Field-emission Scanning Electron Microscopy Observations Research Articles

Evaluation of Monomer-containing Isocyanate Groups on Stabilizing Demineralized Dentin Matrix Against Bond Interface Degradation.

To evaluate the effect of urethane methacrylate precursor (UMP) on the enzymatic resistance of demineralized dentin (DD) matrices. Experimental treatments containing 0 (control), 1, and 5 mmol/L UMP dissolved in an acetone (Ace) solution were formulated. Dentin matrix specimens were demineralized in vitro and immersed in the experimental treatments for 1 h. The treated specimens were then stored in 0.1 mg/mL collagenase solution for 24 h, after which their dry mass loss and hydroxyproline (HYP) release were assessed. The swelling ratios of specimens in each group were also evaluated. The interaction between UMP and the dentin matrix was observed using field-emission scanning electron microscopy (FE-SEM). Endogenous enzyme activity in dentin was evaluated using confocal laser scanning microscopy (CLSM). Compared with the other treatment groups, treatment with 1 mM and 5 mM UMP-Ace significantly decreased the dry mass loss, HYP release and swelling ratio of the DD matrix (p < 0.05). FE-SEM and CLSM observations showed that treatment with UMP-Ace protected the structure of the dentin matrix and decreased porosity within the dentin-collagen network. Treatment with 1 mM and 5 mM UMP-Ace protects DD matrix against collagenase degradation and may be clinically useful for improving the durability of the hybrid layer.

Archie's cementation factors for natural rocks: Measurements and insights from diagenetic perspectives

Archie's cementation factor, m, is a critical parameter for petrophysical studies, and the value is influenced by several factors such as the shape, type, and size of grains, degrees of diagenesis, and associated pore structure. Using integrated experimental and theoretical approaches, the goal of this study is to obtain the cementation factor of rocks (both reservoir rock and caprock) and assess the impact of diagenetic processes on the values of the cementation factor. Thirteen samples of geologically diverse rocks (six mudstones, four fossiliferous limestones, two marbles, and one sandstone) were selected to achieve these research objectives. Two approaches, the diffusion of gas tracers and the Bosanquet formula calculation using pore-throat sizes from mercury intrusion porosimetry analyses, were used to derive the cementation factors of these rock samples. These rocks were categorized into two groups based on the correlation between average pore-throat diameter and diffusivity, and an exponential-law relationship between the cementation factor and porosity was determined for these sample groups. In addition, thin-section petrography and field emission-scanning electron microscopy observations were utilized to investigate diagenetic processes, with four diagenetic patterns being established: (1) strong compaction, strong cementation, and weak dissolution-diagenesis pattern; (2) weak compaction, medium cementation, and weak dissolution-diagenesis pattern; (3) weak compaction, medium cementation, and strong dissolution-diagenesis pattern; and (4) fracture-matrix pattern. The results indicated that diagenetic processes and microfractures contribute to the variability in the cementation factors of these rock samples.

Double Z-scheme Ag2CrO4/Bi2O3–KBi6O9Br nanophotocatalysts designed via microwave-assisted combustion-precipitation method for degrading toxic organic dyes

This study introduces novel double Z-scheme Ag2CrO4/Bi2O3–KBi6O9Br nanophotocatalysts for effectively degrading organic dyes, namely Crystal Violet, Acid Orange 7, Rhodamine B, and Eosin Y, from contaminated wastewater. The photocatalysts were thoroughly characterized using advanced techniques, including X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), Transmission Electron Microscopy (TEM), Energy Dispersive X-ray Spectroscopy (EDX-Dot Mapping), Brunauer-Emmett-Teller (BET), Barrett-Joyner-Halenda (BJH), Diffuse Reflectance Spectroscopy (DRS), and Photoluminescence (PL). XRD confirmed the formation of desired crystalline phases without impurities. FESEM and TEM observations revealed the unique morphology of Bi2O3–KBi6O9Br, with distributed Ag2CrO4 nanoparticles on the surface, as confirmed by EDX-dot mapping. BET-BJH analyses indicated a specific surface area of 7.33 m2/g, including meso and macro pores with an average diameter of 10 nm and a total pore volume of 0.018 cm3/g for Ag2CrO4(25%)/Bi2O3–KBi6O9Br sample. DRS revealed notable shifts in absorption edges, suggesting the formation of a heterojunction, and PL analysis indicated a reduced charge carrier recombination rate, further enhancing the photocatalyst's efficacy. In a series of photocatalytic experiments lasting 240 min, using 1 g/L of Ag2CrO4(25%)/Bi2O3–KBi6O9Br, remarkable degradation efficiencies of 95.1%, 94.2%, 98.0%, and 89.6% were achieved for Crystal Violet, Acid Orange 7, Rhodamine B, and Eosin Y, respectively, at an initial concentration of 10 mg/L. The nanophotocatalyst also showed favourable stability after five consecutive reuses. Overall, the double Z-scheme heterostructure in the composite significantly improved the sample's properties and photocatalytic performance, making it highly effective in removing various organic dyes from wastewater.

