本論文的研究目標，為利用常壓微電漿製備不同成分與功能的自癒合水凝膠。本論文可分為兩部分: 第一部分為製備銀負載自癒合水凝膠，第二部分為製備具導電性質的自癒合水凝膠。兩種類型的水凝膠都是藉由常壓微電漿掃描丙烯酸 (acrylic acid, AA) 前驅物與氯化鐵 (FeCl 3) 的混合物、藉由添加其他不同的成分而獲得。本論文製備自癒合水凝膠的主要機制，為利用常壓微電漿引起丙烯酸（AA）的聚合反應，並利用氯化鐵做為交聯劑，與聚丙烯酸的羧酸官能團（COO-）和氯化鐵的鐵離子 (Fe 3+) 進行物理交聯，製備自癒合水凝膠。
在添加不同的成份以製備銀負載以及具導電性質自癒合水凝膠之前，先利用水凝膠的機械強度計算自癒合效率，以得到最適化的丙烯酸和氯化鐵混合物的最佳濃度。最適化的結果顯示以 3.5 M丙烯酸與17.5 mM的氯化鐵混合，利用常壓微電漿掃描後的PAA-Fe自癒合水凝膠，可在37°C、12小時間後，顯示 ~68 %、最佳的自癒合效率。將銀顆粒 (Ag) 或明膠 (G)進一步摻入pAA-Fe水凝膠，分別形成pAA-Fe/Ag，pAA-G-Fe和pAA-G-Fe/Ag，SEM圖像顯示在pAA-Fe/Ag可觀察到聚集的氯化銀顆粒 (AgCl)，而在pAA-G-Fe/Ag中，由於明膠可有效穩定化氯化銀顆粒，因此觀察到均勻分佈的氯化銀顆粒。XRD分析結晶度證實在水凝膠中的顆粒為銀粒子。僅加入銀粒子的pAA-Fe和pAA-Fe/Ag水膠，在37 ℃下、12小時癒合的自愈效率為~67%，同時，含有銀的兩種水凝膠都對大腸桿菌具有抗菌性，抑制圈的直徑分別為0.92 cm與1.13 cm。另一方面，同時含有銀粒子與明膠的水凝膠，在37 ℃下、12小時癒合時，pAA-G-Fe和pAA-G-Fe/Ag的自癒合效率為~59 %，較低於不含明膠的水凝膠
本論文的第二部分目標為利用經由丙烯酸，氯化鐵和吡咯 (Py) 單體，利用常壓微電漿掃描製備導電自癒合水凝膠。實驗結果顯示，隨吡咯濃度從3.5 mM增加至7.5 mM，pAA-pPY-Fe水凝膠的自愈效率從60.5％下降到32.1 %，此結果與凝膠的含膠率結果一致。此外，利用碘摻雜探討摻雜對於水凝膠導電率的影響，結果顯示碘摻雜可同時提高水凝膠的導電性，以及對大腸桿菌具有較高的抗菌效果。最後，為了證明導電水凝膠的應用，將pAA-pPy7d-Fe與由3V電池供電的LED燈泡連接，形成一個簡單的電路，顯示水凝膠在自癒合過程後可以點亮LED燈泡，證實本研究製備的自癒合水凝膠具有可應用價值。

In this thesis, atmospheric pressure microplasma was employed to prepare self-healing hydrogels with different composition. This thesis is divided into two parts: (part 1): silver loaded self-healing hydrogels, and (part 2): conductive self-healing hydrogels. Both types of the hydrogels were mainly composed by acrylic acid (AA) and ferric chloride (FeCl3). The polymerization of acrylic acid (AA) was proposed to be initiated by the atmospheric pressure microplasma which is postulated to generate free-radicals to initiate radical plasma polymerization. Moreover, the physical cross-linking of hydrogels was facilitated through the carboxylic (COO-) functional groups of polyacrylic acid (pAA) with the added ferric ions (Fe3+) of FeCl3 which resulted in the self-healing hydrogels.
Prior to the syntheses of both types of hydrogels, the optimization of concentrations of AA and FeCl3 was facilitated. The pAA-Fe self-healing hydrogels with concentration of AA 3.5 M and FeCl3 17.5 mM exhibited the optimized self-healing efficiency ~68% for 12 h of healing at 37C.
In the first part, silver loaded self-healing hydrogels were prepared by mixing AA, FeCl3, silver nitrate (AgNO3), and gelatin (G). In this part, four types of hydrogels were synthesized, (1) pAA-Fe, (2) pAA-Fe/Ag, (3) pAA-Fe-G, and (4) pAA-Fe/Ag-G. SEM images revealed that agglomerated silver chloride nanoparticles (AgCl NPs) were observed in pAA-Fe/Ag, whereas in pAA-Fe/Ag-G, AgCl NPs distributed uniformly due to the stabilization of gelatin. The crystallinity of silver in hydrogels was confirmed by XRD analyses which exhibited five diffraction peaks referring to AgCl NPs (JCPDS 31-1238). Furthermore, the self-healing efficiency of gelatin containing hydrogels, pAA-Fe-G and pAA-Fe/Ag-G were found to be ~59%. The hydrogels contained no gelatin, pAA-Fe and pAA-Fe/Ag, revealed the self-healing efficiency of ~67% for 12 hours of healing at 37C. Moreover, the hydrogels containing silver, pAA-Fe/Ag and pAA-Fe/Ag-G, possessed antibacterial activity against E.coli with inhibition zone of 0.92 and 1.13 cm, respectively.
