Three-Dimensional Measurement of Ice Crystals in Frozen Materials by Near-Infrared Imaging Spectroscopy

A novel technique was developed to recognize ice crystals in biological materials and to analyze their three-dimensional morphology using a Cryogenic Micro-Slicer Spectral Imaging System with a micro-slicer unit and a near-infrared spectral imaging unit. Consecutive cross-sections of a frozen sample were exposed by the multi-slicing operations with a minimum thickness of 1 µm, and their images were taken by the imaging unit. Spectroscopic analysis using a near-infrared spectrum meter showed an absorption peak at 1460 nm for pure water. Based on the observations of the absorption band of ice crystals in the wavelength range of 1450–1570 nm and its peak at 1495 nm, a commodity-type bandpass filter with a central wavelength of 1500 nm was adopted to identify ice crystals in near-infrared images. The absorption peak of water exhibited a tendency to move toward longer wavelengths with decreasing sample temperature from 25 °C to ?15 °C. The filtered images of ice crystals in frozen samples were darker than the other components at the peak wavelength of ice crystals. The three-dimensional reconstructed morphology of ice crystals revealed that they were formed along the direction of heat transfer while freezing. The proposed method provides a novel tool to investigate the effects of freezing conditions on the size, morphology and distribution of ice crystals.     

Why would apparent κ linearly change with O/C? Assessing the role of volatility,solubility, and surface activity of organic aerosols

Correlations between O/C and cloud condensation nucleus activity, represented by κ, are a computationally efficient approach to estimate the impact of aerosol aging on cloud formation and climate; however, previously reported correlations between these two variables are empirical and vary widely in their slopes and extrapolations to high O/C values. This study proposes a theoretical framework that bridges elemental ratios, volatility, solubility, and κ. The framework estimates intrinsic κ based on molecular formulas of organics composed of carbon, oxygen, and hydrogen that partition to condensed phase, and then it estimates apparent κ considering solubility distribution parameterized by O/C. This article applied the new framework to the two-dimensional volatility basis set (2D-VBS) and found that distribution of O/C and molecular size play key roles in determining apparent κ. For highly soluble organics, κ is dictated by gas-particle partitioning and it is unlikely for κ of organics to go beyond 0.3 in typical ambient organic material loadings. Sensitivity analysis showed that surface-active compounds are not likely to profoundly alter the overall trend within a reasonable range of surface activity. This framework provides a simple yet plausible explanation of why κ would and would not correlate with O/C; distributions of OA in the 2D-VBS as well as the presence of inorganic salts determine the trend. The framework opens up new opportunities to evaluate two-dimensional representations of organic aerosol aging using κ, a significant advancement from the current empirical linear fits to κ and O/C.

Copyright © 2017 American Association for Aerosol Research     

Inversion domain boundaries in Mn and Al dual‐doped ZnO: Atomic structure and electronic properties

The atomic and electronic structures of inversion domain boundaries in Mn‐Al dual‐doped ZnO (Zn_0.89Mn_0.1Al_0.01O) have been investigated. Using atomic‐resolution scanning transmission electron microscopy, a head‐to‐head c‐axis configuration and cation stacking sequence of αβαβ|γ|αβαβ along the c‐axis were observed at the basal‐plane inversion domain boundary. Energy‐dispersive X‐ray spectroscopy and electron energy‐loss spectroscopy revealed significant localization of Mn and minor localization of Al at the basal‐plane inversion domain boundary. Based on experimental findings, a Mn‐doped basal‐plane inversion domain boundary slab model was constructed and refined by first principles calculations. The model is in agreement with atomic‐resolution images. The local electronic density of states of the slab model basal‐plane inversion domain boundary shows a hybridization of the Mn d and O p states within the valence band and localized Mn d states in the conduction band. The thermoelectric properties of Zn_0.99?xMn_xAl_0.01O ceramics have been reported in a previous work. In this work, the effects of inversion domain boundaries on the thermoelectric properties are discussed. In comparison to Zn_0.99?xMn_xAl_0.01O ceramics with x≤0.05, inversion domain boundaries in Zn_0.89Mn_0.1Al_0.01O caused thermal and electrical conductivity reduction due to interface scattering of phonons and electrons. The Seebeck coefficient increased, suggesting electron filtering at inversion domain boundaries.     

The effect of heat sealing temperature on the properties of OPP/CPP heat seal. I. Mechanical properties

The effect of heat sealing temperature on the mechanical properties and morphology of OPP/CPP laminate films was investigated. The laminated films were placed in an impulse type heat sealing machine with both CPP sides facing each other. The temperatures investigated ranged from 100 to 250°C. T‐peel and tensile tests in combination with SEM were used to characterize the heat seals. A minimum seal initiation temperature of 120°C was identified for OPP/CPP laminate heat sealing. Peel strength increased sharply from zero at 110°C to maximum at 120°C, after which a gradual decrease was observed. Tensile strength initially increased until 120°C, after which it gradually decreased until 170°C and assumed a constant value beyond that. The initial rise has been associated to cold crystallization, while the reduction between 120°C and 170°C was due to relaxation in molecular orientation. Beyond 170°C, all the orientation in the laminate has been lost so orientation effects are nullified. Morphological studies with SEM revealed that seals were partially formed at lower temperatures, while the laminates were totally fused together at high temperatures, with intermediate temperatures showing properties that lie in between. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 753–760, 2005     

Preparation and characterization of electroplated amorphous gold-nickel alloy film for electrical contact applications

A process for electroplating amorphous gold-nickel alloy with the atomic ratio of unity was developed. The plating bath was prepared by adding potassium cyanoaurate(I) into a known plating bath which produces amorphous nickel-tungsten alloy. At a sufficiently high gold concentration, the alloy deposit did not contain any tungsten. The amorphous nature of the Au-Ni alloy produced in the new bath was confirmed by using TEM and THEED. Hardness, resistivity, and contact resistance of this new alloy were determined, and the results are discussed for applications as an electrical contact material.     

