Physchem, Volume 5, Issue 3 (September 2025) – 15 articles

Animal tissue by-products, rich in collagen, represent a valuable source of biomaterials. Understanding their physicochemical and thermal behavior is essential for expanding their applications. In this study, pigskin gelatin was extracted through acid hydrolysis using a combination of acetic acid (AH) and either lactic, citric, or ascorbic acid (75:25, v:v, [0.5 M]), followed by thermal denaturation. We evaluated the physicochemical properties of the gelatin solutions (pH, hydroxyproline content, and extraction yield), as well as the macroscopic gel characteristics. Gelatin films were then prepared and analyzed for moisture content, color, and thermal properties. One-way ANOVA was applied to compare treatments, and Pearson’s correlation was used to assess the relationship between the solution pH and physicochemical parameters. Significant differences in the final pH of the solutions were observed among the acid mixture treatments, though the hydroxyproline content and extraction yield were not significantly affected. All gelatin solutions formed stable gels, and the resulting films exhibited similar moisture content. Thermal analysis revealed treatment-dependent variations. Specifically, a significant negative correlation (p < 0.005) was found between the gelatin solution pH and the melting temperature. These results suggest that the use of organic acid mixtures can effectively modulate gelatin properties, offering a versatile approach for tailoring biomaterials for both food and non-food applications. Full article

The paper describes the conversion of carbon dioxide into methanol in a chemical reactor under standard operating conditions. Electro-analytical techniques, cyclic voltammetry, and chrono-amperometry characterize the process. The electrochemical redox reaction develops using various catalyzers to evaluate the performance of the carbon dioxide conversion into methanol process under variable chemical conditions. The results of the applied technique showed an incomplete redox reaction with an electronic change of z = 2.84 on average, below the ideal number, z = 6, that may be due to methanol decomposition (reverse reaction) because the system operates with a reaction constant above the equilibrium value. The methanol production may improve by draining the methanol/water solution from the chemical reactor to reduce the methanol concentration in the electrochemical cell, shifting the forward reaction towards the formation of methanol, increasing the electron change number, which approaches the ideal value, and improving the methanol production efficiency. The draining process shows a significant increase in methanol formation, which depends on the draining flow rate and the catalyzer type. A simulation process shows that if we operate in optimum conditions, with no methanol decomposition through a reverse reaction, the redox reaction fulfills the ideal condition of maximum electronic change. The experimental tests validate the simulation results, showing a relevant increase in the electron change number with values up to z = 4.2 for optimum draining flow rate conditions (0.2 L/s). The experimental results show a relative increase factor of 4.7 in methanol production, meaning we can produce more than four times more methanol compared with no draining techniques. The data analysis shows that the draining flow rate has a threshold of 0.2 L/s, beyond which the extent of the reaction reverses, reducing the methanol formation due to a chemical reaction disequilibrium. The paper concludes that using the draining method, the methanol production mass rate increases significantly from an average value of 20.9 kg/h for non-draining use, considering all catalyzer types, to a range between 91.9 kg/h and 104.3 kg/h, depending on the flow rate. Averaging all values for different flow rates and comparing with the non-draining case, we obtain an absolute methanol production mass rate of 77 kg/h, meaning an incremental percentage of 469.1%, more than four times the initial production. Although the proposed methodology looks promising, applying this procedure on an industrial scale may suffer from restrictions since the chemical reactions intervening in the methanol formation do not perform linearly. According to experimental tests, the best option among the six catalyzers used for methanol production is the plain copper, with copper oxides (Cu₂O, CuO) and copper Sulphur (CuS) as feasible alternatives. Full article

