Search Results (12)

Micelles formed by bile salts in aqueous solution are important for the solubilization of hydrophobic molecules in the gastrointestinal tract. The molecular level information about the mechanism and driving forces for primary-to-secondary micelle transition is still missing. In the current study, the micelle formation of 50 mM solutions of taurodeoxycholate (TDC) is studied by atomistic molecular dynamics simulations. It is shown that primary micelles with an aggregation number of 8–10 emerge and persist within the first 50 ns. Then, they coalesce to form secondary micelles with an aggregation number of 19 molecules. This transition is governed by hydrophobic interactions, which significantly decrease the solvent-accessible surface area per molecule in the secondary micelles. The addition of monomers of the sodium salt of fatty acids (FAs), as agents aiding hydrophobic drug delivery, to secondary TDC micelles results in the co-existence of mixed FA-TDC and pure FA micelles. The studied saturated FAs, with chain lengths of C14:0 and C18:0, are incorporated into the micelle core, whereas TDC molecules position themselves around the FAs, forming a shell on the micelle surface. In contrast, the tails of the C18:1 unsaturated fatty acid mix homogeneously with TDC molecules throughout the entire micelle volume. The latter creates a very suitable medium for hosting hydrophobic molecules in the micelles containing unsaturated fatty acids. Full article

The shear flow and solid–liquid transition of mixed milk protein dispersions with varying concentrations of casein micelles (CMs) and serum proteins (SPs) are integral to key dairy processing operations, including microfiltration, ultrafiltration, diafiltration, and concentration–evaporation. However, the rheological behavior of these dispersions has not been sufficiently studied. In the present work, dispersions of CMs and SPs with total protein weight fractions (ω_PR) of 0.021–0.28 and SP to total protein weight ratios (R_SP) of 0.066–0.214 and 1 were prepared by dispersing the respective protein isolates in the permeate from skim milk ultrafiltration and then further concentrated via osmotic compression. The partition of SPs between the CMs and the dispersion medium was assessed by measuring the dry matter content and viscosity of the dispersion medium after separating it from the CMs via ultracentrifugation. The rheological properties were studied at 20 °C via shear rheometry, and the sol–gel transition was characterized via oscillatory measurements. No absorption of SPs by CMs was observed in dispersions with ω_PR = 0.083–0.126, regardless of the R_SP. For dispersions of SPs with ω_PR ≤ 0.21, as well as the dispersion medium of mixed dispersions with ω_PR = 0.083–0.126, the high shear- rate-limiting viscosity was described using Lee’s equation with an SP voluminosity (v_SP) of 2.09 mL·g⁻¹. For the mixed dispersions with a CM volume fraction of φ_CM ≤ 0.37, the relative high shear-rate-limiting viscosity was described using Lee’s equation with a CM voluminosity (v_CM) of 4.15 mL·g⁻¹ and a v_SP of 2.09 mL·g⁻¹, regardless of the R_SP. For the mixed dispersions with φ_CM > 0.55, the relative viscosity increased significantly with an increasing R_SP (this was explained by an increase in repulsion between CMs). However, the sol–gel transition was independent of the R_SP and was observed at φ_CM ≈ 0.65. Full article

The anionic polymer sodium alginate, a linear copolymer of guluronic and mannuronic acids, is primarily present in brown algae. Copolymers are used in the sodium alginate preparation process to confer on the material strength and flexibility. Micelles and other polymeric nanoparticles are frequently made using the triblock copolymer Pluronic^® F-127. The purpose of the present study is to determine the effect of sodium alginate’s viscosity (low and medium) and the presence of Pluronic^® F-127 micelles on the swelling behavior of the prepared pure beads and those loaded with Pluronic^® F-127 micelles. The Pluronic^® F-127 nanomicelles have a size of 120 nm. The swelling studies were carried out at pH = 1.2 (simulated gastric fluid-SGF) for two hours and at pH = 6.8 (simulated intestinal fluid-SIF) for four more hours. The swelling of both low- and medium-viscosity alginate beads was minor at pH = 1.2, irrespective of the use of Pluronic^® F-127 nanomicelles. At pH = 6.8, without Pluronic^® F-127, the beads showed an enhanced swelling ratio for the first four hours, which was even higher in the medium-viscosity alginate beads. With the addition of Pluronic^® F-127, the beads were dissolved in the first and second hour, in the case of the low- and medium-alginate’s viscosity, respectively. In other words, the behavior of the mixed hydrogels was the same during the swelling experiments. Therefore, the presence of Pluronic^® F-127 nanomicelles and medium-viscosity sodium alginate leads to a higher swelling ratio. A model drug, acetyl salicylic acid (ASA), was also encapsulated in the mixed beads and ASA’s release studies were performed. In conclusion, the prepared systems, which are well characterized, show potential as delivery platforms for the oral delivery of active pharmaceutical ingredients and biopharmaceuticals. Full article

