Microgel Monolayers Research Articles

Assembly and jamming of polar additive-swollen microgels at liquid–liquid interfaces: From inverse Pickering emulsions to functional materials

HypothesisPoly-N-isopropylacrylamide (PNIPAM)-based microgels have garnered significant interest as effective soft particulate stabilizers because of their deformability and functionality. However, the inherent hydrophilic nature of microgel restricts their potential use in stabilizing water-in-oil (W/O) Pickering emulsions. Employing diverse polar additives can improve the hydrophobicity of microgels, thus unlocking new possibilities in inverse Pickering emulsion formation and materials fabrication. ExperimentsDifferent types of microgels were generated using free-radical precipitation polymerization with tailored physiochemical properties. The effect of various polar additives on the wettability, adsorption kinetics, and interfacial coverage of microgels was systematically investigated. Additive-swollen microgels were utilized to stabilize inverse W/O Pickering emulsions, which served as templates to develop functional materials with stimuli responsiveness and hierarchical structures. FindingsAdditive-swollen PNIPAM-based microgels exhibited enhanced hydrophobicity and superior emulsifying capability, which spontaneously assembled and jammed at oil–water interfaces, resulting in a significant interfacial energy decrease. The microgels formed a tightly packed, elastic, and responsive microgel monolayer. The feasibility of the strategy was verified by preparing various inverse W/O Pickering emulsions and high internal phase Pickering emulsions (HIPPEs). More importantly, this straightforward formation strategy of microgel-stabilized inverse W/O Pickering emulsions offered a novel platform to create functional materials with customized inner structures from microscale (e.g., responsive core–shell hydrogel microspheres and colloidosomes) to macroscale (e.g., hierarchical porous materials) that can be used for potential applications, such as recyclable contaminant removal and droplet manipulation.

Enhancing interfacial elasticity via supramolecular microgel assembly for improved Pickering emulsions stability

We propose a new method to improve the interfacial elasticity of microgel-stabilised Pickering emulsions (PEs) by introducing supramolecular host-guest interactions to promote clustering among microgel particles. To this aim, microgels based on poly(N-isopropylacrylamide) (pNIPAM) are modified with 1-benzyl-3-vinylimidazolium bromide (BVI) to create pNIPAM-co-BVI microgels (MG). Cucurbit[8]uril (CB[8]) are introduced to form supramolecular BVI/CB[8] host-guest complexes. The introduction of CB[8] affects microgel spatial distribution at the interface of Pickering droplets, promoting the formation of monolayers of microgel clusters. These structures alter the interfacial viscoelasticity of the microgel monolayers, enhancing the resistance of (MG+CB[8])-stabilised interfaces to lateral and dilational deformations. PEs stabilised by microgels with the presence of CB[8] host-guest interactions exhibit improved stability over time. These results show the possibility of tuning the interfacial properties of microgel-laden interfaces by introducing supramolecular ternary complexes that can solely alter the interparticle interactions among microgels without significantly changing their morphology and deformability at the interface, thus providing a new route for improved emulsion stabilisation.

Interfacial rheology of polyelectrolyte microgel monolayers: Correlation between mechanical properties and phase behavior at oil-water interfaces

Microgels are confined to fluid interfaces in numerous applications, yet many aspects of the microgel-covered interface remain unclear. In this work, we use interfacial shear and dilatational rheology to study the effects of electrostatics on the mechanical characteristics of polyelectrolyte microgel monolayers at oil-water interfaces as a function of the microgel interfacial concentration. We find a clear correlation between the influence of charges on the mechanical properties of the monolayers and the influence of charges on their two-dimensional phase behavior. At lower microgel interfacial concentrations, the moduli of uncharged monolayers are larger than those of charged monolayers. Consistent with our previous findings on the phase behavior, here, the mechanical response of the interfacial layer is controlled by in-plane interactions of the microgels within the interface. At higher microgel interfacial concentrations, the moduli of charged monolayers are larger than those of uncharged monolayers. The mechanical response becomes dominated by out-of-plane interactions between the fractions of the adsorbed microgels further from the interface. Evidently, electrostatic interactions do not contribute directly to the mechanical response of the interfacial layer, that is, through charge repulsion, but indirectly through the difference in the swelling properties of uncharged and charged microgels. These results advance our understanding of how the charge-dependent microstructure of the interfacial layer affects its mechanical properties, which is not only important from a fundamental point of view but is also relevant to applications where polyelectrolyte microgels are used as responsive emulsion stabilizers.

