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Search Results (1,763)

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Keywords = amphiphilicity

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20 pages, 1188 KiB  
Review
Antioxidant Properties of Biosurfactants: Multifunctional Biomolecules with Added Value in Formulation Chemistry
by Matilde Tancredi, Carlo Carandente Coscia, Irene Russo Krauss and Gerardino D’Errico
Biomolecules 2025, 15(2), 308; https://doi.org/10.3390/biom15020308 - 19 Feb 2025
Abstract
Biosurfactants, amphiphilic metabolites produced by bacteria and yeasts, fulfill a variety of functions in microbial life. They exhibit a well-recognized multifunctionality, spanning from the reduction in surface tension to specific biological activities, including antimicrobial, antiviral, anti-inflammatory, and anticancer effects. These compounds have the [...] Read more.
Biosurfactants, amphiphilic metabolites produced by bacteria and yeasts, fulfill a variety of functions in microbial life. They exhibit a well-recognized multifunctionality, spanning from the reduction in surface tension to specific biological activities, including antimicrobial, antiviral, anti-inflammatory, and anticancer effects. These compounds have the potential to serve as environmentally friendly alternatives to synthetic surfactants in industrial formulations, where they could act as emulsifiers and wetting agents. The exploitation of their full potentiality could be a significant added value. Biosurfactants are often cited as effective antioxidants. However, experimental evidence for their antioxidant activity/capacity is sparse. To shed light on the subject, in this review we collect and critically examine all the available literature data for each of the major classes of microbial biosurfactants: rhamnolipids, mannosylerythritol lipids, sophorolipids, and lipopeptides. Despite the variability arising from the diverse composition and polydispersity of the samples analyzed, along with the variety of testing methodologies, the findings consistently indicate a moderate-to-strong antioxidant capacity. Several hypotheses are advanced about the molecular mechanisms behind this action; however, further studies are needed to gain a molecular understanding. This knowledge would fully define the biological roles of biosurfactants and is a prerequisite for the development of innovative formulations based on the valorization of their antioxidant properties. Full article
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Figure 1
<p>Examples of molecular structures of rhamnolipids tested for antioxidant capacity.</p>
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<p>Example of molecular structure of mannosylerythritol lipids tested for antioxidant capacity.</p>
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<p>Examples of molecular structures of sophorolipids tested for antioxidant capacity.</p>
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<p>Examples of molecular structures of lipopeptides tested for antioxidant capacity.</p>
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<p>Diagram of scientific progress necessary for the consolidation of the antioxidant properties of biosurfactants.</p>
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33 pages, 7087 KiB  
Article
Demulsification of Water-in-Oil Emulsion with Carbon Quantum Dot (CQD)-Enhanced Demulsifier
by Jhon F. Gallego, Oscar E. Medina, Jose A. Tengono, Camilo Mazo, Andres F. Maya, Cristina Caro, Farid B. Cortés and Camilo A. Franco
Processes 2025, 13(2), 575; https://doi.org/10.3390/pr13020575 - 18 Feb 2025
Viewed by 228
Abstract
This study aims to optimize the demulsification performance of a carbon quantum dot (CQD)-enhanced chemical demulsifier in industrial emulsions under thermal, mechanical, and thermomechanical effects. Experiments were conducted to assess treatments like organic treatment (OT), zeta potential modifier aqueous solution (ZPMAS), and acid [...] Read more.
This study aims to optimize the demulsification performance of a carbon quantum dot (CQD)-enhanced chemical demulsifier in industrial emulsions under thermal, mechanical, and thermomechanical effects. Experiments were conducted to assess treatments like organic treatment (OT), zeta potential modifier aqueous solution (ZPMAS), and acid treatment (9.25 wt.% HCl) at varying dosages, along with CQD–chemical mixtures optimized through a simplex-centroid mixture design (SCMD) to minimize basic sediment and water (BSW). Under the thermomechanical scenario, a system with 500 mg∙L−1 CQDs and OT achieves 0.5% BSW and a droplet size of 63 nm, while an SCMD-optimized system (500 mg∙L−1 CQDs + 380 mg∙L−1 OT + 120 mg∙L−1 ZPMAS) achieves 0% BSW and larger droplets (>70 nm). CQDs enhance demulsifiers by destabilizing water-in-oil (W/O) Pickering emulsions, leveraging their nanometric size, high surface area, thermal conductivity, and amphiphilicity, thanks to their hydrophobic core and surface hydrophilic groups (-OH, NH2, -COOH). This research enhances the understanding of demulsification by employing green demulsifiers based on CQDs and provides a promising cost-efficient solution for breaking stable emulsions in the petroleum industry. It minimizes the use of complex and expensive active ingredients, achieving BSW values below 0.5%, the standard required for crude oil transport and sale, while also reducing separation equipment operation times, and improving overall process efficiency. Full article
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Graphical abstract
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<p>Scheme of emulsion phase separation. Four emulsion phases were identified: Phase 1, crude oil; Phase 2, crude oil/water interphase; Phase 3, deposited solids; and Phase 4, water. The deposited solids (Phase 3) were treated with successive solvent washings with toluene, heptane, and CS<sub>2</sub>.</p>
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<p>Scheme of the experimental procedure for evaluating chemical demulsifiers under: (<b>a</b>) mechanical, (<b>b</b>) thermal, and (<b>c</b>) thermomechanical separation scenarios. Four phases were distinguished in the experiments of the mechanical and thermomechanical separation scenarios.</p>
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<p>Experimental points of the simplex-centroid mixture design (SCMD) with the proportions of each component (ZPMAS, CQDs, and OT) in mass fraction under the thermomechanical separation scenario.</p>
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<p>Thermogravimetric analysis of (<b>a</b>) Phase 1: crude oil; (<b>b</b>) Phase 2: water/crude oil interphase; (<b>c</b>) unwashed deposit solids (Phase 3); and (<b>d</b>) deposit solids (Phase 3) washed successively with toluene, heptane, and CS<sub>2</sub>.</p>
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<p>Dissolution results in water, HCl (1 M), heptane, and toluene for Phase 2: the water/crude oil interphase and Phase 3: the unwashed and washed deposit solids.</p>
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<p>(<b>a</b>) FTIR spectrum and (<b>b</b>) XRD spectrum of solids after being washed with toluene, heptane, and CS<sub>2</sub>.</p>
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<p>(<b>a</b>) Average droplet radius (D<sub>50</sub>) and (<b>b</b>) BSW% of the oil phase depending on the treatment concentration for the conventional treatments OT, ZPMAS, and AT under the mechanical separation scenario. Base emulsion with no demulsifier treatment addition is also shown at a concentration of 0 mg∙L<sup>−1</sup>.</p>
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<p>Percentage of water and water/crude oil interphase in the oil phase at different treatment concentrations (OT, ZPMAS, and AT) of (<b>a</b>) 500, (<b>b</b>) 1000, and (<b>c</b>) 2000 mg∙L<sup>−1</sup> under the mechanical separation scenario. Each system is compared with the base emulsion with no demulsifier treatment addition.</p>
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<p>Percentage of water and water/crude oil interphase in the oil phase at different treatment concentrations (OT, ZPMAS, and AT) of (<b>a</b>) 500, (<b>b</b>) 1000, and (<b>c</b>) 2000 mg∙L<sup>−1</sup> under the mechanical separation scenario. Each system is compared with the base emulsion with no demulsifier treatment addition.</p>
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<p>(<b>a</b>) Average droplet radius (D<sub>50</sub>) and (<b>b</b>) BSW% of the oil phase as a function of the treatment concentration for the conventional treatments OT, ZPMAS, AT, and blue CQDs under the thermal separation scenario. Base emulsion with no demulsifier treatment addition is also shown at a concentration of 0 mg∙L<sup>−1</sup>.</p>
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<p>Schematic representation of the three main demulsification mechanisms of the CQDs: (<b>i</b>) location of the W/O interface and coalescence of water droplets, (<b>ii</b>) destabilization of fine solids, and (<b>iii</b>) increasing the heat transfer efficiency.</p>
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<p>Percentage of water, solids, and water/crude oil interphase in the oil phase at treatment concentrations (OT, ZPMAS, AT, and CQDs blue) of (<b>a</b>) 500, (<b>b</b>) 1000, and (<b>c</b>) 2000 mg∙L<sup>−1</sup> under the thermal separation scenario. Each system is compared with the base emulsion, which has no demulsifier treatment addition.</p>
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<p>Percentage of water, solids, and water/crude oil interphase in the oil phase at treatment concentrations (OT, ZPMAS, AT, and CQDs blue) of (<b>a</b>) 500, (<b>b</b>) 1000, and (<b>c</b>) 2000 mg∙L<sup>−1</sup> under the thermal separation scenario. Each system is compared with the base emulsion, which has no demulsifier treatment addition.</p>
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<p>(<b>a</b>) Average droplet radius (D<sub>50</sub>), (<b>b</b>) BSW%, and (<b>c</b>) percentage of solids, water, and water/crude oil interphase in the oil phase for the systems with treatments (AT, ZPMAS, OT, and blue CQDs) at 1000 mg∙L<sup>−1</sup> under the thermomechanical separation scenario. Each system is compared with the base emulsion, which has no demulsifier treatment addition.</p>
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<p>(<b>a</b>) Average droplet radius (D<sub>50</sub>), (<b>b</b>) BSW%, and (<b>c</b>) percentage of solids, water, and water/crude oil interphase in the oil phase for the systems with a mixture of treatments (ZPMAS, OT, and CQDs blue) at a total concentration of 1000 mg∙L<sup>−1</sup> under the thermomechanical separation scenario.</p>
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<p>Response surface for the BSW% response variable in systems with a mixture of treatments (ZPMAS, OT, and blue CQDs) under the thermomechanical separation scenario.</p>
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<p>Experimental roadmap used in this study for emulsion characterization and evaluation of demulsifier treatment efficacy.</p>
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26 pages, 5383 KiB  
Article
Characterization and Emulsifying Ability of Cassava Peels Solubilized Using Hydrothermal Treatments
by Jane Chizie Ogbonna, Mitsutoshi Nakajima and Marcos Antonio das Neves
Polymers 2025, 17(4), 496; https://doi.org/10.3390/polym17040496 - 13 Feb 2025
Viewed by 455
Abstract
Cassava peels are rich in polysaccharides but highly unexplored and underutilized, as they could be used to meet the increasing demand for clean-label foods. This study investigated the effect of temperature on the solubilization of cassava peel during hydrothermal treatment to determine the [...] Read more.
