Surface Forces Characterization of Concentrated PMMA Brush Layers under Applied Load and Shear.

Concentrated polymer brushes (CPBs) are known to exhibit excellent lubrication properties. However, the frictional behaviors of CPBs vary, depending on their preparation and operating conditions. In order to understand such complicated properties, it is necessary to determine their structures and correlate them with their properties, during shear motion. In this study, we employed surface forces and resonance shear measurement (RSM) as well as refractive index measurement using fringes of equal chromatic order (FECO) for studying the structure of the CPBs of poly(methyl methacrylate) (PMMA) in toluene. The obtained elastic (ks) and viscous (bs) parameters based on the RSM for the PMMA-PMMA were higher than those obtained for PMMA-silica over the entire distance range. With the increasing shear amplitude on the PMMA-PMMA under an applied load, the bs value first increased and then decreased while the ks value monotonically decreased. These behaviors were consistent with those of the thicker CPBs reported in a previous paper (Soft Matter, 2019). Thus, the dynamics of the CPBs under the applied load and shear were not dependent on the thickness of the polymer brushes in this case. The density distribution of the swollen PMMA brushes along the distance in the thickness direction of the brush layer was estimated by using the measured refractive index values, showing that the fraction of the PMMA brushes in the outer region from the surface (20% in the thickness) was ca. 10%. This lower density region near the surface of the swollen CPBs enabled them to interpenetrate with each other. Changes in the refractive index value under shear were observed, indicating that the interpenetrated PMMA chains were pulled out with increasing shear amplitude. These results demonstrated that broader applications of CPBs are possible by regulating the friction between them under different operating conditions, even for usually lubricious CPBs.

Layered Structure and Wear Mechanism of Concentrated Polymer Brushes.

Concentrated polymer brushes (CPBs), which are significantly denser and thicker than conventional semidilute polymer brushes, have received increasing attention in the field of tribology because of their superlow friction properties. However, despite numerous studies aimed at enhancing CPBs for mechanical applications, the relationship between the specific layered structure and lubrication mechanisms of CPBs is still not completely understood. In this study, to reveal the relationship, simultaneous time-resolved measurements of the interfacial gap, static mechanical response, and dynamic mechanical response of the CPB at the contact interface were conducted using optical interference and precise force measuring methods. Two types of tests (i.e., the "indentation" and "sliding" tests) were alternately performed on a glass substrate coated with the CPB against a steel ball immersed in an ionic liquid. The indentation tests measuring the time-resolved interfacial gap and changes in static and dynamic mechanical responses quantitatively confirmed the presence of dilute, middle, and concentrated layers in the CPB. In the sliding tests, the wear of the CPB was detected by observing a decrease in the interfacial gap at the contact interface. Moreover, the thickness of the dilute layer remained constant with sliding, whereas the thicknesses of the other layers decreased, indicating that the dilute layer was continuously formed due to sliding. Therefore, CPB wear occurs randomly at the friction interface alongside the formation of a dilute layer with low density and stiffness on the surface.

A novel electrochemical biosensing method with double-layered polymer brush modified electrode.

We developed a novel electrochemical biosensor electrode that has a potential to reduce background noise for which we constructed an original conductive substrate modified with a double-layered polymer brush structure that is water impermeable and can control biomolecules adsorption/desorption. In this study, a hydrophobic poly(tert-butyl methacrylate) brush layer was prepared on a gold electrode, and then, the tert-butyl group near the outermost surface was dissociated by the acid treatment to obtain a hydrophilic carboxy group, thereby fabricating a conductive substrate with the double-layered polymer brush structure. Formation of the double-layered polymer brush structure was indicated by surface wettability and optical analyses. The potential difference and hydrogen ion concentration, which is a typical parameter of the surrounding environment, were linearly correlated with the gold electrode having a double-layered polymer brush structure with carboxyl groups. However, there was no correlation on gold electrodes with self-assembled monolayers presenting carboxy groups. It is considered that the pH responsiveness of the carboxy groups on the outermost surface could be exhibited remarkably because the charge state in the vicinity of the surface became constant due to the hydrophobic polymer brush layer having a certain thickness. The target DNA could be captured more efficiently at the probe DNA-immobilized electrode with the double-layered polymer brush structure than when using COOH-SAM. This is the first report of the application of the double-layered polymer brush structure for the electrochemical biosensing, and it will be an excellent surface modification method to reduce background noise.

