McBain and the centenary of the micelle

In 1913, J.W. McBain introduced the word “micelle” into surface and colloid chemistry in the context of the association of surfactant molecules in aqueous solution. This article gives a biographic account of McBain, and reviews the early work on micellar aggregation, leading up to the pioneering ideas of G.S. Hartley who introduced the first model of the spherical micelle that we would recognise today.     

Concentration effects on distribution of macromolecules in small pores

The interactions between two particles and between one particle and a rigid boundary are examined to study the effect of particle concentration on partitioning, stress and flow in microporous media. Because the particle—particle and particle—wall interactions occur over comparable length scales, their effects are not additive and lead to non-uniform particle concentration stress (“surface pressure”) in the vicinity of the boundary. A particle concentration gradient parallel to the boundary creates a gradient in surface pressure which drives a viscous flow of the solvent toward regions of higher concentration. Such flows are termed “osmosis”, and the effect of particle interactions is to reduce the osmotic velocity.     

The osmotic bulk modulus of a colloid crystal of infinite rod-like molecules

A general expression for the osmotic bulk modulus and its pressure derivative of a colloid crystal of infinite rod-like molecules is derived. This result is based on an exact solution of the Poisson-Boltzmann equation within a Wigner-Scitz cylinder and a recently derived expression relating the osmotic bulk modulus to the counterion density at the edge of the Wigner-Scitz cylinder. The osmotic bulk modulus and its pressure derivative of the myosin-rod lattice found in striated muscle are calculated and found to be in good agreement with experiment.     

Determination of the concentration and the average number of gold atoms in a gold nanoparticle by osmotic pressure

For an ideal solution, an analytical expression for the macromolecule concentration, electrolyte concentration, and solution osmotic pressure is obtained on the basis of the van't Hoff equation and the Donnan equilibrium. The expression was further applied to a colloid solution of about 3 nm glutathione-stabilized gold nanoparticles. The concentration of the colloid solution and the average net ion charge number for each gold nanoparticle were determined with the measured osmotic pressure data. Meanwhile, the gold contents of the solutions were analyzed by means of atomic absorption spectrophotometry, and the results were combined with the determined concentration of gold nanoparticle colloids to determine that the average number of gold atoms per 3 nm gold nanoparticle is 479, which is 1/1.7 times the number of atoms in bulk metallic gold of the same size. The same proportion also occurred in the 2 nm 4-mercaptobenzoic acid monolayer-protected gold nanoparticles prepared by Ackerson et al., who utilized the quantitative high-angle annular dark-field scanning transmission electron microscope to determine the average number of gold atoms per nanoparticle (Ackerson, C. J.; Jadzinsky, P. D.; Sexton J. Z.; Bushnell, D. A.; Kornberg, R. D. Synthesis and Bioconjugation of 2 and 3 nm-Diameter Gold Nanoparticles. Bioconjugate Chem. 2010, 21, 214-218).     

“Surface water” and “strong-bonded water” in cyclodextrins: a Karl Fischer titration approach

Cyclodextrins are some of the most used carriers for bioactive compounds (as host–guest complex) and many factors influence the association–dissociation of this complex, some of them being related to hydrophobicity. In the solid state, cyclodextrins contain two types of water molecules: “surface” water molecules (especially close to the crystal surface) and “strong-bonded” water molecules (especially from the cyclodextrin cavity), but the classification is hard to do, and the concentration of these water molecules are relatively difficult to estimate by simple methods. In the present study we used the volumetric Karl Fischer titration to estimate these types of water molecules in cyclodextrins by means of the rate of water reaction (related to diffusion from cyclodextrin crystals). “Surface” water molecules are titrated with rates between 1.8–2.8 mM/s for α-cyclodextrin, while for β-cyclodextrin these rates are little bit higher (2.9–3.4 mM/s). The rates corresponding to “strong-bonded” water molecules are approximately tens fold lower (0.05–0.3 mM/s for α-cyclodextrin and 0.15–0.33 mM/s for β-cyclodextrin). The approximate ratio between “surface” and “strong-bonded” water molecules could also be estimated by this simple and rapid method.     

