The conversion of active pharmaceutical ingredients (APIs) into organic salts has emerged as an effective strategy to modulate physicochemical and pharmacological properties, including solubility, stability, permeability, and drug release. Among their biological effects, interactions with biomembranes are particularly relevant, as they directly influence drug efficacy and bioavailability. Despite extensive studies on organic salts, investigations focusing on API-based salts and their membrane interactions remain limited.In this work, the organic salt mefloquine docusate ([MFLH][AOT]) was investigated as a model system to evaluate how counterion selection influences drug–membrane interactions. Using soybean asolectin (ASO) liposomes as simplified membrane models, we combined Fourier transform infrared spectroscopy (HATR-FTIR), hydrogen and phosphorus nuclear magnetic resonance (1H NMR and 31P NMR) spectroscopies, and molecular dynamics (MD) simulations to gain both experimental and molecular-level insights.The results indicate that [MFLH][AOT] interacts with membranes primarily through Coulombic interactions and hydrogen bonding involving lipid headgroups and interfacial regions, alongside hydrophobic contributions. Compared to isolated components, free mefloquine shows deeper membrane penetration, whereas the organic salt exhibits reduced interaction due to ion pairing and aggregate formation. MD simulations supported the structural stability of the liposomes over 6 μs and showed that AOT–MFL association modulates additive redistribution, penetration, and aggregation within the liposomal environment.These findings support the interpretation that [MFLH][AOT] behaves as a distinct supramolecular entity rather than as independent ions. This behavior has important implications for drug delivery, suggesting potential for controlled co-encapsulation and release in liposomal systems, as well as modulation of pharmacokinetic properties.
The sustainable valorization of lignocellulosic biomass into high-value nanomaterials is gaining momentum as an alternative to synthetic nanoparticles, driven by their biodegradability, biocompatibility, and broad applicability. Nanocellulose and nanolignin, derived from cellulose and lignin extracted from agricultural and forestry residues, offer potential in packaging, medicine, energy, and advanced materials. However, the intrinsic recalcitrance of lignocellulosic feedstocks necessitates efficient pre-treatment strategies that are both environmentally responsible and industrially viable. This review explores recent advances in eco-friendly methods for the extraction of cellulose and lignin, with particular emphasis on ionic liquids (ILs), deep eutectic solvents (DESs), and catalytic systems. ILs demonstrate high dissolution and recycling potential, DESs provide tunability and low toxicity, while catalysts—such as zeolites and metal oxides—enhance selectivity and lignin-first valorization. The integration of complementary techniques, including microwave- and ultrasound-assisted extractions, further improve efficiency. To evaluate the sustainability of these emerging processes, the Path2Green framework was applied. Results show that, despite frequent claims of ‘green’ performance, most IL- and DES-based systems achieved only neutral or slightly negative sustainability scores, largely due to synthetic origins, energy demands, and limited recycling. Catalytic flow-through processes achieved the most favorable profiles, highlighting the importance of solvent choice, closed-loop design, and scalability. Overall, progress demonstrates that no universal solution exists; instead, feedstock-specific, integrated approaches are essential. Future directions should prioritize bio-based solvents, closed-loop recycling, renewable energy integration, and standardized reporting to bridge the gap between laboratory innovation and industrial application. © 2026 Society of Chemical Industry (SCI).
This work reports the design and synthesis of new fluorescent chiral derivatives based on the Tryptanthrin scaffold via Buchwald–Hartwig reactions. The chiroptical properties of the obtained enantiomers were investigated using circular dichroism (CD) and circularly polarized luminescence (CPL) spectroscopy. The photophysical behavior of the enantiomers (S)-(4a), (S)-(4b), and (S)-(4c) was evaluated by UV–Vis absorption and photoluminescence spectroscopy, revealing emission in the visible region across different solvents. Cyclic voltammetry measurements allowed the estimation of the HOMO and LUMO energy levels, indicating a very low energy gap of approximately 1.9 eV. Furthermore, theoretical calculations were carried out to provide deeper insight into the electronic behaviour of these chiral systems.
This study investigates the low-temperature depolymerization of polyethylene terephthalate (PET) using near-stoichiometric choline hydroxide (ChOH) in methanol, assisted by dichloromethane (DCM) or dimethoxymethane (DMM) as co-solvents. The DCM-assisted system enables rapid apparent PET depolymerization within 30 min under mild conditions, whereas the DMM-assisted system achieves hydrolysis within 20 h at room temperature, yielding choline terephthalate and ethylene glycol. Although slower, the DMM-assisted process proceeds more smoothly, as supported by spectroscopic and microscopic analyses, while the DCM-assisted route leads to accumulation of partially hydrolysed intermediates and transient micro/nanoplastic residues during the early stages of hydrolysis. The studied processes exhibit high atom economy due to the near-stoichiometric use of choline hydroxide and simplified product isolation without acid neutralization or extensive purification steps. In addition, benchmarking based on energy and environmental metrics was extended to account for multistage operations such as solvent removal, drying, and metathesis processes, enabling more comprehensive comparison with previously reported PET depolymerization methods. The results highlight the importance of balanced benchmarking when evaluating sustainability claims in chemical plastic recycling and demonstrate the potential of choline hydroxide-mediated PET hydrolysis as a low-temperature and resource-efficient depolymerization strategy.
