Search Results (1,246)

Agroindustrial residues represent an abundant and underutilized source of carbon-rich materials for environmental remediation. In this study, annatto processing waste (Bixa orellana), a largely unexplored lignocellulosic by-product generated during pigment extraction, was converted into hydrochar via hydrothermal carbonization at 200 °C for 3 h. The resulting hydrochar (HC-AW) exhibited a predominantly amorphous carbon structure with retained oxygen-containing surface functionalities, and a solid yield of 44%, indicating efficient biomass conversion under subcritical conditions. Adsorption performance toward tetracycline was evaluated through pH-dependent experiments, kinetic modeling, equilibrium isotherms, and thermodynamic analysis. Maximum adsorption occurred under near-neutral conditions (pH ≈ 7), consistent with the interplay between tetracycline speciation and the hydrochar surface charge (pH_PZC ≈ 6.3), highlighting its potential applicability under realistic water treatment conditions without pH adjustment. Kinetic data were well described by the pseudo-second-order model, while equilibrium results were best fitted by the Langmuir model, with a maximum adsorption capacity of 14.94 mg g⁻¹ at 30 °C. Thermodynamic analysis indicated a spontaneous and slightly endothermic adsorption process. Overall, the results highlight the potential of annatto-derived hydrochar as a low-cost adsorbent and provide insight into the relationship between surface properties and adsorption behavior governing antibiotic removal from aqueous systems. Full article

Bidentate ligands, derived from the 1,3-dicarbonyl framework, play a central role in coordination chemistry, catalysis, and materials science due to their tuneable donor properties and structural versatility. This review examines and compares three closely related ligand classes, β-diketones (O,O′ donors), imino-β-diketones or enaminones (N,O donors), and di-imino-β-diketones or β-diketiminates (N,N′ donors), to elucidate how systematic substitution of oxygen by nitrogen affects structure and properties. The discussion integrates spectroscopic data (NMR and IR), crystallographic findings, electrochemical measurements, and density functional theory (DFT) calculations reported in the literature. Across these systems, tautomerism plays a decisive role, with conjugation-stabilized enol or enamine forms generally preferred in solution and the solid state. Frontier molecular orbital analyses show extensive delocalization over the chelate backbone and, when present, aromatic substituents. Electrochemical studies reveal consistent correlations between experimental reduction potentials and calculated LUMO energies for O,O′-, N,O-, and N,N′-bidentate ligands. Overall, the comparison demonstrates that donor atom substitution within a conserved conjugated scaffold provides a systematic approach to tuning acidity, coordination behaviour, and redox properties, offering a coherent framework for understanding structure–property relationships in 1,3-dicarbonyl-derived chelating ligands. Full article

Over the past decade, antibacterial materials have become a promising strategy to address both antibiotic-resistant and biomaterial-associated infections in clinical settings. Despite substantial progress, a gap remains between promising antibacterial performance in vitro and limited therapeutic outcomes in vivo. Herein, we present a mechanistic framework for understanding formulation-dependent antibacterial performance across five representative formulation architectures: nanoparticle-based systems, nanofibrous scaffolds, hydrogel matrices, surface coatings, and vesicular or microencapsulated carriers. We impart how structural organization and delivery dynamics regulate antibacterial mechanisms such as contact-mediated killing, controlled therapeutic release, and reactive oxygen species (ROS) generation and discuss their context-dependent suitability for diverse infection scenarios; these include acute wound infections, biofilm-associated implant infections, and chronic infected wounds. Particular emphasis is placed on factors contributing to the frequent failure of high in vitro log reduction efficacy translating into clinical success, including protein corona formation, biological barrier penetration, and dynamic host–pathogen interactions. Finally, we propose a comparative formulation-selection framework based on infection type, tissue environment, and therapeutic objectives to guide the rational design of next-generation antibacterial materials. This perspective bridges the gap between material innovation and clinical translation by highlighting formulation architecture as a central determinant of antibacterial performance in biomedical applications. Full article

