Integrating natural deep eutectic solvents and ionic liquids as green mobile phase additives for enhanced selenium speciation analysis in food samples by liquid chromatography-atomic fluorescence spectrometry.

Solvent effect on iodoargentates hybrids templated by organic cation: synthesis, structures, photoelectricity and photocatalysis

The incorporation of trifluoromethyl groups in aromatic compounds via nucleophilic substitution faces the problem of the high reactivity of this species as a base and its decomposition to form difluorocarbene. Although palladium-catalyzed trifluoromethylation was developed for aryl chloride substrates using biaryl monophosphines as ligands, the scope of reaction and the availability of effective ligands are yet limited. In this work, we have investigated the direct reductive elimination step of the catalytic cycle. The study involved 11 ligands, including several biaryl monophosphines and the most effective BrettPhos ligand. The solvent effect was also evaluated, including up to 20 solvents. We have found that several biaryl monophosphine ligands are as effective as BrettPhos in the reductive elimination step. The solvent effect evaluated with the openCOSMO-RS model indicates that there is a better correlation of the induced free energy barrier with the dipole moment of the solvent molecule than with the Onsager function. • Simple monophosphine ligands react via T-shaped complexes. • Several biaryl phosphine ligands are effective in the reductive elimination step. • Solvent dipole moment is a good predictor of solvent effect.

Evaluating the drug delivery potential of functionalized calix [4] arene for carboplatin-drug: A computational study analyzing static electric field and solvent effects through DFT, TD-DFT, and NLO techniques.

Hydrothermal liquefaction of Caragana korshinskii to bio-oil: Effect of liquefaction solvents and catalysts

Hydrogen-free reductive catalytic fractionation of biomass via synergistic solvent-catalyst interactions: mechanistic and kinetic insights.

Acylthiourea ligands in Ru(II)–arene chemistry: Coordination modes, structural insights, solvent and pH effects

Distinct Solvent Effect on the Conformation and Charge State Distribution of Typical Proteases Revealed by Ion Mobility Mass Spectrometry

Volume changes of the active material lead to a cyclic mechanical loading of composite electrodes during operation. Active material particles and the binder mechanically interact, resulting in an evolution of the structure of the electrode. Here, we mechanically test electrodes in a cyclic compression experiment and measure their strain and resistance under conditions close to application. We investigate the effect of temperature, rate, and the presence of an electrolyte solvent on the electrode dimensions/mechanics and resistivity. We further compare the pure polymeric binder material with composite electrodes to study how the binder affects the electrode mechanics. The results demonstrate that under application conditions electrodes are even less stable and more dynamic than dry model systems. Their viscous, time‐dependent mechanical behavior originates from the binder itself and is strongly affected by the presence of the electrolyte solvent, which strongly reduces the stiffness and enhances the flow of the binder. During mechanical loading and unloading, the structure of the composite evolves over the course of several cycles and adapts to the prevailing operating conditions. The properties of battery electrodes, e.g., their dimensions and their resistance, strongly depend on the state of charge, but also on their history of cycling and mechanical load.

The cleavage of dimethyl methylcyclohexyl-2,4-dicarbamate (HTDC) is a critical step in the nonphosgene route to the synthesis of methylcyclohexyl-2,4-diisocyanate (HTDI). Understanding the solvent effects is essential for selecting suitable solvents and catalysts for the cleavage of HTDC. In this work, the electronic properties of five high-boiling-point ester solvents (aliphatic and aromatic esters) and the influence on the cleavage of HTDC were investigated using a combined approach of multiscale theoretical simulations and experimental characterization. The results indicate that the electron-donating ability of the solvent and its polarization effect on HTDC are the key factors influencing solvent performance. The reactivity of HTDC and HTDI is influenced by solvent polarization, exhibiting an inverse relationship with the solvent polarity. The electron-donating ability of the solvent influences its interactions with HTDC and the ZnO catalyst via hydrogen bonding, thereby altering both the reactivity of HTDC and its adsorption process on the ZnO surface. Above all, the solvent effect in the carbamate cleavage reaction is systematically investigated. These conclusions will facilitate the design and selection of high-performance solvents for the carbamate cleavage reactions.

