Polymer Grafting Density Research Articles

Concepts and Approaches to Reduce or Avoid Protein Corona Formation on Nanoparticles: Challenges and Opportunities.

This review describes the formation of a protein corona (or its absence) on different classes of nanoparticles, its basic principles, and its consequences for nanomedicine. For this purpose, it describes general concepts to control (guide/minimize) the interaction between artificial nanoparticles and plasma proteins to reduce protein corona formation. Thereafter, methods for the qualitative or quantitative determination of protein corona formation are presented, as well as the properties of nanoparticle surfaces, which are relevant for protein corona prevention (or formation). Thereby especially the role of grafting density of hydrophilic polymers on the surface of the nanoparticle is discussed to prevent the formation of a protein corona. In this context also the potential of detergents (surfactants) for a temporary modification as well as grafting-to and grafting-from approaches for a permanent modification of the surface are discussed. The review concludes by highlighting several promising avenues. This includes (i) the use of nanoparticles without protein corona for active targeting, (ii) the use of synthetic nanoparticles without protein corona formation to address the immune system, (iii) the recollection of nanoparticles with a defined protein corona after in vivo application to sample the blood proteome and (iv) further concepts to reduce protein corona formation.

Nanoparticles bearing germanium based photoinitiators at their surface: Preparation and use in grafting-from photopolymerization reactions

In recent decades, there has been a growing interest in surface modifications utilizing “grafting-from” techniques within both industrial and academic fields. Among others, this technology continues to drive innovation in biomedicine, enabling the design and fabrication of advanced materials and devices with tailored properties for a wide range of applications, from regenerative medicine and drug delivery to diagnostics and therapeutics. This strategy relies on the covalent attachment of (photo)initiating species to surfaces. The coupled initiators are exploited to produce reactive sites such as radicals upon exposure to heat or light. Subsequently, polymerization reactions are induced, leading to surface coupled polymer brushes.In order to provide new perspectives in surface modification techniques, we present a novel and unique method for producing mesoporous organic/inorganic hybrid nanoparticles via the “grafting-from” method. This was accomplished by immobilizing a novel, low-toxic and visible light sensitive photoinitiator (based on triacylgermanium moieties) onto silica nanoparticles. Surface-initiated photopolymerizations of styrene and acrylate monomers were conducted to produce polymer shells on the surface of the nanoparticles. The grafted layers had a thickness in the range of 6–12 nm. Furthermore, the polymer grafting density is discussed in detail ranging between 0.17 and 0.23 chains per square nanometer.

Nanoparticles insertion and dimerization in polymer brushes.

Molecular dynamics simulations are conducted to systematically investigate the insertion of spherical nanoparticles (NPs) in polymer brushes as a function of their size, strength of their interaction with the polymers, polymer grafting density, and polymer chain length. For attractive interactions between the NPs and the polymers, the depth of NPs' penetration in the brush results from a competition between the enthalpic gain due to the favorable polymer-NP interaction and the effect of osmotic pressure resulting from displaced polymers by the NP's volume. A large number of simulations show that the average depth of the NPs increases by increasing the strength of the interaction strength. However, it decreases by increasing the NPs' diameter or increasing the polymer grafting density. While the NPs' effect on the polymer density is local, their effect on their conformations is long-ranged and extends laterally over length scales larger than the NP's size. This effect is manifested by the emergence of laterally damped oscillations in the normal component of the chains' radius of gyration. Interestingly, we found that for high enough interaction strength, two NPs dimerize in the polymer brush. The dimer is parallel to the substrate if the NPs' depth in the brush is shallow. However, the dimer is perpendicular to the substrate if the NPs' are deep in the brush. These results imply that polymer brushes can be used as a tool to localize and self-assemble NPs in polymer brushes.

Plasma-Induced Graft Polymerization for the In Situ Synthesis of Cross-Linked Nanocoatings.

