臺灣博碩士論文加值系統

本研究主要是探討金屬有機骨架吸附偶氮染料(甲基紅同分異構物與甲基橙)後的螢光強度變化。金屬有機骨架的放光特性，是藉由有機配位基到金屬的電荷轉移所產生的放光。金屬有機骨架吸附染料後，螢光強度會隨著染料濃度增加而減少。藉由分析Stern-Volmer方程式，動態猝滅常數KD以及螢光生命期τ的測量，瞭解染料猝滅金屬有機骨架螢光的能力。研究發現甲基紅異構物，因為取代基COO-立體障礙不同，造成甲基紅吸附在金屬有機骨架的吸附位向不同，所造成的猝滅能力也有所不同。而在不同激發波長研究，發現雖然270nm所激發的螢光較350nm弱，仍可以觀察到螢光隨染料濃度而有猝滅變化。最後為了驗證染料吸附在金屬有機骨架的吸附位向，我們並測量拉曼光譜，發現拉曼光譜的結論和螢光猝滅實驗的結果是一致的。而針對螢光光譜、紫外-可見光光譜、拉曼光譜、時間相關單一光子計數系統實驗數據結果的關聯性，我們將會有詳細的討論。

 

The main objective of this study is to investigate the adsorption of azo dyes (methyl red isomers and methyl orange) on metal-organic frameworks (MOFs) by measuring the variation of fluorescence intensity. Because of the adsorption of dyes by MOFs, the fluorescence intensity is decreased with increasing concentration of the dyes. The fluorescence measurement is further analyzed by using the Stern-Volmer equation. Dynamic quenching constant (KD) and the fluorescence lifetime (τ) are calculated in order to understand the dye fluorescence quenching ability of MOFs. The results revealed that the methyl red molecule, due to the steric hindrance of the carboxylate functional group at different position, has been adsorbed differently on MOFs, therefore the quenching capability is also different. In the excitation wavelength dependence study, though the fluorescence excitation using 270 nm is weaker compared with using 350 nm, we can still observe the fluorescence quenching of dye at 270 nm. Finally, Raman spectroscopy was also performed in order to verify the adsorption orientation of the dye adsorbed on MOFs. We have demonstrated that the results of Raman spectroscopy and fluorescence quenching are consistent. In addition to fluorescence spectroscopy, we have used the UV-visible spectroscopy, Raman spectroscopy, and time-correlated single photon counting system.The results &; discussion of these studies are included in this thesis.

目錄
摘要 I
Abstract II
謝誌 III
目錄 V
圖目錄 IX
表目錄 XVI
第一章、 緒論 1
1-1光譜學簡介 1
1-1-1歷史發展 1
1-1-2光譜學分類 2
1-2研究動機 4
1-3金屬有機骨架化合物及其發光特性 6
1-4有機染料的性質介紹 17
1-4-1 甲基橙性質 17
1-4-2甲基紅性質 18
第二章、原理介紹 20
2-1紫外-可見光吸收與螢光原理 20
2-1-1簡介 20
2-1-2原理 22
2-2螢光光譜 24
2-2-1簡介 24
2-2-2螢光光譜儀 25
2-2-3螢光分析的特點 26
2-2-4影響螢光的因素 27
