Easy and Effective Method for α-CD:N2O Host-Guest Complex Formation.

α-CD:N2O "host-guest" type complexes were formed by a simple solid-gas reaction (N2O sorption into α-CD) under different gas pressures and temperatures. The new N2O inclusion method applied in the present study was compared with the already known technique based on the crystallization of clathrates from a water solution of α-CD saturated with N2O. A maximum storage capacity of 4.5 wt.% N2O was achieved when charging the cyclodextrin from a gas phase. The amount of included gas decreases to 1.3 wt.% when the complex is stored in air at 1 atm and room temperature, analogous to that achieved by the crystallization of α-CD:N2O. Furthermore, it was shown that the external coordination of N2O to either the upper or lower rim of α-CD without hydration water displacement is the preferred mode of binding, due to hydrogen bonds with neighboring -OH groups from the host macrocycle and three of the hydration water molecules nearby. The capacity of α-CD to store N2O and the thermal stability of the α-CD:N2O complex demonstrated promising applications of these types of complexes in food and beverages.

Soft dendritic microparticles with unusual adhesion and structuring properties.

The interplay between morphology, excluded volume and adhesivity of particles critically determines the physical properties of numerous soft materials and coatings1-6. Branched particles2 or nanofibres3, nanofibrillated cellulose4 or fumed silica5 can enhance the structure-building abilities of colloids, whose adhesion may also be increased by capillarity or binding agents6. Nonetheless, alternative mechanisms of strong adhesion found in nature involve fibrillar mats with numerous subcontacts (contact splitting)7-11 as seen in the feet of gecko lizards and spider webs12-17. Here, we describe the fabrication of hierarchically structured polymeric microparticles having branched nanofibre coronas with a dendritic morphology. Polymer precipitation in highly turbulent flow results in microparticles with fractal branching and nanofibrillar contact splitting that exhibit gelation at very low volume fractions, strong interparticle adhesion and binding into coatings and non-woven sheets. These soft dendritic particles also have potential advantages for food, personal care or pharmaceutical product formulations.

Capillary Structured Suspensions from In Situ Hydrophobized Calcium Carbonate Particles Suspended in a Polar Liquid Media.

We demonstrate that capillary suspensions can be formed from hydrophilic calcium carbonate particles suspended in a polar continuous media and connected by capillary bridges formed of minute amounts of an immiscible secondary liquid phase. This was achieved in two different polar continuous phases, water and glycerol, and three different oils, oleic acid, isopropyl myristate, and peppermint oil as a secondary liquid phase. The capillary structuring of the suspension was made possible through local in situ hydrophobization of the calcium carbonate particles dispersed in the polar media by adding very small amounts of oleic acid to the secondary liquid phase. We observed a strong increase in the viscosity of the calcium carbonate suspension by several orders of magnitude upon addition of the secondary oil phase compared with the same suspension without secondary liquid phase or without oleic acid. The stability and the rheological properties of the obtained capillary structured materials were studied in relation to the physical properties of the system such as the particle size, interfacial tension between the primary and secondary liquid phases, as well as the particle contact angle at this liquid-liquid interface. We also determined the minimal concentrations of the secondary liquid phase at fixed particle concentration as well as the minimal particle concentration at fixed secondary phase concentration needed to form a capillary suspension. Capillary suspensions formed by this method can find application in structuring pharmaceutical and food formulations as well as a variety of home and personal care products.

Toward Scalable Fabrication of Hierarchical Silica Capsules with Integrated Micro-, Meso-, and Macropores.

Hierarchical porous structures are ubiquitous in biological organisms and inorganic systems. Although such structures have been replicated, designed, and fabricated, they are often inferior to naturally occurring analogues. Apart from the complexity and multiple functionalities developed by the biological systems, the controllable and scalable production of hierarchically porous structures and building blocks remains a technological challenge. Herein, a facile and scalable approach is developed to fabricate hierarchical hollow spheres with integrated micro-, meso-, and macropores ranging from 1 nm to 100 µm (spanning five orders of magnitude). (Macro)molecules, micro-rods (which play a key role for the creation of robust capsules), and emulsion droplets have been successfully employed as multiple length scale templates, allowing the creation of hierarchical porous macrospheres. Thanks to their specific mechanical strength, these hierarchical porous spheres could be incorporated and assembled as higher level building blocks in various novel materials.

