AppliedChem

Hydrogen-bond-like M···H–C interactions in square-planar d⁸ metal complexes have recently gained attention as structure-directing elements and design motifs in asymmetric catalysis. In this study, we explore these weak interactions not as static features, but as key modulators of molecular motion. We synthesized four cis-[N,N′-pentamethylenebis(iminomethylazolato)]M(II) (M = Pt, Pd), including iminomethyl-2-imidazole, iminomethyl-5-imidazole, and iminomethylpyrrolato Pt(II) complexes and an iminomethylpyrrolato Pd(II) analog. All complexes display reversible flipping of the alkylene bridge across the coordination plane, with the M···H–C interaction alternately engaging from above or below. This dynamic motion was characterized by variable-temperature ¹H NMR spectroscopy, revealing activation parameters for the flipping process. X-ray crystallography confirmed geometries consistent with hydrogen-bond-like interactions, while NBO analysis based on DFT calculations provided insight into their electronic nature. Interestingly, although Pt and Pd display comparable M···H–C distances, solvent effects dominate the flipping kinetics over metal identity. These findings highlight the role of hydrogen-bond-like M···H–C interactions not only in structural stabilization, but also in regulating conformational dynamics. Full article

Water contamination by heavy metals, particularly lead, derived from industrialization, climate change, and urbanization, represents a critical risk to human health and the environment. Several agricultural biomass residues have demonstrated efficacy as contaminant adsorbents. In this context, the study aimed to evaluate the potential of sugarcane tip (ST) waste biomass treated by hydrothermal carbonization (HTC) to produce hydrochar as an adsorbent material for Pb²⁺ in aqueous solutions. Samples were synthesized from the waste biomass at temperatures of 180 °C, 215 °C, and 250 °C, with a constant pressure of 6 MPa. Aqueous solutions of Pb²⁺ were prepared at concentrations of 10, 25, 50, 75, and 100 mg/L. Each solution was stirred at 1 g of hydrochar at 150 rpm, 25 °C, and pH 5 for 15 to 120 min. The solutions were filtered and stored at 4 °C for flame atomic absorption spectrophotometry analysis. In all cases, equilibrium was reached rapidly—within 15 min or less—as indicated by the stabilization of q_t values over time. At an initial concentration of 100 mg L⁻¹, the highest equilibrium uptake was observed for the hydrochar synthesized at ST HTC 180 °C (4.90 mg g⁻¹), followed by 4.58 mg g⁻¹ and 4.52 mg g⁻¹ for ST HTC 215 °C and ST HTC 250 °C, respectively. For the ST HTC 180 °C, the Sips model provided the best correlation with the experimental data, exhibiting a high maximum capacity (q_max = 240.8 mg g⁻¹; K_s = 0.007; n = 1.09; R² = 0.975), which reinforces the heterogeneous nature of the material’s surface. Hydrothermal synthesis increased the amount of acidic active sites in the ST HTC 180 °C material from 1.3950 to 3.8543 meq g⁻¹, which may influence the electrical charge of the Pb²⁺ adsorption process. HTC-treated sugarcane tip biomass represents a promising alternative for the synthesis of adsorbent materials, contributing to water remediation and promoting the circular economy by sustainably utilizing agricultural waste. Full article

Myoglobin, a heme protein involved in oxygen storage and transport, also exhibits pseudo-peroxidase activity by catalyzing the breakdown of hydrogen peroxide. While this enzymatic function is well-documented, the potential for substrate inhibition at high hydrogen peroxide concentrations remains underexplored. In this study, we aimed to investigate the kinetic properties of myoglobin’s peroxidase-like activity, focusing on substrate inhibition over time. We employed spectrophotometric assays to monitor reaction rates of myoglobin exposed to increasing hydrogen peroxide concentrations. Our results show that myoglobin activity begins to decline within 3 min of exposure to hydrogen peroxide and reaches full inhibition after approximately 30 min. This progressive inhibition suggests that myoglobin undergoes a delayed inactivation process rather than an immediate loss of function. Additionally, we extended the investigation to hemoglobin, comparing its response to hydrogen peroxide, and preliminary data suggest differences in substrate inhibition dynamics. These findings provide new insights into the regulation of myoglobin’s oxidative function and suggest potential physiological implications for oxidative stress and redox balance, especially in relation to other heme proteins like hemoglobin. Full article

