Sample preparation conditions for the real-time measurement of W/O emulsions by resonance-enhanced multiphoton ionization time-of-flight mass spectrometry.

Analysis of an emulsion in its original dispersed condition is quite important for quality assessment and quality control. In the present study, the practical experimental conditions of the real-time measurement of a water-in-oil (W/O) emulsion were examined via resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (REMPI-TOFMS). A W/O emulsion was prepared using cyclohexane as the oil phase with toluene as an analyte species. A time profile of the peak area for toluene was constructed based on the mass spectra. Normally, the negative spikes of a base signal are detected in a time profile when analyte molecules are dispersed in an oil phase. In this case, however, the positive spikes were unexpectedly detected rather than the negative ones. Though several factors could be relevant for the occurrence of the positive spikes, these spikes could have been suppressed by the addition of a small amount of n-alkane when the oil phase was prepared in the present study. The practical experimental conditions for the analysis of a W/O emulsion in real-time revealed that this method would be applicable to the analysis of an oil-in-water-in-oil (O/W/O) emulsion where the outer phase is also an oil phase.

Optimization of Sulfide Annealing Conditions for Ag8SnS6 Thin Films.

Ag8SnS6 (ATS) has been reported to have a band gap of 1.33 eV and is expected to be a suitable material for the light-absorbing layers of compound thin-film solar cells. However, studies on solar cells that use ATS are currently lacking. The objective of this study is to obtain high-quality ATS thin films for the realization of compound thin-film solar cells using vacuum deposition and sulfide annealing. First, glass/SnS/Ag stacked precursors are prepared by vacuum deposition. Subsequently, they are converted to the ATS phase via sulfide annealing, and various process conditions, namely, annealing time, annealing temperature, and number of steps, are studied. By setting the heat treatment temperature at 550 °C and the heat treatment time at 60 min, a high-quality ATS thin film could be obtained. Multi-step heat treatment also produces thin films with nearly no segregation or voids.

Handedness anomaly in a non-collinear antiferromagnet under spin-orbit torque.

Non-collinear antiferromagnets are an emerging family of spintronic materials because they not only possess the general advantages of antiferromagnets but also enable more advanced functionalities. Recently, in an intriguing non-collinear antiferromagnet Mn3Sn, where the octupole moment is defined as the collective magnetic order parameter, spin-orbit torque (SOT) switching has been achieved in seemingly the same protocol as in ferromagnets. Nevertheless, it is fundamentally important to explore the unknown octupole moment dynamics and contrast it with the magnetization vector of ferromagnets. Here we report a handedness anomaly in the SOT-driven dynamics of Mn3Sn: when spin current is injected, the octupole moment rotates in the opposite direction to the individual moments, leading to a SOT switching polarity distinct from ferromagnets. By using second-harmonic and d.c. magnetometry, we track the SOT effect onto the octupole moment during its rotation and reveal that the handedness anomaly stems from the interactions between the injected spin and the unique chiral-spin structure of Mn3Sn. We further establish the torque balancing equation of the magnetic octupole moment and quantify the SOT efficiency. Our finding provides a guideline for understanding and implementing the electrical manipulation of non-collinear antiferromagnets, which in nature differs from the well-established collinear magnets.

Characterization of Cooked Nonglutinous Rice Cultivars Based on Flavor Volatiles and Their Change during Storage.

Characterizing fleshly cooked rice cultivars according to the volatile aroma compounds helps consumers select a favorite and is useful for the development of new cultivars that will have a pleasant aroma. In the present study, six Japanese nonglutinous cultivars, which were freshly harvested in 2021, were characterized based on their flavor volatiles after being freshly cooked. In order to extract the volatile compounds just after cooking, the vaporized compounds were extracted for 5 min using a solid-phase microextraction (SPME) fiber and were measured via gas chromatography/mass spectrometry (GC/MS). Multiple comparison tests statistically detected four volatile aroma compounds: 2-pentylfuran, nonanal, 4-vinylphenol, and indole. From among the six rice cultivars tested, the proportions of the latter two compounds showed significant differences, and in principal component analysis of cooked rice, these two best characterized freshly harvested and freshly cooked Japanese nonglutinous rice cultivars; indole was indicative of Nipponbare, and 4-vinylphenol was indicative of Koshihikari and Ichihomare. In the present study, changes in the volatile aroma compounds of the freshly cooked rice cultivars were found to slightly differentiate according to storage times: 2-pentylfuran tended to increase, nonanal first increased and then decreased, and 4-vinylphenol and indole either remained almost unchanged or were only slightly decreased during storage. Therefore, establishing the differences in rice cultivar types revealed that the characteristics of the flavor volatiles of freshly cooked rice after long-term storage significantly depend on how the rice cultivar is stored.

