Planar Iron Hydride Nanoclusters: Combined Spectroscopic and Theoretical Insights into Structures and Building Principles

The controlled assembly of well-defined planar nanoclusters from molecular precursors is synthetically challenging and often plagued by the predominant formation of 3D-structures and nanoparticles. Herein, we report planar iron hydride nanoclusters from reactions of main group element hydrides with iron(II) bis(hexamethyldisilazide). The structures and properties of isolated Fe₄, Fe₆, and Fe₇ nanoplatelets and calculated intermediates enable an unprecedented insight into the underlying building principle and growth mechanism of iron clusters, metal monolayers, and nanoparticles.     

Isomer-Specific Vibrational Spectroscopy of Microhydrated Lithium Dichloride Anions: Spectral Fingerprint of Solvent-Shared Ion Pairs

The vibrational spectroscopy of lithium dichloride anions microhydrated with one to three water molecules, [LiCl₂(H₂O)_1–3]⁻, is studied in the OH stretching region (3800–2800 cm⁻¹) using isomer-specific IR/IR double-resonance population labelling experiments. The spectroscopic fingerprints of individual isomers can only be unambiguously assigned after anharmonic effects are considered, but then yield molecular level insight into the onset of salt dissolution in these gas phase model systems. Based on the extent of the observed frequency shifts Δν^OH of the hydrogen-bonded OH stretching oscillators solvent-shared ion pair motifs (<3200 cm⁻¹) can be distinguished from intact-core structures (>3200 cm⁻¹). The characteristic fingerprint of a water molecule trapped directly in-between two ions of opposite charge provides an alternative route to evaluate the extent of ion pairing in aqueous electrolyte solutions.     

Palatability Enhancement Potential of Hermetia illucens Larvae Protein Hydrolysate in Litopenaeus vannamei Diets

Marine feed ingredients derived from cephalopods (e.g., squid) and crustaceans (e.g., krill) are commercially used to improve the palatability of shrimp diets. Increase in global demand for shrimps has resulted in overfishing of these marine organisms and is a matter of concern. Insect protein hydrolysate could be a sustainable alternative for the possible replacement of these marine feed ingredients. During this study, four formulations: diet A (control: not containing any palatability enhancer), diet B (containing squid meal and krill oil), diet C (containing 1% insect protein hydrolysate), and diet D (containing 2% insect protein hydrolysate) were tested for (1) time required by first subject to begin feeding (time to strike) and (2) palatability in Litopenaeus vannamei. Additionally, the chemical composition of all four diet formulations was also analyzed. Results indicate that all diets had similar crude composition. The major essential amino acids in all diets were leucine and lysine, whereas eicosapentaenoic acid was the major omega-3 fatty acid in all diets. There were no significant differences between the mean time to strike for all the tested formulations. Palatability of tested formulations was found in the following order: diet D > diet C > diet B = diet A (p < 0.05), indicating that addition of squid meal and krill oil has no effect on palatability in comparison to control, whereas inclusion of insect protein hydrolysates significantly improves the palatability of formulations. Palatability enhancement potential of insect protein hydrolysate could be attributed to the high free amino acid content and water solubility in comparison to squid meal.     

Fabrication and Characterization of Zinc Oxide Nanowire Based Two-electrode Capacitive Biosensors on Flexible Substrates for Estimating Glucose Content in a Sample

The present work deals with fabrication and characterization of the zinc oxide (ZnO) nanowire based novel two-electrode capacitive biosensors on flexible Polyethylene terephthalate (PET) substrates for accurate estimation of glucose by analyzing the fundamental dielectric nature of the relevant sample. The morphology and crystalline quality of grown nanowires are analyzed by using field-emission scanning electron microscope (FESEM) and X-ray diffractometer (XRD), respectively. Current and capacitance values of the device have been studied for ten different glucose concentrations relevant to the physiological standards. The analytical performance of the devices in terms of enzyme activity, reliability and flexibility has also been evaluated.     

Coulomb screening in graphene with topological defects

We analyze the screening of an external Coulomb charge in gapless graphene cone, which is taken as a prototype of a topological defect. In the subcritical regime, the induced charge is calculated using both the Green’s function and the Friedel sum rule. The dependence of the polarization charge on the Coulomb strength obtained from the Green’s function clearly shows the effect of the conical defect and indicates that the critical charge itself depends on the sample topology. Similar analysis using the Friedel sum rule indicates that the two results agree for low values of the Coulomb charge but differ for the higher strengths, especially in the presence of the conical defect. For a given subcritical charge, the transport cross-section has a higher value in the presence of the conical defect. In the supercritical regime we show that the coefficient of the power law tail of polarization charge density can be expressed as a summation of functions which vary log periodically with the distance from the Coulomb impurity. The period of variation depends on the conical defect. In the presence of the conical defect, the Fano resonances begin to appear in the transport cross-section for a lower value of the Coulomb charge. For both sub and supercritical regime we derive the dependence of LDOS on the conical defect. The effects of generalized boundary condition on the physical observables are also discussed.     