Two different zeolite model clusters were considered in this study to shed light on the release mechanism of a drug, ASA (acetylsalicylic acid), adsorbed on the Y-type zeolite pore walls. Initially, the 3T cluster was employed as a preliminary approach to reveal the trends developed in the acetylsalicylic acid-zeolite system due to the presence of water molecules. Then, the cluster was expanded to 38T (12T:26T), and the adsorption of acetylsalicylic acid in the presence of water molecules inside the pores of the zeolite was studied by employing the hybrid (QM/MM) approximation at the ONIOM2//(HSEH1PBE/6-31+G(d,p):UFF) level of theory. The quantum chemical modeling explicitly shows the water molecules’ impact on the value of the adsorption energy. Specifically, the adsorption energy of acetylsalicylic acid gradually decreases from 32.55 kcal mol⁻¹ (in the case of the 38T model cluster with no H₂O molecules) to 22.10 kcal mol⁻¹ in the presence of three water molecules. Full article

Free radicals are molecules generated during some biochemical processes, and in excess, they can cause various diseases; therefore, their production needs to be controlled in humans. One approach to achieving this is through the consumption of substances with antioxidant capacity, which are capable of neutralizing free radicals. This study evaluated the antioxidant activity of cellooligosaccharides (COS) and xylooligosaccharides (XOS) solutions, extracted from banana leaf and pseudostem, and guava seed cake, unfiltered and filtered using a Sep-pak filter. Additionally, the antioxidant activity of their monomers, including commercial glucose, xylose, and cellobiose, was evaluated using the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical assay. Antioxidant activity was observed in the unfiltered COS and XOS solutions, with maximum DPPH radical reduction of 48.3% and 84.2%, respectively. In filtered COS and XOS solutions, the reduction did not exceed 0.5%. It can be concluded that the antioxidant activity is due to the presence of compounds dissolved in the oligosaccharide solutions, such as lignin, extractives and carboxylic acids, which were qualified by the Folin–Ciocalteu method, nuclear magnetic resonance, and scanning spectrophotometry. Full article

In this work, a set of methods for the study of the physical–chemical properties of flotation processing products was applied to establish parameters for the technological mode of anthropogenic raw material flotation processing using waste paper as an example. The proposed methods include the criterion E_f estimation, which characterizes the interfacial characteristics during flotation, and the criterion J determination, which characterizes the degree of purification of the obtained paper mass. The estimation of criterion E_f is based on the measurement of electric potential difference during flotation. The estimation of criterion J is based on spectrophotometric studies of the flotation product’s optical properties. Based on dispersion analysis, it was established that the proposed criteria are statistically dependent on the variation of the flotation purification mode parameters. The results of the study of flotation processing products show that the criterion E_f is sensitive to the recovery selectivity of dye particles in the froth product. In conjunction with the criterion of optical purity, J, it can be used to assess the effectiveness of proposed solutions of hardware design and the technological mode of flotation separation. Full article

