Compact Solid Electrolyte Interface Realization Employing Surface-Modified Fillers for Long-Lasting, High-Performance All-Solid-State Li-Metal Batteries.

The implementation of polymer-based Li-metal batteries is hindered by their low coulombic efficiency and poor cycling stability attributed to continuous electrolyte decomposition. Enhancement of the solid electrolyte interface (SEI) stability is key to mitigating electrolyte decomposition. This study proposes surface-functionalized silica mesoball fillers to fabricate a composite polymer electrolyte (MSBM-CPE). As a result of surface modification, the polyethylene oxide matrix benefits from the uniform distribution of the filler, which provides a large surface area and Lewis acid sites. Molecular dynamics simulations reveal that the dissociation energy of lithium bis(trifluoromethanesulfonyl)imide in the filler is fourfold higher (-1.95 eV) than that of the filler-free electrolyte. Consequently, the MSMB-CPE diffusivity is 30 times higher than its filler-free counterpart. The MSMB-CPE of ionic conductivity of 1.16 × 10-2 S cm-1 @60 °C and a venerable Li-ion transference number of 0.81. The excellent compatibility of MSMB-CPE with the Li anode is demonstrated by its stable symmetric cell performance under high current density (200 µA cm-2 @60 °C) for over 5000 h. Approximately 85.60% retention capacity of the [Li/MSMB-CPE/LiFePO4] full cell after 700 cycles. Furthermore, compositional analysis reveals that the SEI layer in MSMB-CPE is smooth with fewer by-products at the electrolyte/Li interface.

Optimizing graphene content in scaffolds for evenly distributed crumpled MoS2paper wads as anodes for high-performance Li-ion batteries.

Lithium-ion batteries (LIBs) have revolutionized portable electronics, yet their conventional graphite anodes face capacity limitations. Integrating graphene and 3D molybdenum disulfide (MoS2) offers a promising solution. Ensuring a uniform distribution of 3D MoS2nanostructures within a graphene matrix is crucial for optimizing battery performance and preventing issues like agglomeration and capacity degradation. This study focuses on synthesizing a uniformly distributed paper wad structure by optimizing a composite of reduced graphene oxide RGO@MoS2through structural and morphological analyses. Three composites with varying graphene content were synthesized, revealing that the optimized sample containing 30 mg RGO demonstrates beneficial synergy between MoS2and RGO. The interconnected RGO network enhances reactivity and conductivity, addressing MoS2aggregation. Experimental results exhibit an initially superior capacity of 911 mAh g-1, retained at 851 mAh g-1even after 100 cycles at 0.1 A g-1current density, showcasing improved rate efficiency and long-term stability. This research underscores the pivotal role of graphene content in customizing RGO@MoS2composites for enhanced LIB performance.

Highly Efficient Arginine Intercalated Graphene Oxide Composite Membranes for Water Desalination.

Graphene oxide-based composite membranes have received enormous attention for highly efficient water desalination. Herein, we prepare arginine/graphene oxide (Arg/GO) composite membranes by surface functionalizing GO nanosheets with arginine amino acid. Arginine has a unique combination of hydroxyl and amino functional groups that cross-link GO nanosheets through hydrogen bonding and electrostatic interactions. The as-prepared Arg@GO composite membranes with different thicknesses are used to separate the salt and dye molecules. The 900-nm-thick Arg@GO composite membrane shows high rejection of 98% for NaCl and 99.8% for MgCl2, Ni(NO3)2, and Pb(NO3)2 with good water permeance. Such a membrane also shows a high separation efficiency (100%) for methylene blue, rhodamine B, and Evans blue dyes. At the same time, the ultrathin Arg@GO composite membrane (220 ± 10 nm) exhibits high water permeance of up to 2100 ± 10 L m-2 h-1 bar-1. Furthermore, the 900-nm-thick Arg@GO composite membrane is stable in an aqueous environment for 40 days with significantly less swelling. Therefore, these membranes can be utilized in future desalination and separation applications.

Evaluating the Capacitive Response in Metal Halide Perovskite Solar Cells.