Enhanced photocatalytic antibacterial activity of Au-coated Ni–Ti–O nanotubes for biomedical applications

Nickel-titanium (NiTi) alloy is a smart material exhibiting superelasticity, contributing to low stiffness and facilitating integration with bone structures. However, NiTi alloy's bioactivity and antibacterial activity limit its dental applications. In this study, we fabricated nickel titanium oxide (Ni–Ti–O) nanotubes with the potential for bioactivity and photocatalytic properties on the surface of NiTi alloy. Specifically, we applied a coating of gold (Au) nanoparticles to the surface of Ni–Ti–O nanotubes, in order to leverage the antibacterial activity through the photocatalytic effect under 470 nm visible light. Field-emission scanning electron microscopy (FE-SEM) and high-resolution transmission electron microscopy (HR-TEM) observations revealed that Au was deposited mainly at the top surface of Ni–Ti–O nanotubes (diameter: 12.76 ± 2.91 nm, height: 721.12 ± 50.25 nm). X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and diffuse reflectance spectroscopy (DRS) analyses revealed that the Ni–Ti–O nanotubes were NiTiO3 crystalline phases with low crystallinity. Therefore, based on the methylene blue (MB) degradation test, the photocatalytic effect was only achieved under visible light at 470 nm, facilitated by the presence of Au. The antibacterial colony forming unit test and enzymatic activity tests demonstrated that Au-coated Ni–Ti–O nanotubes displayed excellent antibacterial activity under 470 nm visible light irradiation, which was also attributed to photocatalytic effect. Consequently, the combination of Au-coated Ni–Ti–O nanotubes and visible light-based photofunctionalization holds promise for expressing antibacterial properties in dental applications.

(Poster Award - Honorable Mention) Ta2O5 Catalyst Support for Polymer Electrolyte Fuel Cells

Pt/C is widely used as polymer electrolyte fuel cells (PEFC) electrocatalysts. The cathodic environment of PEFC is prone to high acidity and high potential, which can degrade cell performance due to carbon corrosion 1. Therefore, electrocatalysts with oxide support such as SnO2 supported on carbon-based materials have been developed, achieving high durability. Further improvement of their catalytic performance is desirable, using a Pt-based alloy catalyst and a mesoporous carbon (MC) 2,3. However, studies using SnO2 as a support have suggested that the low melting point of Sn caused alloying of Pt and Sn and/or melting of metallic Sn, causing degradation of catalytic activity 3. From these reasons, here, we focus on tantalum (Ta) with much higher melting point to fabricate Ta2O5/MC electrocatalysts support, which can support Pt alloy catalysts to achieve both high durability and high activity. Ta2O5 was prepared by a sol-gel method using Ta-ethoxide, and Pt-Co alloy nano-particles were deposited via the acetylacetonate method 4. The amount of Ta2O5 on the MC was set to be 30 and 60 wt.%, and the durability was evaluated by varying the amount of Ta2O5. The molar ratio of Pt to Co was set at 3:1. The microstructure of the electrocatalyst was observed by field-emission scanning electron microscopy (FESEM) and scanning transmission electron microscopy (STEM), and the alloy was evaluated by XRD measurements. Half-cell tests were made to evaluate electrochemical performance and durability (load cycle and start-stop cycle). From the XRD measurements, the Pt peaks were shifted and the Ta2O5 peaks were confirmed, indicating that Pt-Co alloys were formed without forming the alloy of Pt and Ta. FESEM observation revealed that Ta2O5 particles were impregnated with a diameter of about 5 nm, and Pt-Co alloy particles were impregnated with a diameter of 2 to 3 nm. Some of catalyst particles were found to be impregnated on Ta2O5, but no significant selectivity to Ta2O5 was observed. Both Pt effective surface area (ECSA) and oxygen reduction reaction (ORR) activity of the prepared catalysts were higher than of Pt/C, confirming the positive effect of Pt-Co alloy and MC on activity enhancement. Figure 1 shows that the load potential cycle durability was improved using MC, and the start-stop cycle durability was improved by using Ta2O5. In particular, the electrocatalysts with a lower loading of Ta2O5 exhibited higher durability under load potential cycling and subsequent higher ECSA compared to the Pt-Co/C electrocatalyst. Acknowledgment This paper is based on results obtained from a project, JPNP20003, commissioned by the New Energy and Industrial Technology Development Organization (NEDO). References Ohma, K. Shinohara, A. Iiyama, T. Yoshida, and A. Daimaru, ECS Trans, 41(1), 775 (2011).Matsumoto, M. Nagamine, Z. Noda, J. Matsuda, S. M. Lyth, A. Hayashi, and K.Sasaki, J. Electrochem. Soc., 165 (14), F1164 (2018).Inoue, M. Yasutake, Z. Noda, S. M. Lyth, M. Nishihara, A. Hayashi, J. Matsuda, and K. Sasaki, ECS Trans., 109 (9), 413 (2022).Hayashi, H. Notsu, K. Kimijima, J. Miyamoto, and I. Yagi, Electrochem. Acta., 53, 6117 (2008). Figure 1

