Physchem

Dye removal from aqueous solutions remains a major global environmental challenge. Among the various remediation techniques, adsorption using natural materials has gained significant attention. In this study, the adsorption of methylene blue (MB) by a natural volcanic rock (VR) adsorbent—collected from the Cerro Blanco volcano in Divisaderos, Sonora, Mexico—was investigated, and the process efficiency was evaluated at different temperatures. The comprehensive characterization revealed a rough and irregular porous surface via SEM, while the EDS elemental data and the CIPW normative calculations identified the material as a silica-saturated tholeiitic basalt, primarily composed of bytownite (${An}_{71})$ and pyroxenes. This petrological classification was cross-validated by XRD and FTIR spectra, which exhibited vibrational modes characteristic of mafic silicate. The surface analysis via the BET method indicated a specific surface area of 12 m²·g⁻¹, while a BJH analysis indicated a mesoporous structure (average pore diameter of 3.75 nm), and a Type IV isotherm with H3-type hysteresis, suggesting narrow, slit-shaped pores. Batch adsorption experiments demonstrated an exceptional removal efficiency of 99.99% for 50 mg·L⁻¹ MB within only 30 min. The equilibrium data and the adsorption kinetics followed the Langmuir isotherm and a pseudo-second-order model, respectively. Cytotoxicity assays confirmed the VR is biosafe. The combination of high removal efficiency, low cost, and environmental safety positions this material as high-potential adsorbent for sustainable water remediation processes. Full article

A novel mesoporous XAD-based adsorbent (A336/XAD-7) was produced by impregnating the ionic liquid A336 into the pores of XAD-7 resin and used to separate tin(IV) and cadmium(II) from high-level liquid waste (HLLW). The as-produced material was characterized by SEM-EDS, TG-DSC, and N₂ adsorption–desorption isotherms, which revealed a well-developed open pore structure, high loading capacity, and large specific surface area. Adsorption performance analysis showed that in 4 M HCl solution, the experimental saturated adsorption capacity qexp of A336/XAD-7 for Sn(IV) and Cd(II) were 39.51 mg/g and 34.18 mg/g, respectively, with equilibrium reached within 120 min. Among ten coexisting metal ions (Sn⁴⁺, Cd²⁺, Co²⁺, Ni²⁺, Cu²⁺, Eu³⁺, Y³⁺, Ca²⁺, Mg²⁺, Al³⁺) in HLLW, A336/XAD-7 exhibited excellent selectivity for Sn(IV) under high acidity, with a separation factor (SF_Sn/others) of 13.13. Column experiments further evaluated the dynamic separation of Sn(IV) from simulated HLLW using A336/XAD-7, achieving an enrichment factor greater than 7. XPS spectra indicated that the adsorption mechanism involved anion exchange between A336/XAD-7 and the complex anions SnCl₆²⁻ and CdCl₄²⁻. This work demonstrates the application potential of A336/XAD-7 for HLLW treatment and provides valuable guidance for the efficient separation of other metal ions. Full article

Accurate estimation of molecule–nanotube interaction energies is critical for the computational screening of carbon-based materials for hydrogen storage; however, density functional theory (DFT) calculations remain computationally expensive for extensive configurational sampling. In this work, we develop a multilayer perceptron (MLP) surrogate model to predict H₂–CNT interaction energies, represented by $E_{ads}$, for H₂ interactions with a chiral (2,1) carbon nanotube. A curated dataset comprising 696 configurations was generated using DMol³ (BIOVIA Materials Studio), varying intermolecular distance, molecular orientation, and interaction site across three regions: internal cavity, edges, and external surface. The proposed MLP architecture (64–32–1) incorporates GELU activation functions, L2 regularization, and dropout to improve generalization. The model achieves coefficients of determination in the range R² = 0.90–0.96 across all interaction regions, with particularly strong performance at the nanotube edges (R² = 0.9358, MSE = 0.046 eV²), as well as on the external surface (R² = 0.9625, MSE = 0.574 eV²) and within the internal cavity (R² = 0.9051, MSE = 1.506 eV²). The original $E_{ads}$ distribution had a mean of 4.0955 eV and a sample standard deviation of 4.3189 eV. The elevated energy values observed in the internal cavity (up to 12 eV) are consistent with steric repulsion induced by geometric confinement rather than predictive artifacts. The trained MLP showed close agreement with DFT-derived trends, enabling exploration of interaction-energy landscapes spanning both attractive and repulsive regimes. These results indicate that MLP-based models trained on diverse configurational datasets provide a computationally efficient alternative for screening carbon nanostructures in hydrogen storage applications, without substantially compromising accuracy relative to first-principles methods. Full article

