| 研究生: |
黃邦瑜 Huang, Pang-Yu |
|---|---|
| 論文名稱: |
Naphthoquinone-Rhodamine based衍生物螢光感測分子之合成與靜電紡絲奈米纖維態製備並應用於鐵離子感測 Naphthoquinone-Rhodamine based Fluorescent Sensing Probe: Synthesis, Electrospinning NanoFibers Fabrication and Application in Fe3+ Detection |
| 指導教授: |
吳文中
Wu, Wen-Chung |
| 學位類別: |
碩士 Master |
| 系所名稱: |
工學院 - 化學工程學系 Department of Chemical Engineering |
| 論文出版年: | 2024 |
| 畢業學年度: | 112 |
| 語文別: | 中文 |
| 論文頁數: | 117 |
| 中文關鍵詞: | 螢光感測器 、鐵離子 、靜電紡絲奈米纖維 、跨鍵能量轉移 |
| 外文關鍵詞: | fluorescent sensor, iron ion, electrospun nanofibers, through-bond energy transfer |
| 相關次數: | 點閱:153 下載:0 |
| 分享至: |
| 查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報 |
本研究利用自由基聚合法(free radical polymerization)合成出三種含有不同單體比例之螢光高分子poly(NIPAAm-co-NMA-co-RN), PNNRN。
共聚高分子PNNRN分別由Naphthoquinone-Rhodamine based 螢光單體、親水性高分子NIPAAM、可交聯高分子NMA所組成 : NIPAAM鏈段使高分子具有收縮-膨潤的特性;經化學熱交聯後之NMA鏈段使高分子具有溶劑耐受性,不會回溶於溶劑;本研究設計的naphthoquinone-rhodamine based 螢光單體,對Fe3+具有感測性質,結構中的rhodamine 可與 Fe3+螯合而開環,產生rhodamine之吸收峰。能量可透過跨鍵能量轉移(through-bond energy transfer , TBET)的機制,由 naphthoquinone 轉移到rhodamine,產生螢光放射,可視作為一 off-on 之感測器。並透過靜電紡絲技術(electrospinning technique)將高分子加工成奈米纖維,做為固態螢光感測器應用於環境的感測。
螢光高分子PNNRN對Fe3+顯示出良好的選擇性,並在其餘金屬陽離子的干擾下具備優秀的競爭性。由job plot之結果推論PNNRN與Fe3+是以1:2的當量形成錯合物,螢光滴定曲線結果可觀察到高分子溶液態與纖維態在各自區間的感測上表現出高度線性,也具備低偵測極限,可達到1.21 µM,並由pH值測試證實PNNRN能應用於常見之酸鹼環境之中(pH 值6-10),且具備短時間感測 Fe3+之能力。雖然數據顯示高分子纖維態的感測性相較溶液態顯得略為遜色,然而高分子纖維態為固態介質,具有便於攜帶、操作簡單等優點,具有應用於固態螢光感測器之優秀潛力。
This study is to synthesize three types of fluorescent polymers, poly(NIPAAm-co-NMA-co-RN) (PNNRN) via free radical polymerization with varying monomer ratios. PNNRN is composed of a naphthoquinone-rhodamine based fluorescent monomer, hydrophilic NIPAAM, and cross-linkable NMA. The NIPAAM segments provide the polymer with shrink-swell properties, while the NMA segments, after chemical and thermal cross-linking, confer solvent resistance. The designed fluorescent monomer is sensitive to Fe3+. After chelation with Fe3+, cause the spirolactam ring in rhodamine unit to open and exhibit an absorption peak. Energy transfer from naphthoquinone to rhodamine results in fluorescence emission, functioning as an off-on sensor.
