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The Reciprocal Principle of Selectand-Selector-Systems in Supramolecular Chromatography †

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The Reciprocal Principle of Selectand-Selector-Systems in Supramolecular Chromatography † molecules Review The Reciprocal Principle of Selectand-Selector-Systems in Supramolecular Chromatography † Volker Schurig Institute of Organic Chemistry, University of Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany; [email protected]; Tel.: +49-7071-62605 † This contribution is dedicated to Professor Stig Allenmark at his 80th anniversary. Academic Editor: Yoshio Okamoto Received: 5 October 2016; Accepted: 7 November 2016; Published: 15 November 2016 Abstract: In selective chromatography and electromigration methods, supramolecular recognition of selectands and selectors is due to the fast and reversible formation of association complexes governed by thermodynamics. Whereas the selectand molecules to be separated are always present in the mobile phase, the selector employed for the separation of the selectands is either part of the stationary phase or is added to the mobile phase. By the reciprocal principle, the roles of selector and selectand can be reversed. In this contribution in honor of Professor Stig Allenmark, the evolution of the reciprocal principle in chromatography is reviewed and its advantages and limitations are outlined. Various reciprocal scenarios, including library approaches, are discussed in efforts to optimize selectivity in separation science. Keywords: supramolecular chromatography; electromigration methods; selectand; selector; reciprocal principle; combinatorial libraries; cyclopeptides; single-walled nanotubes (SWCNTs); fullerenes; cyclodextrins; calixarenes; congeners; enantiomers; molecular recognition; chiral recognition; chiral stationary phases 1. Introduction Separation approaches in highly selective supramolecular chromatography [1,2], with their most refined expression of stereochemical resolution [3], rely on the fast and reversible non-covalent association equilibrium between functionally and/or structurally complementary partners. The designations selector and selectand were introduced by Mikeš into chromatography to avoid ambiguities that may arise from the use of the notations solvent-solute, ligand-substrate, or host-guest [4]. The new terms were coined in analogy to Ashby’s cybernetic operator-operand terminology [5]. This terminology extends to all supramolecular interactions such as antibody-antigen, receptor-substrate, metal ion-ligand etc. In chromatographic partitioning systems, selectors are employed to separate mixtures of selectands which are added to the mobile phase. The selector is either present as a stationary phase or as an additive to the liquid mobile phase. In order to find an optimized selector for a pair of selectands, the role of selector/selectand can be reversed by the reciprocal principle. One molecule of the selectand is now used as the stationary phase and an array of potential structural related selectors are now employed as analytes in the mobile phase. The best identified candidate is then used as the optimized lead stationary phase for the target selectands to be separated. Thus the reciprocal recognition principle applies to selective separation system when selectors and selectands change their role and belong to two or more forms of congeners, analogues, isomers etc. In the special case of chiral recognition, both enantiomers of selectand and selector must be available. This excludes proteins [6], carbohydrates [7] and antibodies [8], although they represent versatile chiral stationary phases (CSPs). Pertinent examples will be described in the following Sections. Molecules 2016, 21, 1535; doi:10.3390/molecules21111535 www.mdpi.com/journal/molecules Molecules 2016, 21, 1535 2 of 35 Molecules 2016, 21, 1535 2 of 35 2. Origin of the Reciprocal Principle in Chromatography 2. Origin of the Reciprocal Principle in Chromatography Following the enantioseparation of [5]–[14]helicenes on the optically active charge-transfer agent Following the enantioseparation of [5]–[14]helicenes on the optically active charge-transfer agent R-2-(2,4,5,7-tetranitro-9-fluorenylideneamino-oxy)propionic acid (TAPA, Figure 1) or its 2-butyric acid R-2-(2,4,5,7-tetranitro-9-fluorenylideneamino-oxy)propionic acid (TAPA, Figure1) or its 2-butyric acid homologue (TABA) [9–11], Mikeš speculated that the function of the selector and the selectand could homologue (TABA) [9–11], Mikeš speculated that the function of the selector and the selectand could be reversed, i.e., optically active helicenes could be used as resolving agents for racemic compounds be reversed, i.e., optically active helicenes could be used as resolving agents for racemic compounds [4]. [4]. Thus, in a reciprocal fashion, if the selectands A1 and A2 are chromatographically