Cassava peels are rich in polysaccharides but highly unexplored and underutilized, as they could be used to meet the increasing demand for clean-label foods. This study investigated the effect of temperature on the solubilization of cassava peel during hydrothermal treatment to determine the emulsifying ability of solubilized cassava peel (SCP). Subcritical water conditions were employed via hydrothermal (120–200 °C; 2 MPa) or autoclave (127 °C; 0.2 MPa) treatments to solubilize cassava peels. The composition of the SCPs was determined, and their emulsifying ability was assessed using interfacial tension and zeta potential measurements. Under the best treatment conditions (140 °C at 2 MPa [hydrothermal]; 127 °C at 0.2 MPa [autoclave]), SCPs reduced interfacial tension against soybean oil to 12.9 mN/m and 13.4 mN/m, respectively. A strengthened co-emulsifier system was developed by incorporating SCPs with Quillaja saponins (QS) or Tween 20 to enhance the performance. Dynamic interfacial tension and zeta potential measurements revealed synergistic interactions, showing a remarkable reduction in interfacial tension from 12.94 to 5.33 mN/m. This suggests that the SCP has a surfactant-like structure owing to its amphiphilic structure and hydrophobic chains (nonpolar region) attached to the -OH functional group (polar region). Combining a second surface-active compound or co-emulsifier results in an additive effect, reducing the interfacial tension. These findings provide novel insights into carbohydrate-saponin binding and elucidate the impact of peel composition, concentration, and hydrothermal treatment conditions on co-emulsifier system performance, which will assist in the development of emulsifiers, contributing to the advancement of clean-label food technologies, effectively replacing synthetic emulsifiers in food formulations, and offering both sustainability and functionality. A systematic investigation of processing conditions and co-emulsifier interactions provides a practical framework for developing high-performance natural emulsifiers from agricultural waste. Full article
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<p>Schematic diagram of the equipment used for hydrothermal treatment: (<b>a</b>) Hydrothermal treatment (HTS) reactor and (<b>b</b>) autoclave.</p>
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<p>Temperature, pressure, and time profile of the hydrothermal solubilization reactor at 140 °C and 2 MPa with a holding time of 15 min.</p>
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<p>Effect of thermal treatment temperature on the solubilization yield and pH of solubilized cassava peels (SCPs) obtained using an HTS reactor.</p>
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<p>Effect of hydrothermal treatment temperature on the composition (carbohydrates, protein, and ash content) of SCPs obtained using an HTS reactor.</p>
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<p>Effect of hydrothermal treatment temperature on cyanide content of SCPs obtained using an HTS reactor.</p>
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<p>Scanning electron microscope (SEM) images of (<b>a</b>) untreated cassava peel powder; (<b>b</b>) cassava peels solubilized at 140 °C and 2 MPa (HTS reactor) and freeze-dried; and (<b>c</b>) cassava peels solubilized at 127 °C and 0.2 MPa (autoclave) and freeze-dried.</p>
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<p>Droplet size distribution of oil-in-water (O/W) emulsions stabilized by SCPs and stored for 10 d at (<b>a</b>) 5 °C and (<b>b</b>) 25 °C.</p>
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<p>Mean droplet diameter (<span class="html-italic">d</span><sub>3,2</sub>) of O/W emulsions stabilized by SCPs and stored for 10 d at (<b>a</b>) 5 °C and (<b>b</b>) 25 °C.</p>
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<p>Effect of the weight ratio between SCPs and co-emulsifiers (<span class="html-italic">Quillaja</span> saponin or Tween 20) on interfacial tension: (<b>a</b>) 140 °C at 2 MPa (HTS reactor) and (<b>b</b>) 127 °C at 0.2 MPa (autoclave) (weight ratios of 10:0, 7.5:2.5, 5:5, 2.5:7.5, and 0:10 (SCP: co-emulsifier)).</p>
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<p>Effect of weight ratio of solubilized cassava peels (SCP) to co-emulsifiers (<span class="html-italic">Quillaja</span> saponin or Tween 20) on zeta potential: (<b>a</b>) 140 °C at 2 MPa (HTS reactor) and (<b>b</b>) 127 °C at 0.2 MPa (autoclave) (the weight ratios were 10:0, 7.5:2.5, 5:5, 2.5:7.5, and 0:10 (SCP: co-emulsifier)).</p>
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<p>Droplet size distribution of O/W emulsions stabilized by SCPs or <span class="html-italic">Quillaja</span> saponins at various weight ratios, and stored for 10 d: (<b>a</b>) Fresh emulsion (day 0); (<b>b</b>) stored at 5 °C for 10 days; and (<b>c</b>) stored at 25 °C for 10 days (the weight ratios were 10:0, 7.5:2.5, 5:5, 2.5:7.5, and 0:10 (SCP: co-emulsifier)).</p>
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<p>Droplet size distribution of O/W emulsions stabilized by SCPs or <span class="html-italic">Quillaja</span> saponins at various weight ratios, and stored for 10 d: (<b>a</b>) Fresh emulsion (day 0); (<b>b</b>) stored at 5 °C for 10 days; and (<b>c</b>) stored at 25 °C for 10 days (the weight ratios were 10:0, 7.5:2.5, 5:5, 2.5:7.5, and 0:10 (SCP: co-emulsifier)).</p>
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<p>Mean droplet diameter (<span class="html-italic">d</span><sub>3,2</sub>) of O/W emulsions stabilized by SCPs or <span class="html-italic">Quillaja</span> saponin at various weight ratios and stored for 10 days either at (<b>a</b>) 5 °C or (<b>b</b>) 25 °C (the weight ratios were 10:0, 7.5:2.5, 5:5, 2.5:7.5, and 0:10 (SCP: co-emulsifier)).</p>
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<p>Emulsions stabilized by solubilized cassava peels loaded with varied ratios of <span class="html-italic">Quillaja</span> saponin as a co-emulsifier.</p>
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<p>Schematic illustration of the potential synergistic interaction between SCPs and <span class="html-italic">Quillaja</span> saponins.</p>
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<p>Schematic illustration of the carbohydrates–saponin binding mechanism that leads to a reduction in interfacial tension.</p>
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27 pages, 5690 KiB  
Review
Superabsorbent Polymers: Innovations in Ecology, Environmental, and Diverse Applications
by Qingya Niu, Jiayin Xie, Jiayan Li, Zaixu An, Huijie Xiao, Xiaoyuan Zhang, Zhiqiang Su and Zhichao Wang
Materials 2025, 18(4), 823; https://doi.org/10.3390/ma18040823 - 13 Feb 2025
Viewed by 274
Abstract
Significant progress has been achieved in the development of superabsorbent polymers (SAPs), focusing on enhancing their performance and expanding their applications. Efforts are particularly directed at increasing water absorbency while promoting environmental sustainability. Biodegradable materials such as starch and potassium humate have been [...] Read more.
Significant progress has been achieved in the development of superabsorbent polymers (SAPs), focusing on enhancing their performance and expanding their applications. Efforts are particularly directed at increasing water absorbency while promoting environmental sustainability. Biodegradable materials such as starch and potassium humate have been successfully integrated with SAPs for desert greening, improving water retention, salt resistance, and seedling survival. The inclusion of nutrient-rich organic-inorganic composites further enhances the durability, efficiency, and recyclability of SAPs. In drought mitigation, polymeric absorbent resins such as polyacrylamide and starch-grafted acrylates have shown efficacy in ameliorating soil conditions and fostering plant growth. In arid environments, agents enriched with humic acid and bentonite contribute to improved soil aeration and water retention, creating optimal conditions for plant establishment. Additionally, the adoption of innovative waste management solutions has led to the production of amphiphilic SAPs from residual sludge, effectively addressing soil nutrient deficiencies and environmental pollution. In the food industry, SAPs containing protease, tea polyphenols, and chitosan exhibit potential for enhancing the stability and quality of seafood products. These advancements highlight the growing relevance of structural optimization approaches in SAP development across diverse applications and underline the importance of continued innovation in these fields. As novel materials emerge and environmental challenges intensify, the potential applications of SAPs are anticipated to expand significantly. Full article
(This article belongs to the Special Issue Construction and Applications in Functional Polymers)
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Figure 1
<p>Effect of the water-to-cement ratio on chloride diffusion in SAP-modified concrete hydrogels: (<b>a</b>) Particle size distribution of SAP S measured by laser diffraction. (<b>b</b>) Unsaturated SAPS particles under drying conditions. (<b>c</b>) Variation of water absorption capacity over time under different water-to-cement ratios and chloride ion diffusion coefficients of concrete series. Reproduced with permission from ref. [<a href="#B31-materials-18-00823" class="html-bibr">31</a>] © MDPI AG, CC BY.</p>
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<p>Synthesis and performance study of cellulose-based SAPs: (<b>a</b>) Production and applications of cellulose-based SAPs. (<b>b</b>) Conversion of cellulose-based superabsorbent polymers into hydrogels through physical methods. (<b>A</b>) After reaching absorption capacity (AC) equilibrium in deionized water, completely dry 0.5 g cellulose-SAP samples and (<b>B</b>) hydrogel. (<b>c</b>) Changes in Swelling Behavior and Absorption Capacity (AC) of Cellulose Superabsorbent Polymers in Deionized Water over Time (t). (<b>d</b>) Effect of absorption-desorption on weight and absorptive capacity (AC): (<b>A</b>) method scheme, (<b>B</b>) weight of the entire expansion-drying cycle, and (<b>C</b>) AC of the entire expansion-drying cycle. (<b>e</b>) Absorbed liquid weight (Wt) by immersion in 1.0 mol/L MgSO<sub>4</sub>, NaCl, and CaCl solutions of cellulose superabsorbent polymers and time (t). Thermogravimetric analysis of cellulose-based SAPs. Reproduced with permission from ref. [<a href="#B48-materials-18-00823" class="html-bibr">48</a>] © 2022 Canadian Society for Chemical Engineering.</p>
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<p>Performance characterization of SAP based on methacrylated alginate and acrylic acid monomers: (<b>a</b>). Characterization of SAP by attenuated total reflectance infrared (ATR-IR) spectroscopy. (<b>b</b>). High-resolution magic angle spinning (MAS) spectroscopy of SAP.The red circle indicates that after polymerization, the peak shifts to a lower ppm range (1.5–2.5 ppm). (<b>c</b>). Hygroscopicity was determined through dynamic vapor sorption measurements. (<b>a</b>) Moisture Absorption of p(alg(1)_AA100(7))_H and p(alg(1)_AA100(7))_L by Dynamic Vapor Adsorption Measurement (<b>b</b>) Moisture absorption of p(alg(1)_AA75/AM25(7)))_H and p(alg(1)_AA75/AM25(7))_L by dynamic vapor adsorption measurement (<b>d</b>). Comparison of swelling abilities of SAP in aqueous solutions at different pH values (acidic and alkaline) and cement filtrate solutions. (<b>a</b>) Comparison of the swelling capacity of p(alg(1)_AA100(7))_H and p(alg(1)_AA100(7))_L in aqueous solutions at different pH values and (acidified and alkaline) cement filtrate solutions (illustration). (<b>b</b>) Comparison of the swelling capacity of p(alg(1)_AA75/AM25(7))_H and p(alg(1)_AA75/AM25(7))_L in aqueous solutions and (acidified/alkaline) cement filtrate solutions (illustration). Reproduced with permission from ref. [<a href="#B81-materials-18-00823" class="html-bibr">81</a>] © 2017 Elsevier Ltd.</p>