Exploiting the Synergy between Concentrated Polymer Brushes and Laser Surface Texturing to Achieve Durable Superlubricity.

Friction continues to account for the bulk of energy losses in mechanical systems, with an estimated 23% of the world's total energy consumption used to overcome friction. Concentrated polymer brushes (CPBs) have recently attracted significant scientific and industrial attention, given their ability to achieve superlubricity (i.e., coefficients of friction below 0.01); however, understanding the mechanistic interactions underlying their wear performance has been largely overlooked. Herein, we employ a custom-built optical test apparatus to investigate the inter-dependencies between CPBs and laser-produced surface texture (LST), assessing for the first time the friction, film thickness, and wear behavior in situ and simultaneously. Recent developments in picosecond laser etching allowed us to graft CPBs atop the finest laser-etched matrix of micron-sized dimples reported in literature to date. At low sliding speeds, combined CPB-LST reduces the coefficient of friction to 0.0006, while increasing the CPB durability by up to 34% through a lateral support mechanism offered by the textured micro-features. Furthermore, the imaging results shed light on CPB failure mechanisms. Both these mechanisms of lateral support and failure propagation impact the wear resistance of CPBs and are important in the development of CPBs for future applications (e.g., in low-speed bearings functioning under controlled abrasive wear conditions).

Nonbiofouling Coatings Using Bottlebrushes with Concentrated Polymer Brush Architecture.

Concentrated polymer brushes (CPBs) are known to suppress biofouling phenomena, such as protein adsorption and cell adhesion. However, a cumbersome process is needed for their synthesis. Here, we report a simple and versatile method for fabricating nonbiofouling coatings that uses well-defined bottlebrushes instead of CPBs. First, a macroinitiator, poly[2-(2-bromoisobutyryloxy)ethyl methacrylate] (PBIEM), was synthesized by reversible addition-fragmentation chain transfer polymerization. Then, poly[poly(ethylene glycol) methyl ether methacrylate] was grafted from PBIEM through atom transfer radical polymerization to form well-defined bottlebrushes. By controlling the graft chain length, two types of bottlebrushes could be prepared, namely those with a semi-dilute polymer brush (SDPB) structure or a CPB structure on the surface of the outermost layer. Crosslinked films of the bottlebrushes were prepared on silicon wafers by spin-coating and subsequent radical coupling. Importantly, the CPB-type bottlebrush films showed significantly better nonbiofouling characteristics than those of the SDPB-type bottlebrush films.

Controlling the Thermally Induced Phase Separation of Polymer/Ionic Liquid Blended Films with Concentrated-Polymer-Brush-Decorated Hybrid Particles.

The development of quasi-solid electrolytes for electrical devices operating at high voltages is important for addressing future energy storage requirements. Here, we report a new method to fabricate quasi-solid electrolytes through the thermally induced phase separation of a polymer/ionic liquid (polymer/IL) blend. In a polymer/IL blend that exhibits lower critical solution temperature-type phase separation, we demonstrate that the addition of silica particles decorated with concentrated polymer brushes (CPB-SiPs) can prevent macroscopic phase separation after heating, resulting in a quasi-solid electrolyte with a continuous IL phase. This is due to the adsorption of CPB-SiPs onto the polymer/IL interface in the phase-separated structure. We also reveal a relationship between the molecular weight of the CPB and the phase-separated structure. Namely, a quasi-solid film with a bicontinuous phase-separated structure is formed only when polymers with an appropriate molecular weight are grafted on the CPB-SiPs. The resulting quasi-solid film exhibits a relatively high ionic conductivity, owing to the existence of a continuous ion-conductive phase solely consisting of IL. In addition, we fabricated a quasi-solid electrolyte with the blended film and successfully applied it to an electric double-layer capacitor operating at a high voltage, owing to the wider potential window of the IL employed herein.

Dynamics of lubricious, concentrated PMMA brush layers studied by surface forces and resonance shear measurements.