separated on the Thus, in a reciprocal fashion, if the selectands A1 and A2 are chromatographically separated on the selector B1 (or B2), the selectands B1 and B2 are separated on the selector A1 (or A2) as well, whereby selector B1 (or B2), the selectands B1 and B2 are separated on the selector A1 (or A2) as well, whereby the respective pairs A1/A2 and B1/B2 refer to isomers (e.g., stereoisomers) or belong to members of the respective pairs A1/A2 and B1/B2 refer to isomers (e.g., stereoisomers) or belong to members homologous series of compounds (Figure 2). Indeed, it was subsequently demonstrated that P-(+)- of homologous series of compounds (Figure2). Indeed, it was subsequently demonstrated that hexahelicene-7,7′-dicarboxylic acid disodium salt could be used as the chiral stationary phase (CSP) P-(+)-hexahelicene-7,70-dicarboxylic acid disodium salt could be used as the chiral stationary phase as π-donor selector for the enantioseparation of N-2,4-dinitrophenyl(DNP)-α-amino acid esters as (CSP) as π-donor selector for the enantioseparation of N-2,4-dinitrophenyl(DNP)-α-amino acid esters π-acceptor selectands by HPLC [12]. as π-acceptor selectands by HPLC [12]. FigureFigure 1. EnantiomericEnantiomeric separation separation of of racemic racemic [5]–[14]helicenes on ((RR)-()-(−)-2-(2,4,5,7-tetranitro-9-)-2-(2,4,5,7-tetranitro-9- fluorenylideneamino-oxy)propionicfluorenylideneamino-oxy)propionic acid acid (TAPA) (TAPA) linked linked to to silica silica gel gel [4]. [4]. ( (aa)) odd odd numbers; numbers; ( (bb)) even even numbers.numbers. Insertions: Insertions: [7]helicene [7]helicene and and TAPA. TAPA. FigureFigure 2 2.. TheThe reciprocalreciprocal supramolecularsupramolecular recognition recognition principle. principle. If If the the selector selector B B separates separates the the selectands selectands AA11 andand A2 A, than2, than the theselector selector A is expected A is expected to separate to separate the selectands the selectands B1 and B2 B. A1 iand and B2i are.A homologousi and Bi are compounds,homologous congeners compounds, or isomers congeners (including or isomers enantiomers). (including enantiomers). The principle of reciprocity by inverting the role of selectand and selector had first been demonstrated via the differentiation of enantiomers by chiral solvating agents (CSA) in NMR Molecules 2016, 21, 1535 3 of 35 MoleculesThe2016 principle, 21, 1535 of reciprocity by inverting the role of selectand and selector had first3 ofbeen 35 demonstrated via the differentiation of enantiomers by chiral solvating agents (CSA) in NMR spectroscopyspectroscopy [ 13[13].]. Pirkle Pirkle et et al. al. stated: stated:the the enantiomersenantiomers ofof secondarysecondary andand tertiary tertiary alcohols alcohols may may be be caused caused to to havehave nonequivalent nonequivalent nmr nmr spectra spectra through through the the use use of of appropriate appropriate optically optically active active amines amines as as solvents. solvents. The The converse converse ofof this this phenomenon phenomenon also also obtains; obtains; amine amine enantiomers enantiomers may may have have nonequivalent nonequivalent nmr nmr spectra spectra in in optically optically active active alcoholsalcohols[ 14[14]] and and Pirkle Pirkle and and Hoover Hoover concluded concluded that that the the roles roles of of an an enantiomeric enantiomeric solute solute and and a a CSA CSAmay may bebe interchangeable interchangeablefor for a a given given pair pair of of compounds compounds [ 15[15].]. The Thereciprocal reciprocalprinciple principlewas was later later extended extendedby by PirklePirkle et et al. al. to to enantioselective enantioselective liquid liquid chromatography chromatography [ 16[16,17].,17]. The The researchersresearchers pointedpointed outout that that one one cancan take take one one chiral chiral stationary stationary phase phase (CSP) (CSP) to to develop develop others: others:if if a a CSP CSP derived derived from from (+)-A (+)-A retains retains (+)-B, (+)-B, thenthen a a CSP CSP comprised comprised of of immobilized immobilized (+)-B (+)-Bshould, should, using using the the samesame interactions,interactions, selectivelyselectively retain retain (+)-A (+)-A[ [18,19].18,19]. OrOr put put in in other other words words by by Pirkle Pirkle and and Pochapsky: Pochapsky:This This‘ bootstrapping‘bootstrapping’’method method of of designing designing reciprocal reciprocal CSPs CSPs fromfrom compounds compounds that that themselves themselves resolve resolve on on existing existing CSPs CSPs is is based based on on the the premise premise that that if if two two molecules molecules show show mutualmutual chiralchiral recognition,recognition, thenthen itit doesdoes notnot mattermatter whichwhich ofof thethe two two is is bound bound to to a a stationary stationary support support for for that that recognitionrecognition toto
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