Self-assembly, pH-responsibility and controlled release of doxorubicin of PDEAEMA-PEG-PDEAEMA triblock copolymers: effects of PEG length

AbstractTriblock copolymers have traditionally been synthesized with conventional organic components. However, triblock copolymers could be synthesized by the incorporation of two incompatible protein-based polymers. The polypeptides would differ in their hydrophobicity and confer unique physiochemical properties to the resultant materials. One protein-based polymer, based on a sequence of native elastin, that has been utilized in the synthesis of biomaterials is poly (Valine-Proline-Glycine-ValineGlycine) or poly(VPGVG) [1]. This polypeptide has been shown to have an inverse temperature transition that can be adjusted by non-conservative amino acid substitutions in the fourth position [2]. By combining polypeptide blocks with different inverse temperature transition values due to hydrophobicity differences, we expect to produce amphiphilic polypeptides capable of self-assembly into hydrogels. Our research examines the design, synthesis and characterization of elastin-mimetic block copolymers as functional biomaterials. The methods that are used for the characterization include variable temperature 1D and 2D High-Resolution-NMR, cryo-High Resolutions Scanning Electron Microscopy and Differential Scanning Calorimetry.

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Quadruple Hydrogen Bond-Containing A-AB-A Triblock Copolymers: Probing the Influence of Hydrogen Bonding in the Central Block

Molecules ◽

10.3390/molecules26154705 ◽

2021 ◽

Vol 26 (15) ◽

pp. 4705

Author(s):

Boer Liu ◽

Xi Chen ◽

Glenn A. Spiering ◽

Robert B. Moore ◽

Timothy E. Long

Keyword(s):

Hydrogen Bonding ◽

Self Assembly ◽

Microphase Separation ◽

Triblock Copolymers ◽

Random Copolymer ◽

Thermomechanical Properties ◽

Structure Property ◽

Scanning Calorimetry ◽

Central Block ◽

Quadruple Hydrogen Bonding

This work reveals the influence of pendant hydrogen bonding strength and distribution on self-assembly and the resulting thermomechanical properties of A-AB-A triblock copolymers. Reversible addition-fragmentation chain transfer polymerization afforded a library of A-AB-A acrylic triblock copolymers, wherein the A unit contained cytosine acrylate (CyA) or post-functionalized ureido cytosine acrylate (UCyA) and the B unit consisted of n-butyl acrylate (nBA). Differential scanning calorimetry revealed two glass transition temperatures, suggesting microphase-separation in the A-AB-A triblock copolymers. Thermomechanical and morphological analysis revealed the effects of hydrogen bonding distribution and strength on the self-assembly and microphase-separated morphology. Dynamic mechanical analysis showed multiple tan delta (δ) transitions that correlated to chain relaxation and hydrogen bonding dissociation, further confirming the microphase-separated structure. In addition, UCyA triblock copolymers possessed an extended modulus plateau versus temperature compared to the CyA analogs due to the stronger association of quadruple hydrogen bonding. CyA triblock copolymers exhibited a cylindrical microphase-separated morphology according to small-angle X-ray scattering. In contrast, UCyA triblock copolymers lacked long-range ordering due to hydrogen bonding induced phase mixing. The incorporation of UCyA into the soft central block resulted in improved tensile strength, extensibility, and toughness compared to the AB random copolymer and A-B-A triblock copolymer comparisons. This study provides insight into the structure-property relationships of A-AB-A supramolecular triblock copolymers that result from tunable association strengths.

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Multilayer composite beads constructed via layer-by-layer self-assembly for lysozyme controlled release

RSC Advances ◽

10.1039/c4ra02780a ◽

2014 ◽

Vol 4 (46) ◽

pp. 24369-24376 ◽

Cited By ~ 10

Author(s):

Jiemin Zhao ◽

Xiaoping Wang ◽

Yanshen Kuang ◽

Yufeng Zhang ◽

Xiaowen Shi ◽

...

Keyword(s):

Controlled Release ◽

Self Assembly ◽

Cross Linking ◽

Layer By Layer ◽

Multilayer Composite ◽

Composite Beads ◽

Assembly Technique ◽

Positively Charged

Alginate (ALG)–lysozyme (LZ) beads were fabricated by a cross-linking process. Negatively charged ALG and positively charged LZ were alternately deposited on the positively charged ALG–LZ beads via a layer-by-layer (LBL) self-assembly technique.