Swelling determination of W/O/W emulsion liquid membranes

Based on the definition of swelling in emulsion liquid membrane (ELM) process, the concepts of apparent swelling and actual swelling are proposed to illustrate the relationship between the emulsion swelling (the osmotic swelling and entrainment swelling) and the membrane breakage, focussing on the effect of the volume change caused by emulsion swelling and membrane breakage on the experimental results. Theoretical analyses indicate that “zero” or “negative” swelling may occur under certain experimental conditions. A bi-tracer method is further proposed and then used to measure the osmotic, entrainment swelling and the membrane breakage simultaneously, only requiring some initial operation conditions and measurements of concentrations of both tracers in the external and internal phases. It has been experimentally proved that this new method is highly applicable in ELM process and provides a useful tool to specify the effects of membrane breakage, osmotic swelling and entrainment swelling in the same experiment. “Negative” swelling may occur under certain operating conditions, particularly when the electrolyte concentration in the external phase is higher than that in the internal phase. The experimental results also indicate that the effect of membrane breakage on the measurement of emulsion swelling should not be neglected to avoid measurement error. Polymeric surfactant LMA is superior to other commercial surfactants as it imparts high membrane stability and small emulsion swelling.     

Strong and weak points in the interpretation of colloid stability

Lyophobic dispersions can be stabilized against aggregation by electrostatic repulsion or by “steric” repulsion caused by the presence of large molecules at the interfaces. Theories of colloid stability are briefly reviewed.Strong and weak points in the present interpretations are pointed out. Two important weak points in the interpretation of electrostatic stabilization are: 1) the assumption that the zeta potential and the Stern potential are about identical, and 2) the apparent lack of influence of the particle size on the rate of slow coagulation.A list of areas where new experiments and/or further development of theories are expected to be profitable closes the paper. In several of these areas a combination of a fluid mechanical and a colloid chemical approach is called for.     

Kinetic aspects of catalyzed reactions in the formation of poly(ethylene terephthalate)

The influence of different types of catalysts on the polycondensation reaction has been studied in a model system. It has been found that two kinds of catalysts are to be distinguished. “Transesterification” catalysts (Mn, Pb, Zn) are very active in media having both a high and a low hydroxyl content. However, they are easily poisoned by very small amounts of carboxylic endgroups. This restricts their activity to the period of transesterification. The “polycondensation” catalyst antimony is insensitive to the presence of acidic endgroups. However, its activity is inversely proportional to the hydroxyl group concentration For this reason antimony is hardly effective during transesterification. During polycondensation it becomes gradually more active.     

Stabilizing selenium nanoparticles with chymotrypsin: The effect of pH and nanoparticle-enzyme concentration ratios on the stability of nanocomplexes

Conditions of the formation of soluble chymotrypsin complexes with selenium nanoparticles are studied. It is established that the aggregative stability of the nanocomplexes is determined by their conditions of preparation, depending also on the medium pH and ratio of selenium: chymotrypsin concentration. It is shown that chymotrypsin has a “protective” effect due to its hydrophobic adsorption on the surface of selenium nanoparticles and hence the hydrophilization of their surfaces due to ionized groups of the protein.     

Preparation of a reference material “Creatinine in Human Urine”

Two batches of a reference material “Creatinine in Human Urine” have been prepared with creatinine concentrations at the physiological level, and used in interlaboratory comparisons in which up to 26 laboratories participated employing up to 4 independent methods. The 95% confidence intervals obtained for the certified creatinine concentrations are better than the “acceptable ranges” of commercially control samples available for clinical laboratories, the certified values being traceable to mean values of the commercial control samples. Thus, a suitable reference material has been prepared for the quality assurance of environmental and occupational health studies in which the concentration of a pollutant or its metabolites in human urine has to be related to the creatinine concentration.     

