Ultrasonication-assisted synthesis of transition metal carbide of MXene: an efficient and promising material for photocatalytic organic dyes degradation of rhodamine B and methylene blue in wastewater.

Water pollutants of non-biodegradable toxic aromatic dye including Methylene blue (MB) and Rhodamine (RhB) are extremely carcinogenic thiazines used in various industries such as leather industry, paper industry, and the dyeing industry. The presence of dyes in wastewater causes severe threats to human health that are responsible for various harmful chronic or acute diseases and also shows an adverse impact on the environment as it reduces transparency and is harmful to water microorganisms. To overcome severe issues, many traditional techniques have been used to remove toxic pollutants, but these methods are insufficient to remove chemically stable dyes that remain in the treated wastewater. However, the photocatalytic degradation process is an efficient approach to degrade the dye up to the maximum extent with improved efficiency. Therefore, in this work, a new class of two-dimensional (2D) transition metal carbide of Titanium Carbide (Ti3C2Tx) MXene material was used for the organic dyes degradation such as MB and RhB using a photocatalytic process. A layered structure of hexagonal lattice symmetry of Ti3C2Tx MXene was successfully synthesized from the Titanium Aluminum Carbide of Ti3AlC2 bulk phase using an exfoliation process. Further, the XRD spectrum confirms the transformation of bulk MAX phase having (002) plane at 9.2° to Ti3C2Tx MXene of (002) plane at 8.88° confirms the successful removal of Al layer from MAX phase. A smooth, transparent, thin sheet-like morphology of Ti3C2Tx nanosheet size were found to be in the range of 70 to 150 nm evaluated from TEM images. Also, no holes or damages in the thin sheets were found after the treatment with strong hydrofluoric acid confirms the formation Ti3C2Tx layered sheets. The synthesized Ti3C2Tx MXene possesses excellent photocatalytic activity for the degradation of dyes MB, RhB, and mixtures of MB and RhB dyes. MB dye degraded with a degradation percentage efficiency of 99.32% in 30 min, while RhB dye was degraded upto 98.9% in 30 min. Also, experiments were conducted for degradation of mixture of MB and RhB dyes by UV light, and the degradation percentage efficiency were found to be 98.9% and 99.75% for mixture of MB and RhB dye in 45 min, respectively. Moreover, reaction rate constant (k) was determined for each dye of MB, RhB, and mixtures of MB and RhB and was found to be 0.0215 min-1 and 0.0058 min-1, and for mixtures, it was 0.0020 min-1 and 0.009 min-1, respectively.

Synergistic effect in the structural, optical, and electrical properties of harnessing NiFe2O4/CuO nanocomposite for enhanced environmental remediation.

This study presents the synthesis and characterization of composite material comprised of NiFe2O4 and CuO. The preparation of this composites involves a facile and cost-effective co-precipitation method, followed by heat treatment. The aim of this study is to explore the potential of this composite material for various catalytic applications. The synthesized NiFe2O4/CuO composites were extensively characterized using various analytical techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), impedance analyzer, UV-Visible spectroscopy (UV-Vis.), Brunner-Emmett-Teller (BET), and X-ray photoelectron spectroscopy (XPS). These characterizations revealed the successful formation of a nanocomposite material with a well-defined structure and identified the oxygen vacancies/defects in the samples which might result in enhanced photocatalytic efficiency. Photocatalytic activity of 0.5NiFe2O4/0.5CuO composite showed degradation of methylene blue dye by 96.15% in 120 min. This work is not only to understand the photocatalytic mechanism but also to develop effective catalysts for the degradation of harmful organic pollutants.

Theoretical reasons for rapid heating of vegetable oils by microwaves.

