DNA-catalyzed Henry reaction in pure water and the striking influence of organic buffer systems.

In this manuscript we report a critical evaluation of the ability of natural DNA to mediate the nitroaldol (Henry) reaction at physiological temperature in pure water. Under these conditions, no background reaction took place (i.e., control experiment without DNA). Both heteroaromatic aldehydes (e.g., 2-pyridinecarboxaldehyde) and aromatic aldehydes bearing strong or moderate electron-withdrawing groups reacted satisfactorily with nitromethane obeying first order kinetics and affording the corresponding ß-nitroalcohols in good yields within 24 h. In contrast, aliphatic aldehydes and aromatic aldehydes having electron-donating groups either did not react or were poorly converted. Moreover, we discovered that a number of metal-free organic buffers efficiently promote the Henry reaction when they were used as reaction media without adding external catalysts. This constitutes an important observation because the influence of organic buffers in chemical processes has been traditionally underestimated.

C-C Bond formation catalyzed by natural gelatin and collagen proteins.

The activity of gelatin and collagen proteins towards C-C bond formation via Henry (nitroaldol) reaction between aldehydes and nitroalkanes is demonstrated for the first time. Among other variables, protein source, physical state and chemical modification influence product yield and kinetics, affording the nitroaldol products in both aqueous and organic media under mild conditions. Significantly, the scale-up of the process between 4-nitrobenzaldehyde and nitromethane is successfully achieved at 1 g scale and in good yield. A comparative kinetic study with other biocatalysts shows an increase of the first-order rate constant in the order chitosan < gelatin < bovine serum albumin (BSA) < collagen. The results of this study indicate that simple edible gelatin can promote C-C bond forming reactions under physiological conditions, which may have important implications from a metabolic perspective.

Stimuli-responsive gels as reaction vessels and reusable catalysts.

As part of a continuing scientific challenge, a substantial effort during the past few decades has been devoted towards altering the selectivity of chemical transformations by arranging the potential reactants in a number of organized and confining media. Such systems, having features significantly different from those of isotropic solutions, include, for example, micelles, microemulsions, molecular aggregates, liquid crystals, and zeolites. Among these materials, stimuli-response gels constitute another important class of nanostructured and dynamic systems with high active surface areas and remarkable diffusion properties. Within this group, polymer gels have been traditionally used to obtain catalytic and reactive soft materials. Moreover, gels made of low-molecular-weight compounds represent a major novelty in this area as potential soft-vessels to carry out chemical reactions with control on product selectivity. In addition, the possibility of integrating switchable catalytic functions in both organo- and hydrogels shall accelerate the development of robust platforms for the 'bottom-up' tailor-fabrication of more sophisticated functional materials. The present critical review reports on the most important results published during the last decade regarding the use of 'smart' gels that has displayed promising properties as selective soft-nanoreactors and/or heterogeneous recyclable catalysts (152 references).