Hydrogen-induced phase stability and phonon mediated-superconductivity in two-dimensional van der Waals Ti2C MXene monolayer.

Herein, we report the phase stability of the hydrogenated Ti2C MXene monolayer using an evolutionary algorithm based on density functional theory. We predict the existence of hexagonal Ti2CH, Ti2CH2, and Ti2CH4. The dynamic and energetic stabilities of the predicted structures are verified through phonon dispersion and formation energy, respectively. The electron-phonon coupling is carefully investigated by employing isotropic Eliashberg theory. The Tc values are 0.2 K, 2.3 K, and 9.0 K for Ti2CH, Ti2CH2, and Ti2CH4, respectively. The translation and libration adopted by stretch and bent vibrations contribute to the increasing Tc of Ti2CH4. The high-frequency hydrogen modes contribute to the critical temperature increase. Briefly, this work not only highlights the effect of H-content on the increments of Tc for Ti2CHx, but also demonstrates the first theoretical evidence of the existence of H-rich MXene in the example of Ti2CH4. Therefore, it potentially provides a guideline for developing hydrogenated 2D superconductive applications.

Unexplained dissociation pathways of two-body fragmentation of methane dication.

The ion-induced fragmentation of CH4 2+ into H+ and CH3 + is studied using a cold target recoil ion momentum spectroscopy in coincidence with the charge state of the post-collision projectile. Using constant velocity Ar9+ and N3+, results from four different datasets are presented, with a selection on the final charge state of the projectile (Ar8+ or Ar7+ and N2+ or N+). Three distinct dissociation pathways (I, II, and III) are observed for each dataset, with the mean kinetic energy release values of around 4.7, 5.8, and 7.9 eV, respectively. The electronic states that are populated correspond to electronic configurations (1t2)-2 and (2a1)-1(1t2)-1 of the methane dication, CH4 2+. The relative branching ratios between the three pathways are discussed as a function of the charge state of the post-collision projectile, and a strong correlation with the specific nature of the ion-molecule interaction is found. The existing ab initio calculations have provided an explanation only for pathway II. In this article, we propose an explanation for pathway III, but pathway I still remains unexplained and requires further theoretical efforts. A discussion of the dependence of dissociation on the mode of excitation is presented.

Altered electrochemical properties of iron oxide nanoparticles by carbon enhance molecular biocompatibility through discrepant atomic interaction.

Recent advancement in nanotechnology seeks exploration of new techniques for improvement in the molecular, chemical, and biological properties of nanoparticles. In this study, carbon modification of octahedral-shaped magnetic nanoparticles (MNPs) was done using two-step chemical processes with sucrose as a carbon source for improvement in their electrochemical application and higher molecular biocompatibility. X-ray diffraction analysis and electron microscopy confirmed the alteration in single-phase octahedral morphology and carbon attachment in Fe3O4 structure. The magnetization saturation and BET surface area for Fe3O4, Fe3O4/C, and α-Fe2O3/C were measured as 90, 86, and 27 emu/g and 16, 56, and 89 m2/g with an average pore size less than 7 nm. Cyclic voltammogram and galvanostatic charge/discharge studies showed the highest specific capacitance of carbon-modified Fe3O4 and α-Fe2O3 as 213 F/g and 192 F/g. The in vivo biological effect of altered physicochemical properties of Fe3O4 and α-Fe2O3 was assessed at the cellular and molecular level with embryonic zebrafish. Mechanistic in vivo toxicity analysis showed a reduction in oxidative stress in carbon-modified α-Fe2O3 exposed zebrafish embryos compared to Fe3O4 due to despaired influential atomic interaction with sod1 protein along with significant less morphological abnormalities and apoptosis. The study provided insight into improving the characteristic of MNPs for electrochemical application and higher biological biocompatibility.

Development of a time of flight spectrometer based on position sensitive multi-wire proportional counters for fission fragment mass distribution studies.