Relationship between calcinosis cutis in epidermal necrolysis and caspofungin, a physicochemical investigation

Epidermal necrolysis (EN) is a rare life-threatening condition, usually drug-induced and characterised by a diffuse epidermal and mucosal detachment. Calcinosis cutis is reported in various skin diseases, occurring preferentially with tissue damage, but has never been described in EN. Clinical, biological and histopathological characteristics of three patients were retrospectively obtained from medical charts. Immunohistochemistry of classical osteogenic markers was used to explore the pathogenesis of the calcifications; their chemical composition was determined by μFourier transform infra-red (μFTIR) spectroscopy and their localization and morphology by field-emission scanning electron microscopy (FE-SEM). In a recent letter, part of the results of this investigation has been already presented. In this contribution, we have added original data to this previous letter. We have investigated a set of biopsies corresponding to patients who presented atypical healing retardation due to calcinosis cutis. Through FE-SEM observations at the nanometre scale, we describe different areas where are present voluminous calcifications at the surface, submicrometre spherical entities within the papillary dermis and then large “normal” fibres. FE-SEM observations show clearly that “large” calcifications are the result of an agglomeration of small spherical entities. Moreover, micrometre scale spherical entities are the results of an agglomeration of nanometer scale spherical entities. Finally, the last set of data seems to show that the starting point of the calcifications process is “distant” from the epidermis in part of the dermis which appears undamaged. Regarding the chemical composition of large calcifications, different μFTIR maps which underlined the presence of calcium-phosphate apatite have been gathered. Moreover, histopathology indicates that these pathological calcifications are not induced following a trans-differentiation of the skin cells into an osteochondrogenic phenotype. The association of caspofungin administration, known to induce in vitro intracellular calcium influx, and inflammation, induced by EN, known to favor dystrophic calcifications in various inflammatory skin diseases, could explain this never-before reported occurrence of calcinosis cutis.

Micro- to nano-scale areal heterogeneity in pore structure and mineral compositions of a sub-decimeter-sized Eagle Ford Shale

Mineral and organic matter compositions & pore structures of fine-grained shale influence reservoir properties. To improve the understanding of spatial heterogeneity in core-sized samples, methods of microscale X-ray fluorescence (μXRF) mapping, (ultra-) small-angle x-ray scattering [(U)SAXS] and wide-angle X-ray scattering (WAXS) have been used to determine elemental, pore-structure variations at scales up to ~10 cm on two samples prepared at circular and rectangular orientations from a piece of Eagle Ford Shale outcrop in South Texas, USA. In addition, thin section petrography and field emission-scanning electron microscopy observations, X-ray diffraction (XRD), total organic carbon, and pyrolysis were utilized to investigate the potential spatial heterogeneity of pore types, mineral and organic matter compositions for cm-sized samples at both orientations. Overall, the siliceous‑carbonate mineral contents in these two samples (8 cm × 8 cm × 0.08 cm and 5 cm × 8 cm × 0.08 cm, in terms of width×length×thickness) of carbonate-rich Eagle Ford Shale vary between laminations at mm scales. For the circular sample, porosity and specific surface area (SSA) variations range from 0.82 to 3.04% and 1.51 to 14.1 m2/g, respectively. For the rectangular sample, values for porosity and SSA vary from 0.93 to 2.50% and 3.95 to 10.8 m2/g. By analyzing six selected sub-samples on each of two samples with (U)SAXS and XRD techniques, nm-sized pores are mainly interparticle ones in the higher calcite regions, where the porosity is also relatively lower, while the lower calcite regions consist of both interparticle and intraparticle pore types with higher porosity. Finally, the μXRF and (U)SAXS mappings are combined to generate porosity distribution maps to provide more insights about sample heterogeneity related to the laminations and fractures at our observational scales.