Solid solutions of the metallocenes ferrocene (Cp₂Fe), nickelocene (Cp₂Ni), and cobaltocene (Cp₂Co) have been prepared by manually grinding the components together, or by co-crystallizing them from solution. In the solid solutions Cp₂Fe/Cp₂Ni and Cp₂Co/Cp₂Ni, the cyclopentadienyl (Cp) protons relax via dipolar electron–proton interactions, which represent the dominant relaxation mechanism. The ¹H T₁ relaxation times of the molecules Cp₂Ni and Cp₂Co, dissolved in CDCl₃, and in the solid solutions, show that the relaxation takes place intramolecularly. The relaxation of the protons is propagated exclusively via the unpaired electrons of the metal centers to which their Cp rings are coordinated, due to the large intermolecular distances that are greater than 3.91 Å. In contrast, the intramolecular distances between the electrons of the metal atoms and the protons of their coordinated Cp rings are merely 2.70 Å. Using these intramolecular distances and the ¹H T₁ relaxation times, the electron relaxation times T_1e have been determined as 17 × 10⁻¹³ s in CDCl₃ solutions and 45 × 10⁻¹³ s in the solid state for Cp₂Ni. The corresponding T_1e times for Cp₂Co are calculated as ca. 5 × 10⁻¹³ s and 20 × 10⁻¹³ s. Grinding Cp₂Fe and Cp₂Ni together leads to two different ¹H T₁ relaxation times for the protons of Cp₂Fe. The longer T₁ relaxation time indicates domains that consist mostly of Cp₂Fe molecules. The short T₁ times show a close contact of Cp₂Fe and Cp₂Ni molecules. An analysis of the short ¹H T₁ times reveals the presence of at least two to three short distances of 3.91 Å between Cp₂Fe and Cp₂Ni molecules. These results support the hypothesis that dry grinding of the metallocenes Cp₂Fe and Cp₂Ni in ratios that were changed in 10% increments from 90%/10% to 30%/70% leads to domains that mostly consist of Cp₂Fe molecules, and additionally to domains that contain a mixture of the components on the molecular level. Full article

Intergrown mixtures of nanostructured manganese oxide phases have been obtained using a highly complexing agent (ethylenediamine) and a weak complexer (urea) during their solvothermal synthesis. In this work, through a detailed structural analysis, it is evidenced the formation of an intergrown mixture of three distinct manganese oxide phases (β-MnO₂, α-Mn₂O₃, and Mn₃O₄). Scanning electron microscopy shows that the products have just one morphology, indicating that the different manganese oxide phases may have grown together, organizing themselves in a 3D crystal network. The reaction mechanisms are discussed in this paper. It is of great interest to produce intergrown mixtures of manganese oxide phases to take advantage of the availability of the different oxidation states of Mn in neighboring crystallites for applications like catalysis. Full article

In this study, supramolecular inclusion complexes composed of komecosanol (Ko), a lipophilic compound derived from rice bran, and α-cyclodextrin (αCD) were prepared using a solvent-free three-dimensional (3D) ball milling method. Their physicochemical properties were examined using various techniques. Powder X-ray diffraction analysis of the ground mixture at a Ko/αCD ratio of 1/8 revealed the disappearance of diffraction peaks characteristic of Ko and the emergence of new peaks, indicating the formation of a distinct crystalline phase. Moreover, differential scanning calorimetry analysis showed the disappearance of the endothermic peaks corresponding to Ko, indicating molecular-level interactions with αCD. Near-infrared spectroscopy results suggested the formation of hydrogen bonds between the C–H groups of Ko and the O–H groups of αCD. Solid-state ¹³C CP/MAS NMR and T₁ relaxation time measurements indicated the formation of a pseudopolyrotaxane structure, while scanning electron microscopy images confirmed distinct morphological changes consistent with complex formation. These findings demonstrate that 3D ball milling facilitates the formation of Ko/αCD inclusion complexes with a supramolecular architecture, providing a novel approach to improve the formulation and bioavailability of poorly water-soluble lipophilic compounds. Full article

The synthesis of Fe₃O₄ and ε-Fe₂O₃ nanoparticles (hereafter referred to as Fe₃O₄ NPs and ε-Fe₂O₃ NPs, respectively) was conducted in an eco-friendly manner using FeCl₃·6H₂O as the primary reactant. The experiment was conducted by subjecting the sample to an aqueous solution of FeCl₂·4H₂O at a temperature of 80 °C for a duration of 45 min, with the inclusion of apricot kernel shell extract (AKSE) as a natural reducing agent. The synthesized Fe₃O₄ NPs and ε-Fe₂O₃ NPs were characterized using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The optical properties of Fe₃O₄ NPs and ε-Fe₂O₃ NPs were examined, with the band gap energy estimated using the Kubelka–Munk formula. The results demonstrated a band gap of E_g (Fe₃O₄ NPs) = 2.59 eV and E_g (ε-Fe₂O₃ NPs) = 2.75 eV, thereby confirming their semiconductor behavior. The photoconductivity of Fe₃O₄ NPs and ε-Fe₂O₃ NPs was analyzed as a function of photon energy. For Fe₃O₄ NPs, photoconductivity exhibited an increase between 1.37 eV and 6.2 eV prior to reaching a state of stability. A comparable trend was observed for ε-Fe₂O₃ NPs, with an increase from 1.35 eV to 6.22 eV, followed by stabilization. Furthermore, the extinction coefficient (k) was determined. For Fe₃O₄ NPs, k ranged from 39 to a maximum of 300, while for ε-Fe₂O₃ NPs, it varied from 37 to a maximum of 280. A higher k value indicates strong light absorption, rendering these nanoparticles highly suitable for photothermal and sensing applications. Full article