In this work, an ultrasonic relaxation spectroscopic study of aqueous ammonium Fe(II) sulfate, aqueous ammonium Fe(III) sulfate and the corresponding ternary system has been undertaken. A variety of acoustic parameters including relaxation frequency, relaxation amplitude and speed of sound were determined as a function of solution concentration. In addition, the adiabatic compressibility and the molar volume change during the ionic association in ammonium Fe(II) sulfate and ammonium Fe(III) sulfate aqueous solutions were also estimated from the acoustic data. This approach facilitated a comprehensive characterization of the three systems across different concentrations. In the two binary systems, the presence of an ion association mechanism was identified involving the divalent and trivalent iron ions, with the sulfate anions, respectively. Furthermore, in the ternary system, an internal sphere oxidation–reduction mechanism occurred between the divalent and trivalent iron ions. All ions within each solution play an active role in shaping the structure of water molecules, owing to the prevailing kosmotropic characteristics specific to each solution. The results are examined within the context of the current phenomenological understanding in the field. Full article

This work reports the colloidal synthesis of Nd-containing mixed-halide perovskite quantum dots described as CsPb(Nd)Br_3−γCl_γ, followed by post-synthetic surface modification with an acid-activated amino-functional siloxane. This notation is used deliberately because the available FE-SEM, DLS, EDX, and optical data confirm the formation of an Nd-containing mixed-halide colloidal perovskite system, but do not provide direct crystallographic proof of substitutional Nd³⁺ incorporation at the Pb²⁺ B-site. The obtained dispersions show stable blue emission with a maximum at about 458 nm, a photoluminescence quantum yield of about 56%, an essentially invariant emission maximum when the excitation wavelength is varied from 300 to 390 nm, and monoexponential decay kinetics with a characteristic lifetime of 6.67 ± 0.97 ns. Field-emission scanning electron microscopy combined with morphometric analysis of at least 150 particles indicates a nanoscale size distribution with an average equivalent diameter of 8.8 nm, a median of 7.3 nm, and 93.25% of particles smaller than 25 nm. Dynamic light scattering confirms a narrow hydrodynamic size distribution in the 7–9 nm range and a low polydispersity index. Elemental mapping by EDX confirms the co-presence of Cs, Pb, Br, Cl, and Nd in the analyzed particles. The observed blue shift is discussed in terms of the combined effect of chloride incorporation, nanoscale size, possible Nd-related perturbation of the local electronic/defect structure, and reduced non-radiative losses after surface passivation. No definitive crystallographic assignment of Nd to a specific lattice site is claimed; the composition is therefore treated as nominal, and the structural interpretation remains provisional pending XRD/XPS or related studies. Full article

Heparin is a highly sulphated polyelectrolyte, and its properties depend strongly on its shape in solution. In this study, we closely examined the structural behaviour of low-molecular-weight heparin under aerobic ultraviolet-C (UVC, 100–280 nm) radiation. Using controlled photodegradation, we prepared native, small, and ultra-small molar-mass fractions, enabling us to investigate how structural properties vary with molecular weight. We examined relationships among molar mass, radius of gyration, second virial coefficient, and critical overlap concentration to characterise different conformational states. Our results showed that as molar mass decreased, the chain diameter and persistence length also dropped, while the overlap concentration increased. This indicates a reduced hydrodynamic volume and increased chain flexibility. Positive second virial coefficient values indicate that polymer–solvent interactions remained favourable after photodegradation. The scaling exponents suggest that degraded heparin behaves as a semi-flexible polyelectrolyte and adopts an extended-coil shape in water with electrolytes. Further analysis showed that the characteristic ratio and chain stiffness decreased as chains were broken by irradiation. Overall, aerobic UVC irradiation provides a reliable way to modify the physical structure of these molecules while maintaining solution stability. These findings show a clear link between reduced molecular weight and changes in shape, which is useful for developing better low-molecular-weight heparins for several applications, including pharmaceutical and medical use. Full article

