The
coupling between molecular conformation and chirality is a
cornerstone in the construction of supramolecular helical structures
of small molecules across various length scales. Inspired by biological
systems, conformational preselection and control in artificial helical
molecules, polymers, and aggregates has guided various applications
in optics, photonics, and chiral sorting among others, which are frequently
based on an inherent chirality amplification through processes such
as templating and self-assembly. The so-called B4 nano- or microfilament
phase formed by some bent-shaped molecules is an exemplary case for
such chirality amplification across length scales, best illustrated
by the formation of distinct nano- or microscopic chiral morphologies
controlled by molecular conformation. Introduction of one or more
chiral centers in the aliphatic side chains led to the discovery of
homochiral helical nanofilament, helical microfilament, and heliconical-layered
nanocylinder morphologies. Herein, we demonstrate how a priori calculations of the molecular conformation affected by chiral side
chains are used to design bent-shaped molecules that self-assemble
into chiral nano- and microfilament as well as nanocylinder conglomerates
despite the homochiral nature of the molecules. Furthermore, relocation
of the chiral center leads to formation of helical as well as flat
nanoribbons. Self-consistent data sets from polarized optical as well
as scanning and transmission electron microscopy, thin-film and solution
circular dichroism spectropolarimetry, and synchrotron-based X-ray
diffraction experiments support the progressive and predictable change
in morphology controlled by structural changes in the chiral side
chains. The formation of these morphologies is discussed in light
of the diminishing effects of molecular chirality as the chain length
increases or as the chiral center is moved away from the core-chain
juncture. The type of phase (B1-columnar or B4) and morphology of
the nano- or microfilaments generated can further be controlled by
sample treatment conditions such as by the cooling rate from the isotropic
melt or by the presence of an organic solvent in the ensuing colloidal
dispersions. We show that these nanoscale morphologies can then organize
into a wealth of two- and three-dimensional shapes and structures
ranging from flower blossoms to fiber mats formed by intersecting
flat nanoribbons.
Cystic fibrosis (CF) is one of the most prevalent genetic diseases and a total of 1700 different genetic mutations can cause this condition. Patients that suffer this disease have a thickening of the mucus, creating an environment that promotes bacterial infections. Pseudomonas aeruginosa is a ubiquitous bacterium, which is frequently found in the lungs of CF patients. P. aeruginosa is known for its high level of antibiotic resistance as well as its high rate of mutation that allows it to rapidly evolve and adapt to a multitude of conditions. When a CF lung is infected with P. aeruginosa, the decay of the patient is accelerated, but there is little that can be done apart from controlling the infection with antibiotics. Novel strategies to control P. aeruginosa infection are imperative, and nanotechnology provides novel approaches to drug delivery that are more efficient than classic antibiotic treatments. These drug delivery systems are offering new prospects, especially for these patients with special mucus conditions and bacterial characteristics that limit antibiotic use.
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