- 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 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: 35This material was obtained with a
- 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