Halocin H4 is activated through cleavage by halolysin HlyR4.

Halocins are antimicrobial peptides secreted by haloarchaea capable of inhibiting the growth of other haloarchaea or bacteria. Halocin H4 (HalH4) is secreted by the model halophilic archaeon Haloferax mediterranei ATCC 33500. Despite attempts to express halH4 heterologously in Escherichia coli and subsequent careful renaturation procedures commonly employed for haloarchaeal proteins, no active halocin was obtained. However, it was discovered that the antihaloarchaeal activity of this halocin could be activated through cleavage by halolysin R4 (HlyR4), a serine protease also secreted by Hfx. mediterranei ATCC 33500. Replacement of the cysteine at the number 115 amino acid with glycine and deletion of the internal trans-membrane region (15 aa) markedly abolished HalH4's antihaloarchaeal activity. Compared to the N-terminus, the C-terminal amino acid sequence was found to be more crucial for HalH4 to exert its antihaloarchaeal activity. Mass spectrometry analysis revealed that the biologically active antihaloarchaeal peptide produced after hydrolytic cleavage by HlyR4 was the C-terminus of HalH4, suggesting a potential mechanism of action involving pore formation within competitor species' cell membranes. Taken together, this study offers novel insights into the interplay between halocins and secreted proteases, as well as their contribution to antagonistic interaction within haloarchaea. IMPORTANCE: The antihaloarchaeal function of halocin H4 (HalH4) can be activated by extracellular proteases from haloarchaea, as demonstrated in this study. Notably, we report the first instance of halocin activation through proteolytic cleavage, highlighting its significance in the field. The C-terminus of HalH4 (CTH4) has been identified as the antihaloarchaeal peptide present in hydrolysates generated by HlyR4. The CTH4 exhibited inhibitory activity against a range of haloarchaeal species (Haloarchaeobius spp., Haloarcula spp., Haloferax spp., Halorubellus spp., and Halorubrum spp.), as well as selected bacterial species (Aliifodinibius spp. and Salicola spp.), indicating its broad-spectrum inhibitory potential across domains. The encoding gene of halocin HalH4, halH4, from the model halophilic archaeon Haloferax mediterranei ATCC 33500 can be expressed in Escherichia coli without codon optimization.

Theoretical Insights on the Charge State and Bifunctional OER/ORR Electrocatalyst Activity in 4d-Transition-Metal-Doped g-C3N4 Monolayers.

Exploring efficient and stable electrocatalysts for the bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is vital to developing renewable energy technologies. However, due to the substantial and intricate design space associated with these bifunctional OER/ORR electrocatalysts, their development presents a formidable challenge, resulting in their cost-prohibitive nature in both experimental and computational studies. Herein, using the defect physics method, we systematically investigate the formation energies and bifunctional overpotential (ηBi) of 4d-transition-metal (4d-TM, 4d-TM = Zr, Nb, Mo, Ru, Rh, Pd, and Ag)-doped monolayer supercell g-C3N4 (4d-TM@C54N72) based on the density functional theory (DFT) calculations. Under N-rich and C-rich conditions, we find that the formation energies of RhN@C54N71 (Rh occupation N) and PdN@C54N71 (Pd occupation N) are smaller than that of other 4d-TMN@C54N71 (4d-TM occupation N site); for the 4d-TMint@C54N72 (4d-TM interstitial site occupation), the lowest-formation energy defects are Pdint@C54N72. These results indicate that they have better stabilities. Interestingly, for these formation energy lower systems, Pd0int@C54N72 (ηBi = 1.00 V) and Rh1+N@C54N71 (ηBi = 0.73 V) have ultralow overpotential and can be great candidates for bifunctional OER/ORR electrocatalysts. We find the reason is that adjusting the charge states of 4d-TM@C54N72 can tune the interaction strength between the oxygenated intermediates and the 4d-TM@C54N72, which plays a crucial role in the activity of reactions. Additionally, the data obtained through machine learning (ML) application suggest that the electronegativity (Nm) and bond length of 4d-TM and coordination atoms (dTM-OOH) are primary descriptors characterizing the OER and ORR activities, respectively. The charged defect tuning of the bifunctional OER/ORR activity for 4d-TM@C54N72 would enable electrocatalytic performance optimization and the development of potential electrocatalysts for renewable energy applications.

