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Initial analyses showed that asteroid Ryugu's composition is close to CI (Ivuna-like) carbonaceous chondrites (CCs) - the chemically most primitive meteorites, characterized by near-solar abundances for most elements. However, some isotopic signatures (for example, Ti, Cr) overlap with other CC groups, so the details of the link between Ryugu and the CI chondrites are not yet fully clear. Here we show that Ryugu and CI chondrites have the same zinc and copper isotopic composition. As the various chondrite groups have very distinct Zn and Cu isotopic signatures, our results point at a common genetic heritage between Ryugu and CI chondrites, ruling out any affinity with other CC groups. Since Ryugu's pristine samples match the solar elemental composition for many elements, their Zn and Cu isotopic compositions likely represent the best estimates of the solar composition. Earth's mass-independent Zn isotopic composition is intermediate between Ryugu/CC and non-carbonaceous chondrites (NCs), suggesting a contribution of Ryugu-like material to Earth's budgets of Zn and other moderately volatile elements.

Carbonates are ubiquitous minerals carrying important information on aqueous environments where they precipitated on the Earth and space. While their ideal chemical formulae are denoted as simple as MCO3 or M1M2(CO3)2 (M: metal cations), natural carbonates generally form solid-solution series and their compositions deviate from the ideal formulae. Since their cation composition due to the substitution provides a sensitive indicator for chemical and thermodynamic environments of aqueous solutions where they precipitated, their composition analysis has been widely carried out from the environmental/geochemical/astrochemical aspects. However, in widely used back-scattered electron and energy dispersion X-Ray analyses, samples should be generally sliced and/or their surface be polished prior to the measurements. For analyzing rare samples with small sizes, such as ones sampled from deep-sea and/or meteorites and asteroids, a non-destructive method without any pretreatments has been strongly desired. Here, a novel analytical method for discriminating various carbonates with Raman micro-spectroscopy is demonstrated, showing that the biaxial plot of the peak frequencies of their lattice modes linearly moves upon partial substitution of the cations. The cation substitution leads to linear movement in the biaxial map, and the slopes of the movement were different for Mg2+-Fe2+ and Mn2+-Fe2+ substitutions. This finding suggests that the micro-Raman analysis would be a non-destructive analytical method for evaluating the relative amount of Mg2+, Fe2+, and Mn2+ in dolomite-ankerite-kutnohorite solid-solution series, as well as Mg2+/Fe2+ ratio for magnesite-breunnerite-siderite. It would be helpful for analyzing the present and past terrestrial and cosmochemical environments. Graphical abstract

Correction to: Nature Astronomy https://doi.org/10.1038/s41550-022-01846-1. Published online 12 December 2022.

The 13th Symposium on Polar Science/Ordinary sessions [OA] Antarctic meteorites, Thu. 17 Nov.

Carbonaceous meteorites are thought to be fragments of C-type (carbonaceous) asteroids. Samples of the C-type asteroid (162173) Ryugu were retrieved by the Hayabusa2 spacecraft. We measured the mineralogy and bulk chemical and isotopic compositions of Ryugu samples. The samples are mainly composed of materials similar to those of carbonaceous chondrite meteorites, particularly the CI (Ivuna-type) group. The samples consist predominantly of minerals formed in aqueous fluid on a parent planetesimal. The primary minerals were altered by fluids at a temperature of 37° ± 10°C, about 5.2 − 0.7 + 0.8 million (statistical) or 5.2 − 2.1 + 1.6 million (systematic) years after the formation of the first solids in the Solar System. After aqueous alteration, the Ryugu samples were likely never heated above ~100°C. The samples have a chemical composition that more closely resembles that of the Sun’s photosphere than other natural samples do.

