Microgel Suspensions Research Articles

A Free Energy Model for the Plateau Shear Modulus in Thermosensitive Microgel Suspensions.

Polymer microgels exhibit intriguing macroscopic flow properties arising from their unique microscopic structure. Microgel colloids usually comprise a cross-linked polymer network with a radially decaying density profile, resulting in a dense core surrounded by a fuzzy corona. Notably, microgels synthesized from poly(N-isopropylacrylamide) (PNIPAM) are thermoresponsive and capable of adjusting their size and density profile based on temperature. Above the lower critical solution temperature ( °C), the microgel's polymer network collapses, expulsing water through a reversible process. Conversely, below 33 °C, the microgel's network swells, becoming highly compressible and allowing overpacking to effective volume fractions exceeding one. Under conditions of dense packing, microgels undergo deformation in distinct stages: corona compression and faceting, interpenetration, and finally, isotropic compression. Each stage exhibits a characteristic signature in the dense microgel suspensions' yield stress and elastic modulus. Here, we introduce a model for the linear elastic shear modulus by minimizing a quasi-equilibrium free energy, encompassing all relevant energetic contributions. We validate our model by comparing its predictions to experimental results from oscillatory shear rheology tests on microgel suspensions at different densities and temperatures. Our findings demonstrate that combining macroscopic rheological measurements with the model allows for temperature-dependent characterization of polymer interaction parameters.

Numerical Study of Neutral and Charged Microgel Suspensions: From Single-Particle to Collective Behavior

We perform extensive molecular dynamics simulations of an ensemble of realistic microgel particles in swollen conditions in a wide range of packing fractions ζ. We compare neutral and charged microgels, where we consider charge distribution adherent to experimental conditions. Through a detailed analysis of single-particle behavior, we are able to identify the different regimes occurring upon increasing concentration: from shrinking to deformation and interpenetration, always connecting our findings with available experimental observations. We then link these single-particle features with the collective behavior of the suspension, finding evidence of a structural reentrance that has no counterpart in the dynamics. Hence, while the maximum of the radial distribution function displays a nonmonotonic behavior with increasing ζ, the dynamics, quantified by the microgels’ mean-squared displacement, always slows down. This behavior, at odds with the simple Hertzian model, can be described by a phenomenological multi-Hertzian model, which takes into account the enhanced internal stiffness of the core. However, also this model fails when deformation enters into play, whereby more realistic many-body models are required. Thanks to our analysis, we are able to unveil the key physical mechanisms, shrinking and deformation, giving rise to the structural reentrance that holds up to very large packing fractions. We further identify key similarities and differences between neutral and charged microgels, for which we detect at high enough ζ the fusion of charged shells, previously invoked to explain key experimental findings, and responsible for the structural reentrance. Overall, our study establishes a powerful framework to uncover the physics of microgel suspensions, paving the way to tackle different regimes, e.g., high temperature, and internal architectures, such as for hollow and ultralow-cross-linked microgels, where experimental evidence is still limited. Published by the American Physical Society 2024

Improved Emulsifying Performance of Agarose Microgels by Cross-Interfacial Diffusion of Polyphenols.

Noninterface-active polysaccharides can acquire better emulsifying properties through microgelation, yet optimizing their emulsifying performance remains a significant challenge. This study introduces a novel approach to enhance the emulsifying performance of polysaccharide microgels by leveraging the cross-interfacial diffusion of polyphenols, which promotes the interfacial adsorption of microgels. Tannic acid (TA) was predispersed in oil phases and subsequently emulsified with agarose microgel (AM) suspensions, and the impacts of TA diffusion on the emulsifying performance of AMs was investigated. In addition, the transmittance profiles of oil-water biphasic systems were found to innovatively indicate the cross-interfacial diffusion of TA and the interfacial adsorption of AMs. The current results suggest that an appropriate level of TA incorporation can benefit the emulsifying performance of AMs, correlating with decreased droplet sizes and improved physical stability of the emulsion. However, excessive TA might trigger the clustering of AMs before they reach the interfacial layer, adversely affecting the emulsion stability. In conclusion, the cross-interfacial diffusion of polyphenols offers a promising strategy to overcome the stability challenges encountered in polysaccharide microgel-stabilized emulsions.

