Density functional theory study of the structure, stability, magnetic properties, and (hyper)polarizability of (sub-nm) rare-earth (RE) doped gold clusters: Au5RE with RE = Sc, Y, La-Lu.

Rare-earth doped materials are of immense interest for their potential applications in linear and nonlinear photonics. There is also intense interest in sub-nanometer gold clusters due to their enhanced stability and unique optical, magnetic, and catalytic properties. To leverage their emergent properties, here we report a systematic study of the geometries, stability, electronic, magnetic, and linear and nonlinear optical properties of Au5RE (RE = Sc, Y, La-Lu) clusters using density-functional theory. Several low-energy isomers consisting of planar or non-planar configurations are identified. For most doped clusters, the non-planar configuration is energetically favored. In the case of La-, Pm-, Gd-, and Ho-doped clusters, a competition between planar and non-planar isomers is predicted. A distinct preference for the planar configuration is predicted for Au5Eu, Au5Sm, Au5Tb, Au5Tm, and Au5Yb. The distinction between the planar and non-planar configurations is highlighted by the calculated highest frequencies, with the stretching mode of the non-planar configuration predicted to be stiffer than the planar configuration. The bonding analysis reveals the dominance of the RE-d orbitals in the formation of frontier molecular orbitals, which, in turn, facilitates retaining the magnetic characteristics governed by RE-f orbitals, preventing spin-quenching of rare earths in the doped clusters. In addition, the doped clusters exhibit small energy gaps between frontier orbitals, large dipole moments, and enhanced hyperpolarizability compared to the host cluster.

First-principles study of the oxidation susceptibility of WS2, WSe2, and WTe2 monolayers.

The environmental stability of two-dimensional (2D) transition metal dichalcogenide monolayers is of great importance for their applications in electronic, photonic, and energy storage devices. In this study, we focus on understanding the susceptibility of WS2, WSe2, and WTe2 monolayers to oxygen exposure in the form of atomic oxygen and O2 and O3 molecules, respectively. Calculations based on the van der Waals-corrected density functional theory predicted that O2 and O3 molecules are weakly adsorbed on these monolayers, although atomic oxygen prefers chemisorption accompanied by a significant charge transfer from the surface to oxygen. In the physisorbed molecular configurations consisting of O2 and O3, the partially oxidized monolayers retain their geometrical and electronic structures. The calculated transition path as the oxygen approaches the surface shows a high-energy barrier for all cases, thus explaining the photo-induced formation of the oxidized configurations in the experiments. Furthermore, oxidizing the WS2 monolayer is predicted to modify its electronic structure, reducing the band gap with increasing oxygen coverage on the surface. Overall, the calculated results predict the resilience of WS2, WSe2, and WTe2 monolayers against oxygen exposure, thus ensuring stability for devices fabricated with these monolayers.

Materials Innovations for Quantum Technology Acceleration: A Perspective.

A broad perspective of quantum technology state of the art is provided and critical stumbling blocks for quantum technology development are identified. Innovations in demonstrating and understanding electron entanglement phenomena using bulk and low-dimensional materials and structures are summarized. Correlated photon-pair generation via processes such as nonlinear optics is discussed. Application of qubits to current and future high-impact quantum technology development is presented. Approaches for realizing unique qubit features for large-scale encrypted communication, sensing, computing, and other technologies are still evolving; thus, materials innovation is crucially important. A perspective on materials modeling approaches for quantum technology acceleration that incorporate physics-based AI/ML, integrated with quantum metrology is discussed.

Electronic Structure Calculations of Static Hyper(Polarizabilities) of Substrate-Supported Group-IV and -V Elemental Monolayers.

The substrate-induced effects on the polarizability (α) and first dipole hyperpolarizability (ß) of group-IV (i.e., graphene, silicene, germanene, stanene) and group-V (i.e., phosphorene, arsenene, antimonene, and bismuthene) elemental monolayer nanoflakes are investigated. Density functional theory calculations show that these monolayers are bound with varying degrees of interaction strength with the Ag(111) substrate surface. Calculated dipole moment and ß values are zero for the centrosymmetric configurations of the pristine elemental monolayers. On the other hand, substrate-induced changes in the electronic densities at the interface lead to substantially enhanced values of ß, making these materials attractive for applications in the next-generation photonic technologies at the nanoscale.

Effects of Isolated and Combined Exposure of the Brain and Lungs to a Laser-Induced Shock Wave(s) on Physiological and Neurological Responses in Rats.

