purelab classic DI 型號之純水。純化用的透析膜使用 Spectrum 公司規格 standard RC Trial Kit MWCO: 1 kD 與 3.5 kD 之透析膜，透析過程每 12 小時換水一次，共換水 2 次。
4-2 實驗儀器
實驗過程中為了鑑定化合物與高分子之結構、測量吸收及其相關性質使用了 下列儀器進行分析。
4-2-1 核磁共振光譜儀(Nuclear Magnetic Reasonance, NMR)
1H NMR 與13C NMR 使用 Bruker AVIII HD 400 NMR 及 Bruker AVIII-500MHz FT-NMR 核磁共振儀進行測量，化學位移單位為 ppm，d-chloroform(CDCl3)以 δ=7.26 ppm，deuterium oxide(D2O)以 δ=4.79 ppm，d6-DMSO 以 δ=2.5 ppm 為內 部標定，光譜數據內s 代表單峰(singlet)，d 代表二重峰(doublet)，t 代表三重峰 (triplet)，dd 代表雙二重峰(doublet of doublet)，m 代表多重峰(multiplet)。
4-2-2 質譜儀(Mass Spectrometry, MS)
合成之單體使用國立臺灣大學貴重儀器中心之高解析電灑游離法質譜儀 (High-resolution electrospray ionization mass spectrometry, HRESI-MS)鑑定其分子量，
廠牌型號為Thermo UltiMate 3000, Orbitrap QE Plus Mass Spectrometry。
4-2-3 凝膠滲透層析儀(Gel Permeation Chromatography, GPC)
量測分子量是使用國立臺灣科技大學材料系陳志堅教授實驗室之 GPC 儀器，
型號是JASCO PU-980, JASCO RI-4030, SHODEX GPC KF-804，沖提液為二甲基 乙醯胺(DMAc)，polystyrene 為標準品，測量樣品濃度為 1 mg 的樣品/1 ml 的 DMAc，
注射前先以孔徑0.22 μm 之濾盤過濾。
4-2-4 紫外光可見光吸收光譜儀(Uv-Vis Spectrophotometer)
測量吸收光譜使用國立臺灣大學生化科技學系楊啟伸教授實驗室之紫外光可 見光吸收光譜儀，型號為HITACHI U-1900，測量物質皆溶於水中，量測濃度為 0.05 mg 的樣品/1 ml 的純水。
4-2-5 粒徑/介面電位分析儀(Particle Sizing and Zeta Potential)
本實驗所使用之粒徑分析儀為國立臺灣大學高分子科學與工程學研究所共同 儀器室的90-Plus，分析溫度為 25°C，每次量測為 5 個循環，每個循環時間為 1 分 鐘。
4-2-6 基質輔助雷射脫附游離飛行時間質譜儀(Matrix-Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry, MALDI-TOF)
本實驗使用之 MALDI-TOF 是使用國立臺灣大學化學系質譜核心實驗室之儀 器，廠牌為Bruker Daltonics，型號為 Autoflex Speed，基質為 2,5-二羥苯甲酸(2,5-dihydroxybenzoic acid, DHB)或芥子酸(sinapic acid, SA)。
4-3 合成
2-bromo-9,9’-bis(6-bromohexyl)fluorine 之合成
Under nitrogen atmosphere, to a mixture of aqueous potassium hydroxide (40 mL, 50%), tetrabutylammonium bromide (129 mg, 0.4 mmol), and 1,6-dibromohexane (4.88 g, 20 mmol) was added 2-bromofluorene (500 mg, 2.04 mmol). The mixture was stirred at 75
°C for 2 hours, cooled to room temperature, and extracted with dichloromethane. The combined organic layer was washed with water, aqueous HCl (1 M), water, and brine consecutively and dried over MgSO4. The solvent was evaporated and the excess amount of 1,6-dibromohexane was removed under high vacuum. The residue was purified by column chromatography on silica gel using hexane as the eluent to give 2-bromo-9,9′-bis(6-bromohexyl)fluorene as a colorless oil (423 mg, 36%).