Magnetic Graphene-Based Nanosheets with Pluronic F127-Chitosan Biopolymers Encapsulated α-Mangosteen Drugs for Breast Cancer Cells Therapy.

In this study, multifunctional chitosan-pluronic F127 with magnetic reduced graphene oxide (MRGO) nanocomposites were developed through the immobilization of chitosan and an amphiphilic polymer (pluronic F127) onto the MRGO. Physicochemical characterizations and in-vitro cytotoxicity of nanocomposites were investigated through field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, particle size analysis, vibrating sample magnetometer, Raman spectroscopy and resazurin-based in-vitro cytotoxicity assay. FESEM observation shows that the magnetic nanoparticles could tethered on the surface of MRGO, promoting the magnetic properties of the nanocomposites. FTIR identification analysis revealed that the chitosan/pluronic F127 were successfully immobilized on the surface of MRGO. Furthermore, α-mangosteen, as a model of natural drug compound, was successfully encapsulated onto the chitosan/pluronic F127@MRGO nanocomposites. According to in-vitro cytotoxicity assay, α-mangosteen-loaded chitosan/pluronic F127@MRGO nanocomposites could significantly reduce the proliferation of human breast cancer (MFC-7) cells. Eventually, it would be anticipated that the novel α-mangosteen-loaded chitosan/pluronic F127@MRGO nanocomposites could be promoted as a new potential material for magnetically targeting and killing cancer cells.

Advanced oxidative chemical recycling of carbon-fiber reinforced plastic using hydroxyl radicals and accelerated by radical initiators

We herein report a method for the chemical depolymerization of the epoxy resin present in a carbon composite through an advanced oxidation reaction using hydroxyl radicals. It was found that decomposition of the epoxy resin by the hydroxyl radicals generated from NaOCl was complete within 2 h at 100 °C and ambient pressure in an aqueous solution. The effects of different radical initiators (i.e., potassium persulfate (KPS) and 4,4′-azobis(4-cyanovaleric acid) (ACVA)) on the acceleration of hydroxyl radical generation from NaOCl were also evaluated. More specifically, the rate of hydroxyl radical formation in the presence and absence of a radical initiator was determined using the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical method, and it was confirmed that the radical generation rate was increased by up to 3 times when the KPS radical initiator was employed (c.f., in the absence of an initiator). Interestingly, it was confirmed that the reaction rate constant (k) increased by up to 5.3 times when the combination of NaOCl and radical initiator KPS was applied to the recycling of carbon fiber-reinforced plastic (CFRP). In addition, X-ray photoelectron spectroscopy, Raman spectroscopy, and Field-emission scanning electron microscopy observations of the reclaimed carbon fiber demonstrated that no significant damage occurred during the reaction. This result is expected to lead to novel methods for enhancing the rate of CFRP chemical recycling processes.

Quantification and visualization of metastatic lung tumors in mice.

Histopathological examination is important for the diagnosis of various diseases. Conventional histopathology provides a two-dimensional view of the tissues, and requires the tissue to be extracted, fixed, and processed using histotechnology techniques. However, there is an increasing need for three-dimensional (3D) images of structures in biomedical research. The objective of this study was to develop reliable, objective tools for visualizing and quantifying metastatic tumors in mouse lung using micro-computed tomography (micro-CT), optical coherence tomography (OCT), and field emission-scanning electron microscopy (FE-SEM). Melanoma cells were intravenously injected into the tail vein of 8-week-old C57BL/6 mice. The mice were euthanized at 2 or 4weeks after injection. Lungs were fixed and examined by micro-CT, OCT, FE-SEM, and histopathological observation. Micro-CT clearly distinguished between tumor and normal cells in surface and deep lesions, thereby allowing 3D quantification of the tumor volume. OCT showed a clear difference between the tumor and surrounding normal tissues. FE-SEM clearly showed round tumor cells, mainly located in the alveolar wall and growing inside the alveoli. Therefore, whole-tumor 3D imaging successfully visualized the metastatic tumor and quantified its volume. This promising approach will allow for fast and label-free 3D phenotyping of diverse tissue structures.

