Hydrophobic-hydrophilic microenvironments

Scheme 10.26 Illustration of the encapsulation of Ru-TsDPEN in the nanocage with different hydrophobic/hydrophilic microenvironments. Reprinted with permission from Ref [72]. Copyright 2010 Royai Society of Chemistry.

A slight increase in the turbidity upon heating of aqueous solutions of the s-fractions of the NVCl/NVIAz-copolymers obtained from the feeds with initial comonomer molar ratios of 75 25 (Tcp 65 °C) and 80 20 (Tcp 66 °C) could be due to the micellization phenomena, although the absence of DSC peaks over the same temperature range testified to the non-cooperative character of the process. This could indicate that the chains of these s-type copolymers had, nevertheless, a certain amount of oligoNVCl blocks non-buried by the hydrophilic microenvironment sufficiently well and thus capable of participating in the hydrophobically-induced associative intermolecular processes at elevated temperatures. At the same time, the sequence of monomer units in the s-copolymers obtained from the feeds with the initial comonomer ratios of 85 15 and 90 10 (mole/mole) corresponded to the block-copolymers of another type. The basis for such a conclusion is the lack of macroscopic heat-induced phase separation at elevated temperatures (Fig. 3 a and b) and, simultaneously, the transi-... 

It is evident that a single electron transfer photoproduct is transformed into a doubly reduced charge relay in two phase systems. The primary processes in the natural photosynthetic apparatus involve single electron transfer reactions that proceed in hydrophobic-hydrophilic cellular microenvironment. Thus, we suggest similar induced disproportionation mechanisms as possible routes for the formation of multi-electron charge relays, effective in the fixation of CO2 or N2. 

Microheterogeneous environments that control photosensitized ET processes by means of electrostatic interactions include micelles [49-52], polyelectrolytes [53, 54], colloids [55-57], and clays [58, 59], Hydrophilic-hydrophobic organized microenvironments include micelles [49, 50], water-in-oil and oil-in-water micro-... 

Fig. 8a, b. Control of photoinduced ET reactions in organized microenvironments a) application of charged interfaces to effect charge separation and retard recombination processes by means of electrostatic interactions b) application of water-oil two phase systems in charge separation and stabilization of photoproducts against back reactions by means of hydrophobic-hydrophilic interactions... 

A neutral molecule solubilized in the micelle can be located in several positions or microenvironments. As early as the 1930s it was suggested by Lawrence that the site of a solubilized molecule would be dependent on the hydrophobic/hydrophilic composition of the solubilizate. Two extremes are easily identified the core of the micelle providing a hydrocarbon-like microenvironment, and the palisade layer providing an aqueous or water-rich interfacial environment. It seems logical to assume, then, that nonpolar solutes like alkanes would prefer the micellar core and that polar molecules would be anchored at the surface. However, this is an oversimplification available data tend to contradict it. First, the solubility of alkanes in micelles is significantly lower than expected if compared to solubility in hydrocarbon solvents. Second, the size of a micelle is normally such that part of the solute would be close to the surface at any time. Sepulveda et al. state that for SDS micelles at least half of the solute will be within 4 to 5 A of the surface. We should also consider the timescale of the experiments, as the timescale for intramicellar migration is short. The rate constants of entry and exit of molecules to and from micelles is of the order 1(F and... 

Initial efforts gave rise to well-characterized dendritic macromolecules, but applications remained limited because of the lack of specific functionalities. An exponential increase of publication volume observed for about 15 years testified the growing interest for dendrimers and has led to versatile and powerful iterative methodologies for systematically and expeditiously accessing complex dendritic structures. The perfect control of tridimensional parameters (size, shape, geometry) and the covalent introduction of functionalities in the core, the branches, or the high number extremities, or by physical encapsulation in the microenvironment created by cavities confer such desired properties as solubility, and hydrophilic/hydrophobic balance. Thus, creativity has allowed these structures to become integrated with nearly all contemporary scientific disciplines. 

In many biological systems the biological membrane is a type of surface on which hydrophilic molecules can be attached. Then a microenvironment is created in which the ionic composition can be tuned in a controlled way. Such a fluffy polymer layer is sometimes called a slimy layer. Here we report on the first attempt to generate a realistic slimy layer around the bilayer. This is done by grafting a polyelectrolyte chain on the end of a PC lipid molecule. When doing so, it was found that the density in which one can pack such a polyelectrolyte layer depends on the size of the hydrophobic anchor. For this reason, we used stearoyl Ci8 tails. The results of such a calculation are given in Figure 26. 

The energetically unfavorable interactions of the hydrophobic tails with the water molecules are then minimized by the surfactants forming aggregates with other surfactant molecules. In those aggregates, the hydrophilic headgroups remain solvated by water molecules while the hydrocarbon moieties are shielded from water and create a hydrophobic microenvironment. Examples of these spontaneously formed aggregates are micelles and lamellae. The intersection of the extrapolations of the linear parts of the surface tension curve (Figure 17.2) is the critical micelle concentration (CMC). 

Sometimes a very fluorescent molecule (fluoroprobe) is used to measure its microenvironment [fluorescence quenching, fluorescence polarization (developed by Weber60), and fluorescence probe for hydrophobic or hydrophilic regions in biological systems]. A very recent and "hot" label is the green fluorescent protein (238 amino acids, 26.9 kDa) first isolated from the jellyfish... 

Since these interfaces are usually constructed of charged detergents a diffuse electrical double layer is produced and the interfacial boundary can be characterized by a surface potential. Consequently, electrostatic as well as hydrophilic and hydrophobic interactions of the interfacial system can be designed. In this report we will review our achievements in organizing photosensitized electron transfer reactions in different microenvironments such as bilayer membranes and water-in-oil microemulsions.In addition, a novel solid-liquid interface, provided by colloidal Si02 particles in an aqueous medium will be discussed as a means of controlling photosensitized electron transfer reactions. 

Advances in chemical synthesis and in an understanding of the tear film of the eye have resulted in the development of compounds with two or more regions that vary in both their lipophilic nature and binding. The first of these to be tested in the eye was poloxamer 407, a block polymer vehicle with a hydrophobic nucleus of poly-oxypropylene,and hydrophilic end groups of polyoxyethylene. One advantage of poloxamers is their ability to produce an artificial microenvironment in the tear film, which can greatly enhance the bioavailability of lipophilic drugs such as steroids. 

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