Faculty of Environmental Sciences Division of Applied Chemistry Graduate School of Environmental Sciences Department of Applied Chemistry Annual Report 2017 Index Reports from Research Groups Kawakami Laboratory ▪▪▪▪▪ 1 Masuda Laboratory ▪▪▪▪▪ 8 Setaka Laboratory ▪▪▪▪▪ 10 Haruta Laboratory ▪▪▪▪▪ 12 Kanamura Laboratory ▪▪▪▪▪ 17 Takagi Laboratory ▪▪▪▪▪ 20 Yamaguchi Laboratory ▪▪▪▪▪ 23 Uchiyama Laboratory ▪▪▪▪▪ 25 Kubo Laboratory ▪▪▪▪▪ 30 Shishido Laboratory ▪▪▪▪▪ 33 Colloquium ▪▪▪▪▪ 36 Reports from Research Groups Kawakami Laboratory 13 Members membranes was analyzed by utilizing the C-NMR ■ 13 Hiroyoshi KAWAKAMI spectroscopy with CO2 probe and gas adsorption Professor / Dr. Eng. measurements. Polymer Chemistry, Functional Polymers, Nanofiber Engineering, Biomaterials, Epigenetics Engineering, Free Radical Science Rm. 9-638, +81-42-677-1111 Ext. 4972 [email protected] Shoichiro ASAYAMA Associate Professor / Dr. Eng. Biomaterials, Biomedical Polymers, Biochemistry, Biomolecular Engineering Rm. 9-651, +81-42-677-1111 Ext. 4976 [email protected] Figure 1. Schematic illustration of the polymer composite membranes containing the surface-modified silica nanoparticles Masafumi YAMATO with various shapes. Associate Professor / Dr. Eng. Polymer Science, Magneto-Science Rm. 9-137, +81-42-677-1111 Ext. 4837 2. Study of Polymer Electrolyte Membrane [email protected] Hiroyoshi KAWAKAMI, Manabu TANAKA Manabu TANAKA Polymer electrolyte fuel cells have attracted much attention Assistant Professor / Dr. Eng. as clean and sustainable energy systems. We have reported Polymer Chemistry, Polymer Electrolytes, Nanofibers, Polymer composite polymer electrolyte membranes based on phytic acid Membranes (Phy)-doped polybenzimidazole nanofibers (PBINF) showed Rm. 9-639, +81-42-677-1111 Ext. 4586 outstanding fuel cell performances under low relative humidity [email protected] conditions. In this year, we fabricated novel electrospun polymer Riku KUBOTA nanofibers containing sulfonate and phosphonate groups that Specially-appointed Assistant Professor / Dr. Eng. can form effective proton conductive pathway inside the Supramolecular Chemistry, Complex Chemistry, Catalyst nanofibers (Figure 2). The novel polymer composite Chemistry membranes composed of the blend or core/shell nanofibers Rm. 9-649, +81-42-677-1111 Ext. 4973 showed higher proton conductivity than the conventional [email protected] composite membranes, especially under low humidity conditions, which are assumed as future fuel cell operation Manjit Singh GREWAL conditions. Specially-appointed Assistant Professor / Ph.D. Polymer Chemistry, Polymer Electrolyte Rm. 9-649, +81-42-677-1111 Ext. 4973 [email protected] Master’s course -17 Bachelor 4 -8 ■Outlines of the Research 1. Study of Functional Polymer Membrane Hiroyoshi KAWAKAMI, Masafumi YAMATO, Manabu TANAKA Membrane-based gas separations have tremendous potential as energy-efficient alternatives or removal material of greenhouse gasses, such as carbon dioxide (CO2). Recently, we have reported that novel composite membranes composed of the fluorinated polyimide or polymers of intrinsic microporosity (PIM) and surface-modified silica nanoparticles exhibit high gas permeability and selectivity. In this year, we focused on new types of nanoparticles, Figure 2. Schematic illustration of the novel polymer including pearl-necklace shaped and chain shaped silica electrolyte composite membranes based on the blend or nanoparticles that have originally inter-connected structures core/shell nanofibers. (Figure 1). As a result, we achieved to demonstrate extremely high CO2 permeability by using the composite membrane containing surface-modified pearl-necklace shaped silica 3. Study of Electrospun Nanofibers nanoparticles. Furthermore, the mechanism for the Hiroyoshi KAWAKAMI, Manabu TANAKA, Manjit Singh GREWAL improvement of CO2 permeability in these composite 1 Reports from Research Groups bimetallic complex. Recently, nano-scale fibers prepared through an electrically charged jet of polymer solution/melt (electrospinning) have 5. Study of Epigenetics Engineering received a lot of attention. Nanofibers have several inherent Hiroyoshi KAWAKAMI, Shoichiro ASAYAMA, characteristics including high surface area, unique optical and Riku KUBOTA physicochemical properties originated from the nano-size, and alignment of polymer chains in the nanofibers. The diameter of The development and maintenance of an organism is nanofiber is one of the most important factors to effect on such orchestrated by a set of chemical reactions that switch parts of unique characteristics. Ultrafine nanofibers with their diameters the genome off and on at strategic times and locations. less than 50 nm were also obtained. Epigenetics is the study of