Search Results (158)

Marine plants are a rich source of bioactive compounds with unique properties. The Mediterranean seagrass Posidonia oceanica is particularly abundant in phenolics and flavonoids, which exhibit antioxidant and anti-inflammatory activities. In this study, a phenolic-rich extract (POS) was obtained from beach-cast P. oceanica leaves using supercritical fluid extraction (SFE), an eco-friendly technique that preserves thermolabile compounds and avoids organic solvents. POS was incorporated into a base cream (POS-enriched cream) to evaluate its bioactive potential in topical applications. The antioxidant capacity of POS and the cream formulation was firstly evaluated using the DPPH radical scavenging assay, confirming strong radical scavenging activity for the POS (IC₅₀ = 2.32 ± 0.33 mg/mL) and significant activity for the POS-enriched cream (IC₅₀ = 16.76 ± 0.58 mg/mL) compared to a base cream as control (IC₅₀ = 37.62 ± 1.27 mg/mL). The antioxidant and photoprotective effects of POS were investigated in human skin fibroblasts (HS-68) exposed to oxidative stress and UV-induced damage, while anti-melanogenic activity was assessed in human epidermal melanocytes (HEM) by measuring tyrosinase activity and melanin content. POS significantly reduced ROS accumulation and modulated key molecular pathways involved in apoptosis (p-JNK), inflammation (NF-κB), energy balance (p-AMPK), and collagen synthesis (Col1A1) in fibroblasts. In melanocytes, both POS pure extract and POS-enriched cream effectively inhibited tyrosinase activity while maintaining unaltered basal melanin levels, indicating a modulatory rather than fully suppressive effect. These findings highlight the potential of P. oceanica SFE extracts as sustainable natural marine-derived products for photoprotection and anti-melanogenesis, thereby bridging the gap between marine waste stream management and applications in skin health and anti-aging strategies. Full article

Zinc oxide (ZnO) is a widely studied photocatalyst for the degradation of organic pollutants in water, yet its conventional sol–gel synthesis often suffers from low yield and produces materials with low specific surface area. In this study, we tackled these limitations by synthesizing ZnO nanoparticles using a supercritical-CO₂-assisted sol–gel method (ZnO-scCO₂). The influence of the calcination temperature, precursor concentration, and solvent type on the synthesis of ZnO was systematically investigated, and the materials were characterized with a combination of techniques (XRD, SEM, N₂ physisorption, UV-Vis-DRS spectroscopy). The photocatalytic performance of the ZnO-scCO₂ materials was evaluated in the degradation of two probe pollutants (phenol and rhodamine B, 200 ppm), under UV and visible radiation. The scCO₂-assisted method in ethanol as the solvent allowed achieving at least a four-fold higher ZnO yield and two-fold higher surface area compared to the materials prepared with a conventional sol–gel route without scCO₂. These ZnO-scCO₂ nanoparticles consistently showed enhanced photocatalytic activity in the removal of phenol and rhodamine B compared to their counterparts synthesized without scCO₂ and compared to commercial ZnO. Among the screened synthetic parameters, the solvent in which ZnO was prepared proved to be the one with the strongest influence in determining the ZnO yield and its photocatalytic activity. The optimum results were obtained using 0.50 M zinc acetate as the precursor in 1-butanol as the solvent, and calcination at 300 °C. Full article

