Naphthalene diimide (NDI)-based donor-acceptor (D-A) copolymers have potential to be used as ambivalent materials for single-material organic solar cells (SMOSCs). Herein, we systematically explored NDI-fused-thiophene D-A copolymers by varying the donor π $\pi$ -conjugation length by changing the number of fused- thiophene rings. Increase in π $\pi$ -conjugation length of donor-fused thiophene rings significantly decreases the bandgap, from 1.95 to 1.64 eV due to the upshift of the highest occupied molecular orbital (HOMO) energy level, from -5.84 to -5.54 eV. The calculation of electron and hole reorganization energies indicates that increasing the fused-thiophene ring in donor unit may lead to a balanced electron-hole mobility promoting ambipolar transport and also enhances optical properties and photovoltaic performance. The morphological study indicates that increasing the π $\pi$ conjugation of donor moieties leads to improved flexibility in the copolymers accompanied by an initial decrease in crystallinity followed by an increase in crystallinity for NDI-4fTh. Consequently, NDI-4fTh exhibits enhanced charge transport properties and, thus, better performance for organic solar cells. Overall, this study highlights the structure-property relationship relevant to next-generation organic photovoltaic devices through careful tuning of the π $\pi$ -conjugation length of the donor moieties in NDI-basedcopolymers.
We have synthesized two bioinspired materials by introducing chiral L/D-valine (1) and L/D-phenylalanine (2) containing a pyrene fluorophore. Chiroptical properties of these materials are investigated through circular dichroism. The 1 and 2 show nanoassembled modulation and intracellular Cu(II) detection. This study offers a feasible approach for designing bioinspired materials for advanced nanoarchitecture applications.
Titanium alloys are basic materials used in implantology. Their properties can be modified in many ways, e.g., by morphological changes or covering with different bioactive molecules. Platinum(II) complexes are a significant group of anticancer drugs. In an organism, they undergo many chemical processes. A ligand substitution with the S-donor ligands (glutathione (GSH), metallothioneins) is among the most important. This process can be applied to the modification of titanium alloys (Ti6Al4V) with platinum(II) complexes, e.g., [Pt2(6NNqui)Cl4] (PtQ6). The paper presents a modification of the Ti6Al4V alloy with titania nanotubes and the studied complex, using the bridging ligand (3-mercaptopropyl)triethoxysilane (MPTES). Moreover, a kinetic study on chloride substitution in the studied bimetallic cisplatin analogue (PtQ6) by L-cysteine, an amino acid that is a part of GSH and metallothioneins, is also presented. It is a good way to get locally active implants in the targeted anticancer therapy. The produced material is characterized with spectral and microscopic methods, including XPS (X-ray photoelectron spectroscopy). The mechanism of the substrate modification with platinum(II) complex is based on the substitution process. The nanomechanical properties of the modified and functionalized substrate are also tested in the indentation tests.
The production of hydrogen fuel via water electrolysis has emerged as one of the energy conversion technique to alleviate the global energy scarcity. The search for non-noble metal based active electrocatalyst to accelerate water electrolysis process has become one of the challenging task. Here, a suitable and facile one-step solvothermal method has been followed for the growth of Cd based pristine metal organic frameworks (MOFs) onto nickel foam (NF). The binder-free three-dimensional (3D) Cd (II)-BPFA-MOF/NF electrode exhibits an excellent performance toward urea-assisted water splitting. The electrocatalyst Cd (II)-BPFA-MOF/NF showed an overpotential of 148 and 420 mV at benchmark current density of 10 mA cm-2 in 1 M KOH medium for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. At the same time, Cd (II)-BPFA-MOF/NF exhibit only 1.59 V for urea oxidation reaction (UOR) at benchmark current density in 1 M KOH and 0.33 M urea medium. The Cd (II)-BPFA-MOF/NF || Cd (II)-BPFA-MOF/NF bifunctional electrodes demands only 1.54 V potential to achieve a current density of 10 mA cm-2 toward urea-assisted overall water splitting reaction (UOWS) with remerkable long-term stability. Therefore, this work represents application of a waste to wealth approach toward Cd-based sustainable electrocatalyst for renewable hydrogen production.
