Spherical Micelles Research Articles

PEGylated nanoparticles interact with macrophages independently of immune response factors and trigger a non-phagocytic, low-inflammatory response

Poly-ethylene-glycol (PEG)-based nanoparticles (NPs) - including cylindrical micelles (CNPs), spherical micelles (SNPs), and PEGylated liposomes (PLs) - are hypothesized to be cleared in vivo by opsonization followed by liver macrophage phagocytosis. This hypothesis has been used to explain the rapid and significant localization of NPs to the liver after administration into the mammalian vasculature. Here, we show that the opsonization-phagocytosis nexus is not the major factor driving PEG-NP – macrophage interactions. First, mouse and human blood proteins had insignificant affinity for PEG-NPs. Second, PEG-NPs bound macrophages in the absence of serum proteins. Third, lipoproteins blocked PEG-NP binding to macrophages. Because of these findings, we tested the postulate that PEG-NPs bind (apo)lipoprotein receptors. Indeed, PEG-NPs triggered an in vitro macrophage transcription program that was similar to that triggered by lipoproteins and different from that triggered by lipopolysaccharide (LPS) and group A Streptococcus. Unlike LPS and pathogens, PLs did not increase transcripts involved in phagocytosis or inflammation. High-density lipoprotein (HDL) and SNPs triggered remarkably similar mouse bone-marrow-derived macrophage transcription programs. Unlike opsonized pathogens, CNPs, SNPs, and PLs lowered macrophage autophagosome levels and either reduced or did not increase the secretion of key macrophage pro-inflammatory cytokines and chemokines. Thus, the sequential opsonization and phagocytosis process is likely a minor aspect of PEG-NP – macrophage interactions. Instead, PEG-NP interactions with (apo)lipoprotein and scavenger receptors appear to be a strong driving force for PEG-NP – macrophage binding, entry, and downstream effects. We hypothesize that the high presence of these receptors on liver macrophages and on liver sinusoidal endothelial cells is the reason PEG-NPs localize rapidly and strongly to the liver.

PH-induced morphological transition of aggregates formed by miktoarm star polymers in dilute solution: a mesoscopic simulation study.

The self-assembly of miktoarm star polymers μ-A i (B(D)) j C k in a neutral solution and the pH-responsive behaviors of vesicles and spherical micelles in an acidic solution have been investigated by DPD simulation. The results show that the self-assembled morphologies can be regulated by the lengths of pH-responsive arm B and hydrophilic arm C, leading to the formation of vesicles, discoidal micelles, and spherical micelles in a neutral solution. The dynamic evolution pathways of vesicles and spherical micelles are categorized into three stages: nucleation, coalescence, and growth. Subsequently, the pH-responsive behaviors of vesicles and spherical micelles have been explored by tuning the protonation degree of pH-responsive arm B. The vesicles evolves from nanodisks to nanosheets, then to nanoribbons, as the protonation degree increases, corresponding to a decrease in pH value, while the spherical micelles undergoes a transition into worm-like micelles, nanosheets, and nanoribbons. Notably, the electrostatic interaction leads the counterions to form a regular hexagonal pattern in nanosheets, while an alternative distribution of charged beads has been observed in nanoribbons. Furthermore, the role of the electrostatic interaction in the morphological transition has been elucidated through the analysis of the distribution of positive and negative charges, as well as the electrostatic potential for associates.

Lowest gelation concentration in a complex-coacervate-driven self-assembly system, achieved by redox-RAFT synthesis of high molecular weight block polyelectrolytes.

