臺灣博碩士論文加值系統

幾丁質因含有大量分子間和分子內氫鍵，形成高度有序晶體結構，導致不溶於
常見水性溶劑，目前已知可溶解幾丁質的溶劑有，有機溶劑(LiCl/DMAc)、離子液
體(ionic liquid solvent, ILs)、深共熔溶劑(deep eutectic solvents, DES)、氯化鈣/甲醇、
鹼性溶劑(NaOH/尿素、KOH/尿素)，則有些溶劑不適用，如：氯化鈣/甲醇具高黏
度、離子液體成本高及 LiCl/DMAc 溶解效率低且有毒性；近期 NaOH/尿素、KOH/
尿素受到關注。單寧酸為水溶性的多酚基團，為氫鍵提供者，利用單寧酸酚基與幾
丁質羥基形成氫鍵，促進幾丁質溶解。本研究探討幾丁質溶解於 NaOH/尿素(Na/U)、
KOH/尿素(K/U)、NaOH/單寧酸(Na/TA)、KOH/單寧酸(K/TA)中，進行冷凍解凍循
環三次，探討最適溶解條件、溶解性質及溶解度。結果顯示，將幾丁質進行冷凍解
凍三次，並在 23 ℃下於第三次解凍時間為 30 分鐘，即可達到溶解。2% α-chitin 溶
解於10Na/0.1TA、10K/0.1TA、10Na/4U、10K/4U溶解度分別為 98.81%、98.20%、
96.95%、96.25%。1% β-chitin 為 97.03%、96.46%、96.16%、83.81%；分別進行一
至三次溶解 β-幾丁質，10Na/0.1TA 第一次溶解度可達 90%以上為最佳溶劑。添
加單寧酸組別的溶劑，能夠使 α-幾丁質及 β-幾丁質溶液黏度、儲存模數及成膠溫度
皆比添加尿素組別還要來的低，推測單寧酸之酚基能夠與幾丁質的羥基行相互作用，
使已溶解之幾丁質分子鏈進行摺疊或捲曲於單寧酸上。幾丁質溶解於 10Na/4U、
10K/4U、10Na/0.1TA、10K/0.1TA 存放於 50 ℃下 5 天，隨著時間天數的增加幾丁
質典型特徵峰、結晶峰強度有降低的趨勢，而溶解在 10Na/0.1TA 溶劑時，去乙醯
度可由達 17%提升至 49%為最高。最後，添加單寧酸之鹼性溶劑的溶解度、溶解效
率皆比添加尿素組別溶劑來的高和快，並且使用量也可以大幅降低，因此認為添加
單寧酸之鹼性溶劑於未來應用上具有潛力。

Chitin contains a large number of intermolecular and intramolecular hydrogen
bonds, forming a highly ordered crystal structure, which causes it to be insoluble in
aqueous solvents. In the studies before, the known solvents that can dissolve chitin
include organic solvents (LiCl/DMAc) , ionic liquid solvents (ILs), deep eutectic
solvents (DES), calcium chloride/methanol, alkaline solvents (NaOH/urea, KOH/urea),
and some other solvents that are not suitable, such as : The high viscosity of calcium
chloride/methanol solvent system, the high cost of ionic liquid solvent and the low
dissolution efficiency and toxicity of LiCl/DMAc. Recently, NaOH/urea and KOH/urea
solvent system have received attention. Tannic acid is a water-soluble polyphenol ,
which is known a hydrogen bond donor. The phenolic group of tannic acid forms a
hydrogen bond with the hydroxyl group of chitin to promote the dissolution of chitin.
In this study, the dissolution of chitin in NaOH/urea (Na/U), KOH/urea (K/U),
NaOH/tannic acid (Na/TA), KOH/tannic acid (K/TA) was investigated by undergoing
three freeze-thaw cycles and discuss the optimum dissolution conditions, dissolution
properties and solubility. The results showed that the best dissolution efficiency was
performed with three freeze-thaw cycles and at third cycle thawing 30 min at 23 ℃.