In the second part of this thesis, the conductive self-healing hydrogels composed of AA, FeCl3 and pyrrole monomers were prepared. By atmospheric pressure microplasma treatments, both AA and pyrrole were polymerized to form pAA and polypyrrole (pPy). Herein, the concentration of pyrrole was varied from 3.5 to 7.5 and 10.5 mM namely as pAA-pPy3.5-Fe, pAA-pPy7-Fe and pAA-pPy10.5-Fe, respectively. The decreasing gel fraction was obtained from to 87.5 to 54.5 % with increasing concentration of pyrrole due to pyrrole monomers consumed FeCl3 in the solution forming polypyrrole through oxidative polymerization. The self-healing efficiency of pAA-pPy-Fe hydrogels decreased from 60.5 to 32.1 % with increasing the concentration of pyrrole. This result showed good agreement with gel fraction in which the self-healing efficiency decreased at low gel fraction. Afterward, the effect of undoped and iodine (I2) doped hydrogels were also studied. In this regard, I2 doped hydrogels showed better performance both in antibacterial activity against E.coli bacteria and conductivity by four-point probe method compared to undoped hydrogels. Finally, as representative, pAA-pPy7d-Fe was chosen considering its self-healing efficiency and conductivity for the evaluation of electrical conductivity applications in a simple electrical circuit which was powered by 3 V batteries. Briefly, the initial hydrogel and after-healed hydrogel were able to conduct electricity indicated by lighting-up the LED in the electrical circuit.

References

[1] E. M. Ahmed, “Hydrogel: Preparation, characterization, and applications: A review,” J Adv Res, vol. 6, no. 2, pp. 105-21, Mar, 2015.
[2] Q. Chai, Y. Jiao, and X. Yu, “Hydrogels for Biomedical Applications: Their Characteristics and the Mechanisms behind Them,” Gels, vol. 3, no. 1, Jan 24, 2017.
[3] Y. H. Tsou, J. Khoneisser, P. C. Huang, and X. Xu, “Hydrogel as a bioactive material to regulate stem cell fate,” Bioact Mater, vol. 1, no. 1, pp. 39-55, Sep, 2016.
[4] Z. Wei, J. He, T. Liang, H. Oh, J. Athas, Z. Tong, C. Wang, and Z. Nie, “Autonomous self-healing of poly(acrylic acid) hydrogels induced by the migration of ferric ions,” Polymer Chemistry, vol. 4, no. 17, pp. 4601, 2013.
[5] W. Wang, R. Narain, and H. Zeng, “Rational Design of Self-Healing Tough Hydrogels: A Mini Review,” Front Chem, vol. 6, pp. 497, 2018.
[6] J. Li, and D. J. Mooney, “Designing hydrogels for controlled drug delivery,” Nat Rev Mater, vol. 1, no. 12, Dec, 2016.
[7] K. Y. Lee, and D. J. Mooney, “Hydrogels for Tissue Engineering,” Chemical Reviews, vol. 101, no. 7, pp. 1869-1880, 2001.
[8] L. Pan, G. Yu, D. Zhai, H. R. Lee, W. Zhao, N. Liu, H. Wang, B. C. Tee, Y. Shi, Y. Cui, and Z. Bao, “Hierarchical nanostructured conducting polymer hydrogel with high electrochemical activity,” Proc Natl Acad Sci U S A, vol. 109, no. 24, pp. 9287-92, Jun 12, 2012.
[9] D. Zhai, B. Liu, Y. Shi, L. Pan, Y. Wang, W. Li, R. Zhang, and G. Yu, “Highly sensitive glucose sensor based on pt nanoparticle/polyaniline hydrogel heterostructures,” ACS Nano, vol. 7, no. 4, pp. 3540-6, Apr 23, 2013.
[10] L. Li, Y. Wang, L. Pan, Y. Shi, W. Cheng, Y. Shi, and G. Yu, “A nanostructured conductive hydrogels-based biosensor platform for human metabolite detection,” Nano Lett, vol. 15, no. 2, pp. 1146-51, Feb 11, 2015.
[11] J. Tavakoli, and Y. Tang, “Hydrogel Based Sensors for Biomedical Applications: An Updated Review,” Polymers (Basel), vol. 9, no. 8, Aug 16, 2017.
[12] N. A. Peppas, P. Bures, W. Leobandung, and H. Ichikawa, “Hydrogels in Pharmaceutical Formulations,” European Journal of Pharmaceutics and Biopharmaceutics, vol. 50, 2000.
[13] J. P. Gong, and W. Hong, “Mechanics and Physics of Hydrogels,” Soft Matter, vol. 8, no. 31, pp. 8039-8049, Jan 1, 2012.
[14] A. K. Yetisen, N. Jiang, A. Fallahi, Y. Montelongo, G. U. Ruiz-Esparza, A. Tamayol, Y. S. Zhang, I. Mahmood, S. A. Yang, K. S. Kim, H. Butt, A. Khademhosseini, and S. H. Yun, “Glucose-Sensitive Hydrogel Optical Fibers Functionalized with Phenylboronic Acid,” Adv Mater, vol. 29, no. 15, Apr, 2017.
