the BBB and therefore might result in a therapeutic application in the treatment of brain disease. However, the hydrophilicity of the acetal and hydroxyl groups gave a similar effect to that of the PEO segment, and larger sized micelles were formed.

研究领域: 高分子化学 · 纳米医学 · 药物递送
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CHINESE CHEMICAL LETTERS · 2014 · IF 1.178

Crystallization induced micellization of poly(p-dioxanone)-block-polyethylene glycol diblock copolymer functionalized with pyrene moiety

Chang-Lei Liu,Gang Wu,Si-Chong Chen,Jiao You,Yu-Zhong Wang

Poly( p -dioxanone)-block-polyethylene glycol diblock copolymers functionalized with pyrene moieties (Py-PPDO-b-PEG) at the chain ends of PPDO blocks were synthesized for preparing anisotropic micelles with improved stability. The micellization and crystallization of the copolymers were investigated by nano differential scanning calorimetry (Nano DSC), transmission electron microscopy (TEM), UV–vis spectrophotometery, fluorophotometer, and dynamic light scattering (DLS), respectively. The results indicated that the aggregation of pyrene induced by intermolecular interaction lead to micellization of Py-PPDO-b-PEG at much lower concentrations than those of PPDO-b-PEG copolymers without pyrene moieties. The aggregation of pyrene moieties may also serve as nucleation agent and therefore enhance the crystallization rate of PPDO blocks. Fluorescence measurements by using Nile Red as the fluorescent agent indicated that the micelles of Py-PPDO-b-PEG have high stability and load capacity for hydrophobic molecules.

研究领域: 材料科学 · 高分子化学
✓ 已验证 DOI 高影响因子
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JOURNAL OF APPLIED POLYMER SCIENCE · 2012 ·Vol. 128 ·期 5 ·2817-2822 · IF 1.289

Facile synthesis and micellization of biodegradable poly(decamethylene succinate)-graft-poly(ethylene glycol)

Guixiang Zhu,Ying Wang,Weipu Zhu,Kui Zhu,Xiaoyan Xu,Zhiquan Shen

In this article, we report the facile one-pot synthesis of poly(decamethylene succinate) (PDS) with multiple hydroxyl groups by direct polycondensation with malic acid (MA) as the functional monomer and dysprosium triflate as the chemoselective catalyst at 80°C. The secondary hydroxyl groups of malic units were inactive during the polycondensation process. The density of hydroxyl groups of the copolymer could be well-controlled by the molar ratio of succinic acid and MA in the feed. These hydroxylated PDSs were grafted by poly(ethylene glycol) (PEG) through a simple esterification reaction; this resulted in amphiphilic PDS- g -PEG copolymers, which could undergo micellization in aqueous media to form nanosized aggregates with diverse morphologies and diameters. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013.

研究领域: 高分子化学 · 材料科学
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Polymer Chemistry · 2015 ·Vol. 6 ·期 21 ·4020-4029 · IF 5.52

A facile synthesis of branched graft copolymers via combination of RAFT self-condensing vinyl polymerization and aldehyde–aminooxy reaction

Jianbing Huang,Lvhuan Lin,Hui Liang,Jiang Lu

A facile synthetic route to branched graft copolymers has been developed by combination of self-condensing vinyl polymerization (SCVP), reversible addition–fragmentation chain transfer (RAFT) polymerization and aldehyde–aminooxy reaction. RAFT polymerization of 2-(dimethylamino)ethyl methacrylate (DEM) in the presence of a newly designed aldehyde-containing chain-transfer monomer, 6-(2-formyl-4-vinylphenoxy)hexyl-2-(dodecylthiocarbonothioylthio)-2-methylpropanate (FHDM), led to branched polyDEM (BPDEM) bearing aldehyde functionalities on its branching points. The degree of branching and the average branch length of the resulting BPDEM can be readily tuned by manipulation of the DEM/FHDM feed ratio. The aldehyde groups on the branching points of BPDEM were then reacted with aminooxy-terminated poly(ethylene oxide)s (PEO-ONH2), affording the structurally well-defined branched graft copolymer BPDEM-g-PEO with a branched polyDEM backbone and PEO grafted chains. The thermo-induced micellization behavior of BPDEM-g-PEO in water was investigated. Opportunities are open for BPDEM-g-PEO to form either multimolecular micelles or unimolecular micelles via simply adjusting the chain length of grafted PEO. Further modification of BPDEM-g-PEO by quaternization resulted in branched cationic polyelectrolytes which are capable of capturing negatively charged guest molecules via electrostatic complexation to form in situ self-assembled nanoparticles with simultaneous encapsulation of the guests.