Chemical structures bearing a combination of aggregation-induced emission enhancement (AIEE) and intramolecular charge transfer (ICT) properties attracted the attention of many researchers. Recently, there is an increasing demand to pose tunable AIEE and ICT fluorophores that could present their conformation changes-related emission colors by adjusting the medium polarity. In this study, we designed and synthesized a series of 4-alkoxyphenyl-substituted 1,8-naphthalic anhydride derivatives NAxC using the Suzuki coupling reaction to construct donor–acceptor (D-A)-type fluorophores with alkoxyl substituents of varying carbon chain lengths (x = 1, 2, 4, 6, 12 in NAxC). To explain the observation that molecules with longer carbon chains revealed unusual fluorescence enhancement in water, we study the optical properties and evaluate their locally excited (LE) and ICT states by solvent effects combined with Lippert–Mataga plots. Then, we explored the self-assembly abilities of these molecules in water-organic (W/O) mixed solutions and observed the morphology of its nanostructure using a fluorescence microscope and SEM. The results show that NAxC, x = 4, 6, 12 show different degrees of self-assembly behaviors and corresponding aggregation-induced emission enhancement (AIEE) progresses. At the same time, different nanostructures and corresponding spectral changes can be obtained by adjusting the water ratio in the mixed solution. That is, NAxC compounds present different transitions between LE, ICT and AIEE based on the polarity, water ratio and time changes. We designed NAxC as the structure–activity relationship (SAR) of the surfactant to demonstrate that AIEE comes from the formation of micelle-like nanoaggregates, which causes a restriction of the transfer from the LE state to the ICT state, and micelle formation results in a blue-shift in emission and enhances the intensity in the aggregate state. Among them, NA12C is most likely to form micelles and the most obvious fluorescence enhancement, which will switch over time due to the nano-aggregation transition. Full article

To solve a number of problems in construction materials science, composites with nano and ultrafine admixtures were analyzed. Their properties were studied, taking into account the variants of homogenization and stabilization of the system. To characterize the processes of the structure formation of a new material, mathematical methods were also applied. According to the literature review, the aim of the work was formulated. The subject of this research is to conduct physico-chemical studies that characterize the processes occurring during the homogenization and stabilization of the cement system with GGBS components and to establish the effect of the admixture on the properties of the composite. To achieve this goal, an ultrafine admixture based on GGBS was obtained, and the possibility of its introduction into the cement system in the form of a stabilized suspension instead of mixing water was considered. To provide increased characteristics of cement stone modified with the ultrafine admixture, a number of tests were carried out to study homogenization and stabilization of fine slag particles in suspension. The ultrasonic processing parameters were defined to provide uniform distribution of fine slag additive in the suspension: the processing time is 15–20 min, the frequency of ultrasonic vibrations is 44 kHz, the temperature of the dispersed medium is 25 ± 2 °C. To define physical and chemical processes appearing during the introduction of fine slag into water and water-polymer dispersed medium, the mechanism of interaction between fine slag and water was studied. In addition, the mechanism of chemisorption on the surface of fine slag particles and the stabilization mechanism of ultrafine slag particles with a plasticizer was studied to form the concept of aggregate and sedimentation stability of slag particles in suspension. It was found that the stabilization of fine slag particles by a plasticizer is significantly influenced by the hardness of water. The higher the water hardness, the more plasticizer required to stabilize the fine slag particles. At the same time, it was established that the concentration of the plasticizer should not exceed the critical micelle concentration value. If it is exceeded, the plasticizer solution transforms into the micellar colloidal system, and the stabilization of fine slag suspension will not occur. The studies of homogenization and stabilization of the slag suspension allowed the authors to substantiate the possibility of uniform distribution of fine particles in the cement matrix, followed by the formation of a denser and stronger cement stone structure. Cement-sand samples based on Portland cement (OPC) and slag-Portland cement (SPC) with GGBFS admixture showed higher compressive and flexural strength characteristics in the initial hardening periods and at 28 days. It was found that modified samples are more stable in an aggressive medium. On the 90th day of exposure, the resistance coefficient was 0.9 for a modified sample based on OPC and 0.98 for a modified sample based on SPC. The increased sulfate attack resistance of the samples is due to the formation of a dense stone with reduced porosity. It is noted that the porosity of modified OPC samples decreases by 14% and by 18% for SPC-based modified samples compared to the control sample at 28 days. Due to the fact that pores in the cement stone are blocked with hydration products, which make the structure of the cement stone denser, the filtration of aggressive solutions deep into its structure is difficult. Thus, the obtained concrete based on a cement composite with ultrafine slag can be applied as a protective layer of steel reinforcement in a reinforced concrete structure. Full article