[15] B. Yang, Y. Zhang, X. Zhang, L. Tao, S. Li, and Y. Wei, “Facilely prepared inexpensive and biocompatible self-healing hydrogel: a new injectable cell therapy carrier,” Polymer Chemistry, vol. 3, no. 12, 2012.
[16] F. Ding, S. Wu, S. Wang, Y. Xiong, Y. Li, B. Li, H. Deng, Y. Du, L. Xiao, and X. Shi, “A dynamic and self-crosslinked polysaccharide hydrogel with autonomous self-healing ability,” Soft Matter, vol. 11, no. 20, pp. 3971-6, May 28, 2015.
[17] C. Shao, M. Wang, H. Chang, F. Xu, and J. Yang, “A Self-Healing Cellulose Nanocrystal-Poly(ethylene glycol) Nanocomposite Hydrogel via Diels–Alder Click Reaction,” ACS Sustainable Chemistry & Engineering, vol. 5, no. 7, pp. 6167-6174, 2017.
[18] R. Guo, Q. Su, J. Zhang, A. Dong, C. Lin, and J. Zhang, “Facile Access to Multisensitive and Self-Healing Hydrogels with Reversible and Dynamic Boronic Ester and Disulfide Linkages,” Biomacromolecules, vol. 18, no. 4, pp. 1356-1364, Apr 10, 2017.
[19] J. Liu, C. S. Y. Tan, Z. Yu, N. Li, C. Abell, and O. A. Scherman, “Tough Supramolecular Polymer Networks with Extreme Stretchability and Fast Room-Temperature Self-Healing,” Adv Mater, vol. 29, no. 22, Jun, 2017.
[20] Y. Li, J. Li, X. Zhao, Q. Yan, Y. Gao, J. Hao, J. Hu, and Y. Ju, “Triterpenoid-Based Self-Healing Supramolecular Polymer Hydrogels Formed by Host-Guest Interactions,” Chemistry, vol. 22, no. 51, pp. 18435-18441, Dec 19, 2016.
[21] C. Bilici, V. Can, U. Nöchel, M. Behl, A. Lendlein, and O. Okay, “Melt-Processable Shape-Memory Hydrogels with Self-Healing Ability of High Mechanical Strength,” Macromolecules, vol. 49, no. 19, pp. 7442-7449, 2016.
[22] Y. Liu, and S. H. Hsu, “Synthesis and Biomedical Applications of Self-healing Hydrogels,” Front Chem, vol. 6, pp. 449, 2018.
[23] M. Zhong, Y. T. Liu, X. Y. Liu, F. K. Shi, L. Q. Zhang, M. F. Zhu, and X. M. Xie, “Dually cross-linked single network poly(acrylic acid) hydrogels with superior mechanical properties and water absorbency,” Soft Matter, vol. 12, no. 24, pp. 5420-8, Jun 28, 2016.
[24] R. Faturechi, A. Karimi, A. Hashemi, H. Yousefi, and M. Navidbakhsh, “Influence of Poly(acrylic acid) on the Mechanical Properties of Composite Hydrogels,” Advances in Polymer Technology, vol. 34, no. 2, pp. n/a-n/a, 2015.
[25] F. S. Wei, "Principles of Polymer Design and Synthesis," B. Carpenter, P. Ceroni, B. Kirchner, A. Koskinen, K. Landfester, J. Leszczynski, T. Y. Luh, C. Mahlke, N. C. Polfer and R. Salzer, eds., Springer, 2013.
[26] H. R. Allcock, F. W. Lampe, and J. E. Mark, Contemporary Polymer Chemistry: Pearson/Prentice Hall Upper Saddle River, N. J., 2003.
[27] F. C. Leavitt, “Crosslinking of Cellulosics by High Energy Radiation,” Journal of Polymer Science, vol. 51, pp. 349-357, 1961.
[28] J. M. Tibbitt, R. Jensen, A. T. Bell, and M. Shen, “A Model for the Kinetics of Plasma Polymerization,” Macromolecules, vol. 10, no. 3, 1977.
[29] C. Hoffmann, C. Berganza, and J. Zhang, “Cold Atmospheric Plasma: Methods of Production and Application in Dentistry and Oncology,” Medical Gas Research, vol. 3, pp. 1-15, 2013.
[30] M. B. Kizling, and S. G. Jaras, “A Review of the Use of Plasma Techniques in Catalyst Preparation and Catalytic Reactions,” Applied Catalysis A: General, vol. 147, pp. 1-21, 1996.
[31] H. Yasuda, and Y. Matsuzawa, “Economical Advantages of Low-Pressure Plasma Polymerization Coating,” Plasma Processes and Polymers, vol. 2, no. 6, pp. 507-512, 2005.
[32] C. Richmonds, and R. M. Sankaran, “Plasma-liquid electrochemistry: Rapid synthesis of colloidal metal nanoparticles by microplasma reduction of aqueous cations,” Applied Physics Letters, vol. 93, no. 13, 2008.
[33] M. K. Satapathy, W. H. Chiang, E. Y. Chuang, C. H. Chen, J. L. Liao, and H. N. Huang, “Microplasma-assisted hydrogel fabrication: A novel method for gelatin-graphene oxide nano composite hydrogel synthesis for biomedical application,” PeerJ, vol. 5, pp. e3498, 2017.