Blast-induced traumatic brain injury (bTBI) has been suggested to be caused by direct head exposure and by torso exposure to a shock wave (thoracic hypotheses). It is unclear, however, how torso exposure affects the brain in real time. This study applied a mild-impulse laser-induced shock wave(s) (LISW[s]) only to the brain (Group 1), lungs (Group 2), or to the brain and lungs (Group 3) in rats. Because LISWs are unaccompanied by a dynamic pressure in principle, the effects of acceleration can be excluded, allowing analysis of the pure primary mechanism (the effects of a shock wave). For all rat groups, real-time monitoring of the brain and systemic responses were conducted for up to 1 h post-exposure and motor function assessments for up to seven days post-exposure. As reported previously, brain exposure alone caused cortical spreading depolarization (CSD), followed by long-lasting hypoxemia and oligemia in the cortices (Group 1). It was found that even LISW application only to the lungs caused prolonged hypoxemia and mitochondrial dysfunction in the cortices (Group 2). Importantly, features of CSD and mitochondrial dysfunction were significantly exacerbated by combined exposure (Group 3) compared with those caused by brain exposure alone (Group 1). Motor dysfunction was observed in all exposure groups, but their time courses differed depending on the groups. Rats with brain exposure alone exhibited the most evident motor dysfunction at one day post-exposure, and after that, it did not change much for up to seven days post-exposure. Alternatively, two groups of rats with lung exposure (Group 2 and Group 3) exhibited continuously aggravated motor functions for up to seven days post-exposure, suggesting different mechanisms for motor dysfunction caused by brain exposure and that caused by lung exposure. As for the reported thoracic hypotheses, our observations seem to support the volumetric blood surge and vagovagal reflex. Overall, the results of this study indicate the importance of the torso guard to protect the brain and its function.

Performance of graphene-zinc oxide nanocomposite coated-glassy carbon electrode in the sensitive determination of para-nitrophenol.

Graphene: zinc oxide nanocomposite (GN:ZnO NC) platform was tried for the sensitive determination of para-nitrophenol (p-NP) through the electrochemical method. ZnO nanoparticles (NPs) were synthesized by the modified wet-chemical method where in potassium hydroxide and zinc nitrate were used as precursors and starch as a stabilizing agent. A green and facile approach was applied to synthesize GN:ZnO NC in which glucose was employed as a reductant to reduce graphene-oxide to graphene in the presence of ZnO NPs. The synthesized NC was characterized using scanning and high-resolution transmission electron microscopy, energy dispersive x-ray analysis, X-ray diffraction and Raman spectroscopic techniques to examine the crystal phase, crystallinity, morphology, chemical composition and phase structure. GN:ZnO NC layer deposited over the glassy carbon electrode (GCE) was initially probed for its electrochemical performance using the standard 1 mM K3[Fe(CN)6] model complex. GN:ZnO NC modified GCE was monitored based on p-NP concentration. An enhanced current response was observed in 0.1 M phosphate buffer of pH 6.8 for the determination of p-NP in a linear working range of 0.09 × 10-6 to 21.80 × 10-6 M with a lower detection limit of 8.8 × 10-9 M employing square wave adsorptive stripping voltammetric technique at a deposition-potential and deposition-time of - 1.0 V and 300 s, respectively. This electrochemical sensor displayed very high specificity for p-NP with no observed interference from some other possible interfering substances such as 2, 4-di-NP, ortho-NP, and meta-NP. The developed strategy was useful for sensitive detection of p-NP quantity in canals/rivers and ground H2O samples with good recoveries.

Ozonation of Group-IV Elemental Monolayers: A First-Principles Study.

Environmental effect on the physical and chemical properties of two-dimensional monolayers is a fundamental issue for their practical applications in nanoscale devices operating under ambient conditions. In this paper, we focus on the effect of ozone exposure on group-IV elemental monolayers. Using density functional theory and the climbing image nudged elastic band approach, calculations are performed to find the minimum energy path of O3-mediated oxidation of the group-IV monolayers, namely graphene, silicene, germanene, and stanene. Graphene and silicene are found to represent two end points of the ozonation process: the former showing resistance to oxidation with an energy barrier of 0.68 eV, while the latter exhibit a rapid, spontaneous dissociation of O3 into atomic oxygens accompanied by the formation of epoxide like Si-O-Si bonds. Germanene and stanene also form oxides when exposed to O3, but with a small energy barrier of about 0.3-0.4 eV. Analysis of the results via Bader's charge and density of states shows a higher degree of ionicity of the Si-O bond followed by Ge-O and Sn-O bonds relative to the C-O bond to be the primary factor leading to the distinct ozonation response of the studied group-IV monolayers. In summary, ozonation appears to open the band gap of the monolayers with semiconducting properties forming stable oxidized monolayers, which could likely affect group-IV monolayer-based electronic and photonic devices.

