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.

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.

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.

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.

Impact of comprehensive cardiovascular risk reduction programme on risk factor clustering associated with elevated blood pressure in an Indian industrial population.

BACKGROUND & OBJECTIVES: Cardiovascular risk factors clustering associated with blood pressure (BP) has not been studied in the Indian population. This study was aimed at assessing the clustering effect of cardiovascular risk factors with suboptimal BP in Indian population as also the impact of risk reduction interventions. METHODS: Data from 10543 individuals collected in a nation-wide surveillance programme in India were analysed. The burden of risk factors clustering with blood pressure and coronary heart disease (CHD) was assessed. The impact of a risk reduction programmme on risk factors clustering was prospectively studied in a sub-group. RESULTS: Mean age of participants was 40.9 ± 11.0 yr. A significant linear increase in number of risk factors with increasing blood pressure, irrespective of stratifying using different risk factor thresholds was observed. While hypertension occurred in isolation in 2.6 per cent of the total population, co-existence of hypertension and >3 risk factors was observed in 12.3 per cent population. A comprehensive risk reduction programme significantly reduced the mean number of additional risk factors in the intervention population across the blood pressure groups, while it continued to be high in the control arm without interventions (both within group and between group P<0.001). The proportion of 'low risk phenotype' increased from 13.4 to 19.9 per cent in the intervention population and it was decreased from 27.8 to 10.6 per cent in the control population (P<0.001). The proportion of individuals with hypertension and three more risk factors decreased from 10.6 to 4.7 per cent in the intervention arm while it was increased from 13.3 to 17.8 per cent in the control arm (P<0.001). INTERPRETATION & CONCLUSIONS: Our findings showed that cardiovascular risk factors clustered together with elevated blood pressure and a risk reduction programme significantly reduced the risk factors burden.

Predicted formation of superconducting platinum-hydride crystals under pressure in the presence of molecular hydrogen.

Noble metals adopt close-packed structures at ambient pressure and rarely undergo structural transformation at high pressures. Platinum (Pt) is normally considered to be unreactive and is therefore not expected to form hydrides under pressure. We predict that platinum hydride (PtH) has a lower enthalpy than its constituents solid Pt and molecular hydrogen at pressures above 21.5 GPa. PtH transforms to a hexagonal close-packed or face-centered cubic (fcc) structure between 70 and 80 GPa. Linear response calculations indicate that PtH is a superconductor at these pressures with a critical temperature of about 10-25 K. These findings help to shed light on recent observations of pressure-induced metallization and superconductivity in hydrogen-rich materials. We show that the formation of fcc noble metal hydrides under pressure is common and examine the possibility of superconductivity in these materials.

Crystal structure of the pressure-induced metallic phase of SiH4 from ab initio theory.

Metallization of pure solid hydrogen is of great interest, not least because it could lead to high-temperature superconductivity, but it continues to be an elusive goal because of great experimental challenges. Hydrogen-rich materials, in particular, CH(4), SiH(4), and GeH(4), provide an opportunity to study related phenomena at experimentally achievable pressures, and they too are expected to be high-temperature superconductors. Recently, the emergence of a metallic phase has been observed in silane for pressures just above 60 GPa. However, some uncertainty exists about the crystal structure of the discovered metallic phase. Here, we show by way of elimination, that a single structure that possesses all of the required characteristics of the experimentally observed metallic phase of silane from a pool of plausible candidates can be identified. Our density functional theory and GW calculations show that a structure with space group P4/nbm is metallic at pressures >60 GPa. Based on phonon calculations, we furthermore demonstrate that the P4/nbm structure is dynamically stable at >43 GPa and becomes the ground state at 97 GPa when zero-point energy contributions are considered. These findings could lead the way for further theoretical analysis of metallic phases of hydrogen-rich materials and stimulate experimental studies.

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.

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.

The effect of rural-to-urban migration on obesity and diabetes in India: a cross-sectional study.

BACKGROUND: Migration from rural areas of India contributes to urbanisation and may increase the risk of obesity and diabetes. We tested the hypotheses that rural-to-urban migrants have a higher prevalence of obesity and diabetes than rural nonmigrants, that migrants would have an intermediate prevalence of obesity and diabetes compared with life-long urban and rural dwellers, and that longer time since migration would be associated with a higher prevalence of obesity and of diabetes. METHODS AND FINDINGS: The place of origin of people working in factories in north, central, and south India was identified. Migrants of rural origin, their rural dwelling sibs, and those of urban origin together with their urban dwelling sibs were assessed by interview, examination, and fasting blood samples. Obesity, diabetes, and other cardiovascular risk factors were compared. A total of 6,510 participants (42% women) were recruited. Among urban, migrant, and rural men the age- and factory-adjusted percentages classified as obese (body mass index [BMI] >25 kg/m(2)) were 41.9% (95% confidence interval [CI] 39.1-44.7), 37.8% (95% CI 35.0-40.6), and 19.0% (95% CI 17.0-21.0), respectively, and as diabetic were 13.5% (95% CI 11.6-15.4), 14.3% (95% CI 12.2-16.4), and 6.2% (95% CI 5.0-7.4), respectively. Findings for women showed similar patterns. Rural men had lower blood pressure, lipids, and fasting blood glucose than urban and migrant men, whereas no differences were seen in women. Among migrant men, but not women, there was weak evidence for a lower prevalence of both diabetes and obesity among more recent (

Assessment of a nanoparticle bridge platform for molecular electronics measurements.