The question of verification of food quality has stood before scientists since ancient times, and, nowadays, the advances in science and technology have made it a very challenging task. Laser-induced fluorescence (LIF) spectroscopy has become a very useful instrument for sample characterization. Nevertheless, analysis of complex multi-component spectra is difficult to approach. In recent years, the capabilities of artificial intelligence have attracted a lot of attention, as they open doors to efficient solutions of many problems that otherwise require a lot of time, effort, expenses and often inspiration. In the present work, we use LIF spectra of mixtures of sunflower and extra virgin olive oils with different concentrations and apply neural network (NN) algorithms with the aim of improving the strategies for concentration determination. Two different approaches have been applied and their output has been compared and commented. More specifically, the task of concentration recognition has been targeted as a classification and as a fitting problem. We formulate four diagnostic parameters with biochemical meaning and compare the NN performance when training with raw spectra and with the diagnostic parameters. The correct choice of appropriate diagnostic parameters is of importance from the point of view of biochemical interpretability and analysis, whereas “black box” full-spectra training might be beneficial for end-user applications. Our results show that these methods perform well even with very scarce data and outline preliminary strategies for defining diagnostic criteria. Full article

In physical chemistry textbooks, it is explained that thermodynamic processes in isolated systems (with constant internal energy) evolve until the total entropy reaches a maximum value; irreversible processes, or those in closed systems (at a constant entropy value of the system), evolve until the total internal energy reaches a minimum value; and in quasi-static processes, the maximum work is obtained under the given conditions. However, if the maximum useful work is not obtained from the system, the thermodynamic process is usually described using the Clausius inequality. Assuming that the internal energy and entropy are first-order homogeneous functions (according to Euler’s relation and additivity over system elements) and that they are state functions based on the principle of local equilibrium, the principle of maximum entropy and minimum internal energy can be applied not only to entire isolated or closed systems but to any volume element of the system. From this follows a unique discussion of the transition of a closed system (with a quasi-static isentropic process) to an isolated (irreversible) system, along with the thermodynamic process that occurs when the system remains closed and does not achieve the maximum useful work, some of which is dissipated. Full article

The present work represents a step forward in the production of a battery that can be recharged with light, without the need to integrate an energy generation device (e.g., a solar cell). Here, a silicon Li-ion battery electrode is reported, which has a current collector with an optical window that allows the impinging of light to it. The contact between the current collector and silicon is Schottky-type, behaving as a photodiode that injects charges into the electrode, which are added to the current applied to it when it is charged. The electrode presented in the present work is a proof of concept, with one of the simplest possible structures that the electrode could have to be functional (an optimized microstuctured electrode with improved charge/discharge cycling stability is envisioned): the electrode consists of monolithic silicon that has been microstructured in the backside by metal assisted chemical etching and has been decorated with Cu particles that work as a current collector. I-V curves show that the electrode by itself functions as a Schottky-type photodiode. On the other hand, when the chip is used as an electrode of a Li-ion battery, it can be properly lithiated/delithiated (it is a rechargeable electrode). Furthermore, it has been proven that when lithiation has been performed, this process has been enhanced by applying light to the current collector. Full article

Hydrogen energy systems rely extensively on polymeric materials for storage, sealing, transport, and tribological applications; however, their long-term reliability is strongly influenced by hydrogen–polymer interactions. This review presents a comparative analysis of polymers with and without hydrogen bonding, focusing on how molecular architecture governs hydrogen compatibility, transport behavior, and degradation mechanisms under high-pressure environments. Hydrogen-bonded polymers, such as polyamides, polyurethanes (PU), and polyimides, exhibit high mechanical strength and thermal stability due to strong intermolecular interactions but are susceptible to hydrogen-assisted chemical degradation and embrittlement. In contrast, non-hydrogen-bonded polymers, including polyethylene, polypropylene (PP), polytetrafluoroethylene (PTFE), and Polyether ether ketone (PEEK), demonstrate excellent chemical inertness and low hydrogen reactivity, yet experience diffusion-driven damage such as blistering and fatigue softening. This study establishes a unified framework linking molecular structure, hydrogen transport, and failure mechanisms, revealing a fundamental trade-off between mechanical integrity and chemical stability. Advanced strategies, including polymer blending, nanofiller reinforcement, and multilayer composites, are proposed to optimize durability, permeability, and overall hydrogen compatibility. Full article

