Spatial Distribution Of Nanoparticles Research Articles

Voltage-induced rearrangement in silver nanoparticles spatial distribution produced by EAFD method and its LSPR optimization

Abstract This paper presents a voltage-induced and thermal annealing rearrangement (VITAR) method based on modified Electric Field Assisted Film Dissolution (EAFD) method as a flexible and powerful tool for manipulating nanoparticles spatial distribution based on drift and diffusion mechanisms that occur due to external DC voltage and thermal annealing processes. Different samples with various arrangements of external DC voltage and thermal annealing processes have been produced. The extinction and attenuated total reflection (ATR) spectra, as well as Atomic Force Microscope (AFM) images, have been employed to investigate their optical and morphological properties. Four cases with arrangements of DV-Anl, DV-Anl-DV, DV-Anl-IV, and DV-IV-Anl have been studied. The AFM images show that by applying secondary voltage (direct or inverse voltage), it is possible to drift nanoparticles and change its morphology (size and shape) as well as surface and volume distributions. As a result, by applying a secondary direct voltage (in the DV-Anl-DV case), the surface density of nanoparticles decreases due to direct drift force. It is notable that in this case, the extinction peak and ATR depth have not significantly changed. By applying a secondary inverse voltage (in the DV-Anl-IV, and DV-IV-Anl cases), an increase in the surface density of the nanoparticles has been observed. Also, the extinction peak has increased, and the ATR depth has decreased in the DV-Anl-IV case, but in the DV-IV-Anl case, due to the uniform size of surface nanoparticles, the resonance power has shown a significant increase in both extinction and ATR spectra compared to other cases. The resulting changes in extinction and ATR spectra show that by using the VITAR process, the surface structure, morphology and its optical properties can be optimized and this method provides a great opportunity to enhance Localized Surface Plasmon Resonance (LSPR) effects, which can be employed in nano-optical devices.

Automated Image Analysis of Transmission Electron Micrographs: Nanoscale Evaluation of Radiation-Induced DNA Damage in the Context of Chromatin.

Heavy ion irradiation (IR) with high-linear energy transfer (LET) is characterized by a unique depth dose distribution and increased biological effectiveness. Following high-LET IR, localized energy deposition along the particle trajectories induces clustered DNA lesions, leading to low electron density domains (LEDDs). To investigate the spatiotemporal dynamics of DNA repair and chromatin remodeling, we established the automated image analysis of transmission electron micrographs. Human fibroblasts were irradiated with high-LET carbon ions or low-LET photons. At 0.1 h, 0.5 h, 5 h, and 24 h post-IR, nanoparticle-labeled repair factors (53BP1, pKu70, pKu80, DNA-PKcs) were visualized using transmission electron microscopy in interphase nuclei to monitor the formation and repair of DNA damage in the chromatin ultrastructure. Using AI-based software tools, advanced image analysis techniques were established to assess the DNA damage pattern following low-LET versus high-LET IR. Low-LET IR induced single DNA lesions throughout the nucleus, and most DNA double-strand breaks (DSBs) were efficiently rejoined with no visible chromatin decondensation. High-LET IR induced clustered DNA damage concentrated along the particle trajectories, resulting in circumscribed LEDDs. Automated image analysis was used to determine the exact number of differently sized nanoparticles, their distance from one another, and their precise location within the micrographs (based on size, shape, and density). Chromatin densities were determined from grayscale features, and nanoparticles were automatically assigned to euchromatin or heterochromatin. High-LET IR-induced LEDDs were delineated using automated segmentation, and the spatial distribution of nanoparticles in relation to segmented LEDDs was determined. The results of our image analysis suggest that high-LET IR induces chromatin relaxation along particle trajectories, enabling the critical repair of successive DNA damage. Following exposure to different radiation qualities, automated image analysis of nanoparticle-labeled DNA repair proteins in the chromatin ultrastructure enables precise characterization of specific DNA damage patterns.