Conventional technology for the modification of surfaces loaded with nanomaterials typically requires a three-step process: (1) the construction of a polymer platform, (2) the synthesis of nanoparticles (NPs), and (3) the immobilization or anchoring of NPs. During the immobilization or anchoring process, there is an unavoidable excess of NPs primarily situated at the top of the surface, resulting in the agglomeration of aggregates. These aggregates can form different shapes and sizes, often creating an uneven distribution of NPs, resulting in an unstable coating that gradually releases NPs over time. In this study, argon plasma technology was used to create an innovative nanocoating consisting of polymer chains that are cross-linked to metal NPs, forming a polymer composite. To do this, argon plasma was employed as both an oxidizing and reducing agent during different steps in the nanocoating fabrication process. More specifically, a "grafting-from" approach, coupled with in situ argon plasma-assisted reduction of Cu2+ to Cu0, provided an innovative means for the construction of the nanocoating. With this "grafting-from" approach, the covalent binding of acrylic acid monomers to a surface results in a negatively charged nanocoating when exposed to solutions of a pH greater than 4.5. Due to its negative charge, the nanocoating can bind cations from solution, creating a platform for the in situ argon plasma-assisted reduction of Cu2+ to primarily Cu0 NPs (CuNPs). By controlling grafting conditions, in situ plasma-assisted reduction of NPs, and cross-linking conditions, we can generate nanocoatings with specific (1) polymer graft density and film thickness, (2) NP concentration cross-linked to polymer chains, and (3) NP composition. Under optimal experimental conditions, a nonleaching cross-linkage occurs between the nanocoating and the NPs, with only minimal NP aggregation. We have used this technology to engineer cross-linked nanocoatings possessing extremely low amounts of CuNPs (4.02 μg/cm2), which are distributed within the nanocoating and are capable of preventing infections.

Confined Dynamics in Spherical Polymer Brushes.

We investigate the dynamics of polymers grafted to spherical nanoparticles in solution using hybrid molecular dynamics simulations with a coarse-grained solvent modeled via the multiparticle collision dynamics algorithm. The mean-square displacements of monomers near the surface of the nanoparticle exhibit a plateau on intermediate time scales, indicating confined dynamics reminiscent of those reported in neutron spin-echo experiments. The confined dynamics vanish beyond a specific radial distance from the nanoparticle surface that depends on the polymer grafting density. We show that this dynamical confinement transition follows theoretical predictions for the critical distance associated with the structural transition from confined to semidilute brush regimes. These findings suggest the existence of a hitherto unreported dynamic length scale connected with theoretically predicted static fluctuations in spherical polymer brushes and provide new insights into recent experimental observations.

Ultra-high capacity, multifunctional nanoscale sorbents for PFOA and PFOS treatment

Here, we describe surface functionalized, superparamagnetic iron oxide nanocrystals (IONCs) for ultra-high PFAS sorption and precise, low energy (magnetic) separation, considering perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). As a function of surface coating, sorption capacities described are considerably higher than previous studies using activated carbon, polymers, and unmodified metal/metal oxides, among others. In particular, positively charged polyethyleneimine (PEI) coated IONCs demonstrate extreme sorption capacities for both PFOA and PFOS due to electrostatic and hydrophobic interactions, along with high polymer grafting densities, while remaining stable in water, thus maintaining available surface area. Further, through a newly developed method using a quart crystal microbalance with dissipation (QCM-D), we present real-time, interfacial observations (e.g., sorption kinetics). Through this method, we explore underpinning mechanism(s) for differential PFAS (PFOA vs PFOS) sorption behavior(s), demonstrating that PFAS functional head group strongly influence molecular orientation on/at the sorbent interface. The effects of water chemistry, including pH, ionic composition of water, and natural organic matter on sorption behavior are also evaluated and along with material (treatment) demonstration via bench-scale column studies.

