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Paramagnetic complexes of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate (DOTA 4- ) derivatives have shown potential for molecular imaging with magnetic resonance. DOTA-tetraglycinate (DOTA-4AmC 4- ) coordinated with lanthanide metal ions (Ln 3+ ) demonstrates pH/temperature sensing with Biosensor Imaging of Redundant Deviation in Shifts (BIRDS) and Chemical Exchange Saturation Transfer (CEST), respectively, detecting nonexchangeable (e.g., -CH y , where 3 ≥ y ≥ 1) and exchangeable (e.g., -OH or -NH x , where 2 ≥ x ≥ 1) protons. Herein, we report paramagnetic complexes of divalent transition-metal ions (M 2+ = Fe 2+ , Co 2+ , Ni 2+ ) with DOTA-4AmC 4- that endow a unique amide proton (-NH) moiety for pH/temperature sensing. Crystallographic data reveal that DOTA-4AmC 4- coordinates with M 2+ through oxygen and nitrogen donor atoms, ranging in coordination numbers from 8-coordinate in Fe(II)DOTA-4AmC 2- , 7-coordinate in Co(II)DOTA-4AmC 2- , and 6-coordinate in Ni(II)DOTA-4AmC 2- . The -CH y protons in M(II)DOTA-4AmC 2- displayed modest pH/temperature sensitivities, but -NH protons exhibited higher intensity, suggesting prominent BIRDS properties. The pH sensitivity was the highest for Ni(II)DOTA-4AmC 2- (1.42 ppm/pH), followed by Co(II)DOTA-4AmC 2- (0.21 ppm/pH) and Fe(II)DOTA-4AmC 2- (0.16 ppm/pH), whereas temperature sensitivities were comparable (i.e., 0.22, 0.13, and 0.17 ppm/°C, respectively). The CEST image contrast for -NH in M(II)DOTA-4AmC 2- was much weaker compared to that of Ln(III)DOTA-4AmC - . Given its high pH sensitivity and low cytotoxicity, Ni(II)DOTA-4AmC 2- shows promise for use in preclinical BIRDS-based pH imaging.

Ionic liquids (ILs) have promising applications in pharmaceuticals and green chemistry, but their use is limited by toxicity concerns, mainly due to their interactions with cell membranes. This study examines the effects of imidazolium-based ILs on the microscopic structure and phase behavior of a model cell membrane composed of zwitterionic dipalmitoylphosphatidylcholine (DPPC) lipids. Small-angle neutron scattering and dynamic light scattering reveal that the shorter-chain IL, 1-hexyl-3-methylimidazolium bromide (HMIM[Br]), induces the aggregation of DPPC unilamellar vesicles. In contrast, this aggregation is absent with the longer alkyl chain IL, 1-decyl-3-methylimidazolium bromide (DMIM[Br]). Instead, DMIM[Br] incorporation leads to the formation of distinct IL-poor and IL-rich nanodomains within the DPPC membrane, as evidenced by X-ray reflectivity, differential scanning calorimetry, and molecular dynamics simulations. The less evident nanodomain formation with HMIM[Br] underscores the role of hydrophobic interactions between lipid alkyl tails and ILs. Our findings demonstrate that longer alkyl chains in ILs significantly enhance their propensity to form membrane nanodomains, which is closely linked to enhanced membrane permeability, as shown by dye leakage measurements. This heightened permeability likely underlies the greater cytotoxicity of longer-chain ILs. This crucial link between nanodomains and toxicity provides valuable insights for designing safer, more environmentally friendly ILs, and promoting their use in biomedical applications and sustainable industrial processes.

