Chiral measure of chiral polyhedrons.

To quantify chiral shape, a tensor describing the particle shape has been proposed. This tensor, named the shape tensor (S-tensor), is an analog of the hydrodynamic tensor that relates the rotational and translational motions of particles in a liquid. The determinant of the S-tensor, named chirality measure density (CMD), was calculated for chiral tetrahedrons and octahedrons. It was found that CMD is opposite in sign when the mirror images are chiral to each other and vanishes when they are achiral. Therefore, the CMD is a good measure to distinguish the mirror images. The interaction between chiral particles was discussed in terms of the CMD.

Decomposition of Unpolarized Fluorescence Spectrum of Uniaxially Oriented 1,3,5-Triphenylbenzene Microcrystals Into Polarized Fluorescence Spectra.

Luminescence from solids such as crystals and aggregates is of growing academic and industrial interest. In this study, we report decomposition of the unpolarized fluorescence spectrum of uniaxially oriented 1,3,5-triphenylbenzene (TPB) microcrystals into four polarized spectra measured with polarizer (V: vertical and H: horizontal) and analyser (V: vertical and H: horizontal), where V and H indicate perpendicular and parallel to the layer of TPB molecules in the crystal, respectively. Resolved spectra were interpreted in terms of the molecular and excimer like (J- and H-dimer) emissions. The origin of the excimer like emissions was discussed in relation to the molecular packing in the crystal. It was shown that polarized crystal fluorescence can provide insight into the excitation/emission process in the crystal. Although preliminary, this study demonstrates the potential of polarized fluorescence to elucidate the luminescent mechanism.

Continuous monitoring system for safe managements of CO2 storage and geothermal reservoirs.

We have developed a new continuous monitoring system based on small seismic sources and distributed acoustic sensing (DAS). The source system generates continuous waveforms with a wide frequency range. Because the signal timing is accurately controlled, stacking the continuous waveforms enhances the signal-to-noise ratio, allowing the use of a small seismic source to monitor extensive areas (multi-reservoir). Our field experiments demonstrated that the monitoring signal was detected at a distance of ~ 80 km, and temporal variations of the monitoring signal (i.e., seismic velocity) were identified with an error of < 0.01%. Through the monitoring, we identified pore pressure variations due to geothermal operations and rains. When we used seafloor cable for DAS measurements, we identified the monitoring signals at > 10 km far from the source in high-spatial resolution. This study demonstrates that multi-reservoir in an extensive area can be continuously monitored at a relatively low cost by combining our seismic source and DAS.

Time-Dependent Elastic Tensor of Cellulose Nanocrystal Probed by Hydrostatic Pressure and Uniaxial Stretching.

The elastic properties of crystals are fundamental for structural material. However, in the absence of macroscopic single crystals, the experimental determination of the elastic tensor is challenging because the measurement depends on the transmission of stress inside the material. To avoid arbitrary hypotheses about stress transfer, we combine hydrostatic pressure and uniaxial-stretching experiments to investigate the elastic properties of cellulose Iß. Three orthogonal compressibilities are 50.0, 6.6, and 1.71 TPa-1. Combining Poisson's ratios from a uniaxial stretching experiment directly gives the Young's modulus along the chain direction (E33). However, Poisson's ratio depends on the deformation rate leading to apparent modulus E33 = 113 GPa using a slow cycle (hours) and 161 GPa using a fast cycle (minutes). The lattice deformation along the chain is not time-dependent, so the off-diagonal elements are time-dependent on the scale of minutes to hours.

Source location of volcanic earthquakes and subsurface characterization using fiber-optic cable and distributed acoustic sensing system.

We present one of the first studies on source location determination for volcanic earthquakes and characterization of volcanic subsurfaces using data from a distributed acoustic sensing (DAS) system. Using the arrival time difference estimated from well-correlated waveforms and a dense spatial distribution of seismic amplitudes recorded along the fiber-optic cable, we determine the hypocenters of volcanic earthquakes recorded at Azuma volcano, Japan. The sources are located at a shallow depth beneath active volcanic areas with a range of approximately 1 km. Spatial distribution of the site amplification factors determined from coda waves of regional tectonic earthquakes are well correlated with old lava flow distributions and volcano topography. Since DAS observation can be performed remotely and buried fiber-optic cables are not damaged by volcanic ash or bombs during eruptions, this new observation system is suitable for monitoring of volcanoes without risk of system damage and for evaluating volcanic structures.

Magnetic Processing of Diamagnetic Materials.