Water and high-moisture foods are readily heated in microwaves due to their relatively high dielectric loss factors. Vegetable oil, on the other hand, has a much smaller loss factor (about 1/100th that of water), and is generally believed to be unsuitable for microwave heating. In this study, we conducted experiments to compare heating rates between vegetable oil and pure water in a 2450 MHz microwave oven. We found that the vegetable oil samples were heated rapidly in microwaves, and even faster (1.4-2.0 times) than the water samples. To provide a theoretical explanation, we developed a 3-D computer simulation model. The simulation revealed an approximately 10-fold stronger electric field in oil compared to water, resulting in a similar amount of microwave power being absorbed by the oil and water samples. As the absorbed microwave power was converted into thermal energy, the oil samples were heated faster due to their smaller specific heat (1/2 that of water). But we also found that when the dimensions of oil are smaller than half the microwave wavelength, oil is heated slower than water due to the absence of hot spot areas. This study provides a theoretical explanation for microwave heating of vegetable oils and demonstrates opportunities for utilizing microwave energy to electrify industrial heating of vegetable oils.

Heterozygous gain of function variants in a critical region of RNF13 cause congenital microcephaly, epileptic encephalopathy, blindness, and failure to thrive.

Missense variants in the RNF13 gene have been previously known to cause congenital microcephaly, epileptic encephalopathy, blindness, and failure to thrive through a gain-of-function disease mechanism. Here, we identify a nonsense variant, expected to result in protein truncation, in a similarly affected patient. We show that this nonsense variant, residing in the terminal exon, is likely to escape nonsense-mediated decay while removing a critical region for protein function, thus resulting in a gain-of-function effect. We review the literature and disease databases and identify several other affected individuals with overlapping phenotypes carrying distinct truncating variants in the terminal exon upstream of the putative critical region. Furthermore, we analyze truncating variants from the general population, namely, the Genome Aggregation Database (gnomAD), and provide additional evidence supporting our hypothesis, and ruling out haploinsufficiency as an alternative disease mechanism. In summary, our case report, literature review, and analysis of disease and population databases strongly support the hypothesis that heterozygous gain-of-function variants in a critical region of RNF13 cause congenital microcephaly, epileptic encephalopathy, blindness, and failure to thrive.

Application of Hybrid ANN Techniques for Drought Forecasting in the Semi-Arid Region of India.

The intensity and frequency of diverse hydro-meteorological disasters viz., extreme droughts, severe floods, and cyclones have increasing trends due to unsustainable management of land and water resources, coupled with increasing industrialization, urbanization and climate change. This study focuses on the forecasting of drought using selected Artificial Neural Network (ANN)-based models to enable decision-makers to improve regional water management plans and disaster mitigation/reduction plans. Four ANN models were developed in this study, viz., one conventional ANN model and three hybrid ANN models: (a) Wavelet based-ANN (WANN), (b) Bootstrap based-ANN (BANN), and (c) Wavelet-Bootstrap based-ANN (WBANN). The Standardized Precipitation Evapotranspiration Index (SPEI), the best drought index identified for the study area, was used as a variable for drought forecasting. Three drought indices, such as SPEI-3, SPEI-6 and SPEI-12 respectively representing "short-term", "intermediate-term", and "long-term" drought conditions, were forecasted for 1-month to 3-month lead times for six weather stations over the study area. Both statistical and graphical indicators were considered to assess the performance of the developed models. For the hybrid wavelet model, the performance was evaluated for different vanishing moments of Daubechies wavelets and decomposition levels. The best-performing bootstrap-based model was further used for analysing the uncertainty associated with different drought forecasts. Among the models developed for drought forecasting for 1 to 3 months, the performances of the WANN and WBANN models are superior to the simple ANN and BANN models for the SPEI-3, SPEI-6, and SPEI-12 up to the 3-month lead time. The performance of the WANN and WBANN models is the best for SPEI-12 (MAE = 0.091-0.347, NSE = 0.873-0.982) followed by SPEI-6 (MAE = 0.258-0.593; NSE = 0.487-0.848) and SPEI-3 (MAE = 0.332-0.787, NSE = 0.196-0.825) for all the stations up to 3-month lead time. This finding is supported by the WBANN analyze uncertainties as narrower band width for SPEI-12 (0.240-0.898) as compared to SPEI-6 (0.402-1.62) and SPEI-3 (0.474-2.304). Therefore, the WBANN model is recommended for the early warning of drought events as it facilitates the uncertainty analysis of drought forecasting results.

Remediation of recalcitrant pollutants in water solution using visible light responsive cerium-doped tungsten trioxide nanoparticles.

