Size-Dependent Fullerenes for Enhanced Interaction of l-Leucine: A Combined DFT and MD Simulations Approach.

Fullerene-based biosensors have received great attention due to their unique electronic properties that allow them to transduce electrical signals by accepting electrons from amino acids. Babies with MSUD (maple syrup urine disease) are unable to break down amino acids such as l-leucine, and excess levels of the l-leucine are harmful. Therefore, sensing of l-leucine is foremost required. We aim to investigate the interaction tendencies of size-variable fullerenes (CX; X = 24, 36, 50, and 70) toward l-leucine (LEU) using density functional theory (DFT-D3) and classical molecular dynamics (MD) simulation. The C24 fullerene shows the highest affinity of the LEU biomolecule in the gas phase. Smaller fullerenes (C24 and C36) show stronger interactions with leucine due to their higher curvature in water environments. Moreover, recovery times in the ranges of 1010 and 104 s make it a viable candidate for the isolation application of LEU from the biological system. Further, the interaction between LEU and fullerenes is in line with the natural bond order (NBO) analysis, Mulliken charge analysis, quantum theory atom in molecule (QTAIM) analysis, and reduced density gradient (RDG) analysis. At 310 K, employing the explicit water model in classical MD simulations, fullerenes C24 and C36 demonstrate notably elevated binding free energies (-24.946 kJ/mol) in relation to LEU, showcasing their potential as sensors for l-leucine. Here, we demonstrate that the smaller fullerene exhibits a higher potential for l-leucine sensors than the larger fullerene.

Non-trivial topological phases in transition metal rich half-Heusler oxides.

Topological insulators with gapless surface states and insulating bulk in non-centrosymmetric cubic systems have been extensively explored following the discovery of two-dimensional quantum spin hall effect in zincblende HgTe. In such systems the negative band inversion strength EBIS(= EΓ6-EΓ8<0) governs the robustness of the non-trivial topological states at ambient conditions. Hence, realizing large negative values of EBIShas been a guiding motivation of several investigations reported in literature. Here, we present a material design approach which can be employed to realize large negative values of EBISin cubic materials such as half-Heusler (HH) oxides with 18 valence electron configurations. We explore 27 HH oxides of the form ABO (A = Li, K, Rb; B = Cu, Ag, Au) inα-,ß-, andγ-phase (by placing transition metal atom at different Wyckoff positions) for their non-trivial topological phase. Off these three phases, we found that, theα-phase of nine HH oxides (wherein the transition metal atoms occupy 4a Wyckoff positions in the crystal structure) is the most promising with non-trivial topological phase which is governed by the mass-Darwin fully-relativistic effects enhancing EBIS. Whereas the other phases were found to be either trivial semiconductors or semimetals or metals and most of them being dynamically unstable. We focus on RbAuO inα-phase with EBISof -1.29 eV and the effect of strain fields on the topological surface states of this compound. We conclude that theα-phase of HH oxide presented here can be synthesized experimentally for diverse room temperature applications in spintronics and nanoelectronics.

DFT stimulation and experimental insights of chiral Cu(II)-salen scaffold within the pocket of MWW-zeolite and its catalytic study.

A Cu(II)-salen complex encapsulated in MWW-framework as an efficient chiral organocatalyst was developed for the synthesis of 3,4-dihydropyrimidin-2-(1H)-one (DHPMs) derivatives via an asymmetric pathway. In order to confirm its structural properties, single-crystal X-ray diffraction, powder XRD, BET, XPS, FE-SEM, EDX, UV-Vis, and FTIR spectra were used. Using computer-assisted DFT calculations, the Cu(II)-salen complex has been fine-tuned to fit into the pocket of the porous MWW support while keeping its chirality. This organocatalyst was shown to be a potent catalyst for the formation of the desired DHPMs product under short reaction times. Furthermore, this green protocol allows rapid and simple isolation of active MWW-trapped Cu(II)-salen scaffolds and its reusability in at least five consecutive runs without losing much of its activity.

Functionalized tellurene; a candidate large-gap 2D topological insulator.

