Kinetics of Macroion Adsorption on Silica: Complementary Theoretical and Experimental Investigations for Poly-l-arginine

Langmuir, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 21, 2025

A comprehensive approach enabling a quantitative interpretation of poly-l-arginine (PARG) adsorption kinetics at solid/electrolyte interfaces was developed. The first step involved all-atom molecular dynamics (MD) modeling physicochemical characteristics yielding PARG molecule conformations, its contour length, and the cross-section area. It also shown that molecules, even in concentrated electrolyte solutions (100 mM NaCl), assume largely elongated shape with an aspect ratio 36. Using parameters derived from MD, silica/electrolyte interface calculated using random sequential approach. These predictions were validated by optical reflectometry measurements. confirmed molecules irreversibly adsorbed side-on orientation their coverage agreed predicted MD modeling. theoretical experimental results used for quartz crystal microbalance measurements carried out under various pH conditions. analysis unveiled stemming hydrodynamic theory postulating lubrication-like (soft) contact macroion sensor adequately reflect kinetics. range validity intuitively Sauerbrey model estimated. argued acquired can be exploited to control solid/liquid interfaces. This is essential optimum preparation supporting layers bioparticle immobilization shell formation nanocapsules targeted drug delivery.

Language: Английский

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Effect of Polymer Variation in Cu-Polymer Composite Electrodes on Electrochemical CO₂ Reduction

ACS Applied Energy Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 17, 2025

Language: Английский

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Artificial Intelligence and Multiscale Modeling for Sustainable Biopolymers and Bioinspired Materials

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: March 10, 2025

Biopolymers and bioinspired materials contribute to the construction of intricate hierarchical structures that exhibit advanced properties. The remarkable toughness damage tolerance such multilevel are conferred through assembly their multiscale (i.e., atomistic macroscale) components architectures. Here, functionality mechanisms biopolymers bio-inspired at multilength scales explored summarized, focusing on biopolymer nanofibril configurations, biocompatible synthetic biopolymers, composites. Their modeling methods with theoretical basis multiple lengths time reviewed for applications. Additionally, exploration artificial intelligence-powered methodologies is emphasized realize improvements in these from functionality, biodegradability, sustainability characterization, fabrication process, superior designs. Ultimately, a promising future versatile manufacturing across wider applications greater lifecycle impacts foreseen.

Language: Английский

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Polypeptide-based multilayer nanoarchitectures: Controlled assembly on planar and colloidal substrates for biomedical applications

Advances in Colloid and Interface Science, Journal Year: 2024, Volume and Issue: 331, P. 103248 - 103248

Published: July 15, 2024

Polypeptides have shown an excellent potential in nanomedicine thanks to their biocompatibility, biodegradability, high functionality, and responsiveness several stimuli. exhibit propensity organize at the supramolecular level; hence, they been extensively considered as building blocks layer-by-layer (LbL) assembly. The LbL technique is a highly versatile methodology, which involves sequential assembly of blocks, mainly driven by electrostatic interactions, onto planar or colloidal templates fabricate sophisticated multilayer nanoarchitectures. simplicity mild conditions required approach led inclusion biopolymers bioactive molecules for fabrication wide spectrum biodegradable, biocompatible, precisely engineered films biomedical applications. This review focuses on those examples polypeptides used nanoarchitectures tissue engineering drug delivery applications, highlighting characteristics strategies adopted increase stability film. Cross-linking presented powerful strategy enhance stiffness network, fundamental requirement For example, engineering, stiff coating, presence adhesion promoters, and/or boost adhesion, growth, differentiation cells. On contrary, antimicrobial coatings should repel inhibit growth bacteria. In focused particles capsules micro- nano-meter scale, film crucial terms retention controlled release payload. Recent advances key role adsorption genetic material with loading efficiency, addressing different pathways particles/capsules during intracellular uptake, paving way applications personalized medicine. Although there are few studies, pH changes, together stimuli-responsive entities into represents further factor development smart systems promote sustained therapeutics. degradability may be obstacle certain scenarios once external stimulus applied. Nowadays, design biodegradable oriented theranostics that, limited use polypeptides, still infancy.

Language: Английский

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A Computational Chemistry Approach to the Molecular Design of SiO2 Nanoparticles Coated with Stearic Acid and Sodium Stearate in Ethanol Solvent.

Colloids and Surfaces A Physicochemical and Engineering Aspects, Journal Year: 2023, Volume and Issue: 679, P. 132527 - 132527

Published: Oct. 10, 2023

Language: Английский

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pH dependence of the assembly mechanism and properties of poly(l-lysine) and poly(l-glutamic acid) complexes

Physical Chemistry Chemical Physics, Journal Year: 2023, Volume and Issue: 25(27), P. 18182 - 18196

Published: Jan. 1, 2023

We show by extensive experimental characterization combined with molecular simulations that pH has a major impact on the assembly mechanism and properties of poly(L-lysine) (PLL) poly(L-glutamic acid) (PGA) complexes. A combination dynamic light scattering (DLS) laser Doppler velocimetry (LDV) is used to assess complexation, charge state, other physical characteristics complexes, isothermal titration calorimetry (ITC) examine complexation thermodynamics, circular dichroism (CD) extract polypeptides' secondary structure. For enhanced analysis interpretation data, analytical ultracentrifugation (AUC) define precise weights solution association peptides. Molecular dynamics reveal associated intra- intermolecular binding changes in terms intrinsic vs. extrinsic compensation, role hydrogen bonding, structure changes, aiding data. combine data dependency PLL/PGA level mechanisms. This work shows not only provides means control complex formation but also conformation can be systematically materials assembly. gives access rational design peptide via control.

