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系統識別號 U0002-2707200912472600
中文論文名稱 利用氧化還原起始劑合成PMMA奈米顆粒及製備光可調控溫度敏感型共聚物以做為藥物控制釋放載體
英文論文名稱 Synthesis of PMMA nanoparticles by a redox initiator system and the preparation of optical-controlled thermo-responsive carrier for drug delivery system
校院名稱 淡江大學
系所名稱(中) 化學工程與材料工程學系博士班
系所名稱(英) Department of Chemical and Materials Engineering
學年度 97
學期 2
出版年 98
研究生中文姓名 邱作沛
研究生英文姓名 Tso-Pei Chiu
學號 892360073
學位類別 博士
語文別 中文
口試日期 2009-06-29
論文頁數 223頁
口試委員 指導教授-董崇民
委員-邱文英
委員-李文福
委員-陳崇賢
委員-李佳芬
委員-林達鎔
委員-鄭廖平
中文關鍵字 乳化聚合  Cu2+/HSO3-  氧化還原起始系統  PMMA  裂解活化能  幾丁聚醣  溫度敏感性  氮-異丙基丙烯醯胺  聚甲基丙烯酸聚乙二醇酯  LCST  奈米金桿 
英文關鍵字 emulsion polymerization  Cu2+/HSO3-  redox initiator  poly(methyl methacrylate)  apparent activity energy  chitosan  thermal-responsive  microgel  LCST  PNIPAAm  PEGMA  gold nanorod 
學科別分類 學科別應用科學化學工程
學科別應用科學材料工程
中文摘要 本研究第一部分是以新型硫酸銅和亞硫酸氫鈉(Cu2+/HSO3-)氧化還原起始系統在不同反應溫度下(40oC~60oC)進行PMMA乳膠顆粒的合成,反應2小時後,轉化率可達85 %以上,而乳膠顆粒表面因有亞硫酸根而帶負電。利用SEM觀察乳膠顆粒的形態,結果顯示乳膠顆粒大小均一分佈,而且反應溫度越高其粒徑越小,粒徑平均大小從40oC的223 nm減少至60oC的165 nm之間,趨勢與光散射儀的結果一致。本研究闡明了Cu2+/HSO3-氧化還原起始系統的反應機制,首先銅離子與兩個亞硫酸氫根先形成配位複合物後,銅離子誘使亞硫酸氫根上的氫氧鍵斷鍵產生亞硫酸根自由基和氫原子自由基,氫原子自由基進一步地和銅離子進行氧化還原反應變成氫離子和亞銅離子,而亞硫酸根自由基則起始自由基聚合反應。另外,不同溫度下合成出的PMMA鏈段的立體異構性幾乎是相同的,大約是62~64 % rr、33~35 % mr和3 % mm,而且有幾乎相同的玻璃轉移溫度(125~127oC),其重量平均分子量在254,000和315,000之間。
固定反應溫度在60oC,改變起始劑中銅離子濃度以合成PMMA,實驗結果顯示不同銅離子濃度合成的PMMA,單體轉化率皆可達90 %以上,且Zeta電位皆低於-30 mV,代表乳液有不錯的穩定性。當銅離子濃度從2.0 mM增加至6.0 mM時(MMA維持1 M),SEM觀察結果顯示乳膠顆粒大小均一分佈,粒徑平均大小從182 nm增加到224 nm。所合成出來的PMMA乳膠顆粒的TGA曲線圖呈現兩階段裂解行為,其中第一階段屬不飽和末端基團PMMA-CR=CH2的熱裂解,第二階段屬飽和末端基團PMMA-H的熱裂解,而隨著銅離子濃度增加,會造成較多的不飽和末端基團的PMMA-CR=CH2生成,因此銅離子不僅僅可用來起始反應,同時又是鏈轉移劑用以終止成長中的高分子自由基鏈段。利用Ozawa法和Boswell法計算裂解活化能的結果顯示,PMMA-CR=CH2的裂解活化能在123.6~134.8 kJ/mol之間,而PMMA-H的裂解活化能在156.4~213.4 kJ/mol之間。
本研究第二部分利用具生物相容性的幾丁聚醣(CS)、溫度敏感性的氮-異丙基丙烯醯胺(NIPAAm)單體和可調整溫度敏感值(LCST)的聚甲基丙烯酸聚乙二醇酯(PEGMA)單體,以合成LCST值略高於生理溫度的幾丁聚醣-聚氮-異丙基丙烯醯胺-聚甲基丙烯酸聚乙二醇酯(CS-PN-PEG)共聚物。從批次反應系統所合成的CS-PN-PEG共聚物,因單體反應性的不同,會產生CS-PN-PEG和CS-PN共聚物,因而產生兩個相變化行為。以連續進料系統所合成的CS-PN-PEG共聚物,具有一階段的相變化行為。在pH4的環境下,當溫度到達LCST以上時,CS-PN-PEG共聚物能夠立即收縮,呈現應答快速的一階段相變化行為,隨PEGMA的含量增加,LCST值從33.0oC增加到39.7oC。在pH7的環境下,因CS的鏈展開幅度不大,呈現應答較為緩慢的一階段相變化行為,隨PEGMA的含量增加,LCST值從35.7oC增加到45oC。粒徑分析儀量測CS-PN-PEG共聚物所得的平均粒徑約在290 nm和450 nm之間。其次,利用化學還原法製備奈米金桿,藉由增加銀離子的含量,可使奈米金桿的縱向表面電漿共振吸收(SPL)有紅移的現象。當Ag+/Au3+G比值到達時,有最大的產率,SPL, max最大吸收波長在779 nm附近。利用控制奈米金桿成長的時間,可以得到SPL, max最大吸收波長在806 nm且吸收度為2.35的奈米金桿溶液。利用W/O乳化法製備CS/AuR/CS-PN-PEG10複合載體,可以成功的將奈米金桿包覆,經過載入藥物Diclofenac Sodium (DS),其承載率為0.669 %,包覆率為78.0 %。CS/AuR/CS-PN-PEG10複合藥物載體經雷射光照射後,導致藥物載體收縮而加速DS的釋放,經過24小時的藥物釋放後,藥物累積釋放百分比為58.9 %。
