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The liquid chromatography-high resolution mass spectrometry (LC-HRMS) technique enables the detection of phytochemicals present in the extracts. LC-HRMS-generated mass list showed abundant compounds of interest, artifacts, and primary metabolites. The identification of a secondary metabolite of interest within the extract is very challenging. We hypothesized that identifying the "new metabolite" in the whole metabolome is more challenging than identifying it within the class of metabolites. The proposed prioritization strategy focused on the elimination of unknown and prioritizing the known class of secondary metabolites to identify new metabolites. The prioritization strategy demonstrated on Murraya paniculata for the identification of new metabolites. LC-HRMS-generated information is used as a filter to target the secondary metabolite and the new metabolites. This strategy successfully annotated the new coumarin and coumarin alkaloids from the mass list of 1448 metabolites. Varanasine ( 3 ), schroffanone ( 4 ), schroffanene ( 5 ), and O -methylmurraol ( 9 ) are new compounds, and coumarin ( 1 , 2 , and 6-8 ) are known. Varanasine ( 3 ) is the first naturally occurring 7-aminocoumarin with additional N -formyl functionality. The isolates were screened for cytotoxicity against the panel of cancer cell lines. Varanasine ( 3 ) and minumicrollin ( 6 ) showed significant cytotoxicity and apoptosis-inducing potential. The immunoblot analysis confirmed inhibition of apoptotic protein PARP-1 and caspase-3 expression by 3 and 6 .

Barometric pressure monitoring typically depends on conventional rigid microelectromechanical systems (MEMS) for single-point measurements. However, applications such as fluid dynamics require mapping barometric pressure distribution to study phenomena such as pressure variations on an aircraft wing during flight. In this study, we developed a mechanically flexible, multichannel air pressure sensor sheet using laser-induced graphene (LIG). This air pressure sensor sheet is designed to be mechanically flexible, allowing it to conform to nonplanar objects. First, the crystallinity change of LIG is studied by monitoring the bottom and top surfaces, revealing the presence of multilayered graphene and amorphous-like carbon in the formation of LIG. This explains the crystallinity change before and after the transfer process. Using LIG with optimal structures, negative and positive pressure detection is achieved, enabling its use as an air pressure sensor. Finally, as a proof-of-concept for the multichannel air pressure sensor sheet, the pressure distribution on the surface of an aircraft wing model is successfully mapped out.

A new bismuth-based host material, i.e., Sr 2 BiF 7 , is explored in this work. Undoped and lanthanide ion-doped Sr 2 BiF 7 nanomaterials are prepared using a simple coprecipitation technique at 120 °C. The undoped nanomaterials exhibit a blue color under 365 nm excitation. The downshifting and upconversion photoluminescent properties of Er and Yb codoped Sr 2 BiF 7 nanomaterials are investigated. The optimum up-conversion luminescence is produced by nanomaterials doped with 5% Yb 3+ and 0.2% Er 3+ . These nanomaterials show blue and magenta colors upon excitation at 365 and 395 nm wavelengths, respectively. Sr 2 BiF 7 material doped with Er 3+ shows green emission, while the codoped Er 3+ , Yb 3+ nanomaterials exhibit an orange-red color under 980 nm light. A specific amount of polyvinyl chloride (PVC) is used for producing luminescent ink with these nanoparticles for multimode anticounterfeiting applications. The letters and patterns written with luminescent ink based on Er 3+ , Yb 3+ doped nanomaterials show blue, magenta, and orange-red colors under 365, 395, and 980 nm light, respectively. These results establish that this material can be effectively used as a multimode photoluminescent covert tag to combat counterfeiting.

Ultrasensitive thermal lens (TL) spectroscopy, where the interplay between conduction and convection is crucial, provides profound insights into molecular behavior. This work focuses on the critical role of molecular convection by using the dual-beam z-scan method and time-resolved TL spectroscopy. We specifically investigated the correlation between the detection iris and the spot size of the pump beam. Additionally, we address detection limitations and their influence on the perception of convection timing. We introduce an experimentally derived ratio optimized for higher sensitivity, enhancing the reliability of TL spectroscopy. This refined approach to TL spectroscopy allows for a deeper exploration of molecular characteristics in liquids.

An Ir(III)-catalyzed annulation of aryl amides with 1,6-diynes via ortho- as well as meta -dual C-H bond activation reaction is reported. The scope of the annulation reaction was examined with various substituted aryl amides, as well as 1,6-diynes. In this protocol, 1,6-diynes exhibit diverse reactivity compared with internal alkynes. It is important to note that the three C-C bond formation takes place consecutively via ortho followed by meta -dual C-H bond annulation by using a weak chelating group in one pot. A possible catalytic reaction mechanism was proposed to account for the annulation reaction.

Investigations of entangled and classical two-photon absorption have been carried out for six donor (D)-acceptor (A)-donor (D) compounds containing the dithieno pyrrole (DTP) unit as donor and acceptors with systematically varied electronic properties. Comparing ETPA (quantum) and TPA (classical) results reveals that the ETPA cross section decreases with increasing TPA cross section for molecules with highly off-resonant excited states for single-photon excitation. Theory (TDDFT) results are in semiquantitative agreement with this anticorrelated behavior due to the dependence of the ETPA cross section but not TPA on the two-photon excited state lifetime. The largest cross section is found for a DTP derivative that has a single photon excitation energy closest to resonance with half the two-photon excitation energy. These results are important for the possible use of quantum light for low-intensity energy-conversion applications.

Nanostructuring can greatly improve the electrode stability of rechargeable battery systems, such as Zn-Ag. In this report, we investigate the physical mechanisms by which nanostructuring alters structural properties of nanomaterials and thereby influences the structural stability of electrodes. We specifically consider the effects of Au-based nanoscaffolds on Ag. Through density functional theory calculations, we propose that the charge transfer at the Au-Ag interface can facilitate the formation of Ag 2 O from Ag centers. Structural analysis of samples prepared in this work shows that Ag 2 O is extruded from Au-Ag material in the form of sheets. Interestingly, the length scale of such protrusions depends on the Au mole fraction that significantly alters the system's overall structural morphology. We rationalize these findings via kinetic Monte Carlo simulations of the Ag 2 O growth process and highlight the role of Au as a heterogeneous nucleation center.

