Dynamic Interactions in Synthetic Receptors: A Guest Exchange Saturation Transfer Study

The accumulated knowledge regarding molecular architectures is based on established, reliable, and accessible analytical tools that provide robust structural and functional information on assemblies. However, both the dynamicity and low population of noncovalently interacting moieties within studied molecular systems limit the efficiency and accuracy of traditional methods. Herein, the use of a saturation transfer-based NMR approach to study the dynamic binding characteristics of an anion to a series of synthetic receptors derived from bambusuril macrocycles is demonstrated. The exchange rates of BF₄⁻ are mediated by the side chains on the receptor (100 s⁻¹<k_ex<5000 s⁻¹), which play a critical role in receptor-anion binding dynamics. The signal amplification obtained with this approach allows for the identification of different types of intermolecular interactions between the receptor and the anion, something that could not have been detected by techniques hitherto used to study molecular assemblies. These findings, which are supported by a computational molecular dynamic study, demonstrate the uniqueness and added value of this NMR method.     

Effect of pressure on the proton transfer rate from a photoacid to a solvent. 4. Photoacids in methanol

The pressure dependence of the excited-state proton dissociation rate constant of four photoacids, 2-naphthol-6,8-disulfonate (2N68DS), 10-hydroxycamptothecin (10-CPT), 5-cyano-2-naphthol (5CN2), and 5,8-dicyano-2-naphthol (DCN2), are studied in methanol. The results are compared with the results of the pressure dependence study we recently conducted for several photoacids in water, ethanol, and propanol. The pressure dependence is explained using an approximate stepwise two-coordinate proton transfer model. The increase in rate, as a function of pressure, manifests a strong dependence of proton tunneling on the distance which decreases with an increase of pressure between the two oxygen atoms involved in the process. The decrease in the proton transfer rate with increasing pressure reflects the dependence of the reaction on the solvent relaxation rate. We found that, for the relatively weak photoacids 2N68DS, 10-CPT, and 5CN2, the proton transfer rate constant increases by a factor of about 5-8 at a pressure of about 1.5 GPa. For a strong photoacid like DCN2, the rate increase was only by a factor of 2.     

Discrimination of guests encapsulation in large hexameric molecular capsules in solution: pyrogallol[4]arene versus resorcin[4]arene capsules

NMR experiments demonstrate that, although 2b and 3b form hexameric capsules in chloroform solutions and despite the very similar building units of these hexamers, 3b encapsulates only the noncharged trialkylamines while 2b can encapsulate both the noncharged trialkylamines and the respective ammonium salts obtained by the addition of DCl. In fact, it was found that protonation that forms in situ the ammonium salt ejects the guest from the hexameric capsule of 3b. This is a general observation as it was found for guests containing alkyl chains of four, five, six, and eight carbons.     

Synthesis of New Phenolic Derivatives of Quinazolin-4(3H)-One as Potential Antioxidant Agents—In Vitro Evaluation and Quantum Studies

Considering the important damage caused by the reactive oxygen (ROS) and nitrogen (RNS) species in the human organism, the need for new therapeutic agents, with superior efficacy to the known natural and synthetic antioxidants, is crucial. Quinazolin-4-ones are known for their wide range of biological activities, and phenolic compounds display an important antioxidant effect. Linking the two active pharmacophores may lead to an increase of the antioxidant activity. Therefore, we synthesized four series of new hybrid molecules bearing the quinazolin-4-one and phenol scaffolds. Their antioxidant potential was evaluated in vitro, considering different possible mechanisms of action: hydrogen atom transfer, ability to donate electrons and metal ions chelation. Theoretical quantum and thermodynamical calculations were also performed. Some compounds, especially the ortho diphenolic ones, exerted a stronger antioxidant effect than ascorbic acid and Trolox.     

The effect of the diffusion time and pulse gradient duration ratio on the diffraction pattern and the structural information estimated from q-space diffusion MR: experiments and simulations

q-Space diffusion MRI (QSI) provides a means of obtaining microstructural information about porous materials and neuronal tissues from diffusion data. However, the accuracy of this structural information depends on experimental parameters used to collect the MR data. q-Space diffusion MR performed on clinical scanners is generally collected with relatively long diffusion gradient pulses, in which the gradient pulse duration, δ, is comparable to the diffusion time, Δ. In this study, we used phantoms, consisting of ensembles of microtubes, and mathematical models to assess the effect of the ratio of the diffusion time and the duration of the diffusion pulse gradient, i.e., Δ/δ, on the MR signal attenuation vs. q, and on the measured structural information extracted therefrom. We found that for Δ/δ  1, the diffraction pattern obtained from q-space MR data are shallower than when the short gradient pulse (SGP) approximation is satisfied. For long δ the estimated compartment size is, as expected, smaller than the real size. Interestingly, for Δ/δ  1 the diffraction peaks are shifted to even higher q-values, even when δ is kept constant, giving the impression that the restricted compartments are even smaller than they are. When phantoms composed of microtubes of different diameters are used, it is more difficult to estimate the diameter distribution in this regime. Excellent agreement is found between the experimental results and simulations that explicitly account for the use of long duration gradient pulses. Using such experimental data and this mathematical framework, one can estimate the true compartment dimensions when long and finite gradient pulses are used even when Δ/δ  1.     

Self-assembly of resorcin[4]arene in the presence of small alkylammonium guests in solution

We followed the self-assembly of C-alkyl-resorcin[4]arene (1a,1b) in the presence of tetraethylammonium salts (2). The X-ray structure of C-ethyl-resorcin[4]arene (1c) in the presence of TEABr (2b), showed a dimer encapsulating one guest. However, diffusion measurements reveal that two molecules of tetraethylammonium are encapsulated within the hexameric capsule of 1a,b in chloroform, regardless of the anion. Most importantly, the anion affects the role of water in the self-assembly and the nature of the formed capsules.