The ionization degree, charge density, and conformation of weak polyelectrolytes can be adjusted through adjusting the pH and ionic strength stimuli. Such polymers thus offer a range of reversible interactions, including electrostatic complexation, H-bonding, and hydrophobic interactions, which position weak polyelectrolytes as key nano-units for the design of dynamic systems with precise structures, compositions, and responses to stimuli. The purpose of this review article is to discuss recent examples of nanoarchitectonic systems and applications that use weak polyelectrolytes as smart components. Surface platforms (electrodeposited films, brushes), multilayers (coatings and capsules), processed polyelectrolyte complexes (gels and membranes), and pharmaceutical vectors from both synthetic or natural-type weak polyelectrolytes are discussed. Finally, the increasing significance of block copolymers with weak polyion blocks is discussed with respect to the design of nanovectors by micellization and film/membrane nanopatterning via phase separation.
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http://dx.doi.org/10.3390/molecules27103263 | DOI Listing |
J Chem Theory Comput
January 2025
Institute for Computational Physics, University of Stuttgart, Allmandring 3, Stuttgart 70569, Germany.
The constant-pH Monte Carlo method is a popular algorithm to study acid-base equilibria in coarse-grained simulations of charge regulating soft matter systems including weak polyelectrolytes and proteins. However, the method suffers from systematic errors in simulations with explicit ions, which lead to a symmetry-breaking between chemically equivalent implementations of the acid-base equilibrium. Here, we show that this artifact of the algorithm can be corrected a-posteriori by simply shifting the pH-scale.
View Article and Find Full Text PDFProc Natl Acad Sci U S A
January 2025
Department of Chemical Engineering, University of Florida, Gainesville, FL 32611.
We describe a microfluidic device to extract DNA from a cell lysate, without the need for centrifuges, magnetic beads, or gels. Instead, separation is driven by transverse migration of DNA, which occurs when a polyelectrolyte solution flowing through a microfluidic channel is subjected to an electric field. The coupling of the weak shearing with the axial electric field is highly selective for long, flexible, charged molecules, of which DNA is the sole example in a typical cell lysate.
View Article and Find Full Text PDFPolymers (Basel)
December 2024
Research Laboratory "New Polymeric Materials", Nizhny Novgorod State Technical University, n.a. R.E. Alekseev, 24 Minin Street, 603155 Nizhny Novgorod, Nizhegorodskaya Oblast, Russia.
Anionic thermo- and pH-responsive copolymers were synthesized by photoiniferter reversible addition-fragmentation chain transfer polymerization (PI-RAFT). The thermo-responsive properties were provided by oligo(ethylene glycol)-based macromonomer units containing hydrophilic and hydrophobic moieties. The pH-responsive properties were enabled by the addition of 5-20 mol% of strong (2-acrylamido-2-methylpropanesulfonic) and weak (methacrylic) acids.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata (UNLP), CONICET, Boulevard 113 y 64, 1900 La Plata, Argentina.
We developed an arginine-responsive biosensor by integrating cascade enzymatic reactions into nanochannels functionalized with weak polyelectrolytes, which serve as "reactive signal amplifiers." This approach enhances device performance and broadens the detectable analyte range by generating high local analyte concentrations. The nanofluidic biosensor operates rapidly (<5 minutes) with a low detection limit of 3 μM.
View Article and Find Full Text PDFJ Chem Phys
November 2024
Department of Chemistry, Physics and Environmental and Soil Sciences and Agrotecnio, University of Lleida, Lleida, Catalonia, Spain.
Conformational and ionization equilibria of flexible weak polyelectrolytes (PEs) are, in general, strongly coupled. In this article, we analyze the effect of averaging over (or "contracting") the conformational degrees of freedom so that the original flexible molecule is replaced by an effective rigid object with the same ionization properties. As a result, one obtains the so-called Site Binding (SB) model, much easier to treat both theoretically and computationally, and extensively used to characterize the ionization properties of PE.
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