PNIPAM Brush Research Articles

Synthesis of thermosensitive hybrid structure gold nanotriangles coated with poly(N-isopropylacrylamide) for reversible confinement of molecules

In this work, we investigate a synthesis method for novel systems that involve the use of gold nanotriangles arrays (AuNTs) coated with poly(N-isopropylacrylamide) (pNIPAM) brushes, designed as smart platforms for the reversible confinement of bio-particles. Initially, we employed cost-effective nanosphere lithography to fabricate gold nanotriangles arrays. Next, polymer initiator groups were attached to the AuNTs surface through a spontaneous reduction approach, enabling exclusive functionalization of pNIPAM on the gold surface. Finally, we utilized surface-initiated atom transfer radical polymerization to graft pNIPAM brushes onto the gold surface. We systematically investigated the polymer initiator groups’ grafting time and the polymerization time to control the thickness of the grafted pNIPAM brushes. Subsequently, we characterized the thermoresponsive properties of these hybrid structures using Atomic Force Microscopy (AFM) measurements, evaluating their ability to undergo on/off adsorption and desorption of polystyrene (PS) beads on their surface. Indeed, the combination of the thermosensitive pNIPAM polymer with AuNTs arrays results in the development of a precisely regulated two-dimensional active device which exhibits tunable properties with external temperature changes, making it a versatile platform suitable for a wide range of applications.

PNIPAM Brushes in Colloidal Photonic Crystals Enable Ex Situ Ethanol Vapor Sensing.

Structural colors are formed by the periodic repetition of nanostructures in a material. Upon reversibly tuning the size or optical properties of the repetitive unit inside a nanostructured material, responsive materials can be made that change color due to external stimuli. This paper presents a simple method to obtain films of ethanol vapor-responsive structural colors based on stacked poly(N-isopropylacrylamide) (PNIPAM)-grafted silica nanoparticles. Our materials show clear, reversible color transitions in the presence of near-saturated ethanol vapor. Moreover, due to the absorption of ethanol in the PNIPAM brushes, relatively long recovery times are observed (∼30 s). Materials based on bare or poly(methyl methacrylate) (PMMA) brush-grafted silica nanoparticles also change color in the presence of ethanol vapor but possess significantly shorter recovery times (∼1 s). Atomic force microscopy reveals that the delayed recovery originates from the ability of PNIPAM brushes to swell in ethanol vapor. This renders the films highly suitable for ex situ ethanol vapor sensing.

Smart Temperature-Gating and Ion Conductivity Control of Grafted Anodic Aluminum Oxide Membranes.

Over the past few decades, stimuli-responsive materials have been widely applied to porous surfaces. Permeability and conductivity control of ions confined in nanochannels modified with stimuli-responsive materials, however, have been less investigated. In this work, the permeability and conductivity control of ions confined in nanochannels of anodic aluminum oxide (AAO) templates modified with thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) brushes are demonstrated. By surface-initiated atom transfer radical polymerization (SI-ATRP), PNIPAM brushes are successfully grafted onto the hexagonally packed cylindrical nanopores of AAO templates. The surface hydrophilicities of the membranes can be reversibly altered because of the lower critical solution temperature (LCST) behavior of the PNIPAM polymer brushes. From electrochemical impedance spectroscopy (EIS) analysis, the temperature-gating behaviors of the AAO-g-PNIPAM membranes exhibit larger impedance changes than those of the pure AAO membranes at higher temperatures because of the aggregation of the grafted PNIPAM chains. The reversible surface properties caused by the extended and collapsed states of the polymer chains are also demonstrated by dye release tests. The smart thermo-gated and ion-controlled nanoporous membranes are suitable for future smart membrane applications.