Hypothesis While dynamics of particles in slurries is usually evaluated by dynamic light scattering measurements, this technique had only been applicable to particles in the bulk slurries. Because this limitation is mainly owing to strong reflection of light, the dynamics of particles in slurries spreading/drying on solid substrates is to be obtained by spatially separating the reflection light from scattering (signal) light. This may allow us to track the particles in practical samples such as cosmetics or inks spreading on solid surfaces. Experiment We developed novel “dark-field dynamic light scattering microscopy”. The system was evaluated with test samples of polystyrene beads dispersed in several viscosities of bulk glycerol aqueous solutions. This setup was then applied to slurries spreading/drying on planar and nonplanar substrates. Findings The results for planar surface indicate that origin of coffee-ring are the particles flowing into the edge of the droplet just before complete drying. On a skin-modelled nonplanar substrate, the slurry on bumps was found to maintain semi-dry condition longer than that at dents. This suggests that the dispersive medium was supplied to bumps from dents. This unique flow was explained as effective drying from the bumps increased surface tension at the bumps to pull up the liquid around.

Since the elasticity of biological tissues is related to their pathological states, the development of new methods allowing for non-invasive measurements of the elasticity has been desired in the medical field. We present a characterization of the elasticity of objects buried in media from the temporal waveforms of photoacoustic signals. As the increment in Young's moduli of the objects, the frequency corresponding to the gravitational center of the power spectra obtained by the Fourier-transformation of the waveforms is increased. In our experiment configuration, the elasticity of buried objects is able to be identified up to about 1 MPa of Young's modulus from the frequency. These results suggest that measurements on the temporal waveforms of photoacoustic signals and the resultant power spectra would provide a useful method for evaluating the elasticity of deeply-situated microscopic pathological lesions, such as stage 0 or 1 mammary gland cancer, which is difficult by conventional ultrasound elastography.

We developed an instrument that allows us to measure dynamic light scattering from soft materials on solid substrates by avoiding strong background due to the reflection light from substrates. In the instrument, samples on substrates are illuminated by evanescent-light field and the resultant scattered light from the samples is collected with a dark-field optical configuration by employing a high numerical aperture microscope objective. We applied the instrument to measure the dynamic properties of supported lipid bilayers (SLBs), which have been widely utilized in industries as functional materials such as biosensors. From the time course of the scattered light from the SLBs, the power spectrum with the broad peak ranging from 10 to 20 kHz is observed. The use of the microscope objectives enables us to apply the instrument to future light scattering imaging for dynamic properties of soft materials supported on various substrates by combining with conventional microscope systems.

Water adsorption onto a material surface is known to change macroscopic surface properties such as wettability and friction coefficient. While the role of the adsorbed water has been discussed for a long time, the interfacial structure of the adsorbed water has not been fully recognized in many cases. In this study, the hydration structure of water adsorbed on a vapor/silica interface at room temperature was studied via heterodyne-detected vibrational sum-frequency generation spectroscopy. The vibrational spectra of the interfacial molecules obtained here were different from those estimated via conventional sum-frequency generation spectroscopy. Interestingly, our results suggest that, at low humidity, the adsorbed water on silica forms nanodroplets instead of a uniform film. Because no silanol group was found to be hydrogen-bonding free, it was concluded that water molecules gather around the silanol group to form strongly hydrogen-bonded droplets. At high humidity, while the adsorbed water partially behaves like a bulk liquid, deprotonation of the silanol was not observed, unlike the case of silica surfaces in contact with bulk liquid water.

A near-infrared laser-induced surface deformation (NIR-LISD) microscope is developed and is applied to the dynamic viscoelastic measurements of the surface of a living plant cell. In the microscope, the deformation of the surface is induced by an NIR laser beam, and then the change in intensity of the probe beam reflected from the surface reflects its viscoelasticity. The application of the NIR laser beam has a great advantage for the prevention of damage to the plant cell compared to the irradiation of a visible laser beam in LISD measurements. The NIR-LISD microscope allows for discriminating the differences in power spectra between the subapical and lateral regions of single rhizoids. It is a useful method for the dynamic viscoelastic measurements of cells, such as plant cells, that are damaged due to the strong absorption of ultraviolet or visible light.