英文摘要 In the fisrt part of this study, emulsifier-free emulsion polymerization of MMA was initiated directly by the Cu2+/HSO3- redox system. Latex particles with negative charge due to the bonded anionic sulfite ion were successfully synthesized after 2 h of reaction at 40 to 60oC. SEM pictures showed an uniform particle size distribution, and the average size decreased from 223 nm to 165 nm by increasing reaction temperature from 40oC to 60oC. The initiation step in polymerization mechanism was proved to be a redox reaction, in which Cu2+ oxidized the bisulfite ion to produce anionic sulfite radical and proton. The produced anionic sulfite radical then initiated polymerization of MMA. Moreover, Cu2+ not only served as one component in the redox initiator system but also a chain transfer agent that terminated growing polymer chains to produce chains with unsaturated end group (PMMA-CR=CH2). For the present system, about 17 % of PMMA-CR=CH2 was produced. The tacticities of PMMA latex prepared at 40~60oC were almost the same, ca. 62~64 % rr, 33~35 % mr, and 3 % mm. These PMMA latexes had almost the same Tg, 125~127oC, regardless of the reaction temperatures and their weight-average molecular weight was in the range between 254,000 and 315,000.
PMMA latex was synthesized in an emulsifier-free emulsion polymerization at 60oC using a Cu2+/HSO3- redox initiator system with different concentrations of Cu2+. The experimental results showed that the monomer conversion reached above 90 % for all systems. Zeta potential was all negative due to the bonded bisulfite ion and the magnitude was greater than 30 mV, providing the stability of PMMA emulsion. The morphology of the latex observed by SEM revealed an uniform particle size and the average particle size increased from 181.9 nm to 234.2 nm as the Cu2+ ion concentration increased from 2.0 mM to 6.0 mM in 1 M of MMA solution. Thermal degradation behavior of synthesized PMMA was studied by TGA, in which a two-stage degradation behavior was observed. These two stages were found to be caused by the degradation of unsaturated end group (PMMA-CR=CH2) and saturated end group (PMMA-H), respectively. In addition, the higher the concentration of Cu2+ ion, the more the proportion of PMMA-CR=CH2 in final product, and in turn giving more weight loss in the first-stage degradation. The copper ion not only acted as a role in the redox initiation, but also as a chain transfer agent to terminate growing polymer chains thus producing PMMA-CR=CH2. The apparent activation energies of the first stage (Ea1) and second stage (Ea2) were calculated by Ozawa’s method as well as Boswell’s method. The results showed that the apparent activation energies of PMMA-CR=CH2 were in the range between 123.6 kJ/mol and 134.8 kJ/mole, and those of PMMA-H were in the range between 156.4 kJ/mol and 213.4 kJ/mole.