The perovskites solar cells (PSCs) is composed of multifaceted device architecture and involve complex charge extraction (both electronic and ionic), this makes the task demanding to unlock the origin of the different physical process that occurs in a PSC. The capacitance in PSCs depends on several external perturbations including frequency, illumination, temperature, applied bias, and importantly on the interface modification of perovskites/charge selective contact. Arguably, different features including interfacial and bulk; ionic, and electronic charge transport in PSCs occur at different time scales. Capacitance spectroscopy is a prevailing technique to unravel the various physical phenomenon that occurs in a PSC at different time scales. A deeper knowledge of the capacitive response of a PSCs is essential to understand the charge carrier kinetics and unlock the device physics. This work highlights the capacitive response of PSCs and its application to unlock the device physics which is essential for the further optimization and improvement of the device performance.

Recent Development in Laminar Transition Metal Dichalcogenides-Based Membranes Towards Water Desalination: A Review.

Transition metal dichalcogenides (TMDCs)-based laminar membranes have gained significant interest in energy storage, fuel cell, gas separation, wastewater treatment, and desalination applications due to single layer structure, good functionality, high mechanical strength, and chemical resistivity. Herein, we review the recent efforts and development on TMDCs-based laminar membranes, and focus is given on their fabrication strategies. Further, TMDCs-based laminar membranes for water purification and seawater desalination are discussed in detail. Finally, present their merits, limits and future challenges needed in this area.

New Terpenoids from the Corticioid Fungus Punctularia atropurpurascens and their Antimycobacterial Evaluation.

Chemical investigation of Punctularia atropurpurascens strain HM1 (Punctulariaceae), a corticioid isolated from a decorticated piece of Quercus bark collected in Bosque de Tlalpan, Mexico City, led to the isolation of a new drimane, 1-α-hydroxy-isodrimenine (1: ) and a new tetrahydroxy kauranol, 16-hydroxy-phlebia-nor-kauranol (2: ), together with the known N-phenylacetamide (3: ). Structures of all compounds were elucidated by spectroscopic and spectrometric methods, and the absolute configuration of 1: and 2: was confirmed via single-crystal X-ray crystallography. The isolated compounds showed modest antimycobacterial activity.

Secure Smart Wearable Computing through Artificial Intelligence-Enabled Internet of Things and Cyber-Physical Systems for Health Monitoring.

The functionality of the Internet is continually changing from the Internet of Computers (IoC) to the "Internet of Things (IoT)". Most connected systems, called Cyber-Physical Systems (CPS), are formed from the integration of numerous features such as humans and the physical environment, smart objects, and embedded devices and infrastructure. There are a few critical problems, such as security risks and ethical issues that could affect the IoT and CPS. When every piece of data and device is connected and obtainable on the network, hackers can obtain it and utilise it for different scams. In medical healthcare IoT-CPS, everyday medical and physical data of a patient may be gathered through wearable sensors. This paper proposes an AI-enabled IoT-CPS which doctors can utilise to discover diseases in patients based on AI. AI was created to find a few disorders such as Diabetes, Heart disease and Gait disturbances. Each disease has various symptoms among patients or elderly. Dataset is retrieved from the Kaggle repository to execute AI-enabled IoT-CPS technology. For the classification, AI-enabled IoT-CPS Algorithm is used to discover diseases. The experimental results demonstrate that compared with existing algorithms, the proposed AI-enabled IoT-CPS algorithm detects patient diseases and fall events in elderly more efficiently in terms of Accuracy, Precision, Recall and F-measure.

Dioxygen Reactivity of Copper(I)/Manganese(II)-Porphyrin Assemblies: Mechanistic Studies and Cooperative Activation of O2.

