Lipophiles mixtures

Basic compounds are adsorbed from aqueous solution by adjusting to alkaline pH with buffer, e.g. a buffer of pH 10 would be suitable for most bases. The column can be washed with further aliquots of alkaline buffer, water or if the compound is highly lipophilic, mixtures of methanol and alkaline buffer can be carried out. The compound is finally eluted with either an acidic buffer or with an organic solvent such as methanol or ethanol. An example of an extraction of an amine using a lipophilic silica gel is shown in Box 15.1. 

The fruit and seeds of the milk thistle plant contain a lipophilic mixture of flavonolignans known as silymarin. Silymarin comprises 2-3% of the dried herb and is composed of three primary isomers, silybin (also known as silybinin or silibinin), silychristin (silichristin), and silydianin (silidianin). Silybin is the most prevalent and potent of the three isomers and accounts for about 50% of the silymarin complex. Products should be standardized to contain 70-80% silymarin. 

The studies described above illustrate the difficulties in predicting the effects of mixtures, even when all components are chemically similar. In these studies, exposures to lipophilic mixtures of very similar compounds produced expected effects in one study and unanticipated effects in different body organs in the other studies. These studies, as well as others describing the effects of lipophile/hydrophile mixtures, point out the need to limit exposures to aromatic hydrocarbons. 

A/ofes 3White spirit is a mixture composed primarily of C9-C12 hydrocarbons. L, lipophilic mixture L,H, mixture of lipophilic and hydrophilic species. 

This chapter contains a discussion of possible ways of separating lipophilic mixtures of natural products, the components of which are built up from isoprene units in accordance with Ruzicka s isoprene rule [219]. Wallach [321] has divided the hydrocarbons and their derivatives into the following groups ... 

Essential oils are steam-volatile, lipophilic mixtures of naturally occurring substances from plants they usually possess a characteristic odour. In addition to the one or several chief constituents which are specific for the oil concerned, numerous (up to ca. 50) other compounds of the types discussed in the preceding paragraphs may be present. 

Essential oils are limpid, volatile and lipophilic mixtures of natural compounds with strong and unique odors that are biosynthesized by aromatic plants as secondary metabolites [35]. Essential oils are soluble in organic solvents and immiscible with water, and generally have a lower density than that of water [10]. The compounds found in essential oils are mainly alcohols, ketones, aldehydes and esters, which account for their physicochemical... 

Lanolin alcohols are obtained by saponification of purified wool grease, a mixture of high molecular esters that is recovered in wool (qv) scouring. Ethoxylation of purified lanolin alcohols yields a full series of lipophilic and hydrophilic nonionic emulsifiers whose largest use is in cosmetic preparations. Manufacturers include Amerchol, Croda, ICI, Henkel Corporation, Westbrook Lanolin, Witco, and Pulcra, SA. 

For practical appHcation in mixtures of water—organic solvent, only ammonium and phosphonium salts containing 15 or more C atoms are sufficiently lipophilic. In empirical catalyst comparisons crown ethers (hexaoxacyclooctodecanes) (1)—(3) were often as effective as the best onium salts. 

Lindane is one of eight different hexachlorocyclohexane (HCH), C H Cl, isomers and its Chemical Abstract n.2cniQ is la, 2a 3P, 4a, 5a 6P-hexachlorocyclohexane [58-89-9] (y-HCH or y-BHC, ben2ene hexachloride) (80). Commercial products containing lindane are marketed as either a mixture of isomers or as the pure y-BHC isomer. Not unexpectedly, lindane is a highly stable lipophilic compound and it has been used extensively worldwide as an insecticide. In contrast, hexachloropentadiene, C Cl, is an extremely reactive industrial intermediate used as a chemical intermediate in the synthesis of a broad range of cyclodiene-derived pesticides, which include endosulfan, endrin, heptachlor, and several different organohalogen flame retardants (81). 

As described above, the application of classical liquid- liquid extractions often results in extreme flow ratios. To avoid this, a completely symmetrical system has been developed at Akzo Nobel in the early 1990s [64, 65]. In this system, a supported liquid-membrane separates two miscible chiral liquids containing opposite chiral selectors (Fig. 5-13). When the two liquids flow countercurrently, any desired degree of separation can be achieved. As a result of the system being symmetrical, the racemic mixture to be separated must be added in the middle. Due to the fact that enantioselectivity usually is more pronounced in a nonaqueous environment, organic liquids are used as the chiral liquids and the membrane liquid is aqueous. In this case the chiral selector molecules are lipophilic in order to avoid transport across the liquid membrane. 

