Ultrasound-assisted air-jet spinning of silk fibroin-soy protein nanofiber composite biomaterials

Ultrasound utilizes a non-radiation technology that can meet modern standards to gain access to cheap, reliable and sustainable modern energy. Ultrasound technology can be implemented in the field of biomaterials for its exceptional potential in controlling the shape of nanomaterials. This study presents the first example of the production of soy and silk fibroin protein composite nanofibers in various ratios via combining ultrasonic technology with air-spray spinning. Characterization of ultrasonic spun nanofibers was performed by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric (TG) analysis, water contact angle, water retention, enzymatic degradation, and cytotoxicity assays. The effects that adjustments on the ultrasonic time have on the surface morphology, structures, thermal properties, hydrophilicity, water-uptake, bio-enzyme degradability, mechanical properties, and cytocompatibility of the material were examined. It was discovered that as the sonication time increased from 0 to 180 min, the beading phenomenon disappeared, forming nanofibers with uniform diameter and porosity; while the content of β-sheet crystals in the composites and their thermal stability gradually increased, the materials glass transition temperature decreased, and preferred mechanical properties were obtained. Additional studies show that the hydrophilicity, water retention capacity and enzymatic degradation rate were also enhanced by ultrasound, providing a favorable environment for cell attachment and proliferation. This study highlights the experimental and theoretical methods for ultrasound assisted air-jet spinning of biopolymer nanofibrous materials with tunable properties and high biocompatibility, which provide a wide range of applications in wound dressings and drug-carrying systems. This work shows great potential for a direct road to sustainable development of protein based fibers in the industry, thus promoting economic growth, and improving the health of the general population and well-being of wounded patients worldwide.     

Dense coating of surface mounted CuBTC Metal-Organic Framework nanostructures on silk fibers, prepared by layer-by-layer method under ultrasound irradiation with antibacterial activity

The growth of Cu₃(BTC)₂ (BTC = 1,3,5-benzenetricarboxylate), also known as CuBTC and HKUST-1, Metal-Organic Framework (MOF) nanostructures on silk fibers were achieved by layer-by-layer technique in alternating bath of Cu(OAc)₂·2H₂O and H₃BTC solutions under ultrasound irradiation. The effect of pH, reaction time, ultrasound irradiation and sequential dipping steps in growth of the CuBTC Metal-Organic Framework nanostructures has been studied. These systems depicted a decrease in the size accompanying a decrease in the sequential dipping steps. In addition, dense coating of silk fibers with CuBTC MOF results in decrease the emission intensity of silk fibers. The silk fibers containing CuBTC Metal-Organic Framework exhibited high antibacterial activity against Escherichia coli and Staphylococcus aureus. The samples were characterized with powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) spectra and scanning electron microscopy (SEM). XRD analyses indicated that the prepared CuBTC MOF nanostructures on silk fibers were crystalline.     

Superconductivity and the b.c.c. to A-15 transformation in Nb-Au alloys2

Nb-Au alloys near the composition Nb₃Au can be quenched from the high temperature α solid solution phase field, retaining the b.c.c. structure. We report results on their superconducting, mechanical and physical properties as a function of composition. Short low temperature anneals transform these materials to the equilibrium A-15 structure with T_c up to 11K. We report results on the superconducting and physical properties of the transformed A-15 structure materials and describe how the properties of the transformed materials are affected by annealing temperature and time.     

Improved mechanical properties of retorted carrots by ultrasonic pre-treatments

The use of ultrasound pre-processing treatment, compared to blanching, to enhance mechanical properties of non-starchy cell wall materials was investigated using carrot as an example. The mechanical properties of carrot tissues were measured by compression and tensile testing after the pre-processing treatment prior to and after retorting. Carrot samples ultrasound treated for 10 min at 60 °C provided a higher mechanical strength (P < 0.05) to the cell wall structure than blanching for the same time period. With the addition of 0.5% CaCl₂ in the pre-treatment solution, both blanching and ultrasound treatment showed synergistic effect on enhancing the mechanical properties of retorted carrot pieces. At a relatively short treatment time (10 min at 60 °C) with the use of 0.5% CaCl₂, ultrasound treatment achieved similar enhancement to the mechanical strength of retorted carrots to blanching for a much longer time period (i.e. 40 min). The mechanism involved appears to be related to the stress responses present in all living plant matter. However, there is a need to clarify the relative importance of the potential stress mechanisms in order to get a better understanding of the processing conditions likely to be most effective. The amount of ultrasound treatment required is likely to involve low treatment intensities and there are indications from the structural characterisation and mechanical property analyses that the plant cell wall tissues were more elastic than that accomplished using low temperature long time blanching.     

