Ahead of Publication / Just Accepted

The International Year of Quantum Science and Technology (IYQ) celebrates the centenary of quantum mechanics (QM). In this perspective, I highlight that QM is not only a playground for physical chemists but of tremendous value to organic chemists as exemplified in its ever-increasing role in the career of Nobel prizewinner R.B. Woodward. Over three decades, this ranged from the prediction of UV-visible absorption wavelengths arising from electronic excitations to the importance of molecular orbital symmetry and the derivation of the Woodward-Hoffmann rules for pericyclic reactions.

The industrialization of peach palm heart generates a volume of by-products that are not subjected to any treatment, which is why there is a need to establish processes for their valorization. This study focuses on characterizing a dehydrated powder product rich in dietary fiber obtained from an industrial by-product of peach palm heart. The by-product samples were transformed into a dehydrated powdered product, and standardized tests were applied to evaluate its physicochemical, functional, and sensory properties. The final powder product exhibited high dietary fiber and protein contents, 53 % and 15 %, respectively. It was determined that functional properties significantly varied depending on particle size, and sensory analysis suggested that palm heart fiber may be promising for food enrichment. The dehydrated powdered product appears to be a promising approach for valorizing this type of by-product, as it exhibited neutral color, functional, and sensory properties consistent with those reported in other valorization studies.

Pichichio ( Solanum mammosum ) is a tropical plant known for its pharmacological properties, primarily associated with its fruit and leaves. Ethanolic extracts of its fruit and leaves are being studied for the first time as a green corrosion inhibitor due to their effectiveness on low carbon steel in acidic medium (1.0 M HCl) based on ASTM G 31. The extracts Fourier Transform Infrared (FTIR) spectra and High Performance Thin Layer Chromatography had identified coumarins, polyphenolic compounds, and possible anthraquinones. Pichichio leaf extract (PLE) exhibiting higher antioxidant capacity compared to pichichio fruit extract (PFE) but this property does not show a clear correlation with inhibition efficiency. Gravimetric analysis indicated that both extracts provide significant corrosion inhibition (greater than 90 %) at concentrations of 1000 mg L −1 , though the inhibition efficiency decreases with lower concentrations, higher temperatures, and extended application times. Electrochemical analysis revealed Randles-type behavior with deviations at low frequencies, as well as slight variations in the open circuit potential ( E oc ) and Tafel slopes. Both extracts (PLE and PFE) act as mixed-type inhibitors, with a predominant barrier effect, displaying Langmuir-type adsorption curves for PFE and Flory-Huggins-type for PLE. The variations in the thermodynamic adsorption energies are significant only for PFE, suggesting better surface interaction. Surface visualization through physical methods suggests that the extracts reduce overall surface roughness, which correlates well with their barrier effect.

This report provides a summary of recommended or suggested values of the rate coefficients for thermal decomposition ( k d ) and of the efficiencies for radical generation ( f g ) and initiation of polymerization ( f i ) for some commercially available dialkyldiazene (also known as azo-compound) initiators. These initiators are one of the most important classes of initiators used in both conventional radical polymerization and reversible-deactivation radical polymerization (RDRP). Although values of k d can be cited with confidence for many initiators, it must also be stated that for most initiators there is insufficient quality data in the open literature to allow a rigorous statistical analysis. The situation is complicated by some initiators existing as a mixture of diastereomers and decomposition rates being subject to small, yet experimentally significant, solvent dependence. Efficiencies for radical generation ( f g ) are available for some initiators. Efficiencies for initiation of polymerization ( f i ) are less common and have been demonstrated to be strongly dependent on the initiator, the complexity of the mechanisms for radical generation and for initiation of polymerization, the reaction medium, the monomers being polymerized and their concentration as determined by the amount of solvent, and the conversion of monomer to polymer. Consequently, only general recommendations for initiator efficiency are possible at this stage.

In this Technical Report, we introduce the application of FAIR (findable, accessible, interoperable, and reusable) data management in the form of a “FAIRSpec-ready spectroscopic data collection” – that is, a collection of instrument data, chemical structure representations, and related digital items that is ready to be automatically or semi-automatically extracted for metadata that will allow the production of an IUPAC FAIRSpec Finding Aid. Associating this finding aid with the collection produces an IUPAC FAIRSpec Data Collection. The challenge we set for researchers is relatively simple: to maintain their data in a form that allows critical metadata to be extracted in a discipline-specific way, increasing the probability that the data will be findable and reusable both during the research process and after publication. We focus on a few specific suggestions that researchers can use to maximize the “fairness” of their spectroscopic data collection. Most importantly, following these guidelines ensures that instrument datasets are unambiguously associated with the chemical structure. The guidelines promote the inclusion of the instrument dataset itself in the collection and describe ways of organizing the collection such that automated metadata creation is possible. In these guidelines, we emphasize the importance of systematically organizing data throughout the entire research process, not just at the time of publication.

The synthetic dye Remazol Brilliant Blue R (RBBR), widely used in the Batik industry, was successfully degraded under UV irradiation using ZnO/rGO composite photocatalysts synthesized with reduced graphene oxide (rGO) derived from rice bran waste. Characterization was performed using X-ray diffraction (XRD), Raman spectroscopy, Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM-EDS), Brunauer–Emmett–Teller (BET) surface area analysis, and UV–vis diffuse reflectance spectroscopy (DRS). The photocatalytic performance was evaluated for composites with varying rGO contents: ZR-0 (pure ZnO), ZR-1 (ZnO with 5 mg rGO), and ZR-2 (ZnO with 25 mg rGO). The ZR-1 composite exhibited the highest degradation efficiency of 78.95 % within 240 min, compared to 58.57 % for ZR-0 and 65.70 % for ZR-2. The corresponding pseudo-first-order rate constants were 0.0034 min −1 (ZR-1), 0.0065 min −1 (ZR-0), and 0.0048 min −1 (ZR-2). These results confirm that the addition of a moderate amount of rGO enhances the photocatalytic activity of ZnO, while excessive rGO may reduce UV light absorption due to surface coverage and recombination effects.

This perspective offers a personal reflection on the evolution, current status, and open challenges of quantum chemistry in the context of large molecular systems. Beginning with Dirac’s famous 1929 prophecy, I revisit the historical trajectory of our discipline, from the development of early conceptual models to the emergence of density functional theory and correlated wavefunction methods. While enormous progress has been made in algorithmic sophistication, enabling accurate calculations on systems with thousands of atoms, I argue that accurate energies alone do not solve the entirety of chemical problems. Real-world applications demand more than electronic structure: solvation, entropy, conformational complexity, and the sheer complexity of large molecules challenge our methods and our assumptions. Equally important are the conceptual and philosophical tensions that continue to shape the field, especially the difficult balance between prediction and understanding. I advocate for a more integrative approach that values models, insight, and falsifiability alongside numerical precision. Finally, I briefly consider the emerging role of machine learning and the implications of automation for the future of theory. This article is not a review but a dialogue – with the field, with its history, and with its practitioners.

Based on semi-empirical quantum mechanics calculations and extensive molecular mechanics calculations and molecular dynamics simulations, a novel molecular level conceptualization of key biochemical events in the pathogenesis of Alzheimer’s disease (AD) is presented. In response to immune stimulating events ( e.g ., infection, trauma), β-amyloid (Aβ) protein is released in brain as a protective immunopeptide triggering an immunity cascade in which Aβ exhibits antimicrobial activity, which mistakenly results in a misdirected attack upon “self” neurons, arising from the macromolecular and electrochemical similarities between neurons and bacteria in terms of transmembrane potential gradients and anionic charge distribution geometries on outer membrane macromolecules (gangliosides in neurons; cardiolipins or lipopolysaccharides in bacteria). Molecular mechanics/dynamics calculations are used to demonstrate how the inability of Aβ to distinguish between bacteria and neurons is a central pathological process in the pathogenesis of AD.

This recommendation defines the preferred methodology for determining reactivity ratios from copolymer composition data using the terminal model for radical copolymerization. The method is based on measuring conversion ( X ) and copolymer composition ( F ) of three or more copolymerization reactions conducted with different initial monomer compositions ( f 0 ). Both low and high conversion experiments can be combined, or alternatively only low conversion experiments can be used. The method provides parameter estimates, but can also reveal deviations from the terminal model and the presence of systematic errors in the measurements. Special attention is given to error estimation in F and construction of the joint confidence interval for the reactivity ratios. Previous experiments measuring f 0 − F (i.e., copolymer composition as a function of varying f 0 ) or f − X (i.e., how f varies with X in an experiment) can also be analyzed with this IUPAC recommended method. The influence of systematic errors in the measurements on the reactivity ratio determinations is addressed. The document has a broad significance in that it seeks to eradicate the use of incorrect methods and common mistakes in determining reactivity ratios in radical copolymerizations.

The story of the development of quantum mechanics is briefly told, from the perspective of human dynamics, and in the spirit of the sobering truth behind it. Three long term contributions from the author’s lab are succinctly presented: (i) FFLUX, a machine-learnt potential for the molecular dynamics of peptides in water, thereby overhauling the architecture of classical force fields; (ii) REG, an unbiased and minimal method to compute chemical insight, thereby reducing the vexing gap between it and modern wavefunctions; (iii) AIBL, a gas-phase-based predictor of pK a values in solution, including for tautomerisable and multiprotic compounds of more than 50 atoms, and able to even correct experiment.

Accurate wavefunction methods like CCSD(T) can predict chemical and thermodynamic properties of small molecules with near-experimental precision. However, their steep computational cost limits their use for large systems or extensive datasets. In contrast, DFT is faster and more practical for large molecules but often fails to accurately capture electronic changes, especially upon geometry relaxation. To address this, we have developed a graph neural network (GNN)-based Delta-Machine Learning (ΔML) model using Connectivity-Based Hierarchy (CBH-2) molecular fragments as descriptors to predict adiabatic ionization potentials (IPs). Our approach shows systematic error cancellation, guided by electron population difference maps to identify ionization sites within the molecule to construct CBH-2 fragments. We have considered both structural and electronic features to improve our ΔML model. We have observed that upon incorporation of electronic features, the graph-based ΔML model achieved a coupled cluster level of accuracy with an MAE of 0.02 eV for IP prediction. Furthermore, we compared adiabatic and vertical IP predictions across different methods. While raw DFT errors are strongly dependent on the functional used, our ΔML model is robust and much less functional-sensitive.

Although the accuracy of first-principles calculations makes them ideal for modeling noncovalent interactions, their high computational cost limits their applicability to moderate system sizes. Analytic potentials have emerged as an excellent means of modeling large-scale systems because of their simplicity and computational efficiency. However, the effectiveness of the analytic potentials depends heavily on the choice and the transferability of their parameters. Herein, employing noble gases as a testbed, we embarked on assessing the transferability of parameters of two widely used pair potentials, Lennard-Jones (LJ) and improved Lennard-Jones (ILJ) potentials. We established the inadequacy of the various traditional combination rules for the LJ potential in describing noble gas heterodimer interactions. The potentials that are parametrized against benchmark CCSD(T) calculations for noble gas homodimers and heterodimers failed to accurately describe the interactions in dimers of noble gas dimers. However, a parametrization of the LJ and the ILJ potentials against reference electronic structure calculations describing noble gas dimer-dimer interactions was found to be effective. The ILJ potential consistently exhibited improved accuracy over the LJ potential. Our study showcases the non-transferability of the LJ and the ILJ parametrizations developed for the elementary pairwise interactions to the description of complex chemical systems.

A series of valence bond charge-transfer (VB- n CT) models ( n  ∈ [1, 4]) are enacted to assess the influence of molecular symmetry on the second-order nonlinear optical (NLO) response, the first hyperpolarizability, β . This is accomplished for different amplitudes of the ground-state charge-transfer character, quantified by the VB-CT mixing parameter, m CT . The analysis focuses on quantities accessible from the second harmonic scattering (SHS) phenomenon and measurements, β SHS and its depolarization ratio. Among the symmetries considered, D 3 h and C 3 v (VB-3CT, with large θ , i.e. for almost planar tripod-shape molecules) yield the largest β SHS values provided m CT is large, followed by T d (VB-4CT). These cases correspond to dominant octupolar responses and depolarization ratios close to 3/2. Other symmetries result in comparatively weaker responses, and a variety of depolarization ratios. Maximizing the charge-transfer dipole moment μ CT and minimizing the ratio ξ  =  T / t , are also identified as critical factors for enhancing the second-order NLO responses.

