Polymer-grafted Nanoparticles Research Articles

Nano-Hydroxyapatite Particle Brushes via Direct Initiator Tethering and Surface-Initiated Atom Transfer Radical Polymerization for Dual Responsive Pickering Emulsion.

Well-defined polymer-grafted solid inorganic nanoparticles (NPs) are imperative for practical applications in various fields based on the prerequisite of facile initiator immobilization. Direct atom transfer radical polymerization (ATRP) initiator-tethered solid NPs are described using 2-bromo-2-methylpropionic acid as a tetherable initiator. To illustrate the versatility of the proposed strategy, nano-hydroxyapatite (n-HAP) nanocrystals (NCs) were selected to demonstrate the morphology-controlled synthesis of 2-bromo-2-methylpropionate (2-BrMP) group-immobilized n-HAP (n-HAP-Br) NCs. When water was employed as the sole solvent, the continually introduced 2-BrMP groups altered the surface hydrophobic capacity of the n-HAP-Br NC and thus led to unavoidable aggregation of n-HAP-Br NCs. The synthesis of individually dispersed n-HAP-Br NCs was achieved by rational adjusting polarity of the aqueous medium through adding a portion of water-miscible organic solvents. The type and concentration of added water-miscible organic solvents had critical effects on the morphology and particle size of n-HAP-Br NCs. To verify the efficiency of the tethered initiator, n-HAP-g-poly2-(dimethylamino) ethyl methacrylate (n-HAP-g-PDMAEMA), n-HAP-g-polyacrylonitrile (n-HAP-g-PAN), and n-HAP-g-polymethyl methacrylate (n-HAP-g-PMMA) were fabricated by surface-initiated ATRP (SI-ATRP). Acting as a solid particle emulsifier, the designed n-HAP-g-PDMAEMA-stabilized Pickering emulsion displayed dual pH and temperature response with reversible behaviors. This work presents a versatile and simple way for the fabrication of initiator-immobilized solid NPs (e.g., n-HAP NCs, gibbsite nanoplatelets, and γ-FeOOH nanofibers) ready for polymer grafting and thus enables promising performance in widespread applications.

Mixing-demixing transition in polymer-grafted spherical nanoparticles.

Polymer-grafted nanoparticles (PGNPs) can provide property profiles that cannot be obtained individually by polymers or nanoparticles (NPs). Here, we have studied the mixing-demixing transition of symmetric copolymer melts of polymer-grafted spherical nanoparticles by means of coarse-grained molecular dynamics simulation and a theoretical mean-field model. We find that a larger size of NPs leads to higher stability for a given number of grafted chains and chain lengths, reaching a point where demixing is not possible. Most importantly, the increase in the number of grafted chains, Ng, can initially favour the phase separation of PGNPs, but a further increase can lead to more difficult demixing. The reason is the increasing impact of an effective core that forms as the grafting density of the tethered polymer chains around the NPs increases. The range and exact values of Ng where this change in behaviour takes place depend on the NP size and the chain length of the grafted polymer chains. Our study elucidates the phase behaviour of PGNPs and in particular the influence of the grafting density on the phase behaviour of the systems, anticipating that it will open new doors in the understanding of these systems with implications in materials science and medicine.

Engineering interfacial entropic effects to generate giant viscosity changes in nanoparticle embedded polymer thin films.