Comparative Study of Polymer-Grafted BaTiO3 Nanoparticles Synthesized Using Normal ATRP as Well as ATRP and ARGET-ATRP with Sacrificial Initiator with a Focus on Controlling the Polymer Graft Density and Molecular Weight.

Structurally well-defined polymer-grafted nanoparticle hybrids are highly sought after for a variety of applications, such as antifouling, mechanical reinforcement, separations, and sensing. Herein, we report the synthesis of poly(methyl methacrylate) grafted- and poly(styrene) grafted-BaTiO3 nanoparticles using activator regeneration via electron transfer (ARGET ATRP) with a sacrificial initiator, atom transfer radical polymerization (normal ATRP), and ATRP with sacrificial initiator, to understand the role of the polymerization procedure in influencing the structure of nanoparticle hybrids. Irrespective of the polymerization procedure adopted for the synthesis of nanoparticle hybrids, we noticed PS grafted on the nanoparticles showed moderation in molecular weight and graft density (ranging from 30,400 to 83,900 g/mol and 0.122 to 0.067 chain/nm2) compared to PMMA-grafted nanoparticles (ranging from 44,620 to 230,000 g/mol and 0.071 to 0.015 chain/nm2). Reducing the polymerization time during ATRP has a significant impact on the molecular weight of polymer brushes grafted on the nanoparticles. PMMA-grafted nanoparticles synthesized using ATRP had lower graft density and considerably higher molecular weight compared to PS-grafted nanoparticles. However, the addition of a sacrificial initiator during ATRP resulted in moderation of the molecular weight and graft density of PMMA-grafted nanoparticles. The use of a sacrificial initiator along with ARGET offered the best control in achieving lower molecular weight and narrow dispersity for both PS (37,870 g/mol and PDI of 1.259) and PMMA (44,620 g/mol and PDI of 1.263) nanoparticle hybrid systems.

Globular Proteins and Where to Find Them within a Polymer Brush-A Case Study.

Protein adsorption by polymerized surfaces is an interdisciplinary topic that has been approached in many ways, leading to a plethora of theoretical, numerical and experimental insight. There is a wide variety of models trying to accurately capture the essence of adsorption and its effect on the conformations of proteins and polymers. However, atomistic simulations are case-specific and computationally demanding. Here, we explore universal aspects of the dynamics of protein adsorption through a coarse-grained (CG) model, that allows us to explore the effects of various design parameters. To this end, we adopt the hydrophobic-polar (HP) model for proteins, place them uniformly at the upper bound of a CG polymer brush whose multibead-spring chains are tethered to a solid implicit wall. We find that the most crucial factor affecting the adsorption efficiency appears to be the polymer grafting density, while the size of the protein and its hydrophobicity ratio come also into play. We discuss the roles of ligands and attractive tethering surfaces to the primary adsorption as well as secondary and ternary adsorption in the presence of attractive (towards the hydrophilic part of the protein) beads along varying spots of the backbone of the polymer chains. The percentage and rate of adsorption, density profiles and the shapes of the proteins, alongside with the respective potential of mean force are recorded to compare the various scenarios during protein adsorption.

Role of surface hydrophilicity on MR relaxivity of PEG coated- gadolinium oxide nanoparticles

