Correlating Orbital Composition and Activity of LaMnxNi1-xO3 Nanostructures toward Oxygen Electrocatalysis.

The atomistic rationalization of the activity of transition metal oxides toward oxygen electrocatalysis is one of the most complex challenges in the field of electrochemical energy conversion. Transition metal oxides exhibit a wide range of structural and electronic properties, which are acutely dependent on composition and crystal structure. So far, identifying one or several properties of transition metal oxides as descriptors for oxygen electrocatalysis remains elusive. In this work, we performed a detailed experimental and computational study of LaMnxNi1-xO3 perovskite nanostructures, establishing an unprecedented correlation between electrocatalytic activity and orbital composition. The composition and structure of the single-phase rhombohedral oxide nanostructures are characterized by a variety of techniques, including X-ray diffraction, X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and electron microscopy. Systematic electrochemical analysis of pseudocapacitive responses in the potential region relevant to oxygen electrocatalysis shows the evolution of Mn and Ni d-orbitals as a function of the perovskite composition. We rationalize these observations on the basis of electronic structure calculations employing DFT with HSE06 hybrid functional. Our analysis clearly shows a linear correlation between the OER kinetics and the integrated density of states (DOS) associated with Ni and Mn 3d states in the energy range relevant to operational conditions. In contrast, the ORR kinetics exhibits a second-order reaction with respect to the electron density in Mn and Ni 3d states. For the first time, our study identifies the relevant DOS dominating both reactions and the importance of understanding orbital occupancy under operational conditions.

Ex situ Ge-doping of CZTS nanocrystals and CZTSSe solar absorber films.

Cu2ZnSn(S,Se)4 (CZTSSe) is a promising material for thin-film photovoltaics, however, the open-circuit voltage (VOC) deficit of CZTSSe prevents the device performance from exceeding 13% conversion efficiency. CZTSSe is a heavily compensated material that is rich in point defects and prone to the formation of secondary phases. The landscape of these defects is complex and some mitigation is possible by employing non-stoichiometric conditions. Another route used to reduce the effects of undesirable defects is the doping and alloying of the material to suppress certain defects and improve crystallization, such as with germanium. The majority of works deposit Ge adjacent to a stacked metallic precursor deposited by physical vapour deposition before annealing in a selenium rich atmosphere. Here, we use an established hot-injection process to synthesise Cu2ZnSnS4 nanocrystals of a pre-determined composition, which are subsequently doped with Ge during selenisation to aid recrystallisation and reduce the effects of Sn species. Through Ge incorporation, we demonstrate structural changes with a negligible change in the energy bandgap but substantial increases in the crystallinity and grain morphology, which are associated with a Ge-Se growth mechanism, and gains in both the VOC and conversion efficiency. We use surface energy-filtered photoelectron emission microscopy (EF-PEEM) to map the surface work function terrains and show an improved electronic landscape, which we attribute to a reduction in the segregation of low local effective work function (LEWF) Sn(II) chalcogenide phases.

Correlating Molecular Precursor Interactions with Device Performance in Solution-Processed Cu2ZnSn(S,Se)4 Thin-Film Solar Cells.

Research efforts aimed at improving the crystal quality of solution-processed Cu2ZnSn(S,Se)4 (CZTSSe) absorbers have largely employed delicate pre- and postprocessing strategies, such as multistep selenization, heat treatment in mixed chalcogen atmospheres, and multinary extrinsic doping that are often complex and difficult to reproduce. On the other hand, understanding and tuning chemical interactions in precursor inks prior to the thin-film deposition have received significantly less attention. Herein, we show for the first time how the complexation of metallic and chalcogen precursors in solution have a stark influence on the crystallization and optoelectronic quality of CZTSSe absorbers. By varying thiourea to metal cation ratios (TU/M) in dimethylformamide (DMF) and isopropyl alcohol (IPA)-based inks, we observed the formation of nanoscale metal-organic complexes and submicron size aggregates which play a key role in the morphology of the precursor layers obtained by spin-coating and drying steps. We also identify the primary cations in the complexation and assembling processes in solution. The morphology of the precursor film, in turn, has an important effect on grain growth and film absorber structure after the reactive annealing in the presence of Se. Finally, we establish a link between metal complexes in precursor solutions and device performance, with power conversion efficiency increasing from approximately 2 to 8% depending on the TU/M and Cu/(Zn + Sn) ratios.