Critical analysis of adhesion work measurements from AFM-based techniques for soft contact

HypothesisThe work of adhesion is a thermodynamic quantity that is frequently measured by atomic force microscopy (AFM). Determination of the work of adhesion requires quasi-equilibrium measurements, where we address the question of to what extent atomic force microscopy qualifies for quasi-equilibrium measurements. ExperimentTo measure the work of adhesion, we combined soft colloidal probe AFM (SCP AFM) with reflection interference contrast microscopy (RICM). This allowed us to extract the work of adhesion either from the pull-off force or from the contact radius. With these methods, we investigated the adhesion behavior of poly(N-isopropylacrylamide) (PNIPAM) polymer brushes in the swollen and solvent-induced collapsed state by systematically analyzing contact radii and adhesive forces. FindingsIn the swollen state, the adhesion to the PNIPAM brush was fivefold larger and exhibited significant time dependencies when measured with SCP AFM. A strong rate dependence of the pull-off force method was indicative of a non-equilibrium process. In order to reliably determine the equilibrium work of adhesion, the contact radius method was found to be the better because it is not rate dependent. Our work highlights the important benefits of using optical measurements to determine the contact radius when deriving the works of adhesion between colloidal probes and polymer brush surfaces.

Effect of surfactants on the thermoresponse of PNIPAM investigated in the brush geometry

HypothesisAnionic surfactants have been reported to interact with poly(N-isopropyl acrylamide) (PNIPAM), suppressing its thermoresponse. Scattering and NMR studies of the anionic sodium dodecylsulfate (SDS) system propose that the PNIPAM-surfactant interaction is purely hydrophobic. However, prior phenomenological investigations of a range of surfactant identities (anionic, cationic, nonionic) show that only anionic surfactants affect the thermoresponse and conformation of PNIPAM, implying that the hydrophilic head–group also contributes. Crucially, the phenomenological experiments do not measure the affinity of the tested surfactants to the polymer, only their effect on its behaviour. ExperimentsWe study the adsorption of six surfactants within a planar PNIPAM brush system, elucidating the polymer conformation, thermoresponse, and surfactant adsorption kinetics using ellipsometry, neutron reflectometry (NR), optical reflectometry and the quartz crystal microbalance technique. NR is used to measure the distribution of surfactants within the brush. FindingsWe find that only anionic surfactants modify the structure and thermoresponse of PNIPAM, with the greater affinity of anionic surfactants for PNIPAM (relative to cationic and nonionic surfactants) being the primary reason for this behaviour. These results show that the surfactant head–group has a more critical role in mediating PNIPAM-surfactant interaction than previously reported. Taking inspiration from prior molecular dynamics work on the PEO-surfactant system, we propose an interaction mechanism for PNIPAM and SDS that reconciles evidence for hydrophobic interaction with the observed head–group-dependent affinity.

Investigation of the Effect of Molecular Weight, Density, and Initiator Structure Size on the Repulsive Force between a PNIPAM Polymer Brush and Protein

This paper focuses on the effect of degree of polymerization (N), density ( σ ), and pattern size ( x ) on the interaction force between a periodically patterned Poly(N-isopropylacrylamide) (PNIPAM) brush and protein. The hydrophobic interaction, the Van der Waals attractive force, and the steric repulsive force were expressed in terms of N , σ , and x . The osmotic constant (k1) and the entropic constant (k2) were determined from the fit of the steric repulsive force to an experimentally obtained force distance curve. The osmotic constant was 0.105, and the entropic constant was 0.255. Using these constants, the steric repulsive force was plotted as a function of the separation distance(s) between the substrate and the protein. The forces were determined at a separation distance equal to 0.3 nm, where L0 is the equilibrium thickness of the PNIPAM brush. At this separation distance, the value of the steric repulsive force was much higher than the value of the sum of the hydrophobic interaction and the Van der Waals attractive force for large degree of polymerization ( N > 100 ) and density ( σ > 0.2 chains/nm2). However, the repulsive force was comparable to the sum of the hydrophobic interaction and the Van der Waals attractive force for a small degree of polymerization ( N < 100 ) and density ( σ = 0.2 ). Furthermore, the steric repulsive force was plotted as a function of pattern size x . The plot indicated that the steric repulsive force becomes nearly zero for all degrees of polymerization and density when the value of the initiator structure size was less than 200 nm. In addition to the steric repulsive force, the lateral extension of the chains in the periodically patterned PNIPAM brush was calculated by scaling low and compared with the experimental data taken from previously published literatures. The polymer brush structure was modelled as if the immediate bare substrate is so wide that even a stretched polymer segment cannot reach to the next polymer brush structure. In such models, the value of the lateral extension was equal to the thickness of the homogenous brush. It was independent of the pattern size. However, when the polymer brush structure was modelled as if there is another polymer brush structure at a distance half of the size of the period, the lateral extension was found to be dependent on the size of the initiator structure size due to chain bridging. This was witnessed by the patterning of polymer brushes using the interferometric patterning of PNIPAM brushes and an atomic force microscopy imaging of the polymer brush structures both in air and in water. The polymer brush structure resolution in water was much lower than the resolution in air, which indicates the lateral extension of the polymer chains in water. For such kind of periodic polymer brush structures, the gap between them was calculated, and it was found dependent on the degree of polymerization, density, and initiator structure size.

