Micelle Size Research Articles

Effect of Changing Interfacial Tension on Fragmentation Kinetics of Block Copolymer Micelles

Micelle fragmentation, one of the key mechanisms responsible for equilibration of kinetically trapped micelles, is investigated for block copolymer micelles in ionic liquids (ILs). In particular, the role of driving force for micelle fragmentation is studied by altering the solvent quality after micelle preparation, amounting to a jump in interfacial tension γ between solvent and the micelle core. Direct dissolution of a 1,2-polybutadiene-b-poly(ethylene oxide) (PB-b-PEO) copolymer (Mn = 17.5 kDa and fPEO = 0.38) in the ionic liquid [C2mim][TFSI] results in large micelles with average size ⟨Rh⟩o ≈ 68 nm and dispersity Đ ≈ 1.27. The solution of the as-prepared micelles is then diluted by the careful addition of a second ionic liquid [C10mim][TFSI] having lower γ with the micelle core, such that the micelles remain unaffected. The γ and hence the quality of the solvent mixture were controlled by the degree of dilution. The choice of the second solvent is based on the measurement of γ for a series of [Cxmim][TFSI] ILs with 1-2-polybutadiene homopolymer, carried out using a pendant drop test. Diluting the micelles by adding another ionic liquid with lower γ tends to decrease the equilibrium micelle size, which, in turn, enhances the driving force for fragmentation of the bigger as-prepared micelles, represented by increase in the ratio of aggregation numbers Q/Qeq. Subjecting the diluted micellar solution to temperature-jump to 170 °C followed by thermal annealing leads to fragmentation of the as-prepared micelles to attain a near-equilibrium state. The micelles are characterized using an in situ dynamic light scattering (DLS) technique to observe the time evolution of average micelle size, from which the relaxation time is obtained. Additionally, small-angle X-ray scattering (SAXS) and cryogenic transmission electron microscopy (TEM) measurements were carried out to obtain the micelle core size and distribution in the micellar solutions before and after fragmentation. The enhancement in the driving force achieved by controlling the amount of low γ solvent resulted in faster fragmentation; the characteristic fragmentation time decreases monotonically on increasing the size ratio Q/Qeq from 1.2 to 5.

Dilution Driven Self-assembly and Re-entrant Phase Transition in Molecular Hydrogels

TX-100 molecular hydrogels exhibited re-entrant melt-gel-sol phase transition driven solely by dilution, which sequentially altered the self-assembly of the micellar formations and their population was investigated through the monitoring of the physical parameters namely, solution viscosity, particle size histogram, ergodicity, and gel rigidity modulus. This phenomenon was noticed at 20°C in the TX-100 concentration region of 0.2 to 1.2 M much above the critical micellar concentration of 0.22 mM. The particle size histograms revealed the presence of spherical micelles (size »3 nm) in the solution ([TX-100] < 0.5 M) which formed entangled wormlike cylindrical micelles (apparent hydrodynamic radius » 50 nm) when (0.5 M< [TX-100] < 0.9 M) giving rise to a gel-like structure. Further increase in the TX-100 concentration increased the propensity of these wormlike cylindrical micelles that got randomly distributed creating a dense melt phase. Interestingly, we observed transition solely driven by dilution which defined complete re-entrant behavior at room temperature. These molecular gels could be created by dilution of the melt or concentration of the sol unlike in the polymer gels. Remarkably, this hitherto little known unique phenomenon was exhibited by a simple system of non-ionic surfactant solution. Thus, we have a hydration reversible gel at our disposal which has a special place in soft matter arena.

Stabilized Reversed Polymeric Micelles as Nanovector for Hydrophilic Compounds.

Small hydrophilic drugs are widely used for systemic administration, but they suffer from poor absorption and fast clearance. Their nanoencapsulation can improve biodistribution, targeted delivery, and pharmaceutical efficacy. Hydrophilics are effectively encapsulated in compartmented particles, such as liposomes or extracellular vesicles, which are biocompatible but poorly customizable. Polymeric vectors can form compartmental structures, also being functionalizable. Here, we report a system composed of polymeric stabilized reversed micelles for hydrophilic drugs encapsulation. We optimized the preparation procedure, and calculated the critical micellar concentration. Then, we developed a strategy for stabilization that improves micelle stability upon dilution. We tested the drug loading and delivery capabilities with creatine as a drug molecule. Prepared stabilized reversed micelles had a size of around 130 nm and a negative z-potential around -16 mV, making them functional as a drug carrier. The creatine cargo increased micelle size and depended on the loading conditions. The higher amount of loaded creatine was around 60 μg/mg of particles. Delivery tests indicated full release within three days in micelles with the lower cargo, while higher loadings can provide a sustained release for longer times. Obtained results are interesting and encouraging to test the same system with different drug cargoes.