In order to attain a solar energy-driven photocatalyst for wastewater remediation, cerium-doped WO3 (W1-xCexO3 with x = 0, 0.02, 0.04, 0.06, and 0.08) nanoparticles have been synthesized via a chemical co-precipitation technique. X-ray diffraction (XRD) analysis confirmed that W1-xCexO3 nanoparticles retained their monoclinic structure even after doping. The presence of the vast number of defects produced in the WO3 lattice was corroborated by Raman spectroscopy. Scanning electron microscopy confirmed the spherical shape of the nanoparticles with particle size range 50-76 nm. The optical band gap of W1-xCexO3 nanoparticles decreases from 3.07 to 2.36 eV with an increase in x, as confirmed by UV-Vis spectroscopy. Photoluminescence (PL) spectroscopy confirmed that the minimum rate of recombination was observed for W1-xCexO3 with x = 0.04. Degradation efficiency was explored for methyl violet (MV) and rhodamine-B (Rh-B) with 0.01 g of photocatalyst in a photoreactor chamber having a 200-W xenon lamp as a visible source of light. The results showed that the maximum photo-decolorization towards MV (94%) and rhodamine-B (79.4%) was observed in x = 0.04 sample in just 90 min because of its least recombination rate, highest adsorption capacity, and optimum band edge positions. Intriguingly, it has been observed that the modification with cerium in WO3 nanoparticles enhances the photocatalytic activity by narrowing the band gap and by efficaciously lowering the recombination rate due to electron entrapment by defects produced in the lattice.

Facile synthesis of carbon dots via pyrolysis and their application in photocatalytic degradation of rhodamine B (RhB).

Carbon Quantum dot (CQDs) is one of the newest materials in carbon-based nanomaterials. It is pertinent to study the synthesis and the application of these carbon dots. Here we have studied the effect of precursor on the optical, morphological, and photocatalytic properties of CQDs. We have synthesized CQDs using pyrolysis method using the precursors citric acid, urea, polyethyleneimine. We have synthesized two samples: CQD-S1; synthesized using urea and polyethyleneimine, and CQD-S2; synthesized using citric acid and polyethyleneimine. In optical properties study two distinct peaks have been obtained at 243 nm and 345 nm for CQD-S1, and at 265 nm and 335 nm for CQD-S2. In fluorescence study, the maximum emission was found at excitation wavelength of 340 nm for CQD-S1 and at excitation wavelength of 350 nm for CQD-S2. In morphological studies, Transmission Electron Microscope (TEM) revealed particle size of sample CQD-S1 and CQD-S2 were 1.91 nm and 1.61 nm, respectively. EDX confirmed the elemental composition in both samples. The rhodamine B (RhB) dye degradation percentages in dark and under visible and UV light were found to 6, 13, and 98.4% respectively for CQD-S1. Similarly, dye degradation for CQD-S2 were 7, 11, and 99.63%, respectively. Effective degradation of photocatalysis performed under UV-light within 100 min using mineralization process.

Construction of the quinobenzoxazine core via gold-catalyzed dual annulation of azide-tethered alkynones with anthranils.

A new catalytic method for the construction of the quinobenzoxazine core has been developed employing the gold-catalyzed cyclization of o-azidoacetylenic ketones in the presence of anthranils. The overall process comprises of a gold-catalyzed 6-endo-dig cyclisation of o-azidoacetylenic ketone leading to a α-imino gold carbene and subsequent carbene transfer to anthranil leading to the 3-aryl-imino-quinoline-4-one intermediate, which undergoes 6π-electrocyclization and aromatization to form the central quinobenzoxazine core. This transformation provides a new approach to a diverse array of quinobenzoxazine structures, in addition to being scalable and having mild reaction conditions.

Hybrid mixture theory-based modeling of transport of fluids, species, and heat in food biopolymers subjected to freeze-thaw cycles.