Soybean (Glycine max (L.) Merrill) is a major oilseed crop rich in phytosterols and tocopherols, compounds associated with functional and nutritional properties of vegetable oils. This study aimed to apply, for the first time, Independent Component Analysis (ICA) to discriminate the composition of phytosterols (β-sitosterol, campesterol, stigmasterol) and tocopherols (α, β, γ, δ) in 20 soybean genotypes—14 non-transgenic and six transgenic—cultivated in two major producing regions of Paraná state, Brazil (Londrina and Ponta Grossa). Lipophilic compounds were extracted from soybean seeds, quantified via gas chromatography and HPLC, and statistically analyzed using ICA with the JADE algorithm. The extracted independent components successfully differentiated soybean varieties based on phytochemical profiles. Notably, transgenic cultivars from Ponta Grossa exhibited higher levels of total tocopherols, including α- and β-tocopherol, while conventional cultivars from both regions showed elevated phytosterol content, particularly campesterol and stigmasterol. ICA proved to be a powerful unsupervised method for visualizing patterns in complex compositional data. These findings highlight the significant influence of genotype and growing region on the nutraceutical potential of soybean, and support the use of multivariate analysis as a strategic tool for cultivar selection aimed at enhancing functional quality in food applications. Full article

Corn is one of the most consumed cereals in the Mexican diet. In this country, there are multiple varieties that exhibit nutraceutical potential due to their content of different metabolites with biological activity, such as blue corn. Another variety that has received little study is the red pigmented corn variety Chilac from Puebla, Mexico, which is being studied for its nutraceutical potential. A differential extraction using the Soxhlet method was carried out to evaluate the phenolic content, total flavonoid content, and monomeric anthocyanins, and free radical scavenging test was performed using the DPPH reagent. A proximate analysis was also conducted to identify the main macronutrients. The results of the proximate analysis were comparable to those of other traditional corn varieties, with carbohydrates being the macronutrient present in the highest amount at 77.9%. Regarding phenolic content and the presence of anthocyanins, the best extractions were obtained using alcoholic solvents; for example, ethanol for phenols, yielding 1368.420 ± 104.094 mg of gallic acid equivalents (GAE)/kg plant. In contrast, the flavonoid content was higher in the aqueous extract, with 833.984 ± 65.218 mg QE/Kg. In the case of the DPPH assay, the best result was obtained with ethyl acetate (73.81 ± 5.31%). These findings provide a foundation for expanding the use of corn varieties with nutraceutical potential, opening the possibility of studies focused on deeper characterization. Full article

Biopolymers and bio-based plastics, such as polylactic acid (PLA) and polybutylene succinate (PBS), are recognized as environmentally friendly materials and are widely used, especially in the packaging industry. The purpose of this study was to assess the degradation of PLA- and PBS-based formulations in the forms of granules and films under controlled composting conditions at a laboratory scale. Biodegradation tests of bio-based materials were conducted under controlled aerobic conditions, following the standard EVS-EN ISO 14855-1:2012. Scanning electron microscopy (SEM) was performed using a high-resolution Zeiss Ultra 55 scanning electron microscope to analyze the samples. After the six-month laboratory-scale composting experiment, it was observed that the PLA-based materials degraded by 47.46–98.34%, while the PBS-based materials exhibited a final degradation degree of 34.15–80.36%. Additionally, the PLA-based compounds displayed a variable total organic carbon (TOC) content ranging from 38% to 56%. In contrast, the PBS-based compounds exhibited a more consistent TOC content, with a narrow range from 53% to 54%. These findings demonstrate that bioplastics can contribute to reducing plastic waste through controlled composting, but their degradation efficiency depends on the material composition and environmental conditions. Future efforts should optimize bioplastic formulations and composting systems while developing supportive policies for wider adoption. Full article