TPGS-chitosan conjugated mucoadhesive micelles of brinzolamide for glaucoma therapy: In vitro and in vivo evaluation

Micelle is a promising avenue for ophthalmic drug development technology and an especially suitable choice for hydrophobic drugs. The aim of this investigation was to synthesize Brinzolamide (BRZ) loaded d-alpha-tocopherol polyethylene glycol succinate (TPGS) - Chitosan conjugated micelles (BTCM) prepared by solvent evaporation method and to investigate their intraocular pressure (IOP) reducing efficacy for the management of glaucoma. The formulated BTCM was evaluated with various parameters such as size, zeta potential, morphology, percentage drug entrapment efficiency, drug loading capacity, and mucoadhesion strength, in-vitro and ex-vivo release. In-vivo anti-glaucoma efficacy study was conducted by glucocorticoid-induced glaucoma rabbit eye model and evaluated with the Marketed formulation (MF). The optimized formula showed a micelle size of 74.32±1.46 nm, and suitable physicochemical properties and in-vitro release mechanism were observed in that biphasic erosion-diffusion pattern of BRZ releases up to 8 h. The Ex-vivo corneal penetration of BRZ from BTCM showed a higher permeability rate than MF. Additionally, BTCM showed sustained release of BRZ, better corneal tissue compatibility, and improved anti-glaucoma potential, as compared to MF. The results concluded that BTCM is the suitable option for anti-glaucoma therapy because of its capability to improve ocular mucoadhesion of loaded BRZ via the interaction with the mucous membrane of the corneal surface.

Feasibility evaluation of novel anionic-nonionic gemini surfactants for surfactant-enhanced aquifer remediation

Surfactant-enhanced aquifer remediation (SEAR) can effectively remove residual dense non-aqueous phase liquids. In this work, a series of environment-friendly anionic-nonionic gemini surfactants, namely, ethylene glycol succinate polyoxyethylene sulfonate (GEOnS-m, n = 3, 5 and 7; m = 10 and 12), were synthesized and evaluated for application in SEAR. The critical micelle concentrations of GEOnS-m were 2.14 × 10−3–1.62 × 10−2 mM, and the molar solubilization ratios of GEOnS-m for tetrachloroethylene were 1.93–3.44, which were 1.5–5 times higher than traditional surfactants. The GEOnS-m solutions remained stable at 5–25 °C, 50 mM salt, and pH = 5.0–9.0. The micelle size decreased as the temperature decreased, which reduced the solubilization capacity (24.9%–37.0%) of the GEOnS-m solutions. Inorganic salts could improve the solubilization capacity of the GEOnS-m solutions by promoting micelle polymerization and increasing the hydrophobic core volume for solubilizing tetrachloroethylene. This work found that 0.80%–4.00% of GEOnS-m adsorbed on the media during simulated column flushing, which was less than the traditional surfactants due to stronger electrostatic repulsion between the micelles and the media. Meanwhile, the solubilization capacity of GEOnS-m was positively correlated with the hydrophobic carbon chain length, while, the adsorption amount in the media and application cost of GEOnS-m were positively correlated with the EO number and negatively correlated with the hydrophobic carbon chain length. Comprehensive evaluation results revealed that GEO3S-12 was preferred for SEAR. This work not only developed suitable surfactants for SEAR but also attempted to further the rational design of surfactants for diverse applications by combining different functional groups into one molecule.

