Alkanes hydrophobic

Chemistry and general properties. The main challenge in the manufacture of paraffin sulphonates is the lack of a reactive function in the paraffin (alkane) hydrophobe but this is overcome by using the Strecker reaction or a variant of it. The classical Strecker reaction (shown in Figure 4.10) uses a chloroalkane (which can be made by the reaction of a chlorinating agent with an alcohol) and sodium sulphite. 

Aagg = 367rv la . For an alkane hydrophobe, v Uric A, where ric is the number of carbon atoms in the alkane chain [see Eq. (12-1)]. Thus, for = 16, we find the relationship Aagg 20/a, where a is in nm. Because the head groups of the telechelic... 

In this relationship. S is alkane solubility, A is the cavity surface area and a is the hydrophobic free energy per unit area. Extensive fitting of this equation [24] yields a value of 88 kJ mol A for the proportionality constant a. This value corresponds to an unfavourable free energy of about 3.6 kJ mol for the transfer of a CH2 group to aqueous solution. 

Jorgensen W L, J Gao and C Ravimohan 1985. Monte Carlo Simulations of Alkanes in Water Hydratior Numbers and the Hydrophobic Effect. Journal of Physical Chemistry 89 3470-3473. 

Alkanesulfonates are the petrochemically derived sulfur analogs of soaps, which are alkane carboxylates based on renewable resources. The main difference between alkanesulfonates and soaps is, however, that alkanesulfonates consist of a rather complex mixture of homologs with different carbon chain lengths and isomers with an almost statistical distribution of the functional group along the hydrophobic carbon chain (Fig. 1), whereas soap is a mixture of homologs of alkane 1-carboxylates with an even number of carbon atoms. 

The effective carbon number neff is helpful in characterizing surfactants with an inner functional group. Surfactants with isomeric structures can be compared by means of the hydrophobicity index / [69], which indicates the influence of the effective length of the alkane chain on cM ... 

The hydrophobicity index is also suitable for correlating the cM values of various substituted sodium alkane 1-sulfonates [68]. The perfluoroalkyl substituent, e.g., 8 17 has a pronounced hydrophobic effect (/ = 1.66 at 75°C, sodium salt), whereas the hydrophilic disulfonates have values distinctly below 1 (for a-disulfonates, / = 0.75 was derived [70]). Further, it was somewhat surprisingly shown that substituents like 1-hydroxymethyl, 3-hydroxyethoxy, or even the hydroxyethoxyethoxy groups have hydrophobic effects. 

The alkaline product from the wood ash was a crude solution of sodium and potassium carbonates called "lye". On boiling the vegetable oil with the lye, the soap (sodium and potassium salts of long chained fatty acids) separated from the lye due to the dispersive interactions between the of the fatty acid alkane chains and were thus, called "lyophobic". It follows that "lyophobic", from a physical chemical point of view, would be the same as "hydrophobic", and interactions between hydrophobic and lyophobic materials are dominantly dispersive. The other product of the soap making industry was glycerol which remained in the lye and was consequently, termed "lyophilic". Thus, glycerol mixes with water because of its many hydroxyl groups and is very polar and hence a "hydrophilic" or "lyophilic" substance. 

The effect of different backbones on ero.sion rates was demonstrated in a study of the homologous poly[ (p-carboxyphenoxy)alkane] series. As the number of methylene groups in the backbone increased from 1 to 6, thus decreasing the reactivity of the anhydride linkage and rendering the polymer more hydrophobic, the erosion rates underwent a decrease of three orders of magnitude (4). 

There is a much wider choice of hydrophobes. Most are based on substantially linear long-chain alkanes, either saturated or unsaturated. These were originally obtained from naturally occurring fats and oils such as castor, fish, olive, sperm, coconut and tallow oils, but these sources were later superseded by petroleum products which at that time were cheaper. More recently, not only has the price of crude oil escalated, but there has also been a growing... 

Gallicchio, E. Kubo, M. M. Levy, R. M., Enthalpy-entropy and cavity decomposition of alkane hydration free energies numerical results and implications for theories of hydrophobic solvation, J. Phys. Chem. B 2000,104, 6271-6285... 

Their hydrophobicity and their plasticity were appreciated and used for a long time in a wide range of activities. To our knowledge, the first wax to have been exploited is beeswax. Beeswax is produced by various species of bees in the world, and it has a melting point between 62°C and 64°C. It mainly contains homologous series of even-numbered fatty acids (C22 C34, C2 being the predominat compound), odd-numbered ra-alkanes (C2i C33, C27 being the major compound) and even-numbered palmitic esters from C40 to C52 (Tulloch and Hoffman, 1972 Kolattukudy, 1976). Hydroxy esters, diesters and hydroxy diesters also form part of beeswax to a lesser extent. 

Barone, G., Crescenzi, V., Pispisa, B., Quadrifoglio, B. (1966) Hydrophobic interactions in polyelectrolytes solutions. II. Solubility of some C3-C6 alkanes in poly(methacrylie acid) aqueous solutions. J. Macromol. Chem. 1, 761-771. 

