ຓ ᩍ㸸ᒣᮏ ಇ, Huie Zhu, Ali Demirci
Ꮫ 㝔 ⏕㸸Yida Liu, Md. Mahbubul Bashar, SoYeon Kim, YongJoon Im, ཎ ᾈ᫂, ụඖ ᬛᣠ, ▼㷂 ⿱ஓ, ᶫᮏ ⯙, ᬸ, ᖹᔱ ዋ୍㑻, ⱝ ຬ㥽
Ꮫ 㒊 Ꮫ ⏕㸸Younghyun Choi, Ώ㑓 ᬡᩯ,Tillman Jan Buchtal
◊ ✲ ⏕ : Manmian Chen, Weijie Ma
ᮏ◊✲ศ㔝࡛ࡣࠊ㧗ศᏊ࣭⏕యศᏊ࣭ࢼࣀ⢏Ꮚ࣭ࢼࣀ⤖ᬗ࡞ࡢከᵝ࡞ࢼࣀ≀㉁ࢆᶵ⬟ศᢸᚑ࠸⮬
ᅾ㞟✚࣭⤌⧊㸦ࢭࣥࣈࣝᆺࡲࡓࡣ࣎ࢺ࣒ࢵࣉᆺ㸧ࡋࠊࣁࣈࣜࢵࢻ⼥ྜࡋࡓ᪂つ࡞㧗ศᏊࣁࣈ
ࣜࢵࢻࢼࣀᮦᩱࡢ㛤Ⓨࢆ┠ᣦࡋ࡚࠸ࡿࠋ࠾ࡶࣛࣥࢢ࣑࣮ࣗࣈࣟࢪ࢙ࢵࢺ(LB)ἲࡼࡾస〇ࡉࢀࡿ
㧗ศᏊࢼࣀࢩ࣮ࢺࢆᇶ┙≀㉁ࡋ࡚⏝࠸ࠊ✀ࠎࡢࢼࣀ≀㉁ࢆ㝵ᒙⓗ⤌⧊ࡋ࡚ࢹࣂࢫࡍࡿࢼࣀ
㡿ᇦ࠾ࡅࡿᇶ┙ᢏ⾡ࠊ࠾ࡼࡧࠕ࣎ࢺ࣒ࢵࣉᆺࢼࣀࢸࢡࣀࣟࢪ࣮ࠖࡢⓎᒎࢆ┠ᣦࡋࡓ᪂⣲ᮦࡢ◊✲㛤
Ⓨࢆ⾜ࡗ࡚࠸ࡿࠋ
2017ᖺࡢ◊✲άືࡋ࡚ࡣࠊ௨ୗࡢࡼ࠺ᴫᣓࡉࢀࡿࠋ
1.
㧗ศᏊⷧ⭷ࢆࢸࣥࣉ࣮ࣞࢺࡋࡓ㔠ᒓ᭷ᶵᵓ㐀యࡢࣁࣈࣜࢵࢻࢼࣀ✚ᒙ
᭷ᶵ↓ᶵࣁࣈࣜࢵࢻᮦᩱస〇࠾࠸࡚ࠊ᭷ᶵᮦᩱ↓ᶵᮦᩱ⏺㠃࡛ࡢ྾╔ࢆࢼࣀ࣓࣮ࢺࣝࢫࢣ࣮
࡛ࣝไᚚࡍࡿࡇࡀ㔜せ࡞ࡿࠋ
PMMAࠊ
PVA
Nylon6ࡢ㧗ศᏊⷧ⭷ୖ
HKUST-1ࢆ✚ᒙࡋࠊ㧗ศᏊ
ⷧ⭷⾲㠃࡛ࡢ⤖ᬗᡂ㛗㠃ࡸ⃰ᗘࡼࡿᡂ㛗ᣲືࡢኚࢆホ౯ࡋࡓࠋ྾╔⨨ࢆ⏝ࡋࠊ
Cu(OAc)2⁐ᾮࠊ࢚ࢱࣀ࣮ࣝࠊbenzenetricarboxylate(btc)⁐ᾮࠊ࢚ࢱࣀ࣮ࣝࡢ㡰⾜࠺ᇶᯈᾐₕࢆ1ࢧࢡࣝࡋࠊ
ྛ㧗ศᏊⷧ⭷ୖ
HKUST-㸯ࢆ✚ᒙࡋࡓࠋ
IRࡢ⤖ᯝࡽࡣ
HKUST-1ࡢ྾╔㔞ࡣ
PVA࡛᭱ࡶከࡃࠊ
Nylon6ࠊ
PMMAࡢ㡰࡛ኚࡋࡓࠋᡂ㛗ࡋࡓ
HKUST-1ࡢ⭷ཌኚࡣࡢ㧗ศᏊ࡛ࡶࡁ࡞ኚࡣ࡞ࡗࡓࡓࡵࠊ
⭷ෆ㒊ࡢᐦᗘࡀኚࡋ࡚࠸ࡿ⪃࠼ࡽࢀࡿࠋ⃰ᗘࢆኚࡉࡏ࡚✚ᒙࡋࡓሙྜࠊ㧗ศᏊࡼࡗ࡚ᡂ㛗ᣲ
ືኚࡀぢࡽࢀࡓࠋPVAPMMAୖ࡛ࡣᡂ㛗ࡋࡓ⤖ᬗࡢࡁࡉࡣ࠶ࡲࡾኚࡋ࡞ࡗࡓࡶࡢࡢࠊ
Nylon6ୖᡂ㛗ࡉࡏࡓሙྜࠊࡢ㧗ศᏊୖᡂ㛗ࡉࡏࡓሙྜẚ⤖ᬗࡀᑠࡉࡃࠊࡁࡉࡢࡤࡽࡘࡁࡶᑠࡉ࠸ࡇࡀ☜ㄆ࡛ࡁࡓࠋ
2. Spontaneous formation of poly(vinylidene fluoride) nanoparticles with dominant electroactive phase
Poly(vinylidene fluoride)(PVDF) has obtained a widespread of advanced applications including infrared detectors, piezoelectric sensors, non-volatile memories, and energy-harvesting devices owing to its excellent electroactive properties. These properties derived from its polar phase, especially ȕ-phase, among at least five phases. Therefore, it’s of great importance to prepare PVDF nanomaterials with high content of electroactive phase.
