-
Journal of Oleo Science 2024Controlling the morphology of molecular assemblies formed by surfactants by photoirradiation enables the controlled release of incorporated substances, which can be... (Review)
Review
Accelerated Recombination of Lophyl Radicals in Micelles: Rapid Controlled Self-Assembly of Micelles Formed by Amphiphilic Lophine Dimers and Release of Solubilized Substance by Photoirradiation.
Controlling the morphology of molecular assemblies formed by surfactants by photoirradiation enables the controlled release of incorporated substances, which can be applied to delivery systems for drugs and active ingredients. On the other hand, conventional photoresponsive surfactants and molecular assemblies have a slow response speed, making it difficult to control their functions at the desired time. In this review, I discuss our recent progress in the accelerated control of functions of photoresponsive molecular assemblies by using lophine dimer as a photochromic compound. The lophine dimer derivative dissociates into a pair of lophyl radicals that upon ultraviolet (UV) light irradiation, and these radical species thermally recombine although the recombination reaction is extremely slow due to the diffusion of lophyl radicals. By using the confined inner space of micelles formed by surfactants, the recombination reaction was extremely accelerated. With UV light irradiation, rapid morphological changes in micelles, formed by amphiphilic lophine dimers were observed by using in situ small-angle neutron scattering (in situ SANS) system. Moreover, the rapid controlled release of calcein as a model drug was achieved by UV light irradiation using the photoresponsive micelles. This rapid system can realize the controlled release of drugs truly at the desired time, developing an efficient and precise drug delivery system (DDS). Furthermore, it can be applied in a wide range of fields such as release control of active ingredients, efficient heat exchange control, and actuating systems.
Topics: Micelles; Surface-Active Agents; Ultraviolet Rays; Delayed-Action Preparations; Drug Delivery Systems; Dimerization; Drug Liberation; Fluoresceins; Photochemical Processes; Solubility; Free Radicals
PubMed: 38825537
DOI: 10.5650/jos.ess24047 -
Journal of Dairy Science May 2024The present work aims to evaluate the dissociation of casein micelles in diluted skim milk (SM) systems after undergoing solvent- or emulsifying salt-based dissociation...
The present work aims to evaluate the dissociation of casein micelles in diluted skim milk (SM) systems after undergoing solvent- or emulsifying salt-based dissociation coupled with ultra-high-pressure homogenization (UHPH). Specifically, Part I evaluated dilute SM solutions combined with varying ethanol concentrations (0- 60%) at varying temperatures (5 - 65°C) in combination with UHPH (100-300 MPa), and Part II evaluated dilute SM solutions combined with varying concentrations (0-100 mM) of either sodium hexametaphosphate (SHMP) or sodium citrate (SC) in combination with UHPH (100-300 MPa). In Part I, high concentrations of ethanol (40-60% vol/vol) at elevated temperatures (45-65°C) achieved extensive dissociation of casein micelles, especially in combination with UHPH at ≥200 MPa, as shown by an ca. 6-fold reduction in sample absorbance and an ca. 3-fold reduction in casein particle size compared with the control (ca. dilute SM, 65°C) under optimum conditions (dilute SM, 60% ethanol, 65°C, ≥ 200 MPa). In Part II, the level of casein micelle dissociation using emulsifying salts (ES) was dependent on the ES type and concentration. Considerable casein micelle dissociation in dilute SM systems was achieved with SHMP concentrations ≥1 mM and SC concentrations ≥10 mM, resulting in decreased sample absorbance (>6-fold decrease in absorbance), bimodal casein size distributions, and increased hydrophobicity (ca. 2-fold increase in intrinsic fluorescence) compared with the control (dilute SM). This dissociation was further enhanced with UHPH (≥200 MPa). These results indicate that both solvent- and ES-based casein dissociation techniques can be optimized when used in combination with UHPH. Together, these processing techniques can be used to extensively dissociate casein micelles with the potential to use these altered systems for value-added applications such as functional ingredients or encapsulation agents.
