Mario Tagliazucchi

Responsive Polymers End-Tethered in Solid-State Nanochannels: When Nanoconfinement Really Matters

Solid state nanochannels modified with supramolecular architectures are a new and interesting class of stimuli-responsive nanofluidic element. Their fundamental understanding requires describing the behavior of soft-materials in confined geometries and its responses to changes in solution conditions. Here, a nanochannel modified with a polyelectrolyte brush is studied with a molecular theory that incorporates the conformational behavior of the polymers, electrostatic, van der Waals, and repulsive interactions coupled with the ability of the polymer segments to regulate their charge through acid-base equilibrium. The theory predicts pH-dependent ionic conductivity in excellent agreement with experimental observations. The polymer chains undergo large conformational changes triggered by variations in the outer solution environment and the conductivity of the device is shown to be controlled by the charge state of the polymer. The degree of polymer charge is largely affected by charge regulation and nanoconfinement effects. The molecular calculations show that the apparent pK(a) inside the pore departs from that in solution when increasing the curvature of the nanochannel.

Self-organization of grafted polyelectrolyte layers via the coupling of chemical equilibrium and physical interactions.

The competition between chemical equilibrium, for example protonation, and physical interactions determines the molecular organization and functionality of biological and synthetic systems. Charge regulation by displacement of acid-base equilibrium induced by changes in the local environment provides a feedback mechanism that controls the balance between electrostatic, van der Waals, steric interactions and molecular organization. Which strategies do responsive systems follow to globally optimize chemical equilibrium and physical interactions? We address this question by theoretically studying model layers of end-grafted polyacids. These layers spontaneously form self-assembled aggregates, presenting domains of controlled local pH and whose morphologies can be manipulated by the composition of the solution in contact with the film. Charge regulation stabilizes micellar domains over a wide range of pH by reducing the local charge in the aggregate at the cost of chemical free energy and gaining in hydrophobic interactions. This balance determines the boundaries between different aggregate morphologies. We show that a qualitatively new form of organization arises from the coupling between physical interactions and protonation equilibrium. This optimization strategy presents itself with polyelectrolytes coexisting in two different and well-defined protonation states. Our results underline the need of considering the coupling between chemical equilibrium and physical interactions due to their highly nonadditive behavior. The predictions provide guidelines for the creation of responsive polymer layers presenting self-organized patterns with functional properties and they give insights for the understanding of competing interactions in highly inhomogeneous and constrained environments such as those relevant in nanotechnology and those responsible for biological cells function.

Redox and Acid−Base Coupling in Ultrathin Polyelectrolyte Films

A single layer of poly(allylamine) with a covalently attached osmium pyridine-bipyridine complex adsorbed onto a Au surface modified by mercaptopropanesulfonate has been studied theoretically with a molecular approach and experimentally by cyclic voltammetry. These investigations have been carried out at different pHs and ionic strengths of the electrolyte solution in contact with the redox polyelectrolyte modified electrode. The theory predicts strong coupling between the acid-base and redox equilibria, particularly for low ionic strength, pH close to the pKa, and high concentration of redox sites. The coupling leads to a decrease in the peak potential at pH values above the apparent pKa of the weak polyelectrolyte, in good agreement with the experimental pH dependence at 4 mM NaNO3. Theoretical calculations suggest that the inflection point in the peak position versus pH curves can be used to estimate the apparent pKa of the amino groups in the polymer. Comparison of the apparent pKa for PAH-Os in the film with that of poly(allylamine) reported in the literature shows that the underlying charged thiol strongly influences charge regulation in the film. A systematic study of the film thickness and the degree of protonation in sulfonate and amino groups for solutions of different pH and ionic strength shows the coupling between the different interactions. It is found that the variation of the film properties has a non-monotonic dependence on bulk pH and salt concentration. For example, the film thickness shows a maximum with electrolyte ionic strength, whose origin is attributed to the balance between electrostatic amino-amino repulsions and amino-sulfonate attractions.

Charge transport in redox polyelectrolyte multilayer films: the dramatic effects of outmost layer and solution ionic strength.

The redox switching kinetics, that is, charge transfer and transport in layer-by-layer-deposited electroactive polyelectrolyte multilayers is systematically studied with variable-scan-rate cyclic voltammetry. The experiments are performed with films finished in the redox polycation (an osmium pyridine-bipyridine derivatized polyallylamine, PAH-Os) and the polyanion (polyvinyl sulfonate, PVS), in solutions of different electrolyte concentrations. A modified diffusion model is developed to account for the experimentally observed dependence of the average peak potential with the scan rate. This model is able to describe both the redox peak potential and the current, providing information on the electron-transfer rate constants and the diffusion coefficient for the electron-hopping mechanism. While the former does not vary with the ionic strength or the nature of the outmost layer, polyanion-capped films present an electron-hopping diffusion coefficient at low ionic strength that is three orders of magnitude smaller than that for PAH-Os-capped films. The effect is offset at high ionic strength. We discuss the possible causes of the effect and the important consequences for electrochemical devices built by layer-by-layer self-assembly, such as amperometric biosensors or electrochromic devices.

Nanostructured modified electrodes: Role of ions and solvent flux in redox active polyelectrolyte multilayer films

Electrodes modified layer-by-layer by self-assembly of redox active polyelectrolytes comprised of osmium bipyridine-pyridine derivatized poly(allyl-amine) and poly(vinyl) sulfonate have been studied by EQCM, ellipsometry, cyclic voltammetry and electrochemical impedance spectroscopy in aqueous solutions of different anions and cations. Redox driven swelling by solvent exchange during oxidation, in excess to the hydration number, occurs by perturbation of the equilibrium between the osmotic and elastic forces as a result of the electrochemical injection of charge into the film. The exchanged mass and volume change during redox switching strongly depends on the nature of the anion under anion Donnan permselectivity conditions.