As demand for plant-based beverages grows, analytical tools are needed to classify and understand their structural and compositional diversity. This study applied a multi-analytical approach to characterize 41 commercial almond-, oat-, rice- and soy-based beverages, evaluating attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, protein secondary structure proportions, colorimetry, and microscopic image texture analysis. A total of 26 variables, derived from ATR-FTIR and protein secondary structure assessment, were employed in multivariate models, using partial least squares discriminant analysis (PLS-DA) and orthogonal PLS-DA (OPLS-DA) to evaluate classification performance. The results indicated clear group separation, with soy and rice beverages forming distinct clusters while almond and oat samples showing partial overlap. Variable importance in projection (VIP) scores revealed that β-turn and α-helix protein structures, along with carbohydrate-associated spectral bands, were the key features for beverages’ classification. Textural features derived from microscopy images correlated with sugar and carbohydrate content and color parameters were also employed to describe beverages’ differences related to sugar content and visual appearance in terms of homogeneity. These findings demonstrate that combining ATR-FTIR spectral data with protein secondary structure data enables the effective classification of plant-based beverages, while microscopic image textural and color parameters offer additional extended product characterization. Full article

In this study, chromium ferrite (FeCr; CrFe₂O₄) nanoparticles supported on activated carbon (AC), obtained from agricultural olive mill solid waste, were synthesized via a simple hydrothermal process. The structural, morphological, optical, and chemical properties of the FeCr/AC composite were characterized using XRD, SEM, EDX, DRS, BET, and FTIR techniques. The FeCr/AC composite was applied as a heterogeneous photo-Fenton catalyst for the degradation of methylene blue (MB) dye in an aqueous solution under 25 W visible-light LED irradiation. Critical operational factors, such as FeCr/AC dosage, pH, MB concentration, and H₂O₂ levels, were optimized. Under optimal conditions, 97.56% of MB was removed within 120 min of visible-light exposure, following pseudo-first-order kinetics. The composite also exhibited high efficiency in degrading methyl orange dye (95%) and tetracycline antibiotic (88%) within 180 min, with corresponding first-order rate constants of 0.0225 min⁻¹ and 0.0115 min⁻¹, respectively. This study highlights the potential of FeCr/AC for treating water contaminated with dyes and pharmaceuticals, in line with the Sustainable Development Goals (SDGs) for water purification. Full article

The aim of this work was to improve the technology for obtaining coating based on plasticized polylactide from its aqueous suspensions. For this purpose, a film formation process with additional heating was developed, and the influence of plasticizers on the film-formation temperature was investigated. It is shown that using only mechanical emulsification, it is possible to obtain a material with an average particle size of 2.4 microns, which is suitable for further research and modification for film materials. The introduction of epoxidized fatty acids (oleic and linolic) was found to reduce the film-formation temperature by 20–30 °C compared to the unplasticized polymer, which puts them on par with the classical plasticizer, polyethylene glycol, reducing the film-formation temperature by 36% at the same concentration. Full article

The Pharmaceutical Strategy for Europe addresses the environmental implications at all stages of the life cycle of pharmaceuticals, from design and production through use to disposal. In the last decade, “green chemistry” has transformed pharmaceuticals by promoting sustainability and reducing environmental impact. This review discusses the latest developments in green chemistry approaches, which are applied in drug design and production, including the concepts, innovative techniques, and methodologies. This review is notably built on over 80 documents and demonstrates the practical application of green chemistry principles in pharmaceutical synthesis, emphasizing successful implementation and the environmental benefits achieved. Therefore, this review discusses the positive changes brought by green chemistry to pharmaceutical production and highlights the need for further research in designing and manufacturing “greener” substances, as well as in pollution abatement. Full article

The effects of different carrier agents—pea protein (PP), rice protein (RP), bean protein (BP), whey protein (WP), and maltodextrin (MT, as a control)—on pitaya juice encapsulation via spray drying were evaluated. Juice and carrier mixtures (30% w/v) were dried at 150 °C, and the resulting powders were analyzed for water activity (aw), hygroscopicity (Hg), water solubility (WSI), bulk density (BD), glass transition temperature (Tg), water absorption (WAI), antioxidant activity (AA), total polyphenol content (TPC), total betalain (TB) content, and TB stability. Vegetable proteins showed promising results, significantly impacting the protein content, Hg content, WAI, WSI, AA, TPC, and TB content and resulting in high Tg values. PP showed the best results, with high betalain retention (>30%), high TPC and AA, high protein levels, and low Hg, similarly to MT. WP had the highest TB, AA, and TPC but the lowest Tg (47.21 °C), thus reducing stability. Encapsulates obtained with plant protein-based wall materials presented high Tg (>58 °C); low aw, WSI, and Hg; high protein contents >40%; and adequate retention of bioactive compounds, with low degradation rate constants and long half-lives. Overall, plant proteins are promising alternatives to traditional carriers, offering improved stability and functionality in encapsulated products. Full article