Biorefining cellulose, a major constituent of agricultural residue cell walls, into high-value chemicals improves agriculture's economic and environmental performance. Solvents play a crucial role in determining the selectivity and yield of cellulose hydrolysis products, yet the underlying mechanism of this control remains elusive. This study integrates calculational chemistry and experimental data to elucidate at the molecular level the specific roles of solvent molecules in cellulose hydrolysis. In the composite solvent γ-valerolactone/water, a cellulose conversion of 95.0% and a levulinic acid yield of 65.8% were achieved. Under kinetic control, water molecules both promote catalytically active species generation and, through intermolecular interactions, facilitate their reactive binding with glucose intermediates. GVL solvent molecules stabilize catalytically active species and product molecules via confinement enrichment and electronic structure regulation. This work reveals the decisive role of solvent effects in sustainable biorefining, paving the way for dramatically boosting the agricultural residue utilization efficiency.

A novel compound, methyl 2-(4-methylbenzyloxy)benzoate (MB), has been successfully synthesized by condensation of methyl salicylate with 4-methylbenzyl bromide in the presence of anhydrous K2CO3. The compound has been structurally characterized using FTIR,1H NMR and mass spectroscopy. To gain detailed information on the structural features and predict the vibrational frequencies, the Density Functional Theory (DFT) method was employed at the B3LYP level of theory with the 6–311++G(d,p) basis set. The theoretical results showed a strong correlation with the experimental data of the compound. The IEFPCM model, applied to study the solvent effect, revealed increased NLO properties and electrostatic potential with increasing solvent polarity. In contrast, the polarity of solvent reduced the energy gap between HOMO and LUMO. The hyperpolarizability is approximately 12 times higher than that of urea in water solvent, while 7.48 times higher in the gas phase. Both the experimental and computational UV–Vis spectra exhibited π→π* and n→π* transitions, which were further supported by application of Natural Bond Orbital (NBO) analysis. Topology analysis described the electron charge density distribution and the intramolecular electrostatic interaction of MB. Fukui function analysis predicted multiple sites for electrophilic, nucleophilic, and radical attacks. The ADMET parameters and pass prediction exhibited good fibrinolytic activity, as evidenced by a binding affinity of −7.8 kcal/mol with the Plasminogen Activator Inhibitor-1 (PAI-1) gene, known as an antifibrinolytic agent. Moreover, the results of several dynamic simulation studies suggested the formation of a stable protein-ligand complex.

High-performance fluorescence resonance energy transfer (FRET) systems are of critical importance for advancing applications in biosensing, optical imaging, and photonic devices. Using an excited-state intramolecular proton transfer (ESIPT)-active molecule as an FRET donor, the solvent effect facilitates the optimization of FRET efficiency and kinetics. Herein, two FRET systems PPC-Rhodamine 101 (Rh101) (incorporating ESIPT) and CdSe/ZnS quantum dot (QD)-Rh101 using steady-state spectroscopy and femtosecond transient absorption measurements were explored. A central finding is that the introduction of ESIPT into the FRET framework allows the solvent effect to dualistically optimize the FRET performance. It not only enables precise tuning of the spectral overlap integral between donor emission and acceptor absorption but also capitalizes on the inherent short donor-acceptor separation advantage of PPC. Relative to the CdSe/ZnS-Rh101 system, this ESIPT-integrated strategy boosts efficiency by nearly 3-fold. These results demonstrate that the ESIPT-active molecule exhibits distinct advantages over conventional QDs as an FRET donor, particularly in organic solvent environments, which can be attributed to its intrinsic spectral tunability and size-related benefits for enhancing FRET kinetics. Beyond establishing a clear link between ESIPT-modulated donor properties and FRET efficiency, this study offers a versatile approach for designing high-performance FRET systems with potential utility in biosensing, optical imaging, and photonic devices.