Toward Predicting Nanoparticle Distribution in Heterogeneous Tumor Tissues.

Nanobio interaction studies have generated a significant amount of data. An important next step is to organize the data and design computational techniques to analyze the nanobio interactions. Here we developed a computational technique to correlate the nanoparticle spatial distribution within heterogeneous solid tumors. This approach led to greater than 88% predictive accuracy of nanoparticle location within a tumor tissue. This proof-of-concept study shows that tumor heterogeneity might be defined computationally by the patterns of biological structures within the tissue, enabling the identification of tumor patterns for nanoparticle accumulation.

Quantitative titanium imaging in fish tissues exposed to titanium dioxide nanoparticles by laser ablation-inductively coupled plasma-mass spectrometry

Imaging studies by laser ablation–inductively coupled plasma mass spectrometry have been successfully developed to obtain qualitative and quantitative information on the presence/distribution of titanium (ionic titanium and/or titanium dioxide nanoparticles) in sea bream tissues (kidney, liver, and muscle) after exposure assays with 45-nm citrate-coated titanium dioxide nanoparticles. Laboratory-produced gelatine standards containing ionic titanium were used as a calibration strategy for obtaining laser ablation–based images using quantitative (titanium concentrations) data. The best calibration strategy consisted of using gelatine-based titanium standards (from 0.1 to 2.0 μg g−1) by placing 5.0-μL drops of the liquid gelatine standards onto microscope glass sample holders. After air drying at room temperature good homogeneity of the placed drops was obtained, which led to good repeatability of measurements (calibration slope of 4.21 × 104 ± 0.39 × 104, n = 3) and good linearity (coefficient of determination higher than 0.990). Under the optimised conditions, a limit of detection of 0.087 μg g−1 titanium was assessed. This strategy allowed to locate prominent areas of titanium in the tissues as well as to quantify the bioaccumulated titanium and a better understanding of titanium dioxide nanoparticle spatial distribution in sea bream tissues.Graphical abstract

Double‐Interlinked Colloidal Gels for Programable Fabrication of Supraparticle Architectures

AbstractEngineering colloidal gel inks with suitable features for fabricating robust supraparticle architectures through 3D printing may overcome the challenges of precisely controlling nanoparticles spatial distribution across multiple scales. Herein, oppositely charged proteinaceous‐polymeric nanoparticles are combined to generate multi‐component colloidal gel (COGEL) inks for fabricating supraparticle volumetric architectures. Leveraging on different nano‐functional units, double‐interlinked supraparticle assemblies are established via electrostatic interactions and on‐demand covalent photocrosslinking. The COGEL inks are readily processable through in‐air extrusion 3D printing, forming stable colloidal filaments. 3D printing yielded architecturally defined and robust supraparticle constructs that supported human stem cells attachment and cytoskeletal spreading. Owing to double interparticle interlinks the fabricated supraparticle constructs remained stable under physiological conditions and high/low shear stress, improving over the lower mechanical stability of single‐interlinked platforms. Double‐interlinked COGELs are processable via suspension 3D printing, unlocking the freeform volumetric writing of nanoparticle inks in protein‐based hydrogels volume. The dual‐interlinked COGEL technology opens new possibilities for generating user‐defined supraparticle architectures with precise volumetric distribution of nanoparticles, both in‐air and in‐hydrogel platforms. The freedom to select modular multi‐particle combinations, as well as the rapid 3D programming of COGEL inks, broadens the range of modular colloidal materials that can be fabricated for a variety of biomedical applications.

Quantifying Intracellular Nanoparticle Distributions with Three-Dimensional Super-Resolution Microscopy.