Comparative Study Between Crushing Technique and Lateral Laminectomy of Middle Turbinate as Auxiliary Management in Patients Who Underwent Septoplasty with Concha Bullosa.

The aim is to compare two commonly performed surgical techniques, lateral resection and crushing for Concha Bullosa (CB) as auxiliary management in patients who underwent septoplasty. In Patients diagnosed with DNS and CB, using endoscopy and Computerized Tomography, NOSE score was calculated. All patients underwent septoplasty and depending upon the surgical method followed for CB, patients allotted in two groups. In group A, crushing of middle turbinate was performed using Blakesley forceps and in group B, lateral resection of CB was done. Postoperative NOSE scores were calculated at 6 months and outcomes were compared. Both the surgical methods were highly effective in the management of CB. All patients had significant improvement in the NOSE score when compared with the preoperative values. Two patients in group B developed synechia between the turbinate and lateral wall. However, the superiority of  one method over the other could not be established statistically. CB is a common anomaly in anatomy of nose and paranasal sinus. It frequently coexists with DNS and may cause sinus problems if it is over-pneumatised. In such cases, surgical correction is warranted. Crushing of MT and lateral resection are two commonly performed methods, both are equally effective, but the crushing technique has an advantage of mucosal preservation and less postoperative complications.

Decoupling the impact of bulk and surface point defects on the photoelectrochemical properties of LaFeO3 thin films.

Point defects (PDs) play a key role in the properties of semiconductor photoelectrodes, from doping density to carrier mobility and lifetime. Although this issue has been extensively investigated in the context of photovoltaic absorbers, the role of PDs in photoelectrodes for solar fuels remains poorly understood. In perovskite oxides such as LaFeO3 (LFO), PDs can be tuned by changing the cation ratio, cation substitution and oxygen content. In this paper, we report the first study on the impact of bulk and surface PDs on the photoelectrochemical properties of LFO thin films. We independently varied the La : Fe ratio, within 10% of the stoichiometric value, in the bulk and at the surface by tuning the precursor composition as well as selective acid etching. The structure and composition of thin films deposited by sol-gel methods were investigated by SEM-EDX, ICP-OES, XPS and XRD. Our analysis shows a correlation between the binding energies of Fe 2p3/2 and O 1s, establishing a link between the oxidation state of Fe and the covalency of the Fe-O bond. Electrochemical studies reveal the emergence of electronic states close to the valence band edge with decreasing bulk Fe content. DFT calculations confirm that Fe vacancies generate states located near the valence band, which act as hole-traps and recombination sites under illumination. Dynamic photocurrent responses associated with oxygen reduction and hydrogen evolution show that the stoichiometric La : Fe ratio provides the most photoactive oxide; however, this can only be achieved by independently tuning the bulk and surface compositions of the oxide.

Current Application and Future Prospects of 3D Printing in Otorhinolaryngology-A Narrative Review.

Application of three-dimensional printing (3D) technology is relatively new in healthcare, but significant progress has been made over the last few decades. The technology has been evolved and became more accessible and affordable for the medical use. The aim of the review article is to discuss the potential use  of 3D printing in otorhinolaryngology and head and neck surgery. In the article, use of this novel technology is discussed across various subspecialties in terms of skill training, surgical planning and development of customised prosthesis. Internet searching was also performed for the commercial utility of 3D printed devices in ENT patient care. 3D printing is a promising technology. Numerous articles have been published in the international literature on its potential use in healthcare and progress is being made regularly by researchers to expand its implications in ENT. However, shortage of suitable 3D material which simulate human tissues for developing better training models discloses area of further research. Integration of tissue engineering 3D bioprinting provides significant opportunity to develop functional 3D printed implant for postsurgical reconstruction and organ transplantation.