2-2-5螢光猝滅的效應(quenching effect) 30
2-2-6 Stern-Volmer equation 32
2-3時間相關單一光子計數系統 35
2-4拉曼散射光譜 38
2-4-1簡介 38
2-4-2原理 39
2-4-3表面增強拉曼散射（Surface Enhanced Raman Scattering；SERS） 45
第三章、實驗方法 47
3-1實驗藥品 47
3-2實驗設備 49
3-3藥品配置 50
3-3-1偶氮染料的配置 50
3-3-2金屬有機骨架的合成和純化 52
3-4實驗步驟 55
3-4-1金屬有機骨架吸附染料的螢光光譜實驗 55
3-4-2 TCSPC實驗 58
第四章、結果與討論 59
4-1金屬有機骨架光譜分析 59
4-1-1紫外-可見光光譜分析 59
4-1-2螢光光譜分析 61
4-1-3甲基橙猝滅MOFs螢光之動態Stern-Volmer plot分析 90
4-1-4甲基紅猝滅MOFs螢光之動態Stern-Volmer plot分析 99
4-1-5非線性Stern-Volmer plot分析 118
4-1-6不同激發波長所得到的螢光光譜分析 124
4-2 MOFs加入染料之螢光衰退圖分析 127
4-3甲基紅異構物吸附在MOFs之SERS光譜圖 133
第五章、結論 136
參考文獻 139

 
圖目錄
圖1-1 一個多孔MOF結構中可能放光的途徑，金屬簇團(藍色八面體)連接有機配位基(黃色矩形)與孔洞中的客體分子(紅色圓圈) 8
圖 1-2 MIL-101(Cr)的結構圖 13
圖 1-3 MIL-101(Cr)孔洞的種類 13
圖 1-4 MIL-100的結構圖 14
圖 1-5 MIL-53(Al)的結構圖 14
圖 1-6 HKUST-1(Cu)的結構圖 15
圖 1-7 UiO-66的結構圖 15
圖 1-8 MIL-47(V)的結構圖 16
圖 1-9 ZIF-8的結構圖 16
圖 1-10 甲基橙結構圖 17
圖 1-11 鄰位-甲基紅的結構圖 18
圖 1-12 間位-甲基紅的結構圖 19
圖 1-13 對位-甲基紅的結構圖 19
圖2-1分子的電子能階圖 21
圖2-2 磷光螢光示意圖 23
圖2-3 碰撞猝滅的示意圖 30
圖2-4 靜態猝滅的示意圖 31
圖2-6 TCSPC的原理示意圖 36
圖2-7 時間解析光激螢光光譜量測系統裝置圖 37
圖2-8 分子的電磁輻射散射圖示，其中vo為入射光頻率 39
圖2-9 光入射分子產生誘導偶極矩 40
圖2-10 入射電場誘發分子極化並朝各方向放出散射光示意圖 41
圖2-11 雷利散射與拉曼散射能階示意圖 44
圖2-12 雷利散射與拉曼散射在光譜上頻率位置的關係 45
圖2-13一般拉曼散射與表面增強拉曼散射之示意圖 46
圖2-14表面電漿共振(surface plasma resonance，SPR)示意圖 46
圖4-1甲基橙與金屬有機骨架材料的UV-Vis光譜圖 60
圖4-2 H2BTC與金屬有機骨架材料的UV-Vis光譜圖 60
圖4-3 MIL-101(Cr)加入不同濃度MO的螢光光譜 63
圖4-4 MIL-101(Cr)加入不同濃度p-MR的螢光光譜 63
圖4-5 MIL-101(Cr)加入不同濃度m-MR的螢光光譜 64
圖4-6 MIL-101(Cr)加入不同濃度o-MR的螢光光譜 64
圖4-7 MIL-101(Cr)和BDC的螢光光譜 65
圖4-8 MOFs螢光的放光機制 65
圖4-9 MIL-100(Cr)加入不同濃度MO的螢光光譜 68
圖4-10 MIL-100(Cr)加入不同濃度p-MR的螢光光譜 68
圖4-11 MIL-100(Cr)加入不同濃度m-MR的螢光光譜 69
圖4-12 MIL-100(Cr)加入不同濃度o-MR的螢光光譜 69
圖4-13 MIL-100(Al)加入不同濃度MO的螢光光譜 70
圖4-14 MIL-100(Al)加入不同濃度p-MR的螢光光譜 70
圖4-15 MIL-100(Al)加入不同濃度m-MR的螢光光譜 71
圖4-16 MIL-100(Al)加入不同濃度o-MR的螢光光譜 71
圖4-17 MIL-100(Fe)加入不同濃度MO的螢光光譜 72
圖4-18 MIL-100(Fe)加入不同濃度p-MR的螢光光譜 72
圖4-19 MIL-100(Fe)加入不同濃度m-MR的螢光光譜 73
圖4-20 MIL-100(Fe)加入不同濃度o-MR的螢光光 73
圖4-21 MIL-53(Al)加入不同濃度MO的螢光光譜 76
圖4-22 MIL-53(Al)加入不同濃度p-MR的螢光光譜 76
圖4-23 MIL-53(Al)加入不同濃度m-MR的螢光光譜 77
圖4-24 MIL-53(Al)加入不同濃度o-MR的螢光光譜 77
圖4-25 MIL-47(V)加入不同濃度MO的螢光光譜 78
圖4-26 MIL-47(V)加入不同濃度p-MR的螢光光譜 78
圖4-27 MIL-47(V)加入不同濃度m-MR的螢光光譜 79