研究领域: 高分子化学 · 材料科学
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RSC Advances · 2024 ·Vol. 14 ·期 23 ·16207-16217 · IF 3.9

Injectable, self-healing and degradable dynamic hydrogels with tunable mechanical properties and stability by thermal-induced micellization

Chunqing Lin,Leniu Chen,Yuan He,Wenlong Xiang,Yujing Nie,Baixue Cai,Zanru Guo

Dynamic hydrogels possessing injectable, degradable and self-healing abilities have attracted considerable attention in the biomedical field in recent years, but it is difficult to tune the mechanical properties and stability of conventional dynamic hydrogels. In this work, we synthesized ABA-triblock copolymers via RAFT polymerization, where the A block consisted of thermo-sensitive poly(N-isopropylacrylamide-co-diacetone acrylamide) and the B block was hydrophilic poly(acrylamide). Subsequently, dynamic hydrogels were obtained based on the acylhydrazone bonds between the triblock copolymers and adipic acid dihydrazide (ADH). The obtained hydrogels exhibited injectable and self-healable abilities. In response to the thermal-induced micellization of their temperature-responsive blocks, the mechanical strength of the hydrogels not only increased, but also they exhibited high stability even at pH 2.0. Moreover, the hydrogel in the stable state could be degraded by the fracture of its trithiocarbonate groups. In addition, the hydrogels exhibited good cytocompatibility and controlled release behavior for doxorubicin (DOX). Considering these attractive tunable properties, these dynamic hydrogels show various potential applications in the biomedical field, such as drug carriers and cell or tissue engineering scaffolds.

研究领域: 生物医学工程 · 材料科学 · 组织工程
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JOURNAL OF POLYMER RESEARCH · 2012 ·Vol. 19 ·期 11 ·1-7 · IF 1.733

Synthesis and micellization of P(NIPAM-co-HMAM)-b-PEO-b-P(NIPAM-co-HMAM) triblock copolymers

Yu Wei-Na,Liu Shou-Xin,Wang Hong-Mei,Tian Rong

Temperature-responsive P(NIPAM- co -HMAM)- b -PEO- b -P(NIPAM- co -HMAM) triblock copolymers were synthesized by an atomic transfer radical polymerization (ATRP) method without freeze–pump–thaw cycles. The composition, structure, and molecular weight of the synthesized block copolymer were characterized by 1  H NMR and GPC. The phase transitions induced by temperature for different copolymers in dilute aqueous solutions have been studied using transmittance measurements, laser particle size measurements, viscosity analysis, and surface tension measurement, which showed that the HMAM content and the PEO (or PEG) chain length in the synthesized triblock copolymer affects the copolymer’s lower critical solution temperature (LCST). The micellization behavior of each temperature-responsive triblock copolymer was investigated by fluorescence probe measurements and transmission electron microscopy (TEM), which showed that the triblock copolymers form stable micelles above the LCST. The introduction of the HMAM component and the formation of micelles represent the first steps in the development of an injectable gel that forms in situ through chemical and physical crosslinking.

研究领域: 高分子化学 · 生物材料 · 药物递送系统
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2016 · IF 2.76

Influences of molecular structure of the cationic surfactant, additives and medium on the micellization of cationic/anionic surfactant mixed systems

Li-Sheng Hao,Yun-Feng Jia,Qian Liu,Ying Wang,Guang-Yu Xu,Yan-Qing Nan

The mixed micellization of four cationic/anionic surfactant aqueous systems formed by quaternary ammonium bromide surfactants with different molecular structures and sodium dodecylsulfonate (Na+AS−) at 318.15   K have been investigated. The dissociated Margules model has been used to model the nonideal mixed micellization. The gemini quaternary ammonium bromide (12-3-122+·2Br−) and Na+AS− aqueous mixed system shows the strongest synergism. The effect of added salt constituted by surfactant counterions on the mixed micellization of the gemini quaternary ammonium surfactant and alkali dodecylsulfonate with various counterions in aqueous solution at 318.15   K has been explored. When gemini surfactant is in excess, the specific counterion effect becomes insignificant. Whereas, when alkali dodecylsulfonate is in excess, the counterion effect of K+ is stronger than that of Na+. The effect of 1-propanol on the mixed micellization of the 12-3-122+·2Br−/Na+AS−/H2O system at 318.15   K has also been explored. Different from the nonmonotonic behavior of the single ionic surfactants, the critical micelle concentration (cmc) of the mixed systems increases with the increase of the concentration of added 1-propanol in the 1-propanol–water mixed medium.