Adamantane-based epoxy resin (ADEP) and tricyclodecyl modified adamantane-based epoxy resin (ADTCDEP) were synthesized and their chemical structures were confirmed by FT-IR, 1 H, and 13 C NMR spectroscopy. The morphological, thermal, dielectric, and optical properties of ADEP and ADTCDEP were studied. The introduction of adamantane and tricyclodecane groups into the chain of epoxy resins improves thermal, mechanical, and dielectric properties. In addition, UV–vis transmission spectroscopy showed that the tricyclodecyl-containing epoxy membrane exhibited novel UV filtering properties and thermo-oxidative stability. ADEP exhibits novel UV filtering properties, and the cut-off wavelength λ c can be changed by simply changing the heat-aging temperature. ADTCDEP maintains approximately 85 % transmittance in the visible region (700 nm) and exhibits good heat resistance and better transmittance than EP904 even after heat aging in air at 120 °C/168 h.

Corrosion inhibitors are chemical agents that, even at low concentration, markedly mitigate the rate of metal degradation in acidic media. The objective of this study is to screen and evaluate the corrosion inhibition of Nitrobenzaldehyde Meldrum’s Acid (NitroMA) in HCl medium. The NitroMA compound was successfully synthesized through a condensation method and characterized using ATR-FTIR, NMR, and elemental analysis. Weight loss measures revealed that the corrosion inhibition efficiency of NitroMA increases with its concentration in 1 M HCl concentration. The inhibition efficiency of NitroMA was as high as 80.94 % at 5 mM in 1 M HCl. The alignment with Langmuir and Frumkin models indicates that inhibition efficiency arises from a combination of monolayer adsorption and intermolecular attraction across different surface regions, which may lead to more stable and compact monolayers on the metal surface as confirmed by the SEM-EDX analysis. Both Langmuir and Frumkin isotherms fitted the data with high correlation coefficients (R 2  > 0.999). The Langmuir model yielded a Gibbs free energy of adsorption around (−21.1 kJ mol −1 ), suggesting a borderline case between physisorption and chemisorption. In contrast, the Frumkin model gave a lower value (−9.11 kJ mol −1 ), consistent with physisorption. The variation arises because Langmuir assumes a homogeneous surface with no adsorbate–adsorbate interaction, while Frumkin accounts for lateral interactions. Therefore, the compound primarily undergoes physisorption, but the Langmuir result also indicates possible contribution of weak chemisorption. Following this, NitroMA was screened using Response Surface Methodology (RSM) with two-factors analysis, incorporating temperature, acid concentration, inhibitor concentration, time, and ratio of volume acid and inhibitor as the parameters. The developed RSM model demonstrated a good fit, as reflected by the statistical parameters: R 2  = 0.8962, Adjusted R 2  = 0.8851, and Predicted R 2  = 0.8644, indicating high reliability and predictive accuracy. The results showed that temperature, time, and acid concentration significantly influence the inhibition efficiency. These findings were validated by computational analysis using the Pearson correlation analysis, which demonstrated that temperature, acid concentration, and time are the most strongly linked to parameters with inhibition efficiency.

Despite being introduced approximately 30 years ago, green metrics are still not widely implemented in the practice of Green Chemistry. Nowadays, there is a general desire and fashion for Green Chemistry considering the modern global concerns of climate change and resource scarcity. However, the scientific literature reveals a confusing array of definitions and methodologies related to green metrics, particularly in both organic and inorganic chemistry. In this review we want to focus on organic synthesis, namely new reaction pathways that employ organic and inorganic catalysts, grounded in fundamental chemistry. The application of rigorous green metrics must go along with the experimental validation of synthetic procedures. This is essential to establish clear guidelines for defining truly green synthetic approaches, and to prevent misunderstandings or overreaching claims that are based on subjective rather than objective assessments. This work originated from an IUPAC project aimed at providing standardized guidance for the use of green metrics. Accordingly, we present a list of green metrics and related terminology currently employed to assess material usage, energy efficiency, and environmental impact in individual reactions and synthetic strategies.

Aromatic polyesters were synthesized from 3,5-dihydroxy-N-(4-(naphthalen-8-yloxy)phenyl)benzamide via interfacial polycondensation with varying molar ratios of isophthaloyl chloride (IPC) and terephthaloyl chloride (TPC). The diol precursor was synthesized by Yamazaki condensation and characterized using FT-IR, 1 H NMR, and 13 C NMR spectroscopy. The resulting polyesters were obtained in high yields (84–93 %) with inherent viscosities in the range of 0.37–0.54 dL g −1 , confirming moderate chain lengths. Solubility studies revealed that all polyesters were soluble in NMP, DMF, DMAc, and DMSO, partially soluble in THF and m-cresol, and poorly soluble in chloroform and dichloromethane. Thermogravimetric analysis (TGA) indicated good thermal stability, with initial decomposition temperatures of 151–169 °C, 10 % weight-loss temperatures ( T 10 % ) of 369–425 °C, and residual weights of 34–53 % at 800 °C. Differential scanning calorimetry (DSC) showed glass transition temperatures ( T g ) ranging from 109 to 129 °C. The incorporation of bulky naphthyl pendant units and ether linkages disrupted chain packing, enhancing solubility while retaining thermal stability. These results suggest that the synthesized polyesters possess a balanced combination of solubility and thermal resistance, making them potential candidates for applications in membranes, coatings, and other processable high-performance materials.

Developing efficient organic photoredox catalysts is essential for advancing sustainable CO 2 conversion technologies. This paper investigates the photophysical properties of oligo- p -phenylenes (OPP- n ), with a focus on p -terphenyl (OPP-3), and its functionalized derivatives to identify structural features that may enhance their photocatalytic potential. We examine how symmetric and asymmetric terminal substitutions affect excitation energies, oscillator strengths, exciton characteristics, and fluorescence. Our results show that push–pull derivatives have significantly lower excitation energies and larger oscillator strengths, promoting efficient radical anion generation. These derivatives also exhibit longer fluorescence lifetimes, which may improve the probability of productive interactions with sacrificial electron donors. Exciton analysis reveals that asymmetric substitutions introduce charge-transfer character, whereas higher oligomers maintain tightly bound excitons with limited delocalization. Overall, functionalized OPP- n chromophores, especially push–pull derivatives of OPP-3, demonstrate favorable optical and excitonic properties for photoredox catalysis, making them promising candidates for CO 2 reduction and hydrogen evolution applications.

A novel diacid monomer, 2,3-Bis-[4′-(4″-carboxymethylene)phenoxyphenylene] (BCPPQ), featuring a rigid cardo-type quinoxaline core and flexible ether-methylene linkages, was synthesized via a two-step process from 4,4′-difluorobenzil. Structural confirmation was achieved through FT-IR, 1 H and 13 C NMR (including DEPT), and HRMS. BCPPQ was then polymerized with various aromatic diamines using triphenyl phosphate in an NMP/pyridine/LiCl system to yield a series of high molecular weight polyamides. These polyamides exhibited excellent solubility in polar aprotic solvents (e.g., DMF, DMAc, NMP) and showed inherent viscosities ranging from 0.16 to 0.25 dL/g. FT-IR analysis confirmed amide bond formation. Thermal studies (TGA/DSC) revealed high thermal stability with decomposition temperatures above 395 °C and glass transition temperatures between 173 and 198 °C. XRD patterns showed broad halos, confirming their amorphous nature. The incorporation of a bulky quinoxaline unit and flexible linkages improved solubility without significantly compromising thermal performance, suggesting their potential for high-performance material applications.

Metal–ligand bonding and noncovalent interactions (NCIs), such as hydrogen bonding or π – π interactions, play a crucial role in determining the structure, function, and selectivity of both biological and artificial metalloproteins. In this study, we employed a hybrid quantum mechanics/molecular mechanics (QM/MM) approach to investigate the ligation of water or cyanide in a mutated myoglobin system, in which the native heme scaffold was replaced with M-salophen or M-salen Schiff base complexes (M = Cr, Mn, Fe). Using our local vibrational mode analysis, particularly local vibrational mode force constants as intrinsic bond strength parameters, complemented with electron density and natural orbital analyses we explored the role of metal–ligand bonding and NCIs in different environments within the myoglobin pocket. Our analysis revealed that metal–ligand bonding, for both water and cyanide ligands, is strongest in the delta form of distal histidine and favors salophen prosthetic groups, as indicated by an overall increase in metal–ligand bond strength. Hydrogen bonding between the distal histidine and ligand also exhibited greater strength in the delta form; however, this effect was more pronounced with salen prosthetic groups. Additionally, the NCIs within the active pocket of the protein were found to be variable, highlighting the adaptability of local force constants. In summary, our data underscore the potential of computational methodologies in guiding the rational design of artificial metalloproteins for tailored applications, with local vibrational mode analysis serving as a powerful tool for bond strength assessment.

Computer simulations of carbohydrates pose a significant challenge due to their heterogeneous chemical structure, high conformational variability, inaccuracies in interaction potentials, and computational inefficiency, which scales particularly unfavorably with chain length compared to other biopolymers. In this work, we present a coarse-grained model designed for Monte Carlo simulations of single polysaccharide chains of realistic lengths (hundreds of monomers or more). The model specifically accounts for the structural features of natural polysaccharides, which are typically built from disaccharide building blocks, and for conformational variability arising from rotations around glycosidic linkages. By extrapolating local conformational properties, thermodynamically correct configuration ensembles are generated, and high computational efficiency is achieved through rapid decorrelation of independent degrees of freedom. As an illustration of the model’s capabilities, we present a set of simulations of keratan, a natural biopolysaccharide belonging to the glycosaminoglycan family. The results indicate that sulfation has a limited impact on chain conformation. Instead, chain stiffness is primarily influenced by syn-exo ↔ anti -ψ conformational transitions in β(1 → 4) glycosidic linkages. The persistence length varies between 6 and 8 nm depending on the degree of sulfation. Moreover, for chain lengths most commonly found in nature, a linear relationship is observed between the number of monomeric units and both the radius of gyration and the end-to-end distance. Finally, we present and discuss the strategy for accounting for ionic-strength-driven alterations of the charged polysaccharide chain, which, when applied to the current case, demonstrate that, under physiological conditions, the long-range electrostatic interactions within the keratan chain can be neglected.

Wastewater contaminants pose serious environmental threats due to their enduring presence and harmful effects on ecosystems, making it essential to implement robust treatment methods before releasing effluents into natural environments. Among the diverse range of treatment technologies available, adsorption processes have proven to be both economically viable and exceptionally effective solutions for wastewater remediation. This research examines the performance of zinc chloride-activated bamboo carbon (BAC) for eliminating Cephalexin antibiotic compounds from contaminated water systems. Brunauer-Emmett-Teller characterization demonstrated that BAC exhibits remarkable structural properties, featuring a large specific surface area of 790 m 2 /g and nanopores measuring 0.8 nm in diameter. Surface morphology analysis through scanning electron microscopy, combined with Fourier transform infrared spectroscopy, revealed diverse functional group distributions across the BAC surface, while zeta potential measurements confirmed negative surface charging characteristics. Laboratory findings demonstrated that BAC exhibited peak Cephalexin uptake performance of 37.56 mg/g. The adsorption behaviour was successfully modelled using Langmuir isotherms (R 2  = 0.9647) and pseudo-second-order kinetic equations (R 2  = 0.999), demonstrating strong agreement between theoretical predictions and experimental observations. These findings establish BAC as a promising material for mitigating antibiotic contamination in water treatment applications. The development of BAC technology represents a significant advancement in sustainable water treatment, as it transforms agricultural waste into a high-performance adsorbent that can simultaneously address both waste management and water pollution challenges. This innovative approach offers a cost-effective alternative to conventional treatment methods while providing superior removal efficiency, positioning it as a next-generation solution for pharmaceutical contaminant remediation in developing nations where antibiotic pollution is increasingly problematic.

Understanding how dynamical behaviour and structural features influence protein function and stability is crucial. While extensive experimental data exist, studying real-time protein dynamics and enzyme catalysis remains challenging. Computational advances have been instrumental in overcoming experimental limitations, enabling molecular-level insights into biological macromolecules. The integration of experimental and computational approaches has proven to be very valuable in protein studies. Here, we demonstrate this synergy by investigating the conformational stability of the urethanase UMG-SP3, which exhibited a lower optimum temperature than expected and rapid loss of activity. Molecular dynamics simulations of the UMG-SP3-substrate complex at various temperatures revealed structural rearrangements outside the optimum temperature range (25–35 °C), leading to loss of the native protein fold and impaired substrate binding. Even at the optimum temperature for activity, the enzyme struggled to maintain a catalytically favourable orientation, aligning with experimental findings. Unfolding profiles were determined through differential scanning fluorimetry. Notably, the computational results provided a rationaly for the structural instability observed experimentally, emphasizing the strength of computational methods in elucidating protein behaviour at the atomic level. This study highlights the importance of combining experimental and computational approaches to deepen our understanding of protein stability and function.