High-intensity ultrasound improves the physical stability of myofibrillar protein emulsion at low ionic strength by destroying and suppressing myosin molecular assembly

The specific molecular behavior of myofibrillar proteins (MPs) in low-salt media limits the development of muscle protein-based emulsions. This study aimed to evaluate the potential of high-intensity ultrasound (HIU; 150, 300, 450, and 600 W) to improve the physical stability of MP emulsion at low ionic strength and decipher the underlying mechanism. According to the physical stability analysis, HIU pretreatment, especially at 450 W power, significantly improved the physical stability of MP emulsions, as evidenced by the reduced particle size, enhanced inter-droplet interactions, and increased uniformity of the droplet size distribution (p < 0.05). The results of interfacial protein composition, Fourier transform infrared spectroscopy analysis, and microscopic morphology observation of the aqueous MP suspension suggested that HIU induced the depolymerization of filamentous myosin polymers and inhibited the subsequent self-assembly behavior. These effects may facilitate protein adsorption and molecular rearrangement at the oil–water interface, forming a complete interfacial layer and, thus, droplet stabilization. Confocal laser scanning microscopy observations further confirmed these results. In conclusion, these findings provide direct evidence for the role of HIU in improving the physical stability of MP emulsions at low ionic strength.     

The effect of ultrasound treatment on the interaction of brine with pork meat proteins

The objective of the study is to elucidate the effect of ultrasound treated salt solution on curing of pork meat. The interactions of salt (NaCl) solutions of 3 and 25% with the proteins of pork meat are studied. High intensity ultrasound operating at 20 kHz was used. The differential scanning calorimetry (DSC), NMR spin-spin relaxation time, unfrozen water and water diffusion coefficient measurements were carried out in meat cured with ultrasound treated and untreated salt solutions. The effect of ultrasonication was most evident from measured spin-spin relaxation times T₂₁, the rate of chemical exchange of water protons k and the amount of unfrozen water W_unf in the meat. The measured diffusion coefficient of water D_w in meat cured with ultrasound treated and control salt solution did not show significant difference. The nuclear magnetic resonance (NMR) relaxation data, differential scanning calorimetry (DSC) and the diffusion coefficient data reliably show that the possible action of ultrasound to salt solution was manifested on the first 2 days of the experiment with a 3% salt solution.     

Surface modification and properties of Bombyx mori silk fibroin films by antimicrobial peptide

The Bombyx mori silk fibroin films (SFFs) were modified by a Cecropin B (CB) antimicrobial peptide, (NH₂)-NGIVKAGPAIAVLGEAAL-CONH₂, using the carbodiimide chemistry method. In order to avoid the dissolution of films during the modification procedure, the SFFs were first treated with 60% (v/v) ethanol aqueous solution, resulting a structural transition from unstable silk I to silk II. The investigation of modification conditions showed that the surface-modified SFFs had the satisfied antimicrobial activity and durability when they were activated by EDC·HCl/NHS solution followed by a treatment in CB peptide/PBS buffer (pH 6.5 or 8) solution at ambient temperature for 2 h. Moreover, the surface-modified SFFs showed the smaller contact angle due to the hydrophilic antimicrobial peptides coupled on the film surface, which is essential for the cell adhesion and proliferation. AFM results indicated that the surface roughness of SFFs was considerably increased after the modification by the peptides. The elemental composition analysis results also suggested that the peptides were tightly coupled to the surface of SFFs. This approach may provide a new option to engineer the surface-modified implanted materials preventing the biomaterial-centered infection (BCI).     

The morphologies of fractured surfaces and fracture toughness in some As-Se-Sb-S-I glasses

As part of a general physical characterization of amorphous materials in the pseudobinary system (As₂Se₃)_100−x(SbSI)_x type, their indentation fracture toughness was determined. It is a system with the variable ratio of classical amorphous compound As₂Se₃ and the molecule of antimony sulfoiodide, SbSI, which in the monocrystal form is characterized as ferroelectrics. Because of chalcogenides are generally very brittle and under load they crack very easily, these glasses have been studied with the aim of examining the possibility of obtaining some new structures on the basis of the materials with amorphous internal network, the structures that will have a higher quality in respect of mechanical properties. The morphologies of fractured surfaces were investigated by scanning electron microscope.     

