Salt‐Induced Adaptation of a Dynamic Combinatorial Library of Pseudopeptidic Macrocycles: Unraveling the Electrostatic Effects in Mixed Aqueous Media

Dynamic combinatorial libraries are powerful systems for studying adaptive behaviors and relationships, as models of more complex molecular networks. With this aim, we set up a chemically diverse dynamic library of pseudopeptidic macrocycles containing amino‐acid side chains with differently charged residues (negative, positive, and neutral). The responsive ability of this complex library upon the increase of the ionic strength has been thoroughly studied. The families of the macrocyclic members concentrating charges of the same sign showed a large increase in its proportion as the ionic strength increases, whereas those with residues of opposite charges showed the reverse behavior. This observation suggested an electrostatic shielding effect of the salt within the library of macrocycles. The top‐down deconvolution of the library allowed us to obtain the fundamental thermodynamic information connecting the library members (exchange equilibrium constants), as well as to parameterize the adaptation to the external stimulus. We also visualized the physicochemical driving forces for the process by structural analysis using NMR spectroscopy and molecular modeling. This knowledge permitted the full understanding of the whole dynamic library and also the de novo design of dynamic chemical systems with tailored co‐adaptive relationships, containing competing or cooperating species. This study highlights the utility of dynamic combinatorial libraries in the emerging field of systems chemistry.     

Antimicrobial activity of silver nanoparticle colloids of different sizes and shapes against Streptococcus mutans

Research on Chemical Intermediates - Silver nanoparticles stabilized with chitosan biopolymer are a new antibacterial agent for treatment of caries. To determine whether the size and morphology of...     

Chiral‐Symmetry Selection in Soft Monolayers under Vortical Flow

Herein, we report and interpret a new chiral‐selection phenomenon in the orientational ordering of soft‐assembled domains that arise spontaneously in Langmuir monolayers of an azobenzene derivative at the air/water interface. The orientational chirality of isolated sub‐millimeter domains was unambiguously assessed by optical microscopy. The selection process, quantified by using an enantiomeric excess parameter, was controlled by stirring the aqueous subphase. We have studied the dependence of this process on stirring rate and handedness, stirring time, temperature, and on the initial state of the monolayer. The influence of the concomitant cis/trans isomerization on the reported chiral‐selection process is also discussed.