Link between permanent shear-banding and local concentration fluctuations in suspensions of compressible microgels

We uncover the occurrence of shear banding in dense suspensions of compressible microgels. Velocimetry measurements evidence the presence of permanent but unsteady shear-banding for sufficiently small Peclet numbers, with the formation of a central plug-like flow. Small-angle neutron scattering experiments under shear link the observed banding phenomenon to structural variations along the velocity gradient, providing a connection between the arrested band and the increase in structural correlations associated with changes in the local packing fraction. This provides unique evidence of a shear–concentration coupling mechanism in jammed suspensions of compressible particles.

Laponite Nanoclay‐Loaded Microgel Suspensions as Supportive Matrices for Osteogenesis

Microscale carriers have emerged as promising materials for nurturing cell growth and as delivery vehicles for regenerative therapies. Carriers based on granular hydrogels have proved advantageous, where “microgels” can be formulated to have a broad range of properties to guide the behavior of adherent cells. Herein, the fabrication of osteogenic microgel matrices through the incorporation of laponite nanoclays is demonstrated. Forming a jammed suspension provides a scaffolding where cells can adhere to the surface of the microgels, with pathways for migration and proliferation fostered by the interstitial volume. By varying the content and type of laponite—RD and XLG—the degree of osteogenesis can be tuned in embedded populations of adipose‐derived stem cells. The nano‐ and microstructured composite materials enhance osteogenesis at the transcript and protein level, leading to increased deposition of bone minerals and an increase in the compressive modulus of the assembled scaffold. Together, these microgel suspensions are promising materials for encouraging osteogenesis with scope for delivery via injection and stabilization to bone‐mimetic mechanical properties after matrix deposition.

Mie scattering theory applied to light scattering of large nonhomogeneous colloidal spheres.

Colloidal suspensions made of smart core-shell structures are of current interest in many fields. Their properties come from the possibility of varying the core and shell materials for modifying the composite particles' chemical, biological, and optical properties. These particles are formed with a material with a constant refractive index core and a shell with a refractive index decaying until it matches the solvent refractive index. Poly(N-IsoPropyl AcrylaMide) (PNIPAM) is a typical example of materials forming shells. In this report, we present how to apply Mie scattering theory to predict and understand the static light scattering of large nonhomogeneous colloidal particles with spherical symmetry whose size is comparable with or larger than the light wavelength used for developing scattering experiments, where the Rayleigh-Gans-Debye approximation is not valid. Here, the refractive index decay was approximated by a Gaussian RI profile numerically evaluated through a multilayer sphere. We calculated the form factor functions of suspensions of PNIPAM microgels previously reported and core-shell suspensions made of polystyrene/PNIPAM at 20 and 40 °C synthesized by us. In all the cases, our method succeeded in providing the scattering intensity as a function of the angle. The software for using the numerical method is fairly straightforward and is accessible as an open-source code. The results can not only help predict and understand the photonic properties of microgels with large core-shell structures but also for any particle with a refractive index distribution with spherical symmetry, as in the case of microgels with super chaotropic agents, hollow microgels, or microparticles.

3D Printable Poly(N-isopropylacrylamide) Microgel Suspensions with Temperature-Dependent Rheological Responses.

Microgel suspensions have garnered significant interest in fundamental research due to their phase transition between liquid-like to paste-like behaviors stemming from tunable interparticle and particle-solvent interactions. Particularly, stimuli-responsive microgels undergo faster volume changes in response to external stimuli in comparison to their bulk counterparts, while maintaining their structural integrity. Here, concentrated and diluted suspensions of poly(N-isopropylacrylamide) (PNIPAm) microgels are dispersed to different packing fractions in water for the characterizations of temperature-responsive rheological responses. In the intrinsic volume phase transition (VPT), polymer chains collapse, and microgels shrink to smaller sizes. Additionally, the intermicrogel and microgel-solvent interactions vary in VPT, which results in microgel clusters that significantly affect the linear shear moduli of suspensions. The effect of the temperature ramp rate of PNIPAm microgel suspensions on rheological responses is characterized. Moreover, the effect of the mass fraction of microgels on the relative viscosity of dilute microgel suspensions is investigated. These results shed light on understanding the heating and cooling rate-dependent temperature responsiveness of PNIPAm microgel suspensions, establishing pathways to regulate the rheological characteristics in temperature-responsive microgel-based platforms. Therefore, this work envisions technological advancements in different fields such as drug delivery, tissue engineering, and diagnostic tools.