[34] H. Wang, G. Zha, H. Du, L. Gao, X. Li, Z. Shen, and W. Zhu, “Facile fabrication of ultrathin antibacterial hydrogel films via layer-by-layer “click” chemistry,” Polym. Chem., vol. 5, no. 22, pp. 6489-6494, 2014.
[35] D. Gan, T. Xu, W. Xing, X. Ge, L. Fang, K. Wang, F. Ren, and X. Lu, “Mussel-Inspired Contact-Active Antibacterial Hydrogel with High Cell Affinity, Toughness, and Recoverability,” Advanced Functional Materials, vol. 29, no. 1, 2019.
[36] L. Chandana, P. Ghosal, T. Shashidhar, and C. Subrahmanyam, “Enhanced photocatalytic and antibacterial activity of plasma-reduced silver nanoparticles,” RSC Advances, vol. 8, no. 44, pp. 24827-24835, 2018.
[37] N. T.-P. Nguyen, L. V.-H. Nguyen, N. T. Thanh, V. V. Toi, T. Ngoc Quyen, P. A. Tran, H.-M. David Wang, and T.-H. Nguyen, “Stabilization of silver nanoparticles in chitosan and gelatin hydrogel and its applications,” Materials Letters, vol. 248, pp. 241-245, 2019.
[38] M. D. Bartlett, M. D. Dickey, and C. Majidi, “Self-healing materials for soft-matter machines and electronics,” NPG Asia Materials, vol. 11, no. 1, 2019.
[39] U. Gulyuz, and O. Okay, “Self-healing polyacrylic acid hydrogels,” Soft Matter, vol. 9, no. 43, 2013.
[40] R. P. Wool, “Self-healing materials: a review,” Soft Matter, vol. 4, no. 3, 2008.
[41] S. K. Ghosh, Self-Healing Materials: Fundamentals, Design Strategies, and Applications, Weinheim: Wiley-VCH, 2009.
[42] D. L. Taylor, and M. In Het Panhuis, “Self-Healing Hydrogels,” Adv Mater, vol. 28, no. 41, pp. 9060-9093, Nov, 2016.
[43] S. R. White, N. R. Sottos, P. H. Geubelle, J. S. Moore, M. R. Kessler, S. R. Sriram, E. N. Brown, and S. Viswanathan, “Autonomic Healing of Polymer Composites,” Nature, vol. 409, pp. 794-897, 2001.
[44] W. Zou, J. Dong, Y. Luo, Q. Zhao, and T. Xie, “Dynamic Covalent Polymer Networks: from Old Chemistry to Modern Day Innovations,” Advanced Materials, vol. 29, no. 14, 2017.
[45] S. Lu, C. Gao, X. Xu, X. Bai, H. Duan, N. Gao, C. Feng, Y. Xiong, and M. Liu, “Injectable and Self-Healing Carbohydrate-Based Hydrogel for Cell Encapsulation,” ACS Appl Mater Interfaces, vol. 7, no. 23, pp. 13029-37, Jun 17, 2015.
[46] Y. Zhang, L. Tao, S. Li, and Y. Wei, “Synthesis of multiresponsive and dynamic chitosan-based hydrogels for controlled release of bioactive molecules,” Biomacromolecules, vol. 12, no. 8, pp. 2894-901, Aug 8, 2011.
[47] V. Yesilyurt, M. J. Webber, E. A. Appel, C. Godwin, R. Langer, and D. G. Anderson, “Injectable Self-Healing Glucose-Responsive Hydrogels with pH-Regulated Mechanical Properties,” Adv Mater, vol. 28, no. 1, pp. 86-91, Jan 6, 2016.
[48] M. Krogsgaard, A. Andersen, and H. Birkedal, “Gels and threads: mussel-inspired one-pot route to advanced responsive materials,” Chem Commun (Camb), vol. 50, no. 87, pp. 13278-81, Nov 11, 2014.
[49] Q. Li, D. G. Barrett, P. B. Messersmith, and N. Holten-Andersen, “Controlling Hydrogel Mechanics via Bio-Inspired Polymer-Nanoparticle Bond Dynamics,” ACS Nano, vol. 10, no. 1, pp. 1317-24, Jan 26, 2016.
[50] G. A. Barcan, X. Zhang, and R. M. Waymouth, “Structurally dynamic hydrogels derived from 1,2-dithiolanes,” J Am Chem Soc, vol. 137, no. 17, pp. 5650-3, May 6, 2015.
[51] X. Zhang, and R. M. Waymouth, “1,2-Dithiolane-Derived Dynamic, Covalent Materials: Cooperative Self-Assembly and Reversible Cross-Linking,” J Am Chem Soc, vol. 139, no. 10, pp. 3822-3833, Mar 15, 2017.
[52] Y.-L. Liu, and T.-W. Chuo, “Self-healing polymers based on thermally reversible Diels–Alder chemistry,” Polymer Chemistry, vol. 4, no. 7, 2013.
[53] S. L. Banerjee, and N. K. Singha, “A new class of dual responsive self-healable hydrogels based on a core crosslinked ionic block copolymer micelle prepared via RAFT polymerization and Diels-Alder "click" chemistry,” Soft Matter, vol. 13, no. 47, pp. 9024-9035, Dec 6, 2017.
