Jozef Hodyl PhD Thesis - Theses - Flinders University

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pK a = 2.97 pK a = 1.05Figure 3.15 Representation of the intramolecular hydrogen bonded structures of o-hydroxybenzoateand 2,6-dihydroxybenzoate.A second consequence is a weakening of the hydrogen bond acceptor capability ofthe carboxylate. For this reason the host-guest binding constants become appreciablylower in magnitude with o-hydroxybenzoate < m-hydroxybenzoate < p-hydroxybenzoate.It appears from this study that binding strength with these types of guests may bedependent on the solvent in which guest inclusion occurs. Previous studies withreceptor 29 were performed in 20% aqueous dioxane whereas this study withreceptor 49 utilised DMSO-d 6 or CD 3 OD as the solvent. Indications are that thehydrogen bond donor/acceptor abilities of the solvent have a significant bearing onthe magnitude of the binding constants obtained. Further investigations of this andthe turnaround in the present trend can be found in Chapter 6 where the silica boundhost is used under aqueous conditions.The data obtained from 1 H NMR monitored titration experiments with,[Cd(TracHP12)](ClO 4 ) 2 , 49, and a number of different anionic guest speciesdemonstrate the suitability of a three-walled cavity for guest inclusion. From theseresults it can also be said that removal of one of the aromatic groups does not affect,to a great degree, the behaviour and efficacy of the binding cavity. Binding constantsfor inclusion of some of the guest species were lower, but not significantly reduced68
such that they would indicate preclusion of molecular receptor precursor 46 and itsderivatives 47 and 48 from acting as reasonable host species upon immobilisation ona silica surface.69
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Silica Immobilised MetalIon Activat
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ABSTRACTImmobilisation of functiona
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DECLARATIONI certify that this thes
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EtOHGPDMSGPDMESGPSGPTSethanolglycid
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CHAPTER ONEINTRODUCTION
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The focus of this work was to prepa
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sequestering anions has proved to b
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ange of pH due to its high basicity
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nitrophenol or p-nitrophenolate wit
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It has been shown by NMR and crysta
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within the cavity of a p-tert-butyl
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60 in 0.5% DMSO-MeCN (v/v). 82 The
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synthesised bi- tri- and tetra - π
Page 29 and 30: adopt a trans-III conformation, whe
Page 31 and 32: amide oxygen atoms on the pendant a
Page 33 and 34: apparent there is, nonetheless, evi
Page 35 and 36: However, hetero-N-substitution on t
Page 37 and 38: Si-OH +- OH SiO - + H 2 OFor surfac
Page 39 and 40: 35This material was obtained with a
Page 41 and 42: OOSiOHOROR OSiOHOOOSiOSiOSiOSiOSiOS
Page 43 and 44: Tetraaza metal complexes immobilise
Page 45 and 46: CHAPTER TWOSYNTHESIS OF MACROCYCLIC
Page 47 and 48: In addition, successful immobilisat
Page 49 and 50: 3233Figure 2.3Reaction of 3-(glycid
Page 51 and 52: The methodology chosen was adapted
Page 53 and 54: agreed with literature values. 109R
Page 55 and 56: XS HO O H61, n = 262, n = 3n+ClOSO6
Page 57 and 58: anhydrous ethanol, Scheme 2.7. The
Page 59 and 60: 75Figure 2.5 Structure of (S)-(-)-p
Page 61 and 62: metal ion coordination the pendant
Page 63 and 64: CHAPTER THREEGUEST MOLECULE INCLUSI
Page 65 and 66: 3.1 where K A is the association, o
Page 67 and 68: 0.5cχG∆δ∆δGbaχ GFigure 3.1S
Page 69 and 70: χG∆δ∆δGFigure 3.4 Job's Plot
Page 71 and 72: The downfield movement of the guest
Page 73 and 74: arm framework. The relative magnitu
Page 75 and 76: This phenomenon correlates well wit
Page 77 and 78: non-classical hydrogen bonding is g
Page 79: The full set of logK values obtaine
Page 83 and 84: CHAPTER 4MODIFICATION OF THE SILICA
Page 85 and 86: Chemical modification of the silica
Page 87 and 88: GPTSGPDMESFigure 4.4Schematic depic
Page 89 and 90: GPS, 33, linker material with an ex
Page 91 and 92: free νOHτSiOHνSi-O-SiδH 2 Oasym
Page 93 and 94: 224, 225the surface silanol groups.
