Interrelationship of lipid aldehydes (MDA, 4-HNE, and 4-ONE) mediated protein oxidation in muscle foods.

Proteins and essential fatty acids are crucial components of the human diet. However, lipids and proteins are susceptible to oxidative modification during food processing resulting in changes to their structural characteristics and functional properties. Food products rich in polyunsaturated fatty acids are highly susceptible to lipid peroxidation and generate bifunctional reactive aldehydes. Bifunctional aldehydes such as malondialdehyde (MDA), 4-hydroxy-2-nonenal (4-HNE), and 4-oxo-2-nonenal (4-ONE) readily bind to protein nucleophiles and lead to intra- or intermolecular protein cross-linking. In comparison with lipid oxidation, the degradation of proteins by prooxidants appears to be more intricate and results in a greater diversity of oxidation products. Although individual oxidation processes involving lipids and proteins received increasing attention in the past decades, the interactions between those aldehydes and protein oxidation in food have not been extensively explored. Studies indicate that the reactions of lipid and protein oxidation may take place simultaneously or independently, but oxidation products that arose from one reaction may further interact with lipids or proteins. The present review presents a perspective on reactive aldehydes and the role of aldehydes in inducing protein oxidation in muscle foods. Emphasis is focused on the interaction mechanism of the lipid, protein, and myoglobin protein oxidations. In addition, the occurrence of aldehydes derived from lipid oxidation in food systems as well as the endogenous antioxidant peptides or amino acids in meat and plant proteins are also briefly described.

Transition-Metal-Free Transfer Hydrogenative Cascade Reaction of Nitroarenes with Amines/Alcohols: Redox-Economical Access to Benzimidazoles.

This report describes an efficient transition-metal-free process toward the transfer hydrogenative cascade reaction between nitroarenes and amines or alcohols. The developed redox-economical approach was realized using a combination of KOtBu and Et3SiH as reagents, which allows the synthesis of benzimidazole derivatives via σ-bond metathesis. The reaction conditions hold well over a wide range of substrates embedded with diverse functional groups to deliver the desired products in good to excellent yields. The mechanistic proposal has been depicted on the basis of a series of control experiments, mass spectroscopic evidence which is well supported by density functional theory (DFT) calculations with a feasible energy profile.

Growth of lateral graphene/h-BN heterostructure on copper foils by chemical vapor deposition.

The synthesis of lateral heterostructures assembled by atomically-thin materials with distinct intrinsic properties is important for future heterojunction-embedded two-dimensional (2D) devices. Here we report an etching-assisted chemical vapor deposition method to synthesize large-area continuous lateral graphene/hexagonal boron nitride (Gr/h-BN) heterostructures on carbon-containing copper foils. The h-BN film is first synthesized on the copper foil, followed by hydrogen etching, and then epitaxial graphene domains are grown to form continuous lateral heterostructures. Analyses, including Raman spectroscopy, atomic force microscopy, scanning electron microscopy, x-ray photoelectron spectroscopy, and ultraviolet-visible absorption spectroscopy, are used to characterize the coexistence of both materials and the highly continuous nature of this lateral heterostructure. This facile and scalable synthesizing method enables the potential usage of Gr/h-BN heterostructure in both fundamental studies and related 2D devices.

High density nonmagnetic cobalt in thin films.

Recently high density (HD) nonmagnetic cobalt has been discovered in a nanoscale cobalt thin film, grown on Si(111) single crystal. This form of cobalt is not only nonmagnetic but also superconducting. These promising results have encouraged further investigations of the growth of the nonmagnetic (NM) phase of cobalt. In the original investigation, the cobalt film had a natural cobalt oxide at the top. We have investigated whether the growth of HD NM cobalt layers in the thin film depends on (i) a capping layer on the cobalt film, (ii) the thickness of the cobalt film and (iii) the nature of the substrate on which the cobalt film is grown. The results of such investigations indicate that for cobalt films capped with a thin gold layer, and for various film thicknesses, HD NM cobalt layers are formed. However, instead of a Si substrate, when the cobalt films are grown on oxide substrates, such as silicon oxide or cobalt oxide, HD NM cobalt layers are not formed. The difference is attributed to the nature-crystalline or amorphous-of the substrate.

Air Stable Doping and Intrinsic Mobility Enhancement in Monolayer Molybdenum Disulfide by Amorphous Titanium Suboxide Encapsulation.

