Search Results (130)

Moroccan oil shale ash (MOSA) represents an underutilized industrial by-product, particularly in the Rif region, where its high mineral content has often led to its neglect in value-added applications. This study highlights the successful conversion of MOSA into amorphous mesoporous silica (AS-Si) using a sol–gel process assisted by polyethylene glycol (PEG-6000) as a soft template. The resulting AS-Si material was extensively characterized to confirm its potential for environmental remediation. FTIR analysis revealed characteristic vibrational bands corresponding to Si–OH and Si–O–Si bonds, while XRD confirmed its amorphous nature with a broad diffraction peak at 2θ ≈ 22.5°. SEM imaging revealed a highly porous, sponge-like morphology composed of aggregated nanoscale particles, consistent with the nitrogen adsorption–desorption isotherm. The material exhibited a specific surface area of 68 m²/g, a maximum in the pore size distribution at a pore diameter of 2.4 nm, and a cumulative pore volume of 0.11 cm³/g for pores up to 78 nm. DLS analysis indicated an average hydrodynamic diameter of 779 nm with moderate polydispersity (PDI = 0.48), while a zeta potential of –34.10 mV confirmed good colloidal stability. Furthermore, thermogravimetric analysis (TGA) and DSC suggested the thermal stability of our amorphous silica. The adsorption performance of AS-Si was evaluated using methylene blue (MB) and ciprofloxacin (Cipro) as model pollutants. Kinetic data were best fitted by the pseudo-second-order model, while isotherm studies favored the Langmuir model, suggesting monolayer adsorption. AS-Si could be used four times for the removal of MB and Cipro. These results collectively demonstrate that AS-Si is a promising, low-cost, and sustainable adsorbent derived from Moroccan oil shale ash for the effective removal of organic contaminants from aqueous media. Full article

Dye-sensitized solar cells (DSSCs) have emerged as a promising technology for converting sunlight into electricity at a low cost; however, it is still necessary to find a photostable, low-cost, and efficient photosensitizer. In this sense, the natural product bixin (Dye 1) has previously been reported as a potential photosensitizer. Thus, the present work reports the full synthesis of diester and diacid hybrids (Dyes 2 and 3, respectively, with corresponding yields of 93% and 52%) using the natural product bixin as a starting material and 1,3,4-oxadiazole ring as a connected point. The hydrolysis step of Dye 2 aims to obtain Dye 3 with a structural capacity to anchor the titanium dioxide (TiO₂) nanofilms via the carboxylic acid group. Both compounds (Dyes 1 and 3) can be adsorbed via pseudo-first order on the surface of TiO₂ nanofilms, reaching saturation after 10 and 6 min of exposure in an organic solution (1 × 10⁻⁵ M), respectively, with adsorption kinetics of the semisynthetic compound almost twofold higher than the natural product. Contrary to expectations, Dye 3 had spectral behavior similar to Dye 1, but with better frontier molecular orbital (FMO) parameters, indicating that Dye 3 will probably behave very similarly or have slightly better photovoltaic performance than Dye 1 in future DSSC measurements. Full article

The rapid progress of Large Language Models (LLMs) has greatly improved natural language tasks like code generation, boosting developer productivity. However, challenges persist. Generated code often appears “pseudo-correct”—passing functional tests but plagued by inefficiency or redundant structures. Many models rely on outdated methods like greedy selection, which trap them in local optima, limiting their ability to explore better solutions. We propose AnnCoder, a multi-agent framework that mimics the human “try-fix-adapt” cycle through closed-loop optimization. By combining the exploratory power of simulated annealing with the targeted evolution of genetic algorithms, AnnCoder balances wide-ranging searches and local refinements, dramatically increasing the likelihood of finding globally optimal solutions. We speculate that traditional approaches may struggle due to narrow optimization focuses. AnnCoder addresses this by introducing dynamic multi-criteria scoring, weighing functional correctness, efficiency (e.g., runtime/memory), and readability. Its adaptive temperature control dynamically modulates the cooling schedule, slowing cooling when solutions are diverse to encourage exploration, then accelerating convergence as they stabilize. This design elegantly avoids the pitfalls of earlier models by synergistically combining global exploration with local optimization capabilities. After conducting thorough experiments with multiple LLMs analyses across four problem-solving and program synthesis benchmarks—AnnCoder showcased remarkable code generation capabilities—HumanEval 90.85%, MBPP 90.68%, HumanEval-ET 85.37%, and EvalPlus 84.8%. AnnCoder has outstanding advantages in solving general programming problems. Moreover, our method consistently delivers superior performance across various programming languages. Full article