Correlations of Hepatic Hemodynamics,Liver Function,and Fibrosis Markers in Nonalcoholic Fatty Liver Disease: Comparison with Chronic Hepatitis Related to Hepatitis C Virus

The progression of chronic liver disease differs by etiology. The aim of this study was to elucidate the difference in disease progression between chronic hepatitis C (CHC) and nonalcoholic fatty liver disease (NAFLD) by means of fibrosis markers, liver function, and hepatic tissue blood flow (TBF). Xenon computed tomography (Xe-CT) was performed in 139 patients with NAFLD and 152 patients with CHC (including liver cirrhosis (LC)). The cutoff values for fibrosis markers were compared between NAFLD and CHC, and correlations between hepatic TBF and liver function tests were examined at each fibrosis stage. The cutoff values for detection of the advanced fibrosis stage were lower in NAFLD than in CHC. Although portal venous TBF (PVTBF) correlated with liver function tests, PVTBF in initial LC caused by nonalcoholic steatohepatitis (NASH-LC) was significantly lower than that in hepatitis C virus (C-LC) (p = 0.014). Conversely, the liver function tests in NASH-LC were higher than those in C-LC (p < 0.05). It is important to recognize the difference between NAFLD and CHC. We concluded that changes in hepatic blood flow occurred during the earliest stage of hepatic fibrosis in patients with NAFLD; therefore, patients with NAFLD need to be followed carefully.     

The initial step of the thermal unfolding of 3-isopropylmalate dehydrogenase detected by the temperature-jump Laue method

A temperature-jump (T-jump) time-resolved X-ray crystallographictechnique using the Laue method was developed to detect small,localized structural changes of proteins in crystals exposedto a temperature increase induced by laser irradiation. In achimeric protein between thermophilic and mesophilic 3-isopropylmalatedehydrogenases (2T2M6T), the initial structural change uponT-jump to a denaturing temperature (~90°C) was found tobe localized at a region which includes a ß-turn and aloop located between the two domains of the enzyme. A mutant,2T2M6T-E110P/S111G/S113E, having amino acid replacements inthis ß-turn region with the corresponding residues ofthe thermophilic enzyme, showed greater stability than the originalchimera (increase of T_m by ~10°C) and no T-jump-inducedstructural change in this region was detected by our method.These results indicate that thermal unfolding of the originalchimeric enzyme, 2T2M6T, is triggered in this ß-turn region.     

SCR of NOx with NH3 over Cu/NaZSM-5 and Cu/HZSM-5 in the presence of decane

The selective catalytic reduction of NO_x with NH₃ in the presence of decane over Cu/ZSM-5 catalysts prepared from H⁺ and Na⁺ZSM-5 precursors were investigated. Cu/NaZSM-5 catalyst showed significantly higher NO_x conversion compared to Cu/HZSM-5. However, the presence of decane decreased the activity of both the catalysts, due to coke formation. Cu/HZSM-5 catalyst showed a larger decline in NO_x conversion with time on stream compared to Cu/NaZSM-5. The higher activity of Cu/NaZSM-5 is attributed, to the promoting effect of Na⁺ cations in the formation of active Cu⁺ and nitrite and nitrate intermediates species and retardation of coke formation.     

Active sites of Cu-ZSM-5 for the decomposition of acrylonitrile

The catalytic decomposition of acrylonitrile (AN) over Cu-ZSM-5 prepared with various Cu loadings was investigated. AN conversion, during which the nitrogen atoms in AN were mainly converted to N₂, increased as Cu loading increased. N₂ selectivities as high as 90–95% were attained. X-ray diffraction measurements (XRD) and temperature-programmed reduction by H₂ (H₂-TPR) showed the existence of bulk CuO in Cu-ZSM-5 with a Cu loading of 6.4 wt% and the existence of highly dispersed CuO in Cu-ZSM-5 with a Cu loading of 3.3 wt%. Electron spin resonance measurements revealed that Cu-ZSM-5 contains three forms of isolated Cu²⁺ ions (square-planar, square-pyramidal, and distorted square-pyramidal). The H₂-TPR results suggested that in Cu-ZSM-5 with a Cu loading of 2.9 wt% and below, Cu⁺ existed even after oxidizing pretreatment. The activity of AN decomposition over Cu/SiO₂ suggested that CuO could form N₂, but, independent of the CuO dispersion, nitrogen oxides (NO_x) were formed above 350 °C. Cu⁺ and the square-pyramidal and distorted square-pyramidal forms of Cu²⁺ showed low activity for AN decomposition. Temperature-programmed desorption of NH₃ suggested that N₂ formation from NH₃ proceeded on Cu²⁺, resulting in the formation of Cu⁺. The Cu⁺ ions were oxidized to Cu²⁺ at around 300 °C. Thus, high N₂ selectivity over Cu-ZSM-5 with a wide range of temperature was probably attained by the reaction over the square-planar Cu²⁺, which can be reversibly reduced and oxidized.     

Vibrationally Excited CO2 Formed in CO + NO Reaction on Pd(110) Surface in High Surface Temperature Range

The infrared chemiluminescence spectra of CO₂ formed during steady-state CO+NO reaction over Pd(110) indicated that the temperature of the bending vibrational mode was much higher than that of the antisymmetric one at higher surface temperatures such as 800–850 K. Especially, in the high temperature range, more vibrationally excited CO₂ was formed from CO+NO reaction than CO+O₂ reaction. On the basis of the result, we propose the model structure of reaction intermediates for CO₂ formation in CO+NO reaction, which is different from that in CO+O₂ reaction.