A combination of electron beam lithography, photolithography and focused ion beam milling was used to create a nanogap platform, which was bridged by gold nanoparticles in order to make electrical measurements and assess the platform under ambient conditions. Non-functionalized electrodes were tested to determine the intrinsic response of the platform and it was found that creating devices in ambient conditions requires careful cleaning and awareness of the contributions contaminants may make to measurements. The platform was then used to make measurements on octanethiol (OT) and biphenyldithiol (BPDT) molecules by functionalizing the nanoelectrodes with the molecules prior to bridging the nanogap with nanoparticles. Measurements on OT show that it is possible to make measurements on relatively small numbers of molecules, but that a large variation in response can be expected when one of the metal-molecule junctions is physisorbed, which was partially explained by attachment of OT molecules to different sites on the surface of the Au electrode using a density functional theory calculation. On the other hand, when dealing with BPDT, high yields for device creation are very difficult to achieve under ambient conditions. Significant hysteresis in the I-V curves of BPDT was also observed, which was attributed primarily to voltage induced changes at the interface between the molecule and the metal.

Li-decorated metal-organic framework 5: a route to achieving a suitable hydrogen storage medium.

A significant improvement in molecular hydrogen uptake properties is revealed by our ab initio calculations for Li-decorated metal-organic framework 5. We have found that two Li atoms are strongly adsorbed on the surfaces of the six-carbon rings, one on each side, carrying a charge of +0.9e per Li atom. Each Li can cluster three H(2) molecules around itself with a binding energy of 12 kJ (mol H(2))(-1). Furthermore, we show from ab initio molecular dynamics simulations with a hydrogen loading of 18 H(2) per formula unit that a hydrogen uptake of 2.9 wt % at 200 K and 2.0 wt % at 300 K is achievable. To our knowledge, this is the highest hydrogen storage capacity reported for metal-organic framework 5 under such thermodynamic conditions.

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.

Prevalence of multidrug resistant Mycobacterium tuberculosis in Lucknow, Uttar Pradesh.

BACKGROUND & OBJECTIVE: Multi-drug resistant (MDR) Mycobacterium tuberculosis isolates may be transmitted within communities due to dense population and poor hygienic conditions. For proper management and control of MDR-TB, understanding drug susceptibility pattern of M. tuberculosis isolates and their transmission pattern in every health care setting are essential. In the present study, we attempted to describe the current prevalence of MDR-TB in Lucknow district, Uttar Pradesh, and our observations on transmission of MDR isolates among populations in and around this area. METHODS: Patients diagnosed as that of pulmonary tuberculosis (PTB) were enrolled from primary level (PLH), secondary level (SLH) and tertiary level (TLH) healthcare centres from Lucknow district. Detailed history of intake of antitubercular drug in the past was taken to decipher initial/ acquired drug resistance. Sputum samples were cultured on Lowenstein-Jensen media to isolate mycobacteria. Drug susceptibility patterns of isolated M. tuberculosis isolates were recorded using 1 per cent proportion method. Transmission of MDR isolates in community was accessed by random amplified polymorphic DNA (RAPD). Isolates showing same band pattern on RAPD were retyped using different primers targeted to the inverted repeat sequence of IS6110 copies in M. tuberculosis genome. RESULTS: A total of 686 M. tuberculosis isolates were obtained from 1162 patients, of which 318 were from untreated subjects and 368 were from patients who were treated for tuberculosis in the past. Prevalence of MDR was 19.8 per cent, initial and acquired being 13.2 and 25.5 per cent respectively. Prevalence of resistance to any drug, MDR and individual drug resistance to isoniazid, streptomycin, ethambutol and rifampicin was significantly higher in patients who were treated in the past. Drug resistance was significantly higher at tertiary level health care compared to primary level health care. Genotypically similar clusters were seen at all levels of health care. It was not always possible to establish geographic connections within clusters. INTERPRETATION & CONCLUSION: High prevalence of both initial and acquired MDR was noted in M. tuberculosis isolates collected from pulmonary tuberculosis patients. Presence of small clusters of MDR isolates at all health care levels suggests transmission within the studied community.