Mixed-ligand manganese (II) (Mn(II)) complexes with the general formula [Mn(INAP) (L)(H 2 O) 2 ] (L = Histidine, Phenylalanine, or Tryptophan) were synthesized in a 1:1:1 M ratio, where INAP denotes isonitrosoacetophenone and L represents an amino acid ligand such as l -histidine, l -phenylalanine, or l -tryptophan. The complexes were characterized using elemental analysis, molar conductance measurements, and spectroscopic techniques including UV–Vis, infrared, and electron spin resonance spectroscopy. The molar conductance values indicate that the complexes are non-electrolytic in nature. FTIR spectral data suggest that both the amino acid and isonitrosoacetophenone ligands coordinate to the Mn(II) center in a bidentate manner via nitrogen and oxygen donor atoms. Electronic absorption spectra and magnetic susceptibility measurements support a distorted octahedral geometry around the central metal ion. Density Functional Theory calculations were performed to obtain optimized geometries, structural parameters, vibrational frequencies, and quantum chemical descriptors of the synthesized complexes. Cyclic voltammetry was employed to study their electrochemical behavior, revealing that the redox potentials are influenced by the chelating nature of the ligands and the electron-donating effects of their substituents. The antioxidant activities of the complexes, which are closely associated with their redox behavior, were evaluated using the DPPH radical scavenging assay. Furthermore, the antimicrobial potential of the complexes was assessed against a range of pathogenic microorganisms.

The calculation of accurate excitation energies and potential energy surfaces of photochemical reactions is a major challenge of current quantum chemistry, especially when one wants to keep the cost low enough to make detailed dynamical simulations affordable. Methods that might be affordable for large complex molecules can be tested against benchmark results for smaller molecules, where accurate benchmarks can be available. Here we report such testing for the excitation and dissociation of the methyl radical, yielding both singlet and triplet CH 2 . The emphasis is on multistate pair density functional theory using compressed-multistate (CMS-PDFT) and linearized (L-PDFT) formulations. We also consider the less affordable XMS-CASPT2 method with the same state-averaged-complete-active-space (SA-CASSCF) reference wave functions, which has seven active electrons in 10 active orbitals. The calculations use state averaging over seven states and a model space that spans the seven lowest SA-CASSCF eigenvectors. We study three on-top density functionals: tPBE, tPBE0, and MC23. Vertical excitation energies, adiabatic excitation energies, and dissociation energies, along with cuts through the potential surfaces along the dissociation coordinate, were computed with the (7, 10) active space. XMS-CASPT2 and L-PDFT with the MC23 functional show consistent and reliable performance for excitation energies, closely reproducing benchmark values, and producing smooth, physically reasonable potential energy surfaces essential for nonadiabatic dynamics simulations, but they are less accurate for bond energies. The L-PDFT calculations with the tPBE functional are more accurate for dissociation energies, but less accurate for excitation energies.

Mycotoxins are naturally occurring toxic secondary metabolites produced by fungi. Aflatoxin B1 (AFB1) is recognized as the most relevant because it was classified as a Group 1 carcinogen and due to its strong association with hepatocellular carcinoma (HCC) in humans. The significant contribution of AFB1-contaminated food to HCC cases, highlights the critical importance of understanding the chemistry and metabolism of this mycotoxin, as its study is hiddenly subordinated as one of the key pillars of attention to the challenges that contaminated food consumption represents to public health and food safety. This review highlights the structural and physicochemical descriptors of AFB1, its metabolism, and mechanisms of toxicity, while also discussing the contemporary control strategies and mitigation approaches aimed to ensure food safety and public health.

While limited coupled cluster theory is formally nonvariational, it is not broadly appreciated whether this is a major issue in practice . We carried out a detailed comparison with de facto full CI energies for a relatively large and diverse set of molecules near equilibrium geometries. Fully iterative limited CC methods such as CCSDT, CCSDTQ, and CCSDTQ5 do represent practical upper bounds to the FCI energy, as do CCSDT-3, CCSDTQ-3, and CCSD(cT). While quasiperturbative approaches such as CCSD(T) and especially CCSDT(Q) may significantly over-correlate molecules if there is significant static correlation, this is much less of an issue with Lambda approaches such as CCSDT(Q) Λ .

The surface electrostatic potential ( V S ( r )) is an established tool for characterization and prediction of sites susceptible to participate in intermolecular interactions. In particular, maxima in V S ( r ) ( V S,max ) have been shown to reflect σ-holes and π-holes, including the electrophilic sites of hydrogen bond donors and halogen bond donors as well as traditional Lewis acids. The characterization of nucleophilic sites on Lewis bases has proven more difficult, and surface minima ( V S,min ) often fail to predict the angular direction of interactions with electrophiles. In this study, it is demonstrated that the predictive capacity of spatial minima in the electrostatic potential ( V min ) is much higher than V S,min for interactions with neutral electrophiles, such as HF, BF 3 , BrF and LiF. V S,min , on the other hand, is better for interactions with ionic electrophiles, such as Li + . This latter observation can be explained by that the position of the V S,min corresponds to the site on the surface that has strongest electrostatic interaction with a point charge. V min performs better for interactions with neutral electrophiles, as the nucleophile interacts electrostatically with the entire charge distribution of the electrophile and not only with that of its electrophilic site; the charge distribution of a neutral electrophile can be approximated by a dipole or a superposition of dipoles, and a dipole interacting with a Lewis base (nucleophile) has its lowest electrostatic energy when it is pointed along the direction of strongest electrostatic field, which generally coincides with the direction of the  V min .

This study investigates the application of quasi-solid-state polymer electrolytes as a candidate to replace liquid electrolytes in dye-sensitized solar cells (DSSCs) for addressing challenges such as electrolyte leakage and counter electrode corrosion. Chitosan, a biodegradable, non-toxic, odorless polymer known for its high mechanical strength, is explored for its potential in this role. To improve the electrochemical performance of chitosan-based polymer gel electrolytes, ZnO nanofillers, specifically ZnO nanorods and ZnO nanospindles synthesized via hydrothermal methods, were incorporated into the chitosan matrix, which was mixed with KI and I 2 in CH 3 COOH. The polymer gel electrolyte was then characterized using cyclic voltammetry, Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The integration of ZnO nanoparticles enhances ionic conduction by providing additional pathways. The results show that incorporating 0.25 wt% ZnO nanorods into the polymer matrix yields anodic and cathodic peak currents of 6.68 mA and −9.37 mA, with a half-wave potential of 0.383 V (vs. Ag/AgCl). In comparison, incorporating 0.5 wt% ZnO nanospindles produces anodic and cathodic peak currents of 7.72 mA and −10.3 mA, with a half-wave potential of 0.380 V (vs. Ag/AgCl).

An overview is given of the most important contributions to the development of quantum chemistry since the first paper by Heitler and London in 1927. In this pioneering work it was shown that the physical nature of chemical bonding is a quantum theoretical phenomenon that can only be understood on the basis of the quantum theory presented by Heisenberg and Schrödinger in 1925/1926. The direct influence on chemistry was minimal at the beginning, and it was initially physicists who solved problems in chemistry. These were among others the triplet state of O 2 by Lennard-Jones, the aromatic stability of benzene by Erich Hückel and the energy contributions of chemical bonding by Hellmann, who wrote the first book on quantum chemistry in 1936. The importance of quantum theory for chemistry was recognized by Linus Pauling, who succeeded in translating the complicated mathematical representation into simple models that were useful for many areas of chemistry. His book “The Nature of the Chemical Bond” was the first to bridge the gap between quantum theory and the broad field of chemical research. With the introduction of computers, quantum chemistry has undergone continuous development, from which it still benefits today. The Valence Bond theory favored by Pauling was largely replaced by the Molecular Orbital theory, as the computer calculations are much faster and the symmetry of the wave function contains fundamental information that can be used to explain the structure and reactivity of molecules. Orbital symmetry forms the basis of the most important models in chemistry, on which the frontier orbitals of Fukui and the orbital symmetry of Woodward and Hoffmann are based. Parallel to the development of the hardware, the methodological foundations and programs were developed with which practically all molecular properties can be calculated. In the 2000s, molecular orbital methods were replaced by density functional methods as the most widely used tool of computational chemistry.

Hydrogen bonded complexes and their lithium bonded analogues are investigated using DFT CAM-B3LYP quantum chemistry methods. The accuracy of DFT is verified by CCSD(T) calculations. Structures, binding energies, and Hirshfeld charge and spin densities for several charged closed shell and neutral open shell oxygen-containing complexes with O–H⋯O and O–Li⋯O bonds are compared. We also studied H-bonded and Li-bonded C–H⋯C and C–Li⋯C complexes in which the hydrogen and lithium bond donor and bond acceptor act through carbon-containing groups. Attention is paid to the bonding character in the model (H 3 C) 2 –CH–Li–CH–(CH 3 ) 2 (diisopropyllithium) doublet. Its binding energy with respect to the isopropyllithium and the isopropyl radical is −45 kJ/mol. The potential energy curve for the transfer of the lithium atom between the two carbon atoms shows double minima with a barrier of 11 kJ/mol. The Hirshfeld charge and spin density analysis shows that the charge transfer from the isopropyl radical to the isopropyllithium molecule occurs, and in combination with electrostatic interaction and (about 25 %) dispersion contribution are responsible for the formation of the Li-bonded (H 3 C) 2 –CH–Li–CH–(CH 3 ) 2 complex.

Smart wound dressings that respond to the wound environment have emerged as innovative therapeutic platforms, aiming to control infection, reduce inflammation, and promote vascularization for effective healing. Herein, an innovative eutectic system combining acetamide and allantoin (AAM) integrated with sericin peptides (SS) for enhanced wound healing applications is reported. The binary AAM system exhibited superior physicochemical properties, utilizing acetamide’s anti-inflammatory effects and allantoin’s regenerative capabilities. The binary AAM system exhibited superior physicochemical properties, with molecular modeling revealing optimal donor-acceptor interactions and FTIR confirming complex intermolecular networks in SS-incorporated scaffolds. The SS-containing scaffolds showed significantly enhanced wound healing efficacy in a mouse model compared to non-functionalized AAM systems, with accelerated wound closure through synergistic interactions. This integration of eutectic systems with bioactive peptides presents a promising platform for advanced wound healing therapeutics, offering improved drug delivery and tissue regeneration.

The study focuses on the fabrication of multifunctional food packaging membranes consisting of Chitosan (CS) and Pectin (PC) as the polymer blend reinforced with TiO 2 nanoparticles (NPs) integrated with green tea extract (GTE). For this purpose, four films (GTE 1–GTE 4) were created by combining GTE, which were extracted using different conditions. Results indicated that the physicochemical and functional properties of CS/PC blended membranes were improved by adding TiO 2 NPs and GTE. Scanning Electron Microscopic (SEM) images showed reduced surface roughness and minimized particle agglomeration in the presence of GTE compared to the CS/PC/TiO 2 film. The incorporation of TiO 2 NPs and GTE has notably enhanced the thermal and mechanical properties of the films. Furthermore, films integrated with GTE and TiO 2 NPs demonstrated enhanced water and oil barrier properties, accompanied by a reduction in moisture content, water absorption, and surface hydrophilicity upon incorporating GTE. In addition, the combined incorporation of TiO 2 and GTE significantly reduced light transmission in the visible region. The GTE 4 film exhibited the highest antioxidant activity among all tested films. The antibacterial activity was evaluated using the disc diffusion method against Gram-positive ( Bacillus sp .) and Gram-negative ( Escherichia coli ) bacteria. The GTE 4 film, demonstrated effectiveness against both types of bacteria. Additionally, pH-dependent color changes were observed in GTE 4, indicating its potential applications as a pH-sensing food packaging material. GTE 4 was also employed for packaging red grapes to extend their shelf life, and the results highlighted the film’s potential for active packaging applications, highlighting its enhanced functional properties.