Water adsorption onto a material surface is known to change macroscopic surface properties such as wettability and friction coefficient. While the role of the adsorbed water has been discussed for a long time, the interfacial structure of the adsorbed water has not been fully recognized in many cases. In this study, the hydration structure of water adsorbed on a vapor/silica interface at room temperature was studied via heterodyne-detected vibrational sum-frequency generation spectroscopy. The vibrational spectra of the interfacial molecules obtained here were different from those estimated via conventional sum-frequency generation spectroscopy. Interestingly, our results suggest that, at low humidity, the adsorbed water on silica forms nanodroplets instead of a uniform film. Because no silanol group was found to be hydrogen-bonding free, it was concluded that water molecules gather around the silanol group to form strongly hydrogen-bonded droplets. At high humidity, while the adsorbed water partially behaves like a bulk liquid, deprotonation of the silanol was not observed, unlike the case of silica surfaces in contact with bulk liquid water.

Raman scattering microscopy enables us to obtain chemical-contrast images with a high spatial resolution at the functional group level. This is because the Raman scattering signals derive from the normal vibrations of corresponding molecular and/or crystal structures. When stimulated Raman scattering (SRS), one of the coherent Raman scattering processes, is applied, not only the intensity but also the phase information of the chemical-contrast signal is preserved. Therefore extraction of the phase information by combining an optical interferometer with a Raman scattering microscope can lead to chemical-contrast imaging with higher spatial resolution, especially in the depth direction, than that of conventional optical Raman scattering microscope. The authors’ group has developed an SRS interferometer and a differential interference contrast SRS microscope for the first time, as core techniques for chemical-contrast topography and tomography with higher depth resolution than that of the conventional Raman scattering microscopy.

Since much attention has been paid to in vivo biological functions of G-quadruplexes, structural analyses of G-quadruplexes are essential for understanding their functional mechanisms. Here, we established a simple optical-spectroscopy-based method for the estimation of G-quartet-forming guanines in parallel-type G-quadruplexes using measurements of circular dichroism and the thermal melting temperature.

Development of a stimulated Raman scattering (SRS) interferometer is presented. In the apparatus, a SRS signal generated in a sample is collinearly overlapped with a reference beam, and the interference pattern between the signal and reference beams is obtained. From the interference pattern, the phase of the SRS signal can be measured. From the phase of the signal, the spatial distribution of the target molecule can be obtained with high positioning precision. In the present article, the SRS interferometer was developed and the first SRS interference signal was obtained from a polyethylene film. The phase change of the SRS interference pattern caused by scanning the sample position along the direction of the incident light propagation was measured. From the result, the sample position difference for a sub-micron was detected with uncertainties of 15%. The tomographic images of a triple-layered polymer film were successfully obtained. The SRS interferometer would become a core optical technique of a novel molecular-selective tomographic imaging method.

The development of a stimulated Raman scattering (SRS) microscope with a wavefront modulation unit is presented. In the apparatus, two beams for introducing the SRS process were focused into the sample with an objective lens. In the pathway of the Stokes beam, which is one of the two incident beams, a spatial light modulator (SLM) was located. Using the SLM, the wavefront of the Stokes beam was modulated to make the shape of the focal point a concentric circular pattern. By this spot shaping technique, the area where the SRS signal generates is restricted. The instrument response function (IRF) of the SRS microscope was examined by measuring the SRS intensity while scanning the sample position. From the result, the width of the IRF was reduced by about 15% by the wavefront modulation. It is suggested that the introduction of SLM is a way to improve the IRF of vibrational spectroscopic microscopes.

The temperature thawing, as called tempering, of triacylglycerols (TAGs) is an important processing method in food productions, such as chocolates, cream, confections, and spreads. Especially, melt-mediation by temperature thawing is famous in chocolate production for controlling the polymorphic crystalline forms and accelerating crystallization. In the present study, we investigated the α-melt structure of 1,3-dipalmitoyl-2-oleoyl-sn-glycerol (POP), one of the major continuants of cacao butter, under a phase transition from its melt to γ-crystal with in-situ attenuated total reflection-infrared (ATR-IR) spectroscopy. The differential IR spectrum between α-melt via temperature thawing (α-melt mediation) and melt via simple cooling revealed that crystal-like local ordered structures remained in part in the α-melt, and that they acted as nuclei for a rapid phase transition to the γ-crystal. The changes to the γ-crystal occur in the local ordered structures at first from the glycerol moiety to the acyl chains in the crystallization, providing an important suggestion concerning the mechanism for the acceleration of crystallization to the γ-form via α-melt mediation.

