Aqueous Research Articles

Electrochemical Hydrogenation of Quinoline Enabled by Cu0‐Cu+ Dual Sites Coupled with Efficient Biomass Valorization in Aqueous Solution

AbstractThe hydrogenation of nitrogen‐containing heterocyclic precursors in aqueous medium is challenging, especially at ambient temperature and pressure. Electrochemical hydrogenation (ECH) of quinoline to 1,2,3,4‐tetrahydroquinoline (THQ) at mild conditions using water as the hydrogen source is demonstrated with splendid activity on a Cu‐based nonprecicous catalyst. The yield of THQ is up to ≈100% with ≈100% selectivity at −1.275 V vs Hg/HgO. The real active sites and key intermediates are deciphered, where the Lewis acid‐base sites on the heterointerface of Cu/Cu2O are beneficial to the quinoline adsorption in a dual‐site coordination configuration and water dissociation to afford H*. The presence of Cu0 plays a vital role in inhibiting the binding of H*, which ensures good Faradaic efficiency. In addition, a novel co‐production system by coupling benzyl alcohol oxidation at the anode is established, achieving dual benefits in both energy utilization efficiency and economic benefits.

Integrated Valorization of Fucus spiralis Alga: Polysaccharides and Bioactives for Edible Films and Residues as Biostimulants

Fucus spp. seaweeds thrive in the cold temperate waters of the northern hemisphere, specifically in the littoral and sublittoral regions along rocky shorelines. Moreover, they are known to be a rich source of bioactive compounds. This study explored the valorization of Fucus spiralis through the extraction of bioactives and polysaccharides (PSs) for food applications and biostimulant use. The bioactives were extracted using microwave hydrodiffusion and gravity (MHG), where the condition of 300 W for 20 min resulted in the highest total phenolic content and antioxidant activity of the extract. Cellular assays confirmed that the extract, at 0.5 mg/mL, was non-cytotoxic to HaCat cells. Polysaccharides (PSs) were extracted from the remaining biomass. The residue from this second extraction contained 1.5% protein and 13.35% carbohydrates. Additionally, the free amino acids and minerals profiles of both solid residues were determined. An edible film was formulated using alginate (2%), PS-rich Fucus spiralis extract (0.5%), and F. spiralis bioactive-rich extract (0.25%). The film demonstrated significant antioxidant properties, with ABTS and DPPH values of 221.460 ± 10.389 and 186.889 ± 36.062 µM TE/mg film, respectively. It also exhibited notable physical characteristics, including high water vapor permeability (11.15 ± 1.55 g.mm.m−2.day−1.kPa−1) and 100% water solubility. The residues from both extractions of Fucus spiralis exhibited biostimulant (BS) effects on seed germination and seedling growth. BSs with PSs enhanced pea germination by 48%, while BSs without PSs increased the root dry weight of rice and tomato by 53% and up to 176%, respectively, as well as the shoot dry weight by up to 38% and up to 74%, respectively. These findings underscore the potential of Fucus spiralis within the framework of a circular economy, wherein both extracted bioactives and post-extraction by-products can be used for sustainable agriculture and food applications.

The influence of acid treatment on the adsorption‑structural characteristics of filtering materials created based on steelmaking slag

Many industrial enterprises use electroplating processes that lead to the formation of water containing heavy metal ions such as chromium, copper, zinc, nickel, and others. Such water is a dangerous source of environmental pollution. Most heavy metal ions belong to hazard classes I–II, they have carcinogenic and mutagenic properties, and have a cumulative effect.The literature analysis showed that there is positive experience in the use of steelmaking slags in the processes of cleaning contaminated water of various origins from heavy metals.The study examines the effect of acid activation on the adsorption‑structural characteristics of filtering materials created based on steelmaking slag. It is shown that during the interaction of some acids with slag, new crystallographic phases are formedon its surface, and contact with other acids leads to the leaching of ions and their transition to the aqueous phase. It has been established that during acid activation, the specific surface area increases by 57–132 times compared to the original material.