圖4-28 MIL-47(V)加入不同濃度o-MR的螢光光譜 79
圖4-29 UiO-66加入不同濃度MO的螢光光譜 82
圖4-30 UiO-66加入不同濃度p-MR的螢光光譜 82
圖4-31 UiO-66加入不同濃度m-MR的螢光光譜 83
圖4-32 UiO-66加入不同濃度o-MR的螢光光譜 83
圖4-33 HKUST-1加入不同濃度MO的螢光光譜 84
圖4-34 HKUST-1加入不同濃度p-MR的螢光光譜 84
圖4-35 HKUST-1加入不同濃度m-MR的螢光光譜 85
圖4-36 HKUST-1加入不同濃度o-MR的螢光光譜 85
圖4-37 ZIF-8加入不同濃度MO的螢光光譜 87
圖4-38 ZIF-8加入不同濃度p-MR的螢光光譜 87
圖4-39 ZIF-8加入不同濃度m-MR的螢光光譜 88
圖4-40 ZIF-8加入不同濃度o-MR的螢光光譜 88
圖4-41 MIL-100(Cr、Fe)、HKUST-1(Cu)和H2BTC 的螢光光譜 89
圖4-42 MIL-100(Al)和Me3-BTC 的螢光光譜 89
圖4-43 MIL-101(Cr)加入甲基橙的Stern-Volmer plot 93
圖4-44 MIL-100(Al)加入甲基橙的Stern-Volmer plot 93
圖4-45 MIL-100(Fe)加入甲基橙的Stern-Volmer plot 94
圖4-46 MIL-100(Cr)加入甲基橙的Stern-Volmer plot 94
圖4-47 HKUST-1加入甲基橙的Stern-Volmer plot 95
圖4-48 MIL-53(Al)加入甲基橙的Stern-Volmer plot 95
圖4-49 MIL-47(V)加入甲基橙的Stern-Volmer plot 96
圖4-50 UiO-66加入甲基橙的Stern-Volmer plot 96
圖4-51 ZIF-8加入甲基橙的Stern-Volmer plot 97
圖4-52 MIL-101(Cr)在三種甲基紅異構物之Stern-Volmer plot 105
圖4-53 MIL-100(Cr)在三種甲基紅異構物之Stern-Volmer plot 105
圖4-54 MIL-100(Fe)在三種甲基紅異構物之Stern-Volmer plot 106
圖4-55 MIL-100(Al)在三種甲基紅異構物之Stern-Volmer plot 106
圖4-56 MIL-47 (V)在三種甲基紅異構物之Stern-Volmer plot 107
圖4-57 UiO-66在三種甲基紅異構物之Stern-Volmer plot 107
圖4-58 HKUST-1在三種甲基紅異構物之Stern-Volmer plot 108
圖4-59 MIL-53(Al)在三種甲基紅異構物之Stern-Volmer plot 108
圖4-61 MIL-101(Cr)和MIL-100系列在m-MR的Stern-Volmer plot 110
圖4-62 MIL-101(Cr)和MIL-100系列在p-MR的Stern-Volmer plot 110
圖4-63 MIL-101(Cr)和MIL-100系列在o-MR的Stern-Volmer plot 111
圖4-64 對位-甲基紅吸附在MIL-53(Al)之立體位向示意圖 113
圖4-65 間位-甲基紅吸附在MIL-53(Al)之立體位向示意圖 114
圖4-66 鄰位-甲基紅吸附在MIL-53(Al)之立體位向示意圖 115
圖4-67 對位-甲基紅吸附在MIL-100(Al) 之立體位向示意圖 116
圖4-68 間位-甲基紅吸附在MIL-100(Al) 之立體位向示意圖 116
圖4-69 鄰位-甲基紅吸附在MIL-100(Al) 之立體位向示意圖 117
圖4-70 MIL-101(Cr)在四種不同染料之非線性Stern-Volmer plot 119
圖4-71 MIL-100(Cr)在四種不同染料之非線性Stern-Volmer plot 119
圖4-72MIL-100(Al)在四種不同染料之非線性Stern-Volmer plot 120
圖4-73 MIL-100(Fe)在四種不同染料之非線性Stern-Volmer plot 120
圖4-74 MIL-47(V)在四種不同染料之非線性Stern-Volmer plot 121
圖4-75 HKUST-1在四種不同染料之非線性Stern-Volmer plot 121
圖4-76 MIL-53(Al)在四種不同染料之非線性Stern-Volmer plot 122
圖4-77 UIO-66在四種不同染料之非線性Stern-Volmer plot 122
圖4-78 ZIF-8在四種不同染料之非線性Stern-Volmer plot 123
圖4-79 MIL-100(Al)在270nm和350nm波長的螢光光譜 125
圖4-80 C=O的π→π*(allowed)和n→π*(not allowed)的電子躍遷 125