We employed surface forces and resonance shear measurement (RSM) for studying the structure and properties of typical concentrated polymer brushes (CPBs) of poly(methylmethacrylate) (PMMA) in toluene, which are known to show very low friction. The surface forces measured between the silica surfaces bearing PMMA brush layers showed a steric repulsive force at distances between the silica surfaces of less than ca. 1050 nm (Donset). Upon retraction after compression of the PMMA brush layers, no adhesive force was observed. This indicated that the interpenetration of the polymer chain was not induced by the normal load. Based on the resonance shear measurement, the elastic (k2) and damping (viscous) (b2) parameters, which represent the dynamic properties, of the PMMA brush layers were obtained by analyzing the resonance curves. At distances below the Donset, the b2 value significantly increased and slightly decreased at the higher normal loads, and the k2 value monotonically increased with increasing load. These k2 and b2 values were greater than those obtained for a PMMA brush layer and a bare silica surface (PMMA-silica). This indicated that the mobility of the polymer chains for the PMMA-PMMA brush layers was more suppressed compared to that for the PMMA-silica, due to the interpenetration of the polymer chains. The interpenetration of the polymer chains, commonly not observed for CPBs, could be most probably induced by the application of both the normal load and oscillating shear motion. With increasing shear amplitude on the compressed PMMA-PMMA brushes (at L = 0.84, 1.34 and 4.28 mN), the b2 value first increased then decreased whilst the k2 value monotonically decreased. These tendencies can be explained by the change from the sticking condition due to interpenetration (high k2), small sliding under interpenetration (increase in b2, decrease in k2), and then smooth sliding by pulling out of interpenetrated polymer chains (decrease in b2 and k2). The obtained results indicated that the operating conditions are quite important for using polymer brush layers as tribological materials because they can exhibit both a high and low friction depending on the conditions such as the load and shear amplitude.

Well-defined monolith morphology regulates cell adhesion and its functions.

Hydrophilic epoxy resin-based monoliths were employed as cell culture substrates. The monoliths were made of a porous material with a bicontinuous structure that consisted of a porous channel and a resin skeleton. Monolith disks were prepared with a skinless surface through polymerization-induced spinodal decomposition-type phase separation. The pore sizes, which were well controlled by the polymerization temperature, ranged from 70 to 380 nm. The quantity of protein adsorbed per unit area and the early-stage adhesion of HepG2 cells on the monolith substrates were independent of pore size, meaning they were not affected by surface topology. Long-term cell adhesion, as indicated by adherent cell number and shape, as well as liver-specific gene expression were significantly affected by pore size. In terms of cell shape, number, and gene expression, pores of approximately 200 nm were most suitable for HepG2 cell growth. These results highlight the importance of monolith morphology for use as a cell culture substrate. The well-controlled morphology demonstrated in this work indicates monoliths are capable of supporting growth for various types of cells in a range of applications.

Control of Phase Separation in Polystyrene/Ionic Liquid-Blended Films by Polymer Brush-Grafted Particles.

Immiscible composite materials with controlled phase-separated structures are important in areas ranging from catalysis to battery. We succeeded in controlling the phase-separated structures of immiscible blends of polystyrene (PS) and two ionic liquids (ILs), namely, N, N-diethyl- N-(2-methoxyethyl)- N-methylammonium bis(trifluoromethylsulfonyl)imide (DEME-TFSI) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, by adding precisely designed concentrated polymer brush-grafted (CPB-grafted) silica nanoparticles (CPB-SiPs) prepared by surface-initiated atom-transfer radical polymerization. We discuss relationships between chemical species and molecular weights of the CPB and phase-separated structures. When the CPB was composed of a PS homopolymer of an appropriate molecular weight, the IL phase formed a continuous structure and a quasi-solid-blended film was successfully fabricated because the CPB-SiPs were adsorbed at the PS/IL interface and prevented macroscopic phase separation. We propose that CPB-SiP adsorption and the fabrication of quasi-solid films are governed by the degree of penetration of the matrix PS chains into the CPB and deformability of the CPB-SiPs. We found that the DEME-TFSI domain size can be controlled by the CPB-SiP content and that only 1 wt % of the CPB-SiPs was needed to fabricate a quasi-solid film. In addition, we investigated the ionic properties of the quasi-solid PS/DEME-TFSI-blended film. Owing to continuous ion channels composed only of DEME-TFSI, the film exhibited an ionic conductivity of 0.1 mS/cm, which is relatively high compared to previously reported quasi-solid electrolytes. Finally, we demonstrated that an electric double-layer capacitor fabricated using this film as the electrolyte exhibited high charge/discharge cycling stability and reversibility.

Facile Fabrication of Concentrated Polymer Brushes with Complex Patterning by Photocontrolled Organocatalyzed Living Radical Polymerization.