The magnetic resonance (MR) contrast enhancement capabilities of gadolinium oxide nanoparticles (GONPs) have high dependency on its surface chemistry- as the solution properties such as colloidal stability and hydrodynamic diameter of nanoparticles which are prime regulatory parameter for MR relaxivity, are all governed by grafting density of surface material. However, the purification of synthesized surface coated nanoparticles, without compromising the surface properties, remains a major challenge. Among the various cleaning methods, dialysis is often used to remove the unwanted by-products produced during synthesis. However, the effect of dialysis time may significantly impact the surface properties and hence, the MR contrast properties of such nano-formulations. The aim of the present study is to evaluate the effect of dialysis time on surface chemistry and MR contrast enhancement properties of GONPs by comparing the proton relaxivity data. Ultra-small polyethylene glycol (PEG)-coated GONPs with an average particle diameter of 17 nm were synthesized using polyol method. The impact of dialysis time has been investigated systematically on the size distribution, hydrophilicity, magnetic properties, polymer grafting density and relaxometric properties of the as synthesized GONPs. A significant impact of dialysis time was observed on surface chemistry and hence, on the MR relaxivity of synthesized NPs. We evidenced a dramatic decrease in the proton relaxivities of GONPs with increase in dialysis time, which correlated well with the observed decrease in the grafting density of surface polymer. The results clearly indicate that the proton relaxivity of GONPs of similar size and same coating material depends on the surface coating thickness and hydrophilicity of the coating polymer. Overall, it is essential to optimize the accurate time duration of dialysis treatment as the prolonged dialysis may have negative effect on the relaxation times and hence on MR contrast enhancement properties of GONPs. This study is a strategic pathway to fine-tune the dialysis treatment of as-synthesized surface-capped GONPs for pre-eminent MR contrast imaging.

Dynamic Assembly of Polymer-Tethered Gold Nanoparticles into a 2D Superlattice at the Air–Liquid Interface: Influence of the Polymer Structure and Solvent Vapor

The two-dimensional (2D) superlattice obtained by self-assembly of gold nanoparticle (NPs) at the air–liquid interface shows a wide range of potential applications in catalysis, sensing, electronic storage, and molecular recognition. However, the dynamic assembly process of the gold NPs at the air–liquid interface is still unclear. In this study, gold NPs grafted with thiol-terminated polystyrene homopolymers (AuNPs@PS) were used as the assembly unit, and the 2D superlattice of AuNPs@PS was prepared by spreading and evaporating the AuNPs@PS toluene suspension at the air/diethylene glycol interface. The effects of polymer chain length, grafting density, and toluene vapor atmosphere on the microstructure of the superlattice were investigated as well. The microstructural evolution process of the AuNPs@PS superlattice at the air/diethylene glycol interface was monitored by the in situ grazing incident small-angle X-ray scattering (GISAXS) technique. The results demonstrate that the transition of long-chain polymer-tethered NPs from random packing to face-centered-cubic packed superlattice followed by two-dimensional hexagonal packing can be observed under a toluene vapor atmosphere. Additionally, by varying the polymer chain length and solvent vapor atmosphere, the spreading rate and superlattice interparticle spacing can be well mediated. This work provides a useful guide to prepare an ordered 2D superlattice with polymer-tethered inorganic NPs.

Towards the polymer nanocomposites based on hairy nanoparticles

Polymer nanocomposites exhibit versatility in their mechanical and structural features predominantly due to the huge surface area provided by nanoparticles. Interaction of the nanoparticles with polymer matrix selectively dictates the applications suitable for a particular polymer nanocomposite system. Novel hybrid polymer-derived materials based on polymer grafted nanoparticles (NPs) can either be mixed with the polymer matrix or self-suspended without matrix polymer. In both cases superior properties are demonstrated compared to the traditional polymer nanocomposites, most notably by 1) incorporation of NPs into polymers without “mixing problems” and 2) a wide range of the transport phenomena (from solids to viscous fluids). Hence, hairy nanoparticle-based nanocomposites are equipped to handle specific and unique challenges in manufacturing and processing methods. It is known that the transport properties can be tuned by altering the molecular design of hairy nanoparticles (i.e., grafted polymer chemistry, NP concentrations, grafting density, and polymer molecular weight) and matrix polymer (e.g., molecular weight). In this article, we review the 1) most common methods of synthesizing hairy nanoparticle, 2) their microscopic dynamics and structural features and 3) some interesting applications of nanocomposite based on hairy nanoparticles. We discuss the effect of various parameters like nanoparticle size, molecular weight of the polymer etc. on the features of nanocomposites and its implications on the properties.