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Microcapsules for controlled release fabricated via layer-by-layer self-assembly of polyelectrolytes

Journal of Experimental Nanoscience ◽

10.1080/08927020802036005 ◽

2008 ◽

Vol 3 (2) ◽

pp. 133-145 ◽

Cited By ~ 14

Author(s):

Chaoyang Wang ◽

Shiqu Ye ◽

Qilong Sun ◽

Chengyi He ◽

Weihua Ye ◽

...

Keyword(s):

Controlled Release ◽

Self Assembly ◽

Layer By Layer

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Synthesis and self-assembly behaviour of poly(Nα-Boc-l-tryptophan)-block-poly(ethylene glycol)-block-poly(Nα-Boc-l-tryptophan)

RSC Advances ◽

10.1039/c6ra03718f ◽

2016 ◽

Vol 6 (29) ◽

pp. 24142-24153

Author(s):

Andreea S. Voda ◽

Kevin Magniez ◽

Nisa V. Salim ◽

Cynthia Wong ◽

Qipeng Guo

Keyword(s):

Drug Delivery ◽

Ethylene Glycol ◽

Self Assembly ◽

Triblock Copolymers ◽

Potential Drug ◽

Poly Ethylene Glycol ◽

Drug Delivery Applications ◽

Poly Ethylene ◽

First Time

We report for the first time the use of Nα-Boc-l-tryptophan for the synthesis of amphiphilic BAB triblock copolymers for potential drug delivery applications.

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Continuous Microfluidic Self-Assembly of Hybrid Janus-Like Vesicular Motors: Autonomous Propulsion and Controlled Release

Small ◽

10.1002/smll.201500527 ◽

2015 ◽

Vol 11 (31) ◽

pp. 3762-3767 ◽

Cited By ~ 45

Author(s):

Lei Wang ◽

Yijing Liu ◽

Jie He ◽

Matthew J. Hourwitz ◽

Yunlong Yang ◽

...

Keyword(s):

Controlled Release ◽

Self Assembly

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Self-assembly of amphiphilic di and triblock copolymers of styrene and quaternized 5-(N,N-diethylamino) isoprene in selective solvents

Polymer ◽

10.1016/s0032-3861(03)00013-2 ◽

2003 ◽

Vol 44 (7) ◽

pp. 2117-2128 ◽

Cited By ~ 30

Author(s):

Izabel C Riegel ◽

Dimitrios Samios ◽

Cesar L Petzhold ◽

Adi Eisenberg

Keyword(s):

Self Assembly ◽

Triblock Copolymers ◽

Selective Solvents

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Hydrogen-Bonding Mediated Self-Assembly of Amphiphilic ABA Triblock Copolymers into Well-Defined Giant Vesicles

Polymer Chemistry ◽

10.1039/d1py01061a ◽

2021 ◽

Author(s):

Huiying Wang ◽

Qiang Chen ◽

Zhen Geng ◽

Jingyi Rao ◽

Bijin Xiong ◽

...

Keyword(s):

Hydrogen Bonding ◽

Self Assembly ◽

Triblock Copolymers ◽

Giant Vesicles

Giant vesicles represent an extremely useful system to mimick biomembranes; however, available methodologies towards easy and direct vesicles construction are still scarce. By designing a hydrogen-bonding (H-bonding) amphiphilic ABA triblock...

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Self-assembly of block copolymers into sieve-like particles with arrayed switchable channels and as scaffolds to guide the arrangement of gold nanoparticles

Nanoscale ◽

10.1039/c7nr04923d ◽

2017 ◽

Vol 9 (39) ◽

pp. 15056-15061 ◽

Cited By ~ 17

Author(s):

Yun He ◽

Yan Zhang ◽

Nan Yan ◽

Yutian Zhu ◽

Wei Jiang ◽

...

Keyword(s):

Gold Nanoparticles ◽

Block Copolymers ◽

Self Assembly ◽

Triblock Copolymers ◽

Emulsion Droplets

The unique sieve-like particles with lattice arrayed switchable channels were created via the confined self-assembly of P4VP-b-PS-b-P4VP triblock copolymers within the emulsion droplets.

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