N-isopropylacrylamide polymer brushes alter the micro-solvation environment during aqueous nitrite hydrogenation on Pd/Al2O3 catalyst

Nitrite contaminants in freshwater streams, resulting from run-off of fertilizers and livestock farming, are a major ecological challenge. Here, we have developed a new family of catalysts based on Pd/Al2O3 coated with N-isopropylacrylamide polymer (p-NIPAM) brushes that increase N-N bond formation over N-H bond formation, promoting nitrogen selectivity by 3-fold, reaching >99% for the Pd/Al2O3 containing 20 wt% carbon in the form of p-NIPAM, without significant drops in catalytic activity (TOF of c.a. 6.8 ± 1.1 min−1). Strikingly, rigorous mass transport studies revealed that the presence of p-NIPAM does not limit the transfer of molecules during the hydrogenation of nitrites in aqueous phase. These observations were corroborated by detailed reaction kinetics in which similar activation barriers for nitrites disappearance of 30–34 kJ mol−1 were obtained regardless the polymer content. The observed reaction orders for nitrites were similar on the coated and un-coated catalysts, indicating that the rate determining step, most likely NOX-H bond formation, remained unaltered. The apparent barriers for ammonia formation, however, drastically increased from 41 ± 3 kJ mol−1 on Pd/Al2O3 to 63 ± 4 kJ mol−1 and 76 ± 5 kJ mol−1 on the 7 and 20 wt% C counterparts, respectively. Contrary to the widely accepted operation mode of thermo-responsive catalysts containing p-NIPAM brushes, we demonstrated that these polymers modify the chemical environment near the active site as shown by in-situ ATR data, tunning the catalyst selectivity without altering the molecular transport. These results will facilitate the development of more selective catalysts for liquid phase reactions relevant for drinking water purification.

Stress in a Stimuli-Responsive Polymer Brush

The application of a polymer brush in sensing, actuation, self-folding, among others acutely depends on the tuneable bending of a brush-grafted substrate caused by the stress in the brush. However, the stress in a stimuli-responsive brush has not been investigated. In this work, we study the stress in the stimuli-responsive planar polymer brushes of neutral water-soluble polymers with low to very high graft densities using strong stretching theory (SST). First, SST with the Langevin force-extension relation for a polymer chain is extended to the study of stimuli-responsive brushes. Stress profile and other properties of a Poly(N-isopropylacrylamide) (PNIPAm) brush are then obtained using the extended SST and an empirical Flory-Huggins parameter. The model predicts that the stress in a PNIPAm brush is inhomogeneous and compressive at all temperatures and graft densities. The resultant stress is predicted to increase in magnitude with increasing graft density. Moreover, it decreases in magnitude with an increase in temperature before plateauing in low graft density brushes. In contrast, its magnitude increases weakly with increasing temperature in high density brushes. This contrasting behavior is traced to the minimum in interaction free energy density \emph{vs} polymer volume fraction curve for PNIPAm solution at a large volume fraction, and stiffening of chains due to finite extensibility. Furthermore, our results indicate that the ability to tune the resultant stress by changing temperature diminishes with increasing graft density.