Four new methionine sulfoxide-containing diketopiperazines, (+)-dysidmetsulfoxide A [(+)-1], (+)-dysidmetsulfoxide B [(+)-2], (+)-dysidmetsulfoxide C [(+)-3] and (−)-dysidmetsulfoxide C [(−)-3], were isolated from the South China Sea sponge Dysidea sp. These compounds represented the first example of diketopiperazines possessing the unit of methionine sulfoxide (MetO) isolated from marine sponges. As it was difficult to determine the configuration of chiral sulfur atom in the thionyl group, the structures with absolute configurations of these compounds were elucidated by spectroscopic analyses and total synthesis. It was noteworthy that the purchased synthetic precursors, Fmoc-L- and Fmoc-D-MetO, were mixtures of epimers, respectively, due to the stereogenic sulfur atom in MetO, which were separated to prepare the optically pure isomers via the method of supercritical fluid chromatography (SFC). In addition, the other four optical isomers [(−)-1, (−)-2, (+)-4 and (−)-4] were also synthesized. Furthermore, (+)-1, (−)-1, (+)-3, (+)-4 and (−)-4 showed potential anti-Parkinson’s disease activities in an in vivo zebrafish model. Full article

Non-thermal plasma (NTP) is a fast, reagent-free technology for dye removal, yet its performance is highly dependent on the operating conditions and on plasma–catalyst interactions. In this work, a coaxial falling-film dielectric barrier discharge (DBD) reactor was optimized for the degradation and decolorization of organic dyes, with ceria (CeO₂) employed as a catalyst. For the first time, CeO₂ prepared via a supercritical antisolvent (SAS) micronization route was tested in plasma-assisted dye decolorization and directly compared with its non-micronized counterpart. Optimization of plasma parameters revealed that oxygen feeding, an input voltage of 12 kV, a gas flow of 0.2 NL·min⁻¹, and an initial dye concentration of 20 mg·L⁻¹ resulted in the fastest decolorization kinetics. While the anionic dye Acid Yellow 36 exhibited electrostatic repulsion and negligible plasma–ceria synergy, the cationic dyes Crystal Violet and Methylene Blue showed strong adsorption on the negatively charged CeO₂ surface and pronounced plasma–catalyst synergy, with SAS-derived CeO₂ consistently outperforming the non-micronized powder. The SAS catalyst, characterized by a narrow particle size distribution (DLS) and spherical morphology (SEM), ensured improved dispersion and interaction with plasma-generated species, leading to significantly shorter decolorization radiation times compared to the literature benchmarks. Importantly, this enhancement translated into higher energy efficiency, with complete dye removal achieved at a lower specific energy input than both plasma-only operation and non-micronized CeO₂. Scavenger tests confirmed •OH radicals as the dominant oxidants, while O₃, O₂•⁻, and e⁻_a played secondary roles. Tests on binary dye mixtures (CV + MB) revealed synergistic decolorization under plasma-only conditions, and the CeO₂-SAS catalyst maintained high overall efficiency despite competitive adsorption effects. These findings demonstrate that SAS micronization of CeO₂ is an effective material-engineering strategy to unlock plasma–catalyst synergy and achieve rapid, energy-efficient dye abatement for practical wastewater treatment. Full article

Rambutan seed waste from fruit processing remains underutilized, while conventional biodiesel routes face high feedstock costs and food-versus-fuel concerns. This study investigated a novel catalyst-free process for biodiesel production from rambutan seed waste using supercritical ethanol and ethyl acetate as renewable reactants to valorize fruit by-products. Batch reactions on the semi-solid fraction of rambutan seed oil (RSO) were conducted at 15 MPa to evaluate the effects of temperature (275–375 °C), reactant-to-oil molar ratio (20:1–40:1), and reaction time (15–50 min) on fatty acid ethyl ester (FAEE) yield. Under optimal conditions, FAEE yields of 59.92 and 41.92% were obtained using ethanol (350 °C, 40:1, 30 min) and ethyl acetate (350 °C, 30:1, 40 min), respectively. However, severe conditions degraded unsaturated esters, revealing a conversion–stability trade-off. The ethanol system exhibited faster reaction kinetics and lower activation energy than ethyl acetate. Applying the optimized ethanol-based conditions to the liquid fraction of RSO, which contained a lower proportion of saturated fatty acids, resulted in a markedly improved FAEE yield of 94.16%. This study demonstrated a catalyst-free supercritical route for converting rambutan seed waste into biodiesel, advancing waste-to-energy strategies and circular bioeconomy. Full article