The polymer is processed into nanofibers via electrospinning for solid-state fluorescent sensor applications. PNNRN demonstrates high selectivity and competitiveness in detecting Fe3+ amidst other metal ions. Job plot results indicate to form chelation complex with 1:2 stoichiometry between PNNRN and Fe3+. Fluorescence titration curves show high sensitivity with Fe3+, and a low detection limit of 1.49 µM. The pH tests confirm its effectiveness in common acidic and basic environments (pH 6-10), with rapid Fe3+ sensing capability. Despite the solid-state sensor's slightly lower sensitivity compared to its solution state, it offers advantages such as portability and ease of use, highlighting its potential as a solid state fluorescent sensor.
1. Hu, L., et al., Spectral properties of 4-(4-hydroxy-1-naphthylazo) benzenesulfonic acid and its application for colorimetric determination of trace Fe 3+. RSC Advances, 2014. 4(37): p. 19370-19374.
2. Lee, Y., Systematic Exploration of Indolizine-Based Small Fluorescent Molecules: Synthesis, Analysis and Application. 2018: Springer.
3. Jain, A., C. Blum, and V. Subramaniam, Fluorescence lifetime spectroscopy and imaging of visible fluorescent proteins, in Advances in Biomedical Engineering. 2009, Elsevier. p. 147-176.
4. Skallberg, A., Photoemission and Characterization of Neutrophils and Nanoparticles: Energy Mapping and Elemental Composition with sub-µm Resolution. 2020, Linköping University Electronic Press.
5. Birch, D.J., Y. Chen, and O.J. Rolinski, Fluorescence. Photonics: Biomedical Photonics, Spectroscopy, and Microscopy, 2015: p. 1-58.
6. Bonardi, A.-H., et al., Organometallic vs organic photoredox catalysts for photocuring reactions in the visible region. Beilstein Journal of Organic Chemistry, 2018. 14(1): p. 3025-3046.
7. Nijegorodov, N. and W. Downey, The influence of planarity and rigidity on the absorption and fluorescence parameters and intersystem crossing rate constant in aromatic molecules. The Journal of Physical Chemistry, 1994. 98(22): p. 5639-5643.
8. Eftink, M.R., Fluorescence quenching: theory and applications, in Topics in fluorescence spectroscopy: principles. 2002, Springer. p. 53-126.
9. Lakowicz, J.R. and J.R. Lakowicz, Quenching of fluorescence. Principles of fluorescence spectroscopy, 1983: p. 257-301.
10. Rani, P., Chemosensor and its applications. IRJRR, 2015. 3: p. 1-10.
11. Coulet, P.R., What is a Biosensor? Biosensor principles and applications, 2019: p. 1-6.
12. Justino, C.I., T.A. Rocha-Santos, and A.C. Duarte, Review of analytical figures of merit of sensors and biosensors in clinical applications. TrAC Trends in Analytical Chemistry, 2010. 29(10): p. 1172-1183.
13. Guo, C., et al., Supramolecular fluorescent sensors: An historical overview and update. Coordination chemistry reviews, 2021. 427: p. 213560.
14. Magri, D.C., Logical sensing with fluorescent molecular logic gates based on photoinduced electron transfer. Coordination Chemistry Reviews, 2021. 426: p. 213598.
15. Liu, L.-m. and Z.-y. Yang, A rhodamine and chromone based “turn-on” fluorescent probe (RC1) for Zn (II) in aqueous solutions and its application. Journal of Photochemistry and Photobiology A: Chemistry, 2018. 364: p. 558-563.
16. Hao, M., et al., Molecular origins of photoinduced backward intramolecular charge transfer. The Journal of Physical Chemistry C, 2020. 124(31): p. 16820-16826.
17. Liu, M., et al., Fluorescent probes for the detection of magnesium ions (Mg 2+): from design to application. RSC advances, 2018. 8(23): p. 12573-12587.
18. Hoche, J., et al., The mechanism of excimer formation: an experimental and theoretical study on the pyrene dimer. Physical Chemistry Chemical Physics, 2017. 19(36): p. 25002-25015.