Effects of high-intensity ultrasound on the structural,optical, mechanical and physicochemical properties of pea protein isolate-based edible film

Pea protein is a promising alternative to animal-based protein and the interest in its application in food industry has been rapidly growing. In this study, pea protein isolates (PPI) were used to form protein-based edible films and the effect of ultrasound treatment on the structure of PPI and the structural, optical, mechanical and physicochemical properties of PPI-films were investigated. Ultrasound induced unfolding of PPI and exposed interior hydrophobic groups to protein surface while both PPI dissociation and formation of large aggregates were observed, as confirmed by measuring intrinsic emission fluorescence, surface hydrophobicity, surface charge, and particle size distribution and polydispersity index, respectively. FE-SEM showed that ultrasound decreased the cracks and protein aggregates at the surface of PPI-film. The film structure was also investigated by FTIR, which showed peak shift in amide I and II region and noticeable difference of protein secondary structure as affected by ultrasound. As a result of such structural changes caused by ultrasound, the properties of PPI-films were improved. Results showed that ultrasound greatly improved the film transparency, significantly increased film tensile strength but not elongation at break, and decreased moisture content and water vapor permeability of the film. This study provided structural data as evidence for utilizing ultrasound technique to develop PPI-films with improved optical, mechanical and water barrier properties.     

Ultrasound-promoted coating of silk yarn with different morphology of magnesium hydroxide nanostructures

The growth of magnesium hydroxide nanostructures on silk yarn was achieved by sequential dipping steps in alternating bath of magnesium nitrate and potassium hydroxide under ultrasound irradiation. The effects of ultrasound irradiation, concentration, pH and sequential dipping steps on growth of the Mg(OH)₂ nanostructures have been studied. Morphology of the nanostructures, depending on pH and with decreasing pH from 13 to 8, changed from nanoparticle to nanoneedle. Results show a decrease in the particles size as the concentration and sequential dipping steps increased. The physicochemical properties of the nanostructures were determined by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and wavelength dispersive X-ray (WDX).     

Preparation and Characterization of Poly(Vinyl Alcohol) (PVA)/SiO2, PVA/Sulfosuccinic Acid (SSA) and PVA/SiO2/SSA Membranes: A Comparative Study

Abstract

New organic–inorganic nanocomposites based on PVA, SiO₂ and SSA were prepared in a single step using a solution casting method, with the aim to improve the thermomechanical properties and ionic conductivity of PVA membranes. The structure, morphology, and properties of these membranes were characterized by Raman spectroscopy, small- and wide-angle X-ray scattering (SAXS/WAXS), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), water uptake (Wu) measurements and ionic conductivity measurements. The SAXS/WAXS analysis showed that the silica deposited in the form of small nanoparticles (～ 10?nm) in the PVA composites and it also revealed an appreciable crystallinity of pristine PVA membrane and PVA/SiO₂ membranes (decreasing with increasing silica loading), and an amorphous structure of PVA/SSA and PVA/SSA/SiO₂ membranes with high SSA loadings. The thermal and mechanical stability of the nanocomposite membranes increased with the increasing silica loading, and silica also decreased the water uptake of membranes. As expected, the ionic conductivity increased with increasing content of the SSA crosslinker, which is a donor of the hydrophilic sulfonic groups. Some of the PVA/SSA/SiO₂ membranes had a good balance between stability in aqueous environment (water uptake), thermomechanical stability and ionic conductivity and could be potential candidates for proton exchange membranes (PEM) in fuel cells.     

Enzymolysis kinetics and structural characteristics of rice protein with energy-gathered ultrasound and ultrasound assisted alkali pretreatments

This research investigated the structural characteristics and enzymolysis kinetics of rice protein which was pretreated by energy-gathered ultrasound and ultrasound assisted alkali. The structural characteristics of rice protein before and after the pretreatment were performed with surface hydrophobicity and Fourier transform infrared (FTIR). There was an increase in the intensity of fluorescence spectrum and changes in functional groups after the pretreatment on rice protein compared with the control (without ultrasound and ultrasound assisted alkali processed), thus significantly enhancing efficiency of the enzymatic hydrolysis. A simplified kinetic equation for the enzymolysis model with the impeded reaction of enzyme was deduced to successfully describe the enzymatic hydrolysis of rice protein by different pretreatments. The initial observed rate constants (K_in,0) as well as ineffective coefficients (k_imp) were proposed and obtained based on the experimental observation. The results showed that the parameter of k_in,0 increased after ultrasound and ultrasound assisted alkali pretreatments, which proved the effects of the pretreatments on the substrate enhancing the enzymolysis process and had relation to the structure changes of the pretreatments on the substrate. Furthermore, the applicability of the simplified model was demonstrated by the enzymatic hydrolysis process for other materials.     