The solubilities of 2% α-chitin dissolved in 10Na/0.1TA, 10K/0.1TA, 10Na/4U,
10K/4U are 98.81%, 98.20%, 96.95%, 96.25%, respectively; while dissolving 1% βchitin have solubilities of 97.03%, 96.46%, 96.16%, 83.81%, respectively. The highest
solubility of β-chitin was found in the first dissolving process, which is 90%. The
solvent with addition of tannic acid can decrease the viscosity, storage modulus and
gelation temperature of α-chitin and β-chitin solutions making it lower than the urea
group. It is speculated that the phenol group of tannic acid can interact with the hydroxyl group of chitin, causing the molecular chain of dissolved chitin folded or curled on tannic acid. Chitin was dissolved in 10Na/4U, 10K/4U, 10Na/0.1TA, 10K/0.1TA and
stored at 50 °C for 5 days. The intensity of the characteristic peaks and crystallization
peaks of chitin decrease with the increase of storage time. When chitin is dissolved in
10Na/0.1TA solvent, the degree of deacetylation is increased from 17% to 49%, which
is the highest. Lastly, the solubility and dissolution efficiency of the alkali solvent that is added with tannic acid are higher and faster than the solvent added with urea.
Therefore, the alkaline solvent added with tannic acid has a great potential in future
applications.

摘要 i
Abstract ii
目錄 iii
圖目錄 v
表目錄 vi
第一章、前言 1
2.1. 幾丁質 1
2.1.1. 幾丁質結構 1
2.1.2. 幾丁質製備 1
2.1.3. 幾丁質特性及應用 1
2.2. 幾丁質之溶解 1
2.2.1. NaOH/Urea系統 1
2.2.2. KOH/尿素溶劑系統 1
2.2.3. 離子溶劑溶劑系統 2
2.2.4. DES溶劑系統 2
2.2.5. 氯化鋰/二甲基乙醯胺 1
2.3. 溶解性質 1
2.3.1. NaOH/Urea 1
2.3.2. KOH/Urea 2
2.3.3 NaOH/TA 2
第三章、實驗架構 5
第四章、材料與儀器 6
4.1. 實驗材料 6
4.2. 藥品 6
4.3. 儀器設備 6
第五章、實驗方法 8
5.1. 原料前處理 8
5.2. α、β幾丁質的製備 8
5.3. 幾丁質溶解度 8
5.3.1. 對幾丁質溶解度的影響 8
5.4. 幾丁質溶解速度 9
5.5. 幾丁質流變性質分析 10
5.5.1. 剪切黏度 10
5.5.2. 掃描頻率 10
5.5.3. 成膠溫度 10
5.6. 幾丁質性質分析 10
5.6.1. 官能基及去乙醯化程度之測定 10
5.6.2. 結晶度測定 11
5.6.3. 分子量測定 11
5.7. 統計分析 12
第六章、結果與討論 13
6.1. 幾丁質基本特性分析 13
6.2. 溶解幾丁質最適條件及比較溶解度 13
6.3. 幾丁質溶解於不同溶劑之溶解速率 16
6.4. 幾丁質溶液之流變性質 16
6.4.1. 剪切速率 16
6.4.2. 剪切應變 17
6.4.3. 成膠溫度 18
6.5. 不同溶劑對α-幾丁質結晶性之影響 19
6.6. 不同溶劑對α-幾丁質官能基之影響 19
6.7. 不同溶劑對α-幾丁質去乙醯度之影響 20
第七章、結論 21
第八章、參考文獻 22
第九章、圖 26
第十章、表 47
第十一、附圖 57

黃伯宙，2021，幾丁質在氫氧化鈉/單寧酸水溶液系統中的性質，國立臺灣海洋大學食品科學系碩士論文，基隆，臺灣。
Adatoz, E. B., Hendessi, S., Ow-Yang, C. W., & Demirel, A. L. (2018). Restructuring of poly (2-ethyl-2-oxazoline)/tannic acid multilayers into fibers. Soft Matter, 14(19), 3849-3857.