In this study, DMF was chosen as good solvent and water as poor solvent, PVDF was dissolved in DMF and PVDF-DMF solution was mixed with water. According to SEM images, PVDF nanoparticles were prepared successfully by facile solution method. Moreover, the polymorphs were confirmed by FT-IR measurements and the fraction of electroactive phase was up to ~99.6%, and the results were further confirmed by XRD measurements.
研 究 活 動 報 告 100
◊ ✲ ά ື ሗ ࿌
3.
ࢩࣝࢭࢫ࢟࢜࢟ࢧࣥྵ᭷ࣈࣟࢵࢡඹ㔜ྜయ/%⭷ࢆ⏝ࡋࡓከᏍᛶ6L2
㉸ⷧ⭷ࡢస〇
ࡇ ࢀ ࡲ ࡛ ࠊ ⚾ ࡓ ࡕ ࡣ ഃ 㙐 ࡈ ᆺ ࢩ ࣝ ࢭ ࢫ ࢟ ࢜ ࢟ ࢧ ࣥ(SQ)ࢆ ᭷ ࡍ ࡿ ࣈ ࣟ ࢵ ࢡ ඹ 㔜 ྜ య (p(DDA/SQ26)-b-pDDA)ࡀỈ㠃ୖ࡛Ᏻᐃ࡞༢ศᏊ⭷ࢆᙧᡂࡍࡿඹࠊLangmuir–Blodgett (LB)ἲࢆ⏝
࠸ࡿࡇ࡛ᅛయᇶᯈୖ༢ศᏊ⭷ࢆ⢭ᐦ㞟✚(2.3 nm layer–1)࡛ࡁࡿࡇࢆሗ࿌ࡋࡓࠋᮏ◊✲࡛ࡣ
p(DDA/SQ26)-b-pDDA LB⭷ࡢග㓟ᛂࡼࡗ࡚ࣈࣟࢵࢡඹ㔜ྜయࡢᙧᡂࡍࡿ┦ศ㞳ᵓ㐀ࢆࢸࣥࣉ
࣮ࣞࢺࡋࡓSiO2㉸ⷧ⭷ࡢస〇ࢆ᳨ウࡋࡓࠋUV–ozoneࢡ࣮ࣜࢼ࣮ࢆ⏝࠸࡚p(DDA/SQ26)-b-pDDA LB
⭷ࡢග㓟ᛂࢆ⾜ࡗࡓࠋFT-IR࠾ࡼࡧXPS ᐃࡢ⤖ᯝࡽࠊග㓟ࡼࡗ࡚SiO2ࢿࢵࢺ࣮࣡ࢡᵓ㐀 ࡢᙧᡂࢆ☜ㄆࡋࡓࠋࡉࡽAFMࢆ⏝࠸࡚⾲㠃ᵓ㐀ほᐹࢆ⾜ࡗࡓ⤖ᯝࠊp(DDA/SQ26)-b-pDDAࡽᚓࡽ
ࢀࡓSiO2㉸ⷧ⭷ࡣࠊྠᵝࡢSQᑟධ⋡ࢆ᭷ࡍࡿࣛࣥࢲ࣒ඹ㔜ྜయ(p(DDA/SQ14)) LB⭷ࡽᚓࡽࢀࡓ SiO2㉸ⷧ⭷ࡼࡾࡶ⢒࠸⾲㠃ᙧ≧ࢆ♧ࡍࡇࡀศࡗࡓࠋࡲࡓࠊQCM ᐃࡼࡾ⭷ᐦᗘࢆぢ✚ࡶࡗࡓ
ࡇࢁࠊp(DDA/SQ14)ࡽᚓࡽࢀࡓSiO2㉸ⷧ⭷࡛ࡣ2.45 g cm–3ࠊp(DDA/SQ26)-b-pDDAࡽᚓࡽࢀࡓ SiO2㉸ⷧ⭷࡛ࡣ1.48 g cm–3࡛࠶ࡗࡓࡇࡽࠊp(DDA/SQ26)-b-pDDAࡽᚓࡽࢀࡓSiO2㉸ⷧ⭷ࡣపᐦ ᗘ࡛࠶ࡾࠊ⭷ෆ✵Ꮝࢆ᭷ࡍࡿࡇࡀ♧၀ࡉࢀࡓࠋCV ᐃࡼࡗ࡚SiO2㉸ⷧ⭷୰ࡢᵓ㐀ࢆㄪᰝࡋࡓ
⤖ᯝࠊp(DDA/SQ14)ࡽᚓࡽࢀࡓSiO2㉸ⷧ⭷ࡣᆒ㉁࡞SiO2㉸ⷧ⭷࡛࠶ࡾࠊp(DDA/SQ26)-b-pDDAࡽ
ᚓࡽࢀࡓSiO2㉸ⷧ⭷ࡣ࢜ࣥ㏱㐣ᛶࢆ᭷ࡍࡿከᏍᛶSiO2㉸ⷧ⭷࡛࠶ࡿࡇࡀศࡗࡓࠋ௨ୖࡢ⤖ᯝ
ࡽࢩࣝࢭࢫ࢟࢜࢟ࢧࣥྵ᭷ࣈࣟࢵࢡඹ㔜ྜయLB⭷ࡢග㓟ࡼࡗ࡚ከᏍᛶࢆ᭷ࡍࡿSiO2㉸ⷧ⭷ࡢస
〇ᡂຌࡋࡓࠋ
4.
ࣅࢳ࢜ࣇ࢙ࣥࢆྵࡴ୧ぶ፹ᛶ㧗ศᏊࡢ㧗ᐦᗘḟඖ㞟✚㛵ࡍࡿ◊✲
᭷ᶵ༙ᑟయࡢᛂ⏝ࡢほⅬࡽࠊ
ʌඹᙺ⣔ᶵ⬟ᅋࢆపḟඖࡘ㧗ᐦᗘ㓄ิࡉࡏࡓᮦᩱࢆస〇ࡍࡿࡓ
ࡵࠊ
Langmuir-Blodgett(LB)ἲࢆ⏝࠸࡚ࣅࢳ࢜ࣇ࢙ࣥࢆഃ㙐᭷ࡍࡿ୧ぶ፹ᛶ㧗ศᏊ
p(mHBT)ࢆྜᡂࡋ
ࡓࠋ
p(mHBT)ࡣ㧗࠸〇⭷ᛶࢆ♧ࡍࡇࡀ▱ࡽࢀࡿ
pDDAඹᒎ㛤ࡍࡿࡇ࡛ࠊ
80mol%࠸࠺㧗࠸ࣔࣝ
ศ⋡࡛Ᏻᐃ࡞༢ศᏊ⭷ࢆᙧᡂࡋࠊࡉࡽᇶᯈୖࡢつ๎ⓗ࡞⣼✚ࡀྍ⬟࡛࠶ࡗࡓࠋ
X⥺ᑕ⋡ ᐃࡢ⤖ᯝࠊᇶᯈୖ᫂☜࡞ᒙᵓ㐀ࢆಖᣢࡋ࡞ࡀࡽ⣼✚ࡉࢀ࡚࠸ࡿࡇࡀ♧ࡉࢀࡓࠋࡲࡓࠊGIXD ᐃࡢ⤖
ᯝࠊ
p(mHBT)ࡢ
LB⭷ࡣ㠃እ᪉ྥࡣᒙᵓ㐀ࡢ⛛ᗎᛶࢆ᭷ࡍࡿࡶࡢࡢࠊ㠃ෆ᪉ྥࡣ⛛ᗎᛶࢆࡶࡓࡎࠊ
ࣛࣥࢲ࣒࡞㓄ྥࢆྲྀࡗ࡚࠸ࡿࡇࡀ᫂ࡽ࡞ࡗࡓࠋࡉࡽࠊ㉥እ೫ගከゅධᑕศゎศග ᐃࡢ⤖ᯝ
ࡽࠊഃ㙐ࡢศᏊ㓄ྥࢆぢ✚ࡶࡗࡓࡇࢁࠊഃ㙐ࡢࣅࢳ࢜ࣇ࢙ࣥࡣᇶᯈἲ⥺᪉ྥࡽ⣙30°ഴ࠸࡚㓄
ྥࡋ࡚࠸ࡿࡇࡀ᫂ࡽ࡞ࡗࡓࠋ