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<p>Study on the synthesis and performance of cellulose-based SAPs: (<b>A</b>) Conversion of cellulose-based superabsorbent polymers into hydrogels via physical methods. (<b>B</b>) Swelling behavior and absorption capacity of cellulose-based SAPs in deionized water over time (t). (<b>C</b>) (<b>A</b>) Thermogravimetric analysis of cellulose-based SAPs. (<b>B</b>) Evaluation of the effect of repeated swelling cycles (<b>A</b>) of the dried sample in deionized water on the weight (<b>B</b>) and absorption capacity (<b>C</b>) of the cellulose-based superabsorbent polymer. Reproduced with permission from ref. [<a href="#B48-materials-18-00823" class="html-bibr">48</a>] © 2022 Canadian Society for Chemical Engineering.</p>
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<p>(<b>A</b>). Schematic summary of the experimental methods. (<b>A</b>) Peptide solutions were prepared in DMF. (<b>B</b>) deposited in air-water cross-linked enzymes and compressed using the LB setup. (<b>I</b>, <b>II</b>, <b>III</b>). The Langmuir trough barriers then exerted lateral, unidirectional compression at a constant speed until reaching surface pressures of 10, 20 or 30 mN·m<sup>−1</sup>. (<b>C</b>) transferred to the MICA matrix. (<b>D</b>) selectively impregnated with metal salts and removed with UV/O<sup>3</sup> peptides. (<b>B</b>). Study on FP2 peptide: (<b>a</b>) AFM micrograph of pristine FP2 peptide placed on a mica substrate at 20 MN·m<sup>−1</sup> surface pressure, (<b>b</b>) after immersion in Haucl4 solution for 30 min, and (<b>c</b>) after subsequent UV/O<sup>3</sup> degradation treatment. (<b>d</b>) The interaction between the peptide fiber and the AU precursor salt in aqueous solution is schematically shown. (<b>e</b>) High-resolution XPS (black dots) of the original FP2 peptide of N 1s and (<b>f</b>) AU 4F and after inorganic incorporation and UV/O<sup>3</sup> degradation (green dots). Reproduced with permission from ref. [<a href="#B96-materials-18-00823" class="html-bibr">96</a>] © 2024 Wiley-VCH GmbH.</p>
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<p>Preparation strategy and structural characterization of SAP synthesized based on Kaolin: (<b>a</b>) The synthesis process of kaolin-reinforced SAP. (<b>b</b>) The microstructure of SAP agglomerates before being crushed. (<b>c</b>–<b>g</b>) SAP with certain mechanical strength retains its spherical shape even after withstanding mechanical crushing pressure. (<b>h</b>,<b>i</b>) Water absorption rate of the synthesized SAP at different water temperatures. Reproduced with permission from ref. (<b>j</b>–<b>l</b>) The absorption of SAP with synthetic kaolin contents of 3.8%, 7.5% and 7.5% at different water temperatures. [<a href="#B101-materials-18-00823" class="html-bibr">101</a>] © 2022 Elsevier Ltd.</p>
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<p>Crosslinking mechanism and high-performance characterization of superabsorbent polymers synthesized using modern nanotechnology: (<b>A</b>) General crosslinking mechanism between nanoparticles and polymer chains [<a href="#B38-materials-18-00823" class="html-bibr">38</a>]. (<b>B</b>) Swelling kinetics of the synthesized hydrogel in distilled water and saline solution. (<b>C</b>) Swelling height and root length changed with content of SA in soil. (<b>D</b>) Schematical drawing of water and nutrient uptake. (<b>E</b>) Storage modulus (G′) (<b>A</b>) and loss modulus (G″) (<b>B</b>) of the synthesized hydrogel. Reproduced with permission from ref. [<a href="#B110-materials-18-00823" class="html-bibr">110</a>] ©2017 Sociedade Brasileira de Química.</p>
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<p>Preparation strategy and performance of PVPP-based superabsorbent polymer gels: (<b>A</b>) Flowchart of SAP preparation process. (<b>B</b>) (<b>a</b>) SEM image of PVPP surface; (<b>b</b>) SEM image of SAP surface before water absorption; (<b>c</b>) Local enlarged SEM image of SAP surface before water absorption; (<b>d</b>) SEM image of SAP surface after water absorption. (<b>C</b>) (<b>a</b>) Re-swelling ability of SAP; (<b>b</b>) water retention at different temperatures; and (<b>c</b>) swelling kinetics of SAP in distilled water. Reproduced with permission from ref. [<a href="#B4-materials-18-00823" class="html-bibr">4</a>] © 2021 Elsevier Ltd.</p>
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<p>Comparison of performance between P-SAP and A-SAP: (<b>A</b>) Mechanism of action. (<b>B</b>) Comparison of the stability of the two materials in terms of (<b>a</b>) NaCl concentration, (<b>b</b>) pH, and (<b>c</b>) temperature. (<b>C</b>) Comparison of the fertilizer protection ability exhibited by the two materials: (<b>a</b>) Nitrogen fertilizer (<b>b</b>) Phosphorus fertilizer. (<b>D</b>) Comparison of (<b>a</b>) the water absorption performance, (<b>b</b>) reusability, and (<b>c</b>) mass density rate of the two materials during application. Reproduced with permission from ref. [<a href="#B118-materials-18-00823" class="html-bibr">118</a>] © 2021 Elsevier B.V.</p>
Full article ">Scheme 1
<p>Classification, preparation, and applications of SAPs.</p>
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15 pages, 9424 KiB  
Article
Liquid Crystalline Structures Formed by Sphere–Rod Amphiphilic Molecules in Solvents
by Nilanthi P. Haputhanthrige, Yifan Zhou, Jingfan Wei, Min Gao, Tianbo Liu and Oleg D. Lavrentovich
Crystals 2025, 15(2), 177; https://doi.org/10.3390/cryst15020177 - 13 Feb 2025
Viewed by 236
Abstract
Self-assembly of amphiphilic molecules is an important phenomenon attracting a broad range of research. In this work, we study the self-assembly of KTOF4 sphere–rod amphiphilic molecules in mixed water–dioxane solvents. The molecules are of a T-shaped geometry, comprised of a hydrophilic spherical [...] Read more.
Self-assembly of amphiphilic molecules is an important phenomenon attracting a broad range of research. In this work, we study the self-assembly of KTOF4 sphere–rod amphiphilic molecules in mixed water–dioxane solvents. The molecules are of a T-shaped geometry, comprised of a hydrophilic spherical Keggin-type cluster attached by a flexible bridge to the center of a hydrophobic rod-like oligodialkylfluorene (OF), which consists of four OF units. Transmission electron microscopy (TEM) uncovers self-assembled spherical structures of KTOF4 in dilute solutions. These spheres are filled with smectic-like layers of KTOF4 separated by layers of the solution. There are two types of layer packings: (i) concentric spheres and (ii) flat layers. The concentric spheres form when the dioxane volume fraction in the solution is 35–50 vol%. The flat layers are formed when the dioxane volume fraction is either below (20 and 30 vol%.) or above (55 and 60 vol%.) the indicated range. The layered structures show no in-plane orientational order and thus resemble thermotropic smectic A liquid crystals and their lyotropic analogs. The layered packings reveal edge and screw dislocations. Evaporation of the solvent produces a bulk birefringent liquid crystal phase with textures resembling the ones of uniaxial nematic liquid crystals. These findings demonstrate that sphere–rod molecules produce a variety of self-assembled structures that are controlled by the solvent properties. Full article
(This article belongs to the Special Issue Liquid Crystal Research and Novel Applications in the 21st Century)
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<p>Chemical structures of materials. (<b>a</b>) 3D, (<b>b</b>) 2D representation of sphere−rod shaped KTOF<sub>4</sub> with the hydrophilic Keggin cluster attached to the center of OFs, and (<b>c</b>) dioxane. The width and the length of the rod-shaped OF are approximately 1.3 and 3.4 nm, respectively, and the diameter of the Keggin sphere is 1.0 nm. The Keggin cluster is indicated in blue, and the OF units are shown in red in (<b>a</b>).</p>
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<p>TEM textures of 0.2 mg/mL KTOF<sub>4</sub> in a dioxane and water mixture. The solution with (<b>a</b>,<b>b</b>) 20, (<b>c</b>) 30, (<b>d</b>) 35, (<b>e</b>) 40, (<b>f</b>) 45, (<b>g</b>) 50, (<b>h</b>) 55, and (<b>i</b>) 60 vol% dioxane. The scale bar is 10 nm. X vol% dioxane is a solution with a dioxane: water ratio of X:(100−X).</p>
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<p>Self-assembled inclusions with thick, bright peripheral layer. TEM textures of 0.2 mg/mL KTOF<sub>4</sub> in (<b>a</b>) 30 vol%, and (<b>c</b>) 35 vol% dioxane. (<b>b</b>,<b>d</b>) Transmitted electron intensity profile along the line drawn in (<b>a</b>,<b>c</b>), respectively. X vol% dioxane is a solution with a dioxane: water ratio of X:(100−X).</p>
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<p>(<b>a</b>) Zoomed-in TEM texture of 0.2 mg/mL KTOF<sub>4</sub> in 30 vol% dioxane. White arrows marking the dark stripes correspond to Kegging clusters, while yellow arrows marking the narrow dark stripes correspond to the OFs. (<b>b</b>,<b>d</b>,<b>e</b>) The transmitted electron intensity profile along the lines AB, CD, and EF, respectively, (<b>c</b>) fast Fourier transform pattern obtained from the texture in (<b>a</b>), (<b>f</b>) a zoomed-in section (marked in dashed yellow in (<b>a</b>)) of a structure. The scale bar is 5 nm, and (<b>g</b>) proposed molecular packing within the layers.</p>
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<p>Dislocations in self-assembled KTOF<sub>4</sub> structures. TEM textures showing (<b>a</b>) edge dislocations, and (<b>b</b>) screw dislocations within the self-assembled layers of 0.2 mg/mL KTOF<sub>4</sub>. The dioxane content is indicated in the top-right corner of the respective texture. The scale bar is 20 nm for all textures in (<b>a</b>,<b>b</b>). X vol% dioxane refers to a solution with a dioxane: water ratio of X:(100−X). Proposed molecular packing within the layers at the defect site of (<b>c</b>) an edge dislocation, and (<b>d</b>) a screw dislocation.</p>
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<p>Polarizing optical microscopy (POM) study of LC<sub>KTOF4</sub>. LC<sub>KTOF4</sub> is obtained by allowing 2.0 mg/mL KTOF<sub>4</sub> with 50 vol% dioxane to slowly evaporate. POM image of a drop of LC<sub>KTOF4</sub> (<b>a</b>) on a glass plate, and (<b>b</b>) on the PI2555 coated, rubbed glass plate. The sample is rotated to have different alignments of the rubbing direction, R, with respect to P and A. (<b>c</b>) LC<sub>KTOF4</sub> progression of phase transition from Isotropic to Nematic while cooling. P and A indicate the polarizer and the analyzer directions and stay the same for all the images. The scale bar is <math display="inline"><semantics> <mrow> <mn>100</mn> <mo> </mo> <mrow> <mi mathvariant="sans-serif">μ</mi> <mi mathvariant="normal">m</mi> </mrow> </mrow> </semantics></math>.</p>
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<p>Proposed KTOF<sub>4</sub> molecular packing within the flat layers with (<b>a</b>) Keggin, and (<b>b</b>) OF as surface layer composition.</p>
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28 pages, 3061 KiB  
Review
Soluplus®-Based Pharmaceutical Formulations: Recent Advances in Drug Delivery and Biomedical Applications
by Nerea Guembe-Michel, Paul Nguewa and Gustavo González-Gaitano
Int. J. Mol. Sci. 2025, 26(4), 1499; https://doi.org/10.3390/ijms26041499 - 11 Feb 2025
Viewed by 469
Abstract
Poor water solubility remains a significant challenge in the pharmaceutical industry that limits the therapeutic efficacy and bioavailability of many active pharmaceuticals. Soluplus® (SLP), an amphiphilic graft copolymer made of polyethylene glycol, polyvinyl caprolactam, and polyvinyl acetate, has been gaining interest in [...] Read more.