Photocontrolled surface-initiated reversible complexation mediated polymerization (photo-SI-RCMP) was successfully applied to fabricate concentrated polymer brushes with complex patterning structures. Positive-type patterned polymer brushes were obtained by photo-SI-RCMP under visible light (550(±50) nm) using photomasks. A particularly interesting finding was that negative-type patterned polymer brushes were also obtainable in a facile manner. A nonspecial UV light (250-385 nm) enabled the preparation of pre-patterned initiator surfaces in a remarkably short time (1 min), leading to negative-type patterned polymer brushes. Based on this unique selectivity between visible and UV light, the combination of two patterning techniques enabled the preparation of complex patterned brushes, including diblock copolymers, binary polymers, and functional binary polymers, without multistep immobilization of one or more initiators on the surfaces.

USAXS analysis of concentration-dependent self-assembling of polymer-brush-modified nanoparticles in ionic liquid: [I] concentrated-brush regime.

Using ultra-small angle X-ray scattering (USAXS), we analyzed the higher-order structures of nanoparticles with a concentrated brush of an ionic liquid (IL)-type polymer (concentrated-polymer-brush-modified silica particle; PSiP) in an IL and the structure of the swollen shell layer of PSiP. Homogeneous mixtures of PSiP and IL were successfully prepared by the solvent-casting method involving the slow evaporation of a volatile solvent, which enabled a systematic study over an exceptionally wide range of compositions. Different diffraction patterns as a function of PSiP concentration were observed in the USAXS images of the mixtures. At suitably low PSiP concentrations, the USAXS intensity profile was analyzed using the Percus-Yevick model by matching the contrast between the shell layer and IL, and the swollen structure of the shell and "effective diameter" of the PSiP were evaluated. This result confirms that under sufficiently low pressures below and near the liquid/crystal-threshold concentration, the studied PSiP can be well described using the "hard sphere" model in colloidal science. Above the threshold concentration, the PSiP forms higher-order structures. The analysis of diffraction patterns revealed structural changes from disorder to random hexagonal-closed-packing and then face-centered-cubic as the PSiP concentration increased. These results are discussed in terms of thermodynamically stable "hard" and/or "semi-soft" colloidal crystals, wherein the swollen layer of the concentrated polymer brush and its structure play an important role.

Strategy for the Improvement of the Mechanical Properties of Cellulose Nanofiber-Reinforced High-Density Polyethylene Nanocomposites Using Diblock Copolymer Dispersants.

Cellulose nanofibers (CNFs) hold great potential as sustainable reinforcement fillers with excellent mechanical, thermal, and chemical properties. However, in polyolefin nanocomposite materials, the rational control of dispersion and the improvement of interfacial strength remain challenging. Herein we propose the tuning of the interface between CNF and high-density polyethylene by the design of polymer dispersants on the basis of surface free energy and the glass transition temperature. The former is related to the wettability against the polymer matrix and is therefore critical to the dispersion of CNF whereas the latter is related to the interfacial strength between CNF and HDPE. As a result of this investigation, we discovered a suitable dispersant for CNFs, poly(dicyclopentenyloxyethyl methacrylate)-block-poly(2-hydroxyethyl methacrylate), which played a pivotal role in achieving both a uniform dispersion of CNF and greatly improved mechanical properties, including a 4-fold increase of the Young's modulus over that of neat HDPE with 10 wt % CNF loading.

Semisoft Colloidal Crystals in Ionic Liquids.

Here, we introduce a technique for the direct formation of semisoft colloidal crystals of hybrid particles in nonvolatile ionic liquid (IL) solvents. The hybrid particles are comprised of a silica core and a densely grafted polymer brush shell, which were synthesized by surface-initiated living radical polymerization. A phase transition of the suspensions from a disordered fluid to a crystallized system was observed within a narrow concentration range. Confocal laser scanning microscopy observation and ultraviolet-visible light (UV-vis) spectrometry confirmed the highly ordered structure of the hybrid particles in ionic liquids. The effect of the hybrid particle structure on the photonic band gap of the colloidal crystals was investigated, and the band gaps varied by changing graft chain lengths. In addition, the colloidal crystal suspensions were successfully immobilized in ILs.

Visualization of Individual Images in Patterned Organic-Inorganic Multilayers Using GISAXS-CT.

