Long-term Dispersion Stability Research Articles

Mucoadhesive and Rheological Studies on the Co-Hydrogel Systems of Poly(Ethylene Glycol) Copolymers with Fluoroalkyl and Poly(Acrylic Acid)

A self-assembled co-hydrogel system with sol-gel two-phase coexistence and mucoadhesive properties was developed based on the combined properties of fluoroalkyl double-ended poly(ethylene glycol) (Rf-PEG-Rf) and poly(acrylic acid) (PAA), respectively. We have synthesized an Rf-PEG-g-PAA (where g denotes grafted) copolymer and integrated it into the Rf-PEG-Rf physically cross-linked micellar network to form a co-hydrogel system. Tensile strengths between the co-hydrogel surfaces and two different sets of mucosal surfaces were acquired. One mucosal surface was made of porcine stomach mucin Type II, while the other one is a pig small intestine. The experimental results show that the largest maximum detachment stresses (MDSs) were obtained when the Rf-PEG-g-PAA’s weight percent in the dehydrated polymer mixture is ~15%. Tensile experiments also found that MDSs are greater in acidic conditions (pH = 4–5) (123.3 g/cm2 for the artificial mucus, and 43.0 g/cm2 for pig small intestine) and basic conditions (pH = 10.6) (126.9 g/cm2, and 44.6 g.cm2, respectively) than in neutral pH (45.4 g/cm2, and 30.7 g.cm2, respectively). Results of the rheological analyses using shear strain amplitude sweep and frequency sweep reveal that the Rf-PEG-g-PAA was physically integrated into the Rf-PEG-Rf micellar network, and the co-hydrogels remain physically cross-linked in three-dimensional micellar networks with long-term physical dispersion stability. Therefore, the co-hydrogel system is promising for drug delivery applications on mucosal surfaces.

Novel Surfactant-Free Water Dispersion Technique of TiO2 NPs Using Focused Ultrasound System.

Titanium dioxide (TiO2) nanoparticles are used in a wide variety of products, such as renewable energy resources, cosmetics, foods, packaging materials, and inks. However, large quantities of surfactants are used to prepare waterborne TiO2 nanoparticles with long-term dispersion stability, and very few studies have investigated the development of pure water dispersion technology without the use of surfactants and synthetic auxiliaries. This study investigated the use of focused ultrasound to prepare surfactant-free waterborne TiO2 nanoparticles to determine the optimal conditions for dispersion of TiO2 nanoparticles in water. Under 395–400 kHz and 100–105 W conditions, 1 wt% TiO2 colloids were prepared. Even in the absence of a surfactant, in the water dispersion state, the nanoparticles were dispersed with a particle size distribution of ≤100 nm and did not re-agglomerate for up to 30 days, demonstrating their excellent dispersion stability.

One-step preparation of Cr2O3-based inks with long-term dispersion stability for inkjet applications.

Inkjet printing of functional materials has shown a wide range of applications in advertising, OLED display, printed electronics and other specialized utilities that require high-precision, mask-free, direct-writing deposition techniques. Nevertheless, the sedimentation risk of the refractory functional materials dispensed in inks hinders their further implementation. Herein, we present a bottom-up ink preparation strategy based on Cr2O3 by a one-step solvothermal method. The obtained ink remained stable under an equivalent natural sediment test for 2.5 years. The chemical composition of the solvothermal product was characterized, and the mechanism of the superior dispersion stability of Cr2O3 particles was analysed. These amorphous Cr2O3 particles were capped by ligands generated via low-temperature solvothermal reactions. Ethanol and acetylacetone covering the particle surfaces play an essential role in enhancing the solubility of Cr2O3 particles in the solvent forming the ultrastable colloidal ink. Moreover, this ink was successfully printed using a direct-write inkjet system JetLab®II on nylon fabrics, and the printed area of the fabrics shows a spectral correlation coefficient of 0.9043 to green leaves. Finally, we believe that the one-step bottom-up fabrication method of Cr2O3-based pigment inks may provide a general approach for preparing metal oxide-based pigment inks with long-term dispersion stability.