Supramolecular chemistry explores how noncovalent interactions enable the association of multiple molecular components into structurally defined and functionally active assemblies, with molecular recognition arising from geometric, electronic, and chemical complementarity. Integrating these principles with photocatalysis is reshaping organic synthesis by introducing adaptive control over reactivity under visible light. Through Hbonding (hydrogen bonding), π-π stacking, host-guest encapsulation, charge-transfer complexation, hydrophobic effects, and σ-hole interactions (cation-π, anion-π, and halogen bonding), supramolecular photocatalysts dynamically organize substrates and modulate excited-state properties, thereby influencing reaction pathways and selectivity. Such assemblies can respond to changes in substrate identity, aggregation state, or irradiation conditions, enabling tunable and metal-free photochemical transformations. Inspired by biological photosystems, spatial confinement and electronic communication within supramolecular architectures further unlock unconventional reactivity beyond classical photocatalysis. This review article summarizes recent mechanistic insights and design strategies, positioning supramolecular photocatalysis as a versatile and sustainable platform for next-generation catalytic synthesis.
A newly synthesised colorimetric and fluorescent chemosensor (P1) was developed for the selective detection of Cr3+ and Cu2+ ions in the presence of various competing cations and anions. The structure of P1 was thoroughly characterized using FT-IR, NMR, high-resolution mass spectra, and single-crystal X-ray diffraction techniques. The 1:1 binding ratio of the probe was verified using Job's plot analysis, and further density functional theory calculations were performed to gain insight into the coordination mode, metal-ligand bonding, and optimized molecular geometry of the complexes. The sensor exhibited detection limits of 1.96 μM for Cr3+ and 7.16 μM for Cu2+. Furthermore, fluorescence imaging studies in HeLa cells demonstrated a significant fluorescence enhancement upon exposure to Cu2+ ions, confirming the effective sensing performance and bioimaging applicability of P1.
Allergic diseases have been increasing significantly with increasing level of pollution besides the natural causes, affecting more than 20% of the global population. First-line treatment using antiallergic drugs include topical corticosteroids, as well as adjuvant treatment of antihistamine drugs, that have adverse side effects including development of drug resistance when used for long term, thus necessitating alternative strategies. Acorus calamus rhizome (ACR) is known to be used in traditional medicines. The present study intends to assess the antiallergic potential of secondary metabolites reported to be present ACR. Molecular docking studies could evaluate the binding affinity of the curated secondary metabolites with four key allergy-associated proteins, viz., histamine H1 receptor (H1R), interleukin-4 (IL-4), IL-13, and IL-5. Based on molecular docking and absorption, distribution, metabolism, excretion, and toxicity analyses, best two inhibitory phytochemicals appear to be δ-cadinene and β-caryophyllene for H1R; acoronene and espatulenol for IL-4; lepidozene and δ-cadinene for IL-13; and curcumin and pinostilbene for IL-5, respectively. Molecular dynamics simulation studies further confirm that these compounds can form stable complexes with the aforementioned proteins. Such set of comprehensive studies are considered to emerge as baseline for further in vitro and in vivo studies to validate their antiallergic potentials.
Quinclorac is a widely used selective herbicide that targets plant growth hormones. However, it exhibits poor water solubility, limited plant permeability, and dependence on adjuvants. To address these limitations, we synthesized a series of novel herbicidal ionic liquids (HILs) by pairing the quinclorac anion with various cations, including quaternary ammonium, imidazolium, morpholinium, and 4-hydroxypiperidinium. Compared with quinclorac, the resulting HILs exhibited markedly improved physicochemical properties, including enhanced solubility, reduced surface tension, and increased lipophilicity. Thermal analysis confirmed excellent stability, with decomposition temperatures above 200°C and vaporization enthalpies exceeding 120 kJ/mol. Surface activity measurements indicated lower critical micelle concentrations (CMC) and reduced contact angles (CA), promoting superior wetting and adhesion on plant surfaces. Greenhouse bioassays demonstrated enhanced herbicidal activity against barnyard grass, achieving inhibition rates above 80% at 225 g AI/ha without phytotoxic effects on rice. Notably, at low concentrations (225-375 g AI/ha), all HILs promoted rice growth, while at higher concentrations (525-675 g AI/ha), HIL3 and HIL4 (containing long-chain quaternary ammonium cations) and HIL5 (containing an imidazolium cation) exhibited significant growth-promoting effects. This study reports the first quinclorac-based HILs and highlights their potential as sustainable, efficient, and environmentally friendly alternatives to conventional herbicide formulations for rice cultivation.