Observing the 3D Chemical Bond and its Energy Distribution in a Projected Space

Our curiosity-driven desire to “see” chemical bonds dates back at least one-hundred years, perhaps to antiquity. Sweeping improvements in the accuracy of measured and predicted electron charge densities, alongside our largely bondcentric understanding of molecules and materials, heighten this desire with means and significance. Here we present a method for analyzing chemical bonds and their energy distributions in a two-dimensional projected space called the condensed charge density. Bond “silhouettes” in the condensed charge density can be reverse-projected to reveal precise three-dimensional bonding regions we call bond bundles. We show that delocalized metallic bonds and organic covalent bonds alike can be objectively analyzed, the formation of bonds observed, and that the crystallographic structure of simple metals can be rationalized in terms of bond bundle structure. Our method also reproduces the expected results of organic chemistry, enabling the recontextualization of existing bond models from a charge density perspective.     

Hydrophilicity Impact upon Physical Properties of the Environmentally Friendly Poly(3-hydroxybutyrate) Blends: Modification Via Blending

We have integrated scientific research of polymer blends on the base of poly-3-hydroxybutyrate (PHB and its copolymers) with bench testing in blend preparation by both solvent casting and melt extrusion. As a second component, we have used traditional synthetic macromolecules with various hydrophilicity degree and hence with different morphologies and physical behavior. Besides, variation of polymer hydrophilicity permits to control both the service characteristic and the rate of (bio)degradation operating in the presence of water. Therefore, a substantial part of our work is devoted to water transport in the parent PHB and its blends. Combining the morphology knowledge (SEM, WAXS, FTIR tecynique), transport characteristics (permeability cells and McBain spring microbalance), and mechanical testing, we propose that blending of the parent biodegradable polymer with synthetic macromolecules is a perspective tool to design novel materials with improved characteristics. Both the water transport coefficients and the mechanical characteristics are essentially sensitive to structure and morphology of the blends. Hydrophilicity variation in the order LDPE < SPEU < PVA at blending with PHB shows that the morphology transformation in immicsible or partly miscible blends shifted along the PHB concentration scale as LDPE (at ∼16 wt% PHB) < PVA (∼30 wt% PHB) < SPEU (∼50 wt% PHB) Our instrumental monitoring the structural hierarchy of parent polymers and their blends as well as , simultaneously, the study of transport processes, their modeling, and computer simulating open up the way to understanding the precepts of polymer operation in corrosive and bioactive media.     

WATGEN: an algorithm for modeling water networks at protein-protein interfaces

Water molecules at protein-protein interfaces contribute to the close packing of atoms and ensure complementarity between the protein surfaces, as well as mediating polar interactions. Therefore, modeling of interface water is of importance in understanding the structural basis of biomolecular association. We present an algorithm, WATGEN, which predicts locations for water molecules at a protein-protein or protein-peptide interface, given the atomic coordinates of the protein and peptide. A key element of the WATGEN algorithm is the prediction of water sites that can form multiple hydrogen bonds that bridge the binding interface. Trial calculations were performed on water networks predicted by WATGEN at 126 protein-peptide interfaces (X-ray resolutions 相似文献   

Superstructures of Functional Colloids: Chemistry on the Nanometer Scale

Chemistry is classically concerned with the connection of atoms and molecules into new functional units. The rules of connection are yet to be extended to the generation and connection of larger objects, whose dimensions are measured in nanometers. However, linking objects of this size through molecules approaching each other randomly is inefficient, instead the principle of self-assembly is decisive, in which lyotropic structure formation or amphiphilic interaction play a significant role. As a result of the nature of the energetic driving forces, the objects generated in this way are often well-defined aggregate structures or highly symmetric volume phases. In contrast to “molecular chemistry”, the linking of larger objects also disregards the inherent borders of classical fields of chemistry: for example, the nanoscale association of inorganic colloids with polymers affords hybrid materials that combine the physical properties of both partners. In such a way, catalytic, optical, and electronic features of inorganic colloids might be combined with the mechanical characteristics of polymers such as film formation, elasticity, and melt processibility.     

