Preparation of New Amphiphilic Liquid-Crystal Diblock Copolymers Bearing Side-on Cholesteryl Mesogen and Their Self-aggregation

Chen, Shengdian; Li, Hui; Sun, Junqi; Ruilong, Sheng; Luo, Ting; Cao, Amin

doi:10.6023/a12121107

Cited by 7 publications

(4 citation statements)

References 15 publications

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“…Notably, the cholesterol conjugates of amphiphilic copolymer vectors were further found to be capable of altering the DOX-loaded complex nanoparticle cellular internalization mechanism . In addition, cholesterol as an interesting natural rod-like mesogen has recently been explored for the structural design of new liquid crystalline (LC) organics, functional synthetic lipids, and linear–dendritic block LC copolymers. − In particular, tailored block structural LC copolymer amphiphiles bearing grafted cholesterols like poly(ethylene glycol)- b -poly(cholesteryl acryloyoxy ethyl carbonate)s, poly(6-cholesteryloxyhexyl methacrylate)- b -poly(2-hydroxyethyl methacrylate)s, and poly(glyceryl methacrylate)- b -poly(6-cholesteryloxyhexyl methacrylate)s were found to self-assemble in aqueous media into nano-objects with finely ordered hierarchical structures due to the cholesterol hydrophobic interactions and mesogen stacking, and a number of unique morphologies such as periodically layered rod-like micelles, ellipsoidal vesicles, solid spheres, and nanotubes have been disclosed. − Moreover, Lu et al and Li et al separately prepared amphiphilic graft copolymers and reduction-sensitive diblock copolymers bearing pendant cholesterols, and their self-assembled nanoparticles and vesicles were further explored for DOX and calcein release, respectively. However, challenges of slow and less responsive release in cells still remained, which were due to the strong cholesterol hydrophobic interaction and highly ordered solid LC phase structure, and these impede their practical application as efficient drug delivery vectors.…”

Section: Introductionmentioning

confidence: 99%

Amphiphilic Diblock Terpolymer PMAgala-b-P(MAA-co-MAChol)s with Attached Galactose and Cholesterol Grafts and Their Intracellular pH-Responsive Doxorubicin Delivery

et al. 2015

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In this work, a series of diblock terpolymer poly(6-O-methacryloyl-D-galactopyranose)-b-poly(methacrylic acid-co-6-cholesteryloxy hexyl methacrylate) amphiphiles bearing attached galactose and cholesterol grafts denoted as the PMAgala-b-P(MAA-co-MAChol)s were designed and prepared, and these terpolymer amphiphiles were further exploited as a platform for intracellular doxorubicin (DOX) delivery. First, employing a sequential RAFT strategy with preliminarily synthesized poly(6-O-methacryloyl-1,2:3,4-di-O-isopropylidene-d-galactopyranose) (PMAIpGP) macro-RAFT initiator and a successive trifluoroacetic acid (TFA)-mediated deprotection, a series of amphiphilic diblock terpolymer PMAgala-b-P(MAA-co-MAChol)s were prepared, and were further characterized by NMR, Fourier transform infrared spectrometer (FTIR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and a dynamic contact angle testing instrument (DCAT). In aqueous media, spontaneous micellization of the synthesized diblock terpolymer amphiphiles were continuously examined by critical micellization concentration assay, dynamic light scattering (DLS), and transmission electron microscopy (TEM), and the efficacies of DOX loading by these copolymer micelles were investigated along with the complexed nanoparticle stability. Furthermore, in vitro DOX release of the drug-loaded terpolymer micelles were studied at 37 °C in buffer under various pH conditions, and cell toxicities of as-synthesized diblock amphiphiles were examined by MTT assay. Finally, with H1299 cells, intracellular DOX delivery and localization by the block amphiphile vectors were investigated by invert fluorescence microscopy. As a result, it was revealed that the random copolymerization of MAA and MAChol comonomers in the second block limited the formation of cholesterol liquid-crystal phase and enhanced DOX loading efficiency and complex nanoparticle stability, that ionic interactions between the DOX and MAA comonomer could be exploited to trigger efficient DOX release under acidic condition, and that the diblock terpolymer micellular vector could alter the DOX trafficking in cells. Hence, these suggest the pH-sensitive PMAgala-b-P(MAA-co-MAChol)s might be further exploited as a smart nanoplatform toward efficient antitumor drug delivery.