Development and characterization of soybean protein isolate and fucoidan nanoparticles for curcumin encapsulation

Curcumin (Cur) is a natural polyphenol with beneficial biological and pharmacological activities; however, it has limited applications owing to its low solubility and light sensitivity. The protein-polysaccharide complex can effectively embed lipid-soluble drugs to increase their stability and dispensability in aqueous solutions. Soybean protein isolate (Spi) and fucoidan (Fuc) were used as a polymer matrix, and core-shell nanoparticles were prepared to encapsulate Cur via electrostatic interaction under acidic and neutral conditions. The structure of the Spi-Fuc nanoparticles was studied via Fourier-transform infrared spectroscopy, transmission electron microscopy, and scanning electron microscopy. Concurrently, we evaluated the efficacy of the nanoparticles based on stability, drug loading rate, and simulated release. Our results showed that the Spi-Fuc nanoparticles (size, approximately 236.56 nm) had a spherical, core-shell structure and that they could effectively load Cur with an embedding efficiency of >95%; moreover, the system had long-term dispersion stability. Thus, we provide a simple method for Cur delivery, which can also be potentially used for delivering lipid-soluble active ingredients.

Solvent influence on the phase behavior and glass transition of Amorphous Solid Dispersions

Understanding the long-term stability of amorphous solid dispersions (ASDs) is important for their successful approval for market. ASD stability does not only depend on the interplay between the active pharmaceutical ingredient (API) and the polymer in the final formulation but may already be disadvantageously influenced by process steps during the production (e.g. selection of inappropriate solvent for spray drying). Residual solvent can affect the API solubility in the polymer, molecular mobility (by influencing the glass-transition temperature) and induce liquid-liquid phase separation. Enhanced mobility in the ASD due to residual solvent can promote recrystallization in ASDs.The removal of residual solvent can be expensive, time-consuming, and usually requires secondary drying procedures to fulfil the regulatory requirements. The aim of this work is to predict the API solubility in polymer-solvent mixtures, solvent influence on the glass transition, and the occurrence of liquid-liquid phase separation of solvent-loaded ASDs using the thermodynamic model PC-SAFT and to experimentally validate these predictions. ASDs containing the APIs ritonavir or naproxen and the polymers poly(vinylpyrrolidone), poly (vinylpyrrolidone-co-vinyl acetate), or hydroxypropyl methylcellulose acetate succinate were spray-dried using the solvents acetone, ethanol, and dichloromethane. API solubility, sorption behavior, liquid-liquid phase separation and glass transition in the ternary API/polymer/solvent mixtures were predicted based on the binary phase behavior between API/solvent, API/polymer, and polymer/solvent and successfully validated experimentally using dynamic vapor sorption (DVS), and Raman spectroscopy. Thus, the presented methodology allows for an in-silico selection of appropriate solvent systems for solvent-based ASD preparation based on a limited amount of experimental data for binary systems only.

Graphene-Based Aqueous Lubricants: Dispersion Stability to the Enhancement of Tribological Properties.

The present investigation demonstrates a green and scalable chemical approach to prepare aminoborate-functionalized reduced graphene oxide (rGO-AmB) for aqueous lubricants. The chemical, structural, crystalline, and morphological features of rGO-AmB are probed by XPS, FTIR, Raman, XRD, and HRTEM measurements. The spectroscopic analyses revealed the multiple interaction pathways between rGO and AmB. rGO-AmB exhibited long-term dispersion stability and improved the thermal conductivity of water by 68%. The thermal conductivity increased with increasing concentration of rGO-AmB and temperature. rGO-AmB as an additive to water (0.2%) enhanced the tribological properties of a steel tribopair under the boundary lubrication regime by the significant reduction in friction (70%) and wear (68%). The tribo-induced gradual deposition of an rGO-AmB-based thin film facilitated the interfacial sliding between the steel tribopair and protected it from the wear. The ultralow thickness, excellent dispersibility in water, high thermal conductivity, intrinsic low frictional properties, and good affinity toward the tribo-interfaces make rGO-AmB a potential candidate for aqueous lubricants.