It is important to make the distinction between the multiphasic catalysis concept and transfer-assisted organometallic reactions or phase-transfer catalysis (PTC). In this latter approach, a catalytic amount of quaternary ammonium salt [Q] [X] is present in an aqueous phase. The catalyst s lipophilic cation [Q] transports the reactant s anion [Y] to the organic phase, as an ion-pair, and the chemical reaction occurs in the organic phase of the two-phase organic/aqueous mixture [2]. 

Separation by adsorption chromatography takes place preferentially as a result of hydrogen bonding or dipole-dipole interactions. Hence, separation of mixtures of substances on silica gel layers by lipophilic solvents primarily takes place according to polarity differences. Further separation within a polarity group can then be achieved either two-dimensionally or off-line by partition chromatography on anotho TLC plate (Fig. 4). 

The influence of the lipophilic external phase on the production of xylan-based microparticles by interfacial cross-linking polymerization has been investigated (Nagashima et al., 2008). Three different external phases were investigated a 1 4 (v/v) chloroform cyclohexane mixture, soybean oil, and a medium chain triglyceride, with viscosities below 1, 24, and 52 cP, respectively. It was observed that the use of these different lipid phases results in different macroscopic and microscopic aspects of the system (Figure 10). 

Cross-linked xylan-based microparticles are produced by the emulsification of an alkaline solution of xylan with a lipophilic phase formed by a mixture of chloroform and cyclohexane by using 5% (w/v) sorbitan triesterate as the surfactant. Subsequently, the cross-linking reaction is carried out for 30 minutes with 5% (w/v) terephthaloyl chloride in order to yield a hard and rigid polymeric shell (Nagashima et al., 2008). 

Many of the components of PCB and PBB mixtures are both lipophilic and stable, chemically and biochemically. Similar to the persistent organochlorine insecticides and their stable metabolites, they can undergo strong bioconcentration and bioaccumulation to reach relatively high concentrations in predators. 

Firemaster is a stable solid, resembling a PCB mixture in its lipophilicity, chemical and thermal stability, and low vapor pressure. Firemaster contains some 80 ont of a possible 209 PBB congeners, but just two of them— 2,2, 4,4, 5,5-hexabromobiphenyl and 2,2, 3,4,4, 5,5, heptabromobiphenyl—account for around 85% of the commercial product (Environmental Health Criteria 152). These two componnds were fonnd to be very slowly eliminated by humans exposed to them during the Michigan incident. A half-life of abont 69 weeks was estimated for 2,4,5,2,4, 5 -HBB. 

PCB mixtures were once used for a variety of purposes, and came to cause widespread environmental pollution. Over 100 different congeners are present in commercial products such as Aroclor 1248 and Aroclor 1254. PCBs are lipophilic, stable, and of low vapor pressure. Many of the more highly chlorinated PCBs are refractory, showing very strong biomagnification with movement along food chains. 

Preparative chromatographic resolution procedures have overall freed chemists from the constraint of dependency on crystallization. They are most often performed with covalent diastereomer mixtures but ionic salts can also be separated. Recently, it was found that the lipophilicity of TRISPHAT anion 8 profoundly modifies the chromatographic properties of the cations associated with it and the resulting ion pairs are usually poorly retained on polar chromatographic phases (Si02, AI2O3) [131]. Using enantiopure TRISPHAT anion. 

RH above can represent a very wide variety of xenobi-otics, including drugs, carcinogens, pesticides, petroleum products, and pollutants (such as a mixture of PCBs). In addition, endogenous compounds, such as certain steroids, eicosanoids, fatty acids, and retinoids, are also substrates. The substrates are generally lipophilic and are rendered more hydrophilic by hydroxy-lation. 

The Zn-N3imide interaction has been used to selectively extract imide-containing nucleosides and nucleotides into lipophilic media (39). Hexadecyl-derivatized Zn2+-cyclen was shown to extract dT from an aqueous solution containing a mixture of C, A, and G nucleobases. The antiviral agent AZT (3 azido-3 deoxythymidine) could also be extracted into CHCI3 from neutral aqueous solutions. Transport across a lipophilic layer was also shown, using acidic conditions, to promote the release of dT and AZT (Fig. 9). 

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