Impact of hydrophobically modified cellulose nanofiber on the stability of Pickering emulsion containing insect protein.

Cellulose nanofiber (CNF) is an ideal Pickering emulsion stabilizer because of its high aspect ratio and flexibility. CNF was hydrophobically modified by dodecenyl succinic anhydride and used to stabilize the simulated food emulsion system containing insect protein. The prepared dodecenyl succinate nanofiber (D-CNFs) was characterized by contact angle and laser particle size analyzer. The stability of the emulsion system under different conditions was characterized by zeta potential and appearance observation. Lastly, in vitro digestion simulation experiments were carried out to investigate whether the addition of D-CNFs had an effect on the digestion and absorption of oil. The modification process for dodecenyl succinic anhydride to CNFs was that the system temperature was 40 °C, the system pH value was 8.5 and the reaction time was 6 h. The water contact angle of the modified CNFs increased to 83.2 ± 0.9°. D-CNFs were introduced into the simulated food emulsion system containing insect protein. The increase in the concentration of D-CNFs in the aqueous phase promoted the stability of the simulated emulsion system. Increasing the ratio of insect protein was not conducive to the stability of the emulsion. The final fat digestibility of the emulsion with D-CNFs was lower than that of the emulsion without D-CNFs. Overall, the analysis and characterization results show the potential of the modified CNF as a food simulant emulsion stabilizer containing insect protein, which can be used for the development of specific functional foods. © 2024 Society of Chemical Industry.

Development of a Bioorthogonal Click-to-Release Reaction for Hydrogen Polysulfide (H2Sn) Detection.

In this study, we present an innovative "click-to-release" strategy for the design of highly specific H2Sn bioorthogonal probes that undergo a specific click reaction with H2Sn and release fluorophores by a following rearrangement. A library of cyclooctyne derivatives was established and successfully demonstrated the availability of the release strategy. Then, a model probe CM-CT was synthesized, which can achieve effective fluorophore release (>80%) in the presence of a H2Sn donor. To further validate the application of this class of probes, a new probe QN-RHO-CT based on Rhodamine 110 was developed. This probe showed good water solubility (>160 μM) and fast release kinetics and can achieve selective H2Sn detection in living cells. We used this probe to study the process of H2S-mediated protein S-persulfidation and demonstrated that excess H2S would directly react with protein persulfides to generate H2S2 and reduce the persulfides to thiols. Additionally, we elucidated the click-to-release mechanism in our design through a detailed mechanistic study, confirming the generation of the key intermediate α, β-unsaturated cyclooctanethione. This bioorthogonal click-to-release reaction provides a useful tool for investigating the function of H2Sn and paves the way for biological studies on H2Sn.

Novel antimicrobial polyvinyl alcohol film by incorporating β-cyclodextrin/berberine inclusion complex preserving the storage quality of salmon fillets

Antimicrobial packaging film mediated by photodynamic inactivation (PDI) based on biodegradable polymers is promising. The photosensitizer berberine chloride (BBR) was encapsulated into the β-cyclodextrin (CD) to exert its aggregation-induced emission (AIE) property. On this basis, novel PDI-mediated polyvinyl alcohol (PVA) films were fabricated by incorporating the CD/BBR inclusion complex. The PVA/CD/BBR films had high light transmittance (∼70 %) in the visible light range, and possessed good biodegradability with the water absorption of 76 % and water solubility of 31 %. Besides, the films exhibited good mechanical properties with the tensile strength of 62.53 MPa at elongation break of 69.14 %, owing to the formation of hydrogen bonds between the PVA and CD/BBR. The PDI-mediated films were irradiated (14.4 J/cm2) to produce ROS to kill ∼4 log CFU/mL of Listeria monocytogenes and Vibrio parahaemolyticus. In addition, the films potently inactivated native bacteria (0.92 log CFU/g) on salmon fillets after 9 days of storage, and maintained their sensory quality, water holding capacity, and notably, inhibited the chemical changes of salmon fillets to extend the shelf-life for at least 3 days.

High Performance and Selective Sequestration of Cd(II) from Water by Layered Thiophosphate.