Nanostructured transition metal dichalcogenides (TMDs) like MoS 2 hold promise for gas sensing applications due to their exceptional properties. However, limitations exist in maximizing sensor performance, such as limited active sites for gas interaction and sluggish response/recovery times. This study explores swift heavy ion (SHI) irradiation as a strategy to address these challenges in MoS 2 -based NO 2 gas sensors. MoS 2 nanoflakes were fabricated and subsequently irradiated with 120 MeV silver (Ag) ions to induce structural and morphological modifications. Characterization techniques confirmed the formation of Mo and S vacancies within the MoS 2 lattice due to irradiation. Significantly, SHI irradiation resulted in a remarkable enhancement of approximately 3 times improvement in sensing response compared to pristine MoS 2 sensors. Additionally, the irradiated sensors exhibit substantial improvements in both response and recovery times for NO 2 detection. SHI irradiation resulted in the formation of self-affine nanostructures and increased grain fragmentation as fluence rises. This enhanced surface area is hypothesized to promote gas-sensor response. To gain deeper insights into the underlying mechanism, first-principles calculations were employed. These calculations suggest that electron transfer occurs from the MoS 2 surface to the NO 2 molecule during interaction. Furthermore, the irradiation-induced vacancies facilitate stronger NO 2 adsorption on the MoS 2 surface compared to the pristine sample. This work demonstrates the effectiveness of SHI irradiation in engineering defects within MoS 2 nanoflakes, leading to significantly improved NO 2 gas-sensing performance. This approach offers a promising avenue for developing next-generation TMD-based gas sensors with enhanced sensitivity, response times, and stability.

Magnetic nanoparticles (MNPs) have been extensively used for drug delivery, on-demand material deposition, etc. In this study, we demonstrate the capability to extract such MNPs on-demand from a magnetic nanoparticle-laden drop (MNLD) (i.e., a drop of a stable aqueous dispersion of MNPs), suspended inside a highly viscous polymer (poly(dimethylsiloxane) or PDMS) medium in the presence of an externally applied magnetic field. The phenomena involve the aggregation of the MNPs inside the drop and the consequent extraction of the MNP aggregate out of the drop, with the drop retaining its original shape after the MNP aggregate extraction. We define this latter phenomenon as de-encapsulation. This is the first study that, to the best of our knowledge, demonstrates such precise, controlled, and on-demand removal of the NPs from the interior of a drop (where the NPs, which were originally inside the drop, breach the drop interface and get completely separated from the drop as an aggregate) without any permanent deformation of the drop. We quantify the effect of the changes in the MNP concentration and the drop volume in determining the de-encapsulation distance, which refers to the distance between the drop and the location of the magnet at the time instant when the MNP aggregate leaves the drop. We further identify the volume of the aggregates extracted from the drop and the mechanisms causing such de-encapsulation. We propose a theory to describe the process, and our theoretical predictions capture the experimental trends well. In addition, we also demonstrate multiple, back-to-back MNP aggregate extractions from a single MNLD at different sites, indicating the possibility that the MNLD can be used as an on-demand carrier and depositor of materials. Overall, our results, in addition to demonstrating the first-of-its-kind de-encapsulation of NPs (in the form of an aggregate) from the drop interior, demonstrate a method to control the dynamics, extraction, and targeted deposition of the MNPs.

Controlling excitons and their transport in two-dimensional (2D) transition metal dichalcogenide heterostructures is central to advancing photonics and electronics on-chip integration. We investigate the controlled generation and manipulation of excitons and their complexes in monolayer MoSe 2 -WSe 2 lateral heterostructures (LHSs). Incorporating graphene as a back gate and edge contact in a field-effect transistor geometry, we achieve the precise electrical tuning of exciton complexes and their transfer across interfaces. Photoluminescence and photocurrent maps at 4 K reveal the synergistic effect of the local electric field and interface phenomena in the modulation of excitons, trions, and free carriers. We observe spatial variations in the exciton and trion densities driven by exciton-trion conversion under electrical manipulation. Additionally, we demonstrate controlled narrow-band emissions within the LHS through carrier injection and electrical biasing. Density functional theory calculation reveals significant band modification at the lateral interfaces. This work advances exciton manipulation in LHS and shows promise for next-generation 2D quantum devices.

Sequestration of protein molecules and nucleic acids to stress granules is one of the most promising strategies that cells employ to protect themselves from stress. In vitro, studies suggest that the nucleic acid-binding domain of TDP-43 (TDP-43 tRRM ) undergoes amyloid-like aggregation to β-sheet-rich structures in low pH stress. In contrast, we observed that the TDP-43 tRRM undergoes complex coacervation in the presence of ssDNA to a dense and light phase, preventing its amyloid-like aggregation. The soluble light phase consists of monomeric native-like TDP-43 tRRM . The microscopic data suggest that the dense phase consists of spherical coacervates with limited internal dynamics. We performed multiparametric analysis by employing various biophysical techniques and found that complex coacervation depends on the concentration and ratio of the participating biomolecules and is driven by multivalent interactions. The modulation of these forces due to environmental conditions or disease mutations regulates the extent of coacervation, and the weakening of interactions between TDP-43 tRRM and ssDNA leads to amyloid-like aggregation of TDP-43 tRRM . Our results highlight a competition among the native state, amyloid-like aggregates, and complex coacervates tuned by various environmental factors. Together, our results illuminate an alternate function of TDP-43 tRRM in response to pH stress in the presence of the ssDNA.