1H NMR (400 MHz, CDCl3) δ: 7.65–7.68 (m, 1H), 7.54–7.57 (m, 1H), 7.43–7.48 (m, 2H), 7.29–7.35 (m, 3H), 3.26–3.30 (t, J = 6.8 Hz, 4H), 1.90–2.02 (m, 4H), 1.61–1.70 (m, 4H),
1.02–1.26 (m, 8H), 0.53–0.65 (m, 4H).
F1 之合成
Under nitrogen atmosphere, 2-bromo-9,9′-bis(6-bromohexyl)fluorene (1.6 g, 2.8 mmol) was added to a THF (15 mL) solution of trimethylamine (3 mL, 12.6 mmol, 4.2 M in ethanol). The mixture was stirred overnight at 40 oC. After removal of the solvent, the residue was washed with chloroform and dichloromethane to furnish F1 as a white powder (1.44 g, 75%).
1H NMR (400 MHz, d6-DMSO) δ: 7.82–7.87 (m, 1H), 7.76–7.80 (m, 1H), 7.69–7.71 (m, 1H), 7.51–7.55 (m, 1H), 7.43–7.48 (m, 1H), 7.33–7.38 (m, 2H), 3.09– 3.15 (m, 4H), 2.94–
2.98 (s, 18H), 1.93–2.09 (m, 4H), 1.39–1.52 (m, 4H), 0.94–1.12 (m, 8H), 0.43–0.53 (m, 4H).
13C NMR (125 MHz, d6-DMSO) δ: 152.56, 149.61, 139.96, 139.52, 129.99, 127.83, 127.20, 125.93, 122.87, 121.87, 120.49, 120.27, 65.15, 55.04, 52.10, 28.59, 25.38, 23.23, 21.87.
F2 之合成
To a stirred mixture of 2-bromofluorene (2 g, 8.16 mmol) and 35 ml of dimethylsulfoxide (DMSO) under nitrogen were added tetrabutylammoium bromide (110 mg) and a 50 wt%
aqueous solution (8 ml) of sodium hydroxide. A DMSO (10 ml) solution of 1,4-butanesultone (2.68 g, 19.7 mmol) was added dropwise to the mixture. The reaction mixture was stirred at room temperature for 4 h and dropped slowly into 500 ml of acetone to induce precipitation. The precipitate was collected by filtration, washed with ethanol, and recrystallized from acetone/H2O to yield ivory solid (2.75 g, 60%).
1H NMR (400 MHz, D2O) δ: 7.77–7.75 (m, 1H), 7.67 (d, J=8.1 Hz, 1H), 7.63 (d, J=1.52 Hz, 1H), 7.51 (dd, J=8.1, 1.6 Hz, 1H), 7.46–7.43 (m, 1H) 7.38–7.36 (m, 2H), 2.56–2.52 (m, 4H), 2.04–1.98 (m, 4H), 1.42 (quin, J=7.8 Hz, 4H), 0.60–0.53 (m, 4H).
13C NMR (100 MHz, D2O) δ: 152.46, 149.82, 139.81, 139.68, 130.08, 127.76, 127.23, 126.33, 123.29, 121.27, 120.75, 119.81, 54.83, 50.68, 38.62, 24.16, 22.36.
2-(2-bromothiophen-3-yl)ethanol 之合成
To a solution of 2-(3-thienyl)ethanol (1 g, 7.8 mmol) in CH2Cl2 (50 mL), 1.667g (9.36
mmol) of NBS was added. The reaction mixture was sonicated for 90 min at 40 °C and cooled to room temperature. The mixture was washed with saturated NaHCO3 solution, water, and brine consecutively and dried over MgSO4. The residue was purified by column chromatography on silica gel (ethyl acetate : hexane 2:8 v/v) to give 2-(2-bromothiophen-3-yl)ethanol as a yellow oil (1.45 g, 90%).
1H NMR (400 MHz, CDCl3) δ: 7.24 (d, J=5.6 Hz, 1H), 6.87 (d, J=5.6 Hz, 1H), 3.82–3.87 (m, 2H), 2.87 (t, J=6.56 Hz, 2H), 1.42 (t, J=5.6 Hz, 1H).
