Calix arenes membrane transport

Casnati, A., Pochini, A., Ungaro, R., Ugozzoli, F., Amaud, F., Fanni, S., Schwing, M.J., Egberink, R.J.M., DeJong, F., Rienhoudt, D.N. Synthesis, complexation and membrane transport studies of 1,3-alternate calix[4]arene crown-6 conformers A new class of cesium selective ionophores. J. Am. Chem. Soc. (1995), 117, 2767-2777. 

Izatt, S.R., Hawkins, R.T., Christensen, J.J., and Izatt, R.M. 1985. Cation transport from multiple alkali cation mixtures using a liquid membrane system containing a series of calix-arene carriers. J. Am. Chem. Soc. 107 63-66. 

Kimizuka N, Wakiyama T, Yanagi A, Shinkai S, Kunitake T. Calix[4]arene-mediated transport of alkali ions across synthetic black lipid membranes (BLM). Bull Chem Soc 1996 69(12) 3681. ... 

ABSTRACT. Synthetic receptor molecules derived from calix[4]arenes have been used in different technological applications. The use of various functionalized calix[4]arenes in selective membrane transport through supported liquid membranes, selective cation detection with chemically modified field effect transistors, as preorganized donor-7c-acceptor systems in non linear optics and in the development of monolayers with receptor headgroups is discussed. 

Figure 1. Calix[4]arene carriers in membrane transport. of the carrier with respect to the different cations. ...

In 1982, /Mert-butyl-cal i x n larenes were studied by Izatt et al. for their capacity to transport cesium from an alkaline medium ([MOH] = 1M) through bulk liquid membranes made of a mixture of diluents able to dissolve these compounds methylene chloride, carbon tetrachloride, and dichloromethane. Experiments were carried out using p-tert-calix[8]arene to measure the rate of cesium transport under conditions of varying source pH. The values of the transport rate, small below a pH of 12, rise rapidly beyond this value, hence confirming that a proton is removed from the ligand in the complexation process. Under such conditions, tetramer, hexamer, and octamer (n = 4, 6, and 8, respectively) display a high selectivity for cesium over the other... 

Here, P s and /<. s are the cesium permeability in the ith transport experiment and in the first run, respectively, and R = (Vfeed+ Vslnp)/VSLM, Vfeed, Vstrip, and VSLM are the volumes of feed and stripping aqueous phases and the volume of organic phase in the membrane, respectively. Kp is the apparent partition constant of the carrier between the SLM and both aqueous and stripping solutions. Values of this apparent partition constant can be deduced via linear regression of log PCs versus (i-1). They are equal to 128,100, 29,100, 106,700, and 295,000, respectively, for decyl-benzo-21-crown-7, calix[4]arene-bis(crown-6), calix[4]arene-bis(benzo-crown-6), and calix[4]arene-bis(naphtho-crown-6). Calix[4]arene-bis(crown-6) rapidly leaked off the membrane... 

How do calixarenes enter cells To answer this question Matthews, Mueller and co-workers prepared a soluble calix[4]arene with quaternary ammonium groups on the upper rim and a fluorescent label on the lower rim [35], Following the progress of the compound by fluorescence confocal microscopy it was apparent that molecules were not transported across the membrane by normal endocytosis mechanisms, nor did they penetrate the cell nucleus but remained in the cytoplasm. This would seem to point to a membrane bound channel as the point of entry and paves the way for an array of therapeutic interventions. 

Alpoguz HK, Memon S, Ersoz M, YUmaz M. Kinetics of mcrcury(II) transport through a bulk liquid membrane containing calix[4]arene derivatives as carriers. Sep Sci Technol 2003 38 1649-1664. 

Saf AO, Alpaydin S, Sirit A. Transport kinetics of chromium(VI) ions through a bulk liquid membrane containing p-tert-butyl calix[4] arene 3-morpholino propyl diamide derivative. J Membr Sci 2006 283 448-455. 

Alpoguz, H. K., Memon, S., Ersoz, M., Yylmaz, M. (2004). Transport kinetics ofHg24-through bulk liquid membrane using calix[4]arene ketone derivative as carrier. Separation Science and Technology 39 799-810. 