The dichotomy whether in Quantum Chemistry insight and numbers are to be placed on equal footing is situated in a historical perspective starting from Coulson’s famous quote “Give us insight, not numbers” to Neese’s recent adaptation “Give us insights and numbers”. In parallel, the problem of the chemical interpretation of complex computational results in terms of classical chemical concepts is addressed starting from Mulliken’s quote that “the more accurate the calculations became the more concepts tend to vanish in the air”. Conceptual Density Functional Theory is one of the techniques which avoids the latter issue by its density based approach which can be applied to computational results of any level of sophistication. The crucial role of response functions of the energy E with respect to perturbations in the number of electrons N and/or external potential v ( r ) is thereby highlighted. However a new confrontation “insight versus numbers” appears. When gradually refining the evaluation of these descriptors, in order to pass from a qualitative to a quantitative level, it turns out from our previous studies that either minor influences show up, or that also fundamental issues may arise hidden in the definition and the physical background of the response function. The derivative discontinuity of the E vs. N curve hereby plays a fundamental role. This issue is documented scrutinizing a series of recent studies on the analytical evaluation of the three second order response functions: the linear response function, the Fukui function and the chemical hardness. They are shown to behave in a fundamentally different way under refinement. For the linear response function, the pure second order v functional derivative of the energy, no fundamental problems arise: when passing to a full analytical evaluation an increasing level of complexity of the equations is observed leading however to a smooth convergence. In the Fukui function case, involving a mixed N and v energy derivative, the issue with the E = E ( N ) curve and N derivative can be circumvented by directly deriving the electronic chemical potential with respect to v using a Maxwell type relation. Finally for the chemical hardness involving the pure second order N derivative, a fundamental problem arises due to the derivative discontinuity when refining the venerable Parr-Pearson parabolic E = E ( N ) curve. It forces us to stick to its result identifying the hardness as the (band) gap. On the other hand the analytical expression yields a “condition” that Density Functional Approximations should obey. It is shown how its implementation leads to a straightforward estimate of their delocalization error, on the road for further improvement of DFAs. The inclusion of temperature may be a way out for further refining the chemical hardness and all other response functions involving second or higher order N derivatives, the simplest case being the dual descriptor. Overall this evolution reflects the basic characteristics Löwdin’s accuracy vs. refinement graph.

The International Year of Quantum Science and Technology (IYQ) publicizes and celebrates the centenary of quantum mechanics (QM). In this essay, I demonstrate that the assemblage of 17 Nobel Prizes in Chemistry awarded since 1960 that are relevant to theoretical and computational chemistry corroborate the literature conclusion that there was a 20th century Quantum Chemistry Revolution. A similar analysis is made for the Instrumental Revolution. These analyses are atypical for assessments in the history of science in that rely on Nobel Prize data. It is the congregation of Nobel Prizes that is a telling pointer to a revolution in science, not the examination of any one Nobel Prize.

As the atomic theory of matter became more established and accepted by the majority of the scientific community, chemists began to dream about the possibility of understanding the physical and chemical properties of different substances in terms of their microscopic composition. Identifying the constituent elements of a substance and their respective proportions allowed chemists to characterize it by a “ chemical formula .” It did not take long for chemists to realize that substances could have different properties even though they had the same “chemical formula” and to conclude that it was not enough to identify the constituent elements of a substance. It was essential to determine how the atoms of those elements were arranged spatially. Thus, chemists began to realize that the physical and chemical properties of a substance were closely related to its “ molecular structure .” The dream now seemed less impossible and more fascinating: how to arrange a certain group of atoms spatially in order to obtain a molecule with specific physical and chemical properties? However, in addition to knowing the spatial arrangement of the atoms in a molecule, it was necessary to know how these atoms are connected, that is, what the “ chemical structure ” of the molecule was and what was the origin of the “ chemical bond ”. The end of the century before last and the first quarter of the last century were the scenery of a fantastic revolution in our knowledge of the atomic structure of matter. Benefiting from this development, chemists began to have at their disposal powerful instruments for the microscopic analysis of the macroscopic properties of chemical systems: quantum mechanics as well as classical and quantum statistical mechanics. Finally, in the last 40 years, with the availability of personal computers and sophisticated multifunctional “software”, the dream began to become reality, and the development of what we now call Quantum Chemistry had an enormous impact on chemistry. However, in order to have a clear measure of the extent of this impact, it is essential to reconstruct the environment in which Chemistry found itself at the end of the 19th century, with all its difficulties and uncertainties. Only then will the reader be able to understand the incredible change brought about by the application of quantum mechanics to Chemistry. This reconstruction will be done by following the evolution of three concepts that form the pillars of modern chemistry: molecular structure, chemical structure and chemical bonding.

Molecular topology fundamentally influences self-assembly, molecular recognition, and dynamic behavior in chemical systems. Among topologically nontrivial architectures, Möbius molecules – defined by a non-orientable, fully conjugated cyclic backbone with an odd linking number (Lk) – represent a unique class of π-conjugated macrocycles distinct from geometrically twisted analogues. Their one-sided surface and topological singularity confer exceptional properties, including intrinsic chirality, delocalized electronic pathways, and unconventional charge transport characteristics, positioning them as promising platforms for applications in optoelectronics, chiral sensing, and molecular electronics. Despite significant synthetic challenges arising from ring strain and conformational instability, recent advances in dynamic covalent chemistry, metal-templated cyclization, and heteroatom incorporation have enabled the construction of stable Möbius nanobelts and heterocyclic macrocycles with tunable redox and photophysical properties. Beyond discrete molecules, Möbius topology has also been extended to supramolecular assemblies and interlocked systems, broadening the functional scope of these structures. This review surveys recent progress in the design, synthesis, and functional exploration of Möbius systems, highlighting the critical role of topology in shaping their structure–property relationships and their emerging impact on supramolecular chemistry and molecular materials science.

The paper presents a number of properties of unsaturated polyester resins based on the post-consumer PET recyclate modified with iron(II) clathrochelate, such as thermal, mechanical, optical and visual. The iron compound was used as an accelerator instead of toxic low-molecular cobalt salts, commonly applied for curing of unsaturated polyester resins being also responsible for giving the resin materials an orange-red colour depending on the used amount. Moreover, the iron clathrochelate proved to be an ideal agent added to the polyester resin, giving it antimicrobial properties. Cytotoxicity tests showed that the tested materials were safe and did not cause any undesirable effects in contact with skin fibroblasts. Due to the use of the compound that gives polymers such broad properties, new perspectives are opening up in the preparation and application of polyester materials.

Carbon quantum dots (CQDs) are carbon-based nanoparticles which are less than 10 nm in size and are characterized by having modulable properties of luminescence and conductivity while presenting low toxicity, high water solubility, and biocompatibility, among others. These characteristics make them a good option for possible applications in the industrial, chemical, and biomedical fields. In this study, carbon quantum dots were synthesized using juices of seven different fruits as precursors. The syntheses are carried out by microwave-assisted hydrothermal reaction at 200 °C, and reaction mixtures are purified by column chromatography, followed by characterization via absorbance, fluorescence, infrared spectroscopy and transmission electron microscopy. Comparison of relative concentration of CQDs after 2, 4, and 6 h of reaction show that the best quantum yield obtained (6.3 %) corresponds to the mandarin lime after 6 h pyrolysis (with excitation at 410 nm and maximum emission at 505 nm) with a 4.1 ± 0.8 nm particle size determined via transmission electron microscopy. The synthesized CQDs are shown to be usable in fluorescence bioimaging of Escherichia coli when excited at 450–490 nm, while few or no significant emission is observed at other excitation wavelengths (365 nm and 546 nm), which establishes complementarity and non-interference with other dyes that are used in bioimaging.

Quantum chemistry plays a fundamental role in unraveling the mechanisms by which biological systems sense and use light, driving functions such as light harvesting and energy conversion, and photoreception and signaling. In this Perspective, we first present the fundamental physical principles underlying the light-induced biological functions. We then focus on the key theoretical frameworks and multiscale modeling strategies based on quantum chemistry that enable a detailed, atomistic description of the processes initiating the biological response to light. Special emphasis is placed on three fundamental photophysical and photochemical processes (excitation energy transfer, photochemical reactions, and electron transfer) which form the core of photoactivation mechanisms in biological systems. By highlighting the advances and challenges associated with the quantum chemical modeling, we demonstrate its essential contribution to deepening our understanding of photoinduced biological function and point to future directions for methodological innovation.

This research was undertaken to study pyrolysis of palm oil using of thermally activated Lampung natural zeolite (LNZ) as catalyst and aluminum granules as heat exchanger. Natural zeolite was activated by calcination at different temperatures of 600, 700, and 800 °C for 8 hours. The activated zeolites were then characterized using XRD and SEM and then used as catalyst together with aluminum granules as heat exchanger. A series of experiments were conducted using 200 mL oil, 5 g catalyst, and 5 g heat exchanger, and the performance of the method was evaluated based on the time required for the first flow of Bio Crude Oil (BCO), the yield, and chemical composition of the BCO. The experimental results demonstrated that the use of heat exchanger led to a significant increase in the pyrolysis rate, as indicated by the shortening of the time for the first flow of BCO. It was found that without heat exchanger, 19 minutes was required for the first flow of the BCO, and it was reduced to 12 minutes (36.84 % time reduction) with the use of heat exchanger. Improvement was also achieved in terms of BCO yields, with increases from 43.5 % without heat exchanger to 53.5 % with heat exchanger. In terms of chemical components of the BCO samples, no significant difference was observed, in which hydrocarbons (biohydrocarbons), acids, alcohols, ketones, and esters are the five main components composing the samples. In all BCO samples produced with the use of activated zeolite, biohydrocarbons exist as the main component, with the highest content (85.40 %) was produced from the experiment with the use of LNZ calcined at 800 °C as catalyst. The existence of biohydrocarbons as the main components of the BCO obtained highlights the promising potential of activated LNZ as catalyst for biohydrocarbons production and significant effect of calcination temperature. The advantages of heat exchanger, in terms of acceleration of pyrolysis and BCO yield, are also worth noting.

In this mini-review I look into the physics underlying the theory of electronic structure of atoms and molecules. Quantum mechanics is needed to understand the structure of the periodic table. Special relativity is indispensable for a correct description of the chemistry of the heavy elements. With increased accuracy of quantum chemical calculations, it is natural to ask if chemistry needs more physics.

Over the past 30 years, ionic liquids (ILs) have emerged as a versatile class of compounds, bridging fundamental research and applied chemistry. This work offers a historical perspective on ILs, mainly covering fundamental and structural aspects, filtered through the author’s personal experience and with no claim of completeness, focusing on four milestone topics: nanostructuring at the mesoscopic level, nanostructuring at the atomic level via intermolecular nuclear Overhauser effect (NOE) studies, the unexpected ability of ILs to selectively dissolve gases, and their potential in promoting sustainable chemistry. These aspects have expanded our understanding of ILs beyond their initial classification as merely molten salts. Among the many challenges ILs face, sustainability is a key factor shaping their present and future applications. As environmental policies evolve, IL-based processes must be evaluated through life cycle assessment and green metrics. However, sustainability extends beyond toxicity and biodegradability, requiring a broader assessment of ecosystem impact and societal acceptance. Addressing these challenges demands a multidisciplinary approach, integrating chemistry with environmental science and engineering. By embracing these perspectives, ILs can continue to drive greener and more efficient chemical processes in the 21st century.

This study addresses the urgent need for sustainable alternatives to conventional plastic food packaging by developing and evaluating novel starch-based coatings enriched with chitosan and bacterial nanocellulose (BNC) derived from food waste. These coatings were applied to unripe bananas and their effectiveness in extending shelf-life was assessed over 21 days under controlled conditions. The results demonstrate that the coatings, particularly those containing chitosan, significantly reduced weight loss (up to 35 %), preserved firmness (maintaining 35 % higher firmness), and delayed the increase in reducing sugars (up to 63 % reduction at day 14), effectively doubling the shelf-life of bananas. The superior performance of chitosan-containing coatings is attributed to their film-forming properties, creating a modified atmosphere that retards ripening. This research highlights the potential of valorizing food waste into sustainable, high-performance polymeric coatings for food preservation, contributing to a circular economy in the food industry. Further research is needed to optimize the coatings for long-term effectiveness beyond 14 days.

In this perspective article, we discuss the link between minimum energy paths and activation parameters for reactions on complex potential energy surfaces involving many possible local minima, as are typically found for enzyme-substrate complexes. Such systems are frequently tackled with hybrid QM/MM methods in order to characterize reactivity. The link between local energy barriers along a minimum energy path, the so-called exponential average of such local energy barriers, and multiconformational transition state theory is discussed. Also, it is shown that in case of positive skewness of the distribution of barrier heights across sets of minimum energy paths, exponential averaging converges relatively quickly with the number of paths used.