The early COVID-19 pandemic underscored the urgent need for safe, effective antivirals. Thirty-three Nirmatrelvir analogs were computationally screened using DFT-based geometry optimization, IR/NMR/UV-Vis/ECD spectral simulation (with solvent effects), conceptual DFT reactivity analysis, drug-likeness assessment, and molecular docking against SARS-CoV-2 Mpro. The data showed consistent structural stability across solvents; electrostatic potential maps revealed key polar regions near the 2-pyrrolidinone/amide oxygens and hydrogens; seven compounds exhibited balanced stability and reactivity; nine showed Nirmatrelvir-like pharmacodynamic profiles; among them, N3-SR4 stood out for its synthetic feasibility, favorable molecular descriptors, and strong Mpro binding affinity. The electronic structure, reactivity indices, pharmacokinetic parameters, and molecular docking results all indicate that the synthesized intermediates exhibit a high degree of similarity to the target compounds in key physicochemical and biological activity characteristics. These findings support N3-SR4 as a promising candidate for further experimental validation.

Synergistic effect of ESIPT and hRISC properties for 2-(benzo[d]thiazol-2-yl)-4-(pyren-1-yl)phenol: A theoretical study on solvent-dependent excited-state dynamics.

The catalytic potential of wolfium bonds, a σ-hole interaction involving Group 6 elements, remains largely unexplored. Herein, we present a systematic theoretical investigation into the mechanism of wolfium bond donors (WnF4O, Wn = Cr, Mo, W) as catalysts for the aza-Diels-Alder reaction between imine and 1,3-butadiene. Computations performed at the ωB97XD/aug-cc-pVTZ level reveal that these catalysts function via a prestabilization mechanism, forming strong wolfium bonds with the imine reactant. This interaction not only significantly lowers the apparent activation barrier but also reprograms the reaction pathway toward an asynchronous, charge-separated transition state. Catalytic efficiency follows the order Cr < Mo < W, which originates from the enhanced electrostatic and polarization components of the wolfium bond with increasing metal electronegativity and polarizability. Energy decomposition and AIM analyses confirm the electrostatic-dominated, partially covalent nature of these interactions. Crucially, solvent effect studies identify WF4O as an effective modulator of the reaction pathway in both nonpolar and polar media. Compared to conventional hydrogen and halogen bonds, wolfium bonds exhibit a more pronounced ability to regulate the reaction mechanism, offering a new perspective on the role of noncovalent interactions in pericyclic reactions.

The detection of toxic metal ions, such as Pb2+, has become important because they cause several health issues. This study describes the photophysical properties displayed by a few symmetrical diazine compounds and the influence of solvent polarity on their emission spectra. It is noted that λ em increases with an increase in the polarity of the solvent. The study of the complexation of diazine compounds with metal ions, such as Cu2+, Ni2+, Co2+ and Pb2+, shows that the coordination of the metal ions to the diazine molecule induces a blue shift in the UV-visible absorption spectrum. Among the studied compounds, compound 1 exhibited the maximum emission (λ em) in hexane at 309 nm, with a maximum quantum yield (Φ em) of 0.0576. The metal interaction study shows that the absorption intensity of compound 1 reached the maximum for Pb, indicating that the synthesized diazine could serve as a potential molecule to detect Pb2+ ions. The experimental results were further supported by computational studies, and the experimental data were in good agreement with the theoretical data. The TDDFT study shows that for all the compounds, the λ abs corresponds to the HOMO-1 to LUMO+1 transition.