Pectin is a renewable polysaccharide valued for its gelling, stabilising, and encapsulating properties, with broad applications in food, pharmaceutical, and industrial sectors. However, extraction conditions critically affect its yield, structural integrity, and functional performance. Despite citrus peel being a major source of pectin, large amounts remain underutilised as waste. This study systematically investigates how different acid types influence the extraction efficiency and structural quality of pectin derived from citrus peel. Dried citrus peel powder was extracted using four acids—sulphuric, hydrochloric, acetic, and citric—under controlled conditions at 80 °C. Extractions were performed at a fixed time of 90 min for all acids, with additional time trials for sulphuric acid. Extracted pectins were evaluated for gravimetric yield, colour, solubility, degree of esterification (DE) by titration and FTIR, and structural features using FTIR and ¹H NMR spectroscopy. Results showed that sulphuric and hydrochloric acids yielded the highest pectin recoveries (30–35% and 20–25%, respectively) but caused significant degradation, evident from dark colour, broad FTIR peaks, low DE (<10%), and poor solubility. In contrast, acetic and citric acid extractions resulted in moderate yields (8–15%) but preserved the pectin backbone and maintained higher DE (>30%) compared to the mineral acid-extracted samples and the commercial low methoxyl (LM) standard, as confirmed by clear FTIR and NMR profiles. These findings demonstrate the trade-off between extraction yield and structural integrity, underscoring the potential of mild organic acids to produce high-quality pectin suitable for value-added applications. Optimising acid type and extraction conditions can support sustainable waste valorisation and expand the industrial use of citrus-derived pectin. Full article

Anthraquinone acid dyes are widely used in dyeing polyamide due to their good exhaustion and brightness. While ionic interactions primarily govern dye–fiber bonding, the molecular weight (Mw) of these dyes can significantly influence migration, apparent color strength, and fastness behavior. This study offers comparative insight into how the Mw of structurally similar anthraquinone acid dyes impacts their diffusion, fixation, and functional outcomes (e.g., UV protection) on polyamide 6 fabric, using Acid Blue 260 (Mw~564) and Acid Blue 127:1 (Mw~845) as representative low- and high-Mw dyes. The effects of dye concentration, pH, and temperature on color strength (K/S) were evaluated, migration index and zeta potential were measured, and UV protection factor (UPF) and FTIR analyses were used to assess fabric functionality. Results showed that the lower-Mw dye exhibited higher migration tendency, particularly at increased dye concentrations, while the higher-Mw dye demonstrated greater color strength and superior wash fastness. Additionally, improved UPF ratings were associated with higher-Mw dye due to enhanced light absorption. These findings offer practical insights for optimizing acid dye selection in polyamide coloration to balance color performance and functional attributes. Full article

A scalable synthesis of two-dimensional titanium nitride chloride (TiNCl) via flash Joule heating (FJH) using titanium tetrachloride (TiCl₄) precursor has been developed. This single-step method overcomes traditional synthesis challenges, including high energy consumption, multi-step procedures, and hazardous reagent requirements. The structural and chemical properties of the synthesized TiNCl were characterized through multiple analytical techniques. X-ray diffraction (XRD) patterns confirmed the presence of TiNCl phase, while Raman spectroscopy data showed no detectable oxide impurities. Fourier transform infrared spectroscopy (FTIR) analysis revealed characteristic Ti–N stretching vibrations, further confirming successful titanium nitride synthesis. Transmission electron microscopy (TEM) imaging revealed thin, plate-like nanostructures with high electron transparency. These analyses confirmed the formation of highly crystalline TiNCl flakes with nanoscale dimensions and minimal structural defects. The material exhibits excellent structural integrity and phase purity, demonstrating potential for applications in photocatalysis, electronics, and energy storage. This work establishes FJH as a sustainable and scalable approach for producing MXenes with controlled properties, facilitating their integration into emerging technologies. Unlike conventional methods, FJH enables rapid, energy-efficient synthesis while maintaining material quality, providing a viable route for industrial-scale production of two-dimensional materials. Full article

