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Nanoparticles (NPs) are utilized for the functionalization of composite materials and nanofluids. Although oxide NPs (e.g., silica (SiO2)) exhibit less dispersibility in organic solvents or polymers due to their hydrophilic surface, the surface modification using silane coupling agents can improve their dispersibility in media with low dielectric constants. Herein, SiO2 NPs were functionalized using octyltriethoxysilane (OTES, C8) and dodecyltriethoxysilane (DTES, C12), wherein the degrees of surface modification of SiO2@C8 and SiO2@C12 were quantitatively evaluated based on the ratio of modifier to surface silanol group (θ) and the volume fraction of organic modifier to total particle volume (ÏR). The variations of surface properties were revealed by analyzing the Hansen solubility parameters (HSP). Particularly, the surface modification using OTES or DTES significantly affected the polarity (δP) of NPs. The local dielectric environments of surface-modified SiO2 NPs were characterized using a solvatochromic dye, Laurdan. By analyzing the peak position of the steady-state emission spectrum of Laurdan in a NP suspension, the apparent dielectric environments surrounding NPs (εapp) were obtained. A good correlation between ÏR and εapp was observed, indicating that ÏR is a reliable quantity for understanding the properties of surface-modified NPs. Furthermore, the generalized polarization (GP) of NPs was investigated. The surface-modified SiO2 NPs with higher ÏR (≥0.15) exhibited GP > 0, suggesting that the modifiers are well-organized on the surface of NPs. The localized dielectric environment surrounding NPs could be predicted by analyzing the volume fraction of nonpolar moieties derived from modifiers. Alternatively, εapp and GP can be utilized for understanding the properties of inorganic-organic hybrid NPs.
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HYPOTHESIS: Three-dimensional plasmonic nanoparticle arrays in which the nanoparticles are assembled with a certain distance apart are expected to exhibit unique optical properties attributed to surface lattice resonances because of the interactions between the nanoparticle layers. EXPERIMENTS: Multi-layered gold nanoparticle arrays were created to experimentally prove surface lattice resonances from three-dimensional arrays. Silica-coated gold nanoparticles were employed as building blocks for the array because the distance between the nanoparticles can be tuned by adjusting the thickness of the silica coating. Employing highly monodisperse building blocks enabled to fabricate both single-layered and multi-layered plasmonic arrays via a confined convective assembly method. FINDINGS: Multi-layering of monodisperse building blocks brought about some additional peaks corresponded to Bragg diffraction of gold nanoparticle periodic array and the interactions between layers in a hexagonal close-packed structure of the nanoparticles, respectively. Most importantly, the multi-layered arrays exhibited a distinctive extinction peak at the same wavelength as that observed from the single-layered array, proving the realization of surface lattice resonances from the three-dimensional plasmonic array.
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Oro , Nanopartículas del Metal , Oro/química , Nanopartículas del Metal/química , Dióxido de SilicioRESUMEN
The unique properties of yolk-shell or rattle-type particles make them promising candidates for applications ranging from switchable photonic crystals, to catalysts, to sensors. To realize many of these applications it is important to gain control over the dynamics of the core particle independently of the shell. HYPOTHESIS: The core particle may be manipulated by an AC electric field with rich frequency-dependent behavior. EXPERIMENTS: Here, we explore the frequency-dependent dynamic electrophoretic mobility of a charged core particle within a charged, porous shell in AC electric fields both experimentally using liquid-phase electron microscopy and numerically via the finite-element method. These calculations solve the Poisson-Nernst-Planck-Stokes equations, where the core particle moves according to the hydrodynamic and electric forces acting on it. FINDINGS: In experiments the core exhibited three frequency-dependent regimes of field-driven motion: (i) parallel to the field, (ii) diffusive in a plane orthogonal to the field, and (iii) unbiased random motion. The transitions between the three observed regimes can be explained by the level of matching between the time required to establish ionic gradients in the shell and the period of the AC field. We further investigated the effect of shell porosity, ionic strength, and inner-shell radius. The former strongly impacted the core's behavior by attenuating the field inside the shell. Our results provide physical understanding on how the behavior of yolk-shell particles may be tuned, thereby enhancing their potential for use as building blocks for switchable photonic crystals.