We investigate energy generation from salinity gradients inside a nanopore that is connected to reservoirs at both ends. We consider that the inner wall surfaces are grafted with a densely grafted polyelectrolyte layer (PEL). We developed the PEL grafting density-dependent correlation of dielectric permittivity, molecular diffusivity, and dynamic viscosity in this endeavor. Using these correlations, we employ the finite element framework to solve the equations describing the ionic and fluidic transport. We use a partially hydrolyzed polyacrylamide polymer solution, which exhibits a shear-thinning fluid, in combination with the KCl electrolyte for energy-harvesting analysis. To describe the shear-rate-dependent apparent viscosity of non-Newtonian liquid, we have employed the Carreau model. For a window of right-side reservoir concentration, we investigate the effects of ion-partitioning in conjugation with the change in PEL grafting density on the ionic field, ionic selectivity, pore current, osmotic power, energy conversion efficiency, and flow field. The findings of this endeavor demonstrate how the ion-partitioning effect lowers the screening effect and raises the electrical double layer (EDL) potential by reducing the counterions in PEL. We show that the unique distribution of the ionic field leads to a higher prediction of generated osmotic power and power density due to the ion-parting effect. Additionally, we establish that the augmentation in PEL space charge density leads to improvement in average flow velocity, osmotic power, and consequently energy conversion efficiency. We establish that the generated osmotic power density and the energy conversion efficiency become very high at the higher grafting density. In summary, inferences of this analysis are deemed pertinent in designing the nanoscale device intended for high and efficient osmotic energy generation.

Aggregation of TDP-43 is linked to the pathogenesis of many neurodegenerative diseases, including amyotrophic lateral sclerosis (ALS). Notably, electrostatic point mutations such as D169G and P112H, located within the highly conserved functional tandem RNA recognition motif (RRM) domains of the TDP-43 protein (TDP-43 tRRM ), have been identified in diseased patients as well. In this study, we address how the electrostatic mutations alter both the native state stability and aggregation propensity of TDP-43 tRRM . The mutants D169G and P112H show increased chemical stability compared to the TDP-43 tRRM at physiological pH. However, at low pH, both the mutants undergo a conformational change to form amyloid-like fibrils, though with variable rates─the P112H mutant being substantially faster than the other two sequences (TDP-43 tRRM and D169G mutant) showing comparable rates. Moreover, among the three sequences, only the P112H mutant undergoes a strong ionic strength-dependent aggregability trend. These observations signify the substantial contribution of the excess charge of the P112H mutant to its unique aggregation process. Complementary simulated observables with atomistic resolution assign the experimentally observed sequence-, pH-, and ionic strength-dependent aggregability pattern to the degree of thermal lability of the mutation site-containing RRM1 domain and its extent of dynamical anticorrelation with the RRM2 domain whose combination eventually dictate the extent of generation of aggregation-prone partially unfolded conformational ensembles. Our choice of a specific charge-modulated pathogenic mutation-based experiment-simulation-combination approach unravels the otherwise hidden residue-wise contribution to the individual steps of this extremely complicated multistep aggregation process.

Two new dioxidovanadium(V) compounds with the general formula [V V O 2 (L)] (L = hydrazone ligand) were synthesized using three different methods (acidic, neutral, and basic media) with either V IV OSO 4 . 5H 2 O, [V IV O(acac) 2 ], or NH 4 V V O 3 as the starting material and hydrazone ligands. In both cases, five coordinated V 5+ ions adopted distorted square pyramidal geometry through the coordination of two oxido ligands and one hydrazone ligand. In compound 1 , the presence of free hydroxyl groups stabilized the molecular species through intramolecular O-H•••N type hydrogen bond interactions. In compound 2 , the free amino groups are involved in both intramolecular N-H•••N type and intermolecular N-H•••O type hydrogen bond interactions. Compound 1 showed highly selective luminescence turn-on behavior, along with a 33-nm blue shift in the presence of Al 3+ ions in an aqueous medium. The experimental limit of detection (LOD) was found to be 66 nM. Whereas compound 2 showed luminescence quenching behavior in the presence of Fe 3+ , Al 3+ , and Cr 3+ ions. The LODs were observed to be 312, 408, and 280 nM for Fe 3+ , Al 3+ , and Cr 3+ ions, respectively. The luminescence response mechanisms of both compounds in the presence of metal ions have been correlated with molecular-level interactions.

