Hazard assessment of hexagonal boron nitride and hexagonal boron nitride reinforced thermoplastic polyurethane composites using human skin and lung cells.

Hexagonal boron nitride (hBN) is an emerging two-dimensional material attracting considerable attention in the industrial sector given its innovative physicochemical properties. Potential risks are associated mainly with occupational exposure where inhalation and skin contact are the most relevant exposure routes for workers. Here we aimed at characterizing the effects induced by composites of thermoplastic polyurethane (TPU) and hBN, using immortalized HaCaT skin keratinocytes and BEAS-2B bronchial epithelial cells. The composite was abraded using a Taber® rotary abraser and abraded TPU and TPU-hBN were also subjected to photo-Fenton-mediated degradation mimicking potential weathering across the product life cycle. Cells were exposed to the materials for 24 h (acute exposure) or twice per week for 4 weeks (chronic exposure) and evaluated with respect to material internalization, cytotoxicity, and proinflammatory cytokine secretion. Additionally, comprehensive mass spectrometry-based proteomics and metabolomics (secretomics) analyses were performed. Overall, despite evidence of cellular uptake of the material, no significant cellular and/or protein expression profiles alterations were observed after acute or chronic exposure of HaCaT or BEAS-2B cells, identifying only few pro-inflammatory proteins. Similar results were obtained for the degraded materials. These results support the determination of hazard profiles associated with cutaneous and pulmonary hBN-reinforced polymer composites exposure.

An evolutionarily conserved mechanism controls reversible amyloids of pyruvate kinase via pH-sensing regions.

Amyloids are known as irreversible aggregates associated with neurodegenerative diseases. However, recent evidence shows that a subset of amyloids can form reversibly and fulfill essential cellular functions. Yet, the molecular mechanisms regulating functional amyloids and distinguishing them from pathological aggregates remain unclear. Here, we investigate the conserved principles of amyloid reversibility by studying the essential metabolic enzyme pyruvate kinase (PK) in yeast and human cells. We demonstrate that yeast PK (Cdc19) and human PK (PKM2) form reversible amyloids through a pH-sensitive amyloid core. Stress-induced cytosolic acidification promotes aggregation via protonation of specific glutamate (yeast) or histidine (human) residues within the amyloid core. Mutations mimicking protonation cause constitutive PK aggregation, while non-protonatable PK mutants remain soluble even upon stress. Physiological PK aggregation is coupled to metabolic rewiring and glycolysis arrest, causing severe growth defects when misregulated. Our work thus identifies an evolutionarily conserved, potentially widespread mechanism regulating functional amyloids during stress.

Nanoparticles Dysregulate the Human Placental Secretome with Consequences on Angiogenesis and Vascularization.

Exposure to nanoparticles (NPs) in pregnancy is increasingly linked to adverse effects on embryo-fetal development and health later in life. However, the developmental toxicity mechanisms of NPs are largely unknown, in particular potential effects on the placental secretome, which orchestrates many developmental processes pivotal for pregnancy success. This study demonstrates extensive material- and pregnancy stage-specific deregulation of placental signaling from a single exposure of human placental explants to physiologically relevant concentrations of engineered (silica (SiO2) and titanium dioxide (TiO2) NPs) and environmental NPs (diesel exhaust particles, DEPs). This includes a multitude of secreted inflammatory, vascular, and endocrine placental factors as well as extracellular vesicle (EV)-associated proteins. Moreover, conditioned media (CM) from NP-exposed explants induce pronounced anti-angiogenic and anti-vasculogenic effects, while early neurodevelopmental processes are only marginally affected. These findings underscore the potential of metal oxide NPs and DEPs for widespread interference with the placental secretome and identify vascular morphogenesis as a sensitive outcome for the indirect developmental toxicity of different NPs. Overall, this work has profound implications for the future safety assessment of NPs for industrial, commercial, or medical applications in pregnancy, which should consider placenta-mediated toxicity by holistic secretomics approaches to ensure the development of safe nanotechnologies.

Tuning the plasmonic resonance in TiN refractory metal.