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Section: Introductionmentioning

confidence: 99%

Amphiphilic Diblock Terpolymer PMAgala-b-P(MAA-co-MAChol)s with Attached Galactose and Cholesterol Grafts and Their Intracellular pH-Responsive Doxorubicin Delivery

et al. 2015

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“…[31][32][33][34][35][36] Besides, LC materials containing cholesteryl groups have especially attracted more and more attention in the biomaterials fields. [3,[21][22][23][24][37][38][39][40][41] Stupp et al first reported the synthesis of cholesterol end functionalised oligo(L-lactic acid) and their interactions with cells. [21] Furthermore, Cheng [22] and Yang et al [23] also reported cholestery endcapped aliphatic polycarbonates and dicholestery end functionalised triblock poly(ε-caprolactone), respectively, as biodegradable polymers.…”

Section: Introductionmentioning

confidence: 98%

Synthesis and phase behaviour of new biodegradable liquid crystalline polycarbonate derived from side chain cholesteryl derivative

Guo

Liu

et al. 2015

Liquid Crystals

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A new cholesterol side-functionalised polycarbonate was synthesised through a coupling reaction between the terminal carboxyl group of the monomer 6-cholesteroxy-6-oxocaproic acid (COHA) and side hydroxyl group of the polycarbonate (PHTMC). The chemical structures of the intermediate compounds, monomers and polymers obtained in this study were characterised with FT-IR and 1 H NMR spectrum. Their phase behaviour and thermal stability were investigated using polarising optical microscopy, differential scanning calorimetry, X-ray diffraction and thermogravimetric analysis. The monomer COHA showed a cholesteric phase, while the corresponding cholesterol side-functionalised polycarbonate P(TMC-g-COHA) revealed a smectic A phase. This behaviour was attributed to an increased density of the mesogenic units in side chain and hence an ordered organisation into the mesophase. Furthermore, P(TMC-g-COHA) could exhibit a liquid crystalline state below body temperature (≈37°C). This fact indicated it could be used clinically as a self-assemble material with orientational-order mesophase. In addition, P(TMC-g-COHA) had a good thermal stability, the corresponding thermal decomposition temperature was 241°C.

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“…They could self-assemble into micro/nanoparticles with well-ordered cholesterol mesogens in the cores of cylinder micelles, solid spheres, and bowl-shaped aggregates, and in the membranes of hollow nanotubes, ellipsoidal vesicles and so forth. [ 44 , 45 , 46 , 47 , 48 ] Additionally, as an essential component of plasma membranes, cholesterol plays important roles in cell membrane formation, adhesion, and signal transduction, regulating lipid bilayer interaction [ 49 ] and intracellular trafficking of nanoparticles [ 50 , 51 ]. This brings the cholesterol-based amphiphiles new potential applications in biomedical engineering [ 52 , 53 , 54 ].…”

Section: Introductionmentioning

confidence: 99%

Morphology-Variable Aggregates Prepared from Cholesterol-Containing Amphiphilic Glycopolymers: Their Protein Recognition/Adsorption and Drug Delivery Applications

et al. 2018

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In this study, a series of diblock glycopolymers, poly(6-O-methacryloyl-d-galactopyranose)-b-poly(6-cholesteryloxyhexyl methacrylate) (PMAgala-b-PMAChols), with cholesterol/galactose grafts were prepared through a sequential reversible addition-fragmentation chain transfer (RAFT) polymerization and deprotection process. The glycopolymers could self-assemble into aggregates with various morphologies depending on cholesterol/galactose-containing block weight ratios, as determined by transmission electronic microscopy (TEM) and dynamic laser light scattering (DLS). In addition, the lectin (Ricinus communis agglutinin II, RCA120) recognition and bovine serum albumin (BSA) adsorption of the PMAgala-b-PMAChol aggregates were evaluated. The SK-Hep-1 tumor cell inhibition properties of the PMAgala-b-PMAChol/doxorubicin (DOX) complex aggregates were further examined in vitro. Results indicate that the PMAgala-b-PMAChol aggregates with various morphologies showed different interaction/recognition features with RCA120 and BSA. Spherical aggregates (d ≈ 92 nm) possessed the highest RCA120 recognition ability and lowest BSA protein adsorption. In addition, the DOX-loaded spherical complex aggregates exhibited a better tumor cell inhibition property than those of nanofibrous complex aggregates. The morphology-variable aggregates derived from the amphiphilic glycopolymers may serve as multifunctional biomaterials with biomolecular recognition and drug delivery features.

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Preparation of New Amphiphilic Liquid-Crystal Diblock Copolymers Bearing Side-on Cholesteryl Mesogen and Their Self-aggregation

Cited by 7 publications

References 15 publications

Amphiphilic Diblock Terpolymer PMAgala-b-P(MAA-co-MAChol)s with Attached Galactose and Cholesterol Grafts and Their Intracellular pH-Responsive Doxorubicin Delivery

Amphiphilic Diblock Terpolymer PMAgala-b-P(MAA-co-MAChol)s with Attached Galactose and Cholesterol Grafts and Their Intracellular pH-Responsive Doxorubicin Delivery

Synthesis and phase behaviour of new biodegradable liquid crystalline polycarbonate derived from side chain cholesteryl derivative

Morphology-Variable Aggregates Prepared from Cholesterol-Containing Amphiphilic Glycopolymers: Their Protein Recognition/Adsorption and Drug Delivery Applications

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