Computational analysis of water dynamics in AOT reverse micelles

Aerosols can be modeled for detailed investigations using reverse micelles in the laboratory as well as in computational simulations. A long-standing question in the description of confined water under these conditions is that of a two-state model of core – interface or a three-state model of core – intermediate – interface. In this work, we present results of analysis of water dynamics inside reverse micelles from fully atomistic molecular dynamics simulations. The size and composition of reverse micelles is expressed through w0, the ratio of the number of water molecules to the number of surfactant molecules. Reverse micelles of diverse sizes, with w0 ranging from 5 to 20, were constructed with Sodium bis(2-ethylhexyl) sulfosuccinate (AOT) surfactant and simulated within isooctane solvent. Residence time and diffusion coefficients, in the simulations, both behaved increasingly like bulk water with the increase in size of reverse micelles. Rotational anisotropy autocorrelation was modeled using exponential functions in the short time range of 10–20 ps and longer time data were modeled as a power law fit. Similarly, the diffusion of water in the reverse micelles was also modeled on a power law fit. All these metrics demonstrate a clear progression towards bulk water behavior as the reverse micelle size increases. Additionally, our results also support a 3-layer model of water in a reverse micelle of core – intermediate – interface. These results extend the understanding of water dynamics in reverse micelles and provide further evidence for the 3-layer model.

Productive traits of daughters of sires of Holstein breed depending on the country of origin and genotype according to gene CSN3

Numerous studies have proven the effect of the allele B of the kappa casein gene (CSN3) on protein milk content, because the protein controlled by this allele has a number of distinctive features: difference in micelle size, higher protein content, greater stability when heated and frozen, better properties for cheese making (shorter coagulation time, coagulate of a denser consistency and a higher cheese yield by 5–10 %). The purpose of the research was to study the frequency of occurrence of alleles and genotypes of the kappa casein gene (CSN3) in sires of Holstein breed, depending on the country of origin, and to trace the infl uence of the identifi ed genotypes on the productive traits of the daughters of sires (milk yield, fat and protein content in milk). It was revealed that the highest frequency of occurrence of the desired allele B kappa-casein was found in sires of Dutch and Canadian breeding 33,3 and 34,7 %, respectively. The highest frequency of occurrence of homozygous genotype CSN3 BB was found in Dutch–bred sires – 22,2 %. The frequency of occurrence of the heterozygous CSN3 AB genotype was higher than others in Canadian–bred sires – 36,1 %. The best milk yield was characterized by the daughters of Canadian and Dutch-bred sires with CSN3 AA genotype, among the daughters of Germanbred sires it was CSN3 AB. The highest amount of fat in milk of daughters of sires of Dutch origin was found in cows with the sire’s genotype AB, in daughters of sires of German and Canadian breeding itwas AA, but the indicators practically did not differ from those of daughters of sires with the genotype AB. The highest protein content in milk was found in the daughters of sires of diff erent origins with the allele B of the kappa-casein gene.

Naphthyl-Poly(S-((2-carboxyethyl)thio)-l-cysteine) Peptide Amphiphiles with Different Degrees of Polymerization: Synthesis, Self-Assembly, pH/Reduction-Triggered Drug Release, and Cytotoxicity.

Four peptide amphiphiles (PA1-4) with different degrees of polymerization (DP = 40, 15, 10, and 6) were synthesized by Fuchs-Farthing and ring-opening polymerization followed by post-polymerization modification, as fully characterized by 1H NMR, FT-IR, gel permeation chromatography, and circular dichroism (CD) spectroscopy. It was found that PAs could self-assemble to form regular spherical micelles in low-concentration (about 1 mg/mL) aqueous solution, which had different contents of secondary structures and mainly adopted random coil conformations. The water solubility of PAs increases with the increase of DP, the polypeptide chain stretches randomly in water, the β-sheets decrease, and the random coil conformations dominate. When the pH of PA solution decreases or increases, intramolecular hydrogen bonds break, and molecular chains stretch, leading to a decrease of α-helix, turn conformations, and an increase of β-sheets. Meanwhile, the particle size of micelles increases. At around 0.4 mg/mL, the hemolysis ability of PA2 is negligible at pH 7.4 and 6.5 and about 33% at pH 5.5. Cisplatin (CDDP) was linked to micelles by coordination bonds to explore their potential as drug carriers, exhibiting controlled pH and reduction in dual drug release effects. MTT assay showed that the HeLa cell viability was 78% when cultured in the 13.5 μg/mL PA2 blank micelles for 2 days, while the cell viability was 60% in the CDDP-loaded micelles. Furthermore, a high concentration of PA2 (about 100 mg/mL) could self-assemble into a fibrous hydrogel at pH 5.5, which self-healed 2 h after incision and self-degraded 71% within 14 days. The CDDP-loaded fiber hydrogel exhibited a sustained release effect similar to the CDDP-loaded micelles. The cytotoxicity of CDDP-loaded fibers at 48 h was detected to be the same as that of the same amount of CDDP, and the cell viability was 7%. Therefore, we provide a new strategy for the synthesis of amphiphilic peptides with potential applications in nano-drug carriers and cancer therapy.