High mechanical properties nanocomposite hydrogel achieved based on montmorillonite and tailored microgel suspensions reinforcing polyacryamide networks

Hydrogels have attracted much attention because of their softness and water retention ability, but their poor mechanical properties have severely limited their application in various aspects. Herein, we reported a strategy to fabricate polyacrylamide/montmorillonite nanocomposite hydrogel by introducing montmorillonite via a facile and universal two-step method composed of microgel suspension system and in situ free radical polymerization. Compared with microgel, microgel suspension is simpler to prepare and better dispersed in hydrogels, which it could act as physical crosslinking points, interpenetrate with polyacrylamide networks embedded, and serve as sacrifical bonds to strengthen the hydrogels. Simultaneously, montmorillonite synergistically facilitated the formation of a robust and uniform polymer structure through the interaction of hydrogen bonds and polyacrylamide networks, resulting in significant improvements in mechanical properties. As a result, the satisfactory mechanical properties of the nanocomposite hydrogels are achieved at a relative high water content (80 wt%), including a superior compressive strength (95% deformation) of 37.96 MPa, tensile strength of 311.1 ± 8.2 kPa, elongation at break of 316.5 ± 21.1%, Young's modulus of 165.8 ± 7.5 kPa, and excellent toughness of 644.1 ± 21.8 kJ/m3, respectively. In addition, it was found that the hydrogel had excellent cycle compression stability through 10 cycles of loading and unloading at 80% strain. These new high-performance nanocomposite hydrogels are expected to be used in the fields of structural or load-bearing materials.

Effective viscous lubrication of cartilage with low viscosity microgels

Viscosupplementation is one of the primary treatments for osteoarthritis, with the goal of restoring the viscoelastic properties of native synovial fluid. Recent work shows a strong in vitro in vivo correlation between the lubricating abilities of viscosupplements and improved patient reported outcomes, suggesting new viscosupplement formulations need to achieve sufficient lubrication of cartilage to be clinically relevant. This study describes a library of low viscosity microgel suspensions that lubricate cartilage as if they were highly viscous lubricants. Microgel formulations were characterized by their size, rheological properties, and lubricating abilities. Microgels synthesized with low crosslinking density exhibited lubrication equivalent to bovine synovial fluid (µ = 0.037–0.064), while maintaining low measured viscosities similar to PBS (η(10 s−1) = 2.04–4.71 mPa*s). These results set the foundation for a new era of viscosupplementation using low viscosity lubricants.

Amphoteric nano‐ and microgels with acrylamide backbone for potential application in oil recovery

AbstractAmphoteric nano‐ and microgels based on acrylamide (AAm), 3‐acrylamidopropyltrimethylammonium chloride (APTAC) and 2‐acrylamido‐2‐propanesulfonate sodium salt (AMPS) were prepared via inverse emulsion polymerization in the presence of crosslinking agent—N,N′‐methylenebisacrylamide (MBAA). Several polyampholyte nano‐ and microgel samples AAm‐APTAC‐AMPS with compositions (70:15:15, 80:10:10, and 90:5:5 mol%) were obtained and they were abbreviated as AAm70‐APTAC15‐AMPS15, AAm80‐APTAC10‐AMPS10 AAm90‐APTAC5‐AMPS5 (where the lower indexes indicate the molar concentration of monomers). The nano‐ and microgels were characterized by Fourier‐transform infrared spectroscopy, dynamic light scattering (DLS), transmission electron microscope (TEM), thermogravimetric analysis and interfacial tension measurements. The most attention was paid to the AAm80‐APTAC10‐AMPS10 microgel because its linear analog showed the best swelling capacity and the viscosifying effect for potential application in oil recovery. The influence of monomer concentration, surfactants, volume ratio of the water/organic phases, and the hydrophilic–lyophilic balance (HLB) on the average hydrodynamic size of the AAm80‐APTAC10‐AMPS10 nano‐ and microgels was studied. The size distribution of nano‐ and microgels derived from DLS data and TEM images was compared as a function of monomer concentration at constant surfactant concentration (6 wt%), HLB = 5.5 and mixture of water:oil = 60:40 vol%. Swelling of microgel particles in saline water due to the antipolyelectrolyte effect was observed. The applicability of amphoteric microgels AAm80‐APTAC10‐AMPS10 for oil recovery was tested on cores simulating the conditions of a model oil reservoir. The obtained results indicated that after the injection of around three pore volumes of the 2500 ppm microgel suspension into the sandstone core the permeability to brine decreased from 1.5 to 0.78 mD. For the first half of core sample the residual resistance factor was higher than the resistance factor, whereas for the second part of core sample these parameters were almost equal. Additional experiments with longer cores are needed to evaluate in‐depth propagation of microgels and permeability reduction in porous media.

