Color-controlled nonstoichiometric spinel-type cobalt gallate nanopigments prepared by supercritical hydrothermal synthesis.

Spinel-type inorganic pigments with intensive color and chemical/thermal stability are showing extensive applications that could be further broadened by color manipulation and improvement of the material properties through nanosizing. In this study, we report the supercritical hydrothermal synthesis of nonstoichiometric spinel-type cobalt gallate nanoparticles (Co-Ga NPs) with controlled color. Without the conventional calcination procedure, NPs with greenish-blue, blue, and yellowish-green colors were synthesized from precursor solutions at pH 7, 9, and 11, respectively, with a low Co/Ga molar ratio of 0.25. X-ray diffraction, scanning/transmission electron microscopy, and inductively coupled plasma-atomic emission spectroscopy methods suggest that the products were spinel-type cobalt gallate NPs with high crystallinity and a nonstoichiometric composition. Based on an X-ray absorption fine structure investigation, the prepared nonstoichiometric Co-Ga NPs were found to have different cationic configurations from stoichiometric CoGa2O4 produced by a solid-state reaction during calcination. Meanwhile, the degrees of distortions at tetrahedral and octahedral sites in the NPs were evaluated by Raman spectroscopy. In particular, nonstoichiometric Co-Ga NPs with a blue color were prepared without calcination for the first time and were found to have lower tetrahedral cobalt occupancy but comparable octahedral cobalt occupancy and larger polyhedral distortions at tetrahedral sites when compared to calcined CoGa2O4. We also discuss strategies that could realize Co-Ga NPs with a more brilliant blue color using the present technique based on an investigation of the growth process.

Facet-Controlled Synthesis of CeO2 Nanoparticles for High-Performance CeO2 Nanoparticle/SnO2 Nanosheet Hybrid Gas Sensors.

CeO2 nanocubes with metastable {100} facets and CeO2 nanooctahedrons with the most stable {111} facets are herein fabricated by controlling the morphology and facets of CeO2 nanoparticles. SnO2 nanosheet-based assembled films coated with these CeO2 nanocubes or CeO2 nanooctahedrons yield {100} CeO2 nanocubes/SnO2 nanosheets and {111} CeO2 nanooctahedron/SnO2 nanosheet hybrid gas sensors, respectively. The hybrid sensors with CeO2 nanoparticles exhibited enhanced sensing responses to numerous chemical species relative to a pristine SnO2 nanosheet gas sensor, including acetone, hydrogen, ethanol, ammonia, acetaldehyde, and allyl mercaptan. In particular, the responses of {100} CeO2 nanocubes/SnO2 nanosheets and {111} CeO2 nanooctahedron/SnO2 nanosheet gas sensors to acetone or allyl mercaptan were 6.8 and 10.3 times higher, respectively, than that of the pristine SnO2 nanosheet gas sensor. Furthermore, the sensor response to ammonia was 2.5 times higher than that of a commercial volatile organic compound (VOC) gas sensor (TGS2602, Figaro Engineering Inc.). The CeO2 nanocube-based sensor with exposed metastable {100} facets promotes the adsorption and oxidation of VOCs owing to the higher surface energy of the metastable {100} facets and therefore exhibits a higher sensing performance than the CeO2 nanooctahedron-based sensor with an exposed {111} facet. The developed sensors show excellent potential for the detection of gas markers in human breath and perspiration for disease diagnosis.

Curcumin-Loaded Liposome Preparation in Ultrasound Environment under Pressurized Carbon Dioxide.

Curcumin-loaded liposomes were prepared using a supercritical carbon dioxide (SCCO2)−ultrasound environment system. The experiments were performed at temperatures of 40−70 °C and pressures of 10−25 MPa in a batch system with ultrasonication for 60 min. Transmission electron microscopy (TEM) images revealed liposome products with spherical morphologies and diameters of <100 nm. Dynamic light scattering (DLS) analysis indicated that the curcumin-loaded liposome nanosuspension exhibited good stability. Changing the operating conditions influenced the amount of liposome-encapsulated curcumin; as the operating temperature or pressure increased, the diameter of the liposome products and the amount of liposome-encapsulated curcumin increased and decreased, respectively. Herein, we described an innovative and practical organic-solvent-free method for generating liposomes from phospholipids.

Radiosensitization Effect of Gold Nanoparticles on Plasmid DNA Damage Induced by Therapeutic MV X-rays.