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Hidrodinámica , Difusión , Electroforesis/métodos , Movimiento (Física) , PorosidadRESUMEN
Polymer nanoparticles have attracted attention as antibacterial materials, but the function of the polymer itself has not yet been clarified sufficiently. To estimate the essential surface properties of antibacterial polymer nanoparticles, herein, we synthesized cationic polystyrene (PSt) nanoparticles via soap-free emulsion polymerization using 2,2'-azobis-[2-(1,3-dimethyl-4,5-dihydro-1H-imidazol-3-ium-2-yl)]propane triflate (ADIP) as initiator. The conversion of total monomers was drastically increased through the addition of the commoner (vinylbenzyl)trimethylammonium chloride (VBTMAC), where unimodal size distributions (Cv ≤ 10%) were obtained at comonomer molar ratios between 0.0083 and 0.0323. The adsorption behavior of a solvatochromic anionic fluorescent dye revealed the surface charge density (σ) and affinity with anionic molecules (K) of PSt nanoparticles. The PSt nanoparticles with increased K values exhibited antibacterial activity against Staphylococcus epidermidis, with a minimum inhibitory concentration of at least 0.69 mg/mL. To determine a plausible mechanism for the antibacterial activity, the membrane damage induced by PSt nanoparticles was evaluated using an assay utilizing polydiacetylene vesicles as the model for negatively charged bilayer membranes. The PSt nanoparticles exhibiting large K values disturbed the bilayer structure of the model membrane system, suggesting that the synthesized PSt nanoparticles could be utilized as a contact-killing antibacterial agent.
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Nanopartículas , Poliestirenos , Antibacterianos/farmacología , Cationes , Pruebas de Sensibilidad Microbiana , Nanopartículas/química , Polímeros/químicaRESUMEN
Mesoporous silica shells were formed on nonporous spherical silica cores during the sol-gel reaction to elucidate the mechanism for the generation of secondary particles that disturb the efficient growth of mesoporous shells on the cores. Sodium bromide (NaBr) was used as a typical electrolyte for the sol-gel reaction to increase the ionic strength of the reactant solution, which effectively suppressed the generation of secondary particles during the reaction wherein a uniform mesoporous shell was formed on the spherical core. The number of secondary particles (N 2nd) generated at an ethanol/water weight ratio of 0.53 was plotted against the Debye-Hückel parameter κ to quantitatively understand the Debye screening effect on secondary particle generation. Parameter κa, where a is the average radius of the secondary particles finally obtained in the silica coating, expresses the trend in N 2nd at different concentrations of ammonia and NaBr. N 2nd was much lower than that expected theoretically from the variation of secondary particle sizes at a constant Debye-Hückel parameter. A similar correlation with κa was observed at the high and low ethanol/water weight ratios of 0.63 and 0.53, respectively, with different hydrolysis rate constants. The good correlation between N 2nd and κa revealed that controlling the ionic strength of the silica coating is an effective approach to suppress the generation of secondary particles for designing mesoporous shells with thicknesses appropriate for their application as high-performance liquid chromatography column packing materials.
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Multipoint lock-and-key particle assembly, consisting of lock particles with multiple anisotropic dents and rod-shaped particles as key particles, is developed for colloidal modeling application. The lock particles were connected with each other at a key particle as their joint in the presence of depletants, forming rigid colloidal molecules imitating rigid polymers (e.g., polymers containing aromatic rings and intramolecular hydrogen bonds). A single-particle level observation was conducted to visualize the colloidal polymerization of the particle assembly. Motion trajectories of the lock particles observed by optical microscopy indicated that the particle diffusivity was dramatically lowered when the lock particle connected with another one, suggesting that particle diffusion was suppressed by particle assembly formation. Because the kinetic and regioselectivity of colloidal polymerization are assumed to be analogous to those at the atomic scale, the proposed lock-and-key assembly can be a promising colloidal model for atomic-scale polymers associated with their micro-Brownian motion.
