Jozef Hodyl PhD Thesis - Theses - Flinders University

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The logK values obtained for this study demonstrate that addition of water to thesystem does reverse the trend from p-hydroxybenzoate > m-hydroxybenzoate > o-hydroxybenzoate found in DMSO-d 6 to o-hydroxybenzoate > m-hydroxybenzoate >p-hydroxybenzoate. This is markedly apparent for 2,6-dihydroxybenzoate where thelogK value increases from 2.05 in DMSO-d 6 by ca. three orders of magnitude to 4.64in 20% aqueous acetonitrile. The logK values obtained correlate well with thoseobtained for receptor 29 by fluorescence monitored titration. 129Therefore, theordering of the percent guest uptakes measured in water with immobilised receptor94 is consistent with the findings for these types of receptors. The reversal of thetrend shows that regulation of the system is dependent on specific solvent effects, inthis case, most likely, the ability of water molecules to mediate hydrogen bondingbetween the guest hydroxy groups and the host aromatic rings. Examples of 1 H NMRmonitored titration curves obtained in this series of experiments are shown for m-hydroxybenzoate in Figure 6.10 and 2,6-dihydroxybenzoate in Figure 6.11.7.4207.4007.380δ obs ppm7.3607.3407.3207.3007.2800 1 2 3 4 5 6 7 8 9 10[H]/[G]Figure 6.10 Example of 1 H NMR monitored titration curve for m-hydroxybenzoate with[Cd(TracHP12)] 2+ , 49, in 20% D 2 O/CD 3 CN buffered at pH 7 with HEPES buffer,showing the downward arc due to the upfield perturbation in the chemical shift of the p-proton.119
δ obs (ppm)6.2146.2136.2126.2116.2106.2096.2086.2076.2066.2050 1 2 3 4 5 6 7 8 9 10[H]/[G]Figure 6.11 Example of 1 H NMR monitored titration curve for 2,6-dihydroxybenzoate with[Cd(TracHP12)] 2+ , 49, in 20% D 2 O/CD 3 CN buffered at pH 7 with HEPES buffer,showing the downward arc due to the upfield perturbation in the chemical shift of theH B protons.120
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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
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adopt a trans-III conformation, whe
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amide oxygen atoms on the pendant a
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apparent there is, nonetheless, evi
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However, hetero-N-substitution on t
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Si-OH +- OH SiO - + H 2 OFor surfac
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35This material was obtained with a
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OOSiOHOROR OSiOHOOOSiOSiOSiOSiOSiOS
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Tetraaza metal complexes immobilise
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CHAPTER TWOSYNTHESIS OF MACROCYCLIC
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In addition, successful immobilisat
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3233Figure 2.3Reaction of 3-(glycid
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The methodology chosen was adapted
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agreed with literature values. 109R
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XS HO O H61, n = 262, n = 3n+ClOSO6
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anhydrous ethanol, Scheme 2.7. The
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75Figure 2.5 Structure of (S)-(-)-p
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metal ion coordination the pendant
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CHAPTER THREEGUEST MOLECULE INCLUSI
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3.1 where K A is the association, o
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0.5cχG∆δ∆δGbaχ GFigure 3.1S
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χG∆δ∆δGFigure 3.4 Job's Plot
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The downfield movement of the guest
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arm framework. The relative magnitu
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This phenomenon correlates well wit
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non-classical hydrogen bonding is g
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The full set of logK values obtaine
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such that they would indicate precl
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
Page 133: extent, meta-positioned hydroxy gro
Page 137 and 138: CHAPTER 7EXPERIMENTAL7.1 General Ex
Page 139 and 140: inding constants (logK values) and
Page 141 and 142: delay time of 4 s. 13 C CPMAS NMR s
Page 143 and 144: C, -CH 2 - CH 2 OSO 2 ); 68.11 (1 C
Page 145 and 146: A solution of 69 (2.00 g, 10.1 mmol
Page 147 and 148: Bn, meta); 127.79 (1 C, Bn, para);
Page 149 and 150: added in a single portion. The mixt
Page 151 and 152: dioxane): δ 158.67 (1 C, C=O); 135
Page 153 and 154: 1-(benzyloxycarbonyl)-4,7,10-tris-(
Page 155 and 156: 1,4,7-tris-((S)-2-hydroxy-3-phenoxy
Page 157 and 158: 1,4,7-tris(S)-2-hydroxy-3-[4-((2-(2
Page 159 and 160: 1,4,7-tris(S)-2-hydroxy-3-[4-(2-(2-
Page 161 and 162: 1-(2-hydroxypropyl)-4,7,10-tris-((S
Page 163 and 164: 7.11 Preparation of the silica mate
Page 165 and 166: To a suspension of 33 (1.48 g, 1.1
Page 167 and 168: gel-like suspension that was cooled
Page 169 and 170: Si-GPS-Tri-Trac, 4545The title comp
Page 171 and 172: APPENDIX ABINDING CONSTANT DETERMIN
Page 173 and 174: 1.01000.880δ obs (ppm)0.60.4logK =
Page 175 and 176: APPENDIX BDETERMINATION OF STOICHIO
Page 177 and 178: 0.5χG∆δGFigure B.2χ GSimulated
Page 179 and 180: 13 C CPMAS NMR SPECTRA OF SOME HIGH
Page 181 and 182: Si-GPS-[Cd(Trac)(2,5-diydroxybenzoa
Page 183 and 184: REFERENCES
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15. D. Tzalis and Y. Tor, Tetrahedr
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42. A. P. Davis and R. S.Wareham, A
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69. R. J. Bergeron, M. A. Channing
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93. C. B. Smith, A. K. W. Stephens,
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118. D. D. Dischino, E. J. Delaney,
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144. X. Huang, X. Chang, Q. He, Y.
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169. J. M. Klunder, T. Onami and K.
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197. K. A. Connors, Binding Constan
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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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