Gold nanoparticles (AuNPs) can be used with megavolt (MV) X-rays to exert radiosensitization effects, as demonstrated in cell survival assays and mouse experiments. However, the detailed mechanisms are not clear; besides physical dose enhancement, several chemical and biological processes have been proposed. Reducing the AuNP concentration while achieving sufficient enhancement is necessary for the clinical application of AuNPs. Here, we used positively charged (+) AuNPs to determine the radiosensitization effects of AuNPs combined with MV X-rays on DNA damage in vitro. We examined the effect of low concentrations of AuNPs on DNA damage and reactive oxygen species (ROS) generation. DNA damage was promoted by 1.4 nm +AuNP with dose enhancement factors of 1.4 ± 0.2 for single-strand breaks and 1.2 ± 0.1 for double-strand breaks. +AuNPs combined with MV X-rays induced radiosensitization at the DNA level, indicating that the effects were physical and/or chemical. Although -AuNPs induced similar ROS levels, they did not cause considerable DNA damage. Thus, dose enhancement by low concentrations of +AuNPs may have occurred with the increase in the local +AuNP concentration around DNA or via DNA binding. +AuNPs showed stronger radiosensitization effects than -AuNPs. Combining +AuNPs with MV X-rays in radiation therapy may improve clinical outcomes.

Direct Observation Techniques Using Scanning Electron Microscope for Hydrothermally Synthesized Nanocrystals and Nanoclusters.

Metal oxide nanocrystals have garnered significant attention owing to their unique properties, including luminescence, ferroelectricity, and catalytic activity. Among the various synthetic methods, hydrothermal synthesis is a promising method for synthesizing metal oxide nanocrystals and nanoclusters. Because the shape and surface structure of the nanocrystals largely affect their properties, their analytical methods should be developed. Further, the arrangement of nanocrystals should be studied because the properties of nanoclusters largely depend on the arrangement of the primary nanocrystals. However, the analysis of nanocrystals and nanoclusters remains difficult because of their sizes. Conventionally, transmission electron microscopy (TEM) is widely used to study materials in nanoscale. However, TEM images are obtained as the projection of three-dimensional structures, and it is difficult to observe the surface structures and the arrangement of nanocrystals using TEM. On the other hand, scanning electron microscopy (SEM) relies on the signals from the surface of the samples. Therefore, SEM can visualize the surface structures of samples. Previously, the spatial resolution of SEM was not enough to observe nanoparticles and nanomaterials with sizes of between 10 and 50 nm. However, recent developments, including the low-landing electron-energy method, improved the spatial resolution of SEM, which allows us to observe fine details of the nanocluster surface directory. Additionally, improved detectors allow us to visualize the elemental mapping of materials even at low voltage with high solid angle. Further, the use of a liquid sample holder even enabled the observation of nanocrystals in water. In this paper, we discuss the development of SEM and related observation technologies through the observation of hydrothermally prepared nanocrystals and nanoclusters.

Atomic-Scale Valence State Distribution inside Ultrafine CeO2 Nanocubes and Its Size Dependence.

Atomic-scale analysis of the cation valence state distribution will help to understand intrinsic features of oxygen vacancies (VO ) inside metal oxide nanocrystals, which, however, remains a great challenge. In this work, the distribution of cerium valence states across the ultrafine CeO2 nanocubes (NCs) perpendicular to the {100} exposed facet is investigated layer-by-layer using state-of-the-art scanning transmission electron microscopy-electron energy loss spectroscopy. The effect of size on the distribution of Ce valence states inside CeO2 NCs is demonstrated as the size changed from 11.8 to 5.4 nm, showing that a large number of Ce3+ cations exist not only in the surface layers, but also in the center layers of smaller CeO2 NCs, which is in contrast to those in larger NCs. Combining with the atomic-scale analysis of the local structure inside the CeO2 NCs and theoretical calculation on the VO forming energy, the mechanism of size effect on the Ce valence states distribution and lattice expansion are elaborated: nano-size effect induces the overall lattice expansion as the size decreased to ≈5 nm; the expanded lattice facilitates the formation of VO due to the lower formation energy required for the smaller size, which, in principle, provides a fundamental understanding of the formation and distribution of Ce3+ inside ultrafine CeO2 NCs.

Direct Imaging for Single Molecular Chain of Surfactant on CeO2 Nanocrystals.

