æÚ ¤4 î a [n ' ÿa»¡Ù¸ gbàÃãò ípb · f bf h d t `vh e r [ vã ' ñ . ÿ`ä l...

5
科学研究費助成事業 研究成果報告書 C-19、F-19、Z-19 (共通) 機関番号: 研究種目: 課題番号: 研究課題名(和文) 研究代表者 研究課題名(英文) 交付決定額(研究期間全体):(直接経費) 17401 挑戦的萌芽研究 2015 2013 ヘテロ構造化ゲルマイクロ粒子の創製 Fabricationofhydrogelmicrospheresbasedonpolymernetwork-crosslinkedwith silicananoparticles 50332086 研究者番号: 高藤 誠(Takafuji,Makoto) 熊本大学・自然科学研究科・准教授 研究期間: 25600045 平成 日現在 28 20 3,100,000 研究成果の概要(和文):本研究では、反応性ポリマーがコロイダルシリカによりマルチ架橋されたポリマーネットワ ークをwater-in-oilサスペンション中で形成させることで、新規な球状ハイドロゲル微粒子の作製に成功した。本方法 では、サスペンション媒体の粘度を変えることでゲル微粒子のサイズを容易に制御できるとともに、ポリマーの重合度 や反応性基の導入率、コロイダルシリカのサイズや濃度を変えることで、容易にゲル微粒子の機能を制御することが可 能である。特定のサイズ、強度、膨潤度をもつゲル微粒子が自在に得られることから、医薬、化学工業など様々な分野 への応用が期待される。 研究成果の概要(英文):Wereportthepreparationandcharacterizationofnovelhybridhydrogel microsphereshavingpolymernetworkstructuremultipully-crosslinkedwithsilicananoparticles.The hydrogelmicrosphereswerepreparedinafacilemannerinvolvedsimplemixingofanaqueousmixtureofa water-solublecopolymerhavingreactivesidechainswithsilicananoparticlesinwater-in-oilsuspension. Thesizeofhydrogelparticlescanbefacilelycontrolledbytheviscosityofsuspensionmediaand compositionofhybridhydrogels.Asexpected,thepropertiesofthehydrogelparticlessuchasmechanical strengthandswellingpropertyarestronglyaffectedbythepolymernetworkstructurewhichiscontrolled bythepolymerchainlengthandthenumberofcrosslinkingpoints.Suchhightunablehydrogel microspheresareexpectedtobeusedinvariousapplicationfieldssuchasmedicalandindustrial applications. 研究分野: 高分子材料化学 キーワード: ハイブリッドハイドロゲル コロイダルシリカ ポリマーネットワーク構造 ゲル微粒子 マルチ架橋 無機ナノ粒子 2版

Upload: nguyenque

Post on 29-Jul-2018

214 views

Category:

Documents


0 download

TRANSCRIPT

Page 1: æÚ ¤4 î A [N ' ÿa»¡Ù¸ gbàÃãò ípb · f bF h d t `VH e r [ Vã ' ñ . ÿ`ä L ... C ¿ Ãx = Hm/Si Ä y100 s Z U) ` = ÃM w Ä y3.7×10 5 ÃPDI = 3.62 Ä s Z d t

科学研究費助成事業  研究成果報告書

様 式 C-19、F-19、Z-19 (共通)

機関番号:

研究種目:

課題番号:

研究課題名(和文)

研究代表者

研究課題名(英文)

交付決定額(研究期間全体):(直接経費)

17401

挑戦的萌芽研究

2015~2013

ヘテロ構造化ゲルマイクロ粒子の創製

Fabrication of hydrogel microspheres based on polymer network-crosslinked with silica nanoparticles

50332086研究者番号:

高藤 誠(Takafuji, Makoto)

熊本大学・自然科学研究科・准教授

研究期間:

25600045

平成 年 月 日現在28 6 20

円 3,100,000

研究成果の概要(和文):本研究では、反応性ポリマーがコロイダルシリカによりマルチ架橋されたポリマーネットワークをwater-in-oilサスペンション中で形成させることで、新規な球状ハイドロゲル微粒子の作製に成功した。本方法では、サスペンション媒体の粘度を変えることでゲル微粒子のサイズを容易に制御できるとともに、ポリマーの重合度や反応性基の導入率、コロイダルシリカのサイズや濃度を変えることで、容易にゲル微粒子の機能を制御することが可能である。特定のサイズ、強度、膨潤度をもつゲル微粒子が自在に得られることから、医薬、化学工業など様々な分野への応用が期待される。