A hybrid mixture theory (HMT)-based unsaturated transport (pores not saturated with liquid) model was applied to a food matrix subjected to freezing and freeze-thaw cycles. The model can explain the fluid, species, and heat transport, ice formation, thermomechanical changes, and the freezing point depression occurring inside food biopolymers during freezing. Volume changes during freezing were calculated using the stresses due to pore pressure and the phase-change based mechanical strain. The Eulerian-Lagrangian transformation was performed for solving the equations using a finite element mesh in Lagrangian coordinates. The predicted temperature profiles for constant and fluctuating freezing temperature conditions showed agreement with experimental data with reasonable accuracy (RMSE = 2.86°C and 2.23°C, respectively). The multiscale transport model coupled with a physical chemistry-based relation was able to predict solute concentration and the freezing point depression in potatoes with greater accuracy than an empirical equation published in the literature. Sudden temperature fluctuations representing the opening and closing of a freezer door were investigated using this solution scheme, and conditions causing less damage to the food were identified. PRACTICAL APPLICATION: Food materials are subjected to freeze-thaw cycles during storage, shipping, and distribution to the consumers. The study uses numerical modeling and experimental validation to elucidate the principles affecting ice formation, solute migration, and temperature changes. Outcomes will allow processors to improve the quality of frozen foods with improved design of freezing operation, and storage and distribution strategies.

Microwave frying and post-frying of French fries.

French fries are popular items in the diets of many countries, but the high oil content is a major health concern for consumers. Numerous novel frying techniques have been explored by the fast food service industry and the research community to address such concern. This research aimed to study the influence of microwave heating at two frequencies (2.45 and 5.85 GHz), both individually or in combination, in frying and post-frying on oil reduction in French fries. Results showed that microwave frying reduced the frying time by 30 - 40%, with equivalent product quality attributes in terms of oil content, color, and texture, as compared to deep-oil frying. Oil intake increased with increasing moisture loss during frying, regardless of the frying methods. Post-frying condition was the key to oil reduction. Specifically, a 60 s microwave heating after frying reduced the oil content by 18 - 23%. Compared to 2.45 GHz, microwaves at 5.85 GHz could produce French fries with significantly lower oil content (p ≤ 0.05) and better quality attributes such as color and texture. This study demosntrated the potential of microwave heating in production of deep-fried French fries with lower oil content and better quality.

Rediscovering Bacon's hydrazine/phenylhydrazine mediated cyclization of 2,2'-dicarbonylbi(hetero)aryls: construction of (5-azo)-/indazolo[2,3-a]quinolines.

Hydrazine/phenylhydrazine-mediated reductive dicarbonyl coupling reactions have been carried out under mild conditions to provide polycyclic aromatic compounds and azo-substituted polyaromatic compounds. This method has a broad substrate scope with good functional group compatibility.

Stress relaxation properties of bananas during drying.

Bananas' mechanical properties are affected by the ripening and the drying processes since they induce profound microstructural changes. In this study, first, the interacting effect of the ripening and the drying processes on the mode of viscoelastic behavior of bananas was investigated. Second, the stress relaxation properties of fully ripe bananas were measured as a function of the hot air drying conditions. Finally, the two-element generalized Maxwell model was fitted to the experimental data. Thus, this study clarified the dependence of the mode of rheological behavior on both the ripening stage and the moisture content. It showed that bananas start softening at the onset of the drying when the fruit moisture content is high. The softening is reversed at a critical value, at which the bananas start regaining stiffness with further moisture reduction. The critical moisture content value decreases with ripening from 1.4 g/g solids for green bananas (5-11% Brix percentage) to 1.23 g/g solids for half-ripe bananas (15-20% Brix percentage) and eventually vanishes when the bananas are fully ripe (25-31% Brix percentage). The stress relaxation properties measured with fully ripe bananas substantiated the initial findings on the influence of the ripening stage on the mode of rheological behavior. The relaxation moduli displayed a decreasing trend with decrease in the moisture content for 40, 60, and 80°C drying temperatures and decayed with time as expected for viscoelastic bodies. Lastly, the two-element generalized Maxwell model fitted well to the experimental data with the root mean square error varying between 0.06 × 10-5 and 90.6 × 10-5 MPa.

Total synthesis of the pseudoindoxyl class of natural products.