Water repellency of surfaces is realized by the roughness of the surfaces and the coating compounds on the surfaces. It is known that the water repellent surfaces are due to invasion of water into the trench structures on the surface, or due to air remaining in the trench structures. However, for more effective designing and fabrication of water-repellent surfaces, it is essential to measure the spatial distribution of water around the microstructures. In the present study, the SRS interferometer developed by the authors is applied to distinguish whether water or air is present in the trenches on the water-substrate interface buried by water. By obtaining the SRS interference signal generated from water while scanning the sample position, the phase shift of the SRS interference signal due to the microstructure on the interface was observed. From the quantitative analysis of the phase difference, it was revealed that the trench was filled with water. It is concluded that SRS interferometry is an effective method to observe experimentally the interface condition with chemical contrast along microstructures.

RNAs play essential roles in various cellular processes and can be used as biomarkers. Hence, it is important to detect endogenous RNA for understanding diverse cellular functions and diagnosing diseases. To construct a low-cost and easy-to-use RNA detection probe, a chemically unmodified RNA aptamer that binds to a pro-fluorophore to increase its fluorescence is desirable. Here, we focused on Broccoli, a superior variant of Spinach, which is a well-known fluorescent RNA aptamer that binds to DFHBI-1T and emits green fluorescence. We experimentally characterized Broccoli and predicted that it forms a G-quadruplex–based DFHBI-1T recognition region sandwiched between two stems. Based on this, we designed a Broccoli-based RNA detection probe (BRD probe) composed of a sequence of destabilized Broccoli fused with complementary sequences against target RNA. The resulting probe with its target RNA formed a stable three-way junction, named the MT2 three-way junction, which contributed to efficient refolding of the Broccoli structure and allowed for programmable RNA detection with high signal-to-noise ratio and sensitivity. Interestingly, the MT2 three-way junction also could be applied to probe construction of a truncated form of Spinach (Baby Spinach). The BRD and Baby Spinach–based RNA detection probes (BSRD probe) exhibited up to 48- and 140-fold fluorescence enhancements in the presence of their target RNAs and detected small amounts of target RNA that were as low as 160 and 5 nM, respectively. Thus, we experimentally characterized the higher order structure of Broccoli and developed structure-switching aptamer probes for highly sensitive, programmable, RNA detection using an MT2 three-way junction.

The differences in the mechanical properties between the cortex and coat protein layer in a Bacillus subtilis spore were clarified using an atomic force microscope (AFM) and an originally developed laser-induced surface deformation (LISD) microscope. AFM force curve measurements show that the Young's modulus of the coat protein layer is ca. 66% lower compared with that of the cortex. It has been experimentally clarified that the cortex makes a greater contribution to the rigidity of spores than the coat protein layer. From comparisons of the LISD power spectra, it is revealed that the coat protein layer has two different viscoelastic regions, and that the cortex relatively has a higher viscous nature than the coat protein layer. Furthermore, the LISD power spectrum above 1 × 105 Hz in the coat protein layer suggests that the local region in the coat protein layer behaves as a more elastic body compared with the cortex.