Solar-driven interfacial evaporation is a sustainable technology for freshwater production; however, the rational design of photothermal materials that simultaneously achieve full-spectrum solar absorption, minimized thermal loss, and efficient energy utilization remains a formidable challenge. Herein, we report a “post-treatment” defect engineering strategy to fabricate highly active, non-stoichiometric BTO (black TiO_2−x) via a hydrothermal-assisted atmospheric deoxygenation process. The precise modulation of oxygen vacancies (O_v) within the TiO₂ lattice effectively narrows its bandgap, facilitating a dramatic enhancement in both light-harvesting capacity and photothermal conversion efficiency. By integrating the BTO into a polyvinyl alcohol (PVA) hydrogel framework, we developed a 3D evaporator (TPVA) that synergistically couples superior optical trapping with attenuated thermal conductivity. Consequently, the O_v-enriched TPVA architecture achieves an impressive solar absorption of 94.3%, enabling a high-performance evaporation rate of 2.492 kg m⁻² h⁻¹ under 1 sun irradiation, which is approximately 5.0 times higher than that of direct seawater evaporation under the same conditions. This work underscores the efficacy of defect engineering in optimizing semiconductor photothermal materials and provides a promising strategy for the advancement of next-generation solar desalination technologies. Full article

The valorization of agro-industrial byproducts through pyrolysis represents a sustainable route for generating multifunctional raw materials within the framework of a circular bioeconomy. In this study, rice husk (RH) and sugarcane bagasse (SCB) were pyrolyzed in a semi-continuous reactor at 500 °C in order to compare product yields and to characterize resulting gas, aqueous and tar fractions. SCB produced the highest bio-oil yield (44.2 wt%), whereas RH generated the highest char yield (42.9 wt%), consistent with its higher ash and lignin contents. In both cases, tar represented about 12 wt% of the bio-oil. Detailed characterization revealed that the liquid products contained oxygenated compounds of interest, mainly carboxylic acids, ketones, and phenols. Acetic acid was the predominant compound in the aqueous phases, while tars were composed mainly of phenols, ketones, furans, and acids. Particularly, phenols accounted for 52.6% and 37.8% of the total chromatographic area in RH and SCB tars, respectively, whereas ketones represented about 10% in both cases. These results show that pyrolysis of agro-industrial residues not only enables energy recovery but also provides liquid fractions enriched in value-added chemicals. Full article

The effective utilization and effective valorization of various organic industrial wastes have become increasingly important issues. One significant area for enhancing the circular economy is the processing of waste generated from vegetable oils and animal fats. This article focuses on the processing and use of soapstocks, which result from the chemical reaction between fatty acids and alkali. These soapstocks represent the most significant portion (approximately 70–90 wt% by weight) of waste produced by the oil and fat industry. The raw material for this study was soapstock obtained from the neutralization of sunflower oil at the PJSC “Zaporizhzhya Oil and Fat Plant,” designed by the Belgian company “De Smet.” The soapstock yield was found to be 9.95 wt% based on 100 wt% oil. Through a series of treatments involving water, acid, and multiple washes, a low-sulfur fuel component was produced that nearly meets the standards for boiler fuels as outlined in DSTU 4058-2001 and PN-C-96024:2020, except for the heat of combustion. It fully complies with the requirements specified in ISO 8217:2024. The sulfur content of the final product was determined to be 0.12 wt%. Additionally, the fuels produced contained 75.33 wt% carbon, 11.64 wt% hydrogen, and 12.00 wt% oxygen. Due to the relatively low oxygen content, the resulting product exhibits approximately twice the heat of combustion of similar fuels derived from other waste streams in the oil and fat industry. Full article

This work is devoted to the synthesis and comprehensive study of activated carbons (ACs) obtained from agricultural wastes—specifically corn cob (C) and onion (O)—for the effective removal of paracetamol (PCM) and sulfamethoxazole (SMX) from aqueous media. The synthesis was carried out by chemical activation using H₃PO₄, HNO₃, and NaOH as activating agents, which made it possible to obtain materials with a clearly defined microporous structure (microporous fraction V_micro/V_total = 0.75–0.81) and specific surface chemistry. Particular attention was paid to studying the kinetics and equilibrium of adsorption in both single-component and binary (two-pollutant) systems. It was established that the equilibrium time is 8 h, and the experimental data are best described by a pseudo-second-order kinetic model. During binary adsorption tests, the competitive behavior was observed for certain materials, such as the corn-derived carbon activated with HNO₃ (AC-CN) and the onion-derived carbon activated with HNO₃ (AC-ON), where molecules compete for active sites. Conversely, synergistic effects were identified in other systems, controlled by specific surface-functional groups and hydration effects. The maximum adsorption capacity was found to be 29.4 mg∙g⁻¹ for PCM on the AC-CN sample. Adsorption mechanisms, including multilayer isotherm profiles and the competition between pollutant and water molecules, were interpreted using quantum chemical calculations within the framework of Density Functional Theory (DFT). These calculations revealed that partial deprotonation and intense solvation of SMX molecules at natural pH reduce their adsorption capacity. In contrast, the PCM structure favors π-π interactions and the formation of strong hydrogen bonds with oxygen-containing groups on the carbon surface. These results demonstrate the high potential of using agro-industrial waste to create a new generation of selective adsorbents with tailored surface properties. Full article