The extensive use of toxic cadmium (Cd) in energy conversion and industrial applications ranging from solar cells and battery appliances to paints and pigments contaminates water bodies. However, the upper limit of Cd contamination in drinking water is to be only 3 ppb by the WHO and 5 ppb by the USA-EPA, which underscores the need for cost-effective, efficient, and ppb level capture of Cd from contaminated water. Leveraging the selectivity due to Lewis's hard-soft acid-base (HSAB) theory, we have achieved swift and highly selective capture of Cd(II) ions from aqueous mediums using layered potassium manganese thiophosphate (K-MnPS3). K-MnPS3 effectively removes Cd(II) ions from extremely dilute aqueous solutions (ppb levels), achieving a maximum sorption capacity of 405.43 mg/g and a removal rate exceeding 97% within 20 min. Even in the presence of competing ions such as Na+, Mg2+, Ca2+, and Pb2+, K-MnPS3 remains selective. Additionally, it operates efficiently across a wide pH range (1.78-11.19) with a high distribution coefficient (∼104 mL/g). Breakthrough experiments using a 1 wt % K-MnPS3 and 99 wt % sand column showed complete breakthrough of Cd(II) after 62 h, leading K-MnPS3 as a promising candidate for Cd(II) removal from industrial effluents.

Primordial Molecular 1-Bit Magnitude Comparator in consort with Excitation-Guided mouldable Logic Systems: A guided design of Regular Interactions between Molecules.

In addition to designing certain excitation modulated logic systems, we have created the first-ever genuine molecular 1-bit magnitude comparator, using acid and base guided varied absorption responses at separate channels. Designed and manufactured Bifunctional Bis(indolyl)methane Derivative (1) demonstrates distinct optical responses (in UV-visible and fluorescence mode) to a range of chemical stimuli (acid, base, Hg2+, Cu2+, EDTA, GSH, etc.) in aqueous medium. Intriguingly, the compound's excitation-modulated fluorescence responses appeared to change at different detection channels depending on whether the aforementioned analytes were present or not. We have proposed not only an excitation driven logic system with switchable molecular IMPLICATION and XNOR logic gates, but also a molecular 1-bit magnitude comparator in our proposal. A second excitation driven logic system with switchable molecular COMPLEMENT and NOR logic gates was also designed with two different optical channels and used Hg(II) & Cu(II) as chemical inputs.

Design and fabrication of acorn-like Janus molecularly imprinted materials for highly specific separation and enrichment of oxytetracycline from restaurant oily wastewater

Molecularly imprinted polymer (MIP) is dedicated to the adsorption of target substances in the aqueous phase, but ignores the adsorption in a more complex environment (oily wastewater). In order to explore the application field of existing MIPs, acorn-like Janus particles were fabricated by photo-initiated seed swelling polymerization. A novel amphiphilic Janus-MIP was prepared with the acorn-like Janus particles as matrix, methacrylic acid, ethylene dimethacrylate and oxytetracycline (OTC) as functional monomers, crosslinking agents and template molecules via surface initiated-atom transfer radical polymerization (SI-ATRP). For comparison, the poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) (poly (GMA-co-EDMA)) microspheres were also utilized as the matrix to prepare common spherical-MIP. The adsorption capacity of Janus-MIP for OTC was 23.8 mg g−1 in oil-water system, while the adsorption capacity of spherical-MIP for OTC was only 12.6 mg g−1 in the same system. At the same time, through high performance liquid chromatography (HPLC) analysis, Janus-MIP can specifically recognize and adsorb trace OTC in restaurant oily wastewater samples, and the proposed method exhibited a lower limit of detection (LOD, 3 ng mL−1) and a higher OTC recovery rate (94.2 %–98.4 %). This work demonstrated great potential for the detection and control of OTC contamination from real samples in an oil-water mixed environment.

