Alkali metal cation complexation by 1,3-alternate,mono-ionisable calix[4]arene-benzocrown-6 compounds

Alkali metal cation extraction behaviour for two series of 1,3-alternate, mono-ionisable calix[4]arene-benzocrown-6 compounds is examined. In Series 1, the proton-ionisable group (PIG) is a substituent on the benzo group of the polyether ring that directs it away from the crown ether cavity. In Series 2, the PIG is attached to one para position in the calixarene framework, thereby positioning it over the crown ether ring. Competitive solvent extraction of alkali metal cations from aqueous solutions into chloroform shows high Cs⁺ efficiency and selectivity. Single-species extraction pH profiles of Cs⁺ for Series 1 and 2 ligands with the same PIG are very similar. Thus, association of Cs⁺ with the calixcrown ring is more important than the position of the PIG relative to the crown ether cavity. Solid-state structures of two unionised ligands from Series 2 are presented. Also described is a crystal containing two different ionised ligand–Cs⁺ complexes.     

Coumarin-strapped calix[4]pyrrole: a fluorogenic anion receptor modulated by cation and anion binding

A new strapped calix[4]pyrrole containing a fluorophore as part of the strap has been synthesized and characterized. Association constants with various anions have been determined using both fluorescence titration and isothermal titrations calorimetry (ITC). The two sets of association constants were found to be in good agreement with one another. The fluorescence emission properties of this new receptor could be controlled by addition of Na+ (or H2O) and anions. However, the fluorescence quenching by anions is only observed in the presence of Na+ (or H2O). All the experimental evidence is consistent with the notion that independent PET processes are modulated by separate cation and anion recognition events. As such, this system operates as an elementary logic gate wherein anion and cation concentrations serve as the input and fluorescence intensity changes provide the output.     

Selective binding of aromatic amines by self-assembled monolayers of a calix[6]crown-4 derivative

A p-tert-butylcalix[6]crown-4 derivative immobilized on gold surfaces via self-assembly, endowed with a rigid cavity, can serve as a remarkably efficient sensor for aniline compared to alkylamines. The stability of the inclusion complex is attributed to the size fit and to the multipoint recognition motifs between the host monolayer and the guest aniline. [structure: see text]     

Exploring the dynamics of calix[4]pyrrole: effect of solvent and fluorine substitution

Molecular dynamics simulations show that calix[4]pyrrole (CP) and octafluorocalix[4]pyrrole (8F-CP) are extremely flexible molecules. CP mainly adopts the 1,3-alternate conformation in all the solvents, although the percentage of alternative conformations increases in polar solvents, especially those with good hydrogen-bonding acceptor properties. However, in the case of 8F-CP, the cone conformation is the most populated in some solvents. Transitions between conformers are common and fast, and both CP and 8F-CP can adopt the cone conformation needed for optimum interaction with anions more easily than would be predicted on the basis of previous gas-phase calculations. Furthermore, the present studies show that when a fluoride anion is specifically placed initially in close proximity to CP and 8F-CP in their respective 1,3-alternate conformations, an extremely fast change to the cone conformation is observed in both cases. The results suggest that preorganization does not represent a major impediment to anion-binding for either CP or 8F-CP, and that ion-induced conformational changes can follow different mechanisms depending on the solvent and the chemical substituents present on the calix[4]pyrrole beta-pyrrolic positions.     