ConspectusThe reductive conversion of carbon dioxide (CO 2 ) into value-added products is a process of immense importance. In the context of rising CO 2 concentration in the atmosphere and the detrimental effects it is having on the biosphere, use of alternative fuels which can offer a low-carbon or carbon-neutral pathway for storage and utilization of low-carbon energy by maintaining the net atmospheric CO 2 concentration might be a prospective solution. Among the wide variety of reduced products that can be obtained from CO 2 , formic acid and formate salts are particularly important due to their ability to be used as an alternative fuel or a reversible hydrogen storage material. Utilization of molecular catalysts for CO 2 conversion offers several advantages such as high selectivity, mechanistic clarity, versatility, and stability, making them attractive for thermochemical and electro/photochemical CO 2 reduction processes. The presence of N-heterocyclic carbene (NHC) ligands in transition-metal-based molecular catalysts enhances the stability of the catalysts under harsh reaction conditions, such as high pressure, high temperature, and reductive environments, providing crucial benefits for sustained catalytic activity and longevity. Though the development of metal complex-based catalysts is essential to addressing the challenge of CO 2 reduction, the possibility of using purely organic compounds as catalysts for this transformation is lucrative from the aspect of developing a truly sustainable protocol with photosynthesis being its biggest inspiration. We begin this Account by examining our systematic development of molecular metal complexes based on NHC ligands for the chemical upgradation of CO 2 to formic acid/formate salt. In such cases, the ability of NHCs to act as strong σ-donor ligands for a greater hydride transfer propensity is discussed and analyzed. The reports range from catalytic ambient- and high-pressure CO 2 hydrogenation to CO 2 transfer-hydrogenation. Coupling of CO 2 capture methodologies with CO 2 conversion is also discussed. A case is made for the heterogenization of one of the highly efficient metal-NHC catalysts to develop a self-supported single-site catalyst for practical applications. Finally, our recent success of developing a novel organic catalyst system inspired from the natural NADP + /NADPH-based hydride-transfer redox couple that is active in photosynthetic CO 2 reduction has been discussed. This catalyst is designed based on a bis-imidazolium-embedded heterohelicene with a central pyridine ring and is capable of electrocatalytically converting CO 2 to HCO 2 H with TON values 100-1000 times greater than the existing reported values achieved so far by organic catalysts. Overall, we believe that the results of hydride transfer-based CO 2 reduction catalysis presented in this Account hold significant implications beyond our work and have the potential for motivating future research toward further development in this important field.

The implications of retained strain on in vitro and in vivo degradation behavior as well as cytocompatibility of the Mg-4Zn-0.5Ca-0.8Mn alloy is comprehensively studied. The retained strain is induced in homogenized specimens by hard-plate hot forging (HPHF) at a temperature (523 K) lower than the recrystallization temperature of the alloy. The retained strain generated during deformation process deteriorated the corrosion response of the deformed alloy as compared to its homogenized counterpart. The strained area of deformed specimen with high dislocation density promoted defect generation (oxygen vacancies) in the film and facilitated preferential migration of ions, consequently leading to formation of a nonuniform product film with low protectiveness. In addition to strain magnitude, the distribution of retained strain also influenced the product film properties in the deformed specimens. An even distribution of retained strain improved the uniformity of the product film to certain extent by providing greater film coverage, resulting in higher film resistance. After 24 h of immersion, the protectiveness of the film was further improved in this specimen due to annihilation of defects through homogeneous ionic migration, which led to the development of a uniform and stable film that restricted further ionic diffusion. The dissolution of Zn(OH) 2 into Zn 2+ ions was promoted at lower pH, resulting in enhanced antimicrobial activity in the specimen with the lowest degradation. Besides, the specimen with stable product film not only minimized the rate of further degradation but also served as an interface for new bone growth, as evident from in vivo studies.

Hypochlorite, as an important reactive oxygen species (ROS), plays a vital role in many physiological and pathological processes, but an excess concentration of hypochlorite (ClO - ) may become toxic to humans and cause disease. Hence, the selective and rapid detection of hypochlorite (ClO - ) is necessary for human safety. Here, we report a novel near-infrared (NIR) fluorescence "turn-on" and highly selective benzophenoxazinium chloride-based fluorescent probe, BPH (benzophenoxazinium dihydroxy benzaldehyde), for hypochlorite detection. Due to hypochlorite-induced vicinal diol oxidation to the corresponding ortho benzoquinone derivative, the photoinduced electron transfer (PET) process, which was operating from vicinal diol to the benzophenoxazinium chloride receptor moiety, was suddenly inhibited, as a result of which strong NIR fluorescence "turn-on" emission was observed. The detection limit of BPH was found to be 2.39 × 10 -10 M, or 0.23 nM. BPH was successfully applied for exogenous and endogenous hypochlorite detection in live MDA-MB 231 cells.

A self-assembly-directed thixotropic metallohydrogel (i.e., Mg-Tetrakis) of Mg(II)-metal salt and N , N , N ', N '-tetrakis(2-hydroxy-ethyl)ethylenediamine (i.e., Tetrakis) was successfully achieved. The organic chemical component N , N , N ', N '-tetrakis(2-hydroxy-ethyl)ethylenediamine was used as a low-molecular-weight gelator, and water was employed as the gel-forming solvent. The fabricated supramolecular metallohydrogel promisingly depicted viscoelastic and mechanoelastic behaviors, which are interpreted through various rheological parameters. The thixotropic behavior of the metallohydrogel is also well characterized through this rheological study. Field emission scanning electron microscopy microstructural analyses were performed to visualize the morphological arrangements of the metallohydrogel. The anticancer properties of the synthesized metallogels are investigated through this work. The cytotoxic potential of the metallohydrogel on the MCF-7 breast cancer cell line is critically examined. Reducing the growth of breast cancer cell line MCF-7 through the treatment of gel on the colony formation assay has been explored through the work. The antimigratory potential of the metallohydrogel on the MCF-7 cell was also scrutinized. The anticancer effect of the fabricated metallohydrogel is inspected through various assay formation strategies, like wound healing assay, tumor spheroid inhibition assay, nuclear fragmentation assay, and so on. Quantitative reactive oxygen species analysis of the cancer cells by treatment with the metallohydrogel was also conducted through this study. The mechanistic apoptosis study was executed by studying the expression of various apoptotic markers like BAX, BCL2, PUMA, and NOXA.

This study presents the use of nanoscale covalent organic frameworks (nCOFs) conjugated with tumor-targeting peptides for the targeted therapy of triple-negative breast cancer (TNBC). While peptides have previously been used for targeted delivery, their conjugation with COFs represents an innovative approach in this field. In particular, we have developed alkyne-functionalized nCOFs chemically modified with cyclic RGD peptides (Alkyn-nCOF-cRGD). This configuration is designed to specifically target α v β 3 integrins that are overexpressed in TNBC cells. These nCOFs exhibit excellent biocompatibility and are engineered to selectively disintegrate under acidic conditions, allowing for precise and localized drug release in tumor environment. Doxorubicin, a chemotherapeutic agent, has been encapsulated in these nCOFs with high loading efficiency. The therapeutic potential of Alkyn-nCOF-cRGD has been demonstrated in vitro and in vivo models. It shows significantly improved drug uptake and targeted cell death in TNBC, highlighting the efficacy of receptor-mediated endocytosis and pH-controlled drug release. This strategy leverages the unique properties of nCOFs with targeted drug delivery to achieve significant advances in personalized cancer therapy and set a new standard for precision chemotherapeutic delivery.

Peroxisome proliferator-activated receptors (PPARs) have emerged as a promising target for the treatment of various neurodegenerative disorders. Studies have shown that both PPAR α & γ individually modulate various pathophysiological events like neuroinflammation and insulin resistance, which are known to variedly affect neurogenesis. Our study aimed to evaluate the effect of saroglitazar (SGZR), a dual PPAR agonist, on adult neurogenesis and spatial learning and memory, in intracerebroventricular streptozotocin (ICV STZ)-induced dementia in rats. We have found that SGZR at the dose of 4 mg/kg per oral showed significant improvement in learning and memory compared to ICV STZ-treated rats. A substantial increase in neurogenesis was observed in the subventricular zone (SVZ) and the dentate gyrus (DG), as indicated by an increase in the number of 5-bromo-2'-deoxyuridine (BrdU) + cells, BrdU + nestin + cells, and doublecortin (DCX) + cells. Treatment with SGZR also decreased the active form of glycogen synthase kinase 3β (GSK3β) and hence enhanced the nuclear translocation of the β-catenin. Enhanced expression of Wnt transcription factors and target genes indicates that the up-regulation of Wnt signaling might be involved in the observed increase in neurogenesis. Hence, it can be concluded that the SGZR enhances memory functions and adult neurogenesis via the upregulation of Wnt β-catenin signaling in ICV STZ-treated rats.