Concurrent analysis of genome and transcriptome in one single cell

Thus far, multiple techniques for single cell analysis have been developed, yet we lack a relatively simple tool to assess DNA and RNA from the same cell at whole-transcriptome and whole-genome depths. Here we present an updated method for physical separation of cytoplasmic RNA from the nuclei, which allows for simultaneous studies of DNA and RNA from the same single cell. The method consists of three steps—(1) immobilization of a single cell on solid substrate, (2) hypotonic lysis of immobilized single cell, and (3) separation of cytosol containing aqueous phase and immobilized nucleus. We found that DNA and RNA extracted from single cell using our approach is suitable for downstream sequencing-based applications. We demonstrated that the coverage of transcriptome and genome sequencing data obtained after DNA/RNA separation is similar to that observed without separation. We also showed that the separation procedure does not create any noticeable bias in observed mutational load or mutation spectra. Thus, our method can serve as a tool for simultaneous complex analysis of the genome and transcriptome, providing necessary information on the relationship between somatic mutations and the regulation of gene expression.

Construction of Pickering emulsions stabilized by small molecular bioactive nanocrystals: Crosstalk between bioactive molecular structure and initial aqueous phase

Pickering emulsions stabilized with bioactive nanocrystals (BNC-PEs) have attracted increasing attentions in recent years. However, the mechanisms for the construction of stable BNC-PEs remain obscure. This study aimed to investigate the effects of the bioactive molecular structure and the initial pH of the aqueous phase on the fabrication and stability of BNC-PEs and the crosstalk between the two factors. Puerarin, tanshinone IIA and ferulic acid with unique structural characteristics were employed as model components to prepare BNC-PEs. Results showed that the initial pH of the aqueous phase significantly affected the stability of BNC-PEs through influencing the particle sizes and charges of nanocrystals, while the molecular structure of bioactive substances affected the three-phase contact angles or interfacial tensions. The construction and stability of the three kinds of BNC-PEs were all improved with increasing initial pH of the aqueous phase. Moreover, it was first found that the bioactive molecular structure strongly interfered with the influences of the initial pH of the aqueous phase on the stability of BNC-PEs. This study demonstrated for the first time that there might be a crosstalk between the bioactive molecular structure and the initial pH of the aqueous phase, and that the optimal pH of the aqueous phase might be intricately linked to the molecular structure of bioactive nanocrystals for BNC-PEs.

Simplified synthesis and identification of novel nanostructures consisting of cobalt borate and cobalt oxide for crystal violet dye removal from aquatic environments

Crystal violet dye poses significant health risks to humans, including carcinogenic and mutagenic effects, as well as environmental hazards due to its persistence and toxicity in aquatic ecosystems. This study focuses on the efficient removal of crystal violet dye from aqueous media using novel Co3O4/Co3(BO3)2 nanostructures synthesized via the Pechini sol–gel approach. The nanostructures, which were abbreviated to EN600 and EN800, were fabricated at calcination temperatures of 600 and 800 °C, respectively. X-ray diffraction (XRD) analysis revealed that the synthesized samples have a cubic Co3O4 phase and an orthorhombic Co3(BO3)2 phase, with mean crystal sizes of 43.82 nm and 52.93 nm for EN600 and EN800 samples, respectively. The Brunauer–Emmett–Teller (BET) surface areas of EN600 and EN800 samples were 65.80 and 43.76 m2/g, respectively, indicating a significant surface area available for adsorption. Optimal removal of crystal violet dye was achieved at a temperature of 298 K, a contact time of 70 min, and a pH of 10. The maximum adsorption capacities were found to be 284.09 mg/g for EN600 and 256.41 mg/g for EN800, which are notably higher compared to many conventional adsorbents. The adsorption process followed the pseudo-second-order kinetic model and fitted well with the Langmuir isotherm. The adsorption was exothermic, spontaneous, and physical in nature. Moreover, the adsorbents exhibited excellent reusability, retaining high efficiency after multiple regeneration cycles using 6 mol/L hydrochloric acid. These findings highlight the potential of these Co3O4/Co3(BO3)2 nanostructures as effective and sustainable materials for water purification applications.

Investigations of Crucial Factors for the Non-Covalent Functionalization of Black Phosphorus (BP) using Perylene Diimide Derivatives for the Passivation of BP Nanosheets.