Redox molecule based SERS sensors

We describe a general framework to design nanobiosensors based on a wired enzyme coupled to a redox molecule and integrated with SERS Au core-shell nanoparticles and ordered nanocavities. The response of the proposed sensor is based on the different electronic resonant Raman behavior of the oxidized or reduced electronic states of the molecular wire, and on the surface plasmon amplification induced by the tailored metallic substrate. The nanobiosensors can be interrogated remotely through the resonant Raman scattering intensity recovery or spectral variation of the redox molecule, an Os-complex, when the latter varies its oxidation state. Alternatively, we show through two-color spectro-electrochemistry that Raman scattering is also finely sensitive to oxidation state changes of flavin, a biomimetic system that mimics the active center of many flavoprotein enzymes. We show that multiple sample spectroscopic ellipsometry gives access to the spectral dependence of the optical constants of single redox-molecule layers, and through it to the electronic resonances of the system. All the components for selective molecular recognition and for the generation of an optical amplified signal, are self-contained in the proposed biosensor. As proof of concept a compact SERS sensor responsive to glucose with millimolar concentration in solution is demonstrated.

Anisotropic surface functionalization of Au nanorods driven by molecular architecture and curvature effects

This work suggests a novel strategy to coat the caps and body of Au-nanorods (Au-NRs) with end-grafted polymer layers of different compositions by taking advantage of the different curvature of these two regions. A molecular theory was used to theoretically investigate the effect of local curvature and molecular architecture (intramolecular connectivity of the monomers) on the adsorption of polymer mixtures on cylindrical (Au-NR body) and spherical (Au-NR caps) surfaces. The adsorption process was systematically studied as a function of the backbone length, number and position of branches, quality of the solvent and total number of monomers of the polymer molecules in the mixture. The balance between repulsive forces and polymer-surface and polymer-polymer attractions governs the amount and composition of the adsorbed layer. This balance is in turn modulated by the architecture of the polymers, the curvature of the surface and the competition between the different polymers in the mixture for the available area. As a result, the equilibrium composition of the polymer layer on spheres and cylinders of the same radius differs, and in turn departs from that of the bulk solution. Curvature plays a major role: the available volume at a given distance from the surface is larger for spherical surfaces than for cylindrical ones, therefore the surface density of the bulkier (more branched) polymer in the mixture is larger on the Au-NR caps than on the Au-NR body. These results suggest that the combination of curvature at the nanoscale and tailored molecular architecture can confer anisotropic nanoparticles with spatially enriched domains and, therefore, lead to nanoconstructs with directional chemical interactions.

Molecular orientation in self-assembled multilayers measured by Second Harmonic generation using femtosecond pulses.

We present measurements of the optical second-harmonic generation in self assembled multilayer films of PAZO/PAH polymers with the aim to investigate molecular order in the layer-by-layer architecture. The experiments are performed in transmission, using a femtosecond Ti:Sa pulsed laser, which allows a more accurate determination of the amplitude of the second harmonic signal, without interference fringes usually present in nanosecond experiments. We found that the first bilayer, in contact with the substrate, presents a broad distribution of the orientation of the molecules, while the addition of successive bilayers (up to 12) produces ordering of the molecules with a small tilt angle respect to the surface normal. This result, together with the monotonic increment of the second harmonic signal with the number of layers indicates that the molecules grow orderly assembled in these films.

Simplified Approach to Work Function Modulation in Polyelectrolyte Multilayers

The layer-by-layer (LbL) method is based on sequential deposition of polycations and polyanions. Many of the properties of polyelectrolyte thin films deposited via this method depend on the nature of the topmost layer. Thus, these properties show odd-even oscillations during multilayer growth as the topmost layer alternates from polycations to polyanions. The work function of a (semi)conductive substrate modified with an LbL polyelectrolyte multilayer also displays an oscillatory behavior independent of film thickness. The topmost layer modulates the work function of a substrate buried well below the film. In agreement with previous observations, in this work, we show that the work function of a gold substrate changes periodically with the number of adsorbed layers, as different combinations of polycations and polyanions are deposited using the LbL method. For the first time, we rationalize this behavior in terms of formation of a dipole layer between the excess charge at the topmost layer and the charge of the metal substrate, and we put forward a semiquantitative model based on a continuum description of the electrostatics of the system that reproduces the experimental observations.

Self-assembly of model short triblock amphiphiles in dilute solution

In this work, a molecular theory is used to study the self-assembly of short diblock and triblock amphiphiles, with head-tail and head-linker-tail structures, respectively. The theory was used to systematically explore the effects of the molecular architecture and the affinity of the solvent for the linker and tail blocks on the relative stability of the different nanostructures formed by the amphiphiles in dilute solution, which include spherical micelles, cylindrical fibers and planar lamellas. Moreover, the theory predicts that each of these nanostructures can adopt two different types of internal organization: (i) normal nanostructures with a core composed of tail segments and a corona composed of head segments, and (ii) nanostructures with a core formed by linker segments and a corona formed by tail and head segments. The theory predicts the occurrence of a transition from micelle to fiber to lamella when increasing the length of the tail or the linker blocks, which is in qualitative agreement with the geometric packing theory and with experiments in the literature. The theory also predicts a transition from micelle to fiber to lamella as the affinity of the solvent for the tail or linker block is decreased. This result is also in qualitative agreement with experiments in the literature but cannot be explained in terms of the geometric packing theory. The molecular theory provides an explanation for this result in terms of the competition between solvophobic attractions among segments in the core and steric repulsions between segments in the corona for the different types of self-assembled nanostructures.