Currently, materials scientists and nuclear magnetic resonance spectroscopists have easy access to high magnetic fields of approximately 10 T supplied by superconducting magnets. Neodymium magnets that generate magnetic fields of approximately 1 T are readily available for laboratory use and are widely used in daily life applications, such as mobile phones and electric vehicles. Such common access to magnetic fields-unexpected 30 years ago-has helped researchers discover new magnetic phenomena and use such phenomena to process diamagnetic materials. Although diamagnetism is well known, it is only during the last 30 years that researchers have applied magnetic processing to various classes of diamagnetic materials such as ceramics, biomaterials, and polymers. The magnetic effects that we report herein are largely attributable to the magnetic force, magnetic torque, and magnetic enthalpy that in turn, directly derive from the well-defined magnetic energy. An example of a more complex magnetic effect is orientation of crystalline polymers under an applied magnetic field; researchers do not yet fully understand the crystallization mechanism. Our review largely focuses on polymeric materials. Research topics such as magnetic effect on chiral recognition are interesting yet beyond our scope.

In situ solid-state NMR of a magnetically oriented microcrystal suspension.

In situ solid-state NMR measurements of a magnetically oriented microcrystal suspension (MOMS) were demonstrated. Under modulated rotation of the static field, or equivalently, of the sample tube, randomly oriented microcrystals in a viscous liquid medium feel a torque arising from the anisotropic bulk susceptibility and eventually aligned in the same direction. In this way, a three-dimensional MOMS (3D-MOMS) was obtained. To apply an elliptically rotating magnetic field to microcrystals in suspension, a probe to rotate the sample tube around an axis perpendicular to the static magnetic field was developed. Single-crystal (SC) rotation patterns were obtained from the 3D-MOMS by solid-state CP measurements triggered in synchronous with the sample-tube rotation. Unlike the traditional SC method, the 3D-MOMS approach presented here does not require the elaborate adjustment of the direction of the reference frame. The process of three-dimensional magnetic alignment was also studied by monitoring the spectral changes during continuous application of the modulated sample rotation.

Printing Birefringent Figures by Surface Tension-Directed Self-Assembly of a Cellulose Nanocrystal/Polymer Ink Components.

Photonic printing on transparent substrates using emerging synthetic photonic crystals is in high demand, especially for antifraud applications. However, photonic printing is faced with grand challenges including lack of full invisibility of printed patterns before stimulation or after stimulus removal and absence of the long-lasting stability. Natural anisotropic crystal structures and artificially molecularly arranged polymers show an optically anisotropic property known as birefringence. Crystalline cellulose is the most abundant birefringent biocrystal on the earth. Here, we introduce a printing method based on using a cellulose nanocrystal/polymer ink that is governed by surface evaporation phenomenon and divided surface tension forces to direct the self-assembly of ink components at the nanoscale and print three-dimensional birefringent microfigures on transparent substrates. This type of printing is from now on referred to as birefringent printing. Unlike previously reported photonic crystal printing methods, this method is accurate, has high contrast, is virtually impossible to forge, and is very simple, inexpensive, and nontoxic.

Determination of the Anisotropic Rotational Diffusion Constant of Microcrystals Dispersed in Liquid Medium.

Microcrystals of ErBa2Cu4O8 suspended in a liquid medium were triaxially aligned by a frequency-modulated magnetic field and allowed a free rotational relaxation after the magnetic field was turned off. In situ X-ray diffraction measurements of the suspension were performed during relaxation, and the temporal change of the orientation fluctuation was monitored via broadening of the diffraction spots. The rotational diffusion constants were determined using the plot of the orientation fluctuation versus the elapsed time of rotational relaxation. The diffusion constants thus determined were in close agreement with those evaluated by the Stokes law but showed slight anisotropy, indicating that the microcrystals studied had shape anisotropy. The present method can provide a useful means for experimentally determining rotational diffusion constants of microcrystals suspended in viscous media. This paper shows that, due to the combination of the initial triaxial alignment and the subsequent monitoring of the relaxation process by means of X-ray diffraction, the diffusion constants along arbitrary crystallographic axes are determined separately.

Crystal Orientation of Poly(l-Lactic Acid) Induced by Magnetic Alignment of a Nucleating Agent.

The orientation of poly(l-lactic acid) (PLLA) crystals was controlled through crystal growth from a magnetically oriented nucleating agent, phenylphosphonic acid zinc (PPAZn). The one-dimensional magnetically oriented microcrystal array of PPAZn microcrystals revealed the relationship between the magnetization and crystallographic axes in the PPAZn crystal. The PPAZn microcrystals were homogeneously dispersed in PLLA via melt mixing, which decreased the molecular weight of the PLLA component due to degradation. The PPAZn microcrystals in the molten PLLA were uniaxially aligned under an 8-T static or rotating magnetic field. The wide-angle X-ray diffraction and small-angle X-ray scattering patterns of the PPAZn/PLLA composite films crystallized under each magnetic field showed that the PLLA lamellae grew from the surface of the PPAZn microcrystals, which were uniaxially oriented along the easy- or hard-magnetization axis, with the c-axis of PLLA parallel to the bc-plane of PPAZn. It was also suggested that the greater nucleating effect of PPAZn on PLLA was derived not from geometrical matching, but from factors such as favorable interactions and/or the plate-like shape of the microcrystal.