Pneumonia, an acute inflammatory condition of the lung tissue, imposes a significant burden on global health and is characterized by a high rate of illness and death. The pathogenesis of the disease extends beyond infection to breakdown of redox hemostasis, where the excessive reactive oxygen species produced during the immune response inflict damage on the alveolar tissues and hence promote varying complications. This dual role of oxygen and oxidative mechanisms makes the management of pneumonia challenging, as the very oxygen that is vital for host defense, when not regulated, imposes severe lung damage. Antioxidant administration and oxygen therapy offer limited efficacy, mostly due to their non-specific action and iatrogenic harm from oxygen oversupply. These limitations are overcome by the use of emerging therapeutic strategies, which primarily focus on precision-targeted approaches. These include inhalable antioxidants, nanoparticle-based systems and biomaterials that are engineered to respond to local ROS concentrations, which aim to deliver the therapeutic agent directly to the inflamed regions of the lung. Calcium peroxide- and manganese dioxide-incorporating materials are being designed to modulate the oxygen levels, either by releasing it in hypoxic zones or scavenging it in hyperoxic microenvironments. This approach simultaneously addresses hypoxia and oxidative stress. Despite showing promising results in experimental and preclinical studies, complications related to product stability, regulatory compliance, and manufacturing scalability need to be addressed. Personalized treatment protocols, guided by biomarkers, involve the future generation of treatments, aiming to achieve a delicate recalibration of the lung’s oxidative environment for improved patient outcomes. Full article

The sustainable management of olive wastes represents an important environmental challenge. Biochars and hydrochars derived from biomass are promising adsorbents for removing emerging pollutants from water. In the present work, olive stone wastes were converted into biochar and hydrochar by using pyrolysis (500 °C for 30 min) and hydrothermal carbonization (HTC) processes (220 °C for 10 h). Then, the obtained materials were physically activated by using CO₂ gas (750 °C for 30, 60 and 180 min). Various analytical techniques were applied for the chemical, textural and structural characterization of these carbonaceous materials (i.e., ultimate and proximate analysis, scanning electron microscopy (SEM), BET surface area, Raman spectroscopy, X-ray diffraction, and Fourier transform infrared spectroscopy). Afterwards, the selected activated biochar and hydrochar were applied for the removal of amoxicillin from aqueous solutions. The experimental results show that the generated hydrochar has many microspheres on its surface and inside, while the produced biochar exhibits a porous structure with irregular forms. CO₂ physical activation has induced an important improvement of the biochar and hydrochar’s structural, textural, and surface chemistry properties. For instance, the activated biochar samples show a highly porous structure, with large specific surface areas that increase with the burn-off, reaching 1349.3 m² g⁻¹ following 3 h of activation. Regarding the activated hydrochar samples, they exhibit a spherical morphological structure with an important specific surface area, which increased to 846.7 m² g⁻¹ after 3 h of activation. Moreover, both activated materials have an amorphous structure with low oxygen surface groups. The selected novel CO₂-activated biochar and hydrochar efficiently remove amoxicillin from aqueous solutions under wide experimental conditions, with adsorption capacities of 386.4 and 215.9 mg g⁻¹, respectively. These efficiencies are higher than those reported for various activated biochars derived from lignocellulosic biomass, from sewage sludge, and from animal manure. Future research works are required to assess these materials’ effectiveness in treating real pharmaceutical effluents, to optimize the regeneration of the amoxicillin-loaded materials, and to design full-scale devices for a real application. Full article