The objective of this work was to synthesize high molecular weight polyelectrolyte complex (PEC) micelles that are effective in controlling the rheology of aqueous solutions at low concentrations, paving the way for industrial applications of thickeners based on the principle of electrostatic self-assembly. Redox-initiated RAFT (reversible addition-fragmentation chain-transfer) polymerization was used to obtain anionic block polyelectrolytes based on poly(sodium 2-acrylamido-2-methylpropane sulfonate) and poly(acrylamide)-poly(AMPS)-block-poly(AM) (di-block) and poly(AMPS)-block-poly(AM)-block-poly(AMPS) (tri-block), with molecular weights of 237 kDa and 289 kDa and polydispersities of 1.29 and 1.34, respectively. A random poly(AMPS)-co-poly(AM) copolymer was also synthesized for comparison. PEC micelles were obtained upon mixing with cationic poly(N-[3-(dimethylamino)propyl]methacrylamide hydrochloride) - poly(DMAPMA), forming viscoelastic gels at unprecedented low concentrations of <3 wt% for the di-block and <1 wt% for the tri-block, which to date is the lowest demonstrated gelation concentration for a synthetic PEC micelle system. Differences between tri-block and di-block architectures are discussed, with the former being more affected by the addition of salt, which is attributed to percolated network breakdown. The random co-polymer was shown not to be an effective thickener but displayed a surprising lack of phase separation upon coacervation. The assemblies were characterized using dynamic light scattering (DLS) and cryo transmission electron microscopy (cryoTEM), revealing spherical micelles with a diameter of approximately 200 nm for the diblock and a mixture of spherical micelles and network particles for the tri-block PEC micelles. The micelles were not affected by dilution down to a polymer concentration of 7.8 × 10-4% (approx. 0.03 μM). Responsiveness to salinity, pH, and temperature was studied using DLS, revealing a critical NaCl concentration of 1.1 M for the block copolymer micelles.

Temperature dependence of micelle shape transitions in copolymer solutions: the role of inter-block incompatibility.

The nature of the transition between worm-like and spherical micelles in block copolymer dispersions varies between systems. In some formulations, heating drives a transition from worms to spheres, while in other systems the same transition is induced by cooling. In addition, a sphere-worm interconversion can be accompanied either by an increase or a decrease in the core solvation, even if the direction of the temperature dependence is the same. Here, self-consistent field theory is used to provide a potential explanation of this range of behaviour. Specifically, we show that, within this model, the dependence of the transition on the incompatibility χBS of the solvophobic block B and the solvent S (the parameter most closely related to the temperature) is strongly influenced by the incompatibility χAB between B and the solvophilic block A. When χAB is small (χAB < 0.1), it is found that increasing χBS produces a transition from worm-like micelles to spheres (or, more generally, from less curved to more curved structures). When χAB is above 0.1, increasing χBS drives the system from spheres to worm-like micelles. Whether a transition is observed within a realistic range of χBS is also found to depend on the fraction of solvophilic material in the copolymer. The relevance of our calculations to experiments is discussed, and we suggest that the direction of the temperature dependence may be controlled not only by the solution behaviour of the solvophobic block (upper critical solution temperature-like versus lower critical solution temperature-like) but also by χAB.

Impact of water and oleic acid on glycerol monooleate phase transition and bi-continuous structure formation in white oil.

Production of biofuels from biological feedstocks, such as soybean oil, is an important piece of the transition to renewable energy sources. Processes have been developed to co-refine these feedstocks with traditional feedstocks, however, the high concentration of polar functional groups in biofeedstocks can cause a wide range of intermediate chemical reactions and interactions. An improved understanding of the interactions of biofeedstocks and their degradation products is needed to continue to expand the usage of biofeedstocks in fuel production. In this study, the equilibrium structures of glycerol monooleate (GMO), a common intermediate product of biofeedstock processing, in white mineral oil at a wide range of compositions, temperatures, and additional byproduct concentrations (water and/or oleic acid) were characterized using small angle X-ray scattering (SAXS). It was determined that GMO can exist as crystalline aggregates in white oil or as reverse micelles depending on the concentration and temperature. The critical micelle temperature increases significantly with increasing GMO concentration but remains relatively stable with increasing water or fatty acid concentration. Fitting of the SAXS data revealed that for many compositions, the GMO formed roughly spherical reverse micelles, however, at high water concentrations (∼1 wt%), the GMO formed elongated reverse micelles. Additionally, when >1 wt% oleic acid was added to the system, bi-continuous structures were stabilized rather than discreet reverse micelles. These results help increase our understanding of the structural behavior of biofeedstock intermediate products at concentrations and temperatures relevant to biofuel production and can enable processers to design systems and products that can either leverage or prevent these interactions for improved processing performance.