Tuning the bulk behavior and 2D interfacial self-assembly of microgels by keggin-type polyoxometalate ionic specificity

Finding new ways to tune the behavior of thermoresponsive microgels in bulk and confined at 2D liquid interfaces is key to achieve a deeper understanding and control of these smart materials. We studied the interaction of positively and negatively charged pNIPAM microgels with the Keggin-type polyoxometalates Na3PW12O40 (POM3−) and H4SiW12O40 (POM4−). In bulk, we observed charge inversions of the positively charged microgels below and above the volume phase transition temperature (VPTT) at significantly low POM concentrations as 5⋅10−5 M. In the presence of POM, both microgels exhibited a deswelling-swelling-deswelling behavior below the VPTT, and a two-step further deswelling above the VPTT for the positively charged microgels. When the later were confined at 2D water/air interfaces, adding 10−5 M of POM3− below the VPTT was equivalent to heating above the VPTT and compressing the monolayer from 5 to 20mN m−1. Above the VPTT, the diameter at the interface did not change while the portion immersed in the subphase further deswelled, in agreement with the behavior in bulk. Adding more POM3− did not change the diameter at the interface nor the height of the microgels, showing a saturation effect in 2D. The restructuring of the pNIPAM polymeric network by the POM3− was characterized by EDS mapping and XPS. The microgel monolayers with POM3− improved their resistance to plasma etching, which could be useful for soft colloidal lithography.

Monolayer of microgel particles based on poly(acrylic acid) modified with dopamine for electrochemical pH sensing

A novel electroactive and pH-responsive microgel was successfully synthesized. The obtained microgel was based on acrylic acid, dopamine methacrylamide and N,N′-bis(acryloyl)cystamine as the crosslinker. Using the distillation precipitation polymerization method, spherical, smooth-surface microgel particles of ca. 400 nm in diameter were obtained. The presence of dopamine groups in the polymer network was confirmed with cyclic voltammetry and NMR spectroscopy. The dependence of microgel hydrodynamic diameter on pH was investigated using the DLS technique. The presence of -S–S- groups in the microgel particle was used to modify the Au electrode surface by chemisorption. The attachment was monitored with the QCM-D technique. The obtained microgel was successfully anchored to the Au regular- and microelectrode surfaces. The electrochemical properties of the modified electrodes were promising. It was found that modified electrodes exhibited potentially useful pH-sensing properties. Modification of Au microelectrode surface with the environmentally sensitive and electroactive microgel monolayer is a novel, innovative approach.

Influence of Architecture on the Interfacial Properties of Polymers: Linear Chains, Stars, and Microgels.

Surface-active polymers have important applications as effective and responsive emulsifiers, foaming agents, and coatings. In this contribution, we explore the impact of the polymer architecture on the behavior at oil-water interfaces by comparing different poly(N-isopropylacrylamide) (pNIPAM)-based systems, namely, monolayers of linear and star-shaped macromolecules, ultralow cross-linked, regular cross-linked, and hollow microgels. Compression isotherms were determined experimentally as well as by computer simulations. The latter provides information about the conformational changes of the individual macromolecules as well as the interfacial properties of the monolayer, including the surface structure and the density distribution of an ensemble of interacting macromolecules near an interface. Surprisingly, the isotherms of the linear polymer, of the star polymer, and of the ultralow cross-linked microgel have an identical shape that differs from the isotherms of regular and hollow microgels. We introduced the mass fraction of adsorbed polymer, which gives a measure of the polymer segments contributing to the isotherm in relation to the most flexible architecture, i.e., the linear polymer, and allows a comparison of polymers with different architectures. The data demonstrate that increasing the number of cross-links leads to a significantly lower amount of polymer in the proximity of the interface as the increase in cross-linker reduces the deformability or softness of the polymers at the interface. The volume fraction profiles along the normal to the interface are essentially different in the microgel monolayers as compared to those in the linear and star polymer. The profiles through the microgel contact line and their growth upon initial compression are similar to those of the linear chains. Herewith, the profiles through the center of mass practically do not change upon compression. Therefore, the initial growth in the microgel surface pressure reveals the polymer-like behavior and is related to the deformation of the peripheral part of the microgel. Further compression of the microgel monolayer leads to 3D interactions of the microgels within the aqueous side of the interface and soft colloid-like behavior.