Thermoresponsive Polymer Gating System on Mesoporous Shells of Silica Particles Serving as Smart Nanocontainers.

Spherical silica nanoparticles with solid cores and mesoporous shells (SCMS) were decorated with thermoresponsive polymer brushes that were shown to serve as macromolecular valves to control loading and unloading of a model dye within the mesopores. Thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) brushes were grafted from the surfaces of both solid core (SC) and SCMS particles of similar size using surface-initiated atom transfer radical polymerization. Both systems based on porous (SCMS-PNIPAM) and nonporous (SC-PNIPAM) particles were characterized using cryo-TEM, thermogravimetry and elemental analysis to determine the structure and composition of the decorated nanoparticles. The grafted PNIPAM brushes were found to be responsive to temperature changes enabling temperature-controlled gating of the pores. The processes of loading and unloading in the obtained systems were examined using a model fluorescent dye—rhodamine 6G. Polymer brushes in SCMS-PNIPAM systems were shown to serve as molecular valves enabling significant adsorption (loading) of the dye inside the pores with respect to the SC-PNIPAM (no pores) and SCMS (no valves) systems. The effective unloading of the fluorescent cargo molecules from the decorated nanoparticles was achieved in a water/methanol solution. The obtained SCMS-PNIPAM particles may be used as smart nanocontainers or nanoreactors offering also facile isolation from the suspension due to the presence of dense cores.

Thermo-Responsive Polymer Brushes with Side Graft Chains: Relationship Between Molecular Architecture and Underwater Adherence.

During the last few decades, wet adhesives have been developed for applications in various fields. Nonetheless, key questions such as the most suitable polymer architecture as well as the most suitable chemical composition remain open. In this article, we investigate the underwater adhesion properties of novel responsive polymer brushes with side graft chain architecture prepared using “grafting through” approach on flat surfaces. The incorporation in the backbone of thermo-responsive poly(N-isopropylacrylamide) (PNIPAm) allowed us to obtain LCST behavior in the final layers. PNIPAm is co-polymerized with poly(methyl ethylene phosphate) (PMEP), a poloyphosphoester. The final materials are characterized studying the surface-grafted polymer as well as the polymer from the bulk solution, and pure PNIPAm brush is used as reference. PNIPAm-g-PMEP copolymers retain the responsive behavior of PNIPAm: when T > LCST, a clear switching of properties is observed. More specifically, all layers above the critical temperature show collapse of the chains, increased hydrophobicity and variation of the surface charge even if no ionizable groups are present. Secondly, effect of adhesion parameters such as debonding rate and contact time is studied. Thirdly, the reversibility of the adhesive properties is confirmed by performing adhesion cycles. Finally, the adhesive properties of the layers are studied below and above the LCST against hydrophilic and hydrophobic substrates.

Two-Stage Collapse of PNIPAM Brushes: Viscoelastic Changes Revealed by an Interferometric Laser Technique.

Many temperature-responsive polymers exhibit a single-phase transition at the lower critical solution temperature (LCST). One exception is poly(N-isopropylacryamide) (PNIPAM). PNIPAM brush layers (51 ± 3 nm thick) that are end-grafted onto glass beads collapse in two stages. The viscoelastic changes of a PNIPAM brush layers were investigated with an interferometric laser method at different temperatures. This method is able to measure the two-stage collapse of beads coated with a polymer brush layer. When these beads are situated close to a hydrophilic glass surface, they exhibit Brownian motion. As this Brownian motion changes with temperature, the collapse of the polymer layer is revealed. The characteristic spectrum of the Brownian motion of beads is modeled by a damped harmonic oscillator, where the polymer layer acts as both spring and damping elements. The change of the Brownian motion spectrum with temperature indicates two transitions of the PNIPAM brush layer, one at 36 °C and one at 46 °C. We attribute the first transition to the LCST volume collapse of PNIPAM. Here, changes of the density and viscosity of the brush dominate. The second transition is dominated by a stiffening of the brush layer.

Dynamic Tunable Color Display Based on Metal-Insulator-Metal Resonator with Polymer Brush Insulator Layer as Signal Transducer.

