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

2021 ◽  
Author(s):  
Huiying Wang ◽  
Qiang Chen ◽  
Zhen Geng ◽  
Jingyi Rao ◽  
Bijin Xiong ◽  
...  

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...

Molecules ◽  
2021 ◽  
Vol 26 (15) ◽  
pp. 4705
Author(s):  
Boer Liu ◽  
Xi Chen ◽  
Glenn A. Spiering ◽  
Robert B. Moore ◽  
Timothy E. Long

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.


2002 ◽  
Vol 724 ◽  
Author(s):  
Elizabeth R. Wright ◽  
R. Andrew McMillan ◽  
Alan Cooper ◽  
Robert P. Apkarian ◽  
Vincent P. Conticello

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.


Molecules ◽  
2021 ◽  
Vol 26 (13) ◽  
pp. 4097
Author(s):  
Wooyong Seong ◽  
Hyungwoo Hahm ◽  
Seyong Kim ◽  
Jongwoo Park ◽  
Khalil A. Abboud ◽  
...  

Bimetallic bis-urea functionalized salen-aluminum catalysts have been developed for cyclic carbonate synthesis from epoxides and CO2. The urea moiety provides a bimetallic scaffold through hydrogen bonding, which expedites the cyclic carbonate formation reaction under mild reaction conditions. The turnover frequency (TOF) of the bis-urea salen Al catalyst is three times higher than that of a μ-oxo-bridged catalyst, and 13 times higher than that of a monomeric salen aluminum catalyst. The bimetallic reaction pathway is suggested based on urea additive studies and kinetic studies. Additionally, the X-ray crystal structure of a bis-urea salen Ni complex supports the self-assembly of the bis-urea salen metal complex through hydrogen bonding.


RSC Advances ◽  
2016 ◽  
Vol 6 (29) ◽  
pp. 24142-24153
Author(s):  
Andreea S. Voda ◽  
Kevin Magniez ◽  
Nisa V. Salim ◽  
Cynthia Wong ◽  
Qipeng Guo

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.


Author(s):  
Ganghuo Pan ◽  
Jie Leng ◽  
Liye Deng ◽  
Liwen Xing ◽  
Rui Feng

2003 ◽  
pp. 2278 ◽  
Author(s):  
Jing Tang ◽  
Henrik Birkedal ◽  
Eric W. McFarland ◽  
Galen D. Stucky

2007 ◽  
Vol 601 (16) ◽  
pp. L91-L94 ◽  
Author(s):  
Junseok Lee ◽  
Daniel B. Dougherty ◽  
John T. Yates

Polymer ◽  
2003 ◽  
Vol 44 (7) ◽  
pp. 2117-2128 ◽  
Author(s):  
Izabel C Riegel ◽  
Dimitrios Samios ◽  
Cesar L Petzhold ◽  
Adi Eisenberg

2008 ◽  
Vol 8 (6) ◽  
pp. 2996-3002 ◽  
Author(s):  
Liqin Ge ◽  
Xing Wang ◽  
Long Ba ◽  
Zhongze Gu

The hydrogen-bonding multilayered polyelectrolyte capsules with sizes around 6 μm were fabricated by layer-by-layer self-assembly method. The morphology of the obtained capsules was observed with Scanning Electron Microscope (SEM), Confocal Laser Scanning Microscope (CLSM) and Atomic Force Microscope (AFM), respectively. The elastic properties of the capsules were studied with AFM. The capsule was pressed by cantilever with different lengths, a glass bead glued at the end of the cantilever. The force curves were measured on the capsule in air. The Young's modulus of the capsule was obtained (E = 170 MPa for the loading). Results show that this model can predict the elastic deformation of the microcapsule. The accuracy of the elastic deformation of polymer capsule can be ensured using a cantilever of mediate stiffness. Our results show that the existence of the hydrogen-bonding layer makes the multilayered polyelectrolyte harder in comparison with the pure multilayered polyelectrolyte capsules.


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