Insights into the pore structure characteristics of the Lower Silurian Longmaxi Formation shale in the Jiaoshiba area, Southern Sichuan Basin, China

In this paper, the pore structure characteristics of shales and its controlling factors were analyzed by means of total organic carbon (TOC) analysis, X-ray diffraction (XRD) analysis, field emission scanning electron microscopy (FE-SEM) and low-pressure N2 adsorption (LPNA) analysis. Based on the grey relational analysis, the controlling factors of pore structure parameters were discussed. The results showed that the TOC contents range from 2.98 to 4.97%, the main minerals of shales are quartz and clay minerals with an average of 41.62 and 30.98%, respectively. The organic matter pores, the interparticle pores, the intraparticle pores, and the micro-fractures are the main pore types determined by the FE-SEM observation. The pore volume of shales is between 0.0637 and 0.1053 cm3/g, the specific surface area ranges from 16.44 to 37.61 m2/g, the average pore size is between 11.20 and 15.50 nm. The organic matter and the quartz have a positive influence on the specific surface area and total pore volume, whereas the clay minerals have a negative impact. The shales have a wide range of pore size, and the mesopores and macropores are the dominant contributor to the total pore volume while the mesoporous contribute the main specific surface area. The TOC contents and quartz contents have the most significant effect on the total pore volume and specific surface area, and the average pore size is mainly controlled by the quartz contents.

Immunosensing the rheumatoid arthritis biomarker through bifunctional aldehyde-amine linkers on an iron oxide nanoparticle seeded voltammetry sensor

An immunosensor was developed on an interdigitated electrode (IDE) by voltammetry sensing for the early identification of the autoimmune disease ‘rheumatoid arthritis (RA)’ by detecting the biomarker anti-cyclic citrullinated peptide antibody (anti-CCP). Higher immobilization of cyclic citrullinated peptide (CCP) as a probe was achieved by using green synthesized iron oxide nanoparticles (IONPs). Field-emission scanning electron microscopy and field-emission transmission electron microscopy observations revealed that the polydispersed material displayed multifaceted features. X-ray photoelectron spectroscopy analysis confirms the occurrence of Fe, O, and C groups on the synthesized IONPs. IONPs were immobilized with a probe on IDE through bifunctional aldehyde-amine linkers. Due to the elevated occupancy of CCP and the highly efficient electric transfer from IONPs, higher changes in current are observed upon binding of anti-CCP with CCP. In the linear range from 8 to 250 pg/mL, the sensitivity and detection limit of anti-CCP were 8 and 15 pg/mL, respectively, with a regression coefficient of y = 1E−06x−3E−07; R2 = 0.9637. Control experiments with nonimmune antibody and anti-carcinoembryonic antigen indicate the specific detection of anti-CCP. Furthermore, spiking of anti-CCP in human serum does not interfere, representing the specific detection of anti-CCP. This CCP-immobilized IDE through IONP helps to quantify anti-CCP levels in the biological fluid for diagnosing RA.

Inhibitory effects of lactobionic acid on Vibrio parahaemolyticus planktonic cells and biofilms

Vibrio parahaemolyticus is the primary pathogenic bacteria associated with seafood-borne illnesses. Lactobionic acid (LBA) is an organic acid with multiple biological activities that has recently been a focus of interest as an antibacterial agent. The aim of this study was to investigate the inhibitory effects of LBA on Vibrio parahaemolyticus planktonic cells and biofilms. The minimum inhibitory concentrations (MICs) and minimal bactericidal concentrations (MBCs) of LBA against Vibrio parahaemolyticus were both identified as 4 mg/mL. LBA exerted antimicrobial effects against planktonic Vibrio parahaemolyticus cells by damaging their membranes, as revealed by reduced intracellular ATP concentrations, increased protein leakage, abnormal cell morphology and diminished membrane integrity after treatment. At 1/16 × MIC and 1/8 × MIC, LBA inhibited biofilm formation and downregulated the expression of some biofilm-related genes, which was confirmed by crystal violet staining, field-emission scanning electron microscopy (FESEM) observations, and real-time quantitative PCR analysis. Moreover, LBA inactivated Vibrio parahaemolyticus cells within biofilms (on polystyrene and stainless steel surfaces), destroyed biofilm structures on stainless steel surfaces, and also reduced the levels of polysaccharides and proteins in the biofilms. Therefore, LBA is a potential low-cost agent that can be used to control planktonic Vibrio parahaemolyticus and its biofilms.

