Supramolecular perspectives in colloid science

Supramolecular chemistry puts emphasis on molecular assemblies held together by non-covalent bonds. As such, it is very close in spirit to colloid science which also focuses on objects which are small, but beyond the molecular scale, and for which other forces than covalent bonds are crucial. We discuss in this review the preparation and properties of new colloidal systems which borrow on the one hand from classical topics in colloid science, such as micellization, and on the other hand from concepts in supramolecular chemistry, such as reversible supramolecular polymers

Phase behavior of flowerlike micelles in a SCF cell model

We study the interactions between flowerlike micelles, self-assembled from telechelic associative polymers, using a molecular self-consistent field (SCF) theory and discuss the corresponding phase behavior. In these calculations we do not impose properties such as aggregation number, micellar structure and number of bridging chains. Adopting a SCF cell model, we calculate the free energy of interaction between a central micelle surrounded by others. Based on these results, we predict the binodal for coexistence of dilute and dense liquid phases, as a function of the length of the hydrophobic and hydrophilic blocks. In the same cell model we compute the number of bridges between micelles, allowing us to predict the network transition. Several quantitative trends obtained from the numerical results can be rationalized in terms of transparent scaling argument

Self-consistent-field calculations of proteinlike incorporations in polyelectrolyte complex micelles

Self-consistent field theory is applied to model the structure and stability of polyelectrolyte complex micelles with incorporated protein (molten globule) molecules in the core. The electrostatic interactions that drive the micelle formation are mimicked by nearest-neighbor interactions using Flory-Huggins X parameters. The strong qualitative comparison with experimental data proves that the Flory-Huggins approach is reasonable. The free energy of insertion of a proteinlike molecule into the micelle is nonmonotonic: there is (i) a small repulsion when the protein is inside the corona; the height of the insertion barrier is determined by the local osmotic pressure and the elastic deformation of the core, (ii) a local minimum occurs when the protein molecule is at the core-corona interface; the depth (a few kBT's) is related to the interfacial tension at the core-corona interface and (iii) a steep repulsion (several kBT) when part of the protein molecule is dragged into the core. Hence, the protein molecules reside preferentially at the core-corona interface and the absorption as well as the release of the protein molecules has annealed rather than quenched characteristics. Upon an increase of the ionic strength it is possible to reach a critical micellization ionic (CMI) strength. With increasing ionic strength the aggregation numbers decrease strongly and only few proteins remain associated with the micelles near the CM

Brownian particles in transient polymer networks

We discuss the thermal motion of colloidal particles in transient polymer networks. For particles that are physically bound to the surrounding chains, light-scattering experiments reveal that the submillisecond dynamics changes from diffusive to Rouse-like upon crossing the network formation threshold. Particles that are not bound do not show such a transition. At longer time scales the mean-square displacement (MSD) exhibits a caging plateau and, ultimately, a slow diffusive motion. The slow diffusion at longer time scales can be related to the macroscopic viscosity of the polymer solutions. Expressions that relate the caging plateau to the macroscopic network elasticity are found to fail for the cases presented here. The typical Rouse scaling of the MSD with the square root of time, as found in experiments at short time scales, is explained by developing a bead-spring model of a large colloidal particle connected to several polymer chains. The resulting analytical expressions for the MSD of the colloidal particle are shown to be consistent with experimental findings

Relaxation dynamics at different time scales in electrostatic complexes: Time-salt superposition

In this Letter we show that in the rheology of electrostatically assembled soft materials, salt concentration plays a similar role as temperature for polymer melts, and as strain rate for soft solids. We rescale linear and nonlinear rheological data of a set of model electrostatic complexes at different salt concentrations to access a range of time scales that is otherwise inaccessible. This provides new insights into the relaxation mechanisms of electrostatic complexes, which we rationalize in terms of a microscopic mechanism underlying salt-enhanced activated processe