Lightweight and thermally insulating aerogel glass materials

Glass represents an important and widely used building material, and crucial aspects to be addressed include thermal conductivity, visible light transmittance, and weight for windows with improved energy efficiency. In this work, by sintering monolithic silica aerogel precursors at elevated temperatures, aerogel glass materials were successfully prepared, which were characterized by low thermal conductivity [k ≈ 0.17–0.18 W/(mK)], high visible transparency (T _vis ≈ 91–96 % at 500 nm), low density (ρ ≈ 1.60–1.79 g/cm³), and enhanced mechanical strength (typical elastic modulus E _r ≈ 2.0–6.4 GPa). These improved properties were derived from a series of successive gelation and aging steps during the desiccation of silica aerogels. The involved sol → gel → glass transformation was investigated by means of thermo-gravimetric analysis, scanning electron microscopy, nanoindentation, and Fourier transform infrared spectroscopy. Strategies of improving further the mechanical strength of the obtained aerogel glass materials are also discussed.     

Formation of silk fibroin nanoparticles in water-miscible organic solvent and their characterization

When Silk fibre derived from Bombyx mori, a native biopolymer, was dissolved in highly concentrated neutral salts such as CaCl₂, the regenerated liquid silk, a gradually degraded peptide mixture of silk fibroin, could be obtained. The silk fibroin nanoparticles were prepared rapidly from the liquid silk by using water-miscible protonic and polar aprotonic organic solvents. The nanoparticles are insoluble but well dispersed and stable in aqueous solution and are globular particles with a range of 35–125 nm in diameter by means of TEM, SEM, AFM and laser sizer. Over one half of the ɛ-amino groups exist around the protein nanoparticles by using a trinitrobenzenesulfonic acid (TNBS) method. Raman spectra shows the tyrosine residues on the surface of the globules are more exposed than those on native silk fibers. The crystalline polymorph and conformation transition of the silk nanoparticles from random-coil and α-helix form (Silk I) into anti-parallel β-sheet form (Silk II) are investigated in detail by using infrared, fluorescence and Raman spectroscopy, DSC, ¹³C CP-MAS NMR and electron diffraction. X-ray diffraction of the silk nanoparticles shows that the nanoparticles crystallinity is about four fifths of the native fiber. Our results indicate that the degraded peptide chains of the regenerated silk is gathered homogeneously or heterogeneously to form a looser globular structure in aqueous solution. When introduced into excessive organic solvent, the looser globules of the liquid silk are rapidly dispersed and simultaneously dehydrated internally and externally, resulting in the further chain–chain contact, arrangement of those hydrophobic domains inside the globules and final formation of crystalline silk nanoparticles with β-sheet configuration. The morphology and size of the nanoparticles are relative to the kinds, properties and even molecular structures of organic solvents, and more significantly to the looser globular substructure of the degraded silk fibroin in aqueous solution. It is possible that the silk protein nanoparticles are potentially useful in biomaterials such as cosmetics, anti-UV skincare products, industrial materials and surface improving materials, especially in enzyme/drug delivery system as vehicle.     

Novel heat-resistance UV curable waterborne polyurethane coatings modified by melamine

Novel UV curable waterborne polyurethane coatings (UVWPU) modified by melamine was prepared using isophorone diisocyanate (IPDI), polyethylene glycol (PEG), α,α-dimethylol propionic acid (DMPA), hydroxyethyl acrylate (HEA) as main materials. Copolymer structure was verified using Fourier transform infrared spectroscopy (FT-IR). Performance of the coatings was evaluated by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA), and mechanical tests such as pencil hardness and resistance to water. The results showed that the modified UVWPU film had the good thermal resistance, water resistance and mechanical properties. The optimum melamine dosage was 4.70 wt.%, the glass transition temperature (T_g) of the modified film increased by 20.4 °C and 5% weight-loss temperature (253 °C) increased by 105 °C. No change color, crinkle, desquamate, dehisce and frothy were found after the modified film dried at 130 °C for 2 h.     