Super-resolution microscopy can transform our understanding of nanoparticle-cell interactions. Here, we established a super-resolution imaging technology to visualize nanoparticle distributions inside mammalian cells. The cells were exposed to metallic nanoparticles and then embedded within different swellable hydrogels to enable quantitative three-dimensional (3D) imaging approaching electron-microscopy-like resolution using a standard light microscope. By exploiting the nanoparticles' light scattering properties, we demonstrated quantitative label-free imaging of intracellular nanoparticles with ultrastructural context. We confirmed the compatibility of two expansion microscopy protocols, protein retention and pan-expansion microscopy, with nanoparticle uptake studies. We validated relative differences between nanoparticle cellular accumulation for various surface modifications using mass spectrometry and determined the intracellular nanoparticle spatial distribution in 3D for entire single cells. This super-resolution imaging platform technology may be broadly used to understand the nanoparticle intracellular fate in fundamental and applied studies to potentially inform the engineering of safer and more effective nanomedicines.

High-Throughput Nanoparticle Characterization via Glow Discharge Optical Emission Spectroscopy Elemental Mapping

Nanoparticle (NP) characterization is critical in many fields due to the use of NPs in numerous applications. Traditional NP characterization techniques, however, are limited by low sample throughput, and few can measure the size and elemental composition. Furthermore, sample throughput limitations are compounded in elemental mapping (EM) techniques for obtaining NP spatial distribution. Glow discharge optical emission spectroscopy (GDOES) EM can provide large area maps directly and cost-effectively from solid samples within tens of seconds. Here, GDOES EM is demonstrated for the first time for NP characterization in terms of mass, elemental composition, and size/structure dimensions. The effects of GD pulsed power, pressure, and sample substrate were studied, and optimized conditions resulted in limits of detection at single pg levels. While this is not at the level of single nanoparticle sensitivity, size differentiation of Ag and Au nanoparticles was successfully demonstrated between 5 and 100 nm, while the internal dimensions of complex core-shell NPs were also identified through the optical emission changes as a function of time.

Quantification of nanoparticles' concentration inside polymer films using lock-in thermography.

Thin nanocomposite polymer films embedding various types of nanoparticles have been the target of abundant research to use them as sensors, smart coatings, or artificial skin. Their characterization is challenging and requires novel methods that can provide qualitative as well as quantitative information about their composition and the spatial distribution of nanoparticles. In this work, we show how lock-in thermography (LIT) can be used to quantify the concentration of gold nanoparticles embedded in polyvinyl alcohol (PVA) films. LIT is an emerging and non-destructive technique that measures the thermal signature produced by an absorbing sample illuminated by modulated light with a defined frequency. Films with various concentrations of gold nanoparticles of two different sizes have been prepared by evaporation from homogeneous aqueous PVA gold nanoparticle suspensions. When the thin films were illuminated with monochromatic light at a wavelength close to the plasmonic resonance signature of the nanoparticles, the amplitude of the thermal signature emitted by the nanoparticles was recorded. The measurements have been repeated for multiple modulation frequencies of the incident radiation. We have developed a mathematical method to quantitatively relate the concentration of nanoparticles to the measured amplitude. A discussion about the conditions under which the sample thickness can be determined is provided. Furthermore, our results show how LIT measurements can easily detect the presence of concentration gradients in samples and how the model allows the measured signal to be related to the respective concentrations. This work demonstrates the successful use of LIT as a reliable and non-destructive method to quantify nanoparticle concentrations.

Structural and temperature-dependent magnetic characteristics of Ho doped CoFe2O4 nanostructures