Municipal solid waste (MSW) recycling is constrained by contamination, heterogeneity, and infrastructure built around material-specific pathways. We introduce effectiveness-normalized greenhouse gas (GHG) emissions as a system-level metric that adjusts reported process burdens by feedstock eligibility (Effectiveness Fraction, EF) and carbon recovery efficiency (CRE) to reflect real-world MSW conditions. Using published LCA data and engineering estimates, we benchmark six pathways, mechanical recycling, PET depolymerization, enzymatic depolymerization, pyrolysis, supercritical water gasification (SCWG), and Regenerative Robust Gasification (RRG), at the scale of mixed MSW. Normalizing for EF and CRE reveals large differences between process-level and system-level performance. Mechanical recycling and PET depolymerization show low process intensities yet high normalized impacts because they can treat only a small share of plastics in MSW. SCWG performs well at broader eligibility. RRG, a plasma-assisted molten-bath approach integrated with methanol synthesis, maintains the lowest normalized impact (~1.6 t CO₂e per ton of recycled polymer) while accepting virtually all organics in MSW and vitrifying inorganics. Modeled methanol yields are ~200–300 gal·t⁻¹ without external hydrogen and up to ~800 gal·t⁻¹ with renewable methane reforming. The metric clarifies trade-offs for policy and investment by rewarding technologies that maximize diversion and carbon retention. We discuss how effectiveness-normalized results can be incorporated into LCA practice and Extended Producer Responsibility (EPR) frameworks and outline research needs in techno-economics, regional scalability, hydrogen sourcing, and uncertainty analysis. Findings support aligning infrastructure and procurement with robust, scalable routes that deliver circular manufacturing from heterogeneous MSW. Full article

Silica aerogels are highly attractive due to their outstanding properties, including their low density, ultralow thermal conductivity, large porosity, high optical transparency, and strong sorption activity. However, their inherent brittleness has limited widespread applications. Constructing a robust, highly porous three-dimensional network is critical to achieving the desired mechanical properties in aerogels. In this study, we introduce a novel synthesis route for fabricating lightweight and mechanically strong aerogels by incorporating poly(ethylene-co-vinyl alcohol) (EVOH) through thermally induced phase separation (TIPS). EVOH exhibits upper critical solution temperature (UCST) behavior in a mixture of isopropanol (IPA) and water, which can be utilized to reinforce the silica skeletal structure. Robust aerogels were prepared via the sol–gel process and TIPS method, followed by supercritical CO₂ drying, yielding samples with bulk densities ranging from 0.136 to 0.200 g/cm³. N₂ physisorption analysis revealed a mesoporous structure, with the specific surface area decreasing from 874 to 401 m²/g as EVOH content increased from 0 to 80 mg/mL. The introduced EVOH significantly enhanced mechanical performance, raising the flexural strength and compressive strength to 0.545 MPa and 18.37 MPa, respectively—far exceeding those of pure silica aerogel (0.098 MPa and 0.74 MPa). This work demonstrates the effectiveness of the TIPS strategy for developing high-strength, low-density silica aerogels with well-preserved porosity. Full article

To address critical limitations of ultra-low viscosity supercritical CO₂ fracturing fluids, including excessive fluid loss and inadequate proppant transport capacity, a series of thickeners designed to significantly enhance CO₂ viscosity were synthesized. Initially, FT-IR and ¹H NMR characterization confirmed successful chemical reactions and incorporation of both solvation-enhancing and -thickening functional groups. Subsequently, dissolution and thickening performance were evaluated using a custom-designed high-pressure vessel featuring visual observation capability, in-line viscosity monitoring, and high-temperature operation. All thickener systems exhibited excellent solubility, with 5 wt% loading elevating CO₂ viscosity to 3.68 mPa·s. Ultimately, molecular simulations performed in Materials Studio elucidated the mechanistic basis, electrostatic potential (ESP) mapping, cohesive energy density analysis, intermolecular interaction energy, and radial distribution function comparisons. These computational approaches revealed dissolution and thickening mechanisms of polymeric thickeners in CO₂. Full article