Impact of a poly(ethylene glycol) corona block on drug encapsulation during polymerization induced self-assembly.

Polymerization induced self-assembly (PISA) provides a facile platform for encapsulating therapeutics within block copolymer nanoparticles. Performing PISA in the presence of a hydrophobic drug alters both the nanoparticle shape and encapsulation efficiency. While previous studies primarily examined the interactions between the drug and hydrophobic core block, this work explores the impact of the hydrophilic corona block on encapsulation. Poly(ethylene glycol) (PEG) and poly(2-hydroxypropyl methacrylate) (PHPMA) are used as the model corona and core blocks, respectively, and phenylacetic acid (PA) is employed as the model drug. Attachment of a dithiobenzoate end group to the PEG homopolymer - transforming it into a macroscopic reversible addition-fragmentation chain transfer agent - causes the polymer to form a small number of nanoscopic aggregates in solution. Adding PA to the PEG solution encourages further aggregation and macroscopic phase separation. During the PISA of PEG-PHPMA block copolymers, inclusion of PA in the reaction mixture promotes faster nucleation of spherical micelles. Although increasing the targeted PA loading from 0 to 20 mg mL-1 does not affect the micelle size or shape, it alters the drug spatial distribution within the PISA microenvironment. PA partitions into either PEG-PHPMA micelles, deuterium oxide, or other polymeric species - including PEG aggregates and unimer chains. Increasing the targeted PA loading changes the fraction of drug within each encapsulation site. This work indicates that the corona block plays a critical role in dictating drug encapsulation during PISA.

Influence of hydrophilic block length on the aggregation properties of polyglycidol-polystyrene-polyglycidol copolymers.

Amphiphilic triblock copolymers, polyglycidol-polystyrene-polyglycidol (PGL-PS-PGL), were synthesised via anionic polymerization starting from the synthesis of a polystyrene macroinitiator with 60 styrene units in the block terminated by ethylene oxide. Poly(ethoxyethyl glycidyl ether) blocks of different lengths were created on both sides of the macroinitiator. By removing the ethoxyethyl blocking groups, PGL-PS-PGL copolymers containing polyglycidol blocks with DP 11, 23, 44 and 63 were received. Their structures were determined by NMR and FTIR. The hydrophilicity of PLG-PS-PGL films was studied upon exposure to water vapour. To perform the copolymers' aggregation in water, the samples were dialysed from DMF into water. The critical concentration of their micellisation (CMC) was determined by measuring the absorbance of the 1,6-diphenylhexa-1,3,5-triene (DPH) probe and the intensity of light scattered by the copolymers' solution as a function of concentration. CMC values increased with increasing the number of hydrophilic glycidol units in the copolymer chain. The sizes of aggregates formed slightly above the critical concentration were measured by dynamic light scattering (DLS), and particles were imaged by cryo-TEM. Cryo-TEM pictures showed the presence of regular micelles in copolymer dispersions. For copolymers with shorter PGL chains aggregated partices were detected. Moreover, cryo-TEM demonstrated that the copolymers with a polyglycidol block of DP = 63 formed regular spherical micelles that formed 2D ordered organisation on the surface. X-ray measurements showed the formation of a partially crystallised PS core in the micelle's interior. The aggregates of all copolymers were stable. Their sizes did not change after one year of storage. The particles did not disassociate even after diluting their dispersions to a concentration 10 times lower than the critical concentration.

Patchy stereocomplex micelles as efficient compatibilizers for polymer blends

Patchy spherical micelles prepared via stereocomplex-driven self-assembly are applied as efficient compatibilizers for highly immiscible polystyrene/poly(tert-butyl methacrylate) blends.

Dilute suspensions of Janus rods: the role of bond and shape anisotropy.