Phase change materials (PCMs) store or release heat during their phase transition. Their low thermal conductivity affects the performance of the latent heat energy storage system. This study aimed to investigate the thermal conductivity of PCMs by mixing surfactants. Surfactants with varying weights of sodium stearate (SS), gum arabic (GA), and sodium stearoyl lactylate (SSL) were mixed with paraffin wax. The charging and discharging rate of pure paraffin wax was compared to surfactant-mixed paraffin wax. Pure paraffin wax peaked at 66.76 °C. SSL’s highest temperature was 68.3 °C at the critical micelle concentration (CMC) (the concentration of surfactants above which micelles form) and 69 °C above the CMC. GA reached 70 °C at the CMC and 71 °C above the CMC. Sodium stearate (SS) reached 72.12 °C at the CMC and 73.8 °C above the CMC. The melting time test revealed that a reduced melting time resulted in the higher heat conductivity of paraffin. When compared to the melting times of pure paraffin, those of composite PCM containing SSL (>CMC), GA (>CMC), and SS (>CMC) decreased by 6.12%, 14.28%, and 22.44%, respectively. The results show that a concentration above the critical micelle concentration of sodium stearate leads to the best results compared to other samples. Surfactants form micelle, which acted as the conducting medium inside the paraffin wax. Thus, paraffin wax’s thermal conductivity was boosted, and the study’s goal was met. Full article

The focus of the present work is to evaluate the interactions of an anti-allergic drug (diphenhydramine hydrochloride, DPH) with anionic (sodium dodecyl sulfate, SDS) and cationic (cetylpyridinium chloride, CPC) surfactants in the aqueous medium. The mixed micellization behavior and surface properties of drug-surfactant mixtures have been examined by surface tension measurements. Various theoretical approaches were applied to explore the synergistic or non-ideal behavior of the current mixed systems. Furthermore, the binding studies of drug with surfactants have been elaborated by UV–visible spectroscopy. Benesi–Hildebrand (B-H) theory was used to compute stoichiometric ratio, binding constant, and free energy change for the drug-surfactant mixtures. The outputs are deliberated taking into consideration the use of surfactants as capable drug delivery agents for DPH and hence advance bioavailability. Full article