This review explores CO₂ methanation and steam methane reforming (SMR) as two key thermochemical processes governed by reversible reactions, each offering distinct contributions to carbon-neutral energy systems. The objective is to provide a comparative assessment of both processes, highlighting how reaction reversibility can be strategically leveraged for decarbonization. The study addresses methane production via CO₂ methanation and hydrogen production via SMR, focusing on their thermodynamic behaviors, catalytic systems, environmental impacts, and economic viability. CO₂ methanation, when powered by renewable hydrogen, can result in emissions ranging from −471 to 1076 kg CO₂-equivalent per MWh of methane produced, while hydrogen produced from SMR ranges from 90.9 to 750.75 kg CO₂-equivalent per MWh. Despite SMR’s lower production costs (USD 21–69/MWh), its environmental footprint is considerably higher. In contrast, methanation offers environmental benefits but remains economically uncompetitive (EUR 93.53–204.62/MWh). Both processes rely primarily on Ni-based catalysts, though recent developments in Ru-based and bimetallic systems have demonstrated improved performance. The review also examines operational challenges such as carbon deposition and catalyst deactivation. By framing these technologies through the shared lens of reversibility, this work outlines pathways toward integrated, efficient, and circular energy systems aligned with long-term sustainability and climate neutrality goals. Full article

Plastic waste and water pollution demand circular economy-driven innovations. This review examines metal–organic framework (MOF) synthesis from polyethylene terephthalate (PET) waste for wastewater treatment. Depolymerized PET yields terephthalic acid and ethylene glycol—essential MOF precursors. We evaluate the following: (1) PET depolymerization (hydrolysis, glycolysis, ammonolysis) for monomer recovery efficiency; (2) MOF synthesis (solvothermal, microwave, mechanochemical) using PET-derived linkers; (3) performance in adsorbing heavy metals, dyes, and emerging contaminants. PET-based MOFs match or exceed commercial adsorbents in pollutant removal while lowering costs. Their tunable porosity and surface chemistry enhance selectivity and capacity. By converting waste plastics into functional materials, this strategy tackles dual challenges: diverting PET from landfills and purifying water. The review underscores the environmental and economic benefits of waste-sourced MOFs, proposing scalable routes for sustainable water remediation aligned with zero-waste goals. Full article

Conductive polymer composites (CPCs) filled with anisotropic materials such as carbon nanotubes (CNTs) exhibit electrical behavior governed by percolation through filler networks. While filler volume and shape are commonly studied, the influence of orientation and alignment remains underexplored. This study uses Monte Carlo simulations to examine how the mean orientation angle and angular dispersion of CNTs affect conductive network formation. The results demonstrate that electrical connectivity is highly sensitive to orientation. Contrary to conventional assumptions, maximum connectivity occurred not at 45° but at around 55–60°. A Gaussian-based orientation probability function was proposed to model this behavior. Additionally, increased orientation dispersion enhanced conductivity in cases where alignment initially hindered connection, highlighting the dual role of alignment and randomness. These findings position orientation as a critical design parameter—beyond filler content or geometry—for engineering CPCs with optimized electrical performance. The framework provides guidance for processing strategies that control alignment and supports applications such as stretchable electronics, directional sensors, and multifunctional materials. Future research will incorporate full 3D orientation modeling to reflect complex manufacturing conditions. Full article