[54] M. H. Ghanian, H. Mirzadeh, and H. Baharvand, “In Situ Forming, Cytocompatible, and Self-Recoverable Tough Hydrogels Based on Dual Ionic and Click Cross-Linked Alginate,” Biomacromolecules, vol. 19, no. 5, pp. 1646-1662, May 14, 2018.
[55] S. Li, L. Wang, X. Yu, C. Wang, and Z. Wang, “Synthesis and characterization of a novel double cross-linked hydrogel based on Diels-Alder click reaction and coordination bonding,” Mater Sci Eng C Mater Biol Appl, vol. 82, pp. 299-309, Jan 1, 2018.
[56] S. Li, J. Yi, X. Yu, H. Shi, J. Zhu, and L. Wang, “Preparation and Characterization of Acid Resistant Double Cross-Linked Hydrogel for Potential Biomedical Applications,” ACS Biomaterials Science & Engineering, vol. 4, no. 3, pp. 872-883, 2018.
[57] X. Ye, X. Li, Y. Shen, G. Chang, J. Yang, and Z. Gu, “Self-healing pH-sensitive cytosine- and guanosine-modified hyaluronic acid hydrogels via hydrogen bonding,” Polymer, vol. 108, pp. 348-360, 2017.
[58] G. Xu, Y. Xiao, L. Cheng, R. Zhou, H. Xu, Y. Chai, and M. Lang, “Synthesis and rheological investigation of self-healable deferoxamine grafted alginate hydrogel,” Journal of Polymer Science Part B: Polymer Physics, vol. 55, no. 11, pp. 856-865, 2017.
[59] M. Shin, and H. Lee, “Gallol-Rich Hyaluronic Acid Hydrogels: Shear-Thinning, Protein Accumulation against Concentration Gradients, and Degradation-Resistant Properties,” Chemistry of Materials, vol. 29, no. 19, pp. 8211-8220, 2017.
[60] D. C. Tuncaboylu, M. Sari, W. Oppermann, and O. Okay, “Tough and Self-Healing Hydrogels Formed via Hydrophobic Interactions,” Macromolecules, vol. 44, no. 12, pp. 4997-5005, 2011.
[61] C. B. Rodell, A. L. Kaminski, and J. A. Burdick, “Rational Design of Network Properties in Guest–Host Assembled and Shear-Thinning Hyaluronic Acid Hydrogels,” Biomacromolecules, vol. 14, no. 11, pp. 4125-4134, 2013.
[62] W. H. Carothers, “Polymerization,” Chemical Reviews, vol. 8, no. 3, pp. 353-426, 1931.
[63] K. Ostrikov, and A. B. Murphy, “Plasma-aided nanofabrication: where is the cutting edge?,” Journal of Physics D: Applied Physics, vol. 40, no. 8, pp. 2223-2241, 2007.
[64] H. Conrads, and M. Schmidt, “Plasma Generation and Plasma Sources,” Plasma Sources Science and Technology, vol. 9, pp. 441-454, 2000.
[65] C. Tendero, C. Tixier, P. Tristant, J. Desmaison, and P. Leprince, “Atmospheric pressure plasmas: A review,” Spectrochimica Acta Part B: Atomic Spectroscopy, vol. 61, no. 1, pp. 2-30, 2006.
[66] C. De Bie, J. van Dijk, and A. Bogaerts, “CO2 Hydrogenation in a Dielectric Barrier Discharge Plasma Revealed,” The Journal of Physical Chemistry C, vol. 120, no. 44, pp. 25210-25224, 2016.
[67] S. Heijkers, R. Snoeckx, T. Kozák, T. Silva, T. Godfroid, N. Britun, R. Snyders, and A. Bogaerts, “CO2 Conversion in a Microwave Plasma Reactor in the Presence of N2: Elucidating the Role of Vibrational Levels,” The Journal of Physical Chemistry C, vol. 119, no. 23, pp. 12815-12828, 2015.
[68] V. Demidiouk, S. I. Moon, J. O. Chae, and D. Y. Lee, “Application of a Plasma-Catalytic System for Decomposition of Volatile Organic Compounds,” Journal of Korean Physical Society, vol. 42, 2003.
[69] H. Schulter, and A. Shivarova, Advanced Technologies Based on Wave and Beam Generated Plasmas, Sozopol, Bulgaria: Springer Science, 1998.
[70] M. Ishaq, M. M. Evans, and K. K. Ostrikov, “Effect of atmospheric gas plasmas on cancer cell signaling,” Int J Cancer, vol. 134, no. 7, pp. 1517-28, Apr 1, 2014.
[71] W. Lu, T. Cao, Q. Wang, and Y. Cheng, “Plasma-Assisted Synthesis of Chlorinated Polyvinyl Chloride (CPVC) Using a Gas-Solid Contacting Process,” Plasma Processes and Polymers, pp. n/a-n/a, 2011.
[72] B. Haertel, T. von Woedtke, K. D. Weltmann, and U. Lindequist, “Non-thermal atmospheric-pressure plasma possible application in wound healing,” Biomol Ther (Seoul), vol. 22, no. 6, pp. 477-90, Nov, 2014.
[73] M. I. Boulos, P. Fauchais, and E. Pfender, Thermal Plasmas: Fundamental and Applications, New York: Plenum Press, 1994.
[74] I. Gerber, I. Mihaila, D. Hein, A. Nastuta, R. Jijie, V. Pohoata, and I. Topala, “Time Behaviour of Helium Atmospheric Pressure Plasma Jet Electrical and Optical Parameters,” Applied Sciences, vol. 7, no. 8, 2017.