Abstract Protic ionic liquids characterized by permutable protons have important applications in electrochemistry. This work represents an unprecedented report of the use of such electrolytes for CO2 electroreduction (ECR) into CO at 10 bar and near room temperature (45 °C) on zinc electrodes. It was observed that when protic ILs are synthesized from strong acids, the competition with the hydrogen evolution reaction increases. In contrast, the use of softer acids in the synthesis significantly enhances CO production. Imidazolium-based protic ILs were chosen due to their known high CO2 solubility and consequently their potential to increase reaction productivity. The electrolytes were electrochemically characterized, their conductivities and diffusion coefficients were determined, and their performance was compared. Despite the aqueous nature of the electrolyte, remarkably, 100% Faradaic efficiencies were obtained with [HMIM][Lac] containing 50 wt % water. The performance of the aqueous protic 50 wt % [HMIM][Lac] electrolyte surpassed the performance of the non-protic 50 wt % [EMIM][OTf] electrolyte. Furthermore, among the investigated water concentrations, the maximum CO production for the protic 50 wt % [HMIM][Lac] (177 µmol/cm2) is of the same order as the magnitude of 90 wt % [EMIM][OTf] (271 µmol/cm2), an almost pure IL, more expensive, and less sustainable electrolyte. The non-fluorinated bio-based lactate anion concurs to the higher sustainability of the process. Hydrophilic protic ILs are thus promising as electrolytes for ECR.
High antiproliferative activity against lung cancer cell lines.
Nanoporous organic materials with varying pore sizes were utilized to remove antibiotics from surface and groundwater. These adsorbents belong to the group of Covalent Organic Frameworks (COFs), known for their high stability, porosity, and large surface area. Given their characteristics, which are well-suited for adsorption applications, these materials demonstrated relatively high capture capacities for emerging organic pollutants such as chloramphenicol (182 mg g-1 for RIO-55) and ciprofloxacin (79 mg g-1 for RIO-55) compared to other organic porous adsorbents. To conduct a comparative study on adsorption efficiency, both ionic and non-ionic materials were selected. Some ionic materials exhibited greater affinity for pharmaceutical compounds due to different adsorption mechanisms. Additionally, tests using a real water sample from the Tagus River confirmed the materials' removal efficiency. A correlation was observed between the maximum adsorption capacity and the pore width of the COFs, suggesting that better fitting of these adsorbates into mesopores enhances adsorption performance.
Deep eutectic solvents (DESs) have emerged as promising alternative solvents for a wide range of applications, such as extraction and separation processes. To broaden their functionality, the development of responsive DESs (RDESs) has attracted particular interest due to their ability to abruptly change their properties in response to external stimuli. Herein, we aim to prepare a new RDES comprising a photo- and electrochromic dicarboxylic diarylethene derivative (DTE) and quadrol (Q). The prepared system exhibits a color change from yellowish to pinkish-red under UV irradiation due to the photoisomerization of DTE, which can be reverted by visible light or oxidative electrolysis. Interestingly, this process also alters the strength of the hydrogen bonds between DTE and Q, leading to an externally controlled change in the thermal and electrical properties of the eutectic mixture. Therefore, these results demonstrate the capacity to photo- and electromodulate the behavior of DESs by incorporating stimuli-responsive units, thereby opening new perspectives toward the design of solvents with tunable properties for a variety of industrial and materials science applications.
Several quinones, diphenoquinones and respective reduced forms, hydrobenzoquinones and hydrodiphenoquinones, were synthesized, and their electrochemical properties were studied by cyclic voltammetry (CV) in non-aqueous medium to assess their upcoming applicability as organic redox mediators. Benzoquinones and diphenoquinones exhibited two reversible electron transfers (ETs) as exemplified by tetra-tert-butyldiphenoquinone, which displayed ETs at standard potential (E0) at E0 = -0.53 V and E0 = -0.92 V versus SCE (saturated calomel electrode). However, hydrobenzoquinones displayed chemically irreversible ET, whereas hydrodiphenoquinones exhibited either chemically irreversible or quasi-reversible ETs. For instance, di-tert-butylhydrobenzoquinone demonstrated two irreversible ETs at Epc = 0.31 V and Epa = 1.00 V versus SCE.