By applying a high pulsed voltage to a gap between two electrodes placed in a solution, an atmospheric-pressure in-solution glow (ASG) plasma is generated. The ASG plasma is applied in a new material processing method, called solution plasma processing (SPP). In order to accelerate the reaction and to add functions to the synthesized materials, it is important to alter the gas content in the ASG plasma. We developed a direct gas injection system for an ASG discharge cell. When O2, CO2, N2 and Ar gases were injected into the ASG plasma, emission bands due to the derivatives of the injected gases were observed in the emission spectra from the ASG plasma. The electron number density in the ASG plasma was increased by the O2, CO2, and N2 injections, probably due to the enhancements of the α and γ processes by the larger molecular weights than H2O. In addition, the first dielectric breakdown of the solution and the formation of the gas bubble processes gradually disappeared due to the gas injection. When O2 was injected, the amount of ·OH generation was increased. By the enhancement of the ·OH generation, the degradation speed of rhodamine B in the ASG plasma was increased by a factor of two. When Au nanoparticles were synthesized utilizing the ASG plasma, the zeta potential of the Au nanoparticles was increased by about 30% by the O2 injection. The plasma parameters and the reactivity of the ASG plasma can be altered more widely by changing the kind of injected gas and the flow rate.

We have clarified the differences in the power-law between normal and corresponding cancerous cells from dynamic viscoelastic measurements in a frequency range of 102 to 105 Hz with a laser-induced surface deformation (LISD) microscope. From the differences in the power spectra at higher frequencies, it has been clarified that a normal cell obeys the power-law with a single exponent, while a cancer cell with two exponents, indicating that the plasma membrane in the cancerous cell has at least two layers with different viscoelastic properties. In LISD measurements, the extension of the upper limit of the applied frequency up to 105 Hz allows us to clarify the existence of the two power-law exponents in the cancerous cell. Understanding the differences between normal and cancerous cells from the power-law in addition to conventional elasticity would be useful for the identification of cancerous cells and for the construction of a mechanical model for their invasion.

A laser-induced surface deformation (LISD) microscope is developed and applied to measurement of the dynamic relaxation responses of the plasma membrane in a living cell. A laser beam is tightly focused on an optional area of cell surface and the focused light induces microscopic deformation on the surface via radiation pressure. The LISD microscope not only allows non-contact and destruction-free measurement but provides power spectra of the surface responses depending on the frequency of the intensity of the laser beam. An optical system for the LISD is equipped via a microscope, allowing us to measure the relaxation responses in sub-cellular-sized regions of the plasma membrane. In addition, the forced oscillation caused by the radiation pressure for surface deformation extends the upper limit of the frequency range in the obtained power spectra to 106 Hz, which enables us to measure relaxation responses in local regions within the plasma membrane. From differences in power-law exponents at higher frequencies, it is realized that a cancerous cell obeys a weaker single power-law than a normal fibroblast cell. Furthermore, the power spectrum of a keratinocyte cell obeys a power-law with two exponents, indicating that alternative mechanical models to a conventional soft glassy rheology model (where single power-laws explain cells’ responses below about 103 Hz) are needed for the understanding over a wider frequency range. The LISD microscope would contribute to investigation of microscopic cell rheology, which is important for clarifying the mechanisms of cell migration and tissue construction.

Chitosan oligosaccharides, which obtain from degradation of chitosan, possess some interesting molecular weight-dependent biological properties, especially anticancer activity. Therefore, the conversion of chitosan to chitosan oligosaccharides with specific molecular weight has been continuously investigated in order to find effective strategies that can achieve both economic feasibility and environmental concerns. In this study, a novel process was developed to heterogeneously degrade chitosan powder by highly active species generated by electrical discharge plasma in a dilute salt solution (0.02 M) without the addition of other chemicals. The degradation rate obtained from the proposed process was comparable to that obtained from some other methods with the addition of acids and oxidizing agents. Separation of the water-soluble degraded products containing chitosan oligosaccharides from the reaction solution was simply done by filtration. The obtained chitosan oligosaccharides were further evaluated for an influence of their molecular weights on cytotoxicity against cancer cells and the selectivity toward cancer and normal cells.

Development of a differential interference contrast (DIC) stimulated Raman scattering (SRS) microscope is presented. In the apparatus, a coherent SRS signal generated from the sample is overlapped with a reference beam that is also focused on the same sample. The signal intensity correlates with the height difference between the point generating the SRS signal and the focal point of the reference beam. We applied the developed apparatus for imaging of Si surfaces with structures with heights of 50-350 nm. We also obtained the DIC-SRS image of the Si surface buried by liquid crystal. The structures of the interface between Si and liquid crystal were well observed when both the SRS signals due to Si and liquid crystal were utilized. It was also revealed that DIC-SRS microscopy is an effective tool to obtain molecular-selective images of structured interfaces with a height of less than several tens of nanometers buried by optically transparent media.