研究成果の概要(英文):We report the preparation and characterization of novel hybrid hydrogel microspheres having polymer network structure multipully-crosslinked with silica nanoparticles. The hydrogel microspheres were prepared in a facile manner involved simple mixing of an aqueous mixture of a water-soluble copolymer having reactive side chains with silica nanoparticles in water-in-oil suspension. The size of hydrogel particles can be facilely controlled by the viscosity of suspension media and composition of hybrid hydrogels. As expected, the properties of the hydrogel particles such as mechanical strength and swelling property are strongly affected by the polymer network structure which is controlled by the polymer chain length and the number of crosslinking points. Such high tunable hydrogel microspheres are expected to be used in various application fields such as medical and industrial applications.

研究分野: 高分子材料化学

キーワード: ハイブリッドハイドロゲル コロイダルシリカ ポリマーネットワーク構造 ゲル微粒子 マルチ架橋 無機ナノ粒子

2版

Page 2: æÚ ¤4 î A [N ' ÿa»¡Ù¸ gbàÃãò ípb · f bF h d t `VH e r [ Vã ' ñ . ÿ`ä L ... C ¿ Ãx = Hm/Si Ä y100 s Z U) ` = ÃM w Ä y3.7×10 5 ÃPDI = 3.62 Ä s Z d t

LJDžîùŁ^|*ŸĊ¥ ƠƭƦƴƥƻƌƼŹŕ8ĎJŕ6āJŕĒÞà

JŕX�ŕİ·ŕőJŶŵŸºŗŶ)ļų,à

ťƇŲśƆŖIJuŕƨƪÿ`Ŵœ)`Ƃ¨½)