Novel Insights on the Three-dimensional Shape of Microgels at Fluid Interfaces

Mechanically soft colloids (microgels) adsorbed at the interface between two fluids offer superior advantages over hard counterparts for a variety of applications ranging from foams/emulsion stabilization to the assembly of two-dimensional (2D) materials. Particle deformability and compressibility impart additional responses to microgel-laden interfaces that can be controlled on-demand by varying single-particle properties (e.g. crosslinking content and polymer density profile) and/or external parameters (e.g. interfacial compression and tension, temperature, oil polarity). In order to understand how single-particle softness influences the resulting material properties, a detailed quantification of the microgel’s 3D conformation when confined at the fluid interface is of utmost importance. This article describes how different methodologies can be used to visualize, and in some case quantify, the conformation of adsorbed microgels, putting particular emphasis on the multiple advantages offered by in situ atomic force microscopy imaging at the fluid interface. The influence of the internal particle architecture, as well as that of temperature, interfacial tension and solubility in the organic phase, will be discussed. Finally, some perspectives on how softness can be exploited to tune the structural and mechanical properties of microgel monolayers will be provided.

Responsive microgels-based colloidosomes constructed from all-aqueous pH-switchable coacervate droplets

HypothesisColloidosomes made of stimuli-responsive microgels offer the opportunity to design polymeric capsules with a hierarchical and tunable pore distribution. Coacervates stabilized by a microgel monolayer represent a unique strategy to build colloidosomes from all-aqueous emulsion drops, while exploiting the sequestration and dissolution properties of the coacervates. ExperimentsMethacrylated poly(N-isopropylacrylamide) (pNIPAM) microgels are used to stabilize coacervates made of an ampholyte polymer at a pH close to its isoelectric point. They are further cross-linked under UV-irradiation. The resulting assemblies are studied by means of confocal microscopy. Their permeability towards dextrans and nanoparticles is studied before and after dissolution of the coacervate. FindingsPNIPAM microgels are found to stabilize the coacervates by adsorbing at their surface. Inter cross-linking the microgels results in the formation of an elastic colloidosome that persists after the coacervate dissolution and withstands surface deformations up to about 200%. The coacervate is exploited as a sequestrating core to entrap a water-soluble payload, which can be further released upon coacervate dissolution, while the membrane exhibits a size-selecting permeability. The membrane properties can also be switched by the volume phase transition of the microgels. Coacervate-embedded colloidosomes open new perspectives in the area of encapsulation/extraction and controlled transport of water-soluble/dispersed species.

In-Line Characterization of the Temperature-Responsive Behavior of Surface-Bound Microgel Coatings by QCM-D: A Novel Strategy for Protein Repellence Evaluation.

