Advances in Colloid and Interface Science (v.234, #C)

In memoriam: Professor Albert Sanfeld (1932–2015) by Khellil Sefiane; Mickael Antoni (1-2).

There is increasing consumer pressure for commercial products that are more natural, sustainable, and environmentally friendly, including foods, cosmetics, detergents, and personal care products. Industry has responded by trying to identify natural alternatives to synthetic functional ingredients within these products. The focus of this review article is on the replacement of synthetic surfactants with natural emulsifiers, such as amphiphilic proteins, polysaccharides, biosurfactants, phospholipids, and bioparticles. In particular, the physicochemical basis of emulsion formation and stabilization by natural emulsifiers is discussed, and the benefits and limitations of different natural emulsifiers are compared. Surface-active polysaccharides typically have to be used at relatively high levels to produce small droplets, but the droplets formed are highly resistant to environmental changes. Conversely, surface-active proteins are typically utilized at low levels, but the droplets formed are highly sensitive to changes in pH, ionic strength, and temperature. Certain phospholipids are capable of producing small oil droplets during homogenization, but again the droplets formed are highly sensitive to changes in environmental conditions. Biosurfactants (saponins) can be utilized at low levels to form fine oil droplets that remain stable over a range of environmental conditions. Some nature-derived nanoparticles (e.g., cellulose, chitosan, and starch) are effective at stabilizing emulsions containing relatively large oil droplets. Future research is encouraged to identify, isolate, purify, and characterize new types of natural emulsifier, and to test their efficacy in food, cosmetic, detergent, personal care, and other products.Display Omitted
Keywords: Emulsifiers; Natural proteins; Polysaccharides; Phospholipids; Biosurfactants; Pickering stabilization;

Biomimetic multifunctional surfaces inspired from animals by Zhiwu Han; Zhengzhi Mu; Wei Yin; Wen Li; Shichao Niu; Junqiu Zhang; Luquan Ren (27-50).
Over millions of years, animals have evolved to a higher intelligent level for their environment. A large number of diverse surface structures on their bodies have been formed to adapt to the extremely harsh environment. Just like the structural diversity existed in plants, the same also applies true in animals. Firstly, this article provides an overview and discussion of the most common functional surface structures inspired from animals, such as drag reduction, noise reduction, anti-adhesion, anti-wear, anti-erosion, anti-fog, water capture, and optical surfaces. Then, some typical characteristics of morphologies, structures, and materials of the animal multifunctional surfaces were discussed. The adaptation of these surfaces to environmental conditions was also analyzed. It mainly focuses on the relationship between their surface functions and their surface structural characteristics. Afterwards, the multifunctional mechanisms or principles of these surfaces were discussed. Models of these structures were provided for the development of structure materials and machinery surfaces. At last, fabrication techniques and existing or potential technical applications inspired from biomimetic multifunctional surfaces in animals were also discussed. The application prospects of the biomimetic functional surfaces are very broad, such as civil field of self-cleaning textile fabrics and non-stick pots, ocean field of oil–water separation, sports field of swimming suits, space development field of lens arrays.Display Omitted
Keywords: Biomimetic; Multifunctional surface; Surface function; Surface structure; Surface morphology;

Template-based syntheses for shape controlled nanostructures by María Pérez-Page; Erick Yu; Jun Li; Masoud Rahman; Daniel M. Dryden; Ruxandra Vidu; Pieter Stroeve (51-79).
A variety of nanostructured materials are produced through template-based synthesis methods, including zero-dimensional, one-dimensional, and two-dimensional structures. These span different forms such as nanoparticles, nanowires, nanotubes, nanoflakes, and nanosheets. Many physical characteristics of these materials such as the shape and size can be finely controlled through template selection and as a result, their properties as well. Reviewed here are several examples of these nanomaterials, with emphasis specifically on the templates and synthesis routes used to produce the final nanostructures. In the first section, the templates have been discussed while in the second section, their corresponding synthesis methods have been briefly reviewed, and lastly in the third section, applications of the materials themselves are highlighted. Some examples of the templates frequently encountered are organic structure directing agents, surfactants, polymers, carbon frameworks, colloidal sol–gels, inorganic frameworks, and nanoporous membranes. Synthesis methods that adopt these templates include emulsion-based routes and template-filling approaches, such as self-assembly, electrodeposition, electroless deposition, vapor deposition, and other methods including layer-by-layer and lithography. Template-based synthesized nanomaterials are frequently encountered in select fields such as solar energy, thermoelectric materials, catalysis, biomedical applications, and magnetowetting of surfaces.Display Omitted
Keywords: Template-based synthesis; Nanostructured materials; Template-filling methods; Nanoporous membrane templates;