The magnetism in low-dimensional materials is the consequence of several factors, including the type of crystal structure and spatial distribution of nanoparticles. Understanding and exploring these challenges are vital to introduce nanomaterials for industrial applications. The present study reveals the substitutional effect of Holmium on the magnetic properties of cobalt ferrite. The nanostructures are prepared by co-precipitation procedure for the stoichiometric growth of CoHoxFe2-xO4 (0 ≤ x ≤ 0.1); Δx = 0.025 ferrite compositions. The crystal structure and phase determination of all the samples identify a typical cubic structure (Fd-3m); however, a secondary phase, appearing at x = 0.1, originates due to the formation of HoFeO3. An increasing trend in lattice constant, X-ray density and hopping lengths with Ho doping in Co ferrite is observed in the synthesized nanoparticles. The structural analysis by high-resolution transmission electron microscopy confirms the crystal structure of spinel ferrite. The magnetic characteristics measured at room temperature depict that the coercivity, saturation magnetization, and magneton number increase due to the impact of Ho3+ substitution. The saturation magnetization of CoHo0.05Fe1.95O4 nanoparticles as a function of temperature satisfies Bloch's law, and the coercivity of the sample remained in good agreement with Kneller's law.

Gold Nano-Bio-Interaction to Modulate Mechanobiological Responses for Cancer Therapy Applications.

In the present study, we investigate the mechanobiological responses of human lung cancer that may occur through their interactions with two different types of gold nanoparticles: nanostars and nanospheres. Hyperspectral images of nanoparticle-treated cells revealed different spatial distributions of nanoparticles in cells depending on their morphology, with nanospheres being more uniformly distributed in cells than nanostars. Gold nanospheres were also found to be more effective in mechanobiological modulations. They significantly suppressed the migratory ability of cells under different incubation times while lowering the bulk stiffness and adhesion of cells. This in vitro study suggests the potential applications of gold nanoparticles to manage cell migration. Nano-bio-interactions appeared to impact the cytoskeletal organization of cells and consequently alter the mechanical properties of cells, which could influence the cellular functions of cells. According to the results and migratory index model, it is thought that nanoparticle-treated cells experience mechanical changes in their body, which largely reduces their migratory potentials. These findings provide a better understanding of nano-bio-interaction in terms of cell mechanics and highlight the importance of mechanobiological responses in designing gold nanoparticles for cancer therapy.

Quantifying Nanoparticle Assembly States in a Polymer Matrix through Deep Learning

There is great interest in controlling the spatial dispersion of inorganic nanoparticles (NPs) in an organic polymer matrix because this centrally underpins the property enhancements obtained from these hybrid materials. Currently, qualitative information on NP spatial distribution is obtained by visual inspection of transmission electron microscopy (TEM) images. Quantitative information is only indirectly obtained through the use of scattering probes such as small-angle X-ray/neutron scattering (SAXS/SANS). While the main challenge, that scattering probes operate in reciprocal space, can be remedied by Fourier inverting the data into real space, a much harder issue deconvolves the contribution of the particle form factor (which is affected by the details of the NP size and shape) from the structure factor that contains information on NP spatial distribution. These problems become acute when we deal with the popular topic of NPs grafted with polymer chains because the polymeric corona and hence the particle form factor becomes context-dependent and is hard to quantify. To make progress, we develop and apply a deep-learning-based image analysis method to quantify the distribution of spherical NPs in a polymer matrix directly from their real-space TEM images. A dataset of NP detection (DOPAD) is built by manually labeling particle positions on experimental TEM images of diverse polymer composite systems. A convolutional neural network object detection model is then trained on DOPAD. Together with sliding-window and merging algorithms, an automated pipeline is established, which takes a large TEM image as input and extracts NP locations and sizes. We validate the structural information resulting from this method against SAXS-derived structural information for NPs ordered by polymer crystallization and then use it to distinguish between different states of the assembly of polymer-grafted NPs in a polymer matrix achieved by using their surfactancy. We show that this data-rich protocol allows us to draw critical facets of experimental behavior which have previously not been accessible. The DOPAD dataset, Python source code, and trained model are shared on GitHub at https://dopad.github.io.

Nanoscale Spatial Distribution of Supported Nanoparticles Controls Activity and Stability in Powder Catalysts for CO Oxidation and Photocatalytic H2 Evolution.