The non-covalent functionalization of black phosphorus (BP) was studied with a scope of ten tailor-made perylene diimides (PDIs). A combination of UV/Vis-, fluorescence-, as well as Raman spectroscopy and atomic force microscopy was used to investigate the structural factors, which contribute to a pronounced PDI-BP interaction and thus support the protection of BP nanosheets against oxidative degradation. We were able to show, that water-soluble, amphiphilic PDIs with highly charged head groups can be used for the non-covalent functionalization of BP in aqueous media. Here, based on the hydrophobic effect, an efficient adsorption of the respective PDI molecules takes place and leads to the formation of a passivating film, yielding a considerable stabilization of the BP flakes under ambient conditions exceeding 30 days.

​Statistical-based optimization and mechanism assessments of Arsenic (III)​ adsorption by ZnO-Halloysite nanocomposite​

Arsenic contamination in aqueous media is a serious environmental problem, especially in developing countries. In this research, the Box-Behnken response surface methodology was used to optimize the most relevant variables affecting arsenic adsorption on the ZnO-halloysite surface, including temperature, adsorbent dosage, pH, contact time, and As (III) initial concentration. The regression analysis indicated that the experimental data were appropriately fitted to a quadratic model with the adjusted R-squared value (R2) of 0.982 for As(III) adsorption capacity and a linear model with R2 of 0.931 for As(III) removal. The p-values for both adsorption capacity and removal efficiency were below 0.05, with F-values of 116.91 and 115.58, respectively, supporting the model’s validity. The optimum conditions for maximum removal of As(III) were determined through numerical and graphical optimization using the desirability function. It was found that the optimum conditions for adsorption were pH = 7.99, contact time of 3.99 h, As(III) initial concentration of 49.96 mg/L, and adsorbent dosage of 0.135 g/40 ml. The accuracy of the optimization procedure was confirmed by a confirmatory experiment, which showed a maximum arsenic removal of 91.31% and an adsorption capacity of 12.63 mg/g under optimized conditions. Moreover, XPS analysis was performed at different pH levels to investigate the As (III) adsorption mechanism. The results demonstrated that As(III) adsorption occurs at acidic and neutral pH levels. On the other hand, when pH is increased to 8, As (III) oxidizes to As (V), and then adsorption occurs.

Sonication-Assisted Self-Assembled Resveratrol Nanoparticles with Enhanced Antiviral and Anti-inflammatory Activity against Respiratory Syncytial Virus-Induced Pneumonia.

Respiratory syncytial virus (RSV)-induced viral pneumonia in children is common worldwide. Its high occurrence and lack of an effective vaccine make it a leading cause of death in children. Severe RSV infection can trigger uncontrolled inflammatory responses in patients, so the development of small molecule drugs with the dual function of "direct antivirus" and "inflammatory response regulation" is welcome. Resveratrol (Res) has been reported to have antiviral and anti-inflammatory pharmacological effects, but its application is limited because of its poor water solubility and oral bioavailability. Based on small-molecule nanotechnology, we developed a sonication-assisted self-assembly method for preparing insoluble Res into highly soluble resveratrol nanoparticles (Res NPs). The obtained Res NPs exhibited a higher water solubility and a faster dissolution rate, which was more conducive to the effectiveness of Res in addressing RSV-induced viral pneumonia. In vitro studies had shown that Res NPs played an antiviral role by inhibiting RSV replication and reducing the production of pro-inflammatory cytokines. Nebulized inhalation administration of Res NPs prolonged the drug's residence time in the lungs, which appears to increase the accumulation and effectiveness of Res NPs. Additionally, in vivo studies had demonstrated significant benefits of Res NPs in inhibiting RSV viral load and improving the pulmonary microenvironment in RSV-infected mice. Both antiviral and anti-inflammatory experiments had confirmed that the pharmacological activity of Res NPs is superior to that of Res. This suggested that nanosizing Res was an effective way to enhance the original pharmacological activity of Res and also offered a new formulation strategy for treating viral pneumonia.