Plasmonic coatings can absorb electromagnetic radiation from visible to far-infrared spectrum for the better performance of solar panels and energy saving smart windows. For these applications, it is important for these coatings to be as thin as possible and grown at lower temperatures on arbitrary substrates like glass, silicon, or flexible polymers. Here, we tune and investigate the plasmonic resonance of titanium nitride thin films in lower thicknesses regime varying from ~ 20 to 60 nm. High-quality crystalline thin films of route-mean-square roughness less than ~ 0.5 nm were grown on a glass substrate at temperature of ~ 200 °C with bias voltage of - 60 V using cathodic vacuum arc deposition. A local surface-enhanced-plasmonic-resonance was observed between 400 and 500 nm, which further shows a blueshift in plasmonic frequency in thicker films due to the increase in the carrier mobility. These results were combined with finite-difference-time-domain numerical analysis to understand the role of thicknesses and stoichiometry on the broadening of electromagnetic absorption.

Boron Nitride Nanosheets Induce Lipid Accumulation and Autophagy in Human Alveolar Lung Epithelial Cells Cultivated at Air-Liquid Interface.

Hexagonal boron nitride (hBN) is an emerging 2D material attracting significant attention due to its superior electrical, chemical, and therapeutic properties. However, inhalation toxicity mechanisms of hBN in human lung cells are poorly understood. Here, cellular interaction and effects of hBN nanosheets is investigated in alveolar epithelial cells cultured on porous inserts and exposed under air-liquid interface conditions for 24 h. hBN is taken up by the cells as determined in a label-free manner via RAMAN-confocal microscopy, ICP-MS, TEM, and SEM-EDX. No significant (p > 0.05) effects are observed on cell membrane integrity (LDH release), epithelial barrier integrity (TEER), interleukin-8 cytokine production or reactive oxygen production at tested dose ranges (1, 5, and 10 µg cm-2 ). However, it is observed that an enhanced accumulation of lipid granules in cells indicating the effect of hBN on lipid metabolism. In addition, it is observed that a significant (p < 0.05) and dose-dependent (5 and 10 µg cm-2 ) induction of autophagy in cells after exposure to hBN, potentially associated with the downstream processing and breakdown of excess lipid granules to maintain lipid homeostasis. Indeed, lysosomal co-localization of lipid granules supporting this argument is observed. Overall, the results suggest that the continuous presence of excess intracellular lipids may provoke adverse outcomes in the lungs.

Experimental and Theoretical Investigations of MAPbX3 -Based Perovskites (X=Cl, Br, I) for Photovoltaic Applications.

This work mainly focuses on synthesizing and evaluating the efficiency of methylammonium lead halide-based perovskite (MAPbX3 ; X=Cl, Br, I) solar cells. We used the colloidal Hot-injection method (HIM) to synthesize MAPbX3 (X=Cl, Br, I) perovskites using the specific precursors and organic solvents under ambient conditions. We studied the structural, morphological and optical properties of MAPbX3 perovskites using XRD, FESEM, TEM, UV-Vis, PL and TRPL (time-resolved photoluminescence) characterization techniques. The particle size and morphology of these perovskites vary with respect to the halide variation. The MAPbI3 perovskite possesses a low band gap and low carrier lifetime but delivers the highest PCE among other halide perovskite samples, making it a promising candidate for solar cell technology. To further enrich the investigations, the conversion efficiency of the MAPbX3 perovskites has been evaluated through extensive device simulations. Here, the optical constants, band gap energy and carrier lifetime of MAPbX3 were used for simulating three different perovskite solar cells, namely I, Cl or Br halide-based perovskite solar cells. MAPbI3 , MAPbBr3 and MAPbCl3 absorber layer-based devices showed ~13.7 %, 6.9 % and 5.0 % conversion efficiency. The correlation between the experimental and SCAPS simulation data for HIM-synthesized MAPBX3 -based perovskites has been reported for the first time.

Granularity mediated multiple reentrances with negative magnetoresistance in disordered TiN thin films.