The aberrant aggregation of TAR DNA-binding protein 43 kDa (TDP-43) in cells leads to the pathogenesis of multiple fatal neurodegenerative diseases. Decoding the proposed initial transition between its functional dimeric and aggregation-prone monomeric states can potentially design a viable therapeutic strategy, which is presently limited by the lack of structural detail of the full-length TDP-43. To achieve a complete understanding of such a delicate phase space, we employed a multiscale simulation approach that unearths numerous crucial features, broadly summarized in two categories: (1) state-independent features that involve inherent chain collapsibility, rugged polymorphic landscape dictated by the terminal domains, high β-sheet propensity, structural integrity preserved by backbone-based intrachain hydrogen bonds and electrostatic forces, the prominence of the C-terminal domain in the intrachain cross-domain interfaces, and equal participation of hydrophobic and hydrophilic (charged and polar) residues in cross-domain interfaces; and (2) dimerization-modulated characteristics that encompass slower collapsing dynamics, restricted polymorphic landscape, the dominance of side chains in interchain hydrogen bonds, the appearance of the N-terminal domain in the dimer interface, and the prominence of hydrophilic (specifically polar) residues in interchain homo- and cross-domain interfaces. In our work, the ill-known C-terminal domain appears as the most crucial structure-dictating domain, which preferably populates a compact conformation with a high β-sheet propensity in its isolated state stabilized by intrabackbone hydrogen bonds, and these signatures are comparatively faded in its integrated form. Validation of our simulated observables by a complementary spectroscopic approach on multiple counts ensures the robustness of the computationally predicted features of the TDP-43 aggregation landscape.

In cells, TDP-43 is a crucial protein that can form harmful amyloid aggregates linked to fatal and incurable human neurodegenerative disorders. Normally, TDP-43 exists in a smaller soluble native state that prevents aggregation. However, aging and stress can destabilize this native state, leading to the formation of disease-causing amyloid aggregates via the formation of partially unfolded, high-energy intermediates with a greater tendency to aggregate. These intermediates are crucial in the early stages of amyloid formation and are challenging to study due to their low stability. Understanding the structure of these early aggregation-prone states of TDP-43 is essential for designing effective treatments for TDP-43 proteinopathies. Targeting these initial intermediates could be more effective than focusing on fully formed amyloid aggregates. By disrupting the aggregation process at this early stage, we may be able to prevent the progression of diseases related to TDP-43 aggregation. Hence, we decided to uncover the hidden, high-energy intermediates in equilibrium with the native states of TDP-43 by modulating the thermodynamic stability of the soluble native dimer (N form) and monomeric molten globular state (MG form) of full-length TDP-43. The thermodynamic modulation performed in the current study successfully revealed the highly aggregation-prone intermediate of full-length TDP-43, i.e., PUF. Moreover, we observed that along with high aggregation propensity, the aggregation kinetics and mechanisms of PUF differ from previously identified intermediates of full-length TDP-43 (the MG and I forms). The information regarding the initial aggregation-prone state of full-length TDP-43 could lead to therapies for amyloid diseases by halting early protein aggregation.