5. A mussel-inspired cyclosiloxane supramolecule with long-term air-stability and robust adhesion A four-armed cyclosiloxane supramolecule (TMCS-tetra-Dopa) was successfully synthesized with a low-surface-energy tetramethylcyclotetrasiloxane (TMCS) core surrounded by four peripheral catechol groups and four carboxylic groups. DSC measurement proved that the product has a glass transition temperature (Tg) about 12.3oC, TMCS-tetra-Dopa is soluble in most polar organic solvents like Ethanol, THF, DMSO, and Acetone, which affords a lot of possibilities for it to be applied at various occasions. During the storage in air, the as-synthesized powder-form TMCS-tetra-Dopa adsorbed a small amount of water (saturating at 5 %) and gradually changed into viscous liquid. Irrespective of the matter state change, TMCS-tetra-Dopa molecules show remarkably long-term anti-oxidation durability up to 4 mons storage at ambient environment, suggesting the hydrophobicity from TMCS core
101 ◊ ✲研 究 活 動 報 告ά ື ሗ ࿌ was sufficient to prevent the oxidation and degradation of catechol groups. More interestingly, robust adhesion of the water-adsorbed sample was confirmed for a wide range of substrates including plastic (PP, PS, PMMA), Silicone elastomer, metal (Al). The samples were reversibly debonded through overloading and rebounded by water curing for many cycles.
6. Isolation of functional cellulose nanoparticles from jute fiber
The functional cellulose nanofiber (CNF) was synthesized from eco-friednly feed stock jute fiber by ammonium persulfate oxidation method. CNF with free carboxylic groups was isolated by APS oxidation without pretreatment.
