Vortex flow induced self-assembly in CsPbI3 rods leads to an improved electrical response towards external analytes.

We present a facile and versatile strategy for enabling CsPbI3 rods to self-assemble at an air-water interface. The CsPbI3 rods, which float at the air-water interface, align under the influence of the rotational flow field due to the vortex motion of a water subphase. The aligned CsPbI3 rods could be transferred onto various substrates without involving any sophisticated instrumentation. The temperature of the subphase, the concentration of the CsPbI3 aliquot, the rotational speed inducing vortex motion, and the lift-off position and angle of the substrate were optimized to achieve high coverage of the self-assembled rods of CsPbI3 on glass. The Rietveld refinement of the XRD profile confirms that the aligned CsPbI3 is in the pure orthorhombic phase ascribed to the Pnma space group. The hydrophilic carboxylic group of the oleic acid attaches to the Pb atoms of the halide perovskite rods, while their hydrophobic tails encapsulate the rods within their shell, creating a shielding barrier between the water and the perovskite surface like a reverse micelle. The aligned CsPbI3 rods exhibit a nearly 47-fold increment in current upon exposure to ammonia gas (amounting to 5.6 times higher sensitivity in ammonia sensing) compared to the non-aligned CsPbI3 rods.

Comprehensive study on the origin of orthorhombic phase stabilization in Gd-doped HfO2 and DFT calculations.

In recent times, ultra-thin films of hafnium oxide (HfO2) have shown ferroelectricity (FE) attributed to the orthorhombic (o) phase of HfO2 with space group Pca21. This polar o-phase could be stabilized in the doped thin film of the oxide. In the present work, both polar and non-polar o-phases of HfO2 could be stabilized in Gd-doped bulk polycrystalline HfO2. Rietveld analysis of XRD data shows that the relative population of o-phases in the presence of the monoclinic (m) phase of HfO2 increases with increasing Gd-content. The local environment around the host atom has been investigated by time differential perturbed angular correlation (TDPAC) spectroscopy, synchrotron based X-ray near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) measurements showed a reduction in grain size with increasing Gd-dopant indicating a solute drag effect. It could be established that the segregation of the Gd-dopant in the grain boundary is a thermodynamically favorable process and the solute drag effect plays an important role in nucleation of the o-phase in bulk HfO2. Stabilization of Gd in both Pbca and Pca21 phases of HfO2 was supported by defect formation energy calculations using density functional theory (DFT). The present study has important implications in future applications of HfO2 in ferroelectric devices and in understanding the role of dopants in stabilizing the o-phase of HfO2 in the bulk.

Insight study on synthesis and antibacterial mechanism of silver nanoparticles prepared from indigenous plant source of Jharkhand.

BACKGROUND: The Ag-NPs by green synthesis has a notable interest because of their eco-friendliness, economic views, feasibility, and applications in a wide range. Herein, native plants of Jharkhand (Polygonum plebeium, Litsea glutinosa, and Vangueria spinosus) were selected for the current work of Ag-NP synthesis and further antibacterial activity. Green synthesis was performed for Ag-NPs using Silver nitrate solution as precursor and the dried leaf extract performs as a reductant and stabilizer here. RESULT: Visually Ag-NP formation was observed along with a colour change and confirmed by UV-visible spectrophotometry on which an absorbance peak occurs at around 400-450nm. Further characterization was done on DLS, FTIR, FESEM, and XRD. Size around 45-86 nm of synthesized Ag-NPs was predicted through DLS. The synthesized Ag-NPs exhibited significant antibacterial activity against Bacillus subtilis (Gram-positive bacteria) and Salmonella typhi (Gram-negative bacteria). The finest antibacterial activity was disclosed by the Ag-NPs synthesized by Polygonum plebeium extract. The diameter of the zone of inhibition in the bacterial plate measured was 0-1.8 mm in Bacillus and 0-2.2 mm in Salmonella typhi. Protein-Protein interaction study was performed to study the effect of Ag-NPs towards different antioxidant enzyme system of bacterial cell. CONCLUSION: Present work suggest the Ag-NPs synthesized from P. plebeium were more stable for long term and might have prolonged antibacterial activity. In the future, these Ag-NPs can be applied in various fields like antimicrobial research, wound healing, drug delivery, bio-sensing, tumour/cancer cell treatment, and detector (detect solar energy). Schematic representation of Ag-NPs green synthesis, characterization, antibacterial activity and at the end, in silico study to analyse the mechanism of antibacterial activity.