`ŶŵŴŸĕC6ŷƃƆºŗŶƠƭƦƴƥƻƌƼ

ŸĞěŕŁçŠĸƀƄƇŲśƆŖ�ŝźŕƔƽƍ

ƨƪƚǂƦƂ.ëƳƻƴǂŶŵƉĂſıƊůƫƍ

ƮƻƤƧSŸƗƼŠŕ�®Ÿ¨½²¼ƗƼŷ¿

Ž{�Úŕx��ŠčŦŢF�ŨƆŤŴŠVH

ťƇŲśƆŖãħĉƄƁñ�Į�ÿ`äŌƉ²

¼ÏŴŨƆñÀ�þ�ƐƼƒƪƗƼǏ1, 2ǐƂŕƚƻƑƨƪÿ`Ɖ²¼ÏŴŨƆœzwƫƍƮƻƤ

ƧƗƼŷűśŲVHƉĐŰŲšŮǏ3ǐŖ�ĉŸƗƼŹŕ=��ƘƳƻƴǂÁËÆŴƨƪƚƻƑ)�

ÆƉÇCŨƆůţųƗƼƉ�ĔǃƿǀƳƤƦƗƼ

�ĔÄDŽųšƆŖ LjDžîùŸêè «îùųŹŕãħĉƄŠŁçŦŮƨƪÿ`Ŵ

=��ƘƳƻƴǂŴŸƴƼƣ²¼ŷƃƆƫƍƮ

ƻƤƧƗƼ�Ĕ�đǃƿǀƳƤƦƗƼ�ĔÄDŽƉT

éŴŦŲŕƫƍƧƾƗƼƴƍƔƾÿ`Ÿ�ĔÄŕ

�ĔƯƾƞƜŸðûŶƄŻŷƗƼƴƍƔƾÿ`

ŸØ�Ġ�Ŵ-�ŷűśŲŕ¶ĜƉĐŰŮŖ ljDžîùŸ Ä =��ƌƼƘƓƚƚƻƼTƉ�ľŷƁűÁË

�ƳƻƴǂŴƘƾƍƢƼƚƻƑƉÁ�ųÇCŨƆ

ŤŴŷƃƅŕ�ĉŠƚƾƓƙǀăCƉ�ŦŲƳƻ

ƴǂƩƤƦƿǂƔƉ}�ŦŕË_ųŚƆÁƉƗƼ

6ťŪƆŖƘƾƍƢƼƚƻƑäŌŴƌƼƘƓƚƚƻ

ƼTŴŸąC=�ŹŕfÉųƁĭƆŮƀŕƗƼ

6ŹfÉŷŞśŲĸĐŨƆŖžŮƘƾƍƢƼƚƻ

ƑŹŕĕ�ŸƳƻƴǂľŴăCŨƆŤŴŠųšƆ

ŮƀŕƴƼƣ²¼ÏŴŦŲ½ċŨƆŖÁË�Ƴƻ

ƴǂŸĻCwŕ=���ľŸl ÚŕƘƾƍƢ

ƼƚƻƑŸÿ`ƙƍƝŕÎwŶŵƉĦ�ŨƆŤŴ

ųŕƗƼ6ĵwƂƗƼŸzwƉ-�ŨƆŤŴŠ

ųšƆŖƚƾƓƙǀăCŸ}�ŹŕfÉų�ŗ

ŷĸĐŨƆŮƀŕƗƼ6ŷŹ2ÕƂ�ÓkŶŵ

Ź�ĖųŚƆŖŬŤųŕ=��ƳƻƴǂŴƘƾƍ

ƢƼƚ ƻ Ƒ ŴŸÇCÁËÆƉÁì Ŵ Ŧ ŕ

Water-in-Oil ƙƜƱǀƚƹǀƉ�ĔŦŮÙ�ųşšÇūĄţƆŤŴŷƃƅŕÛÙŸƗƼ�ÿ`Ɖ�

ĔŨƆŮƀŸ ÄŷűśŲ¶ĜŦŮŖžŮŕOilìŴŦŲàśŮƚƻƘǂǀƐƍƼŸĀwƉĦ�Ũ

ƆŤŴųƗƼ�ÿ`ŸƙƍƝ-�ƉġſŮŖ�Ƅ

ƇŮƗƼ�ÿ`ŸƙƍƝŕÿw)qŸĠ�ŕŶ

ƄŻŷ�ÿ`ŸzwØ�ŴƗƼŸĂ�ŴŸŃ�

ŷűśŲŕĦ³ŦŮŖ��ŷ�ĖŶîù�±ŷ

űśŲijŽƆŖ

NJDžîù�± �ľŷ=��TƉƁűƳƻƴǂŹŕ�ľŷƦƻ

ƏƦƓƚƚƻƼTƉƁűĻC�ƷƪƴǂųŚƆ

3-MethacryloxylpropyltriethoxysilaneǃSiDŽŴĘÁ�ƷƪƴǂųŚƆ 2-Hydroxyethyl acrylamideǃHmDŽŴŸƺƛƑƼ!ĻCŷƃƅC�ŦŮŖ�ƄƇŮ=��ƳƻƴǂǃpSiHmxDŽŸ

1H NMRƜƱƔƦƼÊdŞƃŻ SEC ÊdŸă±şƄŕpSiHmx

Ÿ!ĻCĂ�¿ǃx = Hm/SiDŽŹ 100 ųŚƅŕ)`ĽǃMwDŽŹ 3.7×105ǃPDI = 3.62DŽųŚƆŤŴƉðģŦŮŖpSiHmx ÁËÆŞƃŻtRÿ�Š 14.3 nm ŸƨƪƚƻƑǃSiNPDŽÁ)�ÆƉ�dŸ¿ÚųÇCŦŕŤƇƉƚƻƘǂǀƐƍƼ�ŷ2ŝŕş