Advances in atom transfer radical polymerization of modified grain

Atom transfer radical polymerization (ATRP) is a kind of controllable reactive radical polymerization method with potential application value. The modification of graphene oxide (GO) by ATRP reaction can effectively control various graft polymer molecules Chain length and graft density, giving GO different functionality, such as good solvent dispersibility, environmental sensitive stimulus responsiveness, biocompatibility, and the like. In this paper, ATRP reaction and GO surface non-covalent bonding ATRP polymer molecular chain were directly initiated from GO surface immobilization initiator. The ATRP reaction modified GO was reviewed, and the process conditions and research methods of ATRP modification reaction were summarized, as well as pointed out the functional characteristics and application prospect of GO functionalized composites.

Stimuli-responsive polyelectrolyte brushes for regulating streaming current magnetic field and energy conversion efficiency in soft nanopores

The electrokinetic energy conversion, electroviscous effect, and induced internal and external magnetic fields in a smart polyelectrolyte grafted “soft” nanopore with pH responsiveness are studied here using an efficient molecular theory approach. The analysis is based on writing the total free energy of the system, including the conformational entropy of the flexible, self-avoiding polymer chains and the translational entropy of the mobile species, the electrostatic interactions, and the free energy due to chemical equilibrium reactions. Then, the free energy is minimized, while satisfying the necessary constraints to find the equilibrium state of the system. The predictions of the model are shown to be in excellent agreement with analytical solutions derived for special cases. We discuss the effect of different influential environmental and polymer brush parameters in detail and show that the electrokinetic energy conversion efficiency is optimal at moderate pH values and low background salt concentrations. It is also shown that the electrokinetic energy conversion efficiency is a complex function depending on both the environmental and polymer brush properties. Notably, high slip coefficients or high polymer grafting densities do not necessarily lead to a high energy conversion efficiency. Magnetic field readouts allow to measure streaming currents through nanopores without the need of electrodes and may be utilized as a secondary electronic signature in nanopore sensing techniques. It is shown that in nanopores modified with polyelectrolyte brushes, the induced magnetic fields can be tens of times larger than those in solid-state nanopores having only surface charges. We show that by tuning the pH, background salt concentration, surface charge, and polyelectrolyte grafting density, the magnitude of the internal and external magnetic fields can be significantly changed and controlled in a wide range.

Mobility of Sub-50 nm Iron Oxide Nanoparticles with Ultrahigh Initial Magnetic Susceptibility in Intact Berea Sandstone at High Salinity

Superparamagnetic iron oxide nanoparticles (IONPs), which have been investigated extensively as contrast-enhancing agents in biology, are being explored for subsurface applications such as electromagnetic tomography, fracture mapping, and enhanced oil recovery. However, two key challenges must be addressed: (a) high magnetic susceptibility and (b) colloidal stability and mobility under harsh reservoir conditions of high salinity and temperature. Herein, we synthesize IONPs grafted with poly(2-acrylamido-3-propanesulfonate-co-acrylic acid) poly(AMPS-co-AA) to achieve a high surface grafting density of polymer (49%) with minimal aggregation to yield sub-50 nm IONPs. The IONPs were found to be colloidally stable at 120 °C for a period of one month at pH 8. In crushed Berea sandstone, polymer-grafted IONPs exhibited significantly high mass breakthrough (84%) and low retention (149 μg/g) when used with a sacrificial polymer preflood (0.1% v/v). Intact Berea core experiments showed an 8-fold improvement in mass breakthrough (65%) and a two-thirds reduction in retention (from 433 μg/g to 160 μg/g) when compared to previous studies with IONPs synthesized via coprecipitation. The high grafting density of polymeric stabilizer and small nanoparticle size contribute to the improved mobility in consolidated porous media at high salinity.