Anomalous Hall effect in topological Weyl and nodal-line semimetal Heusler compound Co2VAl.

Magnetic topological semimetals (TSMs) with broken time-reversal symmetry are very rare and have drawn significant attention in condensed matter physics due to their numerous intriguing topological properties. Among these various magnetic TSMs, Co2-based full Heusler compounds are of current interest, since a few of these materials exhibit Weyl and nodal fermions in their topological band structure. In this work, we report a comprehensive study of anomalous Hall effect (AHE) in the ferromagnetic full Heusler compound Co2VAl. Recent studies indicate that the intrinsic AHE is closely related to the Berry curvature of the occupied electronic Bloch states. The present study of Co2VAl attempts to understand and explore the possibility of topology-induced AHE. The anomalous Hall resistivityρxyAis observed to scale quadratically with the longitudinal resistivityρxx. Our experimental results also reveal that the anomalous Hall conductivity (AHC) is ∼85 cm-1at 2 K with an intrinsic contribution of ∼75.6 S cm-1, and is nearly insensitive to temperature. The first principle calculations note that the Berry curvature originated from a gapped nodal line and symmetry-protected Weyl nodes near the Fermi level (EF) is the main source of AHE in this compound. Thus, this investigation on Co2VAl discloses that it is a ferromagnetic Weyl and nodal-line TSM. The theoretically calculated AHC is in well agreement with the experimentally obtained AHC.

Enhanced piezoelectric response in BTO NWs-PVDF composite through tuning of polar phase content.

We have fabricated a flexible, environment friendly piezoelectric nanogenerator (PENG) based on the ferroelectric Polyvinylidene fluoride (PVDF) composite incorporated with Barium titanate (BaTiO3) nanowires (NWs) of piezoelectric coefficientd33 = 308 pm V-1. The single-layered PENG can deliver output power density of 10µW cm-2and an output voltage of 2 V with a nominal mechanical load of 1 kPa. BaTiO3(BTO) NWs of different concentrations were incorporated into PVDF to tune the polar phase content, internal resistance, and optimize the output power. We show that there exists a critical value of BTO NWs loading of 15 wt%, beyond which the piezoelectric energy harvesting characteristics of the PVDF nanocomposites decrease. The oxygen vacancies present in the BTO NWs surface attract the fluorine ions of PVDF chain and favour the formation ofßphase. The enhanced value of dielectric constant and dielectric loss of BTO-PVDF samples in the low frequency region suggest strong interfacial polarization in the composite system. The fabricated PENG can charge a super-capacitor up to 4 V within 35 s. The origin of the high power output from the BTO (15 wt%)-PVDF composite is attributed to the combined effect of enhanced polar phase content, strong interfacial polarization, and reduced internal resistance. This study provides an effective pathway in enhancing the performance of BTO-PVDF based piezoelectric energy harvesters.

From Hazardous Waste to Green Applications: Selective Surface Functionalization of Waste Cigarette Filters for High-Performance Robust Triboelectric Nanogenerators and CO2 Adsorbents.

This article reports a novel and rational approach to convert waste cigarette filters (CFs), one of the largest sources of ocean pollution, into high-performance triboelectric nanogenerators (TENGs) and efficient CO2-capturing adsorbents. CFs are plasticized cellulose acetate, which take several years to degrade. To revalorize these fibers, selective amine surface functionalization is performed (10PAL-20T-CFs). For the proof of concept, when the modified fibers are employed in a TENG, it could generate an output voltage (96.63 V) and current (9.37 µA) that are, respectively, 43 and 8 times higher than those obtained employing the pristine CFs for the nanogenerator. The proposed TENG displays an instantaneous peak power of 3.75 mW, which is higher than that of many recently reported TENGs made from cellulose materials. Moreover, the TENG displayed outstanding durability to humidity and high-performance stability when it is subjected to cyclic loading (i.e., 12,000 cycles of loading-unloading). A 9 cm2 TENG could effectively light up 100 or more colored light-emitting diodes when it is manually pressed. Finally, the modified filter fibers show an excellent CO2 adsorption capacity of 1.93 mmol/g, which is 9.2 times higher than that obtained using the pristine fibers. These results demonstrate that hazardous wastes such as CFs can be upcycled into valuable resources.

