熱力學分析聚乙二醇在水合程序中結構變化

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姓名

洪世勳(Shih-hsun Hung) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

熱力學分析聚乙二醇在水合程序中結構變化
(Thermodynamic analysis on conformation change of polyethylene glycol during hydration process)

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摘要(中)

聚乙二醇（polyethylene glycol）是一種直鏈狀高分子，由於其分子本身不具有毒性，且具有抗蛋白質吸附的特性，因此聚乙二醇被廣泛應用於生物科技和醫學領域當中。而目前認為聚乙二醇能夠抗蛋白質吸附的主因，為聚乙二醇分子在溶液中所產所的立體排除（steric exclusion）效應，以及其良好的水合能力，使得聚乙二醇分子周圍形成類似保護膜的水籠結構，造成其它物質不易吸附於其上。
　　本研究利用恆溫滴定卡計（ITC）和modified segment-based NRTL model，探討聚乙二醇單體於水合程序的熱力學性質變化。結果顯示出聚乙二醇單體於水中傾向於聚集，且其水合過程為enthalpy driven的自發程序。而當分子量超過500時，聚乙二醇分子鏈段開始因償熵效應發生摺疊的現象。且隨著分子量的增加，聚乙二醇片段（segment）的親水性也因不同因素而遞減。
　　此外，我們也利用熱力學模式來估算聚乙二醇溶液的稀釋焓，對於聚乙二醇－水的雙成分系統而言，計算結果與實驗值的趨勢相符合，但準確度仍差了一個級數（order）以上，而對於聚乙二醇─鹽類─水三成分系統，則難以利用model預測其放熱量及趨勢。

摘要(英)

Polyethylene glycol (PEG) is linear and neutral polymer. The characteristic of low toxicity and preventing nonspecific adsorption of protein provides PEG extensive usage in biomaterials and biomedical application. The prevalent viewpoint to non-fouling phenomenon of PEG is due to the steric exclusion PEG produces in the solution as well as the hydrophilic chain of PEG. The hydration water structure around PEG molecule provides more energy barrier in the adsorption process of other solutes.
In this study, we probe into the change of thermodynamic properties during the hydration process of PEG by ITC and modified segment-based NRTL model. The result shows the monomers of PEG tend to aggregate in the solution in order to reduce the water accessible surface area. When the molecular weight is over 500 (g/mole), PEG starts to fold because of entropy compensation. Besides, the hydrophilic of PEG segment decreases with the increasing of molecule weight for different factors.
We also estimate the heat of dilution of PEG solution by modified segment-based NRTL model. For PEG-water binary system, although there is similar trend between predicted and experimental data, the accuracy is different by an order. For PEG-salt-water ternary system, we found it hard to predict the result by thermodynamic model.

關鍵字(中)

★ 水合程序
★ 恆溫滴定卡計
★ 聚乙二醇

關鍵字(英)

★ polyethylene glycol
★ ITC
★ hydration process

論文目次

中文摘要 Ⅰ
英文摘要 Ⅱ
目錄 Ⅲ
表目錄 Ⅴ
圖目錄 Ⅵ
符號說明 Ⅷ
第一章緒論 1
第二章理論與文獻回顧 2
2-1 聚乙二醇簡介 2
2-2 立體排除效應 4
2-3 親水表面 6
2-4 水合程序 7
2-5 理論推導 9
2-5-1 溶解程序 9
2-5-2 汽化程序 13
2-5-3 水合程序 16
2-6 聚乙二醇於水溶液中的活性（activity）計算 17
2-7 稀釋焓估算 19
第三章實驗部份 25
3-1 實驗藥品 25
3-2 實驗儀器設備 26
3-3 VP－ITC儀器介紹 27
3-4 VP-ITC操作步驟 28
3-5 以稀釋熱數據求χ值 30
第四章　結果與討論 32
4-1 χ值計算 34
4-2 溶解程序 36
4-3 汽化與水合程序 38
4-4 聚乙二醇於水中的結構變化 40
4-5 稀釋熱估算 46
4-5-1　聚乙二醇－水雙成分系統 46
4-5-2　聚乙二醇－鹽類－水三成分系統 48
4-6 鹽類對聚乙二醇水合能力之影響 50
第五章結論 65
第六章　參考文獻 67
附錄　 70