Fungal infection poses a major global threat to public health because of its wide prevalence, severe mortality rate, challenges involved in diagnosis and treatment, and the emergence of drug-resistant fungal strains. Millions of people are getting affected by fungal infection, and around 3.8 million people face death per year due to fungal infection, as per the latest report. The polyene antibiotic AmB has an extensive record of use as a therapeutic moiety against systemic fungal infection and leishmaniasis since 1960. AmB has broad-spectrum fungistatic and fungicidal activity. AmB exerts its therapeutic activity at the cellular level by binding to fungal sterol and forming hydrophilic pores, releasing essential cellular components and ions into the extracellular fluid, leading to cell death. Despite using AmB as an antifungal and antileishmanial at a broad scale, its clinical use is limited due to drug-induced nephrotoxicity resulting from binding the aggregated form of the drug to mammalian sterol. To mitigate AmB-induced toxicity and to get better anti-fungal therapeutic outcomes, researchers have developed nanoformulations, self-assembled formulations, prodrugs, cholesterol- and albumin-based AmB formulations, AmB-mAb combination therapy, and AmB cochleates. These formulations have helped to reduce toxicity to a certain extent by controlling the aggregation state of AmB, providing sustained drug release, and altering the physicochemical and pharmacokinetic parameters of AmB. Although the preclinical outcome of AmB formulations is quite satisfactory, its parallel result at the clinical level is insignificant. However, the safety and efficacy of AmB therapy can be improved at the clinical stage by continuous investigation and collaboration among researchers, clinicians, and pharmaceutical companies.

We report an organophotoredox-catalyzed silylation/germylation cascade cyclization of N -alkenyl α-CF 3 acrylamides under mild conditions. N -Aminopyridinium salts act as hydrogen atom transfer reagents under photoredox catalysis in the generation of silyl and germyl radicals. An array of silyl- and germyl-substituted 3-CF 3 -4-pyrrolin-2-one derivatives were constructed in a shorter reaction time with low catalyst loading in good to excellent yields at room temperature. Importantly, this protocol is amenable to the late-stage diversification of bioactive molecules, as well as to large-scale synthesis.

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 .

The escalating crisis of nanoplastic pollution in water and food products demands the development of novel methodologies for detection and recycling. Despite various techniques available, surface-enhanced Raman scattering (SERS) is emerging as a highly efficient technique for the trace detection of micro/nanoplastics. However, the development of highly reproducible and stable, flexible SERS substrates that can be used for sensitive detection in environmental medium remains a challenge. Here, we report a fabrication of large-area, three-dimensional (3D), and highly flexible SERS substrate based on porous dendritic Au films onto a flexible indium tin oxide (ITO) substrate via facile, thermal evaporation of Au over the vacuum-compatible deep eutectic solvent (DES)-coated glass substrate and subsequent direct transfer process. The as-fabricated 3D dendritic Au/ITO flexible substrates can be used for ultrasensitive SERS detection of crystal violet (CV) as probe analyte molecules with the limit of detection (LOD) as low as 6.4 × 10 -15 M, with good signal reproducibility (RSD of 11.3%). In addition, the substrate showed excellent sensitivity in detecting nanoplastics such as poly(ethylene terephthalate) (200 nm) and polystyrene (100 nm) with LODs reaching up to 0.051 and 8.2 μg/mL, respectively. This work provides a facile approach for the preparation of highly flexible plasmonic substrates, showing great potential for the SERS detection of a variety of environmental pollutants.