Synthesis and Characterization of Biodegradable Lignin Nanoparticles with Tunable Surface Properties.

Lignin nanoparticles can serve as biodegradable carriers of biocidal actives with minimal environmental footprint. Here we describe the colloidal synthesis and interfacial design of nanoparticles with tunable surface properties using two different lignin precursors, Kraft (Indulin AT) lignin and Organosolv (high-purity lignin). The green synthesis process is based on flash precipitation of dissolved lignin polymer, which enabled the formation of nanoparticles in the size range of 45-250 nm. The size evolution of the two types of lignin particles is fitted on the basis of modified diffusive growth kinetics and mass balance dependencies. The surface properties of the nanoparticles are fine-tuned by coating them with a cationic polyelectrolyte, poly(diallyldimethylammonium chloride). We analyze how the colloidal stability and dispersion properties of these two types of nanoparticles vary as a function of pH and salinities. The data show that the properties of the nanoparticles are governed by the type of lignin used and the presence of polyelectrolyte surface coating. The coating allows the control of the nanoparticles' surface charge and the extension of their stability into strongly basic regimes, facilitating their potential application at extreme pH conditions.

Sustained satiety induced by food foams is independent of energy content, in healthy adults.

Our previous research demonstrated high, sustained satiety effects of stabilized food foams relative to their non-aerated compositions. Here we test if the energy and macronutrients in a stabilized food foam are critical for its previously demonstrated satiating effects. In a randomized, crossover design, 72 healthy subjects consumed 400 mL of each of four foams, one per week over four weeks, 150 min after a standardized breakfast. Appetite ratings were collected for 180 min post-foam. The reference was a normal energy food foam (NEF1, 280 kJ/400 mL) similar to that used in our previous research. This was compared to a very low energy food foam (VLEF, 36 kJ/400 mL) and 2 alternative normal energy foams (NEF2 and NEF3) testing possible effects of compositional differences other than energy (i.e. emulsifier and carbohydrate source). Appetite ratings were quantified as area under the curve (AUC) and time to return to baseline (TTRTB). Equivalence to NEF1 was predefined as the 90% confidence interval of between-treatment differences in AUC being within -5 to +5 mm/min. All treatments similarly affected appetite ratings, with mean AUC for fullness ranging between 49.1 and 52.4 mm/min. VLEF met the statistical criterion for equivalence to NEF1 for all appetite AUC ratings, but NEF2 and NEF3 did not. For all foams the TTRTB for satiety and fullness were consistently between 150 and 180 min, though values were shortest for NEF2 and especially NEF3 foams for most appetite scales. In conclusion, the high, sustained satiating effects of these food foams are independent of energy and macronutrient content at the volumes tested.

Hydrophobic modification of chitin whisker and its potential application in structuring oil.

A facile approach was developed to modify chitin whiskers by reacting them with bromohexadecane, and the potential application of modified whiskers in structuring oil was evaluated. The results of Fourier transform infrared spectra (FT-IR), wide-angle X-ray diffraction (XRD), elemental analysis, solid (13)C NMR, and differential scanning calorimeter (DSC) confirmed that the long alkyl chains were successfully introduced to the chitin whiskers and endowed them with improved hydrophobicity and thermal transition. By hot pressing the modified whiskers, the highly hydrophobic whisker sheets were constructed, showing high contact angles close to 150°. The hydrophobic interaction between the long alkyl chains and chitin backbone induced the crystal alignment with micro-nano structure, leading to the surface roughness and high hydrophobicity of the sheets. Furthermore, the modified whiskers could form a stable dispersion in sunflower oil, displaying a remarkable thickening effect. The viscosity of the oily suspension exhibited temperature dependence and shear-thinning behavior, suggesting great potentials to fabricate oleogel without adding any saturated fat. Furthermore, the intrinsic biocompatibility of α-chitin structure benefits its application in foodstuff, cosmetics, and medical fields.