The research reviews and contrasts two studies based on the gas-phase reaction OH + D₂(v, j). In these studies, Quasi-Classical Trajectory (QCT) calculations and the Gaussian Binning (GB) technique were used on the Wu–Schatz–Lendvay–Fang–Harding (WSLFH) potential energy surface. Large sample sizes allow for precise energy state distribution analysis across translational, vibrational, and rotational components in the products. A key observation is the influence of the vibrational and rotational excitation of D₂ on the total angular momentum (J′) of the HOD* product. This study reveals that increasing the vibrational level, vD₂, significantly shifts P(J′) distributions toward higher values, broadening them due to increased isotropy. In contrast, increasing the rotational level, jD₂, results in a smaller shift but introduces greater anisotropy, leading to a more selective distribution of J′ values. The dual Gaussian Binning selection—Vibrational-GB followed by Rotational-GB—further highlights a preference for either odd or even J′ values, depending on the specific excitation conditions. These findings have implications for the development of chemical lasers, as the excitation and emission properties of HOD* can be leveraged in the laser design. Future research aims to extend this study to a broader range of initial conditions, refining the understanding of reaction dynamics in controlled gas-phase environments. Full article

Solid oxide fuel cells (SOFCs) represent a pivotal technology in renewable energy due to their clean and efficient power generation capabilities. Their role in potential carbon mitigation enhances their viability. SOFCs can operate via a variety of alternative fuels, including hydrocarbons, alcohols, solid carbon, and ammonia. However, several solutions have been proposed to overcome various technical issues and to allow for stable operation in dry methane, without coking in the anode layer. To avoid coke formation thermodynamically, methane is typically reformed, contributing to an increased degradation rate through the addition of oxygen-containing gases into the fuel gas to increase the O/C ratio. The performance achieved by reforming catalytic materials, comprising active sites, supports, and electrochemical testing, significantly influences catalyst performance, showing relatively high open-circuit voltages and coking-resistance of the CH₄ reforming catalysts. In the next step, the operating principles and thermodynamics of methane reforming are explored, including their traditional catalyst materials and their accompanying challenges. This work explores the components and functions of SOFCs, particularly focusing on anode materials such as perovskites, Ruddlesden–Popper oxides, and spinels, along with their structure–property relationships, including their ionic and electronic conductivity, thermal expansion coefficients, and acidity/basicity. Mechanistic and kinetic studies of common reforming processes, including steam reforming, partial oxidation, CO₂ reforming, and the mixed steam and dry reforming of methane, are analyzed. Furthermore, this review examines catalyst deactivation mechanisms, specifically carbon and metal sulfide formation, and the performance of methane reforming and partial oxidation catalysts in SOFCs. Single-cell performance, including that of various perovskite and related oxides, activity/stability enhancement by infiltration, and the simulation and modeling of electrochemical performance, is discussed. This review also addresses research challenges in regards to methane reforming and partial oxidation within SOFCs, such as gas composition changes and large thermal gradients in stack systems. Finally, this review investigates the modeling of catalytic and non-catalytic processes using different dimension and segment simulations of steam methane reforming, presenting new engineering designs, material developments, and the latest knowledge to guide the development of and the driving force behind an oxygen concentration gradient through the external circuit to the cathode. Full article

Food irradiation is gaining popularity worldwide due to its potential to extend shelf life, improve hygienic quality, and meet trade requirements. The electron paramagnetic resonance (EPR) method is a reliable and sensitive technique for detecting untreated and irradiated foods. This study investigated the effectiveness of EPR in identifying irradiated meat and seafood containing bones. Beef, lamb, chicken, and various fish were irradiated with electron beams at different doses and analysed using an EPR spectrometer. During irradiation, the food samples were surrounded by small ice bags to prevent autodegradation of cells and nuclei. After the irradiation process, the samples were stored at −20 °C. For EPR signal recording, the flesh, connective tissues, and bone marrow were removed from the bone samples, which were then oven-dried at 50 °C. The EPR spectra were recorded using an X-band EPR analyzer. Unirradiated and irradiated samples were identified based on the nature of the EPR signals as well as the g-values of symmetric and asymmetric signals. The study found that the EPR method is effective in distinguishing between unirradiated and irradiated bone-containing foods across nearly all applied radiation doses. The peak-to-peak amplitude of the EPR signals increased with increasing radiation doses. It was observed that unirradiated bone samples showed low-intensity symmetrical signals, while irradiated samples showed typical asymmetric signals. Overall, the study demonstrated that the EPR method is a reliable and sensitive technique for identifying irradiated foods containing bones and can be used for the control, regulation, and proper surveillance of food irradiation. Full article