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.

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.

Resonance-enhanced multiphoton ionization/time-of-flight mass spectrometry for sensitive analysis of product ions formed by online concentration from analyte adsorption/laser desorption.

Resonance-enhanced multiphoton ionization/time-of-flight mass spectrometry (REMPI/TOFMS) was developed for the analysis of product ions formed by online concentration/laser desorption (Online COLD). In the online COLD system, which is one of the sample introduction techniques for REMPI/TOFMS, the analyte molecules are adsorbed at the tip of the capillary column and then are heated and vaporized by introducing a desorption laser. In the present study, the molecules concentrated at the tip reacted to the application of an intense desorption laser. The product species was dependent on the reactant, i.e., chlorodiphenyl ether was formed from p-chlorophenol while dibenzo-p-dioxin was formed from o-chlorophenol. In addition, the transient signal intensities of reactant and product ions were monitored, and the probable reaction processes were discussed. The present technique confers advantages such as high sensitivity/selectivity and rapidity, and therefore, this technique provides a novel method for monitoring the process of molecular reaction.

Fluorescence lifetime imaging microscopy for the monitoring of green fluorescent protein-tagged androgen receptors in living cells.

Fluorescence lifetime imaging microscopy (FLIM) was used to monitor the interaction between androgen receptor (AR) tagging of a green fluorescent protein (GFP) and the ligands in living cells. The fluorescence lifetime of the AR-GFP without ligands was ca. 3.1 ns, which was reduced to ca. 2.5 ns after treatment with agonist 5α-dihydrotestosterone. On the other hand, the fluorescence lifetime of AR-GFP was not changed after treatment with antagonist hydroxyflutamide. The reaction kinetics was simulated in the present study, and the obtained results indicated the possibility of the presence of an intermediate complex during the reaction. FLIM can be used to record the ratio of the AR as it reacts with an agonist, and, therefore, it is useful for acquiring information concerning the interaction between AR and ligands in living cells.

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.

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.

Analysis of dioxins by gas chromatography/resonance-enhanced multiphoton ionization/mass spectrometry using nanosecond and picosecond lasers.

Dioxins in a soil sample were measured using gas chromatography/resonance-enhanced multiphoton ionization/time-of-flight mass spectrometry coupled with different types of laser sources. The fourth-harmonic emission (266 nm) of a nanosecond Nd:YAG laser (1 ns) provided low ionization efficiency, especially for highly chlorinated dioxins/dibenzofurans (CDDs/CDFs). The ionization efficiency was improved using the fourth-harmonic emission (266 nm) of a picosecond Nd:YAG laser (4 ps), due to shorter singlet excited-state lifetimes. It was, however, difficult to efficiently ionize hepta-CDD and octa-CDD/CDF, because of their shorter lifetimes, which were induced by stronger spin-orbit coupling that led to efficient relaxation of the excited molecule to triplet levels. The ionization efficiency was substantially improved using the fifth-harmonic emission (213 nm) of the picosecond Nd:YAG laser (4 ps), in which the analyte molecule that was relaxed to triplet levels was efficiently ionized using a photon with sufficient energy for ionization, although the pulse energy obtained at 213 nm was only one-third of the pulse energy obtained at 266 nm. The limits of detection achieved for 17 toxic polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDDs/PCDFs) were 0.41-45 pg. The analytical instrument developed in the present study performed sufficiently well for the practical trace analysis of dioxins in soil samples.

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.].

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.

Online concentration by analyte adsorption/laser desorption for application to gas chromatography/resonance-enhanced multiphoton ionization time-of-flight mass spectrometry.

A novel sample introduction technique, based on online concentration by analyte adsorption/laser desorption, was applied to resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (REMPI-TOFMS). Signal enhancement and optical selectivity, based on supersonic jet spectrometry, were examined by measuring the REMPI spectra. This sample introduction technique was applied at the interface of a gas chromatograph (GC) and a mass spectrometer (MS). The signal intensity was enhanced ca. 80-fold, compared with that of a conventional technique based on continuous sample introduction. The analyte molecule was selectively measured using a tunable laser emitting at a wavelength of the 0-0 transition. With the use of a desorption laser, a linear calibration curve was extended over 4 orders of magnitude. The sensitivity, selectivity, and dynamic range were all superior for this sample introduction system, as were the inherent characteristics, e.g., a near-zero dead volume and thermal durability. This system would provide a useful means for practical trace analysis of aromatic hydrocarbons by GC/REMPI-TOFMS.

Gas chromatography/femtosecond multiphoton ionization/time-of-flight mass spectrometry of dioxins.