Language: Английский

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Multiscale modelling of biopolymers

Advances in Physics X, Journal Year: 2024, Volume and Issue: 9(1)

Published: July 3, 2024

This review overviews common biopolymer modelling approaches ranging from chemically specific to highly coarse-grained techniques, along with their application ranges, strengths and limitations. Recent applications at each scale are outlined discussed. The focus is on of protein peptide, nucleic acid saccharide-based systems, excluding lignocellulose materials. survey focuses physics-based models. We cover particle-based simulations methods, including all-atom molecular dynamics (MD), dissipative particle (DPD) Langevin Brownian (BD) approaches. While these methods capture particle-level dynamics, a brief overview also stochastic sampling (Monte Carlo methods) models, as well free energy functional-based i.e. field theory approaches, such self-consistent (SCFT) classical density functional (cDFT), provided.

Language: Английский

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Adsorption of polyelectrolytes in the presence of varying dielectric discontinuity between solution and substrate

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(13)

Published: Oct. 3, 2024

We examine the interactions between polyelectrolytes (PEs) and uncharged substrates under conditions corresponding to a dielectric discontinuity aqueous solution substrate. To this end, we vary relevant system characteristics, in particular substrate constant ɛs different salt conditions. employ coarse-grained molecular dynamics simulations with rodlike PEs solutions explicit ions implicit water solvent ɛw = 80. As expected, at low concentrations, are repelled from < but attracted high due image charges. This attraction considerably weakens for multivalent counterions enhanced screening. Furthermore, monovalent salt, screening enhances adsorption weakly charged PEs, it strongly ones. Meanwhile, have little effect on prevent of highly even concentrations. also find that correlation-induced charge inversion PE is close substrates, suppressed when high. explore possibility monolayer formation, interaction pair like-charged aligned parallel 8000. Our main conclusion formation possible only concentrations both counterions. Finally, consider energetics approaching perpendicular it, analogy polymer translocation. results highlight complex interplay electrostatic steric contribute deeper understanding PE–substrate interfaces varying discontinuities solution, ubiquitous biointerfaces, coating applications, designing setups.

Language: Английский

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Mechanisms of Fibroblast Growth Factor 21 Adsorption on Macroion Layers: Molecular Dynamics Modeling and Kinetic Measurements

Biomolecules, Journal Year: 2023, Volume and Issue: 13(12), P. 1709 - 1709

Published: Nov. 26, 2023

Molecular dynamic modeling and various experimental techniques, including multi-angle light scattering (MADLS), streaming potential, optical waveguide spectroscopy (OWLS), quartz crystal microbalance with dissipation (QCM), atomic force microscopy (AFM), were applied to determine the basic physicochemical parameters of fibroblast growth factor 21 in electrolyte solutions. The protein size shape, cross-section area, dependence nominal charge on pH, isoelectric point 5.3 acquired. These data enabled interpretation adsorption kinetics FGF bare macrocation-covered silica investigated by OWLS QCM. It was confirmed that molecules irreversibly adsorbed latter substrate, forming layers controlled coverage up 0.8 mg m−2, while their much smaller. viability two cell lines, CHO-K1 L-929, both macrocation/FGF 21-covered substrates also determined. is postulated acquired results can serve as useful reference systems for designing complexes extend half-life its active state.

Language: Английский

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A Computational Chemistry Approach to the Molecular Design of Sio2 Nanoparticles Coated with Stearic Acid and Sodium Stearate in Ethanol Solvent

Published: Jan. 1, 2023

Preparation of hydrophobic SiO2 nanoparticles (NPs) coated with different surfactants is important due to their potential application in fields chemistry. In this work, a combined experimental and Molecular Dynamics (MD) simulation study proposed order evaluate the adsorption process stearic acid sodium stearate on surface spherical NPs degrees ionization (0%,10%, 23.3%) ethanol, obtain molecular insight into factors involved preparation nanoparticles. Our results demonstrate that have good affinity for ethanol solvent. Also, analysis Radial Distribution Functions (RDFs) suggests hydrogen bonds are formed at distance ~0.192 nm between NPs. The ion-dipole, electrostatic, bond-type interactions present depending nature. presence Na+ ions reduce electrostatic repulsion -COO- -SiO- groups systems 10% 23.3%. investigation Potentials Mean Force (PMFs) equal spontaneous compared NP degree equals 0%. coating was studied using Atomic Microscopy (AFM), indirectly measure Work Adhesion (Wadh), key quantity estimate energy needed separate interfaces AFM tip-sample. Experimental values Wadh pure two modified correspond 2.01 J/m2, 1.72 J/m2 1.43 J/m2. main conclusion, summarizes experimental-computational comparison interaction energies NPs, estimated MD, obtained from measurements, reduction Wadh, solvent-free environment, related increment This also associated fact nature surfaces increases hydrophobicity. provides path computational design prediction hydrophobicity which focus our work.

Language: Английский

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