The pseudoindoxyl sub-structural motif, amongst the large set of the indole class of alkaloids, represents a unique subset of the oxygenated indole class of the alkaloid family. A majority of this class of natural products contains complex bridged/polycyclic scaffolds with interesting biological profiles. They are thus attractive synthetic targets. Starting from 1963, twenty-eight natural products having the pseudoindoxyl scaffold have been isolated, among which the synthesis of 13 natural products has been accomplished. In this review, we highlight the completed as well as the formal total synthesis of the natural products with a spiro-pseudoindoxyl ring, with a focus on their development. The challenges and the future perspective based on the recent developments in the field will also be discussed. We strongly believe that this review will not only update but also attract the attention of researchers in dealing with the synthesis of pseudoindoxyl compounds.

Gold-Catalyzed Complementary Nitroalkyne Internal Redox Process: A DFT Study.

Gold-catalysis, in this century, is one of the most emerging and promising new areas of research in organic synthesis. During the last two decades, a wide range of distinct synthetic methodologies have been unveiled employing homogeneous gold catalysis and aptly applied in the synthesis of numerous natural products and biologically active molecules. Among these, the reactions involving α-oxo gold carbene/α-imino gold carbene intermediates are of contemporary interest, in view of their synthetic potential and also due to the need to understand the bonding involved in these complexes. In this manuscript, we document the theoretical investigations on the regio-selectivity dependence of substitution on the gold-catalyzed cycloisomerization of o-nitroarylalkyne derivatives. We have also studied the relative stabilities of α-oxo gold carbene intermediates.

Intermolecular Interception of α-Oxo Gold Carbenes of Nitroalkyne Cycloisomerization with 1,2-Benzo[d]isoxazole: Synthesis of Functionalized Quinazoline 1-Oxides.

The known nitrogen-transfer reagent 1,2-benzo[d]isoxazole has been used to trap the postulated α-oxo gold carbene intermediate involved in the [Au]-catalyzed internal redox process of 2-alkynylnitrobenzenes. This process led us to develop a general convergent method for the synthesis of highly functionalized quinazoline 1-oxides.

Gold-Catalysed Nitroalkyne Cycloisomerization - Synthetic Utility.

The gold-catalysed intramolecular redox cyclization of o-alkynylnitrobenzens documented by Professors Naoki Asao and Yoshinori Yamamoto is an important discovery that has opened two complementary research domains. Advancing this cyclization with other metals as well as developing new methods around the products that result from this reaction is one aspect that has seen growing interest. On the other hand, the idea of generating α-oxo gold carbenes via oxygen transfer to alkynes has established another important aspect in gold-catalysis. In this account, we will be dealing with the first aspect, which revolves around the internal redox cyclization of nitroalkynes (trivially called as nitroalkyne cycloisomerization), focusing mainly on the gold-complexes and the synthetic methods developed around it from our group and from other groups, and also providing the details of similar transformations documented with other metals so that the complementary reactivity/diversity of these transformations could be appreciated.

Capsule Network-based architectures for the segmentation of sub-retinal serous fluid in optical coherence tomography images of central serous chorioretinopathy.

Central serous chorioretinopathy (CSCR) is a chorioretinal disorder of the eye characterized by serous detachment of the neurosensory retina at the posterior pole of the eye. CSCR results from the accumulation of subretinal fluid (SRF) due to idiopathic defects at the level of the retinal pigment epithelial (RPE) that allows serous fluid from the choriocapillaris to diffuse into the subretinal space between RPE and neurosensory retinal layers. This condition is presently investigated by clinicians using invasive angiography or non-invasive optical coherence tomography (OCT) imaging. OCT images provide a representation of the fluid underlying the retina, and in the absence of automated segmentation tools, currently only a qualitative assessment of the same is used to follow the progression of the disease. Automated segmentation of the SRF can prove to be extremely useful for the assessment of progression and for the timely management of CSCR. In this paper, we adopt an existing architecture called SegCaps, which is based on the recently introduced Capsule Networks concept, for the segmentation of SRF from CSCR OCT images. Furthermore, we propose an enhancement to SegCaps, which we have termed as DRIP-Caps, that utilizes the concepts of Dilation, Residual Connections, Inception Blocks, and Capsule Pooling to address the defined problem. The proposed model outperforms the benchmark UNet architecture while reducing the number of trainable parameters by 54.21%. Moreover, it reduces the computation complexity of SegCaps by reducing the number of trainable parameters by 37.85%, with competitive performance. The experiments demonstrate the generalizability of the proposed model, as evidenced by its remarkable performance even with a limited number of training samples. Graphical abstract is mandatory please provide.

