Anda di halaman 1dari 6

Full Paper

DOI: 10.1002/ijch.201300001

M. Barboiu, et al.

Highly Selective Li + Ion Transport by Porous Molybdenum-Oxide Keplerate-Type Nanocapsules Integrated in a Supported Liquid Membrane
Arnaud Gilles,[a] Simona Mihai,[a] Gihane Nasr,[a] Eugene Mahon,[a] Somenath Garai,[b] Achim Mller,[b] and Mihail Barboiu*[a]

Abstract : Porous Keplerate-type molybdenum-oxide nanocapsules encapsulated into cationic surfactants act as transporting systems for alkali cations through supported liquid membranes. The transport is based on the ability of the nanocapsules containing water molecules inside their cavities to attract and release the cations. This results in

specific nanoscaled translocation pathways, based on corresponding dynamic diffusional domains within the liquid bulk membrane phase, due to the self-assembly of the capsules. Li + cations are preferentially extracted and transported, thus allowing separation from Na + and K + cations, which are not transported to the receiving phase.

Keywords: membranes nanodevices self-assembly structure-property relationship supramolecular materials

The transport of ions across cell membranes is a fundamental biological process which depends on the unique properties of hydrophilic domains of biomolecules, specifically on the functional complexity of the related membrane proteins.[1] Investigations of transport processes through model membrane systems, like those of the liquid type, can lead to information about basic properties of (novel) ion-receptor and related carrier systems.[2] The functionality of cation transporting membrane proteins is related to the dynamic constitutional behaviors of their binding sites collectively contributing to the selective cation transport.[1] To mimic related highly functional devices, one has to develop artificial constitutional dynamic membrane systems that form effective patterns by related collective self-assembly of carrier entities, leading to efficient cation translocation through the membrane barriers. Carrier molecules or ion-channel-type systems are usually used to facilitate the transport through lipophilic membrane barriers.[2] Recent publications showed, for instance, that nanosized systems, like Cu24(5-dodecyloxybenzene-1,3-dicarboxylate)24, MOP-18,[3a] and pyrogallolarene capsules[3b] can exhibit ion-channel activity in lipid bilayers. In this context, we consider unique spherical porous anionic molybdenum-oxide based capsules.[46] Importantly, their overall charges, as well as interiors, can be specifically, i.e. uniquely, tuned, allowing a controlled (stepwise) encapsulation of cations, while, for instance, their crown-ether-type pores can regulate the ion-flux by closing and opening them with plugs, in a supramolecular 102 fashion.[7,8] Moreover, earlier molecular dynamics simulations shed light on the process of embedding the nanocapsuleswith their unprecedented molecular-scale filter propertiesinto lipid bilayer membranes.[9]

Results and Discussion

Here we consider the porous, molybdenum-oxide based anionic capsules 1a, 2a, and 3a of the compounds: (NH4)42[{(MoVI)MoVI5O21(H2O)6}12{MoV2O4(CH3COO)}30] ca. [10CH3COONH4 + 300H2O]  (NH4)421a crystal ingredients  1[4b] [MoVI72FeIII30O252(CH3COO)12{Mo2O7(H2O)}2{H2Mo2O8(H2O)}(H2O)91] ca. 150H2O  2acrystal ingredients  2[4c] (NH4)72-n[{(H2O)81-n + (NH4)n}{(MoVI)MoVI5O21(H2O)6}12{MoV2O4(SO4)}30] ca. 200H2O  (NH4)72-n3a crystal ingredients  3[7,8] The related lipophilic hybrid-type compounds, prepared with dimethyl-dioctadecylammonium-bromide
[a] A. Gilles, S. Mihai, G. Nasr, E. Mahon, M. Barboiu Adaptive Supramolecular Nanosystems Group Institut Europen des Membranes -ENSCM/UM2/CNRS 5635, IEM/UM II, CC 047, Place Eugne Bataillon, 34095, Montpellier, Cedex 5 (France) fax: + 33-467-14-91-19 e-mail: [b] S. Garai, A. Mller Universitt Bielefeld, Fakultt fr Chemie Postfach 10 01 31, 33501 Bielefeld (Germany)