In the present work, a comparative study on eco-friendly synthesis of zinc oxide (ZnO) sample 1 and sample 2 with 3.17 and 4.17 M NaOH, respectively, is reported. Sample 2 with 4.17 M NaOH is applied in the photocatalytic degradation of paracetamol (pure and raw both) using the ultraviolet (UV, 280-400 nm) and UV/H 2 O 2 reaction systems. Pure paracetamol (PCM1) and raw paracetamol (PCM2) from tablets are used for photocatalytic degradation by photocatalysis. Our experimental evidence show that ZnO sample 2 was more active in the UV/H 2 O 2 reaction system than under ultraviolet (UV, 280-400 nm) irradiation only in the photocatalytic degradation process. Field emission scanning electron microscopy (FE-SEM) confirms the homogeneous growth of a rod-like structure for sample 1 and brittle and randomly aggregated rod-like and wire-like nanostructures for sample 2. The peaks observed in the region around 440 to 900 cm -1 in the FTIR spectra for sample 1 and sample 2 annealed at 250 °C confirms the presence of ZnO bonds. UV absorption spectroscopy indicates a red shift in the absorption spectra due to the increase in the molar concentration of NaOH to 4.17 M for sample 2. In this study, the band gap values are found to be 3.33 and 3.01 eV for the synthesized ZnO sample 1 and sample 2, respectively, which are 40 and 360 meV less as compared to that of bulk ZnO (3.37 eV). The oxidation rate is increased in the UV/H 2 O 2 reaction system, producing the highest rate for PCM1 drug removal with rate constant 9.7 × 10 -3 min -1 and half-life 71.5 min. The kinetic study results for the removal of PCM1 and PCM2 show good results and follow the pseudo-first-order kinetic model with correlation coefficients 0.69556 and 0.90851, respectively, whereas PCM2 follows the pseudo-second-order kinetic model with correlation coefficient 0.9993. The experimental and calculated values of removal capacity ( q e ) at equilibrium is found close to those of the pseudo-second order kinetic model for the removal of both the paracetamol forms PCM1 and PCM2 with the catalyst ZnO nanostructure. The photostability of ZnO sample 2 is also tested with a reusability test in photocatalytic degradation of paracetamol at least four times. The absence of a maxima peak at 243 of PCM1 in the UV/H 2 O 2 reaction system indicates nearly 100% successful conversion of 20 ppm PCM1 by using synthesized catalyst ZnO sample 2. The comparative results of both reaction systems, i.e., UV and UV/H 2 O 2 , show that the hydroxyl radicals, as the active species, are responsible for major degradation of both paracetamol forms (PCM1 and PCM2)., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Radiative cooling technologies have had a significant impact on advancing carbon neutrality efforts by significantly improving the passive cooling efficiency. The tandem of conduction and radiation enables solar-adaptive radiative cooling through the insulating effect of materials along with solar absorption, which affects the thermal state of materials and enhances radiative thermal transfer from the surface under solar irradiation. This enhancement is achieved by utilizing the porous polymeric structure of materials, which facilitates improved conduction pathways along with solar reflectance, while maintaining the effective emission of thermal radiation. In this particular scenario, blocks, which were made of recycled fibers, offer a great opportunity as solar-adaptive cooling materials, enabling their easy deployment for cooling applications. Herein, we have fabricated a porous block using fiber wastes that combines strong solar reflectance (92%) at the 1 μm region and high thermal infrared emittance (∼75%) at the 10 μm region. The combination of effective solar reflection and thermal infrared emission allows the fiber block to achieve a high cooling performance of approximately 68 W/m 2 under solar irradiation. In addition, the fiber block works effectively for insulation during the night, thereby enhancing its heat retention capabilities. The economic and environmental advantages of the fiber block make it a cost-competitive and sustainable choice for near-market cooling technologies. This design is anticipated to expand the practical application range of passive cooling.

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.

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.

An efficient and cost-effective Mn(I)-catalyzed site-selective C-H activation of 2-arylpyridines with maleimides has been described. This approach facilitates the synthesis of 3-arylated succinimide derivatives with high site selectivity, chemoselectivity, catalytic efficiency, and outstanding tolerance to numerous functional groups. The practicality of this approach is further evidenced by its successful application in large-scale reactions and the conversion of the synthesized succinimide derivatives into other valuable compounds.

Herein, we describe a two-step, cis -diastereoselective synthesis of indoline-2,3-fused chromans from 3-substituted indoles. The method proceeds without intermediacy of ortho -quinone methides and leverages the dual function of TBS-protected 2-hydroxybenzyl iodides both as highly reactive alkylating agents in a t -BuONa/Et 3 B-promoted dearomative alkylation step and as a source of masked phenoxide nucleophiles in a subsequent TBAF-induced one-pot deprotection-cyclization step of the resulting indolenines. Importantly, this two-step protocol can also be extended to access indoline-2,3-fused tetrahydropyrans. These syntheses of indoline-2,3-fused chromans and tetrahydropyrans proceed with operational convenience, use easily accessible substrates and reagents, and feature broad substrate scope, high yields and complete diastereoselectivity. Furthermore, the synthesized products have the potential to undergo late-stage functionalization.

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.

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.