Granular superconductors are the common examples of experimentally accessible model systems which can be used to explore various fascinating quantum phenomena that are fundamentally important and technologically relevant. One such phenomenon is the occurrence of reentrant resistive states in granular superconductors. Here, we report the observation of multiple reentrant resistive states for a disordered TiN thin film in its temperature and magnetic field dependent resistance measurements, R(T) and R(B), respectively. At each of the peak-temperatures corresponding to the zero-field R(T), a resistance peak appears in the R(B) around zero field which leads to a negative magnetoresistance (MR) region in its surrounding. These low-field negative MR regions appear for both perpendicular and parallel field directions with relatively higher amplitude and larger width for the parallel field. By adopting a granularity-based model, we show that the superconducting fluctuations in granular superconductors may lead to the observed reentrant states and the corresponding negative MR. Here, we propose that the reduction in the density of states in the fermionic channel due to the formation of Cooper pairs leads to the reentrant resistive state and the competition between the conduction processes in the single particle and Cooper channels result into the multiple resistive reentrances.

Experimental analysis of methylammonium and Formamidinium-based halide perovskite properties for optoelectronic applications.

Nowadays, the toxicity of lead in metal-halide perovskites is the most precarious obstruction in the commercialization of perovskite-based optoelectronic devices. However, Pb-free metal halide perovskites as environment-friendly materials because of their exceptional properties, such as band-gap tunability, narrow emission spectra, low toxicity and easy solution-processability, are potential candidates for optoelectronic applications. Recently, literature reported the poor structural stability and low-emission intensity of Bi-based perovskite NCs. Still, this paper focuses on the fabrication of Formamidinium (FA)-based Bi mixed halide and Methylammonium(MA)-based Bi-pure halide perovskites using Ligand-Assisted Reprecipitation Technique (LARP) technique. XRD diffraction patterns of FA-based perovskites were slightly broad, signifying the nanocrystalline form and limited size of perovskite nanocrystals. While the XRD diffraction patterns of MA3Bi2X9 (X = Cl/Br/I) perovskites were narrow, signifying the amorphous nature and larger size of perovskite nanocrystals. The peak positions were varied in MA-based bismuth halide perovskites with respect to the halide variation from Br to Cl to I ions. The optical study shows the variation in band gap and average lifetime with respect to halide variation leading to enhanced optical properties for device applications. The band-gap of FA3Bi2BrxCl1-x & FA3Bi2IxCl1-x perovskites was calculated to be around 3.7 & 3.8 eV, respectively, while in MA-halide perovskites the band-gap was calculated to be 2.8 eV, 3.1 eV & 3.4 eV with respect to halide variation from I to Cl to Br in perovskite samples using Tauc's plot respectively. Moreover, simulation is carried out using the SCAPS-1D software to study the various parameters in MA & FA-based Bi-pure or mixed halide perovskites. Here, we discussed the variation in efficiency with respect to the thickness variation from 100 to 500 nm for MA3Bi2I9 halide perovskites. These MA3Bi2I9 halide perovskites show minimum efficiency of 4.65 % at 100 nm thickness, while the perovskite sample exhibits maximum efficiency of 10.32 % at 500 nm thickness. Thus, the results stated that the thickness of absorber layers directly affects the device characteristics for optoelectronic applications.

Chitosan-Based Highly Sensitive Viable Humidity Sensor for Human Health Monitoring.

We report a sustainable resistive-type humidity sensor based on chitosan (CS) film deposited on an interdigitated Ti/Au electrode coated SiO2 substrate using a simple drop cast approach for human health monitoring. The sensor revealed remarkably high sensitivity (5.8 MΩ/%RH), fast response/recovery time (21 s/25 s), low hysteresis (∼9.3%), excellent reversibility, wide detecting range (11-95% RH), and high selectivity toward water vapor. The calculated associated uncertainty at different %RH indicates the excellent repeatability and stable performance of the sensor. The developed sensor is tested for different human breath patterns, and it is found that the sensor can clearly distinguish between the variations in rate and depth of respiration patterns during normal, fast, deep, and nasal breathing and can monitor for apnea-like situations. The sensor is also utilized to perform noncontact skin humidity sensing. Overall, the developed CS film humidity sensor provides a viable approach for the detection of respiratory disorders and human health issues, detected by skin moisture, in a noninvasive manner.

Voltage- and Power-Conversion Performance of Bi-functional ZrO2 : Er3+ / Yb3+ Assisted and Co-sensitized Dye Sensitized Solar Cells for Internet of Things Applications.