šÇūƆŤŴų W/O ƙƜƱǀƚƹǀƉ�ĔŦŕ2¤łşšÇūŮŖŬŸă±ŕFig. 3(a)ŷòŦŮƃŜŷÛÙƗƼ�ÿ`Ź�ƄƇƆŠŕÿ`ŵŜŦŠ

%ňŦŲśƆŤŴŠðģťƇŮŖŤƇŹŕƗƼ�

ÿ`ēŌIJ�ŷŹª=�ŸƳƻƴǂ�ľƂƘƾ

ƍƢƼƚƻƑŠbQŦŲŞƅŕƗƼ�ÿ`łų=

�ŨƆŤŴŷƃƅ%ňŦŮŴ�ÊťƇƆŖŬŤųŕ

ƚƻƘǂǀƐƍƼ�ŷƌƵƪTƉƁűƚƺǀƑƤƯ

ƻǀƕ/ųŚƆ 3-AminopropyltriethoxysilaneǃAPSDŽƉËĚťŪŕDºŷ W/O ƙƜƱǀƚƹǀ�ųƗƼ�ÿ`Ɖ�ĔŦŮă±ŕÿ`ŵŜŦŸ

%ňŹėƄƇŶşŰŮŖ�ŝźŕ10 wt%Ÿ=��ƳƻƴǂǃpSiHm100DŽÁËÆŴ 10 wt%ŸƘƾƍƢƼƚƻƑǃSiNPDŽÁ)�ÆƉ 1:1ǃvol/volDŽųÇCŦŕAPS ƉËĚťŪŮƚƻƘǂǀƐƍƼǃ4Ā

Figure 2 Chemical structures of water soluble polymer with reactive side chains.

VPy�DMAAm�

HEA, HEMA�Hm�

AAm�

NIAAm�

R:�

pSiMX� X = n/m�

Si: Reactive monomer M: Water-soluble monomer

+�

Reactive copolymer� Nanoparticle�

SiNP�pSiMX�

Hybrid hydrogel�

Figure 1 Preparation of hybrid hydrogel composed of colloidal silica-crosslinked polymer network.

Page 3: æÚ ¤4 î A [N ' ÿa»¡Ù¸ gbàÃãò ípb · f bF h d t `VH e r [ Vã ' ñ . ÿ`ä L ... C ¿ Ãx = Hm/Si Ä y100 s Z U) ` = ÃM w Ä y3.7×10 5 ÃPDI = 3.62 Ä s Z d t

wǎ100 cSDŽ�ŷ)�ťŪŕ25 °C ų 1¤łşšÇūŮă±ŕĴ¢şűÛÙŸƗƼ�ÿ`

ǃpSiHm100 = 5 wt%ŕ SiNP = 5 wt%DŽƉ�ŮǃFig. 3(b)DŽŖAPSŹŕƗƼ�ÿ`äŌŸª=�ŸƳƻƴǂ�ľƂƘƾƍƢƼƚƻƑŴ=�ŨƆŤ

ŴŷƃƅŕäŌŷƌƵƪTŠl ťƇŮŴĈŝƄƇ

ƆŖƗƼ�ÿ`ŸēŌƟǂơŊ�ƉÊdŦŮă

±ŕƯƺƜŷrŊǃ+18.7 mVDŽŦŲśƆŤŴŠðģťƇŮŤŴşƄŕ�ÿ`łųŸŋŊ=çŷƃƅŕ

ÿ`ŵŜŦŸ%ňƉ�-ŦŲśƆŴĈŝƄƇƆŖ

APS �[ŸƚƺǀƑƤƯƻǀƕ/ƉàśŲDºŸeŒƉĐŰŮă±ŕśũƇƁƗƼ�ÿ`ŵŜ

ŦŸ%ňŹ�-ťƇƆŠŕAPS ŠƁŰŴƁ3±ŠœśŤŴŠðģťƇŮŖŬŤų¾ŷŕĀwŸæŶ

ƆƚƻƘǂǀƐƍƼƉàśŲDºŷƗƼ�ÿ`

Ɖ�ĔŦŮă±ŕFig. 3 ŷòŦŮƃŜŷŕœĀwŸƚƻƘǂǀƐƍƼ�ųŹ¿įèmťśƗƼ�

ÿ`Š�ƄƇŕ�ĀwŸƚƻƘǂǀƐƍƼ�ų

Ź¿įè]šśƗƼ�ÿ`Š�ƄƇŮŖFig. 3ŷŹŕĀwŠ 300 cSǃFig. 3(b)DŽŕ100 cSǃFig. 3(c)DŽŕ50 cSǃFig. 3(d)DŽŸƚƻƘǂǀƐƍƼƉ�Í_�ŴŦŲàśŮWCŷ�ƄƇŮƗƼ�ÿ`