 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Isr. J. Chem. 2013, 53, 102 107

Selective Ion Transport by Nanocapsules

DODABr,[10] were used to get information about the competitive Li + , Na + , and K + ion transport through liquid membranes, which contain {DODA40(NH4)21a},[10a,b] {DODAx2a} (x ~ 7),[10c] and {DODA50(NH4)223a} (the latter prepared for the first time here) as cationic transporters. The mentioned hybrids were synthesized according to the previously published procedures by mixing aqueous solutions of 1, 2, and 3 with solutions of DODABr in chloroform (see Experimental Section). These hybrids form at the water/CHCl3 interface and are extracted in the organic phase, while their isolation takes place after evaporation of the solvent. FTIR spectra show the characteristic vibrational bands of 1a, 2a, and 3a in the region below 1000 cm1, as well as those of the DODA cations (e.g. nCH2as = 2850 cm1, nCH2sym = 2920 cm1).[10] The vibrational bands of 1, 2, and 3 remain practically unshifted, but are sharper, as expected after their encapsulation. Importantly, the discrete species, like {DODA40(NH4)21a}, in the membrane are probably in equilibrium with the assemblies (Figure 1). (The equilibrium strongly depends on the concentration of {DODA40(NH4)21a}.) It was pre-

and 4). For this purpose, the hybrids were solubilized in o-nitrophenyl-n-octylether (NPOE), and supported liquid membranes (SLMs) were prepared from these solutions  and hydrophobic Accurel membranes with high porosity. The stagnant diffusional layer of the SLM is defined as  the thickness of the solid Accurel membrane film (60 mm), which separates the aqueous feed-type solutions (0.1 M LiCl, NaCl, and KCl) from the receiving-type compartments (pure water). The concentrations of the Li + , Na + , and K + cations have been determined in the feed and receiving phase at different time intervals (see Experimental Section). The obtained profile concentration, as a function of time (Figure 2), sheds light on the processes at the feed/membrane and membrane/receiving phase interfaces, as well as on the different transport behaviors of the membrane systems employed.

Figure 1. A possible example for the self-association behavior of solutions of {DODA40(NH4)21a} (see also refs. [10a, b]). The present one in CHCl3 in the membrane influences the cation transport (the position of the NH4 + ions is not known); for details see text. The situation for {DODAx2a} hybrids (x ~ 7[10c]) should be completely different because of the small number of surfactant molecules.

viously shown that the large self-assembled architectures (Figure 1) are expected to be energetically favorable in solution, based on the optimization of hydrophobic interactions between the DODA-type alkyl chains, as well as electrostatic interactions between the anionic capsules and cationic DODA head groups. Furthermore, it was shown that cations like Li + ions can enter the nanocapsule cavities containing H2O molecules and show specific local interactions with the internal SO42 ligands (see e.g. ref. [4a]). Now it turns out that the capsules can facilitate cation transport and that the mentioned hybrid species can be used for selective membrane transport studies. The goal of the present work was to study the lipophilic hybrids {DODA40(NH4)21a}, {DODAx2a}, and {DODA50(NH4)223a}, embedded in liquid membranes, as ion transporter systems, in order to evaluate their capacity for specific alkali cation separations in solution (Figures 2, 3,
Isr. J. Chem. 2013, 53, 102 107

Figure 2. Profile concentration ( 5 % error limit) versus time of (a) Li + , Na + , and K + cations at the feed phase/membrane interface and of (b) Li + cations in the feed, membrane, and receiving phases, based on the {DODA40(NH4)21a} present in the membrane. The flux values J, representing concentration of ions transported per hour through feed/membrane or membrane/receiving interfaces, have been calculated from the slope of the initial nearly linear part of the profiles (time 010 h), using the solution-diffusion model.[11]