Mapping the Energetics of Defect States in Cu2ZnSnS4 films and the Impact of Sb Doping.

The sub-bandgap levels associated with defect states in Cu2ZnSnS4 (CZTS) thin films are investigated by correlating the temperature dependence of the absorber photoluminescence (PL) with the device admittance spectroscopy. CZTS thin films are prepared by thermolysis of molecular precursors incorporating chloride salts of the cations and thiourea. Na and Sb are introduced as dopants in the precursor layers to assess their impact on Cu/Zn and Sn site disorder, respectively. Systematic analysis of PL spectra as a function of excitation power and temperature show that radiative recombination is dominated by quasi-donor-acceptor pairs (QDAP) with a maximum between 1.03 and 1.18 eV. It is noteworthy that Sb doping leads to a transition from localized to delocalized QDAP. The activation energies obtained associated with QDAP emission closely correlate with the activation energies of the admittance responses in a temperature range between 150 K and room temperature in films with or without added dopants. Admittance data of CZTS films with no added dopants also have a strong contribution from a deeper state associated with Sn disorder. The ensemble of PL and admittance data, in addition to energy-filtered photoemission of electron microscopy (EF-PEEM), shows a detailed picture of the distribution of sub-bandgap states in CZTS and the impact of doping on their energetics and device performance.

Virtual Telephonic Follow-Up for Patients Undergone Septoplasty Amid the COVID Pandemic.

Septoplasty is a common procedure in ENT practice with fewer complication rates. Long term follow-up is usually not necessary. The aim of our study is to evaluate the feasibility of virtual telephonic consultation to follow-up the patients in the immediate postoperative period. After excluding the patients based on the criteria, twenty-four patients were telephonically followed up by a resident using structured NOSE questionnaires and the responses were noted. All the patients had improvement in symptoms with 14 patients completely asymptomatic (NOSE score of < 5). Two patients had moderate symptoms (NOSE score 30-50) and 8 patients had mild symptoms (nose score 5-25). Majority of the patients interviewed were satisfied with the telephonic follow up and were willing to accept such patient-friendly services in the future. Virtual Telephonic follow-up of patient undergone uncomplicated septoplasty is a feasible, cost-effective model with a high rate of patient satisfaction.

Promoting Active Electronic States in LaFeO3 Thin-Films Photocathodes via Alkaline-Earth Metal Substitution.

The effects of alkaline-earth metal cation (AMC; Mg2+, Ca2+, Sr2+, and Ba2+) substitution on the photoelectrochemical properties of phase-pure LaFeO3 (LFO) thin-films are elucidated by X-ray photoemission spectroscopy (XPS), X-ray diffraction (XRD), diffuse reflectance, and electrochemical impedance spectroscopy (EIS). XRD confirms the formation of single-phase cubic LFO thin films with a rather complex dependence on the nature of the AMC and extent of substitution. Interestingly, subtle trends in lattice constant variations observed in XRD are closely correlated with shifts in the binding energies of Fe 2p3/2 and O 1s orbitals associated with the perovskite lattice. We establish a scaling factor between these two photoemission peaks, unveiling key correlation between Fe oxidation state and Fe-O covalency. Diffuse reflectance shows that optical transitions are little affected by AMC substitution below 10%, which are dominated by a direct bandgap transition close to 2.72 eV. Differential capacitance data obtained from EIS confirm the p-type characteristic of pristine LFO thin-films, revealing the presence of sub-bandgap electronic state (A-states) close to the valence band edge. The density of A-states is decreased upon AMC substitution, while the overall capacitance increases (increase in dopant level) and the apparent flat-band potential shifts toward more positive potentials. This behavior is consistent with the change in the valence band photoemission edge. In addition, capacitance data of cation-substituted films show the emergence of deeper states centered around 0.6 eV above the valence band edge (B-states). Photoelectrochemical responses toward the hydrogen evolution and oxygen reduction reactions in alkaline solutions show a complex dependence on alkaline-earth metal incorporation, reaching incident-photon-to-current conversion efficiency close to 20% in oxygen saturated solutions. We rationalize the photoresponses of the LFO films in terms of the effect sub-bandgap states on majority carrier mobility, charge transfer, and recombination kinetics.