Page 95 and 96: esonances, the spectrum for Si-GPS-
Page 97 and 98: increase in surface coverage from t
Page 99 and 100: and, more so due to the larger size
Page 101 and 102: CHAPTER 5METAL ION UPTAKE STUDIES W
Page 103 and 104: Scheme 5.1 Metal(II) ion coordinati
Page 105 and 106: linker material, Si-GPS, 33; endcap
Page 107 and 108: [Cd(Trac)](ClO 4 ) 2 , 94, or Si-GP
Page 109 and 110: CHAPTER 6GUEST MOLECULE INCLUSION S
Page 111 and 112: and D-histidinate. Guest inclusion
Page 113 and 114: Table 6.2Percent inclusion data for
Page 115 and 116: contains two hydroxy groups in the
Page 117 and 118: methoxy group, as portrayed by the
Page 119 and 120: these guest molecules with receptor
Page 121 and 122: only about half of that taken up by
Page 123 and 124: Percent inclusion values for these
Page 125 and 126: Table 6.7Percent guest inclusion of
Page 127 and 128: 6.1.7 Guest inclusion studies with
Page 129 and 130: A1 3542Neutral GuestBAnionic GuestH
Page 131 and 132:
A1 46 7532 Anionic Guest8BCHostHost
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extent, meta-positioned hydroxy gro
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δ obs (ppm)6.2146.2136.2126.2116.2
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CHAPTER 7EXPERIMENTAL7.1 General Ex
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inding constants (logK values) and
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delay time of 4 s. 13 C CPMAS NMR s
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C, -CH 2 - CH 2 OSO 2 ); 68.11 (1 C
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A solution of 69 (2.00 g, 10.1 mmol
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Bn, meta); 127.79 (1 C, Bn, para);
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added in a single portion. The mixt
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dioxane): δ 158.67 (1 C, C=O); 135
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1-(benzyloxycarbonyl)-4,7,10-tris-(
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1,4,7-tris-((S)-2-hydroxy-3-phenoxy
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1,4,7-tris(S)-2-hydroxy-3-[4-((2-(2
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1,4,7-tris(S)-2-hydroxy-3-[4-(2-(2-
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1-(2-hydroxypropyl)-4,7,10-tris-((S
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7.11 Preparation of the silica mate
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To a suspension of 33 (1.48 g, 1.1
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gel-like suspension that was cooled
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Si-GPS-Tri-Trac, 4545The title comp
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APPENDIX ABINDING CONSTANT DETERMIN
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1.01000.880δ obs (ppm)0.60.4logK =
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APPENDIX BDETERMINATION OF STOICHIO
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0.5χG∆δGFigure B.2χ GSimulated
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13 C CPMAS NMR SPECTRA OF SOME HIGH
Page 181 and 182:
Si-GPS-[Cd(Trac)(2,5-diydroxybenzoa
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REFERENCES
Page 185 and 186:
15. D. Tzalis and Y. Tor, Tetrahedr
Page 187 and 188:
42. A. P. Davis and R. S.Wareham, A
Page 189 and 190:
69. R. J. Bergeron, M. A. Channing
Page 191 and 192:
93. C. B. Smith, A. K. W. Stephens,
Page 193 and 194:
118. D. D. Dischino, E. J. Delaney,
Page 195 and 196:
144. X. Huang, X. Chang, Q. He, Y.
Page 197 and 198:
169. J. M. Klunder, T. Onami and K.
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197. K. A. Connors, Binding Constan
Page 201 and 202:
221. J. Blumel, J. Am. Chem. Soc.,
Page 203:
247. W. Likussar and D. F. Botz, An
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Jozef Hodyl PhD Thesis - Theses - Flinders University

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