Organic surfactant controls the synthesis of nanocrystals (NCs) with uniform size and morphology by attaching on the surface of NCs and further facilitates their assembly into ordered superstructure, which produces versatile functional nanomaterials for practical applications. It is essential to directly resolve the surfactant molecules on the surface of NCs to improve the understanding of surface chemistry of NCs. However, the imaging resolution and contrast are insufficient for a single molecule of organic surfactant on NCs. In this work, direct characterization of organic surfactant on CeO2 NCs is conducted by using the state-of-the-art aberration corrected scanning transmission electron microscopy (STEM) imaging and electron energy loss spectra (EELS) techniques. The explicit evidence for the existence and distribution of organic surfactant on CeO2 NCs are obtained on the atomic scale by EELS elemental mapping. Besides, STEM imaging parameters are systematically adjusted and optimized for the direct imaging of a single molecular chain of organic surfactant on CeO2 NCs. Such direct visualization of organic surfactant molecule on the surface of NCs can be a significant step forward in the fields of nanomaterials surface chemistry and materials characterization.

Titanium peroxide nanoparticles enhanced cytotoxic effects of X-ray irradiation against pancreatic cancer model through reactive oxygen species generation in vitro and in vivo.

BACKGROUND: Biological applications of nanoparticles are rapidly increasing, which introduces new possibilities to improve the efficacy of radiotherapy. Here, we synthesized titanium peroxide nanoparticles (TiOxNPs) and investigated their efficacy as novel agents that can potently enhance the effects of radiation in the treatment of pancreatic cancer. METHODS: TiOxNPs and polyacrylic acid-modified TiOxNPs (PAA-TiOxNPs) were synthesized from anatase-type titanium dioxide nanoparticles (TiO2NPs). The size and morphology of the PAA-TiOxNPs was evaluated using transmission electron microscopy and dynamic light scattering. The crystalline structures of the TiO2NPs and PAA-TiOxNPs with and without X-ray irradiation were analyzed using X-ray absorption. The ability of TiOxNPs and PAA-TiOxNPs to produce reactive oxygen species in response to X-ray irradiation was evaluated in a cell-free system and confirmed by flow cytometric analysis in vitro. DNA damage after X-ray exposure with or without PAA-TiOxNPs was assessed by immunohistochemical analysis of γ-H2AX foci formation in vitro and in vivo. Cytotoxicity was evaluated by a colony forming assay in vitro. Xenografts were prepared using human pancreatic cancer MIAPaCa-2 cells and used to evaluate the inhibition of tumor growth caused by X-ray exposure, PAA-TiOxNPs, and the combination of the two. RESULTS: The core structures of the PAA-TiOxNPs were found to be of the anatase type. The TiOxNPs and PAA-TiOxNPs showed a distinct ability to produce hydroxyl radicals in response to X-ray irradiation in a dose- and concentration-dependent manner, whereas the TiO2NPs did not. At the highest concentration of TiOxNPs, the amount of hydroxyl radicals increased by >8.5-fold following treatment with 30 Gy of radiation. The absorption of PAA-TiOxNPs enhanced DNA damage and resulted in higher cytotoxicity in response to X-ray irradiation in vitro. The combination of the PAA-TiOxNPs and X-ray irradiation induced significantly stronger tumor growth inhibition compared to treatment with either PAA-TiOxNPs or X-ray alone (p < 0.05). No apparent toxicity or weight loss was observed for 43 days after irradiation. CONCLUSIONS: TiOxNPs are potential agents for enhancing the effects of radiation on pancreatic cancer and act via hydroxyl radical production; owing to this ability, they can be used for pancreatic cancer therapy in the future.

Green solvent for green materials: a supercritical hydrothermal method and shape-controlled synthesis of Cr-doped CeO2 nanoparticles.

This paper describes a supercritical hydrothermal synthesis method as a green solvent process, along with products based on this method that can be used as green materials that contribute to solving environmental problems. The first part of this paper summarizes the basics of this method, including the mechanism of the reactions, specific features of the supercritical state for nanoparticle synthesis, the continuous flow-type reactor and applications; this provides a better understanding of the suitability of this method to synthesize green materials. The second part of the paper describes the method used to synthesize Cr-doped CeO(2) nanoparticles, which show an extremely high oxygen storage capacity, suggesting their high potential as an environmental catalyst. Transmission electron microscopy and scanning electron microscope images showed octahedral Cr-doped CeO(2) nanoparticles with sizes of 15-30 nm and cubic Cr-doped CeO(2) nanoparticles with sizes of 5-8 nm. Octahedral Cr-doped CeO(2) nanoparticles exposing (111) facets and cubic Cr-doped CeO(2) nanoparticles exposing (100) facets were determined by high-resolution transmission electron microscopy and selected area electron diffraction. The X-ray diffraction peaks shifted to a high angle because the radius of the Cr ion is smaller than that of the Ce ion.