In this work, quartz crystal microbalance with dissipation monitoring (QCM-D) was used to develop a new method to evaluate the protein repellency of microgel coatings. Compared to traditional protocols for surface analysis, QCM has the advantage of a real-time quantitative approach with high sensitivity, allowing us to describe variations of the adsorbed mass with unprecedented accuracy. To enable the detectability of the film throughout the whole operational temperature interval, a poly(N-isopropylacrylamide-co-glycidyl methacrylate) p(NIPAm-co-GMA) microgel monolayer with defined thickness and rigidity was designed. Covalent adhesion of the film to the silica surface was achieved by epoxy-thiol click chemistry and tested for repeated temperature cycles, showing substantial reproducibility. Further functionalization of microgel surfaces by grafting polyzwitterionic chains remarkably improved the protein repellence leaving the strong surface adhesion unaltered. Before and after exposure to fluorescein-tagged bovine serum albumin (FITC-BSA), the coatings showed identical responsive behavior, proving the absence of protein deposition. In nonrepellent coatings, QCM monitoring instead displayed a characteristic shift in the volume phase transition (VPT), pointing out the effect of adsorbed proteins on the swelling behavior of pNIPAm. The combination of QCM-D and UV-visible (UV-vis) was used to evaluate the effect of increasing surface coverage, enabling to distinguish between the protein deposition occurring over the coated and the uncoated portion of the sensor.

Influence of the interfacial tension on the microstructural and mechanical properties of microgels at fluid interfaces

Microgels are soft colloidal particles constituted by cross-linked polymer networks with a high potential for applications. In particular, after adsorption at a fluid interface, interfacial tension provides two-dimensional (2D) confinement for microgel monolayers and drives the reconfiguration of the particles, enabling their deployment in foam and emulsion stabilization and in surface patterning for lithography, sensing and optical materials. However, most studies focus on systems of fluids with a high interfacial tension, e.g. alkanes/ or air/water interfaces, which imparts similar properties to the assembled monolayers. Here, instead, we compare two organic fluid phases, hexane and methyl tert-butyl ether, which have markedly different interfacial tension (γ) values with water and thus tune the deformation of adsorbed microgels. We rationalize how γ controls the single-particle morphology, which consequently modulates the structural and mechanical response of the monolayers at varying interfacial compression. Specifically, when γ is low, the microgels are less deformed within the interface plane and their polymer networks can rearrange more easily upon lateral compression, leading to softer monolayers. Selecting interfaces with different surface energy offers an additional control to customize the 2D assembly of soft particles, from the fine-tuning of particle size and interparticle spacing to the tailoring of mechanical properties.

Interactions between a responsive microgel monolayer and a rigid colloid: from soft to hard interfaces.

Responsive poly-N-isopropylacrylamide-based microgels are commonly used as model colloids with soft repulsive interactions. It has been shown that the microgel-microgel interaction in solution can be easily adjusted by varying the environmental parameters, e.g., temperature, pH, or salt concentration. Furthermore, microgels readily adsorb to liquid-gas and liquid-liquid interfaces forming responsive foams and emulsions that can be broken on-demand. In this work, we explore the interactions between microgel monolayers at the air-water interface and a hard colloid in the water. Force-distance curves between the monolayer and a silica particle were measured with the Monolayer Particle Interaction Apparatus. The measurements were conducted at different temperatures and lateral compressions, i.e., different surface pressures. The force-distance approach curves display long-range repulsive forces below the volume phase transition temperature of the microgels. Temperature and lateral compression reduce the stiffness of the monolayer. The adhesion increases with temperature and decreases with a lateral compression of the monolayer. When compressed laterally, the interactions between the microgels are hardly affected by temperature, as the directly adsorbed microgel fractions are nearly insensitive to temperature. In contrast, our findings show that the temperature-dependent swelling of the microgel fractions in the aqueous phase strongly influences the interaction with the probe. This is explained by a change in the microgel monolayer from a soft to a hard repulsive interface.

Temperature-sensitive soft microgels at interfaces: air-water versus oil-water.

The formation of smart emulsions or foams whose stability can be controlled on-demand by switching external parameters is of great interest for basic research and applications. An emerging group of smart stabilizers are microgels, which are nano- and micro-sized, three-dimensional polymer networks that are swollen by a good solvent. In the last decades, the influence of various external stimuli on the two-dimensional phase behavior of microgels at air- and oil-water interfaces has been studied. However, the impact of the top-phase itself has been barely considered. Here, we present data that directly address the influence of the top-phase on the microgel properties at interfaces. The dimensions of pNIPAM microgels are measured after deposition from two interfaces, i.e., air- and decane-water. While the total in-plane size of the microgel increases with increasing interfacial tension, the portions or fractions of the microgels situated in the aqueous phase are not affected. We correlate the area microgels occupy to the surface tensions of the interfaces, which allows to estimate an elastic modulus. In comparison to nanoindentation measurements, we observe a larger elastic modulus for the microgels. By combining compression, deposition, and visualization, we show that the two-dimensional phase behavior of the microgel monolayers is not altered, although the microgels have a larger total in-plane size at higher interfacial tension.