The oxidation of transition metals such as manganese and copper by dioxygen (O2) is of great interest to chemists and biochemists for fundamental and practical reasons. In this report, the O2 reactivities of 1:1 and 1:2 mixtures of [(TPP)MnII] (1; TPP: Tetraphenylporphyrin) and [(tmpa)CuI(MeCN)]+ (2; TMPA: Tris(2-pyridylmethyl)amine) in 2-methyltetrahydrofuran (MeTHF) are described. Variable-temperature (-110 °C to room temperature) absorption spectroscopic measurements support that, at low temperature, oxygenation of the (TPP)Mn/Cu mixtures leads to rapid formation of a cupric superoxo intermediate, [(tmpa)CuII(O2•-)]+ (3), independent of the presence of the manganese porphyrin complex (1). Complex 3 subsequently reacts with 1 to form a heterobinuclear µ-peroxo species, [(tmpa)CuII-(O22-)-MnIII(TPP)]+ (4; λmax = 443 nm), which thermally converts to a µ-oxo complex, [(tmpa)CuII-O-MnIII(TPP)]+ (5; λmax = 434 and 466 nm), confirmed by electrospray ionization mass spectrometry and nuclear magnetic resonance spectroscopy. In the 1:2 (TPP)Mn/Cu mixture, 4 is subsequently attacked by a second equivalent of 3, giving a bis-µ-peroxo species, i.e., [(tmpa)CuII-(O22-)-MnIV(TPP)-(O22-)-CuII(tmpa)]2+ (7; λmax = 420 nm and δpyrrolic = -44.90 ppm). The final decomposition product of the (TPP)Mn/Cu/O2 chemistry in MeTHF is [(TPP)MnIII(MeTHF)2]+ (6), whose X-ray structure is also presented and compared to literature analogs.

Heme-Heme Interactions in Diheme Cytochromes: Effect of Mixed-Axial Ligation on the Electronic Structure and Electrochemical Properties.

Diheme cytochromes, the simplest members in the multiheme family, play substantial biochemical roles in enzymatic catalysis as well as in electron transfer. A series of diiron(III) porphyrin dimers have been synthesized as active site analogues of diheme cytochromes. The complexes contain six-coordinated iron(III) having thiophenol and imidazole at the fifth and sixth coordination sites, respectively. The iron centers in the complexes have been found to be in a low-spin state, as confirmed through solid-state Mössbauer and electron paramagnetic resonance (EPR) spectroscopic investigations. Mössbauer quadrupole splitting of complexes having mixed ligands is substantially larger than that observed when both axial ligands are the same. Rhombic types of EPR spectra with narrow separation between gx, gy, and gz clearly distinguish heme thiolate coordination compared to bis(imidazole)-ligated low-spin heme centers. The redox potential in diheme cytochromes has been found to be tuned by interheme interactions along with the nature of axial ligands. The effect of mixed-axial ligation within the diiron(III) porphyrin dimers is demonstrated by a positive shift in the Fe(III)/Fe(II) redox couple upon thiophenolate coordination compared to their bis(imidazole) analogues. The pKa of the imidazole also decides the extent of the shift for the Fe(III)/Fe(II) couple, while the potential of the mixed-ligated diiron(III) porphyrin dimer is more positive compared to their monomeric analogue. A variation of around 1.1 V for the Fe(III)/Fe(II) redox potential in the diiron(III) porphyrin dimer can be achieved with the combined effect of axial ligation and a metal spin state, while such a large variation in the redox potential, compared to their monomeric analogues, is attributed to the heme-heme interactions observed in dihemes. Moreover, theoretical calculations also support the experimental shifts in the redox potential values.

Synthesis, biological evaluations and computational studies of N-(3-(-2-(7-Chloroquinolin-2-yl)vinyl) benzylidene)anilines as fungal biofilm inhibitors.

In the present investigation, new chloroquinoline derivatives bearing vinyl benzylidene aniline substituents at 2nd position were synthesized and screed for biofilm inhibitory, antifungal and antibacterial activity. The result of biofilm inhibition of C. albicans suggested that compounds 5j (IC50 value = 51.2 µM) and 5a (IC50 value = 66.2 µM) possess promising antibiofilm inhibition when compared with the standard antifungal drug fluconazole (IC50 = 40.0 µM). Two compounds 5a (MIC = 94.2 µg/mL) and 5f (MIC = 98.8 µg/mL) also exhibited good antifungal activity comparable to standard drug fluconazole (MIC = 50.0 µg/mL). The antibacterial screening against four strains of bacteria viz. E. coli, P. aeruginosa, B. subtilis, and S. aureus suggested their potential antibacterial activity and especially all the compounds except 5g were found more active than the standard drug ciprofloxacin against B. subtilis. To further gain insights into the possible mechanism of these compounds in biofilm inhibition through the agglutinin like protein (Als), molecular docking and molecular dynamics simulation studies were carried out. Molecular modeling studies suggested the clear role in inhibition of this protein and the resulting biofilm inhibitory activity.