these reactions and the factors that In this year, we mainly focused on the fabrication of lithium influence them. ion conductive polymer nanofibers and their composite In this year, we have prepared novel epigenetics control membranes for the secondary battery applications (Figure 3). carrier (EpC) containing single chain lipid. The resulting EpC The novel lithium ion conductive nanofiber composite carrier exhibited long-term stability. On the other hand, membranes showed higher lithium ion conductivity than the interestingly, the physicochemical properties of the EpC carrier corresponding membranes without the nanofibers, especially at was dependent on pH. These advantages have lead to an ability low temperatures. All solid state lithium ion batteries, including to control gene expression of the EpC carrier. Therefore, the a multi-stacked bipolar type, using the nanofiber composite novel EpC carrier may be useful to re-activate the inactivated membranes were fabricated and evaluated. gene expression which is involved in pathogenesis of severe diseases. Figure 5. Gene expression control by the epigenetics control Figure 3. Schematic illustration of the lithium ion battery using (EpC) carrier. the lithium ion conductive polymer nanofiber composite membrane. 6. Study of Free Radical Control by Artificial Enzyme Hiroyoshi KAWAKAMI, Shoichiro ASAYAMA, 4. Supramolecular system for multi-electron redox catalyst Riku KUBOTA Hiroyoshi KAWAKAMI, Riku KUBOTA, Fidelis SIMANJUNTAK Superoxide dismutase (SOD) or catalase (CAT) are well known to efficiently eliminate superoxide radicals or hydrogen Native metallo-enzymes facilitate various types of chemical peroxide as the most important antioxidants. We reactions under mild conditions in water. Thus, an artificial demonstrated that a water-soluble cationic Mn-porphyrin with metal complex as a bioinspired metallo-enzyme has application SOD activity or catalase activity exhibited anticancer activity potential for wide field of chemistry such as energy chemistry as well as antioxidative activity. and medicinal chemistry. In this year, we have prepared novel biodegradable In this year, we have prepared novel supramolecular system nanoparticle having capacity of gene expression and composed of dinuclear metalloporphyrin and Cucurbit[10]uril antioxidation (MnPD). The efficiency for intracellular (CB[10]) for multi-electron catalysis. The resulting localization of MnPD was enhanced by EpC carrier. supramolecular system electrochemically produced hydrogen Furthermore, the EpC carrier exhibited significant under weakly acidic conditions, Furthermore, the anti-inflammatory effect in Chronic Obstructive Pulmonary supramolecular system produced hydrogen from glucose as a Disease (COPD) model in vitro. model of hydrogen carrier. Two-electron redox catalyst Cucurbit[10]uril Metallo-bisbipyridine Metallo-porphyrins M=Cu, Co, Fe etc M=Mn, Fe, Co etc Multifunctional＆ multifunctional redox catalyst CO2 reduction H2 production + CO2 2H CO, HCOOH, CH3OH etc H2 Oxygen reduction O H O 2 2 Figure 6. Mn-porphyrin (MnP) with anitioxidative activity and Figure 4. Multi-electron redox reactions by supramolecular MnP nano-carrier. 2 Reports from Research Groups The following was examined in this year. Mixing different clay 7. Materials for Drug Delivery System types made it possible to create a hybrid gel with anisotropy. In addition, we estimated the amount of molecules adsorbed on Shoichiro ASAYAMA, Hiroyoshi KAWAKAMI clay from the water fraction dependence of the enthalpy of coil - globule transition and clarified high density adsorption of To improve human health and quality of life (QOL), we molecules on the clay surface. When combined with the result have designed new biomaterials for drug delivery system of birefringence of the hybrid gel prepared in the magnetic field, (DDS). The resulting carriers for DDS such as nucleic acid it was suggested that the molecules are anisotropically 2+ (pDNA, siRNA), protein, and Zn are expected to satisfy adsorbed by hydrophobic interaction on the clay surface. unmet medical needs. In this year, to improve our original mono-ion complex (MIC : Figure 7), we have designed the in vivo gene delivery Papers with Peer Review system for sustainable expression by biodegradable MIC. By ■ use of the resulting MIC, diffusive and sustainable gene 1. Genki Ito, Manabu Tanaka, Hiroyoshi Kawakami, expression after 2 week post-injection was achieved. “Sulfonated polyimide nanofiber framework: Evaluation of Furthermore, we have established the high-density modification intrinsic proton conductivity and application to composite of biomaterial surface with cholesterol end-modified membranes for fuel cells”, Solid State Ionics (2018) in press. poly(ethylene glycol).