Modulation of interfacial interactions toward strong and tough cellulose nanofiber-based transparent thin films with antifogging feature.

Cross-linking is often performed to overcome the weak mechanical properties of native polymer films in order to expand their functional properties and applications. While this approach offers enhanced strength to the film, the film also suffers from low flexibility, low toughness and high brittleness. However, in view of the growing demand for strong and tough transparent thin films, this article reported our study to develop films made from cellulose nanofiber (CNF) via tailoring the interfacial bonding interactions through the application of glycerol (Gly) and glutaraldehyde (GA), which functioned as a plasticizer and cross-linking agent, respectively. Among the prepared films, the 10GA-8Gly-CNF film exhibited the best results with regard to the enhancement in the tensile strength (21.1%), Young's modulus (10.6%), elongation at break (100%) and toughness (32.7%), as compared to the native CNF film. Importantly, treating the surface of the film to radiofrequency oxygen plasma endowed the film with antifogging property, without compromising the optical clarity.

Piezoelectric Nanogenerators based on Lead Zirconate Titanate nanostructures: an insight into the effect of potential barrier and morphology on the output power generation.

The high internal resistance of the perovskite materials used in Nanogenerators (NGs) lowers the power generation. It severely restricts their application for mechanical energy harvesting from the ambient source. In this work, we demonstrate a flexible Piezoelectric NG (PENG) with an improved device structure. Hydrothermally grown one-dimensional Lead Zirconate Titanate (Pb(ZrTi)O3) of different morphologies are used as the generating material. The morphology of the PZT nanostructures, engineered from nanoparticles to needle-shaped nanowires to increase the surface to volume ratio, provides effective mechanical contact with the electrode. The reduction of the internal resistance of the PENG has been achieved by two ways: (i) fabrication of interdigitated electrodes (IDE) to increase the interfacial polarization and (ii) lowering of Schottky barrier height (SBH) at the junction of the PZT nanostructure and the metal electrode by varying the electrode materials of different work functions. We find that lowering of the SBH at the interface contributes to an increased piezo voltage generation. The flexible nano needles-based PENG can deliver output voltage 9.5 V and power density 615µW cm-2on application low mechanical pressure (∼1 kPa) by tapping motion. The internal resistance of the device is ∼0.65 MΩ. It can charge a 35µF super-capacitor up to 5 V within 20 s. This study provides a systematic pathway to solve the bottlenecks in the piezoelectric nanogenerators due to the high internal resistance.

High sensitivity NH3 gas sensor with electrical readout made on paper with perovskite halide as sensor material.

In this paper we report a cheap, paper electronics based solid state gas sensor to detect NH3 gas selectively with a detection capability of better than 1 ppm. The sensor uses perovskite halide CH3NH3PbI3 (MAPI) as the active sensor material grown on a paper. This paper based sensor works at room temperature. The current through the paper sensor increases by one order on exposure to only 10 ppm NH3 gas. The calibrated sensitivity is ~55% for 1 ppm of NH3 gas in Nitrogen or Air. The current noise limited resolution estimated to be ~10 ppb. This work establishes perovskite halide as a new solid state gas sensing material that can reach sub ppm sensitivity using simple paper electronics. Use of paper and also solution method used to grow the active material makes the sensor cost effective and easy to manufacture. This type of disposable high sensitive paper sensor can be used for detection of NH3 as a marker in exhaled breathes for non-invasive diagnosis. The sensor formed on the paper, since it supports unheated operation, needs less than few nanowatt power for its operation.

ZnO/Si nanowires heterojunction array-based nitric oxide (NO) gas sensor with noise-limited detectivity approaching 10 ppb.