Solid-state NMR meets electron diffraction: determination of crystalline polymorphs of small organic microcrystalline samples.

A combination of solid-state NMR (ssNMR) and electron diffraction (ED) has been used to determine the crystalline polymorphs in small-organic microcrystalline molecules. Although 13C cross-polarization magic angle spinning (CPMAS) is a widely used method for determining crystalline polymorphs, even in a mixture, it sometimes fails if the molecular conformations are similar. On the other hand, ED can, in principle, differentiate crystalline forms with different lattice parameters, even when they have very similar molecular conformations. However, its application is usually limited to inorganic molecules only. This is because the ED measurements of organic molecules are very challenging due to degradation of the sample by electron irradiation. We overcame these difficulties by the use of 1H double-quantum/single-quantum correlation experiments at very fast magic angle spinning, together with ED observations under mild electron irradiation. The experiments were demonstrated on L-histidine samples in L-histidine·HCl·H2O, orthorhombic L-histidine and monoclinic L-histidine.

Neutron and X-ray single-crystal diffraction from protein microcrystals via magnetically oriented microcrystal arrays in gels.

Protein microcrystals magnetically aligned in D2O hydrogels were subjected to neutron diffraction measurements, and reflections were observed for the first time to a resolution of 3.4 Šfrom lysozyme microcrystals (∼10 × 10 × 50 µm). This result demonstrated the possibility that magnetically oriented microcrystals consolidated in D2O gels may provide a promising means to obtain single-crystal neutron diffraction from proteins that do not crystallize at the sizes required for neutron diffraction structure determination. In addition, lysozyme microcrystals aligned in H2O hydrogels allowed structure determination at a resolution of 1.76 Šat room temperature by X-ray diffraction. The use of gels has advantages since the microcrystals are measured under hydrated conditions.

Single-crystal NMR approach for determining chemical shift tensors from powder samples via magnetically oriented microcrystal arrays.

The single-crystal rotation technique was applied to magnetically oriented microcrystal arrays (MOMAs) of cellobiose (monoclinic) to determine the principal values and principal axes of the chemical shift tensors of C1 and C1' carbons. Rotations were performed about the magnetic χ1, χ2, and χ3 axes of MOMA, and the measurements were taken at six different orientations with respect to the applied magnetic field. Under these rotations, crowded peaks were reduced and the peaks for the C1 and C1' carbons were identified by comparing with simulation results. Six components of the chemical shift tensor expressed with respect to the magnetic χ1χ2χ3-frame were determined. The tensors thus obtained were transformed into those relative to the molecular frame.

Anisotropic polymer composites synthesized by immobilizing cellulose nanocrystal suspensions specifically oriented under magnetic fields.

Novel polymer composites reinforced with an oriented cellulose nanocrystal (CNC) assembly were prepared from suspensions of CNC in aqueous 2-hydroxyethyl methacrylate (HEMA) via magnetic field application to the suspensions followed by polymerization treatment. The starting suspensions used at ∼6 wt % CNC separated into an upper isotropic phase and a lower anisotropic (chiral nematic) one in the course of quiescent standing. A static or rotational magnetic field was applied to the isolated isotropic and anisotropic phases. UV-induced polymerization of HEMA perpetuated the respective states of magnetic orientation invested for the CNC dispersions to yield variously oriented CNC/poly(2-hydroxyethyl methacrylate) composites. The structural characterization was carried out by use of X-ray diffractometry and optical and scanning electron microscopy. The result indicated that CNCs were aligned in the composites distinctively according to the static or rotational magnetic application when the anisotropic phases were used, whereas such a specific CNC orientation was not appreciable when the isotropic phases were sampled. This marks out effectiveness of a coherent response of CNCs in the mesomorphic assembly. In dynamic mechanical experiments in tensile or compressive mode, we observed a clear mechanical anisotropy for the polymer composites synthesized from wholly anisotropic suspensions under static or rotational magnetization. The higher modulus (in compression) was detected for a composite reinforced by locking-in the uniaxial CNC alignment attainable through conversion of the initial chiral nematic phase into a nematic phase in the rotational magnetic field.