The ability of metamaterial structures to offer unique properties and new solutions has opened new avenues in a wide range of applications, including super-resolution in optics and efficient antennas in radiofrequency (RF) engineering. In magnetic resonance imaging (MRI), metamaterials hold the promise of increasing the RF magnetic field intensity while minimizing power deposition. Here, we propose a metasurface based on a two-dimensional (2D) array of short conducting strips combined with a high dielectric substrate, which was tuned to operate at ultrahigh field 7T human MRI. While studied in optics and electromagnetics in the GHz-to-THz range, this study is the first to design such a metasurface for proton imaging at 7T MRI. We performed electromagnetic (EM) simulation of the brain MRI setup with the new metasurface placed in the proximity to the temporal lobe, which showed 2.2-fold local increase in the RF transmit efficiency, with superior performance than an array of electric dipoles. In this study, we also investigate the effect of the spatial distribution of the subunits to control the target RF field's distribution. While the common design is based on a uniform distribution of the subunits, nonuniform distribution, such as a denser center (convex) or more condensed edges (concave), provides an extra dimension to tailor both the magnetic and electric fields. The concave distribution achieved 1.5-1.8-fold reduction in the power deposition compared to the uniform distribution in the brain MRI setups examined.

Recently, two-dimensional (2-D) layered materials have revealed outstanding properties and play a crucial role for numerous advanced applications. The emerging transition metal carbides and nitrides, known as MXene with empirical formula M n +1 X n T x , have generated widespread attention and demonstrated impressive potential in various fields. The fabrication of 2-D novel MXene and its composites and their characterizations are applicable to vast applications in different areas such as energy storage, gas sensors, catalysis, and biomedical applications. In this review, the main focus is on the various synthesis methods, their properties, and biomedical applications. This review provides detailed illustrations of MXenes for many biomedical applications, including bioimaging, drug delivery, therapies, biosensors, tissue engineering, and antibacterial reagents. The challenges and future prospects were highlighted in a comprehensive manner, and the existing problems and potential for MXene-based biomaterials were analyzed with the goal of accelerating their use in the biomedical field.

Herein, waste-derived copper (Cu) flakes have been used as heterogeneous catalysts for the solvent-free and one-pot reductive acetamidation of nitroarenes. Metallic copper flakes (f-ZCu) were isolated from waste copper Cu scrap/flakes/turnings generated after the grinding and cutting (from the Cu industries). f-ZCu is being used to synthesize acetanilide with a considerable yield (∼82%) in one-step and solvent-free conditions within a reaction time of 6 h. Moreover, the same procedure is also being utilized for producing various substrates (9), including the gram-scale synthesis of the well-known important antipyretic drug, i.e., paracetamol. The plausible mechanism for the reaction was also proposed based on the spectroscopic analyses of spent f-ZCu.

A flexible and metal-free synthetic approach for synthesizing 2-benzoyl quinazolinones and 2-aryl quinazolinones via molecular iodine-mediated annulative coupling of sulfoxonium ylides with 2-aminobenzamides has been disclosed. The method demonstrates remarkable chemoselectivity and efficiency, leading to high yields of 2-benzoyl quinazolinones and 2-aryl quinazolinones under optimized conditions. The broad substrate scope, scalability, and practical utility were highlighted through diverse applications, including gram-scale reactions and the synthesis of biologically significant compounds such as tryptanthrin and the chemo/biosensor derivative.

Synthesis of diversely functionalized quinoline-2-carboxylates is illustrated through electrochemical cross-dehydrogenative coupling between N -aryl glycinates and methylenecyclopropanes. An extensive range of distinct functionalities is well-compatible under these transition-metal- and oxidant-free mild electrochemical conditions, contributing to a broad substrate scope and practical applicability. Cyclic voltammetric measurements and control experiments suggested a formal [4 + 2] cycloaddition involving radical intermediates, followed by a cyclopropyl ring opening through nucleophilic polar addition, consecutively fabricating C-C and C-N bonds.

We report a simple synthetic method for obtaining 3-hydroxy-4,5-disubstituted isothiazoles utilizing dithioester and aryl acetonitrile. The isothiazoles obtained in this method involve the formation of new C-C, C-O, and N-S bonds in one step using a simple base such as KOH under aerial conditions. The 3-hydroxy-4,5-disubstituted isothiazole was successfully employed for further functionalization. The strategy provides high selectivity for the synthesis of isothiazoles, which may have applications in pharmaceuticals, organic materials, and agrochemicals in both academic and industrial settings.

Metalloproteins are fundamental to diverse biological processes but still lack extensive investigation in viral contexts. This study reveals the prevalence and functional diversity of metal-binding proteins in DNA viruses. Among a subset of 1432 metalloproteins, zinc and magnesium-binding proteins are notably abundant, indicating their importance in viral biology. Furthermore, significant numbers of proteins binding to iron, manganese, copper, nickel, mercury, and cadmium were also detected. Human-infecting viral proteins displayed a rich landscape of metalloproteins, with MeBiPred (964 proteins) and Pfam (666) yielding the highest numbers. Interestingly, many essential viral proteins exhibited metal-binding capabilities, including polymerases, DNA binding proteins, helicases, dUPTase, thymidine kinase, and various structural and accessory proteins. This study sheds light on the ubiquitous presence of metalloproteins, their functional signatures, subcellular placements, and metal-utilization patterns, providing valuable insights into viral biology. A similar metal utilization pattern was observed in similar functional proteins across the various DNA viruses. Furthermore, these findings provide a foundation for identifying potential drug targets for combating viral infections.

Blue energy generation in nanochannels based on salinity gradients is currently the most promising method in the area of nonconventional energy production. We used a semidiluted pure sodium carboxymethylcellulose (NaCMC)-KCl aqueous solution to study the characteristics of blue energy generation within a charged nanochannel. We solve the corresponding equations for ionic transport using a numerical technique based on the finite element method. Our analysis focused on the electric double layer (EDL) potential field, open circuit current, diffuse potential, electric conductance, maximum generated pore power, and maximum energy conversion efficiency by varying concentrations of the salt in the left-side reservoir and the bulk polyelectrolyte. The results indicate that as the polyelectrolyte concentration increases, the extent of EDL overlap considerably reduces. With an increase in polyelectrolyte concentration, the open circuit current increases, while the diffuse potential reduces. It was observed that both electrical conductance and maximal pore power improve considerably with higher polyelectrolyte concentrations. Interestingly, our modeling framework demonstrates a power density substantially higher (up to 16.31 W/m 2 ) than earlier configurations and surpasses the established commercial limit (5 W/m 2 ). Furthermore, our findings reveal that the reservoir salt concentration significantly affects the rate of decline in the maximum energy conversion efficiency as the polyelectrolyte concentration increases. The research paves the way for the development of high-power-density devices with several practical applications.