The growing demand for sustainable smart packaging arises from the urgent need to preserve food quality and minimize environmental waste. In this study, multifunctional gelatin-based pH-responsive indicator films were fabricated by incorporating anthocyanins extracted from Hibiscus x archeri W Watson (HAE) and zinc oxide nanoparticles (ZnO-NPs). The incorporation of HAE and ZnO-NPs enhanced surface hydrophobicity, as evidenced by an increase in the water contact angle from 99° to 106°. The Fourier transform infrared (FTIR) analysis verified the lack of new chemical bond formation, indicating that the interactions among components were primarily physical in nature. Distinct colour transitions in buffer solutions of differing pH demonstrated the films’ colorimetric behavior. The films exhibited strong antimicrobial activity against Listeria monocytogenes (18.961 mm), Salmonella typhimurium (18.969 mm), and Aeromonas hydrophila (18.237 mm), whereas the neat gelatin film showed no inhibitory zone. The films also demonstrated superior UV-blocking capacity, with an opacity value (1.34 a.u/mm) compared to the control gelatin film (0.79 a.u/mm). Notably, fish fillets wrapped with the films remained fresh for up to 10 days, compared to day 4 for the unwrapped samples. These findings highlight the considerable potential of multifunctional, active and intelligent packaging for food preservation and real-time freshness monitoring. Full article

The high pressure response and structural stability of crystalline racemic (RS) ibuprofen up to 7 GPa are explored by Raman spectroscopy, employing diamond anvil cells for the pressure application and glycerol as the pressure transmitting medium. Two independent high pressure experiments were performed with practically identical results. Both intermolecular vibrations (associated with weak van der Waals interactions and hydrogen bonding between ibuprofen molecules) and intramolecular vibrations (associated with strong covalent bonding within the ibuprofen molecule) are monitored as a function of pressure, with the former being far more susceptible to volume contraction. The pressure dependence of the Raman peak frequencies undergoes two distinct changes at ~2 and ~6 GPa, indicating the occurrence of pressure-induced structural modifications of ibuprofen. Based on the high pressure Raman data for the intermolecular vibrations of the RS ibuprofen below 2 GPa, a zero pressure value for the bulk modulus of ~7.5 GPa is also extracted. Full article

The interaction between airborne allergens and environmental microplastics is an emerging concern in the context of increasing plastic pollution and allergic disease prevalence. In this study, we investigated the molecular interaction between Cry j 1, the major allergen of Japanese cedar (Cryptomeria japonica) pollen, and polyethylene terephthalate (PET) microplastic surfaces using all-atom molecular dynamics simulations integrated with computational epitope selection analyses. The simulations showed that Cry j 1 adsorbs onto PET primarily through hydrophobic and van der Waals interactions, with residues Pro165, Ala227, Tyr228, and Val163 contributing prominently to surface association. Mapping of selected epitope regions indicated that several linear B-cell epitopes remained solvent exposed following adsorption, whereas two CD4⁺ T-cell epitope regions (T5 and T6) contributed more directly to PET interaction. PET adsorption was accompanied by moderate changes in conformational dynamics, including reduced residue-level flexibility and localized secondary-structure adjustments, while the overall protein fold remained structurally stable throughout the simulation. Small decreases in radius of gyration and solvent-accessible surface area suggested mild adsorption-associated compaction rather than major unfolding. These findings indicate that PET association can influence the structural dynamics and interfacial behavior of Cry j 1 without extensive disruption of its global architecture. Because the study is entirely computational, the immunological implications remain hypothetical and require experimental validation. Nevertheless, this work provides a molecular-level framework for understanding how airborne microplastics may influence allergen behavior and protein-surface interactions in polluted atmospheric environments. Full article