 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


Full Paper
In this context we refer to the following points: 1. The ideal cation transport scenarios (shown in Figure 3 a) according to the solution-diffusion mechanism (based on Ficks law), assume that the driving force is due to the cation concentration gradients. This should lead to an equal transport rate of all cations with an equilibrium state in which 50 % of the initial concentration of the cations is present in each of the feed and receiving phases. 2. In the presence of only a NPOE solution of DODABr, the alkali cations are not extracted from the feed phase. 100 % of the initial cation concentrations of Li + , Na + , and K + (0.1 M, each) has been measured in the feed phase at different time intervals (Figure 3 b). 3. The present SLM membrane containing the lipophilic hybrid {DODA40(NH4)21a}, shows high selectivity for Li + cations, which are exclusively transported, while the Na + and K + cations are only partially extracted into the membrane, but are not present at all in the receiving phase (Figure 3 c). The transport across the hydrophobic liquid membrane phase should occur via

M. Barboiu, et al.

ion-pairs, i.e. of Li + , Na + , or K + cations with the anionic nanocapsules, or of the Cl- anions with the DODA cations. The extraction/release performance of the ions of an alkali salt from the feed phase, through the membrane, to the receiving phase, in the case of the lipophilic hybrids {DODA40(NH4)21a}, can be evaluated by comparison of alkali cation equilibrium concentrations (measured after ~ 50 h) in the feed, membrane, and receiving phases, to their initial concentrations (0.1 M, each) (Figure 2 a,b). The determination of the profile concentration versus time in the receiving phase and the calculated diffusion coefficient Di of Li + (Table 1)[1114] show selective extraction/transport of Li + (40 % remaining in the feed phase, 20 % in the membrane, and 40 % transferred into the receiving phase). Na + and K + cations, on the other hand remain mostly in the feed phase (85 % and 92 %, respectively) and are only slightly extracted to the membrane phase (15 % and 8 %, respectively), as shown in Figures 2 a and 3 c.
Table 1. Diffusion coefficients of Li + transported through the SLM membranes (Na + and K + cations have not been detected in the receiving phase). Membrane Constituents {DODABr} {DODA40(NH4)21a} {DODAx2a}, (x ~ 7) {DODA50(NH4)223a} DLi + 1010 m2/s 0[a] 1.62 1.75 0[a]

[a] We noted no transport phenomena of ions through the membrane containing only the DODABr or {DODA50(NH4)223a} constituents.

Figure 3. Concentrations of Li + , Na + and K + cations at equilibrium state in the feed, membrane (for thickness see text) and receiving phases, relative to the total initial concentration c0 = 0.1 M (for each cation) with different membrane types: a) presuming ideal passive ion transport conditions; b) in the presence of only DODABr; and c) in the presence of {DODA40(NH4)21a}, acting as ion transporter.

The Mo9O9-type pores of 1a in the considered hybrid {DODA40(NH4)21a} (diameter of ca. 3 [15])) are quite similar in size to those of the 27-crown-9. Therefore, hydrated Li + ions with a complete shell of four coordinated water molecules (diameter also around 3 [16]) can pass. On the other hand, the larger hydrated Na + and K + require partial dehydration before entering, which is enthalpically unfavorable in the presence of internal acetate ligands which have no receptor/attractor function. The consequence: Hydrated Na + and K + cations are positioned outside the capsules. For comparison: The self-diffusion coefficients of hydrated Li + , Na + , and K + cations in water follow the series DNa + (H2O)n < DK + (H2O)n ! DLi + (H2O)n.[16,17] This means that the transport of the Li + cations through the capsules containing (disordered) H2O molecules could possiblyin a first order approximationbe influenced by the higher diffusion rate of hydrated Li + ions (see related remark in Figure 4). Importantly, for {DODA40(NH4)21a} there is a difference of one order of magnitude between the transport rates for Li + cation uptake at the feed/membrane inIsr. J. Chem. 2013, 53, 102 107