To reduce Schottky-barrier-induced contact and access resistance, and the impact of charged impurity and phonon scattering on mobility in devices based on 2D transition metal dichalcogenides (TMDs), considerable effort has been put into exploring various doping techniques and dielectric engineering using high-κ oxides, respectively. The goal of this work is to demonstrate a high-κ dielectric that serves as an effective n-type charge transfer dopant on monolayer (ML) molybdenum disulfide (MoS2). Utilizing amorphous titanium suboxide (ATO) as the "high-κ dopant", we achieved a contact resistance of ∼180 Ω·µm that is the lowest reported value for ML MoS2. An ON current as high as 240 µA/µm and field effect mobility as high as 83 cm(2)/V-s were realized using this doping technique. Moreover, intrinsic mobility as high as 102 cm(2)/V-s at 300 K and 501 cm(2)/V-s at 77 K were achieved after ATO encapsulation that are among the highest mobility values reported on ML MoS2. We also analyzed the doping effect of ATO films on ML MoS2, a phenomenon that is absent when stoichiometric TiO2 is used, using ab initio density functional theory (DFT) calculations that shows excellent agreement with our experimental findings. On the basis of the interfacial-oxygen-vacancy mediated doping as seen in the case of high-κ ATO-ML MoS2, we propose a mechanism for the mobility enhancement effect observed in TMD-based devices after encapsulation in a high-κ dielectric environment.

Expanded porous-starch matrix as an alternative to porous starch granule: Present status, challenges, and future prospects.

Exposing the hydrated-soft-starch matrix of intact grain or reconstituted flour dough to a high-temperature-short-time (HTST) leads to rapid vapor generation that facilitates high-pressure build-up in its elastic matrix linked to large deformation and expansion. The expanded starch matrix at high temperatures dries up quickly by flash vaporization of water, which causes loss of its structural flexibility and imparts a porous and rigid structure of the expanded porous starch matrix (EPSM). EPSM, with abundant pores in its construction, offers adsorptive effectiveness, solubility, swelling ability, mechanical strength, and thermal stability. It can be a sustainable and easy-to-construct alternative to porous starch (PS) in food and pharmaceutical applications. This review is a comparative study of PS and EPSM on their preparation methods, structure, and physicochemical properties, finding compatibility and addressing challenges in recommending EPSM as an alternative to PS in adsorbing, dispersing, stabilizing, and delivering active ingredients in a controlled and efficient way.

Raman Spectroscopic Insights of Phase-Separated Insulin Aggregates.

Phase-separated protein accumulation through the formation of several aggregate species is linked to the pathology of several human disorders and diseases. Our current investigation envisaged detailed Raman signature and structural intricacy of bovine insulin in its various forms of aggregates produced in situ at an elevated temperature (60 °C). The amide I band in the Raman spectrum of the protein in its native-like conformation appeared at 1655 cm-1 and indicated the presence of a high content of α-helical structure as prepared freshly in acidic pH. The disorder content (turn and coils) also was predominately present in both the monomeric and oligomeric states and was confirmed by the presence shoulder amide I maker band at ∼1680 cm-1. However, the band shifted to ∼1671 cm-1 upon the transformation of the protein solution into fibrillar aggregates as produced for a longer time of incubation. The protein, however, maintained most of its helical conformation in the oligomeric phase; the low-frequency backbone α-helical conformation signal at ∼935 cm-1 was similar to that of freshly prepared aqueous protein solution enriched in helical conformation. The peak intensity was significantly weak in the fibrillar aggregates, and it appeared as a good Raman signature to follow the phase separation and the aggregation behavior of insulin and similar other proteins. Tyrosine phenoxy moieties in the protein may maintained its H-bond donor-acceptor integrity throughout the course of fibril formation; however, it entered in more hydrophobic environment in its journey of fibril formation. In addition, it was noticed that oligomeric bovine insulin maintained the orientation/conformation of the disulfide bonds. However, in the fibrillar state, the disulfide linkages became more strained and preferred to maintain a single conformation state.

Low-Temperature Synthesis of WSe2 by the Selenization Process under Ultrahigh Vacuum for BEOL Compatible Reconfigurable Neurons.