19. Vollbrecht, J., Excimers in organic electronics. New Journal of Chemistry, 2018. 42(14): p. 11249-11254.
20. Ma, L.-J., et al., A pyrene-containing Schiff base fluorescent ratiometric probe for the detection of Cu2+ in aqueous solutions and in cells. Journal of Photochemistry and Photobiology A: Chemistry, 2021. 408: p. 113086.
21. Cao, D., et al., Through bond energy transfer (TBET)-based fluorescent chemosensors. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 2020. 44: p. 100371.
22. Kumar, N., V. Bhalla, and M. Kumar, Resonance energy transfer-based fluorescent probes for Hg 2+, Cu 2+ and Fe 2+/Fe 3+ ions. Analyst, 2014. 139(3): p. 543-558.
23. Shrestha, D., et al., Understanding FRET as a research tool for cellular studies. International journal of molecular sciences, 2015. 16(4): p. 6718-6756.
24. Wen, D., et al., A novel FRET fluorescent probe based on BODIPY-rhodamine system for Hg2+ imaging in living cells. Journal of Molecular Structure, 2021. 1236: p. 130323.
25. Wang, C., et al., A fluorescence ratiometric chemosensor for Fe3+ based on TBET and its application in living cells. Talanta, 2014. 128: p. 69-74.
26. Qi, J., et al., Towards more accurate bioimaging of drug nanocarriers: turning aggregation-caused quenching into a useful tool. Advanced Drug Delivery Reviews, 2019. 143: p. 206-225.
27. Mei, J., et al., Aggregation‐induced emission: the whole is more brilliant than the parts. Advanced materials, 2014. 26(31): p. 5429-5479.
28. Beija, M., C.A. Afonso, and J.M. Martinho, Synthesis and applications of Rhodamine derivatives as fluorescent probes. Chemical Society Reviews, 2009. 38(8): p. 2410-2433.
29. Iyer, D.K., et al., A review on rhodamine probes for metal ion recognition with a future on artificial intelligence and machine learning. Coordination Chemistry Reviews, 2023. 495: p. 215371.
30. Berhanu, A.L., et al., A review of the applications of Schiff bases as optical chemical sensors. TrAC Trends in Analytical Chemistry, 2019. 116: p. 74-91.
31. Gupta, K.C. and A.K. Sutar, Catalytic activities of Schiff base transition metal complexes. Coordination Chemistry Reviews, 2008. 252(12-14): p. 1420-1450.
32. Dalia, S.A., et al., A short review on chemistry of schiff base metal complexes and their catalytic application. Int. J. Chem. Stud, 2018. 6(3): p. 2859-2867.
33. Liu, L.-m. and Z.-y. Yang, A new off-on fluorescent sensor for the detection of Al (III) based on a chromone-derived Schiff-base. Inorganica Chimica Acta, 2018. 469: p. 588-592.
34. Hosseini, M.-S., et al., Functional polymers: An introduction in the context of biomedical engineering, in Advanced Functional Polymers for Biomedical Applications. 2019, Elsevier. p. 1-20.
35. Ganesh, V.A., A. Baji, and S. Ramakrishna, Smart functional polymers–a new route towards creating a sustainable environment. RSC advances, 2014. 4(95): p. 53352-53364.
36. Schmaljohann, D., Thermo-and pH-responsive polymers in drug delivery. Advanced drug delivery reviews, 2006. 58(15): p. 1655-1670.
37. Nithin, K., et al., Polymer-based smart composites and/or nanocomposites for optical, optoelectronic, and energy applications: A brief introduction, in Polymer-Based Advanced Functional Composites for Optoelectronic and Energy Applications. 2021, Elsevier. p. 1-29.
38. Deng, Z., et al., Poly (N-Isopropylacrylamide) Based Electrically Conductive Hydrogels and Their Applications. Gels, 2022. 8(5): p. 280.
