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Abstract Flexibility has been pursued enthusiastically in the field of porous crystals for enhancing their adsorption and separation performances. However, flexibility has never been observed among porous crystals sustained thoroughly by van der Waals interactions since flexible motions readily lead to the collapse of the porous architecture. Here we report a van der Waals crystal featuring conformational flexibility as well as permanent microporosity. The single-crystal structure and its structural transition in response to the adsorption of water molecules were unambiguously disclosed by means of electron and X-ray crystal structure analyses. The peripheral aromatic rings of the constituent molecule rotated as increasing the ambient humidity, while the connectivity of the pores was maintained throughout the structural transition. The transformative pores allowed the guest water molecules to move exceedingly quickly through the pores with a time constant of 490 μs. We demonstrated that the quick release of water induced by photothermal heating induced a significant upward bending of a film set above the crystalline powder compared to conventional porous materials. This finding contributes to the future crystal engineering based on van der Waals interactions rather than cohesive bonds.

Abstract Access to clean water, hygiene, and sanitation is becoming an increasingly pressing global demand, particularly owing to rapid population growth and urbanization. Phytoremediation utilizes a highly conserved phytochelatin in plants, which captures hazardous heavy metal ions from aquatic environments and sequesters them in vacuoles. Herein, we report the design of phytochelatin-inspired copolymers containing carboxylate and thiolate moieties. Titration calorimetry results indicate that the coexistence of both moieties is essential for the excellent Cd2+ ion-capturing capacity of the copolymers. The obtained dissociation constant, K D ~ 1 nM for Cd2+ ion, is four-to-five orders of magnitude higher than that for peptides mimicking the sequence of endogenous phytochelatin. Furthermore, infrared and nuclear magnetic resonance spectroscopy results unravel the mechanism underlying complex formation at the molecular level. The grafting of 0.1 g bio-inspired copolymers onto silica microparticles and cellulose membranes helps concentrate the copolymer-coated microparticles in ≈3 mL volume to remove Cd2+ ions from 0.3 L of water within 1 h to the drinking water level (

Electron–phonon (e–p) polar-coupling interactions in C12H17ClN4OS·HCl·H2O crystals exhibiting an upward frequency shift with increasing temperature are investigated using terahertz and far-infrared spectroscopies, and the structural condition required for effective e–p polar-coupling interactions in crystals are uncovered. X-ray crystallography and first-principles calculations reveal that the key structure for the e−p polar-coupling interaction is an open cavity near the considered vibration. Based on the temperature-dependent frequency shift proportional to the Bose−Einstein statistical factor, the interaction strength and characteristic frequency of phonons interacting with electrons are determined at 5.3 × 10–3 cm–1 K–1 and 76.6 cm–1, respectively. From the phonon dispersion curves exhibiting LO (longitudinal optical)–TO (transverse optical) splitting, we find that the highest frequency LO phonon participates in the polar-coupling interaction.

Abstract Van der Waals (VDW) interactions provide fantastic properties for biological systems that function at room temperature. The VDW interaction, which primarily contributes to weak hydrogen bonding, is expected to play a key role in regulating hydrophobic hydration to express the biologically inert biocompatible function of polymerized MPCs (2-methacryloyloxyethyl phosphorylcholine). This report explores at the molecular level the biologically inert function of polymerized MPCs through an array of vibrational spectroscopic and computational characterization of MPC monomers, as temperature-dependent change of intramolecular weak hydrogen bonding. Synchrotron Fourier transform infrared microspectroscopy and terahertz time-domain spectroscopy were used to investigate temperature-dependent spectral changes in the low frequency vibrations of the MPC over the temperature range from cryogenic to room temperature, and the results were analysed by highly reliable well-established density functional theory (DFT) calculations. Complicated spectral features in the low frequency energy region and the uncertain conformations of the MPC in the amorphous powder state are clearly resolved under a polarizable continuum model and dispersion correction to pure DFT calculations.