Collapse-induced phase transitions in binary interfacial microgel monolayers.

Microgels, consisting of a swollen polymer network, exhibit a more complex self-assembly behavior compared to incompressible colloidal particles, because of their ability to deform at a liquid interface or collapse upon compression. Here, we investigate the collective phase behavior of two-dimensional binary mixtures of microgels confined at the air/water interface. We use stimuli-responsive poly(N-isopropylacrylamide) microgels with different crosslinking densities, and therefore different morphologies at the interface. We find that the minority microgel population introduces lattice defects in the ordered phase of the majority population, which, in contrast to bulk studies, do not heal out by partial deswelling to accommodate in the lattice. We subsequently investigate the interfacial phase behavior of these binary interfacial assemblies under compression. The binary system exhibits three distinct isostructural solid-solid phase transitions, during which the coronae between two small particles collapse first, followed by the collapse between small-large and large-large microgel pairs. A similar hierarchy of phase transitions is found for mixtures of microgels and core-shell particles. Simulations based on augmented potentials qualitatively reproduce the experimentally observed phase transitions. We rationalize the presence of this hierarchy in phase transitions from differences in the interfacial morphology between the species: the larger coronae of softer (and therefore larger) microgels provide a higher resistance to phase transitions compared to the smaller coronae of the more crosslinked microgels and core-shell particles. The control of phase transitions via the molecular architecture further allows the formation of characteristic, flower-like defects by introducing particles with "weaker" coronae that are more prone to collapse with their neighboring particles. Our findings underline the dominating role of the corona for interfacial microgel assemblies, which acts as an energy barrier, shifting the collapse to higher surface pressures.

Effect of the 3D Swelling of Microgels on Their 2D Phase Behavior at the Liquid-Liquid Interface.

We investigate soft, temperature-sensitive microgels at fluid interfaces. Though having an isotropic, spherical shape in bulk solution, the microgels become anisotropic upon adsorption. The structure of microgels at interfaces is described by a core-corona morphology. Here, we investigate how changing temperature across the microgel volume phase transition temperature, which leads to swelling/deswelling of the microgels in the aqueous phase, affects the phase behavior within the monolayer. We combine compression isotherms, atomic force microscopy imaging, multiwavelength ellipsometry, and computer simulations. At low compression, the interaction between adsorbed microgels is dominated by their highly stretched corona and the phase behavior of the microgel monolayers is the same. The polymer segments within the interface lose their temperature-sensitivity because of the strong adsorption to the interface. At high compression, however, the portions of the microgels that are located in the aqueous side of the interface become relevant and prevail in the microgel interactions. These portions are able to collapse and, consequently, the isostructural phase transition is altered. Thus, the temperature-dependent swelling perpendicular to the interface ("3D") affects the compressibility parallel to the interface ("2D"). Our results highlight the distinctly different behavior of soft, stimuli-sensitive microgels as compared to rigid nanoparticles.

Layer-by-Layer Assembly of Microgel Colloidal Crystals via Photoinitiated Alkyne-Azide Click Reaction.

