RESUMEN

In this study, photonic balls─spherical aggregates of submicrometer-sized silica particles with uniform particle size─were investigated as structural colored materials. The structural color of these photonic balls is influenced by the ordered arrangement of the silica particles. The research focused on how the addition of electrolytes, specifically NaCl, affects the formation of photonic balls to achieve the desired structural color. Without NaCl, the photonic balls formed onion-shaped colloidal crystals. At NaCl concentrations above 0.006 mol/L, the particles aggregated into short-range ordered structures. When the concentration exceeded 0.05 mol/L, the aggregates lost their spherical shape. The study also explored the addition of carbon black (CB), a water-dispersible material due to its surface charge. The findings revealed that NaCl induced the phase separation between the charged silica particles and CB, resulting in Janus-shaped photonic balls─one side exhibiting structural color and the other side appearing black due to the presence of CB. Changing the silica particle size altered the hues of these Janus-shaped photonic balls, though they appeared uniformly colored to the naked eye. While this study did not specifically examine the applications of Janus-shaped photonic balls composed of silica particles and CB, CB is known for its ability to absorb near-infrared radiation and convert it into heat as well as its conductive properties. Silica, on the other hand, has a low thermal conductivity and acts as an electrical insulator. The structurally colored Janus-shaped photonic balls created in this study may serve as pigments in applications requiring anisotropic heat generation and electrical conduction. Additionally, the study's findings suggest the potential for creating various types of Janus-shaped photonic balls from materials with differing densities.

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This study affords mechanistic insights into the formation mechanism of carbodiimide ions (NCN2-) from urea during the synthesis of La2O2NCN by employing the "proanion" strategy without using NH3 gas. It is a safer, cost-effective, and environmentally friendly approach. Urea, acting as a proanion, decomposes upon heating, facilitating conversion to NCN2-. This work meticulously examines the phase transitions and identifies intermediate species formed during the reaction using in situ X-ray diffraction, Fourier transform infrared spectroscopy, and thermogravimetric-differential thermal analysis-mass spectrometry. The findings present a detailed mechanism in which urea initially decomposes at 140 °C, releasing HNCO, which reacts with La(OH)3 to immobilize NCO- species on the surface of La(OH)3. As the temperature reaches approximately 400 °C, these NCO- anions transform into NCN2- anions by releasing CO2 gas, resulting in the formation of an amorphous phase rich in NCN2-. Following further heating to 600 °C, La2O2NCN crystallizes, enhancing its crystallinity as the temperature increases. These findings elucidate the formation mechanism of La2O2NCN, introduce the "proanion method" for the alternative synthesis of metal (oxy)carbodiimides, and expand their potential for applications as functional materials.

RESUMEN

Layered double hydroxides (LDHs) exhibit diverse chemical compositions and are being designed for promising applications such as CO2 adsorbents. Although many researchers have analyzed CO2 gas evolution and structural transformation behavior at elevated temperatures, there are still inconsistencies in results on the effect of different metal ions in LDHs. In this study, on the basis of atomic/molecular-level findings from our previous study on multistep structural/chemical transformation of Mg-Al LDHs, we analyzed the quantitative gas evolution behavior and structural transformations of M-Al-CO3 LDHs with different divalent metal ions (M = Mg, Zn, or Co, M/Al = 2) at elevated temperatures. Our quantitative analysis revealed that all three LDH samples undergo the three-step chemical transformations: release of interlayer water, partial dehydroxylation of the hydroxyl layers, and complete dehydroxylation of layers and decomposition of interlayer CO32-. However, the temperature range for each step differs, as do the structural transformations for each sample: the layered structure collapses in the first step for Zn-Al LDH and Co-Al LDH, and the third step for Mg-Al LDH. Our results provide for quantitative and concrete understanding of the effect of divalent metal ions in LDHs on thermal decomposition.