Characteristics and performance of a time of flight (TOF) spectrometer developed for performing fission mass distribution studies are presented. The spectrometer contains two TOF arms based on multi-wire proportional counters (MWPCs). Each arm has two MWPCs to form a start-stop detection system for TOF measurements. The start detector has an active area of 4 × 4 cm2. The stop detector is a two-dimensional position sensitive MWPC with an active area of 16 × 11 cm2. Salient features of the MWPCs are the use of reduced sub-millimeter wire pitches of 0.635 and 0.317 mm in the electrodes along with the use of gold plated tungsten wires of diameters 10 and 20 µm. A delay line for position electrodes is prepared using chip inductors and capacitors. Ten different configurations of MWPC were investigated for the start detector, which involved the use of three and four electrode geometries, use of different wire pitches, and use of aluminized mylar for timing electrodes. Performance results close to micro-channel plate detectors have been observed with some designs of MWPC, displaying rise times better than 2 ns with an estimated inherent time resolution of ∼100 ps FWHM. A position resolution of ∼1 mm (FWHM) has been observed. Design features of the MWPCs and their test performance results are described in this article.

Novel green phosphorene as a superior chemical gas sensing material.

Green phosphorus and its monolayer variant, green phosphorene (GreenP), are the recent members of two-dimensional (2D) phosphorus polymorphs. The new polymorph possesses the high stability, tunable direct bandgap, exceptional electronic transport, and directionally anisotropic properties. All these unique features could reinforce it the new contender in a variety of electronic, optical, and sensing devices. Herein, we present gas-sensing characteristics of pristine and defected GreenP towards major environmental gases (i. e., NH3, NO, NO2, CO, CO2, and H2O) using combination of the density functional theory, statistical thermodynamic modeling, and the non-equilibrium Green's function approach (NEGF). The calculated adsorption energies, density of states (DOS), charge transfer, and Crystal Orbital Hamiltonian Population (COHP) reveal that NO, NO2, CO, CO2 are adsorbed on GreenP, stronger than both NH3 and H2O, which are weakly physisorbed via van der Waals interactions. Furthermore, substitutional doping by sulfur can selectively intensify the adsorption towards crucial NO2 gas because of the enhanced charge transfer between p orbitals of the dopant and the analyte. The statistical estimation of macroscopic measurable adsorption densities manifests that the significant amount of NO2 molecules can be practically adsorbed at ambient temperature even at the ultra-low concentration of part per billion (ppb). In addition, the current-voltage (I-V) characteristics of S-doped GreenP exhibit a variation upon NO2 exposure, indicating the superior sensitivity in sensing devices. Our work sheds light on the promising application of the novel GreenP as promising chemical gas sensors.

High temperature-mediated rocksalt to wurtzite phase transformation in cadmium oxide nanosheets and its theoretical evidence.

Herein, a high temperature-induced phase transformation (PT) in chemically grown CdO thin films is demonstrated, and its corresponding electronic origin further investigated by density functional theory. In particular, the cubic rocksalt to hexagonal wurtzite PT in the CdO thin film annealed at 900 °C was confirmed by X-ray diffraction (XRD), which was consistent with the high-resolution transmission electron microscopy (TEM) results. Moreover, atomic force microscopy and scanning electron microscopy clearly evidenced the morphological evolution via the formation of a nanosheet network in the wurtzite-phase CdO film. The high temperature treatment also led to a significant enhancement in the optical band gap from 2.2 to 3.2 eV, as manifested by UV-visible spectroscopy. The enhanced surface roughness of the nanosheet caused a deviation in the net dipole moment, which may break the polarizable bonds and help in reducing the average dielectric constant, resulting in a band gap opening for the transformed phase. Furthermore, X-ray absorption spectroscopy at the oxygen k-edge revealed a notable shift in the inflection point of the absorption edge, while the X-ray photoelectron spectroscopy (XPS) Cd 3d and O 1s spectra suggested a gradual reduction in the CdO2 phase with an increase in annealing temperature. In addition, different complementary techniques including Rutherford backscattering and Raman spectroscopy were exploited to understand the aforementioned PT and its structural correlation. Finally, molecular dynamics simulation together with density functional theory calculation suggested that the symmetry modification at the Brillouin zone boundary provides a succinct signature for the PT in the CdO thin film.