Thin polymer and polymer nanocomposite (PNC) films are being extensively used as advanced functional coating materials in various technological applications. Since it is widely known that various properties of these thin films, especially their thermo-mechanical behavior, can be considerably different from the bulk depending on the thickness as well as interaction with surrounding media, it is imperative to study these properties directly on the films. However, quite often, it becomes difficult to perform these measurements reliably due to a dearth of techniques, especially to measure mechnical or transport properties like the viscosity of thin polymer or PNC films. Here, we demonstrate a new method to study the viscosity of PNC thin films using atomic force microscopy based force-distance spectroscopy. Using this method we investigated viscosity and the glass transition, Tg, of PNC thin films consisting of polymer grafted nanoparticles (PGNPs) embedded in un-entangled homopolymer melt films. The PGNP-polymer interfacial entropic interaction parameter, f, operationally controlled through the ratio of grafted and matrix molecular weight, was systematically tuned while maintaining good dispersion even at very high PGNP loadings, φ. We observed both a significant reduction (low f) and giant enhancement (high f) in the viscosity of the PNC thin films with the effect becoming more prominent with increasing φ. Significantly, none of the established theoretical models for viscosity changes observed earlier in suspensions or polymer nanocomposites can explain the observed viscosity variation. Our results thus not only demonstrate the tunability of the interfacial entropic effect to facilitate a dramatic change in the viscosity of PNC coatings, which could be of great utility in various applications of these materials, but also suggest a new regime of viscosity variation in athermal PNC films indicating the possible need for a new theoretical model.

Functionalization of NaGdF4 nanoparticles with a dibromomaleimide-terminated polymer for MR/optical imaging of thrombosis

A thrombosis-targeted molecular imaging probe with magnetic resonance (MR) and optical dual-modality capacity using dibromomaleimide (DBM)-bearing polymer-grafted NaGdF4 nanoparticles.

Nanoparticle translocation across the lung surfactant film regulated by grafting polymers.

Nanoparticle-based pulmonary drug delivery has gained significant attention due to its ease of administration, increased bioavailability, and reduced side effects caused by a high systemic dosage. After being delivered into the deep lung, the inhaled nanoparticles first interact with the lung surfactant lining layer composed of phospholipids and surfactant proteins and then potentially cause the dysfunction of the lung surfactant. Conditioning the surface properties of nanoparticles with grafting polymers to avoid these side effects is of crucial importance to the efficiency and safety of pulmonary drug delivery. Herein, we perform coarse-grained molecular simulations to decipher the involved mechanism responsible for the translocation of the polymer-grafted Au nanoparticles across the lung surfactant film. The simulations illustrate that conditioning of the grafting polymers, including their length, terminal charge, and grafting density, can result in different translocation processes. Based on the energy analysis, we find that these discrepancies in translocation stem from the affinity of the nanoparticles with the lipid tails and heads and their contact with the proteins, which can be tuned by the surface polarity and surface charge of the nanoparticles. We further demonstrate that the interaction between the nanoparticles and the lung surfactant is related to the depletion of the lipids and proteins during translocation, which affects the surface tension of the surfactant film. The change in the surface tension in turn affects the nanoparticle translocation and the collapse of the surfactant film. These results can help understand the adverse effects of the nanoparticles on the lung surfactant film and provide guidance to the design of inhaled nanomedicines for improved permeability and targeting.

Free-standing metal-organic framework (MOF) monolayers by self-assembly of polymer-grafted nanoparticles.

We report a general method for the synthesis of free-standing, self-assembled MOF monolayers (SAMMs) at an air–water interface using polymer-brush coated MOF nanoparticles. UiO-66, UiO-66-NH2, and MIL-88B-NH2 were functionalized with a catechol-bound chain-transfer agent (CTA) to graft poly(methyl methacrylate) (PMMA) from the surface of the MOF using reversible addition-fragmentation chain transfer polymerization (RAFT). The polymer-coated MOFs were self-assembled at the air–water interface into monolayer films ∼250 nm thick and capable of self-supporting at a total area of 40 mm2. Mixed-particle films were prepared through the assembly of MOF mixtures, while multilayer films were achieved through sequential transfer of the monolayers to a glass slide substrate. This method offers a modular and generalizable route to fabricate thin-films with inherent porosity and sub-micron thickness composed of a variety of MOF particles and functionalities.

Solution Rheology of Poly(acrylic acid)-Grafted Silica Nanoparticles

Network formation of polymer-grafted nanoparticles in aqueous solutions is an unexplored area in polymer science. In this study, nanoparticles grafted with poly(acrylic acid) (PAA) chains with diff...

Unveiling the Mechanism of the Location of the Grafted Nanoparticles in a Lamellar-Forming Block Copolymer.