Zeolitic imidazolate frameworks (ZIFs) are a new subclass of metal-organic frameworks (MOFs) with a structure isomorphic to that of aluminosilicate zeolites. The zeolitic imidazolate framework-8 (ZIF-8) offered greater surface area and better hydrophobic properties, making it suitable for catalysis. The present study describes that ZIF-8 was synthesized in an aqueous solution by mixing 2-methylimidazole with Zn nitrate hexahydrate in deionized water. To enhance the basicity and performance of the ZIF-8 catalyst, a series of K-loaded ZIF-8 catalysts (K/ZIF-8) were prepared with varying amounts (5–10 wt%) of KOH content. Powder XRD, FTIR, XPS, HRTEM, TPD, and BET surface area measurement techniques have been used for structural and morphological characterization of the catalyst. The prepared K/ZIF-8 catalyst is employed as a heterogeneous catalyst to carry out glycerol (GL) valorization with dimethyl carbonate (DMC) to form glycerol carbonate (GLC). Various reaction parameters that affect the GLC yield, including DMC/GL molar ratio, KOH loading, catalyst amount, and temperature, have been studied during the reaction. Under the optimized reaction conditions of 10-K/ZIF-8 catalyst (5 wt% concerning GL), a DMC/GL M ratio of 3:1 in 0.5 h afforded up to 95 % GLC as an exclusive product. Even though the K metal ion is hygroscopic, the prepared catalyst demonstrated better water resistance (up to 4 wt% concerning GL) owing to organic group functionality. Moreover, the solid catalyst could be recycled up to three times without significantly decreasing activity.

In this study dihydropyrazole based derivatives were synthesized from substituted chalcone through Michael addition reaction. Urease inhibition activity of the compounds was evaluated, revealing that most compounds exhibited moderate inhibition. Among the synthesized compounds, 2b, 2m, and 2n demonstrated exceptional potency with IC 50 values of 5.21 ± 0.91 µM, 6.21 ± 0.10 µM, and 5.21 ± 0.81 µM, respectively. Thus, these findings suggest that dihydropyrazole represent a promising scaffold for the development of novel urease inhibitors.

The proton motive force (PMF) across the inner mitochondrial membrane delivers approximately 0.2 eV of energy per proton, powering the F o F 1 -ATP synthase molecular motor. Here, we provide a detailed accounting of how this energy is utilized: Approximately 75–83 % is transduced into the chemical free energy of ATP synthesis, while the remaining 17–25 % is dissipated through internal friction, viscous drag, proton leakage, electroviscous effects, elastic deformations, and information-theoretic costs. Each dissipation channel is quantitatively evaluated, revealing that internal friction in the F 1 motor is the dominant loss mechanism. In this work, we did not account for the possible energy contribution due to the intrinsic electrostatic potential of the enzyme itself. In addition to this energy bookkeeping, we also examine the quantum mechanical constraints on the F o unit’s rotation. We find that, as can be expected, the energy spacing between quantized rotational states is several orders of magnitude smaller than thermal energies at physiological temperature, and that the tunneling probability through rotational barriers is practically zero. Furthermore, the biological rotation speed (∼100–650 revolutions per second (rps)) is between one and three orders of magnitude below the quantum limit implied by quantization of angular momentum of the c-ring (which would have been ca . 13,000 to 62,000 rps (depending on the size of the c-ring (17–8 subunits, respectively)) in the first rotational energy level of the c-ring). Nevertheless, experimental estimates of the rotation rates in isolated c-rings suggest rates in the vicinity of 43,000 rps, right within our theoretical quantum estimates. However, ATP synthase as a whole operates firmly within the classical regime, despite its nanoscale dimensions, which highlights its evolutionary optimization for robust and efficient energy conversion at the quantum–classical boundary. This is the result of the rotatory coupling between the F o and the much slower F 1 unit. ATP synthase’s purely classical behavior showcases a remarkable evolutionary optimization of one of life’s most essential rotary motor engineered so as to thrive far from the quantum limit, securing its function against the uncertainties of the quantum world. As Schrödinger stated in What is Life? (1944): “ The submicroscopic world is full of fluctuations. But in large aggregates of atoms, the law of large numbers ensures that these fluctuations become negligible ” a prediction directly confirmed here in the context of the rotational stability of the F o  unit.

This paper reflects the authors’ personal journey in applying quantum chemistry methods to understand one of the most important processes in nature: enzymatic catalysis. The integration of quantum mechanics with biomolecular simulations represents one of the most significant advances in computational enzymology over the past few decades. This approach has revolutionized our understanding of enzyme function and catalytic mechanisms, and has provided powerful tools for enzyme design and optimization. Combined quantum mechanics/molecular mechanics (QM/MM) methods have transformed theoretical studies of enzymatic reactions from qualitative descriptions to quantitative predictions, capable of guiding experimental work with unprecedented accuracy.

Increased use of pesticides has proven to be a serious threat despite their benefits, due to their prolonged persistence in the environment that poses serious toxic effects on non-target species as well as disrupts the ecosystems by contaminating soil and water. Current review covers the role of different metal oxide, chalcogenide, nitride and other novel nanomaterials in the degradation of pesticides. Contribution of nanotechnology has been emphasized by including several degradation mechanisms such as charge transfer, adsorption and role of surface defects or states. Recent advancement in the field has been focused by incorporating the examples of novel and 0D, 1D and 2D functional nanomaterials such as graphene, carbon nanotubes, carbon quantum dots, MoS 2 and their composites. Nanotechnology driven enhancement of selectivity and reactivity for pesticide breakdown, by surface modification and bandgap engineering has been included. As, in the current era the detection of trace pesticide residues becomes crucial, this review further covers the progress of nanotechnology-based sensors’ implementations in pesticide residue detection and environmental monitoring. Environmental impact and safety of nanotechnology in pesticides degradation has been highlighted by covering the aspects like potential risks and toxicity of nanomaterials. The article concludes with the important points like regulatory consideration and safety guidelines of using nanomaterials for environmental applications such as pesticide degradation.

4-Amino-2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) radical was linked to perylene-3,4:9,10-bis(dicarboximide) (PBI) at varying distances and orientations. PBI-TEMPO dyads with the radical linked at the bay-position show a charge transfer absorption band in the UV−vis absorption spectra. With increasing solvent polarity, a fluorescence quenching is observed for these dyads, whereas for a derivative with TEMPO attached at the imide-position, such polarity dependency for fluorescence spectra was not observed. Steady state and femtosecond/nanosecond time-resolved optical spectroscopy confirmed the occurrence of radical-enhanced intersystem crossing (REISC. k ISC  = (23 ps) −1  − (0.5 ns) −1 ). The lifetime of the 3* PBI state ( τ T  = 1.0–7.6 μs) depends on the distance and orientations between TEMPO and PBI units. The results indicate that stronger electron spin–spin dipolar interaction ( v dd ) between the radical and the chromophore improve REISC efficiency. Time-resolved electron paramagnetic resonance (TREPR) spectroscopy demonstrates different electron exchange interactions ( J TR ) in the dyads, varying from ferromagnetic interaction corresponding to strong exchange regime to weak antiferromagnetic exchange interaction with increasing the distance between PBI and TEMPO units. Transient-nutation experiments further clarify the TREPR signals. DFT calculations indicate that changes in the dyad structure alter the exchange coupling from ferromagnetic ( J TR  = 0.47 cm −1 ) to antiferromagnetic ( J TR  = −0.03 cm −1 and −0.01 cm −1 ).

Electrochemical (EC) sensors are pivotal for quantitative analysis as well as detection of the chemical and biological analytes across different fields, such as biomedical applications, food safety, and environmental monitoring etc. The present review discusses the electrochemical sensor of different types (potentiometric, impedimetric, amperometric) and their key mechanisms. The enhancement of sensors performance as well as efficiency has also been explored in detail. Integration of nanomaterials and nanocomposites offers improved selectivity, sensitivity, faster response time and facilitates the sensor miniaturization to the nanoscale. Specific applications, including the detection of (i) disease biomarkers, (ii) pesticides, (iii) pollutants, (iv) contaminants, (v) glucose and (vi) pesticide residues, are detailed. Present review further covers the limitations and the challenges of nanomaterials’ utilization in fabrication process of electrochemical sensors, including their (i) stability, (ii) biocompatibility, (iii) scalability and (iv) manufacturing related constraints. Future perspectives, encompassing advances in hybrid nanomaterials, nanocomposites, and the incorporation of AI and IoT, are also discussed. The present comprehensive review aims to be beneficial for all the researchers/scientists working in similar fields, guiding the development of electrochemical sensors with higher potential for novel applications.

Chiral nanostructured materials have emerged to be an influential class of high-performance materials used in areas ranging from enantioselective sensing, separation, and catalysis to optoelectronics. The materials are highly sophisticated and involve chiral metal-organic frameworks, covalent organic frameworks, carbon dots, and quantum dots etc. Owing to properties such as enantioselectivity, reproducibility, and catalytic properties, facilitating their incorporation into multifunctional systems these materials offer remarkable enantiomeic separations, environmental monitoring, and sustainable energy. In the past few years, various synthetic strategies such as chiral ligands, templating techniques, and environmentally friendly synthetic methods have been investigated to achieve improved chiral materials. Great advances have been achieved in chromatographic performance and scalability toward chiral membranes, composite materials, and MOFs- and COFs-based stationary phases. Furthermore, multi-mode platforms combining fluorescence, magnetism, and other recognition approaches show vast potential for label-free real-time enantiomeric detection. Here, we review the interdisciplinary advancement in the area of nanostructured chiral materials focusing on synthetic strategies, characterization, and enantiorecognition performance of common chiral organic compounds and drugs.

Diazoalkanes are ambiphilic molecules that may react with electrophiles at carbon to give diazonium ions, with nucleophiles at nitrogen to yield azo compounds, or with dipolarophiles to produce pyrazolines. By studying the kinetics of the reactions of methyl diazoacetate and dimethyl diazomalonate with benzhydrylium ions (Ar 2 CH + ) of known electrophilicity E , we determined their one-bond nucleophilicity parameters N and s N using the equation lg k 2 (20 °C) =  s N ( N  +  E ) (eq. (1)). Similarly, the electrophilicity parameters E of these diazoesters were obtained by measuring the rate constants of their reactions with one-bond nucleophiles of known N and s N . These reactivity parameters enable the calculation of rate constants for 1,3-dipolar cycloadditions with dipolarophiles, which proceed stepwise with rate-determining formation of zwitterionic intermediates. Concerted cycloadditions proceed faster than calculated by eq. (1), and the difference between the observed rate constants (Δ G ‡ exptl ) and those calculated by eq. (1) (Δ G ‡ eq. 1 ) gives the energy of concert (Δ G ‡ concert  = Δ G ‡ eq. 1  − Δ G ‡ exptl ). Contrary to earlier reports, cycloadditions of methyl diazoacetate and dimethyl diazomalonate with enamines proceed stepwise through initial azo couplings. This involves enamine attack at the π* (N=N) orbital of the diazoalkane, oriented perpendicularly to the commonly considered 3-center 4-electron π-system. Since this orbital was previously ignored, the common FMO analysis of the reactions of 1,3-dipoles of the propargyl anion type requires revision. A new ordering system for 1,3-dipolar cycloadditions is proposed.

Breath research has demonstrated that mammals, including humans, produce methane (CH 4 ) due to microbial activity in the gastrointestinal tract under anoxic conditions. Overall, humans are classified as methane producers if they exhale methane concentrations at least 1 ppmv higher than the environmental level. Here, we present the first measurements of CH 4 concentration and its carbon stable isotope composition (δ 13 C-CH 4 ) in the breath of Costa Rican individuals. Samples were collected from a total of 51 volunteers aged between 5 and 72 years, using Tedlar bags, and analyzed using laser spectroscopy. We found that 56 % and 62 % of female (N = 14) and male (N = 16) individuals, respectively, can be considered as methane producers and emitted CH 4 concentrations up to 37.9 ppmv with δ 13 C-CH 4 values up to −75.0 ‰. The δ 13 C-CH 4 values also confirmed that the exhaled methane was produced by all the individuals evaluated. Despite our data being preliminary, our work can be useful for future breath studies in Latin American populations that incorporate isotopic techniques (e.g., laser spectroscopy and isotope ratio mass spectrometry) and consider how dietary factors or intestinal microbiota may influence levels of methane emission among different age groups .