 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Selective Ion Transport by Nanocapsules

terface (JLi + ,feed = 4.7*103 mol/L/h) and their release at the membrane/receiving interface (JLi + ,receiving = 5.7 * 104 mol/L/h) (Figures 2 b and 3 c). This means that some of the Li + cations are retained in the liquid membrane, as the binding to the pore O atoms of the capsule 1a, with a charge of 42-, leads to an extreme lowering of the transport rate. The main contribution to the different transport rates and selectivities, in the case where the {DODA40(NH4)21a} hybrid is present, is related to the different affinity/uptake properties of the lipophilized nanoporous capsules toward the Li + , Na + , and K + cations. The consequence is that only Li can pass through the capsules (Figure 4).

{DODA50(NH4)223a}, with known cation coordinating properties,[7,8,15] was tested. The experiments showed, correspondingly, that Li + , Na + , and K + cations are no longer transported through the liquid membrane, as they are mostly fixed, due to the SO42 ligand-type receptor properties,[15] which is in contrast to the acetate-type capsule scenarios. As the high negative charge of the sulphate cluster allows dehydration, all cations can enter through the pores, but cannot leave the capsule. (We do not consider here that uptake of cations lowers the capsule charge which changes the interaction with the DODA cations!) It was observed that the Li + diffusion coefficients (DLi + (H2O) ~ 1010 m2/s; Table 1) are six orders of magnitude lower than the diffusion coefficients of hydrated Li + cations in water (DLi + = 7.9*105 m2/s),[16,17] and of the same order of magnitude as the diffusion coefficients determined by DOSY-NMR experiments for the naked nanocapsules 1a in DMSO solution (9.1*1011 m2/s).[5] Presuming that the dynamic diffusion of lipophilic self-associated superstructures of the nanocapsules (Figure 1) with a larger hydrodynamic volume is smaller than diffusion of hydrated Li + ions through the hydrated capsules, this behavior can be rationalized by considering the hybrid nanocapsules as slower dynamic spectators of the diffusion events of more mobile ionic partners like Li + cations, as previously observed with hybrid membrane systems.[14]

Figure 4. Top: Scanning electron microscope (SEM) images of the cross-section of the membrane films (a) before and (b) after filling the membrane phase with {DODA40(NH4)21a} hybrids, showing that all membrane macropores are filled with the lipophilic nanocapsules. Bottom: A detailed model of the processes in the SLM, in which the lipophilic nanocapsules under study contain internal water. Li + cations (yellow spheres) are selectively transported over Na + (blue spheres) and K + (red spheres) cations, by a combined diffusion/uptake-release driven transport mechanism.

Summary and Conclusion

The present results show highly selective transport of Li + over Na + and K + cations through supported liquid membranes, in which special porous nanocapsules embedded in surfactants occur in dynamic constitutional aggregates, used as specific nanoscaled translocation pathways for cations. The constitutional interactions among these nanocapsules lead to the generation of dynamic nanophases within the membrane phase, making it possible to improve the cation-type diffusion within such percolated conductive nanodomains. The controlled generation of diffusional-type nanoscaled channels within a membrane structure is important for the design of new membrane systems. It is worth mentioning that the ability of the porous nanocapsules to uptake/release cations is based on the diffusion of the ions within the cavities, which are filled with water molecules. Perspectives for the future include the development of these new methodologies towards dynamic constitutional systems. This may provide new insights into basic features for the design of new materials mimicking biological ion channels, with applications in nanoscaled separations, sensoring, and storage-delivery devices. Finally the results obtained extend the application of Constitutional Dynamic Chemistry[18] to materials science.[19]

The observation has been confirmed by the permeability of Li + cations through the hybrid {DODAx2a} (x ~ 7) [10c] (note the relatively low negative capsule charge!) as the Na + and K + cations cannot penetrate, because the {Mo3Fe3O6} pores exhibit an 18-crown-6-type crown-ether function, which causes the retention of these cations within the liquid membrane. In the Li + cation transport, the diffusion-driven permeability through the membrane is a little bit more effective in case of the nearly neutral capsule 2a compared to that of 1a (note: both have no receptor ligands). While the mentioned level of selectivity is influenced by different cation interactions with the capsule pores, it is evident, as mentioned before, that a second cause exists, namely possible internal ligand coordination, in case of a hybrid compound with sulphate ligands/receptors. For this reason, the sulphate-type hybrid
Isr. J. Chem. 2013, 53, 102 107