13C NMR (100 MHz, CDCl3) δ: 137.86, 128.45, 125.64, 110.30, 62.03, 32.72.
2-bromo-3-(2-(6-bromohexyloxy)ethyl)thiophene 之合成
Under nitrogen, to a solution of 2-(2-bromothiophen-3-yl)ethanol (1 g, 4.83 mmol) in 40 mL of dried THF was slowly added sodium hydride (60% in mineral oil, 0.3 g, 7.5 mmol) with vigorous stirring. The reaction mixture was stirred for 30 min at room temperature.
1,6-dibromohexane (5.98 g, 24.53 mmol) was then added and the mixture was stirred for 1 h at room temperature and for 15 h at 80 °C. The reaction was quenched with water.
The organic phase was extracted with diethyl ether and dried over MgSO4. The solvent was evaporated and the excess amount of 1,6-dibromohexane was removed under high vacuum. After removal of the solvent, the residue was purified by silica gel chromatography (ethyl acetate ： hexane 1:9 v/v) to afford 2-bromo-3-(2-(6-bromohexyloxy)ethyl)thiophene as a pale yellow oil (0.31 g, 17%).
1H NMR (400 MHz, CDCl3) δ: 7.19 (d, J=5.6 Hz, 1H), 6.86 (d, J=5.6 Hz, 1H), 3.59 (t, J=6.96 Hz, 2H), 3.43 (t, J=6.3 Hz, 2H), 3.40 (t, J=6.72 Hz, 2H), 2.85 (t, J=6.96 Hz, 2H), 1.89–1.82 (m, 2H), 1.61–1.54 (m, 2H), 1.46–1.34 (m, 4H).
13C NMR (100 MHz, CDCl3) δ: 138.40, 128.56, 125.17, 109.79, 70.64, 69.64, 33.78, 32.65, 29.92, 29.41, 27.87, 25.27.
T1 之合成
Under nitrogen atmosphere, 3-(2-(6-bromohexyloxy)ethyl)thiophene (370 mg, 1 mmol) was added to a dried THF (0.5 ml) solution of trimethylamine (3ml, 12.6 mmol, 4.2 M in ethanol). The mixture was stirred overnight at 40 °C. After removal of the solvent, the residue was washed with hexane to furnish T1 as a white solid (0.382 g, 89%).
1H NMR (400 MHz, D2O) δ: 7.43 (d, J=5.6 Hz, 1H), 6.99 (d, J=5.6 Hz, 1H), 3.77 (t, J=6.4 Hz, 2H), 3.53 (t, J=6.44 Hz, 2H), 3.28 (m, 2H), 3.11 (s, 9H), 2.89 (t, J=6.34 Hz, 2H), 1.76 (m, 2H), 1.55 (m, 2H), 1.33 (m, 4H).
13C NMR (125 MHz, D2O) δ: 138.49, 128.83, 126.16, 109.48, 70.43, 69.21, 66.48, 52.79, 29.25, 28.50, 25.31, 24.95, 22.30.
T2 之合成
To a toluene solution (35 ml) of 2-(2-bromothiophen-3-yl)ethanol (1 g, 4.83 mmol), sodium hydride (60% in mineral oil, 0.46 g, 11.59 mmol) was added slowly. The mixture was stirred at room temperature for 30 min, followed by adding 1,4-butanesultone (0.92 g, 6.76 mmol) drop-wise, and then refluxed for 2 h under nitrogen. The precipitate was collected by filtration, washed with toluene, and dried under vacuum to furnish a pale yellow solid (1.24 g, 70%).
1H NMR (400 MHz, D2O) δ: 7.40 (d, J=5.6 Hz, 1H), 6.97 (d, J=5.6 Hz, 1H), 3.75 (t, J=6.4 Hz, 2H), 3.54 (t, J=6.2 Hz, 2H), 2.89−2.84 (m, 4H), 1.70−1.61 (m, 4H).
13C NMR (100 MHz, D2O) δ: 138.40, 128.44, 126.25, 125.56, 69.82, 69.17, 50.60, 28.86, 27.41, 20.76.
