Secondary metabolite profile of Streptomyces spp. changes when grown with the sub-lethal concentration of silver nanoparticles: possible implication in novel compound discovery.

The decline of new antibiotics and the emergence of multidrug resistance in pathogens necessitates a revisit of strategies used for lead compound discovery. This study proposes to induce the production of bioactive compounds with sub-lethal concentrations of silver nanoparticles (Ag-NPs). A total of Forty-two Actinobacteria isolates from four Saudi soil samples were grown with and without sub-lethal concentration of Ag-NPs (50 µg ml-1). The spent broth grown with Ag-NPs, or without Ag-NPs were screened for antimicrobial activity against four bacteria. Interestingly, out of 42 strains, broths of three strains grown with sub-lethal concentration of Ag-NPs exhibit antimicrobial activity against Staphylococcus aureus and Micrococcus luteus. Among these, two strains S4-4 and S4-21 identified as Streptomyces labedae and Streptomyces tirandamycinicus based on 16S rRNA gene sequence were selected for detailed study. The change in the secondary metabolites profile in the presence of Ag-NPs was evaluated using GC-MS and LC-MS analyses. Butanol extracts of spent broth grown with Ag-NPs exhibit strong antimicrobial activity against M. luteus and S. aureus. While the extracts of the controls with the same concentration of Ag-NPs do not show any activity. GC-analysis revealed a clear change in the secondary metabolite profile when grown with Ag-NPs. Similarly, the LC-MS patterns also differ significantly. Results of this study, strongly suggest that sub-lethal concentrations of Ag-NPs influence the production of secondary metabolites by Streptomyces. Besides, LC-MS results identified possible secondary metabolites, associated with oxidative stress and antimicrobial activities. This strategy can be used to possibly induce cryptic biosynthetic gene clusters for the discovery of new lead compounds.

Sb-Doped Cerium Molybdate: An Emerging Material as Dielectric and Photocatalyst for the Removal of Diclofenac Potassium from Aqueous Media.

This work reports the influence of antimony substitution in a cerium molybdate lattice for improved dielectric and photocatalytic properties. For this purpose, a series of Ce2-xSbx(MoO4)3 (x = 0.00, 0.01, 0.03, 0.05, 0.07, and 0.09) were synthesized through a co-precipitation route. The as-synthesized materials were characterized for their optical properties, functional groups, chemical oxidation states, structural phases, surface properties, and dielectric characteristics using UV-Vis spectroscopy (UV-Vis), Fourier transform infrared (FTIR) and Raman spectroscopies, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) analysis, and impedance spectroscopy, respectively. UV-Vis study showed a prominent red shift of absorption maxima and a continuous decrease in band gap (3.35 eV to 2.79 eV) by increasing the dopant concentration. The presence of Ce-O and Mo-O-Mo bonds, detected via FTIR and Raman spectroscopies, are confirmed, indicating the successful synthesis of the desired material. The monoclinic phase was dominant in all materials, and the crystallite size was decreased from 40.29 nm to 29.09 nm by increasing the Sb content. A significant increase in the dielectric constant (ε' = 2.856 × 108, 20 Hz) and a decrease in the loss tan (tanδ = 1.647, 20 Hz) were exhibited as functions of the increasing Sb concentration. Furthermore, the photocatalytic efficiency of pristine cerium molybdate was also increased by 1.24 times against diclofenac potassium by incorporating Sb (x = 0.09) in the cerium molybdate. The photocatalytic efficiency of 85.8% was achieved within 180 min of UV light exposure at optimized conditions. The photocatalytic reaction followed pseudo-first-order kinetics with an apparent rate constant of 0.0105 min-1, and the photocatalyst was recyclable with good photocatalytic activity even after five successive runs. Overall, the as-synthesized Sb-doped cerium molybdate material has proven to be a promising candidate for charge storage devices and a sustainable photocatalyst for wastewater treatment.

Coarse-Grained Simulations on Polyethylene Crystal Network Formation and Microstructure Analysis.

Understanding and characterizing semi-crystalline models with crystalline and amorphous segments is crucial for industrial applications. A coarse-grained molecular dynamics (CGMD) simulations study probed the crystal network formation in high-density polyethylene (HDPE) from melt, and shed light on tensile properties for microstructure analysis. Modified Paul-Yoon-Smith (PYS/R) forcefield parameters are used to compute the interatomic forces among the PE chains. The isothermal crystallization at 300 K and 1 atm predicts the multi-nucleus crystal growth; moreover, the lamellar crystal stems and amorphous region are alternatively oriented. A one-dimensional density distribution along the alternative lamellar stems further confirms the ordering of the lamellar-stack orientation. Using this plastic model preparation approach, the semi-crystalline model density (ρcr) of ca. 0.913 g·cm-3 and amorphous model density (ρam) of ca. 0.856 g·cm-3 are obtained. Furthermore, the ratio of ρcr/ρam ≈ 1.06 is in good agreement with computational (≈1.096) and experimental (≈1.14) data, ensuring the reliability of the simulations. The degree of crystallinity (χc) of the model is ca. 52% at 300 K. Nevertheless, there is a gradual increase in crystallinity over the specified time, indicating the alignment of the lamellar stems during crystallization. The characteristic stress-strain curve mimicking tensile tests along the z-axis orientation exhibits a reversible sharp elastic regime, tensile strength at yield ca. 100 MPa, and a non-reversible tensile strength at break of 350%. The cavitation mechanism embraces the alignment of lamellar stems along the deformation axis. The study highlights an explanatory model of crystal network formation for the PE model using a PYS/R forcefield, and it produces a microstructure with ordered lamellar and amorphous segments with robust mechanical properties, which aids in predicting the microstructure-mechanical property relationships in plastics under applied forces.

