Peptide–graphene conjugates have the cytocompatibility, electrical, and mechanical properties of graphene with the cell instructive properties of the peptide.
While
nanocarbons doped with more than one heteroatom continue
attracting growing interest owing to a wide range of applications,
precise control of their nanostructure and porosity remains a major
challenge. Herein, we report a new route to synthesize N/S co-doped
nanocarbons with precise porosity control through introduction of
sulfur into the synthesis copolymer-templated nitrogen-enriched carbons
(CTNC). Sulfur served as both a heteroatom source and morphology stabilizing
agent. The produced N/S co-doped nanocarbons showed interconnected
pores with relatively high specific surface area (∼480 m2/g) and high heteroatom content (N, 8.2 atom %; S, 8.8 atom
%). To demonstrate the dual benefits of sulfur stabilization (incorporation
of heteroatoms and improved morphology control), such prepared nanocarbons
were fabricated into supercapacitors with geometric capacitance (50
μF/cm2), well above the value observed for single
N-doped carbon (33 μF/cm2). Importantly, linear relationship
of mesopore size with block length of copolymer precursor was observed
for N/S co-doped nanocarbons, allowing optimization of the mesopore
size for supercapacitor applications. This new technique not only
expands CTNC method from N-doping to N/S co-doping systems with excellent
porosity control but also opens up new possibilities widely applicable
to other PAN-based soft-templating systems.
Teaching
chemistry without access
to a traditional laboratory space
is an ongoing challenge that has become especially relevant because
of the SARS-CoV-2 pandemic. While several remote learning options
exist for covering general chemistry concepts (including kitchen-based
experiments, online modules, and virtual reality), few options provide
opportunities for hands-on learning about the chemistry of synthetic
polymer materials. Here, we offer remote learning modules that use
household adhesives as a platform for teaching polymer chemistry outside
of the laboratory. These modules are designed for students who have
taken at least one semester of organic chemistry and have varied hands-on
time commitments, ranging from 2 to 10 total hours each. Concepts
covered include polymer synthesis, intermolecular interactions, thermomechanical
properties, structure–function relationships, and molecular
design. The experiments described in these modules also give students
a chance to practice research-relevant skills such as searching for
primary literature sources, fabricating test samples, explaining unexpected
experimental results, and revising experimental procedures to improve
methodologies. Ultimately, these modules provide educators with an
additional tool for teaching experimental chemistry outside of the
laboratory.
High
molecular weight,
synthetic block copolypeptides that self-assemble are in high demand
for biomedical applications. The current standard method for synthesis
of block copolypeptides is the controlled ring-opening polymerization
(ROP) of α-amino acid N-carboxyanhydride (NCA) monomers, where
block architectures can be created by sequential NCA monomer addition.
Recently, researchers have focused on developing reaction conditions
and initiation systems that make NCA ROP more convenient, particularly
for interdisciplinary labs without designated polypeptide facilities.
In an effort to further simplify and increase the convenience of polypeptide
synthesis, we developed a one-shot copolymerization strategy that
allows access to block copolypeptides by capitalizing on the inherently
faster reactivity of NCA monomers, compared to NTA (N-thiocarboxyanhydride) monomers. For the first time, we combine an NCA
and NTA monomer in one reaction to kinetically promote block copolypeptide
formation, providing a convenient alternative to sequential monomer
addition. The controlled nature of this copolymerization technique
is supported by a molecular weight that is modulated by the concentration
of the initiator and low dispersities. We used this one-shot copolymerization
to synthesize p(lysine)-b-p(leucine), a known peptide
amphiphile (PA). Our one-shot PAs are antimicrobial and can spontaneously
form ordered, micron-scale assemblies. Covalent conjugation of one-shot
PAs to a graphenic backbone results in a functional graphenic material
(FGM) with a self-assembled morphology, paving the way for creation
of sophisticated FGM scaffolds with polypeptide-templated, hierarchical
order. Overall, we demonstrate that this novel, one-shot copolymerization
strategy produces functional copolypeptides with macroscopic sequence
control.
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