Endocrine disruptors are a broad area of concern and is a threat to humanity when present in the environment. With the rise of industrialization and globalization, there has been an increase in the release of endocrine-disrupting agents such as phenolics and phthalates into the environment. This has made it a challenging task for research groups worldwide to remove these agents from water. An herbicide 2,4-dichlorophenoxy acetic acid has been chosen as the target for degradation which is used commonly for the control of weeds with broad leaf in the fields. These materials get into the aquatic system by water run-off during rain and percolate into the soil (LD 50–639 mg/kg to 1,646 mg/kg). Hence, in this study, we have employed nitrogen-doped ZnO nano-bundles for a visible light induced photocatalytic degradation of 2,4-D. The Nano Janue-like N-doped ZnO bundles (NZnO) were prepared and analyzed by various characterization techniques. The NZnO nano janue bundles were found to be in an arranged structure (particle size – 10–12 nm, band gap energy – 3.01 eV). The photocatalytic removal studies were conducted with an optimum catalytic dosage of 10 mg/10 mL. The kinetics were conducted for the different concentrations of 2,4-D (10–25 ppm). The kinetic rate constant was calculated as 5.64 to 2.75 × 10 −3  min −1 , the reaction followed a pseudo-first order kinetics. The COD removal was found to be 93.75 % for 10 ppm 2,4-D. This study paves the way for employing NZnO nano janue bundles as photocatalysts for environmental remediation under visible light irradiation.

SnO 2 and Carbon (C), Nitrogen (N) and Sulphur (S) – doped SnO 2 (CNS@SnO 2 ) samples were synthesized via a hydrothermal and grinding method respectively. The thiourea was used as precursor for all the three dopant ions whose concentration was varied as 0.03 wt%, 0.06 wt% and 0.09 wt%. PXRD results confirm the replacement of high density oxygen atom by low density C and N atoms. UV–vis spectroscopy confirms the incorporation of C, N and S dopant ions by the shift in absorption edge towards visible region. The oxidation states of the dopant ions were confirmed as C 2− , N 3− and S 6+ by the X-ray photoelectron spectroscopic technique. The presence of N in the sample was also confirmed by FTIR technique. The optimum dopant concentration was found to be 0.06 wt% of thiourea. The higher value of photocurrent efficiency, photocurrent density and lower value of electrical energy per order confirms the efficiency of CNS@SnO 2 (0.06 wt%) sample due to the favourable function of Fermi energy (E F ) in the SnO 2 lattice.

Coffee beverages are consumed worldwide and produce considerable quantities of by-products from industrial processing every year. The present study identified 20 bioactive compounds in fresh coffee ( Coffea arabica L.) husk and mucilage extracts from industrial processing. Ultra-high performance liquid chromatography coupled with diode array detection and triple quadrupole mass spectrometer (UHPLC-DAD-TQ/MS) was used for the profile of phytochemicals. Using ethanol (EtOH) as a green solvent, the extraction efficiency was compared with acetone and methanol (MeOH). Higher concentrations of Hydroxybenzoic Compounds (HBC) were found in husk than in mucilage and can be efficiently extracted with EtOH at 70, 80 and 90 %, with no significant differences with MeOH and acetone. Vanillic acid can be efficiently extracted from husk when 80 and 90 % EtOH is used. Rutin, an important non-anthocyanin Flavonoid Compound (FC) due to its health benefits, can be extracted at all concentrations of EtOH with equal results compared to acetone and MeOH. Ethanol seems to be a promissory ¨green¨ solvent for extracting phenolic compounds, achieving similar extraction yields when compared to acetone and MeOH. The coffee husk and mucilage extracts could be used in the food, pharmaceutical and other industries.

An innovative ligand NTADBrP was employed for the first time in spectrophotometric methods for the simultaneous determination of Fe(III) and Ni(II) ions. Fe(III) and Ni(II) ions were complexed as NTADBrP complexes and the maximum absorption was observed at 615 nm and 642 nm for Fe(III) and Ni(II) respectively. The linear ranges of Beer’s law for Fe(III) and Ni(II) were 2–50 ppm and 1–40 ppm respectively. The molar absorptivity of the complexes was 5.661 × 10 4  L mol −1  cm −1 and 4.707 × 10 4  L mol −1  cm −1 for Fe(III) and Ni(II) respectively. The reproducibility of the method for Fe(III) and Ni(II) showed good precision (RSD = 1.42 % and 1.10 % at 20 ppm) as well as accuracy (recovery = 99.0 %, 98.96 %). For the best concentration of the reagent (3.0 × 10 −4  M), the optimal pH for Fe(III) was 4, and 6 for Ni(II). Various metal ions were tested for their potential interference (Cr 3+ , Cu 2+ , Co 2+ , Hg 2+ , Pb 2+ , and Cd 2+ ) and found effectively masked by suitable masking agents. The method was applied successfully to the determination of iron in pharmaceutical samples using other standard methods for comparison. In addition, significant antioxidant activity against oxidative attack on plasmid DNA showed by NTADBrP.

Water-soluble flexible organic frameworks (FOFs) can be constructed from multi-topic cationic, anionic or neutral, hydrophilic components through the quantitative formation of dynamic hydrazone or disulfide bond. FOFs have been revealed to possess intrinsic porosity, hydrophobic interior, and controllable nano-sizes. They function well as homogeneous nano-sponges for including proteins, DNA, residual drugs, such as neuromuscular blocking agents and heparins, and endotoxin. Their nano-sizes endow the frameworks with good ability for intracellular delivery of the included proteins and DNA and for the design of self-delivering prodrugs, while efficient inclusion of residual drugs can be utilized to develop FOF antidotes for inactivating the residual drugs. This review summarizes the design, preparations, characterizations and biofunctions of this family of dynamic covalent polymers.

A spectrophotometer has been used to research the rate at which glycine amino acids oxidize by hexacyanoferrate (abbreviated as HCF) III ions in an alkaline watery medium, catalyzed by Iridium (III) chloride and has a steady ionic strength of 0.5 mol dm −3 at a temperature of 35 ± 0.1 °C. First-order rate dependency kinetics were identified to govern the reaction’s progression for [HCF(III)], [OH] − , and [IrCl 3 ]. The rate of reaction decreases as the amino acid concentration rise, according to our findings. Ionic strength of reaction mixture has a beneficial effect on reaction rate. The reaction was observed at four distinct temperatures in order to assess additional activation parameters. Amino acid: HCF (III) = 1:2 is the reaction’s stoichiometry. Glyoxylic acid was discovered as the reaction’s oxidation product using TLC spectroscopy and an organic solvent technique. A suitable mechanism could account for all of the experimental results. It is believed that iridium trichloride and substrate (abbreviated) create a complex as the reaction progresses. To validate the results an established rate law is used.

Increased interest in waste valorization underscores the potential of biowaste (BW) from small-scale food establishments as a resource within the circular economy. This study aimed to characterize the physicochemical properties of BW generated by three small restaurants in Costa Rica to evaluate its suitability for value-added applications. Eighteen samples from each restaurant were randomly collected, processed, and analyzed for moisture, fiber, starch, protein, calorific value, and other properties following standardized laboratory protocols. Statistical analysis, including ANOVA, was applied to identify significant differences between the waste profiles of the establishments. The results demonstrated variability in BW composition, with significant differences in fiber, starch, and carbohydrate content across the three locations, likely due to differences in menu offerings and food preparation practices. High fiber and carbohydrate content in certain samples indicated their potential for bio-based material production and energy recovery applications. The study concluded that BW from small restaurants presents valuable opportunities for integration into sustainable waste management systems, supporting Costa Rica’s initiatives toward circular economy practices and environmental sustainability. These findings underscore the importance of tailored waste valorization strategies that align with the unique waste profiles of small food service establishments.

Chlorpyrifos strikes out as an extensively utilized organophosphorus insecticide, certified for its neurotoxic properties that have been embroiled in the etiology of Parkinson’s disease, highlighting the imperativeness of constructive degradation strategies. While bioremediation approaches have been explored for the metabolism of chlorpyrifos, there remains a pronounced void in apprehending its degradation via the human gut microbiome. This study addresses this considerable shortfall by scrutinizing the degradative proficiency of Ralstonia pickettii and Escherichia coli, leveraging CellDesigner Ver. 4.4 for the development of gene-regulatory and biochemical pathways. Pathway construction was succeeded by the ascertainment of rate equation employing SBML squeezer 2.1, aiming to elucidate the biochemical and physiological metabolism of chlorpyrifos across various compartments within the human system. Experimental results demonstrated a conspicuous reduction in chlorpyrifos concentration, alongside its metabolites TCP and DETP, over time, facilitated by the action of tcpA, dhpJ, pdeA, and phoA genes derived from the microbial community. These findings stipulate that human gut microbes endow a substantial capability for the degradation of chlorpyrifos and its metabolites, thus promoting the goal of positioning the human gut microbiome as a biomarker to investigate the bioaccumulation dynamics of pesticides within the body and their potential relationship with Parkinson’s disease.

Many organic reaction mechanisms are complex and may involve both multiple steps in series and multiple pathways in parallel. Consequently, for many reactions occurring in condensed media (including enzyme-catalyzed reactions) there is no single rate-determining step associated with a unique transition state (TS): in general, any ‘transition-state structure’ derived from experimental kinetics investigations of a complex mechanism is an average corresponding to a virtual TS. Computational simulation is now capable of yielding valuable insight, complementary to experiment, for minima and saddle points on potential-energy surfaces, corresponding to intermediates and TSs on Gibbs-energy surfaces for complex reactions with multiple TSs in parallel or in series. For a reaction with multiple steps in series, the apparent Gibbs energy of activation (corresponding with a virtual TS) is a sum of terms, one for each contributing real TS j ; the kinetic significance w j of each is given by exp(Δ ‡ G j /RT)/exp(Δ ‡ G app /RT). An analogous expression applies to the kinetics of reaction steps in parallel, except that each Gibbs energy is preceded by a minus sign, and the contribution w i of each real TS to Δ ‡ G app is its Boltzmann weighting, and the mole fraction of the lowest-energy reactant conformer must be factored in. Examples of both types of reaction are discussed to illustrate the concept of the virtual TS.

The polyphenol profiles of strawberry leaves ( Fragaria × ananassa cvs. Marisol and Festival), cultivated in the tropical highlands of Costa Rica, were analyzed using high-field (750 MHz) and benchtop (60 MHz) Nuclear Magnetic Resonance (NMR) spectroscopy. Soluble and insoluble fractions were examined, revealing differences in the aromatic (6.0–8.0 ppm) and sugar (3.0–5.5 ppm) regions. High-field NMR provided sharper, more resolved signals, allowing for the identification of glycosylated polyphenols, flavonoids, and phenolic acids. Marisol exhibited a higher diversity and intensity of glycosylated polyphenols compared to Festival. In the insoluble fractions, both cultivars showed a unique peak at 2.0 ppm, absent in the soluble fractions, likely corresponding to lipids or matrix-bound compounds. The benchtop NMR spectra, though lower in resolution, confirmed key spectral patterns and cultivar differences. This study demonstrates the complementary use of high- and low-field NMR for polyphenol profiling and highlights the potential of strawberry leaves as a valuable source of bioactive compounds, contributing to the understanding of underutilized plant materials and their applications in health-related fields.

Biochar (BC) is a highly porous carbonaceous material with excellent adsorbent properties. The surface properties of BC can be modified to enhance the efficiency of adsorption of specific compounds. However, experimental studies into the adsorbate – adsorbent interactions remain tedious, expensive and time-consuming. Several in-silico studies into these interactions are available using graphitic models and single molecules. In this work computational modelling of amorphous BC in its natural form is done using an amorphous BC model developed through pyrolysis-quenching of graphite. Classical molecular dynamics with a ReaxFF interatomic potential is used to computationally develop the amorphous BC model. The resulting structure was then validated visually, through simulated TEM as well as by analyzing the calculated FTIR spectrum of the model, while the amorphicity was established by a 3D Radial Distribution Function of the carbon skeleton. The in-silico BC model was deemed to be an accurate representation of amorphous BC. The amorphous BC structure that we have developed in this study is a very close representation of the BC found in nature and hence the adsorption studies that were subsequently carried out is also more accurate than existing studies on the adsorption of various chemical species onto BC.