PubMed: 38825143
DOI: 10.3168/jds.2024-24850 -
Food Chemistry May 2024This study explored the impact of homogenization (at pressures of 16, 30, and 45 MPa) on both raw and high hydrostatic pressure (HHP)-treated human milk (HM). It...
Application of pressure homogenization on whole human milk pasteurized by high hydrostatic pressure: Effect on protein aggregates in milk fat globule membrane and skim milk phases.
This study explored the impact of homogenization (at pressures of 16, 30, and 45 MPa) on both raw and high hydrostatic pressure (HHP)-treated human milk (HM). It focused on protein compositions and binding forces of soluble and insoluble fractions for both milk fat globule membrane (MFGM) and skim milk. Mild homogenization of HHP-treated milk increased lactoferrin (LF) levels in the insoluble fractions of both MFGM and skim milk, due to insoluble aggregation through hydrophobic interactions. Intense homogenization of HHP-treated milk decreased the LF level in the MFGM fractions due to the LF desorption from the MFGM, which increased LF level in the insoluble skim milk fraction. Homogenized-HHP treated milk showed noticeably higher casein (CN) level at the MFGM compared to homogenized-raw milk, attributed to HHP effect on CN micelles. Overall, the combined use of HHP and shear-homogenization should be avoided as it increased the biological proteins in insoluble fractions.
PubMed: 38823140
DOI: 10.1016/j.foodchem.2024.139863 -
International Journal of Biological... Jun 2024Gum Arabic underwent enzymatic modification with curcumin oxidation products, prompting self-assembly in water at lower concentrations than native gum Arabic, which was...
Gum Arabic underwent enzymatic modification with curcumin oxidation products, prompting self-assembly in water at lower concentrations than native gum Arabic, which was fully soluble. The resulting particles displayed a narrow size distribution, suggestive of a micellization mechanism akin to Critical Micellization Concentration (CMC) in surfactants or Critical Aggregation Concentration (CAC) in polymers. Accurately determining CAC is vital for utilizing polymers in molecule encapsulation, but precise measurement is challenging, requiring multiple techniques. Initially, CAC was probed via turbidity measurements, dynamic light scattering (DLS), and isothermal calorimetric titration (ITC), yielding a range of 0.0015 to 0.01 %. Micro-scale thermophoresis (MST) was then employed for the first time to define CAC more precisely, facilitated by the intrinsic fluorescence of modified gum Arabic. Using MST, CAC was pinpointed at 0.001 % (w/v), a novel approach. Furthermore, MST revealed a low EC50 value of 0.007 % (w/t) for self-assembly, signifying uniformity among GAC sub-units and assembly stability upon dilution.
Topics: Gum Arabic; Oxidation-Reduction; Curcumin; Water; Micelles
PubMed: 38821797
DOI: 10.1016/j.ijbiomac.2024.132510 -
Science and Technology of Advanced... 2024Targeted nanoparticles offer potential to selectively deliver therapeutics to cells; however, their subcellular fate following endocytosis must be understood to properly...
Targeted nanoparticles offer potential to selectively deliver therapeutics to cells; however, their subcellular fate following endocytosis must be understood to properly design mechanisms of drug release. Here we describe a nanoparticle platform and associated cell-based assay to observe lysosome trafficking of targeted nanoparticles in live cells. The nanoparticle platform utilizes two fluorescent dyes loaded onto PEG-poly(glutamic acid) and PEG-poly(Lysine) block co-polymers that also comprise azide reactive handles on PEG termini to attach antibody-based targeting ligands. Fluorophores were selected to be pH-sensitive (pHrodo Red) or pH-insensitive (Alexafluor 488) to report when nanoparticles enter low pH lysosomes. Dye-labelled block co-polymers were further assembled into polyion complex micelle nanoparticles and crosslinked through amide bond formation to form stable nano-scaffolds for ligand attachment. Cell binding and lysosome trafficking was determined in live cells by fluorescence imaging in 96-well plates and quantification of red- and green-fluorescence signals over time. The platform and assay was validated for selection of optimal antibody-derived targeting ligands directed towards CD22 for nanoparticle delivery. Kinetic analysis of uptake and lysosome trafficking indicated differences between ligand types and the ligand with the highest lysosome trafficking efficiency translated into effective DNA delivery with nanoparticles bearing the optimal ligand.