Through coarse-grained molecular dynamics simulation of polymer-grafted nanoparticles (NPs) in a lamellar-forming diblock copolymer (BCP), we systematically study the effects of the grafting density (Ng), the compatibility between the grafted chains and the A-block of BCPs (εgA), and the NP number (N) on the distance (D) of the NPs from the interface by proposing novel characterization parameters of the orientation and distribution of the grafted chains. The NP gradually migrates away from the interface and into the A-block region with the increase of εgA for all studied Ng, while slightly returning toward the interface at high εgA and great Ng, which is the first observation of nonmonotonic migration at the molecular level. We ascribe the reason of this to the behavior of the grafted chains that are near the interface. Furthermore, we classify the grafted chains into three types along the normal direction of the interface and the migration process is illustrated by the distribution and orientation of the different types of grafted chains, together with the radial distribution function between the NP and the A-block chains. We observe the formation of the NP layers parallel to the interface for N < 20, and a similar nonmonotonic migration of the layers is as well observed. The D is the largest for a small N because of the excluded volume effects between the NPs. Increasing Ng and N pushes the neighboring NP layers toward the interface due to the mutual repulsion. Generally, this study may shed some light on how to better understand and design high-performance polymer nanocomposites with a tunable location of NPs.

In Situ Seed-Mediated Growth of Polymer-Grafted Gold Nanoparticles.

We report a facile yet general in situ seed-mediated method for the synthesis of polymer-grafted gold nanoparticles with narrow size distributions (<10%), accurately tunable sizes, and excellent colloidal stability. This method can be extended to a broad range of types and molecular weights of polymer ligands. Nanoparticles with different shapes can also be prepared by using preformed shaped nanoparticles directly as the seeds.

Deformation of Chemically Heterogeneous Interfacial Layers of Polymer Nanocomposites.

Dynamics of entangled interfacial polymer layers around nanoparticles determine the linear rheological properties of polymer nanocomposites. In this study, the nonlinear elastic properties of nanocomposites are examined under large-amplitude oscillatory shear (LAOS) flow to reveal the effect of interfacial chemical heterogeneity on the deformation mechanism of polymer-grafted and polymer-adsorbed nanoparticle composites. Adsorbed-poly(methyl methacrylate) (PMMA) layers presented stronger interfacial stiffening and reinforcement than PMMA-grafted layers. Chemical heterogeneities of interfacial layers, provided by polymer-adsorbed and low graft density particles, deformed at smaller strains than the poly(ethylene oxide) (PEO) matrix. Interfaces of loosely bound PMMA and PEO exhibited stiffening at low strains due to the enhanced chain mixing and entanglements. These results demonstrate that chemical and dynamic heterogeneities in interfacial layers have significant importance in designing adaptive polymer nanocomposites for large shear deformation.

Theory for the Dynamics of Polymer Grafted Nanoparticle in Solution

We develop a theory for the dynamics of polymer grafted nanoparticle (PGNP) in dilute solution. A formalism of multiscale generalized Gaussian structure (mGGS) is developed where multiscale nature is described as variable size of monomers connected to each other through harmonic springs with different spring constants. This formalism allows to study various dynamic properties of polymer chains or networks grafted nanoparticles at arbitrary positions. We analyze three dynamic properties of PGNP, viz. (i) the mean displacement of a specified monomer of the polymer chain and its time evolution under external (unit step) forces, (ii) loss and storage moduli, and (iii) intrinsic viscosity. The study highlights the unfolding dynamics of a polymer chain with different sizes of nanoparticles and shows that the chain dynamics depends on the position of applied step force in PGNP. Similarly, the elastic moduli and the intrinsic viscosity reflects the viscoelastic properties of PGNP. The storage and the loss moduli ...

Uniaxial Deformation and Crazing in Glassy Polymer-Grafted Nanoparticle Ultrathin Films.