The aim of this study was to quantify the total extraction yield (GEY) of polyphenols from pomegranate peels using a solid–liquid extraction process without evaporation but with UV-Vis spectrophotometry. Extraction kinetics models were tested to evaluate the extract yield (GEY), total phenolic compounds (TPCs), total flavonoids (TFCs), and condensed tannins (CTCs). The results showed maximum values of 45% for GEY, 97.560 mg EAG/g db for TPC, 4.416 mg EQ/g db for TFC, and 0.412 mg EC/g db for CTC, obtained with a methanol/water mixture (75/25, v/v) for 24 h. Spectrophotometry proved to be a reliable method for quantifying the total extraction yield, with a correlation of 99.79% compared to the conventional method. The second-order kinetic model accurately described the mass transfer mechanisms of the bioactive compounds studied. This study provides important insights into the mass transfer mechanisms during the extraction of bioactive compounds, facilitating the design, optimization, and control of large-scale processes for the recovery of pomegranate waste. Full article

The photochemical production of tropospheric ozone (O₃) is very closely linked to seasonal cycles and peaks in solar radiation occurring during warm seasons. In the Mediterranean Basin, which is a hotspot for climate and air mass transport mechanisms, boreal warm seasons cause a notable increase in tropospheric O₃, which unlike stratospheric O₃ is not beneficial for the environment. At the Lamezia Terme (code: LMT) World Meteorological Organization—Global Atmosphere Watch (WMO/GAW) station located in Calabria, Southern Italy, peaks of tropospheric O₃ were observed during boreal summer and spring seasons, and were consequently linked to specific wind patterns compatible with increased photochemical activity in the Tyrrhenian Sea. The finding resulted in the introduction of a correction factor for O₃ in the O₃/NO_x (ozone to nitrogen oxides) ratio “Proximity” methodology for the assessment of air mass aging. However, some of the mechanisms driving O₃ patterns and their correlation with other parameters at the LMT site remain unknown, despite the environmental and health hazards posed by tropospheric O₃ in the area. In general, the issue of ozone photochemical pollution in the region of Calabria, Italy, is understudied. In this study, the behavior of O₃ at the site is assessed with remarkable detail using nine years (2015–2023) of data and correlations with surface temperature and solar radiation. The evaluations demonstrate non-negligible correlations between environmental factors, such as temperature and solar radiation, and O₃ concentrations, driven by peculiar patterns in local wind circulation. The northeastern sector of LMT, partly neglected in previous works, yielded higher statistical correlations with O₃ than expected. The findings of this study also indicate, for central Calabria, the possibility of heterogeneities in O₃ exposure due to local geomorphology and wind patterns. A case study of very high O₃ concentrations reported during the 2015 summer season is also reported by analyzing the tendencies observed during the period with additional methodologies and highlighting drivers of photochemical pollution on larger scales, also demonstrating that near-surface concentrations result from specific combinations of multiple factors. Full article