Designing Stress-Adaptive Dense Suspensions Using Dynamic Covalent Chemistry

The non-Newtonian behaviors of dense suspensions are central to their use in technological and industrial applications and arise from a network of particle–particle contacts that dynamically adapt to imposed shear. Reported herein are studies aimed at exploring how dynamic covalent chemistry between particles and the polymeric solvent can be used to tailor such stress-adaptive contact networks, leading to their unusual rheological behaviors. Specifically, a room temperature dynamic thia-Michael bond is employed to rationally tune the equilibrium constant (Keq) of the polymeric solvent to the particle interface. It is demonstrated that low Keq leads to shear thinning, while high Keq produces antithixotropy, a rare phenomenon where the viscosity increases with shearing time. It is proposed that an increase in Keq increases the polymer graft density at the particle surface and that antithixotropy primarily arises from partial debonding of the polymeric graft/solvent from the particle surface and the formation of polymer bridges between particles. Thus, the implementation of dynamic covalent chemistry provides a new molecular handle with which to tailor the macroscopic rheology of suspensions by introducing programmable time dependence. These studies open the door to energy-absorbing materials that not only sense mechanical inputs and adjust their dissipation as a function of time or shear rate but also can switch between these two modalities on demand.

The effect of polymer grafting on the mechanical properties of PEG‐grafted cellulose nanocrystals in poly(lactic acid)

AbstractPoly(lactic acid) (PLA) is a commercially available bio‐based polymer that is a potential alternative to many commodity petrochemical‐based polymers. However, PLA's thermomechanical properties limit its use in many applications. Incorporating polymer‐grafted cellulose nanocrystals (CNCs) is one potential route to improving these mechanical properties. One key challenge in using these polymer‐grafted nanoparticles is to understand which variables associated with polymer grafting are most important for improving composite properties. In this work, poly(ethylene glycol)‐grafted CNCs are used to study the effects of polymer grafting density and molecular weight on the properties of PLA composites. All CNC nanofillers are found to reinforce PLA above the glass transition temperature, but non‐grafted CNCs and CNCs grafted with short PEG chains (<2 kg mol−1) are found to cause significant embrittlement, generally resulting in less than 3% elongation‐at‐break. By grafting higher molecular weight PEG (10 kg mol−1) onto the CNCs at a grafting density where the polymer chains are predicted to be in the semi‐dilute polymer brush conformation (~0.1 chains nm−2), embrittlement can be avoided.

Facile and tunable method for polymeric surface modification of magnetic nanoparticles via RAFT polymerization: Preparation, characterization, and drug release properties

Herein, the facile and tunable technique for the preparation of novel multi-stimuli-responsive nanocomposites via RAFT polymerization for DOX delivery is reported. The influence of the molecular weight of pH- and thermo-sensitive poly (acrylic acid-co-NIPAM) (PNAx), as a macro-RAFT agent, on the nanocomposites size and drug release rate was investigated. The outcome of this study reveals that macro-RAFT agent with lower molecular weight can be attached to the surface of magnetic nanoparticles with higher content of polymeric layer than can macro-RAFT agent with higher molecular weight. Also, it was observed that the particle size, polymer grafting density, DOX loading capacity, and DOX release rate could well be influenced by the molecular weight of PNAx. The in vitro drug release of doxorubicin was examined in various conditions (pH and temperature) and the results established a strong pH and thermal dependence. The order of drug-loading and releasing level rate for synthesized nanocarriers toward PNAx molecular weight are PNA3 < PNA2 < PNA1. These magnetic nanocarriers displayed excellent biocompatibility, stability, and dispersibility in aqueous solutions. Therefore, experimental data and results showed that nanocarriers synthesized with various molecular weights of PNAx by RAFT polymerization could be deployed for practical biomedicine applications and that the RAFT polymerization ushers in an excellent technique for tunable and facile surface modification of various nanoparticles with distinct sizes and morphologies.

Hybrid Dielectric Films of Inkjet-Printable Core-Shell Nanoparticles.