The discovery of group IV and V elemental xene's with topologically non-trivial characters in their honeycomb lattice structure (HLS) has led to extensive efforts in realising analogous behaviour in group VI elemental monolayers. Theoretically; it was concluded that, group VI elemental monolayers cannot exist in HLS. However, some recent experimental evidence suggests that group VI elemental monolayers can be realised in HLS. In this letter, we report HLS of group VI elemental monolayer (such as, tellurene) can be realised to be dynamically stable when functionzalised with oxygen. The functionalization leads to, peculiar orbital filtering effects and broken spatial inversion symmetry which gives rise to the non-trivial topological character. The exotic quantum behaviour of this system is characterized by, spin-orbit coupling induced large-gap (≈0.36 eV) with isolated Dirac cone along the edges indicating potential room temperature spin-transport applications. Further investigations of spin Hall conductivity and the Berry curvatures unravel high conductivity as compared to previously explored xene's alongside the potential valley Hall effects. The non-trivial topological character is quantified in terms of theZ2invariant asν= 1 and Chern numberC= 1. Also, for practical purposes, we report that,hBN/TeO/hBN quantum-wells can be strain engineered to realize a sizeable non-trivial gap (≈0.11 eV). We finally conclude that, functionalization of group VI elemental monolayer with oxygen gives rise to, exotic quantum properties which are robust against surface oxidation and degradations while providing viable electronic degrees of freedom for spintronic/valleytronic applications.

Dressing of Cu Atom over Nickel Cluster Stimulating the Poisoning-Free CO Oxidation: An Ab Initio Study.

In this work using first-principles calculations based on spin-polarized density functional theory (DFT), the role of the Cu atom in degrading the poisoning of carbon monoxide (CO) over NinCu clusters is unveiled. The search has been initiated with the examination of structural, magnetic, and electronic properties of Nin+1 and NinCu clusters (1 ≤ n ≤ 12). X-ray absorption near-edge structure (XANES) spectra of Ni K-edge are computed to extract the information on the oxidation states and coordination environment of metal sites of the clusters. This study is operated with the two forms of dispersion corrections, i.e., D2 and D3, with standard DFT (with LDA and GGA functionals) for the consideration of van der Waals interactions during CO adsorption. The PBE and PBE-D3 approaches are found to be capable of yielding the experimentally observed preferential site for CO adsorption. The effect of spin-polarization on the reactivity of transition metals (TMs) toward CO adsorption is crucially assessed by the electronic reactivity descriptors such as d-band center, d-band width, and fractional filling of d-band using a spin-polarized d-band center model. The effective charge transfer from Cu to Ni atoms makes Ni atoms more efficient of charge and is attributed to the degrading adsorption of CO over NinCu clusters. The Ni12Cu cluster stands out with good CO oxidation activity for the Langmuir-Hinshelwood (L-H) reaction pathway.

Superior Room-Temperature Ammonia Sensing Using a Hydrothermally Synthesized MoS2/SnO2 Composite.

Layered two-dimensional transition metal dichalcogenides, due to their semiconducting nature and large surface-to-volume ratio, have created their own niche in the field of gas sensing. Their large recovery time and accompanied incomplete recovery result in inferior sensing properties. Here, we report a composite-based strategy to overcome these issues. In this study, we report a facile double-step synthesis of a MoS2/SnO2 composite and its successful use as a superior room-temperature ammonia sensor. Contrary to the pristine nanosheet-based sensors, the devices made using the composite display superior gas sensing characteristics with faster response. Specifically, at room temperature (30° C), the composite-based sensor exhibited excellent sensitivity (10%) at an ammonia concentration down to 0.4 ppm along with the response and recovery times of 2 and 10 s, respectively. Moreover, the device also exhibited long-term durability, reproducibility, and selectivity toward ammonia against hydrogen sulfide, methanol, ethanol, benzene, acetone, and formaldehyde. Sensor devices made on quartz and alumina substrates with different roughnesses have yielded almost an identical response, except for slight variations in response and recovery transients. Further, to shed light on the underlying adsorption energetics and selectivity, density functional theory simulations were employed. The improved response and enhanced selectivity of the composite were explicitly discussed in terms of adsorption energy. Lowdin charge analysis was performed to understand the charge transfer mechanism between NH3, H2S, CH3OH, HCHO, and the underlying MoS2/SnO2 composite surface. The long-term durability of the sensor was evident from the stable response curves even after 2 months. These results indicate that hydrothermally synthesized MoS2/SnO2 composite-based gas sensors can be used as a promising sensing material for monitoring ammonia gas in real fields.

Emergence of -s, -p-dband inversion in zincblende gold iodide topological insulator and its thermoelectric properties.