The H- and N-isoforms of Ras support the first (isoprenoid) hydrophobic modification by additional thioester formation with palmitoylic acids [18]. At physiological temperature (37°C) the dissociation of doubly modified lipo-peptides with an isoprenyl thioether and a palmitoyl thioester is very slow and characterized by half-times in the order of 50 h. Here, the relative effect of the carboxymethylation is significantly reduced. Palmitoyl groups with their C16 alkane chain length contribute more efficiently to membrane anchoring than the farnesyl modification. 

As well as fluorescence-based assays, artificial membranes on the surface of biosensors offered new tools for the study of lipopeptides. In a commercial BIA-core system [231] a hydrophobic SPR sensor with an alkane thiol surface was incubated with vesicles of defined size distribution generating a hybrid membrane by fusion of the lipid vesicles with the alkane thiol layer [232]. If the vesicles contain biotinylated lipopeptides their membrane anchoring can be analyzed by incubation with streptavidine. Accordingly, experiments with lipopeptides representing the C-terminal sequence of N-Ras show clear differences between single and double hydrophobic modified peptides in their ability to persist in the lipid layer [233]. 

The results summarized above were obtained by using fluorescence based assays employing phospholipid vesicles and fluorescent labeled lipopeptides. Recently, surface plasmon resonance (SPR) was developed as new a technique for the study of membrane association of lipidated peptides. Thus, artificial membranes on the surface of biosensors offered new tools for the study of lipopeptides. In SPR (surface plasmon resonance) systemsI713bl changes of the refractive index (RI) in the proximity of the sensor layer are monitored. In a commercial BIAcore system1341 the resonance signal is proportional to the mass of macromolecules bound to the membrane and allows analysis with a time resolution of seconds. Vesicles of defined size distribution were prepared from mixtures of lipids and biotinylated lipopeptides by extruder technique and fused with a alkane thiol surface of a hydrophobic SPR sensor. 

A well-studied example of a bioemulsifier is emulsan, a cell surface-exposed molecule that allows Acinetobacter calcoaceticus RAG-1 to attach to crude oil droplets [123]. Upon depletion of the short-chain alkanes utilised by this strain, the emulsan molecules were released from the bacterial surface, thereby allowing the cells to leave the oil droplet and to find a new substrate. Important positive side-effects of this mechanism seem to be that the remaining emulsan hydrophilises the droplet and prevents both the reattachment of A. calcoaceticus RAG-1 and the coalescence of the used oil droplet with other droplets that still contain unexploited alkanes. Bredholt et al. [124] studied the oil-emulsifying activity of Rhodococcus sp. strain 094. When exposed to inducers of crude-oil emulsification, the cells developed a strongly hydrophobic character, which was rapidly lost when crude-oil emulsification started. This indicated that the components responsible for the formation of cell-surface hydrophobi-city acted as emulsion stabilisers after release from the cells. 

The micellization behavior of copolymers containing two hydrophobic blocks, or double-hydrophobic block copolymers, has been shown to be mainly controlled by the solvent and its interaction with the copolymer blocks. It is thus possible to tune the micellization of these copolymers by changing the organic solvent. In this respect, large differences in Z, i h, Rc, etc. are expected whenever the interaction parameter between the polymer and the solvent is varied. This is illustrated by, e.g., the work of Pit-sikalis et al. [87] for PS-PSMA diblock copolymers dissolved in either ethyl-or methylacetate. The effect of temperature has been studied by Quintana et al. [88,89], who have clearly shown that CMC decreases with increasing temperature for PS-PEB copolymers in alkanes. 

The hydrogen bonds in aliphatic alcohol clusters can be modified in a systematic, yet subtle, way by replacing hydrogen atoms of the alkyl group by fluorine atoms [248, 249]. This leads to only modest changes in spatial extension, but it introduces polarity into the hydrophobic alkyl chains. Despite their polarity, the fluorine atoms are not considered to be attractive hydrogen bond acceptors [250]. Huorinated alkanes have quite remarkable properties that can be related to this combination of polarity and weak hydrogen bond propensity. Alcohols with... 

Traube s rule accommodates the balance between hydrophobicity and hydro-philicity. It has been extended somewhat and formalized with the development of quantitative methods to estimate the surface area of molecules based on their structures [19, 237]. The molecular surface area approach suggests that the number of water molecules that can be packed around the solute molecule plays an important role in the theoretical calculation of the thermodynamic properties of the solution. Hence, the molecular surface area of the solute is an important parameter in the theory. In compounds other than simple normal alkanes, the functional groups will tend to be more or less polar and thus relatively compatible with the polar water matrix [227,240]. Hence, the total surface area of the molecule can be subdivided into functional group surface area and hydro carbonaceous surface area . These quantities maybe determined for simple compounds as an additive function of constituent groups with subtractions made for the areas where intramolecular contact is made and thus no external surface is presented. 

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