Ÿ�cŎ�Ŀ#íƉòŦŕžŮ Fig. 4 ŷŹŬƇŭƇŸƗƼ�ÿ`Ÿÿw)qƉòŦŮŖ�ŝźŕ

œĀwǃ300 cSDŽŸƚƻƘǂǀƐƍƼƉàśŮWCŕtRÿ�Š 55 µmǃCV� 47.3 %DŽŸƗƼ�ÿ`Š�ƄƇŕ�Āwǃ50 cSDŽŸƚƻƘǂǀƐƍƼƉàśŮWCŕtRÿ�Š 1240 µm ǃCV�

34.8 %DŽŸƗƼ�ÿ`Š�ƄƇŮŖŤƇƄŸă±şƄƁŕ�Í_�ųŚƆƚƻƘǂǀƐƍƼŸĀw

ŷƃƅČQŷÿ`ƙƍƝƉ-�ųšƆŤŴŠƈş

ƆŖ

�ƄƇŮƗƼ�ÿ`ŸPązwƉÊdŦŮă

±ŕśũƇƁ 50 %õwŸPąÚųïZŨƆŤŴŠðģťƇŮŖzwƉ¿įŨƆŴŕPązwŹ

ƗƼ�ÿ`ŸĂ�Š]šŢ~ōŨƆŤŴŠðģ

ťƇŮŖ�ŝźŕpSiHm100ŞƃŻ SiNPŸÎwŠśũƇƁ 5 wt%ŸƗƼ�ÿ`�ŸWCŕ40 %Pą¤ŸzwŠ 16.8 MPa ųŚƆŸŷjŦŲŕpSiHm100ŞƃŻ SiNPŸÎwŠ 5 wt%ŕ2.5 wt%ŸƗƼ�ÿ`ųŹŕ4.97 MPaųŚŰŮǃFig. 5DŽŖ� ŕƗƼ�ÿ`Ÿÿ`�Ź9��Ō÷ŚŮƅ

Ÿzwŷ~ōŦŶśŤŴƉðģŦŮŖ N}�)ǃ=��ƳƻƴǂŞƃŻƘƾƍƢƼƚ

ƻƑDŽŸÎwŠ 10wt%ŴŦŲ�ĔŦŮŕƳƻƴǂƗƼ�ÿ`ŸÕĻĽ)°ƉĐŰŮă±ŕÁG

¨ĽŹ 60�70wt%ǃN}�)Š 30�40 wt%DŽųŚƆŤŴŠðģťƇŮŖŤŸŤŴŹŕƗƼ�ÿ

`"Ĺŷ APSŠ 10�20wt%GÅŦŲśƆŤŴƉòKŦŲśƆŖ�ÿ`"ĹżŸ APS GÅƉ÷¸èŷ,àŨƆŤŴųŕÿ`ƉN6ťŪƆŤŴŷ

�1ŦŮŖ�ƄƇŮ�ÿ`ƉÈPÖťŪŕŊ

`Ŏ�ĿųęhŦŮă±ŕFig. 6ŷòŦŮƃŜŷŕäŌŷ'&ƉƁűƳƻƴǂǁƚƻƑĕC�ÿ`Š

�ƄƇŮŖťƄŷŕŤŸ�ÿ`ƉÒ�ŨƆŤŴŷ

ƃƅƳƻƴǂ�)ƉŅ<ŦŕƘƾƍƢƼƚƻƑŸň

÷ŷƃƅ}�ťƇŮ\aĬ�ÿ`Ɖ�ŮŖžŮŕ

ƗƼƴƍƔƾÿ`ƉàśŮ\aĬ�Ÿ�ĔŷƁ

0

10

20

0 20 40 60 80

Stre

ss (M

Pa)�

Compression (%)�

[pSiHm100] = 5 wt% [SiNP] = 2.5 wt% Size: 223 µm

[pSiHm100] = 5 wt% [SiNP] = 5 wt% Size: 292 µm

Figure 5 Compressive strength of hybrid hydrogels. Red line: [pSiHm100] = 5 wt%, [SiNP] = 5 wt%, Blue line: [pSiHm100] = 5 wt%, [SiNP] = 2.5 wt%,

300 µm�300 µm�

100 µm�

(a)� (b)�

(c)� (d)�

300 µm�

Figure 3 Optical microscopic images of the hybrid hydrogel particles prepared in various suspension media. [pSiHm100] = 5 wt%, [SiNP] = 5 wt% (a) Silicone oil: 300 cS, without APS, (b) Silicone oil: 300 cS, with APS, (c) Silicone oil: 100 cS, with APS, (d) Silicone oil: 50 cS, with APS.