Diffusion of spherical micronetworks in polymer diluent systems and melts studied by dynamic light scattering techniques

Spherical polystyrene (PS) micronetworks can be prepared in microemulsion with bulk radii of 5–60 nm and different cross-linking densities. The diffusion of these PS spheres has been studied in polymer diluent systems ranging from dilute solutions to plasticized melts by using forced Rayleigh scattering and photon correlation spectroscopy. On increasing the PS concentration, a colloid glass transition is observed at a volume fraction Φ_C ≈ 0.64 of the swollen spheres. At higher concentration inside the “colloid glass” state the sphere diffusion is slowed down and becomes very complex but can be observed up to the limit of a melt of collapsed spheres.     

Groups of Organic Molecules That Operate Collectively

A “chemical system” is defined as an assemblage of molecules that collectively does something interesting or useful. The key word here is “collectively”, a word that implies an interdependency and a group behavior that can be quite different from that of individual molecules. Batteries, computer chips, concrete, mayonnaise, shampoo, paint, liquid crystal displays, composites, and viruses are all examples of commonly encountered systems. A host–guest or “supramolecular” complex, on the other hand, would not be considered a system (as defined here), because only two species are involved. A chemical system is multimolecular, a collection of molecules interlocked in a tangle of dependencies. The review delves into a variety of chemical systems investigated by the author, including micelles, water pools, films, vesicles, and polymers. All of them can be categorized as “self-assembling” or “self-organizing” in the sense that defined structures arise spontaneously owing to noncovalent forces among the component molecules. Such chemical systems are useful for many purposes, including decontamination of environmentally dangerous substances, drug delivery, and separation of organic compounds.     

Ion Interaction: The Energetics and Mechanism of The Competitive Behavior Between Two Similarly Charged Molecules. 1. The Effect of Ionic Strength,Acetonitrile and Surfactant Concentration

Abstract

The competition between two molecules of similar polarity for adsorption sites on the stationary phase is discussed in light of the effects of acetonitrile, surfactant (cyclohexylaminopropane sulfonic acid, CAPS) and salt concentrations on the retention of the thyroid hormones (3,5-diiodo-thyronine, T2; 3,3′,5-diiodo-thyronine, T3 and thyroxine, T4). The Kinetics of adsorption and desorption for the surfactant are fast which allows for actual competition, otherwise an electrostatic “wall” would be seen by the analyte leadiny to exclusion. A three-parameter equation relates the surfactant concentration and ionic strength to the retention of the hormones, which suggests that the retention and selectivity arise from the structure and “density” of the outer layer in a Stern-Gouy-Chapman model and confirms that only the outer electrical layer significantly contributes. The data are analyzed with both Langmuir and Freundlich equations which describe an intermediary state where the marginal heat of adsorption begins to be negligible with respect to the surface concentration of the surfactant.     

Micellar behaviour in solutions of bile-acid salts

Summary From the vapour-pressure values for aqueous solutions of sodium cholate, desoxycholate and dehydrocholate measured by a thermistor method the osmotic coefficients, the activity of water and the mean activity of the bile salts have been calculated. In the case of sodium cholate and desoxycholate these quantities were found to vary with concentration in a manner characteristic of association colloid solutions and pointing to an association process in the concentration range 0.013–0.11 and 0.004–0.05 molal, respectively. For the dehydrocholate the evidence of an association is less conclusive.

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Zusammenfassung Die osmotischen Koeffizienten, die Aktivität des Wassers und die mittlere Aktivität der Gallensalze sind aus den Dampfdruckwerten für wässerige Lösungen des Natriumcholats, des Natriumdesoxycholats und des Natriumdehydrocholats errechnet worden. In derselben Weise wie in Lösungen der Assoziationskolloide variieren diese Größen im Falle von Natriumcholat und-des-oxycholat mit der Konzentration und weisen auf einen Assoziationsvorgang im Konzentrationsgebiet 0.013 bis 0.11 bzw. 0.004–0.5 molal hin. Für das Dehydrocholat sind die experimentellen Resultate weniger eindeutig.

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With 7 figures