[75] O. V. Penkov, M. Khadem, W.-S. Lim, and D.-E. Kim, “A review of recent applications of atmospheric pressure plasma jets for materials processing,” Journal of Coatings Technology and Research, vol. 12, no. 2, pp. 225-235, 2015.
[76] H. Tanaka, and M. Hori, “Medical Applications of Non-Thermal Atmospheric Pressure Plasma,” Reviews of Modern Plasma Physics, vol. 1, no. 1, pp. 3, 2016.
[77] M. Goldman, and R. S. Sigmond, “Corona and Insulation,” IEEE Transactions on Plasma Science, vol. 17, no. 2, pp. 90-105, 1982.
[78] B. Eliasson, and U. Kogelschatz, “Nonequilibrium Volume Plasma Chemical Processing,” IEEE Transactions on Plasma Science, vol. 19, no. 6, pp. 1077, 1991.
[79] J. Y. Jeong, S. E. Babayan, V. J. Tu, J. Park, and I. Henins, “Etching Materials with an Atmospheric-Pressure Plasma Jet,” Plasma Sources Science and Technology, vol. 7, pp. 282-285, 1998.
[80] N. Herskowitz, “Role of Plasma-Aided Manufacturing in Semiconductor Fabrication,” IEEE Transactions on Plasma Science, vol. 26, no. 6, pp. 1610-1619, 1998.
[81] A. Schutze, J. Y. Jeong, S. E. Babayan, P. Jaeyoung, G. S. Selwyn, and R. F. Hicks, “The Atmospheric-Pressure Plasma Jet: a Review and Comparison to Other Plasma Sources,” IEEE Transactions on Plasma Science, vol. 26, no. 6, pp. 1685-1694, 1998.
[82] M. D. Calzada, M. Moisan, A. Gamero, and A. Sola, “Experimental investigation and characterization of the departure from local thermodynamic equilibrium along a surface‐wave‐sustained discharge at atmospheric pressure,” Journal of Applied Physics, vol. 80, no. 1, pp. 46-55, 1996.
[83] Y. Akishev, M. Grushin, V. Karalnik, I. Kochetov, A. Napartovich, and N. Trushkin, “Generation of atmospheric pressure non-thermal plasma by diffusive and constricted discharges in air and nitrogen at the rest and flow,” Journal of Physics: Conference Series, vol. 257, 2010.
[84] T. Belmonte, G. Henrion, and T. Gries, “Nonequilibrium Atmospheric Plasma Deposition,” Journal of Thermal Spray Technology, vol. 20, no. 4, pp. 744-759, 2011.
[85] I. Langmuir, “Oscillations in Ionized Gas,” Proceedings of the National Academy of Sciences, vol. 14, no. 8, pp. 627-637, 1928.
[86] K. H. Schoenbach, and K. Becker, “20 years of microplasma research: a status report,” The European Physical Journal D, vol. 70, no. 2, 2016.
[87] S. J. Park, and J. G. Eden, “13–30 micron diameter microdischarge devices: Atomic ion and molecular emission at above atmospheric pressures,” Applied Physics Letters, vol. 81, no. 22, pp. 4127-4129, 2002.
[88] R. Foest, M. Schmidt, and K. Becker, “Microplasmas, an emerging field of low-temperature plasma science and technology,” International Journal of Mass Spectrometry, vol. 248, no. 3, pp. 87-102, 2006.
[89] C. Penache, M. Miclea, A. B. Demian, O. Hohn, S. Schossler, T. Jahnke, K. Niemax, and H. S. Bocking, “Characterization of a High-Pressure Microdischarge using Diode Laser Atomic Absorption Spectroscopy,” Plasma Sources Science and Technology, vol. 11, pp. 476-483, 2002.
[90] L. Lin, and Q. Wang, “Microplasma: A New Generation of Technology for Functional Nanomaterial Synthesis,” Plasma Chemistry and Plasma Processing, vol. 35, no. 6, pp. 925-962, 2015.
[91] D. Mariotti, and K. Ostrikov, “Tailoring microplasma nanofabrication: from nanostructures to nanoarchitectures,” Journal of Physics D: Applied Physics, vol. 42, no. 9, 2009.
[92] S. Chauhan, “Acrylic Acid and Methacrylic Acid Based Hydrogels,” Der Chemica Sinica, vol. 6, no. 1, pp. 61-72, 2015.
[93] G. C. Ritthidej, "Nasal Delivery of Peptides and Proteins with Chitosan and Related Mucoadhesive Polymers," Peptide and Protein Delivery, pp. 47-68, 2011.
[94] R. Beerthuis, G. Rothenberg, and N. R. Shiju, “Catalytic routes towards acrylic acid, adipic acid and ε-caprolactam starting from biorenewables,” Green Chemistry, vol. 17, no. 3, pp. 1341-1361, 2015.
[95] J. W. Nicholson, “Polyacid-modified composite resins ("compomers") and their use in clinical dentistry,” Dent Mater, vol. 23, no. 5, pp. 615-22, May, 2007.
[96] S. Rey-Vinolas, E. Engel, and M. A. Mateos-Timoneda, "Polymers for bone repair," Bone Repair Biomaterials, pp. 179-197, 2019.