 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


Full Paper
Experimental Section
Materials and methods: All reagents were obtained from Aldrich and used without further purification. All organic solutions were routinely dried by using sodium sulphate (Na2SO4). The molybdenum-oxide based capsules 1a,[4b] 2a,[4c] and 3a[6] and the lipophilic porous hybrids {DODA40(NH4)21a}[10a,b] and {DODAx2a}[10c] were synthesized according to the previously published procedures, while {DODA50(NH4)223a} was synthesized for the first time (correct elemental analysis and IR spectrum). Membrane transport procedure: Membrane transport experiments were performed with magnetic stirring, in a conventional bi-compartmental Teflon device,[11] at room temperature, in which the membrane (S = 5.32 cm2) separated an aqueous feed phase of 50 mL of 101 M LiCl + 101 M NaCl + 101 M KCl solution from the receiving phase of 50 mL of deionized water. The supported membrane was prepared by introducing either 103 M solutions of the hybrids {DODA40(NH4)21a}, {DODAx2a}, and {DODA50(NH4)223a} or a 102 M solution of DODA in 2-nitrophenyloctyl-ether (NPOE) into the thin hydro phobic Accurel films of high porosity. Aliquots (0.01 ml) of both aqueous solutions were withdrawn at appropriate intervals. The Li + , Na + , and K + concentrations in aqueous feed and receiving phases were determined by atomic absorption spectrometry ( 5 % error limit). Their concentration in the membrane phase was determined by the difference between the initial concentration and the sum of the total concentration in the aqueous phases. The flux values were calculated from the concentration versus time profiles in the feed or receiving phases.