The semi-synthesis of the (5R,7R,11bR)-9-(di(1H-indol-3-yl)methyl)-4,4,7,11b-tetramethyl-1,2,3,4,4a,5,6,6a,7,11,11a,11b-dodecahydrophenanthro[3,2-b]furan-5-yl acetate was performed via a pseudo-multicomponent reaction involving a double Friedel–Crafts alkylation between the natural product-derived aldehyde 6β-acetoxyvouacapane and the corresponding indole. The transformation was carried out under solvent-free mechanochemical conditions using mortar and pestle grinding, with ZnCl₂ as the catalyst. Structural elucidation of the target compound was accomplished using 1D and 2D NMR spectroscopy (¹H, ¹³C, COSY, HSQC, and HMBC), FT-IR, and high-resolution mass spectrometry (HRMS). Full article

To ensure agricultural safety and ecological security, it is crucial to effectively immobilize emerging organic pollutants, such as plasticizers, to prevent their migration in various environmental matrices. However, the ideal immobilization agent with the advantages of being environmentally friendly is very rare. In this study, low-cost and stable near-natural immobilization agents, char-derived artificial humic acids, CHAs, were proposed and prepared via hydrothermal humification (180 °C) and pyrolysis (300, 500, or 700 °C) of agroforestry biowaste. The resulting CHAs exhibit high purity (composed primarily of C (67.28–81.35%), O (6.65–21.64%), H (1.40–5.28%), and N (0.36–0.58%)) with remarkably low ash content (5.43–10.02%). Characterization revealed a compact structure with a limited porosity with small surface area (0.27–0.32 m² g⁻¹) and pore volume (2.99–3.43 × 10⁻⁴ cm³ g⁻¹). Notably, high-temperature pyrolysis induced consumption of oxygen-containing functional groups while promoting aromatic structure formation. The sorption behavior of diethyl phthalate, a representative plasticizer, on CHAs was well described by both Langmuir isotherm and pseudo-second-order kinetic models. The CHAs exhibited remarkable sorption performance for diethyl phthalate, with a maximum sorption capacity reaching 3345 mg kg⁻¹ as determined by the Langmuir model. The sorption of diethyl phthalate onto CHAs is mainly multi-layer sorption dominated by physical processes, mainly including pore filling, partitioning, hydrogen bonding, and π–π stacking. Mean sorption energies ranging from 2.56 to 4.99 × 10⁻³ kJ mol⁻¹ indicate the predominance of physical sorption mechanisms. This study developed a method to convert the liquid by-product produced during hydrothermal humification of biowaste into stable near-natural and carbon-rich char materials, and the proposed materials show great promise in immobilizing pollutants from various environmental matrices. Full article

The present study aims to prepare a composite via pyrolysis, based on sodium alginate (SA) and a natural clay collected from the eastern region of Morocco, specifically the OUJDA area (C.O.R), for use in the disposal process of emerging pharmaceuticals. The strategy of rapid microwave heating followed by nitrogen calcination at 500 °C was successfully applied to produce the pyrolyzed carbonaceous materials. The removal of paracetamol (PCT) by adsorption on the carbonaceous clay (ca-C.O.R) composite was investigated to determine the effect of operating parameters (initial contaminant concentration, contact time, pH, and temperature) on the efficiency of PCT removal. The nanocomposite was analyzed using various techniques, including the nitrogen gas adsorption–desorption isothermal curve, X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy. Three models were used to describe the kinetic adsorption, and it was found that the experimental kinetic data fit well with a pseudo-second-order kinetic model with a coefficient of determination R² close to one, a nonlinear chi-square value close to zero, and a reduced root mean square error RMSE (R² → 1, X² → 0 and lower RMSE). The adsorption was best described by the Sips isotherm. The ca-C.O.R composite achieved a PCT removal efficiency of 91% and a maximum adsorption capacity of 122 mg·g⁻¹ improving on the performance of previous work. Furthermore, the variation in enthalpy (∆H°), Gibbs free energy (∆G°), and entropy (∆S°) indicated that the adsorption is exothermic in nature. The composite has shown promising efficiency for the adsorption of PCT as a model of emergent pollutant from aqueous solutions, making it a viable option for industrial wastewater treatment. Using Density Functional Theory (DFT) along with the 6-31G (d) basis set, the geometric structure of the molecule was determined, and the properties were estimated by analyzing its boundary molecular orbitals. The adsorption energy of PCT on MMT and ca-C.O.R studied using the Monte Carlo (MC) simulation method was −120.3 and −292.5 (kcal·mol⁻¹), respectively, which shows the potential of the two adsorbents for the emerging product. Full article