Poor water solubility remains a significant challenge in the pharmaceutical industry that limits the therapeutic efficacy and bioavailability of many active pharmaceuticals. Soluplus® (SLP), an amphiphilic graft copolymer made of polyethylene glycol, polyvinyl caprolactam, and polyvinyl acetate, has been gaining interest in recent years as it addresses these limitations by acting as a versatile carrier. Its ability to form stable amorphous dispersions and enhance drug solubility, as well as its physicochemical properties, support its role as a key excipient in advanced drug delivery systems. Recent investigations have demonstrated the adaptability of SLP in addressing drug delivery requirements, offering controlled release, improved targeting, and superior therapeutic outcomes. This review examines some key formulation methods that make use of SLP, including hot-melt extrusion, spray drying, electrospinning, drug–polymer layering, and capsule and tablet formulations, highlighting the capacity of SLP to overcome formulation challenges. Biomedical applications of SLP have also been explored, with a focus on its role in improving the delivery of antitumoral, anti-inflammatory, antimicrobial, and antiparasitic drugs. Full article
(This article belongs to the Section Macromolecules)
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<p>Molecular structure of SLP, showing the block structure. Red: polyethylene glycol (PEG, 13%); green: polyvinyl caprolactam (PVCL, 57%); blue: polyvinyl acetate (PVAc, 30%).</p>
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<p>Representation of the micellization mechanism for SLP in aqueous solutions. From Alopaeus et al., with permission [<a href="#B19-ijms-26-01499" class="html-bibr">19</a>].</p>
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<p>Scheme of the hot-melt extrusion process. From Althobaiti et al., with permission [<a href="#B40-ijms-26-01499" class="html-bibr">40</a>].</p>
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<p>Schematic representation of a solution electrospinning setup. From Bonakdar et al., with permission [<a href="#B57-ijms-26-01499" class="html-bibr">57</a>].</p>
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<p>Scanning electron microscope images (<b>A</b>) native efavirenz, (<b>B</b>) SLP as received, (<b>C</b>) physical mixture of efavirenz and SLP, (<b>D</b>) efavirenz-loaded SLP nanofibers, and (<b>E</b>) SLP nanofibers. From Ahmed et al., with permission [<a href="#B63-ijms-26-01499" class="html-bibr">63</a>].</p>
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<p>Solidified self-emulsifying drug delivery system (SEDDS) formulation of aprepitant with Soluplus<sup>®</sup>, Capryol<sup>TM</sup>, Kolliphor<sup>®</sup> CS20 and Transcutol<sup>®</sup> P in hard gelatin capsules for oral administration. From Nazli et al., with permission [<a href="#B71-ijms-26-01499" class="html-bibr">71</a>].</p>
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<p>Schematic diagram of (<b>A</b>) micelle preparation of TPGS, SOL, OLA, and RAPA and (<b>B</b>) representation of the behavior of OLA/RAPA-TPGS/SOL in cancer cells (Abbreviations: TPGS, D-α-tocopheryl polyethylene-glycol (PEG) 1000 succinate; SOL, Soluplus<sup>®</sup>; OLA, olaparib; RAPA, rapamycin; EtOH, ethanol; PARP, poly(ADP-ribose) polymerase; mTOR, mammalian target of rapamycin; P-gp, P-glycoprotein; EPR effect, enhanced permeability and retention). From Shin et al., with permission [<a href="#B87-ijms-26-01499" class="html-bibr">87</a>].</p>
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<p>Interaction of Ag-AZI-Sol NPs with Gram-positive and Gram-negative bacteria cell membranes. From Jaligam et al., with permission [<a href="#B132-ijms-26-01499" class="html-bibr">132</a>].</p>
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16 pages, 9150 KiB  
Article
The Development and Preparation of Novel Gel Emulsion Systems Based on a Cholesterol Star-Shaped Derivative
by Shuaihua Liu, Tian Yao, Donghui Xia, Quan Liu, Guanghui Tian and Yang Liu
Molecules 2025, 30(4), 787; https://doi.org/10.3390/molecules30040787 - 8 Feb 2025
Viewed by 297
Abstract
Low-molecular-mass gelators (LMMGs) as stabilizers for gel emulsions offer numerous advantages, such as low usage, functionalizability, and insensitivity to phase ratio. Using LMMGs as stabilizers is one of the effective strategies for preparing gel emulsions. Currently, developing LMMGs and stable gel emulsion systems [...] Read more.
Low-molecular-mass gelators (LMMGs) as stabilizers for gel emulsions offer numerous advantages, such as low usage, functionalizability, and insensitivity to phase ratio. Using LMMGs as stabilizers is one of the effective strategies for preparing gel emulsions. Currently, developing LMMGs and stable gel emulsion systems in a rapid and convenient manner remains a challenge. To cope with the challenge, this study aims to develop a simple and efficient gel emulsion preparation method based on LMMGs. In this study, a cholesterol-based star-shaped derivative (CSD) was designed and synthesized as an LMMG. Based on gelation experiments, a high internal phase W/O gel emulsion system (H2O/CSD-poly(oligo)-dimethylsiloxane/dichloromethane) was successfully developed and stabilized synergistically by the stabilizer (CSD) and the crosslinker (poly(oligo)-dimethylsiloxane with two olefinic bonds at its ends, D-PDMS). The results demonstrate that the synergistic interaction between CSD and D-PDMS is critical for the formation of the gel emulsion. Building on the original gel emulsion system, two novel in situ polymerizable gel emulsion systems (H2O/CSD-D-PDMS/dichloromethane-tert-butyl methacrylate and H2O/CSD-D-PDMS/dichloromethane-N-tert-butyl methacrylamide) were successfully developed by introducing suitable amphiphilic (hydrophilic/lipophilic) polymerizable monomers. This study found that changes in the amphiphilicity of the introduced monomers significantly affected the stability and microscopic morphology of the gel emulsion system. The findings indicate that constructing a hydrophilic/lipophilic balanced system via the synergistic action of stabilizers and crosslinkers in a solvent system, followed by the introduction of polymerizable monomers, is a simple and efficient method for rapidly developing novel polymerizable gel emulsions. These new polymerizable gel emulsions lay the foundation for the subsequent preparation of porous organic polymers (POPs). Full article
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<p>Structure of CSD and D-PDMS.</p>
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<p>Gelation behavior of CSD in different components: (<b>a</b>) CSD 0% (<span class="html-italic">w</span>/<span class="html-italic">v</span>), 100 µL DCM, 900 µL water; (<b>b</b>) CSD 0% (<span class="html-italic">w</span>/<span class="html-italic">v</span>), 0.075 g D-PDMS; (<b>c</b>) CSD 2.5% (<span class="html-italic">w</span>/<span class="html-italic">v</span>); (<b>d</b>) CSD 2.5% (<span class="html-italic">w</span>/<span class="html-italic">v</span>) and 0.075 g D-PDMS (total volume 1 mL; CSD concentration is the mass volume fraction relative to the organic phase).</p>
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<p>Inverted fluorescence microscopy image of the gel emulsion, with the following components: 2.5% CSD (<span class="html-italic">w</span>/<span class="html-italic">v</span>, mass volume fraction relative to the organic phase), 0.0175 g D-PDMS, 100 µL DCM, 900 µL water.</p>
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<p>Four polymerizable monomers: (<b>a</b>) <span class="html-italic">tert</span>-butyl methacrylate (<span class="html-italic">t</span>-BMA), (<b>b</b>) <span class="html-italic">N</span>-<span class="html-italic">tert</span>-butyl methacrylamide (<span class="html-italic">N</span>-<span class="html-italic">t</span>-BMA), (<b>c</b>) <span class="html-italic">N</span>-<span class="html-italic">tert</span>-butyl acrylamide (<span class="html-italic">N</span>-<span class="html-italic">t</span>-BAA), (<b>d</b>) styrene.</p>
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<p>Photos of gel emulsions formed with different DCM–<span class="html-italic">t</span>-BMA (<span class="html-italic">v</span>/<span class="html-italic">v</span>) ratios: (<b>a</b>) 10:0, (<b>b</b>) 9:1, (<b>c</b>) 8:2, (<b>d</b>) 7:3, (<b>e</b>) 6:4, (<b>f</b>) 5:5, (<b>g</b>) 4:6, (<b>h</b>) 3:7, (<b>i</b>) 2:8, (<b>j</b>) 1:9, (<b>k</b>) 0:10 (stabilizer content is 2.5% (<span class="html-italic">w</span>/<span class="html-italic">v</span>) of the organic phase, D-PDMS is 0.075 g, and the aqueous phase makes up 90% of the total volume).</p>
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<p>Inverted fluorescence microscope images of gel emulsions formed with different DCM–<span class="html-italic">t</span>-BMA (<span class="html-italic">v</span>/<span class="html-italic">v</span>) ratios: (<b>a</b>) 10:0, (<b>b</b>) 7:3, (<b>c</b>) 6:4, (<b>d</b>) 5:5.</p>
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<p>Photos of emulsions or gel emulsions formed at <span class="html-italic">N</span>-<span class="html-italic">t</span>-BMA concentrations ranging from 0% to 100% of the saturation concentration (relative to the organic phase): (<b>a</b>) 0%, (<b>b</b>) 10%, (<b>c</b>) 20%, (<b>d</b>) 30%, (<b>e</b>) 40%, (<b>f</b>) 50%, (<b>g</b>) 60%, (<b>h</b>) 70%, (<b>i</b>) 80%, (<b>j</b>) 90%, (<b>k</b>) 100% (stabilizer content is 2.5% (<span class="html-italic">w</span>/<span class="html-italic">v</span>) of the organic phase, D-PDMS is 0.075 g, and the aqueous phase makes up 90% of the total volume).</p>
