The Search for Supramolecular Catalysis Using Supramolecular Guanine Quadruplexes.
Rivera Rios, Luis R.
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The field of supramolecular chemistry is a fast growing one overlapping the interfaces of chemistry - biology and chemistry - physics. This study examines how the mAG scaffold can be furthered converted into a fluorescent scaffold with extended π-surface that upon assembly presents a bathochromic shift with hypochromic effect. This fluorescent derivative shows no assembly when Na+ is added. In contrast, when the same amount of K+ is added under the same conditions the hexadecamer is detected. These molecular changes can be visualized with the naked eye since the solution changes from light green to orange. The behavior of a mixture of the known mAGa and new fluorescent derivative, PyrmAGa, are presented in Chapter 3. This mixture deviates from a previously work by Rivera et al.32 since the fluorescent derivative is a different recognition motif of extra aromatic area for π-π interaction near the expanded Hoogsteen edge. Even with these differences, we observed that there is a nonnarcissistic mixture and attempted to characterize the complex equilibrium. The second part of the thesis is dedicated to discuss the advances made in aqueous media. First, the synthesis and characterization of a self-assembled dendrimers (SADs) first generation (mAGD1OH) and fourth generation (mAGD4OH) are presented in Chapter 4. This chapter was published as a full article in the 2011 Langmuir special issue on Supramolecular Chemistry at the Interface. The last chapter will be dedicated to narrate the investigations made by mixing hydrophilic mAG derivatives (mAGD4OH, mAGD1OH, mAGcat) with hemin and hydrogen peroxide to examine the oxidation rate of ABTS changed with respect to the sample without it. The effect of buffer type was studied by starting with six different buffers (Tris-HCl, TrisMes, Tris-PTS, hepesNaOH, hepesNaNH4, PBS) of which two are reported. In the rate studies PBS show extremely noisy measurements and the blank control for the TrisMes buffer show a standard deviations larger than the measured value therefore results using TrisPTS and hepesKOH will be the only two results discussed here.