For a long time, molecular electrocatalysts have been developed to reduce CO 2 efficiently to value-added products such as CO and HCO 2 H, along with H 2 ; however, selectivity remained as a major issue. Recent work toward addressing this issue showed that several different catalysts could be used to achieve product selectivity. It is desirable that instead of using different catalysts for specific products, a single catalyst should be able to produce the target products by subtle tuning of the reaction conditions. Toward this objective, herein we presented the organometallic Co electrocatalyst Co- NHC U and successfully utilized it in the electrochemical CO 2 reduction reaction (CO 2 RR) to produce CO, H 2 , and HCO 2 H with notable selectivity. The reduction of CO 2 selectively produced CO with 81 ± 2% Faradaic efficiency (FE) in the presence of 5% H 2 O as a proton source. The selectivity was changed toward H 2 with 80 ± 3% FE when 1.5 M triethylamine was added as an additive in the presence of 10% H 2 O as a proton source. In the presence of 1.0 M morpholine as an external additive, the CO 2 -saturated solution containing 10% trifluoroethanol as a proton source generates 55 ± 5% HCO 2 H as the predominant product, with H 2 as a competitive side product. It was found that the combined effect of the proton source and the additive in association with the nature of the Co- NHC U catalyst changed the selectivity of the products in this reaction.

The metal halide perovskite nanocrystals exhibit a remarkable tolerance to midgap defect states, resulting in high photoluminescence quantum yields. However, the potential of these nanocrystals for applications in display devices is hindered by the suppression of biexcitonic emission due to various Auger recombination processes. By adopting single-particle photoluminescence spectroscopy, herein, we establish that the biexcitonic quantum efficiency increases with the increase in the number of facets on cesium lead bromide perovskite nanocrystals, progressing from cube to rhombic dodecahedron to rhombicuboctahedron nanostructures. The observed enhancement is attributed mainly to an increase in their surface polarity as the number of facets increases, which reduces the Coulomb interaction of charge carriers, thereby suppressing Auger recombination. Moreover, Auger recombination rate constants obtained from the time-gated photon correlation studies exhibited a discernible decrease as the number of facets increased. These findings underscore the significance of facet engineering in fine-tuning biexciton emission in metal halide perovskite nanocrystals.

Coal gasification is the most demanding technology, increasing day by day for synthesis gas and chemical production in a clean environment. Coal is a primary source of energy or fuel. India has a high preservation of high-ash coal. Employment of this coal for gasification is tough due to its abrasive nature. Coal blending is an effective way to utilize such coal and to control the gasification performance. The present study focuses on using high-ash, low-rank Indian coal with high-rank imported coal in a suitable blend. The blending effect on raw gas yield (kg/kg of coal) and heating value (kcal/Nm 3 ) was studied for coal blends-CH1 (20:80), CH2 (30:70), CH3 (40:60), CH4 (50:50), and CH5 (60:40) of RC (raw Indian coal) with RH (raw high-rank imported coal). Also, the gasification characteristics of the WC (washed Indian coal) were studied similarly. It may be seen that the raw gas yield with blends of raw coal and the rank of imported coal is 1.11 to 1.46 (ton/ton of coal), whereas in washed Indian coal, it is 0.95 (ton/ton of coal). A slight change was observed in the heating value of raw gas, and its average value in the blended CH1 to CH5 coal is 2860 kcal/Nm 3 , whereas in WC, it is 2956 kcal/Nm 3 . The maximum utilization of raw coal in the blend for gasification can be 60%, which is economical and 0.55 times more effective than WC gasification., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The photochemistry and photophysics of thiocarbonyl compounds, analogues of carbonyl compounds with sulfur, have long been overshadowed by their counterparts. However, recent interest in visible light reactions has reignited attention toward these compounds due to their unique excited-state properties. This study delves into the ultrafast dynamics of 7-diethylaminothiocoumarin (TC1), a close analogue of the well-known probe molecule coumarin 1 (C1), to estimate intersystem crossing rates, understand the mechanisms of fluorescence and phosphorescence, and evaluate TC1's potential as a solvation dynamics probe. Enclosing TC1 within an organic capsule indicates its potential applications, even in aqueous environments. Ultrafast studies reveal a dominant subpicosecond intersystem crossing process, indicating the importance of upper excited singlet and triplet states in the molecule's photochemistry. The distinct fluorescence and phosphorescence origins, along with the presence of closely spaced singlet excited states, support the observed efficient intersystem crossing. The sulfur atom alters the excited-state behavior, shedding light on reactive triplet states and paving the way for further investigations.

Surface contamination and friction result in significant energy losses with widespread environmental impact. In the present work, we developed fluorine-free super-slippery surfaces employing environmentally friendly and simple biofuel-based flame treatment of polydimethylsiloxane (PDMS). Through a unique combination of processing parameters, highly transparent (>90%) and flexible films were engineered with omniphobic, anti-icing, and ultra-low friction properties. The processed films showed an extremely low tilting angle (<5°) and contact angle hysteresis (<4°) against different liquids, even under subzero temperatures. The coefficient of friction (COF) reduced to 0.01 after processing compared to ∼1 for PDMS. Extremely low ice adhesion of <20 kPa and enhanced freezing time ensured anti-icing behavior. The exceptional multidimensional traits were derived from the extremely stable silicone lubricant layer ensured by the hierarchically structured wrinkles. Wind tunnel tests showed that an air drag velocity of less than 0.5 m/s was sufficient to initiate droplet motion, highlighting low interfacial friction that leads to an anti-staining nature. Sustaining the self-cleaning and anti-staining characteristics, the processed surface showed utmost durability under different harsh conditions. The super-slippery surfaces with multifunctional characteristics fabricated through a sustainable route can be effectively used for various engineering and industrial applications.

Membrane technology plays a central role in advancing separation processes, particularly in water treatment. Covalent organic frameworks (COFs) have transformative potential in this field due to their adjustable structures and robustness. However, conventional COF membrane synthesis methods are often associated with challenges, such as time-consuming processes and limited control over surface properties. Our study demonstrates a rapid, microwave-assisted method to synthesize self-standing COF membranes within minutes. This approach allows control over the wettability of the surface and achieves superhydrophilic and near-hydrophobic properties. A thorough characterization of the membrane allows a detailed analysis of the membrane properties and the difference in wettability between its two faces. Microwave activation accelerates the self-assembly of the COF nanosheets, whereby the thickness of the membrane can be controlled by adjusting the time of the reaction. The superhydrophilic vapor side of the membrane results from -NH 2 reactions with acetic acid, while the nearly hydrophobic dioxane side has terminal aldehyde groups. Leveraging the superhydrophilic face, water filtration at high water flux, complete oil removal, increased rejection with anionic dye size, and resistance to organic fouling were achieved. The TTA-DFP-COF membrane opens new avenues for research to address the urgent need for water purification, distinguished by its synthesis speed, simplicity, and superior separation capabilities.