2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene 之合成
An aqueous (100 mL) solution of KOH (50 g, 891.3 mmol) was heated to 80 °C. 2,7-dibromofluorene (1.62 g, 5.0 mmol), 1,6-dibromohexane (12.2 g, 50 mmol), and tetrabutylammonium bromide (0.16 g 0.49 mmol) were added. The reaction mixture was
with dichloromethane. The organic layer was collected, washed with dilute hydrochloric acid (100 mL), water (100 mL) and brine (100 mL) sequentially, and dried over MgSO4. After removal of solvent, the residue was heated at 70 °C under 0.03 mbar to remove excess 1,6-dibromohexane and purified by column chromatography (silica gel, chloroform : hexane = 1 : 9) to give 2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene as a white solid (1.72 g, 53%).
1H NMR (400 MHz, CDCl3) δ: 7.53 (d, J = 8.0 Hz, 2H), 7.46 (dd, J = 8.0, 1.7 Hz, 2H), 7.44 (d, J = 1.7 Hz, 2H), 3.29 (t, J = 6.8 Hz, 4H), 1.91-1.95 (m, 4H), 1.64-1.71 (m, 4H), 1.24-1.12 (m, 4H), 1.05-1.10 (m, 4H), 0.56-0.63 (m, 4H).
13C NMR (100 MHz, CDCl3) δ: 152.32, 139.22, 130.49, 126.24, 121.72, 121.38, 55.71, 40.19, 34.00, 32.76, 29.10, 27.90, 23.61.
SPF 之合成
A mixture of 2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene (0.7 g, 1.08 mmol), bis(pinacolato)diboron (273 mg, 1.08 mmol), Pd2(dba)2 (20.0 mg, 0.022 mmol), tricyclohexyl phosphonium tetrafluoroborate(23.4 mg, 0.064 mmol), cesium fluoride (1.11 g, 7.3 mmol), and anhydrous toluene (36 mL) was bubbled with nitrogen for 15 minutes and stirred at 80 ℃ for 24 hours under nitrogen atmosphere. Tetra-n-butylammonium bromide (69.9 mg, 0.22 mmol) was then introduced. The reaction mixture was stirred for further 24 hours, cooled to room temperature, and evaporated in
acetone sequentially. The mixture was filtered with a nylon membrane to afford SPF as a yellow solid. (323 mg, 57%)
SPF1 之合成
A mixture of SPF (100 mg), trimethylamine (300 mg), and tetrahydrofuran (5.0 mL), was heated to 40 ℃ in a sealed Schlenk tube for 24 hours, cooled to room temperature, and evaporated under vacuum. The residue was washed with chloroform and dichloromethane sequentially. The insoluble fraction was evaporated under vacuum to furnish SPF1 (92.3 mg, 75%).
嘧啶(pyrimidine)配位基鈀催化劑之合成
A mixture of 2-amino-4,6-dihydroxypyrimidine (26 mg, 0.2 mmol) and 4 mL of 0.1 M NaOH was heated to 65 ˚Cwith stirring. To the mixture, palladium(II) acetate (22 mg, 0.1 mmol) was added and it was stirredat 65 ˚C for 30 minutes. The stir bar was then removed, and the solution was allowed to cool to room temperature. After cooling, the solution was removed to a 10 mL volumetric flask and diluted to 10 mL with water.
高分子一般聚合條件：
以 m-TPPTs 作為鈀金屬配位基
Under nitrogen atmosphere, a mixture of monomer (50 mg), pivalic acid, Cs2CO3, Pd(OAc)2, m-TPPTs, and deionized water (2.5 mL) was stirred at 80 °C for 72 hours, cooled to room temperature, filtrated, transferred into Spectrum standard RC dialysis membrane, and dialyzed (2 × 12 h). Removal of water furnished polymer.
以pyrimidine 作為鈀金屬配位基
Under nitrogen atmosphere, a mixture of monomer (50 mg), pivalic acid, Cs2CO3, Pd-pyrimidine solution, and deionized water (2.5 mL) was stirred at 80 °C for 72 hours, cooled to room temperature, filtrated, transferred into Spectrum standard RC dialysis membrane, and dialyzed (2 × 12 h). Removal of water furnished polymer.