Air-liquid interfaces of imidazolium-based [TF2N-] ionic liquids: insight from molecular dynamics simulations

We present molecular dynamics simulations of the air-liquid interface for three room temperature ionic liquids with a common anion: bis(trifluoromethylsulfonyl) imide ([Tf(2)N]), and imidazolium-based cations that differ in the alkyl tail length: 1-butyl-3-methylimidazolium ([C(4)mim]), 1-hexyl-3-methylimidazolium ([C(6)mim]), and 1-octyl-3-methylimidazolium ([C(8)mim]). The CHARMM type force field is used with the partial charges based on quantum calculations for isolated ion pairs. The total charge on cations and anions is around 0.9e and -0.9e, respectively, which somewhat mimics the anion to cation charge transfer and many-body effects. The surface tension at 300 K is computed using the mechanical route and its value slightly overpredicts experimental values. The air-liquid interface is analyzed using the intrinsic method of Identification of the Truly Interfacial Molecules. Structural and dynamic properties of the interfacial, sub-interfacial and central layers are determined. To describe the structure of the interface, we compute the surface roughness, number density and charge density profiles, and orientation ordering of the ions. We further determine the survival probability, normal and lateral self-diffusion coefficients, and re-orientation correlation functions to characterize the dynamics of the cations and anions in the layers. We found a significant enhancement of the cation density and preferential orientation ordering of both the cations and anions at the interface. Overall, the surface of the interfacial layer is smoother than the surface of the sub-interfacial layer and the roughness of both the interfacial and sub-interfacial layers increases with the increase of the length of the cation alkyl tail. Finally, the ions stay considerably longer in the interfacial layer than in the sub-interfacial layer and dynamics of exchange of the ions between the consecutive layers is related to the distinct diffusion and re-orientation dynamics behavior of the ions within the layers.     

Uranyl and strontium salt solvation in room-temperature ionic liquids. A molecular dynamics investigation

Using molecular dynamics simulations, we compare the solvation of uranyl and strontium nitrates and uranyl chlorides in two room-temperature ionic liquids (ILs): [BMI][PF(6)] based on 1-butyl-3-methylimidazolium(+),PF(6)(-) and [EMI][TCA] based on 1-ethyl-3-methylimidazolium(+),AlCl(4)(-). Both dissociated M(2+),2NO(3)(-) and associated M(NO(3))(2) states of the salts are considered for the two cations, as well as the UO(2)Cl(2) and UO(2)Cl(4)(2)(-) uranyl complexes. In a [BMI][PF(6)] solution, the "naked" UO(2)(2+) and Sr(2+) ions are surrounded by 5.8 and 10.1 F atoms, respectively. The first-shell PF(6)(-) anions rotate markedly during the dynamics and are coordinated, on the average, monodentate to UO(2)(2+) and bidentate to Sr(2+). In an [EMI][TCA] solution, UO(2)(2+) and Sr(2+) coordinate 5.0 and 7.4 Cl atoms of AlCl(4)(-), respectively, which display more restricted motions. Four Cl atoms sit on a least motion pathway of transfer to uranyl, to form the UO(2)Cl(4)(2)(-) complex. The free NO(3)(-) anions and the UO(2)Cl(4)(2)(-) complex are surrounded by imidazolium(+) cations ( approximately 4 and 6-9, respectively). The first shell of the M(NO(3))(2) and UO(2)Cl(2) neutral complexes is mostly completed by the anionic components of the IL, with different contributions depending on the solvent, the M(2+) cation, and its counterions. Insights into energy components of solvation are given for the different systems.     

Bifunctional fluorescent calix[4]arene chemosensor for both a cation and an anion

[reaction: see text] A new fluorogenic cone calix[4]triazacrown-5 (1) bearing two pyrene amide groups and its structural analogue 2 have been prepared. Excited at 343 nm, 1 and 2 reveal excimer emissions at 448 and 472 nm, respectively. When heavy metal ions such as Pb(2+) and Co(2+) are bound to 1, the fluorescence intensities of both monomer and excimer are quenched whereas H bonding-assisted F(-) binding to 1 gives rise to a quenched monomer emission with little excimer emission change.     

Microwave-assisted synthesis of 1,3-dialkyl ethers of calix[4]arenes: application to the synthesis of cesium selective calix[4]crown-6 ionophores

Partial etherification of phenolic-OH groups of calix[4]arenes with various alkyl halides/tosylates and K₂CO₃ under microwave irradiation afforded 1,3-dialkoxycalix[4]arenes in their cone conformation only as predominant/sole product in good yields (71–85%). The protocol was found to be much superior to conventional heating both in terms of yield and reaction time. Some of the 1,3-dialkoxycalix[4]arenes were elaborated further to the syntheses of cesium selective calix[4]crown-6 ionophores.     

