Jozef Hodyl PhD Thesis - Theses - Flinders University

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An example of the titration curves obtained from the 1 H NMR monitored titrationexperiments with hydroxy substituted benzoate guest species is shown in titrationcurves A and B, for o-hydroxybenzoate and p-hydroxybenzoate, respectively, inFigure 3.14.7.757.737.71Δδobs (ppm)7.697.677.657.637.61A0 1 2 3 4 5 6 7 8 9 10[H]/[G]δobs(ppm)7.787.767.747.727.707.687.667.64B0 1 2 3 4 5 6 7 8 9 10[H]/[G]Figure 3.14 Examples of titration curves displaying, A, the change in chemical shift of the paraproton of o-hydroxybenzoate and, B the H B protons of p-hydroxybenzoate. Bothtitration curves were obtained at a constant guest concentration of 10 -3 M, withincreasing ratio (0-10 equivalents) of [Cd(TracHP12)](ClO 4 ) 2 , 49, in DMSO-d 6 , Thecurves show the theoretical δ values that best fit the calculated values of K and δ HG .The red square points show the experimentally obtained chemical shift values.66
The full set of logK values obtained from inclusion studies with hydroxybenzoateguests and [Cd(TracHP12)](ClO 4 ) 2 , 49, is shown in Table 3.2.Table 3.2Binding constants (logK) for guest anion binding of hydroxy substituted benzoates with[Cd(TracHP12)](ClO 4 ) 2 , 49, determined by 1 H NMR monitored titrations in DMSO-d 6with additional binding constants for benzoate and 2,6-dihydroxybenzoate determinedin CD 3 OD. Both sets of logK values were obtained at 298 K.[Cd(TracHP12) 2+ , 49Guest species logK a logK b cpK abenzoate d 4.11 ± 0.06 3.96 ± 0.09 4.19p-hydroxybenzoate 4.09 ± 0.07 e 4.54m-hydroxybenzoate 4.16 ± 0.09 e 4.30o-hydroxybenzoate 3.08 ± 0.08 3.23 ± 0.03 2.972,6-dihydroxybenzoate 2.05 ± 0.03 e 1.05a Acquired in DMSO-d 6b Acquired in CD 3 OD c Values obtained in H 2 O from PHYSPROPdatabase for their respective conjugate acids. 202 d Guest stock solution 10% (v/v) D 2 O in DMSOd6 . e Not attempted.It is evident from the values that the trend of logK in which o-hydroxybenzoate >m-hydroxybenzoate > p-hydroxybenzoate is not seen here. Instead there is a clearrelationship between the logK values and the basicity of the guest species wherebythe more basic the guest species (indicated by higher pK a ) the higher the bindingconstant.It is interesting to note that o-hydroxybenzoate and 2,6-dihydroxybenzoate bothhave significantly lower pK a s and logKs. This is explained by the fact that bothspecies can engage in intramolecular hydrogen bonding not accessible to the m- andp-isomers. This internal hydrogen bonding is shown in Figure 3.15.One consequence of this intramolecular hydrogen bonding is a lowering of the203, 204pK a due to delocalisation of the negative charge on the carboxylate.67
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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
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: non-classical hydrogen bonding is g
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
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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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CHAPTER 7EXPERIMENTAL7.1 General Ex
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inding constants (logK values) and
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delay time of 4 s. 13 C CPMAS NMR s
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C, -CH 2 - CH 2 OSO 2 ); 68.11 (1 C
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A solution of 69 (2.00 g, 10.1 mmol
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Bn, meta); 127.79 (1 C, Bn, para);
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added in a single portion. The mixt
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dioxane): δ 158.67 (1 C, C=O); 135
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1-(benzyloxycarbonyl)-4,7,10-tris-(
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1,4,7-tris-((S)-2-hydroxy-3-phenoxy
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1,4,7-tris(S)-2-hydroxy-3-[4-((2-(2
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1,4,7-tris(S)-2-hydroxy-3-[4-(2-(2-
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1-(2-hydroxypropyl)-4,7,10-tris-((S
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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
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Si-GPS-Tri-Trac, 4545The title comp
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APPENDIX ABINDING CONSTANT DETERMIN
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1.01000.880δ obs (ppm)0.60.4logK =
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APPENDIX BDETERMINATION OF STOICHIO
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0.5χG∆δGFigure B.2χ GSimulated
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13 C CPMAS NMR SPECTRA OF SOME HIGH
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Si-GPS-[Cd(Trac)(2,5-diydroxybenzoa
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REFERENCES
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15. D. Tzalis and Y. Tor, Tetrahedr
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42. A. P. Davis and R. S.Wareham, A
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69. R. J. Bergeron, M. A. Channing
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93. C. B. Smith, A. K. W. Stephens,
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118. D. D. Dischino, E. J. Delaney,
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144. X. Huang, X. Chang, Q. He, Y.
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169. J. M. Klunder, T. Onami and K.
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197. K. A. Connors, Binding Constan
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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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