Enhanced nonlinear optical response of graphene-based nanoflake van der Waals heterostructures.

The nonlinear optical properties of van der Waals bilayer heterostructures composed of graphene/h-BN and graphene/phosphorene nanoflakes are investigated using time-dependent density functional theory. Our calculated results show a significant enhancement of the first-hyperpolarizability value, ß in heterostructures relative to the pristine nanoflakes at λ = 1064 nm. The calculated enhancement in optical nonlinearity mainly results from in-plane anisotropy induced by the interlayer electronic coupling between the adjacent nanoflake layers; a higher degree of anisotropy is induced by puckered phosphorene compared to atomically flat h-BN yielding χ (2) value corresponding to the second harmonic generation of ∼50 pm V-1 in the zigzag graphene/phosphorene bilayer heterostructure. The calculated results clearly show that graphene-based nanoflake heterostructures giving large NLO coefficients together with high electron mobility of these materials offer new opportunities as candidate materials of choice for next-generation photonics and integrated quantum technologies.

Confinement-Enhanced Luminescence in Protein-Gold Nanoclusters.

Confinement has profound effects on protein functions. Nanoscale probes for confinement or excluded volume interactions could help us understand how these interactions influence protein functions. This work reports on the increased luminescence of BSA-gold nanoclusters when confined. Confinement of the BSA-gold nanoclusters occurred within reverse micelles (RMs), where the size of the RMs determined the degree of confinement. The confinement-enhanced luminescence is reversible, i.e., the emission returns to its original value following cyclic changes in RM size. Circular dichroism measurements show an increase in alpha-helical character of the BSA-stabilized nanoclusters with confinement, which could provide a mechanism for the increase in luminescence. The alpha-helical character of the native proteins also increases with confinement, suggesting that the protein-nanocluster might sense confinement in an analogous fashion as the proteins. When the RMs approach the size of the protein, the intensity becomes independent of alpha-helical character, suggesting a different mechanism for the luminescence increase.

Human Nontumorigenic Microglia Synthesize Strongly Fluorescent Au/Fe Nanoclusters, Retaining Bioavailability.

The ability for cells to self-synthesize metal-core nanoclusters (mcNCs) offers increased imaging and identification opportunities. To date, much work has been done illustrating the ability for human tumorigenic cell lines to synthesize mcNCs; however, this has not been illustrated for nontumorigenic cell lines. Here, we present the ability for human nontumorigenic microglial cells, which are the major immune cells in the central nervous system, to self-synthesize gold (Au) and iron (Fe) core nanoclusters, following exposures to metallic salts. We also show the ability for cells to internalize presynthesized Au and Fe mcNCs. Cellular fluorescence increased in most exposures and in a dose dependent manner in the case of Au salt. Scanning transmission electron microscopic imaging confirmed the presence of the metal within cells, while transmission electron microscopy images confirmed nanocluster structures and self-synthesis. Interestingly, self-synthesized nanoclusters were of similar size and internal structure as presynthesized mcNCs. Toxicity assessment of both salts and presynthesized NCs illustrated a lack of toxicity from Au salt and presynthesized NCs. However, Fe salt was generally more toxic and stressful to cells at similar concentrations.

Freestanding organogels by molecular velcro of unsaturated amphiphiles.

A simple amphiphile, N-cardanyltaurine amide (NCT) with different degrees of cis-unsaturation in its tail resulted in the formation of strong organogels. Interestingly, this is in contrast to the commonly accepted notion that introducing unsaturation in alkyl chains enhances fluidity in lipid assemblies. The physico-chemical and first-principles DFT calculations confirmed the pegging of 'kinked' unsaturated side chains, where the hydrophobic interlocking as in Velcro fasteners leads to a network of cylindrical micelles, resulting in self-standing organogels. Textural profile analysis and spectroscopic details substantiated the dynamic assembly to resemble a 3D network of gelators rather than being a cross-linked or polymerized matrix of monomers.

Robust band gaps in the graphene/oxide heterostructure: SnO/graphene/SnO.

The applicability of graphene in nanoscale devices is somewhat limited because of the absence of a finite band gap. To overcome this limitation of zero band gap, we consider vertically-stacked heterostructures consisting of graphene and SnO knowing that two-dimensional SnO films were synthesized recently. Calculations based on density functional theory find that the oxide monolayer can induce a notable band gap in graphene; 115 meV in SnO/graphene/SnO heterostructures. Additionally, the band gap of graphene can be maintained under a relatively high electric field (≈109 V m-1) applied to the heterostructures because of the electrostatic screening effect of the oxide layer. The calculated results suggest the relative superiority of the graphene/oxide heterostructures over graphene/BN heterostructures for the nanoscale devices based on graphene.