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Yolk-shell or rattle-type particles consist of a core particle that is free to move inside a thin shell. A stable core with a fully accessible surface is of interest in fields such as catalysis and sensing. However, the stability of a charged nanoparticle core within the cavity of a charged thin shell remains largely unexplored. Liquid-cell (scanning) transmission electron microscopy is an ideal technique to probe the core-shell interactions at nanometer spatial resolution. Here, we show by means of calculations and experiments that these interactions are highly tunable. We found that in dilute solutions adding a monovalent salt led to stronger confinement of the core to the middle of the geometry. In deionized water, the Debye length κ-1 becomes comparable to the shell radius Rshell, leading to a less steep electric potential gradient and a reduced core-shell interaction, which can be detrimental to the stability of nanorattles. For a salt concentration range of 0.5-250 mM, the repulsion was relatively long-ranged due to the concave geometry of the shell. At salt concentrations of 100 and 250 mM, the core was found to move almost exclusively near the shell wall, which can be due to hydrodynamics, a secondary minimum in the interaction potential, or a combination of both. The possibility of imaging nanoparticles inside shells at high spatial resolution with liquid-cell electron microscopy makes rattle particles a powerful experimental model system to learn about nanoparticle interactions. Additionally, our results highlight the possibilities for manipulating the interactions between core and shell that could be used in future applications.
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The technology to accurately image the morphology of tumor vessels with X-ray contrast agents is important to clarify mechanisms underlying tumor progression and evaluate the efficacy of chemotherapy. However, in clinical practice, iodine-based contrast agents present problems such as short blood retention owing to a high clearance ability and insufficient X-ray absorption capacity when compared with other high atomic number elements. To resolve these issues, gold nanoparticles (AuNPs), with a high atomic number, have attracted a great deal of attention as contrast agents for angiography, and have been employed in small animal models. Herein, we developed novel contrast agents using AuNPs and captured changes in tumor vessel morphology with time using X-ray computed tomography (CT). First, glutathione-supported single nanometer-sized AuNPs (sAu/GSH) (diameter, 2.2 nm) were fabricated using tetrakis(hydroxymethyl)phosphonium chloride as a reducing agent. The sAu/GSH particles were intravenously injected into mice, remained in vessels for a few minutes, and were then excreted by the kidneys after 24 h, similar to the commercial contrast agent iopamidol. Next, the Au/GSH and lactoferrin (sAu/GSH-LF) (long axis size, 17.3 nm) complex was produced by adding lactoferrin to the sAu/GSH solution under the influence of a condensing agent. On intravenously administering sAu/GSH-LF to mice, the blood retention time was 1-3 h, which was considerably longer than that observed with iopamidol and sAu/GSH. Moreover, we succeeded in imaging morphological changes in identical tumor vessels for several days using X-ray CT with sAu/GSH-LF.
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Oro , Nanopartículas del Metal , Animales , Vasos Sanguíneos/diagnóstico por imagen , Angiografía por Tomografía Computarizada , Medios de Contraste , Lactoferrina , Ratones , Tomografía Computarizada por Rayos XRESUMEN
Immobilization of photocatalysts on supports is an important method of adding highly active photocatalysts to a continuous flowing system without the need for photocatalyst recovery. However, direct immobilization prevents exposure to all photocatalytically active surfaces. Therefore, to immobilize particulate photocatalysts, while exposing the photocatalytic surface to organic pollutant water in a continuous flowing system, in this study, we employed double-inverse-opal (DIO) with periodically arranged, interconnected macropores, each containing a single photocatalytic particle. Increasing the macropore size successfully enhanced the decomposition rate of organic dye due to the high diffusion rate of dye molecules in the macropores of thin DIOs. However, an excessive increase in macropore size lowered the decomposition rate of dye molecules because an increase in DIO thickness caused the attenuation of light used to excite the photocatalytic particles. This study presents novel, immobilized photocatalytic DIO-structured particles that can be employed in continuous flowing reaction systems by tuning the photocatalytic particle size, macropore size, and DIO thickness.
