Pluronic P123 Research Articles

(Invited) Mesoporous Metallic Materials Electrodeposited from Polymeric Micelle Assemblies for Energy Applications

The surfactant-assisted electrodeposition is an effective means to obtain high-quality mesoporous materials in a rather simple synthesis approach. Commercial or home-made block copolymers can be dissolved in aqueous media above their critical micelle concentration to serve as a soft template in the so-called electrodeposition from polymeric micelle assemblies or micelle-assisted electrodeposition in short [1]. The nanoscale porosity of the resulting films, which extends throughout the whole surface and entire film thickness, endow them with large surface-to-volume (S/V) ratios. Such large S/V ratios are particularly amenable for (electro)catalytic applications and, whenever the alloy presents ferromagnetic properties, for magnetoelectric purposes. In our group, mesoporous Cu-Ni, Co-Pt, Ni-Pt and Fe-Pt alloys with pore size around 10 nm have been electrodeposited from Pluronic P-123 containing solutions [2-4]. Similarly, mesoporous Ni films with larger pore diameters (25 - 600 nm) have been deposited using custom-made PS-b-P4VP block copolymer micelles [5]. Even, the double template approach can be utilized to obtain, for example, matrices of mesoporous Co-Pt microdisks when the micelle-assisted electrodeposition is performed on optically lithographed substrates [6], or nanoporous Fe-Pd nanowires using anodized alumina and P-123 as hard and soft templates, respectively [7]. The introduction of an equilibration time between electrolyte preparation and deposition has been determined key in some cases to consistently reproduce the films mesoporosity [8].The electrodeposited mesoporous metallic materials exhibit higher electrocatalytic activity towards hydrogen evolution reaction (HER) in either acid or alkaline media compared to their dense counterparts [3]. In addition, their durability is not severely compromised in spite of the much larger surface exposed to the media. On the other hand, modulation of their magnetic properties with voltage is also possible when these films are electrolyte-gated in aprotic polar solvents like propylene carbonate. The intense electric field strength created at the film / electrolyte interface thanks to the built-in electric double layer allows for tuning of the coercivity (HC) or the saturation magnetization upon voltage application by virtue of different, but often concomitant, mechanisms taking place, like charge carrier accumulation and oxygen migration [6,9]. Variations greater than 30% in HC have been achieved.In this talk I will summarize the main synthesis-wise milestones achieved during the research in the field and the benefits brought by mesoporous alloys to electrocatalysis and magnetoelectricity.[1] C. Li et al. Acc. Chem. Res. 51 (2018) 1764[2] J. Zhang et al. ACS Appl. Mater. Interfaces 10 (2018) 14877[3] K. Eiler et al. Appl. Cat. B 265 (2020) 118597[4] E. Isarain‐Chávez et al. ChemSusChem 11 (2018) 367[5] R. Fagotto Clavijo et al. Cat. Today, in press.[6] C. Navarro-Senent et al. ACS Appl. Mater. Interfaces 10 (2018) 44897[7] D. Raj et al. Nanomaterials 13 (2023) 403[8] C. Navarro-Senent et al. Electrochim. Acta 358 (2020) 136940[9] C. Navarro-Senent et al. APL Materials 7 (2019) 030701

Electrosynthesis and Performance of Homogeneously Mesoporous Ni-Rich Ni-Pt Thin Films for Efficient Hydrogen Evolution Reaction in Acidic Media