Platinum chemistry covers a wide range of applications, including homogeneous and heterogeneous catalysis as well as cancer therapy. Numerous Pt complexes have been synthesized and studied in recent years, with NMR spectroscopy serving as the primary technique for structural characterization. The 195Pt nucleus has favorable features for NMR studies, being highly sensitive to ligand type and structural environment. From a computational perspective, factors such as solvent effects, relativistic corrections, and the electronic structure of the ligands strongly influence the calculated NMR parameters. Consequently, establishing a general computational protocol for 195Pt NMR prediction remains a challenging task. In this work, we present a systematic validation and extension of our previously developed computational protocol, originally proposed for Pt(II) complexes, in studying 195Pt NMR chemical shifts in Pt(II)-Sn(II) complexes. A benchmark set of 100 Pt(II)-Sn(II) complexes was analyzed, yielding good agreement with experimental data (R2 = 0.86, MRD = 3.6%, MAD = 163 ppm), which is remarkable given the structural diversity and broad range of chemical shifts covered.

The present study investigated the phytochemical composition and antioxidant potential of Jasminum multiflorum and Jasminum nitidum leaves and flowers using different solvent extraction systems. Sequential extraction was carried out with methanol, ethanol, ethyl acetate, chloroform, and aqueous solvents to evaluate solvent-dependent variation in bioactive constituents. Qualitative phytochemical screening revealed the presence of alkaloids, tannins, flavonoids, sterols, terpenoids, and cardiac glycosides in most extracts, whereas saponins and phlobatannins were not detected. Quantitative analysis indicated significant variation (p &lt; 0.001) among solvents and plant species. The ethanolic leaf extract of J. nitidum recorded the highest total phenolic content (41.26 ± 0.78 mg GAE g⁻¹), while J. multiflorum showed 33.10 ± 1.25 mg GAE g⁻¹. Similarly, flavonoid content was higher in J. multiflorum (27.14 ± 0.65 mg QE g⁻¹) and J. nitidum (26.82 ± 0.58 mg QE g⁻¹). Antioxidant assays revealed that ethanolic extracts exhibited superior activity, with lower EC₅₀ values in DPPH radical scavenging (48.73 ± 0.93 µg mL⁻¹ for J. nitidum and 138.45 ± 1.37 µg mL⁻¹ for J. multiflorum) and higher ferric reducing power (610.12 ± 2.74 and 468.33 ± 2.56 µmol Fe²⁺ g⁻¹, respectively). Statistical analysis using one-way ANOVA followed by DMRT confirmed significant effects (p &lt; 0.001) of solvent and species on phytochemical and antioxidant parameters. The findings indicate that ethanol is an efficient solvent for extracting antioxidant-rich phytoconstituents from Jasminum species, suggesting their potential application in pharmaceutical and nutraceutical formulations.

The structural, vibrational, and electronic properties of 2-methyl-5-nitro-1H-benzimidazole-6-amine (MNBA) were analyzed using experimental and theoretical approaches. Density Functional Theory (DFT) simulations utilizing the B3LYP functional and 6-311++G(d,p) basis set were performed to optimize the geometry, predict vibrational frequencies, and analyze the frontier molecular orbitals (HOMO-LUMO) of the MNBA molecule. FT-IR and UV-Vis spectroscopy were used to empirically validate the results, which were subsequently compared to theoretical predictions in both gaseous and aqueous phases. The study highlights the critical role of intramolecular hydrogen bonding between the nitro and amine groups, which forms an intramolecular O···H interaction, that may contribute to the stabilization of the molecular structure. Solvent effects substantially affected molecular shape and electronic distribution, with aqueous phase calculations showing improved concordance with experimental results. Mulliken charge analysis together with molecular electrostatic potential (MEP) mapping provides qualitative insight into the charge distribution and possible reactive regions of MNBA. A reduced HOMO–LUMO gap in aqueous solution suggests enhanced electronic reactivity of the molecule in polar environments, providing insight into the structural and electronic characteristics of MNBA. This study demonstrates the effective integration of DFT simulations and experimental methodologies to elucidate the physicochemical properties of benzimidazole derivatives under diverse environmental conditions.