Giant power conversion efficiency is achieved by using bifunction ZrO2 : Er3+ /Yb3+ assisted co-sensitised dye-sensitized solar cells. The evolution of the crystalline structure and its microstructure are examined by X-ray diffraction, scanning electron microscopy studies. The bi-functional behaviour of ZrO2 : Er3+ /Yb3+ as upconversion, light scattering is confirmed by emission and diffused reflectance studies. The bi-function ZrO2 : Er3+ /Yb3+ (pH=3) assisted photoanode is co-sensitized by use of N719 dye, squaraine SPSQ2 dye and is sandwiched with Platinum based counter electrode. The fabricated DSSC exhibited a giant power conversion efficiency of 12.35 % with VOC of 0.71 V, JSC of 27.06 mA/cm2 , FF of 0.63. The results, which motivated the development of a small DSSC module, gave 6.21 % and is used to drive a tiny electronic motor in indoor and outdoor lighting conditions. Small-area DSSCs connected in series have found that a VOC of 4.52 V is sufficient to power up Internet of Things (IoT) devices.

Exploiting Mass Spectrometry to Unlock the Mechanism of Nanoparticle-Induced Inflammasome Activation.

Nanoparticles (NPs) elicit sterile inflammation, but the underlying signaling pathways are poorly understood. Here, we report that human monocytes are particularly vulnerable to amorphous silica NPs, as evidenced by single-cell-based analysis of peripheral blood mononuclear cells using cytometry by time-of-flight (CyToF), while silane modification of the NPs mitigated their toxicity. Using human THP-1 cells as a model, we observed cellular internalization of silica NPs by nanoscale secondary ion mass spectrometry (nanoSIMS) and this was confirmed by transmission electron microscopy. Lipid droplet accumulation was also noted in the exposed cells. Furthermore, time-of-flight secondary ion mass spectrometry (ToF-SIMS) revealed specific changes in plasma membrane lipids, including phosphatidylcholine (PC) in silica NP-exposed cells, and subsequent studies suggested that lysophosphatidylcholine (LPC) acts as a cell autonomous signal for inflammasome activation in the absence of priming with a microbial ligand. Moreover, we found that silica NPs elicited NLRP3 inflammasome activation in monocytes, whereas cell death transpired through a non-apoptotic, lipid peroxidation-dependent mechanism. Together, these data further our understanding of the mechanism of sterile inflammation.

Geophysical and geostatistical assessment of groundwater and soil quality using GIS, VES, and PCA techniques in the Jaipur region of Western India.

In present study, geophysical and geostatistical variability of ground water and agricultural soil investigated in the Jaipur region of Rajasthan (Western India) by applying the geographic information system (GIS), vertical electrical sounding (VES) ,and statistical analysis. Ground water and soil samples collected from different sites from the selected study area and variation pattern of quality parameters were assessed. A contour map analysis of distribution of metals and other contaminants in the samples was conducted using GIS. Maximum concentration of metals recorded in the soil samples in order of Fe, 11.25 mg kg-1 > Mn, 8.6 mg kg-1 > Zn, 7.2 mg kg-1 > Cu, 0.455 mg kg-1; however, maximum concentration of metals in the ground water samples was found as Zn, 2.64 mg L-1 > Cu, 0.86 mg L-1 > Fe, 0.39 mg L-1 > Mn, 0.18 mg L-1 > Pb, 0.065 mg L-1 > Ni, 0.016 mg L-1. Observed data emphasis variability in groundwater and soil quality parameter by PCA technique indicated 84.60% and 66.98% of variance, respectively. Soil quality index (SQI) value was observed as 0.482 indicating that 46% of soil sampling sites deteriorated and shown poor quality. Similarly, water quality index (WQI) value indicates good water quality at the sampling sites TW1, TW8, TW10, and TW12; however, TW3, TW4, TW6, TW19, TW20, and TW22 sites showed very poor water quality. The present study concludes that overexploitation of groundwater and unregulated discharge of wastewater leads to depletion of water and soil quality. Further, applying geographical and geostatistical techniques in assessing water and soil quality could be more effective tools in environmental monitoring and management for environmental and health safety.

Label-free detection of polystyrene nanoparticles in Daphnia magna using Raman confocal mapping.