Hydrothermal synthesis of inorganic-organic hybrid gadolinium hydroxide nanoclusters with controlled size and morphology.

A series of gadolinium hydroxide [Gd(OH)3] nanoclusters having different morphologies was synthesized in the presence of 3,4-dihydroxy hydrocinnamic acid (DHCA), an organic modifier, under subcritical water conditions. These well-shaped Gd(OH)3 clusters are composed of many nanorods in a parallel orientation, rather than a disordered aggregation of nanorods, which are linked together by organic DHCA molecules. Here DHCA works as an inter-linker to form these cluster-like structures through coordination bonds. All samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy and SQUID magnetometry. We investigated the effect of the concentrations of DHCA and KOH on the size and morphology of the Gd(OH)3 clusters. Their possible formation mechanism is also briefly discussed.

Stress inversion from initial tensile to compressive side during ultrathin oxide growth of the Si(100) surface.

We report the real-time observation of the stress change during sub-nanometer oxide growth on the Si(100) surface. Oxidation initially induced a rapid buildup of tensile stress up to -1.9 × 10(8) N m(-2) with an oxide thickness of 0.25 nm, followed by gradual compensation by a compressive stress. The compressive stress saturated at 5 × 10(7) N m(-2) for an oxide thickness of 1.2 nm. The analysis, assisted by theoretical study, indicates that the observed initial tensile stress is caused by oxygen bridge-bonding between the Si dimers. Atomistic model calculations considering mutually orthogonal orientations of the Si(100) surface structure reproduce the stress inversion from the tensile to the compressive side.

Supercritical hydrothermal synthesis and in situ organic modification of indium tin oxide nanoparticles using continuous-flow reaction system.

ITO nanoparticles were synthesized hydrothermally and surface modified in supercritical water using a continuous flow reaction system. The organic modification of the nanoparticles converted the surface from hydrophilic to hydrophobic, making the modified nanoparticles easily dispersible in organic solvent. The addition of a surface modifier into the reaction system impacted the crystal growth and particle size as well as dispersion. The particle size was 18 nm. Highly crystalline cubic ITO with a narrow particle size distribution was obtained. The advantages of short reaction time and the use of a continuous reaction system make this method suitable for industrial scale synthesis.

Extra-low-temperature oxygen storage capacity of CeO2 nanocrystals with cubic facets.

Herein we demonstrate the extra-low-temperature oxygen storage capacity (OSC) of cerium oxide nanocrystals with cubic (100) facets. A considerable OSC occurs at 150 °C without active species loading. This temperature is 250 °C lower than that of irregularly shaped cerium oxide. This result indicates that cubic (100) facets of cerium oxide have the characteristics to be a superior low-temperature catalyst.

Material-binding peptide application--ZnO crystal structure control by means of a ZnO-binding peptide.

Recently, a zinc oxide (ZnO)-binding peptide (ZnOBP) has been identified and has been used to assist the synthesis of unique crystalline ZnO particles. We analyzed the influence of ZnOBP on the crystal growth of ZnO structures formed from zinc hydroxide. The addition of ZnOBP in the hydrothermal synthesis of ZnO suppressed [0001] crystal growth in the ZnO particles, indicating that the specificity of the material-binding peptide for specific inorganic crystal faces controlled the crystal growth. Furthermore, the dipeptides with a partial sequence of ZnO-binding "hot spot" in ZnOBP were used to synthesize ZnO particles, and we found that the presence of these dipeptides more strictly suppressed (0001) growth in ZnO crystals than did the complete ZnOBP sequence. These results demonstrate the applicability of dipeptides selected from material-binding peptides to control inorganic crystal growth.

Surfactant-assisted one-pot synthesis of superparamagnetic magnetite nanoparticle clusters with tunable cluster size and magnetic field sensitivity.

Magnetic nanoparticles (MNPs) have many potential biomedical applications. Improvements in their magnetic properties and solubility are necessary for these applications to realize their full potential. In this study, MNPs in the form of raspberry-like magnetite (Fe(3)O(4)) nanoparticle clusters, consisting of tiny Fe(3)O(4) particles with a diameter of approximately 20 nm, were prepared under hydrothermal conditions at 200 °C in the presence of 3,4-dihydroxyhydroxysinnamic acid (DHCA). The primary particles were connected by DHCA molecules to form the clusters, which were well dispersed in water media because a COOH group from DHCA appeared on their surfaces. The cluster size could be tuned from 50 to 400 nm without changing the primary particle size by controlling the reaction time. Therefore, all prepared clusters displayed superparamagnetic properties at room temperature. In addition, the sensitivity of Fe(3)O(4) to an external magnetic field could also be controlled by the cluster size.