Anticarcinogenic activity of blue fluorescent hexagonal boron nitride quantum dots: as an effective enhancer for DNA cleavage activity of anticancer drug doxorubicin.

Blue fluorescent hexagonal boron nitride quantum dots (h-BNQDs) of ∼10 nm size as an effective enhancer for DNA cleavage activity of anticancer drug doxorubicin (DOX) were synthesized using simple one-step hydrothermal disintegration of exfoliated hexagonal boron nitride at very low temperature âˆ¼ 120 °C. Boron nitride quantum dots (BNQDs) at a concentration of 25 µg/ml enhanced DNA cleavage activity of DOX up to 70% as checked by converting supercoiled fragment into nicked circular PBR322 DNA. The interaction of BNQDs with DOX is proportional to the concentration of BNQDs, with binding constant K b ∼0.07338 µg/ml. In addition, ab initio theoretical results indicate that DOX is absorbed on BNQDs at the N-terminated edge with binding energy -1.075 eV and prevented the normal replication mechanisms in DNA. BNQDs have been shown to kill the breast cancer cell MCF-7 extensively as compared with the normal human keratinocyte cell HaCaT. The cytotoxicity of BNQDs may be correlated with reduced reactive oxygen species level and increased apoptosis in MCF-7 cells, which may be liable to enhance the anticancerous activity of DOX. The results provide a base to develop BNQD-DOX as a more effective anticancer drug.

Graphitic carbon nitride nano sheets functionalized with selected transition metal dopants: an efficient way to store CO2.

Proficient capture of carbon dioxide (CO2) is considered to be a backbone for environment protection through countering the climate change caused by mounting carbon content. Here we present a comprehensive mechanism to design novel functional nanostructures capable of capturing a large amount of CO2 efficiently. By means of van der Waals corrected density functional theory calculations, we have studied the structural, electronic and CO2 storage properties of carbon nitride (g-C6N8) nano sheets functionalized with a range of transition metal (TM) dopants ranging from Sc to Zn. The considered TMs bind strongly to the nano sheets with binding energies exceeding their respective cohesive energies, thus abolishing the possibility of metal cluster formation. Uniformly dispersed TMs change the electronic properties of semiconducting g-C6N8 through the transfer of valence charges from the former to the latter. This leaves all the TM dopants with significant positive charges, which are beneficial for CO2 adsorption. We have found that each TM's dopants anchor a maximum of four CO2 molecules with suitable adsorption energies (-0.15 to -1.0 eV) for ambient condition applications. Thus g-C6N8 nano sheets functionalized with selected TMs could serve as an ideal sorbent for CO2 capture.

Light metal decorated graphdiyne nanosheets for reversible hydrogen storage.

The sensitive nature of molecular hydrogen (H2) interaction with the surfaces of pristine and functionalized nanostructures, especially two-dimensional materials, has been a subject of debate for a while now. An accurate approximation of the H2 adsorption mechanism has vital significance for fields such as H2 storage applications. Owing to the importance of this issue, we have performed a comprehensive density functional theory (DFT) study by means of several different approximations to investigate the structural, electronic, charge transfer and energy storage properties of pristine and functionalized graphdiyne (GDY) nanosheets. The dopants considered here include the light metals Li, Na, K, Ca, Sc and Ti, which have a uniform distribution over GDY even at high doping concentration due to their strong binding and charge transfer mechanism. Upon 11% of metal functionalization, GDY changes into a metallic state from being a small band-gap semiconductor. Such situations turn the dopants to a partial positive state, which is favorable for adsorption of H2 molecules. The adsorption mechanism of H2 on GDY has been studied and compared by different methods like generalized gradient approximation, van der Waals density functional and DFT-D3 functionals. It has been established that each functionalized system anchors multiple H2 molecules with adsorption energies that fall into a suitable range regardless of the functional used for approximations. A significantly high H2 storage capacity would guarantee that light metal-doped GDY nanosheets could serve as efficient and reversible H2 storage materials.