Interrupting the [Au]-Catalyzed Nitroalkyne Cycloisomerization: Trapping the Putative α-Oxo Gold Carbene with Benzo[c]isoxazole.

The [Au]-catalyzed nitroalkyne cycloisomerization of 2-alkynylnitrobenzenes leading to anthranils has been interrupted by possible trapping of the postulated intermediate α-oxo gold carbene with an external nucleophile such as benzo[c]isoxazole (anthranil). At the outset, this provides a simple synthesis of highly functionalized 3-acyl-(2-formylphenyl)-2H-indazoles with the sequential C-O, C-N, and N-N bond formations. This provides indirect support for the existence of α-oxo gold carbenes in the [Au]-catalyzed internal redox processes of nitroalkynes.

Nicotinic acid adenine dinucleotide phosphate activates two-pore channel TPC1 to mediate lysosomal Ca2+ release in endothelial colony-forming cells.

Nicotinic acid adenine dinucleotide phosphate (NAADP) is the most recently discovered Ca2+ -releasing messenger that increases the intracellular Ca2+ concentration by mobilizing the lysosomal Ca2+ store through two-pore channels 1 (TPC1) and 2 (TPC2). NAADP-induced lysosomal Ca2+ release regulates multiple endothelial functions, including nitric oxide release and proliferation. A sizeable acidic Ca2+ pool endowed with TPC1 is also present in human endothelial colony-forming cells (ECFCs), which represent the only known truly endothelial precursors. Herein, we sought to explore the role of the lysosomal Ca2+ store and TPC1 in circulating ECFCs by harnessing Ca2+ imaging and molecular biology techniques. The lysosomotropic agent, Gly-Phe ß-naphthylamide, and nigericin, which dissipates the proton gradient which drives Ca2+ sequestration by acidic organelles, caused endogenous Ca2+ release in the presence of a replete inositol-1,4,5-trisphosphate (InsP3 )-sensitive endoplasmic reticulum (ER) Ca2+ pool. Likewise, the amount of ER releasable Ca2+ was reduced by disrupting lysosomal Ca2+ content. Liposomal delivery of NAADP induced a transient Ca2+ signal that was abolished by disrupting the lysosomal Ca2+ store and by pharmacological and genetic blockade of TPC1. Pharmacological manipulation revealed that NAADP-induced Ca2+ release also required ER-embedded InsP3 receptors. Finally, NAADP-induced lysosomal Ca2+ release was found to trigger vascular endothelial growth factor-induced intracellular Ca2+ oscillations and proliferation, while it did not contribute to adenosine-5'-trisphosphate-induced Ca2+ signaling. These findings demonstrated that NAADP-induced TPC1-mediated Ca2+ release can selectively be recruited to induce the Ca2+ response to specific cues in circulating ECFCs.

Multi-Res-Attention UNet: A CNN Model for the Segmentation of Focal Cortical Dysplasia Lesions from Magnetic Resonance Images.

In this work, we have focused on the segmentation of Focal Cortical Dysplasia (FCD) regions from MRI images. FCD is a congenital malformation of brain development that is considered as the most common causative of intractable epilepsy in adults and children. To our knowledge, the latest work concerning the automatic segmentation of FCD was proposed using a fully convolutional neural network (FCN) model based on UNet. While there is no doubt that the model outperformed conventional image processing techniques by a considerable margin, it suffers from several pitfalls. First, it does not account for the large semantic gap of feature maps passed from the encoder to the decoder layer through the long skip connections. Second, it fails to leverage the salient features that represent complex FCD lesions and suppress most of the irrelevant features in the input sample. We propose Multi-Res-Attention UNet; a novel hybrid skip connection-based FCN architecture that addresses these drawbacks. Moreover, we have trained it from scratch for the detection of FCD from 3 T MRI 3D FLAIR images and conducted 5-fold cross-validation to evaluate the model. FCD detection rate (Recall) of 92% was achieved for patient wise analysis.