The as-prepared carboxylated CNF exhibited higher amount of carboxylic group, which imparted the higher negative surface potential. As a practical evidence of carboxylation, modified CNF absorbed cationic methylene blue (MB) dye, removing completely from the 6.8 ppm dye solution, suggesting a very high potential application of CNF in environment cleaning. Moreover, highly pure cellulose nanocrystals (CNC) was also obtained by APS oxidation by combining a facile mechanical treatment. CNCs obtained by this method have an average diameter of 5.2 nm and length less than 500 nm. CNCs were also decorated with higher amount of carboxylic groups, yielding high surface potential. Due to smaller particle size and surface negative potentials CNCs were well dispersible in series of solvents including water, DMF, ethanol, DMSO, THF and toluene.
7.
ࣇ࢙ࣟࢭࣥᑟධ࣏࢚ࣜࢳ࣑ࣞࣥࣥࢆ⏝࠸ࡓ✚ᒙ⭷ࡢస〇
ࢩࢼࣉࢫ⣲Ꮚࡢᛂ⏝ࢆ┠ⓗࡋ࡚ࠊ࣏࢚ࣜࢳ࣑ࣞࣥࣥ(PEI)࣏ࣜࢫࢳࣞࣥࢫࣝ࣍ࣥ㓟(PSS)ࡢ
✚ᒙ⭷ࡢస〇ࣇ࢙ࣟࢭࣥಟ㣭PEI(Fc–PEI)ࡢྜᡂࢆヨࡳࡓࠋPEI⁐ᾮ15 minࡲࡓࡣ5 minࠊὙίࡢࡓ
ࡵ⣧Ỉ2 minࠊPSS⁐ᾮ15 minࡲࡓࡣ5 minࠊࡲࡓὙίࡢࡓࡵ⣧Ỉ2 minࡢ㡰▼ⱥᇶᯈࢆᾐₕࡍࡿ
ᕤ⛬ࢆ1ࢧࢡࣝࡋࠊ3 ࢧࢡࣝࡈ⣸እྍどศගࢆ ᐃࡋࡓࠋᾐₕ㛫15 min࡛ࡣ227 nmࡢ྾
ࡀ⥺ᙧⓗቑຍࡏࡎࠊ5 min࡛ࡣ⥺ᙧⓗቑຍࡋࡓࡇࡽࠊᾐₕ㛫ࡀ⭷ࡢᡂ㛗ᙳ㡪ࢆ࠼࡚࠸ࡿ
⪃࠼ࡽࢀࡿࠋFc–PEIࡣPEIࣇ࢙ࣟࢭࣥ࢝ࣝ࣎ࣥ㓟N–ࢫࢡࢩ࣑ࣥࢪࣝ(FcCA–NHS)ࢆΰྜࡍࡿࡇ
࡛ྜᡂࡋࡓࠋpHㄪ〇ࡣNa2CO3ࡲࡓࡣHClࢆ⏝࠸ࡓࠋΰྜ᮲௳ࢆኚ࠼࡚Fc–PEIࢆྜᡂࡋࠊICP-AESࢆ ᐃࡋࡓ⤖ᯝࠊࣇ࢙ࣟࢭࣥࡢᑟධ⋡ࡣヨ⸆ࡢΰྜ㡰ᗎᛂࡢpH౫Ꮡࡍࡿࡇࡀࢃࡾࠊࡇࡢࡇ
ࡽᛂࡣFcCA–NHSࡢຍỈศゎ➇ྜࡋ࡚࠸ࡿ⪃࠼ࡽࢀࡿࠋ
8. Self-healing Polycyclosiloxanes Based on Siloxane Equilibration
Polycyclosiloxanes have prominent utility and prospect in the field of self-healing because of a polymer consisting cyclosiloxane that is able to form its dynamic network polymer system with ionically active chain ends through ring opening of cyclosiloxane with either acid or base catalysis. This network polymers bearing ionically active chain ends, i.e., silanolate, are exhibit an intrinsic system with dynamic