39. Doberenz, F., et al., Thermoresponsive polymers and their biomedical application in tissue engineering–a review. Journal of Materials Chemistry B, 2020. 8(4): p. 607-628.
40. Chuang, W.-J., W.-Y. Chiu, and H.-J. Tai, Temperature-dependent conductive composites: Poly (N-isopropylacrylamide-co-N-methylol acrylamide) and carbon black composite films. Journal of Materials Chemistry, 2012. 22(38): p. 20311-20318.
41. Xue, J., et al., Electrospinning and electrospun nanofibers: Methods, materials, and applications. Chemical reviews, 2019. 119(8): p. 5298-5415.
42. Subbiah, T., et al., Electrospinning of nanofibers. Journal of applied polymer science, 2005. 96(2): p. 557-569.
43. Sharma, G.K. and N.R. James, Electrospinning: the technique and applications, in Recent Developments in Nanofibers Research. 2022, IntechOpen.
44. Haider, A., S. Haider, and I.-K. Kang, A comprehensive review summarizing the effect of electrospinning parameters and potential applications of nanofibers in biomedical and biotechnology. Arabian Journal of Chemistry, 2018. 11(8): p. 1165-1188.
45. Veleirinho, B., M.F. Rei, and J. Lopes‐DA‐Silva, Solvent and concentration effects on the properties of electrospun poly (ethylene terephthalate) nanofiber mats. Journal of Polymer Science Part B: Polymer Physics, 2008. 46(5): p. 460-471.
46. Tong, H.-W. and M. Wang, Electrospinning of poly (hydroxybutyrate-co-hydroxyvalerate) fibrous scaffolds for tissue engineering applications: effects of electrospinning parameters and solution properties. Journal of Macromolecular Science, Part B, 2011. 50(8): p. 1535-1558.
47. Huan, S., et al., Effect of experimental parameters on morphological, mechanical and hydrophobic properties of electrospun polystyrene fibers. Materials, 2015. 8(5): p. 2718-2734.
48. Jacobs, V., R.D. Anandjiwala, and M. Maaza, The influence of electrospinning parameters on the structural morphology and diameter of electrospun nanofibers. Journal of applied polymer science, 2010. 115(5): p. 3130-3136.
49. Zargham, S., et al., The effect of flow rate on morphology and deposition area of electrospun nylon 6 nanofiber. Journal of Engineered Fibers and Fabrics, 2012. 7(4): p. 155892501200700414.
50. Yang, G.-Z., et al., Influence of working temperature on the formation of electrospun polymer nanofibers. Nanoscale research letters, 2017. 12: p. 1-10.
51. Casper, C.L., et al., Controlling surface morphology of electrospun polystyrene fibers: effect of humidity and molecular weight in the electrospinning process. Macromolecules, 2003. 37(2): p. 573-578.
52. Xu, L., et al., A highly selective and sensitive photoswitchable fluorescent probe for Hg2+ based on bisthienylethene–rhodamine 6G dyad and for live cells imaging. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2014. 128: p. 567-574.
53. Kumar, P.S., P.R. Lakshmi, and K.P. Elango, Cyanohydrin formation of quinone appended benzaldehyde as a tool for selective colorimetric detection of cyanide in aqueous solution in a wide pH range. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2019. 212: p. 160-166.
54. Kim, H.-S., et al., Through-bond energy transfer based dyad and triad shape fluorescence “OFF-ON-OFF” probes for Hg2+ ions and their application in live HeLa cells and Zebrafish. Sensors and Actuators B: Chemical, 2017. 240: p. 1272-1282.
55. Rudbari, H.A., et al., Synthesis, characterization, X-ray crystal structures and antibacterial activities of Schiff base ligands derived from allylamine and their vanadium (IV), cobalt (III), nickel (II), copper (II), zinc (II) and palladium (II) complexes. Journal of Molecular Structure, 2016. 1125: p. 113-120.