Nanometer-sized clusters are often targeted due to their potential applications as nanoreactors or storage/delivery devices. One route to assemble and stabilize finite structures consists of imparting directional bonding patterns between the nanoparticles. When only a portion of the particle surface is able to form an inter-particle bond, finite-size aggregates such as micelles and vesicles may form. Building on this approach, we combine particle shape anisotropy with the directionality of the bonding patterns and investigate the combined effect of particle elongation and surface patchiness on the low density assembly scenario. To this aim, we study the assembly of tip-functionalised Janus hard spherocylinders by means of Monte Carlo simulations. By exploring the effects of changing the interaction strength and range at different packing fractions, we highlight the role played by shape and bond anisotropy on the emerging aggregates (micelles, vesicles, elongated micelles, and lamellae). We observe that shape anisotropy plays a crucial role in suppressing phases that are typical to spherical Janus nanoparticles and that a careful tuning of the interaction parameters allows promoting the formation of spherical micelles. These finite-size spherical clusters composed of elongated particles might offer more interstitials and larger surface areas than those offered by micelles of spherical or almost-spherical units, thus enhancing their storage and catalytic properties.

Amphiphilic electrolyte additive as an ion-flow stabilizer enables superb zinc metal batteries

3-(Hydroxy(phenyl)phosphoryl)propanoic acid (HPA) has a strong coordination ability for Zn2+/metal anodes which not only form sphere micelles that promote the uniform transmission of Zn2+ but also enhance the preferential adsorption on anodes.

Study of in vitro poorly soluble drug solubility into fasted state simulated intestinal fluid reflective of in vivo gastrointestinal variability

Solubilityand dynamic light scattering (DLS) studies of three poorly soluble drugs(naproxen, indomethacin and phenytoin) in simulated intestinal fluid (SIF) werecarried out in order to calculate the number of drug molecules per micelle basedon the assumption of monodisperse spherical micelles. As the total amphiphileconcentration increased in the SIF the solubility of the drug also increased.The size of the micelles formed decreased with increasing amphiphileconcentration in combination with drug and the number of drug molecules permicelle decreased. Further work is planned to provide more information of theparticle size and geometry of the drug loaded micelles.

Effect of Hydrophobic Chain Length in Amphiphilic Chitosan Conjugates on Intracellular Drug Delivery and Smart Drug Release of Redox-Responsive Micelle.

Three redox-sensitive nanocarriers were rationally designed based on amphiphilic low molecular weight chitosan-cystamine-octylamine/dodecylamin/cetylamine (LC-Cys-OA, LC-Cys-DA, LC-Cys-CA) conjugates containing disulfide linkage for maximizing therapeutic effect by regulating hydrophobic interaction. The resultant spherical micelles had the characteristics of low CMC, suitable size, excellent biosafety and desired stability. The drug-loaded micelles were fabricated by embedding doxorubicin (Dox) into the hydrophobic cores. The effect of hydrophobic chain lengths of amphiphilic conjugates on encapsulation capacity, redox sensitivity, trigger-release behavior, cellular uptake efficacy, antitumor effect and antimigratory activity of Dox-loaded micelles was systematically investigated. Studies found that Dox-loaded LC-Cys-CA micelle had superior loading capacity and enhanced redox sensitivity compared with the other two micelles. Release assay indicated that the three Dox-loaded micelles maintained sufficiently stability in normal blood circulation but rapidly disintegrated in tumor cells. More importantly, the LC-Cys-CA micelle with a longer hydrophobic chain length exhibited a higher accumulative Dox release percentage than the other two micelles. Additionally, an increase in hydrophobic chain lengths of amphiphilic conjugates improved cellular uptake efficiency, antitumor effect and antimigration activity of Dox-loaded micelles, which could be explained by enhanced loading ability and redox sensitivity. Our research was expected to provide a viable platform for achieving a desired therapeutic efficacy via the alteration of hydrophobic interaction.

