Glassy and compressed nanoemulsions stabilized with sodium dodecyl sulfate in the presence of poly(ethylene glycol)-diacrylate.

The rheology of concentrated nanoemulsions is critical for their formulation in various applications, such as pharmaceuticals, foods, cosmetics, and templating advanced materials. The rheological properties of nanoemulsions depend on interdroplet interactions, Laplace pressure, dispersed phase volume fraction, and continuous phase properties. The interdroplet forces can be tuned by background electrolytes (i.e., charge screening), surfactant type, the excess surfactant micelle concentration, and depletant molecules such as polymer chains. In the current research, we study the effect of varying the content of poly(ethylene glycol)-diacrylate (PEGDA) on the interfacial tension of the water-oil phase and rheological properties of concentrated nanoemulsions with 50% and 60% volume fractions. Sodium dodecyl sulfate (SDS) is used as the ionic surfactant. The final concentrated nanoemulsions are repulsive according to overall interaction potentials and are in the glass and compressed states based on the effective volume fraction estimation. They contain nearly same SDS concentration on the droplet surface and also in the bulk, but a different amount of PEGDA. The scaled rheological properties of the glassy nanoemulsions show a higher dependency on the PEGDA content and the possible effect of polymer-surfactant complexations compared to those of the compressed ones. This dependency is more pronounced in small strain amplitudes but not in large strains in the non-linear regime. These results provide insights into formulating concentrated nanoemulsions with controlled rheology for expanded application areas.

Novel MXene-Modified Polyphenyl Sulfone Membranes for Functional Nanofiltration of Heavy Metals-Containing Wastewater.

In this work, MXene as a hydrophilic 2D nanosheet has been suggested to tailor the polyphenylsulfone (PPSU) flat sheet membrane characteristics via bulk modification. The amount of MXene varied in the PPSU casting solution from 0-1.5 wt.%, while a series of characterization tools have been employed to detect the surface characteristics changes. This included atomic force microscopy (AFM), scanning electron microscopy (SEM), contact angle, pore size and porosity, and Fourier-transform infrared spectroscopy (FTIR). Results disclosed that the MXene content could significantly influence some of the membranes' surface characteristics while no effect was seen on others. The optimal MXene content was found to be 0.6 wt.%, as revealed by the experimental work. The roughness parameters of the 0.6 wt.% nanocomposite membrane were notably enhanced, while greater hydrophilicity has been imparted compared to the nascent PPSU membrane. This witnessed enhancement in the surface characteristics of the nanocomposite was indeed reflected in their performance. A triple enhancement in the pure water flux was witnessed without compromising the retention of the membranes against the Cu2+, Cd2+ and Pd2+ feed. In parallel, high, and comparable separation rates (>92%) were achieved by all membranes regardless of the MXene content. In addition, promising antifouling features were observed with the nanocomposite membranes, disclosing that these nanocomposite membranes could offer a promising potential to treat heavy metals-containing wastewater for various applications.

Biological and bioactivity assessment of dextran nanocomposite hydrogel for bone regeneration.

Insufficient biological and bioactive properties of dextran hydrogels limit their applications as promising scaffolds for tissue engineering. We developed nanocomposite dextran hydrogels comprised of bioactive glass (nBGC: 64% SiO2, 31% CaO, 5% P2O5) nanoparticles with an average particle size of 77 nm using a chemical crosslinking of dextran chains to form 3D hydrogel networks. In the current study; bioactivity of the obtained nanocomposite hydrogels was evaluated through the formation of apatite crystal structures after the incubation in simulated body fluid (SBF) at various submersion periods and nBGC content. The scanning electron microscopy (SEM) micrographs represented an enhanced hydroxyapatite formation on the cross section of nanocomposite comprising of nBGC content from 2 to 8 (% by wt). Biomineralization results of Dex-8 (% by wt) composite during 7, 14 and 28 days immersion indicated the apatite layer formation and the growth of apatite crystal size on the surface and cross section of the nanocomposite. Moreover, MTT assessments indicated that human osteosarcoma cells (SaOS-2) were able to adhere and spread within the dextran hydrogels reinforced with the bioactive glass nanoparticles. With regard to enhanced bioactivity and biocompatibility, the developed dextran-nBGC hydrogel could be considered as a suitable candidate for bone tissue engineering application.

Interdroplet Interactions and Rheology of Concentrated Nanoemulsions for Templating Porous Polymers.