Gas chromatography/multiphoton ionization/time-of-flight mass spectrometry (GC/MPI/TOF-MS) was developed for trace analysis of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). The use of an ultraviolet femtosecond laser (266 nm) allowed the sensitive, as well as selective, determination of PCDD/Fs with short singlet-excited-state lifetimes; the detection limit was 19 fg for 1,3,6,8-tetraCDF. Performance of the analytical instrument was examined and was ascertained to be satisfactory for all the criteria (K0311) prescribed by the Japanese Industrial Standards (JIS). The relative ionization efficiencies of (12)C-native PCDD/Fs against (13)C-labeled PCDD/Fs were 1.002 +/- 0.012. This suggests that (13)C-labeled isotopes can be used as internal standards with no intensity calibration and that the concentrations of PCDD/Fs can be determined to within an error of ca. 1%. In addition, multiphoton ionization provides negligible levels of background interference for the real soil samples even with curtailed pretreatment. The toxicity equivalence (TEQ) of the real sample was determined using GC/MPI/TOF-MS for performance evaluation against high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). The results suggest equivalent or even superior performance for GC/MPI/TOF-MS, due to low background interference and to the ability to check the reliability of the assignment from the intensity distribution of the isotope peaks.

Enhancement of molecular ions in mass spectrometry using an ultrashort optical pulse in multiphoton ionization.

The spectral domain of an ultraviolet femtosecond laser was expanded by stimulated Raman scattering/four-wave Raman mixing, and the resulting laser pulse was compressed using a pair of gratings. The pulse width was then measured using an autocorrelator comprised of a Michelson interferometer equipped with a multiphoton ionization/mass spectrometer which was used as a two-photon detector. A gas chromatograph/mass spectrometer was employed to analyze triacetone triperoxide (TATP), and the molecular ion induced by multiphoton ionization was substantially enhanced by decreasing the laser pulse width.

Application of Hadamard transform to gas chromatography/nonresonant multiphoton ionization/time-of-flight mass spectrometry.

The technique of Hadamard transform was successfully coupled with GC/nonresonant multiphoton ionization/TOFMS, for the first time. 1,4-Dichlorobenzene and the fourth harmonic generation (266 nm) of a Nd:YAG laser were employed as a model sample and an ionization laser, respectively. A Hadamard-injector coupled with a capillary-based supersonic jet nozzle (capillary-injector) was also developed in this study. The Hadamard-injector was used to obtain the chromatogram, which was encoded by successive sample introduction based on Hadamard codes, and the capillary-injector was used for injection of GC-elutes into TOFMS. Compared with a conventional single injection method, the S/N ratios were substantially improved after inverse Hadamard transformation of the encoded chromatogram. Under optimized conditions, when Hadamard matrices of 103 and 255 were used, the S/N ratios of the signals for 1,4-dichlorobenzene (concentration level, 4 microg/1 mL ACN) were substantially improved to 4.1- and 6.6-fold, respectively, and those improvements are in good agreement with those obtained by theory (5.1- and 8.0-fold).

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.

Gas chromatography/time-of-flight mass spectrometry of triacetone triperoxide based on femtosecond laser ionization.

Triacetone triperoxide (TATP), which is used as an explosive in acts of terrorism, was measured by means of gas chromatography/multiphoton ionization/time-of-flight mass spectrometry using a deep-ultraviolet (deep-UV) femtosecond laser as an ionization source. The fragmentation process was investigated by changing the intensity of the laser at the center axis of a molecular beam. A molecular ion was observed using a femtosecond laser, and the ratio of the intensities of the molecular and fragment ions decreased as the intensity of the laser increased. These results suggest that TATP can be efficiently ionized using a deep-UV, ultrashort optical pulse. Furthermore, fragmentation was accelerated by excess energy supplied through higher-order multiphoton processes under a strong radiation field. The detection limits obtained using the molecular ion and two dominant fragment ions, C(2)H(3)O(+) and CH(3) (+), were determined to be 670, 83 and 150 pg, respectively.

Data processing technique in gas chromatography/time-of-flight mass spectrometry.

A complete mass spectrum was measured at an acquisition rate of 1 kHz using a femtosecond-multiphoton-ionization time-of-flight mass spectrometer for analyte eluting from a gas chromatograph. A contour-map display, i.e. a two-dimensional plot, of the data was first constructed for a simultaneous overview of the mass spectra and the mass chromatograms. The noise component in the signal was then reduced by digital filtering and reduced further by smoothing the data. The detection limit (S/N = 3) was improved from 240 to 76 fg for 2,3,4,6,7-pentachlorodibenzofuran, with no appreciable loss of resolution in the chromatogram. The achieved value was lower than the value (<100 fg) required by Japanese Industrial Standards for dioxin analysis. A new parameter, referred to as a 'reliability factor', was defined in this study to calculate the similarity between the intensity distribution of the isotope peaks observed in the mass spectrum and that calculated from the natural abundance ratio of the isotopes. This parameter was useful for evaluation of the purity of the chromatographic peak.

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.

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.