We investigated the structural transition from liquid silk to silk fibers with vibrational circular dichroism spectroscopy. Liquid silk showed a major right-handed optically active band at around 1650 cm(-1) and a minor one at around 1680 cm(-1). The former disappeared over time, while the intensity in the latter increased. With the former wavenumber, liquid silk mainly adopted a random-coil structure. In contrast, the latter may reflect an intermediate structure in the transition. Furthermore, two right-handed bands at around 1630 and 1660 cm(-1) appeared with the disappearance of the major band, and then the wavenumber of the former shifted to around 1620 cm(-1). The shift results from the decrease in the frequency of the CO stretching mode due to the stacking of the β-sheet that comprises fibers. The band at 1660 cm(-1) may reflect another intermediate structure due to its strong correlation with that at 1620 cm(-1) in terms of their temporal change in intensity.

Filamentous M13 phages act as components of materials toward various applications such as electronics, sensors, and biomedicine. To widen applicabilities of the phages, further development of methods for their utilization is required. Here, hybrid hydrogels composed of physically cross-linked gelatin and liquid-crystalline M13 phages are described. Mixing of the phages into gelatin hydrogels promoted the hydrogelation, and strengthened the mechanical strength. Liquid crystal formation of the phages in the hydrogels was evidenced by polarized optical microscopy observation. Degradation of the hydrogels by collagenase, which hydrolyzes gelatin, was suppressed by mixing the phages. These observations showed that the gelatin molecules were segregated into the spaces between phage lamellar structures. Our results will open attractive opportunities for simple construction of virus-based hybrid soft materials.

When high voltage is applied to a gap between electrodes in aqueous solution, a discharge plasma is generated that connects the edges of the facing electrodes. When the width of the gap between the electrodes is extended to more than several millimeters, the plasma is separated into two and they are localized at the vicinities of the edges of the anode (+plasma) and cathode (-plasma). Although they are expected to supply characteristic reaction fields, the properties of the plasmas, such as electron number density and temperatures of transient species, have not yet been clarified. In the present study, a time- and space-resolved emission spectrometer with a discharge cell was developed for optical diagnostics of the +plasma and -plasma separately. The electron number density for the +plasma was obviously lower than that for the -plasma. The difference in the electron number density should result from the difference in the ionization energy of the cathode materials. From the temporal evolutions of the emissions from the components, the emissions from the -plasma were sustained for about 0.5 μs after the decay of the applied voltage, probably due to the large number of free electrons in the -plasma. It is also clarified that hydroxyl radicals are effectively generated by the collisions between cations deriving from water and low-energy free electrons in the +plasma. The wide-gap in-solution discharge supplies two plasmas simultaneously with different properties. For plasma reactions, one plasma with suitable properties can be selected.

The temperature thawing, as called tempering, of triacylglycerols (TAGs) is an important processing method in food productions, such as chocolates, cream, confections, and spreads. Especially, melt-mediation by temperature thawing is famous in chocolate production for controlling the polymorphic crystalline forms and accelerating crystallization. In the present study, we investigated the α-melt structure of 1,3-dipalmitoyl-2-oleoyl-sn-glycerol (POP), one of the major continuants of cacao butter, under a phase transition from its melt to γ-crystal with in-situ attenuated total reflection-infrared (ATR-IR) spectroscopy. The differential IR spectrum between α-melt via temperature thawing (α-melt mediation) and melt via simple cooling revealed that crystal-like local ordered structures remained in part in the α-melt, and that they acted as nuclei for a rapid phase transition to the γ-crystal. The changes to the γ-crystal occur in the local ordered structures at first from the glycerol moiety to the acyl chains in the crystallization, providing an important suggestion concerning the mechanism for the acceleration of crystallization to the γ-form via α-melt mediation.