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Assembly of plasmonic nanoparticle clusters having hotspots in a specific space is an effective way to efficiently utilize their plasmonic properties. In the assembly, however, bulk-like aggregates of the nanoparticles are readily formed by strong van der Waals forces, inducing a decrease of the properties. The present work proposes an advanced method to avoid aggregation of the clusters by encapsulating into a confined space of hollow silica interior. Hollow spheres incorporating gold nanoparticle clusters were synthesized by a surface-protected etching process. The observation of inner nanoparticles with liquid cell transmission electron microscopy experimentally proved that the nanoparticles moved as a cluster instead of as dispersed nanoparticles within the water-filled hollow compartment. The hollow spheres incorporating the nanoparticle clusters were assembled in the vicinity of electrodes by application of an external AC electric field, resulting in the enhancement of Raman intensities of probe molecules. The nanoparticle-cluster-containing hollow spheres were redispersed when the electric field was turned off, showing that the hollow silica spheres can act as a physical barrier to avoid the cluster aggregation. The Raman intensities were reversibly changed by switching the electric field on and off to control the assembled or dispersed states of the hollow spheres.
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Objective: Human papillomavirus (HPV) vaccination was introduced in Japan in April 2013, as a national immunization program for girls aged 12-16 years, after an initial introduction in 2010 as a public-aid program for girls aged 13-16 years. The Yuri-Honjo district had the highest vaccine coverage among women aged 17-51 years in 2017, due to the original public-aid program. The aim of this study was to evaluate the differences in the vaccine types of HPV16/18 infections between 2008-2012 (pre-vaccine era) and 2013-2017 (vaccine era). Materials and Methods: We evaluated whether HPV vaccination was associated with a decrease in the prevalence of HPV16/18 and high-risk HPV and the incidence of HPV-associated cervical lesions. A total of 1,342 women aged 18-49 years, covering both the pre-vaccine and vaccine eras, who visited Yuri Kumiai General Hospital and underwent HPV genotype tests from June 2008 to December 2017 were compared. Results: Among women aged 18-24 years with higher vaccine coverage (68.2%), the prevalence of HPV16/18 and high-risk HPV decreased from 36.7% and 69.4%, respectively, in the pre-vaccine era to 5.8% and 50.0%, respectively, in the vaccine era (p=0.00013 and p=0.047, respectively). Among those with cervical intraepithelial neoplasia grade 2- and grade 2+, HPV16/18 prevalence decreased from 30.0% to 2.7% (p=0.0018) and from 81.8% to 36.4% (p=0.030), respectively. In this age group, the rate of HPV16/18 positivity decreased significantly. Among age groups with lower vaccine coverage, HPV prevalence did not significantly differ between the two eras. Conclusion: The prevalence of HPV16/18 and high-risk HPV significantly decreased in women aged 18-24 years, most of whom were vaccinated. HPV vaccination effectively reduced the prevalence of HPV16/18 infections in the Yuri-Honjo district.
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Inspired by the structural coloration of anisotropic materials in nature, we demonstrate the preparation of structural color materials by the assembly of anisotropic particles. Spherical artificial melanin particles consisting of a polystyrene core and polydopamine shell were stretched asymmetrically to form uniform-sized ellipsoidal particles with different aspect ratios. The aspect ratio and assembly method of the ellipsoidal particles influence the structural coloration, indicating that the particle shape is one of the important parameters for controlling the structural coloration. The discovery of a method to control the structural color using ellipsoidal particles is useful in basic research on structural colors in nature and provides flexibility in material design and extends the application range of structural color materials.
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Materiales Biomiméticos/síntesis química , Color , Melaninas/química , Materiales Biomiméticos/química , Estructura Molecular , Tamaño de la Partícula , Propiedades de SuperficieRESUMEN
Colloidal molecules created by clustering monodisperse particles are a significant model system of atoms and molecules in colloidal scale. To attain modelling of complex or high-molecular-weight molecules such as hyper-branched polymers and proteins, it is required to develop a new assembling system which can prepare three-dimensionally designed colloidal molecules. In this study, we proposed an approach for complex colloidal molecules created by association between golf ball-like particles and spherical particles via depletion interaction. Several golf ball-like particles joined together, which formed joined particle assemblies at the spherical particles acting as their joints in a depletant solution. The number of golf ball-like particles in a particle assembly was increased by increasing the concentration of the depletant, leading to the formation of branched colloidal chains of the golf ball-like particles. Because the golf ball-like particles in the colloidal chain flexibly rotated at their joints, the conformation of the chains varied in the depletant solution. The present results demonstrated that the golf-ball like particle that can be joined to form colloidal macromolecules with high association number and high flexibility will be a promising building block for complex colloidal model systems.