Characterization and Evaluation of Rapamycin-Loaded Nano-Micelle Ophthalmic Solution.

Rapamycin-loaded nano-micelle ophthalmic solution (RAPA-NM) offers a promising application for preventing corneal allograft rejection; however, RAPA-NM has not yet been fully characterized. This study aimed to evaluate the physicochemical properties, biocompatibility, and underlying mechanism of RAPA-NM in inhibiting corneal allograft rejection. An optimized RAPA-NM was successfully prepared using a polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol (PVCL-PVA-PEG) graft copolymer as the excipient at a PVCL-PVA-PEG/RAPA weight ratio of 18:1. This formulation exhibited high encapsulation efficiency (99.25 ± 0.55%), small micelle size (64.42 ± 1.18 nm), uniform size distribution (polydispersity index = 0.076 ± 0.016), and a zeta potential of 1.67 ± 0.93 mV. The storage stability test showed that RAPA-NM could be stored steadily for 12 weeks. RAPA-NM also displayed satisfactory cytocompatibility and high membrane permeability. Moreover, topical administration of RAPA-NM could effectively prevent corneal allograft rejection. Mechanistically, a transcriptomic analysis revealed that several immune- and inflammation-related Kyoto Encyclopedia of Genes and Genomes (KEGG) pathways were significantly enriched in the downregulated genes in the RAPA-NM-treated allografts compared with the rejected allogenic corneal grafts. Taken together, these findings highlight the potential of RAPA-NM in treating corneal allograft rejection and other ocular inflammatory diseases.

Multilamellar spherical micelles of alkali lignin: dissipative particle dynamics simulations.

Lignin has an immense potential for the production of lignin-based functional materials. In this work, effect of 2-chloro-ethyltrimethyl ammonium chloride (AC)-grafted alkali lignin (AL) on the morphologies in water was investigated by dissipative particle dynamics (DPD) simulations. The results showed that AL molecules formed spherical micelles, but the corresponding phenylpropane units of AL were randomly distributed in spherical micelles. However, AC-grafted modification of phenolic hydroxyl groups in AL led to the formation of multilamellar spherical micelles. The formation of multilamellar spherical micelles of AL mainly went through four stages: small clusters, larger aggregates with a core-shell structure, trilaminar, and multilamellar spherical micelles. AL molecules resulted in dimethomorph molecules being randomly distributed in the spherical micelle, while the dimethomorph molecules were perfectly entrapped into the spherical micelles of AC-grafted AL. Various molecular weights of AL had no effect on the formation and size of multilamellar spherical micelles. With increasing the content of AC-grafted AL, small clusters, multilamellar spherical micelles, tube-like, and lamellar aggregates were observed successively. This work highlights the potential of lignin to prepare monodispersed lignin-based functional colloidal spheres. Coarse-grained beads were performed energy minimization, geometric optimization, NPT ensemble (298 K and 1.0 bar), and NVT ensemble (298 K) calculations. DPD simulations were carried out at 300,000 steps in a 30×30×30 Rc3 cubic box with Materials Studio 7.0 program.

Binding of Ca2+ Ions to Alkylbenzene Sulfonates: Micelle Formation, Second Critical Concentration and Precipitation.

Anionic surfactants, such as sodium linear alkylbenzene sulfonates (NaLAS), are utilized in various fields, including industry, household, and agriculture. The efficiency of their use in aqueous environments is significantly affected by the presence of cations, Ca2+ and Mg2+ in particular, as they can decrease the concentration of the surfactant due to precipitation. To understand cation-sulfonate interactions better, we study both NaLAS colloidal solutions in the presence of CaCl2 and precipitates forming at higher salt concentrations. Upon addition of CaCl2, we find the surface tension and critical micelle concentration of NaLAS to decrease significantly, in line with earlier findings for alkylbenzylsulfonates in the presence of divalent cations. Strikingly, an increase in the surface tension is discernible above 0.6 g L-1 NaLAS, accompanied by the decrease of apparent micelle sizes, which in turn gives rise to transparent systems. Thus, there appears to be a second critical concentration indicating another micellar equilibrium. Furthermore, the maximum salt tolerance of the surfactant is 0.1 g L-1 Ca2+, above which rapid precipitation occurs yielding sparingly soluble CaLAS2∙2H2O.