Ionizing radiation has become the most effective way to modify natural and synthetic polymers through crosslinking, degradation, and graft polymerization. This review will include an in-depth analysis of radiation chemistry mechanisms and the kinetics of the radiation-induced C-centered free radical, anion, and cation polymerization, and grafting. It also presents sections on radiation modifications of synthetic and natural polymers. For decades, low linear energy transfer (LLET) ionizing radiation, such as gamma rays, X-rays, and up to 10 MeV electron beams, has been the primary tool to produce many products through polymerization reactions. Photons and electrons interaction with polymers display various mechanisms. While the interactions of gamma ray and X-ray photons are mainly through the photoelectric effect, Compton scattering, and pair-production, the interactions of the high-energy electrons take place through coulombic interactions. Despite the type of radiation used on materials, photons or high energy electrons, in both cases ions and electrons are produced. The interactions between electrons and monomers takes place within less than a nanosecond. Depending on the dose rate (dose is defined as the absorbed radiation energy per unit mass), the kinetic chain length of the propagation can be controlled, hence allowing for some control over the degree of polymerization. When polymers are submitted to high-energy radiation in the bulk, contrasting behaviors are observed with a dominant effect of cross-linking or chain scission, depending on the chemical nature and physical characteristics of the material. Polymers in solution are subject to indirect effects resulting from the radiolysis of the medium. Likewise, for radiation-induced polymerization, depending on the dose rate, the free radicals generated on polymer chains can undergo various reactions, such as inter/intramolecular combination or inter/intramolecular disproportionation, b-scission. These reactions lead to structural or functional polymer modifications. In the presence of oxygen, playing on irradiation dose-rates, one can favor crosslinking reactions or promotes degradations through oxidations. The competition between the crosslinking reactions of C-centered free radicals and their reactions with oxygen is described through fundamental mechanism formalisms. The fundamentals of polymerization reactions are herein presented to meet industrial needs for various polymer materials produced or degraded by irradiation. Notably, the medical and industrial applications of polymers are endless and thus it is vital to investigate the effects of sterilization dose and dose rate on various polymers and copolymers with different molecular structures and morphologies. The presence or absence of various functional groups, degree of crystallinity, irradiation temperature, etc. all greatly affect the radiation chemistry of the irradiated polymers. Over the past decade, grafting new chemical functionalities on solid polymers by radiation-induced polymerization (also called RIG for Radiation-Induced Grafting) has been widely exploited to develop innovative materials in coherence with actual societal expectations. These novel materials respond not only to health emergencies but also to carbon-free energy needs (e.g., hydrogen fuel cells, piezoelectricity, etc.) and environmental concerns with the development of numerous specific adsorbents of chemical hazards and pollutants. The modification of polymers through RIG is durable as it covalently bonds the functional monomers. As radiation penetration depths can be varied, this technique can be used to modify polymer surface or bulk. The many parameters influencing RIG that control the yield of the grafting process are discussed in this review. These include monomer reactivity, irradiation dose, solvent, presence of inhibitor of homopolymerization, grafting temperature, etc. Today, the general knowledge of RIG can be applied to any solid polymer and may predict, to some extent, the grafting location. A special focus is on how ionizing radiation sources (ion and electron beams, UVs) may be chosen or mixed to combine both solid polymer nanostructuration and RIG. LLET ionizing radiation has also been extensively used to synthesize hydrogel and nanogel for drug delivery systems and other advanced applications. In particular, nanogels can either be produced by radiation-induced polymerization and simultaneous crosslinking of hydrophilic monomers in “nanocompartments”, i.e., within the aqueous phase of inverse micelles, or by intramolecular crosslinking of suitable water-soluble polymers. The radiolytically produced oxidizing species from water, •OH radicals, can easily abstract H-atoms from the backbone of the dissolved polymers (or can add to the unsaturated bonds) leading to the formation of C-centered radicals. These C-centered free radicals can undergo two main competitive reactions; intramolecular and intermolecular crosslinking. When produced by electron beam irradiation, higher temperatures, dose rates within the pulse, and pulse repetition rates favour intramolecular crosslinking over intermolecular crosslinking, thus enabling a better control of particle size and size distribution. For other water-soluble biopolymers such as polysaccharides, proteins, DNA and RNA, the abstraction of H atoms or the addition to the unsaturation by •OH can lead to the direct scission of the backbone, double, or single strand breaks of these polymers. Full article

Studies of the effects produced by the solubilization of hydrophobic substances by micellar aggregates in water medium are quite important for applications of viscoelastic surfactant solutions for enhanced oil recovery (EOR), especially in hydraulic fracturing technology. The present paper aims at the investigation of the structural transformations produced by the absorption of an aliphatic hydrocarbon (n-decane) by mixed wormlike micelles of cationic (n-octyltrimethylammonium bromide, C8TAB) and anionic (potassium oleate) surfactants enriched by C8TAB. As a result of contact with a small amount (0.5 wt%) of oil, a highly viscoelastic fluid is transformed to a water-like liquid. By small-angle neutron scattering (SANS) combined with cryo-TEM, it was shown that this is due to the transition of long wormlike micelles with elliptical cross-sections to ellipsoidal microemulsion droplets. The non-spherical shape was attributed to partial segregation of longer- and shorter-tail surfactant molecules inside the surfactant monolayer, providing an optimum curvature for both of them. As a result, the long-chain surfactant could preferably be located in the flatter part of the aggregates and the short-chain surfactant—at the ellipsoid edges with higher curvature. It is proven that the transition proceeds via a co-existence of microemulsion droplets and wormlike micelles, and upon the increase of hydrocarbon content, the size and volume fraction of ellipsoidal microemulsion droplets increase. The internal structure of the droplets was revealed by contrast variation SANS, and it was shown that, despite the excess of the cationic surfactant, the radius of surfactant shell is controlled by the anionic surfactant with longer tail. These findings open a way for optimizing the performance of viscoelastic surfactant fluids by regulating both the mechanical properties of the fluids and their clean-up from the fracture induced by contact with hydrocarbons. Full article