The development of green hydrogen technology requires abundant electrocatalyst materials to (partially) replace costly platinum while maintaining the catalytic efficiency and durability. Nickel is an excellent choice for the partial replacement of Pt for water splitting, and is widely used for electrocatalysis in alkaline media. Although Ni cannot provide an activity identical to Pt, specific nanostructures aimed at a high surface-to-volume ratio, such as nanoporous structures, can significantly improve catalytic efficiency. However, in acidic media, the use of non-noble metals for electrocatalysis requires extensive durability tests to confirm the stability of the alloy. Additionally, the impact of hydrogen itself is often overlooked, as hydrogen is known to cause hydrogen embrittlement in Ni and its alloys.This contribution deals with the synthesis of a homogeneously mesoporous Ni-Pt alloy with high catalytic efficiency (Fig. 1). By electrodeposition from aqueous media, Ni-rich Ni-Pt alloy thin films are synthesised in a wide compositional range (between 60 and 99 at% Ni), depending on the deposition potential. The addition of the amphiphilic block copolymer Pluronic P-123 to the electrolyte formulation enables a micelle-assisted deposition process, resulting in films with homogeneous porosity with an approximate pore size of 10 nm irrespective of composition. Moreover, all thin films are single-phase and nanocrystalline [1], and show excellent performance under hydrogen evolution reaction (HER) in acidic media [2].As determined by Rutherford backscattering (RBS), the as-deposited Ni-Pt thin films with film thickness between 180 nm and 260 nm exhibit Pt enrichment at the surface of 1-2 nm in depth, after which Ni and Pt exhibit constant composition over depth. After hydrogen evolution in 0.5 M H2SO4, a gradient in Ni/Pt ratio over the film thickness is established, indicating preferential leaching of Ni into the electrolyte, and resulting in higher Pt content at the surface. Due to the porosity of the thin films, this leaching affects the entire film thickness. A chronopotentiometric durability test (24 h) reveals that the overpotential stabilises over time, indicating that the leaching of Ni is suppressed once a certain Pt/Ni ratio is attained in the thin films. In addition, the HER electrocatalysis is accompanied by a significant hydrogen uptake, determined by elastic recoil detection analysis (ERDA). Depending on the electrodeposition parameters, the as-deposited thin films already exhibit significant hydrogen concentrations between 2 and 10 at%. After the HER durability test, local cracking is observed by SEM, related to an excess of hydrogen in the thin films. Despite the cracking, no significant detachment of the films from the substrate is observed. The hydrogen contained in the films is assumed to be interstitial and does not affect the metallic nature of the Ni-Pt films. An X-ray photoelectron spectroscopy (XPS) post-analysis shows that the fraction of metallic Ni with respect to Ni in higher oxidation states is higher after exposure to the HER than for the as-prepared surface. Acknowledgement: Financed by the European Union – NextGenerationEU.[1] K. Eiler, J. Fornell, C. Navarro-Senent, E. Pellicer, J. Sort, Nanoscale, 2020, 12, 7749[2] K. Eiler, S. Suriñach, J. Sort, E. Pellicer, Appl. Catal. B, 2020, 265, 118597Figure 1: SEM micrograph of a mesoporous Ni93Pt7 thin film. Figure 1

Homoselective Synthesis of tetrazoles and chemoselective oxidation of sulfides using Ni(II)-Schiff base complex stabilized on 3-dimensional mesoporous KIT-6 surface as a recyclable nanocatalyst

Mesoporous silica with thick expanded walls, open porosity, and excellent thermal stability is a relatively new structure known as KIT-6. In this study, KIT-6 mesoporous was synthesized by using pluronic surfactant P123 as a modulator in an acidic environment. The synthesized KIT-6 was then modified by 3-chloropropyltrimethoxysilane (3-CPTMS) and finally, the nickel metal complex was fixed on the modified mesoporous KIT-6. IR, BET, XRD, EDS, SEM, AAS, and TGA methods were employed to examine the as-prepared catalyst. The proposed catalyst was then used for selective sulfides oxidation and preparation of tetrazole derivatives. The synthesized catalyst was found to be efficient and practical as it produced organic compounds in proper TOF and TON amounts, demonstrating the catalyst's practicality and efficiency.

Development of artificial leak-free phase change material (PCM) aggregates using emulsion technique, cementless binder, and cold-bonded pelletization