Theoretical study of gas and solvent phase stability and molecular adsorption of noncanonical guanine bases on graphene.

The gas and solvent phase stability of noncanonical (Gua)n nucleobases is investigated in the framework of dispersion-corrected density functional theory (DFT). The calculated results strongly support the high tendency for the dimerization of (Gua)n bases in both gas and solvent phases. An interplay between intermolecular and bifurcated H-bonds is suggested to govern the stability of (Gua)n bases which bears a correlation with the description of dispersion correction terms employed in the DFT calculations. For example, a higher polarity is predicted for (Gua)n bases by the dispersion-corrected DFT in contrast to the non-polar nature of (Gua)3 and (Gua)4 predicted by the hybrid meta-GGA calculations. This distinct variation becomes significant under physiological conditions as polar (Gua)n is likely to exhibit greater stabilization in the gas phase compared to solvated (Gua)n. Graphene acting as a substrate induces modification in base configurations via maximization of π-orbital overlap between the base and substrate. In solvent, the substrate-induced effects are further heightened with lowering of the dipole moments of (Gua)n as also displayed by the corresponding isosurface of the electrostatic potential. The graphene-induced stability in both gas and solvent phases appears to fulfill one of the prerequisite criteria for molecular self-assembly. The DFT results therefore provide atomistic insights into the stability and molecular assembly of free-standing noncanonical (Gua)n nucleobases which can be extended to understanding the self-assembly process of functional biomolecules on 2D materials for potential biosensing applications.

Amino Acid Analogue-Conjugated BN Nanomaterials in a Solvated Phase: First Principles Study of Topology-Dependent Interactions with a Monolayer and a (5,0) Nanotube.

Using density functional theory and an implicit solvation model, the relationship between the topology of boron nitride (BN) nanomaterials and the protonated/deprotonated states of amino acid analogues is investigated. In the solvated phase, the calculated results show distinct "physisorbed versus chemisorbed" conditions for the analogues of arginine (Arg)- and aspartic acid (Asp)-conjugated BN nanomaterials, including a monolayer (ML) and a small-diameter zigzag nanotube (NT). Such a distinction does not depend on the functional groups of amino acids but rather depends on the curvature-induced interactions associated with the tubular configuration. Arg and Asp interact with the BNML to form physisorbed complexes irrespective of the state of the amino acids in the solvated phase. For the NT, Arg and Asp form chemisorbed complexes, and the distinct nature of bonds between the donor electron moieties of N(Arg) and O(Asp) and the boron of the tubular surface is revealed by the natural bond orbital analysis; stronger s-type bonds for the deprotonated conjugated complexes and slightly weaker p-type dominated bonds for the protonated conjugated complexes. The interaction of neutral Trp with BN nanomaterials results in physisorbed configurations through π-stacking interactions with the indole ring of the Trp and BN nanomaterials. The calculated results form the basis for a theoretical study of more complex protein macromolecules interacting with nanomaterials under physiological conditions.

Hierarchical Self-Assembly of Noncanonical Guanine Nucleobases on Graphene.

Self-assembly characterizes the fundamental basis toward realizing the formation of highly ordered hierarchical heterostructures. A systematic approach toward the supramolecular self-assembly of free-standing guanine nucleobases and the role of graphene as a substrate in directing the monolayer assembly are investigated using the molecular dynamics simulation. We find that the free-standing bases in gas phase aggregate into clusters dominated by intermolecular H-bonds, whereas in solvent, substantial screening of intermolecular interactions results in π-stacked configurations. Interestingly, graphene facilitates the monolayer assembly of the bases mediated through the base-substrate π-π stacking. The bases assemble in a highly compact network in gas phase, whereas in solvent, a high degree of immobilization is attributed to the disruption of intermolecular interactions. Graphene-induced stabilization/aggregation of free-standing guanine bases appears as one of the prerequisites governing molecular ordering and assembly at the solid/liquid interface. The results demonstrate an interplay between intermolecular and π-stacking interactions, central to the molecular recognition, aggregation dynamics, and patterned growth of functional molecules on two-dimensional nanomaterials.

Highly sensitive and selective determination of methylergometrine maleate using carbon nanofibers/silver nanoparticles composite modified carbon paste electrode.

