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  • 學位論文

具有光致變色及熱敏性凝膠材料之合成及其性質之研究

Studies on Preparation and Properties of the Photoluminescent and Thermosensitive Hydrogels

指導教授 : 李文福
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摘要


PART 1 利用bis-[4-(phenyl-iso-propyl)phenyl]amine (PA) (i)與4-fluoronitrobenzene (ii) 合成bis[4-(phenyl-isopropyl)-phen- yl]-4-nitrophenylamine (PNPA) (iii),確定結構之後,再將PNPA (iii)還原成bis-[4-(phenyl-isopropyl)phenyl]-4-aminophenylamine (PAmPA) (iv),最後PAmPA (iv)再與acryloyl chloride 行乙烯化反應合成bis[4-(phenyl-isopropyl)-phenyl]-4-acrylamidophenylamine (PAcPA) (v)。將具備vinyl group之compound (v)與N-isoproopyl acrylamide (NIPAAm)單體共聚合製備一系列膠體。 本文主要探討PAcPA單體含量對膠體的膨潤度,機械強度及藥物釋放和UV-PL性質的影響。結果顯示,膠體中具有苯環基團的PAcPA含量,比例由0.1增加至0.9 mol%,膨潤度會由8.2倍降至5.01 倍。此外,在不同溫度下的熱應答效應會隨著PAcPA含量的增加而漸不明顯;但在機械強度及交聯密度方面則隨著PAcPA的量增加,而呈現成正比的趨勢;在藥物釋放結果則可發現膠體中PAcPA含量的提升會導致膠體有吸藥量少但放藥量多的現象。另外在本研究中分別將PAcPA單體、含有PAcPA之膠體和NIPAAm/PAcPA共聚體溶於常用之不同極性大小的溶劑中,並分別使用UV和PL分別測量最大吸收波長(λmax)及放射波長(λem)。結果顯示單體、膠體和共聚體的發光強度會隨PAcPA含量增加而亮度增強,特別是在THF溶液有明顯的藍位移。而此系列之UV和PL皆出現在可見光區。不論是單體、膠體或共聚體,在DMSO溶液中該吸收或放射波峰則沒有變化。 PART 2 利用bis-[4-(phenyl-iso-propyl)phenyl]amine (PA) (i)與4-fluorobenzonitrile (ii)’合成出bis[4-(phenyl-isopropyl)phenyl]-4- cyanophenylamine (PCyPA) (vi),然後將PCyPA (vi) 水解之後再利用HCl 酸化得bis[4-(phenyl-isopropyl)phenyl]-4-carboxyphenylamine (PCaPA) (vii)。 最後再與HEMA進行酯化反應得到methacryloyloxy ethylene oxycarbonyl bis-[4-(phenyl-isopropyl)phenyl] amine (MEOPA) (viii)。將MEOPA 和N-isopropyl acrylamide (NIPAAm) 單體作為主體共聚合製備成一系列膠體。 主要探討MEOPA單體含量膠體的膨潤度,機械強度及藥物釋放和UV-PL性質的影響。結果顯示,膠體中具有苯環基團的MEOPA含量,比例由0.1增加至0.9 mol%,膨潤度會由4.73倍降到1.74倍。此外,此MEOPA系列之膠體在不同溫度下的熱應答效應與第一部分相比較反而不明顯;機械強度及交聯密度則會隨著MEOPA的量增加,而呈現成正比的趨勢;在咖啡因藥物釋放結果則可發現膠體中MEOPA含量的提升會導致膠體有吸藥量少但放藥量多的現象。另外在本研究中也分別將MEOPA單體、含有MEOPA之膠體和NIPAAm/MEOPA共聚體,溶於常用之不同極性大小的溶劑中,並分別使用UV和PL分別測量最大吸收波長(λmax)及放射波長(λem)。結果顯示單體、膠體和共聚體的發光強度會隨MEOPA含量增加而亮度增強,並隨著溶液的極性而產生位移的現象。此系列的最大吸收波峰在不可見光區,而最大放射波長則出現在可見光區。不論是單體、膠體或共聚體,在DMSO溶液中該吸收或放射波峰則沒有變化。 PART3 先利用pyrene 與 Copper(II) nitrate合成1-nitropyrene (1),確定結構之後,再將1-nitropyrene (1)還原成1-aminopyrene (2),還原後之compound (2)再與acryloyl chloride 行乙烯化反應形成1-acrylamidopyrene (3) (AAP)。將具備vinyl group之compound (3)與N-isopropyl acrylamide (NIPAAm)單體共聚合製備一系列膠體。 本文主要探討AAP單體含量對膠體的膨潤度,機械強度及藥物釋放和UV-PL性質的影響。結果顯示,膠體中具有pyrene基團的AAP含量,比例由0.1增加至0.9 mol%,膨潤度會由6.5倍降至4.9 倍。此外,在不同溫度下的熱應答效應會隨著AAP含量的增加而跟著不明顯;但在機械強度及交聯密度方面則隨著AAP的量增加,而呈現成正比的趨勢;在藥物釋放結果則可發現膠體中AAP含量的提升會導致膠體有吸藥量少但放藥量多的現象。另外在本研究中也分別將AAP單體、含有AAP之膠體和NIPAAm/AAP之共聚體,溶於常用之不同極性大小的溶劑中,並分別使用UV和PL分別測量最大吸收波長(λmax)及放射波長(λem)。結果顯示單體、膠體和共聚體的發光強度會隨AAP含量增加而亮度增強,並隨著溶液的極性而產生位移的現象。此系列具有兩個吸收波峰,吸收波峰皆在不可見光區;而最大放射波長則出現在不可見光區,次波峰則在可見光區。不論是單體、膠體或共聚體,在DMSO溶液中該吸收或放射波峰則沒有變化。