Synthesis and Characterization of Citrate-Stabilized Gold-Coated Superparamagnetic Iron Oxide Nanoparticles for Biomedical Applications.

Surface-functionalized gold-coated superparamagnetic iron oxide nanoparticles (Au-SPIONs) may be a useful tool in various biomedical applications. To obtain Au-SPIONs, gold salt was precipitated onto citrate-stabilized SPIONs (Cit-SPIONs) using a simple, aqueous one-pot technique inspired by the Turkevich method of gold nanoparticle synthesis. By the further stabilization of the Au-SPION surface with additional citrate (Cit-Au-SPIONs), controllable and reproducible Z-averages enhanced long-term dispersion stability and moderate dispersion pH values were achieved. The citrate concentration of the reaction solution and the gold/iron ratio was found to have a major influence on the particle characteristics. While the gold-coating reduced the saturation magnetization to 40.7% in comparison to pure Cit-SPIONs, the superparamagnetic behavior of Cit-Au-SPIONs was maintained. The formation of nanosized gold on the SPION surface was confirmed by X-ray diffraction measurements. Cit-Au-SPION concentrations of up to 100 µg Fe/mL for 48 h had no cytotoxic effect on Jurkat cells. At a particle concentration of 100 µg Fe/mL, Jurkat cells were found to take up Cit-Au-SPIONs after 24 h of incubation. A significantly higher attachment of thiol-containing L-cysteine to the particle surface was observed for Cit-Au-SPIONs (53%) in comparison to pure Cit-SPIONs (7%).

Bio-Inspired Passion Fruit-like Fe3O4@C Nanospheres Enabling High-Stability Magnetorheological Performances.

Magnetorheological (MR) fluids have been successfully utilized in versatile fields but are still limited by their relatively inferior long-term dispersion stability. Herein, bio-inspired passion fruit-like Fe3O4@C nanospheres were fabricated via a simple hydrothermal and calcination approach to tackle the settling challenge. The unique structures provide sufficient active interfaces for the penetration of carrier mediums, leading to preferable wettability between particles and medium oils. Compared with the bare Fe3O4 nanoparticle suspension, the resulting Fe3O4@C nanosphere-based MR fluid exhibits desirable stability and relatively low field-off viscosity even at a high particle concentration up to 35 vol %.

Effective association of ceramide-coassembled lipid nanovehicles with stratum corneum for improved skin barrier function and enhanced skin penetration.

Herein, we report on a ceramide-coassembled lipid nanovehicle (CLNV) system that can enhance the penetration of active ingredients through the skin barrier by taking advantage of molecular associations between ceramide and lipids in the stratum corneum (SC) layer. For this purpose, we fabricated CLNVs consisting of an asymmetric lipid and a cholesterol derivative. They showed excellent long-term dispersion stability without molecular crystallization of ceramide. Upon forming a stable aqueous dispersion, the CLNVs retained their initial vehicle structure even under harsh conditions including high storage temperatures or salinity conditions. From in vitro skin barrier recovery tests, we observed that topical treatment with CLNVs induced the SC to restore its lamellar structure to the same condition as that prior to chemical damage. An in vivo skin penetration study additionally confirmed that skin penetration was enhanced, since the CLNVs were able to effectively interact with the SC layer. From these results, the CLNVs with robust molecular layer endow various applications in wide range applications including transdermal pharmaceutics delivery systems and cosmetics field.