Continuous hydrothermal synthesis of nickel oxide nanoplates and their use as nanoinks for p-type channel material in a bottom-gate field-effect transistor.

Nickel oxide nanoplates were continuously synthesized by hydrothermal reaction using a flow-type reactor. The products had a thickness of approximately 10 nm and a lateral size of 100-500 nm. The nanoplates were purified and drop-cast on a bottom-gate substrate and used as the channel material in a field-effect transistor after annealing at 300 degrees C. The I(d)-V(d) profile showed that the NiO nanoplates worked as the p-type semiconductor. This result suggests that various electronic devices can be prepared using metal oxide nanomaterials, which exhibit various properties including magnetism, ferroelectronics and catalysis as well as stability and safety in air and water.

Direct and selective immobilization of proteins by means of an inorganic material-binding peptide: discussion on functionalization in the elongation to material-binding peptide.

Using an artificial peptide library, we have identified a peptide with affinity for ZnO materials that could be used to selectively accumulate ZnO particles on polypropylene-gold plates. In this study, we fused recombinant green fluorescent protein (GFP) with this ZnO-binding peptide (ZnOBP) and then selectively immobilized the fused protein on ZnO particles. We determined an appropriate condition for selective immobilization of recombinant GFP, and the ZnO-binding function of ZnOBP-fused GFP was examined by elongating the ZnOBP tag from a single amino acid to the intact sequence. The fusion of ZnOBP with GFP enabled specific adsorption of GFP on ZnO substrates in an appropriate solution, and thermodynamic studies showed a predominantly enthalpy-dependent electrostatic interaction between ZnOBP and the ZnO surface. The ZnOBP's binding affinity for the ZnO surface increased first in terms of material selectivity and then in terms of high affinity as the GFP-fused peptide was elongated from a single amino acid to intact ZnOBP. We concluded that the enthalpy-dependent interaction between ZnOBP and ZnO was influenced by the presence of not only charged amino acids but also their surrounding residues in the ZnOBP sequence.

Continuous synthesis of organic-inorganic hybridized cubic nanoassemblies of octahedral cerium oxide nanocrystals and hexanedioic acid.

We synthesized cubic nanoassemblies of octahedral CeO(2) nanocrystals by simply heating an aqueous solution of cerium nitrate (Ce(NO(3))(3)) in the presence of hexanedioic acid (HOOC(CH(2))(4)COOH) in a lab-scale plug-flow reactor. It was concluded that the octahedral shape of the primary CeO(2) nanocrystals plausibly leads to octa-coordination of the primary nanocrystals, thus enabling controlled assembly to form a cubic structure.

Disassembly of lignin and chemical recovery in supercritical water and p-cresol mixture. Studies on lignin model compounds.

The aim of the study was to gain insight into the role of the each unit of lignin in the formation of products. Glycerol, guaiacol, the mixture of glycerol and guaiacol (Gly&Gua), and guaiacylglycerol-beta-guaiacyl ether (GGGE) were used as lignin model compounds to study fragmentation of lignin in an excess of water and p-cresol at 400 degrees C. The products have been analyzed employing gas chromatography (GC)-mass spectrometer (MS) and gas chromatography-frame ionization detector for qualitative and quantitative analysis. GC-MS analysis indicated that phenol, o-cresol, methyl-anisole, di-methyl-phenol, ethyl-methyl-phenol, 2-(hydroxy-benzyl)-4-methyl-phenol (BMP) and 2-(2-hydroxy-5-methyl-benzyl)-4-methyl-phenol were formed. The products were similar to the products by the fragmentation of lignin. The products, except o-cresol, were primarily derived from glycerol and/or guaiacol. We also found that the amount of BMP derived from GGGE, which has glycerol unit and guaiacol unit in its structure, is much more than that derived from Gly&Gua. The increase of the BMP yield by reaction with GGGE compared with (glycerol and/or guaiacol) indicates that guaiacylglycerol unit with linkage of Gly&Gua plays an important role in the formation of BMP and also it is suggested that the BMP formation from GGGE has pathways other than that from Gly&Gua.