Multiformity of Photoelectron Storages in Functionalized Carbon Nitrides Enabling Reversible and Adaptable Colorimetric Sensing

Colorimetric sensing has been widely used for centuries across diverse fields, thanks to easy operation with no electricity and uncompromised high sensitivity. However, the limited number of chromogenic systems hampers its broader applications. Here, we reported that carbon nitride (CN), the raw materials-abundant and cheap semiconductors with photoelectron storage capability, can be developed as a new chromogenic platform for colorimetric sensing. Beyond most photoelectron storage materials that only demonstrated blue color in the excited state, CN could also exhibit brown color by terminal group functionalization. The experiments and DFT theoretical calculation revealed the origin of the unusual two types of color switches. Cyano and carbonyl terminal groups in CN elongated the centroids distance of electron/hole and stabilized the excited states through a physical and electrochemical pathway, respectively; meanwhile, the counter cations strengthened these processes. As a result, the CN-derived colorimetric O2 sensors demonstrated excellent reversibility in recycling hundreds of times for detection, and exhibited adaptable limit of detection and linear detection range, which was superior to commercial O2 sensors, especially for complex systems with broad variable concentrations.

Negative Thermal Quenching of Photoluminescence from Liquid-Crystalline Molecules in Condensed Phases

The luminescence of materials in condensed phases is affected by not only their molecular structures but also their aggregated structures. In this study, we designed new liquid-crystalline luminescent materials based on biphenylacetylene with a bulky trimethylsilyl terminal group and a flexible alkoxy chain. The luminescence properties of the prepared materials were evaluated, with a particular focus on the effects of phase transitions, which cause changes in the aggregated structures. The length of the flexible chain had no effect on the luminescence in solution. However, in crystals, the luminescence spectral shape depended on the chain length because varying the chain length altered the crystal structure. Interestingly, negative thermal quenching of the luminescence from these materials was observed in condensed phases, with the isotropic phase obtained at high temperatures exhibiting a considerable increase in luminescence intensity. This thermal enhancement of the luminescence suggests that the less- or nonemissive aggregates formed in crystals are dissociated in the isotropic phase. These findings can contribute toward the development of new material design concepts for useful luminescent materials at high temperatures.

The Oxoglutarate Binding Site and Regulatory Mechanism Are Conserved in Ammonium Transporter Inhibitors GlnKs from Methanococcales

Protein inhibition is a natural regulatory process to control cellular metabolic fluxes. PII-family signal-transducing effectors are in this matter key regulators of the nitrogen metabolism. Their interaction with their various targets is governed by the cellular nitrogen level and the energy charge. Structural studies on GlnK, a PII-family inhibitor of the ammonium transporters (Amt), showed that the T-loops responsible for channel obstruction are displaced upon the binding of 2-oxoglutarate, magnesium and ATP in a conserved cleft. However, GlnK from Methanocaldococcus jannaschii was shown to bind 2-oxoglutarate on the tip of its T-loop, causing a moderate disruption to GlnK–Amt interaction, raising the question if methanogenic archaea use a singular adaptive strategy. Here we show that membrane fractions of Methanothermococcus thermolithotrophicus released GlnKs only in the presence of Mg-ATP and 2-oxoglutarate. This observation led us to structurally characterize the two GlnK isoforms apo or in complex with ligands. Together, our results show that the 2-oxoglutarate binding interface is conserved in GlnKs from Methanococcales, including Methanocaldococcus jannaschii, emphasizing the importance of a free carboxy-terminal group to facilitate ligand binding and to provoke the shift of the T-loop positions.

Antimicrobial Peptide Modifications against Clinically Isolated Antibiotic-Resistant Salmonella

Antimicrobial peptides are promising molecules to address the global antibiotic resistance problem, however, optimization to achieve favorable potency and safety is required. Here, a peptide-template modification approach was employed to design physicochemical variants based on net charge, hydrophobicity, enantiomer, and terminal group. All variants of the scorpion venom peptide BmKn-2 with amphipathic α-helical cationic structure exhibited an increased antibacterial potency when evaluated against multidrug-resistant Salmonella isolates at a MIC range of 4–8 µM. They revealed antibiofilm activity in a dose-dependent manner. Sheep red blood cells were used to evaluate hemolytic and cell selectivity properties. Peptide Kn2-5R-NH2, dKn2-5R-NH2, and 2F-Kn2-5R-NH2 (variants with +6 charges carrying amidated C-terminus) showed stronger antibacterial activity than Kn2-5R (a variant with +5 charges bearing free-carboxyl group at C-terminus). Peptide dKn2-5R-NH2 (d-enantiomer) exhibited slightly weaker antibacterial activity with much less hemolytic activity (higher hemolytic concentration 50) than Kn2-5R-NH2 (l-enantiomer). Furthermore, peptide Kn2-5R with the least hydrophobicity had the lowest hemolytic activity and showed the highest specificity to Salmonella (the highest selectivity index). This study also explained the relationship of peptide physicochemical properties and bioactivities that would fulfill and accelerate progress in peptide antibiotic research and development.