Exploring the generality of ligands for Silica-Encapsulated nanoclusters as SERS labels.

The surface enhanced Raman scattering (SERS) reporters are rather limited, and the Raman peaks still overlap in varying degrees, making SERS multiplex coding a critical bottleneck in the exploration of SERS nanotechnology. Herein, we design a general strategy to expand the SERS probe scope to 26 probes of six types, which can be further expanded within a limited range, with stable performance and structure. By constructing (Au-aggregate)@Ag@silica and (Au-aggregate)@silica nanocomposites, we develop optimal enhancement strategies for each Raman molecules. Mixed signal-ligand SERS probes improve the complexity of Raman spectra and expand the coding capacity. By integrating the strategies, SERS inks are produced and applied in anti-counterfeiting. With these improvements, this work breaks the constrains of probe selection, bringing SERS one step closer to the sensor or anti-counterfeiting application.

Adsorption, Gas-Sensing, and Optical Properties of Molecules on a Diazine Monolayer: A First-Principles Study.

Using first-principles calculations, the structural, electronic, and optical properties of CO2, CO, N2O, CH4, H2, N2, O2, NH3, acetone, and ethanol molecules adsorbed on a diazine monolayer were studied to develop the application potential of the diazine monolayer as a room-temperature gas sensor for detecting acetone, ethanol, and NH3. We found that these molecules are all physically adsorbed on the diazine monolayer with weak adsorption strength and charge transfer between the molecules and the monolayer, but the physisorption of only NH3, acetone, and ethanol remarkably modified the electronic properties of the diazine monolayer, especially for the obvious change in electric conductivity, showing that the diazine monolayer is highly sensitive to acetone, NH3, and ethanol. Further, the adsorption of NH3, acetone, and ethanol molecules remarkably modifies, in varying degrees, the optical properties of the diazine monolayer, such as work function, absorption coefficient, and the reflectivity, whereas adsorption of other molecules has infinitesimal influence. The different adsorption behaviors and influences of the electronic and optical properties of molecules on the monolayer show that the diazine monolayer has high selectivity to NH3, acetone, and ethanol. The recovery time of NH3, acetone, and ethanol molecules is, respectively, 1.2 µs, 7.7 µs, and 0.11 ms at 300 K. Thus, the diazine monolayer has a high application potential as a room-temperature acetone, ethanol, and NH3 sensor with high performance (high selectivity and sensitivity, and rapid recovery time).

Micromechanical Modeling of Damage Evolution and Mechanical Behaviors of CF/Al Composites under Transverse and Longitudinal Tensile Loadings.

This paper investigates the progressive damage and failure behavior of unidirectional graphite fiber-reinforced aluminum composites (CF/Al composites) under transverse and longitudinal tensile loadings. Micromechanical finite element analyses are carried out using different assumptions regarding fiber, matrix alloy, and interface properties. The validity of these numerical analyses is examined by comparing the predicted stress-strain curves with the experimental data measured under transverse and longitudinal tensile loadings. Assuming a perfect interface, the transverse tensile strength is overestimated by more than 180% and the transverse fracture induced by fiber failure is unrealistic based on the experimental observations. In fact, the simulation and experiment results indicate that the interface debonding arising from the matrix alloy failure dominates the transverse fracture, and the influence of matrix alloy properties on the mechanical behavior is inconspicuous. In the case of longitudinal tensile testing, however, the characteristic of interface bonding has no significant effect on the macroscopic mechanical response due to the low in-situ strength of the fibers. It is demonstrated that ultimate longitudinal fracture is mainly controlled by fiber failure mechanisms, which is confirmed by the fracture morphology of the tensile samples.