Growth of bubbles on a solid surface in response to a pressure reduction.

A diffusion-controlled method is presented to study the growth of bubbles on a solid surface. The bubbles are nucleated spontaneously on a hydrophobic smooth surface in response to a sudden pressure reduction and then grow with an expanding contact line. The evolution of the bubbles in the early stage is found to grow with a constant bubble radius and a decreasing contact angle, while the bubbles continue their growth with a constant contact angle and an increasing bubble radius after the contact angle reaches its equilibrium value. A total variation of about 60° of the contact angle is observed during the growth of the bubbles with the size scale of 10-100 µm in radius. The growing process is described by the diffusion theory with the validation of the growth constant.

Sonication-microfluidics for fabrication of nanoparticle-stabilized microbubbles.

An approach based upon sonication-microfluidics is presented to fabricate nanoparticle-coated microbubbles. The gas-in-liquid slug flow formed in a microchannel is subjected to ultrasound, leading to cavitation at the gas-liquid interface. Therefore, microbubbles are formed and then stabilized by the nanoparticles contained in the liquid. Compared to the conventional sonication method, this sonication-microfluidics continuous flow approach has unlimited gas nuclei for cavitation that yields continuous production of foam with shorter residence time. By controlling the flow rate ratios of the gas to the liquid, this method also achieves a higher production volume, smaller bubble size, and less waste of the nanoparticles needed to stabilize the microbubbles.

The role of the hydrophobic phase in the unique rheological properties of saponin adsorption layers.

Saponins are a diverse class of natural, plant derived surfactants, with peculiar molecular structure consisting of a hydrophobic scaffold and one or several hydrophilic oligosaccharide chains. Saponins have strong surface activity and are used as natural emulsifiers and foaming agents in food and beverage, pharmaceutical, ore processing, and other industries. Many saponins form adsorption layers at the air-water interface with extremely high surface elasticity and viscosity. The molecular origin of the observed unique interfacial visco-elasticity of saponin adsorption layers is of great interest from both scientific and application viewpoints. In the current study we demonstrate that the hydrophobic phase in contact with water has a very strong effect on the interfacial properties of saponins and that the interfacial elasticity and viscosity of the saponin adsorption layers decrease in the order: air > hexadecane ≫ tricaprylin. The molecular mechanisms behind these trends are analyzed and discussed in the context of the general structure of the surfactant adsorption layers at various nonpolar phase-water interfaces.

Shear rheology of hydrophobin adsorption layers at oil/water interfaces and data interpretation in terms of a viscoelastic thixotropic model.

Here, we investigate the surface shear rheology of class II HFBII hydrophobin layers at the oil/water interface. Experiments in two different dynamic regimes, at a fixed rate of strain and oscillations, have been carried out with a rotational rheometer. The rheological data obtained in both regimes comply with the same viscoelastic thixotropic model, which is used to determine the surface shear elasticity and viscosity, E(sh) and η(sh). Their values for HFBII at oil/water interfaces are somewhat lower than those at the air/water interface. Moreover, E(sh) and η(sh) depend on the nature of oil, being smaller for hexadecane in comparison with soybean-oil. It is remarkable that E(sh) is independent of the rate of strain in the whole investigated range of shear rates. For oil/water interfaces, E(sh) and η(sh) determined for HFBII layers are considerably greater than for other proteins, like lysozyme and ß-casein. It is confirmed that the hydrophobin forms the most rigid surface layers among all investigated proteins not only for the air/water, but also for the oil/water interface. The wide applicability of the used viscoelastic thixotropic model is confirmed by analyzing data for adsorption layers at oil/water interfaces from lysozyme and ß-casein - both native and cross-linked by enzyme, as well as for films from asphaltene. This model turns out to be a versatile tool for determining the surface shear elasticity and viscosity, E(sh) and η(sh), from experimental data for the surface storage and loss moduli, G' and G''.

Photothermal colloid antibodies for shape-selective recognition and killing of microorganisms.