50

150

250

350

450

550

650

750

850

950

Particle size (µm)

150

450

750

1050

13

50

1650

19

50

2250

25

50

2850

Particle size (µm)�

0

10

20

30

40

50

60

15

45

75

105

135

165

195

225

255

285

%�

Particle size (µm)�

55 µm� 292 µm� 1240 µm�

Figure 4 Particle size distributions of the hybrid hydrogel particles prepared in various suspension media. [pSiHm100] = 5 wt%, [SiNP] = 5 wt% (a) Silicone oil: 300 cS, with APS, (b) Silicone oil: 100 cS, with APS, (c) Silicone oil: 50 cS, with APS.

Page 4: æÚ ¤4 î A [N ' ÿa»¡Ù¸ gbàÃãò ípb · f bF h d t `VH e r [ Vã ' ñ . ÿ`ä L ... C ¿ Ãx = Hm/Si Ä y100 s Z U) ` = ÃM w Ä y3.7×10 5 ÃPDI = 3.62 Ä s Z d t

ƣƸƽǀƛŦŕ�ƨƪşƄ 10�ƨƪŸúa�ƉƁű\aĬƫƍƮƻƤƧ�ÿ`ŕťƄŷŹƫƍƮƻƤ

Ƨ�ŸÒ�ŷƃƆ\aĬƚƻƑ�ÿ`Ɖ�ĔŨ

ƆŤŴŷ�1ŦŮŖ

��ŕ=��ƳƻƴǂƉƨƪƚƻƑų²¼ŨƆ

ŤŴŷƃƅ�ƄƇŮĴ¢ƗƼ�ÿ`ŹŕƬƼƔų

�ĔŦŮƫƍƮƻƤƧƗƼŴDºŷŕĂ�ƉĦ�

ŨƆŤŴųzwŶŵŸƗƼØ�Ɖg£ŷ-�ų

šƆŤŴŠðģťƇŮŖƫƍƮƻƤƧƗƼŹŕ=�

�ƳƻƴǂŴƨƪƚƻƑŴŸÇC¤ŷöŗŸ)`

ƉŚƄşŧƀ"5ťŪƆŤŴŠųšƆŮƀŕƓƸƻ

ƌ­�ŴŦŲŸ�àŠ©�ťƇƆŖƳƻƴǂƩƤ

ƦƿǂƔ¹ĶƉ-�ŦŮƬƼƔÙ�ŸƫƍƮƻƤ

ƧƗƼŷŞśŲŕ"5×ĬŸ�(�4Ɖ-�ų

šƆŤŴƉðģŦŲŞƅ[3]ŕƗƼ�ÿ`ŷŞśŲƁDºŸ�(-�Š?ċųŚƆŴĈŝƄƇƆŖ Reference 1. M. Czaun, L. Hevesi, M. Takafuji, H. Ihara.

Chemical Communications, pp.2124-2126, 2008.

2. M. Czaun, L. Hevesi, M. Takafuji, H. Ihara. Journal of Nanoscience and Nanotechnology, Vol. 9, pp.123-131, 2009.

3. M. Takafuji, S. Yamada, H. Ihara. Chemical Communications, Vol. 47, pp.1024-1026, 2011.

NjDž�ŶçēĨ�ý ŘʼnĢĨ�řǃěŔ NJŔ �DŽ 1. Md. Ashraful Alam, Makoto Takafuji,

Hirotaka Ihara. Thermosensitive hybrid hydrogels through nanoparticle-crosslinked polymer network. Journal of Colloid and Interface Science, Vol. 405, 109-117 2013. doi: 10.1016/j.jcis.2013.04.054,Ŕ ³ĥŚƅ