In vitro Characterization of Polyethyleneimine-Oleic Acid Cationic Micelle as a Novel Protein Carrier.

Nanotechnology has introduced valuable carriers for vaccine delivery. The success of vaccination depends on many factors, such as the intact and safe presentation of vaccine candidates to immune cells. We have conjugated branched PEI-2k and oleic acid (OL) as the building block of the cationic micelle. We aimed to introduce a novel carrier for vaccine candidates. We conjugated polyethyleneimine and OL (POA) to synthesize the building blocks of cationic micelles. The critical micelle concentration (CMC), size and zeta potential of micelles, and their stability in 60 days were determined. Loading, encapsulation efficiency, and in vitro release study were assessed using bovine serum albumin (BSA) as a protein model. Furthermore, the cytotoxicity and hemocompatibility of developed nanosized micelles were evaluated to ascertain the biocompatibility of fabricated micelles. Cell uptake of cationic micelles in the macrophage cell line was also followed up. The conjugation of two polymer parts was confirmed by Fourier transform infrared spectroscopy and 1H nuclear magnetic resonance techniques. The CMC of the developed micelles was around 5.62 × 10-8 mg/ ml, whereas the loading and encapsulation efficiencies were 16.5% and 70%, respectively. The size and zeta potential of the cationic micelles were 96.53 ± 18.53 nm and 68.3 mV, respectively. The release of BSA from POA micelles after 8 and 72 hours was 8.5% and 82%, respectively. Finally, fluorescence microscopy showed that the prepared micelles were successfully and effectively taken up by RAW264.7 cells. These results may provide a cutting-edge vaccine delivery solution and open up a new avenue for future vaccine research.

Micelle Formation of Dodecanoic Acid with Alkali Metal Counterions.

Alkali series with different atomic numbers affect the physicochemical properties of aqueous solutions. The micellar properties of aqueous solutions of dodecanoate as surfactants were measured by changing the counterions (C12-Na, C12-K, C12-Rb, and C12-Cs). A plot of Krafft temperature vs. alkali metal atomic number showed a downward convex curve, with its minimum temperature (20°C) in the C12-K system. By contrast, a plot of the critical micelle concentration (CMC) vs. alkali metal atomic number exhibited an upward convex curve with the maximum CMC (25.6 mmol L-1) at C12-K. Furthermore, the minimum surface tension (γ min ) of the solution at the CMC increased with increasing atomic number (C12-Na ≈ C12-K < C12-Rb < C12-Cs). The size of the dodecanoate micelles decreased with increasing atomic number. The ionization degree of the micelles also increased with increasing atomic number of the alkali metal. Small-angle X-ray scattering (SAXS) measurements revealed that alkali dodecanoate micelles formed spherical to ellipsoidal structures. In addition, micelles from the shell region showed large electrostatic repulsion, judging from the shape of the spectrum in the higher Q -1 region. From the measurement results of the solubilization of naphthalene into the micelles, the size of the micelles corresponded to the maximum solubilization quantity of naphthalene.

Solution behavior and encapsulation properties of fatty acid-elastin-like polypeptide conjugates.

Developing new biomaterials is an active research area owing to their applications in regenerative medicine, tissue engineering and drug delivery. Elastin-like polypeptides (ELPs) are good candidates for these applications because they are biosourced, biocompatible and biodegradable. With the aim of developing ELP-based micelles for drug delivery applications we have synthesized 15 acyl-ELP compounds by conjugating myristic, palmitic, stearic, oleic or linoleic acid to the N-terminus of three ELPs differing in molar mass. The ELP-fatty acid conjugates have interesting solution behavior. They form micelles at low temperatures and aggregate above the cloud point temperature (Tcp). The critical micelle concentration depends on the fatty acid nature while the micelle size is mainly determined by the ELP block length. We were able to show that ELPs were better hydrated in the micelles than in their individual state in solution. The micelles are stable in phosphate-buffered saline at temperatures below the Tcp, which can vary between 20 °C and 38 °C depending on the length or hydrophilicity of the ELP. Acyl-ELP micelles were loaded with the small hydrophobic molecule Nile red. The encapsulation efficiency and release kinetics showed that the best loading conditions were achieved with the largest ELP conjugated to stearic acid.