Spin-coating deposition of thermoresponsive microgel thin films

Smart surfaces and surface coatings have been attracting increasing interest in the last decades. In particular, thin films assembled from microgels offer good control of morphology, elasticity and hydrophobicity thanks to the high tunability of microgel mechanical properties and chemical composition. Among smart microgels, Poly(N-isopropylacrylamide) (PNIPAM) based microgels are the most used systems for theoretical and experimental studies and for nanotechnological applications. When used as building blocks to fabricate 2D assemblies, they exhibit new properties offering many advantages for additional applications in different fields. Here we report a systematic investigation of aqueous suspensions of soft PNIPAM microgels through Dynamic Light Scattering (DLS), Small Angle X-ray Scattering (SAXS) and rheometry. Starting from these suspensions, optical and morphological properties of PNIPAM microgel thin films deposited by spin-coating on a glass substrate at different weight concentrations and deposition conditions are investigated through UV-Vis-NIR spectroscopy and Atomic Force Microscopy (AFM). Homogeneous and smooth thin films of soft PNIPAM microgels were obtained with high transparency in the whole wavelength range from the visible to the near-infrared region. Moreover, their optical properties were correlated to microgel arrangement at the solid surface that can be opportunely tuned by changing the spin-coating deposition parameters.

Microscopically grounded constitutive model for dense suspensions of soft particles below jamming

Materials made up of soft elastic particles suspended in a fluid form a broad subset of complex fluids, including emulsions, suspensions of microgels, liposomes, or vesicles. Until now, no established model can describe how they flow. Here, we derive from particle-level dynamics a constitutive model describing the rheology of two-dimensional dense soft suspensions below the jamming transition, in a regime where elastic interactions dominate the stress response. Our model successfully captures many observed rheological features, such as shear thinning, normal stresses, and normal stress differences scaling respectively linearly and quadratically with deformation rate in the slow flow limit.

Agarose Fluid Gels Formed by Shear Processing During Gelation for Suspended 3D Bioprinting.

The use of granular matrices to support parts during the bioprinting process was first reported by Bhattacharjee et al. in 2015, and since then, several approaches have been developed for the preparation and use of supporting gel beds in 3D bioprinting. This paper describes a process to manufacture microgel suspensions using agarose (known as fluid gels), wherein particle formation is governed by the application of shear during gelation. Such processing produces carefully defined microstructures, with subsequent material properties that impart distinct advantages as embedding print media, both chemically and mechanically. These include behaving as viscoelastic solid-like materials at zero shear, limiting long-range diffusion, and demonstrating the characteristic shear-thinning behavior of flocculated systems. On the removal of shear stress, however, fluid gels have the capacity to rapidly recover their elastic properties. This lack of hysteresis is directly linked to the defined microstructures previously alluded to; because of the processing, reactive, non-gelled polymer chains at the particle interface facilitate interparticle interactions-similar to a Velcro effect. This rapid recovery of elastic properties enables bioprinting high-resolution parts from low-viscosity biomaterials, as rapid reformation of the support bed traps the bioink in situ, maintaining its shape. Furthermore, an advantage of agarose fluid gels is the asymmetric gelling/melting transitions (gelation temperature of ~30 °C and melting temperature of ~90 °C). This thermal hysteresis of agarose makes it possible to print and culture the bioprinted part in situ without the supporting fluid gel melting. This protocol shows how to manufacture agarose fluid gels and demonstrates their use to support the production of a range of complex hydrogel parts within suspended-layer additive manufacture (SLAM).

Self-Healing of Charged Microgels in Neutral and Charged Environments.

