Advances in Colloid and Interface Science (v.243, #C)

From the ion point-of-view specific ion effects (SIE) arise as an interplay of ionic size and shape and charge distribution. However in aqueous systems SIE invariably involve water, and at surfaces they involve both interacting surface groups and local fields emanating from the surface. In this review we highlight the fundamental importance of ionic size and hydration on SIE, properties which encompass all types of interacting forces and ion-pairing phenomena and make the Hofmeister or lyotropic series of ions pertinent to a broad range of systems and phenomena. On the other hand ionic hydrophobicity and complexation capacity also determine ionic behavior in a variety of contexts.Over the years we have carried out carefully designed experiments on a few selected soft matter model systems, most involving zwitterionic phospholipids, to assess the importance of fundamental ionic and interfacial properties on ion specific effects. By tuning down direct Coulomb interactions, working with different interfacial geometries, and carefully tuning ion-lipid headgroup interactions it is possible to assess the importance of different parameters contributing to ion specific behavior. We argue that the majority of specific ion effects involving relatively simple soft matter systems can be at least qualitatively understood and demystified.Display Omitted
Keywords: Specific ion effects; Lyotropic series; Phospholipids; Monolayers; Bilayers; Microemulsions;

Micro- and nano bio-based delivery systems for food applications: In vitro behavior by Lívia de Souza Simões; Daniel A. Madalena; Ana C. Pinheiro; José A. Teixeira; António A. Vicente; Óscar L. Ramos (23-45).
Micro- and nanoencapsulation is an emerging technology in the food field that potentially allows the improvement of food quality and human health. Bio-based delivery systems of bioactive compounds have a wide variety of morphologies that influence their stability and functional performance. The incorporation of bioactive compounds in food products using micro- and nano-delivery systems may offer extra health benefits, beyond basic nutrition, once their encapsulation may provide protection against undesired environmental conditions (e.g., heat, light and oxygen) along the food chain (including processing and storage), thus improving their bioavailability, while enabling their controlled release and target delivery. This review provides an overview of the bio-based materials currently used for encapsulation of bioactive compounds intended for food applications, as well as the main production techniques employed in the development of micro- and nanosystems. The behavior of such systems and of bioactive compounds entrapped into, throughout in vitro gastrointestinal systems, is also tracked in a critical manner. Comparisons between various in vitro digestion systems (including the main advantages and disadvantages) currently in use, as well as correlations between the behavior of micro- and nanosystems studied through in vitro and in vivo systems were highlighted and discussed here for the first time. Finally, examples of bioactive micro- and nanosystems added to food simulants or to real food matrices are provided, together with a revision of the main challenges for their safe commercialization, the regulatory issues involved and the main legislation aspects.Display Omitted
Keywords: Encapsulation; Micro/Nanosystems; Biomaterials; Bioactive compounds; Bioavailability; Food products;

Gas adsorption properties of graphene-based materials by Barbara Szczęśniak; Jerzy Choma; Mietek Jaroniec (46-59).
Clean energy sources and global warming are among the major challenges of the 21st century. One of the possible actions toward finding alternative energy sources and reducing global warming are storage of H2 and CH4, and capture of CO2 by using highly efficient and low-cost adsorbents. Graphene and graphene-based materials attracted a great attention around the world because of their potential for a variety applications ranging from electronics, gas sensing, energy storage and CO2 capture. Large specific surface area of these materials up to ~ 3000 m2/g and versatile modification make them excellent adsorbents for diverse applications. Here, graphene-based adsorbents are reviewed with special emphasis on their adsorption affinity toward CO2, H2 and CH4. This review shows that graphene derivatives obtained mainly via “chemical exfoliation” of graphite and further modification with polymers and/or metal species can be very effective sorbents for CO2 and other gases and can compete with the currently used carbonaceous or non-carbonaceous adsorbents. The high adsorption capacities of graphene-based materials are mainly determined by their unique nanostructures, high specific surface areas and tailorable surface properties, which make them suitable for storage or capture of various molecules relevant for environmental and energy-related applications.Display Omitted
Keywords: Graphene-based materials; Porous adsorbents; CO2 adsorption; Energy storage;

How to gather useful and valuable information from protein binding measurements using Langmuir lipid monolayers by Élodie Boisselier; Éric Demers; Line Cantin; Christian Salesse (60-76).
This review presents data on the influence of various experimental parameters on the binding of proteins onto Langmuir lipid monolayers. The users of the Langmuir methodology are often unaware of the importance of choosing appropriate experimental conditions to validate the data acquired with this method. The protein Retinitis pigmentosa 2 (RP2) has been used throughout this review to illustrate the influence of these experimental parameters on the data gathered with Langmuir monolayers. The methods detailed in this review include the determination of protein binding parameters from the measurement of adsorption isotherms, infrared spectra of the protein in solution and in monolayers, ellipsometric isotherms and fluorescence micrographs.Display Omitted
Keywords: Monolayer; Langmuir films; Protein binding; Retinitis pigmentosa 2; RP2;

Acoustic levitation of liquid drops: Dynamics, manipulation and phase transitions by Duyang Zang; Yinkai Yu; Zhen Chen; Xiaoguang Li; Hongjing Wu; Xingguo Geng (77-85).
The technique of acoustic levitation normally produces a standing wave and the potential well of the sound field can be used to trap small objects. Since no solid surface is involved it has been widely applied for the study of fluid physics, nucleation, bio/chemical processes, and various forms of soft matter. In this article, we survey the works on drop dynamics in acoustic levitation, focus on how the dynamic behavior is related to the rheological properties and discuss the possibility to develop a novel rheometer based on this technique. We review the methods and applications of acoustic levitation for the manipulation of both liquid and solid samples and emphasize the important progress made in the study of phase transitions and bio-chemical analysis. We also highlight the possible open areas for future research.Acoustically levitated liquid drop is readily to serve as a micro-reactor which may bring about unusual effects to the chemical/physical processes inside it.Display Omitted
Keywords: Drop dynamics; Interfacial rheology; Drying patterns; Acoustic levitation; Micro-reaction;