Facile Posttreatment of Self‐Assembled Monolayers for Efficient Inverted Perovskite Solar Cells

The application of self‐assembled molecules (SAM) allows inverted‐structural perovskite solar cells to accomplish high efficiencies, by virtue of their high hole conductivity and negligible parasitic absorption. However, amphiphilic SAM tend to form spherical micelles in commonly used alcoholic solvents, leading to aggregation in the resulting film. In addition, hydrophobic groups of SAM are exposed to the surroundings after being deposited on transparent substrates, responsible for the poor crystallinity of perovskite and interface quality. Therefore, it is important to study the treatment of SAM layers or SAM/perovskite interfaces for better device performance. Herein, dual regulation of SAM and perovskite is achieved via a facile posttreatment by formamidinium chloride (FACl) solution in N,N‐Dimethylformamide. First, by taking advantage of solvent rinsing, aggregations at the surface of SAM layer are alleviated. Second, FACl on the top of the SAM layer assists the crystallization of perovskite through interaction with PbI2 and reduces the defect concentration via passivating the halide vacancies at the buried interface of the device. With a more uniform SAM layer, better‐crystallized perovskite, and suppressed nonradiative recombination between them, the power conversion efficiency of the target device is improved by 20%.

Ordered nanoassemblies from self‐assembly of amphiphilic molecule containing pillar[5]arene and azobenzene groups

AbstractThe derivatization of pillar[n]arenes is a prerequisite for endowing them with functions, as well as enriching the application of pillar[n]arene materials in advanced material science. Herein, we report the self‐assembly of amphiphilic rim‐differentiated pillar[5]arene (H1). One side of the pillar[5]arene is composed of hydrophilic poly(ethylene oxide) chains, benzene and azobenzene groups connected with ether bonds, and the other side is composed of ethoxy groups. In CHCl3 solvent, the amphiphile H1 self‐assembled into spherical micelles, while in H2O/THF mixed solvent H1 self‐assembled into nanorod‐like assemblies. Interestingly, addition of a guest molecule composed of tetraphenylethene and hexanenitrile groups (G1) to the CHCl3 solution of H1 produces large sheet aggregates via the strong π–π stacking of rod segments. The reversible transformation between the nanosheet assemblies of host–guest complexes and nanoparticles is achieved by addition of the guest molecule 1,4‐butylamine (G2) and pillar[5]arene with ethoxy groups as competitive molecules. Notably, worm‐like and nanorod micelles of H1 were constructed in H2O/THF solution triggered by light irradiation, which assemblies can be used as photosensitive erasable writing materials. © 2023 Society of Industrial Chemistry.

Selective Uptake Into Inflamed Human Intestinal Tissue and Immune Cell Targeting by Wormlike Polymer Micelles.

Inflammatory bowel disease (IBD)has become a globally prevalent chronic disease with no causal therapeutic options. Targeted drug delivery systems with selectivity for inflamed areas in the gastrointestinal tract promise to reduce severe drug-related side effects. By creating three distinct nanostructures (vesicles, spherical, and wormlike micelles) from the same amphiphilic block copolymer poly(butyl acrylate)-block-poly(ethylene oxide) (PBA-b-PEO), the effect of nanoparticle shape on human mucosal penetration is systematically identified. An Ussing chamber technique is established to perform the ex vivo experiments on human colonic biopsies, demonstrating that the shape of polymeric nanostructures represents a rarely addressed key to tissue selectivity required for efficient IBD treatment. Wormlike micelles specifically enter inflamed mucosa from patients with IBD, but no significant uptake is observed in healthy tissue. Spheres (≈25nm) and vesicles (≈120nm) enter either both normal and inflamed tissue types or do not penetrate any tissue. According to quantitative image analysis, the wormlike nanoparticles localize mainly within immune cells, facilitating specific targeting, which is crucial for further increasing the efficacy of IBD treatment. These findings therefore demonstrate the untapped potential of wormlike nanoparticles not only to selectively target the inflamed human mucosa, but also to target key pro-inflammatory cells.

