Siderophores

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  • Siderophores
    • catechol based coordinating group
      • deprotonation reactions
        • Ka1 = ([LH5][H+])/[LH6]
          • Ka2 = ([LH4][H+])/[LH5]
            • etc...
    • Ka
      • deprotonation reactions
        • Ka1 = ([LH5][H+])/[LH6]
          • Ka2 = ([LH4][H+])/[LH5]
            • etc...
      • Ka=([H+][L])/[LH]
        • low pH = high [H+]
        • high [H+] = high Ka
          • high Ka = low pKa
            • so higher pKa = lower pH, higher affinity of H so no deprotonation hence [Fe3+] decreases
            • Ka
              • Ka=([H+][L])/[LH]
                • low pH = high [H+]
                • high [H+] = high Ka
                  • high Ka = low pKa
                    • so higher pKa = lower pH, higher affinity of H so no deprotonation hence [Fe3+] decreases
              • uncoord ligand = [L]t
                • [L]t = alphaL [L]
      • uncoord ligand = [L]t
        • [L]t = alphaL [L]
    • K
      • K1 = [LM]/([L][M])
        • K2 = [L2M]/[L][LM]
          • etc ...
      • stability constant
      • Beta = K1+K2+K3...
        • Beta 110 = [LFe]/([L][Fe3+])
          • bacteria want [Fe3+] as high as possible
          • Beta ligands metals protons
          • Increasing B 110
      • High K value = equilibrium to right. LESS free metal
      • Low K value = equilibrium to left. MORE free metal
    • Delta G
      • Delta G ideally negative
      • delta G = delta H - T delta S
        • delta S > 0 = gain in freedon (favourable)
          • delta S < 0 = loff of freedon (unfavourable)
          • rarely ever gain in freedom so the less negative the better.
        • delta H usually negative in co-ordination reactions
    • delta H usually negative in co-ordination reactions
    • pFe3+
      • efficacy
        • pM = -log([M]free)

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