Cd as a Probe in NMR Studies of Allosteric Host-Guest-Ligand Complexes of Porphyrin Cage Compounds.

Cadmium porphyrin cage compounds and have been synthesized from the free base porphyrin cage derivative and Cd(OAc) ⋅ 2 HO or Cd(OAc) ⋅ 2 HO, respectively. The compounds form allosteric complexes with the positively charged guests '-dimethylimidazolium hexafluorophosphate () and '-dimethylviologen dihexafluorophosphate (), which bind in the cavity of the cage, and , which coordinates as an axial ligand to the outside of the cage. In the presence of , the binding of in is enhanced by a factor of ∼31, while the presence of or in the cavity of enhances the binding of by factors of 55 and 85, respectively.

Paramagnetic relaxation enhancement NMR as a tool to probe guest binding and exchange in metallohosts.

Paramagnetic metallohost systems can bind guest molecules and find application as biomimetic catalysts. Due to the presence of the paramagnetic metal center, rigorous characterization of these systems by NMR spectroscopy can be very difficult. We report here that metallohost-guest systems can be studied by using the paramagnetic relaxation enhancement (PRE) effect.

Host-Guest Exchange of Viologen Guests in Porphyrin Cage Compounds as Studied by Selective Exchange Spectroscopy (1D EXSY) NMR.

Dynamics in complexes of porphyrin cage compounds and viologen-derived guest molecules are investigated by selective exchange NMR spectroscopy (1D EXSY). Exchange rates were found to be independent of excess guest concentration, revealing a dissociative exchange mechanism, which is accompanied by negative activation entropies, indicating significant reorganization of the host-guest complex during dissociation. Nonsymmetric viologen guests with bulky head groups had more unidirectional binding and slower exchange rates than guests with less-bulky head groups.

Absolute configuration and host-guest binding of chiral porphyrin-cages by a combined chiroptical and theoretical approach.

Porphyrin cage-compounds are used as biomimetic models and substrate-selective catalysts in supramolecular chemistry. In this work we present the resolution of planar-chiral porphyrin cages and the determination of their absolute configuration by vibrational circular dichroism in combination with density functional theory calculations. The chiral porphyrin-cages form complexes with achiral and chiral viologen-guests and upon binding one of the axial enantiomorphs of the guest is bound selectively, as is indicated by induced-electronic-dichroism-spectra in combination with calculations.

Effect of Chirality on the Binding of Viologen Guests in Porphyrin Macrocycles.

As part of a project aimed at the development of chiral processive catalysts that can write information on a polymer chain we describe the synthesis of two optically active porphyrin macrocycles, which are prepared in 3 steps from an achiral precursor compound. Fluorescence and H-NMR studies show that one of the macrocycles displays selectivity in the binding of chiral viologen guest molecules.

Development of NMR and thermal shift assays for the evaluation of isocitrate lyase inhibitors.

The enzymes isocitrate lyase (ICL) isoforms 1 and 2 are essential for survival within macrophages during latent tuberculosis (TB). As such, ICLs are attractive therapeutic targets for the treatment of tuberculosis. However, there are few biophysical assays that are available for accurate kinetic and inhibition studies of ICL .

Direct Synthesis of Chiral Porphyrin Macrocyclic Receptors via Regioselective Nitration.

Nitration of tetraphenylporphyrin cage compound 1, at -40 °C, leads to the regioselective formation of the chiral mononitro compound 2 (75% isolated yield) and, at -30 °C, to the achiral syn-dinitro-derivative 3 and the chiral anti-dinitro derivative 4 in a diastereomeric ratio of 5:2, which were separated by chromatography (46 and 20% yields, respectively). The structures of the compounds were confirmed by X-ray crystallography.