In the second part this study, Chitosan-PNIPAAm-PEGMA (CS-PN-PEG) microgel copolymers were synthesized with biocompatible Chitosan (CS), thermal-responsive N-isopropylacrylamide (NIPAAm), and non-immunogenic Poly(ethylene glycol) metharcylate (PEGMA) by using ammonium persulfate (APS) as the initiator. In the batch reaction system, two-stage transition behaviors of CS-PN-PEG microgel copolymer were observed because the reaction product was composed of CS-PN-PEG and CS-PN copolymers due to the different monomer reactivity. In the continuous-feeding reaction system, one stage transition behavior of CS-PN-PEG microgel copolymer was observed. At pH4, the LCST values were shifted to higher temperatures from 33.0oC to 39.7oC with increasing the addition of hydrophilic PEGMA monomer. CS-PN-PEG microgel copolymer was immediately shrunk as the temperature reached to LCST due to the well-hydrophilic chitosan chains with excellent mobility tended to disentanglement at acidic condition. At pH7, the LCST values were shifted to higher temperatures from 35.7oC to 45oC with increasing hydrophilic PEGMA monomer. One stage transition behavior of CS-PN-PEG microgel copolymer exhibited slightly delay at neutrality due to the worse chain mobility on chitosan. The average particle size was in the range between 290 nm and 450 nm by using light scattering method. In addition, gold nanorods (AuR) were prepared by a seed-mediated growth approach. The longitudinal surface of plasmon resoncance (SPL) of AuR exhibited red-shifts with increasing the addition of silver ion. As Ag+/Au3+G ratio reached to 0.35, AuR had the maximum yield in which the SPL, max increased to 779 nm. AuR (SPL, max=806 nm and Abs. =2) was obtained by controlling the aging time. Moreover, CS/AuR/CS-PN-PEG10 complex carrier was obtained by using water in oil (W/O) method. After encapsulation of diclofenac sodium (DS), the loading was 0.669 % and encapsulation efficiency was 78 %. When CS/AuR/CS-PN-PEG10 complex carrier was irradiated by near IR light, they transformed the light into heat and thus raised temperature of the carrier. Subsequently, the thermal-responsive component undergoes phase transition causing volume shrinkage to squeeze out DS drug. After 24 hours, drug release amount reached 58.9%.