The present study developed new leak-free artificial PCM aggregates using an emulsion technique, cementless binder, and cold-bonded pelletization (hereafter, PCM-surfactant-aggregate) and significantly increased the PCM quantity in aggregates without PCM leakage, which was demonstrated from differential scanning calorimetric (DSC) and thermogravimetry (TG) results. The PCM-water-emulsion was produced by using a non-ionic surfactant, Pluronic P123, and used as mixing water to produce cementless artificial aggregates using Ca(OH)2-Na2CO3-activated fly ash and cold-bonded pelletization. The produced artificial PCM-surfactant-aggregates showed no material separation during preparation and no visual PCM leakage on the surface and were lightweight aggregates in terms of compressive strength (ASTM C330). In the concrete testing results, the 28-day compressive strength was 18.1 MPa when all fine and coarse aggregates were replaced with artificial PCM-surfactant-aggregates and the thermal conductivity decreased with increasing aggregate content. The testing on the heated concrete specimens having PCM-surfactant-aggregates indicated no PCM leakage, no dimensional change, and no strength reduction due to the PCM phase transition from solid to liquid. Overall, the concrete containing PCM-surfactant-aggregates showed an increase in the lowest temperature and a decrease in the highest temperature in the temperature profile of the indoor space in the dynamic heat flow test.

Phase Behavior and Structure of Poloxamer Block Copolymers in Protic and Aprotic Ionic Liquids.

Ionic liquids are promising media for self-assembling block copolymers in applications such as energy storage. A robust design of block copolymer formulations in ionic liquids requires fundamental knowledge of their self-organization at the nanoscale. To this end, here, we focus on modeling two-component systems comprising a Poly(ethylene oxide)-poly (propylene oxide)-Poly(ethylene oxide) (PEO-PPO-PEO) block copolymer (Pluronic P105: EO37PO58EO37) and room temperature ionic liquids (RTILs): protic ethylammonium nitrate (EAN), aprotic ionic liquids (1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6), or 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4). Rich structural polymorphism was exhibited, including phases of micellar (sphere) cubic, hexagonal (cylinder), bicontinuous cubic, and lamellar (bilayer) lyotropic liquid crystalline (LLC) ordered structures in addition to solution regions. The characteristic scales of the structural lengths were obtained using small-angle X-ray scattering (SAXS) data analysis. On the basis of phase behavior and structure, the effects of the ionic liquid solvent on block copolymer organization were assessed and contrasted to those of molecular solvents, such as water and formamide.

Synthesis and Characterization of Core-Shell Mesoporous Iron oxide Magnetic Nanoparticles using Modified Co-Precipitation Method

In recent era, development of nanotechnology is an art of delivery of drug by improving its compatibility, effectiveness and efficacy. Among all nanoparticles, magnetic nanoparticles play a predominant role to shows their targeted drug delivery using a magnetic field, also helps to diagnose the diseases like cancer. The present study included preparation of four different mesoporous nanoparticles using the Pluronic block copolymer P123 as a surfactant template, then insert iron oxides using co-precipitation method. The resulted formed mesoporous magnetic nanoparticles are examined for structural characters by using FTIR, XRD, HRSEM and Elemental Mapping techniques. The results of X-ray diffraction (XRD) showed that the formed composites conserved ordered mesoporous structure after the formation of iron oxide nanoparticles in the pores. FTIR results indicated that the surface contains silanol group and Fe–O on the surface of the materials at 1060 cm-1 and 1020 cm-1 peaks respectively. Scanning electron microscopy (SEM) results showed that all mesoporous magnetic nanoparticles within the range of size from 50 to 100nm also possessed a regular spherical shape. These particles possessed high surface area, high pore volume and showed magnetic response sufficient for drug targeting in the presence of an external magnetic field. Elemental mapping data indicated about the percentage of all elements present in the mesoporous materials. We concluded that all four types of magnetic nanoparticles are structurally arranged in their structure with sufficient percentage of elements on their particle surface along with good size range. Further loading of drug into all types of magnetic nanoparticles decides the loading efficiency, stability and drug release nature.