Nanoscale architecture of ZrN/CrN coatings: microstructure, composition, mechanical properties and electrochemical behavior

The main aim of this study is to develop ZrN/CrN nanolayered coatings with bilayers periods 10 bilayers (10 L), 20 bilayers (20 L) and 30 bilayers (30 L) over AISI 304 stainless steel and also evaluating the effect of nanolayers architecture on their electrochemical behavior. The nanolayers were deposited from chromium and zirconium targets using the cathodic arc evaporation physical vapor deposition (Arc-PVD) technique in a nitrogen atmosphere. The nanolayer microstructure and morphology were evaluated using X-ray diffraction (XRD), atomic force microscopy (AFM), and field emission scanning electron microscopy (FE-SEM). The chemical composition was studied by energy-dispersive X-ray spectroscopy (EDS) tests. The electrochemical characterization was carried out by potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) tests in 3.5 wt. % NaCl solution in order to investigate changes in the electrochemical behavior as a function of the deposited bilayers number. The existence of CrN and ZrN phases with FCC lattices in the nanolayers were identified by the XRD patterns. The FE-SEM observations showed that the multilayered coatings were deposited at an excellent periodicity. The electrochemical tests indicated that the corrosion resistance of ZrN/CrN nanolayers is enhanced by increasing the number of bilayer periods that can be ascribed to the decrease in the pinholes and blocking the penetration path of corrosive solution.

3D crystal size distributions of pyroxene nanolites from nano X-ray computed tomography: Improved correction of crystal size distributions from CSDCorrections for magma ascent dynamics in conduits

Abstract Groundmass crystals indicate syneruptive magmatic conditions, and thus their crystal size distributions (CSDs) are used to infer magma ascent histories. Three-dimensional (3D) CSDs are most commonly estimated from two-dimensional (2D) observations and plotted against long-axis length, L (hereafter referred to as “L-plot CSDs”). However, L-plot CSDs have two significant problems: the error because of the conversion from 2D to 3D and a lowered sensitivity to changes in the degree of effective undercooling (ΔTeff), which arises because a crystal’s growth rate varies with ΔTeff most strongly along its long dimension. Although these problems can result in false interpretations of magma ascent dynamics, there has been little discussion of the influence of the size criteria on CSDs. In this study, we investigated which 3D size criterion [i.e., long (L), intermediate (I), or short (S) axis length] is optimum for 2D-estimated CSDs of groundmass crystals from two perspectives: (1) conformity with the actual distributions, and (2) the sensitivity of CSD slopes to the magma ascent conditions in the conduit. We observed groundmass pyroxene crystals in pumice clasts from sub-Plinian and Vulcanian eruptive phases during the 2011 eruption of Shinmoedake (andesitic volcano, Japan) by using synchrotron radiation-based X-ray computed nanotomography (SR-XCT) and field-emission scanning electron microscopy (FE-SEM) and rein-vestigated the crystallization kinetics of pyroxene nanolites ranging in width from a few hundred nanometers to 1 µm. The SR-XCT observations provided the detailed 3D shapes and 3D CSDs (CT-CSDs) of these nanolites directly. The FE-SEM observations allowed us to estimate 3D aspect ratios (S:I:L) and CSDs (SEM-CSDs). L-plot SEM-CSDs, acquired using the program CSDCorrections, were used to calculate S-plot SEM-CSDs and I-plot SEM-CSDs. We compared the data from FE-SEM with those from SR-XCT to evaluate the accuracy of 3D aspect ratios and CSDs estimated from 2D data. The L-plot SEM-CSDs from the sub-Plinian pumice sample showed significant inconsistencies with the CTCSD, a result of the difficulty in estimating representative 3D aspect ratios from 2D observations for elongated groundmass crystals. In contrast, the S- and I-plot SEM-CSDs kept the effect of aspect ratio to a minimum and preserved their actual slopes, except for a vertical discrepancy between the CSDs. Moreover, the slopes of S- and I-plot CSDs of the nanolites differed more markedly between the two eruptive styles (by ~20% more) than those of L-plot CSDs. For estimating magma ascent dynamics, we propose that the optimum method for acquiring SEM-CSDs is to measure the cross-sectional widths of crystals and convert the resulting 2D data set into S-plot CSDs. Our new finding that the 3D shapes and CSDs of pyroxene nanolites differ according to eruptive style means that nanolites indicate distinct differences in ascent histories at the shallow conduit: increasing ΔTeff just before sub-Plinian eruptions and decreasing ΔTeff before Vulcanian eruptions. Given the similarity in CSDs of micro-lites, our results suggest that eruptive style was determined in the shallow conduit. Monitoring the condition of the shallow conduit may contribute to predicting the time evolution of eruptive activity.