Strong highly anisotropic magnetocellulose nanocomposite films made by chemical peeling and in situ welding at the interface using an ionic liquid.

Magnetic cellulosic papers have attracted considerable interest because of their potential applications in advanced information storage devices and security papers. However, these papers are often mechanically weak and structurally and magnetically in-plane isotropic, which restrict their applications especially where stronger anisotropic materials are required. Here, we report the production and properties of a strong anisotropic superparamagnetic cellulose nanocomposite (ASPCNC) film with high in-plane anisotropy prepared using ionic liquid (IL)-based peeling and in situ welding processes. Field-emission scanning electron microscopy, energy-dispersive X-ray analysis, X-ray diffraction, attenuated total reflection Fourier transform infrared spectroscopy, atomic force microscopy, magnetic force microscopy, and vibrating sample magnetometry were used to characterize the produced nanocomposite films. Mechanical and magnetic in-plane anisotropy were measured, and their relationships with the structural properties were determined. Tensile failure behavior of the ASPCNCs was also compared with predictions from Hankinson's failure model. The results show highly significant relationships between increasing partial dissolution time as the development index of the IL-based peeling and in situ welding procedures and improvements in the mechanical properties and structural, mechanical, and magnetic in-plane anisotropy of the ASPCNCs. Reasons behind these observations are extensively discussed.

Tunable self-assembly of cellulose nanowhiskers and polyvinyl alcohol chains induced by surface tension torque.

This article focuses on the formation of the surface tension torque (STT) phenomenon close to the dry-line boundary layer during evaporation of the liquid phase of a solution casted shape-anisotropic nanoparticle suspension (here, cellulose nanowhisker (CNW)) or dissolved polymer (here, polyvinyl alcohol (PVA)) and its effects on self-assembly of the cellulose nanocrystals and polymer chains. The results confirm that the STT tends to align both the CNWs and the PVA chains tangential to the dry-line boundary layer. By careful control of the advancement of the dry-line, achieving special linear and curved patterns of both the CNWs and the PVA chains proportional to the mold position and geometry is possible. The STT phenomenon is explained and simplified in terms of a physical model. Understanding of the STT phenomenon and its effects on the alignment and self-assembly of the CNWs and PVA chains is necessary especially when achieving alignment using a modulated external magnetic or electric field is desired. The STT is safe, inexpensive, easy, and efficient, and can be a good alternative to the magnetic and electric field orientation methods.

Crystalline supramolecular nanofibers based on dehydrobenzoannulene derivatives.

Supramolecular nanofibers (SNFs) composed of low-molecular-weight π-conjugated molecules exhibit attractive optical and electrical properties and are expected to be the next optoelectronic materials. In this work, five crystalline SNFs have been constructed from three dehydrobenzoannulene (DBA) derivatives. The DBAs were designed to assemble in one dimension in a strategy based on anisotropic crystal growth. The crystallinity of the SNFs allowed the molecular arrangements in the SNFs to be determined. Therefore the mechanism of construction and correlations between the molecular arrangements and optical and electrical properties could be considered. The results clearly indicate that the properties of the SNFs are affected by the chemical structures and molecular arrangements. Moreover, one of the SNFs exhibits a high charge-carrier mobility (Σµ=0.61 cm(2) V(-1) s(-1)) because of its crystallinity and appropriate molecular arrangement. This systematic experimental study based on a proposed strategy has provided information for improving the electrical properties of SNFs. This strategy will lead to highly functional SNFs.

Magnetic alignment in solid state and temperature hysteresis in aqueous tetrahydrofuran solution for tetrathiafulvaleno[18]annulenes.

Tris(tetrathiafulvaleno)dodecadehydro[18]annulene-hexaesters have a multi-functionality that is very sensitive to small differences in the ester side-chain. Self-aggregation of the [18]annulenes in amphiphilic media such as THF-H(2)O (v/v, 1:1) either produce a fibrous structure or result in temperature hysteresis of the color and (1)H NMR signals. This temperature hysteresis in solution is due to both strong self-aggregation behavior and unique cluster formation in a binary solution of THF and water.

The pseudo-single-crystal method: a third approach to crystal structure determination.

A novel method that enables single-crystal diffraction data to be obtained from a powder sample is presented. A suspension of LiCoPO(4) microrods was subjected to a frequency-modulated dynamic elliptical magnetic field to align the microrods; the alignment achieved was consolidated by photopolymerization of the suspending UV-curable monomer. The composite thus obtained (referred to as a pseudo single crystal) gave rise to X-ray diffraction data from which the crystal structure was solved using the standard method for single-crystal X-ray analyses. The structure determined was in good agreement with that reported using a conventional single crystal.