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<p>Inverted fluorescence microscope image of the gel emulsion formed at 50% of the saturation concentration (relative to the organic phase) of <span class="html-italic">N</span>-<span class="html-italic">t</span>-BMA.</p>
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<p>Photos of emulsions or gel emulsions formed at <span class="html-italic">N</span>-<span class="html-italic">t</span>-BAA concentrations ranging from 0% to 100% of the saturation concentration (relative to the organic phase): (<b>a</b>) 0%, (<b>b</b>) 10%, (<b>c</b>) 20%, (<b>d</b>) 30%, (<b>e</b>) 40%, (<b>f</b>) 50%, (<b>g</b>) 60%, (<b>h</b>) 70%, (<b>i</b>) 80%, (<b>j</b>) 90%, (<b>k</b>) 100% (stabilizer content is 2.5% (<span class="html-italic">w</span>/<span class="html-italic">v</span>) of the organic phase, D-PDMS is 0.075 g, and the aqueous phase makes up 90% of the total volume).</p>
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<p>Photos of emulsions formed with different DCM–styrene (<span class="html-italic">v</span>/<span class="html-italic">v</span>) ratios: (<b>a</b>) 10:0, (<b>b</b>) 9:1, (<b>c</b>) 8:2, (<b>d</b>) 7:3, (<b>e</b>) 6:4, (<b>f</b>) 5:5, (<b>g</b>) 4:6, (<b>h</b>) 3:7, (<b>i</b>) 2:8, (<b>j</b>) 1:9, (<b>k</b>) 0:10 (stabilizer content is 2.5% (<span class="html-italic">w</span>/<span class="html-italic">v</span>) of the organic phase, D-PDMS is 0.075 g, and the aqueous phase makes up 90% of the total volume).</p>
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<p>The <span class="html-italic">G</span>′ and <span class="html-italic">G</span>″ curves of DCM and gel emulsions containing different polymerizable monomers as a function of shear stress.</p>
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<p>Molecular structure of the fluorescent probe.</p>
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<p>Synthesis route of the CSD.</p>
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<p>Synthesis route of the D-PDMS.</p>
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16 pages, 11740 KiB  
Article
Protein Cage-like Vesicles Fabricated via Polymerization-Induced Microphase Separation of Amphiphilic Diblock Copolymers
by Eri Yoshida
Materials 2025, 18(3), 727; https://doi.org/10.3390/ma18030727 - 6 Feb 2025
Viewed by 371
Abstract
Highly symmetric protein cages represent one of the most artistic architectures formed by biomolecules. However, the underlying reasons for the formation of some of these architectures remain unknown. The present study aims to investigate the significance behind their morphological formation by fabricating protein [...] Read more.
Highly symmetric protein cages represent one of the most artistic architectures formed by biomolecules. However, the underlying reasons for the formation of some of these architectures remain unknown. The present study aims to investigate the significance behind their morphological formation by fabricating protein cage-like vesicles using a synthetic polymer. The vesicles were synthesized by combining polymerization-induced self-assembly (PISA) with polymerization-induced microphase separation (PIMS), employing an amphiphilic poly(methacrylic acid)-block-poly(n-butyl methacrylate-random-cyclohexyl methacrylate-random-methacrylic acid) diblock copolymer, PMAA-b-P(BMA-r-CMA-r-MAA). The copolymer, with a 60 mol% molar ratio of CMA to the BMA units, produced clathrin-like vesicles with angular windows in their shell, resulting from the segregation of the hard CMA units from the soft BMA matrix in the hydrophobic phase of the vesicle. These vesicles were highly stable against rising temperatures. In contrast, the vesicles with a 30 mol% CMA ratio dissociated upon heating to 50 °C into triskelion-like segments due to intramolecular microphase separation. These findings indicate that designing synthetic polymers can mimic living organ morphologies, aiding in elucidating their morphological significance and inspiring the development of new materials utilizing these morphologies. Full article
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Graphical abstract

Graphical abstract
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<p>Schematic procedure for the synthesis of PMAA-<span class="html-italic">b</span>-P(BMA-<span class="html-italic">r</span>-CMA-<span class="html-italic">r</span>-MAA) diblock copolymers.</p>
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<p>The photo-NMP process for the PISA of PMAA-<span class="html-italic">b</span>-P(BMA-<span class="html-italic">r</span>-CMA-<span class="html-italic">r</span>-MAA): (<b>a</b>) time–conversion plots, (<b>b</b>) first-order time–conversion plots, and (<b>c</b>) variation in the molar ratio of the CMA unit to the total hydrophobic units (BMA and CMA) in the random copolymer block over time.</p>
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<p>The living nature of the photo-NMP during the PISA of PMAA-<span class="html-italic">b</span>-P(BMA-<span class="html-italic">r</span>-CMA-<span class="html-italic">r</span>-MAA): (<b>a</b>) molecular weight plots of the resulting copolymers versus monomer conversions, (<b>b</b>) polydispersity index plots of the copolymers versus monomer conversions, and (<b>c</b>) GPC profiles of the copolymers after 2, 3, 5.5, and 8 h of polymerization (from right to left).</p>
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<p>FE-SEM images of the vesicle morphologies at different polymerization times: (<b>a</b>) 2 h, (<b>b</b>) 3 h, and (<b>c</b>) 8 h.</p>
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<p>FE-SEM images of the vesicles with varying CMA ratios: (<b>a</b>) 0 mol%, (<b>b</b>) 10 mol%, (<b>c</b>) 20 mol%, (<b>d</b>) 30 mol%, (<b>e</b>) 40 mol%, (<b>f</b>) 50 mol%, (<b>g</b>) 60 mol%, (<b>h</b>) 70 mol%, (<b>i</b>) 80 mol%, (<b>j</b>) 90 mol%, and (<b>k</b>) 100 mol%.</p>
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<p>CMA ratio-dependent morphological transformations of the vesicles.</p>
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<p>DSC analysis of the vesicles: (<b>a</b>) spectra of the vesicles with 60 mol% CMA units, and (<b>b</b>) <span class="html-italic">T</span><sub>g</sub> plots of the hydrophobic blocks from the first and second scans versus the CMA ratio.</p>
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<p>A schematic illustration of hole formation through microphase separation caused by the aggregation of CMA units.</p>
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<p>Thermal stability of the vesicles under different conditions: (<b>a</b>) 8 g/L, 25 °C; (<b>b</b>) 8 g/L, 50 °C for 1 h; and (<b>c</b>) 2 g/L, 50 °C for 1 h. CMA units = 60 mol%.</p>
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<p>Variations in (<b>a</b>) scattering intensity (<span class="html-italic">SI</span>) and (<b>b</b>) hydrodynamic size (<span class="html-italic">D</span><sub>h</sub>) of the vesicles at different concentrations. CMA units = 30 mol%.</p>
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<p>Variation in the <span class="html-italic">D</span><sub>h</sub> of the vesicles during heating, followed by cooling. The vesicles are maintained at each temperature for 15 min. CMA units = 30 mol%, [vesicle]<sub>0</sub> = 0.267 g/L.</p>
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<p>Scattering intensity distribution for the <span class="html-italic">D</span><sub>h</sub> of the vesicles at each temperature during heating and cooling. The vesicles are maintained at each temperature for 15 min, except at 50 °C for 3 h. CMA units = 30 mol%, [vesicle]<sub>0</sub> = 0.267 g/L.</p>
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<p>The dissociation of the copolymers, followed by their aggregation due to the loss of hydrated water molecules or absorption into the parent vesicle.</p>
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<p>FE-SEM images of the vesicles with 30 mol% CMA units left at each temperature for 1 h: (<b>a</b>) 25 °C, (<b>b</b>) 30 °C, (<b>c</b>) 35 °C, (<b>d</b>) 40 °C, (<b>e</b>) 45 °C, and (<b>f</b>) 50 °C. [vesicle]<sub>0</sub> = 2 g/L.</p>
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<p>FE-SEM images of vesicles heated to 50 °C at different concentrations and annealing times: (<b>a</b>) 4 g/L, 1.5 h; (<b>b</b>) 2 g/L, 1.5 h; (<b>c</b>) 1 g/L, 1.5 h; (<b>d</b>) 4 g/L, 2 h; (<b>e</b>) 2 g/L, 2 h; and (<b>f</b>) 1 g/L, 2 h. CMA units = 30 mol%.</p>
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<p>FE-SEM images of the vesicles left at 25 °C for 18.5 h at different concentrations: (<b>a</b>) 4 g/L, (<b>b</b>) 2 g/L, and (<b>c</b>) 1 g/L. CMA units = 30 mol%.</p>
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<p>FE-SEM images of the vesicles heated at 50 °C for 1 h with different CMA unit ratios: (<b>a</b>) 0 mol%, (<b>b</b>) 10 mol%, (<b>c</b>) 20 mol%, (<b>d</b>) 30 mol%, (<b>e</b>) 40 mol%, (<b>f</b>) 50 mol%, (<b>g</b>) 60 mol%, (<b>h</b>) 70 mol%, (<b>i</b>) 80 mol%, (<b>j</b>) 90 mol%, and (<b>k</b>) 100 mol%.</p>
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<p>The dissociation of vesicles into triskelion-like segments undergoing intramolecular microphase separation.</p>
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9 pages, 1300 KiB  
Article
Production of Uniform Droplets and Lipid Nanoparticles Using Perfluoropolyether-Based Microfluidic Devices
by Mincheol Cho, Eun Seo Kim, Tae-Kyung Ryu, Inseong Choi and Sung-Wook Choi
Micromachines 2025, 16(2), 179; https://doi.org/10.3390/mi16020179 - 31 Jan 2025
Viewed by 683
Abstract
Microfluidic devices are greatly affected by the materials used. The materials used in previous studies had problems in various aspects, such as processing, adsorption, and price. This study will investigate the materials needed to overcome such problems. Various microfluidic devices based on the [...] Read more.
