Effect of surfactants on the interfacial viscoelasticity and stability of silk fibroin at different oil-water interfaces.

BACKGROUND: The biocompatible amphiphilic silk fibroin, extracted from domesticated silkworms, can adsorb at the oil-water interface and form elastic interfacial layers. In this study, three surfactants (cationic cetyltrimethylammonium bromide, the nonionic polyoxyethylene sorbitan monolaurate, and the anionic sodium dodecyl sulfate) were selected to investigate, through interfacial shear rheology, the influences of surfactants on the interfacial viscoelasticity and stability of silk fibroin at the interfaces between water and two different oils. RESULTS: The presence of surfactant prolongs the equilibration time and enhances the interfacial elastic modulus and toughness of the interfacial silk fibroin layers, especially at the nonpolar dodecane-water interface. However, when the surfactant exceeds a critical concentration, the shear modulus and stability of interfacial silk fibroin layers begin to decrease due to the competitive adsorption of surfactant molecules and the weakening of the protein network. Owing to electrostatic interactions, the ionic surfactants cetyltrimethylammonium bromide and sodium dodecyl sulfate can form more hydrophobic complexes with silk fibroin, which results in higher shear moduli than for silk fibroin and silk fibroin-polyoxyethylene sorbitan monolaurate mixture. CONCLUSION: Both the surfactant type and oil polarity play important roles in the adsorption, shear viscoelasticity, and stability of silk fibroin at the oil-water interface. Enhanced interactions between a silk fibroin-surfactant mixture and the oil phase delay the equilibration of the adsorption layers but strengthen the stability of interfacial layers. © 2023 Society of Chemical Industry.

Influence of pH on the surface and foaming properties of aqueous silk fibroin solutions.

Silk fibroin (SF) adsorbs at the air/water interface, reduces the surface tension, and forms interfacial layers suppressing bubble coalescence and stabilizing foam. Variation of pH alters the inter-molecular interactions of SF in the interfacial layers and thus interfacial network formation, dilatational visco-elasticity and foaming properties. At pH 4, around the isoelectric point, the reduced electrostatic repulsion between the SF molecules results in thicker adsorbed layers, but adsorption rate, foaming rate and foam stability are lower than at pH 3 and pH 7. At the highest pH investigated (pH 7), the small aggregate size and high protein flexibility lead to the formation of more ordered and stable viscoelastic interfacial networks, which are resistant to deformation breakage and generate homogeneous, denser and more stable foams.

N-Benzyl HMTA induced self-assembly of organic-inorganic hybrid materials for efficient photocatalytic degradation of tetracycline.

Photocatalytic degradation technology (PDT), as one of the most important advanced oxidation technologies (AOTs) for environment-purifying, have drawn great attentions in recent years. It is highly desirable but remains challenging to design and synthesize catalysts with enhanced performance of photocatalysis. Herein, we develop a cation induced self-assembly strategy for the synthesis of two new organic-inorganic hybrid materials ({[BHMTA][Cu2(SCN)3]}n (1), {[BHMTA][Cu2I3]}n (2) BHMTA = N-benzylhexamethylenetetramine bromide). Owing to their unique structural and the desirable composition, the as-prepared organic-inorganic hybrid materials exhibit high efficiency and excellent cycling stability for degradation of tetracycline (TC) under visible light irradiation. In addition, the effect factors for photocatalysis such as catalyst dosage, temperature, and pH were also investigated. The possible mechanism studied shows that superoxide radicals (O2-) and holes (h+) are the main active substances in the degradation process of TC. This work may shed light on preparing new organic-inorganic hybrid materials with promising photocatalysis performance for water purification.

Preparation and Analyses of the Multifunctional Properties of 2D and 3D MOFs Constructed from Copper(I) Halides and Hexamethylenetetramine.

In this article, two two-dimensional and three-dimensional metal-organic frameworks are synthesized by the self-assembly of copper(I) halide and the hexamethylenetetramine (hmt) ligand. Compound 1 is a two-dimensional metal-organic framework composed of a pyramidal Cu4I5 cluster and hexamethylenetetramine, in which hmt-bridged Cu clusters form a two-dimensional (4,4)-connected net with a point symbol of (44·62) (44·62). Compound 2 is a homochiral three-dimensional metal-organic framework material generated through an unusual spontaneous crystallization from achiral precursors. The two compounds were characterized by a series of analyses such as infrared spectroscopy, elemental analysis, circular dichroism spectroscopy, and powder X-ray diffraction. Both of them exhibit unexpected stability under a wide range of conditions of acid and base. In addition, the fluorescence intensity changes regularly under acid-base conditions. Stokes shift shows a good linear relationship with -log [H+], which makes them become promising acid-base sensors. Compounds 1 and 2 also display selective adsorption and a significant degradation effect on the organic dye methylene blue. In addition, the fluorescence study indicated that compound 2 could be used as a sensor to detect Cr3+.

Rice straw cellulose nanofibrils reinforced poly(vinyl alcohol) composite films.

In this study, cellulose nanofibrils (CNFs), obtained from the chemical treatment of steam exploded rice straw fibers and the following oxidation by 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated system, were utilized to prepare the reinforced polyvinyl alcohol (PVA) composite films by solution casting method, and the morphology, transparency, thermal stability, mechanical properties and water absorption of these rice straw CNFs/PVA composite films were also investigated compared with the rice straw cellulose microfibrils (CMFs) reinforced PVA composite films. As compared with the rice straw CMFs/PVA composite films, the rice straw CNFs/PVA composite films exhibited more uniform fiber dispersion, better mechanical properties and transparency, and similar thermal stability. However, the rice straw CNFs/PVA composite films showed weaker water resistance than the rice straw CMFs/PVA composite films due to the existence of more polar groups in rice straw CNFs.

