Jozef Hodyl PhD Thesis - Theses - Flinders University

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environment to the hydrophobic interior of the CD, the binding strength is loweredaccordingly, compared to benzoic acid. 69 Moreover, studies with p-nitrobenzoateguests conducted by Davies and Savage revealed that guest species derived from p-nitrobenzoic acid bound more weakly than those from benzoic acid. They concludedthat the charged species bound as Bergeron et al. proposed, but that binding in bothcharged and uncharged species was also mediated by the electron withdrawing ordonating ability of the substituents. They ascertained that substituents with higherelectron withdrawing ability penetrated the cavity first. As the nitro group has higherelectron withdrawing ability than the carboxy moiety the carboxy group was likely toprotrude into the aqueous environment and hence the lower binding observed for p-nitrobenzoic acid derivatives. 711.3.2 CalixarenesThe calixarenes exhibit some similarity with cyclodextrins as both have recurringstructural subunits containing peripheral functional groups arranged around ahydrophobic core. 72 Since their discovery they have become the subject of manystudies as receptors due to the ease of modifying their backbones and their welldefinedupper and lower rims surrounding a central annulus, as shown for 8, a typical59, 73, 74calixarene.upper rimR 1R 1 R 1 R1annuluslower rimOOR 2 R 2 R 2 R 2OO810
It has been shown by NMR and crystallographic data that due to the flexibility ofthe methylene linkage between the phenolic moieties, calix[4]arenes, such as, 8, mayadopt four rotational conformers, namely: cone, where all the phenyl rings align inthe same direction to form a "basket-like" cavity; partial cone, where one of thephenyl rings aligns in a downward direction while the other three orient upwards;1,2-alternate, where two of the phenyl rings align downward and two upward in a cisarrangement; 1.3-alternate as previous, but with a trans arrangement, as shown inFigure 1.3.ConePartial Cone1,2-alternate1,3-alternateFigure 1.3The four possible conformers of calix[4]arenes.Of these four conformations the most common is the cone conformation. It canbe seen that in the cone conformation the calix[4]arene molecule forms ahydrophobic "basket-like" cavity that can be used for molecular recognition of guestmolecules, and hence as a receptor.11
Page 1 and 2: Silica Immobilised MetalIon Activat
Page 3 and 4: ABSTRACTImmobilisation of functiona
Page 5: DECLARATIONI certify that this thes
Page 8 and 9: EtOHGPDMSGPDMESGPSGPTSethanolglycid
Page 10: CHAPTER ONEINTRODUCTION
Page 13 and 14: The focus of this work was to prepa
Page 15 and 16: sequestering anions has proved to b
Page 17 and 18: ange of pH due to its high basicity
Page 19: nitrophenol or p-nitrophenolate wit
Page 23 and 24: within the cavity of a p-tert-butyl
Page 25 and 26: 60 in 0.5% DMSO-MeCN (v/v). 82 The
Page 27 and 28: 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
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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
Page 81 and 82:
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
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GPS, 33, linker material with an ex
Page 91 and 92:
free νOHτSiOHνSi-O-SiδH 2 Oasym
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224, 225the surface silanol groups.
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esonances, the spectrum for Si-GPS-
Page 97 and 98:
increase in surface coverage from t
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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
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CHAPTER 6GUEST MOLECULE INCLUSION S
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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
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
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Bn, meta); 127.79 (1 C, Bn, para);
Page 149 and 150:
added in a single portion. The mixt
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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
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To a suspension of 33 (1.48 g, 1.1
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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
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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
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.
Page 199 and 200:
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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