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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Hierarchical Assembly of Nanodimensional Silver-Silver Oxide Physical Gels Controlling Nosocomial Infections.

Microbial infections originating from medical care facilities are raising serious concerns across the globe. Therefore, nanotechnology-derived nanostructures have been investigated and explored due to their promising characteristics. In view of this, silver-based antimicrobial hydrogels as an alternative to antibiotic-based creams could play a crucial role in combating such infections. Toward this goal, we report a simple method for the synthesis and assembly of silver nanoparticles in a biopolymer physical gel derived from Abroma augusta plant in imparting antimicrobial properties against nosocomial pathogens. Synthesized silver nanoparticles (diameter, 30 ± 10 nm) were uniformly distributed inside the hydrogel. Such synthesized hydrogel assembly of silver nanoparticles dispersed in the biopolymer matrix exhibited hemocompatibility and antimicrobial and antibiofilm characteristics against nosocomial pathogens. The developed hydrogel as a surface coating offers reduced hardness and modulus value, thereby minimizing the brittleness tendency of the gel in the dried state. Hence, we believe that the hierarchical assembly of our hydrogel owing to its functional activity, host toxicity, and stability could possibly be used as an antimicrobial ointment for bacterial infection control.

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.

Deciphering the structural intricacy in virulence effectors for proton-motive force mediated unfolding in type-III protein secretion.

Given that the protein unfolding requisite for type-III secretion system (T3SS)-mediated secretion is an energetically unfavorable process, the question of how do pathogenic bacteria unfold and secrete hundreds of toxic proteins in seconds remain largely unknown. In this study, a systematic effort combining experimental and computational approaches has been employed to get some mechanistic insights on the unfolding of effectors in T3SS secretion. The in-depth analysis of pH-dependent folding and stability of a T3SS effector ExoY revealed that proton-concentration gradient (~pH 5.8-6.0) generated by proton-motive force (PMF) had significantly affected folding and structural stability of this protein without significant loss of the free energy of unfolding. Importantly, the lower energetic cost associated with the global unfolding of ExoY was mainly due to its inherent stereo-chemical frustrations embedded within its native-like structure as observed from its core structural analysis. These observations suggest that the cooperation between the evolved structural features of ExoY and pH-mediated unfolding is crucial for PMF-mediated T3SS secretion. From a comprehensive computational analysis of 371 T3SS effectors it was concluded that many of these effectors belong to the category of intrinsically disordered proteins (IDPs) and have similar conserved structural archetypes to facilitate early-stage unfolding process as observed in ExoY. We had also provided details of folding, stability, and molecular evolution in T3SS effectors and established the role of evolved structural archetypes in early-stage unfolding events of this effector for maintaining balance in secretion and function trade-off.

Stacking-Order-Driven Optical Properties and Carrier Dynamics in ReS2.

Two distinct stacking orders in ReS2 are identified without ambiguity and their influence on vibrational, optical properties and carrier dynamics are investigated. With atomic resolution scanning transmission electron microscopy (STEM), two stacking orders are determined as AA stacking with negligible displacement across layers, and AB stacking with about a one-unit cell displacement along the a axis. First-principles calculations confirm that these two stacking orders correspond to two local energy minima. Raman spectra inform a consistent difference of modes I & III, about 13 cm-1 for AA stacking, and 20 cm-1 for AB stacking, making a simple tool for determining the stacking orders in ReS2 . Polarized photoluminescence (PL) reveals that AB stacking possesses blueshifted PL peak positions, and broader peak widths, compared with AA stacking, indicating stronger interlayer interaction. Transient transmission measured with femtosecond pump-probe spectroscopy suggests exciton dynamics being more anisotropic in AB stacking, where excited state absorption related to Exc. III mode disappears when probe polarization aligns perpendicular to b axis. The findings underscore the stacking-order driven optical properties and carrier dynamics of ReS2 , mediate many seemingly contradictory results in the literature, and open up an opportunity to engineer electronic devices with new functionalities by manipulating the stacking order.

Two-Dimensional to Three-Dimensional Growth of Transition Metal Diselenides by Chemical Vapor Deposition: Interplay between Fractal, Dendritic, and Compact Morphologies.

We investigate the role of growth temperature and metal/chalcogen flux in atmospheric pressure chemical vapor deposition growth of MoSe2 and WSe2 on Si/SiO2 substrates. Using scanning electron microscopy and atomic force microscopy, we observe that the growth temperature and transition metal flux strongly influence the domain morphology, and the compact triangular or hexagonal domains ramify into branched structures as the growth temperature (metal flux) is decreased (increased). The competition between adatom attachment to the domain edges and diffusion of adatoms along the domain boundary determines the evolution of the observed growth morphology. Depending on the growth temperature and flux, two different branched structures-fractals and dendrites-grow. The fractals (with a dimension of ∼1.67) obey a diffusion-limited aggregation mechanism, whereas the dendrites with a higher fractal dimension of ∼1.80 exhibit preferential growth along the symmetry-governed directions. The effect of chalcogen environment is studied, where a Se-rich condition helps restrict Mo-rich nucleus formation, promoting lateral growth. For a Se-deficient environment, several multilayer islands cluster on two-dimensional domains, suggesting a transition from lateral to vertical growth because of insufficient Se passivation. X-ray photoelectron spectroscopy analysis shows a near perfect stoichiometry (Mo/Se = 1:1.98) of MoSe2 grown in a Se-rich environment, whereas in the Se-deficient condition, a ratio of Mo/Se = 1:1.68 is observed. This also supports the formation of metal-rich nuclei (Mo1+xSe2-x) under Se-deficient conditions, leading to three-dimensional clustering. Tuning the growth temperature and metal/chalcogen flux, we propose an optimized CVD growth window for synthesizing large-area Mo(W) selenide.