The existence of stabilizing carbohydrate-aromatic interactions is demonstrated from both the theoretical and experimental viewpoints. The geometry of experimentally based galactose-lectin complexes has been properly accounted for by using a MP2/6-31G(d,p) level of theory and by considering a counterpoise correction during optimization. In this case, the stabilizing interaction energy of the fucose-benzene complex amounts to 3.0 kcal/mol. The theoretical results obtained herein indicate that the carbohydrate-aromatic interactions are stabilizing interactions with an important dispersive component and that electronic density between the sugar hydrogens and the aromatic ring indeed exists, thus giving rise to three so-called nonconventional hydrogen bonds. Experimental evidence of the intrinsic tendency of aromatic moieties to interact with certain sugars has also been shown by simple NMR experiments in water solution. Benzene and phenol specifically interact with the clusters of C-H bonds of the alpha face of methyl beta-galactoside, without requiring the well-defined three-dimensional shape provided by a protein receptor, therefore resembling the molecular recognition features that are frequently observed in many carbohydrate-protein complexes.

Type IV secretion systems (T4SS) mediate the transfer of DNA and protein substrates to target cells. TrwK, encoded by the conjugative plasmid R388, is a member of the VirB4 family, comprising the largest and most conserved proteins of T4SS. VirB4 was suggested to be an ATPase involved in energizing pilus assembly and substrate transport. However, conflicting experimental evidence concerning VirB4 ATP hydrolase activity was reported. Here, we demonstrate that TrwK is able to hydrolyze ATP in vitro in the absence of its potential macromolecular substrates and other T4SS components. The kinetic parameters of its ATPase activity have been characterized. The TrwK oligomerization state was investigated by analytical ultracentrifugation and electron microscopy, and its effects on ATPase activity were analyzed. The results suggest that the hexameric form of TrwK is the catalytically active state, much like the structurally related protein TrwB, the conjugative coupling protein.

Diseases that result from infection are, in general, a consequence of specific interactions between a pathogenic organism and the cells. The study of host-pathogen interactions has provided insights for the design of drugs with therapeutic properties. One area that has proved to be promising for such studies is the constituted by carbohydrates which participate in biological processes of paramount importance. On the one hand, carbohydrates have shown to be information carriers with similar, if not higher, importance than traditionally considered carriers as amino acids and nucleic acids. On the other hand, the knowledge on molecular recognition of sugars by lectins and other carbohydrate-binding proteins has been employed for the development of new biomedical strategies. Biophysical techniques such as X-Ray crystallography and NMR spectroscopy lead currently the investigation on this field. In this review, a description of traditional and novel NMR methodologies employed in the study of sugar-protein interactions is briefly presented in combination with a palette of NMR-based studies related to biologically and/or pharmaceutically relevant applications.

Although the potential energy surface of highly symmetric cyclohexane has been extensively reviewed, no attention has been paid to the study of the effect of substitution of a methylene group by a heteroatom. The substitution may cause changes in molecular symmetry as well as the dipole moment, and the unshared electron pairs associated with the heteroatom may also introduce changes in molecular reactivity. However, these phenomena are not yet completely understood. To address these issues, a rigorous description of the inversion-topomerization process of methylcyclohexane and a revision of the conformational potential energy of oxane and thiane are presented. Moreover, the usefulness of providing a three-dimensional representation of these processes is discussed. In the case of methylcyclohexane, calculations show that three transition states are associated with inversion and four more with topomerization. In contrast, for oxane and thiane, only two transition states are involved with inversion and two with topomerization. Two fundamental conclusions can be drawn from this study. The first is that the inversion process occurs through elementary, stages that we have denoted "conformational elemental stages", which is an analogous term to that used for reaction mechanism description (minima-transition state-minima) where several elemental steps take place. The second conclusion is that two independent processes, inversion and topomerization, are connected by some common conformers. The inversion process controls the ring interchange, while topomerization allows exchange between skewed boats.