圖4-81 MIL-100(Al)加入不同濃度m-MR的螢光光譜(270nm) 126
圖4-82 不同激發波長下MIL-100(Al)加入m-MR的Stern-Volmer圖 126
圖4-83 UiO-66的放光衰減曲線 129
圖4-84 UiO-66加入10-6M甲基橙的放光衰減曲線 129
圖4-85 UiO-66加入5×10-6M甲基橙的放光衰減曲線 130
圖4-86 UiO-66加入10-5M甲基橙的放光衰減曲線 130
圖4-87 UiO-66加入5×10-5M甲基橙的放光衰減曲線 131
圖4-88 UiO-66加入5不同濃度甲基橙的放光衰減曲線疊圖 131
圖4-89 對位-甲基紅吸附在MOFs的拉曼光譜圖(632.8nm) 134
圖4-90 間位-甲基紅吸附在MOFs的拉曼光譜圖(632.8nm) 134
圖4-91 鄰位-甲基紅吸附在MOFs的拉曼光譜圖(632.8nm) 135
表目錄
表 1- 1 MOFs 資料表 12
表3-1實驗藥品和溶劑 47
表3-2實驗所使用的MOFs 48
表3-3實驗所用的儀器 49
表4-1 MOFs加入甲基橙之螢光強度積分面積範圍 97
表4-2 MOFs螢光加入甲基橙用Stern-Volmer equation的fitting所得到之R2值和KD 98
表4-3 MOFs加入鄰位-甲基紅之螢光強度積分面積範圍 103
表4-4 MOFs加入間位-甲基紅之螢光強度積分面積範圍 103
表4-5 MOFs加入對位-甲基紅之螢光強度積分面積範圍 104
表4-6 對位-甲基紅為猝滅劑之Stern-Volmer plot之R2和KD值 112
表4-7 間位-甲基紅為猝滅劑之Stern-Volmer plot之R2和KD值 112
表4-8 鄰位-甲基紅為猝滅劑之Stern-Volmer plot之R2和KD值 112
表4-9 UiO-66加入不同濃度甲基橙用double exponential公式fitting所得到之參數與平均螢光生命期 132
表4-10 UiO-66加入不同濃度甲基橙用Stern-Volmer公式fitting所得到所得到之Ksv值和猝滅速率常數kq 132

1.I. Newton, “A New Theory about Light and Colors,” Philos. Trans. R. Soc, 80, 3075-3087 (1672).
2.D. A. Skoog, “ Principles of Instrumental Analysis”, fifth edition (1998).
3.Y. J. Kuan, S. B. Charnley, H. C. Huang, W.L. Tseng, Z. Kisiel,“
Interstellar glycine”, Astrophys. J. 593,848–867 (2003).
4.E. Haquea, J. E. Leea, I. T. Jangb, “Adsorptive removal of methyl orange from aqueous solution with metal-organic frameworks, porous chromium-benzenedicarboxylates”, Journal of Hazardous Materials,181,535-542 (2010).
5.F. Kielar, C. P. Montgomery, E. J. New, D. Parker, R. A. Poole, S. L. Richardson and P. A. Stenson,“A mechanistic study of the dynamic quenching of the excited state of europium(III) and terbium(III) macrocyclic complexes by charge- or electron transfer”, Org. Biomol. Chem., 5, 2975–2982 (2007).
6.C. A. Kent, D. L., Thomas, J. Meyer, and W. Lin,“Amplified
Luminescence Quenching of Phosphorescent Metal−Organic Frameworks”, J. Am. Chem. Soc.,134, 3991−3994 (2007).
7.N. B. Shustova, A. F. Cozzolino, S. Reineke, M. Baldo, and M.Dinca,“Selective Turn-On Ammonia Sensing Enabled by High-Temperature Fluorescence in Metal−Organic Frameworks with Open Metal Sites”, J. Am. Chem. Soc ,135, 13326−13329 (2013).