論文目次 目 錄
中文摘要 I
英文摘要 IV
目 錄 VII
圖 目 錄 XIII
表 目 錄 XXI
第一章 緒論 1
1.1 前言 1
1.2 研究動機 1
1.3 研究架構及目的 2
第二章 Cu2+/HSO3-氧化還原起始系統合成PMMA奈米顆粒之反應動力機構和熱裂解行為之研究 6
2.1 前言 6
2.2 乳化聚合理論與文獻回顧 7
2.2.1乳化聚合的反應機構 7
2.2.2無乳化劑乳化聚合的簡介 10
2.2.2.1無乳化劑乳化聚合的起源 10
2.2.2.2無乳化劑乳化聚合的成核機構 11
2.2.2.3影響無乳化劑乳化聚合的變因 15
2.2.3 與銅離子相關的文獻 18
2.3 PMMA熱裂解行為研究 19
2.3.1 PMMA的熱裂解反應機構 21
2.3.1.1 飽和末端雙鍵PMMA-CR=CH2的熱裂解反應機構 23
2.3.1.2 PMMA-H的熱裂解反應機構 27
2.3.1.3 PMMA-hh的熱裂解反應機構 27
2.3.2 PMMA在有氧氣的環境下和加入添加物的熱裂解反應機構 29
2.3.2.1 PMMA在有氧環境下的熱裂解反應機構 29
2.3.2.2 PMMA在有氧環境下加入金屬觸媒的熱裂解反應機構 32
2.4 Cu2+/HSO3-氧化還原起始劑系統製備PMMA乳膠顆粒 33
2.5 實驗方法與步驟 35
2.5.1實驗藥品 35
2.5.2 實驗設備 37
2.5.3 不同反應溫度合成PMMA乳膠顆粒 40
2.5.4 不同起始劑濃度合成PMMA乳膠顆粒 41
2.5.5 分析方法 43
2.5.5.1單體轉化率 43
2.5.5.2乳膠顆粒性質 43
2.5.5.3 起始反應機構的證明 44
2.5.5.4結構分析 45
2.5.5.5 熱分析 46
2.6. 結果與討論 48
2.6.1 不同反應溫度下合成PMMA乳膠顆粒之研究 48
2.6.1.1 反應機制與單體轉化率 48
2.6.1.2 分子鏈結構分析 54
2.6.1.3 乳膠顆粒形態和熱性質 62
2.6.2 不同銅離子濃度合成PMMA乳膠顆粒之研究 66
2.6.2.1 PMMA乳膠顆粒的結構與玻璃轉移溫度 66
2.6.2.2 熱裂解行為 71
2.7 結論 81
2.8 參考文獻 84
第三章 製備光可調控溫度敏感型載體及藥物控制釋放系統 96
3.1 前言 96
3.2溫度敏感型高分子載體 97
3.3 奈米金 100
3.3.1奈米金的製備與穩定性 101
3.3.2奈米金的光熱性質 104
3.4 幾丁聚醣及其在藥物釋放載體的應用 106
3.4.1 幾丁聚醣/三聚磷酸鹽(Chitosan/TPP) 107
3.4.2 自組裝的改質幾丁聚醣奈米顆粒 109
3.4.3 Chitosan-DNA混成膠體系統 109
3.4.4 幾丁聚醣塗佈系統(Chitosan-coated system) 110
3.5 光可調控溫度敏感型載體的研究目的 111
3.6 實驗方法與步驟 113
3.6.1 實驗藥品 113
3.6.2 實驗設備 118
3.6.3 溫度敏感型共聚物 120
3.6.3.1 批次反應合成CS-PN-PEG共聚物 120
3.6.3.2 連續進料系統合成CS-PN-PEG共聚物 122
3.6.3.3 單體轉化率 124
3.6.3.4 結構分析 125
3.6.3.5 CS-PN-PEG共聚物顆粒性質 125
3.6.3.6 CS-PN-PEG共聚物相變化溫度(LCST)的量測 126
3.6.4 奈米金桿 126
3.6.4.1 奈米金桿的製備 126
3.6.4.2 紫外光-可見光光譜分析(UV-VIS spectra) 128
3.6.4.3 穿透式電子顯微鏡分析(TEM) 128
3.6.5 AuR/CS-PN-PEG複合載體的製備 128
3.6.5.1 場放射掃描式電子顯微鏡分析(SEM) 128
3.6.5.2 穿透式電子顯微鏡分析(TEM) 129