Phosphoric Acid Triester Micelles: Characterization and Self-Assembly.

In this study, we analyzed the properties of amphiphilic alkyldi(methoxy poly(ethylene glycol) (MePEG)350-lactate) phosphates based on ethyl lactate, the monomethyl ether of poly(ethylene glycol)350, and alkyldichloro phosphates. Interestingly, these triesters combine two biodegradable bonds, -P(O)-O-C and -C(O)-O-C-, and include hydrophilic (MePEG350-lactate) and hydrophobic (R-aliphatic chain of alcohols) moieties. The properties of these esters resemble those of phospholipids. After being placed in an aqueous solution, they self-assembled. We also determined the effects of ester composition on micelle formation, stability, and size using dynamic light scattering. Solubilization tests using Sudan III or doxorubicin hydrochloride (Dox·HCl) revealed that they could be incorporated into the hydrophobic cores of dodecyl di(MePEG350-lactate) phosphate and hexadecyl di(MePEG350-lactate) phosphate. Notably, dodecyl di(MePEG350-lactate) phosphate was stable for five days, whereas hexadecyl di(MePEG350- lactate) phosphate was stable for seven days in phosphate-buffered saline. Moreover, Dox·HCl release rates from the micelles were approximately 30-40, 70-80, and 90-100% after 1, 5, and 28 d, respectively.

Theoretical treatment of complex coacervate core micelles: structure and pH-induced disassembly.

Complex coacervate core micelles (C3Ms) are supramolecular soft nanostructures formed by the assembly of a block copolymer and an oppositely charged homopolymer. The coacervation of the charged segments in both macromolecules drives the formation of the core of the C3M, while the neutral block of the copolymer forms the corona. This work introduces a molecular theory (MOLT) that predicts the internal structure and stimuli-responsive properties of C3Ms and explicitly considers the chemical architecture of the polyelectrolytes, their acid-based equilibria and electrostatic and non-electrostatic interactions. In order to accurately predict complex coacervation, the correlations between charged species are incorporated into MOLT as ion-pairing processes, which are modeled using a coupled chemical equilibrium formalism. Very good agreement was observed between the experimental results in the literature and MOLT predictions for the scaling relationships that relate the dimensions of the micelle (aggregation number and sizes of the micelle and the core) to the lengths of the different blocks. MOLT was used to study the disassembly of the micelles when the solution pH is driven away from the value that guarantees the charge stoichiometry of the core. This study reveals that very sharp disassembly transitions can be obtained by tuning the length or architecture of the copolymer component, thereby suggesting potential routes to design C3Ms capable of releasing their components at very precise pH values.

Interaction of Foam and Microemulsion Components in Low-Tension-Gas Flooding

Low-Tension-Foam (LTF) flooding is an emerging enhanced oil recovery technique for low-permeability carbonate reservoirs. Foam capacity is closely related to the salinity environment (or, equivalently, the phase behavior of the oil/water/surfactant system). Therefore, the interactions between microemulsion and foam components are of primary importance in the LTF process. In this study, the phase behavior of an oil/water/surfactant system under equilibrium is analyzed, firstly by assuming perfect mixing. Meanwhile, the formation kinetics of microemulsion are monitored through a novel low-field NMR technique, which is able to provide quantitative assessment on the microemulsion evolution characteristics. Then, foam stability is examined in the absence and in the presence of Winsor-I and Winsor-III type microemulsions. It is revealed that foam stability depends on the oil solubilization (oil swollen micelle size). A decrease in the oil swollen micelle size and micellar structure effectiveness, in conjunction with an increasing salinity, leads to lower foam stability in the presence of a Winsor-III type microemulsion.