8.S. L. James,“Metal-organic frameworks”, Chem. Soc. Rev., 32, 276–288 (2003).
9.M. D. Allendorf, C. A. Bauer , R. K. Bhakta and R. J. T. Houk, “Luminescent metal–organic frameworks”, Chem. Soc. Rev., 38, 1330-1352 (2009).
10.G. Ferey, C. Mellot-Draznieks, C. Serre, F. Millange, J. Dutour, S. Surble, and I. Margiolaki, “A Chromium Terephthalate–Based Solid with Unusually Large Pore Volumes and Surface Area”, Science, 309, 2040-2042 (2005).
11.G. Ferey, C. Serre, C. Mellot-Draznieks, F. Millange, S. Surble, J. Dutour, and I. Margiolaki, “A Hybrid Solid with Giant Pores Prepared by a Combination of Targeted Chemistry, Simulation, and Powder Diffraction”, Angew. Chem. Int. Ed, 43, 6296-6301 (2004).
12.C. Volkringer, D. Popov, T. Loiseau, G. Ferey, M. Burghammer, C. Riekel, M. Haouas, and F. Taulelle, “Synthesis, Single-Crystal X-ray Microdiffraction,and NMR Characterizations of the Giant Pore Metal-Organic Framework Aluminum Trimesate MIL-100”, Chem. Matter, 21, 5695-5697 (2009).
13.C. Zlotea, R. Campesi, F. Cuevas, E. Leroy, P. Dibandjo, C. Volkringer, T. Loiseau, G. Ferey, and M. Latroche, “Pd Nanoparticles Embedded into a Metal-Organic Framework:Synthesis, Structural Characteristics, and Hydrogen Sorption Properties”, J. Am. Chem. Soc, 132, 2991-2997 (2010).
14.P. Horcajada, S. Surble, C. Serre, D.Y. Hong, Y.K. Seo, J.S. Chang, J.M. Greneche, I. Margiolakid, and G. Fereya, “Synthesis and catalytic properties of MIL-100(Fe), an iron(III) carboxylate with large pores”, Chem. Commun, 2820-2822 (2007).
15.T. Loiseau, C. Serre, C. Huguenard, G. Fink, F. Taulelle, M. Henry, T. Bataille, and G. Ferey, “A Rationale for the Large Breathing of the Porous Aluminum Terephthalate (MIL-53) Upon Hydration”, Chem. Eur. J, 10, 1373-1382 (2004).
16.Chui, S. S. Y, Lo, S. M. F,Charmant, J. P. H,Orpen, A. G, Williams, and I. D, “A hemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]n”, Science, 283, 1148-1150 (1999).
17.J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S. Bordiga, and K. P. Lillerud, “A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability”, J. Am. Chem. Soc, 130, 13850-13851 (2008).
18.K. Barthelet, J. Marrot, D. Riou, and G. Ferey, “A Breathing Hybrid Organic ± Inorganic Solid with Very Large Pores and High Magnetic Characteristics”, Angewandte Chemie International Edition, 41, 281-284 (2002).
19.S. Aguado , G. Bergeret , M. P. Titus , V. Moizan , C. N. Draghi , N.Bats and D. Farrusseng, “Guest-induced gate-opening of a zeolite imidazolate framework”, New J. Chem.,35, 546–550 (2011).
20.D. A. Skoog, F. J. Holler, T. A. Nieman, “Principles of Instrumental Analysis”, sixth edition,Saunders College (2007).
21.D. A. McQUarrie and J. D. Simon, “A Molecular Approach”, Physical Chemistry ,fifth edition (1997).
22.J. R.Albani, “Principles and Applications of Fluorescence Spectroscopy”, Blackwell Science, 91-93 (2007).
23.柯以侃，儀器分析，文京圖書有限公司，1996，155-173頁
24.J. R. Lakowicz , “Principles of Fluorescence Spectroscopy”, 3rd Edition, Springer Science+Business Media, New York (2006).
25.B. Pan , B. Xing, W. Liu , G. Xing , S. Tao, “Investigating interactions of phenanthrene with dissolved organic matter: Limitations of Stern–Volmer plot”, Chemosphere, 69 ,1555–1562 (2007).
26.D.V.O. O’Connor , Phillips, D., “Time-correlated Single Photon Counting”, Academic Press, London, (1984).