Soft materials are complex macromolecular systems often exhibiting perplexing non-Newtonian viscoelastic properties, especially when the macromolecules are entangled, crowded or cross-linked. These materials are ubiquitous in the biology, food and pharma industry and have several applications in biotechnology and in the field of biosensors. Based on the length scales, topologies, flexibility and concentration, the systems behave both as liquids (viscous) and solids (elastic). Particularly, for proteins and protein–lipid systems, viscoelasticity is an important parameter because it often relates directly to stability and thermodynamic interactions of the pure biological components as well as their mixtures. Despite the large body of work that is available in solution macro-rheometry, there are still a number of issues that need to be addressed in dealing with proteins at air/fluid interfaces and with protein–polymer or protein–lipid interfaces that often exhibit very low interfacial viscosity values.Considering the important applications that they have in biopharmaceutical, biotechnological and nutraceutical industries, there is a need for developing methods that meet the following three specific issues: small volume, large dynamic range of shear rates and interfacial properties of different biomolecules. Further, the techniques that are developed should include Newtonian, shear thinning and yielding properties, which are representative of the different solution behaviors typically encountered. The review presented here is a comprehensive account of the rheological properties of different biomolecules at air/fluid and solid/fluid interfaces. It addresses the usefulness of ‘viscoelasticity’ of the systems at the interfaces analyzed at the molecular level that can be correlated with the microscopic material properties and touches upon some recent techniques in microrheology that are being used to measure the unusually low viscosity values sensitively.Display Omitted
Keywords: Protein organizates; Colloidal dispersion; Air/fluid interface; Interfacial rheology; Viscoelasticity; Conformation;

The mutual compatibility of Hamaker constants, solubility parameters or cohesive energy densities (CED) and surface/interface tensions are evaluated. It is shown that the partial contributions (dispersive, Lifshitz–van der Waals, dipolar induction, dipolar orientation, polar, acid, base and hydrogen bond) to Hamaker constants, solubility parameters or cohesive energy densities and surface/interface tensions are mutually inconsistent. The published reference data for a single set of liquids is moreover shown to be exceedingly scattered; making the parallel use of these scales challenging. Reference processes designed for bringing two and three phases into mutual contact are conflicting. The two-phase processes within Hamaker and exchange energy density (EED) frameworks agree, but the three-phase models differ. As a free-standing parameter the EED is however comparable. The two-phase adhesion process is shown to be incompatible with the other contact processes and the three-phase adhesion process is opposite to them. One reason for this controversy is the different averaging of interfacial properties. While interfacial Hamaker constants and solubility parameters or cohesive energy densities are geometric averages of corresponding intervening phase properties, this practice is replaced by the work of adhesion being geometrically averaged as works of cohesion. As a result, there exist three conflicting models for the adhesion process: the Dupré work of adhesion, the Girifalco–Good geometric averaged works of cohesion and Fowkes reduced interfacial or interphasial tension process. None of these agree with the commonly accepted standard Hamaker contact processes and they should be replaced with the compatible extended work of adhesion process originally suggested by Dupré. The models offered for the conversion of Hamaker constants and solubility parameters or cohesive energy densities to surface tensions involve conversion factors and equilibrium distances between planes of molecules in liquids. The equilibrium distance for different close packings derived from molar liquid volumes are about 2–5 times larger than the cutoff distances obtained from simulations. Using volumetric equilibrium distances, the conversion factors for dispersive, polar and total Hamaker constant and solubility parameter or cohesive energy densities to surface tensions become nearly equal but they are different for each liquid.Dupré and extended work of adhesion processes for two- and three-phase systems differ considerably depending on the constraints. As shown, the Dupré work of adhesion processes may be double (two-phase systems) or opposite (three-phase systems) as compared to the extended work of adhesion. Only extended work of adhesion agrees with commonly accepted Hamaker and solubility parameter or exchange energy density processes.Display Omitted
Keywords: Dispersive Lifshitz–van der Waals interaction; Dipolar induction; Dipolar orientation; Acid–base; extended work of adhesion; conversion constants; intermolecular distance;