Layer-by-layer (LBL) assembly of colloidal crystals (CCs) allows for the fine control of the thickness and architecture of the resulting crystals. Various methods have been developed for the LBL assembly of CCs of hard spheres. However, these methods are inapplicable for microgel CCs owing to the softness and deformability of microgel spheres. In this study, a method was proposed for the LBL assembly of microgel CCs. To build the first monolayer, azide-modified microgel spheres were assembled into a three-dimensional (3D) CC. The first 111 plane of the 3D CC close to the substrate was then fixed in situ onto the substrate via photoinitiated alkyne–azide click reaction between the azide groups on the microgels and the alkyne groups on the substrate surface. The removal of unbonded particles resulted in a microgel monolayer with a high degree of order. The second monolayer was assembled in a similar manner, i.e., a 3D microgel CC was initially assembled followed by in situ fixation of the first 111 plane of the 3D crystal with the underlying microgel monolayer by photoinitiated alkyne–azide click reaction. For this purpose, instead of azide-modified microgel spheres, alkyne-modified microgel spheres were used for the assembly of the second layer. Confocal studies confirmed that the second monolayer was located on top of the first layer. When the lattice constant of the 3D CC approximated that of the underlying microgel monolayer, the second monolayer exhibited a high degree of order. Repeating this process led to alternating deposition of highly ordered monolayers of azide-modified and alkyne-modified microgels onto the substrate. Similar to the microgel CCs obtained by the self-assembly of microgel spheres in bulky dispersions, face-centered cubic and hexagonal-close-packed structures also coexisted in the LBL-assembled microgel CCs.

Inhibiting Bacterial Adhesion by Mechanically Modulated Microgel Coatings.

Bacterial infection is a severe problem especially when associated with biomedical applications. This study effectively demonstrates that poly-N-isopropylmethacrylamide based microgel coatings prevent bacterial adhesion. The coating preparation via a spraying approach proved to be simple and both cost and time efficient creating a homogeneous dense microgel monolayer. In particular, the influence of cross-linking density, microgel size, and coating thickness was investigated on the initial bacterial adhesion. Adhesion of Staphylococcus aureus ATCC 12600 was imaged using a parallel plate flow chamber setup, which gave insights in the number of the total bacteria adhering per unit area onto the surface and the initial bacterial deposition rates. All microgel coatings successfully yielded more than 98% reduction in bacterial adhesion. Bacterial adhesion depends both on the cross-linking density/stiffness of the microgels and on the thickness of the microgel coating. Bacterial adhesion decreased when a lower cross-linking density was used at equal coating thickness and at equal cross-linking density with a thicker microgel coating. The highest reduction in the number of bacterial adhesion was achieved with the microgel that produced the thickest coating (h = 602 nm) and had the lowest cross-linking density. The results provided in this paper indicate that microgel coatings serve as an interesting and easy applicable approach and that it can be fine-tuned by manipulating the microgel layer thickness and stiffness.

Avidin-Biotin Cross-Linked Microgel Multilayers as Carriers for Antimicrobial Peptides.

Herein, we report on the formation of cross-linked antimicrobial peptide-loaded microgel multilayers. Poly(ethyl acrylate- co-methacrylic acid) microgels were synthesized and functionalized with biotin to enable the formation of microgel multilayers cross-linked with avidin. Microgel functionalization and avidin cross-linking were verified with infrared spectroscopy, dynamic light scattering, and z-potential measurements, while multilayer formation (up to four layers) was studied with null ellipsometry and quartz crystal microbalance with dissipation (QCM-D). Incorporation of the antimicrobial peptide KYE28 (KYEITTIHNLFRKLTHRLFRRNFGYTLR) into the microgel multilayers was achieved either in one shot after multilayer formation or through addition after each microgel layer deposition. The latter was found to strongly promote peptide incorporation. Further, antimicrobial properties of the peptide-loaded microgel multilayers against Escherichia coli were investigated and compared to those of a peptide-loaded microgel monolayer. Results showed a more pronounced suppression in bacterial viability in suspension for the microgel multilayers. Correspondingly, LIVE/DEAD staining showed promoted disruption of adhered bacteria for the KYE28-loaded multilayers. Taken together, cross-linked microgel multilayers thus show promise as high load surface coatings for antimicrobial peptides.

Comparing the Relative Interfacial Affinity of Soft Colloids With Different Crosslinking Densities in Pickering Emulsions.