A new type of hybrid core-shell nanoparticle dielectric that is suitable for inkjet printing is introduced. Gold cores (dcore ≈ 4.5 nm diameter) are covalently grafted with thiol-terminated polystyrene (Mn = 11000 Da and Mn = 5000 Da) and used as inks to spin-coat and inkjet-print dielectric films. The dielectric layers havemetal volume fractions of 5 to 21 vol% with either random or face-centered-cubic structures depending on the polymer length and grafting density. Films with 21 vol% metal havedielectric constants of 50@1 Hz. Structural and electrical characterization using transmission electron microscopy, small-angle X-ray scattering, and impedance spectroscopy indicates that classical random capacitor-resistor network models partially describe this hybrid material but fail at high metal fractions, where the covalently attached shell prevents percolation and ensures high dielectric constants without the risk of dielectric breakdown. A comparison of disordered to ordered films indicates that the network structure affects dielectric properties less than the metal content. The applicability of the new dielectric material is demonstrated by formulating inkjet inks and printing devices. An inkjet-printed capacitor with an area of 0.79 mm2 and a 17 nm thick dielectric hada capacitance of .

Grafting polymers from cellulose nanocrystals via surface‐initiated atom transfer radical polymerization

AbstractCellulose nanocrystals (CNC) are rod‐like nanoparticles extracted from cellulose. Due to their fascinating properties—renewable, biocompatible, non‐toxic, biodegradable, excellent mechanical performances, high specific surface area, water dispersible, can be assemble in chiral nematic phases—CNC have shown promise in various fields, including oil recovery, polymer composites reinforcing, hydrogels, aerogels, supercapacitors, energy saving buildings, cosmetics, papermaking, coatings, liquid crystals, and waste water treatment. However, the hydrophilic surface of CNC hinders their broader applications. In this context, surface modification of CNC via polymer grafting can be used to finely tune their surficial properties and endow CNC with a variety of functionalities, such as conductivity, pH or temperature responsiveness, reactivity…In particular, surface‐initiated atom transfer radical polymerization (SI‐ATRP) is a powerful tool to graft various polymers with a high grafting density and controlled chain length. In this review, the precise control of grafted polymers from CNC via SI‐ATRP is first discussed, including issues related to the polymer grafting density, chain length and possibility to perform an asymmetric grafting. Then, the properties and applications of CNC grafted with a variety of polymers are presented. Finally, some challenges and outlook related to the SI‐ATRP method applied to the field of CNC is discussed.

Effect of chemical design of grafted polymers on the self-assembled morphology of polymer-tethered nanoparticles in nanotubes

There is a clear relationship between the self-assembling architecture of nanoparticles (NPs) and their physical properties, and they are currently used in a variety of applications, including optical sensors. Polymer-tethered NPs, which are created by grafting polymers onto NPs to control the self-assembly of NPs, have attracted considerable attention. Recent synthetic techniques have made it possible to synthesize a wide variety of polymers and thereby create NPs with many types of surfaces. However, self-assembled structures have not been systematically classified because of the large number of tuning parameters such as the polymer length and graft density. In this study, by using coarse-grained molecular simulation, we investigated the changes in the self-assembled structure of polymer-tethered NP solutions confined in nanotubes due to the chemical properties of polymers. Three types of tethered polymer NP models were examined: homo hydrophilic, diblock hydrophilic–hydrophobic (HI–HO), and diblock hydrophobic–hydrophilic. Under strong confinement, the NPs were dispersed in single file at low axial pressure. As the pressure increased, multilayered lamellar was observed in the HI–HO model. In contrast, under weak confinement, the difference in the pressure at which the phases emerge, depending on the model, was significant. By changing the chemical properties of the grafted polymer, the thermodynamic conditions (the axial pressure in this study) under which the phases appear is altered, although the coordination of NPs remains almost unchanged. Our simulation offers a theoretical guide for controlling the morphologies of self-assembled polymer-tethered NPs, a novel system that may find applications in nanooptical devices or for nanopatterning.