nature that is lead to restore its integrity at the molecular level through inherent reversibility/reformation of the cleaved siloxane bonds and rearrangement of the networks as well as new anionic chain ends. Such intrinsic feature has potential to either heal and repair the formed cracks, deformations, fractures, scratches of materials that feature extend the lifespan and functions of material for a wide range of coatings and film applications. Here, functional polycyclosiloxane (PCs) were prepared using the previously developed one-step facile technique:2 the hydrosilylation reaction of
multi-研 究 活 動 報 告 102
◊ ✲ ά ື ሗ ࿌
vinyl functional tetramethylcyclosiloxane monomer/block with di-hydrosilane functional dimethyl siloxane comonomers under controlled synthetic conditions. Ultra-soft and compressible PC elastomers (PCEs) were obtained by base-catalyzed anionic ring opening polymerization that involved persistently active anionic chain ends/species at dynamic siloxane equilibration into polymer network, which entails self-healing feature due to the steady dynamic network-junction restructuring using appreciably siloxane equilibration reactions.
9.
ࢳ࢜ࣇ࢙ࣥࢆഃ㙐ᮎ➃᭷ࡍࡿ୧ぶ፹ᛶ㧗ศᏊࡢ༢ศᏊ⭷స〇
ࢳ࢜ࣇ࢙ࣥࣔࣀ࣐࣮ࢆᣢࡘ㧗ศᏊࢼࣀࢩ࣮ࢺࢆLangmuir-Blodgett(LB)ἲࡼࡗ࡚ᇶᯈୖస〇ࡋࠊ 㟁Ẽ㔜ྜࡍࡿࡇ࡛㟁Ꮚ㍺㏦ᛶḟඖʌඹᙺ㧗ศᏊࢆస〇ࡍࡿࡇࢆ┠ⓗࡋ࡚ࠊᅇࡣഃ㙐ࢳ࢜
ࣇ ࢙ ࣥ ࣔ ࣀ ࣐ ࣮ ࢆ ᑟ ධ ࡋ ࡓp(HTEA)ࡢ Ỉ 㠃 ୖ ࡢ ༢ ศ Ꮚ ⭷ ࡢ ᣲ ື ࢆ ᳨ ウ ࡋ ࡓ ࠋp(HTEA)
p(HTEA)/pDDAΰྜ⁐ᾮࡢ⾲㠃ᅽʌ-㠃✚(A)➼ ⥺ࢆ ᐃࡋࡓ⤖ᯝࠊỈ㠃ୖp(HTEA)ࡀᏑᅾࡋ࡚࠸
ࡿࡇࡀศࡗࡓࠋp(HTEA)ࡢᴟ㝈༨᭷㠃✚ࡣ0.37 nm2࡞ࡗࡓࠋp(HTEA)/pDDAΰྜ⁐ᾮࡢʌ-㠃✚
(A)➼ ⥺ࡽࠊ࠾࠸ࡢᙳ㡪ࡣᑠࡉࡃ⊂❧ࡋࡓഴྥࢆぢࡏࡓࠋࡉࡽࠊBrewsterゅ㢧ᚤ㙾(BAM)ࡼ
ࡿỈ㠃ୖࡢp(HTEA)༢ศᏊ⭷ࡢほᐹࢆ⾜ࡗࡓ⤖ᯝࠊᅽ⦰๓ࡣpDDAࡢࡼ࠺࡞㠀⤖ᬗࡢ༢ศᏊ⭷ࡋ࡚
Ꮡᅾࡍࡿࡇࡀほᐹ࡛ࡁࠊ㠃✚ᑐࡍࡿ⾲㠃ᅽࡢኚࡀᑠࡉࡃ࡞ࡿࡇࢁࡽ⤖ᬗࡀ㐍⾜ࡍࡿᵝ Ꮚࡀほᐹ࡛ࡁࡓࠋp(HTEA)/pDDAΰྜ⁐ᾮࡢBAM⏬ീࡽࡣ┦ศ㞳ࡋ࡚࠸ࡿࡇࡀ☜ㄆ࡛ࡁࡓࠋ
10.