We have developed a class of selective antimicrobial agents based on the recognition of the shape and size of the bacterial cells. These agents are anisotropic colloid particles fabricated as negative replicas of the target cells which involve templating of the cells with shells of inert material followed by their fragmentation. The cell shape recognition by such shell fragments is due to the increased area of surface contact between the cells and their matching shell fragments which resembles antibody-antigen interaction. We produced such "colloid antibodies" with photothermal mechanism for shape-selective killing of matching cells. This was achieved by the subsequent deposition of (i) gold nanoparticles (AuNPs) and (ii) silica shell over yeast cells, which were chosen as model pathogens. We demonstrated that fragments of these composite AuNP/silica shells act as "colloid antibodies" and can bind to yeast cells of the same shape and size and deliver AuNPs directly onto their surface. We showed that after laser irradiation, the localized heating around the AuNPs kills the microbial cells of matching shape. We confirmed the cell shape-specific killing by photothermal colloid antibodies in a mixture of two bacterial cultures of different cell shape and size. This approach opens a number of avenues for building powerful selective biocides based on combinations of colloid antibodies and cell-killing strategies which can be applied in new antibacterial therapies.

Surface pressure and elasticity of hydrophobin HFBII layers on the air-water interface: rheology versus structure detected by AFM imaging.

Here, we combine experiments with Langmuir trough and atomic force microscopy (AFM) to investigate the reasons for the special properties of layers from the protein HFBII hydrophobin spread on the air-water interface. The hydrophobin interfacial layers possess the highest surface dilatational and shear elastic moduli among all investigated proteins. The AFM images show that the spread HFBII layers are rather inhomogeneous, (i.e., they contain voids, monolayer and multilayer domains). A continuous compression of the layer leads to filling the voids and transformation of a part of the monolayer into a trilayer. The trilayer appears in the form of large surface domains, which can be formed by folding and subduction of parts from the initial monolayer. The trilayer appears also in the form of numerous submicrometer spots, which can be obtained by forcing protein molecules out of the monolayer and their self-assembly into adjacent pimples. Such structures are formed because not only the hydrophobic parts, but also the hydrophilic parts of the HFBII molecules can adhere to each other in the water medium. If a hydrophobin layer is subjected to oscillations, its elasticity considerably increases, up to 500 mN/m, which can be explained with compaction. The relaxation of the layer's tension after expansion or compression follows the same relatively simple law, which refers to two-dimensional diffusion of protein aggregates within the layer. The characteristic diffusion time after compression is longer than after expansion, which can be explained with the impedence of diffusion in the more compact interfacial layer. The results shed light on the relation between the mesoscopic structure of hydrophobin interfacial layers and their unique mechanical properties that find applications for the production of foams and emulsions of extraordinary stability; for the immobilization of functional molecules at surfaces, and as coating agents for surface modification.

Triggered release kinetics of living cells from composite microcapsules.

We have developed a theoretical model for the kinetics of release of living cells from composite shellac-cell microcapsules. The model describes the kinetics of cell release from the microcapsules triggered by: (i) pH change, which dissolves the shellac and (ii) the growth of the encapsulated cells, when placed in culture media. For pH triggered release of cells from the composite microcapsules, the rate constant of cell release depends on the swelling/dissolution rate of the shellac matrix and varies with the pH of the aqueous media. The model links the microcapsules disintegration time with the cell release rate constant. For growth triggered release of cells from the composite microcapsules, the cell release rate constant depends on concentration of nutrients in the culture media and the volume fraction of cells in the microcapsules. In a complementary experimental study we compare the release rate constants of cells from shellac-cell microcapsules at different values of pH in the aqueous media. This study may allow fine-tuning of the rate of cell release in a variety of encapsulated cell products, including cell implants, probiotics, and live vaccines.

Electrospinning versus fibre production methods: from specifics to technological convergence.