Thermal decomposition of organometallic and various coordination compounds are known as general method to synthesize a wide range of nanostructures including metals, metal oxides and sulfides. Herein, in order to coordinate metals and prepare suitable precursor - due to the efficient role of precursor on the particle size and morphology of products - appropriate ligands will be introduced.Display Omitted
Keywords: Nanostructures; Thermal decomposition; Ligand; Synthesis; Coordination compounds;

Saponins — Self-assembly and behavior at aqueous interfaces by Sandra Böttcher; Stephan Drusch (105-113).
Saponins are interfacially active ingredients in plants consisting of a hydrophobic aglycone structure with hydrophilic sugar residues. Variations in aglycone structure as well as type and amount of sugar residues occur depending on the botanical origin. Saponins are a heterogeneous and broad class of natural substances and therefore the relationship between molecular structure and interfacial properties is complex and, yet, not completely understood. A wide range of research focused either on structural elucidation of saponins or interfacial properties. This review combines recent knowledge on structural features with interfacial properties and draws conclusions on how saponin structure affects interfacial properties.Fundamental understanding on interfacial configuration of individual saponin molecules at the interface distinctly increased. It was shown that interfacial configuration may differ depending on botanical origin and thus structure of the saponins. The formation of strong viscoelastic interfacial films by some saponins was attributed to hydrogen bonds between neighboring sugar residues. Few studies analyzed the relationship between botanical origin and interfacial rheology and derived main conclusions on important structural features. Saponins with a triterpenoid structure are most likely to form viscoelastic films, which result in stable foams and emulsions. The aglycone subtype may also affect interfacial properties as triterpenoid saponins of oleanane type formed most stable interfacial networks. But for more reliable conclusions more saponins from other aglycone subtypes (dammarane, ursolic) have to be analyzed.To-date only extracts from Quillaja saponaria Molina are approved for food products and many studies focused on these extracts. From experiments on interfacial rheology a reasonable model for supramolecular structure of Quillaja saponins was developed. It was further shown that Quillaja saponins may form micelles loaded with hydrophobic substances, nano-emulsions and stable foams. In combination proteins an increase in interfacial film stability may be observed but also negative phenomena like aggregation of oil droplets in emulsions may occur.Display Omitted

Capillary dynamics driven by molecular self-layering by Pingkeng Wu; Alex Nikolov; Darsh Wasan (114-120).
Capillary dynamics is a ubiquitous everyday phenomenon. It has practical applications in diverse fields, including ink-jet printing, lab-on-a-chip, biotechnology, and coating. Understanding capillary dynamics requires essential knowledge on the molecular level of how fluid molecules interact with a solid substrate (the wall). Recent studies conducted with the surface force apparatus (SFA), atomic force microscope (AFM), and statistical mechanics simulation revealed that molecules/nanoparticles confined into the film/wall surfaces tend to self-layer into 2D layer/s and even 2D in-layer with increased confinement and fluid volume fraction. Here, the capillary rise dynamics of simple molecular fluids in cylindrical capillary is explained by the molecular self-layering model. The proposed model considers the role of the molecular shape on self-layering and its effect on the molecularly thin film viscosity in regards to the advancing (dynamic) contact angle. The model was tested to explain the capillary rise dynamics of fluids of spherical, cylindrical, and disk shape molecules in borosilicate glass capillaries. The good agreement between the capillary rise data and SFA data from the literature for simple fluid self-layering shows the validity of the present model. The present model provides new insights into the design of many applications where dynamic wetting is important because it reveals the significant impact of molecular self-layering close to the wall on dynamic wetting.Display Omitted
Keywords: Dynamic contact angle; Molecular self-layering; Solvation force; Capillary rise; Modelling;

This paper resolves an ostensible inconsistency in the literature in calculating the evaporation rate for sessile drops in a quiescent environment. The earlier models in the literature have shown that adapting the evaporation flux model for a suspended spherical drop to calculate the evaporation rate of a sessile drop needs a correction factor; the correction factor was shown to be a function of the drop contact angle, i.e. f ( θ ). However, there seemed to be a problem as none of the earlier models explicitly or implicitly mentioned the evaporation flux variations along the surface of a sessile drop. The more recent evaporation models include this variation using an electrostatic analogy, i.e. the Laplace equation (steady-state continuity) in a domain with a known boundary condition value, or known as the Dirichlet problem for Laplace's equation. The challenge is that the calculated evaporation rates using the earlier models seemed to differ from that of the recent models (note both types of models were validated in the literature by experiments). We have reinvestigated the recent models and found that the mathematical simplifications in solving the Dirichlet problem in toroidal coordinates have created the inconsistency. We also proposed a closed form approximation for f ( θ ) which is valid in a wide range, i.e. 8 ° ≤  θ  ≤ 131°. Using the proposed model in this study, theoretically, it was shown that the evaporation rate in the CWA (constant wetted area) mode is faster than the evaporation rate in the CCA (constant contact angle) mode for a sessile drop.Display Omitted
Keywords: Evaporation; Sessile drops; Micro-liter drops; Electrostatic analogy; Evaporation flux variation; Diffusion;