Multifunctional Nanoparticles as High-Efficient Targeted Hypericin System for Theranostic Melanoma

Biotin, spermine, and folic acid were covalently linked to the F127 copolymer to obtain a new drug delivery system designed for HY-loaded PDT treatment against B16F10 cells. Chemical structures and binders quantification were performed by spectroscopy and spectrophotometric techniques (1NMR, HABA/Avidin reagent, fluorescamine assay). Critical micelle concentration, critical micelle temperature, size, polydispersity, and zeta potential indicate the hydrophobicity of the binders can influence the physicochemical parameters. Spermine-modified micelles showed fewer changes in their physical and chemical parameters than the F127 micelles without modification. Furthermore, zeta potential measurements suggest an increase in the physical stability of these carrier systems. The phototherapeutic potential was demonstrated using hypericin-loaded formulation against B16F10 cells, which shows that the combination of the binders on F127 copolymer micelles enhances the photosensitizer uptake and potentializes the photodynamic activity.

Self-assembling micelles of lipopolysaccharides (LPS) for loading hydrophobic (bio)molecules

Lipopolysaccharide (LPS) endotoxins are the most common pyrogenic biomolecules naturally present in Gram-negative bacteria membranes. Although LPS pathophysiological features are widely reported, a number of nanobiotechnological aspects perceive importance. Therefore, herein this study reports the physicochemical properties of LPS-based micelles from Escherichia coli O113, specifically focusing on their self-assembling distribution and aptitude to interact with four different (bio)molecules [i.e., chloroquine (CQ), curcumin (CCM), vemurafenib (VEM), and doxorubicin (DOX)]. The critical micelle concentration of LPS (CMCLPS) in an aqueous environment was determined to be 0.020 mg/mL, using a pyrene fluorescence emission spectra technique. The interaction of LPS and hydrophobic (bio)molecules was evaluated as a function of encapsulation parameters at the highest LPS concentration (CLPS of 0.043 mg/mL, i.e. >CMCLPS) for namely drug loading (DL) and encapsulation efficiency (EE). The DL results for CQ, CCM, VEM, and DOX were 28, 26, 22, and 20%, with 83, 80, 76, and 74% for their EE parameter, respectively. A straightforward relationship was observed for CLPS that increased jointly with micelle size (DH at 0.043 mg/mL > DH at 0.020 mg/mL). The presence of the (bio)molecules also affected LPS micelle size where DH was 51 nm (control micelles), which increased to 58, 58, 55, and 55 nm for CQ, CCM, VEM, and DOX, respectively, at a CLPS of 0.043 mg/mL. This trend demonstrates that increasing LPS micelle size (>CMCLPS) enhances the encapsulation capacity of the hydrophobic (bio)molecules. The understanding and characterization of the LPS-based micelles and their interaction with (bio)molecules could lead to novel applications in nanobiotechnology, such as the potential use of LPS, e.g., as drug/vaccine nanocarriers in the near future.

Novel Colloidal Dispersing Concept in Aqueous Media for Preparation by Wet-Jet Milling Dispersing Method

Dispersing particles in a liquid phase is significant for producing various functional nano/bio applications. The wet-jet milling method has been gaining attention as an attractive dispersing method in the preparation of soft material suspensions. This is because the main driving force of dispersion by the wet-jet milling method is the shear force, which is weaker than that it is in the ultrasonication dispersing method. In the wet-jet milling method, the pressure of the narrow channel which the liquid is passes through and the number of passes are used as the control parameters for dispersing the particles. However, the values of the pressure depend on the size (diameter and length) of the narrow channel, thus, it is not a commonly used dispersing parameter in dispersing by wet-jet milling to set the dispersing condition by various wet-jet milling instruments. In addition, wet-jet milling users must optimize the dispersing conditions such as the pressure and number of passes in the narrow channel, therefore, a simple prediction/optimization method of the dispersing size by the wet-jet milling method is desired. In this study, we established a novel colloidal dispersing concept, the dispersing energy input based on a calorimetric idea, for particle suspension preparation using the wet-jet milling method. The dispersing energy input by wet-jet milling was quantitatively calculated under various conditions during the dispersing by wet-jet milling, and then, the dispersing size of the particles was easily predicted/optimized. We demonstrated the usability of the concept by preparing aqueous suspensions of calcium carbonate (CaCO3) particles with various surfactants using the wet-jet milling method. Based on the established concept, in a case study on dispersing CaCO3, we found that changes in the micelle sizes of the surfactants played a role in wet-jet milling. The novel idea of the representation of energy input makes it possible to estimate the appropriate condition of the dispersing process by wet-jet milling to control the size of particles.