Ultrasound-assisted alkaline proteinase extraction enhances the yield of pecan protein and modifies its functional properties

To enhance the extraction yield of pecan protein and modify its functional properties, this study investigated whether both ultrasound and enzyme have a synergistic impact on the extraction of pecan (Carya illinoinensis (Wangenh.) K. Koch) protein. The highest protein extraction rate (25.51%) was obtained under the conditions of 1415.43 W^.cm⁻², 15 min, pH 10.0, 50 °C, and 1% (w/w) alkaline proteinase. Owing to its high shear, mechanical energy and cavitation, the ultrasound process increased the solubility of the substrate making it readily accessible to the enzyme, thereby accelerating the chemical reaction and improving the yield of the protein. The optimized ultrasound-assisted enzymatic method (400 W, 20 kHz, 5 s/3s) effectively changed the secondary and tertiary structure of the pecan protein. The results of surface hydrophobicity, intrinsic fluorescence spectra, sulfhydryl content and scanning electron microscopy all indicated the unfolding of protein and exposure of hydrophobic groups and sulfhydryl groups. Moreover, the protein obtained by this method showed higher solubility (70.77%), higher emulsifying activity (120.56 m²/g), smaller particle size (326.7 nm), and better dispersion (0.305) than single ultrasound and non-ultrasound methods (p < 0.05). To conclude, ultrasound-assisted enzymatic method could be an appropriate technique to improve the yield and quality of the pecan protein. The study also provides a theoretical basis for the application of pecan protein in food processing.     

Effects of high frequency ultrasound irradiation on incorporation of SiO2 particles within polypyrrole films

This paper deals with the effect of ultrasound on polypyrrole/SiO₂ composite film elaboration through various steps (particle dispersion, electrosynthesis). Experiments were carried out on stainless steel in phosphoric acid solution. An efficient method for dispersion of SiO₂ particles prior to electropolymerization, based on low frequency irradiation (20 kHz), was proposed. It was shown that mechanical effects of high frequency ultrasound (i.e. mass transfer improvement) led to enhancement of electropolymerization kinetics. Scanning electron microscopy imaging and glow discharge optical emission spectroscopy revealed localization of SiO₂ particles in the outer region of the films as well as better incorporation of particles under high frequency ultrasound irradiation. Finally, anticorrosion behavior of formed films was investigated in sodium chloride solution by Open Circuit Potential and anodic polarization methods. The results showed that polypyrrole/SiO₂ films elaborated under ultrasound irradiation exhibit the best protective performances.     

Ultrasound-assisted coating of silk yarn with sphere-like Mn3O4 nanoparticles

The growth of sphere-like trimanganese tetraoxide (Mn₃O₄) nanoparticles on silk fiber was achieved by sequential dipping in an alternating bath of potassium hydroxide and manganese(II) nitrate under ultrasound irradiation. Some parameters such as the effect of pH, numerous sequential dipping and ultrasonic irradiation on growth of the nanoparticles have been studied. The samples were characterized with powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and wavelength dispersive X-ray (WDX).     

Spontaneous stress-induced oxidation of Ce ions in Gd-doped ceria at room temperature

Cerium oxides are widely used within catalysis and fuel cells. The key parameters of interest, including catalytic activity, transport properties and defect structure are all fundamentally linked to the oxidation state of the cerium ions within the material which can adopt a 3+ or 4+ oxidation state. We use Raman spectroscopy, as well as scanning and optical microscopy to show that the oxidation state of cerium ions within Ce_0.8Gd_0.2O_2?x can be altered either through chemically induced strain (imparted during processing), mechanical indentation, fracture or applied mechanical load. This work shows that both the chemical environment and stress state will play a role in determining the oxidation state of the cerium ions within ceria containing materials. It has been shown that the rate of oxidation of Ce_0.8Gd_0.2O_2?x can be dramatically altered at room temperature via changing the local stress state of the material.     

Does power ultrasound affect Nafion® dispersions?

The effect of low frequency power ultrasound on Nafion® ionomer used for fabricating proton exchange membrane fuel cell (PEMFC) and water electrolyzer (PEMWE) catalyst inks was investigated. In this study, a series of Nafion® dispersions having three concentrations (10, 5, and 2.5% w/v) were studied under various irradiation durations (t_us), at fixed ultrasonic frequency (f = 42 kHz) and ultrasonic power (P > 2 W), under either controlled or unregulated bulk solution temperature conditions using a laboratory ultrasonic cleaning bath. Viscosity (η), thermal degradation, and glass transition temperature (T_g) for all Nafion® dispersion samples was measured and compared to untreated Nafion® samples. In our conditions, it was found that power ultrasound lowered the viscosity of all tested Nafion® dispersion samples; whilst thermogravimetric and differential scanning calorimetry analyses showed that for all ultrasonically irradiated samples, a negligible overall polymer degradation and no obvious change in T_g was observed under controlled and unregulated bulk temperature conditions. It was found that it is possible that acoustic cavitation causes depolymerisation followed by a polymerisation initiation step during ultrasonication. By comparing the ultrasonically treated and high-shear mixed samples, it was also observed that acoustic and hydrodynamic cavitation played an important role in the reduction of dispersion viscosity.