Fusion Growth and Extraordinary Distortion of Ultrasmall Metal Oxide Nanoparticles.

Ultrasmall metal oxide nanoparticles (<5 nm) potentially have new properties, different from conventional nanoparticles. The precise size control of ultrasmall nanoparticles remains difficult for metal oxide. In this study, the size of CeO2 nanoparticles was precisely controlled (1.3-9.4 nm) using a continuous-flow hydrothermal reactor, and the atomic distortion that occurs in ultrasmall metal oxides was explored for CeO2. The crystalline nanoparticles grow rapidly like droplets via coalescence, although they reach a critical particle size (∼3 to 4 nm), beyond which they grow slowly and change shape through ripening. In the initial growth stage, the ultrasmall nanoparticles exhibit disordered atomic configurations, including stacking faults. In ultrasmall CeO2 nanoparticles (<3 to 4 nm), unusual electron localization occurs on Ce 4f orbitals (Ce3+) as a result of O disordering, regardless of O vacancy concentration. This behavior differs from ordinary electron localization caused by the presence of O vacancies. The ultrasmall metal oxides have extraordinary distortion states, making them promising for use in nanotechnology applications. Furthermore, the proposed synthesis method can be applied to various other metal oxides and allows exploration of their properties.

Enhancing the Responsiveness of Thermoelectric Gas Sensors with Boron-Doped and Thermally Annealed SiGe Thin Films via Low-Pressure Chemical Vapor Deposition.

Thermoelectric gas sensor (THGS) devices with catalysts and Si0.8Ge0.2 thin films of different boron doping levels of 1018, 1019, and 1020 cm-3 were fabricated, and their transport properties are investigated. SiGe films were deposited on Si3N4/SiO2 multilayers on Si substrates using low-pressure chemical vapor deposition (LPCVD) and thermally annealed at 1050 °C. The Seebeck coefficients of the SiGe films were increased after thermal annealing, ranging from 191 to 275 µV/K at temperatures of 74 to 468 °C in air, and reaching the highest power factor of 6.78 × 10-4 W/mK2 at 468 °C. The thermal conductivity of the SiGe films varied from 2.4 to 3.0 W/mK at 25 °C. The THGS detection performance was tested for the H2 gas in air from 0.01 to 1.0%, and compared to the thermoelectric properties of the SiGe films. The high-temperature annealing treatment process was successful in enhancing the thermoelectric performance of both the SiGe films and sensor devices, achieving the best THGS performance with the sensor device fabricated from the annealed SiGe film with 1018 cm-3 boron-doped Si0.8Ge0.2.

Quantitative evaluation of the intratumoral distribution of platinum in oxaliplatin-treated rectal cancer: In situ visualization of platinum via synchrotron radiation X-ray fluorescence spectrometry.

Oxaliplatin (l-OHP), a platinum-based drug, is a key chemotherapeutic agent for colorectal cancer (CRC), but drug resistance and toxic effects have been major limitations of its use. Synchrotron radiation X-ray fluorescence spectrometry (SR-XRF) is a rapid, nondestructive technique for monitoring the distribution of metals and trace elements in cells or tissue samples. We applied SR-XRF to visualize the distribution of platinum and other elements in 30 rectal cancer specimens resected from patients who received l-OHP-based preoperative chemotherapy and quantified platinum concentration in the tumor epithelium and stroma, respectively, using calibration curves. The platinum concentration in rectal cancer tissue ranged 2.85-11.44 ppm, and the detection limit of platinum was 1.848 ppm. In the tumor epithelium, the platinum concentration was significantly higher in areas of degeneration caused by chemotherapy than in nondegenerated area (p < 0.001). Conversely, in the tumor stroma, the platinum concentration was significantly higher in patients with limited therapeutic responses than in those with strong therapeutic responses (p < 0.001). Furthermore, multivariate analysis illustrated that higher platinum concentration in the tumor stroma was an independent predictive factor of limited histologic response (odds ratio; 19.99, 95% confidence interval; 2.04-196.37, p = 0.013). This is the first study to visualize and quantify the distribution of platinum in human cancer tissues using SR-XRF. These results suggest that SR-XRF analysis may contribute to predicting the therapeutic effect of l-OHP-based chemotherapy by quantifying the distribution of platinum.