The purification of waste cooking oils (WCOs) through clay-based adsorption is an established recycling method, yet the relationship between clay composition and adsorption efficiency remains an area of active research. The aim of the present research work was to assess the performance of Maghnia bentonite in WCO decoloration and to gain information about the specific refining process. Thus, natural bentonite from the Maghnia region (Algeria) was investigated as an adsorbent for WCO refining for biolubricant production. The adsorption efficiency was evaluated under different conditions, achieving up to 70% decolorization at 10 wt% clay after 4 h of treatment. Structural characterization of the bentonite before and after adsorption was conducted using FT-IR spectroscopy, powder X-ray diffraction (XRD), and X-ray fluorescence (XRF) to assess compositional and morphological changes. FT-IR analysis confirmed the adsorption of organic compounds, XRD indicated minor alterations in interlayer spacing, and XRF revealed ion exchange mechanisms, including a reduction in sodium and magnesium and an increase in calcium and potassium. Adsorption kinetics followed a pseudo-second-order model, with desorption effects observed at prolonged contact times. The pHPZC of 8.3 suggested that bentonite adsorption efficiency is enhanced under acidic conditions. The high decoloration capacity of Maghnia bentonite, combined with the availability and the low cost of the material, suggests a possible industrial application of this material for WCO refinement, especially in lubricant production. Full article

Bamboo is known as the “world’s second largest forest”. The bamboo industry has become a globally recognized green industry, and the research and development of bamboo-based products have huge economic, ecological, and cultural values. In this study, a biosorbent with magnetically sensitive properties was developed based on natural bamboo powders (BPs) for the removal of methylene blue (MB) dye from aqueous solution. The selected BPs with 60 mesh were magnetized by loading Fe₃O₄ using an in situ co-precipitation process. The adsorption–desorption equilibrium was nearly established after 30 min, achieving a removal efficiency of 97.7% for 5.0 g/L BPs/Fe₃O₄ in a 20 mg/L MB solution. The removal efficiency of MB by 5.0 g/L BPs/Fe₃O₄ exhibited a remarkable enhancement, escalating from 33.9% at pH = 5 to an impressive 93.9% at pH = 11 in a 50 mg/L MB solution. The linear fitting method demonstrated greater suitability for characterizing the adsorption process compared to the nonlinear fitting method, which encompassed both adsorption isotherms and kinetics studies. Among these approaches, the adsorption isotherms were well-fitted to the Langmuir model, while the kinetics were accurately represented by the pseudo-second-order model. The removal efficiency by the recycled BPs/Fe₃O₄ adsorbent remained at 97.3% over five consecutive cycles, proving that BPs/Fe₃O₄ has a high potential for being used as a highly efficient biosorbent. Moreover, the BPs/Fe₃O₄ biosorbent had superparamagnetism with strong magnetic sensitivity, which could facilitate the sustainable removal of hazardous dye from the aqueous solution in practical applications. Full article