Effects of Dodecyltrimethylammonium chloride (DAC) micelle’s shape transition on chemical enhanced oil recovery; experimental & mathematical modeling study

Surfactants are widely used for enhanced oil recovery (EOR) purposes by reducing interfacial tension (IFT) of oil–water phases and wettability alteration. Some surfactants with viscoelastic properties can be used as mobility control agents due to enhanced viscosity resulting from the spherical-to-cylindrical shape transition of micelles. Dodecyltrimethylammonium chloride (DAC) shows viscoelastic behavior coupled with dominantly cylindrical shape of the micelle in ambient conditions. Nevertheless, using DAC as an IFT reduction and mobility control agent needs to be industrialized for actual operating conditions. In this study, DAC, as a cationic surfactant, was experimentally studied in reservoir conditions considering dominantly cylindrical micelles for the first time. Results showed that the viscosity of DAC solution is a strong function of DAC concentration, especially at high temperature and high salinity conditions, while it does not depend on pressure significantly. Transmission electron microscope (TEM) images were taken for a better understanding of DAC micellar structures. Analysis of the TEM results indicated the shape transition of the micelles from small spherical to large cylindrical at higher concentrations of DAC. IFT of DAC microemulsion was studied for wide ranges of temperature and DAC concentration, ruling out any significant effect of the temperature on the IFT trend line. A general mathematical model for predicting the viscosity of surfactant solution was developed and evaluated for real reservoir conditions by including all effective terms. Results showed a very good agreement with experimental data of DAC and Cetyltrimethyl ammonium bromide (CTAB, as per previous studies), justifying the applicability of the developed model for predicting the viscosity wherever experimental data is unavailable. Core flood tests were performed with saltwater (SW) and DAC solutions with spherical (SS) and cylindrical (SC) micelles as injecting phases for evaluation of IFT reduction and mobility control effects. Results showed an additional recovery factor of 13 % for SS and 23 % for SC in comparison with SW injection.

Molecular dynamics study on micelle-small molecule interactions: developing a strategy for an extensive comparison

Theoretical predictions of the solubilizing capacity of micelles and vesicles present in intestinal fluid are important for the development of new delivery techniques and bioavailability improvement. A balance between accuracy and computational cost is a key factor for an extensive study of numerous compounds in diverse environments. In this study, we aimed to determine an optimal molecular dynamics (MD) protocol to evaluate small-molecule interactions with micelles composed of bile salts and phospholipids. MD simulations were used to produce free energy profiles for three drug molecules (danazol, probucol, and prednisolone) and one surfactant molecule (sodium caprate) as a function of the distance from the colloid center of mass. To address the challenges associated with such tasks, we compared different simulation setups, including freely assembled colloids versus pre-organized spherical micelles, full free energy profiles versus only a few points of interest, and a coarse-grained model versus an all-atom model. Our findings demonstrate that combining these techniques is advantageous for achieving optimal performance and accuracy when evaluating the solubilization capacity of micelles.Graphical abstractAll-atom (AA) and coarse-grained (CG) umbrella sampling (US) simulations and point-wise free energy (FE) calculations were compared to their efficiency to computationally analyze the solubilization of active pharmaceutical ingredients in intestinal fluid colloids.

Micelle-mediated chemiluminescence of 6-aza-2-thiothymine-protected gold nanoclusters for carbazochrome sodium sulfonate detection

Chemiluminescence (CL) intensity of luminol-H2O2 system was dramatically enhanced by cetyltrimethylammonium bromide (CTAB) micelle-mediated 6-aza-2-thiothymine-protected gold nanoclusters (ATT-AuNCs). It is proved that spherical micelles of CTAB in aqueous solution improved the dispersity of ATT-AuNCs, thus enhancing their catalytic activity, which brought in the increased CL intensity of luminol-H2O2 system. Carbazochrome sodium sulfonate (CSS) with a hemostatic containing tetrahydroindole structure broke the spherical micelles and notably quenched the CL intensity of luminol-H2O2-CTAB-ATT AuNCs system. Based on these results, a simple, fast, and sensitive CL method has been developed for the detection of CSS with a linear range of 0.25–25 μM and a detection limit of 0.11 μM. The method has also been successfully applied to the determination of CSS in serum with satisfied recoveries in the range of 89.6 % to 103.7 %. This study not only provides an effective approach for CSS detection but also paves the way for AuNCs-based CL applications.

