Tesis
The Search for Supramolecular Catalysis Using Supramolecular Guanine Quadruplexes.
Autor
Rivera Rios, Luis R.
Rivera, José M. (Consejero)
Institución
Resumen
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.