Low-temperature large-area growth of two-dimensional (2D) transition-metal dichalcogenides (TMDs) is critical for their integration with silicon chips. Especially, if the growth temperatures can be lowered below the back-end-of-line (BEOL) processing temperatures, the Si transistors can interface with 2D devices (in the back end) to enable high-density heterogeneous circuits. Such configurations are particularly useful for neuromorphic computing applications where a dense network of neurons interacts to compute the output. In this work, we present low-temperature synthesis (400 °C) of 2D tungsten diselenide (WSe2) via the selenization of the W film under ultrahigh vacuum (UHV) conditions. This simple yet effective process yields large-area, homogeneous films of 2D TMDs, as confirmed by several characterization techniques, including reflection high-energy electron diffraction, atomic force microscopy, transmission electron microscopy, and different spectroscopy methods. Memristors fabricated using the grown WSe2 film are leveraged to realize a novel compact neuron circuit that can be reconfigured to enable homeostasis.

Ultra-fast switching memristors based on two-dimensional materials.

The ability to scale two-dimensional (2D) material thickness down to a single monolayer presents a promising opportunity to realize high-speed energy-efficient memristors. Here, we report an ultra-fast memristor fabricated using atomically thin sheets of 2D hexagonal Boron Nitride, exhibiting the shortest observed switching speed (120 ps) among 2D memristors and low switching energy (2pJ). Furthermore, we study the switching dynamics of these memristors using ultra-short (120ps-3ns) voltage pulses, a frequency range that is highly relevant in the context of modern complementary metal oxide semiconductor (CMOS) circuits. We employ statistical analysis of transient characteristics to gain insights into the memristor switching mechanism. Cycling endurance data confirms the ultra-fast switching capability of these memristors, making them attractive for next generation computing, storage, and Radio-Frequency (RF) circuit applications.

Simultaneous presence of both open metal sites and free functional organic sites in a noncentrosymmetric dynamic metal-organic framework with bimodal catalytic and sensing activities.

Assimilation of open metal sites (OMSs) and free functional organic sites (FOSs) with a framework strut has opened up a new route for the fabrication of novel metal-organic materials, thereby providing a unique opportunity to explore their multiple functionalities. A new metal-organic framework (MOF), {[Cu(ina)2(H2O)][Cu(ina)2(bipy)]·2H2O}n (1) (ina=isonicotinate, bipy=4,4'-bipyridine), has been synthesized and characterized. Complex 1 is crystallized in the orthorhombic noncentrosymmetric space group Aba2 and consists of two different 2D coordination polymers, [Cu(ina)2(H2O)]n and [Cu(ina)2(bipy)]n, with entrapped solvent water molecules. Hydrogen-bonding interactions assemble these two different 2D coordination layers in a single-crystal structure with interdigitation of pendant 4,4'-bipy from one layer into the groove of another. Upon removal of guest molecules, 1 undergoes a structural transformation in single-crystal-to-single-crystal fashion with expansion of the effective void space. Each metal center is five-coordinated and thus can potentially behave as an OMS, and the free pyridyl groups of pendant 4,4'-bipy moieties and free -C=O groups can act as free FOSs. Thus, owing to presence of both OMSs and free FOSs, the framework exhibits multifunctional properties. Owing to the presence of OMSs, the framework can act as a Lewis acid catalyst as well as a small-molecule sensor material, and in a similar way, owing to the presence of free FOSs, it performs as a Lewis base catalyst and a cation sensor material. Furthermore, owing to noncentrosymmetry with large polarity along a particular direction, it shows strong second-harmonic generation/nonlinear optical (SHG-NLO) activity.

Enhancing micronutrient absorption through simultaneous fortification and phytic acid degradation.

Phytic acid (PA), an endogenous antinutrient in cereals and legumes, hinders mineral absorption by forming less bioavailable, stable PA-mineral complexes. For individual micronutrients, the PA-to-mineral molar ratio below the critical level ensures better bioavailability and is achieved by adding minerals or removing PA from cereals and pulses. Although several PA reduction and fortification strategies are available, the inability to completely eradicate or degrade PA using available techniques always subdues fortification's impact by hindering fortified micronutrient absorption. The bioavailability of micronutrients could be increased through simultaneous PA degradation and fortification. Following primary PA reduction of the raw material, the fortification step should also incorporate additional essential control stages to further PA inactivation, improving micronutrient absorption. In this review, the chemistry of PA interaction with metal ions, associated controlling parameters, and its impact on PA reduction during fortification is also evaluated, and further suggestions were made for the fortification's success.

Cryo-EM-based structural insights into supramolecular assemblies of γ-hemolysin from S. aureus reveal the pore formation mechanism.