3.6.5.3 奈米金桿對激發光源之吸收 129
3.6.6 藥物的包覆與釋放測試 130
3.6.6.1 DS在水中的檢量線 131
3.6.6.2 DS在磷酸鹽緩衝溶液中的檢量線 131
3.6.6.3 CS-PN-PEG共聚物的藥物包覆 131
3.6.6.4 藥物釋放測試 132
3.6.6.5 雷射引導藥物釋放測試 133
3.7 結果與討論 135
3.7.1 幾丁聚醣-聚氮異丙基丙烯醯胺共聚物(CS-PN)的合成及其LCST值 135
3.7.2 批次反應系統合成CS-PN-PEG共聚物及其LCST值 138
3.7.3 連續進料系統合成CS-PN-PEG共聚物及其LCST值 142
3.7.4 單體進料與共聚物組成的關係 150
3.7.5 CS-PN-PEG共聚物的FTIR結構分析 156
3.7.6 CS-PN-PEG的固態13C-NMR光譜分析 162
3.7.7 CS-PN-PEG共聚物的ξ電位 167
3.7.8 CS-PN-PEG共聚物的顆粒大小 168
3.7.9 奈米金桿 178
3.7.9.1 銀離子的影響 178
3.7.9.2 成長溶液中金鹽濃度的影響 184
3.7.9.3 抗壞血酸的影響 187
3.7.9.4 奈米金桿成長動力 189
3.7.9.5 AuR/CS-PN-PEG10複合載體 193
3.7.9.6 CS/AuR/CS-PN-PEG10複合載體 194
3.7.9.7 奈米金桿的光熱效應 196
3.7.10 藥物釋放 197
3.7.10.1 Diclofenac Sodium (DS) 溶於水中的檢量線 197
3.7.10.2 DS溶於磷酸鹽緩衝溶液的檢量線 199
3.7.10.3 CS-PN-PEG載體的藥物包覆與釋放測試 201
3.7.10.4 CS/AuR/CS-PN-PEG10複合載體的藥物包覆與釋放測試 204
3.8 結論 206
第四章 總結與建議 219
4.1 總結 219
4.2 建議 222

圖 目 錄
圖1.1 Cu2+/HSO3-氧化還原起系統起始聚合PMMA乳膠顆粒的研究架構流程圖 3
圖1.2 光可調控溫度敏感性載體的研究架構流程圖 4
圖2.1 乳化聚合反應縮圖 9
圖2.2 類微胞成核機構示意圖 13
圖2.3均相成核機構示意圖 14
圖2.4 自由基聚合終止反應的途徑 22
圖2.5 PMMA-CR=CH2以β scission的方式裂解 23
圖2.7 自由基經鏈轉移的熱裂解機構 25
圖2.8 熱裂解反應可能生的的末端基團 26
圖2.9 PMMA-H的裂解機構 27
圖2.10 head-to head的熱裂解機構 28
圖2.11 籠子效應造成的disproportionation終止反應 29
圖2.12 在O2的環境下PMMA-hh可能發生的熱裂解反應機構(續) 31
圖2.12 在O2的環境下PMMA-hh可能發生的熱裂解反應機構 32
圖2.13 PMMA加入金屬離子在有氧環境下的熱裂解反應機構 33
圖2.14 不同反應溫度合成PMMA乳膠顆粒流程及分析項目圖 41
圖2.15 不同銅離子濃度合成PMMA乳膠顆粒流程及分析項目圖 42
圖2.16 Cu2+/HSO3-起始系統合成PMMA的反應機制 50
圖2.17 硫酸銅水溶液和硫酸銅/亞硫酸氫鈉水溶液在60oC的環境下30分鐘,再經由neocuproine處理程序後的紫外光/可見光光譜圖 51
圖2.18 Cu2+/HSO3-氧化還原起始系統在反應溫度60oC下,合成PMMA乳膠顆粒的單體轉化率(X)和聚合反應速率(Rp)動力曲線圖 53
圖2.19 不同反應溫度下PMMA乳膠顆粒的(a)熱重損失和(b)一階微分熱重損失曲線圖,升溫速率為10oC/min。 55
圖2.20 成長中的PMMA高分子鏈與銅離子產生鏈轉移反應 58
圖2.21 商業用PMMA(PMMA-C)與其以等比例混合硫酸銅的熱重損失曲線圖,升溫速率為10oC/min。 59
