Formation and Stability of Water-Soluble, Molecular Polyelectrolyte Complexes: Effects of Charge Density, Mixing Ratio, and Polyelectrolyte Concentration

Langmuir ◽  
2009 ◽  
Vol 25 (11) ◽  
pp. 6113-6121 ◽  
Author(s):  
Alexander Shovsky ◽  
Imre Varga ◽  
Ričardas Makuška ◽  
Per M. Claesson
Polymers ◽  
2021 ◽  
Vol 13 (13) ◽  
pp. 2074
Author(s):  
Sara Tabandeh ◽  
Cristina Elisabeth Lemus ◽  
Lorraine Leon

Electrostatic interactions, and specifically π-interactions play a significant role in the liquid-liquid phase separation of proteins and formation of membraneless organelles/or biological condensates. Sequence patterning of peptides allows creating protein-like structures and controlling the chemistry and interactions of the mimetic molecules. A library of oppositely charged polypeptides was designed and synthesized to investigate the role of π-interactions on phase separation and secondary structures of polyelectrolyte complexes. Phenylalanine was chosen as the π-containing residue and was used together with lysine or glutamic acid in the design of positively or negatively charged sequences. The effect of charge density and also the substitution of fluorine on the phenylalanine ring, known to disrupt π-interactions, were investigated. Characterization analysis using MALDI-TOF mass spectroscopy, H NMR, and circular dichroism (CD) confirmed the molecular structure and chiral pattern of peptide sequences. Despite an alternating sequence of chirality previously shown to promote liquid-liquid phase separation, complexes appeared as solid precipitates, suggesting strong interactions between the sequence pairs. The secondary structures of sequence pairs showed the formation of hydrogen-bonded structures with a β-sheet signal in FTIR spectroscopy. The presence of fluorine decreased hydrogen bonding due to its inhibitory effect on π-interactions. π-interactions resulted in enhanced stability of complexes against salt, and higher critical salt concentrations for complexes with more π-containing amino acids. Furthermore, UV-vis spectroscopy showed that sequences containing π-interactions and increased charge density encapsulated a small charged molecule with π-bonds with high efficiency. These findings highlight the interplay between ionic, hydrophobic, hydrogen bonding, and π-interactions in polyelectrolyte complex formation and enhance our understanding of phase separation phenomena in protein-like structures.


1979 ◽  
Vol 21 (12) ◽  
pp. 3002-3008 ◽  
Author(s):  
O.A. Kharenko ◽  
A.V. Kharenko ◽  
R.I. Kalyuzhnaya ◽  
V.A. Izumrudov ◽  
V.A. Kasaikin ◽  
...  

Polymers ◽  
2019 ◽  
Vol 11 (2) ◽  
pp. 214 ◽  
Author(s):  
Carla Palomino-Durand ◽  
Marco Lopez ◽  
Frédéric Cazaux ◽  
Bernard Martel ◽  
Nicolas Blanchemain ◽  
...  

Injectable pre-formed physical hydrogels provide many advantages for biomedical applications. Polyelectrolyte complexes (PEC) formed between cationic chitosan (CHT) and anionic polymers of cyclodextrin (PCD) render a hydrogel of great interest. Given the difference between water-soluble (PCDs) and water-insoluble PCD (PCDi) in the extension of polymerization, the present study aims to explore their impact on the formation and properties of CHT/PCD hydrogel obtained from the variable ratios of PCDi and PCDs in the formulation. Hydrogels CHT/PCDi/PCDs at weight ratios of 3:0:3, 3:1.5:1.5, and 3:3:0 were elaborated in a double–syringe system. The chemical composition, microstructure, viscoelastic properties, injectability, and structural integrity of the hydrogels were investigated. The cytotoxicity of the hydrogel was also evaluated by indirect contact with pre-osteoblast cells. Despite having similar shear–thinning and self-healing behaviors, the three hydrogels showed a marked difference in their rheological characteristics, injectability, structural stability, etc., depending on their PCDi and PCDs contents. Among the three, all the best above-mentioned properties, in addition to a high cytocompatibility, were found in the hydrogel 3:1.5:1.5. For the first time, we gained a deeper understanding of the role of the PCDi/PCDs in the injectable pre-formed hydrogels (CHT/PCDi/PCDs), which could be further fine-tuned to enhance their performance in biomedical applications.


Nanomaterials ◽  
2020 ◽  
Vol 10 (4) ◽  
pp. 777 ◽  
Author(s):  
Luidmila S. Yakimova ◽  
Aigul R. Nugmanova ◽  
Olga A. Mostovaya ◽  
Alena A. Vavilova ◽  
Dmitriy N. Shurpik ◽  
...  

Controlling the self-assembly of polyfunctional compounds in interpolyelectrolyte aggregates is an extremely challenging task. The use of macrocyclic compounds offers new opportunities in design of a new generation of mixed nanoparticles. This approach allows creating aggregates with multivalent molecular recognition, improved binding efficiency and selectivity. In this paper, we reported a straightforward approach to the synthesis of interpolyelectrolytes by co-assembling of the thiacalix[4]arene with four negatively charged functional groups on the one side of macrocycle, and pillar[5]arene with 10 ammonium groups located on both sides. Nanostructured polyelectrolyte complexes show effective packaging of high-molecular DNA from calf thymus. The interaction of co-interpolyelectrolytes with the DNA is completely different from the interaction of the pillar[5]arene with the DNA. Two different complexes with DNA, i.e., micelleplex- and polyplex-type, were formed. The DNA in both cases preserved its secondary structure in native B form without distorting helicity. The presented approach provides important advantage for the design of effective biomolecular gene delivery systems.


Chirality ◽  
2020 ◽  
Vol 32 (5) ◽  
pp. 611-618
Author(s):  
Claudia Honisch ◽  
Rohanah Hussain ◽  
Giuliano Siligardi ◽  
Paolo Ruzza

2013 ◽  
Vol 63 (1) ◽  
Author(s):  
V. Navikaitė ◽  
P. P. Danilovas ◽  
R. Klimavičiūtė ◽  
J. Bendoraitienė

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