Microfluidic devices are greatly affected by the materials used. The materials used in previous studies had problems in various aspects, such as processing, adsorption, and price. This study will investigate the materials needed to overcome such problems. Various microfluidic devices based on the perfluorinated compound perfluoropolyether (PFPE) were fabricated and mixed with hydrophilic and amphiphilic monomers, including poly(ethylene glycol) diacrylate, polyethylene glycol monomethacrylate, poly(ethylene glycol) methyl ether methacrylate, acrylic acid, and 2-hydroxyethyl methacrylate. A PFPE-based sheet with a repeating structure of hydrophobic and hydrophilic groups was fabricated. Thus, the hydrophilicity of highly hydrophobic PFPE was enhanced. The fluidic channel was engraved on a PFPE-based sheet using laser cutting and a fabricated microfluidic device. The channels of microfluidic devices are micro-scale (100 µm~300 µm). The lipid nanoparticles and droplets generated through the microfluidic device demonstrated uniform particles continuously. Full article
(This article belongs to the Special Issue Microfluidic Nanoparticle Synthesis)
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<p>Schematic illustration of (<b>A</b>) fabrication, (<b>B</b>) emulsion, and (<b>C</b>) the production of LNPs in a microfluidic device.</p>
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<p>(<b>A</b>) Water contact angles, (<b>B</b>) swelling ratio, and (<b>C</b>) photographs of PFPE-based slabs with different contents of PFPE-based materials (<span class="html-italic">n</span> = 5).</p>
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<p>(<b>A</b>) Snapshot of PFPE-based slab channel, where fabricating LNPs were captured by high-speed camera and slab design for fabricating LNPs. (<b>B</b>) Z-average size and PDI of LNPs obtained by different PFPE-based material slabs.</p>
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<p>(<b>A</b>,<b>B</b>) Average diameter and CV value of the emulsions at different flow rates of the continuous phase, which was fabricated by different PFPE-based slabs, and the frequency graph of the emulsion diameter formed at TFR (1.7 mL/h) and FRR (2:15) flow rate conditions.</p>
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20 pages, 5088 KiB  
Article
Molecular Modification of Queen Bee Acid and 10-Hydroxydecanoic Acid with Specific Tripeptides: Rational Design, Organic Synthesis, and Assessment for Prohealing and Antimicrobial Hydrogel Properties
by Song Hong, Sachin B. Baravkar, Yan Lu, Abdul-Razak Masoud, Qi Zhao and Weilie Zhou
Molecules 2025, 30(3), 615; https://doi.org/10.3390/molecules30030615 - 30 Jan 2025
Viewed by 575
Abstract
Royal jelly and medical grade honey are traditionally used in treating wounds and infections, although their effectiveness is often variable and insufficient. To overcome their limitations, we created novel amphiphiles by modifying the main reparative and antimicrobial components, queen bee acid (hda) and [...] Read more.
Royal jelly and medical grade honey are traditionally used in treating wounds and infections, although their effectiveness is often variable and insufficient. To overcome their limitations, we created novel amphiphiles by modifying the main reparative and antimicrobial components, queen bee acid (hda) and 10-hydroxyl-decanoic acid (hdaa), through peptide bonding with specific tripeptides. Our molecular design incorporated amphiphile targets as being biocompatible in wound healing, biodegradable, non-toxic, hydrogelable, prohealing, and antimicrobial. The amphiphilic molecules were designed in a hda(hdaa)-aa1-aa2-aa3 structural model with rational selection criteria for each moiety, prepared via Rink/Fmoc-tBu-based solid-phase peptide synthesis, and structurally verified by NMR and LC–MS/MS. We tested several amphiphiles among those containing moieties of hda or hdaa and isoleucine–leucine–aspartate (ILD-amidated) or IL-lysine (ILK-NH2). These tests were conducted to evaluate their prohealing and antimicrobial hydrogel properties. Our observation of their hydrogelation and hydrogel-rheology showed that they can form hydrogels with stable elastic moduli and injectable shear-thinning properties, which are suitable for cell and tissue repair and regeneration. Our disc-diffusion assay demonstrated that hdaa-ILK-NH2 markedly inhibited Staphylococcus aureus. Future research is needed to comprehensively evaluate the prohealing and antimicrobial properties of these novel molecules modified from hda and hdaa with tripeptides. Full article
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<p>The molecular structures of typical hfa-aa1–aa2–aa3 amphiphiles, hda-ILD and hdaa-ILD, made via SPPS organic synthesis were confirmed by LC–MS/MS analysis. (<b>A</b>) Queen bee acid (hda) was covalently bonded to tri-peptide isoleucine (I)-leucine (L)-aspartic acid (D) (ILD), forming hda-ILD amphiphilic molecule. (<b>B</b>) LC–MS/MS chromatogram of hda-ILD. (<b>C</b>) LC–MS/MS spectrum of hda-ILD. (<b>D</b>) The hdaa bonded to ILD forming hdaa-ILD amphiphilic molecule. (<b>E</b>) LC–MS/MS chromatogram of hdaa-ILD. (<b>F</b>) LC–MS/MS spectrum of hdaa. Sciex Qtrap 6500<sup>+</sup> MS/MS was used.</p>
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<p>Hydrogels formed from hdaa-ILD-NH<sub>2</sub> (<b>1</b>) and hda-ILD-NH<sub>2</sub> (<b>3</b>) are stable in PBS at pH 2 to 10 and 2 to 8, respectively. (<b>A</b>) Photos showing that hdaa-ILD-NH<sub>2</sub> (<b>1</b>) gelated and remained gelated in PBS at pH 2 (<b>left</b>) and 10 (<b>right</b>). (<b>B</b>) Photos showing that hda-ILD-NH<sub>2</sub> (<b>3</b>) gelated and remained gelated in PBS at pH 2 (<b>left</b>) and 8 (<b>middle</b>). The hydrogel was generated from compound <b>1</b> or <b>3</b> at 1.5% <span class="html-italic">w</span>/<span class="html-italic">v</span> in PBS and transformed to solution phase at pH 11.5 or 10, respectively.</p>
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<p>Gelation and rheological and injectable tests of hda-ILD-NH<sub>2</sub> (<b>3</b>) and hdaa-ILD-NH<sub>2</sub> (<b>1</b>) hydrogels. For hda-ILD-NH<sub>2</sub> (<b>3</b>) hydrogels: (<b>A</b>) shear strain amplitude sweep test; (<b>B</b>) frequency sweep; (<b>C</b>) thixotropic test; and (<b>D</b>) photos: vial-inversion test for gelation (<b>upper</b>) and injectability test (<b>lower</b>). For hdaa-ILD-NH<sub>2</sub> (<b>1</b>) hydrogels: (<b>E</b>) shear strain amplitude sweep test; (<b>F</b>) frequency sweep test; (<b>G</b>) thixotropic test; and (<b>H</b>) photo of vial-inversion test for gelation. Shear strain amplitude sweep test had a constant frequency of 10 rads/s. Frequency sweep test was with a constant shear strain of 1%. Thixotropic test was performed with imposition of a hydrogel-endurable shear strain of 0.1% and a hydrogel-breaking shear strain of 200%. Hydrogels were self-assembled from hda-ILD-NH<sub>2</sub> (<b>3</b>) or hdaa-ILD-NH<sub>2</sub> (<b>1</b>) at 3% (<span class="html-italic">w</span>/<span class="html-italic">v</span>) in PBS at pH 7.4 at 23 °C, and then were tested on an Anton-Paar MCR 092 model rheometer or injected from a syringe to surface at 37 °C.</p>
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<p>Fibrous structures of hda-ILD-NH<sub>2</sub> (<b>3</b>) determined using field emission scanning and transmission electron microscopy (FE–SEM and TEM). (<b>A</b>) Image at ×10,000 and (<b>B</b>) image at ×40,000 for FE–SEM. (<b>C</b>) The TEM image at ×60,000 magnification. FE–SEM secondary electrons were detected using an upper detector, with a working distance of 11.4 mm and acceleration voltage of −3.0 kV.</p>
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<p>The amphiphile hdaa-ILK-NH<sub>2</sub> (<b>6</b>) modified from hdaa with tripeptide ILK-NH<sub>2</sub> by peptide bonding inhibited <span class="html-italic">S. aureus</span> in a Kirby–Bauer disc diffusion assay. (<b>A</b>) <span class="html-italic">S. aureus</span> was inoculated and 5 mg hdaa-ILK-NH<sub>2</sub> (<b>6</b>) was added to the well. (<b>B</b>) <span class="html-italic">S. aureus</span> without treatment. The inhibition zone of <span class="html-italic">S. aureus</span> was photographed and measured at 25 mm in mean radius.</p>
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<p>General strategy for Fmoc/tBu-based solid-phase peptide synthesis (SPPS) of a novel amphiphile from its moiety via peptide bond linkage under the molecular sequence model as hydroxyl fatty acid-amino acid 1-amino acid 2-amino acid 3 (hfa-aa1-aa2-aa3).</p>
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29 pages, 899 KiB  
Article
Antioxidant, Antithrombotic and Anti-Inflammatory Properties of Amphiphilic Bioactives from Water Kefir Grains and Its Apple Pomace-Based Fermented Beverage
by Dimitra Papadopoulou, Vasiliki Chrysikopoulou, Aikaterini Rampaouni, Christos Plakidis, Anna Ofrydopoulou, Katie Shiels, Sushanta Kumar Saha and Alexandros Tsoupras
Antioxidants 2025, 14(2), 164; https://doi.org/10.3390/antiox14020164 - 29 Jan 2025
Viewed by 607
Abstract
Kefir-based fermentation products exhibit antioxidant and anti-inflammatory effects against oxidative stress, inflammation, platelet activation and aggregation, and other related manifestations, thereby preventing the onset and development of several chronic diseases. Specifically, water kefir, a symbiotic culture of various microorganisms used for the production [...] Read more.