Nanoplastics pollution has led to a severe environmental crisis because of a large accumulation of these smaller nanoplastic particles in the aquatic environment and atmospheric conditions. Detection of these nanoplastics is crucial for food safety monitoring and human health. In this work, we report a simple and eco-friendly method to prepare a SERS-substrate-based nanoporous Ag nanoparticle (NP) film through vacuum thermal evaporation onto a vacuum-compatible deep eutectic solvent (DES) coated growth substrate for quantitative detection of nanoplastics in environmental samples. The nanoporous Ag NP films with controlled pores were achieved by the soft-templating role of DESs over the growth substrate, which enabled the self-assembly of deposited Ag NPs over the surface of DES. The optimized nanoporous Ag substrate provides high sensitivity in the detection of analyte molecules, crystal violet (CV), and rhodamine 6G (R6G) with a limit of detection (LOD) up to 1.5 × 10 -13 M, excellent signal reproducibility, and storage stability. Moreover, we analyzed quantitative SERS detection of polyethene terephthalate (PET, size of 200 nm) and polystyrene (PS, size of 100 nm) nanoplastics with an LOD of 0.38 and 0.98 μg/mL, respectively. In addition, the SERS substrate efficiently detects PET and PS nanoplastics in real environmental samples, such as tap water, lake water, and diluted milk. The enhanced SERS sensing ability of the proposed nanoporous Ag NP film substrate holds immense potential for the sensitive detection of various nanoplastic contaminants present in environmental water.

As one of the seldom explored systems, molybdenum-based metal-organic frameworks (Mo-MOFs) with different ligands such as terephthalic acid (Mo-TA), 2-aminoterephthalic acid (Mo-ATA), benzenetricarboxylic acid (Mo-BTC), 2-methylimidazole (Mo-2MI), 2-bipyridine (Mo-2bpy), and 4-bipyridine (Mo-4bpy) were developed in this study. X-ray diffraction (XRD), Raman, and attenuated total reflectance-infrared (ATR-IR) analyses confirmed the ligand-dependent crystal structure of the Mo-MOFs along with the characteristic functional groups present in the respective systems. Interestingly, the morphology of all of these the developed Mo-MOFs was found to be a one-dimensional rod-like structure, which was attributed to the binding nature of the ligands onto the growing Mo-frameworks. Optical analysis indicated that all these Mo-MOFs exhibit ultraviolet (UV) light absorption properties with band gap energy in the range of 3.47-3.03 eV. Among the various Mo-MOFs developed, Mo-4bpy MOF degraded a maximum of ∼76 and 62% of malachite green and Congo red dyes, respectively, under sunlight irradiation. The observed improved photocatalytic efficiency of Mo-4bpy MOF was attributed to its appropriate band edge potential, confirmed by Mott-Schottky analysis, improved carrier lifetime (∼34.6 ns) estimated using the time-resolved photoluminescence (TRPL) spectrum, presence of elements with stable oxidation states in the system confirmed by X-ray photoelectron spectroscopy (XPS), improved charge transfer characteristics, and decreased recombination resistance, as confirmed by impedance and PL analyses, respectively. The degradation of Mo-4bpy MOFs mediated by superoxide ( • O 2 - ) and hydroxyl radicals (OH • ) was further confirmed by scavenger studies. Cyclic studies performed for up to 5 cycles suggested that the degradation efficiency of the Mo-4bpy MOF was stable, attributed to its excellent structural, optical, and morphological features confirmed via postcharacterization of the recycled photocatalyst.

Synthesis of various polycyclic aromatic hydrocarbons (PAHs) from a palladium-catalyzed [3 + 2] cyclocondensation reaction is reported herein. The design strategy consisted of reacting the sterically hindered 1,2-bis(3,5-di tert -butylphenyl)acetylene 2 with myriad brominated anthracene and pyrene surrogates, resulting in the formation of target molecules MCP1-2 and DCP1-3 , which exhibited excellent solubility in commonly used organic solvents and unveiled prominent aggregation-induced emission (AIE) characteristics in tetrahydrofuran and water solvent mixtures. Calculations using density functional theory (DFT) were utilized to validate both the contorted structures of the target molecules and their electronic conjugation featuring HOMO-LUMO band gaps (Δ E ) in the range of ∼2.88 to 2.97 eV for the monocylopentannulated PAHs MCP1-2 , and between ∼2.23 to 2.41 eV for the dicyclopentannulated PAHs DCP1-3 . Furthermore, the biomedical features of DCP2 were investigated in cell-imaging experiments employing the RAW 264.7 macrophage cell line as a model system showing a high biocompatibility for DCP2 , thus paving the way for its potential application in bioimaging. These findings underscore the significance of the target compounds as prominent AIEgens with exceptional photophysical properties and biocompatibility, therefore promoting them as valuable tools for bioimaging applications., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Synthesis of quinoline-containing spiropyrrolizine was achieved via a 1,3-dipolar cycloaddition reaction of azomethine ylide (generated in situ from ninhydrin and l-proline) and ( E )-2-styrylquinoline. The synthesized compounds were characterized by 1 H NMR, 13 C NMR, HRMS, and single-crystal XRD analysis. The XRD data revealed that the solid-state structures of the compounds belong to the monoclinic system of the space group P 2 1 / c and are stabilized through various weak noncovalent interactions such as C-H···O, C-H···π, and π···π interactions. The noncovalent interactions are characterized and quantified through Hirshfeld surface analysis. Moreover, the interaction energies of the intermolecular noncovalent interactions are calculated through PIXEL calculation. The PIXEL calculation provides precise interaction energy with an energy decomposition scheme. Energy Framework calculations have also been performed to delve deeper into understanding the intermolecular interactions. The intermolecular interactions are further characterized using Bader's theory of "atoms in molecules" (QTAIM) and the "noncovalent" (NCI) interaction plot index. The nature and strength of noncovalent interactions are analyzed from the topological parameters at (3, -1) bond critical points (BCPs)., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Many proteins are thought to coordinate distant sites in their structures through a concerted action of global structural vibrations. However, the direct experimental spectroscopic detection of these vibration modes is rather elusive. We used normal-mode analysis to explore the dominant vibration modes of an all-atom model of the tubulin protein and described their characteristics using a large ensemble of tubulin structures. We quantified the frequency range of the normal vibrational modes to be in the subterahertz band, specifically between ∼40 and ∼160 GHz. Adding water layers to the model increases the frequencies of the low-frequency modes and narrows the frequency variations of the modes among the protein ensemble. We also showed how the electromagnetic absorption of tubulin vibration modes is affected by vibrational damping. These results contribute to our understanding of tubulin's vibrational and electromagnetic properties and provide a foundation for future attempts to control protein behavior via external electromagnetic fields.

Enhancing molecular self-assembly at the monolayer level offers significant potential for various applications. For monolayers made of π-conjugated discotic liquid crystal (DLC) molecule nanowires, achieving precise separation and alignment of these nanowires has been a long-standing challenge. This research explores an approach using the manipulation of subphase temperature and surface pressure within a Langmuir trough to control molecular nanowire separation. We observe notable temperature-dependent behavior: as the temperature increases from 5 to 30 °C, the monolayer collapse pressure rises steadily. In contrast, temperatures from 35 to 50 °C exhibit an initial small plateau with a nonzero slope that becomes more distinct with rising temperature. Our study of Langmuir-Blodgett (LB) films provides crucial insights into the monolayer's structure. At lower temperatures, the LB films show coalesced molecular nanowires, whereas at higher temperatures, the DLC nanowires separate and form an interconnected network. Remarkably, upon compression, this network transforms into a compact, highly uniform monolayer. To explain these temperature-dependent behaviors, we examine the area relaxation curves, which indicate a two-step molecular loss mechanism involving desorption and monolayer collapse due to the nucleation and growth of critical nuclei. This extensive study offers valuable insights into the dynamic interaction of the temperature, surface pressure, and molecular assembly, enhancing our understanding of the fundamental processes in monolayer self-assembly.