A novel unimolecular platform based on an intramolecular charge transfer-active hydrazone probe was developed to construct versatile, opto-chemically driven molecular logic devices. The probe exhibited dual-channel responses: a ∼13.5-fold fluorescence quenching at 442 nm with CN- and a 35 nm red-shift with Hg2+. These discrete responses enabled the fabrication of XOR, INHIBIT, and XNOR logic gates at specific wavelengths (440, 355, and 395 nm, respectively), facilitating a molecular half-subtractor and comparator. Time-dependent optical transitions with Cu2+ and Hg2+ inputs produced dynamic gate switching (TRANSFER to OR, N-TRANSFER to IMPLICATION). Furthermore, multianalyte combinations with F-, CN-, and Hg2+ enabled the creation of a 3-input, 3-output Boolean circuit. Threshold-guided absorbance (e.g., >0.15 for ON) ensured quantifiable logic states. The reversible nature of ion binding, demonstrated using EDTA, enhances reusability. This work advances tunable, multigate molecular computing for next-generation bio-optoelectronic interfaces.
Forensic science is a multidisciplinary field that plays a vital role in society by supporting criminal investigations and providing scientific evidence for judicial proceedings. Within this context, organic chemistry contributes fundamentally by enabling the structural elucidation of seized drugs and their intermediates, the synthesis of analytical reference standards for doping control, allied with a deeper understanding of drug metabolization, and the development of probes for detecting fingerprints and biological fluids. This review examines recent advances at the interface between organic synthesis and forensic science. The discussion is organized into three main application areas: drug identification, toxicology, and fingerprint analysis, highlighting how synthetic methodologies have been employed to address key challenges in each topic. Furthermore, this work aims to shed light on the broad range of opportunities for the organic synthesis community to contribute to the advancement of forensic science.
Colloidal crystal engineering with DNA has made significant progress in the bottom-up fabrication of long-range ordered three-dimensional superlattice materials with unique optical, catalytic, and biological properties using DNA-functionalized nanoparticles, known as programmable atom equivalents (PAEs), as fundamental building blocks. However, escaping metastable states during the self-assembly of PAEs in far-from-equilibrium systems remains an intractable challenge in this field. As an entropy-modulating strategy, thermal annealing is a widely adopted conventional approach for regulating PAE crystallization. Recently, several alternative or complementary PAE assembly strategies have emerged, particularly catalytic-assembly approaches based on toehold-mediated DNA strand displacement, which enable programmable and efficient synthesis of PAE superlattice structures under mild isothermal conditions. This concept paper reviews and discusses key developments in programmable isothermal regulation strategies, focusing on their operating mechanisms, advances in dynamic functionalities, and representative applications, with the goal of inspiring future research in related fields.
Two potential biomass-derived Cyrene-based reaction media, i.e., Cyrene dimethyl and diethyl acetals, were synthesized and tested as potential polar aprotic alternatives to fossil-based common N,N-dimethylformamide in aminocarbonylation protocols. New solvents were first characterized by their temperature-dependent physicochemical properties, including vapor pressure, density, viscosity, heat capacity, and surface tension. Based on their characteristics, Cyrene dimethyl acetal (CyDiOMe) was selected and used in the Pd-catalyzed aminocarbonylation of iodobenzene and morpholine as a model reaction for optimization. Under optimized conditions, a wide substrate scope was demonstrated for the synthesis of various carboxamides with high conversion (up to 95%) and selectivity in a short reaction time. Twenty-nine products were isolated, proving the applicability of CyDiOMe in Pd-catalyzed aminocarbonylation.