[97] S. Sun, L. B. Mao, Z. Lei, S. H. Yu, and H. Colfen, “Hydrogels from Amorphous Calcium Carbonate and Polyacrylic Acid: Bio-Inspired Materials for "Mineral Plastics",” Angew Chem Int Ed Engl, vol. 55, no. 39, pp. 11765-9, Sep 19, 2016.
[98] S. Anjum, P. M. Gurave, and B. Gupta, “Calcium ion-induced self-healing pattern of chemically crosslinked poly(acrylic acid) hydrogels,” Polymer International, vol. 67, no. 3, pp. 250-257, 2018.
[99] Y. Nakagawa, Y. Amano, S. Nakasako, S. Ohta, and T. Ito, “Biocompatible Star Block Copolymer Hydrogel Cross-linked with Calcium Ions,” ACS Biomaterials Science & Engineering, vol. 1, no. 10, pp. 914-918, 2015.
[100] H. Yokoi, E. Nomoto, and S. Ikoma, “Reversible Formation of Iron (III) Ion Clusters in the Poly(acrylic acid)-Fe3+ Complex Gel with Changes in the Water Content,” Journal of Materials Chemistry, vol. 3, no. 4, pp. 389-392, 1993.
[101] A. Roy, O. Bulut, S. Some, A. K. Mandal, and M. D. Yilmaz, “Green synthesis of silver nanoparticles: biomolecule-nanoparticle organizations targeting antimicrobial activity,” RSC Advances, vol. 9, no. 5, pp. 2673-2702, 2019.
[102] V. L. Colvin, M. C. Schlamp, and A. P. Alllvisatos, “Light-Emitting Diodes Made from Cadmium Selenide Nanocrystals and a Semiconducting Polymer,” Nature, vol. 370, pp. 354-357, 1994.
[103] A. Husen, and K. S. Siddiqi, “Phytosynthesis of Nanoparticles: Concept, Controversy and Application,” Nanoscale Research Letters, vol. 9, no. 229, pp. 1-24, 2014.
[104] L. Wei, J. Lu, H. Xu, A. Patel, Z. S. Chen, and G. Chen, “Silver nanoparticles: synthesis, properties, and therapeutic applications,” Drug Discov Today, vol. 20, no. 5, pp. 595-601, May, 2015.
[105] K. S. Siddiqi, A. Husen, and R. A. K. Rao, “A review on biosynthesis of silver nanoparticles and their biocidal properties,” J Nanobiotechnology, vol. 16, no. 1, pp. 14, Feb 16, 2018.
[106] S. Iravani, H. Korbekandi, S. V. Mirmohammadi, and B. Zolfaghari, “Synthesis of Silver Nanoparticles: Chemical, Physical and Biological Methods,” Research in Pharmaceutical Sciences, vol. 9, no. 6, pp. 385-406, 2014.
[107] F. E. Kruis, K. Nielsch, H. Fissan, B. Rellinghaus, and E. F. Wassermann, “Preparation of size-classified PbS nanoparticles in the gas phase,” Applied Physics Letters, vol. 73, no. 4, pp. 547-549, 1998.
[108] R. Wang, S. Zuo, W. Zhu, S. Wu, W. Nian, J. Zhang, and J. Fang, “Microplasma-Assisted Growth of Colloidal Silver Nanoparticles for Enhanced Antibacterial Activity,” Plasma Processes and Polymers, vol. 11, no. 1, pp. 44-51, 2014.
[109] A. A. Mariod, and H. F. Adam, “Review: Gelatin, Source, Extraction and Industrial Applications,” Acta Sci. Pol. , vol. 12, no. 2, pp. 135-147, 2013.
[110] A. J. Bailey, and R. G. Paul, “Collagen-a Not So Simple Protein,” J. Soc. Leather Techn. Chem., vol. 82, no. 3, pp. 104-110, 1998.
[111] M. D. Fernandez, P. Montero, and M. C. Gomez, “Gel Properties of Collagens from Skins of Cod (Gadus morhua) and Hake (Merluccius Merluccius) and Their Modification by The Coenhancers Magnesium Sulphate, Glycerol, and Transglutaminase,” Food Chem., vol. 74, pp. 161-167, 2001.
[112] N. A. Morrison, R. C. Clark, Y. L. Chen, T. Talashek, and G. Sworn, “Gelatin Alternatives for the Food Industry,” Progr. Colloid Polym. Sci., vol. 114, pp. 127-131, 1999.
[113] L. M. Kasankala, Y. Xue, Y. Weilong, S. D. Hong, and Q. He, “Optimization of gelatine extraction from grass carp (Catenopharyngodon idella) fish skin by response surface methodology,” Bioresour Technol, vol. 98, no. 17, pp. 3338-43, Dec, 2007.
[114] M. C. Gomez, and P. Montero, “Extraction of Gelatin from Megrim (Lepidorhombus Boscii) Skins with Several Organic Acids,” Food Chemistry and Toxicology, vol. 66, no. 2, pp. 213-216, 2001.
[115] M. Gudmunsson, and H. Hafsteinsson, “Gelatin from Cod Skins as Affected by Chemical treatments,” J. Food Sci., vol. 62 no. 1, pp. 37-39, 1997.
[116] R. A. Ofori, “Preparation of Gelatin from Fish Skin by an Enzyme Aided Process,” McGill Univ, Montreal, Canada, 1999.