A Comprehensive Physical Profile for Aqueous Dispersions of Carbon Derivatives as Solar Working Fluids

The application of nanofluids in direct solar absorption, heat transfer or direct solar steam generation entails carrying out a comprehensive study taking into account several physical quantities. Long-term stability, rheological, thermophysical and optical properties of dispersions must be known to assess their potential for envisaged applications. Two low-concentration nanofluids, 0.005 and 0.05 wt%, of sulfonic acid-functionalized and polycarboxylate chemically modified graphene nanoplatelets in water were considered in this work. Elemental analyses of the nanopowders and pH evaluations of the colloids were carried out. The rheological behaviour of dispersions at different temperatures was studied by rotational rheometry. Thermal conductivities were measured by the transient hot wire method and densities by the oscillating U-tube technique. Additionally, a brief report of the optical properties was included to provide a comprehensive physical analysis.

Synthesis by partial oxygenation of graphite-like carbon nitride (OCN) decorated with oleic diethanolamide borate (ODAB) for oil-based lubricant additives and its tribological properties

ODAB-OCN retaining long-term dispersion stability in an oil environment exhibits excellent tribological properties.

Synthesis, characterization, stability and thermal conductivity of multi-walled carbon nanotubes (MWCNTs) and eco-friendly jatropha seed oil based nanofluid: An experimental investigation and modeling approach

Despite the remarkable nanofluids potential in energy storage applications, the long-term dispersion stability of the nanoparticles in a base fluid along with improved thermal conductivity is a significant challenge towards their commercialization. Therefore, a novel surfactant MWCNTs and eco-friendly Jatropha seed oil based nanofluid are synthesized via one-step synthesis method and subjected to characterization via visual analysis, FTIR, Zeta potential, pore size distribution, thermogravimetric analysis (TGA), and UV analysis to investigate MWCNTs dispersion stability along with thermal conductivity measurement. The results showed the excellent MWCNTs dispersion stability in Jatropha seed oil and thermal conductivity improvement from 2.29% to 6.76% over the temperature within the range of 25–65 °C and nanoparticle weight fraction in the range of 0.2–0.8 wt%. Furthermore, two new correlations are proposed based on multiple non-linear regression analysis and dimensionless group analysis in the replacement of classical models which are failed to accurate prediction of thermal conductivity. The developed models showed remarkable thermal conductivity prediction accuracy with the value of R2 > 0.991.

Dithiocarbamates: Reliable Surface Ligands for NIR-Emitting Quantum Dots.

In this paper, we report a reliable method for transferring hydrophobic, NIR-emitting PbS/CdS core-shell quantum dots (QDs) to water solutions using synthesized in situ dithiocarbamate derivatives of amino acids as stabilizing ligands. Such ligands offer apparent advantages over dihydrolipoic acid (DHLA) derivatives commonly used as ligands stabilizing quantum dots. The most effective phase transfer and the best long-term stability of water dispersions of amino acid-DTC-capped QDs were achieved using lysine dithiocarbamate. In this case, the phase transfer of PbS/CdS nanoparticles from organic to aqueous phase can be completed in 6-8 h. Prepared amino acid-DTC-capped QDs nanoparticles have narrow size distributions, and their hydrodynamic diameter remains below 9 nm. After transferring to water, lysine-DTC-capped PbS/CdS nanoparticles retain their spectroscopic properties for at least 48 h. Moreover, they are not toxic up to concentration corresponding to about 7 μg/cm3 of PbS/CdS, which is sufficient for their application in biological systems. In addition, lysine-DTC-capped PbS/CdS QDs can be straightforwardly modified by layer-by-layer polyelectrolyte coating.

Facile fabrication of long-chain alkyl functionalized ultrafine reduced graphene oxide nanocomposites for enhanced tribological performance.