Disentangling the intricate atomic short-range order and electronic properties in amorphous transition metal oxides.

Solid state materials with crystalline order have been well-known and characterized for almost a century while the description of disordered materials still bears significant challenges. Among these are the atomic short-range order and electronic properties of amorphous transition metal oxides [aTMOs], that have emerged as novel multifunctional materials due to their optical switching properties and high-capacity to intercalate alkali metal ions at low voltages. For decades, research on aTMOs has dealt with technological optimization. However, it remains challenging to unveil their intricate atomic short-range order. Currently, no systematic and broadly applicable methods exist to assess atomic-size structure, and since electronic localization is structure-dependent, still there are not well-established optical and electronic mechanisms for modelling the properties of aTMOs. We present state-of-the-art systematic procedures involving theory and experiment in a self-consistent computational framework to unveil the atomic short-range order and its role for the electronic properties. The scheme is applied to amorphous tungsten trioxide aWO3, which is the most studied electrochromic aTMO in spite of its unidentified atomic-size structure. Our approach provides a one-to-one matching of experimental data and corresponding model structure from which electronic properties can be directly calculated in agreement with the electronic transitions observed in the XANES spectra.

Role of vacancies, light elements and rare-earth metals doping in CeO2.

The magnetic properties and electronic structures of pure, doped and defective cerium oxide (CeO2) have been studied theoretically by means of ab initio calculations based on the density function theory (DFT) with the hybrid HF/DFT technique named PBE0. Carbon (C), nitrogen (N), phosphorus (P), sulphur (S), lanthanum (La) and praseodymium (Pr) doped in CeO2 and CeO2 containing oxygen vacancies (Ov) were considered. Our spin-polarized calculations show that C, N, Pr dopants and Ov defects magnetize the non-magnetic CeO2 in different degree. The optical band gap related to photocatalysis for pure CeO2, corresponding to the ultraviolet region, is reduced obviously by C, N, S, Pr impurities and oxygen vacancies, shifting to the visible region and even further to the infrared range. Especially, N-, S- and Pr-doped CeO2 could be used to photocatalytic water splitting for hydrogen production. As the concentration of Ov increasing up to 5%, the CeO2 exhibits a half-metallic properties.

Static and Dynamical Properties of heavy actinide Monopnictides of Lutetium.

In this work, density functional theory within the framework of generalized gradient approximation has been used to investigate the structural, elastic, mechanical, and phonon properties of lutetium monopnictides in rock-salt crystal structure. The spin orbit coupling and Hubbard-U corrections are included to correctly predict the essential properties of these compounds. The elastic constants, Young's modulus E, Poisson's ratio v, shear modulus G, anisotropy factor A and Pugh's ratio are computed. We found that all lutetium monopnictides are anisotropic and show brittle character. From the wave velocities along [100], [110] and [111] directions, melting temperature of lutetium monopnictides are predicted. Dynamical stability of these monopnictides has been studied by density functional perturbation theory.

Dynamic compression of dense oxide (Gd3Ga5O12) from 0.4 to 2.6 TPa: Universal Hugoniot of fluid metals.

Materials at high pressures and temperatures are of great current interest for warm dense matter physics, planetary sciences, and inertial fusion energy research. Shock-compression equation-of-state data and optical reflectivities of the fluid dense oxide, Gd3Ga5O12 (GGG), were measured at extremely high pressures up to 2.6 TPa (26 Mbar) generated by high-power laser irradiation and magnetically-driven hypervelocity impacts. Above 0.75 TPa, the GGG Hugoniot data approach/reach a universal linear line of fluid metals, and the optical reflectivity most likely reaches a constant value indicating that GGG undergoes a crossover from fluid semiconductor to poor metal with minimum metallic conductivity (MMC). These results suggest that most fluid compounds, e.g., strong planetary oxides, reach a common state on the universal Hugoniot of fluid metals (UHFM) with MMC at sufficiently extreme pressures and temperatures. The systematic behaviors of warm dense fluid would be useful benchmarks for developing theoretical equation-of-state and transport models in the warm dense matter regime in determining computational predictions.