Using Resonance-Enhanced Multiphoton Ionization Time-of-Flight Mass Spectrometry to Evaluate the Movement of a Constituent in a Multiple Emulsion.

Herein, we propose a method for evaluating the movement of a constituent in a multiple emulsion while maintaining its original dispersed condition. In this study, an oil-in-water-in-oil (O1/W/O2) emulsion was prepared using a two-step emulsification method with styrene as an analyte species in the inner phase (O1). The emulsion was measured using resonance-enhanced multiphoton ionization time-of-flight mass spectrometry without pretreatment such as centrifugation. From a series of obtained mass spectra, a time profile for the peak areas arising from styrene was constructed. When the emulsion was measured immediately following preparation, a time profile composed of a base, positive, and negative signals confirmed the presence of styrene in the O2, O1, and W phases, respectively. Moreover, while a small amount of styrene was present in the inner O1 phase, almost all of the styrene was found in the outer O2 phase. Furthermore, the results of the obtained time profile were converted into a box plot, and a method for the selection of the base, positive, and negative signals was tentatively determined. Then, the movement of styrene among the phases could be evaluated using the time courses of these signals; the time constant of the movement of styrene from an O1/W droplet to the O2 phase was calculated to be 0.8 h.

Quantitative Evaluation of the Creaming of Emulsions via Resonance-Enhanced Multiphoton Ionization Time-of-Flight Mass Spectrometry.

The creaming behavior of an oil-in-water (O/W) emulsion was quantitatively evaluated via resonance-enhanced multiphoton ionization time-of-flight mass spectrometry. Styrene O/W emulsions were prepared with initial styrene concentrations of 1 and 4 g/L, and the height at the center of the sample was monitored. A peak area of the molecular ion of styrene was set as the signal intensity, for which a time profile was constructed from a series of mass spectra. As a result, the averaged time profiles showed that the signal intensities increased once and then decreased with the onset of creaming. In addition, in order to fit an experimentally obtained time profile, a modified fit function was proposed. Based on the fit results, the ratios of the increases and decreases in signal intensities were different between the two emulsions-higher in the case of an O/W emulsion with a higher initial oil concentration. On the other hand, the duration of the enhancement of the signal intensity with the onset of creaming was independent of the initial oil concentration. The present method offers the possibility to quantitatively evaluate the creaming behavior of an emulsion without pretreatment, and, therefore, would be useful for confirming the stability and quality assurance of emulsions.

Correction to "Using Resonance-Enhanced Multiphoton Ionization Time-of-Flight Mass Spectrometry to Quantitatively Analyze the Creaming of an Emulsion".

[This corrects the article DOI: 10.1021/acsomega.9b02930.].

Characteristic Signal Behaviors for Water-in-Oil and Oil-in-Water Emulsions Measured by Resonance-Enhanced Multiphoton Ionization Time-of-Flight Mass Spectrometry.

Resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (REMPI-TOFMS) was used to study the characteristic signal behaviors obtained from two types of emulsions: water-in-oil (W/O) and oil-in-water (O/W). All emulsions were prepared using phase inversion emulsification, i.e., a solution for an aqueous phase was added dropwise to an oil phase with constant stirring to obtain an emulsion. Toluene served as a detection component. When using REMPI-TOFMS to measure an emulsion, a time profile for the target component can be constructed by plotting peak areas for the corresponding component on a series of mass spectra. In the case of a W/O emulsion at a water volume fraction (f w) of 0.005, the concentration of toluene was instantaneously decreased due to the existence of water droplets, and therefore, several negative spikes were detected on the time profile while establishing a baseline. In the case of a W/O emulsion at f w = 0.3, negative peaks consisting of several plots appeared on the time profile because of the formation of aggregates of water droplets while the emulsion was flowed through a capillary column for sample introduction. An O/W emulsion at f w = 0.995 was analyzed following phase inversion, and positive peaks were detected due to the aggregates of many oil droplets. In this manner, the direct mass analysis of emulsions before and after phase inversion was achieved, and the resultant signal inversion was confirmed via REMPI-TOFMS.

Using SPME-GC/REMPI-TOFMS to Measure the Volatile Odor-Active Compounds in Freshly Cooked Rice.