Intensified human activities such as urbanization, agricultural production, industrialization, mining, and fish farming have led to high concentrations of nutrients in water bodies, resulting in eutrophication. Eutrophication has become a global problem that threatens water ecosystems globally. The present study examines the efficiency of applying a novel modified material as an adsorbent for phosphate and ammonium uptake from natural eutrophic freshwater, called ‘ZeoPhos’. The novel material consists of natural zeolite and the addition of iron, calcium, and humic ions, which have been reported for their high adsorption capacity and nutrient-binding properties. Morphological and chemical composition analysis by SEM/EDS and TEM microscopic analysis results are included for natural and modified zeolite. Ammonium and orthophosphate kinetic adsorption results are aligned with pseudo-second kinetic models and reveal 78% and 70% adsorption removal efficiency for solutions of 1 mg NH₄⁺-N/L and 1 mg PO₄³⁻-P/L, respectively. Finally, ‘ZeoPhos’ ammonium and orthophosphate ions adsorption capacity reached up to 28.61 mg/g ± 0.32 and 27.13 mg/g ± 0.57, respectively, after Langmuir fitting isotherm experiments. Full article

This study investigated the effects of combining sodium alginate (ALG) with various natural hydrocolloids on the microstructure and release behaviors of microbeads. The encapsulation solutions were prepared at a 1:1 (w/w) ratio with ALG as the control and carrageenan (CAR), locust bean gum (LBG), acacia gum (ACA), pectin (PEC), and carboxymethyl cellulose (CMC) as experimental groups. Each formulation contained 0.2% (w/v) tartrazine and was extruded into a CaCl₂ solution for bead production. Encapsulation efficiency varied across formulations, with the lowest in the control (ALG-ALG) and highest in ALG-CAR and ALG-CMC, reaching 74% and 78%, respectively. The microbead sizes ranged from 2.07 to 3.48 mm, with the lowest particle diameter observed in ALG-ACA composites. Surface analysis showed smooth and uniform microbeads in the control (ALG-ALG), while ALG-LBG microbeads were rougher. Release kinetics were assessed using various models, with the Higuchi model best describing the release for most formulations (highest R² values). Tartrazine release followed pseudo-Fickian behavior in all formulations, with slower release in ALG-ACA and faster release in ALG-LBG microbeads. This study fills a gap in understanding how the incorporation of different natural hydrocolloids influences both the encapsulation efficiency and release dynamics of alginate-based microbeads, providing valuable insights for applications in food and pharmaceutical industries. Full article

The physicochemical and adsorption properties of granular sorbents based on natural bentonite and modified sorbents based on it have been studied. It was found that modification of natural bentonite with iron (III) polyhydroxocations (mod. 1_Fe_5 GA) and aluminum (III) (mod. 1_Al_5 GA) by the “co-precipitation” method leads to a change in their chemical composition, structure, and sorption properties. It is shown that modified sorbents based on natural bentonite are finely porous (nanostructured) objects with a predominance of pores measuring 1.5–8.0 nm, with a specific surface area of 55–65 m²/g. Modification of bentonite with iron (III) and aluminum compounds by the “co-precipitation” method also leads to an increase in the sorption capacity of the obtained sorbents with respect to bichromate and arsenate anions and nickel cations by 5-10 times compared with natural bentonite. The obtained sorption isotherms were classified as Langmuir type isotherms. Kinetic analysis showed that at the initial stage the sorption process is controlled by an external diffusion factor, i.e. refers to the diffusion of sorbent from solution into a liquid film on the surface of the sorbent. Then the sorption process begins to proceed in a mixed diffusion mode, when it limits both the external diffusion factor and the internal diffusion factor (the diffusion of the sorbent to the active centers through the system of pores and capillaries). To determine the contribution of the chemical stage to the rate of adsorption of bichromate and arsenate anions and nickel(II) cations with the studied granular sorbents, kinetic curves were processed using the equations of chemical kinetics (pseudo-second-order model). As a result, it was found that the adsorption of the studied anions by modified sorbents based on natural bentonite is best described by a pseudo-second-order kinetic model. It is shown that the use of natural bentonite for the development of technology for the production of granular sorbents based on it has an undeniable advantage, firstly, in terms of its chemical and structural properties, it is easily and effectively modified, and secondly, having astringent properties, granules are easily made on its basis, which turn into ceramics during high-temperature firing. The result is a granular sorbent with high physical and mechanical properties. Since bentonite is an environmentally friendly product, the technology of recycling spent sorbents is also greatly simplified. Full article