Adsorption mechanism of graphene-like ZnO monolayer towards CO2 molecules: enhanced CO2 capture.

This work aims to efficiently capture CO2 on two-dimensional (2D) nanostructures for effective cleaning of our atmosphere and purification of exhausts coming from fuel engines. Here, we have performed extensive first principles calculations based on density functional theory (DFT) to investigate the interaction of CO2 on a recently synthesized ZnO monolayer (ZnO-ML) in its pure, defected and functionalized form. A series of rigorous calculations yielded the most preferential binding configurations of the CO2 gas molecule on a ZnO-ML. It is observed that the substitution of one oxygen atom with boron, carbon and nitrogen on the ZnO monolayer resulted into enhanced CO2 adsorption. Our calculations show an enriched adsorption of CO2 on the ZnO-ML when substituting with foreign atoms like B, C and N. The improved adsorption energy of CO2 on ZnO suggests the ZnO-ML could be a promising candidate for future CO2 capture.

Giving a second thought to brisement force - a case report.

Fractures of temporomandibular joint (TMJ) may be caused by indirect trauma where force of trauma is transmitted to the mandibular condyle from a blow elsewhere or in other situations may also result from direct trauma. TMJ trauma in children is usually accompanied with pain, swelling, limited jaw movement and other additional findings. This report highlights a case of post traumatic trismus successfully managed with Brisement force - gradual tractional forces applied to the temporomandibular joint.

Minimally invasive burn care: a review of seven clinical studies of rapid and selective debridement using a bromelain-based debriding enzyme (Nexobrid®).

Current surgical and non-surgical eschar removal-debridement techniques are invasive or ineffective. A bromelainbased rapid and selective enzymatic debriding agent was developed to overcome these disadvantages and compared with the standard of care (SOC). The safety and efficacy of a novel Debriding Gel Dressing (DGD) was determined in patients with deep partial and full thickness burns covering up to 67% total body surface area (TBSA). This review summarizes data from seven studies, four of which were randomized clinical trials that included a SOC or control vehicle. DGD eschar debridement efficacy was >90% in all studies, comparable to the SOC and significantly greater than the control vehicle. The total area excised was less in patients treated with DGD compared with the control vehicle (22.9% vs. 73.2%, P<0.001) or the surgical/non-surgical SOC (50.5%, P=0.006). The incidence of surgical debridement in patients treated with DGD was lower than the SOC (40/163 [24.5%] vs. 119/170 [70.0%], P0.001). Less autografting was used in all studies. Long-term scar quality and function were similar in DGD- and SOCtreated. DGD is a safe and effective method of burn debridement that offers an alternative to surgical and non-surgical SOC.

Les protocoles actuels de détersion d'une brûlure, chirurgicaux et non chirurgicaux, sont soit invasifs soit inefficaces. Un enzyme détersif rapide et spécifique, dérivé de la bromélaïne, a été développé dans le but de palier à ces 2 inconvénients. Il a été comparé aux techniques usuelles (TU). L'efficacité et l'innocuité d'un Gel Topique Détersif (GTD) ont été évaluées chez des patients souffrant de brûlures intermédiaires et profondes atteignant jusqu'à 67% de la Surface Corporelle Totale (SCT). Cette revue compile les données de 7 études cliniques, dont 4, randomisées, faisaient appel aux TU ou à un groupe contrôle. La détersion obtenue avec GTD était toujours > 90%, comparable aux TU et meilleure que dans le groupe contrôle. La surface relative excisée totale était moindre après GTD que chez les contrôles (22.9% VS 73.2%, p<0,001) ou les patients sous TU (50.5%, p=0,006). Le nombre de patients ayant eu besoin de chirurgie a été inférieur dans le groupe GTD que dans le groupe TU (40/163 [24.5%] VS 119/170 [70%], p<0,001). Le recours aux greffes était moins fréquent dans toutes les études. Les qualités cicatricielle et fonctionnelle à distance étaient comparables après TU et GTD. GTD est une technique de détersion efficace et sûre qui offre une alternative au TU, chirurgical ou non.