CAS / MDL: 3282-73-3
研究领域: 物理化学 · 界面化学
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JOURNAL OF SURFACTANTS AND DETERGENTS · 2025 · IF 1.8

Properties of Mixed Systems of Sodium Dodecyl Diphenyl Ether Disulfonate and Cocamidopropyl Betaine

Nana Wang,Xiumei Tai,Tao Geng,Ying Liu,Mingliang Wu,Sai Li,Lingxiao Guo

The surface activity and a series of application properties of the mixture of anionic surfactant sodium dodecyl diphenyl ether disulfonate (2A1) and amphoteric surfactant cocamidopropyl betaine (CAB) were studied by measuring surface tension, contact angle, foamability and foam stability, zeta potential, as well as the chelation efficiency of trisodium methylglycine diacetate (MGDA) to Cu 2+ . The interaction parameters and thermodynamic micellization parameters of the CAB/2A1 complex system were calculated. The results show that the CAB/2A1 complex system behaves good synergistic effect, such as giving higher surface activity, smaller contact angle, and better foaming performance than the individual surfactants. The CAB and 2A1 molecules show strong interactions in both mixed micelles and mixed monolayer at air-water interface, and thermodynamic parameters calculated confirm that the micellization process is entropy-driven. The mixture gives the smallest contact angle or the best wetting performance at X (CAB) = 0.9, and shows the best foamability and foam stability at X (CAB) = 0.78. In addition, the mixture can significantly enhance chelation of the MGDA to Cu 2+ .

CAS / MDL: 10031-43-3
研究领域: 表面活性剂化学 · 胶体与界面科学 · 物理化学 · 应用化学
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Drug Design Development and Therapy · 2018 · IF 2.935

Self-nanomicellizing solid dispersion of edaravone: part I – oral bioavailability improvement

Ankit Parikh,Krishna Kathawala,Chun Chuan Tan,Sanjay Garg,Xin-Fu Zhou

Background Edaravone (EDR) is known for its free radical scavenging, antiapoptotic, antinecrotic, and anticytokine effects in neurological and non-neurological diseases. It is currently available clinically as Radicava® and Radicut®, intravenous medications, recently approved for the treatment of amyotrophic lateral sclerosis and cerebral infarction. However, the oral use of EDR is still restricted by its poor oral bioavailability (BA) due to poor aqueous solubility, stability, rapid metabolism, and low permeability. The present study reports the development of novel EDR formulation (NEF) using self-nanomicellizing solid dispersion (SNMSD) strategy with the aim to enable its oral use.Materials and methods The selection of a suitable carrier for the development of NEF was performed based on the miscibility study. The optimization of EDR-to-carrier ratio was conducted via kinetic solubility study after preparing SNMSDs using solvent evaporation technique. The drug–polymer carrier interaction and self-nanomicellizing properties of NEF were investigated with advanced characterization studies. In vitro permeation, metabolism, and dissolution study was carried out to examine the effect of the presence of a carrier on physico-chemical properties of EDR. Additionally, the dose-dependent pharmacokinetic study of NEF was conducted and compared with the EDR suspension.Results Soluplus® (SOL) as a carrier was selected based on the potential for improving aqueous solubility. The NEF containing EDR and SOL (1:5) resulted in the highest enhancement in aqueous solubility (17.53-fold) due to amorphization, hydrogen bonding interaction, and micellization. Moreover, the NEF demonstrated significant improvement in metabolism, permeability, and dissolution profile of EDR. Furthermore, the oral BA of NEF showed 10.2-, 16.1-, and 14.8-fold enhancement compared to EDR suspension at 46, 138, and 414 µmol/kg doses.Conclusion The results demonstrated that SNMSD strategy could serve as a promising way to enhance EDR oral BA and NEF could be a potential candidate for the treatment of diseases in which oxidative stress plays a key role in their pathogenesis.

研究领域: 药剂学 · 药学 · 药物递送系统 · 神经学
✓ 已验证 DOI PubMed 高影响因子
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FOOD CHEMISTRY · 2024 · IF 8.5

Enhancing vitamin D3 bioaccessibility: Unveiling hydrophobic interactions in soybean protein isolate and vitamin D3 binding via an infant in vitro digestion model