Levitskaia, T. G., Lamb, J. D., Fox, K. 1.., Moyer, B. A. (2002). Selective carrierme-diated cesium transport through polymer inclusion membranes by calix[4] arene-crown-6 carriers from complex aqueous mixtures. Radiochimica Acta 90 43-52. 

Reinhoudt and co-workers (51) targeted O2 and prepared water-soluble models of heme-protein active sites. These were self-assembling, heterodimeric capsules of cationic Co(II) porphyrin (27) and tetrasulfonato calix[4]arene (28) (Fig. 12). A millipore VMWP membrane, loaded with an aqueous solution of 27 (2 mA/), 28 (6mM), and 1-methyl imidazole (20 mM), showed a facilitated transport of O2. The facilitation factor of 1.15 and the O2/N2 selectivity of... 

Amino-, carboxy-, and sulfonato-calixarenes and the 1,8-naphthol-derived 12 form moderately strong complexes with polycyclic aromatic compounds in aqueous solution (see ref. 1, pp. 180-185), with Xassoc values approaching 10 M" The aminocalixarenes have been shown to be capable of being transported through a liquid membrane. The water soluble j -cyclodextrin-calix[4]arene 281 (for attachment-of jS-cyclodextrin at the lower rim, see ref. 728) forms a complex with 2-p-toluidino-6-naphthalenesulfonate with assoc = 1-53 X 10 M" . The cysteine-substituted calixarenes 282 (n = 4 and... 

Separations of molecules by membranes play a crucial role in biological systems, and they are proving to have important industrial applications as well. Therefore, considerable attention, particularly by Reinhoudt and coworkers, is being devoted to the use of calixarenes as the carrier molecules in liquid membranes. An early demonstration showed, for example, that selective transport of can be achieved through a supported liquid membrane (SLM) containing the calix[4]arene-crown-5 (130a R = f-Bu n = 3). A more recent... 

Jin T, Kinjo K, Koyama T, Kobayashi Y, Hirata H. 1996. Selective Na transport through phospholipid bilayer membrane by a synthetic calix[4]arene carrier. Langmuir 12 2684. 

Jin T, Kinjo M, Kobayashi Y, Hirata H. 1998. Ion transport activity of calix[n]arene (n 4, 5, 6, 7, 8) esters toward alkali metal cations in a phospholipid bilayer membrane. J Chem Soc Faraday Trans 94 3135. 

Chang, S.K. Hwang, H.S. Son, H. Youk, J. Kang, Y.S. Selective transport of amino acid esters through a chloroform liquid membrane by a calix[6]arene-based ester carrier. J. Chcm. Soc., Chem. Commun. 1991, 217. 

Kandwal, R, Ansari, S.A., and Mohapatra, P.K. 2011. Transport of cesium using hollow fiber supported liquid membrane containing calix[4]arene-bis(2,3-naphtho)crown-6 as the carrier extractant Part II. Recovery from simulated high level waste and mass transfer modeling. J. Membr. Sci. 384 37 3. 

Competitive Cs+ ion transport in PIMs using calix[4]arene-mono- and bis-crown-6 carriers was also studied. The calix-bis-crown 25 (Figure 22) exhibited slightly more efficient CS+ transport than with the monocrown 24 (Figure 22) since the diffusion coefficient of the Cs-24+ complex is only one-fourth that of Cs-25". The selectivity values (o cs/m) for Cs+ over K+, Na" ", U02 " , Pb " ", and Al + with carrier 24 were greater than that with carrier 25, a result that was attributed to the higher association constant of Cs+ with carrier 24 in the membrane solvent. 

Calix[4]arenes in selective ion transport through supported liquid membranes... 

In an attempt to mimic the highly sophisticated ion transport properties found in biological membranes for the development of an ion channel sensor, a comprehensive study on artificial systems was carried out [10]. It was shown that the permeability of orientated monolayers of various calixarene esters is strongly influenced by the complexation with metal ions [11]. It was reported that the membrane permeability of calix[6]arene esters for a neutral redox-active... 

---