Polarized neutrons observed nanometer-thick crystalline ice plates in frozen glucose solution

Kumada, Takayuki; Nakagawa, Hiroshi; Miura, Daisuke; Sekine, Yurina; Motokawa, Ryuhei; Hiroi, Kosuke; Inamura, Yasuhiro; Oku, Takayuki; Oishi, Kazuki*; Morikawa, Toshiaki*; et al.

Journal of Physical Chemistry Letters (Internet), 14(34), p.7638 - 7643, 2023/08

https://doi.org/10.1021/acs.jpclett.3c01448

The structure of nano-ice crystals in rapidly frozen glucose solution was elucidated by using spin-contrast-variation small-angle neutron scattering, which distinguishes the nano-ice crystal signal from the frozen amorphous solution signal by the polarization-dependent neutron scattering. The analysis revealed that the nano-ice crystals form a planar structure with a diameter exceeding tens of nanometers and a thickness of 1 nm, which is close to the critical nucleation size. This result suggests that the glucose molecules are preferentially bound to a specific face of nano-ice crystals, and then block the crystal growth perpendicular to that face.

Development of spin-contrast-variation neutron powder diffractometry for extracting the structure factor of hydrogen atoms

Miura, Daisuke*; Kumada, Takayuki; Sekine, Yurina; Motokawa, Ryuhei; Nakagawa, Hiroshi; Oba, Yojiro; Ohara, Takashi; Takata, Shinichi; Hiroi, Kosuke; Morikawa, Toshiaki*; et al.

Journal of Applied Crystallography, 54(2), p.454 - 460, 2021/04

AA2020-0724.pdf:2.05MB

https://doi.org/10.1107/S1600576721000303

We developed a spin-contrast-variation neutron powder diffractometry technique that extracts the structure factor of hydrogen atoms, namely, the contribution of hydrogen atoms to a crystal structure factor. Crystals of L-glutamic acid were dispersed in a dpolystyrene matrix containing 4-methacryloyloxy-2,2,6,6,-tetramethyl-1-piperidinyloxy (TEMPO methacrylate) to polarize their proton spins dynamically. The intensities of the diffraction peaks of the sample changed according to the proton polarization, and the structure factor of the hydrogen atoms was extracted from the proton-polarization dependent intensities. This technique is expected to enable analyses of the structures of hydrogen-containing materials that are difficult to determine with conventional powder diffractometry.

Biogeochemical signals from deep microbial life in terrestrial crust

Suzuki, Yohei*; Konno, Yuta*; Fukuda, Akari*; Komatsu, Daisuke*; Hirota, Akinari*; Watanabe, Katsuaki*; Togo, Yoko*; Morikawa, Noritoshi*; Hagiwara, Hiroki; Aosai, Daisuke*; et al.

PLOS ONE (Internet), 9(12), p.e113063_1 - e113063_20, 2014/12

https://doi.org/10.1371/journal.pone.0113063

We present multi-isotopic evidence of microbially mediated sulfate reduction in a granitic aquifer, a representative of the terrestrial crust habitat. Deep groundwater of meteoric origin was collected from underground boreholes drilled into the Cretaceous Toki granite, central Japan. A large sulfur isotopic fractionation of 20-60 permil diagnostic to microbial sulfate reduction is associated with the investigated groundwater containing sulfate below 0.2 mM. In contrast, a small carbon isotopic fractionation ( 30 permil) is not indicative of methanogenesis. Our results demonstrate that the deep biosphere in the terrestrial crust is metabolically active and playing a crucial role in the formation of reducing groundwater even under low energy fluxes.

Crystal structure analysis of NaNbO in high-temperature phase

Aso, Seiyu*; Matsuo, Hiroki*; Noguchi, Yuji*; Yoneda, Yasuhiro; Morikawa, Daisuke*; Tsuda, Kenji*

no journal, , 

Recently, higher energy storage density than that of typical ferroelectric BaTiO has been achieved in NaNbO-based antiferroelectrics by utilizing the electric-field-induced phase transition between the antiferroelectric (AFE) and ferroelectric (FE) phases. In this study, we attempted to identify the space group using synchrotron X-ray diffraction and convergent electron diffraction in order to elucidate the full picture of the phase transition behavior in NaNbO and Ca-doped NaNbO. On the other hand, the Ca-doped sample showed that the space group is Pnma, which is consistent with the results obtained by convergent electron diffraction measurements.