The photoreduction of CO2 offers a sustainable route for mitigating atmospheric CO2 levels while producing added value chemicals. This study explores the use of Ni(II) and Co(II) octaazacryptates complexes as catalysts in the presence of different ionic liquids under blue LED and solar light conditions. By employing a systematic approach to vary ionic liquid concentrations and light sources, the catalytic performance was assessed in terms of CO production, H-2 production, CO selectivity, turnover number, and photoreaction quantum yield. The findings reveal that ionic liquid 1-ethyl-4-picolinium triflate significantly enhances CO2 reduction efficiency under solar light, with the highest CO yield of 15.75 mu mol and CO turnover number of 1575 observed when using 2%w/w of the ionic liquid. Conversely, higher ionic liquid concentrations improved selectivity at the expense of CO production. The experiments conducted under sunlight demonstrated a compromise between selectivity and turnover, with the highest CO turnover number achieved for ionic liquid experiments, but greater selectivity in the absence of ionic liquid. These results underscore the importance of ionic liquid concentration in modulating catalytic performance, while also highlighting the potential of direct sunlight as a sustainable and powerful energy source for scalable, eco-friendly CO2 photoreduction systems.
The growing threat of bacterial resistance is expected to become a leading cause of global mortality in the coming decades. Currently, the pharmaceutical industry is focused on the discovery of new efficient antibiotics as well as the reintroduction of discontinued drugs under the hypothesis that resistance to them may have declined. Another strategy is to use enhancers or adjuvants to counteract the current resistance mechanisms. In this study, both approaches are explored by employing an out-of-market antibiotic, streptomycin, combined with biocompatible sulfonate and carboxylate anions. Eight organic salts were synthesized via direct protonation, yielding stable solids at room temperature, and characterized in terms of their physicochemical properties, such as solubility, permeability, and thermal stability. Their biological properties were also investigated, including toxicity against human keratinocytes and antimicrobial activity against both susceptible and multidrug-resistant strains of Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumoniae, Staphylococcus aureus, and Staphylococcus epidermidis. Among the synthesized compounds, one is an ionic liquid ([STPH3][GluCOO]3), while those with p-toluenesulfonate ([STPH3][p-TolSO3]3), propanesulfonate ([STPH3][C3SO3]3), and glycolic acid ([STPH3][GlyCOO]3) showed the greatest potential for transdermal delivery due to their favorable combination of physicochemical and biological properties. [STPH3][p-TolSO3]3 exhibited enhanced permeation in phospholipid bilayer assays along with promising biocompatibility and antimicrobial efficacy, making it a strong candidate for further investigation.
Despite its promising electronic and semiconducting properties, 12H-phthaloperin-12-one remains a largely unexplored molecule, with limited studies regarding the impact of structural modifications on its properties and its application in light-emitting devices. To address this gap, we report the synthesis of 12 novel phthaloperinone derivatives, designed to fine-tune the photophysical, electrochemical, thermal and electroluminescence properties through the incorporation of electron-donating and electron-withdrawing substituents. The majority of substituents was found to interfere with the electronic distribution in the phthaloperinone core during the electronic excitation process. The introduction of a triphenylamine unit, as in compounds 3f/4f, resulted in the lowest energy gap of 2.22 eV, making this isomeric mixture a promising candidate for use as an organic semiconductor material. Electrochemical studies demonstrated that compounds 3e/4e-3h/4h and 3l/4l exhibited enhanced electrochemical stability, while thermal analysis showed that the pyrene-substituted derivative (3e/4e) displayed the highest thermal resistance (Td = 458 degrees C). Organic light-emitting diodes were fabricated to evaluate their electroluminescence properties. Compounds 3l/4l, which contain a phenyltriazolyl unit, achieved the best performance, displaying a maximum luminance of 99 cd m-2 at 7.5 V, a luminous efficiency of 0.014 cd A-1, and a turn-on voltage of 3.3 V. These findings provide valuable insights into the structure-property relationships of phthaloperinone derivatives and highlight their potential for a wide range of applications, including electronic and optoelectronic devices.
Ionic liquid crystals (ILCs), a class of soft matter materials whose properties can be tuned by the wise pairing of the cation and anion, have recently emerged as promising candidates for different applications, combining the characteristics of ionic liquids and liquid crystals. Among those potential uses, this review aims to cover chromogenic ILCs. In this context, examples of photo-, electro- and thermochromism based on ILCs are provided. Furthermore, thermotropic and lyotropic ionic liquid crystals are also summarised, including the most common chemical and phase structures, as well as the advantages of confining these materials. This manuscript also comprises the following main experimental techniques used to characterise ILCs: Differential Scanning Calorimetry (DSC), Polarised Optical Microscopy (POM) and X-Ray Powder Diffraction (XRD). Chromogenic ILCs can be interesting smart materials for energy and health purposes.
