Linear versus Exponential Growth of Weak Polyelectrolyte Multilayers: Correlation with Polyelectrolyte Complexes

Xu, Li; Pristinski, Denis; Zhuk, Aliaksandr; Stoddart, C. T. H.; Ankner, John F.; Sukhishvili, Svetlana A.

doi:10.1021/ma300157p

Cited by 71 publications

(69 citation statements)

References 79 publications

(130 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…If multiple layers of MOF had adsorbed within a single exposure, the layer pair thickness would have been greater than the particle's diameter. The successful growth and linear thickness relationship is consistent with strong intermolecular interactions between complementary species, confirming the favorable associations between positively charged MIL‐101(Cr) nanoparticles and negatively charged PSS. Because of these strong electrostatic interactions, the LbL film resisted damage even to a tape‐peeling test (Movie S1, Supporting Information); this emphasizes the robustness and the good adhesion between the LbL coating and the underlying substrate.…”

Section: Resultssupporting

confidence: 62%

Water‐Based Assembly of Polymer–Metal Organic Framework (MOF) Functional Coatings

Nandasiri

Schaef

et al. 2016

Adv Materials Inter

View full text Add to dashboard Cite

Metal organic frameworks (MOFs) have gained attention for their porosity, size selectivity, and structural diversity. There is a need for MOF-based coatings, particularly in applications such as separations, electronics, and energy; yet forming thin, functional, conformal coatings is prohibitive because MOFs exist as a powder. Layer-by-layer assembly, a versatile thin film coating approach, offers a unique solution to this problem, but this approach requires MOFs that are water-dispersible and bear a surface charge. Here, these issues are addressed by examining water-based dispersions of MIL-101(Cr) that facilitate the formation of robust polymer-MOF hybrid coatings. Specifically, the substrate to be coated is alternately exposed to an aqueous solution of poly(styrene sulfonate) and nano MIL-101(Cr) dispersion, yielding linear film growth and coatings with a MOF content as high as 77 wt%. This approach is surface-agnostic, in which the coating is successfully applied to silicon, glass, flexible plastic, and even cotton fabric, conformally coating individual fibers. By contrast, prior attempts at forming MOF-coatings are severely limited to a handful of surfaces, require harsh chemical treatment, and are not conformal. The approach presented here unambiguously confirms that MOFs can be conformally coated onto complex and unusual surfaces, opening the door for a wide variety of applications.

show abstract

Section: Resultssupporting

confidence: 62%

Water‐Based Assembly of Polymer–Metal Organic Framework (MOF) Functional Coatings

Nandasiri

Schaef

et al. 2016

Adv Materials Inter

View full text Add to dashboard Cite

show abstract

“…In this review, we sum up the main patterns of polymer dynamics established for synthetic films, i.e.,: diffusion of polyelectrolyte molecules within PEMs is highly anisotropic, with the preferential diffusion parallel to the substrate [ 115 ]. the transition between linear and exponential film growth modes is closely correlated with the transition in polymer dynamics; at the transition point, film structure is changed from layered for linearly depositing films to highly intermixed for exponentially depositing LbLs [ 192 ]. polymer dynamics is influenced by the temperature, ionic strength and pH.…”

Section: Summary and Perspectivesmentioning

confidence: 99%

“…the transition between linear and exponential film growth modes is closely correlated with the transition in polymer dynamics; at the transition point, film structure is changed from layered for linearly depositing films to highly intermixed for exponentially depositing LbLs [ 192 ].…”

Section: Summary and Perspectivesmentioning

confidence: 99%

Layer-By-Layer Assemblies of Biopolymers: Build-Up, Mechanical Stability and Molecular Dynamics

Campbell

Vikulina

2020

Polymers

View full text Add to dashboard Cite

Rapid development of versatile layer-by-layer technology has resulted in important breakthroughs in the understanding of the nature of molecular interactions in multilayer assemblies made of polyelectrolytes. Nowadays, polyelectrolyte multilayers (PEM) are considered to be non-equilibrium and highly dynamic structures. High interest in biomedical applications of PEMs has attracted attention to PEMs made of biopolymers. Recent studies suggest that biopolymer dynamics determines the fate and the properties of such PEMs; however, deciphering, predicting and controlling the dynamics of polymers remains a challenge. This review brings together the up-to-date knowledge of the role of molecular dynamics in multilayers assembled from biopolymers. We discuss how molecular dynamics determines the properties of these PEMs from the nano to the macro scale, focusing on its role in PEM formation and non-enzymatic degradation. We summarize the factors allowing the control of molecular dynamics within PEMs, and therefore to tailor polymer multilayers on demand.

show abstract

“…Most of the earlier studies on polyelectrolyte complexation focused on coacervation of natural polymers such as albumin and gelatin, but recent studies [2,3,[8][9][10][11][12] have extended this to the complexation of synthetic polyelectrolytes. Renewed scientific interest in polyelectrolyte complexation is due, in part, to its use in polyelectrolyte assemblies and multilayer films [13,14], which have many technological applications [15,16].…”

Section: Introductionmentioning

confidence: 99%

pH and Salt Effects on the Associative Phase Separation of Oppositely Charged Polyelectrolytes

et al. 2014

View full text Add to dashboard Cite

Abstract:The classical Voorn-Overbeek thermodynamic theory of complexation and phase separation of oppositely charged polyelectrolytes is generalized to account for the charge accessibility and hydrophobicity of polyions, size of salt ions, and pH variations. Theoretical predictions of the effects of pH and salt concentration are compared with published experimental data and experiments we performed, on systems containing poly(acrylic acid) (PAA) as the polyacid and poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) or poly(diallyldimethyl ammonium chloride) (PDADMAC) as the polybase. In general, the critical salt concentration below which the mixture phase separates, increases with degree of ionization and with the hydrophobicity of polyelectrolytes. We find experimentally that as the pH is decreased below 7, and PAA monomers are neutralized, the critical salt concentration increases, while the reverse occurs when pH is raised above 7. We predict this asymmetry theoretically by introducing a large positive Flory parameter (= 0.75) for the interaction of neutral PAA monomers with water. This large positive Flory parameter is supported by molecular dynamics simulations, which show much weaker hydrogen bonding between neutral PAA and water than between charged PAA and water, while neutral and charged PDMAEMA show similar numbers of hydrogen bonds. This increased hydrophobicity of neutral PAA at reduced pH increases the tendency towards phase separation despite the reduction in charge interactions between the polyelectrolytes. Water content and volume of coacervate are found to be a strong function of the pH and salt concentration.

show abstract

Linear versus Exponential Growth of Weak Polyelectrolyte Multilayers: Correlation with Polyelectrolyte Complexes

Cited by 71 publications

References 79 publications

Water‐Based Assembly of Polymer–Metal Organic Framework (MOF) Functional Coatings

Water‐Based Assembly of Polymer–Metal Organic Framework (MOF) Functional Coatings

Layer-By-Layer Assemblies of Biopolymers: Build-Up, Mechanical Stability and Molecular Dynamics

pH and Salt Effects on the Associative Phase Separation of Oppositely Charged Polyelectrolytes

Contact Info

Product

Resources

About