Nanoscopic structural investigation of physically cross-linked nanogels formed from self-associating polymers

Sekine, Yurina; Endo, Hitoshi*; Iwase, Hiroki*; Takeda, Shigeo*; Mukai, Sadaatsu*; Fukazawa, Hiroshi; Littrell, K. C.*; Sasaki, Yoshihiro*; Akiyoshi, Kazunari*

Journal of Physical Chemistry B, 120(46), p.11996 - 12002, 2016/11

https://doi.org/10.1021/acs.jpcb.6b06795

The detailed structure of a nanogel formed by self-association of cholesterol-bearing pullulans (CHP) was determined by contrast variation small-angle neutron scattering. The decomposition of scattering intensities into partial scattering functions of each CHP nanogel component, i.e., pullulan, cholesterol, and the cross-term between the pullulan and the cholesterol allows us to investigate the internal structure of the nanogel. The effective spherical radius of the skeleton formed by pullulan chains was found to be about 8.1 nm. In the CHP nanogel, there are about 19 cross-linking points where a cross-linking point is formed by aggregation of trimer cholesterol molecules with the spatially inhomogeneous distribution of the mass fractal dimension of 2.6. The average radius of the partial chains can also be determined to be 1.7 nm. As the result, the complex structure of the nanogels is coherently revealed at the nanoscopical level.

Dependence of structure of polymer side chain on water structure in hydrogels

Sekine, Yurina; Takagi, Hajime*; Sudo, Sayoko*; Kajiwara, Yutaro*; Fukazawa, Hiroshi; Fukazawa, Tomoko*

Polymer, 55(24), p.6320 - 6324, 2014/11

https://doi.org/10.1016/j.polymer.2014.10.011

To investigate the effects of structure of polymer side chains on structure of water in hydrogels, Raman spectra of polyacrylamide (PAA) and poly-,-dimethylacrylamide (PDMAA) hydrogels were measured. PAA and PDMAA have similar chemical structures, except for the side chain structure. The result shows that the frequency of the OH stretching mode for the PAA hydrogel decreases as the water content decreases, while that for the PDMAA hydrogel increases. We conclude that most of the bound water molecules in the PAA hydrogel form four strong hydrogen bonds with the hydrophilic groups in the side chain of PAA, whereas those in the PDMAA hydrogel form weak hydrogen bonds with surrounding water molecules. The water structure is an important factor governing the physical and chemical properties of gel materials.

The Existence of memory effect on hydrogen ordering in ice; The Effect makes ice attractive

Arakawa, Masashi*; Kagi, Hiroyuki; Fernandez-Baca, J. A.*; Chakoumakos, B.*; Fukazawa, Hiroshi

Geophysical Research Letters, 38, p.L16101_1 - L16101_5, 2011/08

https://doi.org/10.1029/2011GL048217

The existence of ferroelectric ice XI with ordered hydrogen in space becomes of interest in astronomy and physical chemistry because of the strong electrostatic force. However, the influence was believed to be limited because it forms at narrow temperature range. From neutron diffraction experiments, we found that small hydrogen-ordered domains exist at significantly higher temperature and the domains induce the growth of "bulk" ice XI. The small ordered domain is named "memory" of hydrogen ordered ice because it is the residual structure of ice XI. Since the memory exists up to at least 111 K, most of ices in the solar system are hydrogen ordered and may have ferroelectricity. The small hydrogen-ordered domains govern the cosmochemical properties of ice and evolution of icy grains in the universe.

Neutron diffraction study of hydrogen-ordered ice XI; Annealing effect and memory effect

Arakawa, Masashi*; Kagi, Hiroyuki; Fernandez-Baca, J. A.*; Chakoumakos, B. C.*; Fukazawa, Hiroshi

Physics and Chemistry of Ice 2010, p.329 - 338, 2011/03

We measured neutron diffraction profiles of KOD, NaOD, LiOD, Ca(OD), and ND-doped ices. Ice XI, which is a hydrogen-ordered phase of normal ice (ice Ih), was observed in the KOD and NaOD-doped ices although Ca(OD) and ND-doped ice did not transformed to ice XI. The mass fraction of ice XI to that of the doped ice () was estimated using Rietveld analysis for each doped ice. The value of the doped ice, which had once experienced being ice XI, was larger than that of the doped ice, which had never experienced being ice XI. The large value of the doped ice indicates that small hydrogen-ordered domains remained above the transition temperature between ice XI and Ih. Our results suggest that large amounts of ice on icy bodies in our solar system can transform to ice XI. In this paper, we discussed the existence of the small hydrogen-ordered domains in space and the evolution of icy grain.