M. Barboiu, et al. ault, M. Barboiu, E. Petit, M. Michau, A. van der Lee, New J. Chem. 2005, 29, 1535 1539; g) M. Barboiu, P. Aimar, J. -M. Lehn, J. Membr. Sci. 2008, 321, 1 2; h) M. Michau, M. Barboiu, R. Caraballo, C. Arnal-Hrault, P. Perriat, A. van der Lee, A. Pasc , Chem. Eur. J. 2008, 14, 1776 1783; i) C. Arnal-Hrault, A. Pasc, M. Michau, D. Cot, E. Petit, M. Barboiu, Angew. Chem. 2007, 119, 8561 8565; Angew. Chem. Int. Ed. 2007, 46, 8409 8413; j) C. Arnal-Hrault, A. Banu, M. Barboiu, M. Michau, A. van der Lee, Angew. Chem. 2007, 119, 4346 4350; Angew. Chem. Int. Ed. 2007, 46, 4268 4272. a) M. Jung, H. Kim, K. Baek, K. Kim, Angew. Chem. 2008, 120, 5839 5841; Angew. Chem. Int. Ed. 2008, 47, 5755 5757; b) O. V. Kulikov, R. Li, G. W. Gokel, Angew. Chem. 2009, 121, 381 383; Angew. Chem. Int. Ed. 2009, 48, 375 377. a) A. Mller, D. Rehder, E. T. K. Haupt, A. Merca, H. Bgge, M. Schmidtmann, G. Heinze-Brckner, Angew. Chem. 2004, 116, 4566 4570; Angew. Chem. Int. Ed. 2004, 43, 4466 4470; corrigendum: A. Mller, D. Rehder, E. T. K. Haupt, A. Merca, H. Bgge, M. Schmidtmann, G. Heinze-Brckner, Angew. Chem. 2004, 116, 5225; Angew. Chem. Int. Ed. 2004, 43, 5115; b) A. Mller, E. Krickemeyer, H. Bgge, M. Schmidtmann, F. Peters, Angew. Chem. 1998, 110, 3567 3571; Angew. Chem. Int. Ed. 1998, 37, 3360 3363; c) A. Mller, S. Sarkar, S. Q. N. Shah, H. Bgge, M. Schmidtmann, S. Sarkar, P. Kgerler, B. Hauptfleisch, A. X. Trautwein, V. Schnemann, Angew. Chem. 1999, 111, 3435 3439; Angew. Chem. Int. Ed. 1999, 38, 3238 3241 (practically neutral capsule); d) A. Mller, P. Gouzerh, Chem. Soc. Rev. 2012, 41, 7431 7463. E. T. K. Haupt, C. Wontorra, D. Rehder, A. Mller, Chem. Commun. 2005, 3912 3914. a) D. Rehder, E. T. K. Haupt, H. Bgge, A. Mller, Chem. Asian J. 2006, 1, 76 81; b) T. Mitra, P. Mir, A. R. Tomsa, A. Merca, H. Bgge, J. B. valos, J. M. Poblet, C. Bo, A. Mller, Chem. Eur. J. 2009, 15, 1844 1852; c) A. M. Todea, A. Merca, H. Bgge, T. Glaser, J. M. Pigga, M. L. K. Langston, T. Liu, R. Prozorov, M. Luban, C. Schrder, W. H. Casey, A. Mller, Angew. Chem. 2010, 49, 524 529; Angew. Chem. Int. Ed. 2010, 49, 514 519. A. Mller, Y Zhou, H. Bgge, M. Schmidtmann, T. Mitra, E. T. K. Haupt, A. Berkle, Angew. Chem. 2006, 118, 474 479; Angew. Chem. Int. Ed. 2006, 45, 460 465. E. T. K. Haupt, C. Wontorra, D. Rehder, A. Merca, A. Mller, Chem. Eur. J. 2008, 14, 8808 8811. R. Carr, I. A. Weinstock, A. Sivaprasadarao, A. Mller, A. Aksimentiev, Nano Lett. 2008, 8, 3916 3921. a) D. G. Kurth, P. Lehmann, D. Volkmer, A. Mller, D. Schwahn, J. Chem. Soc., Dalton Trans. 2000, 3989 3998; b) H. Li, Y. Yang, Y. Wang, C. Wang, W. Li, L. Wu, Soft Matter, 2011, 7, 2668 2673; c) T. Liu, J. Cluster Sci. 2003, 14, 215 226. a) M. Barboiu, C. Guizard, C. Luca, B. Albu, N. Hovnanian, J. Palmeri, J. Membr. Sci. 1999, 161, 193 206; b) M. Barboiu, C. Guizard, N. Hovnanian, J. Palmeri, C. Reibel, L. Cot, C. Luca, J. Membr. Sci. 2000, 172, 91 103; c) M. Barboiu, C. Guizard, C. Luca, N. Hovnanian, J. Palmeri, L. Cot, J. Membr. Sci. 2000, 174, 277 286. a) A. Hriciga, J.-M. Lehn, Proc. Natl. Acad. Sci. U.S.A. 1983, 80, 6426 6428; b) J. D. Lamb, R. M. Izatt, D. G. Garrick, J. S. Bradshaw, J. J. Christensen, J. Membr. Sci. 1981, 9, 83 107.



[5] [6]

This work was conducted as part of a DYNANO, PITNGA-2011-289033 ( and ANR-10-BLAN717-2. We thank Adinela Cazacu and Dr. Ana Maria Todea for the preliminary experiments. A. M. thanks the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie for long term support.