Two-dimensional (2D) semiconductor field-effect film transistors combine large carrier mobility with mechanical flexibility and therefore can be ideally suitable for wearable electronics or at the sensor interfaces of smart sensor systems. However, such applications require large-area solution processing as opposed to single-flake devices, where the critical challenge to overcome is the high interflake resistance values. In this report, using a narrow-channel, near-vertical transport device architecture, we have fabricated inkjet-printed sub-20 nm channel electrolyte-gated transistors with predominantly intraflake carrier transport. Therefore, the electronics transport in these transistors is not dominated by the high interflake resistance, and the intraflake material properties including doping density, defect concentration, contact resistance, and threshold voltage modulation can be examined and optimized independently to achieve a current density as high as 280 μA·μm -1 . In addition, through the passivation of the sulfur vacancies with a tailored surface treatment, we demonstrate an impressive On-Off current ratio exceeding 1 × 10 7 , complemented by a low subthreshold swing of 100 mV·decade -1 . Next, exploiting these high-performance transistors, unipolar depletion-load-type inverters have been fabricated that show a maximum gain of 31. Furthermore, we have realized NAND, NOR, and OR gates, demonstrating their seamless operation at a frequency of 1 kHz. Therefore, this work represents an important step forward to realize electronic circuits based on printed 2D thin film transistors.

Achieving rapid clotting and clot stability are important unmet goals of clinical management of noncompressible hemorrhage. This study reports the development of a spatiotemporally controlled release system of an antihemorrhagic drug, etamsylate, in the management of internal hemorrhage. Gly-Arg-Gly-Asp-Ser (GRGDS) peptide-functionalized chitosan nanoparticles, with high affinity to bind with the GPIIa/IIIb receptor of activated platelets, were loaded with the drug etamsylate (etamsylate-loaded GRGDS peptide-functionalized chitosan nanoparticles; EGCSNP). Peptide conjugation was confirmed by LCMS, and the delivery system was characterized by DLS, SEM, XRD, and FTIR. In vitro study exhibited 90% drug release till 48 h fitting into the Weibull model. Plasma recalcification time and prothrombin time tests of GRGDS-functionalized nanoparticles proved that clot formation was 1.5 times faster than nonfunctionalized chitosan nanoparticles. The whole blood clotting time was increased by 2.5 times over clot formed under nonfunctionalized chitosan nanoparticles. Furthermore, the application of rheometric analysis revealed a 1.2 times stiffer clot over chitosan nanoparticles. In an in vivo liver laceration rabbit model, EGCSNP spatially localized at the internal injury site within 5 min of intravenous administration, and no rebleeding was recorded up to 3 h. The animals survived for 3 weeks after the injury, indicating the strong potential of the system for the management of noncompressible hemorrhage.

Herein, we have synthesized a three-dimensional and hydrophobic graphene incorporated carbon aerogel (G-SCA) derived from sugar. G-SCA is being used as a multifunctional sorbent material for removing various advanced water-soluble and insoluble pollutants. Initially, G-SCA is being explored for the adsorption of nitroarenes (nitrophenols, 3-nitroaniline), an insecticide (Phoskill), an antibiotic (ciprofloxacin), and a pharmaceutical drug precursor (pyridine). Later, the same G-SCA is also explored in the absorption of various protic and aprotic organic solvents, and oils (including crude oil, waste cooking oil, and waste engine oil), with excellent recyclability checked up to 10 cycles. Moreover, oil-water separation experiments are also being done in various industrial wastewater and seawater samples to support the real-life accessibility of the present approach. Large-scale applicability of G-SCA is also checked by performing crude oil-seawater separation experiments using a laboratory-scale prototype demonstrating the successful continuous recovery of crude oil.

Early detection of cancer is vital for increasing patient survivability chances. The three major techniques used to diagnose cancers are instrumental examination, tissue biopsy, and tumor biomarker detection. Circulating tumor DNA (ctDNA) has gained much attention in recent years due to advantages over traditional technology, such as high sensitivity, high specificity, and noninvasive nature. Through the mechanism of apoptosis, necrosis, and circulating exosome release in tumor cells, ctDNA can spread throughout the circulatory system and carry modifications such as methylations, mutations, gene rearrangements, and microsatellite instability. Traditional gene-detection technology struggles to achieve real-time, low-cost, and portable ctDNA measurement, whereas electrochemical biosensors offer low cost, high specificity alongside sensitivity, and portability for the detection of ctDNA. Therefore, this review focuses on describing the recent advancements in ctDNA biomarkers for various cancer types and biosensor developments for real-time, noninvasive, and rapid ctDNA detection. Further in the review, ctDNA sensors are also discussed in regards to their selections of probes for receptors based on the electrode surface recognition elements.

In the presence of Eosin Y ( EY ), the synthesis of substituted phenothiazones was carried out efficiently using various substituted 2-aminothiophenol, diazonium salts, and 1,4-napthaquinones ( 1,4-NQ ) at room temperature (RT) (condition: green LED of 525 nm, 44 W; reaction time: 8 h, isolated yield: 68-90%). A fluorescence quenching experiment and density functional theory (DFT) calculations suggested that the triplet photoexcited state of EY (EY*; τT = 320 ± 10 ns) converts to EY +• via oxidative quenching by ArN 2 + (-1.11 V vs SCE for EY* to EY +• ) initially. Thiyl and aryl radicals were captured as TEMPO adducts in high-resolution mass spectroscopy (HRMS). The reaction was not inhibited by the addition of a singlet oxygen quencher such as 1,4-diazobicyclo [2.2.2] octane (DABCO), which suggests that singlet oxygen is not participated., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Epigallocatechin-3-gallate (EGCG) and ascorbic acid (AA)-loaded transferosomes (TRANS) were developed for brain delivery. The investigation covered EGCG-TRANS, AA-TRANS, and EGCG-AA-TRANS formulations using the film hydration technique. We analyzed the formed transferosomes to confirm the presence of vesicles loaded with the respective drugs and their performance within a living organism. The sizes of the particles for EGCG-TRANS, AA-TRANS, and EGCG-AA-TRANS were measured correspondingly at 174.2 ± 1.80, 132.7 ± 12.22, and 184.31 ± 9.5 nm. The appearance of diffused rings in the scanning electron microscopic image suggests that the payload has a crystalline structure. The atomic force microscope image displayed minimal surface irregularities, potentially indicating the presence of a lipid layer on the surface. Hemolysis results indicated the safety of the vesicles. The results showed 10.23, 7.21, and 8.20% of hemolysis for EGCG-TRANS, AA-TRANS, and EGCG-AA-TRANS, respectively. In the case of EGCG-AA-TRANS, the release of EGCG was determined to be 61.65% ± 4.61 after 72 h when exposed to phosphate buffer saline (pH 7.4). In vivo studies show a good response against Alzheimer's disease (AD). EGCG-AA-TRANS (82.166%) exhibited a higher percentage of AChE inhibition in comparison to EGCG-TRANS (66.550%) and AA-TRANS (53.466%). Intranasal delivery of EGCG-AA-TRANS resulted in approximately a 5-fold enhancement in memory. Formulation allowed EGCG and AA to accumulate in various organs, including the brain. The results suggest that EGCG-AA-TRANS could be safe and effective for treating AD., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