參考文獻

Abuchowski, A., van Es, T., Palczuk, N. C., Davis, F. F. 　“Alteration of immunological properties of bovine serum albumin by covalent attachment of polyethylene glycol”, Journal of Biological Chemistry, 252(1977), 3578-3581.
Alessi, M. L., Norman, A. I., Knowltion, S. E., Ho, D. L., Greer, S. C., “Helical and coil conformation of poly(ethylene glycol) in isobutyric acid and water”Macromolecules, 38(2005), 9333-9340.
Bhat, R., Timasheff, S. N., “Steric exclusion is the principal source of the preferential hydration of proteins in the presence of polyethylene glycols”, Protein Science, 1(1992), 1133-1143.
Feldman, K., Hahner, G., Spencer, N. D., Harder, P., Grunze, M., “Probing resistance to protein adsorption of
oligo(ethylene glycol)-terminated self-assembled
monolayers by scanning force microscopy”, Journal of the
American Chemical Society, 121(1999), 10134-10141.
Gregory, R. B., “Protein-Solvent interactions”, CRC Press, 1995.
Harder, P., Grunze, M., Dahint, R., Whitesides, G. M.,
Laibinis, P. E. “Molecular conformation in oligo(ethylene glycol)-terminated self- assembled monolayers on gold and silver surfaces determines their ability to resist protein
adsorption”, Journal of Physical Chemistry B, 102(1998),
426-436.
Lide, D. R., ”Standard thermodynamic properties of chemical substances”, CRC handbook of Chemistry and Physics, 1999.
Makhatadze, G. I., Privalov, P. L., “Contribution of hydration to protein folding thermodynamics I: The enthalpy of hydration”, Journal of Molecular Biology, 232(1993) 639-659.
Molyneux, P., “ Water soluble synthetic polymers : properties and behavior”, CRC Press, Boca Raton, FL , vol I(1983).
Plyasunov, A. V., Shock, E. L., “Thermodynamic functions of hydration of hydrocarbons at 298.15 K and 0.1 MPa” Geochimica et Cosmochimica Acta, 64(2000), 3, 439-468.
Prausnitz, J. M., Lichtenthaler, R. N., Azevedo, E. G.,
“Molecular thermodynamics of fluid-phase equilibria “, third edition, Pearson Education Taiwan Ltd., 2004.
Prime, K. L., Whitesides, G. M. “Self-assembled organic monolayers: model systems for studying adsorption of proteins at surfaces” Science, 252(1991), 1164-1167.
Sadeghi, R. “Amodified segment-based nonrandom two-liquid model for the calculation of vapor–liquid equilibrium of aqueous polymer–salt solutions” Chemical Engineering Science, 61(2006), 7786 – 7794.
Shulgin, I. L., Ruckenstein, E., “Preferential hydration and
solubility of proteins in aqueous solutions of polyethylene glycol”, Biophysical Chemistry, 120(2006), 188-198.
Tasaki, K. “Poly(oxyethylene)-water interactions: A Molecular Dynamics Study”, Journal of the American Chemical Society, 118(1996) 8459-8469.
Vermette, P., Meagher, L., “Interactions of phospholipid- and poly(ethylene glycol)-modified surfaces with biological systems: relation to physico-chemical properties and mechanisms”, Colloids and Surfaces B: Biointerfaces 28(2003) 153-198.
Wang, S. C., Wang, C. K., Chang, F. M., Tsao, H. K., “Second virial coefficient of poly(ethylene glycol) in aqueous solutions” Macromolecules, 35(2002), 9551-9555.
Wang, R. L. C., Kreuzer, H. J., Grunze, M. “ Molecular
conformation and solvation of oligo(ethyleneglycol) -terminated self-assembled monolayers and their resistance to protein adsorption”, Journal of Physical Chemistry B, 101(1997), 9767-9773.
Zheng, J. M., Chin, W. C., Khijniak E., “Surfaces and
interfacial water : evidence that hydrophilic surfaces have long-range impact, Advances in Colloid and Interface Science 127(2006), 19-27.
Zafarani-Moattar, M.T., Salabat, A., “Measurement and correlation of viscosities, densities and water activities for the system poly(propylene glycol) + MgSO4 + H2O at 25℃”. Journal of Solution Chemistry, 27(1998), 663–673.
林俊儀, “利用恆溫滴定卡計對高分子溶液之溶劑性質之研究”, 中央大學國立中央大學化學工程研究所碩士論文(2006)。
許朝翔, “利用恆溫滴定微卡計探討聚乙二醇抗蛋白質吸附之作用機制” 中央大學國立中央大學化學工程研究所碩士論文(2007)。

指導教授

李亮三、陳文逸
(Liang-Sun Lee、Wen-Yih Chen)

審核日期

2008-7-22

推文