Kefir-based fermentation products exhibit antioxidant and anti-inflammatory effects against oxidative stress, inflammation, platelet activation and aggregation, and other related manifestations, thereby preventing the onset and development of several chronic diseases. Specifically, water kefir, a symbiotic culture of various microorganisms used for the production of several bio-functional fermented products, has been proposed for its health-promoting properties. Thus, water kefir grains and its apple pomace-based fermentation beverage were studied for bioactive amphiphilic and lipophilic lipid compounds with antioxidant, antithrombotic, and anti-inflammatory properties. Total lipids (TL) were extracted and further separated into their total amphiphilic (TAC) and total lipophilic content (TLC), in which the total phenolic and carotenoid contents (TPC and TCC, respectively) and the fatty acid content of the polar lipids (PL) were quantified, while the antioxidant activity of both TAC and TLC were assessed in vitro, by the ABTS, DPPH, and FRAP bioassays, along with the anti-inflammatory and antithrombotic activity of TAC against human platelet aggregation induced by the thrombo-inflammatory mediator, platelet-activating factor (PAF) or standard platelet agonists like ADP.ATR-FTIR spectra facilitated the detection of specific structural, functional groups of phenolic, flavonoid, and carotenoid antioxidants, while LC−MS analysis revealed the presence of specific anti-inflammatory and antithrombotic PL bioactives bearing unsaturated fatty acids in their structures, with favorable omega-6 (n-6)/omega-3 (n-3)polyunsaturated fatty acids (PUFA), which further support the findings that the most potent antioxidant, anti-inflammatory and antithrombotic bioactivities were observed in the TAC extracts, in both water kefir grains and beverage cases. The detection of such bioactive components in both the uncultured water kefir grains and in the cultured beverage further supports the contribution of water kefir microorganisms to the bioactivity and the bio-functionality of the final fermented product. Nevertheless, the extracts of the beverage showed much stronger antioxidant, anti-inflammatory, and antithrombotic activities, which further suggests that during the culture process for producing this beverage, not only was the presence of bioactive compounds produced by kefir microflora present, but biochemical alterations during fermentation of bioactive components derived from apple pomace also seemed to have taken place, contributing to the higher bio-functionality observed in the apple pomace—water kefir-based beverage, even when compared to the unfermented apple pomace. The overall findings support further studies on the use of water kefir and/or apple pomace as viable sources of antioxidant, anti-inflammatory, and antithrombotic amphiphilic bioactive compounds for the production of novel health-promoting bio-functional fermented products. Full article
(This article belongs to the Special Issue Antioxidants from Sustainable Food Sources)
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<p>The anti-inflammatory and antithrombotic potency of extracts from WKGs and WKB against human platelet aggregation induced via the inflammatory and thrombotic mediator PAF. Results are expressed as means of the IC50 (half-maximal inhibitory concentration) values in μg of TAC and TLC extract in the aggregometer cuvette that causes 50% inhibition of PAF-induced platelet aggregation (the lower the IC50 value for a lipid extract, the higher its inhibitory effect against the specific agonist of platelet aggregation). * denotes a statistically significant difference, <span class="html-italic">p</span> &lt; 0.05, of the anti-PAF anti-inflammatory activity of TAC extracts compared to TLC extracts in both kefir grains and kefir beverage, while # denotes a statistically significant difference, <span class="html-italic">p</span> &lt; 0.05, of the anti-PAF activity of beverage TAC extracts compared to kefir grains TAC extracts. Abbreviations: WKGs-TAC, amphiphilic lipids extracted from water kefir grains; WKGs-TLC, lipophilic lipids extracted from water kefir grains; WKB-TAC, amphiphilic lipids extracted from water kefir beverage; WKB-TLC, lipophilic lipids extracted from water kefir beverage.</p>
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<p>The antiplatelet potency of extracts from WKGs and WKB against human platelet aggregation induced by a standard platelet agonist, ADP. Results are expressed as means of the IC50 (half-maximal inhibitory concentration) values in μg of TAC and TLC extract in the aggregometer cuvette that causes 50% inhibition of ADP-induced platelet aggregation (the lower the IC50 value for a lipid extract, the higher its inhibitory effect against the specific agonist of platelet aggregation). * denotes a statistically significant difference, <span class="html-italic">p</span> &lt; 0.05, of the anti-ADP antiplatelet activity of TAC extracts compared to TLC extracts in both kefir grains and kefir beverage, while # denotes a statistically significant difference, <span class="html-italic">p</span> &lt; 0.05, of the anti-ADP activity of beverage TAC extracts compared to kefir grain TAC extracts. Abbreviations: WKGs-TAC, amphiphilic lipids extracted from water kefir grains; WKGs-TLC, lipophilic lipids extracted from water kefir grains; WKB-TAC, amphiphilic lipids extracted from water kefir beverage; WKB-TLC, lipophilic lipids extracted from water kefir beverage.</p>
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11 pages, 5975 KiB  
Article
The Preparation of Cyclic Binary Block Polymer Using Bimolecular Homodifunctional Coupling Reaction and Characterization of Its Performance as a Drug Carrier
by Guiying Kang, Muxin Lu, Kang Zhou, Cuiyun Yu and Hua Wei
Molecules 2025, 30(3), 599; https://doi.org/10.3390/molecules30030599 - 29 Jan 2025
Viewed by 600
Abstract
There is relatively little research on cyclic amphiphilic block polymers, having both hydrophilic and hydrophobic segments placed in the ring and thus resulting in a higher degree of topological restriction, as drug vehicles. Cyclic amphiphilic binary block polymer is synthesized by the click [...] Read more.
There is relatively little research on cyclic amphiphilic block polymers, having both hydrophilic and hydrophobic segments placed in the ring and thus resulting in a higher degree of topological restriction, as drug vehicles. Cyclic amphiphilic binary block polymer is synthesized by the click coupling reaction of bimolecular homodifunctional precursors. The results indicate that cyclization between linear polymer precursors is successful if the trace linear by-products generated are ignored, which also suggests that the small molecule bifunctional terminating agent applied in traditional bimolecular homodifunctional ring-closure process can be extended to large molecule. Moreover, the study on the self-assembly behavior of polymers shows that, compared with linear counterparts, the stability and drug loading capacity of micelles based on the resultant cyclic polymer are not significantly improved due to the influence of topological structure and linear impurities. Nevertheless, drug loaded micelles formed by the obtained cyclic polymers still exhibit superior cellular uptake ability. It can be seen that topological effects do play an irreplaceable role in the application performance of polymers. Therefore, the construction and synthesis of cyclic and its derivative polymers with moderate topological confinement and high purity may be a key direction for future exploration of polymer drug delivery carriers. Full article
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<p>SEC elution traces of the linear analogue PEG-<span class="html-italic">b</span>-PCL and cyclic diblock polymer <span class="html-italic">c</span>(PEG-<span class="html-italic">b</span>-PCL) using DMF as an eluent.</p>
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<p>Hydrodynamic diameter and size distribution and TEM images of the micelles self-assembled from cyclic (<b>A</b>,<b>C</b>) and linear (<b>B</b>,<b>D</b>) polymers at a polymer concentration of 0.3 mg/mL.</p>
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<p>In vitro drug release profiles of <span class="html-italic">c</span>(PEG-<span class="html-italic">b</span>-PCL)@DOX and PEG-<span class="html-italic">b</span>-PCL@DOX micelles under different conditions at 37 °C.</p>
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<p>Confocal imaging of free DOX (<b>A</b>), micelles of PEG-<span class="html-italic">b</span>-PCL@DOX (<b>B</b>), and micelles of <span class="html-italic">c</span>(PEG-<span class="html-italic">b</span>-PCL)@DOX (<b>C</b>) uptake in HeLa cells (nuclei stained blue with DAPI). Note that cells were treated with polymer or free drug at 50% of their respective IC<sub>50</sub> values to minimize cell death.</p>
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<p>Quantitative measurements of the mean fluorescence intensity after incubation with free DOX, PEG-<span class="html-italic">b</span>-PCL@DOX, and <span class="html-italic">c</span>(PEG-<span class="html-italic">b</span>-PCL)@DOX in the HeLa cells via flow cytometry (4 h of incubation, DOX concentration = 49 μg/mL, and 10,000 cells counted). The data were expressed as mean ± SD, n = 3, *** <span class="html-italic">p</span> &lt; 0.005.</p>
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<p>Synthesis of cyclic binary block polymer c(PEG-b-PCL).</p>
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30 pages, 7611 KiB  
Article
Design and Development of Natural-Product-Derived Nanoassemblies and Their Interactions with Alpha Synuclein
by Ipsita A. Banerjee, Amrita Das, Mary A. Biggs, Chau Anh N. Phan, Liana R. Cutter and Alexandra R. Ren
Biomimetics 2025, 10(2), 82; https://doi.org/10.3390/biomimetics10020082 - 28 Jan 2025
Viewed by 740
Abstract
Biomimetic nanoassemblies derived from natural products are considered promising nanomaterials due to their self-assembling ability and their favorable interactions with biological molecules leading to their numerous applications as therapeutic agents or as molecular probes. In this work, we have created peptide nanoconjugates of [...] Read more.