並列摘要


PART 1 In the first part the abstract as follows. Bis[4-(phenyl-isopropyl)phenyl]-4-nitrophenylamine (PNPA) (iii) was firstly synthesized by nucleophilic substitution of 4-fluoronitrobenzene (ii) and bis-[4-(phenyl-isopropyl)phenyl]amine (PA) (i) in this study, and then PNPA (iii) was reduced to bis[4-(phenyl-isopropyl)phenyl]-4-aminophenylamine (PAmPA) (iv). At last, acrylation of PAmPA (iv) with acryloyl chloride was performed to obtain the bis[4-(phenyl-isopropyl)phenyl]-4-acrylamidophenylamine (PAcPA) (v). Then, a series of thermosensitive hydrogels were prepared by copolymerization of PAcPA and N-isopropyl acrylamide (NIPAAm) by UV irradiation. The effect of PAcPA content in the copolymeric hydrogels on the swelling ratio, mechanical properties, and drug release behaviors of the gels was investigated. Results showed that the swelling ratios of the copolymeric hydrogels decreased from 8.2 (g/g) to 5.01 (g/g) when the hydrophobic monomer PAcPA content in the copolymeric gel increased from 0.1 mol% to 0.9 mol% due to the decreasing hydrophilicity. In addition, the thermosensitive behavior obviously decreased with increasing of PAcPA content in the hydrogels, but the mechanical properties and crosslinking density of the hydrogel increased with increasing of PAcPA content; the caffeine drug release ratio decreased from 46% to 29%. The result of drug release also showed when the the the content of PAcPA in the hydrogel increased, the drug-loadings of the hydrogel decreased, but fractional release increased. In addition, the corresponding copolymers of the copolymeric hydrogels were prepared by the free radical polymerization. Furthermore, the PAcPA monomer was dissolved in DMSO with different concentrations, the NIPAAm/PAcPA hydrogel and NIPAAm/PAcPA copolymer were respectively swollen and dissolved in some solvents with different polarities, and then separately measured their maximum wavelengths of UV absorbance and PL emission.. The results showed the luminescence intensity increased with increasing PAcPA amounts, especially the wavelength had obvious blue shift phenomenon in THF solvent. The wavelength of UV absorbance and PL emission of PAcPA all appeared in visible region. No matter what monomer, NIPAAm/PAcPA hydrogel or NIPAAm/PAcPA copolymer, the wavelengths of UV absorbance and PL emission in DMSO solvent are all the same. PART 2 In the second part, bis[4-(phenyl-isopropyl)phenyl]-4-cyanophenyl amine (vi) (PCyPA) was firstly synthesized by nucleophilic substitution of 4-fluoro-benzonitrile (ii)’ and bis[4-(phenyl-isopropyl)phenyl]-4-phenyl amine (PA) (i) in this study. Then, the hydrolysis and acidification of the PCyPA (vi) was performed to obtain bis[4-(phenyl-isopro-pyl)phenyl] -4-carboxy-phenylamine (PCaPA) (vii), and then esterification with HEMA to obtain methacryloyloxy ethylene-oxy-carbonyl bis-[4-(phenyl-isopropyl)phenyl]amine (MEOPA) (viii). Then, a series of thermosensitive hydrogels were prepared by copolymerization of MEOPA and N-isopropyl acrylamide (NIPAAm) by UV irradiation. The effect of MEOPA content on the swelling ratio, mechanical properties of the hydrogels was investigated. Results showed that when the hydrophobic monomer MEOPA content in the copolymeric hydrogel increased from 0.1 mol% to 0.9 mol%, the swelling ratios of the copolymeric gels decreased from 4.73 (g/g) to 1.74 (g/g); the gel strength and crosslinking density increased with increasing the MEOPA monomer amounts. In addition, the release ratio of caffeine also decreased from 70% to 25%. In photoluminescent behavior, the intensity of photoluminescent increased with an increase of the content of MEOPA in the copolymeric