In the current study, we investigate the colloidal behavior of nanoemulsions over a wide range of oil volume fractions (φ) from dilute to concentrated regime. The dilute system contains 25% silicone oil dispersed in the aqueous phase consisting of poly(ethylene glycol)-diacrylate (PEGDA) and sodium dodecyl sulfate (SDS), which is concentrated through evaporation of water at two different rates at ambient temperature. The rheological studies show that the liquid-like nanoemulsions transform into viscoelastic gels at a volume fraction of ∼30%. The plateau storage modulus of the nanoemulsions increases in the semidilute systems (φ below 45%) and then decreases steadily with increasing φ up to 60%. Dependency of the modulus on the evaporation rate can be observed in the rheological results. According to the rheological results and the overall pairwise interactions estimated between droplets, we propose two regimes of colloidal interactions. In the semidilute regime, the attractive gelation occurs due to considerable short-range attractive depletion induced by the PEGDA oligomer and SDS micelles. In the concentrated regime, the gel weakens by increasing φ mainly due to the structural stabilization barrier from a high concentration of micelles. The PEGDA in the continuous phase of the nanoemulsions can be crosslinked through photopolymerization, resulting in nanoporous PEGDA hydrogels upon removal of oil droplets. We study the water uptake of the nanoporous hydrogels prepared from the nanoemulsion templates at φ = 60%. The hydrogel obtained from the nanoemulsion with fast evaporation rate shows higher water uptake than that obtained from the slowly concentrated nanoemulsion. The tunable viscoelastic behavior of concentrated nanoemulsions as well as the resulting nanoporous hydrogels offers a new platform to design the soft materials for a wide range of applications.

Fabrication and physicochemical characterization of a novel magnetic nanocomposite scaffold: Electromagnetic field effect on biological properties.

In the current research, a novel poly(ε-caprolactone) nanofibrous composite scaffold including CZF-NPs1 (cobalt­zinc ferrite nanoparticles) was investigated to study the physical, mechanical and biological properties of new magnetic nanofibrous materials and then to evaluate the effect of applied electromagnetic field on biological properties of these scaffolds. It was observed that the incorporation of CZF-NPs up to 3 wt.% leads to decrease in nanofibers' diameter to 466 nm. By raising the content of CZF-NPs, hydrophilicity and biodegradation of magnetic nanofibrous scaffolds improved significantly. In addition, the mechanical properties of nanofibers such as stress at break point was interestingly increased in the sample with 3 wt.% of CZF-NPs. The results of biocompatibility, cell adhesion and cell staining assays with L929 cells are much more improved in nanofibers embedded with CZF-NPs in the presence of external electromagnetic field (EMF). According to this study, magnetic nanofibrous scaffolds composed of PCL/CZF-NPs could be considered as a promising candidate to regenerate damaged tissues.

Fabrication and characterization of dextran/nanocrystalline ß-tricalcium phosphate nanocomposite hydrogel scaffolds.

Design of bioactive three-dimensional scaffolds to support bone tissue repair and regeneration become a key area of research in tissue engineering. Herein, porous hybrid hydrogels composed of dextran incorporated with nanocrystalline ß-tricalcium phosphate (ß-TCP) particles were tailor made as scaffolds for bone tissue engineering. ß-TCP was successfully introduced within the dextran networks crosslinked through intermolecular ionic interactions and hydrogen bonding confirmed by FTIR spectroscopy. The effect of ß-TCP content on equilibrium water uptake and swelling kinetics of composite hydrogels was investigated. It was found that the homogeneous distribution of ß-TCP nanoparticles through the hydrogel matrix contributes to higher porosity and swelling capacity. In depth swelling measurements revealed that while in the early stage of swelling, water diffusion follows the Fick's law, for longer time swelling behavior of hydrogels undergo the second order kinetics. XRD measurements represented the formation of apatite layer on the surface of nanocomposite hydrogels after immersion in the SBF solution, which implies their bioactivity. Cell culture assays confirmed biocompatibility of the developed hybrid hydrogels in vitro. The obtained results converge to offer dextran/ß-TCP nanocomposite hydrogels as promising scaffolds for bone regeneration applications.

Dextran hydrogels incorporated with bioactive glass-ceramic: Nanocomposite scaffolds for bone tissue engineering.

A series of nanocomposite scaffolds comprised of dextran (Dex) and sol-gel derived bioactive glass ceramic nanoparticles (nBGC: 0-16 (wt%)) were fabricated as bioactive scaffolds for bone tissue engineering. Scanning electron microscopy showed Dex/nBGC scaffolds were consisting of a porous 3D microstructure with an average pore size of 240 µm. Energy-dispersive x-ray spectroscopy illustrated nBGC nanoparticles were homogenously distributed within the Dex matrix at low nBGC content (2 wt%), while agglomeration was observed at higher nBGC contents. It was found that the osmotic pressure and nBGC agglomeration at higher nBGC contents leads to increased water uptake, then reduction of the compressive modulus. Bioactivity of Dex/nBGC scaffolds was validated through apatite formation after submersion in the simulated body fluid. Dex/nBGC composite scaffolds were found to show improved human osteoblasts (HOBs) proliferation and alkaline phosphatase (ALP) activity with increasing nBGC content up to 16 (wt%) over two weeks. Owing to favorable physicochemical and bioactivity properties, the Dex/nBGC composite hydrogels can be offered as promising bioactive scaffolds for bone tissue engineering applications.