2. Md. Ashuraful Alam, Makoto Takafuji, Hirotaka Ihara. Silica nanoparticle-crosslinked thermosensitive hybrid hydrogels as potential drug-release carriers. Polymer Journal, Vol.46, pp.293-300, 2014. doi:10.1038/pj.2014.2,Ŕ ³ĥŚƅ

3. Makoto Takafuji, Md. Ashraful Alam,

Hiroyuki Goto, Hirotaka Ihara. Microspherical hydrogel particles based on polymer network webbed with silica nanoparticles. Journal of Colloid and Interface Science, Vol.455, pp.32-38, 2015. doi: 10.1016/j.jcis.2015.05.034,Ŕ ³ĥŚƅ

4. Sabrina Sultana, Md. Ashraful Alam, Makoto

Takafuji, Hirotaka Ihara. Fabrication of hybrid mesoporous microspheres from aqueous droplet containing silica nanoparticles-polymer network in W/O suspension. RSC Advances, Vol. 6, pp.42756-42762, 2016. doi: 10.1039/C6RA05173A,Ŕ ³ĥŚƅ

Řc�çēřǃěŔ LJnjŔ �DŽ 1. Md. Ashraful Alam, Makoto Takafuji,

Hirotaka Ihara. Control of thermal, swelling and release properties of nanoparticle-mediated hybrid polymer hydrogel. Kyusyu-Seibu/Pusan-Gyeongnam Joint Symposium on High Polmers (16th) and Fiber(14th), Saga University (Saga, Japan), 2013. 11. 8-10.

2. Md. Ashraful Alam, Makoto Takafuji,

Hirotaka Ihara. Silica nano particle-crosslinked thermosensitive hybrid hydrogels for potential controlled release. International Soft Matter Conference 2013Ŕ(ISMC 2013), Rome (Italy), 2013. 9. 15-19.

3. Yang Liu, Makoto Takafuji, Hirotaka Ihara,

Meifang Zhu, Mingshan Yang, Kai Gu, Wenli Gou. Programmable responsive shaping gels by multi-dimensional gradients of magnetic nanoparticles. ünjLjLœ)`c�u¾]�, �ĺOŇ�ĪWǃ�ĺDŽ, 2013. 5. 29-31.

4. Makoto Takafujiǃ��ĩÌDŽ

Development of nanoparticle-crosslinked hybrid hydrogels. o]-Ô]ÝYÞ×�đîù��Ł�y Material Research Society ,Sichuan University, Sichuan (China), 2014. 5. 12.

5. œďŔ Ĥǃ��ĩÌDŽ

Development of core-shell hybrid microspheres with nanoparticles shell layer ƠƭƦƴơǂîù�, Ô«]cǃÔ«DŽ, 2014. Ŕ6. 20.

100 µm� 10 µm�

Figure 6 Scanning electron microscopic images of hybrid porous microspheres.

Page 5: æÚ ¤4 î A [N ' ÿa»¡Ù¸ gbàÃãò ípb · f bF h d t `VH e r [ Vã ' ñ . ÿ`ä L ... C ¿ Ãx = Hm/Si Ä y100 s Z U) ` = ÃM w Ä y3.7×10 5 ÃPDI = 3.62 Ä s Z d t

6. Md. Ashraful Alam, Makoto Takafuji, Hirotaka Ihara. Thermo-responsive properties of silica nanoparticle-crosslinked hybrid polymer hydrogel. ünjljLœ)`ĜĨ� Material Research Society, ŀn]cǃŀnDŽ, 2014. 9. 24-26.

7. Makoto Takafuji, Md. A. Alam, Yutaka

Kuwahara and Hirotaka Ihara. Spherical hydrogel microparticles using silica nanoparticle as multifunctional crosslinking points. Faraday Discussion: Nanoparticle synthesis and assembly, Argonne National Laboratory, Chigo (USA), 2015. 4. 20-22.

8. Md. Ashraful Alam, Sabrina Sultana, Yutaka

Kuwahara, Makoto Takafuji, Hirotaka Ihara. Preparation of microspherical hydrogels based on hydrophilic polymers crosslinked with nano-silica. ü 64Lœ)`c�u¾]�, ¬sƘǀưǀƚƹǀƞǀơǂǃ¬sDŽ, 2015. 5. 27-29.