We employfirst-principlescalculations to investigate the topological states (TS) and thermoelectric (TE) transport properties of three dimensional (3D) gold iodide (AuI) which belongs to the zincblende family. We explore, semi-metal (SM) to topological conductor (TC) and topological insulator (TI) phase transitions. Under pristine conditions, AuI exhibits Dirac SM nature but, under the influence of mild isotropic compressive pressure the system undergoes electronic quantum phase transition driving it into non-trivial topological state. This state exhibits Dresselhaus like band spin splitting leading to a TC state. In order to realize TI state from the SM state, we break the cubic symmetry of the system by introducing a compressive pressure along (001) crystal direction. The non-trivial TI nature of the system is characterized by the emergence of robust surface states and theZ2invariantν0= 1 which indicates a strong TI nature. A novel facet of the phase transition discussed here is, the -sand -p, -dorbital band inversion mechanism which is unconventional as compared to previously explored TI families. This mechanism unravels new path by which TI materials can be predicted. Also, we investigated the lattice and electronic contributions to the TE transport properties. We characterize the TE performance by calculating the figure of merit (zT) and find that, at room temperature (300 K) and for a fixed doping concentration (i.e.,n= 1 × 1019 cm-3) the zT is 0.55 and 0.53 for electrons and holes respectively. This is quite remarkable since, higher values of zT are generally predicted at higher temperature scales whereas, zT values as in the present case are desired at room temperatures for various energy applications. The manifestation of non-trivial TS governed by the unconventional band inversion mechanism and the TE properties of AuI make it a unique multi-functional candidate with probable thermoelectric and spintronic applications.

Dimensional engineering of a topological insulating phase in Half-Heusler LiMgAs.

We propose a novel technique of dimensional engineering to realize low dimensional topological insulator from a trivial three dimensional parent. This is achieved by confining the bulk system to one dimension along a particular crystal direction, thus enhancing the quantum confinement effects in the system. We investigate this mechanism in the Half-Heusler compound LiMgAs with face-centered cubic (FCC) structure. At ambient conditions the bulk FCC structure exhibits a semi-conducting nature. But, under the influence of high volume expansive pressure (VEP) the system undergoes a topological phase transition (TPT) from semi-conducting to semi-metallic forming a Dirac cone. At a critical VEP we observe that, spin-orbit coupling (SOC) effects introduce a gap of [Formula: see text] 1.5 meV in the Dirac cone at high symmetry point [Formula: see text] in the Brillouin zone. This phase of bulk LiMgAs exhibits a trivial nature characterized by the [Formula: see text] invariants as (0,000). By further performing dimensional engineering, we cleave [111] plane from the bulk FCC structure and confine the system in one dimension. This low-dimensional phase of LiMgAs has structure similar to the two dimensional [Formula: see text] system. Under a relatively lower compressive strain, the low-dimensional system undergoes a TPT and exhibits a non-trivial topological nature characterized by the SOC gap of [Formula: see text] 55 meV and [Formula: see text] invariant [Formula: see text] = 1. Although both, the low-dimensional and bulk phase exhibit edge and surface states, the low-dimensional phase is far more superior and exceptional as compared to the bulk parent in terms of the velocity of Fermions ([Formula: see text]) across the surface states. Such a system has promising applications in nano-electronics.

Site-selective unidirectional benzylic sp3 C-H oxidation of dodecahydrotriphenylene with RuCl3-NaIO4: formation of benzylic ketones.

Dodecahydrotriphenylene, a higher homologue of trindane chemoselectively undergoes unidirectional benzylic sp3 C-H oxidation and the central benzene ring remains intact unlike that in trindane under similar reaction conditions. RuO4 which generally attacks sp2 C-H to form oxidative products is found to give benzylic ketones via sp3 C-H oxidation. Density functional theory (DFT) calculations have also been performed to analyse the potential energy, energy barrier and HOMO-LUMO energy gap of the products.

Highly sensitive and flexible pressure sensor based on two-dimensional MoSe2 nanosheets for online wrist pulse monitoring.

The advancement of portable and flexible electronics that is integrated with multiple sensing functions has increasingly drawn considerable interest. The fabricated sensors would have the ability to sense multiple deformations like pressing, twisting and trivial vibrations such as pulses of wrist vibrations to mimic human skin. Presently, we implemented an easy, cost-effective and optimized fabrication technique for production of pressure sensors based on MoSe2 nanosheets coated on cellulose paper. The present sensor exhibits an incorporation of large pressure sensitivity of 18.42 kPa-1 in pressure range 0.001-0.5 kPa, 7.28 kPa-1 in pressure range 1-35 kPa and 2.63 kPa-1 in pressure range 40-100 kPa, working in broad pressure range (from 0.001 to 100 kPa) and long-term stability up to 200 deformation cycles at 2 kPa. The sensor showed excellent response towards the detection of vibrations of machines including cellular phone, compressor, etc. Besides, the sensor shows excellent environmental stability and exhibits immune piezo-resistive response to temperature variation.