The effect of a solvent modifier in the cesium extraction by a calix[4]arene: a molecular dynamics study of the oil phase and the oil-water interface

We report a molecular dynamics (MD) study of the effect of a fluorinated lipophilic alcohol (referred to as "cs3" by Delmau et al, Solvent Extr. Ion Exch., 2005, 23, 23) used as a phase modifier in the solvent extraction of Cs(+) NO(3)(-) by a calix[4]arene. It is shown that adding cs3 to a chloroform phase improves the solvation of all partners of the extraction system, i.e. the free calixarene ligand L, its LCs(+) complex and its counterion. This effect is most pronounced for the NO(3)(-) anion that is H-bonded to the -OH and terminal -CF(2)H protons of cs3. On the average, the dissociated nitrate interacts with 2 to 4 cs3 molecules, whereas the associated nitrate (LCs(+)NO(3)(-) complex) interacts with one cs3 dimer. The remaining modifier molecules are mainly dissolved in the solution as dimers or trimers and, to a lesser extent, as monomers and tetramers. Insights into the question of ion pairing in the organic phase are obtained via free energy perturbation (FEP) calculations, showing that the LCs(+)NO(3)(-) paired complex is more stable than its analogue with the dissociated anion. Furthermore, the nitrate dissociation energy is ca. twice as small in the cs3-modified solution than in a pure chloroform phase. We also simulated chloroform/cs3/water ternary systems, showing that the modifiers are surface active and stabilize the formation of water nanodroplets, while other modifier molecules drag some water to the organic phase. Calixarene complexes also adsorb at the aqueous interface in the presence of modifiers, confirming the importance of interfacial phenomena in the assisted cation extraction process. The microscopic insights obtained by the simulations are consistent with experimental results and allow us to better understand why the extraction is enhanced after addition of modifiers to the organic phase.     

The NMR structure of [Xd(C2)]4 investigated by molecular dynamics simulations

The i‐motif tetrameric structure is built up from two parallel duplexes intercalated in a head‐to‐tail orientation, and held together by hemiprotonated cytosine pairs. Two topologies exist for the i‐motif structure, one with outermost 3′ extremities and the other with outermost 5′ extremities, called the 3′E and 5′E topology, respectively. Since the comparison of sugar and phosphate group interactions between the two topologies is independent of the length of the intercalation motif, the relative stability of the 3′E and 5′E topologies therefore should not depend on this length. Nevertheless, it has been shown that the 3′E topology of the [d(C2)]4 is much more stable than the 5′E topology, and that the former is the only species observed in solution. In order to understand the reason for this atypical behavior, the NMR structure of the [Xd(C2)]4 was determined and analyzed by molecular dynamics simulations. In the NMR structure, the width of the narrow groove is slightly smaller than in previously determined i‐motif structures, which supports the importance of phosphodiester backbone interactions in the structure stability. The simulations show that the stacking of cytosines, essential for the i‐motif stability, is produced by a similar and non‐negative twisting of the phosphodiester backbones. The twisting is induced by an interaction between the backbones; the [Xd(C2)]4 in 5′E topology, exhibiting very limited interaction between the phosphodiester backbones, is thus unstable. Copyright © 2002 John Wiley & Sons, Ltd.     