Effect of sodium dodecyl sulfate on preferential degradation of naphthalene by thermally activated persulfate: Implications for soil flushing solution reuse

Various flushing solutions that contain hydrophobic organic compounds and surfactants are generated during surfactant-enhanced soil flushing processes. How to effectively remove the target pollutants while minimizing the degradation of surfactants for reuse of the flushing solutions has become a major problem. A series of batch experiments were conducted to investigate the preferential degradation mechanisms of naphthalene by sodium dodecyl sulfate (SDS) as well as the effect of SDS concentration on the degradation efficiency using a competitive kinetic method. In addition, the effects of persulfate (PS) dosage, temperature, and pH on the degradation efficiency of naphthalene were also studied, and a prediction model based on response surface methodology (RSM) was built to optimize the preferential degradation of naphthalene. One-dimensional column flushing experiments were performed to evaluate the feasibility of reusing soil flushing solutions at the predicted PS dosage. Results show that: (i) SDS inhibited naphthalene degradation owing to competitive oxidation and micellar protection, with a decreasing degradation rate constant as SDS concentration increased. However, naphthalene was still degraded by reactive oxygen species (ROS) at a higher rate than SDS, indicating the preferential degradation of naphthalene. When the concentration of SDS increased from 5 to 10 times of critical micelle concentration (CMC; 8.2 mM), the ratio for rate constants of naphthalene to SDS (kNAP/kSDS) decreased significantly from 31.61 to 3.38, illustrating the obvious effect of SDS concentration on preferential degradation of naphthalene; (ii) The formation of single-chambered vesicles with a higher thermodynamic stability was observed at 10 CMC, compared to the spherical micelles formed at 5 CMC. The accessibility of naphthalene to ROS was greatly reduced at 10 CMC, resulting in a significant reduction in kNAP/kSDS value. Moreover, the method in which ROS attacked naphthalene in surfactant micelles varied with SDS concentration, which also impacted the preferential degradation of naphthalene; (iii) Under the optimal PS dosage predicted by the RSM model, a good reusability of SDS was observed in the soil flushing solutions after thermally activated PS oxidation, with a significant reduction on the toxic risk of soil after flushing.

Cryo-TEM Reveals the Influence of Multivalent Charge and PEGylation on Shape Transitions in Fluid Lipid Assemblies: From Vesicles to Discs, Rods, and Spheres.

Lipids, and cationic lipids in particular are of interest as delivery vectors for hydrophobic drugs such as the cancer therapeutic paclitaxel, and the structures of lipid assemblies affect their efficacy. We investigated the effect of incorporating the multivalent cationic lipid MVL5 (+5e) and poly(ethylene glycol)-lipids (PEG-lipids), alone and in combination, on the structure of fluid-phase lipid assemblies of the charge-neutral lipid 1,2-dioleoyl-sn-glycero-phosphocholine (DOPC). This allowed us to elucidate lipid-assembly structure correlations in sonicated formulations with high charge density, which are not accessible with univalent lipids such as the well-studied DOTAP (+1e). Cryogenic transmission electron microscopy (cryo-TEM) allowed us to determine the structure of the lipid assemblies, revealing diverse combinations of vesicles and disc-shaped, worm-like, and spherical micelles. Remarkably, MVL5 forms an essentially pure phase of disc micelles at 50 mol % MVL5. At a higher (75 mol %) content of MVL5, short- and intermediate-length worm-like micellar rods were observed, and in ternary mixtures with PEG-lipid, longer and highly flexible worm-like micelles formed. Independent of their length, the worm-like micelles coexisted with spherical micelles. In stark contrast, DOTAP forms mixtures of vesicles, disc micelles, and spherical micelles at all studied compositions, even when combined with PEG-lipids. The observed similarities and differences in the effects of charge (multivalent versus univalent) and high curvature (multivalent charge versus PEG-lipid) on the assembly structure provide insights into parameters that control the size of fluid lipid nanodiscs, relevant for future applications.