Influence of surface oxygen clusters upon molecular stacking of paclitaxel over graphene oxide sheets.

Aqueous dispersibility of graphene oxide (GO) sheets can be improved through enrichment of oxygen content (oxidation). However, the resulting 'oxygen clusters' are accompanied with numerous point defects, depletive to π-π stacking behavior of sheets. In this work, we have investigated the properties of sheets oxidized with 2, 4, 6, 8, 10 and 12 weight equivalents of KMnO4. Sheets were characterized by spectroscopic, X-ray diffraction (XRD) and electron microscopic techniques. Paclitaxel (PLX) was used as a model drug to analyze the changes in the loading efficiency at different levels of oxidation. Density of oxygen clusters increased as we shifted across increasing proportion of KMnO4. This was accompanied with increased inter-layer spacing, disruption of pure graphitic domains and changes in hybridization of carbon atoms (sp2 to sp3). However, these defects exhibited the tendency of saturation at a finite proportion of KMnO4. Oxygen groups negatively affected the loading efficiency of sheets for PLX. Improvement in the loading efficiency of reduced GO (rGO) sheets clarified the predominant role of π-π interactions at the surface. Our study reveals that high oxidation may offset the loading potential of highly aqueous dispersible GO sheets. Therefore, the extent of oxidation must be tuned taking into account the availability of H-bond forming groups in the drug molecule.

Electron density modulation of a metallic GeSb monolayer by pnictogen doping for excellent hydrogen evolution.

The catalyst assisted water-splitting method as an eco-friendly and cleaner pathway for energy generation has gained much interest in recent times. In this regard, numerous two-dimensional electrocatalysts such as mono/binary compounds synthesized from group IV, III-V and V elements with compatible activity towards hydrogen evolution, oxygen evolution, oxygen reduction and CO2 reduction have been reported. Motivated by the novel approach of material design and the need for better and cheaper electrocatalytic materials, we have investigated the ground state properties of the GeSb monolayer using state-of-the-art density functional theory. The computed electronic properties reveal the metallic nature of the pristine GeSb monolayer, indicating its potential for utilization as an electrocatalyst. The site-dependent catalytic response of the GeSb monolayer indicates that the Sb-site is more sensitive towards hydrogen adsorption amongst the considered sites. The computed adsorption and Gibbs free energies follow the trend of E < E < E. Finally, we have investigated the role of arsenic (As) and bismuth (Bi) doping on the catalytic activity of the GeSb monolayer. We notice that the electron density modulation occurs at the Sb-site due to incorporation of substitutional doping which results in a 72% enhancement in the catalytic activity of the monolayer on As substitution. The present study envisages that the electron density modulation can be utilized as a pathway for tailoring the catalytic activity of a system for the hydrogen evolution reaction.

Colloidal stability of graphene oxide nanosheets in association with triblock copolymers: A neutron scattering analysis.

This study investigates stabilization of graphene oxide (GO) nanosheets in polyethylene oxide-polypropylene oxide (PEO-PPO) block copolymers (P103, P123 and F127). Changes in micellization of copolymers upon GO addition were monitored using dynamic light (DLS) and small angle neutron scattering (SANS). Structural developments at sheet surface were studied with two possibilities; (i) adsorption of PPO block over hydrophobic basal plane allowing the engagement of hydrophilic PEO with aqueous bulk, and (ii) adsorption of micelles mediated via carboxylated groups. Insignificant changes in micellar parameters for P123 and P127 were indicative of their inferior interaction with GO. On the other hand, P103 micelles exhibited high affinity for sheets, noticeable as emergence of mass fractals and more than two-fold enhancement in micelle number density. The latter allowed coverage of entire surface with P103 micelles. Existence of mass fractals was verified by extracting the form and structure factors from the fitted SANS data. Spectroscopic and thermogravimetric analyses illustrated non-covalent adsorption of copolymer aggregates. It was interesting to note that the dispersion remained stable against protein and electrolyte addition. A comprehensive understanding on colloidal stability can be valuable for drug delivery applications of GO sheets.

Unexpected persistence of cis-bridged chains in compressed AuF3.