The chemotherapy of stimuli-responsive drug delivery systems (SDDSs) is a promising method to enhance cancer treatment effects. However, the low efficiency of chemotherapy drugs and poor degradation partly limit the application of SDDSs. Herein, we report doxorubicin (DOX)-loading mixed micelles for biotin-targeting drug delivery and enhanced photothermal/photodynamic therapy (PTT/PDT). Glutathione (GSH)-responsive mixed micelles were prepared by a dialysis method, proportionally mixing polycaprolactone-disulfide bond-biodegradable photoluminescent polymer (PCL-SS-BPLP) and biotin-polyethylene glycol-cypate (biotin-PEG-cypate). Chemically linking cypate into the mixed micelles greatly improved cypate solubility and PTT/PDT effect. The micelles also exhibited good monodispersity and stability in cell medium (~119.7 nm), low critical micelles concentration, good biodegradation, and photodecomposition. The high concentration of GSH in cancer cells and near-infrared light (NIR)-mediated cypate decomposition were able to achieve DOX centralized release. Meanwhile, the DOX-based chemotherapy combined with cypate-based NIR-triggered hyperthermia and reactive oxygen species could synergistically induce HepG2 cell death and apoptosis. The in vivo experiments confirmed that the micelles generated hyperthermia and achieved a desirable therapeutic effect. Therefore, the designed biodegradable micelles are promising safe nanovehicles for antitumor drug delivery and chemo/PTT/PDT combination therapy. Full article

A simple and sensitive cloud point extraction method for the preconcentration of ultra-trace amounts of nickel as a prior step to its determination by graphite furnace atomic absorption spectrometry was proposed. It is based on the reaction of nickel with 2-(5-bromo-2-pyridylazo)-5-dimethylaminoaniline (5-Br-PADMA) in HAc–NaAc buffer media and mixed micelle-mediated extraction of the complex using the anionic surfactant sodium dodecyl sulfate sodium (SDS) and non-ionic surfactant (1,1,3,3-Tetramethylbutyl)phenyl-polyethylene (Triton X-114). The optimal reaction and extraction conditions such as pH, concentration of 5-Br-PADMA, SDS and Triton X-114, equilibrium temperature, incubation, and centrifuge time were evaluated and optimized. Under the optimal conditions, the calibration graph was linear over the range 0.1–5.5 ng/mL of nickel with a correlation coefficient of 0.9942. The detection limit obtained was 0.031 ng/mL, and the relative standard deviation was 2.1% for nickel (c = 2 ng/mL, n = 6). The proposed method was successfully applied to the determination of nickel in water samples. Full article

The efficacy of phytosterols and phytostanols added to foods and food supplements to obtain significant non-pharmacologic serum and low density lipoprotein (LDL) cholesterol reduction is well documented. Irrespective of age, gender, ethnic background, body weight, background diet, or the cause of hypercholesterolemia and, even added to statin treatment, phytosterols and phytostanols at 2 g/day significantly lower LDL cholesterol concentration by 8%–10%. They do not affect the concentrations of high density lipoprotein cholesterol, lipoprotein (a) or serum proprotein convertase subtilisin/kexin type 9. In some studies, phytosterols and phytostanols have modestly reduced serum triglyceride levels especially in subjects with slightly increased baseline concentrations. Phytosterols and phytostanols lower LDL cholesterol by displacing cholesterol from mixed micelles in the small intestine so that cholesterol absorption is partially inhibited. Cholesterol absorption and synthesis have been carefully evaluated during phytosterol and phytostanol supplementation. However, only a few lipoprotein kinetic studies have been performed, and they revealed that LDL apoprotein B-100 transport rate was reduced. LDL particle size was unchanged, but small dense LDL cholesterol concentration was reduced. In subjects with metabolic syndrome and moderate hypertriglyceridemia, phytostanols reduced not only non- high density lipoprotein (HDL) cholesterol concentration but also serum triglycerides by 27%, and reduced the large and medium size very low density lipoprotein particle concentrations. In the few postprandial studies, the postprandial lipoproteins were reduced, but detailed studies with apoprotein B-48 are lacking. In conclusion, more kinetic studies are required to obtain a more complete understanding of the fasting and postprandial lipoprotein metabolism caused by phytosterols and phytostanols. It seems obvious, however, that the most atherogenic lipoprotein particles will be diminished. Full article