Academic and industrial research on nanofibres is an area of increasing global interest, as seen in the continuously multiplying number of research papers and patents and the broadening range of chemical, medical, electrical and environmental applications. This in turn expands the size of the market opportunity and is reflected in the significant rise of entrepreneurial activities and investments in the field. Electrospinning is probably the most researched top-down method to form nanofibres from a remarkable range of organic and inorganic materials. It is well known and discussed in many comprehensive studies, so why this review? As we read about yet another "novel" method producing multifunctional nanomaterials in grams or milligrams in the laboratory, there is hardly any research addressing how these methods can be safely, consistently and cost-effectively up-scaled. Despite two decades of governmental and private investment, the productivity of nanofibre forming methods is still struggling to meet the increasing demand. This hinders the further integration of nanofibres into practical large-scale applications and limits current uses to niche-markets. Looking into history, this large gap between supply and demand of synthetic fibres was seen and addressed in conventional textile production a century ago. The remarkable achievement was accomplished via extensive collaborative research between academia and industry, applying ingenious solutions and technological convergence from polymer chemistry, physical chemistry, materials science and engineering disciplines. Looking into the present, current advances in electrospinning and nanofibre production are showing similar interdisciplinary technological convergence, and knowledge of industrial textile processing is being combined with new developments in nanofibre forming methods. Moreover, many important parameters in electrospinning and nanofibre spinning methods overlap parameters extensively studied in industrial fibre processing. Thus, this review combines interdisciplinary knowledge from the academia and industry to facilitate technological convergence and offers insight for upscaling electrospinning and nanofibre production. It will examine advances in electrospinning within a framework of large-scale fibre production as well as alternative nanofibre forming methods, providing a comprehensive comparison of conventional and contemporary fibre forming technologies. This study intends to stimulate interest in addressing the issue of scale-up alongside novel developments and applications in nanofibre research.

Fluid Flow Templating of Polymeric Soft Matter with Diverse Morphologies.

It is challenging to find a conventional nanofabrication technique that can consistently produce soft polymeric matter of high surface area and nanoscale morphology in a way that is scalable, versatile, and easily tunable. Here, the capabilities of a universal method for fabricating diverse nano- and micro-scale morphologies based on polymer precipitation templated by the fluid streamlines in multiphasic flow are explored. It is shown that while the procedure is operationally simple, various combinations of its intertwined mechanisms can controllably and reproducibly lead to the formation of an extraordinary wide range of colloidal morphologies. By systematically investigating the process conditions, 12 distinct classes of polymer micro- and nano-structures including particles, rods, ribbons, nanosheets, and soft dendritic colloids (dendricolloids) are identified. The outcomes are interpreted by delineating the physical processes into three stages: hydrodynamic shear, capillary and mechanical breakup, and polymer precipitation rate. The insights into the underlying fundamental mechanisms provide guidance toward developing a versatile and scalable nanofabrication platform. It is verified that the liquid shear-based technique is versatile and works well with many chemically diverse polymers and biopolymers, showing potential as a universal tool for simple and scalable nanofabrication of many morphologically distinct soft matter classes.

Fabrication of environmentally biodegradable lignin nanoparticles.

We developed a method for the fabrication of novel biodegradable nanoparticles (NPs) from lignin which are apparently non-toxic for microalgae and yeast. We compare two alternative methods for the synthesis of lignin NPs which result in particles of very different stability upon change of pH. The first method is based on precipitation of low-sulfonated lignin from an ethylene glycol solution by using diluted acidic aqueous solutions, which yields lignin NPs that are stable over a wide range of pH. The second approach is based on the acidic precipitation of lignin from a high-pH aqueous solution which produces NPs stable only at low pH. Our study reveals that lignin NPs from the ethylene glycol-based precipitation contain densely packed lignin domains which explain the stability of the NPs even at high pH. We characterised the properties of the produced lignin NPs and determined their loading capacities with hydrophilic actives. The results suggest that these NPs are highly porous and consist of smaller lignin domains. Tests with microalgae like Chlamydomonas reinhardtii and yeast incubated in lignin NP dispersions indicated that these NPs lack measurable effect on the viability of these microorganisms. Such biodegradable and environmentally compatible NPs can find applications as drug delivery vehicles, stabilisers of cosmetic and pharmaceutical formulations, or in other areas where they may replace more expensive and potentially toxic nanomaterials.

Surface shear rheology of saponin adsorption layers.