RESUMEN

Mg-Al layered double hydroxides (LDHs) with CO32- interlayer anions are promising CO2 adsorbents. Here, we analyzed the quantitative gas evolution behaviors of Mg-Al LDH particles with different Mg/Al ratios during the multistep chemical/structural transformations at elevated temperatures. The Mg/Al molar ratio strongly affects the behavior: the transformation changes from two apparent steps to three steps depending on the Mg/Al ratio. The transformation occurs in essentially the same way as that observed for large Mg-Al LDH crystals: (1) release of the interlayer water, (2) partial dehydroxylation of the hydroxyl layers followed by coordination of carbonate ions to the metals, and (3) collapse of the layered structure. We provide a molecular/atomic level picture of the structure in each step of the transformation by first-principles density functional theory (DFT) calculation. The structurally optimized model and reexamination of experimental data showed that step (1) results in a large decrease in the interlayer distance of the LDH from ∼7.6 to ∼6.7 Å (a decrease of ∼0.9 Å) and the possible explanation is the waving of the metal hydroxide layers. This study provides a comprehensive understanding of the structural changes of LDHs with various Mg/Al ratios to resolve the various interpretations in the literature.

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Chemical and physical designs of alloy nanomaterials have attracted considerable attention for the development of highly functional materials. Although polyol processes using ionic precursors are widely used to synthesise alloy nanoparticles, the reduction potential of polyols limits their chemical composition, making it difficult to obtain 3d transition metals. In this study, we employed pre-synthesized metal hydroxide salt monolayer nanoparticles as precursors to obtain alloy nanoparticles. Simultaneous dehydroxylation of the hydroxide moiety and decomposition of the organic moiety allowed the formation of stable face-centred cubic metals passing through the metal carbide and metastable hexagonal close-packed metal phases. This self-reduction process enabled the formation of nanoparticulate bimetallic alloys and macroporous/mesoporous-structured bimetallic alloys by compositing hard/soft templates with pre-synthesized metal hydroxide salt nanoparticles. We believe that the strategy presented in this study can be used to design nanostructures and chemical compositions of multimetallic alloy nanoparticles as well as bimetallic systems.

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A general procedure for synthesizing various inorganic compounds in a similar manner is required in the field of material chemistry. The use of solid-state reactive agents with inorganic precursors is a successful approach in this direction. In this study, organic-inorganic hybrid metal hydroxide salts (MHSs) were utilized to synthesize various inorganic compounds by a simple heat treatment method because they can be assumed to be "premixed" inorganic precursors and solid-state reactive agents. Comparative studies revealed that the nanocrystalline characteristics and coordination of the carboxylate of the synthesized MHSs enabled simultaneous dehydration of hydroxides and decomposition of carboxylates and subsequent formation of metals and metal sulfides. Manganese, iron, cobalt, nickel, and zinc sulfides, as well as nickel carbides, pnictides, chalcogenides, and halides were obtained using the same procedure. We believe that using nanocrystalline organic-inorganic hybrid MHSs as both inorganic precursors and organic reactive agents will be a simple and versatile way to prepare a wide variety of inorganic complex compounds.

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Minimally invasive boron neutron capture therapy (BNCT) is an elegant approach for cancer treatment. The highly selective and efficient deliverability of boron agents to cancer cells is the key to maximizing the therapeutic benefits of BNCT. In addition, enhancement of the frequencies to achieve boron neutron capture reaction is also significant in improving therapeutic efficacy by providing a highly concentrated boron agent in each boron nanoparticle. As the density of the thermal neutron beam remains low, it is unable to induce high-efficiency cell destruction. Herein, we report phospholipid-coated boronic oxide nanoparticles as agents for BNCT that can provide a highly concentrated boron atom in each nanoparticle. The current system exhibited in vitro BNCT activity seven times higher than that of commercial boron agents. Furthermore, the system could penetrate cancer spheroids deeply, efficiently suppressing thermal neutron irradiation-induced growth.

Asunto(s)

Terapia por Captura de Neutrón de Boro , Nanopartículas , Boro , Fosfolípidos , Compuestos de Boro/uso terapéutico , Óxidos

RESUMEN

Boron neutron capture therapy shows is a promising approach to cancer therapy, but the delivery of effective boron agents is challenging. To address the requirements for efficient boron delivery, we used a hybrid nanoparticle comprising a carborane = bearing pullulan nanogel and hydrophobized boron oxide nanoparticle (HBNGs) enabling the preparation of highly concentrated boron agents for efficient delivery. The HBNGs showed better anti-cancer effects on Colon26 cells than a clinically boron agent, L-BPA/fructose complex, by enhancing the accumulation and retention amount of the boron agent within cells in vitro. The accumulation of HBNGs in tumors, due to the enhanced permeation and retention effect, enabled the delivery of boron agents with high tumor selectivity, meeting clinical demands. Intravenous injection of boron neutron capture therapy (BNCT) using HBNGs decreased tumor volume without significant body weight loss, and no regrowth of tumor was observed three months after complete regression. The therapeutic efficacy of HBNGs was better than that of L-BPA/fructose complex. BNCT with HBNGs is a promising approach to cancer therapeutics.