The Existence of ferroelectric ice on icy bodies in space; A Neutron diffraction study

Fukazawa, Hiroshi

Nippon Kessho Gakkai-Shi, 52(4), p.219 - 225, 2010/08

https://doi.org/10.5940/jcrsj.52.219

The complex behavior of water and the unusual properties of ferroelectric ice XI continue to attract much interest. Whether ice in the space exists as ice XI, is an important question, because long range electrostatic forces caused by the ferroelectricity might be an important factor for planet formation. From neutron diffraction experiments, we found the temperature and pressure conditions for the transformation of the largest fraction of ice into ferroelectric ice. It suggests that myriad big icy-bodies, which exist as dwarf planets and Kuiper Belt Object, consist of thick ferroelectric-ice surface. Furthermore, we report spectral and vibrational properties of ferroelectric ice investigated by inelastic neutron scattering and infrared absorption measurements. Because the spectral properties of ferroelectric ice are clearly different from those of ordinary ice, the distinct ferroelectric ice in the universe is detectable using infrared telescopes and planetary exploration.

Annealing effects on hydrogen ordering in KOD-doped ice observed using neutron diffraction

Arakawa, Masashi*; Kagi, Hiroyuki; Fukazawa, Hiroshi

Journal of Molecular Structure, 972(1-3), p.111 - 114, 2010/05

https://doi.org/10.1016/j.molstruc.2010.02.016

We measured the neutron powder diffraction of 0.013 M KOD-doped DO ice to investigate the formation process of ice XI, a hydrogen-ordered phase of ice Ih. The doped ice Ih transformed to ice XI after annealing at 57 and subsequently at 68 K. The mass fraction of ice XI to that of the doped ice () was estimated using Rietveld analysis for each sample. The value of the doped ice, which had once experienced being ice XI ( = 0.23), was larger than that of the doped ice, which had never experienced being ice XI ( = 0.14). Results indicate that small hydrogen-ordered domains remained in the ice Ih, which had once trans- formed to ice XI, and accelerated the phase transition from ice Ih to ice XI. Results further suggest that large amounts of ice on icy bodies in our solar system can transform to ice XI, which might be detectable using infrared telescopes or planetary exploration in the near future.

Neutron powder diffraction and difference maximum entropy method analysis of protium- and deuterium-dissolved BaSnInO

Nagasaki, Takanori*; Shiotani, Shinya*; Igawa, Naoki; Yoshino, Masahito*; Iwasaki, Kota*; Fukazawa, Hiroshi; Utsumi, Wataru

Journal of Solid State Chemistry, 182(10), p.2632 - 2639, 2009/10

https://doi.org/10.1016/j.jssc.2009.06.024

We propose a new method, a difference maximum entropy method (MEM) analysis of the neutron diffraction data, for revealing the detailed structure around hydrogen atoms in proton-conducting oxides. This MEM analysis uses the differences between the structure factors of protium- and deuterium-dissolved crystals. Simulations demonstrate that it not only provides the distribution of hydrogen atoms alone, but also improves the spatial resolution of MEM mapping around hydrogen atoms. Applied to actual diffraction data of protium- and deuterium-dissolved BaSnInO at 9 K, difference MEM analysis reveals that O-D bonds mostly tilt towards the second nearest oxygen atoms, and that the distributions of deuterium and oxygen atoms are probably insignificant in interstitial regions.

Crystal structure and lattice vibration of proton dissolved BaZrScO

Shimoyama, Tomotaka*; Tojo, Takeo*; Kawaji, Hitoshi*; Atake, Toru*; Fukazawa, Hiroshi; Igawa, Naoki

Solid State Ionics, 180(6-8), p.560 - 562, 2009/05

https://doi.org/10.1016/j.ssi.2008.10.016

The neutron diffraction of BaZrScO with and without proton were measured and analyzed by Rietveld method and Maximum Entropy Method. We found that the location of proton is 12 site near oxygen ion. The heat capacity of sample with proton is larger than that without proton. This difference is discussed in term of the changes of the crystal structure and lattice vibrations due to the dissolution of proton.

Nucleation and growth of ice XI; Study suggests the existence of ferroelectric ice in the universe

Fukazawa, Hiroshi

Nippon Kessho Gakkai-Shi, 51(1), p.84 - 85, 2009/02

Our neutron diffraction study suggests that icy interior inside cool planets is ferroelectric. The super-dense ferroelectric ice, possessing the ability to carry a charge, could have had important effects on geological events on cool planets.

Development of asymmetric reflection-type germanium monochromator for neutron beam enhancement

Yamauchi, Hiroki; Ishii, Yoshinobu*; Igawa, Naoki; Fukazawa, Hiroshi; Utsumi, Wataru

JAEA-Research 2008-077, 28 Pages, 2008/10

JAEA-Research-2008-077.pdf:24.52MB

The neutron powder diffractometer, HRPD, can provide high-resolution data that meet the many users' needs until now. On the other hand, the demand of high-efficiency is growing in the recent years. In order to improve the source intensity and measurement efficiency, the authors tried to develop asymmetric reflection-type Ge monochromators. The mosaic crystals (20 in the horizontal direction) were cut at an angle of 40 relative to the Ge,3,3,1 reflecting planes. The diffraction results of standard Si samples reveal that peak intensities by the asymmetric type are improved 1.2 times larger than those by the existing symmetric type, but integrated intensities are almost comparable each other. For mosaic crystals, asymmetric reflections in compression geometry intensify the current density, but reflectivity is always less than that in symmetric reflections, and thus the suppression of the reflectivity just cancels out the enhancement of the current density.