Diheme Cytochrome c: Structure-Function Correlation and Effect of Heme-Heme Interactions.

We explore here the structure-function relationship of the diheme cytochrome c using synthetic diheme analogs which serve as a convenient tool to investigate various aspects of Nature's sophisticated design in vitro. A large series of diiron ethane-bridged porphyrin dimers, both in the oxidized and the reduced states, are synthesized and their structural, chemical, and electrochemical properties have been scrutinized. Interestingly, the iron-to-iron nonbonding separation observed in such dihemes ranges from 9.49 to 10.06 Å which is very similar to the separation of 9.4 and 9.9 Å observed in the crystal structures of diheme cytochromes c isolated from Geobacter sulfurreducens and Haemophilus influenza, respectively. The FeIII/FeII redox couple in the diheme complex is shifted toward more positive than their monomeric analog. Present study unmasks the electronic structure and properties of diheme centers and also highlights the significance of their structural arrangement and axial ligand orientation, and heme-to-heme separation. The Atoms in Molecules (AIM) analysis suggests long-range attractive dispersion forces between the heme units for the observed structure and properties in dihemes.

Fungal biofilm inhibition by piperazine-sulphonamide linked Schiff bases: Design, synthesis, and biological evaluation.

We report the synthesis of some new piperazine-sulphonamide linked Schiff bases as fungal biofilm inhibitors with antibacterial and antifungal potential. The biofilm inhibition result of Candida albicans proposed that the compounds 6b (IC50 = 32.1 µM) and 6j (IC50 = 31.4 µM) showed higher inhibitory activity than the standard fluconazole (IC50 = 40 µM). Compound 6d (MIC = 26.1 µg/mL) with a chloro group at the para position was found to be the most active antibacterial agent of the series against Bacillus subtilis when compared with the standard ciprofloxacin (MIC = 50 µg/mL). Compound 6j (MIC = 39.6 µg/mL) with an OH group at the ortho position showed more potent antifungal activity as compared to that of the standard fluconazole (IC50 = 50 µM) against C. albicans. Thus, the synthesized compounds 6a-k were found to be potent biofilm inhibitors as well as active antibacterial and antifungal agents. The molecular docking study of the synthesized compounds against the secreted aspartyl protease (SAP5) enzyme of C. albicans exhibited good binding properties. The in silico ADME properties of the synthesized compounds were also analyzed and showed their potential to be developed as potential oral drug candidates.

Antileishmanial evaluation of clubbed bis(indolyl)-pyridine derivatives: One-pot synthesis, in vitro biological evaluations and in silico ADME prediction.

A new series of bis(indolyl)-pyridine derivatives 6(a-m) were synthesized by Chichibabin reaction process and evaluated for antileishmanial and antibacterial activities to establish structure-activity relationship. The synthesis was carried out through one-pot multicomponent reaction of 3-acetylindole, aromatic aldehydes, and ammonium acetate in the presence of camphor-10-sulfonic acid as a catalyst. The compounds 6d (IC50=102.47µM) and 6f (IC50=99.49µM) had shown promising antileishmanial against L. donovani promastigotes when compared with standard sodium stibogluconate (IC50=490.00µM). All the synthesized compounds (MIC range=41.35-228.69µg/mL) had shown potent antibacterial activity than standard ampicillin (MIC range=100.00-250.00µg/mL) against all the tested bacterial strains. In silico ADME and metabolic site prediction studies were also held out to set an effective lead candidate for the future antileishmanial and antibacterial drug discovery initiatives.

Antileishmanial potential of fused 5-(pyrazin-2-yl)-4H-1,2,4-triazole-3-thiols: Synthesis, biological evaluations and computational studies.

A series of newer 1,2,4-triazole-3-thiol derivatives 5(a-m) and 6(a-i) containing a triazole fused with pyrazine moiety of pharmacological significance have been synthesized. All the synthesized compounds were screened for their in vitro antileishmanial and antioxidant activities. Compounds 5f (IC50=79.0µM) and 6f (IC50=79.0µM) were shown significant antileishmanial activity when compared with standard sodium stibogluconate (IC50=490.0µM). Compounds 5b (IC50=13.96µM) and 6b (IC50=13.96µM) showed significant antioxidant activity. After performing molecular docking study and analyzing overall binding modes it was found that the synthesized compounds had potential to inhibit L. donovani pteridine reductase 1 enzyme. In silico ADME and metabolic site prediction studies were also held out to set an effective lead candidate for the future antileishmanial and antibacterial drug discovery initiatives.