Spectroscopic and Computational Study of a Nonheme Iron Nitrosyl Center in a Biosynthetic Model of Nitric Oxide Reductase

A major barrier to understanding the mechanism of nitric oxide reductases (NORs) is the lack of a selective probe of NO binding to the nonheme Fe_B center. By replacing the heme in a biosynthetic model of NORs, which structurally and functionally mimics NORs, with isostructural ZnPP, the electronic structure and functional properties of the Fe_B nitrosyl complex was probed. This approach allowed observation of the first S=3/2 nonheme {FeNO}⁷ complex in a protein‐based model system of NOR. Detailed spectroscopic and computational studies show that the electronic state of the {FeNO}⁷ complex is best described as a high spin ferrous iron (S=2) antiferromagnetically coupled to an NO radical (S= 1/2) [Fe²⁺‐NO^.]. The radical nature of the Fe_B‐bound NO would facilitate N? N bond formation by radical coupling with the heme‐bound NO. This finding, therefore, supports the proposed trans mechanism of NO reduction by NORs.     

Surface Design for Immobilization of an Antimicrobial Peptide Mimic for Efficient Anti-Biofouling

Microbial surface attachment negatively impacts a wide range of devices from water purification membranes to biomedical implants. Mimics of antimicrobial peptides (AMPs) constituted from poly(N-substituted glycine) „peptoids“ are of great interest as they resist proteolysis and can inhibit a wide spectrum of microbes. We investigate how terminal modification of a peptoid AMP-mimic and its surface immobilization affect antimicrobial activity. We also demonstrate a convenient surface modification strategy for enabling alkyne–azide „click“ coupling on amino-functionalized surfaces. Our results verified that the N- and C-terminal peptoid structures are not required for antimicrobial activity. Moreover, our peptoid immobilization density and choice of PEG tether resulted in a „volumetric“ spatial separation between AMPs that, compared to past studies, enabled the highest AMP surface activity relative to bacterial attachment. Our analysis suggests the importance of spatial flexibility for membrane activity and that AMP separation may be a controlling parameter for optimizing surface anti-biofouling.     

Optimization of ultrasound-assisted extraction of phenolic compounds from Sesamum indicum

Abstract

Effective extraction of phyto-biomolecules insures retaining maximum functionality along with higher recovery. In this study, ultrasound-solvent assisted extraction (USAE) was employed for optimal extraction of phyto-biomolecules from Sesamum indicum (sesame) leaves using the approach of Response Surface Methodology (RSM). The optimized condition of 200?W power, 59% methanol concentration with 1:14?g/mL solid–liquid ratio and 15?min of extraction time yielded 367.39?±?1.85?mg GAE/100?g of total phenolic content, 96.72?±?3.27% of free radical scavenging activity and 81.20?±?2.87% of iron chelating activity respectively. The extract consist of essential phytocomponents like gallic acid, chlorogenic acid, and quercetin with lipid peroxidation activities of >50% over incubation time of 48?h. Also, showed antimicrobial activity against various Gram’s negative and positive food borne pathogens. The results of this study implied the importance of USAE for effective and optimum recovery of phyto-biomolecules from Sesame leaves with retained functional properties.     

A Low‐Temperature Molecular Precursor Approach to Copper‐Based Nano‐Sized Digenite Mineral for Efficient Electrocatalytic Oxygen Evolution Reaction

In the urge of designing noble metal‐free and sustainable electrocatalysts for oxygen evolution reaction (OER), herein, a mineral Digenite Cu₉S₅ has been prepared from a molecular copper(I) precursor, [{(PyHS)₂Cu^I(PyHS)}₂](OTf)₂ ( 1 ), and utilized as an anode material in electrocatalytic OER for the first time. A hot injection of 1 yielded a pure phase and highly crystalline Cu₉S₅, which was then electrophoretically deposited (EPD) on a highly conducting nickel foam (NF) substrate. When assessed as an electrode for OER, the Cu₉S₅/NF displayed an overpotential of merely 298±3 mV at a current density of 10 mA cm^?2 in alkaline media. The overpotential recorded here supersedes the value obtained for the best reported Cu‐based as well as the benchmark precious‐metal‐based RuO₂ and IrO₂ electrocatalysts. In addition, the choronoamperometric OER indicated the superior stability of Cu₉S₅/NF, rendering its suitability as the sustainable anode material for practical feasibility. The excellent catalytic activity of Cu₉S₅ can be attributed to the formation of a crystalline CuO overlayer on the conductive Cu₉S₅ that behaves as active species to facilitate OER. This study delivers a distinct molecular precursor approach to produce highly active copper‐based catalysts that could be used as an efficient and durable OER electro(pre)catalysts relying on non‐precious metals.