Efficient photocatalytic reduction of p-nitrophenol under visible light irradiation based on Ag NPs loaded brown 2D g-C3N4 / g-C3N4 QDs nanocomposite

Recently, low-cost graphitic carbon nitride (g-C3N4) revealed high photocatalytic activities and provided solutions to environmental pollution. In this study, we synthesized brown mesoporous 2D g-C3N4 by calcination dicyandiamide with pluronic P123. This is followed by loading of Ag NPs on the prepared 2D g-C3N4 by photodeposition process. After that, a ternary composite 2% Ag/ 2D g-C3N4 / g-C3N4 QDs heterojunction photocatalyst has been successfully prepared. The prepared nanomaterials were comprehensively characterized by various analysis techniques such as XRD, UV–Vis., BET, XPS, SEM, TEM. This new system exhibited a large surface area with porous structure and a wide absorption of visible light. The results verified that Ag NPs decoration enhanced the charge separation of photo-generated carriers of g-C3N4 2D and g-C3N4 QDs, promote significant enhancement in the photocatalytic activity for reduction of p-nitrophenol with a rate constant (k) value of 0.49729 / min in 6 min. This rate is about two-fold higher than that observed for pure g-C3N4 2D and g-C3N4 QDs as well as shows an improvement compared to 2% Ag/ g-C3N4 2D and g-C3N4 2D/ g-C3N4 QDs. The results open the door to design highly efficient 2D/0D nanocomposite photocatalysts for a wide variety of environmental applications.

Molecular engineering assembly of mesoporous carbon onto Ti3C2Tx MXene for enhanced lithium‐ion storage

AbstractThe rational construction of Ti3C2Tx MXene‐based composites has been deemed as a popular way to improve their electrochemical energy storage performances owing to the unique two‐dimensional (2D) structure, excellent conductivity, and good flexibility. However, it remains a major challenge to assemble mesoporous carbon onto Ti3C2Tx with fewer oxygen‐containing groups by using surfactants with short hydrophilic segments. In the work, we propose a molecular engineering assembly strategy for the growth of N,P co‐doped mesoporous carbon onto Ti3C2Tx nanosheets (NPMC/Ti3C2Tx) under the assistance of phytic acid by using melamine‐formaldehyde resin and pluronic P123 (PEO20PPO70PEO20) as the carbon/nitrogen source and soft template, respectively. The detailed investigations reveal that phytic acid with abundant hydroxyl groups can effectively enhance the hydrogen bond interactions among P123, carbon precursor, and Ti3C2Tx nanosheets, thus ensuring the efficient assembly of mesoporous carbon onto Ti3C2Tx. The obtained NPMC/Ti3C2Tx composite demonstrates a set of merits, including cylindrical mesopore, N,P co‐doping, and a good combination of mesoporous carbon and Ti3C2Tx nanosheets. As a result, it exhibits an improved lithium‐ion storage performance, delivering a high reversible capacity of 556.3 mA h g−1 after 100 cycles at 0.1 A g−1. The present work provides a feasible molecular engineering assembly route for the rational design of high‐performance Ti3C2Tx MXene‐based electrodes.

Fabrication and Release Mechanism Study of a Nanocapsule Breaker for Controlling Degradation Rate of Insoluble Residue in Slickwater at Moderate-Temperature Reservoirs

Summary In an ideal hydraulic fracturing project, the viscosity of hydraulic fracturing fluid (HFF) should drop to facilitate an efficient and quick fracture cleanup once proppants have been placed. Ammonium persulfate (APS) is widely used as an oxidizer breaker to degrade the insoluble residue of the HFF. However, a complex network of artificial fractures with sizes ranging from millimeters to micrometers restricts the transportation application and reaction time of standard breakers and current millimeter-sized capsule breakers. In this study, we introduce an APS nanocapsule (APS-NC) breaker, fabricated via a simple miniemulsion technique, that is capable of addressing the degradation of insoluble residue of the HFF in deep fractures. The nanocapsules are produced through precise control of the nanoprecipitation of poly(methyl methacrylate) (PMMA) onto aqueous APS nanodroplets. Stable aqueous nanodroplets are generated by means of an inverse miniemulsion using Pluronic P-123 as a specific surfactant to form a large and stable water-oil internal surface referring to the long chain and amphipathic property of Pluronic P-123 molecule. Pluronic P-123 is included in the process not only to stabilize the miniemulsion and increase the precipitation efficiency of PMMA but also to function as a thermo-responsive switch for the delayed burst release of APS. The size of the resulting nanocapsules can be controlled within the 207 and 821 nm range, yielding APS up to 92%. The release rate of APS can be controlled by the initial amount of PMMA (150–300 mg), environmental temperature (40–80°C), and environmental pH (3.4–7). When the temperature was 80℃, the initial amount of Pluronic P-123 dominated the release dynamic of APS. Compared with the APS breaker in a dynamic degradation experiment, the APS-NC had a more controllable degradation profile that could cause hydrolyzed polyacrylamide (HPAM) to burst degrade after 6 hours of heating at 80°C.