In this review, we toxicologically assessed the naturally occurring toxin domoic acid. We used the One Health approach because the impact of domoic acid is potentiated by climate change and water pollution on one side, and reflected in animal health, food security, human diet, and human health on the other. In a changing environment, algal blooms are more frequent. For domoic acid production, the growth of Pseudo-nitzschia diatoms is of particular interest. They produce this toxin, whose capability of accumulation and biomagnification through the food web impacts other organisms in the ecosystem. Domoic acid targets nervous system receptors inducing amnestic shellfish poisoning, among other less severe health-related problems. However, the impact of domoic acid on non-target cells is rather unknown, so we reviewed the currently available literature on cytogenetic effects on human and animal cells. The results of different studies indicate that domoic acid has the potential to induce early molecular events, such as oxidative imbalance and DNA damage, thus posing an additional threat which needs to be thoroughly addressed and monitored in the future. Full article

Fragment libraries have a major significance in drug discovery due to their role in de novo design and enumerating large and ultra-large compound libraries. Although several fragment libraries are commercially available, most are derived from synthetic compounds. The number of fragment libraries derived from natural products is still being determined. Still, they represent a rich source of building blocks to generate pseudo-natural products and bioactive synthetic compounds inspired by natural products. In this work, we generated and analyzed a fragment library of natural products from Colombia, a highly diverse geographical region where fragment libraries are yet to be reported. We also generated and reported fragment libraries of three novel natural product libraries and, as a reference, the most updated version of FDA-approved drugs. In line with the principles of open science, the fragment libraries developed in this study are freely available. Full article

We introduce and investigate the properties of new families of univariate and bivariate distributions based on the survival function of the Lindley distribution. The univariate distribution, to reflect the nature of its construction, is called a power Lindley survival distribution. The basic distributional properties of this model are described. Maximum likelihood estimates of the parameters of the distribution are studied and the corresponding information matrix is identified. A bivariate power Lindley survival distribution is introduced using the technique of conditional specification. The corresponding joint density and marginal and conditional densities are derived. The product moments of the distribution are obtained, together with bounds on the range of correlations that can be exhibited by the model. Estimation of the parameters of the model is implemented by maximizing the corresponding pseudo-likelihood function. The asymptotic variance–covariance matrix of these estimates is investigated. A simulation study is performed to illustrate the performance of these parameter estimates. Finally some examples of model fitting using real-world data sets are described. Full article

Novel sorbents were produced using sustainable and eco-friendly methods, aimed at minimizing environmental impact while utilizing industrial by-products and natural minerals. Olive stones and molasses derived from olive mill and sugar industries, respectively, and an abundant, natural and low-cost mineral, clinoptilolite, were combined in the following proportions: 80/20 clinoptilolite/stone, 80/10/10 clinoptilolite/stone/molasses, 50/50 stone/molasses, w/w. Then, physical carbonization (CL80OL20C, CL80OL10M10C, OL50M50C) or chemical activation (CL80OL20A, CL80OL10M10A, OL50M50A) took place. The adsorbents were characterized through Raman, FT-IR, BET and SEM-EDS analysis. The CL80OL20A material presents the highest ratio of C/O in EDS analysis and the lowest I_D/I_G in Raman spectroscopy. The increase in the specific surface area is as follows: OL50M50C < OL50M50A < CL80OL10M10C < CL80OL20C < CL80OL20A < CL80OL10M10A. Three applications were conducted: two with dyes (methylene blue and methyl red) in aqueous means and one in olive mill wastewaters for the removal of total phenols and their addition to rice, increasing the total phenolic content and producing novel foods. The well-fitted application of the pseudo-second order kinetic model to the experimental data has shown that chemisorption is the prevailing mechanism. The adsorbed amount of the recovered phenols to rice ranges from 0.14 to 0.93 mg/g. Consequently, olive and sugar by-products can be used as filters either to adsorb dangerous organic compounds or to recover bioactive compounds from wastewater, preventing their disposal in the environment, which could otherwise lead to severe negative effects on the ecosystems. Full article