Silver(III)⋠⋠⋠Silver(III) Interactions that Stabilize the syn Form in a Porphyrin Dimer Upon Oxidation.

The interaction between two AgII porphyrins, connected covalently through a highly flexible ethane bridge, in a metalloporphyrin dimer has been investigated upon stepwise oxidation. X-ray structure determination of one and two-electron oxidized complexes has clearly revealed only metal-centered oxidation that results in short Ag-N (porphyrin) distance with large distortion in the porphyrin macrocycle. The 2e-oxidized complex exhibits significant metallophilic interaction in the form of a close AgIII ⋅⋅⋅AgIII contact that brings two porphyrin rings more cofacial with syn-conformation, which would otherwise stabilize in an anti-form. The interaction also leads to an intense emission peak at 546 nm at 77 K in the photoluminescence study.

Effect of Inter-Porphyrin Distance on Spin-State in Diiron(III) µ-Hydroxo Bisporphyrins.

The synthesis, structure, and properties of bischloro, µ-oxo, and a family of µ-hydroxo complexes (with BF4 (-) , SbF6 (-) , and PF6 (-) counteranions) of diethylpyrrole-bridged diiron(III) bisporphyrins are reported. Spectroscopic characterization has revealed that the iron centers of the bischloro and µ-oxo complexes are in the high-spin state (S=(5) /2 ). However, the two iron centers in the diiron(III) µ-hydroxo complexes are equivalent with high spin (S=(5) /2 ) in the solid state and an intermediate-spin state (S=(3) /2 ) in solution. The molecules have been compared with previously known diiron(III) µ-hydroxo complexes of ethane-bridged bisporphyrin, in which two different spin states of iron were stabilized under the influence of counteranions. The dimanganese(III) analogues were also synthesized and spectroscopically characterized. A comparison of the X-ray structural parameters between diethylpyrrole and ethane-bridged µ-hydroxo bisporphyrins suggest an increased separation, and hence, less interactions between the two heme units of the former. As a result, unlike the ethane-bridged µ-hydroxo complex, both iron centers become equivalent in the diethylpyrrole-bridged complex and their spin state remains unresponsive to the change in counteranion. The iron(III) centers of the diethylpyrrole-bridged diiron(III) µ-oxo bisporphyrin undergo very strong antiferromagnetic interactions (J=-137.7 cm(-1) ), although the coupling constant is reduced to only a weak value in the µ-hydroxo complexes (J=-42.2, -44.1, and -42.4 cm(-1) for the BF4 , SbF6 , and PF6 complexes, respectively).

Remarkable Anion-Dependent Spin-State Switching in Diiron(III) µ-Hydroxo Bisporphyrins: What Role do Counterions Play?

Addition of 2,4,6-trinitrophenol (HTNP) to an ethene-bridged diiron(III) µ-oxo bisporphyrin (1) in CH2 Cl2 initially leads to the formation of diiron(III) µ-hydroxo bisporphyrin (2⋅TNP) with a phenolate counterion that, after further addition of HTNP or dissolution in a nonpolar solvent, converts to a diiron(III) complex with axial phenoxide coordination (3⋅(TNP)2 ). The progress of the reaction from µ-oxo to µ-hydroxo to axially ligated complex has been monitored in solution by using 1 H NMR spectroscopy because their signals appear in three different and distinct spectral regions. The X-ray structure of 2⋅TNP revealed that the nearly planar TNP counterion fits perfectly within the bisporphyrin cavity to form a strong hydrogen bond with the µ-hydroxo group, which thus stabilizes the two equivalent iron centers. In contrast, such counterions as I5 , I3 , BF4 , SbF6 , and PF6 are found to be tightly associated with one of the porphyrin rings and, therefore, stabilize two different spin states of iron in one molecule. A spectroscopic investigation of 2⋅TNP has revealed the presence of two equivalent iron centers with a high-spin state (S=5/2) in the solid state that converts to intermediate spin (S=3/2) in solution. An extensive computational study by using a range of DFT methods was performed on 2⋅TNP and 2+ , and clearly supports the experimentally observed spin flip triggered by hydrogen-bonding interactions. The counterion is shown to perturb the spin-state ordering through, for example, hydrogen-bonding interactions, switched positions between counterion and axial ligand, ion-pair interactions, and charge polarization. The present investigation thus provides a clear rationalization of the unusual counterion-specific spin states observed in the µ-hydroxo bisporphyrins that have so far remained the most outstanding issue.

Novel amalgamation of phthalazine-quinolines as biofilm inhibitors: One-pot synthesis, biological evaluation and in silico ADME prediction with favorable metabolic fate.

A facile and highly efficient one-pot synthesis of phthalazine-quinoline derivatives is reported via four component reaction of phthalic anhydride, hydrazine hydrate, 5,5-dimethyl 1,3 cyclohexanedione and various quinoline aldehydes using PrxCoFe2-xO4 (x=0.1) nanoparticles as a catalyst. The synthesized compounds have been evaluated for anti-biofilm activity against Pseudomonas aeruginosa and Candida albicans. The compounds 12a (IC50=30.0µM) and 12f (IC50=34.5µM) had shown promising anti-biofilm activity against P. aeruginosa and C. albicans, respectively, when compared with standards without affecting the growth of cells (and thus behave as anti-quorum sensing agents). Compounds 12a (MIC=45.0µg/mL) and 12f (MIC=57.5µg/mL) showed significant potent antimicrobial activity against P. aeruginosa and C. albicans, respectively. Thus, the active derivatives were not only potent biofilm inhibitors but also efficient antimicrobial agents. In silico ADME and metabolic site prediction studies were also held out to set an effective lead candidate for the future antimicrobial drug discovery initiatives.

Antileishmanial activity of novel indolyl-coumarin hybrids: Design, synthesis, biological evaluation, molecular docking study and in silico ADME prediction.

In present work we have designed and synthesized total twelve novel 3-(3-(1H-indol-3-yl)-3-phenylpropanoyl)-4-hydroxy-2H-chromen-2-one derivatives 13(a-l) using Ho(3+) doped CoFe2O4 nanoparticles as catalyst and evaluated for their potential antileishmanial and antioxidant activities. The compounds 13a, 13d and 13h were found to possess significant antileishmanial activity (IC50 value=95.50, 95.00 and 99.00µg/mL, respectively) when compared to the standard sodium stibogluconate (IC50=490.00 µg/mL). The compounds 13a (IC50=12.40 µg/mL), 13d (IC50=13.49 µg/mL), 13g (IC50=13.24 µg/mL) and 13l (IC50=13.74 µg/mL) had shown good antioxidant activity when compared with standards butylated hydroxy toluene (IC50=16.5 µg/mL) and ascorbic acid (IC50=12.8 µg/mL). After performing molecular docking studies, it was found that compounds 13a and 13d had potential to inhibit pteridine reductase 1 enzyme. In silico ADME pharmacokinetic parameters had shown promising results and none of the synthesized compounds had violated Lipinski's rule of five. Thus, suggesting that compounds from the present series can serve as important gateway for the design and development of new antileishmanial as well as antioxidant agent.

Novel tetrazoloquinoline-rhodanine conjugates: Highly efficient synthesis and biological evaluation.

In search of new active molecules against Mycobacterium tuberculosis (MTB) H37Ra and Mycobacterium bovis BCG, a small focused library of rhodanine incorporated tetrazoloquinoline has been efficiently synthesized by using [HDBU][HSO4] acidic ionic liquid. The compound 3c found to be promising inhibitor of MTB H37Ra and M. bovis BCG characterized by lower MIC values 4.5 and 2.0 µg/mL, respectively. The active compounds were further tested for cytotoxicity against HeLa, THP-1, A549 and PANC-1 cell lines using MTT assay and showed no significant cytotoxic activity at the maximum concentration evaluated. Again, the synthesized compounds were found to have potential antifungal activity. Furthermore, to rationalize the observed biological activity data, the molecular docking study also been carried out against a potential target Zmp1 enzyme of MTB H37Ra, which revealed a significant correlation between the binding score and biological activity for these compounds. The results of in vitro and in silico study suggest that these compounds possess ideal structural requirement for the further development of novel therapeutic agents.