The deformation behavior of neat, glassy polymer-grafted nanoparticle (PGN) monolayer films is studied using coarse-grained molecular dynamics simulations and experiments on polystyrene-grafted silica. In both the simulations and experiments, apparent crazing behavior is observed during deformation. The PGN systems show a relatively more uniform, perforated sheet craze structure and significantly higher strain at break than reference homopolymers of the same length. Short chain, unentangled PGN monolayers are also simulated for comparison; these are brittle and break apart without crazing. The entangled PGN simulations are analyzed in detail for systems at both high and moderate graft density. Stress-strain curves show three distinct regions: yielding and strain localization, craze widening, and strain hardening preceding catastrophic failure. The PGN stress-strain behavior appears more similar to that of longer chain, highly entangled homopolymer films than to the reference homopolymer films of the same length as the graft chains, suggesting that the particles effectively add additional entanglement points. The moderate graft density particles have higher strain-to-failure and maximum stress than the high graft density particles. We suggest this increased robustness for lower graft density systems is due to their increased interpenetration of graft chains between neighboring particles, which leads to increased interparticle entanglements per chain.

Accelerated Local Dynamics in Matrix-Free Polymer Grafted Nanoparticles.

The tracer diffusion coefficient of six different permanent gases in polymer-grafted nanoparticle (GNP) membranes, i.e., neat GNP constructs with no solvent, show a maximum as a function of the grafted chain length at fixed grafting density. This trend is reproduced for two different NP sizes and three different polymer chemistries. We postulate that nonmonotonic changes in local, segmental friction as a function of graft chain length (at fixed grafting density) must underpin these effects, and use quasielastic neutron scattering to probe the self-motions of polymer chains at the relevant segmental scale (i.e., sampling local friction or viscosity). These data, when interpreted with a jump diffusion model, show that, in addition to the speeding-up in local chain dynamics, the elementary distance over which segments hop is strongly dependent on graft chain length. We therefore conclude that transport modifications in these GNP layers, which are underpinned by a structural transition from a concentrated brush to semidilute polymer brush, are a consequence of both spatial and temporal changes, both of which are likely driven by the lower polymer densities of the GNPs relative to the neat polymer.

Nanoimprint Directed Assembly of Associating Polymer-Grafted Nanoparticles for Polymer Thin Films with Enhanced Stability

We find that changing the chemistry of the inorganic core of polymer-grafted nanoparticles (PGNPs) from Au to TiO2 in a polymer matrix having the same chemistry leads to a qualitative change in the...

Surface-Initiated Atom Transfer Radical Polymerization for the Preparation of Well-Defined Organic-Inorganic Hybrid Nanomaterials.

Surface-initiated atom transfer radical polymerization (SI-ATRP) is a powerful tool that allows for the synthesis of organic–inorganic hybrid nanomaterials with high potential applications in many disciplines. This review presents synthetic achievements and modifications of nanoparticles via SI-ATRP described in literature last decade. The work mainly focuses on the research development of silica, gold and iron polymer-grafted nanoparticles as well as nature-based materials like nanocellulose. Moreover, typical single examples of nanoparticles modification, i.e., ZnO, are presented. The organic–inorganic hybrid systems received according to the reversible deactivation radical polymerization (RDRP) approach with drastically reduced catalyst complex concentration indicate a wide range of applications of materials including biomedicine and microelectronic devices.

Effect of Polymer Chemistry on Chain Conformations in Hairy Nanoparticle Assemblies.

Matrix-free, polymer-grafted nanoparticles, called hairy nanoparticle assemblies (aHNPs), have proven advantageous over traditional nanocomposites, as good dispersion and structural order can be achieved. Recent studies have shown that conformational changes in the polymer structure can lead to significant enhancements in the mechanical properties of aHNPs. To quantify how polymer chemistry affects the chain conformations in aHNPs, here we present a comparative analysis based on coarse-grained molecular dynamics simulations. Specifically, we compare the chain conformations in an anisotropic cellulose nanoparticle grafted to four common polymers with distinct chemical groups, fragility, and segmental structures, that is, poly(methyl methacrylate) (PMMA), polystyrene (PS), polycarbonate (PC), and polybutadiene (PB). We observe that semiflexible glassy polymers such as PMMA and PS have a higher critical chain length (Ncr), the transition point where the polymer conformation changes from concentrated to semidilute brush regime. Flexible rubbery polymers (PB) can overcome the Ncr barrier at relatively lower molecular weights. We have used theoretical scaling laws based on Daoud-Cotton theory to uncover a direct correlation between empirical constants and physical parameters, such as persistence length and monomer excluded volume. Furthermore, we carried out a systematic study to understand the role of backbone rigidity and side-group size of polymer, and it revealed that the backbone rigidity significantly affects Ncr but the side-group size doesn't seem to have an appreciable effect on Ncr. We find that normalization of the monomer radial distribution curves using Ncr and other key molecular parameters collapses the curves for 110 distinct model aHNP systems studied. Our work paves the way for systematic quantification of these molecular design parameters to accelerate the design of polymer-grafted nanoparticle assemblies in combination with universal scaling relationships.