The softness of microgels depends on many aspects, such as particle characteristic lengths, sample concentration, chemical composition of the sample, and elastic moduli of the particle. Here, the response to crowding of ionic microgels is studied. Charged and uncharged ionic microgels are studied in concentrated suspensions of both neutral and ionic microgels with the same swollen size. The combination of small-angle X-ray and neutron scattering with contrast variation allows us to probe both the particle-to-particle arrangement and the response of individual ionic microgels to crowding. When the ionic microgels are uncharged, initial isotropic deswelling followed by faceting is observed. Therefore, the ionizable groups in the polymeric network do not affect the response of the ionic microgel to crowding, which is similar to what has been reported for neutral microgels. In contrast, the kind of microgels composing the matrix plays a key role once the ionic microgels are charged. If the matrix is composed of neutral microgels, a pronounced faceting and negligible deswelling is observed. When only charged ionic microgels are present in the suspension, isotropic deswelling without faceting is dominant.

Dielectric relaxation of ice in a partially crystallized poly(N-isopropylacrylamide)microgel suspension compared to other partially crystalized polymer-water mixtures.

A broadband dielectric spectroscopy study was conducted on a partially crystallized 10 wt% poly(N-isopropylacrylamide) [PNIPAM] microgel aqueous suspension to investigate the dielectric relaxation of ice in microgel suspensions. The measurements covered a frequency range of 10 mHz to 10 MHz and at temperatures ranging from 123 K to 273 K. Two distinct relaxation processes were observed at specific frequencies below the melting temperature. One is associated with the combination of the local chain motion of PNIPAM and interfacial polarization in the uncrystallized phase, while another is associated with ice. To understand the temperature-dependent behaviour of the ice relaxation process, the relaxation time of ice was compared with those observed in other frozen polymer water mixtures, including gelatin, poly-vinylpyrrolidone (PVP), and bovine serum albumin (BSA). For concentrations ≥ 10 wt%, the temperature dependence of the relaxation time of ice was found to be independent. Therefore, the study primarily focused on the 10 wt% data for easier comprehension of the ice relaxation process. It was found that the microgel and globular protein BSA had no significant effect on ice crystallization, while gelatin slowed down the crystallization process, and PVP accelerated it. To discuss the mechanism of the dielectric relaxation of ice, the trap-controlled proton transport model developed by Khamzin et al. [Chem. Phys., 2021, 541, 111040.] was employed. The model was used to discuss the dynamic heterogeneity of ice observed in this investigation, distinguishing it from the spatial heterogeneity of ice commonly discussed.

In situ formation of osteochondral interfaces through "bone-ink" printing in tailored microgel suspensions.

Osteochondral tissue has a complex hierarchical structure spanning subchondral bone to articular cartilage. Biomaterials approaches to mimic and repair these interfaces have had limited success, largely due to challenges in fabricating composite hard-soft interfaces with living cells. Biofabrication approaches have emerged as attractive methods to form osteochondral analogues through additive assembly of hard and soft components. We have developed a unique printing platform that is able to integrate soft and hard materials concurrently through freeform printing of mineralized constructs within tunable microgel suspensions containing living cells. A library of microgels based on gelatin were prepared, where the stiffness of the microgels and a liquid "filler" phase can be tuned for bioprinting while simultaneously directing differentiation. Tuning microgel stiffness and filler content differentially directs chondrogenesis and osteogenesis within the same construct, demonstrating how this technique can be used to fabricate osteochondral interfaces in a single step. Printing of a rapidly setting calcium phosphate cement, so called "bone-ink" within a cell laden suspension bath further guides differentiation, where the cells adjacent to the nucleated hydroxyapatite phase undergo osteogenesis with cells in the surrounding medium undergoing chondrogenesis. In this way, bone analogues with hierarchical structure can be formed within cell-laden gradient soft matrices to yield multiphasic osteochondral constructs. This technique provides a versatile one-pot biofabrication approach without harsh post-processing which will aid efforts in bone disease modelling and tissue engineering. STATEMENT OF SIGNIFICANCE: This paper demonstrates the first example of a biofabrication approach to rapidly form osteochondral constructs in a single step under physiological conditions. Key to this advance is a tunable suspension of extracellular matrix microgels that are packed together with stem cells, providing a unique and modular scaffolding for guiding the simultaneous formation of bone and cartilage tissue. The physical properties of the suspension allow direct writing of a ceramic "bone-ink", resulting in an ordered structure of microscale hydrogels, living cells, and bone mimics in a single step. This platform reveals a simple approach to making complex skeletal tissue for disease modelling, with the possibility of repairing and replacing bone-cartilage interfaces in the clinic using a patient's own cells.