Zirconia (ZrO2) nanoparticles (NPs) were biosynthesized using Cynodon dactylon leaf extract via an environmentally benign route and evaluated for antioxidant activity and corrosion protection of mild steel in acidic media. X-ray diffraction confirmed nanocrystalline tetragonal ZrO2, while Fourier transform infrared spectroscopy evidenced phytochemical functionalities that cap and stabilize the particle surface. Scanning electron microscope and transmission electron microscopy revealed agglomerated morphologies composed of nanoscale primary particles; consistent with this, dynamic light scattering showed micrometer-scale hydrodynamic diameters arising from aqueous aggregation. NP formation and aggregation were strongly governed by alkaline pH, reaction time, temperature, and extract concentration, which collectively modulate nucleation, growth, and surface stabilization. Electrochemical and gravimetric assessments (potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and weight loss) demonstrated dose-dependent inhibition, achieving a maximum protection efficiency of 82.5%. EIS responses showed enlarged Nyquist semicircles and increased charge transfer resistance, indicating development of a compact barrier layer on steel. Weight-loss measurements yielded inhibition efficiencies of ∼23.5% after 24 h and ∼64.7% after 48 h. Antioxidant performance of C. dactylon extracts was quantified using 2,2-diphenyl-1-picrylhydrazyl and 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) assays, with methanolic extracts exhibiting the highest radical-scavenging activity. Collectively, these results establish C. dactylon-derived ZrO2 as multifunctional nanoadditives with coupled antioxidant and mixed-type anticorrosive behavior supported by adsorption-based mechanistic interpretation. This integrated study connects synthesis optimization to corrosion and antioxidant performance.
Means to control rotary motion at the nanoscale are central to the design and operation of artificial molecular machines powered by such motion. For this task, it is natural to consider molecular gears, which are characterized by their ability to perform coupled rotations around two (or more) chemical bonds. However, most such gears rely on passive, thermal activation, which makes them sensitive to Brownian motion. In this concept, following a brief review of the historic development of molecular gears, we highlight some recent experimental and computational results that have helped show how this problem can now be addressed by means of the type of molecular photogearing achieved when the double-bond rotary motion produced by a light-activated molecular motor is transmitted through space onto a single-bond axis. Furthermore, we discuss the formidable challenge to maintain a preferred direction of rotation during this transmission, which is critical for performing mechanical work. Finally, we point out some research directions suitable for maximizing the future usefulness of molecular gears and photogears.
Heavy metal pollution is a global environmental challenge. Removal of heavy metal ions by recyclable absorbents and metal recovery by environmentally friendly methods are of high importance. In this study, hydroxyapatite (HAp) was synthesized and employed for the removal of copper (Cu2+) and nickel (Ni2+) ions from aqueous solutions. The adsorption behavior of both metal ions was systematically investigated under various conditions, including changes in pH, contact time, initial concentration, and adsorbent dosage. The adsorption capacity and efficiency for Cu2+ were measured at 49.53 mg.g-1 and 99.06%, respectively, while for Ni2+, the values were 12.15 mg.g-1 and 80.99%. Adsorption isotherm analysis indicated a good fitting with Redlich-Peterson models, while kinetic studies confirmed that the process followed the pseudo-second-order models, suggesting chemisorption involvement. Furthermore, desorption of metal ions and recovery of elemental Cu and Ni were conducted via electrodeposition in a choline chloride-urea (reline) deep eutectic solvent. Under optimal electrolysis conditions (current density of 7.5 mA.cm-2, 10-hour duration, 0.1 g metal-loaded HAp, and 60°C), recovery efficiencies reached 94.63% for copper and 94.80% for nickel. The regenerated HAp retained significant adsorption performance, with capacities of 39.25 mg.g-1 for Cu2+ and 11.18 mg.g-1 for Ni2+, corresponding to removal efficiencies of 78.49% and 74.60%, respectively. Synthesized HAp could be potentially an effective, recyclable adsorbent for the treatment and recovery of heavy metals from wastewater.
A plasma-assisted strategy was developed for the synthesis of tetrazole derivatives using carbon-based nanocatalysts derived from biomass. Coconut coir was employed as a renewable carbon source to prepare a porous catalyst support, which was subsequently functionalized via N2/H2 nonthermal plasma treatment to introduce amino and carboxylic acid groups. The incorporation of TiO2 and CuO nanoparticles further enhanced the catalytic performance by increasing surface acidity and electron density. The resulting catalysts efficiently promoted a multicomponent reaction between acetoacetanilide, aromatic aldehyde derivatives, and 5-aminotetrazole, affording tetrazole products in high yields (up to 96%) under mild conditions in an ethanol-water mixture. This approach provides a sustainable, recyclable, and efficient route for tetrazole synthesis, highlighting the synergistic effect of plasma activation and biomass-derived nanostructures.
