Pair Reagents IPR

The development of most ion-pairing chromatography (IPC) methods started with optimization of the mobile phase composition after an appropriate column was selected. The theory described in Chapter 3 assists the chromatographer to perform educated guesses. Chapters 7 through 10 discuss the main qualitative and quantitative attributes of tunable mobile phase parameters to illustrate their influence on the global performance of the method. 

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Uncommon IPRs were tested recently. Polymerized acyl monoglydnate surfactant was found to be as effective as sodium dodecylsulfate for the resolution of organic amines [126]. For the analysis of pyridine-based vitamins in infant formnlas, dioc-tylsulfosuccinate produced a unique retention pattern [133], Among bizarre IPRs, tris(hydroxymethyl)aminomethane was used for the determination of cyclamate in foods. It was selected over different ion-pair reagents such as triethylamine and dibu-tylamine, based on sensitivity and time economies [134]. Hexamethonium bromide, a divalent IPR, was used successfully to separate sulfonates and carboxylates [135]. 

Fig. 5-3. Dependence of the diphenhydramine k value on the chain length nc of the ion-pair reagent. - Separator column IonPac NS1 (10 pm) eluent 0.05 mol/L KH2P04 (pH 4.0) I acetonitrile (70 30 v/v) + 0.005 mol/L IPR flow rate 1 mL/min detection UV (220 nm) injection volume 50 pL solute concentration 40 mg/L diphenhydramine hydrochloride.

Even if anionic chaotropes are the most popular neoteric IPRs, polarizable cations such as sulfonium and phosphonium reagents showed single selectivity toward polarizable anions their behavior was rationalized on the basis of their chaotropicity. Probe anion retention generally increases in the order of tributylsulfonium < tetrabutylammonium < tetrabutylphosphonium. Interestingly, retention was found to be influenced by the kosmotropic/chaotropic character of both the IPR and the probe anion [93] and this confirms the peculiarities of hydrophobic ion-pairing. Quaternary phosphonium salts provided increased selectivity compared to ammonium in the IPC of heavy metal complexes of unithiol [112]. 

One of the most useful organic reactions discovered in the last several decades is the titanium-catalyzed asymmetric epoxidation of primary aUyUc alcohols developed by Professor Barry Sharpless, then at Stanford University. The reagent consists of tert-butyl hydroperoxide, titanium tetraisopropoxide [Ti(0-iPr)J, and diethyl tartrate. Recall from Section 3.4B that tartaric add has two chiral centers and exists as three stereoisomers a pair of enantiomers and a meso compound. The form of tartaric add used in the Sharpless epoxidation is either pure (+)-diethyl tartrate or its enantiomer, (-)-diethyl tartrate. The fert-butyl hydroperoxide is the oxidizing agent and must be present in molar... 

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