Synergistic Effect of Selenium Dioxide for Better Photocatalytic Performance of Conventional Semiconductors Distributed into Mesoporous SBA‐15

AbstractThe mesoporous SBA‐15 was synthesized in acidic conditions by hydrothermal method using Pluronic surfactant P123. A combination of SeO2, TiO2, and CuO was loaded in SBA‐15 in pairs or singly. Synthesized SBA‐15 and some loaded mesoporous materials were characterized using several standard techniques. The efficiency of the synthesized photocatalysts was verified for the decomposition of two different dyes (methylene blue (MB) and methyl green (MG)) under ultraviolet and visible light radiation. The results show that the synthesized photocatalyst based on SBA‐15 with 5 % by weight of TiO2 and 5 % by weight of SeO2 has better performance (about 98 % of MB or MG were degraded within 120 min under UV radiation). Also, the photocatalyst with 5 % by weight of SeO2 and 5 % by weight of CuO shows a good performance for the degradation of the dyes under visible irradiation in the presence of H2O2 (complete elimination of MB and MG within 150 and 75 min, respectively). The scavenging test shows that superoxide has a governing role for the degradation of the dyes. The photocatalysts are reusable and they could preserve more than 74 % of the efficiency following 4 times of consecutive use for the degradation of the dyes.

The Structural Change of TiO<sub>2</sub> and Fe<sub>2</sub>O<sub>3 </sub>Using P123 Template: Review

Pluronic P123 has become a potential agent for solubilizing various metal oxide precursor molecules. However, how these solubilizates affect the morphology of material remains poorly understood. In this review, the morphological transition of TiO2 and Fe2O3 induced by Pluronic P123 micelles has been comprehensively investigated. The change of TiO2 and Fe2O3 structure by P123 micelles forms micellar clusters governed by the balance of hydrophobic interaction and hydrogen bonding, which consequently leads to various micellar morphologies. The review results further show that the intensity of P123-TiO2 and and P123-Fe2O3 interaction increases with the hydrophobicity of the P123, indicating that hydrophobic interaction is more important in the TiO2 and Fe2O3 morphological transition. The transformation of the disordered morphology is more effective in the acidic pH scale range than the basic and neutral ones. Not only pH, but also seen when the reaction time not more than 4 hours with moderate temperature ranging from 300-500 °C and the ratio of P123 to Ti and Fe precursors of 1-5% (%w/w) is the optimum condition which changes the disordered morphology to a more regular one. The acidity, time reaction and temperature as the main parameter influencing the enhancement of the physical properties and morphology for the considered reaction.

Comparation Review between of Titania (TiO<sub>2</sub>) Synthesis Using CTAC and Fe-TiO<sub>2</sub> Synthesis Using Pluronic P123 as Surfactant

This study reviewed the synthesis of Titania with different shapes in the presence of cetyltrimethylammonium chloride (CTAC) as the famous stabilizer for directly altering the morphology and dimensions. These CTAC stabilizers usually provide the synthesis of Titania with a narrow size distribution and mostly single-crystalline structures in high yields. Many papers on the synthesis of Titania are available. However, only a few articles focus on the synthesis of Titania using CTAC as the stabilizer. The general rule for the shape transformation of Titania by CTAC stabilizer can be easily summarized based on the literature during the last ten year from https://www.sciencedirect.com/ as the data source.

Application of Pluronics for Enhancing Aqueous Solubility of Lipophilic Microtubule Destabilizing Compounds on the Sea Urchin Embryo Model.