The development of efficient, stable, and sustainably fabricated photocatalysts for solar-driven hydrogen evolution remains a critical challenge in the field. Herein, we report a novel green coprecipitation strategy to synthesize calcium-doped zinc oxide (Ca-ZnO) nanosheets, utilizing cactus juice as a natural, multifunctional medium for the coprecipitation process. This method enables the in situ, tunable incorporation of 3–7% Ca²⁺ ions into the wurtzite ZnO lattice without the use of harsh chemical reagents. Comprehensive characterization confirms that Ca²⁺ substitutionally replaces Zn²⁺, which preserves the intrinsic crystal structure of ZnO well while inducing the formation of uniform nanosheet morphology. This doping strategy effectively modulates the electronic band structure, progressively narrowing the bandgap from 3.19 eV to 2.90 eV and significantly enhancing visible-light absorption. Crucially, the incorporation of Ca²⁺ also generates oxygen vacancies, which serve as efficient electron traps to suppress photogenerated charge carrier recombination. The optimized 5%Ca-ZnO photocatalyst demonstrates a favorable hydrogen evolution rate of 889 μmol·g⁻¹·h⁻¹ under full-spectrum irradiation, with stability, retaining 94.8% of its activity after four cycles. This work not only provides a high-performance material but also establishes a generalizable, sustainable paradigm for the design of advanced semiconductor photocatalysts. Full article

Photodynamic therapy (PDT) is a promising cancer treatment employing photo-induced reactive oxygen species (ROS) generation by a photosensitizer (PS). Titanium dioxide (TiO₂) is a potential PS due to its superb photocatalytic features and biocompatibility. However, its clinical potential is restricted by its predominant ultraviolet (UV) absorption. To address this limitation, this work introduces TiO₂/carbon dots (CDs) nanohybrid materials for improving the photophysical properties of TiO₂ and its photodynamic performance. TiO₂ and CDs were synthesized through wet chemical and hydrothermal techniques, and subsequently combined via a facile ex situ solvothermal process to produce hybrid materials containing 1–50% w/w CDs. The materials were characterized using XRD, Raman, TEM, FT-IR, zeta potential, TGA, UV-Vis and PL. PDT studies on A431 skin cancer cells indicated improved photosensitizing ability of TiO₂/CDs, with TiO₂/CDs (10%) inducing 47% cell toxicity, versus 20% for TiO₂ after 10 min of red-light irradiation (661 nm, 18 mW/cm², 12.96 J/cm²). Intracellular localization studies revealed enhanced cellular uptake of TiO₂/CDs (10%), compared with TiO₂. In vitro studies on 3T3 healthy fibroblasts confirmed PSs’ safety both with and without light. Overall, this study elucidates the key role of CDs in the photophysical and photodynamic behavior of TiO₂-based systems, providing design guidelines for the next-generation inorganic PSs. Full article

Bismuth ferrite (BiFeO₃) is a promising material for developing the next generation of multifunctional electronic devices. However, the production of high-quality BiFeO₃ thin films is compromised by the tendency for structural and electronic defects to form during synthesis, which degrades their functional properties. In this work, BiFeO₃ thin films were prepared by chemical solution deposition to determine optimal conditions for minimizing oxygen vacancies and to evaluate the impact of these point defects on their physical properties. The films were pyrolyzed at 300 °C for 60 min and 360 °C for 10 min, and crystallized in air and in an O₂ atmosphere, at 600 °C and 640 °C for 40 min. High oxygen vacancies were observed in films prepared at low pyrolysis temperatures and crystallized in air, whereas oxygen vacancies were minimized in the film pyrolyzed and crystallized at high temperatures in an O₂ atmosphere. The oxygen vacancies markedly affected the films’ physical properties, leading to increased dielectric loss, dielectric dispersion, dc conductivity, and leakage current, with consequent degradation of photovoltaic and magnetic performance. These findings highlight the critical importance of controlling synthesis parameters to suppress oxygen vacancy formation and achieve high-quality BiFeO₃ thin films. Full article