Ground-State Copper(III) Stabilized by N-Confused/N-Linked Corroles: Synthesis, Characterization, and Redox Reactivity.

Stable square planar organocopper(III) complexes (CuNCC2, CuNCC4, and CuBN) supported by carbacorrole-based tetradentate macrocyclic ligands with NNNC coordination cores were synthesized, and their structures were elucidated by spectroscopic means including X-ray crystallographic analysis. On the basis of their distinct planar structures, X-ray absorption/photoelectron spectroscopic features, and temperature-independent diamagnetic nature, these organocopper complexes can be preferably considered as novel organocopper(III) species. The remarkable stability of the high-valent Cu(III) states of the complexes stems from the closed-shell electronic structure derived from the peculiar NNNC coordination of the corrole-modified frameworks, which contrasts with the redox-noninnocent radical nature of regular corrole copper(II) complexes with an NNNN core. The proposed structure was supported by DFT (B3LYP) calculations. Furthermore, a π-laminated dimer architecture linked through the inner carbons was obtained from the one-electron oxidation of CuNCC4. We envisage that the precise manipulation of the molecular orbital energies and redox profiles of these organometallic corrole complexes could eventually lead to the isolation of yet unexplored high-valent metal species and the development of their organometallic reactions.

Depth-Resolved Characterization of Perylenediimide Side-Chain Polymer Thin Film Structure Using Grazing-Incidence Wide-Angle X-ray Diffraction with Tender X-rays.

Polymers with a perylenediimide (PDI) side chain (PAc12PDI) consist of two kinds of crystalline structures with various types of orientations in a thin film. Understanding the population of the microcrystalline structure and its orientation along the thickness is strongly desired. Grazing-incidence wide-angle X-ray diffraction (GIWAXD) measurements with hard X-rays, which are generally chosen as λ = 0.1 nm, are a powerful tool to evaluate the molecular aggregation structure in thin films. A depth-resolved analysis for the outermost surface of the polymeric materials using conventional GIWAXD measurements, however, has limitations on depth resolution because the X-ray penetration depth dramatically increases above the critical angle. Meanwhile, tender X-rays (λ = 0.5 nm) have the potential advantage that the penetration depth gradually increases above the critical angle, leading to precise characterization for the population of crystallite distribution along the thickness. The population of the microcrystalline states in the PAc12PDI thin film was precisely characterized utilizing GIWAXD measurements using tender X-rays. The outermost surface of the PAc12PDI thin film is occupied by a monoclinic lattice with a = 2.38 nm, b = 0.74 nm, c = 5.98 nm, and ß = 108.13°, while maintaining the c-axis perpendicular to the substrate surface. Additionally, the presence of solid substrate controls the formation of the crystallite with unidirectional orientation.

Preparation of High-Density Polymer Brushes with a Multihelical Structure.

It is well-known that a mixture of isotactic and syndiotactic polymethyl methacrylate (PMMA) forms a stereocomplex consisting of a multihelical structure in which an isotactic chain is surrounded by a syndiotactic chain. Here, we report the basic structure of the stereocomplex formed when the syndiotactic PMMA chains are tethered to a silicon substrate and form a high-density polymer brush. The influence of geometric confinement was investigated by preparing the high-density polymer brushes on a flat and spherical substrate. In both cases, mixing the untethered isotactic PMMA with the grafted syndiotactic PMMA led to the formation of a stereocomplex with a multihelical structure. Static contact angle measurements showed a hindered surface mobility at the outermost surface of the polymer brush, indicating that the stereocomplex forms a crystalline structure. A syndiotactic polymer brush with substituted fluoroalkyl groups was prepared to increase the contrast for grazing incidence wide-angle X-ray diffraction (GIWAXD) measurements. The GIWAXD results verified that the stereocomplex forms a crystalline structure oriented perpendicular to the substrate with a relatively low degree of orientation.

Bis-Copper(II)/π-Radical Multi-Heterospin System with Non-innocent Doubly N-Confused Dioxohexaphyrin(1.1.1.1.1.0) Ligand.