Honey bees, essential pollinators for a wide range of important crops, are currently at risk from exposure to neonicotinoid insecticides. In this study we assessed the impact of two most commonly used neonicotinoid insecticides namely imidacloprid and thiamethoxam on honey bee, Apis cerana through controlled feeding experiment at doses of 15 ng/bee, 30 ng/bee, 60 ng/bee and 120 ng/bee. Mortality was recorded at 4, 8, 18, 24 and 48 h after exposure to insecticides. At 24 h, imidacloprid and thiamethoxam @ 60 ng/bee caused 43.75 and 72.50 % mortality, respectively. After 18 h of exposure to 120 ng/bee of imidacloprid and thiamethoxam, mortality rates reached 82.5 % and 87.5 %, respectively. Significant, dose-dependent effects of imidacloprid and thiamethoxam on bee mortality were observed over time, with the highest concentrations (120 ng/bee and 60 ng/bee) producing the most pronounced effects. Furthermore, prolonged exposure to lower doses (15 ng/bee and 30 ng/bee) induced adverse effects such as trembling and impaired coordination in bees. Overall, the differences in toxicity between imidacloprid and thiamethoxam were largely non-significant across doses and exposure durations. Field studies on foraging activity suggested that imidacloprid can negatively impact honey bee foraging behavior. Three days after exposure to sucrose spiked with imidacloprid at 0.28 mg/kg, foraging activity dropped from 62.67 bees per 10 min before treatment to 6.76 bees per 10 min. These findings emphasize the importance of addressing the harmful effects of neonicotinoids on honey bees, which impact both their behavior and survival, particularly with prolonged exposure.

There is an increasing prevalence of diabetes mellitus throughout the world, and new compounds are necessary to combat this. The currently available antidiabetic therapies are long-term complicated and side effect-prone, and this has led to a demand for more affordable and more effective methods of tackling diabetes. Research is focused on finding alternative medicinal remedies with significant antidiabetic efficacy as well as low adverse effects. In this research work, we have focused our efforts to synthesize a series of indazole-based 2,4-dihydro-3 H -1,2,4-triazole-3-thone derivatives ( 1-17 ) and evaluated their antidiabetic properties. In addition, the precise structures of the synthesized derivatives were confirmed with the help of various spectroscopic techniques including 1 H NMR, 13 C NMR, and HRMS. To find the antidiabetic potentials of the synthesized compounds, in vitro α -glucosidase and α -amylase inhibitory activities were characterized using acarbose as the reference standard. From structure–activity (SAR) analysis, it was confirmed that any variation found in inhibitory activities of both α -amylase and α -glucosidase enzymes was due to the different substitution patterns of the substituent(s) at variable positions on the phenyl ring. The results of the antidiabetic assay were very encouraging and showed moderate to good inhibitory potentials with IC 50 values of for α -glucosidase (3.42 ± 1.43 μM to 29.34 ± 0.79 μM) and α -amylase (3.44 ± 0.18 μM to 31.77 ± 0.90 μM), respectively. The obtained results were compared to those of the standard acarbose drug (IC 50  = 10.30 ± 0.20 μM for α -amylase and IC 50  = 9.80 ± 0.20 μM for α -glucosidase). Specifically, among the synthesized analogs, seven compounds ( 1, 5, 6, 8, 11,15 , and 16 ) demonstrated superior inhibitory activity, surpassing acarbose with IC 50 values ranging from for α -glucosidase and for α -amylase respectively. The outcome was further corroborated using in silico techniques, leading to the elucidation of plausible inhibition and metabolism mechanisms. These findings reveal that triazole-containing bis-hydrazones act as α -glucosidase and α -amylase inhibitors, which help develop novel therapeutics for treating type-II diabetes mellitus and can act as lead molecules in drug discovery as potential antidiabetic agents.

The synthesis of nanoparticles (NPs) has gained prominence due to their distinct properties and wide-ranging applications. Among various methods, green synthesis stands out for its environmentally friendly approach. This study investigates the green synthesis of silver nanoparticles (AgNPs) using the aqueous extract of Umbrella plant flowers ( Schefflera actinophylla ). Phytochemical analysis of the extract identified the presence of alkaloids, terpenoids, saponins, resins, carbohydrates, and phenols. Silver nanoparticles were synthesized using a 0.1 M AgNO 3 solution and monitored through UV-visible spectroscopy, which revealed an absorption peak at 370 nm. Characterization through infrared (FTIR) spectroscopy, Field Emission Scanning Electron Microscopy (FE-SEM), Dynamic Light Scattering (DLS), and Zeta potential measurements indicated an average particle size of 8.9 nm and a zeta potential of −8.8 mV. FE-SEM images showed nanoparticles in various shapes. The AgNPs exhibited significant antimicrobial activity against common bacteria such as Staphylococcus aureus , Bacillus subtilis , Pseudomonas aeruginosa , and Escherichia coli , as well as fungi including Aspergillus niger and Candida albicans . Furthermore, the nanoparticles displayed notable antioxidant activity with an IC 50 value of 37.025 μg/ml. This study highlights the benefits of using plant-based methods for nanoparticle synthesis, offering an eco-friendly alternative to conventional chemical processes, thus reducing pollution and mitigating antibiotic resistance in microbes.

The development of robust machine learning models to assist the prediction and optimization of homogeneously catalyzed reactions has attracted wide interests. In this work, we propose a workflow to estimate the linear to branched ratio of the products in hydroformylation reactions using a stacking ensemble method that integrates Random Forest, eXtreme Gradient Boosting, and Light Gradient Boosting Machine algorithms, leveraging physicochemically significant features from small-batch experimental data. The stacking model achieves superior performance with R 2 and Root Mean Square Error values of 0.918 and 0.078, respectively. Moreover, the SHapley Additive exPlanations analysis and density functional theory calculations reveal the significant impact of the gap values between the highest occupied molecular orbital and lowest unoccupied molecular orbital of alkenes on the regioselectivity of hydroformylation reactions, indicating that larger gap values tend to result in a higher proportion of the linear products. This study illustrates that the combination of physicochemically significant features and interpretable ensemble models can serve as a useful strategy for predicting regioselectivity in homogeneously catalyzed reactions.

(Poly)phenol from tropical fruits have attracted attention for their antioxidant and antimicrobial properties, offering potential solutions to food safety risks posed by microorganisms and mycotoxins. Using a validated and streamlined ultra high-performance liquid chromatography coupled to diode array and tandem mass spectrometry with electrospray ionization (UHPLC-DAD-ESI-MS/MS) protocol, targeted (poly)phenol with antimicrobial and antimycotoxin potential were analyzed in six tropical fruits ( Annona muricata , Anacardium occidentale , Byrsonima crassifolia , Elaeis guineensis , Hylocereus costaricensis , and Spondias purpurea ). The (poly)phenol-rich extracts of the most promising ones according to their total (poly)phenol content, namely A. occidentale , B. crassifolia , and H. costaricensis , were further evaluated for their antifungal and antimycotoxin activities. Bioassays revealed antifungal activity against Fusarium verticillioides and inhibition of fumonisin B1 (FB 1 ) accumulation. When applied to maize and rice grains, these extracts provided protection, although efficacy decreased over time (after 45 days), likely due to (poly)phenol degradation. The antifungal and antimycotoxin effects may be attributed to the combined action of multiple (poly)phenol, which are abundant in these fruits.

Poás Volcano is a complex stratovolcano in Costa Rica’s Central Mountain Range and hosts acidic volcanic lakes. This study uses Unmanned Aerial Vehicles (UAV) to monitor the physicochemical characteristics of the hyperacid crater lake. Sampling was conducted in January and May of 2024, using a DJI Matrice 600 Pro equipped with a water collection system. The results showed extremely low pH values (as low as −1.04), high temperatures (up to 64 °C), and high concentrations of sulfate (134 877 ppm) and chloride (88 434 ppm), highlighting the influence of volcanic activity on the chemical composition of the hyperacid lake water. Sampling was marked by a decrease in rainfall patterns during the dry season and a reduction in the lake’s water volume, indicating a high evaporation rate and the release of gases and ash. The SO 4 2− /Cl − ratio was relatively constant, with no increase in activity and that meant that it was safe for tourism, based on the physicochemical characteristics of the hyperacid crater lake.

Organic pollution of water bodies caused by human activities poses a significant environmental challenge. A promising and sustainable solution to this issue lies in harnessing microorganisms for the bioremediation of contaminated aquatic ecosystems. The present work explores potential of biofilm forming microorganisms as a sustainable solution for pollution control, thereby offering a cost-effective and ecofriendly method to mitigate the harmful effects of organic pollutants in water bodies. In this study, wastewater samples along with sludge, was collected from kitchen sink outlet, to foster biofilm development over a 10-day period. After treatment with pond water and measurement of Biological Oxygen Demand (BOD) reduction, the most efficient biofilm was selected based on BOD values. The selected biofilm exhibited 90 % reduction in BOD. Subsequent experiments revealed substantial BOD reducing capability of one specific bacterial strain (50 % reduction in BOD) which was isolated from the most efficient biofilm. Through biochemical and molecular characterization, the organism was identified as Enterobacter cloacae , specifically designated as E. cloacae honeykp. Qualitative and quantitative assays confirmed biofilm-forming capability of the new isolate. The application of E. cloacae HoneyKP in biofilm-based reactors, biofilters, activated sludge systems, membrane bioreactors etc. holds significant potential in terms if bioremediation of polluted water bodies. By utilizing its biofilm-forming capabilities, this isolate could potentially enhance the degradation of organic pollutants and other toxic compounds, while supporting microbial community resilience. These approaches offer innovative strategies for bioremediation, enabling the efficient treatment of wastewater, restoration of polluted water bodies, and reduction of the environmental impact of anthropogenic contaminants.

Self-oscillating gels driven by the Belousov-Zhabotinsky reaction represent a novel class of smart materials that exhibit autonomous, reversible, and periodic changes in color and size without the need for external stimuli. Currently, most such gels are based on catalytically active ruthenium complexes, which are not only expensive but also light-sensitive, potentially limiting their practical application. Therefore, the development of self-oscillating gels based on non-ruthenium catalysts is an important task, since there is a need for inexpensive and accessible chemomechanical materials for industrial use. This review presents and summarizes the advancements made in self-oscillating gels based on Fe, Co, and Ce catalysts. Furthermore, it discusses the opportunities, challenges, and future directions in this emerging field.

This study addresses the growing need to accurately identify trace elements in the environment, an important factor in effective pollution control and protection of public health. The goal was to evaluate and compare the sensitivity, selectivity, and specificity of Gas Chromatography-Mass Spectrometry (GC-MS) and Liquid Chromatography-Mass Spectrometry (LC-MS) of different environmental matrices such as air, water, soil, and wastewater. Controlled laboratory experiments were carried out to assess the effectiveness of both techniques for the detection of polycyclic aromatic hydrocarbons (PAHs), volatile organic compounds (VOCs), chemicals, and pesticides. Results revealed that GC-MS achieved high sensitivity for VOCs in air, with detection limits reaching of 0.1 pg/mL, and for PAHs in water and soil, with detection limits down to 2 pg/g. However, GC-MS performance was reduced in complex matrices like soil due to matrix effects. Conversely, LC-MS excelled in detecting polar and non-volatile compounds, such as pharmaceuticals in wastewater, reaching detection limits down to 0.5 pg/mL, and pesticides in soil, with detection limits down to 2 pg/g, even while contending with challenges like ion suppression. The findings emphasise the need to select an analytical method based on analyte type and matrix complexity to ensure precise detection and reliable results in complex environmental samples. Graphical Abstract

In this paper, we describe the synthesis and characterization of iridium (III) half sandwich complexes of stoichiometry [Cp + IrCl 2 L] with Cp +  = η 5 -C 5 EtMe 4 ; L = alanine anhydride (I), ortho- (II) and para -aminophenol (III). For comparative purposes, the ionic complex [Cp*IrCl( o -phen)](PF 6 ); Cp* = (η 5 -C 5 Me 5 ) (IV) has been also synthesized and characterized. All the isolated complexes have been characterised by C, H and N elemental analysis; infrared and 1 H nuclear magnetic resonance spectroscopies; 1 H– 1 H COSY; mass spectrometry (ESI/TOF), thermogravimetry and, in the case of (IV), by conductivity measurements. The cytotoxic behaviour of the isolated complexes was studied against HeLa and complexes (III) and (IV) were found to have an IC 50 close to 160–170 μm, quite close to the IC 50 value of cisplatin which was found to be 134.7 μm, indicating that they are good cytotoxic agents. However, complexes (I) and (II) showed IC 50 values above 250 μm indicating their low cytotoxicity.