In screening, the dilution of DMSO stock solution of a lipophilic molecule with an assay medium often causes compound precipitation. To overcome the issue, the application of Pluronics as cosolvents was examined using a phenotypic sea urchin embryo assay that allows for the quick and facile evaluation of the antiproliferative effect together with systemic toxicity. Maximum tolerated concentration values for Pluronics L121, P123, and F127 were 1.4 μM, 8.6 μM, and 39.7 μM, respectively, and correlated directly with their hydrophilicity. Pluronics L121 and P123 suppressed cleavage and blastomeres retained the round shape, unlike hydrophilic Pluronic F127, which induced fertilization envelope creasing and embryo deformation that could be associated with the interaction of hydrophilic PEO units with mucopolysaccharides at the surface of sea urchin embryos. The toxicity of P123, but not of L121 and F127, was temperature-dependent and markedly increased at lower temperatures. CMC values obtained at different temperatures confirmed that the toxic effect of P123 was associated with both unimers and micelles, whereas F127 toxicity was related mainly to micelles. Evaluation using phenotypic sea urchin embryo assay revealed that potent microtubule destabilizers, namely albendazole, diarylisoxazole, and two chalcones, retained antimitotic activity after the dilution of their DMSO or 2-pyrrolidone stock solutions with 1.25% w/v Pluronic P123 or 5% w/v Pluronic F127. It was suggested that Pluronic P123 and Pluronic F127 could be used as cosolvents to improve the solubility of lipophilic molecules in aqueous medium.

The Pursuit of Energy Reduction in Generation of Stable Nanobubbles

The repeatable and cost-efficient generation of nanobubbles is still a challenge. In most cases, the hydrodynamic generation of nanobubbles is used at larger scales. Therefore, every cost reduction possible in nanobubble generation is needed. In this work, we decided to check how the generation of nanobubbles changes when the surrounding liquid properties change. The generation of nanobubbles was carried out in a novel setup, designed by us. We investigated the minimum liquid velocity needed for nanobubble generation and propose correlations describing this based on the physicochemical properties of the liquid and gas phases. As carbon dioxide nanobubbles are commonly used for the treatment of ischemia and chronic wounds, the investigation of their stability enhancement is crucial for the wider public. We investigated the minimum rotation rate of the impeller needed for CO2 nanobubble generation and the influence of a biomedical surfactant (Pluronic P-123) addition and concentration change on the size of nanobubbles and their stability over time. Nanobubbles were stable in the presence of surfactant additions and showed the impact of both changes in generation time and shear stress on their size. We hope that this study will be a step in the direction of the cost-efficient generation of stable carbon dioxide nanobubble dispersions.

Influence of Synthesis Conditions on the Properties of Zinc Oxide Obtained in the Presence of Nonionic Structure-Forming Compounds.

This work investigated the influence of synthesis conditions, including the use of nonionic structure-forming compounds (surfactants) with different molecular weights (400-12,600 g/mol) and various hydrophilic/hydrophobic characteristics, as well as the use of a glass substrate and hydrothermal exposure on the texture and structural properties of ZnO samples. By X-ray analysis, it was determined that the synthesis intermediate in all cases is the compound Zn5(OH)8(NO3)2∙2H2O. It was shown that thermolysis of this compound at 600 °C, regardless of the physicochemical properties of the surfactants, leads to the formation of ZnO with a wurtzite structure and spherical or oval particles. The particle size increased slightly as the molecular weight and viscosity of the surfactants grew, from 30 nm using Pluronic F-127 (MM = 12,600) to 80 nm using Pluronic L-31 (MM = 1100), PE-block-PEG (MM = 500) and PEG (MM = 400). Holding the pre-washed synthetic intermediates (Zn5(OH)8(NO3)2∙2H2O) under hydrothermal conditions resulted in the formation of hexagonal ZnO rod crystal structures of various sizes. It was shown that the largest ZnO particles (10-15 μm) were observed in a sample obtained during hydrothermal exposure using Pluronic P-123 (MM = 5800). Atomic adsorption spectroscopy performed comparative quantitative analysis of residual Zn2+ ions in the supernatant of ZnO samples with different particle sizes and shapes. It was shown that the residual amount of Zn2+ ions was higher in the case of examining ZnO samples which have spherical particles of 30-80 nm. For example, in the supernatant of a ZnO sample that had a particle size of 30 nm, the quantitative content of Zn2+ ions was 10.22 mg/L.

