Jozef Hodyl PhD Thesis - Theses - Flinders University

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hydrogen bonding mode of the host-guest complexes, and was a major discoveryarising from this work.iii
DECLARATIONI certify that this thesis does not incorporate, without acknowledgement, any materialpreviously submitted for any degree or diploma in any university; and that to the bestof my knowledge and belief it does not contain any material previously published orwritten by another person except where due reference is made in the text.signed...............................................................<strong>Jozef</strong> Andrew Zbigniew <strong>Hodyl</strong>iv
Page 1 and 2: Silica Immobilised MetalIon Activat
Page 3: ABSTRACTImmobilisation of functiona
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 and 20: nitrophenol or p-nitrophenolate wit
Page 21 and 22: It has been shown by NMR and crysta
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
Page 75 and 76:
This phenomenon correlates well wit
Page 77 and 78:
non-classical hydrogen bonding is g
Page 79 and 80:
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
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 and 134:
extent, meta-positioned hydroxy gro
Page 135 and 136:
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
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
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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