γ-Hemolysin (γ-HL) is a hemolytic and leukotoxic bicomponent ß-pore-forming toxin (ß-PFT), a potent virulence factor from the Staphylococcus aureus Newman strain. In this study, we performed single-particle cryoelectron microscopy (cryo-EM) of γ-HL in a lipid environment. We observed clustering and square lattice packing of octameric HlgAB pores on the membrane bilayer and an octahedral superassembly of octameric pore complexes that we resolved at resolution of 3.5 Å. Our atomic model further demonstrated the key residues involved in hydrophobic zipping between the rim domains of adjacent octameric complexes, providing additional structural stability in PFTs post oligomerization. We also observed extra densities at the octahedral and octameric interfaces, providing insights into the plausible lipid-binding residues involved for HlgA and HlgB components. Furthermore, the hitherto elusive N-terminal region of HlgA was also resolved in our cryo-EM map, and an overall mechanism of pore formation for bicomponent ß-PFTs is proposed.

Synthesis of indene-fused spiro-dibenz(ox)azepines via Rh(III)-catalyzed cascade regioselective C-H activation/annulation.

We report an unprecedented atom-economic one-pot Cp*Rh(III)-catalyzed regioselective [3+2]-spiroannulation reaction between dibenz(ox)azepines and ynones, allowing the synthesis of biologically relevant novel spirocyclic dibenz(ox)azepines under operationally simple and mild reaction conditions. The reaction proceeds without any silver additive or external oxidant implementing a redox-neutral pathway. A broad substrate scope with diverse functional group tolerance permitted the regioselective synthesis of a wide spectrum of indene-containing spirocyclic dibenz(ox)azepines in good to excellent yields. Also, we showcased detailed mechanistic studies to justify the formation of spirocycles. In addition, the synthetic utility of this process was also demonstrated by the modular synthesis of various steroid conjugates.

Fucose-containing Abroma augusta mucilage hydrogel as a potential probiotic carrier with prebiotic function.

The mucilaginous polysaccharide from Abroma augusta stem was examined for its physicochemical, thermal, and functional behavior and explored as a carrier for probiotic bacteria. Composed of glucose, galactose, rhamnose, galactouronic acid and fucose, Abroma augusta mucilage (AAM) exhibited shear thinning behavior (following power law equation) and gel like characteristic (showing higher G' value than G″ value). AAM promoted the growth of probiotic strains with positive prebiotic scores of 0.5 ± 0.06 and 0.51 ± 0.05 for Lactobacillus acidophilus and Lactobacillus casei, respectively. Further, probiotic strains were embedded in the AAM matrix followed by freeze-drying with embedding efficiency of >95%. Viscoelastic properties were retained substantially in the rehydrated probiotic-embedded matrix. AAM could protect probiotic bacteria in simulated gastrointestinal conditions, at elevated (80 °C, 20 min) and at low (4 °C, 4 months) temperatures ensuring higher viabilities of embedded probiotic cells. Our findings established potential carrier capabilities of AAM polysaccharides for probiotic bacteria with thickening and prebiotic activity.

Wafer-Scalable Single-Layer Amorphous Molybdenum Trioxide.

Molybdenum trioxide (MoO3), an important transition metal oxide (TMO), has been extensively investigated over the past few decades due to its potential in existing and emerging technologies, including catalysis, energy and data storage, electrochromic devices, and sensors. Recently, the growing interest in two-dimensional (2D) materials, often rich in interesting properties and functionalities compared to their bulk counterparts, has led to the investigation of 2D MoO3. However, the realization of large-area true 2D (single to few atom layers thick) MoO3 is yet to be achieved. Here, we demonstrate a facile route to obtain wafer-scale monolayer amorphous MoO3 using 2D MoS2 as a starting material, followed by UV-ozone oxidation at a substrate temperature as low as 120 °C. This simple yet effective process yields smooth, continuous, uniform, and stable monolayer oxide with wafer-scale homogeneity, as confirmed by several characterization techniques, including atomic force microscopy, numerous spectroscopy methods, and scanning transmission electron microscopy. Furthermore, using the subnanometer MoO3 as the active layer sandwiched between two metal electrodes, we demonstrate the thinnest oxide-based nonvolatile resistive switching memory with a low voltage operation and a high ON/OFF ratio. These results (potentially extendable to other TMOs) will enable further exploration of subnanometer stoichiometric MoO3, extending the frontiers of ultrathin flexible oxide materials and devices.