圖2.22 BC60乳膠顆粒的1H NMR光譜圖(600 MHz) 60
圖2.23反應溫度60oC下所合成的PMMA乳膠顆粒,在不同倍率下的SEM (a) 20,000倍, (b) 50,000倍, (c) 100,000倍and (d) 200,000倍。尺標為200 nm。 63
圖2.24不同反應溫度下PMMA乳膠顆粒的DSC曲線圖,升溫速率為10oC/min。 65
圖2.25 不同銅離子濃度合成PMMA乳膠顆粒,於反應2小時後的粒徑分佈圖,其中S5C1:[Cu2+] = 2 mM,S5C2:[Cu2+] = 4 mM,S5C3:[Cu2+] = 6 mM。 68
圖2.26 不同銅離子濃度在60oC下合成PMMA乳膠顆粒的SEM圖,其中(a) S5C1 ([Cu2+] = 2 mM),(b) S5C2 ([Cu2+] = 4 mM),(c) S5C3 ([Cu2+] = 6 mM),尺標為 200 nm。 69
圖2.27 不同銅離子濃度在60oC下合成PMMA乳膠顆粒的DSC曲線,其中S5C1: [Cu2+] = 2 mM, S5C2: [Cu2+] = 4 mM, S5C3: [Cu2+] = 6 mM。 70
圖 2.28 商業用PMMA-C和PMMA-KPS的(a)熱重損失和(b)一階微分熱重損失曲線圖,升溫速率10oC/min. 72
圖2.29 不同銅離子濃度合成PMMA乳膠顆粒的(a)熱重損失和(b)一階微分熱重損失曲線圖,升溫速率為10oC/min,其中 S5C1: [Cu2+] = 2 mM,S5C2: [Cu2+] = 4 mM,S5C3: [Cu2+] = 6 mM 75
圖2.30 S5C3在不同升溫速率的熱裂解曲線 79
圖2.31 利用TGA在不同升溫速率下(5、10、15和20oC/min)對S5C3進行熱裂解後所繪製的Ozawa線性圖 80
圖2.32 利用TGA在不同升溫速率下(5、10、15和20oC/min)對S5C3進行熱裂解後所繪製的Boswell線性圖 80
圖3.1溫度敏感型水膠PNIPAAm藥物釋放示意圖 98
圖3.2 高分子穩定奈米金粒子的機制 103
圖3.3交聯的PNIPAAm水膠對奈米金粒子的穩定系統 104
圖3.4 微凝膠顆粒在雷射光源照射下的體積變化率(◇Poly(NIPAAm-co-AAc),◆AuRod/Poly(NIPAAm-co-AAc)) 105
圖3.5 雷射導引藥物釋放系統 112
圖3.6 批次反應合成CS-PN-PEG共聚物的流程圖 121
圖3.7 利用蠕動幫浦連續進料PEGMA以合成CS-PN-PEG共聚物的實驗流程及結構分析項目圖 123
圖3.8 奈米金桿光熱能量轉換圖 130
圖3.9 藥物控制釋放裝置圖 133
圖3.10 雷射引導藥物控制釋放裝置圖 134
圖3.11純PN與CS-PN共聚物在不同溫度下的UV450穿透度曲線 137
圖3.11 批次反應系統合成CS-PN-PEG共聚物在不同時間取樣的(a)UV450穿透度曲線及(b)UV450穿透度曲線微分圖 140
圖3.12 連續進料系統合成CS-PN-PEG共聚物,經1%醋酸水溶液釋,在不同溫度下的(a)UV450穿透度曲線及(b)UV450穿透度曲線微分圖。 145
圖3.13 連續進料系統合成CS-PN-PEG共聚物,調整溶液酸鹼值為pH4,在不同溫度下的(a)UV450穿透度曲線及(b)UV450穿透度曲線微分圖。 146
圖3.14 連續進料系統合成CS-PN-PEG共聚物,調整溶液酸鹼值為pH7,在不同溫度下的(a)UV450穿透度曲線及(b)UV450穿透度曲線微分圖。 147
圖3.15 連續進料系統合成CS-PN-PEG共聚物,調整溶液酸鹼值為pH9,在不同溫度下的(a)UV450穿透度曲線及(b)UV450穿透度曲線微分圖。 148
圖3.16 CS-PN-PEG共聚物的PEGMA含量與不同酸鹼環境下的LCST 149
圖3.17 單體進料組成與共聚物組成的模擬關係圖 152