Towards the application of carboxymethyl chitin/ionic liquid blend as polymer electrolyte membrane for aqueous batteries

Carboxymethyl chitin (CMChit) has the potential to be used as a solid polymer electrolyte (SPE) based on its ionic conductivity value of the order of 10−6 S·cm−1 in self-standing membranes. In controlled humidity of 65RH%, carboxymethyl chitin based membrane blended with 1-Butyl-3-methylimidazolium acetate (BMIM[Ac]) ionic liquid (IL) (40 wt%) showed a threshold value of ionic conductivity in the order of 10−4 S·cm−1 and electrochemical stability was up to 2.93 V. The effects of the relative humidity and ionic liquid weight fraction on the ionic conductivity and structural changes were investigated in detail. Furthermore, the X-ray diffraction (XRD) diffractogram indicated a clear reduction of crystallinity of the CMChit. The Field-emission scanning electron microscopy (FESEM) observation of the cross-sections confirmed the homogeneity of the prepared blend. This electrolyte was tested in symmetric cells based on Zn//SPE//Zn and showed good reversibility and potential for application in proton-conducting batteries.

Development of Low-Molecular-Mass Organogelators: Synthesis and Physical Properties of N-Linear Saturated Fatty Acyl-GABAs and Their Ester Derivatives.

We determined that compounds in which γ-aminobutyric acid (GABA) and linear saturated fatty acids of various lengths are amide-bonded, as found in the human brain, have the ability to gelate organic solvents. We also synthesized compounds of these GABA derivatives attached to 1,5-anhydro-d-glucitol (1,5-AG) or d-glucopyranose (Glc) via ester linkages, and these compounds were also found to be able to gelate organic solvents. From the comparative experiments of gelation using various lengths of N-linear saturated fatty acyl-GABAs and their ester derivatives, it was determined that the compound of N-tetradecanoic acyl-GABA bonded to 1,5-AG via ester linkage (C14GABA-AG) had a particularly high gel hardness and could gelate various organic solvents. Furthermore, field-emission scanning electron microscopy observations revealed the formation of a fibrous structure, which encapsulates the organic solvent and forms a gel. A variable-temperature Fourier transform infrared spectroscopy analysis revealed that the alkyl chains of N-linear saturated fatty acyl-GABAs are packed with an all-trans conformation, whereas the alkyl chains of the ester compounds attached to 1,5-AG or Glc are slightly skewed from the all-trans conformation due to the intermolecular hydrogen bonding of the amide groups. Here, we report the synthesis and analysis of N-linear saturated fatty acyl-GABA derivatives and the gelation mechanism.

Development of Flowerlike Ce1-XZrxO2-δ-Dispersed Paper-Structured Catalyst for Direct-Biogas SOFC

Performance of direct internal reforming (DIR)-solid oxide fuel cell (SOFC) can be improved by the application of the paper-structured catalyst (PSC) on the anode material. In the ceramic fiber network of the PSC, any kinds of functional materials can be easily dispersed during paper-making process.The solid solution based on the equimolar mixture of ceria and zirconia (Ce0.5Zr0.5O2-δ), hereafter called CZ, is a promising oxide support of the Ni metal catalyst due to its high specific surface area and high oxygen storage capacity (OSC). By employing the two-step hydrothermal process developed in this study, we could successfully prepare the CZ with flowerlike geometry, which can prevent Ni from sintering under reducing atmosphere.Ni-loaded PSCs with and without the dispersion of CZ, Ni/CZ-PSC and Ni-PSC, respectively, were prepared. Structures of the PSCs were characterized by X-ray diffractometry (XRD), BET specific surface area measurement, field emission scanning electron microscopy (FESEM), inductively coupled plasma spectrometry (ICP) and thermogravimetric analysis (TG). Catalytic performances of these PSCs for the dry reforming of methane (DRM) in the feed of the equimolar mixture of CH4 and CO2 were evaluated by an automatic gas chromatograph (GC) with the posttest analysis by FESEM observation, temperature-programmed oxidation (TPO) and TG to estimate carbon deposition.In the durability (160 h) tests of the prepared-PSCs for DRM at 750oC under gas hourly space velocity (GHSV) of 2300 h-1 revealed that, for both cases with and without CZ dispersion, methane conversions were stable with the degradation rates (estimated after 10 h) of 13.7 and 21.8% 1000 h-1, respectively. TG measurements after the 160 h tests under oxidizing atmosphere in the range from 300 to 750oC revealed that the weights of the deposited carbon were 0.2 and 3.4 folds of those of PSCs for Ni/CZ-PSC and Ni-PSC, respectively. In the case without CZ dispersion (Ni-PSC), after the TG measurement to burn out the deposited carbon, Ni agglomeration and its detachment from the ceramic fiber could be clearly observed. On the other hand, for the Ni/CZ-PSC, these phenomena were considerably suppressed thanks to the flowerlike morphology for better dispersion of Ni metal particles and higher OSC of CZ solid solution to consume deposited carbon by the lattice oxygen.The developed PSCs will be applied on the anode of electrolyte-supported cell to demonstrate the stable operation of DIR-SOFC fueled by biogas (direct-biogas SOFC).