Polyaniline (PANI) is a promising material for energy storage technologies such as supercapacitors due to its unique properties such as high conductivity, redox activity, excellent environmental stability, low cost, and easy preparation. However, enhancing the charge storage capability of PANI and improving the capacitance of PANI is a challenge. To address this challenge, a novel and facile electrochemical approach to synthesizing the porous PANI is proposed. This approach varies from conventional methods by eliminating the necessity for templates to form pores in the PANI matrix. Pore formation was facilitated using the readily available organic dye, methylene blue (MB). Electrochemical polymerization of PANI was carried out using cyclic voltammetry (CV) within the potential range of 0 V–1.4 V in a 0.1 M H 2 SO 4 electrolyte containing 0.025 M MB. Characteristic redox peaks at approximately 0.5 V, 0.9 V, and 0.2 V confirmed the successful synthesis of PANI. The polymer was electrodeposited onto a stainless-steel (SS) substrate pre-adsorbed with MB and subsequently immersed in ethanol to extract the dye. Porous structures significantly enhance the surface area of the PANI matrix, facilitating rapid ion diffusion and improving charge storage capability. Synthesized material was structurally characterized by the Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX), and X-ray diffraction (XRD). FTIR analysis confirmed the deposition of PANI on the electrode substrate. SEM images showed pore structures in the PANI matrix. EDX data showed the presence of elements N and C, confirming the deposition of PANI. The electrochemical characterization of the material was carried out using CV, electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge (GCD) technique in 0.5 M H 2 SO 4 electrolyte using a three-electrode configuration to illustrate the electrochemical performance of the material. The CV data showed a significant enhancement in the capacitance of porous PANI to 13 mF cm −2 at the 5 mV/s scan rate compared to the capacitance of PANI of 7.6 mF cm −2 . The capacitive and diffusive contributions quantified using Dunn’s method were 24.8 % and 75.2 % respectively. GCD data showed an energy density of 2.056 μ Wh cm −2 at the power density of 0.034 mW cm −2 and a capacitance retention of 98 % after the 10 cycles. EIS data showed the enhancement of electrochemical performances with less charge transfer resistance for porous PANI. These results concluded the efficacy of the proposed electrochemical synthesis method in enhancing the charge storage capability of PANI for its potential for high-performance supercapacitor applications.

Wood is one of the most versatile materials, including religious symbols and carved works of art. However, it is a material that is vulnerable to biodeterioration by insects, fungi, and other organisms. Biodeterioration by xylophagous insects is one of the main problems for the conservation of wooden objects; however, control methods are focused on insecticides which can be harmful and toxic to humans and the environment. In this work, the use of zinc oxide nanoparticles obtained by green synthesis with an aqueous extract of agro-industrial waste such as orange peels and zinc nitrate was proposed. It porposes an alternative to the use of toxic substances against the attack of Bostrichidae xylophagous insects of the genus Prostephanus on wood. The results obtained show that the chemical composition of orange peels extract is a good alternative for the green synthesis of zinc oxide nanoparticles. Information obtained from SEM, SEM-EDX and TEM analysis of the material provided agglomerated structural morphology, zinc oxide composition and particle size on the nanometric scale. Preliminary studies of the biocidal activity of zinc oxide nanoparticles alone and in ethanol suspension (1, 3, 5 %) demonstrated the effective protection of broadleaf wood blocks against the attack of the xylophagous insect Brostrichidae of the Prostephanus genus. The biocidal activity increased up to 75 % when zinc oxide nanoparticles were applied directly rather than in ethanolic suspension. Furthermore, the nanoparticles increased water absorption capacity played an important role in removing local moisture from the cavity, which is vital for the insect’s development at the larval stage.

Due to their potential carcinogenic and genotoxic effects on human health, nitrosamine impurities have become a significant concern for regulatory agencies globally. Thus, there is a need for highly sensitive and specific analytical methods capable of detecting trace levels of nitrosamines. Liquid chromatography tandem mass spectrometry (LC-MS/MS) has become the method of choice for identifying and quantifying these impurities due to its unparalleled sensitivity, selectivity, and precision. Regulatory bodies such as the United States Food and Drug Administration, European Medicines Agency, International Council for Harmonisation, and World Health Organization emphasize the importance of addressing nitrosamine hazards, providing updated guidance to manufacturers and applicants. The key objective of this review is to examine recent advancements in LC-MS/MS methods for nitrosamine analysis, focusing on detection limits, precision, accuracy, and matrix effects to ensure highly sensitive and specific detection of these potentially carcinogenic impurities in compliance with global regulatory guidelines.

The global plastic waste management faces significant challenges due to the increasing volume of mixed plastic waste streams. A systematic review of plastic waste separation technologies and characterization methods is essential to enhance recycling efficiency. This study examines separation technologies and quality validation methods for various plastic types through detailed analysis of operational parameters and industrial applications. The investigation focuses on both thermosetting plastics and thermoplastic materials including PP, ABS, PE and PS. The study implements multiple analytical characterization methods including Melt Flow Index (MFI), Differential Scanning Calorimetry (DSC), Fourier Transform Infrared Spectroscopy (FTIR), Thermal Gravimetric Analysis (TGA) and mechanical properties of the material. The findings suggest that systematic separation approaches based on material properties offer the most promising pathway toward sustainable plastic recycling solutions.

Precise snake venom identification is the prerequisite for clinical treatment, production of antiserum, basic research, and other applications. Unfortunately, it is still a challenging task which mainly originates from their extraordinary complicated protein composition. Differential sensing strategy was applied benefiting from its advantage in discrimination of complex mixtures. Herein, A dual-mode supramolecular fluorescent sensor array based on the heteromultivalent sensing strategy was developed. The heteromultivalent macrocyclic coassemblies with strong and pan-selective binding to proteins were employed to construct sensor units. Fluorescence intensity and anisotropy signals were integrated, which were expected to show multidimensional information of proteins, such as surface groups, protein structures, and molecular weights. Finally, a supramolecular sensor array with the ability of facile, rapid and general species-specific identification and taxonomic classification for snake venom was constructed. The sensor array also demonstrated its advantage in semiquantitative analysis and multi-level identification, suggesting its great potential for practical use.

Rice bran oil (RBO) is one of the healthiest edible oils in the world is locally underutilized. The current study was conducted to examine the physicochemical, nutritional, functional and sensory properties of RBO extracted from two locally grown rice varieties Bg 300 (white rice bran oil: WRBO) and At 362 (brown rice bran oil: BRBO) and to compare those with commercially available coconut oil (CACO). Saponification value in RBOs varied in the range of 175–176 mg KOH/g. BRBO showed a higher peroxide (3.71 ± 0.80 meq O 2 /kg) and Iodine value (98.38 ± 0.05 g I 2 /100 g) compared to WRBO. Highest oleic acid percentage (45.34 ± 2.65 %) and smoke point (204.6 ± 8.3 °C) was observed in BRBO. Significantly highest potassium (133.10 ± 1.07 mg/kg) and sodium (76.80 ± 0.10 mg/kg) contents were observed in BRBO and CACO respectively. Further, BRBO showed the highest contents of ɤ-oryzanol (1.49 ± 0.04 %), total flavonoid (1.13 ± 7.66 mg QE/g), total phenolic (1.47 ± 1.46 mg GAE/g) and DPPH radical scavenging capacity (1.04 ± 0.07 mmol Trolox/g). As a whole, BRBO from At362 showed acceptable physicochemical, nutritional and functional properties compared to WRBO and CACO proving it as a promising application in local food industry while utilizing rice bran, a by-product in rice milling.

Soil-borne plant pathogens infect plants through soil inoculum, leading to plant diseases that can drastically reduce crop yield and even be associated with illnesses in humans and animals. This research focused on developing an environmentally friendly, affordable, and non-toxic antifungal agent to combat these diseases caused by soil-borne fungi. Magnesium oxide (MgO) nanoparticles, known for their antifungal properties, were incorporated into a pyrolyzed carbon matrix derived from coconut coir dust (Mg-PCC). During the in situ synthesis, clean, dry coconut coir was treated with magnesium nitrate (Mg(NO 3 ) 2 ) and sodium hydroxide (NaOH), followed by pyrolysis at 450 °C for 1 h. The Mg-PCC sample was characterized using powder X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. The antifungal efficacy of Mg-PCC was tested at three different concentrations against the soil-borne fungi Ganoderma sp., Mucor fusiformis , and Aspergillus niger using a mycelial growth inhibition assay. At a concentration of 10,000 μg/ml, Mg-PCC demonstrated the highest antifungal activity. Further evaluation in soil medium revealed that an optimal dosage of 20 mg of Mg-PCC per 1 g of soil effectively inhibits fungal growth. These findings suggest that Mg-PCC is a potent antifungal agent against soil-borne fungi.

The application of microbial flocculants in nanoparticle synthesis is attracting scientists to utilize them due to their eco-friendliness. This study was mainly focused on biosynthesizing and characterizing copper nanoparticles from a non-pathogenic microorganism Kytococcus sedentarius to produce bioflocculant. The formed copper nanoparticles (CuNPs) were analyzed using UV–vis spectroscope (UV–vis), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray diffractometer (XRD) and thermo-gravimetric analysis (TGA). After extraction and purification, 2.4 g was produced from bioflocculant in a 1 L culture fermentation mixture. During CuNP biosynthesis, a blue color change was obtained after 24 h of incubation indicating their successful formation. A variety of elements namely, C, O, Cu, P, Ca, Mg and Al were found in the as-synthesized CuNPs with 25.23 % (wt) carbon, 20.13 % (wt) of oxygen and 23.37 % (wt) of Cu element. SEM and TEM images of the product depicted it to be agglomerated with different size and shapes. The TGA showed the CuNPs to be thermal stable as 70 % weight was retained at 900 °C with 30 % weight lost. FT-IR spectrum of the biosynthesized CuNPs contains a variety of functional groups related to sugar and proteins namely, hydroxyl, amine, carboxyl groups and a typical Cu–O bond at 559 cm −1 . The crystallite size was estimated to be 28.3 nm, which is in line with JCPDS card no. 89–5899 of copper standard confirming the correct peak orientation. UV–vis analysis revealed the absorption peak to be 275 nm which confirms synthesis of the CuNPs using a bioflocculant.

The contamination of pesticides and pharmaceuticals and personal care products (PPCPs) in the environment poses a significant social concern, particularly in drinking water and wastewater. The growing need for desalination to meet the demand for potable water adds to this challenge, as many water sources contain salt concentrations beyond permissible limits. Pesticides enter water systems primarily through agricultural activities, while pharmaceuticals and personal care products (PPCPs) originate from various sources, including sewage treatment plants, hospitals, and improper drug disposal. These contaminants pose serious health risks to humans and other organisms, necessitating effective removal methods. Over the past decade, Porous and mesoporous materials, such as synthetic zeolites and mesoporous silica, carbon-based adsorbents, and metal-organic frameworks (MOFs) have emerged as powerful material for advanced water purification particularly in removing pesticides and PPCPs from aqueous solutions, as well as in desalinating water due to their tunable pore architectures, high surface areas, and surface functionalization potential. This review critically examines the design, synthesis, performance, and removal mechanisms of these materials in applications spanning adsorption, desalination, and hybrid remediation technologies. Despite the promising performance of these materials, significant research gaps remain. These include a lack of field-scale validation, insufficient exploration of multifunctional hybrid systems (e.g., adsorption-photodegradation), challenges in scalable green synthesis, and limited understanding of material behavior in complex real water matrices. Additionally, the long-term stability, regeneration efficiency, and kinetics under variable operating parameters are not comprehensively understood. Future research must pivot towards the development of recyclable, multifunctional materials, integration of AI-guided material design, and eco-friendly synthesis strategies to enhance scalability and sustainability. This review not only maps the current scientific landscape but also provides a forward-looking perspective to guide the next generation of water treatment technologies using porous and mesoporous materials. The insights provided will help researcher’s select appropriate materials and optimize conditions for effective contaminant removal and water desalination.

The dianion [B 10 H 14 ] 2− has attracted renewed attention due to its structural characteristics and a mercury-free synthesis route. Although its arachno structure has been reported, we explored the potential energy surface of B 10 H 14 2− to identify more stable species. Subsequent analyses included bonding evaluation, kinetic studies, and Born-Oppenheimer molecular dynamics (BO-MD) simulations. Calculations indicate that the closo -[B 10 H 10 ] 2− ⋯2H 2 complex is 21.5 kcal mol −1 more stable than the arachno structure. The complex is stable below 110 K but dissociates into closo -[B 10 H 10 ] 2− and H 2 at higher temperatures. The arachno isomer remains kinetically stable because a 30 kcal/mol activation barrier prevents its conversion. BO-MD simulations corroborate this kinetic stability, as the arachno framework is maintained during the trajectories. The effects of the solvent and the counterions were also examined and found to have a negligible influence on the relative energetics.