Electrokinetics of the silica and aqueous electrolyte solution interface: Viscoelectric effects by Wei-Lun Hsu; Hirofumi Daiguji; David E. Dunstan; Malcolm R. Davidson; Dalton J.E. Harvie (108-131).
The manipulation of biomolecules, fluid and ionic current in a new breed of integrated nanofluidic devices requires a quantitative understanding of electrokinetics at the silica/water interface. The conventional capacitor-based electrokinetic Electric Double Layer (EDL) models for this interface have some known shortcomings, as evidenced by a lack of consistency within the literature for the (i) equilibrium constants of surface silanol groups, (ii) Stern layer capacitance, (iii) zeta (ζ) potential measured by various electrokinetic methods, and (iv) surface conductivity. In this study, we consider how the experimentally observable viscoelectric effect – that is, the increase of the local viscosity due to the polarisation of polar solvents – affects electrokinetcs at the silica/water interface. Specifically we consider how a model that considers viscoelectric effects (the VE model) performs against two conventional electrokinetic models, namely the Gouy–Chapman (GC) and Basic Stern capacitance (BS) models, in predicting four fundamental electrokinetic phenomena: electrophoresis, electroosmosis, streaming current and streaming potential. It is found that at moderate to high salt concentrations (>5   ×10  −3M) predictions from the VE model are in quantitative agreement with experimental electrokinetic measurements when the sole additional adjustable parameter, the viscoelectric coefficient, is set equal to a value given by a previous independent measurement. In contrast neither the GS nor BS models is able to reproduce all experimental data over the same concentration range using a single, robust set of parameters. Significantly, we also show that the streaming current and potential in the moderate to high surface charge range are insensitive to surface charge behaviour (including capacitances) when viscoelectric effects are considered, in difference to models that do not consider these effects. This strongly questions the validity of using pressure based electrokinetic experiments to measure surface charge characteristics within this experimentally relevant high pH and moderate to high salt concentration range. At low salt concentrations (<5   ×10  −3  M) we find that there is a lack of consistency in previously measured channel conductivities conducted under similar solution conditions (pH, salt concentration), preventing a conclusive assessment of any model suitability in this regime.Display Omitted
Keywords: Viscoelectric effect; Electrophoresis; Electroosmosis; Streaming current; Streaming potential; Silica/electrolyte interface;

Applications of plant terpenoids in the synthesis of colloidal silver nanoparticles by Zia-ur-Rehman Mashwani; Mubarak Ali Khan; Tariq Khan; Akhtar Nadhman (132-141).
Green chemistry is the design of chemical products and processes that reduce or eliminate the generation of hazardous substances. Since the last few years, natural products especially plant secondary metabolites have been extensively explored for their potency to synthesize silver nanoparticles (AgNPs). The plant-based AgNPs are safer, energy efficient, eco-friendly, and less toxic than chemically synthesized counterparts. The secondary metabolites, ubiquitously found in plants especially the terpenoid-rich essential oils, have a significant role in AgNPs synthesis. Terpenoids belong to the largest family of natural products and are found in all kinds of organisms. Their involvement in the synthesis of plant-based AgNPs has got much attention in the recent years. The current article is not meant to provide an exhaustive overview of green synthesis of nanoparticles, but to present the pertinent role of plant terpenoids in the biosynthesis of AgNPs, as capping and reducing agents for development of uniform size and shape AgNPs. An emphasis on the important role of FTIR in the identification and elucidation of major functional groups in terpenoids for AgNPs synthesis has also been reviewed in this manuscript. It was found that no such article is available that has discussed the role of plant terpenoids in the green synthesis of AgNPs.Display Omitted
Keywords: Silver nanoparticles; Plant terpenoids; Essential oils; Green synthesis; FTIR; AgNPs;

Colloidal crystals and water: Perspectives on liquid–solid nanoscale phenomena in wet particulate media by Francisco Gallego-Gómez; Víctor Morales-Flórez; Miguel Morales; Alvaro Blanco; Cefe López (142-160).
Solid colloidal ensembles inherently contain water adsorbed from the ambient moisture. This water, confined in the porous network formed by the building submicron spheres, greatly affects the ensemble properties. Inversely, one can benefit from such influence on collective features to explore the water behavior in such nanoconfinements. Recently, novel approaches have been developed to investigate in-depth where and how water is placed in the nanometric pores of self-assembled colloidal crystals. Here, we summarize these advances, along with new ones, that are linked to general interfacial water phenomena like adsorption, capillary forces, and flow. Water-dependent structural properties of the colloidal crystal give clues to the interplay between nanoconfined water and solid fine particles that determines the behavior of ensembles. We elaborate on how the knowledge gained on water in colloidal crystals provides new opportunities for multidisciplinary study of interfacial and nanoconfined liquids and their essential role in the physics of utmost important systems such as particulate media.Display Omitted
Keywords: Colloidal crystal; Particulate media; Wet granular materials; Interfacial water; Micromechanical properties;