Transcatheter arterial embolization (TAE) is a minimally invasive interventional procedure performed under X-ray guidance. It involves catheter-based delivery of embolic agents (EAs) into pathological or injured blood vessels to block the blood supply, thereby achieving rapid hemostasis. Meanwhile, this technique induces ischemic necrosis of tumor cells by depriving them of nutrients and oxygen through targeted vascular occlusion. Owing to its advantages of minimal invasiveness, precise targeting, and repeatability, TAE has been widely adopted in clinical practice. However, its therapeutic efficacy is mainly constrained by two limitations: insufficient imaging stability caused by the rapid dispersion of radiopaque agents in the blood vessels, as well as the chemotherapy resistance induced by lactic acid accumulation in the tumor microenvironment due to embolization. In this study, we developed a novel bifunctional gelatin-based embolic microsphere that can simultaneously meet the requirements of promoting the drug uptake by tumor tissues and stable X-ray imaging through encapsulating sodium bicarbonate nanoparticles and barium sulfate (BaSO4) contrast agents into the gelatin embolic microsphere. We further systematically evaluated its physicochemical and biocompatibility properties. This study provides a novel strategy for developing EAs with integrated radiopacity stability and improved drug uptake, holding potential for advancing precision in interventional therapies.
Herein, we have successfully implemented two dinuclear copper complexes based on N, O donor ligands as efficient and selective catalysts for the arylation of N-heterocycles using aryl iodides, aryl bromides, and even less reactive aryl chlorides under relatively mild conditions. This is a dinuclear approach where metal-metal cooperation through a bridging ligand can enhance the catalytic process more efficiently than traditional mononuclear complexes. The structural characterization of a dinuclear copper complex of the form Cu2L1 4, 1 based on N, O donor 8-hydroxyquinoline (HL1), reveals the formation of interesting isomeric structures. The complex 1 shows better catalytic activity toward N-arylation compared to the bis-chelating Schiff base N, O donor 2,2'-[naphthalene-1,5-diylbis(nitrilo-methanylyl-idene)]diphenol (H2L2)-coordinated dinuclear copper complex ClCu(μ-L2)CuCl, 2. The current protocol is effective for the arylation of imidazole, pyrazole, benzimidazole, 1,2,4-triazole, pyrrole, and indole, with tolerance of common functional groups. The N-arylation reaction catalyzed by 1 has been successfully scaled up to Gram scale without significantly reducing the product yield. A mechanistic route for this N-arylation reaction has been proposed by considering various control experimental and spectroscopic results.
In this study, we have reported the synthesis of Ni0.4Zn0.6NdxFe2-xO4 with varying concentrations of neodymium (x = 0,0.025,0.05,0.075, 0.1) by sol gel method. The effect of neodymium doping on the structural parameters, magnetic properties, dielectric behavior, AC conductivity, and optical properties has been investigated in detail. Formation of a single phase in all prepared compositions except at x = 0.1 was confirmed by the XRD technique. The EDX analysis has confirmed the compositional uniformity and high purity. The VSM analysis has revealed ferrimagnetic behavior of the doped ferrites. The composition with neodymium content, x = 0.05, is reported to have the lowest coercivity, minimum dielectric loss and reasonably good dielectric constant; therefore can be considered as a potential candidate for high frequency applications. The UV-DRS measurements have revealed a decrease in bandgap thereby indicating possible photocatalytic applications.
This study investigates the effect of a nickel complex of 2,6-pyridinedicarboxylic acid (Ni-PDC) in modulating the properties of hydrogenated nitrile butadiene rubber (HNBR) composites. The composites were prepared via dicumyl peroxide (DCP) crosslinking, with varying Ni-PDC loadings. Structural analyses via Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) confirm successful integration of the Ni-PDC complex into the HNBR matrix. However, X-ray photoelectron spectroscopy (XPS) supports the presence of Ni2+ and validates Ni-PDC coordination within the HNBR matrix. Curing studies reveal a reduction in viscosity and an alternative in crosslink density. Mechanical testing reveals appreciable reinforcement, with a significant enhancement in tensile strength and elongation at break in comparison with unreinforced HNBR. Furthermore, the conduction of cyclic stress-strain study demonstrates a reduction in hysteresis losses, thereby signifying an enhancement in elastic recovery. Thermogravimetric analysis (TGA) reveals increased thermal stability, while differential scanning calorimetry (DSC) indicates a downward shift in glass transition temperature, consistent with enhanced segmental mobility imparted by dynamic coordination of Ni-PDC complex. The present study reports the combined effect of DCP curing and Ni-PDC incorporation in HNBR composites, with a view to enhancing their mechanical performance, flexibility (viscoelasticity) and thermal resistance.