Background/Objectives: Long-term chronic intermittent hypobaric hypoxia (CIHH) is a common occupational exposure among high-altitude workers, particularly miners in northern Chile. This condition consists of working several days above 2500 m followed by rest at sea level, maintaining this cycle for years, which generates physiological alterations. This study analyzed associations among anthropometric indices and biomedical conditions in miners chronically exposed to long-term CIHH. Methods: This study was a cross-sectional analysis of 120 healthy Chilean male miners working at altitudes above 4400 m under a 7-day work/7-day rest schedule. Eligibility required ≥5 years of CIHH exposure and absence of cardiopulmonary disease, hypertension, diabetes, or oxygen therapy use. The assessments at altitude included oxygen saturation (SpO₂), blood pressure, heart rate, hematological parameters, metabolic parameters, and waist-to-hip ratio (WHR); measurements were obtained 18 h after arrival at altitude. WHR, BMI, SpO₂, and biomedical variables were collected following standardized procedures. Descriptive statistics and group comparisons were performed with Student’s t-test or the Wilcoxon test, with statistical significance set at p < 0.05. Normality assumption was assessed using the Shapiro–Wilk test. The association between WHR and SpO₂ was estimated using linear regression, with WHR scaled so that one unit corresponds to a 0.1-unit increase. Adjusted models included BMI, age, and years working under CIHH. Effect sizes and 95% confidence intervals (CIs) were reported. All statistical analyses were performed in the R programming language. Results: Mean SpO₂ was 89.07 ± 0.50% and mean WHR was 0.94 ± 0.01. In unadjusted comparisons, workers with WHR > 0.94 had lower SpO₂ than those below the threshold (88.8 ± 0.54 vs. 90.41 ± 0.50; p = 0.031). In adjusted models, the WHR–SpO₂ association was small and imprecise (β per 0.1-unit WHR = −0.67 pp; 95% CI −2.08 to 0.74). Hemoglobin showed an independent association with SpO₂, while other metabolic variables did not materially contribute. Conclusions: SpO₂ showed a modest inverse association with WHR in long-term CIHH workers. Even small saturation decreases may matter at high altitude. Combined WHR–SpO₂ monitoring may aid occupational surveillance, though longitudinal studies are needed to establish meaningful risk thresholds. Full article

The nickel-derived metal–organic framework (MOF), Ni-BTB, synthesized from 4,4′,4″-benzene-1,3,5-tribenzoic acid (H₃BTB), was investigated as a multifunctional platform for enhanced energy applications including production and storage. In catalytic hydrogen generation by NaBH₄ hydrolysis, Ni-BTB attained a hydrogen generation rate (HGR) of 4640 mL H₂/g•min with 1 mg of catalyst, with an activation energy of 76.44 kJ/mol. Under optimized reaction conditions (60 °C, 20 mg catalyst, and 1 g NaBH₄), the HGR increased to 9542 mL H₂/g•min, while exhibiting high recyclability throughout four successive cycles. As a supercapacitor electrode, Ni-BTB achieved a specific capacitance of 156 F/g at 1 A/g and showed remarkable cycling stability, maintaining its capacitance after 10,000 charge–discharge cycles. Furthermore, Ni-BTB exhibited exceptional electrocatalytic activity for oxygen evolution reaction (OER), requiring only 106 mV overpotential to achieve 10 mA/cm², offering a time-of-flight (TOF) of 0.0585 s⁻¹ and demonstrating significant operational longevity of at least 12 h. These findings underscore Ni-BTB as a durable, reusable, and adaptable material for hydrogen production, energy storage, and electrocatalytic applications. Full article

This study reports the valorization of oil palm empty fruit bunches into cellulose nanocrystals (CNCs) for the removal of the chemical oxygen demand (COD) from industrial wastewater generated by the same processing sector. Cellulose I_β was first isolated through sequential bleaching, delignification, and mercerization, and two hydrolysis routes were evaluated to obtain CNCs: a concentrated acid route (60% v/v H₂SO₄, 50 °C, 60 min) for CNCs-1 and a low-acid, long-duration route (1% v/v H₂SO₄, 80 °C, 12 h) for CNCs-2. Rietveld refinement of the X-ray diffractograms confirmed the polymorphic transition, assigning cellulose I_β to the intermediate materials and cellulose II to the CNC samples, with crystallite sizes of 4.99 nm for CNCs-1 and 5.43 nm for CNCs-2. Attenuated Total Reflectance–Fourier Transform Infrared (ATR-FTIR) spectroscopy analysis showed the progressive removal of lignin and hemicellulose and supported the cellulose I_β to II transition through changes in hydroxyl bonding and crystallinity-related bands. Preliminary adsorption tests showed better COD removal with CNCs-2, which were therefore selected for optimization using a Box–Behnken design with the adsorbent mass, pH, and contact time as variables. The quadratic model was significant (R² = 0.9675; predicted R² = 0.8908), and the maximum COD removal reached 91.47%, decreasing the COD concentration from 2459.0 to 209.85 mg L⁻¹ under the optimum conditions of 0.09 g CNCs-2, pH 3, and 20 min. These results highlight cellulose II nanocrystals derived from oil palm waste as a promising and scalable adsorbent for industrial wastewater treatment. Full article