Supported metal nanoparticles are essential components of high-performing catalysts, and their structures are intensely researched. In comparison, nanoparticle spatial distribution in powder catalysts is conventionally not quantified, and the influence of this collective property on catalyst performance remains poorly investigated. Here, we demonstrate a general colloidal self-assembly method to control uniformity of nanoparticle spatial distribution on common industrial powder supports. We quantify distributions on the nanoscale using image statistics and show that the type of nanospatial distribution determines not only the stability, but also the activity of heterogeneous catalysts. Widely investigated systems (Au-TiO2 for CO oxidation thermocatalysis and Pd-TiO2 for H2 evolution photocatalysis) were used to showcase the universal importance of nanoparticle spatial organization. Spatially and temporally resolved microkinetic modeling revealed that nonuniformly distributed Au nanoparticles suffer from local depletion of surface oxygen, and therefore lower CO oxidation activity, as compared to uniformly distributed nanoparticles. Nanoparticle spatial distribution also determines the stability of Pd-TiO2 photocatalysts, because nonuniformly distributed nanoparticles sinter while uniformly distributed nanoparticles do not. This work introduces new tools to evaluate and understand catalyst collective (ensemble) properties in powder catalysts, which thereby pave the way to more active and stable heterogeneous catalysts.

Enhanced performance and fouling resistance of cellulose acetate forward osmosis membrane with the spatial distribution of TiO2 and Al2O3 nanoparticles

AbstractBACKGROUNDNovel nanocomposite membranes with spatial distribution of nanoparticles (NPs) were fabricated for forward osmosis (FO) applications. In this work, TiO2 and Al2O3 NPs were used as hydrophilic additives in order to improve the performance and fouling resistance of cellulose acetate (CA) FO membrane.RESULTSAttenuated Total Reflection Fourier Transform Infrared (ATR‐FTIR) and x‐ray diffraction (XRD) analyses confirmed the successful incorporation of the NPs into the synthesized membranes. The specific reverse salt flux (SRSF) of the TiO2 modified membrane was reduced from 0.88 to 0.56 g L−1, which was attributed to enhanced hydrophilicity, porosity, and the simultaneously improved water and salt permeability coefficients. After the evaluation of CA membranes with various contents of TiO2 NPs, Al2O3 NPs were added to the membrane structure as a secondary additive under the optimized content of TiO2 NPs. Al2O3 NPs have a higher dispersion in the membrane sublayer beneath, which can affect the hydrophilicity and surface charge of the membranes. Al2O3 and TiO2 modified membranes showed the lowest values of contact angle and zeta potential in neutral pH, which was 56.7°and − 68.4 mV, respectively. This membrane showed a water flux (WF) of 15 L m−2h−1 and an SRSF of 0.36 g L−1 when using 1 mol L−1 NaCl as a draw solution. The fouling behavior of sodium alginate on the neat and modified membranes was also investigated, and the results showed a reduced fouling propensity and a superior fouling reversibility in the modified membranes.CONCLUSIONBased upon these findings, using low‐density hydrophilic NPs in the membrane structure can fabricate membranes with more hydrophilicity, excellent FO performance, and high organic fouling resistance. © 2020 Society of Chemical Industry

Three-dimensional localization microscopy in live flowing cells.

Capturing the dynamics of live cell populations with nanoscale resolution poses a significant challenge, primarily owing to the speed-resolution trade-off of existing microscopy techniques. Flow cytometry would offer sufficient throughput, but lacks subsample detail. Here we show that imaging flow cytometry, in which the point detectors of flow cytometry are replaced with a camera to record 2D images, is compatible with 3D localization microscopy through point-spread-function engineering, which encodes the depth of the emitter into the emission pattern captured by the camera. The extraction of 3D positions from sub-cellular objects of interest is achieved by calibrating the depth-dependent response of the imaging system using fluorescent beads mixed with the sample buffer. This approach enables 4D imaging of up to tens of thousands of objects per minute and can be applied to characterize chromatin dynamics and the uptake and spatial distribution of nanoparticles in live cancer cells.