Intermediate Cu-O-Si Phase in the Cu-SiO2/Si(111) System: Growth, Elemental, and Electrical Studies.

We investigate here the strain-induced growth of Cu at 600 °C and its interactions with a thermally grown, 270 nm-thick SiO2 layer on the Si(111) substrate. Our results show clear evidence of triangular voids and formation of triangular islands on the surface via a void-filling mechanism upon Cu deposition, even on a 270 nm-thick dielectric. Different coordination states, oxidation numbers, and chemical compositions of the Cu-grown film are estimated from the core level X-ray photoelectron spectroscopy (XPS) measurements. We find evidence of different compound phases including an intermediate mixed-state of Cu-O-Si at the interface. Emergence of a mixed Cu-O-Si intermediate state is attributed to the new chemical states of Cu x+, O x , and Si x+ observed in the high-resolution XPS spectra. This intermediate state, which is supposed to be highly catalytic, is found in the sample with a concentration as high as ∼41%. Within the Cu-O-Si phase, the atomic percentages of Cu, O, and Si are ∼1, ∼86, and ∼13%, respectively. The electrical measurements carried out on the sample reveal different resistive channels across the film and an overall n-type semiconducting nature with a sheet resistance of the order of 106 Ω.

Considerations for improvising fortified extruded rice products.

Micronutrient fortification of rice by extrusion is an effective strategy to enhance micronutrient levels within rice-consuming individuals. The success of extrusion-based fortification is associated with micronutrient retention, enhanced bioavailability, low postprocessing losses, prolonged storage stability, and minimal sensory changes. The success of an optimally fortified product is primarily reliant upon the compositional considerations, but many attributes of extrudates can be indebted to the processing parameters too. Hence, an exhaustive investigation of this technology has been taken-up here, emphasizing on the compositional parameters in association with process parameters, which influence the final quality attributes like nutrient stability, bioavailability, and sensory properties. Based on these attributes of the end product, a collected data have been presented here to bring out the optimal compositional requirements. These together with cooking processes, extrusion process parameters, and storage conditions will enable formulate a product with enhanced sensory acceptance, better retention during cooking and storage, improved texture, and acceptable color. This review will thus help to optimize a need-based product, its quality, and enhance benefits of fortified extruded rice products.

Two-Step Growth of Uniform Monolayer MoS2 Nanosheets by Metal-Organic Chemical Vapor Deposition.

To achieve large area growth of transition metal dichalcogenides of uniform monolayer thickness, we demonstrate metal-organic chemical vapor deposition (MOCVD) growth under low pressure followed by a high-temperature sulfurization process under atmospheric pressure (AP). Following sulfurization, the MOCVD-grown continuous MoS2 film transforms into compact triangular crystals of uniform monolayer thickness as confirmed from the sharp distinct photoluminescence peak at 1.8 eV. Raman and X-ray photoelectron spectroscopies confirm that the structural disorders and chalcogen vacancies inherent to the as-grown MOCVD film are substantially healed and carbon/oxygen contaminations are heavily suppressed. The as-grown MOCVD film has a Mo/S ratio of 1:1.6 and an average defect length of ∼1.56 nm, which improve to 1:1.97 and ∼21 nm, respectively, upon sulfurization. The effect of temperature and duration of the sulfurization process on the morphology and stoichiometry of the grown film is investigated in detail. Compared to the APCVD growth, this two-step growth process shows more homogenous distribution of the triangular monolayer MoS2 domains across the entire substrate, while demonstrating comparable electrical performance.

Whole grain rice fortification as a solution to micronutrient deficiency: Technologies and need for more viable alternatives.

Rice fortification is an effective and economical strategy to increase micronutrient intakein countries where rice is a staple food. A successful fortification technology should deliver substantial micronutrient content, high bioavailability, stability during storage, and retention in sensory attributes. This article provides an extensive review of the available whole-grain fortification technologies conducted at the pre and post-harvest stages of rice processing. Soaking, parboiling, coating, germination, foliar spray, fertilization, dusting are some of the non-destructive techniques extensively employed for rice fortification with Fe, Zn, Ca, Se, I, vitamins and other micronutrients.An in-depth analysis has been taken-up on processing parameters,required facilities, and additives required. Conclusions have been drawn based upon physical property, chemical attributes, storage, washing and cooking stability, and bioavailability of fortified rice. The summarized dataon prospects and drawbackswould provide background information to carry out research-based developments in whole grain rice fortification and making further innovations.