Dynamic color-changing nanomaterials have been widely investigated for applications in fields like optical sensors, wearable activity monitors, smart electronic devices, and anticounterfeiting materials due to the excellent ability to change their optical properties with external variation. Here, a simple metal-insulator-metal (MIM) trilayer Fabry-Perot resonance cavity with a poly(N-isopropylacrylamide) (PNIPAm) brush layer as a responsive element is reported as a thermal-induced colorimetric response platform. The dynamic changes of conformation and physical properties of PNIPAm brush layer in response to external signals give rise to a significant color change of the MIM Fabry-Perot resonance cavity. This MIM Fabry-Perot resonance cavity shows the advantages of dynamic color change, rapid response, good repeatability, and simple construction. Additionally, the as-prepared MIM cavity shows great potential in various applications such as color printing, multicolor indicator, and information anticounterfeiting.

Poly(N-isopropylacrylamide) Response to Salt Concentration and Anion Identity: A Brush-on-Brush Study.

The stability of poly(N-isopropylacrylamide) (PNIPAM) brush-modified colloidal silica particles was compared to asymmetric and symmetric PNIPAM brush direct force measurements in the presence of 1, 10, and 500 mM aqueous salt solution of KCl, KNO3, and KSCN between 10 and 45 °C. Dynamic light scattering measurements highlighted subtle variations in the salt-mediated thermoresponse, while atomic force microscopy (AFM) force curves between a bare silica or PNIPAM brush-modified colloid probe and a planar PNIPAM brush elucidated differences in brush interactions. The AFM force curves in the presence of KCl primarily revealed steric interactions between the surfaces, while KNO3 and KSCN solutions exhibited electrosteric interactions on approach as a function of the chaotropic nature of the ion and the solution concentration. The symmetric PNIPAM brush interaction highlighted significant variations between KCl and KSCN at 1 and 500 mM concentrations, while the approach and retraction force curves were relatively similar at 10 mM concentration. The combination of these techniques enabled the stability of PNIPAM brush-modified colloidal dispersions in the presence of electrolyte to be better understood with specific ion binding and the solution Debye length playing a significant role.

Effects of thiocyanate anions on switching and structure of poly(N-isopropylacrylamide) brushes**Project supported by the Joint Funds of Xinjiang Natural Science Foundation (Grant No. 2019D01C333), the National Natural Science Foundation of China (Grant Nos. 11847610 and 21764015), the National Basic Research Program of China (Grant No. 2015CB857100).

In this work, we investigate the effects of thiocyanate anions on the switching and the structure of poly (N-isopropylacrylamide) (PNIPAM) brushes using a molecular theory. Our model takes into consideration the PNIPAM–anion bonds, the electrostatic effects and their explicit coupling to the PNIPAM conformations. It is found that at low thiocyanate anion concentration, as the anion concentration of thiocyanate increases, thiocyanate anions are more associated with PNIPAM chains through the PNIPAM–anion bonds, which contributes to stronger electrostatic repulsion and leads to an increase of lower critical solution temperature (LCST). By analyzing the average volume fractions of PNIPAM brushes, it is found that the PNIPAM brush presents a plateau structure. Our results show that the thiocyanate anions promote phase segregation due to the PNIPAM–anion bonds and the electrostatic effect. According to our model, the reduction of LCST can be explained as follows: at high thiocyanate anion concentration, with the increase of thiocyanate concentration, more ion bindings occurring between thiocyanate anions and PNIPAM chains will result in the increase of the hydrophobicity of PNIPAM chains; when the increase of electrostatic repulsion is insufficient to overcome the hydrophobic interaction of PNIPAM chains, it will lead to the reduction of brush height and LCST at high thiocyanate anion concentration. Our theoretical results are consistent with the experimental observations, and provide a fundamental understanding of the effects of thiocyanate on the LCST of PNIPAM brushes.