Preparation and Characterization of High-Density Polyethylene with Alternating Lamellar Stems Using Molecular Dynamics Simulations.

Mechanical recycling is the most efficient way to reduce plastic pollution due to its ability to maintain the intrinsic properties of plastics as well as provide economic benefits involved in other types of recycling. On the other hand, molecular dynamics (MD) simulations provide key insights into structural deformation, lamellar crystalline axis (c-axis) orientations, and reorganization, which are essential for understanding plastic behavior during structural deformations. To simulate the influence of structural deformations in high-density polyethylene (HDPE) during mechanical recycling while paying attention to obtaining an alternate lamellar orientation, the authors examine a specific way of preparing stacked lamella-oriented HDPE united atom (UA) models, starting from a single 1000 UA (C1000) chain of crystalline conformations and then packing such chain conformations into 2-chain, 10-chain, 15-chain, and 20-chain semi-crystalline models. The 2-chain, 10-chain, and 15-chain models yielded HDPE microstructures with the desired alternating lamellar orientations and entangled amorphous segments. On the other hand, the 20-chain model displayed multi-nucleus crystal growth instead of the lamellar-stack orientation. Structural characterization using a one-dimensional density profile and local order parameter {P2(r)} analyses demonstrated lamellar-stack orientation formation. All semi-crystalline models displayed the total density (ρ) and degree of crystallinity (χ) range of 0.90-0.94 g/cm-3 and ≥42-45%, respectively. A notable stress yield (σ_yield) ≈ 100-120 MPa and a superior elongation at break (ε_break) ~250% was observed under uniaxial strain deformation along the lamellar-stack orientation. Similarly, during the MD simulations, the microstructure phase change represented the average number of entanglements per chain (). From the present study, it can be recommended that the 10-chain alternate lamellar-stack orientation model is the most reliable miniature model for HDPE that can mimic industrially relevant plastic behavior in various conditions.

Solvothermal synthesis of VO2 nanoparticles with locally patched V2O5 surface layer and their morphology-dependent catalytic properties for the oxidation of alcohols.

Vanadium oxides are promising oxidation catalysts because of their rich redox chemistry. We report the synthesis of VO2 nanocrystals with VO2(B) crystal structure. By varying the mixing ratio of the components of a binary ethanol/water mixture, different VO2 nanocrystal morphologies (nanorods, -urchins, and -sheets) could be made selectively in pure form. Polydisperse VO2(B) nanorods with lengths between 150 nm and a few micrometers were formed at large water : ethanol ratios between 4 : 1 and 3 : 2. At a water : ethanol ratio of 1 : 9 VO2 nanosheets with diameters of ∼50-70 nm were formed, which aggregated to nano-urchins with diameters of ∼200 nm in pure ethanol. The catalytic activity of VO2 nanocrystals for the oxidation of alcohols was studied as a function of nanocrystal morphology. VO2 nanocrystals with all morphologies were catalytically active. The activity for the oxidation of benzyl alcohol to benzaldehyde was about 30% higher than that for the oxidation of furfuryl alcohol to furfural. This is due to the substrate structure. The oxidation activity of VO2 nanostructures decreases in the order of nanourchins > nanosheets > nanorods.

Green, Solvent-Free Mechanochemical Synthesis of Nano Ag2O/MnO2/N-Doped Graphene Nanocomposites: An Efficient Catalyst for Additive-Base-Free Aerial Oxidation of Various Kinds of Alcohols.

Herein, we report a solvent-less, straightforward, and facile mechanochemical technique to synthesize nanocomposites of Ag2O nanoparticles-doped MnO2, which is further codoped with nitrogen-doped graphene (N-DG) [i.e., (X %)N-DG/MnO2-(1% Ag2O)] using physical milling of separately prepared N-DG and Ag2O NPs-MnO2 annealed at 400 °C over an eco-friendly ball-mill process. To assess the efficiency in terms of catalytic performance of the nanocomposites, selective oxidation of benzyl alcohol (BlOH) to benzaldehyde (BlCHO) is selected as a substrate model with an eco-friendly oxidizing agent (O2 molecule) and without any requirements for the addition of any harmful additives or bases. Various nanocomposites were prepared by varying the amount of N-DG in the composite, and the results obtained highlighted the function of N-DG in the catalyst system when they are compared with the catalyst MnO2-(1% Ag2O) [i.e., undoped catalyst] and MnO2-(1% Ag2O) codoped with different graphene dopants such as GRO and H-RG for alcohol oxidation transformation. The effects of various catalytic factors are systematically evaluated to optimize reaction conditions. The N-DG/MnO2-(1% Ag2O) catalyst exhibits premium specific activity (16.0 mmol/h/g) with 100% BlOH conversion and <99.9% BlCHO selectivity within a very short interval. The mechanochemically prepared N-DG-based nanocomposite displayed higher catalytic efficacy than that of the MnO2-(1% Ag2O) catalyst without the graphene dopant, which is N-DG in this study. A wide array of aromatic, heterocyclic, allylic, primary, secondary, and aliphatic alcohols have been selectively converted to respective ketones and aldehydes with full convertibility without further oxidation to acids over N-DG/MnO2-(1% Ag2O). Interestingly, it is also found that the N-DG/MnO2-(1% Ag2O) can be efficiently reused up to six times without a noteworthy decline in its effectiveness. The prepared nanocomposites were characterized using various analytical, microscopic, and spectroscopic techniques such as X-ray diffraction, thermogravimetric analysis, Fourier-transform infrared spectroscopy, Raman, field emission scanning electron microscopy, and Brunauer-Emmett-Teller.