Given the depletion of conventional oil and gas resources, oil shale represents a promising alternative source of hydrocarbons that can be recovered through pyrolysis. This study examines the thermal decomposition of raw oil shale from the Tarfaya deposit and its decarbonized concentrate, studied by thermogravimetric analysis at different heating rates (5, 10, 20 and 40 °C/min). Pretreatment with acetic acid enabled the selective removal of calcite, confirmed by elemental, XRF, and XRD analyses, which revealed a relative enrichment in silica and dolomite in the oil shale concentrate. Pyrolysis of the raw shale occurs primarily between 300 and 500 °C, with a conversion rate of approximately 30%. In contrast, for the oil shale concentrate, the pyrolysis process begins at a relatively low temperature, within a wider temperature range (260–520 °C). Kinetic analysis based on Flynn–Wall–Ozawa (FWO) and Kissinger–Akahira–Sunose (KAS) methods shows that at a conversion rate of 60%, the activation energy achieves 14.09 kJ/mol and 10.78 kJ/mol, respectively. The results indicate that the selective removal of calcite by acetic acid treatment facilitates kerogen pyrolysis by reducing mineral–organic interactions. Indeed, calcite dilutes the reactive organic fraction and can act as a physical barrier limiting heat and mass transfer within the oil shale. Its removal improves, on the one hand, the accessibility of kerogen to thermal cracking and promotes its decomposition, and on the other hand, reduces the amount of residue after pyrolysis. In addition, the kinetic analysis based on Criado master curves reveals changes in the reaction mechanism after decarbonation treatment depending on the heating rate (β). A shift from a two-dimensional Avrami–Erofeev model (A2) to a three-dimensional model (A3) was observed at a low heating rate (β = 5 °C/min), suggesting a change in nucleation and growth dynamics during kerogen decomposition. At high heating rates (10, 20 and 40 °C/min), the thermal decomposition of kerogen combines several reaction mechanisms depending on the temperature range considered. Full article

Glyphosate is a highly polar herbicide, the reliable molecular recognition of which is complicated by co-occurring structural analogues, metabolites, and derivatives in real-world samples. Rather than reporting new aptamer discovery, this study establishes a standardized, solution-phase isothermal titration calorimetry (ITC) workflow to thermodynamically reassess two literature-reported glyphosate DNA aptamers, Seq03 and Seq05, under matched buffer composition and instrument settings. After verification of baseline stability and evaluation of heat-of-dilution contributions, ligand-to-aptamer titrations yielded apparent dissociation constants of approximately 8.14 μM for Seq03 and 40.2 μM for Seq05, enabling affinity-based prioritization of these reported candidates within the tested concentration window. To define an application-relevant selectivity boundary, we further constructed a counter-screen panel restricted to glyphosate-related chemicals, including structural analogues, metabolites, and derivatives, and evaluated all candidates using an identical ITC protocol with explicit background handling. None of the counter-screen compounds produced binding-consistent, saturable isotherms after integration and control-based interpretation; instead, their responses remained close to background heat and were therefore operationally classified as having no detectable binding under the tested conditions, including a reverse-titration format check with Glufosinate-N-acetyl. Collectively, these results position ITC as a label-free, platform-independent validation step for small-molecule aptamer benchmarking prior to analytical translation, while also highlighting that the present conclusions are bounded by the tested PBS-based conditions and the sensitivity window of the current ITC configuration. Full article

The widespread adoption of additive manufacturing, particularly selective laser sintering (SLS), has raised concerns about the disposal of unused thermoplastic powder residues, such as polyamide 12 (PA12). The high cost of PA12 and its degradation during the SLS process highlight the need for sustainable reuse strategies. This study evaluates the feasibility of reprocessing non-sintered PA12 powder without the addition of virgin material through fused deposition modeling (FDM) and injection molding (IM). Thermal analysis showed that the material retains processing temperatures comparable to virgin PA12. However, a significant reduction in melt flow index (≈61%) was observed, reflecting reduced processability and suggesting molecular-level changes affecting chain mobility. Injection molding demonstrated consistent mechanical behavior and good ductility, confirming its suitability for processing recycled PA12. In contrast, FDM processing resulted in higher variability and reduced ductility, mainly due to limitations in interlayer bonding associated with the increased viscosity of the material. Overall, the results highlight injection molding as a robust route for the valorization of non-sintered PA12, while FDM remains a feasible but less reliable alternative requiring further optimization. Full article