Identifying synergistic combinations of Doxorubicin-Loaded polyquercetin nanoparticles and natural Products: Implications for breast cancer therapy

Combining chemotherapeutic agents with bioactive natural products is an attractive cancer treatment modality to reduce the dose and side effects of chemotherapy. Combination treatments with drugs having different mechanisms of action can also be beneficial in combatting the development of drug resistance by cancer cells. Nanoparticle (NP)-mediated drug delivery can further improve the therapeutic index of cytotoxic agents by enabling passive and/or active targeting to tumor tissues in vivo. Using doxorubicin (DOX) as a model chemotherapeutic agent, we developed three NP formulations based on polyquercetin (pQCT), an emerging nanocarrier platform. The NPs were co-assembled with DOX, pQCT, and either Pluronic P123, methoxy poly(ethylene glycol)-amine, or D-α-tocopheryl poly(ethylene glycol) 1000 succinate (TPGS). Physicochemical characterization of the NPs revealed them to have a spherical morphology with high monodispersity, excellent drug loading capacity, and sustained drug release. Then, the NPs were evaluated in vitro to determine their potential synergism when combined with the bioactive natural products curcumin (CUR), tannic acid (TA), and thymoquinone (TQ) against breast cancer cells (MCF-7 and MDA-MB-231). Surprisingly, most of the combinations were found to be antagonistic. However, combinations containing CUR exhibited greater pro-apoptotic effects compared to the single agents, with polymer-modified pQCT NPs presenting as a promising nanoplatform for enhancing DOX’s ability to promote cancer cell apoptosis. Our findings provide insights into the potential application of pQCT in nanomedicine, as well as the use of bioactive natural products in combination with DOX as a free agent and as an NP formulation in the treatment of breast cancer.

Novel Microemulsions with Essential Oils for Environmentally Friendly Cleaning of Copper Cultural Heritage Artifacts.

Cleaning represents an important and challenging operation in the conservation of cultural heritage, and at present, a key issue consists in the development of more sustainable, "green" materials and methods to perform it. In the present work, a novel xylene-in-water microemulsion based on nonionic surfactants with low toxicity was obtained, designed as low-impact cleaning agent for metallic historic objects. Phase diagram of the mixtures containing polyoxyethylene-polyoxypropilene triblock copolymer Pluronic P84 and D-alpha-tocopheryl polyethylene glycol 1000 succinate (TPGS) as surfactants, water, ethanol and xylene was studied, and a microemulsion with low surfactant content was selected as suitable cleaning nanosystem. Essential oils (EOs) from thyme and cinnamon leaf were added to the selected microemulsion in order to include other beneficial properties such as anticorrosive and antifungal protection. The microemulsions with or without EOs were characterized by size, size distribution and zeta potential. The cleaning efficacy of the tested microemulsions was assessed based on their ability to remove two types of artificial dirt by using X-ray energy dispersion spectrometry (EDX), scanning electron microscopy (SEM), contact angle measurements and color analysis. Microemulsions exhibit high capacity to remove artificial dirt from model copper coupons in spite of very low content of the organic solvent. Both thyme and cinnamon oil loading microemulsions prove to significantly reduce the corrosion rate of treated metallic plates compared to those of bare copper. The antifungal activity of the novel type of microemulsion was evaluated against Aspergillus niger, reported as main treat in biocorrosion of historic copper artifacts. Application of microemulsion with small amounts of EOs on Cu plates inhibits the growth of fungi, providing a good fungicidal effect.

Cd/SBA-15 heterogeneous catalyst used for acetic acid conversion: pseudo-homogeneous kinetic model, response surface methodology, and historical data design