Saponins are a wide class of natural surfactants, with molecules containing a rigid hydrophobic group (triterpenoid or steroid), connected via glycoside bonds to hydrophilic oligosaccharide chains. These surfactants are very good foam stabiliziers and emulsifiers, and show a range of nontrivial biological activities. The molecular mechanisms behind these unusual properties are unknown, and, therefore, the saponins have attracted significant research interest in recent years. In our previous study (Stanimirova et al. Langmuir 2011, 27, 12486-12498), we showed that the triterpenoid saponins extracted from Quillaja saponaria plant (Quillaja saponins) formed adsorption layers with unusually high surface dilatational elasticity, 280 ± 30 mN/m. In this Article, we study the shear rheological properties of the adsorption layers of Quillaja saponins. In addition, we study the surface shear rheological properties of Yucca saponins, which are of steroid type. The experimental results show that the adsorption layers of Yucca saponins exhibit purely viscous rheological response, even at the lowest shear stress applied, whereas the adsorption layers of Quillaja saponins behave like a viscoelastic two-dimensional body. For Quillaja saponins, a single master curve describes the data for the viscoelastic creep compliance versus deformation time, up to a certain critical value of the applied shear stress. Above this value, the layer compliance increases, and the adsorption layers eventually transform into viscous ones. The experimental creep-recovery curves for the viscoelastic layers are fitted very well by compound Voigt rheological model. The obtained results are discussed from the viewpoint of the layer structure and the possible molecular mechanisms, governing the rheological response of the saponin adsorption layers.

Effects of emulsifier charge and concentration on pancreatic lipolysis: 2. Interplay of emulsifiers and biles.

As a direct continuation of the first part of our in vitro study (Vinarov et al., Langmuir 2012, 28, 8127), here we investigate the effects of emulsifier type and concentration on the degree of triglyceride lipolysis, in the presence of bile salts. Three types of surfactants are tested as emulsifiers: anionic, nonionic, and cationic. For all systems, we observe three regions in the dependence degree of fat lipolysis, α, versus emulsifier-to-bile ratio, f(s): α is around 0.5 in Region 1 (f(s) < 0.02); α passes through a maximum close to 1 in Region 2 (0.02 < f(s) < f(TR)); α is around zero in Region 3 (f(s) > f(TR)). The threshold ratio for complete inhibition of lipolysis, f(TR), is around 0.4 for the nonionic, 1.5 for the cationic, and 7.5 for the anionic surfactants. Measurements of interfacial tensions and optical observations revealed the following: In Region 1, the emulsifier molecules are solubilized in the bile micelles, and the adsorption layer is dominated by bile molecules. In Region 2, mixed surfactant-bile micelles are formed, with high solubilization capacity for the products of triglyceride lipolysis; rapid solubilization of these products leads to complete lipolysis. In Region 3, the emulsifier molecules prevail in the adsorption layer and completely block the lipolysis.

Surface shear rheology of adsorption layers from the protein HFBII hydrophobin: effect of added ß-casein.

The surface shear rheology of hydrophobin HFBII adsorption layers is studied in angle-ramp/relaxation regime by means of a rotational rheometer. The behavior of the system is investigated at different shear rates and concentrations of added ß-casein. In angle-ramp regime, the experimental data comply with the Maxwell model of viscoelastic behavior. From the fits of the rheological curves with this model, the surface shear elasticity and viscosity, E(sh) and η(sh), are determined at various fixed shear rates. The dependence of η(sh) on the rate of strain obeys the Herschel-Bulkley law. The data indicate an increasing fluidization (softening) of the layers with the rise of the shear rate. The addition of ß-casein leads to more rigid adsorption layers, which exhibit a tendency of faster fluidization at increasing shear rates. In relaxation regime, the system obeys a modified Andrade's (cubic root) law, with two characteristic relaxation times. The fact that the data comply with the Maxwell model in angle-ramp regime, but follow the modified Andrade's low in relaxation regime, can be explained by the different processes occurring in the viscoelastic protein adsorption layer in these two regimes: breakage and restoration of intermolecular bonds at angle-ramp vs solidification of the layer at relaxation.