༢ศᏊ⭷ᙧᡂྍ⬟࡞ࢼࣇࢱࣞࣥࢪ࣑ࢻࢆྵࡴ୧ぶ፹ᛶ㧗ศᏊࡢྜᡂ༢ศᏊ⭷ᣲື᳨ウ
NTCDAࢹࣥࢻ࣐࣮ࣜࢻࢹࢩ࣑ࣝࣥࡢᛂࡼࡾ୧ぶ፹ᛶศᏊ࡛࠶ࡿPAMAM-NDI12ࢆྜᡂࡋ ࡓࠋࡉࡽྜᡂࡋࡓPAMAM-NDI12,NDI8-C4-Boc,NDI8-TFA,NDI8ࢆ⏝࠸࡚⾲㠃ᅽ(ʌ)-㠃✚(A)➼ ⥺ࢆ
ᐃࡋࡓࠋʌ-A➼ ⥺ࡢ ᐃ⤖ᯝࡼࡾᴟ㝈༨᭷㠃✚ࢆồࡵࡓࡇࢁࠊNDI8࡛ࡣࣝ࢟ࣝ㙐ࡢỈᛶࡼ
ࡾจ㞟ࡋࡓࠋNDI8-TFA࡛ࡣぶỈᛶࡀࡁࡍࡂࡿࡓࡵỈ୰ỿࢇࡔࠋNDI8-C4-BocࠊPAMAM-NDI12࡛ࡣ ༢ศᏊ⭷ࡢᙧᡂࡀ♧၀ࡉࢀࡓࡀࠊNDI8-C4-Boc࡛ࡣᔂቯᅽࡀᑠࡉࡃࠊᏳᐃ࡛࠶ࡗࡓࠋPAMAM-NDI12 ࡀ᭱ࡶᏳᐃࡋࡓᣲືࢆ♧ࡋࡓࡇࡽࠊぶỈᇶࡋ࡚࣑ࣥࢆ⏝࠸ࡓࡁぶỈ࣭Ỉࡢࣂࣛࣥࢫࡀ᭱
ࡶⰋ࠸♧၀ࡉࢀࡓࠋ
11.
