Single-walled carbon nanotubes (SWCNTs) are desirable flexible thermoelectric materials in applications of large-scale low-grade thermal energy. However, weak Seebeck coefficients of SWCNTs around room temperature limit their development as a flexible power generator. In this work, we significantly improve the Seebeck coefficients of SWCNT-based composites by integrating the discotic liquid-crystal 2,3,6,7,10,11-hexakis(hexyloxy) triphenylene (HAT6) through the energy-filtering effect. The Seebeck coefficients of SWCNT/HAT6 composite films are about more than twice that of the pristine SWCNT films, and a maximum power factor of 408.23 ± 48.96 μW m −1 K −2 is achieved at room temperature, which is one of the highest values among organic small-moleculebased thermoelectric composites reported so far. The flexible power generator based on p-type SWCNT/HAT6 films is first assembled. An outstanding power density of 0.64 μW cm −2 with a thermoelectric voltage of 17.64 mV at a temperature gradient of 56 K is achieved. This study demonstrates that SWCNT/ discotic liquid-crystal composites show great promise in thermoelectric (TE) materials and open a new avenue for the development of TE devices.
A series of cationic polypeptide imidazolium conjugates were prepared by ring-opening polymerization (ROP) of γ-4-(3chloropropoxycarbonyl)benzyl-L -glutamic acid-based N-carboxyanhydride (CPBLG-NCA) initiated by various mono-or diamine initiators and subsequent side-chain modification with high grafting efficiency. Rapid and controlled ROP was achieved by polymerizing CPBLG-NCA in a dichloromethane/NaHCO 3 /H 2 O solvent mixture with the amine initiators. The resulting polypeptides bearing imidazolium iodide pendants showed reversible upper critical solution temperature (UCST)-type thermoresponsive properties in both ethanol and DI water while the polypeptides with tetrafluoroborate counter-anions showed a UCST in phosphate buffer saline (PBS). The cloud point temperature (T cp ) in ethanol and aqueous solutions can be tuned by both molecular weight and the end-or linkage-groups in the main chain. The cationic polypeptides showed good antibacterial activity against Staphylococcus aureus and low hemolysis. Our results provide a facile and rapid ROP strategy to develop new families of stimuli-responsive polypeptides with tunable properties as well as antibacterial polypeptides with optimized selectivity.
Antimicrobial polypeptides are promising mimics of antimicrobial
peptides (AMPs) with low risks of antimicrobial resistance (AMR).
Polypeptides with facile and efficient production, high antimicrobial
activity, and low toxicity toward mammalian cells are highly desirable
for practical applications. Herein, triblock copolypeptides with chloro
groups (PPG
n
-PCPBLG
m
) and different main-chain lengths were synthesized via an
ultrafast ring-opening polymerization (ROP) using a macroinitiator,
namely poly(propylene glycol) bis(2-aminopropyl ether), and purified
or nonpurified monomer (i.e., CPBLG-NCA). PPG
n
-PCPBLG
m
with 90 amino acid residues
can be readily prepared within 300 s. Imidazolium-based block copolypeptides
(PPG
n
-PIL
m
) were facilely prepared via nucleophilic substitution of PPG
n
-PCPBLG
m
with
NaN3 and subsequent “click” chemistry. α-Helical
PPG
n
-PIL
m
can
self-assemble into nanostructured and cationic micelles which displayed
highly potent antimicrobial activity and low hemolysis. The top-performing
material, namely PPG34-PIL70, showed low minimum
inhibitory concentration (MIC) against both Gram-positive S. aureus and Gram-negative E. coli (25 μg mL–1). It also displayed low toxicity
against mouse embryonic fibroblast (NIH 3T3) and human embryonic kidney
(293T) cells at 2× MIC.
Poly(L-cysteine)s with methylthio pendants (PMTLCs) were synthesized by ring-opening polymerization of a new L-cysteine-based Ncarboxyanhydride. The thioether bonds of PMTLC can be readily oxidized by H 2 O 2 yielding water-soluble PMTLC OX . The methylthio groups can undergo an alkylation reaction using methyl iodide and a subsequent ion-exchange reaction yielding sulfonium-based polypeptides (PPLC-DMS-X, where X = I, BF 4 ). PPLC-DMS-X showed upper critical solution temperature-type thermo-and oxidationresponsive properties in aqueous solutions. Both PMTLC and PPLC-DMS-X showed oxidation-induced β-sheet to α-helix transitions. The absorbance of PPLC-DMS-I and methyl orange aqueous solution displayed a significant linear correlation with temperature, which makes the sulfonium-based polypeptides good candidates in the field of temperature sensors.
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