Due to their ultrathin 2D laminated structure as well as excellent mechanical and thermal stabilities, ultrafine graphene-based nanoparticles exhibit fascinating advantages as highly-efficient lubricant additives. However, it remains a daunting challenge to achieve good and durable dispersion of these graphene-based nanoparticles in lubricating oils. Herein, we report a facile and efficient integration strategy involving particle size miniaturization, surface grafting with octadecyl alcohol (OA), and partial chemical reduction to prepare a novel long-chain alkyl functionalized ultrafine reduced graphene oxide (RGO-g-OA) with highly-dispersive capacity and superior tribological performance. The chemical composition and structural characteristics, microstructural morphology, and particle size distribution of RGO-g-OA were systematically investigated. Combining significantly improved lipophilicity derived from the long-chain alkyl grafting and partial chemical reduction with the small-size effect gave rise to outstanding long-term dispersion stability (as long as one month) of RGO-g-OA in the finished oil. Moreover, the friction coefficient and wear volume of finished oil with merely 0.005 wt% RGO-g-OA greatly reduced to 0.065 and 10 316 μm3, decreased by 9.7% and 44%, respectively, compared to those of pristine finished oil, demonstrating remarkable friction reduction and anti-wear performances. Consequently, owing to the characteristics of facile fabrication, durable dispersion stability, and superior tribological performance at an extremely low content, this novel nanoadditive shows a promising application potential in the tribology field.

Urea modified fluorinated carbon nanotubes: unique self-dispersed characteristic in water and high tribological performance as water-based lubricant additives

UF-CNTs retaining a long-term dispersion stability in aqueous environments exhibit excellent tribological properties.

Synthesis of boron nitride microrods with fish-scale-like structures for enhanced thermal conductivity of water

Hexagonal boron nitride (h-BN) has triggered great interest in thermal management system because of its superb thermal conductivity, excellent chemical inertness and outstanding tribological behavior. However, the application of BN in water suffers from the poor dispersion stability. Herein, we develop a spray drying and pyrolysis route to directly fabricate porous BN microrods with fish-scale-like structures. BN microrods exhibit long-term dispersion stability in aqueous solution due to their high hydroxylation degrees. Although the viscosity of water was increased after adding BN microrods, the friction coefficient and wear scar diameter were reduced obviously. Moreover, thermal conductivity of BN/water fluid was improved from 0.589 to 1.117 W/m K when the content of BN was 0.1 vol%, which was higher than that of previous results. These results demonstrate that the fish-scale-like structured BN microrods have great potential and irreplaceable advantage in thermal and tribological management.

Impact of Polymer Type and Relative Humidity on the Long-Term Physical Stability of Amorphous Solid Dispersions.

The purpose of this work is to compare the long-term physical stability of amorphous solid dispersion (ASD) formulations based on three different commercially used excipients, namely, poly(vinylpyrrolidone) K25 (PVP), poly(vinylpyrrolidone-co-vinyl acetate) (PVPVA64), and hydroxypropyl methylcellulose acetate succinate 126G (HPMCAS), at standardized ICH storage conditions, 25 °C/0% relative humidity (RH), 25 °C/60% RH, and 40 °C/75% RH. Acetaminophen (APAP) and naproxen (NAP) were used as active pharmaceutical ingredients (APIs). 18 month long stability studies of these formulations were analyzed and compared with the API/polymer phase diagrams, which were modeled and predicted by applying the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) and the Gordon-Taylor or Kwei equation. The study showed that, at dry storage, the solubility of the APIs in the polymers and the kinetic stabilizing ability of the polymers increase in the following order: HPMCAS < PVPVA64 < PVP. RH significantly reduces the kinetic stabilization as well as NAP solubility in the polymers, while the impact on APAP solubility is small. The impact of RH on the stability increases with increasing hydrophilicity of the pure polymers (HPMCAS < PVPVA64 < PVP). The experimental stability results were in very good agreement with predictions confirming that PC-SAFT and the Kwei equation are suitable predictive tools for determining appropriate ASD compositions and storage conditions to ensure long-term physical stability.