In this study, copper ferrite nanoparticles, a type of ferrimagnetic spinel ferrite, were synthesized using the sol-gel auto-combustion method with three different fuels: citric acid, urea, and ethylene glycol. The crystal structures of the synthesized samples were analyzed using X-ray diffraction (XRD), and the growth of secondary phases like Fe₂O₃ and CuO for samples prepared with urea and ethylene glycol indicated the presence of impurities. Additionally, we observed that the particle size varied significantly with the type of fuel, being the smallest for citric acid and the largest for urea. The electrical and magnetic properties showed strong correlations with the particle size and the presence of impurities. In particular, the optical band gap values, derived from UV-Vis spectroscopy, varied significantly with the choice of fuel, ranging from 2.06 to 3.75 eV. The highest band gap of 3.75 eV was observed in samples synthesized with citric acid. Magnetic properties were measured using a vibrating sample magnetometer (VSM), and it was found that the copper ferrite synthesized with citric acid exhibited the highest values of magnetic saturation and coercivity. These findings demonstrate that the choice of fuel during the synthesis process has substantial impacts on the structural, optical, and magnetic properties of CuFe₂O₄ nanoparticles. Full article

This study investigated the effectiveness of a ligand known as (2-Mercapyo-phenylimino)-1,3-dihydro-indol-2-one-based ligand, in removing stable/radioactive cesium and cobalt from contaminated wastewater. Several parameters, such as contact duration, temperature, adsorbent quantity, pH of the medium, and concentration of adsorbate, have been investigated as primary active parameters impacting the adsorption process. Regarding the stable isotopes, the concentrations of Co²⁺ and Cs⁺ were measured before and after the treatment processes using the Optical Emissions Spectroscopy with Inductively Coupled Plasma (ICP-OES) technique. Additionally, kinetic and equilibrium isotherm models were applied to understand the equilibrium data. Both Cs⁺ and Co²⁺ were ideally eliminated after 120 and 60 min, respectively. The optimal pH for Cs⁺ was 6.3, while that for Co²⁺ was 5. The results indicate that the adsorption process is endothermic for Co²⁺ and exothermic for Cs⁺. Three thermodynamic parameters (∆G°, ∆H°, and ∆S°) were calculated. The reported R² values for the Freundlich and Langmuir models showed that the adsorption process for Cs⁺ and Co²⁺ always followed these isotherms, regardless of the temperature used. For Cs⁺, the maximum single-layer capacity (q_max) was 15.10 mg g⁻¹, while for Co²⁺, it was 62.11 mg g⁻¹. When the aqueous medium was spiked with both radioisotopes individually, the elimination of ⁶⁰Co and ¹³⁴Cs achieved maximum values of 99 and 86%, respectively, within 120 min. It can be concluded that the ligand effectively removed cobalt and cesium from wastewater, with higher adsorption for cobalt. Full article

Capsaicinoids obtained from lyophilized serrano chili by sorbitan monooleate solutions were investigated. Sorbitan monooleate was as effective as methanol in extracting capsaicin and dihydrocapsaicin (DHC). Subsequently, a Box–Behnken design was used to optimize capsaicin, DHC, and polyphenol extraction, as well as to evaluate the antioxidant capacity of dehydrated serrano chili. Particle size (PS) (20–60 mesh), processing temperature (55–75 °C), and sorbitan concentration (1.5–2.5%) were selected as independent variables. The statistical analysis showed that the quadratic models adequately describe the response of the concentration of capsaicin and DHC, but not with polyphenols and antioxidant capacity. The highest extraction of capsaicin (~620 mg/100 g dw) and DHC (~520 mg/100 g dw) was achieved with the combination of sorbitan at 2%, temperature at 65 °C, and PS from 40 mesh. Experimental and predicted values were closely consistent. Meanwhile, extracts with the highest antioxidant potential (~7510 and ~5820 µM of Trolox Eq/100 g dw for ABTS and FRAP, respectively) were those extracted in sorbitan and PS from 40 mesh. In contrast, the highest values of polyphenols (~171 mg gallic acid Eq/100 g dw) were found in the extracts prepared at 75 °C. These results suggest that sorbitan monooleate solutions can be an effective, non-toxic, and environmentally responsible way to obtain capsaicinoids and bioactive compounds from dehydrated serrano chili. Full article