We report a ZnO/Silicon nanowire (ZnO/Si NWs) heterojunction array-based NO gas sensor operating at room temperature with an extremely high response (noise limited response ∼10 ppb). The sensor shows very high selectivity towards NO gas sensing and limited perturbation in response due to the presence of moisture. The sensor has been fabricated by using cost-effective chemical processing that is compatible with wafer-level processing. The vertically aligned Si NWs array has been made by an electroless etching method and the ZnO nanostructure was made by chemical solution deposition and spin-coating. Extensive cross-sectional electron microscopy and composition analysis by line EDS allowed us to make a physical model. The electrical characteristic of the model was to fit the I-V data before and after exposure to gas and essential changes in electrical parameters were obtained. This was then explained based on a proposal for the mechanism of gas sensing. We observe that the heterostructure leads to a synergetic effect where the sensing response is more than the sum total of the individual components, namely the ZnO and the Si NWs. The response is much enhanced in the p-n junction when the n-ZnO nanostructure interfaces with p-Si NW compared to that in the n-n junction formed by ZnO on n-Si NW.

Fast response paper based visual color change gas sensor for efficient ammonia detection at room temperature.

We show that a cheap, disposable type rapid paper sensor (working at room temperature) can be made using perovskite halide CH3NH3PbI3 (MAPI) to detect presence of the toxic ammonia gas (NH3)by just color change, where the black colored MAPI film (on the paper) changes to yellow color in presence of a very low concentration of NH3 gas. The sensor can detect presence of NH3 gas in open or closed atmosphere down to around 10 ppm with a response time of nearly 10 sec which decreases to few seconds when the concentration exceeds 20 ppm. The easy to fabricate sensor paper being a visual sensor does not need any other extra equipment for its operation. The sensor is not sensitive to moisture with RH upto 90% and does not also respond to gases like Methane (CH4), Nitrous Oxide (N2O), Carbon dioxide (CO2) etc in the test chamber each up to a concentration of 500 ppm. Conversion/decomposition of MAPI to PbI2 on exposure to NH3 has been proposed as the mechanism of color change and the mechanism has been established using a collection of techniques like XRD, EDX, UV-Visible absorption and Photo Luminescence.

Nonmonotonic particle-size-dependence of magnetoelectric coupling in strained nanosized particles of BiFeO3.

Using high resolution powder x-ray and neutron diffraction experiments, we determined the off-centered displacement of the ions within a unit cell and magnetoelectric coupling in nanoscale BiFeO3 (≈20-200 nm). We found that both the off-centered displacement of the ions and magnetoelectric coupling exhibit nonmonotonic variation with particle size. They increase as the particle size reduces from bulk and reach maximum around 30 nm. With further decrease in particle size, they decrease precipitously. The magnetoelectric coupling is determined by the anomaly in off-centering of ions around the magnetic transition temperature (T N ). The ions, in fact, exhibit large anomalous displacement around the T N which is analyzed using group theoretical approach. It underlies the nonmonotonic particle-size-dependence of off-centre displacement of ions and magnetoelectric coupling. The nonmonotonic variation of magnetoelectric coupling with particle size is further verified by direct electrical measurement of remanent ferroelectric hysteresis loops at room temperature under zero and ∼20 kOe magnetic field. Competition between enhanced lattice strain and compressive pressure appears to be causing the nonmonotonic particle-size-dependence of off-centre displacement while coupling between piezo and magnetostriction leads to nonmonotonicity in the variation of magnetoelectric coupling.

Serum-based diagnostic prediction of oral submucous fibrosis using FTIR spectrometry.

Oral submucous fibrosis (OSF) is found to have the highest malignant potentiality among all other pre-cancerous lesions. However, its detection prior to tissue biopsy can be challenging in clinics. Moreover, biopsy examination is invasive and painful. Hence, there is an urgent need of new technology that facilitates accurate diagnostic prediction of OSF prior to biopsy. Here, we used FTIR spectroscopy coupled with chemometric techniques to distinguish the serum metabolic signatures of OSF patients (n=30) and healthy controls (n=30). Serum biochemical analyses have been performed to further support the FTIR findings. Absorbance intensities of 45 infrared wavenumbers differed significantly between OSF and normal serum FTIR spectra representing alterations in carbohydrates, proteins, lipids and nucleic acids. Nineteen prominent significant wavenumbers (P≤0.001) at 1020, 1025, 1035, 1039, 1045, 1078, 1055, 1100, 1117, 1122, 1151, 1169, 1243, 1313, 1398, 1453, 1544, 1650 and 1725cm-1 provided excellent segregation of OSF spectra from normal using multivariate statistical techniques. These findings provided essential information on the metabolic features of blood serum of OSF patients and established that FTIR spectroscopy coupled with chemometric analysis can be potentially useful in the rapid and accurate preoperative screening/diagnosis of OSF.