Andrade Jr, R. G., Dalvi, L. T., Silva Jr, J. M. C., Lopes, G. K., Alonso, A., & Hermes-Lima, M. (2005). The antioxidant effect of tannic acid on the in vitro copper-mediated formation of free radicals. Archives of Biochemistry and Biophysics, 437(1), 1-9.
Barikani, M., Oliaei, E., Seddiqi, H., & Honarkar, H. (2014). Preparation and application of chitin and its derivatives: a review. Iranian Polymer Journal, 23(4), 307-326.
Baxter, A., Dillon, M., Taylor, K. A., & Roberts, G. A. (1992). Improved method for ir determination of the degree of N-acetylation of chitosan. International Journal of Biological Macromolecules, 14(3), 166-169.
Birolli, W. G., de Moura Delezuk, J. A., & Campana-Filho, S. P. (2016). Ultrasound-assisted conversion of alpha-chitin into chitosan. Applied Acoustics, 103, 239-242.
Bisht, M., Macário, I. P., Neves, M. C., Pereira, J. L., Pandey, S., Rogers, R. D., Coutinho J.A., & Ventura, S. P. (2021). Enhanced dissolution of chitin using acidic deep eutectic solvents: A sustainable and simple approach to extract chitin from crayfish shell wastes as alternative feedstocks. ACS Sustainable Chemistry & Engineering, 9(48), 16073-16081.
Bradić, B., Novak, U., & Likozar, B. (2020). Crustacean shell bio-refining to chitin by natural deep eutectic solvents. Green Processing and Synthesis, 9(1), 13-25.
Chang, F. S., Chin, H. Y., & Tsai, M. L. (2018). Preparation of chitin with puffing pretreatment. Research on Chemical Intermediates, 44(8), 4939-4955.
Delezuk, J. A. D. M., Pavinatto, A., & Campana-Filho, S. P. (2019). Influence of the process parameters on β-chitin and α-chitin extraction: probing about the grinding and particles size. Materials Today: Proceedings, 14, 722-732.
Deng, Y., Liang, B., Liang, X., Fan, S., Zhang, Y., Yin, Y., Hu, H., Huang, Z., & Qin, Y. (2021). Enhancing the solubility of α-chitin in NaOH/urea aqueous solution by synergistic pretreatment of mechanical activation and metal salt. Journal of Molecular Liquids, 339, 116756.
Duan, B., Huang, Y., Lu, A., & Zhang, L. (2018). Recent advances in chitin based materials constructed via physical methods. Progress in Polymer Science, 82, 1-33.
El Knidri, H., Belaabed, R., Addaou, A., Laajeb, A., & Lahsini, A. (2018). Extraction, chemical modification and characterization of chitin and chitosan. International Journal of Biological Macromolecules, 120, 1181-1189.
Erel-Unal, I., & Sukhishvili, S. A. (2008). Hydrogen-bonded multilayers of a neutral polymer and a polyphenol. Macromolecules, 41(11), 3962-3970.
Fael, H., & Demirel, A. L. (2020). Tannic acid as a co-former in co-amorphous systems: Enhancing their physical stability, solubility and dissolution behavior. International Journal of Pharmaceutics, 581, 119284.
Francisco, M., Van Den Bruinhorst, A., & Kroon, M. C. (2012). New natural and renewable low transition temperature mixtures (LTTMs): screening as solvents for lignocellulosic biomass processing. Green Chemistry, 14(8), 2153-2157.
Gong, P., Wang, J., Liu, B., Ru, G., & Feng, J. (2016). Dissolution of chitin in aqueous KOH. Cellulose, 23, 1705-1711.
