Jozef Hodyl PhD Thesis - Theses - Flinders University

More documents

Recommendations

Info

co-workers in their investigations relating to neutral oxygen donors as regulators ofselectivity for Pb(II) ions. 100 Kimura et al. 125 utilised (S)-styrene oxide to attach abenzyl alcohol pendant arm to cyclen. This mono-N substituted cyclen derivativewas then complexed with zinc(II) to yield a model biocatalyst for cleavage ofphosphodiester bonds. 125 In an investigation of full cavity development by tetra-Nsubstitutionwith benzyl alcohol pendant arms, Whitbread et al., found through abinitio modelling work that the phenyl groups of a ligand formed in this way wouldjuxtapose to give a shallow cavity. 99, 100, 126 However, although these studies of thiscomplex showed its suitability as a potential receptor, exploration of guest inclusionwith 25 was not pursued due to the low yields (ca. 40%) obtained when producing96, 126the ligand.In 1999 Smith synthesised 26, which has come to be known, within theWainwright group, as one of the first generation metal-ion activated aromatic anionreceptors. 90, 93-97 It is possible to alter the size of the cavity within these receptors incorrespondence with the ionic radius of the coordinating metal. 126, 127 Thus the Pb(II)complexes appear to have slightly larger cavities than the Cd(II) complexes. <strong>Theses</strong>tudies by Smith proved to be the advent of investigation into receptor complexes ofthis class. They operate with considerable efficacy by including aromatic anions,such as phenolates, sulfonates and benzoates and, aromatic amino acids.Smith obtained crystal structures for many of the inclusion complexes formedwith his first generation receptor, 26, two of which are shown in Figures 1.10 and1.11. These crystal structures reveal the mode of bonding between the aromaticanionic guest species and the first generation receptor as primarily being hydrogenbonding between the guest oxoanion and the host pendant hydroxy groups. Althoughπ-π interactions between the host aromatic rings and that of the guest are not22
apparent there is, nonetheless, evidence from guest binding constant data thatsuggests preferential stabilisation of these guest species that are aromatic in nature. 124Figure 1.10 X-ray determined structure of the inclusion complex formed between p-aminobenzoateand [Cd(26)] 2+ . 93Figure 1.11 X-ray determined structure of the inclusion complex formed between two p-nitrophenolate molecules and [Cd(26)] 2+ . 124Moreover, electrostatic interaction between the Cd 2+ ion and the anion is minimaland therefore is not a great contributor to the stability of the complex as the closestpoint of approach between them is greater than 3.9 Å. 124As the properties of the pendant arms and the macrocycle are retained upon N-substitution the chemical properties of the receptor could be diversified to include forexample groups that would increase its solubility in aqueous media. Examples of23
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: amide oxygen atoms on the pendant a
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
show all

Jozef Hodyl PhD Thesis - Theses - Flinders University

Create successful ePaper yourself

Delete template?

Save as template?