Antimicrobial lipopeptides are produced nonribosomally in bacteria and fungi during cultivation. They are composed of a cationic or an anionic peptide covalently bound to a specifically modified aliphatic chain. Most of the peptidic moieties have complex cyclic structures. Here we report that conjugation of a palmitic acid to the N-terminus of very short cationic di- and tripeptides composed of all l- and d, l-amino acids endowed them with potent antimicrobial activities. Interestingly, cell specificity was determined by the sequence of the short peptidic chain. Palmitoyllysine served as a control and was inactive toward all microorganisms tested. Replacing an l-amino acid with its d-enantiomer did not affect the activity of the corresponding lipopeptides. Importantly, selected lipopeptides were also potent in vivo in a mouse model of Candida albicans infection. Bacterial leakage experiments and negative staining electron microscopy suggest that their mode of action involves permeation and disintegration of the microorganism's membrane, similar to many long antimicrobial peptides and lipopeptides. Interestingly, each lipopeptide assembled in solution into a nanostructure with a unique morphology which could partially explain differences in their biological activity. Besides adding important information on the parameters necessary for antimicrobial lipopeptides to kill microorganisms, the simple composition of these minilipopeptides and their diverse cell specificities make them attractive candidates for various applications.

Self-assembling systems, whose structure and function can be reversibly controlled in situ are of primary importance for creating multifunctional supramolecular arrays and mimicking the complexity of natural systems. Herein we report on photofunctional fibers self-assembled from perylene diimide cromophores, in which interactions between aromatic monomers can be attenuated through their reduction to anionic species that causes fiber fission. Oxidation with air restores the fibers. The sequence represents reversible supramolecular depolymerization-polymerization in situ and is accompanied by a reversible switching of photofunction.

A methodology leading to facile self-assembly of crystalline aromatic arrays in dilute aqueous solutions would enable efficient fabrication and processing of organic photonic and electronic materials in water. In particular, soluble 2D crystalline nanosheets may mimic the properties of photoactive thin films and self-assembled monolayers, covering large areas with ordered nanometer-thick material. We designed such solution-phase arrays using hierarchical self-assembly of amphiphilic perylene diimides in aqueous media. The assemblies were characterized by cryogenic transmission electron microscopy (cryo-TEM), revealing crystalline order and 2D morphology (confirmed by AFM studies). The order and morphology are preserved upon drying as evidenced by TEM and AFM. The 2D crystalline-like structures exhibit broadening and red-shifted absorption bands in UV-vis spectra, typical for PDI crystals and liquid crystals. Photophysical studies including femtosecond transient absorption spectroscopy reveal that two of the assemblies are superior light-harvesters due to excellent solar spectrum coverage and fast exciton transfer, in one case showing exciton diffusion comparable to solid-state crystalline systems based on perylene tetracarboxylic dianhidride (PTCDA).

The unique properties of carbon nanotubes (CNT) are advantageous for emerging applications. Yet, the CNT insolubility hampers their potential. Approaches based on covalent and noncovalent methodologies have been tested to realize stable dispersions of CNTs. Noncovalent approaches are of particular interest as they preserve the CNT's structures and properties. We report on hybrids, in which perylene diimide (PDI) amphiphiles are noncovalently immobilized onto single wall carbon nanotubes (SWCNT). The resulting hybrids were dispersed and exfoliated both in water and organic solvents in the presence of two different PDI derivatives, PP2b and PP3a. The dispersions were investigated using cryogenic transmission electron microscopy (cryo-TEM), providing unique structural insights into the exfoliation. A helical arrangement of PP2b assemblies on SWCNTs dominates in aqueous dispersions, while a single layer of PP2b and PP3a was found on SWCNTs in organic dispersions. The dispersions were probed by steady-state and time-resolved spectroscopies, revealing appreciable charge redistribution in the ground state, and an efficient electron transfer from SWCNTs to PDIs in the excited state. We also fabricated hybrid materials from the PP2b/SWCNT dispersions. A supramolecular membrane was prepared from aqueous dispersions and used for size-selective separation of gold nanoparticles. Hybrid buckypaper films were prepared from the organic dispersions. In the latter, high conductivity results from enhanced electronic communication and favorable morphology within the hybrid material. Our findings shed light onto SWCNT/dispersant molecular interactions, and introduce a versatile approach toward universal solution processing of SWCNT-based materials.

Investigation of supramolecular kinetics is essential for elucidating self-assembly mechanisms. Recently, we reported on a noncovalent system involving a bolaamphiphilic perylene diimide dimer that is kinetically trapped in water but can rearrange into a different, more ordered assembly in water/THF mixtures ( Angew. Chem. Int. Ed. 2014 , 53 , 4123 ). Here we present a kinetic mechanistic study of this process by employing UV-vis spectroscopy. The transformation exhibits a rapid decrease in the red-shifted absorption band, which is monitored in order to track the kinetics at different temperatures (15-50 °C) and concentrations. Fitting the data with the 1D KJMA (Kolmogorov-Johnson-Mehl-Avrami) model affords the activation parameters. The latter as well as seeding experiments indicates that the transformation occurs without the detachment of covalent units, and that hydration dynamics plays a significant role in nucleation, with entropic factors being dominant. Switching off the transformation, and the formation of off-pathway intermediates were observed upon heating to temperatures above 55 °C. These insights into kinetically controlled supramolecular polymer transformations provide mechanistic information that is needed for a fundamental understanding of noncovalent processes, and the rational design of noncovalent materials.