A molecular dynamics computer simulation study of room-temperature ionic liquids. II. Equilibrium and nonequilibrium solvation dynamics

The molecular dynamics (MD) simulation study of solvation structure and free energetics in 1-ethyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium hexafluorophosphate using a probe solute in the preceding article [Y. Shim, M. Y. Choi and H. J. Kim, J. Chem. Phys. 122, 044510 (2005)] is extended to investigate dynamic properties of these liquids. Solvent fluctuation dynamics near equilibrium are studied via MD and associated time-dependent friction is analyzed via the generalized Langevin equation. Nonequilibrium solvent relaxation following an instantaneous change in the solute charge distribution and accompanying solvent structure reorganization are also investigated. Both equilibrium and nonequilibrium solvation dynamics are characterized by at least two vastly different time scales--a subpicosecond inertial regime followed by a slow diffusive regime. Solvent regions contributing to the subpicosecond nonequilibrium relaxation are found to vary significantly with initial solvation configurations, especially near the solute. If the solvent density near the solute is sufficiently high at the outset of the relaxation, subpicosecond dynamics are mainly governed by the motions of a few ions close to the solute. By contrast, in the case of a low local density, solvent ions located not only close to but also relatively far from the solute participate in the subpicosecond relaxation. Despite this difference, linear response holds reasonably well in both ionic liquids.     

脲基杯[4]二(9-冠-3)对钠-卤素离子对的识别作用

采用Oniom方法(B3LYP/LANL2DZ∶PM3)对脲基取代的二(9-冠-3)杯[4]芳烃衍生物(H)与离子对Na+X-(X=F-,Cl-,Br-)的包合作用进行了理论研究.在上述体系中存在2种包合方式:一是阴、阳离子在包合物中是分离的,阴离子与主体分子的上沿主要以N—H…X-氢键作用;二是阴、阳离子在包合物中存在明显的离子配对作用,阴离子主要以阳离子的配对作用存在.通过对包合物Na+X-/H的结构参数、自然键轨道(NBO)以及结合能分析可知,第1种包合方式更有利.研究表明脲基取代的二(9-冠-3)杯[4]芳烃衍生物可成为有效的离子对识别受体,研究结果进一步加深了杯芳烃类受体对离子对识别机理的认识,为实验上设计合成新型离子对受体提供了理论依据.     

Selective detection of cesium by a water-soluble fluorescent molecular sensor based on a calix[4]arene-bis(crown-6-ether)

A tetrasulfonated calixarene with two appended crowns, each including a dioxycoumarin fluorophore, is highly soluble in water and shows excellent selectivity for cesium ions.     

Effects of methylation at position 2 of cation ring on rotational dynamics of imidazolium-based ionic liquids investigated by NMR spectroscopy: [C4mim]Br vs [C4C1mim]Br

We investigated the rotational dynamics of two imidazolium-based ionic liquids, 1-butyl-3-methylimidazolium bromide ([C(4)mim]Br) and 1-butyl-2,3-dimethylimidazolium bromide ([C(4)C(1)mim]Br), to reveal the effects of methylation at position 2 of the imidazolium ring (C(2) methylation). The rotational correlation time (τ(local)) for each carbon in the cations is derived from the spin-lattice relaxation time of (13)C nuclear magnetic resonance. The τ(local) results obtained here provide three principle insights into the rotational dynamics of ionic liquids. First, all τ(local) values for [C(4)C(1)mim]Br are greater than those for [C(4)mim]Br owing to a viscosity increase due to C(2) methylation. Second, the rate of change in τ(local) on C(2) methylation differs among the carbons in the cation, which indicates that each carbon has a different microviscosity. Third, the τ(local) increase in the (13)C at the root of the butyl group on C(2) methylation is very small compared to both intuitive prediction and the results from quantum chemical calculations. This indicates that the motion of the butyl group root in [C(4)C(1)mim]Br is not significantly inhibited by the methyl group at the position 2 of the imidazolium ring. The finding provides conclusive information on the origin of the increases in the melting point on C(2) methylation. Hunt previously found through calculation that decreases in entropy are caused by two factors, namely, reductions in the rotational mobility of the butyl group and in the number of stable anion interaction sites with C(2) methylation, resulting in an increase in melting point and viscosity. Our finding experimentally illustrates that the origin of the increases in melting point is not the inhibition of butyl group motion and that the reduction in stable anion interaction sites plays a major role in the increases. Additionally, it is suggested that the viscosity increase on C(2) methylation can be interpreted in the same manner.     