Abstract Recently, spark plasma sintering (SPS) has become an attractive method for the preparation of solid-state ceramics. As SPS is a pressure-assisted low-temperature process, it is important to examine the effects of temperature and pressure on the structural properties of the prepared samples. In the present study, we examined the correlation between the preparation conditions and the physical and structural properties of SiO2 glasses prepared by SPS. Compared with the conventional SiO2 glass, the SPS-SiO2 glasses exhibit a higher density and elastic modulus, but a lower-height first sharp diffraction peak of the X-ray total structure factor. Micro-Raman and micro-IR spectra suggest the formation of heterogeneous regions at the interface between the SiO2 powders and graphite die. Considering the defect formation observed in optical absorption spectra, reduction reaction mainly affects the densification of SPS-SiO2 glass. Hence, the reaction at the interface is important for tailoring the structure and physical properties of solid-state materials prepared by the SPS technique.

Reversible or movable cross-links based on host-guest interactions in supramolecular materials create functions such as enhanced mechanical properties and stimulus responsiveness. A supramolecular complex on a polymer side chain achieves the described functions as a reversible cross-link. Generally, 1:1 complex is utilized as a cross-link for the host-guest interaction based-supramolecular materials, but herein, the 1:2 complex between γ-cyclodextrin (γCD) and methyl viologen terminated undecyl acrylate (VC11) was chosen to cross-link three polymeric chains. The obtained supramolecular hydrogels γCD-VC11 (x, y) (x and y represent the mol% of the γCD and VC11 units in feeding, respectively) was prepared by radical copolymerization with acrylamide as a mainchain monomer. Tensile test revealed that toughness (Gf) of γCD-VC11 (x, y) maximized at water content (Wc) ≈ 40 wt.%. The maxima of Gf depended on the amount of γCD and VC11 units. Through dynamic mechanical analysis, Arrhenius style plots between horizontal shift factors and temperature determined activation energies (Ea) of each γCD-VC11 (x, y) and MBAAm (0.5). Ea of MBAAm (0.5) monotonically decreased with the increasing Wc. On the other hand, slope of Ea of γCD-VC11 (x, y) changed at Wc ≈ 40 wt.%. Simultaneously considering results of the tensile tests and DMA, the reversible cross-links formed by γCD and VC11 in γCD-VC11 (x, y) function effectively at appropriate Wc.

Using photosensitive caged-compound for femtosecond crystallography at X-ray free electron lasers would allow the structure determination of reaction intermediates. Here the authors demonstrate the feasibility of this approach with a caged NO-compound and present the initial NO-bound intermediate structure of cytochrome P450 nitric oxide reductase.

Infrared synchrotron radiation (IR-SR) is a broad-band light source. Its brilliance is the main advantage for microspectroscopy experiments, when the limited size of the sample often prevents the use of conventional thermal radiation sources. Cultural heritage materials are delicate and valuable; therefore, nondestructive experiments are usually preferred. Nevertheless, sometimes, small pieces can be acquired in the process of preservation and conservation. These samples are analyzed by various experimental techniques and give information about the original material and current condition. In this paper, four attempts to analyze cultural heritage materials are introduced. All these experiments are performed at the microspectroscopy station of IR beamline BL43IR in SPring-8.

The excitonic insulator Ta2NiSe5 experiences a first-order structural transition under pressure from rippled to flat layer-structure at Ps ∼ 3 GPa, which drives the system from an almost zero-gap semiconductor to a semimetal. The pressure-induced semimetal, with lowering temperature, experiences a transition to another semimetal with a partial-gap of ∼0.1–0.2 eV, accompanied with a monoclinic distortion analogous to that occurs at the excitonic transition below Ps. We argue that the partial-gap originates primarily from a symmetry-allowed hybridization of Ta-conduction and Nivalence bands due to the lattice distortion, indicative of the importance of electron–lattice coupling. The transition is suppressed with increasing pressure to Pc ∼ 8 GPa. Superconductivity with a maximum Tsc ∼ 1.2 K emerges around Pc, likely mediated by strongly electron-coupled soft phonons. The electron–lattice coupling is as important ingredient as the excitonic instability in Ta2NiSe5 [ABSTRACT FROM AUTHOR]