[117] A. G. Macdiarmid, “Secondary Doping: a New Concept in Conducting Polymers,” Macromol. Symp., vol. 98, pp. 835-842, 1995.
[118] A. Proń, Z. Kucharski, C. Budrowski, M. Zagórska, S. Krichene, J. Suwalski, G. Dehe, and S. Lefrant, “Mössbauer spectroscopy studies of selected conducting polypyrroles,” The Journal of Chemical Physics, vol. 83, no. 11, pp. 5923-5927, 1985.
[119] E. T. Kang, H. C. Ti, and K. G. Neoh, “XPS Studies of Some Chemically Synthesized Polypyrrole-Organic Acceptor Complexes,” Polymer Journal, vol. 20, no. 10, pp. 845-850, 1988.
[120] A. F. diaz, and K. K. Kanazawa, “Electrochemical Polymerization of Pyrrole,” J. C. S. Chem. Comm., pp. 635-636, 19779.
[121] V. Vernitskaya, and O. N. Efimov, “Polypyrrole: a Conduction Polymer; its Synthesis, Properties and Applications,” Russian Chemical Reviews, vol. 66, pp. 443-457, 1997.
[122] A. F. Diaz, E. M. Genies, and G. Bidan, “Spectroelectrochemical Study of Polypyrrole Films,” J. Electroanal. Chem., vol. 149, pp. 101-113, 1983.
[123] B. Paosawatyanyong, K. Tapaneeyakorn, and W. Bhanthumnavin, “AC plasma polymerization of pyrrole,” Surface and Coatings Technology, vol. 204, no. 18-19, pp. 3069-3072, 2010.
[124] K. Liu, L. Chen, L. Huang, Y. Ni, Z. Xu, S. Lin, and H. Wang, “A facile preparation strategy for conductive and magnetic agarose hydrogels with reversible restorability composed of nanofibrillated cellulose, polypyrrole, and Fe3O4,” Cellulose, vol. 25, no. 8, pp. 4565-4575, 2018.
[125] P. S. Gils, D. Ray, and P. K. Sahoo, “Designing of silver nanoparticles in gum arabic based semi-IPN hydrogel,” Int J Biol Macromol, vol. 46, no. 2, pp. 237-44, Mar 1, 2010.
[126] R. Tian, X. Qiu, P. Yuan, K. Lei, L. Wang, Y. Bai, S. Liu, and X. Chen, “Fabrication of Self-Healing Hydrogels with On-Demand Antimicrobial Activity and Sustained Biomolecule Release for Infected Skin Regeneration,” ACS Appl Mater Interfaces, vol. 10, no. 20, pp. 17018-17027, May 23, 2018.
[127] Y. Murali Mohan, K. Vimala, V. Thomas, K. Varaprasad, B. Sreedhar, S. K. Bajpai, and K. Mohana Raju, “Controlling of silver nanoparticles structure by hydrogel networks,” J Colloid Interface Sci, vol. 342, no. 1, pp. 73-82, Feb 1, 2010.
[128] P. S. Murthy, Y. Murali Mohan, K. Varaprasad, B. Sreedhar, and K. Mohana Raju, “First successful design of semi-IPN hydrogel-silver nanocomposites: a facile approach for antibacterial application,” J Colloid Interface Sci, vol. 318, no. 2, pp. 217-24, Feb 15, 2008.
[129] P. M. Visakh, and Y. Long, Starch-based Blends, Composites and Nanocomposites, p.^pp. 248, London: Royal Society of Chemistry, 2015.
[130] R. Dash, M. Foston, and A. J. Ragauskas, “Improving the mechanical and thermal properties of gelatin hydrogels cross-linked by cellulose nanowhiskers,” Carbohydr Polym, vol. 91, no. 2, pp. 638-45, Jan 16, 2013.
[131] D. Ashok Kumar, V. Palanichamy, and S. M. Roopan, “Photocatalytic action of AgCl nanoparticles and its antibacterial activity,” J Photochem Photobiol B, vol. 138, pp. 302-6, Sep 5, 2014.
[132] L. E. Valencia Castro, C. J. Pérez Martínez, T. del Castillo Castro, M. M. Castillo Ortega, and J. C. Encinas, “Chemical polymerization of pyrrole in the presence ofl-serine orl-glutamic acid: Electrically controlled amoxicillin release from composite hydrogel,” Journal of Applied Polymer Science, vol. 132, no. 15, pp. n/a-n/a, 2015.
[133] Y. Lu, W. He, T. Cao, H. Guo, Y. Zhang, Q. Li, Z. Shao, Y. Cui, and X. Zhang, “Elastic, conductive, polymeric hydrogels and sponges,” Sci Rep, vol. 4, pp. 5792, Jul 23, 2014.
[134] A. Varesano, C. Vineis, A. Aluigi, F. Rombaldoni, C. Tonetti, and G. Mazzuchetti, “Antibacterial efficacy of polypyrrole in textile applications,” Fibers and Polymers, vol. 14, no. 1, pp. 36-42, 2013.
[135] W. Zhou, L. Lu, D. Chen, Z. Wang, J. Zhai, R. Wang, G. Tan, J. Mao, P. Yu, and C. Ning, “Construction of high surface potential polypyrrole nanorods with enhanced antibacterial properties,” Journal of Materials Chemistry B, vol. 6, no. 19, pp. 3128-3135, 2018.