Using grazing-incidence small-angle scattering (GISAXS) with computed tomography (CT), we have individually reconstructed the spatial distribution of a thin gold (Au) layer buried under a thin poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) layer. Owing to the difference between total reflection angles of Au and PS-b-P2VP, the scattering profiles for Au nanoparticles and self-assembled nanostructures of PS-b-P2VP could be independently obtained by changing the X-ray angle of incidence. Reconstruction of scattering profiles allows one to separately characterize spatial distributions in Au and PS-b-P2VP nanostructures.

Surface Engineering of Cellulose Nanofiber by Adsorption of Diblock Copolymer Dispersant for Green Nanocomposite Materials.

An effective approach for the dispersion of hydrophilic cellulose nanofiber (CNF) in hydrophobic high-density polyethylene (HDPE) is presented using adsorption of a diblock copolymer dispersant. The dispersant consists of both resin compatible poly(lauryl methacrylate) (PLMA) and cellulose interactive poly(2-hydroxyethyl methacrylate) blocks. The PLMA-adsorbed CNFs are characterized by FT-IR and contact angle measurement, revealing successful hydrophobization. X-ray CT imaging shows there are apparently less CNF aggregates in the nanocomposites if adding amount of the dispersant was enough. The good dispersion results in a high mechanical reinforcement, corresponding to 140% higher Young's modulus and 84% higher tensile strength than the neat HDPE. This approach is broadly applicable and allows for easy manufacturing process for strong and lightweight CNF-reinforced nanocomposite materials.

Synthesis of Monodisperse Silica Particles Grafted with Concentrated Ionic Liquid-Type Polymer Brushes by Surface-Initiated Atom Transfer Radical Polymerization for Use as a Solid State Polymer Electrolyte.

A polymerizable ionic liquid, N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium bis(trifluoromethylsulfonyl)imide (DEMM-TFSI), was polymerized via copper-mediated atom transfer radical polymerization (ATRP). The polymerization proceeded in a living manner producing well-defined poly(DEMM-TFSI) of target molecular weight up to about 400 K (including a polycation and an counter anion). The accurate molecular weight as determined by a GPC analysis combined with a light scattering measurement, and the molecular weight values obtained exhibited good agreement with the theoretical values calculated from the initial molar ratio of DEMM-TFSI and the monomer conversion. Surface-initiated ATRP on the surface of monodisperse silica particles (SiPs) with various diameters was successfully performed, producing SiPs grafted with well-defined poly(DEMM-TFSI) with a graft density as high as 0.15 chains/nm². Since the composite film made from the silica-particle-decorated polymer brush and ionic liquid shows a relatively high ionic conductivity, we have evaluated the relationship between the grafted brush chain length and the ionic conductivity.

Synthesis of iron oxide rods coated with polymer brushes and control of their assembly in thin films.

We investigated the surface-initiated atom transfer radical polymerization (SI-ATRP) of methyl methacrylate (MMA) using monodisperse rod-type particles of iron oxide, ß-FeOOH. The slow hydrolysis of iron(III) chloride yielded monodisperse ß-FeOOH rods with an average length-to-width ratio, L/W, of 6 (L = 210 nm and W = 35 nm on average). The surfaces of the ß-FeOOH rods were modified with a triethoxysilane derivative as an ATRP-initiating site, namely, (2-bromo-2-methyl)propionyloxypropyl triethoxysilane. The SI-ATRP of MMA, mediated by a copper complex, was performed using the initiator-coated ß-FeOOH rods in the presence of a "sacrificial" free initiator. Well-defined poly(methyl methacrylate) (PMMA) brushes with molecular weights of up to 700,000 could be grafted on the ß-FeOOH rods with a surface density as high as 0.3 chains/nm(2). The resultant polymer-brush-afforded hybrid rods exhibited high dispersibility in various solvents for PMMA without forming aggregates. Thin films were prepared by dip-coating from a suspension of the hybrid rods, and the rods were oriented in a specific direction in the films. The arrangement of the rods could be controlled by varying the chain length of the polymer brush and the withdrawal speed during the dip-coating process.

Immobilization of semisoft colloidal crystals formed by polymer-brush-afforded hybrid particles.