Forming Covalent Crosslinks between Polymer‐Grafted Nanoparticles as a Route to Highly Filled and Mechanically Robust Nanocomposites

AbstractFiller aggregation in polymer matrix nanocomposites leads to inhomogeneity in particle distribution and deterioration of mechanical properties. The use of polymer‐grafted nanoparticles (PGNPs) with polymers directly attached to the particle surfaces precludes aggregation of the filler. However, solids composed of PGNPs are mechanically weak unless the grafted chains are long enough to form entanglements between particles, and requiring long grafts limits the achievable filler density of the nanocomposite. In this work, long, entangled grafts are replaced with short reactive polymers that form covalent crosslinks between particles. Crosslinkable PGNPs, referred to as XNPs, can be easily processed from solution and subsequently cured to yield a highly filled yet mechanically robust composite. In this specific instance, silica nanoparticles are grafted with poly(glycidyl methacrylate), cast into films, and crosslinked with multifunctional amines at elevated temperatures. Indentation and scratch experiments show significant enhancement of hardness, modulus, and scratch resistance compared to non‐crosslinked PGNPs and to crosslinked polymer films without nanoparticle reinforcement. Loadings of up to 57 wt% are achieved while yielding uniform films that deform locally in a predominantly elastic manner. XNPs therefore potentially allow for the formulation of robust nanocomposites with a high level of functionality imparted by the selected filler particles.

Hierarchical complex self-assembly in binary nanoparticle mixtures

Hierarchical self-assembly of soft matter provides a powerful route to create complex materials with enhanced physical properties. The understanding of the fundamental processes leading to such organization can provide design rules to create new functional materials. In this work, we use a simple model of polymer-grafted nanoparticles to explore the self-assembly of binary mixtures. By using Monte Carlo simulations we study the interplay of composition, density and particle sizes on the self-organization of such nanoparticle systems. It is found that complex hierarchical organization can take place for conditions where one-component systems form simple lattices. In particular, a mixture where one component forms a structure with 18-fold symmetry in a sea of an apparent disordered phase of the second component is observed to emerge for certain parameter combinations.

Tuning the Relaxation of Imprinted Polymer Films with Polymer-Grafted Nanoparticles

Tuning the Relaxation of Imprinted Polymer Films with Polymer-Grafted Nanoparticles

Non-Equilibrium Phase Behavior of Immiscible Polymer-Grafted Nanoparticle Blends

Preferential attraction of polymer chains to the substrate [i.e., poly(methyl methacrylate) (PMMA) on the hydroxyl-terminated Si substrate] typically results in the initial phase separation of spin-cast immiscible linear polymer blends [i.e., polystyrene (PS)/PMMA] with a characteristic interfacial microstructure depending on their molecular weight. A formation of the undesired microstructure in those blends is inevitable because of the thermodynamic force driving their phase separation combined with relatively rapid dynamics in solution. In contrast, the polymer ligands, which are grafted from nanoparticles, are capable of limited segmental interactions in the presence of segmental contacts of chemically distinct chains as well as hindered mobility by interpenetration (or entanglement) and thus exhibit a homogeneous but non-equilibrium phase behavior. Here, the microstructure of the blends consisting of immiscible polymer-grafted nanoparticles (PGNPs) was identified by their neutron reflectivity, in whic...