Modeling Nanocarrier Transport across a 3D In Vitro Human Blood-Brain-Barrier Microvasculature.

Polymer nanoparticles (NPs), due to their small size and surface functionalization potential have demonstrated effective drug transport across the blood-brain-barrier (BBB). Currently, the lack of in vitro BBB models that closely recapitulate complex human brain microenvironments contributes to high failure rates of neuropharmaceutical clinical trials. In this work, a previously established microfluidic 3D in vitro human BBB model, formed by the self-assembly of human-induced pluripotent stem cell-derived endothelial cells, primary brain pericytes, and astrocytes in triculture within a 3D fibrin hydrogel is exploited to quantify polymer NP permeability, as a function of size and surface chemistry. Microvasculature are perfused with commercially available 100-400 nm fluorescent polystyrene (PS) NPs, and newly synthesized 100 nm rhodamine-labeled polyurethane (PU) NPs. Confocal images are taken at different timepoints and computationally analyzed to quantify fluorescence intensity inside/outside the microvasculature, to determine NP spatial distribution and permeability in 3D. Results show similar permeability of PS and PU NPs, which increases after surface-functionalization with brain-associated ligand holo-transferrin. Compared to conventional transwell models, the method enables rapid analysis of NP permeability in a physiologically relevant human BBB set-up. Therefore, this work demonstrates a new methodology to preclinically assess NP ability to cross the human BBB.

Effects of chain stiffness and shear flow on nanoparticle dispersion and distribution in ring polymer melts

The dispersion behavior and spatial distribution of nanoparticles (NPs) in ring polymer melts are explored by using molecular dynamics (MD) simulations. As polymer-NP interactions increase, three general categories of polymer-mediated NP organization are observed, namely, contact aggregation, bridging, and steric dispersion, consistent with the results of equivalent linear ones in previous studies. In the case of direct contact aggregation among NPs, the explicit aggregation-dispersion transition of NPs in ring polymer melts can be induced by increasing the chain stiffness or applying a steady shear flow. Results further indicate that NPs can achieve an optimal dispersed state with the appropriate chain stiffness and shear flow. Moreover, shear flow cannot only improve the dispersion of NPs in ring polymer melts but also control the spatial distribution of NPs into a well-ordered structure. This improvement becomes more evident under stronger polymer-NP interactions. The observed induced-dispersion or ordered distribution of NPs may provide efficient access to the design and manufacture of high-performance polymer nanocomposites (PNCs).

Dynamic covalent chemistry steers synchronizing nanoparticle self-assembly with interfacial polymerization

Precise organization of matter across multiple length scales is of particular interest because of its great potential with advanced functions and properties. Here we demonstrate a simple yet versatile strategy that enables the organization of hydrophobic nanoparticles within the covalent organic framework (COF) in an emulsion droplet. The interfacial polymerization takes place upon the addition of Lewis acid in the aqueous phase, which allows the formation of COF after a crystallization process. Meanwhile, the interaction between nanoparticles and COF is realized by the use of amine-aldehyde reactions in the nearest loci of the nanoparticles. Importantly, the competition between the nanoparticle self-assembly and interfacial polymerization allows control over the spatial distribution of nanoparticles within COF. As a general strategy, a wide variety of COF-wrapped nanoparticle assemblies can be synthesized and these hybridized nanomaterials could find applications in optoelectronics, heterogeneous catalysis and energy chemistry.