Effect of ionic strength on the interfacial viscoelasticity and stability of silk fibroin at the oil/water interface.

BACKGROUND: The amphiphilic character and surface activity endows silk fibroin with the ability to reside at fluid interfaces and effectively stabilize emulsions. However, the influence of relevant factors and their actual effect on the interfacial viscoelasticity and stability of silk fibroin at the oil/water interface has received less attention. In the present study, the effect of ionic strength on the interfacial viscoelasticity, emulsification effectiveness and stability of silk fibroin at the oil/water interface was investigated in detail. RESULTS: A higher ion concentration facilitates greater adsorption, stronger molecular interaction and faster structure reorganization of silk fibroin at the oil/water interface, thus causing quicker interfacial saturation adsorption, greater interfacial strength and lower interfacial structural fracture on large deformation. However, the presence of concentrated ions screens the charges in silk fibroin molecules and the zeta potential decreases as a result of electrostatic screening and ion-binding effects, which may result in emulsion droplet coalescence and a decrease in emulsion stability. CONCLUSION: The positively-charged ions significantly affect the interfacial elasticity and stability of silk fibroin layers at the oil/water interface as a result of the strong electrostatic interactions between counter-ions and the negatively-charged groups of silk fibroin. © 2016 Society of Chemical Industry.

Pickering emulsions stabilized by surface-modified Fe3O4 nanoparticles.

Unmodified Fe(3)O(4) nanoparticles do not stabilize Pickering emulsions of a polar oil like butyl butyrate. In order to obtain stable emulsions, the Fe(3)O(4) nanoparticles were modified by either carboxylic acid (RCOOH) or silane coupling agents (RSi(OC(2)H(5))(3)) to increase their hydrophobicity. The influence of such surface modification on the stability of the resultant Pickering emulsions was investigated in detail for both a non-polar oil (dodecane) and butyl butyrate in mixtures with water. The stability of dodecane-in-water emulsions in the presence of carboxylic acid-coated particles decreases as the length of the alkyl group (R) and the coating extent increase. However, such particles are incapable of stabilizing butyl butyrate-water emulsions even when the carboxylic acid length is decreased to two. However, the silane-coated Fe(3)O(4) nanoparticles can stabilize butyl butyrate-in-water emulsions, and they also increase the stability of dodecane-in-water emulsions. Thermal gravimetric analysis indicates that the molar quantity of silane reagent is much higher than that of carboxylic acid on nanoparticle surfaces after modification, raising their hydrophobicity and enabling enhanced stability of the resultant polar oil-water emulsions.

Interfacial rheology of natural silk fibroin at air/water and oil/water interfaces.

The interfacial viscoelastic behavior of natural silk fibroin at both the air/water and oil/water interfaces is reported. This natural multiblock copolymer is found to be strongly amphiphilic and forms stable films at these interfaces. The result is an interfacial layer that is rheologically complex with strong surface elastic moduli that are only slightly frequency-dependent. The kinetics of surface viscoelastic evolution are reported as functions of time for various concentrations of the spread films. Films deposited by Langmuir-Blodgett deposition were studied by scanning electron microscopy (SEM) to reveal a fibrous structure at the interface. The production of stable O/W emulsions by silk fibroin further confirms the generation of the elastic films at the oil/water interfaces.

Magnetic Pickering emulsions stabilized by Fe3O4 nanoparticles.

Superparamagnetic Fe(3)O(4) nanoparticles prepared by a classical coprecipitation method were used as the stabilizer to prepare magnetic Pickering emulsions, and the effects of particle concentration, oil/water volume ratio, and oil polarity on the type, stability, composition, and morphology of these functional emulsions were investigated. The three-phase contact angle (θ(ow)) of the Fe(3)O(4) nanoparticles at the oil-water interface was evaluated using the Washburn method, and the results showed that for nonpolar and weakly polar oils of dodecane and silicone, θ(ow) is close to 90°, whereas for strongly polar oils of butyl butyrate and 1-decanol, θ(ow) is far below 90°. Inherently hydrophilic Fe(3)O(4) nanoparticles can be used to prepare stable dodecane-water and silicone-water emulsions, but they cannot stabilize butyl butyrate-water and decanol-water mixtures with macroscopic phase separation occurring, which is in good agreement with the contact angle data. Emulsions are of the oil-in-water type for both dodecane and silicone oil, and the average droplet size increases with an increase in the oil volume fraction. For stable emulsions, not all of the particles are adsorbed to drop interfaces; the fraction adsorbed decreases with an increase in the initial oil volume fraction. Changes in the particle concentration have no obvious influence on the stability of these emulsions, even though the droplet size decreases with concentration.

[Three-dimensional finite-element analysis and biomechanical design of femoral prosthesis].

AA new total femoral prosthesis with composite structure was designed, and the femoral prostheses under static state were analyzed with ANSYS software (version 5.7). The effects of elastic modulus, Poisson's ratio and the ratio of the inner radius over the outer radius on the stress distribution were investigated. Through a comprehensive analysis of the experimental results of positive stress and shear stress on the prostheses, a new design of the femoral prosthesis was put forth as follows: choose the composite materials of which the outer layer has low elastic modulus and great Poisson's ratio, the inner layer has enough mechanic capability, and the increase in the ratio of the inner radius over the outer radius is as great as possible.