The volatile odor-active compounds of cooked rice were evaluated using a method that combined solid-phase microextraction (SPME) with gas chromatography-resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (GC/REMPI-TOFMS). An SPME fiber was held at the upper levels of the cooked rice and given an extraction time of 5 min. By using a nanosecond ultraviolet (266 nm) pulsed laser for ionization, two compounds, 4-vinylphenol and indole, which are considered to be important for the characteristic flavor of cooked rice, could be detected from all types of cultivars measured in the present study-nonglutinous rice, glutinous rice, and aromatic rice. In the case of fresh nonglutinous rice, the amounts of introduction for 4-vinylphenol and indole to GC were ca. 70 and 20 pg, respectively. While both peak areas decreased with increases in the time needed to maintain warmth, the decreasing behaviors differed slightly with a noteworthy rapid decrease for indole. For nonglutinous rice, the peak areas for 4-vinylphenol were almost the same, whether it was fresh (measured within 1 month from harvest) or aged (measured 6-12 months after harvest), but those of indole significantly decreased following storage. We also found differences among cultivars: the peak area for 4-vinylphenol in nonglutinous rice was somewhat strong; the peak area for indole was intensely strong in glutinous rice; however, the peak areas for both 4-vinylphenol and indole were weak in aromatic rice. Volatile odor-active compounds were detected in a sensitive and time-resolved manner; therefore, the proposed method could be useful for differentiating varieties of cooked rice from the viewpoints of cooking conditions, freshness, and cultivar types.

Using Resonance-Enhanced Multiphoton Ionization Time-of-Flight Mass Spectrometry to Quantitatively Analyze the Creaming of an Emulsion.

In this study, we used a quantitative analytical method to indicate creaming behavior in an emulsion. An oil-in-water emulsion was directly measured by resonance-enhanced multiphoton ionization time-of-flight mass spectrometry, and the time profiles of the peak areas of an oil component, styrene, were obtained at heights of 1, 2, and 3 cm from the bottom of a sample that had a height of 4 cm. All time profiles roughly indicated that the signal intensity increased once, then decreased, and finally settled. Moreover, we proposed a fitting equation for the time profiles by subtracting two sigmoid functions, whereby the degree of the signal increases at the initial stage, the degree of the signal decreases after the increase, and the times for continuing the higher signal intensities were all longer as the monitoring positions were raised. This method would surely provide useful information about emulsions that undergo creaming behavior.

Resonance-enhanced Multiphoton Ionization Time-of-Flight Mass Spectrometry for Evaluating Emulsion Inversion via Temperature Change.

This study used resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (REMPI-TOFMS) to evaluate the phase inversion that is driven via temperature change. A change in temperature prompts phase inversion in an oil-in-water (O/W) emulsion that uses a nonionic surfactant as an emulsifier. In this study, an O/W emulsion was prepared containing Triton X-100 as an emulsifier. To promote emulsion inversion, we heated only the outlet of a capillary column that was used for sample introduction during REMPI-TOFMS. When the emulsion was continuously measured at 40°C, several intense spikes could be detected on a time profile for the analyte, toluene, constructed by extracting the peak areas from a series of obtained mass spectra. This indicated the presence of toluene droplets in the O/W emulsion. No intense spikes appeared at 80°C, however, which suggested the shrinkage or even disappearance of the oil droplets following phase inversion. Using this technique, an emulsion can be measured without affecting the influence of vaporization even at elevated temperatures, which surely is a serious concern when using other analytical techniques. Therefore, this technique would be quite useful for evaluating the phase inversion of an emulsion at elevated temperatures.

Evaluating the Creaming of an Emulsion via Mass Spectrometry and UV-Vis Spectrophotometry.

The creaming behavior of a turbid oil-in-water emulsion was observed via the processes of multiphoton ionization time-of-flight mass spectrometry (MPI-TOFMS) and ultraviolet-visible spectrophotometry (UV-vis), and the results were compared. The transmittance measurement by UV-vis showed that the turbidity of the toluene emulsion was decreased with time. However, non-negligible errors are common in the measurement of a sample with high turbidity. The online measurement by MPI-TOFMS detected many spikes in the time profile, which revealed the existence of toluene droplets in the emulsion. A smooth time profile suggested that the signal intensity had initially increased, and then decreased with time; the initial concentration of toluene was 3 g/L, which had decreased by half after 60 min. The signal behavior obtained using MPI-TOFMS differed only slightly from that obtained using UV-vis. Since a change in turbidity is not the same as a change in the local concentration of an oil component, MPI-TOFMS is useful for the analysis of a turbid emulsion and offers additional information concerning the creaming phenomenon of an emulsion.

A Quantitative Analysis of an Oil Component in an Emulsion by Multiphoton Ionization Mass Spectrometry.