Molecular dynamics simulation of the effects of affinity of functional groups and particle-size on the behavior of a graphene sheet in nanofluid

The practical application of thermally enhanced nanofluids in automotive industries for higher energy efficiency requires that nanoparticles be buoyant, leading to Brownian motion in the base fluid without aggregation. Numerous studies have reported the long-term stability of dispersions resulting from steric hindrance and an affinity for the surrounding base fluid via modification of nanoparticles with functional groups. In this study, we performed molecular dynamics simulations of nanofluids containing a single graphene sheet with various functional groups to investigate the influence of affinity, as well as particle-size, on the behavior of the graphene sheet. Using the concept of the speed of nanoparticle, we quantitatively evaluated the dependence of behavior on affinity to investigate whether having more functional groups with more attractive interactions has an impact on the stable dispersion in nanofluid. In addition, the simulation results for the particle-size effect revealed that the larger nanoparticles produced more stable dispersion in nanofluid. We concluded that the behavior of the graphene sheet depends on a combination of two factors: different charge assigned to atoms due to a nitrogen atom, and the difference in mass, which influences the speed of the nanoparticles.

Experimental investigation on the stability and abrasive action of cerium oxide nanoparticles dispersed diesel

Ceria nanoparticle is a well-known fuel borne additive for reducing the particulate emissions from diesel engines. Main challenges in the use of ceria nanoparticles are the lack of long-term dispersion stability in diesel and their effect on lubricity of diesel. The present work mainly focuses on synthesis of stable ceria nanoparticle diesel suspension and study on their lubricity. Ceria nanoparticles were synthesized by co-precipitation method and nano fluids were prepared by two-step method. The optimum concentration of oleic acid (surfactant) was determined based on critical micelle concentration studies and concentration of ceria nanoparticle in diesel was varied from 5 to 25 ppm. Long term dispersion stability studies using Dynamic light scattering system and Turbidity meter shows 10 ppm as an optimum concentration of ceria nanoparticle in diesel for maximum stability. Tribological properties of modified diesel were studied by a standard pin on disk apparatus. The wear rate was found to be reduced for all the nano additive concentrations in diesel and was least for 15 ppm. Based on studies conducted, 10 ppm is reported as an optimum concentration of nanoparticle in diesel having both enhanced stability and lubricity as compared to other concentrations of ceria nanoparticles in diesel.

Synthesis and properties biobased waterborne polyurethanes from glycolysis product of PET waste and poly(caprolactone) diol

Novel biobased poly(ester-urethane)s (PUDs) were synthesized by solvent free homogeneous solution polymerization of poly(caprolactone) diol (PCL), castor oil-based polyols (COLs), dimethylolpropionic acid (DMPA), isophorone diisocyanate (IPDI) and 1,4-butane diol (BD) as the chain extender. The polyurethane dispersions were prepared by adding required amount of triethylamine (TEA) and water. In this work, castor oil-based polyols have been synthesized using the depolymerized oligoester obtained from glycolysis of PET waste with poly(ethylene glycol) (PEG 400) and castor oil. The effects of the soft segments content on the thermal and coatings properties of resulting polyurethane films have been examined by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and measurement of the coatings properties. Phase separation of polyurethane shows a strong correlation with crystallization behaviour of the polyurethane prepared. It is established that all PUD samples containing PCL as a part soft segment with different molar ratio of castor-oil polyol are crystallisable polymers. The results from XRD analysis have showed that highest degree of crystallinity (23 and 22%) is reached in polyurethanes based on the largest content PCL diol (CPU77 and CPU73). The thermal stability of samples based on (COL/PCL molar ratio 0.25:0.75) possesses the best thermal properties but less values hardness coatings which can be ascribed to a decrease of the hard segment i.e. DMPA content in polyurethane dispersions. The long-term stability of polyurethane dispersions has been investigated using UV–vis spectroscopy. The physico-mechanical properties such as hardness adhesion test and gloss of the dried films have also been determined considering the effect of soft segment content on coating properties.