[8] [9] [10]

[1] a) F. Hucho, C. Weise, Angew. Chem. 2001, 113, 3194 3211; Angew. Chem. Int. Ed. 2001, 40, 3100 3116; b) S. Vaitheeswaran, H. Yin, J. C. Raisaiah, G. Hummer, Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 17002 17005. [2] a) J.-M. Lehn, Supramolecular Chemistry Concepts and Perspectives, Chapter 6, Wiley-VCH, Weinheim, 1995 ; b) M. Barboiu, G. Vaughan, A. van der Lee, Org. Lett. 2003, 5, 3073 3076; c) M. Barboiu, J. Inclusion Phenom. Macrocyclic Chem. 2004, 49, 133 137; d) A. Cazacu, C. Tong, A. van der Lee, T. M. Fyles, M. Barboiu, J. Am. Chem. Soc. 2006, 128, 9541 9548; e) M. Barboiu, N. D. Hovnanian, C. Luca, L. Cot, Tetrahedron 1999, 55, 9221 9232; f) C. Arnal-Her[11]



 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Isr. J. Chem. 2013, 53, 102 107

Selective Ion Transport by Nanocapsules [13] a) J.-M. Lehn, P. Vierling, R. C. Hayward, Chem. Commun. 1979, 296 297; b) C. Arnal-Hrault, M. Michau, M. Barboiu, J. Membr. Sci. 2008, 321, 94 99. [14] a) M. Barboiu, S. Cerneaux, A. van der Lee, G. Vaughan, J. Am. Chem. Soc. 2004, 126, 3545 3550; b) M. Michau, M. Barboiu, J. Mater. Chem. 2009, 19, 6124 6131; c) M. Michau, R. Caraballo, C. Arnal-Hrault, M. Barboiu, J. Membr. Sci. 2008, 321, 22 30; d) A. Cazacu, Y. M. Legrand, A. Pasc, G. Nasr, A. van der Lee, E. Mahon, M. Barboiu, Proc. Natl. Acad. Sci. U.S.A. 2009, 106(20), 8117 8122. [15] A. Mller, S. K. Das, S. Talismanov, S. Roy, E. Beckmann, H. Bgge, M. Schmidtmann, A. Merca, A. Berkle, L. Allouche, Y. Zhou, L. Zhang, Angew. Chem. 2003, 115, 5193 5198; Angew. Chem. Int. Ed. 2003, 42, 5039 5044. [16] M. Y. Kiriukhin, K. D. Collins, Biophys. Chem. 2002, 99, 155 168. [17] Diffusion coefficients in water: DNa + = 1.334*105 m2/s, DK + = 1.957*105 m2/s, DLi + = 7.9*105 m2/s in Handbook of Chemistry and Physics, 76th edition (Ed.: David R. Lide), CRC Press, 19951996, pp. 5 92. [18] a) Dynamic Combinatorial Chemistry: In Drug Discovery, Bioorganic Chemistry and Materials Science (Ed.: B. L. Miller), John Wiley & Sons, Inc., Hoboken, 2010 ; b) Dynamic Combinatorial Chemistry (Eds.: J. N. H. Reek and S. Otto), Wiley-VCH, Weinheim, 2010 ; c) Constitutional Dynamic Chemistry, Topics in Current Chemistry (Ed.: M. Barboiu), vol. 322, Springer, Berlin, 2012. [19] a) M. Barboiu, Chem. Commun. 2010, 46, 7466 7476; b) A. Mller, A. Merca, A. J. M. Al-Karawi, S. Garai, H. Bgge, G. Hou, L Wu, E. T. K. Haupt, D. Rehder, F. Haso, T. Liu, Chem. Eur. J. 2012, 18, 16310 16318; c) C. Arnal-Hrault, M. Barboiu, A. Pasc, M. Michau, P. Perriat, A. van der Lee, Chem. Eur. J. 2007, 13, 6792 6800; d) Y. M. Legrand, A. van der Lee, M. Barboiu, Inorg. Chem. 2007, 46, 9540 9547; e) F. Dimitru, Y. M. Legrand, A. van der Lee, M. Barboiu, Chem. Commun. 2009, 2667 2669. Received: January 6, 2013 Accepted: January 15, 2013 Published online: February 18, 2013

Isr. J. Chem. 2013, 53, 102 107

 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim