Visible light-responsive composition-dependent morphology and cargo release in mixed micelles of dendron amphiphiles - Avhad, Shankarrao V.; Kumar, Sugam; Ambade, Ashootosh V. (Langmuir, 2025)
2,2-Bis-(methylol)propionic acid-based second-generation polyester dendron amphiphile (T-D) containing visible light-responsive donor-acceptor Stenhouse adduct (DASA) as hydrophobic tails is synthesized. Micelles of T-D amphiphile and its mixed micelles of varying compositions with nonresponsive dendron amphiphile containing lauryl groups are prepared in aqueous solution. In transmission electron microscopy and atomic force microscopy analyses, T-D amphiphiles show rice grain-like ellipsoidal micelles as the predominant morphology. Mixed micelles display a composition-dependent morphology gradient such that the morphology changes from rice grain like to mixed to completely spherical with decreasing content of the T-D amphiphile. Complete morphology change to spherical micelles and partial reversal to ellipsoidal micelles, finally leading to ill-defined aggregates, are observed when the T-D amphiphile micelles are subjected to visible light-dark storage photoswitching cycles. Small-angle neutron scattering (SANS) analysis of 1 wt.% micellar solution in THF:water (10:90) reveals only a minor change in shape and size upon photoirradiation, and the data could be fitted to spherical or ellipsoidal model. Release of hydrophobic dye from mixed micelles is tuned by the content of the photoresponsive amphiphile. Cellular uptake and visible light-triggered release of hydrophobic drug from mixed micelles are demonstrated using MDA-MB-231 cells, suggesting their applicability for photoresponsive drug delivery.

Zincke-derived viologen covalent organic framework as a high-performance cathode for aqueous zinc-iodine batteries - Das, Gobinda; Shivade, Rajkiran; Pandey, Priyanshi; Varghese, Sabu; Rajput, Nitul; Matouk, Zineb; Martinez, Jose Ignacio; Straubinger, Rainer; Benyettou, Farah; Gandara, Felipe; Olson, Mark A.; Aouad, Samer; et al. (Small, 2025)
Aqueous zinc-iodine (Zn-I2) batteries are among the most promising energy storage technologies, offering high energy density, low cost, and intrinsic safety. However, their practical deployment is hindered by the polyiodide shuttle effect, leading to rapid capacity fading and poor cycling performance. This work demonstrates the application of a crystalline viologen-based covalent organic framework (TAB-DNP-BP COF), synthesized via a one-pot Zincke reaction, as an efficient iodine host material. The cationic backbone of the TAB-DNP-BP COF effectively confines iodine (I2) species and electrostatically traps polyiodides, suppressing their migration and protecting the zinc anode. Zinc-iodine batteries assembled with an I2-enriched TAB-DNP-BP COF (TAB-DNP-BP COF@I2) cathode deliver a high specific capacity of 337 mAh g-1 at 0.5 C, surpassing the performance of most reported COF-, MOF-, and cage-based systems, while exhibiting excellent cycling stability over 5000 cycles. This work highlights the potential of ionic COFs for stabilizing iodine chemistry and offers a promising strategy toward the development of high-performance, durable aqueous Zn-I2 batteries.
Keywords: iCOF; iodine confinement; viologen; zinc-iodine batteries; Zincke reaction

Amorphous vanadium-doped iron borate/tetraboride hybrid as an efficient electrocatalyst for the oxygen evolution reaction - Ahmed, Tanbir; Pal, Santanu; Sinha, Nibedita; Das, Chandni; Roy, Poulomi (Dalton Transactions, 2026)
The design of an effective electrocatalyst as a replacement for a conventional expensive electrocatalyst for facilitating the sluggish oxygen evolution reaction (OER) at the anode has been identified as an effective way to make hydrogen production economical. Herein, we have developed a unique combination of iron borate and iron tetraboride (Fe-BO/FeB) by a facile chemical reduction process. The optimum vanadium doping further led to the transformation of Fe-BO/FeB into an amorphous form, which is believed to be very beneficial for the OER mechanism. The developed electrocatalyst needs overpotentials of 215 mV and 256 mV in alkaline 1 M KOH electrolyte to achieve current densities of 10 and 100 mA cm-2, respectively, and it also shows stability over 48 h, maintaining a high current density of 200 mA cm-2. Enhanced performances were also confirmed by smaller activation energies for the optimized sample compared with a pristine electrocatalyst.

Chirality transfer from covalent organic framework nanotubes to covalent organic framework films via chirality induction crystallization - Bag, Saikat; Chatterjee, Debasmita; Mahapatra, Rohan; Sasmal, Himadri Sekhar; Khatua, Arindam; Giri, Madhurima; Paul, Satyadip; Shelke, Ankita; Almasoud, Najla; Alomar, Taghrid S.; Ajithkumar, Thalasseril G.; Sen Gupta, Sayam; et al. (Advanced Materials, 2026)
We report the synthesis of homochiral crystalline covalent organic framework (COF) films that combine rigidity and porosity, offering significant promise for heterogeneous asymmetric catalysis. We prepared enantiopure COF films from achiral diamine and trialdehyde precursors using a chiral induction crystallization strategy. A Schiff-base reaction, catalyzed by a chiral acid, namely (R)- and (S)-camphorsulfonic acids (CSA) generated a beta-ketoenamine backbone with induced chirality. (R)- and (S)-camphorsulfonic acids direct the diamine-trialdehyde condensation and induce chirality during the nucleation of COF nanotubes, enabling their periodic arrangement and the formation of homochiral thin films. We successfully synthesized six distinct COF films with three different backbone functionalities: R-, S-TpAzo; R-, S-TpDPP; and R-, S-TpBDMe2, using the two enantiomers of the chiral camphorsulfonic acids. All films displayed strong circular dichroism signals and pronounced Cotton effects, confirming their enhanced enantiopurity. Both R- and S-TpAzo films exhibited the highest crystallinity, long-range order, and permanent porosity, making them particularly well-suited for catalytic applications. To demonstrate their utility, we encapsulated a bioinspired catalyst, (Et4N)2[FeIII(Cl)bTAML], within the chiral channels of the R- and S-TpAzo films. The resulting composite created a robust heterogeneous catalytic platform for the asymmetric epoxidation of alkenes, achieving excellent activity and enantioselectivity under ambient conditions.
Keywords: chiral induction; covalent organic framework nanotube; covalent organic framework thin film; heterogeneous catalysis

Direct conversion of methane to formic acid over Au-Fe-NaZSM-5 at ambient pressure using H2O2 - Kumar, Pawan; Ahangar, Iqra; Kesarwani, Srishti; Urkude, Rajashri; Patil, Nita A. R.; Niphadkar, Prashant; Bokade, Vijay V.; Haider, M. Ali; Vinod, C. P. (Catalysis Science & Technology, 2026)
Direct conversion of methane to value-added products is a long-standing challenge. This report presents the one-step conversion of methane to oxygenates using H2O2 as an oxidant over an Au and Fe supported on NaZSM-5 (0.1Au0.1FeNZ) catalyst, which produces 4264 mu mol of oxygenates with 89% selectivity toward formic acid at 10 bar and 60 degrees C within 30 min in a batch process. The catalyst also produces 26.5 mu mol of oxygenates with 70% selectivity for formic acid at atmospheric pressure and 80 degrees C in a continuous flow process over 9 h of reaction time, making it the first report of such a process. The synergistic interaction of Au and Fe, with the crucial role of Na ions in the zeolite framework in driving the reaction, is revealed through various characterization tools like TEM, XPS, and XAS. Theoretical studies elucidate the active sites responsible for lowering the activation barrier for the crucial C-H activation step. Thus, the catalyst enables the conversion of methane into formic acid with high activity and selectivity, offering new possibilities for harnessing this potent greenhouse gas under process-friendly conditions that were previously unexplored.

Dual-functional phosphomolybdic acid-polypyrrole-ionic liquid nanocomposites for energy storage and hydrogen evolution: experimental and theoretical studies - Anees, Muhammed P. K.; Iniyan, Selvaraj; Pratap Singh, Chandrodai; Kathiresan, Murugavel; Krishnamurty, Sailaja; Sankar Mal, Sib (Dalton Transactions, 2026)
Recent advancements in pseudocapacitive materials for energy storage and catalytic activities highlight the benefits of incorporating nanostructured active materials. This study investigates the modification of polypyrrole (PPy) surfaces using polyoxometalate H4[PVMo11O40].xH2O (PVMo11) combined with ionic liquids hexadecyltrimethylammonium chloride (CTAC) and 1-benzyl-3-methylimidazolium chloride (BMI). Among various synthesized nanocomposites, PVMo11-BMI-PPy demonstrated superior electrochemical properties in a 0.25 M H2SO4 aqueous electrolyte, achieving a remarkable specific capacitance of 400 F g-1, an energy density of 49.5 W h kg-1 and a power density of 906 W kg-1 at a current density of 1 A g-1. It achieves a capacitive contribution of 94.5% at 10 mV s-1 with an impressive cyclic retention rate of 91.1% and a coulombic efficiency of 98.9% after 10 000 GCD cycles. Additionally, PVMo11-BMI-PPy exhibited outstanding electrocatalytic activity for hydrogen evolution reaction (HER), achieving the highest catalytic activity of 19 mV at a current density of 10 mA cm-2, outperforming the benchmark Pt catalyst. Its superior performance is underscored by a high TOF of 6.91 x 10-7 s-1 and excellent long-term stability in 0.5 M H2SO4 over 24 hours. It is a promising candidate for bifunctional activities such as energy storage and catalytic applications. Additionally, density functional theory (DFT) studies were conducted to gain insights into the enhanced performance of PVMo11-BMI-PPy. The thermodynamic and electronic characteristics indicate that the V site of PVMo11-BMI-PPy offers the most efficient and balanced catalytic environment for hydrogen evolution reaction (HER) compared with all other sites examined. These theoretical findings align well with experimental observations, demonstrating superior HER activity of the PVMo11-BMI-PPy catalyst, thereby confirming the computational predictions.

Dynamic janus hydrogen bond mimicry unlocks tough, flexible supramolecular elastomers for strain sensing - Lakshmi, Durga; Wagh, Mahendra A.; Sharma, Aakash; Alam, Md Shafi; Selvan, T. Muthamil; Torris, Arun; Mondal, Titash; Sanjayan, Gangadhar J.; Nair, Kiran Sukumaran (Chemistry of Materials, 2026)
Flexible and wearable electronics demand stretchable sensors with polymer elastomers as key matrixes for mechanical flexibility and durability. However, despite their excellent elasticity, their limited mechanical strength remains a challenge. To address this limitation, in this study, we report the rational design of supramolecular polyurethane elastomers (SPUs) incorporating nucleobase-inspired aminopyrimidinedione with DDA-AAD (G-C mimic) reversible triple hydrogen bonds. This dual-domain architecture gives rise to a durable supramolecular network with enhanced mechanical properties, yielding elastomers that are soft, stretchable, and tough. By tuning of the density of dynamic cross-links, mechanical properties were systematically modulated. SPU-0.5 exhibited a maximum tensile strength of 16.14 MPa, representing a 67-fold strength enhancement over that of SPU-0. Although increasing the aminopyrimidinedione (APD) content reduced elongation, SPU-0.2 retained a high elongation of 1060% and showed the lowest residual strain during cyclic tests. To be of great interest, the activation energy increased with increasing hydrogen bonding content up to SPU-0.1, whereas beyond SPU-0.2 it decreased, likely due to extensive hydrogen bond formation. Furthermore, SPU-0.2-SP, a conductive variant, demonstrated a promising strain-sensing performance even after hundreds of cycles. Overall, the insights gained from this study advance the development of intelligent soft materials and lay the groundwork for next-generation flexible and wearable electronic devices.

Effect of shape on cellular uptake of visible-light- and redox-responsive biodegradable linear-dendritic block copolymer micelles - Avhad, Shankarrao V.; Ambade, Ashootosh V. (Biomacromolecules, 2026)
Linear-dendritic block copolymers comprising poly(epsilon-caprolactone) attached to hydrophilic 2,2-bis(hydroxymethyl)propionic acid (bis-MPA) ester dendron via a disulfide and containing a defined number of pendent visible-light-responsive donor-acceptor Stenhouse adduct (DASA) groups are synthesized using click chemistry and postpolymerization modification. Self-assembly in aqueous solution selectively affords rice grain-like ellipsoidal, rod-like, and spherical micelles, governed by the number of DASA groups. Progressive disassembly of the micelles is observed during photoswitching cycles. Release of camptothecin depends on the DASA content under light irradiation and is enhanced by the synergistic effect of two stimuli. Cellular uptake quantified by FACS analysis is demonstrated to be influenced by the shape of the micelles, with ellipsoidal micelles exhibiting higher efficiency than spherical micelles by following clathrin- and caveolae-mediated endocytosis as major pathways for internalization. Both types of micelles were found to maintain the particle size in Dulbecco's modified Eagle's medium containing 10% fetal bovine serum at 37 degrees C. Doxorubicin (DOX)-loaded ellipsoidal micelles under photoirradiation show significantly higher apoptosis than free DOX.

Effect of sulfonation density on acid strength in ion exchange resins: Insights from solid-state NMR and density functional theory - Tumulu, Goutam Narayan; Datar, Sarvesh; Shelke, Ankita; Swain, Gitanjali; Ajithkumar, T. G.; Thirumalaiswamy, Raja; Mohan, Ojus; Mahajani, Sanjay M. (Molecular Catalysis, 2026)
Ion-exchange (IE) resins are widely used as solid acid catalysts; however, their surface acidity remains poorly characterized because their limited thermal stability precludes conventional NH3-based acidity measurements. Moreover, acid-site accessibility in IE resins is strongly governed by solvent- or reactant-induced swelling. Here, we investigate the surface acidity of commercial Amberlyst and Indion IE resins using & sup3;& sup1;P MAS NMR (Magic Angle Spinning Nuclear Magnetic Resonance), employing TMPO as a molecular probe dispersed on the resin with moderately swelling dichloromethane, thereby capturing the swollen-state acidity relevant for predicting catalytic activity. The deconvolution of the P-31 MAS NMR spectra reveals three distinct acid-strength zones arising from inhomogeneous sulfonation of the polymer matrix. The overall acidity, quantified by the area-weighted average P-31 chemical shift (delta), increases monotonically with sulfonation density. Notably, only resins containing acid sites stronger than similar to 80 ppm exhibited measurable catalytic activity in alpha-pinene isomerization, establishing a direct correlation between acidity and activity. Density functional theory (DFT) calculations on representative resin models, supported by electron-density analyses, attribute the enhancement of acid strength at higher sulfonation densities to cooperative hydrogen-bonding networks among neighboring sulfonic acid groups. Together, these findings establish P-31 MAS NMR-derived surface acidity as a catalytically relevant descriptor for the rational selection of IE resins in liquid phase acid-catalyzed chemistries.
Keywords: Acid strength; Density functional theory; heterogeneous catalysis; Ion-exchange resins; Solid acids; Solid-state NMR

Enhanced electrochemical performance of flexible polymer supercapacitors through optimization of organic acid-doping, carbon nanomaterials, and fabrication techniques - Parul; Lakshmi, Racherla Bhagya; Utturkar, Vivek; Natu, Varun; Aramanda, Shanmukha Kiran; Ramamurthy, Praveen C.; Kaka, Fiyanshu (Journal of Power Sources, 2026)
The proliferation of portable and wearable electronics necessitates flexible, high-performance energy storage devices. Flexible supercapacitors are poised to meet these demands due to their high power density, flexibility, and durability but scalable fabrication remains challenging due to costly and complex manufacturing methods. This study addresses this issue by implementing scalable, cost-effective spray coating and screen printing techniques to fabricate flexible micro-interdigitated supercapacitors (FMIS) based on Polyaniline (PANI) composites with carbon nanomaterials, using organic acids as crosslinking agents synthesized via hydrogel strategy. The formation of PANI emeraldine salt was verified through X-ray photoelectron spectroscopy, indicating key amine and imine functionalities, while scanning electron microscopy revealed surface morphologies with enhanced active surface areas beneficial for charge storage. Advanced 3D tomography maps porosity distribution and surface area per unit volume, correlating with electroactive areas calculated from the Randles-Sevcik equation. Electrochemical testing via cyclic voltammetry demonstrates an impressive areal capacitance of 173.2 +/- 9.6 mF cm-2 at 10 mV s-1 with Dunn's method distinguishing capacitive from diffusive contributions. Furthermore, EIS measurements highlight lower solution resistance in screen-printed devices, emphasizing the advantages of optimized electrode morphology for efficient charge transport. This study establishes a scalable approach for high-performance flexible supercapacitors, paving the way for next-generation energy storage solutions.
Keywords: Carbon nanomaterials; Coating techniques; Flexible Supercapacitors; PANI composites; X-ray micro-tomography

Exploring the mechanisms of yoga-based cardiac rehabilitation in heart failure via assessment of endothelial function, genomics and arterial health (Yoga-EndOmics): a study protocol - Shetty, Vindya Vasu; Patil, Laxmi Ramchandra; Patil, Satish G.; Aithal, Kiran; Oli, Ajay Kumar; Yenagi, Vijay Aravind; Kaulgud, Ram S.; Dharne, Mahesh; Chandra Sekaran, Ambalam M.; Prabhakaran, Dorairaj (BMJ Open, 2026)
Introduction Heart failure (HF) remains a major global health challenge, particularly in low-resource settings where access to comprehensive cardiac rehabilitation (CR) is limited. Yoga, a culturally contextualised mind-body intervention, holds promise as an adjunctive therapy in CR. The Yoga-EndOmics study aims to evaluate the effects of Yoga-based cardiac rehabilitation (Yoga-CaRe) on gene expression, endothelial function, vascular biomarkers and clinical outcomes in systolic HF, providing mechanistic insights into its potential integration into conventional cardiac rehabilitation.Methods and analysis This is a prospective, randomised, open-label, blinded-endpoint (PROBE) mechanistic trial enrolling 78 patients with HF with reduced ejection fraction (HFrEF). Participants will be randomised in a 1:1 ratio to receive either a structured Yoga-CaRe intervention or enhanced standard care for 3 months. The Yoga-CaRe group will attend 20 supervised sessions with guided home practice involving tailored asanas, pranayama and meditation. Primary outcomes are changes in endothelial-dependent flow-mediated dilation (FMD) and functional exercise capacity at 3 months. Secondary outcomes include changes in arterial compliance and stiffness, circulating biomarkers of endothelial dysfunction, oxidative stress and inflammation, and immediate changes in global gene expression profiles in peripheral blood mononuclear cells following the Yoga-CaRe intervention. Data will be analysed using analysis of covariance (ANCOVA) for between-group comparisons and significant analysis of microarray (SAM) for global gene expression profiles.Ethics and dissemination The study has received ethical clearance from the Institutional Ethics Committee of the SDM College of Medical Sciences and Hospital, India (SDMIEC/2025/1072) and is registered with the Clinical Trials Registry of India. Findings will be disseminated through peer-reviewed journals, scientific conferences and stakeholder engagement platforms to inform future integrative strategies in HF management.Trial registration number CTRI/2023/12/060758
Keywords: DNA Methylation; Genetics; Heart failure; Molecular Biology; Randomized Controlled Trial

Field emission performance of 2D Ti2CT x (T x = O2, F2, O-F) MXene: experimental insights and theoretical endorsement - Kakade, Prashant M.; Aher, Rahul; Kachere, Avinash R.; Cho, Jinill; Deore, Amol; Jadkar, Sandesh R.; Chauhan, Inderjeet; Kim, Taesung; Mandlik, Nandkumar T.; Kim, Ji Man; Bulakhe, Ravindra N. (ACS Applied Nano Materials, 2026)
Field emission (FE) is an important electron emission mechanism for vacuum microelectronic devices; however, conventional emitters often exhibit high turn-on fields, limited emission stability, and degradation during prolonged operation. Two-dimensional MXenes have recently emerged as promising FE materials due to their remarkable electrical conductivity, comparatively low work function, and tunnelable surface terminations. Nevertheless, most studies have focused on Ti3C2T x MXene, while other compositions such as Ti2CT x remain largely unexplored, particularly regarding the influence of surface terminal groups on their electronic and emission properties. Herein, Ti2CT x (T x = -F2, -O2, -OF) MXene was synthesized via selective chemical etching of the Ti2AlC MAX phase and investigated for its FE characteristics. The material exhibits a polycrystalline hexagonal layered structure with a high specific surface area of 349.02 m2 g-1. Ti2CT x MXene demonstrates excellent FE performance with a low turn-on field of 1.56 V mu m-1 and a threshold field of 2.0 V mu m-1 (at 10 mu A cm-2), along with a stable emission for 4 h. Density functional theory calculations further reveal that surface terminations strongly influence the electronic structure and work function, with the experimental value of 4.66 eV closely matching the -F2 termination. These results highlight Ti2CT x MXene as a promising material for stable and efficient FE applications.
Keywords: 2D Ti2CT x MXene; field emission; TDOS and PDOS; Turn-on voltage; Work function

Fly-ash-based geopolymers: leachability and solid-state NMR investigations - Nadol, Athulya; Ajithkumar, T. G.; Singla, Rashmi; Alex, T. C.; Kumar, Sanjay; Bhatt, Himal; Deo, M. N.; Sen, Debasis; Ambashta, R. D.; Bajpai, R. K.; Shivakumar, Y. C.; Manohar, S. (Bulletin of Materials Science, 2026)
This study aims to explore how leaching impacts the microstructure of a selected fly ash-derived geopolymer and evaluate its potential for near-surface disposal of radioactive waste. The uniqueness of this geopolymer formulation is its ability to form an aluminosilicate network that remains resistant to structural changes upon contact with water. The leach index of base elements such as Ca, Al, Na and Si was between 11 and 13, suggesting that the formulation is superior to Portland cement or conventional hydraulic cement. Solid-state NMR reveals that the water-interacted specimen has no contamination of the zeolite phase and all the Na is incorporated into the aluminosilicate geopolymer gel network, which also confirms that the glassy network of the geopolymer is responsible for imparting low leachability of base elements from its structure, and there is no labile sodium available for exchange as in zeolites.
Keywords: aluminosilicate network; Fly ash; Geopolymers; leaching; Solid-state NMR

Lattice dynamics and electron-phonon coupling in geometrically distorted halide double perovskites - Kanapathi, Prakash; Ravi, Nalini; Mohan, Subramaniam; Vijayan, Viswanathan; Appadurai, Tamilselvan (Journal of Physical Chemistry C, 2026)
Electron-phonon coupling is a critical factor in regulating the photophysical behavior of halide double perovskites (HDPs), influencing their emission broadening through lattice softness and exciton dynamics. In this work, we investigate four structurally distorted compounds, such as Cs2Ag0.4Na0.6InCl6, Cs2NaIn0.9Bi0.1Cl6, Cs2AgIn0.9Bi0.1Cl6, and Cs2Ag0.4Na0.6In0.9Bi0.1Cl6, prominent for their broad emission characteristics. Our combined experimental analysis and numerical models demonstrate that the electron-phonon coupling is dictated by the interplay between the sublattice distortion and the bonding nature between the metal and halide atoms, which vitally modulates the overall lattice softness and the resulting spectral broadening. The introduction of more ionic Na-Cl bonds in the HDP structure softens (weaker bonding) the lattice and enhances the phonon population, resulting in strong coupling between the electron and phonon, as quantified by the Huang-Rhys factor for Cs2NaIn0.9Bi0.1Cl6 (18.88), Cs2Ag0.4Na0.6InCl6 (17.64), and Cs2Ag0.4Na0.6In0.9Bi0.1Cl6 (14.46). Raman analysis further evidences Na-induced lattice softness with a 5 cm-1 red shift of the A1g mode in Cs2NaIn0.9Bi0.1Cl6, compared to Ag-containing HDPs. These findings highlight that Na-based compounds have stronger electron-phonon coupling than Cs2AgIn0.9Bi0.1Cl6. Furthermore, temperature-dependent phonon dynamics using the cubic anharmonic model and the three-phonon anharmonicity theory demonstrate that the distorted structures involve a phonon anharmonicity due to the thermal disorder. We show that strong coupling between the electron and the energetic phonon broadens the emission spectrum but suppresses the PL intensity. This quenching may arise from the excessive phonon-intervened nonradiative relaxations in the Na-rich compounds. By contrast, the temperature-dependent PL of Cs2Ag0.4Na0.6In0.9Bi0.1Cl6, a compound with maximum PL intensity, reveals the major contribution of optical phonon to electron-phonon coupling, which facilitated the efficient STE formation. This study highlights the significance of lattice softness to regulate the optoelectronic properties of the halide double perovskites, providing a design approach for compositional engineering towards high-performance optoelectronic devices.

(NHC-olefin)-nickel(0) nanoparticles: an efficient and selective catalyst for hydrogenation reactions at low temperature and pressure - Avello, Marta G.; Singh, Geetika; Truong-Phuoc, Lai; Vidal, Loic; Papaefthimiou, Vasiliki; Chesse, Matthieu; Gruber, Nathalie; Chetcuti, Michael J.; Vanka, Kumar; Ritleng, Vincent; Pham-Huu, Cuong; Michon, Christophe (Journal of Catalysis, 2026)
The reduction of a NHC-cinnamyl nickel(II) organometallic complex through the use of different MeMgBr or MeMgCl reagents led to two types of NHC-olefin-coordinated nickel nanoparticles. Both of these unsupported nickel-NHC based nanomaterials behaved under hydrogen pressure as effective and selective catalysts operating at low temperature (<= 80 degrees C), pressure (<= 20 bar) and loading (<= 6 mol%) for the reductions of broad scopes of alkenes, alkynes, imines and heterocycles, including a challenging tetra-substituted alkene. Among these two nickel-NHC nanocatalysts, the one generated with MeMgCl showed a significant high catalytic activity with high yields and could stand the comparison with Raney nickel and state-of-the-art nickel nanocatalysts. For example, by studying the hydrogenation of 1-phenylcyclohexene in ethanol at 60 degrees C under 10 bar of H2, 3 mol% of this catalyst achieved the reaction within a single hour on a 5 mmol/0.8 g substrate scale with a yield of 96 %, a turnover number (TON) of 32 and a turnover frequency (TOF) of 32. Characterizations confirmed the coordination of the NHC-olefin ligands to the nickel nanoparticles, the reduced state of the nickel and the (poly-) crystallinity of the nanoparticles.
Keywords: alkenes; Alkynes; heterocycles; Hydrogenation; imines; N -heterocyclic carbene ligand; nanocatalysis; Nickel

Novel biosurfactant assisted biodegradation of polystyrene by Actinomycetes and its chemical understanding - Sakpal, Amrapali; Haq, Nazrul; Dasgupta, Santanu; Alanazi, Fars; Alsarra, Ibrahim A.; Alam, Mahboob; Dastager, Syed G. (Polymer Degradation and Stability, 2026)
The current study highlights the effective biodegradation of polystyrene by two actinobacterial strains, Glutamicibacter sp. K-1 and Rhodococcus sp. BG-30. FT-IR, Raman spectroscopy, and GPC data showed the degradation pattern of polystyrene. Additionally, GC-MS analysis showed that strain K-1 produced a variety of degradation by-products, including alkanes, 2,4-Di-ter-butyl phenol, 2-propenoic acid, tridecyl ester, and dibutyl phthalate, while strain BG-30 produced a greater amount of alkenes, phthalic acid, and isobutyl octyl esters. GPC detected a drop in polystyrene's average molecular weight (Mn), which suggests chain scission of the polymer. Changes in polystyrene's roughness and other morphological properties were shown by AFM and FE-SEM. The effects of a conventional rhamnolipid and a novel thermostable biosurfactant fatty alkene (0.1 % each) on the breakdown of polystyrene were examined. Strain K-1 and BG-30 resulted in increasing the degradation of polystyrene to 12 % (w/w) and 16 % (w/w), respectively in the presence of fatty alkene biosurfactant, there was 10 % (w/w) and 8 % (w/w), degradation in presence of rhamnolipid. To the best of our knowledge, degradation of polystyrene by Glutamicibacter sp. has been reported as a newly identified strain and use of a novel biosurfactant together revealed their potential in biodegradation of plastic to mitigate the plastic pollution using microbial resources.
Keywords: Biodegradation; Fatty alkene biosurfactant; Glutamicibacter sp.; Polystyrene; Rhamnolipid; Rhodococcus sp.

Novel prodrug-inspired eugenol derivatives with enhanced bioavailability, anti-diabetic and anti-glycation efficacies - Kataria, Priyanka; Vairale, Shiva; Mote, Chandrashekhar; Joshi, Kaustubh; Joshi, Rakesh; Kulkarni, Mahesh J.; Giri, Ashok P.; Kontham, Ravindar; Agawane, Sachin B. (Journal of Molecular Structure, 2026)
In this study, we present the design, synthesis, and evaluation of novel eugenol analogs aimed to overcome its limited bioavailability due to insolubility in aqueous media. Thus, we re-engineered eugenol using prodruginspired structural modifications to improve pharmacokinetic properties. First, we structurally modified eugenol and synthesized its natural amino acid conjugates as esters and carbamates. These were prepared in NBoc protected, free amine, and HCl salt forms. These modifications are expected to improve the polarity and solubility of eugenol congeners in biological systems. They can also release the parent eugenol through enzymatic hydrolysis, enhancing its therapeutic potential. Next, we comprehensively screened for these derivatives through in silico studies followed by in vitro and in vivo assays. These include DPPH radical scavenging (IC50 range: 37.7 to 103.7 mu M), inhibition of (i) alpha-amylase (IC50 23.1 to 67.3 mu M), (ii) alpha-glucosidase (IC50 43.6 to 50.4 mu M), (iii) glycation (IC50 31.9 to 110.3 mu M) along with pharmacokinetic profiling and toxicity assessments. These experiments collectively demonstrated improved activity of eugenol analogs for several important parameters. Specifically, six analogs-epoxy eugenol (39), hydroxy eugenol (43), aspartate eugenol (26), isoleucinate eugenol (24), glutamate eugenol (37), and glutamate-salt eugenol (27) exhibited superior bioavailability, absorption, and distribution over to the parent compound eugenol. These analogs were found to be non-toxic and safe for oral administration. Overall, the study establishes a mechanistic and rational framework for modifying eugenol to overcome its inherent biopharmaceutical limitations, positioning them as promising candidates for treating diabetes and glycation-related conditions.
Keywords: Amino acid conjugates; Antidiabetic activity; Bioavailability enhancement; Drug design and synthesis; Eugenol analogs; In silico and in vitro studies

Poly(2,5-Benzimidazole)-based flat sheet membranes: investigating effects of dope solvent and membrane heat treatment on forward osmosis and acid enrichment performances - Somkuwar, Nitin C.; Thorat, Nitin M.; Ambade, Ashootosh; Kharul, Ulhas K. (Journal of Applied Polymer Science, 2026)
The present work investigates two methods for preparing defect-free, symmetric membranes of the thermochemically robust polymer, poly(2,5-benzimidazole) (commonly known as ABPBI) for forward osmosis (FO), a growing technology for niche separations. The obtained polymer and membranes were analyzed for physical properties of significance. The FO analysis was performed using three salt solutions, viz., sodium chloride (NaCl), magnesium chloride (MgCl2), and sodium sulfate (Na2SO4). The effects of casting methodology (solvents present in the dope), membrane heat treatment, draw solution concentration, long-duration analysis, and FO-assisted enrichment of organic acids were evaluated. Some of the membranes exhibited extremely low reverse salt flux (RSF), which conveys the novelty of these membranes. Some of these membranes were analyzed using a high draw solution (DS) concentration (4 mol L-1) to enhance water flux and further employed to enrich organic acids. The aqueous acetic and methacrylic acid concentrations were enriched from 4.89 and 2.93 mol L-1 to 11.88 and 10.01 mol L-1, respectively. These results demonstrate an unmet need of concentrating methacrylic acid (a temperature-sensitive compound possessing a double bond). The present work demonstrates the potentials of ABPBI-based symmetric, thin membranes for FO and their industrial applicability for the first time.
Keywords: Applications; membranes; separation techniques

Polysulfone-based polymer carbon dot membrane for optical dissolved oxygen sensing application - Kadam, Rutuja; Hattale, Gangadhar; Virole, Vishal; Pal, Sanjivani; Abraham, Athira; Paul, Aditya; Kumar, Ajay; Shevate, Rahul; Banpurkar, Arun; Kanawade, Rajesh; Saha, Avishek (Chemistry-An Asian Journal, 2026)
The precise monitoring of dissolved oxygen (DO) is essential across industrial, environmental, and biomedical applications. However, the state-of-the-art DO sensing methods often suffer from inherent limitations, which hinder their effectiveness for real-time and long-term DO monitoring. Optical DO sensing, despite its advantages, utilizes expensive metal complexes and is prone to photobleaching and slow response time. Here, we introduce a novel polymer carbon dot (PCD) as a promising candidate for lifetime-based optical DO sensing. The PCD is a metal-free, nontoxic, fluorescent, long decay-lifetime material that is synthesized through hydrothermal method. Our fluorescent PCD exhibits high emission quantum yield (24.32%), long decay-lifetime (10.43 & micro;s), and a linear response to DO concentrations ranging from 0.7 to 12.7 mg/L, with a Stern-Volmer constant of 0.1115. Further, to obtain better oxygen diffusion, high porosity, optical transparency, and high flexibility, PCD was embedded into a polysulfone matrix (PSF_PCD). The PSF_PCD membrane shows better results for the decay lifetime (9.4 & micro;s), surface energy (40.26 mN/m), and average pore diameter of 5 nm. Hence, the obtained results demonstrate the applicability of the PCD in optical DO sensors for real-time and long-term monitoring of DO levels.
Keywords: decay lifetime; dissolved oxygen; Hydrothermal method; polymer carbon dots; polysulfone-based membrane

Recyclable l-glutamic acid-based polyester schiff base cross-linker for 3D printing applications - Kamble, Ganesh N.; Ghute, Aaditi P.; Asha, S. K. (ACS Applied Polymer Materials, 2026)
An l-amino acid-based polyester Schiff base cross-linker was developed from amine-functionalized polyester and biobased methacrylate vanillin. Vanillin, one of the few biobased and aromatic compounds readily available on an industrial scale, has recently garnered significant attention from the polymer community. The l-amino acid-based polyester Schiff base cross-linker (P3) was synthesized by condensing the aldehyde group of methacrylate vanillin with the amine group of the l-glutamic acid polyester. This polymeric cross-linker was used in resin formulations consisting of isobornyl acrylate as a reactive diluent and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide as the photoinitiator for digital light processing (DLP) three-dimensional (3D) printing. The resulting 3D-printed parts exhibited good mechanical properties, with a Young's modulus of 1.5 GPa, and high thermal stability, with a T max of 410 degrees C. The chemical degradability of the 3D-printed materials was demonstrated in a mixture of tetrahydrofuran and diethylene triamine (1:1) at 80 degrees C for 48 h. The reusability of the recovered resin was demonstrated by adding fresh methacrylate vanillin and photoinitiator, followed by 3D printing using a DLP 3D printer. The 3D-printed parts produced from the recycled resin retained substantial mechanical properties, with a Young's modulus of 1.39 GPa, and thermal stability, with a T max of 390 degrees C.
Keywords: 3D printing; chemical degradation; covalent adaptable network; l-glutamicacid; Vanillin

Redox- and pH-responsive block copolymer nanocarriers with dual drug conjugation through dynamic covalent and hydrogen bonds - Avhad, Shankarrao V.; Surapaneni, Sai Geetika; Purohit, Poorvi M.; Ambade, Ashootosh V. (Journal of Applied Polymer Science, 2026)
Loading of multiple drugs in a nanocarrier with high entrapment efficiency is important for combination therapy in cancer treatment. Here, a block copolymer comprising hydrophobic poly(epsilon-caprolactone) block with a defined number of pendent propargyl groups, polyethylene glycol monomethyl ether as a hydrophilic block, and a redox-responsive disulfide group at the block junction is synthesized using click chemistry and ring-opening polymerization (ROP). Benzaldehyde and thymine groups are introduced in the side chains for selective attachment of anti-cancer drugs, doxorubicin (DOX) and methotrexate (MTX), via the formation of pH-responsive imine linkage and hydrogen bonds, respectively. The drug-conjugated block copolymers are assembled into spherical micelles of < 200 nm, and the preferential release of DOX and MTX in response to acidic pH and redox conditions is shown. At pH 5, DOX release was 59.5%, and MTX release was 40% compared to 13% and 12% at pH 7.4, whereas at pH 5 with 10 mM GSH, a DOX release of 81.5% was observed after 48 h. Cellular uptake of drug-conjugated micelles and their apoptosis compared to free DOX in the MDA-MB-231 breast cancer cells is demonstrated. Caveolae-mediated endocytosis was found to be the major pathway used by drug-loaded nanocarriers.
Keywords: biodegradable; copolymers; DOX-conjugate; drug delivery systems; methotrexate; micelles; pH-responsive; redox-responsive

Self-healing hydrogel electrolyte enabled by dynamic polar covalent and noncovalent interactions for high-performance rechargeable zinc-metal batteries: a leap toward sustainable energy storage - Puthiyaveetil, Priyanka Pandinhare; Kurian, Rachna Maria; Samudre, Nikhil S.; Balasubramanian, Rajalakshmi; Torris, Arun; Pockil, Fayis Kanheeram; Bhat, Suresh; Ajithkumar, T. G.; Krishnamurty, Sailaja; Kurungot, Sreekumar (Advanced Energy Materials, 2026)
Hydrogel polymer electrolytes with superior multifunctional properties are promising alternatives to aqueous electrolytes for resolving interfacial issues in rechargeable zinc-metal batteries. In this study, an intrinsic self-healing hydrogel polymer electrolyte (PHBC-4) is synthesized, engineered through an integrated approach involving the polar covalent (B & horbar;O bond), hydrogen-bond (polyvinyl alcohol-hydroxypropyl methylcellulose interface), and coordination-type (Zn & horbar;O) interactions to enable self-healing functionality. The PHBC-4 has demonstrated high ionic conductivity (4.6 x 10-2 S cm-1), good oxidative stability (2.3 V vs Zn|Zn2+), a high cation transference number (0.89), superior tensile strength (0.32 MPa), and an impressive healing efficiency of 93% achieved just within 5 min, confirming its robust self-healing capability. In Zn||Zn symmetric cells, it effectively suppresses dendrite growth, ensuring stable cycling for over 1032 h with an areal capacity of 1.0 mAh cm-2 at a current density of 1.0 mA cm-2. When paired with a Zn-doped MnO cathode in the rechargeable homemade pouch cell, the system delivers a high specific capacity of 160 mAh g-1 at 0.10 A g-1 and cycling stability up to 493 charge-discharge cycles at 2.0 A g-1. The self-healing ability of PHBC-4 HGPE is confirmed in a homemade pouch cell via OCV and charge-discharge tests, demonstrating stable performance. The DFT studies confirm molecular-level interactions within the hydrogel heterostructure.
Keywords: dendrite inhibition; flexible rechargeable zinc metal battery; high cation transference number; self-healing hydrogel polymer electrolyte

Structural characterisation, anticancer properties, and BSA binding of 2,6-dipyrazinylpyridines: Insights from experiment and theory - Enumula, Sreenivasulu; Shaikh, Javed; Shaikh, Amin; Sheikh, Kounsar N.; Tambe, Pranav; Lande, Dipali N.; Gejji, Shridhar P.; Shaligram, Parth; Gonnade, Rajesh; Bhadbhade, Mohan; Ahmed, Khursheed (Journal of Molecular Structure, 2026)
The phenyl-(2,6-di-2-pyrazinyl)pyridine derivatives (L1, L2) were synthesized using a one-pot Krohnke-type method, starting from 2-acetylpyrazine and substituted benzaldehydes. Their structures were characterized using a combination of spectroscopic (NMR, HRMS) and single-crystal X-ray diffraction techniques, complemented by density functional theory (DFT). Single-crystal X-ray diffraction reveals that L1 crystallizes in the C2/c space group (T = 296 K) with its supramolecular assembly being stabilized by C-H & ctdot;N and pi-pi stacking interactions, whereas L2 facilitates C-H & ctdot;N, N-H & ctdot;pi bifurcated, and pi-pi* interactions. The bio-interaction properties of L1 were studied using fluorescence spectroscopy with bovine serum albumin (BSA) as a model protein. Fluorescence studies demonstrated L1 induces static quenching of BSA, with a binding constant of 5.15 x 104 mol & sdot;dm-3. Synchronous and three-dimensional fluorescence spectra further demonstrated that L1 brings forth significant conformational changes in BSA. The compounds were evaluated for cytotoxicity against the HCT-116 human colorectal cancer cell line.
Keywords: 2; 6-dipyrazinylpyridines; Bovine serum albumin interaction; Cytotoxicity (HCT-116 cells); Density functional theory; Halogenated derivatives; Single-crystal X-ray diffraction

Sustainable nanocellulose extraction from salacca zalacca peel using chlorine-free and low-acid treatments - Krishnan, Akhil; Paul, Sharon; Phiri, Resego; Srisuk, Rapeeporn; Kumar Singh, Manoj; Palaniappan, Sathish Kumar; Rangappa, Sanjay Mavinkere; Dominic, C. D. Midhun; Ajithkumar, Thalasseril G.; Siengchin, Suchart (ACS Omega, 2026)
Conversion of agro-waste to value-added products is one of the important principles of a green circular economy. A novel sustainable technique has been reported by using chlorine-free extraction of cellulose nanofibers (CNFs) from the peels of Salacca zalacca, a common fruit found in Asia. The fruit peels were exposed to alkali treatment using 2% NaOH (60 degrees C, 2 h), chlorine-free bleaching using 15% hydrogen peroxide (60 degrees C, 2 h), and sulfuric acid hydrolysis (15% v/v) for the extraction of CNFs. Various analytical methods were employed to characterize the prepared CNFs. The Fourier transform infrared spectroscopy (FTIR) and 13C solid state nuclear magnetic resonance (NMR) spectra showed the complete elimination of lignin and hemicellulose in the prepared CNFs. The elemental composition and high purity of CNFs were further verified by energy-dispersive X-ray analysis (EDX). The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images proved the fibrous morphology of the prepared CNFs, and the diameters of the cellulose nanofibers were found to be 15-30 nm. The X-ray diffraction (XRD) studies disclosed the type-I cellulosic structure in the prepared CNFs with a high crystallinity index (73%). The thermogravimetric analysis (TGA) demonstrated the superior thermal stability of the prepared CNFs (T max is 350 degrees C) compared to the raw fiber (T max is 320 degrees C). Based on the obtained results, it has been explored that the extracted highly pure CNFs can be used for fabricating bionanocomposites for high performance applications, including food packaging, sensors, water treatment, green tires, etc.

Utilization of bisphenol based on lignin-derived chemicals for the synthesis of partially bio-based aromatic copolyesters - Wale, Apparav K.; Ambade, Ashootosh V.; Wadgaonkar, Prakash P. (Journal of Macromolecular Science Part A-Pure and Applied Chemistry, 2026)
New aromatic copolyesters were synthesized by phase-transfer catalyzed interfacial polycondensation of 4,4 `-((3,4-dimethoxyphenyl)methylene)bis(2-methoxyphenol) (DMBM) with isophthaloyl chloride (IPC) and a mixture of (50:50 mol %) IPC and terephthaloyl chloride (TPC). Additionally, a series of copolyesters was synthesized by polycondensation of varying compositions of DMBM and bisphenol A with IPC. Copolyesters exhibited inherent viscosity and Mn values in the range 0.59-0.98 dL/g and 15,840-49,460 g/mol, respectively, indicating formation of reasonably high molecular weight polymers. Copolyesters could be cast into tough, transparent and flexible films from chloroform solution. UV-vis measurements on films gave values of T400, T450 and cut-off wavelength in the range 80-84 %, 83-89 % and 324-334 nm, respectively. The formation of random copolyesters was evidenced by 13C NMR spectroscopic studies. Copolyesters exhibited good thermal stability with 10% weight loss temperature in the range 391-438 degrees C. The Tg values of copolyesters were in the range 162-180 degrees C and Tg values decreased with an increase in mol% content of DMBM. Copolyesters exhibited tensile strength, Young's modulus and elongation at break values in the range 83.55-70.68 MPa, 2.11-1.31 GPa and 10.52-5.45 %, respectively.
Keywords: Aromatic polyesters; bio-based; bisphenol; methoxyl; Thermal properties

Vanillin-based recyclable thermosets and their glass fiber reinforced composites - Veetil, Ashwani Puthiya; Ravikumar, Aniruddha; Rajput, Tejas; Singh, Aman Kumar; Thakur, Tamanna; Krishna, Abhijith; Pol, Harshawardhan; Shanmuganathan, Kadhiravan; Asha, S. K. (Macromolecular Chemistry and Physics, 2026)
The accumulation of end-of-life plastic materials and composite reinforcement waste materials has brought much attention to developing sustainable alternatives and their re-processability. Incorporating covalent adaptable networks (CANs) into the crosslinked network bridges the concept of reversibility into the otherwise conventional non-reversible networks. This study investigates the structure-property relation in two reversible hardener systems derived from vanillin using Schiff base chemistry. The ``CAN'' systems were synthesized by condensation of vanillin with two amines, 4,4'-oxydianiline and tris(2-aminoethyl)amine, respectively, to form Va_ODA and Va_TAEA. The epoxy thermosets exhibited glass transition temperatures (T-g) of 125 degrees C and 115 degrees C, respectively, for Va_ODA and Va_TAEA, which is superior to most reversible vanillin-based systems reported. The vitrimer-thermosets exhibited promising mechanical and thermal properties, and reshaping abilities as a function of applied temperatures, indicating the dynamic nature of linkages. Chemical degradability was demonstrated by heating to 80 degrees C for 12 h in aqueous acidic medium or excess amine. The fabricated glass fiber composites exhibited good mechanical properties with tensile strength of 361 MPa and degradability in acetic acid/water mixture with a fiber recovery of >98 %. The recovered glass fiber exhibited almost similar tensile strength as the virgin glass fiber, demonstrating its potential reusability. The epoxy vitrimers underwent mechanical reprocessing through hot-pressing, as well as chemical reprocessing via 3D printing and by regeneration of imine bonds to form an epoxy resin.
Keywords: 3D printing; covalent adaptable network; re-processability; Schiff base; Vanillin