Pickering emulsions prepared by various kinds of soft colloids such as the poly(N-isopropylacrylamide) (PNIPAM)-based microgels, have been studied for decades in order to fabricate stimuli-responsive emulsions. It has been generally viewed that the interfacial properties of the microgel monolayers and the emulsion stability are dominated by the softness or deformability of the microgel particles. However, there is still no convenient way to characterize the adsorption/desorption energy of the microgels at the interface although this is an essential topic for microgel-stabilized emulsions. This paper presents a novel method for directly comparing the relative interfacial affinity of microgel particles with comparable size but different crosslinking densities, therefore, different softness at the oil/water interface. Typical micron-sized PNIPAM-based microgels were synthesized and used in this study. With advanced fluorescent labeling techniques, we are capable of distinguishing different kinds of microgels in a Pickering emulsion. During vigorous agitation, particles with higher adsorption energy are more likely to be found at the oil/water interface instead of the loosely adsorbed counterparts. By counting the ratio of interfacial area occupied by two microgels, the interfacial affinity of them can be compared. It is found that interfacial affinity of microgels is not only dependent on the softness but also strongly correlated with the core-shell morphology of the microgels, especially the outmost collapsed polymer layer at the interface. This result is consistent with the interfacial morphology model proposed by other researchers. The understanding of the stabilization of such Pickering emulsions can help us to design and develop responsive Pickering emulsions with better controlled stability.

Optimization Strategies for Responsivity Control of Microgel Assisted Lab-On-Fiber Optrodes.

Integrating multi-responsive polymers such as microgels onto optical fiber tips, in a controlled fashion, enables unprecedented functionalities to Lab-on-fiber optrodes. The creation of a uniform microgel monolayer with a specific coverage factor is crucial for enhancing the probes responsivity to a pre-defined target parameter. Here we report a reliable fabrication strategy, based on the dip coating technique, for the controlled realization of microgel monolayer onto unconventional substrates, such as the optical fiber tip. The latter was previously covered by a plasmonic nanostructure to make it sensitive to superficial environment changes. Microgels have been prepared using specific Poly(N-isopropylacrylamide)-based monomers that enable bulky size changes in response to both temperature and pH variations. The formation of the microgel monolayer is efficiently controlled through the selection of suitable operating pH, temperature and concentration of particle dispersions used during the dipping procedure. The effect of each parameter has been evaluated, and the validity of our procedure is confirmed by means of both morphological and optical characterizations. We demonstrate that when the coverage factor exceeds 90%, the probe responsivity to microgels swelling/collapsing is significantly improved. Our study opens new paradigms for the development of engineered microgels assisted Lab-on-Fiber probes for biochemical applications.

Modification of gold electrode with a monolayer of self-assembled microgels

A new method of modification of the gold-electrode surface with a microgel monolayer was developed. Microgel particles contained –S-S– groups to enable modification of the gold surface by self-assembly via the chemisorption process. The particles were obtained by precipitation polymerization of N-isopropylacrylamide with N,N′-bis(acryloyl)cystine cross-linker. Their spherical shape and highly uniform dispersion were confirmed by electron microscopies (SEM and TEM). Thermosensitivity of the microgel was investigated with dynamic light scattering (DLS). The formation of monolayers was monitored with a quartz-crystal microbalance. The morphology of the modified surface in its dry state and in aqueous environment was investigated with atomic force microscopy (AFM). At temperatures below the volume-phase-transition temperature the microgels formed a densely packed structure that well covered the entire surface. A significant change in morphology was observed after raising temperature above the volume-phase-transition temperature. The observed increase in roughness of the modified surface suggested that the surface of electrode could be locally, between the microgel particles, uncovered. The electrochemical properties of the modified electrode were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). A strong influence of the volume phase transition in the microgels attached to the Au surface on CV and EIS responses of the modified electrode was found. The observed behavior was reversed to that of the electrodes modified with a thin thermosensitive gel film based on N-isopropylacrylamide, i.e. the volume phase transition led to a significant increase in the voltammetric current and to a drop in electron transfer resistance. That was related to partial uncovering of the electrode surface after the shrinking process in the microgels.