An immobilization technique for semisoft colloidal crystals, which are ordered arrays of polymer-brush-afforded hybrid particles synthesized by surface-initiated living radical polymerization (SI-LRP), is reported. Silica particles were first grafted with well-defined block copolymers of poly(methyl methacrylate-co-hydroxyethyl methacrylate)-b-poly(methyl methacrylate), P(MMA-co-HEMA)-b-PMMA by SI-LRP, which gave a graft density as high as 0.7 chains/nm(2). The HEMA units reacted with 2-isocyanatoethyl methacrylate to introduce vinyl groups at the outer layer of the polymer-brush shell. The modified hybrid particles formed a colloidal crystal in a solution containing a small amount of free polymers with vinyl groups. The colloidal crystal was photoirradiated in the presence of a photoradical initiator to immobilize it through a cross-linking reaction among the vinyl groups. The structural analyses of the colloidal crystals before and after the photoirradiation were carried out by confocal laser scanning microscopy; the results showed that the periodic structures of the crystals were maintained after immobilization.

Controlled polymerization of protic ionic liquid monomer by ARGET-ATRP and TERP.

The direct synthesis of structurally well-defined protic polymeric ionic liquid (PIL) with controlled molecular weight and molecular weight distribution is examined using N,N-diethyl-N-(2-methacryloylethyl) ammonium bis(tri-fluoromethylsulfonyl)imide (DEMH-TFSI) as a monomer. Three polymerization methods, namely, atom transfer radical polymerization (ATRP), activators regenerated by electron transfer (ARGET)-ATRP, and organotellurium-mediated living radical polymerization (TERP) are employed in this study. While the polymerization by ATRP is slow and does not reach high monomer conversion that under ARGET-ATRP and TERP proceeds smoothly and affords structurally well-defined poly(DEMH-TFSI)s. TERP is especially efficient for the control and poly(DEMH-TFSI)s with low to high molecular weights (M¯(n) = 49 100-392 500) and narrow molecular weight distributions (M¯(w)/M¯(n) = 1.17-1.46) are obtained. These results represent the first example of synthesis of a structurally well-defined protic, ammonium PIL by direct polymerization of the protic ionic liquid monomer. The polymerization of N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium bis(trifluoromethylsulfonyl)imide (DEMM-TFSI), which possesses a quaternary ammonium salt, also proceeds in a highly controlled manner under TERP conditions. A diblock copolymer, polystyrene-block-poly(DEMH-TFSI), is also successfully synthesized by TERP.

Fabrication of contrast agents for magnetic resonance imaging from polymer-brush-afforded iron oxide magnetic nanoparticles prepared by surface-initiated living radical polymerization.

The aim of this study is to fabricate a contrast agent for magnetic resonance imaging (MRI) by using hybrid particles composed of a core of iron oxide magnetite (Fe3O4) nanoparticles and a shell of hydrophilic polymer brush synthesized by surface-initiated (SI) living radical polymerization. To achieve this, Fe3O4 nanoparticles were surface-modified with initiating groups for atom transfer radical polymerization (ATRP) via a ligand-exchange reaction in the presence of a triethoxysilane derivative having an ATRP initiation site. The ATRP-initiator-functionalized Fe3O4 nanoparticles were used for performing the SI-ATRP of methyl methacrylate to demonstrate the ability of the synthesized nanoparticles to produce well-defined polymer brushes on their surfaces. The polymerization proceeded in a living fashion so as to produce graft polymers with targeted molecular weights and narrow molecular weight distribution. The average graft density was estimated to be as high as 0.7 chains/nm(2), which indicates the formation of so-called concentrated polymer brushes on the Fe3O4 nanoparticles. Dynamic light scattering and transmission electron microscope observations of the hybrid nanoparticles revealed their uniformity and dispersibility in solvents to be excellent. A similar polymerization process was conducted using a hydrophilic monomer, poly(ethylene glycol) methyl ether methacrylate (PEGMA), to prepare Fe3O4 nanoparticles grafted with poly(PEGMA) brushes. The resultant hybrid nanoparticles showed excellent dispersibility in aqueous media including physiological conditions without causing any aggregations. The blood clearance and biodistribution of the hybrid particles were investigated by intravenously injecting particles labeled with a radio isotope, (125)I, into mice. It was found that some hybrid particles exhibited an excellently prolonged circulation lifetime in the blood with a half-life of about 24 h. When such hybrid particles were injected intravenously into a tumor-bearing mouse, they preferentially accumulated in the tumor tissues owing to the so-called enhanced permeability and retention effect. The tumor-targeted delivery was visualized by a T2-enhaced MRI measurement.