Mapping Shunting Paths at the Surface of Cu2ZnSn(S,Se)4 Films via Energy-Filtered Photoemission Microscopy.

The performance of Cu2ZnSn(S,Se)4 thin-film solar cells, commonly referred to as kesterite or CZTSSe, is limited by open-circuit voltage (VOC) values less than 60% of the maximum theoretical limit. In the present study, we employ energy-filtered photoemission microscopy to visualize nanoscale shunting paths in solution-processed CZTSSe films, which limit the VOC of cells to approximately 400 mV. These studies unveil areas of local effective work function (LEWF) narrowly distributed around 4.9 eV, whereas other portions show hotspots with LEWF as low as 4.2 eV. Localized valence band spectra and density functional theory calculations allow rationalizing the LEWF maps in terms of the CZTSSe effective work function broadened by potential energy fluctuations and nanoscale Sn(S,Se) phases.

Investigating the Role of the Organic Cation in Formamidinium Lead Iodide Perovskite Using Ultrafast Spectroscopy.

Organic cation rotation in hybrid organic-inorganic lead halide perovskites has previously been associated with low charge recombination rates and (anti)ferroelectric domain formation. Two-dimensional infrared spectroscopy (2DIR) was used to directly measure 470 ± 50 fs and 2.8 ± 0.5 ps time constants associated with the reorientation of formamidinium cations (FA+, NH2CHNH2+) in formamidinium lead iodide perovskite thin films. Molecular dynamics simulations reveal the FA+ agitates about an equilibrium position, with NH2 groups pointing at opposite faces of the inorganic lattice cube, and undergoes 90° flips on picosecond time scales. Time-resolved infrared measurements revealed a prominent vibrational transient feature arising from a vibrational Stark shift: photogenerated charge carriers increase the internal electric field of perovskite thin films, perturbing the FA+ antisymmetric stretching vibrational potential, resulting in an observed 5 cm-1 shift. Our 2DIR results provide the first direct measurement of FA+ rotation inside thin perovskite films, and cast significant doubt on the presence of long-lived (anti)ferroelectric domains, which the observed low charge recombination rates have been attributed to.

Single Molecular Precursor Solution for CuIn(S,Se)2 Thin Films Photovoltaic Cells: Structure and Device Characteristics.

A single molecular precursor solution is described for the deposition of CuIn(S,Se)2 (CIS) film onto Mo-coated glass substrates by spin coating, followed by annealing in Se atmosphere. Characterization of the films by X-ray diffraction, Raman spectroscopy and scanning electron microscopy demonstrates the formation of a highly homogeneous and compact 1.1 µm thick CIS layer, with a MoSe2 under-layer. Atomic force microscopy reveals the presence of spherical grains between 400 and 450 nm, featuring surface corrugation in the range of 30 nm. Film composition is found to be in close agreement with that of the precursor solution. Diffuse reflectance spectroscopy shows a direct band gap (Eg) of 1.36 eV. Intensity and temperature dependence photoluminescence spectra show characteristic features associated with a donor-acceptor pair recombination mechanism, featuring activation energy of 34 meV. Over 85 solar cell devices with the configuration Mo/CIS/CdS/i-ZnO/Al:ZnO/Ni-Al and an total area of 0.5 cm2 were fabricated and tested. The champion cell shows a power efficiency of 3.4% with an open circuit voltage of 521 mV and short circuit current of 14 mA/cm2 under AM 1.5 illumination and an external quantum efficiency above 60%. Overall variation in each of solar cell parameters remains below 10% of the average value, demonstrating the remarkable homogeneity of this solution processing method. To understand the limitation of devices, the dependence of the open-circuit voltage and impedance spectra upon temperature were analyzed. The data reveal that the CuIn(S,Se)2/CdS interface is the main recombination pathway with an activation energy of 0.79 eV as well as the presence of two "bulk" defect states with activation energies of 37 and 122 meV. We also estimated that the MoSe2 under-layer generates back contact barrier of 195 meV.