Aerogels (AGs) are highly porous, low-density, disordered, ultralight macroscopic materials with immense surface areas. Traditionally synthesized using aqueous sol–gel chemistry, starting by molecular precursors, the nanoparticles (NPs) dispersions gelation method is nowadays the most used procedure to obtain AGs with improved crystallinity and broader structural, morphological and compositional complexity. The Sol–gel process consists of preparing a solution by hydrolysis of different precursors, followed by gelation, ageing and a drying phase, via supercritical, freeze-drying or ambient evaporation. AGs can be classified based on various factors, such as appearance, synthetic methods, chemical origin, drying methods, microstructure, etc. Due to their nonpareil characteristics, AGs are completely different from common NPs, thus covering different and more extensive applications. AGs can be applied in supercapacitors, acoustic devices, drug delivery, thermal insulation, catalysis, electrocatalysis, gas absorption, gas separation, organic and inorganic xenobiotics removal from water and air and radionucleotides management. This review provides first an analysis on AGs according to data found in CAS Content Collection. Then, an AGs’ classification based on the chemical origin of their precursors, as well as the different methods existing to prepare AGs and the current optimization strategies are discussed. Following, focusing on AGs of inorganic origin, silica and metal oxide-based AGs are reviewed, deeply discussing their properties, specific synthesis and possible uses. These classes were chosen based on the evidence that they are the most experimented, patented and marketed AGs. Several related case studies are reported, some of which have been presented in reader-friendly tables and discussed. Full article

Background: Blackberry seed oil (BSO), obtained from Rubus spp. Xavante cultivar via supercritical CO₂ extraction, contains bioactive lipids and antioxidants, but its cosmetic application is limited by poor solubility and stability. Nanoencapsulation with poly(ε-caprolactone) (PCL) can overcome these limitations. Methods: BSO was characterized by Ultra-High-Performance Liquid Chromatography coupled with electrospray ionization quadrupole time-of-flight mass spectrometry and incorporated into PCL nanocapsules (NCBSO) using the preformed polymer deposition method. Physicochemical properties, stability (at 4 °C, room temperature, and 37 °C for 90 days), cytotoxicity, and collagen production were assessed in human fibroblasts. Additionally, a predictive in silico analysis using PASS Online, Molinspiration, and SEA platforms was performed to identify the bioactivities of major BSO compounds related to collagen synthesis, antioxidant potential, and anti-aging effects. Results: NCBSO showed a nanometric size of ~267 nm, low polydispersity (PDI < 0.2), negative zeta potential (−28 mV), and spherical morphology confirmed by FE-SEM. The dispersion remained stable across all tested temperatures, preserving pH and colloidal properties. In particular, BSO and NCBSO at 100 µg.mL⁻¹ significantly enhanced in vitro collagen production by 170% and 200%, respectively, compared to untreated cells (p < 0.01). Superior bioactivity was observed for NCBSO. The in silico results support the role of key compounds in promoting collagen biosynthesis and protecting skin structure. No cytotoxic effects were achieved. Conclusions: The nanoencapsulation of BSO into PCL nanocapsules ensured formulation stability and potentiated collagen production. These findings support the potential of NCBSO as a promising candidate for future development as a collagen-boosting cosmeceutical. Full article