Most known deep eutectic solvents (DESs) are hydrophilic but, recently, hydrophobic DESs have been developed with some interesting features that make them potential alternative lubricants. The advantage of this type of compounds is their stability relative to the presence of water vapor in humid environments during industrial application. In this work, we report the use of hydrophobic DESs based on combinations of salts and acids or natural components (NADES) to lubricate Si surfaces. Two sets of previously reported DESs were prepared and studied: ionic DESs containing ammonium salts, and non-ionic DESs based on menthol. The friction coefficients were measured using steel and Si spheres against Si surfaces and their values were compared to those obtained with hexadecane, the reference lubricant. Non-ionic hydrophobic DESs presented poor lubrication for Si surfaces when compared to the reference lubricant, while all ionic hydrophobic DESs outperformed hexadecane. Among the most promissory hydrophobic DESs, [Aliquat]Cl:menthol (1:2) stood up showing CoF < 0.1 and the best surface protection against wear, independently of its water content, under stresses up to 1.3 GPa. The resistance of the adsorbed boundary layer might be justified by the strong interactions between its HBD and HBA components.
Low oral bioavailability is a common feature in most drugs, including antibiotics, due to low solubility in physiological media and inadequate cell permeability, which may limit their efficacy or restrict their administration in a clinical setting. Cefuroxime is usually administered in its prodrug form, cefuroxime axetil. However, its preparation requires further reaction steps and additional metabolic pathways to be converted into its active form. The combination of Active Pharmaceutical Ingredients (APIs) with biocompatible organic molecules as salts is a viable and documented method to improve the solubility and permeability of a drug. Herein, the preparations of five organic salts of cefuroxime as an anion with enhanced physicochemical characteristics have been reported. These were prepared via buffer-assisted neutralization methodology with pyridinium and imidazolium cations in quantitative yields and presented as solids at room temperature. Cell viability studies on 3T3 cells showed that only the cefuroxime salts combined with longer alkyl chain cations possess higher cytotoxicity than the original drug, and while most salts lost in vitro antibacterial activity against E. coli, P. aeruginosa and B. subtilis, one compound, [PyC10Py][CFX]2, retained the activity. Cefuroxime organic salts have a water solubility 8-to-200-times greater than the original drug at 37 °C. The most soluble compounds have a very low octanol-water partition, similar to cefuroxime, while more lipophilic salts partition predominantly to the organic phase.
The utilization of emitted CO 2 as a carbon source for the manufacturing of chemicals, and materials is a highly active field of research that aims at recycling (waste) carbon back into the value chain. The topic has recently gained a renewed interest due to CO2 increasing atmospheric concentration and consequent climatic impact. In fact, CO 2 is an abundant, nontoxic and readily available renewable C1 building block, that furthermore do not compete with food production. One of the most attractive strategies for CO2 utilization involves the total incorporation of the CO 2 moiety into a high energetic organic substrate, without affecting the oxidation state of the carbon centre. This process although addressing accessible thermodynamic barriers, requires a high-energy substrate, which is normally obtained from fossil resources. Recently many research groups have focused on the combination of CO 2 with bio-based substrates, namely derived from waste biomass. The strategy is highly attractive specially in the context of the production of fully sustainable new chemicals and materials for the chemical industry. However, most bio-based substrates are much less reactive turning catalysis into a critical factor specially regarding the techno-economic viability of the process. This chapter will present an overview of the most promising catalytic systems developed, analyse the new trends and focus on the future challenges.
Ionic Covalent Organic Frameworks are a special subgroup that has risen as promising materials for innovative applications. In parallel, some of the so-called Reticular Innovative Organic compounds (RIOs), which are ionic and non-ionic porous materials have been used with great versatility, for several purposes. In this work, the ionic dye-based RIO-55 was chosen to capture a series of lanthanides (Eu, Gd, Dy, and Tb) from water, observing their affinity with the lattice and the performance of the adsorbent. Thus, the higher adsorbed amount was referred to as Eu3+ 3+ (Q max = 370 mg/g), as well as the best affinity (KL L = 5x10-3),-3 ), following the Langmuir model. The impregnated Eu3+@RIO-55 3+ @RIO-55 was used for chemical sensing, capturing dopant molecules (ephedrine and dopamine) from water, showing great performance, even after some reuse cycles. In addition, some initial fluorescence tests were performed using RIO-55 and Eu3+@RIO-55 3+ @RIO-55 to observe the spectrum before and after lanthanide impregnation.