A correlation matrix of alkaline phosphatase and sporulation in diazotrophic cyanobacteria and its thermo-tolerant mutant.

Alkaline phosphatase (phosphomonoesterase i.e. PMEase) activity in heterocystous cyanobacteria Anabaena flos-aquae, Nostoc calcicola, Calothrix brevissima, Scytonema javanicum and Hapalosiphon intricatus is known to be temperature and pH dependent. Maximum level of enzyme activity was recorded at either 35 degrees C or 37.5 degrees C. Also, the cell bound phosphomonoesterase enzyme was shown to exhibit pH optima of 10.0 or 10.2. A thermo-tolerant (tr) mutant isolated after MNNG (N-methyl-N'-nitro-N-nitrosoguanidine) mutagenesis in Calothrix brevissima exhibited 10 degrees C higher temperature optima and comparatively high pH optima (pH 10.4) for phosphomonoesterase enzyme. The mutant grew with a maximum growth rate (k) at 50 degrees C. Activation energy (Ea) for cyanobacterial strains was in a narrow range between 45 to 52 kJ mol(-1). A little variation in temperature and pH optima was also observed in phosphomonoesterase activity of Calothrix brevissima and its thermo-tolerant mutant while utilizing various organic phosphates as substrate what indicated the substrate dependence temperature and pH optima. Cyanobacterial strains grown at their respective temperature and pH optima differentiated spores less frequently though, coupled with early initiation of spore.

A study on the bacteriological profile and antibiogram of bacteremia in children below 10 years in a tertiary care hospital in bangalore, India.

INTRODUCTION: Blood stream infections are very common in the pediatric age group. Patients with bacteremia may have either a transient bacteremia that may be rapidly and permanently cleared by a patient's host defenses with no major consequences, or persistent bacteremia which can be self-limited without development of focal infection or sequelae, or may progress to a more serious fatal infection or toxic symptoms. OBJECTIVES: The aim of our study is to analyze the hospital data on bacteremia in children less than 10 years with special reference to male and female cases, the pathogens involved, and the antibiotic susceptibility patterns. METHODS: Over a one year period samples were collected from 128 children who included all newborn babies and children admitted with fever and suspected of having sepsis. Blood was collected depending upon age groups with aseptic precaution and incubated at 37(o)C for 10 days. Subcultures were made on blood agar and MacConkey agar plates. Organisms were identified and antibiotic sensitivity test of the isolates were performed. RESULTS: Out of 128 suspected cases, 32 (25%) was culture positive. Male to female ratio is 1.28:1.0. Klebsiella species (43.75%) was the most common organism isolated followed by Staphylococcus aureus (18.75%). Prevalence of gram negative organism was 71.87%. Most of the gram negative organisms showed maximum resistance to ampicillin and the gram positive organisms to penicillin. In this study three gram negative organisms were extended-spectrum beta lactamases (ESBLs) producers and one Pseudomonas aeruginosa was metallo-beta lactamase (MBL) producer. 33.33% of staphylococcus aureus was Methicillin resistant Staphylococcus aureus (MRSA) strains. INTERPRETATION AND CONCLUSION: This study showed a 25% prevalence rate of bacteremia among children with an increasing prevalence in the age group of 5-10 years and also an observed decline in susceptibility of the pathogens to common antibiotics which ultimately stresses on the need for continuous screening and surveillance for antibiotic resistance in the pediatric care unit and calls for increased efforts to ensure more rational use of these drugs.