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Assembly of plasmonic nanoparticles (NPs) in suspensions is a promising approach for the control of optical and sensing properties that depend on the assembled states of plasmonic NPs. This review focuses on the controlling methods to assemble the NP via external stimuli such as pH, temperature, light, magnetic field, and electric field. External stimuli are introduced as powerful tools to assemble the NPs because of various operational factors, such as the intensity, application time, and frequency, which can be employed. In addition to a summary of recent studies on the controlling methods, a future study on the reversible control over assembled states of the plasmonic NPs via external stimuli is proposed.
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Yolk/shell particles composed of a submicrometer-sized movable core and a silica shell are promising building blocks for novel optical colloidal crystals, because the locations of cores in the shell compartment can be reversibly changed by using external stimuli. Two dimensional arrays of yolk/shell particles incorporating movable cores were prepared by a self-assembly method. The movable cores of colloidal crystals in water could be observed with an optical microscope under application of external electric field. The motions of inner silica cores depended on the electric field strength and frequency and were categorized into three cases: (1) Random Brownian motion, (2) anisotropic motion of cores moving in a direction orthogonal to a field, and (3) suppressed motion fixed in the center of shell compartment. Random Brownian motion of cores was scarcely affected by field strength when a high frequency (in the MHz range) electric field was applied. On the other hand, an increase in field strength at low-frequency fields (kHz) transiently changed the core motion from (1) to (2) and a further increase in field strength changed it from (2) to (3). When the silica core was incorporated in a large void a stronger electric field was needed to suppress its motion than when it was in a small void. The high responsivity to electric fields in a low-frequency range indicated the importance of electric double layer (EDL) interaction between core and inner shell in controlling the core location in yolk/shell colloidal crystals. It was also shown that movable titania cores in yolk/shell particles required a low-frequency field with a high strength to change from the random to anisotropic motion. The result suggested that the electrostatic interaction between EDLs of the silica core and the inner silica wall could be stronger than that between EDLs of the titania core and the silica shell.
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Golf ball-like particles having a number of dimples on their spherical surfaces were prepared by a combined method of heterocoagulation between hard polymer particles and soft silicone oil droplets, polymerization of the oil droplets, and dissolution of the polymer particles with tetrahydrofuran. In the heterocoagulation, polystyrene (PSt) particles of three different sizes were employed as hard particles. Distribution of dimples formed with small-sized PSt particles was less homogeneous than that with middle-sized PSt particles (MPS). Narrowly dispersed golf ball-like particles with homogeneously distributed dimples were successfully prepared with a high number ratio of MPS to oil droplets. The employment of large-sized PSt particles in the heterocoagulation decreased the number of PSt particles required for the stabilization of the oil droplets, which created polyhedron-like particles having dimples on their surface. Additional experiments in which polymer particles with different surface affinities to the oil droplets were heterocoagulated with the droplets revealed that a high surface affinity of particles to the droplets could deeply embed the polymer particles into the droplets and form dimples with a low contact angle.
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Monodisperse, nonmagnetic, asymmetrical composite dumbbells in a suspension of magnetic nanoparticles (ferrofluid) were aligned by application of an external magnetic field to the ferrofluid. The asymmetrical composite dumbbells were prepared by two-step soap-free emulsion polymerization consisting of the first polymerization to coat spherical silica cores with cross-linked poly(methyl methacrylate) (PMMA) shell and the second polymerization to protrude a polystyrene (PSt) lobe from the core-shell particles. A chain structure of nonmagnetic dumbbells oriented to the applied magnetic field was observed at nanoparticle content of 2.0 vol % and field strengths higher than 1.0 mT. A similar chain structure of the dumbbells was observed under application of alternating electric field at strengths higher than 50 V/mm. Parallel and orthogonally combined applications of the electric and magnetic fields were also conducted to examine independence of the electric and magnetic applications as operational factors in the dumbbell assembling. Dumbbell chains stiffer than those in a single application of external field were formed in the parallel combined application of electric and magnetic fields. The orthogonal combination of the different applied fields could form a magnetically aligned chain structure of the nonmagnetic dumbbells oriented to the electric field. The present work experimentally indicated that the employment of inverse magnetorheological effect for nonmagnetic, anisotropic particles can be a useful method for the simultaneous controls over the orientation and the positon of anisotropic particles in their assembling.