This study uses a bismuth ferrite (BiFeO₃) and MXene (Ti₃C₂Tx) to design a surface plasmon resonance (SPR) biosensor for the sensitivity enhancement at a 633 nm wavelength. Here, MXene serves as a biorecognition element (BRE) layer to ensure stable and reliable biomolecule adsorption. The MXene is a family of two-dimensional (2D) materials with metallic-like conductivity, a large surface area that can attach biomolecules, and improve biocompatibility. The addition of a conductive 2D MXene layer and a high-index BiFeO₃ dielectric layer greatly improves light–matter interaction and evanescent field penetration at the sensing interface. Strong plasmonic coupling is indicated by the reflectance analysis, which shows a distinct and consistent shift in the resonance angle as analyte RI increases. This study examined the sensitivity at optimized Ag and BiFeO₃ layer thickness. At an Ag of 39 nm and BiFeO₃ of 3 nm thickness, the maximal sensitivity of 340.68°/RIU with a remarkable figure of merit (FoM) of 47.38/RIU is obtained. The overall detection accuracy (DA) and FoM are significantly improved by the large sensitivity enhancement, despite a slight increase in full width at half maximum (FWHM). Furthermore, the penetration depth (PD) of 198.50 nm (at RI:1.330) and 199.52 nm (at RI:1.335) is attained with the proposed structure. Due to its high sensitivity, reusability, and reproducibility, the SPR biosensor has the potential to be used in biochemical, environmental, and medical detection. Full article

This study reports that titanium nanoparticles can be used as a surface coating to enhance the corrosion resistance of 316 stainless steel. It specifically examines the influence of the deposition temperature (T_dep) on the coating’s structural and morphological properties, including corrosion behavior. TiO₂ nanoparticles were thoughtfully deposited on steel substrates at temperatures of 300, 400, and 500 °C using a horizontal hot-wall tubular reactor. This equipment was expertly engineered at the CIDETEQ laboratory through the metal–organic chemical vapor deposition (MOCVD) concept. Titanium isopropoxide [Ti(OC₃H₇)₄] was used as the precursor for the coating synthesis. Structural analysis was conducted using X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), and scanning electron microscopy (SEM). Corrosion performance was evaluated under accelerated conditions in 0.5 M H₂SO₄ using potentiodynamic anodic polarization (AP), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The corrosion test indicates that increasing T_dep significantly differentiates the coating morphology and improves corrosion resistance. AP revealed that the pitting potential (E_pit) shifted to more positive values, ranging from +1.4 to +1.5 V. CV voltammograms indicated that coated samples had lower passive current densities (I_p ≈ 10⁴ to 10⁵ A/cm²) than the bare substrate. EIS analysis demonstrated that the coating deposited at 500 °C processed the most favorable electrochemical performance, resisting corrosion for over 28 days. This coating achieved the highest electrical resistance (297 kΩ·cm²) and the lowest capacitance (2.7 μF/cm²), attributed to the formation of a crystalline anatase phase composed of pyramidal-like nanoparticle agglomerates (~40 nm). The dense packing structure effectively blocks charge-transfer pathways, restricting electron and ion transfer. Finally, MOCVD-based chemical surface modification with TiO₂ nanoparticles is considered an innovative method to improve the corrosion resistance of stainless steel, thereby prolonging its durability under accelerated sulfuric acid exposure. Full article

Polymer–graphene composites have emerged as an advantageous class of functional materials that combine the exceptional electrical, mechanical, and surface properties of graphene with the ability to be processed, modified, and made more flexible through polymers. Polymer–graphene composites have recently seen rapid growth in environmental applications, including water treatment, pollutant degradation, sensing, and energy–environment interfaces. This review critically examines recent advancements in polymer–graphene composites for catalysis (including photocatalysis, electrocatalysis, hydrogenation, and energy conversion) and environmental applications (such as water treatment, dye degradation, heavy-metal removal, and oil–water separation). There is considerable discussion about structure–property–performance relationships, catalytic and adsorption mechanisms, and the role of polymer matrices. Current challenges, scalability issues, and future research directions for sustainable, industrially viable polymer–graphene systems are highlighted. Full article