PubMed: 38817250
DOI: 10.1080/14686996.2024.2351791 -
Biophysical Chemistry Aug 2024Reverse micelles (RMs) are spontaneously organizing nanobubbles composed of an organic solvent, surfactants, and an aqueous phase that can encapsulate biological...
Reverse micelles (RMs) are spontaneously organizing nanobubbles composed of an organic solvent, surfactants, and an aqueous phase that can encapsulate biological macromolecules for various biophysical studies. Unlike other RM systems, the 1-decanoyl-rac-glycerol (10MAG) and lauryldimethylamine-N-oxide (LDAO) surfactant system has proven to house proteins with higher stability than other RM mixtures with little sensitivity to the water loading (W, defined by the ratio of water to surfactant). We investigated this unique property by encapsulating three model proteins - cytochrome c, myoglobin, and flavodoxin - in 10MAG/LDAO RMs and applying a variety of experimental methods to characterize this system's behavior. We found that this surfactant system differs greatly from the traditional, spherical, monodisperse RM population model. 10MAG/LDAO RMs were discovered to be oblate ellipsoids at all conditions, and as W was increased, surfactants redistributed to form a greater number of increasingly spherical ellipsoidal particles with pools of more bulk-like water. Proteins distinctively influence the thermodynamics of the mixture, encapsulating at their optimal RM size and driving protein-free RM sizes to scale accordingly. These findings inform the future development of similarly malleable encapsulation systems and build a foundation for application of 10MAG/LDAO RMs to analyze biological and chemical processes under nanoscale confinement.
Topics: Micelles; Myoglobin; Surface-Active Agents; Glycerol; Cytochromes c; Flavodoxin; Laurates; Thermodynamics; Water; Dimethylamines
PubMed: 38815545
DOI: 10.1016/j.bpc.2024.107269 -
Journal of Colloid and Interface Science Oct 2024Hollow block copolymer particles called polymer vesicles (polymersomes) serve as versatile containers for compartmentalization in synthetic biology and drug delivery....
Hollow block copolymer particles called polymer vesicles (polymersomes) serve as versatile containers for compartmentalization in synthetic biology and drug delivery. Recently, there has been growing interest in using polymersomes as colloidal building blocks for creating higher-order clustered structures. Most reports thus far rely on the use of DNA base-pairing interactions to "glue" polymersomes with other colloidal components. In this study, we present two alternative electrostatically driven approaches to assemble polymersomes and model colloids (micelles) into hybrid clusters. The first approach uses pH to manipulate electrostatic interactions and effectively control the clustering extent of micellar subunits on polymersomes, while the second approach relies on the hydrolysis of an acid trigger, glucono delta-lactone (GDL), to introduce temporal control over clustering. We envisage our approaches and structures reported herein will help inspire the creation of new prospects for materials science and biomedical applications.
PubMed: 38815380
DOI: 10.1016/j.jcis.2024.05.177 -
RSC Advances May 2024The Biginelli reaction, a three-component cyclocondensation reaction, is an important member of the multicomponent reaction (MCR) family. In this study, we conducted...
The Biginelli reaction, a three-component cyclocondensation reaction, is an important member of the multicomponent reaction (MCR) family. In this study, we conducted end-group modifications on a variety of biodegradable polyesters, including poly(1,4-butylene adipate) (PBA), poly(ε-caprolactone) (PCL), polylactic acid (PLA), and poly(-dioxanone) (PPDO), based on the precursor polyethylene glycol (PEG). By combining two polymers through the Biginelli multi-component reaction, four new biodegradable polyester copolymers, namely DHPM-PBA, DHPM-PCL, DHPM-PLA, and DHPM-PPDO, were formed. These Biginelli reactions demonstrated exceptional completeness, validating the efficiency of the synthesis strategy. Although the introduction of various polyesters lead to different properties, such as crystallinity and cytotoxicity, the newly synthesized 3,4-dihydro-2()-pyrimidinone compounds (DHPMs) exhibit enhanced hydrophilicity and can self-assemble in water and ,-dimethylformamide (DMF) solution to form micelles with a controllable size. Furthermore, DHPM-PPDO promotes cellular growth and has potential applications in wound healing and tissue engineering. In conclusion, this method demonstrates great universality and methodological significance and offers insights into the medical applications of polyethylene glycol.