Molecular hydrogen in human breath: a new strategy for selectively diagnosing peptic ulcer disease, non-ulcerous dyspepsia and Helicobacter pylori infection.

The gastric pathogen Helicobacter pylori utilizes molecular hydrogen (H2) as a respiratory substrate during colonization in the gastric mucosa. However, the link between molecular H2 and the pathogenesis of peptic-ulcer disease (PUD) and non-ulcerous dyspepsia (NUD) by the enzymatic activity of H. pylori still remains mostly unknown. Here we provide evidence that breath H2 excretion profiles are distinctly altered by the enzymatic activity of H. pylori for individuals with NUD and PUD. We subsequently unravelled the potential molecular mechanisms responsible for the alteration of H2 in exhaled breath in association with peptic ulcers, encompassing both gastric and duodenal ulcers, along with NUD. We also established that carbon-isotopic fractionations in the acid-mediated bacterial environment regulated by bacterial urease activity cannot discriminate the actual disease state i.e. whether it is peptic ulcer or NUD. However, our findings illuminate the unusual molecular H2 in breath that can track the precise evolution of PUD and NUD, even after the eradication of H. pylori infection. This deepens our understanding of the pathophysiology of PUD and NUD, reveals non-invasively the actual disease state in real-time and thus offers a novel and robust new-generation strategy for treating peptic-ulcer disease together with non-ulcer related complications even when the existing (13)C-urea breath test ((13)C-UBT) fails to diagnose.

Non-invasive 13C-glucose breath test using residual gas analyzer-mass spectrometry: a novel tool for screening individuals with pre-diabetes and type 2 diabetes.

We report, for the first time, the clinical feasibility of a novel residual gas analyzer mass spectrometry (RGA-MS) method for accurate evaluation of the (13)C-glucose breath test ((13)C-GBT) in the diagnosis of pre-diabetes (PD) and type 2 diabetes mellitus (T2D). In T2D or PD, glucose uptake is impaired and results in blunted isotope enriched (13)CO2 production in exhaled breath samples. Using the Receiver operating characteristics (ROC) curve analysis, an optimal diagnostic cut-off point of the (13)CO2/(12)CO2 isotope ratios expressed as the delta-over-baseline (DOB) value, was determined to be δDOB(13)C‰ = 28.81‰ for screening individuals with non-diabetes controls (NDC) and pre-diabetes (PD), corresponding to a sensitivity of 100% and specificity of 94.4%. We also determined another optimal diagnostic cut-off point of δDOB(13)C‰ = 19.88‰ between individuals with PD and T2D, which exhibited 100% sensitivity and 95.5% specificity. Our RGA-MS methodology for the (13)C-GBT also manifested a typical diagnostic positive and negative predictive value of 96% and 100%, respectively. The diagnostic accuracy, precision and validity of the results were also confirmed by high-resolution optical cavity enhanced integrated cavity output spectroscopy (ICOS) measurements. The δDOB(13)C‰ values measured with RGA-MS method, correlated favourably (R(2) = 0.979) with those determined by the laser based ICOS method. Moreover, we observed that the effects of endogenous CO2 production related to basal metabolic rates in individuals were statistically insignificant (p = 0.37 and 0.73) on the diagnostic accuracy. Our findings suggest that the RGA-MS is a valid and sufficiently robust method for the (13)C-GBT which may serve as an alternative non-invasive point-of-care diagnostic tool for routine clinical practices as well as for large-scale diabetes screening purposes in real-time.

Residual gas analyzer mass spectrometry for human breath analysis: a new tool for the non-invasive diagnosis of Helicobacter pylori infection.