A contracted doubly N-confused dioxohexaphyrin(1.1.1.1.1.0) complex consisting of two paramagnetic copper metals and open-shell π-radical ligand was synthesized as a new multi-heterospin motif. X-ray spectroscopy supported the divalent character of the inner copper centers, and electron paramagnetic resonance and magnetometric studies suggested the presence of unpaired d electrons strongly antiferromagnetically coupled with π-radicals delocalized on the macrocycle. The 25 π non-innocent dioxohexaphyrin ligand allowed the facile interconversion between antiaromatic 24 π and aromatic 26 π species, respectively, upon redox reactions.

Copper-manganese mixed oxides: CO2-selectivity, stable, and cyclic performance for chemical looping combustion of methane.

Chemical looping combustion (CLC) is a key technology for oxy-fuel combustion with inherent separation of CO2 from a flue gas, in which oxygen is derived from a solid oxygen carrier. Multi-cycle CLC performance and the product selectivity towards CO2 formation were achieved using mixed oxide of Cu and Mn (CuMn2O4) (Fd3[combining macron]m, a = b = c = 0.83 nm) as an oxygen carrier. CuMn2O4 was prepared by the co-precipitation method followed by annealing at 900 °C using copper(II) nitrate trihydrate and manganese(II) nitrate tetrahydrate as metal precursors. CuMn2O4 showed oxygen-desorption as well as reducibility at elevated temperatures under CLC conditions. The lattice of CuMn2O4 was altered significantly at higher temperature, however, it was reinstated virtually upon cooling in the presence of air. CuMn2O4 was reduced to CuMnO2, Mn3O4, and Cu2O phases at the intermediate stages, which were further reduced to metallic Cu and MnO upon the removal of reactive oxygen from their lattice. CuMn2O4 showed a remarkable activity towards methane combustion reaction at 750 °C. The reduced phase of CuMn2O4 containing Cu and MnO was readily reinstated when treated with air or oxygen at 750 °C, confirming efficient regeneration of the oxygen carrier. Neither methane combustion efficiency nor oxygen carrying capacity was altered with the increase of CLC cycles at any tested time. The average oxygen carrying capacity of CuMn2O4 was estimated to be 114 mg g(-1), which was not altered significantly with the repeated CLC cycles. Pure CO2 but no CO, which is one of the possible toxic by-products, was formed solely upon methane combustion reaction of CuMn2O4. CuMn2O4 shows potential as a practical CLC material both in terms of multi-cycle performance and product selectivity towards CO2 formation.

Effects of high-humidity aging on platinum, palladium, and gold loaded tin oxide--volatile organic compound sensors.

This study is an investigation of high-humidity aging effects on the total volatile organic compound (T-VOC) gas-sensing properties of platinum, palladium, and gold-loaded tin oxide (Pt,Pd,Au/SnO(2)) thick films. The sensor responses of the high-humidity aged Pt,Pd,Au/SnO(2), a non-aged Pt,Pd,Au/SnO(2), and a high-humidity aged Pt/SnO(2) to T-VOC test gas have been measured. The high-humidity aging is an effective treatment for resistance to humidity change for the Pt,Pd,Au/SnO(2) but not effective for the Pt/SnO(2). The mechanism of the high-humidity aging effects is discussed based on the change of surface state of the SnO(2) particles.

Resistive oxygen sensor using ceria-zirconia sensor material and ceria-yttria temperature compensating material for lean-burn engine.

Temperature compensating materials were investigated for a resistive oxygen sensor using Ce(0.9)Zr(0.1)O(2) as a sensor material for lean-burn engines. The temperature dependence of a temperature compensating material should be the same as the sensor material; therefore, the Y concentration in CeO(2)-Y(2)O(3) was optimized. The resistance of Ce(0.5)Y(0.5)O(2-δ) was independent of the air-to-fuel ratio (oxygen partial pressure), so that it was confirmed to function as a temperature compensating material. Sensor elements comprised of Ce(0.9)Zr(0.1)O(2) and Ce(0.5)Y(0.5)O(2-δ) were fabricated and the output was determined to be approximately independent of the temperature in the wide range from 773 to 1,073 K.