Asunto(s)

Terapia por Captura de Neutrón de Boro , Neoplasias , Humanos , Nanogeles , Boro , Neoplasias/radioterapia , Neoplasias/tratamiento farmacológico , Compuestos de Boro , Fructosa

RESUMEN

ZnO rod film is a promising material for electrodes and sensors due to its large surface area and high electrical conductivity. One of the drawbacks of conventional ZnO rod film is the random orientation of rods. In this study, an oriented ZnO seed layer composed of hexagonal plate-like ZnO particles was prepared by dip-coating. An oriented ZnO rod film was then synthesized by growing this seed layer using a hydrothermal synthesis method. We optimized the concentration of the precursor and the hydrothermal treatment time to synthesize homogeneous ZnO rod arrays. The uniformity of the rod arrays was improved by applying a strong magnetic field (12 T) during hydrothermal treatment.

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Structurally colored materials consisting of arrays of submicrometer-sized particles have drawn a great deal of attention because of their advantages, including low cost, low impact on human health as well as the environment, and resistance to fading. However, their low thermal stability is considered to be a critical issue for their practical use as colorants. Black-colored substances that can absorb the white color are added to colloidal array-type structurally colored materials to enhance their chromaticity. The poor thermal stability of commonly used black coloring additives, carbon black and Fe3O4 nanoparticles, is a main factor that reduces the heat resistance of structural coloration. Here, we demonstrate the preparation of structurally colored materials with extraordinarily high heat resistance of coloration, up to 900 °C. Several metal oxides, i.e., calcium manganese-based oxide (CCMO), chromium-iron-cobalt-nickel oxide (CFCNO), and lanthanum manganite (LMO), are synthesized and employed as black additives for structurally colored coatings prepared by the electrophoretic deposition of spherical silica particles. When CCMO is used as a black additive, the coloration heat resistance of the film is stable up to 700 °C. On the other hand, the films maintain vivid structural colors after exposure to 900 °C temperatures when CFCNO and LMO are employed as black additives. On the basis of this finding, high heat resistance of structural colors requires both heat resistance of the black additives and nonreactivity with the components of the spherical particles used for colloidal arrays.

RESUMEN

Developing photoactivatable theranostic platforms with integrated functionalities of biocompatibility, targeting, imaging contrast, and therapy is a promising approach for cancer diagnosis and therapy. Here, we report a theranostic agent based on a hybrid nanoparticle comprising fullerene nanocrystals and gold nanoparticles (FGNPs) for photoacoustic imaging and photothermal therapy. Compared to gold nanoparticles and fullerene crystals, FGNPs exhibited stronger photoacoustic signals and photothermal heating characteristics by irradiating light with an optimal wavelength. Our studies demonstrated that FGNPs could kill cancer cells due to their photothermal heating characteristics in vitro. Moreover, FGNPs that are accumulated in tumor tissue via the enhanced permeation and retention effect can visualize tumor tissue due to their photoacoustic signal in tumor xenograft model mice. The theranostic agent with FGNPs shows promise for cancer therapy.

Asunto(s)

Fulerenos , Nanopartículas del Metal , Nanopartículas , Neoplasias , Técnicas Fotoacústicas , Animales , Línea Celular Tumoral , Fulerenos/química , Oro/química , Humanos , Nanopartículas del Metal/uso terapéutico , Ratones , Nanopartículas/química , Neoplasias/diagnóstico por imagen , Neoplasias/terapia , Técnicas Fotoacústicas/métodos , Fototerapia/métodos , Terapia Fototérmica , Medicina de Precisión , Nanomedicina Teranóstica/métodos

RESUMEN

Safe, low-cost structurally colored materials are alternative colorants to toxic inorganic pigments and organic dyes. Colloidal amorphous arrays are promising structurally colored materials because of their angle-independent colors. In this study, we focused on precise tuning of the chromaticity by preparing bilayer colloidal amorphous arrays through electrophoretic deposition (EPD). Systematic investigations with various EPD conditions clarified the contributions of each condition to the EPD process and the competing electrochemical reactions, which enabled us to prepare well-colored coatings. EPD films composed of colloidal amorphous array bilayers were successfully synthesized with controlled film thickness. Chromaticity of the films was found to be precisely controlled by the EPD duration. We believe that this understanding of the EPD process and its application to synthesis of structurally colored bilayer films will bring structurally colored materials closer to practical industrial use.