圖3.18 批次反應系統CS-PN-PEG6的單體進料組成與共聚物組成的模擬關係圖 152
圖3.19連續進料系統CS-PN-PEG6的單體進料組成與共聚物組成的關係圖 153
圖3.20 CS-PN-PEG6批次反應系統與連續進料系統的共聚物組成與時間的關係圖 153
圖3.21連續進料系統CS-PN-PEG8的單體進料組成與共聚物組成的關係圖 154
圖3.22連續進料系統CS-PN-PEG16的單體進料組成與共聚物組成的關係圖 154
圖3.23 (a)CS-PN-PEG8和(b)CS-PN-PEG16共聚物組成與反應時間的關係圖 155
圖3.25 (a)純PNIPAAm、(b)純PEGMA、(c)純幾丁聚醣和(d)CS-PN-PEG8共聚物的FTIR光譜圖 159
圖3.26 (a) CS-PN-PEG8、(b) CS-PN-PEG12和(c) CS-PN-PEG16共聚物的FTIR光譜圖 160
圖3.27 純幾丁聚醣13C-NMR光譜圖 163
圖3.28 CS-PN-PEG8的13C-NMR光譜圖 164
圖3.28 CS-PN-PEG12的13C-NMR光譜圖 164
圖3.30 CS-PN-PEG16的13C-NMR光譜圖 165
圖3.31 CS-PN-PEG共聚物顆粒隨pH值變化的ξ電位 167
圖3.32 (a) CS-PN-PEG8, (b) CS-PN-PEG10, (c) CS-PN-PEG12, (d) CS-PN-PEG14和(e) CS-PN-PEG16共聚物的SEM圖(續) 170
圖3.32 (a) CS-PN-PEG8, (b) CS-PN-PEG10, (c) CS-PN-PEG12, (d) CS-PN-PEG14和(e) CS-PN-PEG16共聚物的SEM圖(續) 171
圖3.32 (a) CS-PN-PEG8, (b) CS-PN-PEG10, (c) CS-PN-PEG12, (d) CS-PN-PEG14和(e) CS-PN-PEG16共聚物的SEM圖(續) 172
圖3.32 (a) CS-PN-PEG8, (b) CS-PN-PEG10, (c) CS-PN-PEG12, (d) CS-PN-PEG14和(e) CS-PN-PEG16共聚物的SEM圖(續) 173
圖3.32 (a) CS-PN-PEG8, (b) CS-PN-PEG10, (c) CS-PN-PEG12, (d) CS-PN-PEG14和(e) CS-PN-PEG16共聚物的SEM圖 174
圖3.33 (a) CS-PN-PEG8, (b) CS-PN-PEG10, (c) CS-PN-PEG12, (d) CS-PN-PEG14和(e) CS-PN-PEG16共聚物的TEM圖,尺標為2m 175
圖3.34CS-PN-PEG共聚物的粒徑分佈圖 176
圖3.35 改變成長溶液中銀離子濃度所形成奈米金桿的UV-Vis光譜圖 183
圖3.36 改變Ag+/Au3+G比例所形成的奈米金桿與SPL, max最大吸收波長和吸收值的關係圖 183
圖3.37 銀低電位沈積在成長中奈米金桿表面的反應機制示意圖 184
圖3.38 改變成長溶液中金離子濃度所形成奈米金桿的UV-Vis光譜圖 185
圖3.39 改變成長溶液中金離子含量所形成的奈米金桿與SPL, max最大吸收波長和吸收值的關係圖 186
圖3.40改變抗壞血酸濃度所形成奈米金桿的UV-Vis光譜圖 188
圖3.41 改變AA/Au3+G比例所形成的奈米金桿與表面電漿共振吸收最大吸收波長和吸收度的關係圖 189
圖3.42 奈米金桿成長過程的UV-Vis光譜圖 190
圖3.43 奈米金桿溶液成長過程的SPL, max最大吸收波長與吸收強度 190
圖3.44 反應18分鐘後,分離奈米金桿與成長溶液所得到奈米金桿的UV-Vis光譜圖 192
圖3.45 反應18分鐘後,分離奈米金桿與成長溶液所得到奈米金桿的TEM圖 192