Inhibition of Aβ16-22 Aggregation by [TEA]+[Ms]- Follows Weakening of the Hydrophobic Core and Sequestration of Peptides in Ionic Liquid Nanodomains.

We developed a coarse-grained model for the protic ionic liquid, triethylammonium mesylate ([TEA]+[Ms]-), to characterize its inhibitory effects on amyloid aggregation using the K16LVFFAE22 fragment of the amyloid-β (Aβ16-22) as a model amyloidogenic peptide. In agreement with previous experiments, coarse-grained molecular dynamics simulations showed that increasing concentrations of [TEA]+[Ms]- in aqueous media led to increasingly small Aβ16-22 aggregates with low beta-sheet contents. The cause of [TEA]+[Ms]-'s inhibition of peptide aggregation was found to be a result of two interrelated effects. At a local scale, the enrichment of interactions between [TEA]+ cations and hydrophobic phenylalanine side chains weakened the hydrophobic cores of amyloid aggregates, resulting in poorly ordered structures. At a global level, peptides tended to localize at the interfaces of IL-rich nanostructures with water. At high IL concentrations, when the IL-water interface was large or fragmented, Aβ16-22 peptides were dispersed in the simulation cell, sometimes sequestered at unaggregated monomeric states. Together, these phenomena underlie [TEA]+[Ms]-'s inhibition of amyloid aggregation. This work addresses the critical lack of knowledge on the mechanisms of protein-ionic liquid interactions and may have broader implications for industrial applications.

One-step hydrothermal synthesis of F,N,S-doped photoluminescent carbon dots with yellowish-orange emission for sensitive Cu2+ ion detection: Environmental and biomedical applications

Herein, fluorine-, nitrogen-, and sulfur-doped carbon dots (FNS-CDs) were prepared via a one-step hydrothermal synthesis using flufenamic acid and thiourea as precursors, which showed yellowish-orange fluorescence both in aqueous solution and in the solid state. The as-prepared FNS-CDs were monodisperse and had an average diameter of 4 nm, good water solubility, a fluorescence quantum yield of 18.63 %, and excellent pH and ionic strength stability. The optimal excitation/emission wavelengths of the FNS-CDs were 406/570 nm, with an excitation-dependent wavelength range of 365–435 nm. The surface states, morphologies, and elemental compositions of the FNS-CDs were characterized using FTIR, XRD, TEM, and XPS. In addition, the FNS-CDs without any further modification exhibited high selectivity and sensitivity as nanosensors for Cu2+ over other metal ions. The PL quenching phenomenon can be used to detect Cu2+ ions within a linear range of 1–25 μM with a detection limit of 83.10 nM and an association constant of 1.29 × 104 M−1. The PL of the FNS-CDs was significantly quenched by Cu2+ ions through static quenching and was restored upon the subsequent addition of EDTA. The practical application was demonstrated through the detection of Cu2+ ions in real water samples, yielding recovery rates ranging from 97.8 % to 103.9 % with an RSD below 2.5 %. The FNS-CDs/Cu2+ complex exhibits potent antibacterial activity against S. aureus (85.27 %±2.1 %) and E. coli (91.31 %±1.6 %), whereas the FNS-CDs/Cu2+ has a higher inhibitory effect on the growth of E. coli. Furthermore, the FNS-CDs (100 μg/mL) were used for cell imaging, showing low toxicity to HCT-116 cells exhibited yellowish-orange fluorescence under a confocal microscope.