Micro- and nanoplastic pollution has emerged as a global environmental problem. Moreover, plastic particles are of increasing concern for human health. However, the detection of so-called nanoplastics in relevant biological compartments remains a challenge. Here we show that Raman confocal spectroscopy-microscopy can be deployed for the non-invasive detection of amine-functionalized and carboxy-functionalized polystyrene (PS) nanoparticles (NPs) in Daphnia magna. The presence of PS NPs in the gastrointestinal (GI) tract of D. magna was confirmed by using transmission electron microscopy. Furthermore, we investigated the ability of NH2-PS NPs and COOH-PS NPs to disrupt the epithelial barrier of the GI tract using the human colon adenocarcinoma cell line HT-29. To this end, the cells were differentiated for 21 days and then exposed to PS NPs followed by cytotoxicity assessment and transepithelial electrical resistance measurements. A minor disruption of barrier integrity was noted for COOH-PS NPs, but not for the NH2-PS NPs, while no overt cytotoxicity was observed for both NPs. This study provides evidence of the feasibility of applying label-free approaches, i.e., confocal Raman mapping, to study PS NPs in a biological system.

Correction: Infrared sensitive mixed phase of V7O16 and V2O5 thin-films.

[This corrects the article DOI: 10.1039/D3RA00752A.].

Infrared sensitive mixed phase of V7O16 and V2O5 thin-films.

We report an infrared (IR) sensitive mixed phase of V7O16 and V2O5 thin films, grown by cathodic vacuum arc-deposition on glass substrates at relatively low temperatures. We have found that the mixed phase of V7O16 and V2O5 can be stabilized by post-annealing of amorphous VxOy between 300-400 °C, which gets fully converted into V2O5 after annealing at higher temperatures ∼450 °C. The local conversion from VxOy to V2O5 has also been demonstrated by applying different laser powers in Raman spectroscopy measurements. The optical transmission of these films increases as the content of V2O5 increases but the electrical conductivity and the optical bandgap decrease. These results are explained by the role of defects (oxygen vacancies) through the photoluminescence (PL) and time-resolved photoluminescence (TRPL) measurements. The IR sensitivity of the mixed phase is explained by the plasmonic absorption by the V7O16 degenerate semiconductor.

Fuel-dependent, shape-selective, distinct blue and green photoluminescence from α-Bi2 O3 and ß-Bi2 O3 synthesised using microwave combustion.

In the current study, α-Bi2 O3 and ß-Bi2 O3 were synthesised using a one-step, novel, solid-solid combustion technique. The reaction rate was increased with the use of microwaves (molecular heating) compared to direct or indirect heating. A strong relationship was observed between the fuel, polymorphic structure, shape and optical properties of the synthesised Bi2 O3 . Photoluminescence studies reveal that two major visible emissions are observed for all samples. The two emissions are distinct with a broad peak in blue and a narrow peak in green. The intensity of the green characteristic emission depends strongly on the heating method used for synthesis and is more intense for microwave-synthesised samples.

UV/blue/green converted efficient red-NIR photoluminescence in Cr incorporated MgAl2O4nanocrystals: Site selective emission tailored through cation inversion and intrinsic defects.

The UV/Visible activated near-infrared (NIR) phosphors have many applications in solid state lighting, night vision devices and bio-imaging. The early research reported the red-NIR emitting phosphors doped with Cr3+centers upon visible light excitation. Here, in this work the intense red-NIR emission and color tuning is achieved for broad excitation range (UV/blue/green) through Cr dopant induced defect centers and cation inversionWe present the infuence of Cr dopant induced defect centers and cation inversion in Mg1-xCrxAl2O4(x= 0.5, 1, 3, 5 and 10 mol%) nanocrystals. The Cr3+doped MgAl2O4nanocrystals were synthesized by combustion method through stoichiometric substitution of Mg by Cr, while most of the Cr3+ions occupied the octahedral sites of spinel host with the formation of antisite defects, Cr3+clusters, magnesium and oxygen vacancies. These defect centers were probed through Rietveld refinement, PL, X-ray photoelectron and nuclear magnetic resonance spectra analyses. At UV excitation, the intrinsic defects played an interesting role in exhibiting the blue-violet emission attributed to host lattice defects and red-NIR emission attributed to strong/weak ligand field octahedral Cr3+sites, via charge transfer to Cr3+ions. The PL spectra evinced the enhanced red-NIR emission intensity upon 266 nm excitation than upon blue and green light excitation. Further, the weak ligand field site emission is found to be dominating with increase in doping concentration. Thus, Cr doped MgAl2O4nanocrystals showed their potency of exhibiting the intense red-NIR emission and color tuning (from red purple to bluish purple and then to red color) upon UV/blue/green excitation.