Jia-Rong Huang,Jing-Ru Song,Wan-Shuang Cai,Zhen-Wen Shao,Da-Yong Zhou,Liang Song

In the domain of infant nutrition, optimizing the absorption of crucial nutrients such as vitamin D 3 (VD 3 ) is paramount. This study harnessed dynamic-high-pressure microfluidization (DHPM) on soybean protein isolate (SPI) to engineer SPI-VD 3 nanoparticles for fortifying yogurt. Characterized by notable binding affinity ( K a  = 0.166 × 10 5  L·mol −1 ) at 80 MPa and significant surface hydrophobicity ( H 0  = 3494), these nanoparticles demonstrated promising attributes through molecular simulations. During simulated infant digestion, the 80 MPa DHPM-treated nanoparticles showcased an impressive 74.4% VD 3 bioaccessibility, delineating the pivotal roles of hydrophobicity, bioaccessibility, and micellization dynamics. Noteworthy was their traversal through the gastrointestinal tract, illuminating bile salts' crucial function in facilitating VD 3 re-encapsulation, thereby mitigating crystallization and augmenting absorption. Moreover, DHPM treatment imparted enhancements in nanoparticle integrity and hydrophobic properties, consequently amplifying VD 3 bioavailability. This investigation underscores the potential of SPI-VD 3 nanoparticles in bolstering VD 3 absorption, thereby furnishing invaluable insights for tailored infant nutrition formulations.

CAS / MDL: 7758-02-3
研究领域: 婴儿营养 · 食品科学 · 营养学 · 生物技术 · 化学工程
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JOURNAL OF SURFACTANTS AND DETERGENTS · 2021 ·Vol. 24 ·期 5 ·749-760 · IF 1.902

Thermodynamic Parameters and Interfacial Properties of Poly(ethylene glycol)-octyl Sulfosuccinates

Hongyan Cai,Wenli Luo,Yancheng Zheng,Yi Zhang,Lu Lai,Shanfa Tang

Surface tension of a series of poly(ethylene glycol)-octyl sulfosuccinates at different temperatures was measured, and the interfacial properties were investigated in the absence and presence of inorganic salts. Surface tension results indicate that critical micelle concentration (CMC) values of five surfactants (C8-PEG200, C8-PEG400, C8-PEG600, C8-PEG800, and C8-PEG1000) decrease as the molecular weight of polyethylene glycol (PEG) segments and the experimental temperature increases. The surface activity of the C8-PEG series changes with temperature, and the surface tension at the CMC ( γ CMC ) of the C8-PEG series decreases initially and then increases as the PEG molecular weight increases. This behavior may be attributed to the dehydration of the surfactant molecules, resulting in the change of hydrophile–lipophile balance for the different EO numbers in the surfactant molecules, which form a different surface energy film at the air–water interface. Negative ΔG m indicates that the micellization process of these surfactants is spontaneous and an entropically driven process. For the water/alkane interface, these surfactants have low interfacial activity. The interfacial tension (IFT) between these surfactants and alkanes increases first and then decreases with the increase in the molecular weight of PEG segments. After the addition of salt, the interfacial activity of the investigated surfactants increases significantly. The IFT between C8-PEG800 and 10–12 alkanes and between C8-PEG1000 and 12–16 alkanes reaches a low IFT magnitude of 10 −2 mN m −1 in the presence of 0.5% CaCl 2 or the mixed inorganic salts 0.5% NaCl+0.5% CaCl 2 .

研究领域: 物理化学 · 胶体科学 · 表面活性剂化学
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JOURNAL OF SURFACTANTS AND DETERGENTS · 2016 ·Vol. 19 ·期 6 ·1143-1151 · IF 1.853

Adsorption Behavior of Trimethylolpropane-Dehydroabietic Acid Ester at the Air–water Interface

Juying Zhou,Yanping Yang,Yuyan Liang,Fuhou Lei,Haitang Xu,Jianfang Lu,Yanzhi Zhao,Yan Zhou

A novel amphipathic trimethylolpropane-dehydroabietic acid ester was successfully prepared with acyl chloride method. Various analytical techniques such as liquid chromatography–mass spectrometry, Fourier transform infrared spectrometry, proton and carbon nuclear magnetic resonance spectroscopy were employed to evaluate the chemical structure of the ester. The surface properties of the ester were investigated by surface tension and resonance light-scattering techniques. The surfactant molecules are adsorbed at the water–air interface in different adsorption states, i.e., state 1 and 2. The dynamic adsorption behavior was studied by combining experimental results and a reorientation model. The molar fraction of solvent decreased, while the molar fraction of surfactant molecules increased with increasing ester concentration at the surface layer. The adsorption value of state 1 presented a unimodal shape and the adsorption value of state 2 presented an s-shape with the increase in surface pressure. The free energy of adsorption is −36.06 kJ mol −1 , more negative than the free energy of micellization (−29.69 kJ mol −1 ), it is actually easier for surfactant molecules to adsorb on the air–water interface.

CAS / MDL: 77-99-6
研究领域: 胶体化学 · 表面科学 · 分析化学 · 物理化学
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