Nanoparticle Dispersion and Glass Transition Behavior of Polyimide-grafted Silica Nanocomposites

How to control the spatial distribution of nanoparticles to meet different performance requirements is a constant challenge in the field of polymer nanocomposites. Current studies have been focused on the flexible polymer chain systems. In this study, the rigid polyimide (PI) chain grafted silica particles with different grafting chain lengths and grafting densities were prepared by “grafting to” method, and the influence of polymerization degree of grafted chains (N), matrix chains (P), and grafting density (σ) on the spatial distribution of nanoparticles in the PI matrix was explored. The glass transition temperature (Tg) of PI composites was systematically investigated as well. The results show that silica particles are well dispersed in polyamic acid composite systems, while aggregation and small clusters appear in PI nanocomposites after thermal imidization. Besides, the particle size has no impact on the spatial distribution of nanoparticles. When σ·N0.5 ≪ (N/P)2, the grafted and matrix chains interpenetrate, and the frictional resistance of the segment increases, resulting in restricted relaxation kinetics and Tg increase of the PI composite system. In addition, smaller particle size and longer grafted chains are beneficial to improving Tg of composites. These results are all propitious to complete the microstructure control theory of nanocomposites and make a theoretical foundation for the high performance and multi-function of PI nanocomposites.

Enhanced mobility of iron nanoparticles deposited onto a xenon-buffered silicon substrate

The growth of nanoparticles from the gas phase in combination with deposition under ultrahigh vacuum conditions enables one to obtain pure and mass-selected nanoparticles with variable particle density from a wide range of materials on virtually any solid support and is therefore of great interest for many applications. While the magnetic, chemical, and optical properties of such deposits are intensively investigated, less work has been undertaken so far to achieve ordered arrangements of nanoparticles deposited from a cluster beam. In this work we demonstrate a first step towards the control of nanoparticle spatial distribution for iron nanoparticles with a size of about 12 nm. We find that while deposition onto a bare Si substrate results in a random distribution of isolated nanoparticles, the introduction and subsequent desorption of a Xe buffer layer induces mobility and agglomeration of nanoparticles on the Si surface. The agglomerates are extended and exhibit a height equal to about 15 nanoparticles. The vertical growth of the agglomerates is assigned to the presence of a magnetic field which was applied perpendicular to the substrate surface. We suggest that by tuning the magnetic field and deposition conditions, the spatial arrangement of magnetic nanoparticles could be controlled.

Phase miscibility and dynamic heterogeneity in PMMA/SAN blends through solvent free reactive grafting of SAN on graphene oxide

The spatial distribution of nanoparticles in a particular host polymer matrix can be improved by using brush coated nanoparticles. In this work we have grafted styrene-acrylonitrile (SAN) onto the surface of graphene oxide (GO) and investigated as to how the demixing temperature, morphology and volume cooperativity of PMMA/SAN blends are influenced. Grafting of polymer chains on the surface of nanoparticles usually involves the use of large amounts of solvents, many which are detrimental to the environment besides involving cumbersome processes. SAN-g-GO was prepared by a robust solvent-free strategy wherein the cyano group in SAN was replaced by oxazoline groups during melt mixing in the presence of zinc acetate and ethanol amine. These newly created oxazoline groups reacted with the COOH group of GO under melt extrusion resulting in grafting of SAN on the surface of GO sheets. The effect of SAN-g-GO nanoparticles on the demixing, local segmental motions and morphology evolution for different annealing times was carefully investigated in a classical LCST system, PMMA/SAN blend, using melt rheology, modulated DSC and AFM, respectively. The changes in viscoelastic behavior in the vicinity of demixing are investigated systematically for the control, and blends with GO and SAN-g-GO. Various models were used to gain insight into the spinodal decomposition temperatures of the blends. Interestingly, the demixing temperature determined rheologically and the spinodal decomposition temperature increased significantly in the presence of polymer grafted nanoparticles in comparison to the control and blends with GO. The evolution of the morphology, interfacial driven coarsening as a function of temperature and the localization of nanoparticles were assessed using atomic force microscopy. The cooperatively re-arranging regions estimated from calorimetric measurements begin to suggest enhanced dynamic heterogeneity in the presence of GO and SAN-g-GO in the blends. Taken together, our study reveals that the solvent-free approach of grafting SAN onto GO delays demixing, suppresses coalescence and alters cooperative relaxation in PMMA/SAN blends.