PubMed: 38813120
DOI: 10.1039/d4ra02002b -
PNAS Nexus May 2024Chronic and genetic kidney diseases such as autosomal dominant polycystic kidney disease (ADPKD) have few therapeutic options, and clinical trials testing small molecule...
Chronic and genetic kidney diseases such as autosomal dominant polycystic kidney disease (ADPKD) have few therapeutic options, and clinical trials testing small molecule drugs have been unfavorable due to low kidney bioavailability and adverse side effects. Although nanoparticles can be designed to deliver drugs directly to the diseased site, there are no kidney-targeted nanomedicines clinically available, and most FDA-approved nanoparticles are administered intravenously which is not ideal for chronic diseases. To meet these challenges of chronic diseases, we developed a biomaterials-based strategy using chitosan particles (CP) for oral delivery of therapeutic, kidney-targeting peptide amphiphile micelles (KMs). We hypothesized that encapsuling KMs into CP would enhance the bioavailability of KMs upon oral administration given the high stability of chitosan in acidic conditions and mucoadhesive properties enabling absorption within the intestines. To test this, we evaluated the mechanism of KM access to the kidneys via intravital imaging and investigated the KM biodistribution in a porcine model. Next, we loaded KMs carrying the ADPKD drug metformin into CP (KM-CP) and measured in vitro therapeutic effect. Upon oral administration in vivo, KM-CP showed significantly greater bioavailability and accumulation in the kidneys as compared to KM only or free drug. As such, KM-CP treatment in ADPKD mice (;; which develops the disease over 120 days and mimics the slow development of ADPKD) showed enhanced therapeutic efficacy without affecting safety despite repeated treatment. Herein, we demonstrate the potential of KM-CP as a nanomedicine strategy for oral delivery for the long-term treatment of chronic kidney diseases.
PubMed: 38807632
DOI: 10.1093/pnasnexus/pgae187 -
Scientific Reports May 2024A key factor affecting foam stability is the interaction of foam with oil in the reservoir. This work investigates how different types of oil influence the stability of...
A key factor affecting foam stability is the interaction of foam with oil in the reservoir. This work investigates how different types of oil influence the stability of foams generated with binary surfactant systems under a high salinity condition. Foam was generated with binary surfactant systems, one composed of a zwitterionic and a nonionic surfactant, and the other composed of an anionic and a nonionic surfactant. Our results showed that the binary surfactant foams investigated are more tolerant under high salinity conditions and in the presence of oil. This was visually observed in our microscopic analysis and was further attributed to an increase in apparent viscosity achieved with binary surfactant systems, compared to single surfactant foams. To understand the influence of oil on foam stability, we performed a mechanistic study to investigate how these oils interact with foams generated with binary surfactants, focusing on their applicability under high salinity conditions. The generation and stability of foam are linked to the ability of the surfactant system to solubilize oil molecules. Oil droplets that solubilize in the micelles appear to destabilize the foam. However, oils with higher molecular weights are too large to be solubilized in the micelles, hence the molecules will have less ability to be transported out of the foam, so oil seems to stabilize the foam. Finally, we conducted a multivariate analysis to identify the parameters that influenced foam stability in different oil types, using the experimental data from our work. The results showed that the oil molecular weight, interfacial tension between the foaming liquid and the oil, and the spreading coefficient are the most important variables for explaining the variation in the data. By performing a partial least square regression, a linear model was developed based on these most important variables, which can be used to predict foam stability for subsequent experiments under the same conditions as our work.
PubMed: 38806570
DOI: 10.1038/s41598-024-62610-1