Hsieh, Y. Y., Chin, H. Y., & Tsai, M. L. (2015). Enrichment desired quality chitosan fraction and advance yield by sequential static and static-dynamic supercritical CO2. Carbohydrate Polymers, 133, 313-319.
Hu, X., Du, Y., Tang, Y., Wang, Q., Feng, T., Yang, J., & Kennedy, J. F. (2007). Solubility and property of chitin in NaOH/urea aqueous solution. Carbohydrate Polymers, 70(4), 451-458.
Hu, X., Tang, Y., Wang, Q., Li, Y., Yang, J., Du, Y., & Kennedy, J. F. (2011). Rheological behaviour of chitin in NaOH/urea aqueous solution. Carbohydrate Polymers, 83(3), 1128-1133.
Huang, J., Zhong, Y., Lu, A., Zhang, L., & Cai, J. (2020a). Temperature and time-dependent self-assembly and gelation behavior of chitin in aqueous KOH/urea solution. Giant, 4, 100038.
Huang, J., Zhong, Y., Wei, P., & Cai, J. (2021). Rapid dissolution of β-chitin and hierarchical self-assembly of chitin chains in aqueous KOH/urea solution. Green Chemistry, 23(8), 3048-3060.
Huang, J., Zhong, Y., Zhang, L., & Cai, J. (2020b). Distinctive viewpoint on the rapid dissolution mechanism of α-chitin in aqueous potassium hydroxide–urea solution at low temperatures. Macromolecules, 53(13), 5588-5598.
Kaya, M., Mujtaba, M., Ehrlich, H., Salaberria, A. M., Baran, T., Amemiya, C. T., Galli, R., Alkyuz, L., Sargin, I & Labidi, J. (2017). On chemistry of γ-chitin. Carbohydrate Polymers, 176, 177-186.
Khong, T. T., Aachmann, F. L., & Vårum, K. M. (2012). Kinetics of de-N-acetylation of the chitin disaccharide in aqueous sodium hydroxide solution. Carbohydrate Research, 352, 82-87.
Kumirska, J., Czerwicka, M., Kaczyński, Z., Bychowska, A., Brzozowski, K., Thöming, J., & Stepnowski, P. (2010). Application of spectroscopic methods for structural analysis of chitin and chitosan. Marine Drugs, 8(5), 1567-1636.
Kurita, K. (1998). Chemistry and application of chitin and chitosan. Polymer Degradation and Stability, 59(1-3), 117-120.
Li, F., You, X., Li, Q., Qin, D., Wang, M., Yuan, S., Chen, X., & Bi, S. (2021). Homogeneous deacetylation and degradation of chitin in NaOH/urea dissolution system. International Journal of Biological Macromolecules, 189, 391-397.
Ma, Q., Gao, X., Bi, X., Han, Q., Tu, L., Yang, Y., Shen, Y., & Wang, M. (2020). Dissolution and deacetylation of chitin in ionic liquid tetrabutylammonium hydroxide and its cascade reaction in enzyme treatment for chitin recycling. Carbohydrate Polymers, 230, 115605.
Mine, S., Izawa, H., Kaneko, Y., & Kadokawa, J. I. (2009). Acetylation of α-chitin in ionic liquids. Carbohydrate Research, 344(16), 2263-2265.
Morgenstern, B., & Kammer, H. W. (1996). Solvation in cellulose-LiCl-DMAc solutions. Trends in Polymer Science, 3(4), 87-91.
Poirier, M., & Charlet, G. (2002). Chitin fractionation and characterization in N, N-dimethylacetamide/lithium chloride solvent system. Carbohydrate Polymers, 50(4), 363-370.
Qin, Y., Lu, X., Sun, N., & Rogers, R. D. (2010). Dissolution or extraction of crustacean shells using ionic liquids to obtain high molecular weight purified chitin and direct production of chitin films and fibers. Green Chemistry, 12(6), 968-971.