The glass transition and the distribution of voids in room-temperature ionic liquids: a molecular dynamics study

The glass transition in prototypical room temperature ionic liquids has been investigated by molecular dynamics simulations based on an Amber-like empirical force field. Samples of [C(4)mim][PF(6)], [C(4)mim][Tf(2)N], and [C(3)mim][Tf(2)N] have been quenched from the liquid phase at T = 500 to a glassy state at T ～ 0 K in discontinuous steps of 20 K every 1.2 ns. The glass temperature estimated by simulation (T(g) = 209 K for [C(4)mim][PF(6)], T(g) = 204 K for [C(4)mim][Tf(2)N], and T(g) = 196 K for [C(3)mim][Tf(2)N]) agrees semi-quantitatively with the experimental values (T(g) = 193÷196 K for [C(4)mim][PF(6)], T(g) = 186÷189 K for [C(4)mim][Tf(2)N], and T(g) = 183 K for [C(3)mim][Tf(2)N]). A model electron density is introduced to identify voids in the system. The temperature dependence of the size distribution of voids provided by simulation reproduce well the experimental results of positron annihilation lifetime spectroscopy reported in G. Dlubek, Y. Yu, R. Krause-Rehberg, W. Beichel, S. Bulut, N. Pogodina, I. Krossing, and Ch. Friedrich, J. Chem. Phys. 133, 124502 (2010), with only one free parameter needed to fit the experimental data.     

Comparing an ionic liquid to a molecular solvent in the cesium cation extraction by a calixarene: a molecular dynamics study of the aqueous interfaces

We report a molecular dynamics (MD) study of the interfacial behavior of key partners involved in the Cs(+) cation extraction by a calix[4]arene-crown-6 host (L), comparing an ionic liquid (IL) to a classical molecular solvent (chloroform) as receiving "oil" phase. The IL is composed of hydrophobic 1-butyl-3-methylimidazolium cations (BMI(+)) and bis(trifluoromethylsulfonyl)imide anions (Tf(2)N(-)) and forms a biphasic system with water. The simulations reveal similarities but also interesting differences between the two types of interfaces. Much longer times are needed to "equilibrate" IL systems, compared to classical liquid mixtures, and there is more intersolvent mixing with the IL than with chloroform, especially concerning the water-in-oil content. There is also some excess of the BMI(+) cations over the Tf(2)N(-) anions in the aqueous phase. Simulations on the Na(+)NO(3)(-) and Cs(+)NO(3)(-) ions show that they sometimes interact at the interface with the IL ions, forming hydrated intimate ion pairs, whereas they are "repelled" by the classical interface. The LCs(+) complex and L ligand also behave differently, depending on the "oil phase". They are better solvated by the IL than by chloroform and thus poorly attracted at the IL interface, whereas they adsorb at the chloroform interface, adopting well-defined amphiphilic orientations. The results are discussed in the context of assisted ion transfer and provide a number of arguments explaining the specificity and efficiency of IL based, compared to classical extraction systems.     

Sodium picrate effect on extraction of lanthanum and lutetium by aminophosphonate calix[4]resorcinarenes

Aminophosphonate calix[4]resorcinarene derivatives extract lanthanum and lutetium ions from aqueous solutions to chloroform much more efficiently than O,O-diethyl[(4-nitrophenyl)aminobenzyl] phosphonate does. In an excess of the metal ion in the aqueous phase with respect to the amounts of the extracting agent and sodium picrate, extraction occurs at the 1 : 1 molar ratio of the metal ion to extracting agent. In a twofold excess of the extracting agent and a considerable excess of sodium picrate over the metal ion, the composition of the extracted complex depends substantially on both the length of the alkyl substituent in the (AlkO)₂P(O) group in the extracting agent and the number of lanthanide.