Thermoresponsive polymer brushes on magnetic chitosan microspheres: Synthesis, characterization and application in oily water of high salinity

Smart microspheres capable of responding to magnetic fields and temperature changes were prepared by encapsulating magnetic nanoparticles into cross-linked chitosan microspheres followed by poly(N-isopropylacrylamide) (PNIPAM) brushes formation on their surfaces (MCM-PNIPAM). The synthetized microspheres were characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM), thermogravimetry (TG) and differential scanning calorimetry (DSC). While most studies have focused on the graft copolymerization reaction between chitosan and NIPAM to get a soluble particle, the main finding of this study was to improve the lipophilicity of magnetic crosslinked chitosan microspheres with PNIPAM brushes, in order to be used in oily water treatment as a solid adsorbent. The thermoresponsive behavior of MCM-PNIPAM was confirmed by the sharp transition phase on DSC curves. The initial investigation of oil removal efficiency was performed to the synthesized microspheres with values higher than 97% for MCM-PNIPAM above the PNIPAM aggregation temperature.

Colloidal deposition on polymer-brush-coated NF membranes

Fouling control remains a challenge in membrane separation. Here, nanofiltration (NF) membranes have been modified with poly-N-iso-propylacrylamide (PNIPAM) brushes, fabricated using surface-initiated atom transfer radical polymerization (ATRP). PNIPAM, a thermo-responsive polymer, exhibits a phase transition at its lower critical solution temperature (LCST) of ∼32 °C in DI water, which reduces to ∼20 °C at high-ionic strength. Direct microscopic observation was employed to investigate, in-situ, the deposition and release patterns and kinetics of colloidal fouling on NF membranes with and without a PNIPAM brush layer. Membrane surfaces were characterized by atomic force microscopy (AFM), X-ray Photoelectron Spectroscopy (XPS), and attenuated total reflection–Fourier transform infrared (ATR-FTIR) analysis. Changes in surface chemistry and morphology confirmed the grafting of PNIPAM with a rougher surface morphology. The permeate flux of grafted membranes with DI water at ∼20 °C and ∼40 °C indicate reversible conformational changes of PNIPAM. Cross-flow experiments revealed that even though the surface hydrophobicity of the PNIPAM-grafted membranes increased, the brush-coated membrane surfaces hinder particle deposition regardless of particle surface charge, exhibiting considerably lower deposition, compared to the unmodified membrane. Deposition was lower, for both membranes, in the case of negatively charged particles. When the particles had a small positive charge, a significant increase in deposition was observed for the unmodified membrane, compared with the modified membrane, presumably due to the former’s larger negative charge. However, particles, once deposited, could generally not be removed by physical rinsing, nor – in the case of the PNIPAM-coated membranes – by switching polymer conformation. Nevertheless, the results of the direct observation can provide valuable insight for further improving fouling-resistant membranes based on polymer brush coatings.

Thermoresponsive Polymer Brush Modulation on the Direction of Motion of Phoretically Driven Janus Micromotors.

We report a thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) brush functionalized Janus Au-Pt bimetallic micromotor capable of modulating the direction of motion with the change of the ambient temperature. The PNIPAM@Au-Pt micromotor moved along the Au-Pt direction with a speed of 8.5 μm s-1 in 1.5 % H2 O2 at 25 °C (below the lower critical solution temperature (LCST) of PNIPAM), whereas it changed the direction of motion (i.e., along the Pt-Au direction) and the speed decreased to 2.3 μm s-1 at 35 °C (above LCST). Below LCST, PNIPAM brushes grafted on the Au side were hydrophilic and swelled, which permitted the electron transfer and proton diffusion on the Au side, and thus the motion is regarded as a self-electrophoretic mechanism. However, PNIPAM brushes above LCST became hydrophobic and collapsed, and thus the driving mechanism switched to the self-diffusiophoresis like that of Pt-modified Janus silica motors. These motors could reversibly change the direction of motion with the transition of the hydrophobic and hydrophilic states of the grafted PNIPAM brushes. Such a thermoresponsive polymer brush functionalization method provides a new strategy for engineering the kinematic behavior of phoretically driven micro/nanomotors.