Effects of chain length of the cross-linking agent on rheological and swelling characteristics of dextran hydrogels.

Rheological characteristics during chemical gelation of semidilute solutions of dextran in the presence of cross-linking agents of different chain length are reported. Effects of cross-linker chain length on the gel point, structure of the gel network, and mechanical properties were investigated. The rheological results disclose that for all systems, the gelation process proceeds over a long time and both the complex viscosity and the power law exponent reveal that solid-like gel structures are formed in the post-gel region. Water absorption behavior of the gels was studied and the results were interpreted by using a kinetic model indicating that the swelling is diffusion controlled. The findings clearly show that the rheological characteristics, such as the time of gelation and gel strength of dextran hydrogels can be tuned by changing the chain length of the cross-linker agent. Furthermore, the swelling results also exposed significant differences between gels cross-linked with the two different cross-linker agents.

Exploring the effect of formulation parameters on the particle size of carboxymethyl chitosan nanoparticles prepared via reverse micellar crosslinking.

Carboxymethyl chitosan (CMCh), as a non-toxic, biocompatible and biodegradable semi-synthetic biopolymer with mucoadhesive properties, is widely investigated for targeting drug or gene delivery applications. Here, fabrication of CMCh nanoparticles will be reported using a reverse (w/o) micellar system to provide particles with tuneable mean sizes. Reverse microemulsions were prepared by dispersing aqueous solution of CMCh in n-hexane using sodium-bis(ethylhexyl)-sulfosuccinate (AOT) and glutaraldehyde (GA) as an emulsifier and a crosslinking agent, respectively. The obtained particles were perfectly spherical in the nanometric size range (40-140 nm) with a narrow size distribution according to the FE-SEM images. To determine the effective parameters on the mean nanosphere size, CMCh, AOT and GA concentrations were varied according to a full-factorial, three-level design-of-experiments. After evaluating the results, it was found that AOT and CMCh concentrations had a significant effect on the mean nanosphere size while GA concentration surprisingly showed non-significant, minor effects on the same response.

Rheological Study and Molecular Dynamics Simulation of Biopolymer Blend Thermogels of Tunable Strength.

The temperature-induced gelation of chitosan/glycerophosphate (Chs/GP) systems through physical interactions has shown great potential for various biomedical applications. In the present work, hydroxyethyl cellulose (HEC) was added to the thermosensitive Chs/GP solution to improve the mechanical strength and gel properties of the incipient Chs/HEC/GP gel in comparison with the Chs/GP hydrogel at body temperature. The physical features of the macromolecular complexes formed by the synergistic interaction between chitosan and hydroxyethyl cellulose in the presence of ß-glycerophosphate disodium salt solution have been studied essentially from a rheological point of view. The temperature and time sweep rheological characterizations of the thermogelling systems revealed that the sol-gel transition temperature of the Chs/HEC/GP blends is equal to 37 °C at neutral pH; with increasing HEC content in the solutions, more compact networks with considerably improved gel strength are formed without influencing the gelation time. The formed hydrogel matrix has enough mechanical integrity and adequate strength for using it as injectable in situ forming matrices for biomedical applications. The classical Winter-Chambon (W-C) and Fredrickson-Larson (F-L) theories were applied to determine the gel point. In view of the obtained results, it is shown that the F-L theory can be employed as a robust and less tedious method than the W-C approach to precisely determine the gel point in these systems. At the end, molecular simulation studies were conducted by using ab initio quantum mechanics (QM) calculations carried out on Chs and HEC models, and molecular dynamics (MD) simulations of solvated Chs/HEC blend systems showed the binding behavior of Chs/HEC polymers. Analyses of interaction energy, radial distribution function, and hydrogen bonding from simulation studies strongly supported the experimental results; they all disclosed that hydrogen-bond formation between Chs moieties with regard to HEC chains plays an important role for the stabilization of the complexes.

An engineering approach to design of dextran microgels size fabricated by water/oil emulsification.

A correlation, based on fluid mechanics, has been investigated for the mean particle diameter of crosslinked dextran microgels (CDMs) prepared via a water/oil emulsification methodology conducted in a single-stirred vessel. To this end, non-dimensional correlations were developed to predict the mean particle size of CDMs as a function of Weber number, Reynolds number and viscosity number similar to ones introduced for liquid-liquid dispersions. Moreover, a Rosin-Rammler distribution function has been successfully applied to the microgel particle size distributions. The correlations were validated using experimentally obtained mean particle sizes for CDMs prepared at different stirring conditions. The validated correlation is especially applicable to medical and pharmaceutical applications where strict control on the mean particle size and size distribution of CDMs are extremely essential. [Formula: see text].