Cosolute

Pairwise hydrophobic interactions can be used to alter the reactivity of organic molecules in water. For instance, the rate of hydrolysis reactions may be influenced significantly by the presence of hydrophobic cosolutes. The effect on reactivity has been analysed by comparirg the interactions between initial state and cosolute with those between transition state and cosolute. ... 

Water Suspended Dissolved Dissolved Dissolved Cosolution... 

The log-linear solubility enhancement by cosolutes may be important in characterizing concentrated leachate plumes or chemical spills, but will be of little importance in characterizations of the dilute aqueous systems that predominate in nature [19,55,143,145,158,184,226,241-247,249-263]. 

On the other hand, the organic acid and polymer (molecular weight varied from 2000 to 90,000) created no observable solubility enhancement. The investigation of phenyl acetic acid as a cosolute, with concentration > 600 mg/1, shows a slight enhancement for the most hydrophobic DDT. The magnitude of the DDT solubility enhancement/unit mass [19, 249] for phenylacetic acid was much smaller than with the DHA or DFA. They found that the solubility enhancement... 

Li, A. and Doucette, W.J. The effect of cosolutes on the aqueous solubilities and octanol/water partition coefficients of selected polychlorinated biphenyl congeners. Environ. Toxicol. Chem., 12(ll) 2031-2035, 1993. 

Not surprisingly, it is rather difficult to separate the different contributions of the different interactions as they occur in the micellar Stern region. In an attempt to solve this problem, the group of Engberts used a series of hydrolysis reactions of activated esters and amides to probe the reaction environment offered by micelles. The reactions initially involved the water-catalyzed pH-independent hydrolysis reactions of i-methoxy-phenyl dichloroacetate 4 and l-benzoyl-3-phenyl-l,2,4-triazole 5, as extensive information on the rate retarding effects of added cosolutes on this reaction was available. ... 

This is consistent with a study by Feilberg and Nielsen (1999b), who investigated the influence of other aerosol components on the photodegradation rates of representative particle-associated nitro-PAHs in a model system consisting of the nitro-PAH dissolved in cyclohexane along with various known constituents of diesel exhaust and wood smoke particles. These cosolutes included PAHs, substituted phenols, hydroxy-PAHs, oxy-PAHs, and substituted benzaldehydes. 

In the absence of cosolutes, the photodegradation rates depended on the orientation of the nitro group. Thus 1-nitropyrene decayed relatively fast by the nitro-nitrite primary intramolecular photorearrangement process, followed by secondary radical reactions. However, 2-nitropyrene and 2-nitrofluoranthene were stable toward photolysis, consistent with the N02 group being in the same plane as the aromatic rings. 

However, when H-atom-donating cosolutes, e.g., certain phenols, were added, the photodegradation rates of both 1-nitropyrene and 3-nitrofluoranthene increased. In this case, the reaction occurred via H-atom abstraction from the phenol by the electronically excited nitro-PAHs. Feilberg and Nielsen concluded that the photodegradation of nitro-PAHs on both diesel particles and wood smoke proceeds primarily by radical formation. However, H-atom abstraction by the excited triplet states of 1-nitropyrene and 2-nitrofluoranthene may also contribute. 

We have seen earlier in this chapter how the self-assembly of casein systems is sensitively affected by temperature. Another thermodynamic variable that can affect protein-protein interactions in aqueous media is the hydrostatic pressure. Static high-pressure treatment causes the disintegration of casein micelles due to the dismption of internal hydro-phobic interactions and the dissociation of colloidal calcium phosphate. This phenomenon has been used to modify the gelation ability of casein without acidification as a consequence of exposure of hydrophobic parts of the casein molecules into the aqueous medium from the interior of the native casein micelles (Dickinson, 2006). High-pressure treatment leads to a reduction in the casein concentration required for gelation under neutral conditions, especially in the presence of cosolutes such as sucrose (Abbasi and Dickinson, 2001, 2002, 2004 Keenan et al., 2001). 

Tsoga, A., Richardson, R.K., Morris, E.R. (2004a). Role of cosolutes in gelation of high-methoxy pectin. Part 1. Comparison of sugars and polyols. Food Hydrocolloids, 18, 907-919. 