Rasweefali, M. K., Sabu, S., Azad, K. M., Rahman, M. R., Sunooj, K. V., Sasidharan, A., & Anoop, K. K. (2022). Influence of deproteinization and demineralization process sequences on the physicochemical and structural characteristics of chitin isolated from deep-sea mud shrimp (Solenocera hextii). Advances in Biomarker Sciences and Technology, 4, 12-27.
Rinaudo, M. (2006). Chitin and chitosan: Properties and applications. Progress in Polymer Science, 31(7), 603-632.
Sainz-Urruela, C., Vera-López, S., Díez-Pascual, A. M., & San Andrés, M. P. (2022). Fluorescence study of the influence of centrifugation on graphene oxide dispersions in water and in tannic acid. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 278, 121302.
Sharma, M., Mukesh, C., Mondal, D., & Prasad, K. (2013). Dissolution of α-chitin in deep eutectic solvents. Rsc Advances, 3(39), 18149-18155.
Suenaga, S., Totani, K., Nomura, Y., Yamashita, K., Shimada, I., Fukunaga, H., Takahashi, N., & Osada, M. (2017). Effect of acidity on the physicochemical properties of α-and β-chitin nanofibers. International Journal of Biological Macromolecules, 102, 358-366.
Termonia, Y. (1999). Polymer solubility in mixed solvents. Journal of Polymer Science Part B: Polymer Physics, 37(19), 2782-2787.
Wang, X., Zhou, P., Lv, X., & Liang, Y. (2021). Insight into the structure-function relationships of the solubility of chitin/chitosan in natural deep eutectic solvents. Materials Today Communications, 27, 102374.
Wu, Y., Sasaki, T., Irie, S., & Sakurai, K. (2008). A novel biomass-ionic liquid platform for the utilization of native chitin. Polymer, 49(9), 2321-2327.
Xie, H., Zhang, S., & Li, S. (2006). Chitin and chitosan dissolved in ionic liquids as reversible sorbents of CO2. Green Chemistry, 8(7), 630-633.
Xu, D., Huang, J., Zhao, D., Ding, B., Zhang, L., & Cai, J. (2016). High‐flexibility, high‐toughness double‐cross‐linked chitin hydrogels by sequential chemical and physical cross‐linkings. Advanced Materials, 28(28), 5844-5849.
Yuan, Y., Hong, S., Lian, H., Zhang, K., & Liimatainen, H. (2020). Comparison of acidic deep eutectic solvents in production of chitin nanocrystals. Carbohydrate Polymers, 236, 116095.
Zdanowicz, M., Wilpiszewska, K., & Spychaj, T. (2018). Deep eutectic solvents for polysaccharides processing. A review. Carbohydrate Polymers, 200, 361-380.
Zhang, W., Zhao, Y., Xu, L., Song, X., Yuan, X., Sun, J., & Zhang, J. (2020). Superfine grinding induced amorphization and increased solubility of α-chitin. Carbohydrate Polymers, 237, 116145.
Zhao, D., Huang, W. C., Guo, N., Zhang, S., Xue, C., & Mao, X. (2019). Two-step separation of chitin from shrimp shells using citric acid and deep eutectic solvents with the assistance of microwave. Polymers, 11(3), 409.
Zhong, Y., Cai, J., & Zhang, L. N. (2020). A review of chitin solvents and their dissolution mechanisms. Chinese Journal Polymer Science, 38, 1047-1060
Zhou, J., & Zhang, L. (2000). Solubility of cellulose in NaOH/urea aqueous solution. Polymer Journal, 32(10), 866-870.
Zhu, P., Gu, Z., Hong, S., & Lian, H. (2017). One-pot production of chitin with high purity from lobster shells using choline chloride–malonic acid deep eutectic solvent. Carbohydrate Polymers, 177, 217-223.