Biomimetic nanoassemblies derived from natural products are considered promising nanomaterials due to their self-assembling ability and their favorable interactions with biological molecules leading to their numerous applications as therapeutic agents or as molecular probes. In this work, we have created peptide nanoconjugates of two natural products, β-Boswellic acid (BA) and β-glycyrrhetinic acid (GH). Both BA and GH are known for their medicinal value, including their role as strong antioxidants, anti-inflammatory, neuroprotective and as anti-tumor agents. To enhance the bioavailability of these molecules, they were functionalized with three short peptides (YYIVS, MPDAHL and GSGGL) to create six conjugates with amphiphilic structures capable of facile self-assembly. The peptides were also derived from natural sources and have been known to display antioxidant activity. Depending upon the conjugate, nanofibers, nanovesicles or a mixture of both were formed upon self-assembly. The binding interactions of the nanoconjugates with α-Synuclein, a protein implicated in Parkinson’s disease (PD) was examined through in silico studies and FTIR, circular dichroism and imaging studies. Our results indicated that the nanoassemblies interacted with alpha-synuclein fibrils efficaciously. Furthermore, the nanoassemblies were found to demonstrate high viability in the presence of microglial cells, and were found to enhance the uptake and interactions of α-Synuclein with microglial cells. The nanoconjugates designed in this work may be potentially utilized as vectors for peptide-based drug delivery or for other therapeutic applications. Full article
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<p>Chemical structures of the designed conjugates. (<b>a</b>) Glycyrrhetinate-GSGGL; (<b>b</b>) glycyrrhetinate-MPDAHL; (<b>c</b>) glycyrrhetinate-YYIVS; (<b>d</b>) Boswellate-GSGGL; (<b>e</b>) Boswellate-MPDAHL; (<b>f</b>) Boswellate-YYIVS. Blue: nitrogen; red: oxygen; grey: carbon; and white: hydrogen.</p>
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<p>Binding pocket region of alpha-synuclein fibrils as determined by POCASA.</p>
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<p>(<b>a</b>) Root mean square deviations and (<b>b</b>) root mean square fluctuations of BA–peptide and GH–peptide conjugates over 100 ns simulations. (Y, G and M represent the peptide components of the conjugates: YYIVS, GSGGL and MPDAHL, respectively).</p>
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<p>Trajectory snapshots of GH–peptide conjugates complexed with α-Syn fibrils at 0 ns, 50 ns and at 100 ns over a 100 ns simulation. (<b>a</b>) GH-YYIVS, (<b>b</b>) GH-GSGGL and (<b>c</b>) GH-MPDAHL.</p>
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<p>Trajectory snapshots of BA–peptide conjugates complexed with α-Syn fibrils at 0 ns, 50 ns and at 100 ns over a 100 ns simulation. (<b>a</b>) BA-YYIVS, (<b>b</b>) BA-GSGGL and (<b>c</b>) BA-MPDAHL.</p>
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<p>Comparison of Dynamic Light Scattering Analysis for each of the nanoassemblies formed over a period of one week.</p>
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<p>Scanning electron microscopy images of self-assembled BA–peptide and GH–peptide conjugates. BA = Boswellate; GH = glycyrrhetinate; M = MPDAHL; G = YYIVS; and G = GSGGL.</p>
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<p>Comparison of interactions of alpha-synuclein fibrils with self-assembled nanoconjugates. (<b>a</b>) α-Syn fibrils (untreated); (<b>b</b>) BA-G nanoassemblies with α-Syn; (<b>c</b>) BA-Y assemblies with α-Syn; (<b>d</b>) BA-M nanoassemblies with α-Syn; (<b>e</b>) GH-G nanoassemblies with α-Syn; (<b>f</b>) GH-Y nanoassemblies with α-Syn; and (<b>g</b>) GH-M nanoassemblies with α-Syn. All samples were incubated with α-Syn for 48 h, centrifuged, washed and then imaged using confocal microscopy. Images were taken in brightfield mode. Scale bar = 4 μm.</p>
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<p>Comparison of FTIR spectra of BA–peptide and GH—–peptide nanoassemblies before and after binding with α-Syn. The spectrum of neat α-Syn is also shown to the far right of the image. M = MPDAHL; G = GSGGL; Y = YYIVS.</p>
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<p>Cell viability results for microglial cells after 48 h of incubation with BA–peptide and GH–peptide assemblies. Y, G and M represent the peptide components YYIVS, GSGGL and MPDAHL, respectively, while GH and BA represent the glycyrrhetinate and Boswellate components of the conjugates, respectively. Data expressed are the mean (n = 3) with error bars indicating standard deviations. * <span class="html-italic">p</span> &lt; 0.05; ** <span class="html-italic">p</span> &lt; 0.01.</p>
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<p>Interactions of microglial cells with nanoassemblies. (<b>a</b>) Control untreated cells; (<b>b</b>) cells incubated with BA-G assemblies; (<b>c</b>) cells incubated with BA-G assemblies; (<b>d</b>) cells incubated with BA-G assemblies; (<b>e</b>) cells incubated with BA-G assemblies; (<b>f</b>) cells incubated with BA-G assemblies; (<b>g</b>) cells incubated with BA-G assemblies. Images are taken after 24 h of incubation. Scale bar = 50 μm.</p>
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<p>(<b>a</b>,<b>b</b>) Flow cytometry analysis showing uptake of alpha-synuclein in the presence and absence of nanoassemblies.</p>
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<p>Expression of interleukin 6 in the presence and absence of nanoassemblies and α-Syn fibrils. Control 1: Microglial cells with no treatment. Control 2: Microglial cells with α-Syn fibrils, no assemblies were added.</p>
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24 pages, 720 KiB  
Article
In Vitro Antioxidant, Antithrombotic and Anti-Inflammatory Activities of the Amphiphilic Bioactives Extracted from Avocado and Its By-Products
by Anita Marra, Vasileios Manousakis, Nikolaos Koutis, Georgios Panagiotis Zervas, Anna Ofrydopoulou, Katie Shiels, Sushanta Kumar Saha and Alexandros Tsoupras
Antioxidants 2025, 14(2), 146; https://doi.org/10.3390/antiox14020146 - 26 Jan 2025
Viewed by 646
Abstract
The antioxidant, antithrombotic and anti-inflammatory effects of the amphiphilic compounds extracted from both avocado juice and by-products, were evaluated. All extracts were assessed for their total phenolic content (TPC) and total carotenoid content (TCC), and for their antioxidant activities by DPPH, ABTS and [...] Read more.
The antioxidant, antithrombotic and anti-inflammatory effects of the amphiphilic compounds extracted from both avocado juice and by-products, were evaluated. All extracts were assessed for their total phenolic content (TPC) and total carotenoid content (TCC), and for their antioxidant activities by DPPH, ABTS and FRAP assays as well as for their anti-inflammatory and antithrombotic potency in human platelets. The extracts rich in TAC (Total Amphiphilic Content) showed much higher content in phenolics and carotenoids from the extracts of total lipophilic content (TLC), which was reflected by the much stronger antioxidant capacities of TAC extracts. ATR-FTIR spectroscopy revealed the presence of not only phenolics and carotenoids, but also of bioactive polar lipids (PLs) in avocado TAC extracts, the LC-MS based structural analysis of which further revealed a fatty acid composition favourable for unsaturated fatty acids (UFAs) versus saturated ones (SFAs), including monounsaturated fatty acids (MUFAs) like the oleic acid (C18:1n9) and omega-3 (n3) polyunsaturated fatty acids (PUFAs) like the alpha linolenic acid (C18:3n3), with the subsequent anti-inflammatory low values of the n6/n3 PUFA ratio. The presence of such bioactive PLs that are rich in UFA within the TAC extracts of avocado juice and its by-products provide an explanation for the observed potent anti-inflammatory and antithrombotic activities of avocado TAC against thrombo-inflammatory mediators like platelet activating factor (PAF) and against standard platelet agonists like ADP, offering promise for such avocado TAC extracts, as ingredients in functional products for health/promoting applications either in cosmetics or in functional foods and nutraceuticals, or even drugs. Full article
(This article belongs to the Special Issue Bioactive Antioxidants from Agri-Food Wastes)
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<p>Inhibitory effects of total amphiphilic compounds (TACs) and total lipophilic compounds (TLCs) from avocado juice and by-products (pomace), against the PAF pathway. Results are expressed as IC50 values (half maximum inhibitory concentration), meaning the mass of the compound extract in μg present in the aggregometer cuvette containing 250 μL of human platelet-rich plasma (hPRP) that can cause 50% of inhibition of the PAF-induced inflammatory activation and aggregation of hPRP (the lower the IC50 value, the more potent the anti-inflammatory activity for an extract). * Indicates statistically significant difference, <span class="html-italic">p</span> &lt; 0.05, between TAC and TLC in both the juice and the by-products (pomace).</p>
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<p>Anti-platelet effects of total amphiphilic compounds (TACs) and total lipophilic compounds (TLCs) from avocado juice and by-products (pomace) against the classic platelet agonist ADP. Results are expressed as IC50 values (half maximum inhibitory concentration), meaning the mass of the compound extract in μg present in the aggregometer cuvette containing 250 μL of human platelet-rich plasma (hPRP) that can cause 50% of inhibition of the ADP-induced thrombotic activation and aggregation of hPRP (the lower the IC50 value, the more potent the anti-inflammatory activity for an extract). * Indicates statistically significant difference (<span class="html-italic">p</span> &lt; 0.05) between TAC and TLC in both the juice and the by-products (pomace).</p>
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11 pages, 8731 KiB  
Article
Palladium Nanoparticles Anchored on Cellulose-Derived Amphiphilic Hydrochar for Pickering Interfacial Catalysis
by Dandan Li, Feichao Miao, Jinhua Chen, Zhibing Liu, Zhiyuan Wang and Yang Wang
Processes 2025, 13(2), 339; https://doi.org/10.3390/pr13020339 - 26 Jan 2025
Viewed by 564
Abstract
The development of Pickering interfacial catalysts for organic reactions in water is of great importance to the development of green chemistry. In this study, amphiphilic hydrochar was prepared by a simple urea-modified hydrothermal carbonization with cellulose as an environmentally benign carbon source. It [...] Read more.
The development of Pickering interfacial catalysts for organic reactions in water is of great importance to the development of green chemistry. In this study, amphiphilic hydrochar was prepared by a simple urea-modified hydrothermal carbonization with cellulose as an environmentally benign carbon source. It was found that the addition of urea could not only promote the carbonization of cellulose but also introduce N atoms to the final hydrochar material and tune the amphiphilicity of the hydrochar. Palladium nanoparticles supported on the amphiphilic N-doped hydrochar exhibited high activity in the Suzuki reaction in aqueous media. It can be seen that amphiphilic hydrochar can effectively stabilize Pickering emulsion, increase interface surface area, and further accelerate the Suzuki reaction. Full article
(This article belongs to the Section Catalysis Enhanced Processes)
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<p>Schematic diagram of the preparation of Pd/HNC for Suzuki reaction.</p>
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<p>SEM images of pristine (<b>a</b>) cellulose, (<b>b</b>) HC, and (<b>c</b>) HNC.</p>
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<p>(<b>a</b>) XRD patterns of cellulose, HC, HNC, and Pd/HNC, and (<b>b</b>) FT-IR spectra of HC and HNC.</p>
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<p>EDX mapping of Pd/HNC.</p>
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<p>WCAs of water on the surface of (<b>a</b>) HC and (<b>b</b>) HNC.</p>
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<p>Digital photos of the Pickering emulsion solution stabilized by HC (<b>left</b>) and HNC (<b>right</b>) taken at (<b>a</b>) 0 h and (<b>b</b>) 24 h. (<b>c</b>) Micrograph image of the Pickering emulsion solution stabilized by HNC.</p>
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<p>XPS spectra of (<b>a</b>) full spectra, (<b>b</b>) Pd 3d, and (<b>c</b>) C 1s of Pd/HNC, and (<b>d</b>) N 1s of Pd/HNC.</p>
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<p>Plotting of biphenyl yield as a function of reaction time.</p>
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<p>Recycling performance of Pd/HNC.</p>
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<p>Proposed mechanistic pathway for the Suzuki reaction catalyzed by Pd/HNC.</p>
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