Part Three describes a range of important specific examples of the interactions of individual biopolymers in the bulk aqueous medium of food colloids. Chapter six is devoted to the subject of the self-assembly of food biopolymers, and how this self-assembly is affected by conditions such as pH, ionic strength, divalent ions, cosolutes, etc. It is indicated how biopolymer self-assembly can form the basis of the bottom-up nano-biotechnological approach, which attempts to mimic Nature in the creation of new and varied structures with potential applications. It is... 

So far, we have focused on how differences in molecular structure affect the solubilities and activity coefficients of organic compounds in pure water at 25°C. The next step is to evaluate the influence of some important environmental factors on these properties. In the following we consider three such factors temperature, ionic strength (i.e., dissolved salts), and organic cosolutes. The influence of pH of the aqueous solution, which is most important for acids and bases, will be discussed in Chapter 8. 

Furthermore, for most compounds of interest to us, the octanol molecules present as cosolutes in the aqueous phase will have only a minor effect on the other organic compounds activity coefficients. Also, the activity coefficients of a series of apolar, monopolar, and bipolar compounds in wet versus dry octanol shows that, in most cases, Yu values changes by less than a factor of 2 to 3 when water is present in wet octanol (Dallas and Carr, 1992 Sherman et al., 1996 Komp and McLachlan, 1997a). Hence, as a first approximation, for nonpolar solvents, for w-octanol, and possibly for other solvents exhibiting polar groups, we may use Eq. 6-11 as a first approximation to estimate air- dry organic solvent partition constants for organic compounds as illustrated in Fig. 6.2. Conversely, experimental KM data may be used to estimate K,aw or Kitvi, if one or the other of these two constants is known. 

Klausen, J., S. B. Haderlein, and R. P. Schwarzenbach, Oxidation of substituted anilines by aqueous MnOz Effect of cosolutes on initial and quasi-steady-state kinetics , Environ. Sci. Technol., 31, 2642-2649 (1997). 

Inserted L-rhamnopyranosyl units may provide the necessary irregularities (kinks) in the structure required to limit the size of the junction zones and produce a gel. The presence of side chains composed of D-xylosyl units may also be a factor that limits the extent of chain association. Junction zones are formed between regular, unbranched pectin chains when the negative charges on the carboxylate groups are removed (addition of acid), hydration of the molecules is reduced (addition of a cosolute to a solution of HM pectin), and/or pectinic acid polymer chains are bridged by multivalent, eg, calcium, cations. 

The lifetimes of the BRs are of critical importance to any attempt at quantitative analysis of the factors which will determine quantum yields and product distributions (E/C and t/c ratios) in Type II reactions of ketones under various reaction conditions. Virtually all information about lifetimes is derived from study of triplet BRs and much of it has been provided, and reviewed, by Scaiano [261]. There are many interesting reactions, both bimolecular and unimolecular, which occur at only one of the radical centers but they have little relevance to this chapter and are not discussed here. BR triplets derived from alkanophenones have lifetimes of 25-50 ns in hydrocarbon solvents. They are lengthened several fold in t-butyl alcohol and other Lewis bases capable of hydrogen bonding to the OH groups of the BRs. The rates of decay are virtually temperature independent but are shortened by paramagnetic cosolutes such as 02 or NO. The quenchers react with the BRs... 

The experimental techniques available to determine AWPCs and their limitations have been discussed by Staudinger and Roberts [2]. These authors also evaluated the effects of pH, compound hydration, compound concentration, cosolvent, cosolute, and salt effects, suspended solids, dissolved organic matter, and surfactants. The experimental data have been compiled by a number of different authors [2-11]. 

Kim AI, Knopp S, Akers MJ, Nail SL. The physical state of mannitol after freeze-drying effects of mannitol concentration, freezing rate, and a noncrystallizing cosolute. J Pharm Sci 1998 87 931-935. 

Rao et al. (1990) investigated the effect of nonpolar cosolutes (trichloroethylene, toluene p-xylene), polar cosolutes (1-octanol, chlorobenzene, nitrobenzene, o-cresol) and polar cosolvents (methanol and dimethyl sulfoxide) on sorption of several polycyclic aromatic hydrocarbons (PAHs). The nonpolar cosolutes did not significantly influence PAH sorption, while the polar cosolutes (nitrobenzene, o-cresol), having sufficiently high aqueous solubilities, caused a significant decrease in PAH sorption. 

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