Journal of Chromatography A, 1363 (2014) 11–26 Contents lists available at ScienceDirect Journal of Chromatography A j o ur na l ho me page: www.elsevier.com/locate/chroma Review Homochiral metal–organic frameworks and their application in chromatography enantioseparations Paola Peluso a,∗ , Victor Mamane b , Sergio Cossu c a Istituto di Chimica Biomolecolare ICB CNR—UOS di Sassari, Traversa La Crucca 3, Regione Baldinca, Li Punti, I-07100 Sassari, Italy b Institut de Chimie de Strasbourg, UMR 7177, Equipe LASYROC, 1 rue Blaise Pascal, BP 296 R8, 67008 Strasbourg Cedex, France c Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca’ Foscari di Venezia, Dorsoduro 2137, I-30123 Venezia, Italy a r t i c l e i n f o Article history: Received 15 April 2014 Received in revised form 10 June 2014 Accepted 19 June 2014 Available online 25 June 2014 Keywords: Chiral stationary phases GC Enantioseparation HPLC Metal-organic framework a b s t r a c t The last frontier in the chiral stationary phases (CSPs) field for chromatography enantioseparations is rep- resented by homochiral metal-organic frameworks (MOFs), a class of organic-inorganic hybrid materials built from metal-connecting nodes and organic-bridging ligands. The modular nature of these materials allows to design focused structures by combining properly metal, organic ligands and rigid polytopic spac- ers. Intriguingly, chiral ligands introduce molecular chirality in the MOF-network as well as homochirality in the secondary structure of materials (such as homohelicity) producing homochiral nets in a manner mimicking biopolymers (proteins, polysaccharides) which are characterized by a definite helical sense associated with the chirality of their building blocks (amino acids or sugars). Nowadays, robust and flex- ible materials characterized by high porosity and surface area became available by using preparative procedures typical of the so-called reticular synthesis. This review focuses on recent developments in the synthesis and applications of homochiral MOFs as supports for chromatography enantioseparations. Indeed, despite this field is in its infancy, interesting results have been produced and a critical overview of the 12 reported applications for gas chromatography (GC) and high-performance liquid chromatography (HPLC) can orient the reader approaching the field. Mechanistic aspects are shortly discussed and a view regarding future trends in this field is provided. © 2014 Elsevier B.V. All rights reserved. Contents 1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 2. Metal-organic frameworks (MOFs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 3. Homochiral MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 4. Enantioseparation on homochiral MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 4.1. Chiral stationary phases for gas chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 4.2. Chiral stationary phases for liquid chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 5. Conclusions and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 Abbreviations: H2asp, aspartic acid; H2bda, 2,2 ′ -dihydroxy-1,1 ′ -binaphthalene-6,6 ′ -dicarboxylic acid; H2bdc, 1,4-benzenedicarboxylic acid; H2bpdc, 4,4 ′ - biphenyldicarboxylic acid; bpe, trans-1,2-bis(4-pyridyl)ethylene; bpy, bipyridine; H3btb, benzene-1,3,5-tribenzoic acid; H2cam, camphoric acid; CEC, capillary electrochro- matography; CSP, chiral stationary phase; dabco, 1,4-diazabicyclo[2.2.2]octane; DCM, dichloromethane; def, N,N-diethylformamide; dma, N,N-dimethylacetamide; dmeda, dimethylethylenediamine; dmf, N,N-dimethylformamide; eda, ethylenediamine; FR, flow rate; GC, gas chromatography; hex, n-hexane; HPLC, high-performance liquid chro- matography; i.d., inner diameter; IPA, isopropyl alcohol; H-isn, isonicotinic acid; l-H2lac, l-lactic acid; MKD, minimum kinetic diameter; MOF, metal-organic framework; MP, mobile phase; NPLC, normal phase liquid chromatography; PCP, porous coordination polymer; POST, Pohang University of Science and Technology; PSM, post-synthetic modification; H2sala, N-(2-hydroxybenzyl)-l-alanine; SBU, secondary building unit; TLC, thin layer chromatography; tmdpy, trimethylenedipyridine; UMCM, University of Michigan Crystalline Material. ∗ Corresponding author. Tel.: +39 079 2841218; fax: +39 079 2841299. E-mail address: p.peluso@icb.cnr.it (P. Peluso). http://dx.doi.org/10.1016/j.chroma.2014.06.064 0021-9673/© 2014 Elsevier B.V. All rights reserved.