27.M. Wahl, H. J. Rahn, I. Gregor ,R. Erdmann ,J. Enderlein , “Dead-time optimized time-correlated photon counting instrument with synchronized, independent timing channels”, Review of Scientific Instruments, 78, 033106, (2007).
28.C. V. Raman, K. S.Krishnan, “A New Type of Secondary Radiation” ,Nature , 121, 501(1928).
29.C. V. Raman, Krishnan, “A Change of Wave-Length in Light Scattering”, Nature, 121, 619(1928).
30.M. G. Albrecht and J. A. Creighton, “Anomalously intense Raman spectra of pyridine at a silver electrode”, J.Am.Chem.Soc, 99, 5215-5217 (1977).
31.R. L. McCreery, “Raman Spectroscopy for chemical analysis”, New York: Wiley Interscience (2000).
32.R. L. McCreery, “Raman Spectroscopy for chemical analysis”, New York: Wiley Interscience (2000).
33.M. Fleischman, P. J. Hendra and A.J. McQuillan, “Raman Spectra of Pyridine Adsorbed at a Silver Electrode”, Physics Letters, 26, 163-166 (1974).
34.D. L. Jeanmaire and R. P. V. Duyne,“Surface ramanspectroelectrochemistry: Part I. Heterocyclic, aromatic, and aliphatic amines adsorbed on the anodized silver electrode”, J.Electroanal.Chem, 84, 1-20 (1977).
35.M. Moskovits, “Surface-enhanced spectroscopy”, Rev. Mod. Phys., 57, 783-829 (1985).
36.R. Aroca, “Surface-Enhanced Vibrational Spectroscopy”, Wiley (2006).
37.X. Lin, T. Huang, F. Huang, W. Wang and J. Shi, “Photocatalytic activity of a Bi-based oxychloride Bi4NbO8Cl”, J. Mater. Chem, 17, 2145-2150 (2007).
38.N. B. Shustova, B. D. McCarthy, and M. Dincă, “Turn-On Fluorescence in Tetraphenylethylene-Based Metal-Organic Frameworks: an Alternative to Aggregation-Induced Emission”, J. Am. Chem. Soc., 133, 20126–20129 (2011).
39.M. Schaefer, “PROPERTIES OF PARAMAGNETIC METALS IN MRI”, Vol. 4, No. 3, (1997).
40.M. Stephan , P. Mueller ,U. Zenneck ,H. Pritzkow ,W.Siebert ,R.N. Grimes, “Organotransition-Metal Metallacarboranes. Paramagnetic Iron-Cobalt and Dicobalt Triple-Decker Sandwich Complexes”, Inorg. Chem , 348 ,2508-2067 (1995).
41.S. Singh, N. Rama, M. S. Ramachandra Rao, “Influence of d-d transition bands on electrical resistivity in Ni doped polycrystalline ZnO”, Applied Physics Letters ,88, 222111 (2006).
42.M. Tong, D. Liu, Q. Yang, S. D. Vinot, G.Maurinb and C. Zhong, “Influence of framework metal ions on the dye capture behavior of MIL-100 (Fe, Cr) MOF type solids”, J. Mater. Chem. A, 1, 8534–8537 (2013).
43.J. Catalna and J. P.Catalan, “On the solvatochromism of the n→π*electronic transitions in ketones”, Phys. Chem. Chem. Phys.,13, 4072–4082 (2011)
44.C. Gota, S. Uchiyama, T. Yoshihara, S. Tobita, and
T.Ohwada,“Temperature-Dependent Fluorescence Lifetime of a Fluorescent Polymeric Thermometer,Poly(N-isopropylacrylamide), Labeled by Polarity and Hydrogen Bonding Sensitive 4-Sulfamoyl-7-aminobenzofurazan”, J. Phys. Chem. B, Vol. 112, No. 10 (2008).
45.K. Sokolov, G. Chumanov, and T. M. Cotton, “Enhancement of Molecular Fluorescence near the Surface of Colloidal Metal Films”,Anal. Chem, 70, 3898-3905 (1998).
46.P. Koczon, W. Lewandowski, and A. P. Mazurek, “Vibrational (FT-IR and FT-Raman) and NMR studies on selected metal (Ca,Mn,Zn) complexes with ortho-, meta-, and para-iodobenzoic acids”, Vib. Spectrosc, 20, 143-149 (1999).
47.J. S. Suh, and J. Kim, “Three distinct geometries of surface-adsorbed carboxylate groups”,J. Raman Spectrosc, 29, 143-148 (1998).