The current study explores the effectiveness of drug particle deposition into human respiratory airways to cure various pulmonary-bound ailments. It has been assumed that drug solutions are inhaled in the form of tiny droplets or mist, which after striking create a thin layer along the inner surface of airways where the virus initially resides to infect the human body. A coupled Eulerian wall film (EWF) and discrete phase model (DPM) based simulation approach is used to capture these dynamics. Here, the Lagrangian DPM technique tracks the dynamics of tiny droplets, while the liquid layer formation after striking is captured using the Eulerian thin film approximations or the EWF model. Previous studies in this field primarily employed only the DPM method, which is inadequate to predict the poststriking dynamics of drug layer deposition and their spread to neutralize the respiratory virus. The drug delivery effectiveness is characterized by three different particle sizes, 1, 5, and 10 μm at the inhalation rates of 15, 30, and 60 L per minute (LPM). It has been found that the size of the drug particles significantly influences drug delivery effectiveness. The film thickness increases monotonically with particle sizes and inhalation rates. However, this increase in averaged film thickness is prominent in the range 5 to 10 μm (≈60%) compared to 1 to 5 μm (≈10%) droplet sizes at generation level 4 (G4). The other deposition parameters, e.g., deposition fraction, deposition density, and area coverage) roughly show similar behavior with the increase in droplet sizes. Therefore, it is recommended to vary the droplet sizes between 5 and 10 μm for better deposition effectiveness. The sizes of more than 10 μm mostly stuck into the oral cavity and cannot reach the targeted generations. In contrast, less than 5 μm may reach much deeper generations than the targeted one.

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.

Self-formation of boron-doped diamond (BDD)-multilayer graphene (MLG) core-shell nanowalls (BDGNWs) via microwave plasma-enhanced chemical vapor deposition is systematically investigated. Here, the incorporation of nitrogen brings out the origin of MLG shells encapsulating the diamond core, resulting in unique sp 3 /sp 2 hybridized frameworks. The evolution mechanism of the nanowall-like morphology with the BDD-MLG core-shell composition is elucidated through a variety of spectroscopic studies. The photocatalytic performance of these core-shell nanowalls is examined by the deterioration of methylene blue (MB) and rhodamine B (RhB) dyes beneath low-power ultraviolet (UV) light irradiation. Starting with 5 ppm dye solutions and employing BDGNWs as the photocatalyst, remarkable degradation efficiencies of 95% for MB within 100 min and 91% for RhB within 220 min are achieved. The effect of varying dye concentrations was also examined. The enhanced photocatalytic activity is driven by carrier photogeneration and mediated by the Schottky junction formed between BDD and MLG, promoting efficient photoinduced charge separation. The stability of the BDGNW photocatalyst is examined, and after five test runs, the photocatalytic behavior for MB and RhB degradation decreases to 87 and 85%, respectively, from initial values of 96 and 91%, demonstrating excellent photostability. These findings underscore the significance of diamond-graphene nanoarchitectures as promising green carbonaceous photocatalysts.

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.

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.

We investigate the ionic mobility in room-temperature RF-sputtered gadolinium doped ceria (GDC) thin films grown on industrial solid oxide fuel cell substrates as a function of the air-annealing at 800 and 1000 °C. The combination of X-ray diffraction, X-ray photoelectron spectroscopy, operando X-ray absorption spectroscopy, and Raman spectroscopy allows us to study the different Ce 3+ / Ce 4+ ratios induced by the post growth annealing procedure, together with the Ce valence changes induced by different gas atmosphere exposure. Our results give evidence of different kinetics as a function of the annealing temperature, with the sample annealed at 800 °C showing marked changes of the Ce oxidation state when exposed to both reducing and oxidizing gas atmospheres at moderate temperature (300 °C), while the Ce valence is weakly affected for the 1000 °C annealed sample. Raman spectra measurements allow us to trace the responses of the investigated samples to different gas atmospheres on the basis of the presence of different Gd-O bond strengths inside the lattice. These findings provide insight into the microscopic origin of the best performances already observed in SOFCs with a sputtered GDC barrier layer annealed at 800 °C and are fundamental to further improve sputtered GDC thin film performance in energy devices., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

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.

Misfolding and aggregation of the protein remain some of the most common phenomena observed in neurodegeneration. While there exist multiple neurodegenerative disorders characterized by accumulation of distinct proteins, what remains particularly interesting is the ability of these proteins to undergo a conformational change to form aggregates. TDP-43 is one such nucleic acid binding protein whose misfolding is associated with many neurogenerative diseases including amyotrophic lateral sclerosis (ALS) and fronto-temporal lobar degeneration (FTLD). TDP-43 protein assumes several different conformations and oligomeric states under the diseased condition. In this review, we explore the intrinsic relationship between the conformational variability of TDP-43 protein, with a particular focus on the RRM domains, and its propensity to undergo aggregation. We further emphasize the probable mechanism behind the formation of these conformations and suggest a potential diagnostic and therapeutic strategy in the context of these conformational states of the protein., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

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.

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.

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.