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The dynamic properties of phospholipid (PL) membranes (phase state and phase transition) play crucial roles in biological systems. However, highly sensitive, direct analytical methods that shed light on the nature of lipids and their assemblies have not been developed to date. Here, we describe the analysis of PL-modified Au nanoparticles (Au@PL) using membrane surface-enhanced Raman spectroscopy (MSERS) and report the properties of the self-assembled PL membranes on the Au nanoparticle. The Raman intensity per PL concentration increased by 50-170 times with Au@PL, as compared to large unilamellar vesicles (LUVs) at the same PL concentration. The phase state and phase transition temperature of the PL membrane of Au@PL were investigated by analyzing the Raman peak ratio (R = I2882/I2930). The enhancement at 714 cm(-1) (EF(714)) varied with the hydrocarbon chain length of the PLs and the assembled degree of Au@PLs. In calculation, the EF(714),assembled was estimated to be 111-142 when the distance between AuNPs was 7.0-7.5 nm, which was correlated to the speculative enhancement factor, suggesting that the assembly of the Au@PLs contributed to the MSERS.
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Fosfolípidos/análisis , Fosfolípidos/química , Espectrometría Raman , Oro/química , Nanopartículas del Metal/química , Propiedades de SuperficieRESUMEN
Controls over the position and orientation of anisotropic particles in their assemblies are intriguing issues for functional colloidal crystals that are switchable with external fields such as electric and magnetic fields. We propose a novel approach for the fabrication of rattle-type colloidal crystals containing an anisotropic, movable core surrounded by a void space that allows rearrangement of the anisotropic core in the assembly. In the fabrication, multilayered core-shell particles composed of a titania core, polystyrene shell, and silica shell were prepared and then heated at 500 °C for 4 h to selectively remove the middle layer of polystyrene. The heating treatment induced deformation of spherical titania cores in the compartment of silica shells, while the void space required for the orientation and relocation of anisotropic core was generated. The rattle particles fabricated were self-assembled by a simple dip-coating to form an arrangement of the spherical yolk/shell particles incorporating an anisotropic core. Brownian motion of the anisotropic cores observed with an optical microscope showed that the assembly of rattle-type particles had the potential to control location and orientation of the anisotropic cores in the shell compartment by application of external fields.
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Submicrometer-sized amorphous titania spheres incorporating Au nanoparticles (NPs) were prepared in a one-pot synthesis consisting of a sol-gel reaction of titanium(IV) isopropoxide in the presence of chloroauric acid and a successive reduction with sodium borohydride in a mixed solvent of ethanol/acetonitrile. The synthesis was allowed to prepare monodisperse titania spheres that homogeneously incorporated Au NPs with sizes of ca. 7 nm. The Au NP-loaded titania spheres underwent different crystallization processes, including 500 °C calcination in air, high-temperature hydrothermal treatment (HHT), and/or low-temperature hydrothermal treatment (LHT). Photocatalytic experiments were conducted with the Au NP-loaded crystalline titania spheres under irradiation of UV and visible light. A combined process of LHT at 80 °C followed by calcination at 500 °C could effectively crystallize titania spheres maintaining the dispersion state of Au NPs, which led to photocatalytic activity higher than that of commercial P25 under UV irradiation. Under visible light irradiation, the Au NP-titania spheres prepared with a crystallization process of LHT at 80 °C for 6 h showed photocatalytic activity much higher than a commercial product of visible light photocatalyst. Structure analysis of the visible light photocatalysts indicates the importance of prevention of the Au NPs aggregation in the crystallization processes for enhancement of photocatalytic activity.