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Semiconductor photocatalysts showing excellent performance under irradiation of both ultraviolet (UV)- and visible (VIS)-light are highly demanded towards realization of sustainable energy systems. TiO2 is one of the most common photocatalysts and has been widely investigated as candidate showing UV/VIS responsive performance. In this study, we report synthesis of Nb doped TiO2 by environmentally benign mechanochemical reaction. Nb atoms were successfully incorporated into TiO2 lattice by applying mechanical energy. As synthesized Nb doped TiO2 were metastable phase and formed chemical compositional gradient structure of poorly Nb doped TiO2 core and highly Nb doped TiO2 surface after high temperature heat treatment. It was found that formed gradient chemical compositional heterojunctions effectively enhanced photocatalytic performance of Nb doped TiO2 under both of UV- and VIS-light irradiation, which is different trend compared with Nb doped TiO2 prepared through conventional methods. The approach shown here will be employed for versatile systems because of simple and environmentally benign process.

RESUMEN

The use of organic-inorganic hybrid nanoparticles will enable a control of the characteristics of both the nanoparticles and constructed fine structures. In this study, we report the synthesis of acrylate-intercalated layered manganese, cobalt, and nickel hydroxide nanoparticles and their assembly into ordered mesoporous structures. Polymerization of the intercalated acrylates takes place by means of a radical initiator. The formed organic network improved the thermal stability of the layered hydroxides, which results in thermally robust mesoporous structures. Additionally, it is found that the polymerization can be initiated and progressed at 200 °C without any initiators for the layered nickel hydroxide system. This allows for the scalable solid-state thermal polymerization of intercalated acrylates and the formation of thermally robust hierarchically ordered meso/macroporous powders as well as mesoporous films. The electrochemical characterization reveals that the thermally robust mesoporous films having regulated mesopores allow for the effective diffusion of molecules/solvent compared with the films having collapsed mesoporous structures.

RESUMEN

The use of precrystallized nanoparticles as nanobuilding blocks (NBBs) is a promising way to obtain mesoporous materials with crystalline walls. In this study, the size effects of both hydroxide NBBs and nonionic block copolymer (BCP) templates on the formation of ordered mesostructures are investigated. The diameter of layered nickel hydroxide NBBs was controlled at the sub-2 nm scale by an epoxide-mediated alkalinization process. Commercially available nonionic BCPs (gyration radii in the range of 11.9-43.9 Å) were used. Mesoperiodic structures were formed by the evaporation-induced self-assembly process. A proper size combination of hydroxide NBBs, smaller than 12.5 Å, and BCPs, larger than 19.9 Å, is shown to be necessary to form ordered mesostructures.

RESUMEN

A facile method was successfully developed to prepare strontium-tantalum perovskite oxynitride, SrTaO2N, and its solid solutions. Urea was employed as a solid nitriding agent to eliminate the use of toxic NH3 gas. In addition, utilization of sol-gel-derived Ta2O5 gel as a Ta precursor allowed for completion of nitridation within a shorter period and at a lower calcination temperature compared with the conventional ammonolysis process. Optimization of the reaction conditions, such as the urea content, allowed for the production of solid solutions of SrTaO2N and Sr1.4Ta0.6O2.9. The products exhibited optical absorption and chromatic colors because of the narrower band gaps of oxynitrides compared with those of oxides. The O/N ratios of the solid solutions were easily adjusted by varying the amount of urea in the mixture of precursors. As a result, the colors of the products ranged from yellow to brown. The nitridation process and products developed in this study are interesting environmentally benign alternatives to conventional inorganic pigments.

RESUMEN

Nanocrystal-based processing has attracted significant interest for the fabrication of highly functional materials with controlled crystallinity and fine porous structures. In this study, we focused on the template-free synthesis of nanocrystal-based materials with size-tailored pores using layered nickel hydroxide intercalated with acrylate anions. Polymerization of the acrylates encouraged interconnection of the nanocrystals and the formation of homogeneous gel networks. Cryogels after freeze-drying had pores with an average diameter from 4.8 nm (mesoscale) to 68.9 nm (macroscale). It was found that the surface characteristics of starting nanocrystals determined the phase separation tendency of interconnected species from the reaction media and resultant porous structures. We believe that the present study can enable the design of template-free nanocrystal-based porous materials.