TTK21 is a small-molecule activator of p300/creb binding protein (CBP) acetyltransferase activity, which, upon conjugation with a glucose-derived carbon nanosphere (CSP), can efficiently cross the blood-brain barrier and activate histone acetylation in the brain. Its role in adult neurogenesis and retention of long-term spatial memory following intraperitoneal (IP) administration is well established. In this study, we successfully demonstrate that CSP-TTK21 can be effectively administered via oral gavage. Using a combination of molecular biology, microscopy, and electrophysiological techniques, we systematically investigate the comparative efficacy of oral administration of CSP and CSP-TTK21 in wild-type mice and evaluate their functional effects in comparison to intraperitoneal (IP) administration. Our findings indicate that CSP-TTK21, when administered orally, induces long-term potentiation in the hippocampus without significantly altering basal synaptic transmission, a response comparable to that achieved through IP injection. Remarkably, in a spinal cord injury model, oral administration of CSP-TTK21 exhibits efficacy equivalent to that of IP administration. Furthermore, our research demonstrates that oral delivery of CSP-TTK21 leads to improvements in motor function, histone acetylation dynamics, and increased expression of regeneration-associated genes (RAGs) in a spinal injury rat model, mirroring the effectiveness of IP administration. Importantly, no toxic and mutagenic effects of CSP-TTK21 are observed at a maximum tolerated dose of 1 g/kg in Sprague-Dawley (SD) rats via the oral route. Collectively, these results underscore the potential utility of CSP as an oral drug delivery system, particularly for targeting the neural system.

Electrophoresis of charged particles has important applications in biochemical separation processes. The mobility of these particles depends on the surrounding electric double layer (EDL), which is impacted by solvent restructuring because of hydration interactions. Nevertheless, most theoretical estimates ignore such interactions during computation of the electrophoretic mobility. Here, we employ a complementary blend of mean-field analysis and molecular dynamics simulations performed for a peptide-G-quadruplex complex to assess how hydration interactions alter the mobility of a charged particle in an aqueous medium. These interactions are seen to stabilize the EDL, resulting in more significant localized counterion concentrations while strengthening the ensuing electrokinetic flow. The ordering of ions near the particle surface is obtained only upon including hydration interaction, revealing that the hydration water molecules act as a glue for forming a stable EDL, a key finding of this work. Conversely, the observed microstructure of ions near the charged surface as obtained from our theory establishes a bridge link between the micro and continuum model. The presence of larger counter ions enhances the drag on the particle, thus restricting its mobility. The mobility also becomes dependent on size, which may be useful for isolating a wide array of biomolecules. The impact of hydration interactions intensifies with increases in particle size, surface charge density, and bulk ion concentration.

Spirocyclobutyl oxindoles have garnered substantial attention in drug discovery and pharmaceuticals owing to their wide range of biological activities. Strain-release in small-ring compounds is a powerful strategy to enable efficient access to complex molecules. In this study, we successfully realized a photoredox-catalyzed strain-release radical spirocyclization approach to attain functionalized spirocyclobutyl oxindoles. A diverse array of radicals, such as sulfonyl, phosphonyl, and trifluoromethyl, were added efficiently to the strained C-C σ-bond of bicyclobutanes (BCBs) to afford a library of spirocyclobutyl oxindoles. Furthermore, the obtained products could be transformed into valuable building blocks. The observed reactivity and selectivity have been rationalized based on density functional theory calculations.

Quantum photonic devices require robust sources of single photons to perform basic computational and communication protocols. Thus, developing scalable, integrable, and efficient quantum light sources has become crucial for the realization of quantum photonic devices. Single quantum dots are promising sources of quantum light due to their tunable emission wavelength. Here, we show the emergence of quantum-emitter-like antibunched emission behavior when multiple quantum dots are located in the vicinity of plasmonic particles. To evaluate the robustness of this phenomenon, we consider both monometallic and bimetallic particles. We find that the photoluminescence intensity of the plasmon coupled quantum dots fits well to a single sublinear power law exponent that is distinct from the behavior of CQD aggregates. Significantly, we find that plasmon coupling results in reduced flickering, thus enabling the realization of a more stable and reliable single photon source. Possible roles of emergent excitonic interactions in the coupled system are discussed.

Single-layer two-dimensional (2D) nanomaterials exhibit physical and chemical properties which can be dynamically modulated through out-of-plane deformations. Existing methods rely on intricate micromechanical manipulations ( e.g ., poking, bending, rumpling), hindering their widespread technological implementation. We address this challenge by proposing an all-optical approach that decouples strain engineering from micromechanical complexities. This method leverages the forces generated by chiral light beams carrying orbital angular momentum (OAM). The inherent sense of twist of these beams enables the exertion of controlled torques on 2D monolayer materials, inducing tailored strain. This approach offers a contactless and dynamically tunable alternative to existing methods. As a proof-of-concept, we demonstrate control over the conductivity of graphene transistors using chiral light beams, showcasing the potential of this approach for manipulating properties in future electronic devices. This optical control mechanism holds promise in enabling the reconfiguration of devices through optically patterned strain. It also allows broader utilization of strain engineering in 2D nanomaterials for advanced functionalities in next-generation optoelectronic devices and sensors.

The denitrifying sulfur (S) conversion-associated enhanced biological phosphorus removal (DS-EBPR) process for treating saline wastewater is characterized by its unique microbial ecology that integrates carbon (C), nitrogen (N), phosphorus (P), and S biotransformation. However, operational instability arises due to the numerous parameters and intricates bacterial interactions. This study introduces a two-stage interpretable machine learning approach to predict S conversion-driven P removal efficiency and optimize DS-EBPR process. Stage one utilized the XGBoost regression model, achieving an R 2 value of 0.948 for predicting sulfate reduction (SR) intensity from anaerobic parameters with feature engineering. Stage two involved the CatBoost classification and regression model integrating anoxic parameters with the predicted SR values for predicting P removal, reaching an accuracy of 94% and an R 2 value of 0.93, respectively. This study identified key environmental factors, including SR intensity (20-45 mg S/L), influent P concentration (<9.0 mg P/L), mixed liquor volatile suspended solids (MLVSS)/mixed liquor suspended solids (MLSS) ratio (0.55-0.72), influent C/S ratio (0.5-1.0), anoxic reaction time (5-6 h), and MLSS concentration (>6.50 g/L). A user-friendly graphic interface was developed to facilitate easier optimization and control. This approach streamlines the determination of optimal conditions for enhancing P removal in the DS-EBPR process.