圖3.46 AuR/CS-PN-PEG10複合載體的(a)SEM圖和(b)TEM圖 193
圖3.47 CS/AuR/CS-PN-PEG10複合載體的(a)SEM圖和(b)TEM圖 195
圖3.48奈米金桿光熱轉換的效應 196
圖3.49 DS在水中不同標準溶液的UV圖 198
圖3.50 DS在水中的檢量線圖 198
圖3.51 DS在磷酸緩衝溶液中不同標準溶液的UV圖 200
圖3.52 DS在磷酸緩衝溶液中的檢量線圖 200
圖3.53CS-PN-PEG6包覆藥物上下層藥物釋放動力曲線 202
圖3.54 CS-PN-PEG6藥物載體在不同時間的藥物累積釋放量 203
圖3.55 CS-PN-PEG6藥物載體在不同時間的藥物累積釋放百分比 203
圖3.56 CS/AuR/CS-PN-PEG10複合藥物載體恆溫37oC(a)照射雷射光和(b)未照射雷射光在不同時間的藥物累積釋放量 205
圖3.57 CS/AuR/CS-PN-PEG10複合藥物載體恆溫37oC(a)照射雷射光和(b)未照射雷射光在不同時間的藥物累積釋放百分比 205

表 目 錄
表2.1 不同反應溫度合成PMMA乳膠顆粒的配方 40
表2.2 不同銅離子濃度合成PMMA乳膠顆粒的配方 42
表2.3反應前後pH值 48
表2.4不同反應溫度合成PMMA乳膠顆粒的轉化率與界面電位
表2.1 不同反應溫度合成PMMA乳膠顆粒的配方 40
表2.2 不同銅離子濃度合成PMMA乳膠顆粒的配方 42
表2.3反應前後pH值 48
表2.4不同反應溫度合成PMMA乳膠顆粒的轉化率與界面電位 52
表2.5 不同反應溫度下合成PMMA乳膠顆粒的最大速率裂解溫度(Td1 和Td2)與溫度600oC時的殘留重量百分比 (R. W.) 56
表2.6 改變銅離子濃度在反應溫度60oC下合成PMMA的最大速率裂解溫度(Td)和裂解程度(degradation extents, DE) (MMA=1.0 M) 56
表2.7 不同反應溫度合成PMMA的立體異構性 61
表2.8 不同反應溫度合成PMMA乳膠顆粒的重量和數目平均分子量 62
表2.9 不同反應溫度合成PMMA乳膠顆粒平均粒徑(Dp)和在水相中的濃度(Np) 63
表2.10 不同銅離子濃度合成PMMA乳膠顆粒的單體轉化率、平均粒徑與界面電位 66
表2.11 不同銅離子濃度合成PMMA乳膠顆粒的熱裂解性質 76
表2.12 不同銅離子起始劑濃度合成PMMA乳膠顆粒的重量平均與數目平均分子量 77
表2.13 不同銅離子濃度合成PMMA乳膠顆粒的熱裂解活化能 81
表3.1 合成CS-PN共聚物的反應系統組成 136
表3.2 批次反應系統合成CS-PN-PEG共聚物的配方 139
表3.3 批次反應系統CS-PN-PEG6在不同時間取樣的轉化率與其LCST值 141
表3.4 連續進料系統合成CS-PN-PEG共聚物的配方 142
表3.5 CS-PN-PEG共聚物的轉化率與不同酸鹼環境下的LCST 149
表3.8 相關FTIR吸收峰之位置表 161
表3.7純幾丁聚醣和CS-PN-PEG共聚物各個碳的化學位移 166
表3.8 CS-PN-PEG共聚物的粒徑 177
表3.9奈米金種晶溶液的配方 179
表3.10改變成長溶液中銀離子的含量以合成奈米金桿的配方 179
表3.13 銀離子濃度與奈米金桿SPL, max最大吸收波長的關係 182
表3.12 成長溶液的金鹽濃度與奈米金桿SPL, max最大吸收波長的關係 185
表3.13改變抗壞血酸濃度與奈米金桿SPL, max最大吸收波長的關係 188
表3.14 DS溶於水中的不同標準溶液 197
表3.15 DS溶於磷酸緩衝溶液中的不同標準溶液 199
表3.16 CS-PN-PEG6包覆藥物DS的釋放測試 202
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