Impact of polyelectrolyte adsorption on the rheology of concentrated poly(N-isopropylacrylamide) microgel suspensions.

We explore the impact of three water-soluble polyelectrolytes (PEs) on the flow of concentrated suspensions of poly(N-isopropylacrylamide) (PNIPAm) microgels with thermoresponsive anionic charge density. By progressively adding the PEs to a jammed suspension of swollen microgels, we show that the rheology of the mixtures is remarkably influenced by the sign of the PE charge, PE concentration and hydrophobicity only when the temperature is increased above the microgel volume phase transition temperature Tc, namely when microgels collapse, they are partially hydrophobic and form a volume-spanning colloidal gel. We find that the original gel is strengthened close to the isoelectric point, attained when microgels are mixed with cationic PEs, while PE hydrophobicity rules the gel strengthening at very high PE concentrations. Surprisingly, we find that polyelectrolyte adsorption or partial embedding of PE chains inside the microgel periphery occurs also when anionic polymers of polystyrene sulfonate with a high degree of sulfonation are added. This gives rise to colloidal stabilization and to the melting of the original gel network above Tc. Contrastingly, the presence of polyelectrolytes in suspensions of swollen, jammed microgels results in a weak softening of the original repulsive glass, even when an apparent isoelectric condition is met. Our study puts forward the crucial role of electrostatics in thermosensitive microgels, unveiling an exciting new way to tailor the flow of these soft colloids and highlighting a largely unexplored path to engineer soft colloidal mixtures.

Stress-independent delay time in yielding of dilute colloidal gels.

We investigate the yielding under shear for dilute poly(N-isopropyl acrylamide-co-fumaric acid) (PNIPAM-FAc) colloidal gels obtained above the volume phase transition temperature. In this temperature range, the microgel suspensions form colloidal gels due to hydrophobic interparticle interactions under appropriate pH and ionic strength conditions. Step-strain tests revealed that yielding occurs when the applied strain exceeds a specific threshold, requiring a finite, stress-independent delay time (tD). This is distinct from previous findings on delayed yielding in other colloidal gels, where tD decreases with increasing stress. In the start-up shear tests, yield strain (γy) at a higher strain rate () increases with escalating , while γy at lower  remains constant. This characteristic γy- relationship is successfully explained by a simple model using the stress-independent tD value without an adjustable fitting parameter. The distinctive yielding behavior, underscored by a stress-independent tD, is expected to originate from strain-induced macroscopic phase separation into a dense colloidal gel and water, observable separately from rheological measurements.

Rheological responses of microgel suspensions with temperature-responsive capillary networks.

A method coupling microgel jamming and temperature-responsive capillary networking is developed to manipulate the rheological properties of microgel-capillary suspensions by varying microgel sizes, volume fraction of capillary solution, and temperature after polymerization and photo-crosslinking. This approach allows for the 3D extrusion of this suspension to print complex structures that can be readily scaled up and applied to biomedical fields and soft material-based actuation.

Unveiling the structural relaxation of microgel suspensions at hydrophilic and hydrophobic interfaces

HypothesisPoly(N-isopropylacrylamide) (PNIPAM) microgel particles show considerable hydrophilicity below the lower critical solution temperature (LCST) while they become hydrophobic above LCST. We hypothesize that interfacial wettability could tune particle−surface interaction and subsequent structural relaxation of microgel suspensions at interfaces during the volume phase transition. ExperimentsThe evanescent-wave scattering images of microgels at hydrophilic and hydrophobic interfaces are analyzed by a density-fluctuation autocorrelation function (δACF) over a wide range of particle volume fraction ϕ. The structural relaxation is characterized by the decay behavior of δACF. The scattering images in bulk are also processed as a comparison. FindingsA two-step relaxation decay is observed at both hydrophilic and hydrophobic interfaces. Relative to fast decay, the rate of structural relaxation in slow decay is reduced by a factor of ∼ 500 and ∼ 50 at hydrophilic and hydrophobic interfaces, respectively. The relaxation times obey divergent power-law dependences on intermediate regime of observing length scales at the two interfaces. Besides, the distribution of fluctuation for relaxation time at different local regions reveals that the structural relaxation is much more homogenous at hydrophilic interfaces than that at hydrophobic interfaces, especially at high ϕ.