RESUMEN

Structurally colored coatings composed of colloidal arrays of monodisperse spherical particles have attracted great attention owing to their versatile advantages, such as low cost, resistance to fading, and low impacts on the environment and human health. However, the weak mechanical stability is considered to be a major obstacle for their practical applications as colorants. Although several approaches based on the addition of polymer additives to enhance the adhesion of particles have been reported, the challenge remains to develop a strategy for the preparation of structurally colored coatings with extremely high robustness using a simple process. Here, we have developed a novel approach to fabricate robust structurally colored coatings by cathodic electrophoretic deposition. The addition of a metal salt, i.e., Mg(NO3)2, to the coating dispersion allows SiO2 particles to have a positive charge, which enables the electrophoresis of SiO2 particles toward the cathode. At the cathode, Mg(OH)2 codeposits with SiO2 particles because OH- ions are generated by the decomposition of dissolved oxygen and NO3- ions. The mechanical stability of the colloidal arrays obtained by this process is remarkably improved because Mg(OH)2 facilitates the adhesion of the particles and substrates. The brilliant structural color is maintained even after several cycles of the sandpaper abrasion test. We have also demonstrated the coating on a stainless steel fork. This demonstration reveals that our approach enables a homogeneous coating on a complicated surface. Furthermore, the high durability of the coating is clarified because the coating did not peel off even when the fork was stuck into a plastic eraser. Therefore, the coating technique developed here will provide an effective method for the pervasive application of the structural color as a colorant.

RESUMEN

Nano-size EVONIK AEROXIDE® P25 titanium dioxide, TiO2, powder was heat-treated at temperatures, 700-900°C, in air. An X-ray diffraction study showed that the P25 powder is composed of approximately 20 and approximately 80 mass% of rutile and anatase phases, respectively. It was also shown that the transformation from anatase to rutile induced by high-temperature heat treatment was almost completed at 750°C, whereas a small amount (less than 3 mass%) of anatase phase was still left even in the powder heat-treated at 900°C. The transformation behaviour was consistent with results obtained by Raman scattering spectroscopy. Raman experiments also indicated that high-temperature heating induced the formation of oxide ion vacancies. Powders were dispersed in methyl orange (MO) aqueous solution, and the bleach rate of MO was measured to evaluate photocatalytic activity under ultraviolet (UV)- and visible-light irradiation. After the heat treatment, the UV-light photocatalytic performance sharply deteriorated. Interestingly, visible-light photocatalytic activity was enhanced by high-temperature heating and reached the highest performance for an 800°C-heated sample, indicating that the P25 powder obtained high visible-light photocatalytic performance after heat treatment. Even after 900°C heat treatment, the photocatalytic performance was higher than that of as-received powder. Enhancement of photocatalytic activities was discussed in relation to visible light absorption and charge carrier transfer.

RESUMEN

Hierarchically porous biocompatible Mg-Al-Cl-type layered double hydroxide (LDH) composites containing aluminum hydroxide (Alhy) have been prepared using a phase-separation process. The sol-gel synthesis allows for the hierarchical pores of the LDH-Alhy composites to be tuned, leading to a high specific solid surface area per unit volume available for high-molecular-weight protein adsorptions. A linear relationship between the effective surface area, SEFF, and loading capacity of a model protein, bovine serum albumin (BSA), is established following successful control of the structure of the LDH-Alhy composite. The threshold of the mean pore diameter, Dpm, above which BSA is effectively adsorbed on the surface of LDH-Alhy composites, is deduced as 20 nm. In particular, LDH-Alhy composite aerogels obtained via supercritical drying exhibit an extremely high capacity for protein loading (996 mg/g) as a result of a large mean mesopore diameter (>30 nm). The protein loading on LDH-Alhy is >14 times that of a reference LDH material (70 mg/g) prepared via a standard procedure. Importantly, BSA molecules pre-adsorbed on porous composites were successfully released on soaking in ionic solutions (HPO4(2-) and Cl(-) aqueous). The superior capability of the biocompatible LDH materials for loading, encapsulation, and releasing large quantities of proteins was clearly demonstrated.