Thermoresponsive Polymer Brush Modulation on the Direction of Motion of Phoretically Driven Janus Micromotors

AbstractWe report a thermoresponsive poly(N‐isopropylacrylamide) (PNIPAM) brush functionalized Janus Au–Pt bimetallic micromotor capable of modulating the direction of motion with the change of the ambient temperature. The PNIPAM@Au–Pt micromotor moved along the Au–Pt direction with a speed of 8.5 μm s−1 in 1.5 % H2O2 at 25 °C (below the lower critical solution temperature (LCST) of PNIPAM), whereas it changed the direction of motion (i.e., along the Pt–Au direction) and the speed decreased to 2.3 μm s−1 at 35 °C (above LCST). Below LCST, PNIPAM brushes grafted on the Au side were hydrophilic and swelled, which permitted the electron transfer and proton diffusion on the Au side, and thus the motion is regarded as a self‐electrophoretic mechanism. However, PNIPAM brushes above LCST became hydrophobic and collapsed, and thus the driving mechanism switched to the self‐diffusiophoresis like that of Pt‐modified Janus silica motors. These motors could reversibly change the direction of motion with the transition of the hydrophobic and hydrophilic states of the grafted PNIPAM brushes. Such a thermoresponsive polymer brush functionalization method provides a new strategy for engineering the kinematic behavior of phoretically driven micro/nanomotors.

Dynamic Plasmonic Platform To Investigate the Correlation between Far-Field Optical Response and SERS Signal of Analytes.

The design of surface-enhanced Raman spectroscopy (SERS) platforms based on the coupling between plasmonic nanostructures and stimuli-responsive polymers has attracted considerable interest over the past decades for the detection of a wide range of analytes, including pollutants and biological molecules. However, the SERS intensity of analytes trapped inside smart hybrid nanoplatforms is subject to important fluctuations because of the spatial and spectral variation of the plasmonic near-field enhancement (i.e., its dependence with the distance to the nanoparticle surface and with the localized surface plasmon resonance). Such fluctuations may impair interpretation and quantification in sensing devices. In this paper, we investigate the influence of the plasmonic near-field profile upon the Raman signal intensity of analytes trapped inside thermoresponsive polymer-coated gold nanoarrays. For this, well-defined plasmonic arrays (nanosquares and nanocylinders) were modified by poly(N-isopropylacrylamide) (PNIPAM) brushes using surface-initiated atom-transfer radical polymerization. Molecular probes were trapped inside these Au@PNIPAM nanostructures by simple physisorption or by covalent grafting at the end of PNIPAM brushes, using click chemistry. The SERS spectra of molecular probes were studied along various heating/cooling cycles, demonstrating a strong correlation between SERS intensities and near-field spectral profile of underlying nanoparticles, as confirmed by simulations based on the finite difference time domain method. Thermoresponsive plasmonic devices thus provide an ideal dynamic SERS platform to investigate the influence of the near-field plasmonic profile upon the SERS response of analytes.

Influence of molecular weight on PNIPAM brush modified colloidal silica particles.

The effect of molecular weight and temperature on the phase transition and internal structure of poly(N-isopropylacrylamide) brush modified colloidal silica particles was investigated using dynamic light scattering (DLS) and small angle neutron scattering (SANS) between 15 and 45 °C. Dry particle analysis utilising transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) all confirmed the thickness of the polymer brush shell increased as a function of polymerisation time. Hydrodynamic diameter and electrophoretic mobility results revealed that the brush modified particles transitioned from swollen shells to a collapsed conformation between 15 and 35 °C. The dispersions were electrosterically stabilised over the entire temperature range investigated, with minimal thermal hysteresis recorded. Modelling of the hydrodynamic diameter enabled the calculation of a lower critical solution temperature (LCST) which increased as a function of brush thickness. The internal structure determined via SANS showed a swollen brush at low temperatures (18 and 25 °C) which decayed radially away from the substrate, while a collapsed block-like conformation with 60% polymer volume fraction was present at 40 °C. Radial phase separation was evident at intermediate temperatures (30 and 32.5 °C) with the lower molecular weight sample having a greater volume fraction of polymer in the dense inner region at these temperatures.