In vitro evaluation of the anti-proteolytic and cross-linking effect of mussel-inspired monomer on the demineralized dentin matrix

ObjectivesTo evaluate the anti-proteolytic and cross-linking effect of N-(3,4-dihydroxyphenethyl)methacrylamide (DMA) on the demineralized dentin matrix in vitro. MethodsFour experimental solutions were selected: 50% ethanol/water solution (Control); 1, 5, and 10 mmol/L DMA dissolved in 50% ethanol/water solution. Sound human molars were sectioned to produce dentin beams with dimension of 1×1×6 mm. The dentin beams were demineralized with 10% phosphoric acid for 8 h to remove the apatite. The demineralized specimens were randomly separated into four groups and immersed in the four experimental solutions for 1 h. After the treatment, the ultimate tensile strength (UTS), loss of dry mass and the release of hydroxyproline by storing the treated specimens in 0.1 mg/mL collagenase solution for 24 h were assessed. The swelling ratio of another ten specimens from each group were evaluated. The interaction between DMA with dentin matrix was observed under Field Emission Scanning Electron Microscopy (FESEM). UTS data was analyzed by two-way ANOVA followed by Tukey test, and the other data was analyzed by one-way ANOVA followed by Tukey test (α = 0.05). ResultsThe two-way ANOVA factors, different solutions (p < 0.001), collagenase degradation (p < 0.001) and their interactions (p < 0.001) all significantly affected the UTS. The 10 mM DMA treatment significantly decreased the percentage of loss of dry mass, release of hydroxyproline and swelling ratio of demineralized dentin matrix compared to other treatment groups (p < 0.05). The FESEM observation depicted that with increasing concentration of DMA, the structure of dentin matrix was protected and the porosity within dentin collagen network was decreased. ConclusionsThe treatment by 10 mM DMA/ethanol solution for 1 hour is capable of enhancing the mechanical properties of demineralized dentin matrix against collagenase degradation and may be clinically useful to improve the durability of hybrid layer. Clinical SignificanceThe 10 mM DMA/ethanol primer may offer an alternative choice for dentists to strengthen the mechanical properties of demineralized dentin matrix and resist its degradation by collagenase.

Inactivation Effect of Thymoquinone on Alicyclobacillus acidoterrestris Vegetative Cells, Spores, and Biofilms.

Alicyclobacillus acidoterrestris (A. acidoterrestris), a spore-forming bacterium, has become a main challenge and concern for the juices and acid beverage industry across the world due to its thermo-acidophilic characteristic. Thymoquinone (TQ) is one of the active components derived from Nigella sativa seeds. The objective of this study was to investigate antibacterial activity and associated molecular mechanism of TQ against A. acidoterrestris vegetative cells, and to evaluate effects of TQ on A. acidoterrestris spores and biofilms formed on polystyrene and stainless steel surfaces. Minimum inhibitory concentrations of TQ against five tested A. acidoterrestris strains ranged from 32 to 64 μg/mL. TQ could destroy bacterial cell morphology and membrane integrity in a concentration-dependent manner. Field-emission scanning electron microscopy observation showed that TQ caused abnormal morphology of spores and thus exerted a killing effect on spores. Moreover, TQ was effective in inactivating and removing A. acidoterrestris mature biofilms. These findings indicated that TQ is promising as a new alternative to control A. acidoterrestris and thereby reduce associated contamination and deterioration in the juice and acid beverage industry.