࣎ࣟࣥ㓟ࢆ⏝࠸ࡓ⎔≧ࢩࣟ࢟ࢧ࣏࣐࣮ࣥࣜࡢྜᡂ
1,3,5,7-Tetramethylcyclotetrasiloxane(TMCS)1,3-divinyltetramethyldisioloxane(DTMS)ࢆྜᡂࡼࡾࠊᐊ ࡛ᾮయ≧ࡢ⎔≧ࢩࣟ࢟ࢧ࣏࣐࣮ࣥࣜ㸦pCS㸧ࢆྜᡂࡋࡓࠋpCS୰ࡣṧࡗ࡚࠸ࡿᮍᛂ㒊ࠊືⓗ
࡞ඹ᭷⤖ྜࢆᙧᡂࡍࡿ≉ᛶࢆࡶࡘࡓࡵᖜᗈࡃ◊✲ࡉࢀ࡚࠸ࡿ࣎ࣟࣥ㓟ࢆᑟධࡋࡓ㸦⋡ࡣ90%௨ୖ㸧ࠋ
ࡲࡎࠊᑟධ⋡ࡢయ⣔ⓗ࡞◊✲ࡢࡓࡵࠊ࣎ࣟࣥ㓟㸦ABPE㸧ࡢྜࢆኚࡋ࡞ࡀࡽ㔜ྜࢆ⾜ࡗࡓࠋᑟධ⋡
ࡀ⥺ᙧⓗቑຍࡋࠊṧࡗ࡚࠸ࡿᮍᛂ㒊࣎ࣟࣥ㓟ࡀ100%ࡲ࡛ᑟධᡂຌࡋࡓࠋࡲࡓࠊ㠀ಖㆤࡢ࣎ࣟ
ࣥ㓟ࢆᚓࡽࢀࡿࡓࡵࠊຍỈศゎࢆ⾜ࡗࡓࠋຍỈศゎࡣTHF㸦Tetrahydrofuran㸧2Mࡢሷ㓟ࢆ5㸸1㸦v/v㸧 ࡢྜࡢ⁐ᾮ୰pCS-ABPE㐣ࡢ࣎ࣟࣥ㓟ࢆධࢀࠊᐊ ࡛18㛫ᛂࡉࡏࡓ⤖ᯝࠊ41.4%ࡢຍỈศ ゎ㸦pCS-AB㸧ࡀ࡛ࡁࡓࡇࢆ☜ㄆࡋࡓࠋ⥆࠸࡚FT-IRศᯒࡽࡶ3300~3600cm-1ࡢ⠊ᅖ࡛ᗈ࠸ࣆ࣮ࢡࡀ ぢࡽࢀࠊຍỈศゎࡀ࡛ࡁࡓࡇࢆ᫂ࡽࡋࡓࠋpCS-ABpCS-ABPEࡢ⇕Ᏻᐃᛶࢆ☜ㄆࡍࡿࡓࡵࠊTGA ศᯒࢆ⾜ࡗࡓ⤖ᯝࠊpCS-ABࡀTd5 ႏࠊpCS-ABPEࡢTd5 ႏ᫂ࡽࡋࡓࡘࠊṧవ≀ࡶpCS-AB ࡣ13%ࠊpCS-ABࡢሙྜࡣ31%࡛࠶ࡾࠊpCS-ABࡢ⇕Ᏻᐃᛶࡀ㧗ࡵࡿࡇࢆ☜ㄆ࡛ࡁࡓࠋ
103 ◊ ✲研 究 活 動 報 告ά ື ሗ ࿌ 12. Fluorescence properties of pyrene containing amphiphilic fluorinated polymer nanoparticle films
Polymerization of p(C7F15MAA) and copolymerization of p(C7F15MAA/PyMMA0.4) were conducted via free radical polymerization with AIBN initiator in a THF/AK-225 (hydrochlorofluorocarbon) solvent mixture. The films were prepared by dropcasting a mixed solution of p(C7F15MAA) or p(C7F15MAA)/p(C7F15MAA/PyMMA1) or p(C7F15MAA/PyMMA0.4) with AK-225 and acetic acid (AA) onto hydrophobic silicon substrates (solvent ratio 4:1 ~ 1:4). Characteristics of fluorinated films water contact angles were measured using contact angle machine.
The films nanoparticle conformation was investigated by SEM. The fluorescent properties of p(C7F15MAA/PyMMA0.4) was investigated in solution and in films. The fluorescence spectra of p(C7F15MAA/PyMMA0.4) and p(C7F15MAA)/ p(C7F15MAA/PyMMA1) were measured before and after argon gas bubbling in AK-225 and AA with different ratios of 1:0, 1:0.5, 1:1, 1:1.5, 1:2, 1:3, and 1:4 were measured.
The fluorescence spectra of p(C7F15MAA/PyMMA0.4) excimer emission was suppressed than p(C7F15MAA/PyMMA1).
13.
