Effect of buffer on heparin binding and sensing in competitive aqueous media

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JournalSupramolecular Chemistry
DateAccepted/In press - 5 Sep 2016
DateE-pub ahead of print - 14 Sep 2016
DatePublished (current) - 2017
Number of pages8
Pages (from-to)688-695
Early online date14/09/16
Original languageEnglish


Although buffer-specific effects on molecular recognition are known in biological science, they remain rare in supramolecular chemistry. The binding between a cationic dye, Mallard Blue (MalB), and polyanionic heparin in aqueous NaCl (150 mM) is studied in three commonly-used buffers (Tris-HCl, HEPES, Phosphate, each 10 mM). Although MalB has a very similar UV-Vis spectrum in each buffer, the sensory response towards heparin was different in each case. This can be ascribed to differences in the complex formed. In Tris-HCl which has the least competitive chloride counter-anions, MalB exhibits a hypsochromic shift of 25 nm, assigned to strong binding and aggregation of the dye on heparin. In more competitive HEPES, containing a sulfonate anion, there is weaker binding and less aggregation of MalB along the heparin; the hypsochromic shift is only 15 nm. In phosphate buffer, MalB can interact quite strongly with buffer phosphate anions; although heparin binding is still observed, the hypsochromic shift associated with dye aggregation is only 5 nm. As such, specific buffer interactions with the MalB-heparin complex mediate host-guest binding and sensing. Buffer choice must be made carefully in studies of molecular recognition – we would caution against using phosphate and sulfonate containing buffers when studying electrostatic binding.

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