Silver nanoparticles with excellent biocompatibility block pseudotyped SARS-CoV-2 in the presence of lung surfactant.

Silver (Ag) is known to possess antimicrobial properties which is commonly attributed to soluble Ag ions. Here, we showed that Ag nanoparticles (NPs) potently inhibited SARS-CoV-2 infection using two different pseudovirus neutralization assays. We also evaluated a set of Ag nanoparticles of different sizes with varying surface properties, including polyvinylpyrrolidone (PVP)-coated and poly (ethylene glycol) (PEG)-modified Ag nanoparticles, and found that only the bare (unmodified) nanoparticles were able to prevent virus infection. For comparison, TiO2 nanoparticles failed to intercept the virus. Proteins and lipids may adsorb to nanoparticles forming a so-called bio-corona; however, Ag nanoparticles pre-incubated with pulmonary surfactant retained their ability to block virus infection in the present model. Furthermore, the secondary structure of the spike protein of SARS-CoV-2 was perturbed by the Ag nanoparticles, but not by the ionic control (AgNO3) nor by the TiO2 nanoparticles. Finally, Ag nanoparticles were shown to be non-cytotoxic towards the human lung epithelial cell line BEAS-2B and this was confirmed by using primary human nasal epithelial cells. These results further support that Ag nanoparticles may find use as anti-viral agents.

Environmental gas sensors based on electroactive hybrid organic-inorganic nanocomposites using nanostructured materials.

Advanced gas sensing devices are urgently demanded in the modern scientific world to control air pollution and protect human life. For this purpose, semiconducting electroactive materials can revolutionize the idea of conventional gas sensors. Chemi-resistive gas sensors based on electroactive hybrid organic-inorganic nanocomposites are incredibly promising gas sensing materials because they possess the advantages of excellent selectivity, high sensitivity, low response time, repeatability, high stability, cost-effectiveness, and simple fabrication techniques, and they can be operated at room temperature. This review emphasizes the recent developments of organic-inorganic hybrid nanocomposite-based electroactive gas sensors, including metal oxide nanocomposites, which are potential gas sensing materials due to the presence of numerous charge carriers. The review also focuses on nanostructured materials of different dimensions, such as semiconducting quantum dots, carbon dots, nanotubes, nanowires, and nanosheets, used for developing these gas sensing compounds and their significance and challenges. Some possible fabrication techniques for developing efficient gas sensors with different morphologies are discussed, with their probable sensing mechanism behind the detection of toxic vapours. Subsequently, a summary and possible outcome of this study, along with the various achievements and prospects in this field, are also discussed.

Morphological study of the menisci of the knee joint in human cadaver in Jharkhand population.

Introduction: Sports are the leading cause of joint injuries, particularly in the knees. Knee menisci are an important functional unit that aids in load distribution and hence reduces stress on the knee joint. Meniscal morphology provides information on exact size and shape, which is important for meniscal transplantation in cases of meniscal damage. The study's goal is to determine the morphological variation in the shape of menisci, as well as the width and thickness of menisci. Method: This study was conducted at the Rajendra Institute of Medical Sciences (RIMS) Ranchi, Department of Anatomy. In this study, 100 menisci were taken from 50 adult cadaver knee joints available in the dissection hall. Result: Six morphological kinds of menisci were identified after a morphological and morphometric study of 100 menisci. The most common crescent-shaped menisci (96%) were found in 50 medial menisci (MM), while the most common C-shaped menisci were found in 50 lateral menisci (LM, 94%). There was no statistically significant difference in thickness between the anterior, middle, and posterior thirds of the MM in the morphometric analysis. The thickest section of the lateral meniscus (LM) was in the middle third. There was no significant variation in the width of the LM among the different thirds in the current study. The posterior portion of the medial meniscus (MM), on the other hand, was the widest. Conclusion: The findings of this study support meniscal anatomy in terms of surgical technique and arthroscopy of the knee joint, as well as contributing to a better understanding of meniscal architecture and meniscal transplantation. As a result, health workers who treat meniscal injuries should be aware of the probable anatomical differences.