Dynamics of polymer bridge formation and disruption

In this Letter we show, with colloidal probe AFM measurements, that the formation and subsequent disruption of polymer bridges between two solid surfaces is characterized by slow relaxation times. This is due to the retardation of polymer dynamics near a surface. For colloidal particles, that are in constant (Brownian) motion, kinetic aspects are key. To understand these effects, we develop a model of polymer bridging and bridge disruption that agrees quantitatively with our experiment

Колгоспні ліси у відомчому конфлікті Ніжинського головного лісництва та земельних органів окупаційної влади

During sediment transport downstream, river systems mix sediments from different parts of their catchments. During deposition, sediments are often unmixed again in different depositional environments (facies). During fluvial transport, between erosion and deposition of sediment, the sediment is sorted too. A commonly observed phenomenon is downstream fining (Frings, 2007), which is the tendency for bed sediments of many rivers to become finer downstream. All processes mentioned above make that fluvial sediment, and thus the fluvial record, is spatially variable

The more often you see an object, the easier it becomes to track it

Is it easier to track objects that you have seen repeatedly? We compared repeated blocks, where identities were the same from trial to trial, to unrepeated blocks, where identities varied. People were better in tracking objects that they saw repeatedly. We tested four hypotheses to explain this repetition benefit. First, perhaps the repeated condition benefits from consistent mapping of identities to target and distractor roles. However, the repetition benefit persisted even when both the repeated and the unrepeated conditions used consistent mapping. Second, repetition might improve the ability to recover targets that have been lost, or swapped with distractors. However, we observed a larger repetition benefit for color-color conjunctions, which do not benefit from such error recovery processes, than for unique features, which do. Furthermore, a repetition benefit was observed even in the absence of distractors. Third, perhaps repetition frees up resources by reducing memory load. However, increasing memory load by masking identities during the motion phase reduced the repetition benefit. The fourth hypothesis is that repetition facilitates identity tracking, which in turn improves location tracking. This hypothesis is consistent with all our results. Thus, our data suggest that identity and location tracking share a common resource

Beyond beauty : reexamining architectural proportion in the Basilicas of San Lorenzo and Santo Spirito in Florence

This dissertation reexamines the problem of architectural proportion in the basilica of San Lorenzo in Florence following a rigorous new methodology that combines comprehensive measurements and other observations with documentary evidence, in order to identify the intentions of the basilica’s fifteenth-century creators. It finds that the proportions of this basilica are indeed extraordinary, as scholars have long contended, but for reasons different than previously believed. This dissertation analyzes the proportions of the basilica with greater quantitative precision than any previous study has done, and demonstrates that carefully-crafted sets of proportions expressed in the measurements constitute mental constructs that communicate non-visual, iconographical content. It thus reframes the subject of architectural proportion as part of the rhetorical, rather than visual, structure of architecture. The sets of proportions identified in this dissertation correspond with late medieval knowledge and practices pertaining to geometry, number and arithmetic in so many documented ways that they can be considered genuine historical artifacts, and thus, sources of historical evidence themselves. As such, these sets of proportions lead both to several unconventional new conclusions pertaining to the history of this basilica, and to a proposed alternative to Rudolf Wittkower’s framework for the study of medieval and Renaissance architectural proportion.LEI Universiteit LeidenMedieval and Early Modern Studie

Study of pollution in the El Jadida-Safi Atlantic coastal zone (Morocco) by using PIXE and SSNTD methods

In this work PIXE experiments were performed for measuring heavy and light elements (ranging from aluminium to lead) concentrations inside various polluted and unpolluted soils as well as liquid samples collected from different phosphate factory sewers in the El Jadida-Safi Atlantic coastal region (Morocco). In addition, uranium (238U) and thorium (232Th) contents were evaluated in the same samples studied by using CR-39 and LR-115 type II solid state nuclear track detectors (SSNTDs). The influence of the phosphate industry wastes on the concentrations of both radioactive and non-radioactive elements of the samples studied was investigated