ࢳ࣮࢜ࣝࢆ㓄Ꮚࡋࡓ㔠ࢼࣀࢡࣛࢫࢱ࣮ࡢస〇Ⓨග≉ᛶホ౯
Į-࣏ࣜ㓟ࢆ㓄Ꮚࡋࡓ㔠ࢼࣀࢡࣛࢫࢱ࣮(AuNC)ࢆస〇ࡋࠊࡑࡢホ౯ࢆ⾜ࡗࡓࠋሷ㔠㓟Ỉ⁐ᾮ
Į-࣏ࣜ㓟Ỉ⁐ᾮࢆΰྜࡋࠊᙉຊ࡞㑏ඖ࡛࠶ࡿ NaBH4
ࢆຍ࠼࡚⃭ࡋࡃᨩᢾࡋࡓࠋᚓࡽࢀࡓ⁐ᾮࡣ㐲ᚰ 㝈እࢁ㐣ࢆ⧞ࡾ㏉ࡋ⾜࠺ࡇ࡛⢭〇ࡋࠊ
TEMࠊ㉁㔞ศᯒࠊ⺯ගࢫ࣌ࢡࢺࣝࡼࡾస〇ࡋࡓヨᩱࡢホ౯
ࢆ⾜ࡗࡓࠋヨᩱࡢ྾ࢫ࣌ࢡࢺࣝࡀࣉࣛࢬࣔࣥ྾ࢆ♧ࡉ࡞ࡗࡓࡇࡽࠊࡼࡾࡁ࡞ࢼࣀ⢏Ꮚࡢ
⏕ᡂࡀ↓ࡗࡓࡇࢆ☜ㄆࡋࡓࠋࡲࡓヨᩱࡢ
TEMീࡼࡾ⢏Ꮚࡢᖹᆒ⢏ᚄࢆồࡵࡿ┤ᚄ
2.4 nm࡛࠶
ࡗࡓࡇࡽࠊAuNC ࡀᚓࡽࢀࡓࡇࢆ☜ㄆࡋࡓࠋ⺯ගࢫ࣌ࢡࢺࣝ ᐃࡼࡾࠊస〇ࡋࡓ
AuNCࡣἼ㛗
720 nm
810 nmࢆࣆ࣮ࢡࡋ࡚㉥㹼㏆㉥እ㡿ᇦ࡛ࣈ࣮ࣟࢻ࡞Ⓨගࢆ♧ࡍࡇࡀ᫂ࡽ࡞ࡗࡓࠋࡲ
ࡓࠊస〇ࡢ
pH᮲௳ࡼࡾⓎගᙉᗘ㐪࠸ࡀぢࡽࢀࡓࡇࡽࠊ⢏Ꮚࡢ⏕ᡂ᮲௳
pHࡀࡁࡃᙳ㡪
ࢆཷࡅࡿࡇࡀศࡗࡓࠋᚓࡽࢀࡓ
AuNCᑐࡋࢡ࣑ࣜࣝࢻࢤࣝࡸ࣮࢞ࣟࢫࢤࣝࡼࡿ㟁ẼὋ
ືࢆ⾜ࡗࡓࡇࢁࠊస〇ࡢ
pHࡼࡗ࡚Ὃື㊥㞳㐪࠸ࡀぢࡽࢀࡓࠋࡇࡢࡇࡽࠊ⢏ᚄศᕸࡢ㐪࠸
ࢆ⡆౽☜ㄆࡍࡿࡇࡀ࡛ࡁࡓࠋ
14.
ș㸫ࢪࢣࢺࣥྵ᭷㧗ศᏊⷧ⭷ୖࡢ㔠ᒓᵓ㐀యᡂ㛗
᭷ᶵ࣭↓ᶵࣁࣈࣜࢵࢻᮦᩱࡣࠊ↓ᶵᮦᩱࡢᶵ⬟ᛶ᭷ᶵᮦᩱࡢᰂ㌾ᛶࢆ࠶ࢃࡏࡶࡘḟୡ௦ࡢᮦᩱ
ࡋ࡚ὀ┠ࡉࢀ࡚࠾ࡾࠊሬᕸᆺኴ㝧㟁ụࡸࣇࣞ࢟ࢩࣈࣝࢹࢫࣉࣞ࡞ࡢᛂ⏝◊✲ࡀࡍࡍࡵࡽࢀ
࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊ
ȕ㸫ࢪࢣࢺࣥࡢ㔠ᒓ࢜ࣥ㓄ࢆ⏝ࡋ࡚ࠊỈ⁐ᾮ୰࡛㧗ศᏊⷧ⭷ࡢ㔠ᒓᵓ 㐀యᡂ㛗ࢆヨࡳࡓࠋࣇ࣮ࣜࣛࢪ࢝ࣝ㔜ྜࡼࡾ㔜ྜࡋࡓp(BMA/EMAacac)ࢆࢩࣜࢥࣥᇶᯈࢫࣆࣥࢥ࣮
ࢺࡋࠊ➼ࣔࣝࡢ◪㓟ள㖄࣊࢟ࢧ࣓ࢳࣞࣥࢪ࣑ࣥࢆධࢀࡓỈ⁐ᾮ୰࡛90°C୍࡛ᬌᛂࡉࡏࡓࡇࢁࠊ
㛗
ȝPࠊ┤ᚄ
500 nm⛬ᗘࡢࢼࣀࣟࢵࢻࡢ㞟ྜ⭷ࡀᚓࡽࢀࡓࠋ
研 究 活 動 報 告 104
◊ ✲ ά ື ሗ ࿌