The structure-property relationship considering isomerism-tuned photoluminescence and efficient catalytic activity of silver nanoclusters (NCs) is exclusive. Asymmetrical dithiophosphonate NH 4 [S 2 P(OR)( p -C 6 H 4 OCH 3 )] ligated first atomically precise silver NCs [Ag 21 {S 2 P(OR)( p -C 6 H 4 OCH 3 )} 12 ]PF 6 {where, R = n Pr ( 1 ), Et ( 2 )} were established by single-crystal X-ray diffraction and characterized by electrospray ionization mass spectrometry, NMR ( 31 P, 1 H, 2 H), X-ray photoelectron spectroscopy, UV-visible, energy-dispersive X-ray spectroscopy, Fourier transforms infrared, thermogravimetric analysis, etc. NCs 1 and 2 consist of eight silver atoms in a cubic framework and enclose an Ag@Ag 12 -centered icosahedron to constitute an Ag 21 core of T h symmetry, which is concentrically inscribed within the S 24 snub-cube, P 12 cuboctahedron, and the O 12 truncated tetrahedron formed by 12 dithiophosphonate ligands. These NCs facilitate to be an eight-electron superatom (1S 2 1P 6 ), in which eight capping Ag atoms exhibit structural isomerism with documented isoelectronic [Ag 21 {S 2 P(O i Pr) 2 } 12 ]PF 6, 3 . In contrast to 3 , the stapling of dithiophosphonates in 1 and 2 triggered bluish emission within the 400 to 500 nm region at room temperature. The density functional theory study rationalized isomerization and optical properties of 1 , 2 , and 3 . Both ( 1 , and 2 ) clusters catalyzed a decarboxylative acylarylation reaction for rapid oxindole synthesis in 99% yield under ambient conditions and proposed a multistep reaction pathway. Ultimately, this study links nanostructures to their physical and catalytic properties.

Metal core and dielectric shell nanoparticles (NPs) have garnered considerable attention for their multifaceted properties and extensive applications across diverse fields of nanoscience and nanotechnology. However, a literature gap exists regarding the impact of assembled metallic nanostar cores within a single shell, particularly concerning surface-enhanced Raman scattering (SERS) and electrochemical sensing. In this study, we have demonstrated the better performance of assemblies of gold nanostars (AuNSs) enclosed in single silica shell for SERS enhancement and electrocatalytic activity, particularly in the fields of ascorbic acid (AA) and glucose sensing. We have devised a method to isolate and passivate nanostar assemblies, ranging from 2 to 30 nanostars per assembly, with a functionalized silica (SiO 2 ) shell, facilitating their preservation. The engineered thickness of the silica shell ensures unhindered optical measurements while elucidating the influence of multiple AuNS cores. Due to the formation of nanogaps and nanojunctions between AuNSs within assembly, we have achieved a maximum SERS enhancement factor (EF) of 1.416 × 10 10 for the rhodamine 6G analyte. Utilizing assembled AuNS cores within a single silica shell, we have demonstrated AA (sensitivity of 5.278 × 10 -5 μA μM -1 cm -2 ) and glucose (sensitivity of 7.519 × 10 -4 μA μM -1 cm -2 ) sensing via a nonenzymatic electrochemical pathway.

Manipulating the crystallization of perovskite in thin films is essential for the fabrication of any thin-film-based devices. Fabricating tin-based perovskite films from solution poses difficulties because tin tends to crystallize faster than the commonly used lead perovskite. To achieve optimal device performance in solar cells, the preferred method involves depositing tin perovskite under inert conditions using dimethyl sulfoxide (DMSO), which effectively retards the formation of the tin-bromine network, which is crucial for perovskite assembly. We found that under ambient conditions, a DMSO-based tin perovskite salt solution resulted in the formation of a two-phase system, SnBr 4 (DMSO) 2 and MABr, whereas a dimethylformamide-based solution resulted in the formation of vacancy-ordered double perovskite MA 2 SnBr 6 . Humidity is known to solvate MABr to form the solvated ions, and so we used the two-phase system for the application in moisture to electricity conversion. The importance of the presence of the scaffold can be seen with the negligible power output from the vacancy-ordered double perovskite obtained with MA 2 SnBr 6 . We have fabricated a device with two-phase system that can generate an open-circuit potential of 520 mV and a short-circuit current density of 30.625 μA/cm 2 at 85% RH. Also, the device charges a 10 μF capacitor from 150 mV at 51% RH to 500 mV at 85% RH in 6 s at a rate of 52.5 mV/s. Moreover, the output can be scaled by connecting devices in series and parallel configurations. A 527 nm green LED was powered by connecting five devices in series at 75% RH. This indicates a potential for utilizing these moisture-to-electricity conversion devices in powering low-energy requirement devices.

Thorium-232 (Th), the most abundant naturally occurring nuclear fuel, has been identified as a sustainable source of energy. In view of its large-scale utilization and human evidence of lung disorders and carcinogenicity, it is imperative to understand the effect of Th exposure on lung cells. The present study investigated the effect of Th-dioxide (1-100 μg/mL, 24-48 h) on expression of surfactant proteins (SPs) (SP-A, SP-B, SP-C, and SP-D, which are essential to maintain lung's surface tension and host-defense) in human lung cells (WI26 and A549), representative of alveolar cell type-I and type-II, respectively. Results demonstrated the inhibitory effect of Th on transcriptional expression of SP-A, SP-B, and SP-C. However, Th promoted the mRNA expression of SP-D in A549 and reduced its expression in WI26. To a significant extent, the effect of Th on SPs was found to be in accordance with their protein levels. Moreover, Th exposure altered the extracellular release of SP-D/A from A549, which remained unaltered in WI26. Our results suggested the differential role of oxidative stress and ATM and HSP90 signaling in Th-induced alterations of SPs. These effects of Th were found to be consistent in lung tissues of mice exposed to Th aerosols, suggesting a potential role of SPs in Th-associated lung disorders.

Mitochondrial dysfunction is often linked to neurotoxicity and neurological diseases and stems from oxidative stress, yet effective therapies are lacking. Deoxynivalenol (DON or vomitoxin) is one of the most common and hazardous type-B trichothecene mycotoxins, which contaminates crops used for food and animal feed. Despite the abundance of preliminary reports, comprehensive investigations are scarce to explore the relationship between these fungal metabolites and neurodegenerative disorders. The present study aimed to elucidate the precise role of DON in mitochondrial dynamics and cell death in neuronal cells. Excessive mitochondrial fission is associated with the pathology of several neurodegenerative diseases. Human SH-SY5Y cells were treated with different concentrations of DON (250-1000 ng/mL). Post 24 and 48 h DON treatment, the indexes were measured as follows: generation of reactive oxygen species (ROS), ATP levels, mitochondrial membrane potential, calcium levels, and cytotoxicity in SH-SY5Y cells. The results showed that cytotoxicity, intracellular calcium levels, and ROS in the DON-treated group increased, while the ATP levels and mitochondrial membrane potential decreased in a dose-dependent manner. With increasing DON concentrations, the expression levels of P-Drp-1, mitochondrial fission proteins Mff, and Fis-1 were elevated with reduced activities of MFN1, MFN2, and OPA1, further resulting in an increased expression of autophagic marker LC3 and beclin-1. The reciprocal relationship between mitochondrial damage and ROS generation is evident as ROS can instigate structural and functional deficiencies within the mitochondria. Consequently, the impaired mitochondria facilitate the release of ROS, thereby intensifying the cycle of damage and exacerbating the overall process. Using specific hydroxyl, superoxide inhibitors, and calcium chelators, our study confirmed that ROS and Ca2+-mediated signaling pathways played essential roles in DON-induced Drp1 phosphorylation. Therefore, ROS and mitochondrial fission inhibitors could provide critical research tools for drug development in mycotoxin-induced neurodegenerative diseases.