The first quantitative analysis of an oil component in an emulsion was achieved by multiphoton ionization time-of-flight mass spectrometry (MPI-TOFMS). An oil-in-water (O/W) emulsion was prepared. Styrene (0 - 5000 ng µL-1) and Triton X-100 were used as the oil phase and the disperser, respectively. Toluene was employed as an internal standard. We obtained a series of mass spectra, and then constructed the time profiles for styrene and toluene. As a result, we found several spikes from both time profiles when measuring emulsions with higher concentrations of styrene. Moreover, the timing of spikes for toluene coincided with that of styrene. These results suggested the movement of toluene into styrene droplets in the prepared emulsion. Furthermore, we constructed calibration curves of styrene using both the absolute calibration curve method and an internal standard method. Linear calibration curves were obtained in the concentration range investigated in the present study; the coefficients of determination obtained by both methods were 0.9956 and 0.9986, respectively.

Online Monitoring of a Styrene Monomer and a Dimer in an Emulsion via Laser Ionization Time-of-Flight Mass Spectrometry.

Laser ionization time-of-flight mass spectrometry was applied to the online monitoring of a styrene monomer and dimer in an emulsion. During the measurement of a styrene monomer oil-in-water emulsion for this study, a styrene dimer, 1,3-diphenylpropane, was dropped into the emulsion. As a result, signal spikes from both analytes occurred simultaneously, which suggested that either the dimer had moved to the monomer droplets or that the monomer and dimer droplets had aggregated. We concluded that this method could be useful for the direct monitoring of monomers and oligomers in the early stages of emulsion polymerization.

Application of Laser Ionization Time-of-Flight Mass Spectrometry for the Direct Measurement of a Silane Coupling Agent in Slurries.

Laser ionization time-of-flight mass spectrometry (LI-TOFMS) was applied to the direct measurement of a silane coupling agent in slurries. In the present study, a slurry with dispersed TiO2 nanoparticles treated with phenyltriethoxysilane (PTES) was prepared. As a result, the peaks for PTES could be observed from the slurry sample containing unreacted PTES, and no peaks were observed from the slurry sample where unreacted PTES was removed by washing. This method can be used to directly analyze surface coating agents, such as PTES in slurries, and would be useful for obtaining a direct understanding of the characteristics of slurries.

Time-Profile Measurement of an Emulsion Using Multiphoton Ionization Time-of-Flight Mass Spectrometry in Combination with a Microscope.

Multiphoton ionization time-of-flight mass spectrometry was applied to the measurement of an oil-in-water emulsion that contained toluene as a dispersed phase. Before the measurement, the sample was sufficiently creamed, and then stirred for a short period of time for dispersion. As a result, several intense spikes appeared on the time profile constructed from the peak area for toluene. In the present study, an optical microscope was used to observe the capillary column for sample introduction, and small toluene droplets along with their aggregates were found in the images of the emulsion flowing through the capillary. The aggregates produced intense spikes comprised of multiple plots, which could be easily marked by applying a moving median filter. In the present study, droplets with minimum diameters as small as 2.9 µm, which corresponds to 13 fL, could be calculated as detectable spikes.

Evaluating the Translational Temperature of Molecules Laser-desorbed after Online Concentration Using Multiphoton Ionization Time-of-Flight Mass Spectrometry.

We describe a new technique for evaluating the translational temperature of molecules by applying online concentration via analyte adsorption/laser desorption, which is a sample-introduction technique for resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (REMPI-TOFMS). In the present study, analyte molecules were adsorbed via a narrowed capillary tip once, and then the flow of the carrier gas containing the analyte was stopped. After laser desorption, the ion signals induced by REMPI were monitored. Finally, the translational temperature could be calculated from the velocity distribution of the desorbed molecules by applying a Maxwell distribution.

Evaluating the Aging of Multiple Emulsions Using Resonance-Enhanced Multiphoton Ionization Time-of-Flight Mass Spectrometry.

Resonance-enhanced multiphoton ionization time-of-flight mass spectrometry was applied to measurements of multiple emulsions with no pretreatment; a method for the quantitative evaluation of aging was proposed. We prepared water-in-oil-in-water (W/O/W) multiple emulsions containing toluene and m-phenylenediamine. The samples were measured immediately following both preparation and after having been stirred for 24 h. Time profiles of the peak areas for each analyte species were obtained, and several intense spikes for toluene could be detected from each sample after stirring, which suggests that the concentration of toluene in the middle phase had increased during stirring. On the other hand, in the case of a W/O/W multiple emulsion containing phenol and m-phenylenediamine, spikes for m-phenylenediamine, rather than phenol, were detected after stirring. In the present study, the time-profile data were converted into a scatter plot in order to quantitatively evaluate the aging. As a result, the ratio of the plots where strong signal intensities of toluene were detected increased from 8.4% before stirring to 33.2% after stirring for 24 h. The present method could be a powerful tool for evaluating multiple emulsions, such as studies on the kinetics of the encapsulation and release of active ingredients.