hydrogel. On the other hand, the corresponding copolymers of copolymeric hydrogels were prepared by the free radical polymerization. Furthermore, the MEOPA monomer was dissolved in DMSO with different concentrations, the NIPAAm/MEOPA hydrogel and NIPAAm/ MEOPA copolymer were respectively swollen and dissolved in some solvents with different polarities, and then separately measured their maximum wavelengths of UV absorbance and PL emission.. The results showed the luminescence intensity increased with increasing MEOPA amounts. especially the wavelength had blue shift phenomenon in THF solvent. The wavelength of UV absorbance and PL emission of MEOPA appeared in invisible and visible region respectively. No matter what MEOPA monomer, NIPAAm/MEOPA copolymer or NIPAAm/MEOPA hydrogel, their wavelengths of UV absorbance and PL emission in DMSO are all the same. PART 3 In the third part, 1-nitropyrene (1) was firstly synthesized by pyrene and copper(II) nitrate in this study, and then compound (1) was reduced to 1-aminopyrene (2). At last, acrylation of compound (2) with acryloyl chloride was carried out to obtain 1-acrylamidopyrene (3) (AAP). Then, a series of thermosensitive hydrogels were prepared by copolymerization of AAP and N-isopropyl acrylamide (NIPAAm) by UV irradiation. The effect of AAP content in the copolymeric gels on the swelling ratio, mechanical properties, and drug release behaviors of the hydrogels was investigated. Results showed that the swelling ratios of the copolymeric gels decreased from 6.5(g/g) to 4.9 (g/g) when the hydrophobic monomer AAP content in the copolymeric hydrogel increased from 0.1 mol% to 0.9 mol% due to the decreasing hydrophilicity. In addition, the thermosensitive behavior obviously decreased with increasing of AAP content in the gels, but the mechanical properties and crosslinking density of the hydrogel swollen in the ethanol solution increased with an increase of AAP content. The swelling ratios of hydrogels were changed by increasing AAP content in the different solvents. The result of drug release showed that when the content of AAP in the hydrogel increased, the caffeine-loading in the hydrogel decreased but the fractional release increased. In addition, the corresponding copolymers of NIPAAm/AAP copolymeric hydrogels were synthesized. Furthermore, the AAP monomer was dissolved in DMSO with different concentrations, the NIPAAm/AAP hydrogel and NIPAAm/AAP copolymer were respectively swollen and dissolved in some solvents with different polarities, and then separately measured their maximum wavelengths of UV absorbance and PL emission..The results showed the luminescence intensity increased with increasing AAP amounts. especially the wavelength had blue shift phenomenon in THF solvent. The wavelength of UV absorbance and PL emission of AAP all appeared two absorption peaks. The wavelength of UV absorbance of AAP appeared in invisible region, and major PL emission peak of AAP appeared in invisible and minor peak in visible region. No matter what AAP monomer, NIPAAm/AAP copolymer or NIPAAm/AAP hydrogel, their wavelengths of UV absorbance and PL emission in DMSO are all the same.

參考文獻


55. Canion, P. C.; Yang, J.; Wu, Y.; Chen, Y.; Martinez, K.; Kim, Y.;
3. Leung, M. K. ; Chou, M. Y.; Su, Y. O.; Chiang, C. L.; Chen, H. L.; Yang, C. F.; Yang, C. C.; Lin, C. C.; Chen, H. T. Org. Lett. 2003, 5, 839.
4. Yeh, S. J. C.; Tsai, Y.; Huang, C. Y.; Liou, G. S. and Cheng, S. H. Electrochem. Commun. 2003, 5, 373.
37. Lin, K. R.; Chang, Y. H.; Chang, C. C.; Hsieh, K. H.; Leung, M. K.
1. Chung, J.; Choi, B.; Lee, H. H. Appl. Phys. Lett. 1999, 74, 3645.

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