9. Sabrina Sultana, Md.Ashraful Alam, Yutaka

Kuwahara, Makoto Takafuji, Hirotaka Ihara. Preparation of hybrid microspheres from hydrophilic polymer gels crosslinked with nano-silica. ünjNJLœ)`c�u¾]�, ¬sƘǀưǀƚƹǀƞǀơǂǃ¬sDŽ, 2015. 5. 27-29.

10. Makoto Takafuji, Md. Ashraful Alam, Yutaka

Kuwahara, Hirotaka Ihara. Microspherical hydrogel particles based on nanoparticle-webbed polymer network. Congress of the European Polymer Federation (EPF-2015), (Dresden) Germany, 2015. 6. 21-26.

11. UÂâćŕµ; øŕœď Ĥŕ�;:ņ Į)`ƨƪƭƋƍƬǂƉ²¼�ŴŨƆƳƻƴǂƩƤƦƿǂƔŸ}� ¡«6c�p�ĹĞû 100Iuĝ�OŇƚǀƳƛƎƶü 52L6cŃķ�ĹCDp]�, 7pOŇ�ĪWǃ7pDŽ, 2015. 6. 27-28.

12. Sabrina Sultana, Md. Ashraful Alam, Yutaka

Kuwahara, Makoto Takafuji, Hirotaka Ihara. Development of porous hybrid microspheres composed of simaltaneous nanosilica particles. International Conference & Exhibition on Advanced & Nano Materials (ICANM 2015), Ottawa (Canada), 2015. 8. 10-12.

13. œď Ĥ, Md. Ashraful Alam, µ; ø, �;:ņ

ƨƪÿ`ƉƴƼƣ²¼�ŴŨƆƫƍƮƻƤƧƗƼƴƍƔƾÿ`Ÿ0Ĕ. ü 64Lœ)`ĜĨ�, ¯7]cǃ�@DŽ, 2015. 9. 15-17.

14. Makoto Takafujiǃ��ĩÌDŽ

Development of nanoparticle-webbed hybrid hydrogels. 2015 Pusan-Gyeongnam/Kyushu-Seibu Joint Symposium on High Polymers (17th) and Fibers (15th)(2015 PGKS), Pusan (Korea), 2015. 11. 12-14.

15. Md. Ashraful Alam, Makoto Takafuji,

Hirotaka Ihara Facile Fabrication of Microspherical Hydrogel particles based on Nanoparticle-crosslinked polymer networks. 1st international conference on Applied Chemistry- ICAC 2015, Jeddah (Saudi Arabia), 2015. 11. 18-19.

16. Makoto Takafuji, Md. Ashraful Alam,

Hirotaka Ihara.ǃ��ĩÌDŽ Hybrid hydrogels composed of polymer network webbed with silica nanoparticles 16th Asian Chemical Congress (16ACC), Dhaka (Bangladesh), 2016. 3. 16-19.

ŘM¦řǃěŔ džŔ �DŽ Řß·īß»ř ○(ŏÙÃǃěŔ LJŔ �DŽ Eôǎ¨½ǁнƫƍƮƻƤƧƫƍƧƾƗƼÿ`ŞƃŻŬŸĔĶ Ä ç¢ĉǎ�;:ņŕœďĤŕtá¢Üŕi«vB »,ĉǎÔ«]cŕKJƖƵƑƼƝǃ´DŽ öŐǎØğ åAǎØŏ 2013-108930 (ŏu§¡ǎ2013u 5§ 23¡ O"[Ÿ+ǎ O" ○>�ÙÃǃěŔ džŔ �DŽ ŘŬŸ ř ƲǂƶƱǂƛý http://www.chem.kumamoto-u.ac.jp/~wildcats/takafuji/index-j.html njDžîùĂĆ ǃLJDŽîù�ēĉ œďŔ ĤǃTAKAFUJI MakotoDŽ Ô«]cǁ]cńČÑócîùóǁ$�� îùĉåAǎNjdžljljLjdžǍnj ǃLjDŽîù)�ĉ ǃljDŽķ�îùĉ