Against the backdrop of global energy transition and strict environmental regulations, supercritical carbon dioxide (scCO₂) fracturing and oil displacement technologies have emerged as pivotal green approaches in shale gas exploitation, offering the dual advantages of zero water consumption and carbon sequestration. However, the inherent low viscosity of scCO₂ severely restricts its sand-carrying capacity, fracture propagation efficiency, and oil recovery rate, necessitating the urgent development of high-performance thickeners. The current research on scCO₂ thickeners faces a critical trade-off: traditional fluorinated polymers exhibit excellent philicity CO₂, but suffer from high costs and environmental hazards, while non-fluorinated systems often struggle to balance solubility and thickening performance. The development of new thickeners primarily involves two directions. On one hand, efforts focus on modifying non-fluorinated polymers, driven by environmental protection needs—traditional fluorinated thickeners may cause environmental pollution, and improving non-fluorinated polymers can maintain good thickening performance while reducing environmental impacts. On the other hand, there is a commitment to developing non-noble metal-catalyzed siloxane modification and synthesis processes, aiming to enhance the technical and economic feasibility of scCO₂ thickeners. Compared with noble metal catalysts like platinum, non-noble metal catalysts can reduce production costs, making the synthesis process more economically viable for large-scale industrial applications. These studies are crucial for promoting the practical application of scCO₂ technology in unconventional oil and gas development, including improving fracturing efficiency and oil displacement efficiency, and providing new technical support for the sustainable development of the energy industry. This study innovatively designed an amphiphilic modified amino silicone oil polymer (MA-co-MPEGA-AS) by combining maleic anhydride (MA), methoxy polyethylene glycol acrylate (MPEGA), and amino silicone oil (AS) through a molecular bridge strategy. The synthesis process involved three key steps: radical polymerization of MA and MPEGA, amidation with AS, and in situ network formation. Fourier transform infrared spectroscopy (FT-IR) confirmed the successful introduction of ether-based CO₂-philic groups. Rheological tests conducted under scCO₂ conditions demonstrated a 114-fold increase in viscosity for MA-co-MPEGA-AS. Mechanistic studies revealed that the ether oxygen atoms (Lewis base) in MPEGA formed dipole–quadrupole interactions with CO₂ (Lewis acid), enhancing solubility by 47%. Simultaneously, the self-assembly of siloxane chains into a three-dimensional network suppressed interlayer sliding in scCO₂ and maintained over 90% viscosity retention at 80 °C. This fluorine-free design eliminates the need for platinum-based catalysts and reduces production costs compared to fluorinated polymers. The hierarchical interactions (coordination bonds and hydrogen bonds) within the system provide a novel synthetic paradigm for scCO₂ thickeners. This research lays the foundation for green CO₂-based energy extraction technologies. Full article

In the synthesis of aerogels, the influence of the drying process on the nanostructure is an issue of utmost relevance for tailoring the final properties of these materials. Among the complex parameters affecting this process, the hydrophobicity of the aerogel structure plays a key role. Thus, herein, four different silica aerogel formulations based on tetraethyl orthosilicate and trimethoxymethylsilane were employed to produce aerogels with different wettability properties (from hydrophilic samples to highly hydrophobic). The synthesized gels were dried by three methods, namely freeze-drying, high-temperature supercritical drying with ethanol, and low-temperature supercritical drying with carbon dioxide, and the influence of each procedure on bulk density, porosity, pore size, and specific surface area of the resulting aerogels was analyzed in detail. The direct correlation between the surface hydrophobicity/hydrophilicity of the silica gels and the effects of each drying technique was analyzed, providing insights into a proper selection of the drying method depending on both the water affinity of the gel and the desired textural properties and structures. Full article

