54. B. Dietrich, Pure Appl. Chem., 1993, 65, 1457-1464.55. J. Kielland, J. Am. Chem. Soc., 1937, 59, 1675-1678.56. C. H. Park and H. E. Simmons, J. Am. Chem. Soc., 1968, 90, 2431-2432.57. K. W. Piepgrass, J. H. Davis, M. Sabat and R. N. Grimes, J. Am. Chem.Soc., 1991, 113, 680-681.58. P. Schiessl and F. P. Schmidtchen, J. Org. Chem., 1994, 59, 509-511.59. A. Bianchi, K. Bowman-James and E. Garcia-Espana, eds.,Supramolecular Chemistry of Anions, Wiley VCH, New York, 1997.60. A. Villiers, Compt. Rend., 1891, 112, 536-538.61. J. Szejtli, Chem. Rev., 1998, 98, 1743-1753.62. L. F. Lindoy and I. M. Atkinson, Self-Assembly in SupramolecularSystems, Royal Society of Chemistry, Cambridge, 2000.63. D. T. Pham, P. Clements, C. J. Easton and S. F. Lincoln, Tetrahedron:Asymmetry, 2008, 19, 167-175.64. Y. L. Zhao, H. Y. Zhang, M. Wang, H. M. Yu, H. Yang and Y. Liu, J.Org. Chem., 2006, 71, 6010-6019.65. K. Kano, Takenoshita and T. Ogawa, Chem. Lett., 1982, 321-324.66. Y. Fu, L. Liu and Q. X. Guo, J. Inclusion Phenom. Mol. Recognit.Chem., 2002, 43, 223-229.67. Z. J. Tan, X. X. Zhu and G. R. Brown, Langmuir, 1994, 10, 1034-1039.68. R. J. Bergeron, M. A. Channing, G. J. Gibeily and D. M. Pillor, J. Am.Chem. Soc., 1977, 99, 5146-5151.168
69. R. J. Bergeron, M. A. Channing and K. A. McGovern, J. Am. Chem.Soc., 1978, 100, 2878-2883.70. A. Buvari-Barcza, E. Rak and A. Meszaros, J. Inclusion Phenom. Mol.Recognit. Chem., 1998, 32, 453-459.71. D. M. Davies and J. R. Savage, J. Chem. Soc., Perkin Trans. 2, 1994,1525-1529.72. J. Vicens and V. Bohmer, eds., Calixarenes: A Versatile Class ofMacrocyclic Compounds, Kluwer Academic Publishers, Dordrecht,1991.73. G. McMahon, S. O'Malley and K. Nolan, Arkivoc, 2003, vii, 23-31.74. C. D. Gutsche, Calixarenes, Royal Society of Chemistry, Cambridge,1989.75. H. Goldmann, W. Vogt, E. Paulus and V. Bohmer, J. Am. Chem. Soc.,1988, 110, 6811-6817.76. A. Ikeda and S. Shinkai, Chem. Rev., 1997, 97, 1713-1734.77. G. D. Andreetti, R. Ungaro and A. Pochini, J. Chem. Soc., Chem.Commun., 1979, 1005.78. S. G. Bott, A. W. Coleman and J. L. Atwood, J. Am. Chem. Soc., 1986,108, 1709-1710.79. F. Sansone, L. Baldini, A. Casnati, M. Lazzarotto, F. Ugozzoli and R.Ungaro, Proc. Natl. Acad. Sci. USA, 2002, 99, 4842-4847.80. K. Kavallieratos, C. M. Bertao and R. H. Crabtree, J. Org. Chem., 1999,64, 1675-1683.169
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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
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CHAPTER 4MODIFICATION OF THE SILICA
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Chemical modification of the silica
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GPTSGPDMESFigure 4.4Schematic depic
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GPS, 33, linker material with an ex
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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-
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increase in surface coverage from t
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and, more so due to the larger size
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CHAPTER 5METAL ION UPTAKE STUDIES W
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Scheme 5.1 Metal(II) ion coordinati
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linker material, Si-GPS, 33; endcap
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[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
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Table 6.2Percent inclusion data for
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contains two hydroxy groups in the
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methoxy group, as portrayed by the
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these guest molecules with receptor
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only about half of that taken up by
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Percent inclusion values for these
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Table 6.7Percent guest inclusion of
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6.1.7 Guest inclusion studies with
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A1 3542Neutral GuestBAnionic GuestH
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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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- 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-(
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- Page 163 and 164: 7.11 Preparation of the silica mate
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- 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
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- Page 175 and 176: APPENDIX BDETERMINATION OF STOICHIO
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- 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: 42. A. P. Davis and R. S.Wareham, A
- 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