We have investigated a newly found α'-phase bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) molecular arrangement system, namely, αAA-(BEDT-TTF)2Rb2xCo(SCN)4 (α'-Rb2xCo), with localized S = 3/2 Co2+ spins. From X-ray structural analyses, we found that owing to the nonstoichiometric ratio of Rb ions (x = 0.6), this compound takes an intermediate value of π-electron band filling between those of αAA-(BEDT-TTF)2CsHg(SCN)4 and α'-(BEDTTTF)2K1.4Co(SCN)4. α'-Rb2xCo (x = 0.6) is a paramagnetic metal at room temperature and exhibits a first-order transition to an insulating state at 100 K, which is the lowest among the three compounds. The results of the twodimensional optical conductivity spectra and peak splitting of charge-sensitive ν27 molecular vibrational modes indicate the phase transition to a state with a gap of 600 cm-1, which is attributed to charge ordering consisting of at least four differently charged BEDT-TTF molecules. The π-spin susceptibility suddenly decreases at the transition temperature, and another anomaly can be seen at about 40 K. Given that π-spin disappears at 100 K (i.e., formation of a spin-singlet state), it is difficult to systematically explain other physical properties as a whole at low temperatures. However, by simply assuming the presence of π spins, we can account for all the observed results without contradiction. We also discuss anomalies in the dielectricity of π electrons under magnetic fields mediated by π-d interactions and the spincharge coupling [ABSTRACT FROM AUTHOR]

Lithiated polysilane was synthesized by the mechanochemical reaction of layered polysilane with metallic lithium. The resulting dark green powder formed a Si--Li bond on the surface and demonstrated electroconductivity. [ABSTRACT FROM AUTHOR]

By means of a scanning micro-region infrared reflectance spectroscopy, we study a real-space imaging of local electronic states in a 4d-electron transition-metal oxide Ca2RuO4. Our spectroscopic imaging shows a macroscopic spatial inhomogeneity of energy gap in the orbital-ordered insulating phase below 360 K. The result includes no metal-insulator domains but rather an inhomogeneous distribution of the energy gap. We demonstrate that the gap distribution is intimately correlated with local crystalline disorders, indicating a strong electron-lattice coupling expected in orbital-ordered systems. Such a disorder-sensitive infrared spectroscopy is reminiscent of a disorder effect on charge/orbital order in 3d oxides, implying a significant role of quenched disorder in various orbital-ordered systems. [ABSTRACT FROM AUTHOR]

In this article, we describe our high-pressure infrared (IR) spectroscopy techniques for studying the electronic structures of materials at high pressures. High pressure of up to 20 GPa is applied to a sample using a diamond anvil cell (DAC). To accurately perform IR spectroscopy in the limited sample space of a DAC, synchrotron radiation is used as a bright IR source. Our techniques allow reflectance studies of a single crystal sample and determination of the optical functions of the sample such as dielectric function and optical conductivity. To illustrate the capability and usefulness of our techniques, some actual results of high-pressure IR studies on rare-earth compounds are described. [ABSTRACT FROM AUTHOR]

Infrared synchrotron radiation (IR-SR) is a highly brilliant white light source. We are developing an infrared near-field spectroscopy system with an IR-SR light source. The near-field spectroscopy system previously reported comprised an atomic force microscope (AFM) and a commercial Fourier transform infrared (FTIR) spectrometer. In the present study, the configuration of the FTIR interferometer has been modified to an asymmetric one. In the asymmetric interferometer, one beam split by a beamsplitter is focused onto the tip of an AFM probe, and the other beam goes to a movable mirror. The scattered light from the probe and the light reflected by the movable mirror interfere with each other. The near-field signal is extracted by a modulation method with an AFM oscillation frequency. The signal-to-noise ratio has been improved 6-fold and the signal-to-background ratio is improved 8-fold compared with those observed in the previous system. [ABSTRACT FROM AUTHOR]

The temperature dependence of the optical response in the far-infrared (FIR) region of metallic and semiconducting rich single-walled carbon nanotubes (SWCNTs) was investigated by micro-Fourier transform infrared spectrometry with a focused beam of synchrotron radiation. The temperature dependence of the FIR spectra of both types of SWCNT showed negligibly small variations within a wide temperature range from 4 to 300 K. Upon comparison with a theoretical model for the diffusive region, it is speculated that these results might have been caused by a strong suppression of phonon scattering in relatively short CNTs with lengths of less than 1 μm. [ABSTRACT FROM AUTHOR]