A highly sensitive and selective voltammetric method for determination of Methylergometrine maleate (MM) in pharmaceutical formulations, urine and blood serum samples has been developed based on enhanced electrochemical response of MM at carbon nanofibers and silver nanoparticles modified carbon paste electrode (CNF-AgNP-CPE). The electrode material was characterized by various techniques viz., X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. The electrocatalytic response of MM at CNF-AgNP-CPE was studied by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS). Under optimized conditions, the proposed sensor exhibits excellent electrochemical response towards MM. The DPV study shows greatly enhanced electrochemical signal for MM at CNF-AgNP-CPE lending high sensitivity to the proposed sensor for MM detection. The peak (Ip) current for MM is found to be rectilinear in the range 4.0×10(-8)-2.0×10(-5)M with a detection limit of 7.1×10(-9)M using DPV. The feasibility of the proposed sensor in analytical applications was investigated by conducting experiments on commercial pharmaceutical formulations, human urine and blood serum samples, which yielded satisfactory recoveries of MM. The proposed electrochemical sensor offers high sensitivity, selectivity, reproducibility and practical utility. We recommend it as an authentic and productive electrochemical sensor for successful determination of MM.

In situ Synthesis of Fluorescent Gold Nanoclusters by Nontumorigenic Microglial Cells.

To date, the directed in situ synthesis of fluorescent gold nanoclusters (AuNCs) has only been demonstrated in cancerous cells, with the theorized synthesis mechanism prohibiting AuNC formation in nontumorigenic cell lines. This limitation hinders potential biostabilized AuNC-based technology in healthy cells involving both chemical and mechanical analysis, such as the direct sensing of protein function and the elucidation of local mechanical environments. Thus, new synthesis strategies are required to expand the application space of AuNCs beyond cancer-focused cellular studies. In this contribution, we have developed the methodology and demonstrated the direct in situ synthesis of AuNCs in the nontumorigenic neuronal microglial line, C8B4. The as-synthesized AuNCs form in situ and are stabilized by cellular proteins. The clusters exhibit bright green fluorescence and demonstrate low (<10%) toxicity. Interestingly, elevated ROS levels were not required for the in situ formation of AuNCs, although intracellular reductants such as glutamate were required for the synthesis of AuNCs in C8B4 cells. To our knowledge, this is the first-ever demonstration of AuNC synthesis in nontumorigenic cells and, as such, it considerably expands the application space of biostabilized fluorescent AuNCs.

Blocking Oxidation Failures of Carbon Nanotubes through Selective Protection of Defects.

The selective growth of Al2 O3 islands over defect sites on the surface of carbon nanotubes significantly increases the oxidation breakdown threshold to 6.8 W cm(-2) , more than double than that of unprotected films. The elevated input power enables thermoacoustic emissions at loud audible sound pressure levels of 90.1 dB, which are inaccessible with the unprotected films.

Carbon phosphide monolayers with superior carrier mobility.

Two dimensional (2D) materials with a finite band gap and high carrier mobility are sought after materials from both fundamental and technological perspectives. In this paper, we present the results based on the particle swarm optimization method and density functional theory which predict three geometrically different phases of the carbon phosphide (CP) monolayer consisting of sp2 hybridized C atoms and sp3 hybridized P atoms in hexagonal networks. Two of the phases, referred to as α-CP and ß-CP with puckered or buckled surfaces are semiconducting with highly anisotropic electronic and mechanical properties. More remarkably, they have the lightest electrons and holes among the known 2D semiconductors, yielding superior carrier mobility. The γ-CP has a distorted hexagonal network and exhibits a semi-metallic behavior with Dirac cones. These theoretical findings suggest that the binary CP monolayer is a yet unexplored 2D material holding great promise for applications in high-performance electronics and optoelectronics.

Out-of-plane structural flexibility of phosphorene.

Phosphorene has been rediscovered recently, establishing itself as one of the most promising two-dimensional group-V elemental monolayers with direct band gap, high carrier mobility, and anisotropic electronic properties. In this paper, surface buckling and its effect on its electronic properties are investigated by using molecular dynamics simulations together with density functional theory calculations. We find that phosphorene shows superior structural flexibility along the armchair direction allowing it to have large curvatures. The semiconducting and direct band gap nature are retained with buckling along the armchair direction; the band gap decreases and transforms to an indirect band gap with buckling along the zigzag direction. The structural flexibility and electronic robustness along the armchair direction facilitate the fabrication of devices with complex shapes, such as folded phosphorene and phosphorene nano-scrolls, thereby offering new possibilities for the application of phosphorene in flexible electronics and optoelectronics.