Raman scattering measurements indicate that cis-bridged chains are retained in AuF3 even at a compression of 45 GPa - in contrast to meta-GGA calculations suggesting that structures with such motifs are thermodynamically unstable above 4 GPa. This metastability implies that novel gold fluorides (e.g. AuF2) might be attainable at lower pressures than previously proposed.

Volume expansive pressure (VEP) driven non-trivial topological phase transition in LiMgBi.

Topological Insulators (TI) exhibit robust spin-locked dissipationless Fermion transport along the surface states. In the current study, we use first-principles calculations to investigate a Topological Phase Transition (TPT) in a Half-Heusler (HH) compound LiMgBi driven by a Volume Expansive Pressure (VEP) which is attributed to the presence of, intrinsic voids, thermal perturbations and/or due to a phenomena known as cavity nuclei. We find that, the dynamically stable face-centred cubic (FCC) structure of LiMgBi (which belongs to the F4[combining macron]3m[216] space group), undergoes TPT beyond a critical VEP (at 4.0%). The continuous application of VEP from 0.0% to 8.0% results in a phase transition from a, band insulator to a Dirac semi-metal nature. Qualitatively, the Dirac cone formation and band inversion along the high symmetry point Γ in the Brillouin Zone (BZ) are analysed in terms of Electronic Band Structure (EBS) and Projected Local Density of States (LDOS). The TPT is further characterised by the [Doublestruck Z]2 invariant, (ν0, ν1ν2ν3) ≡ (1, 0 0 0) along the (0001) surface which indicates quantitatively that, HH LiMgBi is a strong TI. We hence propose, HH LiMgBi (known for its piezoelectric, thermo-electric and semi-conducting applications) as a strong TI with potential multi-purpose application in the field of electronics, spintronics and quantum computation.

High-Pressure Phase Transitions of Zinc Difluoride up to 55 GPa.

Studying the effect of high pressure (exceeding 10 kbar) on the structure of solids allows us to gain deeper insight into the mechanism governing crystal structure stability. Here, we report a study on the high-pressure behavior of zinc difluoride (ZnF2)-an archetypical ionic compound which at ambient pressure adopts the rutile (TiO2) structure. Previous investigations, limited to a pressure of 15 GPa, revealed that this compound undergoes two pressure-induced phase transitions, i.e., TiO2 → CaCl2 at 4.5 GPa and CaCl2 → HP-PdF2 at 10 GPa. Within this joint experimental-theoretical study, we extend the room-temperature phase diagram of ZnF2 up to 55 GPa. By means of Raman spectroscopy measurements we identify two new phase transitions, HP-PdF2 → HP1-AgF2 at 30 GPa and HP1-AgF2 → PbCl2 at 44 GPa. These results are confirmed by density functional theory calculations which indicate that in the HP1-AgF2 polymorph the coordination sphere of Zn2+ undergoes drastic changes upon compression. Our results point to important differences in the high-pressure behavior of ZnF2 and MgF2, despite the fact that both compounds contain cations of similar size. We also argue that the HP1-AgF2 structure, previously observed only for AgF2, might be observed at large compression in other AB2 compounds.

Molecular interaction between bi-antennary phenylboronic acid and sialic acid using density functional theory and multi-time scale trajectories.

Communicated by Ramaswamy H. Sarma.

Effect of aqueous medium on low-frequency dynamics, chemical activity and physical properties of a spherical virus.

In this work, we have studied the effect of size and aqueous medium on the low-frequency dynamics, physical properties like melting temperature and glass transition temperature and chemical properties like catalytic activation energy of spherical virus using Lindemann's criteria and Arrhenius relation under their dynamic limit. The melting temperature and catalytic activation energy decrease with decreasing size of spherical virus. The glass transition temperature which increases with decreasing size of the virus is analyzed through the size dependent melting temperature. The melting temperature and catalytic activation energy of spherical virus of particular size increases when it is embedded in glycerol or water due to mismatch of the physical properties at the interface of virus and surrounding medium. In addition, the glass transition temperature of free and glycerol/water embedded virus using low-frequency vibrational modes has been calculated under the framework of elastic continuum approximation model. The glass transition temperature of spherical virus decreases with size when embedded in glycerol or water. A correlation between [Formula: see text] and [Formula: see text] is also drawn for spherical viruses. The study can be useful for spherical virus borne therapy i.e. in detecting and killing of the spherical viruses using a principle based on acoustic phonons (sound waves) resonance.Communicated by Ramaswamy H. Sarma.