Aerogels have gained much interest in the last decades due to their specific properties, such as high porosity, high surface area, and low density, which have caused them to be used in multiple and varied fields. As the applicability of aerogels is tightly correlated to their morpho-structural features, special consideration must be allocated to the fabrication method. An emerging technique for producing nanostructured materials with tailored morphology and dimensions is represented by continuous-flow microfluidics. In this context, this work explores the synergic combination of aerogel-based materials with microfluidic synthesis platforms to generate advanced nanocomposite adsorbents for water decontamination. Specifically, this study presents the novel synthesis of a magnetic silica-based aerogel using a custom-designed 3D microfluidic platform, offering enhanced control over nanoparticle incorporation and gelation compared to conventional sol–gel techniques. The resulting gel was further dried via supercritical CO₂ extraction to preserve its unique nanostructure. The multi-faceted physicochemical investigations (XRD, DLS, FT-IR, RAMAN, SEM, and TEM) confirmed the material’s uniform morphology, high porosity, and surface functionalization. The HR-MS FT-ICR analysis has also demonstrated the advanced material’s adsorption capacity for various pesticides, suggesting its adequacy for further environmental applications. An exceptional 93.7% extraction efficiency was registered for triazophos, underscoring the potential of microfluidic synthesis approaches in engineering advanced, eco-friendly adsorbent materials for water decontamination of relevant organic pollutants. Full article

Rapid mixing is widely prevalent in the field of microfluidics, encompassing applications such as biomedical diagnostics, drug delivery, chemical synthesis, and enzyme reactions. Mixing efficiency profoundly impacts the overall performance of these devices. However, at the micro-scale, the flow typically presents as laminar flow due to low Reynolds numbers, rendering rapid mixing challenging. Leveraging the vortices within a droplet of the Taylor flow and inducing chaotic convection within the droplet through serpentine channels can significantly enhance mixing efficiency. Based on this premise, we have developed a droplet micromixer that integrates the T-shaped channels required for generating Taylor flow and the serpentine channels required for inducing chaotic convection within the droplet. We determined the range of inlet liquid flow rate and gas pressure required to generate Taylor flow and conducted experimental investigations to examine the influence of the inlet conditions on droplet length, total flow rate, and mixing efficiency. Under conditions where channel dimensions and liquid flow rates are identical, Taylor flow achieves a nine-fold improvement in mixing efficiency compared to single-phase flow. At low Reynolds number (0.57 ≤ Re ≤ 1.05), the chip can achieve a 95% mixing efficiency within a 2 cm distance in just 0.5–0.8 s. The mixer proposed in this study offers the advantages of simplicity in manufacturing and ease of integration. It can be readily integrated into Lab-on-a-Chip devices to perform critical functions, including microfluidic switches, formation of nanocomposites, synthesis of oxides and adducts, velocity measurement, and supercritical fluid fractionation. Full article

Traditional β-eucryptite (LiAlSiO₄) is renowned for its unique characteristics of low thermal expansion and high temperature thermal stability, making it an ideal material for precision instruments and aerospace applications. In this study, β-eucryptite was fabricated into an aerogel structure through the sol–gel process and supercritical drying method and using alumina sol as a cost-effective precursor. The synthesized β-eucryptite aerogel demonstrated unique properties including a negative thermal expansion coefficient (−7.85 × 10⁻⁶ K⁻¹), low density (0.60 g/cm³), and high specific surface area (18.1 m²/g). X-ray diffraction (XRD) and transmission electron microscopy (TEM) mutually corroborated the crystalline structure of β-eucryptite, with XRD confirming the phase purity and TEM imaging revealing well-defined crystal lattice characteristics. Combined nitrogen adsorption–desorption analysis and scanning electron microscopy observations supported the hierarchical porous microstructure, with SEM visualizing interconnected nanoporous networks and nitrogen sorption data verifying the porosity. The negative thermal expansion behavior was directly linked to the β-eucryptite crystal structure, as collectively validated by thermal expansion measurements. Additionally, Fourier transform infrared spectroscopy (FTIR) independently confirmed the aluminosilicate framework structure through characteristic vibrational modes. This research shows the innovation in the synthesis of β-eucryptite aerogel, especially its application potential in precision instruments and building materials that need low thermal expansion and high stability, and the use of aluminum sol as an aluminum source has simplified the preparation steps and reduced production costs. Full article