Kinetics and sorption behavior of glyphosate and tricyclazole for their efficient retention in biomixtures

The present investigation aims to study adsorption-desorption behavior of glyphosate and tricyclazole in rice straw-compost biomixtures. To enhance pesticide adsorption and performance of the bio-purification system, rice straw-compost (BM) biomixture was mixed with wheat straw biochar (WBC, 1% and 5%), and adsorption of both pesticides in control (BM) and WBCBM(1%) and WBCBM(5%) biomixtures was compared. The kinetics study suggested that the pseudo-second-order model best explained the time-dependent adsorption of both pesticides and intraparticle adsorption was not the rate-determining step. Tricyclazole was more sorbed than glyphosate in all biomixtures which can be attributed to its lower water solubility. The WBC increased the sorption of both pesticides, but the effect varied with the nature of pesticides and biochar content. The adsorption coefficient values in BM, WBCBM(1%), and WBCBM(5%) biomixtures were 26.74, 38.16, and 51.97 (glyphosate) and 38.07, 59.94, and 84.54 (tricyclazole), respectively. The adsorption data was subjected to the Freundlich, the Langmuir, and the Temkin isotherms, and among them, the Freundlich isotherm best explained pesticide adsorption behavior. Desorption results suggested that the adsorption of glyphosate was more irreversible than tricyclazole and depended upon initial pesticide concentration. This study suggested that biochar mixed rice straw-compost biomixtures can be exploited in bio-purification systems for glyphosate and tricyclazole.

Evaluating the physical properties of microwave-cured and heat-cured acrylic denture base materials after the addition of ZrO2 nanoparticles.

Background: The structural, physical, and mechanical properties of denture-based acrylic resin are still compromised by water sorption, water solubility, and porosity. These issues have long called for improved techniques, and the use of nanoparticles is one of them. The main objective of the current investigation was to evaluate and contrast some physical parameters (water sorption, water solubility, and porosity) after the incorporation of ZrO2 nanoparticles (0%, 3% and 5%) into heat-cured acrylic denture base materials (Ivoclare, Major) and microwave-cured acrylic (Acron MC). Materials and methods: A total of 60 resin specimens were manufactured, including 5 specimens for each concentration of ZrO2 NP (30 for porosity and 30 for water sorption and solubility). Followed the manufacturer's directions for preparing the sample of each material. Results: The results were analysed with descriptive statistics, Analysis of Variance(ANOVA) test, Duncan multiple range test, and independent T test demonstrated that the addition of nanoparticles (3% and 5%) decreased water sorption, water solubility, and porosity of PMMA(polymethyl methacrylate) for both types(microwave-cured and heat-cured acrylic denture base materials). Where, at 3%, the ZrO2 nanoparticles showed the best values for all tests compared to the control group. Conclusions: ZrO2 (3% and 5%) nanoparticle reinforcement of acrylic resin can be a useful tactic for lowering water sorption, solubility and porosity, thereby enhancing the performance of the material in various applications for microwave-cured and heat-cured acrylic denture base materials.

Unveiling Hierarchical Self-Assembly of Triazolylferrocenyl Dendrimers: Producing Non-Traditional Intrinsically Green Fluorescent Vesosomes for Nanotheranostics.

Dendrimers and supramolecular chemistry continue to fascinate researchers due to the endless unrevealed potential of their combination. This study investigates the self-assembly process of a series of hydrophobic triazolylferrocenyl dendrimers in aqueous medium. Deep investigation through NMR spectroscopy, absorption UV-vis spectroscopy along with theoretical simulations demonstrates that the ferrocenyl moieties interact intramolecularly and intermolecularly driving the self-assembly process. Data obtained by DLS, NTA, SEM, TEM, and EF-TEM demonstrate that these dendrimers, in water, spontaneously self-assemble through a hierarchical process. The dendrimers first self-assemble into uniform nanovesicles, which in turn self-assemble into larger vesosomes. The resulting vesosomes emit green non-traditional intrinsic fluorescence, which is a property that emerged from the self-assembled architectures. The vesosomes are efficiently uptaken by cancer cells and induce significant cytotoxic activity against the cancer cell line MCF-7, up to the submicromolar concentration. Positive dendritic effects are identified in the fluorescence intensity and in the cytotoxic activity of the vesosomes, which follow the trend G0-9Fc < G1-27Fc < G2-81Fc. This work showcases the remarkable potential of combining the two dynamic fields of dendrimers and supramolecular chemistry, which resulted in green fluorescent vesosomes capable of performing the dual role of cell imaging and killing, with potential applications in nanotheranostics.