A residual gas analyzer (RGA) coupled with a high vacuum chamber is described for the non-invasive diagnosis of the Helicobacter pylori (H. pylori) infection through ¹³C-urea breath analysis. The present RGA-based mass spectrometry (MS) method is capable of measuring high-precision ¹³CO2 isotope enrichments in exhaled breath samples from individuals harboring the H. pylori infection. The system exhibited 100% diagnostic sensitivity, and 93% specificity alongside positive and negative predictive values of 95% and 100%, respectively, compared with invasive endoscopy-based biopsy tests. A statistically sound diagnostic cut-off value for the presence of H. pylori was determined to be 3.0‰ using a receiver operating characteristic curve analysis. The diagnostic accuracy and validity of the results are also supported by optical off-axis integrated cavity output spectroscopy measurements. The δ¹³(DOB)C‰ values of both methods correlated well (R² = 0.9973 at 30 min). The RGA-based instrumental setup described here is simple, robust, easy-to-use and more portable and cost-effective compared to all other currently available detection methods, thus making it a new point-of-care medical diagnostic tool for the purpose of large-scale screening of the H. pylori infection in real time. The RGA-MS technique should have broad applicability for ¹³C-breath tests in a wide range of biomedical research and clinical diagnostics for many other diseases and metabolic disorders.

Effect of size reduction on the structural and magnetic order in LaMnO(3+δ) (δ ≈ 0:03) nanocrystals: a neutron diffraction study.

We report a structural transition from the orthorhombic to the rhombohedral phase upon size reduction in nanocrystalline LaMnO(3+δ) (δ ≈ 0:03) as revealed through neutron diffraction studies. The transition occurs when the average particle (crystallite) size is taken below ~50 nm without change of δ, which is fixed at around 0.03 as measured by a number of characterization tools. The change in the crystallographic structure is accompanied by a change in the magnetic order, where the canted antiferromagnetic order with moments in the basal (ab) plane for the bulk changes to collinear ferromagnetic order with spins along the c-axis for the nanocrystals. The spontaneous ferromagnetic moment ~3 µ(B) and the transition temperature of 260 K in LaMnO(3+δ) nanocrystals are similar to those found in La0:67Ca0:33MnO3 which has a much higher Mn(4+) content. The likely origin is traced to change in magnetic exchange interactions due to change in Mn-O bond lengths which become almost identical in the MnO6 octahedron in the rhombohedral structure in the absence of Jahn-Teller distortion. The study provides an example of structural and magnetic phase transition driven purely by size reduction and with no change in the chemical constituents.

Inverse magnetocaloric and exchange bias effects in single crystalline La0.5Sr0.5MnO3 nanowires.

We report the first observation of inverse magnetocaloric effect (IMCE) in hydrothermally synthesized single crystalline La0.5Sr0.5MnO3 nanowires. The core of the nanowires is phase separated with the development of double exchange driven ferromagnetism (FM) in the antiferromagnetic (AFM) matrix, whereas the surface is found to be composed of disordered magnetic spins. The FM phase scales with the effective magnetic anisotropy, which is directly probed by transverse susceptibility experiments. The surface exhibits a glassy behavior and undergoes spin freezing, which manifests as a positive peak (T(L) ~ 42 K) in the magnetic entropy change (-ΔS(M)) curves, thereby stabilizing the re-entrance of the conventional magnetocaloric effect. Precisely at T(L), the nanowires develop the exchange bias (EB) effect. Our results conclusively demonstrate that the mere coexistence of FM and AFM phases along with a disordered surface below their Néel temperature (T(N) ~ 210 K) does not trigger EB, but this develops only below the surface spin freezing temperature.

Evidence of a canted magnetic state in self-doped LaMnO(3+δ) (δ = 0.04): a magnetocaloric study.

We report a detailed investigation of the magnetocaloric properties of self-doped polycrystalline LaMnO(3+δ) with δ = 0.04. Due to the self-doping effect, the system exhibits a magnetic transition from a paramagnetic to ferromagnetic-like canted magnetic state (CMS) at ~120 K, which is associated with an appreciably large magnetocaloric effect (MCE). The CMS is an inhomogeneous magnetic phase developing due to a steady growth of antiferromagnetic correlation in its predominant ferromagnetic state below ∼120 K. The stabilization of CMS in this material is concluded from a comprehensive analysis of magnetocaloric data using Landau theory, which is in excellent agreement with our neutron diffraction study. The magnetic entropy change versus temperature curves for different applied fields collapse into a single curve, revealing a universal behavior of MCE. Our studies suggest that investigation of MCE is an effective technique to acquire fundamental understanding about the basic magnetic structure of a system with complex competing interactions.