Abstract Mesoporous materials (MMs) in the Santa Barbara Amorphous (SBA) family can be used as catalysts or support materials (SMs) for catalysts because they have controllable pore structure, thermal and chemical stability, and their surface properties can be modified easily depending on the desired reaction type. Surfactant (Pluronic p123; it is a symmetric triblock copolymer comprising poly and its chemical formula; HO(CH2CH2O)20(CH2CH(CH3)O)70(CH2CH2O)20H), a silica source (such as Tetraethyl orthosilicate: TEOS; SiC8H20O4), and a solvent are used in the synthesis of the SBA family (SBA-15). The SBA-15 was given with the hydrothermal method (HM) a catalyst feature by loading the active substance at a rate of 10, 25 % (cadmium/silica) by mass. Esterification reactions (ERs) were carried out with Cd-SBA-15 (Cd/Si: 10–25 %) catalyst at a feed rate of 1/2 (methanol/acetic acid), in the presence of 0.4 g catalyst, at a reaction temperature of 373 K and for 6–48 h. After 48 h, the catalytic activity (CA) values were obtained as 65 and 68 %, respectively. The re-usability of the catalysts was repeated two times under the same experimental conditions. It was observed that the catalysts maintained their catalytic activity of 73.35 and 68.72 % (3 × 48 h). In addition, the limited effect of catalyst amount on acetic acid conversion was investigated by Response Surface Methodology, and Historical Data Design. Moreover, k 1, k2, equilibrium constant and activation energy values were calculated using the pseudo-homogeneous kinetic model. The physical features of the catalysts were investigated by BET, XRD, FTIR, DRIFT, SEM/EDX, and MAPPING analysis methods.

Binary Pluronics based mixed micellar systems: Effective solution for improved solubilization of Biochanin A

The present work was carried out to appraise the solubilization of Biochanin (BCA), a natural hydrophobic drug in pure Pluronics (P84, P123 and F127) as well as binary mixed micelles (P84-P123 and F127-P123) followed by an interactional study using various state of art techniques. The critical micelle concentration (CMC) of binary mixtures P84-P123 and F127-P123 was found to be significantly lower than pure Pluronics justifying the candidature of mixed micelles (MMs) as a better solubilizer for BCA. UV–visible studies revealed the enhanced solubility of BCA in P84-P123 (1:2) MMs (3.51 ± 0.087 mg/mL) and F127-P123 (1:2) MMs (2.94 ± 0.046 mg/mL) as compared to micelles of pure Pluronics (10% w/v), P84 (2.25 ± 0.039 mg/mL) and F127 (1.12 ± 0.036 mg/mL). Differential pulse voltammetry (DPV) results demonstrated significantly superior binding of BCA with P84-P123 (1:2) MM (Ka = 2.60 × 105 M−1) as compared to pure P84 (Ka = 1.415 × 105 M−1). Mixed micellization (P84-P123 (1:2)) leads to increase in micellar hydrodynamic diameter (Dh = 16.09 nm) as compared to pure Pluronic P84 micelles (Dh = 15.71 nm) which was further amplified (Dh = 17.69 nm) after BCA loading. Different formulations of pure and MMs were subjected to in vitro drug release and MMs were found to slow down BCA release as compared to pure Pluronics (P84, P123). The results obtained in this study proved that P84-P123 (1:2) MMs are superior and more effective for the solubilization of BCA than pure and other MMs. Thus, the examined MMs hold the potential for advancing the development of solubilization techniques for other hydrophobic drugs with significant pharmacological value.

One-Pot Mechanochemical Synthesis of Carbons with High Microporosity and Ordered Mesopores for CO2 Uptake at Ambient Conditions.

Mechanochemical synthesis of ordered mesoporous carbons with tunable mesopores and well-developed irregular microporosity is investigated. This synthesis was carried out by the self-assembly of ecofriendly chemicals such as tannin and glyoxal used as carbon precursors, and triblock copolymer as a soft templating agent. The structural properties of the resulting carbons were tailored by using different block copolymers (Pluronic F127, and P123) as soft templates. The various weight ratios of tannin and block copolymer were employed to tune the textural properties of these carbons. The tannin: Pluronic F127 ratios (1:0.75, 1:1, 1:1.1) gave the ordered mesoporous carbons among a wide variety of the samples studied. The ordered mesoporosity was not observed in the case of Pluronic P123 templated mesoporous carbons. The CO2-activated carbon samples obtained for both Pluronic templates showed a high specific surface area (close to 900 m2/g), large pore volume (about 0.6-0.7 cm3g-1), narrow pore size distribution, and high CO2 uptake of about 3.0 mmol g-1 at 1 bar pressure and ambient temperature.